Thermodynamic Modeling of
Pseudotemary Phase Behavior
William R. Rossen, * U. of Minnesota
Roger G. Brown, MTS Systems Corp.
H. Ted Davis, SPE, U. of Minnesota
Stephen Prager, U. of Minnesota
L.E. Scriven, SPE, U. of Minnesota
Abstract
Phase behavior is the fulcrum at which the chemistry and
physics of surfactant and solvent systems govern the
engineering and economics of chemical flooding. Salient
behavior is represented by pseudoternary diagrams that
account for polar, nonpolar, ~nd amphiphilic com-
ponents. The common l:, 3, 2, phase-split progres-
sion-induced, for example, by salinity change in
microemulsion systems-is required by thermodynamic
principles. Although such progressions can be simulated
semiempirically, modeling them with a suitable free-
energy function or an equation of mixture state is more
reliable for interpolating and extrapolating limited data
on phase splits and coexisting phase compositions for
use in mechanism-based computer simulation of
laboratory experiments and field applications.
Simple equations of mixture state prove inadequate but
lead to the promising new linearly screened Flory-
Huggins (LSFH) equation, which accounts for
simultaneous association of amphiphile with oil and
water and aggregation of surfactant amphiphile into
curved sheetlike structures that separate water-rich from
oil-rich regions. From this equation for a ternary mixture
are calculated representative sets of diagrams with con-
tinuous progressions of tielines and binodals, plait
points, tie-triangles, and three-phase regions with their
critical endpoints. Several overlapping regions of
metastable one- and two-phase equilibria are identified.
Free-energy surfaces are pictured, and the free-energy
factor that jointly controls interfacial tension (IFT) is
computed. Ultralow tensions are favored by low-relief
free-energy surfaces; so also are long-lived metastable
states. The exponentially screened Flory-Huggins
(ESFH) equation, superior in some ways to the linearly
screened version, also is discussed briefly.
• Now with Chevron Oil Field Research Co.
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DECEMBER 1982
Computational methods are described for fitting the
six parameters of the ternary equation to data as well as
for predicting phase behavior from given parameters.
Introduction
Petroleum most often is recovered by causing a second
fluid phase to displace liquid-phase petroleum from the
pore space of reservoir rock. The exception would be a
totally miscible process, which is generally imprac-
ticable. The split of gross local composition into im-
miscible phases and the equilibrium partitioning of com-
ponents among the phases is called phase behavior.
Phase behavior governs the economics and engineering
of chemical flood process design. 1-12
Such chemical flooding processes are of two types: 6
those that rely on altering phase relations per se, as in the
solubilization and swelling mechanisms; and those that
alter fractional flow relations, as in the ultralow tension
mechanism, where the target is the capillary forces that
conspire with pore space to entrap residual oil and hold it
immobilized. That the IFT behind capillary forces cor-
relates with the pattern of phase behavior as a "field"
variable-i.e., a variable that is equal among phases in
equilibrium, or one that is nearly so, like salinity, is
varied-has been recognized for some time. 2 The
recently developed mean field theory of mUlticomponent
IFT's 13-15 confirms that the same free-energy relations
(most easily pictured as a mathematical surface) that dic-
tate phase behavior also rule jointly the IFT's between
phases. This is especially true near plait points, con-
solute points, and other critical points where universal
dimensionless relations called scaling laws govern both
the way that phases approach each other in composition
and the way that IFT vanishes as any critical point is ap-
proached. 12 ,16,17 Now there is experimental 18 and
theoretical 19 evidence that the wettability relations to
which fractional flow is so sensitive 20 also correlate
945
 10-1
~
Y0/M
E 10- 2
~
C1.>
~ 10-3
'"0
10- 4
II 1.3
wt. % Noel
Fig. 1-Schematic of microemulsion phase and 1FT behavior.
strongly with the pattern of phase behavior, at least when
conditions are not too far removed from a critical point.
Salient behavior of the multi phase systems of chemical
flooding is represented by pseudoternary models that ac-
count for polar, nonpolar, and amphiphilic com-
ponents. 1,2. All species present are apportioned in some
way among three generic pseudocomponents: aqueous,
oleic, and amphiphilic; or, more loosely, brine or water,
oil, and amphiphile or surfactant. The resulting two-
dimensional (2D) pseudoternary diagram is of course a
function of the field variables held constant or nearly
constant, as for example the chemical potential of a
minor component that remains predominantly in one
pseudocomponent. Inorganic salts may approach this
ideal. 21 Despite its utility, the pseudoternary approxima-
tion is limited in its accuracy, 21-25 although judicious
apportioning of species among the pseudocomponents
can minimize the errors incurred. 21 - 23 Moreover, a
pseudoternary representation is actually correct for the
representation of a family of phase diagrams as field
Variables are traced along some path, as in a single-
temperature or salinity scan.
A similar pseudoternary representation finds applica-
tion to systems of carbon dioxide, light hydrocarbons,
and heavier hydrocarbons. 26,27
In this paper we concentrate on the phase behavior of
what have come to be called microemulsion systems. In
particular we consider the typical progressions of phase
diagrams with increasing salinity when the surfac-
tant/amphiphile suite has been so matched to the oil and
range of brines (see Fig. I) that the multiphase region at
lower surfactant contents is entirely surrounded by a
single-phase microemulsion zone, all the way from brine
and aqueous micellar solutions, to microemulsions dilute
in no pseudocomponent, to oleic micellar solutions and,
946
1.5 1.7 19
ultimately, oil. l,2 In the miscibility gap, or two-phase
region, at low salinity an ionic surfactant partitions
preferentially into the aqueous phase, as indicated by
tieline slope. Phase volumes can be found from the mix
point and the ends of the tieline passing through it, pro-
vided volumes do not change appreciably on mixing-a
reasonable first approximation. With increasing salinity,
a critical endpoint may appear at which the critical tieline
opens into a three-phase region. Whether the third phase
is seen depends on whether the mix point falls in the
three-phase region; when it does, phase volumes can be
found from it and the vertices of the tie-triangle that
passes through it. With continuing increase in salinity,
the composition of the third, surfactant-rich phase moves
to and beyond equal brine and oil contents, until it disap-
pears in a second critical endpoint, at which the three-
phase region closes down into another critical tieline. At
still higher salinities there is just a two-phase region in
which surfactant partitions preferentially into the oleic
phase. The bellwethers of the two-phase regions are the
plait points, which tieline slopes tend to follow, so that
~lait Eoint right vs. plait point left is a cruc~al di~tinc­
tlon. -II _The sequence of phase counts III Fig. 1
is 2, 3, 2, in the mnemonic notation of Knickerbocker
et aI., 28 which gives the number of equilibrium phases
and, for a two-phase system, indicates whether the sur-
factant is pri~rily in the lower, water-rich (~) or up-
per, oil-rich (2) phase or equally partitioned between
the two m.
The sequence of phase diagrams when a third fluid
phase appears in such a ternary system must be
qualitatively that depicted in Fig. 1, as Knickerbocker et
al. showed. 29 That is, the progression of plait points,
tielines, binodals, and vertices of three-phase tie-
triangles must be continuous, the three-phase progres-
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
sions starting and ending at critical tielines. Each of the
two plait-point curves must start at a critical endpoint.
(In a general case, these two form a single continuous
curve, but here it is interrupted by the inaccessible region .80
of negative surfactant concentration.)
The evolution of phase behavior from plait points and .70
critical tielines can be modeled empirically as Bennett et -n 130
::0
al. 30 did following Hand's scheme for modeling m
m
binodals 31 and Pope and Nelson's approach to modeling m .50
zm
the evolution of the surfactant-rich third phase. 8 In terms ::0 .40
G'>
of the phase diagram, the inputs are (1) the locations of ~
the two critical tielines, (2) the loci of the two plait ::0
-f
30
points, (3) the loci of the three vertices of the three-phase ·~O
triangle when it is present, (4) the slope of each binodal
.10
lobe at its plait point, (5) the limiting slope of each
binodal lobe where it terminates in the vertices of the
three-phase triangle, (6) one tieline of finite length
within each binodal lobe, and (7) a description of the
two-phase region below the three-phase triangle. Ex-
perimental observations of phase behavior, including
unexpected progressions of phase volumes (volume up-
takes), were explained successfully with this empirical Fig. 2-lnverted free-energy surface of a ternary regular
model. It can be used to interpolate and, with greater solution. Parameter values employed are a 12 = 3,
risk, to extrapolate limited experimental data; to estimate a13 =a23 =0.
progressions of phase behavior for interpreting core
floods; to focus on active, important, or complex regions
of the phase diagrams in which more experiments are in-
dicated; and to serve as the basis of the thermodynamic the system. Such a function is conveniently pictured as
part of displacement simulators for process design and an inverted free-energy surface above the ternary com-
optimization. Indeed, a number of authors were attracted position triangle (see Fig. 2). To be stable, an
by the simplicity of this type of pseudoternary represen- equilibrium, single-phase solution must satisfy
tation of phase behavior and used earlier versions in
chemical flooding simulators. 5,6,8,9, II
Thermodynamic modeling by means of suitable free-
energy functions-that is, by equations of mixture
state-is worth investigating as an alternative to such
empirical modeling. It should be possible to relate the and
parameters of a sound thermodynamic model more
closely to molecular thermodynamics and thus to the
molecular natures of the constituents. Therefore, ther- ......... (I)
modynamic modeling should be more reliable for inter-
polation and especially extrapolation of data and thus
could permit design estimates with fewer experimental That is, it must be stable to small fluctuations in com-
data on phase behavior. A good thermodynamic model position (locally stable). Otherwise the phase breaks into
incorporates a massive amount of phase behavior infor- two or more phases, which reduces the free energy. A
mation in a compact formula. Furthermore, its outputs metastable phase is stable to small fluctuations but not to
can be used as inputs to the computationally simpler em- nucleation of some new phase; it may remain
pirical schemes when this is advantageous. The first homogeneous indefinitely if nucleation is suppressed.
challenge is to find the simplest free-energy functions, or Supersaturated salt solutions are examples of metastable
equations of mixture state, that can match qualitatively phases.
the experimentally observed progressions of pseudoter- The chemical potential of species i is given by
nary diagrams at least as well as Bennett et al. 's 30 em-
pirical scheme.
We present in the following a relatively simple equa-
tion of state of ternary liquid systems that appears to do
this. First we review the equations considered and the
criteria by which they were compared. . ........................ (2)

