Phase Behaviour

Ref: ‘The Properties of Petroleum Fluids’ by

William D. McCain, Jr.

1
 Phase Behavior
Phase :
It defines any homogeneous and
physically distinct part of a system which
is separated from other parts of the system
by definite bounding surfaces.
For example, ice, liquid water, and water
vapor are three phases. Each is physically
distinct and homogeneous, and there are
definite boundaries.
2
 Phase Behavior
• Physical properties are termed either intensive
or extensive properties.
• Properties which are independent of the
quantity of material present are intensive.
Specific density, specific volume, and
compressibility factor are intensive examples.

• Properties such as volume and mass are

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

3
Phase Behavior

Three factors are important to the physical behavior of

molecules:
1. Pressure: a reflection of the number of molecules
present and their motion,

2. Temperature: a reflection of the kinetic energy of

the molecules, and

3. Molecular attraction and repulsion.

4
Phase Behavior -Pure Substances
A phase diagram is a graph of pressure plotted against
temperature showing the conditions under which the
various phases of a substance will be present.

Critical temperature of a pure substance may be defined as the temperature

above which the gas cannot be liquefied, regardless of the pressure applied.
The Triple Point : Point T on the vapor-pressure line is called the triple point. This
point represents the pressure and temperature at which solid, liquid, and gas
5 coexist under equilibrium conditions.
• The Melting Point Line: The line separates solid conditions from liquid
conditions. Again, pressure-temperature points which fall exactly on this
line indicate a two-phase system.

• The Sublimation-Pressure Line :

At temperature below the triple- point temperature, the vapor-
pressure line divides the conditions for which the substance is solid
from the conditions for which the substance is gas.

•6
 Use of Phase Diagrams

7
Vaporization of a pure substance at constant temperature.
 Typical phase diagram of a pure substance with two lines of
isothermal expansion: 123 below critical temperature, 45 above
critical temperature.
Line 45: if same process is applied, the removal of mercury will
cause pressure to decrease. There will not be a sudden change in
the density of the substance. The vapor-pressure line will not be
crossed. There is no abrupt phase change.
8
Typical phase diagram of a pure substance with two lines of isobaric
temperature change:
123 below critical pressure,
45 above critical pressure. 
To increase temperature, add heat energy. The addition of heat energy
will cause pressure to increase. But to keep the pressure constant, need
to remove the mercury from the cylinder. See figure next slide.

9
 Vaporization of a pure substance at constant pressure.
10
 Vapor Pressure of a Pure Substance
Clausius-Clapeyron Equation
• The Clausius-Clapeyron equation expresses the
relationship between vapor pressure and temperature. It is
the equation for the vapor pressure line.
• Using thermodynamic theory:

dpv Lv
= T (V  V )
dT Mg ML

dPv/dT is the rate of change of vapor pressure with

temperature. Thus it represents the slope of the vapor-
pressure line. Lv is the heat of vaporization of one mole of
liquid. T is the absolute temperature,
(VMg- VML) represents the change in volume of one mole as it
goes from liquid to gas.

11
Clausius-Clapeyron Equation

• Normally, the molar volume of a liquid is somewhat smaller than the

molar volume of the gas, so we will neglect the molar volume of the
liquid and rewrite Equation 2-1.

dpv = L, v but for an ideal gas P vVMg=RT

dT
 
TVMg
Substitute VMg yields

dpv= p v Lv
dT RT 2
If we assume that L v is a constant, we can rearrange and integrate

12
 Clausius-Clapeyron Equation

dpv Lv dT
 pv
=
R  T2

Lv  1 
ln pv = -    C,
R T 
Where C is the constant of integration, or

pv 2 Lv  1 1 
Ln( ) 
  
pv 2 R  T1 T2 

This is a straight line equation, when the logarithm of vapor pressure is plotted
against the reciprocal of absolute temperature. The slope of this line is –L v/R and
the intercept is C.

13
14
Example

• Given the following data, it is required to determine the

vapor pressure at 220, 300, and 420 oF?

Temperature 0F Vapor pressure of n-hexane psia

155.7 14.7
199.4 29.4
269.1 73.5
331.9 147.0
408.9 293.9
454.6 435.0

15
Solution

• Get (1/T) values

• Plot vapor pressure versus (1/T)
• Draw the Best Straight line.
• Read required values of vapor pressure
corresponding to the values of
temperatures.

