2-1

Petroleum Fluid Properties

CHAPTER 2.
HYDROCARBON PHASE BEHAVIOUR
2-1

BASICS OF PHASE BEHAVIOUR

Petroleum systems are known to exhibit multi-phase behaviour over extremely wide
ranges of pressures and temperatures. In fact hydrocarbon mixtures have been observed
with two or more phases in equilibrium at temperatures as low as -250 oF and higher than
1,000 oF. The molecular compositions of the gas and liquid phases in a reservoir rock are
different, and hence the physical properties of the phases differ. This difference in phase
properties, in conjunction with the reservoir (rock) relative permeability characteristics,
results in the complex behaviour of hydrocarbon reservoirs.
The phase behaviour of hydrocarbon systems takes on a further degree of complexity when
the variables of pressure and temperature are introduced. To circumvent some of the
complexity, a stepwise discussion of phase behaviour of hydrocarbons will be developed
through the following topics:
-

2-1-1

Basic Thermodynamics
Phase Behaviour of a Pure Component System
Binary (two-component) systems
Generalised multi-component systems
THERMODYNAMIC TERMINOLOGY

Before considering the effect of temperature and pressure on hydrocarbon systems, we will
define some terms:
SYSTEM:

amount of substances
specified conditions.

COMPONENTS:

The pure substances that make up the system. For this

purpose they will be considered as molecular species of fixed
elemental composition and molecular weight.

PHASES:

Physically and chemically homogeneous sub-systems

separated by definite boundaries, but which allow mass
transfer to other phases.

EQUILIBRIUM:

An isolated system is in thermodynamic equilibrium if the

properties of the system do not alter as long as the external
environment remains unchanged.

INTENSIVE
PROPERTIES:

within

given

boundaries

under

Physical properties are termed either intensive or

extensive. Intensive properties are independent of the
quantity of material present. i.e. Density, specific volume,
viscosity
and
compressibility
factor,
pressure
and
temperature

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Petroleum Fluid Properties

EXTENSIVE
PROPERTIES:

Properties such as volume and mass are termed

extensive; their values are determined by the total quantity of
matter present.

PHASE BEHAVIOUR OF PURE COMPONENT SYSTEMS

2-1-2

To begin, it is useful to review the behaviour of a pure component under varying pressures
and temperatures to gain an insight into the behaviour of more complex hydrocarbon
systems. Figure 1 shows the pressure-temperature phase boundaries for a singlecomponent system (CO2). The boundaries and their intersections are annotated as follows:

80
C

P/bar

60
(s+l)
40

l
(l+g)

20
0

(s+g)
100

200

300

400

T/K
Figure 1: Phase Diagram for Carbon Dioxide

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Petroleum Fluid Properties

Vapour Pressure Line (l+g)

For a pure substance, the vapour pressure line divides regions where the substance is a
liquid (l) from regions where the substance is a gas (g). Pressure and temperatures above
the line indicate conditions for which the substance is a liquid; points below the line
represent conditions under which it is a gas. Two other terms in common use in relation
to the vapour pressure of a system are the bubble point and the dew point. The bubble
point for a liquid is the first appearance (bubble) of a gas phase on reaching the two-phase
equilibrium line, while for a gas the dewpoint is the first appearance of liquid (dew) at the
two-phase line. For a pure component the bubble point and dew point are co-incident on
the vapour pressure curve; for a mixture there is an important distinction which will be
discussed in detail below.
Critical point (C)
The upper (p,T) limit of the vapour pressure curve is the critical point (C). The temperature
and pressure represented by this point are called the critical temperature, (Tc) and the
critical pressure, (Pc). For a pure substance Tc is the temperature above which a vapour
cannot be 'liquefied' regardless of the applied pressure and above Pc a liquid cannot be
'vaporised' regardless of the temperature. For a pure substance above its critical point (in
either T or p), no distinction can be made between liquid and vapour phases; it is simply
referred to as a 'fluid'. Consider the path shown around the critical point in Figure 2 for a
pure substance confined over mercury in a visual PVT cell. The schematic diagrams
illustrate the behaviour that would be observed, although the phase volumes are not to
scale. It is possible to move from A to D via either: i) the sample undergoing a phase
change (A-E-D) or ii) the sample remaining monophasic (A-B-C-D).

