1

SKPP 2313
RESERVOIR ROCK & FLUID PROPERTIES
Ch. 11a Qualitative Hydrocarbon Phase
Behavior
Assoc. Prof. Abdul Razak Ismail
Petroleum Engineering Dept.
Faculty of Petroleum & Renewable Energy Eng.
Universiti Teknologi Malaysia
Assoc. Prof. Abdul Razak Ismail, UTM

Contents
Single component
Two Components
Multi-Components

Assoc. Prof. Abdul Razak Ismail, UTM

Pressure, Temperature and Intermolecular Forces

Three factors are important to the behavior of molecules:
1. Pressure - a reflection of the number of molecules present and their motion. P is a
reflection of the number of times the molecules of a gas strike the walls of the container.
As the molecules are forced closer together the P increases.
2. Temperature - a reflection of the kinetic energy of the molecules. T is simply a physical
measure of the average kinetic energy of the molecules of the material. As heat is added to
the material the kinetic energy of the molecules is increased, and, as a result, T is increased.
The increase in kinetic energy causes an increase in molecular motion which results in a
tendency for the molecules to move apart.
3. Molecular attraction and repulsion. Intermolecular forces change with distance between
the molecules. The attractive force increases as the distance between the molecules
decreases until the molecules get so close together that their electronic fields overlap. Any
further decrease of the distance between the molecules will cause a repulsive force between
them. This repulsive force will increase as the molecules are forced closer together
P and molecular attraction tend to confine the molecules and pull them together,
whereas T and molecular repulsion tend to separate the molecules.
Assoc. Prof. Abdul Razak Ismail, UTM

Definition of Phase and Component

Phase - any homogenous 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 homogenous and there are definite boundaries
between ice and water, between ice and water vapor, and between liquid water
and water vapor.
It is not necessary for any one particular phase to be continuous. For example,
the ice may exist as several lumps in the water.
Thus, we say that we have a three-phase system: solid, liquid, and gas.
Component - the smallest number of independently variable constituents by means
of which the composition of each phase can be expressed for a system at
equilibrium.
For example, the ice-water-water vapor system mentioned above consists of one
component.
On the other hand, the single phase consisting of natural gas may contain eight
or more components.
Assoc. Prof. Abdul Razak Ismail, UTM

Definition of Intensive and Extensive properties

Intensive properties are independent of the quantity of material present.
Examples: density, specific volume, and compressibility factor
Extensive Properties are determined by the total quantity of matter present
such volume and mass

Assoc. Prof. Abdul Razak Ismail, UTM

Phase diagram for single component (pure substance)

A phase diagram is a graph of P vs T which shows the conditions under
which the various phases of a substance may be present.
Phase diagrams are often called P-T diagrams.
The vapor-pressure line (line TC):
This line divides the liquid region from
the gas region. Points which fall on the
line indicate conditions of both gas and
liquid coexist.
The critical point (C):
The upper limit of the vapor-pressure
line, critical temperature, Tc and the
critical pressure, Pc. Temperature above
Tc, a gas cannot be liquefied, regardless
of the pressure applied. Similarly,
pressure above Pc, liquid and gas cannot
coexist regardless of the temperature.
Assoc. Prof. Abdul Razak Ismail, UTM

The triple point (T):

This point represents the P & T at which
solid, liquid, and gas coexist under
equilibrium conditions.
The sublimation pressure line:
At temperatures below the triple-point, the
vapor-pressure line divides the region
where the substance is solid from the
region where the substance is gas.
Theoretically this line extends to a
temperature of absolute zero.
The melting-point line:
The nearly vertical line above the triple point separates the solid region from the
liquid region. Again, pressure-temperature points which fall exactly on this line
indicate a two-phases system; in this case coexistance of solid and liquid. Phase
diagrams for some pure materials show other lines within the solid region indicating
a change of phase of the solid brought about by a change in crystalline structure.
The upper end of the melting-point line has not been obtained experimentally.
Assoc. Prof. Abdul Razak Ismail, UTM

