CHAPTER II

PROPERTIES OF PURE
SUBSTANCE
 Content
• Pure substance

• Fixing the state of a simple pure substance

• P-V-T diagram

• Thermodynamic Tables

• Equation of State
 2.1 Pure substance
• A substance that has a fixed chemical
composition throughout is called a pure
substance.
Example: Water, nitrogen, air, helium,
carbon dioxide etc.
• Pure substance may exist in different
phases, but the chemical compositions is
the same.
For example water made up of two atoms
of hydrogen and one atom oxygen.
• It will have the same composition when
in ice, liquid and vapor forms.
• But, a mixture of liquid air and gaseous air is
not a pure substance, because the composition of
the liquid phase is different from that of the vapor
phase.
2.2 Fixing the state of a simple pure
substance
• The number of properties required to fix the state
of a system is given by the state postulates.
• The state postulate for a simple pure substance
state that, equilibrium state can be determined by
specifying any two independent intensive
properties.
 Phase of pure substances
• A phase is identified as having a distinct
molecular arrangement that is homogenous
throughout and separated from the others by
easily identifiable boundary surface.
• Under different conditions a substance may
appear in different phases.
• The three principal phases are solid, liquid and
gas.
• Considering water, it can be exist as
▪ Pure solid phase (ice)
▪ Pure liquid phase
▪ Pure vapor phase (steam)
• It can also exist as an equilibrium mixture of
different phase.
 Phase-change processes of pure
substances
• Consider the piston-cylinder device containing liquid water at
20oC and 1atm.

Figure 2.1 At 1atm and 20°C, water exists in

the liquid phase (compressed liquid).

• Under these conditions, water exists in the liquid phase, and it

is called a compressed liquid, or a sub cooled liquid-it is not
about to vaporize.
• As the temperature rises, the liquid water expands slightly,
and so its specific volume increases.
Figure 2.2 At 1atm pressure and 100°C,
water exists as a liquid that is ready to vaporize
(saturated liquid).

• At this point water still a liquid, but any heat

addition will cause some of the liquid to vaporize.
• That is, a phase change process from liquid to
vapor is about to take place.
• A liquid about to vaporize is called saturated
liquid.
 Figure 2.3 As more heat is transferred,
part of the saturated liquid vaporizes
(saturated liquid–vapor mixture).

• Once boiling starts, the temperature stops rising until

the liquid is completely vaporized (it is a constant
phase - change process at p constant).
• During this process the only thing is change in
volume.
• At this stage liquid and vapor phase coexist in
equilibrium and it is called saturated liquid-vapor
mixture.
 Figure 2.4 At 1atm pressure, the temperature
remains constant at 100°C until the last drop of
liquid is vaporized (saturated vapor).

• At this point, the entire cylinder is filled with vapor

that is on the borderline of the liquid phase.
• Any heat loss from this vapor will cause some of the
vapor to condense (phase change from vapor to
liquid).
• The vapor that is about to condense is called a
saturated vapor.
 Figure 2.5 As more heat is transferred,
the temperature of the vapor starts to rise
(superheated vapor).

• At this stage the phase-change process is completed,

back to a single-phase region (vapor).
• Further transfer of heat will result in an increase in
both the temperature and the specific volume.
• A vapor that is not about to condense (i.e. not a
saturated vapor) is called a superheated vapor.
• The above process is shown on a T-V diagram at
constant pressure.
• At a given pressure, the temperature at which a
pure substance changes phase is called the
saturation temperature Tsat.
• Likewise, at a given temperature, the pressure
at which a pure substance changes phases is
called the saturation pressure Psat.
• At a pressure of 101.325 kPa, the saturation
temperature is 99.97oC.
• Conversely, at a temperature of 99.97oC, a
saturation pressure is, 101.325 kPa.
• The amount of energy absorbed or released
during a phase-change process is called the
latent heat.
• More specifically, the amount of energy absorbed
during melting is called the latent heat of fusion
and is equivalent to the amount of energy released
during freezing.
• Similarly, the amount of energy absorbed during
vaporization is called the latent heat of
vaporization and is equivalent to the energy
released during condensation.
• During a phase-change process, pressure and
temperature are obviously dependent properties,
and there is a definite relation between them, that
is, Tsat=f (Psat).
 Figure 2.7 Liquid–vapor saturation curve. (water)