Equations of Ternary Liquid State
Relation to Phase Diagrams
The appropriate thermodynamic function is the Gibbs
free energy of ternary solution-i.e., the solution free
energy per mole, g, over that of the pure components of
DECEMBER 1982
where j and k are the other two species in solution. In
terms of the ternary phase diagram and free-energy sur-
face, it represents the intersection of the plane tangent to
the surface at x with the vertical g axis at Xi = 1. Equality
of the three chemical potentials at two compositions im-
plies that the same plane is tangent to the free-energy
947
surface at both points. Thus, stable two-phase equilibria
must satisfy
Jl-~=Jl-f, i=l, 2, 3 ........................ (3)
The conditions are that each of the three chemical poten-
tials be equal in the two coexisting phases 0' and (3; this
makes a total of three equations for a tieline, which on a
ternary diagram is specified by four independent com-
position fractions, two in each phase. The locus of two-
phase equilibria is called the binodal. In addition, each
phase must be locally stable.
which it is selloidal (saddle-shaped)-that is, it separates
the stable region (with its metastable zones) from the
unstable. In some cases an additional spinodal divides a
selloidal from a convex region and encloses the latter
(see, for example, Ref. 32). The spinodal makes tangent
contact with the binodal at a plait point, the location of a
two-phase tieline of zero length. At a plait point, which
is of course a critical point, the third directional vanishes
in the same direction as the curvature.

( a2~b)
ax I
~O, 0=0', (3 .................... (4a)

With two independent composition fractions, Eq. 7

........................ (4b)
An equilibrium is metastable if each phase is stable to
small perturbations but not to nucleation of a new phase.
Stable three-phase equilibria must satisfy
defines the spinodal curve; Eqs. 7 and 9 define the plait
point.
A critical endpoint is a plait point that is in equilibrium
with another, distinct phase: it is the genesis of a three-
phase equilibrium. At the critical endpoint there are five
conditions to be satisfied by the four independent com-
positions:

Jl-~=Jl-f, i=l, 2, 3 ....................... (Sa) Condition 1.

Jl-~=Jl-f, i=l, 2,3 ....................... (5b) 2g ct 2g

That is, each of three chemical potentials must be equal
( a2~ct)
ax I
(a 2 ) _ ( a ct )
ax 2 ax ax 2 I
2 =0 ...... (lOa)

in the three equilibrium phases; this makes a total of six

equations to be satisfied by six independent composi· Condition 2.
tions. The phases themselves must be stable as well:
3g ct gct
a
( ax 3 dx) (~)3 +3( a: ) (~)2
( a2ax~b)
I
~O, 0=0', (3, 'Y. . ............... (6a) I 2 ax aX2 dx I 2

where
........................ (6b)

The equilibrium may be metastable, however.

On a spinodal curve, the free-energy surface has
vanishing curvature in some direction; thus,
Conditions 3 through 5.

