CLASS

Third Units
 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.

Nitrogen and gaseous air are

pure substances. A mixture of liquid and gaseous
water is a pure substance, but a
mixture of liquid and gaseous air
is not.

2
 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. 3
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).
4
• 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 constant transferred, the
vaporizes (saturated liquid– at 100°C until the last drop of temperature of the
vapor mixture). liquid is vaporized vapor starts to rise
(saturated (superheated vapor).
vapor). 5
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.
6
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).
7
• 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.
8
Some Consequences of
Tsat and Psat Dependence
The variation of
the temperature of
fruits and
vegetables with
pressure during
vacuum cooling
from 25°C to 0°C.

The temperature of liquid

nitrogen exposed to the
atmosphere remains
constant at -196°C, and In 1775, ice was
thus it maintains the test made by
chamber at -196°C. evacuating the
air space in a
water tank. 9
 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).
10
• 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. 11
P-v diagram of a pure substance. The pressure in a piston–cylinder
device can be reduced by reducing
the weight of the piston.
12
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.

P-v diagram of a substance that

contracts on freezing.

P-v diagram of a substance that

expands on freezing (such as water). 13
Sublimation: Passing from Phase Diagram
the solid phase directly into
the vapor phase.

At low pressures (below

the triple-point value), P-T diagram of pure substances.
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).
15
 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
of control The product pressure 
volumes. volume has energy units.
16
 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.

17
Examples:
Saturated liquid
and saturated
vapor states of
water on T-v and
P-v diagrams.

18
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.
19
 y v, u, or h.

Quality is related
to the horizontal
distances on P-v
and T-v
diagrams.

The v value of a
saturated liquid– vapor
mixture lies between
the vf and vg
values at the
specified T or P.
20
Examples: Saturated liquid-vapor
mixture states on T-v and P-v diagrams.

21
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. 22
The compressed liquid properties Compressed Liquid
depend on temperature much more
Compressed liquid is characterized by
strongly than they do on pressure.
y  v, u, or h

A more accurate relation for h

At a given P
and T, a pure
A compressed liquid
substance will
may be approximated as
exist as a
a saturated liquid at the
compressed
given temperature.
liquid if

23
 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.

24
Exercises:

1. What is the difference between saturated liquid and

compressed liquid?

2. What is the difference between saturated vapor and

superheated vapor?

3. Why are the temperature and pressure dependent

properties in the saturated mixture region.

4. What is the physical significance of hfg? Can it be

obtained from a knowledge of hf and hg? How?

5. Is it true that it takes more energy to vaporize 1 kg of

saturated liquid water at 100°C than it would at
120°C? 25
Quiz
• Which is the energy quantity necessary to vaporize 1 Kg of
saturated liquid water at 75 Kpa.

26
Exercices

27
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

Different substances have different

gas constants.
28
Mass = Molar mass  Mole number Ideal gas equation at two
states for a fixed mass

Real gases
behave as an ideal
Various
gas at low
expressions densities (i.e., low
of ideal gas pressure, high
equation temperature).

The ideal-gas
relation often is not
applicable to real
gases; thus, care
should be exercised
when using it.

Properties per
unit mole are
denoted with a
bar on the top. 29
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 air-conditioning applications, the
water vapor in the air can be treated
as an ideal gas. Why?
• 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. 30
 COMPRESSIBILITY FACTOR—A MEASURE
OF DEVIATION FROM IDEAL-GAS BEHAVIOR
Compressibility factor Z The farther away Z is from unity, the more the
A factor that accounts for gas deviates from ideal-gas behavior.
the deviation of real gases Gases behave as an ideal gas at low
from ideal-gas behavior at a densities
given temperature and (i.e., 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

The compressibility factor is ideal-gas behavior (regardless of their
unity for ideal gases. temperature).
31