16
 Cox Chart

• This problem was solved by plotting the

logarithm of vapor pressure against an
arbitrary temperature scale and by drawing a
straight line on the chart and adjusting the
temperature scale so that the vapor pressure
of water corresponded to the straight line.
• This modified graph of vapor pressure data
is known as a Cox Chart.

17
18
Vapour pressure of normal paraffins
Vapour pressure of
isomeric paraffins

19
 Pressure-Volume Diagram for a Pure
Substance

PT - Diagram

Figures show two isotherms.

PV - Diagram

20
Pressure-Volume Diagram for a Pure
Substance
Typical pressure-volume diagram of a pure
substance showing two isotherms: 13 below
critical temperature, 45 above critical
temperature.

On line 13. the point at which the first few

molecules leave the liquid and form a small
bubble of gas is called the bubble point.

The point at which only a small drop of liquid

remains is known as the dew point.

For a pure substance, the pressure at the bubble

point and dew point is equal to the vapor pressure
of the substance at the temperature of interest.

21
 Saturation Envelope
• Figure shows a more nearly
complete pressure-volume
diagram.

• The dashed line shows the

locus of all bubble points
and dew points. The area
within the dashed line
indicates conditions for
which liquid and gas coexist.
Often this area is called the
saturation envelope.

• The bubble-point line and

dew-point line coincide at
the critical point.

Pressure-Volume diagram of ethane

22
 Density-Temperature Diagram for a Pure
Substance
• The line shows the densities of
the liquid and gas that coexist in
the two-phase region. Often these
are called the saturated densities.

• Notice that the densities of the

liquid and gas are identical at the
critical point.

•The average densities of the

liquid and gas will plot as a
straight line which passes
through the critical point.

Typical density-temperature diagram of a

pure substance

23
Fig. Saturated Fluid Densities.
24
 Two-Component Mixture

• The petroleum engineers do not normally work

with two-component systems: usually mixtures
consisting of many components are encountered.

• However, it is instructive to observe the

differences in phase behavior between two-
component mixtures and pure substances. These
differences are amplified in multicomponent
mixtures.

25
 Phase Diagram of Two-Component
Mixture
• The two-phase region of the phase diagram is
bounded on one side by a bubble-point line
and the other side by a dew-point line. The
two lines join at the critical point.

• The pressure at which the first gas is formed

is the bubble-point pressure, pb.
.

26
Typical Phase Diagram of Two-Component Mixture with line of isothermal
expansion 12

27
Critical point of two-component system

• The definition of the critical point as applied to a

pure substance does not apply to a two-component
mixture.

• The definition of the critical point is simply the point

at which the bubble-point line and the dew-point line
join.

• A more rigorous definition of the critical point is that

it is the point at which all properties of the liquid and
the gas become identical.

28
Typical phase diagram of a two-component mixture with vapor-
pressure lines of the two pure components

The critical pressure of a two-component mixture usually will be

higher than the critical pressure of either of the components.
29
• Cricondenth
erm: It is the
highest
temperature
on the
saturation
envelope.
• Cricondenba
r : It is the
highest
pressure on
the
saturation
envelope.

Cricondentherm: The highest temperature on the

saturation envelope.
Cricondenbar: The highest pressure on the
saturation envelope. 30
 Retrograde Condensation
Consider the isothermal decrease in
pressure illustrated by line 123 on
Figure. As pressure is decreased
from point 1 to point 2, the system
is 25 % liquid by volume and 75 %
gas.

• A decrease in pressure has caused

a change from gas to liquid. This is
retrograde condensation.

• Note that an upper dew point and

a lower dew point exist.
• The upper dew point is sometimes
called the retrograde dew point.

31
 Retrograde Condensation

• As a pressure decreased from

point 2 toward point 3, the amount
of liquid decreases, the dew-point
line is crossed a second time, and
the system again becomes gas.

• The region of retrograde

condensation occurs at
temperatures between the critical
temperature and the
cricondentherm.

32
Pressure-Volume Diagram for a Two-Component
Mixture

Fig. Typical pressure-volume diagram of a two-component mixture showing

one isotherm below the critical temperature.