( axa2~)(a2~)_(
I ax
a2g )2=0,
ax ax 2
2 I
......... (7) Jl-~=Jl-f, i=l, 2, 3 ...................... (lOc)

Plait points and critical endpoints can be metastable and

and the direction is given by unstable just as can tie lines and three-phase tie-triangles.
The equations for tielines, tie-triangles, plait points,
and critical endpoints, together with experimentally
( ~) =_ ( a g )/(~)
2
.......... (8) determined compositions, can be used to fit the
dx 2 aXlaX2 ax1' parameters of an equation of state. If an exact solution is
not attainable, either because there are more equations
The free energy of a phase on the spinodal is indifferent than unknown parameters or because the exact solution
to composition fluctuations in this direction. The yields unacceptable parameter values (for instance,
spinodal separates the region in which the free-energy negative molecular size ratios), the remedy is a
surface is concave toward higher free energy from that in residuals-minimization scheme to best fit experimental
948 SOCIETY OF PETROLEUM ENGINEERS JOURNAL
and physical constraints, as discussed in the following.
Another possibility is that the fit of stable, equilibrium
data implies an unstable equilibrium in the model so at-
tained; this too is mentioned later.
In the vicinity of a plait point, the compositions and
other equilibrium properties of two coexisting phases
rapidly approach each other, and the IFT plummets. This
behavior is reflected in both classical equations of state
and critical-scaling property correlations. 12,16,33,34 The
latter are more precise very near a plait point, but for
compositional modeling away from the plait they are not
so precise, predicting, for instance, negative concentra-
tions. 33 Moreover, they require the fitting of many con-
stants,33 including additional constants for each new
mix point. The classical, analytic equations of state ac-
tually locate plait points and of course describe phase
behavior everywhere else. We also are investigating sim-
ple nonanalytic equations of state. *
The molecular theory of multicomponent inter-
faces 13-15 states that the interfacial composition profile
and tension 'Y between phases ex and (3 depend on the
free-energy function and a set of molecular influence
parameters that measure the range of intermolecular
forces. Specifically,
'Y= r
o
.J2tl.wdp , ... , ....... , .............. (11)
where p is an influence-parameter-weighted path length
of the profile on the phase diagram and
tl.w==w-w"', ............ , .... ,., ....... (l2a)
w==f-'L.n;/-t;, .... , .................... (l2b)
where f is the Helmholtz free-energy density, n; is the
molar density of component i, and tl.w is the height of the
free-energy surface above the tangent plane that defines
the phase equilibrium. The composition path defends on
the influence parameters as well as on tl.w. 13,1 For the
incompressible solution models introduced below, the
Helmholtz free energy equals the Gibbs free energy, and
tl.w=n(g-'L.x;/-t;), ........................ (13)
where n is the molar density of the solution. A rough
measure of 1FT between two phases in a ternary incom-
pressible solution is 17
'Y -.Jtl.w max d, ........................... (14)
where tl.w max is the maximum value of tl.w along the
tieline, and d is the length of the tieline.
Prototype Equations
The two simplest equations of nonideal ternary liquid
state are (1) the strictly regular solution,32,35,36 which
has ideal entropy of mixing but nonvanishing and hence
non ideal enthalpy of mixing, and (2) the micro-
segregated solution, 15,37 which has no enthalpy of mix-
ing per se but does have a non ideal entropy of mix-
"Research in progress.
DECEMBER 1982
ing-and entropy that is derived with statistical ther-
modynamical approximation from a segregation model
ofbrineloil surfactant systems. 37,38
The pioneer in thinking about phase behavior of these
systems was Winsor. 39 His intuition was that phase
behavior is set by the relative solubility of surfactant in
brine and in oil. To this should be added the solubility of
brine and oil in each other. The simplest embodiment of
this picture is the ternary, strictly regular solu-
tion,32,35,36 defined by
g
- =xwlnxw +xolnxo +xslnx,
RT .
The solubilities of the binary pairs are determined by the
pair interaction parameter, ex ij, which represents the net
difference between iii, j/j, and ilj interactions. 35 In the
following we demonstrate that this equation cannot ac-
count even qualitatively for the phase behavior of in-
terest. Nevertheless, it is the first step in our develop-
ment of a successful equation. The second step is the
Flory-Hu§gins equation from polymer solution
theory; 40, I in it the composition variables are the
volume fractions, ¢;.
Here n is the molar density of solution; V; is the molar
volume of aggregl:!,!es..,9f each_ cOJ!1ponent and enters
through the ratios V wlVo and V wlVs' In polymer solu-
tions these ratios account for the permanent linkage of
monomers into polymer chains; here they account
qualitatively for reversible aggregation of components
into solution microstructures and in particular for the size
of any aggregates that form. Here again, ex ij reflects pair
interactions between components. As we show,
however, this equation cannot account for the phase
behavior of interest, although it comes significantly
closer than the strictly regular solution.
The difficulty appears to stem from the way in which
the surfactant and other amphiphiles aggregate in
micellar solutions and microemulsions. Winsor imag-
ined that the aggregates are sheetlike and divide water-
rich from oil-rich regions within an equilibrium phase.
From what is known about micelles and swollen micellar
microstructures,42 it appears that the aggregates are like-
ly not only to divide water-rich from oil-rich regions but
to separate them. That is, the aggregates that form from
surfactant and associated amphiphiles are probably either
closed, as in the case of swollen micelles, or bicon-
tinuous, as has been suggested of microemulsions that
are in equilibrium with both oil and water. 38,43 In either
event, the water-rich regions would be segregated entire-
ly from the oil-rich regions.
949

