Moran Safiro Solucionario Inglés (5 Edicion)

5th Edition

Fundamentals of
Engineering Thermodynamics
Michael J. Moran
The Ohio State University
Howard N. Shapiro
Iowa State University of Science and Technology
John Wiley & Sons, Inc.

Fundamentals of
Engineering
Thermodynamics
5th Edition

Fundamentals of
Engineering Thermodynamics
Michael J. Moran
The Ohio State University
Howard N. Shapiro
Iowa State University of Science and Technology
John Wiley & Sons, Inc.

Copyright 2006 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester,
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Library of Congress Cataloging-in-Publication Data
Moran, Michael J.
Fundamentals of engineering thermodynamics: SI version / Michael
J. Moran, Howard N. Shapiro. -- 5th ed.
p. cm.
Includes bibliographical references and index.
ISBN-13 978-0-470-03037-0 (pbk. : alk. paper)
ISBN-10 0-470-03037-2 (pbk. : alk. paper)
1. Thermodynamics. I. Shapiro, Howard N. II. Title.
TJ265.M66 2006
621.4021--dc22
2006008521
ISBN-13 978-0-470-03037-0
ISBN-10 0-470-03037-2
British Library Cataloguing in Publication Data
A catalogue record for this book is available from the British Library
Typeset in 10/12 pt Times by Techbooks

Printed and bound in Great Britain by Scotprint, East Lothian
This book is printed on acid-free paper responsibly manufactured from sustainable forestry in which at least two trees
are planted for each one used for paper production.
Preface
In this fifth edition we have retained the objectives of the first four editions:
to present a thorough treatment of engineering thermodynamics from the classical viewpoint,
to provide a sound basis for subsequent courses in fluid mechanics and heat transfer, and
to prepare students to use thermodynamics in engineering practice.
While the fifth edition retains the basic organization and level of the previous editions,
we have introduced several enhancements proven to be effective for student learning. In-
cluded are new text elements and interior design features that help students understand and
apply the subject matter. With this fifth edition, we aim to continue our leadership in effec-
tive pedagogy, clear and concise presentations, sound developments of the fundamentals, and
state-of-the-art engineering applications.

New in the Fifth Edition
An engaging new feature called Thermodynamics in the News is intro-
duced in every chapter. News boxes tie stories of current interest to concepts discussed
in the chapter. The news items provide students with a broader context for their
learning and form the basis for new Design and Open Ended problems in each chapter.
Other class-tested content changes have been introduced:
A new discussion of the state-of-the-art of fuel cell technology (Sec. 13.4).
Streamlined developments of the energy concept and the first law of thermodynamics
(Secs. 2.3 and 2.5, respectively).
Streamlined developments of the mass and energy balances for a control volume
(Secs. 4.1 and 4.2, respectively).
Enhanced presentation of second law material (Chap. 5) clearly identifies key concepts.
Restructuring of topics in psychrometrics (Chap. 12) and enthalpy of combustion and
heating values (Chap. 13) further promotes student understanding.
Functional use of color facilitates data retrieval from the appendix tables.
End-of-chapter problems have been substantially refreshed. As in previous editions, a
generous collection of problems is provided. The problems are classified under head-
ings to assist instructors in problem selection. Problems range from confidence-building
exercises illustrating basic skills to more challenging ones that may involve several
components and require higher-order thinking.
The end-of-chapter problems are organized to provide students with the opportunity to
develop engineering skills in three modes:
Conceptual. See Exercises: Things Engineers Think About.
Skill Building. See Problems: Developing Engineering Skills.
Design. See Design and Open ended Problems: Exploring Engineering Practice.
The comfortable interior design from previous editions has been enhanced with an even
more learner-centered layout aimed at enhancing student understanding.

Core Text Features
This edition continues to provide the core features that have made the text the global leader
in engineering thermodynamics education.
Exceptional class-tested pedagogy. Our pedagogy is the model that others emulate.
For an overview, see How to Use this Book Effectively inside the front cover of the book.
v
vi Preface
Systematic problem solving methodology. Our methodology has set the standard for
thermodynamics texts in the way it encourages students to think systematically and
helps them reduce errors.
Effective development of the second law of thermodynamics. The text features the
entropy balance (Chap. 6) recognized as the most effective way for students to learn
how to apply the second law. Also, the presentation of exergy analysis (Chaps. 7
and 13) has become the state-of-the-art model for learning that subject matter.
Software to enhance problem solving for deeper learning. We pioneered the use of
software as an effective adjunct to learning engineering thermodynamics and solving
engineering problems.
Sound developments of the application areas. Included in Chaps. 814 are compre-
hensive developments of power and refrigeration cycles, psychrometrics, and combus-
tion applications from which instructors can choose various levels of coverage ranging
from short introductions to in-depth studies.
Emphasis on engineering design and analysis. Specific text material on the design
process is included in Sec. 1.7: Engineering Design and Analysis and Sec. 7.7:
Thermoeconomics. Each chapter also provides carefully crafted Design and Open
Ended Problems that allow students to develop an appreciation of engineering practice
and to enhance a variety of skills such as creativity, formulating problems, making
engineering judgments, and communicating their ideas.
Flexibility in units. The text allows an SI or mixed SI /English presentation. Careful
use of units and systematic application of unit conversion factors is emphasized
throughout the text.

Ways to Meet Different Course Needs
In recognition of the evolving nature of engineering curricula, and in particular of the di-
verse ways engineering thermodynamics is presented, the text is structured to meet a variety
of course needs. The following table illustrates several possible uses of the text assuming a
semester basis (3 credits). Coverage would be adjusted somewhat for courses on a quarter
basis depending on credit value. Detailed syllabi for both semester and quarter bases are pro-
vided on the Instructors Web Site. Courses could be taught in the second or third year to
engineering students with appropriate background.
Type of course Intended audience Chapter coverage

Principles. Chaps. 16.
Non-majors Applications. Selected topics from
Chaps. 810 (omit compressible flow in Chap. 9).
Surveys
Principles. Chaps. 16.
Majors Applications. Same as above plus selected
topics from Chaps. 12 and 13.
First course. Chaps. 18.
Two-course (Chap. 7 may deferred to second course or omitted.)
Majors
sequences Second course. Selected topics from
Chaps. 914 to meet particular course needs.
Preface vii

How to Use This Book Effectively
This book has several features that facilitate study and contribute further to understanding:
Examples
Numerous annotated solved examples are provided that feature the solution methodol-
ogy presented in Sec. 1.7.3 and illustrated in Example 1.1. We encourage you to study
these examples, including the accompanying comments.
Less formal examples are given throughout the text. They open with
for example. . . and close with . These examples also should be studied.
Exercises
Each chapter has a set of discussion questions under the heading Exercises: Things
Engineers Think About that may be done on an individual or small-group basis. They
are intended to allow you to gain a deeper understanding of the text material, think
critically, and test yourself.
A large number of end-of-chapter problems also are provided under the heading
Problems: Developing Engineering Skills. The problems are sequenced to coordinate
with the subject matter and are listed in increasing order of difficulty. The problems are
also classified under headings to expedite the process of selecting review problems to
solve.
Answers to selected problems are provided in the appendix (pp. 865868).
Because one purpose of this book is to help you prepare to use thermodynamics in
engineering practice, design considerations related to thermodynamics are included.
Every chapter has a set of problems under the heading Design and Open Ended
Problems: Exploring Engineering Practice that provide brief design experiences to help
you develop creativity and engineering judgment. They also provide opportunities to
practice communication skills.
Further Study Aids

Each chapter opens with an introduction giving the engineering context and stating the
chapter objective.
Each chapter concludes with a chapter summary and study guide that provides a point
of departure for examination reviews.
Key words are listed in the margins and coordinated with the text material at those
locations.
Key equations are set off by a double horizontal bar, as, for example, Eq. 1.10.
Methodology update in the margin identifies where we refine our problem-solving
methodology, as on p. 9, or introduce conventions such as rounding the temperature
273.15 K to 273 K, as on p. 20.
For quick reference, conversion factors and important constants are provided on the
next page.
A list of symbols is provided on the inside back cover and facing page.
viii Preface

Constants
Universal Gas Constant Standard Atmospheric Pressure
R 8.314 kJ/kmol # K 1 atm 1.01325 bar
Standard Acceleration of Gravity Temperature Relations

g 9.80665 m/s2 T 1C2 T 1K2 273.15

Acknowledgments
We thank the many users of our previous editions, located at more than 200 universities and
colleges in the United States and Canada, and over the globe, who contributed to this revi-
sion through their comments and constructive criticism. Special thanks are owed to Prof. Ron
Nelson, Iowa State University, for developing the EES solutions and for his assistance in up-
dating the end-of-chapter problems and solutions. We also thank Prof. Daisie Boettner, United
States Military Academy, West Point, for her contributions to the new discussion of fuel cell
technology. Thanks are also due to many individuals in the John Wiley and Sons, Inc.,
organization who have contributed their talents and energy to this edition. We appreciate their
professionalism and commitment.
We are extremely gratified by the reception this book has enjoyed, and we have aimed to
make it even more effective in this fifth edition. As always, we welcome your comments,
criticism, and suggestions.
Michael J. Moran
[email protected]
Howard N. Shapiro
[email protected]
John Wiley and Sons Ltd would like to thank Brian J. Woods for his work in adapting the
5th Edition to incorporate SI units.
Contents
CHAPTER 1 CHAPTER 4
Getting Started: Introductory Control Volume Analysis
Concepts and Definitions 1 Using Energy 121
1.1 Using Thermodynamics 1 4.1 Conservation of Mass for a Control Volume 121
1.2 Defining Systems 1 4.2 Conservation of Energy for a Control
1.3 Describing Systems and Their Behavior 4 Volume 128
1.4 Measuring Mass, Length, Time, and Force 8 4.3 Analyzing Control Volumes at Steady
1.5 Two Measurable Properties: Specific Volume and State 131
Pressure 10 4.4 Transient Analysis 152
1.6 Measuring Temperature 14 Chapter Summary and Study Guide 162
1.7 Engineering Design and Analysis 18
Chapter Summary and Study Guide 22
CHAPTER 2 CHAPTER 5
Energy and the First Law of The Second Law of
Thermodynamics 29 Thermodynamics 174
2.1 Reviewing Mechanical Concepts of Energy 29 5.1 Introducing the Second Law 174
2.2 Broading Our Understanding of Work 33 5.2 Identifying Irreversibilities 180
2.3 Broading Our Understanding of Energy 43 5.3 Applying the Second Law to Thermodynamic
2.4 Energy Transfer By Heat 44 Cycles 184
2.5 Energy Accounting: Energy Balance for Closed 5.4 Defining the Kelvin Temperature Scale 190
Systems 48 5.5 Maximum Performance Measures for Cycles
2.6 Energy Analysis of Cycles 58 Operating Between Two Reservoirs 192
Chapter Summary and Study Guide 62 5.6 Carnot Cycle 196
CHAPTER 3
Evaluating Properties 69
3.1 Fixing the State 69
CHAPTER 6
EVALUATING PROPERTIES: GENERAL Using Entropy 206
CONSIDERATIONS 70 6.1 Introducing Entropy 206
3.2 pvT Relation 70 6.2 Defining Entropy Change 208
3.3 Retrieving Thermodynamic Properties 76 6.3 Retrieving Entropy Data 209
3.4 Generalized Compressibility Chart 94 6.4 Entropy Change in Internally Reversible
EVALUATING PROPERTIES USING THE IDEAL Processes 217
GAS MODEL 100 6.5 Entropy Balance for Closed Systems 220
3.5 Ideal Gas Model 100 6.6 Entropy Rate Balance for Control Volumes 231
3.6 Internal Energy, Enthalpy, and Specific Heats of 6.7 Isentropic Processes 240
Ideal Gases 103 6.8 Isentropic Efficiencies of Turbines, Nozzles,
3.7 Evaluating u and h using Ideal Gas Tables, Compressors, and Pumps 246
Software, and Constant Specific Heats 105 6.9 Heat Transfer and Work in Internally Reversible,
3.8 Polytropic Process of an Ideal Gas 112 Steady-State Flow Processes 254
Chapter Summary and Study Guide 114 Chapter Summary and Study Guide 257
ix
x Contents
9.12 Compressible Flow Preliminaries 426

CHAPTER 7 9.13 Analyzing One-Dimensional Steady Flow in
Nozzles and Diffusers 430
Exergy Analysis 272
9.14 Flow in Nozzles and Diffusers of Ideal Gases
7.1 Introducing Exergy 272 with Constant Specific Heats 436
7.2 Defining Exergy 273 Chapter Summary and Study Guide 444
7.3 Closed System Exergy Balance 283
7.4 Flow Exergy 290
7.5 Exergy Rate Balance for Control Volumes 293
CHAPTER 10
7.6 Exergetic (Second Law) Efficiency 303 Refrigeration and Heat Pump
7.7 Thermoeconomics 309 Systems 454
10.1 Vapor Refrigeration Systems 454
10.2 Analyzing Vapor-Compression Refrigeration
CHAPTER 8 Systems 457
10.3 Refrigerant Properties 465
Vapor Power Systems 325 10.4 Cascade and Multistage Vapor-Compression
8.1 Modeling Vapor Power Systems 325 Systems 467
8.2 Analyzing Vapor Power SystemsRankline 10.5 Absorption Refrigeration 469
Cycle 327 10.6 Heat Pump Systems 471
8.3 Improving PerformanceSuperheat and 10.7 Gas Refrigeration Systems 473
Reheat 340 Chapter Summary and Study Guide 479
8.4 Improving PerformanceRegenerative Vapor
Power Cycle 346
8.5 Other Vapor Cycle Aspects 356
CHAPTER 11
8.6 Case Study: Exergy Accounting of a Vapor Power
Plant 358
Thermodynamic Relations 487
Chapter Summary and Study Guide 365 11.1 Using Equations of State 487
11.2 Important Mathematical Relations 494
11.3 Developing Property Relations 497
CHAPTER 9 11.4 Evaluating Changes in Entropy, Internal Energy,
and Enthalpy 504
Gas Power Systems 373
11.5 Other Thermodynamic Relations 513
INTERNAL COMBUSTION ENGINES 373 11.6 Constructing Tables of Thermodynamic
9.1 Introducing Engine Terminology 373 Properties 520
9.2 Air-Standard Otto Cycle 375 11.7 Generalized Charts for Enthalpy and
9.3 Air-Standard Diesel Cycle 381 Entropy 524
9.4 Air-Standard Dual Cycle 385 11.8 pvT Relations for Gas Mixtures 531
11.9 Analyzing Multicomponent Systems 536
GAS TURBINE POWER PLANTS 388
9.5 Modeling Gas Turbine Power Plants 388
9.6 Air-Standard Brayton Cycle 389
9.7 Regenerative Gas Turbines 399 CHAPTER 12
9.8 Regenerative Gas Turbines with Reheat and
Intercooling 404 Ideal Gas Mixtures
9.9 Gas Turbines for Aircraft Propulsion 414 and Psychrometrics
9.10 Combined Gas TurbineVapor Power Applications 558
Cycle 419
IDEAL GAS MIXTURES:
9.11 Ericsson and Stirling Cycles 424 GENERAL CONSIDERATIONS 558
COMPRESSIBLE FLOW THROUGH NOZZLES AND 12.1 Describing Mixture Composition 558
DIFFUSERS 426 12.2 Relating p, V, and T for Ideal Gas Mixtures 562
Contents xi
12.3 Evaluating U, H, S and Specific Heats 564

12.4 Analyzing Systems Involving Mixtures 566
CHAPTER 14
PSYCHROMETRIC APPLICATIONS 579 Chemical and Phase
12.5 Introducing Psychrometric Principles 579 Equilibrium 679
12.6 Psychrometers: Measuring the Wet-Bulb and EQUILIBRIUM FUNDAMENTALS 679
Dry-Bulb Temperatures 590
14.1 Introducing Equilibrium Criteria 679
12.7 Psychrometric Charts 592
12.8 Analyzing Air-Conditioning Processes 593 CHEMICAL EQUILIBRIUM 684
12.9 Cooling Towers 609 14.2 Equation of Reaction Equilibrium 684
Chapter Summary and Study Guide 611 14.3 Calculating Equilibrium Compositions 686
14.4 Further Examples of the Use of the Equilibrium
Constant 695
CHAPTER 13 PHASE EQUILIBRIUM 704
14.5 Equilibrium Between Two Phases of a Pure
Reacting Mixtures and Substance 705
Combustion 620 14.6 Equilibrium of Multicomponent, Multiphase
Systems 706
COMBUSTION FUNDAMENTALS 620
13.1 Introducing Combustion 620
13.2 Conservation of EnergyReacting
Systems 629
APPENDIX
13.3 Determining the Adiabatic Flame
Temperature 641
Appendix Tables, Figures, and
13.4 Fuel Cells 645
13.5 Absolute Entropy and the Third Law of Charts 718
Thermodynamics 648 Index to Tables in SI Units 718
CHEMICAL EXERGY 655 Index to Figures and Charts 814
13.6 Introducing Chemical Exergy 655
13.7 Standard Chemical Exergy 659 Answers to Selected Problems 822
13.8 Exergy Summary 664
Index 825
13.9 Exergetic (Second Law) Efficiencies of Reacting
Systems 667
C
H
A
Getting Started: P
T
Introductory
Concepts and
E
R 1
Definitions
E N G I N E E R I N G C O N T E X T The word thermodynamics stems from
the Greek words therme (heat) and dynamis (force). Although various aspects of what is
now known as thermodynamics have been of interest since antiquity, the formal study of
thermodynamics began in the early nineteenth century through consideration of the motive
power of heat: the capacity of hot bodies to produce work. Today the scope is larger,
dealing generally with energy and with relationships among the properties of matter.
Thermodynamics is both a branch of physics and an engineering science. The scientist
is normally interested in gaining a fundamental understanding of the physical and chemical
behavior of fixed quantities of matter at rest and uses the principles of thermodynamics to
relate the properties of matter. Engineers are generally interested in studying systems and
how they interact with their surroundings. To facilitate this, engineers extend the subject of
thermodynamics to the study of systems through which matter flows.
The objective of this chapter is to introduce you to some of the fundamental concepts chapter objective
and definitions that are used in our study of engineering thermodynamics. In most instances
the introduction is brief, and further elaboration is provided in subsequent chapters.

1.1 Using Thermodynamics
Engineers use principles drawn from thermodynamics and other engineering sciences, such
as fluid mechanics and heat and mass transfer, to analyze and design things intended to meet
human needs. The wide realm of application of these principles is suggested by Table 1.1,
which lists a few of the areas where engineering thermodynamics is important. Engineers
seek to achieve improved designs and better performance, as measured by factors such as an
increase in the output of some desired product, a reduced input of a scarce resource, a
reduction in total costs, or a lesser environmental impact. The principles of engineering
thermodynamics play an important part in achieving these goals.

1.2 Defining Systems
An important step in any engineering analysis is to describe precisely what is being studied.
In mechanics, if the motion of a body is to be determined, normally the first step is to de-
fine a free body and identify all the forces exerted on it by other bodies. Newtons second
1
2 Chapter 1 Getting Started: Introductory Concepts and Definitions
TABLE 1.1 Selected Areas of Application of Engineering Thermodynamics

Automobile engines
Turbines
Compressors, pumps
Fossil- and nuclear-fueled power stations
Propulsion systems for aircraft and rockets
Combustion systems
Cryogenic systems, gas separation, and liquefaction
Heating, ventilating, and air-conditioning systems
Vapor compression and absorption refrigeration
Solar-cell arrays
Heat pumps
Cooling of electronic equipment
Alternative energy systems
Fuel cells
Thermoelectric and thermionic devices
Magnetohydrodynamic (MHD) converters
Solar-activated heating, cooling, and power generation
Geothermal systems
Surfaces with thermal
Ocean thermal, wave, and tidal power generation control coatings
Wind power
Biomedical applications International Space Station
Life-support systems
Artificial organs
Steam generator
Electric
Combustion Stack power
gas cleanup
Turbine
Coal Air Steam Cooling
Generator tower
Condenser
Ash
Condensate
Cooling water
Refrigerator Electrical power plant Automobile engine
Trachea
Lung
Fuel in
Compressor Combustor
Turbine
Air in Hot gases

out
Heart
Turbojet engine Biomedical applications

1.2 Defining Systems 3
law of motion is then applied. In thermodynamics the term system is used to identify the
subject of the analysis. Once the system is defined and the relevant interactions with other
systems are identified, one or more physical laws or relations are applied.
The system is whatever we want to study. It may be as simple as a free body or as com- system
plex as an entire chemical refinery. We may want to study a quantity of matter contained
within a closed, rigid-walled tank, or we may want to consider something such as a pipeline
through which natural gas flows. The composition of the matter inside the system may be
fixed or may be changing through chemical or nuclear reactions. The shape or volume of the
system being analyzed is not necessarily constant, as when a gas in a cylinder is compressed
by a piston or a balloon is inflated.
Everything external to the system is considered to be part of the systems surroundings. surroundings
The system is distinguished from its surroundings by a specified boundary, which may be
at rest or in motion. You will see that the interactions between a system and its surround- boundary
ings, which take place across the boundary, play an important part in engineering thermo-
dynamics. It is essential for the boundary to be delineated carefully before proceeding with
any thermodynamic analysis. However, the same physical phenomena often can be analyzed
in terms of alternative choices of the system, boundary, and surroundings. The choice of a
particular boundary defining a particular system is governed by the convenience it allows in
the subsequent analysis.
TYPES OF SYSTEMS
Two basic kinds of systems are distinguished in this book. These are referred to, respectively,
as closed systems and control volumes. A closed system refers to a fixed quantity of matter,
whereas a control volume is a region of space through which mass may flow.
A closed system is defined when a particular quantity of matter is under study. A closed closed system
system always contains the same matter. There can be no transfer of mass across its bound-
ary. A special type of closed system that does not interact in any way with its surroundings
is called an isolated system. isolated system
Figure 1.1 shows a gas in a pistoncylinder assembly. When the valves are closed, we can
consider the gas to be a closed system. The boundary lies just inside the piston and cylinder
walls, as shown by the dashed lines on the figure. The portion of the boundary between the
gas and the piston moves with the piston. No mass would cross this or any other part of the
boundary.
In subsequent sections of this book, thermodynamic analyses are made of devices such
as turbines and pumps through which mass flows. These analyses can be conducted in prin- control volume
ciple by studying a particular quantity of matter, a closed system, as it passes through the
device. In most cases it is simpler to think instead in terms of a given region of space
through which mass flows. With this approach, a region within a prescribed boundary is
studied. The region is called a control volume. Mass may cross the boundary of a control Gas Boundary
volume.
A diagram of an engine is shown in Fig. 1.2a. The dashed line defines a control volume
that surrounds the engine. Observe that air, fuel, and exhaust gases cross the boundary. A
schematic such as in Fig. 1.2b often suffices for engineering analysis.
The term control mass is sometimes used in place of closed system, and the term open
system is used interchangeably with control volume. When the terms control mass and con-
trol volume are used, the system boundary is often referred to as a control surface.
In general, the choice of system boundary is governed by two considerations: (1) what is
known about a possible system, particularly at its boundaries, and (2) the objective of the
analysis. for example. . . Figure 1.3 shows a sketch of an air compressor connected Figure 1.1 Closed
to a storage tank. The system boundary shown on the figure encloses the compressor, tank, system: A gas in a
and all of the piping. This boundary might be selected if the electrical power input were pistoncylinder assembly.
Air in Drive Air in

shaft
Exhaust
gas out
Fuel in Fuel in
Drive
shaft
Exhaust
gas out
Boundary (control surface)
Boundary (control surface)
(a) (b)
Figure 1.2 Example of a control volume (open system). An automobile engine.
known, and the objective of the analysis were to determine how long the compressor must
operate for the pressure in the tank to rise to a specified value. Since mass crosses the
boundary, the system would be a control volume. A control volume enclosing only the com-
pressor might be chosen if the condition of the air entering and exiting the compressor were
known, and the objective were to determine the electric power input.
1.3 Describing Systems and Their Behavior

Engineers are interested in studying systems and how they interact with their surroundings.
In this section, we introduce several terms and concepts used to describe systems and how
they behave.
MACROSCOPIC AND MICROSCOPIC VIEWS OF THERMODYNAMICS
Systems can be studied from a macroscopic or a microscopic point of view. The macro-
scopic approach to thermodynamics is concerned with the gross or overall behavior. This
is sometimes called classical thermodynamics. No model of the structure of matter at the
molecular, atomic, and subatomic levels is directly used in classical thermodynamics.
Although the behavior of systems is affected by molecular structure, classical thermody-
namics allows important aspects of system behavior to be evaluated from observations of
the overall system.
Air
Tank
Air compressor
Figure 1.3 Air compressor and

+
storage tank.
1.3 Describing Systems and Their Behavior 5
The microscopic approach to thermodynamics, known as statistical thermodynamics, is

concerned directly with the structure of matter. The objective of statistical thermodynamics
is to characterize by statistical means the average behavior of the particles making up a system
of interest and relate this information to the observed macroscopic behavior of the system.
For applications involving lasers, plasmas, high-speed gas flows, chemical kinetics, very low
temperatures (cryogenics), and others, the methods of statistical thermodynamics are essen-
tial. Moreover, the microscopic approach is instrumental in developing certain data, for
example, ideal gas specific heats (Sec. 3.6).
For the great majority of engineering applications, classical thermodynamics not only pro-
vides a considerably more direct approach for analysis and design but also requires far fewer
mathematical complications. For these reasons the macroscopic viewpoint is the one adopted
in this book. When it serves to promote understanding, however, concepts are interpreted
from the microscopic point of view. Finally, relativity effects are not significant for the systems
under consideration in this book.
PROPERTY, STATE, AND PROCESS
To describe a system and predict its behavior requires knowledge of its properties and how
those properties are related. A property is a macroscopic characteristic of a system such as property
mass, volume, energy, pressure, and temperature to which a numerical value can be assigned
at a given time without knowledge of the previous behavior (history) of the system. Many
other properties are considered during the course of our study of engineering thermody-
namics. Thermodynamics also deals with quantities that are not properties, such as mass flow
rates and energy transfers by work and heat. Additional examples of quantities that are not
properties are provided in subsequent chapters. A way to distinguish nonproperties from prop-
erties is given shortly.
The word state refers to the condition of a system as described by its properties. Since state
there are normally relations among the properties of a system, the state often can be speci-
fied by providing the values of a subset of the properties. All other properties can be deter-
mined in terms of these few.
When any of the properties of a system change, the state changes and the system is said
to have undergone a process. A process is a transformation from one state to another. How- process
ever, if a system exhibits the same values of its properties at two different times, it is in the
same state at these times. A system is said to be at steady state if none of its properties steady state
changes with time.
A thermodynamic cycle is a sequence of processes that begins and ends at the same state. thermodynamic cycle
At the conclusion of a cycle all properties have the same values they had at the beginning.
Consequently, over the cycle the system experiences no net change of state. Cycles that are
repeated periodically play prominent roles in many areas of application. For example, steam
circulating through an electrical power plant executes a cycle.
At a given state each property has a definite value that can be assigned without knowl-
edge of how the system arrived at that state. Therefore, the change in value of a property as
the system is altered from one state to another is determined solely by the two end states and
is independent of the particular way the change of state occurred. That is, the change is in-
dependent of the details of the process. Conversely, if the value of a quantity is independent
of the process between two states, then that quantity is the change in a property. This pro-
vides a test for determining whether a quantity is a property: A quantity is a property if its
change in value between two states is independent of the process. It follows that if the value
of a particular quantity depends on the details of the process, and not solely on the end states,
that quantity cannot be a property.
EXTENSIVE AND INTENSIVE PROPERTIES
Thermodynamic properties can be placed in two general classes: extensive and intensive.
extensive property A property is called extensive if its value for an overall system is the sum of its values for
the parts into which the system is divided. Mass, volume, energy, and several other proper-
ties introduced later are extensive. Extensive properties depend on the size or extent of a
system. The extensive properties of a system can change with time, and many thermody-
namic analyses consist mainly of carefully accounting for changes in extensive properties
such as mass and energy as a system interacts with its surroundings.
intensive property Intensive properties are not additive in the sense previously considered. Their values are
independent of the size or extent of a system and may vary from place to place within the
system at any moment. Thus, intensive properties may be functions of both position and time,
whereas extensive properties vary at most with time. Specific volume (Sec. 1.5), pressure,
and temperature are important intensive properties; several other intensive properties are in-
troduced in subsequent chapters.
for example. . . to illustrate the difference between extensive and intensive prop-
erties, consider an amount of matter that is uniform in temperature, and imagine that it is
composed of several parts, as illustrated in Fig. 1.4. The mass of the whole is the sum of the
masses of the parts, and the overall volume is the sum of the volumes of the parts. However,
the temperature of the whole is not the sum of the temperatures of the parts; it is the same
for each part. Mass and volume are extensive, but temperature is intensive.
PHASE AND PURE SUBSTANCE
phase The term phase refers to a quantity of matter that is homogeneous throughout in both chem-
ical composition and physical structure. Homogeneity in physical structure means that the
matter is all solid, or all liquid, or all vapor (or equivalently all gas). A system can contain
one or more phases. For example, a system of liquid water and water vapor (steam) con-
tains two phases. When more than one phase is present, the phases are separated by phase
boundaries. Note that gases, say oxygen and nitrogen, can be mixed in any proportion to
form a single gas phase. Certain liquids, such as alcohol and water, can be mixed to form
a single liquid phase. But liquids such as oil and water, which are not miscible, form two
liquid phases.
pure substance A pure substance is one that is uniform and invariable in chemical composition. A pure
substance can exist in more than one phase, but its chemical composition must be the same
in each phase. For example, if liquid water and water vapor form a system with two phases,
the system can be regarded as a pure substance because each phase has the same composi-
tion. A uniform mixture of gases can be regarded as a pure substance provided it remains a
gas and does not react chemically. Changes in composition due to chemical reaction are
(a) (b)
Figure 1.4 Figure used to discuss the extensive and intensive property concepts.
1.3 Describing Systems and Their Behavior 7
considered in Chap. 13. A system consisting of air can be regarded as a pure substance as
long as it is a mixture of gases; but if a liquid phase should form on cooling, the liquid would
have a different composition from the gas phase, and the system would no longer be con-
sidered a pure substance.
EQUILIBRIUM
Classical thermodynamics places primary emphasis on equilibrium states and changes from
one equilibrium state to another. Thus, the concept of equilibrium is fundamental. In mechanics, equilibrium
equilibrium means a condition of balance maintained by an equality of opposing forces. In
thermodynamics, the concept is more far-reaching, including not only a balance of forces but
also a balance of other influences. Each kind of influence refers to a particular aspect of ther-
modynamic, or complete, equilibrium. Accordingly, several types of equilibrium must exist in-
dividually to fulfill the condition of complete equilibrium; among these are mechanical, ther-
mal, phase, and chemical equilibrium.
Criteria for these four types of equilibrium are considered in subsequent discussions.
For the present, we may think of testing to see if a system is in thermodynamic equilib-
rium by the following procedure: Isolate the system from its surroundings and watch for
changes in its observable properties. If there are no changes, we conclude that the sys-
tem was in equilibrium at the moment it was isolated. The system can be said to be at an
equilibrium state. equilibrium state
When a system is isolated, it does not interact with its surroundings; however, its state
can change as a consequence of spontaneous events occurring internally as its intensive prop-
erties, such as temperature and pressure, tend toward uniform values. When all such changes
cease, the system is in equilibrium. Hence, for a system to be in equilibrium it must be a
single phase or consist of a number of phases that have no tendency to change their condi-
tions when the overall system is isolated from its surroundings. At equilibrium, temperature
is uniform throughout the system. Also, pressure can be regarded as uniform throughout as
long as the effect of gravity is not significant; otherwise a pressure variation can exist, as in
a vertical column of liquid.
ACTUAL AND QUASIEQUILIBRIUM PROCESSES
There is no requirement that a system undergoing an actual process be in equilibrium during

the process. Some or all of the intervening states may be nonequilibrium states. For many
such processes we are limited to knowing the state before the process occurs and the state
after the process is completed. However, even if the intervening states of the system are not
known, it is often possible to evaluate certain overall effects that occur during the process.
Examples are provided in the next chapter in the discussions of work and heat. Typically,
nonequilibrium states exhibit spatial variations in intensive properties at a given time. Also,
at a specified position intensive properties may vary with time, sometimes chaotically. Spa-
tial and temporal variations in properties such as temperature, pressure, and velocity can be
measured in certain cases. It may also be possible to obtain this information by solving ap-
propriate governing equations, expressed in the form of differential equations, either analyt-
ically or by computer.
Processes are sometimes modeled as an idealized type of process called a quasiequilibr- quasiequilibrium
ium (or quasistatic) process. A quasiequilibrium process is one in which the departure from process
thermodynamic equilibrium is at most infinitesimal. All states through which the system
passes in a quasiequilibrium process may be considered equilibrium states. Because
nonequilibrium effects are inevitably present during actual processes, systems of engineer-
ing interest can at best approach, but never realize, a quasiequilibrium process.
Our interest in the quasiequilibrium process concept stems mainly from two consider-
ations:
Simple thermodynamic models giving at least qualitative information about the behav-
ior of actual systems of interest often can be developed using the quasiequilibrium
process concept. This is akin to the use of idealizations such as the point mass or the
frictionless pulley in mechanics for the purpose of simplifying an analysis.
The quasiequilibrium process concept is instrumental in deducing relationships that
exist among the properties of systems at equilibrium (Chaps. 3, 6, and 11).
1.4 Measuring Mass, Length, Time, and Force

When engineering calculations are performed, it is necessary to be concerned with the units
of the physical quantities involved. A unit is any specified amount of a quantity by compar-
ison with which any other quantity of the same kind is measured. For example, meters, cen-
timeters, kilometers, feet, inches, and miles are all units of length. Seconds, minutes, and
hours are alternative time units.
Because physical quantities are related by definitions and laws, a relatively small number
of physical quantities suffice to conceive of and measure all others. These may be called
primary dimensions. The others may be measured in terms of the primary dimensions and
are called secondary. For example, if length and time were regarded as primary, velocity and
area would be secondary.
Two commonly used sets of primary dimensions that suffice for applications in mechanics
are (1) mass, length, and time and (2) force, mass, length, and time. Additional primary
dimensions are required when additional physical phenomena come under consideration.
Temperature is included for thermodynamics, and electric current is introduced for applica-
tions involving electricity.
base unit Once a set of primary dimensions is adopted, a base unit for each primary dimension is
specified. Units for all other quantities are then derived in terms of the base units. Let us
illustrate these ideas by considering briefly the SI system of units.
1.4.1 SI Units
The system of units called SI, takes mass, length, and time as primary dimensions and re-
gards force as secondary. SI is the abbreviation for Systme International dUnits (Interna-
tional System of Units), which is the legally accepted system in most countries. The con-
ventions of the SI are published and controlled by an international treaty organization. The
SI base units SI base units for mass, length, and time are listed in Table 1.2 and discussed in the follow-
ing paragraphs. The SI base unit for temperature is the kelvin, K.
The SI base unit of mass is the kilogram, kg. It is equal to the mass of a particular cylin-
der of platinumiridium alloy kept by the International Bureau of Weights and Measures near
Paris. The mass standard for the United States is maintained by the National Institute of Stan-
dards and Technology. The kilogram is the only base unit still defined relative to a fabricated
object.
The SI base unit of length is the meter (metre), m, defined as the length of the path traveled
by light in a vacuum during a specified time interval. The base unit of time is the second, s.
The second is defined as the duration of 9,192,631,770 cycles of the radiation associated
with a specified transition of the cesium atom.
The SI unit of force, called the newton, is a secondary unit, defined in terms of the base
units for mass, length, and time. Newtons second law of motion states that the net force
acting on a body is proportional to the product of the mass and the acceleration, written
1.4 Measuring Mass, Length, Time, and Force 9
TABLE 1.2 Units and dimensions for Mass, Length, Time

SI
Quantity Unit Dimension Symbol
mass kilogram M kg
length meter L m
time second t s
F ma. The newton is defined so that the proportionality constant in the expression is equal
to unity. That is, Newtons second law is expressed as the equality
F ma (1.1)
The newton, N, is the force required to accelerate a mass of 1 kilogram at the rate of 1 meter
per second per second. With Eq. 1.1
1 N 11 kg2 11 m/s2 2 1 kg # m/s2 (1.2)
for example. . . to illustrate the use of the SI units introduced thus far, let us
determine the weight in newtons of an object whose mass is 1000 kg, at a place on the earths METHODOLOGY
UPDATE
surface where the acceleration due to gravity equals a standard value defined as 9.80665 m/s2.
Recalling that the weight of an object refers to the force of gravity, and is calculated using Observe that in the cal-
the mass of the object, m, and the local acceleration of gravity, g, with Eq. 1.1 we get culation of force in
newtons, the unit
conversion factor is set
F mg
11000 kg219.80665 m/s2 2 9806.65 kg # m/s2
off by a pair of vertical
lines. This device is used
throughout the text to
This force can be expressed in terms of the newton by using Eq. 1.2 as a unit conversion identify unit conversions.
factor. That is
F a9806.65 b` ` 9806.65 N
kg # m 1N
2
s 1 kg # m/s2
Since weight is calculated in terms of the mass and the local acceleration due to gravity,
the weight of an object can vary because of the variation of the acceleration of gravity with
location, but its mass remains constant. for example. . . if the object considered pre-
viously were on the surface of a planet at a point where the acceleration of gravity is, say,
one-tenth of the value used in the above calculation, the mass would remain the same but
the weight would be one-tenth of the calculated value.
SI units for other physical quantities are also derived in terms of the SI base units. Some
of the derived units occur so frequently that they are given special names and symbols, such
as the newton. SI units for quantities pertinent to thermodynamics are given in Table 1.3.
TABLE 1.3
Quantity Dimensions Units Symbol Name

1
Velocity Lt m/s
Acceleration Lt2 m/s2
Force MLt2 kg m/s2 N newtons
Pressure ML1 t2 kg m/s2 (N/m2) Pa pascal
Energy ML2 t2 kg m2/s2 (N m) J joule
Power ML2 t3 kg m2/s3 (J/s) W watt
TABLE 1.4 SI Unit Since it is frequently necessary to work with extremely large or small values when using the
Prefixes SI unit system, a set of standard prefixes is provided in Table 1.4 to simplify matters. For
Factor Prefix Symbol example, km denotes kilometer, that is, 103 m.
1012 tera T
109 giga G 1.4.2 English Engineering Units
106 mega M
Although SI units are the worldwide standard, at the present time many segments of the en-
103 kilo k
102 hecto h gineering community in the United States regularly use some other units. A large portion of
102 centi c Americas stock of tools and industrial machines and much valuable engineering data utilize
103 milli m units other than SI units. For many years to come, engineers in the United States will have
106 micro to be conversant with a variety of units.
109 nano n
1012

pico p
1.5 Two Measurable Properties: Specific

Volume and Pressure
Three intensive properties that are particularly important in engineering thermodynamics are
specific volume, pressure, and temperature. In this section specific volume and pressure are
considered. Temperature is the subject of Sec. 1.6.
1.5.1 Specific Volume

From the macroscopic perspective, the description of matter is simplified by considering it
to be distributed continuously throughout a region. The correctness of this idealization, known
as the continuum hypothesis, is inferred from the fact that for an extremely large class of
phenomena of engineering interest the resulting description of the behavior of matter is in
agreement with measured data.
When substances can be treated as continua, it is possible to speak of their intensive
thermodynamic properties at a point. Thus, at any instant the density at a point is
defined as
r lim a b
m
(1.3)
VSV V
where V is the smallest volume for which a definite value of the ratio exists. The volume
V contains enough particles for statistical averages to be significant. It is the smallest vol-
ume for which the matter can be considered a continuum and is normally small enough that
it can be considered a point. With density defined by Eq. 1.8, density can be described
mathematically as a continuous function of position and time.
The density, or local mass per unit volume, is an intensive property that may vary from
point to point within a system. Thus, the mass associated with a particular volume V is
determined in principle by integration
m V
r dV (1.4)
and not simply as the product of density and volume.

specific volume The specific volume v is defined as the reciprocal of the density, v 1r. It is the volume
per unit mass. Like density, specific volume is an intensive property and may vary from point
to point. SI units for density and specific volume are kg/m3 and m3/kg, respectively. How-
ever, they are also often expressed, respectively, as g/cm3 and cm3/g.
In certain applications it is convenient to express properties such as a specific volume
on a molar basis rather than on a mass basis. The amount of a substance can be given on a
1.5 Two Measurable Properties: Specific Volume and Pressure 11
molar basis in terms of the kilomole (kmol) or the pound mole (lbmol), as appropriate. In molar basis
either case we use
m
n (1.5)
M
The number of kilomoles of a substance, n, is obtained by dividing the mass, m, in kilograms

by the molecular weight, M, in kg/kmol. Appendix Table A-1 provides molecular weights for
several substances.
To signal that a property is on a molar basis, a bar is used over its symbol. Thus, v sig-
nifies the volume per kmol. In this text, the units used for v are m3/kmol. With Eq. 1.10, the
relationship between v and v is
v Mv (1.6)
where M is the molecular weight in kg/kmol or lb/lbmol, as appropriate.
1.5.2 Pressure
Next, we introduce the concept of pressure from the continuum viewpoint. Let us begin by con-
sidering a small area A passing through a point in a fluid at rest. The fluid on one side of the
area exerts a compressive force on it that is normal to the area, Fnormal. An equal but oppositely
directed force is exerted on the area by the fluid on the other side. For a fluid at rest, no other
forces than these act on the area. The pressure p at the specified point is defined as the limit pressure
p lim a b
Fnormal
(1.7)
ASA A
where A is the area at the point in the same limiting sense as used in the definition of
density.
If the area A was given new orientations by rotating it around the given point, and the
pressure determined for each new orientation, it would be found that the pressure at the point
is the same in all directions as long as the fluid is at rest. This is a consequence of the
equilibrium of forces acting on an element of volume surrounding the point. However, the
pressure can vary from point to point within a fluid at rest; examples are the variation of at-
mospheric pressure with elevation and the pressure variation with depth in oceans, lakes, and
other bodies of water.
Consider next a fluid in motion. In this case the force exerted on an area passing through
a point in the fluid may be resolved into three mutually perpendicular components: one normal
to the area and two in the plane of the area. When expressed on a unit area basis, the com-
ponent normal to the area is called the normal stress, and the two components in the plane
of the area are termed shear stresses. The magnitudes of the stresses generally vary with the
orientation of the area. The state of stress in a fluid in motion is a topic that is normally
treated thoroughly in fluid mechanics. The deviation of a normal stress from the pressure,
the normal stress that would exist were the fluid at rest, is typically very small. In this book
we assume that the normal stress at a point is equal to the pressure at that point. This as-
sumption yields results of acceptable accuracy for the applications considered.
PRESSURE UNITS
The SI unit of pressure and stress is the pascal.

1 pascal 1 N/m2
However, in this text it is convenient to work with multiples of the pascal: the kPa, the bar,
and the MPa.
1 kPa 103 N/m2
1 bar 105 N/m2
1 MPa 106 N/m2
Although atmospheric pressure varies with location on the earth, a standard reference value
can be defined and used to express other pressures.
1 standard atmosphere 1atm2 1.01325 105 N/m2
absolute pressure Pressure as discussed above is called absolute pressure. Throughout this book the term
pressure refers to absolute pressure unless explicitly stated otherwise. Although absolute pres-
sures must be used in thermodynamic relations, pressure-measuring devices often indicate
the difference between the absolute pressure in a system and the absolute pressure of the
atmosphere existing outside the measuring device. The magnitude of the difference is called
gage pressure a gage pressure or a vacuum pressure. The term gage pressure is applied when the pressure
in the system is greater than the local atmospheric pressure, patm.
vacuum pressure
p1gage2 p1absolute2 patm 1absolute2 (1.8)
When the local atmospheric pressure is greater than the pressure in the system, the term vac-
uum pressure is used.
p1vacuum2 patm 1absolute2 p1absolute2 (1.9)
The relationship among the various ways of expressing pressure measurements is shown in
Fig. 1.5.
p (gage)
Atmospheric
pressure
Absolute
pressure
that is greater p (absolute) p (vacuum)
than the local
atmospheric
pressure
patm
(absolute)
Absolute
pressure that
p (absolute) is less than
than the local
atmospheric
pressure
Zero pressure Zero pressure

Figure 1.5 Relationships among the absolute, atmospheric, gage, and
vacuum pressures.
1.5 Two Measurable Properties: Specific Volume and Pressure 13
PRESSURE MEASUREMENT patm

Gas at
Two commonly used devices for measuring pressure are the manometer and the Bourdon pressure p
tube. Manometers measure pressure differences in terms of the length of a column of liquid
such as water, mercury, or oil. The manometer shown in Fig. 1.6 has one end open to the at-
mosphere and the other attached to a closed vessel containing a gas at uniform pressure. The
difference between the gas pressure and that of the atmosphere is
Tank L
p patm rgL (1.10)
where is the density of the manometer liquid, g the acceleration of gravity, and L the dif- Manometer
ference in the liquid levels. For short columns of liquid, and g may be taken as constant. liquid
Because of this proportionality between pressure difference and manometer fluid length, pres- Figure 1.6 Pressure
sures are often expressed in terms of millimeters of mercury, inches of water, and so on. It measurement by a
is left as an exercise to develop Eq. 1.15 using an elementary force balance. manometer.
A Bourdon tube gage is shown in Fig. 1.7. The figure shows a curved tube having an
elliptical cross section with one end attached to the pressure to be measured and the other
end connected to a pointer by a mechanism. When fluid under pressure fills the tube, the
elliptical section tends to become circular, and the tube straightens. This motion is
transmitted by the mechanism to the pointer. By calibrating the deflection of the pointer
for known pressures, a graduated scale can be determined from which any applied pres-
sure can be read in suitable units. Because of its construction, the Bourdon tube meas-
ures the pressure relative to the pressure of the surroundings existing at the instrument.
Accordingly, the dial reads zero when the inside and outside of the tube are at the same
pressure.
Pressure can be measured by other means as well. An important class of sensors utilize the
piezoelectric effect: A charge is generated within certain solid materials when they are de-
formed. This mechanical input /electrical output provides the basis for pressure measurement
as well as displacement and force measurements. Another important type of sensor employs
a diaphragm that deflects when a force is applied, altering an inductance, resistance, or
capacitance. Figure 1.8 shows a piezoelectric pressure sensor together with an automatic data
acquisition system.
Elliptical metal Pointer

Bourdon tube
Pinion
gear
Support
Linkage
Gas at pressure p
Figure 1.7 Pressure measurement by a Figure 1.8 Pressure sensor with automatic data
Bourdon tube gage. acquisition.

1.6 Measuring Temperature
In this section the intensive property temperature is considered along with means for meas-
uring it. Like force, a concept of temperature originates with our sense perceptions. It is
rooted in the notion of the hotness or coldness of a body. We use our sense of touch to
distinguish hot bodies from cold bodies and to arrange bodies in their order of hotness, de-
ciding that 1 is hotter than 2, 2 hotter than 3, and so on. But however sensitive the human
body may be, we are unable to gauge this quality precisely. Accordingly, thermometers and
temperature scales have been devised to measure it.
1.6.1 Thermal Equilibrium

A definition of temperature in terms of concepts that are independently defined or accepted
as primitive is difficult to give. However, it is possible to arrive at an objective understand-
ing of equality of temperature by using the fact that when the temperature of a body changes,
other properties also change.
To illustrate this, consider two copper blocks, and suppose that our senses tell us that one
is warmer than the other. If the blocks were brought into contact and isolated from their sur-
thermal (heat) roundings, they would interact in a way that can be described as a thermal (heat) interaction.
interaction During this interaction, it would be observed that the volume of the warmer block decreases
somewhat with time, while the volume of the colder block increases with time. Eventually,
no further changes in volume would be observed, and the blocks would feel equally warm.
Similarly, we would be able to observe that the electrical resistance of the warmer block de-
creases with time, and that of the colder block increases with time; eventually the electrical
resistances would become constant also. When all changes in such observable properties cease,
thermal equilibrium the interaction is at an end. The two blocks are then in thermal equilibrium. Considerations
such as these lead us to infer that the blocks have a physical property that determines whether
temperature they will be in thermal equilibrium. This property is called temperature, and we may postu-
late that when the two blocks are in thermal equilibrium, their temperatures are equal.
The rate at which the blocks approach thermal equilibrium with one another can be slowed
by separating them with a thick layer of polystyrene foam, rock wool, cork, or other insu-
lating material. Although the rate at which equilibrium is approached can be reduced, no ac-
tual material can prevent the blocks from interacting until they attain the same temperature.
However, by extrapolating from experience, an ideal insulator can be imagined that would
preclude them from interacting thermally. An ideal insulator is called an adiabatic wall. When
a system undergoes a process while enclosed by an adiabatic wall, it experiences no thermal
adiabatic process interaction with its surroundings. Such a process is called an adiabatic process. A process
that occurs at constant temperature is an isothermal process. An adiabatic process is not nec-
isothermal process essarily an isothermal process, nor is an isothermal process necessarily adiabatic.
It is a matter of experience that when two bodies are in thermal equilibrium with a third
body, they are in thermal equilibrium with one another. This statement, which is sometimes
zeroth law of called the zeroth law of thermodynamics, is tacitly assumed in every measurement of tem-
thermodynamics perature. Thus, if we want to know if two bodies are at the same temperature, it is not nec-
essary to bring them into contact and see whether their observable properties change with
time, as described previously. It is necessary only to see if they are individually in thermal
equilibrium with a third body. The third body is usually a thermometer.
1.6.2 Thermometers
Any body with at least one measurable property that changes as its temperature changes can
thermometric property be used as a thermometer. Such a property is called a thermometric property. The particular
1.6 Measuring Temperature 15
Thermodynamics in the News...

Mercury Thermometers The safe disposal of millions of
Quickly Vanishing obsolete mercury-filled thermo-
meters has emerged in its own
The mercury-in-glass fever thermometers, once found in right as an environmental issue.
nearly every medicine cabinet, are a thing of the past. The For proper disposal, thermometers
American Academy of Pediatrics has designated mercury as must be taken to hazardous-waste
too toxic to be present in the home. Families are turning to collection stations rather than sim-
safer alternatives and disposing of mercury thermometers. ply thrown in the trash where they
Proper disposal is an issue, experts say. can be easily broken, releasing
The present generation of liquid-in-glass fever thermome- mercury. Loose fragments of bro-
ters for home use contains patented liquid mixtures that are ken thermometers and anything
nontoxic, safe alternatives to mercury. Battery-powered digital that contacted its mercury should
thermometers also are common today. These devices use the be transported in closed containers
fact that electrical resistance changes predictably with tem- to appropriate disposal sites.
perature to safely check for a fever.
substance that exhibits changes in the thermometric property is known as a thermometric

substance.
A familiar device for temperature measurement is the liquid-in-glass thermometer
pictured in Fig. 1.9a, which consists of a glass capillary tube connected to a bulb filled
with a liquid such as alcohol and sealed at the other end. The space above the liquid is
occupied by the vapor of the liquid or an inert gas. As temperature increases, the liquid
expands in volume and rises in the capillary. The length L of the liquid in the capillary
depends on the temperature. Accordingly, the liquid is the thermometric substance and L
is the thermometric property. Although this type of thermometer is commonly used for
ordinary temperature measurements, it is not well suited for applications where extreme
accuracy is required.
OTHER TEMPERATURE SENSORS
Sensors known as thermocouples are based on the principle that when two dissimilar met-
als are joined, an electromotive force (emf ) that is primarily a function of temperature will
exist in a circuit. In certain thermocouples, one thermocouple wire is platinum of a speci-
fied purity and the other is an alloy of platinum and rhodium. Thermocouples also utilize
Liquid Figure 1.9 Thermometers.

(a) Liquid-in-glass. (b) Infrared-
(a) (b) sensing ear thermometer.
Capillary
Mercury
reservoir
L
Gas bulb
Manometer
Figure 1.10 Constant-volume gas
thermometer.
copper and constantan (an alloy of copper and nickel), iron and constantan, as well as sev-
eral other pairs of materials. Electrical-resistance sensors are another important class of
temperature measurement devices. These sensors are based on the fact that the electrical
resistance of various materials changes in a predictable manner with temperature. The ma-
terials used for this purpose are normally conductors (such as platinum, nickel, or copper)
or semiconductors. Devices using conductors are known as resistance temperature detec-
tors. Semiconductor types are called thermistors. A variety of instruments measure tem-
perature by sensing radiation, such as the ear thermometer shown in Fig. 1.9(b). They are
known by terms such as radiation thermometers and optical pyrometers. This type of
thermometer differs from those previously considered in that it does not actually come in
contact with the body whose temperature is to be determined, an advantage when dealing
with moving objects or bodies at extremely high temperatures. All of these temperature
sensors can be used together with automatic data acquisition.
The constant-volume gas thermometer shown in Fig. 1.10 is so exceptional in terms of pre-
cision and accuracy that it has been adopted internationally as the standard instrument for
calibrating other thermometers. The thermometric substance is the gas (normally hydrogen or
helium), and the thermometric property is the pressure exerted by the gas. As shown in the figure,
the gas is contained in a bulb, and the pressure exerted by it is measured by an open-tube mercury
manometer. As temperature increases, the gas expands, forcing mercury up in the open tube.
The gas is kept at constant volume by raising or lowering the reservoir. The gas thermometer is
used as a standard worldwide by bureaus of standards and research laboratories. However, because
gas thermometers require elaborate apparatus and are large, slowly responding devices that de-
mand painstaking experimental procedures, smaller, more rapidly responding thermometers are
used for most temperature measurements and they are calibrated (directly or indirectly) against
gas thermometers. For further discussion of gas thermometry, see box.
M E A S U R I N G T E M P E R AT U R E W I T H T H E G A S
THERMOMETERTHE GAS SCALE
It is instructive to consider how numerical values are associated with levels of tem-
perature by the gas thermometer shown in Fig. 1.10. Let p stand for the pressure in a
constant-volume gas thermometer in thermal equilibrium with a bath. A value can be
assigned to the bath temperature very simply by a linear relation
T ap (1.11)
where is an arbitrary constant. The linear relationship is an arbitrary choice; other

selections for the correspondence between pressure and temperature could also be
made.
1.6 Measuring Temperature 17
Measured data for a

The value of may be determined by inserting the thermometer into another bath fixed level of
maintained at a standard fixed point: the triple point of water (Sec. 3.2) and measuring temperature, extrapolated
to zero pressure O2
the pressure, call it ptp, of the confined gas at the triple point temperature, 273.16 K.
Substituting values into Eq. 1.16 and solving for N2
p
273.16 p
tp
a He
ptp H2
p
The temperature of the original bath, at which the pressure of the confined gas is p, is then T = 273.16 lim p
tp
T 273.16 a b
p ptp
(1.12)
ptp
Figure 1.11 Read-
However, since the values of both pressures, p and ptp, depend in part on the ings of constant-volume
amount of gas in the bulb, the value assigned by Eq. 1.17 to the bath temperature gas thermometers, when
several gases are used.
varies with the amount of gas in the thermometer. This difficulty is overcome in pre-
cision thermometry by repeating the measurements (in the original bath and the ref-
erence bath) several times with less gas in the bulb in each successive attempt. For
each trial the ratio pptp is calculated from Eq. 1.17 and plotted versus the corre-
sponding reference pressure ptp of the gas at the triple point temperature. When several
such points have been plotted, the resulting curve is extrapolated to the ordinate where
ptp 0. This is illustrated in Fig. 1.11 for constant-volume thermometers with a num-
ber of different gases.
Inspection of Fig. 1.11 shows an important result. At each nonzero value of the ref-
erence pressure, the pptp values differ with the gas employed in the thermometer. How-
ever, as pressure decreases, the pptp values from thermometers with different gases
approach one another, and in the limit as pressure tends to zero, the same value for
pptp is obtained for each gas. Based on these general results, the gas temperature scale
is defined by the relationship
p
T 273.16 lim (1.13)
ptp
where lim means that both p and ptp tend to zero. It should be evident that the de-
termination of temperatures by this means requires extraordinarily careful and elabo-
rate experimental procedures.
Although the temperature scale of Eq. 1.18 is independent of the properties of any
one gas, it still depends on the properties of gases in general. Accordingly, the meas-
urement of low temperatures requires a gas that does not condense at these tempera-
tures, and this imposes a limit on the range of temperatures that can be measured by
a gas thermometer. The lowest temperature that can be measured with such an instru-
ment is about 1 K, obtained with helium. At high temperatures gases dissociate, and
therefore these temperatures also cannot be determined by a gas thermometer. Other
empirical means, utilizing the properties of other substances, must be employed to
measure temperature in ranges where the gas thermometer is inadequate. For further
discussion see Sec. 5.5.
1.6.3 Kelvin Scale

Empirical means of measuring temperature such as considered in Sec. 1.6.2 have inherent
limitations. for example. . . the tendency of the liquid in a liquid-in-glass thermometer
to freeze at low temperatures imposes a lower limit on the range of temperatures that can be
measured. At high temperatures liquids vaporize, and therefore these temperatures also can-
not be determined by a liquid-in-glass thermometer. Accordingly, several different ther-
mometers might be required to cover a wide temperature interval.
In view of the limitations of empirical means for measuring temperature, it is desirable

to have a procedure for assigning temperature values that does not depend on the proper-
ties of any particular substance or class of substances. Such a scale is called a thermodyn-
Kelvin scale amic temperature scale. The Kelvin scale is an absolute thermodynamic temperature scale
that provides a continuous definition of temperature, valid over all ranges of temperature.
Empirical measures of temperature, with different thermometers, can be related to the
Kelvin scale.
To develop the Kelvin scale, it is necessary to use the conservation of energy principle
and the second law of thermodynamics; therefore, further discussion is deferred to Sec. 5.5
after these principles have been introduced. However, we note here that the Kelvin scale has
a zero of 0 K, and lower temperatures than this are not defined.
The Kelvin scale and the gas scale defined by Eq. 1.18 can be shown to be identical in
the temperature range in which a gas thermometer can be used. For this reason we may
write K after a temperature determined by means of constant-volume gas thermometry.
Moreover, until the concept of temperature is reconsidered in more detail in Chap. 5, we
assume that all temperatures referred to in the interim are in accord with values given by
a constant-volume gas thermometer.
1.6.4 Celsius Scale

Temperature scales are defined by the numerical value assigned to a standard fixed point. By
triple point international agreement the standard fixed point is the easily reproducible triple point of water:
the state of equilibrium between steam, ice, and liquid water (Sec. 3.2). As a matter of conven-
ience, the temperature at this standard fixed point is defined as 273.16 kelvins, abbreviated as
273.16 K. This makes the temperature interval from the ice point1 (273.15 K) to the steam point2
equal to 100 K and thus in agreement over the interval with the Celsius scale discussed next,
which assigns 100 Celsius degrees to it. The kelvin is the SI base unit for temperature.
Celsius scale The Celsius temperature scale (formerly called the centigrade scale) uses the unit degree
Celsius (C), which has the same magnitude as the kelvin. Thus, temperature differences are
identical on both scales. However, the zero point on the Celsius scale is shifted to 273.15 K,
as shown by the following relationship between the Celsius temperature and the Kelvin
temperature
T1C2 T1K2 273.15 (1.14)
From this it can be seen that on the Celsius scale the triple point of water is 0.01C and that
0 K corresponds to 273.15C.

1.7 Engineering Design and Analysis
An important engineering function is to design and analyze things intended to meet human
needs. Design and analysis, together with systematic means for approaching them, are
considered in this section.
1
The state of equilibrium between ice and air-saturated water at a pressure of 1 atm.
2
The state of equilibrium between steam and liquid water at a pressure of 1 atm.
K C
373.15
100.0
Steam point
Triple point
273.16
0.01
of water
273.15
0.00
Ice point Celsius
Kelvin
273.15
0.00
Absolute zero
Figure 1.12 Comparison of temperature scales.
1.7.1 Design
Engineering design is a decision-making process in which principles drawn from engineer-
ing and other fields such as economics and statistics are applied, usually iteratively, to de-
vise a system, system component, or process. Fundamental elements of design include the
establishment of objectives, synthesis, analysis, construction, testing, and evaluation. Designs
typically are subject to a variety of constraints related to economics, safety, environmental design constraints
impact, and so on.
Design projects usually originate from the recognition of a need or an opportunity that
is only partially understood. Thus, before seeking solutions it is important to define the
design objectives. Early steps in engineering design include pinning down quantitative per-
formance specifications and identifying alternative workable designs that meet the speci-
fications. Among the workable designs are generally one or more that are best accord-
ing to some criteria: lowest cost, highest efficiency, smallest size, lightest weight, etc. Other
important factors in the selection of a final design include reliability, manufacturability,
maintainability, and marketplace considerations. Accordingly, a compromise must be
sought among competing criteria, and there may be alternative design solutions that are
very similar.3
1.7.2 Analysis
Design requires synthesis: selecting and putting together components to form a coordinated
whole. However, as each individual component can vary in size, performance, cost, and so
on, it is generally necessary to subject each to considerable study or analysis before a final
selection can be made. for example. . . a proposed design for a fire-protection sys-
tem might entail an overhead piping network together with numerous sprinkler heads. Once
an overall configuration has been determined, detailed engineering analysis would be nec-
essary to specify the number and type of the spray heads, the piping material, and the pipe
diameters of the various branches of the network. The analysis must also aim to ensure that
all components form a smoothly working whole while meeting relevant cost constraints and
applicable codes and standards.
3
For further discussion, see A. Bejan, G. Tsatsaronis, and M. J. Moran, Thermal Design and Optimization, John
Wiley & Sons, New York, 1996, Chap. 1
Engineers frequently do analysis, whether explicitly as part of a design process or for

some other purpose. Analyses involving systems of the kind considered in this book use, di-
rectly or indirectly, one or more of three basic laws. These laws, which are independent of
the particular substance or substances under consideration, are
the conservation of mass principle
the conservation of energy principle
the second law of thermodynamics
In addition, relationships among the properties of the particular substance or substances
considered are usually necessary (Chaps. 3, 6, 1114). Newtons second law of motion
(Chaps. 1, 2, 9), relations such as Fouriers conduction model (Chap. 2), and principles of
engineering economics (Chap. 7) may also play a part.
The first steps in a thermodynamic analysis are definition of the system and identification
of the relevant interactions with the surroundings. Attention then turns to the pertinent phys-
ical laws and relationships that allow the behavior of the system to be described in terms of
engineering model an engineering model. The objective in modeling is to obtain a simplified representation of
system behavior that is sufficiently faithful for the purpose of the analysis, even if many as-
pects exhibited by the actual system are ignored. For example, idealizations often used in
mechanics to simplify an analysis and arrive at a manageable model include the assumptions
of point masses, frictionless pulleys, and rigid beams. Satisfactory modeling takes experi-
ence and is a part of the art of engineering.
Engineering analysis is most effective when it is done systematically. This is considered next.
1.7.3 Methodology for Solving Thermodynamics Problems

A major goal of this textbook is to help you learn how to solve engineering problems that
involve thermodynamic principles. To this end numerous solved examples and end-of-chapter
problems are provided. It is extremely important for you to study the examples and solve
problems, for mastery of the fundamentals comes only through practice.
To maximize the results of your efforts, it is necessary to develop a systematic approach.
You must think carefully about your solutions and avoid the temptation of starting problems
in the middle by selecting some seemingly appropriate equation, substituting in numbers, and
quickly punching up a result on your calculator. Such a haphazard problem-solving
approach can lead to difficulties as problems become more complicated. Accordingly, we
strongly recommend that problem solutions be organized using the five steps in the box be-
low, which are employed in the solved examples of this text.
Known: State briefly in your own words what is known. This requires that you read the problem carefully and think
about it.
Find: State concisely in your own words what is to be determined.
Schematic and Given Data: Draw a sketch of the system to be considered. Decide whether a closed system or control vol-
ume is appropriate for the analysis, and then carefully identify the boundary. Label the diagram with relevant information from
the problem statement.
Record all property values you are given or anticipate may be required for subsequent calculations. Sketch appropriate prop-
erty diagrams (see Sec. 3.2), locating key state points and indicating, if possible, the processes executed by the system.
The importance of good sketches of the system and property diagrams cannot be overemphasized. They are often instrumen-
tal in enabling you to think clearly about the problem.
Assumptions: To form a record of how you model the problem, list all simplifying assumptions and idealizations made to
reduce it to one that is manageable. Sometimes this information also can be noted on the sketches of the previous step.
Analysis: Using your assumptions and idealizations, reduce the appropriate governing equations and relationships to forms
that will produce the desired results.
It is advisable to work with equations as long as possible before substituting numerical data. When the equations are reduced
to final forms, consider them to determine what additional data may be required. Identify the tables, charts, or property equa-
tions that provide the required values. Additional property diagram sketches may be helpful at this point to clarify states and
processes.
When all equations and data are in hand, substitute numerical values into the equations. Carefully check that a consistent and
appropriate set of units is being employed. Then perform the needed calculations.
Finally, consider whether the magnitudes of the numerical values are reasonable and the algebraic signs associated with the
numerical values are correct.
The problem solution format used in this text is intended to guide your thinking, not sub-
stitute for it. Accordingly, you are cautioned to avoid the rote application of these five steps,
for this alone would provide few benefits. Indeed, as a particular solution evolves you may
have to return to an earlier step and revise it in light of a better understanding of the problem.
For example, it might be necessary to add or delete an assumption, revise a sketch, deter-
mine additional property data, and so on.
The solved examples provided in the book are frequently annotated with various com-
ments intended to assist learning, including commenting on what was learned, identifying
key aspects of the solution, and discussing how better results might be obtained by relaxing
certain assumptions. Such comments are optional in your solutions.
In some of the earlier examples and end-of-chapter problems, the solution format may
seem unnecessary or unwieldy. However, as the problems become more complicated you will
see that it reduces errors, saves time, and provides a deeper understanding of the problem
at hand.
The example to follow illustrates the use of this solution methodology together with im-
portant concepts introduced previously.
EXAMPLE 1.1 Identifying System Interactions
A wind turbine electric generator is mounted atop a tower. As wind blows steadily across the turbine blades, electricity is
generated. The electrical output of the generator is fed to a storage battery.
(a) Considering only the wind turbineelectric generator as the system, identify locations on the system boundary where the
system interacts with the surroundings. Describe changes occurring within the system with time.
(b) Repeat for a system that includes only the storage battery.
SOLUTION
Known: A wind turbineelectric generator provides electricity to a storage battery.
Find: For a system consisting of (a) the wind turbineelectric generator, (b) the storage battery, identify locations where the
system interacts with its surroundings, and describe changes occurring within the system with time.
Schematic and Given Data:
Part (a)
Air flow Turbinegenerator

Assumptions:
1. In part (a), the system is the control volume shown by

the dashed line on the figure.
2. In part (b), the system is the closed system shown by
the dashed line on the figure.
Electric Part (b) 3. The wind is steady.
current
flow
Storage
battery Thermal
interaction
Figure E1.1
Analysis:
(a) In this case, there is air flowing across the boundary of the control volume. Another principal interaction between the
system and surroundings is the electric current passing through the wires. From the macroscopic perspective, such an interaction
is not considered a mass transfer, however. With a steady wind, the turbinegenerator is likely to reach steady-state operation,
where the rotational speed of the blades is constant and a steady electric current is generated.
(b) The principal interaction between the system and its surroundings is the electric current passing into the battery through
the wires. As noted in part (a), this interaction is not considered a mass transfer. The system is a closed system. As the bat-
tery is charged and chemical reactions occur within it, the temperature of the battery surface may become somewhat elevated
and a thermal interaction might occur between the battery and its surroundings. This interaction is likely to be of secondary
importance.
Using terms familiar from a previous physics course, the system of part (a) involves the conversion of kinetic energy to
electricity, whereas the system of part (b) involves energy storage within the battery.
Chapter Summary and Study Guide
In this chapter, we have introduced some of the fundamental states as well as quasiequilibrium processes during which the
concepts and definitions used in the study of thermodynam- departure from equilibrium is negligible.
ics. The principles of thermodynamics are applied by engi- In this chapter, we have introduced SI units for mass,
neers to analyze and design a wide variety of devices intended length, time, force, and temperature. You will need to be fa-
to meet human needs. miliar of units as you use this book.
An important aspect of thermodynamic analysis is to iden- Chapter 1 concludes with discussions of how thermody-
tify systems and to describe system behavior in terms of prop- namics is used in engineering design and how to solve ther-
erties and processes. Three important properties discussed in modynamics problems systematically.
this chapter are specific volume, pressure, and temperature. This book has several features that facilitate study and con-
In thermodynamics, we consider systems at equilibrium tribute to understanding. For an overview, see How To Use
states and systems undergoing changes of state. We study This Book Effectively.
processes during which the intervening states are not equilibrium
Problems: Developing Engineering Skills 23
The following checklist provides a study guide for this work on a molar basis using Eq. 1.5.
chapter. When your study of the text and the end-of-chapter identify an appropriate system boundary and describe the
exercises has been completed you should be able to interactions between the system and its surroundings.
write out the meanings of the terms listed in the margin apply the methodology for problem solving discussed in
throughout the chapter and understand each of the Sec. 1.7.3.
related concepts. The subset of key concepts listed below
is particularly important in subsequent chapters.
Key Engineering Concepts
surroundings p. 3 process p. 5 pure substance p. 6 isothermal

boundary p. 3 thermodynamic equilibrium p. 7 process p. 14
closed system p. 3 cycle p. 5 specific volume p. 10 Kelvin scale p. 18
control volume p. 3 extensive property p. 6 pressure p. 11 Rankine scale p.
property p. 5 intensive property p. 6 temperature p. 14
state p. 5 phase p. 6 adiabatic process p. 14
Exercises: Things Engineers Think About
1. For an everyday occurrence, such as cooking, heating or cool- 5. Air at normal temperature and pressure contained in a closed
ing a house, or operating an automobile or a computer, make a tank adheres to the continuum hypothesis. Yet when sufficient air
sketch of what you observe. Define system boundaries for ana- has been drawn from the tank, the hypothesis no longer applies
lyzing some aspect of the events taking place. Identify interac- to the remaining air. Why?
tions between the systems and their surroundings. 6. Can the value of an intensive property be uniform with posi-
2. What are possible boundaries for studying each of the tion throughout a system? Be constant with time? Both?
following?
7. A data sheet indicates that the pressure at the inlet to a pump
(a) a bicycle tire inflating.
is 10 kPa. What might the negative pressure denote?
(b) a cup of water being heated in a microwave oven.
(c) a household refrigerator in operation. 8. We commonly ignore the pressure variation with elevation for
(d) a jet engine in flight. a gas inside a storage tank. Why?
(e) cooling a desktop computer. 9. When buildings have large exhaust fans, exterior doors can be
(f) a residential gas furnace in operation. difficult to open due to a pressure difference between the inside
(g) a rocket launching. and outside. Do you think you could open a 3- by 7-ft door if the
3. Considering a lawnmower driven by a one-cylinder gasoline inside pressure were 1 in. of water (vacuum)?
engine as the system, would this be best analyzed as a closed sys- 10. What difficulties might be encountered if water were used
tem or a control volume? What are some of the environmental as the thermometric substance in the liquid-in-glass thermome-
impacts associated with the system? Repeat for an electrically ter of Fig. 1.9?
driven lawnmower.
11. Look carefully around your home, automobile, or place of
4. A closed system consists of still air at 1 atm, 20C in a closed
employment, and list all the measuring devices you find. For each,
vessel. Based on the macroscopic view, the system is in equilib-
try to explain the principle of operation.
rium, yet the atoms and molecules that make up the air are in
continuous motion. Reconcile this apparent contradiction.
Problems: Developing Engineering Skills
Exploring System Concepts 1.2 As illustrated in Fig. P1.2, electric current from a storage
1.1 Referring to Figs. 1.1 and 1.2, identify locations on the battery runs an electric motor. The shaft of the motor is con-
boundary of each system where there are interactions with the nected to a pulleymass assembly that raises a mass. Consid-
surroundings. ering the motor as a system, identify locations on the system
boundary where the system interacts with its surroundings and 1.5 As illustrated in Fig. P1.5, water for a fire hose is drawn
describe changes that occur within the system with time. Re- from a pond by a gasoline engine driven pump. Consider-
peat for an enlarged system that also includes the battery and ing the engine-driven pump as a system, identify locations
pulleymass assembly. on the system boundary where the system interacts with its
surroundings and describe events occurring within the sys-
tem. Repeat for an enlarged system that includes the hose and
the nozzle.
Battery Motor
Nozzle
Mass
Figure P1.2
1.3 As illustrated in Fig. P1.3, water circulates between a stor-

age tank and a solar collector. Heated water from the tank is
used for domestic purposes. Considering the solar collector as
a system, identify locations on the system boundary where the
system interacts with its surroundings and describe events that
occur within the system. Repeat for an enlarged system that
includes the storage tank and the interconnecting piping.
Hot water
supply
Intake hose
Pond
Hot water
Solar storage Figure P1.5
collector tank
Circulating
pump Cold water
return 1.6 A system consists of liquid water in equilibrium with a
gaseous mixture of air and water vapor. How many phases
are present? Does the system consist of a pure substance?
+
Explain. Repeat for a system consisting of ice and liquid
water in equilibrium with a gaseous mixture of air and water
Figure P1.3
vapor.
1.4 As illustrated in Fig. P1.4, steam flows through a valve and 1.7 A system consists of liquid oxygen in equilibrium with oxy-
turbine in series. The turbine drives an electric generator. Con- gen vapor. How many phases are present? The system under-
sidering the valve and turbine as a system, identify locations goes a process during which some of the liquid is vaporized.
on the system boundary where the system interacts with its Can the system be viewed as being a pure substance during
surroundings and describe events occurring within the system. the process? Explain.
Repeat for an enlarged system that includes the generator.
1.8 A system consisting of liquid water undergoes a process.
At the end of the process, some of the liquid water has frozen,
Steam + and the system contains liquid water and ice. Can the system
Turbine Generator be viewed as being a pure substance during the process?

Valve Explain.
1.9 A dish of liquid water is placed on a table in a room. Af-
ter a while, all of the water evaporates. Taking the water and
the air in the room to be a closed system, can the system be
Steam regarded as a pure substance during the process? After the
Figure P1.4 process is completed? Discuss.
Working with Force and Mass

1.10 An object weighs 25 kN at a location where the acceler-
ation of gravity is 9.8 m/s2. Determine its mass, in kg.
1.11 An object whose mass is 10 kg weighs 95 N. Determine
(a) the local acceleration of gravity, in m/s2.
(b) the mass, in kg, and the weight, in N, of the object at a
location where g 9.81 m/s2.
1.12 Atomic and molecular weights of some common sub-
stances are listed in Appendix Table A-1. Using data from the
appropriate table, determine the mass, in kg, of 10 kmol of
each of the following: air, H2O, Cu, SO2.
1.13 When an object of mass 5 kg is suspended from a spring, L=2m
the spring is observed to stretch by 8 cm. The deflection of the
z
spring is related linearly to the weight of the suspended mass.
What is the proportionality constant, in newton per cm, if g
9.81 m/s2?
D = 0.5 m
1.14 A simple instrument for measuring the acceleration of Figure P1.20
gravity employs a linear spring from which a mass is sus-
pended. At a location on earth where the acceleration of grav- Using Specific Volume and Pressure
ity is 9.81 m/s2, the spring extends 0.739 cm. If the spring ex-
1.21 Fifteen kg of carbon dioxide (CO2) gas is fed to a cylin-
tends 0.116 in. when the instrument is on Mars, what is the
der having a volume of 20 m3 and initially containing 15 kg
Martian acceleration of gravity? How much would the spring
of CO2 at a pressure of 10 bar. Later a pinhole develops and
extend on the moon, where g 1.67 m/s2?
the gas slowly leaks from the cylinder.
1.15 Estimate the magnitude of the force, in N, exerted by a
(a) Determine the specific volume, in m3/kg, of the CO2 in the
seat belt on a 25 kg child during a frontal collision that decel-
cylinder initially. Repeat for the CO2 in the cylinder after
erates a car from 8 km/h to rest in 0.1 s. Express the cars de-
the 15 kg has been added.
celeration in multiples of the standard acceleration of gravity,
(b) Plot the amount of CO2 that has leaked from the cylinder,
or gs.
in kg, versus the specific volume of the CO2 remaining in
1.16 An object whose mass is 2 kg is subjected to an applied the cylinder. Consider v ranging up to 1.0 m3/kg.
upward force. The only other force acting on the object is the 1.22 The following table lists temperatures and specific vol-
force of gravity. The net acceleration of the object is upward umes of water vapor at two pressures:
with a magnitude of 5 m/s2. The acceleration of gravity is
9.81 m/s2. Determine the magnitude of the applied upward
force, in N. p 1.0 MPa p 1.5 Mpa
3
1.17 A closed system consists of 0.5 kmol of liquid water and T (C) v (m /kg) T (C) v (m3/kg)
occupies a volume of 4 103 m3. Determine the weight of 200 0.2060 200 0.1325
the system, in N, and the average density, in kg/m3, at a loca- 240 0.2275 240 0.1483
tion where the acceleration of gravity is g 9.81 m/s2. 280 0.2480 280 0.1627
1.18 The weight of an object on an orbiting space vehicle is
measured to be 42 N based on an artificial gravitational ac- Data encountered in solving problems often do not fall exactly
celeration of 6 m/s2. What is the weight of the object, in N, on on the grid of values provided by property tables, and linear
earth, where g 9.81 m/s2? interpolation between adjacent table entries becomes neces-
1.19 If the variation of the acceleration of gravity, in m/s2, with sary. Using the data provided here, estimate
elevation z, in m, above sea level is g 9.81 (3.3 106)z, (a) the specific volume at T 240C, p 1.25 MPa, in m3/kg.
determine the percent change in weight of an airliner landing (b) the temperature at p 1.5 MPa, v 0.1555 m3/kg, in C.
from a cruising altitude of 10 km on a runway at sea level. (c) the specific volume at T 220C, p 1.4 MPa, in m3/kg.
1.20 As shown in Fig. P1.21, a cylinder of compacted scrap 1.23 A closed system consisting of 5 kg of a gas undergoes a
metal measuring 2 m in length and 0.5 m in diameter is process during which the relationship between pressure and
suspended from a spring scale at a location where the accel- specific volume is pv1.3 constant. The process begins with
eration of gravity is 9.78 m/s2. If the scrap metal density, in p1 1 bar, v1 0.2 m3/kg and ends with p2 0.25 bar. De-
kg/m3, varies with position z, in m, according to 7800 termine the final volume, in m3, and plot the process on a graph
360(zL)2, determine the reading of the scale, in N. of pressure versus specific volume.
1.24 A gas initially at p1 1 bar and occupying a volume of 1.29 Figure P1.29 shows a tank within a tank, each containing
1 liter is compressed within a pistoncylinder assembly to a air. Pressure gage A is located inside tank B and reads 1.4 bar.
final pressure p2 4 bar. The U-tube manometer connected to tank B contains mercury.
Using data on the diagram, determine the absolute pressures
(a) If the relationship between pressure and volume during the
inside tank A and tank B, each in bar. The atmospheric pres-
compression is pV constant, determine the volume, in
sure surrounding tank B is 101 kPa. The acceleration of grav-
liters, at a pressure of 3 bar. Also plot the overall process
ity is g 9.81 m/s2.
on a graph of pressure versus volume.
(b) Repeat for a linear pressurevolume relationship between
the same end states.
1.25 A gas contained within a pistoncylinder assembly un-
dergoes a thermodynamic cycle consisting of three processes:
Tank B patm = 101 kPa
Process 12: Compression with pV constant from p1 1 bar,
V1 1.0 m3 to V2 0.2 m3
Process 23: Constant-pressure expansion to V3 1.0 m3
Process 31: Constant volume L = 20 cm
Sketch the cycle on a pV diagram labeled with pressure and Tank A

volume values at each numbered state. Gage A
1.26 As shown in Fig. 1.6, a manometer is attached to a tank

of gas in which the pressure is 104.0 kPa. The manometer liq-
uid is mercury, with a density of 13.59 g/cm3. If g 9.81 m/s2 pgage, A = 1.4 bar Mercury ( = 13.59 g/cm3)
and the atmospheric pressure is 101.33 kPa, calculate g = 9.81 m/s2
(a) the difference in mercury levels in the manometer, in cm. Figure P1.29
(b) the gage pressure of the gas, in kPa.
1.27 The absolute pressure inside a tank is 0.4 bar, and the sur-
rounding atmospheric pressure is 98 kPa. What reading would 1.30 A vacuum gage indicates that the pressure of air in a closed
a Bourdon gage mounted in the tank wall give, in kPa? Is this chamber is 0.2 bar (vacuum). The pressure of the surrounding
a gage or vacuum reading? atmosphere is equivalent to a 750-mm column of mercury. The
density of mercury is 13.59 g/cm3, and the acceleration of grav-
1.28 Water flows through a Venturi meter, as shown in Fig. ity is 9.81 m/s2. Determine the absolute pressure within the
P1.28. The pressure of the water in the pipe supports columns chamber, in bar.
of water that differ in height by 30 cm. Determine the dif-
1.31 Refrigerant 22 vapor enters the compressor of a refrigera-
ference in pressure between points a and b, in MPa. Does
tion system at an absolute pressure of .1379 MPa.2 A pressure
the pressure increase or decrease in the direction of flow?
gage at the compressor exit indicates a pressure of 1.93 MPa.2
The atmospheric pressure is 1 bar, the specific volume of water
(gage). The atmospheric pressure is .1007 MPa.2 Determine
is 103 m3/kg, and the acceleration of gravity is g 9.81 m/s2.
the change in absolute pressure from inlet to exit, in MPa.2,
and the ratio of exit to inlet pressure.
1.32 Air contained within a vertical pistoncylinder assembly
is shown in Fig. P1.32. On its top, the 10-kg piston is attached
to a spring and exposed to an atmospheric pressure of 1 bar.
Initially, the bottom of the piston is at x 0, and the spring
exerts a negligible force on the piston. The valve is opened and
patm = 1 bar air enters the cylinder from the supply line, causing the vol-
g = 9.81 m/s2
ume of the air within the cylinder to increase by 3.9 104 m3.
L = 30 cm. The force exerted by the spring as the air expands within the
Water
= 103 m3/kg cylinder varies linearly with x according to
Fspring kx
where k 10,000 N/m. The piston face area is 7.8 103 m2.
Ignoring friction between the piston and the cylinder wall,
a b determine the pressure of the air within the cylinder, in bar,
when the piston is in its initial position. Repeat when the piston
is in its final position. The local acceleration of gravity is
Figure P1.28 9.81 m/s2.
patm 1.37 Derive Eq. 1.10 and use it to determine the gage pressure,
in bar, equivalent to a manometer reading of 1 cm of water (den-
sity 1000 kg/m3). Repeat for a reading of 1 cm of mercury.
Air The density of mercury is 13.59 times that of water.

supply
Exploring Temperature
x=0 line
Valve 1.38 Two temperature measurements are taken with a ther-
Air
mometer marked with the Celsius scale. Show that the
difference between the two readings would be the same if the
temperatures were converted to the Kelvin scale.
1.39 The relation between resistance R and temperature T for
Figure P1.32 a thermistor closely follows
R R0 exp c b a bd
1.33 Determine the total force, in kN, on the bottom of a 1 1
100 50 m swimming pool. The depth of the pool varies lin- T T0
early along its length from 1 m to 4 m. Also, determine the where R0 is the resistance, in ohms ( ), measured at temper-
pressure on the floor at the center of the pool, in kPa. The ature T0 (K) and is a material constant with units of K. For
atmospheric pressure is 0.98 bar, the density of the water is a particular thermistor R0 2.2 at T0 310 K. From a cal-
998.2 kg/m3, and the local acceleration of gravity is 9.8 m/s2. ibration test, it is found that R 0.31 at T 422 K. De-
1.34 Figure P1.34 illustrates an inclined manometer making an termine the value of for the thermistor and make a plot of
angle of with the horizontal. What advantage does an in- resistance versus temperature.
clined manometer have over a U-tube manometer? Explain. 1.40 Over a limited temperature range, the relation between
electrical resistance R and temperature T for a resistance tem-
perature detector is
R R0 31
a1T T0 2 4
where R0 is the resistance, in ohms ( ), measured at reference
temperature T0 (in C) and is a material constant with units
of (C)1. The following data are obtained for a particular re-
sistance thermometer:
Figure P1.34
T (C) R ( )
1.35 The variation of pressure within the biosphere affects not Test 1 (T0) 0 (R0) 51.39
only living things but also systems such as aircraft and under- Test 2 91 51.72
sea exploration vehicles.
What temperature would correspond to a resistance of 51.47
(a) Plot the variation of atmospheric pressure, in atm, versus on this thermometer?
elevation z above sea level, in km, ranging from 0 to 10 km. 1.41 A new absolute temperature scale is proposed. On this scale
Assume that the specific volume of the atmosphere, in the ice point of water is 150S and the steam point is 300S. De-
m3/kg, varies with the local pressure p, in kPa, according termine the temperatures in C that correspond to 100 and 400S,
to v 72.435p. respectively. What is the ratio of the size of the S to the kelvin?
(b) Plot the variation of pressure, in atm, versus depth z be-
low sea level, in km, ranging from 0 to 2 km. Assume that 1.42 As shown in Fig. P1.42, a small-diameter water pipe passes
the specific volume of seawater is constant, v 0.956 through the 6-in.-thick exterior wall of a dwelling. Assuming
103 m3/kg. that temperature varies linearly with position x through the wall
from 20C to 6C, would the water in the pipe freeze?
In each case, g 9.81 m/s2 and the pressure at sea level is
1 atm.
T = 20C T = 6C
1.36 One thousand kg of natural gas at 100 bar and 255 K is
stored in a tank. If the pressure, p, specific volume, v, and tem- Pipe
perature, T, of the gas are related by the following expression
p 3 15.18 103 2T 1v 0.0026682 4 18.91 103 2 v2 3 in.
where v is in m3/kg, T is in K, and p is in bar, determine the 6 in.

volume of the tank in m3. Also, plot pressure versus specific x
volume for the isotherms T 250 K, 500 K, and 1000 K. Figure P1.42
Design & Open Ended Problems: Exploring Engineering Practice

1.1D The issue of global warming is receiving considerable at- 1.7D Obtain manufacturers data on thermocouple and ther-
tention these days. Write a technical report on the subject of mistor temperature sensors for measuring temperatures of hot
global warming. Explain what is meant by the term global combustion gases from a furnace. Explain the basic operating
warming and discuss objectively the scientific evidence that is principles of each sensor and compare the advantages and
cited as the basis for the argument that global warming is disadvantages of each device. Consider sensitivity, accuracy,
occurring. calibration, and cost.
1.2D Economists and others speak of sustainable development 1.8D The International Temperature Scale was first adopted by
as a means for meeting present human needs without com- the International Committee on Weights and Measures in 1927
promising the ability of future generations to meet their own to provide a global standard for temperature measurement. This
needs. Research the concept of sustainable development, and scale has been refined and extended in several revisions, most
write a paper objectively discussing some of the principal recently in 1990 (International Temperature Scale of 1990,
issues associated with it. ITS-90). What are some of the reasons for revising the scale?
1.3D Write a report reviewing the principles and objectives of What are some of the principal changes that have been made
statistical thermodynamics. How does the macroscopic ap- since 1927?
proach to thermodynamics of the present text differ from this? 1.9D A facility is under development for testing valves used in
Explain. nuclear power plants. The pressures and temperatures of flow-
1.4D Methane-laden gas generated by the decomposition of ing gases and liquids must be accurately measured as part of
landfill trash is more commonly flared than exploited for some the test procedure. The American National Standards Institute
useful purpose. Research literature on the possible uses of land- (ANSI) and the American Society of Heating, Refrigerating,
fill gas and write a report of your findings. Does the gas rep- and Air Conditioning Engineers (ASHRAE) have adopted stan-
resent a significant untapped resource? Discuss. dards for pressure and temperature measurement. Obtain copies
1.5D You are asked to address a city council hearing concern- of the relevant standards, and prepare a memorandum discussing
ing the decision to purchase a commercially available 10-kW what standards must be met in the design of the facility and
wind turbinegenerator having an expected life of 12 or more what requirements those standards place on the design.
years. As an engineer, what considerations will you point out 1.10D List several aspects of engineering economics relevant
to the council members to help them with their decision? to design. What are the important contributors to cost that
1.6D Develop a schematic diagram of an automatic data acqui- should be considered in engineering design? Discuss what is
sition system for sampling pressure data inside the cylinder of meant by annualized costs.
a diesel engine. Determine a suitable type of pressure transd- 1.11D Mercury Thermometers Quickly Vanishing (see box
ucer for this purpose. Investigate appropriate computer software Sec. 1.6). Investigate the medical complications of mercury ex-
for running the system. Write a report of your findings. posure. Write a report including at least three references.
C
H
A
P
T
Energy and the
First Law of
E
R 2
Thermodynamics
E N G I N E E R I N G C O N T E X T Energy is a fundamental concept of
thermodynamics and one of the most significant aspects of engineering analysis. In
this chapter we discuss energy and develop equations for applying the principle of
conservation of energy. The current presentation is limited to closed systems. In Chap. 4
the discussion is extended to control volumes.
Energy is a familiar notion, and you already know a great deal about it. In the present
chapter several important aspects of the energy concept are developed. Some of these
you have encountered before. A basic idea is that energy can be stored within systems in
various forms. Energy also can be converted from one form to another and transferred
between systems. For closed systems, energy can be transferred by work and heat
transfer. The total amount of energy is conserved in all conversions and transfers.
The objective of this chapter is to organize these ideas about energy into forms chapter objective
suitable for engineering analysis. The presentation begins with a review of energy
concepts from mechanics. The thermodynamic concept of energy is then introduced as
an extension of the concept of energy in mechanics.
2.1 Reviewing Mechanical

Concepts of Energy
Building on the contributions of Galileo and others, Newton formulated a general descrip-
tion of the motions of objects under the influence of applied forces. Newtons laws of motion,
which provide the basis for classical mechanics, led to the concepts of work, kinetic energy,
and potential energy, and these led eventually to a broadened concept of energy. The present
discussion begins with an application of Newtons second law of motion.
WORK AND KINETIC ENERGY
The curved line in Fig. 2.1 represents the path of a body of mass m (a closed system) mov-
ing relative to the xy coordinate frame shown. The velocity of the center of mass of the
body is denoted by V.1 The body is acted on by a resultant force F, which may vary in
magnitude from location to location along the path. The resultant force is resolved into a
component Fs along the path and a component Fn normal to the path. The effect of the
1
Boldface symbols denote vectors. Vector magnitudes are shown in lightface type.
29
30 Chapter 2 Energy and the First Law of Thermodynamics
y Fs
Path
V
ds
F
s
Body
Fn
0
Figure 2.1 Forces acting on a moving

x system.
component Fs is to change the magnitude of the velocity, whereas the effect of the compo-
nent Fn is to change the direction of the velocity. As shown in Fig. 2.1, s is the instantaneous
position of the body measured along the path from some fixed point denoted by 0. Since the
magnitude of F can vary from location to location along the path, the magnitudes of Fs and
Fn are, in general, functions of s.
Let us consider the body as it moves from s s1, where the magnitude of its velocity is V1,
to s s2, where its velocity is V2. Assume for the present discussion that the only interaction
between the body and its surroundings involves the force F. By Newtons second law of motion,
the magnitude of the component Fs is related to the change in the magnitude of V by
dV
Fs m (2.1)
dt
Using the chain rule, this can be written as
d V ds dV
Fs m mV (2.2)
ds dt ds
where V dsdt. Rearranging Eq. 2.2 and integrating from s1 to s2 gives
s2

V2
mV d V Fs ds (2.3)
V1 s1
The integral on the left of Eq. 2.3 is evaluated as follows

V2
mV d V mV2 d m 1V22 V21 2

V2 1 1
(2.4)
V1 2 V1 2
kinetic energy The quantity 12mV2 is the kinetic energy, KE, of the body. Kinetic energy is a scalar quan-
tity. The change in kinetic energy, KE, of the body is2
KE KE2 KE1 m 1V22 V21 2

1
(2.5)
2
work The integral on the right of Eq. 2.3 is the work of the force Fs as the body moves from s1 to
s2 along the path. Work is also a scalar quantity.
With Eq. 2.4, Eq. 2.3 becomes
s2
m 1V22 V21 2
1
F # ds (2.6)
2 s1
2
The symbol always means final value minus initial value.
2.1 Reviewing Mechanical Concepts of Energy 31
Thermodynamics in the News

Hybrids Harvest Energy stored energy assists
the engine, these cars
Ever wonder what happens to the kinetic energy when you get better fuel econ-
step on the brakes of your moving car? Automotive engineers omy than comparably
have, and the result is the hybrid electric vehicle combining sized conventional
an electric motor with a small conventional engine. vehicles.
When a hybrid is braked, some of its kinetic energy is har- To further reduce fuel consumption, hybrids are designed
vested and stored in batteries. The electric motor calls on the with minimal aerodynamic drag, and many parts are made
stored energy to help the car start up again. A specially de- from sturdy, lightweight materials such as carbon fiber-metal
signed transmission provides the proper split between the en- composites. Some models now on the market achieve gas
gine and the electric motor to minimize fuel use. Because mileage as high as 6070 miles per gallon, manufacturers say.
where the expression for work has been written in terms of the scalar product (dot product)
of the force vector F and the displacement vector ds. Equation 2.6 states that the work of the
resultant force on the body equals the change in its kinetic energy. When the body is accel-
erated by the resultant force, the work done on the body can be considered a transfer of
energy to the body, where it is stored as kinetic energy.
Kinetic energy can be assigned a value knowing only the mass of the body and the mag-
nitude of its instantaneous velocity relative to a specified coordinate frame, without regard
for how this velocity was attained. Hence, kinetic energy is a property of the body. Since
kinetic energy is associated with the body as a whole, it is an extensive property.
UNITS. Work has units of force times distance. The units of kinetic energy are the same as
for work. In SI, the energy unit is the newton-meter, N # m, called the joule, J. In this book
it is convenient to use the kilojoule, kJ.
POTENTIAL ENERGY
Equation 2.6 is the principal result of the previous section. Derived from Newtons second
law, the equation gives a relationship between two defined concepts: kinetic energy and work.
In this section it is used as a point of departure to extend the concept of energy. To begin,
refer to Fig. 2.2, which shows a body of mass m that moves vertically from an elevation z1 R
to an elevation z2 relative to the surface of the earth. Two forces are shown acting on the sys- z2
tem: a downward force due to gravity with magnitude mg and a vertical force with magni-
tude R representing the resultant of all other forces acting on the system.
z mg z1
The work of each force acting on the body shown in Fig. 2.2 can be determined by
using the definition previously given. The total work is the algebraic sum of these indi- Earths surface
vidual values. In accordance with Eq. 2.6, the total work equals the change in kinetic
energy. That is Figure 2.2 Illustra-
z2 z2
tion used to introduce the
m 1V22 V21 2
1 potential energy concept.
R dz mg dz (2.7)
2 z1 z1
A minus sign is introduced before the second term on the right because the gravitational
force is directed downward and z is taken as positive upward.
The first integral on the right of Eq. 2.7 represents the work done by the force R on the
body as it moves vertically from z1 to z2. The second integral can be evaluated as follows
z2
mg dz mg 1z2 z1 2 (2.8)
z1
where the acceleration of gravity has been assumed to be constant with elevation. By incor-
porating Eq. 2.8 into Eq. 2.7 and rearranging
z2
m 1V22 V21 2
mg 1z2 z1 2
1
R dz (2.9)
2 z1
gravitational potential The quantity mgz is the gravitational potential energy, PE. The change in gravitational
energy potential energy, PE, is
PE PE2 PE1 mg 1z2 z1 2 (2.10)
The units for potential energy in any system of units are the same as those for kinetic en-
ergy and work.
Potential energy is associated with the force of gravity and is therefore an attribute of a
system consisting of the body and the earth together. However, evaluating the force of grav-
ity as mg enables the gravitational potential energy to be determined for a specified value of
g knowing only the mass of the body and its elevation. With this view, potential energy is
regarded as an extensive property of the body. Throughout this book it is assumed that ele-
vation differences are small enough that the gravitational force can be considered constant.
The concept of gravitational potential energy can be formulated to account for the variation
of the gravitational force with elevation, however.
To assign a value to the kinetic energy or the potential energy of a system, it is necessary
to assume a datum and specify a value for the quantity at the datum. Values of kinetic and
potential energy are then determined relative to this arbitrary choice of datum and reference
value. However, since only changes in kinetic and potential energy between two states are
required, these arbitrary reference specifications cancel.
When a system undergoes a process where there are changes in kinetic and potential en-
ergy, special care is required to obtain a consistent set of units.
for example. . . to illustrate the proper use of units in the calculation of such terms,
consider a system having a mass of 1 kg whose velocity increases from 15 m/s to 30 m/s
while its elevation decreases by 10 m at a location where g 9.7 m/s2. Then
KE m 1V22 V21 2
1
2
m 2 m 2
11 kg2 c a30 b a15 b d ` ` ` `
1 1N 1 kJ

2 s s 1 kg # m /s2 103 N # m
0.34 kJ
PE mg 1z2 z1 2
11 kg2 a9.7 b 110 m2 ` ` ` `

m 1N 1 kJ
s2 1 kg # m /s2 103 N # m
0.10 kJ
CONSERVATION OF ENERGY IN MECHANICS
Equation 2.9 states that the total work of all forces acting on the body from the surround-
ings, with the exception of the gravitational force, equals the sum of the changes in the kinetic
and potential energies of the body. When the resultant force causes the elevation to be
increased, the body to be accelerated, or both, the work done by the force can be considered
2.2 Broadening Our Understanding of Work 33
a transfer of energy to the body, where it is stored as gravitational potential energy and/or
kinetic energy. The notion that energy is conserved underlies this interpretation.
The interpretation of Eq. 2.9 as an expression of the conservation of energy principle can
be reinforced by considering the special case of a body on which the only force acting is that
due to gravity, for then the right side of the equation vanishes and the equation reduces to
m 1V22 V21 2
mg 1z2 z1 2 0
1
2
z mg
or (2.11)
1 1
mV22
mgz2 mV21
mgz1
2 2
Under these conditions, the sum of the kinetic and gravitational potential energies remains
constant. Equation 2.11 also illustrates that energy can be converted from one form to an-
other: For an object falling under the influence of gravity only, the potential energy would
decrease as the kinetic energy increases by an equal amount.
CLOSURE
The presentation thus far has centered on systems for which applied forces affect only their
overall velocity and position. However, systems of engineering interest normally interact with
their surroundings in more complicated ways, with changes in other properties as well. To
analyze such systems, the concepts of kinetic and potential energy alone do not suffice, nor
does the rudimentary conservation of energy principle introduced in this section. In thermo-
dynamics the concept of energy is broadened to account for other observed changes, and the
principle of conservation of energy is extended to include a wide variety of ways in which
systems interact with their surroundings. The basis for such generalizations is experimental
evidence. These extensions of the concept of energy are developed in the remainder of the
chapter, beginning in the next section with a fuller discussion of work.

2.2 Broadening Our Understanding of Work
The work W done by, or on, a system evaluated in terms of macroscopically observable forces
and displacements is
s2
W s1
F # ds (2.12)
This relationship is important in thermodynamics, and is used later in the present section to
evaluate the work done in the compression or expansion of gas (or liquid), the extension of
a solid bar, and the stretching of a liquid film. However, thermodynamics also deals with
phenomena not included within the scope of mechanics, so it is necessary to adopt a broader
interpretation of work, as follows.
A particular interaction is categorized as a work interaction if it satisfies the following cri-
terion, which can be considered the thermodynamic definition of work: Work is done by a thermodynamic
system on its surroundings if the sole effect on everything external to the system could have definition of work
been the raising of a weight. Notice that the raising of a weight is, in effect, a force acting
through a distance, so the concept of work in thermodynamics is a natural extension of the
Paddle
wheel System A
Gas System B
a b
Battery
Figure 2.3 Two examples of
work.
concept of work in mechanics. However, the test of whether a work interaction has taken
place is not that the elevation of a weight has actually taken place, or that a force has actu-
ally acted through a distance, but that the sole effect could have been an increase in the
elevation of a weight.
for example. . . consider Fig. 2.3 showing two systems labeled A and B. In
system A, a gas is stirred by a paddle wheel: the paddle wheel does work on the gas. In
principle, the work could be evaluated in terms of the forces and motions at the boundary
between the paddle wheel and the gas. Such an evaluation of work is consistent with Eq. 2.12,
where work is the product of force and displacement. By contrast, consider system B, which
includes only the battery. At the boundary of system B, forces and motions are not evident.
Rather, there is an electric current i driven by an electrical potential difference existing
across the terminals a and b. That this type of interaction at the boundary can be classified
as work follows from the thermodynamic definition of work given previously: We can
imagine the current is supplied to a hypothetical electric motor that lifts a weight in the
surroundings.
Work is a means for transferring energy. Accordingly, the term work does not refer to
what is being transferred between systems or to what is stored within systems. Energy is
transferred and stored when work is done.
2.2.1 Sign Convention and Notation

Engineering thermodynamics is frequently concerned with devices such as internal combus-
tion engines and turbines whose purpose is to do work. Hence, in contrast to the approach
generally taken in mechanics, it is often convenient to consider such work as positive. That
is,
W 7 0: work done by the system
sign convention for work
W 6 0: work done on the system
This sign convention is used throughout the book. In certain instances, however, it is con-
venient to regard the work done on the system to be positive, as has been done in the dis-
cussion of Sec. 2.1. To reduce the possibility of misunderstanding in any such case, the
direction of energy transfer is shown by an arrow on a sketch of the system, and work is re-
garded as positive in the direction of the arrow.
To evaluate the integral in Eq. 2.12, it is necessary to know how the force varies with the
displacement. This brings out an important idea about work: The value of W depends on the
details of the interactions taking place between the system and surroundings during a process
and not just the initial and final states of the system. It follows that work is not a property work is not a property
of the system or the surroundings. In addition, the limits on the integral of Eq. 2.12 mean
from state 1 to state 2 and cannot be interpreted as the values of work at these states. The
notion of work at a state has no meaning, so the value of this integral should never be indi-
cated as W2 W1.
The differential of work, W, is said to be inexact because, in general, the following in-
tegral cannot be evaluated without specifying the details of the process
2
1
dW W
On the other hand, the differential of a property is said to be exact because the change in
a property between two particular states depends in no way on the details of the process
linking the two states. For example, the change in volume between two states can be de-
termined by integrating the differential dV, without regard for the details of the process,
as follows

V2
dV V2 V1
V1
where V1 is the volume at state 1 and V2 is the volume at state 2. The differential of every
property is exact. Exact differentials are written, as above, using the symbol d. To stress the
difference between exact and inexact differentials, the differential of work is written as W.
The symbol is also used to identify other inexact differentials encountered later.
2.2.2 Power
Many thermodynamic analyses are concerned with the time rate at which energy # transfer
occurs. The rate of energy transfer by work is called power and is denoted by W. When a power
work interaction involves a macroscopically observable force, the rate of energy transfer
by work is equal to the product of the force and the velocity at the point of application of
the force
#
WF#V (2.13)
#
A dot appearing over a symbol, as in W, is used throughout this book to indicate a time rate.
In principle, Eq. 2.13 can be integrated from time t1 to time t2 to get the total work done dur-
ing the time interval
t2 t2

#
W W dt F # V dt (2.14)
t1 t1
#
The same sign convention applies for W as for W. Since power is a time rate of doing work,
it can be expressed in terms of any units for energy and time. In SI, the unit for power is J/s,
called the watt. In this book the kilowatt, kW, is generally used.
for example. . . to illustrate the use of Eq. 2.13, let us evaluate the power required
for a bicyclist traveling at 8.94 m/s to overcome the drag force imposed by the surrounding
air. This aerodynamic drag force is given by
Fd 12CdArV2
where Cd is a constant called the drag coefficient, A is the frontal area of the bicycle and
rider, and is the air density. By Eq. 2.13 the required power is Fd # V or
W 1 12CdArV2 2 V
#
12CdArV3
Using typical values: Cd 0.88, A 0.362 m2, and 1.2 kg/m3, together with V 8.94 m/s,
the power required is
W 10.882 10.362 m2 2 11.2 kg/m3 218.94 m/s 2 3

# 1
2
136.6 W
2.2.3 Modeling Expansion or Compression Work

There are many ways in which work can be done by or on a system. The remainder of this
section is devoted to considering several examples, beginning with the important case of the
work done when the volume of a quantity of a gas (or liquid) changes by expansion or
compression.
Let us evaluate the work done by the closed system shown in Fig. 2.4 consisting of a gas
(or liquid) contained in a pistoncylinder assembly as the gas expands. During the process
the gas pressure exerts a normal force on the piston. Let p denote the pressure acting at the
interface between the gas and the piston. The force exerted by the gas on the piston is sim-
ply the product pA, where A is the area of the piston face. The work done by the system as
the piston is displaced a distance dx is
dW pA dx (2.15)
The product A dx in Eq. 2.15 equals the change in volume of the system, dV. Thus, the
work expression can be written as
dW p dV (2.16)
Since dV is positive when volume increases, the work at the moving boundary is positive
when the gas expands. For a compression, dV is negative, and so is work found from Eq. 2.16.
These signs are in agreement with the previously stated sign convention for work.
For a change in volume from V1 to V2, the work is obtained by integrating Eq. 2.16

V2
W p dV (2.17)
V1
Although Eq. 2.17 is derived for the case of a gas (or liquid) in a pistoncylinder assembly,
it is applicable to systems of any shape provided the pressure is uniform with position over
the moving boundary.
System boundary
Area = A Average pressure at
the piston face = p
F = pA
Gas or
liquid
Figure 2.4 Expansion or

x x1 x2 compression of a gas or liquid.
ACTUAL EXPANSION OR COMPRESSION PROCESSES p Measured data

To perform the integral of Eq. 2.17 requires a relationship between the gas pressure at the Curve fit
moving boundary and the system volume, but this relationship may be difficult, or even
impossible, to obtain for actual compressions and expansions. In the cylinder of an auto-
mobile engine, for example, combustion and other nonequilibrium effects give rise to
nonuniformities throughout the cylinder. Accordingly, if a pressure transducer were
mounted on the cylinder head, the recorded output might provide only an approximation V
for the pressure at the piston face required by Eq. 2.17. Moreover, even when the measured Figure 2.5 Pressure
pressure is essentially equal to that at the piston face, scatter might exist in the pressure volume data.
volume data, as illustrated in Fig. 2.5. Still, performing the integral of Eq. 2.17 based on
a curve fitted to the data could give a plausible estimate of the work. We will see later that
in some cases where lack of the required pressurevolume relationship keeps us from eval-
uating the work from Eq. 2.17, the work can be determined alternatively from an energy
balance (Sec. 2.5).
QUASIEQUILIBRIUM EXPANSION OR COMPRESSION PROCESSES
An idealized type of process called a quasiequilibrium process is introduced in Sec. 1.3. A

quasiequilibrium process is one in which all states through which the system passes may be quasiequilibrium process
considered equilibrium states. A particularly important aspect of the quasiequilibrium process
concept is that the values of the intensive properties are uniform throughout the system, or
every phase present in the system, at each state visited.
To consider how a gas (or liquid) might be expanded or compressed in a quasiequilib- Incremental masses removed
during an expansion of the
rium fashion, refer to Fig. 2.6, which shows a system consisting of a gas initially at an gas or liquid
equilibrium state. As shown in the figure, the gas pressure is maintained uniform through-
out by a number of small masses resting on the freely moving piston. Imagine that one of
the masses is removed, allowing the piston to move upward as the gas expands slightly.
During such an expansion the state of the gas would depart only slightly from equilibrium.
The system would eventually come to a new equilibrium state, where the pressure and all
other intensive properties would again be uniform in value. Moreover, were the mass re-
placed, the gas would be restored to its initial state, while again the departure from equi-
librium would be slight. If several of the masses were removed one after another, the gas
would pass through a sequence of equilibrium states without ever being far from equilib- Gas or
rium. In the limit as the increments of mass are made vanishingly small, the gas would liquid
undergo a quasiequilibrium expansion process. A quasiequilibrium compression can be
visualized with similar considerations. Boundary
Equation 2.17 can be applied to evaluate the work in quasiequilibrium expansion or com- Figure 2.6 Illustra-
pression processes. For such idealized processes the pressure p in the equation is the pressure tion of a quasiequilibrium
of the entire quantity of gas (or liquid) undergoing the process, and not just the pressure at expansion or compression.
the moving boundary. The relationship between the pressure and volume may be graphical
or analytical. Let us first consider a graphical relationship.
A graphical relationship is shown in the pressurevolume diagram ( pV diagram) of
Fig. 2.7. Initially, the piston face is at position x1, and the gas pressure is p1; at the conclu-
sion of a quasiequilibrium expansion process the piston face is at position x2, and the pres-
sure is reduced to p2. At each intervening piston position, the uniform pressure throughout
the gas is shown as a point on the diagram. The curve, or path, connecting states 1 and 2 on
the diagram represents the equilibrium states through which the system has passed during
the process. The work done by the gas on the piston during the expansion is given by p dV,
which can be interpreted as the area under the curve of pressure versus volume. Thus, the
shaded area on Fig. 2.7 is equal to the work for the process. Had the gas been compressed
from 2 to 1 along the same path on the pV diagram, the magnitude of the work would be
p1 1
Path
W = p dV
Pressure
p2 2
Area =
2
1 p dV
V1 dV V2
Volume
Gas or
liquid
Figure 2.7 Work of a quasiequilibrium

x1 x2
x expansion or compression process.
p the same, but the sign would be negative, indicating that for the compression the energy trans-
1 fer was from the piston to the gas.
The area interpretation of work in a quasiequilibrium expansion or compression process
allows a simple demonstration of the idea that work depends on the process. This can be
brought out by referring to Fig. 2.8. Suppose the gas in a pistoncylinder assembly goes from
A B an initial equilibrium state 1 to a final equilibrium state 2 along two different paths, labeled
2 A and B on Fig. 2.8. Since the area beneath each path represents the work for that process,
Area = work
for process A the work depends on the details of the process as defined by the particular curve and not just
on the end states. Using the test for a property given in Sec. 1.3, we can conclude again
V
(Sec. 2.2.1) that work is not a property. The value of work depends on the nature of the
Figure 2.8 Illustra- process between the end states.
tion that work depends on The relationship between pressure and volume during an expansion or compression process
the process.
also can be described analytically. An example is provided by the expression pV n constant,
where the value of n is a constant for the particular process. A quasiequilibrium process de-
polytropic process scribed by such an expression is called a polytropic process. Additional analytical forms for
the pressurevolume relationship also may be considered.
The example to follow illustrates the application of Eq. 2.17 when the relationship between
pressure and volume during an expansion is described analytically as pV n constant.
EXAMPLE 2.1 Evaluating Expansion Work
A gas in a pistoncylinder assembly undergoes an expansion process for which the relationship between pressure and volume
is given by
pV n constant
The initial pressure is 3 bar, the initial volume is 0.1 m3, and the final volume is 0.2 m3. Determine the work for the process,
in kJ, if (a) n 1.5, (b) n 1.0, and (c) n 0.
SOLUTION
Known: A gas in a pistoncylinder assembly undergoes an expansion for which pV n constant.
Find: Evaluate the work if (a) n 1.5, (b) n 1.0, (c) n 0.
Schematic and Given Data: The given pV relationship and the given data for pressure and volume can be used to construct
the accompanying pressurevolume diagram of the process.
3.0 1 2c
p1 = 3.0 bar
Gas V1 = 0.1 m3
p (bar)
2.0
pV n =
2b constant V2 = 0.2 m3
1.0 Area = work 2a
for part a
0.1 0.2
V (m3)
Figure E2.1
Assumptions:
1. The gas is a closed system.

2. The moving boundary is the only work mode.
3. The expansion is a polytropic process.
Analysis: The required values for the work are obtained by integration of Eq. 2.17 using the given pressurevolume relation.
(a) Introducing the relationship p constantV n into Eq. 2.17 and performing the integration

V2 V2 constant
W p dV dV
V1 V1 Vn
1constant2 V 1n
2 1constant2 V 1n
1

1n
The constant in this expression can be evaluated at either end state: constant p1V 1n p2V 2n. The work expression then
becomes
1 p2V 2n 2 V 1n
2 1p1V 1n 2 V 1n
1 p2V2 p1V1
W (1)
1n 1n
This expression is valid for all values of n except n 1.0. The case n 1.0 is taken up in part (b).
To evaluate W, the pressure at state 2 is required. This can be found by using p1V1n p2V2n, which on rearrangement yields
V1 n 0.1 1.5
p2 p1 a b 13 bar2 a b 1.06 bar
V2 0.2
Accordingly
11.06 bar210.2 m3 2 13210.12
Wa
105 N/m2
b` ` ` 3 # `
1 kJ
1 1.5 1 bar 10 N m

17.6 kJ
(b) For n 1.0, the pressurevolume relationship is pV constant or p constantV. The work is
1constant2 ln 1 p1V1 2 ln
V2 dV V2 V2
W constant (2)
V1 V V1 V1
Substituting values
105 N/m2
W 13 bar2 10.1 m3 2 ` ` ` 3 # ` ln a b
20.79 kJ
1 kJ 0.2
1 bar 10 N m 0.1
(c) For n 0, the pressurevolume relation reduces to p constant, and the integral becomes W p(V2 V1), which is a
special case of the expression found in part (a). Substituting values and converting units as above, W
30 kJ.
In each case, the work for the process can be interpreted as the area under the curve representing the process on the ac-
companying pV diagram. Note that the relative areas are in agreement with the numerical results.
The assumption of a polytropic process is significant. If the given pressurevolume relationship were obtained as a fit to
experimental pressurevolume data, the value of p d V would provide a plausible estimate of the work only when the
measured pressure is essentially equal to that exerted at the piston face.
Observe the use of unit conversion factors here and in part (b).
It is not necessary to identify the gas (or liquid) contained within the pistoncylinder assembly. The calculated values for
W are determined by the process path and the end states. However, if it is desired to evaluate other properties such as tem-
perature, both the nature and amount of the substance must be provided because appropriate relations among the proper-
ties of the particular substance would then be required.
2.2.4 Further Examples of Work

To broaden our understanding of the work concept, we now briefly consider several other
examples.
EXTENSION OF A SOLID BAR. Consider a system consisting of a solid bar under tension,
as shown in Fig. 2.9. The bar is fixed at x 0, and a force F is applied at the other end. Let
the force be represented as F A, where A is the cross-sectional area of the bar and the
normal stress acting at the end of the bar. The work done as the end of the bar moves a
distance dx is given by W A dx. The minus sign is required because work is done on
the bar when dx is positive. The work for a change in length from x1 to x2 is found by
integration
x2
W x1
sA dx (2.18)
Equation 2.18 for a solid is the counterpart of Eq. 2.17 for a gas undergoing an expansion
or compression.
STRETCHING OF A LIQUID FILM. Figure 2.10 shows a system consisting of a liquid film
suspended on a wire frame. The two surfaces of the film support the thin liquid layer inside
by the effect of surface tension, owing to microscopic forces between molecules near the
liquidair interfaces. These forces give rise to a macroscopically measurable force perpen-
dicular to any line in the surface. The force per unit length across such a line is the surface
tension. Denoting the surface tension acting at the movable wire by , the force F indicated
on the figure can be expressed as F 2l, where the factor 2 is introduced because two
film surfaces act at the wire. If the movable wire is displaced by dx, the work is given by
W 2l dx. The minus sign is required because work is done on the system when dx is
Rigid wire frame

Surface of film
Movable
wire
Area = A
F
x F
dx
x1
x2 x
Figure 2.9 Elongation of a solid bar. Figure 2.10 Stretching of a liquid film.
positive. Corresponding to a displacement dx is a change in the total area of the surfaces in

contact with the wire of dA 2l dx, so the expression for work can be written alternatively
as W dA. The work for an increase in surface area from A1 to A2 is found by
integrating this expression

A2
W t dA (2.19)
A1
POWER TRANSMITTED BY A SHAFT. A rotating shaft is a commonly encountered ma- + shaft

W
chine element. Consider a shaft rotating with angular velocity and exerting a torque t on Motor

its surroundings. Let the torque be expressed in terms of a tangential force Ft and radius ,
R: t FtR. The velocity at the point of application of the force is V R , where is in
radians per unit time. Using these relations with Eq. 2.13, we obtain an expression for the
power transmitted from the shaft to the surroundings
W FtV 1tR21Rv2 tv
#
(2.20)
A related case involving a gas stirred by a paddle wheel is considered in the discussion of
Fig. 2.3.
ELECTRIC POWER. Shown in Fig. 2.11 is a system consisting of an electrolytic cell. The

cell is connected to an external circuit through which an electric current, i, is flowing. The i
current is driven by the electrical potential difference e existing across the terminals labeled +
a and b. That this type of interaction can be classed as work is considered in the discussion a b
System
of Fig. 2.3. boundary
The rate of energy transfer by work, or the power, is Electrolytic
# cell
W ei (2.21)
Since the current i equals dZdt, the work can be expressed in differential form as Figure 2.11 Electro-
dW e dZ (2.22) lytic cell used to discuss
electric power.
where dZ is the amount of electrical charge that flows into the system. The minus signs are
required to be in accord with our previously stated sign convention for work. When the power
is evaluated in terms of the watt, and the unit of current is the ampere (an SI base unit), the
unit of electric potential is the volt, defined as 1 watt per ampere.
WORK DUE TO POLARIZATION OR MAGNETIZATION. Let us next refer briefly to the

types of work that can be done on systems residing in electric or magnetic fields, known as
the work of polarization and magnetization, respectively. From the microscopic viewpoint,
electrical dipoles within dielectrics resist turning, so work is done when they are aligned by
an electric field. Similarly, magnetic dipoles resist turning, so work is done on certain other
materials when their magnetization is changed. Polarization and magnetization give rise to
macroscopically detectable changes in the total dipole moment as the particles making up
the material are given new alignments. In these cases the work is associated with forces im-
posed on the overall system by fields in the surroundings. Forces acting on the material in
the system interior are called body forces. For such forces the appropriate displacement in
evaluating work is the displacement of the matter on which the body force acts. Forces act-
ing at the boundary are called surface forces. Examples of work done by surface forces
include the expansion or compression of a gas (or liquid) and the extension of a solid.
2.2.5 Further Examples of Work in Quasiequilibrium Processes

Systems other than a gas or liquid in a pistoncylinder assembly can also be envisioned as
undergoing processes in a quasiequilibrium fashion. To apply the quasiequilibrium process
concept in any such case, it is necessary to conceive of an ideal situation in which the ex-
ternal forces acting on the system can be varied so slightly that the resulting imbalance is
infinitesimal. As a consequence, the system undergoes a process without ever departing sig-
nificantly from thermodynamic equilibrium.
The extension of a solid bar and the stretching of a liquid surface can readily be envisioned
to occur in a quasiequilibrium manner by direct analogy to the pistoncylinder case. For the
bar in Fig. 2.9 the external force can be applied in such a way that it differs only slightly from
the opposing force within. The normal stress is then essentially uniform throughout and can
be determined as a function of the instantaneous length: (x). Similarly, for the liquid
film shown in Fig. 2.10 the external force can be applied to the movable wire in such a way
that the force differs only slightly from the opposing force within the film. During such a
process, the surface tension is essentially uniform throughout the film and is functionally re-
lated to the instantaneous area: (A). In each of these cases, once the required functional
relationship is known, the work can be evaluated using Eq. 2.18 or 2.19, respectively, in terms
of properties of the system as a whole as it passes through equilibrium states.
Other systems can also be imagined as undergoing quasiequilibrium processes. For ex-
ample, it is possible to envision an electrolytic cell being charged or discharged in a quasi-
equilibrium manner by adjusting the potential difference across the terminals to be slightly
greater, or slightly less, than an ideal potential called the cell electromotive force (emf). The
energy transfer by work for passage of a differential quantity of charge to the cell, dZ, is
given by the relation
dW e dZ (2.23)
In this equation e denotes the cell emf, an intensive property of the cell, and not just the po-
tential difference across the terminals as in Eq. 2.22.
Consider next a dielectric material residing in a uniform electric field. The energy trans-
ferred by work from the field when the polarization is increased slightly is
dW E # d1V P2 (2.24)
where the vector E is the electric field strength within the system, the vector P is the elec-
tric dipole moment per unit volume, and V is the volume of the system. A similar equation
for energy transfer by work from a uniform magnetic field when the magnetization is increased
slightly is
dW m0H # d1V M2 (2.25)
where the vector H is the magnetic field strength within the system, the vector M is the mag-
netic dipole moment per unit volume, and 0 is a constant, the permeability of free space.
2.3 Broadening Our Understanding of Energy 43
The minus signs appearing in the last three equations are in accord with our previously stated
sign convention for work: W takes on a negative value when the energy transfer is into the
system.
GENERALIZED FORCES AND DISPLACEMENTS
The similarity between the expressions for work in the quasiequilibrium processes consid-
ered thus far should be noted. In each case, the work expression is written in the form of an
intensive property and the differential of an extensive property. This is brought out by the
following expression, which allows for one or more of these work modes to be involved in
a process
dW p dV sd 1A x2 t dA e dZ E # d1V P2 m0H # d1V M2
# # # (2.26)
where the last three dots represent other products of an intensive property and the differential
of a related extensive property that account for work. Because of the notion of work being
a product of force and displacement, the intensive property in these relations is sometimes
referred to as a generalized force and the extensive property as a generalized displace-
ment, even though the quantities making up the work expressions may not bring to mind
actual forces and displacements.
Owing to the underlying quasiequilibrium restriction, Eq. 2.26 does not represent every
type of work of practical interest. An example is provided by a paddle wheel that stirs a gas Paddle
or liquid taken as the system. Whenever any shearing action takes place, the system necessarily wheel
passes through nonequilibrium states. To appreciate more fully the implications of the qua-
siequilibrium process concept requires consideration of the second law of thermodynamics,
Gas
so this concept is discussed again in Chap. 5 after the second law has been introduced.

