ELSEVIER Fluid Phase Equilibria 126 (1996) 53-70

Calculation of multi-phase equilibria using the equal area rule with

application to hydrocarbon/water mixtures
Nishawn S.M. Hanif, G.-S. Shyu, K.R. Hall, P.T. Eubank *

Department of Chemical Engineering, Texas A & M University, College Station, TX 77843-3122, USA
Received 20 March 1996; accepted 27 May 1996

Abstract

We have used an efficient, new Gibbs minimization method with an equation of state (EOS) model to predict
phase equilibria for hydrocarbon/water binary mixtures. The method utilizes the observation by Eubank and
Hall (1995) that a plot of the derivative of the Gibbs energy of mixing against composition exhibits phase loops
similar to those associated with the Maxwell rule. Equilibrium exists when the positive and negative areas are
equal above and below a specific value of the derivative. Hence, we call the method the Equal Area Rule
(EAR). The EAR application procedure automatically performs a stability analysis for the system.
EAR also presents exciting possibilities when calculating phase equilibria for multi-component mixtures.
Shyu et al. (1995) have applied the method to ternary liquid-phase systems using activity coefficient models.

Keywords: Equal area rule; Hydrocarbon/watermixtures; Multi-phaseequilibria

I. I n t r o d u c t i o n

Classical flash calculations do not always converge to the correct equilibrium compositions as
illustrated by Eubank et al. (1992). They fail more frequently when more than two phases exist at
equilibrium. In such situations, a Gibbs minimization calculation procedure is preferable.
The Tangent Line method, as implemented by Michelsen, 1982a,b) with stability checks, is
currently one of the most widely used minimization techniques. However, Eubank et al. (1992) have
noted that this method only satisfies a necessary condition for equilibrium. These authors propose
another Gibbs minimization technique, the Area Method, which satisfies both necessary and sufficient
conditions for equilibrium. Unfortunately, the Area Method requires more computations than the
Tangent Line method.

* Corresponding author.

0378-3812/96/$15.00 Copyright© 1996ElsevierScienceB.V. All rightsreserved.

PH S0378-3812(96)03141 -X
54 N.S.M. Hanif et al./ Fluid Phase Equilibria 126 (1996) 53-70

Smith et al. (1989) have also developed a Gibbs minimization technique which can be an
alternative to the Area Method and it is simpler and more efficient. Like the Tangent Line method, it
is only a necessary condition for equilibrium.
Our procedures for implementing EAR cover the entire composition space forcing the method to
satisfy also the sufficiency condition. In the method, a plot of the derivative of the Gibbs energy for
the system, G m, against the composition of one component (for example, x~) determines the
maximum number of phases present at equilibrium and the approximate values of their respective
compositions. Then, integration of the function provides equal areas above and below some value of

a /
M1

Xl x I

•:o, iiii
M1

H I
Xl X! x!

Fig. 1. a. A typical graph o f ( a G / ~ x I) versus x I for a binary system existing as LLE at fixed temperature and pressure. G is
determined from an activity coefficient model.b. A typical graph of ( a G / a x j ) versus x I for a binary system existing as
VLE at fixed temperature and pressure. G is determined from the P R / E O S and W S / M C R .
 N.S.M.Hanifet al./ FluidPhaseEquilibria126 (1996)53-70 55

the derivative; this is analogous to the Maxwell Equal Area Rule (MEAR) for pure components. For a
binary mixture, the value of this derivative is the same as that of the tangent which gives equilibrium
compositions in the Tangent Line method.
Smith et al. (1989) have used EAR for two-phase equilibria calculations of binary mixtures. They
use a molecular model for dipolar hard spheres to model their mixtures. Hicks and Young (1977) first
used the construct of Fig. 1a as an aid to locate critical loci for binary mixtures. When approaching
the critical point of a fixed composition mixture from the two-phase side, the equal areas decrease to
exactly zero at the critical point. Thus, EAR is a valuable diagnostic tool for locating mixture critical
points. Fig. l a can also represent liquid-liquid equilibria (LLE) if an activity coefficient model
determines G m. Fig. lb is a typical graph o f (~G//OXI)P,T calculated from an EOS for a binary mixture
which exists as vapor and liquid at equilibrium. Eubank and Hall (1995) first noted this discontinuity.
The convergence rates of the EAR procedure are similar to those for the Tangent Line method for
binary mixtures. However, for multi-component systems, the EAR procedure should have faster
convergence rates than the Tangent Line method because EAR has a smaller dimensionality.
Previous experimental, correlational and predictive efforts involving the fluid phase equilibria of
hydrocarbon/water systems is summarized in Eubank et al. (1994). This article also shows the
necessity for multiple isothermal binary interaction constants (so-called phase-dependent coefficients)
when traditional van der Waals MCR are used with the present EOS.

