J Surfact Deterg (2016) 19:249–263
DOI 10.1007/s11743-016-1787-x
ORIGINAL ARTICLE
A Simplified Methodology to Measure the Characteristic
Curvature (Cc) of Alkyl Ethoxylate Nonionic Surfactants
Silvia Zarate-Muñoz1 • Felipe Texeira de Vasconcelos1 • Khaing Myint-Myat1
Jack Minchom1 • Edgar Acosta1
Received: 8 June 2015 / Accepted: 5 January 2016 / Published online: 19 January 2016
Ó AOCS 2016
Abstract This work introduces a simplified methodology
for measuring the characteristic curvature (Cc) of com-
mercial alkyl ethoxylate nonionic surfactants using care-
fully selected reference surfactants and oils that produce
rapid and well defined separations in salinity scans. The Cc
of the commercial reference surfactants was calculated
using optimal salinities (S*) obtained from solubilization
parameter curves, from interfacial tensions (for a selected
system), and from emulsion stability tests. The latter pro-
vided a fast detection of S*, in a matter of minutes. The
calibrated Cc of the reference surfactants was subsequently
used to measure the Cc of various commercial alkyl
ethoxylate surfactants. The combination of mixtures of test
and reference surfactants and emulsion stability tests pro-
duced reproducible Cc values that could be obtained with
simple bottle tests and in a timely manner. The values
obtained using this methodology were cross-checked, and
proved to be consistent, when using different combinations
of reference surfactants and oils, and when conducted by
different individuals. The standard deviation of Cc from
these measurements was typically ±0.2 Cc units, but it
could be as large as 25 % of the Cc value for highly
hydrophilic surfactants. After comparing the values of Cc
obtained experimentally with values calculated from
nominal structures (via a group contribution model) it
Electronic supplementary material The online version of this
article (doi:10.1007/s11743-016-1787-x) contains supplementary
material, which is available to authorized users.
& Edgar Acosta
edgar.acosta@utoronto.ca
1 conditions where the emulsion or microemulsion phase
Department of Chemical Engineering and Applied
Chemistry, University of Toronto, Wallberg Building, 200
College Street, Toronto, ON M5S 3E5, Canada
•
became clear that there are differences between these
values, likely because of the polydispersity of alkyl
ethoxylate surfactants.
Keywords Characteristic curvature  Commercial
nonionic surfactants  Phase inversion  Emulsion stability 
Hydrophobicity  Microemulsion
Introduction
Microemulsions formulated with commercial nonionic
surfactants are found in drug delivery systems, detergents,
hair/skin care products, used in food processing, environ-
mental remediation, and protein extraction because of their
low toxicity, electrolyte resistance, and large solubilization
capacity and interfacial area [1–6]. Microemulsions are
systems containing surfactant, oil, and water (SOW) that
self-assemble into nanostructures that exist in thermody-
namic equilibrium due to the adsorption of surfactants at
the oil–water interface [1, 7].
The properties of microemulsions (lE) undergo signif-
icant changes around the phase inversion point. For
instance, the interfacial tension tends to reach ultralow
values, the emulsion stability is further reduced to a min-
imum, and important changes in oil and water solubiliza-
tion capacity, viscosity, and detergency performance take
place [8–11].
Microemulsions at the phase inversion point are known
as ‘‘optimal formulations’’; since they have been consid-
ered the best systems to displace oil in enhanced oil
recovery due to their ultra-low interfacial tension [12]. The
inversion occur are ‘‘optimal conditions’’, and include the
temperature, the salinity of the aqueous phase, the
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hydrophobicity of the oil, and the affinity of the surfactant
for the oil and/or for the aqueous phase. The Hydrophilic-
Lipophilic Difference (HLD) is a semi-empirical equation
that describes the combination of conditions that lead to the
phase inversion point in systems containing equal volumes
of oil and aqueous phases [13–16].
The HLD is a normalized expression found to represent
the change in the chemical potential when a surfactant
molecule is transferred from the aqueous phase to the oil
phase [17–19]. Positive values of HLD suggest the pres-
ence of water-swollen reverse micelles dispersed in an oil
continuous phase (w/o lE), whereas negative HLD values
indicate the formation of oil-swollen micelles distributed in
a continuous aqueous phase (o/w lE). The phase inversion
point is observed at an HLD value of zero, which corre-
sponds to the formation of a bicontinuous network of oil
and water channels.
For nonionic surfactants the HLD equation is expressed
as:
 