2.3 Broadening Our Understanding of Energy
The objective in this section is to use our deeper understanding of work developed in Sec. 2.2
F
to broaden our understanding of the energy of a system. In particular, we consider the total
energy of a system, which includes kinetic energy, gravitational potential energy, and other
forms of energy. The examples to follow illustrate some of these forms of energy. Many other
examples could be provided that enlarge on the same idea.
When work is done to compress a spring, energy is stored within the spring. When a bat-
tery is charged, the energy stored within it is increased. And when a gas (or liquid) initially
at an equilibrium state in a closed, insulated vessel is stirred vigorously and allowed to come
to a final equilibrium state, the energy of the gas is increased in the process. In each of these
i
examples the change in system energy cannot be attributed to changes in the systems overall
kinetic or gravitational potential energy as given by Eqs. 2.5 and 2.10, respectively.
The change in energy can be accounted for in terms of internal energy, as considered next.
In engineering thermodynamics the change in the total energy of a system is considered
to be made up of three macroscopic contributions. One is the change in kinetic energy, as-
Battery
sociated with the motion of the system as a whole relative to an external coordinate frame.
Another is the change in gravitational potential energy, associated with the position of the
system as a whole in the earths gravitational field. All other energy changes are lumped to-
gether in the internal energy of the system. Like kinetic energy and gravitational potential internal energy
energy, internal energy is an extensive property of the system, as is the total energy.
Internal energy is represented by the symbol U, and the change in internal energy in a
process is U2 U1. The specific internal energy is symbolized by u or u, respectively, de-
pending on whether it is expressed on a unit mass or per mole basis.
The change in the total energy of a system is
E2 E1 1KE2 KE1 2
1PE2 PE1 2
1U2 U1 2
or (2.27)
E KE
PE
U
All quantities in Eq. 2.27 are expressed in terms of the energy units previously introduced.
The identification of internal energy as a macroscopic form of energy is a significant step
in the present development, for it sets the concept of energy in thermodynamics apart from
that of mechanics. In Chap. 3 we will learn how to evaluate changes in internal energy for
practically important cases involving gases, liquids, and solids by using empirical data.
To further our understanding of internal energy, consider a system we will often encounter
in subsequent sections of the book, a system consisting of a gas contained in a tank. Let us
microscopic develop a microscopic interpretation of internal energy by thinking of the energy attributed
interpretation of internal to the motions and configurations of the individual molecules, atoms, and subatomic parti-
energy for a gas cles making up the matter in the system. Gas molecules move about, encountering other mol-
ecules or the walls of the container. Part of the internal energy of the gas is the translational
kinetic energy of the molecules. Other contributions to the internal energy include the kinetic
energy due to rotation of the molecules relative to their centers of mass and the kinetic energy
associated with vibrational motions within the molecules. In addition, energy is stored in the
chemical bonds between the atoms that make up the molecules. Energy storage on the atomic
level includes energy associated with electron orbital states, nuclear spin, and binding forces
in the nucleus. In dense gases, liquids, and solids, intermolecular forces play an important
role in affecting the internal energy.
Gas

2.4 Energy Transfer by Heat
Thus far, we have considered quantitatively only those interactions between a system and its
Hot plate surroundings that can be classed as work. However, closed systems also can interact with
their surroundings in a way that cannot be categorized as work. for example. . . when
a gas in a rigid container interacts with a hot plate, the energy of the gas is increased even
energy transfer by heat though no work is done. This type of interaction is called an energy transfer by heat.
On the basis of experiment, beginning with the work of Joule in the early part of the nine-
teenth century, we know that energy transfers by heat are induced only as a result of a tem-
perature difference between the system and its surroundings and occur only in the direction
of decreasing temperature. Because the underlying concept is so important in thermody-
namics, this section is devoted to a further consideration of energy transfer by heat.
2.4.1 Sign Convention, Notation, and Heat Transfer Rate

The symbol Q denotes an amount of energy transferred across the boundary of a system in
a heat interaction with the systems surroundings. Heat transfer into a system is taken to be
positive, and heat transfer from a system is taken as negative.
sign convention for Q 7 0: heat transfer to the system
heat transfer Q 6 0: heat transfer from the system
This sign convention is used throughout the book. However, as was indicated for work, it is
sometimes convenient to show the direction of energy transfer by an arrow on a sketch of
2.4 Energy Transfer by Heat 45
the system. Then the heat transfer is regarded as positive in the direction of the arrow. In an
adiabatic process there is no energy transfer by heat.
The sign convention for heat transfer is just the reverse of the one adopted for work, where
a positive value for W signifies an energy transfer from the system to the surroundings. These
signs for heat and work are a legacy from engineers and scientists who were concerned mainly
with steam engines and other devices that develop a work output from an energy input by
heat transfer. For such applications, it was convenient to regard both the work developed and
the energy input by heat transfer as positive quantities.
The value of a heat transfer depends on the details of a process and not just the end states.
Thus, like work, heat is not a property, and its differential is written as Q. The amount of heat is not a property
energy transfer by heat for a process is given by the integral
2
Q 1
dQ (2.28)
where the limits mean from state 1 to state 2 and do not refer to the values of heat at those
states. As for work, the notion of heat at a state has no meaning, and the integral should
never be evaluated as Q2 Q1. #
The net rate of heat transfer is denoted by Q. In principle, the amount of energy trans- rate of heat transfer
fer by heat during a period of time can be found by integrating from time t1 to time t2
t2

#
Q Q dt (2.29)
t1
To perform the integration, it would be necessary to know how the rate of heat transfer varies
with time.
#
In some cases it is convenient to use the heat flux, q, which
# is the heat transfer rate per
#
unit of system surface area. The net rate of heat transfer, Q, is related to the heat flux q by
the integral
q# dA
#
Q (2.30)
A
where A represents the area on the boundary of the system where heat transfer occurs.
# #
UNITS. The units for Q and Q are the same as those introduced previously for W and W,
respectively. The units for the heat flux are those of the heat transfer rate per unit area: kW/m2
or Btu /h # ft2.
2.4.2 Heat Transfer Modes

Methods based on experiment are available for evaluating energy transfer by heat. These
methods recognize two basic transfer mechanisms: conduction and thermal radiation. In ad-
dition, empirical relationships are available for evaluating energy transfer involving certain . T1
Qx
combined modes. A brief description of each of these is given next. A detailed consideration
is left to a course in engineering heat transfer, where these topics are studied in depth. T2
L
Area, A
CONDUCTION x
Energy transfer by conduction can take place in solids, liquids, and gases. Conduction can
be thought of as the transfer of energy from the more energetic particles of a substance to
adjacent particles that are less energetic due to interactions between particles. The time rate Figure 2.12 Illus-
of energy transfer by conduction is quantified macroscopically by Fouriers law. As an ele- tration of Fouriers
mentary application, consider Fig. 2.12 showing a plane wall of thickness L at steady state, conduction law.
where the temperature T(x) varies linearly with position

# x. By Fouriers law, the rate of heat
transfer across any plane normal to the x direction, Qx, is proportional to the wall area, A,
and the temperature gradient in the x direction, dTdx
# dT
Fouriers law Qx kA (2.31)
dx
where the proportionality constant
is a property called the thermal conductivity. The
minus sign is a consequence of energy transfer in the direction of decreasing temperature.
for example. . . in this case the temperature varies linearly; thus, the temperature
gradient is
T2 T1
16 02
dT

dx L
and the rate of heat transfer in the x direction is then
T2 T1
Qx kA c d
#
(2.32)
L
Values of thermal conductivity are given in Table A-19 for common materials. Substances
with large values of thermal conductivity such as copper are good conductors, and those with
small conductivities (cork and polystyrene foam) are good insulators.
RADIATION
Thermal radiation is emitted by matter as a result of changes in the electronic configura-

tions of the atoms or molecules within it. The energy is transported by electromagnetic
waves (or photons). Unlike conduction, thermal radiation requires no intervening medium
to propagate and can even take place in a vacuum. Solid surfaces, gases, and liquids all
emit, absorb,# and transmit thermal radiation to varying degrees. The rate at which energy
is emitted, Qe, from a surface of area A is quantified macroscopically by a modified form
of the StefanBoltzmann law
#
StefanBoltzmann law Qe esAT b4 (2.33)
which shows that thermal radiation is associated with the fourth power of the absolute tem-
perature of the surface, Tb. The emissivity, , is a property of the surface that indicates how
effectively the surface radiates (0 1.0), and is the StefanBoltzmann constant. In
general, the net rate of energy transfer by thermal radiation between two surfaces involves
relationships among the properties of the surfaces, their orientations with respect to each
other, the extent to which the intervening medium scatters, emits, and absorbs thermal radi-
ation, and other factors.
CONVECTION
Energy transfer between a solid surface at a temperature Tb and an adjacent moving gas or
liquid at another temperature Tf plays a prominent role in the performance of many devices
of practical interest. This is commonly referred to as convection. As an illustration, consider
Fig. 2.13, where Tb Tf. In this case, energy is transferred in the direction indicated by the
arrow due to the combined effects of conduction within the air and the bulk motion of the
air. The rate of energy transfer from the surface to the air can be quantified by the following
empirical expression:
Qc hA1Tb Tf 2
#
(2.34)
2.4 Energy Transfer by Heat 47
Cooling air flow .

Tf < Tb Qc
Tb
A
Wire leads
Transistor
Figure 2.13 Illustration of
Circuit board Newtons law of cooling.
known as Newtons law of cooling. In Eq. 2.34, A is the surface area and the proportionality Newtons law of cooling
factor h is called the heat transfer coefficient. In subsequent applications of Eq. 2.34, a minus
sign may be introduced on the right side to conform to the sign convention for heat transfer
introduced in Sec. 2.4.1.
The heat transfer coefficient is not a thermodynamic property. It is an empirical parame-
ter that incorporates into the heat transfer relationship the nature of the flow pattern near the
surface, the fluid properties, and the geometry. When fans or pumps cause the fluid to move,
the value of the heat transfer coefficient is generally greater than when relatively slow
buoyancy-induced motions occur. These two general categories are called forced and free (or
natural) convection, respectively. Table 2.1 provides typical values of the convection heat
transfer coefficient for forced and free convection.
2.4.3 Closure
The first step in a thermodynamic analysis is to define the system. It is only after the sys-
tem boundary has been specified that possible heat interactions with the surroundings are
considered, for these are always evaluated at the system boundary. In ordinary conversation,
the term heat is often used when the word energy would be more correct thermodynamically.
For example, one might hear, Please close the door or heat will be lost. In thermodyn-
amics, heat refers only to a particular means whereby energy is transferred. It does not re-
fer to what is being transferred between systems or to what is stored within systems. Energy
is transferred and stored, not heat.
Sometimes the heat transfer of energy to, or from, a system can be neglected. This might
occur for several reasons related to the mechanisms for heat transfer discussed above. One
might be that the materials surrounding the system are good insulators, or heat transfer might
not be significant because there is a small temperature difference between the system and its
surroundings. A third reason is that there might not be enough surface area to allow signif-
icant heat transfer to occur. When heat transfer is neglected, it is because one or more of
these considerations apply.
TABLE 2.1 Typical Values of the

Convection Heat Transfer Coefficient
Applications h (W/m2 # K)
Free convection
Gases 225
Liquids 501000
Forced convection
Gases 25250
Liquids 5020,000
In the discussions to follow the value of Q is provided, or it is an unknown in the analy-

sis. When Q is provided, it can be assumed that the value has been determined by the meth-
ods introduced above. When Q is the unknown, its value is usually found by using the energy
balance, discussed next.

2.5 Energy Accounting: Energy Balance
for Closed Systems
As our previous discussions indicate, the only ways the energy of a closed system can be changed
are through transfer of energy by work or by heat. Further, based on the experiments of Joule
and others, a fundamental aspect of the energy concept is that energy is conserved; we call this
first law of the first law of thermodynamics. These considerations are summarized in words as follows:
thermodynamics change in the amount net amount of energy net amount of energy
of energy contained transferred in across transferred out across
D within the system T Dthe system boundary byT D the system boundary T
during some time heat transfer during by work during the
interval the time interval time interval
This word statement is just an accounting balance for energy, an energy balance. It requires
that in any process of a closed system the energy of the system increases or decreases by an
amount equal to the net amount of energy transferred across its boundary.
The phrase net amount used in the word statement of the energy balance must be care-
fully interpreted, for there may be heat or work transfers of energy at many different places
on the boundary of a system. At some locations the energy transfers may be into the system,
whereas at others they are out of the system. The two terms on the right side account for the
net results of all the energy transfers by heat and work, respectively, taking place during the
time interval under consideration.
The energy balance can be expressed in symbols as
E2 E1 Q W (2.35a)
energy balance Introducing Eq. 2.27 an alternative form is
KE
PE
U Q W (2.35b)
which shows that an energy transfer across the system boundary results in a change in one
or more of the macroscopic energy forms: kinetic energy, gravitational potential energy, and
internal energy. All previous references to energy as a conserved quantity are included as
special cases of Eqs. 2.35.
Note that the algebraic signs before the heat and work terms of Eqs. 2.35 are different.
This follows from the sign conventions previously adopted. A minus sign appears before W
because energy transfer by work from the system to the surroundings is taken to be positive.
A plus sign appears before Q because it is regarded to be positive when the heat transfer of
energy is into the system from the surroundings.
OTHER FORMS OF THE ENERGY BALANCE
Various special forms of the energy balance can be written. For example, the energy balance
in differential form is
dE dQ dW (2.36)
2.5 Energy Accounting: Energy Balance for Closed Systems 49
where dE is the differential of energy, a property. Since Q and W are not properties, their
differentials are written as Q and W, respectively.
The instantaneous time rate form of the energy balance is
dE # # time rate form of the

QW (2.37) energy balance
dt
The rate form of the energy balance expressed in words is

time rate of change net rate at which net rate at which
of the energy energy is being energy is being
D contained within T D transferred in T D transferred out T
the system at by heat transfer by work at
time t at time t time t
Since the time rate of change of energy is given by
dE d KE d PE dU

dt dt dt dt
Equation 2.37 can be expressed alternatively as
d KE d PE dU # #

QW (2.38)
dt dt dt
Equations 2.35 through 2.38 provide alternative forms of the energy balance that may be
convenient starting points when applying the principle of conservation of energy to closed
systems. In Chap. 4 the conservation of energy principle is expressed in forms suitable for the
analysis of control volumes. When applying the energy balance in any of its forms, it is im-
portant to be careful about signs and units and to distinguish carefully between rates and
amounts. In addition, it is important to recognize that the location of the system boundary can
be relevant in determining whether a particular energy transfer is regarded as heat or work.
for example. . . consider Fig. 2.14, in which three alternative systems are shown
that include a quantity of a gas (or liquid) in a rigid, well-insulated container. In Fig. 2.14a,
the gas itself is the system. As current flows through the copper plate, there is an energy
transfer from the copper plate to the gas. Since this energy transfer occurs as a result of the
temperature difference between the plate and the gas, it is classified as a heat transfer. Next,
refer to Fig. 2.14b, where the boundary is drawn to include the copper plate. It follows from
the thermodynamic definition of work that the energy transfer that occurs as current crosses
the boundary of this system must be regarded as work. Finally, in Fig. 2.14c, the boundary
is located so that no energy is transferred across it by heat or work.
CLOSING COMMENT. Thus far, we have been careful to emphasize that the quantities sym-
bolized by W and Q in the foregoing equations account for transfers of energy and not transfers
of work and heat, respectively. The terms work and heat denote different means whereby en-
ergy is transferred and not what is transferred. However, to achieve economy of expression in
subsequent discussions, W and Q are often referred to simply as work and heat transfer,
respectively. This less formal manner of speaking is commonly used in engineering practice.
ILLUSTRATIONS
The examples to follow bring out many important ideas about energy and the energy balance.
They should be studied carefully, and similar approaches should be used when solving the
end-of-chapter problems.
Copper Rotating
plate shaft
Gas or liquid
+ Gas +
Q or W
liquid
W=0
Electric
generator Q=0
System Insulation System
boundary boundary
Mass
(a) (b)
Gas +
or
liquid
System
boundary
Q = 0, W = 0
(c)
Figure 2.14 Alternative choices for system boundaries.
In this text, most applications of the energy balance will not involve significant kinetic or
potential energy changes. Thus, to expedite the solutions of many subsequent examples and
end-of-chapter problems, we indicate in the problem statement that such changes can be neg-
lected. If this is not made explicit in a problem statement, you should decide on the basis of
the problem at hand how best to handle the kinetic and potential energy terms of the energy
balance.
PROCESSES OF CLOSED SYSTEMS. The next two examples illustrate the use of the energy
balance for processes of closed systems. In these examples, internal energy data are provided.
In Chap. 3, we learn how to obtain thermodynamic property data using tables, graphs, equa-
tions, and computer software.
EXAMPLE 2.2 Cooling a Gas in a PistonCylinder
Four kilograms of a certain gas is contained within a pistoncylinder assembly. The gas undergoes a process for which the
pressurevolume relationship is
pV1.5 constant
The initial pressure is 3 bar, the initial volume is 0.1 m3, and the final volume is 0.2 m3. The change in specific internal energy
of the gas in the process is u2 u1 4.6 kJ/kg. There are no significant changes in kinetic or potential energy. Determine
the net heat transfer for the process, in kJ.
SOLUTION
Known: A gas within a pistoncylinder assembly undergoes an expansion process for which the pressurevolume relation
and the change in specific internal energy are specified.
Find: Determine the net heat transfer for the process.
p 1
u2 u1 = 4.6 kJ/kg
pV 1.5 = constant
Gas
pV 1.5 =
2 constant
Area = work
V
Figure E2.2
Assumptions:
1. The gas is a closed system.

2. The process is described by pV1.5 constant.
3. There is no change in the kinetic or potential energy of the system.
Analysis: An energy balance for the closed system takes the form
0 0
KE
PE
U Q W
where the kinetic and potential energy terms drop out by assumption 3. Then, writing U in terms of specific internal ener-
gies, the energy balance becomes
m1u2 u1 2 Q W
where m is the system mass. Solving for Q
Q m1u2 u1 2
W
The value of the work for this process is determined in the solution to part (a) of Example 2.1: W
17.6 kJ. The change
in internal energy is obtained using given data as
m1u2 u1 2 4 kg a4.6 b 18.4 kJ

kJ
kg
Substituting values
Q 18.4
17.6 0.8 kJ
The given relationship between pressure and volume allows the process to be represented by the path shown on the ac-
companying diagram. The area under the curve represents the work. Since they are not properties, the values of the work
and heat transfer depend on the details of the process and cannot be determined from the end states only.
The minus sign for the value of Q means that a net amount of energy has been transferred from the system to its sur-
roundings by heat transfer.
In the next example, we follow up the discussion of Fig. 2.14 by considering two alter-
native systems. This example highlights the need to account correctly for the heat and work
interactions occurring on the boundary as well as the energy change.
EXAMPLE 2.3 Considering Alternative Systems
Air is contained in a vertical pistoncylinder assembly fitted with an electrical resistor. The atmosphere exerts a pressure of
1 bar on the top of the piston, which has a mass of 45 kg and a face area of .09 m2. Electric current passes through the
resistor, and the volume of the air slowly increases by .045 m3 while its pressure remains constant. The mass of the air is
.27 kg, and its specific internal energy increases by 42 kJ/kg. The air and piston are at rest initially and finally. The
pistoncylinder material is a ceramic composite and thus a good insulator. Friction between the piston and cylinder wall can
be ignored, and the local acceleration of gravity is g 9.81 m/s2. Determine the heat transfer from the resistor to the air, in
kJ, for a system consisting of (a) the air alone, (b) the air and the piston.
SOLUTION
Known: Data are provided for air contained in a vertical pistoncylinder fitted with an electrical resistor.
Find: Considering each of two alternative systems, determine the heat transfer from the resistor to the air.
Piston Piston
patm = 1 bar
System
System m piston = 45 kg boundary
boundary A piston = .09 m2 for part (b)
for part (a)
+ +
Air Air

m air = .27 kg
V2 V1 = .045 m3
u air = 42 kJ/kg.
(a) (b)
Figure E2.3
Assumptions:
1. Two closed systems are under consideration, as shown in the schematic.

2. The only significant heat transfer is from the resistor to the air, during which the air expands slowly and its pressure remains
constant.
3. There is no net change in kinetic energy; the change in potential energy of the air is negligible; and since the piston material
is a good insulator, the internal energy of the piston is not affected by the heat transfer.
4. Friction between the piston and cylinder wall is negligible.
5. The acceleration of gravity is constant; g 9.81 m/s2.
Analysis: (a) Taking the air as the system, the energy balance, Eq. 2.35, reduces with assumption 3 to
1 KE
PE
U2 air Q W
0 0
Or, solving for Q
Q W
Uair
For this system, work is done by the force of the pressure p acting on the bottom of the piston as the air expands. With
Eq. 2.17 and the assumption of constant pressure
p dV p 1V2 V1 2
V2
W
V1
To determine the pressure p, we use a force balance on the slowly moving, frictionless piston. The upward force exerted
by the air on the bottom of the piston equals the weight of the piston plus the downward force of the atmosphere acting on
the top of the piston. In symbols
p Apiston mpiston g
patmApiston
Solving for p and inserting values
mpiston g
p
patm
Apiston
145 kg219.81 m/s2 2
` `
1 bar 1.049 bar
1 bar
p
.09 m2 105 N /m2
Thus, the work is
W p 1V2 V1 2
105 N/m2
11.049 bar2 1.045 m2 2 ` ` ` 3 # ` 4.72 kJ
1 kJ
1 bar 10 N m
With Uair mair(uair), the heat transfer is
Q W
mair 1uair 2
4.72 kJ
11.07 kJ 15.8 kJ
(b) Consider next a system consisting of the air and the piston. The energy change of the overall system is the sum of the
energy changes of the air and the piston. Thus, the energy balance, Eq. 2.35, reads
1 KE
PE
U2 air
1KE
PE
U 2 piston Q W
0 0 0 0
where the indicated terms drop out by assumption 3. Solving for Q
Q W
1 PE2 piston
1U2 air
For this system, work is done at the top of the piston as it pushes aside the surrounding atmosphere. Applying Eq. 2.17
p dV patm 1V2 V1 2
V2
W
V1
105 N/m2
11 bar2 1.045 m2 2 ` ` ` 3 # ` 4.5 kJ
1 kJ
1 bar 10 N m
The elevation change, z, required to evaluate the potential energy change of the piston can be found from the volume
change of the air and the area of the piston face as
V2 V1 .045 m3
z .5 m
Apiston .09 m2
Thus, the potential energy change of the piston is
1 PE2 piston mpiston gz

145 kg2 19.81 m/s2 2 10.5 m2 .22 kJ
Finally
Q W
1PE2 piston
mair uair
4.5 kJ
.22 kJ
11.07 kJ 15.8 kJ
which agrees with the result of part (a).
Using the change in elevation z determined in the analysis, the change in potential energy of the air is about 103 Btu,
which is negligible in the present case. The calculation is left as an exercise.
Although the value of Q is the same for each system, observe that the values for W differ. Also, observe that the energy
changes differ, depending on whether the air alone or the air and the piston is the system.
STEADY-STATE OPERATION. A system is at steady state if none of its properties change

with time (Sec. 1.3). Many devices operate at steady state or nearly at steady state, meaning
that property variations with time are small enough to ignore. The two examples to follow
illustrate the application of the energy rate equation to closed systems at steady state.
EXAMPLE 2.4 Gearbox at Steady State
During steady-state operation, a gearbox receives 60 kW through the input shaft and delivers power through the output shaft.
For the gearbox as the system, the rate of energy transfer by convection is
Q hA1Tb Tf 2
#
where h 0.171 kW/m2 K is the heat transfer coefficient, A 1.0 m2 is the outer surface area of the gearbox, Tb
300 K (27C) is the temperature at the outer surface, and Tf 293 K (20C) is the temperature of the surrounding air
away from the immediate vicinity of the gearbox. For the gearbox, evaluate the heat transfer rate and the power delivered
through the output shaft, each in kW.
SOLUTION
Known: A gearbox operates at steady state with a known power input. An expression for the heat transfer rate from the outer
surface is also known.
Find: Determine the heat transfer rate and the power delivered through the output shaft, each in kW.
Tb = 300 K
W 1 = 60 kW
Tf = 293 K
1
h = 0.171 kW/m2 K
Assumption: The gearbox is a closed system at
Input steady state.
shaft 2
Gearbox
Output
Outer surface
shaft
A = 1.0 m2
Figure E2.4
#
Analysis: Using the given expression for Q together with known data, the rate of energy transfer by heat is
Q hA1Tb Tf 2
#
b 11.0 m2 21300 2932 K

kW
a0.171
m2 # K
1.2 kW
#
The minus sign for Q signals that energy is carried out of the gearbox by heat transfer.
The energy rate balance, Eq. 2.37, reduces at steady state to
0
dE
# # # #
QW or W Q
dt
# # #
The symbol W represents the net power from the system. The net power is the sum of W1 and the output power W2
# # #
W W1
W2
#
With this expression for W, the energy rate balance becomes
# # #
W1
W2 Q
# # #
Solving for W2, inserting Q 1.2 kW, and W1 60 kW, where the minus sign is required because the input shaft brings
energy into the system, we have
# # #
W2 Q W1
11.2 kW2 160 kW2

58.8 kW
#
The positive sign for W2 indicates that energy is transferred from the system through the output shaft, as expected.
In accord with #the sign convention for the heat transfer rate in the energy rate balance (Eq. 2.37), Eq. 2.34 is written with
a minus sign: Q is negative when Tb is greater than Tf.
Properties of a system at steady state do not change with time. Energy E is a property, but heat transfer and work are not
properties.
For this system energy transfer by work occurs at two different locations, and the signs associated with their values differ.
At steady state, the rate of heat transfer from the gear box accounts for the difference between the input and output power.
This can be summarized by the following energy rate balance sheet in terms of magnitudes:
Input Output
60 kW (input shaft) 58.8 kW (output shaft)
1.2 kW (heat transfer)
Total: 60 kW 60 kW
EXAMPLE 2.5 Silicon Chip at Steady State
A silicon chip measuring 5 mm on a side and 1 mm in thickness is embedded in a ceramic substrate. At steady state, the chip
has an electrical power input of 0.225 W. The top surface of the chip is exposed to a coolant whose temperature is 20C. The
heat transfer coefficient for convection between the chip and the coolant is 150 W/m2 # K. If heat transfer by conduction be-
tween the chip and the substrate is negligible, determine the surface temperature of the chip, in C.
SOLUTION
Known: A silicon chip of known dimensions is exposed on its top surface to a coolant. The electrical power input and con-
vective heat transfer coefficient are known.
Find: Determine the surface temperature of the chip at steady state.
Coolant
h = 150 W/m2 K
Tf = 20 C Assumptions:
5 mm
5 mm
Tb 1. The chip is a closed system at steady state.
+ 2. There is no heat transfer between the chip and the substrate.

1 mm
W = 0.225 W
Ceramic substrate
Figure E2.5
Analysis: The surface temperature of the chip, Tb, can be determined using the energy rate balance, Eq. 2.37, which at steady
state reduces as follows
0
dE # #
dt
QW
With assumption 2, the only heat transfer is by convection to the coolant. In this application, Newtons law of cooling, Eq. 2.34,
takes the form
Q hA1Tb Tf 2
#
Collecting results
0 hA1Tb Tf 2 W
#
Solving for Tb
#
W
Tb
Tf
hA
#
In this expression, W 0.225 W, A 25 106 m2, h 150 W/m2 # K, and Tf 293 K, giving
10.225 W2
Tb
293 K
1150 W/m2 # K2125 106 m2 2
353 K 180C2
Properties of a system at steady state do not change with time. Energy E is a property, but heat transfer and work are not
properties.
In accord
# with the sign convention for heat transfer in the energy rate balance (Eq. 2.37), Eq. 2.34 is written with a minus
sign: Q is negative when Tb is greater than Tf.
TRANSIENT OPERATION. Many devices undergo periods of transient operation where the
state changes with time. This is observed during startup and shutdown periods. The next ex-
ample illustrates the application of the energy rate balance to an electric motor during startup.
The example also involves both electrical work and power transmitted by a shaft.
EXAMPLE 2.6 Transient Operation of a Motor
The rate of heat transfer between a certain electric motor and its surroundings varies with time as
Q 0.2 31 e10.05t2 4
#
#
where t is in seconds and Q is in kW. The shaft of the motor rotates at a constant speed of 100 rad/s (about 955 revo-
lutions per minute, or RPM) and applies a constant torque# of t #
# 18 N m to an external load. The motor draws a constant
electric power input equal to 2.0 kW. For the motor, plot Q and W, each in kW, and the change in energy E, in kJ, as func-
tions of time from t 0 to t 120 s. Discuss.
SOLUTION
Known: A motor operates with constant electric power input, shaft speed, and applied torque. The time-varying rate of heat
transfer between the motor and its surroundings is given.
# #
Find: Plot Q, W, and E versus time, Discuss.
= 18 N m
= 100 rad/s
W elec = 2.0 kW
+ W shaft Assumption: The system shown in the accompanying sketch
Motor is a closed system.

= 0.2 [1 e (0.05t)] kW
Q
Figure E2.6a
Analysis: The time rate of change of system energy is

dE # #
QW
dt
# #
W represents the net power from the # system: the sum of the power associated with the rotating shaft, Wshaft, and the power
associated with the electricity flow, Welec
# # #
W Wshaft
Welec
# #
The rate Welec is known from the problem statement: W# elec 2.0 kW, where the negative sign is required because energy is
carried into the system by electrical work. The term Wshaft can be evaluated with Eq. 2.20 as
Wshaft tv 118 N # m21100 rad /s2 1800 W
1.8 kW
#
Because energy exits the system along the rotating shaft, this energy transfer rate is positive.
In summary
W Welec
Wshaft 12.0 kW2
1
1.8 kW2 0.2 kW
# # #
where the minus sign means that the

# electrical power input is greater
# than the power transferred out along the shaft.
With the foregoing result for W and the given expression for Q, the energy rate balance becomes
0.2 31 e10.05t2 4 10.22 0.2e10.05t2

dE
dt
Integrating
t
E 0.2e
0
10.05t2
dt
t
e10.05t2 d 43 1 e10.05t2 4
0.2

10.052 0
# #
The accompanying plots, Figs. E2.6b, c, are developed using the given expression for Q and the # expressions
# for W and
E obtained in the analysis. Because of our sign conventions for heat and work, the values of Q and W are negative. In
the first few seconds, the net rate energy is carried in by work greatly exceeds the rate energy is carried out by heat trans-
fer.
# Consequently, # the energy stored in the motor increases rapidly as the motor warms up. As time elapses, the value of
Q approaches W, and the rate of energy storage diminishes. After about 100 s, this transient operating mode is nearly over,
and there is little further change in the amount of energy stored, or in any other property. We may say that the motor is
then at steady state.
4 0.05
E, kJ
Q, W, kW
3 0.10

Q
2 0.15
W
1 0.20
0 0.25
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
Time, s Time, s
Figure E2.6b, c
Figures E.2.6b, c can be developed using appropriate software or can be drawn by hand.
#
At steady state, the value of Q is constant at 0.2 kW. This constant value for the heat transfer rate can be thought of as
the portion of the electrical power input that is not obtained as a mechanical power output because of effects within the
motor such as electrical resistance and friction.
2.6 Energy Analysis of Cycles

In this section the energy concepts developed thus far are illustrated further by application
to systems undergoing thermodynamic cycles. Recall from Sec. 1.3 that when a system at a
given initial state goes through a sequence of processes and finally returns to that state, the
system has executed a thermodynamic cycle. The study of systems undergoing cycles has
played an important role in the development of the subject of engineering thermodynamics.
Both the first and second laws of thermodynamics have roots in the study of cycles. In ad-
dition, there are many important practical applications involving power generation, vehicle
propulsion, and refrigeration for which an understanding of thermodynamic cycles is neces-
sary. In this section, cycles are considered from the perspective of the conservation of en-
ergy principle. Cycles are studied in greater detail in subsequent chapters, using both the
conservation of energy principle and the second law of thermodynamics.
2.6.1 Cycle Energy Balance

The energy balance for any system undergoing a thermodynamic cycle takes the form
Ecycle Qcycle Wcycle (2.39)
where Qcycle and Wcycle represent net amounts of energy transfer by heat and work,
respectively, for the cycle. Since the system is returned to its initial state after the cycle,
2.6 Energy Analysis of Cycles 59
Hot Hot
body body
Q out
Q in
System System
Wcycle = Q in Q out Wcycle = Q out Q in
Q in
Q out
Cold Cold
body body
(a) (b)
Figure 2.15 Schematic diagrams of two important classes of
cycles. (a) Power cycles. (b) Refrigeration and heat pump cycles.
there is no net change in its energy. Therefore, the left side of Eq. 2.39 equals zero, and the
equation reduces to
Wcycle Qcycle (2.40)
Equation 2.40 is an expression of the conservation of energy principle that must be satisfied
by every thermodynamic cycle, regardless of the sequence of processes followed by the sys-
tem undergoing the cycle or the nature of the substances making up the system.
Figure 2.15 provides simplified schematics of two general classes of cycles considered in METHODOLOGY
this book: power cycles and refrigeration and heat pump cycles. In each case pictured, a sys- UPDATE
tem undergoes a cycle while communicating thermally with two bodies, one hot and the other When analyzing cycles,
cold. These bodies are systems located in the surroundings of the system undergoing the we normally take energy
cycle. During each cycle there is also a net amount of energy exchanged with the surround- transfers as positive in the
ings by work. Carefully observe that in using the symbols Qin and Qout on Fig. 2.15 we have directions of arrows on a
sketch of the system and
departed from the previously stated sign convention for heat transfer. In this section it is ad- write the energy balance
vantageous to regard Qin and Qout as transfers of energy in the directions indicated by the accordingly.
arrows. The direction of the net work of the cycle, Wcycle, is also indicated by an arrow.
Finally, note that the directions of the energy transfers shown in Fig. 2.15b are opposite to
those of Fig. 2.15a.
2.6.2 Power Cycles

Systems undergoing cycles of the type shown in Fig. 2.15a deliver a net work transfer of en-
ergy to their surroundings during each cycle. Any such cycle is called a power cycle. From power cycle
Eq. 2.40, the net work output equals the net heat transfer to the cycle, or
Wcycle Qin Qout 1power cycle2 (2.41)
where Qin represents the heat transfer of energy into the system from the hot body, and Qout
represents heat transfer out of the system to the cold body. From Eq. 2.41 it is clear that Qin
must be greater than Qout for a power cycle. The energy supplied by heat transfer to a system
undergoing a power cycle is normally derived from the combustion of fuel or a moderated
nuclear reaction; it can also be obtained from solar radiation. The energy Qout is generally
discharged to the surrounding atmosphere or a nearby body of water.
The performance of a system undergoing a power cycle can be described in terms of the
extent to which the energy added by heat, Qin, is converted to a net work output, Wcycle. The
extent of the energy conversion from heat to work is expressed by the following ratio, com-
monly called the thermal efficiency
Wcycle
thermal efficiency h 1power cycle2 (2.42)
Qin
Introducing Eq. 2.41, an alternative form is obtained as

Qin Qout
1power cycle2
Qout
h 1 (2.43)
Qin Qin
Since energy is conserved, it follows that the thermal efficiency can never be greater than
unity (100%). However, experience with actual power cycles shows that the value of thermal
efficiency is invariably less than unity. That is, not all the energy added to the system by heat
transfer is converted to work; a portion is discharged to the cold body by heat transfer. Using
the second law of thermodynamics, we will show in Chap. 5 that the conversion from heat
to work cannot be fully accomplished by any power cycle. The thermal efficiency of every
power cycle must be less than unity: 1.
2.6.3 Refrigeration and Heat Pump Cycles

refrigeration and heat Next, consider the refrigeration and heat pump cycles shown in Fig. 2.15b. For cycles of
pump cycles this type, Qin is the energy transferred by heat into the system undergoing the cycle from the
cold body, and Qout is the energy discharged by heat transfer from the system to the hot body.
To accomplish these energy transfers requires a net work input, Wcycle. The quantities Qin,
Qout, and Wcycle are related by the energy balance, which for refrigeration and heat pump
cycles takes the form
Wcycle Qout Qin 1refrigeration and heat pump cycles2 (2.44)
Since Wcycle is positive in this equation, it follows that Qout is greater than Qin.
Although we have treated them as the same to this point, refrigeration and heat pump cy-
cles actually have different objectives. The objective of a refrigeration cycle is to cool a re-
frigerated space or to maintain the temperature within a dwelling or other building below
that of the surroundings. The objective of a heat pump is to maintain the temperature within
a dwelling or other building above that of the surroundings or to provide heating for certain
industrial processes that occur at elevated temperatures.
Since refrigeration and heat pump cycles have different objectives, their performance
parameters, called coefficients of performance, are defined differently. These coefficients of
performance are considered next.
REFRIGERATION CYCLES
The performance of refrigeration cycles can be described as the ratio of the amount of
energy received by the system undergoing the cycle from the cold body, Qin, to the net
2.6 Energy Analysis of Cycles 61
work into the system to accomplish this effect, Wcycle. Thus, the coefficient of perform-
ance, , is
coefficient of
1refrigeration cycle2
Qin
b (2.45) performance:
Wcycle refrigeration
Introducing Eq. 2.44, an alternative expression for is obtained as
1refrigeration cycle2
Qin
b (2.46)
Qout Qin
For a household refrigerator, Qout is discharged to the space in which the refrigerator is
located. Wcycle is usually provided in the form of electricity to run the motor that drives the
refrigerator.
for example. . . in a refrigerator the inside compartment acts as the cold body and
the ambient air surrounding the refrigerator is the hot body. Energy Qin passes to the circu-
lating refrigerant from the food and other contents of the inside compartment. For this heat
transfer to occur, the refrigerant temperature is necessarily below that of the refrigerator con-
tents. Energy Qout passes from the refrigerant to the surrounding air. For this heat transfer to
occur, the temperature of the circulating refrigerant must necessarily be above that of the sur-
rounding air. To achieve these effects, a work input is required. For a refrigerator, Wcycle is
provided in the form of electricity.
HEAT PUMP CYCLES
The performance of heat pumps can be described as the ratio of the amount of energy
discharged from the system undergoing the cycle to the hot body, Qout, to the net work
into the system to accomplish this effect, Wcycle. Thus, the coefficient of performance,
, is
1heat pump cycle2

Qout coefficient of
g (2.47)
Wcycle performance: heat pump
Introducing Eq. 2.44, an alternative expression for this coefficient of performance is

obtained as
1heat pump cycle2

Qout
g (2.48)
Qout Qin
From this equation it can be seen that the value of is never less than unity. For residential
heat pumps, the energy quantity Qin is normally drawn from the surrounding atmosphere, the
ground, or a nearby body of water. Wcycle is usually provided by electricity.
The coefficients of performance and are defined as ratios of the desired heat transfer
effect to the cost in terms of work to accomplish that effect. Based on the definitions, it is
desirable thermodynamically that these coefficients have values that are as large as possible.
However, as discussed in Chap. 5, coefficients of performance must satisfy restrictions im-
posed by the second law of thermodynamics.
In this chapter, we have considered the concept of energy from for a process of a closed system is Eq. 2.35 and an accom-
an engineering perspective and have introduced energy bal- panying time rate form is Eq. 2.37. Equation 2.40 is a special
ances for applying the conservation of energy principle to form of the energy balance for a system undergoing a ther-
closed systems. A basic idea is that energy can be stored within modynamic cycle.
systems in three macroscopic forms: internal energy, kinetic The following checklist provides a study guide for this
energy, and gravitational potential energy. Energy also can be chapter. When your study of the text and end-of-chapter ex-
transferred to and from systems. ercises has been completed, you should be able to
Energy can be transferred to and from closed systems by
write out the meanings of the terms listed in the margins
two means only: work and heat transfer. Work and heat trans-
throughout the chapter and understand each of the related
fer are identified at the system boundary and are not proper-
concepts. The subset of key concepts listed below is par-
ties. In mechanics, work is energy transfer associated with
ticularly important in subsequent chapters.
macroscopic forces and displacements at the system bound-
ary. The thermodynamic definition of work introduced in this evaluate these energy quantities
chapter extends the notion of work from mechanics to in- kinetic and potential energy changes using Eqs. 2.5
clude other types of work. Energy transfer by heat is due to and 2.10, respectively.
a temperature difference between the system and its sur- work and power using Eqs. 2.12 and 2.13,
roundings, and occurs in the direction of decreasing temper- respectively.
ature. Heat transfer modes include conduction, radiation, and expansion or compression work using Eq. 2.17
convection. These sign conventions are used for work and
apply closed system energy balances in each of several
heat transfer:
alternative forms, appropriately modeling the case at
hand, correctly observing sign conventions for work
W, W e
# 7 0: work done by the system
6 0: work done by the system and heat transfer, and carefully applying SI and English
units.
Q, Q e
# 7 0: heat transfer to the system
conduct energy analyses for systems undergoing
6 0: heat transfer from the system
thermodynamic cycles using Eq. 2.40, and evaluating,
Energy is an extensive property of a system. Only changes as appropriate, the thermal efficiencies of power cycles
in the energy of a system have significance. Energy changes and coefficients of performance of refrigeration and heat
are accounted for by the energy balance. The energy balance pump cycles.
kinetic energy p. 30 internal energy p. 43 energy balance p. 48 refrigeration cycle p. 60

potential energy p. 32 heat transfer p. 44 power cycle p. 59 heat pump cycle
work p. 33 first law of p. 6061
power p. 35 thermodynamics p. 48
1. What forces act on the bicyle and rider considered in Sec. 5. List examples of heat transfer by conduction, radiation, and
2.2.2? Sketch a free body diagram. convection you might find in a kitchen.
2. Why is it incorrect to say that a system contains heat? 6. When a falling object impacts the earth and comes to rest,
3. An ice skater blows into cupped hands to warm them, yet at what happens to its kinetic and potential energies?
lunch blows across a bowl of soup to cool it. How can this be in- 7. When you stir a cup of coffee, what happens to the energy
terpreted thermodynamically? transferred to the coffee by work?
4. Sketch the steady-state temperature distribution for a furnace 8. What energy transfers by work and heat can you identify for
wall composed of an 8-inch-thick concrete inner layer and a 1/2- a moving automobile?
inch-thick steel outer layer.
9. Why are the symbols U, KE, and PE used to denote the 12. What form does the energy balance take for an isolated sys-
energy change during a process, but the work and heat transfer tem? Interpret the expression you obtain.
for the process represented, respectively, simply as W and Q? 13. How would you define an appropriate efficiency for the gear-
10. If the change in energy of a closed system is known for a box of Example 2.4?
process between two end states, can you determine if the energy 14. Two power cycles each receive the same energy input Qin
change was due to work, to heat transfer, or to some combina- and discharge energy Qout to the same lake. If the cycles have
tion of work and heat transfer? different thermal efficiencies, which discharges the greater
11. Referring to Fig. 2.8, can you tell which process, A or B, has amount Qout? Does this have any implications for the environ-
the greater heat transfer? ment?
Applying Energy Concepts from Mechanics (b) For a steel flywheel rotating at 3000 RPM, determine the
2.1 An automobile has a mass of 1200 kg. What is its kinetic kinetic energy, in N # m, and the mass, in kg, if R 0.38 m
energy, in kJ, relative to the road when traveling at a velocity and w 0.025 m.
of 50 km/h? If the vehicle accelerates to 100 km/h, what is the (c) Determine the radius, in m, and the mass, in kg, of an alu-
change in kinetic energy, in kJ? minum flywheel having the same width, angular velocity,
and kinetic energy as in part (b).
2.2 An object whose mass is 400 kg is located at an elevation
of 25 m above the surface of the earth. For g 9.78 m/s2, de- 2.8 Two objects having different masses fall freely under the
termine the gravitational potential energy of the object, in kJ, influence of gravity from rest and the same initial elevation.
relative to the surface of the earth. Ignoring the effect of air resistance, show that the magnitudes
of the velocities of the objects are equal at the moment just
2.3 An object of mass 1000 kg, initially having a velocity of
before they strike the earth.
100 m /s, decelerates to a final velocity of 20 m/s. What is the
change in kinetic energy of the object, in kJ? 2.9 An object whose mass is 25 kg is projected upward from
the surface of the earth with an initial velocity of 60 m/s. The
2.4 An airplane whose mass is 5000 kg is flying with a veloc-
only force acting on the object is the force of gravity. Plot the
ity of 150 m/s at an altitude of 10,000 m, both measured rel-
velocity of the object versus elevation. Determine the eleva-
ative to the surface of the earth. The acceleration of gravity
tion of the object, in ft, when its velocity reaches zero. The ac-
can be taken as constant at g 9.78 m/s2.
celeration of gravity is g 9.8 m/s2.
(a) Calculate the kinetic and potential energies of the airplane, 2.10 A block of mass 10 kg moves along a surface inclined
both in kJ. 30 relative to the horizontal. The center of gravity of the
(b) If the kinetic energy increased by 10,000 kJ with no change block is elevated by 3.0 m and the kinetic energy of the block
in elevation, what would be the final velocity, in m/s? decreases by 50 J. The block is acted upon by a constant
2.5 An object whose mass is 0.5 kg has a velocity of 30 m/s. force R parallel to the incline and by the force of gravity.
Determine Assume frictionless surfaces and let g 9.81 m/s2. Deter-
(a) the final velocity, in m/s, if the kinetic energy of the ob- mine the magnitude and direction of the constant force R,
ject decreases by 130 J. in N.
(b) the change in elevation, in ft, associated with a 130 J 2.11 Beginning from rest, an object of mass 200 kg slides
change in potential energy. Let g 9.81 m/s2. down a 10-m-long ramp. The ramp is inclined at an angle of
2.6 An object whose mass is 2 kg is accelerated from a veloc- 40 from the horizontal. If air resistance and friction between
ity of 200 m/s to a final velocity of 500 m/s by the action of the object and the ramp are negligible, determine the veloc-
a resultant force. Determine the work done by the resultant ity of the object, in m/s, at the bottom of the ramp. Let g
force, in kJ, if there are no other interactions between the ob- 9.81 m /s2.
ject and its surroundings.
Evaluating Work
2.7 A disk-shaped flywheel, of uniform density , outer ra-
2.12 A system with a mass of 5 kg, initially moving horizon-
dius R, and thickness w, rotates with an angular velocity ,
tally with a velocity of 40 m/s, experiences a constant hori-
in rad/s.
zontal deceleration of 2 m /s2 due to the action of a resultant
(a) Show that the moment of inertia, I vol rr2 dV, can be force. As a result, the system comes to rest. Determine the
expressed as I wR 42 and the kinetic energy can be length of time, in s, the force is applied and the amount of
expressed as KE I 22. energy transfer by work, in kJ.
2.13 The drag force, Fd, imposed by the surrounding air on a varies linearly from an initial value of 900 N to a final value
vehicle moving with velocity V is given by of zero. The atmospheric pressure is 100 kPa, and the area
of the piston face is 0.018 m2. Friction between the piston
Fd CdA12rV2
and the cylinder wall can be neglected. For the air, determine
where Cd is a constant called the drag coefficient, A is the pro- the initial and final pressures, in kPa, and the work, in kJ.
jected frontal area of the vehicle, and is the air density. De-
termine the power, in kW, required to overcome aerodynamic A = 0.018 m2
drag for a truck moving at 110 km/h, if Cd 0.65, A 10 m2,
and 1.1 kg/m3.
2.14 A major force opposing the motion of a vehicle is the patm = 100 kPa
rolling resistance of the tires, Fr, given by
Air
Fr f w
Spring force varies linearly from 900 N when
where f is a constant called the rolling resistance coefficient V1 = 0.003 m3 to zero when V2 = 0.002 m3
and w is the vehicle weight. Determine the power, in kW,
required to overcome rolling resistance for a truck weighing
Figure P2.19
322.5 kN that is moving at 110 km /h. Let f 0.0069.
2.15 Measured data for pressure versus volume during the ex-
pansion of gases within the cylinder of an internal combustion 2.20 Air undergoes two processes in series:
engine are given in the table below. Using data from the table, Process 12: polytropic compression, with n 1.3, from p1
complete the following: 100 kPa, v1 0.04 m3/kg to v2 0.02 m3/kg
(a) Determine a value of n such that the data are fit by an Process 23: constant-pressure process to v3 v1
equation of the form, pV n constant.
(b) Evaluate analytically the work done by the gases, in kJ, Sketch the processes on a pv diagram and determine the work
using Eq. 2.17 along with the result of part (a). per unit mass of air, in kJ/kg.
(c) Using graphical or numerical integration of the data, eval- 2.21 For the cycle of Problem 1.25, determine the work for each
uate the work done by the gases, in kJ. process and the net work for the cycle, each in kJ.
(d) Compare the different methods for estimating the work 2.22 The driveshaft of a buildings air-handling fan is turned at
used in parts (b) and (c). Why are they estimates? 300 RPM by a belt running on a 0.3-m-diameter pulley. The
net force applied by the belt on the pulley is 2000 N. Deter-
Data Point p (bar) V (cm3) mine the torque applied by the belt on the pulley, in N # m, and
the power transmitted, in kW.
1 15 300
2.23 An electric motor draws a current of 10 amp with a voltage
2 12 361
of 110 V. The output shaft develops a torque of 10.2 N # m and
3 9 459
a rotational speed of 1000 RPM. For operation at steady state,
4 6 644
determine
5 4 903
6 2 1608 (a) the electric power required by the motor and the power de-
veloped by the output shaft, each in kW.
(b) the net power input to the motor, in kW.
2.16 One-fourth kg of a gas contained within a pistoncylinder (c) the amount of energy transferred to the motor by electri-
assembly undergoes a constant-pressure process at 5 bar be- cal work and the amount of energy transferred out of the
ginning at v1 0.20 m3/kg. For the gas as the system, the work motor by the shaft, in kW # h during 2 h of operation.
is 15 kJ. Determine the final volume of the gas, in m3. 2.24 A 12-V automotive storage battery is charged with a con-
2.17 A gas is compressed from V1 0.3 m3, p1 1 bar to stant current of 2 amp for 24 h. If electricity costs $0.08 per
V2 0.1 m3, p2 3 bar. Pressure and volume are related lin- kW # h, determine the cost of recharging the battery.
early during the process. For the gas, find the work, in kJ. 2.25 For your lifestyle, estimate the monthly cost of operating
2.18 A gas expands from an initial state where p1 500 kPa the following household items: microwave oven, refrigerator,
and V1 0.1 m3 to a final state where p2 100 kPa. The electric space heater, personal computer, hand-held hair drier,
relationship between pressure and volume during the process a 100-W light bulb. Assume the cost of electricity is $0.08 per
is pV constant. Sketch the process on a pV diagram and kW # h.
determine the work, in kJ. 2.26 A solid cylindrical bar (see Fig. 2.9) of diameter 5 mm is
2.19 Warm air is contained in a pistoncylinder assembly ori- slowly stretched from an initial length of 10 cm to a final length
ented horizontally as shown in Fig. P2.19. The air cools of 10.1 cm. The normal stress in the bar varies according to
slowly from an initial volume of 0.003 m3 to a final volume C(x x0)x0, where x is the length of the bar, x0 is the
of 0.002 m3. During the process, the spring exerts a force that initial length, and C is a material constant (Youngs modulus).
For C 2 107 kPa, determine the work done on the bar, in 2.35 A closed system of mass 5 kg undergoes a process in which
J, assuming the diameter remains constant. there is work of magnitude 9 kJ to the system from the sur-
roundings. The elevation of the system increases by 700 m
2.27 A wire of cross-sectional area A and initial length x0 is
during the process. The specific internal energy of the system
stretched. The normal stress acting in the wire varies linearly
decreases by 6 kJ/kg and there is no change in kinetic energy
with strain, , where
of the system. The acceleration of gravity is constant at g 9.6
e 1x x0 2 x0 m/s2. Determine the heat transfer, in kJ.
and x is the length of the wire. Assuming the cross-sectional 2.36 A closed system of mass 20 kg undergoes a process in
area remains constant, derive an expression for the work done which there is a heat transfer of 1000 kJ from the system to
on the wire as a function of strain. the surroundings. The work done on the system is 200 kJ. If
the initial specific internal energy of the system is 300 kJ/kg,
2.28 A soap film is suspended on a 5 cm 5 cm wire frame,
what is the final specific internal energy, in kJ/kg? Neglect
as shown in Fig. 2.10. The movable wire is displaced 1 cm by
changes in kinetic and potential energy.
an applied force, while the surface tension of the soap film
remains constant at 25 105 N/cm. Determine the work done 2.37 As shown in Fig. P2.37, 5 kg of steam contained within
in stretching the film, in J. a pistoncylinder assembly undergoes an expansion from state
1, where the specific internal energy is u1 2709.9 kJ/kg,
2.29 Derive an expression to estimate the work required to
to state 2, where u2 2659.6 kJ/kg. During the process, there
inflate a common balloon. List all simplifying assumptions.
is heat transfer to the steam with a magnitude of 80 kJ. Also,
a paddle wheel transfers energy to the steam by work in the
Evaluating Heat Transfer
amount of 18.5 kJ. There is no significant change in the
2.30 A 0.2-m-thick plane wall is constructed of concrete. At kinetic or potential energy of the steam. Determine the en-
steady state, the energy transfer rate by conduction through a ergy transfer by work from the steam to the piston during
1-m2 area of the wall is 0.15 kW. If the temperature distribu- the process, in kJ.
tion is linear through the wall, what is the temperature differ-
ence across the wall, in K?
2.31 A 2-cm-diameter surface at 1000 K emits thermal radia-
tion at a rate of 15 W. What is the emissivity of the surface?
Assuming constant emissivity, plot the rate of radiant emis- 5 kg of
sion, in W, for surface temperatures ranging from 0 to 2000 K. steam
The StefanBoltzmann constant, , is 5.67 108 W/m2 # K4.
Wpiston = ?
2.32 A flat surface having an area of 2 m2 and a temperature Wpw = 18.5 kJ
of 350 K is cooled convectively by a gas at 300 K. Using data
from Table 2.1, determine the largest and smallest heat trans-
fer rates, in kW, that might be encountered for (a) free con-
Q = +80 kJ u1 = 2709.9 kJ/kg
vection, (b) forced convection. u2 = 2659.6 kJ/kg
2.33 A flat surface is covered with insulation with a thermal
conductivity of 0.08 W/m # K. The temperature at the interface
between the surface and the insulation is 300C. The outside
of the insulation is exposed to air at 30C, and the heat trans- Figure P2.37
fer coefficient for convection between the insulation and the
air is 10 W/m2 # K. Ignoring radiation, determine the minimum
thickness of insulation, in m, such that the outside of the in- 2.38 An electric generator coupled to a windmill produces an
sulation is no hotter than 60C at steady state. average electric power output of 15 kW. The power is used to
charge a storage battery. Heat transfer from the battery to the
Using the Energy Balance surroundings occurs at a constant rate of 1.8 kW. Determine,
2.34 Each line in the following table gives information about a for 8 h of operation
process of a closed system. Every entry has the same energy (a) the total amount of energy stored in the battery, in kJ.
units. Fill in the blank spaces in the table. (b) the value of the stored energy, in $, if electricity is valued
at $0.08 per kW # h.
Process Q W E1 E2 E 2.39 A closed system undergoes a process during which there
is energy transfer from the system by heat at a constant rate of
a
50 20
50
10 kW, and the power varies with time according to
b
50
20
20
40
60
20
W e
c # 8t 0 6 t1h
d 90
50 0 8 t 7 1h
e
50
20 100 #
where t is time, in h, and W is in kW.
(a) What is the time rate of change of system energy at t 2.46 A gas contained within a pistoncylinder assembly is
0.6 h, in kW? shown in Fig. P2.46. Initially, the piston face is at x 0, and
(b) Determine the change in system energy after 2 h, in kJ. the spring exerts no force on the piston. As a result of heat
2.40 A storage battery develops a power output of transfer, the gas expands, raising the piston until it hits the
# stops. At this point the piston face is located at x
W 1.2 exp1t602 0.06 m, and the heat transfer ceases. The force exerted by the
# spring on the piston as the gas expands varies linearly with
where W is power, in kW, and t is time, in s. Ignoring heat
x according to
transfer
(a) plot the power output, in kW, and the change in energy of Fspring kx
the battery, in kJ, each as a function of time. where k 9,000 N/m. Friction between the piston and the
(b) What are the limiting values for the power output and the cylinder wall can be neglected. The acceleration of gravity
change in energy of the battery as t S ? Discuss. is g 9.81 m/s2. Additional information is given on
2.41 A gas expands in a pistoncylinder assembly from p1 8 Fig. P2.70.
bar, V1 0.02 m3 to p2 2 bar in a process during which the
relation between pressure and volume is pV1.2 constant. The patm = 1 bar
mass of the gas is 0.25 kg. If the specific internal energy of Apist = 0.0078 m2
the gas decreases by 55 kJ/kg during the process, determine m pist = 10 kg
the heat transfer, in kJ. Kinetic and potential energy effects are
negligible.
2.42 Two kilograms of air is contained in a rigid well-insulated
tank with a volume of 0.6 m3. The tank is fitted with a paddle
wheel that transfers energy to the air at a constant rate of 10 W
for 1 h. If no changes in kinetic or potential energy occur, x=0
Gas
determine
m gas = 0.5 g
(a) the specific volume at the final state, in m3/kg.
(b) the energy transfer by work, in kJ.
(c) the change in specific internal energy of the air, in kJ/kg.
2.43 A gas is contained in a closed rigid tank. An electric
resistor in the tank transfers energy to the gas at a constant rate
of 1000 W. Heat transfer# between the gas #and the surround-
ings occurs at a rate of Q 50t, where Q is in watts, and t
is time, in min. Figure P2.46
(a) Plot the time rate of change of energy of the gas for
0 t 20 min, in watts. (a) What is the initial pressure of the gas, in kPa?
(b) Determine the net change in energy of the gas after 20 (b) Determine the work done by the gas on the piston, in J.
min, in kJ. (c) If the specific internal energies of the gas at the initial and
(c) If electricity is valued at $0.08 per kW # h, what is the cost final states are 210 and 335 kJ/kg, respectively, calculate
of the electrical input to the resistor for 20 min of operation? the heat transfer, in J.
2.44 Steam in a pistoncylinder assembly undergoes a poly-
tropic process, with n 2, from an initial state where p1 3.45 Analyzing Thermodynamic Cycles
MPa, v1 .106 m3/kg, u1 3171 kJ/kg to a final state where 2.47 The following table gives data, in kJ, for a system under-
u2 2304 kJ/kg. During the process, there is a heat transfer going a thermodynamic cycle consisting of four processes in
from the steam of magnitude 361.8. The mass of steam is .544 kg. series. For the cycle, kinetic and potential energy effects can
Neglecting changes in kinetic and potential energy, determine the be neglected. Determine
work, in kJ. (a) the missing table entries, each in kJ.
2.45 Air is contained in a vertical pistoncylinder assembly (b) whether the cycle is a power cycle or a refrigeration
by a piston of mass 50 kg and having a face area of 0.01 m2. cycle.
The mass of the air is 5 g, and initially the air occupies a
volume of 5 liters. The atmosphere exerts a pressure of 100 Process U Q W
kPa on the top of the piston. The volume of the air slowly
12 600 600
decreases to 0.002 m3 as the specific internal energy of the
23 1300
air decreases by 260 kJ/kg. Neglecting friction between the
34 700 0
piston and the cylinder wall, determine the heat transfer to
41 500 700
the air, in kJ.
Design & Open Ended Problems: Exploring Engineering Practice 67
2.48 A gas undergoes a thermodynamic cycle consisting of 2.53 A power cycle has a thermal efficiency of 35% and gen-
three processes: erates electricity at a rate of 100 MW. The electricity is val-
ued at $0.08
# per kW # h. Based on the cost of fuel, the cost to
Process 12: compression with pV constant, from p1 1 supply Qin is $4.50 per GJ. For 8000 hours of operation an-
bar, V1 1.6 m3 to V2 0.2 m3, U2 U1 0 nually, determine, in $,
Process 23: constant pressure to V3 V1 (a) the value of the electricity generated per year.
Process 31: constant volume, U1 U3 3549 kJ (b) the annual fuel cost.
2.54 For each of the following, what plays the roles of the hot
There are no significant changes in kinetic or potential energy.
body and the cold body of the appropriate Fig. 2.15
Determine the heat transfer and work for Process 23, in kJ.
schematic?
Is this a power cycle or a refrigeration cycle?
(a) Window air conditioner
2.49 A gas undergoes a thermodynamic cycle consisting of
(b) Nuclear submarine power plant
three processes:
(c) Ground-source heat pump
Process 12: constant volume, V 0.028 m3, U2 U1 2.55 In what ways do automobile engines operate analogously
26.4 kJ to the power cycle shown in Fig. 2.15a? How are they differ-
Process 23: expansion with pV constant, U3 U2 ent? Discuss.
Process 31: constant pressure, p 1.4 bar, W31 10.5 kJ 2.56 A refrigeration cycle operating as shown in Fig. 2.15b has
heat transfer Qout 2530 kJ and net work of Wcycle 844 kJ.
There are no significant changes in kinetic or potential energy. Determine the coefficient of performance for the cycle.
(a) Sketch the cycle on a pV diagram. 2.57 A refrigeration cycle operates as shown in Fig. 2.15b with
(b) Calculate the net work for the cycle, in kJ. a coefficient of performance 1.5. For the cycle, Qout
(c) Calculate the heat transfer for process 23, in kJ. 500 kJ. Determine Qin and Wcycle, each in kJ.
(d) Calculate the heat transfer for process 31, in kJ.
2.58 A refrigeration cycle operates continuously and removes en-
Is this a power cycle or a refrigeration cycle? ergy from the refrigerated space at a rate of 3.5 kW. For a coef-
2.50 For a power cycle operating as in Fig. 2.15a, the heat trans- ficient of performance of 2.6, determine the net power required.
fers are Qin 50 kJ and Qout 35 kJ. Determine the net work,
2.59 A heat pump cycle whose coefficient of performance is
in kJ, and the thermal efficiency.
2.5 delivers energy by heat transfer to a dwelling at a rate of
2.51 The thermal efficiency of a power cycle operating as 20 kW.
shown in Fig. 2.15a is 35%, and Qout 40 MJ. Determine the (a) Determine the net power required to operate the heat pump,
net work developed and the heat transfer Qin, each in MJ. in kW.
2.52 A power cycle receives energy by heat transfer from the (b) Evaluating electricity at $0.08 per kW # h, determine the
combustion of fuel at a rate of 300 MW. The thermal efficiency cost of electricity in a month when the heat pump oper-
of the cycle is 33.3%. ates for 200 hours.
(a) Determine the net rate power is developed, in MW. 2.60 A household refrigerator with a coefficient of performance
(b) For 8000 hours of operation annually, determine the net of 2.4 removes energy from the refrigerated space at a rate of
work output, in kW # h per year. 200 W. Evaluating electricity at $0.08 per kW # h, determine
(c) Evaluating the net work output at $0.08 per kW # h, deter- the cost of electricity in a month when the refrigerator oper-
mine the value of the net work, in $/year. ates for 360 hours.
2.1D The effective use of our energy resources is an important the extent to which these renewable resources are
societal goal. utilized.
(a) Summarize in a pie chart the data on the use of fuels in 2.2D Among several engineers and scientists who contributed
your state in the residential, commercial, industrial, and to the development of the first law of thermodynamics are:
transportation sectors. What factors may affect the future (a) James Joule.
availability of these fuels? Does your state have a written (b) James Watt.
energy policy? Discuss. (c) Benjamin Thompson (Count Rumford).
(b) Determine the present uses of solar energy, hydropower, (d) Sir Humphrey Davy.
and wind energy in your area. Discuss factors that affect (e) Julius Robert Mayer.
Write a biographical sketch of one of them, including a de- such bottles and explain the basic principles that make them
scription of his principal contributions to the first law. effective.
2.3D Specially designed flywheels have been used by electric 2.8D A brief discussion of power, refrigeration, and heat pump
utilities to store electricity. Automotive applications of fly- cycles is presented in this chapter. For one, or more, of the
wheel energy storage also have been proposed. Write a report applications listed below, explain the operating principles and
that discusses promising uses of flywheels for energy storage, discuss the significant energy transfers and environmental
including consideration of flywheel materials, their properties, impacts:
and costs.
(a) coal-fired power plant.
2.4D Develop a list of the most common home-heating options (b) nuclear power plant.
in your locale. For a 2500-ft2 dwelling, what is the annual fuel (c) refrigeration unit supplying chilled water to the cooling
cost or electricity cost for each option listed? Also, what is the system of a large building.
installed cost of each option? For a 15-year life, which option (d) heat pump for residential heating and air conditioning.
is the most economical? (e) automobile air conditioning unit
2.5D The overall convective heat transfer coefficient is used 2.9D Fossil-fuel power plants produce most of the electricity
in the analysis of heat exchangers (Sec. 4.3) to relate the over- generated annually in the United States. The cost of electric-
all heat transfer rate and the log mean temperature difference ity is determined by several factors, including the power plant
between the two fluids passing through the heat exchanger. thermal efficiency, the unit cost of the fuel, in $ per kW # h,
Write a memorandum explaining these concepts. Include data and the plant capital cost, in $ per kW of power generated.
from the engineering literature on characteristic values of the Prepare a memorandum comparing typical ranges of these
overall convective heat transfer coefficient for the following three factors for coal-fired steam power plants and natural
heat exchanger applications: air-to-air heat recovery, air- gasfired gas turbine power plants. Which type of plant is most
to-refrigerant evaporators, shell-and-tube steam condensers. prevalent in the United States?
2.6D The outside surfaces of small gasoline engines are often 2.10D Lightweight, portable refrigerated chests are available
covered with fins that enhance the heat transfer between the for keeping food cool. These units use a thermoelectric cool-
hot surface and the surrounding air. Larger engines, like auto- ing module energized by plugging the unit into an automobile
mobile engines, have a liquid coolant flowing through passages cigarette lighter. Thermoelectric cooling requires no moving
in the engine block. The coolant then passes through the radi- parts and requires no refrigerant. Write a report that explains
ator (a finned-tube heat exchanger) where the needed cooling this thermoelectric refrigeration technology. Discuss the
is provided by the air flowing through the radiator. Consider- applicability of this technology to larger-scale refrigeration
ing appropriate data for heat transfer coefficients, engine size, systems.
and other design issues related to engine cooling, explain why
2.11D Hybrids Harvest Energy (see box Sec. 2.1). Critically
some engines use liquid coolants and others do not.
compare and evaluate the various hybrid electric vehicles
2.7D Common vacuum-type thermos bottles can keep bever- on the market today. Write a report including at least three
ages hot or cold for many hours. Describe the construction of references.
C
H
A
P
T
Evaluating
Properties
E
R 3
E N G I N E E R I N G C O N T E X T To apply the energy balance to a sys-
tem of interest requires knowledge of the properties of the system and how the properties
are related. The objective of this chapter is to introduce property relations relevant to en- chapter objective
gineering thermodynamics. As part of the presentation, several examples are provided that
illustrate the use of the closed system energy balance introduced in Chap. 2 together with
the property relations considered in this chapter.
3.1 Fixing the State

The state of a closed system at equilibrium is its condition as described by the values of its
thermodynamic properties. From observation of many thermodynamic systems, it is known
that not all of these properties are independent of one another, and the state can be uniquely
determined by giving the values of the independent properties. Values for all other thermo-
dynamic properties are determined once this independent subset is specified. A general rule
known as the state principle has been developed as a guide in determining the number of in- state principle
dependent properties required to fix the state of a system.
For most applications considered in this book, we are interested in what the state princi-
ple says about the intensive states of systems. Of particular interest are systems of commonly
encountered pure substances, such as water or a uniform mixture of nonreacting gases. These
systems are classed as simple compressible systems. Experience shows that the simple com- simple compressible
pressible systems model is useful for a wide range of engineering applications. For such sys- systems
tems, the state principle indicates that the number of independent intensive properties is two.
for example. . . in the case of a gas, temperature and another intensive property such
as a specific volume might be selected as the two independent properties. The state princi-
ple then affirms that pressure, specific internal energy, and all other pertinent intensive prop-
erties could be determined as functions of T and v: p p(T, v), u u(T, v), and so on. The
functional relations would be developed using experimental data and would depend explic-
itly on the particular chemical identity of the substances making up the system. The devel-
opment of such functions is discussed in Chap. 11.
Intensive properties such as velocity and elevation that are assigned values relative to
datums outside the system are excluded from present considerations. Also, as suggested by
the name, changes in volume can have a significant influence on the energy of simple
69
70 Chapter 3 Evaluating Properties
compressible systems. The only mode of energy transfer by work that can occur as a simple
compressible system undergoes quasiequilibrium processes, is associated with volume change
and is given by p dV.
To provide a foundation for subsequent developments involving property relations, we
conclude this introduction with more detailed considerations of the state principle and sim-
ple compressible system concepts. Based on considerable empirical evidence, it has been
concluded that there is one independent property for each way a systems energy can be var-
ied independently. We saw in Chap. 2 that the energy of a closed system can be altered in-
dependently by heat or by work. Accordingly, an independent property can be associated
with heat transfer as one way of varying the energy, and another independent property can
be counted for each relevant way the energy can be changed through work. On the basis of
experimental evidence, therefore, the state principle asserts that the number of independent
properties is one plus the number of relevant work interactions. When counting the number
of relevant work interactions, it suffices to consider only those that would be significant in
quasiequilibrium processes of the system.
simple system The term simple system is applied when there is only one way the system energy can be
significantly altered by work as the system undergoes quasiequilibrium processes. Therefore,
counting one independent property for heat transfer and another for the single work mode
gives a total of two independent properties needed to fix the state of a simple system. This
is the state principle for simple systems. Although no system is ever truly simple, many
systems can be modeled as simple systems for the purpose of thermodynamic analysis.
The most important of these models for the applications considered in this book is the
simple compressible system. Other types of simple systems are simple elastic systems and
simple magnetic systems.
EVALUATING PROPERTIES:
GENERAL CONSIDERATIONS
This part of the chapter is concerned generally with the thermodynamic properties of sim-
ple compressible systems consisting of pure substances. A pure substance is one of uniform
and invariable chemical composition. Property relations for systems in which composition
changes by chemical reaction are considered in Chap. 13. In the second part of this chapter,
we consider property evaluation using the ideal gas model.
3.2 pvT Relation

We begin our study of the properties of pure, simple compressible substances and the rela-
tions among these properties with pressure, specific volume, and temperature. From experi-
ment it is known that temperature and specific volume can be regarded as independent and
pressure determined as a function of these two: p p(T, v). The graph of such a function
pvT surface is a surface, the pvT surface.
3.2.1 pvT Surface

Figure 3.1 is the pvT surface of a substance such as water that expands on freezing.
Figure 3.2 is for a substance that contracts on freezing, and most substances exhibit this char-
acteristic. The coordinates of a point on the pvT surfaces represent the values that pressure,
specific volume, and temperature would assume when the substance is at equilibrium.
3.2 pvT Relation 71
Liquid
Critical
point
Pressure
Liq
Solid uid
Tri va -
ple po
lin r
e
Va Tc
So p or
lid
Sp -va
eci por re
fic atu
vol mper
u me Te
(a) Solid
S L Critical
point
Pressure
Pressure
Critical
Solid Liquid point
L Liquid-
vapor
V Vapor T > Tc
S Vapor Tc
Triple point Triple line
V Solid-vapor T < Tc
Temperature Specific volume
(b) (c)
Figure 3.1 pvT surface and projections for a substance that expands on freez-
ing. (a) Three-dimensional view. (b) Phase diagram. (c) pv diagram.
There are regions on the pvT surfaces of Figs. 3.1 and 3.2 labeled solid, liquid, and
vapor. In these single-phase regions, the state is fixed by any two of the properties: pressure,
specific volume, and temperature, since all of these are independent when there is a single
phase present. Located between the single-phase regions are two-phase regions where two two-phase regions
phases exist in equilibrium: liquidvapor, solidliquid, and solidvapor. Two phases can co-
exist during changes in phase such as vaporization, melting, and sublimation. Within the two-
phase regions pressure and temperature are not independent; one cannot be changed without
changing the other. In these regions the state cannot be fixed by temperature and pressure
alone; however, the state can be fixed by specific volume and either pressure or temperature.
Three phases can exist in equilibrium along the line labeled triple line. triple line
A state at which a phase change begins or ends is called a saturation state. The dome-
saturation state
shaped region composed of the two-phase liquidvapor states is called the vapor dome. The
lines bordering the vapor dome are called saturated liquid and saturated vapor lines. At the vapor dome
top of the dome, where the saturated liquid and saturated vapor lines meet, is the critical
critical point
point. The critical temperature Tc of a pure substance is the maximum temperature at which
liquid and vapor phases can coexist in equilibrium. The pressure at the critical point is called
Solid Liquid
uid
Critical
Solid-Liq
Pressure
point Constant-
pressure line
Va
p or
So
lid
-va Tc
Sp po
eci r t ure
fic era
vo
lum e mp
T
e
(a)
Solid-liquid
S
Solid
L
Critical
Pressure
Pressure
Liquid
Solid point
Critical
point
Liquid-
L vapor
V T > Tc
Triple line Tc
Vapor Vapor
S Triple point T < Tc
V Solid-vapor
Temperature Specific volume
(b) (c)
Figure 3.2 pvT surface and projections for a substance that contracts
on freezing. (a) Three-dimensional view. (b) Phase diagram. (c) pv diagram.
the critical pressure, pc. The specific volume at this state is the critical specific volume. Values
of the critical point properties for a number of substances are given in Tables A-1 located in
the Appendix.
The three-dimensional pvT surface is useful for bringing out the general relationships
among the three phases of matter normally under consideration. However, it is often more
convenient to work with two-dimensional projections of the surface. These projections are
considered next.
3.2.2 Projections of the pvT Surface

THE PHASE DIAGRAM
If the pvT surface is projected onto the pressuretemperature plane, a property diagram
phase diagram known as a phase diagram results. As illustrated by Figs. 3.1b and 3.2b, when the surface
is projected in this way, the two-phase regions reduce to lines. A point on any of these lines
represents all two-phase mixtures at that particular temperature and pressure.
3.2 pvT Relation 73
The term saturation temperature designates the temperature at which a phase change saturation temperature
takes place at a given pressure, and this pressure is called the saturation pressure for the saturation pressure
given temperature. It is apparent from the phase diagrams that for each saturation pressure
there is a unique saturation temperature, and conversely.
The triple line of the three-dimensional pvT surface projects onto a point on the phase
diagram. This is called the triple point. Recall that the triple point of water is used as a ref- triple point
erence in defining temperature scales (Sec. 1.6). By agreement, the temperature assigned to
the triple point of water is 273.16 K. The measured pressure at the triple point of water is
0.6113 kPa.
The line representing the two-phase solidliquid region on the phase diagram slopes to
the left for substances that expand on freezing and to the right for those that contract. Al-
though a single solid phase region is shown on the phase diagrams of Figs. 3.1 and 3.2, solids
can exist in different solid phases. For example, seven different crystalline forms have been
identified for water as a solid (ice).
p v DIAGRAM
Projecting the pvT surface onto the pressurespecific volume plane results in a pv diagram, pv diagram
as shown by Figs. 3.1c and 3.2c. The figures are labeled with terms that have already been
introduced.
When solving problems, a sketch of the pv diagram is frequently convenient. To facili-
tate the use of such a sketch, note the appearance of constant-temperature lines (isotherms).
By inspection of Figs. 3.1c and 3.2c, it can be seen that for any specified temperature less
than the critical temperature, pressure remains constant as the two-phase liquidvapor region
is traversed, but in the single-phase liquid and vapor regions the pressure decreases at fixed
temperature as specific volume increases. For temperatures greater than or equal to the crit-
ical temperature, pressure decreases continuously at fixed temperature as specific volume in-
creases. There is no passage across the two-phase liquidvapor region. The critical isotherm
passes through a point of inflection at the critical point and the slope is zero there.
Tv DIAGRAM
Projecting the liquid, two-phase liquidvapor, and vapor regions of the pvT surface onto
the temperaturespecific volume plane results in a Tv diagram as in Fig. 3.3. Since con- Tv diagram
sistent patterns are revealed in the pvT behavior of all pure substances, Fig. 3.3 showing
a Tv diagram for water can be regarded as representative.
pc = 22.09 MPa
30 MPa
10 MPa
Tc
Critical
point
Temperature
Liquid Vapor
1.014 bar
Liquid-vapor s
100C
f g Figure 3.3 Sketch of a temperature
specific volume diagram for water show-
20C l ing the liquid, two-phase liquidvapor,
Specific volume and vapor regions (not to scale).
As for the pv diagram, a sketch of the Tv diagram is often convenient for problem
solving. To facilitate the use of such a sketch, note the appearance of constant-pressure
lines (isobars). For pressures less than the critical pressure, such as the 10 MPa isobar on
Fig. 3.3, the pressure remains constant with temperature as the two-phase region is tra-
versed. In the single-phase liquid and vapor regions the temperature increases at fixed pres-
sure as the specific volume increases. For pressures greater than or equal to the critical
pressure, such as the one marked 30 MPa on Fig. 3.3, temperature increases continuously
at fixed pressure as the specific volume increases. There is no passage across the two-phase
liquidvapor region.
The projections of the pvT surface used in this book to illustrate processes are not
generally drawn to scale. A similar comment applies to other property diagrams introduced
later.
3.2.3 Studying Phase Change

It is instructive to study the events that occur as a pure substance undergoes a phase change.
To begin, consider a closed system consisting of a unit mass (1 kg) of liquid water at 20C
contained within a pistoncylinder assembly, as illustrated in Fig. 3.4a. This state is repre-
sented by point l on Fig. 3.3. Suppose the water is slowly heated while its pressure is kept
constant and uniform throughout at 1.014 bar.
LIQUID STATES
As the system is heated at constant pressure, the temperature increases considerably while
the specific volume increases slightly. Eventually, the system is brought to the state repre-
sented by f on Fig. 3.3. This is the saturated liquid state corresponding to the specified pres-
sure. For water at 1.014 bar the saturation temperature is 100C. The liquid states along the
subcooled liquid line segment lf of Fig. 3.3 are sometimes referred to as subcooled liquid states because the
temperature at these states is less than the saturation temperature at the given pressure. These
compressed liquid states are also referred to as compressed liquid states because the pressure at each state is
higher than the saturation pressure corresponding to the temperature at the state. The names
liquid, subcooled liquid, and compressed liquid are used interchangeably.
TWO-PHASE, LIQUIDVAPOR MIXTURE
When the system is at the saturated liquid state (state f of Fig. 3.3), additional heat transfer
at fixed pressure results in the formation of vapor without any change in temperature but
with a considerable increase in specific volume. As shown in Fig. 3.4b, the system would
Water vapor Water vapor
Liquid water Liquid water Figure 3.4 Illustration of

constant-pressure change from
(a) (b) (c) liquid to vapor for water.
3.2 pvT Relation 75
now consist of a two-phase liquidvapor mixture. When a mixture of liquid and vapor exists
in equilibrium, the liquid phase is a saturated liquid and the vapor phase is a saturated va-
por. If the system is heated further until the last bit of liquid has vaporized, it is brought to
point g on Fig. 3.3, the saturated vapor state. The intervening two-phase liquidvapor mixture two-phase
states can be distinguished from one another by the quality, an intensive property. liquidvapor mixture
For a two-phase liquidvapor mixture, the ratio of the mass of vapor present to the total
mass of the mixture is its quality, x. In symbols,
mvapor
x (3.1) quality
mliquid
mvapor
The value of the quality ranges from zero to unity: at saturated liquid states, x 0, and
at saturated vapor states, x 1.0. Although defined as a ratio, the quality is frequently
given as a percentage. Examples illustrating the use of quality are provided in Sec. 3.3.
Similar parameters can be defined for two-phase solidvapor and two-phase solidliquid
mixtures.
VAPOR STATES
Let us return to a consideration of Figs. 3.3 and 3.4. When the system is at the saturated va-
por state (state g on Fig. 3.3), further heating at fixed pressure results in increases in both
temperature and specific volume. The condition of the system would now be as shown in
Fig. 3.4c. The state labeled s on Fig. 3.3 is representative of the states that would be attained
by further heating while keeping the pressure constant. A state such as s is often referred to
as a superheated vapor state because the system would be at a temperature greater than the superheated vapor
saturation temperature corresponding to the given pressure.
Consider next the same thought experiment at the other constant pressures labeled on
Fig. 3.3, 10 MPa, 22.09 MPa, and 30 MPa. The first of these pressures is less than the crit-
ical pressure of water, the second is the critical pressure, and the third is greater than the
critical pressure. As before, let the system initially contain a liquid at 20C. First, let us
study the system if it were heated slowly at 10 MPa. At this pressure, vapor would form
at a higher temperature than in the previous example, because the saturation pressure is
higher (refer to Fig. 3.3). In addition, there would be somewhat less of an increase in spe-
cific volume from saturated liquid to vapor, as evidenced by the narrowing of the vapor
dome. Apart from this, the general behavior would be the same as before. Next, consider
the behavior of the system were it heated at the critical pressure, or higher. As seen by fol-
lowing the critical isobar on Fig. 3.3, there would be no change in phase from liquid to
vapor. At all states there would be only one phase. Vaporization (and the inverse process
of condensation) can occur only when the pressure is less than the critical pressure. Thus,
at states where pressure is greater than the critical pressure, the terms liquid and vapor tend
to lose their significance. Still, for ease of reference to such states, we use the term liquid
when the temperature is less than the critical temperature and vapor when the temperature
is greater than the critical temperature.
MELTING AND SUBLIMATION
Although the phase change from liquid to vapor (vaporization) is the one of principal interest
in this book, it is also instructive to consider the phase changes from solid to liquid (melt-
ing) and from solid to vapor (sublimation). To study these transitions, consider a system con-
sisting of a unit mass of ice at a temperature below the triple point temperature. Let us begin
Critical
Liquid point
a b c
Melting
Vaporization
Pressure
a b c
Solid
Triple point Vapor
Sublimation
a b c
Figure 3.5 Phase diagram for water (not to

Temperature scale).
with the case where the system is at state a of Fig. 3.5, where the pressure is greater than
the triple point pressure. Suppose the system is slowly heated while maintaining the pres-
sure constant and uniform throughout. The temperature increases with heating until point b
on Fig. 3.5 is attained. At this state the ice is a saturated solid. Additional heat transfer at
fixed pressure results in the formation of liquid without any change in temperature. As the
system is heated further, the ice continues to melt until eventually the last bit melts, and the
system contains only saturated liquid. During the melting process the temperature and pres-
sure remain constant. For most substances, the specific volume increases during melting, but
for water the specific volume of the liquid is less than the specific volume of the solid. Fur-
ther heating at fixed pressure results in an increase in temperature as the system is brought
to point c on Fig. 3.5. Next, consider the case where the system is initially at state a of
Fig. 3.5, where the pressure is less than the triple point pressure. In this case, if the system
is heated at constant pressure it passes through the two-phase solidvapor region into the
vapor region along the line abc shown on Fig. 3.5. The case of vaporization discussed
previously is shown on Fig. 3.5 by the line abc.
3.3 Retrieving Thermodynamic Properties

Thermodynamic property data can be retrieved in various ways, including tables, graphs,
equations, and computer software. The emphasis of the present section is on the use of tables
of thermodynamic properties, which are commonly available for pure, simple compressible
substances of engineering interest. The use of these tables is an important skill. The ability
to locate states on property diagrams is an important related skill. The software available
with this text, Interactive Thermodynamics: IT, is also used selectively in examples and end-
of-chapter problems throughout the book. Skillful use of tables and property diagrams is
prerequisite for the effective use of software to retrieve thermodynamic property data.
Since tables for different substances are frequently set up in the same general format, the
present discussion centers mainly on Tables A-2 through A-6 giving the properties of water;
steam tables these are commonly referred to as the steam tables. Tables A-7 through A-9 for Refrigerant
22, Tables A-10 through A-12 for Refrigerant 134a, Tables A-13 through A-15 for ammonia,
and Tables A-16 through A-18 for propane are used similarly, as are tables for other sub-
stances found in the engineering literature.
3.3 Retrieving Thermodynamic Properties 77
3.3.1 Evaluating Pressure, Specific Volume, and Temperature

VAPOR AND LIQUID TABLES
The properties of water vapor are listed in Tables A-4 and of liquid water in Tables A-5.
These are often referred to as the superheated vapor tables and compressed liquid tables, re-
spectively. The sketch of the phase diagram shown in Fig. 3.6 brings out the structure of
these tables. Since pressure and temperature are independent properties in the single-phase
liquid and vapor regions, they can be used to fix the state in these regions. Accordingly,
Tables A-4 and A-5 are set up to give values of several properties as functions of pressure
and temperature. The first property listed is specific volume. The remaining properties are
discussed in subsequent sections.
For each pressure listed, the values given in the superheated vapor table (Tables A-4) begin
with the saturated vapor state and then proceed to higher temperatures. The data in the com-
pressed liquid table (Tables A-5) end with saturated liquid states. That is, for a given pres-
sure the property values are given as the temperature increases to the saturation temperature.
In these tables, the value shown in parentheses after the pressure in the table heading is the
corresponding saturation temperature. for example. . . in Tables A-4 and A-5, at a
pressure of 10.0 MPa, the saturation temperature is listed as 311.06C.
for example. . . to gain more experience with Tables A-4 and A-5 verify the following:
Table A-4 gives the specific volume of water vapor at 10.0 MPa and 600C as 0.03837 m3/kg.
At 10.0 MPa and 100C, Table A-5 gives the specific volume of liquid water as 1.0385
103 m3/kg.
The states encountered when solving problems often do not fall exactly on the grid of val-
ues provided by property tables. Interpolation between adjacent table entries then becomes
necessary. Care always must be exercised when interpolating table values. The tables pro-
vided in the Appendix are extracted from more extensive tables that are set up so that linear linear interpolation
interpolation, illustrated in the following example, can be used with acceptable accuracy.
Linear interpolation is assumed to remain valid when using the abridged tables of the text
for the solved examples and end-of-chapter problems.
Compressed liquid
tables give v, u, h, s
versus p, T
Critical
point
Liquid
Pressure
Solid Vapor
Superheated
vapor tables
give v, u, h, s
versus p, T
Figure 3.6 Sketch of the phase diagram
for water used to discuss the structure of the
superheated vapor and compressed liquid
Temperature tables (not to scale).
3
(240C, 0.2275 mkg )

p = 10 bar
v (m3/kg)
(215C, v) T(C) v (m3/kg)
200 0.2060
215 v=?
3
(200C, 0.2060 mkg )

240 0.2275
200 215 240

T(C)
Figure 3.7 Illustration of linear interpolation.
for example. . . let us determine the specific volume of water vapor at a state where
p 10 bar and T 215C. Shown in Fig. 3.7 is a sampling of data from Table A-4. At a
pressure of 10 bar, the specified temperature of 215C falls between the table values of 200
and 240C, which are shown in bold face. The corresponding specific volume values are also
shown in bold face. To determine the specific volume v corresponding to 215C, we may
think of the slope of a straight line joining the adjacent table states, as follows
10.2275 0.20602 m3/kg 1v 0.20602 m3/kg
slope
1240 2002C 1215 2002C
Solving for v, the result is v 0.2141 m3/kg.
SATURATION TABLES
The saturation tables, Tables A-2 and A-3, list property values for the saturated liquid and
vapor states. The property values at these states are denoted by the subscripts f and g, re-
spectively. Table A-2 is called the temperature table, because temperatures are listed in the
first column in convenient increments. The second column gives the corresponding satura-
tion pressures. The next two columns give, respectively, the specific volume of saturated liq-
uid, vf, and the specific volume of saturated vapor, vg. Table A-3 is called the pressure table,
because pressures are listed in the first column in convenient increments. The corresponding
saturation temperatures are given in the second column. The next two columns give vf and
vg, respectively.
The specific volume of a two-phase liquidvapor mixture can be determined by using the
saturation tables and the definition of quality given by Eq. 3.1 as follows. The total volume
of the mixture is the sum of the volumes of the liquid and vapor phases
V Vliq
Vvap
Dividing by the total mass of the mixture, m, an average specific volume for the mixture is
obtained
V Vliq Vvap
v
m m m
Since the liquid phase is a saturated liquid and the vapor phase is a saturated vapor, Vliq
mliq vf and Vvap mvap vg, so
mliq mvap
va b vf
a b vg
m m
Introducing the definition of quality, x mvapm, and noting that mliqm 1 x, the above
expression becomes
v 11 x2 vf
xvg vf
x 1vg vf 2 (3.2)
The increase in specific volume on vaporization (vg vf) is also denoted by vfg.
for example. . . consider a system consisting of a two-phase liquidvapor mixture

of water at 100C and a quality of 0.9. From Table A-2 at 100C, vf 1.0435 103 m3/kg
and vg 1.673 m3/kg. The specific volume of the mixture is
v vf
x 1vg vf 2 1.0435 103
10.92 11.673 1.0435 103 2 1.506 m3/kg
To facilitate locating states in the tables, it is often convenient to use values from the
saturation tables together with a sketch of a Tv or pv diagram. For example, if the specific
volume v and temperature T are known, refer to the temperature table, Table A-2, and deter-
mine the values of vf and vg. A Tv diagram illustrating these data is given in Fig. 3.8. If the
given specific volume falls between vf and vg, the system consists of a two-phase liquidvapor
mixture, and the pressure is the saturation pressure corresponding to the given temperature.
The quality can be found by solving Eq. 3.2. If the given specific volume is greater than vg,
the state is in the superheated vapor region. Then, by interpolating in Table A-4 the pressure
and other properties listed can be determined. If the given specific volume is less than vf,
Table A-5 would be used to determine the pressure and other properties.
for example. . . let us determine the pressure of water at each of three states defined
by a temperature of 100C and specific volumes, respectively, of v1 2.434 m3/kg, v2
1.0 m3/kg, and v3 1.0423 103 m3/kg. Using the known temperature, Table A-2 pro- T
vides the values of vf and vg: vf 1.0435 103 m3/kg, vg 1.673 m3/kg. Since v1 is
greater than vg, state 1 is in the vapor region. Table A-4 gives the pressure as 0.70 bar. Next, 3 f 2 g 1
100C
since v2 falls between vf and vg, the pressure is the saturation pressure corresponding to
100C, which is 1.014 bar. Finally, since v3 is less than vf, state 3 is in the liquid region.
Table A-5 gives the pressure as 25 bar. v
EXAMPLES
The following two examples feature the use of sketches of pv and Tv diagrams in conjunction
with tabular data to fix the end states of processes. In accord with the state principle, two inde-
pendent intensive properties must be known to fix the state of the systems under consideration.
Critical point
Saturated
Saturated
vapor
Liquid liquid Vapor
Temperature
v < vf
vf < v < vg v > vg
f g
Figure 3.8 Sketch of a Tv diagram for

vf vg water used to discuss locating states in the
Specific volume tables.
EXAMPLE 3.1 Heating Water at Constant Volume
A closed, rigid container of volume 0.5 m3 is placed on a hot plate. Initially, the container holds a two-phase mixture of sat-
urated liquid water and saturated water vapor at p1 1 bar with a quality of 0.5. After heating, the pressure in the container
is p2 1.5 bar. Indicate the initial and final states on a Tv diagram, and determine
(a) the temperature, in C, at each state.

(b) the mass of vapor present at each state, in kg.
(c) If heating continues, determine the pressure, in bar, when the container holds only saturated vapor.
SOLUTION
Known: A two-phase liquidvapor mixture of water in a closed, rigid container is heated on a hot plate. The initial pressure
and quality and the final pressure are known.
Find: Indicate the initial and final states on a Tv diagram and determine at each state the temperature and the mass of water
vapor present. Also, if heating continues, determine the pressure when the container holds only saturated vapor.
p1 = 1 bar
x1 = 0.5 3 1.5 bar
p2 = 1.5 bar
x3 = 1.0 V = 0.5 m3
2 1 bar
1
+
Hot plate
v
Figure E3.1
Assumptions:
1. The water in the container is a closed system.

2. States 1, 2, and 3 are equilibrium states.
3. The volume of the container remains constant.
Analysis: Two independent properties are required to fix states 1 and 2. At the initial state, the pressure and quality are
known. As these are independent, the state is fixed. State 1 is shown on the Tv diagram in the two-phase region. The spe-
cific volume at state 1 is found using the given quality and Eq. 3.2. That is
v1 vf1
x 1vgl vfl 2
3
From Table A-3 at p1 1 bar, vfl 1.0432 10 m3/kg and vg1 1.694 m3/kg. Thus
v1 1.0432 103
0.5 11.694 1.0432 103 2 0.8475 m3/kg
At state 2, the pressure is known. The other property required to fix the state is the specific volume v2. Volume and mass are
each constant, so v2 v1 0.8475 m3/kg. For p2 1.5 bar, Table A-3 gives vf2 1.0582 103 and vg2 1.159 m3/kg. Since
vf2 6 v2 6 vg2
state 2 must be in the two-phase region as well. State 2 is also shown on the Tv diagram above.
(a) Since states 1 and 2 are in the two-phase liquidvapor region, the temperatures correspond to the saturation temperatures
for the given pressures. Table A-3 gives
T1 99.63C and T2 111.4C

(b) To find the mass of water vapor present, we first use the volume and the specific volume to find the total mass, m. That is
V 0.5 m3
m 0.59 kg
v 0.8475 m3/kg
Then, with Eq. 3.1 and the given value of quality, the mass of vapor at state 1 is
mg1 x1m 0.5 10.59 kg2 0.295 kg
The mass of vapor at state 2 is found similarly using the quality x2. To determine x2, solve Eq. 3.2 for quality and insert spe-
cific volume data from Table A-3 at a pressure of 1.5 bar, along with the known value of v, as follows
v vf2
x2
vg2 vf2
0.8475 1.0528 103
0.731
1.159 1.0528 103
Then, with Eq. 3.1
mg2 0.731 10.59 kg2 0.431 kg
(c) If heating continued, state 3 would be on the saturated vapor line, as shown on the Tv diagram above. Thus, the pres-
sure would be the corresponding saturation pressure. Interpolating in Table A-3 at vg 0.8475 m3/kg, we get p3 2.11 bar.
The procedure for fixing state 2 is the same as illustrated in the discussion of Fig. 3.8.
Since the process occurs at constant specific volume, the states lie along a vertical line.
If heating continued at constant volume past state 3, the final state would be in the superheated vapor region, and prop-
erty data would then be found in Table A-4. As an exercise, verify that for a final pressure of 3 bar, the temperature would
be approximately 282C.
EXAMPLE 3.2 Heating Ammonia at Constant Pressure
A vertical pistoncylinder assembly containing 0.05 kg of ammonia, initially a saturated vapor, is placed on a hot plate. Due
to the weight of the piston and the surrounding atmospheric pressure, the pressure of the ammonia is 1.5 bars. Heating occurs
slowly, and the ammonia expands at constant pressure until the final temperature is 25C. Show the initial and final states on
Tv and pv diagrams, and determine
(a) the volume occupied by the ammonia at each state, in m3.

(b) the work for the process, in kJ.
SOLUTION
Known: Ammonia is heated at constant pressure in a vertical pistoncylinder assembly from the saturated vapor state to a
known final temperature.
Find: Show the initial and final states on Tv and pv diagrams, and determine the volume at each state and the work for
the process.
25C
2
Ammonia
25.2C
1
+
Hot plate
v
Assumptions:
1. The ammonia is a closed system.

25C 2. States 1 and 2 are equilibrium states.
1.5 bars 2 3. The process occurs at constant pressure.
1
v
Figure E3.2
Analysis: The initial state is a saturated vapor condition at 1.5 bars. Since the process occurs at constant pressure, the final
state is in the superheated vapor region and is fixed by p2 1.5 bars and T2 25C. The initial and final states are shown
on the Tv and pv diagrams above.
(a) The volumes occupied by the ammonia at states 1 and 2 are obtained using the given mass and the respective specific
volumes. From Table A-14 at p1 1.5 bars, we get v1 vg1 0.7787 m3/kg. Thus
V1 mv1 10.05 kg210.7787 m3/kg2
0.0389 m3
Interpolating in Table A-15 at p2 1.5 bars and T2 25C, we get v2 .9553 m3/kg. Thus
V2 mv2 10.05 kg21.9553 m3/kg2 0.0478 m3
(b) In this case, the work can be evaluated using Eq. 2.17. Since the pressure is constant
p dV p1V2 V1 2
V2
W
V1
Inserting values
105 N/m2
W 11.5 bars210.0478 0.03892m3 ` ` ` 3 # `
kJ
1 bar 10 N m
W 1.335 kJ
Note the use of conversion factors in this calculation.

3.3.2 Evaluating Specific Internal Energy and Enthalpy

In many thermodynamic analyses the sum of the internal energy U and the product of pres-
sure p and volume V appears. Because the sum U
pV occurs so frequently in subsequent
discussions, it is convenient to give the combination a name, enthalpy, and a distinct symbol, enthalpy
H. By definition
H U
pV (3.3)
Since U, p, and V are all properties, this combination is also a property. Enthalpy can be
expressed on a unit mass basis
h u
pv (3.4)
and per mole
h u
pv (3.5)
Units for enthalpy are the same as those for internal energy.
The property tables introduced in Sec. 3.3.1 giving pressure, specific volume, and tem-
perature also provide values of specific internal energy u, enthalpy h, and entropy s. Use of
these tables to evaluate u and h is described in the present section; the consideration of en-
tropy is deferred until it is introduced in Chap. 6.
Data for specific internal energy u and enthalpy h are retrieved from the property tables
in the same way as for specific volume. For saturation states, the values of uf and ug, as well
as hf and hg, are tabulated versus both saturation pressure and saturation temperature. The
specific internal energy for a two-phase liquidvapor mixture is calculated for a given qual-
ity in the same way the specific volume is calculated
u 11 x2uf
xug uf
x 1ug uf 2 (3.6)
The increase in specific internal energy on vaporization (ug uf) is often denoted by ufg.
Similarly, the specific enthalpy for a two-phase liquidvapor mixture is given in terms of the
quality by
h 11 x2hf
xhg hf
x 1hg hf 2 (3.7)
The increase in enthalpy during vaporization (hg hf) is often tabulated for convenience
under the heading hfg.
for example. . . to illustrate the use of Eqs. 3.6 and 3.7, we determine the specific
enthalpy of Refrigerant 22 when its temperature is 12C and its specific internal energy is
144.58 kJ/kg. Referring to Table A-7, the given internal energy value falls between uf and ug
at 12C, so the state is a two-phase liquidvapor mixture. The quality of the mixture is found
by using Eq. 3.6 and data from Table A-7 as follows:
u uf 144.58 58.77
x 0.5
ug uf 230.38 58.77
Then, with the values from Table A-7, Eq. 3.7 gives
h 11 x2hf
xhg
11 0.52159.352
0.51253.992 156.67 kJ/kg
In the superheated vapor tables, u and h are tabulated along with v as functions of temperature
and pressure. for example. . . let us evaluate T, v, and h for water at 0.10 MPa and a

Natural RefrigerantsBack to the Future using propane are now available in
Europe. Manufacturers claim they are
Naturally-occurring refrigerants like hydrocarbons, ammonia, safer than gas-burning home appliances.
and carbon dioxide were introduced in the early 1900s. They Researchers are studying ways to elimi-
were displaced in the 1920s by safer chlorine-based synthetic nate leaks so ammonia can find more
refrigerants, paving the way for the refrigerators and air widespread application. Carbon dioxide is
conditioners we enjoy today. Over the last decade, these syn- also being looked at again with an eye to
thetics largely have been replaced by hydroflourocarbons minimizing safety issues related to its
(HFCs) because of uneasiness over ozone depletion. But stud- relatively high pressures in refrigeration
ies now indicate that natural refrigerants may be preferable to applications.
HFCs because of lower overall impact on global warming. This Neither HFCs nor natural refrigerants do well on measures
has sparked renewed interest in natural refrigerants. of direct global warming impact. However, a new index that
Decades of research and development went into the current takes energy efficiency into account is changing how we view
refrigerants, so returning to natural refrigerants creates chal- refrigerants. Because of the potential for increased energy ef-
lenges, experts say. Engineers are revisiting the concerns of ficiency of refrigerators using natural refrigerants, the natu-
flammability, odor, and safety that naturals present, and are rals score well on the new index compared to HFCs.
meeting with some success. New energy-efficient refrigerators
specific internal energy of 2537.3 kJ/kg. Turning to Table A-3, note that the given value of u
is greater than ug at 0.1 MPa (ug 2506.1 kJ/kg). This suggests that the state lies in the
superheated vapor region. From Table A-4 it is found that T 120C, v 1.793 m3/kg, and
h 2716.6 kJ/kg. Alternatively, h and u are related by the definition of h
h u
pv
m3

a105 2 b a1.793 b ` 3 # `
kJ N 1 kJ
2537.3
kg m kg 10 N m
2537.3
179.3 2716.6 kJ/kg
Specific internal energy and enthalpy data for liquid states of water are presented in
Tables A-5. The format of these tables is the same as that of the superheated vapor tables
considered previously. Accordingly, property values for liquid states are retrieved in the same
manner as those of vapor states.
For water, Tables A-6 give the equilibrium properties of saturated solid and saturated vapor.
The first column lists the temperature, and the second column gives the corresponding sat-
uration pressure. These states are at pressures and temperatures below those at the triple point.
The next two columns give the specific volume of saturated solid, vi, and saturated vapor,
vg, respectively. The table also provides the specific internal energy, enthalpy, and entropy
values for the saturated solid and the saturated vapor at each of the temperatures listed.
REFERENCE STATES AND REFERENCE VALUES
The values of u, h, and s given in the property tables are not obtained by direct measurement
but are calculated from other data that can be more readily determined experimentally. The
computational procedures require use of the second law of thermodynamics, so consideration
of these procedures is deferred to Chap. 11 after the second law has been introduced. However,
reference states because u, h, and s are calculated, the matter of reference states and reference values be-
comes important and is considered briefly in the following paragraphs.
reference values
When applying the energy balance, it is differences in internal, kinetic, and potential en-
ergy between two states that are important, and not the values of these energy quantities at
each of the two states. for example. . . consider the case of potential energy. The nu-
merical value of potential energy determined relative to the surface of the earth is different from
the value relative to the top of a tall building at the same location. However, the difference in
potential energy between any two elevations is precisely the same regardless of the datum
selected, because the datum cancels in the calculation.
Similarly, values can be assigned to specific internal energy and enthalpy relative to ar-
bitrary reference values at arbitrary reference states. As for the case of potential energy con-
sidered above, the use of values of a particular property determined relative to an arbitrary
reference is unambiguous as long as the calculations being performed involve only differ-
ences in that property, for then the reference value cancels. When chemical reactions take
place among the substances under consideration, special attention must be given to the mat-
ter of reference states and values, however. A discussion of how property values are assigned
when analyzing reactive systems is given in Chap. 13.
The tabular values of u and h for water, ammonia, propane, and Refrigerants 22 and 134a
provided in the Appendix are relative to the following reference states and values. For water,
the reference state is saturated liquid at 0.01C. At this state, the specific internal energy is
set to zero. Values of the specific enthalpy are calculated from h u
pv, using the tabu-
lated values for p, v, and u. For ammonia, propane, and the refrigerants, the reference state
is saturated liquid at 40C. At this reference state the specific enthalpy is set to zero. Val-
ues of specific internal energy are calculated from u h pv by using the tabulated values
for p, v, and h. Notice in Table A-7 that this leads to a negative value for internal energy at
the reference state, which emphasizes that it is not the numerical values assigned to u and h
at a given state that are important but their differences between states. The values assigned to
particular states change if the reference state or reference values change, but the differences
remain the same.
3.3.3 Evaluating Properties Using Computer Software

The use of computer software for evaluating thermodynamic properties is becoming preva-
lent in engineering. Computer software falls into two general categories: those that provide
data only at individual states and those that provide property data as part of a more general
simulation package. The software available with this text, Interactive Thermodynamics: IT,
is a tool that can be used not only for routine problem solving by providing data at individ-
ual state points, but also for simulation and analysis (see box).
U S I N G I N T E R A C T I V E T H E R M O DY N A M I C S : I T
The computer software tool Interactive Thermodynamics: IT is available for use with
this text. Used properly, IT provides an important adjunct to learning engineering ther-
modynamics and solving engineering problems. The program is built around an equa-
tion solver enhanced with thermodynamic property data and other valuable features.
With IT you can obtain a single numerical solution or vary parameters to investigate
their effects. You also can obtain graphical output, and the Windows-based format allows
you to use any Windows word-processing software or spreadsheet to generate reports.
Other features of IT include:
a guided series of help screens and a number of sample solved examples from the
text to help you learn how to use the program.
drag-and-drop templates for many of the standard problem types, including a list
of assumptions that you can customize to the problem at hand.
predetermined scenarios for power plants and other important applications.
thermodynamic property data for water, refrigerants 22 and 134a, ammonia,
airwater vapor mixtures, and a number of ideal gases.
the capability to input user-supplied data.

the capability to interface with user-supplied routines.
The software is best used as an adjunct to the problem-solving process discussed in
Sec. 1.7.3. The equation-solving capability of the program cannot substitute for care-
ful engineering analysis. You still must develop models and analyze them, perform lim-
ited hand calculations, and estimate ranges of parameters and property values before
you move to the computer to obtain solutions and explore possible variations. Afterward,
you also must assess the answers to see that they are reasonable.
IT provides data for substances represented in the Appendix tables. Generally, data are
retrieved by simple call statements that are placed in the workspace of the program.
for example. . . consider the two-phase, liquidvapor mixture at state 1 of Example
3.1 for which p 1 bar, v 0.8475 m3/kg. The following illustrates how data for saturation
temperature, quality, and specific internal energy are retrieved using IT. The functions for T,
v, and u are obtained by selecting Water/Steam from the Properties menu. Choosing SI units
from the Units menu, with p in bar, T in C, and amount of substance in kg, the IT program is
p = 1 // bar
v = 0.8475 // m3/kg
T = Tsat_P(Water/Steam,p)
v = vsat_Px(Water/Steam,p,x)
u = usat_Px(Water/Steam,p,x)
Clicking the Solve button, the software returns values of T 99.63C, x 0.5, and u
1462 kJ/kg. These values can be verified using data from Table A-3. Note that text inserted
between the symbol // and a line return is treated as a comment.
The previous example illustrates an important feature of IT. Although the quality, x, is im-
plicit in the list of arguments in the expression for specific volume, there is no need to solve
the expression algebraically for x. Rather, the program can solve for x as long as the num-
ber of equations equals the number of unknowns.
Other features of Interactive Thermodynamics: IT are illustrated through subsequent ex-
amples. The use of computer software for engineering analysis is a powerful approach. Still,
there are some rules to observe:
Software complements and extends careful analysis, but does not substitute for it.
Computer-generated values should be checked selectively against hand-calculated,
or otherwise independently determined values.
Computer-generated plots should be studied to see if the curves appear reasonable
and exhibit expected trends.
3.3.4 Examples
In the following examples, closed systems undergoing processes are analyzed using the energy
balance. In each case, sketches of pv and/or Tv diagrams are used in conjunction with
appropriate tables to obtain the required property data. Using property diagrams and table data
introduces an additional level of complexity compared to similar problems in Chap. 2.
EXAMPLE 3.3 Stirring Water at Constant Volume
A well-insulated rigid tank having a volume of .25 m3 contains saturated water vapor at 100C. The water is rapidly stirred
until the pressure is 1.5 bars. Determine the temperature at the final state, in C, and the work during the process, in kJ.
SOLUTION
Known: By rapid stirring, water vapor in a well-insulated rigid tank is brought from the saturated vapor state at 100C to a
pressure of 1.5 bars.
Find: Determine the temperature at the final state and the work.
Water
Boundary
p T
2
T2
1.5 bars 2 1.5 bars
T2
1.014 bars
1.014 bars
100C 1
1 100C
v v
Figure E3.3
Assumptions:
1. The water is a closed system.

2. The initial and final states are at equilibrium. There is no net change in kinetic or potential energy.
3. There is no heat transfer with the surroundings.
4. The tank volume remains constant.
Analysis: To determine the final equilibrium state, the values of two independent intensive properties are required. One of
these is pressure, p2 1.5 bars, and the other is the specific volume: v2 v1. The initial and final specific volumes are equal
because the total mass and total volume are unchanged in the process. The initial and final states are located on the accom-
panying Tv and pv diagrams.
From Table A-2, v1 vg(100C) 1.673 m3/kg, u1 ug(100C) 2506.5 kJ/kg. By using v2 v1 and interpolating in
Table A-4 at p2 1.5 bars.
T2 273C, u2 2767.8 kJ/kg
Next, with assumptions 2 and 3 an energy balance for the system reduces to
0 0 0
U
KE
PE Q W
On rearrangement
W 1U2 U1 2 m1u2 u1 2
To evaluate W requires the system mass. This can be determined from the volume and specific volume
0.25 m3
a b 0.149 kg
V
m
v1 1.673 m3/kg
Finally, by inserting values into the expression for W
W 1.149 kg212767.8 2506.52 kJ/kg 38.9 kJ
where the minus sign signifies that the energy transfer by work is to the system.
Although the initial and final states are equilibrium states, the intervening states are not at equilibrium. To emphasize this,
the process has been indicated on the Tv and pv diagrams by a dashed line. Solid lines on property diagrams are re-
served for processes that pass through equilibrium states only (quasiequilibrium processes). The analysis illustrates the im-
portance of carefully sketched property diagrams as an adjunct to problem solving.
EXAMPLE 3.4 Analyzing Two Processes in Series
Water contained in a pistoncylinder assembly undergoes two processes in series from an initial state where the pressure is
10 bar and the temperature is 400C.
Process 12: The water is cooled as it is compressed at a constant pressure of 10 bar to the saturated vapor state.
Process 23: The water is cooled at constant volume to 150C.
(a) Sketch both processes on Tv and pv diagrams.

(b) For the overall process determine the work, in kJ/kg.
(c) For the overall process determine the heat transfer, in kJ/kg.
SOLUTION
Known: Water contained in a pistoncylinder assembly undergoes two processes: It is cooled and compressed while keep-
ing the pressure constant, and then cooled at constant volume.
Find: Sketch both processes on Tv and pv diagrams. Determine the net work and the net heat transfer for the overall
process per unit of mass contained within the pistoncylinder assembly.
Water
10 bar
Boundary
1
p T 400C
400C
10 bar 2 1 179.9C
2
179.9C
4.758 bar
4.758 bar 150C
3 150C 3
v v
Figure E3.4
Assumptions:
1. The water is a closed system.

