Multiphase Microemulsion Systems
R.N. HEALY EXXON PRODUCTION RESEARCH CO.
R. L. REED
MEMBERS SPE-AIME
D. G. STENMARK
ABSTRACT
Economical microemulsion flooding inevitably
involves microemulsion phases immiscible with oil
or water, or both; oil recovery is largely affected by
displacement efficiency during the immiscible regime.
Therefore, it is essential to understand the role of
interfacial tension m relation to multiphase
microemulsion behavior.
Three basic types of multiphase systems are
identified and used to label phase transitions that
occur when changes are made in salinity, temperature,
oil composition, surfactant structure, cosolvent, and
dissolved solids in the aqueous phase. Directional
effects of these changes on phase behavior,
interfacial tension, and solubilization parameter are
tabulated for the alkyl aryl sufonates studied.
A relationship between interfacial tension and
phase behavior is established. This provides the
basis for a convenient method for preliminary
screening of surfactants for oil recovery.
Interfacial tensions were found to correlate with
the solubilization parameter for the various
microemulsion phases, a result that can substantially
reduce the number of interfacial tensions that must
be determined experimentally for a given application.
INTRODUCTION
A previous paper 1 established that microemulsion
flooding is a locally miscible process until slug
breakdown and is an immiscible, rate-dependent
displacement thereafter; furthermore, for an effective
flood, most of the oil recovered is acquired during
the immiscible regime. An extensive study2 of
single-phase regions defined classes of micellar
structures for a particular surfactant; however, it
was subsequently shown 1 these did not affect oil
recovery, provided viscous, lamellar structures were
avoided. Optimal salinity was introduced as defining
a ternary diagram having the least extensive
<;>riginal manuscript received in Society of Petroleum Engineers
off1ce July 28, 1975. Paper accepted for publication Nov. 14,
1975. Revised manuscript received Feb. 10, 1976. Paper (SPE
5565) was first presented at the SPE-AIME 50th Annual Fall
Technical Conference and Exhibition, held in Dalt"as, Sept.
28-0ct. 1: 1975. ©Copyright 1976 American Institute of Mining,
Metallurg1cal, and Petroleum Engineers, Inc.
1 References given at end of paper.
This paper will be included in the 1976 Transactions volume.
JUNE, 1976
HOUSTON, TEX. "
EXXON RESEARCH AND ENGINEERING CO.
BAYTOWN, TEX.
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multiphase region, a desirable feature in that locally
miscible displacement is prolonged.
Immiscible displacement after slug breakdown is
known to depend on interfacial tension through its
inclusion in the capillary number.l, 3-7 A brief study2
showed that interfacial tension varied widely
throughout the multi phase region; accordingly, it is
anticipated that oil recovery will depend on details
of multiphase behavior in relation to interfacial
tension, as well as on injection composition.
Consider a flood sufficiently advanced that the
microemulsion slug has broken down. A microemulsion
phase remains that is immiscible with water or oil
or both, and displacement has assumed an immiscibl~
character. The problem is twofold: to design a
microemulsion slug that effectively displaces oil at
the front and that is effectively displaced by water
at the back. Both aspects are essential and therefore
both microemulsion-oil and microemuision-wate~
interfacial tensions must be very low. The condition
where these two tensions are low and equal will be
of particular significance.
The purpose of this paper 1s to explore
physicochemical properties of multiphase
microemulsion ·systems with a v1ew toward
understanding immiscible aspects of microemulsion
flooding, and with the expectation of developing
systematic screening procedures useful for design of
optimal floods.
Equilibration is an essential part of this study.
Even the simplest of these systems is so complex
it may well happen that nonequilibrium effects will
never be understood sufficiently to be usefully
accommodated in mathematical simulation of
microemulsion flooding. In any event, equilibration,
although time consuming, leads to a coherent picture
of multiphase behavior that can be correlated with
flooding results.
Multi phase behavior of 11 simple" ternary systems
divides into three basic classes. Dependence of
phase behavior on salinity, with respect to these
classes, leads to correlations of interfacial tension
with the solubilization parameter. These correlations
are studied in relation to surfactant structure,
temperature, co sol vents, oil composition, and brine
composition. Optimal salinity again plays an
important role, especially in relation to interfacial
tension.
147
 GENERAL CONCEPTS
PHASE BEHAVIOR AND MICELLAR STRUCTURE
Simple Systems
It is instructive to study microemulsion systems
in terms of ternary phase diagrams.2,8,9 Although
these diagrams may be quite complex when only oil,
water, and surfactant are involved, addition of an
appropriate alcohol cosolvent causes vast simplifi-
cation in phase behavior and micellar structure. 2
For simple systems, the ternary diagram divides
into two or four regions, as shown in Fig. 1. In each
case, every compositional point within the
single-phase regwn above the binodal curve
corresponds to a microemulsion; but micellar
structure may vary with location. Compositional
points below the binodal curve correspond to multiple
phases, comprising, in general, microemulsions of
various kinds, excess oil, and excess water;
therefore, opaque emulsions of these are observed
upon mixing.
Fig. 1a shows a two-phase region wherein
microemulsions along the binodal curve are in
equilibrium with oil containing molecularly dispersed
surfactant (excess oil). This is Winsor's Type I
system.10 Fig. 1c shows a two-phase region wherein
microemulsions along the binodal curve are 1n
equilibrium with excess water (Winsor's Type II
system). More recently, Type II systems have been
considered by Adamson,11 and by Tosch et al. 1 2
Usually a Type I multiphase region is skewed to the
right and a Type II region is skewed to the left, as
illustrated. Fig. 1b shows Type II in the upper-left
node, Type I in the upper-right node, and Winsor's
Type III in the lower triangle. Any composition within
this triangle equilibrates into three phases:
microemulsion corresponding to compositional point
M, excess water, and excess oil. In this paper,
Winsor's Type I, II, and III systems will be called
lower phase, £,. upper phase, u, and middle phase,
m, respectively. Among the variables that affect the
type of diagram observed are salinity, oil composition,
surfactant molecular structure, alcohol cosolvent, and
temperature.
EQUILIBRATION PROCEDURE
Previously, phase diagrams were determined2 by
equilibrating over 100 compositions placed at grid
SURFACTANT
b
SALINITY----
FIG. 1 - SIMPLE PHASE BEHAVIOR.
148
points of 2 percent in surfactant concentration and
10 percent in oil or water concentration. The multi-
phase boundary was then drawn midway. between
adjacent compos1t1ons where a trans1t1on from
multiphase to single phase occurred. A different
method involves preparation of several multiphase
samples having constant over-all surfactant
concentration but varying water-oil ratios (WOR).
The assumption of negligible surfactant concentration
in excess water and oil phases (Appendix C) allows
calculation of equilibrium microemulsion compositions
from equilibrated phase volumes, and construction of
a binodal curve. If the over-all surfactant
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concentration of the samples is changed, the phase
diagram will change, reflecting the multicomponent
nature of surfactant, cosolvent, brine, and oil used.
Fig. 2 shows binodal curves at two different over-all
surfactant concentrations for the lower-phase
microemulsion system composed of 63/37
MEAC120XS/TAA, 90/10 I/H, and 1-percent NaCl
(Appendix A). The far right portion of the binodal
curve for 1-percent surfactant* was not determined
because it would have required preparation of over-all
compositions containing less than 5-percent brine.
For such low brine concentrations, minor amounts of
salt in the surfactant component can significantly
influence phase behavior.
As over-all surfactant concentration increases,
the binodal curve is raised. Since similar results
have been obtained for a variety of systems, it is
conjectured that the grid-point method yields a phase
boundary correspondisg to the maximal envelope
of all phase boundaries determined at constant
surfactant concentration. This type of relation can
be expected to result as long as the system remains
of a single type (that is, Fig. la, lb or lc)
as concentration changes. The constant surfactant-
concentration method is· particularly applicable to
studies of the multiphase region of the ternary phase
diagram, whereas the grid-point method is more
approptiate for investigations of the single-phase
region.
*Unless stated otherwise, all concentrations, except for salt
concentrations, refer to volume percent. Salt concentrations are
ex pres sed in percent and mean grams per 100 ml.
63/37 MEAC120XS/TAA
••e14>
0
5% SURFACTANT
FIG. 2 -EFFECT OF SURF ACT ANT CONCENTRATION.
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
 63/37 MEAC120XS/TBA
63/37 MEAC120XS/TBA
Real Systems
Fig. 3 comprises phase diagrams of real systems
that approximate simple ones at three different
salinities for 63/37 MEAC120XS/TBA, 90/10 1/H,
and brine. Binodal curves were determined at 3-
percent 63/37 MEAC120XS/TBA. Increasing salinity
from 1.5- to 4.0-percent NaCl causes successive
appearance of lower-phase, middle-phase, and
upper-phase diagrams.
A notable difference between real and simple
systems is the locus of middle-phase compositions
(Fig. 3b) rather than a single point (Fig. 1b).
However, as the base surfactant concentration
increases, the lateral extent of this locus is expected
to decrease. The right-hand portions of the binodal
curves for the lower- and middle-phase systems
(Figs. 3a and 3b) and the left-hand portion of the
upper-phase curve (Fig. 3c) were not determined
experimentally because over-all water or oil contents
were so low that surfactant impurities affected
results.
0.5 1.0
FIG. 4 - PHASE BEHAVIOR AS A FUNCTION OF SALINITY.
JUNE, 1976
Fig. 4 1s a photograph of samples having
over-all compositiOns corresponding to 4-percent
63/37 MEAC120XS/TAA, 48-percent 90/10 I/H, and
48-percent X-percent NaCl, where X varies from 0.5
to 2.5. At this writing, all phase volumes have been
constant for more than 1 year. These samples
illustrate the effect of salinity on phase behavior
when WOR is maintained constant at 1/1 and
surfactant concentration 1s also held constant.
Evidently, increasing salinity causes the
microemulsion phase to undergo the transitions of
lower phase --t middle phase --t upper phase (E --t m --t
u). This remarkable, systematic behavior of complex,
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multicornponent microemulsion systems is essential
to all that follows.
Micellar Structure
Micellar structure of · microemulsion phases
corresponding to 3-percent 63/37 MEAC120XS/TAA,
48.5-percent 90/10 I/H, and 48.5-percent X-percent
NaCl, where X varied from 0.5 to 3.0, has been
investigated using a previously describe~ approach
based on Winsor's intermicellar equilibrium concept 1 0
and measurements of electrical resistivity, viscosity,
and optical birefringence. 2
Fig. 5a shows how microemulsion type (E, m, or u),
resistivity, and viscosity depend on salinity. The
microemulsion phase undergoes the transitions E --t m
--t u as salinity Increases. Since none of the
microemulsions was birefringent or streaming
birefringent, and since resistivity increases contin-
uously, neither of these pfoperties identifies E --t m
or m --t u. However, viscosity changes abruptly at
these transitions and is related to the microemulsion
149
 a b
3o/o 63/37 MEAC120XS/TAA, ...I
3°/o 63/37 MEAC120XS/TAA,
48.5°/o 90/10 1/H, 48.5o/o X 0/o NaCI 48.5o/o 90/10 1/H, 48.5o/o X 0/o NaCI ~
0
1-
a:
w
1-
w
~I
~
:I:
0
I
UPPER
PHASE c.
(.)
c.
(.)
::J~
0'
>...J
Z>
Ow
0

