Chapter 23

Phase Diagrams
F.M. OTKJr., New Mexico Inst. of Mining and Technology
J.J. Taber, New Mexico Inst. of Mining and Technology*

Introduction
Petroleum reservoir fluids are complex mixtures containing many hydrocarbon components that range in size
from light gases such as methane, ethane, and so on to
very large hydrocarbon molecules containing 40 or more
carbon atoms. Nonhydrocarbon components such as
nitrogen, hydrogen sulfide (HzS), or CO2 also may be
present. Water, of course, is usually present in large
quantities in all reservoirs. At a given temperature and
pressure, the components distribute between whatever
solid, liquid, and vapor phases are present. A phase may
be defined as that portion of a system that is
homogeneous, bounded by a surface, and physically
separable from other phases present. Equilibrium phase
diagrams offer convenient representations of the ranges
of temperature, pressure, and composition within which
various combinations of phases coexist. Phase behavior
plays an important role in a variety of reservoir engineering applications ranging from pressure maintenance to
separator design to enhanced oil recovery (EOR) processes. This chapter reviews the fundamentals of phase
diagrams used in such applications.

Single-Component Phase Diagrams

Fig. 23.1 summarizes the phase behavior of a single
component. The saturation curves shown in Fig. 23.1 indicate the temperatures and pressures at which phase
changes occur. At temperatures below the triple point,
the component forms a vapor if the pressure is below that
indicated by the sublimation cuwe, and forms a solid at
pressures above the curve. At pressures and temperatures
lying on the sublimation curve, solid and vapor can
coexist, and on the melting curve, solid and liquid are in
equilibrium. At higher temperatures, liquid and vapor
can coexist along the vaporization or vapor-pressure
curve. If the pressure is greater than the vapor pressure, a
liquid forms, if lower, a vapor. The vapor-pressure curve

terminates at the critical point. At temperatures above

the critical temperature, T,, a single phase forms over
the entire range of pressures. Thus, for a single component, the critical temperature
is the maximum
temperature at which two phases can exist. Critical
temperatures of hydrocarbons vary widely. Small
hydrocarbon molecules have low critical temperatures,
while those of large ones are much higher. Critical
pressures generally decline as the molecular size increases. For instance, the critical temperature and
pressure of methane are - 117F and 668 psia. For
decane, the values are 652F and 304 psia. (Fig. 23.9
shows additional vapor pressure curves and critical
points for several other light hydrocarbon molecules.)
For many reservoir engineering
applications liquid/vapor equilibrium is of greatest interest, though liquid/liquid equilibria are important in some EOR processes. Solid/liquid phase changes, such as asphaltene or
paraffin precipitation, occasionally occur in petroleum
production
operations.
Fig. 23.2 shows typical
volumetric behavior of a single component in the range
of temperatures and pressures near the vapor-pressure
curve in Fig. 23.1. If the substance under consideration
is placed in a pressure cell at constant temperature T1
below T, and at a low pressure (Point A, for instance), it
forms a vapor phase of high volume (low density). If the
volume of the sample is decreased with the temperature
held constant, the pressure rises. When the pressure
reaches p,, (T1 ), the sample begins to condense. The
pressure remains constant at the vapor pressure until the
sample volume is reduced from the saturated vapor
volume (V,.) to that of the saturated liquid (V,). With
further reductions in volume, the pressure rises again as
the liquid phase is compressed. Note that small decreases
in volume give rise to large pressure increases in the liquid phase because of the low compressibility of liquids.
At a temperature Tz above the critical temperature, no
phase change is observed. Instead, the sample can be

PETROLEUM

ENGINEERING

HANDBOOK

MELTING
CURVE

i:

CRITICAL
POINT

SOLID

3
z

Pb

k
a

VAPORIZATION

Pd

VAPOR

SUBLIMATION
CJRVE

PV2

TC

T
Fig. 2X1-Phase

MPERATURE

Tc
I

Vc

Vv

1.0

XE
COMPONENT

of freedom (F=O). Thus, the maximum number of

phases possible is three. Therefore, if three phases coexist in equilibrium (possible only at the triple point), the
pressure and temperature are fixed. If only two phases
are present for a pure component, then either the
temperature or the pressure can be chosen. Once one is
chosen, the other is determined. If the two phases are
vapor and liquid, for example, choice of the temperature
determines the pressure to be the vapor pressure at that
temperature.
These permitted pressure-temperature
values lie on the vapor pressure curve of Fig. 23.1.
In a binary system, two phases can exist over a range
of temperatures and pressures. The number of degrees of
freedom is
F=2-nc,

VOLUME

Fig. 23.2-Volumetric
behavior of a pure component in the
liqutd/vapor region.

compressed from high volume (low density) and low

pressure to low volume (high density) and high pressure
with only one phase present.

. . . . . . . . . . . . . . . . . . . . . . . . . . . . ...(2)

and hence both the temperature and pressure can be

chosen, though there is no guarantee that two phases will
occur at a specific choice of T and p. For multicomponent systems, the phase rule provides little guidance,
since the number of phases is always far less than the
maximum number that can occur. Hence, as the number
of components increases, more component concentrations must be known to determine the system.

Types of Diagrams

Phase Rule
The maximum number of phases that can coexist at fixed
temperature and pressure is determined by the number of
components present. The phase rule states that
F=2+C-P-n,,

FRACTION

Fig. 23.3-Pressure-composition
phase diagram for a binary
mixture at a temperature below the critical
temperature of both components.

behavior of a pure component.

TC

MOLE

Tc

...... .... ....

