Thermodynamics: An Engineering

Approach

Chapter 3
PROPERTIES OF PURE
SUBSTANCES
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.

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 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).

At 1 atm pressure, As more heat

As more heat is the temperature remains is transferred, the
transferred, part of the constant at 100°C until temperature of the
saturated liquid the last drop of liquid is vapor starts to rise
vaporizes (saturated vaporized (superheated
liquid– vapor (saturated vapor).
5
mixture).
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 6
7
 Saturation Temperature and Saturation
• ThePressure
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
8
values are for
• 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.
• 9
The atmospheric pressure, and thus
Some Consequences of
Tsat and
Psat DependenceThe variation
of the
temperature of
fruits and
vegetables with
pressure
during vacuum
cooling from
25°C to 0°C.

In 1775, ice was

made by
evacuating the air 8
 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 9
• saturated liquid line
• saturated vapor line
• compressed liquid
region
• superheated vapor
region
• saturated liquid–vapor
mixture region (wet
region)

At supercritical
Critical point: The
pressures (P >
point at which the
Pcr), there is no
saturated liquid and
distinct phase- saturated vapor
change (boiling) states are identical.
1
0
13
 Extending the For water,
Diagrams to Ttp = 0.01°C
Ptp = 0.6117 kPa
Include
the Solid Phase
At triple-point
pressure and
temperature, a
substance exists in
three phases in
equilibrium.

14
Sublimation: Phase
Passing from the Diagram
solid phase
directly into the
vapor phase.

At low pressures
(below the triple-
point value),
solids evaporate
P-T diagram of pure
without melting
first (sublimation). substances.
15
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.

16
 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
combinatio
n u + Pv
is
frequently
encounter The product pressure
ed 
in the 1
volume has energy 5
 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.

18
Examples:
Saturated
liquid and
saturated
vapor states
of water on T-
v and P-v
diagrams.

19
 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 A two-phase system can be
mixture are treated as a homogeneous
specified by mixture for convenience.
18
the quality x.
y v, u, or
h.

21
Quality Region

The Quality Region, also referred to as the Saturated

Liquid-Vapor Mixture Region, is the area enclosed
between the saturated liquid line and the saturated
vapor line. At any point within this region the quality of
the mixture (sometimes referred to as the dryness
factor) is defined as the mass of vapor divided by the
total mass of the fluid, as shown in the following
diagram:

22
Examples: Saturated liquid-vapor
mixture states on T-v and P-v
diagrams.

23
In the region to the right of Superheated Vapor
the saturated vapor line
and at temperatures Compared to saturated vapor,
above the critical point superheated vapor is
temperature, a substance 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– 2
6. 1
The compressed liquid
properties depend on
Compressed
temperature much more
strongly than they do on
Liquid
pressure. Compressed liquid is
characterized by
y  v, relation
A more accurate u, or h
for h

A compressed liquid
may be
approximated as a
saturated liquid at
the given
temperature.
25
Question: Complete this table for
H2O.

26
27
Question: 1 kg of water fills a 150 L rigid container at an initial pressure of 2
MPa. The container is then cooled to 40 oC. Determine the initial temperature
and final pressure of the water.

28
 Reference State and Reference
• The values ofValues
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.

29
 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.
30
Mass = Molar mass  Mole Ideal gas equation at
number two states for a
fixed mass
Various
expressions of
ideal gas equation

Real gases behave as an ideal gas at

low densities (i.e., low pressure, high
temperature).

Properties per unit mole

are denoted with a bar on 2
8
 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
Percentage of error ([|vtable - videal|/vtable] 100) involved in high; therefore,
assuming steam to be an ideal gas, and the region ideal-gas relations should not
where steam can be treated as an ideal gas with be used.
less 2
than 1 percent error. 9
Question: A 1-m3 tank containing air at 25°C and 500 kPa is connected
through a valve to another tank containing 5 kg of air at 35°C and 200 kPa.
Now the valve is opened, and the entire system is allowed to reach thermal
equilibrium with the surroundings, which are at 20°C. Determine the volume
of the second tank and the final equilibrium pressure of air.

3
0
3
1
 COMPRESSIBILITY FACTOR—A
MEASURE OF DEVIATION FROM IDEAL-
GAS BEHAVIOR The farther away Z is from unity,
Compressibility the
factor Z A factor that more the gas deviates from ideal-gas
accounts for the behavior.
deviation of real gases Gases behave as an ideal gas at low
from ideal-gas densities (i.e., low pressure, high
behavior at a given temperature).
temperature and Question: What is the criteria for low
pressure. pressure and high temperature?
Answer: The pressure or temperature of
a gas is high or low relative to its critical
temperature or pressure.

3
2
 Reduce Reduced
d temperatu
pressur re Z can also be determined
e from a knowledge of
Pseudo-
reduced PR and vR.
specific
volume

Comparison of Z factors for various 3

3
 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 Critical
State isotherm
of a
pure
substance
has an
inflection
point at the
This model includes two effects not
considered in the ideal-gas model: the critical
intermolecular attraction forces and thestate.
volume occupied by the molecules
themselves. The accuracy of the van der 3
4
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 0.8cr.

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 cr.

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. 38
39
 Complex equations
of state represent
the P-v- T behavior
of gases more
Percentage of error involved in various accurately over a
equations of state for nitrogen wider range.
(% error = [(|vtable - vequation|)/vtable] 100).
40
 EXAMPLE : The Use of Generalized Charts

Determine the specific volume of refrigerant-134a at 1 Mpa and 50 ⁰C, using (a) the ideal
gas equation of state and (b) the generalized compressibility chart. Compare the values
obtained to the actual value of 0.021796 m3/kg and determine the error involved in each
case.

SOLUTION :

(a) v = 0.026325 m3/kg

error = 20.8 %
(b) v = 0.022113 m3/kg
error = 1.45 %

41
 Using Generalized Charts to
EXAMPLE :
determine Pressure

Determine the pressure of water at 350 ⁰C and 0.035262 m3/kg, using (a) the steam
tables, (b) the ideal gas equation, and (c) the generalized compressibility chart.

SOLUTION :

(a) P = 7.0 MPa

(b) P = 8.15 MPa
(c) P = 6.84 MPa

42
 Different Methods of Evaluating Gas
EXAMPLE :
Pressure

Predict the pressure of nitrogen gas at T=175 K and v=0.00375 m 3/kg on the basis of (a)
the ideal gas equation of state and (b) the van der Waals equation of state, (c) the
Beattie-Bridgeman equation of state and (d) the Benedict-Webb-Rubin equation of state.
Compare the values obtained to the experimentally determined value of 10,000 kPa.

SOLUTION :

(a) P = 13,851 kPa

error = 38.5 %
(b) P = 9471 kPa
error = 5.3 %
(c) P = 10,110 kPa
error = 1.1 %
(d) P = 10,009 kPa
error = 0.09 %
43