-.....~
~c..
::>~
~<(
>
1-
20
w
u 'i
(.)
w
wCI)
0

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>
i=
16 (/)
M
(/)
M
a:
(.)
(/) 12 N N
u; @) @) ~
8
w
a: >-
1-
>-
1-
4 u; u;
0 0 0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 (.) (.) 0.5 1.0 1.5 2.0 2.5 3.0 3.5
(/) (/)
SALINITY, /o NaCI
0
> > SALINITY, o/o NaCI
FIG. 5 - MICROEMULSION VISCOSITY, RESISTIVITY, AND VOLUME;

phase volume (Fig. 5b). average, spherical, cylindrical, or lamellar.

Micellar structure can be interpreted conveniently
in terms of Winsor's intermicellar· ·equilibrium
concept, provided resistivity and birefringence alone
are considered. These data suggest that increasing
salinity causes a gradual shift of intermicellar
equilibrium from spherical water-external, S b to
spherical oil-external, s2' without an intervening
gel phase. Equilibrium favors S 1 when the
microemulsion is lower phase and S 2 when it is
upper phase. When the microemulsion is middle
phase, both S 1 and S 2 are present to an appreciable
extent, and Winsor represents the micellar structure
by (S 1 , S2).
However, such an interpretation does not appear
to account for the abrupt changes in viscosity and
phase volume that occur at boundary salinities for
the middle phase. These phenomena suggest that
£ ~ m and m ~ u are, in a sense, sharp transitions.
In fact, the following middle-phase properties are
evident:
1. If there 1s an external phase, it is neither oil
nor water.
2. If there are micelles, they are not, on the
63/37 MEAC120XS/TAA
• LOWER PHASE
o MIDDLE PHASE
FIG. 6 - PHASE DIAGRAM AT 1.4-PERCENT NaCl.
An alternate view, then, is that spherical micelles
predominate in the f and u phases, but the m phase
is quite distinct. Although there are insufficient data
to make a judgment, the cosolubilized state
suggested by Shah 13 is a possible middle-phase
model.
A ternary diagram for the system 63/37
MEAC120XS/TAA, 90/10 1/H, 1.4-percent NaCl,
measured at 3 percent of the surfactant coordinate,
appears in Fig. 6. The expected middle-phase region
is bounded on both sides by lower phases and no
upper phase is present. This complex behavior is
discussed later.
INTERFACIAL TENSION
As X increases from 0.5 to 3.0, the system 3-
percent 63/37 MEAC120XS/TAA, 48.5-percent 90/10
1/H, and 48.5-percent X-percent NaCl, makes the
trans1t1ons f ~ m ~ u and assumes, at the various
salinities, appearances qualitatively the same as
Fig. 4. Since both microemulsion-oil and
microemulsion-water interfaces occur, tensions at
both interfaces, Ymo and Ymw' respectively, are of
interest. The previously described sessile drop
technique2 was applied to measure these tensions,
which are plotted as functions of salinity in Fig. 7a.
Whenever both y mo and Ymw are plotted at a given
salinity, a middle phase exists. When lower-phase
microemulsions are mixed with water, they always
take up all the water and often reject oil; hence,
Ymw = 0. Similarly, for upper-phase mi~roemulsions,
Ymo = 0. Definite trends are evident; y mo decreases
as salinity increases, whereas y mw increases with
increasing salinity. The salinity at which the two
functions intersect is termed optimal and is written
Cy; the tension there is called optimal interfacial
tension. For this system, Cy = 1.4 percent and y =
0.0009 dyne/em. .
For these samples, phase volumes depend on
salinity in the same manner as in Fig. 4. As salinity

