J Surfact Deterg (2017) 20:3–19
DOI 10.1007/s11743-016-1883-y
REVIEW ARTICLE
How to Attain Ultralow Interfacial Tension and Three-Phase
Behavior with a Surfactant Formulation for Enhanced Oil
Recovery: a Review—Part 3. Practical Procedures to Optimize
the Laboratory Research According to the Current State
of the Art in Surfactant Mixing
Jean-Louis Salager1 • Ana M. Forgiarini1 • Miguel J. Rondón1,2
Received: 28 June 2016 / Accepted: 19 September 2016 / Published online: 30 September 2016
Ó AOCS 2016
Abstract The minimum interfacial tension to be reached
in enhanced oil recovery by surfactant flooding implies the
attainment of a so-called optimum formulation. Part 1 of
the present review showed that this formulation may be
described as a numerical correlation between the involved
variables defining the oil, the water, the surfactant and the
temperature. Since it is unlikely to find a single surfactant
matching the crude/brine/T/P system characteristic of a
reservoir, a mixture of at least two surfactant species is
always used. The scan technique method to test the mixing
requires about ten interfacial tension or phase behavior
experiments and results in a single data. Hence, the scan
experiments have to be repeated many times to find a
minimum tension which is low enough, e.g. 0.001 mN/m,
for the given crude oil-brine system. Part 2 of this review
has shown that there are many formulation variables and
thus too many possibilities to easily choose experimental
conditions. Since there is no simple method to select two or
more surfactant species, the choice is made from partial
experience or intuition, and sometimes at random. The
laboratory time and cost to reach an appropriate optimum
formulation is often excessive. Part 3 of this review shows
that by cleverly using a three-surfactant mixture, the
experimental work to attain a very low interfacial tension
& Jean-Louis Salager
salager@ula.ve
& Ana M. Forgiarini
anafor@ula.ve
1
Lab FIRP, Universidad de Los Andes, Mérida, Venezuela
2
Present Address: GRM, Universidad Industrial de Santander,
Bucaramanga, Colombia
for a given reservoir case can be considerably reduced. It is
a matter of using the available information along a proper
sequential step by step path toward the optimum.
Keywords Enhanced oil recovery  Ultralow tension 
Surfactant mixture optimization
Basic Formulation Requirements for Enhanced Oil
Recovery
The most difficult and complex matter in enhanced oil
recovery by surfactant flooding is to attain a very low
interfacial tension, say down to 10-3 mN/m, under the
conditions of the reservoir, i.e. the type of crude oil, the salt
type and concentration, as well as temperature and
pressure.
Such an occurrence has been known to take place at the
so-called optimum formulation, which corresponds to an
exact balance between the affinity of the adsorbed sur-
factants for the oil and water molecules close to the
interface. This has been found to correspond to the
Winsor ratio R = 1 or to the surfactant affinity difference
SAD = 0 at which, both the interfacial tension is minimal
and a microemulsion-oil–water three-phase behavior
takes place, as reviewed in the first two parts of this series
[1, 2].
Such a physico-chemical balance has been written for
simple systems containing NaCl electrolyte and n-alkane
oil, as a general correlation for optimum formulation [3–5]
and later as a SAD expression [6] or its dimensionless
equivalent, the so-called hydrophilic-lipophilic deviation
HLD [7]. The HLD expression in which the effect of the
pressure [8–10] has been introduced for a wider general-
ization, is as follows:
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4 J Surfact Deterg (2017) 20:3–19
HLD ¼ SAD=RT ¼ ln S  k ACN  f ðAÞ þ r
 aT ðT  TrefÞ  bP ðP  PrefÞ ¼ 0
for ionic surfactants,
HLD = SAD=RT ¼ bS  k ACN  /ðAÞ þ b þ cT
ðT  TrefÞ  bP ðP  PrefÞ ¼ 0 for ethoxylated nonionics,
where S is the salinity (generally in NaCl wt%, sometimes
in wt% total dissolved solids—TDS—in case of an elec-
trolyte mixture), ACN is the alkane carbon number (re-
placed by the equivalent EACN for oils different from n-
alkane [11, 12]. T is the temperature, and P the pressure. r
and b are the characteristic parameters of the surfactant
substances adsorbed at interface. k, b, aT, bP and cT are
positive constants depending on the nature of the ingredi-
ents. f(A) and /(A) are alcohol cosurfactant contributions,
which are zero in the absence of alcohol, as is mostly the
case nowadays. Since most laboratory experiments are
carried out at atmospheric pressure, in what follows the
pressure term will be eliminated for the sake of simplicity.
These correlations, which are well satisfied for simple
systems [13–15], indicate that the attainment of an optimum
formulation depends on an exact balance between the con-
tributions to the interfacial interactions of the oil, brine, and
surfactant, as well as the temperature and pressure. What is
conceptually crucial in these expressions is that the effects
of the different variables are independent from one another.
However, in practice a crude oil contains many different
oils, the brine many electrolytes, and a commercial sur-
factant is always a mixture of species. This means that each
contribution is no longer a single term as indicated in the
previous equations. It is assumed that these equations can
be expressed as functions that render the effect of the
different component mixtures, as well as temperature and
pressure, provided that the independence of the terms is
satisfied. This has been shown to be quite probable from
the chemical potential analysis of the correlations [16].
HLD ¼ f1 ðsurfactant mixtureÞ þ f2 ðoil mixtureÞ
þ f3 ðsalinity mixtureÞ þ f4 ðTÞ þ f5 ðPÞ ¼ 0:
It is worth remarking that in a real petroleum reservoir
case, the oil and brine characteristics are fixed, as well as
the temperature and pressure. As a consequence, the values
of the corresponding functions f2–f5 are set and the chal-
lenge is to find a f1 (surfactant mixture) satisfying the
HLD = 0 Eq. (3), with a value of the interfacial tension as
low as possible.
This means that for the two classes of surfactants,
Eqs. (1) and (2) may be written as follows, where the right
term of the equation is constant once the petroleum reser-
voir is selected.
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r ¼  ln S þ k EACN þ aT ðT  TrefÞ þ bP ðP  PrefÞ
ð1Þ ¼ Constant, ð4Þ
b ¼ bS þ k EACN  cT ðT  TrefÞ þ bP ðP  PrefÞ
¼ Constant: ð5Þ
These equations can be written as a general expression
ð2Þ where the characteristic parameter of the surfactant is
called Cp, and where the constant, called CSYS, is the
characteristic of the system, that depends on the petroleum
reservoir conditions.
Equations (4) and (5) may be written as Eq. (6), where
CSYS is the constant defined in Eq. (7) by the (E)ACN,
salinity, temperature and pressure of the selected reservoir.
Cp ¼ CSYS ; ð6Þ
where:
CSYS ¼ k EACN  ðln S or bSÞ þ ðcT or  aT ÞðT  TrefÞ
þ bP ðP  PrefÞ: ð7Þ
Equation (6) expresses the condition to attain a mini-
mum tension. It requires a surfactant or a surfactant mix-
ture to have its characteristic parameter Cp exactly
matching the CSYS of the reservoir, as defined in expression
(7). How to attain the optimum formulation in practice, and
how to reach it with the best efficiency, i.e. with the lowest
interfacial tension, is the subject of the present article.
Characteristic Parameter for a Single Surfactant
or for Binary Mixtures
Let us first have a look at the surfactant characteristic
parameter Cp which appears in Eq. (6). In the past, sur-
factants have been characterized in different ways, starting
a long time ago with the hydrophilic-lipophilic balance
(HLB) introduced by Griffins [17, 18] and the critical
packing parameter (CPC) introduced by Israelachvili [19],
which are not going to be dealt with here, because they are
very approximate and are not useful to be applied in the
ð3Þ
known correlations for optimum formulation, as discussed
elsewhere [20].