HLD ¼ bðSÞ  K  EACN þ Cc þ cT T  Tref  /ð AÞ
ð1Þ
where S is the salinity of the system in g of electrolyte/
100 mL, EACN is the number of carbons in the oil mole-
cule for linear alkanes, and an equivalent alkane carbon
number for non-alkane oils, T is the temperature of the
system, /(A) is a function that depends on the concentra-
tion of alcohol (hence ‘‘A’’), or more generally a cosur-
factant (zero if none added), and b, K, cT are constants that
depend on the surfactant used. The term b(s) accounts for
the salting out effect of the surfactant from the aqueous
phase when the electrolyte concentration increases,
K 9 EACN provides an indication of oil-oil interactions
and surfactant-oil interactions, and cT(T - Tref) provides
insight into the weakening of hydrogen bonds between the
ethylene oxide group of surfactant molecules and water at
higher temperatures [20].
The characteristic curvature (Cc) as a term was intro-
duced by Acosta et al. [21], considering the original sur-
factant parameter r, that quantifies the lipophilic and
hydrophilic nature of the surfactant [22]. Nevertheless,
given the curvature interpretation of HLD, i.e., HLD ¼
 Length of the surfactant tail
Radius solubilization [23], the surfactant parameter r was
renamed as Cc, describing at this point the net curvature of
the surfactant at the oil–water interface, normalized by the
length of the surfactant tail, at characteristic (reference)
conditions (T = 25 °C, EACN = 0, no salt or cosurfac-
tant). Consequently, the Cc describes not only the hydro-
philic/lipophilic nature of a surfactant, but the type of
nanostructures the surfactant is likely to form at the ref-
erence conditions. Negative values of Cc indicate the
presence of a hydrophilic surfactant that tends to form oil-
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J Surfact Deterg (2016) 19:249–263
swollen micelles, while positive Cc values, a lipophilic
surfactant that tends to form water-swollen reverse
micelles. The value of Cc can be considered a concept
parallel to the HLB for nonionic surfactants. In fact, linear
correlations between Cc and HLB exist for different sur-
factant families [21]. However, the Cc is a more generic
parameter, which is also compatible with the packing
factor concept that is typically used in characterizing the
type of structures formed by ionic surfactants and lipids
[21, 24].
The characteristic curvature of pure nonionic surfactants
has been calculated by means of a group contribution
correlation introduced by Acosta [20] that for linear alkyl
ethoxylates is:
Cc ¼ 0:28  NCS þ 2:4  NES ð2Þ
where NCS is the number of carbons of the surfactant
hydrophobic tail, and NES is the number of ethylene oxide
groups in the hydrophilic head.
The characteristic curvature of commercial surfactants
has not been reported, with some exceptions [21, 25, 26].
Additionally, r parameters of surfactants have been pub-
lished in the literature [27]. Considering that commercial
nonionic surfactants are usually polydisperse mixtures of
polyoxyethylene surfactant chains, the uncertainty in the
structure of commercial nonionic surfactants puts into
question the use molecular structure correlations to obtain
their Cc, such as the one proposed by Acosta for pure alkyl
ethoxylates. Consequently, there is a need for a more useful
approach to determine the Cc of commercial nonionic
surfactants.
The Cc of surfactants is measured in phase inversion
studies (phase scans), identifying the phase inversion
point of the SOW system (HLD = 0) as a function of a
scanning variable, e.g., temperature (Phase inversion
temperature, PIT), or salinity (optimal salinity, S*). The
PIT is one of the most common methods to detect the
phase inversion point of alkyl ethoxylate surfactants,
since temperature is a formulation variable that strongly
influences their phase behavior. Nevertheless, the PIT is
tracked by conductivity measurements that require spe-
cialized instrumentation and a precise interpretation of
conductivity curves [15, 28, 29].
The optimal salinity (S*) method has been used to
determine the phase inversion point, and the Cc of ionic
surfactants [21, 30]. This methodology includes the use of
a commercial reference surfactant that is mixed with a test
surfactant, whose Cc is to be measured. Castellino et al.
[26], made use of a reference nonionic surfactant
(C11.5E5) to determine the Cc of silicone alkyl polyether
surfactants from surfactant mixtures with silicone oils.
However, the Cc of the reference nonionic surfactant was
determined from molecular structure correlations [31].
J Surfact Deterg (2016) 19:249–263
Determining the optimal salinity of polydisperse non-
ionic surfactants, as opposed to ionic surfactants, is diffi-
cult and time consuming due to the formation of highly
stable emulsions or liquid crystals, preventing an accurate
and prompt detection of the phase inversion point [32, 33].
An alternative to deal with this problem has been the use of
alcohols that help promote phase transitions. However, the
addition of cosolvents is a confounding factor that may
influence the value of the optimal scanning variable (either
S* or PIT), and thus the value of Cc. Consequently, a more
convenient method is required to determine the Cc of
commercial nonionic surfactants. The method needs to
include a simple set of SOW systems capable of producing
clear and rapid phase separations without the use of addi-
tional ingredients or sophisticated equipment and thus,
allowing an easy identification of the phase inversion point.
The purpose of this work is to introduce a simplified
methodology to measure the characteristic curvature of
commercial alkyl ethoxylate nonionic surfactants. To
accomplish this task, readily available commercial refer-
ence surfactants were carefully selected in an effort to
circumvent the formation of stable emulsions typically
found in nonionic SOW systems. Acosta et al. [34],
observed that the stability of emulsions is associated with
the interfacial rigidity of the surfactant film, being larger
for surfactants with long hydrocarbon chains. Therefore,
short-chain, or long-chain but branched surfactants must be
selected to decrease the separation time. This work focused
in two C8-10 linear (DehydolÒ OD 5, and NovelÒ 810FD-
5), and a C13-branched (NovelÒ TDA-6) surfactants as
Fig. 1 Salinity scan for the
commercial alkyl ethoxylate
reference surfactant TDA-6
with hexanes as oil at 23.5 °C.
The concentration of NaCl in
g/100 mL is varied from left to
right (bottom). The
solubilization parameters for oil
(diamonds) and/or for water
(squares) were fitted with the
net average curvature (NAC)
model
251
references, since these short-chain and long-chain but
branched amphiphiles can accomplish fast separations even
when mixed with other nonionic test surfactants. Salinity
scans were subsequently conducted with the reference
surfactants using a variety of oils at different temperatures.
While most salinity scans carried out with nonionic sur-
factants require days—if not weeks—to generate clear
phase separations, these SOW systems produced sharp
phase transitions in a matter of minutes without the use of
alcohols.
The optimal salinities (S*) were detected after simulta-
neously mixing all the vials in the phase scan, and identi-
fying the formulation where the emulsion reached the
equilibrium lE phase volumes in the shortest time, as this
is observed at the phase inversion point [35, 36]. In the
past, this method has been used to obtain S* at very low
coalescence rates only in nonionic SOW systems contain-
ing cosolvents [37]. The optimal salinities found via
emulsion stability were cross-validated with S* obtained
from interfacial tension measurements (for a selected sys-
tem), and from solubilization curves that display the sur-
factant solubilization parameter (sp) as a function of the
salinity of the system. The solubilization parameter relates
the volume of oil or water that can be solubilized per
volume or mass of surfactant (see Fig. 1). The optimal
salinity (S*), corresponding to the electrolyte concentration
at which the maximum amount of oil and water is solubi-
lized per volume or mass of surfactant [13], was deter-
mined by adjusting the experimental sp data with the Net-
Average Curvature (HLD-NAC) model [20, 23].
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The optimal salinities (S*) of reference surfactants
obtained from a relatively simple set of phase scans with a
range of oils, temperatures and electrolyte concentrations
where used to calibrate the HLD parameters of the refer-
ence commercial surfactants. Subsequently, the reference
surfactants were used to calculate the Cc value of other
nonionic surfactant samples.
Experimental Section
Materials
Alkyl ethoxylate reference surfactants were kindly donated
by Sasol North America [NovelÒ 810FD-5 (810-5), 100 %
active, NovelÒ TDA-6 (TDA-6), 100 %], and BASF North
America [DehydolÒ OD 5 (OD-5), 100 %], and were used
without further purification. Commercial alkyl ethoxylate
surfactants with nominal structures C11.5E5 (100 %),
C13E8 (100 %), and the glycerol ethoxylate nonionic
surfactant C9GE6 (100 %) were provided by leading
manufacturers (brand names withheld to prevent commer-
cial inferences from this work), and were used as test
surfactants to cross-validate the Cc measurement method.
Food-grade commercial surfactants TweenÒ 20 (T20)
(100 %), TweenÒ 80 (T80) (100 %), SpanÒ 20 (S20)
(100 %), the ionic surfactant sodium dihexyl sulfosucci-
nate solution (SDHS *80 % solution in water) used to
determine EACN, cyclohexane (C99.5 %), decalin (dec-
ahydronaphthalene mixture of cis ? trans, 98 %), octane
(98 %), dodecane (C90 %), and hexadecane (C99 %) were
purchased from Sigma Aldrich (St. Louis, MO, USA).
Hexanes (n-hexane *62–95 %, isomers of methylpentane
\21 % and methylcyclopentane \17 %), pentane
(C98 %), and heptane (C99.5 %) were obtained from
Caledon Laboratory Chemicals (Georgetown, ON).
Reagent grade sodium chloride (Bioshop Canada Inc.,
Burlington ON) was used to adjust the salinity of deionized
water (\3 ls/cm). All chemicals were used as received.
Salinity and Temperature Scans
Microemulsions (lE) formulated with 2 mL of oil and
2 mL of aqueous phase were prepared by adding surfac-
tant(s), specific amounts of 30 w/v % NaCl solution,
deionized water, and oil to 2 dram flat bottom vials. In the
aqueous phase, the surfactant concentration was main-
tained at 10 wt%, whereas the amount of NaCl was varied
from 0 to 27 g/100 mL. Single surfactant scans were car-
ried out with each reference surfactant, while mixed sur-
factant scans were produced by combing a reference
surfactant with a test surfactant at different molar ratios,
maintaining the total surfactant concentration constant (10
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wt% in water). The salinity scans were also formulated
using different equivalent alkane carbon number (EACN
3–16) oils, one at a time. All formulations were mixed by
hand, turning over gently 20–25 times, and were left to
equilibrate at room temperature (recorded for each scan).
Temperature scans were performed with previously
formulated single surfactant salinity scans containing
higher flash point oils. All the vials contained in one scan
were simultaneously mixed and placed inside a water bath
(Brinkmann Instruments Inc., Westbury, New York) at
controlled temperature starting at 25 °C and up to 80 °C
(or below the flash point of the oil), with temperature
increments of 5 °C. The formulations were left to equili-
brate for 12–24 h before determining the phase inversion
point.
Optimal Salinity (S*) from Solubilization Curves
To obtain the optimal salinity (S*) via solubilization
curves, the surfactant solubilization parameter of oil (spo)
or water (spw) was calculated measuring the volumes of lE
and excess phase(s) produced in each formulation (vial) as
shown in Fig. 1. For the case of salinity scans performed at
room temperature, the volumes were determined from
image analysis of scan pictures. Briefly, pictures containing
4–5 vials were taken with a C-7070 Olympus wide zoom
digital camera placed in front of the vials with no tilt. The
pictures were analyzed in Corel PaintShopÒ Pro X6 soft-
ware by measuring the height of the lE and excess
phase(s) of each vial in pixels. In the case of salinity scans
with increasing temperature, the height of each phase
observed in middle phase bicontinuous lE was measured
using a MastercraftÒ electronic caliper with digital display
(measuring range 0–150 mm, resolution 0.01 mm, accu-
racy 0.02 mm). The uncertainty associated with the height
measurements was determined as ±0.5 mm, equivalent
to ±0.5 mL. Two important aspects were considered when
measuring the heights at elevated temperature. First, each
vial was removed from the bath for no more than 10 s to
perform the measurements since slight changes in tem-
perature can modify the lE phase behavior. Second, cau-
tion was taken in differentiating middle phase bicontinuous
lE from coacervate phases, the latter characterized by a
concentrated surfactant middle phase with little or no oil
solubilized. After all the measurements, the solubilization
parameter (sp) was obtained dividing the volume of oil or
water solubilized by the volume of surfactant added to the
formulation. The solubilization parameter of oil (spo) or
water (spw) from each formulation was plotted against the
electrolyte concentration (g/100 mL), and the solubiliza-
tion curves were fitted with the HLD-NAC model [20, 23].
The optimal salinity (S*) and the b/L parameter of the Net
and Average Curvature equations (see supplementary
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material) were fitted by minimizing the sum of squared
differences between the experimental and the predicted spo
or/and spw for each point, using the Solver tool from Excel.
Optimal Salinity (S*) from Interfacial Tension
Measurements
Interfacial tension measurements were carried out using a
University of Texas spinning drop interfacial tensiometer
model 500, manufactured by Temco Inc. Briefly, a
borosilicate glass tube was completely filled with the
excess aqueous phase extracted from an equilibrated
bicontinuous microemulsion vial. Approximately 4 lL of
the extracted excess oil phase was injected into the filled-
glass tube, followed by spinning, increasing the rpm until
the oil droplet expanded to a length *4 times its width,
and reached equilibrium. Under these conditions, the
interfacial tension was calculated as:
Dqx2 w3
cow ¼ ð3Þ
4 values. The standard deviation for all EACN measurements
where Dq is the density difference between the aqueous
and oil phases, x is the rotational velocity and w is the
width of the expanded oil droplet. To determine the opti-
mal salinity via interfacial tension, the values of interfacial
tension between the excess oil and aqueous phases was
measured for systems that produced middle phase
microemulsions. The optimal salinity corresponds to the
system with the lowest interfacial tension.
Optimal Salinity (S*) from Emulsion Stability
providing a broad EACN window (*3–16). Furthermore,
decalin was included in the selection for having a high flash
point, thus allowing for high temperature scans. The EACN
of decalin was measured along with cyclohexane and a set
of linear alkanes and isomer mixtures using salinity scans
with sodium dihexyl sulfosuccinate (SDHS, Cc = -0.92
[21]). The use of SDHS as a reference surfactant to
determine the EACN of oils as polar as chlorinated sol-
vents, and as hydrophobic as motor oils, squalene, and
silicone oils has been reported in the literature [26, 39, 40].
The EACN values were calculated using the HLD equation
for ionic surfactant systems at 25 °C, with K = 0.17
(typical for ionic lE), without cosurfactant:
HLD ¼ 0 ¼ lnðS Þ  K  EACN / ðT  25Þ þ Cc ð4Þ
Additionally, the EACN of hexadecane was determined
in mixtures with 50 % of hexanes, using the linear mixing
P
rule EACNmixture ¼ Xi  EACNi , where Xi is the vol-
ume fraction of oil i. Table 1 presents the optimal salinities
and the measured EACN of all oils, including the literature
was ±0.2 units. The mean EACN values for C5–C8 alkanes
were in agreement with the number of carbons in the
molecule, according to the definition of alkane carbon
number [41–44]. Moreover, the EACN obtained for hex-
anes agreed with the number of carbons in the linear
molecule, regardless of the percentage of isomers in the
commercial sample.
Optimal Salinity (S*) via Emulsion Stability,
Interfacial Tension and Solubilization Curves