Fig. 3-Symmetric regular solution with a wide three-phase
region. Parameter values employed are "I wo =
C1 ws = "los =3.
The simplest embodiment of this picture is the ternary
micro segregated solution 17,37 in which the volume oc-
cupied by the system is imagined to be partitioned or
tessellated into a random interspersion of oleic microdo-
mains and aqueous microdomains separated by interven-
ing closed sheets of surfactant. The free energy stems ex-
clusively from configurational entropy and is given by
g
-=--=-*
VRT V
(Vm
eV
* * * *) ,
1 In--* +<poln<po +<Pwln<pw ... (17)
where V* is the average volume of a unit of the tessella-
tion, V m is a scale factor, and <p; and <p:, sum to one.
All the surfactant is assumed to be contained in the in-
tervening sheets; its concentration depends on the extent
of sheeting and the curvature of the sheets.
While this equation accounts roughly for the progres-
sion in Fig. 1, 17 it has shortcomings because it does not
do justice to the energetic interactions between oil,
water, and surfactant.
Proposed Equation
On the one hand is the microsegregated solution model
in which surfactant sheets perfectly screen oil and water,
and free energy depends on the statistics of microdomain
distribution. On the other hand is the Flory-Huggins
solution model in which surfactant aggregates into
chains, perhaps networks, and enthalpy depends on in-
teractions of nearly randomly mixed components. A
modified version of the Flory-Huggins model, however,
accounts simultaneously for pair interactions, aggrega-
tion, and surfactant sheeting.
The weakness of the Flory-Huggins bilinear interac-
tion terms shows in the symmetric case (cx it'S = cx os) in
which interaction energy of surfactant in solution is
cxws<p,(<Pw +<Po). Thus, when CX ws is negative, free
energy is reduced when surfactant mingles with oil or
water. As an amphiphile, however, surfactant prefers to
associate simultaneously with oil and water. This
preference is represented most simply by a trilinear
950
term-i.e., a term proportional to <Pw<Po<Ps.44
Moreover, surfactant, by aggregating into sheets,
separates oil and water into microdomains and thereby
reduces oil/water interaction. A simple way of represent-
ing this is to make the binary interaction energy of oil
and water a monotonically decreasing function of surfac-
tant concentration.
cx :'0 = cx ;0 (<p 5)' .......................... (18)
The simplest form is, of course, a linear function.
cx :'0 =cx wo(1-s<p s)· ...................... (19)
Here s is called the "screening" parameter; positive
values mean surfactant associates simultaneously with
oil and water and reduces their repulsion energy, allow-
ing them to dissolve in the presence of a low concentra-
tion of surfactant.
The LSFH model 45 is then
V wng
--=<Pwln<pw+ ( -=-
V w ) <poln<po+ ( V w ) <Psln<ps
--=-
RT Vo Vs
+cx wo<Pw<P 0 +cx ws<P w<P s +cxos<P 0<P s
-cx wos<p w<P 0<P .\' .................. (20)
It contains six independent parameters: V,)V o ' VwlV s '
cx IVO' cx ws' cx os' and s. Each is a function of field or
fieldlike variables such as temperature, pressure,
molecular type, and salinity. On the binary edges of the
ternary phase diagram, the LSFH equation of course
reduces to the binary Flory-Huggins equation. We find
that the linear ternary screening term is sufficient to
model microemulsion phase behavior. The following
sections explain how the proposed equation was reached;
its ability to model phase behavior and, qualitatively,
1FT; and the means of fitting the parameters to ex-
perimental data. The ESFH model, for which
cx :'0 =cx woexp( -s<p,), ..................... (21)
also is discussed.
Equations of Ternary Mixture State
Criterion of Comparison
A key element of the phase behavior of microemulsions
is the ability of surfactant amphiphile in low concentra-
tion to solubilize large amounts of water and oil in
equilibrium with the excess brine and oil phase. 1,2,30 At
the so-called optimal salinity, equal volumes of water
and oil are incorporated into a microemulsion phase of
low surfactant concentration while virtually no surfactant
partitions into the other two phases. Here we idealize the
optimal-salinity tie-triangle as symmetric about the axis
<Pw =<Po (cf. the middle-phase diagram of Fig. 1). The
test of a good equation of state is then its ability to pro-
duce a symmetric, low, wide three-phase region near the
base of the phase diagram.
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
 s
Fig. 4-Symmetric Flory-Huggins solutions with wide, low three-phase regions; minimum heights
for given widths.
Evolution of the Proposed Equation
The regular solution fails to give the low, wide miscibili-
ty gap, or multiphase region, that is characteristic of
practical microemulsion systems. In symmetric diagrams
(a ws =aos), the waterloil (W/O) binodal curve that
defines the miscibility gap is independent of the a ws and
aos interaction energies; from Eq. 3 it is 32
I-x s =(x w -xo)coth[awo(x w -x o )I2]. . ...... (22)
On the binodal, the maximum surfactant concentration is
at the plait point.
x;= I-2Ia wo , x ~ =x t = lIa wo . . .......... (23)
This is the minimum height of the multi phase region in
the diagram, because the upper portion of the binodal
may be overlain by a three-phase triangle. The width of
the binodal at the base of the diagram is (x w - X 0) b ,
given by
1 =(x w - xo) bcoth[a wo (x w - x o ) bI2]. . ........ (24)
Thus, as a wo is lowered to squash the multi phase region,
the base of the region shrinks in width. Moreover, when
the binodal is topped by a three-phase triangle, the base
of the latter can be brought toward the base of the
diagram only by raising a ws and a os' which drives up
the surfactant-rich apex of the triangle and thus heightens
the multiphase region. So it is that in any regular solution
diagram a three-phase triangle with a low, wide base has
unacceptably great height, as indicated by Fig. 3.
DECEMBER 1982
The Flory-Huggins solution doe~ a .little better. In
symmetric diagrams (a ws =aos and V wlVo = 1) the W/O
binodal is exactly that of the regular solution: it, its plait
point, and its width at the base of the diagram are given
by Eqs. 22 through 24, with mole fractions replaced by
volume fractions. Again, as the two-phase region is
squashed, its base shrinks. But when the binodal is
topped by a three-phase triangle, the base of the latter
can be brought arbitrarily close_ to the base of the
diagram by lowering the ratio V wIV" which corresponds
to increasing aggregation of the amphiphile or surfac-
tant. Nevertheless, because the minimum height of the
multi phase region again is set by the height of the binary
plait point, the Flory-Huggins solution fails to model the
phase behavior of practical microemulsion systems (see
Fig. 4).
As explained in the preceding section, the original
Flory-Huggins solution accounts for neither the propen-
sity of surfactant to mingle simultaneously with water
and oil nor, when it aggregates into sheetlike structures,
its ability to separate water-rich from oil-rich regions,
thereby reducing waterloil interactions. The ternary in-
teraction term of the LSFH equation (Eq. 20) accounts
f.Qr .Qoth. In symmetric diagrams (a ws = a os and
V wlVo = 1), the W/O binodal, again independent of a ws
and aos, is
........................ (25)
951
Its plait point is at
¢ P= I +S-.J(I-S)2 + 8s/cy w()
s 2s ' ........... (26)
and the width of the binodal at the base of the diagram is
given, as before, by