Let us first discuss the case of anionic surfactants for
which Eq. (1) was empirically found to be quite exact in
the late 1970s [3, 15]. Expression (8) indicates the condi-
tion to reach an optimum formulation when one of the
formulation variables (salinity, ACN, ionic surfactant type
or temperature) is scanned, i.e. when it is changed con-
tinuously, whereas the three others are kept constant.
ln S  k ACN þ Cp  aT ðT  25Þ ¼ 0: ð8Þ
If the ACN is scanned and the salinity and temperature
are fixed in a selected reference state, typically Sref = 1
J Surfact Deterg (2017) 20:3–19
wt% NaCl and Tref = 25 °C, then the ACN in the scan for
which an optimum formulation is attained, so-called
ACN*, allows us calculate the characteristic parameter Cp,
Cp ¼ k ACN : ð9Þ
Many publications are found using an ACN scan or a
salinity scan in the studies in enhanced oil recovery
[21–23]. However, since the liquid alkane state corre-
sponds to a limited range from 5 to 16, in practice the
salinity scan is used in many studies with ionic surfactants
[24–28]. As a matter of fact it is easy to have a continuous
change in aqueous phase salinity, and it is less expensive
than using pure n-alkanes. The optimum salinity, generally
indicated with an asterisk, is expressed as its Naperian
logarithm lnS* because of the experimental accuracy of
Eq. (8) for ionic surfactants [3, 15].
When a reference is taken selecting a given n-alkane,
e.g. n-heptane for which ACNref = 7, and at reference
temperature Tref (usually ambient temperature 25 °C), then
the salinity at which optimum formulation takes place in
the scan S* allows to calculate the characteristic parameter
Cp. As Eq. (10) shows, the higher S* the more hydrophilic
the surfactant, i.e. the lower its Cp,
Cp ¼  ln S þ k ACNref þ aT ðT  TrefÞ
¼  ln S þ reference constant: ð10Þ
Consequently with selected ACNref and Tref, lnS* is a
direct and equivalent indication of the characteristic
parameter of an ionic surfactant.
With nonionic surfactants the same technique is used,
but this time mostly with temperature as the scanned
variable, and selected references Sref and ACNref. The
corresponding characteristic parameter has been called the
phase inversion temperature (PIT) or the HLB temperature
(THLB) as discussed elsewhere [4, 29–33].
In what follows, the surfactant characteristic parameter
is referred to as Cp, whatever way it is measured or esti-
mated. Equations (6) and (7) allow us to select the sur-
factant to attain an optimum formulation for a system
defined by the reservoir oil, salinity, temperature and
pressure. Since it is very unlikely to have a surfactant with
a characteristic parameter exactly matching the required
system characteristic CSYS, the optimum formulation is
attained in practice by mixing two or more surfactants. It is
worth remarking here that in real cases of surfactant mix-
tures, and in most commercial products, the Cp value
depends on the partitioning of the different species at the
interface, which has been found to depend on the surfactant
concentration a long time ago [3, 4, 15, 16, 33]. This will
not be discussed here, but this is why the actual Cp value of
a typical commercial surfactant or surfactant mixture must
be determined experimentally at a given surfactant con-
centration and water/oil ratio. The following surfactant
5
mixture discussions are thus implicitly carried out for
systems at constant surfactant concentration, typically
0.3–0.6 wt% as it is used in practice for EOR.
Let us first discuss the case of a mixture of two sur-
factants Surf1 and Surf2, with characteristic parameters
Cp1 and Cp2, one below and the other above the system
characteristic CSYS. The simplest expression to calculate
the characteristic parameter of the mixture CpMIX is the
linear average rule:
CpMIX ¼ x1 Cp1 þ x2 Cp2 ¼ x1 Cp1 þ ð1  x1 Þ Cp2 ¼ CSYS ;
ð11Þ
where the x are in theory the molar fractions of species 1
and 2 at the interface, with x2 = 1 - x1. However, since
this is not always easy to know, the x are often taken as the
weight fraction of the species incorporated in the system.
By the way, if the surfactants are relatively close, there is
no significant difference between the molar and weight
fraction. If the surfactants are actually commercial prod-
ucts, they are already mixtures and their molecular weight
is not very well known, so that the molar fraction is not
readily available and the x usually correspond to the weight
fractions.
In any case, the linearity of relation (11) has to be verified
versus the molar/weight fraction x. The work done in the
1970s indicated that in many cases an almost linear rela-
tionship was followed when the characteristic parameter was
expressed as ACN* according to Eq. (9). It was also the case
when the characteristic was expressed as LnS* as seen in
Fig. 1, then using Eq. (10) to relate Cp with lnS*, when
ACN and T are fixed. Other scan variables such as PIT or
ethoxylation degree have been used for nonionic surfactants
in many publications [4, 34–36]. All scans are basically
equivalent to calculate the surfactant characteristic parame-
ter, provided that Eqs. (4) and (5) are satisfied.
It can be seen in Fig. 1a that mixtures of anionic sur-
factants like petroleum sulfonate (TRS 10–80), alkyl ben-
zene sulfonate (ABS), alkyl orthoxylene sulfonate (AOXS)
and linear alcohol sulfate (LAS), in general follow a strict
linear mixing rule. It is worth noting that the difference in
slope is due to the fact that sulfonates and sulfates have a
different k value, as explained elsewhere [35, 36]. It is seen
in Fig. 1a that such a linearity is maintained in the lnS* plot,
when a petroleum sulfonate is mixed with up to 25 % of
nonylphenol ethoxylates which are much more hydrophilic.
In Fig. 1b it is seen that a mixture of two pure alkyl
orthoxylene sulfonates (C9AOXS and C15 AOXS) which
have a difference of six carbons in their main tail, shows a
slight non-linearity. Figure 1b also indicates that the mix-
ture of a petroleum sulfonate with a slightly hydrophilic
nonylphenol ethoxylate, exhibits a highly non-linear rule to
be discussed later.
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6 J Surfact Deterg (2017) 20:3–19

Fig. 1 Optimum formulation

for mixtures of commercial
surfactants, measured as the
optimum salinity expressed as
lnS*, with a typical case of
perfect matching (a) or
deviation (b) to the linearity
expressed in Eq. (11) Adapted
from previous publications
[15, 35, 36]

Fig. 2 Determination of the

optimum formulation in a two-
surfactant mixture according to
the surfactant 1 fraction x1, in
the case of a linear (a) or
approximately linear (b) mixing
rule

The cases of linear or almost linear mixing rules involve
some kind of collective average behavior of the various
ingredients in the mixture. The effects are shown in Fig. 2
schemes as the variation of the characteristic parameter Cp
for the mixture, versus Surf1 surfactant fraction x1 required
to attain the optimum formulation according to Eq. (11).
Figure 2a indicates a perfect linearity, while Fig. 2b indi-
cates a significant deviation in the optimum fraction x1 with
respect to the linear rule, as sometimes happens, in par-
ticular if Cp1 and Cp2 have quite different values.
An almost linear mixing rule is not always valid, and
some surfactant mixtures sometimes exhibit a completely
different behavior because association takes place between
the species involved. For instance, when anionic and
cationic surfactants mix they form a so-called catanionic
species. These associated species are much more
hydrophobic, because of the loss of a part or the totality of
the ionic charges in the combined head groups, and also
because they have a double tail [37–39]. They are not
discussed here because they are very likely to precipitate at
the concentration of interest and are thus not in gen-
eral appropriate for enhanced oil recovery applications.
