Phase Behavior of different System

Dr. Tarun Kumar Naiya

Associate Professor, Department of Petroleum Engineering
IIT (ISM) Dhanbad
Email : [email protected]
Phase Behavior
What is a phase?
A simple definition is that it is a part of a system that is physically distinct from the other
parts of the system by a surface.
Generally, we think of the three phases of matter that we are familiar with — solid, liquid,
and gas.
Each of these are distinct and easily discernible.
There is an ordered phase and a disordered phase that pass light very differently.
The phase behaviour of a pure
compound is shown by the pressure-
temperature diagram in Figure .
All the conditions at which the vapour
and liquid phases can coexist at
equilibrium are shown by the line AC.
Any fluid at any other pressure-
temperature conditions, is unsaturated
single phase as required by the phase
rule.
The fluid above and to the left of the
line is referred to as a compressed or
under saturated liquid, whereas that
below and to the right of the line is
called a superheated vapour or gas.
The line AC is commonly known as the vapour pressure curve,
as it shows the pressure exerted by the vapour coexisting with its
liquid at any temperature.
The temperature corresponding to the atmospheric pressure
is called the normal boiling point or simply the boiling point
of the compound.
The line AB is the solid-liquid equilibrium line, which is also
known as the melting point curve.

The intersection of the vapour-liquid and liquid-solid lines is

the triple point.

It is the only point where the three phases can coexist for a
pure system.

The line AD is the solid-vapour equilibrium line or the

sublimation curve.

The solid carbon dioxide (dry ice) vaporising into its gaseous
form is a common example of this region of the phase
behaviour diagram.
The system bubble points at various temperatures form the
bubble point curve, whereas the dew points form the dew
point curve.

The two curves meet at the critical point and together

identify the phase envelope.

Any fluid within the phase envelope, Point M, forms two

equilibrated phases with the vapour/liquid molar ratio equal
to B M/MD.

The bubble point and dew point curves appear as a single

vapour pressure curve on a pressure-temperature plot for a
pure compound.
The change of phase from liquid to vapour
is accompanied by a large increase in
volume at low temperatures (Figure 1.7).

The expansion reduces as the temperature

approaches the critical point.

Indeed the system changes from all liquid

into all vapour, or vice versa, without any
change in the mixture volume at the critical
point.

An isothermal expansion of a fluid at a

temperature above the critical temperature
does not result in any phase change, Point
N. This fluid is called a supercritical fluid.
Sublimation
Sublimation occurs when a solid goes directly to the gas phase
without passing through a liquid phase.

Solid carbon dioxide, dry ice at ambient pressure and temperature will
sublime.

Water ice on a cold, dry night will sublime from a roadway.

Sublimation is that causes ice cubes to shrink after a long time in the
freezer.
The vapor pressure of H2O at its triple point is about 10-2 bars, at a temperature of 273
K. The very volatile substances methane and nitrogen reach this same vapor pressure
at temperatures of only about 80 K and 50 K respectively.
Melting
Melting occurs when the energy of the system overcomes the intermolecular
interactions and the solid structure transitions to a liquid. This transition is
sharp for pure materials and less so for impure materials.
Melting Point of Straight Chain Hydrocarbons
Liquid — Vapor Equilibrium
A liquid at a constant temperature is in equilibrium with the vapor above it.
In this case, there are as many vapor molecules entering the liquid as there
molecules exiting the liquid. Mathematically, it means that the time
derivative of some measurable property goes to zero, i.e. things quit
changing.
When the temperature or pressure changes, the equilibrium point changes.
Compression Cycle
Vapor Pressure

The pressure exerted by the vapor above a liquid is called the vapor
pressure. It is usually denoted by p* and has units of pressure.

Vapour Pressure is a non linear function of temperature

Figure 1.3 shows the
logarithm of vapour pressure
plotted against an arbitrary
temperature scale for some
compounds.

The scale, which is an

adjusted reciprocal of the
absolute temperature, has
been selcted so that the vapour
pressures of water and most
hydrocarbons can be exhibited
by straight lines.

This plot is known as the Cox

chart.
A pure substance cannot exist as liquid
at a temperature above its critical
temperature.

Hence the vapour pressure values at

temperatures above the critical
temperatures, shown by | in Figure 1.3,
are not real, but simply extrapolated
values.
Figure shows the variation of saturated
fluid density with temperature for a
number of pure hydrocarbons.

All the compounds show a similar trend,

that is, the vapour and liquid densities
become equal at the critical point.

Other properties also show the same

trend.

