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FOR ENGINEERS
FRANCIS J.
DOOLITTLE HALE
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THERMODYNAMICS
FOR ENGINEERS
«
THERMODYNAMICS
FOR ENGINEERS
Jesse S. Doolittle
Francis J. Hale
Department of Mechanical
and Aerospace Engineering
North Carolina State University
10 987654321
PREFACE
v
vi Preface
lems have been devised to show the effects of changes in various parameters
on the performance of engineering devices. For example, the answers to
various problems in the vapor cycles chapter show the precise effect of initial
conditions, exhaust pressure, reheating, and feedwater heating on the
efficiency of steam cycles. Because many instructors believe that students
should not be given answers to problems ahead of time, no answers are given
in the text. However, if some instructors wish to give answers to their
students, they can find answers in the solution manual that will be available to
them.
Recognizing the trend toward the use of the International System of Units
(SI), we use these units throughout the book. However, since the English
system of units is still being used extensively in this country, some work using
English units is given in the first part of the text. Although changes are being
made, the dimensions of much industrial equipment are still given in inches or
feet. For example, common pipes are manufactured to specified dimensions
(both the nominal and actual diameters) in inches. Hence, when dealing with
pipes, we use the sizes as given in inches.
We express our appreciation to Linda Jackson for her excellent help in the
preparation of the manuscript.
Jesse S. Doolittle
Francis J. Hale
CONTENTS
Chapter 1 Introduction 1
2 1 Introduction 31
22 Basis of the First Law 31
23 Energies Involved in the First Law 32
24 Evaluation of Potential and Kinetic Energies 34
25 Evaluation of Transferred Energies 35
26 The First Law Applied to Systems 42
27 Power 43
28 Enthalpy 45
29 FirstLaw Applications 46
Problems 53
31 Introduction 57
32 Ideal Versus Actual Gases 61
■ ■
VII
viii Contents
5 1 Introduction 116
52 The Carnot Cycle 118
53 The Reversed Carnot Cycle 122
54 The Clausius Inequality 125
55 Entropy 127
56 Entropy and Irreversibility 130
57 Uses for Entropy 132
5 8 Various Forms of the Second Law 134
Problems 135
7 1 Introduction 156
72 The Microscopic Approach 156
73 Probability 157
74 Probability and Entropy 161
7 5 Entropy and the Third Law 163
Problems 165
8 1 Introduction 166
82 Internal Energy and Enthalpy 168
83 Entropy Changes 171
84 Specific Heat Relations 172
85 Clapeyron Equation 174
86 JouleThomson Coefficients 175
87 Other General Equations 179
8 8 Summary 180
Problems 181
SYMBOL MEANING
A Area
A Ampere
A Helmholtz function
a Specific Helmholtz function
a Absorptivity
a Acceleration
a Acoustic velocity
Btu British thermal unit
B Magnetic field strength
C Constant (general)
c Specific heat
cv Specific heat for a constantvolume process
Cp Specific heat for a constantpressure process
Cx Specific heat for a polytropic process
cm Centimeter
C.O.P. Coefficient of performance
(C.O.P.)r Coefficient of performance for refrigeration
(C.O.P .)h p Coefficient of performance for a heat pump
Chem. E. Chemical energy
D Diameter
E Voltage
E Emissive power
eV Electron volt
F Force
Fa Shape factor
Fe Emissivity factor
f Fugacity
f Saturated liquid (as a subscript)
fg Change in properties during phase change (as a subscript)
xv
xvi Symbols and Abbreviations
SYMBOL MEANING
ft Foot
G Mass rate of flow per unit area
G Gibbs function (free energy) = H  TS
g Specific Gibbs function
g Gram
g Acceleration due to gravity
g Saturated vapor (as a subscript)
gi Possible number of quantum states
Gr Grashof number
gmole gram mole
H Enthalpy
h Specific enthalpy
h Hour
h Planck constant
h Surface or film heattransfer coefficient
hc Convertive surface or film heattransfer coefficient
hp horsepower
hr Radiant surface or film heattransfer coefficient
I Moment of inertia
I Electric current
I Intensity of radiation
J Current density
J Joule
J Quantum number
Js Entropy current
K Kelvin
K Combined thermal conductivity
KP Chemical equilibrium constant
kl kiloliters
K.E. Kinetic energy
k Boltzmann constant (gas constant per molecule)
k Specific heat ratio (=cp/cj
k Thermal conductivity
kg Kilogram
kW Kilowatt
lb Pound
lb/ Pound force
lbmole Pound mole
Symbols and Abbreviations xvii
SYMBOL MEANING
SYMBOL MEANING
R Electric resistance
Re Reynolds number
r Distance between magnetic poles
r Compression ratio
r Radius
rt Combined electrical resistance
r Rotational (as a subscript)
S Entropy
s Specific entropy
s Second
T Absolute temperature
T Torque
t Degrees Celsius or Fahrenheit
t Time
t Translational (as a subscript)
U Internal energy
u Overall coefficient of heat transfer
uk Internal molecular kinetic energy
Up Molecular potential energy
u Specific internal energy
V Volume
V Volts
v Specific volume
v Vibratory (as a subscript)
V Vapor (as a subscript)
W Work
Wm Mechanical work
W, Electrical work
w Rate of doing work
W' Possible number of macroscopic states
w Watt
w Weight
w Specific weight
X or x Unknown (general)
x Quality, mass fraction of vapor in a twophase mixture
x Thickness
y Moisture content, mass fraction of liquid in a twophase
mixture
Symbols and Abbreviations XIX
SYMBOL MEANING
Z Compressibility factor
z Figure of merit
z Quantum partition function
2 Height
p Coefficient of volume expansion
e Emissivity
e Energy level
V Efficiency
Vm Mechanical efficiency
Vn Nozzle efficiency
Vt Thermal efficiency
A Wavelength
v Kinematic viscosity
V Frequency
Viscosity (absolute)
P' JouleThomson coefficient
a ohm
p Density
p Reflectivity
y Velocity
y' rms Root mean square velocity
T Transmissivity
T Thomson coefficient, thermoelectricity
a Seebeck coefficient, thermoelectricity
IT Peltier coefficient, thermoelectricity
Work function, thermionic generation
& Possible number of microscopic states
<t> Relative humidity
OJ Specific humidity
cr Symmetry number (molecular)
cr Internal electric conductivity
n Product of
*'
_ 1 _
INTRODUCTION
‘The work of Count Rumford in 1798 and Sir Humphry Davy in 1799 contributed to the final
understanding of the nature of heat.
1
2 Introduction
outside of the heated space, some of the energy is lost from the furnace as
heat (see Fig. ll).2 The remainder of the energy of the fuel may be used to
heat the house. To conserve energy in this case, two factors must be
optimized:
1 The second law limits the amount of heat that can be transformed into
work and, for the given conditions, specifies the maximum amount of
work that can be produced from a given quantity of heat.
2 In every actual process some of the ability to do work is lost. Thus the
second law states that energy available for doing work continuously
becomes unavailable for this purpose.
2The term “lost” as used here means that energy of the fuel becomes unavailable for its intended
use; it is not destroyed.
4 Introduction
Consider the automotive engine. By virtue of the second law only a small
portion of the energy of the fuel (perhaps 20 to 25 percent) is delivered to the
pistons. The remainder of the energy of the fuel is:
1 Carried away by the exhaust gases by virtue of their high temperature and
by the products of incomplete combustion, such as the hydrocarbons and
carbon monoxide.
2 Carried away by the jacket water to the radiator where it is dispensed to
the atmosphere.
3 Lost by the engine to the surroundings, largely by radiation and con¬
vection.
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6 Introduction
steam can, even theoretically, be delivered as work by the turbine, with the
actual work being perhaps 75 percent of the theoretical. The remainder of the
heat supplied is removed in the condenser as the exhaust steam from the
turbine is condensed and the resulting condensate is pumped back into the
steam generator. The electrical generator converts about 98 percent of the
work delivered by the turbine into electrical energy. This electrical energy is
transmitted through the transmission system. Because of the electrical resis¬
tance of the transmission system, some of the electrical energy input is
dissipated as heat. The remainder of the electrical energy is delivered to the
various places where it is to be used, such as the motor of the machine in the
factory.
The first law may be applied to the overall process. The energy of the fuel
is not destroyed and an accounting can be made of all the ways in which it is
dissipated. More importantly, the second law is very much in evidence. The
secondlaw limitations on the amount of work that can be produced from a
given quantity of heat are very evident here. The second aspect of the second
law also is very much in evidence as work is transferred from the turbine to
the machine in the factory. In each transfer process, some of the work is
dissipated as heat. As a result, only a portion of the work delivered by the
turbine can be used for the machining operation. In the interest of energy
conservation as well as cost considerations, it is essential that the work output
of the turbine be maximized and that the work dissipation losses be mini¬
mized.
The above three examples of energy conversions and transfers are only a
few of the exceedingly large number of similar problems encountered daily by
engineers. In all energyinvolved problems, the energy produces changes in
the physical and/or chemical aspects of matter. Hence, a complete study of
thermodynamics must involve a study of matter in all of its forms: solid,
liquid, and gaseous. This study must be centered on changes in the properties
of matter produced by the application of energy. Although the engineer is
sometimes concerned with thermodynamic problems dealing with liquids and
solids, he or she is more involved with those problems dealing with gases and
vapors. Hence, the major emphasis in this book is on gases and vapors.
In the early days of thermodynamics, observations were made about the
behavior of matter. Laws were devised to express the effects of variations of
some parameters on the behavior of other parameters. These experimentally
based laws are valid provided that they truly represent the experimental
results and that the experimental results are correct. A further restriction is
that these laws must be applied only to the conditions for which they were
derived. For example, Boyle observed that the pressure of a gas varied
inversely with its volume when the temperature was held constant. This law is
perfectly valid under normal conditions of temperature and pressure for gases
that are hard to liquefy such as oxygen, nitrogen, and hydrogen. But this law
breaks down completely for these gases at very low temperatures and shows
Thermodynamic Systems 7
an appreciable error under normal conditions for gases that are easy to
liquefy.
Thermodynamics uses these experimentally based laws, but it must con¬
sider the limitations of these laws as well as their adaptation to conditions
other than those for which they were devised. It is frequently helpful in the
study of these laws to formulate hypotheses to help explain them. Desirable
as this practice may be, it is important to recognize that the science of
thermodynamics is not based in any way on these hypotheses but rather on
the observable laws.
In the preceding discussion, no attempt was made to study the behavior of
the molecules of which matter is composed, but rather attention was directed
to matter as a composite whole. Such an approach is known as a macroscopic
or classical approach. Since most engineering problems involve finite quan¬
tities of matter containing an extremely large number of molecules, the
macroscopic approach is satisfactory for these types of problems. However,
when one is dealing with matter at extremely low pressures, such as those in
the very upper reaches of the atmosphere, molecules of gases are so far apart
that serious errors may be caused by assuming that matter is continuous and
by applying the laws of classical thermodynamics. Also when gases are
heated to very high temperatures, there will be changes in the molecular
behavior that classical thermodynamics cannot explain. In both of these
examples, as well as several others, it is necessary to study the behavior of
the molecules and, from such a study, to formulate laws that govern the
behavior of the matter. Such an approach is known as the microscopic
approach.
However, because even an extremely small volume of matter under normal
conditions contains billions upon billions of molecules, it is not feasible to
consider the behavior of each and every molecule. This problem may be
solved by formulating a molecular model of matter and then predicting from
this model the probability of the behavior of a large number of molecules.
This study involves the use of statistical thermodynamics.
boundaries of the system be specified very carefully. For example, when one
is dealing with a gas in a cylinder where the boundaries are located on the
outside of the cylinder, the system includes both the cylinder and its con¬
tained gas. On the other hand, when the boundaries are placed at the inner
face of the cylinder, the system consists solely of the gas itself.
When the boundaries of a system are such that it cannot exchange matter
with the surroundings, the system is said to be a closed system (see Fig. l3a).
The system, however, may exchange energy in the form of heat or work with
the surroundings. The boundaries of a closed system may be rigid or may
expand or contract, but the mass of a closed system cannot change. Flence,
the term control mass sometimes is used for this type of system. When the
energy crossing the boundaries of a closed system is zero or substantially so,
the system may be treated as an isolated system (Fig. l3b).
In most engineering problems, matter, generally a fluid, crosses the bound¬
aries of a system in one or more places. Such a system is known as an open
system (see Fig. l3c). The boundaries of an open system are so placed that
their location does not change with time. Thus, the boundaries enclose a fixed
volume, commonly known as the control volume.
Sometimes a system may be a closed system at one moment and an open
one the next. For example, consider the cylinder of an internal combustion
engine with the boundaries at the inner walls. With the valves closed (Fig.
l4a), the system is a closed one. However, with either or both of the valves
open (Fig. l4b), the system becomes an open system. Thus care must be
taken not only to specify the location of the boundaries of the system but also
to specify what is happening at the boundaries.
Frequently the total system to be considered may be large and complicated.
The system may be broken down into component parts and an analysis of the
component parts made. Then the performance of the entire system can be
determined by the summation of the performance of the individual com¬
ponent systems. For example, consider the liquidvapor part of a steam power
plant as an entire system. This system, which is closed, contains the steam
generator (which includes the superheater, the reheater, and the economizer),
the steam turbine, the steam condenser, the feedwater pumps, and the
FIGURE 13 Types of systems, (a) Closed system, (b) Isolated system, (c) Open system.
Thermodynamic Properties 9
From intake
manifold
Spark plug—5—
Water jacket
(b)
FIGURE 14 Internal combustion engine, (a) Valves closed. (b) Valves open.
14 UNITS
Before investigating the various properties of substances, it is desirable to
consider the units used in evaluating these properties. Substantially all coun¬
tries, with the exception of the United States, now use the SI system
(Systeme International). Here in the United States we are now moving from
English units to the SI system. Hence, the SI system will be used primarily in
this book. However, some examples and some problems will employ English
units to prepare students to work in the industrial world where complete
conversion to the SI system will require several years.
The SI system consists of six base units and two supplementary units. The
base units are:
As various properties are discussed, various derived units, some named and
some unnamed, will be introduced.
To avoid the use of very large or very small numbers, prefixes have been
12 Introduction
Standard
mass
Unknown
mass
>■
Knife edge
W = mg 02)
where W is weight
g is the acceleration of gravity
40 w 20
F = ma
1000 X 100
= 0.008 N Answer
Example 12. Determine the mass of an object that has a weight of 180 N
where the gravity acceleration is 9.802 m/s2.
W= 180
18.36 kg Answer
g 9.802
In dealing with mass, force, and weight in English units, confusion arises
because the unit of force is taken as the pound force (lb/) and at the same
14 Introduction
time the unit of mass is taken as the pound mass (lbm).4 The pound mass is
defined in terms of the kilogram mass. The pound mass equals 0.45359237 kg.
The pound force is defined as the force of gravity acting on a pound mass at
standard sea level conditions. But, at this location, the acceleration of gravity
is 32.174 feet per second per second (ft/s2). Thus the pound force produces an
acceleration of the pound mass of 32.174 ft/s2. Under these conditions it is
necessary to introduce a dimensional constant gc. This constant, not to be
confused with g, the acceleration of gravity, has a value of 32.174 lbm ft/lb/ s2.
Equation 11 may now be written as
ma
F = (1la)
gc
Solution. Since the pound mass and the pound force are both to be used, Eq.
13 is to be used. Then
16 PRESSURE
Pressure is defined as the force acting on a unit area. When a force is exerted
on a fluid, this force is transmitted throughout the fluid. If the fluid is
stationary, the pressure within the fluid is uniform throughout the fluid, if we
neglect the force of gravity acting on the fluid. The fluid exerts a pressure on
its containing walls which, in turn, exert the same pressure on the fluid.
^his confusion can be avoided by either taking the unit of force as the poundal or the unit of
mass as the slug. However, since these units are used so infrequently, they will not be discussed
here.
Pressure 15
the pressure. Thus, the product of the specific weight in pounds per cubic inch
and the column height in inches equals the pressure in pounds per square inch
(see Fig. 17). In general terms, since the force exerted by liquid, F = W =
w V = wAz, then
force
p == wz (14)
area
where p = pressure
w = specific weight
z = column height
In Eq. 14, the units of pressure will be fixed by the selection of the units of
specific weight and the column height.
The atmospheric pressure must be added to the gage pressure to obtain the
true or absolute pressure (see Fig. 18). Barometers generally are used to
determine the atmospheric pressure. Hence, atmospheric pressure frequently
is referred to as the barometric pressure. Standard atmospheric pressure (i.e.,
pressure of the standard atmosphere) is defined as being equivalent to a
mercury column 760 mm high, where the mercury has a temperature of 0°C.
This is equivalent to a pressure of 14.6960 psi.
When the pressure is less than atmospheric, a vacuum is said to exist. The
magnitude of the vacuum denotes how much the pressure is below that of the
atmosphere. Vacuum generally is expressed as the height of a mercury
column.
Gage pressure
(negative) or vacuum
J Atmospheric
r
Absolute
pressure
pressure
t
The results of Example 14 point out that, even for low pressures, when
pressures are expressed in pascals, the pressures have very large values. To
avoid this difficulty, except for very low pressures, the term kilopascals (kPa)
is used frequently (1 kPa = 1000 Pa).
Two additional units of pressure are used extensively. One of these is
18 Introduction
1 N/m2 = 1 Pa
1000 Pa = 1 kPa
100,000 Pa  100 kPa = 1 bar
1,000,000 Pa = 1 MPa = 10 bars
101,325 Pa = 1 atm
61,060
pressure ^ = 0.603 atm Answer
1.0135 x 10
or
61,060 n
—jQ?— — 0.6106 bars Answer
17 TEMPERATURE
Temperature is connected with the “hotness” or “coldness” of a body.
However, these terms are purely relative and are not suited for use in a
thermodynamic sense. Experience has shown that when a “hot body” is
brought in contact with a “cold body,” there is a change in the physical
properties of each body. The changes in properties can be correlated with the
“hotness” of the body or with its temperature. Consider two blocks of steel,
A and B. Assume that our senses tell us that block A is “hot” and block B
is “cold.” Assume that the dimensions of the two blocks can be measured with
a high degree of accuracy. Now bring the two blocks together. Assume that a
running check can be made of the dimensions of the two blocks. It will be
found that there is a very small decrease in the dimensions of block A and a
very small increase in those of block B. These dimensions will change with
time, the changes becoming progressively smaller as time passes. Ultimately,
it will be found that there will be no further change in dimensions with time.
As the dimensions approach their final values, it becomes very difficult and
Temperature 19
then impossible for our senses to distinguish between the hot and cold blocks,
even before the blocks reach their final dimensions. When it becomes im¬
possible for our senses to distinguish between the hot and the cold blocks, the
blocks are said to have the same temperature. But this is only an ap¬
proximation since measurements show that the dimensions are not yet stabi¬
lized. Substituting for our senses, we may say that the temperatures of blocks
A and B are equal when there is no further change in measurements. In this
case, temperatures are associated with volumes and temperature changes with
volume changes.
Temperatures may also be associated with other properties. Suppose, as in
Figure 19, gases are confined in adjacent compartments separated from one
another by both a heatconducting partition and a nonconducting partition.
Again, it will be supposed that the temperature of one gas exceeds that of the
other gas. The pressures of the two gases are carefully measured. Now
remove the nonconducting partition (but not the conducting partition), and
continue to observe the pressures. The pressure of the “hot” gas decreases,
while that of the “cold” gas increases. After a lapse of time, the pressures of the
two gases remain stable. It may be concluded that the temperatures of the two
gases are then equal.
From the experiments just described, the following conclusions may be
drawn: When objects or systems that are not at the same temperature are
brought into intimate contact, a change in one or more properties occurs.
When there is equality of temperature, no change in properties takes place.
When equality of temperature exists, it may be said that thermal equilibrium
has been attained.
In the discussion above, it was shown how to ascertain whether or not two
bodies are at the same temperature by bringing the two bodies together. In
most cases, it is not feasible to move the two bodies. Under these conditions,
a third, small, portable body may be selected (see Fig. 110). If by measure¬
ments of the desired properties, it is found that bodies A and C are at the
same temperature and also bodies B and C are at the same temperature, it
may be concluded that bodies A and B are at the same temperature. This
conclusion is expressed in the Zeroth law of thermodynamics that states
Pressure
gage
“when two bodies are each in thermal equilibrium with a third body, they are
in thermal equilibrium with each other.”
It is now possible to determine whether or not the temperature of a body
equals a readily reproducible temperature. Two common reproducible tem¬
peratures are those at the “ice point” and the “steam point.”
The ice point is the freezing temperature of airsaturated water at standard
atmospheric pressure, which is 1.01325 x 105 Pa or 14.6960 psia. Or, stated
differently, the ice point is the temperature at which ice and airsaturated
water are in equilibrium at standard atmospheric pressure. The steam point is
the temperature at which pure water boils, or the temperature at which water
and its vapor are in equilibrium at standard atmospheric pressure. By use of a
suitable thermometric measuring device, it can be ascertained when some
object has a temperature equal to that of the ice point or that of the steam
point. The temperature at each of these two points can be arbitrarily desig¬
nated. In the Celsius (formerly called centigrade) system, the temperature of
the ice point is designated as 0 degrees and that of the steam point as 100
degrees. In the Fahrenheit system, the temperature of the ice point is
specified as 32 degrees and that of the steam point as 212 degrees.
To specify a temperature that is between that of the ice point and the steam
point, it is necessary to establish a scale on our thermometric device. Such a
procedure may be illustrated by use of a mercuryinglass thermometer (see
Fig. 111). If the Celsius scale is to be used, a mark may be etched on the
glass to designate the top of the mercury column when the temperature is
0°C. Likewise a second mark may be etched to designate 100°C. The distance
between the two marks may be divided into 100 equal parts, each division
being a Celsius degree.
The procedure outlined for a mercuryinglass thermometer may be applied
to other thermometric devices. In each case, the assumption is made that the
temperature change is directly proportional to the change in property that is
measured by the device. Unfortunately, the change in various properties as
measured by various thermometric devices is not precisely linear with tem¬
perature change. Hence, the various thermometric devices, with scales
established in the manner previously described, will not indicate exactly the
same temperatures for temperatures in between the steam and ice points. The
differences in the temperature readings indicated by various thermometric
devices are not large, about a maximum of onehalf degree Celsius. However,
for precise work, these differences cannot be ignored.
Temperatures vary almost exactly linearly with such properties as pressure
FIGURE 111 Liquidinglass
thermometer.
22 Introduction
and volume for those gases that are difficult to liquefy. (Such gases are
sometimes called “permanent” gases, because formerly it was thought that
they could not be liquefied.) Some of these gases are oxygen, nitrogen, carbon
monoxide, hydrogen, and helium, particularly the last two. Hence, these gases
are used for accurate temperature measurements in either a constantpressure
or constantvolume thermometer. In the constantpressure thermometer,
measured volume changes are correlated with temperature changes. Hence, it
may be said that temperature is a function of the volume. Thus,
T'=CV (15)
where T' is the indicated temperature and V is the volume observed from the
constantpressure thermometer.
The constantvolume thermometer is shown schematically in Figure 112. A
capillary tube connects the thermometer bulb with a manometer type of
pressuremeasuring device. The liquid in the lefthand liquidcolumn tube may
be brought to the reference line by adjusting the height of the leveling vessel.
A measurement of the height of the liquid in the righthand liquidcolumn tube
permits the calculation of the gas pressure in the thermometer bulb. For this
thermometer,
T' = C'p (16)
If Eq. 16 is applied to the ice and steam points, the result is
where the subscript s refers to the steam point and i to the ice point.
^ = limit (18)
Ii Pj~>0 Pi
where Ts and T, are the true temperatures at the steam and ice points. Very
careful experimental determination shows that the righthand side of Eq. 18
has a value of 1.36609 ± 0.00004.
From the foregoing discussion it may be deduced that the attempt to
establish temperature as a function of a property of substances is not
satisfactory because of lack of uniformity in the variations in the various
properties of substances with a variation in temperature. However, when the
pressure in a gas thermometer at the icepoint temperature is reduced and
approaches zero as a limit, then a temperature may be measured which is
independent of the gas. It is for this reason that the temperatures in Eq. 18
are said to be true temperatures.
Since for the Celsius system of temperature, Ts  T, = 100, and T5/T, =
1.36609,
temperatures are expressed in degrees Kelvin (K) in the Celsius system. Thus
Eq. 19 becomes
T, = 273.15 K
The ratio of one degree Celsius to one degree Fahrenheit equals 180/100 or
1.8. Absolute temperatures are expressed in degrees Rankine (R) in the
Fahrenheit system. Thus, Eq. 19 becomes
In the preceding discussion, one of the two fixed points used was the ice
point. This point was chosen since, by definition, the temperature at this point
is exactly zero degrees on the Celsius scale. However, it is somewhat difficult
to reproduce this temperature precisely. It is somewhat easier to reproduce
the triplepoint temperature, the temperature where ice, water, and water
vapor all are in equilibrium. The temperature at the triple point is 0.01°C or
32.018° F.
To measure a temperature other than that at the steam point, Eq. 18 may
be modified as follows:
T
T,
= limit (—\ (Ml)
Pio \PiJ
The relations between the various temperature scales are shown in Figure
114.
When Pi has a finite value, the temperature determined by use of pressure
measurements is a function of the properties of the gas that is employed
(refer to Eq. 111). However, when p, is reduced to zero, the temperature
determined becomes independent of the properties of the gas. Hence, this
temperature sometimes is known as a thermodynamic temperature. An
entirely different concept of a thermodynamic temperature will be discussed
in Chapter 6, as a consequence of the second law.
Although the concept of a thermodynamic temperature is a basic one, it is
very difficult to use directly in the determination of temperature. Because of
this, many efforts have been made to establish a temperature scale that is
easily reproducible, and yet coincides very closely with the thermodynamic
scale of temperature. The latest of these efforts were those of the International
Committees on Weight and Measures. They adopted the International Practical
Temperature Scale of 1968 (IPTS68), which is reproduced in Table 11 with the
addition of calculated values in degrees Rankine and Fahrenheit.
Rankine Fahrenheit Kelvin Celsius
s~\ A
Table 11
Defined Fixed Point, International
Practical Temperature Scale of 1968 (IPTS68)
Ka °Ca R °F
25
26 Introduction
19 PROCESSES
Engineers are concerned with systems in which changes of some kind take
place. The term process is used to describe how changes in state occur. A
system may change from its initial to final state in one specified manner. Such
a change is said to be a single process. A change in state may start in one
manner and then proceed in one or more different manners before the
terminal state is reached. For these cases, two or more processes are said to
take place between the initial and final states. When a system undergoes a
series of processes and ultimately returns to its initial state, the series of
processes involved constitutes a cycle.
Many open systems operate under steadystate conditions (i.e., the states of
various parts of the system do not change with time). However, there is a
change in state of the fluid as it moves through the system. Thus, for an open
system, the term process is used to describe what happens to the fluid as it
moves through the system.
In some processes, certain properties remain constant throughout the
process. When the pressure remains constant throughout a process, the
process is said to be a constantpressure or isobaric process. As the name
implies, the temperature remains constant in a constanttemperature process.
This process frequently is called an isothermal process. Likewise, a process
may be a constantvolume process.5 Another common process that will be
encountered frequently throughout this text is the adiabatic process. An
adiabatic process is defined as a process that takes place with no heat
exchange between the system and its surroundings, that is, the system is
thermally isolated from its surroundings. (Although no heat is added in an
adiabatic process, such a process definitely is not an isothermal process for
gases and vapors since work exchanges with the surroundings will cause a
temperature change in the system.)
During the change in state of a system, there may be variations in proper¬
ties, such as pressure and temperature, throughout the system. Under these
conditions the state of the system cannot be specified. In most of these cases
it is not possible to describe fully the nature of the process taking place. On
the other hand, when the properties are uniform throughout the system and
remain so, the system is said to be in equilibrium and the type of process can
be fully specified for a change in state of the system. The term equilibrium
will be discussed more extensively later on.
here, consider an ideal gas. The volume of the molecules themselves as well
as their intermolecular attractions can be neglected. The temperature of the
gas can be determined by inserting a thermometer into the gas. If the gas
temperature is high, energy will be transferred from the gas molecules to the
thermometer. Thus, the thermometer measures the energy of the molecules of
an ideal gas. This energy is kinetic energy. Thus, it can be said that tem¬
perature is a measure of the mean kinetic energy of the molecules of an ideal
gas.
In Chapter 15, it is pointed out that the pressure exerted by a molecule as it
strikes its containing wall is a function of its mass and its velocity. The total
pressure is a function of the product of the pressure exerted per impact and
the number of impacts per unit time. The number of impacts per unit time is a
function of the mean velocity of the molecules and the number of molecules.
Thus, the total pressure is a function of the product of mass per molecule and
its velocity, and the number of molecules and their mean molecular velocities,
or, the total pressure is a function of the number of molecules, the mass of
the molecules, and the mean square of their velocity. In other words, the
pressure exerted by the molecules of an ideal gas is proportional to the product
of the mean kinetic energy per molecule and the number of molecules.
The concepts presented here for an ideal gas are of value because they
show the various factors that influence temperature and pressure. The devia¬
tions in these relationships for actual gases are discussed in subsequent
chapters.
Problems 29
PROBLEMS _____
11 State whether the following systems are open or closed: (a) electric
storage battery, (b) incinerator, (c) household refrigerator, (d) fuel cell,
(e) steam turbine.
12 Specify, if possible, where the system boundaries must be placed if
the following systems can be taken as closed systems: (a) air con¬
ditioning unit, (b) nuclear reactor, (c) household heating system, (d)
internal combustion engine.
13 The same as Problem 12 except that the systems are to be open.
14 The refrigerant entering the evaporator of a refrigerating system con¬
sists of a vapor that entrains drops of liquid. Is the refrigerant homo¬
geneous?
15 (a) Is atmospheric air normally homogeneous?
(b) Same as (a) but during a rainstorm.
16 In a gasturbine locomotive, the energy output is taken as the energy
delivered by the wheels. Specify the boundaries of the system.
17 Determine the mass of 122 liters of water having a temperature of 50°C.
18 Determine the weight in newtons of the water in Problem 17 where the
acceleration of gravity is 960 cm/s2.
19 Determine the pressure, in pascals, exerted by a column of mercury
1.87 m high that has a temperature of 90° C.
110 A salt is used in a heat storage system for solar energy. When can the
system be taken to be homogeneous?
111 (a) During expansion in a steam turbine, some of the steam condenses.
Is the steamwater mixture at turbine exit homogeneous?
(b) Is the steam at turbine entrance normally homogeneous?
112 A mercury manometer indicates a vacuum of 62 cm of mercury (20°C)
in a condenser. Determine the absolute pressure in the condenser in
pascals if the barometer pressure is 750 mm of mercury.
113 A water manometer (15°C) indicates a pressure of 32 cm of water
above atmospheric. The barometric pressure is 752 mm of mercury.
Determine the absolute pressure.
114 A tank having a volume of 1.22 m3 contains 6.48 kg of nitrogen and
7.78 kg of oxygen. Determine the density and the specific volume of the
mixture.
115 The pressure in a constantvolume thermometer at the ice point is
12,300 Pa. Calculate the pressure at a temperature of 85°C. Is this
calculated pressure precise or a close approximation?
116 Determine the force required in newtons to give a 4200g mass an
acceleration of 27 cm/s2.
30 Introduction
21 INTRODUCTION
As stated in Chapter 1, the first Saw deals with energy transfers and energy
transformations. Energy was defined in the broad sense as the capacity to do
work. It is difficult to understand energy fully since energy cannot be seen and
does not have substance. It is manifested only by the results it produces.
When added to a system, it produces changes in the physical and/or chemical
aspects of this system. Furthermore, physical or chemical aspects of the
system cannot change unless energy is involved.
31
32 The First Law
where W = work
Fl = the component, in the direction of motion, of the force acting on the
object
/ = distance moved or the displacement of the object
'The term 8W indicates that Eq. 21 is not an exact differential equation. Since work is done only
during a displacement, the terms W, and W2 are wholly nonexistent. The term f2 SW may be
evaluated as WU2, designating the work done between states 1 and 2, for a particular path or
process.
Energies Involved in the First Law 33
\
V
s
s
V
s
s
s 
V
that crosses the boundary of a system is difficult. It is true that when the
thermal conductivity of the heat flow path is known, this factor together with
the temperature difference enables the calculation of the heat flow. However,
the thermal conductivity frequently is unknown and the heat flow must be
determined by indirect means. These means are discussed later on.
Table 21
Forms of Energy
Transferred Energies
datum. The potential energy of an object not on the surface equals the work
required to elevate it from the surface (see Fig. 22). From Eq. 21, the potential
energy,
PE. = Fgz
= Wz (22)
where W is the force of gravity and hence the weight of the object at the
given location, and z is the elevation above the earth’s surface. Unless there
is an extremely large change in elevation, the weight of the object may be
taken as a constant at any given location.
The kinetic energy possessed by a moving object equals the work required
to bring it from rest to its existing velocity. Thus,
dK.E. = 8W = F dl
But
dV _ dl dV dY
F = ma = m mV
dt m dt dl dl
Then
dK.E. = mV dl = mV dV
dl
mV2
K.E. = (23)
In addition to the force of gravity, other forces may act on the system,
causing work to be transferred. Some of these forces are body forces. These
forces act on the system as a whole. A common example of a body force is
the force of gravity.
In the fields of electricity and magnetism there are many examples of body
force. One example is the case of two magnets (see Fig. 23). Flere the north
pole of magnet A is separated from the south pole of magnet B. The force of
attraction between the two poles is
mxm2
(24)
r2
W,„l 2 = f Fm dr (24a)
s r>■
forces tend to be balanced. At the surface of the liquid, molecules are acted
on only by those molecules that are in the liquid. (The molecules in the gaseous
phase above the surface of the liquid normally are so far apart that they do
not offer a significant force on those at the liquid surface.) The net result is
that there is a downward force exerted on the molecules at the surface. This
downward force resists efforts to extend the surface by the application of a
force. Surface tension is defined as the force required per unit area to
increase the surface area of the liquid. The work to overcome this force is
illustrated in Figure 24. A liquid, such as a soap solution, is formed into a
very thin sheet on a wire frame. As a movable wire is pulled downward, the
films are stretched. (Note that there is a surface film on each side of the thin
sheet of liquid.) The work required to stretch the two films,
Wf = 2 a lx (25)
/?///>//>T?m
(a)
the expression
W = FI (26)
In reality, the gas pressure varies during the compression. Then Eq. 26
becomes, in more general form,
Since force is a product of pressure and area, Eq. 27 may be written as
2 2
W,.2 = f pA dl = j p dV (27a)
or
8W = PdV
Note that the work delivered by the face of the piston, Eq. 27a, is in¬
dependent of whether or not the system is closed as in Figure 25 a or open as
in Figure 25 b.
In all cases discussed so far, care must be taken in finding the work
required for the desired effect to use the resisting force. For example, a force
greater than the force of gravity may be applied to the raising of a weight. The
extra force may accelerate the weight or, if the weight was being dragged up
the side of a building, be required to overcome friction. In the use of Eq. 27a,
the pressure that must be used is the gas pressure in direct contact with the
piston and not the mean gas pressure in the cylinder. (In most cases these
pressures will be equal.) Furthermore, the pressure at the piston face at all
times must be specifiable in terms of piston position.
In the SI system, since force is expressed in newtons and distance in
meters, the units of work are newtonmeters (Nm). One joule (J) equals one
newtonmeter. Force may also be expressed in dynes and distance in cen¬
timeters. When this is done, the unit of work is the dynecentimeter. The
dynecentimeter is designated as the erg. There are 107 ergs per joule. In the
English system, the common unit of force is the pound force and distance is
measured in feet. Thus, work has the dimensions of poundfeet. Since torque
in the English system also has the same dimensions but is not energy, work is
expressed in footpounds to distinguish between the two.
of the elevator,
Example 22. Same as Example 21 but determine the work in footpounds.
Solution.
585
mass of the elevator = .   = 1289.7 Ibm
0.45359
where 0.45359 = kilograms per pound
weight of the elevator = 1289.7 lb/
change in elevation = 32 x 3.28 = 104.99 ft
where 3.28 = feet per meter
work = 1289.7 x 104.99 = 135,400 ftlb Answer
b. Heat
Generally, it is more difficult to measure heat transferred to a system than it is
to measure work. It may be rather easy to measure the temperature difference
causing a flow of heat, but unless the conductivity of the heat flow path is
known, the heat flow cannot be determined directly. Rather, it is necessary to
determine the effects of the heat flow on the system or on the source that is
supplying the heat.
