Thermodynamics: An Engineering Approach, 8th Edition

Yunus A. Cengel, Michael A. Boles

McGraw-Hill, 2015

Chapter 3
PROPERTIES OF PURE
SUBSTANCES

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Objectives
Introduce the concept of a pure substance.
Discuss the physics of phase-change processes.
Illustrate the P-v, T-v, and P-T property diagrams.
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 some of the best-known equations of state

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 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 is Even A mixture of

a pure gaseous air but a mixture of
liquid and liquid and
substance. is a pure gaseous water
substance gaseous air is
is a pure not.
substance,
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 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. 4
PHASE-CHANGE PROCESSES OF PURE
SUBSTANCES
Compressed liquid (subcooled liquid): A substance that it
is not about to vaporize. (State 1)
Saturated liquid: A liquid that is about to vaporize. (State 2)

At 1 atm and 20C,

water exists in the
liquid phase
(compressed liquid).

At 1 atm pressure
and 100C, water
exists as a liquid
that is ready to
vaporize
(saturated liquid).
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 Saturated vapor: A vapor that is about to condense. (State 4)
Saturated liquidvapor mixture: The state at which the liquid and
vapor phases coexist in equilibrium. (State 3)
Superheated vapor: A vapor that is not about to condense (i.e., not a
saturated vapor). (State 5)

As more heat is transferred, At 1 atm pressure, the As more heat is

part of the saturated liquid temperature remains transferred, the
vaporizes (saturated liquid constant at 100C until the temperature of the
vapor mixture). last drop of liquid is vaporized vapor starts to rise
(saturated vapor). (superheated vapor).
6
 Sat
liq.

Sat
vap.

T-v diagram for the

heating process of
water at constant
pressure.

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.
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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.

The liquidvapor
saturation curve of a pure
substance (numerical
values are for water). 8
 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
Some Consequences of
Tsat and Psat Dependence
The variation of
the temperature
of fruits and
vegetables with
pressure during
vacuum cooling
from 25C to 0C.

Read from
the book!
The temperature of liquid
nitrogen exposed to the
atmosphere remains
constant at -196C, and In 1775, ice was
thus it maintains the test made by
chamber at -196C. 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.

T-v diagram of
constant-pressure
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)

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. 12
P-v diagram of a pure substance. The pressure in a pistoncylinder
device can be reduced by
reducing the weight of the piston.
13
Extending the For water,
Diagrams to Include Ttp = 0.01C
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). 14
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).

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.

P-v-T surface of a substance P-v-T surface of a substance that

that contracts on freezing. expands on freezing (like water).
16
PHASE-CHANGE PROCESSES FOR CO2

17
 3-5 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 (table for each region).

EnthalpyA Combination Property

The
combination
u + Pv is
frequently
encountered
in the analysis
of control The product pressure
volumes. volume has energy units.
18
Saturated Liquid and Saturated Vapor States
Table A4: Saturation properties of water under temperature.

19
 Table A5: Saturation properties of water under pressure.

20
 Subscript f: to denote properties of saturated liquid
A partial list of Table A4. Subscript g: to denote properties of saturated vapor
Subscript fg: difference

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.

decreases as
the temperature
or pressure
increases
becomes zero
at the critical
point.
21
 Example 3-1
A rigid tank contains 50 kg of saturated
liquid water at 90C. Determine the pressure
in the tank and the volume of the tank.

P= Psat @ 90c
= 70.183 kPa

= sat @ 90c
= 0.001036 m3/kg

= m=
(50 kg)(0.001036 m3/kg)
= 0.0518 m3

Check Example
3-2 on your own
22
Example 3-3
A mass of 200 g of saturated liquid water is completely vaporized at
a constant pressure of 100 kPa. Determine (a) the volume change
and (b) the amount of energy transferred to the water.

23
Example with Interpolation
Interpolation is used to find values that are located between
subsequent rows.
Given: A ~ j
B ~ k?
C ~ l
k= j+ (l-j)(B-A)/(C-A)

Repeat Example 3-3 if P=85 kPa

f@85kPa=0.001037+(0.001043-0.001037)*(85-75)/(100-75)=0.001040 m3/kg
g@85kPa=2.2172+(1.6941-2.2172)*(85-75)/(100-75)=2.0080 m3/kg
fg=2.0069 m3/kg =0.4014 m3 24
Saturated LiquidVapor Mixture
Temperature
and pressure
are dependent
properties for a
mixture.