As seen in Fig. 1b, a mixture of anionic and nonionic
surfactants can result in a significant deviation from a
linear mixing rule, which could however be controlled in
some enhanced oil recovery cases [35, 36]. Such anionic-
nonionic mixtures generally produce a decrease in surfac-
tant hydrophilicity because of some shielding of the ionic
group of one surfactant by the polyether chain group of the
other, as seen in Fig. 3b scheme. It is clear from the opti-
mum formulation variation in Fig. 3a that both anionic and
nonionic surfactants have roughly equal Cp values, since
the lnS* values for the pure components are essentially the
same. However, Fig. 3a indicates that the addition of only
20 % of nonionic surfactant results in a much lower lnS*,
i.e. a higher Cp for the mixture, as if about five more
carbon atoms were added to the anionic surfactant tail.
In Fig. 3c, d schemes, CpMIX  ½x1 Cp1 þ ð1  x1 ÞCp2 .
This particularly happens when the two characteristic
parameters Cp1 and Cp2 are close. Since the non-linearity
is considerable, CpMIX can be outside the Cp1–Cp2 range,
showing an interesting practical case in which there is a
central zone where the mixture characteristic parameter is
more hydrophobic than any of the components alone.

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J Surfact Deterg (2017) 20:3–19
Fig. 3 Determination of the
optimum formulation in a two-
surfactant mixture in case of a
strong interaction between the
components. a LnS* variation in
an anionic-nonionic mixture.
b Scheme of the interaction
between the anionic and
nonionic heads. c,
d Characteristic parameter of
the mixture CpMIX producing a
flat relatively wide optimum
formulation zone as in c and
even two different optimum
formulations as in d
Moreover, it can be seen that the CpMIX value may be
relatively insensitive to composition over some range in
this central zone in case (c), or that Eq. (11) can be satisfied
in two x1 values in case (d).
The data selected in Figs. 1b and 3a indicate that lin-
earity of the Cp mixing rule is not always granted, but that
it can happen in some limited range with anionic-nonionic
mixtures.
However and in order to recognize the difficulty in
mixing, it is worth comparing the data of Figs. 1b and 3a in
which the same nonionic ethoxylate is mixed with similar
petroleum sulfonates in a system with the same hydrocar-
bon (heptane), but with quite different results.
Figure 1b indicates that in the mixture of a relatively
lipophilic petroleum sulfonate (lnS* * 0) with a hydro-
philic ethoxylate (lnS* [ 2), the optimum salinity is
essentially constant up to 30–40 % nonionic. This absence
of a mixture effect in this range is probably due to the fact
that the slight increase in hydrophilicity produced by
adding the nonionic is compensated at first by the shielding
of the anionic group resulting in a decrease in its
hydrophilicity. Then, when the nonylphenol ethoxylate
interaction with the sulfonate no longer changes, e.g. above
30 % in the mixture in Fig. 1b, the nonionic hydrophilic
7
contribution appears to be very significant and the optimum
salinity increases sharply in a logarithmic fashion. It is also
worth remembering that the three-phase behavior range
considerably increases in this region as shown elsewhere
[35].
In Fig. 3a in which the used petroleum sulfonate is more
hydrophilic (lnS* * 1.4) than in Fig. 1b just a few percent
of the same nonionic considerably reduces the
hydrophilicity of the anionic. The shielding interaction
effect is thus much more important when the two surfac-
tants have a similar Cp as in Fig. 3c, d cases. As seen in
Figs. 1b and 3a an almost constant Cp value occurs over a
significant nonionic content range, i.e. before the excess
nonionic prevails at 50 % or more and a considerable
increases in hydrophilicity takes place. The almost constant
Cp zone brings some robustness to the formulation, an
effect which may be crucial when some spontaneous
change takes place during the flooding, such as a chro-
matographic separation of the surfactant species.
It is worth remarking that non-linear mixing with almost
constant Cp is not necessarily an inconvenience in
enhanced oil recovery. In effect, the presence of nonionic
ethoxylates can avoid the precipitation of anionics at high
salinity, and the fact that the resulting Cp is higher could
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8 J Surfact Deterg (2017) 20:3–19
increase the performance, as found in some cases reported
elsewhere [2]. As will be seen later in a proposed anionic-
nonionic example, an almost invariant performance when
the mixture changes may be advantageous in processes
such as the salinity gradient. On the other hand an anionic-
nonionic mixture can be made insensitive to temperature
[40], and to dilution [41], which could be an interesting
property for enhanced oil recovery and other applications.
Experimental Conditions
The reported experiments use commercial surfactants from
different brands manufactured by SASOL, CEPSA and
SHELL indicated by their generic formula. Crude oils are
characterized by their EACN and API number, and brines
by their electrolyte content. All experiments are carried out
without alcohol and at atmospheric pressure.
The performance is estimated either by the direct mea-
surement of the interfacial tension at equilibrium with a
spinning drop tensiometer made in our University, or by
the measurement of the solubilization of oil and water per
gram of surfactant, transformed in the equivalent interfa-
cial tension according to the previously discussed [2]
equivalence based on Chu Hu relationship [42]. Iso-tension
contours are drawn using interfacial tension data point
values in a network of locations in the ternary diagrams and
special scans.
Surfactant Mixture Scans
Finding an optimum formulation with a low interfacial
tension is the first condition to be satisfied in enhanced oil
recovery, and in practice it has to be done with a mixture of
two or more surfactants. The currently used surfactants
[43, 44] are generally commercial surfactants which are a
mixture of similar species with some distribution in the tail,
the head, or in both, as well as in the intermediate part for
extended surfactants. Consequently, they are certainly mix-
tures of mixtures. Nevertheless, the current trend is to mix
commercial products having different structures (e.g. alkyl
benzene sulfonates, internal olefin sulfonates, petroleum
sulfonates, alkyl polypropoxy sulfates or carboxylates, alkyl
ethoxylates, alkyl polyglucosides, etc.) with the purpose of
cumulating advantages and producing some synergy.
Mixing surfactants can satisfy other conditions, not only
cost issues, but also crucial worries such as avoiding pre-
cipitation. This is particularly important at high salinity (in
which case anionics tend to precipitate) or high tempera-
ture (when nonionics tend to become more hydrophobic
and phase separate at the cloud point). This is another
123
reason to mix different structures as discussed elsewhere
[44, 45].
Liquid crystal occurrence, which results in the formation
of a gel, also has to be avoided. In the first studies back in
the late 1970s an alcohol was generally added to a petro-
leum sulfonate to avoid liquid crystal or amorphous gel
formation, if it could not be eliminated just by an increase
in temperature. As discussed in the previous parts of this
review [1, 2], the current strategy is to use surfactants with
branched or ramified alkyl tails, and intermolecular mix-
tures, particularly of nonionics and anionics. In
intramolecular mixtures found in extended surfactants with
both ionic and nonionic parts [46–55], the first propylene
oxide units produce some disorder and are generally suf-
ficient to avoid the formation of rigid association and gels
at interface [56, 57].
This summary gives an idea on how to select the can-
didates for a mixture according to the last drawing in part 2
of the previous review [2], which recommend mixing many
different species, not only two, but at least three as will be
suggested next to increase the probability of improving
performance.
The second problem in enhanced oil recovery is to find
an optimum formulation in a scan with a minimum inter-
facial tension value c* as low as possible. Since there is no
obvious method to predict the performance at the optimum,
the current guidelines are Winsor’s trends to increase the
head and tail size of the surfactant(s) at the interface,
though not too much so as to avoid precipitation. The other
way is to generate a mixture synergy, which is still puz-
zling in practice and sometimes quite mysterious
[45, 58, 59].