ISO SOCIETY OF PETROLEUM ENGINEERS JOURNAL

 a b
3°/o 63/37 MEAC120XS/TAA, 3o/o 63/37 MEAC120XS/TAA,
48.5°/o 90/10 1/H, 48.5o/o Xo/o NaCI 48.5o/o 90/10 1/H, 48.5o/o Xo/o NaCI
~
~ (.)
(.) ......... --e-'Ymo vs. Vo/Vs
......... w 10-1
w 2 --A-.Ymw vs. Vw /Vs
2
>
>
c ••
c '' •
2
2
0 ''
0 en ''
en
2
2
w ' '.,
w ..... '

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.....
...J
...J
~ ''
~ (.) ''
•' '
(.) <(
<( u..
u.. a:
a: w
w .....
..... 10-4 2 10-4
2 0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 0 4 8 12 16 .20 24 28
SALINITY, o/o NaCI Vo/Vs or Vw/Vs
FIG. 7 - INTERFACIAL TENSION, VARIABLE SALINITY.

mcreases, excess water volume increases and , data are averaged with smooth curves that express
excess oil volume decreases.* This suggests a apparent trends. It is obvious that functions having
relationship between y and phase volumes. Such a ~~hyperbolic" character would be more appropriate.
relation appears in Fig. 7b, where log y mo is plotted Robbinsl4, 15 has developed a theory for spherical
vs the ratio of volume of oil in the microemulsion oil-external or water-external microemulsions that
phase to volume of surfactant in that phase, V0 /V 5 ; relates interfacial tension, Yi' within the micelle to
and log Ymw is plotted vs V w/V5 • The volume of Vw/V5 or V0 /V5 , respectively. This model can be
surfactant in the microemulsion phase, V5 , does not shown to be consistent with several of the trends
include the alcohol cosolvent. Both V0 /V 5 and reported here, providing Yi is arbitrarily identified
V w/V5 .were calculated from phase volumes and the with Ymw or Ymo and certain other simplifying
very good assumption that surfactant concentration assumptions are made regarding Robbins' interaction
in excess phases is negligible (Appendix C). In parameters.
these and subsequent y correlations of this type, Data for Fig. 7b were all measured by varying only
salinity. If over-all composition is varied, the same
trend is found, but data scatter is increased. For
63/37 MEAC120XS/TAA, 1o/o NaCI, example, y mo is plotted as a function of V0 /V5 in
90/10 1/H Fig. 8 for a variety of compositions for the system
63/37 MEAC120XS/TAA, 90/10 I/H, and 1-percent
~ NaCl. These are the same y data referred to earlier2
u
......... as • 'not suggesting any obvious correlation."
w
2
>
c
V0 /V8 AND Vw!Vs
Solubility and Solubilization Parameter
2
0 Recognition that volumes of oil or water solubilized
(j)
2 in a microemulsion phase in relation to the amount
w of surfactant are measures of interfacial activity will
1-
...J prove to have practical as well as conceptual value .
~ Although solubility of one aqueous or organic phase
0 in another is quite different from the notion of water
~ • or oil solubilized within surfactant micelles, it is
a:
w interesting to note some parallel, supporting
1- developments.
2
It has long been recognized that solubility
measurements provide a means of studying molecular
interactions. Hansen's approach,16 using the
Vo/Vs
FIG. 8 - INTERFACIAL TENSION CORRELATION *Tosch et al. 12 have observed the effect of salinity on water
VARIABLE COMPOSITION. ' content of an upper-phase microemulsion.

JUNE, 1976 151

solubility parameter concept of Hildebrand and
Scott, 17 • 18 is well known. Other investigators of
nonsurfactant systems have reasoned that, for the
liquid-liquid case, cohesional and adhesional
molecular forces that determine the magnitude of
interfacial tension also determine the extent to which
two liquids are soluble. In 1913, Hardy19 showed
that interfacial tension between aqueous and organic
liquid phases may be reliably considered as a linear
function of the log of the ''degree of miscibility" of
the liquids. More recently, Donahue and Bartell20
made a further study of the relationship between y
and solubility. None of these studies involved
surfactants.
Fig. 9 shows solubilization parameters, V0 /V s
and V w/V5 , as functions of salinity, corresponding
to y data in Fig. 7a. V0 /V5 is plotted only for lower-
or middle-phase microemulsions. V w/V5 for
lower-phase microemulsions would be of less interest
since all the water in the system is always in the
microemulsion phase and, therefore, V wiVs is
plotted only for upper- or middle-phase microemulsions.
Simultaneous occurrence of V0 /V s and Vw /V s for a
given salinity implies a middle-phase microemulsion,
and the two graphs are thereby mutually dependent.
For spherical water-external micelles, the effect of
increasing salinity is to decrease the water-hydrophile
interaction, permitting the micelle to attain a larger
radius and accommodate more oil in its interior.
Optimal Salinity
V0 /V5 and Vw /V5 intersect at e¢, the optimal
salinity for phase behavior. For this system, e ¢ =
1.5 percent (Fig. 9) and ey = 1.4 percent (Fig. 7a)
are nearly the same.
3o/o 63/37 MEAC120XS/TAA,
48.5°/o 90/10 1/H 48.5o/o X 0/o NaCI
I sufficiently accurate determination of optimal
22
20
18
(fJ
>
..........
~ nique is applied along a 1/1 WOR path, it identifies
>"-
0 the water side, depending on the lateral location of
(fJ
>
..........
0
> COHESIVE ENERGY RATIO
___!-OWE~DDLEI UPPER
PHASE . I PHAS__,E~--PHASE-
0.5 1.0 1.5 2.0 2.5
SALINITY, /o NaCI0
FIG. 9 - SOLUBILIZATION PARAMETERS.
152
At this point, one can conjecture that microemulsion
floods conducted in an optimal-salinity environment
recover more oil than otherwise; for this reason it
may be useful to explore sensitivity of optimal
salinity to location on the ternary diagram.
Fig. lOa shows e¢ as a function of over-all
surfactant concentration at constant 1/1 WOR for the
system 63/37 MEAC120XS/TAA, 90/10 I/H, and
brine. As over-all surfactant concentration increases,
C¢ decreases. At 9-percent 63/37 MEAC120XS/TAA
and C¢ = 1.26-percent NaCl, the over-all composition
is single phase. Also V0 /V 5 at C¢ decreases as
over-all surfactant concentration increases ·(Fig.
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lOb). In Fig. lOc, ech at constant surfactant
concentration (3-percent 63/37 MEAC120XS/TAA) is
plotted as a function of the over-all WOR. e¢
increases as WOR increases. These results provide an
explanation for the complex phase behavior illustrated
in Fig. 6. At high WOR' s on the left side of the
diagram, salinity is less than e ¢ and, hence,
surfactant will reside in an aqueous phase (Type I).
In the center, salinity is near optimal so the
expected Type III phase appears there. At low
WOR' s salinity is still close to optimal; hence, the
expected lower-phase microemulsions are found
there. Although there are insufficient data to
analyze a complete flooding situation, it is evident
that dependence of optimal salinity on surfactant
concentration and WOR could have important effects.
Previously ,2 optimal salinity, em' was determined
by measuring the least concentration of surfactant,
as a function of salinity, that would render a 1/1
water-oil mixture single phase. For the system now
under consideration, em 1.25-percent NaCl
(8-percent surfactant plus cosolvent) is approximately
equal to e¢ = 1.26-percent NaCl (9-percent
surfactant plus cosolvent).
In an earlier publication 2 it was 11• • • supposed that
salinity would provide a ternary diagram having a
plait point precisely in the center." This did not
turn out to be the case. However, the reason is now
clear. Near optimal salinity, em, the ternary diagram
resembles Fig. lb. There are two plait points, one
at far left near 100-percent water and one at far right
near 100-percent oil; a plait point is never located
in the center. When the phase disappearance tech-
either the plait point lying on the oil side or that on
M, which is quite sensitive to small changes in
salinity.
It is helpful to consider microemulsion interfacial
activity in terms of the cohesive energy ratio
introduced by Winsor.l 0 If Ehw is the total
interaction energy between the hydrophilic portion
of the surfactant molecule and water and Ez 0 is this
energy between the lipophilic portion and oil, then R,
3.0 3.5
the cohesive energy ratio, is defined as E z0 /E hw·
Interfacial activity depends on the value of R as
well as the magnitude of the terms Ez 0 and Ehw. High
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
interfacial activity corresponds to R - 1, together
with large values of Elo and Ehw' Winsor also
remarks that when micellar structure is spherical
water-external, R < 1; when it is spherical
oil-external, R > 1.
The concept of optimal salinity can be interpreted
in terms of R and the salinity dependence of E hw
and Elo. It seems reasonable to assume Ehw is a
montonicall y descreasing function of salinity,
whereas E lo is independent of salinity. Then ~y
corresponds to the salinity where Elo - Ehw (that 1s,
R- 1).
N, of the alkyl side chain was 9, 12, or 15
(Appendix A). Cosolvents included tertiary amyl and
tertiary buty 1 alcohols. Two oils having different
concentrations of aromatic component were used.
Dissolved solids in the aqueous phase included
NaCl, CaC1 2 • 2H 2 0, and XC biopolymer. Over-all
composition of equilibrated phases was always
3-percent 63/37 MEACNOXS/ alcohol, 48.5-percent
oil, and 48. 5-percent brine.
SURFACTANT STRUCTURE
Fig. 11 shows interfacial tension as a function of
salinity for MEAC9-, -Cl2-, and -Cl50XS/TAA when