The properties of the saturated

liquid are the same whether it
The relative amounts of liquid and exists alone or in a mixture with
vapor phases in a saturated mixture saturated vapor.
are specified by the quality x. A two-phase system can be treated
as a homogeneous mixture for
convenience.

Quality, x : The ratio of the mass of vapor to the total mass of the mixture.
Quality is between 0 and 1 0 x 1

sat. liquid sat. vapor

25
Given x,
find avg

Given avg,
find x

26
 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.
27
Revisit State Postulate~ identifying which
state are we at!
The state of a simple compressible system is
completely specified by two independent,
intensive properties.
system is called a simple compressible system
in the absence of electrical magnetic,
gravitational, motion, and surface tension
effects.
Pressure and Temperature in saturated vapor,
saturated liquid, and saturated liquid-vapor
mixture are not independent.
For a specific T, there is only one Psat and for a
specific P there is only one Tsat.
If state is not defined in the question, we will
need another intensive property to identify the
exact state.
Use , u, h or s of the mixture (if x is not given).
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Example 3-4
A rigid tank contains 10 kg of water at 90C. If 8 kg of the water is in
the liquid form and the rest is in the vapor form, determine (a) the
pressure in a the tank and (b) the volume of the tank.

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Example 3-5
An 80-L vessel contains 4 kg of refrigerant-134a at a pressure of
160 kPa. Determine (a) the temperature, (b) the quality, (c) the
enthalpy of the refrigerant, and (d) the volume occupied by the vapor
phase.
Need to
identify state

Check the rest of solution in text book! 30

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

Region
Identification

31
Sat.
Vapor
yg

See Examples 3-6 and 3-7.

32
Compressed Liquid
In the region to the left of the saturated
liquid line
Compressed liquid is characterized by

Region
ID

Compressed liquid tables are not as commonly available.

Table A-7 (compressed liquid water) is the only available.
The compressed liquid properties depend on temperature much more
strongly than they do on pressure.
A compressed liquid may be approximated as a
saturated liquid at the given temp.
y v, u, or h
A more accurate relation for h
33
See Example 3-8
Example 3-9

35
 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 0.01C and for R-134a is -40C 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.

36
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.
Pabs Ideal gas equation
of state
m3/kg In Kelvin

R: gas constant
M: molar mass (kg/kmol)
Ru: universal gas constant

Different substances have different

gas constants (Check Table A-1).
37
 Mass = Molar mass Mole number

Various
expressions
of ideal gas
equation
Properties per unit
mole are denoted with
Ideal gas equation at two a bar on the top.
states for a fixed mass
See Example 3-10 on your own!

An ideal gas is an imaginary

substance
Real gases behave as an ideal gas at Air, N2, O2, H2, He, Ar, Ne. Kr, CO2
low densities (i.e., low pressure, high ideal gas
temperature). H2O and Refrigerants not always!
The ideal-gas relation often is not
applicable to real gases; thus, care should
be exercised when using it.
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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. 39
 COMPRESSIBILITY FACTORA 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 densities
from ideal-gas behavior at (i.e., low pressure, high temperature).
a given 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.

At very low pressures, all gases approach

The compressibility factor is ideal-gas behavior (regardless of their
unity for ideal gases. temperature).
40
 Z can be determined from a Using
knowledge of PR and TR. compressibility
charts (A-15)
Reduced Reduced
pressure temperature Z can also be determined from
Pseudo-reduced a knowledge of PR and vR.
specific volume Principle of corresponding
states: gases behaving the
same at the same TR and PR
From Compressibility Chart, we
can note that:
TR>2

Near cr

PR<<1

Experimentally determined Z values are at

given PR and TR for several gases. 41
42
43
EXAMPLE 3-11
Determine the specific volume of refrigerant-134a at 1 MPa and
50C, 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.

44
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. 45
Beattie-Bridgeman Equation of State

The constants are given in

Table 34 for various
substances. It is known to be
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 2.5 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.
46
 Complex equations of
state represent the P-v-
T behavior of gases
more accurately over a
Percentage of error involved in various equations of wider range.
state for nitrogen
(% error = [(|vtable - vequation|)/vtable] 100).

47
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
Other equations of state
48
This presentation has been prepared by Mehmet Kanoglu and
modified by Wahib Owhaib
Copyright The McGraw-Hill Companies, Inc. Permission
required for reproduction or display.

49