. . . . . . (1)

where F is the number of degrees of freedom, C is the

number of components, P is the number of phases, and
n c is the number of constraints. For a single-component
system, the maximum number of phases occurs when
there are no constraints (n c =0) and there are no degrees

Binary Phase Diagrams

Fig. 23.3 shows typical vapor/liquid phase behavior for
a binary system at a fixed temperature below the critical
temperature of both components. Such a diagram is
known as a pressure-composition
phase diagram. At
pressures below the vapor pressure of Component 2,
~2, any mixture of the two components forms a single
vapor phase. At pressures between p 1 and p,,~ , two
phases can coexist for some compositions. For instance,
at pressure pb two phases will occur if the mole fraction
of Component 1 lies between xE and xE. If the mixture

PHASE DIAGRAMS

23-3

:i

PUMP

?2!!!%?
MERCURY
PUhlP
Pep,,

PPd

Pr,<P<Pb

PPb

PPb

Fig. 23.4-Volumetric
behavior of a binary mixture at constant temperature

ppdl

--pi pd

---

---

PZPl

PPd2

P3P2

Fig. 23.6-Volumetric
behavior of a binary mixture at a
constant
temperature
showing
retrograde
vaporization.

Pd2

Pdl

PVZ
VAPOR

xI
MOLE

FRACTION

K2
COMPONENT

TEMPERATURE

Fig. 23.5-Pressure-composition
phase diagram for a binary
mixture at a temperature above the critical
temperature of Component 1.

Fig. 23.7--Regions of temperature, pressure, and composition for which two phases occur in a binary liquid/vapor system.

composition is xB, it will be all liquid, if it is xE, all

vapor. For 1 mol of mixture of overall composition, z,
between -xE and xE, the number of moles of liquid
phase is

Phase diagrams such as Fig. 23.3 can be determined

experimentally by placing a mixture of fixed overall
composition in a high-pressure cell and measuring the
pressures at which phases appear and disappear. For example, a mixture of composition xa would show the
behavior indicated qualitatively in Fig. 23.4. At a
pressure less thanpd (Fig. 23.3), the mixture is a vapor.
If the mixture is compressed by injecting mercury into
the cell, the first liquid, which has composition xA, appears at the dewpoint pressure, pd. As the pressure is
further increased, the volume of liquid grows as more
and more of the vapor phase condenses. The last vapor,
of composition X,R, disappears at the bubblepoint
pRssut& pb.
If the system temperature is above the critical
temperature of one of the components, the phase
diagram is similar to that shown in Fig. 23.5. (See Fig.
23.13 for additional examples of this type of phase
diagram.) At the higher temperature, the two-phase
region no longer extends to the pure Component 1 side of

L=-.

XE --z

. . . . . . . . . . . . . . . . . . . . . . . . . . ...(3)

XE -xB

Eq. 3 is known as an inverse lever rule because it is

equivalent to a statement concerning the distances along
a tie line from the overall composition to the liquid and
vapor compositions; L=ZE/BE, where ZE and BE are
lengths on the tie line shown in Fig. 23.3. Thus, the
amount of liquid is proportional to the distance from the
overall composition to the vapor composition divided by
the length of the tie line. The line connecting the compositions of phases in equilibrium is known as a tie line.
In binary phase diagrams such as Fig. 23.3, the tie lines
are always horizontal.

PETROLEUM ENGINEERING

23-4

HANDBOOK

CRITICAL
LOCUS
<

TEMPERATURE
Fig. 23.8-Projection
of the vapor pressure (p,, and pa)
curves and locus of critical points for binary mixtures. Points C, and C2 are the critical points of
the pure components.
Fig. 23.10-Properties

Fig. 23.9-Vapor
pressure curves for light hydrocarbons and
critical loci for selected hydrocarbon pairs.

of ternary diagrams

the diagram. Instead, there is a critical point, C, at which

liquid and vapor phases are identical. The critical point
occurs at the maximum pressure of the two-phase region.
The volumetric behavior of mixtures containing less
Component 1 than the critical mixture is like that shown
in Fig. 23.4. Fig. 23.6 shows the volumetric behavior of
mixtures containing more Component 1. Compression of
mixture of composition x2 (in Fig. 23.5) leads to the appearance of liquid phase of composition xt when
pressure pDl is reached. The volume of liquid first
grows and then declines with increasing pressure. The
liquid phase disappears again when pressure pm is
reached. Such behavior is called retrograde vaporization (or retrograde condensation if the pressure is
decreasing).
If the system temperature is exactly equal to the
critical temperature of Component 1, the critical point on
the binary pressure-composition
phase diagram is
located at a Component 1 mole fraction of 1.O. Fig. 23.7
shows the behavior of the two-phase regions as the
temperature rises. As the temperature increases, the
critical point moves to lower concentrations of Component 1. As the critical temperature of Component 2 is approached, the two-phase region shrinks, disappearing
altogether when the critical temperature is reached. A
typical locus of critical temperatures and pressures for a
pair of hydrocarbons is shown in Fig. 23.8. The critical
locus shown in Fig. 23.8 is the projection of the critical
curve in Fig. 23.7 onto the p-T plane. Thus, each point
on the critical locus represents a critical mixture of different composition, though composition information is
not shown on this diagram. For temperatures between
the critical temperature of Component 1 and Component
2, the critical pressure of the mixtures can be much

PHASE DIAGRAMS

23-5

Fig. 23.11-Ternary
phase diagram at a constant temperature
and pressure for a system that forms a liquid and a
vapor.

Fig. 23.12-Ternary
phase diagram for the methane/
butane/decane system at 160DF 171Cl.

higher than the critical pressure of either component.

Thus, two phases can coexist at pressures much greater
than the critical pressure of either component. If the difference in molecular weight of the two components is
large, the critical locus may reach very high pressures.
Fig. 23.9 gives critical loci for some hydrocarbon
pairs.
The binary phase diagrams reviewed here are those
most commonly encountered. More complex phase
diagrams involving liquid/liquid and liquid/liquid/vapor
equilibria do occur, however, in hydrocarbon systems at
very low temperatures (well outside the range of conditions encountered in reservoirs or surface separators) and
in COz/crude oil systems at temperatures below about
50C. For reviews of such phase behavior see Refs. 2
and 3.