2. Application of EAR using an EOS

Eubank and Hall (1995) have presented the derivation of EAR for binary mixtures. The basic
equation is

i;i,x'[t ~XI
~)G ~
J,>pdXl = G I
-- G I!
=G'I(XI-XII I ) (1)
where G is the Gibbs energy, x denotes mole fraction, G'I represents the derivative of G with respect
to xi, T is temperature, P is pressure, superscripts denote phases and subscripts denote component
number. For use with an EOS, it is more convenient to use the Gibbs energy of mixing

g- AmGR---T-= ~i xi ( ~£i-ld'i
)-R-T (2)

where A m denotes property change upon mixing, R is the gas constant, /, is the chemical potential
and superscript A denotes property of the component in a mixture. Realizing that

~i- ~£i = ln(xi~i) - ln(~i) (3)

RT

where ~b is the fugacity coefficient, the derivative of Eq. (2) with respect to composition is

O(AmG/RT) ] Xl@I
=In (1--" -In (4)
g'l = ax I T,P -x,)4,2
56 N.S.M. Hanif et a l . / Fluid Phase Equilibria 126 (1996) 53-70

in which the Gibbs-Duhem equation permits a reduction of terms. The equation equivalent to Eq. (1)
is

g l - g n = g l (rx iI - x l I) (5)
The function g is not uniformly continuous as calculated from an EOS because of the multiple
volume roots. Fig. 2a shows that g from phase I and g from phase II intersect at some value of x t in
a "comer" which causes a jump discontinuity in the corresponding g'-function (Fig. 2b). In this
paper, it is not necessary to evaluate integrals, but the g'-curve is valuable for determining the initial
guesses for the equilibrium compositions and the number of phases present in the mixture.
In this paper, we have selected the Peng-Robinson EOS ( P R / E O S ) to represent the mixtures. The
mixture combining rule ( W S / M C R ) is that proposed by Wong and Sandier (1992) as modified by
Eubank et al. (1995).

1.0
l\ g=gL a
..... not physical gL
0.8
g = gv I
•, ..... not physical ~ I
0.6 •• COlTler I ~v [
• t 4.5 , ~ ,

g
0.4 • /.--- =o.oL
0.2
_~ / ~, \ 0.~ o.75 I.~

0.0

-0.2
5.0
b
4.0

3.0

2.0
\
g/
l l.O

0.0

101\
t Lw
A I

I Y
0.0 0.2 0.4 0.6 0.8 1.0
Mixture Composition, x t

Fig. 2. Reduced Gibbs energy o f mixing, g, and its composition derivative, g'l, for the n - p e n t a n e ( 1 ) / w a t e r ( 2 ) system at
477.59 K and 48.263 bars.
 N.S.M. Hanif et al./ Fluid Phase Equilibria 126 (1996) 53-70 57

3. Algorithms using EAR

The algorithm for determining the number of phases present and their equilibrium compositions at
given conditions depends upon the number of phases which are present. The procedure is:
A. Initiation
1. Plot the g-curve to determine initial guesses for location of the comers.
2. Determine the comer compositions by equating g l and g lI.
3. Plot the g'l-curve to determine the initial guess for the equilibrium value, m~ (we use the average
of the values at the maximum and at the minimum of the largest loop), and to determine the
number of phases present by observing the number of loops on the g':plot.
B. Two-Phase Calculations
1. Evaluate x II and xl I as solutions to (g'l)l = m I and ( g'l )II = m I respectively.
2. Evaluate g l and g ii.
3. Check if gl _ g l l = ml(x l1 _ x,ll).
4. If the above condition is not satisfied within an acceptable tolerance (we require that successive
iterations on x~ be less than 10 -8 for each phase), then select a new m I (we use the bisection
method) and repeat the procedure from step B1.
5. If condition B3 is satisfied, x I and XllI are the phase compositions at equilibrium.
C. Three-Phase Calculations
1. Plot g against x~ to ascertain that two comers exist.
2. Plot g' against x~ to ascertain that it appears possible to assign an initial value of m~ such that
both sets of loops have equal areas above and below m I.
3. Evaluate x I, xl I and x~II as solutions to (g,)k = ml for k {I, II and III}.
4. Evaluate g k for k {I, II and III}.
5. Test the equalities (i) gl _ g i l l _ ml(x [ _ xlll) and (ii) g i l l _ gll = ml(Xlllt _ xli).
6. If the above conditions are not satisfied within 10 -8 for x~ in each phase, then select a new m~
using the bisection method and repeat the procedure from C2.
7. If the condition in C4 is satisfied then xI~, x] I and xl~H are the correct phase compositions at
equilibrium.
D. Algorithm Limitations
To solve g'l = ml initially for roots, xli (guess) and XllI (guess), it is necessary to choose values
sufficiently close to the true xI~ and x] l, respectively. A plot of g versus x 1 (the g-curve) can
identify the range within which xll and xl I might lie. In Fig. 2b, to solve (g,)i = ml for xil, the initial
x iI (guess) should lie in the composition range (0, comer 1) where comer 1 comes from Fig. 2a.