2. The piston is the only work mode.
3. There are no changes in kinetic or potential energy.
Analysis:
(a) The accompanying Tv and pv diagrams show the two processes. Since the temperature at state 1, T1 400C, is greater
than the saturation temperature corresponding to p1 10 bar: 179.9C, state 1 is located in the superheat region.
(b) Since the piston is the only work mechanism

3 2 3 0
W p dV p dV
p dV
1 1 2
The second integral vanishes because the volume is constant in Process 23. Dividing by the mass and noting that the pres-
sure is constant for Process 12
p 1v2 v1 2
W
m
The specific volume at state 1 is found from Table A-4 using p1 10 bar and T1 400C: v1 0.3066 m3/kg. Also, u1
2957.3 kJ/kg. The specific volume at state 2 is the saturated vapor value at 10 bar: v2 0.1944 m3/kg, from Table A-3. Hence
m3 105 N/m2
110 bar210.1944 0.30662 a b ` ` ` 3 # `
W 1 kJ
m kg 1 bar 10 N m
112.2 kJ/kg
The minus sign indicates that work is done on the water vapor by the piston.
(c) An energy balance for the overall process reduces to
m1u3 u1 2 Q W
By rearranging
1u3 u1 2
Q W
m m
To evaluate the heat transfer requires u3, the specific internal energy at state 3. Since T3 is given and v3 v2, two independent
intensive properties are known that together fix state 3. To find u3, first solve for the quality
v3 vf3 0.1944 1.0905 103
x3 0.494
vg3 vf3 0.3928 1.0905 103
where vf3 and vg3 are from Table A-2 at 150C. Then
u3 uf3
x3 1ug3 uf3 2 631.68
0.49412559.5 631.982
1583.9 kJ/kg
where uf3 and ug3 are from Table A-2 at 150C.
Substituting values into the energy balance
1583.9 2957.3
1112.22 1485.6 kJ/kg
Q
m
The minus sign shows that energy is transferred out by heat transfer.
The next example illustrates the use of Interactive Thermodynamics: IT for solving problems.
In this case, the software evaluates the property data, calculates the results, and displays the re-
sults graphically.
EXAMPLE 3.5 Plotting Thermodynamic Data Using Software
For the system of Example 3.1, plot the heat transfer, in kJ, and the mass of saturated vapor present, in kg, each versus pres-
sure at state 2 ranging from 1 to 2 bar. Discuss the results.
SOLUTION
Known: A two-phase liquidvapor mixture of water in a closed, rigid container is heated on a hot plate. The initial pressure
and quality are known. The pressure at the final state ranges from 1 to 2 bar.
Find: Plot the heat transfer and the mass of saturated vapor present, each versus pressure at the final state. Discuss.
Schematic and Given Data: See Figure E3.1.
Assumptions:
1. There is no work.
2. Kinetic and potential energy effects are negligible.
3. See Example 3.1 for other assumptions.
Analysis: The heat transfer is obtained from the energy balance. With assumptions 1 and 2, the energy balance reduces to
0 0 0
U
KE
PE Q W
or
Q m1u2 u1 2
Selecting Water/Steam from the Properties menu and choosing SI Units from the Units menu, the IT program for obtaining
the required data and making the plots is
// Given dataState 1
p1 = 1 // bar
x1 = 0.5
V = 0.5 // m3
// Evaluate property dataState 1
v1 = vsat_Px(Water/Steam,p1,x1)
u1 = usat_Px(Water/Steam,p1,x1)
// Calculate the mass
m = V/v1
// Fix state 2
v2 = v1
p2 = 1.5 // bar
// Evaluate property dataState 2
v2 = vsat_Px(Water/Steam,p2,x2)
u2 = usat_Px(Water/Steam,p2,x2)
// Calculate the mass of saturated vapor present
mg2 = x2 * m
// Determine the pressure for which the quality is unity
v3 = v1
v3 = vsat_Px(Water/Steam,p3,1)
// Energy balance to determine the heat transfer
m * (u2 u1) = Q W
W=0
Click the Solve button to obtain a solution for p2 1.5 bar. The program returns values of v1 0.8475 m3/kg and m 0.59 kg.
Also, at p2 1.5 bar, the program gives mg2 0.4311 kg. These values agree with the values determined in Example 3.1.
Now that the computer program has been verified, use the Explore button to vary pressure from 1 to 2 bar in steps of 0.1
bar. Then, use the Graph button to construct the required plots. The results are:
600 0.6
500 0.5
400 0.4
mg, kg
Q, kJ
300 0.3
200 0.2
100 0.1
0 0
1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2 1 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2
Pressure, bar Pressure, bar
Figure E3.5
We conclude from the first of these graphs that the heat transfer to the water varies directly with the pressure. The plot of mg
shows that the mass of saturated vapor present also increases as the pressure increases. Both of these results are in accord
with expectations for the process.
Using the Browse button, the computer solution indicates that the pressure for which the quality becomes unity is 2.096
bar. Thus, for pressures ranging from 1 to 2 bar, all of the states are in the two-phase liquidvapor region.
3.3.5 Evaluating Specific Heats cv and cp

Several properties related to internal energy are important in thermodynamics. One of these
is the property enthalpy introduced in Sec. 3.3.2. Two others, known as specific heats, are
considered in this section. The specific heats are particularly useful for thermodynamic cal-
culations involving the ideal gas model introduced in Sec. 3.5.
The intensive properties cv and cp are defined for pure, simple compressible substances
as partial derivatives of the functions u(T, v) and h(T, p), respectively
b
0u
cv (3.8)
0T v
b
0h
cp (3.9)
0T p
where the subscripts v and p denote, respectively, the variables held fixed during differentiation.
Values for cv and cp can be obtained via statistical mechanics using spectroscopic measurements.
They also can be determined macroscopically through exacting property measurements. Since
u and h can be expressed either on a unit mass basis or per mole, values of the specific heats
can be similarly expressed. SI units are kJ/kg # K or kJ/kmol # K.
The property k, called the specific heat ratio, is simply the ratio
cp
k (3.10)
cv
The properties cv and cp are referred to as specific heats (or heat capacities) because un- specific heats
der certain special conditions they relate the temperature change of a system to the amount
of energy added by heat transfer. However, it is generally preferable to think of cv and cp in
terms of their definitions, Eqs. 3.8 and 3.9, and not with reference to this limited interpreta-
tion involving heat transfer.
In general, cv is a function of v and T (or p and T ), and cp depends on both p and T (or
v and T). Figure 3.9 shows how cp for water vapor varies as a function of temperature and
pressure. The vapor phases of other substances exhibit similar behavior. Note that the figure
gives the variation of cp with temperature in the limit as pressure tends to zero. In this limit,
cp increases with increasing temperature, which is a characteristic exhibited by other gases
as well. We will refer again to such zero-pressure values for cv and cp in Sec. 3.6.
Specific heat data are available for common gases, liquids, and solids. Data for gases are
introduced in Sec. 3.5 as a part of the discussion of the ideal gas model. Specific heat val-
ues for some common liquids and solids are introduced in Sec. 3.3.6 as a part of the dis-
cussion of the incompressible substance model.
p = constant 3.3.6 Evaluating Properties of Liquids and Solids

T Saturated
liquid Special methods often can be used to evaluate properties of liquids and solids. These meth-
ods provide simple, yet accurate, approximations that do not require exact compilations like
p = constant the compressed liquid tables for water, Tables A-5. Two such special methods are discussed
next: approximations using saturated liquid data and the incompressible substance model.
f
T = constant APPROXIMATIONS FOR LIQUIDS USING SATURATED LIQUID DATA
Approximate values for v, u, and h at liquid states can be obtained using saturated liquid
v(T, p) vf (T )
data. To illustrate, refer to the compressed liquid tables. Tables A-5. These tables show
v vf v
8
60
7
70
80
6
or
90
ted vap
cp , kJ/kgK
100 60
Satura
70
5
80
90
100 MPa
50
M
4
40
Pa
30
25
20
15
10
3
5
2
1
2 0
Zero pressure limit
1.5
100 200 300 400 500 600 700 800

T, C
Figure 3.9 cp of water vapor as a function of temperature and pressure.
that the specific volume and specific internal energy change very little with pressure at a
fixed temperature. Because the values of v and u vary only gradually as pressure changes
at fixed temperature, the following approximations are reasonable for many engineering
calculations:
v1T, p2 vf 1T 2 (3.11)

u1T, p2 uf 1T 2 (3.12)
That is, for liquids v and u may be evaluated at the saturated liquid state corresponding to
the temperature at the given state.
An approximate value of h at liquid states can be obtained by using Eqs. 3.11 and 3.12
in the definition h u
pv; thus
h1T, p2 uf 1T 2
pvf 1T 2
This can be expressed alternatively as
h1T, p2 hf 1T 2
vf 1T 2 3p psat 1T 2 4 (3.13)
where psat denotes the saturation pressure at the given temperature. The derivation is
left as an exercise. When the contribution of the underlined term of Eq. 3.13 is small,
the specific enthalpy can be approximated by the saturated liquid value, as for v and u.
That is
h1T, p2 hf 1T 2 (3.14)
Although the approximations given here have been presented with reference to liquid
water, they also provide plausible approximations for other substances when the only liquid
data available are for saturated liquid states. In this text, compressed liquid data are pre-
sented only for water (Tables A-5). Also note that Interactive Thermodynamics: IT does not
provide compressed liquid data for any substance, but uses Eqs. 3.11, 3.12, and 3.14 to return
liquid values for v, u, and h, respectively. When greater accuracy is required than provided
by these approximations, other data sources should be consulted for more complete property
compilations for the substance under consideration.
INCOMPRESSIBLE SUBSTANCE MODEL
As noted above, there are regions where the specific volume of liquid water varies little and
the specific internal energy varies mainly with temperature. The same general behavior is
exhibited by the liquid phases of other substances and by solids. The approximations of
Eqs. 3.113.14 are based on these observations, as is the incompressible substance model incompressible
under present consideration. substance model
To simplify evaluations involving liquids or solids, the specific volume (density) is often
assumed to be constant and the specific internal energy assumed to vary only with temper-
ature. A substance idealized in this way is called incompressible.
Since the specific internal energy of a substance modeled as incompressible depends only
on temperature, the specific heat cv is also a function of temperature alone
cv 1T 2 1incompressible2
du
(3.15)
dT
This is expressed as an ordinary derivative because u depends only on T.
Although the specific volume is constant and internal energy depends on temperature only,
enthalpy varies with both pressure and temperature according to
h 1T, p2 u 1T 2
pv 1incompressible2 (3.16)
For a substance modeled as incompressible, the specific heats cv and cp are equal. This is
seen by differentiating Eq. 3.16 with respect to temperature while holding pressure fixed to
obtain
b
0h du
0T p dT
The left side of this expression is cp by definition (Eq. 3.9), so using Eq. 3.15 on the right
side gives
cp cv 1incompressible2 (3.17)
Thus, for an incompressible substance it is unnecessary to distinguish between cp and cv, and
both can be represented by the same symbol, c. Specific heats of some common liquids and
solids are given versus temperature in Tables A-19. Over limited temperature intervals the
variation of c with temperature can be small. In such instances, the specific heat c can be
treated as constant without a serious loss of accuracy.
Using Eqs. 3.15 and 3.16, the changes in specific internal energy and specific enthalpy
between two states are given, respectively, by
c1T 2 dT 1incompressible2
T2
u2 u1 (3.18)
T1
h2 h1 u2 u1
v1 p2 p1 2
c1T 2 dT
v1 p2 p1 2 1incompressible2
T2
(3.19)
T1
If the specific heat c is taken as constant, Eqs. 3.18 and 3.19 become, respectively,
u2 u1 c1T2 T1 2 (3.20a)
h2 h1 c1T2 T1 2
v1p2 p1 2
(incompressible, constant c)
(3.20b)
In Eq. 3.20b, the underlined term is often small relative to the first term on the right side and
then may be dropped.
3.4 Generalized Compressibility Chart

The object of the present section is to gain a better understanding of the relationship
among pressure, specific volume, and temperature of gases. This is important not only as
a basis for analyses involving gases but also for the discussions of the second part of the
chapter, where the ideal gas model is introduced. The current presentation is conducted
in terms of the compressibility factor and begins with the introduction of the universal
gas constant.
3.4 Generalized Compressibility Chart 95
UNIVERSAL GAS CONSTANT, R Measured data

pv extrapolated to
Let a gas be confined in a cylinder by a piston and the entire assembly held at a con- T zero pressure
T1
stant temperature. The piston can be moved to various positions so that a series of
equilibrium states at constant temperature can be visited. Suppose the pressure and spe- T2
cific volume are measured at each state and the value of the ratio pvT 1v is volume per
mole) determined. These ratios can then be plotted versus pressure at constant tempera- R
ture. The results for several temperatures are sketched in Fig. 3.10. When the ratios are T3
extrapolated to zero pressure, precisely the same limiting value is obtained for each curve.
That is, T4
pv p
lim R (3.21)
pS0 T Figure 3.10 Sketch
of pv T versus pressure
where R denotes the common limit for all temperatures. If this procedure were repeated for for a gas at several speci-
other gases, it would be found in every instance that the limit of the ratio pvT as p tends fied values of temperature.
to zero at fixed temperature is the same, namely R. Since the same limiting value is exhib-
ited by all gases, R is called the universal gas constant. Its value as determined experimen- universal gas constant
tally is
R 8.314 kJ/kmol # K (3.22)
Having introduced the universal gas constant, we turn next to the compressibility factor.
COMPRESSIBILITY FACTOR, Z
The dimensionless ratio pvRT is called the compressibility factor and is denoted by Z. compressibility factor
That is,
pv
Z (3.23)
RT
As illustrated by subsequent calculations, when values for p, v, R, and T are used in consis-
tent units, Z is unitless.
With v Mv (Eq. 1.11), where M is the atomic or molecular weight, the compressibility
factor can be expressed alternatively as
pv
Z (3.24)
RT
where
R
R (3.25)
M
R is a constant for the particular gas whose molecular weight is M. The unit for R is
kJ/kg # K.
Equation 3.21 can be expressed in terms of the compressibility factor as
lim Z 1 (3.26)
pS0
1.5
35 K
50 K
100 K
60 K
200 K
1.0
300 K
Z
0.5
Figure 3.11 Variation of the compressibility

0 100 200
factor of hydrogen with pressure at constant
p (atm) temperature.
That is, the compressibility factor Z tends to unity as pressure tends to zero at fixed
temperature. This can be illustrated by reference to Fig. 3.11, which shows Z for hydrogen
plotted versus pressure at a number of different temperatures. In general, at states of a gas
where pressure is small relative to the critical pressure, Z is approximately 1.
GENERALIZED COMPRESSIBILITY DATA, Z CHART
Figure 3.11 gives the compressibility factor for hydrogen versus pressure at specified values
of temperature. Similar charts have been prepared for other gases. When these charts are
studied, they are found to be qualitatively similar. Further study shows that when the coor-
dinates are suitably modified, the curves for several different gases coincide closely when
plotted together on the same coordinate axes, and so quantitative similarity also can be
achieved. This is referred to as the principle of corresponding states. In one such approach,
reduced pressure the compressibility factor Z is plotted versus a dimensionless reduced pressure pR and
and temperature reduced temperature TR, defined as
p T
pR and TR (3.27)
pc Tc
where pc and Tc denote the critical pressure and temperature, respectively. This results in a
generalized generalized compressibility chart of the form Z f (pR, TR). Figure 3.12 shows experimen-
compressibility chart tal data for 10 different gases on a chart of this type. The solid lines denoting reduced
isotherms represent the best curves fitted to the data.
A generalized chart more suitable for problem solving than Fig. 3.12 is given in the
Appendix as Figs. A-1, A-2, and A-3. In Fig. A-1, pR ranges from 0 to 1.0; in Fig. A-2, pR
ranges from 0 to 10.0; and in Fig. A-3, pR ranges from 10.0 to 40.0. At any one tempera-
ture, the deviation of observed values from those of the generalized chart increases with
pressure. However, for the 30 gases used in developing the chart, the deviation is at most
1.1
1.0 TR = 2.00
0.9
TR = 1.50
0.8
0.7 TR = 1.30
Z =
RT
pv
0.6 TR = 1.20
Legend
0.5 Methane Isopentane
TR = 1.10 Ethylene n-Heptane
Ethane Nitrogen
0.4 Propane Carbon dioxide
n-Butane Water
0.3 TR = 1.00 Average curve based on
data on hydrocarbons
0.2
0.1
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
Reduced pressure pR
Figure 3.12 Generalized compressibility chart for various gases.
on the order of 5% and for most ranges is much less.1 From Figs. A-1 and A-2 it can be
seen that the value of Z tends to unity for all temperatures as pressure tends to zero, in
accord with Eq. 3.26. Figure A-3 shows that Z also approaches unity for all pressures at
very high temperatures.
Values of specific volume are included on the generalized chart through the variable vR,
called the pseudoreduced specific volume, defined by
v pseudoreduced
vR (3.28)
RTcpc specific volume
For correlation purposes, the pseudoreduced specific volume has been found to be prefer-
able to the reduced specific volume vR vvc, where vc is the critical specific volume. Using
the critical pressure and critical temperature of a substance of interest, the generalized chart
can be entered with various pairs of the variables TR, pR, and vR: 1TR, pR 2, 1pR, vR 2, or 1TR, vR 2.
Tables A-1 list the critical constants for several substances.
The merit of the generalized chart for evaluating p, v, and T for gases is simplicity cou-
pled with accuracy. However, the generalized compressibility chart should not be used as a
substitute for pvT data for a given substance as provided by a table or computer software.
The chart is mainly useful for obtaining reasonable estimates in the absence of more accurate
data.
The next example provides an illustration of the use of the generalized compressibility
chart.
1
To determine Z for hydrogen, helium, and neon above a TR of 5, the reduced temperature and pressure should be
calculated using TR T(Tc
8) and pR p( pc
8), where temperatures are in K and pressures are in atm.
EXAMPLE 3.6 Using the Generalized Compressibility Chart
A closed, rigid tank filled with water vapor, initially at 20 MPa, 520C, is cooled until its temperature reaches 400C. Using
the compressibility chart, determine
(a) the specific volume of the water vapor in m3/kg at the initial state.
(b) the pressure in MPa at the final state.
Compare the results of parts (a) and (b) with the values obtained from the superheated vapor table, Table A-4.
SOLUTION
Known: Water vapor is cooled at constant volume from 20 MPa, 520C to 400C.
Find: Use the compressibility chart and the superheated vapor table to determine the specific volume and final pressure and
compare the results.
p1 = 20 MPa
T1 = 520C
T2 = 400C
1.0
Closed, rigid tank
1
Z1 TR = 1.3
2 TR = 1.2
Z =
vR Water
RT
= 1.2
pv
vR= 1.1 vapor

TR = 1.05
Cooling
0.5 pR2
Block of ice
0 0.5 1.0
pR
Figure E3.6
Assumptions:
1. The water vapor is a closed system.

2. The initial and final states are at equilibrium.
3. The volume is constant.
Analysis:
(a) From Table A-1, Tc 647.3 K and pc 22.09 MPa for water. Thus
TR1
793
1.23, pR1
20
0.91
647.3 22.09
With these values for the reduced temperature and reduced pressure, the value of Z obtained from Fig. A-1 is approximately
0.83. Since Z pvRT, the specific volume at state 1 can be determined as follows:
RT1 RT1
v1 Z1 0.83
p1 Mp1
N#m
8314
0.83
kmol # K
793 K
0.0152 m3/ kg
kg 6 N
18.02 20 10 2
kmol m
The molecular weight of water is from Table A-1.
Turning to Table A-4, the specific volume at the initial state is 0.01551 m3/kg. This is in good agreement with the com-
pressibility chart value, as expected.
(b) Since both mass and volume remain constant, the water vapor cools at constant specific volume, and thus at constant vR.
Using the value for specific volume determined in part (a), the constant vR value is
m3
a0.0152 b a22.09 106 2 b
N
vpc kg m
vR 1.12
a b 1647.3 K2
RTc 8314 N # m
18.02 kg # K
At state 2
673
TR2 1.04
647.3
Locating the point on the compressibility chart where vR 1.12 and TR 1.04, the corresponding value for pR is about 0.69.
Accordingly
p2 pc 1 pR2 2 122.09 MPa210.692 15.24 MPa
Interpolating in the superheated vapor tables gives p2 15.16 MPa. As before, the compressibility chart value is in good
agreement with the table value.
Absolute temperature and absolute pressure must be used in evaluating the compressibility factor Z, the reduced temper-
ature TR, and reduced pressure pR.
Since Z is unitless, values for p, v, R, and T must be used in consistent units.
EQUATIONS OF STATE
Considering the curves of Figs. 3.11 and 3.12, it is reasonable to think that the variation with
pressure and temperature of the compressibility factor for gases might be expressible as an equa-
tion, at least for certain intervals of p and T. Two expressions can be written that enjoy a theo-
retical basis. One gives the compressibility factor as an infinite series expansion in pressure:
Z 1
B1T 2 p
C1T 2 p2
D 1T 2 p3
# # # (3.29)
where the coefficients B, C, D, . . . depend on temperature only. The dots in Eq. 3.29 repre-
sent higher-order terms. The other is a series form entirely analogous to Eq. 3.29 but ex-
pressed in terms of 1v instead of p
B1T 2 C1T 2 D1T 2
Z1

2
3
# # # (3.30)
v v v
Equations 3.29 and 3.30 are known as virial equations of state, and the coefficients virial equations
B, C, D, . . . and B, C, D, . . . are called virial coefficients. The word virial stems from the
Latin word for force. In the present usage it is force interactions among molecules that are
intended.
The virial expansions can be derived by the methods of statistical mechanics, and physi-
cal significance can be attributed to the coefficients: B v accounts for two-molecule inter-
actions, C v2 accounts for three-molecule interactions, etc. In principle, the virial coefficients
can be calculated by using expressions from statistical mechanics derived from considera-
tion of the force fields around the molecules of a gas. The virial coefficients also can be de-
termined from experimental pvT data. The virial expansions are used in Sec. 11.1 as a
point of departure for the further study of analytical representations of the pvT relation-
ship of gases known generically as equations of state.
The virial expansions and the physical significance attributed to the terms making up the
expansions can be used to clarify the nature of gas behavior in the limit as pressure tends to
zero at fixed temperature. From Eq. 3.29 it is seen that if pressure decreases at fixed tem-
perature, the terms Bp, Cp2, etc. accounting for various molecular interactions tend to de-
crease, suggesting that the force interactions become weaker under these circumstances. In
the limit as pressure approaches zero, these terms vanish, and the equation reduces to Z 1
in accordance with Eq. 3.26. Similarly, since volume increases when the pressure decreases
at fixed temperature, the terms B v, C v2, etc. of Eq. 3.30 also vanish in the limit, giving
Z 1 when the force interactions between molecules are no longer significant.
EVALUATING PROPERTIES USING

THE IDEAL GAS MODEL
As discussed in Sec. 3.4, at states where the pressure p is small relative to the critical pres-
sure pc (low pR) and/or the temperature T is large relative to the critical temperature Tc (high
TR), the compressibility factor, Z pvRT, is approximately 1. At such states, we can assume
with reasonable accuracy that Z 1, or
ideal gas equation of
pv RT (3.32)
state
Known as the ideal gas equation of state, Eq. 3.32 underlies the second part of this chapter
dealing with the ideal gas model.
Alternative forms of the same basic relationship among pressure, specific volume, and
temperature are obtained as follows. With v Vm, Eq. 3.32 can be expressed as
pV mRT (3.33)
In addition, since v vM and R RM, where M is the atomic or molecular weight,
Eq. 3.32 can be expressed as
pv RT (3.34)
or, with v Vn, as
pV nRT (3.35)
3.5 Ideal Gas Model

For any gas whose equation of state is given exactly by pv RT, the specific internal en-
ergy depends on temperature only. This conclusion is demonstrated formally in Sec. 11.4. It
is also supported by experimental observations, beginning with the work of Joule, who showed
in 1843 that the internal energy of air at low density depends primarily on temperature. Fur-
ther motivation from the microscopic viewpoint is provided shortly. The specific enthalpy of
a gas described by pv RT also depends on temperature only, as can be shown by com-
bining the definition of enthalpy, h u
pv, with u u(T ) and the ideal gas equation of
state to obtain h u(T )
RT. Taken together, these specifications constitute the ideal gas
model, summarized as follows
pv RT (3.32)
ideal gas model u u1T 2 (3.36)
h h1T 2 u1T 2
RT (3.37)
3.5 Ideal Gas Model 101
The specific internal energy and enthalpy of gases generally depend on two independent METHODOLOGY
properties, not just temperature as presumed by the ideal gas model. Moreover, the ideal gas UPDATE
equation of state does not provide an acceptable approximation at all states. Accordingly, To expedite the solutions
whether the ideal gas model is used depends on the error acceptable in a given calculation. of many subsequent
Still, gases often do approach ideal gas behavior, and a particularly simplified description is examples and end-of-
chapter problems
obtained with the ideal gas model.
involving air, oxygen (O2),
To verify that a gas can be modeled as an ideal gas, the states of interest can be located nitrogen (N2), carbon
on a compressibility chart to determine how well Z 1 is satisfied. As shown in subsequent dioxide (CO2), carbon
discussions, other tabular or graphical property data can also be used to determine the suit- monoxide (CO), hydrogen
ability of the ideal gas model. (H2), and other common
gases, we indicate in the
problem statements that
MICROSCOPIC INTERPRETATION. A picture of the dependence of the internal energy of the ideal gas model
should be used. If not
gases on temperature at low density can be obtained with reference to the discussion of
indicated explicity, the
the virial equations in Sec. 3.4. As p S 0 (v S ), the force interactions between mole- suitability of the ideal gas
cules of a gas become weaker, and the virial expansions approach Z 1 in the limit. The model should be checked
study of gases from the microscopic point of view shows that the dependence of the in- using the Z chart or other
ternal energy of a gas on pressure, or specific volume, at a specified temperature arises data.
primarily because of molecular interactions. Accordingly, as the density of a gas decreases
at fixed temperature, there comes a point where the effects of intermolecular forces are
minimal. The internal energy is then determined principally by the temperature. From the
microscopic point of view, the ideal gas model adheres to several idealizations: The gas
consists of molecules that are in random motion and obey the laws of mechanics; the total
number of molecules is large, but the volume of the molecules is a negligibly small frac-
tion of the volume occupied by the gas; and no appreciable forces act on the molecules
except during collisions.
The next example illustrates the use of the ideal gas equation of state and reinforces the
use of property diagrams to locate principal states during processes.
EXAMPLE 3.7 Air as an Ideal Gas Undergoing a Cycle
One pound of air undergoes a thermodynamic cycle consisting of three processes.
Process 12: constant specific volume

Process 23: constant-temperature expansion
Process 31: constant-pressure compression
At state 1, the temperature is 300K, and the pressure is 1 bar. At state 2, the pressure is 2 bars. Employing the ideal gas equa-
tion of state,
(a) sketch the cycle on pv coordinates.

(b) determine the temperature at state 2, in K;
(c) determine the specific volume at state 3, in m3/ kg.
SOLUTION
Known: Air executes a thermodynamic cycle consisting of three processes: Process 12, v constant; Process 23,
T constant; Process 31, p constant. Values are given for T1, p1, and p2.
Find: Sketch the cycle on pv coordinates and determine T2 and v3.
2
p2 = 2 bars
Assumptions:
1. The air is a closed system. v=C

T=C
2. The air behaves as an ideal gas.
1 3
p1 = 1 bar p=C
600 K
300 K
v
Figure E3.7
Analysis:
(a) The cycle is shown on pv coordinates in the accompanying figure. Note that since p RTv and temperature is constant,
the variation of p with v for the process from 2 to 3 is nonlinear.
(b) Using pv RT, the temperature at state 2 is
T2 p2v2 R
To obtain the specific volume v2 required by this relationship, note that v2 v1, so
v2 RT1p1
Combining these two results gives
T a b 1300 K2 600 K
p2 2 bars
T2
p1 1 1 bar
(c) Since pv RT, the specific volume at state 3 is
v3 RT3 p3
Noting that T3 T2, p3 p1, and R RM
RT2
v3
Mp1
kJ
8.314
103 N # M
a ba 5 b a b
kmol # K 600 K 1 bar
kg 1 bar 10 N/m2 1 kJ
28.97
kmol
1.72 m3/kg
where the molecular weight of air is from Table A-1.
Table A-1 gives pc 37.3 bars, Tc 133 K for air. Therefore pR2 .053, TR2 4.51. Referring to A-1 the value of the
compressibility factor at this state is Z 1. The same conclusion results when states 1 and 3 are checked. Accordingly,
pv RT adequately describes the pvT relation for gas at these states.
Carefully note that the equation of state pv RT requires the use of absolute temperature T and absolute pressure p.
3.6 Internal Energy, Enthalpy, and Specific Heats of Ideal Gases 103

3.6 Internal Energy, Enthalpy, and Specific
Heats of Ideal Gases
For a gas obeying the ideal gas model, specific internal energy depends only on temperature.
Hence, the specific heat cv, defined by Eq. 3.8, is also a function of temperature alone. That is,
cv 1T 2 1ideal gas2
du
(3.38)
dT
This is expressed as an ordinary derivative because u depends only on T.
By separating variables in Eq. 3.38
du cv 1T 2 dT (3.39)
On integration
u1T2 2 u1T1 2 cv 1T 2 dT 1ideal gas2

T2
(3.40)
T1
Similarly, for a gas obeying the ideal gas model, the specific enthalpy depends only on
temperature, so the specific heat cp, defined by Eq. 3.9, is also a function of temperature
alone. That is
cp 1T 2 1ideal gas2
dh
(3.41)
dT
Separating variables in Eq. 3.41
dh cp 1T 2 dT (3.42)
On integration
h1T2 2 h1T1 2 cp 1T 2 dT 1ideal gas2

T2
(3.43)
T1
An important relationship between the ideal gas specific heats can be developed by dif-
ferentiating Eq. 3.37 with respect to temperature
dh du

R
dT dT
and introducing Eqs. 3.38 and 3.41 to obtain
cp 1T 2 cv 1T 2
R 1ideal gas2 (3.44)
On a molar basis, this is written as
cp 1T 2 cv 1T 2
R 1ideal gas2 (3.45)
Although each of the two ideal gas specific heats is a function of temperature, Eqs. 3.44 and
3.45 show that the specific heats differ by just a constant: the gas constant. Knowledge of
either specific heat for a particular gas allows the other to be calculated by using only the
gas constant. The above equations also show that cp cv and cp 7 cv, respectively.
For an ideal gas, the specific heat ratio, k, is also a function of temperature only
cp 1T 2
k 1ideal gas2
cv 1T 2
(3.46)
Since cp cv, it follows that k 1. Combining Eqs. 3.44 and 3.46 results in
cp 1T 2
kR
(3.47a)
k1
(ideal gas)
cv 1T 2
R (3.47b)
k1
Similar expressions can be written for the specific heats on a molar basis, with R being re-
placed by R.
USING SPECIFIC HEAT FUNCTIONS. The foregoing expressions require the ideal gas specific
heats as functions of temperature. These functions are available for gases of practical interest in
various forms, including graphs, tables, and equations. Figure 3.13 illustrates the variation of cp
(molar basis) with temperature for a number of common gases. In the range of temperature shown,
cp increases with temperature for all gases, except for the monatonic gases Ar, Ne, and He. For
these, cp is closely constant at the value predicted by kinetic theory: cp 52R. Tabular specific
heat data for selected gases are presented versus temperature in Tables A-20. Specific heats are
also available in equation form. Several alternative forms of such equations are found in the
engineering literature. An equation that is relatively easy to integrate is the polynomial form
cp
a
bT
gT 2
dT 3
eT 4 (3.48)
R
Values of the constants , , , , and are listed in Tables A-21 for several gases in the
temperature range 300 to 1000 K.
CO2
7
H2O
cp 5 O2
R CO
H2
4
Air
3
Ar, Ne, He
0
1000 2000 3000
Temperature, K
Figure 3.13 Variation of cp R with temperature for a number of gases
modeled as ideal gases.
3.7 Evaluating u and h Using Ideal Gas Tables, Software, and Constant Specific Heats 105
for example. . . to illustrate the use of Eq. 3.48, let us evaluate the change in spe-
cific enthalpy, in kJ/kg, of air modeled as an ideal gas from a state where T1 400 K to a
state where T2 900 K. Inserting the expression for cp(T ) given by Eq. 3.48 into Eq. 3.43
and integrating with respect to temperature
1a
bT
gT 2
dT 3
eT 4 2 dT
R T2
h2 h1
M T1
c a1T2 T1 2
1T 22 T 21 2
1T 32 T 31 2
1T 42 T 41 2
1T 52 T 51 2 d
R b g d e

M 2 3 4 5
where the molecular weight M has been introduced to obtain the result on a unit mass basis.
With values for the constants from Table A-21
e 3.6531900 4002 19002 2 14002 2

8.314 1.337
h2 h1
28.97 21102 3
19002 3 14002 3 19002 4 14002 4

3.294 1.913

31102 6
41102 9
19002 5 14002 5 f 531.69 kJ/kg

0.2763

51102 12
Specific heat functions cv(T) and cp(T) are also available in IT: Interactive Thermodynamics
in the PROPERTIES menu. These functions can be integrated using the integral function of
the program to calculate u and h, respectively. for example. . . let us repeat the im-
mediately preceding example using IT. For air, the IT code is
cp = cp_T (Air,T)
delh = Integral(cp,T)
Pushing SOLVE and sweeping T from 400 K to 900 K, the change in specific enthalpy is
delh 531.7 kJ/kg, which agrees closely with the value obtained by integrating the spe-
cific heat function from Table A-21, as illustrated above.
The source of ideal gas specific heat data is experiment. Specific heats can be deter-
mined macroscopically from painstaking property measurements. In the limit as pressure
tends to zero, the properties of a gas tend to merge into those of its ideal gas model, so
macroscopically determined specific heats of a gas extrapolated to very low pressures may
be called either zero-pressure specific heats or ideal gas specific heats. Although zero-
pressure specific heats can be obtained by extrapolating macroscopically determined
experimental data, this is rarely done nowadays because ideal gas specific heats can readily
be calculated with expressions from statistical mechanics by using spectral data, which
can be obtained experimentally with precision. The determination of ideal gas specific heats
is one of the important areas where the microscopic approach contributes significantly to
the application of thermodynamics.

3.7 Evaluating u and h Using Ideal Gas
Tables, Software, and Constant
Specific Heats
Although changes in specific enthalpy and specific internal energy can be obtained by
integrating specific heat expressions, as illustrated above, such evaluations are more easily
conducted using the means considered in the present section.
USING IDEAL GAS TABLES
For a number of common gases, evaluations of specific internal energy and enthalpy changes
are facilitated by the use of the ideal gas tables, Tables A-22 and A-23, which give u and h
(or u and h) versus temperature.
To obtain enthalpy versus temperature, write Eq. 3.43 as
h1T 2 cp 1T 2 dT
h1Tref 2
T
Tref
where Tref is an arbitrary reference temperature and h(Tref) is an arbitrary value for enthalpy
at the reference temperature. Tables A-22 and A-23 are based on the selection h 0 at
Tref 0 K. Accordingly, a tabulation of enthalpy versus temperature is developed through
the integral2
h1T 2 cp 1T 2 dT
T
(3.49)
0
Tabulations of internal energy versus temperature are obtained from the tabulated enthalpy
values by using u h RT.
For air as an ideal gas, h and u are given in Table A-22 with units of kJ/kg. Values of mo-
lar specific enthalpy h and internal energy u for several other common gases modeled as ideal
gases are given in Tables A-23 with units of kJ/kmol. Quantities other than specific internal en-
ergy and enthalpy appearing in these tables are introduced in Chap. 6 and should be ignored
at present. Tables A-22 and A-23 are convenient for evaluations involving ideal gases, not only
because the variation of the specific heats with temperature is accounted for automatically but
also because the tables are easy to use.
for example. . . let us use Table A-22 to evaluate the change in specific enthalpy,
in kJ/kg, for air from a state where T1 400 K to a state where T2 900 K, and compare
the result with the value obtained by integrating cp 1T 2 in the example following Eq. 3.48. At
the respective temperatures, the ideal gas table for air, Table A-22, gives
kJ kJ
h1 400.98 , h2 932.93
kg kg
Then, h2 h1 531.95 kJ/kg, which agrees with the value obtained by integration in
Sec. 3.6.
USING COMPUTER SOFTWARE
Interactive Thermodynamics: IT also provides values of the specific internal energy and en-
thalpy for a wide range of gases modeled as ideal gases. Let us consider the use of IT, first
for air, and then for other gases.
AIR. For air, IT uses the same reference state and reference value as in Table A-22, and the
values computed by IT agree closely with table data. for example. . . let us recon-
sider the above example for air and use IT to evaluate the change in specific enthalpy from
a state where T1 400 K to a state where T2 900 K. Selecting Air from the Properties
menu, the following code would be used by IT to determine h (delh), in kJ/kg
h1 = h_T(Air,T1)
h2 = h_T(Air,T2)
T1 = 400 // K
T2 = 900 // K
delh = h2 h1
2
The simple specific heat variation given by Eq. 3.48 is valid only for a limited temperature range, so tabular
enthalpy values are calculated from Eq. 3.49 using other expressions that enable the integral to be evaluated
accurately over wider ranges of temperature.
Choosing K for the temperature unit and kg for the amount under the Units menu, the results
returned by IT are h1 400.8, h2 932.5, and h 531.7 kJ/kg, respectively. As expected,
these values agree closely with those obtained previously.
OTHER GASES. IT also provides data for each of the gases included in Table A-23. For
these gases, the values of specific internal energy u and enthalpy h returned by IT are de-
termined relative to different reference states and reference values than used in Table A-23.
Such reference state and reference value choices equip IT for use in combustion applications;
see Sec. 13.2.1 for further discussion. Consequently the values of u and h returned by IT for
the gases of Table A-23 differ from those obtained directly from the table. Still, the property
differences between two states remain the same, for datums cancel when differences are
calculated.
for example. . . let us use IT to evaluate the change in specific enthalpy, in kJ/kmol,
for carbon dioxide (CO2) as an ideal gas from a state where T1 300 K to a state where T2
500 K. Selecting CO2 from the Properties menu, the following code would be used by IT:
h1 = h_T(CO2,T1)
h2 = h_T(CO2,T2)
T1 = 300 // K
T2 = 500 // K
delh = h2 h1
Choosing K for the temperature unit and moles for the amount under the Units menu, the
results returned by IT are h1 3.935 105, h2 3.852 105, and h 8238 kJ/kmol,
respectively. The large negative values for h1 and h2 are a consequence of the reference state
and reference value used by IT for CO2. Although these values for specific enthalpy at states
1 and 2 differ from the corresponding values read from Table A-23: h1 9,431 and
h2 17,678, which give h 8247 kJ/kmol, the difference in specific enthalpy determined
with each set of data agree closely.
ASSUMING CONSTANT SPECIFIC HEATS
When the specific heats are taken as constants, Eqs. 3.40 and 3.43 reduce, respectively, to
u 1T2 2 u 1T1 2 cv 1T2 T1 2 (3.50)
h 1T2 2 h 1T1 2 cp 1T2 T1 2 (3.51)
Equations 3.50 and 3.51 are often used for thermodynamic analyses involving ideal gases
because they enable simple closed-form equations to be developed for many processes.
The constant values of cv and cp in Eqs. 3.50 and 3.51 are, strictly speaking, mean values
calculated as follows
cv 1T 2 dT cp 1T 2 dT
T2 T2
T1 T1
cv , cp
T2 T1 T2 T1
However, when the variation of cv or cp over a given temperature interval is slight, little error
is normally introduced by taking the specific heat required by Eq. 3.50 or 3.51 as the arithmetic
average of the specific heat values at the two end temperatures. Alternatively, the specific
heat at the average temperature over the interval can be used. These methods are particularly
convenient when tabular specific heat data are available, as in Tables A-20, for then the
constant specific heat values often can be determined by inspection.
The next example illustrates the use of the ideal gas tables, together with the closed system
energy balance.
EXAMPLE 3.8 Using the Energy Balance and Ideal Gas Tables
A pistoncylinder assembly contains 0.9 kg of air at a temperature of 300K and a pressure of 1 bar. The air is compressed
to a state where the temperature is 470K and the pressure is 6 bars. During the compression, there is a heat transfer from the
air to the surroundings equal to 20 kJ. Using the ideal gas model for air, determine the work during the process, in kJ.
SOLUTION
Known: 0.9 kg of air are compressed between two specified states while there is heat transfer from the air of a known
amount.
Find: Determine the work, in kJ.
p2 = 6 bars
2
0.9 kg
of
air
T2 = 470
1
p1 = 1 bar T1 = 300K
v
Figure E3.8
Assumptions:
1. The air is a closed system.

2. The initial and final states are equilibrium states. There is no change in kinetic or potential energy.
3. The air is modeled as an ideal gas.
Analysis: An energy balance for the closed system is

0 0
KE
PE
U Q W
where the kinetic and potential energy terms vanish by assumption 2. Solving for W
W Q U Q m 1u2 u1 2
From the problem statement, Q 20 kJ. Also, from Table A-22 at T1 300 K, u1 214.07 kJ/ kg, and at T2 470K,
u2 337.32 kJ/kg. Accordingly
W 20 10.921337.32 214.072 130.9 kJ
The minus sign indicates that work is done on the system in the process.
Although the initial and final states are assumed to be equilibrium states, the intervening states are not necessarily equi-
librium states, so the process has been indicated on the accompanying pv diagram by a dashed line. This dashed line
does not define a path for the process.
Table A-1 gives pc 37.7 bars, Tc 133K for air. Therefore, at state 1, pR1 0.03, TR1 2.26, and at state 2, pR2
0.16, TR2 3.51. Referring to Fig. A-1, we conclude that at these states Z 1, as assumed in the solution.
In principle, the work could be evaluated through p dV, but because the variation of pressure at the piston face with vol-
ume is not known, the integration cannot be performed without more information.
The following example illustrates the use of the closed system energy balance, together
with the ideal gas model and the assumption of constant specific heats.
EXAMPLE 3.9 Using the Energy Balance and Constant Specific Heats
Two tanks are connected by a valve. One tank contains 2 kg of carbon monoxide gas at 77C and 0.7 bar. The other tank holds
8 kg of the same gas at 27C and 1.2 bar. The valve is opened and the gases are allowed to mix while receiving energy by
heat transfer from the surroundings. The final equilibrium temperature is 42C. Using the ideal gas model, determine (a) the
final equilibrium pressure, in bar (b) the heat transfer for the process, in kJ.
SOLUTION
Known: Two tanks containing different amounts of carbon monoxide gas at initially different states are connected by a valve.
The valve is opened and the gas allowed to mix while receiving a certain amount of energy by heat transfer. The final equi-
librium temperature is known.
Find: Determine the final pressure and the heat transfer for the process.
Assumptions:
1. The total amount of carbon monoxide gas is a closed system. Carbon Carbon
monoxide
2. The gas is modeled as an ideal gas with constant cv. monoxide
3. The gas initially in each tank is in equilibrium. The final state is 2 kg, 77C, Valve 8 kg, 27C,
an equilibrium state. 0.7 bar 1.2 bar
4. No energy is transferred to, or from, the gas by work.
Tank 1 Tank 2
5. There is no change in kinetic or potential energy.
Figure E3.9
Analysis:
(a) The final equilibrium pressure pf can be determined from the ideal gas equation of state
mRTf
pf
V
where m is the sum of the initial amounts of mass present in the two tanks, V is the total volume of the two tanks, and Tf is
the final equilibrium temperature. Thus
1m1
m2 2RTf
pf
V1
V2
Denoting the initial temperature and pressure in tank 1 as T1 and p1, respectively, V1 m1RT1p1. Similarly, if the initial tem-
perature and pressure in tank 2 are T2 and p2, V2 m2RT2p2. Thus, the final pressure is
1m1
m2 2RTf 1m1
m2 2Tf
pf
a b
a b a b
a b
m1RT1 m2 RT2 m1T1 m2 T2
p1 p2 p1 p2
Inserting values
110 kg21315 K2
pf 1.05 bar
12 kg21350 K2 18 kg21300 K2

0.7 bar 1.2 bar

(b) The heat transfer can be found from an energy balance, which reduces with assumptions 4 and 5 to give
0
U Q W
or
Q Uf Ui
Ui is the initial internal energy, given by

Ui m1u 1T1 2
m2u 1T2 2
where T1 and T2 are the initial temperatures of the CO in tanks 1 and 2, respectively. The final internal energy is Uf
Uf 1m1
m2 2 u 1Tf 2
Introducing these expressions for internal energy, the energy balance becomes
Q m1 3u 1Tf 2 u 1T1 2 4
m2 3 u 1Tf 2 u 1T2 2 4
Since the specific heat cv is constant (assumption 2)
Q m1cv 1Tf T1 2
m2cv 1Tf T2 2
Evaluating cv as the mean of the values listed in Table A-20 at 300 K and 350 K, cv 0.745 kJ/kg # K. Hence
Q 12 kg2 a0.745 b 1315 K 350 K2

18 kg2 a0.745 # b 1315 K 300 K2
37.25 kJ
kJ kJ
kg # K kg K
The plus sign indicates that the heat transfer is into the system.
By referring to a generalized compressibility chart, it can be verified that the ideal gas equation of state is appropriate for
CO in this range of temperature and pressure. Since the specific heat cv of CO varies little over the temperature interval
from 300 to 350 K (Table A-20), it can be treated as constant with acceptable accuracy.
As an exercise, evaluate Q using specific internal energy values from the ideal gas table for CO, Table A-23. Observe that
specific internal energy is given in Table A-23 with units of kJ/kmol.
The next example illustrates the use of software for problem solving with the ideal gas
model. The results obtained are compared with those determined assuming the specific heat
cv is constant.
EXAMPLE 3.10 Using the Energy Balance and Software
One kmol of carbon dioxide gas (CO2) in a pistoncylinder assembly undergoes a constant-pressure process at 1 bar from
T1 300 K to T2. Plot the heat transfer to the gas, in kJ, versus T2 ranging from 300 to 1500 K. Assume the ideal gas model,
and determine the specific internal energy change of the gas using
(a) u data from IT.

(b) a constant cv evaluated at T1 from IT.
SOLUTION
Known: One kmol of CO2 undergoes a constant-pressure process in a pistoncylinder assembly. The initial temperature, T1,
and the pressure are known.
Find: Plot the heat transfer versus the final temperature, T2. Use the ideal gas model and evaluate u using (a) u data from
IT, (b) constant cv evaluated at T1 from IT.
Assumptions:
T1 = 300 K 1. The carbon dioxide is a closed system.

Carbon n = 1 kmol
dioxide 2. The process occurs at constant pressure.
p = 1 bar
3. The carbon dioxide behaves as an ideal gas.
Figure E3.10a
Analysis: The heat transfer is found using the closed system energy balance, which reduces to
U2 U1 Q W
Using Eq. 2.17 at constant pressure (assumption 2)
W p 1V2 V1 2 pn 1v2 v1 2
Then, with U n1u2 u1 2, the energy balance becomes
n 1u2 u1 2 Q pn 1v2 v1 2
Solving for Q
Q n 3 1u2 u1 2
p 1v2 v1 2 4
With pv RT, this becomes
Q n 3 1u2 u1 2
R1T2 T1 2 4
The object is to plot Q versus T2 for each of the following cases: (a) values for u1 and u2 at T1 and T2, respectively, are pro-
vided by IT, (b) Eq. 3.50 is used on a molar basis, namely
u2 u1 cv 1T2 T1 2
where the value of cv is evaluated at T1 using IT.
The IT program follows, where Rbar denotes R, cvb denotes cv, and ubar1 and ubar2 denote u1 and u2, respectively.
// Using the Units menu, select mole for the substance amount.
// Given Data
T1 = 300 // K
T2 = 1500 // K
n = 1 // kmol
Rbar = 8.314 // kJ/kmol # K
// (a) Obtain molar specific internal energy data using IT.

ubar1 = u_T(CO2, T1)
ubar2 = u_T(CO2, T2)
Qa = n*(ubar2 ubar1) + n*Rbar*(T2 T1)
// (b) Use Eq. 3.50 with cv evaluated at T1.

cvb = cv_T(CO2, T1)
Qb = n*cvb*(T2 T1) + n*Rbar*(T2 T1)
Use the Solve button to obtain the solution for the sample case of T2 1500 K. For part (a), the program returns Qa 6.16
104 kJ. The solution can be checked using CO2 data from Table A-23, as follows:
Qa n 3 1u2 u1 2
R1T2 T1 2 4
11 kmol2 3 158,606 69392 kJ/kmol
18.314 kJ/kmol # K211500 3002 K 4
61,644 kJ
Thus, the result obtained using CO2 data from Table A-23 is in close agreement with the computer solution for the sample
case. For part (b), IT returns cv 28.95 kJ/kmol # K at T1, giving Qb 4.472 104 kJ when T2 1500 K. This value agrees
with the result obtained using the specific heat cv at 300 K from Table A-20, as can be verified.
Now that the computer program has been verified, use the Explore button to vary T2 from 300 to 1500 K in steps of 10.
Construct the following graph using the Graph button:
70,000
60,000 internal energy data

cv at T1
50,000
40,000
Q, kJ
30,000
20,000
10,000
0
300 500 700 900 1100 1300 1500
T2, K
Figure E3.10b
As expected, the heat transfer is seen to increase as the final temperature increases. From the plots, we also see that using
constant cv evaluated at T1 for calculating u, and hence Q, can lead to considerable error when compared to using u data. The
two solutions compare favorably up to about 500 K, but differ by approximately 27% when heating to a temperature of 1500 K.
Alternatively, this expression for Q can be written as

Q n 3 1u2
pv2 2 1u1
pv1 2 4
Introducing h u
pv, the expression for Q becomes
Q n 1h2 h1 2
It is left as an exercise to verify that more accurate results in part (b) would be obtained using cv evaluated at Taverage
(T1
T2)2.
3.8 Polytropic Process of an Ideal Gas

Recall that a polytropic process of a closed system is described by a pressurevolume rela-
tionship of the form
pV n constant (3.52)
where n is a constant (Sec. 2.2). For a polytropic process between two states
p1V n1 p2V n2
or
V1 n
a b
p2
(3.53)
p1 V2
The exponent n may take on any value from to
, depending on the particular process.
When n 0, the process is an isobaric (constant-pressure) process, and when n , the
process is an isometric (constant-volume) process.
3.8 Polytropic Process of an Ideal Gas 113
For a polytropic process

p2V2 p1V1
1n 12
2
p dV (3.54)
1 1n
for any exponent n except n 1. When n 1,
1n 12
2 V2
p dV p1V1 ln (3.55)
1 V1
Example 2.1 provides the details of these integrations.
Equations 3.52 through 3.55 apply to any gas (or liquid) undergoing a polytropic process.
When the additional idealization of ideal gas behavior is appropriate, further relations can
be derived. Thus, when the ideal gas equation of state is introduced into Eqs. 3.53, 3.54, and
3.55, the following expressions are obtained, respectively
p2 1n12n V1 n1
a b a b 1ideal gas2
T2
(3.56)
T1 p1 V2
mR 1T2 T1 2
1ideal gas, n 12
2
p dV (3.57)
1 1n
2
1ideal gas, n 12
V2
p dV mRT ln (3.58)
1 V1
For an ideal gas, the case n 1 corresponds to an isothermal (constant-temperature) process,
as can readily be verified. In addition, when the specific heats are constant, the value of the
exponent n corresponding to an adiabatic polytropic process of an ideal gas is the specific
heat ratio k (see discussion of Eq. 6.47).
Example 3.11 illustrates the use of the closed system energy balance for a system con-
sisting of an ideal gas undergoing a polytropic process.
EXAMPLE 3.11 Polytropic Process of Air as an Ideal Gas
Air undergoes a polytropic compression in a pistoncylinder assembly from p1 1 bar, T1 22C to p2 5 bars. Employing
the ideal gas model, determine the work and heat transfer per unit mass, in kJ/kg, if n 1.3.
SOLUTION
Known: Air undergoes a polytropic compression process from a given initial state to a specified final pressure.
Find: Determine the work and heat transfer, each in kJ/kg.
p
2 Assumptions:
5 bars
1. The air is a closed system.
Air 2. The air behaves as an ideal
pv1.3 = constant
p1 = 1 bar
T1 = 22C
gas.
p2 = 5 bars 3. The compression is
polytropic with n 1.3.
1
1 bar 4. There is no change in
kinetic or potential energy.
v
Figure E3.11
Analysis: The work can be evaluated in this case from the expression

2
W p dV
1
With Eq. 3.57
W R1T2 T1 2

m 1n
The temperature at the final state, T2, is required. This can be evaluated from Eq. 3.56
p2 1n12n 5 11.3121.3
T2 T1 a b 295 K a b 428K
p1 1
The work is then
R1T2 T1 2 428K 295K
a ba b 127.2 kJ/kg
W 8.314 kJ

m 1n 28.97 kg # K 1 1.3
The heat transfer can be evaluated from an energy balance. Thus

1u2 u1 2 127.2
1306.53 210.492 31.16 kJ/kg
Q W

m m
where the specific internal energy values are obtained from Table A-22.
The states visited in the polytropic compression process are shown by the curve on the accompanying pv diagram. The
magnitude of the work per unit of mass is represented by the shaded area below the curve.
In this chapter, we have considered property relations for a The following checklist provides a study guide for this
broad range of substances in tabular, graphical, and equation chapter. When your study of the text and end-of-chapter
form. Primary emphasis has been placed on the use of tabu- exercises has been completed you should be able to
lar data, but computer retrieval also has been considered.
A key aspect of thermodynamic analysis is fixing states.
This is guided by the state principle for pure, simple com-
concepts. The subset of key concepts listed below is
pressible systems, which indicates that the intensive state is
particularly important in subsequent chapters.
fixed by the values of two independent, intensive properties.
Another important aspect of thermodynamic analysis is lo- retrieve property data from Tables A-1 through A-23,
cating principal states of processes on appropriate diagrams: using the state principle to fix states and linear interpola-
pv, Tv, and pT diagrams. The skills of fixing states and tion when required.
using property diagrams are particularly important when solv- sketch Tv, pv, and pT diagrams, and locate principal
ing problems involving the energy balance. states on such diagrams.
The ideal gas model is introduced in the second part of apply the closed system energy balance with property
this chapter, using the compressibility factor as a point of data.
departure. This arrangement emphasizes the limitations of the
evaluate the properties of two-phase, liquidvapor
ideal gas model. When it is appropriate to use the ideal gas
mixtures using Eqs. 3.1, 3.2, 3.6, and 3.7.
model, we stress that specific heats generally vary with
temperature, and feature the use of the ideal gas tables in estimate the properties of liquids using Eqs. 3.11, 3.12,
problem solving. and 3.14.
apply the incompressible substance model. is warranted, and appropriately using ideal gas table
use the generalized compressibility chart to relate pvT data or constant specific heat data to determine u
data of gases. and h.
apply the ideal gas model for thermodynamic analysis,
including determining when use of the ideal gas model
state principle p. 69 saturation two-phase, liquidvapor enthalpy p. 83

simple compressible temperature p. 73 mixture p. 75 specific heats p. 91
system p. 69 saturation pressure p. 73 quality p. 75 ideal gas model p. 100
pvT surface p. 70 pv diagram p. 73 superheated
phase diagram p. 72 Tv diagram p. 73 vapor p. 75
1. Why does food cook more quickly in a pressure cooker than volume v, can the mass, in kg, of each phase be determined?
in water boiling in an open container? Repeat for a three-phase, solidliquidvapor mixture in equilib-
2. If water contracted on freezing, what implications might this rium at T, v.
have for aquatic life? 11. By inspection of Fig. 3.9, what are the values of cp for water
3. Why do frozen water pipes tend to burst? at 500C and pressures equal to 40 MPa, 20 MPa, 10 MPa,
and 1 MPa? Is the ideal gas model appropriate at any of these
4. Referring to a phase diagram, explain why a film of liquid
states?
water forms under the blade of an ice skate.
12. Devise a simple experiment to determine the specific heat,
5. Can water at 40C exist as a vapor? As a liquid?
cp, of liquid water at atmospheric pressure and room tempera-
6. What would be the general appearance of constant-volume ture.
lines in the vapor and liquid regions of the phase diagram?
13. If a block of aluminum and a block of steel having equal
7. Are the pressures listed in the tables in the Appendix absolute volumes each received the same energy input by heat transfer,
pressures or gage pressures? which block would experience the greater temperature
8. The specific internal energy is arbitrarily set to zero in Table increase?
A-2 for saturated liquid water at 0.01C. If the reference value 14. Under what circumstances is the following statement cor-
for u at this reference state were specified differently, would there rect? Equal molar amounts of two different gases at the same
be any significant effect on thermodynamic analyses using u temperature, placed in containers of equal volume, have the same
and h? pressure.
9. For liquid water at 20C and 1.0 MPa, what percent difference 15. Estimate the mass of air contained in a bicycle tire.
would there be if its specific enthalpy were evaluated using
16. Specific internal energy and enthalpy data for water vapor
Eq. 3.14 instead of Eq. 3.13?
are provided in two tables: Tables A-4 and A-23. When would
10. For a system consisting of 1 kg of a two-phase, liquidvapor Table A-23 be used?
mixture in equilibrium at a known temperature T and specific
Using pvT Data (d) T 160C, p 4.8 bar.

3.1 Determine the phase or phases in a system consisting of (e) T 12C, p 1 bar.
H2O at the following conditions and sketch pv and Tv dia- 3.2 Plot the pressuretemperature relationship for two-phase
grams showing the location of each state. liquidvapor mixtures of water from the triple point tem-
(a) p 5 bar, T 151.9C. perature to the critical point temperature. Use a logarithmic
(b) p 5 bar, T 200C. scale for pressure, in bar, and a linear scale for temperature,
(c) T 200C, p 2.5 MPa. in C.
3.3 For H2O, plot the following on a pv diagram drawn to the final mass of vapor in the tank, in kg, and the final pres-
scale on loglog coordinates: sure, in bar.
(a) the saturated liquid and saturated vapor lines from the triple 3.15 Two thousand kg of water, initially a saturated liquid at
point to the critical point, with pressure in MPa and spe- 150C, is heated in a closed, rigid tank to a final state where
cific volume in m3/kg. the pressure is 2.5 MPa. Determine the final temperature, in
(b) lines of constant temperature at 100 and 300C. C, the volume of the tank, in m3, and sketch the process on
3.4 Plot the pressuretemperature relationship for two-phase Tv and pv diagrams.
liquidvapor mixtures of (a) Refrigerant 134a, (b) ammonia, 3.16 Steam is contained in a closed rigid container with a vol-
(c) Refrigerant 22 from a temperature of 40 to 100C, with ume of 1 m3. Initially, the pressure and temperature of the steam
pressure in kPa and temperature in C. Use a logarithmic scale are 7 bar and 500C, respectively. The temperature drops as a
for pressure and a linear scale for temperature. result of heat transfer to the surroundings. Determine the tem-
3.5 Determine the quality of a two-phase liquidvapor mixture perature at which condensation first occurs, in C, and the
of fraction of the total mass that has condensed when the pres-
sure reaches 0.5 bar. What is the volume, in m3, occupied by
(a) H2O at 20C with a specific volume of 20 m3/kg.
saturated liquid at the final state?
(b) Propane at 15 bar with a specific volume of 0.02997 m3/kg.
(c) Refrigerant 134a at 60C with a specific volume of 0.001 3.17 Water vapor is heated in a closed, rigid tank from satu-
m3/kg. rated vapor at 160C to a final temperature of 400C. Deter-
(d) Ammonia at 1 MPa with a specific volume of 0.1 m3/kg. mine the initial and final pressures, in bar, and sketch the
3.6 For H2O, plot the following on a pv diagram drawn to process on Tv and pv diagrams.
scale on loglog coordinates: 3.18 Ammonia undergoes an isothermal process from an initial
(a) the saturated liquid and saturated vapor lines from the triple state at T1 80F and v1 10 ft3/lb to saturated vapor. De-
point to the critical point, with pressure in KPa and spe- termine the initial and final pressures, in lbf/in.2, and sketch
cific volume in m3/kg 150C the process on Tv and pv diagrams.
(b) lines of constant temperature at 300 and 560C. 3.19 A two-phase liquidvapor mixture of H2O is initially at a
3.7 Two kg of a two-phase, liquidvapor mixture of carbon pressure of 30 bar. If on heating at fixed volume, the critical
dioxide (CO2) exists at 40C in a 0.05 m3 tank. Determine point is attained, determine the quality at the initial state.
the quality of the mixture, if the values of specific volume 3.20 Ammonia undergoes a constant-pressure process at 2.5 bar
for saturated liquid and saturated vapor CO2 at 40C are from T1 30C to saturated vapor. Determine the work for the
vf 0.896 103 m3/kg and vg 3.824 102 m3/kg, process, in kJ per kg of refrigerant.
respectively.
3.21 Water vapor in a pistoncylinder assembly is heated at a
3.8 Determine the mass, in kg, of 0.1 m3 of Refrigerant 134a constant temperature of 204C from saturated vapor to a pres-
at 4 bar, 100C. sure of .7 MPa. Determine the work, in kJ per kg of water
3.9 A closed vessel with a volume of 0.018 m3 contains 1.2 kg vapor, by using IT.
of Refrigerant 22 at 10 bar. Determine the temperature, in C. 3.22 2 kg mass of ammonia, initially at p1 7 bars and
3.10 Calculate the mass, in kg, of 1 m3 of a two-phase liquid T1 180C, undergo a constant-pressure process to a final
vapor mixture of Refrigerant 22 at 1 bar with a quality state where the quality is 85%. Determine the work for the
of 75%. process, kJ.
3.11 A two-phase liquidvapor mixture of a substance has a 3.23 Water vapor initially at 10 bar and 400C is contained
pressure of 150 bar and occupies a volume of 0.2 m3. The masses within a pistoncylinder assembly. The water is cooled at con-
of saturated liquid and vapor present are 3.8 kg and 4.2 kg, re- stant volume until its temperature is 150C. The water is then
spectively. Determine the mixture specific volume in m3/kg. condensed isothermally to saturated liquid. For the water as
3.12 Ammonia is stored in a tank with a volume of 0.21 m3. the system, evaluate the work, in kJ/kg.
Determine the mass, in kg, assuming saturated liquid at 20C. 3.24 Two kilograms of Refrigerant 22 undergo a process for
What is the pressure, in kPa? which the pressurevolume relation is pv1.05 constant. The
3.13 A storage tank in a refrigeration system has a volume of initial state of the refrigerant is fixed by p1 2 bar, T1 20C,
0.006 m3 and contains a two-phase liquidvapor mixture of and the final pressure is p2 10 bar. Calculate the work for the
Refrigerant 134a at 180 kPa. Plot the total mass of refrigerant, process, in kJ.
in kg, contained in the tank and the corresponding fractions of 3.25 Refrigerant 134a in a pistoncylinder assembly under-
the total volume occupied by saturated liquid and saturated goes a process for which the pressurevolume relation is
vapor, respectively, as functions of quality. pv1.058 constant. At the initial state, p1 200 kPa, T1
3.14 Water is contained in a closed, rigid, 0.2 m3 tank at an ini- 10C. The final temperature is T2 50C. Determine the
tial pressure of 5 bar and a quality of 50%. Heat transfer oc- final pressure, in kPa, and the work for the process, in kJ per
curs until the tank contains only saturated vapor. Determine kg of refrigerant.
Using uh Data 8 bar to 50C. For the refrigerant, determine the work and heat
3.26 Using the tables for water, determine the specified prop- transfer, per unit mass, each in kJ/kg. Changes in kinetic and
erty data at the indicated states. Check the results using IT. In potential energy are negligible.
each case, locate the state by hand on sketches of the pv and 3.35 Saturated liquid water contained in a closed, rigid tank is
Tv diagrams. cooled to a final state where the temperature is 50C and the
(a) At p 3 bar, T 240C, find v in m3/kg and u in kJ/kg. masses of saturated vapor and liquid present are 0.03 and
(b) At p 3 bar, v 0.5 m3/kg, find T in C and u in kJ/kg. 1999.97 kg, respectively. Determine the heat transfer for the
(c) At T 400C, p 10 bar, find v in m3/kg and h in kJ/kg. process, in kJ.
(d) At T 320C, v 0.03 m3/kg, find p in MPa and u in 3.36 Refrigerant 134a undergoes a process for which the
kJ/kg. pressurevolume relation is pvn constant. The initial and
(e) At p 28 MPa, T 520C, find v in m3/kg and h in kJ/kg. final states of the refrigerant are fixed by p1 200 kPa, T1
(f) At T 100C, x 60%, find p in bar and v in m3/kg. 10C and p2 1000 kPa, T2 50C, respectively. Calculate
(g) At T 10C, v 100 m3/kg, find p in kPa and h in kJ/kg. the work and heat transfer for the process, each in kJ per kg
(h) At p 4 MPa, T 160C, find v in m3/kg and u in kJ/kg. of refrigerant.
3.27 Determine the values of the specified properties at each of 3.37 A pistoncylinder assembly contains a two-phase
the following conditions. liquidvapor mixture of Refrigerant 22 initially at 24C with a
(a) For Refrigerant 134a at T 60C and v 0.072 m3/kg, quality of 95%. Expansion occurs to a state where the pressure
determine p in kPa and h in kJ/kg. is 1 bar. During the process the pressure and specific volume
(b) For ammonia at p 8 bar and v 0.005 m3/kg, deter- are related by pv constant. For the refrigerant, determine
mine T in C and u in kJ/kg. the work and heat transfer per unit mass, each in kJ/kg.
(c) For Refrigerant 22 at T 10C and u 200 kJ/kg, de- 3.38 Five kilograms of water, initially a saturated vapor at
termine p in bar and v in m3/kg. 100 kPa, are cooled to saturated liquid while the pressure is
3.28 A quantity of water is at 15 MPa and 100C. Evaluate the maintained constant. Determine the work and heat transfer for
specific volume, in m3/kg, and the specific enthalpy, in kJ/kg, the process, each in kJ. Show that the heat transfer equals the
using change in enthalpy of the water in this case.
(a) data from Table A-5. 3.39 One kilogram of saturated solid water at the triple point
(b) saturated liquid data from Table A-2. is heated to saturated liquid while the pressure is maintained
constant. Determine the work and the heat transfer for the
3.29 Plot versus pressure the percent changes in specific vol- process, each in kJ. Show that the heat transfer equals the
ume, specific internal energy, and specific enthalpy for water change in enthalpy of the water in this case.
at 20C from the saturated liquid state to the state where the
pressure is 300 bar. Based on the resulting plots, discuss the 3.40 A two-phase liquidvapor mixture of H2O with an initial
implications regarding approximating compressed liquid prop- quality of 25% is contained in a pistoncylinder assembly as
erties using saturated liquid properties at 20C, as discussed in shown in Fig. P3.40. The mass of the piston is 40 kg, and its
Sec. 3.3.6. diameter is 10 cm. The atmospheric pressure of the surround-
ings is 1 bar. The initial and final positions of the piston are
3.30 Evaluate the specific volume, in m3/kg, and the specific shown on the diagram. As the water is heated, the pressure
enthalpy, in kJ/kg, of ammonia at 20C and 1.0 MPa. inside the cylinder remains constant until the piston hits the
3.31 Evaluate the specific volume, in m3/kg, and the specific stops. Heat transfer to the water continues until its pressure is
enthalpy, in kJ/kg, of propane at 800 kPa and 0C.
patm = 100 kPa
Applying the Energy Balance
3.32 A closed, rigid tank contains 2 kg of water initially at 80C
and a quality of 0.6. Heat transfer occurs until the tank con-
tains only saturated vapor. Kinetic and potential energy effects
are negligible. For the water as the system, determine the
amount of energy transfer by heat, in kJ.
3.33 A two-phase liquidvapor mixture of H2O, initially at 4.5 cm
1.0 MPa with a quality of 90%, is contained in a rigid, well-
insulated tank. The mass of H2O is 2 kg. An electric resistance 1 cm
heater in the tank transfers energy to the water at a constant
rate of 60 W for 1.95 h. Determine the final temperature of the
water in the tank, in C. Q
3.34 Refrigerant 134a vapor in a pistoncylinder assembly un- Diameter = 10 cm Initial quality
dergoes a constant-pressure process from saturated vapor at Mass = 40 kg x1 = 25% Figure P3.40
3 bar. Friction between the piston and the cylinder wall is neg- transfer coefficient. At the initial time, t 0, the tank and
ligible. Determine the total amount of heat transfer, in J. Let its contents are at the temperature of the surroundings.
g 9.81 m/s2. Obtain a differential equation for temperature T in terms of
3.41 Two kilograms of Refrigerant 134a, initially at 2 bar and time t and relevant parameters. Solve the differential equa-
occupying a volume of 0.12 m3, undergoes a process at con- tion to obtain T(t).
stant pressure until the volume has doubled. Kinetic and po-
tential energy effects are negligible. Determine the work and Using Generalized Compressibility Data
heat transfer for the process, each in kJ.
3.48 Determine the compressibility factor for water vapor at
3.42 Propane is compressed in a pistoncylinder assembly from 200 bar and 470C, using
saturated vapor at 40C to a final state where p2 6 bar and
T2 80C. During the process, the pressure and specific vol- (a) data from the compressibility chart.
ume are related by pvn constant. Neglecting kinetic and po- (b) data from the steam tables.
tential energy effects, determine the work and heat transfer per 3.49 Determine the volume, in m3, occupied by 40 kg of
unit mass of propane, each in kJ/kg. nitrogen (N2) at 17 MPa, 180 K.
3.43 A system consisting of 2 kg of ammonia undergoes a cy- 3.50 A rigid tank contains 0.5 kg of oxygen (O2) initially at
cle composed of the following processes: 30 bar and 200 K. The gas is cooled and the pressure drops to
20 bar. Determine the volume of the tank, in m3, and the final
Process 12: constant volume from p1 10 bar, x1 0.6 to
temperature, in K.
saturated vapor
3.51 Five kg of butane (C4H10) in a pistoncylinder assembly
Process 23: constant temperature to p3 p1, Q23
228 kJ
undergo a process from p1 5 MPa, T1 500 K to p2 3
Process 31: constant pressure MPa, T2 450 K during which the relationship between pres-
sure and specific volume is pvn constant. Determine the
Sketch the cycle on pv and Tv diagrams. Neglecting kinetic work, in kJ.
and potential energy effects, determine the net work for the
cycle and the heat transfer for each process, all in kJ.
3.44 A system consisting of 1 kg of H2O undergoes a power Working with the Ideal Gas Model
cycle composed of the following processes: 3.52 A tank contains 0.05 m3 of nitrogen (N2) at 21C and
10 MPa. Determine the mass of nitrogen, in kg, using
Process 12: Constant-pressure heating at 10 bar from satu-
rated vapor. (a) the ideal gas model.
(b) data from the compressibility chart.
Process 23: Constant-volume cooling to p3 5 bar, T3 160C.
Comment on the applicability of the ideal gas model for
Process 34: Isothermal compression with Q34 815.8 kJ. nitrogen at this state.
Process 41: Constant-volume heating. 3.53 Show that water vapor can be accurately modeled as an
ideal gas at temperatures below about 60C.
Sketch the cycle on Tv and pv diagrams. Neglecting kinetic
and potential energy effects, determine the thermal efficiency. 3.54 For what ranges of pressure and temperature can air be
considered an ideal gas? Explain your reasoning.
3.45 A well-insulated copper tank of mass 13 kg contains 4 kg
of liquid water. Initially, the temperature of the copper is 27C 3.55 Check the applicability of the ideal gas model for Refrig-
and the temperature of the water is 50C. An electrical resis- erant 134a at a temperature of 80C and a pressure of
tor of neglible mass transfers 100 kJ of energy to the contents (a) 1.6 MPa.
of the tank. The tank and its contents come to equilibrium. (b) 0.10 MPa.
What is the final temperature, in C?
3.56 Determine the temperature, in K, of oxygen (O2) at 250 bar
3.46 An isolated system consists of a 10-kg copper slab, ini- and a specific volume of 0.003 m3/kg using generalized com-
tially at 30C, and 0.2 kg of saturated water vapor, initially at pressibility data and compare with the value obtained using the
130C. Assuming no volume change, determine the final equi- ideal gas model.
librium temperature of the isolated system, in C.
3.57 Determine the temperature, in K, of 5 kg of air at a pres-
3.47 A system consists of a liquid, considered incompress- sure of 0.3 MPa and a volume of 2.2 m3. Verify that ideal gas
ible with constant specific heat c, filling a rigid tank whose behavior can be assumed for air under these conditions.
surface area is A. Energy transfer by work from a paddle
wheel to the liquid occurs at a constant rate. Energy transfer 3.58 Compare the densities, in kg/m3, of helium and air, each
# at 300 K, 100 kPa. Assume ideal gas behavior.
by heat occurs at a rate given by Q hA (T T0), where
T is the instantaneous temperature of the liquid, T0 is the 3.59 Assuming ideal gas behavior for air, plot to scale the
temperature of the surroundings, and h is an overall heat isotherms 300, 500, 1000, and 2000 K on a pv diagram.
3.60 By integrating cp(T ) obtained from Table A-21, determine of the gas in this temperature interval based on the measured
the change in specific enthalpy, in kJ/kg, of methane (CH4) data.
from T1 320 K, p1 2 bar to T2 800 K, p2 10 bar. 3.66 A gas is confined to one side of a rigid, insulated
Check your result using IT. container divided by a partition. The other side is initially
3.61 Show that the specific heat ratio of a monatomic ideal gas evacuated. The following data are known for the initial
is equal to 53. state of the gas: p1 5 bar, T1 500 K, and V1 0.2 m3.
When the partition is removed, the gas expands to fill the
entire container, which has a total volume of 0.5 m3. As-
Using the Energy Balance with the Ideal Gas Model suming ideal gas behavior, determine the final pressure, in
3.62 One kilogram of air, initially at 5 bar, 350 K, and 3 kg of bar.
carbon dioxide (CO2), initially at 2 bar, 450 K, are confined 3.67 A rigid tank initially contains 3 kg of air at 500 kPa, 290 K.
to opposite sides of a rigid, well-insulated container, as The tank is connected by a valve to a pistoncylinder assem-
illustrated in Fig. P3.62. The partition is free to move and bly oriented vertically and containing 0.05 m3 of air initially
allows conduction from one gas to the other without energy at 200 kPa, 290 K. Although the valve is closed, a slow leak
storage in the partition itself. The air and carbon dioxide each allows air to flow into the cylinder until the tank pressure falls
behave as ideal gases. Determine the final equilibrium tem- to 200 kPa. The weight of the piston and the pressure of the
perature, in K, and the final pressure, in bar, assuming constant atmosphere maintain a constant pressure of 200 kPa in the
specific heats. cylinder; and owing to heat transfer, the temperature stays con-
stant at 290 K. For the air, determine the total amount of en-
ergy transfer by work and by heat, each in kJ. Assume ideal
gas behavior.
Air CO2 3.68 A pistoncylinder assembly contains 1 kg of nitrogen gas
1 kg 3 kg (N2). The gas expands from an initial state where T1 700 K
5 bar 2 bar and p1 5 bar to a final state where p2 2 bar. During the
350 K 450 K
process the pressure and specific volume are related by pv1.3
constant. Assuming ideal gas behavior and neglecting kinetic
and potential energy effects, determine the heat transfer during
Partition Insulation Figure P3.62
the process, in kJ, using
(a) a constant specific heat evaluated at 300 K.
3.63 Consider a gas mixture whose apparent molecular weight (b) a constant specific heat evaluated at 700 K.
is 33, initially at 3 bar and 300 K, and occupying a volume of (c) data from Table A-23.
0.1 m3. The gas undergoes an expansion during which the 3.69 Air is compressed adiabatically from p1 1 bar, T1
pressurevolume relation is pV1.3 constant and the energy 300 K to p2 15 bar, v2 0.1227 m3/kg. The air is then cooled
transfer by heat to the gas is 3.84 kJ. Assume the ideal gas at constant volume to T3 300 K. Assuming ideal gas be-
model with cv 0.6
(2.5 104)T, where T is in K and cv havior, and ignoring kinetic and potential energy effects, cal-
has units of kJ/kg # K. Neglecting kinetic and potential energy culate the work for the first process and the heat transfer for
effects, determine the second process, each in kJ per kg of air. Solve the problem
each of two ways:
(a) the final temperature, in K.
(b) the final pressure, in bar. (a) using data from Table A-22.
(c) the final volume, in m3. (b) using a constant specific heat evaluated at 300 K.
(d) the work, in kJ. 3.70 A system consists of 2 kg of carbon dioxide gas initially at
3.64 Helium (He) gas initially at 2 bar, 200 K undergoes a poly- state 1, where p1 1 bar, T1 300 K. The system undergoes
tropic process, with n k, to a final pressure of 14 bar. De- a power cycle consisting of the following processes:
termine the work and heat transfer for the process, each in kJ
per kg of helium. Assume ideal gas behavior. Process 12: constant volume to p2, p2 p1
3.65 Two kilograms of a gas with molecular weight 28 are Process 23: expansion with pv1.28 constant
contained in a closed, rigid tank fitted with an electric resistor. Process 31: constant-pressure compression
The resistor draws a constant current of 10 amp at a voltage
of 12 V for 10 min. Measurements indicate that when equi- Assuming the ideal gas model and neglecting kinetic and
librium is reached, the temperature of the gas has increased by potential energy effects,
40.3C. Heat transfer to the surroundings is estimated to occur (a) sketch the cycle on a pv diagram.
at a constant rate of 20 W. Assuming ideal gas behavior, de- (b) plot the thermal efficiency versus p2p1 ranging from 1.05
termine an average value of the specific heat cp, in kJ/kg # K, to 4.
3.71 A closed system consists of an ideal gas with mass m and 3.72 Steam, initially at 5 MPa, 280C undergoes a polytropic
constant specific heat ratio k. If kinetic and potential energy process in a pistoncylinder assembly to a final pressure of
changes are negligible, 20 MPa. Plot the heat transfer, in kJ per kg of steam, for
(a) show that for any adiabatic process the work is polytropic exponents ranging from 1.0 to 1.6. Also investigate
the error in the heat transfer introduced by assuming ideal gas
mR1T2 T1 2 behavior for the steam. Discuss.
W
1k
(b) show that an adiabatic polytropic process in which work
is done only at a moving boundary is described by pVk
constant.
3.1D This chapter has focused on simple compressible sys- region. What features of the phase behavior of solids are im-
tems in which magnetic effects are negligible. In a report, portant in the fields of metallurgy and materials processing?
describe the thermodynamic characteristics of simple mag- Discuss.
netic systems, and discuss practical applications of this type 3.7D Devise an experiment to visualize the sequence of
of system. events as a two-phase liquidvapor mixture is heated at con-
3.2D The Montreal Protocols aim to eliminate the use of vari- stant volume near its critical point. What will be observed
ous compounds believed to deplete the earths stratospheric regarding the meniscus separating the two phases when the
ozone. What are some of the main features of these agreements, average specific volume is less than the critical specific
what compounds are targeted, and what progress has been volume? Greater than the critical specific volume? What
made to date in implementing the Protocols? happens to the meniscus in the vicinity of the critical point?
3.3D Frazil ice forming upsteam of a hydroelectric plant can Discuss.
block the flow of water to the turbine. Write a report summa- 3.8D One method of modeling gas behavior from the micro-
rizing the mechanism of frazil ice formation and alternative scopic viewpoint is known as the kinetic theory of gases. Using
means for eliminating frazil ice blockage of power plants. For kinetic theory, derive the ideal gas equation of state and ex-
one of the alternatives, estimate the cost of maintaining a plain the variation of the ideal gas specific heat cv with tem-
30-MW power plant frazil icefree. perature. Is the use of kinetic theory limited to ideal gas
3.4D Much has been written about the use of hydrogen as a behavior? Discuss.
fuel. Investigate the issues surrounding the so-called hydrogen 3.9D Many new substances have been considered in recent
economy and write a report. Consider possible uses of hydro- years as potential working fluids for power plants or refriger-
gen and the obstacles to be overcome before hydrogen could ation systems and heat pumps. What thermodynamic property
be used as a primary fuel source. data are needed to assess the feasibility of a candidate sub-
3.5D A major reason for the introduction of CFC (chlorofluo- stance for possible use as a working fluid? Write a paper
rocarbon) refrigerants, such as Refrigerant 12, in the 1930s was discussing your findings.
that they are less toxic than ammonia, which was widely used 3.10D A system is being designed that would continuously feed
at the time. But in recent years, CFCs largely have been phased steel (AISI 1010) rods of 0.1 m diameter into a gas-fired fur-
out owing to concerns about depletion of the earths stratos- nace for heat treating by forced convection from gases at
pheric ozone. As a result, there has been a resurgence of in- 1200 K. To assist in determining the feed rate, estimate the time,
terest in ammonia as a refrigerant, as well as increased interest in min, the rods would have to remain in the furnace to achieve
in natural refrigerants, such as propane. Write a report outlin- a temperature of 800 K from an initial temperature of 300 K.
ing advantages and disadvantages of ammonia and natural re- 3.11D Natural RefrigerantsBack to the Future (see box
frigerants. Consider safety issues and include a summary of Sec. 3.3). Although used for home appliances in Europe, hy-
any special design requirements that these refrigerants impose drocarbon refrigerants have not taken hold in the United States
on refrigeration system components. thus far owing to concerns about liability if there is an acci-
3.6D Metallurgists use phase diagrams to study allotropic dent. Research hydrocarbon refrigerant safety. Write a report
transformations, which are phase transitions within the solid including at least three references.
C
H
A
P
T
Control Volume
Analysis Using
E
R 4
Energy
E N G I N E E R I N G C O N T E X T The objective of this chapter is to chapter objective
develop and illustrate the use of the control volume forms of the conservation of mass and
conservation of energy principles. Mass and energy balances for control volumes are
introduced in Secs. 4.1 and 4.2, respectively. These balances are applied in Sec. 4.3 to
control volumes at steady state and in Sec. 4.4 for transient applications.
Although devices such as turbines, pumps, and compressors through which mass flows
can be analyzed in principle by studying a particular quantity of matter (a closed system)
as it passes through the device, it is normally preferable to think of a region of space
through which mass flows (a control volume). As in the case of a closed system, energy
transfer across the boundary of a control volume can occur by means of work and heat. In
addition, another type of energy transfer must be accounted forthe energy accompany-
ing mass as it enters or exits.

4.1 Conservation of Mass for a
Control Volume
In this section an expression of the conservation of mass principle for control volumes is
developed and illustrated. As a part of the presentation, the one-dimensional flow model is
introduced.
4.1.1 Developing the Mass Rate Balance

The mass rate balance for control volumes is introduced by reference to Fig. 4.1, which shows
a control volume with mass flowing in at i and flowing out at e, respectively. When applied
to such a control volume, the conservation of mass principle states conservation of mass
time rate of change of time rate of flow time rate of flow
mass contained within of mass in across of mass out across
the control volume at time t inlet i at time t exit e at time t
Denoting the mass contained within the control volume at time t by mcv(t), this statement
of the conservation of mass principle can be expressed in symbols as
dmcv # #
mi me (4.1)
dt
121
122 Chapter 4 Control Volume Analysis Using Energy
Dashed line defines

the control volume
boundary
Inlet i
Exit e
Figure 4.1 One-inlet, one-exit control volume.
# #
where dmcvdt is the time rate of change of mass within the control volume, and mi and me
mass flow rates are
# the instantaneous
# mass flow rates at the inlet and exit, respectively. As for the symbols
# #
W and Q, the dots in the quantities mi and me denote time rates of transfer. In SI, all terms
in Eq. 4.1 are expressed in kg/s. For a discussion of the development of Eq. 4.1, see box.
In general, there may be several locations on the boundary through which mass enters or
exits. This can be accounted for by summing, as follows
mass rate balance dmcv # #

a mi a me (4.2)
dt i e
Equation 4.2 is the mass rate balance for control volumes with several inlets and exits.
It is a form of the conservation of mass principle commonly employed in engineering. Other
forms of the mass rate balance are considered in discussions to follow.
DEVELOPING THE CONTROL VOLUME

MASS BALANCE
For each of the extensive properties mass, energy, and entropy (Chap. 6), the control
Dashed line volume form of the property balance can be obtained by transforming the correspon-
defines the
control volume
ding closed system form. Let us consider this for mass, recalling that the mass of a
boundary closed system is constant.
mi
mcv(t) The figures in the margin show a system consisting of a fixed quantity of matter m
that occupies different regions at time t and a later time t
t. The mass under
Region i consideration is shown in color on the figures. At time t, the mass is the sum m
Time t mcv(t)
mi, where mcv(t) is the mass contained within the control volume, and mi is
the mass within the small region labeled i adjacent to the control volume. Let us study
the fixed quantity of matter m as time elapses.
mcv(t + t) In a time interval t all the mass in region i crosses the control volume bound-
me
ary, while some of the mass, call it me, initially contained within the control volume
Region e exits to fill the region labeled e adjacent to the control volume. Although the mass
Time t + t in regions i and e as well as in the control volume differ from time t to t
t, the
total amount of mass is constant. Accordingly
mcv 1t2
mi mcv 1t
t2
me (a)
or on rearrangement
mcv 1t
t2 mcv 1t2 mi me (b)
Equation (b) is an accounting balance for mass. It states that the change in mass of the
control volume during time interval t equals the amount of mass that enters less the
amount of mass that exits.
4.1 Conservation of Mass for a Control Volume 123
Equation (b) can be expressed on a time rate basis. First, divide by t to obtain
mcv 1t
t2 mcv 1t2 mi me
(c)
t t t
Then, in the limit as t goes to zero, Eq. (c) becomes Eq. 4.1, the instantaneous control
volume rate equation for mass
dmcv # #
mi me (4.1)
dt
where dmcvdt denotes the time rate of change of mass within the control volume, and
# #
mi and me are the inlet and exit mass flow rates, respectively, all at time t.
EVALUATING THE MASS FLOW RATE

#
An expression for the mass flow rate m of the matter entering or exiting a control volume
can be obtained in terms of local properties by considering a small quantity of matter flowing
with velocity V across an incremental area dA in a time interval t, as shown in Fig. 4.2. Vn t
Since the portion of the control volume boundary through which mass flows is not neces-
V t
sarily at rest, the velocity shown in the figure is understood to be the velocity relative to the Volume
of matter
area dA. The velocity can be resolved into components normal and tangent to the plane con-
taining dA. In the following development Vn denotes the component of the relative velocity
dA
normal to dA in the direction of flow. A
The volume of the matter crossing dA during the time interval t shown in Fig. 4.2
is an oblique cylinder with a volume equal to the product of the area of its base dA and Figure 4.2 Illustra-
its altitude Vn t. Multiplying by the density gives the amount of mass that crosses dA tion used to develop an
in time t expression for mass flow
rate in terms of local
amount of mass
crossing dA during r1Vn t2 dA
fluid properties.
the time interval t
Dividing both sides of this equation by t and taking the limit as t goes to zero, the in-
stantaneous mass flow rate across incremental area dA is
instantaneous rate
of mass flow rVn dA
across dA
When this is integrated over the area A through which mass passes, an expression for the
mass flow rate is obtained
#
m rV dA
A
n (4.3)
Equation 4.3 can be applied at the inlets and exits to account for the rates of mass flow into
and out of the control volume.
4.1.2 Forms of the Mass Rate Balance

The mass rate balance, Eq. 4.2, is a form that is important for control volume analysis. In
many cases, however, it is convenient to apply the mass balance in forms suited to particu-
lar objectives. Some alternative forms are considered in this section.
Area = A e
Air
V, T, v
Air compressor
Air
i
Figure 4.3 Figure

illustrating the one-dimensional
+
flow model.
ONE-DIMENSIONAL FLOW FORM
When a flowing stream of matter entering or exiting a control volume adheres to the fol-
one-dimensional flow lowing idealizations, the flow is said to be one-dimensional:
The flow is normal to the boundary at locations where mass enters or exits the control
volume.
All intensive properties, including velocity and density, are uniform with position (bulk
average values) over each inlet or exit area through which matter flows.
METHODOLOGY for example. . . Figure 4.3 illustrates the meaning of one-dimensional flow. The
UPDATE
area through which mass flows is denoted by A. The symbol V denotes a single value that
In subsequent control represents the velocity of the flowing air. Similarly T and v are single values that represent
volume analyses, we rou- the temperature and specific volume, respectively, of the flowing air.
tinely assume that the
idealizations of one-
dimensional flow are When the flow is one-dimensional, Eq. 4.3 for the mass flow rate becomes
appropriate. Accordingly
1one-dimensional flow2
the assumption of one- #
dimensional flow is not
m rAV (4.4a)
listed explicitly in solved
examples. or in terms of specific volume
# AV
m (4.4b)
v
When area is in m2, velocity is in m/s, and specific volume is in m3/kg, the mass flow rate
volumetric flow rate found from Eq. 4.4b is in kg/s, as can be verified. The product AV in Eqs. 4.4 is the volumetric
flow rate. The volumetric flow rate is expressed in units of m3/s.
Substituting Eq. 4.4b into Eq. 4.2 results in an expression for the conservation of mass
principle for control volumes limited to the case of one-dimensional flow at the inlet and
exits
dmcv AiVi AeVe
a a (4.5)
dt i vi e ve
Note that Eq. 4.5 involves summations over the inlets and exits of the control volume. Each
individual term in either of these sums applies to a particular inlet or exit. The area, veloc-
ity, and specific volume appearing in a term refer only to the corresponding inlet or exit.
STEADY-STATE FORM
Many engineering systems can be idealized as being at steady state, meaning that all steady state
properties are unchanging in time. For a control volume at steady state, the identity of the
matter within the control volume changes continuously, but the total amount present at any
instant remains constant, so dmcvdt 0 and Eq. 4.2 reduces to
# #
a mi a me (4.6)
i e
That is, the total incoming and outgoing rates of mass flow are equal.
Equality of total incoming and outgoing rates of mass flow does not necessarily mean that
a control volume is at steady state. Although the total amount of mass within the control vol-
ume at any instant would be constant, other properties such as temperature and pressure might
be varying with time. When a control volume is at steady state, every property is independ-
ent of time. Note that the steady-state assumption and the one-dimensional flow assumption
are independent idealizations. One does not imply the other.
INTEGRAL FORM
We consider next the mass rate balance expressed in terms of local properties. The total mass
contained within the control volume at an instant t can be related to the local density as
follows
mcv 1t2 r dV (4.7)

V
where the integration is over the volume at time t.

With Eqs. 4.3 and 4.7, the mass rate balance Eq. 4.2 can be written as
r dV a a rV dAb a a rV dAb
d
n n (4.8)
dt V i A i e A e
where the area integrals are over the areas through which mass enters and exits the control
volume, respectively. The product Vn appearing in this equation, known as the mass flux, mass flux
gives the time rate of mass flow per unit of area. To evaluate the terms of the right side of
Eq. 4.8 requires information about the variation of the mass flux over the flow areas. The
form of the conservation of mass principle given by Eq. 4.8 is usually considered in detail
in fluid mechanics.
EXAMPLES
The following example illustrates an application of the rate form of the mass balance to a
control volume at steady state. The control volume has two inlets and one exit.
EXAMPLE 4.1 Feedwater Heater at Steady State
A feedwater heater operating at steady state has two inlets and one exit. At inlet 1, water vapor enters at p1 7 bar, T1
200C with a mass flow rate of 40 kg/s. At inlet 2, liquid water at p2 7 bar, T2 40C enters through an area A2 25 cm2.
Saturated liquid at 7 bar exits at 3 with a volumetric flow rate of 0.06 m3/s. Determine the mass flow rates at inlet 2 and at
the exit, in kg/s, and the velocity at inlet 2, in m/s.
SOLUTION
Known: A stream of water vapor mixes with a liquid water stream to produce a saturated liquid stream at the exit. The states at
the inlets and exit are specified. Mass flow rate and volumetric flow rate data are given at one inlet and at the exit, respectively.
Find: Determine the mass flow rates at inlet 2 and at the exit, and the velocity V2.
2 1
T1 = 200 C
A2 = 25 cm2
T2 = 40 C
p1 = 7 bar Assumption: The control volume shown on the accompanying
m1 = 40 kg/s figure is at steady state.
p2 = 7 bar
3 Control volume
boundary
Saturated liquid
p3 = 7 bar
(AV)3 = 0.06 m3/s
Figure E4.1
#
Analysis: The principal relations to be employed are the mass rate balance (Eq. 4.2) and the expression m AVv (Eq. 4.4b).
At steady state the mass rate balance becomes
0
dmcv # # #
m1
m2 m3
dt
#
Solving for m2
# # #
m2 m3 m1
#
The mass flow rate m1 is given. The mass flow rate at the exit can be evaluated from the given volumetric flow rate
# 1AV2 3
m3
v3
where v3 is the specific volume at the exit. In writing this expression, one-dimensional flow is assumed. From Table A-3,
v3 1.108 103 m3/kg. Hence
# 0.06 m3/s
m3 54.15 kg /s
11.108 103 m3/kg2
The mass flow rate at inlet 2 is then
# # #
m2 m3 m1 54.15 40 14.15 kg /s
For one-dimensional flow at 2, m2 A2V2 v2, so
#
#
V2 m2v2 A2
State 2 is a compressed liquid. The specific volume at this state can be approximated by v2 vf 1T2 2 (Eq. 3.11). From Table A-2
at 40C, v2 1.0078 103 m3/kg. So
114.15 kg/s211.0078 103 m3/kg2 104 cm2
V2 ` ` 5.7 m/s
25 cm2 1 m2
At steady state the mass flow rate at the exit equals the sum of the mass flow rates at the inlets. It is left as an exercise to
show that the volumetric flow rate at the exit does not equal the sum of the volumetric flow rates at the inlets.
Example 4.2 illustrates an unsteady, or transient, application of the mass rate balance. In
this case, a barrel is filled with water.
EXAMPLE 4.2 Filling a Barrel with Water
Water flows into the top of an open barrel at a constant mass flow rate of 7 kg/s. Water exits through a pipe near the base
#
with a mass flow rate proportional to the height of liquid inside: me 1.4 L, where L is the instantaneous liquid height, in m.
The area of the base is 0.2 m2, and the density of water is 1000 kg/m3. If the barrel is initially empty, plot the variation of
liquid height with time and comment on the result.
SOLUTION
Known: Water enters and exits an initially empty barrel. The mass flow rate at the inlet is constant. At the exit, the mass
flow rate is proportional to the height of the liquid in the barrel.
Find: Plot the variation of liquid height with time and comment.
mi = 30 lb/s
Boundary of
Assumptions:
control volume
1. The control volume is defined by the dashed line on the accompanying
diagram.
2. The water density is constant.
L (ft)
A = 3 ft2 me = 9L lb/s
Figure E4.2a
Analysis: For the one-inlet, one-exit control volume, Eq. 4.2 reduces to
dmcv # #
mi me
dt
The mass of water contained within the barrel at time t is given by
mcv 1t2 rAL1t2
where is density, A is the area of the base, and L(t) is the instantaneous liquid height. Substituting this into the mass rate
balance together with the given mass flow rates
d 1rAL2
7 1.4L
dt
Since density and area are constant, this equation can be written as

a bL
dL 1.4 7
dt rA rA
which is a first-order, ordinary differential equation with constant coefficients. The solution is
1.4t
L 5
C exp a b
rA
where C is a constant of integration. The solution can be verified by substitution into the differential equation.
To evaluate C, use the initial condition: at t 0, L 0. Thus, C 5.0, and the solution can be written as
L 5.03 1 exp 11.4trA2 4
Substituting r 1000 kg/m and A 0.2 m results in
2 2
L 5 31 exp 10.007t2 4
This relation can be plotted by hand or using appropriate software. The result is
Height, m
0 20 40 60 80 100 120
Time, s
Figure E4.2b
From the graph, we see that initially the liquid height increases rapidly and then levels out. After about 100 s, the height
stays nearly constant with time. At this point, the rate of water flow into the barrel nearly equals the rate of flow out of the
barrel. L S 5.
Alternatively, this differential equation can be solved using Interactive Thermodynamics: IT. The differential equation can
be expressed as
der(L,t) + (1.4 * L)/(rho * A) = 7/(rho * A)

rho = 1000 // kg/m3
A = 0.2 // m2
where der(L,t) is dLdt, rho is density , and A is area. Using the Explore button, set the initial condition at L 0, and
sweep t from 0 to 200 in steps of 0.5. Then, the plot can be constructed using the Graph button.
4.2 Conservation of Energy for a

Control Volume
In this section, the rate form of the energy balance for control volumes is obtained. The
energy rate balance plays an important role in subsequent sections of this book.
4.2.1 Developing the Energy Rate Balance for a Control Volume

We begin by noting that the control volume form of the energy rate balance can be derived
by an approach closely paralleling that considered in the box of Sec. 4.1, where the control
volume mass rate balance is obtained by transforming the closed system form. The present
4.2 Conservation of Energy for a Control Volume 129
Energy transfers can occur

by heat and work
Q
W
Inlet i
Ve2
ue + ___ + gze
2
mi
Control me
volume
Vi2
ui + ___ + gzi Exit e
zi 2
ze
Dashed line defines
the control volume boundary
Figure 4.4 Figure used to develop Eq. 4.9.
development proceeds less formally by arguing that, like mass, energy is an extensive prop-
erty, so it too can be transferred into or out of a control volume as a result of mass cross-
ing the boundary. Since this is the principal difference between the closed system and con-
trol volume forms, the control volume energy rate balance can be obtained by modifying
the closed system energy rate balance to account for these energy transfers.
Accordingly, the conservation of energy principle applied to a control volume states:
time rate of change net rate at which net rate at which net rate of energy
of the energy energy is being energy is being transfer into the
D contained within T D transferred in T D transferred out T
D control volume T
the control volume at by heat transfer by work at accompanying
time t at time t time t mass flow
For the one-inlet one-exit control volume with one-dimensional flow shown in Fig. 4.4
the energy rate balance is
V2i V2e
Q W
mi aui

gzi b me aue

gze b
dEcv # # # #
(4.9)
dt 2 2
# #
where Ecv denotes the energy of the control volume at time t. The terms Q and W account,
respectively, for the net rate of energy transfer by heat and work across the boundary of
the control volume at t. The underlined terms account for the rates of transfer of internal,
kinetic, and potential energy of the entering and exiting streams. If there is no mass flow
in or out, the respective mass flow rates vanish and the underlined terms of Eq. 4.9 drop
out. The equation then reduces to the rate form of the energy balance for closed systems:
Eq. 2.37.
EVALUATING WORK FOR A CONTROL VOLUME
Next, we will place Eq. 4.9 in an alternative form that is more convenient for subsequent
# ap-
plications. This will be accomplished primarily by recasting the work term W, which
represents the net rate of energy transfer by work across all portions of the boundary of the
control volume.
Because work is always done on or by a control volume # where matter flows across the
boundary, it is convenient to separate the work term W into two contributions: One con-
tribution is the work associated with the fluid pressure as mass is introduced at inlets and
#
removed at exits. The other contribution, denoted by Wcv, includes all other work effects,
such as those associated with rotating shafts, displacement of the boundary, and electrical
effects.
Consider the work at an exit e associated with the pressure of the flowing matter. Re-
call from Eq. 2.13 that the rate of energy transfer by work can be expressed as the prod-
uct of a force and the velocity at the point of application of the force. Accordingly, the
rate at which work is done at the exit by the normal force (normal to the exit area in the
direction of flow) due to pressure is the product of the normal force, peAe, and the fluid
velocity, Ve. That is
time rate of energy transfer
by work from the control 1 peAe 2Ve (4.10)
volume at exit e
where pe is the pressure, Ae is the area, and Ve is the velocity at exit e, respectively. A sim-
ilar expression can be written for the rate of energy transfer by work into the control volume
at inlet i. #
With these considerations, the work term W of the energy rate equation, Eq. 4.9, can be
written as
W Wcv
1 peAe 2 Ve 1 piAi 2Vi
# #
(4.11)
where, in accordance with the sign convention for work, the term at the inlet has a negative
sign because energy is transferred into the control volume there. A positive sign precedes the
work term at the exit because energy is transferred out of the control volume there. With
#
AV mv from Eq. 4.4b, the above expression for work can be written as
W Wcv
me 1 peve 2 mi 1 pivi 2
# # # #
(4.12)
# #
where mi and me are the mass flow rates and vi and ve are the specific volumes evaluated at
# #
the inlet and exit, respectively. In Eq. 4.12, the terms mi( pivi) and me(peve) account for the
work associated with the pressure at # the inlet and exit, respectively. They are commonly
flow work referred to as flow work. The term Wcv accounts for all other energy transfers by work across
the boundary of the control volume.
4.2.2 Forms of the Control Volume Energy Rate Balance

Substituting Eq. 4.12 in Eq. 4.9 and collecting all terms referring to the inlet and the exit
into separate expressions, the following form of the control volume energy rate balance
results
V2i V2e
Qcv Wcv
mi aui
pivi

gzi b me aue
peve

gze b
dEcv # # # #
(4.13)
dt 2 2
#
The subscript cv has been added to Q to emphasize that this is the heat transfer rate over
the boundary (control surface) of the control volume.
The last two terms of Eq. 4.13 can be rewritten using the specific enthalpy h introduced
in Sec. 3.3.2. With h u
pv, the energy rate balance becomes
V2i V2e
Qcv Wcv
mi ahi

gzi b me ahe

gze b
dEcv # # # #
(4.14)
dt 2 2
The appearance of the sum u
pv in the control volume energy equation is the principal
reason for introducing enthalpy previously. It is brought in solely as a convenience: The al-
gebraic form of the energy rate balance is simplified by the use of enthalpy and, as we have
seen, enthalpy is normally tabulated along with other properties.
4.3 Analyzing Control Volumes at Steady State 131
In practice there may be several locations on the boundary through which mass enters or
exits. This can be accounted for by introducing summations as in the mass balance. Ac-
cordingly, the energy rate balance is
V2i V2e
Qcv Wcv
a mi ahi

gzi b a me ahe

gze b
dEcv # # # #
(4.15) energy rate balance
dt i 2 e 2
Equation 4.15 is an accounting balance for the energy of the control volume. It states that METHODOLOGY
UPDATE
the rate of energy increase or decrease within the control volume equals the difference be-
tween the rates of energy transfer in and out across the boundary. The mechanisms of en- Equation 4.15 is the most
ergy transfer are heat and work, as for closed systems, and the energy that accompanies the general form of the con-
servation of energy princi-
mass entering and exiting. ple for control volumes
used in this book. It serves
as the starting point for
OTHER FORMS applying the conservation
As for the case of the mass rate balance, the energy rate balance can be expressed in terms of energy principle to con-
trol volumes in problem
of local properties to obtain forms that are more generally applicable. Thus, the term Ecv(t), solving.
representing the total energy associated with the control volume at time t, can be written as
a volume integral
V2
Ecv 1t2 re dV r au

gzb dV (4.16)
V V 2
Similarly, the terms accounting for the energy transfers accompanying mass flow and flow
work at inlets and exits can be expressed as shown in the following form of the energy rate
balance
V2
re dV Qcv Wcv
a c ah

gzb rVn dA d
d # #
dt V i A 2 i
(4.17)
2
a c ah

gzb r Vn dA d
V
e A 2 e
Additional
# forms of the energy rate balance can be obtained by expressing the heat transfer
rate Q cv as the integral of the heat flux over the boundary of the control volume, and the work
#
Wcv in terms of normal and shear stresses at the moving portions of the boundary.
In principle, the change in the energy of a control volume over a time period can be
obtained by integration of the energy rate balance with respect to time. Such integrations re-
quire information about the time dependences of the work and heat transfer rates, the various
mass flow rates, and the states at which mass enters and leaves the control volume. Exam-
ples of this type of analysis are presented in Sec. 4.4. In Sec. 4.3 to follow, we consider forms
that the mass and energy rate balances take for control volumes at steady state, for these are
frequently used in practice.

4.3 Analyzing Control Volumes at
Steady State
In this section steady-state forms of the mass and energy rate balances are developed and
applied to a variety of cases of engineering interest. The steady-state forms obtained do not
apply to the transient startup or shutdown periods of operation of such devices, but only to
periods of steady operation. This situation is commonly encountered in engineering.
4.3.1 Steady-State Forms of the Mass and

Energy Rate Balances
For a control volume at steady state, the conditions of the mass within the control volume and
at the boundary do not vary with time. The mass flow rates and the rates of energy transfer
by heat and work are also constant with time. There can be no accumulation of mass within
the control volume, so dmcvdt 0 and the mass rate balance, Eq. 4.2, takes the form
# #
a mi a me (4.18)
i e
1mass rate in2 1mass rate out2
Furthermore, at steady state dEcvdt 0, so Eq. 4.15 can be written as
V2i V2e
0 Qcv Wcv
a mi ahi

gzi b a me ahe

gze b
# # # #
(4.19a)
i 2 e 2
Alternatively
V2i V2e
Qcv
a mi ahi

gzi b Wcv
a me ahe

gze b
# # # #
(4.19b)
i 2 e 2
1energy rate in2 1energy rate out2
Equation 4.18 asserts that at steady state the total rate at which mass enters the control vol-
ume equals the total rate at which mass exits. Similarly, Eqs. 4.19 assert that the total rate
at which energy is transferred into the control volume equals the total rate at which energy
is transferred out.
Many important applications involve one-inlet, one-exit control volumes at steady state.
It is instructive to apply the mass and energy rate balances to this special case. The mass rate
# #
balance reduces simply to m1 m 2. That is, the mass flow rate must be the same at the
#
exit, 2, as it is at the inlet, 1. The common mass flow rate is designated simply by m. Next,
applying the energy rate balance and factoring the mass flow rate gives
1V21 V22 2
0 Qcv Wcv
m c 1h1 h2 2

g1z1 z2 2 d
# # #
(4.20a)
2
Or, dividing by the mass flow rate
1V21 V22 2
# #
0 # #
1h1 h2 2

g1z1 z2 2
Qcv Wcv
(4.20b)
m m 2
The enthalpy, kinetic energy, and potential energy terms all appear in Eqs. 4.20 as diff-
erences between their values at the inlet and exit. This illustrates that the datums used to
assign values to specific enthalpy, velocity, and elevation
# cancel,
# provided the same ones are
used at the inlet and exit. In Eq. 4.20b, the ratios Qcvm and Wcvm are rates of energy transfer
# #
per unit mass flowing through the control volume.
The foregoing steady-state forms of the energy rate balance relate only energy transfer
quantities evaluated at the boundary of the control volume. No details concerning properties
within the control volume are required by, or can be determined with, these equations. When
applying the energy rate balance in any of its forms, it is necessary to use the same units for
all terms in the equation. For instance, every term in Eq. 4.20b must have a unit such as kJ/kg
or Btu/lb. Appropriate unit conversions are emphasized in examples to follow.
4.3.2 Modeling Control Volumes at Steady State

In this section, we provide the basis for subsequent applications by considering the modeling
of control volumes at steady state. In particular, several examples are given in Sec. 4.3.3 show-
ing the use of the principles of conservation of mass and energy, together with relationships
among properties for the analysis of control volumes at steady state. The examples are drawn
from applications of general interest to engineers and are chosen to illustrate points common
to all such analyses. Before studying them, it is recommended that you review the methodol-
ogy for problem solving outlined in Sec. 1.7.3. As problems become more complicated, the
use of a systematic problem-solving approach becomes increasingly important.
When the mass and energy rate balances are applied to a control volume, simplifications
are normally needed to make the analysis manageable. That is, the control volume of inter-
est is modeled by making assumptions. The careful and conscious step of listing assump-
tions is necessary in every engineering analysis. Therefore, an important part of this section
is devoted to considering various assumptions that are commonly made when applying the
conservation principles to different types of devices. As you study the examples presented in
Sec. 4.3.3, it is important to recognize the role played by careful assumption making in ar-
riving at solutions. In each case considered, steady-state operation is assumed. The flow is
regarded as one-dimensional at places where mass enters and exits the control volume. Also,
at each of these locations equilibrium property relations are assumed
# to apply.
In several of the examples to follow, the heat transfer term Qcv is set to zero in the energy
rate balance because it is small relative to other energy transfers across the boundary. This
may be the result of one or more of the following factors:
The outer surface of the control volume is well insulated.
The outer surface area is too small for there to be effective heat transfer.
The temperature difference between the control volume and its surroundings is so small
that the heat transfer can be ignored.
The gas or liquid passes through the control volume so quickly that there is not enough
time for significant heat transfer to occur.
#
The work term Wcv drops out of the energy rate balance when there are no rotating shafts, dis-
placements of the boundary, electrical effects, or other work mechanisms associated with the
control volume being considered. The kinetic and potential energies of the matter entering and
exiting the control volume are neglected when they are small relative to other energy transfers.
In practice, the properties of control volumes considered to be at steady state do vary with
time. The steady-state assumption would still apply, however, when properties fluctuate only
slightly about their averages, as for pressure in Fig. 4.5a. Steady state also might be assumed
in cases where periodic time variations are observed, as in Fig. 4.5b. For example, in
p p
pave pave
t t
(a) (b)
Figure 4.5 Pressure variations about an average. (a) Fluctuation. (b) Periodic.
Thermodynamics in the News... ES

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Smaller Can Be Better power plant the size of
UNIT
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Engineers are developing miniature systems for use where involves micromotors
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QU
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somewhat larger meso-scale systems can measure up to a few wearing fire-, chemi-
centimeters. cal-, or biological-protection suits might in the future be kept
Microelectromechanical systems (MEMS) combining elec- cool by tiny heat pumps imbedded in the suit material.
trical and mechanical features are now widely used for sens- Engineers report that size reductions cannot go on in-
ing and control. Medical applications of MEMS include minute definitely. As designers aim at smaller sizes, frictional
pressure sensors that monitor pressure within the balloon in- effects and uncontrolled heat transfers pose significant chal-
serted into a blood vessel during angioplasty. Air bags are trig- lenges. Fabrication of miniature systems is also demanding.
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reciprocating engines and compressors, the entering and exiting flows pulsate as valves open
and close. Other parameters also might be time varying. However, the steady-state assumption
can apply to control volumes enclosing these devices if the following are satisfied for each suc-
cessive period of operation: (1) There is no net change in the total energy and the total mass
within the control volume. (2) The time-averaged mass flow rates, heat transfer rates, work
rates, and properties of the substances crossing the control surface all remain constant.
4.3.3 Illustrations
In this section, we present brief discussions and examples illustrating the analysis of several
devices of interest in engineering, including nozzles and diffusers, turbines, compressors and
pumps, heat exchangers, and throttling devices. The discussions highlight some common ap-
plications of each device and the important modeling assumptions used in thermodynamic
analysis. The section also considers system integration, in which devices are combined to
form an overall system serving a particular purpose.
NOZZLES AND DIFFUSERS
nozzle A nozzle is a flow passage of varying cross-sectional area in which the velocity of a gas
or liquid increases in the direction of flow. In a diffuser, the gas or liquid decelerates in
diffuser
the direction of flow. Figure 4.6 shows a nozzle in which the cross-sectional area decreases
V2 > V1 V2 < V1
p2 < p1 p2 > p1
1 2
2 1
Figure 4.6 Illustration of a nozzle and a

Nozzle Diffuser diffuser.
Flow-straightening
screens
Acceleration
Deceleration
Test
section Diffuser Figure 4.7 Wind-tunnel test
Nozzle
facility.
in the direction of flow and a diffuser in which the walls of the flow passage diverge.
In Fig. 4.7, a nozzle and diffuser are combined in a wind-tunnel test facility. Nozzles and
diffusers for high-speed gas flows formed from a converging section followed by diverg-
ing section are studied in Sec. 9.13.
For nozzles and diffusers, the only work
# is flow work at locations where mass enters and
exits the control volume, so the term Wcv drops out of the energy rate equation for these de-
vices. The change in potential energy from inlet to exit is negligible under most conditions.
At steady state the mass and energy rate balances reduce, respectively, to
0
dmcv # #
m1 m2
dt
0
V12 V22
Qcv Wcv
m1 ah1

gz1 b m2 ah2

gz2 b
dEcv # # 0 # #
dt 2 2
where 1 denotes the inlet and 2 the exit. By combining these into a single expression and
dropping the potential energy change from inlet to exit
#
V21 V22
0 #
1h1 h2 2
a b
Qcv
(4.21)
m 2
#
where m is the mass flow rate. The term Qcv m representing heat transfer with the
# #
surroundings per unit of mass flowing through the nozzle or diffuser is often small enough
relative to the enthalpy and kinetic energy changes that it can be dropped, as in the next
example.
EXAMPLE 4.3 Calculating Exit Area of a Steam Nozzle
Steam enters a convergingdiverging nozzle operating at steady state with p1 40 bar, T1 400C, and a velocity of 10 m/s.
The steam flows through the nozzle with negligible heat transfer and no significant change in potential energy. At the exit,
p2 15 bar, and the velocity is 665 m/s. The mass flow rate is 2 kg/s. Determine the exit area of the nozzle, in m2.
SOLUTION
Known: Steam flows at steady state through a nozzle with known properties at the inlet and exit, a known mass flow rate,
and negligible effects of heat transfer and potential energy.
Find: Determine the exit area.

T 1
T1 = 400 C
m = 2 kg/s
Insulation
p = 40 bar
p2 = 15 bar 2
V2 = 665 m/s
p1 = 40 bar
T1 = 400 C p = 15 bar
V1 = 10 m/s
Control volume 2
1 boundary
v
Figure E4.3
Assumptions:
1. The control volume shown on the accompanying figure is at steady state.

#
2. Heat transfer is negligible and Wcv 0.
3. The change in potential energy from inlet to exit can be neglected.
#
Analysis: The exit area can be determined from the mass flow rate m and Eq. 4.4b, which can be arranged to read
#
mv2
A2
V2
To evaluate A2 from this equation requires the specific volume v2 at the exit, and this requires that the exit state be fixed.
The state at the exit is fixed by the values of two independent intensive properties. One is the pressure p2, which is known.
The other is the specific enthalpy h2, determined from the steady-state energy rate balance
V21 V22
0 Qcv Wcv
m ah1

gz1 b m ah2

gz2 b
# 0 # 0 # #
2 2
# #
where Qcv and Wcv are deleted by assumption 2. The change in specific potential energy drops out in accordance with as-
#
sumption 3 and m cancels, leaving
V21 V22
0 1h1 h2 2
a b
2
Solving for h2
V21 V22
h2 h1
a b
2
From Table A-4, h1 3213.6 kJ/kg. The velocities V1 and V2 are given. Inserting values and converting the units of the kinetic
energy terms to kJ/kg results in
1102 2 16652 2 m2
h2 3213.6 kJ/kg
c da b` ` ` 3 # `
1N 1 kJ
2 # 2
2 s 1 kg m /s 10 N m
3213.6 221.1 2992.5 kJ/kg
Finally, referring to Table A-4 at p2 15 bar with h2 2992.5 kJ/kg, the specific volume at the exit is v2 0.1627 m3/kg.
The exit area is then
12 kg/s210.1627 m3/ kg2
A2 4.89 104 m2
665 m/s
Although equilibrium property relations apply at the inlet and exit of the control volume, the intervening states of the steam
are not necessarily equilibrium states. Accordingly, the expansion through the nozzle is represented on the Tv diagram
as a dashed line.
Care must be taken in converting the units for specific kinetic energy to kJ/kg.

#
The area at the nozzle inlet can be found similarly, using A1 mv1 V1.
Figure 4.8 Schematic of an axial-

Stationary blades Rotating blades flow turbine.
TURBINES
A turbine is a device in which work is developed as a result of a gas or liquid passing through turbine
a set of blades attached to a shaft free to rotate. A schematic of an axial-flow steam or gas
turbine is shown in Fig. 4.8. Turbines are widely used in vapor power plants, gas turbine
power plants, and aircraft engines (Chaps. 8 and 9). In these applications, superheated steam
or a gas enters the turbine and expands to a lower exit pressure as work is developed. A hy-
draulic turbine installed in a dam is shown in Fig. 4.9. In this application, water falling through
the propeller causes the shaft to rotate and work is developed.
Water level
Water flow
Water level
Propeller
Figure 4.9 Hydraulic turbine

installed in a dam.
For a turbine at steady state the mass and energy rate balances reduce to give Eq. 4.20b.
When gases are under consideration, the potential energy change is typically negligible. With
a proper selection of the boundary of the control volume enclosing the turbine, the kinetic
energy change is usually small enough to be neglected. The only heat transfer between the
turbine and surroundings would be unavoidable heat transfer, and as illustrated in the next
example this is often small relative to the work and enthalpy terms.
EXAMPLE 4.4 Calculating Heat Transfer from a Steam Turbine
Steam enters a turbine operating at steady state with a mass flow rate of 4600 kg/h. The turbine develops a power output of
1000 kW. At the inlet, the pressure is 60 bar, the temperature is 400C, and the velocity is 10 m/s. At the exit, the pressure
is 0.1 bar, the quality is 0.9 (90%), and the velocity is 50 m/s. Calculate the rate of heat transfer between the turbine and sur-
roundings, in kW.
SOLUTION
Known: A steam turbine operates at steady state. The mass flow rate, power output, and states of the steam at the inlet and
exit are known.
Find: Calculate the rate of heat transfer.
1
T T1 = 400C
p = 60 bar
m 1 = 4600 kg/h
p1 = 60 bar
T1 = 400C
V1 = 10 m/s 1 Wcv = 1000 kW
p = 0.1 bar
2 2
p2 = 0.1 bar
x2 = 0.9 (90%) v
V2 = 50 m/s
Figure E4.4
Assumptions:

2. The change in potential energy from inlet to exit can be neglected.
Analysis: To calculate the heat transfer rate, begin with the one-inlet, one-exit form of the energy rate balance for a control
volume at steady state
V21 V22
0 Qcv Wcv
m ah1

gz1 b m ah2

gz2 b
# # # #
2 2
# #
where m is the mass flow rate. Solving for Qcv and dropping the potential energy change from inlet to exit
V22 V21
Qcv Wcv
m c 1h2 h1 2
a bd
# # #
2
To compare the magnitudes of the enthalpy and kinetic energy terms, and stress the unit conversions needed, each of these
terms is evaluated separately.
First, the specific enthalpy difference h2 h1 is found. Using Table A-4, h1 3177.2 kJ/kg. State 2 is a two-phase
liquidvapor mixture, so with data from Table A-3 and the given quality
h2 hf 2
x2 1hg2 hf 2 2
191.83
10.9212392.82 2345.4 kJ/kg
Hence
h2 h1 2345.4 3177.2 831.8 kJ/kg
Consider next the specific kinetic energy difference. Using the given values for the velocities
V22 V21 1502 2 1102 2 m2
a b c da 2b`
1N
` `
1 kJ
`
2 2 s 1 kg # m/s2 103 N # m
1.2 kJ/kg
#
Calculating Qcv from the above expression
Qcv 11000 kW2

a4600 b 1831.8
1.22 a b ` ` ` `
kg kJ 1h 1 kW
#
h kg 3600 s 1 kJ/s
61.3 kW
The magnitude of the change in specific kinetic energy from inlet to exit is much smaller than the specific enthalpy
change.
#
The negative value
# of Qcv means that there is heat transfer from the turbine to its surroundings, as would be expected. The
magnitude of Qcv is small relative to the power developed.
COMPRESSORS AND PUMPS
Compressors are devices in which work is done on a gas passing through them in order to compressor
raise the pressure. In pumps, the work input is used to change the state of a liquid passing
pump
through. A reciprocating compressor is shown in Fig. 4.10. Figure 4.11 gives schematic di-
agrams of three different rotating compressors: an axial-flow compressor, a centrifugal com-
pressor, and a Roots type.
The mass and energy rate balances reduce for compressors and pumps at steady state, as
for the case of turbines considered previously. For compressors, the changes in specific kinetic
and potential energies from inlet to exit are often small relative to the work done per unit of
mass passing through the device. Heat transfer with the surroundings is frequently a secondary
effect in both compressors and pumps.
The next two examples illustrate, respectively, the analysis of an air compressor and a
power washer. In each case the objective is to determine the power required to operate the
device.
Inlet
Outlet Figure 4.10 Reciprocating compressor.

Outlet
Rotor
Stator Impeller
Impeller
Inlet
Driveshaft
(a) (b)
Outlet
Inlet
(c)
Figure 4.11 Rotating compressors. (a) Axial flow. (b) Centrifugal. (c) Roots type.
EXAMPLE 4.5 Calculating Compressor Power
Air enters a compressor operating at steady state at a pressure of 1 bar, a temperature of 290 K, and a velocity of 6 m/s through
an inlet with an area of 0.1 m2. At the exit, the pressure is 7 bar, the temperature is 450 K, and the velocity is 2 m/s. Heat
transfer from the compressor to its surroundings occurs at a rate of 180 kJ/min. Employing the ideal gas model, calculate the
power input to the compressor, in kW.
SOLUTION
Known: An air compressor operates at steady state with known inlet and exit states and a known heat transfer rate.
Find: Calculate the power required by the compressor.
Assumptions:
Wcv = ?
1. The control volume shown on the accompanying
p1 = 1 bar
figure is at steady state. T1 = 290 K 1 Air 2 p2 = 7 bar
V1 = 6 m/s compressor T2 = 450 K
2. The change in potential energy from inlet to exit V2 = 2 m/s
can be neglected. A1 = 0.1m2
3. The ideal gas model applies for the air.

Q cv = 180 kJ/min
Figure E4.5
Analysis: To calculate the power input to the compressor, begin with the energy rate balance for the one-inlet, one-exit con-
trol volume at steady state:
V21 V22
0 Qcv Wcv
m ah1

gz1 b m ah2

gz2 b
# # # #
2 2
Solving
V21 V22
Wcv Qcv
m c 1h1 h2 2
a bd
# # #
2
The change in potential energy from inlet to exit drops out by assumption 2.
#
The mass flow rate m can be evaluated with given data at the inlet and the ideal gas equation of state.
# A1V1 A1V1p1 10.1 m2 216 m/s21105 N/m2 2
m 0.72 kg/s
1RM2T1
a b 1290
v1 8314 N # m
K2
28.97 kg # K
# from Table A-22. At 290 K, h1 290.16 kJ/kg. At 450 K, h2 451.8 kJ/kg.