Normally, addition of heat produces a temperature rise of the system. The
amount of heat required to produce a given temperature rise of the system
depends on the nature of the system, its mas^s, and also what takes place
within the system during heat addition. It is therefore necessary to determine
the amount of heat that must be added to produce a temperature rise of one
degree of a unit mass of the system for each type of process. This amount of
heat is known as the specific heat of the system. It is also termed the specific
heat capacity and the heat capacity.
From the definition of specific heat, the amount of heat added to a system is
given as
8Q = me (IT (28)
2As in the case of 8W, the term 8Q indicates that this is an inexact differential. Since heat is
transferred only during a change in state, Qi and Q2 are wholly nonexistent. Then /2 8Q becomes
Qi_2, designating the heat added between states 1 and 2 for a particular process.
40 The First Law
With the volume remaining constant, no work is performed. Hence, all of the
heat added must go to increasing the internal energy of the system. Or
8Qv=dU (29)
dU
c = (211)
m dI
This specific heat is also a true property since its value depends solely on the
properties of a system.
Originally, the unit of heat was the calorie (cal), which was defined as the
amount of heat required to increase the temperature of 1 g of water 1°C.
Unfortunately, this amount of heat required varies with the temperature and
the pressure of the water. These effects are shown in Figure 26. To avoid the
dependence of a fundamental unit on such variables, the unit of heat in the SI
system is taken as the joule, which as stated earlier, is one newtonmeter.
Over the period of years, various international conferences have established
relationships between the joule and other forms of energy. There is a very
small difference in these conversion factors. The International Table fixed the
I.T. calorie as equal to 4.1868 International Table joules. This value will be
used here.
The unit of heat in the English system, the British thermal unit (Btu), was
also originally defined in terms of the properties of water, namely, the amount
of heat required to increase the temperature of 1 lb of water 1°F. Since there
are 453.59237 grams per pound and since 1°C equals 1.8°F, 1 Btu equals
251.9958 cal. Using these figures, the I.T. Btu equals 1055.056 J. Since 1 ftlb
equals 1.355818 J, 1 Btu = 778.169 ftlb.
Evaluation of Transferred Energies 41
20 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340
Temperature (° C)
FIGURE 26 Effects of temperature and pressure on the specific heat of water.
Example 23. A tank contains 5.75 kg of air. The addition of 64,100 cal
increases the temperature of the air from 20°C to 85°C. Determine the specific
heat of the air.
c = Ql2
m(T2 —T\)
Example 24. Express the amount of air in Example 23 in pounds, the heat
added in Btu and the temperature in degrees Fahrenheit. Determine the specific
heat, Btu/lb°F.
Solution
5.75
mass of air =  12.68 lb
0.45359
64,100
heat added = = 254.4 Btu
252
temperature change = (85  20) 1.8= 117° F
Q, 2 _ 254.4
c = = 0.1715 Btu/lb° F Answer
m(T2— T,) 12.68 x 117
42 The First Law
Wf = pV (212)
It is difficult to describe this work term in one or two words. It is called flow
work for lack of better terminology and is designated as Wf. It should be
thought of as the equivalent amount of work required to move the fluid
against the resisting pressure. It must not be confused with the work entering
(fWill S \ YYYWS \ \ \ \ SS
System
Flow— p — ■*—P
JL
e/
Where s refers to the system, 1 refers to the initial state of the system and 2
to the final state. V is the total fluid volume entering or leaving during the
process under consideration. Q is the heat added to the system and W is the
net work delivered by the system. In general, flow is involved in Eq. 213.
Hence, care must be taken to examine the system for a specified time interval
and to make certain that all of the energies are evaluated for that time
interval.
Equation 213 can be arranged as follows:
27 POWER
The size of workproducing devices is dependent not on the total work to be
delivered, but on the rate at which it is delivered, that is, on the power
required. Power is defined as the time rate of doing work. In the SI system,
the fundamental unit of power is the watt (W). The watt is defined as the work
done at the rate of a joule per second. Since the watt is a small unit of power,
the kilowatt (kW), which is a thousand watts, is used extensively. For still
44 The First Law
larger amounts of power, the megawatt (MW), which is a million watts, may
be used.
Although rates of heat addition to a system may be expressed in terms of
watts, care must be taken not to think of this amount of heat as being equal to
the electrical energy deliverable. For example, a nuclear reactor, rated at
1000 MW, may produce steam for a steam turbogenerator unit. The electrical
output of the generator may be only 320 MW and not 1000 MW. To avoid this
difficulty when dealing with rates of heat transfers expressed in watts, it is
customary to express them as watts thermal. Thus, the rating of the reactor
could be expressed as 1000 MW(.
Solution. Assume that the acceleration of gravity equals the standard value.
Then the weight of the object,
In the English system, the unit of power is the horsepower (hp), which is
defined as work being done at the rate of 33,000 ftlb/min.
Example 26. For Example 25, determine the mass in pounds and the
distance in feet. Determine the horsepower required.
Solution. The mass equals 210/0.45359 = 463 lb. Assuming that the ac¬
celeration of gravity substantially equals the standard value,
37 200
p0Wer = (33,000/60) x 94 = 0 72 hp Answer
Since there are 778.169 footpounds per Btu, there are 33,000/778.169 =
42.407 Btu per horsepowerminute or 2544.4 Btu per horsepowerhour. Using
the figure of 1055.056 joules per Btu, there are 0.7457 kilowatts per horse¬
power. For these conditions one kilowatt hour (1 kWh) equals 3412 Btu.
Example 27. A solar cell system is to supply 1050 kWh/month. The average
output is 15 percent of the rated power. Determine the rated power required.
Solution. Assume 30 days per month.
Enthalpy 45
1050
average power required =  1.458 kW
30x24
1.458
rated power = = 9.72 kW Answer
0.15
Solution
750,000 kW = 750,000,000 W
= 750,000,000 J/s
2,250,000
steam flow = = 625 kg/s
3600
750,000,000
work = 1,200,000 J/kg Answer
625
Example 29. The power required by a plane flying at 545 km/h is 1800 kW.
Determine the average resisting force in newtons.
Solution
1 W = 1 J/s
power required = 1800 x 1000 = 1,800,000 J/s
545 x 1000
distance traveled per second = 151.4 m/s
3600
r 1,800,000 11CAAXT
force = — = 11,890 N Answer
28 ENTHALPY
In Eq. 213, the terms U and pV represent the energy of a given mass, m, of
fluid entering the system. But U = mu and Vmv. Then U + pV =
m(u + pv), where u is the internal energy per unit mass and v is the specific
volume. As will be discussed in some detail later one, when the state of the
fluid is fixed, the summation of u + pv is also fixed, and hence, has a specific
value. This eliminates the necessity of evaluating each term individually.
Credit for using this combination is given to Professor Williard Gibbs of Yale
University who, in 1879, designated it as his \ (chi) function.3 Unfortunately,
at the turn of the century, other terms such as total heat and heat content,
were applied to this function. These terms are entirely erroneous in their
implications and hence led to considerable confusion. Some years later, the
'This is one of three thermodynamic functions that are credited, in part at least, to Gibbs. The
other two functions will be discussed later on.
46 The First Law
term enthalpy was selected for this function and was given the symbol H. The
defining equation for enthalpy is
H = U + pV (215)
and
h = u + pv (215a)
Since 17, p, and V all are properties, H must also be a property. Because it
is composed of several properties, it is known as a compound property. As a
property, it can be tabulated in tables of properties of various substances.
Methods will be developed later on to evaluate enthalpy changes for both
ideal and actual gases.
Although the concept of enthalpy is a very valuable one when dealing with
flow, care must be taken in its use in nonflow conditions. The term pV was
shown to be the energy necessary to force a given mass of a fluid across a
given boundary of a system; hence, pV represents energy transmitted by the
fluid as it crosses the boundary of the system. Thus, for a fluid in motion, its
enthalpy is truly energy. On the other hand, for a substance at rest, the pV
term cannot represent energy being transmitted since no energy is being
transmitted. Thus, for a substance at rest, the pV term is not energy. Hence,
enthalpy cannot be energy and must not be used as such.
Although enthalpy can be used as energy only in the case of flow, it may be
useful for other purposes. In certain cases, such as for closed systems, it may
be necessary to determine changes in internal energies. However, some tables
of properties list values of enthalpies but not internal energies. Internal
energies may be calculated readily by using the defining equation of enthalpy,
H = U+pV, or U = HpV.
This general equation can be adapted readily to both open and closed
systems.
a. Open Systems
The application of Eq. 216 to open systems is illustrated in Figure 28.
However, before applying Eq. 216 to open (controlvolume) systems, the
problem should be analyzed carefully to eliminate energy quantities that are
either zero or are very small in comparison with other energy terms. For
many opensystems problems, the system may so closely approach steady
state conditions for the period of time under consideration that variations in
state conditions can be neglected. For steadystate conditions, the properties
FirstLaw Applications 47
v u
pV pV
of the system do not vary with time and the total mass rate of flows into and
out from the system are equal. Then, for a steadystate system, Eq. 214
becomes
For a steadystate system where the fluid enters at only one place and leaves
at a second place and does not change in composition within the system, Eq.
217 may be written for a specified time interval as
where subscript 2 designates the fluid leaving the system and 1 the fluid
entering the system. It should be noted that the total energy of the fluid
involved for this specified time interval equals the product of the energy per
unit mass and the mass flow for the time interval. Equation 217a calls for the
determination of the change in enthalpy of the fluid rather than the
specification of the absolute value of the enthalpies.
b. Closed Systems
The application of Eq. 216 to a closed system is illustrated in Figure 29. For
closed systems, Eq. 216 reduces to
Q=u52Us+W (218a)
Direction of
r Mechanicalii
J Electrical f
8Q = dU + 8W
8Q — dU T p dV
dH = dU + p dV+V dp
(dH)p = dU + p dV
Thus, it may be seen that for a constantpressure process (and only for a
constantpressure process) occurring in a closed system at rest, the heat
added is equal, numerically, to the change in enthalpy of the system or
(SQ)P = dH (219)
t J
air flowing from a tank, where it is stored under pressure, into a pipe line.
Assume that the velocity in the pipe line is sufficiently low so that the kinetic
energy of the air can be neglected. Unless the temperature of the air differs
significantly from that of the surroundings, heat exchanges can be neglected.
Applying Eq. 216, the result is 17S]  US2 = Hairout. As the air flows out from
the tank, the temperature of the air remaining in the tank drops. Hence, the
temperature of the air leaving the tank also drops. However, the total
enthalpy of the air leaving the tank in any given time interval equals the total
change in the internal energy of the air in the tank for the time interval.
122 ft. During the process, the system receives 75 Btu of heat and 2800 ftlb of
work and delivers 0.02 kWh of electrical energy. Determine the change in
internal energy of the system.
85(802  302)
2x 32.174x778.16
= 12.33 Btu Answer
Example 212. Air enters a nozzle with a velocity of 30 m/s. The decrease in
enthalpy in the nozzle is 170,000 J/kg. Determine the velocity at exit.
Solution. See Figure 211. Since the air passes through the nozzle in a very
small part of a second, there cannot be a significant amount of heat lost.
Because no work is delivered from the nozzle and there is no change in
elevation, Eq. 217a becomes
K.E.2k.e., = h,h2
or
K.E,= K.E, + HiH2
Then
K.E.
Hn FIGURE 211 Air nozzle.
FirstLaw Applications 51
The specific heat, c*, of air = 0.1715 cal/g°C (Example 23). Since there
are 4.1868 joules per calorie,
87.5
T2 121.9°C
4.1868x0.1715
t2 = 161.9°C Answer
Problems 53
PROBLEMS ____
21 An elevator, having a mass of 972 kg, is to be raised a distance of
14.5 km. Determine the minimum work required.
22 A piston having a diameter of 24 cm moves a distance of 60 cm when
acted on by a gas pressure of 430 kPa. Determine the work done in
joules.
23 Change all data in Problem 22 to English units and then compute the
work done in footpounds.
24 1528 kl of water (temperature = 20°C) are elevated 26 m. Determine the
work required in joules.
25 Determine the kinetic energy possessed by a 1050kg automobile when
it is traveling at a speed of 82 km an hour.
26 The automobile in Problem 25 crashes into an object which it displaces
1.8 m as it comes to rest. Determine the average force exerted on the
object.
27 Water exists in a reservoir at an elevation of 85.3 m above that of the
hydraulic turbine, (a) Determine the potential energy per kilogram of
water, (b) Assuming 100 percent conversion of potential energy into
work, determine the water flow per second to produce 75,000 kW.
28 A force of 16.5 kg, acting on an object at an angle of 20° to the motion
of the object, moves it a distance of 28.5 m. Determine the work done
in joules.
29 (a) In a domestic hot water heater determine the amount of heat to be
added to 72 liters of water to raise the temperature from 9°C to 55°C.
(b) Determine the kilowatthours required.
210 A diesel engine delivers 2860 kW of power when burning 615 kg of fuel
per hour. The heating value of the fuel is 42,000 kJ/kg. Determine the
total amount of the heat loss from the engine and the energy carried
away by the exhaust gases per hour.
211 The enthalpy of air is increased by 139.5 J/g in a compressor. The rate
of air flow is 16.7 kg/min. The power input is 48.2 kW. Determine the
heat loss from the compressor per minute.
212 A reciprocating pump has a displacement of 0.24 m3. During the deliv¬
ery stroke, the mean pressure on the face of the piston is 1024 kPa.
The delivery stroke takes place in 0.006 min. Determine the power
required at this time.
213 A spring is compressed 22.7 cm by the application of an average force
of 452 N. Neglecting heat losses, determine the increase in the internal
energy of the spring. Physically, how can the internal energy of the
spring increase?
214 The spring in Problem 213 is made of steel. Its reported temperature
54 The First Law
rise is 2.5°C. The specific heat of the steel is 0.45 J/g°C and its mass is
76 g. Check this data and make comments.
215 A ball having a weight of 2.32 kg is dropped 22.2 m. It then bounces
8.2 m. Neglecting heat losses, determine the net change in internal
energy of the ball in joules.
216 A storage battery delivers current at the rate of 44.2 A for a 24min
period. The heat lost from the battery during this period is 95 kJ.
Determine the change in internal energy of the battery if the voltage is
12.
217 Air enters a diffuser with a velocity of 280 m/s and leaves with a
velocity of 14 m/s. Determine the change in enthalpy in J/kg of air.
State what assumption must be made and justify this assumption.
218 (a) Water enters a steam generator at a pressure of 20,000 kPa. It has
an internal energy of 837 J/g and a specific volume of 1.138 cm3/g.
Steam leaves the steam generator at a pressure of 18,000 kPa. It has an
internal energy of 3080 J/g and a specific volume of 18.68 cm3/g.
Determine the heat added per minute if the flow of water is
2,130,000 kg/h.
(b) Comment on the necessity of obtaining accurate values of the pV
term for the water and for the steam.
219 (a) Determine the minimum power required to bring a 100car train from
rest up to a speed of 84 km/h in a period of 3 min. The average mass of
each car is 85,000 kg.
(b) State the assumptions made in part (a).
220 An oil pipeline experiences an increase in its elevation of 112 m. Is
there a change in the enthalpy of the oil if heat transfer can be
neglected? Why?
221 A tank of air is heated by the addition of 720 kJ. The increase in
enthalpy of the air is 1008 kJ. Explain why the increase in enthalpy
exceeds the heat added.
222 The heattransfer rate in a pressurized water nuclear reactor is
1120 MW. The water temperature increases from 60° C to 320° C. The
mean specific heat of the water is 4.37 J/g°C. Determine the mass rate
of water flow through the reactor.
223 Air enters the combustion chamber of a household warmair furnace
with an enthalpy of 305 J/g. Gases leave the furnace with an enthalpy of
622 J/g. There are 18 g of air per gram of fuel. The enthalpy of the
entering fuel is 44,500 J/g. The furnace is to deliver 54,800 kJ of heat
per hour. Determine the rate of fuel flow.
224 At a speed of 90 km/h, an automobile requires 20 kW of power to
overcome the wind resistance. Determine the wind resistance in new¬
tons.
Problems 55
225 The heat output for a nuclear reactor is 1240 MW. Determine the heat
output in kJ/s.
226 An elevator and its contents weigh 12,400 kg. Determine the minimum
power required to raise the elevator at a rate of 1.4 m/s.
227 The surface level of water in a reservoir is 92.5 m above that of a
hydraulic turbine. The efficiency (i.e., the portion of the available
potential energy the turbine uses) is 90 percent. Determine the water
flow, in kg/s, needed to produce 100,000 kW.
228 (a) Determine the kinetic energy in joules possessed by a 1020kg car
traveling at 30 km/h.
(b) Same as part (a) but at 120 km/h.
229 (a) How much heat is required to heat 100 kg of water from 40° C to
80°C? The pressure on the water is 100 bars. Refer to Figure 26.
(b) Same as part (a) except from 200° C to 240° C.
230 A jet plane uses four jets, each developing a thrust of 15,000 N.
Determine the total power produced at a speed of 1020 km/h.
231 It requires 9329.4 kJ to heat 120 kg of ice from 40°C to 0°C. Deter¬
mine the mean specific heat of the ice.
232 The enthalpy of a refrigerant is 359 J/g at the compressor entrance and
381 J/g at the compressor exit. The rate of refrigerant flow is 62 kg/min.
The heat lost from the compressor is 12 percent of the work input.
Determine the power input.
233 The motor and the compressor of a heat pump are located within the
building to be heated. The heat pump delivers 2.4 times as much heat
directly to the building as the power it receives. The efficiency of the
electric motor is 82 percent. Determine the power input to the motor
when the total heat to be supplied to the building is 120,000 kJ/h.
234 Hot gases enter the blades of a gas turbine with a velocity of 550 m/s
and leave with a velocity of 120 m/s. There is an increase in the enthalpy of
the gases in the blade passages of 5.1 J/g. The rate of gas flow is 98 kg/min.
Determine the power produced.
235 Humid air enters a dehumidifier with an enthalpy of 50.2 J/g of dry air
and 2550 J/g of water vapor. There are 0.02 g of vapor per gram of dry
air at entrance of 0.009 g at exit. The dry air at exit has an enthalpy of
30.7 J/g. The vapor at exit has an enthalpy of 2522 J/g. The condensate
at exit has an enthalpy of 51.1 J/g. The rate of flow of the dry air is
132.5 kg/min. Determine the rate of heat removal in the dehumidifier.
236 (a) Steam enters a frictionless turbine nozzle with a velocity of 30 m/s
and leaves with a velocity of 550 m/s. Determine the change in enthalpy
in the nozzle. Justify the assumption that must be made.
(b) Same as part (a) except for an actual nozzle. Does the amount of
friction in the nozzle change the answer? Why?
56 The First Law
237 (a) Air flows from a very large tank where conditions are maintained
constant into a small tank that, initially, was completely evacuated.
After a short period of time, the pressure in the small tank is ap¬
proximately equal to that in the large tank. Compare the final tem¬
perature of the air in the small tank with that in the line at the entrance
to the small tank. Explain.
(b) If the temperature of the air in the large tank is 40° C, find the final
maximum temperature in the small tank.
_ 3 _
31 INTRODUCTION
Although the majority of thermodynamic problems encountered by engineers
involve gases and vapors, it is desirable at this time to examine briefly the
existence of substances in each of their three phases; namely, solid, liquid,
and gaseous. Because it is the one substance that is encountered most
frequently in its three phases, water will be used here to illustrate the
existence of substances in their three phases.
Ice at atmospheric pressure and at temperatures below 0°C will sublimate,
that is, pass directly from the solid to gaseous phase. Ice, when surrounded by
air at standard atmospheric pressure, will melt at 0°C when heat is supplied to
it. When ice, water, and water vapor are contained in an isolated system at a
vapor pressure of 611.3 Pa (0.006113 bars)1 and a temperature of 0.01°C, they
will be in a state of equilibrium, that is, there will be no change in the amount
existing in each phase. This condition is known as the triple point, with the
temperature being the triplepoint temperature and the pressure the triple¬
point pressure.
Water existing at a temperature above 0°C has a tendency to vaporize.
When sufficient heat is added to it, it will boil. The temperature at which it
boils is dependent on the pressure imposed on the vapor produced (see Fig.
31). When the vapor pressure is low, say 1227.6 Pa (0.012276 bars)1, water
boils at a temperature of 10°C. At standard atmospheric pressure, water boils
at 100°C. At the very high pressure of 20 MPa (200 bars), water will not boil
until it is heated to 365.81°C.
Because the boiling temperature increases with an increase in pressure, the
specific volume of boiling water also increases with pressure. This is shown in
Figure 32. However, as the pressure is increased, the volume of the vapor
produced by boiling decreases. Thus, with an increase in pressure, the specific
volume of water and its vapor approach each other. At a pressure of
22.09 MPa and a temperature of 374.136°C, the two specific volumes are
equal. An examination of other properties of boiling water and its vapor show
57
Q
FIGURE 31 Liquid boiling under pressure.
Temperature
58
Introduction 59
that they too approach each other as the boiling pressure is increased, and
become equal at the same conditions as do the specific volumes. This state at
which the properties of a boiling liquid and its vapor become equal is known
as the critical state. The pressure at this point is the critical pressure and the
temperature is the critical temperature. At pressures and temperatures greater
than the critical values, there is no distinction between a liquid and its vapor.
Turning to the solid phase, as the pressure on ice is increased, the melting
temperature decreases. At a pressure of approximately 210 MPa (2100 bars),
ice melts at —21°C. At higher pressures ice can have six other phases. Since
the engineer seldom encounters ice under such high pressures, these other
phases will not be discussed here.
The three phases of water are shown on the pT plane, Figure 33, and the
Pia plane. Figure 34. It is to be noted that water expands upon freezing.
Most other substances contract upon freezing. Figures 35 and 36 show the
pT and pv planes for such a substance, in this case, carbon dioxide.
The pv and pT planes may be combined to form a pvT three
dimensional surface for various substances. A p^T surface for water is
shown in Figure 37, and a pvT surface for substances that contract upon
freezing, in Figure 38.
Ideal Versus Actual Gases 61
P=f(v,T) (31)
Two early investigators, Boyle and Charles, made experimental studies of the
relationships among these properties. Both worked with gases that are not
easy to liquefy, such as oxygen, nitrogen, carbon monoxide, and hydrogen.
62 Ideal and Actual Gases
For the most part, their work was done at low or moderate pressures and at
temperatures much in excess of the condensation point of the gases.
Boyle investigated the pressurevolume variations when the temperature
was held constant. His results may be expressed as
(pv)T = C (32)
and
(34)
The subscripts denote the property that is held constant. Equations 32 and
34 may be combined to establish a relationship between pressure, volume,
and temperature. This is done in Appendix A14 and shows that
p v = RT (35)
pV = mRT (35a)
An ideal gas is defined as one that obeys the laws of Boyle and Charles, and
hence Eq. 35. Thus, Eq. 35 is said to be the characteristic equation of an
ideal gas.
Later investigators, such as Amagat, found that many gases deviated greatly
under many conditions from the laws of Boyle and Charles, and that even the
gases they studied showed large deviations from these laws at low temperatures
and high pressures. To investigate these variations, Amagat plotted the pv
product against pressure for various temperatures. Such curves are known as
Amagat’s isothermals. A set of Amagat’s isothermals are shown for carbon
monoxide in Figure 39 and for steam in Figure 310. For an ideal gas, these
isothermals must be horizontal lines. From these two figures it may be noted that,
for steam, the isothermals deviate greatly from the horizontal, the deviations
being greater at low temperatures. For carbon monoxide, the deviations are large
at very low temperatures, but at the relatively low temperature of 300 K, the
isotherm is almost horizontal except for pressures above 150 atm.
Ideal Versus Actual Gases 63
p » = ZRT (36)
pV = ZmRT (36a)
1 Under certain conditions, very serious errors will be caused by assuming that
the gas is an ideal one. For example, for steam at a pressure of 300 bars and a
temperature of 380°C, the compressibility factor is 0.175. This means that the
actual specific volume is only 17.5 percent of that of an ideal gas.
2 At high temperatures and at low and moderate pressures relative to the
critical values, the compressibility factor is close to unity, and hence, the
gas behaves substantially as an ideal gas.
3 For a given temperature and pressure, there may be a large difference
between the compressibility factors of steam and carbon monoxide.
For the conditions used by Boyle and Charles, namely for temperatures
that are not much below normal ambient temperature and for pressures not in
excess of approximately 20 atmospheres, it is evident from Figure 311 that
carbon monoxide may be treated as an ideal gas. A study of the compressibility
Pressure (atm)
Pressure (bars)
pV = c'nT (36b)
Equation 36b cannot be used easily since it calls for a knowledge of the
number of molecules, n, of the gas. The number of molecules present in even
a very small volume of a gas under normal conditions is enormous. For
example, a cubic centimeter of air at standard atmospheric pressure and 25°C
contains approximately 2.46 x 1019 molecules. What is required, then, is an
unit of quantity, similar to the dozen or the gross, but for a very much larger
number of molecules. Such an unit is the mole.
66 Ideal and Actual Gases
In the SI system, the mole is the gram mole (g mole). The gram mole is
defined as the mass of the substance whose mass in grams is equivalent to its
molecular “weight.” There are approximately 6.02486 x 1023 molecules in a
gram mole. This number, designated as n0, is known as Avogradro’s number.
Although the mole has mass and volume, it is not a unit of mass or of volume
but simply is a very definite, specific number of molecules. By definition, the
number of moles present,
tn
N = ™ (37)
m
where m is the mass per mole, which equals, numerically, the molecular
“weight.”
Since the total number of molecules present, n, is the product of the
number of molecules per mole, n0, and the number of moles, N, Eq. 36b may
be written as
pV = c'n0NT (38)
The two constants in Eq. 38, c' and n0, may be combined into a single
constant, which is designated as R0. Since nothing was assumed as to the kind
of gas involved in deriving Eq. 36b, other than that it obeyed certain pos¬
tulates, R0 is independent of the kind of gas under consideration and, hence, it
has a specific value for all gases obeying the postulates set up in Section 110.
For this reason, R0 is known as the universal gas constant. Equation 38 now
becomes
pV = NRqT (39)
When the pressures are expressed in newtons per square meter, volumes in
cubic meters, and temperatures in degrees Kelvin, R0 has the value of
8.314 Nm/g moleK or 8.314 J/g moleK.
Comparing Eqs. 35a and 39, it is evident that the products of mR and NR0
must be equal. Substituting the value of N from Eq. 37, the particular gas
constant,
R=^ (310)
m
The value of R may be calculated readily for any gas by use of Eq. 310,
when the molecular “weight” of the gas is known. Under most conditions, Eq.
35a is more readily usable since the mass of a gas present may be directly
available. For convenience, the values of R are presented in Table 31.
As was done for actual gases in Eq. 6a, the compressibility factor, Z, can
be introduced into Eq. 39. Thus, for actual gases,
PV = ZNR0T (311)
In the English system, the pound mole (lb mole) is defined as the amount of a
substance whose mass in pounds is equivalent to its molecular “weight.”
The Mole 67
Table 31
Properties of Gases
Molecular Gas
Gas Formula Weight Constant, R Cp C ka
Note: The specific heats are for the gases at low pressures and at near room temperatures. The
units are joules per gramdegree K. The units for R are newtonmeters per gramdegree K, or
Nm/gK.
ak is defined as the ratio of cp to cv. See Sections 46 and 47.
When pressures are expressed in pounds per square foot, volumes in cubic
feet, masses in pounds, and temperatures in degrees Rankine, the value of R0
is 1545 lb/ ft/lb moleR.
Solution. Atmospheric pressure equals 1.01325 bars. One bar equals 100,000
newtons per square meter or 10 newtons per square centimeter. Thus, the
pressure of the carbon monoxide,
P
120
10x 1.01325
t1
n84a,m
,
The absolute temperature equals 92 + 273 = 365 K. It is evident for these
conditions, as shown in Figure 39, that the compressibility factor is sub¬
stantially unity.
The number of gram moles of carbon monoxide from Eq. 37 is
4.2 x 1000
N = 150 g moles
28
Example 32. Express the pressure in Example 31 in psia, the temperature
in degrees Rankine, and the mass in pounds. Determine the volume in cubic
feet.
Solution. One newton per square centimeter equals 1.4504 pounds per
square inch.
9.259(1545/28)x 657
volume = 13.39 ft3 Answer
174x 144
Example 33. Determine the density of steam at a pressure of 15.5 MPa and
a temperature of 410°C.
Solution. From Figure 312 the compressibility factor for steam is 0.76.
Using Eq. 310, the volume of 1 mole of steam,
1
= 0.0646 g/cm Answer
15.47
Hemisphere
of action
Values of the constants a and b depend on the kind of gas and the units
used in Eq. 312. When the pressures are expressed in bars, the volume in
cubic meters per kilogram mole, and the temperature in degrees Kelvin, R0
has a value of 0.08314 barm3/kg moleK. Using these units, the values of a
and b are given for various gases in Table 32.
Solution
362.9
v = = 20.16 cm lg Answer
18
This conclusion is based on the assumption that the molecules behave as spheres and is
equivalent to stating that the internal pressure is inversely proportional to the square of the
distance between molecules. In reality, molecules may be very complex in their structures. There
is some evidence to indicate that the internal pressure may be inversely proportional to the
seventh to ninth power of the distance between molecules. This evidence, of course, explains the
serious errors in the predictions by the use of the van der Waals equation under certain
conditions.
Accuracy of the van der Waals Equation 71
Table 32
Constants for van der Waals Equation
Gas aa 6a
(b) van der Waals equation, Eq. 312, is more easily solved by trial and error.
When v = 0.314 m3/g mole, van der Waals equation becomes
or
72.6 = 72.6
Then
0.314 x 106
specific volume = 17.44 cm3/g Answer
18 x 103
The true specific volume of steam as obtained from the Steam Tables3 for
these conditions is 18.18 cm3/g. It should be noted that the volume calculated
by the use of the van der Waals equation, while not very accurate, is much
closer to the true volume than the volume calculated by use of the idealgas
equation.
pressures and high temperatures, there is good agreement between the two
sets of curves; whereas, at high pressures and low temperatures, the idealgas
prediction is almost valueless. The van der Waals isothermal curves (shown in
Figure 316), although far from accurate, are a distinct improvement over
those for an ideal gas.
In addition to the isothermal lines shown in Figure 315, a liquid line and a
vapor line also are shown. The liquid line is the locus of the points represent¬
ing a boiling liquid. The vapor line is the locus of the points representing the
vapor formed from the boiling liquid. Since the phase change from a liquid to
a vapor occurs at constant temperature when the pressure is held constant,
isothermal curves are horizontal in this region. Note the 280° C line in Figure
315. As the pressure is increased, the volume change during vaporization
becomes smaller and becomes zero at a pressure of 220.9 bars, the critical
pressure. At this point the temperature is 374.14°C. (This is the critical
temperature.)
The van der Waals isothermal curve drawn at the critical temperature of
374.14°C (Fig. 316) shows a point of inversion, and hence, recognizes the
Accuracy of the van der Waals Equation 73
R0T a
(312a)
v — b v2
RqTc
=0
T Wcb)2
74 Ideal and Actual Gases
or
Also,
d2p\ _ 2RqTc 6a
0 (314)
sd v2) T (vc — b)2 v
or
3a(vc ~ by
RqTc — (314a)
vc = 3b (315)
T _ 8a
(316)
c~ 21 R0b
Accuracy of the van der Waals Equation 75
a
Pc = (317)
21b
Pc Vc 3
rTt 8
Table 33
Critical Properties3
aThe values for water vapor are based on values in Steam Tables, by J. H. Keenan, F. G. Keyes,
P. G. Hill, and J. G. Moore, Wiley New York, 1978. The properties of all other substances, except
air, were derived from Generalized Thermodynamic Properties of Pure Fluids, by Lydersen,
Greenkorn, and Hougen, Engineering Experiment Station, University of Wisconsin. We believe
that these values for the critical pressure and temperature are reliable. However, those for the
critical volume are subject to some question.
76 Ideal and Actual Gases
Table 34
PvT Relationships at the Critical
PcvJTcRo
Air 0.284
Ammonia nh3 0.243
Argon A 0.292
Carbon dioxide co2 0.275
Carbon monoxide CO 0.294
Helium He 0.306
Hydrogen h2 0.309
Nitrogen n2 0.291
Oxygen 02 0.291
Water vapor h2o 0.232
Actual values of pcvJTcR0, as shown in Table 34, differ significantly from the
value of  or 0.375.
Table 35
Equations of State
Name Equation Constants
Table 36
Constants for the BeattieBridgeman Equation
A0 a Bo b c x 10"4
/atmliters6'\ / liters3 \ / liters3 \ / liters3 \ /liters3K\
V g mole2 ,/ Vgmole/ Vg mole/ \g mole/ V g mole )
Note: When these units are used, the value of R0 is 0.08206 atmliter/g moieK.
The constants B, D, D, and so forth, are known as the virial coefficients. These
coefficients are a function of temperature. B is called the first virial
coefficient, C the second, and D the third, and so on. Equation 319 may also
be expressed as
Equations 319 and 319a are known as the virial equations of state.
Values of the virial coefficients as functions of temperature can be deter¬
mined from experimental data. The virial coefficients also can be deduced
from a study of the intermolecular forces. It might appear that the analysis of
the intermolecular forces would be quite easy and that these forces should be
proportional to the mass of the molecule and inversely proportional to the
78 Ideal and Actual Gases
op
27 b
8a
T = Tr
27bR0
v — 3b v
(a , a .v 8 aR0T
(r^Pr + 9F^)(3b^b) = 2TbRir (320)
or
(Pr + Wr ~ I) = f Tr
According to Eq. 320, all gases existing at the same reduced temperature
and pressure must have the same reduced volume. However, as noted earlier,
no gas obeys the van der Waals equation exactly, the deviations being the
Corresponding States and Reduced Properties 79
largest near the critical state. If, however, all gases deviate from the van der
Waals equation in the same amount, then gases existing at the same reduced
temperature and reduced pressure should have the same reduced properties in
addition to those of pressure and temperature. A careful examination of
various properties of various gases shows that although this statement is not
precisely true, it is approximately so.
When two gases exist at the same reduced temperature and reduced
pressure, they are said to be in corresponding states. Although various
properties have been determined for some substances, such as steam, over a
wide range of temperature and pressure, properties of most substances are
known only rather sketchily and then generally over a rather restricted range
of temperature and pressure. It should be recognized that it is extremely
difficult to determine certain properties of a substance with a high degree of
accuracy. And yet it is desirable to have available the thermodynamic
properties of the very large number of substances that are being used today.
It will be shown in Chapter 8 that when an accurate p^T formulation has
been obtained for any substance, it is possible to determine the changes in
other properties, such as internal energy, enthalpy, and entropy with a high
degree of accuracy. However, when an accurate p^T formulation is not
available, the concept of corresponding states may be used to obtain a good
approximation of the desired properties.
161.1 + 273.15
0.671
647.3
Solution
p = 70
0.947
pc 73.91
For steam, when p = 20.92 MPa and T = 0.80.9 K, v — 9.68 cm3/g. Then
9.68
3.083
3.14
4L. C. Nelson and E. F. Obert, “Generalized pvT properties of Gases,” Transactions of the
ASME, October 1954, pp. 10571066.
rH
o
o o
o
CO
o
00
o
ad
,/J/
% =
d
r'
o
CD
o
d
‘jopej A^iiqissajdiuoo
ID
o
d
o
■sT
o
o
oo
o
o
CO
o
o
o
01
oo
d
O'
o
CD
r^.
o
o
LO
o
d
Reduced Pressure, p
'r
FIGURE 317 Compressibility factors for reduced pressures 0 to 1.0. (Courtesy of Leonard C. Nelson and Edward F.
Obert.)
81
82
Reduced Pressure, p
FIGURE 318 Compressibility factors for reduced pressures 0 to 10.0. (Courtesy of Leonard C. Nelson and Edward F. Obert.)
Corresponding States and Reduced Properties 83
following form:
f(Pn Vn Tr) = 0
It has been found experimentally that for a wide range of temperatures and
pressures, there is a serious error in this type of equation. The curves of the
compressibility chart, on the other hand, are based on the following relation¬
ship:
Z = f(Pn Tr)
Since Nelson and Obert found that over an extensive region of temperature
and pressure, the compressibility factors for various substances did not
deviate by more than a small percentage, it follows that this equation is valid
for a wide range. It should not be inferred, however, that the equation is valid
over the entire range of temperatures and pressures, since there is evidence to
show that it is in considerable error in regions near the critical conditions.