A
liquid

gas

Mercury

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Petroleum Fluid Properties

Figure 2: Phase Behaviour of Carbon Dioxide around the Critical Point

Triple point (T)
This point represents the (only) pressure and temperature at which solid, liquid and
vapour coexist for a pure substance under equilibrium conditions.
Sublimation Curve (s+g)
The sublimation curve is simply the vapour pressure curve for the solid. It is not a smooth
continuation of the gas-liquid vapour pressure curve; there is a discontinuity in curvature
at the triple point. The line divides the area between solid (s) and vapour (g) and continues
down to (T=0, p=0) on absolute scales.
Melting point Line (s+l)
This line divides solid from liquid. For pure hydrocarbons (as for most substances), the
melting point generally increases with pressure so the slope of the line is positive. Water
(and a few other substances) is exceptional in that its melting point initially decreases with
pressure; ie: the melting point line has negative slope from the triple point. At very high
pressures, the melting curve for water reverts to a positive slope (dp/dT>0). Unlike the
vapour pressure curve, the melting line has no known upper limit analogous to the critical
point for liquid and gas.

2-1-3

USE OF PHASE DIAGRAMS

Consider the behaviour of a PVT cell charged with a pure substance and the volume varied
by a piston at constant temperature as shown in Figure 3. Following the path 1-2-3-4, the
gas initially undergoes compression and the pressure rises. When the vapour pressure is
reached (at fixed temperature T) condensation of liquid commences (dewpoint). As the
piston is moved in further, the pressure remains constant and the volume of the gas phase
decreases, while the liquid phase volume increases. When the last bubble of gas
disappears (3) (bubble point), the pressure commences to rise again rapidly, as the liquid
is compressed (4).

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Petroleum Fluid Properties

Liquid

Gas

LIQUID
COMPRESSION

2-PHASE REGION

GAS
COMPRESSION
1
V

Figure 3: p,V Behaviour of a Pure Substance

2-1-4

BINARY SYSTEMS

As described above, pure substances are unique in one sense in that their bubble and dew
points are coincident on the vapour pressure curve. For binary (and all multi-component
systems) vapour liquid equilibrium occurs within a phase envelope. The distinction is
shown schematically in Figure 4. Note that the critical point is no longer necessarily at
the maximum temperature and/or pressure at which gas and liquid coexist. In terms of a
p,V diagram for a mixture (Figure 5), the distinction between bubble and dew point at a
particular temperature is clearly apparent. As a result, mixtures exhibit a number of
additional phase behaviour phenomena not obtainable with pure substances. By way of
example a binary system will be considered in more detail.

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Petroleum Fluid Properties

PURE SUBSTANCE

MIXTURE

P
L

(L + G)
G

G
T

Critical Point

Figure 4: Transition of Vapour Pressure Curve for Pure Component to Phase Envelope
for Multi-component Systems
Ethane/n-Heptane Mixture
Figure 6 is the pressure-temperature diagram for a mixture of ethane and n-heptane. At
all pressures and temperatures outside of the phase diagram, the mixture is in single
phase. At all pressures and temperatures within the phase diagram, the mixture exists in
two phases. Line A-C is the bubble-point locus and B-C is the dewpoint locus. As before,
C is the critical point where the properties of the liquid and gas phases become identical.
Two additional terms in common use to describe the pressure and temperature extremes
of the phase envelope are the cricondenbar and cricondentherm (occasionally referred to
as the maxcondenbar and maxcondentherm respectively).

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Petroleum Fluid Properties

Liquid

Gas
4
LIQUID
COMPRESSION

3
2

GAS
COMPRESSION

2-PHASE REGION

1
V

Figure 5: Volumetric (p,V) Behaviour for a Multicomponent System

1200
96.8 mol% ETHANE + 3.17 mol% HEPTANE

1000

a
b

A
de
B

-100

oi

200

Single Phase
Region
(gas)

cu

400

Two Phase
Region

lo

600

Single Phase
Region
(liquid)

nt

800

bu
bb
lep
oin
tl
oc
us

Pressure/psia

wp

100

200

T/ F

300

Figure 6: Phase Envelope for the binary system ( 0.968 Ethane

+ 0.032 Heptane)
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Petroleum Fluid Properties

Cricondenbar (a---a)
The cricondenbar is defined as the maximum pressure at which gas and liquid can exist in
equilibrium.
Cricondentherm (b---b)
The cricondentherm is defined as the maximum temperature at which gas and liquid can
exist in equilibrium.
Note that for this system the dewpoint curve has two solutions (one high pressure, one low
pressure) for a range of temperatures between the critical point and the cricondentherm.
This is a direct consequence of the critical point no longer being at the extremes of the
phase envelope and that ethane/heptane system exhibits the phenomenon of retrograde
condensation. Retrograde condensation is commonly observed in many petroleum
systems and is illustrated more clearly in Figure 7.