Now, by turning the screening parameter on (s > 0) and
increasing it, the height of the plait, and thus of the entire
multiphase region, whether or not a three-phase triangle
is present in the diagram, can be cut down without
shrinking the width of the region. The desired low, wide
multi phase region can be attained with the LSFH equa-
tion, as the example in Fig. 5 shows.
Having arrived in this way at a promising equation of
state, we must first examine its performance as a
generator of a series of diagrams-indeed, a whole
multidimensional space of diagrams-when its
parameters are varied. If it performs well in modeling
qualitatively the experimental phase behavior of interest,
the next step is to see how best to fit its parameters to
data.
The LSFH Solution
Determining Phase Diagrams
Given an equation of state and values of the parameters
that appear in it, the corresponding phase diagram is
found from the subsidiary equations-e.g., Eqs.
25-27-for critical points, three-phase tie-triangles, two-
phase tielines, and the spinodals that separate regions of
stable phase from regions of unstable phase. The reasons
for doing this depend on the number and nature of
multiphase regions in the diagram. There are a number
of examples. 14,32,36,37
Alternatively, we can proceed by treating some or all
of the parameters as unknowns to be so determined that a
phase diagram will have one or more prescribed features,
s positions that are very small in either phase to limit trun-
w o
Fig. 5-Phase diagram for LSFH solution model base case.
Parameter values are listed in Table 1.
952
such as a certain location of plait point or a certain three-
phase tie-triangle. We can imagine the multidimensional
space of equilibrium phase compositions-2p fractional
compositions for p phases-and equation-of-state
parameters-six for the LSFH equation. In this
(2p+6)-dimensional space, we can search for solutions
of the chosen set of phase equilibrium constraints. If
these are fewer in number than the fractional composi-
tions and parameters that are free, there is in general no
solution; if they are greater in number than the free
variables, a solution, if it exists, in general has extra
degrees of freedom,
The parameters in the LSFH equations enter linearly if
we replace s by cy W()s as a parameter. Thus, if the chosen
phase equilibrium constraints leave only parameters as
unknowns, the equation set for them is linear and easily
solved. But if one or more fractional compositions are
among the unknowns, the equation set is nonlinear. Then
the solution method of choice is Newton's iteration proc-
ess, or Newton-Raphson scheme,46 provided a first ap-
proximation is at hand that falls well enough within the
domain of convergence that only a few iterations are
needed to arrive at a solution of the desired accuracy.
When the Jacobian used in Newton iteration is singular
at or near the solution sought, as near a critical point,
iteration may fail even though the first approximation
lies near the solution. Then the singularity can be
searched out and identified in its own right. 47
We employed Newton iteration, and, after finding the
first solution in each series by one stratagem or another,
we used zeroth-order continuation with an intuitively
chosen size of parameter step. That is, the first approx-
imation after each parameter step is the solution at the
last value of the parameter; the first guess for the next
tieline is the last tieline; for the next tie-triangle, the last
one; and so on. First-order continuation with automatic
adjustment of parameter step may well be more cost ef-
fective. 48
If one or both of V w/V()and V w/V, differ greatly from
unity, a phase not dilute in any component may be in
equilibrium with one virtually free of one or two com-
ponents (e.g., with volume fractions of 10 -100 or less).
Then it is imperative to take as independent those com-
cation error in computation of the third, dependent com-
position. Although bounded iteration guarantees positive
composition, it can be inefficient when the solution lies
so near the bound, Consequently, during iteration we
substituted for independent variable ¢ ~ the surrogates
U~ == In¢ ~; this eliminated the need for a lower bound
and sped convergence.
Newton-Raphson iterative schemes require an initial
guess sufficiently accurate to allow rapid convergence,
The principle we followed was to extend easily derived
binary phase behavior to the ternary. 32 Key elements in
the search are as follows.
I. The spinodals, or stability curves, of the binaries
are useful in guessing a first approximation to the binary
binodal and locate the limits of any ternary spinodals that
extend to a vanishing fraction of one of the three com-
ponents. In the absence of a third component, Eq, 7
simplifies to (0 2 g/ox T) x. =0 =0.
2. The binodals, or c6existence curves, of the binaries
are comparatively simple to find, because the dimen-
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
 TABLE l-PARAMETER VALUES FOR LSFH AND ESFH MODEL-GENERATED PHASE DIAGRAMS
Figure Vw/V S VwtV o
5 through 9, 15 0.01
11 0.01
12a 0.01
12b 0.01
13a 0.01
13b 0.01
16 0.0"
*Shown in figure.
sionality of the search is less than in the ternary. The
binary binodal is a good first approximation to nearby
ternary binodals; alternatively, the formulas for the shift
from a binary to a ternary tieline upon addition of a trace
of the third component can be used. 32
3. The spinodals of the ternary separate stable from
unstable states. A tieline is said to be stable if the two
states it connects on the binodal each fall in the stable
region; such tielincs must cross the spinodal twice or a
larger even number of times. Thus, if the spinodal passes
outside the binodal, the latter consists of unstable states
and in free energy lies above a stable three-phase
equilibrium, which is represented by a tie-triangle. This
is the case, for instance, if the spinodal lies outside the
binodal at the plait point. 32 The shapes of the associated
binodals and spinodals are guides to guessing first ap-
proximations to the coexisting three phases. On the other
hand, if the spinodal lies entirely within the binodal (ex-
cept at a plait point, where the two make tangent con-
tact), the tielines of the latter are stable and in a ternary
represent states of minimum free energy; moreover, the
region between binodal and spinodal represents
metastable states.
4. Certain of the binodals of the ternary can be found
by continuation from binary binodals, as already noted.
Because three stable binodals issue from a stable tie-
triangle, they can be found by continuation from the ver-
tices of the triangle itself. Each binodal also extends
within the tie-triangle, and there, too, the regions be-
tween binodal and spinodal represent metastable states;
there are also metastable states represented by small
regions that lie outside the spinodal yet inside the
triangle.
There are circumstances in which these aids would not
be enough, as when there is a closed, ternary miscibility
gap-a two-phase region that does not reach a binary
edge of the diagram. A check for stability (Eq. I) on a
grid of points spanning the phase diagram can locate
these unforeseen complications. In no case, however,
did we on further checking discover a phase equilibrium
in the LSFH model that these aids had failed to locate.
To work with the volume fractions that appear instead
of mole fractions in the LSFH and ESFH equations (and
Flory-Huggins itself), it is appropri'l!e in Eqs. Lthrou..gh