In these charts, Nelson and Obert used a pseudoreduced volume which is
defined as follows:
= v = ZRTIp = 7Tl
RTJpc RTJpe Z pr
Since Z = f(pr, Tr),
= f'(pn Tr)
The establishment of this relationship enabled them to plot lines of constant
vr' on their charts.
When the compressibility factor is substantially unity, a substance may be
treated as an ideal gas when its pvT relations are considered. This is no
way implies that the specific heat is a constant. It is possible for the specific
heat to vary greatly in regions of high pressure and moderate temperature
where the compressibility factor is close to unity. The use of Figures 317 and
318 can be shown by the following examples.
ZJR0T 0.64x8.314x320
v = = 24.32 x 10 3m3/g mole
P 70 x 10s
or
24.32 x 10“5x 106
V = 5.528 cm'/g Answer
44
Example 38. A tank having a volume of 3.8 m3 contains the refrigerant F12,
at a pressure of 8 bars and a temperature of 60°C. Determine the mass of
84 Ideal and Actual Gases
refrigerant present. The critical pressure is 41.155 bars and the critical
temperature is 112°C.
Solution.
8
0.1944
41.15
= 333
0.864
 385
From tables of properties of this refrigerant, for the given conditions, the
specific volume is 25.25 cnr/g. Then the true mass of the F12 =
(3.8 x 106)/25.25 = 150,500 g or 150.5 kg.
310 SUMMARY
In this chapter, the pvT relationship has been developed for ideal gases.
Methods have been presented to adjust this relationship for actual gases. In
addition, the concept of corresponding states has been utilized to determine
the properties of actual gases. However, when the properties of wellknown
vapors are desired, it is more convenient to refer to tables of their properties.
A discussion of the properties of vapors has been delayed until Chapter 9.
One very important property of vapors is entropy, which is normally included
in tables of vapor properties. Hence, the discussion of vapor properties has
been delayed until the concept of entropy is developed.
Problems 85
PROBLEMS
_ 4 _
CHANGES IN STATE
OF GASES
87
88 Changes in State of Gases
Because of the large weight on the piston, the pressure of the gas in the
cylinder is high. Assume that the piston is weightless and without friction. In
the ideal case, the weight may be removed instantaneously and placed in the
position shown in Figure 44. Since the piston is weightless, it will move
upward instantaneously. This will cause the pressure just beneath the piston
to drop, also instantaneously. Although a pressure wave will travel throughout
the gas at the acoustic velocity, tending to equalize the pressure in the cylinder,
this is a timeconsuming affair. Likewise, there will be nonuniformity of
temperature throughout the gas during the expansion. Since equilibrium does
not exist during the expansion process, the state, and hence, the properties of
the gas cannot be specified during piston motion. After the piston reaches the
end of its travel, equilibrium will be reached rather shortly, and hence, the
final state may be specified. The initial and final states, 1 and 2, are shown on
a pressurevolume diagram, Figure 45a. The dashed line connecting states 1
and 2 indicates that the intermediate states and, hence, the path cannot be
specified.
The system can be restored to its original state only by bringing in work
from outside the system to compress the gas. Then heat must be removed
from the gas to bring the temperature down to its original value.
In Figure 46 the large weight has been replaced by a large number of small
weights. Assume that each weight is removed instantaneously and slid
horizontally to a niche in the wall of the cylinder. Allow time for the system
to reach equilibrium before another weight is removed. Thus, a series of
equilibrium states may be specified for the expansion process. This is shown
in Figure 45c. As the weights become smaller and smaller, more and more
intermediate states may be specified. In the limiting condition with an infinite
number of weights, all intermediate states may be specified, as in Figure 45d.
At any time, the expansion process can be stopped and the gas can be
compressed to its original state by first exerting a sufficient force on the piston
90 Changes in State of Gases
so that it will move down to permit the top weight to be slid horizontally onto
the piston. Then, progressively, each weight is moved back onto the piston.
The only work required to be brought in from the outside is the work required
to depress the piston sufficiently to permit sliding the top weight onto it. As
the number of weights is increased, the work required to be brought in from
the surroundings to restore the system to its original state becomes progres¬
sively smaller and approaches zero as the weights approach zero in size.
As the weights become smaller and smaller in size, the deviations from
equilibrium conditions also become smaller. In the limit, when the weights
Many small
weights
'The atmosphere is pushed out of the way by the piston as it moves upward. This, in itself, is not
a normal desired effect and, hence, is not classified as useful work.
92 Changes in State of Gases
Although all actual processes are irreversible, there are various degrees of
irreversibility. Consider the gas in the cylinder in Figure 44. When the weight
on the piston is removed instantaneously, the gas expands without doing any
work. Hence, the maximum amount of work is required to restore the gas to
its original state. We may say that this process is completely irreversible.
Now consider the piston with a large number of small weights on it in Figure
46. As the weights are removed, one at a time, the gas does some work in
raising the remaining weights. Hence, less work is required to be supplied
from an external source to restore the gas to its initial state. We may say that
such a process is only partially irreversible.
Many irreversible processes take place at a sufficiently low rate that it is
possible to specify at least some of the properties during the process. For
example, assuming that air expands slowly in a cylinder and does work on a
piston as heat is added to it. The process is irreversible since there will be
friction between the piston and the walls and also because there is a
temperature difference throughout the air. Nevertheless, because of the
slowness of the expansion, it is possible to specify the pressure in the cylinder
at all times. In fact, an engine indicator may be used to plot the pressure as a
function of the piston position. A knowledge of the pressure variation permits
the determination of the work delivered to the face of the piston during the
process or any part of the process. Assuming that the mass of air present is
known, the average temperature during any part of the expansion may be
calculated. Knowing the temperature change facilitates the calculation of the
internal energy change. This internal energy change plus the work delivered
from the system will equal the heat added.
Most of our devices that involve some type of a fluid are, in the overall
sense, open systems. However, many of these devices operate as closed
systems for very short periods of time. This is particularly true for recipro¬
cating devices. For example, consider a reciprocating air compressor. During
the compression process, both valves are closed, and hence, the compression
process is a closed system process. Even for devices that are not reciprocat¬
ing, it is possible and, frequently, desirable to analyze the change of state of
the fluid as it flows through the device. Consider a centrifugal air compressor.
Air enters the compressor more or less at constant pressure, is compressed,
and then flows out of the compressor, again at more or less constant pressure.
Thermodynamically, these three processes for the centrifugal compressor are
similar to those taking place in a reciprocating compressor. Thus, the analysis of
various types of processes is in no way limited to those processes taking place
within a system that remains closed at all times.
pVn = C (41)
It is assumed that the process is a quasistatic one, with the properties being
specifiable throughout the process. Equation 41 also approximates the pres¬
surevolume relationship for many phasechange expansions and com¬
pressions. The value of the exponent n in Eq. 41 depends on the type of the
process. For instance, when n is zero, Eq. 41 states that the pressure is
constant. Rewriting Eq. 41 as pUnV = C', it may be seen that when n = oo, the
volume is constant. Various processes are shown in Figure 47 with the value
of n given for each process. Note that there are an infinite number of
processes that follow the law pVn = C, with n ranging from plus to minus
infinity. Processes that obey the law pVn = C are known as polytropic
processes.
V
FIGURE 47 Polytropic processes.
94 Changes in State of Gases
(4la)
Comparing Eqs. 4la and 42, it may be seen that when n = 1, T, = T2, or that
when n = 1 for an ideal gas, the temperature must be constant. Since Eq. 42
is not valid for an actual gas, it follows that there may be a significant change
in temperature for an actual gas undergoing a process in which the value of
the exponent n is unity.
For a constant temperature process, Eq. 42 becomes
a© (42b)
K
r) 9)
1 1/ V \ i 2/ V
(42c)
/mRT]\n (mRT2\n
\JT) =P2VJT)
Then
I, =/piy"1’'"
(44)
T2 \Pi)
Equation 4la may be written as
Evaluation of Work for Polytropic Processes 95
When the system changes from state 1 to state 2, the integration of Eq. 45
yields
CV'~nl2 pVnVx~n pV l2
(1 ~ n)Ji (1  n) (1  n)Ji
or
P2V2P1V1 (46)
1n
Equation 46 is valid for all polytropic processes when the pV variations are
known at the face of the workdelivering portion of the boundary of the
system. However, when n is unity, Eq. 46 becomes indeterminate. For this
special case, when pV = C, Eq. 45 becomes
dV
8W = C(45a)
When the system moves from state 1 to state 2, integration of Eq. 45a yields
Equation 46a is valid for all processes in which the pV product is a constant,
that is, when the exponent n equals unity. For the special case of an ideal gas,
Eq. 46a gives means of evaluating the work done in an isothermal process,
since n is unity in this case.
96 Changes in State of Gases
■)
Example 42. The original volume in Example 41 is 32,000 cm and the
original pressure is 0.96 bars. Determine the work of compression.
V, 32,000
V2 = = 2038 cm
V,/V2 15.7
p2V2p.Vi _ 395.1 x20389.6x 32,000
Wx.2 = 1,423,000 Ncm
1 — n 11.35
14,230 Nm
—14,230 J Answer
The negative sign indicates that there is a work input during the com¬
pression process.
Example 43. Repeat Example 42, using English units and the pressures in
Example 42.
Solution
Answer
Example 44. A refrigerant expands in a cylinder from a volume of 1950 cm3
to a volume of 9800 cm3, the pressure decreasing from 9.8 bars to 1.2 bars.
Determine the work done.
Pi _ (Yi\
P2 WJ
or
9.8
(^5)" 8.17 = 5.026", n = 1.301
1.2 \1950/ ’
work = PiYpPjV, 1.2 x 10 x 9800  9.8 x 10 x 1950
= 240,000 Ncm
1—n 11.301
= 2400 J Answer
Note: 1 bar = 10 N/cm2.
Evaluation of Work for Polytropic Processes 97
cannot be specified for irreversible processes. Dotted lines placed on any sort
of diagram connecting the terminal states of any irreversible process do not
have significance. In any case, the areas beneath these curves do not have
any significance whatsoever.
fi
*  © iT
(48)
du = cv dT (49)
Equations 48 and 49 were derived for ideal gases. As such they are valid for
all possible changes in state of ideal gases, whether with a constant volume or
not.
A more general equation for the change in internal energy will be developed
in Chapter 8, which will be applicable not only to gases and vapor but also to
solids and liquids.
Example 45. Determine the change in internal energy and the heat added for
Ex. 42. Neglect the effect of temperature on the specific heats. Assume that
air alone is being compressed.
The negative sign indicates that heat was removed during the process.
For an ideal gas (p^)T = C. Then [d(p v)/dp]T = 0. Following the same line of
reasoning used in the previous section, (duldp)T = 0 for an ideal gas.
M (w),iT
■ «■■>
In Section 29, it was shown that for a closed system at rest, dh = 8q for a
constant pressure process. Since for a constant pressure process 8q = cp dT,
dhp = cp dT (412)
or
(413)
*  (w\
Substituting into Eq. 411,
dh = cP dT (414)
Equation 414 was derived for an ideal gas. As such it is valid for all possible
changes in state of ideal gases, whether constant pressure or not. A more
general equation for the change in enthalpy will be developed in Chapter 8
which will be applicable not only to gases and vapors but also to solids and
liquids.
Cp dT = c„ dT + R dt
The pv Relationship for a Reversible Adiabatic Process 101
or
cp = c„ + R (415)
R = cp  c„ (415a)
Since R is always positive, the value of cp for an ideal gas must always
exceed cv.
As will be seen in Section 47, it may be desirable to use the ratio of the two
specific heats, cp and cv. The symbol k is used for this ratio. Thus,
k= — (416)
k =—+ 1 (417)
c„
dp
(c. + R) — + c = 0
P
dp
£jlA±+c = 0
Cp d v dp
=0
v
102 Changes in State of Gases
k In v + In p = C'
or
pvk  C (418)
Equation 418 is written on the specific volume basis. For the total volume,
the equation becomes
pVk = C (418a)
Comparison between Eqs. 41 and 418a shows that the reversible adiabatic
process of an ideal gas is a special form of a polytropic process with the
exponent n assuming the special value of k.
pV _ (15.2 x 10)(34,000)
= 467.7 g
RT (0.287 x 100X112 4273)
T} = 385
= 184.2 K
(pnJp2)(k~m (15.2/1.15)04/14'
U2 Ui =  WU2
1/1.4
V, = V, (
 Sf = 34’000 ( iM) = 214,900 cm3
In general, the amount of heat that must be added per unit mass of the
system to produce an unit change in temperature of the system is dependent
on the nature of the process during which the heat is added. This is true
because work normally is done by the system as heat is added to it. The
temperature rise of the system thus is dependent on how much of the heat
added to the system leaves in the form of work and how much remains in the
system to produce a temperature rise.
Although the heat added to a closed system may be determined by evaluat¬
ing the change in internal energy of the system and the work delivered during
a change in state, in certain problems it is desirable to determine the heat
added in terms of the specific heat of the system for a given change in state.
Let cx represent the specific heat of the system, with the subscript x denoting
that the specific heat is unknown until the nature of the process is specified.
For an ideal gas, a relationship between cx and the polytropic exponent n may
be determined as follows. Assume a reversible process taking place in a
closed cylinder, containing a piston.
8q = du + p dv
cx dT = c„dT + pdv
or
p dv
c = c v f
''X ^ 1
dT
Since p v = RT,
p d v + v dp
dT
R
Then
Rp dv
cx cv +
p dv + v dp
From pvn = c,
np vn 'dv + vndp= 0
or
if dp
p dv = 
n
Then
R(—v dpln)
(—if dpln)I v dp
or
R
cx — c„ + (419)
1 —n
104 Changes in State of Gases
Since n can have any value ranging from positive to negative infinity, cx
also will have values ranging from positive to negative infinity. When n = 0, as
it does for a constantpressure process, cx becomes cp. Similarly, for the
constantvolume processes with n = oo, cx becomes cn. When n = 1, cx is infinity.
Example 47. Find the heat added in Example 45 by use of the polytropic
specific heat.
R
Cx~c,,+(\n)
or
0 787
cx = 0.718 +  ' = 0.102
11.35
Q = mcx(T2 T,)  32.14(0.102)(873  333) = 1770 J Answer
Note: When only the heat added is required, the use of the polytropic specific
heat eliminates the necessity of first calculating the internal energy
changes and the work done.
Table 41
Equations for Specific Heats (cp is in J/g moleK)
Temperature Maximum
Range (K) Error (%)
10,n 536.7,3558
o2 cD = 48.211 + 3002800 1.1
Vt T
536.7 3558 , 0.376^
Cp=48.211 + + (T 2222) 28005000 0.3
Vt T 1000
8.07 x 103 1.499 xio6
n2 cp = 39.65 T + J2 3005000 1.7
h2 cCp = 24 12 1344T
1000 + 6241 3002222 0.8
hundred pounds per square inch. The exact effect of pressure on the specific
heat of any substance at a given temperature is discussed in Chapter 8 and is
given by Eqs. 833 and 834. When pv = RT, these equations show that
pressure has no effect on the specific heats.
When a more exact knowledge of specific heats is desired, tables of specific
heats are available for many gases. One widely used table is that of Keenan
and Kaye, entitled Thermodynamic Properties of Gases (John Wiley & Sons,
1948). It should be noted that this table is valid only for gases at low
pressures.
In 1955, the National Bureau of Standards, U.S. Department of Commerce,
issued a very extensive study entitled Tables of Thermal Properties of Gases,
Circular 564. Figures 411, 412, and 413 were prepared based on data from
these tables. Figure 411 shows the effects of pressure and temperature on the
values of the constantvolume specific heat, cv, and the specific heat ratio, k,
for air. Figure 412 is similar to Figure 411 except that it shows the effects on
Specific heat ratio cp/c
Temperature (K)
FIGURE 411 Effects of pressure and temperature on cv and k for air.
Temperature (K)
FIGURE 412 Effects of pressure and temperature on cp for air.
106
Variable Specific Heat 107
I
CD
03
CCD
o
o
0)
a
GO
the constantpressure specific heat, cp. Figure 413 shows the effects of
pressure and temperature on the constantpressure specific heat, cp, of
other gases.
These figures show that at low temperatures, both pressure and temperature
have a marked effect on the specific heat. At very high temperatures, pressure
does not have a significant effect on specific heat. Furthermore, at high
temperatures, for low and moderate temperature changes the average specific
heat for a given temperature range may be used for ordinary engineering
problems.
The specific heats previously discussed are known as instantaneous specific
heats; that is, specific heats at a specific temperature. These are in contrast to
mean specific heats, which are the true mean specific heats between a fixed
reference temperature and the temperature in question. An instantaneous
specific heat may be read directly from figures such as Figure 411, 412, or
413, or may be approximated by substituting the desired temperature in
equations such as those given in Table 41. Instantaneous specific heats also
may be obtained from many published tables. Tables of mean specific heats
are also available or these specific heats may be calculated from the in¬
stantaneous specific heats. An examination of Figures 411 to 413 shows that
the instantaneous specific heat curves may be considered as straight lines
over a small temperature range, and hence, the mean specific heat may be
taken as that specific heat at the mean temperature. However, this method
108 Changes in State of Gases
I cdT
mean c = =
T2 T,
For the most part, specific heats are of value in that they permit the
evaluation of heat added, internal energy changes, and enthalpy changes. In
Chapter 8 it will be shown that specific heats are useful in determining
entropy changes.
The methods of determining energy changes when there is an appreciable
variation in the specific heats are illustrated in the following examples.
Solution. It will be assumed that the pressures are sufficiently low so that the
nitrogen can be treated as an ideal gas for the given temperatures. For an
adiabatic process, W = (U2 U\) = Uj  U2. Per mole,
1123
uiu2= 31.336(1123  351)  8.07 x 103 In
351
1 1
1.499 x 10 ^1123 351
Example 49. Determine the mean specific heat of the nitrogen in Example
48 and compare it with that given in Table 31.
Solution
Solution
At 1123 K, h = 1221.6 J/g and R^T = 9337 J/g mole or 333.5 J/g
At 351 K, h = 382.7 J/g and R0T = 2918 J/g mole or 104.2 J/g
Then
Example 411. Air enters a system at 30° C and leaves at 340° C. The rate of air
flow is 8.52 kg/s. The power input to the system is 8.4 kW. Determine the rate of
heat addition to the system.
Solution. Since the information is not given otherwise, it will be assumed that
the kinetic energy of the air can be neglected. The firstlaw equation for an open
Based on Tables of Thermal Properties of Gases, U.S. Department of Commerce, National Bureau of Standards Circular 564, 1955.
o
re ON Tf NO d OO © ,—i re Tt c~ © Cl >n oo 1—1 'rf NO o Cl
Eh b re
00
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Cl
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n_i i— i—1 l1 Cl Cl Cl
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U. IH d ON c OO
<u o
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Enthalpy of Gases at Standard Atmospheric Pressure, Joules per Gram
On
S' re Cl re re
d ON re in
& >
«
c
NO o lH i—1 d NO NO ©
00
re NO d d oo OO ^4 00 ci oo ON re © m c
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to OO tO Cl NO r—H <o © ON © i—* TH
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to re re to NO On re re
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Note: The datum for this table is the internal of the gas at 0 degrees absolute.
U Q
Table 42
<D
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2 x r4 ON _4 to ,4 oo oo NO re ,H ci d m] >c NO On re On
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c
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ON d d re
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oo ON Cl d NO NO NO © © c oo © Cl in OO Cl in ON oo re
X r—1 Cl C1 re TT *n © r oo On Cl © oo i re to, oo © re
Cl Cl Cl Cl re re
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c
a> 1— o Cl ef er ON © NO © ON c ON m, re C; to 'Tf
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cn ci r ON ,4 to © NO >c NO © in ci NO d re ci to ON
o o »o lH i—i Cl Cl re ef © c~ 1—H in © in i—i C re ON to y—i
i—1 Cl Cl re ef to NO c~ oo ON © re in oo © re in oo © re NO
Cl Cl Cl Cl re re re
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• P—» 00 ON © 1—4 re d re ci re NO OO oo oo oo i—i i4 re re
©
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i—i Cl re Tf >o NO r 00 On © Cl r © Cl to c © Cl to
Cl Cl Cl Cl re re re
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ce o o o O o o o © © © © © © © © © © © © © ©
o o to o o o o © © © © © © © © © © © © © ©
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1 cire Cl to NO r~~ 00 ON © Cl rr NO oo © Cl NO oo ©
Cl Cl Cl Cl Cl re
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110
Internal Energy and Enthalpy Changes of Gases 111
Example 412. Repeat Example 411 using the specific heat from Table 31.
Solution
PROBLEMS ____
41 Air exists in a closed tank. State how the air can be heated in a process
approaching a reversible one.
42 Can the air in the tank in Problem 41 be expanded in close to a
reversible process? If so, how?
43 In a compression ignition engine (termed also as a diesel engine), air,
originally at 49°C, is to be compressed. The compression ratio is 15 to 1
and the compression obeys the law pVlM=C. Determine the tem¬
perature at the end of compression.
44 Gases expand in a gas turbine from a pressure of 5.9 bars to a pressure
of 1.02 bars. The expansion obeys the law pV127= C. The initial gas
temperature is 892°C. Determine the temperature of the gases at the
exit of the turbine.
45 Determine, per kilogram of air, the work of compression and the heat
lost per gram of air in Problem 43. Neglect the effect of temperature on
specific heat.
46 (a) Treating the gas as air, determine the change in internal energy per
kilogram of gas in Problem 44. Calculate a value of cv at the mean
temperature, using Table A9.
(b) Is it reasonable to treat the gases as air?
(c) Is it reasonable to neglect heat losses?
47 Determine the work done per kilogram of gas passing through the
turbine of Problem 44, treating the gas as air and neglecting heat
losses.
48 Calculate the work done per kilogram of gas during its expansion in
Problem 44 using Eq. 46. Compare this answer to the answer of
Problem 46(a) and comment.
49 Air at 1.01 bars, 22°C, is compressed in a reversible adiabatic manner
until its pressure becomes 5.05 bars. It is then heated at constant
pressure until its volume becomes four times that before heating. Next,
it expands in a reversible adiabatic manner until its pressure becomes
1.01 bars. Finally it is cooled at constant pressure until its volume
becomes onefourth that before cooling. Specify the final temperature.
410 Assuming constant specific heat, determine per kilogram of air the heat
added, change in internal energy, and work done for each of the four
processes in Problem 49.
411 (a) During an isothermal heating of nitrogen in a closed cylinder, its
pressure decreases from 5.16 bars to 2.12 bars. The original volume of
the nitrogen was 0.052 m3. Determine the work done during the expan¬
sion.
(b) What assumption was made for work in part (a)?
412 Determine the heat added in Problem 411.
Problems 113
Table 41, derive an equation for the specific heat of air for a tem¬
perature range of 300 K to 2800 K.
424 In a theoretical Otto cycle using air, heat is added at constant volume at
the rate of 1860 J/g. The initial temperature is 540°C. Determine the
temperature after addition of heat by (a) using constant specific heat
from Table 31, and (b) using the specificheat equation derived in
Problem 423. (See Eq. 415 to obtain c„.)
425 Determine the mean value of c in Problem 424(b). Compare it with the
value used in Problem 424(a).
426 10.4 kg of carbon dioxide are heated at constant pressure from 280°C to
840° C. Determine the amount of heat added by (a) using the constant
value of specific heat from Table 31, and (b) using Table 41.
427 Determine the mean specific heat for Problem 426(b).
428 Solve Problem 426 using Table 42.
429 Solve Problem 424 using Table 42.
430 Air enters an axial flow compressor at 35°C, 1.04 bars and leaves at
285°C. The rate of air flow is 102 m3/min. The power delivered to the air
is 98 percent of the power input to the compressor, that is, the
mechanical efficiency is 98 percent. Determine the power input to the
compressor. State any assumptions that must be made.
431 Air enters an axial flow compressor at 32°C, 1.02 bars and leaves at
292°C. The power delivered to the air is 98 percent of the power input
to the compressor. The power input is 892 kW. Determine the volume
rate of air flow. State any assumptions that must be made.
432 (a) Air at 6.2 bars, 65°C is heated in a reversible isothermal manner, its
volume increasing from 0.05 nr to 0.32 m3. Determine the work done,
(b) Does it make a difference in part (a) if the system is open or closed?
Why?
433 A system is cooled at constant volume from state 1 to state 2, the
internal energy decreasing 88 kJ. It is then heated from state 2 to state
3. The total work done between states 1 and 3 is 44 kJ. The system then
progresses to state 4, the internal energy increasing 35 kJ. The system
finally returns to its initial state, the internal energy increasing 53 kJ.
Determine the heat added to the system as it changes from state 2 to
state 3.
434 An ideal gas is heated at constant pressure by the addition of 113.2 J. It
has its temperature increased 110°C. During the heating, the gas does
32.45 J of work. Determine the gas constant R if the mass present is
0.998 g. Determine also the molecular mass of the gas.
435 A hotair furnace heats air from 22°C to 38°C. Assume that the
pressure of the air is 101.5 kPa. Determine the volume rate of air flow
from the furnace when the furnace must deliver 60,200 kJ of heat per
hour. Neglect the water vapor present in the air.
Problems 115
436 Actually there are 0.015 g of water vapor per gram of dry air in Problem
435. Compare the amount of heat picked up in the furnace per gram of
dry air and per gram of wet air.
437 Air enters a centrifugal compressor at 1.018 bars, 31°C at the rate of
11.5 m3/s. The temperature at compressor exit is 281°C. Determine the
power input to the compressor if 98 percent of the power input is
delivered to the air. State any assumptions that are made.
438 Air flows through a heater for a magnetohydrodynamics generator,
where it is heated from 40°C to 1600°C. Determine the heat required
per kilogram of air by (a) using the specific heat in Table 31, and (b)
taking into account variable specific heat.
439 A compression ignition (diesel) locomotive engine uses 635 kg of fuel
per hour. The efficiency of the engine is 35 percent (i.e., the output is 35
percent of the energy supplied). The heating value of the fuel is
42,000 J/g. Determine the output of the engine.
440 The engine in Problem 439 uses 21 g of air per gram of fuel. Air
is supplied at 1.015 bars, 29°C. Determine the volume rate of air flow.
441 Carbon dioxide is heated at constant pressure in a cylinder and per¬
forms 24.2 J of work. Determine the heat added.
_ 5 _
51 INTRODUCTION
In the latter part of the eighteenth century and the earlier part of the
nineteenth century, man learned to produce work from heat by utilizing steam in
engines. This development was to have profound and farreaching effects. Such
an accomplishment was most remarkable, particularly since heat was not
recognized at that time as a form of energy. At first, there was no recognition that
the first law governs the heatwork transformation. There certainly was no
awareness of any limitation in the amount of heat that can be transformed into
work.
The first person credited with recognizing such a limitation was Sadi
Carnot, a remarkable French engineer. In 1824, he published his treatise
entitled Reflections on the Motive Power of Heat} In it, Carnot concluded that
.. heat cannot perform work except when it passes from a higher to a lower
temperature level.” Furthermore he stated that the amount of work that can
be produced by a steam engine from a given quantity of heat is a direct
function of the difference between the temperature at which the steam is
produced and the temperature of the steam at the engine exhaust.
The insight of Carnot was especially remarkable, since his theory was
developed at least 20 years before the brilliant demonstration of James
Prescott Joule convinced the scientific world that heat is a form of energy.
Indeed, it seems probable that Carnot was not aware of the true nature of
heat. In Carnot’s time, the caloric theory of heat was the accepted one. This
theory pictured heat to be an imponderable fluid, having neither mass nor
substance, but occupying all space. To be sure, scientists such as Count
Rumford and Mayer were questioning this concept, but it remained for Joule
to demonstrate so convincingly that heat is a form of energy.
After it was recognized that heat is a form of energy and that some of it can
be transformed into work, many other observations were made relative to
energy transformations. Some of these observations showed that certain
'Carnot was 28 years old at this time. He developed the concepts involved in this treatise several
years earlier.
116
Introduction 117
transformations may take place with the first law holding precisely, but that
these transformations cannot be reversed without energy being supplied
externally. Some examples of these transformations are as follows:
1 Whenever a heatflow path exists, heat flows readily from a region of high
temperature to one at a lower temperature, but the reverse is not true.
Heat does not spontaneously flow “up hill.”
2 Work, of the mechanical form, can be converted completely into heat.
Consider the pushing of a block over a rough surface. The work used in
pushing the block to overcome friction produces a heating effect on the
block and the surface. To restore the temperature of the system to its
original value, heat, equivalent in amount to the work input, must be
removed from the system. But experience has shown that the converse of
this operation is impossible. The heat that was removed will not of its own
accord flow back into the system, restore the block to its original position,
and deliver an amount of work equivalent to the original work input.
Furthermore, heating the block will obviously not cause it to move, either.
3 An electric current flowing through a resistor produces a heating effect.
Heat, in an amount equivalent to the electrical energy input, may be
removed from the resistor. However, the converse of this operation is not
true. The heat that was removed will not flow back into the resistor and
produce electrical energy.
4 An uncontrolled exothermic chemical reaction produces products whose
temperature is in excess of the original temperature. Heat must be
removed from the products to restore their temperature to that of the
original mixture. Thus, there is transformation of chemical energy into
heat. A common example is a mixture of hydrogen and oxygen. The
introduction of a spark into the mixture produces a violent reaction,
forming water vapor that has a temperature much in excess of the original
temperature. The temperature of the water vapor may be restored to that
of the original hydrogenoxygen mixture by removing heat. It is in¬
conceivable, however, that this heat that was removed will flow back into
the water vapor and dissociate it into hydrogen and oxygen.
5 Consider a chamber divided into two parts by means of a partition. Let
one part be occupied by oxygen and the second part by nitrogen. When
the partition is ruptured, mixing of the nitrogen and oxygen takes place
until there is a uniformity of the mixture throughout the chamber.
However, our experience tells us that the mixture will not of its own
accord become “unmixed,” with the oxygen and nitrogen returning to their
original positions.
In the five examples cited above, the first law governs the energies involved
in the transformations. But the first law does not answer many questions,
such as why there cannot be complete transformation of heat into work but
work can be completely transformed into heat. Neither does it answer the
118 The Second Law and Entropy
question of why some processes can proceed in one direction but not in the
other. Further, the first law in no way explains why it is possible for certain
processes to take place but impossible for other processes to occur. The
second law does provide answers to these questions.
The scope of the second law is broad and quite inclusive. At the heart of
the second law is a property called entropy. To understand entropy fully, as
well as make complete use of it, it is necessary to investigate entropy from
the microscopic viewpoint with the aid of statistical thermodynamics. As a
first approach, however, the nature of entropy will be investigated from the
classical viewpoint. This may be done by utilizing the concept of the Carnot
cycle.
(a)
FIGURE 51 Elements of a heat engine, (a) Cyclic operation intermittent heat flow, (b)
Continuous heat flow.
The Carnot Cycle 119
Heat
conductor
\
El
Heat ! (jemperature
sink constant)
Carnot cycle.
working substance in the engine is equal to that of the heat source, the heat
conductor is inserted between the two. By virtue of high gas pressure in the
cylinder, the piston moves outward, tending to decrease the gas temperature.
As soon as this takes place, heat will flow from the heat source into the engine
and will continue to flow until the heat conductor is removed (process 12).
During this process, the temperature within the cylinder is substantially equal
to that of the heat source. After thermal contact with the heat source is broken,
the working substance expands adiabatically until its temperature reaches that
of the heat sink (process 23). Now thermal contact is established with the
heat sink. The piston is pushed to the left, causing heat to flow into the heat
sink in a constant temperature manner (process 34). At the correct time,
thermal contact with the heat sink is broken and an adiabatic compression
takes place (process 41) until the temperature reaches that of the heat source.
The cycle is now complete.
The thermal efficiency of a heat engine is defined as that portion of the heat
supplied to it which is delivered as work. Or, thermal efficiency,
W
v, = Qh (51}
where QH is the heat received from the source and W is the work output of
the engine.
It is desirable to obtain an expression for the thermal efficiency of the
Carnot cycle in order that the effects of the temperature of the heat source
and the heat sink can be evaluated. Carnot stated that thermal efficiency is
independent of the nature of the working substance. This will be discussed in
some detail later on in this chapter. Assume, initially that the working
substance is an ideal gas.
For a heat engine with no extraneous heat transfers (i.e., only receiving
The Carnot Cycle 121
W = QhQl (52)
where QL is the heat rejected to the sink. Substituting into Eq. 51,
v QhQl
(53)
Vt Qh
Qh is transferred at a constant temperature. Hence, from Eq. 46a with
P\V\ — PiV2 and applying the first law,
Qh = Wi.2 = Pi V, In = mRTH In
V 1 V ]
Ql = = p4V4 In Tr = mRTL In ^
V4 V4
Since both processes 23 and 41 are reversible and adiabatic, using Eq. 43,
kl
III (V2)
and
H
Tl Vv3y1
Thus
VT V, V2
and
V2 v4 v, V4
Substituting into Eq. 53a,
thtl II
Vt 1  (54)
Th Th
Equation 54 shows that the thermal efficiency of the Carnot cycle increases
as the temperature difference increases and approaches 100 percent as the
source temperature approaches infinity. Equation 54 also shows that the
thermal efficiency increases as the sink temperature decreases. Hence, it is
desirable to use that available sink having the lowest temperature. Although
Equation 54 indicates that there will be a further gain in thermal efficiency by
artificially lowering the sink temperature, there will be an overall loss by doing
this since the work required to lower the sink temperature will actually
exceed the gain in engine output.
Example 51. 1450 kJ of heat are supplied to a Carnot cycle engine at a
temperature of 820°C. The engine rejects heat to a sink at a temperature of
122 The Second Law and Entropy
40°C. Determine: (a) thermal efficiency, (b) work delivered, (c) heat rejected
to the sink.
Solution
Tl 40 f 273
0.714 or 71.4 percent Answer
Th 820 + 273
1035
= 24.1 kJ/s
43
Since 1 J/s = 1 W,
power produced = 24.1 kW Answer
/
Heat
\
\
conductors I
L /
W = Qh Ql (55)
Qh = Ql+W (57)
Although Eqs. 55, 56, and 57 are equivalent to each other, they are
presented in their different forms so as to place the desired effect on the left
side of the equations.
Example 53. A reversed Carnot cycle engine receives heat at — 10°C and
delivers it at 30°C. The power input is 4.8 kW. Determine (a) the heating effect
and (b) the refrigerating effect.
Solution
Example 54. Determine the heating effect in Example 53 in calories and
Btu/min.
The thermal efficiency of the Carnot cycle engine was derived in Section
52 by assuming that the working substance is an ideal gas. The question must
be raised as to the effect of the nature of the working substance on the thermal
efficiency. The answer is obtained by indirect logic. Consider the possibility
that the thermal efficiency of a Carnot cycle engine using an actual working
substance is higher than that of a Carnot cycle engine using an ideal gas. In
Figure 56, engine A uses the actual fluid and engine B an ideal gas. Let an
amount of heat, QHa, be delivered to engine A. Let its work output be used to
Engine A
Engine B
with actual
Carnot with ideal gas
gas
drive engine B, now operating in reverse. When the efficiencies of the two
engines are equal, engine B will pump an amount of heat, QHb, which exactly
equals QHa, into the heat reservoir. But now assume that, because it is using
an actual gas, the efficiency of engine A exceeds that of engine B. Then
engine A will deliver more work to engine B than formerly. Because of a
larger work input, the amount of heat that engine B now delivers to the heat
reservoir will exceed QHa. This means more heat is delivered to the high
temperature reservoir than is removed from it. An application of the first law
shows that this additional amount of heat comes from the lowtemperature
reservoir. If this be true, then the arrangement in Figure 56 is an isolated
system in which heat flows from a lowtemperature reservoir to one at higher
temperature. But all of our experience has shown that in an isolated system,
heat will not flow from a region of low temperature to one of higher
temperature. It must be concluded, then, that the conditions of operation as
assumed for Figure 56 are impossible, and hence, no heat engine can have an
efficiency higher than that of the Carnot cycle.