Vaporization of a pure substance at constant T

Consider a cylinder in which the temperature can be
controlled and the volume varied by injection of
mercury as shown.
Figure shows that a pure substance has been trapped in
the cylinder at pressure P1 and T < Tc.
Remove mercury at constant temperature, thereby
causing the pressure to be reduced.
Phase diagram for a pure substance at isothermal expansion
Line 1-2: As mercury is removed the P will decrease until
it reaches a value of Pv.
At this point a gas phase will begin to form as molecules
leave the liquid.
As mercury removal continues, the gas phase volume
will increase and the liquid phase volume will decrease.
However, the pressure will remain constant at pv.
Once the liquid phase disappears, further mercury
removal causes a decrease in pressure as the gas phase
expands.
Above the Tc, i.e. line 3 - 4, the removal of mercury will
cause a decrease in pressure; however, there will not be
an abrupt change in the density., and no phase change.
Assoc. Prof. Abdul Razak Ismail, UTM

Phase diagram at isobaric temperature change

Increasing the temperature from T1 to T2 at a constant
pressure. T increases by the addition of heat and maintain
the P constant by removal of mercury as required. Cell A
full of liquid at temperature T1 (less than the vapor-pressure
temperature of the substance).
In cell B the substance has been heated at constant pressure
to the vapor-pressure temperature. A gas phase has formed
and gas and liquid coexist. The injection of heat has caused
the kinetic energy of the molecules to increase so that the
molecules with the highest kinetic energy can escape the
attractive forces and pressure and form a gas phase.
After the vapor-pressure temperature is reached, heat that is
put into the cylinder causes vaporization of the liquid rather
than increase of the temperature. The temperature will
remain constant as long as gas and liquid co-exist.
Cell D indicates that enough heat has been put into the
cylinder to evaporate all the liquid and additional heat has
caused an increase in temperature to T2.
The same process at pressures above the critical pressure,
for example line 3-4 , will not show the abrupt change in
phase that the process below the critical pressure shows.
Assoc. Prof. Abdul Razak Ismail, UTM

10

10

Vapor Pressure of Normal Paraffins

(Data from M. W. Kellogg Co.)

Assoc. Prof. Abdul Razak Ismail, UTM

11

11

Vapor Pressure of Isomeric Paraffins

(Data from M. W. Kellogg Co.)

Assoc. Prof. Abdul Razak Ismail, UTM

Bubble point and dew point

Typical Pressure-Volume diagram for a

pure substance

Two isotherms:
1 - 2 below critical temperature
3 - 4 above critical temperature.

12

12

At point 1 the substance is in liquid phase, at constant T, the P is

reduced from P1 to vapor P (Pv) by removal of mercury.
A relatively large change in P results from a small change in
volume. This is because liquids are relatively incompressible.
When the P is reduced to the Pv, gas begins to form and further
removal of mercury causes vaporization of the liquid. This
continues at constant P until all the liquid is vaporized (a straight
horizontal line)
After all the liquid is vaporized, continued removal of mercury
causes expansion of the gas and reduction in P. Since the gas is
highly compressible, the slope of the gas line is much less steep
than the slope of the liquid line.
Line 3- 4 illustrates the same process at a T above Tc. The line
shows that there is simply an expansion of the substance
and that no phase change occurs.
Point where the first few molecules leave the liquid and form a
small gas bubble is the bubble point.
Point where only small drop of liquid remains is the dew point.
The sharp breaks in the line represent the bubble point and
dew point.
For pure substance the P at the bubble point and dew point are
equal to the Pv at T.
Assoc. Prof. Abdul Razak Ismail, UTM

13

13

Saturation Envelope
Fig. shows several isotherms on the
pressure-volume diagram.
The dashed line shows the locus of all
bubble points at standard conditions.
This dashed line contains the region in
which liquid and gas can coexist, and is
known as saturation envelope.
The critical point is located as the point
at which the bubble point and dew point
coincide.
Notice that the critical temperature
isotherm shows a point of inflection as it
passes through the critical pressure.