P
(A)

(B)
(C)
(D)
(E)

(B)

(C)

(D)

(E)

Figure 7: Schematic Representation of Retrograde Condensation

The path A-B-C-D-E is at constant temperature and crosses the dew curve twice. The
observed behaviour is shown schematically at the bottom of the Figure. As the pressure is
decreased (volume increased) liquid is observed to condense from the single phase fluid.
The volume of liquid builds up to a maximum and as the system is expanded further, the
liquid re-evaporates until the lower dewpoint is reached. A similar phenomenon can be
observed by varying the temperature and moving across the top of the phase envelope at a
constant pressure between the critical pressure and the cricondenbar. Again, the dew
curve is crossed twice and liquid is observed to 'condense' and 'evaporate'.

2-1-5

GENERALISED MULTI-COMPONENT SYSTEMS

Figure 8 is a typical pressure-temperature diagram of multi-component hydrocarbon

systems. The lines within the diagram boundary are called iso-volume or quality lines.
They describe the pressure and temperature conditions for equal volume percentages of
the liquid phase. Note that the quality lines converge at the critical point.
As reservoir fluid is produced, reservoir pressure drops while reservoir temperature
remains constant. The reservoir fluid often enters the two-phase region. The location at
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Petroleum Fluid Properties

'Gas'

Lean Gas
Condensate

Gas C ondensate

Critical Fluid

Volatile Oil

Bl ack Oil

Pressure

which the constant temperature line enters the two phase region depends somewhat on
the reservoir temperature and heavily on the composition of the reservoir fluid.

%
90

Wet Gas
Dry Gas

10
%

20
%

30
%

40
%

50
%

60
%

70
%

%
80

Temperature
Phase Envelope (Bubble & Dew Point Curves)
'Quality' Lines (Constant Phase Volume Fraction)
P,T Path of Producing Fluid
Figure 8: Generalised Phase Diagram for Reservoir Fluids

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Petroleum Fluid Properties

2-2

COMPARISON OF MULTI-COMPONENT HYDROCARBON SYSTEMS

Figure 8 illustrates various hydrocarbon systems and the general position at which they
enter a phase envelope. The compositions of fluids, which enter their phase envelope
towards the left boundary, contain more heavy hydrocarbons than those that enter their
phase envelope towards the right boundary. The fluids that enter to the left of the critical
temperature exist as liquids in the reservoir. Those, which enter to the right of the critical
temperature, exist as gases in the reservoir.
It follows that any suitable hydrocarbon mixture of fixed composition can exhibit all types
of phase behaviour highlighted in the figure, depending upon the temperature. But in
petroleum reservoirs temperature, pressure and fluid composition are not uncorrelated
parameters.
Figure 9 illustrates the interrelation of composition, pressure and
temperature for the various types of fluid. Black and heavy oils contain very involatile
material and their phase envelopes only extend to completion in principle.
At
temperatures above 300 oC, thermal cracking of components prevents any experimental
determination of the phase envelope.

Thermal Decomposition
Dry Gases

Gas Condensates
Black Oils

Heavy Oils

>350 C
Figure 9: Evolution of Reservoir Fluid Phase Diagrams with Composition

2-2-1

BLACK OILS

Figure 10 is the pressure-temperature diagram of a hypothetical black oil mixture.

Assume the reservoir temperature is as shown. If the liquid volumes were measured as
the pressure was lowered, the resultant liquid shrinkage curve is also illustrated in the
Figure. Note that the quality lines of Figure 10 are essentially equally spaced at reservoir
temperature. This results in a liquid volume curve that approximates a straight line
except at very low pressures. This behaviour characterises what is commonly called an
"ordinary black oil".
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Petroleum Fluid Properties

PHASE ENVELOPE
RES. OIL VOLUME
100

Liquid Volume (%)

Pressure

(T res , Pres)

