Lec 9

Thermodynamics - I
Lecture 9
Pure Substance, Phase Change, Property Diagrams

(Ch-3)
Abdullah Jamil
School of Mechanical & Manufacturing Engineering
National University of Sciences & Technology
Objectives
• Introduce the concept of a pure substance.
• Discuss the physics of phase-change processes.
• Illustrate the P-v, T-v property diagrams 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.
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 as long as the mixture is homogeneous
Nitrogen and gaseous air are

pure substances. A mixture of liquid and gaseous
water is a pure substance, but a
• Mixture of oil and water mixture of liquid and gaseous air
is not pure substance is not.
3
PHASE
• Phase: Quantity of matter that is homogeneous
throughout in both chemical composition and physical
structure
A system of liquid water and water vapour (steam): 2 phases
A system of liquid water and ice: 2 phases
A system consists of mixture of oxygen and nitrogen: 1 phase
A system consists of mixture of oil and water: 2 phases
4
PHASES OF A PURE SUBSTANCE
The molecules
in a solid are
kept at their
positions by the
large springlike
inter-molecular
forces. In a solid, the attractive
and repulsive forces
between the molecules
tend to maintain them
at relatively constant
distances from each
other.
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. 5
PHASE-CHANGE PROCESSES OF PURE
SUBSTANCES
• Compressed liquid (subcooled liquid): A substance that it
is not about to vaporize.
• Saturated liquid: A liquid that is about to vaporize.
At 1 atm and 20°C,

water exists in the
liquid phase
(compressed liquid).
At 1 atm pressure
and 100°C, water
exists as a liquid
that is ready to
vaporize
(saturated liquid).
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• Saturated vapor: A vapor that is about to condense.
• Saturated liquid–vapor mixture: The state at which the liquid and
vapor phases coexist in equilibrium.
• Superheated vapor: A vapor that is not about to condense (i.e., not a
saturated vapor).
As more heat is transferred, At 1 atm pressure, the As more heat is

part of the saturated liquid temperature remains transferred, the
vaporizes (saturated liquid– constant at 100°C until the temperature of the
vapor mixture). last drop of liquid is vaporized vapor starts to rise
(saturated vapor). (superheated vapor).
7
If the entire process between state 1 and 5 described in the figure 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.
8
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.
The liquid–
vapor
saturation
curve of a
pure
substance
(numerical
values are for
water).
9
• 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 333.7 kJ/kg and the
latent heat of vaporization is 2256.5 kJ/kg.
• The atmospheric pressure, and thus the
boiling temperature of water, decreases
with elevation.
10
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 and P-v 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). 11
• saturated liquid line
• saturated vapor line
• compressed liquid region
• superheated vapor region
• saturated liquid–vapor
mixture region (wet region)
T-v diagram of a pure substance.

At supercritical
Critical point: The point
pressures (P > Pcr),
at which the saturated
there is no distinct
liquid and saturated vapor
phase-change
states are identical.
(boiling) process. 12
P-v diagram of a pure substance. The pressure in a piston–cylinder
device can be reduced by
reducing the weight of the piston.
13
Sublimation: Passing from the solid phase directly into the vapor
phase.
At low pressures (below

the triple-point value),
solids evaporate without
melting first (sublimation).
14
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.
P-v-T surface of a substance P-v-T surface of a substance that

that contracts on freezing. expands on freezing (like water).
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Thermodynamics - I

Pure Substance, Phase Change, Property Diagrams

Nitrogen and gaseous air are

At 1 atm and 20°C,

As more heat is transferred, At 1 atm pressure, the As more heat is

T-v diagram for the

T-v diagram of a pure substance.

At low pressures (below

P-v-T surface of a substance P-v-T surface of a substance that

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