(Fig. 23.10b). In addition, mixtures lying on any line

connecting a comer with the opposite side contain a constant ratio of the components at the ends of the side (Fig.
23.1Oc). Finally, mixtures of any two compositions,
such as A and B in Fig. 23. lOd, lie on a straight line connecting the two points on the ternary diagram. Compositions represented on a ternary diagram can be expressed
in volume, mass, or mole fractions. For vapor/liquid
equilibrium diagrams, mole fractions are most commonly used.
Typical features of a ternary phase diagram for a
system that forms a liquid and a vapor at fixed
temperature and pressure are shown in Fig. 23.11. Mixtures with overall compositions that lie inside the binodal
curve will split into liquid and vapor. Tie lines connect
compositions of liquid and vapor phases in equilibrium.
Any mixture on one tie line gives the same liquid and
vapor compositions. Only the amounts of liquid and
vapor change as the overall composition changes from
the liquid side of the binodal curve to the vapor side. If
the mole fractions of component i in the liquid, vapor,
and overall mixture are xi, yi, and zi, the fraction of the
total moles in the mixture in the liquid phase is given by

Ternary Phase Diagrams

Phase behavior of mixtures containing three components
is conveniently represented on a triangular diagram such
as that shown in Fig. 23.10a. Such diagrams are based
on the property of equilateral triangles that the sum of the
perpendicular distances from any point to each side of
the diagram is a constant equal to length of any of the
sides. Thus, the composition of a point in the interior of
the triangle is
x, =-)

Ll
LT

x2 =-)

L2
LT

x3 =-)

........

. . . . . . . ......

. . (5)

L3
LT

where
LT=LI +L2 +L3.

L= Yi -zi
yi-xi

......

. . . . . . . . . . . . . (4)

Several other useful propetties of triangular diagrams are

also a consequence of this fact. For mixtures along any
line parallel to a side of the diagram, the fraction of the
component of the comer opposite to that side is constant

Fq. 5 is another lever rule similar to that described for

binary diagrams. The liquid and vapor portions of the
binodal curve meet at the plait point, a critical point
where the liquid and vapor phases are identical. Thus,
the plait point mixture has a critical temperature and
pressure equal to the conditions for which the diagram is
plotted. Depending on the pressure and temperature and
components, a plait point may or may not be present.
Any one tematy
diagram is given for fixed
temperature and pressure. As either the temperature or
pressure is varied, the location of the binodal curve and

PETROLEUM ENGINEERING

23-6

HANDBOOK

1
P
A

,
3
z
i;
1

1000

A
TEMPERATURE

0.2
MOLE

0.4

0.6

FRACTION

METHANE

0.S

:
I 0

Fig. 23.13-Pressure-composition
phase diagrams
for
methane/butane
and methaneldecane
binary
systems at 160F [71C].

slopes of the tie lines may change. Fig. 23.12 shows the
effect of increasing pressure on ternary phase diagrams
for mixtures of methane (C 1), butane (C,), and decane
(COO) at 160F. 4J The sides of the ternary diagram
represent a binary system, so the ternary diagram includes whatever binary tie lines exist at the temperature
and pressure of the diagram. Fig. 23.13 shows the corresponding binary phase diagrams for the C l-C4 and
C 1-C 1o pairs. The Cd-C 10 pair is not shown because it
forms two phases only below the vapor pressure of C4,
about 120 psia at 160F (see Fig. 23.9).
As shown in Fig. 23.12, at 1,000 psia the two-phase
region is a hand that stretches from the C 1-C 10 side of
the diagram to the tie line on the C I -Cd side. If the
pressure is increased above 1,000 psia, the liquid composition line shifts to higher methane concentrations;
methane is more soluble in both C4 and Cl0 at the
higher pressure (see Fig. 23.13). The two-phase region
detaches from the C ,-C4 side of the diagram at the
critical pressure of the C I -C4 pair (about 1,800 psia).
As the pressure increases above that critical pressure, the
plait point moves into the interior of the diagram (Fig.
23.12, lower diagrams). With further increases in
pressure, the two-phase region continues to shrink. It
would disappear completely from the diagram if the
pressure reached the critical pressure of the Cl-C 10
system at 160F (nearly 5,200 psia).
Reservoir Fluid Systems
Real reservoir fluids contain many more than the two or
three components, so phase composition data can no
longer be represented with two or three coordinates. In-

Fig. 23.14-Pressure-temperature
phase diagram for a mixture of fixed composition.

stead, phase diagrams, which give more limited information, are used. Fig. 23.14 shows one such diagram for a
multicomponent mixture. Fig. 23.14 gives the region of
temperatures and pressures at which the mixture forms
two phases. The analog of Fig. 23.14 for a binary system
can be obtained by taking a slice at constant mole fraction of Component 1 through the diagram in Fig. 23.7.
Also given arc contours of liquid volume fractions,
which indicate the fraction of total sample volume occupied by the liquid phase. Fig. 23.14 does not give any
compositional information, however. In general, the
compositions of coexisting liquid and vapor will be different at each temperature and pressure.
At temperatures below the critical temperature (Point
C), a sample of the mixture described in Fig. 23.14 splits
into two phases at the bubblepoint pressure (Fig. 23.4)
when the pressure is reduced from a high level. At
temperatures above the critical temperature, dewpoints
are observed (Fig. 23.6). In this multicomponent
system, the critical temperature is no longer the maximum temperature at which two phases can exist. Instead, the critical point is the temperature and pressure at
which the phase compositions and all phase properties
are identical.
The bubblepoint, dewpoint, and single-phase regions
shown in Fig. 23.14 are sometimes used to classify
reservoirs. At temperatures above the cricondentherm,
the maximum temperature for the formation of two
phases, only one phase occurs at any pressure. For instance, if the hydrocarbon mixture of Fig. 23.14 were to
occur in a reservoir at temperature TA and pressure PA
(Point A), a decline in pressure at approximately constant temperature caused by removal of fluid from the
reservoir would not cause the formation of a second
phase. While the fluid in the reservoir remains a single
phase, the produced gas splits into two phases as it cools
and expands to surface temperature and pressure at Point
A. Thus, some condensate would be collected at the