Some models to estimate the performance as lower
tension or higher solubilization on scientific ground have
been proposed, e.g. HLD-NAC by Acosta [28, 60], Hel-
frich torque by Buijse and Fraaje [61, 62], or packing
parameter by Kunz [63]. They are related to interface
bending and curvature in bicontinuous systems found in
microemulsions at optimum formulation. They are mostly
based on the persistence characteristic length n introduced
by theoricists like De Gennes [64] and Strey [65, 66]. This
characteristic length was found to exponentially vary with
the interface rigidity constant j. When j is lower than a
critical value, the interface becomes wrinkled and exhibits
a somehow random shape and the resulting gain in entropy
in a bicontinuous microemulsion structure overrides the
loss of energy produced by an organized array like a
lamellar liquid crystal.
With the exception of a very simple case in which the
performance (as c* and n) has been precisely linked to
some formulation variables [13], there is still no way to
accurately predict how to improve the performance c* at
J Surfact Deterg (2017) 20:3–19
optimum formulation for a single surfactant type, and even
less for mixtures of different species.
As a consequence, the value of the minimum tension c*
has to be determined experimentally, by measuring either
the interfacial tension or the solubilization, in a sequence of
systems prepared along a formulation scan passing through
an optimum. A typical scan sequence contains about 10
formulations and will produce one performance index
noted for instance as log c* [2]. The formulation scan may
be carried out by changing any formulation variable, or
along a more complex path in the formulation variable
space as recently proposed [13].
In the case of a petroleum reservoir, the brine salinity,
the oil EACN, the temperature and the pressure are fixed,
hence the only variable left to adjust the formulation is the
surfactant characteristic parameter Cp. Since it is not likely
to find a surfactant with the Cp value exactly corresponding
to CpSYS, then, the surfactant mixture is the most logical
way of scanning the formulation from CpMIX [ CSYS to
CpMIX \ CSYS or vice versa.
For a binary mixture of two surfactants (called Surf1 and
Surf2), Eq. (11) is the linear approximation to be used in
what follows, provided that one of the Cp values is higher
than CpSYS and the other lower. Taking into account that
x2 = 1 - x1, Eq. (11) has a single solution x1 corre-
sponding to the minimum interfacial tension shown in
Fig. 4 as a typical example of a surfactant mixture scan,
x1 ¼ ðCSYS  Cp2 Þ=ðCp1  Cp2 Þ: ð12Þ
Fig. 4 Examples of the variation of the interfacial tension for two
surfactant mixture scans
9
Figure 4 shows the variation of the interfacial tension
with the mixture composition for two cases. Both curves
show that the interfacial tension undergoes through a
minimum at a certain mixture composition. It is worth
remarking that both the optimum formulation location and
the minimum tension value (so-called c* in what follows)
are different when the Guerbet extended surfactant (G C12
PO 20 S) is mixed with different surfactants, i.e. a linear
dodecyl alcohol sulfate (C12 LAS) or a dodecyl alcohol
ethoxylate (C12 EO8).
According to Eq. (12), in a scan including two surfac-
tants, only one optimum formulation is found after mea-
suring the equilibrium interfacial tension for typically 8–10
surfactant binary mixture compositions. The first scan has
to be carried with new surfactants, possibly one of them
already selected in a previous scan, if there was some
feeling that it was good, for instance because its minimum
tension was quite low in a salinity scan, or because it
occurred at a salinity not too different from the reservoir
case. The second scan will provide another c* value which
may be better or worse than the first one. Then another
binary mixture scan will be carried out and so on.
If the linear mixing rule is followed, as it may be
supposed as a first approximation, then the selection of
two surfactants to carry out a proper formulation scan
only requires one surfactant to be more hydrophilic and
the other more hydrophobic than a virtual surfactant
with characteristic parameter CpSYS calculated from
Eq. (7). The fact is that if the selection is made at
random, the next found c* could be arbitrarily better or
worse. The formulators knowledge of the literature
[43, 44, 67], his experience and expertise, and some-
times his intuition or his luck, seem thus to be the
driving forces to improve the c* value as the sequence
of scans is carried out.
The know-how reported in many references cited
previously in this series [2] indicates the basic Winsor
premises and several other trends, which could be used
to improve the performance [58] and moreover to avoid
problems like precipitation [68]. Nevertheless, since the
time and money spent in a series of scans is basically
proportional to the number of interfacial tension mea-
surements to be carried out, an efficient strategy would
be to warranty that some improvement in performance,
i.e. in c* value, is happening at each new scan. Also, it
is critical to minimize the total number of measurements,
avoiding random trials and using as much prediction as
possible in the sequence. The following section will
discuss why mixing three surfactants is likely to save
time and money by using a strategic path which con-
siderably reduces the number of interfacial tension
measurements.
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10
Mixing Strategy with Three Surfactants
It was seen in the second part of the review [2] that a
mixture with many different species of surfactants is
probably a good alternative. However too many surfactants
in the mixture would considerably increase the number of
compositions to be tested and thus could reduce the
experimental efficiency necessary to reach a solution
quickly.
Figure 5 shows a ternary diagram with mixtures of three
surfactants, called Surf1, Surf2, Surf3, in which the iso-
tension contours are indicated. The arrows indicate for-
mulation scans between different mixtures of (Sur-
f1 ? Surf2) and Surf3. The minimum interfacial tension in
the scans along the arrows is indicated as a circle. The
point indicated with a star corresponds to the lowest ten-
sion in the diagram and is thus the most efficient mixture of
the three surfactants.
With three surfactants, the mixing Eq. (11) may be
written as follows taking into account that among the three
fractions x’s, two (called here x1 and x2) are independents,
CpMIX ¼ x1 Cp1 þ x2 Cp2 þ x3 Cp3
¼ x1 Cp1 þ x2 Cp2 þ ð1  x1  x2 Þ Cp3 ¼ CSYS :
ð13Þ
This relationship represents a straight line in the ternary
diagram, whose equation expressed as a function of x1 and
x2 is as follows:
ðCp1  Cp3 Þx1 þ ðCp2  Cp3 Þx2 þ Cp3  CSYS ¼ 0:
ð14Þ
Unless one of the Cp values is exactly equal to CpSYS,
two of them are higher than CpSYS, and the last one is
lower, or reciprocally. In Fig. 5 it is assumed that Cp1 and
Cp2 are higher (Surf1 and Surf2 more lipophilic) than CSYS
and Cp3 is lower (Surf3 more hydrophilic). It means that in
this case the three differences (Cp1 - Cp3), (Cp2 - Cp3)
and (CSYS - Cp3) are positive.
In such a case mixing Surf1 with Surf3 will result in an
optimum formulation at point A on the 1–3 side of the
Fig. 5 a The arrows indicate the formulation scans in a diagram with
three surfactants mixtures. The lines in the ternary diagram indicate
the iso-tension contours. b The tension undergoes through a minimum
c* in each scan. The circle indicates the optimum formulation of each
scan
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J Surfact Deterg (2017) 20:3–19
ternary diagram in Fig. 6a. The Surf1 - Surf3 optimum
mixture composition is calculated by making x2 = 0, that
is:
x1 ¼ ðCSYS  Cp3 Þ=ðCp1  Cp3 Þ: ð15Þ
Note that x1 \ 1 at point A on the 1–3 side.