Assoc. Prof. Abdul Razak Ismail, UTM

14

Phase behavior of a single component HC

14

3D diagram of a single component system

Assoc. Prof. Abdul Razak Ismail, UTM

Density-temperature diagram for a pure substance

15

15

The shape of a typical density-temperature

diagram.
The line shows the densities of the liquid
and gas phases that coexist in the twophase region. Often these are called the
saturated densities.
Notice that the density of the liquid and
gas become the same at the critical point.
The average densities (dashed line) of the liquid and vapor will plot as a straight line which passed
through the critical point.
Known as the Law of Rectilinear Diameters.
Assoc. Prof. Abdul Razak Ismail, UTM

16

16

Two component systems (binary system)

P-T diagram for mixtures of two component system: ethane (C2)
and n-heptane (nC7)

A - 90% weight ethane

B - 50 % weight ethane
C - 10 % weight ethane

Each individual mixtures has

its own phase diagram.

Assoc. Prof. Abdul Razak Ismail, UTM

17

17

The critical point for two-component systems

Phase data on seven mixtures of methane and ethane along with the vapor-pressure lines
for pure methane and pure ethane.
Observe that the two-phase region of each of the mixtures lies between the vapor
pressures of the two pure substances and that the critical pressures of the mixtures lie
well above the critical pressures of the pure components.
The dashed line is the locus of critical points of mixtures of methane and ethane.
Assoc. Prof. Abdul Razak Ismail, UTM

18

18

Vapor pressure bubble point and dew point of two-component systems

Typical shape of the phase diagram for a mixture of equal

amounts of two components.

The behavior of a mixture of two

components is not as simple as the
behavior of a pure substance.
Instead of a straight line representing
the vapor-pressure curve there is a broad
region in which two phases coexist.
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.

Consider line 1 2 at constant temperature expansion.

At pressure P1 the substance is a liquid.
As P is decreased the liquid expands until the P reaches a point at which a few molecules
are able to leave the liquid and form a small gas phase.
The P at which the first bubble of gas is formed known as the bubble point pressure, Pb.
As P is decreased below the Pb, liquid and gas coexist.
Finally, only a minute amount of liquid remains. This is known as the dew-point and the
P at this point is known as the dew-point pressure, Pd.
Further reduction of P simply causes an expansion of the gas.
Assoc. Prof. Abdul Razak Ismail, UTM

19

19

Phase behavior of two-component systems

Referring to the figure,
the vapor pressure and
bubble point lines do not
coincide but form an
envelope enclosing a
broad range of T and P at
which two phases (gas
and oil) exist in
equilibrium.
Phase behavior of a 50:50 mixture of two pure HC components

The dew point and bubble point curves meet at the critical point, which is defined
as that T and P at which the liquid and vapor (gas) phases have identical intensive
properties (density, specific volume, etc)
Fluid above the bubble point is in the liquid state and fluid below the dew point is
gas
In the space enveloped between the two lines, liquid and gas are in equilibrium
Assoc. Prof. Abdul Razak Ismail, UTM

20

20

The critical point for two-component systems

The critical loci of binary
systems composed of normal
paraffin HC are shown.
Obviously the critical
pressures of mixtures are
considerably higher than the
critical pressures of the
components of the mixtures.
In fact, the difference in
molecular size of the
components greatly
increases the critical
pressures of the mixtures.
Assoc. Prof. Abdul Razak Ismail, UTM