PHASE DIAGRAMS

surface even though only one phase is present in the formation. The amount of condensate collected depends on
the operating conditions of the separator (or separators).
The lower the temperature at a given pressure, the larger
the volume of condensate collected (Fig. 23.14).
Dewpoint reservoirs are those for which the reservoir
temperature lies between the critical temperature and the
cricondentherm for the reservoir fluid. Production of
fluid from a reservoir starting at Point B in Fig. 23.14
causes liquid to appear in the reservoir when the dewpoint pressure is reached, and as the pressure declines
further, the saturation of liquid increases because of
retrograde condensation. Because the saturation of liquid
is low, only the vapor phase flows to producing wells.
Thus, the overall composition of the fluid remaining in
the reservoir changes continuously. However, the phase
diagram shown in Fig. 23.14 is for the original composition only. The preferential removal of light hydrocarbon
components in the vapor phase generates new hydrocarbon mixtures which have a greater fraction of the heavier
hydrocarbons. Differential liberation experiments, in
which a sample of the reservoir fluid initially at high
pressure is expanded through a sequence of pressures,
can be used to investigate the magnitude of the effect of
pressure reduction on the vapor composition. At each
pressure, a portion of the vapor is removed and analyzed. Such an experiment simulates what happens when
condensate is left behind in the reservoir as the pressure
declines. As the reservoir fluid becomes heavier, the
boundary of the two-phase region in a diagram like Fig.
23.14 shifts to higher temperatures. Thus, the composition change also acts to drive the system toward higher
liquid condensation. Such reservoirs are candidates for
pressure maintenance by lean gas injection to limit the
retrograde loss of condensate or for gas cycling to
vaporize and recover some of the liquid hydrocarbons.
Bubblepoint reservoirs are those in which the
temperature is less than the critical temperature of the
reservoir fluid (Point D in Fig. 23.14). These reservoirs
are sometimes called undersaturated because there is
insufficient gas for a gas phase at that temperature and
pressure. Isothermal pressure reduction causes the appearance of a vapor phase at the bubblepoint pressure.
Because the compressibility of the liquid phase is much
lower than that of a vapor, the pressure in the reservoir
declines rapidly during production in the single-phase
region. The appearance of the much more compressible
vapor phase reduces the rate of pressure decline. The
volume of vapor present in the reservoir grows rapidly
with reduction of reservoir pressure below the bubblepoint. Because the vapor viscosity is much lower than
the liquid viscosity, and the gas relative permeability
goes up markedly with increasing gas saturation, the
vapor phase flows more easily. Hence, the produced
GOR climbs rapidly. Again, pressure maintenance by
water drive, water injection, or gas injection can
substantially improve oil recovery over the 10 to 20%
recovery typical of pressure depletion in these solutiongas-drive reservoirs. As in dewpoint reservoirs, the composition of the reservoir fluid changes continuously once
the two-phase region is reached.
There is, of course, no reason why initial reservoir
temperatures
and pressures cannot lie within the twophase region. Oil reservoirs with gas caps and gas reser-

23-7

r-----Fig. 23.15~Increase
in OAPI gravity with depth: (a) Ordovician
Ellenberger reservoirs in Delaware Val Verde
basin; (b) Pennsylvanian Tensleep reservoirs in
Wyoming.

voirs with some liquids present are common. There also

can be considerable variation in the initial composition
of the reservoir fluid. The discussion of single-phase,
dewpoint, and bubblepoint reservoirs was based on a
phase diagram for one fluid composition. Even for one
fluid, all the types of behavior occur over a range of
temperatures. In actual reservoir settings, the composition of the reservoir fluid correlates with depth and
temperature. Deeper reservoirs usually contain lighter
oils.j Fig. 23.15 shows the relationships between oil
gravity and depth for two basins.
The higher
temperatures of deeper reservoirs alter the original
hydrocarbon mixtures to produce lighter hydrocarbons
over geologic time. 6 Low oil gravity, low temperature,
and relatively small amounts of dissolved gas all combine to produce bubblepoint reservoirs. High oil gravity,
high temperatures, and high GORs produce dewpoint or
condensate systems.
Phase Diagrams for EOR Processes
Phase behavior plays an important role in a variety of
EOR processes. Such processes are designed to overcome, in one way or another, the capillary forces that act
to trap oil during waterflooding. In surfactant/polymer
processes, the effects of capillary forces are reduced by
injection of surfactant solutions that contain molecules
with oil- and water-soluble portions. Such molecules
migrate to the oil/water interface and reduce the interfacial tension, thereby reducing the magnitude of the
capillary forces that resist movement of trapped oil.
Miscible displacement
processes are designed to
eliminate interfaces between the oil and the displacing
phase, thereby removing the effects of capillary forces
between the injected fluid and the oil. Unfortunately,
fluids that are strictly miscible with oil are too expensive
for general use. Instead, fluids such as methane or
methane enriched with intermediate hydrocarbons,
CO*, or nitrogen are injected, and the required miscible
displacing fluid is generated by mixing of the injected
fluid with oil in the reservoir.