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INTERFACIAL TENSION AND
PHASE BEHAVIOR
Interfacial tension as well as solubilization
parameters for microemulsions have been determined
as functions of salinity, temperature, molecular
structure of surfactant and alcohol cosolvent, oil
composition, and composition of dissolved solids in
the aqueous phase. Temperatures considered were
74 112 and 150 °F. Surfactant structures were
m;noeth~nol amine salts of alky 1 orthoxy lene
sulfonic acid, where the predominant carbon number,
the oil component is 90/10 1/H. Although these data
were obtained at 112 °F, similar results occur at 7 4
and 150 °F .21 A conclusion persisting throughout is
that increasing salinity causes a decrease in Ymo
and an increase in y mw· Furthermore, both Cy and
optimal tension depend on surfactant structure.
Increasing N from 9 to 15 causes a corresponding
decrease in Cy from 4.4- to 0.2-percent NaCl. This
is consistent with the notion that, for this system,
increasing N increases solubility of surfactant in
oil. Optimal tension decreased from 0.01 dyne/em
for N = 9 to 0.001 dyne/em for N = 15.

a b
63/37 MEAC120XS/TAA,
63/37 MEAC120XS/TAA, I
1/1 X 0/o NaCI 90/10 1/H
~
20~--------~------~
1/1 Xo/o NaCI / 90/10 1/H
3.0..--------------, 2 18
:::::i 16
<t
en 14
...J
<t 12
SINGLE PHASE ~
~
0
@J

-
t/)
>
0
10.0 > 1 2 3 4 5 6 7 8 9
OVERALL CONC., OVERALL CONC.,
0
/o 63/37 MEAC120XS/TAA c o/o 63/37 MEAC120XS/TAA

3o/o 63/37 MEAC120XS/TAA,

90/10 1/H, X 0/o NaCI
C3
ro

2.0l
2
~
0

~2
1.8
:::::i
<t 1.6
en
...J
1.4
<t
:! 1.2
i=
a.
0 1.00
.1
WATER-OIL RATIO
FIG. 10 - OPTIMAL SALINITY.
JUNE, 1976 153
 3%63/37 MEACNOXS/TAA, 3%63/37 MEAC120XS/TAA,
48.5%90/10 1/H, 48.5% X% NaCI 48.5% 90/10 1/H, '48.5% X% NaCI

::!! ~
u
........ ~
w w
z z
>
>
c
0
z
0 • oe Ymo
z Ci5 e6• Ymw
0 zw
Ci) 1-
z ..J
ct
w 0
1-
....1 ~
<( a:
w
0 1-
~
~

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a:
w 10•0
1-
~ SALINITY, o/o NaCI
10
SALINITY,% NaCI
FIG. 11 -INTERFACIAL TENSION, EFFECT OF
SURF ACT ANT STRUCTURE.
These results can be interpreted in terms of
cohesive energy tatio. Since E hw is a decreasing
function of salinity and E hw - E10 at Cy, both
Ehw (Cy) and £ 10 (Cy) increase as Cy decreases,
resulting in higher interfacial activity and, hence,
lower y. Also, it is noteworthy that sensitivity of
Ymo and Ymw to salinity, in the neighborhood of Cy,
increases with N.
Increasing N at constant salinity causes phase
behavior to move in the direction £ --7 m --7 u. Associ-
ated trends are that Ymo and Vw/V5 decrease, while
Ymw and V0 /V 5 increase.
Fig. 12 shows the corresponding y mo vs V 0 /V s
and y mw vs V w/V5 correlations. The correlations
are dependent on alkyl carbon number since interfa-
cial tension corresponding to a given V6 /V5 or
V w/V5 increases with N.
TEMPERATURE
Fig. 13 shows interfacial tension as a function of
salinity for MEAC120XS at 74, 112, and 150 ° F.
2 3 4 5 6
FIG. 13 - INTERFACIAL TENSION, EFFECT OF
TEMPERATURE.
Evidently, both Cy and optimal tension increase
with temperature. At 74 op, Cr = 1.4-percent NaCl
and tension there is 0.0009 dyne/em; at 150 °F,
C'Y. = 2. 7-percent NaCl and optimal tension is
0. 0024 dyne/ em.
Fig. 14 shows the corresponding interfacial
tension correlations. The y mo vs V 0 /V5 correlation
is not significantly dependent on temperature, but
the Ymw vs Vw/V5 correlation is shifted downward
with temperature.
Fig. 15 summarizes relations among C Y' optimal
interfacial tension, temperature, and surfactant
structure. C y increases with increasing temperature
at constant N and with decreasing N at constant
temperature; where temperature is constant, optimal
tension increases as C increases. An important
application of these resufts is to select a surfactant
structure that gives y mo = y mw at a given temperature
and salinity and to estimate the value of interfacial
tension there, thus providing a guide for surfactant
structure required to be effective in a particular
reservoir environment.
Fig. 16 shows dependence of interfacial tension
and phase behavior on temperature when salinity is