The specific enthalpies h1 and h2 can be found
Substituting values into the expression for Wcv
Wcv a180 b` `
0.72 c 1290.16 451.82
# kJ 1 min kg kJ
min 60 s s kg
162 2 122 2 m2

a ba b` ` ` `d
1N 1 kJ
2 s2 1 kg # m/s2 103 N # m

0.72 1161.64
0.022
kJ kg kJ
3
s s kg
` ` 119.4 kW
kJ 1 kW
119.4
s 1 kJ/s
The applicability of the ideal gas model can be checked by reference to the generalized compressibility chart.
The contribution of the kinetic energy is negligible in this case. Also, the heat transfer rate is seen to be small relative to
the power input.
# #
In this example Qcv and Wcv have negative values, indicating that the direction of the heat transfer is from the compressor
and work is done on the air passing through the compressor. The magnitude of the power input to the compressor is
119.4 kW.
EXAMPLE 4.6 Power Washer
A power washer is being used to clean the siding of a house. Water enters at 20C, 1 atm, with a volumetric flow rate of
0.1 liter/s through a 2.5-cm-diameter hose. A jet of water exits at 23C, 1 atm, with a velocity of 50 m/s at an elevation
of 5 m. At steady state, the magnitude of the heat transfer rate from the power unit to the surroundings is 10% of the
power input. The water can be considered incompressible, and g 9.81 m/s2. Determine the power input to the motor,
in kW.
SOLUTION
Known: A power washer operates at steady state with known inlet and exit conditions. The heat transfer rate is known as a
percentage of the power input.
Find: Determine the power input.

p2 = 1 atm
T2 = 23C
V2 = 50 m/s
z2 = 5 m
2
Assumptions:
5m 1. A control volume enclosing the power unit

and the delivery hose is at steady state.
2. The water is modeled as incompressible.
p1 = 1 atm
T1 = 20C
(AV)1 = 0.1 liter/s
D1 = 2.5 cm
1 Hose
+

Figure E4.6
Analysis: To calculate the power input, begin with the one-inlet, one-exit form of the energy balance for a control volume
at steady state
V21 V22
0 Qcv Wcv
m c 1h1 h2 2
a b
g1z1 z2 2 d
# # #
2
Introducing Qcv 10.12Wcv, and solving for Wcv
# # #
# 1V21 V22 2
c 1h1 h2 2

g 1z1 z2 2 d
# m
Wcv
0.9 2
#
The mass flow rate m can be evaluated using the given volumetric flow rate and v vf (20C) 1.0018 103 m3/kg
from Table A-2, as follows
m 1AV2 1v
#
103 m3
10.1 L /s2 11.0018 103 m3/kg2 ` `
1L
0.1 kg/s
Dividing the given volumetric flow rate by the inlet area, the inlet velocity is V1 0.2 m /s.
The specific enthalpy term is evaluated using Eq. 3.20b, with p1 p2 1 atm and c 4.18 kJ/kg # K from Table A-19
h1 h2 c 1T1 T2 2
v1p1 p2 2
0
14.18 kJ/kg # K2 13 K2 12.54 kJ/kg

Evaluating the specific kinetic energy term
m 2
3 10.22 2 1502 2 4 a b
V21 V22
` ` ` ` 1.25 kJ/kg
s 1N 1 kJ

2 2 1 kg # m /s2 103 N # m
Finally, the specific potential energy term is
g1z1 z2 2 19.81 m /s2 210 52m ` ` ` 3 # ` 0.05 kJ/kg

1N 1 kJ
# 2
1 kg m /s 10 N m
Inserting values
10.1 kg/s2
3 112.542
11.252
10.052 4 a b ` `
# kJ 1 kW
Wcv
0.9 kg 1 kJ/s
Thus
#
Wcv 1.54 kW
where the minus sign indicates that power is provided to the washer.
#
Since power is required to operate the washer, Wcv is negative in# accord with our sign convention. The energy # transfer by
heat is# from the control volume to the surroundings, and thus Q is negative as well. Using the value of W cv found be-
low, Qcv 10.12Wcv 0.154 kW.
# cv
The power washer develops a high-velocity jet of water at the exit. The inlet velocity is small by comparison.
The power input to the washer is accounted for by heat transfer from the washer to the surroundings and the increases in
specific enthalpy, kinetic energy, and potential energy of the water as it is pumped through the power washer.
HEAT EXCHANGERS
Devices that transfer energy between fluids at different temperatures by heat transfer modes
such as discussed in Sec. 2.4.2 are called heat exchangers. One common type of heat ex- heat exchanger
changer is a vessel in which hot and cold streams are mixed directly as shown in Fig. 4.12a.
An open feedwater heater is an example of this type of device. Another common type of heat
(a) (b)
(c) (d)
Figure 4.12 Common heat exchanger types. (a) Direct contact heat
exchanger. (b) Tube-within-a-tube counterflow heat exchanger. (c) Tube-within-
a-tube parallel flow heat exchanger. (d ) Cross-flow heat exchanger.
exchanger is one in which a gas or liquid is separated from another gas or liquid by a wall
through which energy is conducted. These heat exchangers, known as recuperators, take many
different forms. Counterflow and parallel tube-within-a-tube configurations are shown in
Figs. 4.12b and 4.12c, respectively. Other configurations include cross-flow, as in automobile
radiators, and multiple-pass shell-and-tube condensers and evaporators. Figure 4.12d illus-
trates a cross-flow heat exchanger.
The only work interaction at the boundary of a control volume enclosing
# a heat exchanger
is flow work at the places where matter enters and exits, so the term Wcv of the energy rate
balance can be set to zero. Although high rates of energy transfer may be achieved from
stream to stream, the heat transfer from the outer surface of the heat exchanger to the sur-
roundings is often small enough to be neglected. In addition, the kinetic and potential ener-
gies of the flowing streams can often be ignored at the inlets and exits.
The next example illustrates how the mass and energy rate balances are applied to a con-
denser at steady state. Condensers are commonly found in power plants and refrigeration
systems.
EXAMPLE 4.7 Power Plant Condenser
Steam enters the condenser of a vapor power plant at 0.1 bar with a quality of 0.95 and condensate exits at 0.1 bar and 45C.
Cooling water enters the condenser in a separate stream as a liquid at 20C and exits as a liquid at 35C with no change in
pressure. Heat transfer from the outside of the condenser and changes in the kinetic and potential energies of the flowing
streams can be ignored. For steady-state operation, determine
(a) the ratio of the mass flow rate of the cooling water to the mass flow rate of the condensing stream.
(b) the rate of energy transfer from the condensing steam to the cooling water, in kJ per kg of steam passing through the
condenser.
SOLUTION
Known: Steam is condensed at steady state by interacting with a separate liquid water stream.
Find: Determine the ratio of the mass flow rate of the cooling water to the mass flow rate of the steam and the rate of energy
transfer from the steam to the cooling water.
Condensate Steam
0.1 bar 2 1 0.1 bar
45C x = 0.95
Cooling Cooling
water 3 4 water
20C 35C
Control volume for part (a) 0.1 bar
45.8C 1
2 1
Condensate Steam 2
4
3
v
Energy transfer to
cooling water
Control volume for part (b)
Figure E4.7
Assumptions:
1. Each of the two control volumes shown on the accompanying sketch is at steady-state.
#
2. There is no significant heat transfer between the overall condenser and its surroundings, and Wcv 0.
3. Changes in the kinetic and potential energies of the flowing streams from inlet to exit can be ignored.
4. At states 2, 3, and 4, h hf (T ) (see Eq. 3.14).
Analysis: The steam and the cooling water streams do not mix. Thus, the mass rate balances for each of the two streams re-
duce at steady state to give
# # # #
m1 m2 and m3 m4
# #
(a) The ratio of the mass flow rate of the cooling water to the mass flow rate of the condensing steam, m3m1, can be found
from the steady-state form of the energy rate balance applied to the overall condenser as follows:
V21 V23
0 Qcv Wcv
m1 ah1

gz1 b
m3 ah3

gz3 b
# # # #
2 2
V22 V24
m2 ah2

gz2 b m4 ah4

gz4 b
# #
2 2
The underlined terms drop out by assumptions 2 and 3. With these simplifications, together with the above mass flow rate
relations, the energy rate balance becomes simply
0 m1 1h1 h2 2
m3 1h3 h4 2
# #
Solving, we get
#
m3 h1 h2
#
m1 h4 h3
The specific enthalpy h1 can be determined using the given quality and data from Table A-3. From Table A-3 at 0.1 bar, hf
191.83 kJ/kg and hg 2584.7 kJ/kg, so
h1 191.83
0.9512584.7 191.832 2465.1 kJ/kg
Using assumption 4, the specific enthalpy at 2 is given by h2 hf (T2) 188.45 kJ/kg. Similarly, h3 hf (T3) and h4 hf (T4),
giving h4 h3 62.7 kJ/kg. Thus
#
m3 2465.1 188.45
# 36.3
m1 62.7
(b) For a control volume enclosing the steam side of the condenser only, the steady-state form of energy rate balance is
V21 V22
0 Qcv Wcv
m1 ah1

gz1 b m2 ah2

gz2 b
# # # #
2 2
# #
The underlined terms drop out by assumptions 2 and 3. Combining this equation with m1 m2, the following expression for
the rate of energy transfer between the condensing steam and the cooling water results:
Qcv m1 1h2 h1 2
# #
#
Dividing by the mass flow rate of the steam, m1, and inserting values
#
Qcv
# h2 h1 188.45 2465.1 2276.7 kJ/kg
m1
where the minus sign signifies that energy is transferred from the condensing steam to the cooling water.
Alternatively, (h4 h3) can be evaluated using the incompressible liquid model via Eq. 3.20b.
Depending on where the boundary of the control volume is located, two different formulations of the energy rate balance
are obtained. In part (a), both streams are included in the control# volume. Energy transfer between them occurs internally
# volume, so the term Qcv drops out of the energy rate balance. With the control
and not across the boundary of the control
volume of part (b), however, the term Qcv must be included.
Excessive temperatures in electronic components are avoided by providing appropriate

cooling, as illustrated in the next example.
EXAMPLE 4.8 Cooling Computer Components
The electronic components of a computer are cooled by air flowing through a fan mounted at the inlet of the electronics en-
closure. At steady state, air enters at 20C, 1 atm. For noise control, the velocity of the entering air cannot exceed 1.3 m/s.
For temperature control, the temperature of the air at the exit cannot exceed 32C. The electronic components and fan receive,
respectively, 80 W and 18 W of electric power. Determine the smallest fan inlet diameter, in cm, for which the limits on the
entering air velocity and exit air temperature are met.
SOLUTION
Known: The electronic components of a computer are cooled by air flowing through a fan mounted at the inlet of the elec-
tronics enclosure. Conditions are specified for the air at the inlet and exit. The power required by the electronics and the fan
are also specified.
Find: Determine for these conditions the smallest fan inlet diameter.
Electronic T2 32C Air out

components 2
Fan
1 Air in
T1 = 20C
p1 = 1 atm
V1 1.3 m/s
Figure E4.8
Assumptions:

#
2. Heat transfer from the outer surface of the electronics enclosure to the surroundings is negligible. Thus, Qcv 0.
3. Changes in kinetic and potential energies can be ignored.
4. Air is modeled as an ideal gas with cp 1.005 kJ/kg # K.
#
Analysis: The inlet area A1 can be determined from the mass flow rate m and Eq. 4.4b, which can be rearranged to read
#
mv1
A1
V1
The mass flow rate can be evaluated, in turn, from the steady-state energy rate balance
V 21 V 22
0 Qcv Wcv
m c 1h1 h2 2
a b
g1z1 z2 2 d
# # #
2
The underlined terms drop out by assumptions 2 and 3, leaving
0 Wcv
m 1h1 h2 2
# #
# #
where Wcv accounts for the total electric power provided to the electronic components and the fan: Wcv (80 W)
#
(18 W) 98 W. Solving for m, and using assumption 4 with Eq. 3.51 to evaluate (h1 h2)
1Wcv 2
#
#
m
cp 1T2 T1 2
Introducing this into the expression for A1 and using the ideal gas model to evaluate the specific volume v1
1Wcv 2
#
c da b
1 RT1
A1
V1 cp 1T2 T1 2 p1
From this expression we see that A1 increases when V1 and/or T2 decrease. Accordingly, since V1 1.3 m/s and T2 305 K
(32C), the inlet area must satisfy
a b 293 K
8314 N # m
` 3 ` ` `
1 98 W 1 kJ 1 J/s 28.97 kg # K
A1
1.01325 105 N/m2
a1.005 # b 1305 2932 K
1.3 m/s kJ 10 J 1 W
kg K
0.005 m2
Then, since A1 pD214
14210.005 m2 2 102 cm
D1 0.08 m ` `
B p 1m
D1 8 cm
For the specified conditions, the smallest fan inlet diameter is 8 cm.
Cooling air typically enters and exits electronic enclosures at low velocities, and thus kinetic energy effects are insignificant.
The applicability of the ideal gas model can be checked by reference to the generalized compressibility chart. Since the
temperature of the air increases by no more than 12C, the specific heat cp is nearly constant (Table A-20).
THROTTLING DEVICES
A significant reduction in pressure can be achieved simply by introducing a restriction into

a line through which a gas or liquid flows. This is commonly done by means of a partially
opened valve or a porous plug, as illustrated in Fig. 4.13.
For a control volume enclosing such a device, the mass and energy rate balances reduce
at steady state to
# #
0 m1 m2
V21 V22
0 Qcv Wcv
m1 ah1

gz1 b m2 ah2

gz2 b
# # 0 # #
2 2
Inlet Exit
Inlet Exit Porous plug
Partially open valve
Figure 4.13 Examples of throttling devices.
There is usually no significant heat transfer with the surroundings and the change in poten-
tial energy from inlet to exit is negligible. With these idealizations, the mass and energy rate
balances combine to give
V21 V22
h1
h2
2 2
Although velocities may be relatively high in the vicinity of the restriction, measurements
made upstream and downstream of the reduced flow area show in most cases that the change
in the specific kinetic energy of the gas or liquid between these locations can be neglected.
With this further simplification, the last equation reduces to
throttling process h1 h2 (4.22)
When the flow through a valve or other restriction is idealized in this way, the process is
called a throttling process.
An application of the throttling process occurs in vapor-compression refrigeration sys-
tems, where a valve is used to reduce the pressure of the refrigerant from the pressure at the
exit of the condenser to the lower pressure existing in the evaporator. We consider this fur-
ther in Chap. 10. The throttling process also plays a role in the JouleThomson expansion
throttling calorimeter considered in Chap. 11. Another application of the throttling process involves the throttling
calorimeter, which is a device for determining the quality of a two-phase liquidvapor mix-
ture. The throttling calorimeter is considered in the next example.
EXAMPLE 4.9 Measuring Steam Quality
A supply line carries a two-phase liquidvapor mixture of steam at 20 bars. A small fraction of the flow in the line is diverted
through a throttling calorimeter and exhausted to the atmosphere at 1 bar. The temperature of the exhaust steam is measured
as 120C. Determine the quality of the steam in the supply line.
SOLUTION
Known: Steam is diverted from a supply line through a throttling calorimeter and exhausted to the atmosphere.
Find: Determine the quality of the steam in the supply line.
Steam line, 20 bars p
Thermometer
1 1 p1 = 20 bars
Calorimeter
p2 = 1 bar
2 T2 = 120C
p2 = 1 bar
2 T2 = 120C
v
Figure E4.9
Assumptions:

2. The diverted steam undergoes a throttling process.
Analysis: For a throttling process, the energy and mass balances reduce to give h2 h1, which agrees with Eq. 4.22.
Thus, with state 2 fixed, the specific enthalpy in the supply line is known, and state 1 is fixed by the known values of p1
and h1.
As shown on the accompanying pv diagram, state 1 is in the two-phase liquidvapor region and state 2 is in the super-
heated vapor region. Thus
h2 h1 hf1
x1 1hg1 hf1 2
Solving for x1
h2 hf1
x1
hg1 hf1
From Table A-3 at 20 bars, hf1 908.79 kJ/kg and hg1 2799.5 kJ/kg. At 1 bar and 120C, h2 2766.6 kJ/kg from Table A-4.
Inserting values into the above expression, the quality in the line is x1 0.956 (95.6%).
For throttling calorimeters exhausting to the atmosphere, the quality in the line must be greater than about 94% to ensure
that the steam leaving the calorimeter is superheated.
SYSTEM INTEGRATION
Thus far, we have studied several types of components selected from those commonly seen
in practice. These components are usually encountered in combination, rather than individ-
ually. Engineers often must creatively combine components to achieve some overall objec-
tive, subject to constraints such as minimum total cost. This important engineering activity
is called system integration.
Many readers are already familiar with a particularly successful system integration: the
simple power plant shown in Fig. 4.14. This system consists of four components in series, a
turbine-generator, condenser, pump, and boiler. We consider such power plants in detail in
subsequent sections of the book. The example to follow provides another illustration. Many
more are considered in later sections and in end-of-chapter problems.
in
Q
Boiler
W p Pump Turbine W t
Condenser
out
Q Figure 4.14 Simple vapor power plant.

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EXAMPLE 4.10 Waste Heat Recovery System
An industrial process discharges gaseous combustion products at 478K, 1 bar with a mass flow rate of 69.78 kg/s. As shown
in Fig. E 4.10, a proposed system for utilizing the combustion products combines a heat-recovery steam generator with a tur-
bine. At steady state, combustion products exit the steam generator at 400K, 1 bar and a separate stream of water enters at
.275 MPa, 38.9C with a mass flow rate of 2.079 kg/s. At the exit of the turbine, the pressure is 0.07 bars and the quality is
93%. Heat transfer from the outer surfaces of the steam generator and turbine can be ignored, as can the changes in kinetic
and potential energies of the flowing streams. There is no significant pressure drop for the water flowing through the steam
generator. The combustion products can be modeled as air as an ideal gas.
(a) Determine the power developed by the turbine, in kJ/s.
(b) Determine the turbine inlet temperature, in C.
SOLUTION
Known: Steady-state operating data are provided for a system consisting of a heat-recovery steam generator and a turbine.
Find: Determine the power developed by the turbine and the turbine inlet temperature. Evaluate the annual value of the
power developed.
p1 = 1 bar
T1 = 478K
m1 = 69.78 kg/s 1
Assumptions:
1. The control volume shown on the accompany-

ing figure is at steady state.
2. Heat transfer is negligible, and changes in
Turbine
4 Power kinetic and potential energy can be ignored.
2 out
3. There is no pressure drop for water flowing
T2 = 400K Steam
p2 = 1 bar
through the steam generator.
generator
4. The combustion products are modeled as air as
5
an ideal gas.
3 p3 = .275 MPa p5 = .07 bars
T3 = 38.9C x5 = 93%
m3 = 2.08 kg/s Figure E4.10
Analysis:
(a) The power developed by the turbine is determined from a control volume enclosing both the steam generator and the tur-
bine. Since the gas and water streams do not mix, mass rate balances for each of the streams reduce, respectively, to give
# # # #
m1 m2, m3 m5
The steady-state form of the energy rate balance is
V 21 V 23
0 Qcv Wcv
m1 ah1

gz1 b
m3 ah3

gz3 b
# # # #
2 2
V 22 V 25
m2 ah2

gz2 b m5 ah5

gz5 b
# #
2 2
The underlined terms drop out by assumption 2. With these simplifications, together with the above mass flow rate relations,
the energy rate balance becomes
Wcv m1 1h1 h2 2
m3 1h3 h5 2
# # #
# #
where m1 69.78 kg/s, m3 2.08 kg/s
The specific enthalpies h1 and h2 can be found from Table A-22: At 478 K, h1 480.35 kJ/kg, and at 400 K, h2 400.98 kJ/kg.
At state 3, water is a liquid. Using Eq. 3.14 and saturated liquid data from Table A-2, h3 hf 1T3 2 162.9 kJ /kg. State 5 is a
two-phase liquidvapor mixture. With data from Table A-3 and the given quality
h5 161
0.9312571.72 1612 2403 kJ/kg
#
Substituting values into the expression for Wcv
Wcv 169.78 kg/s21480.3 400.982 kJ/kg

#

12.079 kg/s21162.9 24032 kJ/kg
876.8 kJ/s 876.8 kW
(b) To determine T4, it is necessary to fix the state at 4. This requires two independent property values. With assumption 3,
one of these properties is pressure, p4 0.275 MPa. The other is the specific enthalpy h4, which can be found from an en-
ergy rate balance for a control volume enclosing just the steam generator. Mass rate balances for each of the two streams give
# # # #
m1 m2 and m3 m4. With assumption 2 and these mass flow rate relations, the steady-state form of the energy rate balance
reduces to
0 m1 1h1 h2 2
m3 1h3 h4 2
# #
Solving for h4
#
h4 h3
# 1h1 h2 2
m1
m3

a b 1480.3 400.982
kJ 69.78 kJ
162.9
kg 2.079 kg
2825 kJ/kg
Interpolating in Table A-4 at p4 .275 MPa with h4, T4 180C.
Alternatively, to determine h4 a control volume enclosing just the turbine can be considered. This is left as an exercise.
The decision about implementing this solution to the problem of utilizing the hot combustion products discharged from
an industrial process would necessarily rest on the outcome of a detailed economic evaluation, including the cost of pur-
chasing and operating the steam generator, turbine, and auxiliary equipment.
transient
4.4 Transient Analysis
Many devices undergo periods of transient operation in which the state changes with time.
Examples include the startup or shutdown of turbines, compressors, and motors. Additional
examples are provided by vessels being filled or emptied, as considered in Example 4.2 and
in the discussion of Fig. 1.3. Because property values, work and heat transfer rates, and mass
flow rates may vary with time during transient operation, the steady-state assumption is not
appropriate when analyzing such cases. Special care must be exercised when applying the
mass and energy rate balances, as discussed next.
MASS BALANCE
First, we place the control volume mass balance in a form that is suitable for transient analy-
sis. We begin by integrating the mass rate balance, Eq. 4.2, from time 0 to a final time t.
That is
t t t
a b dt a a mi b dt a a m# b dt
dmcv #
e
0 dt 0 i 0 e
This takes the form

t t
mcv 1t2 mcv 102 a a mi dtb a a m# dtb
#
e
i 0 e 0
Introducing the following symbols for the underlined terms
amount of mass
t
mi 0
#
mi dt d
entering the control
volume through inlet i,
from time 0 to t
amount of mass
t
me 0
#
me dt d
exiting the control
volume through exit e,
from time 0 to t
the mass balance becomes
mcv 1t2 mcv 102 a mi a me (4.23)

i e
In words, Eq. 4.23 states that the change in the amount of mass contained in the control vol-
ume equals the difference between the total incoming and outgoing amounts of mass.
ENERGY BALANCE
Next, we integrate the energy rate balance, Eq. 4.15, ignoring the effects of kinetic and
potential energy. The result is
t t
Ucv 1t2 Ucv 102 Qcv Wcv
a a mi hi dtb a a m# h dtb
#
e e (4.24a)
i 0 e 0
where Qcv accounts for the net amount of energy transferred by heat into the control volume
and Wcv accounts for the net amount of energy transferred by work, except for flow work.
4.4 Transient Analysis 153
The integrals shown underlined in Eq. 4.24a account for the energy carried in at the inlets
and out at the exits.
For the special case where the states at the inlets and exits are constant with time, the re-
spective specific enthalpies, hi and he, would be constant, and the underlined terms of Eq. 4.24a
become
t t
0
#
m# dt h m
mihi dt hi
0
i i i
t t
m# h dt h m# dt h m
0
e e e
0
e e e
Equation 4.24a then takes the following special form
Ucv 1t2 Ucv 102 Qcv Wcv

a mihi a mehe (4.24b)
i e
Whether in the general form, Eq. 4.24a, or the special form, Eq. 4.24b, these equations ac-
count for the change in the amount of energy contained within the control volume as the dif-
ference between the total incoming and outgoing amounts of energy.
Another special case is when the intensive properties within the control volume are
uniform with position at each instant. Accordingly, the specific volume and the specific
internal energy are uniform throughout and can depend only on time, that is v(t) and u(t).
Thus
mcv 1t2 Vcv 1t2 v1t2

Ucv 1t2 mcv 1t2u1t2
(4.25)
When the control volume is comprised of different phases, the state of each phase would be
assumed uniform throughout.
The following examples provide illustrations of the transient analysis of control vol-
umes using the conservation of mass and energy principles. In each case considered, we
begin with the general forms of the mass and energy balances and reduce them to forms
suited for the case at hand, invoking the idealizations discussed in this section when
warranted.
The first example considers a vessel that is partially emptied as mass exits through a
valve.
EXAMPLE 4.11 Withdrawing Steam from a Tank at Constant Pressure
A tank having a volume of 0.85 m3 initially contains water as a two-phase liquidvapor mixture at 260C and a quality of
0.7. Saturated water vapor at 260C is slowly withdrawn through a pressure-regulating valve at the top of the tank as energy
is transferred by heat to maintain the pressure constant in the tank. This continues until the tank is filled with saturated vapor
at 260C. Determine the amount of heat transfer, in kJ. Neglect all kinetic and potential energy effects.
SOLUTION
Known: A tank initially holding a two-phase liquidvapor mixture is heated while saturated water vapor is slowly removed.
This continues at constant pressure until the tank is filled only with saturated vapor.
Find: Determine the amount of heat transfer.

Pressure
regulating valve
e e
T
Saturated water-
vapor removed,
1 2, e
260C while the tank
is heated
v Initial: two-phase Final: saturated vapor

liquid-vapor mixture
Figure E4.11
Assumptions:
1. The control volume is defined by the dashed line on the accompanying diagram.
#
2. For the control volume, Wcv 0 and kinetic and potential energy effects can be neglected.
3. At the exit the state remains constant.
4. The initial and final states of the mass within the vessel are equilibrium states.
Analysis: Since there is a single exit and no inlet, the mass rate balance takes the form
dmcv #
me
dt
With assumption 2, the energy rate balance reduces to
dUcv # #
Qcv mehe
dt
Combining the mass and energy rate balances results in
dUcv # dmcv
Qcv
he
dt dt
By assumption 3, the specific enthalpy at the exit is constant. Accordingly, integration of the last equation gives
Ucv Qcv
he mcv
Solving for the heat transfer Qcv
Qcv Ucv he mcv
or
Qcv 1m2u2 m1u1 2 he 1m2 m1 2
where m1 and m2 denote, respectively, the initial and final amounts of mass within the tank.
The terms u1 and m1 of the foregoing equation can be evaluated with property values from Table A-2 at 260C and the
given value for quality. Thus
u1 uf
x1 1ug uf 2
1128.4
10.7212599.0 1128.42 2157.8 kJ/kg
Also,
v1 vf
x1 1vg uf 2
1.2755 103
10.7210.04221 1.2755 103 2 29.93 103 m3/kg
Using the specific volume v1, the mass initially contained in the tank is
V 0.85 m3
m1 28.4 kg
v1 129.93 103 m3/kg2
The final state of the mass in the tank is saturated vapor at 260C, so Table A-2 gives
u2 ug 1260C2 2599.0 kJ/kg, v2 vg 1260C2 42.21 103 m3/kg
The mass contained within the tank at the end of the process is
V 0.85 m3
m2 20.14 kg
v2 42.21 103 m3/kg
Table A-2 also gives he hg 1260C2 2796.6 kJ/kg.

Substituting values into the expression for the heat transfer yields
Qcv 120.14212599.02 128.4212157.82 2796.6120.14 28.42

14,162 kJ
In this case, idealizations are made about the state of the vapor exiting and the initial and final states of the mass con-
tained within the tank.
This expression for Qcv could be obtained by applying Eq. 4.24b together with Eqs. 4.23 and 4.25
In the next two examples we consider cases where tanks are filled. In Example 4.12, an
initially evacuated tank is filled with steam as power is developed. In Example 4.13, a com-
pressor is used to store air in a tank.
EXAMPLE 4.12 Using Steam for Emergency Power Generation
Steam at a pressure of 15 bar and a temperature of 320C is contained in a large vessel. Connected to the vessel through a
valve is a turbine followed by a small initially evacuated tank with a volume of 0.6 m3. When emergency power is required,
the valve is opened and the tank fills with steam until the pressure is 15 bar. The temperature in the tank is then 400C. The
filling process takes place adiabatically and kinetic and potential energy effects are negligible. Determine the amount of work
developed by the turbine, in kJ.
SOLUTION
Known: Steam contained in a large vessel at a known state flows from the vessel through a turbine into a small tank of
known volume until a specified final condition is attained in the tank.
Find: Determine the work developed by the turbine.

Valve Control volume boundary
Steam at
15 bar, Turbine V=
320C 0.6 m3
Initially
evacuated
tank
Figure E4.12
Assumptions:
#
2. For the control volume, Qcv 0 and kinetic and potential energy effects are negligible.
3. The state of the steam within the large vessel remains constant. The final state of the steam in the smaller tank is an equi-
librium state.
4. The amount of mass stored within the turbine and the interconnecting piping at the end of the filling process is negligible.
Analysis: Since the control volume has a single inlet and no exits, the mass rate balance reduces to
dmcv #
mi
dt
The energy rate balance reduces with assumption 2 to
dUcv # #
Wcv
mi hi
dt
Combining the mass and energy rate balances gives
dUcv # dmcv
Wcv
hi
dt dt
Integrating
Ucv Wcv
hi mcv
In accordance with assumption 3, the specific enthalpy of the steam entering the control volume is constant at the value cor-
responding to the state in the large vessel.
Solving for Wcv
Wcv hi mcv Ucv
Ucv and mcv denote, respectively, the changes in internal energy and mass of the control volume. With assumption 4, these
terms can be identified with the small tank only.
Since the tank is initially evacuated, the terms Ucv and mcv reduce to the internal energy and mass within the tank at
the end of the process. That is
Ucv 1m2u2 2 1m1u1 2 ,

0 0
mcv m2 m1
where 1 and 2 denote the initial and final states within the tank, respectively.
Collecting results yields
Wcv m2 1hi u2 2 (1)

The mass within the tank at the end of the process can be evaluated from the known volume and the specific volume of
steam at 15 bar and 400C from Table A-4
V 0.6 m3
m2 2.96 kg
v2 10.203 m3/kg2
The specific internal energy of steam at 15 bar and 400C from Table A-4 is 2951.3 kJ/kg. Also, at 15 bar and 320C,
h1 3081.9 kJ/kg.
Substituting values into Eq. (1)
Wcv 2.96 kg13081.9 2951.32kJ/kg 386.6 kJ
In this case idealizations are made about the state of the steam entering the tank and the final state of the steam in the
tank. These idealizations make the transient analysis manageable.
A significant aspect of this example is the energy transfer into the control volume by flow work, incorporated in the pv
term of the specific enthalpy at the inlet.
If the turbine were removed and steam allowed to flow adiabatically into the small tank, the final steam temperature in
the tank would be 477C. This may be verified by setting Wcv to zero in Eq. (1) to obtain u2 hi, which with p2 15 bar
fixes the final state.
EXAMPLE 4.13 Storing Compressed Air in a Tank
An air compressor rapidly fills a .28m3 tank, initially containing air at 21C, 1 bar, with air drawn from the atmosphere at 21C,
1 bar. During filling, the relationship between the pressure and specific volume of the air in the tank is pv1.4 constant.
The ideal gas model applies for the air, and kinetic and potential energy effects are negligible. Plot the pressure, in atm,
and the temperature, in F, of the air within the tank, each versus the ratio mm1, where m1 is the initial mass in the tank and m is
the mass in the tank at time t 7 0. Also, plot the compressor work input, in kJ, versus mm1. Let mm1 vary from 1 to 3.
SOLUTION
Known: An air compressor rapidly fills a tank having a known volume. The initial state of the air in the tank and the state
of the entering air are known.
Find: Plot the pressure and temperature of the air within the tank, and plot the air compressor work input, each versus mm1
ranging from 1 to 3.
Air
i Ti = 21C
pi = 1 bar
Tank
Air compressor
V = .28 m3
T1 = 21C
p1 = 1 bar
pv1.4 = constant
+
Figure E4.13a
Assumptions:
#
2. Because the tank is filled rapidly, Qcv is ignored.
4. The state of the air entering the control volume remains constant.
5. The air stored within the air compressor and interconnecting pipes can be ignored.
6. The relationship between pressure and specific volume for the air in the tank is pv1.4 constant.
7. The ideal gas model applies for the air.
Analysis: The required plots are developed using Interactive Thermodynamics: IT. The IT program is based on the follow-
ing analysis. The pressure p in the tank at time t 7 0 is determined from
pv1.4 p1v1.4
1
where the corresponding specific volume v is obtained using the known tank volume V and the mass m in the tank at that
time. That is, v Vm. The specific volume of the air in the tank initially, v1, is calculated from the ideal gas equation of
state and the known initial temperature, T1, and pressure, p1. That is
a b 1294K2
8314 N # m
28.97 kg # K
` 5 ` .8437 m3/kg
RT1 1 bar
v1
p1 11 bar2 10 N/m2
Once the pressure p is known, the corresponding temperature T can be found from the ideal gas equation of state, T pvR.
To determine the work, begin with the mass rate balance for the single-inlet control volume
dmcv #
mi
dt
Then, with assumptions 2 and 3, the energy rate balance reduces to

dUcv # #
Wcv
mihi
dt
Combining the mass and energy rate balances and integrating using assumption 4 gives
Ucv Wcv
hi mcv
Denoting the work input to the compressor by Win Wcv and using assumption 5, this becomes
Win mu m1u1 1m m1 2hi (1)
where m1 is the initial amount of air in the tank, determined from
V .28 m3
m1 0.332 kg
v1 0.8437 m3/kg
As a sample calculation to validate the IT program below, consider the case m 0.664 kg, which corresponds to mm1 2.
The specific volume of the air in the tank at that time is
V 0.28 m3
v 0.422 m3/kg
m 0.664 kg
The corresponding pressure of the air is
v1 1.4 0.8437 m3/kg 1.4

p p1a b 11 bar2 a b
v 0.422 m3/kg
2.64 bars
and the corresponding temperature of the air is
12.64 bars21.422 m3/kg2 105 N/m2

` `
pv
T
1 bar
a b
R 8314 J
28.97 kg K
388K 1114.9C2
Evaluating u1, u, and hi at the appropriate temperatures from Table A-22, u1 209.8 kJ/kg, u 277.5 kJ/kg, hi 294.2
kJ/kg. Using Eq. (1), the required work input is
Win mu m1u1 1m m1 2hi
10.664 kg2 a277.5 b 10.332 kg2 a209.8 b 10.332 kg2 a294.2 b

kJ kJ kJ
kg kg kg
16.9 kJ
IT Program. Choosing SI units from the Units menu, and selecting Air from the Properties menu, the IT program for
solving the problem is
// Given data
p1 = 1 // bar
T1 = 21 // C
Ti = 21 // C
V = .28 // m3
n = 1.4
// Determine the pressure and temperature for t > 0

v1 = v_TP(Air, T1, p1)
v = V/m
p * v ^n = p1 * v1 ^n
v = v_TP(Air, T, p)
// Specify the mass and mass ratio r

v1 = V/m1
r = m/m1
r=2
// Calculate the work using Eq. (1)

Win = m * u m1 * u1 hi * (mm1)
u1 = u_T(Air, T1)
u = u_T(Air, T)
hi = h_T(Air, Ti)
Using the Solve button, obtain a solution for the sample case r mm1 2 considered above to validate the program. Good
agreement is obtained, as can be verified. Once the program is validated, use the Explore button to vary the ratio mm1 from
1 to 3 in steps of 0.01. Then, use the Graph button to construct the required plots. The results are:
5 400
350
4
300
3
p, bars
250
T, C
2 200
150
1
100
0 50
1 1.5 2 2.5 3 1 1.5 2 2.5 3
m/m1 m/m1
60
50
40
Win, kJ
30
20
10
0
1 1.5 2 2.5 3
m/m1
Figure E4.13b
We conclude from the first two plots that the pressure and temperature each increase as the tank fills. The work required to
fill the tank increases as well. These results are as expected.
This pressure-specific volume relationship is in accord with what might be measured. The relationship is also consistent
with the uniform state idealization, embodied by Eqs. 4.25.
The final example of transient analysis is an application with a well-stirred tank. Such
process equipment is commonly employed in the chemical and food processing industries.
EXAMPLE 4.14 Temperature Variation in a Well-Stirred Tank
A tank containing 45 kg of liquid water initially at 45C has one inlet and one exit with equal mass flow rates. Liquid water
enters at 45C and a mass flow rate of 270 kg/h. A cooling coil immersed in the water removes energy at a rate of 7.6 kW.
The water is well mixed by a paddle wheel so that the water temperature is uniform throughout. The power input to the water
from the paddle wheel is 0.6 kW. The pressures at the inlet and exit are equal and all kinetic and potential energy effects can
be ignored. Plot the variation of water temperature with time.
SOLUTION
Known: Liquid water flows into and out of a well-stirred tank with equal mass flow rates as the water in the tank is cooled
by a cooling coil.
Find: Plot the variation of water temperature with time.
Mixing m1 = 270 kg/h 318

rotor
Water temperature, K
Constant
liquid level
Tank
Boundary
Cooling coil 296
m2 = 270 kg/h 0 0.5 1.0

Time, h
Figure E4.14
Assumptions:
2. For the control volume, the only significant heat transfer is with the cooling coil. Kinetic and potential energy effects can
be neglected.
3. The water temperature is uniform with position throughout: T T(t).
4. The water in the tank is incompressible, and there is no change in pressure between inlet and exit.
Analysis: The energy rate balance reduces with assumption 2 to
Qcv Wcv
m 1h1 h2 2
dUcv # # #
dt
#
where m denotes the mass flow rate.
The mass contained within the control volume remains constant with time, so the term on the left side of the energy rate
balance can be expressed as
dUcv d1mcvu2 du
mcv
dt dt dt
Since the water is assumed incompressible, the specific internal energy depends on temperature only. Hence, the chain rule
can be used to write
du du dT dT
c
dt dT dt dt
where c is the specific heat. Collecting results
dUcv dT
mcvc
dt dt
With Eq. 3.20b the enthalpy term of the energy rate balance can be expressed as
h1 h2 c1T1 T2 2
v1p1 p2 2
0
where the pressure term is dropped by assumption 4. Since the water is well mixed, the temperature at the exit equals the tem-
perature of the overall quantity of liquid in the tank, so
h1 h2 c1T1 T 2
where T represents the uniform water temperature at time t.
With the foregoing considerations the energy rate balance becomes
Qcv Wcv
mc 1T1 T 2
dT # # #
mcvc
dt
As can be verified by direct substitution, the solution of this first-order, ordinary differential equation is
# # #
Qcv Wcv
T C1 exp a tb
a b
T1
m
#
mcv mc
The constant C1 is evaluated using the initial condition: at t 0, T T1. Finally
# # #
Qcv Wcv
T T1
a b c 1 exp a tb d
m
#
mc mcv
Substituting given numerical values together with the specific heat c for liquid water from Table A-19
37.6 10.62 4 kJ/s
c 1 exp a tb d
270
T 318 K
C 270 kg S
a b a4.2 # b
kJ 45
3600 s
318 22 3 1 exp16t2 4
kg K
where t is in hours. Using this expression, we can construct the accompanying plot showing the variation of temperature with time.
In this case idealizations are made about the state of the mass contained within the system and the states of the liquid en-
tering and exiting. These idealizations make the transient analysis manageable.
As t S , T S 296 K. That is, the water temperature approaches a constant value after sufficient time has elapsed. From
the accompanying plot it can be seen that the temperature reaches its constant limiting value in about 1 h.
The conservation of mass and energy principles for control has been completed you should be able to
volumes are embodied in the mass and energy rate balances
developed in this chapter. Although the primary emphasis write out the meanings of the terms listed in the margins
is on cases in which one-dimensional flow is assumed, mass throughout the chapter and understand each of the
and energy balances are also presented in integral forms that related concepts. The subset of key concepts listed below
provide a link to subsequent fluid mechanics and heat trans- is particularly important in subsequent chapters.
fer courses. Control volumes at steady state are featured, list the typical modeling assumptions for nozzles and
but discussions of transient cases are also provided. diffusers, turbines, compressors and pumps, heat
The use of mass and energy balances for control volumes at exchangers, and throttling devices.
steady state is illustrated for nozzles and diffusers, turbines, apply Eqs. 4.18 4.20 to control volumes at steady state,
compressors and pumps, heat exchangers, throttling devices, and using appropriate assumptions and property data for the
integrated systems. An essential aspect of all such applications case at hand.
is the careful and explicit listing of appropriate assumptions.
Such model-building skills are stressed throughout the chapter. apply mass and energy balances for the transient analysis
The following checklist provides a study guide for this chap- of control volumes, using appropriate assumptions and
ter. When your study of the text and end-of-chapter exercises property data for the case at hand.

mass flow rate p. 122 volumetric flow rate energy rate balance p. 131 compressor p. 139
mass rate balance p. 122 p. 124 nozzle p. 134 pump p. 139
one-dimensional flow steady state p. 125 diffuser p. 134 heat exchanger p. 143
p. 124 flow work p. 130 turbine p. 137 throttling process p. 148
1. Why does the relative velocity normal to the flow boundary, energy rate balances are important to describe steady-state
Vn, appear in Eqs. 4.3 and 4.8? operation?
2. Why might a computer cooled by a constant-speed fan oper- 9. When air enters a diffuser and decelerates, does its pressure
ate satisfactorily at sea level but overheat at high altitude? increase or decrease?
3. Give an example where the inlet and exit mass flow rates for 10. Even though their outer surfaces would seem hot to the touch,
a control volume are equal, yet the control volume is not at steady large steam turbines in power plants might not be covered with
state. much insulation. Why not?
#
4. Does Qcv accounting for energy transfer by heat include heat 11. Would it be desirable for a coolant circulating inside the
transfer across inlets and exits? Under what circumstances might engine of an automobile to have a large or a small specific heat
heat transfer across an inlet or exit be significant? cp? Discuss.
5. By introducing enthalpy h to replace each of the (u
pv) 12. A hot liquid stream enters a counterflow heat exchanger at
terms of Eq. 4.13, we get Eq. 4.14. An even simpler algebraic Th,in, and a cold liquid stream enters at Tc,in. Sketch the variation
form would result by replacing each of the (u
pv
V22
of temperature with location of each stream as it passes through
gz) terms by a single symbol, yet we have not done so. Why not? the heat exchanger.
6. Simplify the general forms of the mass and energy rate bal- 13. What are some examples of commonly encountered devices
ances to describe the process of blowing up a balloon. List all of that undergo periods of transient operation? For each example,
your modeling assumptions. which type of system, closed system or control volume, would
7. How do the general forms of the mass and energy rate bal- be most appropriate?
ances simplify to describe the exhaust stroke of a cylinder in an 14. An insulated rigid tank is initially evacuated. A valve is
automobile engine? List all of your modeling assumptions. opened and atmospheric air at 20C, 1 atm enters until the pres-
8. Waterwheels have been used since antiquity to develop me- sure in the tank becomes 1 bar, at which time the valve is closed.
chanical power from flowing water. Sketch an appropriate Is the final temperature of the air in the tank equal to, greater
control volume for a waterwheel. What terms in the mass and than, or less than 20C?
Applying Conservation of Mass in the amount of mass, in kg, in the control volume versus
4.1 The mass flow rate at the inlet of a one-inlet, one-exit con- time, in s, ranging from 0 to 3600 s.
trol volume varies with time according to mi 10011 e 2t 2,
#
4.3 A 0.5-m3 tank contains ammonia, initially at 40C, 8 bar.
#
where mi has units of kg/h and t is in h. At the exit, the mass A leak develops, and refrigerant flows out of the tank at a con-
flow rate is constant at 100 kg/h. The initial mass in the constant mass flow rate of 0.04 kg/s. The process occurs slowly
trol volume is 50 kg. enough that heat transfer from the surroundings maintains a
(a) Plot the inlet and exit mass flow rates, the instantaneous constant temperature in the tank. Determine the time, in s, at
rate of change of mass, and the amount of mass contained which half of the mass has leaked out, and the pressure in the
in the control volume as functions of time, for t ranging tank at that time, in bar.
from 0 to 3 h. 4.4 A water storage tank initially contains 400 m3 of water. The
(b) Estimate the time, in h, when the tank is nearly empty. average daily usage is 40 m3. If water is added to the tank at
4.2 A control volume has one inlet and one exit. The mass flow an average rate of 20[exp(t20)] m3 per day, where t is time
# # in days, for how many days will the tank contain water?
rates in and out are, respectively, mi 1.5 and me
2, where t is in seconds and m is in kg/s. Plot
0.002t #
1.511 e 4.5 A pipe carrying an incompressible liquid contains an
the time rate of change of mass, in kg/s, and the net change expansion chamber as illustrated in Fig. P4.5.
(a) Develop an expression for the time rate of change of liq- is 350 m/s. The air behaves as an ideal gas. For steady-state
uid level in the chamber, dLdt, in terms of the diameters operation, determine
D1, D2, and D, and the velocities V1 and V2. (a) the mass flow rate, in kg/s.
#
(b) Compare the relative magnitudes of the mass flow rates mi (b) the exit flow area, in cm2.
#
and m2 when dLdt 0, dLdt 0, and dLdt 0,
respectively. 4.9 Infiltration of outside air into a building through miscel-
laneous cracks around doors and windows can represent a
significant load on the heating equipment. On a day when the
outside temperature is 18C, 0.042 m3/s of air enters through
D the cracks of a particular office building. In addition, door
openings account for about .047 m3/s of outside air infiltration.
Expansion
The internal volume of the building is 566 m3, and the inside
chamber L temperature is 22C. There is negligible pressure difference
between the inside and the outside of the building. Assuming
ideal gas behavior, determine at steady state the volumetric
flow rate of air exiting the building through cracks and other
openings, and the number of times per hour that the air within
the building is changed due to infiltration.
V1 V2
4.10 Refrigerant 134a enters the condenser of a refrigeration
m1 m
2 system operating at steady state at 9 bar, 50C, through a
2.5-cm-diameter pipe. At the exit, the pressure is 9 bar, the
D1 temperature is 30C, and the velocity is 2.5 m/s. The mass flow
D2
rate of the entering refrigerant is 6 kg/min. Determine
Figure P4.5
(a) the velocity at the inlet, in m/s.
(b) the diameter of the exit pipe, in cm.
4.6 Velocity distributions for laminar and turbulent flow in a 4.11 Steam at 160 bar, 480C, enters a turbine operating at
circular pipe of radius R carrying an incompressible liquid of steady state with a volumetric flow rate of 800 m3/min. Eighteen
density are given, respectively, by percent of the entering mass flow exits at 5 bar, 240C, with a
velocity of 25 m/s. The rest exits at another location with
VV0 31 1rR2 2 4 a pressure of 0.06 bar, a quality of 94%, and a velocity of
VV0 31 1rR2 4 17 400 m/s. Determine the diameters of each exit duct, in m.
where r is the radial distance from the pipe centerline and V0 4.12 Air enters a compressor operating at steady state with a
is the centerline velocity. For each velocity distribution pressure of 1 bar, a temperature of 20C, and a volumetric flow
(a) plot VV0 versus rR. rate of 0.25 m3/s. The air velocity in the exit pipe is 210 m/s
(b) derive expressions for the mass flow rate and the average and the exit pressure is 1 MPa. If each unit mass of air passing
velocity of the flow, Vave, in terms of V0, R, and , as re- from inlet to exit undergoes a process described by pv1.34
quired. constant, determine the exit temperature, in C.
(c) derive an expression for the specific kinetic energy carried 4.13 Air enters a 0.6-m-diameter fan at 16C, 101 kPa, and is
through an area normal to the flow. What is the percent er- discharged at 18C, 105 kPa, with a volumetric flow rate of
ror if the specific kinetic energy is evaluated in terms of 0.35 m3/s. Assuming ideal gas behavior, determine for steady-
the average velocity as (Vave)22? state operation
Which velocity distribution adheres most closely to the ideal- (a) the mass flow rate of air, in kg/s.
izations of one-dimensional flow? Discuss. (b) the volumetric flow rate of air at the inlet, in m3/s.
4.7 Vegetable oil for cooking is dispensed from a cylindrical (c) the inlet and exit velocities, in m/s.
can fitted with a spray nozzle. According to the label, the can 4.14 Ammonia enters a control volume operating at steady state
is able to deliver 560 sprays, each of duration 0.25 s and each at p1 14 bar, T1 28C, with a mass flow rate of 0.5 kg/s.
having a mass of 0.25 g. Determine Saturated vapor at 4 bar leaves through one exit, with a volu-
(a) the mass flow rate of each spray, in g/s. metric flow rate of 1.036 m3/min, and saturated liquid at 4 bar
(b) the mass remaining in the can after 560 sprays, in g, if the leaves through a second exit. Determine
initial mass in the can is 170 g. (a) the minimum diameter of the inlet pipe, in cm, so the
4.8 Air enters a one-inlet, one-exit control volume at 8 bar, ammonia velocity does not exceed 20 m /s.
600 K, and 40 m/s through a flow area of 20 cm2. At the exit, (b) the volumetric flow rate of the second exit stream, in
the pressure is 2 bar, the temperature is 400 K, and the velocity m3/min.
4.15 At steady state, a stream of liquid water at 20C, 1 bar is (b) the diameters, in cm, of each of the supply pipes if the
mixed with a stream of ethylene glycol (M 62.07) to form velocity in each is 2.5 m/s.
a refrigerant mixture that is 50% glycol by mass. The water 4.16 Figure P4.16 shows a cooling tower operating at steady
molar flow rate is 4.2 kmol/min. The density of ethylene gly- state. Warm water from an air conditioning unit enters at 49C
col is 1.115 times that of water. Determine with a mass flow rate of 0.5 kg/s. Dry air enters the tower at
(a) the molar flow rate, in kmol/min, and volumetric flow rate, 21C, 1 atm with a volumetric flow rate of 1.41 m3/s. Be-
in m3/min, of the entering ethylene glycol. cause of evaporation within the tower, humid air exits at the
Humid air
m 4 = 1.64 kg/s
Cooling tower
4
Fan Warm water inlet Air conditioning unit
m 1 = 0.5 kg/s
1 T1 = 49C
Spray heads
Dry air
T3 = 21C
3 p3 = 1 bar
(AV)3 = 1.41 m3/s
Pump
2 Return water
Liquid +
T2 = 27C

m 2 = m 1
5 Makeup water
Figure P4.16
top of the tower with a mass flow rate of 1.64 kg/s. Cooled with a velocity of 460 m/s. Assuming ideal gas behavior and
liquid water is collected at the bottom of the tower for return neglecting potential energy effects, determine the heat transfer
to the air conditioning unit together with makeup water. per unit mass of air flowing, in kJ/kg.
Determine the mass flow rate of the makeup water, in kg/s.
4.21 Air enters an insulated diffuser operating at steady state
with a pressure of 1 bar, a temperature of 300 K, and a veloc-
Energy Analysis of Control Volumes at Steady State
ity of 250 m/s. At the exit, the pressure is 1.13 bar and the
4.17 Air enters a control volume operating at steady state at velocity is 140 m/s. Potential energy effects can be neglected.
1.05 bar, 300 K, with a volumetric flow rate of 12 m3/min and Using the ideal gas model, determine
exits at 12 bar, 400 K. Heat transfer occurs at a rate of 20 kW
from the control volume to the surroundings. Neglecting ki- (a) the ratio of the exit flow area to the inlet flow area.
netic and potential energy effects, determine the power, in kW. (b) the exit temperature, in K.
4.18 Steam enters a nozzle operating at steady state at 30 bar, 4.22 The inlet ducting to a jet engine forms a diffuser that
320C, with a velocity of 100 m/s. The exit pressure and tem- steadily decelerates the entering air to zero velocity relative to
perature are 10 bar and 200C, respectively. The mass flow rate the engine before the air enters the compressor. Consider a jet
is 2 kg/s. Neglecting heat transfer and potential energy, determine airplane flying at 1000 km/h where the local atmospheric pres-
(a) the exit velocity, in m/s. sure is 0.6 bar and the air temperature is 8C. Assuming ideal
(b) the inlet and exit flow areas, in cm2. gas behavior and neglecting heat transfer and potential energy
effects, determine the temperature, in C, of the air entering
4.19 Methane (CH4) gas enters a horizontal, well-insulated noz-
the compressor.
zle operating at steady state at 80C and a velocity of 10 m/s.
Assuming ideal gas behavior for the methane, plot the tem- 4.23 Refrigerant 134a enters an insulated diffuser as a saturated
perature of the gas exiting the nozzle, in C, versus the exit vapor at 7 bars with a velocity of 370 m/s. At the exit, the pres-
velocity ranging from 500 to 600 m/s. sure is 16 bars and the velocity is negligible. The diffuser
4.20 Air enters an uninsulated nozzle operating at steady state operates at steady state and potential energy effects can be
at 420K with negligible velocity and exits the nozzle at 290K neglected. Determine the exit temperature, in C.
4.24 Air expands through a turbine from 10 bar, 900 K to 1 bar, (a) the mass flow rate of the steam at each of the two exits,
500 K. The inlet velocity is small compared to the exit veloc- in kg/h.
ity of 100 m/s. The turbine operates at steady state and develops (b) the diameter, in m, of the duct through which steam is ex-
a power output of 3200 kW. Heat transfer between the turbine tracted, if the velocity there is 20 m/s.
and its surroundings and potential energy effects are negligi-
ble. Calculate the mass flow rate of air, in kg/s, and the exit 4.30 Air is compressed at steady state from 1 bar, 300 K, to
area, in m2. 6 bar with a mass flow rate of 4 kg/s. Each unit of mass pass-
ing from inlet to exit undergoes a process described by
4.25 A well-insulated turbine operating at steady state develops
pv1.27 constant. Heat transfer occurs at a rate of 46.95 kJ
23 MW of power for a steam flow rate of 40 kg/s. The steam
per kg of air flowing to cooling water circulating in a water
enters at 360C with a velocity of 35 m /s and exits as saturated
jacket enclosing the compressor. If kinetic and potential en-
vapor at 0.06 bar with a velocity of 120 m /s. Neglecting
ergy changes of the air from inlet to exit are negligible, cal-
potential energy effects, determine the inlet pressure, in bar.
culate the compressor power, in kW.
4.26 Nitrogen gas enters a turbine operating at steady state with
a velocity of 60 m/s, a pressure of 0.345 Mpa, and a temper- 4.31 A compressor operates at steady state with Refrigerant 22
ature of 700 K. At the exit, the velocity is 0.6 m/s, the pres- as the working fluid. The refrigerant enters at 5 bar, 10C, with
sure is 0.14 Mpa, and the temperature is 390 K. Heat transfer a volumetric flow rate of 0.8 m3/min. The diameters of the in-
from the surface of the turbine to the surroundings occurs at a let and exit pipes are 4 and 2 cm, respectively. At the exit, the
rate of 36 kJ per kg of nitrogen flowing. Neglecting potential pressure is 14 bar and the temperature is 90C. If the magni-
energy effects and using the ideal gas model, determine the tude of the heat transfer rate from the compressor to its sur-
power developed by the turbine, in kW. roundings is 5% of the compressor power input, determine the
4.27 Steam enters a well-insulated turbine operating at steady power input, in kW.
state with negligible velocity at 4 MPa, 320C. The steam ex-
4.32 Refrigerant 134a enters an air conditioner compressor at
pands to an exit pressure of 0.07 MPa and a velocity of
3.2 bar, 10C, and is compressed at steady state to 10 bar, 70C.
90 m/s. The diameter of the exit is 0.6 m. Neglecting poten-
The volumetric flow rate of refrigerant entering is 3.0 m3/min.
tial energy effects, plot the power developed by the turbine,
The power input to the compressor is 55.2 kJ per kg of re-
in kW, versus the steam quality at the turbine exit ranging
frigerant flowing. Neglecting kinetic and potential energy ef-
from 0.9 to 1.0.
fects, determine the heat transfer rate, in kW.
4.28 The intake to a hydraulic turbine installed in a flood con-
trol dam is located at an elevation of 10 m above the turbine 4.33 A compressor operating at steady state takes in 45 kg/min
exit. Water enters at 20C with negligible velocity and exits of methane gas (CH4) at 1 bar, 25C, 15 m/s, and compresses
from the turbine at 10 m/s. The water passes through the tur- it with negligible heat transfer to 2 bar, 90 m/s at the exit. The
bine with no significant changes in temperature or pressure be- power input to the compressor is 110 kW. Potential energy
tween the inlet and exit, and heat transfer is negligible. The effects are negligible. Using the ideal gas model, determine the
acceleration of gravity is constant at g 9.81 m/s2. If the temperature of the gas at the exit, in K.
power output at steady state is 500 kW, what is the mass flow
rate of water, in kg/s? 4.34 Refrigerant 134a is compressed at steady state from 2.4
bar, 0C, to 12 bar, 50C. Refrigerant enters the compressor
4.29 A well-insulated turbine operating at steady state is
with a volumetric flow rate of 0.38 m3/min, and the power in-
sketched in Fig. P4.29. Steam enters at 3 MPa, 400C, with a
put to the compressor is 2.6 kW. Cooling water circulating
volumetric flow rate of 85 m3/min. Some steam is extracted
through a water jacket enclosing the compressor experiences
from the turbine at a pressure of 0.5 MPa and a temperature
a temperature rise of 4C from inlet to exit with a negligible
of 180C. The rest expands to a pressure of 6 kPa and a quality
change in pressure. Heat transfer from the outside of the water
of 90%. The total power developed by the turbine is 11,400 kW.
jacket and all kinetic and potential energy effects can be
Kinetic and potential energy effects can be neglected.
neglected. Determine the mass flow rate of the cooling water,
Determine
in kg/s.
4.35 Air enters a water-jacketed air compressor operating at

steady state with a volumetric flow rate of 37 m3/min at 136
1
Power out kPa, 305 K and exits with a pressure of 680 kPa and a tem-
p1 = 3MPa Turbine perature of 400 K. The power input to the compressor is
T1 = 400C 155 kW. Energy transfer by heat from the compressed air to
(AV)1 = 85 m3/min 2 3 the cooling water circulating in the water jacket results in an
p2 = 0.5 MPa p3 = 6 kPa increase in the temperature of the cooling water from inlet to
T2 = 180C x3 = 90% exit with no change in pressure. Heat transfer from the outside
V2 = 20 m/s of the jacket as well as all kinetic and potential energy effects
Figure P4.29 can be neglected.
#
(a) Determine the temperature increase of the cooling water, of the liquid entering at inlet 1 is m1 3.2 105 kg/h, de-
#
in K, if the cooling water mass flow rate is 82 kg/min. termine the mass flow rate at inlet 2, m2, in kg/h.
(b) Plot the temperature increase of the cooling water, in K,
4.42 The cooling coil of an air-conditioning system is a heat
versus the cooling water mass flow rate ranging from 75
exchanger in which air passes over tubes through which Re-
to 90 kg/min.
frigerant 22 flows. Air enters with a volumetric flow rate of
4.36 A pump steadily delivers water through a hose terminated 40 m3/min at 27C, 1.1 bar, and exits at 15C, 1 bar. Refrig-
by a nozzle. The exit of the nozzle has a diameter of 2.5 cm erant enters the tubes at 7 bar with a quality of 16% and exits
and is located 4 m above the pump inlet pipe, which has a di- at 7 bar, 15C. Ignoring heat transfer from the outside of the
ameter of 5.0 cm. The pressure is equal to 1 bar at both the in- heat exchanger and neglecting kinetic and potential energy
let and the exit, and the temperature is constant at 20C. The effects, determine at steady state
magnitude of the power input required by the pump is 8.6 kW,
(a) the mass flow rate of refrigerant, in kg/min.
and the acceleration of gravity is g 9.81 m/s2. Determine
(b) the rate of energy transfer, in kJ/min, from the air to the
the mass flow rate delivered by the pump, in kg/s.
refrigerant.
4.37 An oil pump operating at steady state delivers oil at a rate
4.43 Refrigerant 134a flows at steady state through a long hor-
of 5.5 kg/s and a velocity of 6.8 m/s. The oil, which can be
izontal pipe having an inside diameter of 4 cm, entering as
modeled as incompressible, has a density of 1600 kg/m3 and
saturated vapor at 8C with a mass flow rate of 17 kg/min.
experiences a pressure rise from inlet to exit of .28 Mpa. There
Refrigerant vapor exits at a pressure of 2 bar. If the heat trans-
is no significant elevation difference between inlet and exit,
fer rate to the refrigerant is 3.41 kW, determine the exit tem-
and the inlet kinetic energy is negligible. Heat transfer between
perature, in C, and the velocities at the inlet and exit, each
the pump and its surroundings is negligible, and there is no
in m/s.
significant change in temperature as the oil passes through the
pump. If pumps are available in 14-horsepower increments, 4.44 Figure P4.44 shows a solar collector panel with a surface
determine the horsepower rating of the pump needed for this area of 2.97 m2. The panel receives energy from the sun at a
application. rate of 1.5 kW. Thirty-six percent of the incoming energy is
lost to the surroundings. The remainder is used to heat liquid
4.38 Ammonia enters a heat exchanger operating at steady state
water from 40C to 60C. The water passes through the solar
as a superheated vapor at 14 bar, 60C, where it is cooled and
collector with a negligible pressure drop. Neglecting kinetic
condensed to saturated liquid at 14 bar. The mass flow rate of
and potential energy effects, determine at steady state the mass
the refrigerant is 450 kg/h. A separate stream of air enters the
flow rate of water, in kg. How many gallons of water at 60C
heat exchanger at 17C, 1 bar and exits at 42C, 1 bar. Ignor-
can eight collectors provide in a 30-min time period?
ing heat transfer from the outside of the heat exchanger and
neglecting kinetic and potential energy effects, determine the
mass flow rate of the air, in kg/min.
4.39 A steam boiler tube is designed to produce a stream of sat-
urated vapor at 200 kPa from saturated liquid entering at the A = 2.97 m2
same pressure. At steady state, the flow rate is 0.25 kg/min.
Water in
The boiler is constructed from a well-insulated stainless steel
at 40C
pipe through which the steam flows. Electrodes clamped to the
l
1.5 kW
ne
pa
pipe at each end cause a 10-V direct current to pass through

or
ct
the pipe material. Determine the required size of the power

le
ol
rc
supply, in kW, and the expected current draw, in amperes.

la
So
4.40 Carbon dioxide gas is heated as it flows steadily through 36% loss Water out
a 2.5-cm-diameter pipe. At the inlet, the pressure is 2 bar, the at 60C
temperature is 300 K, and the velocity is 100 m /s. At the exit,
the pressure and velocity are 0.9413 bar and 400 m /s, respec-
tively. The gas can be treated as an ideal gas with constant
specific heat cp 0.94 kJ/kg K. Neglecting potential energy Figure P4.44
effects, determine the rate of heat transfer to the carbon
dioxide, in kW.
4.41 A feedwater heater in a vapor power plant operates at 4.45 As shown in Fig. P4.45, 15 kg/s of steam enters a desu-
steady state with liquid entering at inlet 1 with T1 45C and perheater operating at steady state at 30 bar, 320C, where it
p1 3.0 bar. Water vapor at T2 320C and p2 3.0 bar is mixed with liquid water at 25 bar and temperature T2 to pro-
enters at inlet 2. Saturated liquid water exits with a pressure duce saturated vapor at 20 bar. Heat transfer between the de-
of p3 3.0 bar. Ignore heat transfer with the surroundings and vice and its surroundings and kinetic and potential energy
all kinetic and potential energy effects. If the mass flow rate effects can be neglected.
#
(a) If T2 200C, determine the mass flow rate of liquid, m2, cal power. The rate of energy transfer by convection from the
in kg/s. plate-mounted electronics is estimated to be 0.08 kW. Kinetic
and potential energy effects can be ignored. Determine the tube
3 diameter, in cm.
p3 = 20 bar
Saturated vapor
Valve Valve Convection
1 De- 2 cooling on
superheater top surface
p1 = 30 bar p2 = 25 bar
T1 = 320C T2
m 1 = 15 kg/s
Figure P4.45
#
(b) Plot m2, in kg/s, versus T2 ranging from 20 to 220C.
2
4.46 A feedwater heater operates at steady state with liquid Electronic
water entering at inlet 1 at 7 bar, 42C, and a mass flow rate 1 + components
T2 = 24C
of 70 kg/s. A separate stream of water enters at inlet 2 as a
two-phase liquidvapor mixture at 7 bar with a quality of 98%. T1 = 20C
Saturated liquid at 7 bar exits the feedwater heater at 3. Ig- V1 = 0.4 m/s
noring heat transfer with the surroundings and neglecting Water
kinetic and potential energy effects, determine the mass flow Figure P4.50
rate, in kg/s, at inlet 2.
4.47 The electronic components of Example 4.8 are cooled by
air flowing through the electronics enclosure. The rate of energy 4.51 Electronic components are mounted on the inner surface
transfer by forced convection from the electronic components of a horizontal cylindrical duct whose inner diameter is 0.2 m,
to the air is hA(Ts Ta), where hA 5 W/K, Ts denotes the as shown in Fig. P4.51. To prevent overheating of the elec-
average surface temperature of the components, and Ta denotes tronics, the cylinder is cooled by a stream of air flowing
the average of the inlet and exit air temperatures. Referring to through it and by convection from its outer surface. Air enters
Example 4.8 as required, determine the largest value of Ts, in the duct at 25C, 1 bar and a velocity of 0.3 m /s and exits with
C, for which the specified limits are met. negligible changes in kinetic energy and pressure at a temper-
4.47 The electronic components of a computer consume 0.1 kW ature that cannot exceed 40C. If the electronic components
of electrical power. To prevent overheating, cooling air is sup- require 0.20 kW of electric power at steady state, determine
plied by a 25-W fan mounted at the inlet of the electronics en- the minimum rate of heat transfer by convection from the cylin-
closure. At steady state, air enters the fan at 20C, 1 bar and ders outer surface, in kW, for which the limit on the temper-
exits the electronics enclosure at 35C. There is no significant ature of the exiting air is met.
energy transfer by heat from the outer surface of the enclosure
to the surroundings and the effects of kinetic and potential en-
ergy can be ignored. Determine the volumetric flow rate of the
Convection cooling on outer surface
entering air, in m3/s.
4.49 Ten kg/min of cooling water circulates through a water
jacket enclosing a housing filled with electronic components. Air
At steady state, water enters the water jacket at 22C and exits
with a negligible change in pressure at a temperature that can- T1 = 25C T2 40C
not exceed 26C. There is no significant energy transfer by heat p1 = 1 bar 1 2 p2 = 1 bar
from the outer surface of the water jacket to the surroundings, V1 = 0.3 m/s
D1 = 0.2 m Electronic components
and kinetic and potential energy effects can be ignored. + mounted on inner surface
Determine the maximum electric power the electronic compo-
nents can receive, in kW, for which the limit on the temperature Figure P4.51
of the exiting water is met.
4.50 As shown in Fig. P4.50, electronic components mounted
on a flat plate are cooled by convection to the surroundings 4.52 Ammonia enters the expansion valve of a refrigeration sys-
and by liquid water circulating through a U-tube bonded to the tem at a pressure of 1.4 MPa and a temperature of 32C and
plate. At steady state, water enters the tube at 20C and a ve- exits at 0.08 MPa. If the refrigerant undergoes a throttling
locity of 0.4 m /s and exits at 24C with a negligible change in process, what is the quality of the refrigerant exiting the
pressure. The electrical components receive 0.5 kW of electri- expansion valve?
4.53 Propane vapor enters a valve at 1.6 MPa, 70C, and 4.56 Refrigerant 134a enters the flash chamber operating at
leaves at 0.5 MPa. If the propane undergoes a throttling steady state shown in Fig. P4.56 at 10 bar, 36C, with a mass
process, what is the temperature of the propane leaving the flow rate of 482 kg/h. Saturated liquid and saturated vapor exit
valve, in C? as separate streams, each at pressure p. Heat transfer to the
4.54 A large pipe carries steam as a two-phase liquidvapor surroundings and kinetic and potential energy effects can be
mixture at 1.0 MPa. A small quantity is withdrawn through a ignored.
throttling calorimeter, where it undergoes a throttling process (a) Determine the mass flow rates of the exiting streams, each
to an exit pressure of 0.1 MPa. For what range of exit tem- in kg/h, if p 4 bar.
peratures, in C, can the calorimeter be used to determine the (b) Plot the mass flow rates of the exiting streams, each in
quality of the steam in the pipe? What is the corresponding kg/h, versus p ranging from 1 to 9 bar.
range of steam quality values?
4.55 As shown in Fig. P4.55, a steam turbine at steady state is
operated at part load by throttling the steam to a lower pres-
3
Saturated vapor,
Valve pressure p
Valve 1
Flash
1 2 Power out
Turbine chamber
p1 = 10 bar
p1 = 1.5 MPa p2 = 1 MPa T1 = 36C
T1 = 320C m 1 = 482 kg/h
3 Saturated liquid,
p3 = .08 bar pressure p
x3 = 90%
2
Figure P4.55 Figure P4.56
sure before it enters the turbine. Before throttling, the pressure 4.57 Air as an ideal gas flows through the turbine and heat ex-
and temperature are, respectively, 1.5 MPa and 320C. After changer arrangement shown in Fig. P4.57. Data for the two
throttling, the pressure is 1 MPa. At the turbine exit, the steam flow streams are shown on the figure. Heat transfer to the sur-
is at .08 bar and a quality of 90%. Heat transfer with the roundings can be neglected, as can all kinetic and potential en-
surroundings and all kinetic and potential energy effects can ergy effects. Determine T3, in K, and the power output of the
be ignored. Determine second turbine, in kW, at steady state.
(a) the temperature at the turbine inlet, in C. 4.58 A residential heat pump system operating at steady state
(b) the power developed by the turbine, in kJ/kg of steam is shown schematically in Fig. P4.58. Refrigerant 134a circu-
flowing. lates through the components of the system, and property data
at the numbered locations are given on the figure. The mass

Wt1 = 10,000 kW Wt 2 = ?
Turbine Turbine
1 2
p3 = 4.5 bar
T3 = ? T4 = 980 K
T2 = 1100 K
p4 = 1 bar
Air p2 = 5 bar
in
1 2 3 4
T1 = 1400 K
p1 = 20 bar T5 = 1480 K
6 Heat exchanger 5 p5 = 1.35 bar
m 5 = 1200 kg/min
T6 = 1200 K
p6 = 1 bar Air
in Figure P4.57
flow rate of the refrigerant is 4.6 kg/min. Kinetic and poten- flow rate of the water is 109 kg/s. Kinetic and potential energy
tial energy effects are negligible. Determine effects are negligible as are all stray heat transfers. Determine
(a) rate of heat transfer between the compressor and the sur- (a) the thermal efficiency.
roundings, in kJ/min. (b) the mass flow rate of the cooling water passing through
(b) the coefficient of performance. the condenser, in kg/s.
Transient Analysis
4.60 A tiny hole develops in the wall of a rigid tank whose vol-
Return air ume is 0.75 m3, and air from the surroundings at 1 bar, 25C
Heated air to
from house house at T > 20C leaks in. Eventually, the pressure in the tank reaches 1 bar. The
at 20C process occurs slowly enough that heat transfer between the
tank and the surroundings keeps the temperature of the air
inside the tank constant at 25C. Determine the amount of heat
p2 = 8 bar transfer, in kJ, if initially the tank
3 T3 = 30C 2
p3 = 8 bar h 2 = 270 kJ/kg (a) is evacuated.
Condenser Power input (b) contains air at 0.7 bar, 25C.
to compressor 4.61 A rigid tank of volume 0.75 m3 is initially evacuated. A
Expansion = 2.5 kW hole develops in the wall, and air from the surroundings at
Compressor
valve 1 bar, 25C flows in until the pressure in the tank reaches 1 bar.
Heat transfer between the contents of the tank and the sur-
Evaporator roundings is negligible. Determine the final temperature in the
p1 = 1.8 bar
4 T 4 = 12C 1 T1 = 10C tank, in C.
4.62 A rigid, well-insulated tank of volume 0.5 m3 is initially
evacuated. At time t 0, air from the surroundings at 1 bar,
21C begins to flow into the tank. An electric resistor trans-
fers energy to the air in the tank at a constant rate of 100 W
Air exits Outside air enters
at T < 0C at 0C for 500 s, after which time the pressure in the tank is 1 bar.
What is the temperature of the air in the tank, in C, at the
Figure P4.58
final time?
4.63 The rigid tank illustrated in Fig. P4.63 has a volume of
4.59 Figure P4.59 shows a simple vapor power plant operating 0.06 m3 and initially contains a two-phase liquidvapor mix-
at steady state with water circulating through the components. ture of H2O at a pressure of 15 bar and a quality of 20%. As
Relevant data at key locations are given on the figure. The mass the tank contents are heated, a pressure-regulating valve keeps
the pressure constant in the tank by allowing saturated vapor
to escape. Neglecting kinetic and potential energy effects
(a) determine the total mass in the tank, in kg, and the amount
Q in of heat transfer, in kJ, if heating continues until the final
p1 = 100 bar
T1 = 520C quality is x 0.5.
Power out (b) plot the total mass in the tank, in kg, and the amount of
Turbine
1 heat transfer, in kJ, versus the final quality x ranging from
0.2 to 1.0.
p2 = 0.08 bar
Steam x2 = 90% 2 Pressure-regulating valve
generator Cooling
water in at 20C
Condenser
p4 = 100 bar V = 0.06 m3

4 T4 = 43C Cooling p = 15 bar
water out at 35C xinitial = 20%
Pump
3 p3 = 0.08 bar
Power Saturated liquid
in
Figure P4.59 Figure P4.63

4.64 A well-insulated rigid tank of volume 10 m3 is connected 4.68 A well-insulated pistoncylinder assembly is connected by
to a large steam line through which steam flows at 15 bar and a valve to an air supply line at 8 bar, as shown in Fig. P4.68.
280C. The tank is initially evacuated. Steam is allowed to flow Initially, the air inside the cylinder is at 1 bar, 300 K, and the
into the tank until the pressure inside is p. piston is located 0.5 m above the bottom of the cylinder. The
(a) Determine the amount of mass in the tank, in kg, and the atmospheric pressure is 1 bar, and the diameter of the piston
temperature in the tank, in C, when p 15 bar. face is 0.3 m. The valve is opened and air is admitted slowly
(b) Plot the quantities of part (a) versus p ranging from 0.1 to until the volume of air inside the cylinder has doubled. The
15 bar. weight of the piston and the friction between the piston and
the cylinder wall can be ignored. Using the ideal gas model,
4.65 A tank of volume 1 m3 initially contains steam at 6 MPa
plot the final temperature, in K, and the final mass, in kg, of
and 320C. Steam is withdrawn slowly from the tank until the
the air inside the cylinder for supply temperatures ranging from
pressure drops to p. Heat transfer to the tank contents main-
300 to 500 K.
tains the temperature constant at 320C. Neglecting all kinetic
and potential energy effects
(a) determine the heat transfer, in kJ, if p 1.5 MPa.
(b) plot the heat transfer, in kJ, versus p ranging from 0.5 to
6 MPa.
patm =
4.66 A 1 m3 tank initially contains air at 300 kPa, 300 K. Air 1 bar
slowly escapes from the tank until the pressure drops to 100
kPa. The air that remains in the tank undergoes a process de-
scribed by pv1.2 constant. For a control volume enclosing
the tank, determine the heat transfer, in kJ. Assume ideal gas Diameter = 0.3 m
behavior with constant specific heats.
L Initially: L1 = 0.5 m
4.67 A well-insulated tank contains 25 kg of Refrigerant 134a,
T1 = 300 K
initially at 300 kPa with a quality of 0.8 (80%). The pressure p1 = 1 bar
is maintained by nitrogen gas acting against a flexible bladder,
as shown in Fig. P4.67. The valve is opened between the tank
and a supply line carrying Refrigerant 134a at 1.0 MPa, 120C. Valve
The pressure regulator allows the pressure in the tank to re- Air supply line: 8 bar
main at 300 kPa as the bladder expands. The valve between
the line and the tank is closed at the instant when all the liquid
has vaporized. Determine the amount of refrigerant admitted Figure P4.68
to the tank, in kg.
4.69 Nitrogen gas is contained in a rigid 1-m tank, initially at

Pressure-regulating 10 bar, 300 K. Heat transfer to the contents of the tank occurs
valve Nitrogen supply
until the temperature has increased to 400 K. During the
process, a pressure-relief valve allows nitrogen to escape,
maintaining constant pressure in the tank. Neglecting kinetic
and potential energy effects, and using the ideal gas model with
constant specific heats evaluated at 350 K, determine the mass
N2 of nitrogen that escapes, in kg, and the amount of energy trans-
Flexible bladder fer by heat, in kJ.
4.70 The air supply to a 56 m3 office has been shut off
Refrigerant 134a overnight to conserve utilities, and the room temperature has
300 kPa Tank dropped to 4C. In the morning, a worker resets the thermo-
stat to 21C, and 6 m3/min of air at 50C begins to flow in
through a supply duct. The air is well mixed within the room,
and an equal mass flow of air at room temperature is with-
Line: 1000 kPa, 120 C drawn through a return duct. The air pressure is nearly 1 bar
everywhere. Ignoring heat transfer with the surroundings and
kinetic and potential energy effects, estimate how long it takes
for the room temperature to reach 21C. Plot the room tem-
Figure P4.67 perature as a function of time.

4.1D What practical measures can be taken by manufacturers Reflective
to use energy resources more efficiently? List several specific surface
opportunities, and discuss their potential impact on profitabil-
ity and productivity. Glass or Tap water
clear plastic Inlet
4.2D Methods for measuring mass flow rates of gases and liq- Warm water
uids flowing in pipes and ducts include: rotameters, turbine Tank to storage
flowmeters, orifice-type flowmeters, thermal flowmeters, and Exit
Coriolis-type flowmeters. Determine the principles of opera-
tion of each of these flow-measuring devices. Consider the suit-
ability of each for measuring liquid or gas flows. Can any be
Insulated walls
used for two-phase liquidvapor mixtures? Which measure vol-
and hinged covers
umetric flow rate and require separate measurements of pres-
sure and temperature to determine the state of the substance?
Figure P4.6D
Summarize your findings in a brief report.
4.3D Wind turbines, or windmills, have been used for genera-
tions to develop power from wind. Several alternative wind tur-
available head and the river flow, each of which varies con-
bine concepts have been tested, including among others the
siderably throughout the year. Using U.S. Geological Survey
Mandaras, Darrieus, and propeller types. Write a report in
data, determine the typical variations in head and flow for a
which you describe the operating principles of prominent wind
river in your locale. Based on this information, estimate the
turbine types. Include in your report an assessment of the eco-
total annual electric generation of a hydraulic turbine placed
nomic feasibility of each type.
on the river. Does the peak generating capacity occur at the
4.4D Prepare a memorandum providing guidelines for selecting same time of year as peak electrical demand in your area?
fans for cooling electronic components. Consider the advan- Would you recommend that your local utility take advantage
tages and disadvantages of locating the fan at the inlet of the of this opportunity for electric power generation? Discuss.
enclosure containing the electronics. Repeat for a fan at the
4.8D Figure P4.8D illustrates an experimental apparatus for
enclosure exit. Consider the relative merits of alternative fan
steady-state testing of Refrigerant 134a shell-and-tube evap-
types and of fixed- versus variable-speed fans. Explain how
orators having a capacity of 100 kW. As shown by the dashed
characteristic curves assist in fan selection.
lines on the figure, two subsystems provide refrigerant and a
4.5D Pumped-hydraulic storage power plants use relatively water-glycol mixture to the evaporator. The water-glycol
inexpensive off-peak baseload electricity to pump water from mixture is chilled in passing through the evaporator tubes, so
a lower reservoir to a higher reservoir. During periods of peak the water-glycol subsystem must reheat and recirculate the
demand, electricity is produced by discharging water from the mixture to the evaporator. The refrigerant subsystem must re-
upper to the lower reservoir through a hydraulic turbine- move the energy added to the refrigerant passing through the
generator. A single device normally plays the role of the pump evaporator, and deliver saturated liquid refrigerant at 20C.
during upper-reservoir charging and the turbine-generator For each subsystem, draw schematics showing layouts of heat
during discharging. The ratio of the power developed during exchangers, pumps, interconnecting piping, etc. Also, specify
discharging to the power required for charging is typically
much less than 100%. Write a report describing the features
of the pump-turbines used for such applications and their size
and cost. Include in your report a discussion of the economic
feasibility of pumped-hydraulic storage power plants. Refrigerant
subsystem
4.6D Figure P4.6D shows a batch-type solar water heater. With
the exit closed, cold tap water fills the tank, where it is heated
by the sun. The batch of heated water is then allowed to flow
to an existing conventional gas or electric water heater. If the
batch-type solar water heater is constructed primarily from sal- Water-
vaged and scrap material, estimate the time for a typical fam- glycol
subsystem
ily of four to recover the cost of the water heater from reduced
water heating by conventional means.
4.7D Low-head dams (3 to 10 m), commonly used for flood Shell-and-tube
control on many rivers, provide an opportunity for electric evaporator
power generation using hydraulic turbine-generators. Esti-
mates of this hydroelectric potential must take into account the Figure P4.8D
the mass flow rates, heat transfer rates, and power require- 4.10D Smaller can be Better (see box Sec. 4.3). Investigate
ments for each component within the subsystems, as the scope of current medical applications of MEMS. Write a
appropriate. report including at least three references.
4.9D The stack from an industrial paint-drying oven discharges 4.11D Sensibly Built Homes Cost No More (see box Sec. 4.3).
30 m3/min of gaseous combustion products at 240C. Investi- In energy-efficient homes, indoor air quality can be a concern.
gate the economic feasibility of installing a heat exchanger in Research the issue of carbon monoxide and radon buildup in
the stack to heat air that would provide for some of the space tightly sealed houses. Write a report including at least three
heating needs of the plant. references.
C
H
A
P
T
The Second
5 R
E
Law of
Thermodynamics
E N G I N E E R I N G C O N T E X T The presentation to this point has
considered thermodynamic analysis using the conservation of mass and conservation of
energy principles together with property relations. In Chaps. 2 through 4 these fundamen-
tals are applied to increasingly complex situations. The conservation principles do not
always suffice, however, and often the second law of thermodynamics is also required for
chapter objective thermodynamic analysis. The objective of this chapter is to introduce the second law of
thermodynamics. A number of deductions that may be called corollaries of the second law
are also considered, including performance limits for thermodynamic cycles. The current
presentation provides the basis for subsequent developments involving the second law in
Chaps. 6 and 7.
5.1 Introducing the Second Law

The objectives of the present section are to (1) motivate the need for and the usefulness of
the second law, and (2) to introduce statements of the second law that serve as the point of
departure for its application.
5.1.1 Motivating the Second Law

It is a matter of everyday experience that there is a definite direction for spontaneous
processes. This can be brought out by considering the three systems pictured in Fig. 5.1.
System a. An object at an elevated temperature Ti placed in contact with atmospheric
air at temperature T0 would eventually cool to the temperature of its much larger
surroundings, as illustrated in Fig. 5.1a. In conformity with the conservation of energy
principle, the decrease in internal energy of the body would appear as an increase in
the internal energy of the surroundings. The inverse process would not take place
spontaneously, even though energy could be conserved: The internal energy of the
surroundings would not decrease spontaneously while the body warmed from T0 to its
initial temperature.
System b. Air held at a high pressure pi in a closed tank would flow spontaneously to
the lower pressure surroundings at p0 if the interconnecting valve were opened, as
illustrated in Fig. 5.1b. Eventually fluid motions would cease and all of the air would be
174
5.1 Introducing the Second Law 175
Atmospheric air
Q
at T0
Body at Time Time

T0 < T < Ti T0
Ti > T0
(a)
Atmospheric air
at p0
Valve
Air at Air
pi > p0 Air at
p0 < p < pi p0
(b)
Mass
Mass
zi
0 < z < zi Mass
(c)
Figure 5.1 Illustrations of spontaneous processes and the eventual attainment
of equilibrium with the surroundings. (a) Spontaneous heat transfer. (b) Sponta-
neous expansion. (c) Falling mass.
at the same pressure as the surroundings. Drawing on experience, it should be clear that
the inverse process would not take place spontaneously, even though energy could be
conserved: Air would not flow spontaneously from the surroundings at p0 into the tank,
returning the pressure to its initial value.
System c. A mass suspended by a cable at elevation zi would fall when released, as
illustrated in Fig. 5.1c. When it comes to rest, the potential energy of the mass in its
initial condition would appear as an increase in the internal energy of the mass and its
surroundings, in accordance with the conservation of energy principle. Eventually, the
mass also would come to the temperature of its much larger surroundings. The inverse
process would not take place spontaneously, even though energy could be conserved:
The mass would not return spontaneously to its initial elevation while its internal energy
or that of its surroundings decreased.
In each case considered, the initial condition of the system can be restored, but not in a
spontaneous process. Some auxiliary devices would be required. By such auxiliary means
the object could be reheated to its initial temperature, the air could be returned to the tank
176 Chapter 5 The Second Law of Thermodynamics
and restored to its initial pressure, and the mass could be lifted to its initial height. Also in
each case, a fuel or electrical input normally would be required for the auxiliary devices to
function, so a permanent change in the condition of the surroundings would result.
The foregoing discussion indicates that not every process consistent with the principle of
energy conservation can occur. Generally, an energy balance alone neither enables the pre-
ferred direction to be predicted nor permits the processes that can occur to be distinguished
from those that cannot. In elementary cases such as the ones considered, experience can be
drawn upon to deduce whether particular spontaneous processes occur and to deduce their
directions. For more complex cases, where experience is lacking or uncertain, a guiding
principle would be helpful. This is provided by the second law.
The foregoing discussion also indicates that when left to themselves, systems tend to
undergo spontaneous changes until a condition of equilibrium is achieved, both internally
and with their surroundings. In some cases equilibrium is reached quickly, in others it is
achieved slowly. For example, some chemical reactions reach equilibrium in fractions of
seconds; an ice cube requires a few minutes to melt; and it may take years for an iron bar
to rust away. Whether the process is rapid or slow, it must of course satisfy conservation of
energy. However, that alone would be insufficient for determining the final equilibrium state.
Another general principle is required. This is provided by the second law.
OPPORTUNITIES FOR DEVELOPING WORK
By exploiting the spontaneous processes shown in Fig. 5.1, it is possible, in principle, for
work to be developed as equilibrium is attained. for example. . . instead of permit-
ting the body of Fig. 5.1a to cool spontaneously with no other result, energy could be delivered
by heat transfer to a system undergoing a power cycle that would develop a net amount of
work (Sec. 2.6). Once the object attained equilibrium with the surroundings, the process
would cease. Although there is an opportunity for developing work in this case, the oppor-
tunity would be wasted if the body were permitted to cool without developing any work. In
the case of Fig. 5.1b, instead of permitting the air to expand aimlessly into the lower-pressure
surroundings, the stream could be passed through a turbine and work could be developed.
Accordingly, in this case there is also a possibility for developing work that would not be
exploited in an uncontrolled process. In the case of Fig. 5.1c, instead of permitting the mass
to fall in an uncontrolled way, it could be lowered gradually while turning a wheel, lifting
another mass, and so on.
These considerations can be summarized by noting that when an imbalance exists between
two systems, there is an opportunity for developing work that would be irrevocably lost if
the systems were allowed to come into equilibrium in an uncontrolled way. Recognizing this
possibility for work, we can pose two questions:
What is the theoretical maximum value for the work that could be obtained?
What are the factors that would preclude the realization of the maximum value?
That there should be a maximum value is fully in accord with experience, for if it were
possible to develop unlimited work, few concerns would be voiced over our dwindling fuel
supplies. Also in accord with experience is the idea that even the best devices would be
subject to factors such as friction that would preclude the attainment of the theoretical
maximum work. The second law of thermodynamics provides the means for determining the
theoretical maximum and evaluating quantitatively the factors that preclude attaining the
maximum.
SECOND LAW SUMMARY
The preceding discussions can be summarized by noting that the second law and deductions
from it are useful because they provide means for
1. predicting the direction of processes.
2. establishing conditions for equilibrium.
3. determining the best theoretical performance of cycles, engines, and other devices.
4. evaluating quantitatively the factors that preclude the attainment of the best theoretical
performance level.
Additional uses of the second law include its roles in
5. defining a temperature scale independent of the properties of any thermometric substance.
6. developing means for evaluating properties such as u and h in terms of properties that are
more readily obtained experimentally.
Scientists and engineers have found many additional applications of the second law and
deductions from it. It also has been used in economics, philosophy, and other areas far
removed from engineering thermodynamics.
The six points listed can be thought of as aspects of the second law of thermodynam-
ics and not as independent and unrelated ideas. Nonetheless, given the variety of these
topic areas, it is easy to understand why there is no single statement of the second law that
brings out each one clearly. There are several alternative, yet equivalent, formulations of
the second law.
In the next section, two equivalent statements of the second law are introduced as a point
of departure for our study of the second law and its consequences. Although the exact
relationship of these particular formulations to each of the second law aspects listed above
may not be immediately apparent, all aspects listed can be obtained by deduction from these
formulations or their corollaries. It is important to add that in every instance where a con-
sequence of the second law has been tested directly or indirectly by experiment, it has been
unfailingly verified. Accordingly, the basis of the second law of thermodynamics, like every
other physical law, is experimental evidence.
5.1.2 Statements of the Second Law

Among many alternative statements of the second law, two are frequently used in engineer-
ing thermodynamics. They are the Clausius and KelvinPlanck statements. The objective of
this section is to introduce these two equivalent second law statements.
The Clausius statement has been selected as a point of departure for the study of the
second law and its consequences because it is in accord with experience and therefore easy
to accept. The KelvinPlanck statement has the advantage that it provides an effective
means for bringing out important second law deductions related to systems undergoing
thermodynamic cycles. One of these deductions, the Clausius inequality (Sec. 6.1), leads
directly to the property entropy and to formulations of the second law convenient for the
analysis of closed systems and control volumes as they undergo processes that are not
necessarily cycles.
CLAUSIUS STATEMENT OF THE SECOND LAW
The Clausius statement of the second law asserts that: It is impossible for any system to Clausius statement
operate in such a way that the sole result would be an energy transfer by heat from a
cooler to a hotter body.
The Clausius statement does not rule out the possibility of transferring energy by heat
from a cooler body to a hotter body, for this is exactly what refrigerators and heat pumps
accomplish. However, as the words sole result in the statement suggest, when a heat trans-
fer from a cooler body to a hotter body occurs, there must be some other effect within the
Q Hot
system accomplishing the heat transfer, its surroundings, or both. If the system operates in
a thermodynamic cycle, its initial state is restored after each cycle, so the only place that
Yes! Metal No! must be examined for such other effects is its surroundings. for example. . . cooling
bar of food is accomplished by refrigerators driven by electric motors requiring work from their
surroundings to operate. The Clausius statement implies that it is impossible to construct a
Cold Q
refrigeration cycle that operates without an input of work.
KELVINPLANCK STATEMENT OF THE SECOND LAW
thermal reservoir Before giving the KelvinPlanck statement of the second law, the concept of a thermal reser-
voir is introduced. A thermal reservoir, or simply a reservoir, is a special kind of system that
always remains at constant temperature even though energy is added or removed by heat
transfer. A reservoir is an idealization of course, but such a system can be approximated in
a number of waysby the earths atmosphere, large bodies of water (lakes, oceans), a large
block of copper, and a system consisting of two phases (although the ratio of the masses of
the two phases changes as the system is heated or cooled at constant pressure, the tempera-
ture remains constant as long as both phases coexist). Extensive properties of a thermal reser-
voir such as internal energy can change in interactions with other systems even though the
reservoir temperature remains constant.
KelvinPlanck statement Having introduced the thermal reservoir concept, we give the KelvinPlanck statement
of the second law: It is impossible for any system to operate in a thermodynamic cycle
Thermal and deliver a net amount of energy by work to its surroundings while receiving energy
reservoir Qcycle
by heat transfer from a single thermal reservoir. The KelvinPlanck statement does not
rule out the possibility of a system developing a net amount of work from a heat trans-
fer drawn from a single reservoir. It only denies this possibility if the system undergoes
No! Wcycle
a thermodynamic cycle.
The KelvinPlanck statement can be expressed analytically. To develop this, let us study
a system undergoing a cycle while exchanging energy by heat transfer with a single reser-
System undergoing a voir. The first and second laws each impose constraints:
thermodynamic cycle
A constraint is imposed by the first law on the net work and heat transfer between the
system and its surroundings. According to the cycle energy balance
Wcycle Qcycle
In words, the net work done by the system undergoing a cycle equals the net heat
transfer to the system. Although the cycle energy balance allows the net work Wcycle to
be positive or negative, the second law imposes a constraint on its direction, as
considered next.
According to the KelvinPlanck statement, a system undergoing a cycle while
communicating thermally with a single reservoir cannot deliver a net amount of work
to its surroundings. That is, the net work of the cycle cannot be positive. However, the
KelvinPlanck statement does not rule out the possibility that there is a net work
transfer of energy to the system during the cycle or that the net work is zero. Thus, the
analytical form of the KelvinPlanck statement is
1single reservoir2
analytical form:
KelvinPlanck statement
Wcycle 0 (5.1)
where the words single reservoir are added to emphasize that the system communicates
thermally only with a single reservoir as it executes the cycle. In Sec. 5.3.1, we associ-
ate the less than and equal to signs of Eq. 5.1 with the presence and absence of int-
ernal irreversibilities, respectively. The concept of irreversibilities is considered in
Sec. 5.2.
The equivalence of the Clausius and KelvinPlanck statements can be demonstrated
by showing that the violation of each statement implies the violation of the other (see
box).
D E M O N S T R AT I N G T H E E Q U I VA L E N C E O F T H E
C L A U S I U S A N D K E LV I N P L A N C K S TAT E M E N T S
The equivalence of the Clausius and KelvinPlanck statements is demonstrated by

showing that the violation of each statement implies the violation of the other. That
a violation of the Clausius statement implies a violation of the KelvinPlanck state-
ment is readily shown using Fig. 5.2, which pictures a hot reservoir, a cold reservoir,
and two systems. The system on the left transfers energy QC from the cold reservoir
to the hot reservoir by heat transfer without other effects occurring and thus violates
the Clausius statement. The system on the right operates in a cycle while receiving
QH (greater than QC) from the hot reservoir, rejecting QC to the cold reservoir, and
delivering work Wcycle to the surroundings. The energy flows labeled on Fig. 5.2 are
in the directions indicated by the arrows.
Consider the combined system shown by a dotted line on Fig. 5.2, which consists
of the cold reservoir and the two devices. The combined system can be regarded as
executing a cycle because one part undergoes a cycle and the other two parts experi-
ence no net change in their conditions. Moreover, the combined system receives en-
ergy (QH QC) by heat transfer from a single reservoir, the hot reservoir, and pro-
duces an equivalent amount of work. Accordingly, the combined system violates the
KelvinPlanck statement. Thus, a violation of the Clausius statement implies a vio-
lation of the KelvinPlanck statement. The equivalence of the two second-law state-
ments is demonstrated completely when it is also shown that a violation of the
KelvinPlanck statement implies a violation of the Clausius statement. This is left as
an exercise.
System undergoing a
thermodynamic cycle
QC Hot QH
reservoir
Wcycle = Q H Q C
Cold Figure 5.2 Illustration used to

QC reservoir QC
demonstrate the equivalence of the
Clausius and KelvinPlanck state-
Dotted line defines combined system ments of the second law.
5.2 Identifying Irreversibilities

One of the important uses of the second law of thermodynamics in engineering is to deter-
mine the best theoretical performance of systems. By comparing actual performance with the
best theoretical performance, insights often can be gained into the potential for improvement.
As might be surmised, the best performance is evaluated in terms of idealized processes. In
this section such idealized processes are introduced and distinguished from actual processes
involving irreversibilities.
IRREVERSIBLE PROCESSES
irreversible process A process is called irreversible if the system and all parts of its surroundings cannot be
exactly restored to their respective initial states after the process has occurred. A process is
reversible processes reversible if both the system and surroundings can be returned to their initial states.
Irreversible processes are the subject of the present discussion. Reversible processes are
considered again later in the section.
A system that has undergone an irreversible process is not necessarily precluded from
being restored to its initial state. However, were the system restored to its initial state, it
would not be possible also to return the surroundings to the state they were in initially.
As illustrated below, the second law can be used to determine whether both the system
and surroundings can be returned to their initial states after a process has occurred. That
is, the second law can be used to determine whether a given process is reversible or
irreversible.
It might be apparent from the discussion of the Clausius statement of the second law that
any process involving a spontaneous heat transfer from a hotter body to a cooler body is
irreversible. Otherwise, it would be possible to return this energy from the cooler body to
the hotter body with no other effects within the two bodies or their surroundings. However,
this possibility is contrary to our experience and is denied by the Clausius statement.
Processes involving other kinds of spontaneous events are irreversible, such as an unre-
strained expansion of a gas or liquid considered in Fig. 5.1. Friction, electrical resistance,
hysteresis, and inelastic deformation are examples of effects whose presence during a process
renders it irreversible.
In summary, irreversible processes normally include one or more of the following
irreversibilities:
Heat transfer through a finite temperature difference
Unrestrained expansion of a gas or liquid to a lower pressure
Spontaneous chemical reaction
irreversibilities Spontaneous mixing of matter at different compositions or states
Frictionsliding friction as well as friction in the flow of fluids
Electric current flow through a resistance
Magnetization or polarization with hysteresis
Inelastic deformation
Although the foregoing list is not exhaustive, it does suggest that all actual processes are
irreversible. That is, every process involves effects such as those listed, whether it is a naturally
occurring process or one involving a device of our construction, from the simplest mecha-
nism to the largest industrial plant. The term irreversibility is used to identify any of these
effects. The list given previously comprises a few of the irreversibilities that are commonly
encountered.
5.2 Identifying Irreversibilities 181
As a system undergoes a process, irreversibilities may be found within the system as

well as within its surroundings, although in certain instances they may be located pre-
dominately in one place or the other. For many analyses it is convenient to divide the ir-
reversibilities present into two classes. Internal irreversibilities are those that occur within internal and external
the system. External irreversibilities are those that occur within the surroundings, often irreversibilities
the immediate surroundings. As this distinction depends solely on the location of the
boundary, there is some arbitrariness in the classification, for by extending the boundary
to take in a portion of the surroundings, all irreversibilities become internal. Nonethe-
less, as shown by subsequent developments, this distinction between irreversibilities is
often useful.
Engineers should be able to recognize irreversibilities, evaluate their influence, and develop
practical means for reducing them. However, certain systems, such as brakes, rely on the
effect of friction or other irreversibilities in their operation. The need to achieve profitable
rates of production, high heat transfer rates, rapid accelerations, and so on invariably dictates
the presence of significant irreversibilities. Furthermore, irreversibilities are tolerated to some
degree in every type of system because the changes in design and operation required to reduce
them would be too costly. Accordingly, although improved thermodynamic performance can
accompany the reduction of irreversibilities, steps taken in this direction are constrained by
a number of practical factors often related to costs.
for example. . . consider two bodies at different temperatures that are able to
communicate thermally. With a finite temperature difference between them, a spontaneous
heat transfer would take place and, as discussed previously, this would be a source of
irreversibility. It might be expected that the importance of this irreversibility would di-
minish as the temperature difference approaches zero, and this is the case. From the study Q
of heat transfer (Sec. 2.4), we know that the transfer of a finite amount of energy by heat Hot, TH
between bodies whose temperatures differ only slightly would require a considerable Cold, TC
amount of time, a larger (more costly) heat transfer surface area, or both. To eliminate this Area
source of irreversibility, therefore, would require an infinite amount of time and/or an
infinite surface area.
Whenever any irreversibility is present during a process, the process must necessarily be ir-
reversible. However, the irreversibility of the process can be demonstrated using the
KelvinPlanck statement of the second law and the following procedure: (1) Assume there
is a way to return the system and surroundings to their respective initial states. (2) Show that
as a consequence of this assumption, it would be possible to devise a cycle that produces
work while no effect occurs other than a heat transfer from a single reservoir. Since the ex-
istence of such a cycle is denied by the KelvinPlanck statement, the initial assumption must
be in error and it follows that the process is irreversible. This approach can be used to demon-
strate that processes involving friction (see box), heat transfer through a finite temperature
difference, the unrestrained expansion of a gas or liquid to a lower pressure, and other effects
from the list given previously are irreversible. However, in most instances the use of the
KelvinPlanck statement to demonstrate the irreversibility of processes is cumbersome. It is
normally easier to use the entropy production concept (Sec. 6.5).
D E M O N S T R AT I N G I R R E V E R S I B I L I T Y: F R I C T I O N
Let us use the KelvinPlanck statement to demonstrate the irreversibility of a process

involving friction. Consider a system consisting of a block of mass m and an inclined
plane. Initially the block is at rest at the top of the incline. The block then slides down
the plane, eventually coming to rest at a lower elevation. There is no significant heat
transfer between the system and its surroundings during the process.
Applying the closed system energy balance
1Uf Ui 2
mg1zf zi 2
1KEf KEi 2 Q W
0 0 0
or
Uf Ui mg1zi zf 2
where U denotes the internal energy of the block-plane system and z is the elevation
of the block. Thus, friction between the block and plane during the process acts to
convert the potential energy decrease of the block to internal energy of the overall
system. Since no work or heat interactions occur between the system and its sur-
roundings, the condition of the surroundings remains unchanged during the process.
This allows attention to be centered on the system only in demonstrating that the
process is irreversible.
When the block is at rest after sliding down the plane, its elevation is zf and the in-
ternal energy of the blockplane system is Uf. To demonstrate that the process is irre-
versible using the KelvinPlanck statement, let us take this condition of the system,
shown in Fig. 5.3a, as the initial state of a cycle consisting of three processes. We imag-
ine that a pulleycable arrangement and a thermal reservoir are available to assist in
the demonstration.
Process 1: Assume that the inverse process can occur with no change in the sur-
roundings. That is, as shown in Fig. 5.3b, assume that the block returns sponta-
neously to its initial elevation and the internal energy of the system decreases to
its initial value, Ui. (This is the process we want to demonstrate is impossible.)
Process 2: As shown in Fig. 5.3c, use the pulleycable arrangement provided to lower
the block from zi to zf, allowing the decrease in potential energy to do work by
lifting another mass located in the surroundings. The work done by the system
equals the decrease in the potential energy of the block: mg(zi zf).
Process 3: The internal energy of the system can be increased from Ui to Uf by bring-
ing it into communication with the reservoir, as shown in Fig. 5.3d. The heat trans-
fer required is Q Uf Ui. Or, with the result of the energy balance on the system
given above, Q mg(zi zf). At the conclusion of this process the block is again at
elevation zf and the internal energy of the blockplane system is restored to Uf.
The net result of this cycle is to draw energy from a single reservoir by heat
transfer and produce an equivalent amount of work. There are no other effects.
However, such a cycle is denied by the KelvinPlanck statement. Since both the
heating of the system by the reservoir (Process 3) and the lowering of the mass by
the pulleycable while work is done (Process 2) are possible, it can be concluded
that it is Process 1 that is impossible. Since Process 1 is the inverse of the original
process where the block slides down the plane, it follows that the original process
is irreversible.
REVERSIBLE PROCESSES
A process of a system is reversible if the system and all parts of its surroundings can be
exactly restored to their respective initial states after the process has taken place. It should
be evident from the discussion of irreversible processes that reversible processes are purely
hypothetical. Clearly, no process can be reversible that involves spontaneous heat transfer
5.2 Identifying Irreversibilities 183
zi
Block
zf
(a) (b)
Reservoir
Figure 5.3 Figure used to

demonstrate the irreversibility of a
(c) (d) process involving friction.
through a finite temperature difference, an unrestrained expansion of a gas or liquid, friction,

or any of the other irreversibilities listed previously. In a strict sense of the word, a reversible
process is one that is perfectly executed.
All actual processes are irreversible. Reversible processes do not occur. Even so, certain
processes that do occur are approximately reversible. The passage of a gas through a properly
designed nozzle or diffuser is an example (Sec. 6.8). Many other devices also can be made
to approach reversible operation by taking measures to reduce the significance of irre-
versibilities, such as lubricating surfaces to reduce friction. A reversible process is the limiting
case as irreversibilities, both internal and external, are reduced further and further.
Although reversible processes cannot actually occur, they can be imagined. Earlier in this
section we considered how heat transfer would approach reversibility as the temperature dif-
ference approaches zero. Let us consider two additional examples:
A particularly elementary example is a pendulum oscillating in an evacuated space. The
pendulum motion approaches reversibility as friction at the pivot point is reduced. In
the limit as friction is eliminated, the states of both the pendulum and its surroundings
would be completely restored at the end of each period of motion. By definition, such a
process is reversible.
A system consisting of a gas adiabatically compressed and expanded in a frictionless
pistoncylinder assembly provides another example. With a very small increase in the
external pressure, the piston would compress the gas slightly. At each intermediate volume
during the compression, the intensive properties T, p, v, etc. would be uniform through-
out: The gas would pass through a series of equilibrium states. With a small decrease in Gas
the external pressure, the piston would slowly move out as the gas expands. At each inter-
mediate volume of the expansion, the intensive properties of the gas would be at the same
uniform values they had at the corresponding step during the compression. When the gas
volume returned to its initial value, all properties would be restored to their initial values
as well. The work done on the gas during the compression would equal the work done by
the gas during the expansion. If the work between the system and its surroundings were
delivered to, and received from, a frictionless pulleymass assembly, or the equivalent,
there would also be no net change in the surroundings. This process would be reversible.
INTERNALLY REVERSIBLE PROCESSES
In an irreversible process, irreversibilities are present within the system, its surroundings, or
both. A reversible process is one in which there are no internal or external irreversibilities.
internally reversible An internally reversible process is one in which there are no irreversibilities within the
process system. Irreversibilities may be located within the surroundings, however, as when there is
heat transfer between a portion of the boundary that is at one temperature and the surroundings
at another.
At every intermediate state of an internally reversible process of a closed system, all in-
tensive properties are uniform throughout each phase present. That is, the temperature,
pressure, specific volume, and other intensive properties do not vary with position. If there
were a spatial variation in temperature, say, there would be a tendency for a spontaneous
energy transfer by conduction to occur within the system in the direction of decreasing
temperature. For reversibility, however, no spontaneous processes can be present. From these
METHODOLOGY
UPDATE considerations it can be concluded that the internally reversible process consists of a series
of equilibrium states: It is a quasiequilibrium process. To avoid having two terms that refer
Using the internally re-
versible process concept, to the same thing, in subsequent discussions we will refer to any such process as an internally
we refine the definition of reversible process.
the thermal reservoir in- The use of the internally reversible process concept in thermodynamics is comparable to
troduced in Sec. 5.1.2. In the idealizations made in mechanics: point masses, frictionless pulleys, rigid beams, and so
subsequent discussions
on. In much the same way as these are used in mechanics to simplify an analysis and arrive
we assume that no inter-
nal irreversibilities are at a manageable model, simple thermodynamic models of complex situations can be obtained
present within a thermal through the use of internally reversible processes. Initial calculations based on internally
reservoir. That is, every reversible processes would be adjusted with efficiencies or correction factors to obtain
process of a thermal reasonable estimates of actual performance under various operating conditions. Internally
reservoir is internally
reversible processes are also useful in determining the best thermodynamic performance of
reversible.
systems.

5.3 Applying the Second Law to
Thermodynamic Cycles
Several important applications of the second law related to power cycles and refrigera-
tion and heat pump cycles are presented in this section. These applications further our
understanding of the implications of the second law and provide the basis for important
deductions from the second law introduced in subsequent sections. Familiarity with ther-
modynamic cycles is required, and we recommend that you review Sec. 2.6, where cy-
cles are considered from an energy, or first law, perspective and the thermal efficiency of
power cycles and coefficients of performance for refrigeration and heat pump cycles are
introduced.
5.3.1 Interpreting the KelvinPlanck Statement

Let us reconsider Eq. 5.1, the analytical form of the KelvinPlanck statement of the second
Wcycle 0 law. Equation 5.1 is employed in subsequent sections to obtain a number of significant
1single reservoir2 deductions. In each of these applications, the following idealizations are assumed: The ther-
mal reservoir and the portion of the surroundings with which work interactions occur are free
of irreversibilities. This allows the less than sign to be associated with irreversibilities within
the system of interest. The equal to sign is employed only when no irreversibilities of any
kind are present. (See box.)
5.3 Applying the Second Law to Thermodynamic Cycles 185
Thermal reservoir
Heat
transfer
System
Boundary
Figure 5.4 System undergoing a cycle while
Mass exchanging energy by heat transfer with a single
thermal reservoir.
A S S O C I AT I N G S I G N S W I T H T H E
K E LV I N P L A N C K S TAT E M E N T
Consider a system that undergoes a cycle while exchanging energy by heat transfer
with a single reservoir, as shown in Fig. 5.4. Work is delivered to, or received from,
the pulleymass assembly located in the surroundings. A flywheel, spring, or some
other device also can perform the same function. In subsequent applications of Eq. 5.1,
the irreversibilities of primary interest are internal irreversibilities. To eliminate extra-
neous factors in such applications, therefore, assume that these are the only irre-
versibilities present. Hence, the pulleymass assembly, flywheel, or other device to
which work is delivered, or from which it is received, is idealized as free of
irreversibilities. The thermal reservoir is also assumed free of irreversibilities.
To demonstrate the correspondence of the equal to sign of Eq. 5.1 with the ab-
sence of irreversibilities, consider a cycle operating as shown in Fig. 5.4 for which the
equality applies. At the conclusion of one cycle,
The system would necessarily be returned to its initial state.
Since Wcycle 0, there would be no net change in the elevation of the mass used
to store energy in the surroundings.
Since Wcycle Qcycle, it follows that Qcycle 0, so there also would be no net
change in the condition of the reservoir.
Thus, the system and all elements of its surroundings would be exactly restored to their
respective initial conditions. By definition, such a cycle is reversible. Accordingly, there
can be no irreversibilities present within the system or its surroundings. It is left as an
exercise to show the converse: If the cycle occurs reversibly, the equality applies. Since a
cycle is either reversible or irreversible, it follows that the inequality sign implies the
presence of irreversibilities, and the inequality applies whenever irreversibilities are
present.
5.3.2 Power Cycles Interacting with Two Reservoirs

A significant limitation on the performance of systems undergoing power cycles can be
brought out using the KelvinPlanck statement of the second law. Consider Fig. 5.5, which
shows a system that executes a cycle while communicating thermally with two thermal
reservoirs, a hot reservoir and a cold reservoir, and developing net work Wcycle. The thermal
Hot
reservoir QH
Boundary Wcycle = Q H Q C
Figure 5.5 System undergoing a power

Cold QC cycle while exchanging energy by heat transfer
reservoir with two reservoirs.
efficiency of the cycle is

Wcycle QC
METHODOLOGY h 1 (5.2)
UPDATE
QH QH
The energy transfers where QH is the amount of energy received by the system from the hot reservoir by heat
labeled on Fig 5.5 are transfer and QC is the amount of energy discharged from the system to the cold reservoir by
positive in the directions heat transfer.
indicated by the arrows.
If the value of QC were zero, the system of Fig. 5.5 would withdraw energy QH from the
hot reservoir and produce an equal amount of work, while undergoing a cycle. The thermal ef-
ficiency of such a cycle would have a value of unity (100%). However, this method of operation
would violate the KelvinPlanck statement and thus is not allowed. It follows that for any sys-
tem executing a power cycle while operating between two reservoirs, only a portion of the heat
transfer QH can be obtained as work, and the remainder, QC, must be discharged by heat trans-
fer to the cold reservoir. That is, the thermal efficiency must be less than 100%. In arriving at
this conclusion it was not necessary to (1) identify the nature of the substance contained within
the system, (2) specify the exact series of processes making up the cycle, or (3) indicate whether
the processes are actual processes or somehow idealized. The conclusion that the thermal effi-
ciency must be less than 100% applies to all power cycles whatever their details of operation.
This may be regarded as a corollary of the second law. Other corollaries follow.
CARNOT COROLLARIES. Since no power cycle can have a thermal efficiency of 100%, it
is of interest to investigate the maximum theoretical efficiency. The maximum theoretical
efficiency for systems undergoing power cycles while communicating thermally with two
thermal reservoirs at different temperatures is evaluated in Sec. 5.5 with reference to the
following two corollaries of the second law, called the Carnot corollaries.
The thermal efficiency of an irreversible power cycle is always less than the thermal
efficiency of a reversible power cycle when each operates between the same two
Carnot corollaries thermal reservoirs.
All reversible power cycles operating between the same two thermal reservoirs have the
same thermal efficiency.
A cycle is considered reversible when there are no irreversibilities within the system as it
undergoes the cycle and heat transfers between the system and reservoirs occur reversibly.
The idea underlying the first Carnot corollary is in agreement with expectations stemming
from the discussion of the second law thus far. Namely, the presence of irreversibilities dur-
ing the execution of a cycle is expected to exact a penalty. If two systems operating between
the same reservoirs each receive the same amount of energy QH and one executes a reversible
cycle while the other executes an irreversible cycle, it is in accord with intuition that the net
work developed by the irreversible cycle will be less, and it will therefore have the smaller
thermal efficiency.
The second Carnot corollary refers only to reversible cycles. All processes of a re-
versible cycle are perfectly executed. Accordingly, if two reversible cycles operating be-
tween the same reservoirs each receive the same amount of energy QH but one could
produce more work than the other, it could only be as a result of more advantageous se-
lections for the substance making up the system (it is conceivable that, say, air might be
better than water vapor) or the series of processes making up the cycle (nonflow processes
might be preferable to flow processes). This corollary denies both possibilities and indi-
cates that the cycles must have the same efficiency whatever the choices for the working
substance or the series of processes.
The two Carnot corollaries can be demonstrated using the KelvinPlanck statement of the
second law (see box).
D E M O N S T R AT I N G T H E C A R N O T C O R O L L A R I E S
The first Carnot corollary can be demonstrated using the arrangement of Fig. 5.6. A
reversible power cycle R and an irreversible power cycle I operate between the same
two reservoirs and each receives the same amount of energy QH from the hot reser-
voir. The reversible cycle produces work WR while the irreversible cycle produces
work WI. In accord with the conservation of energy principle, each cycle discharges
energy to the cold reservoir equal to the difference between QH and the work pro-
duced. Let R now operate in the opposite direction as a refrigeration (or heat pump)
cycle. Since R is reversible, the magnitudes of the energy transfers WR, QH, and QC
remain the same, but the energy transfers are oppositely directed, as shown by the
dashed lines on Fig. 5.6. Moreover, with R operating in the opposite direction, the hot
reservoir would experience no net change in its condition since it would receive QH
from R while passing QH to I.
The demonstration of the first Carnot corollary is completed by considering the
combined system shown by the dotted line on Fig. 5.6, which consists of the two cy-
cles and the hot reservoir. Since its parts execute cycles or experience no net change,
the combined system operates in a cycle. Moreover, the combined system exchanges
energy by heat transfer with a single reservoir: the cold reservoir. Accordingly, the com-
bined system must satisfy Eq. 5.1 expressed as
Wcycle 6 0 1single reservoir2
where the inequality is used because the combined system is irreversible in its opera-
tion since irreversible cycle I is one of its parts. Evaluating Wcycle for the combined
system in terms of the work amounts WI and WR, the above inequality becomes
WI WR 6 0
which shows that WI must be less than WR. Since each cycle receives the same energy
input, QH, it follows that I R and this completes the demonstration.
The second Carnot corollary can be demonstrated in a parallel way by considering
any two reversible cycles R1 and R2 operating between the same two reservoirs. Then,
letting R1 play the role of R and R2 the role of I in the previous development, a com-
bined system consisting of the two cycles and the hot reservoir may be formed that
must obey Eq. 5.1. However, in applying Eq. 5.1 to this combined system, the equal-
ity is used because the system is reversible in operation. Thus, it can be concluded that
WR1 WR2, and therefore, R1 R2. The details are left as an exercise.
Dotted line defines combined system

Hot reservoir
QH QH
WR
R I WI
Figure 5.6 Sketch for demonstrating that a

reversible cycle R is more efficient than an
QC = QH WR QC = QH WI irreversible cycle I when they operate between
Cold reservoir the same two reservoirs.

Interacting with Two Reservoirs
The second law of thermodynamics places limits on the performance of refrigeration and
heat pump cycles as it does for power cycles. Consider Fig. 5.7, which shows a system
undergoing a cycle while communicating thermally with two thermal reservoirs, a hot and a
cold reservoir. The energy transfers labeled on the figure are in the directions indicated by
the arrows. In accord with the conservation of energy principle, the cycle discharges energy
QH by heat transfer to the hot reservoir equal to the sum of the energy QC received by heat
transfer from the cold reservoir and the net work input. This cycle might be a refrigeration
cycle or a heat pump cycle, depending on whether its function is to remove energy QC from
the cold reservoir or deliver energy QH to the hot reservoir.
For a refrigeration cycle the coefficient of performance is
QC QC
b (5.3)
Wcycle QH QC
The coefficient of performance for a heat pump cycle is
QH QH
g (5.4)
Wcycle QH QC
As the net work input to the cycle Wcycle tends to zero, the coefficients of performance given
by Eqs. 5.3 and 5.4 approach a value of infinity. If Wcycle were identically zero, the system
of Fig. 5.7 would withdraw energy QC from the cold reservoir and deliver energy QC to the
hot reservoir, while undergoing a cycle. However, this method of operation would violate the
Clausius statement of the second law and thus is not allowed. It follows that these coeffi-
cients of performance must invariably be finite in value. This may be regarded as another
corollary of the second law. Further corollaries follow.
Hot QH =
reservoir QC + Wcycle
Boundary Wcycle = Q H Q C
Figure 5.7 System undergoing a refrigera-

Cold QC tion or heat pump cycle while exchanging energy
reservoir
by heat transfer with two reservoirs.

