Thermodynamics:
An Engineering Approach
9th Edition
Yunus A. Cengel, Michael A. Boles,
Mehmet Kanoglu
McGraw-Hill Education, 2019
Chapter 3
PROPERTIES OF
PURE
SUBSTANCES
Copyright © McGraw-Hill Education. Permission
required for reproduction or display.
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.
2
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.
FIGURE 3–1
Nitrogen and gaseous air are
pure substances. FIGURE 3–2
A mixture of liquid and gaseous water
is a pure substance, but a mixture of
liquid and gaseous air is not.
3
FIGURE 3–3
PHASES OF A PURE The molecules
SUBSTANCE in a solid are
kept at their
positions by the
large springlike
inter-molecular
forces.
FIGURE 3–4
The arrangement of atoms in different phases: (a) molecules are at
relatively fixed positions in a solid, (b) groups of molecules move
about each other in the liquid phase, and (c) molecules move about
4
at random in the gas phase..
PHASE-CHANGE PROCESSES
OF PURE SUBSTANCES
Compressed liquid
(subcooled liquid):
A substance that it is not
about to vaporize
FIGURE 3–5
At 1 atm and 20°C, water exists in the
liquid phase (compressed liquid). 5
Saturated liquid:
A liquid that is
about to vaporize
FIGURE 3–6
At 1 atm pressure and 100°C, water
exists as a liquid that is ready to
vaporize (saturated liquid).
6
Saturated liquid–vapor
mixture: The state at which
the liquid and vapor phases
coexist in equilibrium.
FIGURE 3–7
As more heat is transferred, part of the
saturated liquid vaporizes (saturated
liquid–vapor mixture).
7
Saturated vapor: A vapor
that is about to condense.
FIGURE 3–8
At 1 atm pressure, the temperature
remains constant at 100°C until
the last drop of liquid is vaporized
(saturated vapor). 8
Superheated vapor: A
vapor that is not about
to condense (i.e., not a
saturated vapor).
FIGURE 3–9
As more heat is transferred, the
temperature of the vapor starts to rise
(superheated vapor).
9
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.
FIGURE 3–10
T-v diagram for the
heating process of
water at constant
pressure.
10
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 100C 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 FIGURE 3–11
substance changes phase at The liquid–vapor saturation curve of a
a given temperature. pure substance (numerical values are
for water).
11
12
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. 13
Some
Consequences
of Tsat and Psat
Dependence
FIGURE 3–12
The temperature of liquid nitrogen
exposed to the atmosphere remains
constant at −196°C, and thus it
maintains the test chamber at −196°C.
14
FIGURE 3–13
The variation of the temperature of fruits
and vegetables with pressure during vacuum
cooling from 25°C to 0°C.
15
FIGURE 3–14
In 1775, ice was made by evacuating
the airspace in a water tank.
16
PROPERTY DIAGRAMS FOR The variations of
properties during
PHASE-CHANGE PROCESSES 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.
FIGURE 3–15
T-v diagram of
constant-pressure
phase-change
processes of a pure
substance at various
pressures
(numerical values
are for water). 17
Critical point: The
point at which the
saturated liquid and
saturated vapor states
are identical.
FIGURE 3–16
At supercritical pressures (P > Pcr),
there is no distinct phase-change
(boiling) process.
18
Saturated liquid line
Saturated vapor line
Compressed liquid
region
Saturated liquid–
vapor mixture region
(wet region)
Superheated vapor
region
FIGURE 3–17
Property diagrams of a pure substance.
19
FIGURE 3–18
The pressure in a piston–cylinder
device can be reduced by reducing
the weight of the piston.
FIGURE 3–17
Property diagrams of a pure substance.
20
Extending the
Diagrams to Include
the Solid Phase
FIGURE 3–19
P-v diagrams of different substances.
21
For water,
Ttp = 0.01°C
Ptp = 0.6117 kPa
FIGURE 3–20
At triple-point pressure and
temperature, a substance exists in
three phases in equilibrium.
22
Sublimation: Passing from the
solid phase directly into the
vapor phase.
FIGURE 3–21
At low pressures (below the triple-
point value), solids evaporate without
melting first (sublimation).
23
Phase Diagram
FIGURE 3–22
P-T diagram of pure substances.
24
The P-v-T surfaces present a great deal of information at once, but in a
thermodynamic analysis it is more convenient to work with two-dimensional
diagrams, such as the P-v and T-v diagrams.
FIGURE 3–23 FIGURE 3–24
P-v-T surface of a substance that P-v-T surface of a substance that
contracts on freezing. expands on freezing (like water).
25
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.
