Thermodynamics I

Chapter 2
Pure Substances
• Pure substance is a substance that has a fixed
chemical composition throughout.
• Although air is a mixture of several gases, it is
considered to be a pure substance.
Pure substances;
A mixture of
liquid and
gaseous water is
a pure substance

A mixture of liquid
and gaseous air is
not a pure substance
PHASES OF A PURE SUBSTANCE

Solid Liquid Gas

 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).
• 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
As more heat is transferred, part At 1 atm pressure, the temperature transferred, the
of the saturated liquid vaporizes remains constant at 100°C until the temperature of the vapor
(saturated liquid–vapor last drop of liquid is vaporized starts to rise
mixture). (saturated vapor). (superheated vapor).
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.
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.

Water
• 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.
 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).
 At supercritical
pressures (P > Pcr),
there is no distinct
phase-change (boiling)
process.

Critical point:
The point at which the saturated liquid
and saturated vapor states are identical.
P-v diagram of a pure substance.

The pressure in a piston–cylinder

device can be reduced by reducing
the weight of the piston.
 Extending the Diagrams to Include the Solid Phase

P-v diagram of a substance that

P-v diagram of a substance that
contracts on freezing.
expands on freezing (such as
water).

At triple-point pressure and For water,

temperature, a substance exists in Ttp = 0.01°C
three phases in equilibrium. Ptp = 0.6117 kPa
 Sublimation:
Passing from the solid phase
directly into the vapor phase.
Phase Diagram

At low pressures (below the

triple-point value), solids
evaporate without melting
first (sublimation).
 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 product pressure 

volume has energy units.
The combination u + Pv is
frequently encountered in the
analysis of control volumes.
 Saturated Liquid and Saturated Vapor States
Table A–4: Saturation properties of water under temperature.
Table A–5: Saturation properties of water under 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.
For water
 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.)
y => v, u, or h.
 Superheated Vapor
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.
In this region, temperature and pressure are independent properties.

Compared to saturated vapor, superheated

vapor is characterized by
 Compressed Liquid
The compressed liquid properties depend
on temperature much more strongly than Compressed liquid is characterized by
they do on pressure.
y  v, u, or h
A more accurate relation for h (for
low & moderate temp. & pres.)

A compressed liquid may

be approximated as a
saturated liquid at the
given temperature.
 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 referance 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.
 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
Mass = Molar mass  Mole number
Ideal gas equation at two
states for a fixed mass

•Real gases behave as an ideal

gas at low densities (i.e., low
pressure, high temperature).
•The ideal-gas relation often is
not applicable to real gases; thus,
care should be exercised when
using it.
 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, however, the
ideal gas assumption yields
unacceptable errors, particularly
in the vicinity of the critical point
and the saturated vapor line.
• In steam power plant
applications, however, the
pressures involved are usually
very high; therefore, ideal-gas
relations should not be used.

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.
 COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
Compressibility factor Z
The farther away Z is from unity, the more the gas
A factor that accounts for
deviates from ideal-gas behavior.
the deviation of real gases
from ideal-gas behavior at a Gases behave as an ideal gas at low densities (i.e.,
given temperature and low pressure, high temperature).
pressure. 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 ideal-

The compressibility factor is unity gas behavior (regardless of their temperature).
for ideal gases.
 Principle of
corresponding
Reduced Reduced states
pressure temperature
Pseudo-reduced Z can also be determined from a
specific volume knowledge of PR and vR.

Gases deviate the most

from the ideal-gas behavior
in the neighborhood of the
critical point.
Comparison of Z factors for various gases.
OTHER EQUATIONS OF STATE
Several equations have been proposed to
represent the P-v-T behavior of substances
accurately over a larger region with no
limitations.

Van der Waals Equation of State

Critical isotherm
of a pure
substance has an
inflection point
at the critical
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.
 Summary
• Pure substance
• Phases of a pure substance
• Phase-change processes of pure substances
– Compressed liquid, Saturated liquid, Saturated vapor, Superheated vapor
– Saturation temperature and Saturation pressure

• Property diagrams for phase change processes

– The T-v diagram, The P-v diagram, The P-T diagram, The P-v-T surface

• Property tables
– Enthalpy
– Saturated liquid, saturated vapor, Saturated liquid vapor mixture, Superheated vapor,
compressed liquid
– Reference state and reference values

• The ideal gas equation of state

‒ Is water vapor an ideal gas?

• Compressibility factor
• Van der Waals Equation of State