Syllabus

Hydrocarbon phase behavior Students should be able to:

Single component Sketch and label a typical P-T phase diagram for
Two Components single component.
Multi-Components Sketch and label P-T phase diagram for two
components.
Differentiate critical point for pure substance
and critical point for a mixture.
Sketch and label P-T phase diagram for multi
components.
Describe cricondentherm and cricondenbar.
Discuss retrograde vaporization and retrograde
condensation.
 HC Phase Behavior

Three factors are important to the behavior of molecules:

(1) Pressure
-A reflection of the number of molecules present and their motion.
-Pressure 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 pressure increases.

(2) Temperature
-A reflection of the kinetic energy of the molecules.
-Temperature 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, temperature is increased.
-The increase in kinetic energy causes an increase in molecular motion which
results in a tendency for the molecules to move apart.
 HC Phase Behavior

(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

Pressure and molecular attraction tend to confine the molecules and pull
them together, whereas temperature and molecular repulsion tend to
separate the molecules.
 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.

 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 consists of one component.
- On the other hand, the single phase consisting of natural gas may contain
eight or more components.
 Intensive and Extensive Properties

 Intensive Properties
- Independent of the quantity of material present.
- Example: Density, specific volume, and compressibility factor.

 Extensive Properties
- Determined by the total quantity of matter present.
- Example: Volume and mass.
 Phase Diagram: Single Component

 A phase diagram is a graph of pressure plotted against temperature which shows the
conditions under which the various phases of a substance may be present. Phase
diagrams are often called pressure-temperature 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:
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.
 Phase Diagram: Single Component
• The triple point:
Point T on the vapor-pressure line. This point
represents the pressure and temperature 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.
Pure Substance: Isothermal Expansion

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.
 Pure Substance: Isothermal Expansion

• Line 1-2: as mercury is removed, the

pressure 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 critical temperature, 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.
Pure Substance: Isobaric Expansion

• Increasing the temperature from T1 to

T2 at a constant pressure.
Temperature increases by the
addition of heat and maintain the
pressure 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.
Pure Substance: Isobaric Expansion
• 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.
Pure Substance: Isobaric Expansion

• 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.
Vapor Pressure of Normal Paraffins

(Data from M. W. Kellogg Co.)

Vapor Pressure of Isomeric Paraffins

(Data from M. W. Kellogg Co.)

 Bubble Point and Dew Point
Two isotherms:
Typical Pressure-volume diagram for • 1 - 2 below critical temperature
a pure substance • 3 - 4 above critical temperature.

• At point 1 the substance is in liquid phase, at

constant temperature, the pressure is reduced
from P1 to Pv by removal of mercury.
• A relatively large change in pressure results
from a small change in volume. This is
because liquids are relatively incompressible.
• When the pressure is reduced to the vapor
pressure, gas begins to form and further
removal of mercury causes vaporization of
the liquid. This continues at constant
pressure until all the liquid is vaporized (a
straight horizontal line)
 Bubble Point and Dew Point

Typical Pressure-volume diagram for

a pure substance • After all the liquid is vaporized, continued
removal of mercury causes expansion of
the gas and reduction in pressure.
• 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
temperature 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.
 Bubble Point and Dew Point

Typical Pressure-volume diagram for

a pure substance

• 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 pressures at the

bubble
point and dew point are equal to the vapor
pressure at T.
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.
Density-Temperature Diagram

• The shape of a typical density-temperature

diagram.

• The line shows the densities of the liquid

and gas phases that coexist in the two-phase
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.

Density-Temperature Diagram
 Two Component Systems

Two component system:

ethane and n-heptane

P-T Phase diagran for mixtures of C2

B
dan nC7.

A -- 90% weight ethane

ne
A

etha
B -- 50 % weight ethane C

C -- 10 % weight ethane

ne
ta
ep
h
n-
Each individual mixtures has its own
phase diagram.
Critical Point for Two Component

• 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.
 Bubble Point and Dew Point
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.
 Bubble Point and Dew Point

• Consider line 1 – 2 at constant

temperature expansion.
• At pressure P1 the substance is a liquid.
As pressure is decreased the liquid
expands until the pressure reaches a point
at which a few molecules are able to leave
the liquid and form a small gas phase.
• The pressure at which the first bubble of
gas is formed known as the bubble-point
pressure, Pb.

• As pressure is decreased below the bubble-point pressure, liquid and gas coexist.
• Finally, only a minute amount of liquid remains. This is known as the dew-point and the

pressure at this point is known as the dew-point pressure, Pd.

• Further reduction of pressure simply causes an expansion of the gas.
 Critical Point for Two Component
• Liquid and gas can coexist at
temperatures and pressures above the
critical point of a two-component
mixture.

• Notice that the region which

encompasses the two phases exists at
temperatures higher than the critical
temperatures and at pressures higher
than the critical pressure.

• Now that the definition of the critical

point is simply the point at which the
bubble-point line and the dew-point
line join.
• Thus, the critical point for mixtures is the point at which all properties of the liquid and
the gas become identical.
 Critical Point for Two Component

• The vapor-pressure lines of the two

components of mixture superimposed
on the phase diagram of the mixture.

• The region in which the gas and

liquid coexist for the mixture lies
between the vapor-pressure lines for
the two components.

• The critical temperature of the

mixture lies between the critical
temperature of the two pure
components.
• However, the critical pressure is above the critical pressures of both the components.

• The critical pressure of a two-component system will usually be higher than the critical
pressure of either of the components
Critical Point for Two Component

• The critical loci of binary systems

composed of normal paraffin
hydrocarbons 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.
 Pressure – Volume Diagram

 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 pressure 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
Pressure-volume diagram for a region.
two-component system
 Pressure – Volume Diagram

 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
Pressure-volume diagram for a
substance.
two-component system
Pressure – Volume Diagram

• 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.
Cricondentherm and Cricondenbar

 The temperature above which

liquid cannot be formed regardless of
the pressure attained is known as the
cricondentherm.

 The pressure above which no gas

can be formed regardless of the
temperature is known as the
cricondenbar.
 Retrograde condensation
•Another unusual feature of the two-
component system is illustrated by the
shaded portion.
•For a pure substance a decrease in
pressure causes a change of phase from
liquid to gas at the vapor-pressure line.
•Likewise, in the case of the two-
component system a decrease in pressure
causes a change of phase from liquid to gas
at temperatures below the critical
temperature.
• However, consider the isothermal
• As pressure is decreased from point 1 thedecrease in line
dew-point pressure illustrated
is reached by linebegins
and liquid 1—3.
to
form.
• At the position indicated by point 2 the system is 5% liquid and 95% gas.
 Retrograde condensation
• Pressure 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 pressure 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 temperatures between the critical
temperature and the cricondentherm.
• A similar retrograde situation occurs when temperature is decreased at constant
pressure between the critical pressure and the cricondenbar.