33
Three-component mixtures

Ternary diagram

34
Ternary phase diagram of mixtures of methane, propane, and n-
pentane at 500 psia and 1600F with equilibrium tie-line, 123

35
 Uses of Ternary Diagrams
• (1) Analysis of crude oil composition.
• (2) Analysis of miscible displacement.

Two techniques are proposed:

- A. In the first one, the figure gives the phase envelope of
an oil mixed with carbon dioxide. The oil is plotted as
an artificial two-component mixture, with methane as
one component and all other constituents added
together as the other component.
– B. Another technique separates the oil into two pseudo-
components. One contains all compounds of 12 carbon
atoms or less. The other contains all compounds of 13
carbon atoms or more. Carbon dioxide is the third
component of the diagram.

36
 Draw a Ternary Diagram

• Draw an equilateral triangle as a Ternary diagram.

• Assume that this Ternary diagram is used to

describe different compositions of methane,
propane, and n-pentane.

• Plot the following three compositions:

methane Propane n-pentane
50 20 30 mole %
60 30 10 mole %
10 15 75 mole %

37
Application of Ternary Diagram

• Example
• Determine the composition and quantities
of gas and liquid 6 lb moles of a mixture of
50 mole % methane, 15 % mole propane,
and 35 % mole n-pentane at 160 F and
500 psia ethane are considered at
equilibrium.

38
First: Plot the given composition.

39
Read composition of equilibrium gas at point 2 (intersection of tie
line with dew point line as,

Gas composition at point 2

74 mole % methane
75 mole % propane
12 mole % n-pentane
-----------------------------
100 mole %

40
Read composition of equilibrium liquid at point 3 (intersection of
tie line with bubble point line as,

Liquid composition at point 3

13 mole % methane
17 mole % propane
70 mole % n-pentane
------------------
100 mole %

41
Calculate gas and liquid fractions by measuring lengths on the tie
line as,

Gas fraction = (0.65 inch/1.07 inch)

= 0.607 lb mole gas/lb mole
total mix

Liquid fraction = (0.42 inch/1.07 inch)

= 0.393 lb mole liquid/lb
mole total mix
Or = 1.07 - 0.65 = 0.42 inch.

Calculate gas quantity as follows:

Gas quantity = (0.607) x (6.0 lb mole)
= 3.6 lb mole, then
Liquid quantity = 6.0 lb mole – 3.6 lb
mole = 2.4 lb mole.

42
 Why are Petroleum Fluid Properties
important
• To estimate amount of hydrocarbons-initially-in-place
and
• To estimate recoverable fraction of these
hydrocarbons (reserves)
• To understand fluid flow in the reservoir and to predict
changes in reservoir conditions with time, (e.g.
reservoir pressure), during depletion (production)
• To identify processing and refining requirements
• To identify markets for products and to conduct
economic evaluations and risk analyses

43
 Basic Concepts and Phase
diagram
Fluid Phase mainly depends on composition of the
fluid and its ambient pressure (P) and temperature (T)
For example, in a system,

• If P>Pbub, only oil exists; If P<Pbub, oil + gas exist. (at given T)

• Even P>Pbub, one can observe gas + oil production at surface.

gas Low P gas

oil
oil

gas
High P oil
oil
44
If P<Pbub. If P>Pbub.
 Typical Petroleum production
facility
Wellhead Separator Stock-Tank
Tank Gas (sale line)
High Pressure (Low Pressure)
removed
Gas removed
Sale line
Choke
Stock Tank


Tubing Head (‘Bean’) Gas
Pressure  Pressure
Gas


Flow line Oil
Pressure
Oil


Oil produced
as Single Reservoir Pressure


Phase
Oil Zone
Bottom Hole 
Pressure

45
 Introduction

Petroleum production systems

Possible pressure losses in a complete systems

46
 Typical Production System

PTH = 1000 psi (145 kPa)

Pressures drops every
stage in its flow path
dP = 400 psi (58 kPa) during the production
GAS
of reservoir fluids

PSEP =
300 psi
OIL
Large proportion of
(43.5 kPa)
d P = 3000 psi
(435 kPa) CHOKE pressure drops inside
PCHOKE = 300 psi
(43.5 kPa)
the completion
tubulars and surface
WATER facilities
dP = 2000 psi (290 kPa)