PETROLEUM

23-8

TYPE
b1a.b

II(

DEW

ENGINEERING

POINTS

HANDBOOK

O-0-b
SURfACTANl

b. TYPE

III

SURfACTANl

c. TYPE

II( + )

&
BllHE
Fig. 23.16-Ternary

75%
OIL

representation of phase diagrams

Phase diagrams typical of those used to explain the

behavior of surfactant systems are shown in Fig. 23.16.
In those ternary diagrams, the components shown are no
longer true thermodynamic components since they are
mixtures. A crude oil contains hundreds of components,
and the brine and surfactant pseudocomponents may also
be complex mixtures. The simplified representation,
however, has obvious advantages for describing phase
behavior, and it is reasonably accurate as long as each
pseudocomponent has approximately the same composition in each phase. In Fig. 23.16a for instance, the oil
pseudocomponent can appear in an oil-rich phase or in a
phase containing mostly surfactant and brine. If the oil
solubilized into the surfactantlbrine phase is nearly the
same mixture of hydrocarbons as the original oil,
then the representation in terms of pseudocomponents is
reasonable. The compositions shown in Fig. 23.16 are in
volume fractions. An inverse lever rule similar to Eqs. 3
or 5 gives the relationship between the volumes of the
two phases for a given overall composition, as illustrated
in Fig. 23.16.
Fig. 23.16a is a phase diagram for the liquid/liquid
equilibrium behavior typical of mixtures of brines of low
salinity with oil. If there is no surfactant present, the oil
and brine are immiscible; mixture compositions on the
base of the diagram split into essentially pure brine in
equilibrium with pure oil. Addition of surfactant
causes some oil to be solubilized into a microemulsion
rich in brine. That phase is in equilibrium with a phase
containing nearly pure oil. Thus in the low-salinity
brine, the surfactant partitions into the brine phase,

VOLUME

50%
PERCENT

MOLE

25%
LIQUID

PERCENT

5% I

PHASE

CO2

Fig. 23.17-Typical
pressure-composition phase diagram for a
binary mixture of CO, with a crude oil at
temperatures above 120F [49%].

solubilizing some oil. The plait point in Fig. 23.16a lies

close to the oil comer of the diagram. Because only two
phases occur and the tie lines all have negative slope,
such phase is often called Type II( -).
Phase diagrams for high-salinity brines are often
similar to Fig. 23.16~. In the high-salinity systems the
surfactant partitions into the oil phase and solubilizes
water into an oil-external microemulsion. In this case the
plait point is close to the brine apex on the ternary
diagram. For intermediate salinities, the phase behavior
can be more complex, as shown in Fig. 23.16b. According to the phase rule, if the temperature and pressure are
set, then up to three phases can coexist for a three component system. If three phases do occur, then the compositions of the phases are fixed at a given temperature
and pressure. The three-phase region on a ternary
diagram is represented as a triangle (Fig. 23.16b). Any
overall composition lying within the three-phase region
splits into the same three phases. Only the amounts of
each phase change as the overall composition varies in
the three-phase region. The edges of the three-phase
region are tie lines for the associated two-phase regions.
Thus, there is a two-phase region adjacent to each of the
sides of the three-phase triangle. In Fig. 23.16b, the
two-phase region at low surfac.tant concentrations is too
small to show on the diagram. It must be present,
however, since oil and brine form only two phases in the
absence of surfactant.

PHASE DIAGRAMS

23-9

Fig. 23.18-Pressure
composition diagram-Gas
1 system for
Rangely oil: 95% CO, and 5% methane gas
system at 160aF 171Cl.

Phase behavior of COzlcrude oil systems is often

summarized in pressure-composition
(p-x)
diagrams
such as those shown in Fig. 23.17. Fig. 23.18 is an example of a p-x diagram for mixtures of CO1 (containing a small amount of methane contamination) with
crude oil from the Rangely field. 8 In such diagrams, the
behavior of binary mixtures of COZ with a particular oil
is reported for a fixed temperature. Thus, the oil is
represented as a single pseudocomponent on such a
diagram. Such diagrams indicate bubble- and dewpoint
pressures, the regions of pressure and composition for
which two or more phases exist, and information about
the volume fractions of the phases. However, they provide no information about the compositions of the phases
in equilibrium. The reason for the absence of composition data is illustrated in Fig. 23. 19,3 which gives data
reported by Metcalfe and Yarborough9 for a ternary
system of CO*, Cd, and C 10. Binary phase data for the
CO*-Cd (Ref. 10) and COz-C tc (Ref. 11) systems also
are included. Fig. 23.19 shows a triangular solid within
which all possible compositions (mole fractions) of
COz-Cd-C to mixtures for pressures between 400 and
2,000 psia are contained. The two-phase region is
bounded by a surface that connects the binary phase
envelope for the COz-C ra binary pair to that on the
CO+4
side ofthe diagram. That surface is divided into
two parts-liquid compositions and vapor compositions.
Tie lines (heavy dashed lines in Fig. 23.19) connect the
compositions of liquid and vapor phases in equilibrium
at a fixed pressure. Thus, the ternary phase diagram for
CO2-C4-C tc mixtures at any pressure is just a constant

Fig. 23.19-Phase
behavior of CO,-C,-C,,
[71 Cl.

mixtures at 16OOF

pressure (horizontal) slice through the triangular prism.

