Thermodynamics: An Engineering Approach
Chapter 3
PROPERTIES OF PURE
SUBSTANCES
Dr. A. G. Kamble
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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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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PURE SUBSTANCE
• Homogeneous Substance - A substance that has uniform
thermodynamic properties throughout is said to be homogeneous.
• Pure Substance - A pure substance has a homogeneous and
invariable chemical composition and may exist in more than
one phase.
Examples:
1. Water (solid, liquid, and vapor phases)
2. Mixture of liquid water and water vapor
3. Carbon dioxide, CO2
4. Nitrogen, N2
5. Mixtures of gases, such as air, as long as there is no change of
phase
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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.
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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 liquid–vapor mixture: The state at which the liquid and
vapor phases coexist in equilibrium.
• Saturated vapor: A vapor that is about to condense.
• Superheated vapor: A vapor that is not about to condense (i.e., not a
saturated vapor).
At 1 atm pressure, the As more heat is
As more heat is transferred, temperature remains transferred, the
part of the saturated liquid constant at 100°C until the temperature of the
vaporizes (saturated liquid– last drop of liquid is vaporized vapor starts to rise
vapor mixture). (saturated vapor). (superheated vapor).
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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.
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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 substance changes
phase at a given temperature.
The liquid–vapor
saturation curve
of a pure
substance
(numerical
values are for
water).
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• Latent heat: The amount of
energy absorbed or released
during a phase-change
process.
• The magnitudes of the latent
heats depend on the
temperature or pressure at
which the phase change
occurs.
• The atmospheric pressure,
and thus the boiling
temperature of water,
decreases with elevation.
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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). 11
PROPERTY DIAGRAMS FOR PHASE-CHANGE
PROCESSES
• If all of the saturated liquid
states are connected, the
saturated liquid line is
established. If all of the
saturated vapor states are
connected, the saturated vapor
line is established. These two
lines intersect at the critical
point and form what is often
called the “steam dome.”
• The region between the
saturated liquid line and the
saturated vapor line is called by
these terms: saturated liquid-
vapor mixture region, wet region
(i.e., a mixture of saturated
liquid and saturated vapor), two-
phase region
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• saturated liquid line
• saturated vapor line
• compressed liquid region
• superheated vapor region
• saturated liquid–vapor
mixture region (wet region)
At supercritical
pressures (P > Pcr), Critical point: The point
at which the saturated
there is no distinct
liquid and saturated vapor
phase-change
states are identical.
(boiling) process. 13
Critical point: The point at which the latent heat becomes zero.
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Extending the For water,
Diagrams to Include Ttp = 0.01°C
Ptp = 0.6117 kPa
the Solid Phase
At triple-point pressure
and temperature, a
substance exists in three
phases in equilibrium.
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Sublimation
• Two ways a
substance can go
from solid to vapor:
Melts to liquid, then
vaporizes to vapor
Evaporates directly
with out first
melting, sublimation
• Happens at
pressures below
triple point value
Sublimation: Phase Diagram
Passing from the
solid phase directly
into the vapor phase.
At low pressures
(below the triple-point
value), solids
evaporate without
P-T diagram of pure substances.
melting first
(sublimation).
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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.
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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.
Enthalpy—A Combination Property
The
combination
u + Pv is
frequently
encountered
in the analysis The product pressure
of control volume has energy units.
volumes. 19
Saturated Liquid and Saturated Vapor States
A partial list of Table A–4.
Sensible heat, hf : The amount of heat
required to rise temperature of 1 Kg of water
from O Oc to saturation temperature by
maintaining constant pressure.
Enthalpy of vaporization, hfg (Latent heat
of vaporization): The amount of energy
needed to vaporize a unit mass of saturated
liquid at a given temperature or pressure.
Superheated, hsup : The amount of heat
required to rise temperature of dry saturated
steam from dry saturation temperature to
superheated temperature.
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Examples:
Saturated liquid
and saturated
vapor states of
water on T-v and
P-v diagrams.
Dry steam: It is defined as the steam which is
not having any water particles.
Wet steam: It is a mixture of steam and water
particles.
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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.
The relative
amounts of
liquid and
vapor phases
in a saturated
mixture are A two-phase system can be
specified by treated as a homogeneous
the quality x. mixture for convenience.
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y v, u, or h.
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In the region to the right of the Superheated Vapor
saturated vapor line and at
temperatures above the critical Compared to saturated vapor,
point temperature, a substance superheated vapor is characterized by
exists as superheated vapor.
In this region, temperature and
pressure are independent
properties.
At a specified
P, superheated
vapor exists at
a higher h than
the saturated
vapor.
A partial
listing of
Table A–6. 24
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