PRES = 6000 psi (870 kPa)

PWF = 4000 psi (580 kPa)

47
Typical reservoir pressure profile
 Phase Diagram
Single
Single phase
phase Gas
Pressure liquid
C

line
re)

line
ssu

)
ure
pr e

ess
t(
oin

(p r
e -p

t
oin
bbl

w -p
Bu

gas
De

Temperature
48
Pressure Temperature Relations
 Phase Diagram

Definitions:
Pressure

liquid C 1. Bubble-point line: the point where

the first bubble is formed
during pressure decrease at
constant temperature.

60% 2. Dew-point line: the point where

80% the first liquid drop is formed
100%
40% during pressure increase at
liquid
constant temperature.
(0% gas) 0% liquid
20%
(100%
Note: Pure-component system can
gas)
be regarded as a special case
of two-component system
where two-phase region shrinks
gas to form a line.

Critical point: the point where the

Temperature bubble-point line meets the
dew-point line
Pressure Temperature49 Relations
 Phase Diagram
Cricondenbar
Definitions:

Cricondenbar: the
liquid C
Pressure

pressure above which

two phases can no
longer exist.

Cricondentherm: the
Cricondentherm temperature above
which two phases do
gas not exist.

Additional points:

Temperature
50
 Basic definitions (cont.)
Path A Path B Definitions:
Liquid-mixture-gas
Retrograde condensation:
liquid C
Pressure

phenomenon that the

dew point line is
crossed (i.e., from gas
phase to liquid) as
pressure decreases
rather than increases.

Because this is the reverse

of normal behaviour, it
“Retrograde
condensation” is called “retro”.

gas

Temperature
51
 Application of Phase Diagram (P-T
diagram)
P-T diagram essentially help
– Classify Reservoir
– Classify the naturally occurring hydrocarbon
systems (Petroleum Fluid)
– Describe the phase behavior of the reservoir fluid
Basis:
– The composition of the reservoir hydrocarbon
mixture
– Initial reservoir pressure and temperature
– Pressure and temperature at the surface
production system
52
Reservoir Classification
• Oil reservoir
– In general
Tres<Tc of
reservoir fluid
• Gas reservoir
– In general,
Tres>Tc of
reservoir fluid
(hydrocarbon
systems)
53
 Oil Reservoir

• Under-saturated oil
reservoir
initial reservoir pressure, pi
> the bubble-point
pressure, pb of the
reservoir fluid

• Saturated oil reservoir

p i = pb

• Gas-cap reservoir or two

phase reservoir
p i < pb

Note
The appropriate quality
line gives the ratio of
volume of liquid (oil) to
volume of gas 54
 Gas Reservoir
Dry gas reservoir
– initial reservoir temperature
higher than cricondentherm
temperature
– even at low pressure
(separator) and temperature,
fluid is 100% gas

• Wet gas reservoir

– initial reservoir temperature
higher than cricondentherm
temperature
– But even at low pressure
(separator) and temperature,
some gas condensate to liquid

• Retrograde gas-condensate
reservoir
– Reservoir temperature lies
between Tc and Tcri (Tc<Tr<Tcri)

• Near critical gas-condensate

– Reservoir temperature is nearly
equal to critical temperature of
fluid (Tr ~Tc)
55
Petroleum Fluid - Rough Classification
1. Natural gas
– Gas phase at surface condition.
It is condensed into a liquid under compression for convenient
transportation and storage.
2. Crude oil
– wide range of colour, viscosity, density, and impurity.
– API gravity, °API = 141.5 / ( specific gravity) - 131.5
– for water, °API = 10.
Fluid becomes lighter as API gravity increases.