In a similar manner, it may be concluded that the thermal efficiency of any
reversible heat engine receiving the rejecting heat isothermally cannot be less
than that of the Carnot cycle. It is evident, therefore, that the thermal
efficiency of any and all reversible heat engines, which both receive and reject
heat isothermally, must equal that of the Carnot cycle heat engine, which uses
an ideal gas. This statement is in agreement with Carnot when he stated that
“The motive power of heat is independent of the agents employed to realize
it . . . ”
specified. It receives heat from heat reservoirs I and II. It may reject all of the
heat to the heat sink or it may deliver work up to a maximum of that of a
reversible heat engine. The work inputs to the reversed Carnot engines A and
B are so regulated that they deliver to their respective heat reservoirs exactly
as much heat as is removed from these reservoirs to supply the system. Thus,
numerically, QA = QS] and Qb2 = Q^. The system is so operated that there is
no change in its contained energy. When every process occurring in the
system is wholly reversible, the work delivered by the system equals the
summation of the work inputs to engines A and B, and the heat rejected by
the system to the heat sink equals the total delivered by the sink to engines A
and B. An irreversibility in the system causes it to deliver less work and to
reject more heat to the heat sink. Thus, numerically
Substituting,
Qa3 Qa,
Qa3 — Qa, Qa, or (59)
In a similar manner,
Qb3 Qb2
(510)
Consider the heat flows into the system as positive and those from it as
negative. Thus QS) and Q^ are positive and Q^ is negative. Then QAl and QBj
are positive. Since, numerically, Q^= Qa3 + Qb„
Qa, + Qb, + Qs, S 0 (511)
Entropy 127
Qa3 — Qs, j
Qb3 — Qs, jT
or
(512)
(513)
This equation states that the summation of each quantity of heat transferred
to the system divided by the temperature at which it is transferred is equal to
or less than zero. Equation 513 may be written as
(514)
55 ENTROPY
Assume that a completely reversible cycle takes place within a system, such
as the one shown in Figure 58. Consider an infinitesimal amount of heat
added at point P as the cycle is traversed in the clockwise direction. Call this
amount of heat SQd. Since the cycle is a reversible one, when the cycle is
traversed in the opposite direction at point P, an infinitesimal amount of heat,
8Qco, will be removed. Because the process is reversible,
Let the symbol <f stand for integration around a complete cycle. When the
Clausius inequality is written for the cycle traversed in a clockwise direction,
(516)
128 The Second Law and Entropy
(517)
Since 5Qd = SQco, it is evident that neither $(8QJT) or $(8QcolT) can be less
a reversible cycle,
(518)
J T
But
N)
8Q\
0
;stV
II
=
T /,
or
J. U )a J,r ^
V T J B
= a constant (519)
The value of the constant in Eq. 519 is independent of the path chosen to
evaluate it and depends solely on states 1 and 2. As such, it must be a
property. This property was termed entropy by Clausius and is designated by
the symbol S. Then
(520)
8Q = dU + 8W
From Eq. 27a, 8W = p dV or
dU + p dV
dS (521)
T
mcv dT dV
dS + mR (522)
T V
Solution. Since the final pressure equals the initial pressure, the actual
change in entropy equals the change in entropy for a reversible constant
pressure process between the initial and final states. Using Eq. 520,
mcp dT T
S2 mcp In jr
T 11
/282 + 273\
= 4 x 1000 x 1.004 In = 2430 J/K Answer
V 34 + 273 )
Example 56. Air is compressed in an unknown manner from 1.2 bars, 18°C
to 48 bars, 135°C. Determine the change in entropy per gram of air.
Solution
^ = 0.2428, n = 1.321
n
R qio 0.2870 .. ,
cx = c„ + = 0.718 + j—TTTT ~ “0.J/g C
1 —n 1 — 1.321
130 The Second Law and Entropy
Answer
Example 57. Determine the change in entropy per gram of air during its
compression in a diesel engine. The compression ratio is 15 to 1. The original
temperature is 35° C and the final temperature is 620° C.
T2 V,
S2~ Si = mev In — + mR In —
I 1 V!
Note: 8.314 is the gas constant per mole and 28.97 is the number of grams of
air per mole.
3It is conceivable that the removal of heat from a system may exactly neutralize the increase in
entropy produced by irreversibility within the system. Then the entropy of the system will remain
constant. This is very unusual. Hence, normally, the word isentropic denotes a reversible
adiabatic process.
rejected to the sink during process 34. Area 3456 represents this heat. The
difference between these two areas, area 1234, represents the cycle work.
An expression for the thermal efficiency of the Carnot cycle may be derived
by use of the TS plane.
This expression for efficiency is identical to that derived in Section 52 (Eq.
54).
134 The Second Law and Entropy
PROBLEMS _____
512 A reversed Carnot cycle engine removes 140,000 kJ/h of heat from a
heat sink at 2°C and delivers heat at 55°C. Determine the power
required.
513 Same as Problem 512 except the sink temperature is 20°C.
514 In a Carnot cycle engine, the volume after the adiabatic compression is
8.5 percent of that before the compression. The sink temperature is
30°C. Determine the thermal efficiency.
515 The temperature of the hot junction of a thermoelectric generator is
750°C and the cold junction temperature is 150°C. Determine the
maximum possible power output when heat is supplied at the rate of
lOOOkJ/min (see Section 182 for a discussion of thermoelectric
generators).
516 The emitter (heat source) of a thermionic generator has a temperature
of 150Q°C and a collector (heat sink) temperature of 750°C. Determine
the minimum rate of heat input when the generator delivers 2.5 kW (see
Section 183 for a discussion of thermionic generators).
517 The radiation heat losses from the emitter of Problem 516 at 1500°C
are very high and the emitter life is relatively low. Repeat Problem 516
with an emitter temperature of 1200°C.
518 A thermionic generator is cascaded with a thermoelectric generator.
(The collector of the thermionic generator is the heat source for the
thermoelectric generator.) The temperature of the emitter of the ther¬
mionic generator is 1500°C and its collector temperature is 750° C. The
heat sink temperature for the thermoelectric generator is 150°C. The
thermionic generator produces 2.5 kW. For the ideal case determine: (a)
overall efficiency and (b) power output of the thermoelectric generator.
519 Gases enter a magnetohydrodynamic generator at 6.2 bars, 2700°C and
leave at 1.12 bars. Assume that the value of k of the gases for reversible
adiabatic expansion is 1.38. Determine: (a) theoretical gas temperature
at exit and (b) maximum thermal efficiency. (See Section 184 for a
discussion of magnetohydrodynamic generators.)
520 In the early development of the steam power plant approximately
1.12 kg of coal was required per kilowatt hour. Assume that the mean
temperature at which heat was supplied was 175° C and heat was
rejected at 100°C. Today assume that heat is supplied at a mean
temperature of 380° C and rejected at 32° C. Assume that the ratio of the
actual thermal efficiency to that of the Carnot cycle today is 1.15 times
that of the earlier years. Assume that the heating value of the coal is the
same for both cases. Calculate the amount of coal now required per
kilowatt hour.
521 (a) The sink temperature for a Carnot cycle engine is 30°C and the
source temperature is 200°C. Determine the thermal efficiency.
Problems 137
(b) The same as part (a) but for source temperatures of 600°C, 1000°C,
and 1500°C.
(c) Plot the thermal efficiency against source temperature.
522 An actual refrigerating system requires 3.2 times the amount of power
to produce a given amount of refrigeration at specified temperatures as
does a reversed Carnot cycle engine. Refrigeration is desired at — 10°C
and heat is rejected at 35°C. Determine the actual power required to
produce refrigeration at a rate of 500kJ/min.
523 A Carnot cycle engine using air has a clearance volume (the volume at
the end of adiabatic compression) of 0.005 m3. The maximum cylinder
volume is 0.05 m3. The source temperature is 300° C and the sink
temperature is 40°C. Determine the work per cycle if the pressure at
the start of the isothermal compression is 1.02 bars.
524 Repeat Problem 523 for source temperatures of 400° C and 500° C.
525 The engine in Problem 523 is used to produce refrigeration at 10°C.
The engine rejects heat at 40°C and the minimum pressure in the cycle
is 1.02 bars. Determine the amount of refrigeration produced per cycle
and the work required per unit of refrigeration.
526 The same as Problem 525 except for refrigeration produced at —10°C
and 30°C.
527 Is Eq. 53 precise for actual heat engines? Why?
528 (a) A kilogram of air is heated at constant pressure from 30°C to 80°C.
Calculate the change in entropy.
(b) If the heating in part (a) is done in a cylinder having a piston, will
piston friction change the answer?
529 The same as problem 528 except that the air is heated from 30°C to
1000°C.
530 2.25 kg of air are throttled from an initial temperature of 124°C and a
pressure of 21.5 bars to a pressure of 2.15 bars. Determine the change
in entropy. Hint: Assuming no net change in kinetic energy, what
happens overall to the enthalpy and temperature during the throttling?
531 A tank having a volume of 2.82 m3 contains air at 24.5 bars, 32.5°C.
Determine the change in entropy of the air if it receives 720 kJ of heat.
532 2.75 kg of air are heated in a reversible constant pressure process by
the addition of 140.5 kJ of heat. The initial temperature is 42°C.
Determine the change in entropy.
533 4.25 kg of air are heated in a reversible isothermal process. The air
temperature is 38.5°C. The increase in entropy is 1.5kJ/K. Determine
the ratio of the final to initial pressure.
534 Air is compressed from a pressure of 2.13 bars to a pressure of 8.05
bars, its temperature increasing from 36°C to 179°C. Determine the
change in entropy if there are 0.892 kg of air.
138 The Second Law and Entropy
SOME CONSEQUENCES
OF THE SECOND LAW
But
139
140 Some Consequences of the Second Law
{Q 3
Engine 111 1
w3
{04
Then
When the works of the two engines are equated, the result is
Thus,
T,T2= T2T3
This last equation states that when Carnot engines are operated in series
and the engines produce equal amounts of work, then the temperature
differences across the engines must be equal. The magnitude of the tem¬
perature difference (T, T2) can be varied at will by varying the amount of
work produced by engine I. The quantity (Tj— T2) can be established as any
desired unit of temperature by establishing the amount of work to be
produced by engine I.
When enough Carnot engines are added in Figure 61, the total work
produced by all the engines will equal the heat transferred from the heat
reservoir. The temperature of the last heat sink, when all heat transferred
from the heat reservoir is converted into work, is the lowest conceivable
temperature.
No temperature lower than this temperature can be conceived since a lower
temperature will permit the addition of an additional heat engine, which could
produce an additional amount of work. The sum total of the work produced
would then exceed the heat supplied from the heat reservoir, thus violating
the first law.
Availability of Energy Entering a System 141
The shaded portion in Figure 62 represents the unavailable energy added to
the system. By integrating,
8Q
unavailable added = TL (63)
T
But 8Q/T = dS. Then
The available portion of the heat added to the system equals the difference
between the total heat added and the unavailable energy. Thus,
T  t Q 90
44.8° C
2 1 mc„ 2.8 x 0.718
T2 = 26 + 44.8 = 70.8° C or 344 K
Since
jo _
Lt kJ
&Q
rj<
_ mc*<
rj,
dT ^
Solution. Since the pressure is held constant during vaporization, the tem¬
perature also remains constant. The change in entropy of the system,
of work becomes unavailable during the heat transfer process see Figure 63.
The loss in available energy occurring when heat is transferred from a
hightemperature source to a lower temperature system may be determined by
finding the difference between the available energy leaving the source and the
available energy entering the system. This method is illustrated in the follow¬
ing example.
Example 63. Exhaust gases from a gas turbine are used to heat water. The
gases leave the turbine at 650°C and may be cooled to 145°C. The rate of gas
flow is 1510 kg/min and the rate of water flow is 1890 kg/min. The water enters
at 35°C. Assume that the mean specific heats of the gases and water are
1.088 J/gK, and 4.27 J/gK, respectively. The lowest available sink tem¬
perature is 32°C. Determine the loss of available energy resulting from the
heat transfer.
Solution. See Figure 63. The final water temperature can be obtained by
equating the heat given up by the gases to that received by the water. Thus,
or
650 + 273
= (32 + 273)1510 x 1.088 ln( ) = 397,000 kJ/min
.145 + 273
= 709,000 kJ/min
loss in available energy = gain in unavailable energy
= 709,000 — 397,000 = 312,000 kJ/min Answer
Example 64. Determine the loss in power as a result of the heat transfer in
Example 63.
98
T2 = T, + 2
mcp
 = (28 + 273) +
1 x 1.005
= 398.5 K
net change in available energy of the system = 11.7  28.0 = 16.3 kJ Answer
146 Some Consequences of the Second Law
The unavailable energy of a system increases when heat is added to it. This
increase in unavailable energy equals the unavailable energy of the heat that
is added.
Solution. In Example 65, it was found that the unavailable energy portion of
the heat added was 86.3 kJ/lb of air. Work, in the amount of 28.0 kJ, is
delivered to a piston. Lacking other information, it was assumed that this
amount of work was delivered from the system and that none of it became
unavailable because of sidewall piston friction. Then the change in unavail¬
able energy of the system equals 86.3 kJ. Answer
It is to be noted that even though available energy was added to the system
in Example 65, there was an overall decrease in the available energy of the
system because available energy, in an amount larger than that which was
added, was removed from the system in the form of work.
The unavailable energy of a system will also increase when an irreversible
process occurs within the system. For a definite change in the state of a
system, whether by addition of heat or by any irreversibility occurring within
the system, there is a very definite change in the unavailable energy of the
system. It should be noted that the change in unavailable energy of the
system, because of heat addition, was evaluated in terms of the entropy
change of the system. When any irreversibility that produces the same change
in entropy occurs within the system, there must be the same change in
unavailable energy of the system.
Solution. Treat the air as an ideal gas and assume no heat transfer. Then
there will be no net change in temperature. From Eq. 522, the change in
entropy,
S? — S. = me
mffi) + mR ln(© = 01 mR In
©
= 0.995 kJ/K
change in unavailable energy = TL(S2~ Si) = (25 + 273)(0.995) = 296 kJ
Answer
Since no energy crossed the boundaries of the system, this increase in the
unavailable energy could have come only from the available energy of the
Change in Available Energy of Systems 147
system. Hence, the change in available energy of the system is negative and
equal to — 296 kJ. Answer
A = UTS (67)
dA = dU — 8Q  S dT
so that
dU = dA + 8Q + SdT
Substituting this value of dU into Eq. 66 and recognizing that the tem¬
perature is constant,
SQ = dA + §Q T 8W
Then
8W = dA
and
Equation 68 states that the maximum work performed by a system that
changes from state 1 to a final state without a net change in temperature
equals the decrease in the Helmholtz function.
The expansion of a system existing in the atmosphere causes work to be
done against the atmosphere. This work is part of the work given by Eq. 68.
This work p0dV, is not considered to be useful for most purposes (p0 is the
atmospheric pressure). Hence, it must be subtracted from the maximum work
of Eq. 68 to obtain the useful work, or,
and
max WUSefui = (A,  A2)T  p0(V2 VO (610a)
The maximum useful work may be obtained directly for the special case
when initial and final temperatures are equal by the use of another function.
This function, known as the freeenergy, or Gibbs function, is defined as
G = H  TS (611)
Then
dG = dH  T dS  S dT = dU + p dV+V dpTdSSdT
or
dU = dG  p dV  V dp+ TdS + SdT
Substituting this value of dU into Eq. 610 and assuming reversibility yields
For the special case where the initial and final temperatures are equal and
where the pressure of the system is constant and equal to that of the
surroundings,
or
‘in both the Daniels cell and the fuel cell a chemical reaction takes place, producing electric
energy. The supply of the reactants is selfcontained in the Daniels cell. In the fuel cell, the
reactants are supplied to the cell and the products are removed from the cell in a continuous
manner.
Availability of a Closed System 149
of the Daniels cell and the fuel cell is not limited by the Carnot cycle concept,
since the Carnot cycle concept applies only to heatwork transformations.
The action in the Daniels cell and the fuel cell is a chemical energywork
transformation.
Both the Helmholtz and Gibbs functions are potentials; they are driving
forces that can cause reactions to take place. It will be shown in Chapter 11
that a reaction cannot take place in an isolated system unless there can also
be a decrease in the Gibbs function as a result of the reaction.
It should be noted that both the Helmholtz and Gibbs functions contain a
TS term. Normally, during a chemical reaction there will be a change in the
entropy. The entropy of the products generally will not be equal to that of its
reactants, even at the same temperature. Thus, it is essential to use the
absolute values of entropy in determining the Helmholtz and Gibbs functions.
It is possible to determine the absolute values of entropy of a gas by a
stepbystep process. However, statistical thermodynamics, together with
quantum mechanics, provides a more satisfactory method of obtaining ab¬
solute values of entropy. This will be discussed in Chapter 16.
Q= U0U\ + Wmax
or
Wmax = Q + 17,  U0
But
Since 17, T, and S are properties of the system and are dependent on state
only, the maximum work as determined by the use of Eq. 613 is the available
energy of the system in its original state.
Solution. See Figure 64. The available energy equals the maximum work
that can be delivered as the state of the system changes to that of the
surroundings. From Eq. 613,
Pi
Q = mRT0 In
Po
Entropy and Unavailable Energy 151
Then
T„(S0S2)=mRT„ln2
*0
Substituting,
Then
Answer
Example 69. Rework Example 63 by first finding the change in entropy of
the gases and the water.
152 Some Consequences of the Second Law
= 1301 kJ/minK
Example 610. Follow the procedures of Examples 63 and 69, with the
exception that the hot gases are used to boil water at a temperature of 120°C.
Solution
PROBLEMS ___
61 A Carnot cycle engine receiving heat at 200°C and rejecting heat at
20°C delivers 10.8422 kJ of work when its heat input is 28.5 kJ. Cal¬
culate the conversion factor for changing degrees Celsius to degrees
Kelvin.
62 4.85 kg of air are heated in a closed system from 30°C to 90°C at
constant pressure. The temperature of the surroundings is 28°C.
Determine: (a) change in entropy of the air, and (b) available energy
added to air.
63 Same as Problem 62 but the air is heated as it flows through a heater.
64 Boiling water enters a boiler at 240°C at the rate of 4270 kg/min. During
the boiling process, 7,543,000 kJ of heat are added. The temperature of
the surroundings is 25°C. Calculate the available energy added. (The
temperature will not change during boiling.)
65 In an Otto cycle engine, heat is rejected to the atmosphere at constant
volume, the temperature decreasing from 190°C to 40°C. The tem¬
perature of the surroundings is 24° C. Air is the working substance in
the engine. Determine the available energy removed per kilogram of air.
66 The condensing temperature in the condenser of a steam power plant is
30°C. The temperature of the surroundings is 22°C. Steam flows to the
condenser at the rate of 1,287,000 kg/h. Each kilogram gives up 2190 kJ
of heat as it condenses. (Condensation takes place at constant tem¬
perature.) Express the available energy given up in the condenser in
terms of kilowatts.
67 In an air heater, air is heated from 45°C to 245°C by gases that cool
from 345°C to 150°C. Assume that the mean specific heat of the air is
1.017 J/g and of the gases, 1.035 J/g. The temperature of the surround¬
ings is 30° C. Determine the loss of available energy per kilogram of air
as a result of the heat transfer. Note: First find the kilograms of gas per
kilogram of air.
68 A tank of water, containing 893 kg, is heated from 40°C to 80°C by
steam condensing in a steam coil at 120°C. The temperature of the
surroundings is 28°C. Determine the loss of available energy resulting
from the heat transfer.
69 A 2.3kg mass of iron having a temperature of 870°C is quenched by
immersing it in a tank containing 74.5 kg of water with a temperature of
28°C. The specific heat of iron is 0.465 J/gK. Determine: (a) net change
in entropy and (b) loss of available energy if the temperature of the
surroundings is 28° C.
610 A constanttemperature source supplies 24,000 kJ/min to a heat engine.
The source temperature is 665°C, the lowest available temperature is
24°C and the mean temperature at which the engine receives heat is
154 Some Consequences of the Second Law
480°C. Determine the loss of available energy resulting from the heat
transfer.
611 (a) Determine the maximum power that can be produced by the engine
in Problem 610.
(b) Determine the potential percentage loss of power because of heat
transfer.
612 During a reversible expansion of a system 65 kJ of heat are added to
the system and the system delivers 65 kJ of work. Recognizing that only
part of the heat added is available energy and all of the work is
available energy, explain how this is possible.
613 Liquid sodium is used to transfer heat from a nuclear reactor to
produce steam. Steam is produced at 326°C at a rate of 482,000 kg/h.
The steam picks up 1181.3 J/g. The sodium is cooled from 650°C to
345°C. If the temperature of the surroundings is 30°C, determine the
loss of available energy per hour because of heat transfer. Determine
also the maximum amount of power that can be produced by this
available energy.
614 Air is cooled in the intercooler of a twostage air compressor from
105°C to 27°C. The temperature of the surroundings is 25°C. The rate
of air flow is 75.8kg/min. Determine the loss in available energy
resulting from the heat transfer.
615 Air at 14.5 bars 60°C is throttled to 1.15 bars. The temperature of the
surroundings is 24°C. Assume no heat lost and no net change in kinetic
energy. The air flow is 28.5 kg/min. Determine the change in entropy
and the loss in available energy.
616 For control purposes, steam is throttled as it enters a steam turbine,
producing an increase in entropy of 0.29kJ/kgK. The temperature of
the surroundings is 26°C. The rate of steam flow is 52,500 kg/h. Deter¬
mine the loss in available energy resulting from the throttling and the
maximum loss in power.
617 A heat engine receives 1700 kJ of heat per minute from a heat source
whose temperature remains constant at 430°C. The engine receives heat
at a mean temperature of 402°C and rejects heat at a mean temperature
of 40°C. The sink temperature is 33°C. The efficiency of the engine is 55
percent of that of the Carnot engine for the given engine temperatures.
Determine: (a) power lost by heat transfer to the engine, (b) power lost
because the engine is less efficient than the Carnot, and (c) power lost
by heat transfer to the sink. Make an accounting of the available energy
taken from the source.
618 52 kJ of work are added to a system as its entropy increases 0.38 kJ/K.
The temperature of the surroundings is 24°C. Determine the change in
the available energy of the system.
619 (a) Air expands from 8.1 bars, 212°C to 1.75 bars according to the law
Problems 155
1 36 ’
pV = C. The temperature of the surroundings is 28°C. Determine, per
kilogram of air, the increase in the unavailable energy of the air.
(b) Is it necessary to know if the process in part (a) is reversible?
620 Water is to be heated from 27°C to 90°C at the rate of 1050 kg/h by
gases whose temperature drops from 425°C to 95°C. The temperature
of the surroundings is 23°C. Determine the loss of available energy as a
result of the heat transfer. Note: The specific heat and the mass rate of
flow of the gases are unknown.
621 Air enters an air turbine at 6.95 bars, 180°C and leaves at 1.28 bars.
Determine the maximum change in available energy per kilogram of air,
assuming no heat is removed.
622 In Problem 621, the air actually leaves at a temperature of 45°C.
Determine: (a) work delivered per kilogram of air and (b) change in
available energy per kilogram of air.
623 It is proposed to cool a compressionignition (diesel) engine by produc¬
ing steam in the “water” jackets. The steam is to be used in a separate
cylinder to produce work. When the engine is developing 1850 kW, the
heat flow to the jackets is approximately equivalent to the work. Steam
is produced at 110°C. The temperature of the surroundings is 30°C.
Determine the maximum power that can be produced by the steam. Do
you recommend this arrangement?
624 In the regenerator of a gas turbine (see section 1310), the air is heated
before its entrance to the combustion chamber by the exhaust gases
from the turbine. The air flow is 2850kg/min. There are 54 g of air per
gram of fuel. The air is heated from 132°C to 366°C. The gases enter at
534°C. The lowest available temperature is 24°C. Determine the maxi¬
mum amount of power that could be produced from the available
energy lost by heat transfer. Take the value of the specific heat of the
air at its mean temperature. The mean specific heat of the gases is
1.075 J/gK. Hint: find the temperature of the exit gases.
625 Air exists in a closed system at 13.8 bars, 94°C and occupies a volume
of 1.71 m3. If the surroundings are 1.02 bars, 20°C, determine the
available energy of the system.
626 A system undergoes a series of processes and returns to its original
state. The net change in the Gibbs function must be zero. Does this
mean that there is no net work done? Why?
627 A compressor compresses air according to the law pV135 = C. Air
enters the compressor at 1.02 bars, 30°C and leaves at a pressure of
6.78 bars. The rate of air flow into the compressor is 6.75 nr/min. The
temperature of the surroundings is 30°C. Determine: (a) heat lost from
the air per minute, (b) power input, (c) unavailable energy change of the
air, and (d) available energy change of the air.
_ 7 _
71 INTRODUCTION
In Chapter 5 the concept of the property known as entropy was developed
from a macroscopic viewpoint. In Chapters 5 and 6, engineering uses of this
property were presented. In addition, methods of determining entropy
changes were developed and the entropy changes were correlated to changes
in unavailable energy. Thus the engineer has been given means of utilizing
this very important property.
However, we could not investigate the fundamental nature of entropy,
since macroscopic thermodynamics does not lend itself to such an in¬
vestigation. In this chapter, we will use the microscopic approach to gain an
understanding of the nature of entropy.
156
Probability 157
73 PROBABILITY
The probability of predicting the outcome of an occurrence is dependent on
the number of objects involved in the occurrence. Consider two small equally
sized chambers, A and B, each containing a molecule, a and b (see Fig. 71).
Following common practice, these chambers are designated as cells. Let the
two cells be moved together and let the common wall be pierced to permit
the molecules access to both chambers. Since the molecules have high
velocities, they will have a tendency to move between the two cells. At any
given instant, there is a fiftyfifty chance that molecule a will be in the cell B.
The same statement may be made about molecule b. Thus, there are four
possible microscopic states for the two molecules, as shown in Figure 72.
a
FIGURE 71 Two molecules in two cells, A and B.
158 Probability and the Nature of Entropy
FIGURE 72 Possible microscopic states for two molecules in two cells, A and B.
A B A B A B A B A B A B
ab 1 ab 1 ac ab be 1 ab 1 cd
cd c d _d__b_ d c d
1 1 a
A B A B A B A B A B A B
ac 1 bd ad 1 be be I ad bd ac cd 1 ab a 1 be
1 1 1 d
A B A B A B A B
b 1 ac c i ab d I ab ab
1 d 1 d cd
cell, (4) one molecule in cell A and three in cell B, and (5) four molecules in
cell B. The possible number of macroscopic states is given by the following
equation:
(N + n  1)!
W' = (71)
(N — 1)! n !
op = n n
(72)
nA \ nBl... ft*! product of n,!
where & = the possible number of microscopic states for a given macroscopic state
nA the number of molecules in cell A
Hb the number of molecules in cell B
rii the number of molecules in cell i
n the total number of molecules
two cells. For example, with a total of 10 molecules, the probability of finding
at least 40 percent of the molecules in each cell is approximately 656 chances
out of a thousand. With 20 molecules, the probability increases to ap¬
proximately 737 out of 1000 that there will be at least 40 percent of the
molecules in each cell. For two very small ceils, each having a dimension of
one thousandth of a centimeter on a side and existing at standard atmospheric
pressure and 25°C, the total possible number of microscopic states equals
24.928 x 1010. This astronomical figure means that there is almost absolutely
no chance that all the molecules will collect in one cell. Furthermore, there is
an extremely high probability that the division of the molecules between the
two cells will be so nearly equal that it will not be possible to detect a
difference in distribution by any common measuring device.
It is true, by the laws of probability, that there is a possibility of a
significant unbalance in the molecular distribution between the two cells. But,
even for the very small cells under consideration here, such a possibility is
extremely remote. Furthermore, because of the very rapid movement of the
molecules from cell to cell, such an unbalance will last for such a small
fraction of a second that the unbalance cannot be detected by normal
measuring devices.
On the macroscopic basis, when a system is caused to depart from
equilibrium conditions, there is an unbalance of forces acting on the system,
tending to cause equilibrium to be restored. On a microscopic basis, when a
system is not in a state of equilibrium, the molecules are not in their most
probable state. Consider the two interconnected cells in Figure 71. Assume
that there are a large number of molecules present. Let all of the molecules be
moved into cell A and then let the system be isolated. This is a most
improbable state. The molecules will move until the most probable state is
reached, which is substantially equal distribution of the molecules. Thus, an
isolated system always tends to move from a least probable state to the most
probable state.
= (N + n — 1)! = (2+151)!
Answer
(Nl)lnl 1! 15!
Example 73. Determine the possible number of microscopic states for Exs.
71 and 72 for 8 molecules in cell A and 7 molecules in cell B.
Probability and Entropy 161
n’ 15’
& = —. = = 6435 Answer
nA!nB! 8!7!
Since there is no net change in temperature, the change in entropy for the free
expansion of an ideal gas,
V?
S2~ Si = mR —
Vi
= V" (74)
(VA/VT)". The probability of finding all the molecules in the total volume is
unity. The ratio of the probability ^2 of the final state to that of the initial
state, is
0>2_ 1
(75)
(?^ (v,/v2y
or
For one mole of gas, n = n0, the number of molecules per mole. Then
\n(^A = (77)
\VJ no
On the mole basis the change in entropy,
its most probable state, its entropy cannot increase. Thus, if an isolated
system cannot experience a change in entropy, it must be in its most probable
state. But if the entropy of the system can increase, the system cannot be in
its most probable state, and hence, the system is not in equilibrium. These
facts may be used in determining whether or not a system is in equilibrium. If
calculations show that the entropy of an isolated system can increase, then
the system cannot be in equilibrium.
s = k In0> (711)
'G. N. Lewis and M. Randall, Thermodynamics and the Free Energy of Chemical Substances, 1st
ed., McGrawHill, New York, 1923, p. 448.
164 Probability and the Nature of Entropy
There is no rigid proof of this postulate but experience has shown its validity.
A pure crystalline substance is perfectly ordered at a temperature of zero
degrees absolute, that is, there is one probable state. Since & is then unity and
In & = 0, the entropy must be zero at zero degrees absolute temperature.
When changes in entropy are desired for systems in which chemical
reactions are not involved, these changes can be determined by the methods
presented in Chapter 5. However, when chemical reactions are involved,
absolute values of entropy of both the reacting substances and the products
of reactions are required. Absolute values of entropy of a gas may be
obtained by recognizing that the absolute value of entropy of a pure crystal¬
line substance is zero at zero degrees absolute and by finding the summation
of (1) the change in entropy as the substance is heated to its fusion tem¬
perature, (2) the entropy change during melting, (3) the change in entropy as
the liquid is heated to the vaporization temperature, (4) the entropy change
during vaporization, and (5) the entropy change as the gas is heated to the
temperature at which its entropy is desired. This method of determining the
absolute entropy of a gas is a laborious one and, furthermore, requires an
accurate knowledge of the specific heats of the solid, the liquid, and the gas,
the fusion and vaporization temperatures, and also the latent heats of both
fusion and vaporization.
Statistical thermodynamics provides a method for the direct determination
of the absolute value of entropy. This method will be discussed in a later
chapter.
Problems 165
PROBLEMS ____
71 (a) Consider the case of molecules existing in two interconnecting cells.
Determine the possible number of macroscopic states for 2, 4, 6, 8, and
10 molecules.
(b) Determine the possible number of microscopic states for part (a).
72 Determine for Problem 71 the probability that one or the other of the
two cells will be vacant.
73 Determine for the case of molecules existing in two interconnecting cells
the probability of there being at least onethird of the molecules in each
cell for 6, 9, and 12 molecules.
74 Nitrogen occupies a cube at 1.02 bars, 30°C. The cube is 0.1cm on a
side. Determine the number of molecules present. See Section 33.
75 (a) For 6 molecules in two equalsize cells, plot the possible division in
either cell against its microscopic probability (as a fraction). For exam¬
ple, for 4 molecules in one cell, the probability is 30 out of 64 or 0.469.
(b) The same as (a) except for 10 molecules.
Comment on these plots.
_ 8 _
GENERAL EQUATIONS
OF THERMODYNAMICS
81 INTRODUCTION
Certain properties of substances, such as pressure, temperature, volume, and
mass, are relatively easy to measure. Other properties, such as internal
energy, enthalpy, and entropy generally cannot be measured directly but must
be calculated. Methods of determining the changes in these latter properties,
rather than their absolute values, are both acceptable and desirable, since
most engineering problems involve only changes in state. Hence, absolute
values of these properties are not required. In Chapter 4, we developed the
means for the determination of the changes in the internal energy and
enthalpy of an ideal gas. After a discussion of the second law, methods were
developed for the changes in entropy of ideal gases.
Although there are many problems dealing with those gases that show very
little deviation from idealgas behavior, there are many more problems in
which serious errors will be made by the use of idealgas laws. In this chapter,
we develop the general methods of determining changes in the properties of
substances in all phases: solid, liquid, and gaseous. These changes will be
evaluated in terms of changes in pressures, temperatures, volumes and, in
some cases, specific heats. The relationships between these simple properties
were presented in Chapter 4. It will become evident that, for the conditions
under consideration, when relatively simple relations exist between these
simple properties, the equations developed in this chapter will provide a
feasible means of determining changes in the complex properties. It will also
be shown that, when p v = RT, the general relationships developed in this
chapter will reduce to the relationships developed previously for an ideal gas.
For many engineering problems, the accurate pressuretemperaturevolume
relationships required are so involved that it is difficult to use them to
determine changes in other properties. Urtder these conditions, engineers
must resort to tables of the properties of various substances.
Tables of properties of substances are based on extensive laboratory tests;
however, it is very difficult to obtain all the experimental information required
to prepare extensive tables of properties. Furthermore, the accuracy of
experimental data may be subject to question. The equations developed in
166
Introduction 167
this chapter will show that for various processes there are thermodynamic
relationships between the various properties. For example, during the
vaporization of a liquid there is a very precise relationship between the
volume change and the latent heat. Thus, these equations are necessary to
validate experimental data as well as to determine complex properties that
cannot be measured.
The equations developed in this chapter will mathematically verify equa¬
tions that have been used in this text for ideal gases. In addition the equations
developed here can be used to evaluate changes in properties of those actual
gases having simple pvT relationships, such as those of van der Waals. This
chapter will enable the student to understand how thermodynamics is in¬
volved in the preparation of tables of properties of various substances.
Since the methods to be discussed involve the use of partial differential
equations, a brief summary of the required principles is in order.
Assume that Z is a true function of X and Y. Then
dz  (§)/x+(jf)/y (8»
where (dZldX)Y is the rate of change of Z with X when Y is held constant
and (dZldY)x has a similar meaning.
Equation 81 is said to be an exact differential equation, since it involves
quantities X, Y, and Z, which are functions of each other as was originally
assumed. If Z has continuous derivatives, the equality of the second cross
partials becomes a necessary condition for exactness. This principle can be
validated by taking the second cross partials in Eq. 81. Thus,
d(dZldX) _ d(dZldY)
dY dX
or
a2z _ d2z
(8la)
dXdY dXdY
Since there is a mathematical interrelationship between the various properties
of substances and also between the changes in the properties, any differential
equation expressing the relationship must be an exact one.
Some energy quantities, such as heat and work, may be expressed in terms
of the property changes of the system. For instance, for a reversible process
in a closed system, the work transferred is expressed as
8W = pdV
It may appear that W = f(p, V) and that the following differential equation
may be written as follows:
dV
168 General Equations of Thermodynamics
However, the term (dWldp)v has no significance since there is no work done
in a constantvolume process. Neither does the term (dWldV)p have
significance since the work done at a given constant pressure is a constant for
a given volume change. Obviously then, a meaningful differential equation
involving work done by a system and its properties cannot be written. A
similar statement may be made relative to the heat added to the system.
When Z = f(X, Y), a relationship can be established between the partials,
dZldX, dXldY, and dY/dZ by writing an equation similar to Eq. 81 based on
X = f(Y, Z). Thus,
dX = (82)
dX\
dX = dY + dX + dY
( dY )■
Hence,
dY
(84)
When Eq. 84 is divided by (dX/dY)z and the relationship in Eq. 83 is used,
the result is
(85)
or
du = 8q  p d v (87)
Since 8q = T ds,
du = T ds  p dv (88)
(89)
du T — p dv (810)
Equation 810 is a perfectly valid equation for the change in internal energy
for any substance in any phase. However, the partials involving entropy
cannot be measured directly; hence, it is necessary to evaluate these partials
in terms of more readily measurable quantities. In Chapter 4, it was pointed
out that cu is a property and may be expressed as = (duldT)v. This may be
rewritten as
cv = (811)
Therefore,
(812)
The term (dsldv)T in Eq. 810 may be replaced by making use of the
Helmholtz function. This is defined as A = U  TS or, per unit mass, a =
u  Ts. Then
da = du  T ds — s dT
Since a = f(v, T), and since a, v, and T are all true properties, Eq. 813
must be an exact differential equation. From Eq. 8la, it can be shown that
(814)
This is one of the four expressions known as the Maxwell relations. The other
three will be derived later.