• A curve of this kind is characteristic of all pure

substances.
 2.3 Property Diagrams for Phase-
change Processes
• The variations of properties during phase-change
processes are best studied and understood with the
help of property diagrams.
• Next, we develop and discuss the T-v, P-v, P-T
(2D) and P-V-T (3D) diagrams for pure
substances.
Figure 2.8 p–v–T surface and projections for a substance that expands on freezing. (a)
Three-dimensional view. (b) Phase diagram. (c) p–v diagram.
Figure 2.9 p–v–T surface and projections for a substance that contracts
on freezing. (a) Three-dimensional view. (b) Phase diagram. (c) p–v diagram.
2.4 The T-v Diagram
• Experimental result tells us, as the pressure is
increased further, the saturation line of the
process will continue to get shorter and it will
become a point.
• This point is called critical point of the
substance and it may be defined as the point at
which the saturated liquid and saturated vapor
states are identical
• At pressures above the critical pressure, there is not a
distinct phase-change (boiling) process.
• Instead, the specific volume of the substance
continually increases, and at all times there is only
one phase present.
• Eventually, it resembles a vapor, but we can
never tell when the change has occurred.
• Above the critical state, there is no line that
separates the compressed liquid region and the
superheated vapor region.
• However, it is customary to refer to the
substance as superheated vapor at
temperatures above the critical temperature
and as compressed liquid at temperatures
below the critical temperature.
The P-V diagram
It is the same as T-V diagram but the T-constant
line on this diagram have a down ward trend
 The pressure in a piston–cylinder
device can be reduced by reducing
the weight of the piston.

The P-T diagram

This diagram is often called the phase diagram
since all three phases are separated from each
other by three lines.
Melting and Sublimation
• There are two ways a substance can pass from the
solid to vapor phase:
▪ either it melts first into a liquid and subsequently
evaporates, or
▪ it evaporates directly without melting first.
➢Let us consider the piston/cylinder arrangement.
Suppose that the cylinder contains 1 kg of ice at -
20oC, 100 kPa.
• When heat is transferred to the ice, the pressure
remains constant, the specific volume increases
slightly, and the temperature increases until it
reaches 0oC, at which point the ice melts and the
temperature remains constant.
• In this state the ice is called a saturated solid.
➢ If the initial pressure of the ice at -20oC is 0.260
kPa, heat transfer to the ice results in an increase
in temperature to -10oC.
• At this point, however, the ice passes directly from
the solid phase to the vapor phase in the process
known as sublimation.
• Further heat transfer results in superheating of the
vapor.
➢Finally, consider an initial pressure of the ice of
0.6113 kPa and a temperature of -20oC.
• Through heat transfer, let the temperature increase
until it reaches 0.01oC.
• At this point, however, further heat transfer may
cause some of the ice to become vapor and some to
become liquid, for at this point it is possible to
have the three phases in equilibrium.
• This point is called the triple point, defined as the
state in which all three phases may be present in
equilibrium.
This whole matter is best summarized in the
following figure.
• Consider a solid in state A, as shown in above figure.
• When the temperature increases but the pressure (which
is less than the triple-point pressure) is constant, the
substance passes directly from the solid to the vapor
phase.
• Along the constant-pressure line EF, the substance
passes from the solid to the liquid phase at one
temperature and then from the liquid to the vapor phase
at a higher temperature.
• The constant-pressure line CD passes through the triple
point, and it is only at the triple point that the three
phases may exist together in equilibrium.
• At a pressure above the critical pressure, such as GH,
there is no sharp distinction between the liquid and
vapor phases.
 2.4 Thermodynamic Property tables
• Thermodynamic properties of pure substance are
usually given in tabular form to facilitate system
analysis. Among them compressed liquid,
saturated, and superheated steam are most
commonly used.
 Saturated Liquid–Vapor Mixture
• During a vaporization process, a substance exists
as part liquid and part vapor. That is, it is a
mixture of saturated liquid and saturated vapor
(Fig. 3–34).
• To analyze this mixture properly, we need to
know the proportions of the liquid and vapor
phases in the mixture.
• This is done by defining a new property called the
quality x as the ratio of the mass of vapor to the
total mass of the mixture:
• Quality has significance for saturated mixtures
only. It has no meaning in the compressed liquid
or superheated vapor regions.
• Its value is between 0 and 1.
• The quality of a system that consists of saturated
liquid is 0 (or 0 percent), and the quality of a
system consisting of saturated vapor is 1 (or 100
percent).
• In saturated mixtures, quality can serve as one of
the two independent intensive properties needed
to describe a state.
• Note that the properties of the saturated liquid are
the same whether it exists alone or in a mixture
with saturated vapor.
• During the vaporization process, only the
amount of saturated liquid changes, not its
properties.
• The same can be said about a saturated vapor.
• It is often more convenient to imagine that the
two phases are mixed well, forming a
homogeneous mixture.
• Consider a tank that contains a saturated
liquid–vapor mixture.
• The volume occupied by saturated liquid is Vf,
and the volume occupied by saturated vapor is
Vg.
• The total volume V is the sum of the two:
Dividing by mt yields