Pressure-volume diagram for a two-component system

21

21

A single isotherm on a pressure-volume

diagram of a two-component mixture with a
constant over-all composition.
The feature that distinguishes this diagram
from a pressure-volume diagram of a pure
substance is that the P decreases as the
process passes from the bubble point to the
dew point.
This decrease is caused by the change in
composition of the liquid and the vapor as
the process passes through the two-phase
region.
At the bubble point the composition of the liquid is essentially equal to the overall
composition of the mixture but the infinitesimal amount of gas is richer in the more
volatile component
Likewise, at the dew point the composition of the vapor is essentially equal to the overall
composition of the system and the infinitesimal amount of liquid is richer in the less
volatile component
The breaks in the line at the bubble point and dew point are not as sharp as for a pure
substance.
Assoc. Prof. Abdul Razak Ismail, UTM

22

22

Pressure-volume diagram for a two-component system

Pressure-volume diagram for a
mixture of ethane and n-heptane.
Showing several isotherms and the
saturation envelope.
Notice that at the lower temperatures
the dew point breaks in the isotherms
are almost non-existant.
Also notice that the critical point is
not at the top of the saturation
envelope as it was for pure substances
but appears somewhat to the right of
center.
This is a result of the slope of the
isotherms through the two-phase
region.

Assoc. Prof. Abdul Razak Ismail, UTM

23

23

Cricondentherm and Cricondenbar

The T above which liquid cannot be formed regardless of the P

attained is known as the cricondentherm.
The P above which no gas can be formed regardless of the T is
known as the cricondenbar.
Assoc. Prof. Abdul Razak Ismail, UTM

24

Retrograde condensation

24

Another unusual feature of the two-component

system is illustrated by the shaded portion.
For a pure substance a decrease in P causes a
change of phase from liquid to gas at the Pv line.
Likewise, in the case of the two-component
system a decrease in P causes a change of phase
from liquid to gas at temperatures below the
critical T.
However, consider the isothermal decrease in P
illustrated by line 13.
As P is decreased from point 1, the dew-point line
is reached and liquid begins to form.
At the position indicated by point 2 the system is
5% liquid and 95% gas.

P decrease has caused a change from gas to liquid. This is exactly the reverse of the behavior one
would expect.
This behavior is called retrograde condensation.
As P is decreased from point 2 toward point 3 the amount of liquid decreases; the dew-point line is
reached and the system again becomes gas.
The region of retrograde condensation occurs at T between the Tc and the cricondentherm.
A similar retrograde situation occurs when T is decreased at constant P between the Pc and the
cricondenbar.
Assoc. Prof. Abdul Razak Ismail, UTM

25

25

Definition of Solution
Solution

: A homogeneous mixture of two or more

substances, which have the same chemical
composition and the same physical properties
throughout.

Ideal solution : In an ideal solution there are no forces of

attraction between the constituent molecules.

Assoc. Prof. Abdul Razak Ismail, UTM

26

Vapor pressure of an ideal liquid solution

Raoults law states that for an ideal solution, the partial pressure of a
component in the vapor is equal to the product of the mole fraction of that
component in the liquid and the vapor pressure of the pure component.

Pi xi Pvi
PT xi Pvi

where

where

Pi = partial pressure of the ith component in the vapor

xi = mole fraction of the ith component in liquid solution
Pvi = vapor pressure of the pure ith component
PT = total pressure of exerted by the vapor
= vapor pressure of the solution
= bubble point pressure

Daltons law states that for an ideal gas the partial pressure of a component in
the vapor is equal to the product of the mole fraction of that component in the
vapor and the vapor pressure of the solution.

Pi yi PT

or

yi

Pi
PT

27

Example
At 0oF calculate the bubble-point pressure and the composition of the vapor at the bubble point for a twocomponent solution having a mole fraction of propane equal to 0.5 and a mole fraction of butane equal to 0.5.
Repeat these calculations for a solution whose mole fraction of propane is 0.25 and whose mole fraction of butane
is 0.75. The vapor pressures of pure propane and butane at 0oF are 38.20 psia and 7.30 psia, respectively.
For the solution of propane and butane of each 0.5 mole fraction:
Component

