Classical thermodynamics is the only physical theory of universal content,
which I am convinced, will never be overthrown. - Albert Einstein
Chapter 3
Properties of Pure Substances
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The objectives of Chapter 3 are to:
• 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.
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3.1 Pure Substances
A substance that has a fixed chemical composition throughout
is called a pure substance.
Fig. 3-1 Nitrogen and gaseous Fig. 3–2 A mixture of liquid and gaseous
air are pure substances. water is a pure substance, but a mixture of
liquid and gaseous air is not.
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3.2 Phases of a Pure Substance
A phase is identified as having a distinct molecular arrangement
that is homogeneous throughout and separated from the others
by easily identifiable boundary surfaces.
Fig. 3–3 The molecules in a solid are kept at their positions by the large springlike
intermolecular forces.
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3.2 Phases of a Pure Substance
Fig. 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 at random in the gas
phase.
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3.3 Phase change process of pure substances
Compressed liquid Saturated liquid
Fig. 3–6 At 1 atm pressure and 100°C, water
Fig. 3–5 At 1 atm and 20°C, water exists
exists as a liquid that is ready to vaporize
in the liquid phase (compressed liquid).
(saturated liquid).
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3.3 Phase change process of pure substances
Saturated liquid vapor mixture Saturated vapor
Fig. 3–7 As more heat is Fig. 3–8 At 1 atm pressure, the
transferred, part of the saturated temperature remains constant at 100°C
liquid vaporizes (saturated liquid– until the last drop of liquid is vaporized
vapor mixture). (saturated vapor). 8
3.3 Phase change process of pure substances
Superheated Vapor
Fig. 3–9 As more heat is transferred, the
temperature of the vapor starts to rise (superheated
vapor). 9
3.3 Phase change process of pure substances
Fig. 3–10 T-v diagram for the heating process of water at constant pressure.
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3.3 Phase change process of pure substances
Saturation temperature and saturation pressure
Fig. 3–11 The liquid–vapor saturation curve of
a pure substance (numerical values are for
water).
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3.4 Property diagrams for phase change processes
Fig. 3–12 T-v diagram of constant-pressure phase-change processes of a pure substance at
various pressures (numerical values are for water). 12
3.4 Property diagrams for phase change processes
Fig. 3–13 At supercritical pressures (P > Pcr), there is no distinct phase-change (boiling) process.
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3.4 Property diagrams for phase change processes
Fig. 3–14 T-v diagram of a pure substance.
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3.4 Property diagrams for phase change processes
Fig. 3–15 P-v diagram of a pure substance.
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3.4 Property diagrams for phase change processes
Fig. 3–16 At triple-point pressure and temperature, a substance
exists in three phases in equilibrium.
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3.4 Property diagrams for phase change processes
Fig. 3–17 At low pressures (below the triple-point value), solids evaporate without
melting first (sublimation).
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3.4 Property diagrams for phase change processes
Fig. 3–18 P-T diagram of pure substances.
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3.5 Property tables
Saturated liquid and saturated vapor states
Fig. 3–19 A partial list of Table A–4. 19
3.5 Property tables
Saturated liquid–vapor
mixture
Fig. 3–20 The relative amounts of liquid and vapor
phases in a saturated mixture are specified by the
quality x.
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3.5 Property tables
Saturated liquid–vapor mixture
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3.5 Property tables
Superheated vapor
Fig. 3–21 A partial listing of Table A–6.
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3.5 Property tables
Superheated vapor
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3.5 Property tables
Compressed liquid
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3.6 The ideal gas equation of state
In 1802, J. Charles and J. Gay-Lussac, Frenchmen, experimentally
determined that at low pressures the volume of a gas is proportional
to its temperature. That is,
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3.6 The ideal gas equation of state
Fig. 3–22 Different substances have
different gas constants.
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3.6 The ideal gas equation of state
The mass of a system is equal to the product of its molar mass M
and the mole number N:
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