To determine S* using the emulsion stability method, all In order to determine if the phase inversion point (S*) of
vials contained in one salinity scan were simultaneously the commercial alkyl ethoxylates OD-5, 810-5, and TDA-6
mixed and left to equilibrate at room temperature on a flat
surface. The time to separate the excess phases (i.e., the
time when the separation front reached its stable position
[38]) in each formulation was recorded, and the optimal Table 1 Experimental and literature EACN values of oils studied
salinity (S*) was identified as the middle phase bicontin- Oil S* (25 °C) EACN measured EACN
uous lE where the excess phases separated in the shortest in this work literature
time. It is important to note that all the vials contained in
Cyclohexane 4.4 3.3 3a, 3.5b
the scan must be subjected to the same mixing conditions
Pentane 6.0 5.1 5c
since the coalescence of particles can be affected by the
Hexanes 7.0 6.0 6c
mechanical energy input [38].
Decalin 7.3 6.3 n/a
Heptane 8.0 6.8 7c
Octane 9.0 7.5 8c
Results and Discussion
Dodecane 20 12 12c
Choice of Reference Oils Hexadecane 16 16 16c
n/a not available
a
To investigate the influence of different equivalent alkane From Ref. [43]
b
carbon number (EACN) oils on the S* of each surfactant, From Ref. [44]
cyclohexane, dodecane and hexadecane were selected for c
From Refs. [41, 42]