Pi

xi

Pi = xiPvi

yi = Pi/PT

C3H5

38.20

0.50

19.10

0.840

C4H10

7.30

0.50

3.65

0.160

PT = 22.75 psia
Thus, bubble-point pressure for this solution is 22.75 psia at 0oF, and the mole fractions of propane and butane are
0.840 and 0.160, respectively
For the solution of propane = 0.25, and butane = 0.75 mole fractions:
Component

Pi

xi

Pi = xiPvi

yi = Pi/PT

C3H5

38.20

0.25

9.55

0.635

C4H10

7.30

0.75

5.48

0.365

PT = 15.03 psia
Thus, bubble-point pressure for this solution is 15.03 psia at 0oF, and the mole fractions of propane and butane are
0.635 and 0.365, respectively

Liquid and vapor composition of two-component system

in the two-phase region

(1)

x1 Pv1 x 2 Pv2 PT
but, x1 x 2 1 x 2 1 x1

(2) x1 Pv1 1 x1 Pv2 PT

(3)

x1

PT Pv2
P P
, and x 2 T v1 1 x1
Pv1 Pv2
Pv2 Pv1

Daltons Law for the vapor :

P x P
P x P
( 4) y1 1 1 v1 , and y 2 2 2 v2 1 y 2
PT
PT
PT
PT
where PT pressure in the liquid phase

Note: Equations (1) to (4) are applicable anywhere in the two-phase region,
including at the bubble point and dew point.

28

29

Example
Assuming ideal solution behavior for a system of one mole n-butane and one mole n-pentane.
a. Calculate the composition of the liquid and vapor at 180oF and 95 psia.
b. Calculate the bubble point and the composition of the vapor at 180oF.
c. Calculate the dew point pressure and the composition of the liquid at the dew point at 180oF.
a. From graph (page 10), at 180 oF: PvC4 = 160 psia, and PvC5 = 54 psia
Mole faction in the liquid (Eq. 3):

x C4

PT PvC5
95 54

0.394
PvC4 PvC5 160 54

x C5 1 x C4 1 0.394 0.606
Mole faction in the vapor (Eq. 4):

y C4

x c4 PvC4 0.394 x160

0.665
PT
95

y C5 1 y C4 1 0.665 0.335

30

30

b. The bubble point and the composition of the vapor at 180oF?

Since the overall composition and the composition of liquid are equal at bubble point,
xC4 = xC5 = 0.5
From Eq.(3) : 0.5

PT 54
PT 107 psia bubble po int pressure
160 54

From Eq. (4): Mole faction of the vapor at bubble point pressure:

yC4

x c4 Pv4 0.5 x160

0.747
PT
107

yC5 1 y C4 1 0.0.747 0.253

Assoc. Prof. Abdul Razak Ismail, UTM

31

c. The dew point pressure and the composition of the liquid at the dew point at 180oF?
Since the overall composition and the composition of vapor are equal at dew point,
yC4 = yC5 = 0.5.
From Eq.(4) : y C4

From Eq. (3) : x C4

x c4 Pv4
PT

where PT dew point pressure

PT PvC5
Eq.(3) in (4) :
PvC4 PvC5

PT PvC5

Pv4
P

P
y C4 vC4 vC5
PT

PT 54

(160)
160

54

y C4 0.747
PT 80.8 psia (dew point pressure)
PT

From Eq. (3) Mole faction of the liquid at dew point pressure:
80.8 54
x C4
0.243
160 54
x C5 1 0.243 0.757

32

Calculation Summary
For a system composed of 1 mole of n-butane and 1 mole of n-pentane at 180oF.
Bubble point pressure (Pb) = 107 psia
Composition of vapor at Pb:

yC4 = 0.747 , yC5 = 0.253

Compositions of liquid and vapor at 95 psia:

xC4 = 0.394, xC5 = 0.606;
yC4 = 0.665, yC5 = 0.335
Dew point pressure (Pd) = 80.8 psia
Composition of liquid at Pd: xC4 = 0.243, xC5 = 0.757