170 General Equations of Thermodynamics
When the value of (ds/dT)v from Eq. 812 and the value of (ds/dv)T from
Eq. 814 are substituted in Eq. 810 the result is
du = dT + \T d v (815)
m
dp) =R
dT) V
RT
du = dT + p^j dv = cM dT
v
Since RT/v = p.
In a similar manner, an equation may be derived to evaluate the change in
enthalpy of a pure substance. Since h = u + p v,
dh = du + p dv + v dp
dh = T ds + v dp (816)
Also, since s = f(T, p),
ds
(£). MS)* (817)
ds'
dh = T
.dT.
dT +
(S)*l + v dp (818)
dh
cp (819)
.ds ). m.
Then,
ds'
cp = T (820)
JT.
dg = dh  T ds  s dT
dg = v dp  s dT (821)
Since g = /(p, T), Eq. 821 must be an exact differential equation. From Eq.
83,
(822)
dh = CpdT + (823)
[ vT
A knowledge of the relation between cp and T and the equation of state
relating p, V, and T make possible the use of Eq. 823 for evaluating the
change in enthalpy of any pure substance for any process. This statement
may be illustrated for a substance that obeys the law p v = RT. Thus,
/dv\ _ R
\dT)p~ p
dh = cpdT + (v  dp = Cp dT
ds = cv d v (824)
when p v = RT,
172 General Equations of Thermodynamics
Then
d v
ds (824a)
v
A second expression for entropy change may be obtained by the use of Eq.
817. From Eq. 820, (ds/dT)p = cplT; from Eq. 822 (ds/dp)T = —(d WdT)p.
Substituting these values in Eq. 817 gives
When pv = RT,
(w)
\STJP £
P
and
dT dp
ds cp (825a)
~T~rT
dv (826)
Then,
^ j = T (dpi dT) T(dWdT)p
d v + dp (827)
dT = (828)
 c T (829)
1 Since (dp/d^)T is negative for all known substances and since (dWdT)2
must be positive, cp can never be less than cv.
2 When T approaches zero, cp approaches cu.
3 When (dvldT)2p is zero (as it is for water at 4°C), cp must equal cu.
dl  T “T  (If), *
Since s = /(T, p), this is an exact differential equation. Then
(831)
Hence,
or
(832)
(835)
dh\ _ T
ds)p
f!),*T(lr)„ ,836)
When a substance exists as a twophase mixture, as it does when it is
changing from the liquid phase to the vapor phase, (dpi dT)v = (dpi dT)tvap,
where the subscript “evap” refers to the evaporation or phasechange con¬
dition. For the total phase change from liquid to vapor with the pressure held
constant, the ratio of the change in enthalpy to the change in volume is a
constant, or
hlK. — (Ah.\
Vfg \dvJp
(837)
Equation 837, which is the Clapeyron equation, gives the exact relationship
between the change in volume and the latent heat (enthalpy change) when a
liquid changes to a vapor. When experimental data do not agree with results
calculated from this equation, then the experimental data must be in error.
4Because Thomson later became Lord Kelvin, these coefficients are sometimes known as
JouleKelvin coefficients.
5This includes orifices as well as pressure reducing and pressure regulating valves which produce
irregularities in the flow pattern.
1 2 3
of the gas into kinetic energy. This results in a reduction in the temperature of
the gas.
Downstream from the restriction, because of a greater flow area, the gas
stream slows down, with kinetic energy being turned back into enthalpy. This
results in an increase in the temperature of the gas. Assuming that the area of
the restriction is relatively very small, the flow rate is low. This means that
both the initial and final velocities are low and the net change in kinetic
energy may be neglected.
When the gas temperature is close to that of the surroundings or when the
throttling device is well insulated, the heat exchanged between the gas and its
surroundings can be neglected. In the absence of heat transfer and a net
change in kinetic energy, the first law shows that there cannot be an overall
change in enthalpy. Normally these conditions are assumed to be present, and
hence, it may be assumed that there is no net change in enthalpy in a
throttling process. For an ideal gas, dh = cp dT. Thus for an ideal gas, overall,
a throttling process produces no net change in temperature.
Joule and Thomson recognized that even air, oxygen, nitrogen, and similar
gases are not ideal gases and that other gases, such as carbon dioxide, show
marked deviations from the idealgas laws. Hence, it should be expected that
these gases might have measurable net changes in temperature when throt¬
tled. The change in temperature when a gas is throttled can be determined
precisely by use of Eq. 823, which is repeated here for convenience.
dh = cpdT + vT
or (823)
cp dT = dh  v —
[ T
For the overall throttling process, with no net change in kinetic energy and
with no heat transfer, there cannot be a net change in enthalpy. Consequently,
the overall throttling process can be treated as a constantenthalpy process.
(838)
Porous plug
f7/7/77/7
p2, h pi 
(variable) (fixed)

2 1
—
TTTn'n r/j2ZZZZ2 s jV s ? ? s ? 7 s ? ? s s s s a.
(a)
(b)
devices and found that the porousplug type was the most satisfactory.
Because the porous plug is used frequently today in determining the Joule
Thomson coefficients, this type of experimental work is frequently referred to
as the porousplug experiment.
The variations in temperature with the pressure after a gas is throttled from
fixed initial conditions are illustrated in Figure 82. For some gases, at high
temperature and pressure a small amount of throttling produces an increase in
temperature.
The point on the curve where further throttling produces an inversion in the
temperature change is known as the inversion temperature. The nature of the
throttling curve is independent on the initial conditions as is shown in Fig. 83.
When the initial state of the gas is within the inversion curve, throttling
produces a drop in temperature. At room temperatures and at low or
moderate pressures, the states of most gases fall within the inversion curve.
When hydrogen is at room temperature, however, its state falls outside the
inversion curve. Hence, hydrogen undergoes an increase in temperature upon
being throttled.
To see why throttling produces an increase in temperature in some in¬
stances and a drop in temperature in others, the expression for dh should be
examined. Since h = u + pv,
dh = du + d(p v)
6L. S. Marks and H. N. Davis, The Thermal Properties of Saturated and Superheated Steam,
Longmans, Green and Company, New York, 1922.
Other General Equations 179
i Highpressure
gas
Lowpressure
gas Throttling
orifice
Valve
the temperature of the gas after throttling is only a little lower than that
entering the liquefier. However, the lower temperature gas is circulated back
around the tube containing the higher pressure gas, thus reducing its tem¬
perature. Hence, the temperature of the gas after throttling is also reduced.
Continued operation of this apparatus produces successively lower tem¬
peratures of the gas emerging from the orifice. Ultimately the temperature
drops to the condensation temperature for the lowpressure gas, and partial
condensation occurs. The remaining lowpressure gas may be compressed to
be recirculated.
(814)
(822)
du = T ds — p dv (88)
(839)
dh = du + p d v + v dp = T ds + v dp (840)
(841)
The first two Maxwell relationships were used here to determine certain
properties from pv~T measurements. The other two relationships can be
used in a similar manner.
88 SUMMARY
In this chapter the general equations of thermodynamics have been presented,
showing the interrelationships between the various thermodynamic proper¬
ties. When p1< T relationships and, in some cases, the behavior of the
specific heats of any substance are known, the other thermodynamic proper¬
ties can be determined without the necessity of trying to measure them. This
fact is very important since it is extremely difficult to measure many of these
properties.
It has been shown also that when pv = RT, these general equations reduce
to those for ideal gases, some of which were developed earlier in this text. In
other cases these equations point out relationships that had not been
developed previously. For example, Eq. 833 shows that when pv = RT, a
change in pressure at constant temperature produces no effect on the value of
the specific heat cp.
When the experimentally determined properties of substances do not have
the same relationships to each other that the general equations of ther¬
modynamics show they should have, then there must be errors in the
experimental data. Thus tables of properties, to be valid, must be based on
experimental data, verified, and tied together using the general equations of
thermodynamics.
Problems 181
PROBLEMS__
81 Derive an expression for the change in internal energy of a substance
that obeys van der Waals equation of state.
82 Air is compressed from 13.8 bars, 93°C to 138 bars, 205°C. Determine
accurately the change in internal energy and enthalpy per kilogram of
air. Suggestion: Use the mean compressibility factor as a constant.
83 Determine the change in entropy in Problem 82.
84 The lowest available temperature in Problem 83 is 22°C. Determine the
change in available energy of the air.
85 The following boiling temperatures of water have been determined:
814 Derive a general expression for the change in entropy of a gas obeying
the van der Waals equation. Hint: See Eq. 824.
815 For liquids and solids it is relatively easy to measure the volume
expansion (the fractional change in volume per unit increase in
temperature at constant pressure) and the compressibility k (the frac¬
tional decrease in volume per unit increase in pressure at constant
temperature). Derive an equation for the difference between cp and
in terms of £$ and k.
816 Derive an expression for the change in temperature per unit volume
change for the unrestricted expansion of an actual gas. (As used here,
the unrestricted expansion is a free expansion in a closed system.) The
expression is to be in terms of p, v, T, and cv.
817 Using the expression developed in Problem 816, derive an expression
for the temperature change for a free expansion of a gas obeying the
law pv = RT.
818 The same as Problem 817 except for a gas obeying the van der Waals
law.
819 Derive an expression for the change in enthalpy in terms of p, v, T, and
£$ (the fractional increase in volume per unit increase in temperature at
constant pressure).
820 The following boiling temperatures of refrigerant F12 have been
determined:
VAPORS
91 INTRODUCTION
There is no sharp line of distinction between a vapor and a gas. In general, a
gas is considered to be far removed from its liquid state whereas the vapor is
thought to be rather readily liquefiable. However, at very low pressures a
socalled vapor may be treated as an ideal gas for most engineering purposes.
For example, the water vapor in atmospheric air is at such a low partial
pressure that it follows the idealgas laws very closely. On the other hand,
when a vapor exists at very high pressures it deviates significantly from an
ideal gas, even when its temperature is much higher than the boiling tem¬
perature for the given pressure. In general, when the compressibility factor of
a vapor is substantially equal to unity for the existing temperature and
pressure, the vapor may be treated as an ideal gas (see Section 39).
It was pointed out in Chapter 8 that when a pvT relationship is available
for a substance, other properties may be calculated. However, when the
compressibility factor differs greatly from unity, an accurate pvT relation¬
ship is a complicated one. This makes the determination of other properties
by use of the pvT relationship very difficult. Under these circumstances, it
is most desirable to have tables available that give the various properties of
the substance under consideration.
Very extensive and reliable tables are available for the properties of
common vapors, such as steam. Although tables are available for the less
common vapors, generally they are much less extensive and, in some cases,
are of doubtful accuracy. It should be recognized that the compilation of
accurate and extensive tables of properties is extremely difficult. In general,
certain properties, such as pressure, temperature, specific volume, and
specific heat must be determined over a wide range of conditions. The
determination of many of these properties is far from being easy. For
example, a precise determination of the specific volume of a boiling liquid
and of its vapor at the boiling temperature for the given pressure requires
much ingenuity and patience. Once the simple properties have been deter¬
mined experimentally, these properties may be correlated by use of the
equations developed in Chapter 8. Then additional properties can be cal¬
culated, generally by use of these equations and pvT relationships. Since
these equations are precise ones, the accuracy of the calculated properties
depends solely on the experimentally determined properties. However, it
183
184 Vapors
W \
F’istor
Liquid "
II M a
FIGURE 92 TS diagram for heating a liquid and vapor at constant pressure.
186
Vaporization of Liquids 187
'In a nonpolar compound the atoms are arranged symmetrically in the molecule, and there are no
unbalanced electrical charges that tend to rotate the molecule when it is placed in an electrostatic
field.
:J. H. Keenan, F. G. Keyes, P. G. Hill, and J. G. Moore, Steam Tables, Wiley, New York, 1969.
Second edition, 1978.
Compressed Liquids 189
Temp¬ Specific
Pressure erature Volume Internal Energy Enthalpy Entropy
(MPa) (°C) (cm3/g) (J/g) (J/g) (J/gK)
Sat Sat Sat Evap Sat Sat Evap Sat Sat Evap Sat
Liquid Vapor Liquid Vapor Liquid Vapor Liquid Vapor
p t vf vg Uj Ufg Ug hf hfg hg Sf Sfg sg
The unit of pressure used in these tables is the megapascals. In dealing with steam, some authors
express pressures in either kilopascals or bars. A bar equals 100 kilopascals and is approximately
equal to 1 atmosphere.
4Sometimes called subcooled liquids.
190 Vapors
Example 91
(a) Determine the difference between (1) the specific volume and (2) the
enthalpy of saturated water at 40°C and water at a pressure of 5 MPa,
40° C.
(b) Solve the same problem stated in part (a), except the second pressure is
50 MPa.
Solution
(a) From Table A3a in the Appendix at 40°C, = 1.008 cnr/g and hf =
167.57 J/g. From Table A3d, v = 1.0056 cm3/g and h = 171.97 J/g. Then the
increase in pressure from the saturated value of 0.007354 MPa to 5 MPa
has decreased the specific volume 0.0024 cnr/g or 0.24 percent. The
enthalpy has increased 2.6 percent.
(b) From Table A3d in the Appendix, at 40°C, 50 MPa, v = 0.9872 cm3/g and
h = 211.21 J/g. Then the increase in pressure to 500 bars has decreased the
specific volume by 0.0208 cm3/g or 2.06 percent. The increase in pressure
has increased the enthalpy by 43.65 J/g, or 26.1 percent.
Example 92. Determine the difference between the specific volume and the
enthalpy of saturated water at 300°C and water at 300°C under a pressure of
50 MPa.
Solution. From Table A3a in the Appendix, the specific volume of saturated
water at 300°C is 1.4040 cm3/g. From Table A3d, the specific volume of water
at 300°C, 500 bars is 1.2860. This represents a decrease in specific volume of
0.1150 cm3/g or 8.40 percent.
From Table A3a, the enthalpy of saturated water at 300°C is 1344.0 J/g.
From Table A3d, the enthalpy of water 300°C, 50 MPa is 1323.0 J/g. This
represents a decrease of 21 J/g or 1.56 percent.
Properties of a Wet Vapor 191
In a similar manner
hx hg yfyg (93)
or
hx = hf 4 xhfg (94)
and
vx = vg  yvfg (95)
and
5It is preferable to leave this equation in this form when the moisture content of the steam is
known.
Determination of Vapor Properties 193
or the state is steam at a pressure of 0.6 MPa and a moisture content of 8.95
percent. Answer
6It is assumed here that the substance is far removed from its solid phase.
194 Vapors
The enthalpyentropy chart is the most common of several diagrams designed by Mollier.
Vapor Charts 195
Entropy (J/gK)
The subscripts “in” and “out” refer to the fluid conditions at entrance and
exit, respectively, of the section of the flow passage under consideration, and
Q is the heat lost by the fluid in its passage through the section.
In most engineering applications, fluid velocities in pipe lines are relatively
low. Although the throttling action produces an immediate increase in velo¬
city, normally because the flow area after the throttling device increases
greatly, the fluid velocity reduces to close to its original value. Overall, then,
there will be no appreciable change in kinetic energy.
Whether the heat transferred is appreciable is dependent on the tem¬
perature difference between the fluid in the flow section and its surroundings,
the amount of insulation covering the flow section, the length of the flow
section, and the mass rate of flow.
When the throttling action occurs abruptly, as in a valve or orifice, heat
losses are generally negligible. When there are large restrictions in the flow
passages, the rates of flow are low. Hence, the kinetic energies in Eq. 97 may
then be neglected, and Eq. 97 becomes Hm = Hout. This conclusion agrees
with that developed in connection with the discussion of the JouleThomson
effect. The JouleThomson effect for a vapor is large. Therefore, when a
vapor is throttled, an appreciable temperature change takes place, and it
becomes necessary to use vapor tables to predict the state of a vapor after it
is throttled.
dh = Sq and h2=h\ + q
198 Vapors
From Table A3c in the Appendix, hi = 2827.9 J/g. Then h2 = 2827.9 + 223.3 =
3051.2 J/g. From Table A3c, p = 1 MPa and h = 3051.2 J/g. Then t = 300°C.
The final state of the steam is a temperature of 300°C and a pressure of
1 MPa. Answer
Solution. From Table A3c in the Appendix, the initial entropy is 6.9212 J/g
K. This is also the final entropy. Since this entropy exceeds the entropy of dry
saturated steam at 0.6MPa pressure, the steam is still superheated. From
Table A3c, by interpolation, the final temperature is 190.4°C. Answer
Example 99. Determine the work done per pound of steam in Example 98.
Solution. It was not specified whether the system is closed or open. Hence,
solutions will be given for each type.
Closed system. Q = U2~ U\ + W\.2. Since Q = 0, W\.2 = Uj — U2. Using Table
A3c in the Appendix,
Open system. It will be assumed that the steam does not undergo a
significant change in kinetic energy as it passes through the system. Then,
Example 910. Water enters a steam generator at 25 MPa and 240°C. Steam
leaves at 22 MPa and 550°C. Determine the heat added per gram.
Note: The value of Hi was obtained from Table A3d in the Appendix.
Example 911. Steam enters a turbine at 3 MPa and 470° C with a flow rate of
202,000 kg/h. 115,000 kg/h are extracted at 0.24 MPa and 170°C. The turbine
exhausts at 3.8 kPa with a velocity of 140 m/s, and delivers 24,000 kW.
Determine the enthalpy of the exhaust steam.
Solution. Refer to Figure 911. The turbine should be so well insulated that
the heat lost per kilogram of steam is negligible. The energy balance then is
/ 1402 \
202,000 x 1000 x 3055.4 = 115,000 x 1000 x 2807.2 + 87,000 x 1000(h2 + 21~kV00>)
Example 912. Steam at 6 MPa and 480°C is throttled to 4 MPa for partload
operation of a small turbine. Determine:
(a) The final state = 4 MPa and 469.1°C by interpolation from the superheated
tables. Answer
(b) The change in entropy during throttling equals
6.9964  6.8176 = 0.1788 J/gK
Then the final state is wet vapor at a pressure of 2.191 bars and a quality of
17.91 percent. Answer
i
The method of determining the state after a liquid is throttled was illus¬
trated in Example 97. If, instead of being throttled, the refrigerant were
permitted to expand isentropically, it could deliver work. This work equals
the loss of available energy because of throttling. The method of determining
this loss is illustrated in the following example.
Example 914. Determine the loss in available energy per gram of refrigerant
as a result of the throttling process in Example 97.
This loss in available energy of 1.737 J/g means that if the liquid had been
expanded in a reversible adiabatic manner, 1.737 J/g of work would have been
obtained.
Example 915. The moisture content of steam is desired in a line where the
pressure is 1.61 MPa. The barometric pressure is 740 mm of mercury. The
data from the throttling calorimeter shows that the steam pressure is 8.6 mm
of mercury and the temperature is 120°C. Determine the condition in the line.
Solution
740
atmospheric pressure = ^ x 0.101325 = 0.0987 MPa
760
line pressure = 1.61 +0.0987 = 1.7087 MPa
From the superheated tables, the enthalpy in the calorimeter = 2716.6 J/g.
Then, at the line pressure, since hx = hg — yhfg,
When the steam pressure is very low, such as it is when it enters a power
plant condenser, it is very difficult to use most calorimeters to determine the
moisture content. Generally, sufficient information can be obtained to ap¬
proximate the moisture content by application of the first law. This concept
was used in Example 912 to determine the enthalpy of the steam at turbine
exit.
Nonequilibrium States of TwoPhase Mixtures 203
Example 916. Determine the moisture content of the steam leaving the
turbine in Ex. 911.
Constant
pressure
line
The slower moving molecules of the vapor will be attracted into the liquid
phase (condensation) when they approach the surface of the liquid. Equili¬
brium exists between the liquid and vapor phases when the rate of vaporiza¬
tion equals the rate of condensation. For any given fluid the equilibrium
temperature is a function of the vapor pressure. This equilibrium temperature
(i.e., for a liquid with a flat surface) is listed in tables of properties of vapors
for various pressures as the saturation temperature.
Now consider a molecule of a liquid approaching the surface of a drop.
Comparing Figures 916 and 917, it may be seen that for a given molecule
approaching the surface of the drop, Figure 917, there are fewer molecules in
the sphere of action restraining the given molecule from leaving the surface
and passing into the vapor phase. For any given temperature and pressure,
more molecules will be leaving the liquid phase where the liquid exists in the
form of drops than where it has a flat surface. For any given pressure, the
temperature of the drops (and also the vapor) must be lowered to decrease the
rate of vaporization and thus to achieve equilibrium. Therefore, the equili¬
brium temperature between drops of a liquid and its vapor, for any given
pressure, is lower than the tabulated saturation temperature.
It is possible to establish a relationship between equilibrium and saturation
temperatures in terms of drop radii. Such a relationship shows that unless the
drop radius is extremely small, the difference between the saturation tem¬
perature and the equilibrium temperature of the drops and their vapor is
insignificant. However, it has been found that in cases of supersaturation flow
in steamturbine nozzles, condensation at first results in the formation of
droplets that have very small radii. Although these droplets can be in
equilibrium with the vapor as just described, such equilibrium is only tem¬
porary. When a very small droplet loses or gains a very few molecules, its
radius changes and it is no longer in equilibrium with its vapor.
One engineering example of nonequilibrium conditions has been discussed.
Many more nonequilibrium conditions may be encountered. Although con¬
ditions in many engineering problems are so close to equilibrium that equili¬
brium may be assumed to exist, very serious errors may be introduced by
such an assumption in other cases.
Problems 207
PROBLEMS __
91 Specify whether steam is wet, dry, or superheated for the following
conditions:
(a) t = 200°C, p = 1.44 MPa
(b) t = 220°C, p = 2.318 MPa
(c) p = 1.0 MPa, 5  6.672 J/gK
(d) p = 3.0 MPa, t = 234°C (not 234.00°C)
(e) t = 250°C, v = 54.2 cm3/g
(f) p = 11.0 MPa, h = 2805 J/g
(g) p = 4.0 MPa, 5 = 5.897 J/gK
(h) p = 15.0 MPa, t = 310°C
92 Specify when refrigerant F12 is wet, dry, or superheated for the
following conditions:
(a) t = 10°C, p =4.12 bars
(b) t = 80° C, v = 6.974 x 10”3 m3/kg
(c) p = 5 bars, s = 0.982 J/gK
(d) p = 6.516 bars, t = 21°C
(e) p = 1.004 bars, h = 224.14 Jig
(f) p = 1.000 bars, t = 30°C (not 30.00°C)
93 (a) Does an increase in pressure at constant temperature increase the
enthalpy of water?
(b) Does an increase in pressure at constant temperature decrease the
specific volume of water?
94 Determine the percentage of change in the properties of saturated
water (^, h, and s) at 40°C when the pressure is increased to 5 MPa.
95 Determine the percentage of change in the properties of saturated
water (v, h, and s) at 350°C when the pressure is increased to 50 MPa.
96 Draw conclusions from Problems 94 and 95 of the effect of pressure
on the properties of water.
97 (a) Steam at 0.125 MPa has an enthalpy of 2495 J/g. Determine the
moisture content.
(b) Steam at 250°C has an internal energy of 2527 J/g. Determine the
moisture content.
(c) Saturated water at 240°C is throttled to 0.125 MPa. Neglect heat
losses and changes in kinetic energy and determine the final quality.
(d) After expansion to 0.15 MPa steam has an entropy of 6.932 J/gK.
Determine the moisture content.
98 (a) Determine the amount of pressure required to decrease the volume
of saturated water one percent at 40°C.
(b) Same as part (a) except at 300° C.
99 Water enters a pump at 0.12 MPa 80°C and leaves at 20 MPa, 90°C.
Determine the percentage error in determining the pump work by
neglecting the effect of pressure on enthalpy.
208 Vapors
910 Same as Problem 99 except the final conditions are 5 MPa, 82°C.
911 (a) Refrigerant F12 leaves a condenser at 7.8 bars, 30°C. Within
engineering accuracy, specify the specific volume, enthalpy, and
entropy.
(b) Mercury leaves a condenser at 0.025 bar, 200°C. Within engineering
accuracy specify the specific volume, enthalpy and entropy.
912 Steam enters a superheater at 20 MPa with a moisture content of 0.2
percent. It leaves at 19.6 MPa, 550°C. The flow rate is 638,000 kg/h.
Determine the heat added. State any assumptions that are made.
913 Steam is heated at a constant pressure of 2.0 MPa to a temperature of
500°C. The original moisture content is 0.5 percent. Determine the heat
added per kilogram. Is it necessary to know whether this is an open or
closed system?
914 A tank having a volume of 0.685 nr is 48.2 percent full of water at
atmospheric pressure and 40°C. Neglect the water vapor in the air
above the water. How much heat must be added to increase the
pressure to 8 MPa?
915 Steam expands isentropically from 20 MPa, 550°C to 0.01 MPa. Cal¬
culate the work per kilogram of steam for (a) closed system and (b)
open system.
916 Same as Problem 915(b) except the final pressure is 0.005 MPa. Cal¬
culate the percentage of increase in the work.
917 A turbine expands steam from 20 MPa, 550°C to 0.005 MPa. The actual
work is 78 percent of the isentropic work. Specify the enthalpy at the
end of the expansion and the moisture content. What assumptions must
be made?
918 Water enters a steam generator at 25 MPa, 160°C. Steam leaves at
22 MPa, 550°C. Determine the percentage of error caused in finding the
heat added by neglecting the effect of pressure on the enthalpy of the
water.
919 (a) Dry saturated steam at 20 MPa is throttled to 3 MPa. Specify the
steam conditions after throttling.
(b) Dry saturated steam at 2.5 MPa is throttled to 0.10 MPa. Specify the
steam conditions after throttling.
920 Steam enters a condenser at 2.5 kPa with a moisture content of 10.2
percent. Condensate leaves at 20°C. Circulating water (to condense the
steam) enters at 8°C and leaves at 16° C. The rate of steam flow is
892,000 kg/h. Determine the rate of circulating water flow.
921 Refrigerant F12 (liquid) at 35°C is throttled to 2.1912 bars and then
enters an evaporator. It leaves the evaporator at 2.1912 bars, 0°C.
Determine the rate of refrigerant flow if the evaporator is to produce
850 kJ of refrigeration per minute.
Problems 209
922 Refrigerant F12 enters a condenser at 7.449 bars, 60°C, at the rate of
48.5 kg/min. Condensate leaves saturated. Calculate the amount of heat
that must be removed from the condenser per minute.
923 A mercury vapor turbine receives dry saturated mercury vapor at
550°C and expands it to 0.0232 bar. The turbine has an isentropic
efficiency of 78 percent. Determine the rate of mercury vapor flow to
produce 50,000 kW.
924 An ammonia turbine is to produce power by absorbing heat from warm
ocean surface water. Saturated ammonia vapor enters the turbine at
25°C. The vapor expands to a pressure of 728.11 kPa. The turbine has
an isentropic efficiency of 80 percent. Determine the rate of ammonia
flow for a turbine output of 100,000 kW.
925 Assume that the ammonia in Problem 924 leaves the condenser as a
saturated liquid. It is condensed by cool water brought up from the
ocean depths. This water increase in termperature from 5°C to 10°C in
the condenser. Determine the volume rate of flow of this water,
assuming that its density is 1.025 g/cnr and its specific heat is 2.279 J/g
K.
926 Specify the pipe line conditions of steam at a pressure of 2.25 kPa for
the following throttlingcalorimeter conditions:
(a) 0.1 MPa, 100° C
(b) 0.1 MPa, 99.6°C (not 99.63°C)
(c) 0.1 MPa, 200° C
927 Refrigerant F12 is compressed isentropically from 3.0861 bars, 20°C to
a pressure of 9.6065 bars. Calculate the value of the isentropic exponent
k.
928 Steam expands isentropically in a closed system from 15 MPa, 550°C to
4.5 MPa. Calculate the value of k and use this to calculate the work
done per kilogram of steam. Compare this work with that calculated
using the change in internal energy.
929 Steam at 10.0 MPa, 350°C is throttled to 1.0 MPa. The lowest available
temperature is 40°C. Determine the loss of available energy as a result
of the throttling.
930 Determine the compressibility factor for steam for the following con¬
ditions:
(a) 0.01 MPa, 50°C
(b) 0.1 MPa, 100° C
(c) 1.0 MPa, 300° C
(d) 1.0 MPa, 800° C
(e) 10.0 MPa, 325°C
(f) 10.0 MPa, 800° C
931 From the results of Problem 930, is it possible to consider steam to be
an ideal gas under any conditions? If so, specify these conditions.
210 Vapors
NONREACTIVE GASEOUS
AND VAPOR MIXTURES
101 INTRODUCTION
Thus far in this book, it has been assumed that the systems under con¬
sideration contained only a single pure substance. This assumption is
sufficiently accurate for many engineering systems, such as a steam turbine, a
singlefluid gas compressor, a pump, or a refrigerating system. Often,
however, the system may contain two or more substances in sufficient
amounts to make it necessary to examine the effects of each substance on the
properties and the behavior of the system. These substances may or may not be
in chemical equilibrium.
Unless the substances are in gaseous form and at such temperatures and
pressures that they behave as ideal gases, intermolecular forces will exist.
These intermolecular forces do not obey any simple law and, therefore, it is
difficult to determine the properties and behavior of the mixture. However, in
engineering practice many gaseous mixtures are encountered where the gases do
closely resemble ideal gases. Examples of such systems are the gas turbine, the
gas passageways in a steam generator (including the economizer and air
preheater), the internal combustion engine during compression, expansion, and
exhaust, and the gas passageway in a magnetohydrodynamic generator.
In many of these systems, the gaseous mixture is either in chemical
equilibrium or does not undergo a reaction during the time period under
consideration. Hence, it will be assumed that no chemical reaction is involved
in the systems under discussion in this chapter.
211
212 Nonreactive Gaseous and Vapor Mixtures
system. Since both gases are ideal, no intermodular attractions can exist.
Furthermore, since the two gases are at the same temperature, there can be
no net change in molecular kinetic energies. Hence, each gas exists in¬
dependently of the other gas. Gas A will exert the same pressure as it did
prior to the introduction of gas B. Likewise, gas B will exert a pressure equal
to the pressure it would have had if it existed alone in the system. The
pressure exerted by each gas in a gaseous mixture is known as its partial
pressure. Thus, the partial pressure of each gas in a mixture is the pressure
that the gas would exert if it alone occupied the entire volume at a tem¬
perature equal to that of the mixture.
The preceding observations can be formulated as Dalton's law of partial
pressures. This law states that for mixtures of ideal gases, each gas occupies
the entire volume at its own partial pressure, and the total pressure of the
gaseous mixture equals the summation of the individual partial pressures. In
equation form this law is
pV = NR0T (103)
Example 101. A tank having a volume of 0.6 m3 contains oxygen at 25°C and
480 kPa. Nitrogen is introduced into the tank without producing a change in
temperature until the pressure becomes 920 kPa. Determine the mass of each
gas and its partial volume.
_ pV _ 480 x 1000x0.6
116.18 g moles
R0T 8.314(25 + 273.15)
Then
_ 440 x 1000 x 0.6
106.5 g moles
N 8.314(25 + 273.15)'
Each gas occupies the total volume at its own partial pressures. The volume it
would occupy at the total pressure = partial pressure/total pressure x total
volume. For the oxygen,
480
partial volume = x 0.6 = 0.313 Answer
920
U = UA + UB+ (104)
When the gases are ideal ones, the product pV for the mixture equals the
sum of the values of pV of the individual gases. This statement may be
demonstrated as follows:
n = na + nb + nc...
214 Nonreactive Gaseous and Vapor Mixtures
Then
or
Since
H = U+pV
(105)
H = HA + HB +Hc
When the gases are not ideal, the total pressure is not necessarily equal to
the sum of the individual partial pressures. Hence, the product pV does not
necessarily equal the sum of the individual values of pV. Under these
conditions it follows that the enthalpy for a closed system of a mixture of
gases that are not ideal does not necessarily equal the sum of the enthalpies of
the individual components of the mixture.
For ideal gases, with a datum at zero degrees absolute temperature
U = Nc„T
Hence,
(„ —
_(Nc*)a
 + (NcJb + (Nc*)c • • •
(106)
N
In a similar manner,
A useful term, which may be used in connection with Eqs. 106 and 107, is
the mole fraction. The mole fraction is defined as the ratio of the number of
moles of any one gas to the total number of moles present. Thus,
The partial entropy of a gas in a gaseous mixture is the entropy that the
individual gas will possess when it occupies a volume equal to the volume of
the gaseous mixture and has the same temperature. Gibbs’ law of partial
entropies states that the total entropy of a mixture of ideal gases equals the
sum of the partial entropies of the individual constituents. This law may be
demonstrated as follows.
Consider the cylinder in Figure 101. In the cylinder on the righthand side
is a movable gastight piston, which is shown as solid. To the right of this
piston is a complete vacuum. To the left of this piston is a semipermeable
membrane, rigidly attached to the cylinder walls. It will permit the passage of
one gas, gas B, through itself but will not permit gas A to pass through. To the
left of the semipermeable membrane is a mixture of two ideal gases, gas A
and gas B. In the extreme left of the cylinder is a second semipermeable
membrane, which will permit the passage of gas A but not gas B. This
membrane, which is movable, is connected to the solid piston by means of a
piston rod.
(b)
FIGURE 101 Reversible separation of gases, (a) Start. (b) Intermediate, (c) Finish.
216 Nonreactive Gaseous and Vapor Mixtures
Assume that the coupled pistons have been moved an infinitesimal distance
to the right (see Fig. 10la). Gas B in the very small space to the left of the
solid piston exerts a pressure (to the right) of pB on the solid piston. Gas A in
the very small space to the left of the membrane piston exerts a pressure (to
the right) of pA on the membrane piston. These two pressures exactly equal
the pressure of pA I pB acting to the left on the coupled pistons. Assuming an
isolated system and no friction, the application of an infinitesimal force to the
right on the coupled pistons will cause them to move. When the infinitesimal
force is applied intermittently, gas diffusion through the membranes will
maintain equality of the pressures of the gas involved (see Fig. 10lb). Hence
the forces acting on the coupled piston are balanced at all times and remain
so, provided that no finite force is applied to the pistons.
Continued application of the infinitesimal force will cause the pistons to
move completely to the right (see Fig. 10 1c). There will be complete
separation of the gases. Since only an infinitesimal force was required, the
work required for separation also is infinitesimal, and the separation process
may be assumed to be reversible. Hence, no entropy change occurred during
the separation. Thus, the entropy of a gaseous mixture equals the summation
of the entropies of the individual gases existing at their partial pressures in the
mixture and at mixture temperature, or
S = Sa + SB + Sc • • • (108)
where the terms SA, SB, and Sc signify partial entropies.
Removable partition
* ■ .m ■ • ;
Gas A Gas B
1 2 !v!v!
S2~ S, = mR In
pv
In
©
440 x 0.3 ] 0.58
= 0.2465 kJ/K Answer
80 + 273 0.3
Now assume that with the partition in place, compartment 2 in Figure 102
is filled with an ideal gas B, which is not reactive with gas A and which has
the same temperature as gas A. When the partition is removed, gas A expands
and occupies the total volume. The presence of gas B does not change the
final condition of gas A. Since the initial and final conditions of gas A are
independent of the presence of gas B, the change in entropy of gas A must be
the same as it was when that gas expanded into a complete vacuum. Upon
removal of the partition, gas B also expands irreversibly. The change in
entropy for gas B can be found by adopting a procedure similar to that
described for gas A.
Upon removal of the partition, there is a driving force (i.e., the individual
gas pressure) that causes movement of each gas into the other compartment,
tending to equalize the partial pressure of each gas through the cylinder.
Putting it differently, the state of either gas is an improbable one at the time
of removal of the partition and, hence, will move to a more probable state.
As discussed in Chapter 7, when a system moves from a less probable to a
more probable state, there is an increase in entropy.
Now consider the two compartments filled with the same kind of gas under
the same conditions of temperature and pressure. Will there be an increase in
entropy when the partition is removed? The answer is no. It is true that some
molecules in compartment A will move into compartment B and vice versa
upon removal of the partition. But there is no pressure difference or driving
force to cause a change in state. Since there is no change in state of the gas,
there cannot be a change in entropy. Looking at the problem in a different
way, the most probable configuration of the molecules is an equal division
between the two compartments. Since they are in their most probable state,
removal of the partition cannot increase their probability. Hence, the entropy
cannot change.
When two gases are not under the same conditions of temperature and
pressure, there will be an exchange of energy between the two upon mixing.
Hence, the entropy change cannot be found so readily as in the previous case.
If the two gases originally occupied adjacent compartments and the mixing
218 Nonreactive Gaseous and Vapor Mixtures
took place in a closed system, the total internal energy could not change
during the mixing, provided that the system was isolated from its surround¬
ings. Since the two gases will come to equilibrium temperature, this tem¬
perature may be found. The final temperature fixes the final state of each gas.