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Fig. 2 Optimal salinities (S*) obtained via emulsion stability (top)
and solubilization parameter (bottom) methods for the reference
surfactant OD-5 with hexanes as oil at room temperature (22 °C)
used as reference surfactants was accurately determined by
the emulsion stability method, the optimal salinities (S*)
obtained from solubilization parameters were compared
with the S* obtained from coalescence rates, and S*
obtained from interfacial tension measurements (for the
OD-5 system only).
Figure 2 shows the S* values obtained with the solubi-
lization parameter and emulsion stability methodologies
for the reference surfactant OD-5 at room temperature
(22 °C) and hexanes as the oil phase. For the emulsion
stability method, a plot of salinity versus coalescence time
showed a deep minimum at 17 g/100 mL of NaCl corre-
sponding to S*, where the excess phases separated in less
than a minute. In the vicinity of S*, three middle phase
bicontinuous lE reached equilibrium in approximately
1.5 h. The fitting of the experimental solubilization
parameter data using the net average curvature model
(NAC) on the other hand, provided an S* value of 16.6 g
NaCl/100 mL, consistent with the S* obtained from the
emulsion stability method for this reference surfactant.
Additionally, Table 2 presents the interfacial tension
measurements of all middle phase bicontinuous
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Table 2 Interfacial tension between the excess phases of middle
phase bicontinuous lE of OD-5 reference surfactant with hexanes
Salinity (g/100 mL) Interfacial tension (mN/m)
16 0.0048
17 0.0065
18 0.0083
19 0.0117
microemulsions formed with OD-5, hexanes and aqueous
at room temperature (22 °C). As shown in Table 2, there is
not an evident minimum interfacial tension point (S*) that
can be obtained for this system, particularly considering
that at this range of interfacial tension, the error in the
measurement is close to 0.002 mN/m. Nevertheless, the
lowest measured value also corresponded to a value of 16 g
NaCl/100 mL.
Reflecting on the feasibility of the interfacial tension,
solubilization parameter and emulsion stability method-
ologies to determine the optimal salinity (S*), the emulsion
stability method is a simpler and faster alternative for
determining S*, and as precise as the interfacial tension
and solubilization curves if homogeneous mixing condi-
tions are followed. Nevertheless, it could only be per-
formed at room temperature unless modifications to the
equipment can be carried out. The interfacial tension
method, in contrast, requires time and expertise to perform
the measurements. Moreover, to determine S* via solubi-
lization curves, the volumes of lE, and excess phases of
each flat bottom vial from a phase scan need to be deter-
mined, which also involves supplementary time and
resources. It is important to note that solubilization
parameters are calculated assuming that all surfactant
remains in the lE phase (spo = volume of oil/volume of
surfactant, and spw = volume of water/volume of surfac-
tant), however, the partition of surfactant between the oil
and aqueous phases may be important.
The Optimal Salinity (S*) of Reference Surfactants:
Influence of EACN
Figure 3 shows optimal salinities (S*) of the reference
surfactants OD-5, TDA-6, and 810-5 obtained via emulsion
stability and solubilization parameter methods as a function
of the EACN, using cyclohexane (EACN = 3.3), hexanes
(EACN = 6), decalin (EACN = 6.3), dodecane
(EACN = 12), and hexadecane (EACN = 16) as oils at
room temperature (25 °C). As showed in Fig. 3, the S*
determined with the emulsion stability and solubilization
parameter methods were in close agreement and followed
the expected linear trend.
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Fig. 3 Optimal salinities (S*) with different oils (EACN = 3–16) for
a OD-5, b TDA-6, and c 810-5 reference surfactants obtained via
emulsion stability (squares) and solubilization parameter (circles)
methods at room temperature (25 °C)
For all reference surfactants, the use of higher alkane
chain oils required larger electrolyte concentrations to shift
from o/w lE to w/o lE at room temperature. This situation
is noticeable for the reference surfactants OD-5 and 810-5,
where only o/w lE were obtained with hexadecane
(EACN = 16) at room temperature. The use C3-C6
(equivalent) alkane oils on the other hand, provided tran-
sitions within a suitable salinity window (5–10 g NaCl/
100 mL). However the shift from o/w to w/o lE in systems
containing higher alkane chain oils may have been
255
achieved using salts with a larger salting out effect
according to the Hofmeister series, i.e., ammonium sulfate.
The Phase Inversion Point of Reference Surfactants:
Effect of Temperature
After observing the behavior of the commercial alkyl
ethoxylates used as reference surfactants with different
oils, the effect of temperature on the phase inversion point
(S*) of OD 5, TDA-6, and 810-5 was studied using decalin,
dodecane, and hexadecane as oils due to their higher flash
point compared to cyclohexane and hexane. In this case,
the optimal salinities (S*) were determined from solubi-
lization parameter curves by measuring the volumes of the
top middle and bottom excess phases from all middle phase
bicontinuous lE at each temperature. As shown in Fig. 4,
S* decreases in linear fashion with increasing temperature
for all reference surfactants. Slight deviations from lin-
earity were observed for the reference surfactant TDA-6
with decalin and hexadecane, where the formation of
stable emulsions with increasing temperature introduced
uncertainties in the identification of S*. For the reference
surfactants OD-5 and 810-5, a correlation coefficient above
95 % was obtained with all oils tested.
Calibration of the HLD Parameters
for the Reference Commercial Nonionic Surfactants
The preceding phase behavior studies using the reference
surfactants and oils with EACN from 3 to 16 at different
temperatures allowed us to establish a reference system
that can be used to determine the Cc values of other
commercial nonionic surfactants using the HLD equation.
To this end, it was necessary to obtain the constants K, b,
cT, and Cc that are specific of each reference surfactant.
The optimal salinities of the reference surfactants obtained
from solubilization curves with different oils and temper-
atures were compared with the S* calculated using the
HLD framework. Using the Solver tool from Excel, the
values of K, b, cT, and Cc were fitted by minimizing the
sum of the squared differences between the experimental
and predicted S* for each data point. Figure 5 shows the
linear regression curves and the experimental data for the
reference surfactants OD-5, TDA-6, and 810-5.
As shown in Fig. 5, the R2 correlation coefficient for
TDA-6 and 810-5 was above 0.95 of the prediction pro-
vided by the HLD equation. Slight deviations from lin-
earity were observed in the reference surfactant OD-5
where the R2 coefficient was approximately 0.93. This can
be related to random errors when determining the volume
phases of middle phase bicontinuous lE in the vicinity of
20 % salinity. Table 3 summarizes the calibrated values
of the HLD parameters K, b, cT, and the characteristic
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Fig. 4 Optimal salinities (S*) obtained with the solubilization
parameter method at different temperatures for a OD-5, b TDA-6,
and c 810-5 reference surfactants with decalin (triangles), dodecane
(squares) and hexadecane (diamonds)
curvature (Cc), with 95 % confidence of each parameter
for all reference surfactants. Additionally, the 95 % con-
fidence level of each HLD parameter was calculated via
multiple linear regression for normally distributed vari-
ables [45].
The values of K, b, and cT for all reference surfactants
are consistent with the range of values reported in the lit-
erature for alkyl polyoxyethylene surfactants [27, 46].
Moreover, similar values of the constant cT were obtained
for all reference surfactants, likely because they share the
same chemical nature (alkyl ethoxylates). These results are
123
J Surfact Deterg (2016) 19:249–263
Fig. 5 Optimal salinities (S*) obtained with the solubilization
parameter method, and calculated S* using the HLD equation for
nonionic surfactant systems (Eq. 1) for a OD-5, b TDA-6, and c 810-
5 reference surfactants with all oils tested (EACN = 3–16) at
different temperatures (RT to 80 °C)
in agreement with the slopes obtained from the linear
regression equations in Fig. 4 (slope = -cT/b) for each
reference surfactant (cT = 0.039 ± 0.009 for OD-5,
0.040 ± 0.009 for TDA-6, and 0.044 ± 0.008 for 810-5).
As a result, in the following section, it will be assumed that
the cT value found for all reference surfactants is also
applicable for mixtures of alkyl ethoxylate surfactants or
any polyethylene glycol amphiphile. This may not be case
in mixtures of reference surfactants with alkyl polygluco-
sides or polyglycerol nonionic surfactants, where the
J Surfact Deterg (2016) 19:249–263 257