26
27
Enthalpy—A Combination Property
FIGURE 3–25
The combination u + Pv is often
encountered in the analysis of control FIGURE 3–26
volumes. The product pressure X volume
has energy units.
28
Saturated Liquid
and Saturated
Vapor States
FIGURE 3–27
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.
29
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.
30
FIGURE 3–28
Schematic and T-v diagram for Example 3–1.
FIGURE 3–30
Schematic and P-v diagram for
Example 3–3.
Examples: Saturated
liquid and saturated
vapor states of water on
FIGURE 3–29 T-v and P-v diagrams.
Schematic and P-v diagram for Example 3–2. 31
32
33
34
35
36
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.
FIGURE 3–31
The relative amounts of liquid and
vapor phases in a saturated mixture
Temperature and are specified by the quality x.
pressure are dependent
properties for a mixture.
37
FIGURE 3–32
A two-phase system can be treated
as a homogeneous mixture for
convenience.
38
FIGURE 3–33
Quality is related to the horizontal
y v, u, or h
distances on P-v and T-v diagrams.
39
FIGURE 3–34
The v value of a saturated liquid–
vapor mixture lies between the vf and
vg values at the specified T or P.
40
41
42
43
44
45
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.
FIGURE 3–39
In this region, temperature and pressure At a specified P, superheated vapor
are independent properties. exists at a higher h than the saturated
vapor (Example 3–7).
46
FIGURE 3–37
A partial listing of Table A–6.
47
48
49
50
Compressed Compressed liquid is characterized by
Liquid
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
FIGURE 3–41
Schematic and T-u diagram for
Example 3–8.
51
FIGURE 3–40
A compressed liquid may be
approximated as a saturated liquid at
the given temperature.
52
FIGURE 3–42
At a given P and T, a pure substance
will exist as a compressed liquid if
T < Tsat @ P.
53
54
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.
55
56
57
58
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
59
FIGURE 3–43
Different substances have different
gas constants.
60
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
FIGURE 3–44
pressure, high temperature). Properties per unit mole are denoted
with a bar on the top.
61
62
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.
63
FIGURE 3–46
Percentage of error
([∣vtable – videal∣/vtable] × 100)
involved in assuming steam to be an
ideal gas, and the region where steam
can be treated as an ideal gas with less
than 1 percent error.
64
COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
Compressibility factor Z A factor that accounts for
the deviation of real gases from ideal-gas behavior
at a given temperature and pressure.
FIGURE 3–47
The compressibility factor is
unity for ideal gases.
65
The farther away Z is from unity, the more the gas deviates from ideal-
gas behavior.
Gases behave as an ideal gas at low densities (i.e., low pressure, high
temperature).
Question: What is the criteria for low pressure and high temperature?
Answer: The pressure or temperature of a gas is high or low relative
to its critical temperature or pressure.
FIGURE 3–49
At very low pressures, all gases
approach ideal-gas behavior
(regardless of their temperature).
66
Reduced Pseudo-
Reduced
temperature reduced
pressure
specific
volume
FIGURE 3–48
Comparison of Z factors for various gases. 67
FIGURE 3–50 FIGURE 3–51
Gases deviate from the ideal-gas The compressibility factor can also
behavior the most in the neighborhood be determined from a knowledge
of the critical point. of PR and vR.
68
69
OTHER EQUATIONS OF STATE
The ideal-gas equation of state
is very simple, but its range of
applicability is limited.
It is desirable to have
equations of state that
represent the P-v-T behavior of
substances accurately over a
larger region with no
limitations.
Such equations are naturally
more complicated.
Several equations have been
proposed. FIGURE 3–54
Several equations of state have been
proposed throughout history.
70
van der Waals Equation of State
This model includes two effects not
considered in the ideal-gas model:
- the intermolecular attraction forces
- the volume occupied by the
molecules themselves.
The accuracy of the van der Waals FIGURE 3–55
equation of state is often inadequate. Critical isotherm of a pure substance
has an inflection point at the critical
state.
71
Beattie-Bridgeman Equation of State
The constants are given in Table 3–4
for various substances. It is known to
be reasonably accurate for densities up
to about 0.8cr.
72
Benedict-Webb-Rubin Equation of State
The constants are given in Table 3–4.
This equation can handle substances at densities up to about 2.5 cr.
Virial Equation of State
The coefficients a(T), b(T), c(T), and so on, that are
functions of temperature alone are called virial coefficients.
73
74
FIGURE 3–56
Complex equations of state represent
the P-v-T behavior of gases more
accurately over a wider range. 75
FIGURE 3–57
Percentage of error involved in various equations of state for nitrogen
(% error = [(∣vtable – vequation∣)/vtable] × 100). 76
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
77