Hence, the entropy change of each gas can be calculated.
pV 440x 1000x0.3 .. no i
or 1439 g
N°2 ~ R0T ~ 8.314(80 + 273) ~ 44 98 m0 eS
AUq2 = AUn2
1439.0 x 0.651(tf  80) = 1521 x 0.734(130  tf)
The final temperature
tf = 106° C
P o. = N^°T
V
= 44,98 X
0.58
= 244,400 Pa = 244 kPa
54.32x8.314(106 + 273)
P N, = 295,100 Pa = 295.1 kPa
0.58
P_2
S2 — Si = ntCp In — mR In
11 Pi
/106 + 273N 8.314, /244,400\
= 1439x0.908 In 1439 x
V 80 + 273 ) \440,000/
= 92.86 + 219.82 = 0.3127 kJ/K
Note that the change in entropy of the oxygen exceeds that of Example
102. The cause of the increase is the heat the oxygen has received from the
nitrogen.
When gases are mixed in a given space, the temperature and, hence, the
pressure of the mixture are fixed by the total internal energy of the gases
forming the mixture. Therefore, all of the other properties of the mixture are
also fixed.
It has been inferred that the gases under consideration must be nonreactive
(i.e., can never react). Ideal reactive gases (can react under certain conditions)
may be treated in a similar manner, provided that the conditions during
mixing do not permit reaction. Many common reactive gaseous mixtures must
be heated to temperatures much in excess of room temperatures to cause a
measurable reaction to take place.
Example 104. A stream of oxygen at 300 kPa and 25° C, flowing at the rate
of 8 kg/min, mixes with a stream of nitrogen having a pressure of 520 kPa and
a temperature of 80°C. The nitrogen rate of flow is 14 kg/min (see Fig. 103).
Determine the change in entropy of the oxygen per minute.
Solution. Since the velocities of the gases are not given, it will be assumed
that they are sufficiently small to permit changes in kinetic energy to be
neglected. It will be assumed also that the mixing is adiabatic. A third
assumption to be made is that the pressure after mixing equals the lowest gas
stream pressure, namely 300 kPa. For the assumptions made, there can be no
change in the total enthalpy of the gases. Then the change in the enthalpy of
oxygen must equal the change in enthalpy of the nitrogen. Recognizing that
dH = mcp dt, for a time period of a minute,
The final partial pressure of each gas is proportional to the relative number
of moles of that gas.
The number of kilogram moles of oxygen equals 8/32. For nitrogen this
number equals 14/28. Then the final partial pressure of the oxygen,
8/32
Po2 x 300 = 100 kPa
8/32 4 14/28
s2s, = men In T  mR In Pi
T, Pi
61.53 + 273.15
= 8 x 1000 x 0.908 In 8 x 1000 x In P00
( 25 + 273.15 ) 32 V300,
= 3123 J/K Answer
The gravimetric analysis of air is, then, 23.2 percent oxygen and 76.8 percent
atmospheric nitrogen. These calculations also show that the mass of a gram
mole of air is 28.97 g.
A gravimetric analysis may be converted to the volumetric basis in a
reversed manner, as illustrated in the following example.
Solution
(a) The calculations may be arranged as follows:
Grams per Grams Moles per Total Moles per Percent
Substance Gram Gas r per Mole = Gram Gas T Moles  Mole Gas by Volume
co2 0.15  44 = 0.00341 h 0.03341 = 0.102 10.2
o2 0.08  32 = 0.00250 s 0.03341 = 0.075 7.5
n2 0.77  28 = 0.02750 h 0.03341 = 0.823 82.3
0.03341
(b) The calculations show that there is 0.03341 mole/g gas. Hence, the weight
per mole is
1
29.9 g
0.03341
= /jctugl mv_ X
\saturated mv/T V
where <f> is relative humidity. Treating the vapor as an ideal gas, Eq. 109 may
be rewritten as
(pV/JRT)actual vapor P actual
(1010)
(P V/RT) saturated vapor Psaturated
Some authors give Eq. 1010 as the defining equation for relative humidity.
For steadystate conditions, the mass rate of flow of dry air is constant for
the system under consideration. This statement may not be true for the water
vapor, since there may be vaporization of water or condensation of water
vapor in the system. It is desirable to know the mass rate of flow of water
vapor in various parts of the system. Since the mass rate of flow of air is
constant, the mass rate of flow of vapor at any point can be determined by
establishing a relationship between the mass of vapor and the mass of dry air.
The ratio of the mass of vapor to the mass of dry air is known as the humidity
ratio, (o, also called the specific humidity. It is defined by the following
equation:
When the vapor obeys the idealgas laws, Eq. 1011 may be rewritten as
follows: Use the relationship m = pV/RT for both the vapor and dry air in
Eq. 1011 and also R = R0/m (m is the mass per mole). Then
or
'it is possible by chemical or physicalchemical means to remove substantially all water vapor
from air. A measurement of the amount of vapor removed permits a determination of the original
humidity of the air. Such a method, however, calls for considerable equipment.
Dry bulb
both the temperature of the air and that of the water on the wet bulb decrease
until equilibrium is reached. The difference between the wetbulb and dry
bulb temperatures is known as the wetbulb depression. To maintain continued
vaporization, and hence, a constant wetbulb temperature, there must be relative
motion between the wet bulb and the air surrounding it. A common form of the
wetbulb psychrometer is the sling psychrometer, shown in Figure 105. This
psychrometer is twirled around, thus providing the necessary relative motion
between the air and the wet bulb.
The wetbulb temperature is a saturation temperature. So is the dewpoint
temperature. However, the wetbulb temperature is the higher of the two.
Consider air flowing over the wet bulb. Since the air picks up moisture as it
passes over the wet bulb, the saturation temperature of the air leaving the wet
bulb (the wetbulb temperature) must exceed that of the air approaching the
wet bulb (the dewpoint temperature). The relationship between these tem¬
peratures is shown on the Ts plane of Figure 106.
In the ideal case, the process taking place on the surface of the wetbulb
thermometer is an adiabatic saturation process. This process may be con¬
sidered by referring to Figure 107. The chamber in this figure is insulated so
that the process is adiabatic. Here air passes over the surface of water. There
Steam tables may be used to evaluate the enthalpy of water and water
vapor. At very low pressures, that is, below 0.01 MPa, the enthalpy of water
vapor is substantially independent of the pressure. Hence, the enthalpy of
superheated vapor may be taken to be equal to that of dry saturated vapor at
the given temperature. When steam tables are not available, the enthalpy of
water vapor may be determined by use of empirical equations. The following
equation is suggested by the authors:
where t is °C. The maximum error caused by the use of Eq. 1015 is 1.9 J/g
over the temperature range of — 20°C to 100°C and for vapor pressures up to
0.01 MPa. Using a datum of 0°C for evaluating the enthalpy of air and treating
the air as an ideal gas.
2.339
a>wb = 0.622 Pv = 0.622
P, “Pv 401.325 — 2.330,
= 0.0147 gig dry air
This statement is valid for the low vapor pressures normally encountered in airconditioning
work.
perature must equal the enthalpy of saturated air at the given wetbulb
temperature. The enthalpy of saturated air may be computed at each wetbulb
temperature, and the value may be entered at the wetbulb temperature on the
psychrometric chart. When there is a change in conditions and, hence, a
change in the wetbulb temperature of air, the heat added or removed during
the change may be determined by taking the difference between the enthalpies
as found on the psychrometric chart for the two values of the wetbulb
temperature. This statement assumes that the enthalpy of water that may be
added or removed during a change in state can be neglected.
. 0.2342 1A
4> = 2239 x 00 ~ 1002 percent Answer
Example 108. Air at 28°C has a humidity ratio of 0.012g/g dry air. The air
pressure is 98 kPa. Determine the temperature to which the air must be cooled
until its relative humidity becomes 95 percent. Determine also the initial
relative humidity.
Solution. From Eq. 1012,
0.012 = 0.622
98 pv
pv = 1.855 kPa
Since
P actual
Psaturated
P saturated
230 Nonreactive Gaseous and Vapor Mixtures
t = 17.12°C Answer
where hm is the enthalpy of a pound of dry air plus the enthalpy of the vapor
accompanying it.
In a problem involving simple heating or cooling, the difference between the
enthalpies at the two points under consideration is the heat added or removed
per pound of dry air.
Example 109. How much heat must be added per minute for Example 107
if the initial air flow is 31 m '/min?
= 6.465 J/g
temperature that corresponds to the desired vapor pressure of the air after
it is heated.
From the Steam Tables in the Appendix, the saturation temperature cor¬
responding to 1.513 kPa is 13.2°C. Answer
Example 1011. An air conditioner is to supply 125 m3 of air per minute at
26°C, 45 percent relative humidity. Air is supplied to the dehumidifier part of
the unit at 34°C, 65 percent relative humidity. Determine the amount of
refrigeration required for the dehumidifier.
It may be assumed that the air leaving the dehumidifier is saturated. Then
from Example 1010, its temperature is 13.2°C.
The humidity ratio,
Assume that the condensate is removed from the dehumidifier at the rate it
is formed and at the temperature of the air leaving the dehumidifier. The
amount of condensate equals the difference between the humidity ratios at
entrance and exit. Thus,
For the range of temperatures involved here, the specific heat of the water
Humidification and Dehumidification 233
may be taken as 1 cal/°C or 4.1868 J/°C. Then the enthalpy of the condensate
equals
13.2° C
34° C 100 percent relative humidity 26° C
65 percent relative humidity 45 percent relative humidity
3The drytype cooling tower is used in large installations only when there is a shortage of the
makeup water required for a wettype cooling tower. The dry type is in reality a heat exchanger
in which the water is cooled by the air. The cooled water temperature must exceed that of the
drybulb temperature of the air. Hence, for power plant operation, the higher temperature water
from a dry tower produces a higher condensing steam temperature and a higher steam pressure in
the condenser, thus decreasing the efficiency of the power plant.
Cooling by Evaporation 235
As the air passes upward in the tower, it comes in contact with warmer
water. Hence, it is heated as it picks up vapor. This heating causes an increase
in the wetbulb temperature of the air. Where there is intimate contact
between the water and the air, it may be assumed that the air is saturated as it
leaves the cooling tower. The cooling efficiency, as well as the temperature of
the air leaving the tower, is determined by the design of the tower and by its
operating characteristics. For fixed conditions, the amount of air that is to be
forced through the tower must be determined. The rate of evaporation should
also be known, in order that the proper amount of makeup water can be
furnished. The method of determining these quantities will be illustrated in
the following example.
and at exit
6.632
co = 0.622 (■ 0.04356 ^2E2r
101.3256.632 ) §dry air
a, = 0.622 = 0.0201
V101.325  3.169/ gdry
hdawb= 1.004x25 = 25.1 J/g
hda = 1.004x35 = 35.1 J/g
hVwb = 2500 + 1.88 x 25 = 2547 J/g
hu = 4.186x25 = 105 J/g
!iv = 2500 + 1.88 x 35 = 2566 J/g
Cooling by Evaporation 237
PROBLEMS _
(b) Check the humidity ratio found in Example 106 in the text by
using a psychrometric chart.
1014 Air leaves a dehumidifier saturated at 1.012 bars, 14°C. It is heated to
20°C before entering a room. Determine the relative humidity entering
the room.
1015 (a) The air in Problem 1014 leaves the room at 26°C. The heat input
to the room is 20,000 kJ/h. Determine the volume rate of air flow into
the room.
(b) Determine the error that will be caused if the heat picked up by
the water vapor is neglected.
1016 (a) Air leaves a warm air furnace at 38° C, 40 percent relative humi¬
dity. The air is returned to the furnace at 18°C with no gain in
moisture. The furnace is to supply 42,500 kJ of heat per hour. Deter¬
mine the volume rate of air flow. The air pressure is 101.8 kPa.
(b) Determine the error that will be caused if the heat given up by the
water vapor is neglected.
1017 Air enters a dehumidifier at 34°C, 101 kPa, and 60 percent relative
humidity. After being dehumidified, the air is heated to 20°C, with the
relative humidity being 48 percent. Determine the temperature leaving
the dehumidifier if the air is saturated.
1018 Determine the heat removed per minute from the dehumidifier in
Problem 1017 if the rate of air flow is 128 m3/min at 20°C, 48 percent
relative humidity. Neglect the enthalpy of the condensate.
1019 For Problems 1017 and 1018, determine the amount of heat required
to heat the air leaving the dehumidifier.
1020 Repeat Problem 1018 taking the enthalpy of the condensate into
account. Assume that the condensate leaves at the temperature of the
air.
1021 Outside air at 0°C, 85 percent relative humidity is heated to 25° C.
Determine the final relative humidity.
1025 (a) The vapor pressure in air at a pressure of 100.5 kPa is increased
from 1.2 kPa to 2.4 kPa. Determine the percentage change in the
humidity ratio.
(b) Same as for part (a), except the vapor pressure is increased from
13.5 kPa to 27 kPa.
(c) Same as for part (a), except the air pressure is 61 kPa.
(d) Comment on the relationship between vapor pressure changes and
changes in the humidity ratio.
1026 Air enters a heater at 101.5 kPa, 85 percent relative humidity, 0°C, at
the rate of 175 nr/m. Heat is added in the heater at a rate of
11,800 kJ/min. Determine the temperature of the air at exit.
1027 Air enters a cooling tower at 29°C drybulb temperature, 24°C wet
bulb temperature at the rate of 5100 nr/m. It leaves saturated at 38°C.
Water enters the tower at 46°C at the rate of 5950 kg/min. The
barometric pressure is 101.2 kPa. Determine the relative humidity
from the psychrometric chart in Figure A7 of the Appendix. Deter¬
mine the cooling efficiency.
1028 Air enters a cooling tower at 32°C dry bulb, 24°C wet bulb at the rate
of 3400m3/min, and leaves saturated at 39°C. Barometric pressure is
101.2 kPa. Water enters the tower at 45°C. Assume a cooling efficiency
of 78 percent. Use the psychrometric charts in Figure A7 in the
Appendix for the relative humidity. Determine: (a) the temperature of
the water leaving the tower, (b) amount of cool water delivered, and
(c) minimum amount of makeup water required.
1029 A cooling tower receives 33,900 kg of water per second at 43°C. Air
enters the tower at 34°C dry bulb, 26°C wet bulb. Barometric pressure
is 101.4 kPa. The cooling efficiency is 80 percent. Air leaves the tower
saturated at 41°C. Determine: (a) the temperature of the water leaving
the tower, (b) volume rate of air flow to the tower, and (c) minimum
amount of makeup water required.
1030 In Problem 1018, the condensate leaves the dehumidifier at the same
temperature as that of the air. Determine the percentage of error
caused by neglecting the enthalpy of the condensate.
1031 Air is supplied at 101.2 kPa, 12°C and 70 percent relative humidity. It
is to be heated to 38° C and a relative humidity of 60 percent.
Determine per kilogram of dry air: (a) amount of water to be added,
(b) heat added to the water if it is supplied at 18°C, and (c) total heat
added.
_ 11 _
ELEMENTARY CHEMICAL
THERMODYNAMICS
111 INTRODUCTION
In Chapter 10 a study was made of mixtures of ideal gases with no chemical
reactions taking place. In many engineering situations, reactions between
gases do take place. Such reactions produce significant changes in the
properties of the system and also may involve large quantities of energy.
Some examples of common systems in which such reactions occur are the
combustor of a gas turbine, the furnace of a steam generator, the combustion
chamber of an internal combustion engine, and a fuel cell.
Chemical reactions may take place between a very large number of sub¬
stances existing in various phases. The complete analysis of all possible types
of chemical reactions is very involved and completely beyond the scope of
this book. Since the most common type of a chemical reaction encountered
by many engineers is that of combustion, the discussion in this chapter will be
centered on that particular type of chemical reaction. Many of the principles
that will be developed for combustion problems are applicable to chemical
reactions in general.
112 COMBUSTION
Combustion is defined as a chemical reaction in which a fuel combines with
oxygen liberating large quantities of heat and, incidentally, light. A fuel is thus
defined as a substance that combines with oxygen in a combustion process.
(The term “fuel” is also used to designate those fissionable substances that
release energy in a nuclear reactor.) Some fuels, particularly some rocket
fuels, are quite complex. The discussion of the combustion of these fuels is
beyond the scope of this text. Rather, the discussion here will be confined to
those fuels whose burnable constituents are carbon and hydrogen and, to a
minor extent, sulfur. These fuels supply the major portion of our energy
requirements.
These fuels may exist in the solid, the liquid, or the gaseous phase.
Normally a liquid fuel vaporizes before it can be burned and thus is burned in
the gaseous state. Many solid fuels, such as coal, are partly vaporized when
heated. However, there is some carbon in the coal that is not vaporized during
241
242 Elementary Chemical Thermodynamics
C + 02+C02 (111)
As indicated by Eq. 111, one molecule of carbon combines with one
molecule of oxygen to form one molecule of carbon dioxide. Since an actual
combustion process involves an extremely large number of molecules, it is
preferable to write a combustion equation on the molal basis. Because the
number of molecules per mole is the same for all substances, Eq. 111 may be
read as follows:
12 g C + 32 g 02 44 g C02
or
1 g C + 2i g 02 » 3i g C02 (112)
An examination of Eqs. 11la and 112 shows that there may be a change in
the number of moles during a combustion process but that there can be no
change in the total mass present. (This statement disregards the infinitesimal
amount of mass transformed into energy during combustion.)
When the oxygen for combustion is supplied from air, nitrogen will be
present during the combustion process. The amount of nitrogen can be
determined by the oxygennitrogen ratio of air. Since air is 21 percent oxygen
on the volume or molal basis, the amount of air required per mole of oxygen
equals 1/0.21 = 4.76 moles. The number of moles of atmospheric nitrogen per
mole of oxygen is 4.76 1.00 or 1 x (79/21) = 3.76 moles. Nitrogen is some¬
times introduced in the combustion equation to indicate its presence, even
though it does not react. Thus, the equation for carbon may be written as
follows:
C + 02 + 3.76 N2^ C02 + 3.76 N2 (113)
4.76 x 28.97
11.49 g
12
Or, since the mass of air equals the mass of the oxygen plus that of the
nitrogen, the number of grams of air required per gram of carbon is
1 x 32 43.76x28.16
11.49 g
12
244 Elementary Chemical Thermodynamics
This amount of air is known as the theoretical air. It is the amount of air re¬
quired for complete combustion, with no oxygen remaining after the combustion
process. A mixture of the theoretical air and fuel is sometimes known as a
stoichiometric mixture. The equations involving the theoretical amounts of
oxygen or air, such as Eqs. 111, 11la, 112, and 113, are said to be
stoichiometric equations.
The term products of combustion refers to all substances present after
combustion, whether or not they entered into the combustion process. Thus,
the products of the complete combustion of carbon in air are carbon dioxide
and nitrogen. For each mole of carbon there are 3.76 moles of nitrogen and
1 mole of carbon dioxide. The volumetric analysis of the products may be
found as follows:
2 H2 + 02+ 2 H20
Since quantities are desired per mole of fuel, Eq. 114 can be divided by 2.
The result is
The air required for the combustion of hydrogen is 0.5/0.21 = 2.38 moles of
air per mole of hydrogen. The number of grams of air per gram of hydrogen is
2.38x28.97
= 34.5 g/g
2
Combustion of Actual Fuels 245
a. Theoretical Air
Theoretical air has been defined as that amount of air which contains the
amount of oxygen required for complete combustion of the fuel, with no
oxygen remaining after the combustion process. A fuel in the gaseous form
may be a mixture of combustible compounds with some inert gases being
present. Generally, it is desirable to write a combustion equation for each
combustible compound to find both the theoretical amount of air required and
the theoretical products of combustion. A summation of these quantities will
give results for the active gaseous mixture.
In writing the combustion equation for compounds, particularly complex
ones, it is desirable to start with 1 mole of the fuel, since results are normally
expressed initially per mole of fuel. Assuming that the fuel is a hydrocarbon,
the amount of carbon and hydrogen in the fuel determines the amount of
carbon dioxide and water vapor formed as well as the amount of oxygen
required. Consider the combustion of methane, CH4.
Example 111. The analysis of a natural gas follows: CH4 (methane), 88.1
percent; C2H6 (ethane), 11.5 percent; N2, 0.4 percent. Determine: (a) the
theoretical air and (b) the analysis of the dry products of combustion. Dry
products of combustion include all products of combustion except water
vapor. This term is widely used, since the amount of dry gaseous products is
independent of the amount of condensation of water vapor. The amount of
wet gaseous products cannot be specified until the amount of condensation is
known.
Solution. (a) A mole of the fuel contains 0.881 mole of methane and
0.115 mole of ethane. From Eq. 115, the oxygen required to burn the methane
246 Elementary Chemical Thermodynamics
The major constituent of any solid fuel, such as coal, is carbon. Other
constituents are volatile combustibles and inert matter. (Volatile com¬
bustibles are combustible substances, mostly hydrocarbons, which become
gaseous upon application of heat.) The analysis of a coal is made on the mass
basis, and shows the amounts of carbon, hydrogen, sulfur, nitrogen, and ash.
Since the analysis is on the mass basis and since the theoretical air is desired
on the mass basis, combustion calculations generally are made on the mass
basis.
The total oxygen required for 1 g of coal (see the combustion equations of
carbon, hydrogen, and sulfur) is found as follows:
Grams 02 per
Substance
Gram Coal
C 0.74 x 2\ 1.973
H 0.06 x 8 0.480
S 0.01 x 1 0.010
Total 02 required 2.463
Oxygen in coal 0.080
Oxygen from air 2.383
A liquid fuel may have its analysis given on the same basis as for a solid
fuel. In this case, combustion calculations may be made in a manner similar to
that shown in Example 112. Frequently a particular chemical compound is
chosen whose air requirements and whose products are substantially equal to
those of a liquid fuel. For instance, octane (C8H18) is used to make combustion
calculations for gasoline, and dodecane (Ci2H26) is used in place of fuel oil.
For such cases, combustion equations are written in a manner similar to that
shown for gaseous fuels.
Example 113. Treating gasoline as C8Hi8, determine (a) the theoretical air
required and (b) the volumetric analysis of the dry products (theoretical).
The number of moles of air per mole of fuel is 12.5/0.21 = 59.5 moles, and the
number of grams of air per mole of fuel is 59.5 x 28.97 = 1725 g.
The theoretical airfuel ratio is
12.5x28.97
15.12 g air/g fuel Answer
0.21 x (8 x 12+18)
(b) The moles of dry products per mole of fuel are found as follows:
C02, 8 h 55 = 0.1455
N2, 12.5 x (79/21) = 47 55 = 0.8545
55
The molal or volumetric analysis is 14.55 percent C02 and 85.45 percent N2.
Answer
Note that the amount of nitrogen in the products of combustion in
Example 113 exceeds the amount of nitrogen in the air, because some of the
oxygen in the air combines with hydrogen to form water vapor. Since the
water vapor does not appear in the dry products, the nitrogen becomes a
larger percentage of the total.
b. Excess Air
Because it is not possible to obtain perfect mixing of air and fuel, combustion
will be far from complete unless considerable excess air is supplied. Excess
air is defined as that air supplied which is in excess of the theoretical amount.
Percentage of excess air is the excess air expressed as a percentage of the
theoretical. The percentage of excess air that is normally supplied depends on
the type of fuel (which determines the ease of mixing it with air), the type of
combustion equipment, and the type of controls. For example, with good
248 Elementary Chemical Thermodynamics
controls and a gaseous fuel, the required percentage of excess air may be only
10 to 15 percent. With handfiring of coal, the percentage of excess air may
range from 20 percent to 100 or more percent. The excess air in a com¬
pression ignition (diesel) engine may vary from 200 or 300 percent at light load
to roughly 30 percent at full load. To obtain a highpower output in an auto¬
motive type of engine, a deficiency of air is frequently used, even though this
amount results in incomplete combustion and inefficient burning of the fuel.
Theoretically, when excess air is supplied for a fuel, combustion should be
complete. However, since mixing of the air and fuel is never perfect, there
will be at least traces of incomplete combustion in the actual products of
combustion, even with much excess air. Because the degree of mixing cannot
be predicted, the only way of predicting the amount of incomplete combustion
for an actual case is by comparison with similar actual combustion processes.
When considerable excess air is supplied, it is desirable to predict the
analysis of the products of combustion by neglecting the very small amounts
of products of incomplete combustion that may exist.
Example 114. A fuel oil is burned with 50 percent excess air. Determine:
(a) the volumetric analysis of the dry products and (b) the volume rate of
flow of the wet products at a pressure of 1.02 x 102kPa and a temperature of
550° C when the fuel is burned at the rate of 45 kg/min. Assume that the
combustion requirements of the fuel oil are similar to those of Ci2H26.
The volumetric analysis is: C02, 9.55 percent; 02, 7.37 percent; N2, 83.08
percent. Answer
(b) The total moles of wet products per mole of fuel equals the moles of
dry products plus the moles of water vapor, or 125.65 + 13 = 138.65. The
Combustion of Actual Fuels 249
45 x 1000
= 264.7 g moles/min
(12 x 12) + 26
c. Deficiency of Air
Regardless of how perfect the mixing may be, there will be incomplete
combustion when there is a deficiency of air. However, because of imperfect
mixing, at least traces of oxygen may be present in the products when there is
a deficiency in the supply of air. By neglecting the oxygen in the products, it
is possible to predict the composition of the products when a single fuel
element is burned with a deficiency of air
C F O2—* CO2
For the actual case, the number of moles of 02 per mole of C is 0.9(1) =
0.9 mole, and the number of moles of N2 is 0.9 x (79/21) = 3.38 moles per mole
of C.
Because of a deficiency of air, there will be both CO and C02 in the
products. The CO and the C02 together must contain the mole of carbon in
the fuel that was burned. The CO and the C02 together must also contain the
0.9 mole of available 02. A mole of CO is composed of 1 mole of C and \ mole
of 02. A mole of C02 is composed of 1 mole of C and 1 mole of 02. These
statements can be combined in equation form, as follows:
moles CO
+ moles C02 = moles available 02 = 0.9
2
With these two equations are solved simultaneously, the results are
Example 117. The fuel oil in Example 114 produces the following Orsat
analysis: C02, 12.8 percent; 02, 3.5 percent; CO, 0.2 percent. Determine the
moles of dry products per kilogram of fuel oil.
Solution. If the fuel is treated as Cj2H26, a mole of the fuel contains 12 moles
of C. A mole of the dry products contains 0.128+0.002 or 0.13 mole of C.
Then the number of moles of dry products per mole of fuel is
Since the mass of mole of fuel is (12 x 12) + 26 = 170 kg, the number of moles
of dry products per kilogram of fuel is
Example 118. Determine the airfuel ratio of Example 116. Determine also
the percentage of excess air used.
Solution. The number of moles of nitrogen present per mole of dry products
equals 1.000  (0.12 + 0.065 + 0.001) = 0.814 mole. Since air is 79 percent
nitrogen, on the volumetric basis, the number of moles of air per mole of dry
products is
0.814 T 0.79 = 1.03 moles
Hence, the mass of air per kilogram mole of dry products is
1.03 x 28.97 = 29.85 kg
It has been assumed here that all of the nitrogen in the dry products comes
from the air. Since there is nitrogen in the coal, it will contribute to the
nitrogen in the dry products. However, it may be shown that approximately
only 0.1 percent of the nitrogen in the dry products comes from the coal.
Certain gaseous fuels may contain sufficient nitrogen to make it necessary to
consider this nitrogen.
In Example 116, it was determined that there was 0.504 mole of dry
products per kilogram of fuel. Hence, the mass of air per kilogram of fuel is
For Example 112, the theoretical air fuelratio is 10.27 g of air per gram of
coal. Hence, the percent excess air equals
15.0410.27
= 46.4 percent Answer
10.27“
on the gas. Allow combustion to take place and then cool the products down
to the original airfuel temperature. The overall energy equation is
Q + Ur = W + Up (117)
where Ur = the internal energy of the reactants
Up = the internal energy of the products
The net work equals p(Vp Vr). Then Eq. 117 becomes
[Q = Up  Ur + p(Vp  Vr)]T,p
or
The term Qr in Eq. 118 is termed the heat of reaction. It is defined as the
difference between the enthalpies of the products of a reaction and of the
reactants at a given temperature and pressure. Normally, heats of reactions
are specified at the standard temperature of 25° C and standard atmospheric
pressure. For these conditions the heat of reaction is termed the standard
heat of reaction.
For most engineering devices involving combustible mixtures, the system is
an open one. Assuming steadystate conditions with no significant changes in
kinetic and potential energies and no work crossing the boundaries of the
system, the energy equation becomes
Q = HpHr
When the products and reactants are at the same temperature and pressure,
the energy equation for steadystate flow becomes
Equations 119 and 118 are identical. Thus, for a given chemical reaction with
the temperature and pressure of the products equal to those of the reactants,
the heat of reaction is a fixed quantity and is independent of whether the
reaction occurs in an open or a closed system.
When the reaction is an exothermic one, heat is removed from the system.
The enthalpy of the products is less than that of the reactants for a given
temperature. Hence, the heat of reaction is negative. For an endothermic
reaction, the enthalpy of the products exceeds that of the reactants for a
given temperature. Thus, for this condition, the heat of reaction is positive.
1^ Q (= heating value
when combustion
is complete)
Air, T,
Products, T2 = Ty
Fuel, T! Combustion device 5*

negative of the heat of reaction for that process. This means that heating
values are positive quantities.
There are various terms used to describe the heat associated with com¬
bustion processes. In addition to the term heating value, the terms calorific
value and heat of combustion are used also. The term calorific value is
synonymous with heating value. The heat of combustion generally is defined
as equal to the heat of reaction of the complete combustion of the fuel and
oxygen. Since the heat of reaction for a combustion process is negative, the
heat of combustion also is negative.
Thus far it has been assumed that all of the products exist in the gaseous
form. Most fuels contain hydrogen, which upon burning forms water vapor.
As the products are cooled down, some of this water vapor may condense.
The amount of condensation is affected by the amount of excess air used, the
humidity of the air, the original temperature of the airfuel mixture, and the
total pressure. At one extreme, all of the water vapor of combustion will
condense, giving up its latent heat (i.e., the heat of vaporization). The heating
value thus obtained is designated as the higher heating value. It is also termed
the gross heating value. This heating value for common fuels is given in Table
111.
At the other extreme, there is no condensation of the water vapor of
combustion as the products are cooled. This heating value is termed the lower
heating value or net heating value.
In the previous section, it was shown that the heat of reaction for a
steadystate flow process is equal to the constantpressure heat of reaction. In
a similar manner, it can be shown that the heating value for a steadystate
flow process equals the constantpressure heating value.
Let the higher heating value at constant pressure be designated as QHP, and
the lower constant pressure heating value as QLP. Now write Eq. 118 for a
constantpressure combustion with all of the water vapor condensing and then
again with no water vapor condensing, in each case, per gram mole of fuel.
Now subtract these two equations. Recognizing that QP is the negative of the
heat of reaction, the result will become
Table 111
Heating Values at Constant Pressure and 25°Ca
[All fuels except carbon are in the gaseous state.
The products are C02 (gaseous) and H20 (liquid).]
or
Example 119, Determine the lower heating value of gaseous C8H18 at con¬
stant pressure at 25°C.
Note that the lower heating value is approximately 7 percent lower than the
higher heating value.
Example 1110. Determine the higher heating value of liquid C8H18 at con¬
stant pressure at 25°C.
Solution. This heating value of the liquid is less than that of the gaseous fuel
Heating Values 257
In some cases, fuels may be burned at constant volume. The heating values
of solid and the heavier liquid fuels are determined in a bomb calorimeter,
which is a constantvolume device. For a constantvolume combustion, the
energy equation becomes
Qv= Ur Up
But
Qp = Hr Hp
Then
Qv = QP + (NR0T)p  (NR0T)r
Then
Solution. In Eq. 1111, Np = 8 and Nr = 12.5 for the gaseous state. Then
Solution. For the lower heating value, the water vapor is gaseous. Then
Np = 17. Using the value of QLP from Example 119 together with Eq. 1111,
Then
Thus far it has been assumed that the airfuel mixture exists at the standard
temperature of 25°C. Of course, this is rarely the case. The heating value at
other temperatures can be determined by use of Eq. 119, recognizing that the
heating value is the negative of the heat of reaction. Thus, at any temperature
(Qhp = Hr  Hp)T2
and
for the reactants at 100°C, from Table 112, Hr = 14,527 I 12.5 x 2238 = 42,502
Note that a change in the initial temperature of the airfuel mixture from 25° C
to 100° C produces a change in the heating value of only about 0.6 of a
percent. Hence, for most engineering applications, the effect of small changes
in the initial temperature on the heating value can be neglected.
Based largely on Table 45 in J. S. Doolittle, Thermodynamics for Engineers, 2nd ed., International Textbook Company, Scranton, Pa., 1964.
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259
260 Elementary Chemical Thermodynamics
mation of carbon dioxide is 393,761 J/g mole, and the heat of reaction for
converting carbon monoxide to carbon dioxide is 283,110 J/g mole. From
these values, the heat of formation of carbon monoxide is 110,651 J/g mole.
This method is of value in determining the heat of formation of a compound
which cannot be formed directly from its element and also for a compound
which cannot be formed singularly from its elements. This method may also
be used to determine the heat of reaction for a reaction process that cannot be
physically separated from other processes.
In addition to heat of combustion and heat of formation, other specialized
forms of heat of reaction are heat of solution, heat of dilution, heat of
neutralization, and heat of dissociation. The reader is referred to textbooks on
chemical thermodynamics for discussions of these particular types of heat of
reaction.
Qp = (Hr  )
Up molecular + chemical energy (1114)
It is not feasible to determine the chemical energy directly, but it may be
calculated by use of Eq. 1114 by using known heating values.
Various tables of enthalpies of various gases have been prepared. Using
these tables, a calculated value of the chemical energy may be obtained.
Unfortunately, various datum temperatures have been used in preparing
enthalpy tables. Hence, care must be taken to use the calculated value of
chemical energy in conjunction with the enthalpy tables from which it was
calculated. Note that the datum temperature for Table 112 is 25°C.
Since it is common practice to report the higher heating value of a fuel at a
constant pressure, Eq. 1114 may be written as
In the use of Eq. 1115, care must be taken to use the molecular enthalpy of
water in the liquid states. This enthalpy can be determined by subtracting the
heat of vaporization of water from the enthalpy of water vapor in Table 112.
For the normal small changes in the initial temperature of the airfuel
temperature, the change in the heat of vaporization of water can be neglected
except where precision results are required. (The heat of vaporization of
262 Elementary Chemical Thermodynamics
water vapor is 2442.3 J/g at 25°C, 2358.5 J/g at 60°C, and 2257.0 J/g at 100°C.
This change in the heat of vaporization is very small in comparison with the
heating value of the fuels.)
Energy equations can be written for combustion processes. However, in
using these equations with either the heat of reaction or the heating value, it is
necessary first to calculate these energies at the original temperature of the
reactants. On the other hand, for a flow process, the energy equation may be
written as
In Eq. 1116, the enthalpies are the molecular energies, as given in tables such
as Table 112. The chemical energy to be used in Eq. 1116 is calculated by
using these enthalpies. Because chemical energy is a constant, there is an
advantage to using equations involving chemical energy rather than equations
using either heats of reaction or heating values.
Solution. Refer to Example 113 for the combustion equation. Use Eq. 1115
and Table 111 at 25°C.
Example 1115. C8H18 is burned in a furnace with 20 percent excess air. The
initial airfuel temperature is 40° C and the final temperature is 1600°C.
Determine the heat removed per gram mole of fuel. No work is performed.
Hr = 1 x 2,547 = 2,547
15x433 = 6,495
56.43x431 = 24,321
Total = 33,813
Hp = 2.5x54,496 = 136,240
8 x 84,065 = 672,520
9x65,883 = 593,037
56.43x51,677 = 2,916,133
Total =4,317,930
Combustion Temperatures 263
Substituting into Eq. 1116, using the chemical energy from Example 1114,
Q =  828,058
or
This is the total enthalpy of the products. To determine the final temperature,
a trialanderror solution will be used. At 2200°C,
At 2400° C,
Hp = 133,650+ 1.88(80,733) = 285,428 J
By interpolation,
final temperature = 2394° C Answer
devices such as storage batteries and fuel cells, the reactions may approach
reversibility. Then the electrical energy deliverable approaches the decrease
in the Gibbs function.