The critical temperature, Tc, and the

critical pressure, Pc, are the maximum
temperature and pressure at which a
pure compound can form coexisting
phases.
The variation of saturated fluid density with
temperature for a pure compound is shown in
Figure.

The densities of vapour and liquid phases approach

each other as the temperature increases.

They become equal at conditions known as the

critical point.

All the differences between the phases are reduced

as the system approaches the critical point.

Indeed, the phases become the same and

indistinguishable at the critical point.
Figure shows the pressure versus volume
per mole weight (specific volume)
characteristics of a typical pure
hydrocarbon (e.g. propane).

Imagine in the following :

All changes occur isothermally (with no
heat flowing either into or out of the fluid)
and at the same temperature.

Initially the component is in the liquid

phase at 1000 psia, and has a volume of
about 2 ft3/lb.mol. (point A).

Expansion of the system (A to B) results

in large drops in pressure with small
increases in specific volume, due to the
small compressibility of liquids (liquid
hydrocarbons as well as liquid formation
waters have small compressibilities that
are almost independent of pressure for the
range of pressures encountered in
hydrocarbon reservoirs).
 On further expansion, a pressure will be
attained where the first tiny bubble of gas
appears (point B).
This is the bubble point or saturation pressure
for a given temperature.
Further expansion (B to C) now occurs at
constant pressure with more and more of the
liquid turning into the gas phase until no more
fluid remains.
The constant pressure at which this occurs is
called the vapour pressure of the fluid at a
given temperature.

Point C represents the situation where the last

tiny drop of liquid turns into gas, and is called
the dew point.
Further expansion now takes place in the
vapour phase (C to D).
The pistons in Figure demonstrate the changes in fluid phase schematically.
It is worth noting that the process A to B to C to D described above during expansion
(reducing the pressure on the piston) is perfectly reversible.
If a system is in state D, then application of pressure to the fluid by applying pressure to the
pistons will result in changes following the curve D to C to A.
We can examine the curve in Figure for a
range of fluid temperatures.

If this is done, the pressure-volume

relationships obtained can be plotted on a
pressure-volume diagram with the bubble
point and dew point locus also included.

Note that the bubble point and dew point

curves join together at a point (shown by
a dot in Figure). This is the critical point.

The region under the bubble point/dew

point envelope is the region where the
vapour phase and liquid phase can
coexist, and hence have an interface (the
surface of a liquid drop or of a vapour
bubble).

The region above this envelope represents

the region where the vapour phase and
liquid phase do not coexist.
Thus at any given constant low fluid
pressure, reduction of fluid volume will
involve the vapour condensing to a liquid
via the two phase region, where both liquid
and vapour coexist.

But at a given constant high fluid pressure

(higher than the critical point), a reduction
of fluid volume will involve the vapour
phase turning into a liquid phase without
any fluid interface being generated (i.e. the
vapour becomes denser and denser until it
can be considered as a light liquid).

Thus the critical point can also be viewed as

the point at which the properties of the
liquid and the gas become indistinguishable
(i.e. the gas is so dense that it looks like a
low density liquid and vice versa).
Bubble Point and Dew Point
●The dashed line on the G side of the phase envelope is called the
bubble point.
●On the right side HFL of the phase envelope the dashed line is called
the dew point.
●At these points, bubbles of vapor or droplets of liquid just begin to
form.
Suppose that we find the bubble
points and dew points for a range
of different temperatures, and plot
the data on a graph of pressure
against temperature. Figure 2.3
shows such a plot.

Note that the dew point and bubble

points are always the same for a
pure component, so they plot as a
single line until the peak of Figure
2.2 is reached, which is the critical
point.
Two-Component Systems
●Two component systems are considerably more complex than single
component systems.
●The liquid vapor line is no longer parallel to the x- axis.
●The composition of the liquid- vapor region is complicated by the presence of
different amounts of each component
Two-Component System — n-pentane and n-heptane(52.4%)
●The critical point on the chart below is the critical point of the
mixture.
●Notice that the critical point is not at the highest point on the liquid-
vapor envelope.
●Inside the left side of the envelope, the liquid is enriched in the
higher boiling point component and the vapor is enriched in the lower
boiling point component.
 Two-Component Systems
P-T Diagram
●Note that the dew-point curve extends past the critical point.
●The bubble-point curve also extends above the critical point.
●These two things make the behavior
of a multicomponent system in a reservoir complex.
●The cricondenbar is the highest pressure and the cricondentherm is
the highest temperature on the two-phase envelope.
Retrograde Behavior
●Point C is the critical point.
●Looking at a point just above point J and moving downward H decreasing
pressure L through point J, the system passes from the gas phase through the
dew-point line into the liquid-vapor equlibrium region.
●Moving downward along the same line eventually results in crossing the dew-
point line again.
●This results in a transition from a liquid to a vapor with a decrease in pressure!
●Point C is the critical point.
●Looking at point K and moving left decreasing temperature toward point L,
the system passes from the gas phase through the dew-point line into the
liquid-vapor equlibrium region.
●Moving left along the same line eventually results in crossing the dew-point
line again.
●This results in a transition from a liquid to a vapor with a decrease in
temperature!
Retrograde Behavior
●Retrograde behavior causes problems in the production of natural gas
from reservoirs that contain condensible components mixed with the
gas.