Urban Heat Islands Worrisome City planners are com-
bating heat islands. In
Warm blankets of pollution-laden air surround major cities. Chicago, the once gravel-
Sunlight-absorbing rooftops and expanses of pavement, to- roofed City Hall is now
gether with little greenery, conspire with other features of topped by a garden, with
city living to raise urban temperatures as much as 10F 20,000 vines, shrubs, and
above adjacent rural areas. Health-care professionals worry trees that absorb solar en-
about the impact of these heat islands, especially on the ergy without increasing the
elderly. roof temperature. The roof
Paradoxically, the hot exhaust from the air conditioners temperature in August is as
city dwellers use to keep cool also make sweltering much as 75F cooler than on
neighborhoods even hotter. Recent studies indicate that air- nearby buildings, city
conditioner exhaust accounts for as much as 2F of the urban sources report.
temperature rise. Vehicles and commercial activity also
contribute.
COROLLARIES FOR REFRIGERATION AND HEAT PUMP CYCLES. The maximum

theoretical coefficients of performance for systems undergoing refrigeration and heat pump
cycles while communicating thermally with two reservoirs at different temperatures are
evaluated in Sec. 5.5 with reference to the following corollaries of the second law:
The coefficient of performance of an irreversible refrigeration cycle is always less than
the coefficient of performance of a reversible refrigeration cycle when each operates
between the same two thermal reservoirs.
All reversible refrigeration cycles operating between the same two thermal reservoirs
have the same coefficient of performance.
By replacing the term refrigeration with heat pump, we obtain counterpart corollaries for
heat pump cycles.
The first of these corollaries agrees with expectations stemming from the discussion of the
second law thus far. To explore this, consider Fig. 5.8, which shows a reversible refrigeration
cycle R and an irreversible refrigeration cycle I operating between the same two reservoirs.
Each cycle removes the same energy QC from the cold reservoir. The net work input required
to operate R is WR, while the net work input for I is WI. Each cycle discharges energy by heat
transfer to the hot reservoir equal to the sum of QC and the net work input. The directions of
the energy transfers are shown by arrows on Fig. 5.8. The presence of irreversibilities during
the operation of a refrigeration cycle is expected to exact a penalty. If two refrigerators working
QH = QC + WR QH = QC + WI
Hot reservoir
WR R I WI
Figure 5.8 Sketch for demonstrating that a
reversible refrigeration cycle R has a greater co-
Cold reservoir efficient of performance than an irreversible cy-
QC QC cle I when they operate between the same two
reservoirs.
between the same reservoirs each receive an identical energy transfer from the cold reservoir,
QC, and one executes a reversible cycle while the other executes an irreversible cycle, we ex-
pect the irreversible cycle to require a greater net work input and thus to have a smaller
coefficient of performance. By a simple extension it follows that all reversible refrigeration
cycles operating between the same two reservoirs have the same coefficient of performance.
Similar arguments apply to the counterpart heat pump cycle statements.
These corollaries can be demonstrated formally using the KelvinPlanck statement of the
second law and a procedure similar to that employed for the Carnot corollaries. The details
are left as an exercise.
5.4 Defining the Kelvin Temperature Scale

The results of Sec. 5.3 establish theoretical upper limits on the performance of power,
refrigeration, and heat pump cycles communicating thermally with two reservoirs. Expres-
sions for the maximum theoretical thermal efficiency of power cycles and the maximum
theoretical coefficients of performance of refrigeration and heat pump cycles are developed
in Sec. 5.5 using the Kelvin temperature scale defined in the present section.
From the second Carnot corollary we know that all reversible power cycles operating
between the same two thermal reservoirs have the same thermal efficiency, regardless of the
nature of the substance making up the system executing the cycle or the series of processes.
Since the efficiency is independent of these factors, its value can be related only to the
nature of the reservoirs themselves. Noting that it is the difference in temperature between
the two reservoirs that provides the impetus for heat transfer between them, and thereby for
the production of work during the cycle, we reason that the efficiency depends only on the
temperatures of the two reservoirs.
From Eq. 5.2 it also follows that for such reversible power cycles the ratio of the heat
transfers QCQH depends only on the reservoir temperatures. That is
a b rev c1uC, uH 2
QC
(5.5)
QH cycle
where H and C denote the temperatures of the reservoirs and the function is for the present
unspecified. Note that the words rev cycle are added to this expression to emphasize that
it applies only to systems undergoing reversible cycles while operating between two thermal
reservoirs.
KELVIN SCALE
Equation 5.5 provides a basis for defining a thermodynamic temperature scale: a scale inde-
pendent of the properties of any substance. There are alternative choices for the function
Kelvin scale that lead to this end. The Kelvin scale is obtained by making a particularly simple choice,
namely, TCTH, where T is the symbol used to denote temperatures on the Kelvin scale.
With this, Eq. 5.5 becomes
a b
QC TC
(5.6)
QH rev TH
cycle
Thus, two temperatures on the Kelvin scale are in the same ratio as the values of the heat
transfers absorbed and rejected, respectively, by a system undergoing a reversible cycle while
communicating thermally with reservoirs at these temperatures.
5.4 Defining the Kelvin Temperature Scale 191
If a reversible power cycle were operated in the opposite direction as a refrigeration or

heat pump cycle, the magnitudes of the energy transfers QC and QH would remain the same,
but the energy transfers would be oppositely directed. Accordingly, Eq. 5.6 applies to each
type of cycle considered thus far, provided the system undergoing the cycle operates between
two thermal reservoirs and the cycle is reversible.
Equation 5.6 gives only a ratio of temperatures. To complete the definition of the Kelvin scale,
it is necessary to proceed as in Sec. 1.6 by assigning the value 273.16 K to the temperature at
the triple point of water. Then, if a reversible cycle is operated between a reservoir at 273.16 K
and another reservoir at temperature T, the two temperatures are related according to
T 273.16 a b
Q
(5.7)
Qtp rev
cycle
where Qtp and Q are the heat transfers between the cycle and reservoirs at 273.16 K and tem-
perature T, respectively. In the present case, the heat transfer Q plays the role of the ther-
mometric property. However, since the performance of a reversible cycle is independent of
the makeup of the system executing the cycle, the definition of temperature given by Eq. 5.7
depends in no way on the properties of any substance or class of substances.
In Sec. 1.6 we noted that the Kelvin scale has a zero of 0 K, and lower temperatures than
this are not defined. Let us take up these points by considering a reversible power cycle op-
erating between reservoirs at 273.16 K and a lower temperature T. Referring to Eq. 5.7, we
know that the energy rejected from the cycle by heat transfer Q would not be negative, so T
must be nonnegative. Equation 5.7 also shows that the smaller the value of Q, the lower the
value of T, and conversely. Accordingly, as Q approaches zero the temperature T approaches
zero. It can be concluded that a temperature of zero on the Kelvin scale is the lowest con-
ceivable temperature. This temperature is called the absolute zero, and the Kelvin scale is
called an absolute temperature scale.
INTERNATIONAL TEMPERATURE SCALE
When numerical values of the thermodynamic temperature are to be determined, it is not

possible to use reversible cycles, for these exist only in our imaginations. However, temper-
atures evaluated using the constant-volume gas thermometer introduced in Sec. 1.6 are iden-
tical to those of the Kelvin scale in the range of temperatures where the gas thermometer can
be used. Other empirical approaches can be employed for temperatures above and below the
range accessible to gas thermometry. The Kelvin scale provides a continuous definition of
temperature valid over all ranges and provides an essential connection between the several
empirical measures of temperature.
To provide a standard for temperature measurement taking into account both theoretical
and practical considerations, the International Temperature Scale (ITS) was adopted in 1927.
This scale has been refined and extended in several revisions, most recently in 1990. The
International Temperature Scale of 1990 (ITS-90) is defined in such a way that the temper-
ature measured on it conforms with the thermodynamic temperature, the unit of which is the
kelvin, to within the limits of accuracy of measurement obtainable in 1990. The ITS-90 is
based on the assigned values of temperature of a number of reproducible fixed points
(Table 5.1). Interpolation between the fixed-point temperatures is accomplished by formulas
that give the relation between readings of standard instruments and values of the ITS. In the
range from 0.65 to 5.0 K, ITS-90 is defined by equations giving the temperature as functions
of the vapor pressures of particular helium isotopes. The range from 3.0 to 24.5561 K is
based on measurements using a helium constant-volume gas thermometer. In the range from
13.8033 to 1234.93 K, ITS-90 is defined by means of certain platinum resistance ther-
mometers. Above 1234.9 K the temperature is defined using Plancks equation for blackbody
radiation and measurements of the intensity of visible-spectrum radiation.
TABLE 5.1 Defining Fixed Points of the International

Temperature Scale of 1990
T (K) Substancea Stateb
3 to 5 He Vapor pressure point
13.8033 e-H2 Triple point
17 e-H2 Vapor pressure point
20.3 e-H2 Vapor pressure point
24.5561 Ne Triple point
54.3584 O2 Triple point
83.8058 Ar Triple point
234.3156 Hg Triple point
273.16 H2O Triple point
302.9146 Ga Melting point
429.7485 In Freezing point
505.078 Sn Freezing point
692.677 Zn Freezing point
933.473 Al Freezing point
1234.93 Ag Freezing point
1337.33 Au Freezing point
1357.77 Cu Freezing point
a
He denotes 3He or 4He; e-H2 is hydrogen at the equilibrium
concentration of the ortho- and para-molecular forms.
b
Triple point: temperature at which the solid, liquid, and vapor
phases are in equilibrium. Melting point, freezing point: temperature,
at a pressure of 101.325 kPa, at which the solid and liquid phases are
in equilibrium.
Source: H. Preston-Thomas, The International Temperature Scale of
1990 (ITS-90), Metrologia 27, 310 (1990).
5.5 Maximum Performance

Measures for Cycles Operating
Between Two Reservoirs
The discussion of Sec. 5.3 continues in this section with the development of expressions for
the maximum thermal efficiency of power cycles and the maximum coefficients of perform-
ance of refrigeration and heat pump cycles in terms of reservoir temperatures evaluated on
the Kelvin scale. These expressions can be used as standards of comparison for actual power,
refrigeration, and heat pump cycles.
5.5.1 Power Cycles

The use of Eq. 5.6 in Eq. 5.2 results in an expression for the thermal efficiency of a system
undergoing a reversible power cycle while operating between thermal reservoirs at temper-
atures TH and TC. That is
TC
Carnot efficiency hmax 1 (5.8)
TH
which is known as the Carnot efficiency.

5.5 Maximum Performance Measures for Cycles Operating Between Two Reservoirs 193
Recalling the two Carnot corollaries, it should be evident that the efficiency given by
Eq. 5.8 is the thermal efficiency of all reversible power cycles operating between two reser-
voirs at temperatures TH and TC, and the maximum efficiency any power cycle can have while
operating between the two reservoirs. By inspection, the value of the Carnot efficiency in-
creases as TH increases and/or TC decreases.
Equation 5.8 is presented graphically in Fig. 5.9. The temperature TC used in constructing
the figure is 298 K in recognition that actual power cycles ultimately discharge energy by heat
transfer at about the temperature of the local atmosphere or cooling water drawn from a nearby
river or lake. Note that the possibility of increasing the thermal efficiency by reducing TC
below that of the environment is not practical, for maintaining TC lower than the ambient tem-
perature would require a refrigerator that would have to be supplied work to operate.
Figure 5.9 shows that the thermal efficiency increases with TH. Referring to segment ab
of the curve, where TH and are relatively low, we can see that increases rapidly as TH 1.0 b
increases, showing that in this range even a small increase in TH can have a large effect on
max
efficiency. Though these conclusions, drawn as they are from Fig. 5.9, apply strictly only to 0.5
systems undergoing reversible cycles, they are qualitatively correct for actual power cycles. a
The thermal efficiencies of actual cycles are observed to increase as the average tempera- 0
298 1000 2000 3000
ture at which energy is added by heat transfer increases and/or the average temperature at TH (K)
which energy is discharged by heat transfer is reduced. However, maximizing the thermal Figure 5.9 Carnot
efficiency of a power cycle may not be the only objective. In practice, other considerations efficiency versus TH, for
such as cost may be overriding. TC 298 K.
COMMENT. Conventional power-producing cycles have thermal efficiencies ranging up to

about 40%. This value may seem low, but the comparison should be made with an appropri-
ate limiting value and not 100%. for example. . . consider a system executing a power
cycle for which the average temperature of heat addition is 745 K and the average tempera-
ture at which heat is discharged is 298 K. For a reversible cycle receiving and discharging en-
ergy by heat transfer at these temperatures, the thermal efficiency given by Eq. 5.8 is 60%.
When compared to this value, an actual thermal efficiency of 40% does not appear to be so
low. The cycle would be operating at two-thirds of the theoretical maximum.
A more complete discussion of power cycles is provided in Chaps. 8 and 9.

Equation 5.6 is also applicable to reversible refrigeration and heat pump cycles operating
between two thermal reservoirs, but for these QC represents the heat added to the cycle from
the cold reservoir at temperature TC on the Kelvin scale and QH is the heat discharged to the
hot reservoir at temperature TH. Introducing Eq. 5.6 in Eq. 5.3 results in the following
expression for the coefficient of performance of any system undergoing a reversible
refrigeration cycle while operating between the two reservoirs
TC
bmax (5.9)
TH TC
Similarly, substituting Eq. 5.6 into Eq. 5.4 gives the following expression for the coefficient
of performance of any system undergoing a reversible heat pump cycle while operating
between the two reservoirs
TH
gmax (5.10)
TH TC
The development of Eqs. 5.9 and 5.10 is left as an exercise. Note that the temperatures used
to evaluate max and max must be absolute temperatures on the Kelvin or Rankine scale.
From the discussion of Sec. 5.3.3, it follows that Eqs. 5.9 and 5.10 are the maximum
coefficients of performance that any refrigeration and heat pump cycles can have while operating
between reservoirs at temperatures TH and TC. As for the case of the Carnot efficiency, these
expressions can be used as standards of comparison for actual refrigerators and heat pumps. A
more complete discussion of refrigeration and heat pump cycles is provided in Chap. 10.
5.5.3 Power Cycle, Refrigeration and Heat Pump Applications

In this section, three examples are provided that illustrate the use of the second law corollaries
of Secs. 5.3.2 and 5.3.3 together with Eqs. 5.8, 5.9, and 5.10, as appropriate.
The first example uses Eq. 5.8 to evaluate an inventors claim.
In the next example, we evaluate the coefficient of performance of a refrigerator and com-
pare it with the maximum theoretical value.
EXAMPLE 5.1 Evaluating a Power Cycle Performance Claim
An inventor claims to have developed a power cycle capable of delivering a net work output of 410 kJ for an energy input by
heat transfer of 1000 kJ. The system undergoing the cycle receives the heat transfer from hot gases at a temperature of 500 K
and discharges energy by heat transfer to the atmosphere at 300 K. Evaluate this claim.
SOLUTION
Known: A system operates in a cycle and produces a net amount of work while receiving and discharging energy by heat
transfer at fixed temperatures.
Find: Evaluate the claim that the cycle can develop 410 kJ of work for an energy input by heat of 1000 kJ.
Qin = 1000 kJ
500 K
Assumptions:
Power 1. The system is shown on the accompanying figure.

cycle W = 410 kJ
2. The hot gases and the atmosphere play the roles of hot and cold reservoirs, respectively.
300 K
Qout
Figure E5.1
Analysis: Inserting the values supplied by the inventor into Eq. 5.2, the cycle thermal efficiency is
0.41 141% 2
410 kJ
h
1000 kJ
The maximum thermal efficiency any power cycle can have while operating between reservoirs at TH 500 K and TC
300 K is given by Eq. 5.8.
0.40 140%2
TC 300 K
hmax 1
TH
1
500 K
Since the thermal efficiency of the actual cycle exceeds the maximum theoretical value, the claim cannot be valid.
The temperatures used in evaluating max must be in K or R.

5.5 Maximum Performance Measures for Cycles Operating Between Two Reservoirs 195
EXAMPLE 5.2 Evaluating Refrigerator Performance
By steadily circulating a refrigerant at low temperature through passages in the walls of the freezer compartment, a refrigerator
maintains the freezer compartment at 5C when the air surrounding the refrigerator is at 22C. The rate of heat transfer from
the freezer compartment to the refrigerant is 8000 kJ/h and the power input required to operate the refrigerator is 3200 kJ/h.
Determine the coefficient of performance of the refrigerator and compare with the coefficient of performance of a reversible
refrigeration cycle operating between reservoirs at the same two temperatures.
SOLUTION
Known: A refrigerator maintains a freezer compartment at a specified temperature. The rate of heat transfer from the
refrigerated space, the power input to operate the refrigerator, and the ambient temperature are known.
Find: Determine the coefficient of performance and compare with that of a reversible refrigerator operating between reser-
voirs at the same two temperatures.
Surroundings at 22C (295 K)

QH

Wcycle
= 3200 kJ/h
Assumptions:
1. The system shown on the accompanying figure is at steady state.

2. The freezer compartment and the surrounding air play the roles of cold
and hot reservoirs, respectively.
System
boundary

Q C = 8000 kJ/h
Freezer compartment
at 5C (268 K)
Figure E5.2
Analysis: Inserting the given operating data into Eq. 5.3, the coefficient of performance of the refrigerator is
#
QC 8000 kJ/h
b # 2.5
Wcycle 3200 kJ/h
Substituting values into Eq. 5.9 gives the coefficient of performance of a reversible refrigeration cycle operating between
reservoirs at TC 268 K and TH 295 K
TC 268 K
bmax
TH TC

295 K 268 K
9.9
The difference between the actual and maximum coefficients of performance suggests that there may be some potential
for improving the thermodynamic performance. This objective should be approached judiciously, however, for improved
performance may require increases in size, complexity, and cost.
In Example 5.3, we determine the minimum theoretical work input and cost for one day
of operation of an electric heat pump.
EXAMPLE 5.3 Evaluating Heat Pump Performance
A dwelling requires 5 10 5 kJ per day to maintain its temperature at 22C when the outside temperature is 10C. (a) If an elec-
tric heat pump is used to supply this energy, determine the minimum theoretical work input for one day of operation, in kJ.
SOLUTION
Known: A heat pump maintains a dwelling at a specified temperature. The energy supplied to the dwelling, the ambient
temperature, and the unit cost of electricity are known.
Find: Determine the minimum theoretical work required by the heat pump and the corresponding electricity cost.
Assumptions:
Heat pump Dwelling
at 22C 1. The system is shown on the accompanying figure.
Wcycle (295K)
QH 2. The dwelling and the outside air play the roles of hot and cold
reservoirs, respectively.
QC
at 10C (283 K)
Figure E5.3
Analysis:
(a) Using Eq. 5.4, the work for any heat pump cycle can be expressed as Wcycle QH. The coefficient of performance
of an actual heat pump is less than, or equal to, the coefficient of performance max of a reversible heat pump cycle when each
operates between the same two thermal reservoirs: max. Accordingly, for a given value of QH, and using Eq. 5.10 to
evaluate max, we get
QH
Wcycle
gmax
a1 bQ
TC
TH H
Inserting values
Wcycle a1 b 15 105 kJ2 2.03 104 kJ/day

283K
295K
The minimum theoretical work input is 2.03 104 kJ/day.
Note that the reservoir temperatures TC and TH must be expressed here in K.
Because of irreversibilities, an actual heat pump must be supplied more work than the minimum to provide the same heat-
ing effect. The actual daily cost could be substantially greater than the minimum theoretical cost.

5.6 Carnot Cycle
The Carnot cycle introduced in this section provides a specific example of a reversible power
cycle operating between two thermal reservoirs. Two other examples are provided in Chap. 9:
the Ericsson and Stirling cycles. Each of these cycles exhibits the Carnot efficiency given by
Eq. 5.8.
Carnot cycle In a Carnot cycle, the system executing the cycle undergoes a series of four internally
reversible processes: two adiabatic processes alternated with two isothermal processes.
5.6 Carnot Cycle 197
Figure 5.10 shows the pv diagram of a Carnot power cycle in which the system is a gas
in a pistoncylinder assembly. Figure 5.11 provides details of how the cycle is executed.
The piston and cylinder walls are nonconducting. The heat transfers are in the directions of
the arrows. Also note that there are two reservoirs at temperatures TH and TC, respec- p
2
tively, and an insulating stand. Initially, the pistoncylinder assembly is on the insulating
stand and the system is at state 1, where the temperature is TC. The four processes of the
cycle are
TC 3
Process 12: The gas is compressed adiabatically to state 2, where the temperature is TH. TH
Process 23: The assembly is placed in contact with the reservoir at TH. The gas expands 1
isothermally while receiving energy QH from the hot reservoir by heat transfer. 4
Process 34: The assembly is again placed on the insulating stand and the gas is allowed v
to continue to expand adiabatically until the temperature drops to TC. Figure 5.10 pv di-
Process 41: The assembly is placed in contact with the reservoir at TC. The gas is com- agram for a Carnot gas
pressed isothermally to its initial state while it discharges energy QC to the cold reser- power cycle.
voir by heat transfer.
For the heat transfer during Process 23 to be reversible, the difference between the gas tem-
perature and the temperature of the hot reservoir must be vanishingly small. Since the reser-
voir temperature remains constant, this implies that the temperature of the gas also remains
constant during Process 23. The same can be concluded for Process 41.
For each of the four internally reversible processes of the Carnot cycle, the work can be
represented as an area on Fig. 5.10. The area under the adiabatic process line 12 represents
the work done per unit of mass to compress the gas in this process. The areas under process
lines 23 and 34 represent the work done per unit of mass by the gas as it expands in these
processes. The area under process line 41 is the work done per unit of mass to compress
the gas in this process. The enclosed area on the pv diagram, shown shaded, is the net work
developed by the cycle per unit of mass.
The Carnot cycle is not limited to processes of a closed system taking place in a
pistoncylinder assembly. Figure 5.12 shows the schematic and accompanying pv diagram
of a Carnot cycle executed by water steadily circulating through a series of four intercon-
nected components that has features in common with the simple vapor power plant shown
in Fig. 4.14. As the water flows through the boiler, a change of phase from liquid to vapor
at constant temperature TH occurs as a result of heat transfer from the hot reservoir. Since
Adiabatic
expansion
Isothermal Isothermal
expansion compression
Adiabatic
compression
Gas
Insulating QH Insulating QC
stand stand
Hot reservoir, TH Cold reservoir, TC
Boundary
Process 12 Process 23 Process 34 Process 41

Figure 5.11 Carnot power cycle executed by a gas in a pistoncylinder
assembly.
Hot reservoir, TH
QH
4 Boiler 1
p
TH
Pump Turbine TC
Work Work 1
4
3 Condenser 2 TH
3 2
QC TC
Cold reservoir, TC
v
Figure 5.12 Carnot vapor power cycle.
temperature remains constant, pressure also remains constant during the phase change. The
steam exiting the boiler expands adiabatically through the turbine and work is developed. In
this process the temperature decreases to the temperature of the cold reservoir, TC, and there
is an accompanying decrease in pressure. As the steam passes through the condenser, a heat
transfer to the cold reservoir occurs and some of the vapor condenses at constant temperature
TC. Since temperature remains constant, pressure also remains constant as the water passes
through the condenser. The fourth component is a pump, or compressor, that receives a two-
phase liquidvapor mixture from the condenser and returns it adiabatically to the state at the
boiler entrance. During this process, which requires a work input to increase the pressure,
the temperature increases from TC to TH.
Carnot cycles also can be devised that are composed of processes in which a capacitor
is charged and discharged, a paramagnetic substance is magnetized and demagnetized, and
so on. However, regardless of the type of device or the working substance used, the Carnot
cycle always has the same four internally reversible processes: two adiabatic processes al-
ternated with two isothermal processes. Moreover, the thermal efficiency is always given
by Eq. 5.8 in terms of the temperatures of the two reservoirs evaluated on the Kelvin or
Rankine scale.
If a Carnot power cycle is operated in the opposite direction, the magnitudes of all energy
transfers remain the same but the energy transfers are oppositely directed. Such a cycle may
be regarded as a reversible refrigeration or heat pump cycle, for which the coefficients of
performance are given by Eqs. 5.9 and 5.10, respectively. A Carnot refrigeration or heat pump
p TH
cycle executed by a gas in a pistoncylinder assembly is shown in Fig. 5.13. The cycle consists
4
of the following four processes in series:
Process 12: The gas expands isothermally at TC while receiving energy QC from the cold
TC 3 reservoir by heat transfer.
Process 23: The gas is compressed adiabatically until its temperature is TH.
1
Process 34: The gas is compressed isothermally at TH while it discharges energy QH to
2 the hot reservoir by heat transfer.
v Process 41: The gas expands adiabatically until its temperature decreases to TC.
Figure 5.13 pv di-
agram for a Carnot gas It will be recalled that a refrigeration or heat pump effect can be accomplished in a cycle
refrigeration or heat only if a net work input is supplied to the system executing the cycle. In the case of the cycle
pump cycle. shown in Fig. 5.13, the shaded area represents the net work input per unit of mass.
Exercises: Things Engineers Think About 199
In this chapter, we motivate the need for and usefulness of The following checklist provides a study guide for this
the second law of thermodynamics, and provide the basis chapter. When your study of the text and end-of-chapter
for subsequent applications involving the second law in exercises has been completed you should be able to
Chaps. 6 and 7. Two equivalent statements of the second
law, the Clausius and KelvinPlanck statements, are intro-
throughout the chapter and understand each of the
duced together with several corollaries that establish the
related concepts. The subset of key concepts listed below
best theoretical performance for systems undergoing cycles
is particularly important in subsequent chapters.
while interacting with thermal reservoirs. The irreversibil-
ity concept is introduced and the related notions of give the KelvinPlanck statement of the second law,
irreversible, reversible, and internally reversible processes correctly interpreting the less than and equal to signs
are discussed. The Kelvin temperature scale is defined in Eq. 5.1.
and used to obtain expressions for the maximum perform- list several important irreversibilities.
ance measures of power, refrigeration, and heat pump cy- apply the corollaries of Secs. 5.3.2 and 5.3.3 together
cles operating between two thermal reservoirs. Finally, the with Eqs. 5.8, 5.9, and 5.10 to assess the performance of
Carnot cycle is introduced to provide a specific example power cycles and refrigeration and heat pump cycles.
of a reversible cycle operating between two thermal
describe the Carnot cycle.
reservoirs.
Kelvinplanck irreversibilities p. 180 internally reversible Kelvin scale p. 190

statement p. 178 internal and external process p. 184 Carnot efficiency p. 192
irreversible irreversibilities p. 181 Carnot corollaries p. 186
process p. 180
1. Explain how work might be developed when (a) Ti is less than Would you expect the power input to the compressor to be greater
T0 in Fig. 5.1a, (b) pi is less than p0 in Fig. 5.1b. in an internally reversible compression or an actual compression?
2. A system consists of an ice cube in a cup of tap water. The 9. If a window air conditioner were placed on a table in a room
ice cube melts and eventually equilibrium is attained. How might and operated, would the room temperature increase, decrease, or
work be developed as the ice and water come to equilibrium? remain the same?
3. Describe a process that would satisfy the conservation of 10. To increase the thermal efficiency of a reversible power
energy principle, but does not actually occur in nature. cycle operating between thermal reservoirs at temperatures TH
4. Referring to Fig. 2.3, identify internal irreversibilities associ- and TC, would it be better to increase TH or decrease TC by equal
ated with system A. Repeat for system B. amounts?
5. What are some of the principal irreversibilities present during 11. Electric power plants typically reject energy by heat transfer
operation of (a) an automobile engine, (b) a household refriger- to a body of water or the atmosphere. Would it be advisable to
ator, (c) a gas-fired water heater, (d) an electric water heater? reject heat instead to large blocks of ice maintained by a refrig-
eration system?
6. For the gearbox of Example 2.4, list the principal irre-
versibilities and classify them as internal or external. 12. Referring to Eqs. 5.9 and 5.10, how might the coefficients
of performance of refrigeration cycles and heat pumps be
7. Steam at a given state enters a turbine operating at steady state
increased?
and expands adiabatically to a specified lower pressure. Would
you expect the power output to be greater in an internally re- 13. Is it possible for the coefficient of performance of a refrig-
versible expansion or an actual expansion? eration cycle to be less than one? To be greater than one? Answer
the same questions for a heat pump cycle.
8. Air at a given state enters a compressor operating at steady state
and is compressed adiabatically to a specified higher pressure.
Exploring the Second Law more energy QC to the cold reservoir than cycle R. Dis-
5.1 A heat pump receives energy by heat transfer from the out- cuss the implications of this for actual power cycles.
side air at 0C and discharges energy by heat transfer to a (b) If each cycle develops the same net work, show that cycle
dwelling at 20C. Is this in violation of the Clausius statement I necessarily receives more energy QH from the hot
of the second law of thermodynamics? Explain. reservoir than cycle R. Discuss the implications of this
for actual power cycles.
5.2 Air as an ideal gas expands isothermally at 20C from a
volume of 1 m3 to 2 m3. During this process there is heat 5.11 Provide the details left to the reader in the demonstration
transfer to the air from the surrounding atmosphere, mod- of the second Carnot corollary given in Sec. 5.3.2.
eled as a thermal reservoir, and the air does work. Evaluate 5.12 Using the KelvinPlanck statement of the second law of
the work and heat transfer for the process, in kJ/kg. Is this thermodynamics, demonstrate the following corollaries:
process in violation of the second law of thermodynamics?
(a) The coefficient of performance of an irreversible refriger-
Explain.
ation cycle is always less than the coefficient of perform-
5.3 Complete the demonstration of the equivalence of the Clau- ance of a reversible refrigeration cycle when both exchange
sius and KelvinPlanck statements of the second law given in energy by heat transfer with the same two reservoirs.
Sec. 5.1 by showing that a violation of the KelvinPlanck (b) All reversible refrigeration cycles operating between the
statement implies a violation of the Clausius statement. same two reservoirs have the same coefficient of
5.4 An inventor claims to have developed a device that under- performance.
goes a thermodynamic cycle while communicating thermally (c) The coefficient of performance of an irreversible heat pump
with two reservoirs. The system receives energy QC from the cycle is always less than the coefficient of performance of
cold reservoir and discharges energy QH to the hot reservoir a reversible heat pump cycle when both exchange energy
while delivering a net amount of work to its surroundings. by heat transfer with the same two reservoirs.
There are no other energy transfers between the device and its (d) All reversible heat pump cycles operating between the
surroundings. Using the second law of thermodynamics, eval- same two reservoirs have the same coefficient of per-
uate the inventors claim. formance.
5.5 A hot thermal reservoir is separated from a cold thermal 5.13 Before introducing the temperature scale now known as
reservoir by a cylindrical rod insulated on its lateral surface. the Kelvin scale, Kelvin suggested a logarithmic scale in which
Energy transfer by conduction between the two reservoirs takes the function of Eq. 5.5 takes the form
place through the rod, which remains at steady state. Using the
c exp uC exp uH
KelvinPlanck statement of the second law, demonstrate that
such a process is irreversible.
where H and C denote, respectively, the temperatures of the
5.6 Methane gas within a pistoncylinder assembly is com- hot and cold reservoirs on this scale.
pressed in a quasiequilibrium process. Is this process internally
(a) Show that the relation between the Kelvin temperature T
reversible? Is this process reversible?
and the temperature on the logarithmic scale is
5.7 Water within a pistoncylinder assembly cools isothermally
at 120C from saturated vapor to saturated liquid while inter- u ln T
C
acting thermally with its surroundings at 20C. Is the process where C is a constant.
internally reversible? Is it reversible? Discuss. (b) On the Kelvin scale, temperatures vary from 0 to
.
5.8 Complete the discussion of the KelvinPlanck statement of Determine the range of temperature values on the loga-
the second law in Sec. 5.3.1 by showing that if a system un- rithmic scale.
dergoes a thermodynamic cycle reversibly while communicat- (c) Obtain an expression for the thermal efficiency of any sys-
ing thermally with a single reservoir, the equality in Eq. 5.1 tem undergoing a reversible power cycle while operating
applies. between reservoirs at temperatures H and C on the loga-
5.9 A power cycle I and a reversible power cycle R operate rithmic scale.
between the same two reservoirs, as shown in Fig. 5.6. Cycle I 5.14 Demonstrate that the gas temperature scale (Sec. 1.6) is
has a thermal efficiency equal to two-thirds of that for cycle R. identical to the Kelvin temperature scale.
Using the Kelvin-Planck statement of the second law, prove
5.15 To increase the thermal efficiency of a reversible power
that cycle I must be irreversible.
cycle operating between reservoirs at TH and TC, would you
5.10 A reversible power cycle R and an irreversible power increase TH while keeping TC constant, or decrease TC while
cycle I operate between the same two reservoirs. keeping TH constant? Are there any natural limits on the in-
(a) If each cycle receives the same amount of energy QH from crease in thermal efficiency that might be achieved by such
the hot reservoir, show that cycle I necessarily discharges means?
5.16 Two reversible power cycles are arranged in series. The (c) Letting T H TC T0, plot QHQH versus THT0 for
first cycle receives energy by heat transfer from a reservoir at T C T0 0.85, 0.9, and 0.95, and versus T C T0 for TH T0
temperature TH and rejects energy to a reservoir at an inter- 2, 3, and 4.
mediate temperature T. The second cycle receives the energy 5.22 Figure P5.22 shows a system consisting of a power cycle
rejected by the first cycle from the reservoir at temperature T driving a heat pump. At steady state, the power cycle receives
and rejects energy to a reservoir at temperature TC lower than #
Qs by heat# transfer at Ts from the high-temperature source and
#
T. Derive an expression for the intermediate temperature T in delivers Q1 to a dwelling at Td. The heat pump receives Q0
terms of TH and TC when #
from the outdoors at T0, and delivers Q2 to the dwelling.
(a) the net work of the two power cycles is equal.
(b) the thermal efficiencies of the two power cycles are equal.
5.17 If the thermal efficiency of a reversible power cycle oper-
Q1 Dwelling Q2
ating between two reservoirs is denoted by max, develop an ex- at Td
pression in terms of max for the coefficient of performance of
(a) a reversible refrigeration cycle operating between the same
two reservoirs.
Qs Heat pump
(b) a reversible heat pump operating between the same two Air
reservoirs. Power cycle
Ts
5.18 The data listed below are claimed for a power cycle op-
Driveshaft Q0
erating between reservoirs at 527C and 27C. For each case,
Fuel Outdoors at T0
determine if any principles of thermodynamics would be
violated. Figure P5.22
(a) QH 700 kJ, Wcycle 400 kJ, QC 300 kJ.
(b) QH 640 kJ, Wcycle 400 kJ, QC 240 kJ.
(c) QH 640 kJ, Wcycle 400 kJ, QC 200 kJ. (a) Obtain an expression for the maximum # theoretical value
of the performance parameter 1Q1
Q2 2 Qs in terms of
# #
5.19 A refrigeration cycle operating between two reservoirs re-
the temperature ratios TsTd and T0Td.
ceives energy QC from a cold reservoir at TC 280 K and
(b) Plot the result of part (a) versus TsTd ranging from 2 to
rejects energy QH to a hot reservoir at TH 320 K. For each
4 for T0Td 0.85, 0.9, and 0.95.
of the following cases determine whether the cycle operates
reversibly, irreversibly, or is impossible: Power Cycle Applications
(a) QC 1500 kJ, Wcycle 150 kJ. 5.23 A power cycle operates between a reservoir at tempera-
(b) QC 1400 kJ, QH 1600 kJ. ture T and a lower-temperature reservoir at 280 K. At steady
(c) QH 1600 kJ, Wcycle 400 kJ. state, the cycle develops 40 kW of power while rejecting 1000
(d) 5. kJ/min of energy by heat transfer to the cold reservoir. Deter-
5.20 A reversible power cycle receives QH from a hot reservoir mine the minimum theoretical value for T, in K.
at temperature TH and rejects energy by heat transfer to the 5.24 A certain reversible power cycle has the same thermal ef-
surroundings at temperature T0. The work developed by the ficiency for hot and cold reservoirs at 1000 and 500 K, re-
power cycle is used to drive a refrigeration cycle that removes spectively, as for hot and cold reservoirs at temperature T and
QC from a cold reservoir at temperature TC and discharges 1000 K. Determine T, in K.
energy by heat transfer to the same surroundings at T0. 5.25 A reversible power cycle whose thermal efficiency is 50%
(a) Develop an expression for the ratio QCQH in terms of the operates between a reservoir at 1800 K and a reservoir at a
temperature ratios THT0 and TCT0. lower temperature T. Determine T, in K.
(b) Plot QCQH versus THT0 for TCT0 0.85, 0.9, and 0.95, 5.26 An inventor claims to have developed a device that exe-
and versus TCT0 for THT0 2, 3, and 4. cutes a power cycle while operating between reservoirs at 800
5.21 A reversible power cycle receives energy QH from a reser- and 350 K that has a thermal efficiency of (a) 56%, (b) 40%.
voir at temperature TH and rejects QC to a reservoir at tem- Evaluate the claim for each case.
perature TC. The work developed by the power cycle is used 5.27 At steady state, a cycle develops a power output of 10 kW
to drive a reversible heat pump that removes energy QC from for heat addition at a rate of 10 kJ per cycle of operation from
a reservoir at temperature T C and rejects energy QH to a reser- a source at 1500 K. Energy is rejected by heat transfer to cool-
voir at temperature T H . ing water at 300 K. Determine the minimum theoretical num-
(a) Develop an expression for the ratio QHQH in terms of the ber of cycles required per minute.
temperatures of the four reservoirs. 5.28 At steady state, a power cycle having a thermal efficiency of
(b) What must be the relationship of the temperatures TH, TC, 38% generates 100 MW of electricity while discharging energy
T C, and T H for QHQH to exceed a value of unity? by heat transfer to cooling water at an average temperature
of 70F. The average temperature of the steam passing through 5.32 The preliminary design of a space station calls for a power
the boiler is 900F. Determine cycle that at steady state receives energy by heat transfer at
(a) the rate at which energy is discharged to the cooling water, TH 600 K from a nuclear source and rejects energy to space
in Btu /h. by thermal radiation according to Eq. 2.33. For the radiative
(b) the minimum theoretical rate at which energy could be dis- surface, the temperature is TC, the emissivity is 0.6, and the
charged to the cooling water, in Btu/h. Compare with the surface receives no radiation from any source. The thermal ef-
actual rate and discuss. ficiency of the power cycle is one-half that of a reversible
power cycle operating between reservoirs at TH and TC.
5.29 Ocean temperature energy conversion (OTEC) power #
plants generate power by utilizing the naturally occurring de- (a) For TC 400 K, determine Wcycle A, the net power de-
crease with depth of the temperature of ocean water. Near veloped per unit of radiator surface area, in kW/m2, and
Florida, the ocean surface temperature is 27C, while at a depth the thermal
# efficiency.
of 700 m the temperature is 7C. (b) Plot Wcycle A and the thermal efficiency
# versus TC, and de-
termine the maximum value of Wcycle A.
(a) Determine the maximum thermal efficiency for any power
(c) Determine
# the range of temperatures TC, in K, for which
cycle operating between these temperatures.
Wcycle A is within 2 percent of the maximum value ob-
(b) The thermal efficiency of existing OTEC plants is ap-
tained in part (b).
proximately 2 percent. Compare this with the result of part
(a) and comment. The Stefan-Boltzmann constant is 5.67 108 Wm2 K4.
5.30 During January, at a location in Alaska winds at 30C

Refrigeration and Heat Pump Cycle Applications
can be observed. Several meters below ground the temperature
remains at 13C, however. An inventor claims to have devised 5.33 An inventor claims to have developed a refrigeration cy-
a power cycle exploiting this situation that has a thermal cle that requires a net power input of 1.2 kW to remove
efficiency of 10%. Discuss this claim. 25,000 kJ/h of energy by heat transfer from a reservoir at
30C and discharge energy by heat transfer to a reservoir at
5.31 Figure P5.31 shows a system for collecting solar radiation
20C. There are no other energy transfers with the surround-
and utilizing it for the production of electricity by a power cy-
ings. Evaluate this claim.
cle. The solar collector receives solar radiation at the rate of
0.315 kW per m2 of area and provides energy to a storage unit 5.34 Determine if a tray of ice cubes could remain frozen when
whose temperature remains constant at 220C. The power cycle placed in a food freezer having a coefficient of performance
receives energy by heat transfer from the storage unit, generates of 9 operating in a room where the temperature is 32C (90F).
electricity at the rate 0.5 MW, and discharges energy by heat 5.35 The refrigerator shown in Fig. P5.35 operates at steady
transfer to the surroundings at 20C. For operation at steady state, state with a coefficient of performance of 4.5 and a power in-
put of 0.8 kW. Energy is rejected from the refrigerator to the
surroundings at 20C by heat transfer from metal coils whose
average surface temperature is 28C. Determine
(a) the rate energy is rejected, in kW.
(b) the lowest theoretical temperature inside the refrigerator, in
Solar radiation K.
Solar collector (c) the maximum theoretical power, in kW, that could be de-
veloped by a power cycle operating between the coils and
Surroundings at 20C
Area Refrigerator
= 4.5 Surroundings, 20C
Storage +
Power cycle
unit at Coils, 28C
220C
QH
Figure P5.31
(a) determine the minimum theoretical collector area required,

in m2.
(b) determine the collector area required, in m2, as a function
of the thermal efficiency and the collector efficiency, de-
fined as the fraction of the incident energy that is stored.
Plot the collector area versus for collector efficiencies +
equal to 1.0, 0.75, and 0.5. 0.8 kW Figure P5.35
the surroundings. Would you recommend making use of energy by heat transfer to the surroundings, which are at 20C.
this opportunity for developing power? Determine the power input to the refrigerator and compare with
5.36 Determine the minimum theoretical power, in W, re- the power input required by a reversible refrigeration cycle op-
quired at steady state by a refrigeration system to maintain a erating between reservoirs at these two temperatures.
cryogenic sample at 126C in a laboratory at 21C, if energy 5.45 By supplying energy to a dwelling at a rate of 25,000 kJ/h,
leaks by heat transfer to the sample from its surroundings at a a heat pump maintains the temperature of the dwelling at 20C
rate of 900 W. when the outside air is at 10C. If electricity costs 8 cents
5.37 For each kW of power input to an ice maker at steady state, per kW # h, determine the minimum theoretical operating cost
determine the maximum rate that ice can be produced, in kg/h, for each day of operation.
from liquid water at 0C. Assume that 333 kJ/kg of energy Carnot Cycle Applications
must be removed by heat transfer to freeze water at 0C, and
that the surroundings are at 20C. 5.46 Two kilograms of water execute a Carnot power cycle.
During the isothermal expansion, the water is heated until it is
5.38 At steady state, a refrigeration cycle removes 18,000 kJ/h a saturated vapor from an initial state where the pressure is 40
of energy by heat transfer from a space maintained at 40C bar and the quality is 15%. The vapor then expands adiabati-
and discharges energy by heat transfer to surroundings at 20C. cally to a pressure of 1.5 bar while doing 491.5 kJ/kg of work.
If the coefficient of performance of the cycle is 25 percent of
that of a reversible refrigeration cycle operating between ther- (a) Sketch the cycle on pv coordinates.
mal reservoirs at these two temperatures, determine the power (b) Evaluate the heat and work for each process, in kJ.
input to the cycle, in kW. (c) Evaluate the thermal efficiency.
5.39 A refrigeration cycle having a coefficient of performance 5.47 One kilogram of air as an ideal gas executes a Carnot
of 3 maintains a computer laboratory at 18C on a day when power cycle having a thermal efficiency of 60%. The heat trans-
the outside temperature is 30C. The thermal load at steady fer to the air during the isothermal expansion is 40 kJ. At the
state consists of energy entering through the walls and win- end of the isothermal expansion, the pressure is 5.6 bar and
dows at a rate of 30,000 kJ/h and from the occupants, com- the volume is 0.3 m3. Determine
puters, and lighting at a rate of 6000 kJ/h. Determine the power (a) the maximum and minimum temperatures for the cycle, in
required by this cycle and compare with the minimum theo- K.
retical power required for any refrigeration cycle operating (b) the pressure and volume at the beginning of the isother-
under these conditions, each in kW. mal expansion in bar and m3, respectively.
5.40 A heat pump operating at steady state is driven by a 1-kW (c) the work and heat transfer for each of the four processes,
electric motor and provides heating for a building whose inte- in kJ.
rior is to be kept at 20C. On a day when the outside temper- (d) Sketch the cycle on pv coordinates.
ature is 0C and energy is lost through the walls and roof at a 5.48 The pressurevolume diagram of a Carnot power cycle ex-
rate of 60,000 kJ/h, would the heat pump suffice? ecuted by an ideal gas with constant specific heat ratio k is
5.41 A heat pump maintains a dwelling at 20C when the out- shown in Fig. P5.48. Demonstrate that
side temperature is 0C. The heat transfer rate through the walls (a) V4V2 V1V3.
and roof is 3000 kJ/h per degree temperature difference be- (b) T2T3 ( p2p3)(k1)k.
tween the inside and outside. Determine the minimum theo- (c) T2T3 (V3V2)k1.
retical power required to drive the heat pump, in kW.
5.42 A building for which the heat transfer rate through the p
walls and roof is 400 W per degree temperature difference
between the inside and outside is to be maintained at 20C. 1
For a day when the outside temperature is 4C, determine the
power required at steady state, kW, to heat the building using Isothermal
electrical resistance elements and compare with the minimum
theoretical power that would be required by a heat pump. Re-
peat the comparison using typical manufacturers data for the 2
heat pump coefficient of performance. Q41 = 0
5.43 Plot the coefficient of performance max given by Eq. 5.9
for TH 298 K versus TC ranging between 235 and 298 K. Dis- 4 Q23 = 0
cuss the practical implications of the decrease in the coefficient
of performance with decreasing temperature TC.
Isothermal
5.44 At steady state, a refrigerator whose coefficient of per- 3
formance is 3 removes energy by heat transfer from a freezer
compartment at 0C at the rate of 6000 kJ/h and discharges v Figure P5.48
5.49 One-tenth kilogram of air as an ideal gas with k 1.4 at 27C to a final volume of 0.01 m3. Using the results of
executes a Carnot refrigeration cycle, as shown in Fig. 5.13. Prob. 5.64 as needed, determine
The isothermal expansion occurs at 23C with a heat trans- (a) the pressure, in kPa, at each of the four principal states.
fer to the air of 3.4 kJ. The isothermal compression occurs (b) the work, in kJ, for each of the four processes.Design

5.1D Write a paper outlining the contributions of Carnot, Clau- technologies that might lead to appreciable thermal efficiency
sius, Kelvin, and Planck to the development of the second law gains.
of thermodynamics. In what ways did the now-discredited 5.6D Abandoned lead mines near Park Hills, Missouri are filled
caloric theory influence the development of the second law as with an estimated 2.5 108 m3 of water at an almost constant
we know it today? What is the historical basis for the idea of temperature of 14C. How might this resource be exploited for
a perpetual motion machine of the second kind that is some- heating and cooling of the towns dwellings and commercial
times used to state the second law? buildings? A newspaper article refers to the water-filled mines
5.2D The heat transfer rate through the walls and roof of a build- as a free source of heating and cooling. Discuss this charac-
ing is 3570 kJ/h per degree temperature difference between the terization.
inside and outside. For outdoor temperatures ranging from 15 to 5.7D The Minto Wheel is a power-producing device activated
20C, make a comparison of the daily cost of maintaining the by evaporating and condensing a working substance. The only
building at 20C by means of an electric heat pump, direct elec- energy input would be from a waste heat or solar source. Write
tric resistance heating, and a conventional gas-fired furnace. a paper explaining the operating principles of the device. In-
5.3D To maintain the passenger compartment of an automobile dicate whether the Minto wheel operates as a thermodynamic
traveling at 13.4 m/s at 21C when the surrounding air tem- power cycle, and if so give the range of thermal efficiencies
perature is 32C, the vehicles air conditioner removes 5.275 kW that might be achieved. Evaluate propane as a working sub-
by heat transfer. Estimate the amount of engine horsepower stance and suggest an alternative. How would the wheel di-
required to drive the air conditioner. Referring to typical ameter and the volumes of the containers holding the working
manufacturers data, compare your estimate with the actual substance affect performance? Are there any practical appli-
horsepower requirement. Discuss the relationship between the cations for such a device? Discuss.
initial unit cost of an automobile air-conditioning system and 5.8D Figure P5.8D shows a device for pumping water without
its operating cost. the use of an electrical or fuel input. The container (1) holds
5.4D Prepare a memorandum discussing alternative means for a suitable liquid working substance separated from a quantity
achieving the required cooling of a 1000 MW power plant lo- of air by a flexible bladder (2). During the daytime, heat trans-
cated on the river of Problem 5.38. Discuss environmental fer from the warm surroundings vaporizes some of the liquid,
issues related to each of your alternatives. thereby displacing the bladder and forcing air through the pipe
5.5D Figure P5.5D shows that the typical thermal efficiency of (3) into the top of the chamber (4) below. As the air enters the
U.S. power plants increased rapidly from 1925 to 1960, but lower chamber, it pushes against the top of the piston (5). The
has increased only gradually since then. Discuss the most displacement of the piston pumps water from the chamber
important factors contributing to this plateauing of thermal through the lift pipe (6) and into the collection tank (7). At
efficiency and the most promising near-term and long-term night, heat transfer to the cooler surroundings causes the va-
por to condense, thereby restoring the bladder to its original
position and recharging the lower chamber. Critically evaluate
40
this device for pumping water. Specify a suitable working sub-
stance. Does the device operate in a thermodynamic power cy-
cle? If so, estimate the range of thermal efficiencies that might
be expected. Propose a means for pumping water with this type
Thermal efficiency, %
of device more than once a day. Write a report of your findings.

30
5.9D A method for generating electricity using gravitational
energy is described in U.S. Patent No. 4,980,572. The method
employs massive spinning wheels located underground that
serve as the prime mover of an alternator for generating elec-
tricity. Each wheel is kept in motion by torque pulses trans-
20 mitted to it via a suitable mechanism from vehicles passing
overhead. What practical difficulties might be encountered in
0 implementing such a method for generating electricity? If the
1925 1935 1945 1955 1965 1975 1985 vehicles are trolleys on an existing urban transit system, might
Year Figure P5.5D this be a cost-effective way to generate electricity? If the
1 Working substance
2 7
Trapped air
Valve
1. Container
2. Flexible bladder
6 3. Air pipe
4. Chamber with one-way (check) valve
3 5. Piston
6. Water pipe with one-way valve
7. Water collection tank
5
4
One-way valve
Figure P5.8D
vehicle motion were sustained by the electricity generated, been inspired by such an analysis. Does the concept have
would this be an example of a perpetual motion machine? scientific merit? Engineering merit? Discuss.
Discuss. 5.11D Urban Heat Islands Worrisome (see box Sec. 5.3). In-
5.10D A technical article considers hurricanes as an example vestigate adverse health conditions that might be exacerbated
of a natural Carnot engine (K. A. Emmanuel, Toward a Gen- for persons living in urban heat islands. Write a report in-
eral Theory of Hurricanes, American Scientist, 76, 371379, cluding at least three references.
1988). A subsequent U.S. Patent (No. 4,885,913) is said to have
C
H
A
P
T
6 R
E
Using Entropy
E N G I N E E R I N G C O N T E X T Up to this point, our study of the sec-

ond law has been concerned primarily with what it says about systems undergoing
thermodynamic cycles. In this chapter means are introduced for analyzing systems from
the second law perspective as they undergo processes that are not necessarily cycles.
chapter objective The property entropy plays a prominent part in these considerations. The objective of the
present chapter is to introduce entropy and show its use for thermodynamic analysis.
The word energy is so much a part of the language that you were undoubtedly familiar
with the term before encountering it in early science courses. This familiarity probably
facilitated the study of energy in these courses and in the current course in engineering
thermodynamics. In the present chapter you will see that the analysis of systems from a
second law perspective is conveniently accomplished in terms of the property entropy.
Energy and entropy are both abstract concepts. However, unlike energy, the word entropy is
seldom heard in everyday conversation, and you may never have dealt with it quantitatively
before. Energy and entropy play important roles in the remaining chapters of this book.

6.1 Introducing Entropy
Corollaries of the second law are developed in Chap. 5 for systems undergoing cycles while
communicating thermally with two reservoirs, a hot reservoir and a cold reservoir. In the
present section a corollary of the second law known as the Clausius inequality is introduced
that is applicable to any cycle without regard for the body, or bodies, from which the cycle
receives energy by heat transfer or to which the cycle rejects energy by heat transfer. The
Clausius inequality provides the basis for introducing two ideas instrumental for analyses of
both closed systems and control volumes from a second law perspective: the property entropy
(Sec. 6.2) and the entropy balance (Secs. 6.5 and 6.6).
The Clausius inequality states that for any thermodynamic cycle
a T b
dQ
Clausius inequality ~ 0 (6.1)
b
where Q represents the heat transfer at a part of the system boundary during a portion of the
cycle, and T is the absolute temperature at that part of the boundary. The subscript b serves
as a reminder that the integrand is evaluated at the boundary of the system executing the cycle.
The symbol indicates that the integral is to be performed over all parts of the boundary and
206
6.1 Introducing Entropy 207
over the entire cycle. The equality and inequality have the same interpretation as in the
KelvinPlanck statement: the equality applies when there are no internal irreversibilities as
the system executes the cycle, and the inequality applies when internal irreversibilities are
present. The Clausius inequality can be demonstrated using the KelvinPlanck statement of
the second law (see box).
DEVELOPING THE CLAUSIUS INEQUALITY
The Clausius inequality can be demonstrated using the arrangement of Fig. 6.1. A sys-
tem receives energy Q at a location on its boundary where the absolute temperature
is T while the system develops work W. In keeping with our sign convention for heat
transfer, the phrase receives energy Q includes the possibility of heat transfer from
the system. The energy Q is received from (or absorbed by) a thermal reservoir at
Tres. To ensure that no irreversibility is introduced as a result of heat transfer between
the reservoir and the system, let it be accomplished through an intermediary system
that undergoes a cycle without irreversibilities of any kind. The cycle receives energy
Q from the reservoir and supplies Q to the system while producing work W. From
the definition of the Kelvin scale (Eq. 5.6), we have the following relationship between
the heat transfers and temperatures:
a b
dQ dQ
(a)
Tres T b
As temperature may vary, a multiplicity of such reversible cycles may be required.
Consider next the combined system shown by the dotted line on Fig. 6.1. An en-
ergy balance for the combined system is
dEC dQ dWC
where WC is the total work of the combined system, the sum of W and W, and dEC
denotes the change in energy of the combined system. Solving the energy balance for
WC and using Eq. (a) to eliminate Q from the resulting expression yields
dWC Tres a b dEC

dQ
T b
Now, let the system undergo a single cycle while the intermediary system undergoes
one or more cycles. The total work of the combined system is
T res a b dE aTb
dQ 0 dQ
WC ~ ~ C Tres ~ (b)
T b b
Since the reservoir temperature is constant, Tres can be brought outside the integral. The
term involving the energy of the combined system vanishes because the energy change
for any cycle is zero. The combined system operates in a cycle because its parts exe-
cute cycles. Since the combined system undergoes a cycle and exchanges energy by
heat transfer with a single reservoir, Eq. 5.1 expressing the KelvinPlanck statement
of the second law must be satisfied. Using this, Eq. (b) reduces to give Eq. 6.1, where
the equality applies when there are no irreversibilities within the system as it executes
the cycle and the inequality applies when internal irreversibilities are present. This in-
terpretation actually refers to the combination of system plus intermediary cycle. How-
ever, the intermediary cycle is regarded as free of irreversibilities, so the only possible
site of irreversibilities is the system alone.
208 Chapter 6 Using Entropy
Reservoir at Tres
Q
Intermediary
cycle
Combined
system W
boundary
Q
T
System W
Figure 6.1 Illustration used to develop the
System boundary Clausius inequality.
Equation 6.1 can be expressed equivalently as
aTb
dQ
~ scycle (6.2)
b
where cycle can be viewed as representing the strength of the inequality. The value of cycle
is positive when internal irreversibilities are present, zero when no internal irreversibilities
are present, and can never be negative. In summary, the nature of a cycle executed by a sys-
tem is indicated by the value for cycle as follows:
scycle 0 no irreversibilities present within the system
scycle 7 0 irreversibilities present within the system
scycle 6 0 impossible
Accordingly, cycle is a measure of the effect of the irreversibilities present within the system
executing the cycle. This point is developed further in Sec. 6.5, where cycle is identified as
the entropy produced (or generated) by internal irreversibilities during the cycle.
C
2

6.2 Defining Entropy Change
A quantity is a property if, and only if, its change in value between two states is independ-
ent of the process (Sec. 1.3). This aspect of the property concept is used in the present sec-
B
tion together with Eq. 6.2 to introduce entropy.
A Two cycles executed by a closed system are represented in Fig. 6.2. One cycle consists
of an internally reversible process A from state 1 to state 2, followed by internally reversible
1 process C from state 2 to state 1. The other cycle consists of an internally reversible process
Figure 6.2 Two in- B from state 1 to state 2, followed by the same process C from state 2 to state 1 as in the
ternally reversible cycles. first cycle. For the first cycle, Eq. 6.2 takes the form
a b
a b scycle
2 dQ 1 dQ 0
(6.3a)
1 T A 2 T C
and for the second cycle
a b
a b scycle
2 dQ 1 dQ 0
(6.3b)
1 T B 2 T C
In writing Eqs. 6.3, the term cycle has been set to zero since the cycles are composed of
internally reversible processes.
6.3 Retrieving Entropy Data 209
When Eq. 6.3b is subtracted from Eq. 6.3a
a b a b
2 dQ 2 dQ
1 T A 1 T B
This shows that the integral of QT is the same for both processes. Since A and B are ar-
bitrary, it follows that the integral of QT has the same value for any internally reversible
process between the two states. In other words, the value of the integral depends on the end
states only. It can be concluded, therefore, that the integral represents the change in some
property of the system.
Selecting the symbol S to denote this property, which is called entropy, its change is
given by
definition of entropy
S2 S1 a b int
2 dQ
(6.4a) change
1 T rev
where the subscript int rev is added as a reminder that the integration is carried out for
any internally reversible process linking the two states. Equation 6.4a is the definition of
entropy change. On a differential basis, the defining equation for entropy change takes
the form
dS a b int
dQ
(6.4b)
T rev
Entropy is an extensive property.

The SI unit for entropy is J/K. However, in this book it is convenient to work in terms units for entropy
of kJ/K. Units in SI for specific entropy are kJ/kg # K for s and kJ/kmol # K for s.
Since entropy is a property, the change in entropy of a system in going from one state to
another is the same for all processes, both internally reversible and irreversible, between these
two states. Thus, Eq. 6.4a allows the determination of the change in entropy, and once it has
been evaluated, this is the magnitude of the entropy change for all processes of the system
between the two states. The evaluation of entropy change is discussed further in the next
section.
It should be clear that entropy is defined and evaluated in terms of a particular integral
for which no accompanying physical picture is given. We encountered this previously with
the property enthalpy. Enthalpy is introduced without physical motivation in Sec. 3.3.2. Then,
in Chap. 4, enthalpy is shown to be useful for thermodynamic analysis. As for the case of
enthalpy, to gain an appreciation for entropy you need to understand how it is used and what
it is used for.

6.3 Retrieving Entropy Data
In Chap. 3, we introduced means for retrieving property data, including tables, graphs, equa-
tions, and the software available with this text. The emphasis there is on evaluating the prop-
erties p, v, T, u, and h required for application of the conservation of mass and energy
principles. For application of the second law, entropy values are usually required. In this
section, means for retrieving entropy data are considered.
6.3.1 General Considerations

The defining equation for entropy change, Eq. 6.4a, serves as the basis for evaluating en-
tropy relative to a reference value at a reference state. Both the reference value and the ref-
erence state can be selected arbitrarily. The value of the entropy at any state y relative to the
value at the reference state x is obtained in principle from
y
Sy Sx
a b int
dQ
(6.5)
x T rev
where Sx is the reference value for entropy at the specified reference state.
The use of entropy values determined relative to an arbitrary reference state is satisfac-
tory as long as they are used in calculations involving entropy differences, for then the ref-
erence value cancels. This approach suffices for applications where composition remains con-
stant. When chemical reactions occur, it is necessary to work in terms of absolute values of
entropy determined using the third law of thermodynamics (Chap. 13).
ENTROPY DATA FOR WATER AND REFRIGERANTS
Tables of thermodynamic data are introduced in Sec. 3.3 for water and several refrigerants
(Tables A-2 through A-18). Specific entropy is tabulated in the same way as considered there
for the properties v, u, and h, and entropy values are retrieved similarly.
VAPOR DATA. In the superheat regions of the tables for water and the refrigerants, specific
entropy is tabulated along with v, u, and h versus temperature and pressure.
for example. . . consider two states of water. At state 1 the pressure is 3 MPa and the
temperature is 500C. At state 2, the pressure is 0.3 MPa and the specific entropy is the same
as at state 1, s2 s1. The object is to determine the temperature at state 2. Using T1 and p1,
we find the specific entropy at state 1 from Table A-4 as s1 7.2338 kJkg # K. State 2 is
fixed by the pressure, p2 0.3 MPa, and the specific entropy, s2 7.2338 kJkg # K. Returing
to Table A-4 at 0.3 MPa and interpolating with s2 between 160 and 200C results in
T2 183C.
SATURATION DATA. For saturation states, the values of sf and sg are tabulated as a func-
tion of either saturation pressure or saturation temperature. The specific entropy of a two-
phase liquidvapor mixture is calculated using the quality
s 11 x2sf
xsg sf
x1sg sf 2 (6.6)
These relations are identical in form to those for v, u, and h (Sec. 3.3). for example. . .
let us determine the specific entropy of Refrigerant 134a at a state where the temperature
is 0C and the specific internal energy is 138.43 kJ/kg. Referring to Table A-10, we see that
the given value for u falls between uf and ug at 0C, so the system is a two-phase liquidvapor
mixture. The quality of the mixture can be determined from the known specific internal
energy
u uf 138.43 49.79
x 0.5
ug uf 227.06 49.79
Then with values from Table A-10
s 11 x2sf
xsg
10.5210.19702
10.5210.91902 0.5580 kJ/kg # K
LIQUID DATA. Compressed liquid data are presented for water in Tables A-5. In these tables
s, v, u, and h are tabulated versus temperature and pressure as in the superheat tables, and
the tables are used similarly. In the absence of compressed liquid data, the value of the specific
entropy can be estimated in the same way as estimates for v and u are obtained for liquid
states (Sec. 3.3.6), by using the saturated liquid value at the given temperature
s1T, p2 sf 1T 2 (6.7)
for example. . . suppose the value of specific entropy is required for water at 25 bar,
200C. The specific entropy is obtained directly from Table A-5 as s 2.3294 kJkg # K. Using
the saturated liquid value for specific entropy at 200C from Table A-2, the specific entropy
is approximated with Eq. 6.7 as s 2.3309 kJkg # K, which agrees closely with the previous
value.
The specific entropy values for water and the refrigerants given in Tables A-2 through
A-18 are relative to the following reference states and values. For water, the entropy of
saturated liquid at 0.01C is set to zero. For the refrigerants, the entropy of the saturated liq-
uid at 40C is assigned a value of zero.
COMPUTER RETRIEVAL. The software available with this text, Interactive Thermodynam-
ics: IT, provides data for the substances considered in this section. Entropy data are retrieved
by simple call statements placed in the workspace of the program. for example. . .
consider a two-phase liquidvapor mixture of H2O at p 1 bar, v 0.8475 m3/kg. The fol-
lowing illustrates how specific entropy and quality x are obtained using IT
p = 1 // bar
v = 0.8475 // m3/kg
v = vsat_Px(Water/Steam,p,x)
s = ssat_Px(Water/Steam,p,x)
The software returns values of x 0.5 and s 4.331 kJ/kg # K, which can be checked using
METHODOLOGY
data from Table A-3. Note that quality x is implicit in the list of arguments in the expression UPDATE
for specific volume, and it is not necessary to solve explicitly for x. As another example, con-
Note that IT does not
sider superheated ammonia vapor at p 1.5 bar, T 8C. Specific entropy is obtained from
provide compressed liquid
IT as follows: data for any substance. IT
returns liquid entropy data
p = 1.5 // bar
using the approximation of
T = 8 // C
Eq. 6.7. Similarly, Eqs. 3.11,
s = s_PT(Ammonia,p,T) 3.12, and 3.14 are used to
return liquid values for v,
The software returns s 5.981 kJ/kg # K, which agrees closely with the value obtained by
u, and h, respectively.
interpolation in Table A-15.
USING GRAPHICAL ENTROPY DATA
The use of property diagrams as an adjunct to problem solving is emphasized throughout

this book. When applying the second law, it is frequently helpful to locate states and plot
processes on diagrams having entropy as a coordinate. Two commonly used figures having
entropy as one of the coordinates are the temperatureentropy diagram and the enthalpy
entropy diagram.
TEMPERATUREENTROPY DIAGRAM. The main features of a temperatureentropy Ts diagram

diagram are shown in Fig. 6.3. For detailed figures for water in SI, see Fig. A-7. Observe
v = constant
t
ant
p = constan
T h p = constant
p = const
h = constant
T = constant
Critical point
T = constant
p = constant
id
liqu
por
x=
ted
v = constant 0.9
d va
6
ura
nt
nt
sta
rate
S at
sta
con
x=
Sat
con
Satu
0 .9
p=
ura 0
p=
te d
x = 0.2 x = 0.9 v ap
or Critical point
s s
Figure 6.3 Temperatureentropy diagram. Figure 6.4 Enthalpyentropy diagram.
that lines of constant enthalpy are shown on these figures. Also note that in the super-
heated vapor region constant specific volume lines have a steeper slope than constant-
pressure lines. Lines of constant quality are shown in the two-phase liquidvapor region.
On some figures, lines of constant quality are marked as percent moisture lines. The per-
cent moisture is defined as the ratio of the mass of liquid to the total mass.
In the superheated vapor region of the Ts diagram, constant specific enthalpy lines be-
come nearly horizontal as pressure is reduced. These states are shown as the shaded area on
Fig. 6.3. For states in this region of the diagram, the enthalpy is determined primarily by the
temperature: h(T, p) h(T). This is the region of the diagram where the ideal gas model
provides a reasonable approximation. For superheated vapor states outside the shaded area,
both temperature and pressure are required to evaluate enthalpy, and the ideal gas model is
not suitable.
ENTHALPYENTROPY DIAGRAM. The essential features of an enthalpyentropy diagram,

Mollier diagram commonly known as a Mollier diagram, are shown in Fig. 6.4. For detailed figures for water
in SI, see Figs. A-8. Note the location of the critical point and the appearance of lines of
constant temperature and constant pressure. Lines of constant quality are shown in the two-
phase liquidvapor region (some figures give lines of constant percent moisture). The figure
is intended for evaluating properties at superheated vapor states and for two-phase liquid
vapor mixtures. Liquid data are seldom shown. In the superheated vapor region, constant-
temperature lines become nearly horizontal as pressure is reduced. These states are shown,
approximately, as the shaded area on Fig. 6.4. This area corresponds to the shaded area on
the temperatureentropy diagram of Fig. 6.3, where the ideal gas model provides a reasonable
approximation.
for example. . . to illustrate the use of the Mollier diagram in SI units, consider
two states of water. At state 1, T1 240C, p1 0.10 MPa. The specific enthalpy and
quality are required at state 2, where p2 0.01 MPa and s2 s1. Turning to Fig. A-8, state 1
is located in the superheated vapor region. Dropping a vertical line into the two-phase
liquidvapor region, state 2 is located. The quality and specific enthalpy at state 2 read
from the figure agree closely with values obtained using Tables A-3 and A-4: x2 0.98 and
h2 2537 kJ/ kg.
USING THE T dS EQUATIONS
Although the change in entropy between two states can be determined in principle by using
Eq. 6.4a, such evaluations are generally conducted using the T dS equations developed in
this section. The T dS equations allow entropy changes to be evaluated from other more read-
ily determined property data. The use of the T dS equations to evaluate entropy changes for
ideal gases is illustrated in Sec. 6.3.2 and for incompressible substances in Sec. 6.3.3. The
importance of the T dS equations is greater than their role in assigning entropy values, how-
ever. In Chap. 11 they are used as a point of departure for deriving many important property
relations for pure, simple compressible systems, including means for constructing the prop-
erty tables giving u, h, and s.
The T dS equations are developed by considering a pure, simple compressible system un-
dergoing an internally reversible process. In the absence of overall system motion and the
effects of gravity, an energy balance in differential form is
1dQ2 int dU
1dW2 int (6.8)
rev rev
By definition of simple compressible system (Sec. 3.1), the work is
1dW2 int p dV (6.9a)

rev
On rearrangement of Eq. 6.4b, the heat transfer is
1dQ2 int T dS (6.9b)

rev
Substituting Eqs. 6.9 into Eq. 6.8, the first T dS equation results
T dS dU
p dV (6.10) first T dS equation
The second T dS equation is obtained from Eq. 6.10 using H U

pV. Forming the
differential
dH dU
d1 pV2 dU
p dV
V dp
On rearrangement
dU
p dV dH V dp
Substituting this into Eq. 6.10 gives the second T dS equation
T dS dH V dp (6.11) second T dS equation
The T dS equations can be written on a unit mass basis as
T ds du
p dv (6.12a)
T ds dh v dp (6.12b)
or on a per mole basis as
T ds du
pdv (6.13a)
T d s d h v dp (6.13b)
Although the T dS equations are derived by considering an internally reversible process,

an entropy change obtained by integrating these equations is the change for any process, re-
versible or irreversible, between two equilibrium states of a system. Because entropy is a
property, the change in entropy between two states is independent of the details of the process
linking the states.
To show the use of the T dS equations, consider a change in phase from saturated liquid
to saturated vapor at constant temperature and pressure. Since pressure is constant, Eq. 6.12b
reduces to give
dh
ds
T
Then, because temperature is also constant during the phase change
hg hf
sg sf (6.14)
T
This relationship shows how sg sf is calculated for tabulation in property tables.

for example. . . consider Refrigerant 134a at 0C. From Table A-10, hg hf
197.21 kJ/kg, so with Eq. 6.14
197.21 kJ/kg kJ
sg sf 0.7220 #
273.15 K kg K
which is the value calculated using sf and sg from the table.
6.3.2 Entropy Change of an Ideal Gas

In this section the T dS equations are used to evaluate the entropy change between two states
of an ideal gas. It is convenient to begin with Eqs. 6.12 expressed as
du p
ds
dv (6.15)
T T
dh v
ds dp (6.16)
T T
For an ideal gas, du cv(T ) dT, dh cp(T ) dT, and pv RT. With these relations,
Eqs. 6.15 and 6.16 become, respectively
ds cv 1T 2 ds cp 1T 2
dT dv dT dp

R and R (6.17)
T v T p
Since R is a constant, the last terms of Eqs. 6.17 can be integrated directly. However, because
cv and cp are functions of temperature for ideal gases, it is necessary to have information about
the functional relationships before the integration of the first term in these equations can be
performed. Since the two specific heats are related by
cp 1T 2 cv 1T 2
R (3.44)
where R is the gas constant, knowledge of either specific heat function suffices.
On integration, Eqs. 6.17 give, respectively
s1T2, v2 2 s1T1, v1 2 cv 1T 2
T2 dT v2

R ln (6.18)
T1 T v1
s1T2, p2 2 s1T1, p1 2 cp 1T 2
T2 dT p2
R ln (6.19)
T1 T p1
USING IDEAL GAS TABLES. As for internal energy and enthalpy changes, the evaluation
of entropy changes for ideal gases can be reduced to a convenient tabular approach. To in-
troduce this, we begin by selecting a reference state and reference value: The value of the spe-
cific entropy is set to zero at the state where the temperature is 0 K and the pressure is 1 at-
mosphere. Then, using Eq. 6.19, the specific entropy at a state where the temperature is T and
the pressure is 1 atm is determined relative to this reference state and reference value as
cp 1T 2
s1T 2
T
dT (6.20)
0 T
The symbol s(T ) denotes the specific entropy at temperature T and a pressure of 1 atm.
Because s depends only on temperature, it can be tabulated versus temperature, like
h and u. For air as an ideal gas, s with units of kJ/kg # K is given in Tables A-22.Values
of s for several other common gases are given in Tables A-23 with units of kJ/kmol # K.
Since the integral of Eq. 6.19 can be expressed in terms of s

T2 dT T2 dT T1 dT
cp cp cp
T1 T 0 T 0 T
s1T2 2 s1T1 2
it follows that Eq. 6.19 can be written as
s1T2, p2 2 s1T1, p1 2 s1T2 2 s1T1 2 R ln

p2
p1
(6.21a)
or on a per mole basis as
s1T2, p2 2 s1T1, p1 2 s 1T2 2 s 1T1 2 R ln

p2
p1
(6.21b)
Using Eqs. 6.21 and the tabulated values for s or s , as appropriate, entropy changes
can be determined that account explicitly for the variation of specific heat with temperature.
for example. . . let us evaluate the change in specific entropy, in kJkg # K, of air
modeled as an ideal gas from a state where T1 300 K and p1 1 bar to a state where
T2 1000 K and p2 3 bar. Using Eq. 6.21a and data from Table A-22
s2 s1 s1T2 2 s1T1 2 R ln
p2
p1
12.96770 1.702032 #
kJ 8.314 kJ 3 bar
# ln
kg K 28.97 kg K 1 bar
0.9504 kJ/kg K
#
If a table giving s (or s ) is not available for a particular gas of interest, the integrals of
Eqs. 6.18 and 6.19 can be performed analytically or numerically using specific heat data such
as provided in Tables A-20 and A-21.
ASSUMING CONSTANT SPECIFIC HEATS. When the specific heats cv and cp are taken as
constants, Eqs. 6.18 and 6.19 reduce, respectively, to
s1T2, v2 2 s1T1, v1 2 cv ln
T2 v2

R ln (6.22)
T1 v1

s1T2, p2 2 s1T1, p1 2 cp ln R ln
T2 p2
(6.23)
T1 p1
These equations, along with Eqs. 3.50 and 3.51 giving u and h, respectively, are applica-
ble when assuming the ideal gas model with constant specific heats.
for example. . . let us determine the change in specific entropy, in kJ/kg # K, of air
as an ideal gas undergoing a process from T1 300 K, p1 1 bar to T2 400 K, p2 5 bar.
Because of the relatively small temperature range, we assume a constant value of cp evaluated
at 350 K. Using Eq. 6.23 and cp 1.008 kJ/kg # K from Table A-20
T2 p2
s cp ln R ln
T1 p1
a1.008 b ln a ba b ln a b
kJ 400 K 8.314 kJ 5 bar
kg # K 300 K 28.97 kg # K 1 bar
0.1719 kJ/kg # K
COMPUTER RETRIEVAL. For air and other gases modeled as ideal gases, IT directly returns
s(T, p) based upon the following form of Eq. 6.19
cp 1T 2
s1T, p2 s1Tref, pref 2
T p
dT R ln
Tref T pref
and the following choice of reference state and reference value: Tref 0 K (0R), pref
1 atm, and s(Tref, pref) 0, giving
cp 1T 2

T p
s1T, p2 dT R ln
0 T pref
Changes in specific entropy evaluated using IT agree with entropy changes evaluated
using ideal gas tables. for example. . . consider a process of air as an ideal gas from
T1 300 K, p1 1 bar to T2 1000 K, p2 3 bar. The change in specific entropy, denoted
6.4 Entropy Change in Internally Reversible Processes 217
as dels, is determined in SI units using IT as follows:

p1 = 1 // bar
T1 = 300 // K
p2 = 3
T2 = 1000
s1 = s_TP(Air,T1,p1)
s2 = s_TP(Air,T2,p2)
dels = s2 s1
The software returns values of s1 1.706, s2 2.656, and dels 0.9501, all in units of
kJ/kg # K. This value for s agrees with the value obtained using Table A-22 in the example
following Eqs. 6.21. Note that IT returns specific entropy directly and does not use the
special function s.
6.3.3 Entropy Change of an Incompressible Substance

The incompressible substance model introduced in Sec. 3.3.6 assumes that the specific vol-
ume (density) is constant and the specific heat depends solely on temperature, cv c(T). Ac-
cordingly, the differential change in specific internal energy is du c(T ) dT and Eq. 6.15
reduces to
0
c1T 2 dT p dv c1T 2 dT
ds

T T T
On integration, the change in specific entropy is
c1T 2
1incompressible2
T2
s2 s1 dT
T1 T
When the specific heat is assumed constant, this becomes
1incompressible, constant c2
T2
s2 s1 c ln (6.24)
T1
Equation 6.24, along with Eqs. 3.20 giving u and h, respectively, are applicable to liquids
and solids modeled as incompressible. Specific heats of some common liquids and solids are
given in Table A-19.

6.4 Entropy Change in Internally
Reversible Processes
In this section the relationship between entropy change and heat transfer for internally re-
versible processes is considered. The concepts introduced have important applications in sub-
sequent sections of the book. The present discussion is limited to the case of closed systems.
Similar considerations for control volumes are presented in Sec. 6.9.
As a closed system undergoes an internally reversible process, its entropy can increase,
decrease, or remain constant. This can be brought out using Eq. 6.4b
dS a bint
dQ
T rev
which indicates that when a closed system undergoing an internally reversible process receives
energy by heat transfer, the system experiences an increase in entropy. Conversely, when en-
ergy is removed from the system by heat transfer, the entropy of the system decreases. This
can be interpreted to mean that an entropy transfer accompanies heat transfer. The direction
of the entropy transfer is the same as that of the heat transfer. In an adiabatic internally
reversible process, the entropy would remain constant. A constant-entropy process is called
isentropic process an isentropic process.
On rearrangement, the above expression gives
2
1dQ2 int T dS
Qint = 1 T dS rev
rev
T (Q) = T dS 2 Integrating from an initial state 1 to a final state 2
int
rev
1
T dS
2
Qint (6.25)
rev 1
From Eq. 6.25 it can be concluded that an energy transfer by heat to a closed system dur-
S ing an internally reversible process can be represented as an area on a temperatureentropy
Figure 6.5 Area diagram. Figure 6.5 illustrates the area interpretation of heat transfer for an arbitrary inter-
representation of heat nally reversible process in which temperature varies. Carefully note that temperature must
transfer for an internally
be in kelvins or degrees Rankine, and the area is the entire area under the curve (shown
reversible process of a
closed system.
shaded). Also note that the area interpretation of heat transfer is not valid for irreversible
processes, as will be demonstrated later.
To provide an example illustrating both the entropy change that accompanies heat transfer
Carnot cycle and the area interpretation of heat transfer, consider Fig. 6.6a, which shows a Carnot power
cycle (Sec. 5.6). The cycle consists of four internally reversible processes in series: two
isothermal processes alternated with two adiabatic processes. In Process 23, heat transfer
to the system occurs while the temperature of the system remains constant at TH. The sys-
tem entropy increases due to the accompanying entropy transfer. For this process, Eq. 6.25
gives Q23 TH(S3 S2), so area 23ab2 on Fig. 6.6a represents the heat transfer during
the process. Process 34 is an adiabatic and internally reversible process and thus is an isen-
tropic (constant-entropy) process. Process 41 is an isothermal process at TC during which
heat is transferred from the system. Since entropy transfer accompanies the heat transfer, sys-
tem entropy decreases. For this process, Eq. 6.25 gives Q41 TC(S1 S4), which is nega-
tive in value. Area 41ba4 on Fig. 6.6a represents the magnitude of the heat transfer Q41.
Process 12, which completes the cycle, is adiabatic and internally reversible (isentropic).
2 3 4 3
TH TH
T T
TC TC
1 4 1 2
b a b a
S S
(a) (b)
Figure 6.6 Carnot cycles on the temperatureentropy diagram. (a) Power
cycle. (b) Refrigeration or heat pump cycle.
6.4 Entropy Change in Internally Reversible Processes 219
The net work of any cycle is equal to the net heat transfer, so enclosed area 12341
represents the net work of the cycle. The thermal efficiency of the cycle may also be ex-
pressed in terms of areas:
Wcycle area 12341
h
Q23 area 23ab2
The numerator of this expression is (TH TC)(S3 S2) and the denominator is TH(S3 S2),
so the thermal efficiency can be given in terms of temperatures only as 1 TCTH. If
the cycle were executed as shown in Fig. 6.6b, the result would be a Carnot refrigeration or
heat pump cycle. In such a cycle, heat is transferred to the system while its temperature re-
mains at TC, so entropy increases during Process 12. In Process 34 heat is transferred from
the system while the temperature remains constant at TH and entropy decreases.
To further illustrate concepts introduced in this section, the next example considers water
undergoing an internally reversible process while contained in a pistoncylinder assembly.
EXAMPLE 6.1 Internally Reversible Process of Water
Water, initially a saturated liquid at 100C, is contained in a pistoncylinder assembly. The water undergoes a process to the
corresponding saturated vapor state, during which the piston moves freely in the cylinder. If the change of state is brought
about by heating the water as it undergoes an internally reversible process at constant pressure and temperature, determine the
work and heat transfer per unit of mass, each in kJ/kg.
SOLUTION
Known: Water contained in a pistoncylinder assembly undergoes an internally reversible process at 100C from saturated
liquid to saturated vapor.
Find: Determine the work and heat transfer per unit mass.
p T
f g 100C
f g
Water W Q
100C
System boundary m m
v s
Figure E6.1
Assumptions:
1. The water in the pistoncylinder assembly is a closed system.

2. The process is internally reversible.
3. Temperature and pressure are constant during the process.
4. There is no change in kinetic or potential energy between the two end states.
Analysis: At constant pressure the work is

g
p dv p1vg vf 2
W

m f
With values from Table A-2

m3 105 N/m2
11.014 bar2 11.673 1.0435 103 2 a b ` ` ` 3 # `
W 1 kJ
m kg 1 bar 10 N m
170 kJ/kg
Since the process is internally reversible and at constant temperature, Eq. 6.25 gives
g g
Q f
T dS m f
T ds
or
T 1sg sf 2
Q
m
1373.15 K217.3549 1.30692 kJ/ kg # K 2257 kJ/kg

Q
m
As shown in the accompanying figure, the work and heat transfer can be represented as areas on pv and Ts diagrams,
respectively.
The heat transfer can be evaluated alternatively from an energy balance written on a unit mass basis as
Q W
ug uf
m m
Introducing Wm p(vg vf) and solving
1ug uf 2
p1vg vf 2
Q
m
1ug
pvg 2 1uf
pvf 2
hg hf
From Table A-2 at 100C, hg hf 2257 kJ/kg, which is the same value for Qm as obtained in the solution.
6.5 Entropy Balance for Closed Systems

In this section, the Clausius inequality expressed by Eq. 6.2 and the defining equation for
entropy change are used to develop the entropy balance for closed systems. The entropy bal-
ance is an expression of the second law that is particularly convenient for thermodynamic
2 analysis. The current presentation is limited to closed systems. The entropy balance is ex-
R tended to control volumes in Sec. 6.6.
I 6.5.1 Developing the Entropy Balance

Shown in Fig. 6.7 is a cycle executed by a closed system. The cycle consists of process I,
during which internal irreversibilities are present, followed by internally reversible process
1 R. For this cycle, Eq. 6.2 takes the form
Figure 6.7 Cycle
a b
a b int s
2 dQ 1 dQ
used to develop the (6.26)
entropy balance. 1 T b 2 T rev
6.5 Entropy Balance for Closed Systems 221
where the first integral is for process I and the second is for process R. The subscript b in the
first integral serves as a reminder that the integrand is evaluated at the system boundary. The sub-
script is not required in the second integral because temperature is uniform throughout the system
at each intermediate state of an internally reversible process. Since no irreversibilities are
associated with process R, the term cycle of Eq. 6.2, which accounts for the effect of
irreversibilities during the cycle, refers only to process I and is shown in Eq. 6.26 simply as .
Applying the definition of entropy change, we can express the second integral of Eq. 6.26 as
a b int
1 dQ
S1 S2
2 T rev
With this, Eq. 6.26 becomes
a
b
1S1 S2 2 s
2
dQ
1 T b
Finally, on rearranging the last equation, the closed system entropy balance results
a
b
2
dQ
S2 S1 s closed system entropy
1 T b (6.27)
entropy entropy entropy balance
change transfer production
If the end states are fixed, the entropy change on the left side of Eq. 6.27 can be evaluated
independently of the details of the process. However, the two terms on the right side depend
explicitly on the nature of the process and cannot be determined solely from knowledge of
the end states. The first term on the right side of Eq. 6.27 is associated with heat transfer to
or from the system during the process. This term can be interpreted as the entropy transfer entropy transfer
accompanying heat transfer. The direction of entropy transfer is the same as the direction of accompanying heat
the heat transfer, and the same sign convention applies as for heat transfer: A positive value
transfer
means that entropy is transferred into the system, and a negative value means that entropy is
transferred out. When there is no heat transfer, there is no entropy transfer.
The entropy change of a system is not accounted for solely by the entropy transfer, but is
due in part to the second term on the right side of Eq. 6.27 denoted by . The term is pos-
itive when internal irreversibilities are present during the process and vanishes when no in-
ternal irreversibilities are present. This can be described by saying that entropy is produced entropy production
within the system by the action of irreversibilities. The second law of thermodynamics can
be interpreted as requiring that entropy is produced by irreversibilities and conserved only
in the limit as irreversibilities are reduced to zero. Since measures the effect of irre-
versibilities present within the system during a process, its value depends on the nature of
the process and not solely on the end states. It is not a property.
When applying the entropy balance to a closed system, it is essential to remember the re-
quirements imposed by the second law on entropy production: The second law requires that
entropy production be positive, or zero, in value
s: e
7 0 irreversibilities present within the system
(6.28)
0 no irreversibilities present within the system
The value of the entropy production cannot be negative. By contrast, the change in entropy
of the system may be positive, negative, or zero:
7 0
S2 S1: 0 (6.29)
6 0
Like other properties, entropy change can be determined without knowledge of the details
of the process.
This portion of the

boundary is at temperature Tb
Gas or liquid
Q
Reservoir
at Tb
Q/Tb
Figure 6.8 Illustration of the

entropy transfer and entropy production
concepts.
for example. . . to illustrate the entropy transfer and entropy production concepts,
as well as the accounting nature of entropy balance, consider Fig. 6.8. The figure shows a
system consisting of a gas or liquid in a rigid container stirred by a paddle wheel while re-
ceiving a heat transfer Q from a reservoir. The temperature at the portion of the boundary
where heat transfer occurs is the same as the constant temperature of the reservoir, Tb. By
definition, the reservoir is free of irreversibilities; however, the system is not without irre-
versibilities, for fluid friction is evidently present, and there may be other irreversibilities
within the system.
Let us now apply the entropy balance to the system and to the reservoir. Since Tb is con-
stant, the integral in Eq. 6.27 is readily evaluated, and the entropy balance for the system
reduces to
Q
S2 S1
s (6.30)
Tb
where QTb accounts for entropy transfer into the system accompanying heat transfer Q. The
entropy balance for the reservoir takes the form
Qres 0
S4 res
sres
Tb
where the entropy production term is set equal to zero because the reservoir is without irre-
versibilities. Since Qres Q, the last equation becomes
Q
S4 res
Tb
The minus sign signals that entropy is carried out of the reservoir accompanying heat transfer.
Hence, the entropy of the reservoir decreases by an amount equal to the entropy transferred from
it to the system. However, as shown by Eq. 6.30, the entropy change of the system exceeds the
amount of entropy transferred to it because of entropy production within the system.
If the heat transfer were oppositely directed in the above example, passing instead from
the system to the reservoir, the magnitude of the entropy transfer would remain the same,
but its direction would be reversed. In such a case, the entropy of the system would decrease
if the amount of entropy transferred from the system to the reservoir exceeded the amount
of entropy produced within the system due to irreversibilities. Finally, observe that there is
no entropy transfer associated with work.
6.5.2 Other Forms of the Entropy Balance

The entropy balance can be expressed in various forms convenient for particular analyses.
For example, if heat transfer takes place at several locations on the boundary of a system
where the temperatures do not vary with position or time, the entropy transfer term can be
expressed as a sum, so Eq. 6.27 takes the form
Qj
S2 S1 a
s (6.31)
j Tj
where QjTj is the amount of entropy transferred through the portion of the boundary at tem-
perature Tj.
On a time rate basis, the closed system entropy rate balance is
#
dS Qj # closed system entropy
a
s (6.32)
dt j Tj rate balance
#
where dSdt is the time rate of change of entropy of the system. The term QjTj represents
the time rate of entropy transfer through the portion of the boundary whose instantaneous
#
temperature is Tj. The term s accounts for the time rate of entropy production due to irre-
versibilities within the system.
It is sometimes convenient to use the entropy balance expressed in differential form
dS a b
ds
dQ
(6.33)
T b
Note that the differentials of the nonproperties Q and are shown, respectively, as Q and .
When there are no internal irreversibilities, vanishes and Eq. 6.33 reduces to Eq. 6.4b.
6.5.3 Evaluating Entropy Production and Transfer

Regardless of the form taken by the entropy balance, the objective in many applications is
to evaluate the entropy production term. However, the value of the entropy production for a
given process of a system often does not have much significance by itself. The significance
is normally determined through comparison. For example, the entropy production within a
given component might be compared to the entropy production values of the other compo-
nents included in an overall system formed by these components. By comparing entropy pro-
duction values, the components where appreciable irreversibilities occur can be identified
and rank ordered. This allows attention to be focused on the components that contribute most
to inefficient operation of the overall system.
To evaluate the entropy transfer term of the entropy balance requires information re-
garding both the heat transfer and the temperature on the boundary where the heat transfer Boundary of
enlarged system
occurs. The entropy transfer term is not always subject to direct evaluation, however, be-
Temperature
cause the required information is either unknown or not defined, such as when the system T > Tf variation
passes through states sufficiently far from equilibrium. In such applications, it may be con-
venient, therefore, to enlarge the system to include enough of the immediate surroundings
that the temperature on the boundary of the enlarged system corresponds to the tempera-
ture of the surroundings away from the immediate vicinity of the system, Tf. The entropy Tf
transfer term is then simply QTf. However, as the irreversibilities present would not be just
for the system of interest but for the enlarged system, the entropy production term would
account for the effects of internal irreversibilities within the original system and external
irreversibilities present within that portion of the surroundings included within the enlarged
system.
6.5.4 Illustrations
The following examples illustrate the use of the energy and entropy balances for the analy-
sis of closed systems. Property relations and property diagrams also contribute significantly
in developing solutions. The first example reconsiders the system and end states of Exam-
ple 6.1 to demonstrate that entropy is produced when internal irreversibilities are present and
that the amount of entropy production is not a property.
EXAMPLE 6.2 Irreversible Process of Water
Water initially a saturated liquid at 100C is contained within a pistoncylinder assembly. The water undergoes a process to
the corresponding saturated vapor state, during which the piston moves freely in the cylinder. There is no heat transfer with
the surroundings. If the change of state is brought about by the action of a paddle wheel, determine the net work per unit
mass, in kJ/kg, and the amount of entropy produced per unit mass, in kJ/kg # K.
SOLUTION
Known: Water contained in a pistoncylinder assembly undergoes an adiabatic process from saturated liquid to saturated
vapor at 100C. During the process, the piston moves freely, and the water is rapidly stirred by a paddle wheel.
Find: Determine the net work per unit mass and the entropy produced per unit mass.
p T
f g
100C f g System
Water
Area is
100C Area is
boundary
not work
not heat
v s
Figure E6.2
Assumptions:
1. The water in the pistoncylinder assembly is a closed system.

3. The system is at an equilibrium state initially and finally. There is no change in kinetic or potential energy between these
two states.
Analysis: As the volume of the system increases during the process, there is an energy transfer by work from the system
during the expansion, as well as an energy transfer by work to the system via the paddle wheel. The net work can be evalu-
ated from an energy balance, which reduces with assumptions 2 and 3 to
0 0 0
U
KE
PE Q W
On a unit mass basis, the energy balance reduces to
1ug uf 2
W
m
With specific internal energy values from Table A-2 at 100C
W kJ
2087.56
m kg
The minus sign indicates that the work input by stirring is greater in magnitude than the work done by the water as it
expands.
The amount of entropy produced is evaluated by applying an entropy balance. Since there is no heat transfer, the term
accounting for entropy transfer vanishes
0
a b
s
2 dQ
S
1 T b
On a unit mass basis, this becomes on rearrangement
s
sg sf
m
With specific entropy values from Table A-2 at 100C
s
6.048 #
kJ
m kg K
Although each end state is an equilibrium state at the same pressure and temperature, the pressure and temperature are not
necessarily uniform throughout the system at intervening states, nor are they necessarily constant in value during the
process. Accordingly, there is no well-defined path for the process. This is emphasized by the use of dashed lines to
represent the process on these pv and Ts diagrams. The dashed lines indicate only that a process has taken place, and
no area should be associated with them. In particular, note that the process is adiabatic, so the area below the dashed
line on the Ts diagram can have no significance as heat transfer. Similarly, the work cannot be associated with an area
on the pv diagram.
The change of state is the same in the present example as in Example 6.1. However, in Example 6.1 the change of state
is brought about by heat transfer while the system undergoes an internally reversible process. Accordingly, the value of
entropy production for the process of Example 6.1 is zero. Here, fluid friction is present during the process and the en-
tropy production is positive in value. Accordingly, different values of entropy production are obtained for two processes
between the same end states. This demonstrates that entropy production is not a property.
As an illustration of second law reasoning, the next example uses the fact that the entropy
production term of the entropy balance cannot be negative.
EXAMPLE 6.3 Evaluating Minimum Theoretical Compression Work
Refrigerant 134a is compressed adiabatically in a pistoncylinder assembly from saturated vapor at 0C to a final pressure of
0.7 MPa. Determine the minimum theoretical work input required per unit mass of refrigerant, in kJ/ kg.
SOLUTION
Known: Refrigerant 134a is compressed without heat transfer from a specified initial state to a specified final pressure.
Find: Determine the minimum theoretical work input required per unit of mass.
Accessible
states
T Internal
2 energy
decreases
2s
Actual Insulation
compression
Internally
reversible
compression
1 R-134a
s
Figure E6.3
Assumptions:
1. The Refrigerant 134a is a closed system.

3. The initial and final states are equilibrium states. There is no change in kinetic or potential energy between these states.
Analysis: An expression for the work can be obtained from an energy balance. By applying assumptions 2 and 3
0 0 0
U
KE
PE Q W
When written on a unit mass basis, the work input is then
a b u2 u1
W
m
The specific internal energy u1 can be obtained from Table A-10 as u1 227.06 kJ/kg. Since u1 is known, the value for the
work input depends on the specific internal energy u2. The minimum work input corresponds to the smallest allowed value
for u2, determined using the second law as follows.
Applying an entropy balance
0
a b
s
2 dQ
S
1 T b
where the entropy transfer term is set equal to zero because the process is adiabatic. Thus, the allowed final states must satisfy
s
s2 s1 0
m
The restriction indicated by the foregoing equation can be interpreted using the accompanying Ts diagram. Since cannot
be negative, states with s2 s1 are not accessible adiabatically. When irreversibilities are present during the compression, en-
tropy is produced, so s2 s1. The state labeled 2s on the diagram would be attained in the limit as irreversibilities are reduced
to zero. This state corresponds to an isentropic compression.
By inspection of Table A-12, we see that when pressure is fixed, the specific internal energy decreases as temperature
decreases. Thus, the smallest allowed value for u2 corresponds to state 2s. Interpolating in Table A-12 at 0.7 MPa, with
s2s s1 0.9190 kJ/kg K, we find that u2s 244.32 kJ/kg. Finally, the minimum work input is
a b u2s u1 244.32 227.06 17.26 kJ/kg

W
m min
The effect of irreversibilities exacts a penalty on the work input required: A greater work input is needed for the actual
adiabatic compression process than for an internally reversible adiabatic process between the same initial state and the
same final pressure.
To pinpoint the relative significance of the internal and external irreversibilities, the next
example illustrates the application of the entropy rate balance to a system and to an enlarged
system consisting of the system and a portion of its immediate surroundings.
EXAMPLE 6.4 Pinpointing Irreversibilities
#
Referring to Example 2.4, evaluate the rate of entropy production s, in kW/K, for (a) the gearbox as the system and (b) an
enlarged system consisting of the gearbox and enough of its surroundings that heat transfer occurs at the temperature of the
surroundings away from the immediate vicinity of the gearbox, Tf 293 K (20C).
SOLUTION
Known: A gearbox operates at steady state with known values for the power input through the high-speed shaft, power out-
put through the low-speed shaft, and heat transfer rate. The temperature on the outer surface of the gearbox and the temper-
ature of the surroundings away from the gearbox are also known.
#
Find: Evaluate the entropy production rate s for each of the two specified systems shown in the schematic.
At this
boundary the
temperature is Temperature
System Tf = 293 K variation
boundary
Q = 1.2 kW Tb
60 kW 60 kW
Tf
58.8 kW
58.8 kW
Tb = 300 K
Gearbox
(a) (b)
Figure E6.4
Assumptions:
1. In part (a), the gearbox is taken as a closed system operating at steady state, as shown on the accompanying sketch labeled
with data from Example 2.4.
2. In part (b) the gearbox and a portion of its surroundings are taken as a closed system, as shown on the accompanying
sketch labeled with data from Example 2.4.
3. The temperature of the outer surface of the gearbox and the temperature of the surroundings are each uniform.
Analysis:
(a) To obtain an expression for the entropy production rate, begin with the entropy balance for a closed system on a time rate
basis: Eq. 6.32. Since heat transfer takes place only at temperature Tb, the entropy rate balance reduces at steady state to
0 #
dS Q #

s
dt Tb
Solving
#
# Q
s
Tb
#
Introducing the known values for the heat transfer rate Q and the surface temperature Tb
# 11.2 kW2
s 4 103 kW/K
1300 K2
(b) Since heat transfer takes place at temperature Tf for the enlarged system, the entropy rate balance reduces at steady state to
0 #
dS Q #

s
dt Tf
Solving #
# Q
s
Tf
#
Introducing the known values for the heat transfer rate Q and the temperature Tf
# 11.2 kW2
s 4.1 103 kW/K
1293 K2
The value of the entropy production rate calculated in part (a) gauges the significance of irreversibilities associated with fric-
tion and heat transfer within the gearbox. In part (b), an additional source of irreversibility is included in the enlarged system,
namely the irreversibility associated with the heat transfer from the outer surface of the gearbox at Tb to the surroundings at Tf.
In this case, the irreversibilities within the gearbox are dominant, accounting for 97.6% of the total rate of entropy production.
6.5.5 Increase of Entropy Principle

Our study of the second law began in Sec. 5.1 with a discussion of the directionality of
processes. In the present development, it is shown that the energy and entropy balances can
be used together to determine direction.
The present discussion centers on an enlarged system comprising a system and that por-
tion of the surroundings affected by the system as it undergoes a process. Since all energy
and mass transfers taking place are included within the boundary of the enlarged system, the
enlarged system can be regarded as an isolated system.
An energy balance for the isolated system reduces to
E4 isol 0 (6.34a)
because no energy transfers take place across its boundary. Thus, the energy of the isolated
system remains constant. Since energy is an extensive property, its value for the isolated sys-
tem is the sum of its values for the system and surroundings, respectively, so Eq. 6.34a can
be written as
E4 system
E4 surr 0 (6.34b)
In either of these forms, the conservation of energy principle places a constraint on the processes
that can occur. For a process to take place, it is necessary for the energy of the system plus the
surroundings to remain constant. However, not all processes for which this constraint is satis-
fied can actually occur. Processes also must satisfy the second law, as discussed next.
An entropy balance for the isolated system reduces to
0
a b
sisol
2 dQ
S4 isol
1 T b
or
S4 isol sisol (6.35a)
where isol is the total amount of entropy produced within the system and its surroundings.
Since entropy is produced in all actual processes, the only processes that can occur are those
for which the entropy of the isolated system increases. This is known as the increase of increase of entropy
entropy principle. The increase of entropy principle is sometimes considered an alternative principle
statement of the second law.
Since entropy is an extensive property, its value for the isolated system is the sum of its
values for the system and surroundings, respectively, so Eq. 6.35a can be written as
S4 system
S4 surr sisol (6.35b)
Notice that this equation does not require the entropy change to be positive for both the
system and surroundings but only that the sum of the changes is positive. In either of
these forms, the increase of entropy principle dictates the direction in which any process
can proceed: the direction that causes the total entropy of the system plus surroundings
to increase.
We noted previously the tendency of systems left to themselves to undergo processes
until a condition of equilibrium is attained (Sec. 5.1). The increase of entropy principle
suggests that the entropy of an isolated system increases as the state of equilibrium is
approached, with the equilibrium state being attained when the entropy reaches a maxi-
mum. This interpretation is considered again in Sec. 14.1, which deals with equilibrium
criteria.
The example to follow illustrates the increase of entropy principle.
EXAMPLE 6.5 Quenching a Hot Metal Bar
A 0.3 kg metal bar initially at 1200K is removed from an oven and quenched by immersing it in a closed tank containing
9 kg of water initially at 300K. Each substance can be modeled as incompressible. An appropriate constant specific heat value
for the water is cw 4.2 kJ/kg K, and an appropriate value for the metal is cm 0.42 kJ/kg K. Heat transfer from the tank
contents can be neglected. Determine (a) the final equilibrium temperature of the metal bar and the water, in K, and (b) the
amount of entropy produced, in kJ/.
SOLUTION
Known: A hot metal bar is quenched by immersing it in a tank containing water.
Find: Determine the final equilibrium temperature of the metal bar and the water, and the amount of entropy produced.
System boundary
Assumptions:
1. The metal bar and the water within the tank form a closed system,
as shown on the accompanying sketch.
2. There is no energy transfer by heat or work: The system is isolated.
3. There is no change in kinetic or potential energy.
4. The water and metal bar are each modeled as incompressible with
Metal bar: Water: known specific heats.
Tmi = 1200 Twi = 300K
cm = 0.42 kJ/kg cw = 4.2 kJ/kg
mm = 0.3 kg mw = 9 kg
Figure E6.5
Analysis:
(a) The final equilibrium temperature can be evaluated from an energy balance
0 0 0 0
KE
PE
U Q W
where the indicated terms vanish by assumptions 2 and 3. Since internal energy is an extensive property, its value for the over-
all system is the sum of the values for the water and metal, respectively. Thus, the energy balance becomes
Uwater
Umetal 0
Using Eq. 3.20a to evaluate the internal energy changes of the water and metal in terms of the constant specific heats
mwcw 1Tf Twi 2
mmcm 1Tf Tmi 2 0
where Tf is the final equilibrium temperature, and Twi and Tmi are the initial temperatures of the water and metal, respectively. Solv-
ing for Tf and inserting values
mw 1cwcm 2Twi
mmTmi
Tf
mw 1cw cm 2
mm
19 kg211021300K2
10.3 kg211200K2

19 kg21102
10.3 kg2
303K
(b) The amount of entropy production can be evaluated from an entropy balance. Since no heat transfer occurs between the
system and its surroundings, there is no accompanying entropy transfer, and an entropy balance for the system reduces to
a b
s
2 dQ
S
1 T b
Entropy is an extensive property, so its value for the system is the sum of its values for the water and the metal, respectively,
and the entropy balance becomes
Swater
Smetal s
Evaluating the entropy changes using Eq. 6.24 for incompressible substances, the foregoing equation can be written as
Tf Tf
s mwcw ln
mmcm ln
Twi Tmi
Inserting values
s 19 kg2 a4.2 b ln
10.3 kg2 a0.42 # b ln
kJ 303 kJ 303
kg # K 300 kg K 1200
a0.3761
kJ
b
a0.1734 b 0.2027 kJ/K
kJ
K K
The metal bar experiences a decrease in entropy. The entropy of the water increases. In accord with the increase of en-
tropy principle, the entropy of the isolated system increases.
The value of is sensitive to roundoff in the value of Tf.
STATISTICAL INTERPRETATION OF ENTROPY
In statistical thermodynamics, entropy is associated with the notion of disorder and the sec-
ond law statement that the entropy of an isolated system undergoing a spontaneous process
tends to increase is equivalent to saying that the disorder of the isolated system tends to in-
crease. Let us conclude the present discussion with a brief summary of concepts from the
microscopic viewpoint related to these ideas.
6.6 Entropy Rate Balance for Control Volumes 231

RIP
Roll Over Boltzmann no new fundamental
understanding. S = k ln w
Physicist Constantino Tsallis has proposed a new statistical The new statistical
definition of entropy some say will shake the foundations of definition reduces to
science as we know it. The Boltzmann relation, providing the the Boltzmann rela-
link between the microscopic interpretation of entropy and ob- tion for systems at
servations of macroscopic system behavior for over a century, equilibrium. But for
is being called into question. Scientists are weighing in on systems at states far
whether the theory provides new fundamental understanding from equilibrium the
or simply amplifies our thinking. new definition shines, say its supporters. The theory uses the
Supporters of the new definition of entropy say it extends mathematical notion of fractals to account for nonequilibrium
the scope of statistical thermodynamics to new and exciting behavior and describes systems on the verge of chaos by new
classes of problems. They claim it fills a gap in theory first statistical descriptions. Time will tell whether the new defini-
noted by Einstein and allows researchers to explain phenom- tion is accepted as the basis of statistical mechanics, or takes
ena ranging from the movement of microorganisms to the mo- its place on a long list of bright ideas that fell by the wayside
tions of stars, and even swings in the stock market. Skeptics of science.
believe that it only provides an empirical fudge factor with
Viewed macroscopically, an equilibrium state of a system appears to be unchanging, but

on the microscopic level the particles making up the matter are continually in motion. Ac-
cordingly, a vast number of possible microscopic states correspond to any given macroscopic
equilibrium state. The total number of possible microscopic states available to a system is
called the thermodynamic probability, w. Entropy is related to w by the Boltzmann relation
S k ln w (6.36)
where k is Boltzmanns constant. From this equation we see that any process that increases
the number of possible microscopic states of a system increases its entropy, and conversely.
Hence, for an isolated system, processes only occur in such a way that the number of mi-
croscopic states available to the system increases. The number w is referred to as the diso-
rder of the system. We can say, then, that the only processes an isolated system can undergo
are those that increase the disorder of the system.

6.6 Entropy Rate Balance for
Control Volumes
Thus far the discussion of the entropy balance concept has been restricted to the case of
closed systems. In the present section the entropy balance is extended to control volumes.
Like mass and energy, entropy is an extensive property, so it too can be transferred into
or out of a control volume by streams of matter. Since this is the principal difference be-
tween the closed system and control volume forms, the control volume entropy rate balance
can be obtained by modifying Eq. 6.32 to account for these entropy transfers. The result
is
#
dScv Qj # # #
a
a misi a mese
scv (6.37)
dt j Tj control volume entropy
j e

rate of rates of rate of rate balance
entropy entropy entropy
change transfer production
where dScvdt represents the time rate of change of entropy within the control volume.
entropy transfer # #
The terms misi and me se account, respectively, for rates of entropy
# transfer accompany-
accompanying mass flow ing mass flow into and out of the control volume. The term Qj represents the time rate
of heat transfer
# at the location on the boundary where the instantaneous temperature # is
Tj. The ratio QjTj accounts for the accompanying rate of entropy transfer. The term scv
denotes the time rate of entropy production due to irreversibilities within the control
volume.
INTEGRAL FORM
As for the cases of the control volume mass and energy rate balances, the entropy rate bal-
ance can be expressed in terms of local properties to obtain forms that are more generally
applicable. Thus, the term Scv(t), representing the total entropy associated with the control
volume at time t, can be written as a volume integral
Scv 1t2 rs dV
V
where and s denote, respectively, the local density and specific entropy. The rate of entropy
transfer accompanying heat transfer can be expressed more generally as an integral over the
surface of the control volume
time rate of entropy #

transfer accompanying a b dA
q
heat transfer A T b
#
where q is the heat flux, the time rate of heat transfer per unit of surface area, through the
location on the boundary where the instantaneous temperature is T. The subscript b is added
as a reminder that the integrand is evaluated on the boundary of the control volume. In ad-
dition, the terms accounting for entropy transfer accompanying mass flow can be expressed
as integrals over the inlet and exit flow areas, resulting in the following form of the entropy
rate balance
#
a b dA
a a srV dAb a a srV dAb
s#
d q
rs dV n n cv (6.38)
dt V A T b i A i e A e
where Vn denotes the normal component in the direction of flow of the velocity relative to
the flow area. In some cases, it is also convenient to express the entropy production rate as
a volume integral of the local volumetric rate of entropy production within the control vol-
ume. The study of Eq. 6.38 brings out the assumptions underlying Eq. 6.37. Finally, note
that for a closed system the sums accounting for entropy transfer at inlets and exits drop
out, and Eq. 6.38 reduces to give a more general form of Eq. 6.32.
6.6.1 Analyzing Control Volumes at Steady State

Since a great many engineering analyses involve control volumes at steady state, it is in-
structive to list steady-state forms of the balances developed for mass, energy, and entropy.
At steady state, the conservation of mass principle takes the form
# #
a mi a me (4.27)
i e
The energy rate balance at steady state is
V2i V2e
0 Qcv Wcv
a mi ahi

gzi b a me ahe

gze b
# # # #
(4.28a)
i 2 e 2
Finally, the steady-state form of the entropy rate balance is obtained by reducing Eq. 6.37
to give
# steady-state entropy
Qj # # #
0a
a misi a mese
scv (6.39) rate balance
j Tj i e
These equations often must be solved simultaneously, together with appropriate property
relations.
Mass and energy are conserved quantities, but entropy is not conserved. Equation 4.27 in-
dicates that at steady state the total rate of mass flow into the control volume equals the total
rate of mass flow out of the control volume. Similarly, Eq. 4.28a indicates that the total rate
of energy transfer into the control volume equals the total rate of energy transfer out of the
control volume. However, Eq. 6.39 requires that the rate at which entropy is transferred out
must exceed the rate at which entropy enters, the difference being the rate of entropy pro-
duction within the control volume owing to irreversibilities.
ONE-INLET, ONE-EXIT CONTROL VOLUMES
Since many applications involve one-inlet, one-exit control volumes at steady state, let us
also list the form of the entropy rate balance for this important case:
#
Qj

m 1s1 s2 2
scv
# #
0a
j T j
#
Or, on dividing by the mass flow rate m and rearranging
# #
Qj
s2 s1 # a a b
1 scv
# (6.40)
m j Tj m
The two terms on the right side of Eq. 6.40 denote, respectively, the rate of entropy trans-
fer accompanying heat transfer and the rate of entropy production within the control vol-
ume, each per unit of mass flowing through the control volume. From Eq. 6.40 it can be
concluded that the entropy of a unit of mass passing from inlet to exit can increase, de-
crease, or remain the same. Furthermore, because the value of the second term on the
right can never be negative, a decrease in the specific entropy from inlet to exit can be
realized only when more entropy is transferred out of the control volume accompanying
heat transfer than is produced by irreversibilities within the control volume. When the
value of this entropy transfer term is positive, the specific entropy at the exit is greater
than the specific entropy at the inlet whether internal irreversibilities are present or not.
In the special case where there is no entropy transfer accompanying heat transfer, Eq. 6.40
reduces to
#
scv
s2 s1 # (6.41)
m
Accordingly, when irreversibilities are present within the control volume, the entropy of a
unit of mass increases as it passes from inlet to exit. In the limiting case in which no irre-
versibilities are present, the unit mass passes through the control volume with no change in
its entropythat is, isentropically.
6.6.2 Illustrations
The following examples illustrate the use of the mass, energy, and entropy balances for the
analysis of control volumes at steady state. Carefully note that property relations and prop-
erty diagrams also play important roles in arriving at solutions.
In the first example, we evaluate the rate of entropy production within a turbine operat-
ing at steady state when there is heat transfer from the turbine.
EXAMPLE 6.6 Entropy Production in a Steam Turbine
Steam enters a turbine with a pressure of 30 bar, a temperature of 400C, and a velocity of 160 m /s. Saturated vapor at 100C
exits with a velocity of 100 m /s. At steady state, the turbine develops work equal to 540 kJ per kg of steam flowing through
the turbine. Heat transfer between the turbine and its surroundings occurs at an average outer surface temperature of 350 K.
Determine the rate at which entropy is produced within the turbine per kg of steam flowing, in kJ/kg # K. Neglect the change
in potential energy between inlet and exit.
SOLUTION
Known: Steam expands through a turbine at steady state for which data are provided.
Find: Determine the rate of entropy production per kg of steam flowing.
30 bar
T 400C
1
p1 = 30 bar
Wcv
T1 = 400C = 540 kJ/kg
V1 = 160 m/s 1 m
100C 2
T2 = 100C
Tb = 350 K 2 Saturated vapor
V2 = 100 m/s s
Figure E6.6
Assumptions:
1. The control volume shown on the accompanying sketch is at steady state.

2. Heat transfer from the turbine to the surroundings occurs at a specified average outer surface temperature.
3. The change in potential energy between inlet and exit can be neglected.
Analysis: To determine the entropy production per unit mass flowing through the turbine, begin with mass and entropy rate
balances for the one-inlet, one-exit control volume at steady state:
# #
0 m1 m2
#
Qj # # #
0 a
m1s1 m2s2
scv
j Tj
#
Since heat transfer occurs only at Tb 350 K, the first term on the right side of the entropy rate balance reduces to QcvTb.
Combining the mass and entropy rate balances
#

m1s1 s2 2
scv
Qcv # #
0
Tb
where m is the mass flow rate. Solving for scvm

# # #
#
Qcvm
# #

1s2 s1 2
scv
#
m Tb
#
The heat transfer rate, Qcvm, required by this expression is evaluated next.
#
Reduction of the mass and energy rate balances results in
# #
V22 V21
# #
1h2 h1 2
a b
Qcv Wcv
m m 2
where the potential energy change from inlet to exit is dropped by assumption 3. From Table A-4 at 30 bar, 400C, h1
3230.9 kJ/kg, and from Table A-2, h2 hg(100C) 2676.1 kJ/kg. Thus
11002 2 11602 2 m2
#

12676.1 3230.92 a b
c da 2b ` ` ` `
Qcv kJ kJ 1N 1 kJ
# 540
m kg kg 2 s 1 kg # m /s2 103 N # m
540 554.8 7.8 22.6 kJ/kg
From Table A-2, s2 7.3549 kJ/kg # K, and from Table A-4, s1 6.9212 kJ/kg # K. Inserting values into the expression
for entropy production
122.6 kJ/ kg2

#

17.3549 6.92122 a # b
scv kJ
#
m 350 K kg K
0.0646
0.4337 0.4983 kJ/kg # K
If the boundary were located to include a portion of the immediate surroundings so heat transfer would take place at the
temperature of the surroundings, say Tf 293 K, the entropy production for the enlarged control volume would be
0.511 kJ/kg # K. It is left as an exercise to verify this value and to explain why the entropy production for the enlarged
control volume would be greater than for a control volume consisting of the turbine only.
In Example 6.7, the mass, energy, and entropy rate balances are used to evaluate a per-
formance claim for a device to produce hot and cold streams of air from a single stream of
air at an intermediate temperature.
EXAMPLE 6.7 Evaluating a Performance Claim
An inventor claims to have developed a device requiring no energy transfer by work or heat transfer, yet able to produce hot
and cold streams of air from a single stream of air at an intermediate temperature. The inventor provides steady-state test data
indicating that when air enters at a temperature of 39C and a pressure of 5.0 bars, separate streams of air exit at temperatures
of 18C and 79C, respectively, and each at a pressure of 1 bar. Sixty percent of the mass entering the device exits at the lower
temperature. Evaluate the inventors claim, employing the ideal gas model for air and ignoring changes in the kinetic and po-
tential energies of the streams from inlet to exit.
SOLUTION
Known: Data are provided for a device that at steady state produces hot and cold streams of air from a single stream of air
at an intermediate temperature without energy transfers by work or heat.
Find: Evaluate whether the device can operate as claimed.
T1 = 21C
1 p1 = 5.1 bars
2
Inlet
T2 = 79C
p2 = 1 bar
Hot outlet
Cold outlet T3 = 18C

p3 = 1 bar
Figure E6.7
Assumptions:

# #
2. For the control volume, Wcv 0 and Qcv 0.
3. Changes in the kinetic and potential energies from inlet to exit can be ignored.
4. The air is modeled as an ideal gas with constant cp 1.0 kJ/kg # K.
Analysis: For the device to operate as claimed, the conservation of mass and energy principles must be satisfied. The sec-
ond law of thermodynamics also must be satisfied; and in particular the rate of entropy production cannot be negative. Ac-
cordingly, the mass, energy and entropy rate balances are considered in turn.
With assumptions 13, the mass and energy rate balances reduce, respectively, to
# # #
m1 m2
m3
# # #
0 m1h1 m2h2 m3h3
# # # #
Since m3 0.6m1, it follows from the mass rate balance that m2 0.4m1. By combining the mass and energy rate balances
and evaluating changes in specific enthalpy using constant cp, the energy rate balance is also satisfied. That is
0 1m2
m3 2 h1 m2h2 m3h3
# # # #
m2 1h1 h2 2
m3 1h1 h3 2
# #
0.4m1cp 1T1 T2 2
0.6m1cp 1T1 T3 2
# #
0.411052
0.61702
0
Accordingly, with the given data the conservation of mass and energy principles are satisfied.
Since no significant heat transfer occurs, the entropy rate balance at steady state reads
# 0
Qj# # # #
0a
m1s1 m2s2 m3s3
scv
j Tj
Combining the mass and entropy rate balances

0 1m2
m3 2s1 m2s2 m3s3
scv
# # # # #
m2 1s1 s2 2
m3 1s1 s3 2
scv
# # #
0.4m1 1s1 s2 2
0.6m1 1s1 s3 2
scv
# # #
Solving for scvm1 and using Eq. 6.23 to evaluate changes in specific entropy
# #
#
# 0.4 c cp ln R ln d
0.6 c cp ln R ln d
scv T2 p2 T3 p3
m1 T1 p1 T1 p1
0.4 c a1.0 b ln a b ln d
kJ 352 8.314 kJ 1
#
kg K 294 #
28.97 kg K 5.0

0.6 c a1.0 b ln a b ln d
kJ 255 8.314 kJ 1
kg # K 294 28.97 kg # K 5.0
0.454 kJ/kg # K
Thus, the second law of thermodynamics is also satisfied.
On the basis of this evaluation, the inventors claim does not violate principles of thermodynamics.
Since the specific heat cp of air varies little over the temperature interval from 0 to 79C, cp can be taken as constant.
From Table A-20, cp 1.0 kJ /kg # K.
Since temperature differences are involved in this calculation, the temperatures can be either in C or K.
In this calculation involving temperature ratios, the temperatures must be in K.
If the value of the rate of entropy production had been negative or zero, the claim would be rejected. A negative value is
impossible by the second law and a zero value would indicate operation without irreversibilities.
Such devices do exist. They are known as vortex tubes and are used in industry for spot cooling.
In Example 6.8, we evaluate and compare the rates of entropy production for three com-
ponents of a heat pump system. Heat pumps are considered in detail in Chap. 10.
EXAMPLE 6.8 Entropy Production in Heat Pump Components
Components of a heat pump for supplying heated air to a dwelling are shown in the schematic below. At steady state,
Refrigerant 22 enters the compressor at 5C, 3.5 bar and is compressed adiabatically to 75C, 14 bar. From the com-
pressor, the refrigerant passes through the condenser, where it condenses to liquid at 28C, 14 bar. The refrigerant then
expands through a throttling valve to 3.5 bar. The states of the refrigerant are shown on the accompanying Ts diagram.
Return air from the dwelling enters the condenser at 20C, 1 bar with a volumetric flow rate of 0.42 m3/s and exits at
50C with a negligible change in pressure. Using the ideal gas model for the air and neglecting kinetic and potential en-
ergy effects, (a) determine the rates of entropy production, in kW/K, for control volumes enclosing the condenser,
compressor, and expansion valve, respectively. (b) Discuss the sources of irreversibility in the components considered in
part (a).
SOLUTION
Known: Refrigerant 22 is compressed adiabatically, condensed by heat transfer to air passing through a heat exchanger, and
then expanded through a throttling valve. Steady-state operating data are known.
Find: Determine the entropy production rates for control volumes enclosing the condenser, compressor, and expansion valve,
respectively, and discuss the sources of irreversibility in these components.
Indoor return air Supply air

T5 = 20C T = 50C
p5 = 1 bar 5 6 p 6 = 1 bar
6
(AV)5 = 0.42 m3/s
T
75C
3 p2 = 14 bar 2
Condenser 2
p3 = 14 bar T2 = 75C
T3 = 28C 14 bar
Expansion 3
Compressor 28C
valve
p4 = 3.5 bar T1 = 5C
4 p1 = 3.5 bar 3.5 bar 5C
1 1
4
s
Outdoor air
Evaporator
Figure E6.8
Assumptions:
1. Each component is analyzed as a control volume at steady state.