13 tOJeplace g, Xi, fl.i, and dw by V wng, 1>;, V wfl.;IV;,
and V wdw, respectively. This we did.
Phase Behavior
The base case we selected is a diagram with a low, wide,
three-phase region resting on a binary W10 miscibility
gap from 0.01 to 0.99 volume fraction oil, and a middle
DECEMBER 1982
a wo a ws aDS S
1 4.8 -31.35 -31.35 7.29
1 4.8 -31.35 7.29
4.8 -158.09 15.62
4.8 -5.14 3.12
-31.35 7.29
-5.14 3.12
0 0 0 12.46
phase of equal uptake of oil and water with 0.10 surfac-
tant fraction (Table I and Fig. 5). The former conditions
set a wo =4.8. Throughout this study we chose
V,)Vo = 1 and, to reflect surfactant aggregation,
VwIV,=O.OI. The symmetry (ao.\·=a ws ) of the base
case leaves a degree of freedom in the choice of the pair
(a ws and s), which is explored later. Features of the free-
energy surface and phase diagram in the base case il-
lustrate the thermodynamic origins of low 1FT's, sen-
sitivity of phase behavior to experimental conditions,
slow equilibration, and existence of multiple long-lived
metastable states in microemulsion systems.
Systematically varying the parameters causes these
features to evolve in a way that mimics microemulsion
phase behavior in a salinity or temperature scan.
Figs. 5 and 6 give the phase diagram of the LSFH base
case. To the left of the tie-trangle is a binodal lobe in
which surfactant partitions preferent@lly out of the
water-rich phase (behavior denoted by 2). To the right is
a binodal lobe in which it partitions preferentially out of
the oil-rich phase G behavior). Underneath, at
1>" <0.001, is another binodal and two-phase region in
which _surfactant partitions equally into oil and
water (~ behavior); this is made evident by changing to
3 PHASES
1U3
r-----------------------------------~1
2 PHASES
10~~================================~
W o
Fig. 6-Base of the phase diagram in Fig. 5 expanded to
show binodal below the three-phase region.
Fig. 7-Contour plot of ~w for the LSFH solution base case.
Contours are plotted at intervals of 0.04 RT/V w'
953
log 1> s as the coordinate (see Fig. 6, where skewed
tielines are transformed to curves). 4
The free-energy function that relates most closely to
1FT is .1w, defined previously and shown by the contours
in Fig. 7. There are 10w-.1w paths from the water vertex
of the tie-triangle to the middle-phase vertex and on to
the oil vertex, and these paths bypass the high-.1w path
that belongs to the W10 tieline that is the base of the tie-
triangle. The actual paths and the 1FT's they give are
governed by molecular influence parameters, as noted
earlier. But the three edges of the tie-triangle approx-
imate the paths, and .J.1w max d along each edge is a
rough measure of the 1FT between each pair of phases.
In this case, .1w max is sixfold less on the waterl surfactant
(W/S) and oil/surfactant (O/S) sides than on the W/O
base. Thus, if the middle phase locates between oil and
water, low total tensions between those two phases are
promoted by the formation of the third phase, as indeed
is true of middle-phase microemulsion.
Two sources of experimental artifact find explanation
in the flatness of the free-energy surface plotted in Fig.
7. The shallowness of the middle-phase minimum in .1w
BINODALS
Fig. 8-Binodals, spinodal, plait points, and tie-triangle of the LSFH solution base case; see Fig. 5.
lllllIlI METASTABLE 1
~ METASTABLE ~
kW'''''IIIIiIIIIIIIIIIIIIII''I''IIIIIIII''llliIIlliIIll_IIIIIIl''W''~
WI6ii __
Fig. 9-Regions of metastable equilibria for the LSFH solution base case.
954
indicates that slight changes in the environment-for in-
stance, temperature fluctuations and trace im-
purities-can cause significant changes in equilibrium
phase compositions, even though they alter the free-
energy surface topography but little. Moreover, the ther-
modynamic driving force for diffusive re-equilibration is
reduced if, as here, the free-energy surface is nearly
flat. 49
As noted earlier, compositions lying between the
spinodal and stable binodals are metastable as a single
phase. In addition, two or more metastable phases can be
in thermodynamic equilibrium (Eqs. 3 through 6). In
other words, in Fig. 6 each binodal continues within the
multiphase region, and the local stability of a two-phase
equilibrium is determined by the stability, not at the mix
point, but of the equilibrium phases (Eqs. 4 and 6). The
stable symmetric binodal below the tie-triangle (Fig. 6)
enters the three-phase region (Fig. 8), crosses the
spinodal (Eq. 7), and converges on an unstable plait
point (Eqs. 7 through 9). Until it crosses the spinodal, its
tielines represent metastable ~ equilibria. Likewise, each
binodal lobe continues into the metastable region; the
SPINODAL
f'im METASTABLE ~
11\1 METASTABLE 2"
__----------~
o
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
binodals are plotted on Fig. 8 only as far as the spinodal,
but actually each continues to the opposite comer, link-
ing both binodal lobes into a figure eight. Tielines con-
necting metastable compositions are metastable, and
the~ i!re thus four types of metastable equilibria:
I, 2, ~, ~ (Fig. 9). At a single overall composition, as
many as three types of metastable equilibria are possible;
whether anyone of them could appear is a matter of
nucleation and other rate phenomena. Moreover, the
shallow free-energy minimum in the presence of the
third phase (Fig. 7) indicates only slight free-energy in-
centive to drive the mass transfer needed to break down
metastable equilibria once they are established, or to
establish fully stable states in equilibrium. This may ex-
plain why microemulsions are so slow to equilibrate and
so sensitive to the way in which they are mixed.
In the limit of no surfactant in oil and brine phases
there is a locus of (a ws' s) pairs along which the tie-
triangle does not change (Fig. 10). As s diminishes along
this locus, it reaches a value at which the W10 tieline
lifts off the base of the phase diagram. On the other
hand, the intuitive requirement that a;o > 0 (no net at-
traction of oil and water even in the presence of surfac-
tant), at least throughout the part of the phase diagram of
interest, sets a maximum value of s. The thermodynamic
contribution to 1FT as measured by .J~w max d appears to
be lowest near the lowest admissible value of s.
Therefore, in all the cases reported here, s was set near
that value.
Systematically changing one or more parameters from
those of the base case, or of other symmetric cases, pro-
duces progressions of phase diagrams that mimic those
volumes pictured. Because the overall composition, or
mix point, lies above the critical tieline, the oil-rich
phase disappears before the critical endpoint is
reached. 30 The 1FT factors .J~w max d tend toward zero
at the respective critical endpoints and cross over, as
1FT's often do at the condition in which equal volumes
of oil and water are taken up by the middle phase. The
reduction in the 1FT factor at the crossover is less than an
order of magnitude, which suggests the importance of
molecular and microstructural details of surfactant action
not accounted for here. These enter through the
molecular influence parameters already mentioned. The
reduction in tension is greater than allowed by Antonov' s
rule, 50,51 which states that the tension between any two
phases in a three-phase equilibrium is less than the sum
of the tensions between the other two phases; this is
«w.-«.,.
-30
0.20
3- PHASE
TRIANGLE
LIFTS OFF
jVWAMrnax
RT
d OF BASE