4. The g-curve from an EOS

The EAR procedure requires a plot of the dimensionless Gibbs energy of mixing against
composition before its derivative is plotted against composition. We call the former curve the
"g-curve" and the latter the "g'-curve". The g-curve should be drawn first to detect comers which
indicate phase separation. These comers then influence the shape of the g'-curve.
A cubic EOS model, here the P R / E O S , can provide either a vapor volume root, Vv, a liquid
58 N.S.M. Hanif et al./ Fluid Phase Equilibria 126 (1996) 53-70

volume root, Ve, or a vapor volume root and a liquid volume root. In regions where there is only one
root, a single, continuous g-curve exists without comers. If Vv is the root, we term the g-curve "gv"
and if the root is Ve, then we term the g-curve "ge." When the EOS predicts two roots, Vv and VL,
then two g-curves, g v and ge, exist and comers can occur.
The shapes of the g v and gL curves provide indications of the type of phases which exist at
equilibrium. In Fig. 2a, the heavy solid line represents g v and the light solid line represents ge.
Taken separately, the concavity of the vapor line means that vapors of different composition are
miscible in all portions but the mostly convex liquid curve means that water and n-butane are nearly
immiscible. Fig. 2b is the g'-curve which corresponds to Fig. 2a. The experimental VLE data for the
n-pentane(1)/water(2) mixture comes from Gillespie and Wilson (1982).

5. Stability criteria and definitions

The term stability has been used in multiple ways to describe a particular aspect of phase
equilibria. For example, consider a binary mixture which exists as vapor (V) and liquid (L) at
equilibrium with compositions, x v and x~, respectively. The Second Law of Thermodynamics
requires that g be at a minimum for equilibrium. The phases with compositions x v and x~ would be
thermodynamically stable if g were at a global minimum. Any other g minima for the system
represent thermodynamically unstable or metastable phases. If g > 0, the system is thermodynami-
cally unstable with respect to its pure components at the same temperature and pressure. A necessary
condition for mixture thermodynamic equilibrium is that g" > 0. Therefore, in Fig. 2b, only the points
L w and V would be stable. The corresponding g-curve in Fig. 2a would be unstable with respect to
its pure components at the same temperature and pressure in the composition range (0.00105, 0.4)
because g > 0 in this range. Finally, we examine the system in the composition range (0, 0.00105)
and (0.4, 1) because g < 0 and the phases in these regions can be stable.
A single phase is intrinsically stable if g" is greater than zero. The entire vapor curve of Fig. 2a is
intrinsically stable but only the portion with x~ > 0.4 is stable with respect to the pure components.
The phase would be intrinsically unstable if g" < 0. For example, in Fig. 2b, the liquid phase has
g'~ > 0 in the composition range (0, 0.04). However, the corresponding ge values in Fig. 2a are not
negative over this entire region so only in the range (0, 0.00105) could it be stable or metastable. The
liquid phase would be unstable in the range (0.00105, comer 1) and the vapor phase would be
unstable in the region (comer 1, 0.4) because the g values are positive.
It is also possible to investigate the stability of a phase relative to the other phases present which is
called multi-phase stability. Here, a phase is defined as stable if g < 0, g'( > 0 and its g values are
lower than those of the other phases. Heidemann (1974) discusses this situation. A phase would be
metastable if it had g < 0 and g'~ > 0 but a lower g value exists along a tie-line connecting other
phases. Finally, a phase would be unstable if it was neither stable nor metastable. For example, in Fig.
2b, the liquid phase curve has g'~ > 0 from x I = 0 to its maximum at x I = 0.04 and its g values are
lower than those of the vapor phase (see Fig. 2a). However, the gL values in Fig. 2a are only
negative in the range (0, 0.00105), therefore the liquid phase could only be stable in this region. The
liquid phase is not metastable in the region (0.00105, 0.04) although gL < gv and g'( > 0 because
g > 0. In Fig. 2b, the vapor phase has g'~ > 0 over the entire vapor phase range of (comer 1, 1). Also,
gv < ge over this range. However, gv is only negative over the range (0.4, 1). Therefore, the vapor
 N.S.M. Hanif et al./ Fluid Phase Equilibria 126 (1996) 53-70 59

phase could only be stable or metastable over the range (0.4, 1). Of course, the vapor phase would be
unstable over the range (0, comer 1) because its g values are higher than the corresponding liquid
phase values.
The ideas developed here to explain intrinsic and multi-phase stability can be combined to define
the overall thermodynamic stability of the system. It is obvious that a system is thermodynamically
stable only if each of its phases at equilibrium:
1. minimizes the g function
2. has g < 0
3. has g ' ; > 0
4. has the lowest g value compared to those of other phases at its composition.
When an EOS model provides the thermodynamic properties of a multi-component multi-phase
system, the success of the EAR method depends upon the different types of stability. It is important to
determine which portions of the g-curve or the g'-curve should be used in the calculations.