3% 63/37 MEACNOXS/TAA, -o- N=9

48.5% 90/10 1/H, 48.5% X% NaCi --•-- N=12
. 112°F _,.__ N=15
a b

'Ymo vs Vo/Vs 'Ymw vs Vw/Vs

::2E
a:~
ww
~2
<C>
:s:c
12
20
o-
_CJ)
C/)2
...Jw
::)~
::2E...J
W<(
o-
a:u •
u<C
_u.
:Effi
~
2

~~ ~M

FIG. 12- INTERFACIAL TENSION CORRELATIONS, EFFECT OF SURFACTANT STRUCTURE.

154 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

 3% 63/37 MEAC120XS/TAA.
48.5% 90/10 1/H, 48.5% Xo/o NaCI
--o- 74"F
---e--- 112°F
--6-- 150"F
a b
'Ymo vs. Vo!Vs 'Ymw vs. Vw!Vs
:E
~
10-1f::-
f=
~ 10-1
a:--
~'~
w
:::!Z ~ 0 ww
t-Z
\0 ', 0

..
.. 0 '
o> 1- <t>
lc 1-
• ;:c ~ '',,, 0

z .
oz
_o 10-2f::- .... 0 12
z 0 10- 2 \ '•',
Cl)-
...ICI)
=>z
:E~
W...J
f=
~
1-
1-
.. ... ...
0 o-
_CI)
CI)Z
...IW
::>I-
:!:...I
150"F\
\ 112"F',
'
• ''
''
74"F
•
• w<t

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Oc:t
a:-
uu 10- ~
3

. 0 0 u 10-3 ''
''
•
-<t
:Eu.. ~ • C:c:t
Uu..
-a: ' 0
a: 1-
:Ew
w 1- 0
1- 1-
I-
~ ~
10-4 10-4
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20 22

Vo!Vs Vw!Vs

FIG. 14 - INTERFACIAL TENSION CORRELATIONS, EFFECT OF TEMPERATURE.

2-percent NaCl and the surfactant is MEAC120XS.

8~----------------------------------, Increasing temperature causes phase behavior to
e • •, OPTIMAL INTERFACIAL TENSION. change in the direction u ~ m ~ £. As temperature
7 DYNE/CM
increases, y mw and V0 /V5 decrease while y mo and
6 V wiVs increase. Optimal temperature, defined as
the temperature corresponding to the intersection of
(3 5 the two y curves, is 127 °F.
m
z Fig, 17 shows dependence of V0 IV5 and Vw IV s
?F. on temperature and salinity for MEAC120XS. Increas-
-;..3
(.)
ing temperature at constant salinity corresponds to
decreasing V0 /V5 and increasing Vw/V 5 • For this
2
case, then, as temperature is increased, C¢
increases and V0 /V5 decreases. This suggests that
c15 .o.001
o~~--~--~~~~--L-~---~---L-~~
70 80 90 100 110 120 130 140 150 160 170 180
TEMPERATURE. °F 3°/o 63/37 MEAC120XS/TAA,
FIG. 15 - DEPENDENCE OF OPTIMAL SALINITY ON 48.5°/o 90/10 1/H, 48.5o/o X0/o NaCI
TEMPERATURE AND SURFACTANT STRUCTURE. 22
• Vo/Vs, 74°F
20 o Vo/Vs, 150°F
3o/o 63/37 MEAC120XS/TAA,
48.5°/o 90/10 1/H, 48.5°/o Xo/o NaCI 18 • Vw /Vs, 74°F
6 Vw/Vs, 150°F
16
J;---- -6--= 10 1
>
rJ)

c:r--- - - - -0 :=
Vo/Vs ........... 14
~
Vw/Vs = ~
>
-
0 12
2 rJ)
~

0
~-o
0 10-1 ~ 'V,mw -10° > rJ)
10
I
en f- ...........
0 > p
I
2 ~ ~ Ymo > ........... \

:
0
~\ 150°F
w~ 1
8
1-u
...J........._
<(w
~ >
6 \
- 2 10-2 t=-
u> ~
~ 4
~0 I-
I-
~
a: 1-
w I-
2 '-6
1-
2 0
1o-3.__...~...1_---LI------'I_ _..JI'------
60 80 100 120 140 160 0 1.0 2.0 3.0 4.0
TEMPERATURE, °F SALINITY, 0/o NaCI
FIG. 16- EFFECT OF TEMPERATURE ON FIG. 17 - EFFECT OF TEMPERATURE ON
INTERFACIAL TENSION. SOLUBILIZATION PARAMETERS.

JUNE, 1976 155

Cy increases with increasing temperature because
Ez 0 decreases and Ehw increases.
COSOLVENT
Fig. 18 shows interfacial tension as a function of
salinity for two different cosolvents, tertiary butyl
alcohol and tertiary amyl alcohol; the surfactant is
MEAC120XS in both cases. Increasing alcohol-
cosolvent molecular weight causes CY. and optimal
tension to decrease. When TBA (tertiary buty 1) is
the cosolvent, optimal salinity is 2.2-percent NaCl
and tension is 0.0022 dyne/ em, whereas when TAA
(tertiary amyl) is the cosolvent, Cy
= 1.4-percent
dyne/em; for 90/10 Isopar M/HAN, optimal salinity
is 1.4-percent NaCl and the tension there is 0.0009
dyne/em.
Evidently, increasing oil aromaticity causes an
increase in Ez 0 , consistent with the fact that a portion
of the surfactant lipophile is aromatic. The result
that a lower Cy corresponds to a lower optimal tension
is in accordance with the cohesive energy-ratio
concept. Also, increasing oil aromaticity at constant
salinity caused phase behavior to change in the
direction E--) m --) u, while Ymo and V w/V5 decreased
andy mw and V 0 /V5 increased. For Isopar M, the Ymw
correlation lies below that for 90/10 I/H, and they mo