When mixing Surf2 with Surf3 an optimum formulation
is attained at point B where x1 = 0. The optimum com-
position of mixture Surf2 ? Surf3 is given by making
x1 = 0, i.e.,
x2 ¼ ðCSYS  Cp3 Þ=ðCp2  Cp3 Þ: ð16Þ
Note that x2 \ 1 at point B on the 2–3 side.
The mixture of Surf1 with Surf2 cannot produce an
optimum formulation because both surfactants are more
lipophilic than CSYS. If the x3 = 0 condition is applied to
Eq. (13), since x2 = 1 - x1, Eq. (14) becomes:
x1 ¼ ðCSYS  Cp2 Þ=ðCp1  Cp2 Þ: ð17Þ
Both Cp1 and Cp2 are higher than CpSYS. If Cp2 [ Cp1
then x1 is found to be larger than 1, and if Cp2 \ Cp1, then
x1 is found to be negative. In both cases there is no solution
since x1 must be in the 0–1 range.
Both points A and B represent binary surfactant mix-
tures at optimum formulation, so that their characteristic
parameter is equal to CSYS. Any mixture of A and B along
the AB straight line is thus also at optimum formulation,
since:
CpMIXAB ¼ xA CpA þ ð1  xA Þ CpB
¼ xA CSYS þ ð1  xA Þ CSYS ¼ CSYS : ð18Þ
The experimental diagram in Fig. 6b ternary indicates
the interfacial tension iso-contours in a system containing a
22° API crude oil with an EACN = 6.5 and a low salinity
brine (1.05 wt% TDS containing 1 wt% NaCl and
0.05 wt% CaCl2), at high temperature (60 °C), and with a
total surfactant concentration 0.5 wt%.
The CSYS estimated for this system is ?0.65, with the
reasonable assumption that the temperature effect is prac-
tically zero for a mixture containing anionic and nonionic
surfactants [40]. Using salinity expressed in wt% TDS and
a temperature of 60 °C, a salinity scan allows for estima-
tion of the surfactant Cp. A surfactant with Cp \ 0.65
(respectively[0.65) is hydrophilic (respectively lipophilic)
for this system. It is worth remarking that the nonionic
surfactant which contributes to avoid precipitation of the
ionic species by divalent cations, is hydrophilic
(Cp = -0.75). The long tail internal olefin sulfonate
(C20–22 IOS), a typical relatively inexpensive surfactant
for enhanced oil recovery is slightly hydrophilic
(Cp = -0.3). The third component, which is an extended
surfactant with a large polypropylene oxide intermediate
between the n-dodecanol tail and the sulfate group (nC12
J Surfact Deterg (2017) 20:3–19 11

Fig. 6 a Three-surfactant
ternary diagram with the iso-
tension contours and the
optimum formulation (c*)
indicated as the circle points (in
two-surfactant mixture scans on
the sides) and as a dashed line
inside the diagram (with a three-
surfactant mixture).
b Experimental ternary diagram
for such a system

PO13 S), is lipophilic in the system conditions

(Cp = ?0.95).
It is worth remarking that the CpMIX of the optimum
Surf2 - Surf3 mixture at point B is found to be ?0.69
when calculated according to Eq. (11) linear mixing rule.
As expected, this is consistent with the estimated
CSYS = ?0.65. This is not the case for point A, which is
the Surf1 - Surf3 optimum mixture. For A, the linear
mixing rule calculation results in CpMIX = -0.32, which is
very hydrophilic with respect to CSYS = ?0.65. This is not
surprising however, since such a discrepancy from linearity
is expectedly due to the hydrophobic effect produced by
the anionic-nonionic interaction indicated in Fig. 3. The
problem in practice is that the actual change in Cp due to
the shielding cannot be calculated. In the Fig. 3a case with
only 25 % of nonionic surfactant, the Cp increase is con-
siderable, i.e. about 2 units. In the Fig. 6b case 75 % of the
same nonionic surfactant tends to increase the Cp of the
optimum mixture by about one unit, i.e. a significant
interaction, but much less than in the Fig. 3 case. Of
course, the surfactant anionic head group is not the same.
In the Fig. 6b case, the ionic species is a sulfate group and
it is centrally extended with a long polypropylene oxide
chain. This suggests that there is less shielding because the
sulfate is more hydrophilic than the sulfonate. It also may
be because the polypropylene oxide extension is likely to
be partially at the interface [56] producing a disorder and
reducing the shielding efficiency. This corroborates that
even if the Cp values are useful to approximately guess a
mixture effect, the interaction between (ionic and nonionic)
surfactants may be significant enough to produce a non-
linear mixing rule. Consequently it is absolutely necessary
to experimentally determine the position of the optimum
formulation.
Nevertheless, it is seen in Fig. 6b that the AB line
between the best mixtures on the 1–3 and 2–3 sides is
basically straight, as it may be verified by the shape of the
low tension contours at 1 and 0.5 mN/m in Fig. 6b. The
elongation of these contours indicates that the basic
Fig. 7 Formulation scan along the straight (c*) optimum formulation
line (AB) joining the two surfactant mixture optima (a), to determine
the optimum optimorum c** formulation in the three surfactants
mixture (b)
mixture to match an optimum formulation is the Sur-
f2 - Surf3 binary combination. However, it is seen that a
small amount of the nonionic surfactant Surf1 also con-
tributes to attain an even lower minimum tension below
10-3 mN/m, i.e. an outstanding value. As it was shown in
Fig. 3a, this anionic-nonionic interaction not only reduces
the hydrophilicity, but also produces a relatively wide zone
where the CpMIX is almost constant, which results in an
increased robustness. This feature also allows for adjust-
ment of the nonionic proportion according to other
requirements to avoid problems with changing salinity,
particularly with divalent cations.
Binary optimum formulation points A and B are relatively
easy to find, i.e. only two scans have to be carried out, as
indicated by the arrows in Fig. 6a. If the AB line is exactly
straight as in Fig. 6, then only a third scan is necessary. It is a
scan along the AB line shown as an arrow in Fig. 7a which is
going to reach the overall optimum formulation in the ternary
diagram. Figure 7b shows the variation of the minimum
value c* along the AB path. It is seen that somewhere in this
AB scan, c* passes through a minimum indicated with a star.
This point, which is the best of the best in the ternary dia-
gram, has been called optimum optimorum after the Latin
expression, and its value is indicated as c**. It is worth

123
12
Fig. 8 a Determination of the (c*) optimum formulation line (AB)
when it is not a straight line. b Determination of the optimum
optimorum c** formulation in the three surfactants mixture
remarking that this clever strategy only requires three scans,
i.e. it corresponds to only about 24 tension measurements to
find the best Surf1 ? Surf2 ? Surf3 ternary mixture. This is
an amazingly efficient experimentation compared to a
screening of tension measurements everywhere in the dia-
gram, as is usually done.
If there is some non-linearity in the mixing rule, the scan
along the AB straight line is replaced by a series of very
short scans (e.g., 3–4 measurements per scan instead of the
typical 8–10) which are perpendicular to the AB line, as
indicated by double arrows in Fig. 8a diagram. Figure 8b
indicates the minimum interfacial tension, i.e. the c* val-
ues, of these short formulation scans. The lowest c* value,
i.e. c**, is indicated as a star.