0.4

g
0.2

0.0
0 "dl
enlarged -- i /]
-0.2 below "~o.oL ~ / [
> I ,--:7,, .... I
0.0(I0 0.001 0.002
-0.4
. . . . ' . . . . i . . . . . . . . . t . . . . . . . . . ~ . . . . . . . . . i . . . . . . . . .

4.0

3.0

2.0
/
gl 1.0

0.0

-1.0

At L ,E A I -- A 2
-2.0 ,
0.0 0.2 0.4 0.6 0.8 1.0
Mixture Composition, x~

Fig. 3. Reduced Gibbs energy of mixing, g, and its composition derivative, g'~, for the n-pentane(l)/water(2) system at
477.59 K and 136.054 bars.
60 N.S.M. Hanif et al./ Fluid Phase Equilibria 126 (1996) 53-70

6. Predictions using only VL

Fig. 3a presents the g-curve for the n-pentane(1)/water(2) mixture at a fixed temperature and
pressure. The experimental VLE data for this mixture come from Gillespie and Wilson (1982). AmG
is calculated from the EOS model. At the given temperature (477.6 K) and pressure (136.1 bars), the
P R / E O S model indicates only one, real, volume root. This temperature is about 8 K above the
critical temperature of n-pentane which means that on Fig. 3a, at x~ = 1, pure n-pentane is a gas but
pure water ( x 1 = 0) is a liquid. Therefore, a transition exists from liquid to gas using the same volume
root. Hence, it would be fair to call the equilibrium vapor phase, V on Fig. 3b, a fluid. Because only
one EOS volume root exists, the EOS calculates the mixture as a single phase. This means that, at the
given conditions, the mixture appears to exists as a liquid or gas regardless of composition. However,
phase-splitting exists which results in a water-rich liquid phase, L w, and a hydrocarbon-rich fluid
phase, V, in equilibrium. This behavior becomes more apparent when viewing the g'-curve.
Fig. 3b shows the g'-curve corresponding to the g-curve in Fig. 3a. At equilibrium, A 1 = A 2 and
the value of g'~ = m I about which the areas A 1 and A 2 are evaluated is then exactly the slope of the
tangent line which provides equilibrium compositions in the Tangent Line method (Michelsen,
1982a). The equilibrium compositions result from the outer intersections of the m I line with the
g'-curve. These intersections are L w ( x 1 = 4.51 × 10 -4) and V (x I = 0.897) on Fig. 3b.

7. Corners on the g-curve

An intersection of the g v and gL curves is a comer because for any composition, x~, the phase
with the lower value of g is thermodynamically stable with respect to the other phase (Radzyminski
and Whiting, 1987). This means that whichever curve ( g v or gL) has the lower g values within a
particular composition range represents the stable phase. Whenever g v and gL curves intersect, the
g-curve changes from being gv to being gL or v i c e v e r s a . For example, in Fig. 2a, g = gL for the
composition range (0, comer 1) because g L < g V- Also, g = g v for the composition range (comer I,
1) because gv < gL" At comer 1, g changes from gL to gv- Hence, "comer" denotes the point at
which the gv and gL curves intersect.
The corresponding g'-curve for the mixture must have jump discontinuities at the comer composi-
tions. These jumps occur because at the intersection, the gv and gL curves have different slopes,
(g'l) v and (g,)L. The jump in the g'-curve corresponding to the comer in Fig. 2a appears in Fig. 2b
where the jump crosses the composition axis ( g' = 0) because of the sign change between (g'l)v and
(g,)L.

8. Discontinuities on the g-curve

If the cubic EOS does not predict two (stable) volume roots over the entire range of composition,
x~, then some regions exist in which only one volume root is present, Vv or VL. In such regions,
either gv exists and gL is unstable or v i c e v e r s a . Immediately before entering or after leaving this
region, a discontinuity exists in either g v or g L" For example, in Fig. 2a the cubic EOS only predicts
 N.S.M. Hanif et al./ Fluid Phase Equilibria 126 (1996) 53-70 61

a liquid volume root up to a composition of x~ = 0.25. At all higher compositions, the EOS predicts
only a V v value. At lower compositions (below x I = 0.25), V v and VL values exist but the gL curve
is below the g v curve to the left of comer 1. Only gL can be stable or metastable over the range (0,
0.00105) whereas only g v can be stable or metastable over the range (0.4, 1).
The discontinuities which occur on the g-curve do not directly affect the shape of the g'-curve.
However, the presence of discontinuities restricts the initial range of compositions within which may
lie the location of intersection points of the gv and gL curves. For example, in Fig. 2a, if no
discontinuity exists for the gL curve, the entire range of x~, (0, 1), would be available for the
intersection (comer 1) location which occurs at x I = 0.14. However, the presence of the discontinuity
limits the initial range for comer 1 to (0, 0.25). The influence of discontinuities is apparent in Fig. 4a
in which the second intersection of g v and gL (comer 2) lies between two discontinuities which limit
the possible range for comer 2 to (0.63, 0.65). Thus, lacking a plot of the g-curve presents the
possibility of not realizing that comer 2 exists and the corresponding g'-curve would provide

0.8

Pressure = 24.10 bars - - g = gL a

..... not physical gL
0.6 g=gv
comer 1 . - . = . . . . not physical gv
t 1.o ~ /,]
0.4 ~/ ~ o.0
g ~0_1.0 . . . . i . . . .

