CHAPTER
3
Properties of Pure
Substances
1. Pure Substance
2. Phases of a Pure Substance
3. Phase-Change Processes of Pure Substances
4. Property Diagram for Phase-Change Processes
5. Property Tables
6. The Ideal-Gas Equation of State
7. Compressibility Factor-A Measure of Deviation
from Ideal-Gas Behavior
8. Other Equation of State
2022 Spring semester
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Objectives
• Introduce the concept of a pure substance.
• Discuss the physics of phase-change processes.
• Illustrate the P-v, T-v, and P-T property diagrams and P-v-T
surfaces of pure substances.
• Demonstrate the procedures for determining thermodynamic
properties of pure substances from tables of property data.
• Describe the hypothetical substance “ideal gas” and the
ideal-gas equation of state.
• Apply the ideal-gas equation of state in the solution of typical
problems.
• Introduce the compressibility factor, which accounts for the
deviation of real gases from ideal-gas behavior.
• Present some of the best-known equations of state.
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3-1 PURE SUBSTANCE
Pure substance: A substance that has a fixed chemical
composition throughout.
Air is a mixture of several gases, but it is considered to
be a pure substance.
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3-2. PHASES OF A PURE SUBSTANCE
The molecules
in a solid are
kept at their
positions by the
large springlike
inter-molecular
forces.
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3-3. PHASE-CHANGE PROCESSES
Compressed liquid
(subcooled liquid):
A substance that it is not
about to vaporize
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3-3. PHASE-CHANGE PROCESSES
Saturated liquid:
A liquid that is
about to vaporize
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3-3. PHASE-CHANGE PROCESSES
Saturated liquid–vapor
mixture: The state at which
the liquid and vapor phases
coexist in equilibrium.
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3-3. PHASE-CHANGE PROCESSES
Saturated vapor: A vapor
that is about to condense.
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3-3. PHASE-CHANGE PROCESSES
Superheated vapor: A
vapor that is not about
to condense (i.e., not a
saturated vapor).
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3-3. PHASE-CHANGE PROCESSES
If the entire process between state 1 and 5 is reversed by cooling the water
while maintaining the pressure at the same value, the water will go back to
state 1, retracing the same path, and in so doing, the amount of heat released
will exactly match the amount of heat added during the heating process.
T-v diagram for the
heating process of
water at constant
pressure.
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3-3. PHASE-CHANGE PROCESSES
Saturation Temperature and Saturation Pressure
The temperature at which water starts
boiling depends on the pressure;
therefore, if the pressure is fixed, so is
the boiling temperature.
Water boils at 100°C at 1 atm
pressure.
Saturation temperature Tsat: The
temperature at which a pure
substance changes phase at a given
pressure.
Saturation pressure Psat: The
pressure at which a pure substance
changes phase at a given
temperature.
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3-3. PHASE-CHANGE PROCESSES
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3-3. PHASE-CHANGE PROCESSES
Latent heat: The amount of energy absorbed or
released during a phase-change process.
Latent heat of fusion: The amount of energy
absorbed during melting. It is equivalent to the
amount of energy released during freezing.
Latent heat of vaporization: The amount of
energy absorbed during vaporization and it is
equivalent to the energy released during
condensation.
The magnitudes of the latent heats depend on
the temperature or pressure at which the phase
change occurs.
At 1 atm pressure, the latent heat of fusion of
water is 334 kJ/kg and the latent heat of
vaporization is 2257 kJ/kg.
The atmospheric pressure, and thus the boiling
temperature of water, decreases with elevation.
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3-4. 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 such as the T-v, P-v,
and P-T diagrams for pure
substances.
T-v diagram of constant-
pressure phase-change
processes of a pure substance
at various pressures (numerical
values are for water).
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3-4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES
Critical point: The
point at which the
saturated liquid and
saturated vapor states
are identical.
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3-4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES
Saturated liquid line
Saturated vapor line
Compressed liquid region
Saturated liquid–vapor
mixture region (wet
region)
Superheated vapor
region
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3-4. PROPERTY DIAGRAMS FOR PHASE-
CHANGE PROCESSES
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3-5. PROPERTY TABLES
For most substances, the relationships among
thermodynamic properties are too complex to be
expressed by simple equations.
Therefore, properties are frequently presented in the
form of tables.