Several such slices at different pressures are shown in
Fig. 23.19. At pressures below the critical pressure of
CO 2-C 4 mixtures ( 1,184 psia) , both CO 2-C , c mixtures
and CO2-C4 mixtures form two phases for some range
of COz concentrations. At 400 and 800 psia, the twophase region is a band across the diagram. Above the
critical pressure of COz-Cd mixtures, CO2 is miscible
with Cd. and ternary slices at higher pressures show a
continuous binodal curve on which the locus of liquid
compositions meets that of vapor compositions at a plait
point. The locus of plait points (labeled P in Fig.
23.19) connects the critical points of the two binary
pairs.
To see the effect of representing the phase behavior of
a ternary system on a pseudobinary diagram, consider a
p-x diagram for an oil composed of 70 mol% C ,c and
30 mol% CJ. At any fixed pressure, the mixtures of
CO2 and oil which would be investigated in an experiment to determine ap-x diagram lie on a straight line (the
dilution line), which connects the original oil composition with the CO2 apex. Thus, a P-X diagram for this

PETROLEUM ENGINEERING

23-10

LIQUID

HANDBOOK

LIQUID

J
I

-,I
/
/
/

Fig. 23.20-p-x
diagrams for mixtures of CO, with Wasson oil, where L, is Liquid Phase 1 (oil-rich
phase), L, is Liquid Phase 2 (COP-rich phase), and V is the vapor phase. Dashed lines
indicate constant volume fraction of L, phase.

system is a vertical slice through the triangular prism

shown in Fig. 23.19. The saturation pressures on a p-x
diagram are those at which the dilution plane intersects
the surface which bounds the two-phase region. Bubblepoint pressures (B) occur where the dilution plane intersects the liquid composition side of the two-phase surface, while dewpoint pressures (D) occur at the intersection with vapor compositions. Comparison of the phase
envelope on the resulting p-x diagram with binary phase
diagrams yields the following observations.
1. Tie lines do not, in general, lie in the dilution plane.
Instead, they pierce that plane. This means that the composition of vapor in equilibrium with a bubblepoint mixture on the p-x diagram is not the same as that of the
dewpoint mixture at the same pressure.
2. The critical point on the p-x diagram occurs where
the locus of plait points pierces the dilution plane. It is
not, in general, at the maximum saturation pressure on
the p-x diagram. The maximum pressure occurs where
the binodal curve is tangent to the dilution plane. The
critical point on the p-x diagram can lie on either side of
the maximum pressure, depending on the position of
locus of plait points on the two-phase surface.
It is apparent from Fig. 23.19 that the composition of
the original oil has a strong influence on the shape of the
saturation pressure curve, and on the location of the
critical point on the p-x diagram. If the oil had been
richer in C4, the critical pressure and maximum pressure
both would have been lower. Thus, it should be anticipated that the appearance of p-x diagrams for
C02icrude oil systems should depend on the composition of the oil.
Figs. 23.18 and 23.20 illustrate the complexity of

phase behavior observed for COz/crude oil systems.

Fig. 23.18 gives the behavior of mixtures of CO2 (with
about 5 % methane as a contaminant) with Rangely crude
oil at 16OF. The oil itself has a bubblepoint pressure of
about 350 psia. Mixtures containing up to about 80
mol% CO;? (+C 1) show bubblepoints, while those containing more CO2 show dewpoints. At the relatively
high temperature of the Rangely field, only two phases,
a liquid and a vapor, form. At lower temperatures, more
complex phase behavior can occur. Figs. 23.20a, b and c
show the behavior of mixtures of a dead oil from the
Wasson field3 with CO2. At 90F and 105F, the mixtures form a liquid and a vapor at low pressures and two
liquid phases at high pressures and high CO2 concentmtions. They form three phases, two liquids and a vapor,
for a small range of pressures at high CO* concentrations. The liquid/liquid and liquid/liquid/vapor behavior
disappears if the temperature is high enough. At 120F
(Fig. 23.2Oc), the three-phase region had disappeared.
For the systems studied to date, 120F appears to be a
reasonable estimate of the maximum temperature for liquid/liquid/vapor separations. For detailed discussions of
such phase behavior, see Refs. 2 and 3.

Calculation of Phase Compositions

Calculations of the compositions of phases that occur for
multicomponent mixtures are important for the design of
surface separators and for the design of EOR processes
such as high-pressure and condensing-gas drives and
CO1 floods. There are two widely used methods for
such calculations-K-value
correlations and equations of
state (EOSs).

23-l 1

PHASE DIAGRAMS

The use of K-values, also called equilibrium ratios

or equilibrium constants, is based on the behavior of
mixtures of gases at relatively low pressures and
temperatures. According to Raoults law, the partial
vapor pressure phi of component i in a liquid mixture is
equal to the product of the mole fraction of component i
in the liquid and its pure component vapor pressure
p~i=Xjpvj.

...

. . f..

.........

. . (6)

In addition, Daltons law states that the partial

pressure of component i in the vapor is
p;j =yjpr,

.... .........

. . . . . . . . . *. . . . (7)

where yi is the mole fraction of component i in the vapor

andp, is the total pressure. Rearrangement of Eqs. 6 and
7 gives the definition of K-value for an ideal (low
pressure) system:

PRESSURE,PSIA
Fig. 23.21-Typical
equilibrium ratios at 22CPF [104%]
(dashed lines are the ideal ratios).

K.-Y;
I

-pvi
xi

. . . . . . . . . . . . . . . . . . . . . . . . . . . . (8)

Pr

Thus, for a multicomponent mixture at low pressure,

the equilibrium value can be estimated from the vapor
pressure, which is a function of temperature only, and
the total pressure. The assumption of an ideal gas in
Raoults and Daltons laws is reasonable only if the
pressure is below about 50 to 100 psia. * At higher
pressures, equilibrium ratios are functions of pressure,
temperature,
and composition. Fig. 23.21 shows a
typical set of equilibrium ratios for a hydrocarbon system
containing some CO2 at 220F. I3 Also shown (as
dashed lines) are the ideal equilibrium ratios. At high
pressures, the K-values for ethane and heavier hydrocarbons pass through a minimum and appear to converge to
a value of one, in this case at 4,200 psia. This observation is the basis for a widely used empirical correlation
for K-values. K-value charts for a variety of convergence
pressures and a recommended technique for estimating
the convergence pressure are given in GPSAs Engineering Data Book.
If K-values ate known or can be estimated, then
amounts of liquid and vapor and phase compositions can
be calculated easily. Consider 1 mol of a mixture in
which the overall mole fraction of the ith component is
zi . If the mole fractions of component i in the liquid and
vapor are Xi and yi , and the fraction of the mole of mixture that is liquid is L, then a material balance gives
Zi=Xil+y~(l-L).