Figure 9 shows an experimental ternary diagram for a
system containing an EACN = 5.8 heavy crude oil of 14°
API, with a brine containing 1.3 wt% salt (composed of 96 %
NaCl ? 4 % CaCl2) at 30 °C. This time there are two lipo-
philic surfactants in the formulation conditions, i.e. a linear
alkyl benzene sulfonate (C16LAS) and a high molecular
weight extended surfactant with a Guerbet double tail and a
long polypropylene intermediate chain before the sulfate head
(C12 PO20 S). The linear alkyl benzene sulfonate has a
Cp = ?0.80 at 60 °C and Cp = ?0.85 at 45 °C, i.e. slightly
more lipophilic at lower temperature as expected [1, 3, 7]. The
extrapolated value at 30 °C is Cp = ?0.90. The Guerbet
extended surfactant has a Cp = ?0.7 at 30 °C and it is less
lipophilic at 15 °C, i.e. Cp = ?0.3, which is the opposite
temperature effect as expected for this kind of extended sur-
factant [56]. The last surfactant is nonionic of the ethoxylated
dodecanol type (C12EO8). Comparing to the previous non-
ionic iC13EO6, this one has a higher number of EO units, a
shorter tail, and the present system has a lower temperature
(30 °C). All these changes result in a more hydrophilic spe-
cies, with an estimated value of Cp = -4. The total surfactant
concentration is 0.6 wt%.
It can be seen from the iso-tension contours in Fig. 9
that none of the three surfactants is satisfactory as far as the
tension value is concerned at this salinity. Even worse, it
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J Surfact Deterg (2017) 20:3–19
Fig. 9 Experimental ternary diagram at constant salinity
(S = 1.3 wt% salt) indicating the iso-tension contours and the
optimum formulation (AB) line when it is not straight. The separated
stars indicate the possible position(s) of the optimum optimorum
formulation(s)
was found that Surf2 precipitates in the shaded zone
because the 30 °C temperature is below its Krafft point.
Nevertheless, each ionic surfactant presents a mixture with
the nonionic that results in a minimum tension at about
1 mN/m at points A and B. The AB optimum formulation
line was found through the short scans perpendicular to AB
as indicated in Fig. 8a. This AB optimum formulation line
is curved, with an extremely thin and elongated low tension
(c \ 0.5 mN/m) strip zone.
Some points of this zone were found to exhibit a tension
at about 0.2 mN/m. They are indicated with a star. Since the
strip is very narrow, there is not enough accuracy to deter-
mine the exact location of the optimum optimorum c**
point somewhere on the AB line. Moreover, as seen in the
Fig. 3d scheme, two minimum tension points can occur in a
non-linear mixing rule, one close to A and the other close to
B, as the separated star points suggest in this diagram.
Because of the very elongated low tension zone, the
system is robust as far as the composition of the Surf2/
Surf3 mixtures is concerned, a favorable situation since one
of them could adsorb quicker on the reservoir solid and
since the Cp formulation in the fluid could vary because of
the chromatographic separation effect. The fact that the
nonionic surfactant is very hydrophilic and unlikely to
adsorb or to separate at the salinity and temperature con-
ditions, is an additional favorable convenience for
improving the robustness of the process. However, since
the interfacial tension varies very fast in the vertical
direction in Fig. 9 triangle, this system requires an extre-
mely accurate formulation concerning the amount of the
nonionic component Surf1.
If the iso-tension contours are known, another way to be
very efficient in the experimental strategy is to take a step
J Surfact Deterg (2017) 20:3–19 13

by step path, which is always perpendicular to the tension
iso-contours. This is indicated in Fig. 10a diagram starting
from a side, e.g. from points P, Q, or R, and moving toward
the optimum optimorum point along different paths. It is
worth remarking that it is in the direction perpendicular to
the iso-tension contours that the tension variation is locally
steepest. A sequence of steps always using the highest
tension gradient is the best way to attain the optimum
optimorum as soon as possible, along a sometimes curved
path as seen in Fig. 10a diagram.
If the iso-contours are not known, as is generally the
case, the step by step method has to be carried out with the
method estimating at every point the best tension gradient
to select the next step direction. The scheme in Fig. 10b
indicates the way to do this along three steps. Starting at a
given point in the sequence (current best point) the tension
is then measured at different points indicated as (x). These
points are located close to the current point in directions
close to the one which corresponded to the steepest tension
decrease in the ultimate step. In the Fig. 10b scheme there
are five trials indicated by short arrows. One of them (the
second arrow from below) is supposed to be the one
indicating the largest decrease in the interfacial tension
from the current point. This arrow thus indicates the
direction of the steepest decrease in tension, i.e. the
direction perpendicular to the iso-tension contour. The next
trial is hence carried out in that direction at some distance
at the place indicated as the next point.
It is worth noting that the trials at the five x points is
some kind of formulation scan, although not a unidimen-
sional one, because the compositions of the three surfac-
tants are different in all trials. It may be said in practice that
the scan is carried out in a section of circle around the
current point, a non-conventional way which allows a high
laboratory performance in practice.
The sequence of points looks like the paths indicated
from basic points P, Q, and R in Fig. 10a diagram. This is
particularly efficient when the basic point is like the Surf3
surfactant, which is in the present figure the worst one
alone as far as the interfacial tension is concerned. In spite
of that, Surf3 could be a critical ingredient for other
reasons like good solubilization with no gel, or a resistance
to precipitation. This often happens with extended surfac-
tants which are not necessarily good alone, but often pro-
vide an excellent synergy.
Sometimes, one of the three surfactants has a serious
problem and cannot be used alone or in a large proportion
because it precipitates under the salinity and temperature
conditions of the system. This may be the case of a sulfate
or sulfonate with a very long straight tail, which may be
attractive because it often provides a very low tension at a
low cost. In such a case the path to the optimum optimorum
point is limited to a feasible region and the direction of the
step by step sequence must take into account the precipi-
tation boundary as indicated in Fig. 11. Of course a better
selection of the three surfactants, e.g. with a nonionic, or
the addition of a forth one, could be another way to reduce
the prohibited zone or cancel the limitation.
Salinity Variation with a Three-Surfactant
Mixture
In the previous sections the salinity of the aqueous phase
was supposed to be a constant, generally equal to the
salinity of the brine in the reservoir. In practice, the salinity
may be changed during the enhanced oil recovery injection
Fig. 11 Step sequence modification in the case of a ternary diagram
with a prohibited zone

Fig. 10 a Paths to attain the

optimum optimorum
formulation in a ternary diagram
through a curved scan as a step
by step sequence, always in the
direction perpendicular to the
iso-tension contours.
b Determination of the proper
new direction at each step

123
14
process for several reasons. The first one is because the
available aqueous phase salinity is not necessarily equal to
the reservoir brine. On the other hand, the salinity might be
different from place to place in the reservoir, for instance
because of a previous water flood with a brine different
from the connate water. Another reason may be the
injection of a preflush with a different salinity or a different
pH. Finally a salinity gradient [69] may be voluntarily
applied to change the formulation during the injection, so
that the optimum formulation occurrence is warrantied or
surfactant adsorption is reduced. Whatever the reason, it
means that the previous discussion at constant salinity is
not always adequate in practice, and that a change in
salinity should also be considered.
Consequently, it is convenient to describe the change of
the three surfactants ternary diagram with salinity, and a
way to do it is to use an additional dimension as in the
prism shown in Fig. 12, that allows for variation of the
salinity at the same time than the composition of the three-
surfactant mixture changes. To avoid confusion among the
symbols, it is worth remarking that the abbreviations Surf1,
Surf2 or Surf3 refer to surfactant species, whereas S refers
to salinity in general, Sref to a special reference value and
S* to the optimum salinity in the unidimensional salinity
scan. S*1 is the optimum salinity for a system containing
surfactant Surf1 and S*M for a surfactant mixture.
