Thermodynamics: An Engineering Approach

Seventh Edition in SI Units

Yunus A. Cengel, Michael A. Boles
McGraw-Hill, 2011

Chapter
Ch
t 3
PROPERTIES OF PURE
SUBSTANCES
M h
Mehmet
Kanoglu
K
l
University of Gaziantep
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Objectives
Introduce the concept of a pure substance.
physics
y
of p
phase-change
g p
processes.
Discuss the p
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
P
t some off the
th best-known
b tk
equations
ti
off state.
t t
2

PURE SUBSTANCE
Pure substance: A substance that has a fixed chemical
composition
p
throughout.
g
Air is a mixture of several gases, but it is considered to be a
pure substance.

PHASES OF A PURE SUBSTANCE

The molecules
i a solid
in
lid are
kept at their
positions by the
large springlike
inter-molecular
forces.
In a solid, the
attractive and
repulsive forces
b t
between
the
th
molecules tend
to maintain them
att relatively
l ti l
constant
distances from
each other
other.
4

PHASE-CHANGE PROCESSES OF PURE

SUBSTANCES

Compressed liquid (subcooled liquid): A substance that it is not

about to vaporize.
vaporize
Saturated liquid: A liquid that is about to vaporize.
At 1 atm and 20C,
water exists in the
liquid phase
(compressed liquid).

At 1 atm pressure
and 100C, water
exists
i
as a liliquid
id
that is ready to
vaporize
(saturated liquid).
5

Saturated vapor: A vapor that is about to condense.

Saturated liquidvapor mixture: The state at which the liquid and
vapor phases
h
coexist
i t in
i equilibrium.
ilib i
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 transferred,
temperature remains
part of the saturated liquid
constant at 100C until the
vaporizes (saturated liquid llastt drop
d
off liquid
li id iis vaporized
i d
vapor mixture).
(saturated vapor).

As more heat is
transferred, the
temperature of the
vapor starts
t t to
t rise
i
(superheated vapor).
6

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,
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.

Sat. liquid

Sat. vapor

T-v diagram for the

heating process of
water at constant
pressure.
7

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
temperature.

The liquidvapor
saturation curve
of a pure
substance
(numerical
values are for
water).

Latent heat: The amount of energy

absorbed or released during a phasechange process.

Latent heat of fusion: The amount of

energy absorbed
b b dd
during
i melting.
lti
It iis
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
p
on the temperature
p
or p
pressure at
which the phase change occurs.

At 1 atm pressure, the latent heat of

fusion of water is 333
333.7
7 kJ/kg and the
latent heat of vaporization is 2256.5 kJ/kg.

The atmospheric pressure, and thus the

b ili ttemperature
boiling
t
off water,
t decreases
d
with elevation.
9

Some Consequences of
Tsat and Psat Dependence
The variation of
the temperature
of fruits and
vegetables with
pressure during
d i
vacuum cooling
from 25C to 0C.

In 1775,
1775 ice was made
by evacuating the air
space in a water tank.

10

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
substances.

T-v diagram of
constant-pressure
phase change
phase-change
processes of a pure
substance at various
pressures
(numerical values
are for water).

11

saturated liquid line

saturated vapor line

compressed liquid region

superheated vapor region

saturated liquidvapor
mixture region (wet region)

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.

12

Temperature is
maintained
constant

13

Extending the
Diagrams to Include
the Solid Phase

For water,
Ttp = 0
0.01
01C
C
Ptp = 0.6117 kPa

At triple-point pressure
and temperature, a
substance exists in three
phases in equilibrium.

14

Sublimation:
Passing from the
solid phase directly
into the vapor
p p
phase.

At low pressures
(below the triple-point
triple point
value), solids
evaporate without
melting first
(sublimation).

Phase Diagram

P-T diagram of pure 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
p p
are frequently
q
yp
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.

EnthalpyA Combination Property

The
combination
u + Pv is
frequently
encountered
i th
in
the analysis
l i The product pressure
of control
volume has energy units.
17
volumes.

Saturated Liquid and Saturated Vapor States

Table A4: Saturation properties of water under temperature.

Table A5: Saturation properties of water under pressure.

A partial list of Table A4.

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.
pressure

18

Water

Ptank = ?
Vtank = ?

50 kg

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

V = ?
E=?

T=?
m=?

19

Saturated LiquidVapor Mixture

Quality, x : The ratio of the mass of vapor to the total mass of the mixture
Quality
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
vapor.
Temperature and
pressure are dependent
properties for a mixture
mixture.

The relative
amounts of
liquid and
vapor phases
in a saturated
mixture are
specified by
the quality x.

A two-phase system can be

treated as a homogeneous
mixture for convenience.

20

v, u, or h.

21

Examples: Saturated liquid-vapor

mixture states on T-v and P-v diagrams.
Example 3-5

Example 3-4

80-L vessel contains 4 kg of R-134a at 160 kPa

T=? V=?
x=? h=?
Rigid tank contains 10 kg of water at 90C

P=?
V=?