0 2 -q I~1' 0.0 1,0 2.0

" ~ N comer 2 x, x104

0.0 - - - -

-0.2

b
6.0

4.0 I
g[
2.0
i
----A l //
0.0
tA ~ \ I A. Jl

-2.0 /~ V L.c

Lw ~ At VLLE' A' = A2 ~ d A ' =A4

-4.0 . . . . . . . . ~ . . . . . . . . . . . . . . . . . . . . . . . . . . . ' . . . . . . . .
0.0 0.2 0.4 0.6 0.8 1.0
Mixture Composition, x

Fig. 4. Reduced Gibbs energy of mixing, g, and its composition derivative, g'l, for the n-octane(1)/water(2) system at the
predicted three-phase pressure at 477.59 K.
 62 N.S.M. H a n i f et a l . / Fluid Phase Equilibria 126 (1996) 5 3 - 7 0

incorrect predictions. The correct g'-curve is Fig. 4b. The experimental VLLE data for the
n-octane(1)/water(2) mixture come from Heidman et al. (1985).
Discontinuities in either gv or gL do not affect the shape of the g'-curve because the g-curve
which has the discontinuity has higher values than the other curve and its phase is unstable with
respect to the stable phase. In Fig. 2a, gL has a discontinuity at x~ = 0.25 but from comer 1 to this
discontinuity gL > gv SO gv is used as g. The discontinuity never appears on the g'-curve in Fig. 2b
because for the composition range (comer 1, 1), the derivative of the gv curve is g'j. As another
example, Fig. 4a has three discontinuities whereas Fig. 5a has no discontinuities. However, Fig. 4a
and Fig. 5a both have two comers (intersections of their respective gv and gL curves). It is the two
comers which produce similar shapes in the g'-curves shown in Fig. 4b and Fig. 5b. Note that the
discontinuities in Fig. 4a do not change the shape of the g'-curve in Fig. 4b as compared to Fig. 5b.
In summary, it is important to analyze both the g- and g'-curves when using EAR with an EOS
model. Such scrutiny is necessary to understand phase stability over the entire composition range.

1.5
Pressure = 6.504 bars g = gL a I
..... not physical gL [
1.0 g=gv
•" ...... "- -. - .... not physical gvoO

e I B# •

0.5 •" comer 1 ".

g

0.0
<_
enlarged
,,°-5
- o.o
r
-0.5
0.00 0.75 1.50

x I x 105
-1.0 . . . . . . . . I . . . . . . . . . r . . . . . . . . 'l . . . . . . . . . r . . . . . . . . .

8.0
,) b
6.0 I
[
I
4.0 I
I
g( ~ A 1
2.0

0.o II A
/ 3 Ii A4 /
I
-20 / * L.,
Lw At VLLE, A l = A 2 and A 3 = A.
-4.0 . . . . . . . . . I . . . . . . . . . I . . . . . . . . . I . . . . . . . . . I . . . . . . . . .

0.0 0.2 0.4 0.6 0.8 1.0

Mixture Composition, x l

Fig. 5. R e d u c e d G i b b s e n e r g y o f m i x i n g , g, and its c o m p o s i t i o n derivative, g'l, f o r the n - o c t a n e ( l ) / w a t e r ( 2 ) s y s t e m at the

predicted t h r e e - p h a s e p r e s s u r e at 4 2 2 . 0 4 K.
 N . S . M . H a n i f et a l . / F l u i d P h a s e E q u i l i b r i a 126 (1996) 5 3 - 7 0 63

9. D e t e r m i n i n g the n u m b e r o f phases at e q u i l i b r i u m

The g'-curve reveals the number of phases present at equilibrium for a system at a given
temperature and pressure. The analysis depends upon how many comers exist on the corresponding
g-curve.
If no comers exist on the g-curve (jumps on the g'-curve), the maximum number of phases present
depends upon whether any horizontal line (m 1 value) can be drawn on the g'-curve such that equal
areas result about the line. If no such line can be drawn, only one phase exists. A sufficient condition
for one phase to be present is that the corresponding g-curve has no inflections. A sufficient condition
for two phases to exist is that the g-curve has two inflections. An example of this appears in Fig. 3b.
VLE exists because the g'-curve has two extrema at x~ = 0.03 and at x~ = 0.47.