Table 3 Calibrated HLD

Reference surfactant K b (g/100 mL)-1 cT (°C)-1 Cc
parameters for OD-5, TDA-6
and 810-5 reference surfactants OD-5 0.13 ± 0.02 0.12 ± 0.01 0.04 ± 0.01 -0.96 ± 0.17
TDA-6 0.15 ± 0.01 0.11 ± 0.01 0.04 ± 0.01 0.07 ± 0.09
810-5 0.17 ± 0.02 0.10 ± 0.01 0.04 ± 0.01 -0.45 ± 0.13

presence of hydrogen bond donors in the molecule can
change the surfactant-water interactions.
According to the Cc values shown in Table 3, the ref-
erence surfactant OD-5 (C8-10E4.5) is more hydrophilic
than 810-5 (C8-10E5), whereas the nominal structure
apparently contradicts this finding. A possible explanation
to this unexpected behavior is the fact that commercial
surfactants have a polydisperse distribution of EO groups
and different alkyl chain distribution.
Based on the measured Cc values of the reference sur-
factants, this simplified method includes reference surfac-
tants with degrees of hydrophobicity ranging from the
more hydrophobic TDA-6, to the intermediate 810-5, to the
more hydrophilic OD-5, which may be advantageous for
characterizing commercial surfactants with a wide range of
hydrophobicity.
Applying the Simplified Method to Measure the Cc
of Commercial Nonionic Surfactants
In order to test the ability of the simplified method to
measure the Cc of different commercial alkyl ethoxylates
using the HLD equation, the calibrated Cc, b, and cT values
of the reference surfactants were used to determine the Cc
of a series of commercial alkyl ethoxylate nonionic sur-
factants using the HLD framework. Mixed surfactant scans
were prepared using oils with EACN values from 3.3 to
6.3, and combinations of a reference and a test surfactant in
different ratios in the aqueous phase in order to obtain a
shift in optimal salinity as a function of mole fraction (in
the mixture of surfactants) of the surfactant tested (Ytest).
Optimal salinities (S*) were determined through the solu-
bilization parameter and emulsion stability methods.
Considering that at the optimal formulation (HLD = 0)
with no cosurfactant added:
HLD ¼ 0 ¼ bðS Þ  K  EACN þ Cc þ cT ðT  Tref Þ
ð5Þ
The optimal salinity for a reference surfactant (rs) is:
ðKrs  EACNÞ  CCrs  cT ðT  Tref Þ
Srs ¼ ð6Þ
brs
Whereas for a mixture (mix) of reference and test
surfactant:
ðKmix  EACN Þ  CCmix  cT ðT  Tref Þ
Smix ¼ ð7Þ
bmix
If the values of K and b for the mixture are assumed to
be equal to those of the reference surfactant, Eqs. (6) and
(7) would give:
 
 
CCrs CCmix
Smix ¼ Srs þ ð8Þ
b
Although there is some evidence of non-ideal behavior
in mixtures of nonionic surfactants with short hydrophobic
tails at the critical micelle concentration (CMC) [47, 48], a
linear mixing rule can be justified for mixtures of surfac-
tants at concentrations well beyond the CMC, where most
of the surfactant is in micelles:
CCmix ¼ Ytest Cctest þ ð1  Ytest ÞCCrs ð9Þ
In the linear mixing rule above Ytest is the molar fraction
of the test surfactant calculated on the bases of the ratio
between the moles of test surfactant and the total moles of
surfactants in the sample (moles of test and reference
surfactant). Combining Eqs. 8 and 9:
 
  CCrs CCtest
Smix ¼ Srs þ Ytest ð10Þ
b
Rearranging:
  