%
90

60
40
20
0

Pressure

10
%

20
%

30
%

60
%
50
%
40
%

70
%

%
80

80

Temperature

Figure 10: Phase Envelope and Reservoir Oil Volume for a typical 'Black' Oil
Note that the phase envelope is a pressure-temperature diagram of the reservoir fluid
under constant composition conditions. However, the fluid in the reservoir that originally
exists as a single-phase liquid and subsequently exists as two phases, does not produce
under constant composition conditions. Below the bubble point pressure, both the fluid
produced and that remaining in the reservoir have variable compositions but constant
reservoir volumes. The liquid volume curve represents the shrinkage of the liquid phase
occurring in the reservoir under normal pressure depletion conditions.
Typical Black Oil Characteristics
API Gravity
<40
Gas/Oil Ratio
<2,000 scf/bbl (356 m3/m3)
Formation Volume Factor
<2.0 res bbl/STB bbl
Table 1

2-2-2

VOLATILE OILS

Figure 11 illustrates the phase diagram of a reservoir fluid with the reservoir temperature
somewhat nearer the critical temperature, but still below it. Note that the quality lines are
close together near the bubble-point and more widely spaced at lower pressures. This
type of hydrocarbon system is referred to as a volatile oil. These oils are characterised by
rapid shrinkage below the bubble-point. Depending upon the position of the reservoir
temperature relative to the critical temperature, the liquid shrinkage curve may vary from
the near straight line characteristic of a black oil to the highly curved characteristic of a
near critical volatile oil. There is no sharp demarcation between a black oil and a volatile
oil.
Typical Volatile Oil Characteristics
API Gravity
>40
Gas/Oil Ratio
2,000-3000 scf/bbl (356-534 m3/m3)
Formation Volume Factor
>2.0 res bbl/STB bbl
Table 2

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Petroleum Fluid Properties

PHASE ENVELOPE
RES. OIL VOLUME

(Tres, Pres )
Liquid Volume (%)

%
90
%
80
70
%

Pressure

100

80
60
40
20

Pressure

10%

20
%

30
%

40
%

50
%

60
%

Temperature

Figure 11: Phase Envelope and Reservoir Oil Volume for a typical Volatile Oil

2-2-3

GAS CONDENSATES

Figure 12 illustrates a reservoir fluid where the reservoir temperature is located at the
right of the critical point, but still to the left of the cricondentherm. Pressure depletion at
reservoir temperature indicates the retrograde dewpoint is encountered. At a lower
pressure level, the depletion path encounters the phase boundary at the normal dewpoint
where essentially 100 percent gas exists.
However, this phenomenon cannot happen in the reservoir. Figure 12 is a pressuretemperature diagram of the reservoir fluid under constant composition conditions.
However, the fluid in the reservoir which originally exists as a single-phase gas and which
subsequently exists as two phases, does not produce under constant composition
conditions. Below the dewpoint pressure level, both the fluid produced and that
remaining in the reservoir have variable compositions but constant reservoir volume.
Since the gas saturation is high, the relative permeability to the gas phase is virtually
infinite when compared to that of the liquid phase, thus causing the liquid phase to
remain inside the reservoir.
The associated liquid volume curve at the bottom of the figure is a retrograde liquid curve
typical of a gas condensate system. Again it does not reflect directly the quality lines of
the phase envelope because of the depletion process described. Gas condensate fluids
exist which condense trace amounts of less than 0.1 percent (wet gases) up to 55 percent
retrograde liquids during pressure depletion of the reservoir.

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Petroleum Fluid Properties

PHASE ENVELOPE
CONDENSATE VOLUME

(Tres, pr es)
Liquid Volume (%)

20

%
90
%
80

16

Rich

12
8
4
0

Lean

Pressure

10
%

20
%

50
%
40
%
30
%

60
%

70
%

Pressure

Temperature

Figure 12: Phase Envelope and Condensate Volume for a Gas Condensate

2-2-4

NEAR CRITICAL SYSTEMS

Figure 13 illustrates the similarity of near critical systems, whether the system is that of a
volatile oil or of a gas condensate. The compositions of these two systems are similar and
the saturation pressures are similar; however, the original reservoir phases are different
(one is termed an 'oil' and one is treated as a 'gas') at pressures above their saturation
level. At pressure levels within the two-phase region and very close to the saturation
levels, the two curves converge rapidly.
At small pressure increments below the
saturation pressure of each system, the percentages of liquid and gas phases are
essentially equal and follow similar liquid shrinkage.
The surface gas/liquid ratios of these two different reservoir systems are very similar,
making it virtually impossible to infer whether the reservoir is oil or gas. In both cases,
the gas phase saturation within the reservoir will be high and the gas phase will be the
principal fluid produced.