Some thermodynamic properties can be measured
easily, but others cannot and are calculated by using the
relations between them and measurable properties.
The results of these measurements and calculations are
presented in tables in a convenient format.
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3-5. PROPERTY TABLES
Enthalpy—A Combination Property
The product pressure ´ volume
has energy units.
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3-5. PROPERTY TABLES
Saturated Liquid and Saturated Vapor States
A partial list of Table A–4. Table A–4: Saturation properties of
water under temperature.
Table A–5: Saturation properties of
water under pressure.
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3-5. PROPERTY TABLES
Enthalpy of vaporization,
(Latent heat of vaporization) hfg
The amount of energy needed to vaporize a unit
mass of saturated liquid at a given temperature or
pressure.
It represents the amount of energy needed to
vaporize a unit mass of saturated liquid at a given
temperature or pressure.
It decreases as the temperature or pressure
increases and becomes zero at the critical point.
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3-5. PROPERTY TABLES
Examples: Saturated liquid and
saturated vapor states of water on T-v
and P-v diagrams.
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3-5. PROPERTY TABLES
Saturated Liquid–Vapor Mixture
Quality, x : The ratio of the mass of
vapor to the total mass of the mixture.
Quality is between 0 and 1
0: sat. liquid, 1: sat. vapor.
The properties of the saturated liquid
are the same whether it exists alone
or in a mixture with saturated vapor.
Temperature and pressure are
dependent properties for a mixture.
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3-5. PROPERTY TABLES
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3-5. PROPERTY TABLES
y v, u, or h
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3-5. PROPERTY TABLES
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3-5. PROPERTY TABLES
Examples: Saturated liquid-vapor
mixture states on T-v and P-v diagrams.
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3-5. PROPERTY TABLES
Superheated Vapor
Compared to saturated vapor, superheated
vapor is characterized by
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.
In this region, temperature and pressure
are independent properties.
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3-5. PROPERTY TABLES
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3-5. PROPERTY TABLES
Compressed Liquid Compressed liquid is characterized by
The compressed liquid
properties depend on
temperature much more
strongly than they do on
pressure.
y ® v, u, or h
A more accurate relation for h
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3-5. PROPERTY TABLES
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3-5. PROPERTY TABLES
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3-5. PROPERTY TABLES
Reference State and Reference Values
The values of u, h, and s cannot be measured directly, and they are
calculated from measurable properties using the relations between properties.
However, those relations give the changes in properties, not the values of
properties at specified states.
Therefore, we need to choose a convenient reference state and assign a
value of zero for a convenient property or properties at that state.
The reference state for water is 0.01°C and for R-134a is -40°C in tables.
Some properties may have negative values as a result of the reference state
chosen.
Sometimes different tables list different values for some properties at the
same state as a result of using a different reference state.
However, In thermodynamics we are concerned with the changes in
properties, and the reference state chosen is of no consequence in
calculations.
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3-5. PROPERTY TABLES
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3-6. THE IDEAL-GAS EQUATION OF STATE
Equation of state: Any equation that relates the pressure,
temperature, and specific volume of a substance.
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.
Ideal gas
equation of state
R gas constant
M molar mass (kg/kmol)
Ru universal gas constant
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3-6. THE IDEAL-GAS EQUATION OF STATE
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3-6. THE IDEAL-GAS EQUATION OF STATE
Mass = Molar mass ´ Mole number
Various expressions of
ideal gas equation
Ideal gas equation at
two states for a fixed
mass
Real gases behave as an ideal
gas at low densities (i.e., low
pressure, high temperature).
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3-6. THE IDEAL-GAS EQUATION OF STATE
Is Water Vapor an Ideal Gas?
At pressures below 10 kPa, water vapor can be
treated as an ideal gas, regardless of its temperature,
with negligible error (less than 0.1 percent).
At higher pressures, the ideal gas assumption yields
unacceptable errors, particularly in the vicinity of the
critical point and the saturated vapor line.
In air-conditioning applications, the water vapor in the
air can be treated as an ideal gas. Why?
In steam power plant applications, however, the
pressures involved are usually very high; therefore,
ideal-gas relations should not be used.
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3-6. THE IDEAL-GAS EQUATION OF STATE
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Summary
Pure substance
Phases of a pure substance
Phase-change processes of pure substances
Property diagrams for phase change
processes
Property tables
The ideal gas equation of state
Compressibility factor
Other equations of state
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