Smix  Sref
CCtest ¼ CCref  b ð11Þ
Ytest
Greater accuracy may be gained if the values of K, b,
and cT of the test surfactant are obtained by means of
regression analysis. In this case, the HLD equation for the
mixture of surfactants at the phase inversion point is:
0 ¼ HLDmix ¼ HLDrs  Yrs þ HLDtest  Ytest ð12Þ
where HLDtest contains the parameters K, b, cT and Cc of
the test surfactant that can be fitted by minimizing the sum
of the square differences between the experimental and
calculated HLD for the mixture of surfactants, provided
that the values of K, b, cT and Cc of the reference surfactant
are known. However, a minimum of 12 experimental Smix*
values for a given set of reference and test surfactants must
be measured to have a representative sample size.
The change in optimal salinities of mixtures containing
the reference surfactant OD-5 and commercial alkyl
ethoxylate surfactants with nominal structures C11.5E5,
C13E8, the glycerol ethoxylate C9GE6, and reference
surfactant TDA-6 as a function of mole fraction of the test
are shown in Fig. 6. The salinity of the mixtures linearly

123
258
Fig. 6 Optimal salinities (S*) for the test surfactants C11.5E5,
C13E8, C9GE6 and TDA-6 using OD-5 as a reference surfactant and
hexanes as oil at room temperature (22–23 °C)
correlates with Ytest (based on total moles of surfactant
mixture), with R2 values close or above the 95 % for the
test surfactants C9GE6, C13E8, and reference surfactant
TDA-6. These results further support the use of the linear
mixing rule (Eq. 9) to calculate the Cc of the test surfac-
tant. The R2 coefficient for the surfactant with nominal
structure C11.5E5 is close to zero since the slope of the
curve is close to zero, meaning that the reference surfactant
is not promoting the phase transition of the test, and con-
sequently the reference and the test surfactants have similar
values of Cc.
For each test surfactant, the slope of the linear equation
in Fig. 6 was used along with the calibrated Cc and b pa-
rameters for OD-5 to calculate the Cc of each test surfac-
tant using Eq. 11. Additionally, a regression analysis of the
slope of each curve was performed to determine the 95 %
confidence interval of the calculated Cctest.
To evaluate the reproducibility of this simplified
method, the characteristic curvatures of the different test
surfactants were measured by four different subjects,
using different reference surfactants and oils. Table 4
presents the Cc values obtained for all reference, single
and mixed surfactant systems. The calculated Cc values
using S* obtained via emulsion stability (CcE stability) and
solubilization parameter (Ccsp graph) methods appear in
separate columns, along with the calculated Cc using the
nominal structure (Ccmolec. struct.) and the group contri-
bution (Eq. 2).
For the reference surfactants OD-5 and 810-5, standard
deviations of 0.1–0.2 were obtained using the emulsion
stability and solubilization parameter methods. Neverthe-
less, the Cc calculated from the molecular structure differs
significantly from the experimental value for both surfac-
tants. Similar standard deviations of Cc of 0.1–0.2 were
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J Surfact Deterg (2016) 19:249–263
obtained for the reference surfactant TDA-6 using S*
obtained from emulsion stability and solubilization
parameter methods. The Ccmolec. struct for TDA-6 is closer
to the experimental Cc.
The linear correlations predicted by the HLD equation,
and the linear mixing rule (Eqs. 4 and 10, respectively)
were confirmed by the high R2 values of the linear
regressions discussed above. However, for highly
hydrophobic or hydrophilic test surfactants these linear
relationships can break down, particularly Eq. 10. In the
case of highly hydrophobic surfactants such as dodecanol
and oleic acid (in acidic media), these surface active spe-
cies can also partition into the bulk oil phase (i.e. behaving
like an oil co-solvent), thus the added molar fraction into
the system may not be equivalent to the molar fraction at
the interface. The same could occur with a highly hydro-
philic surfactant, but in this case, a good fraction of the
surfactant can act as aqueous co-solvent, or at least remain
in micelle form, but not adsorbed at the oil–water interface.
Examples of these types of surfactants are hydrophilic and
lipophilic linkers used to improve surfactant-water and
surfactant-oil interactions respectively [49]. However, even
for C9GE6, which could be classified as a hydrophilic
linker, linear correlations were obtained with all reference
surfactants, using cyclohexane and hexanes as oils.
For C9GE6, a Cc *-3.3 is obtained when averaging
the Cc values for this surfactant reported in Table 4, except
for those obtained using OD-5 as reference surfactant. For
C9GE6, the molecular group contribution (Eq. 2) predicted
a less hydrophilic surfactant with a Ccmolec. struct approxi-
mately -1, not considering the contribution of the glycerol
group. A similar situation can occur with the commercial
branched surfactant C13E8, where an experimental
Cc approximately -1.2 indicated a slightly more
hydrophobic surfactant compared to the predicted Cc value
using the molecular structure correlation without consid-
ering the effect of branching (Ccmolec. struct approximately
-1.96).
More negative Cctest values were obtained with the
reference surfactant OD-5, compared to those obtained
with 810-5 and TDA-6 as references, in almost all mixed
surfactant systems. This is likely due to the low K and more
negative Cc of OD-5. Due to its highly hydrophilic nature,
less optimal salinities were found with OD-5 than with the
other reference surfactants, situation that might have led to
slightly biased parameters, particularly the value of K.
The difference between the Cc determined experi-
mentally and the values obtained from molecular
structure correlation are likely due to the polydispersity
of the ethylene oxide groups in commercial alkyl
ethoxylate surfactants. The catalyst-based process for
the ethoxylation of alcohols produces a mixture of oli-
gomers with a Poisson’s distribution [50], having an
J Surfact Deterg (2016) 19:249–263 259

Table 4 Characteristic curvature (Cc) of alkyl ethoxylate nonionic surfactants

Surfactant Processed by Oil T (°C) Reference surf. Characteristic Curvature (Cc)
TE. stability Tsp CcE. stability Ccsp Ccmolec. struct.