......

. .

. . . . . . . . . (9)

Substitution of the definition of Ki=yilXi

and rearrangement gives
Zi

xj = Ki +(l-Ki)L.

into Eq. 9

. . . . . . . . . . . . . . . . . . . . . (10)

Similarly, Eq. 9 can be solved for yi, giving

KiZi
Yi= Kj +(l-Ki)L.

.. ..,...... . ....

. -(II)

By definition, cXi=Eyi=l,
SO cXi-Cyi=O
gives the nonlinear function f(L):

f(L)=

Ky;;;;)L
1

=o.

.. .... .. .

which

. (12)

Eq. 12 can be solved for L by application of a NewtonRaphson iteration. If Lk is the kth estimate of the solution, an improved estimate is given by
Lk+l=Lk-

pi
z

) .....,,,...,........(13)
Lk

where

The iterative calculation is complete when AL) as

given by Eq. 12 and AL=Lk+l -Lk are both smaller
than some preset tolerances. Once the liquid mole fraction has been determined, the Xi and yi are obtained
from Eqs. 10 and 11.
If the mixture is at its bubblepoint pressure, then L= 1
and Czi=l, and Eq. 12 reduces to
C(ziKi)=l.

...........,..........

. . . . . ..(15)

Thus, if Kis are known as a function of pressure, then

the bubblepoint pressure can be obtained as the pressure
at which Eq. 15 is satisfied. Bubblepoint pressures are
generally most sensitive to the K-values of the lightest
components, which axe the largest. If the mixture is at its
dewpoint pressure, then L=O, CZi = 1, and
c

=l.

. . . . . . . . . . . . . . . . . . . . . . . . (16)

PETROLEUM ENGINEERING

23-12

HANDBOOK

volume is small enough to be close to the constant h,

then the pressure increases rapidly as the volume is
reduced. Thus, the EOS is qualitatively consistent with
liquid behavior when the pressure is high.
The calculation of phase compositions is based on the
fact that, at thermodynamic equilibrium, the fugacity of
each component must be the same in each phase. The
fugacity of a component in a phase can be calculated if
the volumetric behavior of the phase is known. It can be
shown I4 that the fugacity of component i, fi , in a phase
is given by

RTlnfi=Sm[

(2)

-RTln
Fig. X3.22-Comparison
of calculated and measured phase
compositions
for ternary mixtures of CO,.
methane (C,), and decane (C,,), at 160F [71C]
and 1,250 psia.

Dewpoint pressures are most sensitive to the smallest Kvalues, those of the heavy components, which often are
least accurately known. Thus, there is often more uncertainty in calculated values of dewpoint pressure. The
sums of Eqs. 15 and 16 also are useful for determining
whether the mixture forms one or two phases. If
C(K;z;) < 1, the mixture is all liquid. If C(ziIKi) < 1, the
mixture is all vapor. If both C(K,zi)> 1 and
C(K;Iz,) > 1, the mixture forms two phases.
In recent years, EOSs also have been used extensively
for phase equilibrium calculations. Most of the widely
used EOSs are refinements of the equation proposed by
van der Waals:
RT
p= ---b

a
v2,

,,........................

TV
-$]dV,
3 l,
t

Vt

vt

niRT

.... ...

.. .. .

where T is the temperature, p the pressure, V, the total

volume, ni the number of moles of component i, and R
the gas constant. If the relationship between pressure,
composition, and total volume is known from an EOS,
then taPlaniJT,V ,n can be obtained and the integral
evaluated. A var!e<y of EOSs have been suggested for
hydrocarbon
mixtures. For example, the original
Redlich-Kwong equation has the form
2
ntam

n,RT

P=

V,-0,

T v (v +nb )
t t
,,,

(20)

. . . . .

where n, =Cni is the total number of moles and a,,, and

depend on the mixture composition and the critical
properties of the components as follows.

b,

am=

(EyiA; 1/2)2R2T52
p
)

......... ....

. . (21)

(17)
where

where p is the pressure, R the gas constant, T the

temperature, and V the molar volume. The constants a
and b can be determined for a particular component from
thermodynamic constraints at the critical point, which
requires that
(ap/w)~,

=(ap%v*)T,

=o,

which gives
a=-

A, = Qa(PIpci)
, (T,T,i)5,2

a,=

EO.4275.

..................

9(2 -1)
b

= @Y;BiPT

, . . . . . . . . . . . . . . . . . . . . . . . (24)

PC

. . . (22)

and

21 R2Tc2
64

.. ............

where

and
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (18)

b=F,

B, = nb(P/Pci)
(T,T,i)

. . . . . . .

. . . . .

. .

(25)

(26)

where T, is the critical temperature and pc is the critical

pressure.
van der Waals equation reduces to the ideal gas law if
the molar volume is large (low pressure). If the molar

and
2* -1
fib=3

~0.08664.

...

....