●Two phase flow in reservoirs is more difficult that single phase flow.

●The solution is to keep the pressure up in the reservoir by reinjecting

gas.
The phase rule indicates that in a binary vapour-liquid
system, both the temperature and the pressure are
independent variables.

The phase envelope, inside which the two phases coexist, is

bounded by the bubble point and dew point curves.

The two curves meet at the critical point (C), where all
differences between the two phases vanish and the phases
become indistinguishable.

Note that the two phases can coexist at some conditions

above the critical point.

The highest pressure (B) and the highest temperature (D) on

the phase envelope are called the cricondenbar and the
cricondentherm, respectively.
The pressure-volume diagram of a binary
mixture is schematically shown in Figure.

Note that the system pressure decreases during

an isothermal expansion between its bubble
and dew points, contrary to that for a pure
compound.
The phase diagram of a mixture is determined by
its composition.
Figure shows the phase diagram of ethane-
heptane system.

The critical temperature of different mixtures lies

between the critical temperatures of the two pure
compounds.

The critical pressure, however, exceeds the

values of both components as pure, in most cases.

The locus of critical points is shown by the

dashed line in Figures
The greater the difference between the critical points
of the two components, the higher the mixture
critical pressure can rise as shown in Figure.

No binary mixture can exist as a two-phase system

outside the region bounded by the locus of critical
points.
A typical phase diagram of multi-component
system at constant composition is shown in Figure.

Vapour and liquid phases coexist at any pressure-

temperature conditions within the phase envelope.

The liquid/mixture volumetric ratios are shown by

the constant quality lines.

Note that the distance between iso-volume or

quality lines decreases as the critical point is
approached.

Small pressure or temperature changes at a region

near the critical point cause major phase changes.
An isothermal reduction of pressure for a vapour-like fluid, Point
A, forms the first drop of liquid at the dew point, Point B.

Further reduction of pressure will result in further condensation,

as indicated by the quality lines.

This phenomenon is known as the retrograde condensation.

The condensation will cease at some point, Point D, and the

condensed phase will revaporise by further reduction of pressure.

The shaded region of the phase diagram, where pressure reduction

results in condensation is referred to as the retrograde region.

Note that the above behaviour occurs only if the gas temperature
lies between the critical temperature and the cricondentherm.

Figure shows that there are two dew point pressures at any
temperature for retrograde gases.

The upper dew point is sometimes called the retrograde dew

point.

The lower dew point is of little practical significance for most gas
condensate fluids.
The relative position of the critical point to the
cricondentherm and the cricondenbar on the
phase envelope can lead to other retrograde
phenomena.

Figure shows that an isobaric increase of

temperature from point 1 to point 2 results in
condensation.

This behaviour, which can also be called

retrograde condensation, is of little interest in
reservoir operations.

It indicates, however, that raising the temperature

of a high pressure rich gas may not be a proper
procedure to avoid condensation in fluid
handling.
The vaporisation of liquid by
isobaric temperature decrease,
shown in Figure by isothermal
pressure increase is known as
retrograde vaporisation.
Exceptional cases
An unusual
behaviour for a
naturally occurring
hydrocarbon
mixture as shown in
Figure.

Note that an
isothermal
reduction of
pressure, e.g. at
160°F results in an
increase of the
liquid volume after
an initial normal
behaviour.
A similar behaviour has also been
reported for a multicomponent
hydrocarbon oil, as shown in Figure.

Note that the gas/liquid volumetric ratio

increases initially below the bubble
point, as expected.

The trend reverses over a limited

pressure range, prior to behaving
normally again.

The calculated gas to liquid ratio in

molar term is shown also in Figure.

The ratio increases very gradually over

the whole tested pressure range, without
any peculiarity.

The reason for the apparent

disagreement between the two plots, is
the change in molar volumes of the two
phases.