produced in the laboratory by varying, for example, 0.10

salinity. In Fig. 11 is the right-hand half of such a pro-
gression as aos is decreased, which could reflect the in-
creasing affinity of surfactant for oil as salinity in-
creases. The apex of the tie-triangle falls monotonically 5
as the critical endpoint is approached. For overall com- S
position of 0.05 volume fraction surfactant with equal Fig. 10-Variation of the pair (O! ws' s) giving the same three-
fractions of water and oil, the lever rule yields the phase phase region as in Fig. 5 and effect on 1FT.

o
1,r---------~--------------~~~----~~------~--------~~
o

ME

-30 -31 -32 -33 -34 -35 -36

~r---~========================~~
I WIO S

-30 -31 -32 -34 -35 -36

Fig. 11-Variation in O! as mimicking the right-hand side of a salinity scan. Initial value of 1> Iff is 0,10,
Parameter values are listed in Table 1.

DECEMBER 1982 955

a) LOWER MULTIPHASE REGION
b) HIGHER MUL TlPHASE REGION
Fig. 12-Variation on aDS mimicking the right-hand side of a
salinity scan. Initial values of </> 'tE equal (a) 0.05, (b)
0.20. Parameter values are listed in Table 1.
because we made no allowance for the fonnation of a
small amount of microemulsion phase at the W10 inter-
face.
Similar half-sequences of diagrams from optimal
salinity (equal volumes of oil and water in microemul-
sion phase) to the critical endpoint are produced by ad-
justing ¢ ~E to other values and systematically changing
aos (Fig. 12). In all such cases the water phase stays
nearly free of surfactant, and surfactant concentration in
the middle, or microemulsion, phase drops monotonical-
ly as the critical endpoint is approached. Somewhat dif-
ferent patterns are generated by other courses of the
parameters, as illustrated in Fig. 13, where a wo and a",s
are raised together to model decreasing solubility of
water in surfactant and in oil as salinity is increased. Sur-
factant concentration in the microemulsion rises and then
falls as salinity increases. However, in the cases in
which ¢~E=0.10 and 0.05 (not shown) at optimal
salinity, the water-rich comer of the tie-triangle lifts off
the bllse of the diagram as salinity increases, even with
V wlV~ =0. Such partitioning of surfactant into the
aqueous phase with increasing salinity is not realistic, of
course.
Less symmetric progressions than those shown in
Figs. 11 through 13 can be readily generated. In fact, the
LSFH equation can generate very asymmetric phase
behavior if pseudocomponents are accounted for proper-
ly. The type of asymmetric pseudoternary diagram
reported by Healy et al., 2 for instance (Fig. 14), results
from a scan of oil/water (O/W) ratio at constant salinity
a)
b)
Fig. 13-Variation in a WD and a ws mimicking the right-hand side of a salinity scan. Initial values of
</> 'tE are (a) 0.10 and (b) 0.20. Parameter values are listed in Table 1.
956
and surfactant and alcohol concentration. It is now
known that this kind of scan traverses many pseudoter-
nary phase diagrams when the pseudocomponents are
defined properly. 21 ,25 The LSFH equation readily can
generate these diagrams from a continuous scan of
parameter values; the tielines and mix points, if plotted
together, give the appearance of a single, asymmetric
diagram (Fig. 14).
The LSFH equation plainly can model the way in
which favorable surfactants, or surfactantlamphiphile
blends, lower the height of the multi phase region. To ob-
tain a low, wide, three-phase triangle apparently requires
surfactant interaction parameters quite large in
magnitude. For example, in the preceding base case,
a ws =aos = -31.35, and awos=35, whereas a wo =4.8
is large enough to give an O/W miscibility gap of 0.98
volume fraction. The free-energy surface, more easily
visualized when drawn upside-down as in Fig. IS, then
becomes a steep mountain with the miscibility gap on
one side (cf. the vertical scale in Fig. 2). This may not be
entirely realistic, so other modifications of the Flory-
Huggins equation are under investigation. We employ a
nonlinear extension of linear screening, namely the ex-
ponential function given by Eq. 21. The resulting ESFH
solution model
+(VwIVs)¢ sln¢ s +a woexp( -s¢ s)¢w¢o
generates the same low, wide, three-phase tie-triangle
(Fig. 16) as the LSFH equation. In addition, it has three
advantages over the LSFH model. First, a;o
== a woexp( - s¢ s) is not negative for any value of ¢ s or
s. Second, there is again a degree of freedom in the (a ws'
s) pair along which the tie-triangle does not change (Fig.
17), but a ws need not be as large as in the LSFH model.
Zero or even positive values of a ws are allowed,
although for a ws greater than about 0.5, binary W IS and
O/S miscibility gaps and complex ternary equilibria
erupt. Third, surfactant partitions almost completely into
the microemulsion phase in both binodallobes, as usual-
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
Iy is observed experimentally. 2.21 Llw max between oil,
brine, and microemulsion phases in equilibrium is about
the same in the two models, as comparison of Figs. 10 W ow OW 0
and 17 shows.
Another modification is a hybrid of the micro-
segregated solution and the Flory-Huggins, the former
presumably better suited to the propensity of surfactant
to form sheetlike structures that separate more or less
bL:Q
W 0
random subdomains rich in water or oil-in contrast to
the chainlike aggregates for which the Flory-Huggins Fig. 14-Asymmetric phase behavior generated by the LSFH
equation was designed. solution model. (a) Model-generated phase behavior.
Other models represent moderate association in solu- These are the last diagram in Fig. 12a, the first in Fig.
tion at a considerable expense in complexity, 35,52-55 but 11, and the mirror image of the last in Fig. 12b. (b) In-
none are yet suitable for modeling microemulsions. For ferred phase behavior.
instance, the quasichemical model 35 accounts for
association of components that attract each other. Never-
used previously to fit a phase diagram. The equilibrium
theless, even when adapted to surfactant molecules com-
relations are linear in the parameters, which is a con-
posed of hydrophilic (W) and lipophilic (0) segments, it
siderable advantage. If there are fewer constraints than
fails to reflect realistically the amphiphile screening of
parameters, the extra parameters of course can be set ar-
oil and water. 52 The failure evidently lies in its inability
bitrarily, until more data become available. When there
to distinguish between isomers, for instance WOWOWO
are fewer parameters than constraints, as for instance in
and WWWOOO, and the superior screening of the latter
the fitting of many tielines simultaneously, there is the
over the former. In this respect it is like other "group-
standard problem of finding the set of values that
contribution" models. 53 ,54 Monte Carlo simulation, 33
minimizes the sum of weighted residuals 59: either
in principle capable of modeling complex microstruc-
residuals in the equilibrium conditions, if the experimen-
tures, is too expensive for any but the simplest situa-
tal data are regarded as being exact, or residual dif-
tions. "Decorated lattice" models 55 cannot yet accom-
ferences in compositions between the data-based phase
modate ternary three-phase mixtures. Other models 56,57
diagram and the model-derived one.
make specific assumptions about microemulsion struc-
Two particular problems can occur in the fitting of
ture that do not arpear to be justified throughout the
phase diagram. 38,5 parameters. First, a parameter set may exactly satisfy
stable equilibrium conditions drawn from measurements
Fitting the Model to Data and yet predict an unstable or metastable equilibrium. A
The six parameters of the LSFH equation can be fit to check of the phase diagram implied by the parameter set
experimentally determined compositions of coexisting quickly reveals whether this has happened. Second, a
phases by means of the same equilibrium constraints parameter set may satisfy the equilibrium conditions yet

9.0
8,0
7,0
I

i 6,0
III

m 5,0
III

I..... 4,0
~
3.0
2,0
1,0

U)m'-Jm(Jl~WN>-'

VALUES OF ct>. VAWES OF (/)0

Fig. 15-lnverted free-energy surface of the LSFH base case.

DECEMBER 1982 957

 TABLE 2-SENSITIVITY OF MODEL PARAMETERS TO THREE-PHASE COMPOSITIONS

Composition *
Parameters
<1>£
(%) VwlVs VwtV o "'wo ~ ~ s
6.7 -8.10 -5 0.592 2.93 -1.07 -1.32 4.91
6.0 +0.01 0.575 3.01 -1.21 -1.51 5.71

*Other compositions: cf>: =0.99%, Q~=O.001%, ¢~E =0.25%, cp~E =0.20%, ¢~ =0.05%.