23-13

PHASE DIAGRAMS

In Eqs. 21 through 26, y, is the mole fraction of component i in the mixture, and pci and T,; are the critical
pressure and temperature of component i. The constants
Q, and fib arise from the thermodynamic constraints,
=0, at the critical point. From
cwa v) Tr =(a2piavl)T,
Eqs. 19 through 26, an expression for the fugacity of
each component in a phase can be obtained. To calculate
phase compositions, the following procedure is used.
1. Estimate compositions of liquid and vapor.
2. Calculate fugacities of each component in each
phase.
3. Iff,,, =fiL stop. Otherwise, obtain improved phase
compositions and return to Step 2.
Similar calculations can be performed for liquid/liquid
and even liquid/liquid/vapor systems. Because the equations for fugacities are complex and nonlinear, computer
implementation of this iterative scheme to find phase
compositions is required.
The Redlich-Kwong EOS given as an example here is
by no means the only equation available. Many
modifications to the Redlich-Kwong equation have been
proposed to improve the accuracy of the predictions of
and equations with different
phase compositions,
analytical forms are also in use. The Soave modification
of the Redlich-Kwong equation and the Peng-Robinson
equation are among the most widely used. Ref. 14 gives
details of a variety of EOSs, and Ref. 15 is a useful collection of papers relevant to phase equilibrium calculations for hydrocarbon systems. Computer programs for
such calculations are available. *
EOSs currently in use are quite accurate for mixtures
of light hydrocarbons for which critical properties are
known and extensive phase behavior data are available.
For instance, Fig. 23.22 shows a comparison of phase
compositions calculated with the Peng-Robinson EOS
with measured values for mixtures of CO*, C 1, and C 10
at 1,250 psia and 160F. For this well-characterized
system, the calculated values agreed well with the
measured compositions. For crude oil systems, phase
behavior predictions are less reliable because the
chamcterization of heavy components is less certain. For
such systems some experimental data are required to
tune the EOS to represent the particular hydrocarbon
system. Improvement of the predictive power of EOSs
for complex hydrocarbon systems is an area of active
current research.

Nomenclature
a, = defined by Eq. 21
Ai = defined by Eq. 22
6, = defined by Eq. 24
Bi = defined by Eq. 25
C = critical point when liquid and vapor phases
are identical
fir. = liquid fugacity of Component i
fiV = vapor fugacity of Component i
Ki = K-value of Component i
L = total moles of liquid-phase in mixture
Lk = kth estimate of L by Newton-Raphson
iteration
no = number of constraints
Gas Processors Suppliers Assn

Tulsa, OK

p =
PJ,, =
pd =
pt =
PV =
pVi =

p:i =
PVZ =
pyl

pv2

T,. =
T, =
T2 =
VL =
V, =
Zi =
Q, =
Qb =

pressure
bubblepoint pressure
dewpoint pressure
total pressure
vapor pressure
vapor pressure of Component i in liquid
mixture
partial vapor pressure of Component i in liquid mixture
any mixture of two components which form
a single vapor phase
pressure below vapor pressure of Component z which may form a single vapor
phase
pressure above vapor pressure of Component z which may form a single vapor
phase
critical temperature
constant temperature below T,
constant temperature above T,.
saturated liquid volume
saturated vapor volume
overall mole fraction of the ith component
defined in Eq. 23
defined in Eq. 26

Subscripts
C = number of components
F = number of degrees of freedom
P = number of phases

References
1. Engineering Data Book, Gas Processors Suppliers Assn., ninth
edition, Tulsa (1972).
2. Stalkup, F.I. Jr.: Miscible Displacement, Monograph Series,
SPE, Dallas (1983) 8.
3. Orr, F.M. Jr. and Jensen, C.M.: Interpretation
of PressureComposition Phase Diagrams for CO*-Cmde Oil Systems, Sot.
Pet. Eng. J. (Oct. 1984) 485-97.
4. Reamer, H.H., Fiskin, J.M., and Sage, B.H.: Phase Equilibria
in Hydrocarbon Systems, Ind. Eng. Chem. 41 (Dec. 1949) 2871.
5. Sage, B.H. and Lacey, W.N.: Thermodynamic Properties of the
Lighter Parafin Hydrocarbons and Nitrogen, Monograph on API

6.
7.
8.
9.

10.
11.

12.
13.

Research Project 37, American Petmleum Inst., New York City

(1950).
Hunt, J.M.: Petroleum Geochemistry and Geology, W.H.
Freeman and Co., San Francisco (1979).
Nelson, R.C. and Pope, GA.: Phase Relationships in Chemical
Flooding, Sot. Pet. Enr. 1. (Oct. 1978) 325-38.
Graue, D.J. and Zana, E.T.: Study of a Possible CO, Flood in
the Rangely Field, Colorado, J. Per. Tech. (July 1981) 1312-18.
Metcalfe, R.S. and Yarbomugh, L.: The Effect of Phase
Equilibria on the CO* Displacement Mechanism, Sot. Pet. Eng.
J. (Aug. 1979) 242-52; Trans., AIME, 267.
Olds, R.H. el al.: Phase Equilibria in Hydmcarbon Systems,
Ind. Eng. Chem. 41 (March 1949) 475-82.
Reamer, H.H. and Sage, B.H.: Phase Equilibria in Hydrocarbon
Systems. Volumetric and Phase Behavior of the n-Decane-CO2
System, J. Chem. Eng. Data 8, No. 4 (1963) 508-13.
Standing, M.B.: Volumetric and Phase Behavior of Oil Field
.
Hydrocarbon Sysrems, SPE, Dallas (1977).
Allen, F.H. and Roe, R.P.: Performance Characteristics of a
Volumetric Condensate Reservoir, Trans., AIME (1950) 189,
83-90.

14. Reid, R.C., Prausnitz, J.M., and Sherwood, T.K.: The Properties
of Gases and Liquids, third edition, McGraw-Hill Book Co. Inc.,
New York City (1977).
15. Phase Behavior. Reprint Series, SPE, Dallas (1981) 15.