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NaCl and optimal tension is 0.0009 dyne/ em. correlation is only slightly composition-dependent.21
The TBA y mw and Ymo correlations appearing in
Fig. 19 are excellent and nearly the same. DISSOLVED SOLIDS
Comparison with Fig. 7b shows that the Ymo When the surfactant is MEAC120XS, neither optimal
correlations for TAA and TBA are about the same,
but the y mw correlation for TBA lies below that for
TAA. The fact that the TBA interfacial-tension 3o/o 63/37 MEAC120XS/TBA,
data (Fig. 18) and the correlations (Fig. 19) fit so 48.5°/o 90/10 1/H, 48.5o/o X0/o NaCI
well with smooth curves is consistent with the ------ 'Ymo vs Vo/Vs
nearly simple phase behavior shown by TBA (Figs.
3a through 3c).
An increase in alcohol molecular weight at
constant salinity causes phase behavior to move in
-~
(.)
w
2
>
c
-•- 'Ymw vs Vw/Vs

the direction E --) m --) u, whereas Ymo and V wiV 5

decrease and y mw and V0 /V5 increase. Increasing 2
alcohol molecular weight, or increasing N, 0
(i5
directionally influences y and phase behavior in the 2
same manner. w
1- '
..J
OIL COMPOSITION
<t
Fig. 20 shows interfacial tension as a function of u
<t
salinity for two different oils, 90/10 I/H and Isopar LL
M. Increasing aromatic content of the oil from 0 a:
w
(Isopar M) to 10 percent (90/10 I/H) decreases both 1-
optimal salinity and tension. For Isopar M, Cy_ = 2
1.8-percent NaCl and optimal tension is 0.0026

3% 63/37 MEAC120XS/COSOLVENT,
48.5% 90/10 1/H, 48.5% Xo/o NaCI
Vo/Vs or Vw/Vs
FIG. 19 - INTERFACIAL TENSION CORRELATIONS,
TBA.
~

-
(.)
w
z
> ~
3%63/37 MEAC120XS/TAA,
48.5% X% NaCI, 48.5% OIL

c /
/
/ ~
z /
~
0 17/ w
z
en 6.-/ >
zw ~ /
c
1- ' I
z
0
-1 lATBA en
<t D;l C::.\ z
u TAA q w
1-
<t
LL
\ ...1
<(
a:
w
'0 (3
<(
1- LL
a:
z w
1-
10-4L___L___
L __ _L __ _L---~--~--~~ ~
0 2 4
2 3 4 5
SALINITY,% NaCI
SALINITY,% NaCI
FIG. 1 8 - INTERFACIAL TENSION, EFFECT OF
ALCOHOL. FIG. 20 - INTERFACIAL TENSION, EFFECT OF OIL.

156 SOCIETY OF PETROLEUM ENGINEERS JOURNAL

salinity nor tension 1s significantly affected by the TABLE 1 -SUMMARY OF INFLUENCE OF SOME VARIABLES ON PHASE
presence of 750 ppm by weight of XC biopolymer in BEHAVIOR, INTERFACIAL TENSION, AND SOLUBILIZATION PARAMETER
Resulting Trends
the aqueous phase (Fig. 21). This is in marked
Phase
constrast to the strong detrimental effect that XC Increasing Variable Behavior Ymo Vo!Vs Ymw Vw!~
:i
biopolymer has on the extent of the multi phase region.l Salinity f -> m-> u + +
Alkyl chain carbon number
Biopolymer has little effect on the Ymo correlation, (N}, molecular weight of
alcohol cosolvent, oil
but the Ymw correlation is shifted downward.21 aromaticity, Ca++/NaCI
Fig. 22 shows interfacial tension as a function of ratio e -> m -) u + +
Temperature u -) m ~ e + +
salinity for two different compositions of dissolved XC biopolymer concentration Insignificant changes
- indicates a decrease.
solids in the aqueous phase, NaCl and 10/1 + indicates an increase.
NaCl/CaC1 2 · 2H 2 0. Addition of Ca++ to the water
phase decreased optimal salinity from 1.4-percent
NaCl to 1.1-percent total dissolved solids, but_ the

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effect of Ca++ on optimal tension was small. This is 3o/o 63/37 MEAC120XS/TAA,
similar to the finding that Ca ++ caused a decrease 48.5% 90/10 1/H, 48.5o/o Xo/o TDS
in C m' but the extent of the multi phase region was
not significantly affected. 2 The y mo vs V 0 /V 5
correlation is affected very little by Ca ++, but y mw
is moved downward relative to the no Ca++ case.21
Addition of 750-ppm XC biopolymer to the brine
containing Ca++ (10/1 NaCl/CaC12 • 2H2 0) does not
-
2
>
c
~
(.)
w
t:.'
I
I ....... ,"l:::f",.,.'
_.,6

I
affect interfacial tension behavior in a significant 2 I
manner (Fig. 23). This is similar to the minimal 0 I
Ci5 I I
effect XC biopolymer had on interfacial tension 2 I I
w I I
behavior corresponding to NaCl brines (Fig. 21).
Comparison of y correlations for the case of XC
....
..J
14
I I
biopolymer and Ca++ with corresponding correlations <( \I
for the case of Ca++ only21 indicates that XC u
<(
~NaCI ONLY
biopolymer does not significantly affect the LL lq_
a: I \
6 \
relationships.
....w \
0
2
SUMMARY
For the systems studied here, Table 1 shows
trends in y and phase behavior that result from
increasing a given variable of interest, providing the
SALINITY, o/o TOTAL DISSOLVED SOLIDS
over-all composition is constant. Tabulated results
FIG. 22 - INTERFACIAL TENSION, EFFECT OF Ca ++,

3% 63/37 MEAC120XS/TAA, 3o/o 63/37 MEAC120XS/TAA,

48.5% 90/10 1/H, 48.5% X% NaCI 48.5o/o 90/10 1/H, 48.5o/o Xo/o TDS
o--q 6
\ 750 ppm XC NO XC I

-
I
~ ~

-
(.)
w \/
\
--~ (.)
w
2 I 2 /
> \ > /

c \ I
c lj
\ ~ I
2 I
I 2 I
0 I 0
U5 I Ci5 lea++, 750 ppm XC
2 I
w I 2
w
~
...J
I ....
..J
<( <(
(3
<(
u.
u
<(
a: LL
w a:
~
2 ....w
2

2 3
SALINITY, % NaCI SALINITY, % TDS
FIG. 21 - INTERFACIAL TENSION, EFFECT OF XC FIG. 23 - INTERFACIAL TENSION, EFFECT OF XC
BIOPOLYMER. BIOPOLYMER, ca++.