Figure 12 indicates the variation of the Surf1 - Sur-
f2 - Surf3 ternary diagram previously studied, this time as
a function of salinity. The salinity reference (Sref) cut is
taken as the salinity of the aqueous phase to be injected in
the previous case of constant salinity. The optimum binary
surfactant mixtures A and B are indicated as before at this
reference salinity system in which Surf1 and Surf2 were
hydrophilic surfactants with respect to the required system
CSYS and Surf3 lipophilic, as in Fig. 6 situation.
Fig. 12 Three-dimensional prism indicating the variation of the
three-surfactant ternary diagram with the salinity of the aqueous
phase
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J Surfact Deterg (2017) 20:3–19
When the salinity is increased above Sref, the optimum
formulation line AB is displaced away from the lipophilic
surfactant Surf3 vertex and the Winsor II zone tends to
expand. At some salinity (indicated as S [ Sref in Fig. 12)
Surf2 has became lipophilic, and only Surf1 remains
hydrophilic. Then, at an even higher salinity (indicated as
S  Sref in Fig. 12) the WII zone invades the whole dia-
gram and there is no way to produce an optimum formu-
lation with the three surfactants, because they are all
lipophilic.
An AB line in a constant salinity triangular cut exists
only in the range from the optimum salinity of the most
lipophilic surfactant to the optimum salinity of the most
hydrophilic one. This salinity zone in which an optimum
formulation is attainable (in the fixed conditions EACN,
T and P of a system) is indicated in Fig. 13 as the range
from the optimum salinity S*3 of the most lipophilic sur-
factant (Surf3) to the optimum salinity S*1 of the most
hydrophilic one (Surf1). When these three optimum
salinities S*1, S*2 and S*3 are placed on the salinity axis of
the three surfactants, they form an oblique triangular cut of
the prism. Let us now prepare an aqueous solution of each
surfactant, at the same concentration, but each at the
Fig. 13 a Cut of the Fig. 12 prism with a plane passing through the
optimum salinity points of the involved three surfactants. b Slanting
ternary diagram at variable salinity
J Surfact Deterg (2017) 20:3–19
optimum salinity of the corresponding surfactant. If the
three solutions are mixed to produce a constant volume of
the aqueous phase, the resulting salinity could be calcu-
lated as:
SMIX ¼ x1 S1 þ x2 S2 þ x3 S3
¼ x1 S1 þ x2 S2 þ ð1  x1  x2 Þ S3 ; ð19Þ
where the x represent the fractions of the three solutions, as
well as the fractions of the three surfactants in the system.
Equation (19) is a linear relationship in the three dimen-
sions (S/x1/x2), and is thus the equation of a plane passing
by the three points representing the optimum salinities on
the three axis, i.e. a slanting triangle S*1S*2S*3 indicated in
Fig. 13a prism. This plane is cutting the constant salinity
planes by straight lines as indicated in the prism. These
straight lines go from a point (previously called A) on one
of the side of the constant salinity triangle to another point
(B) on another side.
If the characteristic parameter of the surfactants varies
linearly with salinity as in the case of ethoxylated non-
ionics, then the side S*1 - S*2 of the slanting triangle
indicates a mixture of two surfactants Surf1 and Surf2 at
optimum. According to Eq. (2) the variation of the char-
acteristic parameter with S may be written as follows in
Eq. (20) for ethoxylated nonionic surfactants, where the
constant Cst depends on the surfactant structure and on the
fixed variables (EACN, T, P), but not on salinity,
Cp1 ðSÞ ¼ Cst1  b S and Cp2 ðSÞ ¼ Cst2  b S: ð20Þ
According to Eq. (11) for a binary mixture of two
solutions containing Surf1 at salinity S*1 and Surf2 at
salinity S*2, the final mixture has a salinity SMIX,
SMIX ¼ x1 S1 þ x2 S2 : ð21Þ
MIX
According to Eq. (11) applied at S the characteristic
parameter of the mixture is,
CpMIX ðat SMIX Þ ¼ x1 Cp1 ðat SMIX Þ þ x2 Cp2 ðat SMIX Þ:
ð22Þ
A few calculations using the last three equations show
that the characteristic parameter of the Surf1 ? Surf2
surfactant mixture at some point (located at fractions x1, x2)
on the S*1 - S*2 side of the slanting triangle may be
written as:
CpMIX ðat SMIX ¼ x1 S 1 þx2 S2 Þ
¼ x1 Cp1 ðS1 Þ þ x2 Cp2 ðS2 Þ: ð23Þ
This relationship corroborates that the linear Eq. (22) is
valid with each surfactant characteristic parameter evalu-
ated at its optimum salinity S* (information which is
generally available) provided that Eq. (20) are satisfied,
which is the case with ethoxylated nonionics.
15
The same relationship is found for the other side of the
oblique triangle where there is an optimum. Consequently
the straight line which is the interception of the oblique
triangle S*1S*2S*3 and a constant salinity triangle cut is the
AB optimum formulation line. Since the constant salinity
cuts are parallel planes, all the AB intersections are parallel
and exist only in the range of salinity from the two extreme
of S*, i.e. S*1 and S*3 in the prism.
Measuring the tension along the AB lines at different
salinities provides very useful information to draw the iso-
tension contours in the slanting triangle. This precious
information includes the location and value for the best
minimum c** for each salinity, as well as the super best
minimum location (indicated as a star) and its value c*** in
the slanting triangle with a variable salinity. It corresponds
to the point inside the prism for the selected surfactant
ternary, where the appropriate salinity and mixing produce
the best possible result in terms of interfacial tension
reduction.
If Eqs. (1) and (20) do not apply, for instance because
the characteristic parameter varies as lnS rather than S as
for anionic surfactants, the sides of triangle S*1S*2S*3
representing the mixed salinity are not straight lines and the
pseudo-triangle is not on a plane but on a curved surface.
Consequently, this optimum pseudo-ternary surface inter-
sects the constant salinity triangular cuts somewhere, and
results in AB lines which are not straight.
The Fig. 13b diagram shows a slanting triangle for three
surfactants, two branched sulfonates and an extended sur-
factant with a central nonionic part of propylene oxide, i.e.
a surfactant ternary diagram without ethoxylated nonionic
at a 0.5 wt% total concentration. The oil phase is a light
crude of 37° API with EACN = 7. The brine contains the
indicated wt% of NaCl plus 1 % Na2CO3. The temperature
is 48 °C. The Surf1 is the most hydrophilic surfactant and
Surf3 the most lipophilic, as in the Fig. 13a prism. The
Fig. 13b triangle indicates the iso-tension contours in the
slanting diagram and the optimum formulation AB lines at
different salinities. Although the AB lines are not straight,
they are sufficiently close to it to maintain the previous
reasoning and to save a huge amount of time and money in
selecting a proper formulation in cases in which the salinity
is going to change.
This kind of information is very efficient for modeling
the result of a salinity gradient [67, 69, 70] which could be
an attractive strategy during enhanced oil recovery injec-
tion. Figure 13 data shows that it is valid to approximate
the AB line by straight segments around the super mini-
mum point indicated as a star, and to enter a good
approximation of the actual tension variation versus
salinity for a given mixture. The data in the Fig. 13b tri-
angle also show how to slightly adjust the injected ternary
123
16
Fig. 14 Blow up of the central region of Fig. 13b diagram indicating
the linear approximation of the iso-salinity lines. The arrow indicate
the path to follow for a salinity gradient process with the concomitant
change in the ratio of Surf1 to Surf3
mixture of surfactants when the salinity is changed in the
gradient.
Figure 14 shows a blow up of the center of the Fig. 13b
ternary diagram, in which an efficient program of con-
comitantly changing the salinity and the surfactant mixture,
is indicated by an arrow. The formulation design consists
of changing the salinity from 5 % NaCl to 3 % NaCl, with
an horizontal path from right to left indicated by the arrow.