In addition to predicting the maximum electrical energy deliverable during a
chemical reaction, as was stated above, the Gibbs function is helpful in
determining whether or not a system is in chemical equilibrium. Consider a
system composed of substances that possibly may react and form specific
products. Let the state of the products be so adjusted that their temperature
and pressure equal those of the reactants. Since G = HTS=U+pV TS,
dG = dU +pdV +V dpTdSSdT
(dG)T,p = dU + p dV  T dS (1118)
The entropy of the system may be changed by the addition of heat.
Designate this entropy change as / dSe. The entropy of the system may also
be changed by irreversibilities within the system. Designate this entropy
change as / dSt. dU = 8Q  p dV = T dSep dV and T dS = T dSe + T dSh
Making these substitutions into Eq. 1118 and reducing yields
aA+bB±*cC+dD (1120)
dG = T dS + V dp  T dS — S dT
or
dG = V dp  S dT
Control volume
a moles of A c moles of C
»>
b moles of B d moles of D
dG = Vdp = NR"T dp
P
or
where pA is the partial pressure of substance A in the box and patm is the
atmospheric pressure.
For substance B,
(GBlGB,) = bR0T In(f5)
2 ' \P atm/
For substance C,
For substance D,
Since equilibrium conditions exist in the box, the sum of the Gibbs
functions of the reactants existing in the box must equal the sum of those of
the products, or
(GA2+Gb2)(GCi + GDi) = 0 (1123)
When pressures are expressed in atmospheres, the last term of Eq. 1124 is
zero (since the In 1 = 0). Under these conditions, Eq. 1124 may be written as
follows:
PcPd
or
(1125)
The lefthand side of Eq. 1125 is known as the equilibrium constant and is
designated as Kp. Note that in Eq. 1125, the Gibbs functions of the reactants
and the products are to be evaluated at atmospheric pressure and at the
temperature T. Thus, the lefthand side of Eq. 1125 is a function only of
temperature. Although called the equilibrium constant, Kp is not a constant.
For a mixture of ideal gases, however, Kp is dependent only on temperature.
It should be noted that in Eq. 1125 the reactants and products referred to are
those indicated by the reaction equation and not those that are in equilibrium.
The partial pressures in Eq. 1125 are the partial pressures of the mixture. The
exponents a, b, c, and d are the numbers of moles of the various substances
as given by the reaction equation and are not the numbers of moles of the
substances present in an equilibrium mixture.
Since G is defined as H  TS, the Gibbs function may be calculated for any
substance when the absolute values of enthalpy and entropy are known.
Values of the Gibbs function at standard states have been calculated and are
tabulated in various texts on chemical engineering thermodynamics. The
equilibrium constant for a reaction of ideal gases can be calculated by use of
Eq. 1125 when the Gibbs functions are available. Equilibrium constants for a
few reactions are given in Figure A6 in the Appendix. It should be noted in
this figure that the common logarithm of the constants is given and not the
natural logarithm.
When a compound gas is heated, there is a tendency for the gas to
dissociate. At any temperature there is an equilibrium mixture of the gas and
its dissociated products. The relative amounts of each substance may be
determined by use of the equilibrium constant. The method of making this
determination is illustrated in the following example.
Solution. Start with 1 mole of C02 and heat to 2500 K. Some dissociation will
occur, with CO and 02 being formed. Let X equal the number of moles of
C02 dissociated. Then X moles of CO and X/2 moles of 02 will be formed.
Equilibrium in a Reactive Mixture 269
From Figure A6 in the Appendix, at 2500 K the common log, log Kp = 1.45
for the reaction C0 + 02^C02.
For ideal gases, the partial pressure of each gas is proportional to the
number of moles of that gas. In using Eq. 1125, gas A is CO, gas B is 02, and
gas C is C02. There is no gas D. Setting pt equal to the total pressure,
moles C02 _ 1X 2(1X)
Pc°2 “ total moles P' " (2 + X)/2 P' _ 2 + X P‘
_ moles 02 _ X/2 X
P°2 “ total moles p‘ ~ (2 + X)/2 p‘ ~ 2 + X p‘
_ moles CO _ X 2X
Pco “ total moles Pl ~ (2 + X)/2 Pl ~ 2 + X P‘
Solve this equation for the value of X by trial and error so that log Kp =
1.45. If X =0.1,
(1 0.1)(2 + 0.1)°5
41.25 and log Kp = 1.6154
Od13
If X =0.12,
(1  0.12)(2 + 0.12)0'5
30.8 and log Kp = 1.4855
O?5
If X =0.14,
„ (1  0.14)(2 + 0.14)°5
22.85 and log Kp = 1.3589
K"~ OI17
By interpolation, X 0.126. In other words, 12.6 percent of the carbon
dioxide has dissociated at 2500 K. Of each original mole of carbon dioxide
there will be 0.126 mole of carbon monoxide, 0.063 mole of oxygen, and
0.874 mole of carbon dioxide. Answer
D =X ^2
P°2 2X N2
Pc o — X Pi
N2
From Eq. 1125 the definition of the equilibrium constant, with a = 1, b =5,
and c — 1,
(1 X)p2/N2 (1 — X)2°'5
(b)
p (Xp2IN2)(\l2Xp2IN2yu X'\p2IN2r
For a final assumed temperature, the value of X will be found by trial and
error, using the equilibrium constant together with Eq. (b). With the assumed
temperature and the calculated value of X, the total energy of the products
[the right side of Eq. (a)] will be calculated and compared with the energy of
the reactants [the left side of Eq. (a)]. If the two energies do not balance a
new temperature will be assumed. Assume T2 = 2200°C. From the Appendix,
at T = 2473 K, the common log, log Kp = 1.52, Kp = 33.2.
Assuming X = 0.1 and using Eq. (b) with p2= 1 atm,
(1  0.08)2°'5 x 2.9205
98.2
0.0815
This equation is not valid for gases that are not ideal. However, there must be
some property of a substance which may be substituted for pressure in Eq. 1126
to make the equation applicable for all gases. This property is called fugacity,
and the symbol f is used to denote it. Then,
(dG)r = NR0Td(\nf)= V dp (1127)
The change in the Gibbs function can be obtained by integration of Eq. 1127.
Thus,
Equation 1128 shows that the change in the Gibbs function can be obtained if
an equation of state is available for the condition of the actual gas. As discussed
272 Elementary Chemical Thermodynamics
dG\ = NR0Td(\nf) = V dp =
dp) T dp dp
or
d(lnf)= V
(1129)
dp NR0T
d(ln /)~1 =Z
dp iT P
Hence,
It is evident from Eq. 1131 that fugacity must have the units of pressure.
Gases obey idealgas laws more closely when the pressure is reduced. If the
pressure could be reduced to zero, they would obey the idealgas laws and the
compressibility factor would become unity. For this condition, the fugacity
would be equal to the pressure.
To evaluate the fugacity of an actual gas, subtract d(ln p)T from each side of
Eq. 1130. The result is
or
d(lnA =(Zl)d(lnp):
By integration,
(1132)
Fugacity and Activity Coefficient 273
The ratio (//p)T may be evaluated by use of Eq. 1132 when the compressibility
factor can be expressed in terms of pressure or when a mean compressibility
factor is known for the given pressure range. The ratio (Jlp)r is known as the
activity coefficient.2 It may be calculated and tabulated as a function of
temperature and pressure for various actual gases.
The equilibrium constant for mixtures of reactive actual gases may be
determined by use of the fugacity. For actual gases, Eq. 1128 becomes
This equation may be used to evaluate the change in the Gibbs functions of
actual gases entering and leaving a van’t Hoff equilibrium box (see Section
1112). Thus for actual gases,
fcfo _ TV ,
r aa rr hb ' ^ pr> (1133)
Aj B
where X' is the equilibrium constant for a mixture of actual reactive gases. This
equilibrium constant is a function of both pressure and temperature.
PROBLEMS __
THERMODYNAMICS
OF FLUID FLOW
121 INTRODUCTION
Thermodynamics of fluid flow is concerned with those flowing fluids that
experience a change in their thermodynamic properties during the flow
process. The fluids involved may be gases, vapors, or liquids, Hence, while
some of the fluids may be treated as incompressible, the compressibility of
other fluids must be considered. In some cases, the frictional resistance of the
flow channel may be sufficient to produce significant changes in the fluid
properties. In other cases, factors such as heat addition and work production
may cause such major changes in fluid properties that the effects of sidewall
friction may be neglected.
Because of the generality of the thermodynamics of fluid flow, the prin¬
ciples of such flow are applicable to a wide range of engineering problems.
These include friction losses in pipelines, flow in both steamturbine and
gasturbine nozzles, air flow over airplane wings, the passage of guided
missiles through the atmosphere, flow in jet engines, the heating and cooling
of fluids in highvelocity heat exchangers, and turbomachinery in general.
Fluid flow, in its broadest aspect, is complicated. Under some conditions,
parts of a fluid stream may be flowing in any of three planes. Furthermore,
conditions at a given point may vary with time. However, a large number of
types of flow may be approximated by making the following simplifying
assumptions:
1 Unidirectional flow. This means that all parts of the stream are considered
to flow parallel to the axis of the flow passage. This assumption does not
preclude a change in the flow area nor a change in direction of the flow
passage. Neither does it exclude turbulent flow, where cross flow of
individual particles takes place (see Section 122).
2 Steady flow. This means that the mass rates of flow through all cross
sectional areas of the flow passage are equal and are constant.
3 Steadystate condition. This condition is attained when there is no varia¬
tion in properties with time at any point of the flow passage.
277
278 Thermodynamics of Fiuid Flow
Re = ^ (121)
The Reynolds number is dimensionless when consistent units are used. In the
metric system, the diameter D of the flow system is given in meters, the
velocity T, in m/s, the density p, in kg/m3, and the viscosity p,, in kg/ms.
TZTZZZZZZ^^7777777777777777777?.
V//////7///777777777777777777777777
fmean 05 Imax FIGURE 122 Laminar flow.
Laminar and Turbulent Flows 279
The product pT is the mass rate of flow per unit area. The symbol G is
used to designate this product. Substituting G in Eq. 121,
Re = — (12la)
where FI A = the force per unit area causing shear between adjacent layers of the fluid
dx = the distance between the layers under consideration
dT = the velocity difference between the two layers (see Fig. 124).
Equation 122 applies to true fluids but may not apply to semifluids such as
plastics. A fluid obeying this equation exactly is known as a Newtonian fluid.
In certain cases the kinematic viscosity of the fluid is useful. The kinematic
viscosity, v, is given as
(123)
P
Solution. From the table in Appendix 15, the internal diameter of the
pipe = 2.067 in. or
2.067 x 2.54
0.0525 m
100
Example 122. Air having a pressure of 1.01 bars and a temperature of 35° C
flows through a duct that is 30 cm by 40 cm. Determine the maximum velocity
for laminar flow.
Solution. The hydraulic radius equals
30x40
= 8.571 cm = 0.08571 m
2 x (30 + 40)
m _ p 1.01 x 105
= 1142 g/m3 = 1.142 kg/m3
P~V~RT~ 0.287(35 + 273.15)
pi = 18.2 x 10 hkg/ms
= DTp y Re /x
Re
The maximum velocities for laminar flow of water and air, as determined in
Examples 121 and 122 are very much lower than those normally encoun¬
tered in pipes and ducts. Thus, generally, the flow of these fluids definitely is
turbulent. For this reason, further discussion in this chapter will be limited to
turbulent flows.
V = AY
But the mass rate of flow equals the product of p and V. Hence,
m = pAY (124)
8q = dh + dz + YdY (126)
dh = T dse T T dsi + v dp
282 Thermodynamics of Fluid Flow
r2 y22
~2 ”2 “
But 8q = T dse and v = 1/p, where p is the density. Substituting into Eq. 126,
Each of the terms in Eq. 128 has the dimensions of pressure. The term pT ds,
represents the pressure loss due to irreversibility, that is, friction. The term
p dz is the change in pressure due to a change in elevation and may be termed
the gravity pressure change. pY dY is the change in pressure due to a change
in velocity, known as the velocity pressure change.
Changes in pressure in a flow system frequently are expressed in terms of
feet of the flowing fluid. This may be done by multiplying each term in Eq.
128 by 1 Ip:
1 The fluid is a constantdensity fluid; that is, its density is not materially
influenced by a change in either temperature or pressure.
2 The fluid is an incompressible fluid; that is, its density is not materially
influenced by a change in pressure, although its density is influenced by a
change in temperature. For the given conditions there may not be a
sufficient change in temperature to affect the density materially.
3 The fluid has a density that is materially affected by a change in either
temperature or pressure. Nevertheless, the density may be considered to
be a constant when the changes in the pressure and temperature are such
small percentages of the absolute values that they can be neglected.
Under these conditions, Eq. 128 may be integrated and expressed as
(1210)
where Apf is the pressure loss due to friction and equals / pT ds,.
Example 12.3. Water enters a piping system at a pressure of 250 kPa, 30° C with
a velocity of 2.1 m/s. The centerline of the piping system at exit is 14.2 m above
that at entrance. The pressure at exit is 100 kPa. Determine the frictional loss in
the piping system.
Then
995.7(—14.2)9.807
A pf = 250  100 + = 11.34kPa Answer
1000
Ap, _ 11.34x1000
S' pT 995.7(273.15 + 30)
= 0.0376 Nm/kgK = 0.0376 J/kgK Answer
284 Thermodynamics of Fluid Flow
Example 125. Air enters a round horizontal duct with a diameter of 0.6 m at a
pressure of 1.01 bars and a temperature of 35°C and with a velocity of 41 m/s.
The diameter increases to 0.85 m in a distance of 2.2 m. Determine the final
pressure.
Solution. Since the duct is very short and the velocity is relatively low there
should not be a significant friction loss. Using Eq. 128a and assuming no
significant change in density,
1 142(20 42 — 412)
p2 = 1.01 + ^ = 1.0028 bars Answer
F 2 x 10
h°=h+Y (1211)
or
<Y2
T°=T + y— (1212)
ZCp
2As discussed in Section 28c, when a fluid is brought completely to rest, there is a transformation
of its pv energy into internal energy, which produces a large temperature rise. Hence, the word
“essentially” is used here.
Stagnation Properties 285
The stagnation pressure is defined as the sum of the static pressure and the
velocity pressure, or
o pY2
P =p+ 2
The stagnation pressure can be determined for ideal gases when the static and
stagnation temperatures are known. Thus,
pi  (nyk~i (1213)
where k is the ratio of specific heats (cp/cv). The stagnation density can be
determined by the use of the pvT relationship when the stagnation pressure
and stagnation temperature are known. By definition, the static and stagnation
entropies are equal.
Example 126. Air at a pressure of 8.2 bars and a temperature of 60°C has a
velocity of 180 m/s. Determine the stagnation pressure, temperature, and
density.
1802
TO = 60 + 2x 1.004x 1000 = 7614°C AnSWCr
o 0 „ /76.14 + 273.15314,04 . .
p = 8.21 ^q + 273 ]5 ) = 9.677 bars Answer
Example 127. Steam in a pipeline has a velocity of 130 m/s. It has a tempera¬
ture of 215°C and a pressure of 15 bars. Specify its stagnation properties.
i in2
h° = 2836.8 + 2^joO = 28453 J/8
s° = s =6.5379 J/gK
dp + ydy = 0 (1214)
P
From Eq. 124, pAT is constant. Hence,
y + X + ~° (1215)
Source of
Since A is constant,
dp dY
p r
= o (1215 a)
dh + YdY = 0 (1216)
For an ideal gas, dh = cp dT. When this value of dh and the value of (Y dY)
from Eq. 1214 are substituted,
cp dT ~~7~ = Q (1217)
Cp~ic=R or Cp=rHR
Then,
dp
(1218)
rh8" P
When T = p/pR,
dT = ^ d —
R p
so that,
k [p dp — p dp\ _ dp
k 1 \ p1 / p
This reduces to
dp _ kp
(1219)
dp p
or
y= (1220)
r= = VkRT (1220a)
v P
The velocity in Eq. 1220a is the velocity of the fluid required to maintain
the pressure wave in a stationary position. It must equal the velocity the
pressure wave would have if it were to travel through a still gas. But this
velocity equals the acoustic velocity a.
Therefore, for an ideal gas, the acoustic velocity
a = VkRT (1220b)
As will be seen later on in this chapter, the behavior of a flowing fluid is a
function of the ratio of the fluid velocity to the acoustic velocity. For
instance, when a gas enters a diverging passage with a velocity lower than the
acoustic velocity, an increase occurs in the pressure as the fluid moves
through the passage. On the other hand, when a fluid enters a diverging
passage with a velocity greater than the acoustic velocity, a decrease in
pressure takes place in the passage. It should be noted that the important
criterion is neither the magnitude of the velocity of the fluid nor that of the
acoustic velocity, but is rather the ratio of the fluid velocity to the acoustic
velocity. This ratio is called the Mach number and is symbolized by M. Thus,
y
M=— (1221)
a
When the velocity of the fluid equals the acoustic velocity, the fluid is said
to possess sonic velocity. Any velocity less than sonic velocity is said to be
subsonic, and a velocity greater than sonic velocity is called supersonic.
Insulation
* •' *■ ■. .
1 1 . l 7"T! .;•••• ••
*777777777, G/7>/yy///////777/77//7// 777777777.
7777WA
1 2
hi h2
% ^2
2 2
A line on any diagram representing the properties of a fluid during its flow
(adiabatic) through a constantarea passage is called a Fanno line. Equation
1224 provides information for plotting a Fanno line on an enthalpydensity
plane or on an enthalpyvolume plane. A more common diagram used for
showing a Fanno line is the enthalpyentropy diagram. Equation 1224 may be
used as a basis for calculations for a Fanno line on the hs plane. This
equation gives a means of determining the density for each value of the
enthalpy. Since enthalpy and density are independent properties, they fix the
values of entropy. The determination of the entropy may be relatively easy
for an ideal gas, but it may necessitate a trialanderror solution for vapors.
520,000 , 3
Pl 287(30 + 273.15) 5977kS/m
G = pY = 5.977 x 82 = 490.1 kg/m2s
S2  S\ = C
■©  R '» ©
= 1.004In^4^0.287 In408'74
303.15 520
= 0.006646 + 0.069095
= 0.06245 J/gK or 62.45 J/kgK
From this information just obtained, the Fanno line is plotted in Figure
128. The pressure line is plotted also in this figure. It shows that the specific
entropy has increased by 61.5 J/kgK in the duct and that the static enthalpy
at the exit has decreased to 28,160 J/kg. The temperature at exit is
28,160
28.05°C
(1000 x 1.004)
Example 129. Determine the velocity of the air at exit in Example 128.
Solution. From Example 128, h° = 33,482 J/kg and h = 28,160 J/kg. Then
Eq. 1226,
(1226a)
p a r
When Eq. 1223 is expressed in the differential form, the result, with h°
being constant, is
dh + YdY = 0
— + y dv = o
For very low Mach numbers, the percentage change in density is in¬
significant; that is, dplp is substantially equal to zero. Under these conditions,
Eq. 1227 reduces to
2 dA
dp = Ylp (1227a)
A
Examination of Eq. 1227a shows that for the assumed conditions of the
isentropic flow of an ideal gas at very low Mach numbers, the pressure varies
directly with the area. Hence, a diverging passage produces an increase in
pressure, and a converging passage causes a decrease in pressure.
Equation 1227 indicates that the pressure is proportional to the square of
the velocity. At high Mach numbers, a change in velocity produces a sizable
change in pressure and, hence, in density. Therefore, the term dplp cannot be
neglected. It is difficult to predict from Eq. 1227 what will happen to the
pressure, and hence the velocity, when the flow area is changed. To permit
such a prediction, introduce the Mach number into the equation.
Since a2 = dpi dp,
dp
dp = a2 dp or dp (1228)
pY2 dp 2 dA Y2 dp dA
A
or
dA
A
hence,
2 dA
dp(\ M2) = pY (1229)
A
Adiabatic Flow with Varying Area 293
When the value of dp from Eq. 1228 is substituted in Eq. 1229, the result
is
or
dp _ a2M2 dA _ M2 dA
p <r(lM2) A 1  M2 A
Hence,
dT = dA M2 dA dA / M2 \
r A 1  JVf2 A A V 1 M:j
or
dT dA/ 1 \
(1230)
r a \i m2)
An examination of Eq. 1230 indicates that when the Mach number is less
than unity, the velocity decreases as the area increases, and vice versa. For
supersonic flow, the velocity increases as the area increases. These state¬
ments may be illustrated by considering a venturi tube and a convergent
divergent nozzle. As shown in Figure 129, the two flow passages are similar
r= V2(k^T)*(T#T)
Since T/T° = (plpY~m,
/nvH« r (fcD/k j
T°T = T°T° (A) = T°
1 (v)
~
Then
j \ (k\)lk
•a 1
1_J
n_j*
O
T—
c*
(1232)
II
1
H
vH
V .i
Also,
1
1
rh = pA yjl ^ j) RT° [l  
L
Since
(kl)lk
p _ p /py"'1 pp(i“t),k(p°) p° (i
P RT xftyp) RTs RT° \t
then
Ap°
m = (1233)
VrT*
For isentropic flow in the absence of external work, the stagnation enthalpy
remains constant. Hence, the stagnation temperature remains constant. Fur¬
thermore, the stagnation pressure is also constant. (Since dh° = T ds° +
dp°lp° = 0, it follows that for an isentropic process dp0 = p°T° ds° = 0.) If
Eq. 1233 is written in terms of the initial stagnation pressure and tempera
Adiabatic Flow with Varying Area 295
Ap?
(1234)
VIT?
or
(1234a)
A
The maximum rate of flow per unit area occurs at the minimum cross
sectional area of the nozzle, which is known as the throat. The pressure at
this point can be obtained in terms of the initial stagnation pressure by
differentiating the term [(p/p?)2/k  (p/p?)tk 1)/k] from Eq. 1234a with respect to
p/p? and setting the differential equal to 0. The result of this operation is that
kl(k1)
(1235)
Jc + 1
using
or
y=
or
y = VkRT
This expression for the velocity at the throat is exactly the same as that given
in Eq. 1220a for the acoustic velocity. Thus, the fluid at the throat has a sonic
velocity when the mass flow rate is at a maximum.
296 Thermodynamics of Fluid Flow
When the back pressure equals the initial pressure, and it is assumed that
there is no velocity approaching the nozzle, there is no flow and the velocity
at the throat of the nozzle is zero. As the back pressure is reduced, the
velocity at the throat of the nozzle increases, approaching the sonic velocity
as a limiting value.
When the velocity at the throat is subsonic, the mass rate of flow through
the nozzle is less than the maximum possible. The pressure at the throat is
greater than that existing for sonic velocity. As the back pressure is de¬
creased, the mass rate of flow increases and reaches a maximum value, name¬
ly, that value obtained by substituting the pressure ratio given Eq. 1235 in
Eq. 1234a. A further decrease in back pressure cannot increase the mass
rate of flow at the minimum crosssectional area nor can it increase the
velocity at that point. Hence, the fluid velocity existing at the minimum
crosssectional area when maximum rate of flow is obtained is known as the
critical velocity. This is sonic velocity. The pressure corresponding to the
critical velocity is called the critical pressure. The critical pressure may be
calculated by use of Eq. 1235.
The conditions relative to the throat of a convergentdivergent nozzle for
the isentropic flow of an ideal gas are restated as follows:
Example 1210. Air enters a nozzle at 120°C with a pressure of 1600 kPa and
expands to a pressure of 200 kPa (see Figure 1210). The flow area approach¬
ing the nozzle is large and, hence, the initial velocity can be neglected. The
mass rate of flow is 2 kg/s. Treat the air as an ideal gas and assume an
isentropic expansion. Determine the variations in velocity, specific volume,
and area through the nozzle.
Flow in Ideal Nozzles 297
The results are plotted in Figure 1211. An examination of the curve shows
the following points.
1 Except for the very first part of the nozzle, the velocity increases at
almost a constant rate as the pressure decreases.
2 For a considerable part of the expansion, the specific volume increases
gradually. During the latter part of the expansion, the specific volume
increases very rapidly.
3 Because of the large increase in specific volume, the area of the last part
of the nozzle increases rapidly. This relationship will be particularly
noticeable if the expansion should be continued to a lower pressure.
The curves in Figure 1211 are based on the assumption that an equal
pressure drop occurs in each unit length of the nozzle. It will be difficult to
manufacture such a nozzle. A common form of a convergentdivergent nozzle
was illustrated in Figure 1210. In this type of nozzle there will not be the
same pressure drop in each unit length of the nozzle. Curves showing the
variations in the velocity and specific volume for this type of nozzle will have
the same general shape as those in Figure 1211, but they will be distorted
because of unequal pressure drops.
Pressure (kPa)
298
Nozzle Efficiency 299
The kinetic energy appearing at exit may come partly from kinetic energy
entering the nozzle and partly from enthalpy which is transformed into kinetic
energy because of the expansion occurring in the nozzle. For given conditions,
the maximum enthalpy that can be transformed into kinetic energy is the
enthalpy change which occurs in an isentropic expansion. Then, on the gram
basis,
rli 2 (1237)
T" (rill) + (h,  h2)s
_ (h] h2)actual
(1237a)
V" ~ (h,/i2)s
Extensive experimental work has shown that the nozzle efficiency is
affected by many factors, such as the material of which the nozzle is
constructed, the workmanship in manufacture, the size of the nozzle, the
shape of the nozzle (that is, round, elliptical, or rectangular), the angle of
nozzlewall divergence, whether the nozzle passage is straight or curved, the
nature of the fluid and its state, and the fluid velocity. The investigation of the
magnitude of the effects of each of these factors is beyond the scope of this
text. However, the effect of nozzle efficiency on flow in nozzles will be
investigated.
The primary effect of friction and turbulence within a nozzle is to reduce
the nozzle efficiency and, hence, to reduce the kinetic energy of nozzle exit. A
second effect is to reduce the mass rate of flow through a nozzle of given
area. Expansion in a nozzle may be illustrated on an HS plane, as in Figure
300 Thermodynamics of Fluid Flow
s
FIGURE 1212 Expansion with friction.
1212. Process 12 is an isentropic one, and process 13 is an actual expansion
to the same final pressure. If the kinetic energy at entrance is neglected, the
change in enthalpy must equal the kinetic energy at exit. The difference
between the actual and theoretical changes in enthalpy is called reheat.
Example 1211 illustrates the effect of friction on the performance of a
nozzle.
Example 1211. Steam enters a nozzle at 250°C with a pressure of 1.5 MPa.
The exhaust pressure is 0.9 MPa. The nozzle efficiency is 95 percent. Cal¬
culate the exit area for a mass flow of 1.2 kg/s.
Since the exhaust pressure exceeds the critical pressure, the nozzle should be
a convergent one.
From the Steam Tables in the Appendix, ht = 2923.2 and s, = 6.7090. At the
end of isentropic expansion, p = 0.9 MPa and h = 2813.2. The actual change in
enthalpy in the nozzle from Eq. 1237a equals
For this enthalpy and a pressure of 0.9 MPa, the specific volume is
226.6 cm3/g. The nozzle exit area,
the sidewall friction may be neglected (see Fig. 1214). Assuming one¬
dimensional flow,
P1 P2
% r2
Yz = M2a2 = MlkRT
Substituting this value of Y2 into Eq. 1238 and rearranging,
P i_ 1 + M^c
(1239)
p2 1 + Mxk
Substituting the value of V = VM2kRT into the expression pxYx = p2Y2 and
rearranging,
pxMx p2M2
(1240)
Vt, Vt2
Since h? = h2.
Y2
h 1 + r = h2 +
r2
°"'2
T\ [1 + (k — 1)/2]M2
(1241)
T2 [l + (kl)/2]Mf
When the values of pxlp2 from Eq. 1239 and T,/T2 from Eq. 1241 are
substituted into Eq. 1240, the result is
(1 + M22k)Mx (1 + M2k)M2
Vl + [(k — 1)/2]M2 V1 + [(k  l)/2]Mf
From this,
_2 Mi + 2/(k — 1)
M2— r^Ti TTilTvITTT (1242)
[2k/(k — l)]Mf — 1
The relationship between the Mach numbers at the two faces of the shock
wave, as given by Eq. 1242, is plotted in Figure 1215 for air. Note that the
larger the Mach number before the shock, the smaller will be the Mach
number after the shock.
Since a compression shock is an irreversible process, it is desirable to analyze
the entropy change that takes place. For an ideal gas, the entropy change, using
Eq. 825a, can be written as
Rk
52~ Si = In
k—1
or
k /l + [(kl)/2]M?\
s2  sx = R In  R In (1243)
k^ Vl + [(kl)/2]Af;/
0.6 0.8 1.0 1.2 1.4 1.6
M:
FIGURE 1215 Relationship of Mach numbers for normal shock (for air).
304
Diabatic Flow 305
The entropy changes across normal shocks in air, as determined by Eq. 1243,
are plotted in Figure 1216.
An examination of Figures 1215 and 1216 shows that when a normal shock
occurs in supersonic flow, there is a change from supersonic to subsonic flow
and the entropy increases. This increase in entropy is to be expected since the
shock is an irreversible process.
Assume that a shock can occur in a nozzle when the flow is subsonic. As
shown in Eq. 1242, the flow changes from subsonic across the shock wave to
supersonic. By Eq. 1239 there is a decrease in pressure. Thus, this type of
shock would be expansion shock. However, as shown by Eq. 1243, there
must be a decrease in entropy. But the entropy cannot possibly decrease in an
adiabatic process. Hence, the second law tells us that an expansion shock
cannot occur here. It should be noted, however, that an expansion shock may
occur in other types of flow.
or
or
G2
h1 + 2 T q = h2 + (1245a)
2pi
306 Thermodynamics of Fluid Flow
where q is the heat added per unit mass. Equations 1244 and 1245 may be
used together to determine the conditions after a heating process.
Example 1212. Air enters a tube having an internal diameter of 0.12 m with
a velocity of 90 m/s at a pressure of 620 kPa and a temperature of 80°C. It is
heated by the addition of 800kJ/s. Determine the pressure, temperature, and
velocity after heating.
n =_
620 x 1000
= 6.117 kg/nr
RT, 0.287x 1000x353.15
a ccf\ c 0.122X7T , , . .
GA = 550.5 x= 6.226 kg/s
800
128.5 kJ/kg
6.226
550.5: 550.5'
1.004 x (80 + 273.15) + + 128.5 = 1.004T? +
2x6.117zx 1000 2p2 x 1000
or
303,050  43,315
= 669,540 138,91 lp2
P2
259,735 = 669,540p2 138,911 pi
138,911 pi  669,540p2 + 259,735 = 0
P2~4.8199p2+ 1.8698 = 0
p2 = 4.394 kg/m1
From Eq. (b),
487.15 — 151.525/4.3942
T? =
2 1.004
= 477.39 K Answer
Then
Note that there is a pressure drop of 17.7 kPa. This pressure drop occurs in
the absence of friction and is due solely to the heating. The answers found in
this example are not precise, since the true mean specific heat is slightly
higher than the value assumed. A higher degree of accuracy can be obtained
by taking a new value of cp for the temperatures just calculated and then
repeating that portion of the problem involving cp.
When a vapor, such as steam, is heated in a constantarea passage, it is
necessary to resort to a trialanderror solution, since an accurate equation of
the state of the vapor (relating temperature, pressure, and density) is too complex
to be solved directly.
Although the velocities used in Example 1212 are much higher than those
normally encountered in industrial heating problems, it is desirable to
investigate the effects of heating on fluid properties in order that a more
comprehensive picture can be obtained of the effects of heating fluids in
constantarea passages.
A plot showing the variations in the properties of a fluid as it is heated in a
constantarea passage is known as a Rayleigh line. In Figure 1217, a Rayleigh
line is shown for a gas together with lines of constant entropy. In Figure
1218, a Rayleigh line is shown together with lines of constant enthalpy. An
examination of Figure 1217 shows that as the pressure decreases (due to
addition of heat) there is an increase in the entropy until a maximum value of
entropy is reached. Any further addition of heat results in a decrease in the
entropy. Obviously this condition is impossible since addition of heat should
produce an increase in entropy.
308 Thermodynamics of Fluid Flow
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Specific volume (m3/kg)
p=c = C — G~u
or
dp
= G2 = p2r2 (1246)
d v
For a line of constant entropy, the slope is
(ia  m . ( ^
~P “ dp/ \dp):
(1247)
(1248)
At the point of maximum entropy for the Rayleigh line, its slope must equal
that of the entropy line. From Eq. 1246a, the slope of a Rayleigh line,
Y= p2r2 (1249)
dv
Equating Eq. 1248 and Eq. 1249, it may be seen that when the entropy for
the Rayleigh line is at its maximum velocity, the fluid velocity equals the sonic
velocity.
By definition,
dh°=dh + Ydr
Sq = Tds = dfi  —
P
dP=ydy
P
or
T ds = dh + V dT = dh° (1250)
For the conditions discussed here, the increase in the stagnation enthalpy
equals the heat added. By Eq. 1250, the entropy must increase as heat is
added. But, as just stated, the entropy must decrease after the fluid reaches its
sonic velocity. This means that when heat is added to fluid in a constantarea
passage that has reached sonic velocity, an unstable condition is produced
and the mass rate of flow through the nozzle will change.
When a fluid having a supersonic velocity is heated in a constantarea
passage, there will be an increase in its entropy. This means a moving to the
left in Figure 1217, toward the point of maximum entropy. Under these
conditions, an addition of heat produces an increase in the pressure, an
increase in the density, and a decrease in the velocity until sufficient heat is
added to cause the velocity to be reduced to the sonic value.
1213 SUMMARY
The thermodynamics of fluid flow, in the broader sense, is quite complicated
but, in this chapter it has been greatly simplified by dealing only with
onedimensional flow and, for the most part, considering only ideal gases.
However, some fundamental concepts have been introduced. These include
the concept of sonic velocity and how it affects the performance of nozzles
310 Thermodynamics of Fluid Flow
PROBLEMS ____
121 (a) Water having a temperature of 27°C flows through a standard 1in.
pipe. Determine the maximum velocity that the water may have with
the flow being laminar.
(b) Same as part (a), except the pipe is 12 in.
(c) Draw general conclusions relative to the nature of water flow in
pipes for most engineering problems.
122 (a) Air at 1.012 bars, 28°C flows through a duct having an internal
diameter of 25.6 cm. Determine the maximum velocity that the air can
have with the flow being laminar.
(b) Same as part (a), except for air in a 42.5cmdiameter duct at 20.2
bars, 200°C.
(c) Draw general conclusions relative to the nature of air flow in ducts
for most engineering problems.
123 Air at 1.012 bars, 28°C flows through a rectangular duct, 26.7 cm by
48.5 cm with a velocity of 40 m/s. Determine the Reynolds number.
124 Air enters a constant area duct, 24 cm by 38 cm, at 1.018 bars, 24°C
with a velocity of 42 m/s. It leaves at 1.012 bars, 242°C. Determine the
velocity at exit.
125 Same as Problem 124 except at exit the duct is 18 cm by 26 cm.
126 Water enters a 6in. pipe at 22° C with a velocity of 2.1 m/s and leaves
at 91°C. Determine the Reynolds number at entrance and exit.
127 Water flows through a 4in. pipe at the rate of 14.9 kg/s. The tem¬
perature at exit is 42°C. Determine the Reynolds number.
128 Carbon dioxide at 250°C, 1.82bars flows through a 4in. pipe with a
velocity of 44 m/s. Determine the Reynolds number.
129 Water at 10° C enters a 2in. horizontal pipe with a velocity of 4 m/s at
8.95 bars. Neglect friction. The water temperature at exit is 140°C.
Determine the pressure, (static) at exit in bars.
1210 Same as Problem 129 except the water leaves in a 1in. pipe.
1211 Same as Problem 1210 except the water leaves at an elevation of 44 m
higher than that at entrance.
1212 Water enters a lin. pipe at 13.8 bars, 28°C, with a velocity of 1.8 m/s
and leaves at 120°C at an elevation of 25 m above that at entrance. The
frictional pressure loss in the pipe is 0.12 bar. Determine the pressure
at exit.
1213 (a) Determine the change in entropy for Problem 1212 per second.
(b) Determine the change in entropy in part (a) due to friction if no
heat had been added.
1214 Air at a pressure of 8.2 bars, 70°C has a stagnation temperature of
86°C. Determine: (a) air velocity and (b) stagnation pressure.
312 Thermodynamics of Fluid Flow
1215 Determine the velocity of sound in air (a) at 1.010 bars, 20°C and (b) at
1.015 bars, 300°C.
1216 Treating steam as an ideal gas, determine the velocity of sound in
steam at 0.1015 MPa, 200°C.