JUNE, 1976 157

show that whenever phase behavior changes in the
direction E ~ m ~ u, associated trends are that Ymo
and Vw /Vs decrease, while Ymw and V0 /V s increase.
.
When the direction of phase-behavior change 1s
opposite (u ~ m ~ £), opposite trends are observed.
It is conjectured these results will hold for all
surfactant systems.
SCREENING PROCEDURE
The proposed concept relating changes in any
variable of interest to directional changes in phase
behavior (£ ~ m ~ u or u ~ m ~ £), together with the
general conclusion that these phase behavior
changes are associated with definite interfacial
tension trends, suggests a rapid method for studying
interfacial-tension behavior.
The method consists of preparing a set of samples
corresponding to a fixed over-all composition of
surfactant, alcohol cosolvent, oil, and brine, where
some variable of interest is changed in a systematic,
monotonic manner. In many examples discussed here,
the selected over-all composition was 3-percent
63/37 surfactant/ alcohol co solvent, 48. 5-percent
oil, and 48. 5-percent brine; and salinity was
increased. These samples are thoroughly mixed and
allowed to remain undisturbed at constant temperature
until the initial opaque emulsion completely
disappears, and distinct translucent phases remain.
If the direction of phase-behavior change is
£ ~ m ~ u, it follows that trends are that y mo de-
creases and y mw increases, and the converse. . for the given temperature and alcohol cosolvent.
Quantitive results are obtained by measunng
sufficient interfacial tensions that the y mo vs V0 /V s
and y mw vs Vw /Vs correlations can be established.
Once this is done, no further y measurements are
needed; any additional tenswns can be estimated
using the correlations.
For example this approach finds application 1n
determining, for a given surfactant, the effects of
salinity, oil composition, or temperature on
interfacial tension. Of special interest is the
commonly occurring circumstance wherein salinity, oil
composition, and temperature are fixed for a particular
reservoir application and the method is used to
screen surfactants for domains of requisite low
interfacial tension.
SUMMARY AND CONCLUDING REMARKS
Multiphase behavior of the system monoethanol
amine salt of CN-orthoxy lene sulfonic acid, alcohol,
Isopar M/Heavy Aromatic Naptha, and NaCl has
been studied as a function of N, percent of NaCl,
percent of aromatics, alcohol, temperature, and
presence of Ca++ or XC biopolymer in the aqueous
phase.
Phase behavior is conveniently classified as
Winsor's Type I, II, or III systems, which are referred
to here as lower-, upper- or middle-phase
microemulsions, respectively.
Multiphase compositions of these pseudoternary
systems largely resolve into a microemulsion phase,
an excess water phase containing molecularly
158
dispersed surfactant,lO or an excess oil phase, or
both the latter. Occasionally, two or more
microemulsion phases will coexist. Mixtures of these
phases are ordinary opaque emulsions that are
unstable and will eventually separate on standing.
Increasing salinity causes the microemulsion phase
to undergo transitions in the direction lower~ middle
~upper. In the course of these transitions, resistivity
steadily increases and there are no birefringent or
streaming birefringent phases; however, there are
viscosity and phase volume cusps at the transition
points suggesting micellar changes there. Micellar
structure of the lower phase is thought to be
Downloaded from http://onepetro.org/spejournal/article-pdf/16/03/147/2158634/spe-5565-pa.pdf by Universitatea Petrol-Gaze Ploiesti user on 22 February 2023
dominated by the spherical, water-external config-
uration, and that of the upper phase by the inverted
form. Structure of the middle phase is unknown.
As salinity increases, microemulsion-oil interfacial
tension decreases and microemulsion-water tension
increases. The point of intersection of these
functions, Cy, is termed optimal since it p.rovides
equal interfacial tensions between oil and
microemulsion on the one hand and between water
and microemulsion on the other. It is conjectured
that corresponding middle-phase microemulsions will
have favorable oil-displacing characteristics.
The solubilization parameter for oil in surfactant,
V0 /Vs'. for the microemulsion phase is an increasing
function of salinity, whereas Vw /V5 is a decreasing
function of salinity. The intersection of these
functions, c¢!, is termed optimal because it
represents a balanced oil-water-surfactant system
C¢, Cy, and Cm (see Optimal Salinity) are frequently
close in numerical value.
Real ternary systems of interest for tertiary oil
recovery are exceedingly complex because of the
large number of components. In particular, the
multiphase boundary determined at constant over-all
surfactant concentration depends on the value of
that concentration. Optimal salinity for these
systems depends on surfactant concentration and
WOR; therefore, it is expected that design of
effective microemulsion systems will require
consideration of these complexities.
It is shown that interfacial tensions decrease as
V0 /Vs or Vw /Vs increase. These dependences
provide convenient correlations that can decrease
the number of interfacial tensions that must be
determined experimentally, are useful in microemul-
sion screening procedures, and provide insight
regarding requirements for low interfacial tension.
Effects of the several variables studied on the
interrelations of phase behavior, interfacial tension,
and the solubilization parameter are accumulated in
Table 1 for convenient reference. Further, a graph is
presented (Fig. 15) that relates temperature, optimal
salinity, length of the alky 1 chain (N ), and interfacial
tension. Thus, for a given reservoir and flooding
situation, estimates can be made of the types of
phase trans1t1ons a microemulsion slug will
experience, as well as of bounds on associated
interfacial tensions. With this information, capability
to assess potential flooding effectiveness 1s
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
enhanced.
Finally, detailed study of multi phase aspects of
microemulsion systems is useful for understanding
microemulsions and surfactants in general and
should prove of value in the design of effective
flooding systems for tertiary oil recovery.
NOMENCLATURE
optimal salinity for miscibility, percent
N aCl or percent TDS
optimal salinity for interfacial tension,
percent NaCl or percent TDS
optimal salinity for phase behavior, percent
NaCl or percent TDS
Ehw hydrophile-water interaction energy
Elo lipophile-oil interaction energy
£ lower phase
m middle phase
M compositional point
N alky 1 side-chain carbon number
R cohesive energy ratio
upper phase
solubilization parameter for oil in microe-
mulsion, volume ratio of oil to surfactant
in microemulsion phase
Vo/Vs solubilizatio,n parameter for water in microe-
mulsion, volume ratio of water to
surfactant in microemulsion phase
X a variable
y interfacial tension, dyne/ em
Ymo microemulsion-oil interfacial tension,
dyne/em
microemulsion-water interfacial tension,
Ymw
dyne/em
ACKNOWLEDGMENTS
We are indebted to Patsy Gee who measured most
of the interfacial tensions in addition to acquiring
much of the phase behavior data. We also appreciate
the experimental contributions of George Runberg,
Carl Beitelshees, G. L. Huckaby, and April Grizzle.
REFERENCES
1. Healy, R. N., Reed, R. L., and Carpenter, C. W.: "A
Laboratory Study of Microemulsion Flooding," Soc.
Pet. Eng. ]. (Feb. 1975) 87-103; Trans., AIME Vol.
259.
2. Healy, R. N. and Reed, R. L.: "Physicochemical
Aspects of Microemulsion Flooding," Soc. Pet. Eng.
]. (Oct. 1974) 491-501; Trans., AIME, Vol. 257.
3. Stegemeier, G. L.: "Relationship of Trapped Oil
Saturation to Petrophysical Properties of Porous
Media," paper SPE 4754 presented at the SPE-AIME
Third Symposium on Improved Oil Recovery, Tulsa,
Okla., April 22-24, 1974.
4. Taber, J. J.: "Dynamic and Static Forces Required to
Remove a Discontinuous Oil Phase From Porous
Media Containing Both Oil and Water," Soc. Pet. Eng.
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5. Taber, J. J., Kirby, J. C., and Schroeder, F. U.:
JUNE, 1976
"Studies on the Displacement of Residual Oil:
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Symposium (1973) Vol. 69, 53.
6. Foster, W. R.: "A Low-Tension Waterflooding
Process," ]. Pet. Tech. (Feb. 1973) 205-210; Trans.,
AIME, Vol. 255.
7. Melrose, J. C. and Brandner, C. F.: "Role of Capillary
Forces in Determining Microscopic Displacement
Efficiency for Oil Recovery by Waterflooding," J. Cdn.
Pet. Tech. (Oct'. -Dec. 1974) 54-62.
8. Marsden, S. S., Jr., and McBain, J, W.: "Aqueous
Systems of Nonionic Detergents as Studied by X-Ray
Diffraction," J. Phys. Chem. (1948) Vol. 52, 110-129.
9. Holm, L. W.: "Use of Soluble Oils for Oil Recovery,"
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]. Pet. Tech. (Dec. 1971) 1475-1483; Trans., AIME,
Vol. 251.
10. Winsor, P. A.: Solvent Properties of Amphiphilic
Compounds, Butterworth's Scientific Publication,
London (1954).
11. Adamson, A. W.: "A Model for Micellar Emulsions",
]. Coll. Int. Sci. (1969) Vol. 29, 261-267.
12. Tosch, W. C., Jones, S. C., and Adamson, A. W.:
''Distribution Equilibria in a Micellar Solution System,''
]. Colt. Int. Sci. (1969) Vol. 31, 297-306.
13. Shah, D. 0.: "On Distinguishing Microemulsions From
Cosolubilized Systems," paper presented at 48th
National Colloid Symposium, Austin, Tex., June 1974.
14. Robbins, M. L.: "The Theory of Microemulsions,"
paper presented at the 76th National AIChE Meeting,
Tulsa, Okla., March 7-14, 1974.
15. Robbins, M. L.: "Theory of Microemulsions," paper
presented at the 48th National Colloid Symposium,
Austin, Tex., June 1974.
16. Hansen, C. M.: "The Universality of the Solubility
Parameter," I&EC Prod. Res. and Dev. (March, 1969)
Vol. 8, 2-11.
17. Hildebrand, J. and Scott, R.: Solubility of Non-
Electrolytes, 3rd ed., Reinhold Publishing Corp., New
York ( 1949).
18. Hildebrand, J. and Scott, R.: Regular Solutions,
Prentice-Hall Book Co., Inc., Englewood Cliffs, N. J,
(1962).
19. Hardy, W. B.: Proc., Royal Soc. of London (1913) Vol.
88A, 313.
20. Donahue, D. J. and Bartell, F. E.: "The Boundary
Tension at Water-Organic Liquid Interfaces,"]. Phys.
Chern. (1952) Vol. 56, 480-484.
21. Healy, R. N., Reed, R. L., and Stenmark, D. G.:
"Multiphase Microemulsion Systems," paper SPE
5565 presented at SPE-AIME 50th Annual Fall
TechniCal Conference and Exhibition, Dallas, Sept.
28-0ct. 1, 1975.
22. Prillieux, M. and Tirtiaux, R.: "Enhancing the
Recovery of Oil from Subterranean Formations," U. S.
Patent No. 3, 799,263 (March 26, 1974).
23. Epton, S. R.: "A New Method for the Rapid Titrimetric
Analysis of Sodium Alkyl Sulphates and Related
Compounds," Trans., Faraday Society (1948) Vol. 44,
226-230.
APPENDIX A
CHEMICALS
Anionic surfactants were monoethanol amine salts
of alky 1-orthoxy lene sulfonic acid where the alky 1
side chain was predominately either nonyl, dodecyl,
or pentadecyl. These will be designated by
159
 TABLE 2 - ALKYL SIDE CHAIN MOLECULAR WEIGHT Interfacial tension corresponding to each interface
DISTRIBUTIONS
was measured using a previously describe.d2 sessile
Number of drop apparatus, maintained at the temperature of
Carbon Atoms Distribution (weight percent)
in Side Chain Nonyl .Oodecyl Pentadecyl interest with an air bath. Interfacial tension was
8 1 measured as a function of time until steady state
9 69 was achieved. Usually, this required less than 10
10 23 10.6 minutes. Tensions reporteq here are averages of at
4.8
11 7 16.1 least four measurements made on several different
12 57.2 1.5
9.6 2.6
drops. Precision was about ± 15 percent for y > 10-3
13
14 3.8 10.5 dyne/ em and ± 25 percent when 10-4 < y .S 10-3
15 2.7 56,5 dyne/em.
16 17.7
17 6,4