OD-5 Subject A Cyclohexane 21.5 n/d n/a -0.87 n/d C8–C10 alcohol
Hexane 21.5 22.4 n/a -1.00 -1.10 ethoxylate 4.5EO
Decalin 21.5 n/d n/a -0.96 n/d (C9E4.5)
Subject B Cyclohexane 22.7 22.1 n/a -0.92 -1.05 0.42
Hexane 22.7 22.1 n/a -0.93 -1.23
Decalin 22.7 22.9 n/a -1.01 -1.19
Subject C Cyclohexane 22.9 22.7 n/a -0.93 -0.88
Hexane 22.9 22.3 n/a -0.94 -1.13
Decalin 22.9 22.7 n/a -1.02 -1.05
Dodecane 22.9 21.5 n/a -1.06 -0.93
810-5 Subject B Cyclohexane 22.1 21.4 n/a -0.30 -0.37 C9 alcohol
Subject C Hexane 23.4 21.9 n/a -0.30 -0.51 ethoxylate 5EO
Subject B Decalin 22.3 21.9 n/a -0.40 -0.46 (C9E5)
Subject B Dodecane 21.7 21.4 n/a -0.50 -0.68 -0.08
Subject C Hexadecane 21.7 21.7 n/a n/a n/a
TDA-6 Subject D Cyclohexane 23.5 22.4 n/a 0.01 0.14 Tridecyl (C13)
Subject D Hexane 23.5 22.4 n/a -0.09 -0.02 branched alcohol
Subject C Hexane 23.9 22.9 OD-5 -0.5 ± 0.2 -0.1 ± 0.2 6EO
Subject D Decalin 23.5 22.5 n/a 0.07 0.20 (C13E6)
Subject D Dodecane 23.5 22.4 n/a -0.23 -0.08 0.04
Subject D Hexadecane 23.5 21.1 n/a -0.02 0.09
C11.5E5 Subject D Cyclohexane 24 n/d n/a -0.85 n/d C11–C12 alcohol
Subject D Hexane 24.4 n/d n/a -0.97 n/d Ethoxylate 5EO
Subject D Hexane 21.1 21.9 OD-5 -1.1 ± 0.4 -1.0 ± 0.2 (C11.5E5)
Subject B Decalin 22 n/d n/a -1.10 n/d 0.62
C9GE6 Subject D Cyclohexane 24.3 n/d TDA-6 -3.6 ± 0.7 n/d C8–C10 glycerol
Subject B Cyclohexane 21.7 21.9 810-5 -3.6 ± 0.7 -3.5 ± 0.5 ethoxylate 6EO
Subject B Hexane 22.5 21.5 OD-5 -5.1 ± 1.3 -4.2 ± 1.1 (C9GE6)
Subject C Hexane 21.5 21.3 810-5 -2.9 ± 0.6 -3.1 ± 0.3 -1.08
C13E8 Subject D Cyclohexane 24 n/d TDA-6 -1.0 ± 0.1 n/d Tridecyl (C13)
Subject C Cyclohexane 23.3 n/d OD-5 -1.4 ± 0.1 n/d branched alcohol 8EO
Subject C Hexane 23.9 22.6 OD-5 -1.9 ± 0.2 -1.5 ± 0.1 (C13E8)
Subject C Hexane 22.5 22.1 810-5 -1.1 ± 0.1 -0.8 ± 0.1 -1.96
n/a not applicable, n/d not done

average peak value that corresponds to the nominal
structure given in the product information. Nevertheless,
this average peak value of ethoxylate units represents
only about 30 % of the active ingredients, with 60 %
distributed among structures within ±1 ethoxylate unit
of difference from the peak value, and about 10 % of
components with low ethoxylate units [51, 52]. More-
over, a difference of two ethoxylate units in the struc-
ture of an alkyl ethoxylate surfactant is likely to
produce a change in the Cc of two units according to
the correlation given in Eq. 2 [20].
Accurate predictions of the phase behavior of nonionic
SOW systems can be carried out using the HLD if an
accurate value of the Cc of a surfactant can be provided.
The method proposed in this work can be used to determine
the Cc of a variety of commercial nonionic surfactants
using readily available commercial reference surfactants.
Cross-checked results demonstrate that although the poly-
dispersity of commercial reference surfactants may give
rise to partition phenomena when using different oils and
temperatures, the reliability of the Cc measurements was
not affected when using the reference surfactants and oils.

123
260
Fig. 7 Optimal salinities (S*) determined via emulsion stability tests
at room temperature (22–25 °C) for S20 test surfactant using OD-5 as
a reference surfactant with hexanes as oil, and T20 and T80 test
surfactants with TDA-6 reference surfactant and cyclohexane as oil
Comparison with Alternative Methods for Cc
Determination
To investigate the correspondence between the Cc values
of commercial nonionic surfactants measured in salinity
scans and emulsion stability tests, with the values obtained
from temperature scans and conductivity measurements,
the Cc of S20, T20 and T80 food grade surfactants were
measured in mixed salinity scans at room temperature
(23–25 °C) with the reference surfactants TDA-6 and OD-
5, using cyclohexane and hexanes as oils. The change in
optimal salinities (S*) as a function of the mole fraction of
each food grade commercial surfactant is shown in Fig. 7.
Additionally, PIT data for the same food grade surfactants
(not the same surfactant source) was determined via tem-
perature scans, with conductivity measurements, by Onti-
veros et al. [53] in mixtures of a pure C10E4 reference
surfactant and n-octane as oil. The PIT for these systems is
presented as a function of mole fraction of the test sur-
factants in Fig. 8.
The characteristic curvatures of S20, T20, and T80 test
surfactants measured with the simplified method (salinity
scans/emulsion stability) and temperature scans/conduc-
tivity tests were subsequently calculated with the slope of
the curves in Figs. 7 and 8 respectively, following the
methodology described previously but using a modified
form of Eq. 11. Considering the PIT values of the reference
and mixed surfactant system (Tref*, Tmix*, respectively):
  
