Chapter 3
PROPERTIES OF PURE
SUBSTANCES
SUMMARY
PURE SUBSTANCE
• Pure substance: A substance that has a fixed chemical
composition throughout.
• Compressed liquid (sub-cooled liquid): A substance that it is not
about to vaporize.
• Saturated liquid: A liquid that is about to vaporize.
• 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).
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T-v diagram for the heating process of water at constant pressure. 3
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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• 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 (Enthalpy): 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.
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PROPERTY DIAGRAMS FOR PHASE-CHANGE PROCESSES
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). 6
T-v diagram of a pure substance.
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Critical point: The
point at which the saturated
liquid and saturated vapor
states are identical.
At supercritical pressures (P > Pcr), there is
no distinct phase-change (boiling) process.
8
P-v diagram of a pure substance. The pressure in a piston–cylinder
device can be reduced by
reducing the weight of the piston.
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Extending the Diagrams to Include the Solid
Phase
For water,
Ttp = 0.01°C
Ptp = 0.6117 kPa
At triple-point pressure and
temperature, a substance exists in
three phases in equilibrium.
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Sublimation: Passing from the solid phase directly into the vapor phase.
At low pressures (below
the triple-point value), Phase Diagram
solids evaporate without
melting first (sublimation).
P-T diagram of pure substances.
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Saturated Liquid and Saturated Vapor States
• Table A–4: Saturation properties of water under temperature.
• Table A–5: Saturation properties of water under pressure.
A partial list of Table A–4.
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.
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Liquid – Vapour Mixture
y v, u, or h.
Quality is related to the horizontal
distances on P-v and T-v diagrams.
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Superheated Vapor
Superheated vapor is characterized by
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Compressed 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
A compressed liquid may be
approximated as a saturated liquid at
the given temperature.
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Compressed Liquid
Compressed liquid is characterized by
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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
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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.
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).
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COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
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.
At very low pressures, all gases approach
The compressibility factor is
ideal-gas behavior (regardless of their
unity for ideal gases.
temperature).
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Reduced pressure Reduced temperature
Pseudo-reduced specific volume
Z can also be determined
from a knowledge of PR
and vR.
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Comparison of Z factors for various gases.
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Gases deviate from the ideal-gas behavior the
most in the neighborhood of the critical point.
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OTHER EQUATIONS OF STATE
Van der Waals Equation of State
This model includes two effects not considered in the ideal-
gas model: the intermolecular attraction forces and the
volume occupied by the molecules themselves. The accuracy
of the van der Waals equation of state is often inadequate.
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OTHER EQUATIONS OF STATE
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
0.8ρcr.
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OTHER EQUATIONS OF STATE
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 ρcr.
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.
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Percentage of error involved in various equations of
state for nitrogen (% error = [(|vtable - vequation|)/vtable]
×100).
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THE END
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