be physically unreasonable or merely intuitively unac-

~pt@le. A-D iIl§tance is a negative aggregation number
V wlVs or V wlVo' In this case a penalty function can be
incorporated into the sum-of-residuals function to drive
the parameters to acceptable values. 59
Fig. 16-Phase diagram for the ESFH solution model.
Parameter values are listed in Table 1. Fitting parameters to data and determining the phase
diagram from the parameters is a mapping between
multidimensional parameter and composition spaces. A
simple, instructive case is the fitting of the six model
parameters, e, to the six equilibrium conditions for a
0 three-phase triangle, f(q>, e), given by Eq. 5, which de-
/1 v pend on the six independent compositions, q>. The
ci. ws ) V
(
change in model parameters, de, produced by a small
) change in data, dq>, is
-10 ;t (
de=-(aflae)-'(aflaq»dq>, ................ (29)
II (
I. I where the i, j elements of matrices afl ae and afl aq> are
/ V a/Jao j and a/ilacf>j, respectively. If either of these
0.20 3·PHASE ) o(w,>O.5 r' matrices is nearly singular, small changes in composi-
TRIANGLE BINARY ./
LlFTSOFF~r, W/S.O/S
tions produce large changes in parameters, or vice versa.
OF BASE II I MISCIBILITY We find that the fitting of the parameters to compositions
GAPS Y is sensitive througout much of the phase diagram. In one
/1 Ii
0.10 such case, summarized in Table 2 and Fig. 18, a change
) V in one composition of less than 0.01 causes an important
) V change in parameter values from an unacceptable to an
;t ( acceptable set. Our experience is summarized in Fig. 19;
0~--~8----~1~0~----~12~~--1~4~~ seemingly innocuous compositional inputs can yield
s either unacceptable parameters or acceptable ones, and
small changes in the inputs can make the difference. It
Fig. 17-Variation of the pair ("'ws' s) giving the same three-
phase region as in Fig. 16 and effect on 1FT. appears that this sensitivity is reconciled easily. The key
issue is not, however, whether the parameters that exact-
ly fit inputs are acceptable, but whether nearby composi-
tional inputs that fall within experimental error of
measured compositions give acceptable parameters. This
seems to be the case, and it is not unlikely that there are
unexceptionable compositional sets arbitrarily close to
exceptional ones.
The sequences of phase diagrams in a salinity or
temperature scan all can be fit simultaneously once a
functional form is selected for the dependence of each
parameter. Fitting them all to straight lines requires 12
constants, for instance, two for each parameter.
w
Fig. 18-Three-phase triangle to which the parameters listed
Conclusions
in Table 2 were fitted. Thermodynamic equations of state for ternary mixtures
can be developed, as exemplified by the free-energy
function proposed here, for pseudoternary correlation of
the phase behavior of systems of aqueous, oleic, and am-
phiphilic components. Fitting the parameters of an equa-
tion to measurements of coexisting phase compositions
can be tricky; standard procedures may yield physically
unreasonable parameter values, yet acceptable values ap-
parently can be found by adjusting compositions within
958 SOCIETY OF PETROLEUM ENGINEERS JOURNAL
any experimental uncertainty. This matter deserves fur- _IIETER
COMBINATIONS
ther investigation.
Once the parameters of the equation have been fitted to
experimental data, those data, though limited, can be in-
terpolated and extrapolated as required for process
simulation and other purposes. The equation can be used PHASE
DIAGRAMS
to aim experiments at key features such as plait points
and critical tielines, if these more accurately determined ~_tally
unacceptable
parameters for predicting the rest of a phase diagram are
available. There is additional predictive potential if the
parameters can be connected closely to the molecular
natures of the constituents.
Phase behavior outputs of a thermodynamic equation
of state-locations of plait points, critical tielines, tie-
triangles, shapes of binodal curves, etc.-can be used Physically
realistic
directly or as inputs to computationally simpler empirical
representations that are currently used in simulation.
By relating phase behavior to a free-energy function,
an equation of state reveals thermodynamic stability Fig. 19-Acceptable and unacceptable fits of model
limits and thus the composition ranges where metastable parameters to compositional data.
states, which otherwise might be confusing, may be en-
countered. It can show where free energy varies weakly
with composition and where equilibration may be slow.
It also can make evident which pairs of coexisting phases e = 2.71828
are likely to have lower 1FT by virtue of low relief in the
free-energy surface between them.
f = Helmholtz free-energy density
f = set of equilibrium and mass balance con-
The ability of surfactant amphiphiles to solubilize
large, equal amounts of water and oil in a microemulsion straints used to fit model parameters to
phase in equilibrium with brine and oil phases puts a data (Eq. 29)
special requirement on equations of state for microemul- g = free energy per mole of solution
sion systems. So do the characteristic, regular progres- n = molar density
sions of phase diagrams as field variables or certain com- p = pressure
position variables such as salinity are varied. Satisfying p = influence-parameter-weighted path length
these requirements leads past the simplest nonideal solu- of the profile on the phase diagram
tion models (regular and Flory-Huggins) to the LSFH R = gas constant
and ESFH solution models proposed here. s = screening parameter in LSFH (Eq. 20)
Their success rests on the screening term in the free-
and ESFH (Eq. 28) solution models
energy function. This term is enthalpic, accounting for
the simultaneous association of amphiphile with oil and T = temperature
water and aggregation of surfactant amphiphile into V*, V m = parameters in microsegregated solution
curved sheetlike structures that separate water-rich from model (Eq. 17)
oil-rich microdomains within an equilibrium phase. Thus V,.u:W,Z,>
the screening term is consistent with the physical picture V".i V, parameters in Flory-Huggins (Eq. 16),
=
behind Talmon-Prager's microsegregation model of LSFH (Eq. 20), and ESFH (Eq. 28)
microemulsion phase behavior. solution models
From the LSFH equation we can see four different a
Xi = mole fraction of component i in phase 0
types of metastable behavior, with as many as three
CX WO '
possible at certain overall compositions that in stable Ct ws' Ct as binary interaction parameters of regular
=
equilibrium split into three phases. Moreover, a free-
(Eq. 15), Flory-Huggins (Eq. 16),
energy factor related to 1FT can be calculated from the
equation and shows that there is a partly thermodynamic LSFH (Eq. 20), and ESFH (Eq. 28)
tendency for equally low 1FT's between water and solution models
microemulsion and between microemulsion and oil when ¢ 7 = volume fraction of component i in phase
the microemulsion phase incorporates equal volumes of a
o
water and oil. chemical potential of component i in
P, i =
The results reported here open a way to ther- phase 0
modynamic models with four and more pseudocom- .1w = function defined by Eq. 12
ponents for more accurately representing the phase e = set of parameters in a thermodynamic
behavior of multicomponent microemulsion systems. 60 model (Eq. 29)
Nomenclature
d = Cartesian distance between compositions Superscripts
on an equilateral triangular phase ME = microemulsion phase
diagram (Eq. 14) P = plait point

DECEMBER 1982 959

 Subscripts
b brine
o oil
s surfactant
w water
Acknowledgments
M.S. Bidner and J.J. Kolstad contributed to the early
stages of this research. The work was supported by the
Nat!. Science Foundation, the U. of Minnesota Com-
puter Center, and the Fossil Energy Div. of the U.S.
DOE as part of the Minnesota program on fundamentals
of enhancing petroleum recovery.
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SI Metric Conversion Factors
dyne X 1.0* E-02 mN
in. x 2.54* E+OO em
·Conversion factor is exact. SPEJ
Original manuscript received in Society of Petroleum Engineers office Aug. 3, 1981.
Paper accepted for publication March 24,1982. Revised manuscript received July 28,
1982. Paper (SPE 10062) first presented at the 1981 SPE Annual Technical Con-
ference and Exhibition held in San Antonio Oct. 5-7.
961