 ethoxylates (Eq. 2), the Cc of T20 should be approximately
Tmix  Tref
CCtest ¼ CCref   cT ð13Þ
Ytest
To interpret the data of Ontiveros et al., a Cc of the pure
C10E4 reference surfactant calculated using the group
contribution method (Eq. 2, Ccref = 1.2), and a value of
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J Surfact Deterg (2016) 19:249–263
Fig. 8 Phase inversion temperature (PIT) as a function of mole
fraction of S20, T20 and T80 test surfactants. PIT data from Ontiveros
et al. [53]
Table 5 Characteristic curvature (Cc) values calculated with the PIT
and simplified methodology
Surfactant CCaPIT CcSimpl. methodology CcbEACNscan
S20 4.1 3.5 3.5
T20 -3.2 -4.4 -7.9
T80 -3.2 -3.0 -3.7
a
Calculated with PIT data from Ontiveros et al. [53]
b
Reported by the 30-day formulation challenge consortium [54]
cT = 0.06 valid for most nonionic surfactants [27] were
used. Table 5 shows the Cc values obtained with the sim-
plified methodology and those calculated from the PIT data
detected via conductivity measurements obtained when
conducting temperature scans. Table 5 also includes Cc
values reported by the 30-day formulation challenge con-
sortium that used combined EACN/salinity scans to obtain
the Cc values of test surfactants, without using a reference
surfactant [54]. The Cc value for S20 and T80 are con-
sistent among the three sources, considering that the
deviations in the Cc values could be as large as 25 % of the
measured value. The biggest difference among the three
measurements is for T20. To try to understand which
measurement might be more reliable, we can look at the
value of Cc for T80. The main difference between TweenÒ
surfactants is that T20 has a dodecyl tail group (12 carbons)
and T80 has an oleyl tail (18 carbons with one double
bond). As per the group contribution model for pure alkyl
-1.7 units more negative than the Cc of T80 (6 carbon
difference in tail length, at 0.28 Cc units per carbon). The
PIT data shows that the Cc of T20 and T80 are almost the
same, which does not reflect the difference in the chain
length of these two surfactants. The EACN scan method
J Surfact Deterg (2016) 19:249–263
produced a difference in Cc of -4.2 units between T20 and
T80, whereas the simplified method produced a difference
of -1.4, closer to the expected difference of -1.7 pre-
dicted by the group contribution model.
Estimated Equivalent Alkane Carbon Numbers
(EACN) with Reference Nonionic Surfactants
The preceding sections considered the use of the simpli-
fied methodology of emulsion stability with short tail
reference surfactants to measure the characteristic cur-
vatures of nonionic surfactants. In principle, this
methodology can also be used to determine the EACN of
oils, knowing the HLD parameters for a reference sur-
factant. The literature reports the use of PIT to obtain the
EACN of oils or oil mixtures with pure nonionic surfac-
tants [55–57]. In this section, we explore the potential use
of the simplified methodology to determine the EACN of
unknown oils.
It has been suggested that commercial nonionic surfac-
tants can introduce potential errors in EACN measurements
due to their partition into the oil phase [19, 58, 59]. This
phenomenon can change the nature of the oil phase by
turning it more polar, and thus, producing a systematic
error in the measurement of Ccs, or EACN. The reasoning
behind this potential issue is sound, and was also explored
within this section. Table 6 introduces the optimal salini-
ties (obtained via emulsion stability) for the commercial
reference nonionic surfactants OD-5 and TDA-6 with
various oils. The first of the estimated EACN values was
determined using the HLD parameters (Cc, K, cT, b) for
each surfactant listed in Table 3. It is clear from Table 6
that the values of EACN for the alkanes tend to be over-
estimated in most cases, suggesting a bias in the mea-
surement. To assess the potential magnitude of the bias in
the measured characteristic curvatures, the Cc values of
OD-5 and TDA-6 were fitted to minimize the square
deviations in EACN. The re-calibrated values of Cc for
both surfactants were 0.2 units more hydrophilic (negative
shifts) than the values obtained in the optimization of the
preceding sections. It is however worth noticing that this
deviation is consistent with the level of uncertainty in the
measurement of Cc. One should note, as well, that using
the re-calibrated values one tends to obtain the largest
EACN deviations at lower EACN values. Considering that
Table 6 Experimental EACN
Oil EACNSDHS EACNOD-5
values of oils measured with
reference surfactants Pentane 5.1 6.3
Heptane 6.8 9.1
Octane 7.5 11
Dodecane 12 14
261
the precision in the Cc measurements is about ±0.2 units
and up to 25 % of the Cc value for the most hydrophilic
surfactants, and that k 9 EACN subtracts from Cc in the
HLD equation, then using an average value of K = 0.15,
a ±0.2 error in Cc correspond to a ±1.3 units of EACN.
The discussion above implies that this simplified
methodology might not be precise enough to measure the
EACN of oils, but fortunately, it also shows that potential
drifts in EACN introduced by partition effects play a rel-
atively minor role in the measured values of Cc. The rel-
atively minor role of partition in these studies can also be
traced back to the surfactant concentration used. Using a 10
wt% total surfactant concentration and 1:1 oil/water ratio
suggests that the concentration of surfactant monomers that
partition into the oil phase is relatively small, minimizing
their impact on the EACN. Using higher surfactant con-
centrations could produce substantial deviations associated
with partition effects. Based on potential partition effects,
ionic surfactants are more suitable alternatives for mea-
suring EACN values.
Conclusions
A simplified methodology for measuring the characteristic
curvature (Cc) of commercial alkyl ethoxylate nonionic
surfactants was introduced. The methodology calls for
determining the optimal salinity (S*) of mixtures of refer-
ence and test surfactants with different oils. The S*
obtained via resource-intensive solubility parameter and
interfacial tension methods were consistent with those
identified as the least stable emulsions. The emulsion sta-
bility method provided an accelerated detection of the
optimal salinity (S*), as long as homogeneous mixing
conditions for all formulations contained in the scans are
met. As the method only calls for phase scan studies
without specialized equipment, the testing protocol could
be adapted to be used in laboratory and field applications
where bottle tests are commonly used.
The polydispersity of ethylene oxide groups in com-
mercial nonionic surfactants limits the applicability of
group contribution correlations that use the nominal
structure to estimate their Cc, thus the need for methods
that can produce reliable measurements of Cc of com-
mercial nonionic surfactants.
EACNOD-5 adjusted EACNTDA-6 EACNTDA-6 adjusted
4.1 5.4 4.3
6.8 8.4 7.3
8.7 9.8 8.7
12 13 12
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Acknowledgments The authors thank Sasol North America, and
BASF North America for donating the reference surfactant samples.
This work was supported by the National Science and Engineering
Research Council of Canada (NSERC).
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Silvia Zarate-Muñoz is a Ph.D. student in the Department of
Chemical Engineering and Applied Chemistry at the University of
Toronto, Canada. She obtained her Bachelor’s and Master’s degree in
Chemical Engineering from the National Polytechnic Institute,
Mexico. Her research focuses on characterization and modeling of
complex nonionic surfactant and polymer systems for pharmaceutical,
food, and cosmetic applications.
Felipe Texeira de Vasconcelos was a summer research assistant in
the Laboratory of Colloid and Formulation Engineering at the
University of Toronto. He is currently pursuing food engineering
studies at the Federal University of Triangulo Mineiro (Brazil). His
research interests include complex coacervation, microencapsulation
and surfactants.
Khaing Myint-Myat was a summer research assistant in the
Laboratory of Colloid and Formulation Engineering, and is currently
a chemical engineering student at the University of Toronto. Her
research interests include microemulsion characterization.
Jack Minchom was a summer research assistant in the Laboratory of
Colloid and Formulation Engineering at the University of Toronto. He
is currently pursuing chemical engineering studies at McGill
University. His research interests include surfactant characterization
and synthesis/modeling of nanoparticles.
Edgar Acosta received his B.Sc. in chemical engineering from the
Universidad del Zulia (Venezuela) in 1996, and his M.Sc. and Ph.D.
in chemical engineering from the University of Oklahoma, Norman,
Oklahoma, in 2000 and 2004, respectively. He is currently a professor
in the Department of Chemical Engineering and Applied Chemistry at
the University of Toronto. His research encompasses the area of
colloids, complex fluids, and formulation engineering.
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