2. The compressor operates adiabatically, and the expansion across the valve is a throttling process.
# #
3. For the control volume enclosing the condenser, Wcv 0 and Qcv 0.
4. Kinetic and potential energy effects can be neglected.
5. The air is modeled as an ideal gas with constant cp 1.005 kJ/kg # K.
Analysis:
(a) Let us begin by obtaining property data at each of the principal refrigerant states located on the accompanying schematic and
Ts diagram. At the inlet to the compressor, the refrigerant is a superheated vapor at 5C, 3.5 bar, so from Table A-9,
s1 0.9572 kJ/kg # K. Similarly, at state 2, the refrigerant is a superheated vapor at 75C, 14 bar, so interpolating in Table A-9
gives s2 0.98225 kJ/kg # K and h2 294.17 kJ/kg.
State 3 is compressed liquid at 28C, 14 bar. From Table A-7, s3 sf (28C) 0.2936 kJ/kg # K and h3 hf (28C) 79.05 kJ/kg.
The expansion through the valve is a throttling process, so h3 h4. Using data from Table A-8, the quality at state 4 is
1h4 hf4 2 179.05 33.092
x4 0.216
1hfg 2 4 1212.912
and the specific entropy is
s4 sf4
x4 1sg4 sf4 2 0.1328
0.21610.9431 0.13282 0.3078 kJ/kg # K
Condenser.
Consider the control volume enclosing the condenser. With assumptions 1 and 3, the entropy rate balance reduces to
0 mref 1s2 s3 2
mair 1s5 s6 2
scond
# # #
# # #
To evaluate scond requires the two mass flow rates, mair and mref , and the change in specific entropy for the air. These are ob-
tained next.
Evaluating the mass flow rate of air using the ideal gas model (assumption 5)
1AV2 5
1AV2 5
# p5
mair
v5 RT5
m3 11 bar2 105 N/m2
a0.42 b ` ` ` 3 # ` 0.5 kg/s
1 kJ
a b 1293 K2
s 8.314 kJ 1 bar 10 N m
28.97 kg # K
The refrigerant mass flow rate is determined using an energy balance for the control volume enclosing the condenser together
with assumptions 1, 3, and 4 to obtain
mair 1h6 h5 2
#
#
mref
1h2 h3 2
With assumption 5, h6 h5 cp(T6 T5). Inserting values
a0.5 b a1.005 # b 1323 2932K

kg kJ
# s kg K
mref 0.07 kg/s
1294 .17 79 .052 kJ/kg
Using Eq. 6.23, the change in specific entropy of the air is
T6 p6
s6 s5 cp ln R ln
T5 p5
0
a1.005 # b ln a b R ln a b 0.098 kJ/kg # K

kJ 323 1.0
kg K 293 1.0
#
Finally, solving the entropy balance for scond and inserting values
scond mref 1s3 s2 2
mair 1s6 s5 2
# # #
c a0.07 b 10.2936 0.982252

10.52 10.0982 d ` `
kg kJ 1 kW
s kg # K 1 kJ/s
kW
7.95 104
K
Compressor.
For the control volume enclosing the compressor, the entropy rate balance reduces with assumptions 1 and 3 to
0 mref 1s1 s2 2
scomp
# #
or
scomp mref 1s2 s1 2
# #
a0.07 b 10.98225 0.95722 a # b ` `

kg kJ 1 kW
s kg K 1 kJ/s
17.5 104 kW/K
Valve.
Finally, for the control volume enclosing the throttling valve, the entropy rate balance reduces to
0 mref 1s3 s4 2
svalve
# #
#
Solving for svalve and inserting values
svalve mref 1s4 s3 2 a0.07 b 10.3078 0.29362 a # b ` `

# # kg kJ 1 kW
s kg K 1 kJ/s
9.94 104 kW/K
(b) The following table summarizes, in rank order, the calculated entropy production rates:
.
Component cv (kW/K)
17.5 104
compressor
valve 9.94 104
condenser 7.95 104
Entropy production in the compressor is due to fluid friction, mechanical friction of the moving parts, and internal heat trans-
fer. For the valve, the irreversibility is primarily due to fluid friction accompanying the expansion across the valve. The prin-
cipal source of irreversibility in the condenser is the temperature difference between the air and refrigerant streams. In this
example, there are no pressure drops for either stream passing through the condenser, but slight pressure drops due to fluid
friction would normally contribute to the irreversibility of condensers. The evaporator lightly shown in Fig. E6.8 has not been
analyzed.
Due to the relatively small temperature change of the air, the specific heat cp can be taken as constant at the average of
the inlet and exit air temperatures.
#
Temperatures in K are used to evaluate mref, but since a temperature difference is involved the same result would be ob-
tained if temperatures in C were used. Temperatures in K must be used when a temperature ratio is involved, as in Eq. 6.23
used to evaluate s6 s5.
By focusing attention on reducing irreversibilities at the sites with the highest entropy production rates, thermodynamic
improvements may be possible. However, costs and other constraints must be considered, and can be overriding.
6.7 Isentropic Processes

The term isentropic means constant entropy. Isentropic processes are encountered in many
subsequent discussions. The object of the present section is to explain how properties are re-
lated at any two states of a process in which there is no change in specific entropy.
6.7.1 General Considerations

The properties at states having the same specific entropy can be related using the graphical
and tabular property data discussed in Sec. 6.3.1. For example, as illustrated by Fig. 6.9, tem-
peratureentropy and enthalpyentropy diagrams are particularly convenient for determining
properties at states having the same value of specific entropy. All states on a vertical line
passing through a given state have the same entropy. If state 1 on Fig. 6.9 is fixed by pres-
sure p1 and temperature T1, states 2 and 3 are readily located once one additional property,
such as pressure or temperature, is specified. The values of several other properties at states
2 and 3 can then be read directly from the figures.
Tabular data also can be used to relate two states having the same specific entropy. For
the case shown in Fig. 6.9, the specific entropy at state 1 could be determined from the
superheated vapor table. Then, with s2 s1 and one other property value, such as p2 or T2,
T p1 h p1
1 1 T1
T1
p2 p3
2 T2
p2
T2 T3
2
p3
3
3
T3
s s
Figure 6.9 Ts and hs diagrams showing states having the same value of
specific entropy.
6.7 Isentropic Processes 241
state 2 could be located in the superheated vapor table. The values of the properties v, u, and
h at state 2 can then be read from the table. An illustration of this procedure is given in Sec.
6.3.1. Note that state 3 falls in the two-phase liquidvapor regions of Fig. 6.9. Since s3 s1,
the quality at state 3 could be determined using Eq. 6.6. With the quality known, other prop-
erties such as v, u, and h could then be evaluated. Computer retrieval of entropy data pro-
vides an alternative to tabular data.
6.7.2 Using the Ideal Gas Model

Figure 6.10 shows two states of an ideal gas having the same value of specific entropy. Let T
v2
us consider relations among pressure, specific volume, and temperature at these states, first p2
using the ideal gas tables and then assuming specific heats are constant. 2
T2
IDEAL GAS TABLES

v1
For two states having the same specific entropy, Eq. 6.21a reduces to p1
1
0 s1T2 2 s1T1 2 R ln
p2 T1
(6.42a)
p1
Equation 6.42a involves four property values: p1, T1, p2, and T2. If any three are known, the
s
fourth can be determined. If, for example, the temperature at state 1 and the pressure ratio
Figure 6.10 Two
p2p1 are known, the temperature at state 2 can be determined from
states of an ideal gas
where s2 s1.
s1T2 2 s1T1 2
R ln
p2
(6.42b)
p1
Since T1 is known, s(T1) would be obtained from the appropriate table, the value of s(T2 )
would be calculated, and temperature T2 would then be determined by interpolation. If p1,
T1, and T2 are specified and the pressure at state 2 is the unknown, Eq. 6.42a would be solved
to obtain
s1T2 2 s1T1 2
p2 p1 exp c d (6.42c)
R
Equations 6.42 can be used when s (or s) data are known, as for the gases of Tables A-22
and A-23.
AIR. For the special case of air modeled as an ideal gas, Eq. 6.42c provides the basis for
an alternative tabular approach for relating the temperatures and pressures at two states having
the same specific entropy. To introduce this, rewrite the equation as
p2 exp3s1T2 2 R4

p1 exp3s1T1 2 R4
The quantity exp[s(T )R] appearing in this expression is solely a function of temperature,
and is given the symbol pr(T ). A tabulation of pr versus temperature for air is provided in
Tables A-22.1 In terms of the function pr, the last equation becomes
1s1 s2, air only2

p2 pr2
(6.43)
p1 pr1
1
The values of pr determined with this definition are inconveniently large, so they are divided by a scale factor
before tabulating to give a convenient range of numbers.
where pr1 pr(T1) and pr2 pr(T2). The function pr is sometimes called the relative pres-
sure. Observe that pr is not truly a pressure, so the name relative pressure is misleading. Also,
be careful not to confuse pr with the reduced pressure of the compressibility diagram.
A relation between specific volumes and temperatures for two states of air having the
same specific entropy can also be developed. With the ideal gas equation of state, v RTp,
the ratio of the specific volumes is
a ba b
v2 RT2 p1
v1 p2 RT1
Then, since the two states have the same specific entropy, Eq. 6.43 can be introduced to give
pr 1T1 2
c dc d
v2 RT2
v1 pr 1T2 2 RT1
The ratio RTpr(T ) appearing on the right side of the last equation is solely a function of
temperature, and is given the symbol vr(T ). Values of vr for air are tabulated versus tem-
perature in Tables A-22. In terms of the function vr, the last equation becomes
1s1 s2, air only2

v2 vr2
(6.44)
v1 vr1
METHODOLOGY where vr1 vr(T1) and vr2 vr(T2). The function vr is sometimes called the relative volume.
UPDATE
Despite the name given to it, vr(T ) is not truly a volume. Also, be careful not to confuse it
When applying the with the pseudoreduced specific volume of the compressibility diagram.
software IT to relate two
states of an ideal gas
having the same value of ASSUMING CONSTANT SPECIFIC HEATS
specific entropy, note that
IT returns specific entropy
Let us consider next how properties are related for isentropic processes of an ideal gas when
directly and does not the specific heats are constants. For any such case, Eqs. 6.22 and 6.23 reduce to the equations
employ the special T2 p2
functions s, pr and vr. 0 cp ln R ln
T1 p1
T2 v2
0 cv ln
R ln
T1 v1
Introducing the ideal gas relations
kR R
cp , cv (3.47)
k1 k1
these equations can be solved, respectively, to give
p2 1k12k
a b 1s1 s2, constant k2
T2
(6.45)
T1 p1

v1 k1
T2
(6.46)
T1 v2
The following relation can be obtained by eliminating the temperature ratio from
Eqs. 6.45 and 6.46:
v1 k
p2
p1 v2
(6.47)
p n = 1 T
n=k n=
n = 1
nt
n=0
ta
ns
co
t
an
n st
=
n=0
v
o
p =c
T n=1
=
co
ns
s= ta n
co t
ns n=1
ta nt
n= n=k
v s
Figure 6.11 Polytropic processes on pv and Ts diagrams.
From the form of Eq. 6.47, it can be concluded that a polytropic process pvk constant
of an ideal gas with constant k is an isentropic process. We noted in Sec. 3.8 that a poly-
tropic process of an ideal gas for which n 1 is an isothermal (constant-temperature) process.
For any fluid, n 0 corresponds to an isobaric (constant-pressure) process and n
corresponds to an isometric (constant-volume) process. Polytropic processes corresponding
to these values of n are shown in Fig. 6.11 on pv and Ts diagrams.
The foregoing means for evaluating data for an isentropic process of air modeled as an
ideal gas are considered in the next example.
EXAMPLE 6.9 Isentropic Process of Air
Air undergoes an isentropic process from p1 1 bar, T1 300K to a final state where the temperature is T2 650K.
Employing the ideal gas model, determine the final pressure p2, in atm. Solve using (a) pr data from Table A-22 (b) Int-
eractive Thermodynamics: IT, and (c) a constant specific heat ratio k evaluated at the mean temperature, 475K, from Table
A-20.
SOLUTION
Known: Air undergoes an isentropic process from a state where pressure and temperature are known to a state where the
temperature is specified.
Find: Determine the final pressure using (a) pr data, (b) IT, and (c) a constant value for the specific heat ratio k.
T
p2 = ?
2 T2 = 650 K Assumptions:
1. A quantity of air as the system undergoes an isentropic process.

p1 = 1 bar 2. The air can be modeled as an ideal gas.
1
T1 = 300
3. In part (c) the specific heat ratio is constant.
s
Figure E6.9
Analysis:
(a) The pressures and temperatures at two states of an ideal gas having the same specific entropy are related by Eq. 6.43
p2 pr2

p1 pr1
Solving
pr2
p2 p1
pr1
With pr values from Table A-22
p 11 bar2
21.86
15.77 bars
1.3860
(b) The IT solution follows:
T1 = 300 // K
p1 = 1 // atm
T2 = 650 // K
s_TP(Air, T1,p1) = s_TP(Air,T2,p2)
// Result: p2 = 15.77 bar
(c) When the specific heat ratio k is assumed constant, the temperatures and pressures at two states of an ideal gas having
the same specific entropy are related by Eq. 6.45. Thus
T2 k1k12
p2 p1 a b
T1
From Table A-20 at 202C (475K), k 1.39. Inserting values into the above expression
650 1.390.39
p2 11 bar2 a b 15.81 bar
300
IT returns a value for p2 even though it is an implicit variable in the argument of the specific entropy function. Also note
that IT returns values for specific entropy directly and does not employ special functions such as s, pr and vr.
The close agreement between the answer obtained in part (c) and that of parts (a), (b) can be attributed to the use of an
appropriate value for the specific heat ratio k.
Another illustration of an isentropic process of an ideal gas is provided in the next ex-
ample dealing with air leaking from a tank.
EXAMPLE 6.10 Air Leaking from a Tank
A rigid, well-insulated tank is filled initially with 5 kg of air at a pressure of 5 bar and a temperature of 500 K. A leak de-
velops, and air slowly escapes until the pressure of the air remaining in the tank is 1 bar. Employing the ideal gas model, de-
termine the amount of mass remaining in the tank and its temperature.
SOLUTION
Known: A leak develops in a rigid, insulated tank initially containing air at a known state. Air slowly escapes until the pres-
sure in the tank is reduced to a specified value.
Find: Determine the amount of mass remaining in the tank and its temperature.
Assumptions:
System boundary 1. As shown on the accompanying sketch, the closed system is the mass
initially in the tank that remains in the tank.
Slow leak
2. There is no significant heat transfer between the system and its
surroundings.
Mass initially
in the tank that Mass initially in the
3. Irreversibilities within the tank can be ignored as the air slowly
remains in the tank tank that escapes escapes.
Initial condition of tank
Figure E6.10
Analysis: With the ideal gas equation of state, the mass initially in the tank that remains in the tank at the end of the process is
p2V
m2
1RM2 T2
where p2 and T2 are the final pressure and temperature, respectively. Similarly, the initial amount of mass within the tank, m1, is
p1V
m1
1RM2 T1
where p1 and T1 are the initial pressure and temperature, respectively. Eliminating volume between these two expressions, the
mass of the system is
m2 a b a b m1
p2 T1
p1 T2
Except for the final temperature of the air remaining in the tank, T2, all required values are known. The remainder of the so-
lution mainly concerns the evaluation of T2.
For the closed system under consideration, there are no significant irreversibilities (assumption 3), and no heat transfer oc-
curs (assumption 2). Accordingly, the entropy balance reduces to
0
a b
s 0
2 dQ 0
S
1 T b
Since the system mass remains constant, S m2 s, so
s 0
That is, the initial and final states of the system have the same value of specific entropy.
Using Eq. 6.43
pr2 a b pr1
p2
p1
where p1 5 bar and p2 1 bar. With pr1 8.411 from Table A-22 at 500 K, the previous equation gives pr2 1.6822.
Using this to interpolate in Table A-22, T2 317 K.
Finally, inserting values into the expression for system mass
m2 a ba b 15 kg2 1.58 kg
1 bar 500 K
5 bar 317 K
This problem also could be solved by considering a control volume enclosing the tank. The state of the control volume
would change with time as air escapes. The details of the analysis are left as an exercise.
6.8 Isentropic Efficiencies of Turbines,

Nozzles, Compressors, and Pumps
Engineers make frequent use of efficiencies and many different efficiency definitions are em-
ployed. In the present section isentropic efficiencies for turbines, nozzles, compressors, and
pumps are introduced. Isentropic efficiencies involve a comparison between the actual per-
formance of a device and the performance that would be achieved under idealized circum-
stances for the same inlet state and the same exit pressure. These efficiencies are frequently
used in subsequent sections of the book.
ISENTROPIC TURBINE EFFICIENCY
To introduce the isentropic turbine efficiency, refer to Fig. 6.12, which shows a turbine expan-
sion on a Mollier diagram. The state of the matter entering the turbine and the exit pressure
are fixed. Heat transfer between the turbine and its surroundings is ignored, as are kinetic and
potential energy effects. With these assumptions, the mass and energy rate balances reduce, at
steady state, to give the work developed per unit of mass flowing through the turbine
#
Wcv
# h1 h2
m
Since state 1 is fixed, the specific enthalpy h1 is known. Accordingly, the value of the work
depends on the specific enthalpy h2 only, and increases as h2 is reduced. The maximum value
for the turbine work corresponds to the smallest allowed value for the specific enthalpy at
the turbine exit. This can be determined using the second law. Since there is no heat trans-
fer, the allowed exit states are constrained by Eq. 6.41
#
scv
# s2 s1 0
m
Because the entropy production scvm cannot be negative, states with s2 s1 are not acces-
# #
sible in an adiabatic expansion. The only states that actually can be attained adiabatically
are those with s2 s1. The state labeled 2s on Fig. 6.12 would be attained only in the limit
of no internal irreversibilities. This corresponds to an isentropic expansion through the tur-
bine. For fixed exit pressure, the specific enthalpy h2 decreases as the specific entropy s2
p1
h
1 T1
Actual
expansion
h1 h2
h1 h2s Isentropic
expansion
2
2s
Accessible
states
p2
Figure 6.12 Comparison of actual and

s isentropic expansions through a turbine.
6.8 Isentropic Efficiencies of Turbines, Nozzles, Compressors, and Pumps 247
decreases. Therefore, the smallest allowed value for h2 corresponds to state 2s, and the maxi-
mum value for the turbine work is
#
a # b h1 h2s
Wcv
m s
In an actual expansion through the turbine h2 h2s, and thus less work than the maxi-
mum would be developed. This difference can be gauged by the isentropic turbine efficiency
defined by
#
Wcvm
# isentropic turbine
ht # (6.48)
1Wcvm2 s
# efficiency
Both the numerator and denominator of this expression are evaluated for the same inlet state
and the same exit pressure. The value of t is typically 0.7 to 0.9 (7090%).
ISENTROPIC NOZZLE EFFICIENCY
A similar approach to that for turbines can be used to introduce the isentropic efficiency of
nozzles operating at steady state. The isentropic nozzle efficiency is defined as the ratio of
the actual specific kinetic energy of the gas leaving the nozzle, V22 2, to the kinetic energy
at the exit that would be achieved in an isentropic expansion between the same inlet state
and the same exhaust pressure, 1V22 22 s
V22 2 isentropic nozzle

hnozzle (6.49)
1V22 22 s efficiency
Nozzle efficiencies of 95% or more are common, indicating that well-designed nozzles are
nearly free of internal irreversibilities.
ISENTROPIC COMPRESSOR AND PUMP EFFICIENCIES
The form of the isentropic efficiency for compressors and pumps is taken up next. Refer to
Fig. 6.13, which shows a compression process on a Mollier diagram. The state of the mat-
ter entering the compressor and the exit pressure are fixed. For negligible heat transfer with
Accessible
states
h p2
2
2s
Actual
compression
h2 h1 Isentropic
h2s h1 compression
p1
Figure 6.13 Comparison of actual and

s isentropic compressions.

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the surroundings and no appreciable kinetic and potential energy effects, the work input per
unit of mass flowing through the compressor is
#
a # b h2 h1
Wcv
m
Since state 1 is fixed, the specific enthalpy h1 is known. Accordingly, the value of the work
input depends on the specific enthalpy at the exit, h2. The above expression shows that the
magnitude of the work input decreases as h2 decreases. The minimum work input corresponds
to the smallest allowed value for the specific enthalpy at the compressor exit. With similar
reasoning as for the turbine, the smallest allowed enthalpy at the exit state that would be
achieved in an isentropic compression from the specified inlet state to the specified exit pres-
sure. The minimum work input is given, therefore, by
#
a # b h2s h1
Wcv
m s
In an actual compression, h2 h2s, and thus more work than the minimum would be re-
quired. This difference can be gauged by the isentropic compressor efficiency defined by
1Wcvm2 s
isentropic compressor # #
hc
1Wcvm2
efficiency # # (6.50)
Both the numerator and denominator of this expression are evaluated for the same inlet state
and the same exit pressure. The value of c is typically 75 to 85% for compressors. An
isentropic pump isentropic pump efficiency, p, is defined similarly.
efficiency The series of four examples to follow illustrate various aspects of isentropic efficiencies
of turbines, nozzles, and compressors. Example 6.11 is a direct application of the isentropic
turbine efficiency t to a steam turbine. Here, t is known and the objective is to determine
the turbine work.
EXAMPLE 6.11 Evaluating Turbine Work Using the Isentropic Efficiency
A steam turbine operates at steady state with inlet conditions of p1 5 bar, T1 320C. Steam leaves the turbine at a pres-
sure of 1 bar. There is no significant heat transfer between the turbine and its surroundings, and kinetic and potential energy
changes between inlet and exit are negligible. If the isentropic turbine efficiency is 75%, determine the work developed per
unit mass of steam flowing through the turbine, in kJ/kg.
SOLUTION
Known: Steam expands through a turbine operating at steady state from a specified inlet state to a specified exit pressure.
The turbine efficiency is known.
Find: Determine the work developed per unit mass of steam flowing through the turbine.
p1 = 5 bar
h
1 T1
Actual
expansion
h1 h2 Assumptions:
Isentropic
h1 h2s
expansion
1. A control volume enclosing the turbine is at steady state.
2
2. The expansion is adiabatic and changes in kinetic and potential
2s
energy between the inlet and exit can be neglected.
Accessible
states
p2 = 1 bar
s
Figure E6.11
Analysis: The work developed can be determined using the isentropic turbine efficiency, Eq. 6.48, which on rearrangement
gives
# #
# ht a # b ht 1h1 h2s 2
Wcv Wcv
m m s
From Table A-4, h1 3105.6 kJ/kg and s1 7.5308 kJ/kg # K. The exit state for an isentropic expansion is fixed by
p2 1 bar and s2s s1. Interpolating with specific entropy in Table A-4 at 1 bar gives h2s 2743.0 kJ/kg. Substituting
values
#
Wcv
m
# 0.7513105.6 2743.02 271.95 kJ/kg
The effect of irreversibilities is to exact a penalty on the work output of the turbine. The work is only 75% of what it
would be for an isentropic expansion between the given inlet state and the turbine exhaust pressure. This is clearly illus-
trated in terms of enthalpy differences on the accompanying hs diagram.
The next example is similar to Example 6.11, but here the working substance is air as an
ideal gas. Moreover, in this case the turbine work is known and the objective is to determine
the isentropic turbine efficiency.
EXAMPLE 6.12 Evaluating the Isentropic Turbine Efficiency
A turbine operating at steady state receives air at a pressure of p1 3.0 bar and a temperature of T1 390 K. Air exits the
turbine at a pressure of p2 1.0 bar. The work developed is measured as 74 kJ per kg of air flowing through the turbine.
The turbine operates adiabatically, and changes in kinetic and potential energy between inlet and exit can be neglected. Using
the ideal gas model for air, determine the turbine efficiency.
SOLUTION
Known: Air expands adiabatically through a turbine at steady state from a specified inlet state to a specified exit pressure.
The work developed per kg of air flowing through the turbine is known.
Find: Determine the turbine efficiency.
3.0 bar
T
Air
turbine T1 = 390 K
Wcv
= 74 kJ/kg
p1 = 3.0 bar m Actual
T1 = 390 K expansion
p2 = 1.0 bar
Isentropic
1 2 expansion 1.0 bar
2
2s
s
Figure E6.12
Assumptions:

2. The expansion is adiabatic and changes in kinetic and potential energy between inlet and exit can be neglected.
Analysis: The numerator of the isentropic turbine efficiency, Eq. 6.48, is known. The denominator is evaluated as
follows.
The work developed in an isentropic expansion from the given inlet state to the specified exit pressure is
#
a # b h1 h2s
Wcv
m s
From Table A-22 at 390 K, h1 390.88 kJ/kg. To determine h2s, use Eq. 6.43
pr 1T2s 2 a b p 1T 2
p2
p1 r 1
With p1 3.0 bar, p2 1.0 bar, and pr1 3.481 from Table A-22 at 390 K
pr 1T2s 2 a b 13.4812 1.1603

1.0
3.0
Interpolation in Table A-22 gives h2s 285.27 kJ/kg. Thus

#
a # b 390.88 285.27 105.6 kJ/kg
Wcv
m s
Substituting values into Eq. 6.48
#
Wcvm
#
# 105.6 kJ/kg 0.70 170% 2
74 kJ/kg
ht #
1Wcvm2 s
In the next example, the objective is to determine the isentropic efficiency of a steam
nozzle.
EXAMPLE 6.13 Evaluating the Isentropic Nozzle Efficiency
Steam enters a nozzle operating at steady state at p1 1.0 MPa and T1 320C with a velocity of 30 m/s. The pressure and
temperature at the exit are p2 0.3 MPa and T2 180C. There is no significant heat transfer between the nozzle and its sur-
roundings, and changes in potential energy between inlet and exit can be neglected. Determine the nozzle efficiency.
SOLUTION
Known: Steam expands through a nozzle at steady state from a specified inlet state to a specified exit state. The velocity at
the inlet is known.
Find: Determine the nozzle efficiency.
1.0 MPa
1 320C
h Isentropic
expansion Actual
p1 = 1.0 MPa
expansion
T1 = 320C p2 = 0.3 MPa
V1 = 30 m/s T2 = 180C 0.3 MPa
180C
Steam 2
nozzle
2s
2
1
s
Figure E6.13
Assumptions:
1. The control volume shown on the accompanying sketch operates adiabatically at steady state.
#
2. For the control volume, Wcv 0 and the change in potential energy between inlet and exit can be neglected.
Analysis: The nozzle efficiency given by Eq. 6.49 requires the actual specific kinetic energy at the nozzle exit and the spe-
cific kinetic energy that would be achieved at the exit in an isentropic expansion from the given inlet state to the given exit
pressure. The mass and energy rate balances for the one-inlet, one-exit control volume at steady state reduce to give
V22 V21
h1 h2
2 2
This equation applies for both the actual expansion and the isentropic expansion.
From Table A-4 at T1 320C and p1 1.0 MPa, h1 3093.9 kJ/kg, s1 7.1962 kJ /kg # K. Also, with T2 180C
and p2 0.3 MPa, h2 2823.9 kJ/kg. Thus, the actual specific kinetic energy at the exit in kJ/kg is
V22 1302 2 m 2
a b a ba b
kJ 1N 1 kJ
(3093.9 2823.9)
2 kg 2 s 1 kg # m/s2 103 N # M
kJ
270.45
kg
Interpolating in Table A-4 at 0.3 MPa, with s2s s1, results in h2s 2813.3 kJ/kg. Accordingly, the specific kinetic energy
at the exit for an isentropic expansion is
V22 302
a b 3093.9 2813.3
281.05 kJ /kg
2 s 21103 2
Substituting values into Eq. 6.49
1V2222
0.962 196.2%2
270.45
hnozzle
1V22 22 s 281.05
The principal irreversibility in nozzles is friction between the flowing gas or liquid and the nozzle wall. The effect of fric-
tion is that a smaller exit kinetic energy, and thus a smaller exit velocity, is realized than would have been obtained in an
isentropic expansion to the same pressure.
In Example 6.14, the isentropic efficiency of a refrigerant compressor is evaluated, first

using data from property tables and then using IT.
EXAMPLE 6.14 Evaluating the Isentropic Compressor Efficiency
For the compressor of the heat pump system in Example 6.8, determine the power, in kW, and the isentropic efficiency using
(a) data from property tables, (b) Interactive Thermodynamics: IT.
SOLUTION
Known: Refrigerant 22 is compressed adiabatically at steady state from a specified inlet state to a specified exit state. The
mass flow rate is known.
Find: Determine the compressor power and the isentropic efficiency using (a) property tables, (b) IT.
2
2s
T T2 = 75C
14 bar Assumptions:
1. A control volume enclosing the compressor is at steady state.

2. The compression is adiabatic, and changes in kinetic and potential energy be-
3.5 bar tween the inlet and the exit can be neglected.
1 T1 = 5C
s
Figure E6.14
Analysis: (a) By assumptions 1 and 2, the mass and energy rate balances reduce to give
Wcv m 1h1 h2 2
# #
From Table A-9, h1 249.75 kJ/kg and h2 294.17 kJ/kg. Thus
Wcv 10.07 kg/s21249.75 294.172 kJ/kg ` ` 3.11 kW

# 1 kW
1 kJ/s
The isentropic compressor efficiency is determined using Eq. 6.50
1Wcvm2 s 1h2s h1 2
# #
hc # 1h h 2
1Wcvm2
#
2 1
In this expression, the denominator represents the work input per unit mass of refrigerant flowing for the actual compression
process, as calculated above. The numerator is the work input for an isentropic compression between the initial state and the
same exit pressure. The isentropic exit state is denoted as state 2s on the accompanying Ts diagram.
From Table A-9, s1 0.9572 kJ/kg # K. With s2s s1, interpolation in Table A-9 at 14 bar gives h2s 285.58 kJ/kg. Sub-
stituting values
1285.58 249.752
hc 0.81181%2
1294.17 249.752
# #
(b) The IT program follows. In the program, Wcv is denoted as Wdot, m as mdot, and c as eta_c.
// Given Data:
T1 = 5 // C
p1 = 3.5 // bar
T2 = 75 // C
p2 = 14 // bar
mdot = 0.07 // kg/s
// Determine the specific enthalpies.

h1 = h_PT(R22,p1,T1)
h2 = h_PT(R22,p2,T2)
// Calculate the power.

Wdot = mdot * (h1 h2)
// Find h2s:
s1 = s_PT(R22,p1,T1)
s2s = s_Ph(R22,p2,h2s)
s2s = s1
// Determine the isentropic compressor efficiency.

eta_c = (h2s h1) / (h2 h1)
#
Use the Solve button to obtain: Wcv 3.111 kW and hc 80.58%, which agree closely with the values obtained above.
The minimum theoretical power for adiabatic compression from state 1 to the exit pressure of 14 bar would be
1Wcv 2 s m 1h1 h2s 2 10.0721249.75 285.582 2.51 kW

# #
The magnitude of the actual power required is greater than the ideal power due to irreversibilities.
Note that IT solves for the value of h2s even though it is an implicit variable in the argument of the specific entropy
function.

6.9 Heat Transfer and Work in Internally
Reversible, Steady-State Flow Processes
This section concerns one-inlet, one-exit control volumes at steady state. The objective is to
derive expressions for the heat transfer and the work in the absence of internal irreversibili-
ties. The resulting expressions have several important applications.
HEAT TRANSFER
For a control volume at steady state in which the flow is both isothermal and internally re-
versible, the appropriate form of the entropy rate balance is
#

m 1s1 s2 2
s cv
Qcv # # 0
0
T
#
where 1 and 2 denote the inlet and exit, respectively, and m is the mass flow rate. Solving
this equation, the heat transfer per unit of mass passing through the control volume is
#
# T 1s2 s1 2
Qcv
m
More generally, the temperature would vary as the gas or liquid flows through the control
volume. However, we can consider the temperature variation to consist of a series of infini-
tesimal steps. Then, the heat transfer per unit of mass would be given as
#
a # b int
Qcv 2
T ds (6.51)
m rev 1
The subscript int rev serves to remind us that the expression applies only to control
( )
Qcv

m int
rev
= 2
1 T ds
2
volumes in which there are no internal irreversibilities. The integral of Eq. 6.51 is per-
T
formed from inlet to exit. When the states visited by a unit mass as it passes reversibly
1
from inlet to exit are described by a curve on a Ts diagram, the magnitude of the heat
transfer per unit of mass flowing can be represented as the area under the curve, as shown
in Fig. 6.14.
WORK
s
The work per unit of mass passing through the control volume can be found from an energy
Figure 6.14 Area rate balance, which reduces at steady state to give
representation of heat
# #
transfer for an internally V21 V22
# #
1h1 h2 2
a b
g1z1 z2 2
Wcv Qcv
reversible flow process.
m m 2
This equation is a statement of the conservation of energy principle that applies when irre-
versibilities are present within the control volume as well as when they are absent. However,
if consideration is restricted to the internally reversible case, Eq. 6.51 can be introduced to
obtain
#
V21 V22
a # bint T ds
1h1 h2 2
a b
g1z1 z2 2
Wcv 2
(6.52)
m rev 1 2
6.9 Heat Transfer and Work in Internally Reversible, Steady-State Flow Processes 255
where the subscript int rev has the same significance as before. Since internal irre-
versibilities are absent, a unit of mass traverses a sequence of equilibrium states as it
passes from inlet to exit. Entropy, enthalpy, and pressure changes are therefore related by
Eq. 6.12b
T ds dh v dp
which on integration gives
T ds 1h2 h1 2
2 2
v dp
1 1
Introducing this relation, Eq. 6.52 becomes
#
V21 V22
a # bint v dp
a b
g1z1 z2 2
Wcv 2 p
(6.53a) 2
m rev 1 2
2
1 vdp
When the states visited by a unit of mass as it passes reversibly from inlet to exit are de-
scribed by a curve on a pv diagram as shown in Fig. 6.15, the magnitude of the integral 1
v dp is represented by the shaded area behind the curve.
Equation 6.53a may be applied to devices such as turbines, compressors, and pumps. In v
many of these cases, there is no significant change in kinetic or potential energy from inlet Figure 6.15 Area
to exit, so representation of 12 v dp.
#
a # bint 1 ke pe 02
Wcv 2
v dp (6.53b)
m rev 1
This expression shows that the work is related to the magnitude of the specific volume of
the gas or liquid as it flows from inlet to exit. for example. . . consider two devices:
a pump through which liquid water passes and a compressor through which water vapor
passes. For the same pressure rise, the pump would require a much smaller work input per
unit of mass flowing than would the compressor because the liquid specific volume is much
smaller than that of vapor. This conclusion is also qualitatively correct for actual pumps and
compressors, where irreversibilities are present during operation.
If the specific volume remains approximately constant, as in many applications with liq-
uids, Eq. 6.53b becomes
#
a # bint v1 p2 p1 2 1v constant, ke pe 02
Wcv
(6.53c)
m rev
Equation 6.53a
# can also be applied to study the performance of control volumes at steady
state in which Wcv is zero, as in the case of nozzles and diffusers. For any such case, the
equation becomes
V22 V21
v dp
a b
g1z2 z1 2 0
2
(6.54)
1 2
which is a form of the Bernoulli equation frequently used in fluid mechanics. Bernoulli equation
WORK IN POLYTROPIC PROCESSES
When each unit of mass undergoes a polytropic process as it passes through the control vol-
ume, the relationship between pressure and specific volume is pvn constant. Introducing
this into Eq. 6.53b and performing the integration
#
a # bint v dp 1constant2 1n

Wcv 2 2 dp
1n
m rev 1 1 p
1p v p1v1 2 1polytropic, n 12
n
(6.55)
n1 2 2
for any value of n except n 1. When n 1, pv constant, and the work is

#
a # bint v dp constant

Wcv 2 2 dp
m rev 1 1 p
1p1v1 2 ln1p2 p1 2 1polytropic, n 12 (6.56)

Equations 6.55 and 6.56 apply generally to polytropic processes of any gas (or liquid).
IDEAL GAS CASE. For the special case of an ideal gas, Eq. 6.55 becomes
#
a # bint 1T T1 2 1ideal gas, n 12
Wcv nR
(6.57a)
m rev n1 2
For a polytropic process of an ideal gas, Eq. 3.56 applies:
p2 1n12n
a b
T2
T1 p1
Thus, Eq. 6.57a can be expressed alternatively as
p2 1n12n
#
a # bint ca b 1d 1ideal gas, n 12
Wcv nRT1
(6.57b)
m rev n 1 p1
For the case of an ideal gas, Eq. 6.56 becomes
#
a # bint RT ln1 p2 p1 2 1ideal gas, n 12
Wcv
(6.58)
m rev
In the next example, we consider air modeled as an ideal gas undergoing a polytropic
compression process at steady state.
EXAMPLE 6.15 Polytropic Compression of Air
An air compressor operates at steady state with air entering at p1 1 bar, T1 20C, and exiting at p2 5 bar. Determine
the work and heat transfer per unit of mass passing through the device, in kJ/kg, if the air undergoes a polytropic process with
n 1.3. Neglect changes in kinetic and potential energy between the inlet and the exit. Use the ideal gas model for air.
SOLUTION
Known: Air is compressed in a polytropic process from a specified inlet state to a specified exit pressure.
Find: Determine the work and heat transfer per unit of mass passing through the device.
6.9 Heat Transfer and Work in Internally Reversible, Steady-State Flow Processes 257
p T2 = 425 K
2
5 bar
Assumptions:
pv1.3 = constant 1. A control volume enclosing the compressor is at steady state.

2. The air undergoes a polytropic process with n 1.3.
3. The air behaves as an ideal gas.
1
1 bar 4. Changes in kinetic and potential energy from inlet to exit can be
Shaded area = magnitude of (Wcv/m) int neglected.
rev
v
Figure E6.15
Analysis: The work is obtained using Eq. 6.57a, which requires the temperature at the exit, T2. The temperature T2 can be
found using Eq. 3.56
p2 1n12n 5 11.3121.3
T2 T1 a b 293 a b 425 K
p1 1
Substituting known values into Eq. 6.57a then gives
#
1T T1 2 a b 1425 2932 K
Wcv nR 1.3 8.314 kJ
#
m n1 2 1.3 1 28.97 kg # K
164.2 kJ/kg
The heat transfer is evaluated by reducing the mass and energy rate balances with the appropriate assumptions to obtain
# #
Qcv Wcv
# #
h2 h1
m m
Using the temperatures T1 and T2, the required specific enthalpy values are obtained from Table A-22 as h1 293.17 kJ/kg
and h2 426.35 kJ/ kg. Thus
#
# 164.15
1426.35 293.172 31 kJ/kg
Qcv
m
The states visited in the polytropic compression process are shown by the curve on the accompanying pv diagram. The
magnitude of the work per unit of mass passing through the compressor is represented by the shaded area behind the curve.
In this chapter, we have introduced the property entropy and entropy production. For processes of closed systems, the en-
illustrated its use for thermodynamic analysis. Like mass tropy balance is Eq. 6.27, and a corresponding rate form is
and energy, entropy is an extensive property that can be trans- Eq. 6.32. For control volumes, rate forms include Eq. 6.37 and
ferred across system boundaries. Entropy transfer accompa- the companion steady-state expression given by Eq. 6.39.
nies both heat transfer and mass flow. Unlike mass and energy, The following checklist provides a study guide for this
entropy is not conserved but is produced within systems chapter. When your study of the text and end-of-chapter
whenever internal irreversibilities are present. exercises has been completed you should be able to
The use of entropy balances is featured in this chapter. En-
tropy balances are expressions of the second law that account write out meanings of the terms listed in the margins
for the entropy of systems in terms of entropy transfers and throughout the chapter and understand each of the
related concepts. The subset of key concepts listed determining s of ideal gases using Eq. 6.21 for
below in is particularly important in subsequent variable specific heats together with Tables A-22 and
chapters. A-23, and using Eqs. 6.22 and 6.23 for constant
apply entropy balances in each of several alternative specific heats.
forms, appropriately modeling the case at hand, correctly evaluating isentropic efficiencies for turbines, nozzles,
observing sign conventions, and carefully applying SI compressors, and pumps from Eqs. 6.48, 6.49, and
and English units. 6.50, respectively, including for ideal gases the appro-
priate use of Eqs. 6.436.44 for variable specific
use entropy data appropriately, to include
heats and Eqs. 6.456.47 for constant specific heats.
retrieving data from Tables A-2 through A-18, using
Eq. 6.6 to evaluate the specific entropy of two-phase apply Eq. 6.25 for closed systems and Eqs. 6.51 and
liquidvapor mixtures, sketching Ts and hs 6.53 for one-inlet, one-exit control volumes at steady
diagrams and locating states on such diagrams, and state, correctly observing the restriction to internally
appropriately using Eqs. 6.7 and 6.24. reversible processes.
entropy change p. 209 entropy transfer entropy rate balance isentropic efficiencies
Ts diagram p. 211 p. 221, 232 p. 223, 231, 233 p. 247248
Mollier diagram p. 212 entropy
entropy balance p. 221 production p. 221
1. Of mass, energy, and entropy, which are conserved? T T

2 2 3
2. Both entropy and enthalpy are introduced in this text without
accompanying physical pictures. Can you think of other such
properties?
3. How might you explain the entropy production concept in
terms a child would understand? 1 3 1
4. Referring to Fig. 2.3, if systems A and B operate adiabati- S S
cally, does the entropy of each increase, decrease, or remain
the same? 11. Sketch Ts and pv diagrams of a gas executing a power cy-
5. If a closed system would undergo an internally reversible cle consisting of four internally reversible processes in series: con-
process and an irreversible process between the same end stant specific volume, constant pressure, isentropic, isothermal.
states, how would the changes in entropy for the two processes 12. Sketch the Ts diagram for the Carnot vapor cycle of Fig. 5.12.
compare? How would the amounts of entropy produced 13. All states of an adiabatic and internally reversible process of
compare? a closed system have the same entropy, but is a process between
6. Is is possible for the entropy of both a closed system and its two states having same entropy necessarily adiabatic and inter-
surroundings to decrease during a process? nally reversible?
7. Describe a process of a closed system for which the entropy 14. Discuss the operation of a turbine in the limit as isentropic
of both the system and its surroundings increase. efficiency approaches 100%; in the limit as isentropic efficiency
approaches 0%.
8. How can entropy be transferred into, or out of, a closed sys-
15. What can be deduced from energy and entropy balances
tem? A control volume?
about a system undergoing a thermodynamic cycle while receiv-
9. What happens to the entropy produced in a one-inlet, one-exit ing energy by heat transfer at temperature TC and discharging en-
control volume at steady state? ergy by heat transfer at a higher temperature TH, if these are the
10. The two power cycles shown to the same scale in the figure only energy transfers the system experiences?
are composed of internally reversible processes. Compare the net 16. Reducing irreversibilities within a system can improve its therm-
work developed by these cycles. Which cycle has the greater odynamic performance, but steps taken in this direction are usually
thermal efficiency? constrained by other considerations. What are some of these?
Exploring Fundamentals Surroundings

6.1 A system executes a power cycle while receiving 1000 kJ T0
by heat transfer at a temperature of 500 K and discharging en-
ergy by heat transfer at a temperature of 300 K. There are no
other heat transfers. Applying Eq. 6.2, determine cycle if the
Q0
thermal efficiency is (a) 60%, (b) 40%, (c) 20%. Identify the
cases (if any) that are internally reversible or impossible. Qs Qu
6.2 A reversible power cycle R and an irreversible power cycle I Air

operate between the same two reservoirs. Each receives QH from
the hot reservoir. The reversible cycle develops work WR,
while the irreversible cycle develops work WI. The reversible
cycle discharges QC to the cold reservoir, while the irreversible Ts Tu
Fuel
cycle discharges QC. Figure P6.6
(a) Evaluate cycle for cycle I in terms of WI, WR, and tem-
perature TC of the cold reservoir only.
(b) Demonstrate that WI WR and QC QC. #
Ts, and delivering energy at the rate Qu at a use temperature
6.3 A reversible refrigeration cycle R and an irreversible re- Tu. There are no other energy transfers. For Ts Tu T0,# ob-
frigeration cycle I operate between the same two reservoirs tain an expression for the maximum theoretical value of Qu in
and each removes QC from the cold reservoir. The net work #
terms of Qs and the temperatures Ts, Tu, and T0.
input required by R is WR, while the net work input for I is
WI. The reversible cycle discharges QH to the hot reservoir, 6.7 Answer the following true or false. If false, explain why.
while the irreversible cycle discharges QH. Show that WI WR (a) The change of entropy of a closed system is the same for
and QH QH. every process between two specified states.
(b) The entropy of a fixed amount of an ideal gas increases in
6.4 A reversible power cycle receives energy Q1 and Q2 from
every isothermal compression.
hot reservoirs at temperatures T1 and T2, respectively, and dis-
(c) The specific internal energy and enthalpy of an ideal gas
charges energy Q3 to a cold reservoir at temperature T3.
are each functions of temperature alone but its specific en-
(a) Obtain an expression for the thermal efficiency in terms of tropy depends on two independent intensive properties.
the ratios T1T3, T2T3, q Q2Q1. (d) One of the T ds equations has the form T ds du p dv.
(b) Discuss the result of part (a) in each of these limits: lim (e) The entropy of a fixed amount of an incompressible sub-
q S 0, lim q S , lim T1 S . stance increases in every process in which temperature
decreases.
6.5 Complete the following involving reversible and irreversible
cycles: 6.8 A closed system consists of an ideal gas with constant spe-
cific heat ratio k.
(a) Reversible and irreversible power cycles each discharge
energy QC to a cold reservoir at temperature TC and re- (a) The gas undergoes a process in which temperature in-
ceive energy QH from hot reservoirs at temperatures TH and creases from T1 to T2. Show that the entropy change for
TH, respectively. There are no other heat transfers. Show the process is greater if the change in state occurs at con-
that TH TH. stant pressure than if it occurs at constant volume. Sketch
(b) Reversible and irreversible refrigeration cycles each dis- the processes on pv and Ts coordinates.
charge energy QH to a hot reservoir at temperature TH and (b) Using the results of (a), show on Ts coordinates that a
receive energy QC from cold reservoirs at temperatures TC line of constant specific volume passing through a state
and TC, respectively. There are no other heat transfers. has a greater slope than a line of constant pressure pass-
Show that TC TC. ing through that state.
(c) Reversible and irreversible heat pump cycles each receive (c) The gas undergoes a process in which pressure increases
energy QC from a cold reservoir at temperature TC and dis- from p1 to p2. Show that the ratio of the entropy change
charge energy QH to hot reservoirs at temperatures TH and for an isothermal process to the entropy change for a
TH, respectively. There are no other heat transfers. Show constant-volume process is (1 k). Sketch the processes
that TH TH. on pv and Ts coordinates.
6.6 The system shown schematically in Fig. P6.6 undergoes a 6.9 Answer the following true or false. If false, explain why.
cycle while receiving energy # at the rate Q0 from the sur- (a) A process that violates the second law of thermodynam-
roundings at temperature T0, Qs from a source at temperature ics violates the first law of thermodynamics.
(b) When a net amount of work is done on a closed system and at the other end with a wall at a lower temperature TC. The
undergoing an internally reversible process, a net heat temperature within the rod initially varies linearly with posi-
transfer of energy from the system also occurs. tion z according to
(c) One corollary of the second law of thermodynamics states
TH TC
T 1z2 TH a bz
that the change in entropy of a closed system must be
greater than zero or equal to zero. L
(d) A closed system can experience an increase in entropy only
when irreversibilities are present within the system during The rod is then insulated on its ends and eventually comes to
the process. a final equilibrium state where the temperature is Tf. Evaluate
(e) Entropy is produced in every internally reversible process Tf in terms of TH and TC and show that the amount of entropy
of a closed system. produced is
(f ) In an adiabatic and internally reversible process of a closed
s mc a1
ln Tf
ln TH b
system, the entropy remains constant. TC TH
ln TC
(g) The energy of an isolated system must remain constant, TH TC TH TC
but the entropy can only decrease.
6.10 A fixed mass of water m, initially a saturated liquid, is where c is the specific heat of the rod.
brought to a saturated vapor condition while its pressure and 6.15 A system undergoing a thermodynamic cycle receives QH
temperature remain constant. at temperature TH and discharges QC at temperature TC. There
(a) Derive expressions for the work and heat transfer in terms are no other heat transfers.
of the mass m and properties that can be obtained directly (a) Show that the net work developed per cycle is given by
from the steam tables.
Wcycle QH a1 b T C s
(b) Demonstrate that this process is internally reversible. T C
6.11 A quantity of air is shown in Fig. 6.8. Consider a process T H
in which the temperature of the air increases by some combi-
nation of stirring and heating. Assuming the ideal gas model where is the amount of entropy produced per cycle owing
for the air, suggest how this might be done with to irreversibilities within the system.
(b) If the heat transfers QH and QC are with hot and cold reser-
(a) minimum entropy production.
voirs, respectively, what is the relationship of TH to the
(b) maximum entropy production.
temperature of the hot reservoir TH and the relationship of
6.12 Taken together, a certain closed system and its surround- TC to the temperature of the cold reservoir TC?
ings make up an isolated system. Answer the following true or (c) Obtain an expression for Wcycle if there are (i) no inter-
false. If false, explain why. nal irreversibilities, (ii) no internal or external irre-
(a) No process is allowed in which the entropies of both the versibilities.
system and the surroundings increase. 6.16 A system undergoes a thermodynamic power cycle while
(b) During a process, the entropy of the system might de- receiving energy by heat transfer from an incompressible body
crease, while the entropy of the surroundings increases, of mass m and specific heat c initially at temperature TH. The
and conversely. system undergoing the cycle discharges energy by heat trans-
(c) No process is allowed in which the entropies of both the fer to another incompressible body of mass m and specific heat
system and the surroundings remain unchanged. c initially at a lower temperature TC. Work is developed by the
(d) A process can occur in which the entropies of both the cycle until the temperature of each of the two bodies is the
system and the surroundings decrease. same, T.
6.13 An isolated system of total mass m is formed by mixing (a) Develop an expression for the minimum theoretical
two equal masses of the same liquid initially at the tempera- final temperature, T, in terms of m, c, TH, and TC, as
tures T1 and T2. Eventually, the system attains an equilibrium required.
state. Each mass is incompressible with constant specific (b) Develop an expression for the maximum theoretical
heat c. amount of work that can be developed, Wmax, in terms of
(a) Show that the amount of entropy produced is m, c, TH, and TC, as required.
(c) What is the minimum theoretical work input that would be
T1
T2
s mc ln c d
required by a refrigeration cycle to restore the two bodies
21T1T2 2 12 from temperature T to their respective initial temperatures,
TH and TC?
(b) Demonstrate that must be positive. 6.17 At steady state, an insulated mixing chamber receives two
6.14 A cylindrical rod of length L insulated on its lateral surface liquid streams of the same substance at temperatures T1 and T2
# #
is initially in contact at one end with a wall at temperature TH and mass flow rates m1 and m2, respectively. A single stream
#
exits at T3 and m3. Using the incompressible substance model (b) air as an ideal gas, T1 27C, p1 1.5 bar, T2 127C.
with constant specific heat c, obtain an expression for Find p2 in bar.
(a) T3 in terms of T1, T2, and the ratio of mass flow rates m1m3.
# # (c) Refrigerant 134a, T1 20C, p1 5 bar, p2 1 bar. Find
(b) the rate of entropy production per unit of mass exiting the v2 in m3/kg.
chamber in terms of c, T1T2, and m1m3.
# #
6.23 One kilogram of oxygen (O2) modeled as an ideal gas
(c) For fixed values of c and T1T2, determine the value of undergoes a process from 300 K, 2 bar to 1500 K, 1.5 bar.
m1m3 for which the rate of entropy production is a
# #
Determine the change in specific entropy, in kJ/kg # K, using
maximum. (a) Equation 6.19 with cp 1T 2 from Table A-21.
Using Entropy Data (b) Equation 6.21b with s from Table A-23.
(c) Equation 6.23 with cp at 900 K from Table A-20.
6.18 Using the tables for water, determine the specific entropy (d) IT.
at the indicated states, in kJ/kg # K. Check the results using IT.
In each case, locate the state by hand on a sketch of the Ts 6.24 Five kilograms of ammonia undergo a process from an
diagram. initial state where the pressure is 8 bar and the temperature
is 100C to a final state of 8 bar, 0C. Determine the entropy
(a) p 5.0 MPa, T 400C change of the ammonia, in kJ/K, assuming the process is
(b) p 5.0 MPa, T 100C
(c) p 5.0 MPa, u 1872.5 kJ/kg (a) irreversible.
(d) p 5.0 MPa, saturated vapor (b) internally reversible.
6.19 Using the appropriate table, determine the change in spe- 6.25 A quantity of liquid water undergoes a process from 80C,
cific entropy between the specified states, in kJ/kg # K. Check 5 MPa to saturated liquid at 40C. Determine the change in
the results using IT. specific entropy, in kJkg # K, using
(a) water, p1 10 MPa, T1 400C, p2 10 MPa, (a) Tables A-2 and A-5.
T2 100C. (b) saturated liquid data only from Table A-2.
(b) Refrigerant 134a, h1 111.44 kJ/kg, T1 40C, (c) the incompressible liquid model with a constant specific
saturated vapor at p2 5 bar. heat from Table A-19.
(c) air as an ideal gas, T1 7C, p1 2 bar, T2 327C, (d) IT.
p2 1 bar. 6.26 One-quarter lbmol of nitrogen gas (N2) undergoes a
(d) hydrogen (H2) as an ideal gas, T1 727C, p1 1 bar, process from p1 20 lbf/in.2, T1 500R to p2 150 lbf/in.2,
T2 25C, p2 3 bar. T2 800R. For the process W 500 Btu. Employing the
6.20 One kilogram of Refrigerant 22 undergoes a process from ideal gas model, determine
0.2 MPa, 20C to a state where the pressure is 0.06 MPa. Dur- (a) the heat transfer, in Btu.
ing the process there is a change in specific entropy, s2 s1 (b) the change in entropy, in Btu/R.
0.55 kJ/kg # K. Determine the temperature at the final state, in (c) Show the initial and final states on a Ts diagram.
C, and the final specific enthalpy, in kJ/kg.
6.27 Methane gas (CH4) enters a compressor at 298 K, 1 bar
6.21 Employing the ideal gas model, determine the change in and exits at 2 bar and temperature T. Employing the ideal gas
specific entropy between the indicated states, in kJ/kg # K. model, determine T, in K, if there is no change in specific en-
Solve three ways: Use the appropriate ideal gas table, IT, and tropy from inlet to exit.
a constant specific heat value from Table A-20.
(a) air, p1 100 kPa, T1 20C, p2 100 kPa, T2 Analyzing Internally Reversible Processes
100C. 6.28 A quantity of air amounting to 2.42 102 kg undergoes
(b) air, p1 1 bar, T1 27C, p2 3 bar, T2 377C. a thermodynamic cycle consisting of three internally reversible
(c) carbon dioxide, p1 150 kPa, T1 30C, p2 300 kPa, processes in series.
T2 300C.
Process 12: constant-volume heating at V 0.02 m3 from
(d) carbon monoxide, T1 300 K, v1 1.1 m3/kg, T2 500 K,
p1 0.1 MPa to p2 0.42 MPa
v2 0.75 m3/kg.
(e) nitrogen, p1 2 MPa, T1 800 K, p2 1 MPa, Process 23: constant-pressure cooling
T2 300 K. Process 31: isothermal heating to the initial state
6.22 Using the appropriate table, determine the indicated
property for a process in which there is no change in spe- Employing the ideal gas model with cp 1 kJ/kg # K, evalu-
cific entropy between state 1 and state 2. Check the results ate the change in entropy, in kJ/K, for each process. Sketch
using IT. the cycle on pv and Ts coordinates.
(a) water, T1 10C, x1 0.75, saturated vapor at state 2. 6.29 One kilogram of water initially at 160C, 1.5 bar under-
Find p2 in bar. goes an isothermal, internally reversible compression process
to the saturated liquid state. Determine the work and heat trans- Process 23: adiabatic compression to 550 K, 6.25 bar
fer, each in kJ. Sketch the process on pv and Ts coordinates. Process 31: constant-pressure compression
Associate the work and heat transfer with areas on these
diagrams. Employing the ideal gas model,
6.30 A gas initially at 14 bar and 60C expands to a final pres- (a) sketch the cycle on pv and Ts coordinates.
sure of 2.8 bar in an isothermal, internally reversible process. (b) determine T1, in K
Determine the heat transfer and the work, each in kJ per kg of (c) If the cycle is a power cycle, determine its thermal effi-
gas, if the gas is (a) Refrigerant 134a, (b) air as an ideal gas. ciency. If the cycle is a refrigeration cycle, determine its
Sketch the processes on pv and Ts coordinates. coefficient of performance.
6.31 Reconsider the data of Problem 6.37, but now suppose 6.37 Figure P6.37 gives the schematic of a vapor power plant
the gas expands to 2.8 bar isentropically. Determine the work, in which water steadily circulates through the four components
in kJ per kg of gas, if the gas is (a) Refrigerant 134a, (b) air shown. The water flows through the boiler and condenser at
as an ideal gas. Sketch the processes on pv and Ts constant pressure, and flows through the turbine and pump
coordinates. adiabatically.
6.32 Nitrogen (N2) initially occupying 0.5 m3 at 1.0 bar, 20C (a) Sketch the cycle on Ts coordinates.
undergoes an internally reversible compression during which (b) Determine the thermal efficiency and compare with the
pV1.30 constant to a final state where the temperature is thermal efficiency of a Carnot cycle operating between the
200C. Determine assuming the ideal gas model same maximum and minimum temperatures.
(a) the pressure at the final state, in bar.
(b) the work and heat transfer, each in kJ.
Hot reservoir
(c) the entropy change, in kJ/K.
QH
6.33 Air initially occupying a volume of 1 m3 at 1 bar, 20C
undergoes two internally reversible processes in series
Saturated 4 Boiler 1 Saturated
Process 12: compression to 5 bar, 110C during which liquid at vapor at
pV n constant 10 bar 10 bar
Process 23: adiabatic expansion to 1 bar Pump Turbine

Work Work
(a) Sketch the two processes on pv and Ts coordinates.
(b) Determine n. 0.2 bar, 0.2 bar,
(c) Determine the temperature at state 3, in C. x = 18% 3 Condenser 2 x = 88%
(d) Determine the net work, in kJ.
6.34 One-tenth kilogram of water executes a Carnot power
cycle. At the beginning of the isothermal expansion, the water QC
is a saturated liquid at 160C. The isothermal expansion Cold reservoir
continues until the quality is 98%. The temperature at the Figure P6.37
conclusion of the adiabatic expansion is 20C.
(a) Sketch the cycle on Ts and pv coordinates. Applying the Entropy Balance: Closed Systems
(b) Determine the heat added and net work, each in kJ.
6.38 A closed system undergoes a process in which work is done
(c) Evaluate the thermal efficiency.
on the system and the heat transfer Q occurs only at temperature
6.35 One pound mass of air as an ideal gas undergoes a Carnot Tb. For each case, determine whether the entropy change of the
power cycle. At the beginning of the isothermal expansion, the system is positive, negative, zero, or indeterminate.
temperature is 880K and the pressure is 8 MPa. The isothermal
(a) internally reversible process, Q 0.
compression occurs at 280K and the heat added per cycle is
(b) internally reversible process, Q 0.
42 kW. Assuming the ideal gas model for the air, determine
(c) internally reversible process, Q 0.
(a) the pressures at the end of the isothermal expansion, the (d) internal irreversibilities present, Q 0.
adiabatic expansion, and the isothermal compression, each (e) internal irreversibilities present, Q 0.
in MPa. (f) internal irreversibilities present, Q 0.
(b) the net work developed per cycle, kW.
6.39 For each of the following systems, specify whether the en-
(c) the thermal efficiency.
tropy change during the indicated process is positive, negative,
6.36 A quantity of air undergoes a thermodynamic cycle con- zero, or indeterminate.
sisting of three internally reversible processes in series.
(a) One kilogram of water vapor undergoing an adiabatic com-
Process 12: isothermal expansion from 6.25 to 1.0 bar pression process.
(b) Two kg mass of nitrogen heated in an internally reversible 6.48 For the silicon chip of Example 2.5, determine the rate of
process. entropy production, in kW/K. What is the cause of entropy
(c) One kilogram of Refrigerant 134a undergoing an adiabatic production in this case?
process during which it is stirred by a paddle wheel. 6.49 An electric water heater having a 200 liter capacity
(d) One kg mass of carbon dioxide cooled isothermally. employs an electric resistor to heat water from 23 to 55C. The
(e) Two kg mass of oxygen modeled as an ideal gas undergo- outer surface of the resistor remains at an average temperature
ing a constant-pressure process to a higher temperature. of 80C. Heat transfer from the outside of the water heater is
(f ) Two kilograms of argon modeled as an ideal gas undergo- negligible and the states of the resistor and the tank holding
ing an isothermal process to a lower pressure. the water do not change significantly. Modeling the water as
6.40 A pistoncylinder assembly initially contains 0.04 m3 of incompressible, determine the amount of entropy produced, in
water at 1.0 MPa, 320C. The water expands adiabatically to kJ/K, for
a final pressure of 0.1 MPa. Develop a plot of the work done
(a) the water as the system.
by the water, in kJ, versus the amount of entropy produced, in
(b) the overall water heater including the resistor.
kJ/K.
Compare the results of parts (a) and (b), and discuss.
6.41 An insulated pistoncylinder assembly contains Refriger-
ant 134a, initially occupying 0.017 m3 at .6 MPa, 40C. The 6.50 At steady state, a 20-W curling iron has an outer surface
refrigerant expands to a final state where the pressure is .32 MPa. temperature of 80C. For the curling iron, the rate of entropy
The work developed by the refrigerant is measured as 5.275 kJ. production, in Btu/ h R.
Can this value be correct? 6.51 An electric motor operating at steady state draws a current
6.42 One kilogram of air is initially at 1 bar and 450 K. Can a of 10 amp with a voltage of 220 V. The output shaft rotates
final state at 2 bar and 350 K be attained in an adiabatic process? at 1000 RPM with a torque of 16 N # m applied to an exter-
6.43 Air as an ideal gas is compressed from a state where the nal load. The rate of heat transfer from the motor to its sur-
pressure is 0.1 MPa and the temperature is 27C to a state where roundings is related to the surface temperature Tb and the am-
the pressure is 0.5 MPa and the temperature is 207C. Can this bient temperature T0 by hA(Tb T0), where h 100 W/m2 #
process occur adiabatically? If yes, determine the work per unit K, A 0.195 m2, and T0 293 K. Energy transfers are con-
mass of air, in kJ/kg, for an adiabatic process between these sidered positive in the directions indicated by the arrows on
states. If no, determine the direction of the heat transfer. Fig. P6.51.
6.44 Two kilograms of Refrigerant 134a initially at 1.4 bar, (a) Determine the temperature Tb, in K.
60C are compressed to saturated vapor at 60C. During this (b) For the motor as the system, determine the rate of entropy
process, the temperature of the refrigerant departs by no more production, in kW/K.
than 0.01C from 60C. Determine the minimum theoretical (c) If the system boundary is located to take in enough of the
heat transfer from the refrigerant during the process, in kJ. nearby surroundings for heat transfer to take place at tem-
perature T0, determine the rate of entropy production, in
6.45 A patent application describes a device that at steady state
kW/K, for the enlarged system.
receives a heat transfer at the rate 1 kW at a temperature of
167C and generates electricity. There are no other energy
transfers. Does the claimed performance violate any principles

of thermodynamics? Explain. T0 = 293 K Q
6.46 One-half kilogram of propane initially at 4 bar, 30C
undergoes a process to 14 bar, 100C while being rapidly com-
Wshaft
pressed in a pistoncylinder assembly. Heat transfer with the Welec + Tb = ?
surroundings at 20C occurs through a thin wall. The net work
is measured as 72.5 kJ. Kinetic and potential energy effects
can be ignored. Determine whether it is possible for the work Figure P6.51
measurement to be correct.
6.47 One kilogram mass of air in a pistoncylinder assembly
is compressed adiabatically from 4C, 1 bar to 5 bars. 6.52 At steady state, work at a rate of 25 kW is done by a pad-
(a) If the air is compressed without internal irreversibilities, dle wheel on a slurry contained within a closed, rigid tank. Heat
determine the temperature at the final state, in C, and the transfer from the tank occurs at a temperature of 250C to sur-
work required, in kJ. roundings that, away from the immediate vicinity of the tank,
(b) If the compression requires 20% more work than found in are at 27C. Determine the rate of entropy production, in kW/K,
part (a), determine the temperature at the final state, in F, (a) for the tank and its contents as the system.
and the amount of entropy produced, in kJ/K. (b) for an enlarged system including the tank and enough of
(c) Show the processes of parts (a) and (b) on Ts coordinates. the nearby surroundings for the heat transfer to occur at
Employ the ideal gas model. 27C.
6.53 A system consists of 2 m3 of hydrogen gas (H2), initially which energy is conducted into the rod from the hot wall is
at 35C, 215 kPa, contained in a closed rigid tank. Energy is
transferred to the system from a reservoir at 300C until the # kA1TH TC 2
QH
temperature of the hydrogen is 160C. The temperature at the L
system boundary where heat transfer occurs is 300C. Model-
ing the hydrogen as an ideal gas, determine the heat transfer, where
is the thermal conductivity of the copper rod.
in kJ, the change in entropy, in kJ/K, and the amount of en- (a) For the rod as the system, obtain an expression for the time
tropy produced, in kJ/K. For the reservoir, determine the rate of entropy production in terms of A, L, TH, TC, and k.
change in entropy, in kJ/K. Why do these two entropy changes (b) If TH 327C, TC 77C,
# 0.4 kWm # K, A 0.1
differ? m2, plot the heat transfer rate QH, in kW, and the time rate
6.54 An isolated system consists of a closed aluminum vessel of entropy production, in kW/K, each versus L ranging
of mass 0.1 kg containing 1 kg of used engine oil, each initially from 0.01 to 1.0 m. Discuss.
at 55C, immersed in a 10-kg bath of liquid water, initially at 6.59 A system undergoes a thermodynamic cycle while receiv-
20C. The system is allowed to come to equilibrium. Determine ing energy by heat transfer from a tank of liquid water initially
(a) the final temperature, in degrees centigrade. at 90C and rejecting energy by heat transfer at 15C to the
(b) the entropy changes, each in kJ/K, for the aluminum surroundings. If the final water temperature is 15C, determine
vessel, the oil, and the water. the minimum theoretical volume of water in the tank, m3, for
(c) the amount of entropy produced, in kJ/K. the cycle to produce net work equal to 1.6 105 kJ.
6.55 An insulated cylinder is initially divided into halves by a 6.60 The temperature of an incompressible substance of mass
frictionless, thermally conducting piston. On one side of the m and specific heat c is reduced from T0 to T (T0) by a re-
piston is 1 m3 of a gas at 300 K, 2 bar. On the other side is 1 m3 frigeration cycle. The cycle receives energy by heat transfer at
of the same gas at 300 K, 1 bar. The piston is released and equi- T from the substance and discharges energy by heat transfer at
librium is attained, with the piston experiencing no change of T0 to the surroundings. There are no other heat transfers. Plot
state. Employing the ideal gas model for the gas, determine (WminmcT0) versus TT0 ranging from 0.8 to 1.0, where Wmin
(a) the final temperature, in K. is the minimum theoretical work input required by the cycle.
(b) the final pressure, in bar. 6.61 The temperature of a 12-oz (0.354-L) can of soft drink is
(c) the amount of entropy produced, in kJ/ kg. reduced from 20 to 5C by a refrigeration cycle. The cycle re-
6.56 An insulated, rigid tank is divided into two compartments ceives energy by heat transfer from the soft drink and dis-
by a frictionless, thermally conducting piston. One compart- charges energy by heat transfer at 20C to the surroundings.
ment initially contains 1 m3 of saturated water vapor at 4 MPa There are no other heat transfers. Determine the minimum the-
and the other compartment contains 1 m3 of water vapor at oretical work input required by the cycle, in kJ, assuming the
20 MPa, 800C. The piston is released and equilibrium is soft drink is an incompressible liquid with the properties of
attained, with the piston experiencing no change of state. For liquid water. Ignore the aluminum can.
the water as the system, determine 6.62 As shown in Fig. P6.62, a turbine is located between two
(a) the final pressure, in MPa. tanks. Initially, the smaller tank contains steam at 3.0 MPa,
(b) the final temperature, in C. 280C and the larger tank is evacuated. Steam is allowed to
(c) the amount of entropy produced, in kJ/K. flow from the smaller tank, through the turbine, and into the
6.57 A system consisting of air initially at 300 K and 1 bar ex- larger tank until equilibrium is attained. If heat transfer with
periences the two different types of interactions described the surroundings is negligible, determine the maximum theo-
below. In each case, the system is brought from the initial state retical work that can be developed, in kJ.
to a state where the temperature is 500 K, while volume
remains constant.
(a) The temperature rise is brought about adiabatically by stir-
ring the air with a paddle wheel. Determine the amount of
Initially: steam
entropy produced, in kJ/kg # K. at 3.0 MPa, 280C
(b) The temperature rise is brought about by heat transfer from
a reservoir at temperature T. The temperature at the sys-
tem boundary where heat transfer occurs is also T. Plot the Initially evacuated
amount of entropy produced, in kJ/kg # K, versus T for
T 500 K. Compare with the result of (a) and discuss. Turbine
6.58 A cylindrical copper rod of base area A and length L is in-
sulated on its lateral surface. One end of the rod is in contact 100 m3 1000 m3
with a wall at temperature TH. The other end is in contact with
a wall at a lower temperature TC. At steady state, the rate at Figure P6.62
Applying the Entropy Balance: Control Volumes 6.69 An inventor claims to have developed a device requiring
6.63 A gas flows through a one-inlet, one-exit control# volume no work input or heat transfer, yet able to produce at steady
operating at steady state. Heat transfer at the rate Qcv takes state hot and cold air streams as shown in Fig. P6.69. Em-
place only at a location on the boundary where the tempera- ploying the ideal gas model for air and ignoring kinetic and
ture is Tb. For each of the following cases, determine whether potential energy effects, evaluate this claim.
the specific entropy of the gas at the exit is greater than, equal
to, or less than the specific entropy of the gas at the inlet:
# Qcv = 0, Wcv = 0 Air at 60C,
(a) no internal irreversibilities, Q# cv 0. 2.7 bar
(b) no internal irreversibilities, Q# cv 0. Air at 20C,
(c) no internal irreversibilities,# Qcv 0. 2.74 bar
(d) internal irreversibilities, Q# cv 0. Air at 0C,
(e) internal irreversibilities, Qcv 0. 2.7 bar
6.64 Steam at 10 bar, 600C, 50 m/s enters an insulated turbine Figure P6.69
operating at steady state and exits at 0.35 bar, 100 m/s. The work
developed per kg of steam flowing is claimed to be (a) 1000
6.70 Ammonia enters a valve as a saturated liquid at 7 bar with
kJ/kg, (b) 500 kJ/kg. Can either claim be correct? Explain.
a mass flow rate of 0.06 kg/min and is steadily throttled to a
6.65 Air enters an insulated turbine operating at steady state at pressure of 1 bar. Determine the rate of entropy production in
6.5 bar, 687C and exits at 1 bar, 327C. Neglecting kinetic kW/K. If the valve were replaced by a power-recovery turbine
and potential energy changes and assuming the ideal gas operating at steady state, determine the maximum theoretical
model, determine power that could be developed, in kW. In each case, ignore
(a) the work developed, in kJ per kg of air flowing through heat transfer with the surroundings and changes in kinetic and
the turbine. potential energy. Would you recommend using such a turbine?
(b) whether the expansion is internally reversible, irreversible, 6.71 Air enters an insulated diffuser operating at steady state at
or impossible. 1 bar, 3C, and 260 m /s and exits with a velocity of 130 m/s.
6.66 Methane gas (CH4) at 280 K, 1 bar enters a compressor Employing the ideal gas model and ignoring potential energy,
operating at steady state and exits at 380 K, 3.5 bar. Ignoring determine
heat transfer with the surroundings and employing the ideal (a) the temperature of the air at the exit, in C.
gas model with cp 1T 2 from Table A-21, determine the rate of (b) The maximum attainable exit pressure, in bar.
entropy production within the compressor, in kJ/kg # K.
6.72 According to test data, a new type of engine takes in
6.67 Figure P6.67 provides steady-state operating data for a streams of water at 200C, 3 bar and 100C, 3 bar. The mass
well-insulated device with air entering at one location and ex- flow rate of the higher temperature stream is twice that of the
iting at another with a mass flow rate of 10 kg/s. Assuming other. A single stream exits at 3.0 bar with a mass flow rate of
ideal gas behavior and negligible potential energy effects, de- 5400 kg/h. There is no significant heat transfer between the
termine the direction of flow and the power, in kW. engine and its surroundings, and kinetic and potential energy
effects are negligible. For operation at steady state, determine
the maximum theoretical rate that power can be developed,
in kW.
Power shaft 6.73 At steady state, a device receives a stream of saturated
water vapor at 210C and discharges a condensate stream at
? 20C, 0.1 MPa while delivering energy by heat transfer
? at 300C. The only other energy transfer involves heat trans-
fer at 20C to the surroundings. Kinetic and potential energy
p = 1 bar p = 5 bar changes are negligible. What is the maximum theoretical
T = 600 K T = 900 K amount of energy, in kJ per kg of steam entering, that could be
V = 1000 m/s V = 5 m/s
delivered at 300C?
Figure P6.67
6.74 A patent application describes a device for chilling water.
At steady state, the device receives energy by heat transfer at
6.68 Hydrogen gas (H2) at 35C and pressure p enters an insu- a location on its surface where the temperature is 540F and
lated
# control volume operating at steady state for which discharges energy by heat transfer to the surroundings at an-
Wcv 0. Half of the hydrogen exits the device at 2 bar and other location on its surface where the temperature is 100F.
90C and the other half exits at 2 bar and 20C. The effects A warm liquid water stream enters at 100F, 1 atm and a cool
of kinetic and potential energy are negligible. Employing the stream exits at temperature T and 1 atm. The device requires
ideal gas model with constant cp 14.3 kJ/kg # K, determine no power input to operate, there are no significant effects of
the minimum possible value for the inlet pressure p, in bar. kinetic and potential energy, and the water can be modeled as
incompressible. Plot the minimum theoretical heat addition re- 30-ohm resistor, T = 127C
quired, in Btu per lb of cool water exiting the device, versus +
T ranging from 60 to 100F.
Air in at
6.75 Figure P6.75 shows a proposed device to develop power Air out at 25C
15C, 1 atm
using energy supplied to the device by heat transfer from a
high-temperature industrial process together with a steam in-
put. The figure provides data for steady-state operation. All Figure P6.77
surfaces are well insulated except for the one at 527C, through
which heat transfer occurs at a rate of 4.21 kW. Ignoring
changes in kinetic and potential energy, evaluate the maximum The air enters the duct at 15C, 1 atm and exits at 25C with
theoretical power that can be developed, in kW. a negligible change in pressure. Kinetic and potential energy
changes can be ignored.

Qcv = 4.21 kW (a) For the resistor as the system, determine the rate of en-
tropy production, in kW/K.
(b) For a control volume enclosing the air in the duct and the
resistor, determine the volumetric flow rate of the air en-
Steam at 3 bar Wcv
527C tering the duct, in m3/s, and rate of entropy production, in
500C, 1.58 kg/min
kW/K.
1 2 1 bar Why do the entropy production values of (a) and (b) differ?
Figure P6.75 6.78 For the computer of Example 4.8, determine the rate of
entropy production, in W/K, when air exits at 32C. Ignore the
6.76 Figure P6.76 shows a gas turbine power plant operat- change in pressure between the inlet and exit.
ing at steady state consisting of a compressor, a heat exchanger, 6.79 For the computer of Problem 4.70, determine the rate of
and a turbine. Air enters the compressor with a mass flow rate entropy production, in kW/K, ignoring the change in pressure
of 3.9 kg/s at 0.95 bar, 22C and exits the turbine at 0.95 bar, between the inlet and exit.
421C. Heat transfer to the air as it flows through the heat ex- 6.80 For the water-jacketed electronics housing of Problem
changer occurs at an average temperature of 488C. The com- 4.71, determine the rate of entropy production, in kW/K, when
pressor and turbine operate adiabatically. Using the ideal gas water exits at 26C.
model for the air, and neglecting kinetic and potential energy
effects, determine the maximum theoretical value for the net 6.81 For the electronics-laden cylinder of Problem 4.73,
power that can be developed by the power plant, in MW. determine the rate of entropy production, in W/K, when air
exits at 40C with a negligible change in pressure. Assume con-
vective cooling occurs on the outer surface of the cylinder in
accord with hA 3.4 W/K, where h is the heat transfer coef-
ficient and A is the surface area. The temperature of the
surroundings away from the vicinity of the cylinder is 25C.
T = 488C 6.82 Steam enters a horizontal 15-cm-diameter pipe as a satu-
rated vapor at 5 bar with a velocity of 10 m/s and exits at 4.5 bar
Heat exchanger
with a quality of 95%. Heat transfer from the pipe to the
surroundings at 300 K takes place at an average outer surface
temperature of 400 K. For operation at steady state, determine
Compressor Turbine
(a) the velocity at the exit, in m /s.
Wnet
(b) the rate of heat transfer from the pipe, in kW.
(c) the rate of entropy production, in kW/K, for a control
volume comprising only the pipe and its contents.
1 2 (d) the rate of entropy production, in kW/K, for an enlarged
Air at Air at control volume that includes the pipe and enough of its
0.95 bar, 22C 0.95 bar, 421C immediate surroundings so that heat transfer from the con-
trol volume occurs at 300 K.
Figure P6.76
Why do the answers of parts (c) and (d) differ?
6.77 Figure P6.77 shows a 30-ohm electrical resistor located 6.83 Steam enters a turbine operating at steady state at a
in an insulated duct carrying a stream of air. At steady state, pressure of 3 MPa, a temperature of 400C, and a velocity of
an electric current of 15 amp passes through the resistor, whose 160 m/s. Saturated vapor exits at 100C, with a velocity of
temperature remains constant at 127C. 100 m/s. Heat transfer from the turbine to its surroundings
takes place at the rate of 30 kJ per kg of steam at a location stream with a flow rate of 4 kg/s and exits at 285 K, 0.98 atm.
where the average surface temperature is 350 K. The heat exchanger is at steady state, and there is no appre-
(a) For a control volume including only the turbine and its ciable heat transfer from its outer surface. Neglecting kinetic
contents, determine the work developed, in kJ, and the rate and potential energy effects, determine the mass flow rate of
at which entropy is produced, in kJ/K, each per kg of steam the ammonia, in kg/s, and the rate of entropy production within
flowing. the heat exchanger, in kW/K.
(b) The steam turbine of part (a) is located in a factory where 6.88 A counterflow heat exchanger operates at steady state
the ambient temperature is 27C. Determine the rate of en- with negligible kinetic and potential energy effects. In one
tropy production, in kJ/K per kg of steam flowing, for an stream, liquid water enters at 15C and exits at 23C with a
enlarged control volume that includes the turbine and enough negligible change in pressure. In the other stream, Refrigerant
of its immediate surroundings so that heat transfer takes place 22 enters at 12 bar, 90C with a mass flow rate of 150 kg/h
from the control volume at the ambient temperature. and exits at 12 bar, 28C. Heat transfer from the outer surface
Explain why the entropy production value of part (b) differs of the heat exchanger can be ignored. Determine
from that calculated in part (a). (a) the mass flow rate of the liquid water stream, in kg/h.
6.84 Carbon dioxide (CO2) enters a nozzle operating at steady (b) the rate of entropy production within the heat exchanger,
state at 28 bar, 267C, and 50 m /s. At the nozzle exit, the con- in kW/K.
ditions are 1.2 bar, 67C, 580 m /s, respectively. 6.89 Steam at 0.7 MPa, 355C enters an open feedwater heater
(a) For a control volume enclosing the nozzle only, determine operating at steady state. A separate stream of liquid water en-
the heat transfer, in kJ, and the change in specific entropy, ters at 0.7 MPa, 35C. A single mixed stream exits as saturated
in kJ/K, each per kg of carbon dioxide flowing through the liquid at pressure p. Heat transfer with the surroundings and
nozzle. What additional information would be required to kinetic and potential energy effects can be ignored.
evaluate the rate of entropy production? (a) If p 0.7 MPa, determine the ratio of the mass flow rates
(b) Evaluate the rate of entropy production, in kJ/K per kg of of the incoming streams and the rate at which entropy is
carbon dioxide flowing, for an enlarged control volume produced within the feedwater heater, in kJ/K per kg of
enclosing the nozzle and a portion of its immediate liquid exiting.
surroundings so that the heat transfer occurs at the ambi- (b) Plot the quantities of part (a), each versus pressure p rang-
ent temperature, 25C. ing from 0.6 to 0.7 MPa.
6.85 Air enters a compressor operating at steady state at 1 bar, 6.90 Air as an ideal gas flows through the compressor and heat
22C with a volumetric flow rate of 1 m3/min and is com- exchanger shown in Fig. P6.90. A separate liquid water stream
pressed to 4 bar, 177C. The power input is 3.5 kW. Employing also flows through the heat exchanger. The data given are for
the ideal gas model and ignoring kinetic and potential energy operation at steady state. Stray heat transfer to the surround-
effects, obtain the following results: ings can be neglected, as can all kinetic and potential energy
(a) For a control volume enclosing the compressor only, de- changes. Determine
termine the heat transfer rate, in kW, and the change in (a) the compressor power, in kW, and the mass flow rate of
specific entropy from inlet to exit, in kJ/kg # K. What ad- the cooling water, in kg/s.
ditional information would be required to evaluate the rate (b) the rates of entropy production, each in kW/K, for the com-
of entropy production? pressor and heat exchanger.
(b) Calculate the rate of entropy production, in kW/K, for an
enlarged control volume enclosing the compressor and a
portion of its immediate surroundings so that heat trans-
fer occurs at the ambient temperature, 22C.
Compressor
6.86 Air is compressed in an axial-flow compressor operating TA = 25C TB = 40C
at steady state from 27C, 1 bar to a pressure of 2.1 bar. The
Water Water
work input required is 94.6 kJ per kg of air flowing through in out
the compressor. Heat transfer from the compressor occurs at
the rate of 14 kJ per kg at a location on the compressors surface 1
Air in (A) (B)
where the temperature is 40C. Kinetic and potential energy
changes can be ignored. Determine p1 = 96 kPa Heat
T1 = 27C exchanger
(a) the temperature of the air at the exit, in C. (AV)1 = 26.91 m3/min
(b) the rate at which entropy is produced within the com-
2 3
pressor, in kJ/K per kg of air flowing.
p2 = 230 kPa
6.87 Ammonia enters a counterflow heat exchanger at 20C, T1 = 127C
T3 = 77C
p3 = p2
with a quality of 35%, and leaves as saturated vapor at 20C.
Air at 300 K, 1 atm enters the heat exchanger in a separate Figure P6.90
6.91 Determine the rates of entropy production, each in kW/K, 6.98 Methane (CH4) undergoes an isentropic expansion from
for the turbines and the heat exchanger of Problem 4.82. Place an initial state where the temperature is 1000 K and the pres-
these in rank order beginning with the component contribut- sure is 5 bar to a final state where the temperature is T and the
ing most to inefficient operation of the overall system. pressure is p. Using the ideal gas model together with cp (T )
6.92 Determine the rates of entropy production, each in kW/K, from Table A-21, determine
for the turbine, condenser, and pump of Problem 4.85. Place (a) p when T 500 K
these in rank order beginning with the component contribut- (b) T when p 1 bar.
ing most to inefficient operation of the overall system. (c) Check the results of parts (a) and (b) using IT.
6.93 For the control volume of Example 4.12, determine the
6.99 An ideal gas with constant specific heat ratio k enters a
amount of entropy produced during filling, in kJ/K. Repeat for
nozzle operating at steady state at pressure p1, temperature T1,
the case where no work is developed by the turbine.
and velocity V1. The air expands isentropically to a pressure
6.94 Steam is contained in a large vessel at 100 lbf/in.2, 450F. of p2.
Connected to the vessel by a valve is an initially evacuated
tank having a volume of 1 ft3. The valve is opened until the (a) Develop an expression for the velocity at the exit, V2, in
tank is filled with steam at pressure p. The filling is adiabatic, terms of k, R, V1, T1, p1, and p2, only.
kinetic and potential energy effects are negligible, and the state (b) For V1 0, T1 1000 K, plot V2 versus p2p1 for selected
of the large vessel remains constant. values of k ranging from 1.2 to 1.4.
(a) If p 100 lbf/in.2, determine the final temperature of the 6.100 An ideal gas undergoes a polytropic process from T1, p1
steam within the tank, in F, and the amount of entropy to a state where the temperature is T2.
produced within the tank, in Btu/R. (a) Derive an expression for the change in specific entropy in
(b) Plot the quantities of part (a) versus presssure p ranging terms of n, R, T1, T2, s(T1), and s(T2).
from 10 to 100 lbf/in.2 (b) Using the result of part (a), develop an expression for n if
6.95 A well-insulated rigid tank of volume 10 m3 is connected s 1 s 2.
by a valve to a large-diameter supply line carrying air at 227C
and 10 bar. The tank is initially evacuated. Air is allowed to 6.101 A rigid well-insulated tank having a volume of 0.2 m3 is
flow into the tank until the tank pressure is p. Using the ideal filled initially with Refrigerant 134a vapor at a pressure of
gas model with constant specific heat ratio k, plot tank tem- 10 bar and a temperature of 40C. A leak develops and refrig-
perature, in K, the mass of air in the tank, in kg, and the amount erant slowly escapes until the pressure within the tank becomes
of entropy produced, in kJ/K, versus p in bar. 1 bar. Determine
(a) the final temperature of the refrigerant within the tank, in C.
(b) the amount of mass that exits the tank, in kg.
Using Isentropic Processes/Efficiencies
6.96 A pistoncylinder assembly initially contains 0.1 m3 of 6.102 A rigid tank is filled initially with 5.0 kg of air at a pres-
carbon dioxide gas at 0.3 bar and 400 K. The gas is compressed sure of 0.5 MPa and a temperature of 500 K. The air is allowed
isentropically to a state where the temperature is 560 K. Em- to discharge through a turbine into the atmosphere, developing
ploying the ideal gas model and neglecting kinetic and poten- work until the pressure in the tank has fallen to the atmospheric
tial energy effects, determine the final pressure, in bar, and the level of 0.1 MPa. Employing the ideal gas model for the air,
work in kJ, using determine the maximum theoretical amount of work that could
be developed, in kJ. Ignore heat transfer with the atmosphere
(a) data from Table A-23. and changes in kinetic and potential energy.
(b) IT
(c) a constant specific heat ratio from Table A-20 at the mean 6.103 Air enters a 3600-kW turbine operating at steady state
temperature, 480 K. with a mass flow rate of 18 kg/s at 800C, 3 bar and a velocity
(d) a constant specific heat ratio from Table A-20 at 300 K. of 100 m/s. The air expands adiabatically through the turbine
and exits at a velocity of 150 m/s. The air then enters a dif-
6.97 Air enters a turbine operating at steady state at 6 bar and fuser where it is decelerated isentropically to a velocity of
1100 K and expands isentropically to a state where the tem- 10 m/s and a pressure of 1 bar. Employing the ideal gas model,
perature is 700 K. Employing the ideal gas model and ignoring determine
kinetic and potential energy changes, determine the pressure
at the exit, in bar, and the work, in kJ per kg of air flowing, (a) the pressure and temperature of the air at the turbine exit,
using in bar and C, respectively.
(b) the rate of entropy production in the turbine, in kW/K.
(a) data from Table A-22.
(c) Show the processes on a Ts diagram.
(b) IT.
(c) a constant specific heat ratio from Table A-20 at the mean 6.104 Steam at 5 MPa and 600C enters an insulated turbine
temperature, 900 K. operating at steady state and exits as saturated vapor at
(d) a constant specific heat ratio from Table A-20 at 300 K. 50 kPa. Kinetic and potential energy effects are negligible.
Determine 14 bar. The isentropic compressor efficiency is 75%. Heat

transfer between the compressor and its surroundings can be
(a) the work developed by the turbine, in kJ per kg of steam
ignored. Kinetic and potential energy effects are also negligi-
flowing through the turbine.
ble. Determine
(b) the isentropic turbine efficiency.
6.105 Nitrogen (N2) at 3.8 atm and 170C enters an insulated (a) the exit temperature, in C.
turbine operating at steady state and expands to 1 atm. If the (b) the work input, in kJ per kg of refrigerant flowing.
isentropic turbine efficiency is 83.2%, determine the tempera- 6.111 Air enters an insulated compressor operating at steady
ture at the turbine exit, in C, using the ideal gas model for the state at 1 bar, 350 K with a mass flow rate of 1 kg/s and exits
nitrogen and ignoring kinetic and potential energy changes. at 4 bar. The isentropic compressor efficiency is 82%. Deter-
mine the power input, in kW, and the rate of entropy produc-
6.106 Figure P6.106 provides steady-state operating data for a
tion, in kW/K, using the ideal gas model with
throttling valve in parallel with a steam turbine having an isen-
tropic turbine efficiency of 90%. The streams exiting the valve (a) data from Table A-22.
and the turbine mix in a mixing chamber. Heat transfer with (b) IT.
the surroundings and changes in kinetic and potential energy (c) a constant specific heat ratio, k 1.39.
can be neglected. Determine 6.112 A compressor operating at steady state takes in atmos-
(a) the power developed by the turbine, in horsepower. pheric air at 20C, 1 bar at a rate of 1 kg/s and discharges air
(b) the mass flow rate through the valve, in lb/s. at 5 bar. Plot the power required, in kW, and the exit temper-
(c) Locate the four numbered states on an hs diagram. ature, in C, versus the isentropic compressor efficiency rang-
ing from 70 to 100%. Assume the ideal gas model for the air
t = 90% and neglect heat transfer with the surroundings and changes in
kinetic and potential energy.
Turbine 3
p3 = 1 MPa 6.113 In a gas turbine operating at steady state, air enters the
compressor with a mass flow rate of 5 kg/s at 0.95 bar and 22C
and exits at 5.7 bar. The air then passes through a heat exchanger
before entering the turbine at 1100 K, 5.7 bar. Air exits the tur-
Mixing 4
1 bine at 0.95 bar. The compressor and turbine operate adiabati-
p1 = 4 MPa chamber
p4 = 1 MPa cally and kinetic and potential energy effects can be ignored.
T1 = 360C T4 = 240C Determine the net power developed by the plant, in kW, if
m 1 = 11 kg/s
(a) the compressor and turbine operate without internal irre-
p2 = 1 MPa versibilities.
2
Valve (b) the compressor and turbine isentropic efficiencies are 82
Figure P6.106 and 85%, respectively.
6.107 Water vapor enters an insulated nozzle operating at steady Analyzing Internally Reversible Flow Processes
state at 0.7 MPa, 320C, 35 m/s and expands to 0.15 MPa. If
the isentropic nozzle efficiency is 94%, determine the velocity 6.114 Air enters a compressor operating at steady state at 17C,
at the exit, in m /s. 1 bar and exits at a pressure of 5 bar. Kinetic and potential en-
ergy changes can be ignored. If there are no internal irre-
6.108 Argon enters an insulated nozzle at 2.77 bar, 1300 K, versibilities, evaluate the work and heat transfer, each in kJ per
10 m/s and exits at 1 bar, 645 m/s. For steady-state operation, kg of air flowing, for the following cases:
determine
(a) isothermal compression.
(a) the exit temperature, in K. (b) polytropic compression with n 1.3.
(b) the isentropic nozzle efficiency. (c) adiabatic compression.
(c) the rate of entropy production, in kJ/K per kg of argon
flowing. Sketch the processes on pv and Ts coordinates and associ-
ate areas on the diagrams with the work and heat transfer in
6.109 Air enters an insulated compressor operating at steady state each case. Referring to your sketches, compare for these cases
at 0.95 bar, 27C with a mass flow rate of 4000 kg/h and exits the magnitudes of the work, heat transfer, and final tempera-
at 8.7 bar. Kinetic and potential energy effects are negligible. tures, respectively.
(a) Determine the minimum theoretical power input required, 6.115 Air enters a compressor operating at steady state with a
in kW, and the corresponding exit temperature, in C. volumetric flow rate of 8 m3/min at 23C, 0.12 MPa. The air
(b) If the exit temperature is 347C, determine the power in- is compressed isothermally without internal irreversibilities,
put, in kW, and the isentropic compressor efficiency. exiting at 1.5 MPa. Kinetic and potential energy effects can be
6.110 Refrigerant 134a enters a compressor operating at steady ignored. Evaluate the work required and the heat transfer, each
state as saturated vapor at 4C and exits at a pressure of in kW.
6.116 Refrigerant 134a enters a compressor operating at steady (a) the work required by the pump.
state at 1.8 bar, 10C with a volumetric flow rate of 2.4 (b) the net work developed by the turbine.
102 m3/s. The refrigerant is compressed to a pressure of 9 bar (c) the heat transfer to the boiler.
in an internally reversible process according to pv1.04 constant. 6.120 As shown in Fig. P6.120, water flows from an elevated
Neglecting kinetic and potential energy effects, determine reservoir through a hydraulic turbine. The pipe diameter is con-
(a) the power required, in kW. stant, and operation is at steady state. Estimate the minimum
(b) the rate of heat transfer, in kW. mass flow rate, in kg/s, that would be required for a turbine power
6.117 Compare the work required at steady state to compress output of 1 MW. The local acceleration of gravity is 9.8 m/s2.
water vapor isentropically to 3 MPa from the saturated vapor
state at 0.1 MPa to the work required to pump liquid water
isentropically to 3 MPa from the saturated liquid state at
0.1 MPa, each in kJ per kg of water flowing through the device.
Kinetic and potential energy effects can be ignored. p1 = 1.3 bar
6.118 An electrically-driven pump operating at steady state 1 p2 = 1.0 bar
draws water from a pond at a pressure of 1 bar and a rate of
40 kg/s and delivers the water at a pressure of 4 bar. There is
no significant heat transfer with the surroundings, and changes
Wt = 1 MW
in kinetic and potential energy can be neglected. The isentropic 100 m
pump efficiency is 80%. Evaluating electricity at 8 cents per
kW # h, estimate the hourly cost of running the pump.
2 5m
6.119 Figure P6.119 shows three devices operating at steady
state: a pump, a boiler, and a turbine. The turbine provides the
power required to drive the pump and also supplies power to Figure P6.120
other devices. For adiabatic operation of the pump and turbine,
and ignoring kinetic and potential energy effects, determine,
in kJ per kg of steam flowing 6.121 A 5-kilowatt pump operating at steady state draws in
liquid water at 1 bar, 15C and delivers it at 5 bar at an elevation
6 m above the inlet. There is no significant change in velocity
Qin
between the inlet and exit, and the local acceleration of grav-
ity is 9.8 m/s2. Would it be possible to pump 7.5 m3 in 10 min
or less? Explain.
2 3 6.122 A 4-kW pump operating at steady state draws in liquid
8 bar 8 bar, water at 1 bar, 16C with a mass flow rate of 4.5 kg/s. There
Boiler saturated vapor are no significant kinetic and potential energy changes from
inlet to exit and the local acceleration of gravity is 9.81 m/s2.
Turbine

Wnet
Would it be possible for the pump to deliver water at a pres-
t = 90% sure of 10 bar? Explain.
Pump 6.123 Carbon monoxide enters a nozzle operating at steady
p = 70% state at 5 bar, 200C, 1 m/s and undergoes a polytropic ex-
1 4
pansion to 1 bar with n 1.2. Using the ideal gas model and
ignoring potential energy effects, determine
Feedwater Steam (a) the exit velocity, in m/s.
1 bar, 30C 1 bar (b) the rate of heat transfer between the gas and its surround-
Figure P6.119 ings, in kJ per kg of gas flowing.
6.1D Of increasing interest today are turbines, pumps, and heat irreversibilities related to heat transfer and friction on the de-
exchangers that weigh less than 1 gram and have volumes of sign and operation of micromachines.
1 cubic centimeter or less. Although many of the same design
6.2D The growth of living organisms has been studied and in-
considerations apply to such micromachines as to correspon-
terpreted thermodynamically by I. Prigogine and others, using
ding full-scale devices, others do not. Of particular interest to
the entropy and entropy production concepts. Write a paper
designers is the impact of irreversibilities on the performance
summarizing the main findings of these investigations.
of such tiny devices. Write a report discussing the influence of
6.3D The theoretical steam rate is the quantity of steam re- 6.7D Water is to be pumped from a lake to a reservoir located
quired to produce a unit amount of work in an ideal turbine. on a bluff 290 ft above. According to the specifications, the
The Theoretical Steam Rate Tables published by The American piping is Schedule 40 steel pipe having a nominal diameter of
Society of Mechanical Engineers give the theoretical steam rate 1 inch and the volumetric flow rate is 10 gal/min. The total
in lb per kW # h. To determine the actual steam rate, the theo- length of pipe is 580 ft. A centrifugal pump is specified. Esti-
retical steam rate is divided by the isentropic turbine efficiency. mate the electrical power required by the pump, in kW. Is a
Why is the steam rate a significant quantity? Discuss how the centrifugal pump a good choice for this application? What pre-
steam rate is used in practice. cautions should be taken to avoid cavitation?
6.4D Figure P6.4D illustrates an ocean thermal energy conver- 6.8D Elementary thermodynamic modeling, including the use
sion (OTEC) power plant that generates power by exploiting of the temperatureentropy diagram for water and a form of the
the naturally occurring decrease of the temperature of ocean Bernoulli equation has been employed to study certain types of
water with depth. Warm surface water enters the evaporator volcanic eruptions. (See L. G. Mastin, Thermodynamics of
#
with a mass flow rate of mw at temperature Tw 28C and Gas and Steam-Blast Eruptions, Bull. Volcanol., 57, 8598,
exits at T1 Tw. Cool water brought from a depth of 600 m 1995.) Write a report critically evaluating the underlying
#
enters the condenser with a mass flow rate of mc at tempera- assumptions and application of thermodynamic principles, as
ture Tc 5C and exits at T2 Tc. The pumps for the ocean reported in the article.
water flows and other auxiliary equipment typically require 6.9D An inventor claims to have conceived of a second law-
15% of the gross power generated. Estimate the mass flow rates challenging heat engine. (See H. Apsden, The Electronic Heat
# #
mw and mc, in kg/s, for a desired net power output of 125 MW. Engine, Proceedings 27th International Energy Conversion
Engineering Conference, 4.3574.363, 1992. Also see U.S.
Patent No. 5,101,632.) By artfully using mirrors the heat en-
T1 m w , Tw gine would efficiently convert abundant environmental heat
energy at the ambient temperature to electricity. Write a pa-
Evaporator per explaining the principles of operation of the device. Does
this invention actually challenge the second law of thermody-
namics? Does it have commercial promise? Discuss.
Turbine 6.10D Noting that contemporary economic theorists often draw
Pump on principles from mechanics such as conservation of energy
to explain the workings of economies, N. Georgescu-Roegen
and like-minded economists have called for the use of princi-
ples from thermodynamics in economics. According to this
Condenser view, entropy and the second law of thermodynamics are
relevant for assessing not only the exploitation of natural re-
m c , Tc T2
sources for industrial and agricultural production but also the
Figure P6.4D impact on the natural environment of wastes from such pro-
duction. Write a paper in which you argue for, or against, the
6.5D How might the principal sources of irreversibility be re- proposition that thermodynamics is relevant to the field of
duced for the heat pump components analyzed in Example 6.8? economics.
Carefully consider the effects of a change in any one compo- 6.11D Roll Over Boltzman (see box Sec. 6.5). The new sta-
nent on the performance of each of the others and on the heat tistical definition of entropy is said to give insights about
pump as a whole. Consider the economic consequences of pro- physical systems verging on chaos. Investigate what is meant
posed changes. Summarize your findings in a memorandum. by chaos in this context. Write a report including at least three
6.6D The Bernoulli equation can be generalized to include the references.
effects of fluid friction in piping networks in terms of the con- 6.12D Star Guides Consumer Choices (see box Sec. 6.8).
cept of head loss. Investigate the head loss formulation as it Using the ENERGY STAR Home Improvement Toolbox, ob-
applies to incompressible flows through common pipes and fit- tain a rank-ordered list of the top three cost-effective im-
tings. Using this information, estimate the head, in ft, a booster provements that would enhance the overall energy efficiency
pump would need to overcome because of friction in a 2-in. of your home. Develop a plan to implement the improvements.
galvanized steel pipe feeding water to the top floor of a 20-story Write a report including at least three references.
building.
C
H
A
P
T
7 E
R Exergy Analysis
chapter objective E N G I N E E R I N G C O N T E X T The objective of this chapter is to

introduce exergy analysis, a method that uses the conservation of mass and conservation
of energy principles together with the second law of thermodynamics for the design and
analysis of thermal systems. Another term frequently used to identify exergy analysis is
availability analysis.
The importance of developing thermal systems that make effective use of nonrenewable
resources such as oil, natural gas, and coal is apparent. The method of exergy analysis is
particularly suited for furthering the goal of more efficient resource use, since it enables the
locations, types, and true magnitudes of waste and loss to be determined. This information
can be used to design thermal systems, guide efforts to reduce sources of inefficiency in
existing systems, and evaluate system economics.

7.1 Introducing Exergy
Energy is conserved in every device or process. It cannot be destroyed. Energy entering a
system with fuel, electricity, flowing streams of matter, and so on can be accounted for in
the products and by-products. However, the energy conservation idea alone is inadequate for
depicting some important aspects of resource utilization.
for example. . . Figure 7.1a shows an isolated system consisting initially of a small
container of fuel surrounded by air in abundance. Suppose the fuel burns (Fig. 7.1b) so that
finally there is a slightly warm mixture of combustion products and air as shown in Fig. 7.1c.
Although the total quantity of energy associated with the system would be unchanged, the
initial fuelair combination would have a greater economic value and be intrinsically more
useful than the final warm mixture. For instance, the fuel might be used in some device to
generate electricity or produce superheated steam, whereas the uses to which the slightly
warm combustion products can be put would be far more limited in scope. We might say that
the system has a greater potential for use initially than it has finally. Since nothing but a final
warm mixture would be achieved in the process, this potential would be largely wasted. More
precisely, the initial potential would be largely destroyed because of the irreversible nature
of the process.
272
7.2 Defining Exergy 273
Boundary of the
isolated system
Air at temperature Air and combustion

Ti products at
temperature Ti + dT
Fuel Fuel
(a) (b) (c)

Time
Energy quantity constant
Potential for use decreases
Figure 7.1 Illustration used to introduce exergy.
Anticipating the main results of this chapter, we can read exergy as potential for use
wherever it appears in the text. The foregoing example illustrates that, unlike energy,
exergy is not conserved.
Subsequent discussion shows that exergy not only can be destroyed by irreversibilities but
also can be transferred to a system or from a system, as in losses accompanying heat trans-
fers to the surroundings. Improved resource utilization can be realized by reducing exergy
destruction within a system and/or losses. An objective in exergy analysis is to identify sites
where exergy destructions and losses occur and rank order them for significance. This allows
attention to be centered on the aspects of system operation that offer the greatest opportunities
for improvement.

7.2 Defining Exergy
The basis for the exergy concept is present in the introduction to the second law provided in
Chap. 5. A principal conclusion of Sec. 5.1 is that an opportunity exists for doing work when-
ever two systems at different states are brought into communication. In principle, work can
be developed as the systems are allowed to come into equilibrium. When one of the two sys-
tems is a suitably idealized system called an exergy reference environment or simply, an exergy reference
environment, and the other is some system of interest, exergy is the maximum theoretical environment
work obtainable as they interact to equilibrium.
The definition of exergy will not be complete, however, until we define the reference exergy
environment and show how numerical values for exergy can be determined. These tasks are
closely related because the numerical value of exergy depends on the state of a system of
interest, as well as the condition of the environment.
7.2.1 Exergy Reference Environment

Any system, whether a component of a larger system such as a steam turbine in a power
plant or the larger system itself (power plant), operates within surroundings of some kind. It
is important to distinguish between the environment used for calculating exergy and a sys-
tems surroundings. Strictly speaking, the term surroundings refers to everything not included
in the system. However, when considering the exergy concept, we distinguish between the
274 Chapter 7 Exergy Analysis
Environment Intensive properties of this portion

of the surroundings are not affected
by any process within the power plant
or its immediate surroundings
Delineates the
immediate plant
Immediate surroundingsintensive
Stack surroundings from
properties may vary in interactions
gases the environment
with power plant
Boundary of plant
Fuel
Power Power
Air
River or other body
Cooling water out Cooling water in of water the portion
not interacting with
the power plant would
be in the environment
Figure 7.2 Schematic of a power plant and its surroundings.
immediate surroundings, where intensive properties may vary during interactions with the
system, and the larger portion of the surroundings at a distance, where the intensive proper-
ties are unaffected by any process involving the system and its immediate surroundings. The
term environment identifies this larger portion of the surroundings.
for example. . . Fig. 7.2 illustrates the distinction between a system consisting
of a power plant, its immediate surroundings, and the environment. In this case, the
environment includes portions of the surrounding atmosphere and the river at a distance
from the power plant. Interactions between the power plant and its immediate surround-
ings have no influence on the temperature, pressure, or other intensive properties of the
environment.
MODELING THE ENVIRONMENT
The physical world is complicated, and to include every detail in an analysis is not practical.
Accordingly, in describing the environment, simplifications are made and a model results.
The validity and utility of an analysis using any model are, of course, restricted by the
idealizations made in formulating the model. In this book the environment is regarded to
be a simple compressible system that is large in extent and uniform in temperature, T0, and
pressure, p0. In keeping with the idea that the environment represents a portion of the
physical world, the values for both p0 and T0 used throughout a particular analysis are nor-
mally taken as typical environmental conditions, such as 1 atm and 25C. The intensive
properties of each phase of the environment are uniform and do not change significantly
as a result of any process under consideration. The environment is also regarded as free of
irreversibilities. All significant irreversibilities are located within the system and its imme-
diate surroundings.
Although its intensive properties do not change, the environment can experience changes
in its extensive properties as a result of interactions with other systems. Changes in the
extensive properties internal energy Ue, entropy Se, and volume Ve of the environment are
related through the first T dS equation, Eq. 6.10. Since T0 and p0 are constant, Eq. 6.10 takes
the form
Ue T0 Se p0 Ve (7.1)
In this chapter kinetic and potential energies are evaluated relative to the environment, all
parts of which are considered to be at rest with respect to one another. Accordingly, as indi-
cated by the foregoing equation, a change in the energy of the environment can be a change
in its internal energy only. Equation 7.1 is used below to develop an expression for evaluat-
ing exergy. In Chap. 13 the environment concept is extended to allow for the possibility of
chemical reactions, which are excluded from the present considerations.
7.2.2 Dead State

Let us consider next the concept of the dead state, which is also important in completing our
understanding of the property exergy.
If the state of a fixed quantity of matter, a closed system, departs from that of the envi-
ronment, an opportunity exists for developing work. However, as the system changes state
toward that of the environment, the opportunity diminishes, ceasing to exist when the two
are in equilibrium with one another. This state of the system is called the dead state. At the dead state
dead state, the fixed quantity of matter under consideration is imagined to be sealed in an
envelope impervious to mass flow, at rest relative to the environment, and internally in equi-
librium at the temperature T0 and pressure p0 of the environment. At the dead state, both the
system and environment possess energy, but the value of exergy is zero because there is no
possibility of a spontaneous change within the system or the environment, nor can there be
an interaction between them.
With the introduction of the concepts of environment and dead state, we are in a position
to show how a numerical value can be determined for exergy. This is considered next.
7.2.3 Evaluating Exergy

The exergy of a system, E, at a specified state is given by the expression
E 1E U0 2
p0 1V V0 2 T0 1S S0 2 (7.2) exergy of a system
Wc
Closed
system
Boundary of
the combined
System system.
boundary
Heat and work
interactions with
the environment
Environment at T0 , p0 Figure 7.3 Combined system

of closed system and environment.
METHODOLOGY where E( U

KE
PE), V, and S denote, respectively, the energy, volume, and entropy
UPDATE of the system, and U0, V0, and S0 are the values of the same properties if the system were
In this book, E and e are at the dead state. By inspection of Eq. 7.2, the units of exergy are seen to be the same as
used for exergy and those of energy. Equation 7.2 can be derived by applying energy and entropy balances to
specific exergy, respec- the combined system shown in Fig. 7.3, which consists of a closed system and an environ-
tively, while E and e ment. (See box).
denote energy and specific
energy, respectively. Such
notation is in keeping with
standard practice. The
appropriate concept, E VA L U AT I N G T H E E X E R G Y O F A S Y S T E M
exergy or energy, will be
clear in context. Still, care
Referring to Fig. 7.3, exergy is the maximum theoretical work that could be done by
is required to avoid the combined system if the closed system were to come into equilibrium with the en-
mistaking the symbols for vironmentthat is, if the closed system passed to the dead state. Since the objective
these concepts. is to evaluate the maximum work that could be developed by the combined system, the
boundary of the combined system is located so that the only energy transfers across it
are work transfers of energy. This ensures that the work developed by the combined
system is not affected by heat transfer to or from it. Moreover, although the volumes
of the closed system and the environment can vary, the boundary of the combined sys-
tem is located so that the total volume of the combined system remains constant. This
ensures that the work developed by the combined system is fully available for lifting
a weight in its surroundings, say, and is not expended in merely displacing the sur-
roundings of the combined system. Let us now apply an energy balance to evaluate the
work developed by the combined system.
ENERGY BALANCE. An energy balance for the combined system reduces to

0
Ec Qc Wc (7.3)
where Wc is the work developed by the combined system, and Ec is the energy change
of the combined system, equal to the sum of the energy changes of the closed system
and the environment. The energy of the closed system initially is denoted by E, which
includes the kinetic energy, potential energy, and internal energy of the system. Since
the kinetic energy and potential energy are evaluated relative to the environment, the
energy of the closed system when at the dead state would be just its internal energy,
U0. Accordingly, Ec can be expressed as
Ec 1U0 E2
Ue
Using Eq. 7.1 to replace Ue, the expression becomes
Ec 1U0 E2
1T0 Se p0 Ve 2 (7.4)
Substituting Eq. 7.4 into Eq. 7.3 and solving for Wc gives
Wc 1E U0 2 1T0 Se p0 Ve 2
As noted previously, the total volume of the combined system is constant. Hence, the
change in volume of the environment is equal in magnitude but opposite in sign to
the volume change of the closed system: Ve (V0 V ).With this substitution, the
above expression for work becomes
Wc 1E U0 2
p0 1V V0 2 T0 Se (7.5)
This equation gives the work developed by the combined system as the closed sys-
tem passes to the dead state while interacting only with the environment. The maxi-
mum theoretical value for the work is determined using the entropy balance as follows.
ENTROPY BALANCE. The entropy balance for the combined system reduces to give
Sc sc
where the entropy transfer term is omitted because no heat transfer takes place across
the boundary of the combined system, and sc accounts for entropy production due to
irreversibilities as the closed system comes into equilibrium with the environment. Sc
is the entropy change of the combined system, equal to the sum of the entropy changes
for the closed system and environment, respectively,
Sc 1S0 S2
Se
where S and S0 denote the entropy of the closed system at the given state and the dead
state, respectively. Combining the last two equations
1S0 S2
Se sc (7.6)
Eliminating Se between Eqs. 7.5 and 7.6 results in

Wc 1E U0 2
p0 1V V0 2 T0 1S S0 2 T0sc (7.7)
The value of the underlined term in Eq. 7.7 is determined by the two end states of the
closed systemthe given state and the dead stateand is independent of the details
of the process linking these states. However, the value of the term T0sc depends on the
nature of the process as the closed system passes to the dead state. In accordance with
the second law, T0sc is positive when irreversibilities are present and vanishes in the
limiting case where there are no irreversibilities. The value of T0sc cannot be negative.
Hence, the maximum theoretical value for the work of the combined system is obtained
by setting T0sc to zero in Eq. 7.7. By definition, the extensive property exergy, E, is
this maximum value. Accordingly, Eq. 7.2 is seen to be the appropriate expression for
evaluating exergy.
7.2.4 Exergy Aspects

In this section, we consider several important aspects of the exergy concept, beginning with
the following:
Exergy is a measure of the departure of the state of a system from that of the environ-
E
ment. It is therefore an attribute of the system and environment together. However, once Constant-
the environment is specified, a value can be assigned to exergy in terms of property exergy line
values for the system only, so exergy can be regarded as a property of the system.
The value of exergy cannot be negative. If a system were at any state other than the
dead state, the system would be able to change its condition spontaneously toward the p
dead state; this tendency would cease when the dead state was reached. No work must
be done to effect such a spontaneous change. Accordingly, any change in state of the T E = 0 at
system to the dead state can be accomplished with at least zero work being developed, T0, p0
and thus the maximum work (exergy) cannot be negative.
Exergy is not conserved but is destroyed by irreversibilities. A limiting case is when
exergy is completely destroyed, as would occur if a system were permitted to undergo a
spontaneous change to the dead state with no provision to obtain work. The potential to
develop work that existed originally would be completely wasted in such a spontaneous
process.
Exergy has been viewed thus far as the maximum theoretical work obtainable from
the combined system of system plus environment as a system passes from a given
state to the dead state while interacting with the environment only. Alternatively,
exergy can be regarded as the magnitude of the minimum theoretical work input
required to bring the system from the dead state to the given state. Using energy and
entropy balances as above, we can readily develop Eq. 7.2 from this viewpoint. This
is left as an exercise.
Although exergy is an extensive property, it is often convenient to work with it on a unit
mass or molar basis. The specific exergy on a unit mass basis, e, is given by
e 1e u0 2
p0 1v v0 2 T0 1s s0 2 (7.8)
where e, v, and s are the specific energy, volume, and entropy, respectively, at a given
state; u0, v0, and s0 are the same specific properties evaluated at the dead state. With e
u
V 22
gz,
e 3 1u
V22
gz2 u0 4
p0 1v v0 2 T0 1s s0 2
and the expression for the specific exergy becomes
specific exergy e 1u u0 2
p0 1v v0 2 T0 1s s0 2
V22
gz (7.9)
By inspection, the units of specific exergy are the same as those of specific energy. Also note
that the kinetic and potential energies measured relative to the environment contribute their
full values to the exergy magnitude, for in principle each could be completely converted to
work were the system brought to rest at zero elevation relative to the environment.
Using Eq. 7.2, we can determine the change in exergy between two states of a closed
system as the difference
exergy change E2 E1 1E2 E1 2

p0 1V2 V1 2 T0 1S2 S1 2 (7.10)
where the values of p0 and T0 are determined by the state of the environment.
When a system is at the dead state, it is in thermal and mechanical equilibrium with the
environment, and the value of exergy is zero. We might say more precisely that the therm-
omechanical contribution to exergy is zero. This modifying term distinguishes the exergy
concept of the present chapter from a more general concept introduced in Sec. 13.6, where
the contents of a system at the dead state are permitted to enter into chemical reaction with
environmental components and in so doing develop additional work. As illustrated by
subsequent discussions, the thermomechanical exergy concept suffices for a wide range of
thermodynamic evaluations.
7.2.5 Illustrations
We conclude this introduction to the exergy concept with examples showing how to calculate
exergy and exergy change. To begin, observe that the exergy of a system at a specified state
requires properties at that state and at the dead state. for example. . . let us use Eq. 7.9
to determine the specific exergy of saturated water vapor at 120C, having a velocity of
30 m/s and an elevation of 6 m, each relative to an exergy reference environment where
T0 298 K (25C), p0 1 atm, and g 9.8 m/s2. For water as saturated vapor at 120C,
Table A-2 gives v 0.8919 m3/kg, u 2529.3 kJ/kg, s 7.1296 kJ/kg # K. At the dead state,
where T0 298 K (25C) and p0 1 atm, water is a liquid. Thus, with Eqs. 3.11, 3.12, and
6.7 and values from Table A-2, we get v0 1.0029 103 m3/kg, u0 104.88 kJ/kg, s0 Saturated
0.3674 kJ/kg # K. Substituting values vapor at 120C
30 m/s
V2
e 1u u0 2
p0 1v v0 2 T0 1s s0 2

gz
2
c 12529.3 104.882 d
kJ
kg
6m
m3

c a1.01325 105 2 b 10.8919 1.0029 103 2 d` 3 # `
N 1 kJ
m kg 10 N m
c 1298 K217.1296 0.36742 d

kJ z p0 = 1 atm
T0 = 298 K
kg # K g = 9.8 m/s2
130 m/s2 2

c
a9.8 2 b 16 m2 d ` ` ` `
m 1N 1 kJ
2 s 1 kg # m/s2 103 N # m
12424.42
90.27 2015.14
0.45
0.062
kJ kJ
500
kg kg
The following example illustrates the use of Eq. 7.9 together with ideal gas property
data.
EXAMPLE 7.1 Exergy of Exhaust Gas
A cylinder of an internal combustion engine contains 2450 cm3 of gaseous combustion products at a pressure of 7 bar
and a temperature of 867C just before the exhaust valve opens. Determine the specific exergy of the gas, in kJ/kg. Ig-
nore the effects of motion and gravity, and model the combustion products as air as an ideal gas. Take T0 300 K (27C)
and p0 1.013 bar.
SOLUTION
Known: Gaseous combustion products at a specified state are contained in the cylinder of an internal combustion
engine.
Find: Determine the specific exergy.
2450 cm3 of air Assumptions:

at 7 bar, 867C
1. The gaseous combustion products are a closed system.
2. The combustion products are modeled as air as an ideal gas.
3. The effects of motion and gravity can be ignored.
4. T0 300 K (27C) and p0 1.013 bar.
Figure E7.1
Analysis: With assumption 3, Eq. 7.9 becomes

e u u0
p0 1v v0 2 T0 1s s0 2
The internal energy and entropy terms are evaluated using data from Table A-22, as follows:
u u0 880.35 214.07
666.28 kJ/kg
s s0 s1T 2 s1T0 2
R p
ln
M p0
3.11883 1.70203 a b ln a b
8.314 7
28.97 1.013
0.8621 kJ/kg # K
T0 1s s0 2 1300 K210.8621 kJ/kg # K2
258.62 kJ/kg
The p0(v v0) term is evaluated using the ideal gas equation of state: v (RM )Tp and v0 (R M )T0p0, so
p0 1v v0 2 a T0 b
R p0T
M p
8.314 11.0132111402
c 300 d
28.97 7
38.75 kJ/kg
Substituting values into the above expression for the specific exergy
e 666.28
138.752 258.62
368.91 kJ/kg
If the gases are discharged directly to the surroundings, the potential for developing work quantified by the exergy value
determined in the solution is wasted. However, by venting the gases through a turbine some work could be developed.
This principle is utilized by the turbochargers added to some internal combustion engines.
The next example emphasizes the fundamentally different characters of exergy and energy,
while illustrating the use of Eqs. 7.9 and 7.10.
EXAMPLE 7.2 Comparing Exergy and Energy
Refrigerant 134a, initially a saturated vapor at 28C, is contained in a rigid, insulated vessel. The vessel is fitted with a pad-
dle wheel connected to a pulley from which a mass is suspended. As the mass descends a certain distance, the refrigerant is
stirred until it attains a state where the pressure is 1.4 bar. The only significant changes of state are experienced by the sus-
pended mass and the refrigerant. The mass of refrigerant is 1.11 kg. Determine
(a) the initial exergy, final exergy, and change in exergy of the refrigerant, each in kJ.
(b) the change in exergy of the suspended mass, in kJ.
(c) the change in exergy of an isolated system of the vessel and pulleymass assembly, in kJ.
Discuss the results obtained, and compare with the respective energy changes. Let T0 293 K (20C), p0 1 bar.
SOLUTION
Known: Refrigerant 134a in a rigid, insulated vessel is stirred by a paddle wheel connected to a pulleymass assembly.
Find: Determine the initial and final exergies and the change in exergy of the refrigerant, the change in exergy of the sus-
pended mass, and the change in exergy of the isolated system, all in kJ. Discuss the results obtained.
Isolated system
Q=W=0
Refrigerant 134a
m R = 1.11 kg T
Saturated
1.4 bar
vapor
2 1.0 bar
Initially, saturated
vapor at 28C. mass initially 0 0.93 bar
p2 = 1.4 bar 20C
Dead
state
28C
1
z
mass finally
v
T0 = 293 K, p0 = 1 bar
Figure E7.2
Assumptions:
1. As shown in the schematic, three systems are under consideration: the refrigerant, the suspended mass, and an isolated sys-
tem consisting of the vessel and pulleymass assembly. For the isolated system Q 0, W 0.
2. The only significant changes of state are experienced by the refrigerant and the suspended mass. For the refrigerant, there
is no change in kinetic or potential energy. For the suspended mass, there is no change in kinetic or internal energy. Elevation
is the only intensive property of the suspended mass that changes.
3. For the environment, T0 293 K (20C), p0 1 bar.
Analysis:
(a) The initial and final exergies of the refrigerant can be evaluated using Eq. 7.9. From assumption 2, it follows that for the
refrigerant there are no significant effects of motion or gravity, and thus the exergy at the initial state is
E1 mR 3 1u1 u0 2
p0 1v1 v0 2 T0 1s1 s0 2 4
The initial and final states of the refrigerant are shown on the accompanying Tv diagram. From Table A-10, u1 ug(28C)
211.29 kJ/kg. v1 vg(28C) 0.2052 m3/kg, s1 sg(28C) 0.9411 kJ/kg # K. From Table A-12 at 1 bar, 20C, u0
246.67 kJ/kg, v0 0.23349 m3/kg, s0 1.0829 kJ/kg # K. Then
m3
E1 1.11 kg c 1211.29 246.672
a105 2 b 10.2052 0.233492 ` ` 293 K10.9411 1.08292 d
kJ N 1 kJ kJ
kg m kg 103 N # m kg # K
1.11 kg 3 135.382
12.832
141.552 4
kJ
3.7 kJ
kg
The final state of the refrigerant is fixed by p2 1.4 bar and v2 v1. Interpolation in Table A-12 gives u2 300.16 kJ/kg,
s2 1.2369 kJ/kg # K. Then
E2 1.11 kg3 153.492

12.832
145.122 4
kJ
kg
6.1 kJ
For the refrigerant, the change in exergy is
1 E2 refrigerant E2 E1 6.1 kJ 3.7 kJ 2.4 kJ

The exergy of the refrigerant increases as it is stirred.
(b) With assumption 2, Eq. 7.10 reduces to give the exergy change for the suspended mass
1 E2 mass 1U
p0 V T0 S
KE
PE2 mass
0 0 0 0
1PE2 mass
Thus, the exergy change for the suspended mass equals its change in potential energy.
The change in potential energy of the suspended mass is obtained from an energy balance for the isolated system as fol-
lows: The change in energy of the isolated system is the sum of the energy changes of the refrigerant and suspended mass.
There is no heat transfer or work, and with assumption 2 we have
1 KE
PE
U 2 refrigerant
1 KE
PE
U 2 mass Q W
0 0 0 0 0 0
Solving for (PE)mass and using previously determined values for the specific internal energy of the refrigerant
1 PE2 mass 1U2 refrigerant
11.11 kg21300.16 211.292 a b

kJ
kg
98.6 kJ
Collecting results, (E)mass 98.6 kJ. The exergy of the mass decreases because its elevation decreases.
(c) The change in exergy of the isolated system is the sum of the exergy changes of the refrigerant and suspended mass. With
the results of parts (a) and (b)
1 E2 isol 1 E2 refrigerant
1E2 mass
12.4 kJ2
198.6 kJ2
96.2 kJ
The exergy of the isolated system decreases.
To summarize
Energy Change Exergy Change

Refrigerant
98.6 kJ
2.4 kJ
Suspended mass 98.6 kJ 98.6 kJ
Isolated system 0.0 kJ 96.2 kJ
For the isolated system there is no net change in energy. The increase in the internal energy of the refrigerant equals the
decrease in potential energy of the suspended mass. However, the increase in exergy of the refrigerant is much less than the
decrease in exergy of the mass. For the isolated system, exergy decreases because stirring destroys exergy.
Exergy is a measure of the departure of the state of the system from that of the environment. At all states, E 0. This ap-
plies when T T0 and p p0, as at state 2, and when T T0 and p p0, as at state 1.
The exergy change of the refrigerant can be determined more simply with Eq. 7.10, which requires dead state property
values only for T0 and p0. With the approach used in part (a), values for u0, v0, and s0 are also required.
The change in potential energy of the suspended mass, (PE)mass, cannot be determined from Eq. 2.10 (Sec. 2.1) since the
mass and change in elevation are unknown. Moreover, for the suspended mass as the system, (PE)mass cannot be obtained
from an energy balance without first evaluating the work. Thus, we resort here to an energy balance for the isolated system,
which does not require such information.
As the suspended mass descends, energy is transferred by work through the paddle wheel to the refrigerant, and the re-
frigerant state changes. Since the exergy of the refrigerant increases, we infer that an exergy transfer accompanies the work
interaction. The concepts of exergy change, exergy transfer, and exergy destruction are related by the closed system exergy
balance introduced in the next section.