The proportion of Surf2 intermediate surfactant is kept
constant at about 45 %, while the proportion of the most
hydrophilic surfactant Surf1 will be decreased from 22 to
15 %, along the arrow. These ranges of salinity and sur-
factant mixture composition will keep the tension below
0.1 mN/m according to the iso-tension contours, which is a
very attractive performance in practice.
Additionally, it should be remarked that the increase in
the most lipophilic surfactant Surf3 will be accompanied
by a decrease in salinity, a safe concomitant change for
avoiding the possible precipitation of the most hydrophobic
ingredient. By the way, it should be noted that the selection
of the surfactants were in accordance with the experience
found in the literature [43] to avoid precipitation when
there is no ethoxylated surfactant in the mixture. It is worth
remarking that in this selection the sulfonates have a
branched tail, and the extended surfactant also has a non-
linear tail. The mixture of an internal olefin sulfonate and
an extended surfactant was also selected to increase the
surfactant mixture solubilization as reported in the litera-
ture [68].
Figure 15 shows a cut of the prism similar to the
slanting triangle for a system containing a nonionic
ethoxylate whose optimum salinity is very high, out of the
feasible range. It also contains a linear alcohol sulfate and a
Guerbet extended surfactant, at a total 0.6 wt% surfactant
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J Surfact Deterg (2017) 20:3–19
Fig. 15 Same system as in Fig. 9, but this time at variable salinity.
This diagram is in a slanting cut of the prism as in Fig. 13a. The AB
optimum formulation lines at constant salinity are indicated as in
Fig. 13b. AB lines are somehow more curved in this case, probably
because of the presence of a nonionic component and a strong
interaction with the anionics. Dashed line indicates an almost constant
minimum tension value in spite of a considerable gradient in salinity
and a concomitant change in the fraction of the nonionic surfactant
concentration. It is actually the same system ternary shown
in Fig. 9, but this time at variable salinity, and is thus a
slanting diagram. At each salinity, an optimum formulation
line from the best Surf1 - Suf2 mixture to the best Sur-
f1 - Surf3 mixture is drawn and the tension is registered
along it. Figure 15 shows that these iso-salinity optimum
lines (called AB in previous diagrams are not straight but
relatively close to it).
The drawn iso-tension contours indicate that there is an
optimum optimorum on each iso-salinity line when
S [ 1 wt%. The behavior in the 1–2.5 % salinity zone is
the same as in Fig. 9 which corresponds to S = 1.3 wt%
salt. There is a strong variation in the attainable minimum
tension when the concentration of Surf1 nonionic surfac-
tant is changed, in accordance with the very thin low-ten-
sion zone around the AB line found in both Figs. 9 and 15.
In other words, it is obvious that some nonionic surfactant
is required to attain a low-tension zone, but that any excess
or default would produce a high penalty in the minimum
tension value. This is an usual effect for commercial
nonionics, which are known to be generally associated with
higher tension [2], although some exception have been
found for extremely pure alcohol ethoxylates [66].
Figure 15 ternary diagram at variable salinity presents
an additional feature which is not usual. At and above
2.5 wt% salinity, the optimum optimorum takes place with
J Surfact Deterg (2017) 20:3–19
Fig. 16 Variation of the interfacial tension versus salinity with the
change of nonionic surfactant fraction (in a 0.6 wt% surfactant total
concentration) along the path indicated by a dashed line in Fig. 15
the same relation between the two anionic surfactants Surf2
and Surf3, i.e. at exactly four times more Surf2 than Surf3.
This means that the most hydrophilic surfactant (Surf1) is
the one that exactly compensates the change in salinity, as
is almost the case in the Fig. 6b diagram, which in addition
deals with a similar surfactant ternary mixture.
What is unusual in the Fig. 15 diagram is that the
optimum optimorum situation along the indicated dashed
line stays essentially at the same c* value, i.e. around
0.2–0.3 lN/m, as it is corroborated by the data shown in
Fig. 16. The reason is not known for sure, but it could be
suggested that such non-collective behavior may be due to
the screening effect produced by the polyethylene oxide
chain of the nonionic surfactant surrounding both ionic
heads and reducing their hydrophilicity as showed in Fig. 3
[36]. Because of this effect, the characteristic parameter Cp
of the anionic/nonionic surfactant mixture could remain the
same over a wide range as seen in Fig. 3a, i.e. it does not
depend much on the proportion of Surf1.
Whatever the exact reason, this feature is interesting in
practice because it allows for a change in the salinity and to
keep the low-tension performance at the same time, which is
a quite unexpected occurrence. In this case, a wide salinity
gradient (e.g. from 10 to 2 % salt) could be carried out
robustly maintaining the same low-tension, provided that the
nonionic surfactant amount is concomitantly changed with
salinity to exactly match the narrow low tension range at
optimum for each mixture, as shown in Fig. 16.
Conclusion
Most people working on enhanced oil recovery formula-
tions use a pair of surfactants to formulate a low tension
system, and generally think that incorporating a third one
17
(or more) requires a lot of extra time and expenses that
could require high throughput work. However, even with
robotic equipment, the number of variables is so large that
a high throughput random search is likely to produce a
large amount of data with little practical value.
The present article explains why understanding the
complexities and using clever guidelines are probably the
most important strategy features for this kind of research. It
specifically shows that the use of a mixture of three sur-
factants is quite advantageous in practice, because an
ultralow tension formulation can be attained through a
systematic sequence reducing the time consuming experi-
mental work.
Acknowledgments The authors thank SASOL for providing a spe-
cially prepared extended surfactant with a Guerbert C12 PO20 S
formula, CEPSA for sending a C16 LAS sample, and SHELL for
supplying some of its Enordet commercial products.
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Jean-Louis Salager earned a B.Sc. in chemistry and a B.Sc. in
chemical engineering from the University of Nancy (France), as well
as a M.Sc. and a Ph.D. from the University of Texas at Austin (USA)
in enhanced oil recovery formulation. For the past 45 years he has
been involved in teaching and research at the University of the Andes
(Mérida-Venezuela) where he is the founder and former director of
the FIRP laboratory. He is currently an emeritus professor and
consultant in surfactant science and technology with applications in
petroleum production, health and personal care, as well as detergent
products.
Ana M. Forgiarini earned a B.Sc. in chemical engineering from the
Technological Institute in Barquisimeto (Venezuela) and a M.Sc. in
chemical engineering from University of the Andes (Mérida-
Venezuela). She received her Ph.D. from University of Barcelona
(Spain) and spent a year as a postdoctoral fellow at North Carolina
State University (USA). Over the past 30 years she has been involved
in teaching and research at the University of the Andes, where she is
currently an active retired professor, Deputy Director of the FIRP
laboratory, and head of the micro and nanoemulsions research and
development group, particularly with applications to improved
petroleum production.
Miguel J. Rondón earned a B.Sc. in chemical engineering from the
University de Los Andes (Mérida-Venezuela), a M.Sc. in drilling
engineering from Universidad del Zulia (Maracaibo-Venezuela) and a
Ph.D. in Energy and Dispersed Systems from University of Pau
(France). He worked as a postdoc fellow in crude oil dehydration at
the University of the Andes and in tertiary oil recovery at the
University of Kansas (Lawrence-USA). He was an assistant professor
for 3 years at University Simon Bolivar (Caracas-Venezuela), and
worked as an applied research scientist in petroleum exploration-
production for 6 years at Petroleos de Venezuela R&D center
INTEVEP (Caracas). He is currently an investigator in enhanced oil
recovery at Santander Industrial University in Bucaramanga
(Colombia).
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