i
Temperature = 344.26 K g = gL a I
3.0 2, Pressure = 6.895 bars ..... not physical g [
•• L
• g=gv I
2.5 ", ..... not physical gv[

2.0
"-, /LI
• ,. come : o.o k / / [ !
1.5 d -.. /
,/_.__
~-I.o Ii . . .~. ~ ....
II
I
"- - - . . o.0 1.5 3.01
1.0

0.5

0.0

8.0
b
6.0

4.0

gl /
2.0

0.0
\
-2.o Lw

At VLE, A 1 = A
-4.o ......... E,,,. ....
0.o 0.2 0.4 0.6 0.8 1.0
Mixture Composition, x

Fig. 6. R e d u c e d Gibbs energy, g , and its c o m p o s i t i o n derivative, g'l, for the n - b u t a n e ( l ) / w a t e r ( 2 ) s y s t e m b e l o w the
t h r e e - p h a s e pressure.
64 N.S.M. Hanif et al. / Fluid Phase Equilibria 126 (1996) 53-70

If one comer exists on the g-curve, exactly two phases are present. Two phases are present because
a horizontal line (mm) can be drawn on the g'-curve such that equal areas exist above and below this
line as shown on Fig. 2b.
If the g-curve has two comers, at least two phases and at most three phases are present at
equilibrium. At least two phases must exist because a horizontal line can pass through each jump in
the g'-curve (comer 1 or comer 2) with equal areas above and below the line. Fig. 6a contains an
example of this behavior; the corresponding g'-curve is Fig. 6b. The experimental VLE data for the
n-butane(1)/water(2) system come from Reamer et al. (1952).
Fig. 7 presents the n-butane(1)/water(2) mixture at 344.26 K and 9.0 bars. This pressure is slightly
greater than the three-phase pressure (8.95 bars). This figure demonstrates why it is not necessary that
three phases coexist. At the given conditions, equilibrium occurs when A~ + A 3 = A 2 + A 4 but
A 1 ~ A 2 and A 3 4: A 4. Therefore, only two phases are present at equilibrium.
Fig. 8a and b illustrate when the presence of two comers leads to three-phase equilibrium. Fig. 8a
is the g-curve which contains two comers. The inserts in Fig. 8b show that it is possible for the three
phases to exist at equilibrium because they each have intrinsically stable regions where g < 0 and
g'( > 0. The gv curve does not extend to x I = 1 because the EOS predicts only a liquid volume root
in the composition range (0.995, 1). The area equalities of A 1 - - A 2 and A 3 = A 4 in Fig. 8b indicate
that the system is exactly at the three-phase pressure with the phase points, L w being the water-rich
liquid, LHc the n-butane-rich liquid, and V the vapor phase. Only one three-phase pressure can exist
and the compositions of the three phases shown in Fig. 8b agree closely with experiment (see Table
1). At a higher pressure, A 1 -1-A 3 = A 2 + A 4 but AI ~ A 2 so only the L w - L H c equilibrium is present.
Below the three-phase pressure, an equal area exists between points L w and V but not between V and
LHC, providing only water-rich liquid/vapor equilibrium. This is also the water-rich liquid dew-point
where A~ = A 2 but the liquid curve of Fig. 8a remains well above that of the vapor to the right of
comer 1 and comer 2 is absent.

6.0
Temperature = 344.26 K
Pressure = 9.00 bars
4.0 ~ AtLLE, A l + A 3 = A 2 + A 4
but Al:;e A3 and A2¢: A4

/ 2.0 A1 L~!

gJ A3
0.0

-2.0 1

-4.0
0.0 0.2 0.4 0.6 0.8 1.0
Mixture Composition, x 1

Fig. 7. Composition derivative of the reduced Gibbs energy of mixing, g'l, for the n-butane(l)/wateff2) system slightly
above the three-phase pressure.
 N.S.M. Hanif et al./ Fluid Phase Equilibria 126 (1996) 53-70 65

1
Temperature = 344.26 K 8t
3.0 i• Pressure 8,63 bars g = gL
• ..... not physical g
• g=gv
2.5 ~ . ~ ..... not physical gv

2.0 • / ,,,x I 10~:~

g
1.5
'%•
•
""/
comer 1
0. 5
l--lL:
~ J x , 0

10
--

1.0
xx16,~>'~ ~ "'-.. tr I

0.5

0.0

6.0
b
4.0

2.0
/
gl 0.0 -

-2.0

2.0

40 ol oO

-6.0 d.o - l
-~.o' i
I A,
At VLLE, A 1 = A2 and A 3 -- A4 0.9o 0.95 1.00
-8.0 . . . . . . . . . , . . . . . . . . . ~ . . . . . . . . . , . . . . . . . . . , .........
0.0 0.2 0.4 0,6 0.8 1.0
Mixture Composition, x l

Fig. 8. Reduced Gibbs energy of mixing, g, and its composition derivative, g'l, for the n-butane(l)/water(2) system at the
predicted three-phase pressure.