This relation can also be expressed as

Solving for quality, we obtain
Saturated Liquid and Saturated Vapor
States
• The properties of saturated liquid and saturated
vapor for water are listed in thermodynamic
property tables.
There are two tables
• Temperature table and
• Pressure table
 Superheated Vapor Table
• In the region to the right of the saturated vapor
line and at temperatures above the critical
point temperature, a substance exists as
superheated vapor.
• Since the superheated region is a single-phase
region (vapor phase only), temperature and
pressure are no longer dependent properties
and they can conveniently be used as the two
independent properties in the tables.
 Compressed Liquid Table
• Compressed liquid tables are not as commonly
available.
• One reason for the lack of compressed liquid
data is the relative independence of
compressed liquid properties from pressure.
• Compressed liquid properties depend on
temperature much more strongly than they do
on pressure.
• In the absence of compressed liquid data, a
general approximation is to treat compressed
liquid as saturated liquid at the given
temperature.
 2.5 Equation of State
• Any equation that relates the pressure, temperature,
and specific volume of a substance is called an
equation of state.
• Property relations that involve other properties of a
substance at equilibrium states are also referred to as
equations of state.
• There are several equations of state, some simple and
others very complex.
• The simplest and best-known equation of state for
substances in the gas phase is the ideal-gas equation
of state.
• This equation predicts the P-v-T behavior of a gas
quite accurately within some properly selected region.
• Equation of state for an ideal gas is given by:

• Known as ideal gas equation of state or simply the

ideal-gas relation, and a gas that obeys this
relation is called an ideal gas.
• It is also given by:

•
• The gas constant R is different for each gas
and is determined from
• Where Ru is the universal gas constant and M is
the molar mass (also called molecular weight) of
the gas. The constant Ru is the same for all
substances, and its value is 8.314kJ/kmol∙K.

• The ideal-gas equation of state can be written in

several different forms

• For a fixed mass and simplifying, the properties of

an ideal gas at two different states are related to
each other by
• Air, nitrogen, oxygen, hydrogen, helium, argon
etc can be treated as ideal gases.
 Compressibility Factor—a Measure of
Deviation From Ideal-gas Behavior
• The ideal-gas equation is very simple and thus very
convenient to use.
• However, gases deviate from ideal-gas behavior
significantly at states near the saturation region and
the critical point.
• This deviation from ideal-gas behavior at a given
temperature and pressure can accurately be
accounted for by the introduction of a correction
factor called the compressibility factor Z defined
as:
• Obviously, Z = 1 for ideal gases. For real gases Z
can be greater than or less than unity.
• The Z factor for all gases is approximately the
same at the same reduced pressure and
temperature.
• This is called the principle of corresponding
states.
• Temperatures and pressures normalized with
respect to their critical temperatures and pressures.

• Here, PR is called the reduced pressure and TR the

reduced temperature.
• Z values are plotted against PR and TR for several
gases.
 EXAMPLES
3.1. A rigid tank contains 50 kg of saturated
liquid water at 90°C. Determine the
pressure in the tank and the volume of the tank.
3.2. A mass of 200 g of saturated liquid water is
completely vaporized at a constant pressure of
100kPa. Determine (a) the volume change and
(b) the amount of energy transferred to the
water.
3.3. A rigid tank contains 10000 g of water at 90°C.
If 8000 g of the water is in the liquid form and the
rest is in the vapor form, determine (a) the pressure
in the tank and (b) the volume of the tank.
 quiz
A rigid tank contains 12 kg of water at 90°C. If 3
kg of the water is in the liquid form and the rest
is in the vapor form, determine (a) the pressure
in the tank and (b) the volume of the tank and
amount of energy transferred to the water.