7.3 Closed System Exergy Balance
A system at a given state can attain a new state through work and heat interactions with its
surroundings. Since the exergy value associated with the new state would generally differ
from the value at the initial state, transfers of exergy across the system boundary can be in-
ferred to accompany heat and work interactions. The change in exergy of a system during a
process would not necessarily equal the net exergy transferred, for exergy would be destroyed
if irreversibilities were present within the system during the process. The concepts of exergy
change, exergy transfer, and exergy destruction are related by the closed system exergy bal-
ance introduced in this section. The exergy balance concept is extended to control volumes
in Sec. 7.5. These balances are expressions of the second law of thermodynamics and provide
the basis for exergy analysis.
7.3.1 Developing the Exergy Balance

The exergy balance for a closed system is developed by combining the closed system energy
and entropy balances. The forms of the energy and entropy balances used in the develop-
ment are, respectively
dQ W
2
E2 E1
1
a b
s
dQ 2
S2 S1
T 1 b
where W and Q represent, respectively, work and heat transfers between the system and its
surroundings. These interactions do not necessarily involve the environment. In the entropy
balance, Tb denotes the temperature on the system boundary where Q is received and the
term accounts for entropy produced by internal irreversibilities.
As the first step in deriving the exergy balance, multiply the entropy balance by the tem-
perature T0 and subtract the resulting expression from the energy balance to obtain
1E2 E1 2 T0 1S2 S1 2 a b W T0s

2 2 dQ
dQ T0
1 1 T b
Collecting the terms involving Q and introducing Eq. 7.10 on the left side, we can rewrite
this expression as
1E2 E1 2 p0 1V2 V1 2 a1 b dQ W T0s

2 T0
1 Tb
Rearranging, the closed system exergy balance results
a1 b dQ 3W p0 1V2 V1 2 4
2 T0
E2 E1 T0s (7.11) closed system
1 Tb
exergy balance
exergy exergy exergy
change transfers destruction
Since Eq. 7.11 is obtained by deduction from the energy and entropy balances, it is not an
independent result, but it can be used in place of the entropy balance as an expression of the
second law.
INTERPRETING THE EXERGY BALANCE
For specified end states and given values of p0 and T0, the exergy change E2 E1 on the left
side of Eq. 7.11 can be evaluated from Eq. 7.10. The underlined terms on the right depend
explicitly on the nature of the process, however, and cannot be determined by knowing only
the end states and the values of p0 and T0. The first underlined term on the right side of
Eq. 7.11 is associated with heat transfer to or from the system during the process. It can be
interpreted as the exergy transfer accompanying heat. That is
a1 b dQ
exergy transfer exergy transfer 2 T0
B R (7.12)
accompanying heat accompanying heat 1 Tb
The second underlined term on the right side of Eq. 7.11 is associated with work. It can be
interpreted as the exergy transfer accompanying work. That is
R 3W p0 1V2 V1 2 4
exergy transfer exergy transfer
B (7.13)
accompanying work accompanying work
The exergy transfer expressions are discussed further in Sec. 7.3.2. The third underlined term
on the right side of Eq. 7.11 accounts for the destruction of exergy due to irreversibilities
within the system. It is symbolized by Ed.
exergy destruction Ed T0s (7.14)
To summarize, Eq. 7.11 states that the change in exergy of a closed system can be accounted
for in terms of exergy transfers and the destruction of exergy due to irreversibilities within
the system.
When applying the exergy balance, it is essential to observe the requirements imposed by
the second law on the exergy destruction: In accordance with the second law, the exergy de-
struction is positive when irreversibilities are present within the system during the process
and vanishes in the limiting case where there are no irreversibilities. That is
Ed: e
7 0 irreversibilities present with the system
(7.15)
0 no irreversibilities present within the system
The value of the exergy destruction cannot be negative. It is not a property. By contrast, ex-
ergy is a property, and like other properties, the change in exergy of a system can be posi-
tive, negative, or zero
7 0
E2 E1: 0 (7.16)
6 0
To close our introduction to the exergy balance concept, we note that most thermal sys-
tems are supplied with exergy inputs derived directly or indirectly from the consumption of
fossil fuels. Accordingly, avoidable destructions and losses of exergy represent the waste
of these resources. By devising ways to reduce such inefficiencies, better use can be made of
fuels. The exergy balance can be used to determine the locations, types, and magnitudes
of energy resource waste, and thus can play an important part in developing strategies for
more effective fuel use.
OTHER FORMS OF THE EXERGY BALANCE
As in the case of the mass, energy, and entropy balances, the exergy balance can be expressed
in various forms that may be more suitable for particular analyses. A form of the exergy bal-
ance that is sometimes convenient is the closed system exergy rate balance.
closed system
a a1 b Qj aW p0 b Ed
dE T0 # # dV #
(7.17) exergy rate balance
dt j Tj dt
#
where dEdt is the time rate of change of exergy. The term (1 T# 0 Tj)Qj represents the time
rate of exergy transfer accompanying heat transfer at the rate Qj occurring
# at the location
on the boundary where the instantaneous temperature is Tj. The term W represents the time
rate
# of energy transfer by work. The accompanying rate of exergy transfer is given # by
(W p0 dVdt), where dVdt is the time rate of change of system volume. The term Ed ac-
counts for the time rate of exergy destruction due to irreversibilities within the system
# and
#
is related to the rate of entropy production within the system by the expression Ed T0s.
For an isolated system, no heat or work interactions with the surroundings occur, and thus
there are no transfers of exergy between the system and its surroundings. Accordingly, the
exergy balance reduces to give
E 4 isol Ed 4 isol (7.18)
Since the exergy destruction must be positive in any actual process, the only processes of an iso-
lated system that occur are those for which the exergy of the isolated system decreases. For ex-
ergy, this conclusion is the counterpart of the increase of entropy principle (Sec. 6.5.5) and, like
the increase of entropy principle, can be regarded as an alternative statement of the second law.
7.3.2 Conceptualizing Exergy Transfer

Before taking up examples illustrating the use of the closed system exergy balance, we con-
sider why the exergy transfer expressions take the forms they do. This is accomplished through
simple thought experiments. for example. . . consider a large metal part initially at the
dead state. If the part were hoisted from a factory floor into a heat-treating furnace, the exergy
of the metal part would increase because its elevation would be increased. As the metal part
was heated in the furnace, the exergy of the part would increase further as its temperature in-
creased because of heat transfer from the hot furnace gases. In a subsequent quenching process,
the metal part would experience a decrease in exergy as its temperature decreased due to heat
transfer to the quenching medium. In each of these processes, the metal part would not actu-
ally interact with the environment used to assign exergy values. However, like the exergy val-
ues at the states visited by the metal part, the exergy transfers taking place between the part
and its surroundings would be evaluated relative to the environment used to define exergy.
The following subsections provide means for conceptualizing the exergy transfers that ac-
company heat transfer and work, respectively.
EXERGY TRANSFER ACCOMPANYING HEAT
Consider a system undergoing a process in which a heat transfer Q takes place across a por-
tion of the system boundary where the temperature Tb is constant at Tb T0. In accordance
with Eq. 7.12, the accompanying exergy transfer is given by
R a1 bQ
exergy transfer T0
B (7.19)
accompanying heat Tb
Gas Q
p Volume constant
T0
Dead state
p0
Final state,
2
T2 < T0
1
Initial state,
T1 < T2 < T0 Figure 7.4 Illustration used to discuss an
exergy transfer accompanying heat transfer when
V T T0.
Q Tb
The right side of Eq. 7.19 is recognized from the discussion of Eq. 5.8 as the work, WR,
that could be developed by a reversible power cycle R receiving Q at temperature Tb and dis-
charging energy by heat transfer to the environment at T0. Accordingly, without regard for
R the nature of the surroundings with which the system is actually interacting, we may inter-
WR =
pret the magnitude of an exergy transfer accompanying heat transfer as the work that could
( T
)
1 __0 Q
Tb be developed by supplying the heat transfer to a reversible power cycle operating between
T0 Tb and T0. This interpretation also applies for heat transfer below T0, but then we think of
the magnitude of an exergy transfer accompanying heat as the work that could be developed
by a reversible power cycle receiving a heat transfer from the environment at T0 and dis-
charging Q at temperature Tb T0.
Thus far, we have considered only the magnitude of an exergy transfer accompanying heat.
It is necessary to account also for the direction. The form of Eq. 7.19 shows that when Tb is
greater than T0, the heat transfer and accompanying exergy transfer would be in the same
direction: Both quantities would be positive, or negative.
However, when Tb is less than T0, the sign of the exergy transfer would be opposite to the
sign of the heat transfer, so the heat transfer and accompanying exergy transfer would be
oppositely directed. for example. . . refer to Fig. 7.4, which shows a system consisting
of a gas heated at constant volume. As indicated by the pV diagram, the initial and final
temperatures of the gas are each less than T0. Since the state of the system is brought closer
to the dead state in this process, the exergy of the system must decrease as it is heated.
Conversely, were the gas cooled from state 2 to state 1, the exergy of the system would
increase because the state of the system would be moved farther from the dead state. In
summary, when the temperature at the location where heat transfer occurs is less than the
temperature of the environment, the heat transfer and accompanying exergy transfer are
oppositely directed. This becomes significant when studying the performance of refrigera-
tors and heat pumps, where heat transfers can occur at temperatures below that of the
environment.
EXERGY TRANSFER ACCOMPANYING WORK
We conclude the present discussion by taking up a simple example that motivates the form
taken by the expression accounting for an exergy transfer accompanying work, Eq. 7.13.
for example. . . consider a closed system that does work W while undergoing a
process in which the system volume increases: V2 V1. Although the system would not
necessarily interact with the environment, the magnitude of the exergy transfer is evaluated
Initial location Final location

of boundary, of boundary,
volume = V1 volume = V2
Expanding
system
does
work W Wc = W p0(V2 V1)
Environment Environment displaced

at T0 , p0 as system expands.
Work done by system
on environment
= p0(V2 V1)
Figure 7.5 Illustration used to

Boundary of the combined discuss the expression for an exergy
system of system plus environment transfer accompanying work.
as the maximum work that could be obtained were the system and environment interact-
ing. As illustrated by Fig. 7.5, all the work W of the system in the process would not be
available for delivery from a combined system of system plus environment because a por-
tion would be spent in pushing aside the environment, whose pressure is p0. Since the sys-
tem would do work on the surroundings equal to p0(V2 V1), the maximum amount of
work that could be derived from the combined system would thus be
Wc W p0 1V2 V1 2
which is in accordance with the form of Eq. 7.13.
As for heat transfer, work and the accompanying exergy transfer can be in the same di-
rection or oppositely directed. If there were no change in the system volume during the
process, the transfer of exergy accompanying work would equal the work W of the system.
7.3.3 Illustrations
Further consideration of the exergy balance and the exergy transfer and destruction concepts
is provided by the two examples that follow. In the first example, we reconsider Examples 6.1
and 6.2 to illustrate that exergy is a property, whereas exergy destruction and exergy trans-
fer accompanying heat and work are not properties.
EXAMPLE 7.3 Exploring Exergy Change, Transfer, and Destruction
Water initially a saturated liquid at 100C is contained in a pistoncylinder assembly. The water undergoes a process to the
corresponding saturated vapor state, during which the piston moves freely in the cylinder. For each of the two processes de-
scribed below, determine on a unit of mass basis the change in exergy, the exergy transfer accompanying work, the exergy
transfer accompanying heat, and the exergy destruction, each in kJ/kg. Let T0 20C, p0 1.014 bar.
(a) The change in state is brought about by heating the water as it undergoes an internally reversible process at constant tem-
perature and pressure.
(b) The change in state is brought about adiabatically by the stirring action of a paddle wheel.
SOLUTION
Known: Saturated liquid at 100C undergoes a process to the corresponding saturated vapor state.
Find: Determine the change in exergy, the exergy transfers accompanying work and heat, and the exergy destruction for
each of two specified processes.
Schematic and Given Data: See Figs. E6.1 and E6.2.
Assumptions:
1. For part (a), see the assumptions listed for Example 6.1. For part (b), see the assumptions listed for Example 6.2.
2. T0 20C, p0 1.014 bar.
Analysis:
(a) The change in specific exergy is obtained using Eq. 7.9

e ug uf
p0 1vg vf 2 T0 1sg sf 2
Using data from Table A-2
m3

a1.014 105 2 b a1.672 b ` 3 # ` 1293.15 K2 a6.048 b
kJ N 1 kJ kJ
e 2087.56
kg m kg 10 N m kg # K
484 kJ kg
Using the expression for work obtained in the solution to Example 6.1, Wm pvfg, the transfer of exergy accompanying
work is
p0 1vg vf 2
exergy transfer W
B R
accompanying work m
1 p p0 2vfg 0
Although the work has a nonzero value, there is no accompanying exergy transfer in this case because p p0.
Using the heat transfer value calculated in Example 6.1, the transfer of exergy of accompanying heat transfer in the constant-
temperature process is
R a1 b
exergy transfer T0 Q
B
accompanying heat T m
a1 b a2257 b
293.15 K kJ
373.15 K kg
484 kJ/kg
The positive value indicates that exergy transfer occurs in the same direction as the heat transfer.
Since the process is accomplished without irreversibilities, the exergy destruction is necessarily zero in value. This can be
verified by inserting the three exergy quantities evaluated above into an exergy balance and evaluating Edm.
(b) Since the end states are the same as in part (a), the change in exergy is the same. Moreover, because there is no heat trans-
fer, there is no exergy transfer accompanying heat. The exergy transfer accompanying work is
p0 1vg vf 2
exergy transfer W
B R
accompanying work m
With the net work value determined in Example 6.2 and evaluating the change in specific volume as in part (a)
m3
a1.014 105 2 b a1.672 b ` 3 # `
exergy transfer kJ N 1 kJ
B R 2087.56
accompanying work kg m kg 10 N m
2257 kJ/kg
The minus sign indicates that the net transfer of exergy accompanying work is into the system.
Finally, the exergy destruction is determined from an exergy balance. Solving Eq. 7.11 for the exergy destruction per unit
mass
e c p0 1vg vf 2 d 484 122572 1773 kJ/kg

Ed W
m m
The numerical values obtained can be interpreted as follows: 2257 kJ/kg of exergy is transferred into the system accom-
panying work; of this, 1773 kJ/kg is destroyed by irreversibilities, leaving a net increase of only 484 kJ/kg.
Exergy is a property and thus the exergy change during a process is determined solely by the end states. Exergy de-
struction and exergy transfer accompanying heat and work are not properties. Their values depend on the nature of the
process.
Alternatively, the exergy destruction value of part (b) could be determined using Edm T0(m), where m is obtained
from the solution to Example 6.2. This is left as an exercise.
In the next example, we reconsider the gearbox of Examples 2.4 and 6.4 from an exergy
perspective to introduce exergy accounting.
EXAMPLE 7.4 Exergy Accounting for a Gearbox
For the gearbox of Examples 2.4 and 6.4(a), develop a full exergy accounting of the power input. Let T0 293 K.
SOLUTION
Known: A gearbox operates at steady state with known values for the power input, power output, and heat transfer rate. The
temperature on the outer surface of the gearbox is also known.
Find: Develop a full exergy accounting of the input power.
Schematic and Given Data: See Fig. E6.4a.
Assumptions:
1. See the solution to Example 6.4(a).

2. T0 293 K.
Analysis: Since the gearbox volume is constant, the rate of exergy transfer accompanying power, namely 1W p0 dVdt2,
#
reduces to the power itself. Accordingly, exergy is transferred into the gearbox via the high-speed shaft at a rate equal to the
power input, 60 kW, and exergy is transferred out via the low-speed shaft at a rate equal to the power output, 58.8 kW.
Additionally, exergy is transferred out accompanying heat transfer and destroyed by irreversibilities within the gearbox.
Let us evaluate the rate of exergy transfer accompanying heat transfer. Since the temperature Tb at the outer surface of the
gearbox is uniform with position
R a1 b Q
time rate of exergy T0 #
B
transfer accompanying heat Tb
#
With Q 1.2 kW and Tb 300 K from Example 6.4a, and T0 293 K
R a1 b 11.2 kW2
time rate of exergy 293
B
transfer accompanying heat 300
0.03 kW
where the minus sign denotes exergy transfer from the system.
# #
Next, the rate of exergy destruction is calculated from Ed T0s, where s is the rate of entropy production. From the so-
# 3
lution to Example 6.4(a), s 4 10 kW/K. Then
# #
Ed T0s
1293 K214 103 kW/K2
1.17 kW
The analysis is summarized by the following exergy balance sheet in terms of exergy magnitudes on a rate basis:
Rate of exergy in:

high-speed shaft 60.00 kW (100%)
Disposition of the exergy:
Rate of exergy out
low-speed shaft 58.80 kW (98%)
heat transfer 0.03 kW (0.05%)
Rate of exergy destruction 1.17 kW (1.95%)
60.00 kW (100%)
Alternatively, the rate of exergy destruction can be determined from the steady-state form of the exergy rate balance,
Eq. 7.17. This is left as an exercise.
The difference between the input and output power is accounted for primarily by the rate of exergy destruction and only
secondarily by the exergy transfer accompanying heat transfer, which is small by comparison. The exergy balance sheet
provides a sharper picture of performance than the energy balance sheet of Example 2.4, which ignores the effect of irre-
versibilities within the system and overstates the significance of the heat transfer.

7.4 Flow Exergy
The objective of the present section is to develop the flow exergy concept. This concept is
important for the control volume form of the exergy rate balance introduced in Sec. 7.5.
When mass flows across the boundary of a control volume, there is an exergy transfer ac-
companying mass flow. Additionally, there is an exergy transfer accompanying flow work.
The specific flow exergy accounts for both of these, and is given by
V2
specific flow exergy ef h h0 T0 1s s0 2

gz (7.20)
2
In Eq. 7.20, h and s represent the specific enthalpy and entropy, respectively, at the inlet or
exit under consideration; h0 and s0 represent the respective values of these properties when
evaluated at the dead state.
EXERGY TRANSFER ACCOMPANYING FLOW WORK
As a preliminary to deriving Eq. 7.20, it is necessary to account for the exergy transfer ac-
companying flow work.
When one-dimensional flow is assumed, the work at the inlet or exit of a control volume,
# #
the flow work, is given on a time rate basis by m(pv), where m is the mass flow rate, p is
7.4 Flow Exergy 291
the pressure, and v is the specific volume at the inlet or exit (Sec. 4.2.1). The following ex-
pression accounts for the exergy transfer accompanying flow work
c d m 1pv p0v2
time rate of exergy transfer # exergy transfer:
(7.21)
accompanying flow work flow work
For the development of Eq. 7.21, see box.
Control volume
ACCOUNTING FOR EXERGY TRANSFER boundary
A C C O M PA N Y I N G F L O W W O R K
Let us develop Eq. 7.21 for the case pictured in Fig. 7.6. The figure shows a closed
system that occupies different regions at time t and a later time t
t. The fixed
quantity of matter under consideration is shown in color. During the time interval
t, some of the mass initially within the region labeled control volume exits to fill
the small region e adjacent to the control volume, as shown in Fig. 7.6b. We assume
that the increase in the volume of the closed system in the time interval t is equal
to the volume of region e and, for further simplicity, that the only work is associ-
ated with this volume change. With Eq. 7.13, the exergy transfer accompanying
work is (a) Time t.
exergy transfer
B R W p0 V (7.22a)
accompanying work
where V is the volume change of the system. The volume change of the system equals
the volume of region e. Thus, we may write V meve, where me is the mass within
region e and ve is the specific volume, which is regarded as uniform throughout Region e
region e. With this expression for V, Eq. 7.22a becomes me, ve
R W me 1 p0ve 2
exergy transfer
B (7.22b)
accompanying work
(b) Time t + t.
Equation 7.22b can be placed on a time rate basis by dividing each term by the time Figure 7.6 Illustra-
interval t and taking the limit as t approaches zero. That is tion used to introduce the
flow exergy concept.
R lim a b lim c 1 p0ve 2 d
time rate of exergy W me
B (7.23)
transfer accompanying work t S 0 t t S 0 t
In the limit as t approaches zero, the boundaries of the closed system and control vol-
ume coincide. Accordingly, in this limit the rate of energy transfer by work from the
closed system is also the rate of energy transfer by work from the control volume. For
the present case, this is just the flow work. Thus, the first term on the right side of
Eq. 7.23 becomes
lim a b me 1 peve 2
W #
(7.24)
tS0 t
#
where me is the mass flow rate at the exit of the control volume. In the limit as t ap-
proaches zero, the second term on the right side of Eq. 7.23 becomes
lim c 1 p0ve 2 d m e 1 p0ve 2

me #
(7.25)
tS0 t
In this limit, the assumption of uniform specific volume throughout region e corre-
sponds to the assumption of uniform specific volume across the exit (one-dimensional
flow).
Substituting Eqs. 7.24 and 7.25 into Eq. 7.23 gives
R me 1 peve 2 me 1 p0ve 2
time rate of exergy transfer # #
B
accompanying flow work
me 1 peve p0ve 2
#
(7.26)
Extending the reasoning given here, it can be shown that an expression having the
same form as Eq. 7.26 accounts for the transfer of exergy accompanying flow work at
inlets to control volumes as well. The general result applying at both inlets and exits
is given by Eq. 7.21.
DEVELOPING THE FLOW EXERGY CONCEPT
With the introduction of the expression for the exergy transfer accompanying flow work, at-
tention now turns to the flow exergy. When mass flows across the boundary of a control vol-
ume, there is an accompanying energy transfer given by
time rate of energy transfer #
B R me
accompanying mass flow
V2
m au
#

gzb (7.27)
2
where e is the specific energy evaluated at the inlet or exit under consideration. Likewise,
when mass enters or exits a control volume, there is an accompanying exergy transfer
given by
time rate of exergy transfer #
B R me
m 3 1e u0 2
p0 1v v0 2 T0 1s s0 2 4
#
(7.28)
where e is the specific exergy at the inlet or exit under consideration. In writing Eqs. 7.27
and 7.28, one-dimensional flow is assumed. In addition to an exergy transfer accompanying
mass flow, an exergy transfer accompanying flow work takes place at locations where mass
enters or exits a control volume. Transfers of exergy accompanying flow work are accounted
for by Eq. 7.21.
Since transfers of exergy accompanying mass flow and flow work occur at locations where
mass enters or exits a control volume, a single expression giving the sum of these effects is
convenient. Thus, with Eqs. 7.21 and 7.28,
R m 3e
1 pv p0v2 4
time rate of exergy transfer #
B
accompanying mass flow and flow work
m 3 1e u0 2
p0 1v v0 2 T0 1s s0 2 (7.29)
#

1 pv p0v2 4
The underlined terms in Eq. 7.29 represent, per unit of mass, the exergy transfer accom-
panying mass flow and flow work, respectively. The sum identified by underlining is the spe-
cific flow exergy ef. That is
ef 1e u0 2
p0 1v v0 2 T0 1s s0 2
1 pv p0v2 (7.30a)

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The specific flow exergy can be placed in a more convenient form for calculation by intro-
ducing e u
V22
gz in Eq. 7.30a and simplifying to obtain
V2
ef au

gz u0 b
1 pv p0v0 2 T0 1s s0 2
2
V2
1u
pv2 1u0
p0v0 2 T0 1s s0 2

gz (7.30b)
2
Finally, with h u
pv and h0 u0
p0v0, Eq. 7.30b gives Eq. 7.20, which is the prin-
cipal result of this section. Equation 7.20 is used in the next section where the exergy rate
balance for control volumes is formulated.
A comparison of the current development with that of Sec. 4.2 shows that the flow exergy
evolves here in a similar way as does enthalpy in the development of the control volume energy
rate balance, and they have similar interpretations: Each quantity is a sum consisting of a term
associated with the flowing mass (specific internal energy for enthalpy, specific exergy for flow
exergy) and a contribution associated with flow work at the inlet or exit under consideration.

7.5 Exergy Rate Balance for Control Volumes
In this section, the exergy balance is extended to a form applicable to control volumes. The
control volume form is generally the most useful for engineering analysis.
GENERAL FORM
The exergy rate balance for a control volume can be derived using an approach like that
employed in the box of Sec. 4.1, where the control volume form of the mass rate balance is
obtained by transforming the closed system form. However, as in the developments of the
energy and entropy rate balances for control volumes, the present derivation is conducted
less formally by modifying the closed system rate form, Eq. 7.17, to account for the exergy
transfers accompanying mass flow and flow work at the inlets and exits.
The result is the control volume exergy rate balance
a a1 b Qj aWcv p0 b
a miefi a meefe Ed
dEcv T0 # # dVcv # # #
(7.31)
dt j Tj dt i e
control volume rate of rate of rate of
exergy rate balance
exergy exergy exergy
change transfer destruction
As for control volume rate balances considered previously, i denotes inlets and e denotes
exits.
In Eq. 7.31 the term# dEcvdt represents the time rate of change of the exergy of the con-
trol volume. The term Qj represents the time rate of heat transfer at the location on the bound-
ary where the instantaneous
# temperature
# is Tj. The accompanying exergy transfer rate is given
by (1 T0 Tj)Qj. The term Wcv represents the time rate of energy transfer
# rate by work other
than flow work. The accompanying exergy transfer rate is given by (Wcv p0 dVcvdt), where
#
dVcvdt is the time rate of change of volume. The term miefi accounts for the time rate of ex-
#
ergy transfer accompanying mass flow and flow work at inlet i. Similarly, miefe accounts for
the time rate of exergy transfer accompanying mass flow and flow work at exit e. The flow
exergies efi and efe appearing in these expressions are evaluated using Eq. 7.20. In writing
Eq. 7.31, #one-dimensional flow is assumed at locations where mass enters and exits. Finally,
the term Ed accounts for the time rate of exergy destruction due to irreversibilities within the
control volume.
STEADY-STATE FORMS
Since a great many engineering analyses involve control volumes at steady state, steady-
state forms of the exergy rate balance are particularly important. At steady state, dEcvdt
dVcvdt 0, so Eq. 7.31 reduces to the steady-state exergy rate balance
steady-state exergy
0 a a1 b Qj Wcv
a miefi a meefe Ed
T0 # # #
rate balance: # #
(7.32a)
j Tj i e
control volumes
This equation indicates that the rate at which exergy is transferred into the control volume
must exceed the rate at which exergy is transferred out, the difference being the rate at which
exergy is destroyed within the control volume due to irreversibilities.
Equation 7.32a can be expressed more compactly as
# # # # #
0 a Eq j Wcv
a Efi a Efe Ed (7.32b)
j i e
where
Eq j a1 b Qj
# T0 #
(7.33)
Tj
# #
Efi mi efi (7.34a)
# #
Efe mee fe (7.34b)
are
# exergy transfer rates. At steady state, the rate of exergy transfer accompanying the power
Wcv is the power itself.
If there is a single inlet and a single exit, denoted by 1 and 2, respectively, Eq. 7.32a re-
duces to
0 a a1 b Qj Wcv
m 1ef1 ef2 2 Ed
T0 # # # #
(7.35)
j Tj
# METHODOLOGY
where m is the mass flow rate. The term (ef1 ef2) is evaluated using Eq. 7.20 as UPDATE
When the rate # of exergy

V21 V22
ef1 ef2 1h1 h2 2 T0 1s1 s2 2

g1z1 z2 2
destruction Ed is the
(7.36) objective, it can be
2 determined either from an
exergy# rate balance or
#
from Ed T0scv, where
#
scv is the rate of entropy
ILLUSTRATIONS production evaluated from
an entropy rate balance.
The following examples illustrate the use of the mass, energy, and exergy rate balances for The second of these pro-
the analysis of control volumes at steady state. Property data also play an important role in cedures normally requires
arriving at solutions. The first example involves the expansion of a gas through a valve fewer property evalua-
(a throttling process, Sec. 4.3). From an energy perspective, the expansion of the gas occurs tions and less
computation.
without loss. Yet, as shown in Example 7.5, such a valve is a site of thermodynamic ineffi-
ciency quantified by exergy destruction.
EXAMPLE 7.5 Exergy Destruction in a Throttling Valve
Superheated water vapor enters a valve at 3.0 MPa, 320C and exits at a pressure of 0.5 MPa. The expansion is a throt-
tling process. Determine the specific flow exergy at the inlet and exit and the exergy destruction per unit of mass flowing,
each in kJ/kg. Let T0 25C, p0 1 atm.
SOLUTION
Known: Water vapor expands in a throttling process through a valve from a specified inlet state to a specified exit pressure.
Find: Determine the specific flow exergy at the inlet and exit of the valve and the exergy destruction per unit of mass flowing.
Assumptions:
1. The control volume shown in the accompanying figure is at steady

1 2 state.
# #
2. For the throttling process, Qcv Wcv 0, and kinetic and poten-
tial energy effects can be ignored.
Steam
3.0 MPa 0.5 MPa 3. T0 25C, p0 1 atm.
320C
Figure E7.5
Analysis: The state at the inlet is specified. The state at the exit can be fixed by reducing the steady-state mass and energy
rate balances to obtain
h2 h1
Thus, the exit state is fixed by p2 and h2. From Table A-4, h1 3043.4 kJ/s, s1 6.6245 kJ/kg # k. Interpolating at a pressure
of 0.5 MPa with h2 h1, the specific entropy at the exit is s2 7.4223 kJ/kg # k. Evaluating h0 and s0 at the saturated liquid
state corresponding to T0, Table A-2 gives h0 104.89 kJ/kg, s0 0.3674 kJ/kg # k.
Dropping V22 and gz, we obtain the specific flow exergy from Eq. 7.20 as
ef h h0 T0 1s s0 2
Substituting values into the expression for ef, the flow exergy at the inlet is
ef1 13043.4 104.892 29816.6245 0.36742 1073.89 kJ/kg
At the exit
ef2 13043.4 104.892 29817.4223 0.36742 836.15 kJ/kg
With assumptions listed, the steady-state form of the exergy rate balance, Eq. 7.35, reduces to
0
0 a a1 b Qj Wcv
m 1ef1 ef2 2 Ed
T0 # #0 # #
j Tj
#
Dividing by the mass flow rate m and solving, the exergy destruction per unit of mass flowing is
#
# 1ef1 ef2 2
Ed
m
Inserting values
#
Ed
m
# 1073.89 836.15 237.7 kJ/kg
Since h1 h2, this expression for the exergy destruction reduces to

#
# T0 1s2 s1 2
Ed
m
Thus, the exergy destruction can be determined knowing only T0 and # the specific entropies s1 and s2. The foregoing equa-
#
tion can be obtained alternatively beginning with the relationship Ed T0scv and then evaluating the rate of entropy pro-
#
duction scv from an entropy balance.
Energy is conserved in the throttling process, but exergy is destroyed. The source of the exergy destruction is the uncon-
trolled expansion that occurs.
Although heat exchangers appear from an energy perspective to operate without loss when
stray heat transfer is ignored, they are a site of thermodynamic inefficiency quantified by ex-
ergy destruction. This is illustrated in the next example.
EXAMPLE 7.6 Exergy Destruction in a Heat Exchanger
Compressed air enters a counterflow heat exchanger operating at steady state at 610 K, 10 bar and exits at 860 K, 9.7 bar. Hot
combustion gas enters as a separate stream at 1020 K, 1.1 bar and exits at 1 bar. Each stream has a mass flow rate of 90 kg/s.
Heat transfer between the outer surface of the heat exchanger and the surroundings can be ignored. Kinetic and potential energy
effects are negligible. Assuming the combustion gas stream has the properties of air, and using the ideal gas model for both
streams, determine for the heat exchanger
(a) the exit temperature of the combustion gas, in K.

(b) the net change in the flow exergy rate from inlet to exit of each stream, in MW.
(c) the rate exergy is destroyed, in MW.
Let T0 300 K, p0 1 bar.
SOLUTION
Known: Steady-state operating data are provided for a counterflow heat exchanger.
Find: For the heat exchanger, determine the exit temperature of the combustion gas, the change in the flow exergy rate from
inlet to exit of each stream, and the rate exergy is destroyed.
Tave
T3
T4 T2
T1
Assumptions:
T3 = 1020 K 1. The control volume shown in the accompanying figure
p4 = 1 bar 4 3 p3 = 1.1 bar is at steady state.
# #
Combustion Fuel 2. For the control volume, Qcv 0, Wcv 0, and changes
gases in kinetic and potential energy from inlet to exit are
negligible.
2 3. Each stream has the properties of air modeled as an
Combustor
ideal gas.
1 T1 = 610 K T2 = 860 K
4. T0 300 K, p0 1 bar.
p1 = 10 bar p2 = 9.7 bar
Compressor Turbine
Air
Figure E7.6
Analysis:
(a) The temperature T4 of the exiting combustion gases can be found by reducing the mass and energy rate balances for the
control volume at steady state to obtain
V21 V22 V23 V24
0 Qcv Wcv
m c 1h1 h2 2
a b
g1z1 z2 2 d
m c 1h3 h4 2
a b
g1z3 z4 2 d
# # # #
2 2
#
where m is the common mass flow rate of the two streams. The underlined terms drop out by listed assumptions, leaving
0 m 1h1 h2 2
m 1h3 h4 2
# #
#
Dividing by m and solving for h4
h4 h3
h1 h2
From Table A-22, h1 617.53 kJ/kg, h2 888.27 kJ/kg, h3 1068.89 kJ/kg. Inserting values
h4 1068.89
617.53 888.27 798.15 kJ/kg
Interpolating in Table A-22 gives T4 778 K (505C).
(b) The net change in the flow exergy rate from inlet to exit for the compressed air stream can be evaluated using Eq. 7.36,
neglecting the effects of motion and gravity. With Eq. 6.21a and data from Table A-22
m 1ef2 ef1 2 m 1h2 h1 2 T0 1s2 s1 2

# #
m c 1h2 h1 2 T0 as 2 s1 R ln b d
# p2
p1
c 1888.27 617.532 300 K a2.79783 2.42644 b # d

kg kJ 8.314 9.7 kJ
90 ln
s kg 28.97 10 kg K
` ` 14.1 MW
kJ 1 MW
14,103
s 103 kJ/s
Thus, as the air passes from 1 to 2, its flow exergy increases.

Similarly, the change in the flow exergy rate from inlet to exit for the combustion gas is
m 1ef4 ef3 2 m c 1h4 h3 2 T0 as 4 s 3 R ln b d

# # p4
p3
90 c 1798.15 1068.892 300 a2.68769 2.99034 ln b d

8.314 1
28.97 1.1
` ` 16.93 MW
kJ 1 MW
16,934
s 103 kJ/s
Thus, as the combustion gas passes from 3 to 4, its flow exergy decreases.
(c) The rate of exergy destruction within the control volume can be determined from an exergy rate balance
0 a a1 b Qj Wcv
m 1ef1 ef2 2
m 1ef3 ef4 2 Ed
T0 # #0 # # #
j Tj
#
Solving for Ed and inserting known values
Ed m 1ef1 ef2 2
m 1ef3 ef4 2
# # #
114.1 MW2
116.93 MW2 2.83 MW
Comparing results, we see that the exergy increase of the compressed air stream is less than the exergy decrease of the com-
bustion gas stream, even though each has the same energy change. The difference is accounted for by exergy destruction.
Energy is conserved but exergy is not.
Heat exchangers of this type are known as regenerators (see Sec. 9.7).
The variation in temperature of each stream passing through the heat exchanger is sketched in the schematic.
#

# #
Alternatively, the rate of exergy destruction can be determined using Ed T0scv, where scv is the rate of entropy produc-
tion evaluated from an entropy rate balance. This is left as an exercise.
Exergy is destroyed by irreversibilities associated with fluid friction and stream-to-stream heat transfer. The pressure drops
for the streams are indicators of frictional irreversibility. The temperature difference between the streams is an indicator
of heat transfer irreversibility.
The next two examples provide further illustrations of exergy accounting. The first in-
volves the steam turbine with stray heat transfer considered previously in Ex. 6.6.
EXAMPLE 7.7 Exergy Accounting of a Steam Turbine
Steam enters a turbine with a pressure of 30 bar, a temperature of 400C, a velocity of 160 m/s. Steam exits as saturated va-
por at 100C with a velocity of 100 m /s. At steady state, the turbine develops work at a rate of 540 kJ per kg of steam flow-
ing through the turbine. Heat transfer between the turbine and its surroundings occurs at an average outer surface tempera-
ture of 350 K. Develop a full accounting of the net exergy carried in by the steam, per unit mass of steam flowing. Neglect
the change in potential energy between inlet and exit. Let T0 25C, p0 1 atm.
SOLUTION
Known: Steam expands through a turbine for which steady-state data are provided.
Find: Develop a full exergy accounting of the net exergy carried in by the steam, per unit mass of steam flowing.
Schematic and Given Data: See Fig. E6.6.
Assumptions:
1. The turbine is at steady state.
2. Heat transfer between the turbine and the surroundings occurs at a known temperature.
3. The change in potential energy between inlet and exit can be neglected.
4. T0 25C, p0 1 atm.
Analysis: The net exergy carried in per unit mass of steam flowing is obtained using Eq. 7.36
V21 V22
ef1 ef2 1h1 h2 2 T0 1s1 s2 2
a b
2
where the potential energy term is dropped by assumption 3. From Table A-4, h1 3230.9 kJ/kg, s1 6.9212 kJ/kg # K. From
Table A-2, h2 2676.1 kJ /kg, s2 7.3549 kJ/kg # K. Hence, the net rate exergy is carried in is
11602 2 11002 2
ef1 ef2 c 13230.9 2676.12 29816.9212 7.35492
d
2 103
691.84 kJ/kg
The net exergy carried in can be accounted for in terms of exergy transfers accompanying work and heat from the control
volume and # exergy destruction within the control
# volume. At steady state, the exergy transfer accompanying work is the work
itself, or Wcvm 540 kJ/kg. The quantity
# #
# Q cv m is evaluated in the solution to Example 6.6 using the steady-state forms of
the mass and energy rate balances: Qcvm 22.6 kJ/kg. The accompanying exergy transfer is
#
# #
Eq
a1 b a # b
T0 Qcv
#
m Tb m
a1 b a22.6 b
298 kJ
350 kg
kJ
3.36
kg
where Tb denotes the temperature on the boundary where heat transfer occurs.
The exergy destruction can be determined by rearranging the steady-state form of the exergy rate balance, Eq. 7.35, to give
# # #
# a1 b a # b #
1ef1 ef2 2
Ed T0 Qcv Wcv
m Tb m m
Substituting values
#
Ed
# 3.36 540
691.84 148.48 kJ/kg
m
Net rate of exergy in: 691.84 kJ/kg (100%)

Rate of exergy out
work 540.00 kJ/kg (78.05%)
heat transfer 3.36 kJ/kg (0.49%)
Rate of exergy destruction 148.48 kJ/kg (21.46%)
691.84 kJ/kg (100%)
Note that the exergy transfer accompanying heat transfer is small relative to the other terms.
#

# #
The exergy destruction can be determined alternatively using Ed T0scv, where scv is the rate of entropy production from
an entropy balance. The solution to Example 6.6 provides scvm 0.4983 kJ/kg # K.
# #
The next example illustrates the use of exergy accounting to identify opportunities for
improving thermodynamic performance.
EXAMPLE 7.8 Exergy Accounting of a Waste Heat Recovery System
Suppose the system of Example 4.10 is one option under consideration for utilizing the combustion products discharged from
an industrial process.
(a) Develop a full accounting of the net exergy carried in by the combustion products.
(b) Discuss the design implications of the results.
SOLUTION
Known: Steady-state operating data are provided for a heat-recovery steam generator and a turbine.
Find: Develop a full accounting of the net rate exergy is carried in by the combustion products and discuss the implications
for design.
m 1 = 69.78 kg/s
p1 = 1 bar 1
T1 = 478K

Turbine Wcv = 877 kW Assumptions:
4
2 1. See solution to Example 4.10.
T4 = 180C
T2 = 400K Steam p4 = 0.275 MPa 2. T0 298K.
p2 = 1 bar generator
5
3 p3 = .275 MPa p5 = 0.07 bar

Water in T3 = 38.9C x5 = 93%
m 3 = 2.08 kg/s
Figure E7.8
Analysis:
(a) We begin by determining the net rate exergy is carried into the control volume. Modeling the combustion products as an
ideal gas, the net rate is determined using Eq. 7.36 together with Eq. 6.21a as
m1 3ef1 ef2 4 m1 3 h1 h2 T0 1s1 s2 2 4
# #
m1 c h1 h2 T0 as 1 s 2 R ln b d
# p1
p2
With data from Table A-22, h1 480.35 kJ/kg, h2 400.97 kJ/kg, s 1 2.173 kJ/kg # K, s 2 1.992 kJ/kg # K, and p2 p1,
we have
m1ef1 ef2 69.8 kg/s c 1480.35 400.972

kJ kJ
d kJ/s
#
298K12.173 1.9922
kg kg # C
1775.78 kJ/s
Next, we determine the rate exergy is carried out of the control volume. Exergy is carried out of the control volume
by work at a rate of 876.8 kJ/s, as shown on the schematic. Additionally, the net rate exergy is carried out by the water
stream is
m3ef5 ef3 m3h5 h3 T0 1s5 s3 2

# #
From Table A-2E, h3 hf 139C2 162.82 kg/s, s3 sf 139C2 0.5598 kJ/kg # K. Using saturation data at 0.07 bars from
Table A-3 with x5 0.93 gives h5 2403.27 kJ/kg and s5 7.739 kJ/kg # K. Substituting values
c 12403.27 162.822 d
# kg kJ kJ
m3ef5 ef3 2.08 29817.739 0.55982
s kg kg # K
209.66 kJ/s
Next, the rate exergy is destroyed in the heat-recovery steam generator can be obtained from an exergy rate balance ap-
plied to a control volume enclosing the steam generator. That is
0
0 a a1 b Qj Wcv
m1 1ef1 ef2 2
m3 1ef3 ef4 2 Ed
T0 # #0 # # #
j Tj
Evaluating 1ef3 ef4 2 with Eq. 7.36 and solving for Ed

#
Ed m1 1ef1 ef2 2
m3h3 h4 T0 1s3 s4 2
# # #
The first term on the right is evaluated above. Then, with h4 2825 kJ/kg, s4 7.2196 kJ/kg # K at 180C, .275 MPa from
Table A-4, and previously determined values for h3 and s3
Ed 1775.78
2.08 c 1162 28252 d
# kJ kg kJ kJ
2981.559 7.21962 #
s s kg kg K
366.1 kJ/s
Finally, the rate exergy is destroyed in the turbine can be obtained from an exergy rate balance applied to a control vol-
ume enclosing the turbine. That is
0
0 a a1 b Qj Wcv
m4 1ef4 ef5 2 Ed
T0 # # # #
j T j
Solving for Ed, evaluating 1ef4 ef5 2 with Eq. 7.36, and using previously determined values
#
Ed Wcv
m4 h4 h5 T0 1s4 s5 2
# # #
876.8
2.08 c 12825 24032 298K 17.2196 7.7392 # d
kJ kg kJ kJ
s s kg kg C
320.2 kJ /s
Net rate of exergy in: 1772.8 kJ/s (100%)

Rate of exergy out
power developed 876.8 kJ/s (49.5%)
water stream 209.66 kJ/s (11.8%)
Rate of exergy destruction
heat-recovery steam generator 366.12 kJ/s (20.6%)
turbine 320.2 kJ/s (18%)
(b) The exergy balance sheet suggests an opportunity for improved thermodynamic performance because about 50% of the
net exergy carried in is either destroyed by irreversibilities or carried out by the water stream. Better thermodynamic per-
formance might be achieved by modifying the design. For example, we might reduce the heat transfer irreversibility by spec-
ifying a heat-recovery steam generator with a smaller stream-to-stream temperature difference, and/or reduce friction by
specifying a turbine with a higher isentropic efficiency. Thermodynamic performance alone would not determine the preferred
option, however, for other factors such as cost must be considered, and can be overriding. Further discussion of the use of
exergy analysis in design is provided in Sec. 7.7.1.
Alternatively, the rates of # exergy destruction in control volumes enclosing the heat-recovery steam generator and turbine
# #
can be determined using Ed T0 scv, where scv is the rate of entropy production for the respective control volume evalu-
ated from an entropy rate balance. This is left as an exercise.
In previous discussions we have noted the effect of irreversibilities on thermodynamic

performance. Some economic consequences of irreversibilities are considered in the next
example.
EXAMPLE 7.9 Cost of Exergy Destruction
For the heat pump of Examples 6.8 and 6.14, determine the exergy destruction rates, each in kW, for the compressor, condenser,
and throttling valve. If exergy is valued at $0.08 per kW # h, determine the daily cost of electricity to operate the compressor
and the daily cost of exergy destruction in each component. Let T0 273 K (0C), which corresponds to the temperature of
the outside air.
SOLUTION
Known: Refrigerant 22 is compressed adiabatically, condensed by heat transfer to air passing through a heat exchanger, and
then expanded through a throttling valve. Data for the refrigerant and air are known.
Find: Determine the daily cost to operate the compressor. Also determine the exergy destruction rates and associated daily
costs for the compressor, condenser, and throttling valve.

See Examples 6.8 and 6.14.
Assumptions:
1. See Examples 6.8 and 6.14.

2. T0 273 K (0C).
Analysis: The rates of exergy destruction can be calculated using

# #
Ed T0s
7.6 Exergetic (Second Law) Efficiency 303
together with data for the entropy production rates from Example 6.8. That is
1Ed 2 comp 1273 K2117.5 104 2 a b 0.478 kW

# kW
K
1Ed 2 valve 1273219.94 10 2 0.271 kW
# 4
1Ed 2 cond 1273217.95 104 2 0.217 kW

#
The costs of exergy destruction are, respectively
a b 10.478 kW2 a b` ` $0.92

Daily cost of exergy destruction due $0.08 24 h
to compressor irreversibilities kW # h day
a b 10.271210.082 0 24 0 $0.52
Daily cost of exergy destruction due to
irreversibilities in the throttling valve
a b 10.271210.082 0 24 0 $0.42
Daily cost of exergy destruction due to
irreversibilities in the condenser
From the solution to Example 6.14, the magnitude of the compressor power is 3.11 kW. Thus, the daily cost is
a b 13.11 kW2 a b` ` $5.97

Daily cost of electricity $0.08 24 h
to operate compressor kW # h day
Note that the total cost of exergy destruction in the three components is about 31% of the cost of electricity to operate the
compressor.
Associating exergy destruction with operating costs provides a rational basis for seeking cost-effective design improve-
ments. Although it may be possible to select components that would destroy less exergy, the trade-off between any re-
sulting reduction in operating cost and the potential increase in equipment cost must be carefully considered.

7.6 Exergetic (Second Law) Efficiency
The objective of this section is to show the use of the exergy concept in assessing the ef-
fectiveness of energy resource utilization. As part of the presentation, the exergetic efficiency exergetic efficiency
concept is introduced and illustrated. Such efficiencies are also known as second law
efficiencies.
7.6.1 Matching End Use to Source

Tasks such as space heating, heating in industrial furnaces, and process steam generation
commonly involve the combustion of coal, oil, or natural gas. When the products of com-
bustion are at a temperature significantly greater than required by a given task, the end use
is not well matched to the source and the result is inefficient use of the fuel burned. To il-
lustrate this simply, refer to Fig. 7.7, which shows a closed system receiving a heat transfer

Q1
T1

Air Qs Qu
Ts Tu
System boundary Figure 7.7 Schematic used to discuss the

Fuel efficient use of fuel.
# #
at the rate Qs at a source temperature Ts and delivering# Qu at a use temperature Tu. Energy
is lost to the surroundings by heat transfer at a rate Ql across a portion of the surface at Tl.
All energy transfers shown on the figure are in the directions indicated by the arrows.
Assuming that the system of Fig. 7.7 operates at steady state and there is no work, the
closed system energy and exergy rate balances reduce, respectively, to
0
1Qs Qu Ql 2 W
dE # # # #0
dt
0 0
c a1 b Qs a1 b Qu a1 b Q1 d c W p0 d Ed
dE T0 # T0 # T0 # #0 dV #
dt Ts Tu T1 dt
These equations can be rewritten as follows
# # #
Qs Qu
Ql (7.37a)
a1 b Qs a1 b Qu
a1 b Ql
Ed
T0 # T0 # T0 # #
(7.37b)
Ts Tu Tl
# #
Equation 7.37a indicates that
# the energy carried in by heat transfer, Qs, is either used, Qu,
or lost to the surroundings, Ql. This can be described by an efficiency in terms of energy
rates in the form product/input as
#
Qu
h # (7.38)
Qs
In principle, the value # of h can be increased by applying insulation to reduce the loss. The
limiting value, when Ql 0, is h 1 (100%).
Equation
# 7.37b shows that the exergy carried into the system accompanying # the heat #
transfer Qs is either transferred from the system accompanying the heat transfers Qu and Ql
or destroyed by irreversibilities within the system. This can be described by an efficiency in
the form product/input as
11 T0Tu 2Qu
#
e
11 T0Ts 2Qs
# (7.39a)
Introducing Eq. 7.38 into Eq. 7.39a results in

1 T0Tu
e ha b (7.39b)
1 T0Ts
The parameter e, defined with reference to the exergy concept, may be called an exergetic
efficiency. Note that and e each gauge how effectively the input is converted to the prod-
uct. The parameter does this on an energy basis, whereas e does it on an exergy basis. As
discussed next, the value of e is generally less than unity even when 1.
Equation 7.39b indicates that a value for as close to unity as practical is important for
proper utilization of the exergy transferred from the hot combustion gas to the system. How-
ever, this alone would not ensure effective utilization. The temperatures Ts and Tu are also
important, with exergy utilization improving as the use temperature Tu approaches the source
temperature Ts. For proper utilization of exergy, therefore, it is desirable to have a value
for as close to unity as practical and also a good match between the source and use
temperatures.
To emphasize the central role of temperature in exergetic efficiency considerations, a graph
of Eq. 7.39b is provided in Fig. 7.8. The figure gives the exergetic efficiency e versus the
use temperature Tu for an assumed source temperature Ts 2200 K. Figure 7.8 shows that
e tends to unity (100%) as the use temperature approaches Ts. In most cases, however, the
1.0
1 (100%)
as Tu Ts
Heating in industrial furnaces

0.5
Process steam generation
Space heating
300 500 K 1000 K 1500 K Tu

540 900R 1800R 2700R
Figure 7.8 Effect of use temperature Tu on the exergetic efficiency e
(Ts 2200 K, h 100% ).
use temperature is substantially below Ts. Indicated on the graph are efficiencies for three
applications: space heating at Tu 320 K, process steam generation at Tu 480 K, and
heating in industrial furnaces at Tu 700 K. These efficiency values suggest that fuel is used
far more effectively in the higher use-temperature industrial applications than in the lower
use-temperature space heating. The especially low exergetic efficiency for space heating re-
flects the fact that fuel is consumed to produce only slightly warm air, which from an ex-
ergy perspective has considerably less utility. The efficiencies given on Fig. 7.8 are actually
on the high side, for in constructing the figure we have assumed to be unity (100%). More-
over, as additional destruction and loss of exergy would be associated with combustion, the
overall efficiency from fuel input to end use would be much less than indicated by the val-
ues shown on the figure.
COSTING HEAT LOSS. For the system in Fig. 7.7,

# it is instructive to consider
# further the
rate of exergy loss accompanying the heat loss Ql, that is (1 T0 T1)Q1. This expression
measures the true thermodynamic value of the heat loss and is graphed in Fig. 7.9. The fig-
ure shows that the thermodynamic value of the heat loss depends significantly
# on the tem-
perature at which the heat loss occurs. Stray heat transfer, such as Ql, usually occurs at rel-
atively low temperature, and thus has relatively low thermodynamic value. We might expect
that the economic value of such a loss varies similarly with temperature, and this is the case.
for example. . . since the source of the exergy loss by heat transfer is the fuel input
(see Fig. 7.7), the economic value of the loss can be accounted for in terms of the unit cost
of fuel based on exergy, cF (in $/kW # h, for example), as follows
# rate of heat lossR cF 11 T0Tl 2Ql

Cost #
B (7.40)
Ql at temperature Tl

Ql

T
1 __0 Q l
Tl
Figure 7.9 Effect of the
temperature ratio TlT0 on the
0 exergy loss associated with heat
1 2 3 4 5 6 Tl / T0 transfer.
Equation 7.40 shows that the cost of such a loss is less at lower temperatures than at higher
temperatures.
The above example illustrates what we would expect of a rational costing method. It would
not be rational to assign the same economic value for a heat transfer occurring near ambi-
ent temperature, where the thermodynamic value is negligible, as for an equal heat transfer
occurring at a higher temperature, where the thermodynamic value is significant. Indeed, it
would be incorrect to assign the same cost to heat loss independent of the temperature at
which the loss is occurring. For further discussion of exergy costing, see Sec. 7.7.2.
7.6.2 Exergetic Efficiencies of Common Components

Exergetic efficiency expressions can take many different forms. Several examples are given
in the current section for thermal system components of practical interest. In every instance,
the efficiency is derived by the use of the exergy rate balance. The approach used here serves
as a model for the development of exergetic efficiency expressions for other components.
Each of the cases considered involves a control volume at steady state, and we assume no
heat transfer between the control volume and its surroundings. The current presentation is
not exhaustive. Many other exergetic efficiency expressions can be written.
TURBINES. For a turbine operating at steady state with no heat transfer with its surround-
ings, the steady-state form of the exergy rate balance, Eq. 7.35, reduces as follows:
0
0 a a1 b Qj Wcv
m 1ef1 ef2 2 Ed
T0 # # # #
j Tj
This equation can be rearranged to read
# #
Wcv Ed
ef1 ef2 #
# (7.41)
m m
The term on the left of Eq. 7.41 is the decrease in flow exergy from turbine inlet to# exit.
exergy decreases because the turbine develops work, Wcvm,
#
The equation shows that the
# flow
and exergy is destroyed, Ed m. A parameter that gauges how effectively the flow exergy de-
#
crease is converted to the desired product is the exergetic turbine efficiency
#
Wcvm
#
e (7.42)
ef1 ef2
This particular exergetic efficiency is sometimes refered to as the turbine effectiveness. Care-
fully note that the exergetic turbine efficiency is defined differently from the isentropic tur-
bine efficiency introduced in Sec. 6.8.
for example. . . the exergetic efficiency of the turbine considered in Example 6.11
is 81.2% when T0 298 K. It is left as an exercise to verify this value.
COMPRESSORS AND PUMPS. For a compressor or pump operating at steady state with
no heat transfer with its surroundings, the exergy rate balance, Eq. 7.35, can be placed in the
form
# #
a # b ef2 ef1
#
Wcv Ed
m m
Hot 2 1
stream,
m h
Cold
stream,
m
c 3 4
Figure 7.10 Counterflow heat exchanger.
#
Thus, the exergy input to the device, Wcvm, is accounted for either as an increase in the
#
flow exergy between inlet and exit or as exergy destroyed. The effectiveness of the conver-
sion from work input to flow exergy increase is gauged by the exergetic compressor (or pump)
efficiency
ef2 ef1
e
1Wcvm2
# # (7.43)
for example. . . the exergetic efficiency of the compressor considered in Example

6.14 is 84.6% when T0 273 K. It is left as an exercise to verify this value.
HEAT EXCHANGER WITHOUT MIXING. The heat exchanger shown in Fig. 7.10 operates
at steady state with no heat transfer with its surroundings and both streams at temperatures
above T0. The exergy rate balance, Eq. 7.32a, reduces to
0 0
0 a a1 b Qj Wcv
1m hef1
mcef3 2 1m hef2
m cef4 2 Ed
T0 # # # # # # #
j Tj
# #
where mh is the mass flow rate of the hot stream and mc is the mass flow rate of the cold
stream. This can be rearranged to read
mh 1ef1 ef2 2 mc 1ef4 ef3 2

Ed
# # #
(7.44)
The term on the left of Eq. 7.44 accounts for the decrease in the exergy of the hot stream.
The first term on the right accounts for the increase in exergy of the cold stream. Regarding
the hot stream as supplying the exergy increase of the cold stream as well as the exergy de-
stroyed, we can write an exergetic heat exchanger efficiency as
mc 1ef4 ef3 2
#
e #
mh 1ef1 ef2 2
(7.45)
for example. . . the exergetic efficiency of the heat exchanger of Example 7.6 is 83.3%.
It is left as an exercise to verify this value.
DIRECT CONTACT HEAT EXCHANGER. The direct contact heat exchanger shown in
Fig. 7.11 operates at steady state with no heat transfer with its surroundings. The exergy rate
balance, Eq. 7.32a, reduces to
0 0
0 a a1 b Qj Wcv
m1ef1
m2ef2 m3ef3 Ed
T0 # # # # # #
j Tj
1 Hot stream, m 1
3 2
Mixed stream, m 3 Cold stream, m 2
Figure 7.11 Direct contact heat
exchanger.
# # #
With m3 m1
m2 from a mass rate balance, this can be written as
m1 1ef1 ef3 2 m2 1ef 3 ef 2 2
Ed
# # #
(7.46)
The term on the left Eq. 7.46 accounts for the decrease in the exergy of the hot stream
between inlet and exit. The first term on the right accounts for the increase in the exergy of
the cold stream between inlet and exit. Regarding the hot stream as supplying the exergy in-
crease of the cold stream as well as the exergy destroyed by irreversibilities, we can write
an exergetic efficiency for a direct contact heat exchanger as
m2 1ef3 ef2 2
#
e #
m1 1ef1 ef3 2
(7.47)
7.6.3 Using Exergetic Efficiencies

Exergetic efficiencies are useful for distinguishing means for utilizing energy resources that
are thermodynamically effective from those that are less so. Exergetic efficiencies also can
be used to evaluate the effectiveness of engineering measures taken to improve the per-
formance of a thermal system. This is done by comparing the efficiency values determined
before and after modifications have been made to show how much improvement has been
achieved. Moreover, exergetic efficiencies can be used to gauge the potential for improve-
ment in the performance of a given thermal system by comparing the efficiency of the sys-
tem to the efficiency of like systems. A significant difference between these values would
suggest that improved performance is possible.
It is important to recognize that the limit of 100% exergetic efficiency should not be re-
garded as a practical objective. This theoretical limit could be attained only if there were no
exergy destructions or losses. To achieve such idealized processes might require extremely
long times to execute processes and/or complex devices, both of which are at odds with the
objective of profitable operation. In practice, decisions are usually made on the basis of total
costs. An increase in efficiency to reduce fuel consumption, or otherwise utilize resources
better, normally requires additional expenditures for facilities and operations. Accordingly,
an improvement might not be implemented if an increase in total cost would result. The trade-
off between fuel savings and additional investment invariably dictates a lower efficiency than
might be achieved theoretically and may even result in a lower efficiency than could be
achieved using the best available technology.
Various methods are used to improve energy resource utilization. All such methods must
cogeneration achieve their objectives cost-effectively. One method is cogeneration, which sequentially pro-
duces power and a heat transfer (or process steam) for some desired use. An aim of cogen-
eration is to develop the power and heat transfer using an integrated system with a total ex-
penditure that is less than would be required to develop them individually. Further discussions
of cogeneration are provided in Secs. 7.7.2 and 8.5. Two other methods employed to improve
power recovery energy resource utilization are power recovery and waste heat recovery. Power recovery can
be accomplished by inserting a turbine into a pressurized gas or liquid stream to capture some
waste heat recovery
of the exergy that would otherwise be destroyed in a spontaneous expansion. Waste heat re-
covery contributes to overall efficiency by using some of the exergy that would otherwise be
discarded to the surroundings, as in the exhaust gases of large internal combustion engines.
An illustration of waste heat recovery is provided by Example 7.8.
7.7 Thermoeconomics 309

7.7 Thermoeconomics
Thermal systems typically experience significant work and/or heat interactions with their sur-
roundings, and they can exchange mass with their surroundings in the form of hot and cold
streams, including chemically reactive mixtures. Thermal systems appear in almost every in-
dustry, and numerous examples are found in our everyday lives. Their design involves the
application of principles from thermodynamics, fluid mechanics, and heat transfer, as well
as such fields as materials, manufacturing, and mechanical design. The design of thermal
systems also requires the explicit consideration of engineering economics, for cost is always
a consideration. The term thermoeconomics may be applied to this general area of applica- thermoeconomics
tion, although it is often applied more narrowly to methodologies combining exergy and
economics for optimizing the design and operation of thermal systems.
7.7.1 Using Exergy in Design

To illustrate the use of exergy in design, consider Fig. 7.12 showing a thermal system consist-
ing of a power-generating unit and a heat-recovery steam generator. The power-generating unit
develops an electric power output and combustion products that enter the heat recovery unit.
#
Feedwater also enters the heat-recovery steam generator with a mass flow rate of m w, receives
exergy by heat transfer from the combustion gases, and exits as steam at some desired condi-
tion for use in another process. The combustion products entering the heat-recovery steam gen-
erator can be regarded as having economic value. Since the source of the exergy of the com-
bustion products is the fuel input (Fig. 7.12), the economic value can be accounted for in terms
of the cost of fuel, as we have done in Sec. 7.6.1 when costing heat loss.
From our study of the second law of thermodynamics we know that the average temper-
ature difference, Tave, between two streams passing through a heat exchanger is a measure
of irreversibility and that the irreversibility of the heat transfer vanishes as the temperature
difference approaches zero. For the heat-recovery steam generator in Fig. 7.12, this source
of exergy destruction exacts an economic penalty in terms of fuel cost. Figure 7.13 shows
the annual fuel cost attributed to the irreversibility of the heat exchanger as a function of
Tave. The fuel cost increases with increasing Tave, because the irreversibility is directly
related to the temperature difference.
From the study of heat transfer, we know that there is an inverse relation between Tave
and the surface area required for a specified heat transfer rate. More heat transfer area means
a larger, more costly heat exchangerthat is, a greater capital cost. Figure 7.13 also shows
the annualized capital cost of the heat exchanger as a function of Tave. The capital cost
decreases as Tave increases.

We
Fuel
Heat-recovery
steam generator Combustion
Power-generating unit gases
Air
Steam Feedwater, m w
Figure 7.12 Figure used to illustrate the use of exergy in design.
Annualized cost, dollars per year

Total cost = Capital Cost + Fuel Cost
a a a
Capital cost
Fuel cost
0
0 Nearly
optimal
Average temperature difference, Tave
Figure 7.13 Cost curves for a single heat exchanger.
The total cost is the sum of the capital cost and the fuel cost. The total cost curve shown
in Fig. 7.13 exhibits a minimum at the point labeled a. Notice, however, that the curve is rel-
atively flat in the neighborhood of the minimum, so there is a range of Tave values that could
be considered nearly optimal from the standpoint of minimum total cost. If reducing the fuel
cost were deemed more important than minimizing the capital cost, we might choose a de-
sign that would operate at point a. Point a would be a more desirable operating point if
capital cost were of greater concern. Such trade-offs are common in design situations.
The actual design process can differ significantly from the simple case considered here.
For one thing, costs cannot be determined as precisely as implied by the curves in Fig. 7.13.
Fuel prices may vary widely over time, and equipment costs may be difficult to predict as
they often depend on a bidding procedure. Equipment is manufactured in discrete sizes, so
the cost also would not vary continuously as shown in the figure. Furthermore, thermal sys-
tems usually consist of several components that interact with one another. Optimization of
components individually, as considered for the heat exchanger, usually does not guarantee
an optimum for the overall system. Finally, the example involves only Tave as a design vari-
able. Often, several design variables must be considered and optimized simultaneously.
7.7.2 Exergy Costing of a Cogeneration System

Another important aspect of thermoeconomics is the use of exergy for allocating costs to the
products of a thermal system. This involves assigning to each product the total cost to pro-
duce it, namely the cost of fuel and other inputs plus the cost of owning and operating the
system (e.g., capital cost, operating and maintenance costs). Such costing is a common prob-
lem in plants where utilities such as electrical power, chilled water, compressed air, and steam
are generated in one department and used in others. The plant operator needs to know the
cost of generating each utility to ensure that the other departments are charged properly ac-
cording to the type and amount of each utility used. Common to all such considerations are
fundamentals from engineering economics, including procedures for annualizing costs, ap-
propriate means for allocating costs, and reliable cost data.
To explore further the costing of thermal systems, consider the simple cogeneration system
operating at steady state shown in Fig. 7.14. The system consists of a boiler and a turbine, with
each having no significant heat transfer to its surroundings. The figure is labeled with exergy

EfP
Combustion Turbine-electric
Boiler products generator
Fuel
High-pressure
EfF, cF
steam Zt We, ce
Air
Zb 1
Efa
Ef1, c1
2 Low-pressure steam
Feedwater Figure 7.14 Simple

Efw Ef2, c2 cogeneration system.
transfer rates associated with the flowing streams, where the subscripts F, a, P, and w denote
fuel, combustion air, combustion products, and feedwater, respectively. The subscripts 1 and 2
denote high- and low-pressure steam, respectively. Means for evaluating the exergies of the fuel
and combustion products are introduced # in Chap. 13. The cogeneration system has two prin-
cipal products: electricity, denoted by We, and low-pressure steam for use in some process. The
objective is to determine the cost at which each product is generated.
BOILER ANALYSIS. Let us begin by evaluating the cost of the high-pressure steam pro-
duced by the boiler. For this, we consider a control volume enclosing the boiler. Fuel and air
enter the boiler separately and combustion products exit. Feedwater enters and high-pressure
steam exits. The total cost to produce the exiting streams equals the total cost of the enter-
ing streams plus the cost of owning and operating the boiler. This is expressed by the following
cost rate balance for the boiler
# # # # # #
C1
CP CF
Ca
Cw
Zb (7.48) cost rate balance
# #
where C is the cost rate of the respective stream and Zb accounts for the cost rate associated
with owning and operating
# the boiler (each in $ per hour, for example). In the present dis-
cussion, the cost rate Zb is presumed known
# from a previous economic analysis.
Although the cost rates denoted by C in Eq. 7.48 are evaluated by various means in prac-
tice, the present discussion features the use of exergy for this purpose. Since exergy meas-
ures the true thermodynamic values of the work, heat, and other interactions between a sys-
tem and its surroundings as well as the effect of irreversibilities within the system, exergy is
a rational basis for assigning costs. With exergy costing, each of the cost rates is evaluated
in terms of the associated rate of exergy transfer and a unit cost. Thus, for an entering or ex-
iting stream, we write
# #
C cEf (7.49)
#
#
where c denotes the cost per unit of exergy (in cents per kW h, for example) and Ef is the exergy unit cost
associated exergy transfer rate.
For simplicity, we assume the feedwater and combustion air enter the boiler with negli-
gible exergy and cost, and the combustion products are discharged directly to the surround-
ings with negligible cost. Thus Eq. 7.48 reduces as follows
# # 0 # # 0 # 0 #
C1
CP CF
Ca
Cw
Zb
Then, with Eq. 7.49 we have
# # #
c1Ef1 cFEf F
Zb (7.50a)
Solving for c1, the unit cost of the high-pressure steam is

# #
c1 cF a # b
#
Ef F Zb
(7.50b)
Ef1 Ef1
This equation shows that the unit cost of the high-pressure steam is determined by two
contributions related, respectively, to the cost of the fuel and the cost of owning and operating
the boiler. Due to exergy destruction and loss,# less# exergy exits the boiler with the high-
pressure steam than enters with the fuel. Thus, Ef FEf1 is invariably greater than one, and the
unit cost of the high-pressure steam is invariably greater than the unit cost of the fuel.
TURBINE ANALYSIS. Next, consider a control volume enclosing the turbine. The total cost
to produce the electricity and low-pressure steam equals the cost of the entering high-pres-
sure steam plus the cost of owing and operating the device. This is expressed by the cost rate
balance for the turbine
# # # #
Ce
C2 C1
Zt (7.51)
# # #
where Ce is the cost rate associated with the electricity, C1 and
# C2 are the cost rates associ-
ated with the entering and exiting steam, respectively, and Zt accounts for the cost rate as-
sociated
# # with# owning and operating the turbine. With exergy costing, each of the cost rates
Ce, C1, and C2 is evaluated in terms of the associated rate of exergy transfer and a unit cost.
Equation 7.51 then appears as
# # # #
ceWe
c2Ef2 c1Ef1
Zt (7.52a)
The unit cost c1 in Eq. 7.52a is given by Eq. 7.50b. In the present discussion, the same
unit cost is assigned to the low-pressure steam; that is, c2 c1. This is done on the basis that
the purpose of the turbine is to generate electricity, and thus all costs associated with own-
ing and operating the turbine should be charged to the power generated. We can regard this
decision as a part of the cost accounting considerations that accompany the thermoeconomic
analysis of thermal systems. With c2 c1, Eq. 7.52a becomes
ceWe c1 1Ef1 Ef2 2
Zt
# # # #
(7.52b)
The first term on the right side accounts for the cost of the exergy used and the second term
accounts for the cost of the system itself.
Solving Eq. 7.52b for ce, and introducing the exergetic turbine efficiency e from Eq. 7.42
#
c1 Zt
ce
# (7.52c)
e We
This equation shows that the unit cost of the electricity is determined by the cost of the high-
pressure steam and the cost of owning and operating the turbine. Because of exergy de-
struction within the turbine, the exergetic efficiency is invariably less than one, and therefore
the unit cost of electricity is invariably greater than the unit cost of the high-pressure steam.
SUMMARY. By applying cost rate balances to the boiler and the turbine, we are able to de-
termine the cost of each product of the cogeneration system. The unit cost of the electricity
is determined by Eq. 7.52c and the unit cost of the low-pressure steam is determined by the
expression c2 c1 together with Eq. 7.50b. The example to follow provides a detailed
illustration. The same general approach is applicable for costing the products of a wide-
ranging class of thermal systems.1
1
See A. Bejan, G. Tsatsaronis, and M. J. Moran, Thermal Design and Optimization, John Wiley & Sons,
New York, 1996.
EXAMPLE 7.10 Exergy Costing of a Cogeneration System
A cogeneration system consists of a natural gas-fueled boiler and a steam turbine that develops power and provides steam for
an industrial process. At steady state, fuel enters the boiler with an exergy rate of 100 MW. Steam exits the boiler at 50 bar,
466C with an exergy rate of 35 MW. Steam exits the turbine at 5 bar, 205C and a mass flow rate of 26.15 kg/s. The unit
cost of the fuel is 1.44 cents per kW # h of exergy. The costs of owning and operating the boiler and turbine are, respectively,
$1080/h and $92/h. The feedwater and combustion air enter with negligible exergy and cost. The combustion products are dis-
charged directly to the surroundings with negligible cost. Heat transfer with the surroundings and kinetic and potential energy
effects are negligible. Let T0 298 K.
(a) For the turbine, determine the power and the rate exergy exits with the steam, each in MW.
(b) Determine the unit costs of the steam exiting the boiler, the steam exiting the turbine, and the power, each in cents per
kW # h of exergy.
(c) Determine the cost rates of the steam exiting the turbine and the power, each in $/h.
SOLUTION
Known: Steady-state operating data are known for a cogeneration system that produces both electricity and low-pressure
steam for an industrial process.
Find: For the turbine, determine the power and the rate exergy exits with the steam. Determine the unit costs of the steam
exiting the boiler, the steam exiting the turbine, and the power developed. Also determine the cost rates of the low-pressure
steam and power.
Turbine-electric
Combustion generator
Boiler products
Gaseous fuel

EfF = 100 MW
cents Zt = $92/h We, ce
cF = 1.44 _____ Zb = $1080/h 1
kWh
Ef1 = 35MW
Air p1 = 50 bar
T1 = 466C
p2 = 5 bar
Process steam 2 T2 = 205C
Feedwater m 2 = 26.15 kg/s
Figure E7.10
Assumptions:
1. Each control volume shown in the accompanying figure is at steady state.

#
2. For each control volume, Qcv 0 and kinetic and potential energy effects are negligible.
3. The feedwater and combustion air enter the boiler with negligible exergy and cost.
4. The combustion products are discharged directly to the surroundings with negligible cost.
5. For the environment, T0 298 K.
Analysis:
(a) With assumption 2, the mass and energy rate balances for a control volume enclosing the turbine reduce at steady state
to give
We m 1h1 h2 2
# #
From Table A-4, h1 3353.54 kJ/kg and h2 2865.96 kJ/kg. Thus
We a26.15 b 13353.54 2865.962 a b ` 3 `

# kg kJ 1 MW
s kg 10 kJ/s
12.75 MW
Using Eq. 7.36, the difference in the rates exergy enters and exits the turbine with the steam is
Ef2 Ef1 m 1ef2 ef1 2

# # #
m h2 h1 T0 1s2 s1 2
#
#
Solving for Ef2
Ef2 Ef1
m h2 h1 T0 1s2 s1 2
# # #
# #
With known values for Ef1 and m, and data from Table A-4: s1 6.8773 kJ/kg # K and s2 7.0806 kJ/kg # K, the rate exergy
exits with the steam is
Ef2 35 MW
a26.15 b c 12865.96 3353.542 298 K 17.0806 6.87732 # d ` 3 `
# kg kJ kJ 1 MW
s kg kg K 10 kJ/s
20.67 MW
(b) For a control volume enclosing the boiler, the cost rate balance reduces with assumptions 3 and 4 to give
# # #
c1Ef1 cFEfF
Zb
#
where
# EfF is the exergy rate of the entering fuel, cF and c1 are the unit costs of the fuel and exiting steam, respectively, and
Zb is the cost rate associated with the owning and operating the boiler. Solving for c1 and inserting known values
# #
c1 cF a # b
#
EfF Zb
Ef1 Ef1
a1.44 ba b
a b ` 3 ` ` `
cents 100 MW 1080 $/h 1 MW 100 cents
kW # h 35 MW 35 MW 10 kW 1$
14.11
3.092
cents cents
7.2
kW # h kW # h
The cost rate balance for the control volume enclosing the turbine is
# # # #
ceWe
c2Ef2 c1Ef1
Zt
#
where ce and c2 are the unit costs of the power and the exiting steam, respectively, and Zt is the cost rate associated with own-
ing and operating the turbine. Assigning the same unit cost to the steam entering and exiting the turbine, c2 c1
7.2 cents/kW # h, and solving for ce
# # #
Ef1 Ef2
ce c1 c d
#
Zt
#
We We
Inserting known values
135 20.672 MW
ce a7.2 bc d
a b` ` ` `
cents 92$/h 1 MW 100 cents
kW h# 12.75 MW 12.75 MW 103 kW 1$
18.09
0.722
cents cents
# 8.81
kW h kW # h
Key Engineering Concepts 315
(c) For the low-pressure steam and power, the cost rates are, respectively
# #
C2 c2Ef2
103 kW
a7.2 b 120.67 MW2 ` ` ` `
cents 1$
kW h# 1 MW 100 cents
$1488/h
# #
Ce ceWe
103 kW
a8.81 b 112.75 ` ` ` `
cents 1$
# MW2
kW h 1 MW 100 cents
$1123/h
The purpose of the turbine is to generate power, and thus all costs associated with owning and operating the turbine are
charged to the power generated.
Observe that the unit costs c1 and ce are significantly greater than the unit cost of the fuel.
Although the unit cost of the steam is less than the unit cost of the power, the steam cost rate is greater because the as-
sociated exergy rate is much greater.
In this chapter, we have introduced the property exergy and write out meanings of the terms listed in the margins
illustrated its use for thermodynamic analysis. Like mass, en- throughout the chapter and understand each of the
ergy, and entropy, exergy is an extensive property that can be related concepts. The subset of key concepts listed below
transferred across system boundaries. Exergy transfer ac- is particularly important.
companies heat transfer, work and mass flow. Like entropy, evaluate exergy at a given state using Eq. 7.2 and exergy
exergy is not conserved. Exergy is destroyed within systems change between two states using Eq. 7.10, each relative
whenever internal irreversibilities are present. Entropy pro- to a specified reference environment.
duction corresponds to exergy destruction.
apply exergy balances in each of several alternative
The use of exergy balances is featured in this chapter. Ex-
ergy balances are expressions of the second law that account forms, appropriately modeling the case at hand, correctly
for exergy in terms of exergy transfers and exergy destruc- observing sign conventions, and carefully applying SI
tion. For processes of closed systems, the exergy balance is and English units.
Eq. 7.11 and a corresponding rate form is Eq. 7.17. For con- evaluate the specific flow exergy relative to a specified
trol volumes, rate forms include Eq. 7.31 and the companion reference environment using Eq. 7.20.
steady-state expressions given by Eqs. 7.32. Control volume define and evaluate exergetic efficiencies for thermal
analyses account for exergy transfer at inlets and exits in terms system components of practical interest.
of flow exergy.
apply exergy costing to heat loss and simple cogenera-
The following checklist provides a study guide for this
tion systems.
chapter. When your study of the text and end-of-chapter ex-
ercises has been completed you should be able to
exergy p. 273 closed system exergy exergy destruction p. 284 exergetic

exergy reference balance p. 283 flow exergy p. 290 efficiency p. 303
environment p. 273 exergy transfer exergy rate
dead state p. 275 p. 284, 291 balance p. 285, 294
1. When you hear the term energy crisis used by the news me- 7. Can an energy transfer by heat and the associated exergy trans-
dia, do the media really mean exergy crisis? fer be in opposite directions? Repeat for work.
2. For each case illustrated in Fig. 5.1 (Sec. 5.1), identify the rel- 8. When evaluating exergy destruction, is it necessary to use an
evant intensive property difference between the system and its exergy balance?
surroundings that underlies the potential for work. For cases 9. For a stream of matter, how does the definition of flow exergy
(a) and (b) discuss whether work could be developed if the par- parallel the definition of enthalpy?
ticular intensive property value for the system were less than for
10. Is it possible for the flow exergy to be negative?
the surroundings.
11. Does the exergetic efficiency given by Eq. 7.45 apply when
3. Is it possible for exergy to be negative? For exergy change to
both the hot and cold streams are at temperatures below T0?
be negative?
12. A gasoline-fueled generator is claimed by its inventor to pro-
4. Does an airborne, helium-filled balloon at temperature T0 and
duce electricity at a lower unit cost than the unit cost of the fuel
pressure p0 have exergy?
used, where each cost is based on exergy. Comment.
5. Does a system consisting of an evacuated space of volume V
13. A convenience store sells gasoline and bottled drinking water
have exergy?
at nearly the same price per gallon. Comment.
6. When an automobile brakes to rest, what happens to the exergy
associated with its motion?
Evaluating Exergy (a) air as an ideal gas at 400C and 0.35 bar.
7.1 A system consists of 5 kg of water at 10C and 1 bar. De- (b) water vapor at 400C and 0.35 bar.
termine the exergy, in kJ, if the system is at rest and zero ele- Ignore the effects of motion and gravity and let T0 17C,
vation relative to an exergy reference environment for which p0 1 atm.
T0 20C, p0 1 bar.
7.8 Air as an ideal gas is stored in a closed vessel of volume V
7.2 Determine the exergy, in kJ, at 0.7 bar, 90C for 1 kg of
at temperature T0 and pressure p.
(a) water, (b) Refrigerant 134a, (c) air as an ideal gas with cp
constant. In each case, the mass is at rest and zero evaluation (a) Ignoring motion and gravity, obtain the following expres-
relative to an exergy reference environment for which sion for the exergy of the air:
T0 20C, p0 1 bar.
E p0V a1
ln b
p p p
7.3 Determine the specific exergy, in kJ/kg, at 0.01C of water
p0 p0 p0
as a (a) saturated vapor, (b) saturated liquid, (c) saturated solid.
In each case, consider a fixed mass at rest and zero elevation (b) Using the result of part (a), plot V, in m3, versus pp0 for
relative to an exergy reference environment for which T0 E 1 kW # h and p0 1 bar.
20C, p0 1 bar. (c) Discuss your plot in the limits as p p0 S , pp0 S 1, and
7.4 A balloon filled with helium at 20C, 1 bar and a volume p p0 S 0.
of 0.5 m3 is moving with a velocity of 15 m /s at an elevation 7.9 An ideal gas is stored in a closed vessel at pressure p and
of 0.5 km relative to an exergy reference environment for which temperature T.
T0 20C, p0 1 bar. Using the ideal gas model, determine
the specific exergy of the helium, in kJ. (a) If T T0, derive an expression for the specific exergy in
7.5 Determine the specific exergy, in kJ/kg, at 0.6 bar, 10C terms of p, p0, T0, and the gas constant R.
of (a) ammonia, (b) Refrigerant 22, (c) Refrigerant 134a. Let (b) If p p0, derive an expression for the specific exergy in
T0 0C, p0 1 bar and ignore the effects of motion and terms of T, T0, and the specific heat cp, which can be taken
gravity. as constant.
7.6 Consider a two-phase solidvapor mixture of water at Ignore the effects of motion and gravity.
10C. Each phase present has the same mass. Determine the 7.10 Equal molar amounts of carbon dioxide and helium are
specific exergy, in kJ/kg, if T0 20C, p0 1 atm, and there maintained at the same temperature and pressure. Which has the
are no significant effects of motion or gravity. greater value for exergy relative to the same reference environ-
7.7 Determine the exergy, in kJ, of the contents of a 2-m3 ment? Assume the ideal gas model with constant cv for each gas.
storage tank, if the tank is filled with There are no significant effects of motion and gravity.
7.11 Refrigerant 134a vapor initially at 1 bar and 20C fills a rigid Applying the Exergy Balance: Closed Systems
vessel. The vapor is cooled until the temperature becomes 32C. 7.15 One kilogram of water initially at 1.5 bar and 200C cools
There is no work during the process. For the refrigerant, deter- at constant pressure with no internal irreversibilities to a final
mine the heat transfer per unit mass and the change in specific state where the water is a saturated liquid. For the water as
exergy, each in kJ/kg. Comment. Let T0 20C, p0 0.1 MPa. the system, determine the work, the heat transfer, and the
7.12 As shown in Fig. P7.12, two kilograms of water undergo amounts of exergy transfer accompanying work and heat
a process from an initial state where the water is saturated vapor transfer, each in kJ. Let T0 20C, p0 1 bar.
at 120C, the velocity is 30 m /s, and the elevation is 6 m to a 7.16 One kilogram of air initially at 1 bar and 25C is heated
final state where the water is saturated liquid at 10C, the at constant pressure with no internal irreversibilities to a final
velocity is 25 m /s, and the elevation is 3 m. Determine in kJ, temperature of 177C. Employing the ideal gas model, deter-
(a) the exergy at the initial state, (b) the exergy at the final mine the work, the heat transfer, and the amounts of exergy
state, and (c) the change in exergy. Take T0 25C, p0 1 atm transfer accompanying work and heat transfer, each in kJ. Let
and g 9.8 m /s2. T0 298 K, p0 1 bar.
7.17 One kilogram of helium initially at 20C and 1 bar is con-
Saturated tained within a rigid, insulated tank. The helium is stirred by
vapor at 120C a paddle wheel until its pressure is 1.45 bar. Employing the
1
ideal gas model, determine the work and the exergy destruc-
30 m/s tion for the helium, each in kJ. Neglect kinetic and potential
energy and let T0 20C, p0 1 bar.
7.18 A rigid, well-insulated tank consists of two compartments,
each having the same volume, separated by a valve. Initially,
Saturated one of the compartments is evacuated and the other contains
liquid at 10C 0.25 kmol of nitrogen gas at 0.35 MPa and 38C. The valve
2
6m 25 m/s is opened and the gas expands to fill the total volume, even-
tually achieving an equilibrium state. Using the ideal gas model
for the nitrogen
3m (a) determine the final temperature, in C, and final pressure,

z p0 = 1 atm, in MPa.
T0 = 25C, (b) evaluate the exergy destruction, in kJ.
g = 9.8 m/s2 (c) What is the cause of exergy destruction in this case?
Let T0 21C, p0 1 bar.
Figure P7.12 7.19 One kilogram of Refrigerant 134a is compressed adiabat-
ically from the saturated vapor state at 10C to a final state
where the pressure is 8 bar and the temperature is 50C. De-
7.13 Consider 1 kg of steam initially at 20 bar and 240C as termine the work and the exergy destruction, each in kJ/kg. Let
the system. Determine the change in exergy, in kJ, for each of T0 20C, p0 1 bar.
the following processes: 7.20 Two solid blocks, each having mass m and specific heat
(a) The system is heated at constant pressure until its volume c, and initially at temperatures T1 and T2, respectively, are
doubles. brought into contact, insulated on their outer surfaces, and
(b) The system expands isothermally until its volume allowed to come into thermal equilibrium.
doubles. (a) Derive an expression for the exergy destruction in terms
Let T0 20C, p0 1 bar. of m, c, T1, T2, and the temperature of the environment, T0.
7.14 A flywheel with a moment of inertia of 6.74 kg # m2 (b) Demonstrate that the exergy destruction cannot be
rotates as 3000 RPM. As the flywheel is braked to rest, its negative.
rotational kinetic energy is converted entirely to internal (c) What is the cause of exergy destruction in this case?
energy of the brake lining. The brake lining has a mass of 7.21 As shown in Fig. P7.21, a 0.3 kg metal bar initially at
2.27 kg and can be regarded as an incompressible solid with 1200 K is removed from an oven and quenched by immers-
a specific heat c 4.19 kJ/kg # K. There is no significant heat ing it in a closed tank containing 9 kg of water initially at
transfer with the surroundings. (a) Determine the final tem- 300 K. Each substance can be modeled as incompressible.
perature of the brake lining, in C, if its initial temperature is An appropriate constant specific heat for the water is cw
16C. (b) Determine the maximum possible rotational speed, 4.2 kJ/kg # K, and an appropriate value for the metal is
in RPM, that could be attained by the flywheel using energy cm .42 kJ/kg # K. Heat transfer from the tank contents can
stored in the brake lining after the flywheel has been braked be neglected. Determine the exergy destruction, in kJ. Let
to rest. Let T0 16C. T0 25C.
System boundary For each device, evaluate, in kW, the rates of exergy transfer
accompanying heat and work, and the rate of exergy destruc-
tion. Can either device operate as claimed? Let T0 27C.
7.25 For the silicon chip of Example 2.5, determine the rate of
exergy destruction, in kW. What causes exergy destruction in
this case? Let T0 293 K.
7.26 Two kilograms of a two-phase liquidvapor mixture of
water initially at 300C and x1 0.5 undergo the two differ-
ent processes described below. In each case, the mixture is
Metal bar: Water: brought from the initial state to a saturated vapor state, while
Tmi = 1200 K Twi = 300 K
cm = 0.42 kJ/kgK cw = 4.2 kJ/kgK the volume remains constant. For each process, determine the
mm = 0.3 kg mw = 9 kg change in exergy of the water, the net amounts of exergy trans-
fer by work and heat, and the amount of exergy destruction,
Figure P7.21
each in kJ. Let T0 300 K, p0 1 bar, and ignore the effects
of motion and gravity. Comment on the difference between the
7.22 As shown in Fig. P7.22, heat transfer equal to 5 kJ exergy destruction values.
takes place through the inner surface of a wall. Measurements (a) The process is brought about adiabatically by stirring the
made during steady-state operation reveal temperatures of mixture with a paddle wheel.
T1 1500 K and T2 600 K at the inner and outer surfaces, (b) The process is brought about by heat transfer from a ther-
respectively. Determine, in kJ mal reservoir at 900 K. The temperature of the water at
(a) the rates of exergy transfer accompanying heat at the in- the location where the heat transfer occurs is 900 K.
ner and outer surfaces of the wall. 7.27 For the water heater of Problem 6.48, determine the ex-
(b) the rate of exergy destruction. ergy transfer and exergy destruction, each in kJ, for
(c) What is the cause of exergy destruction in this case?
(a) the water as the system.
Let T0 300 K. (b) the overall water heater including the resistor as the system.
Compare the results of parts (a) and (b), and discuss. Let
T0 20C, p0 1 bar.
7.28 For the electric motor of Problem 6.50, evaluate the rate
of exergy destruction and the rate of exergy transfer accompa-
nying heat, each in kW. Express each quantity as a percentage
of the electrical power supplied to the motor. Let T0 293 K.
7.29 A thermal reservoir at 1200 K is separated from another
Q1 = K kJ Q2
thermal reservoir at 300 K by a cylindrical rod insulated on its
lateral surfaces. At steady state, energy transfer by conduction
takes place through the rod. The rod diameter is 2 cm, the
T1 = 1500 K T2 = 600 K length is L, and the thermal conductivity is 0.4 kW/m # K. Plot
the following quantities, each in kW, versus L ranging from
Figure P7.22 0.01 to 1 m: the rate of conduction through the rod, the rates
of exergy transfer accompanying heat transfer into and out of
the rod, and the rate of exergy destruction. Let T0 300 K.
7.23 For the gearbox of Example 6.4(b), develop a full exergy
7.30 A system undergoes a refrigeration cycle while receiving
accounting of the power input. Compare with the results of
QC by heat transfer at temperature TC and discharging energy
Example 7.4 and discuss. Let T0 293 K.
QH by heat transfer at a higher temperature TH. There are no
7.24 The following steady-state data are claimed for two other heat transfers.
devices:
(a) Using an exergy balance, show that the net work input to
Device 1. Heat transfer to the device occurs at a place on its the cycle cannot be zero.
surface where the temperature is 52C. The device delivers (b) Show that the coefficient of performance of the cycle can
electricity to its surroundings at the rate of 10 kW. There are be expressed as
no other energy transfers.
ba b a1 b
TC THEd
T0 1QH QC 2
Device 2. Electricity is supplied to the device at the rate of
TH TC
10 kW. Heat transfer from the device occurs at a place on
its surface where the temperature is 52C. There are no other where Ed is the exergy destruction and T0 is the tempera-
energy transfers. ture of the exergy reference environment.
(c) Using the result of part (b), obtain an expression for the 7.37 Water vapor enters a valve with a mass flow rate of
maximum theoretical value for the coefficient of 2.7 kg/s at a temperature of 280C and a pressure of 30 bar
performance. and undergoes a throttling process to 20 bar.
(a) Determine the flow exergy rates at the valve inlet and exit
Applying the Exergy Balance: Control Volumes and the rate of exergy destruction, each in kW.
(b) Evaluating exergy at 8 cents per kW h, determine the
7.31 The following conditions represent the state at the inlet to
annual cost associated with the exergy destruction, as-
a control volume. In each case, evaluate the specific exergy
suming 7500 hours of operation annually.
and the specific flow exergy, each in kJ/kg. The velocity is rel-
ative to an exergy reference environment for which T0 20C, Let T0 25C, p0 1 atm.
p0 1 bar. The effect of gravity can be neglected. 7.38 Steam enters a turbine operating at steady state at 6 MPa,
(a) water vapor at 100 bar, 520C, 100 m/s. 500C with a mass flow rate of 400 kg/s. Saturated vapor exits
(b) Ammonia at 3 bar, 0C, 5 m /s. at 8 kPa. Heat transfer from the turbine to its surroundings takes
(c) nitrogen (N2) as an ideal gas at 50 bar, 527C, 200 m/s. place at a rate of 8 MW at an average surface temperature of
180C. Kinetic and potential energy effects are negligible.
7.32 For an ideal gas with constant specific heat ratio k, show
that in the absence of significant effects of motion and grav- (a) For a control volume enclosing the turbine, determine the
ity the specific flow exergy can be expressed as power developed and the rate of exergy destruction, each
in MW.
p 1k12k
1 ln
ln a b
ef T T (b) If the turbine is located in a facility where the ambient

cpT0 T0 T0 p0 temperature is 27C, determine the rate of exergy de-
(a) For k 1.2 develop plots of efcpT0 versus TT0 for struction for an enlarged control volume that includes the
pp0 0.25, 0.5, 1, 2, 4. Repeat for k 1.3 and 1.4. turbine and its immediate surroundings so the heat trans-
(b) The specific flow exergy can take on negative values when fer takes place from the control volume at the ambient tem-
pp0 1. What does a negative value mean physically? perature. Explain why the exergy destruction values of
parts (a) and (b) differ.
7.33 A geothermal source provides a stream of liquid water at Let T0 300 K, p0 100 kPa.
temperature T ( T0) and pressure p. Using the incompress-
ible liquid model, develop a plot of efcT0, where ef is the spe- 7.39 Air at 1 bar, 17C, and a mass flow rate of 0.3 kg/s enters
cific flow exergy and c is the specific heat, versus TT0 for an insulated compressor operating at steady state and exits at
pp0 1.0, 1.5, and 2.0. Neglect the effects of motion and 3 bar, 147C. Determine, the power required by the compres-
gravity. Let T0 60F, p0 1 atm. sor and the rate of exergy destruction, each in kW. Express the
rate of exergy destruction as a percentage of the power required
7.34 The state of a flowing gas is defined by h, s, V, and z, by the compressor. Kinetic and potential energy effects are neg-
where velocity and elevation are relative to an exergy refer- ligible. Let T0 17C, p0 1 bar.
ence environment for which the temperature is T0 and the pres-
7.40 Refrigerant 134a at 10C, 1.4 bar, and a mass flow rate
sure is p0. Determine the maximum theoretical work, per unit
of 280 kg/h enters an insulated compressor operating at steady
mass of gas flowing, that could be developed by any one-inlet,
state and exits at 9 bar. The isentropic compressor efficiency
one-exit control volume at steady state that would reduce the
is 82%. Determine
stream to the dead state at the exit while allowing heat transfer
only at T0. Using your final expression, interpret the specific (a) the temperature of the refrigerant exiting the compressor,
flow exergy. in C.
(b) the power input to the compressor, in kW.
7.35 Steam exits a turbine with a mass flow rate of 2 105
(c) the rate of exergy destruction expressed as a percentage of
kg/h at a pressure of 0.008 MPa, a quality of 94%, and a ve-
the power required by the compressor.
locity of 70 m /s. Determine the maximum theoretical power
that could be developed, in MW, by any one-inlet, one-exit Neglect kinetic and potential energy effects and let T0 20C,
control volume at steady state that would reduce the steam to p0 1 bar.
the dead state at the exit while allowing heat transfer only at 7.41 Water vapor at 4.0 MPa and 400C enters an insulated tur-
temperature T0. The velocity is relative to an exergy reference bine operating at steady state and expands to saturated vapor at
environment for which T0 15C, p0 0.1 MPa. Neglect the 0.1 MPa. Kinetic and potential energy effects can be neglected.
effect of gravity.
(a) Determine the work developed and the exergy destruction,
7.36 Water at 25C, 1 bar is drawn from a mountain lake 1 km each in kJ per kg of water vapor passing through the turbine.
above a valley and allowed to flow through a hydraulic (b) Determine the maximum theoretical work per unit of mass
turbine-generator to a pond on the valley floor. For operation flowing, in kJ/kg, that could be developed by any one-
at steady state, determine the minimum theoretical mass flow inlet, one-exit control volume at steady state that has wa-
rate, in kg /s, required to generate electricity at a rate of 1 MW. ter vapor entering and exiting at the specified states, while
Let T0 25C, p0 1 bar. allowing heat transfer only at temperature T0.
Compare the results of parts (a) and (b) and comment. Let 7.48 Saturated water vapor at 0.008 MPa and a mass flow rate
T0 27C, p0 0.1 MPa. of 2.6 105 kg/h enters the condenser of a 100-MW power
7.42 Air enters an insulated turbine operating at steady state at plant and exits as a saturated liquid at 0.008 MPa. The cool-
8 bar, 500 K, and 150 m/s. At the exit the conditions are 1 bar, ing water stream enters at 15C and exits at 35C with a neg-
320 K, and 10 m/s. There is no significant change in eleva- ligible change in pressure. At steady state, determine
tion. Determine (a) the net rate energy exits the plant with the cooling water
stream, in MW.
(a) the work developed and the exergy destruction, each in kJ
(b) the net rate exergy exits the plant with the cooling water
per kg of air flowing.
stream, in MW.
(b) the maximum theoretical work, in kJ per kg of air flow-
ing, that could be developed by any one-inlet, one-exit con- Compare these values. Is the loss with the cooling water sig-
trol volume at steady state that has air entering and exit- nificant? What are some possible uses for the exiting cooling
ing at the specified states, while allowing heat transfer only water? Let T0 20C, p0 0.1 MPa.
at temperature T0. 7.49 Air enters a counterflow heat exchanger operating at
Compare the results of parts (a) and (b) and comment. Let steady state at 22C, 0.1 MPa and exits at 7C. Refrigerant
T0 300 K, p0 1 bar. 134a enters at 0.2 MPa, a quality of 0.2, and a mass flow rate
7.43 For the compressor of Problem 6.84, determine the rate of 30 kg/h. Refrigerant exits at 0C. There is no significant
of exergy destruction and the rate of exergy transfer accom- change in pressure for either stream.
panying heat, each in kJ per kg of air flow. Express each as a (a) For the Refrigerant 134a stream, determine the rate of heat
percentage of the work input to the compressor. Let T0 20C, transfer, in kJ/h.
p0 1 atm. (b) For each of the streams, evaluate the change in flow exergy
rate, in kJ/h. Compare the values.
7.44 A compressor fitted with a water jacket and operating at
steady state takes in air with a volumetric flow rate of 900 m3/h Let T0 22C, p0 0.1 MPa, and ignore the effects of motion
at 22C, 0.95 bar and discharges air at 317C, 8 bar. Cooling and gravity.
water enters the water jacket at 20C, 100 kPa with a mass 7.50 Determine the rate of exergy destruction, in kW, for
flow rate of 1400 kg/h and exits at 30C and essentially the (a) the computer of Example 4.8, when air exits at 32C.
same pressure. There is no significant heat transfer from the (b) the computer of Problem 4.70, ignoring the change in pres-
outer surface of the water jacket to its surroundings, and ki- sure between the inlet and exit.
netic and potential energy effects can be ignored. For the water- (c) the water-jacketed electronics housing of Problem 4.71,
jacketed compressor, perform a full exergy accounting of the when water exits at 24C.
power input. Let T0 20C, p0 1 atm. Let T0 293 K, p0 1 bar.
7.45 Steam at 1.4 MPa and 350C with a mass flow rate of 7.51 Determine the rate of exergy destruction, in kW, for the
0.125 kg/s enters an insulated turbine operating at steady state electronics-laden cylinder of Problems 4.73 and 6.108. Let
and exhausts at 100 kPa. Plot the temperature of the exhaust T0 293 K, p0 1 bar.
steam, in C, the power developed by the turbine, in kW, and 7.52 Helium gas enters an insulated nozzle operating at steady
the rate of exergy destruction within the turbine, in kW, each state at 1300 K, 4 bar, and 10 m/s. At the exit, the temperature
versus the isentropic turbine efficiency ranging from 0 to and pressure of the helium are 900 K and 1.45 bar, respec-
100%. Neglect kinetic and potential energy effects. Let T0 tively. Determine
20C, p0 0.1 MPa.
(a) the exit velocity, in m /s.
7.46 If the power-recovery device of Problem 6.102 develops (b) the isentropic nozzle efficiency.
a net power of 6 kW, determine, in kW (c) the rate of exergy destruction, in kJ per kg of gas flowing
(a) the rate exergy enters accompanying heat transfer. through the nozzle.
(b) the net rate exergy is carried in by the steam. Assume the ideal gas model for helium and ignore the effects
(c) the rate of exergy destruction within the device. of gravity. Let T0 20C, p0 1 atm.
Let T0 293 K, p0 1 bar. 7.53 As shown schematically in Fig. P7.53, an open feedwater
7.47 A counterflow heat exchanger operating at steady state has heater in a vapor power plant operates at steady state with liq-
ammonia entering at 60C, 14 bar with a mass flow rate of uid entering at inlet 1 with T1 40C and p1 7.0 bar. Water
0.5 kg/s and exiting as saturated liquid at 14 bar. Air enters in vapor at T2 200C and p2 7.0 bar enters at inlet 2. Saturated
a separate stream at 300 K, 1 bar and exits at 335 K with a liquid water exits with a pressure of p3 7.0 bar. Ignoring
negligible change in pressure. Heat transfer between the heat heat transfer with the surroundings and all kinetic and potential
exchanger and its surroundings is negligible as are changes in energy effects, determine
kinetic and potential energy. Determine (a) the ratio of mass flow rates, m1m2.
# #
(a) the change in the flow exergy rate of each stream, in kW. (b) the rate of exergy destruction, in kJ per kg of liquid
(b) the rate of exergy destruction in the heat exchanger, in kW. exiting.
Let T0 300 K, p0 1 bar. Let T0 25C, p0 1 atm.
7.60 For the compressor and heat exchanger of Problem 6.88,

develop a full exergy accounting, in kW, of the compressor
Liquid water 1 Water vapor power input. Let T0 300 K, p0 96 kPa.
40C, 7 bar 2 200C, 7 bar
Using Exergetic Efficiencies
3 7.61 Plot the exergetic efficiency given by Eq. 7.39b versus

TuT0 for TsT0 8.0 and 0.4, 0.6, 0.8, 1.0. What can be
Saturated liquid learned from the plot when TuT0 is fixed? When e is fixed?
7 bar
Discuss.
Figure P7.53
7.62 The temperature of water contained in a closed, well-
insulated tank is increased from 15 to 50C by passing an
7.54 Reconsider the open feedwater heater of Problem 6.87a. electric current through a resistor within the tank. Devise and
For an exiting mass flow rate of 1 kg/s, determine the cost of evaluate an exergetic efficiency for this water heater. Assume
the exergy destroyed for 8000 hours of operation annually. that the water is incompressible and the states of the resistor
Evaluate exergy at 8 cents per kW h. Let T0 20C, p0 and the enclosing tank do not change. Let T0 15C.
1 atm. 7.63 Measurements during steady-state operation indicate that
7.55 Steam at 3 MPa and 700C is available at one location warm air exits a hand-held hair dryer at a temperature of 83C
in an industrial plant. At another location, steam at 2 MPa, with a velocity of 9.1 m/s through an area of 18.7 cm2. As
400C, and a mass flow rate of 1 kg/s is required for use in shown in Fig. P7.63, air enters the dryer at a temperature of
a certain process. An engineer suggests that steam at this 22C and a pressure of 1 bar with a velocity of 3.7 m/s. No
condition can be provided by allowing the higher-pressure significant change in pressure between inlet and exit is ob-
steam to expand through a valve to 2 MPa and then flow served. Also, no significant heat transfer between the dryer and
through a heat exchanger where the steam cools at constant its surroundings occurs, and potential energy effects can be ig-
pressure to 400C by heat transfer to the surroundings, which nored.
# Let T0 22C. For the hair dryer (a) evaluate the power
are at 20C. Wcv, in kW, and (b) devise and evaluate an exergetic efficiency.
(a) Determine the total rate of exergy destruction, in kW, that
would result from the implementation of this suggestion.
(b) Evaluating exergy at 8 cents per kW # h, determine the 2 T2 = 83C
Air p2 = 1 bar
annual cost of the exergy destruction determined in part V2 = 9.1 m/s
T1 = 22C 1
(a) for 8000 hours of operation annually. p1 = 1 bar A2 = 18.7 cm2
Would you endorse this suggestion? Let T0 20C, p0 V1 = 3.7 m/s
0.1 MPa.
7.56 For the compressor and turbine of Problem 6.110, deter-
mine the rates of exergy destruction, each in kJ per kg of
air flowing. Express each as a percentage of the net work de-
veloped by the power plant. Let T0 22C, p0 0.95 bar.
+
7.57 For the turbines and heat exchanger of Problem 4.57, de-
termine the rates of exergy destruction, each in kW. Place in Figure P7.63
rank order, beginning with the component contributing most
to inefficient operation of the overall system. Let T0 300 K,
p0 1 bar. 7.64 From an input of electricity, an electric resistance furnace
7.58 For the turbine, condenser, and pump of Problem 4.59, de- operating at steady state
# delivers energy by heat transfer to a
termine the rates of exergy destruction, each in kW. Place in process at the rate Qu at a use temperature Tu. There are no
rank order, beginning with the component contributing most other significant energy transfers.
to inefficient operation of the overall system. Let T0 293 K, (a) Devise an exergetic efficiency for the furnace.
p0 1 bar. (b) Plot the efficiency obtained in part (a) versus the use tem-
7.59 If the gas turbine power plant of Problem 6.74 develops perature ranging from 300 to 900 K. Let T0 20C.
a net power output of 0.7 MW, determine, in MW, 7.65 Hydrogen at 25 bar, 450C enters a turbine and expands
(a) the rate of exergy transfer accompanying heat transfer to to 2 bar, 160C with a mass flow rate of 0.2 kg/s. The turbine
the air flowing through the heat exchanger. operates at steady state with negligible heat transfer with its
(b) the net rate exergy is carried out by the air stream. surroundings. Assuming the ideal gas model with k 1.37 and
(c) the total rate of exergy destruction within the power plant. neglecting kinetic and potential energies, determine
Let T0 295 K (22C), p0 0.95 bar. (a) the isentropic turbine efficiency.
(b) the exergetic turbine efficiency. 7.71 Liquid water at 95C, 1 bar enters a direct-contact heat ex-
Let T0 25C, p0 1 atm. changer operating at steady state and mixes with a stream of
liquid water entering at 15C, 1 bar. A single liquid stream ex-
7.66 An ideal gas with constant specific heat ratio k enters a its at 1 bar. The entering streams have equal mass flow rates.
turbine operating at steady state at T1 and p1 and expands adi- Neglecting heat transfer with the surroundings and kinetic and
abatically to T2 and p2. When would the value of the exergetic potential energy effects, determine for the heat exchanger
turbine efficiency exceed the value of the isentropic turbine ef-
ficiency? Discuss. Ignore the effects of motion and gravity. (a) the rate of exergy destruction, in kJ per kg of liquid
exiting.
7.67 Air enters an insulated turbine operating at steady state
(b) the exergetic efficiency given by Eq. 7.47.
with a pressure of 4 bar, a temperature of 450 K, and a volu-
metric flow rate of 5 m3/s. At the exit, the pressure is 1 bar. Let T0 15C, p0 1 bar.
The isentropic turbine efficiency is 84%. Ignoring the effects 7.72 Refrigerant 134a enters a counterflow heat exchanger op-
of motion and gravity, determine erating at steady state at 20C and a quality of 35% and ex-
(a) the power developed and the exergy destruction rate, each its as saturated vapor at 20C. Air enters as a separate stream
in kW. with a mass flow rate of 4 kg/s and is cooled at a constant pres-
(b) the exergetic turbine efficiency. sure of 1 bar from 300 to 260 K. Heat transfer between the
Let T0 20C, p0 1 bar. heat exchanger and its surroundings can be ignored, as can all
changes in kinetic and potential energy.
7.68 Argon enters an insulated turbine operating at steady state
at 1000C and 2 MPa and exhausts at 350 kPa. The mass flow (a) As in Fig. E7.6, sketch the variation with position of the
rate is 0.5 kg/s. Plot each of the following versus the turbine temperature of each stream. Locate T0 on the sketch.
exit temperature, in C (b) Determine the rate of exergy destruction within the heat
exchanger, in kW.
(a) the power developed, in kW. (c) Devise and evaluate an exergetic efficiency for the heat
(b) the rate of exergy destruction in the turbine, in kW. exchanger.
(c) the exergetic turbine efficiency.
Let T0 300 K, p0 1 bar.
Neglect kinetic and potential energy effects. Let T0 20C,
p0 1 bar. 7.73 Determine the exergetic efficiencies of the turbines and
heat exchanger of Problem 4.57. Let T0 300 K, p0 1 bar.
7.69 A compressor operating at steady state takes in 1980 kg/h
of air at 1 bar and 25C and compresses it to 10 bar and 200C. 7.74 Determine the exergetic efficiencies of the compressor and
The power input to the compressor is 160 kW, and heat trans- condenser of the heat pump system of Examples 6.8 and 6.14.
fer occurs from the compressor to the surroundings at an Let T0 273 K, p0 1 bar.
average surface temperature of 60C.
7.75 Determine the exergetic efficiencies of the compressor
(a) Perform a full exergy accounting of the power input to the and heat exchanger of Problem 6.88. Let T0 300 K, p0
compressor. 96 kPa.
(b) Devise and evaluate an exergetic efficiency for the
compressor. 7.76 Determine the exergetic efficiencies of the steam genera-
(c) Evaluating exergy at 8 cents per kW h, determine the tor and turbine of Examples 4.10 and 7.8. Let T0 298C, p0
hourly costs of the power input, exergy loss associated with 1 atm.
heat transfer, and exergy destruction.
Neglect kinetic and potential energy changes. Let T0 25C, Considering Thermoeconomics
p0 1 bar. 7.77 The total cost rate for a device varies with the pressure
7.70 In the boiler of a power plant are tubes through which wa- drop for flow through the device, ( p1 p2), as follows:
C c1 1 p1 p2 2 13
c2 1 p1 p2 2
#
ter flows as it is brought from 0.8 MPa, 150C to 240C at es-
sentially constant pressure. The total mass flow rate of the wa-
ter is 100 kg/s. Combustion gases passing over the tubes cool where the cs are constants incorporating economic factors.
from 1067 to 547C at essentially constant pressure. The com- The first term on the right side of this equation accounts for
bustion gases can be modeled as air as an ideal gas. There is the capital cost and the second term on the right accounts for
no significant heat transfer from the boiler to its surroundings. the operating cost (pumping power).
#
Assuming steady state and neglecting kinetic and potential en- (a) Sketch a plot of C versus ( p1 p2).
ergy effects, determine (b) At the point of minimum total cost rate, evaluate the con-
(a) the mass flow rate of the combustion gases, in kg/s. tributions of the capital and operating cost rates to the total
(b) the rate of exergy destruction, in kJ/s. cost rate, each in percent. Discuss.
(c) the exergetic efficiency given by Eq. 7.45. 7.78 A system # operating at steady state generates# electricity
#
Let T0 25C, p0 1 atm. at the rate We. The cost rate of the fuel input is CF cFEfF,
where cF is the unit cost of fuel based on exergy. The cost of 7.81 A cogeneration system operating at steady state is shown
owning and operating the system is schematically in Fig. P7.81. The exergy transfer rates of the
entering and exiting streams are shown on the figure, in MW.
Z ca b We
# e #
The fuel, produced by reacting coal with steam, has a unit
1e cost of 5.85 cents per kW # h of exergy. The cost of owning
# #
# WeEfF# , and c is a constant incorporating economic
where e and operating the system is $1800/h. The feedwater and com-
factors. CF and Z are the only significant cost rates for the bustion air enter with negligible exergy and cost. The com-
system. bustion products are discharged directly to the surroundings
with negligible cost. Heat transfer with the surroundings can
(a) Derive an expression
# for the unit cost of electricity, ce, be ignored.
based on We in terms of e and the ratios cecF and ccF
only. (a) Determine the rate of exergy destruction within the
(b) For fixed ccF, derive an expression for the value of e cor- cogeneration system, in MW.
responding to the minimum value of cecF. (b) Devise and evaluate an exergetic efficiency for the system.
(c) Plot the ratio cecF versus e for ccF 0.25, 1.0, and 4.0. (c) Assuming the power and steam each have the same unit
For each specified ccF, evaluate the minimum value of cost based on exergy, evaluate the unit cost, in cents per
cecF and the corresponding value of e. kW # h. Also evaluate the cost rates of the power and steam,
each in $/h.
7.79 At steady state, a turbine with an exergetic efficiency of
85% develops 18 107 kW h of work annually (8000 oper-
ating hours). The annual cost of owning and operating the
turbine is $5.0 105. The steam entering the turbine has a
Combustion products
specific flow exergy of 645 Btu/lb, a mass flow rate of 32
EfP = 5 MW
104 lb/h, and is valued at $0.0182 per kW h of exergy. Cogeneration system
2 Steam

(a) Evaluate the unit cost of the power developed, in $ per Ef2 = 15 MW
kW # h. 1 Fuel
Z = $1800/h
(b) Evaluate the unit cost based on exergy of the steam en- EfF = 80 MW Power

cF = 5.85 cents per kWh We = 25 MW
tering and exiting the turbine, each in cents per lb of steam 3
flowing through the turbine.
Combustion Feedwater
7.80 Figure P7.80 shows a boiler at steady state. Steam hav- air
ing a specific flow exergy of 1300 kJ/kg exits the boiler at a Figure P7.81
mass flow rate of 5.69 104 kg/h. The cost of owning and
operating the boiler is $91/h. The ratio of the exiting steam
exergy to the entering fuel exergy is 0.45. The unit cost of
the fuel based on exergy is $1.50 per 106 kJ. If the cost rates 7.82 Consider an overall control volume comprising the boiler
of the combustion air, feedwater, heat transfer with the and steam turbine of the cogeneration system of Example 7.10.
surroundings, and exiting combustion products are ignored, Assuming the power and process steam each have the same
develop unit cost based on exergy: ce c2, evaluate the unit cost, in
(a) an expression for the unit cost based on exergy of the steam cents per kW # h. Compare with the respective values obtained
exiting the boiler. in Example 7.10 and comment.
(b) Using the result of part (a), determine the unit cost of the
7.83 The table below gives alternative specifications for the
steam, in cents per kg of steam flowing.
state of the process steam exiting the turbine of Example 7.10.
The cost of owning# and operating the turbine,
# in# $/h, varies
with the power We, in MW, according to Zt 7.2We. All other
data remain unchanged.
p2 1bar2
Combustion
Boiler products 40 30 20 9 5 2 1
T21C2
Fuel
436 398 349 262 205 128 sat
cF = $1.50 per 106 kJ Zb = $91/h Steam
ef = 1300 kJ/kg
m = 5.69 104 kg/h Plot versus p2, in bar
#
Air (a) the power We, in MW.
(b) the unit costs of the power and process steam, each in cents
per kW # h of exergy.
Feedwater (c) the unit cost of the process steam, in cents per kg of steam
Figure P7.80 flowing.
7.1D A utility charges households the same per kW h for space discharges exergy by heat transfer to the natural environment.
heating via steam radiators as it does for electricity. Critically Discuss practical difficulties that require actual power plant op-
evaluate this costing practice and prepare a memorandum sum- eration to depart from your theoretical cycle.
marizing your principal conclusions. 7.6D Define and evaluate an exergetic efficiency for an electric
7.2D For what range of steam mass flow rates, in kg/s, would heat pump system for a 2500 ft2 dwelling in your locale. Use
it be economically feasible to replace the throttling valve of manufacturers data for heat pump operation.
Example 7.5 with a power recovery device? Provide support- 7.7D Using the key words exergetic efficiency, second law
ing calculations. What type of device might you specify? efficiency, and rational efficiency, develop a bibliography of
Discuss. recent publications discussing the definition and use of such
7.3D A vortex tube is a device having no moving mechanical efficiencies for power systems and their components. Write a
parts that converts an inlet stream of compressed air at an in- critical review of one of the publications you locate. Clearly
termediate temperature into two exiting streams, one cold and state the principal contribution(s) of the publication.
one hot. 7.8D The initial plans for a new factory space specify 1000 flu-
(a) A product catalogue indicates that 20% of the air entering orescent light fixtures, each with two 8-ft conventional tubes
a vortex tube at 21C and 5 bar exits at 37C and 1 bar sharing a single magnetic ballast. The lights will operate from
while the rest exits at 34.2C and 1 bar. An inventor pro- 7 AM to 10 PM, 5 days per week, 350 days per year. More ex-
poses operating a power cycle between the hot and cold pensive high-efficiency tubes are available that require more
streams. Critically evaluate the feasibility of this proposal. costly electronic ballasts but use considerably less electricity
(b) Obtain a product catalogue from a vortex tube vendor lo- to operate. Considering both initial and operating costs, deter-
cated with the help of the Thomas Register of American mine which lighting system is best for this application, and
Manufacturers. What are some of the applications of prepare a report of your findings. Use manufacturers data and
vortex tubes? industrial electric rates in your locale to estimate costs. As-
sume that comparable lighting levels would be achieved by the
7.4D A government agency has solicited proposals for tech-
conventional and high-efficiency lighting.
nology in the area of exergy harvesting. The aim is to develop
small-scale devices to generate power for rugged-duty appli- 7.9D A factory has a 120 kW screw compressor that takes in
cations with power requirements ranging from hundreds of mil- 0.5 m3/s of ambient air and delivers compressed air at 1 MPa
liwatts to several watts. The power must be developed from for actuating pneumatic tools. The factory manager read in a
only ambient sources, such as thermal and chemical gradients, plant engineering magazine that using compressed air is more
naturally occurring fuels (tree sap, plants, waste matter, etc.), expensive than the direct use of electricity for operating such
wind, solar, sound and vibration, and mechanical motion in- tools and asks for your opinion. Using exergy costing with
cluding human motion. The devices must also operate with lit- electric rates in your locale, what do you say?
tle or no human intervention. Devise a system that would meet 7.10D Pinch analysis (or pinch technology) is a popular
these requirements. Clearly identify its intended application methodology for optimizing the design of heat exchanger net-
and explain its operating principles. Estimate its size, weight, works in complex thermal systems. Pinch analysis uses a pri-
and expected power output. marily graphical approach to implement second-law reason-
7.5D In one common arrangement, the exergy input to a power ing. Write a paper discussing the role of pinch analysis within
cycle is obtained by heat transfer from hot products of com- thermoeconomics.
bustion cooling at approximately constant pressure, while ex- 7.11D Wind Power Looming Large (see box Sec. 7.4) Iden-
ergy is discharged by heat transfer to water or air at ambient tify sites in your state where wind turbines for utility-scale
conditions. Devise a theoretical power cycle that at steady state electrical generation are feasible, considering both engineer-
develops the maximum theoretical net work per cycle from the ing and societal issues. Write a report including at least three
exergy supplied by the cooling products of combustion and references.
C
H
A
P
T
Vapor Power
Systems R
E
8
E N G I N E E R I N G C O N T E X T An important engineering goal is to
devise systems that accomplish desired types of energy conversion. The present chapter
and the next are concerned with several types of power-generating systems, each of
which produces a net power output from a fossil fuel, nuclear, or solar input. In these
chapters, we describe some of the practical arrangements employed for power production
and illustrate how such power plants can be modeled thermodynamically. The discussion is
organized into three main areas of application: vapor power plants, gas turbine power
plants, and internal combustion engines. These power systems, together with hydroelectric
power plants, produce virtually all of the electrical and mechanical power used worldwide.
The objective of the present chapter is to study vapor power plants in which the working chapter objective
fluid is alternately vaporized and condensed. Chapter 9 is concerned with gas turbines and
internal combustion engines in which the working fluid remains a gas.