Table 1
Vapor pressures and mixture parameters for the systems studied
System T/K P~/bars P~'/bars k12 At2 A21
n-Butane(1)/water(2) 344.26 8.31 0.33 0.585 9.36 8.82
n-Pentane(1)/water(2) 477.59 SC a 17.05 0.596 9.70 4.50
n-Octane( l )/water(2) 422.04 1.86 4.62 0.675 15.70 5.15
477.59 6.00 17.05 0.675 13.83 3.14

a At 477.59 K, n-pentane is supercritical (SC).

66 N.S.M. Hanif et al./ Fluid Phase Equilibria 126 (1996) 53-70

10. Difficulties with classical flash calculations

W e define the classical flash calculation (CFC) as one which uses the K-value approach with
neither stability analysis nor Gibbs minimization. It is well known that the CFC does not always
converge to the correct number a n d / o r type of phases in difficult regions of the phase diagram.
However, Gibbs minimization procedures (properly applied) always converge to the correct number
of phases and their corresponding compositions because they minimize g across the entire composi-
tion range. The n-butane/water data set at 344.26 K is a good example to illustrate when CFC does
not converge to the correct phases.
In this data set, at 6.895 bars, VLE exists. Fig. 6a presents the g-curve at this pressure. Comer I
appears and at higher compositions g v < gL- The g'-curve would have a jump at comer 1, and at
higher compositions the g'-curve (Fig. 6b) represents the slope of gv- From Fig. 6b, it is clear that
VLE exists and that EAR predicts the equilibrium compositions, x~ = 7.04 × 10 -5 and x v = 0.954.

~, Temperature= 344.26 K ~ g gL
---- a
3.0 -~ i• Pressure = 10.34bars . . . . . not physicalg

2.5 ~
• ,b g=gv
. . . . . not physical
"" "--.../ 4.0
2.0 ~ 1 [~[~'q''"k ~ 0.0
0~ / corner 1
1.5 ~-1 '~'~ / -4.0
0 2 4 __... 0.99 1.00 ,

" ' . corner 2

0.5

0.0 ', . . . . . . . . . , . . . . . . . .
8.0
b
6.0

4.0
/
gl 2.0
LHC~

0.0

-2.0
At LLE, AI = A2
-4.0 ......... I ......... i ......... i ..................
0.0 0.2 0.4 0.6 0.8 1.0
Mixture Composition,x
Fig. 9. Reduced Gibbs energy, g, and its composition derivative, g'l, for the n-butane(l)/water(2) system above the
three-phase pressure.
 N.S.M. Hanif et al. / Fluid Phase Equilibria 126 (1996) 53-70 67

Aqueous Liquid Composition, xw x 10~

0.0 3.0 6.0 9.0 12.0 15.0
14.0 I I I I
0

12.0 x 3 Phase exp. data ~ i / J// i

o Experimental data /
I0.0 - EAR prediction ~ /
:/
8.0
- - - Classical Flash prediction /X ~-~
/
.o
d
6.0

4.0 /0/ ¢
J
o/
2.0-
ff.~. . . . . . . . . . . . . . . . . . ....... ._-J •
0.0 ! - I I 7---- I
0.0 0.2 0.4 0.6 0.8 1.0
HC
Composition of Vapor and HC-rich Liquid Phases, Yl or x l

Fig. 10. P - x - y d i a g r a m for the n - b u t a n e ( 1 ) / w a t e r ( 2 ) s y s t e m at 344.26 K. Points are e x p e r i m e n t a l data f r o m R e a m e r et al.

(1952).

The classical flash calculation also gives the same prediction because it uses the same liquid and
volume roots when converging to a liquid phase and a vapor phase.
The three-phase pressure at 344.26 K for the normal n-butane/water mixture is about 8.65 bars,
and at 13.79 bars Reamer et al. (1952) observe LLE under these conditions. Therefore, the mixture
must exhibit LLE for any pressure between 8.65 and 13.79 bars. Fig. 9a is the g-curve for this system
at 10.34 bars. Two comers appear, so at compositions near unity the liquid phase is stable. In terms of
stability with respect to the pure components, the vapor phase cannot be stable because g > 0 over the
entire composition range. Fig. 9b, the g'-curve corresponding to Fig. 9a, indicates that VLLE cannot

Table 2
Equilibria data c o m p a r i s o n for the s y s t e m s studied
System T/K P/bars L w : XHC × 105 LHc: Xw X 102 YHC Phase See figures
Exp. Calc. Exp. Calc. Exp. Calc. Exp. Calc. equilibria