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MEACNOXS, where the predominant carbon number
(N) of the alkyl chain is either 9, 12, or 15.
Side-chain molecular weight distributions for these
surfactants are given in Table 2. Dodecyl orthoxylene
sulfonate 22 was supplied by Exxon Chemical Co.,
U.S.A., and is designated Sulfonate FA-400. The
specific dodecyl sulfonate used was specially
prepared and was ~ 92-percent active. Inactive
components were unreacted oil and salt.
The nonyl and pentadecyl surfactants were
laboratory-synthesized specifically for this work.
They were ~ 75-percent active; inactives were ~
2-percent salt, and ~ 23-percent unreacted oil. All
surfactant concentrations reported here are on a
100-percent active basis.
Alcohol cosolvents were ccBaker analyzed" tertiary
butyl (TBA) and tertiary amyl (TAA) reagents
obtained from J. T. Baker Chemical Co., Phillipsburg,
N.J. In all cases, a volumetric mixture of 63-percent
surfactant and 37-percent cosolvent (63/37
MEACNOXS/ alcohol) was used.
Oils were Isopar M and a mixture of 90-percent
Isopar M and 10-percent Heavy Aromatic Naphtha
(90/10 I/H). Isopar M and Heavy Aromatic Naphtha
are trade names for refined paraffinic and aromatic
oils, respectively, sold by Exxon Co., U.S.A.
APPENDIX B
PROCEDURES
INTERFACIAL TENSION
Multiphase samples were thoroughly mixed in
100-ml graduated cylinders and were allowed to
equilibrate at the temperature of interest until the
initial emulsions separated into distinct, translucent
phases having volumes that did not change with time.
This pre-equilibration procedure was necessary for
reproducible and interpretable y measurements. Time
required for the emulsion to completely disappear
varied from minutes to months.
Volume of oil, V0 , or water, Vw, contained in an
equilibrated microemulsion phase was determined
from measurement of the corresponding excess phase
volume. For the 100-ml samples used here, these V 0
and Vw were accurate within ± 1 ml. Most samples
involved 3-percent 63/37 MEACNOXS/alcohol or,
alternatively, 1.89-ml surfactant. For these, the
accuracy of determining V0 /V5 and Vw /V5 was ±
0.5, assuming negligible surfactant concentration in
excess phases.
APPENDIX C
PROPERTIES OF EXCESS PHASES
Excess water and oil phases corresponding to a
specific middle-phase composition (3-percent 63/37
MEAC120XS/TAA, 48.5-percent 90/10 I/H, and
48.5-percent 1.5-percent NaCl) were analyzed for
MEAC120XS. X-ray fluorescence was used to deter-
mine total sulphur in the excess oil phase, and
Epton's method2 3 was applied to determine sulfonate
content for excess water. MEAC120XS concentration
was < 0.1 weight percent in the excess oil and was
0.02 weight percent in the excess water. It is
concluded that the assumption of negligible sulfonate
concentration in excess phases is a good one. A
corresponding assumption is not tenable for the
cosolvent, and it is expected that alcohols will be
variously distributed among microemulsion, excess
water, and excess oil phases)O, 11 The result is
that V0 /V5 and Vw /V5 numbers are very good, but
binodal curves may be somewhat in error since
alcohol is included in the ccsurfactant" coordinate.
The density of all excess phases discussed here
was the same as either the corresponding oil or
water component. Also, all excess phases involving
MEAC120XS had the same colorless appearance as
the water or oil ·component. In a very few cases,
excess phases involving MEAC90XS and MEAC150XS
were slightly colored.
***

160 SOCIETY OF PETROLEUM ENGINEERS JOURNAL