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Petroleum Fluid Properties

100
NEAR CRITICAL SYSTEMS
Volatile Oil
Gas Condensate

Liquid Volume (%)

80

60

40

20

4
2
Pressure (kpsi)

Figure 13: Liquid Volume Curves for Near Critical Systems

Because the primary fluid produced from either system is the gas phase, the phase is
examined thoroughly when laboratory reservoir fluid studies are made. A laboratory
"constant volume depletion" study is routinely performed on these types of systems to
examine the produced gas in detail. This depletion is discussed further in the "Reservoir
Fluid Study - Gas Condensate" section of this manual.

2-3

TYPICAL SOLUTION GAS/LIQUID RATIO FOR VARIOUS HYDROCARBON

SYSTEMS

On first appearance Figure 14 appears similar to the pressure-temperature diagrams

examined in previous sections. However, it should be noted that the X-axis has been
changed from temperature to Gas-Liquid Ratio (GLR), ie: composition. The oil systems are
at GLR's to the left of the critical GOR, while the gas systems are located to the right of the
critical point.

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Petroleum Fluid Properties

Pr essure

%
90

10
%

20
%

30
%

40
%

60
%
50
%

70
%

%
80

Composition (GLR)
Figure 14: Generalised Pressure-Composition (p,x) Phase Diagram for Oil-Gas Systems

2-3-1

RESERVOIRS WITH GAS CAP AND ASSOCIATED OIL ZONE

Figure 15 illustrates the relationship of the pressure-temperature diagram of a typical oil

and a gas cap associated with the oil. The oil and gas each has its unique phase diagram,
yet they are related since the bubble-point pressure of the oil will be equal to the dewpoint
pressure of the gas cap. Moreover, both of these values will be equal to the static
reservoir pressure at the gas-oil contact. These relationships are theoretically true only
at the gas-oil contact; however, they can be considered true from a practical viewpoint if
the reservoir is small in area and is relatively thin.

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Petroleum Fluid Properties

ga
sc
ap

reservoir oi l

P res

Tres

Figure 15: Interrelation between the Phase Envelopes of a Reservoir Oil and its
Associated Gas Cap
Other Considerations
When reservoirs are large in area, or there is a tall hydrocarbon column, the composition
(and hence the physical properties) of the hydrocarbon fluids will usually change within
the reservoir. Such compositional changes occur for several reasons, such as an active
aquifer below the oil zone, secondary influx into the reservoir or simply due to
gravitational segregation. Samples should be taken to investigate if the need exists to
account for these variations in subsequent reservoir engineering calculations.
Both the static and bubble-point pressures vary with depth in reservoirs with large vertical
closure. The rate of change with depth below the gas-oil contact is greater for the static
pressure. This results in continually increasing undersaturation of the oil as depth
increases. Conversely, the bubble-point pressure increases as a function of the reservoir
temperature increase with depth. However the effect of pressure dominates and the
overall saturation pressure of the fluid decreases with depth, in the hydrocarbon column.

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Petroleum Fluid Properties

PHASE BEHAVIOUR OF PRODUCING FLUIDS

2-4

Up to this point we have considered in detail the phase relationships of fluids in the
reservoir. However, once in the wellbore the temperature and pressure of the flowing fluid
begins to fall rapidly and it is normal for gas and oil to be produced from the wellhead,
even if the fluid entered the wellbore single phase at the perforations. Figure 16
illustrates this process schematically.
The separation of gas and oil is occurring
continuously, although during flow in the wellbore, they are in intimate contact and
remain near to compositional equilibrium. Once in the separator they are still assumed to
be equilibrium phases as shown in Figure 17 before undergoing separate processing.
Providing the separator conditions are stable, this assumption of equilibrium is used
routinely to validate separator samples in the laboratory.

GAS
Producing
Fluid
P

(a)

Separate
Phases
GAS

(b)
(c)
(d)
(a)

SEPARATOR

OIL
GAS

(c)

(b)
(c)
(c)

(d)

(d)

(d)

CHOKE

(c)
(b)

OIL
STOCK
TANK

OIL

(a)

WELL BORE

(b)

(a)

(a)

RESERVOI R

Figure 16: Phase Relationship for Producing Fluids

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Petroleum Fluid Properties

feed

gas
.
p
se

sep. oil

Psep

Tsep

Figure 17: Phase Relationship Between Separator Gas and Oil

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