6.895 6.895 7.10 7.18 - - 0.956 0.954 VLE Fig. 6a,b

8.650 8.630 8.70 8.73 0.210 0.201 0.966 0.967 VLLE Fig. 8a,b,c
n-Butane(l)/ 344.26 - 9.000 - 8.74 - 0.201 - - LLE Fig. 7
water(2)
- 10.340 - 8.76 - 0.200 - - LLE Fig. 9a,b,c
13.790 13.790 8.80 8.83 0.200 0.200 - - LLE -
n-Pentane(l)/ 477.59 48.263 48.263 32.6 31.1 - - 0.683 0.671 VLE Fig. 2a,b
water(2)
136.054 136.054 40.0 45.1 - - 0.900 0.897 VLE Fig. 3a,b
n-Octane(l)/ 422.04 6.639 6.504 0.38 0.38 3.94 3.93 0.264 0.304 VLLE Fig. 5a,b
water(2)
477.59 25.373 24.098 4.00 4.00 12.6 12.6 0.296 0.297 VLLE Fig. 4a,b
68 N.S.M. Hanif et al. / Fluid Phase Equilibria 126 (1996) 53-70

exist because there is not an m~ value about which equal area loops can appear. Therefore, the actual
m~ value at equilibrium indicates LLE and the composition of the phases result in the usual manner.
Note that the gv curve still determines the final LLE even though it is not stable. This is usual when
an EOS models the system. These compositions agree well with experiment. At this pressure, the CFC
still converges to VLE because it still uses both Vv and VL roots as it does at 6.895 bars. In this case,
CFC misses the fact that one liquid can be in equilibrium with another liquid of different composition.
Therefore, the CFC uses the incorrect roots and predicts VLE instead of LLE which then produces
incorrect equilibrium compositions. CFC, expecting VLE, fails to predict the LLE. This analysis
explains the problems first observed by Baker et al. (1982) for the CO2/n-decane system near its
three-phase pressure.
Fig. 10 is a P-x-y diagram of the n-butane(1)/water(2) mixture at 344.26 K with experimental
data from Reamer et al. (1952). This figure illustrates that CFC may fail to predict the three-phase
pressure and then LLE as pressure increases. EAR, however, provides accurate predictions of the
three-phase pressure and equilibrium compositions (see Table 2) when used with the P R / E O S and
the W S / M C R as modified by Eubank et al. (1995).

11. Conclusions

Smith et al. (1989) and Hicks and Young (1977) have used the equal area construct with simple
molecular-based models for G E in binary mixtures. We have recognized the usefulness of EAR as an
efficient Gibbs minimization method applicable to multi-component, multi-phase equilibria. We have
shown that EAR works well with a reasonably complicated model ( P R / E O S and W S / M C R ) and
have presented a detailed analysis of two-phase and three-phase equilibria predictions with EAR.
EAR is an exciting new method for calculating multi-phase equilibria in multi-component
mixtures. Shyu et al. (1995) have applied the method to ternary liquid-phase systems using activity
coefficient models. We are developing the procedures for EAR needed to calculate phase behavior of
ternary mixtures with an EOS model. The procedures appear to be general, so the step to higher
component mixtures should not be prohibitive.
Our results in Table 2 show that the W S / M C R with the P R / E O S can provide accurate a priori
predictions of VLE, LLE and VLLE for w a t e r / H C systems. We have used the procedures in Eubank
et al. (1995) to determine the WS kl2.

12. List of symbols

AI2 natural logarithm of the Margules infinite dilution

activity coefficient of component (1)
A21 natural logarithm of the Margules infinite dilution
activity coefficient of component (2)
CFC classical flash calculation
EAR equal area rule
EOS equation of state
G molar Gibbs free energy
 N.S.M. Hanif et al. / Fluid Phase Equilibria 126 (1996) 53-70 69

AmG Gibbs energy of mixing

g Gibbs energy of mixing reduced by RT
kl2 binary interaction constant
LLE liquid-liquid equilibrium
m a specific value of the derivative of g with respect to composition
MCR mixture combining rule(s)
MEAR Maxwell's equal area rule
P pressure
PR Peng-Robinson
R gas constant
T temperature
V molar volume
VLE vapor-liquid equilibrium
VLLE vapor-liquid-liquid equilibrium
WS Wong-Sandler
X mole fraction of liquid or gas
Y mole fraction of gas

12.1. Subscripts

C critical property
HC hydrocarbon phase
i pure component (i) property
i molecular species or term in an expansion
L liquid phase
m mixture property
r reduced property
V vapor phase
W water phase

12.2. Superscripts

E excess property upon mixing

I, II different phases which are in equilibrium with each other
k phase counter
r derivative with respect to temperature or composition
second derivative with respect to temperature or composition

Acknowledgements

The National Science Foundation (Grant CTS-9021129) and the U.S. Department of Energy (Grant
DE-FG03-93AR14357) have provided financial support for this research.
70 N.S.M. Hanif et al./ Fluid Phase Equilibria 126 (1996) 53-70

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