Table A-4

Table A-12

22

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
vapor.
In this region, temperature and
pressure are independent
p ope es
properties.

Superheated Vapor
Compared to saturated vapor,
superheated vapor is characterized by

At a specified
P, superheated
vapor exists
i t att
a higher h than
the saturated
vapor
vapor.
Ap
partial listing
g
of Table A6.
23

The compressed liquid properties

depend
p
on temperature
p
much more
strongly than they do on pressure.

Compressed Liquid
Compressed liquid is characterized by

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.
24

Example 3-9 The use of steam tables

Determine the missing properties and the phase descriptions in the

following table for water:

T (C)
A
B
C
D
E

P (kPa)

u (kJ/kg)

200
125
75

1000
500
850

Phase
Ph
description

0.6
1600
2950
0.0
25

Reference State and Reference Values

The values of u,
u h,
h and s cannot be measured directly
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.
Th f
Therefore,
we need
d to
t choose
h
a convenient
i t reference
f
state
t t and
d assign
i a value
l off zero for
f
a convenient property or properties at that state.
The reference state for water is 0.01C and for R-134a is -40C in tables.
properties
p
may
y have negative
g
values as a result of the reference state chosen.
Some p
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
calculations.

26

THE IDEAL-GAS EQUATION OF STATE

Equation of state: Any equation that relates the pressure, temperature,

and specific volume of a substance.
Th simplest
The
i l t and
db
best-known
tk
equation
ti off state
t t for
f substances
b t
in
i the
th 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
M:
l mass (k
(kg/kmol)
/k l)
Ru: universal gas constant

Different substances have different

gas constants.

27

Mass = Molar mass Mole number

Ideal gas equation at two

states for a fixed mass

Various expressions
off ideal
id l gas equation
ti

Real gases behave as an ideal gas at low

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

Properties per unit mole are

denoted with a bar on the top.

28

Problem 3-77 Temperature rise of air in a tire

The pressure in an automobile tire depends on the temperature of

the air in the tire
tire. When the air temperature is 25C
25C, the pressure
gage reads 210 kPa. If the volume of the tire is 0.025 m3,
determine the pressure rise in the tire when the air temperature in
the tire rises to 50C
50C. Also determine the amount of air that must be
bled off to restore pressure to its original value at this temperature.
Assume the atmospheric pressure is 100 kPa.
Before
Pg = 210 kPa
T = 25 C
V = 0.025 m3
After
T = 50 C
V = 0.025 m3
Pg = ? kPa
mbled = ? @ Pg = 210 kPa
29

Is Water Vapor an Ideal Gas?

At pressures below 10 kPa

kPa, water
vapor can be treated as an ideal
gas, regardless of its temperature,
g g
error ((less than 0.1
with negligible
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

t bl - videal
id l|/vtable
t bl ] 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 FACTORA MEASURE

OF DEVIATION FROM IDEAL-GAS
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).
Question: What is the criteria for low p
pressure
and high temperature?
Answer: The pressure or temperature of a gas
is high
g or low relative to its critical temperature
p
or pressure.

31

Reduced
pressure

Reduced
temperature
Pseudo-reduced
specific volume

Comparison of Z factors for various gases.

Z can also be determined from

a knowledge of PR and vR.

32

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.

33

Beattie-Bridgeman Equation of State

The constants are given in
Table 34 for various
substances.
b t
It is
i known
k
to
t be
b
reasonably accurate for
densities up to about 0.8cr.

Benedict-Webb-Rubin Equation of State

The constants are given in Table 34. This equation can handle substances
at densities up to about 2
2.5
5 cr.

Virial Equation of State

The coefficients a(T),

a(T) b(T),
b(T) c(T),
c(T) and so on
on, that are
functions of temperature alone are called virial coefficients.
34

35

Percentage of error involved in various equations of

state for nitrogen
(% error = [(|vtable - vequation|)/vtable] 100).

Complex equations of
state represent the P-vT behavior of gases
more accurately over a
wider range.

36

Summary

Pure substance
Phases of a pure substance
Phase change processes of pure substances
Phase-change
9 Compressed liquid, Saturated liquid, Saturated vapor, Superheated vapor
9 Saturation temperature and Saturation pressure

P
Property
t diagrams
di
ffor phase
h
change
h
processes
9 The T-v diagram, The P-v diagram, The P-T diagram, The P-v-T surface

Property tables
9 Enthalpy
9 Saturated liquid, saturated vapor, Saturated liquid vapor mixture, Superheated
vapor, compressed liquid
9 Reference
R f
state
t t and
d reference
f
values
l

The ideal gas equation of state

9 Is water vapor an ideal gas?

Compressibility factor
Other equations of state
9 van der Waals Equation
q
of State,, Beattie-Bridgeman
g
Equation
q
of State
9 Benedict-Webb-Rubin Equation of State, Virial Equation of State
37