1217 Determine and compare the acoustic velocity of air and hydrogen at
0.1015 MPa, 25°C.
1218 (a) Air at 1.012 bars, 40°C flows in a duct with a velocity of 275 m/s.
Using a datum of 0°C for enthalpy, determine (a) stagnation enthalpy,
(b) stagnation temperature, and (c) stagnation pressure.
1219 Steam at 1.35 MPa, 200°C has a velocity of 200 m/s. Determine: (a)
stagnation enthalpy, (b) stagnation temperature, and (c) stagnation
pressure.
1220 Air expands isentropically from 13.5 bars, 105°C to 8.1 bars. Deter¬
mine the ratio of the final to initial acoustic velocity.
1221 (a) Air enters a constantarea duct at 1.52 bars, 43°C with a velocity
of 300 m/s. The pressure at duct exit is 1.44 bars. Neglect heat
transfer. Determine the velocity and temperature at exit.
(b) For this problem, what is the effect of friction in the duct on
velocity and temperature?
1222 Same as Problem 1220 except that the velocity at entrance is 580 m/s.
The pressure at duct exit is 1.60 bars.
1223 Determine the critical pressure for a fluid entering a nozzle under the
following conditions.
(a) Air at 0.1014 MPa, 25°C.
(b) Air at 13.5 MPa, 1000°C.
(c) Steam at 0.1014 MPa, 150°C.
(d) Steam at 13.5 MPa, 550°C.
(e) Hydrogen at 0.1014 MPa, 25°C.
1224 Air enters a nozzle at 2.21 bars, 88°C with a velocity of 80 m/s.
Neglect friction. Determine the pressure in the nozzle at the point the
velocity of the air reaches acoustic velocity.
1225 Same as Problem 1222 except neglect the initial velocity.
1226 Air enters a nozzle at 21.8 bars, 92°C with negligible velocity. The exit
pressure is 3.18 bars. Neglect friction. Determine the throat and mouth
areas flow at a flow of 1.42 kg/s.
1227 Same as Problem 1226 except the velocity at entrance is 42 m/s.
1228 (a) The overall nozzle efficiency in Problem 1226 is 94 percent.
Determine the exit area.
(b) The efficiency of the nozzle up to the throat for Problem 1226 is
97 percent. Determine the throat area.
(c) Comment on the necessity of taking the nozzle efficiency into
account in calculating the nozzle and throat areas.
Problems 313
1229 Steam at 6.5 MPa, 350° C expands to 4.0 MPa. The nozzle efficiency is
95 percent. The nozzle exit area is 6.54 cm2. Determine the mass rate
of flow.
1230 Steam at 6.0 MPa, 350°C expands to 0.80 MPa. Neglect friction up to
the throat. The overall nozzle efficiency is 95 percent. The throat area
is 8.6 cm2. Determine: (a) mass rate of flow and (b) exit area.
1231 Steam at 7.0 kPa, 6.5 percent moisture content enters the last stage of
a steam turbine at the rate of 1,487,000 kg/h. The nozzle efficiency is
95 percent. The pressure at nozzle exit is 4.0 kPa. Determine the total
exit area required.
1232 Air at 15.2 bars, 90°C expands in an ideal nozzle. An exit velocity of
560 m/s is desired. Neglect the initial velocity. Determine the exit
pressure.
1233 Same as Problem 1232 except that the efficiency of the nozzle is 95
percent.
1234 A compression shock occurs in a divergent flow passage. On the
upstream side of the shock, the fluid (air) has a velocity of 420 m/s and
is at 2.06 bars, 43°C. Determine: (a) the Mach number on the down¬
stream side of the shock and (b) the velocity and pressure on the
downstream side of the shock.
1235 Determine the change in entropy per kilogram of air as the result of
the shock in Problem 1234.
1236 Same as Problem 1234 except that the initial velocity is 370 m/s.
Comment on the effect of the initial velocity on the percentage of
change in the Mach number.
1237 Determine the change in entropy per kilogram of air as the result of
the shock in Problem 1236.
1238 If it is possible for a shock to occur in air having a velocity of 300 m/s,
determine the Mach number, the velocity, and the pressure on the
downstream side of the shock. The initial conditions are 2.06 bars,
43°C.
1239 Determine the change in entropy per kilogram of air for Problem
1238. Comment on the answer.
1240 A compression shock occurs in steam having a Mach number of 1.25.
Assuming a value of k = 1.3, determine the ratio of the pressure after
the shock to that before the shock.
1241 Steam enters a standard 4in. pipe at 1.45 MPa, 205° C with a velocity
of 25 m/s. It leaves at a pressure of 1.44 MPa. Neglecting friction,
determine the rate of heat addition.
1242 Air enters a constantarea tube at 1.42 bars, 90°C with a velocity of
460 m/s. 20J/g of heat are removed per gram of air. Determine the
velocity, pressure, and temperature at exit. Neglect friction.
314 Thermodynamics of Fluid Flow
131 INTRODUCTION
When a system undergoes a series of processes and then returns to its original
state, the series of processes is known as a cycle. Cycles are further defined
as closed or thermodynamic cycles and as open cycles. In the closed cycle,
there is no exchange of mass between the system and its surroundings. The
working substance of the system may expand or contract with work and heat
being added to or removed from it. An example of such a system is the steam
in a steam power plant. The system includes all devices through which the
steam or its condensate flows, namely: (1) the steam generator including the
superheater, the economizer, and the reheater, (2) the steam turbine, (3) the
condenser, (4) the boiler feed pump, and (5) feed water heaters of various
types. Another example of the closed cycle is the vapor compression refri¬
geration system.
In the open cycle, the system undergoes a series of processes during which
some of the fluid within the system is delivered to the surroundings with
additional fluid being drawn from the outside to replace it. Consider an
internal combustion engine of the automotive type. A mixture of air and fuel
is drawn into the cylinder, compressed, and burned. The resulting gases
expand and then are exhausted from the engine. This series of processes can
now be repeated. The conditions of the system at the start of intake are the
same as originally, even though the gases themselves are not returned to their
original state. Thus the series of processes may be termed an open cycle.
Nature may attempt to reduce the carbon dioxide produced to carbon and
oxygen, and hence, in a way, nature may close the cycle. However, the series
of processes that occur do not constitute a closed thermodynamic cycle.
In general, gas turbines1 are of the open type although a very few operate
with a closed cycle. The socalled hotair engines operate, overall, in a closed
cycle.
315
316 Gas Cycles and Applications
When an actual engine operates with a vapor, its ideal cycle is analyzed by using the particular
vapor.
The Otto Cycle 317
degree, the inherently low mean effective pressure4 means that any actual
engine approximating the Carnot cycle and using a gas as a working substance
will be a feeble engine. One type of internal combustion engine, the Lenoir,
had no compression before the combustion process. It may be discovered by
an airstandard analysis that when the cycle operates without compression, its
thermal efficiency is inherently low. Although Lenoir engines were actually
built, they became obsolete when internal combustion engines, which have
compression before combustion, came into use.
In the following sections, several cycles will be analyzed on the air
standard basis to explore their inherent characteristics. The thermodynamic
superiorities of some cycles will be indicated, as well as their thermodynamic
and practical limitations.
The first successful engine to operate on this series of events was built by
the German Nicolaus Otto. Hence, the theoretical cycle embodying these
events is known as the Otto cycle. The airstandard Otto cycle is shown in
Figure 131, in the pv and Ts planes.
Air in the Otto cycle is compressed isentropically from state 1 to state 2. The
original engines were lowspeed ones. Hence, combustion was completed with
very little piston motion, thus approaching a constantvolume process. In the
airstandard cycle, this process is simulated by the addition of heat at
constant volume, process 23 in Figure 131. Then the air was expanded in an
isentropic manner until the piston reached the end of its stroke. In the original
engines, the exhaust valve was opened close to the end of the expansion
stroke, with the pressure dropping with little change in the position of the
piston. This process is simulated in the airstandard cycle by a constant
volume cooling of the air (process 41) until the state of the air reaches the
original state, state 1. Although modern engines operate at such high speeds
that neither the combustion process nor the initial pressure drops through the
exhaust valves approximate constantvolume processes, the airstandard Otto
cycle is still used as a basis of comparison in judging the performance of
sparkignition types of engines.
An objective in analyzing airstandard cycles is to obtain values of thermal
(a)
T2=T,r‘“‘ (131)
and the pressure at the end of compression is
Pi = Pirk (132)
Since heat is added at constant volume, the heat supplied is
The Otto Cycle 319
Also
T3
P3 = Pi
t2
where T3 and p3 are the maximum cycle temperature and pressure. The
thermal efficiency, by definition, is
_  W_Q,Q, (135)
v‘ ~ Qs Qs
where Qr is the heat rejected per cycle.
Since the heat is rejected at constant volume.
(137)
But
so that
T4T, . T3T2
T, T2
Substituting into Eq. 137,
Equation 138 shows that the efficiency of the airstandard Otto cycle
depends solely on the compression ratio and is independent of factors such as
the heat added per cycle and the conditions at the start of compression.
A factor that is very useful in determining the work delivered per unit of
cylinder volume is the mean effective pressure (mep). Mean effective pressure
is defined as the mean pressure which, acting on the piston for one stroke,
produces work equivalent to the net cycle work. By definition
Then
1850
= 687.27 +
1 x 0.718
= 3263.9 K Answer
T _ T3 3263.9
J 4 ~ “T^T = 1420.7 K
r  8l
Qr = mcXT4Tx) = 1 x 0.718(1420.7  299.15)
= 805.3 kJ/kg
_Qs~Qr_ 1850805.3
Vt = 0.5647 or 56.47 percent
Qs 1850
The initial volume of the air is
mRTi 1 x 287x299.15
= 0.833 m3/kg
Pi 103 x 103
1044.7
1433.2 kPa Answer
mep 0.7289
Table 131
Thermal Efficiency
of AirStandard Otto Cycle
Thermal Efficiency
Compression Ratio (percent)
4.0 42.6
5.0 47.5
6.0 51.2
6.0 54.1
8.0 56.5
9.0 58.5
10.0 60.2
11.0 61.7
12.0 63.0
The reason for this is that even when small amounts of heat are added in the
Carnot cycle, the cylinder volumes required are exceedingly large. For ex¬
ample, use the same conditions as in Example 131 except only 370 kJ of
heat are added per kilogram of air.5 The maximum cylinder volume is
5.444 m3, which is 6.535 times that of the Otto cycle, while the cycle work
produced is only onefifth of that in Example 131. The mep for this Carnot
cycle is 39.13 kPa, which is only 2.7 percent of that for the Otto cycle. (This
low mep of the Carnot cycle makes it impractical to try to operate an engine
having a gaseous working substance on the Carnot cycle). The calculated
maximum temperature and pressure as determined in Example 131 are much
higher than those encountered in practice. One reason is that the variations in
specific heat are neglected in the air standard. Another reason is that the
actual combustion process is far from being at constant volume. In addition,
there are significant heat losses in an actual engine. However, the airstandard
analysis indicates inherently high pressures and temperatures in the Otto
cycle.
The airstandard method of analysis shows that it is essential to use a
highcompression ratio to obtain a high thermal efficiency. This relationship is
illustrated in Table 131, which was prepared by use of Eq. 138.
5If 1850 kJ of heat were to be added in this case for the Carnot cycle, the total cylinder volume
would be found to be tremendous and the mep only slightly above zero.
322 Gas Cycles and Applications
(a)
Qs = mcp(T3— T2)
6In the modern “diesel” engines, particularly those operated at high speeds, the combustion
process does not come close to a constantpressure one. Hence, these engines are also, and more
correctly, called compressionignition engines.
The Diesel Cycle 323
or
Also,
T
4 = (v4/v\y'
It should be noted that the expansion ratio VJV3 in the Diesel cycle is less
than the compression ratio Vx/V2.
The basic expression for thermal efficiency applied to the Diesel cycle is
(1310)
It is not possible to simplify the expression for the thermal efficiency of the
airstandard Diesel cycle in the manner shown for the airstandard Otto cycle,
since the expansion ratio in the Diesel cycle is not equal to the compression
ratio.
Answer
Ti = (P3/P4)(k)rt
The Brayton or Joule Cycle 325
(a)
(b)
or
But
Tj = (2i\(t~m = (PiYk~m = h
T4 \pj W T,
or
T,
T,
326 Gas Cycles and Applications
Hence,
or
and
T4 Ti Tx
t3  T2 t2
Substituting in Eq. 1311 gives
1
T2/T,
But
(131 la)
Also,
(131 lb)
(pTpJ1™
Comparison of Eqs. 138 and 131 la shows that the thermal efficiencies of the
airstandard Otto and Brayton cycles are the same for the same isentropic
compression ratio. (This statement may also be applied to the Carnot cycle.)
Example 133. The conditions at the start of compression in an airstandard
Brayton cycle engine are 103 kPa pressure, 26°C. The heat added per kilo¬
gram of air is 1850 kJ. The compression ratio is 8 to 1. Determine the maxi¬
mum temperature and pressure, the thermal efficiency, and the mep.
Solution. Refer to Figure 133. The maximum pressure equals p2. From
Example 131,
p2 = 1893 kPa
Q = mcp(T3 — T2) Answer
1850
T3= t2 + = 687.27 + 1842.63 = 2529.90 K Answer
1 x 1.004
Stirling and Ericsson (Regenerative) Cycles 327
(T2 is obtained from Example 131.) From Eq. 131 la, the thermal efficiency
A 26 + 273 A cr An cr a^
r/t = 1 —£on = 0.5647 or 56.4/ percent Answer
687.27
/0.833V2529.90\ a 3„
*3  (t)  (s%T$ 687 ^) = °'3833 m /kg
,0.5647(1850)
mep 2.962 352. / kra Answer
(a)
(b)
Regenerator
minimum cycle temperature. After heat rejection, the air is heated up to the
maximum cycle temperature, process 41, by being passed through the
regenerator. Because of the equality of temperatures, the heat given up by the
air as it is cooled in the regenerator is exactly equal to the heat it picks up in
passing back through the regenerator. Thus, the only exchanges of heat
between the air in the engine and the surroundings are those involving the
heat source and the heat sink. These are constanttemperature processes.
Since for a constanttemperature process of an ideal gas,
Q = W = pVln(U)
Qs ~ Q, plV,ln(V2/V,)p3V3ln(V3/V4)
7,1 Qs PiV, ln(Vj/V,)
_ mRT, ln(V2/V,)  mRT} In(V3/V4)
mRT, ln(V2/Vi)
But
V2 = V3 and V\ = V4
(1312)
It should be noted that the efficiency of the Stirling cycle is exactly equal to
that of the Carnot cycle for the same maximum and minimum cycle tem¬
peratures.
The Ericsson cycle is similar to the Stirling cycle except the heat exchanges
with the regenerator take place at constant pressure. The airstandard Erics¬
son cycle is shown in Figure 136. Since heat is exchanged with the heat
Pressure 4 1
2
3
Volume
1 2
Temperature
Entropy
330
Interna! Combustion Engines 331
source and the heat sink at constant temperature as it is in the Stirling cycle,
the ideal thermal efficiencies of the two cycles are equal, namely, 1 TJTH.
Many years ago, the socalled hotair engines were designed, built, and used
extensively. Their cycles of operation were designed to approximate either
the Stirling or Ericsson cycles. In spite of the inherently high thermal
efficiency of these cycles, the actual thermal efficiencies of hotair engines
were poor. The main reason for these low efficiencies was the fact that heat
must be transferred in all four processes through gas films on the heat
transfer surfaces. Since gas films offer much resistance to heat transfer, the
mean cycle temperatures were very much lower than the theoretical tem¬
peratures. The resulting low thermal efficiency together with high main¬
tenance problems, high engine bulk, and the development of the sparkignition
and the compressionignition engines led to the disuse of hotair engines.
However, recent engineering developments have caused a renewed interest in
Stirling cycle engines for specialized applications.
To exhaust
manifold
(c) (d)
FIGURE 137 Fourcycle engine, (a) Suction. (b) Compression, (c) Expansion. (d) Exhaust.
1 Actually an airfuel charge is drawn into the cylinder and exhaust gases
are expelled from it.
2 There is friction between the piston and the cylinder.
3 Heat exchange takes place between the cylinder contents and the walls in
all four processes.
4 Particularly in a highspeed engine, there is much piston motion, and
hence, changes in volume during such processes as combustion, intake,
and the opening and closing of the exhaust valves.
5 In the actual engine, the cylinder contents are a real mixture, which changes
in composition throughout the cycle. In particular, the state of this real
mixture is affected by variable specific heats. The combustion process is a
complex one in which the phenomenon of dissociation is a part.
Table 132
Thermal Efficiencies, Percent
exchange between the cylinder and its contents, and such events as com¬
bustion and valve openings and closings take place instantaneously. On the
other hand, an airfuel mixture is drawn into the cylinder where it mixes with
hot clearance gases (i.e., gases left in the clearance space at the end of
exhaust). The specific heat of this mixture varies during mixing and during
compression. Dissociation, as discussed in Section 1010, controls the tempera¬
ture reached during combustion.
By using charts entitled Thermodynamic Charts for Combustion Processes1
the effects of compression ratio and percentage of excess air on the thermal
efficiency of an ideal airfuel cycle (i.e., an ideal engine using a real airfuel
mixture) can be determined. The results of these determinations are shown in
Table 132.
The cycle of operation of a compressionignition engine, particularly of the
highspeed type, differs greatly from the airstandard diesel cycle. One of the
main differences occurs during the combustion process. There is an ignition
lag period after injection first starts, during which time the fuel is heated up to
its ignition temperature. Then a very rapid combustion of fuel takes place,
which causes a large rise in pressure, and thus deviates greatly from the
constantpressure addition of heat that occurs in the Diesel cycle.
power. Since there are two values of Work, the indicated and the brake,
there are two thermal efficiencies. The indicated thermal efficiency,
indicated work
indicated rft = (1313)
Qhp
where QHP is the heating value of the fuel required to produce the indicated
work.
The brake thermal efficiency is
brake work
brake pt = (1314)
Qhp
, , 2400 x 3600 ,, ,
Answer
brake Vl = 545x437920 = 3bl perCer
(1 kW = IkJ/s)
. „ , (2400 4260)3600 _
indicated r,( = “^45^43^20~ = 40 0 percent Answer
mechanical output
(1315)
mechanical input
Substituting Eq. 1313 and 1314 into Eq. 1315 for an internal combustion
engine,
_ brake Tjf
(1315a)
indicated r]t
2400
Vm = 90.2 percent Answer
2400 + 260
or
36.1
Vm = 90.2 percent
40.1
336 Gas Cycles and Applications
cycle work
mep = (1316)
Lx A
Since the mep is related to the cycle work, it may be used to determine the
power of the engine. Thus
= 203.2 kW Answer
Note: The number of cycles per minute = \ revolutions per minute (rpm).
Example 137. The actual engine in Example 136 has an indicated thermal
efficiency of 75 percent of that of the airfuel cycle, when supplied with the
theoretical amount of air. The heating value of the charge is 3722 kJ/m3. The
volumetric efficiency8 is 78 percent. Determine the power output of the
engine.
4 2
8 Volumetric efficiency is the ratio of the volume actually drawn into the theoretical volume that
can be drawn in.
9In a fourcycle engine, a suction stroke occurs once every two revolutions.
Gas Compressors 337
8.51 x 0.78
0.1106 m3/s
60
The airfuel cycle efficiency, Table 132, is 39.8 percent. Then the actual work
equals
97,090
231.8 Nm Answer
2tt x 4000/60
or
Since
In Eq. 1320, V\ is the cylinder volume and also is the volume of gas drawn
into the cylinder. A pV diagram for an idealgas compressor with clearance
is shown in Figure 1311. At the end of the delivery of the compressed gas,
the clearance10 is filled with highpressure gas, V3. This gas expands until its
pressure becomes equal to the suction pressure, state 0. Gas is drawn into the
cylinder between state 0 and 1. The theoretical cycle work equals VVV, 4 Wx_2
+ W23 + W3.4. It may be shown that this cycle work equals
i(V,  Vo)
But V] — V0 is the volume of the gas drawn into the cylinder. Thus, for an
ideal compressor, with or without clearance,
(n —l)/n
n
cycle work = (1321)
n — 1
l0The volume between the piston and the cylinder heat at the end of the stroke.
340 Gas Cycles and Applications
where internal work is the power delivered by the piston to the air.
The work input to the compressor, the shaft power, exceeds the work input to
the air because of mechanical frictional losses. Applying Eq. 1315 to an air
compressor, the mechanical efficiency
indicated work
(1325)
shaft work
•rZ7Z?//////Z22jy/////////////////??//////////////.
77ZZZZZZZZZZZZZZZZZZZZZZZZZZZZZZZZZZZZ1
£22
6596/0.78 = 8456 kW
342 Gas Cycles and Applications
8456
= 8629 kW Answer
0.98
The power input to the air is the internal power and the mechanical losses
occur outside of the compressor.
internal work H2 ~
(b) internal power = Hx
rhcp(T2— Tj)
time time
8456
T2 = 30 + = 246.8° C Answer
38.5 x 1.004
Gas Turbines 343
FIGURE 1315 Ideal gas turbine cycle, (a) Compressor. (fc>) Turbine, (c) Combined.
r, 1050 + 273.15
JTWO = 835.43 K
(P3/P4)'*‘,W*
(a) Since the expansion in the ideal turbine is isentropic, the turbine work is
Example 1311. Use the same conditions as for Example 1310 but assume
identical turbine and compressor internal efficiencies1' of 80 percent and
mechanical efficiencies12 of 97 percent. Neglect the variation in specific heats
and also the difference between the mass rate of flow of the air and the mass
rate of flow of the gases.
175 92
internal compressor work = — = 219.9 kJ/kg
0.8
219.9
compressor shaft work =  226.7 kJ/kg
0.97
Then
net work = 379.98  226.7  153.28 kJ/kg
Because of losses within the compressor, the temperature of the air leaving
the compressor and entering the combustor is higher than the theoretical
value of 475.37 K. See Figure 1316. Since there are no appreciable heat losses
from the compressor, the actual internal compressor work equals h2 — hj =
cp(T2~ Ti), where the subscript 2' indicates the actual property at compressor
exit. Then
rr, _ rr , internal work _ ,,AA 1. , 219.9
T2T+ Tp " 300 15 +L004
= 519.17 K
W 153.28 1QOQ . a
Vt=Q = 8q7~2' = 18 99 percent Answer
Solution. Neglecting the heat losses in the turbine, the decrease in enthalpy
in the turbine equals the internal turbine work. Then,
Using Eq. 1326a, the temperature of the air leaving the regenerator,
Fuel
r? (1327)
2cp
The pressure at the diffuser exit may be computed by using the isentropic
pressuretemperature relationship.
The action in the nozzle is the reverse of that in the diffuser. For sim¬
plification it may be assumed that the velocity at the nozzle entrance is
negligible. Assuming that the pressure at the nozzle exit is known, the
temperature, and hence, the velocity at the nozzle exit can be determined.
The propulsive force developed by the turbojet engine is
FP = m(YnYd) (1328)
where m is the mass flow rate of the air (assumed to equal the gas flow), Yn is
the gas velocity at nozzle exit, and Yd is the air velocity at diffuser entrance.
350 Gas Cycles and Applications
(222.2)'
T7 =  24.6 + = 0°C
2 x 1.004 x 1000
Then
/273 15\14/04
p2 = 46.57(^j = 64.8 kPa
^248.55
0.4/1.4
(; = 414.94 K
t>273 15®
PROBLEMS ____
131 (a) Same as Example 131 in the text except that the compression
ratio is 12 to 1.
(b) Compare these results with those of Example 131.
132 (a) Same as Example 131 in the text except that the initial tem¬
perature is 70°C.
(b) Compare these results with those of Example 131.
133 Compression starts in an airstandard Otto cycle at 103 kPa and 26°C.
The compression ratio is 8 to 1. The maximum allowable pressure is
7500 kPa. Determine the mean effective pressure.
134 Compression starts in an airstandard Otto cycle at 103 kPa, 26°C. The
compression ratio is 8 to 1. The maximum allowable temperature is
2800 K. Determine: (a) maximum pressure and (b) mean effective
pressure.
135 Same as Example 132 in the text except the initial temperature is
70° C.
136 Compression starts in an airstandard Diesel cycle at 103 kPa, 26°C.
The compression ratio is 16 to 1. The maximum cycle temperature is
2200 K. Determine the thermal efficiency and the mean effective
pressure.
137 Same as Example 132 in the text except the compression ratio is 12 to
1.
138 Same as Example 133 in the text except the initial temperature is
70° C.
139 Compression starts in an airstandard Brayton cycle at 103 kPa and
26°C. The compression ratio is 8 to 1. The maximum temperature is
2200 K. Determine the thermal efficiency and the mean effective
pressure.
1310 Same as Example 133 in the text except the compression ratio is 12 to 1.
1311 In an airstandard Stirling cycle, heat is received at 840°C and is
rejected at 220°C. The minimum cycle pressure is 120 kPa. The ratio
of the volume at the end of addition of heat to that before addition of
heat is 3.5 to 1. Determine: (a) thermal efficiency, (b) maximum
pressure, and (c) mean effective pressure.
1312 Determine the heat transferred per cycle in the regenerator of Prob¬
lem 1311 per kilogram of air.
1313 In an ideal Stirling cycle, the working fluid is helium. Heat is received
at 840°C and rejected at 220°C. The minimum cycle pressure is
120 kPa. The ratio of the volume after the end of addition of heat to
that before heat addition is 3.5 to 1. Determine: (a) thermal efficiency,
(b) maximum pressure, and (c) mean effective pressure. Compare the
results with those of Problem 1311.
Problems 353
1314 (a) Same as Problem 137 except that the maximum cycle temperature
is 1500 K.
(b) Using results from Problems 137 and 1314(a), plot efficiency
against heat added. Extrapolate the curve to zero heat added. Com¬
ment on the results.
1315 Same as Example 133 in the text except that the initial pressure is
400 kPa. Compare the results with those of Example 133.
1316 In an airstandard Diesel cycle, the cutoff ratio (the ratio of the
volume after heat addition to that before heat addition) is 3 to 1. The
initial conditions are 101 kPa, 20°C. The compression ratio is 18 to 1.
Determine the thermal efficiency and mean effective pressure.
1317 The thermal efficiency of an airstandard Otto cycle is 54 percent. The
mean effective pressure is 1400 kPa. The initial conditions are
100.5 kPa, 22°C. Determine: (a) maximum temperature and (b)
maximum pressure.
1318 In an airstandard Otto cycle engine, the temperatures at the start and
end of the adiabatic expansion are 3260 K and 1420 K. The heat added
per cycle is 1850kJ/kg of air. Determine the compression ratio and the
cycle work per kilogram of air.
1319 The compression ratio of a sparkignition engine is 8 to 1, the in¬
dicated engine efficiency is 80 percent, and the mechanical efficiency is
76 percent when 20 percent excess air is used. Determine the brake
thermal efficiency.
1320 Assume that the gasoline used in Problem 1319 is equivalent in
heating value to C8Hi8. Determine the amount of fuel used per hour
when the brake power is 76 kW.
1321 A sparkignition engine has a compression ratio of 8 to 1. Assume that
the fuel is equivalent to C8H18. The engine uses 268 g of fuel per
kilowatthour. The mechanical efficiency is 78 percent. Determine the
indicated thermal efficiency.
1322 A compressionignition engine has an output of 3100 kW when it uses
682 kg of fuel per hour. The higher heating value of the fuel is
44,100 kJ/kg. The indicated efficiency is 40.2 percent. Determine:
(a) brake thermal efficiency and (b) frictional loss in the engine.
1323 The charge in the cylinders of a sparkigniton engine is 0.980 bar and
40°C at the start of compression. The compression ratio is 8 to 1.
Assume the fuel is to be C8H18. The indicated engine efficiency is 80
percent when the theoretical amount of air is used. Determine the
mean effective pressure.
1324 To make certain that the fuel in Problem 1323 is fully vaporized at the
start of compression, the charge is heated so that its temperature at
the start of compression is 70°C. Determine the new mean effective
pressure.
354 Gas Cycles and Applications
1325 The engine in Problem 1323 has six cylinders and operates at
3800 rpm. It is a fourcycle engine. The bore is 9.8 cm, and the stroke
is 11.8 cm. The mechanical efficiency is 82 percent. Determine the
power output of the engine.
1326 By use of a supercharger, the pressure in the cylinders at the start of
compression of the engine in Problem 1323 is increased to 1.42 bars.
Determine the new mean effective pressure.
1327 Determine the torque of the engine in Problem 1325.
1328 A sixcylinder, twocycle engine with a 20.2cm bore and a 29.8cm
stroke has an indicated mean effective pressure of 5.94 bars and a
mechanical efficiency of 81 percent. Determine the torque at 2200 rpm.
1329 A fourcycle compressionignition engine uses 231 g of fuel per kilo¬
watthour and 22 g of air per gram of fuel when it delivers 2450 kW.
This power requires the use of a blower that receives air at 0.95 bar, 21° C
and delivers it at 1.35 bars. The theoretical power required for the blower
is 60 percent of the actual power required. (To obtain the theoretical
power of the blower, assume a rectangular pV diagram, i.e., neglect the
change in volume of the air in the blower.) Determine the power required
for the blower.
1330 Since a blower uses some of the power output of a supercharged
engine, will the thermal efficiency of a supercharged engine be less
than that of an engine without a supercharger? Why?
1331 A theoretical gas turbine receives air at a pressure of 100.5 kPa, 26°C.
The pressure ratio is 6 to 1. The heat supplied per kilogram of air is
780 kJ. Determine per kilogram of air, (a) turbine work, (b)
compressor work, (c) work delivered, and (d) cycle efficiency.
1332 Repeat Problem 1331 for an actual turbine. Assume the internal
efficiencies of both turbine and compressor are 81 percent and the
mechanical efficiencies are both 97.5 percent. Neglect variations in
specific heats and also the difference between the mass flow of gases
and air. Assume the same maximum temperature.
1333 Same as Problems 1331 and 1332 except the heat supplied per
kilogram of air is 990 kJ. Comment on the effect of the maximum
temperature on the efficiency of a gas turbine.
1334 The fuel used in Problem 1332 is similar to Ci2H26. (a) Determine the
mass of fuel per unit mass of air needed to provide the given amount
of heating, (b) Determine the percentage of excess air used.
1335 Repeat Problems 1331 and 1332 using a pressure ratio of 9 to 1.
1336 Determine the mass rate of flow of air for Problem 1334 if the output
of the gas turbine unit is 12,000 kW.
1337 A regenerator having an effectiveness of 81 percent is added to the gas
turbine of Problem 1232. Determine the new thermal efficiency,
neglecting pressure and heat losses in the regenerator.
Problems 355
1338 Same as Problem 1337 but the regenerator is added to the gas turbine
in Problem 1333.
1339 Same as Problem 1337 but the regenerator is added to the gas turbine
in Problem 1335.
1340 An airplane is flying at 900 km/h, at an altitude where the pressure is
45.2 kPa and the temperature is 25.8°C. The airplane is powered by a
jet engine having a maximum cycle pressure of 292 kPa and a maxi¬
mum cycle temperature of 1120°C. Determine for the ideal case the air
flow required to produce a propulsive force of 68,700 N.
_ 14 _
141 INTRODUCTION
The maximum thermal efficiency of a heat engine is obtained when heat is
transferred to the working substance in the engine at the source temperature
and is rejected from the engine at a temperature equal to that of the heat sink.
When the working substance is gaseous throughout the cycle, it is impractical
to hold the temperature of the working substance constant during heat
transfer. Thus, the thermal efficiencies of the gas cycles discussed in Chapter
13, such as the Otto, Diesel, and Brayton, are much lower than they should be
for the given source and sink temperatures.
On the other hand, when the pressure is held constant during a phase
change of a simple substance, the temperature remains constant. Hence, if
heat is added to a vaporizing liquid and is removed from a condensing vapor,
the desired constanttemperature heat transfer can be obtained, provided that
the pressure is held constant. A vaporliquid cycle, commonly called a vapor
cycle, embodies these processes and, hence, has the potential for high thermal
efficiencies. Likewise, when a reversed vapor cycle is used for refrigeration,
the amount of refrigeration obtained from a given work input exceeds that
obtained by the use of most reversed gas cycles.
356
Temperature
357
358 Vapor Cycles and Applications
However, there are two difficulties. First, the condensation must be stopped
at the right place (state 4). Second, a very wet vapor must be compressed
until, for this case, it becomes a liquid. Thus, in spite of its high thermal
efficiency, the Carnot vapor cycle is not very practical.
‘The internal processes are reversible. The actual process of transferring heat from the sources to
the working substance is irreversible.
Heat
discussions of the Rankine cycle that follow. However, other fluids are now
being considered for use in the Rankine cycle in newer energy conversion
systems such as geothermal energy, ocean thermal gradients energy, and
some aspects of solar energy. The principles developed for the use of steam
apply equally well to other vapors.
The work output of the Rankine cycle is the difference between the work
output of the expander (normally a turbine) and the work input to the pump.
Since the expansion is isentropic, the turbine work,
Wt=(h2h3)s (141)
Wp=(h4h1)s (142)
where v is the specific volume of the water entering the pump. Applying Eq.
143 to the pump of Figure 145,
Heat is supplied in the steam generator. This heat equals the difference
between the enthalpies of the steam at exit and the water at entrance. Or,
using Figures 143 and 144,
Solution. Carnot (see Figures 141 and 142). The heat supplied equals
w 766.4
= 42.68 percent Answer
Vt =
qs 1795.6
or
233.9 17.5
= 42.68 percent
233.9 + 273.15
h2 = 2802.4 s2 = 6.1869 = s3
y = 29.28 percent
h3 = 2533.5  0.2928(2460.0) = 1813.2 J/g
For this problem, the very small pump work may be neglected. Then hi = h4.
The turbine work is
W 989 2
rjt = — = = 36.25 percent Answer
qs LlLo.y
Because the pump work does become significant when steam is generated
at very high pressures, it is desirable to illustrate how the pump work is to be
used in determining the thermal efficiency.
Example 142. Repeat Example 141 for the Rankine cycle taking into
account the pump work.
Solution. The delivered (or net) work equals the turbine work minus the
pump work. Or
The enthalpy of the water entering the steam generator equals that leaving
the condenser plus the pump work. Or
The moisture content of the steam after expansion in the Rankine cycle in
Example 141 is almost 30 percent. Since wet steam is not a uniform mixture,
a distinct loss in efficiency will occur. There will be continuous impact
between the highvelocity steam molecules and the slower moving water
droplets, resulting in an appreciable loss in kinetic energy. In addition, there
will be mechanical difficulties including erosion in handling this very large
amount of water. These problems can be minimized by superheating the
steam before it leaves the steam generator. In addition to minimizing these
problems, in superheating the steam heat is added at a mean temperature
higher than the boiling temperature; inherently, this increases the thermal
efficiency.
Example 143. The conditions are the same as for the Rankine cycle in
Example 141 except that the steam leaving the steam generator has a
temperature of 560° C.
y = 15.15 percent
W 1430.9
Vt = = 40.67 percent Answer
Qs 3518.2
The increase in the thermal efficiency from 36.25 to 40.67 percent is due solely
to the addition of some of the heat at a higher mean temperature. For the
actual case, there would be an added gain due to the reduction in the moisture
content of the steam at turbine exit. Also, because of losses within the
turbine, the moisture content of the steam at turbine exit would be much less
than the 15 percent calculated in this problem.
In the illustrative examples used thus far, the steam was generated at a
moderate pressure. In large modern plants, much higher pressures are used,
Volume
364
Reheating Cycle 365
approaching the critical pressure of 22.09 MPa in many instances and exceed¬
ing it in some. For these high pressure plants, the theoretical pump work may
be approximately 1 percent of the turbine and, hence, must be taken into
account when accurate results are desired.
h2 = 3591.7 s2 = 7.4022= s3
Q.
CO
c
LU
Entropy
At 0.26 MPa, with s = 7.4022, the steam is superheated and its enthalpy is
2877.7 J/g. After resuperheating, h4 = 3615.9 and s4 = 8.5528 = s5.
At 2.0 kPa, 8.5528 = 8.7237  y(8.4629)
y = 2.02 percent
= 1846.1 J/g
= 4256.4 J/g
w 1846.1
= 43.37 percent
Vt =
Qs 4256.4
Not only has the moisture content at the turbine exhaust been greatly
reduced, but there is a material gain in the theoretical thermal efficiency. The
desirability of reheating the steam increases with increased initial pressures.
For very high initial pressures, it may be desirable to use two stages in
resuperheating the steam.
Regenerative Feedwater Heating 367