56
 Components of Petroleum Fluids
• Contain mostly hydrocarbon (HC) such as
– C1, (Methane, CH4)
– C2 (Ethane, C2H6)
– C3 (Propane, C3H8)
– .
– .
– .
– C7+ including some % of non-hydrocarbons such as:

• Sulfur compounds (most common)

• Oxygen compounds
• Nitrogen Compounds
• Carbon dioxide
• H2S
• Metals, Salts

57
 Reservoir Fluid Classification
Depending on components (light or heavy),
gravity, GOR and so on, one can classify
reservoir fluids into five categories

Higher GOR, higher API gravity

1. Dry gas

heavy components dominant,

higher specific gravity
2. Wet gas
3. Retrograde condensate gas
4. Light oil (volatile oil)
5. Heavy oil (black oil)

58
Heavy oil Light oil
 Fluid Type Identification
Types of the fluid can be confirmed only by
laboratory observation

Some readily available indications can

identify the types, such as:
– Initial Producing Gas Oil Ratio
– Gravity of Stock Tank Liquid
– Color of Stock Tank Liquid

59
 Reservoir Fluid Classification
Dry Gas • Dry gas is
3000 primarily
Initial Conditions methane with
Critical Point
some
intermediate
• This gas does
Pressure, psia

not contains
1500 enough heavy
molecules to
Abandonment form liquid HC
50 20
Separator
Single Phase Gas
at the surface
5 2 (High Pressure)
in Reservoir & Production • Often called
Vol % Liq. Equipment
0
0 simply gas
100 200 reservoir
Temperature, C
o
Field Characteristics are:
- no petroleum liquid production 60
 Reservoir Fluid Classification
Wet Gas • Gas exists solely as gas
in the reservoir through
3000 out the reduction of
Initial Conditions pressure
Critical • Separator conditions
Point some lies with phase

rve
rve

envelop causing some

oint Cu
liquid to be formed at the
t Cu

Single Phase Gas

Pressure, psia

In Reservoir surface (condensate

o in

gas)
Dew P
eP

1500 • Field Characteristics are:

bbl

• - very high gas-oil ratios

(GOR)
Bu

100
Abandonment • - a tank liquid gravity
50 • of <0.78(>50oAPI)
20
10 Separator
5 • - a tank liquid colour
2 0 (High Pressure) GAS
• that is “water” white
Vol % Liq.
0
100 Temperature (oC) 200
61
 Reservoir Fluid Classification
Field Characteristics are:
Retrograde Condensate Gas - a producing gas-oil ratio of
1,000 to 10,000 v/v
3000 - a tank liquid gravity of 0.75
Single Phase “Gas” to 0.825 (60o - 40oAPI)
Critical Point
Dew Point -a stock tank liquid can be
lightly colored, brown color,
LIQUID greenish, or water-white

Curve
GAS
Pressure, psia

e
rv

Also called gas-condensates

Cu
in t

t
1500

Poin
Po
le
bb

w
Bu

De
60 40 Abandonment
20
100
80 Separator
(High Pressure) 10
0
Vol % Liq.
0
100 Temperature, oC 200
62
 Reservoir
Light Oil (Volatile oil)
Fluid Classification
Contain relatively fewer
heavy molecules, and
3000 more intermediate
Undersaturated Oil
Saturated (Bubble Point) molecules than heavy
oil (commonly up to C6)
Critical Point
Field Characteristics

rve
LIQUID are:

Point Cu
- a high “shrinkage”
ve
Pressure, psia

(FVF>2)
Cu

- a gas-to-oil ratio of
int

1500 400 to 1,000 v/v

Po

- a tank-oil gravity of
e

Dew
l
bb

<0.825 (>40oAPI)
Bu

80 - a tank-oil that is
Abandonment deeply
100
60
40
coloured (brown,
orange or green)
VAPOUR
20
0
Separator Vol % Liq.
0
100 200
Temperature, oC

63
 Reservoir Fluid Classification
Heavy Oil (Black-oil)
3000
Undersaturated Oil
Contain large
Saturated (Bubble Point) number of heavy
LIQUID Critical components of
Point HC

Field

Point Curve
ve
Pressure, psia

ur

Characteristics:
tC

- a low
in

1500
Po

“shrinkage”
le

(FVF<2)
bb

90
- Initial gas-to-oil
Bu

Dew
80 ratio of <400 v/v
70 Abandonment - a tank-oil gravity
100 of >0.825
60 (<40oAPI)
20 0
40 VAPOUR - a tank-oil that is
Separator Vol % Liq.
0 black or
100 200 very dark
Temperature, oC
64
Note: Does not mean to be the color is black. Some time called ordinary crude oil