8.1 Modeling Vapor Power Systems
The processes taking place in power-generating systems are sufficiently complicated that
idealizations are required to develop thermodynamic models. Such modeling is an important
initial step in engineering design. Although the study of simplified models generally leads
only to qualitative conclusions about the performance of the corresponding actual devices,
models often allow deductions about how changes in major operating parameters affect actual
performance. They also provide relatively simple settings in which to discuss the functions
and benefits of features intended to improve overall performance.
The vast majority of electrical generating plants are variations of vapor power plants in
which water is the working fluid. The basic components of a simplified fossil-fuel vapor
power plant are shown schematically in Fig. 8.1. To facilitate thermodynamic analysis, the
overall plant can be broken down into the four major subsystems identified by the letters A
through D on the diagram. The focus of our considerations in this chapter is subsystem A,
where the important energy conversion from heat to work occurs. But first, let us briefly con-
sider the other subsystems.
The function of subsystem B is to supply the energy required to vaporize the water passing
through the boiler. In fossil-fuel plants, this is accomplished by heat transfer to the work-
ing fluid passing through tubes and drums in the boiler from the hot gases produced by the
combustion of a fossil fuel. In nuclear plants, the origin of the energy is a controlled nu-
clear reaction taking place in an isolated reactor building. Pressurized water, a liquid metal,
325
326 Chapter 8 Vapor Power Systems
Stack
A D C
Combustion gases
to stack
Electric +
Turbine generator
Boiler
Cooling tower
Fuel Condenser
Air Warm water
B
Pump Cooled water
Feedwater pump Makeup water
Figure 8.1 Components of a simple vapor power plant.
or a gas such as helium can be used to transfer energy released in the nuclear reaction to
the working fluid in specially designed heat exchangers. Solar power plants have receivers
for concentrating and collecting solar radiation to vaporize the working fluid. Regardless of
the energy source, the vapor produced in the boiler passes through a turbine, where it ex-
pands to a lower pressure. The shaft of the turbine is connected to an electric generator (sub-
system D). The vapor leaving the turbine passes through the condenser, where it condenses
on the outside of tubes carrying cooling water. The cooling water circuit comprises sub-
system C. For the plant shown, the cooling water is sent to a cooling tower, where energy
taken up in the condenser is rejected to the atmosphere. The cooling water is then recircu-
lated through the condenser.
Concern for the environment and safety considerations govern what is allowable in the
interactions between subsystems B and C and their surroundings. One of the major difficulties
in finding a site for a vapor power plant is access to sufficient quantities of cooling water.
For this reason and to minimize thermal pollution effects, most power plants now employ
cooling towers. In addition to the question of cooling water, the safe processing and delivery
of fuel, the control of pollutant discharges, and the disposal of wastes are issues that must
be dealt with in both fossil-fueled and nuclear-fueled plants to ensure safety and operation
with an acceptable level of environmental impact. Solar power plants are generally regarded
as nonpolluting and safe but as yet are not widely used.
Returning now to subsystem A of Fig. 8.1, observe that each unit of mass periodically
undergoes a thermodynamic cycle as the working fluid circulates through the series of four
interconnected components. Accordingly, several concepts related to thermodynamic power
cycles introduced in previous chapters are important for the present discussions. You will
recall that the conservation of energy principle requires that the net work developed by a
power cycle equals the net heat added. An important deduction from the second law is that
the thermal efficiency, which indicates the extent to which the heat added is converted to a
net work output, must be less than 100%. Previous discussions also have indicated that
8.2 Analyzing Vapor Power SystemsRankine Cycle 327
improved thermodynamic performance accompanies the reduction of irreversibilities. The

extent to which irreversibilities can be reduced in power-generating systems depends on
thermodynamic, economic, and other factors, however.

8.2 Analyzing Vapor Power
SystemsRankine Cycle
All of the fundamentals required for the thermodynamic analysis of power-generating systems
already have been introduced. They include the conservation of mass and conservation of energy
principles, the second law of thermodynamics, and thermodynamic data. These principles ap-
ply to individual plant components such as turbines, pumps, and heat exchangers as well as to
the most complicated overall power plants. The object of this section is to introduce the Rankine Rankine cycle
cycle, which is a thermodynamic cycle that models the subsystem labeled A on Fig. 8.1. The
presentation begins by considering the thermodynamic analysis of this subsystem.
8.2.1 Evaluating Principal Work and Heat Transfers

The principal work and heat transfers of subsystem A are illustrated in Fig. 8.2. In subsequent METHODOLOGY
discussions, these energy transfers are taken to be positive in the directions of the arrows. UPDATE
The unavoidable stray heat transfer that takes place between the plant components and their When analyzing vapor
surroundings is neglected here for simplicity. Kinetic and potential energy changes are also power cycles, we take en-
ignored. Each component is regarded as operating at steady state. Using the conservation of ergy transfers as positive
in the directions of arrows
mass and conservation of energy principles together with these idealizations, we develop
on system schematics and
expressions for the energy transfers shown on Fig. 8.2 beginning at state 1 and proceeding write the energy balance
through each component in turn. accordingly.
TURBINE. Vapor from the boiler at state 1, having an elevated temperature and pressure,
expands through the turbine to produce work and then is discharged to the condenser at state 2
with relatively low pressure. Neglecting heat transfer with the surroundings, the mass and
energy rate balances for a control volume around the turbine reduce at steady state to give
0 0
V21 V22
0 Qcv Wt
m c h1 h2

g 1z1 z2 2d
# 0 # #
2
or
#
Wt
# h1 h2 (8.1)
m
Turbine t
W
1
2
in
Q
Boiler out
Q
Cooling water
Pump
Condenser
4
3
Figure 8.2 Principal work and heat
p
W
transfers of subsystem A.
# #
where m denotes the mass flow rate of the working fluid, and Wt m is the rate at which work
#
is developed per unit of mass of steam passing through the turbine. As noted above, kinetic
and potential energy changes are ignored.
CONDENSER. In the condenser there is heat transfer from the vapor to cooling water flow-
ing in a separate stream. The vapor condenses and the temperature of the cooling water in-
creases. At steady state, mass and energy rate balances for a control volume enclosing the
condensing side of the heat exchanger give
#
Qout
# h2 h3 (8.2)
m
#
where Qout m is the rate at which energy is transferred by heat from the working fluid to the
#
cooling water per unit mass of working fluid passing through the condenser. This energy
transfer is positive in the direction of the arrow on Fig. 8.2.
PUMP. The liquid condensate leaving the condenser at 3 is pumped from the condenser into
the higher pressure boiler. Taking a control volume around the pump and assuming no heat
transfer with the surroundings, mass and energy rate balances give
#
Wp
# h4 h3 (8.3)
m
# #
where Wp m is the rate of power input per unit of mass passing through the pump. This
energy transfer is positive in the direction of the arrow on Fig. 8.2.
BOILER. The working fluid completes a cycle as the liquid leaving the pump at 4, called
feedwater the boiler feedwater, is heated to saturation and evaporated in the boiler. Taking a control
volume enclosing the boiler tubes and drums carrying the feedwater from state 4 to state 1,
mass and energy rate balances give
#
Qin
# h1 h4 (8.4)
m
#
where Qin m is the rate of heat transfer from the energy source into the working fluid per
#
unit mass passing through the boiler.
PERFORMANCE PARAMETERS. The thermal efficiency gauges the extent to which the en-
ergy input to the working fluid passing through the boiler is converted to the net work out-
put. Using the quantities and expressions just introduced, the thermal efficiency of the power
cycle of Fig. 8.2 is
1h1 h2 2 1h4 h3 2
# # # #
Wt m Wp m
thermal efficiency h # (8.5a)
Qin m
#
h1 h4
The net work output equals the net heat input. Thus, the thermal efficiency can be expressed
alternatively as
# # #
Qinm Qoutm Qoutm
# # #
h # 1 #
Qinm Qinm
# #
1h2 h3 2
1
1h1 h4 2
(8.5b)

Cleaner Is Better One promising tech-
nology is fluidized bed
The United States relies heavily upon abundant coal re- combustion, where a
serves to generate electric power, but these systems require powdered coal-lime-
a great deal of clean-up, experts say. Awareness of the health stone mixture churns
and environmental impacts of coal have led to increasingly- in air to enhance the
stringent regulations on coal-burning power plants. As a burning. The limestone
result, the search for new clean-coal technologies has removes some sulfur
intensified. during combustion rather than waiting to remove the sulfur
According to industry sources, controlling particulate emis- after combustion, as in conventional boilers. Nitric oxide
sions and safely disposing of millions of tons of coal waste formation is also less because of the relatively low tempera-
once were the main concerns. Sulfur dioxide removal then be- tures of fluidized bed combustion. Another innovation is the
came an issue due to concern over acid rain. More recently, integrated gasification combined-cycle plant, or IGCC, that
nitric oxide (NOX), mercury, and fine particle (less than 3 promises to be cleaner and have higher thermal efficiency than
microns) emissions were recognized as especially harmful. conventional plants. In an IGCC, coal is converted to a cleaner-
Strides have been made in developing more effective sulfur burning combustible gas that is used in a power plant
dioxide scrubbers and particulate capture devices, but stricter combining gas and steam turbines.
environmental standards demand new approaches.
Another parameter used to describe power plant performance is the back work ratio, or back work ratio
bwr, defined as the ratio of the pump work input to the work developed by the turbine. With
Eqs. 8.1 and 8.3, the back work ratio for the power cycle of Fig. 8.2 is
1h4 h3 2
# #
Wp m
bwr # #
1h1 h2 2
(8.6)
Wt m
Examples to follow illustrate that the change in specific enthalpy for the expansion of vapor
through the turbine is normally many times greater than the increase in enthalpy for the liq-
uid passing through the pump. Hence, the back work ratio is characteristically quite low for
vapor power plants.
Provided states 1 through 4 are fixed, Eqs. 8.1 through 8.6 can be applied to determine
the thermodynamic performance of a simple vapor power plant. Since these equations
have been developed from mass and energy rate balances, they apply equally for actual
performance when irreversibilities are present and for idealized performance in the ab-
sence of such effects. It might be surmised that the irreversibilities of the various power
plant components can affect overall performance, and this is the case. Even so, it is in-
structive to consider an idealized cycle in which irreversibilities are assumed absent, for
such a cycle establishes an upper limit on the performance of the Rankine cycle. The ideal
cycle also provides a simple setting in which to study various aspects of vapor power
plant performance.
8.2.2 Ideal Rankine Cycle

If the working fluid passes through the various components of the simple vapor power cycle
without irreversibilities, frictional pressure drops would be absent from the boiler and
condenser, and the working fluid would flow through these components at constant pressure.
Also, in the absence of irreversibilities and heat transfer with the surroundings, the processes
through the turbine and pump would be isentropic. A cycle adhering to these idealizations is
the ideal Rankine cycle shown in Fig. 8.3. ideal Rankine cycle
T
1
1
a
4
3 2 2
Figure 8.3 Temperatureentropy diagram of
c b s the ideal Rankine cycle.
Referring to Fig. 8.3, we see that the working fluid undergoes the following series of in-
ternally reversible processes:
Process 12: Isentropic expansion of the working fluid through the turbine from saturated
vapor at state 1 to the condenser pressure.
Process 23: Heat transfer from the working fluid as it flows at constant pressure through
the condenser with saturated liquid at state 3.
Process 34: Isentropic compression in the pump to state 4 in the compressed liquid region.
Process 41: Heat transfer to the working fluid as it flows at constant pressure through the
boiler to complete the cycle.
The ideal Rankine cycle also includes the possibility of superheating the vapor, as in cycle
12341. The importance of superheating is discussed in Sec. 8.3.
Since the ideal Rankine cycle consists of internally reversible processes, areas under the
process lines of Fig. 8.3 can be interpreted as heat transfers per unit of mass flowing. Ap-
plying Eq. 6.51, area 1bc4a1 represents the heat transfer to the working fluid passing
through the boiler and area 2bc32, is the heat transfer from the working fluid passing
through the condenser, each per unit of mass flowing. The enclosed area 1234a1 can
be interpreted as the net heat input or, equivalently, the net work output, each per unit of
mass flowing.
Because the pump is idealized as operating without irreversibilities, Eq. 6.53b can be in-
voked as an alternative to Eq. 8.3 for evaluating the pump work. That is
#
Wp
a # b int
4
v dp (8.7a)
m rev 3
where the minus sign has been dropped for consistency with the positive value for pump
work in Eq. 8.3. The subscript int rev has been retained as a reminder that this expression
METHODOLOGY is restricted to an internally reversible process through the pump. No such designation is re-
UPDATE
quired by Eq. 8.3, however, because it expresses the conservation of mass and energy prin-
For cycles, we modify the ciples and thus is not restricted to processes that are internally reversible.
problem-solving methodol-
Evaluation of the integral of Eq. 8.7a requires a relationship between the specific volume
ogy: The Analysis begins
with a systematic evalua- and pressure for the process. Because the specific volume of the liquid normally varies only
tion of required property slightly as the liquid flows from the inlet to the exit of the pump, a plausible approximation
data at each numbered to the value of the integral can be had by taking the specific volume at the pump inlet, v3,
state. This reinforces what as constant for the process. Then
we know about the com-
#
ponents, since given infor- Wp
mation and assumptions a # b int v3 1 p4 p3 2 (8.7b)
are required to fix the m rev
states.
The next example illustrates the analysis of an ideal Rankine cycle.
EXAMPLE 8.1 Ideal Rankine Cycle
Steam is the working fluid in an ideal Rankine cycle. Saturated vapor enters the turbine at 8.0 MPa and saturated liquid exits
the condenser at a pressure of 0.008 MPa. The net power output of the cycle is 100 MW. Determine for the cycle # (a) the
thermal efficiency, (b) the back work ratio, (c) the mass flow rate of the steam, in kg/h, #(d) the rate of heat transfer, Qin, into
the working fluid as it passes through the boiler, in MW, (e) the rate of heat transfer, Qout, from the condensing steam as it
passes through the condenser, in MW, (f) the mass flow rate of the condenser cooling water, in kg/ h, if cooling water enters
the condenser at 15C and exits at 35C.
SOLUTION
Known: An ideal Rankine cycle operates with steam as the working fluid. The boiler and condenser pressures are specified,
and the net power output is given.
Find: Determine the thermal efficiency, the back work ratio, the mass flow rate of the steam, in kg/h, the rate of heat transfer
to the working fluid as it passes through the boiler, in MW, the rate of heat transfer from the condensing steam as it passes
through the condenser, in MW, the mass flow rate of the condenser cooling water, which enters at 15C and exits at 35C.
in
Q
p1 =
Boiler 8.0 MPa t
W
Turbine
T
1
Saturated 1
vapor 8.0 MPa
2
Condenser
out
Q
4 0.008 MPa
Pump Cooling
water 3 2
4
s
3
p
W Saturated
liquid at 0.008 MPa
Figure E8.1
Assumptions:
1. Each component of the cycle is analyzed as a control volume at steady state. The control volumes are shown on the
accompanying sketch by dashed lines.
2. All processes of the working fluid are internally reversible.
3. The turbine and pump operate adiabatically.
5. Saturated vapor enters the turbine. Condensate exits the condenser as saturated liquid.
Analysis: To begin the analysis, we fix each of the principal states located on the accompanying schematic and Ts diagrams.
Starting at the inlet to the turbine, the pressure is 8.0 MPa and the steam is a saturated vapor, so from Table A-3, h1 2758.0
kJ/kg and s1 5.7432 kJ/kg # K.
State 2 is fixed by p2 0.008 MPa and the fact that the specific entropy is constant for the adiabatic, internally reversible ex-
pansion through the turbine. Using saturated liquid and saturated vapor data from Table A-3, we find that the quality at state 2 is
s2 sf 5.7432 0.5926
x2 0.6745
sg sf 7.6361
The enthalpy is then
h2 hf
x2hfg 173.88
10.674522403.1
1794.8 kJ/kg
State 3 is saturated liquid at 0.008 MPa, so h3 173.88 kJ/kg.

State 4 is fixed by the boiler pressure p4 and the specific entropy s4 s3. The specific enthalpy h4 can be found by inter-
polation in the compressed liquid tables. However, because compressed liquid data are relatively sparse, it is more convenient
to solve Eq. 8.3 for h4, using Eq. 8.7b to approximate the pump work. With this approach
h4 h3
Wp m h3
v3 1 p4 p3 2
# #
By inserting property values from Table A-3
106 N/m2
h4 173.88 kJ/kg
11.0084 10 3 m3/kg218.0 0.0082 MPa ` ` ` 3 # `
1 kJ
1 MPa 10 N m
173.88
8.06 181.94 kJ/kg
(a) The net power developed by the cycle is

# # #
Wcycle Wt Wp
Mass and energy rate balances for control volumes around the turbine and pump give, respectively
# #
Wt Wp
# h1 h2 and # h4 h3
m m
#
where m is the mass flow rate of the steam. The rate of heat transfer to the working fluid as it passes through the boiler is
determined using mass and energy rate balances as
#
Qin
# h1 h4
m
The thermal efficiency is then
1h1 h2 2 1h4 h3 2
# #
Wt Wp
h #
Qin h1 h4
3 12758.0 1794.82 1181.94 173.882 4 kJ/kg

12758.0 181.942 kJ/kg
0.371 137.1% 2
(b) The back work ratio is
1181.94 173.882 kJ/kg

#
Wp h4 h3
bwr #
Wt h 1 h2

12758.0 1794.82 kJ/kg
8.37 103 10.84% 2

8.06

963.2
(c) The mass flow rate of the steam can be obtained from the expression for the net power given in part (a). Thus
#
# Wcycle
m
1h1 h2 2 1h4 h3 2
1100 MW2 103 kW/MW 3600 s/h

1963.2 8.062 kJ/kg
3.77 105 kg/h
#
(d) With the expression for Qin from part (a) and previously determined specific enthalpy values
Qin m 1h1 h4 2
# #
13.77 105 kg/ h212758.0 181.942 kJ/kg

3600 s/h 103 kW/MW
269.77 MW
(e) Mass and energy rate balances applied to a control volume enclosing the steam side of the condenser give
Qout m 1h2 h3 2
# #
13.77 105 kg/h211794.8 173.882 kJ/kg

3600 s/h 103 kW/MW
169.75 MW
# #
Note that the ratio # of Qout to Qin is 0.629 (62.9%).
Alternatively, Qout can be determined from an energy rate balance on the overall vapor power plant. At steady state, the
net power developed equals the net rate of heat transfer to the plant
# # #
Wcycle Qin Qout
Rearranging this expression and inserting values
# # #
Qout Qin Wcycle 269.77 MW 100 MW 169.77 MW
The slight difference from the above value is due to round-off.
(f) Taking a control volume around the condenser, the mass and energy rate balances give at steady state
0 Qcv Wcv
mcw 1hcw,in hcw,out 2
m 1h2 h3 2
#0 #0 # #
# #
where mcw is the mass flow rate of the cooling water. Solving for mcw
m 1h2 h3 2
#
#
mcw
1hcw,out hcw,in 2
The numerator in this expression is evaluated in part (e). For the cooling water, h hf ( T), so with saturated liquid enthalpy
values from Table A-2 at the entering and exiting temperatures of the cooling water
# 1169.75 MW2 103 kW/MW 3600 s/h
mcw 7.3 106 kg/h
1146.68 62.992 kJ/kg
Note that a slightly revised problem-solving methodology is used in this example problem: We begin with a systematic
evaluation of the specific enthalpy at each numbered state.
Note that the back work ratio is relatively low for the Rankine cycle. In the present case, the work required to operate the
pump is less than 1% of the turbine output.
In this example, 62.9% of the energy added to the working fluid by heat transfer is subsequently discharged to the cool-
ing water. Although considerable energy is carried away by the cooling water, its exergy is small because the water exits
at a temperature only a few degrees greater than that of the surroundings. See Sec. 8.6 for further discussion.
8.2.3 Effects of Boiler and Condenser Pressures

on the Rankine Cycle
In discussing Fig. 5.9 (Sec. 5.5.1), we observed that the thermal efficiency of power cycles
tends to increase as the average temperature at which energy is added by heat transfer increases
and/or the average temperature at which energy is rejected decreases. (For elaboration, see
box.) Let us apply this idea to study the effects on performance of the ideal Rankine cycle
of changes in the boiler and condenser pressures. Although these findings are obtained with
reference to the ideal Rankine cycle, they also hold qualitatively for actual vapor power plants.
C O N S I D E R I N G T H E E F F E C T O F T E M P E R AT U R E O N
THERMAL EFFICIENCY
Since the ideal Rankine cycle consists entirely of internally reversible processes, an
expression for thermal efficiency can be obtained in terms of average temperatures dur-
ing the heat interaction processes. Let us begin the development of this expression by
recalling that areas under the process lines of Fig. 8.3 can be interpreted as the heat
transfer per unit of mass flowing through the respective components. For example, the
total area 1bc4a1 represents the heat transfer into the working fluid per unit of
mass passing through the boiler. In symbols,
#
a # b int
Qin 1
T ds area 1bc4a1
m rev 4
The integral can be written in terms of an average temperature of heat addition, Tin, as
follows:
#
a # b int Tin 1s1 s4 2
Qin
m rev
where the overbar denotes average. Similarly, area 2bc32 represents the heat trans-
fer from the condensing steam per unit of mass passing through the condenser
#
a # b int Tout 1s2 s3 2 area 2bc32
Qout
m rev
Tout 1s1 s4 2
where Tout denotes the temperature on the steam side of the condenser of the ideal
Rankine cycle pictured in Fig. 8.3. The thermal efficiency of the ideal Rankine cycle
can be expressed in terms of these heat transfers as
1Qout m2 int
# #
rev Tout
hideal 1 # 1
1Qin m2 int
# (8.8)
Tin
rev
By the study of Eq. 8.8, we conclude that the thermal efficiency of the ideal cycle tends
to increase as the average temperature at which energy is added by heat transfer in-
creases and/or the temperature at which energy is rejected decreases. With similar rea-
soning, these conclusions can be shown to apply to the other ideal cycles considered
in this chapter and the next.
Figure 8.4a shows two ideal cycles having the same condenser pressure but different
boiler pressures. By inspection, the average temperature of heat addition is seen to be
greater for the higher-pressure cycle 12341 than for cycle 12341. It follows
that increasing the boiler pressure of the ideal Rankine cycle tends to increase the thermal
efficiency.
Figure 8.4b shows two cycles with the same boiler pressure but two different condenser
pressures. One condenser operates at atmospheric pressure and the other at less than at-
mospheric pressure. The temperature of heat rejection for cycle 12341 condensing at
atmospheric pressure is 100C (212F). The temperature of heat rejection for the lower-
pressure cycle 12341 is correspondingly lower, so this cycle has the greater thermal
efficiency. It follows that decreasing the condenser pressure tends to increase the thermal
efficiency.
T T
Increased Fixed boiler pressure

1 boiler pressure
1 1 Decreased
condenser pressure
4
4 patm
Fixed
4 condenser pressure 100 C 2
(212 F) 4 3 p < patm
2
3 2 2 3
Ambient temperature
s s
(a) (b)
Figure 8.4 Effects of varying operating pressures on the ideal Rankine cycle. (a) Effect of
boiler pressure. (b) Effect of condenser pressure.
The lowest feasible condenser pressure is the saturation pressure corresponding to the am-
bient temperature, for this is the lowest possible temperature for heat rejection to the sur-
roundings. The goal of maintaining the lowest practical turbine exhaust (condenser) pressure
is a primary reason for including the condenser in a power plant. Liquid water at atmospheric
pressure could be drawn into the boiler by a pump, and steam could be discharged directly
to the atmosphere at the turbine exit. However, by including a condenser in which the steam
side is operated at a pressure below atmospheric, the turbine has a lower-pressure region in
which to discharge, resulting in a significant increase in net work and thermal efficiency. The
addition of a condenser also allows the working fluid to flow in a closed loop. This arrange-
ment permits continual circulation of the working fluid, so purified water that is less corro-
sive than tap water can be used economically.
COMPARISON WITH CARNOT CYCLE. Referring to Fig. 8.5, the ideal Rankine cycle
123441 has a lower thermal efficiency than the Carnot cycle 12341 having the
same maximum temperature TH and minimum temperature TC because the average temper-
ature between 4 and 4 is less than TH. Despite the greater thermal efficiency of the Carnot
Cooling curve for the

products of combustion
T
t
tan
s
con
p
TH 4 1
4
TC
3 3 2
Figure 8.5 Illustration used to compare
s the ideal Rankine cycle with the Carnot cycle.
cycle, it has two shortcomings as a model for the simple vapor power cycle. First, the heat
passing to the working fluid of a vapor power plant is usually obtained from hot products of
combustion cooling at approximately constant pressure. To exploit fully the energy released
on combustion, the hot products should be cooled as much as possible. The first portion of
the heating process of the Rankine cycle shown in Fig. 8.5, Process 44, is achieved by
cooling the combustion products below the maximum temperature TH. With the Carnot cycle,
however, the combustion products would be cooled at the most to TH. Thus, a smaller por-
tion of the energy released on combustion would be used. The second shortcoming of the
Carnot vapor power cycle involves the pumping process. Note that the state 3 of Fig. 8.5 is
a two-phase liquidvapor mixture. Significant practical problems are encountered in devel-
oping pumps that handle two-phase mixtures, as would be required by Carnot cycle
12341. It is far easier to condense the vapor completely and handle only liquid in the
pump, as is done in the Rankine cycle. Pumping from 3 to 4 and constant-pressure heating
without work from 4 to 4 are processes that can be closely achieved in practice.
8.2.4 Principal Irreversibilities and Losses

Irreversibilities and losses are associated with each of the four subsystems shown in Fig. 8.1.
Some of these effects have a more pronounced influence on performance than others. Let us
consider the irreversibilities and losses associated with the Rankine cycle.
TURBINE. The principal irreversibility experienced by the working fluid is associated with
the expansion through the turbine. Heat transfer from the turbine to the surroundings repre-
sents a loss, but since it is usually of secondary importance, this loss is ignored in subse-
quent discussions. As illustrated by Process 12 of Fig. 8.6, an actual adiabatic expansion
through the turbine is accompanied by an increase in entropy. The work developed per unit
of mass in this process is less than for the corresponding isentropic expansion 12s. The isen-
tropic turbine efficiency ht introduced in Sec. 6.8 allows the effect of irreversibilities within
the turbine to be accounted for in terms of the actual and isentropic work amounts. Desig-
nating the states as in Fig. 8.6, the isentropic turbine efficiency is
1Wt m2
# #
h1 h2
ht # #
1Wt m2 s
(8.9)
h1 h2s
where the numerator is the actual work developed per unit of mass passing through the tur-
bine and the denominator is the work for an isentropic expansion from the turbine inlet state
4
4s
3 2s 2
Figure 8.6 Temperatureentropy diagram
showing the effects of turbine and pump
s irreversibilities.
to the turbine exhaust pressure. Irreversibilities within the turbine significantly reduce the net
power output of the plant.
PUMP. The work input to the pump required to overcome frictional effects also reduces
the net power output of the plant. In the absence of heat transfer to the surroundings, there
would be an increase in entropy across the pump. Process 3 4 of Fig. 8.6 illustrates the
actual pumping process. The work input for this process is greater than for the corre-
sponding isentropic process 3 4s. The isentropic pump efficiency p introduced in Sec. 6.8
allows the effect of irreversibilities within the pump to be accounted for in terms of the
actual and isentropic work amounts. Designating the states as in Fig. 8.6, the isentropic
pump efficiency is
1Wp m2 s
# #
h4s h3
hp # #
1Wp m2
(8.10)
h4 h3
In this expression, the pump work for the isentropic process appears in the numerator. The
actual pump work, being the larger quantity, is the denominator. Because the pump work is
so much less than the turbine work, irreversibilities in the pump have a much smaller impact
on the net work of the cycle than do irreversibilities in the turbine.
OTHER NONIDEALITIES. The turbine and pump irreversibilities mentioned above are
internal irreversibilities experienced by the working fluid as it flows around the closed loop
of the Rankine cycle. The most significant sources of irreversibility for a fossil-fueled vapor
power plant, however, are associated with the combustion of the fuel and the subsequent heat
transfer from the hot combustion products to the cycle working fluid. These effects occur in
the surroundings of the subsystem labeled A on Fig. 8.1 and thus are external irreversibilities
for the Rankine cycle. These irreversibilities are considered further in Sec. 8.6 and Chap. 13
using the exergy concept.
Another effect that occurs in the surroundings is the energy discharge to the cooling water
as the working fluid condenses. Although considerable energy is carried away by the cool-
ing water, its utility is extremely limited. For condensers in which steam condenses near the
ambient temperature, the cooling water experiences a temperature rise of only a few degrees
over the temperature of the surroundings in passing through the condenser and thus has lim-
ited usefulness. Accordingly, the significance of this loss is far less than suggested by the
magnitude of the energy transferred to the cooling water. The utility of condenser cooling
water is considered further in Sec. 8.6 using the exergy concept.
In addition to the foregoing, there are several other sources of nonideality. For example,
stray heat transfers from the outside surfaces of the plant components have detrimental ef-
fects on performance, since such losses reduce the extent of conversion from heat input to
work output. Frictional effects resulting in pressure drops are sources of internal irreversibility
as the working fluid flows through the boiler, condenser, and piping connecting the various
components. Detailed thermodynamic analyses would account for these effects. For sim-
plicity, however, they are ignored in the subsequent discussions. Thus, Fig. 8.6 shows no
pressure drops for flow through the boiler and condenser or between plant components. An-
other effect on performance is suggested by the placement of state 3 on Fig. 8.6. At this state,
the temperature of the working fluid exiting the condenser would be lower than the satura-
tion temperature corresponding to the condenser pressure. This is disadvantageous because
a greater heat transfer would be required in the boiler to bring the water to saturation.
In the next example, the ideal Rankine cycle of Example 8.1 is modified to include the
effects of irreversibilities in the turbine and pump.
EXAMPLE 8.2 Rankine Cycle with Irreversibilities
Reconsider the vapor power cycle of Example 8.1, but include in the analysis that the turbine and the pump each have an isen-
tropic efficiency of 85%. Determine for the modified cycle (a) the # thermal efficiency, (b) the mass flow rate of steam, in kg/h,
for a net power output of 100 MW, # (c) the rate of heat transfer Qin into the working fluid as it passes through the boiler, in
MW, (d) the rate of heat transfer Qout from the condensing steam as it passes through the condenser, in MW, (e) the mass flow
rate of the condenser cooling water, in kg/h, if cooling water enters the condenser at 15C and exits as 35C. Discuss the
effects on the vapor cycle of irreversibilities within the turbine and pump.
SOLUTION
Known: A vapor power cycle operates with steam as the working fluid. The turbine and pump both have efficiencies of 85%.
Find: Determine the thermal efficiency, the mass flow rate, in kg/h, the rate of heat transfer to the working fluid as it passes
through the boiler, in MW, the heat transfer rate from the condensing steam as it passes through the condenser, in MW, and
the mass flow rate of the condenser cooling water, in kg/h. Discuss.
Assumptions:
T
1. Each component of the cycle is analyzed as a control volume at steady
8.0 MPa state.
1
2. The working fluid passes through the boiler and condenser at constant
pressure. Saturated vapor enters the turbine. The condensate is saturated
4
at the condenser exit.
4s
3. The turbine and pump each operate adiabatically with an efficiency
3 0.008 MPa
of 85%.
2s 2
s
Figure E8.2
Analysis: Owing to the presence of irreversibilities during the expansion of the steam through the turbine, there is an increase
in specific entropy from turbine inlet to exit, as shown on the accompanying Ts diagram. Similarly, there is an increase in
specific entropy from pump inlet to exit. Let us begin the analysis by fixing each of the principal states. State 1 is the same
as in Example 8.1, so h1 2758.0 kJ/kg and s1 5.7432 kJ/kg # K.
The specific enthalpy at the turbine exit, state 2, can be determined using the turbine efficiency
# #
Wt m h1 h2
ht # #
1Wt m2 s h1 h2s
where h2s is the specific enthalpy at state 2s on the accompanying Ts diagram. From the solution to Example 8.1, h2s
1794.8 kJ/ kg. Solving for h2 and inserting known values
h2 h1 ht 1h1 h2s 2
2758 0.8512758 1794.82 1939.3 kJ/kg
State 3 is the same as in Example 8.1, so h3 173.88 kJ/kg.
To determine the specific# enthalpy at the pump exit, state 4, reduce mass and energy rate balances for a control volume
around the pump to obtain Wpm h4 h3. On rearrangement, the specific enthalpy at state 4 is
#
# #
h4 h3
Wp m
To determine h4 from this expression requires the pump work, which can be evaluated using the pump efficiency hp, as follows.
By definition
1Wp m2 s
# #
hp # #
1Wp m2
The term 1Wp m2 s can be evaluated using Eq. 8.7b. Then solving for Wp m results in
# # # #
v3 1 p4 p3 2
#
Wp
#
m hp
The numerator of this expression was determined in the solution to Example 8.1. Accordingly,
#
Wp 8.06 kJ/kg
# 9.48 kJ/kg
m 0.85
The specific enthalpy at the pump exit is then
# #
h4 h3
Wp m 173.88
9.48 183.36 kJ/kg
Wcycle Wt Wp m 3 1h1 h2 2 1h4 h3 2 4

# # # #
The rate of heat transfer to the working fluid as it passes through the boiler is
Qin m 1h1 h4 2
# #
Thus, the thermal efficiency is
1h1 h2 2 1h4 h3 2
h
h1 h4
Inserting values
12758 1939.32 9.48

h 0.314 131.4% 2
2758 183.36
(b) With the net power expression of part (a), the mass flow rate of the steam is
#
# Wcycle
m
1h1 h2 2 1h4 h3 2
1100 MW2 3600 s/h 103 kW/MW
4.449 105 kg/h
1818.7 9.482 kJ/kg
#
(c) With the expression for Qin from part (a) and previously determined specific enthalpy values
Qin m 1h1 h4 2
# #
14.449 105 kg/h212758 183.362 kJ/kg

318.2 MW
3600 s/h 103 kW/MW
(d) The rate of heat transfer from the condensing steam to the cooling water is
Qout m 1h2 h3 2
# #
14.449 105 kg/h211939.3 173.882 kJ/kg

218.2 MW
3600 s/h 103 kW/MW
(e) The mass flow rate of the cooling water can be determined from
m 1h2 h3 2
#
#
mcw
1hcw,out hcw,in 2
1218.2 MW2 103 kW/MW 3600 s/h
9.39 106 kg/h
1146.68 62.992 kJ/kg
The effect of irreversibilities within the turbine and pump can be gauged by comparing the present values with their coun-
terparts in Example 8.1. In this example, the turbine work per unit of mass is less and the pump work per unit of mass is
greater than in Example 8.1. The thermal efficiency in the present case is less than in the ideal case of the previous example.
For a fixed net power output (100 MW), the smaller net work output per unit mass in the present case dictates a greater mass
flow rate of steam. The magnitude of the heat transfer to the cooling water is greater in this example than in Example 8.1;
consequently, a greater mass flow rate of cooling water would be required.
8.3 Improving PerformanceSuperheat

and Reheat
The representations of the vapor power cycle considered thus far do not depict actual vapor
power plants faithfully, for various modifications are usually incorporated to improve over-
all performance. In this section we consider two cycle modifications known as superheat and
reheat. Both features are normally incorporated into vapor power plants.
Let us begin the discussion by noting that an increase in the boiler pressure or a decrease
in the condenser pressure may result in a reduction of the steam quality at the exit of the tur-
bine. This can be seen by comparing states 2 and 2 of Figs. 8.4a and 8.4b to the corre-
sponding state 2 of each diagram. If the quality of the mixture passing through the turbine
becomes too low, the impact of liquid droplets in the flowing liquidvapor mixture can erode
the turbine blades, causing a decrease in the turbine efficiency and an increased need for
maintenance. Accordingly, common practice is to maintain at least 90% quality (x 0.9) at
the turbine exit. The cycle modifications known as superheat and reheat permit advantageous
operating pressures in the boiler and condenser and yet offset the problem of low quality of
the turbine exhaust.
superheat SUPERHEAT. First, let us consider superheat. As we are not limited to having saturated
vapor at the turbine inlet, further energy can be added by heat transfer to the steam, bring-
ing it to a superheated vapor condition at the turbine inlet. This is accomplished in a sepa-
rate heat exchanger called a superheater. The combination of boiler and superheater is re-
ferred to as a steam generator. Figure 8.3 shows an ideal Rankine cycle with superheated
vapor at the turbine inlet: cycle 12341. The cycle with superheat has a higher aver-
age temperature of heat addition than the cycle without superheating (cycle 12341), so
the thermal efficiency is higher. Moreover, the quality at turbine exhaust state 2 is greater
than at state 2, which would be the turbine exhaust state without superheating. Accordingly,
superheating also tends to alleviate the problem of low steam quality at the turbine exhaust.
With sufficient superheating, the turbine exhaust state may even fall in the superheated vapor
region.
reheat REHEAT. A further modification normally employed in vapor power plants is reheat. With
reheat, a power plant can take advantage of the increased efficiency that results with higher
boiler pressures and yet avoid low-quality steam at the turbine exhaust. In the ideal reheat
cycle shown in Fig. 8.7, the steam does not expand to the condenser pressure in a single
stage. The steam expands through a first-stage turbine (Process 12) to some pressure be-
tween the steam generator and condenser pressures. The steam is then reheated in the steam
generator (Process 23). Ideally, there would be no pressure drop as the steam is reheated.
After reheating, the steam expands in a second-stage turbine to the condenser pressure
(Process 34). The principal advantage of reheat is to increase the quality of the steam at the
turbine exhaust. This can be seen from the Ts diagram of Fig. 8.7 by comparing state 4 with
8.3 Improving PerformanceSuperheat and Reheat 341
Reheat section
3 Low-pressure
turbine
2
in
Q W t
1
1
T1
High- T
pressure 4 T3
3
turbine
2
Steam
generator
out
Q
Condenser 6
6 5 4 4
Pump
W p s
5
Figure 8.7 Ideal reheat cycle.
state 4, the turbine exhaust state without reheating. When computing the thermal efficiency
of a reheat cycle, it is necessary to account for the work output of both turbine stages as well
as the total heat addition occurring in the vaporization/superheating and reheating processes.
This calculation is illustrated in Example 8.3.
SUPERCRITICAL CYCLE. The temperature of the steam entering the turbine is restricted by T 1
3
metallurgical limitations imposed by the materials used to fabricate the superheater, reheater,
and turbine. High pressure in the steam generator also requires piping that can withstand
great stresses at elevated temperatures. Although these factors limit the gains that can be re- 2
alized through superheating and reheating, improved materials and methods of fabrication
have permitted significant increases over the years in the maximum allowed cycle tempera-
tures and steam generator pressures, with corresponding increases in thermal efficiency. This
6
has progressed to the extent that vapor power plants can be designed to operate with steam
generator pressures exceeding the critical pressure of water 22.1 MPa, and turbine inlet tem- 5 4
peratures exceeding 600C. Figure 8.8 shows an ideal reheat cycle with a supercritical steam s
generator pressure. Observe that no phase change occurs during the heat addition process Figure 8.8 Super-
from 6 to 1. critical ideal reheat cycle.
In the next example, the ideal Rankine cycle of Example 8.1 is modified to include
superheat and reheat.
EXAMPLE 8.3 Ideal Reheat Cycle
Steam is the working fluid in an ideal Rankine cycle with superheat and reheat. Steam enters the first-stage turbine at 8.0 MPa,
480C, and expands to 0.7 MPa. It is then reheated to 440C before entering the second-stage turbine, where it expands to the
condenser pressure of 0.008 MPa. The net power output is 100 MW. # Determine (a) the thermal efficiency of the cycle,
(b) the mass flow rate of steam, in kg/h, (c) the rate of heat transfer Qout from the condensing steam as it passes through the
condenser, in MW. Discuss the effects of reheat on the vapor power cycle.
SOLUTION
Known: An ideal reheat cycle operates with steam as the working fluid. Operating pressures and temperatures are specified,
and the net power output is given.
Find: Determine the thermal efficiency, the mass flow rate of the steam, in kg/h, and the heat transfer rate from the con-
densing steam as it passes through the condenser, in MW. Discuss.
Turbine 1
Turbine 2
T1 = 480C
Steam p1 = 8.0 MPa
generator 1
p2 = 0.7 MPa T 1
T1
2 T3
4 3
3 T3 = 440C
8.0 MPa
Condenser
0.7 MPa 2
pcond = 0.008 MPa
6
Pump
6 5 0.008 MPa 4
5 Saturated liquid s
Figure E8.3
Assumptions:
1. Each component in the cycle is analyzed as a control volume at steady state. The control volumes are shown on the ac-
companying sketch by dashed lines.
2. All processes of the working fluid are internally reversible.
4. Condensate exits the condenser as saturated liquid.
Analysis: To begin, we fix each of the principal states. Starting at the inlet to the first turbine stage, the pressure is 8.0 MPa
and the temperature is 480C, so the steam is a superheated vapor. From Table A-4, h1 3348.4 kJ/kg and s1
6.6586 kJ/kg # K.
State 2 is fixed by p2 0.7 MPa and s2 s1 for the isentropic expansion through the first-stage turbine. Using saturated
liquid and saturated vapor data from Table A-3, the quality at state 2 is
s2 sf 6.6586 1.9922
x2 0.9895
sg sf 6.708 1.9922
The specific enthalpy is then
h2 hf
x2hfg
697.22
10.989522066.3 2741.8 kJ/kg
State 3 is superheated vapor with p3 0.7 MPa and T3 440C, so from Table A-4, h3 3353.3 kJ/kg and s3 7.7571
kJ/kg # K.
To fix state 4, use p4 0.008 MPa and s4 s3 for the isentropic expansion through the second-stage turbine. With data
from Table A-3, the quality at state 4 is
s4 sf 7.7571 0.5926
x4 0.9382
sg sf 8.2287 0.5926
The specific enthalpy is
h4 173.88
10.938222403.1 2428.5 kJ/kg
State 5 is saturated liquid at 0.008 MPa, so h5 173.88 kJ/kg. Finally, the state at the pump exit is the same as in
Example 8.1, so h6 181.94 kJ/kg.

# # # #
Wcycle Wt1
Wt2 Wp
Mass and energy rate balances for the two turbine stages and the pump reduce to give, respectively
#
Wt1m h1 h2
#
Turbine 1:
#
Wt2m h3 h4
#
Turbine 2:
# #
Pump: Wpm h6 h5
#
where m is the mass flow rate of the steam.
The total rate of heat transfer to the working fluid as it passes through the boilersuperheater and reheater is
#
# 1h1 h6 2
1h3 h2 2
Qin
m
Using these expressions, the thermal efficiency is
1h1 h2 2
1h3 h4 2 1h6 h5 2
h
1h1 h6 2
1h3 h2 2
13348.4 2741.82
13353.3 2428.52 1181.94 173.882

13348.4 181.942
13353.3 2741.82
606.6
924.8 8.06
0.403 140.3% 2
1523.3 kJ/kg

3166.5
611.5 3778 kJ/kg
(b) The mass flow rate of the steam can be obtained with the expression for net power given in part (a).
#
# Wcycle
m
1h1 h2 2
1h3 h4 2 1h6 h5 2
1100 MW2 3600 s/h 103 kW/MW
2.363 105 kg/h
1606.6
924.8 8.062 kJ/kg
(c) The rate of heat transfer from the condensing steam to the cooling water is
Qout m 1h4 h5 2
# #
2.363 105 kg/h 12428.5 173.882 kJ/kg

148 MW
3600 s/h 103 kW/MW
To see the effects of reheat, we compare the present values with their counterparts in Example 8.1. With superheat
and reheat, the thermal efficiency is increased over that of the cycle of Example 8.1. For a specified net power output
(100 MW), a larger thermal efficiency means that a smaller mass flow rate of steam is required. Moreover, with a greater
thermal efficiency the rate of heat transfer to the cooling water is also less, resulting in a reduced demand for cooling
water. With reheating, the steam quality at the turbine exhaust is substantially increased over the value for the cycle of
Example 8.1.
The following example illustrates the effect of turbine irreversibilities on the ideal reheat
cycle of Example 8.3.
EXAMPLE 8.4 Reheat Cycle with Turbine Irreversibility
Reconsider the reheat cycle of Example 8.3, but include in the analysis that each turbine stage has the same isentropic effi-
ciency. (a) If t 85%, determine the thermal efficiency. (b) Plot the thermal efficiency versus turbine stage efficiency rang-
ing from 85 to 100%.
SOLUTION
Known: A reheat cycle operates with steam as the working fluid. Operating pressures and temperatures are specified. Each
turbine stage has the same isentropic efficiency.
Find: If t 85%, determine the thermal efficiency. Also, plot the thermal efficiency versus turbine stage efficiency rang-
ing from 85 to 100%.
T 1
T1
T3 Assumptions:
3
8.0 MPa 1. As in Example 8.3, each component is analyzed as a control volume at
steady state.
2
2. Except for the two turbine stages, all processes are internally reversible.
0.7 MPa 2s
4. The condensate exits the condenser as saturated liquid.
6
5 0.008 MPa 4s 4
s
Figure E8.4a
Analysis:
(a) From the solution to Example 8.3, the following specific enthalpy values are known, in kJ/kg: h1 3348.4, h2s 2741.8,
h3 3353.3, h4s 2428.5, h5 173.88, h6 181.94.
The specific enthalpy at the exit of the first-stage turbine, h2, can be determined by solving the expression for the turbine
efficiency to obtain
h2 h1 ht 1h1 h2s 2
3348.4 0.8513348.4 2741.82 2832.8 kJ/kg
The specific enthalpy at the exit of the second-stage turbine can be found similarly:
h4 h3 ht 1h3 h4s 2
3353.3 0.8513353.3 2428.52 2567.2 kJ/kg
1h1 h2 2
1h3 h4 2 1h6 h5 2
h
1h1 h6 2
1h3 h2 2
13348.4 2832.82
13353.3 2567.22 1181.94 173.882

13348.4 181.942
13353.3 2832.82
0.351 135.1% 2
1293.6 kJ/kg

3687.0 kJ/kg
# #
(b) The IT code for the solution follows, where etat1 is t1, etat2 is t2, eta is , Wnet Wnetm, and Qin Qinm.
# #
// Fix the states

T1 = 480 // C
p1 = 80 // bar
h1 = h_PT(Water/Steam, p1, T1)
s1 = s_PT(Water/Steam, p1, T1)
p2 = 7 // bar
h2s = h_Ps(Water/Steam, p2, s1)
etat1 = 0.85
h2 = h1 etat1 * (h1 h2s)
T3 = 440 // C
p3 = p2
h3 = h_PT(Water/Steam, p3, T3)
s3 = s_PT(Water/Steam, p3, T3)
p4 = 0.08 // bar
h4s = h_Ps(Water/Steam, p4, s3)
etat2 = etat1
h4 = h3 etat2 * (h3 h4s)
p5 = p4
h5 = hsat_Px(Water/Steam, p5, 0) // kJ/kg
v5 = vsat_Px(Water/Steam, p5, 0) // m3/kg
p6 = p1
h6 = h5 + v5 * (p6 p5) * 100 // The 100 in this expression is a unit conversion factor.
// Calculate thermal efficiency
Wnet = (h1 h2) + (h3 h4) (h6 h5)
Qin = (h1 h6) + (h3 h2)
eta = Wnet /Qin
Using the Explore button, sweep eta from 0.85 to 1.0 in steps of 0.01. Then, using the Graph button, obtain the following plot:
0.42
0.40
Cycle thermal efficiency
0.38
0.36
0.34
0.32
0.85 0.90 0.95 1.00
Isentropic turbine efficiency
Figure E8.4b
From Fig. E8.4b, we see that the cycle thermal efficiency increases from 0.351 to 0.403 as turbine stage efficiency increases
from 0.85 to 1.00, as expected based on the results of Examples 8.3(a) and 8.4(a). Turbine isentropic efficiency is seen to have
a significant effect on cycle thermal efficiency.
Owing to the irreversibilities present in the turbine stages, the net work per unit of mass developed in the present case is
significantly less than in the case of Example 8.3. The thermal efficiency is also considerably less.
8.4 Improving PerformanceRegenerative

Vapor Power Cycle
Another commonly used method for increasing the thermal efficiency of vapor power plants
regeneration is regenerative feedwater heating, or simply regeneration. This is the subject of the present
section.
To introduce the principle underlying regenerative feedwater heating, consider Fig. 8.3
once again. In cycle 1234a1, the working fluid would enter the boiler as a compressed
liquid at state 4 and be heated while in the liquid phase to state a. With regenerative feed-
water heating, the working fluid would enter the boiler at a state between 4 and a. As a result,
the average temperature of heat addition would be increased, thereby tending to increase the
thermal efficiency.
8.4.1 Open Feedwater Heaters

open feedwater heater Let us consider how regeneration can be accomplished using an open feedwater heater, a di-
rect contact-type heat exchanger in which streams at different temperatures mix to form a stream
at an intermediate temperature. Shown in Fig. 8.9 are the schematic diagram and the associ-
ated Ts diagram for a regenerative vapor power cycle having one open feedwater heater. For
this cycle, the working fluid passes isentropically through the turbine stages and pumps, and
the flow through the steam generator, condenser, and feedwater heater takes place with no pres-
sure drop in any of these components. Steam enters the first-stage turbine at state 1 and expands
to state 2, where a fraction of the total flow is extracted, or bled, into an open feedwater heater
operating at the extraction pressure, p2. The rest of the steam expands through the second-stage
turbine to state 3. This portion of the total flow is condensed to saturated liquid, state 4, and
then pumped to the extraction pressure and introduced into the feedwater heater at state 5. A
single mixed stream exits the feedwater heater at state 6. For the case shown in Fig. 8.9, the
mass flow rates of the streams entering the feedwater heater are chosen so that the stream exiting
the feedwater heater is a saturated liquid at the extraction pressure. The liquid at state 6 is then
pumped to the steam generator pressure and enters the steam generator at state 7. Finally, the
working fluid is heated from state 7 to state 1 in the steam generator.
(1 y)
Qin
(1)
1 Wt
T 1
( y) 2
(1 y)
Steam 3
generator 7
Condenser 2

Qout
a 6
(1 y)
Open
(1) feedwater 5
heater 3
7 6 5 4
4
Pump 2 Pump 1 s

Wp2 Wp1
Figure 8.9 Regenerative vapor power cycle with one open feedwater heater.
8.4 Improving PerformanceRegenerative Vapor Power Cycle 347
Referring to the Ts diagram of the cycle, note that the heat addition would take place
from state 7 to state 1, rather than from state a to state 1, as would be the case without re-
generation. Accordingly, the amount of energy that must be supplied from the combustion
of a fossil fuel, or another source, to vaporize and superheat the steam would be reduced.
This is the desired outcome. Only a portion of the total flow expands through the second-
stage turbine (Process 23), however, so less work would be developed as well. In practice,
operating conditions are chosen so that the reduction in heat added more than offsets the
decrease in net work developed, resulting in an increased thermal efficiency in regenerative
power plants.
CYCLE ANALYSIS. Consider next the thermodynamic analysis of the regenerative cycle
illustrated in Fig. 8.9. An important initial step in analyzing any regenerative vapor cy-
cle is the evaluation of the mass flow rates through each of the components. Taking a
single control volume enclosing both turbine stages, the mass rate balance reduces at
steady state to
# # #
m2
m3 m1
# #
where m1 is the rate at which mass enters the first-stage turbine at state 1, m2 is the rate at
#
which mass is extracted and exits at state 2, and m3 is the rate at which mass exits the
#
second-stage turbine at state 3. Dividing by m1 places this on the basis of a unit of mass
passing through the first-stage turbine
# #
m2 m3
#
# 1
m1 m1
Denoting the fraction of the total flow extracted at state 2 by y (y m2 m1), the fraction of
# #
the total flow passing through the second-stage turbine is
#
m3
# 1y (8.11)
m1
The fractions of the total flow at various locations are indicated on Fig. 8.9.
The fraction y can be determined by applying the conservation of mass and conservation
of energy principles to a control volume around the feedwater heater. Assuming no heat trans-
fer between the feedwater heater and its surroundings and ignoring kinetic and potential en-
ergy effects, the mass and energy rate balances reduce at steady state to give
0 yh2
11 y2h5 h6
Solving for y
h6 h5
y (8.12)
h2 h5
Equation 8.12 allows the fraction y to be determined when states 2, 5, and 6 are fixed.
Expressions for the principal work and heat transfers of the regenerative cycle can be de-
termined by applying mass and energy rate balances to control volumes around the individ-
ual components. Beginning with the turbine, the total work is the sum of the work developed
by each turbine stage. Neglecting kinetic and potential energy effects and assuming no heat
transfer with the surroundings, we can express the total turbine work on the basis of a unit
of mass passing through the first-stage turbine as
#
# 1h1 h2 2
11 y21h2 h3 2
Wt
(8.13)
m1
The total pump work is the sum of the work required to operate each pump individually. On
the basis of a unit of mass passing through the first-stage turbine, the total pump work is
#
Wp
# 1h7 h6 2
11 y21h5 h4 2 (8.14)
m1
The energy added by heat transfer to the working fluid passing through the steam generator,
per unit of mass expanding through the first-stage turbine, is
#
Qin
# h1 h7 (8.15)
m1
and the energy rejected by heat transfer to the cooling water is
#
# 11 y2 1h3 h4 2
Qout
(8.16)
m1
The following example illustrates the analysis of a regenerative cycle with one open feed-
water heater, including the evaluation of properties at state points around the cycle and the
determination of the fractions of the total flow at various locations.
EXAMPLE 8.5 Regenerative Cycle with Open Feedwater Heater
Consider a regenerative vapor power cycle with one open feedwater heater. Steam enters the turbine at 8.0 MPa, 480C and
expands to 0.7 MPa, where some of the steam is extracted and diverted to the open feedwater heater operating at 0.7 MPa.
The remaining steam expands through the second-stage turbine to the condenser pressure of 0.008 MPa. Saturated liquid ex-
its the open feedwater heater at 0.7 MPa. The isentropic efficiency of each turbine stage is 85% and each pump operates isen-
tropically. If the net power output of the cycle is 100 MW, determine (a) the thermal efficiency and (b) the mass flow rate of
steam entering the first turbine stage, in kg/h.
SOLUTION
Known: A regenerative vapor power cycle operates with steam as the working fluid. Operating pressures and temperatures
are specified; the efficiency of each turbine stage and the net power output are also given.
Find: Determine the thermal efficiency and the mass flow rate into the turbine, in kg/h.
(1 y)
(1)
Steam T1 = 480C 1
p1 = 8.0 MPa T T1
generator Wt
1
8.0 MPa
( y)
2 3 7 0.7 MPa 2s 2
Condenser
6
Saturated (1 y)
liquid at (1 y) 5 0.008 MPa
0.7 MPa Open
(1) 4 3s 3
feedwater pcond =
heater 0.008 MPa
7 6 5 4 s
Saturated liquid
Pump 2 Pump 1 at 0.008 MPa

Wp2 Wp1
Figure E8.5
Assumptions:
1. Each component in the cycle is analyzed as a steady-state control volume. The control volumes are shown in the accom-
panying sketch by dashed lines.
2. All processes of the working fluid are internally reversible, except for the expansions through the two turbine stages and
mixing in the open feedwater heater.
3. The turbines, pumps, and feedwater heater operate adiabatically.
5. Saturated liquid exits the open feedwater heater, and saturated liquid exits the condenser.
Analysis: The specific enthalpy at states 1 and 4 can be read from the steam tables. The specific enthalpy at state 2 is eval-
uated in the solution to Example 8.4. The specific entropy at state 2 can be obtained from the steam tables using the known
values of enthalpy and pressure at this state. In summary, h1 3348.4 kJ/kg, h2 2832.8 kJ/kg, s2 6.8606 kJ/kg # K, h4
173.88 kJ/kg.
The specific enthalpy at state 3 can be determined using the efficiency of the second-stage turbine
h3 h2 ht 1h2 h3s 2
With s3s s2, the quality at state 3s is x3s 0.8208; using this, we get h3s 2146.3 kJ/kg. Hence
h3 2832.8 0.8512832.8 2146.32 2249.3 kJ/kg
State 6 is saturated liquid at 0.7 MPa. Thus, h6 697.22 kJ/kg.
Since the pumps are assumed to operate with no irreversibilities, the specific enthalpy values at states 5 and 7 can be
determined as
h5 h4
v4 1 p5 p4 2
106 N/m2
173.88
11.0084 103 21m3/kg210.7 0.0082 MPa ` ` ` 3 # ` 174.6 kJ/kg
1 kJ
1 MPa 10 N m
h7 h6
v6 1 p7 p6 2
697.22
11.1080 103 218.0 0.72 103 705.3 kJ/kg
Applying mass and energy rate balances to a control volume enclosing the open heater, we find the fraction y of the flow
extracted at state 2 from
h6 h5 697.22 174.6
y 0.1966
h2 h5 2832.8 174.6
(a) On the basis of a unit of mass passing through the first-stage turbine, the total turbine work output is
#
# 1h1 h2 2
11 y21h2 h3 2
Wt
m1
13348.4 2832.82
10.8034212832.8 2249.32 984.4 kJ/kg
The total pump work per unit of mass passing through the first-stage turbine is
#
Wp
# 1h7 h6 2
11 y21h5 h4 2
m1
1705.3 697.222
10.803421174.6 173.882 8.7 kJ/kg
The heat added in the steam generator per unit of mass passing through the first-stage turbine is
#
Qin
# h1 h7 3348.4 705.3 2643.1 kJ/kg
m1
# # # #
Wt m1 Wp m1 984.4 8.7
h # 0.369 136.9% 2
Qin m1
# 2643.1
#
(b) The mass flow rate of the steam entering the turbine, m1, can be determined using the given value for the net power out-
put, 100 MW. Since
# # #
Wcycle Wt Wp
and
# #
Wt Wp
# 984.4 kJ/kg and # 8.7 kJ/kg
m1 m1
it follows that
1100 MW2 3600 s/h 103 kJ/s
` ` 3.69 105 kg/h
#
m1
1984.4 8.72 kJ/kg 1 MW
Note that the fractions of the total flow at various locations are labeled on the figure.
8.4.2 Closed Feedwater Heaters

closed feedwater heater Regenerative feedwater heating also can be accomplished with closed feedwater heaters.
Closed heaters are shell-and-tube-type recuperators in which the feedwater temperature in-
creases as the extracted steam condenses on the outside of the tubes carrying the feedwater.
Since the two streams do not mix, they can be at different pressures. The diagrams of Fig. 8.10
show two different schemes for removing the condensate from closed feedwater heaters. In
Fig. 8.10a, this is accomplished by means of a pump whose function is to pump the con-
densate forward to a higher-pressure point in the cycle. In Fig. 8.10b, the condensate is al-
lowed to pass through a trap into a feedwater heater operating at a lower pressure or into the
condenser. A trap is a type of valve that permits only liquid to pass through to a region of
lower pressure.
A regenerative vapor power cycle having one closed feedwater heater with the condensate
trapped into the condenser is shown schematically in Fig. 8.11. For this cycle, the working
fluid passes isentropically through the turbine stages and pumps, and there are no pressure
drops accompanying the flow through the other components. The Ts diagram shows the
principal states of the cycle. The total steam flow expands through the first-stage turbine from
state 1 to state 2. At this location, a fraction of the flow is bled into the closed feedwater
heater, where it condenses. Saturated liquid at the extraction pressure exits the feedwater
heater at state 7. The condensate is then trapped into the condenser, where it is reunited with
Extraction steam
Extraction steam
Feedwater Feedwater
out in
Condensate Condensate Steam trap

Pump
To higher To lower-
pressure line pressure heater
or condenser
(a) (b)
Figure 8.10 Examples of closed feedwater heaters.

Qin
(1 y)
(1)
Wt
1
T
2 3 1
(1 y)
(y)
Steam
generator Condenser Qout
(1) (1) 2
7
Pump
6
4
6 5
Closed 5
Wp
feedwater 4 8 3
heater Trap (y)
7 8
(y) s
Figure 8.11 Regenerative vapor power cycle with one closed feedwater heater.
the portion of the total flow passing through the second-stage turbine. The expansion from
state 7 to state 8 through the trap is irreversible, so it is shown by a dashed line on the Ts
diagram. The total flow exiting the condenser as saturated liquid at state 4 is pumped to the
steam generator pressure and enters the feedwater heater at state 5. The temperature of the
feedwater is increased in passing through the feedwater heater. The feedwater then exits at
state 6. The cycle is completed as the working fluid is heated in the steam generator at con-
stant pressure from state 6 to state 1. Although the closed heater shown on the figure oper-
ates with no pressure drop in either stream, there is a source of irreversibility due to the
stream-to-stream temperature differences.
CYCLE ANALYSIS. The schematic diagram of the cycle shown in Fig. 8.11 is labeled with
the fractions of the total flow at various locations. This is usually helpful in analyzing such
cycles. The fraction of the total flow extracted, y, can be determined by applying the con-
servation of mass and conservation of energy principles to a control volume around the closed
heater. Assuming no heat transfer between the feedwater heater and its surroundings and ne-
glecting kinetic and potential energy effects, the mass and energy rate balances reduce at
steady state to give
0 y 1h2 h7 2
1h5 h6 2
Solving for y
h6 h5
y (8.17)
h2 h7
The principal work and heat transfers are evaluated as discussed previously.
8.4.3 Multiple Feedwater Heaters

The thermal efficiency of the regenerative cycle can be increased by incorporating several
feedwater heaters at suitably chosen pressures. The number of feedwater heaters used is based
on economic considerations, since incremental increases in thermal efficiency achieved with
each additional heater must justify the added capital costs (heater, piping, pumps, etc.). Power
5
Steam
generator
4
Qin
1
Wt
2 3
6 7
8
Condenser
21 Qout
Closed Closed Closed

heater 14 heater Deaerating 11 heater
open
heater
13 12 10 9 20
Wp2 Wp1
15 16 19
17 Main boiler Condensate
18 feed pump pump
Figure 8.12 Example of a power plant layout.
plant designers use computer programs to simulate the thermodynamic and economic per-
formance of different designs to help them decide on the number of heaters to use, the types
of heaters, and the pressures at which they should operate.
Figure 8.12 shows the layout of a power plant with three closed feedwater heaters and
one open heater. Power plants with multiple feedwater heaters ordinarily have at least one
open feedwater heater operating at a pressure greater than atmospheric pressure so that oxygen
deaeration and other dissolved gases can be vented from the cycle. This procedure, known as deaeration,
is needed to maintain the purity of the working fluid in order to minimize corrosion. Actual
power plants have many of the same basic features as the one shown in the figure.
In analyzing regenerative vapor power cycles with multiple feedwater heaters, it is good
practice to base the analysis on a unit of mass entering the first-stage turbine. To clarify the
quantities of matter flowing through the various plant components, the fractions of the total
flow removed at each extraction point and the fraction of the total flow remaining at each
state point in the cycle should be labeled on a schematic diagram of the cycle. The fractions
extracted are determined from mass and energy rate balances for control volumes around each
of the feedwater heaters, starting with the highest-pressure heater and proceeding to each
lower-pressure heater in turn. This procedure is used in the next example that involves a
reheatregenerative vapor power cycle with two feedwater heaters, one open feedwater heater
and one closed feedwater heater.
EXAMPLE 8.6 ReheatRegenerative Cycle with Two Feedwater Heaters
Consider a reheatregenerative vapor power cycle with two feedwater heaters, a closed feedwater heater and an open feed-
water heater. Steam enters the first turbine at 8.0 MPa, 480C and expands to 0.7 MPa. The steam is reheated to 440C be-
fore entering the second turbine, where it expands to the condenser pressure of 0.008 MPa. Steam is extracted from the first
turbine at 2 MPa and fed to the closed feedwater heater. Feedwater leaves the closed heater at 205C and 8.0 MPa, and con-
densate exits as saturated liquid at 2 MPa. The condensate is trapped into the open feedwater heater. Steam extracted from
the second turbine at 0.3 MPa is also fed into the open feedwater heater, which operates at 0.3 MPa. The stream exiting the
open feedwater heater is saturated liquid at 0.3 MPa. The net power output of the cycle is 100 MW. There is no stray heat
transfer from any component to its surroundings. If the working fluid experiences no irreversibilities as it passes through the
turbines, pumps, steam generator, reheater, and condenser, determine (a) the thermal efficiency, (b) the mass flow rate of the
steam entering the first turbine, in kg/h.
SOLUTION
Known: A reheatregenerative vapor power cycle operates with steam as the working fluid. Operating pressures and tem-
peratures are specified, and the net power output is given.
Find: Determine the thermal efficiency and the mass flow rate entering the first turbine, in kg/h.
T 1
T1 = 480C
4 T4 = 440C
8.0 MPa 2
11 12 2.0 MPa
10
0.7 MPa 3
5
9 13 0.3 MPa
8
0.008 MPa
T4 = 440C 7 6
4 s
Steam
generator (1 y) 3

Qin
(1)
1
Wt
T1 = 480C
2
5
6 (1 y' y'')
(y') (y'')
Condenser
0.008 MPa

Qout
Closed
(1) heater Open
heater
11 (1) 0.3 MPa
T11 = 205C 2.0 MPa
10 9 8 7

Wp1
12 13
Wp2
Pump 2 Pump 1
(y') Trap
Figure E8.6
Assumptions:
1. Each component in the cycle is analyzed as a control volume at steady state. The control volumes are shown on the
accompanying sketch by dashed lines.
2. There is no stray heat transfer from any component to its surroundings.
3. The working fluid undergoes internally reversible processes as it passes through the turbines, pumps, steam generator,
reheater, and condenser.
4. The expansion through the trap is a throttling process.
6. Condensate exits the closed heater as a saturated liquid at 2 MPa. Feedwater exits the open heater as a saturated liquid at
0.3 MPa. Condensate exits the condenser as a saturated liquid.
Analysis: Let us determine the specific enthalpies at the principal states of the cycle. State 1 is the same as in Example 8.3,
so h1 3348.4 kJ/kg and s1 6.6586 kJ/kg # K.
State 2 is fixed by p2 2.0 MPa and the specific entropy s2, which is the same as that of state 1. Interpolating in Table A-4,
we get h2 2963.5 kJ/kg. The state at the exit of the first turbine is the same as at the exit of the first turbine of Example 8.3, so
h3 2741.8 kJ/kg.
State 4 is superheated vapor at 0.7 MPa, 440C. From Table A-4, h4 3353.3 kJ/kg and s4 7.7571 kJ/kg # K. Interpo-
lating in Table A-4 at p5 0.3 MPa and s5 s4 7.7571 kJ/kg # K, the enthalpy at state 5 is h5 3101.5 kJ/kg.
Using s6 s4, the quality at state 6 is found to be x6 0.9382. So
h6 hf
x6 hfg
173.88
10.938222403.1 2428.5 kJ/kg
At the condenser exit, h7 173.88 kJ/kg. The specific enthalpy at the exit of the first pump is
h8 h7
v7 1 p8 p7 2
173.88
11.0084210.3 0.0082 174.17 kJ/kg
The required unit conversions were considered in previous examples.
The liquid leaving the open feedwater heater at state 9 is saturated liquid at 0.3 MPa. The specific enthalpy is h9 561.47
kJ/kg. The specific enthalpy at the exit of the second pump is
h10 h9
v9 1 p10 p9 2
561.47
11.0732218.0 0.32 569.73 kJ/kg
The condensate leaving the closed heater is saturated at 2 MPa. From Table A-3, h12 908.79 kJ/kg. The fluid passing
through the trap undergoes a throttling process, so h13 908.79 kJ/kg.
The specific enthalpy of the feedwater exiting the closed heater at 8.0 MPa and 205C is found using Eq. 3.13 as
h11 hf
vf 1 p11 psat 2
875.1
11.1646218.0 1.732 882.4 kJ/kg
where hf and vf are the saturated liquid specific enthalpy and specific volume at 205C, respectively, and psat is the saturation
pressure in MPa at this temperature. Alternatively, h 11 can be found from Table A-5.
The schematic diagram of the cycle is labeled with the fractions of the total flow into the turbine that remain at various
locations. The fractions of the total flow diverted to the closed heater and open heater, respectively, are y m2 m1 and
# #
y m5 m1, where m1 denotes the mass flow rate entering the first turbine.
# # #
The fraction y can be determined by application of mass and energy rate balances to a control volume enclosing the closed
heater. The result is
h11 h10 882.4 569.73
y 0.1522
h2 h12 2963.5 908.79
The fraction y can be determined by application of mass and energy rate balances to a control volume enclosing the open
heater, resulting in
0 yh5
11 y y 2h8
yh13 h9
Solving for y
11 y2h8
yh13 h9
y
h8 h5
10.84782174.17
10.15222908.79 561.47

174.17 3101.5
0.0941
(a) The following work and heat transfer values are expressed on the basis of a unit mass entering the first turbine. The work
developed by the first turbine per unit of mass entering is the sum
#
# 1h1 h2 2
11 y21h2 h3 2
Wt1
m1
13348.4 2963.52
10.8478212963.5 2741.82
572.9 kJ/kg
Similarly, for the second turbine
#
# 11 y21h4 h5 2
11 y y 21h5 h6 2
Wt2
m1
10.8478213353.3 3101.52
10.7537213101.5 2428.52
720.7 kJ/kg
For the first pump #
Wp1
# 11 y y 21h8 h7 2
m1
10.753721174.17 173.882 0.22 kJ/kg
and for the second pump #
Wp2
# 1h10 h9 2
m1
569.73 561.47 8.26 kJ/kg
The total heat added is the sum of the energy added by heat transfer during boiling/superheating and reheating. When
expressed on the basis of a unit of mass entering the first turbine, this is
#
# 1h1 h11 2
11 y21h4 h3 2
Qin
m1
13348.4 882.42
10.8478213353.3 2741.82
2984.4 kJ/kg
With the foregoing values, the thermal efficiency is
# # # #
Wt1m1
Wt2m1 Wp1m1 Wp2 m1
# # # #
h #
Qinm1
#
572.9
720.7 0.22 8.26
0.431 143.1% 2
2984.4
(b) The mass flow rate entering the first turbine can be determined using the given value of the net power output. Thus
#
# Wcycle
m1 # # # #
Wt1m1
Wt2m1 Wp1m1 Wp2 m1
# # # #
1100 MW2 3600 s/h 103 kW/MW

2.8 105 kg / h
1285.1 kJ/kg
Compared to the corresponding values determined for the simple Rankine cycle of Example 8.1, the thermal efficiency of
the present regenerative cycle is substantially greater and the mass flow rate is considerably less.
8.5 Other Vapor Cycle Aspects

In this section we consider aspects of vapor cycles related to working fluid characteristics,
binary vapor cycles, and cogeneration systems.
WORKING FLUID CHARACTERISTICS. Water is used as the working fluid in the vast majority
of vapor power systems because it is plentiful and low in cost, nontoxic, chemically stable, and
relatively noncorrosive. In addition, water has a relatively large change in specific enthalpy
when it vaporizes at ordinary steam generator pressures, which tends to limit the mass flow
rate for a desired power plant output. The properties of liquid water and water vapor are also
such that the back work ratios achieved are characteristically quite low, and the techniques of
superheat, reheat, and regeneration can be effective for increasing power plant efficiencies.
Water is less satisfactory insofar as some other desirable working fluid characteristics
are concerned. For example, the critical temperature of water is only 374.14C, which
is about 225C below the maximum allowable turbine inlet temperatures. Accordingly,
to achieve a high average temperature of heat addition and realize the attendant higher
thermal efficiency, it may be necessary for the steam generator to operate at supercritical
pressures. This requires costly piping and heat exchanger tubes capable of withstanding great
stresses. Another undesirable characteristic of water is that its saturation pressure at ordinary
condenser temperatures is well below atmospheric pressure. As a result, air can leak into the
system, necessitating the use of special ejector pumps attached to the condenser or deaera-
ting feedwater heaters to remove the air.
Although water has some shortcomings as a working fluid, no other single working fluid
has been found that is more satisfactory overall for large electrical generating plants. Still,
vapor power cycles intended for special uses may employ working fluids that are better
matched to the application at hand than water. Cycles that operate at relatively low temper-
atures may perform best with a refrigerant such as ammonia as the working fluid. Power sys-
tems for high-temperature applications may employ substances having desirable performance
characteristics at these temperatures. Moreover, water may be used together with some other
substance in a binary vapor cycle to achieve better overall performance than could be real-
ized with water alone.
binary cycle BINARY VAPOR CYCLE. In a binary vapor power cycle two working fluids are used, one
with good high-temperature characteristics and another with good characteristics at the lower-
temperature end of the operating range. for example. . . Fig. 8.13 shows a schematic
diagram and an accompanying Ts diagram of a binary vapor cycle using water and a suitable
liquid metal, with each substance in both the liquid and vapor phases. In this arrangement,
two ideal Rankine cycles are combined, with the heat rejection from the high-temperature cy-
cle (the topping cycle) being used as the energy input for the low-temperature cycle. This
energy transfer is accomplished in an interconnecting heat exchanger, which serves as the
condenser for the metal cycle and the boiler for the water cycle. Since the increase in the spe-
cific enthalpy of the water as it passes through the heat exchanger is typically several times
the magnitude of the specific enthalpy decrease of the metal, several units of mass of metal
must circulate in the topping cycle for each unit of mass of water in the other cycle.
Binary vapor power cycles can operate with higher average temperatures of heat addition
than conventional cycles using water only and thus can attain higher thermal efficiencies.
However, the higher efficiencies achieved in this manner must justify the increased costs
related to the construction and operation of the more complex cycle arrangement.
COGENERATION. The binary cycle considered above is just one example of how systems
can be linked to obtain overall systems that utilize fuel more effectively. Other examples are
8.5 Other Vapor Cycle Aspects 357
a Water vapor
e Water cycle:
Wt 2
1 abcde
Turbine
Wt 1
Turbine
Steam Metal
condenser topping cycle:
2
b 12341
Steam superheater
and metal boiler T
1
Metal condenser
and steam boiler a
4
c 3 2
Liquid metal
3 e
d
d c b
s
Pump Pump
4
Figure 8.13 Watermetal binary vapor cycle.
discussed in Secs. 7.6 and 7.7, including the multiple-use strategy known as cogeneration. cogeneration
In each of the following two paragraphs we consider applications of cogeneration.
Direct combustion heating and the generation of process steam together account for a sub-
stantial portion of industrial energy resource use. But because the heat and steam are often
required at a relatively low temperature, good use is not made of the relatively high-
temperature products of combustion obtained by burning fuel. This source of inefficiency
can be reduced with a cogeneration arrangement in which fuel is consumed to produce both
electricity and steam (or heat), but with a total cost less than would be required to produce
them individually. A schematic of such a cogeneration system is shown in Fig. 8.14. The
figure is labeled with the fractions of the total flow entering the steam turbine that remain at
various locations. On the basis of a unit of mass entering the turbine at state 1, a fraction y
is extracted at an intermediate point 2 and diverted to some process that requires steam at

Wt
(1) (1 y)
1 Turbine 3
2
y
Steam
generator Condenser
System
requiring
process
Qin steam
y
Pump 2 Pump 1
6 5
Figure 8.14 Schematic
(1) (1 y) 4 of a cogeneration system in

Wp2 Wp1 which process steam is bled
from the turbine.
this condition. The remaining fraction, 1 y, expands to the turbine exit at state 3, producing
power in addition to that developed by the first turbine stage. Eventually this fraction rejoins
the amount extracted and the combined stream is returned to the steam generator. When no
process steam is required, all of the steam generated by the steam generator is allowed to
expand through the turbine.
Industries such as pulp and paper production and food processing, which require steam
for various processes in addition to electricity for operating machines, lighting, etc., are
particularly well suited for the use of cogeneration. Another cogeneration arrangement
district heating being used increasingly involves district heating. In this application a power plant is in-
tegrated into a community so that it provides electricity for industrial, commercial, and do-
mestic use together with steam for process needs, space heating, and domestic water heat-
ing. District heating is commonly used in northern Europe and is being increasingly used
in the United States.
8.6 Case Study: Exergy Accounting of a

Vapor Power Plant1
The discussions to this point show that a useful picture of power plant performance can be
obtained with the conservation of mass and conservation of energy principles. However,
these principles provide only the quantities of energy transferred to and from the plant and
do not consider the utility of the different types of energy transfer. For example, with the
conservation principles alone, a unit of energy exiting as generated electricity is regarded
as equivalent to a unit of energy exiting in relatively low-temperature cooling water, even
though the electricity has greater utility and economic value. Also, nothing can be learned
with the conservation principles alone about the relative significance of the irreversibilities
present in the various plant components and the losses associated with those components.
The method of exergy analysis introduced in Chap. 7 allows issues such as these to be dealt
with quantitatively.
EXERGY ACCOUNTING. In this section we account for the exergy entering a power plant
with the fuel. (Means for evaluating the fuel exergy are introduced in Sec. 13.6.) A portion
of the fuel exergy is ultimately returned to the plant surroundings as the net work developed.
However, the largest part is either destroyed by irreversibilities within the various plant com-
ponents or carried from the plant by the cooling water, stack gases, and unavoidable heat
transfers with the surroundings. These considerations are illustrated in the present section by
three solved examples, treating respectively the boiler, turbine and pump, and condenser of
a simple vapor power plant.
The irreversibilities present in each power plant component exact a tariff on the ex-
ergy supplied to the plant, as measured by the exergy destroyed in that component. The
component levying the greatest tariff is the boiler, for a significant portion of the exergy
entering the plant with the fuel is destroyed by irreversibilities within it. There are two
main sources of irreversibility in the boiler: (1) the irreversible heat transfer occurring be-
tween the hot combustion gases and the working fluid of the vapor power cycle flowing
through the boiler tubes, and (2) the combustion process itself. To simplify the present
discussion, the boiler is considered to consist of a combustor unit in which fuel and air
are burned to produce hot combustion gases, followed by a heat exchanger unit where the
cycle working fluid is vaporized as the hot gases cool. This idealization is illustrated in
Fig. 8.15.
1
Chapter 7 is a prerequisite for the study of this section.
8.6 Case Study: Exergy Accounting of a Vapor Power Plant 359
Exiting stack gases
Combustor Heat exchanger unit

unit
Hot combustion
Fuel products
Air
Cycle working
fluid
Pump Turbine
Net power out
Condenser
Figure 8.15 Power
Cooling Cooling plant schematic for the
water in water out exergy analysis case study.
For the purposes of illustration, let us assume that 30% of the exergy entering the com-
bustion unit with the fuel is destroyed by the combustion irreversibility and 1% of the fuel
exergy exits the heat exchanger unit with the stack gases. The corresponding values for an
actual power plant might differ from these nominal values. However, they provide charac-
teristic values for discussion. (Means for evaluating the combustion exergy destruction and
the exergy accompanying the exiting stack gases are introduced in Chap. 13.) Using the fore-
going values for the combustion exergy destruction and stack gas loss, it follows that a maxi-
mum of 69% of the fuel exergy remains for transfer from the hot combustion gases to the
cycle working fluid. It is from this portion of the fuel exergy that the net work developed by
the plant is obtained. In Examples 8.7 through 8.9, we account for the exergy supplied by
the hot combustion gases passing through the heat exchanger unit. The principal results of
this series of examples are reported in Table 8.1. Carefully note that the values of Table 8.1
are keyed to the vapor power plant of Example 8.2 and thus have only qualitative signifi-
cance for vapor power plants in general.
CASE STUDY CONCLUSIONS. The entries of Table 8.1 suggest some general observa-
tions about vapor power plant performance. First, the table shows that the exergy destruc-
tions are more significant than the plant losses. The largest portion of the exergy entering
the plant with the fuel is destroyed, with exergy destruction in the boiler overshadowing
all others. By contrast, the loss associated with heat transfer to the cooling water is rela-
tively unimportant. The cycle thermal efficiency (calculated in the solution to Ex. 8.2) is
31.4%, so over two-thirds (68.6%) of the energy supplied to the cycle working fluid is
subsequently carried out by the condenser cooling water. By comparison, the amount of
exergy carried out is virtually negligible because the temperature of the cooling water is
raised only a few degrees over that of the surroundings and thus has limited utility. The
loss amounts to only 1% of the exergy entering the plant with the fuel. Similarly, losses
accompanying unavoidable heat transfer with the surroundings and the exiting stack gases
typically amount only to a few percent of the exergy entering the plant with the fuel and
are generally overstated when considered from the perspective of conservation of energy
alone.
TABLE 8.1 Vapor Power Plant Exergy Accountinga

Outputs
Net power outb 30%
Losses
Condenser cooling waterc 1%
Stack gases (assumed) 1%
Exergy Destruction
Boiler
Combustion unit (assumed) 30%
Heat exchanger unitd 30%
Turbinee 5%
Pump f
Condenser g 3%
Total 100%
a c
All values are expressed as a percentage of Example 8.9.
the exergy carried into the plant with the fuel. d
Example 8.7.
Values are rounded to the nearest full percent. e
Example 8.8.
Exergy losses associated with stray heat trans-
f
fer from plant components are ignored. Example 8.8.
b g
Example 8.8 Example 8.9.
An exergy analysis allows the sites where destructions or losses occur to be identified and
rank ordered for significance. This knowledge is useful in directing attention to aspects of
plant performance that offer the greatest opportunities for improvement through the applica-
tion of practical engineering measures. However, the decision to adopt any particular modi-
fication is governed by economic considerations that take into account both economies in
fuel use and the costs incurred to achieve those economies.
The calculations presented in the following examples illustrate the application of exergy
principles through the analysis of a simple vapor power plant. There are no fundamental dif-
ficulties, however, in applying the methodology to actual power plants, including consider-
ation of the combustion process. The same procedures also can be used for exergy accounting
of the gas turbine power plants considered in Chap. 9 and other types of thermal systems.
The following example illustrates the exergy analysis of the heat exchanger unit of the
boiler of the case study vapor power plant.
EXAMPLE 8.7 Cycle Exergy AnalysisHeat Exchanger Unit
The heat exchanger unit of the boiler of Example 8.2 has a stream of water entering as a liquid at 8.0 MPa and exiting as a satu-
rated vapor at 8.0 MPa. In a separate stream, gaseous products of combustion cool at a constant pressure of 1 atm from 1107 to
547C. The gaseous stream can be modeled as air as an ideal gas. Let T0 22C, p0 1 atm. Determine (a) the net rate at which
exergy is carried into the heat exchanger unit by the gas stream, in MW, (b) the net rate at which exergy is carried from the heat
exchanger by the water stream, in MW, (c) the rate of exergy destruction, in MW, (d) the exergetic efficiency given by Eq. 7.45.
SOLUTION
Known: A heat exchanger at steady state has a water stream entering and exiting at known states and a separate gas stream
entering and exiting at known states.
Find: Determine the net rate at which exergy is carried into the heat exchanger by the gas stream, in MW, the net rate at
which exergy is carried from the heat exchanger by the water stream, in MW, the rate of exergy destruction, in MW, and the
exergetic efficiency.
547C, e Air i 1107C,

1 atm 1 atm
Liquid, 4 1 Steam
8.0 MPa saturated vapor,
8.0 MPa
Figure E8.7
Assumptions:
# #
1. The control volume shown in the accompanying figure operates at steady state with Qcv Wcv 0.
2. Kinetic and potential energy effects can be ignored.
3. The gaseous combustion products are modeled as air as an ideal gas.
4. The air and the water each pass through the steam generator at constant pressure.
5. Only 69% of the exergy entering the plant with the fuel remains after accounting for the stack loss and combustion exergy
destruction.
6. T0 22C, p0 1 atm.
Analysis: The analysis begins by evaluating the mass flow rate of the air in terms of the mass flow rate of the water. The
air and water pass through the boiler in separate streams. Hence, at steady state the conservation of mass principle requires
1air2
# #
mi me
1water2
# #
m4 m1
Using these relations, an energy rate balance for the overall control volume reduces a steady state to
0 Qcv Wcv
ma 1hi he 2
m 1h4 h1 2
# 0 # 0 # #
# #
where Qcv Wcv 0 by assumption 1, and the kinetic and potential energy terms are dropped by assumption 2. In this equa-
# #
tion ma and m denote, respectively, the mass flow rates of the air and water. On solving
#
ma h1 h4
#
m hi he
The solution to Example 8.2 gives h1 2758 kJ/kg and h4 183.36 kJ/kg. From Table A-22, hi 1491.44 kJ/kg and he
843.98 kJ/kg. Hence
kg 1air2
#
ma 2758 183.36
# 3.977
m 1491.44 843.98 kg 1steam2
# #
From Example 8.2, m 4.449 10 kg/h. Thus, ma 17.694 10 kg/h.
5 5
(a) The net rate at which exergy is carried into the heat exchanger unit by the gaseous stream can be evaluated using Eq. 7.36
net rate at which exergy

is carried in by the ma 1e fi efe 2
#
gaseous stream
mahi he T0 1si se 2
#
Since the gas pressure remains constant, Eq. 6.21a giving the change in specific entropy of an ideal gas reduces to si se
si se. Thus, with h and s values from Table A-22
ma 1efi efe 2 117.694 105 kg/h2 11491.44 843.982 kJ/kg 1295 K213.34474 2.745042 kJ/kg # K
#
8.326 108 kJ/h 1 MW

` 3 ` 231.28 MW
3600 s/ h 10 kJ/s
(b) The net rate at which exergy is carried out of the boiler by the water stream is determined similarly
is carried out by the m 1e f1 ef4 2
#
water stream
m h1 h4 T0 1s1 s4 2
#
From Table A-3, s1 5.7432 kJ/kg # K. Double interpolation in Table A-5 at 8.0 MPa and h4 183.36 kJ/kg gives s4
0.5957 kJ/kg # K. Substituting known values
m 1ef1 ef4 2 14.449 105 212758 183.362 29515.7432 0.59572
#
4.699 108 kJ/h 1 MW

` 3 ` 130.53 MW
3600 s / h 10 kJ/s
(c) The rate of exergy destruction can be evaluated by reducing the exergy rate balance to obtain
Ed ma 1efi efe 2
m1ef4 ef1 2
#
# #
With the results of parts (a) and (b)

#
Ed 231.28 MW 130.53 MW 100.75 MW
(d) The exergetic efficiency given by Eq. 7.45 is
m 1ef1 ef4 2
#
0.564 156.4% 2
130.53 MW
e #
ma 1efi efe 2 231.28 MW
This calculation indicates that 43.6% of the exergy supplied to the heat exchanger unit by the cooling combustion prod-
ucts is destroyed. However, since only 69% of the exergy entering the plant with the fuel is assumed to remain after the stack
loss and combustion exergy destruction are accounted for (assumption 5), it can be concluded that 0.69 43.6% 30% of
the exergy entering the plant with the fuel is destroyed within the heat exchanger. This is the value listed in Table 8.1.
Since energy is conserved, the rate at which energy is transferred to the water as it flows through the heat exchanger equals
the rate at which energy is transferred from the cooling gas passing through the heat exchanger. By contrast, the decrease
in exergy of the gas as it passes through the heat exchanger exceeds the increase in the exergy of the water by the amount
of exergy destroyed.

#
The rate of exergy destruction can be determined alternatively
# by evaluating the rate of entropy production, scv, from an
#
entropy rate balance and multiplying by T0 to obtain Ed T0 scv.
Underlying the assumption that each stream passes through the heat exchanger at constant pressure is the neglect of fric-
tion as an irreversibility. Thus, the only contributor to exergy destruction in this case is heat transfer from the higher-
temperature combustion products to the vaporizing water.
In the next example, we determine the exergy destruction rates in the turbine and pump
of the case study vapor power plant.
EXAMPLE 8.8 Cycle Exergy AnalysisTurbine and Pump
Reconsider the turbine and pump of Example 8.2. Determine for each of these components the rate at which exergy is de-
stroyed, in MW. Express each result as a percentage of the exergy entering the plant with the fuel. Let T0 22C, p0 1 atm.
SOLUTION
Known: A vapor power cycle operates with steam as the working fluid. The turbine and pump each has an isentropic effi-
ciency of 85%.
Find: For the turbine and the pump individually, determine the rate at which exergy is destroyed, in MW. Express each result
as a percentage of the exergy entering the plant with the fuel.
Boiler p1 =
8.0 MPa
Wt
Q in Turbine
1
Saturated
vapor T
2
Condenser 8.0 MPa

1
Q out
4
Cooling
water
4s
Pump 0.008 MPa
3 2s 2
4 3 Saturated
liquid at
0.008 MPa s
Wp
Figure E8.8
Assumptions:
1. The turbine and the pump can each be analyzed as a control volume at steady state.
2. The turbine and pump operate adiabatically and each has an efficiency of 85%.
4. Only 69% of the exergy entering the plant with the fuel remains after accounting for the stack loss and combustion exergy
destruction.
5. T0 22C, p0 1 atm.
Analysis:
# The rate of exergy destruction can be found by reducing the exergy rate balance or by use of the relationship
# #
Ed T0 scv, where scv is the rate of entropy production from an entropy rate balance. With either approach, the rate of ex-
ergy destruction for the turbine can be expressed as
Ed mT0 1s2 s1 2
# #
From Table A-3, s1 5.7432 kJ/kg # K. Using h2 1939.3 kJ/kg from the solution to Example 8.2, the value of s2 can be
determined from Table A-3 as s2 6.2021 kJ/kg # K. Substituting values
Ed 14.449 105 kg/h21295 K216.2021 5.743221kJ/ kg # K2
#
a0.602 108 b` ` ` ` 16.72 MW

kJ 1h 1 MW
h 3600 s 103 kJ/s
From the solution to Example 8.7, the net rate at which exergy is supplied by the cooling combustion gases is 231.28 MW.
The turbine rate of exergy destruction expressed as a percentage of this is (16.72231.28)(100%) 7.23%. However, since
only 69% of the entering fuel exergy remains after the stack loss and combustion exergy destruction are accounted for, it can
be concluded that 0.69 7.23% 5% of the exergy entering the plant with the fuel is destroyed within the turbine. This is
the value listed in Table 8.1.
Similarly, the exergy destruction rate for the pump is
Ed mT0 1s4 s3 2
# #
With s3 from Table A-3 and s4 from the solution to Example 8.7
Ed 14.449 105 kg/h21295 K210.5957 0.592621kJ/kg # K2
#
a4.07 105 b` ` ` 3 ` 0.11 MW

kJ 1h 1 MW
h 3600 s 10 kJ/s
Expressing this as a percentage of the exergy entering the plant as calculated above, we have (0.11231.28)(69%) 0.03%.
This value is rounded to zero in Table 8.1.
The net power output of the vapor power plant of Example 8.2 is 100 MW. Expressing this as a percentage of the rate at
which exergy is carried into the plant with the fuel, (100231.28)(69%) 30%, as shown in Table 8.1.
The following example illustrates the exergy analysis of the condenser of the case study
vapor power plant.
EXAMPLE 8.9 Cycle Exergy AnalysisCondenser
The condenser of Example 8.2 involves two separate water streams. In one stream a two-phase liquidvapor mixture enters
at 0.008 MPa and exits as a saturated liquid at 0.008 MPa. In the other stream, cooling water enters at 15C and exits at 35C.
(a) Determine the net rate at which exergy is carried from the condenser by the cooling water, in MW. Express this result as
a percentage of the exergy entering the plant with the fuel. (b) Determine for the condenser the rate of exergy destruction, in
MW. Express this result as a percentage of the exergy entering the plant with the fuel. Let T0 22C and p0 1 atm.
SOLUTION
Known: A condenser at steady state has two streams: (1) a two-phase liquidvapor mixture entering and condensate exiting
at known states and (2) a separate cooling water stream entering and exiting at known temperatures.
Find: Determine the net rate at which exergy is carried from the condenser by the cooling water stream and the rate of ex-
ergy destruction for the condenser. Express both quantities in MW and as percentages of the exergy entering the plant with
the fuel.
Saturated 3 2 Two-phase
liquid, liquid-vapor mixture,
0.008 MPa 0.008 MPa
i e
Liquid, Liquid,
15C 35C
Figure E8.9
Assumptions:
# #
1. The control volume shown on the accompanying figure operates at steady state with Qcv Wcv 0.
3. Only 69% of the fuel exergy remains after accounting for the stack loss and combustion exergy destruction.
4. T0 22C, p0 1 atm.
Analysis:
(a) The net rate at which exergy is carried out of the condenser can be evaluated by using Eq. 7.36:

is carried out by the mcw 1e fe efi 2
#
cooling water
mcwhe hi T0 1se si 2
#
#
where mcw is the mass flow rate of the cooling water from the solution to Example 8.2. With saturated liquid values for spe-
cific enthalpy and entropy from Table A-2 at the specified inlet and exit temperatures of the cooling water
mcw 1efe efi 2 19.39 106 kg/h2 1146.68 62.992 kJ/kg 1295 K210.5053 0.22452 kJ/kg # K
#
8.019 106 kJ/h 1 MW

` 3 ` 2.23 MW
3600 s/h 10 kJ/s
Expressing this as a percentage of the exergy entering the plant with the fuel, we get (2.23231.28)(69%) 1%. This is the
value listed in Table 8.1.
(b) The rate #of exergy destruction for the condenser can be evaluated by reducing the exergy rate balance. Alternatively, the
# #
relationship Ed T0scv can be employed, where scv is the time rate of entropy production for the condenser determined from
an entropy rate balance. With either approach, the rate of exergy destruction can be expressed as
Ed T0 m 1s3 s2 2
mcw 1se si 2
# # #
Substituting values
Ed 29514.449 105 210.5926 6.20212

19.39 106 210.5053 0.22452
#
416.1 105 kJ/h 1 MW

` 3 ` 11.56 MW
3600 s/h 10 kJ/s
Expressing this as a percentage of the exergy entering the plant with the fuel, we get (11.56231.28)(69%) 3%. This is the
value listed in Table 8.1.
The cycle thermal efficiency evaluated in the solution to Example 8.2 is 31.4%. Thus, it can be concluded that over two-
thirds (68.6%) of the energy supplied by the cooling combustion gas to the cycle working fluid is subsequently carried out
by the condenser cooling water. However, the amount of exergy carried out with the cooling water is relatively minor be-
cause the temperature of the water is raised only a few degrees over that of the surroundings.
In this chapter we have considered practical arrangements for related concepts. The subset of key concepts listed below
vapor power plants producing a net power output from a fos- is particularly important.
sil fuel, nuclear, or solar input. We have illustrated how vapor sketch schematic diagrams and accompanying Ts dia-
power plants are modeled thermodynamically and considered grams of Rankine, reheat, and regenerative vapor power
the principal irreversibilities and losses associated with such cycles.
plants. The main components of simple vapor power plants
apply conservation of mass and energy, the second law,
are modeled by the Rankine cycle. In this chapter, we also
have introduced modifications to the simple vapor power cycle and property data to determine power cycle performance,
aimed at improving overall performance. These include su- including thermal efficiency, net power output, and mass
perheat, reheat, regeneration, supercritical operation, cogen- flow rates.
eration, and binary cycles. We have also included a case study discuss the effects on Rankine cycle performance of
to illustrate the application of exergy analysis to vapor power varying steam generator pressure, condenser pressure,
plants. and turbine inlet temperature.
The following checklist provides a study guide for this discuss the principal sources of exergy destruction and
chapter. When your study of the text and end-of-chapter ex- loss in vapor power plants.
ercises has been completed you should be able to
write out the meanings of the terms listed in the margin
throughout the chapter and understand each of the
Rankine cycle p. 327 back work ratio p. 329 reheat p. 340 cogeneration p. 357
thermal efficiency p. 328 superheat p. 340 regeneration p. 346
1. Do you know what kinds of power plants (coal-fired, hydro- plant is ultimately rejected to cooling water flowing through the
electric, nuclear, etc.) generate the electricity provided by your condenser. Is the heat rejected an indicator of the inefficiency of
local utility company? the power plant?
2. Referring to your monthly electric bill, determine how much 8. Brainstorm some ways to use the cooling water exiting the
you pay per kW # h of electricity. condenser of a large power plant.
3. Might the thermal efficiency of a vapor power plant be 9. What effects on a rivers ecology might result from a power
different in the winter than in the summer? plants use of river water for condenser cooling?
4. Power plants located in arid areas may accomplish condensa- 10. Referring to Fig. 8.1, what environmental impacts might
tion by air cooling instead of cooling with water flowing through result from the two plumes shown on the figure?
the condenser. How might air cooling affect the thermal 11. Referring to Example 8.5, what are the principal sources of
efficiency? internal irreversibility?
5. Is the Carnot vapor power cycle a suitable model for the sim- 12. Why is water the most commonly used working fluid in vapor
ple vapor power plant? power plants?
6. Keeping states 1 and 2 fixed, how would Fig. 8.6 be modified 13. What do you think about using solar energy to generate
if the frictional pressure drops through the boiler and condenser electric power?
were considered?
7. Based on thermal efficiency, approximately two-thirds of the
energy input by heat transfer in the steam generator of a power
Analyzing Rankine Cycles (a) the thermal efficiency.

8.1 Water is the working fluid in an ideal Rankine cycle. The (b) the back work ratio.
condenser pressure is 8 kPa, and saturated vapor enters the tur- (c) the heat transfer to the working fluid per unit mass pass-
bine at (a) 18 MPa and (b) 4 MPa. The net power output of ing through the boiler, in kJ/kg.
the cycle is 100 MW. Determine for each case the mass flow (d) the heat transfer from the working fluid per unit mass pass-
rate of steam, in kg /h, the heat transfer rates for the working ing through the condenser, in kJ/kg.
fluid passing through the boiler and condenser, each in kW, (e) Compare the results of parts (a)(d), with the correspon-
and the thermal efficiency. ding values of Example 8.1, and comment.
8.2 Water is the working fluid in an ideal Rankine cycle. Su- 8.4 Plot each of the quantities calculated in Problem 8.2 versus
perheated vapor enters the turbine at 8 MPa, 480C. The con- condenser pressure ranging from 6 kPa to 0.1 MPa. Discuss.
denser pressure is 8 kPa. The net power output of the cycle is 8.5 Plot each of the quantities calculated in Problem 8.2 versus
100 MW. Determine for the cycle steam generator pressure ranging from 4 MPa to 24 MPa.
(a) the rate of heat transfer to the working fluid passing Maintain the turbine inlet temperature at 480C. Discuss.
through the steam generator, in kW. 8.6 Water is the working fluid in an ideal Rankine cycle. Sat-
(b) the thermal efficiency. urated vapor enters the turbine at 18 MPa. The condenser pres-
(c) the mass flow rate of condenser cooling water, in kg/h, if sure is 6 kPa. Determine
the cooling water enters the condenser at 15C and exits (a) the net work per unit mass of steam flowing, in kJ/kg.
at 35C with negligible pressure change. (b) the heat transfer to the steam passing through the boiler,
8.3 Water is the working fluid in a Carnot vapor power cycle. in kJ per kg of steam flowing.
Saturated liquid enters the boiler at a pressure of 8 MPa, and (c) the thermal efficiency.
saturated vapor enters the turbine. The condenser pressure is (d) the heat transfer to cooling water passing through the con-
8 kPa. Determine denser, in kJ per kg of steam condensed.
8.7 Water is the working fluid in a Carnot vapor power cycle. (a) 90%, (b) 80%, (c) 70%. Answer the same questions for the
Saturated liquid enters the boiler at a pressure of 18 MPa, and modified cycle as in Problem 8.8.
saturated vapor enters the turbine. The condenser pressure is 8.15 Superheated steam at 8 MPa and 480C leaves the steam
6 kPa. Determine generator of a vapor power plant. Heat transfer and frictional
(a) the thermal efficiency. effects in the line connecting the steam generator and the tur-
(b) the back work ratio. bine reduce the pressure and temperature at the turbine inlet
(c) the net work of the cycle per unit mass of water flowing, to 7.6 MPa and 440C, respectively. The pressure at the exit
in kJ/kg. of the turbine is 10 kPa, and the turbine operates adiabatically.
(d) the heat transfer from the working fluid passing through Liquid leaves the condenser at 8 kPa, 36C. The pressure is in-
the condenser, in kJ per kg of steam flowing. creased to 8.6 MPa across the pump. The turbine and pump
(e) Compare the results of parts (a)(d) with those of Problem isentropic efficiencies are 88%. The mass flow rate of steam
8.6, respectively, and comment. is 79.53 kg/s. Determine
8.8 Plot each of the quantities calculated in Problem 8.6 versus (a) the net power output, in kW.
turbine inlet temperature ranging from the saturation temper- (b) the thermal efficiency.
ature at 18 MPa to 560C. Discuss. (c) the rate of heat transfer from the line connecting the steam
8.9 A power plant based on the Rankine cycle is under generator and the turbine, in kW.
development to provide a net power output of 10 MW. Solar (d) the mass flow rate of condenser cooling water, in kg/s, if
collectors are to be used to generate Refrigerant 22 vapor at the cooling water enters at 15C and exits at 35C with
1.6 MPa, 50C, for expansion through the turbine. Cooling negligible pressure change.
water is available at 20C. Specify the preliminary design of 8.16 Superheated steam at 18 MPa, 560C, enters the turbine
the cycle and estimate the thermal efficiency and the refriger- of a vapor power plant. The pressure at the exit of the turbine
ant and cooling water flow rates, in kg/h. is 0.06 bar, and liquid leaves the condenser at 0.045 bar, 26C.
The pressure is increased to 18.2 MPa across the pump. The
8.10 Refrigerant 134a is the working fluid in a solar power plant
turbine and pump have isentropic efficiencies of 82 and 77%,
operating on a Rankine cycle. Saturated vapor at 60C enters
respectively. For the cycle, determine
the turbine, and the condenser operates at a pressure of 6 bar.
The rate of energy input to the collectors from solar radiation (a) the net work per unit mass of steam flow, in kJ/kg.
is 0.4 kW per m2 of collector surface area. Determine the min- (b) the heat transfer to steam passing through the boiler, in kJ
imum possible solar collector surface area, in m2, per kW of per kg of steam flowing.
power developed by the plant. (c) the thermal efficiency.
(d) the heat transfer to cooling water passing through the con-
8.11 The cycle of Problem 8.3 is modified to include the ef-
denser, in kJ per kg of steam condensed.
fects of irreversibilities in the adiabatic expansion and com-
pression processes. If the states at the turbine and pump inlets 8.17 In the preliminary design of a power plant, water is chosen
remain unchanged, repeat parts (a)(d) of Problem 8.3 for the as the working fluid and it is determined that the turbine inlet
modified Carnot cycle with t 0.80 and p 0.70. temperature may not exceed 520C. Based on expected cool-
ing water temperatures, the condenser is to operate at a pres-
8.12 Steam enters the turbine of a simple vapor power plant
sure of 0.06 bar. Determine the steam generator pressure
with a pressure of 10 MPa and temperature T, and expands
required if the isentropic turbine efficiency is 80% and the
adiabatically to 6 kPa. The isentropic turbine efficiency is 85%.
quality of steam at the turbine exit must be at least 90%.
Saturated liquid exits the condenser at 6 kPa and the isentropic
pump efficiency is 82%.
Considering Reheat and Supercritical Cycles
(a) For T 580C, determine the turbine exit quality and the
8.18 Steam at 10 MPa, 600C enters the first-stage turbine of
cycle thermal efficiency.
an ideal Rankine cycle with reheat. The steam leaving the
(b) Plot the quantities of part (a) versus T ranging from 580
reheat section of the steam generator is at 500C, and the con-
to 700C.
denser pressure is 6 kPa. If the quality at the exit of the second-
8.13 Reconsider the analysis of Problem 8.2, but include in the stage turbine is 90%, determine the cycle thermal efficiency.
analysis that the turbine and pump have isentropic efficiencies
8.19 The ideal Rankine cycle of Problem 8.2 is modified to in-
of 85 and 70%, respectively. Determine for the modified cycle
clude reheat. In the modified cycle, steam expands though the
(a) the thermal efficiency. first-stage turbine to 0.7 MPa and then is reheated to 480C.
(b) the mass flow rate of steam, in kg/h, for a net power out- If the net power output of the modified cycle is 100 MW,
put of 100 MW. determine for the modified cycle
(c) the mass flow rate of condenser cooling water, in kg/h, if
(a) the rate of heat transfer to the working fluid passing
the cooling water enters the condenser at 15C and exits
through the steam generator, in MW.
at 35C with negligible pressure change.
(b) the thermal efficiency.
8.14 Reconsider Problem 8.8, but include in the analysis that (c) the rate of heat transfer to cooling water passing through
the turbine and pump each have isentropic efficiencies of the condenser, in MW.
8.20 For the cycle of Problem 8.19, investigate the effects on 8.28 For the cycle of Problem 8.25, investigate the effects on cy-
cycle performance as the reheat pressure and final reheat tem- cle performance as the feedwater heater pressure takes on other
perature take on other values. Construct suitable plots and dis- values. Construct suitable plots and discuss. Assume that each
cuss. Reconsider the analysis assuming that the pump and each turbine stage and each pump has an isentropic efficiency of 80%.
turbine stage has an isentropic efficiency of 80%. 8.29 Modify the ideal Rankine cycle of Problem 8.6 to include
8.21 Steam at 32 MPa, 520C enters the first stage of a super- superheated vapor entering the first turbine stage at 18 MPa,
critical reheat cycle including three turbine stages. Steam ex- 560C, and one open feedwater heater operating at 1 MPa. Sat-
iting the first-stage turbine at pressure p is reheated at constant urated liquid exits the open feedwater heater at 1 MPa. Deter-
pressure to 440C, and steam exiting the second-stage turbine mine for the modified cycle
at 0.5 MPa is reheated at constant pressure to 360C. Each tur- (a) the net work, in kJ per kg of steam entering the first tur-
bine stage and the pump has an isentropic efficiency of 85%. bine stage.
The condenser pressure is 8 kPa. (b) the thermal efficiency.
(a) For p 4 MPa, determine the net work per unit mass of (c) the heat transfer to cooling water passing through the con-
steam flowing, in kJ/kg, and the thermal efficiency. denser, in kJ per kg of steam entering the first turbine stage.
(b) Plot the quantities of part (a) versus p ranging from 0.5 to 8.30 Reconsider the cycle of Problem 8.29, but include in the
10 MPa. analysis that each turbine stage and pump has an isentropic
efficiency of 85%.
8.22 An ideal Rankine cycle with reheat uses water as the work-
8.31 Modify the ideal Rankine cycle of Problem 8.2 to include
ing fluid. The conditions at the inlet to the first-stage turbine
one closed feedwater heater using extracted steam at 0.7 MPa.
are 14 MPa, 600C and the steam is reheated between the
Condensate drains from the feedwater heater as saturated liquid
turbine stages to 600C. For a condenser pressure of 6 kPa,
at 0.7 MPa and is trapped into the condenser. The feedwater
plot the cycle thermal efficiency versus reheat pressure for
leaves the heater at 8 MPa and a temperature equal to the satu-
pressures ranging from 2 to 12 MPa.
ration temperature at 0.7 MPa. Answer the same questions about
the modified cycle as in Problem 8.2 and discuss the results.
Analyzing Regenerative Cycles 8.32 For the cycle of Problem 8.31, investigate the effects on cy-
8.23 Modify the ideal Rankine cycle of Problem 8.2 to include cle performance as the extraction pressure takes on other values.
one open feedwater heater operating at 0.7 MPa. Saturated liq- Assume that condensate drains from the closed feedwater heater
uid exits the feedwater heater at 0.7 MPa. Answer the same as saturated liquid at the extraction pressure. Also, feedwater
questions about the modified cycle as in Problem 8.2 and leaves the heater at 8 MPa and a temperature equal to the satu-
discuss the results. ration temperature at the extraction pressure. Construct suitable
plots and discuss. Reconsider the analysis assuming that each
8.24 For the cycle of Problem 8.23, investigate the effects on turbine stage and the pump has an isentropic efficiency of 80%.
cycle performance as the feedwater heater pressure takes on
8.33 A power plant operates on a regenerative vapor power cycle
other values. Construct suitable plots and discuss. Reconsider
with one closed feedwater heater. Steam enters the first turbine
the analysis assuming that each turbine stage and each pump
stage at 120 bar, 520C and expands to 10 bar, where some of
has an isentropic efficiency of 80%.
the steam is extracted and diverted to a closed feedwater heater.
8.25 A power plant operates on a regenerative vapor power cy- Condensate exiting the feedwater heater as saturated liquid at
cle with one open feedwater heater. Steam enters the first tur- 10 bar passes through a trap into the condenser. The feedwater
bine stage at 12 MPa, 520C and expands to 1 MPa, where exits the heater at 120 bar with a temperature of 170C. The
some of the steam is extracted and diverted to the open feed- condenser pressure is 0.06 bar. For isentropic processes in each
water heater operating at 1 MPa. The remaining steam expands turbine stage and the pump, determine for the cycle (a) the
through the second turbine stage to the condenser pressure of thermal efficiency and (b) the mass flow rate into the first-stage
6 kPa. Saturated liquid exits the open feedwater heater at turbine, in kg/h, if the net power developed is 320 MW.
1 MPa. For isentropic processes in the turbines and pumps, de- 8.34 Reconsider the cycle of Problem 8.33, but include in the
termine for the cycle (a) the thermal efficiency and (b) the analysis that each turbine stage has an isentropic efficiency of
mass flow rate into the first turbine stage, in kg/h, for a net 82%. The pump efficiency remains 100%.
power output of 330 MW.
8.35 Modify the cycle of Problem 8.31 such that the saturated
8.26 Reconsider the cycle of Problem 8.25 as the feedwater liquid condensate from the feedwater heater at 0.7 MPa is
heater pressure takes on other values. Plot the thermal effi- pumped into the feedwater line rather than being trapped into
ciency and the rate of exergy destruction within the feedwater the condenser. Answer the same questions about the modified
heater, in kW, versus the feedwater heater pressure ranging cycle as in Problem 8.31. List advantages and disadvantages
from 0.5 to 10 MPa. Let T0 293 K. of each scheme for removing condensate from the closed feed-
8.27 Compare the results of Problem 8.25 with those for an water heater.
ideal Rankine cycle having the same turbine inlet conditions 8.36 Modify the ideal Rankine cycle of Problem 8.6 to include
and condenser pressure, but no regenerator. superheated vapor entering the first turbine stage at 18 MPa,
560C, and one closed feedwater heater using extracted steam fed into an open feedwater heater operating at that pressure.
at 1 MPa. Condensate drains from the feedwater heater as sat- Saturated liquid at 0.15 MPa leaves the open feedwater heater.
urated liquid at 1 MPa and is trapped into the condenser. The For isentropic processes in the pumps and turbines, determine
feedwater leaves the heater at 18 MPa and a temperature equal for the cycle (a) the thermal efficiency and (b) the mass flow
to the saturation temperature at 1 MPa. Determine for the rate into the first-stage turbine, in kg/h, if the net power
modified cycle. developed is 320 MW.
(a) the net work, in kJ per kg of steam entering the first tur- 8.42 Reconsider the cycle of Problem 8.41, but include in the
bine stage. analysis that each turbine stage has an isentropic efficiency of
(b) the thermal efficiency. 82% and each pump an efficiency of 100%.
(c) the heat transfer to cooling water passing through the con- 8.43 Modify the ideal Rankine cycle of Problem 8.6 to include
denser, in kJ per kg of steam entering the first turbine stage. superheated vapor entering the first turbine stage at 18 MPa,
8.37 Reconsider the cycle of Problem 8.36, but include in the 560C, and two feedwater heaters. One closed feedwater heater
analysis that the isentropic efficiencies of the turbine stages uses extracted steam at 4 MPa, and one open feedwater heater
and the pump are 85%. operates with extracted steam at 0.3 MPa. Saturated liquid con-
8.38 Referring to Fig. 8.12, if the fractions of the total flow en- densate drains from the closed heater at 4 MPa and is trapped
tering the first turbine stage (state 1) extracted at states 2, 3, into the open heater. The feedwater leaves the closed heater at
6, and 7 are y2, y3, y6, and y7, respectively, what are the frac- 18 MPa and a temperature equal to the saturation temperature
tions of the total flow at states 8, 11, and 17? at 4 MPa. Saturated liquid leaves the open heater at 0.3 MPa.
8.39 Consider a regenerative vapor power cycle with two feed- Determine for the modified cycle
water heaters, a closed one and an open one. Steam enters the (a) the net work, in kJ per kg of steam entering the first turbine
first turbine stage at 8 MPa, 480C, and expands to 2 MPa. stage.
Some steam is extracted at 2 MPa and fed to the closed feed- (b) the thermal efficiency.
water heater. The remainder expands through the second-stage (c) the heat transfer to cooling water passing through the con-
turbine to 0.3 MPa, where an additional amount is extracted denser, in kJ per kg of steam entering the first turbine stage.
and fed into the open feedwater heater, which operates at
8.44 Reconsider the cycle of Problem 8.43, but include in the
0.3 MPa. The steam expanding through the third-stage turbine
analysis that the isentropic efficiencies of the turbine stages
exits at the condenser pressure of 8 kPa. Feedwater leaves the
and pumps are 85%.
closed heater at 205C, 8 MPa, and condensate exiting as
saturated liquid at 2 MPa is trapped into the open heater. 8.45 Modify the regenerative vapor power cycle in Problem
Saturated liquid at 0.3 MPa leaves the open feedwater heater. 8.39 to include reheat at 2 MPa. The portion of the flow that
The net power output of the cycle is 100 MW. If the turbine passes through the second turbine stage is reheated to 440C
stages and pumps are isentropic, determine before it enters the second turbine stage. Determine the ther-
mal efficiency of the modified cycle.
(a) the thermal efficiency.
(b) the mass flow rate of steam entering the first turbine, in 8.46 Reconsider the cycle of Problem 8.45, but include in the
kg/h. analysis that each turbine stage has an isentropic efficiency of
8.40 For the cycle of Problem 8.39, investigate the effects on 85% and each pump an efficiency of 82%.
cycle performance as the higher extraction pressure takes on 8.47 Steam enters the first turbine stage of a vapor power cy-
other values. The operating conditions for the open feedwater cle with reheat and regeneration at 32 MPa, 600C, and ex-
heater are unchanged from those in Problem 8.39. Assume that pands to 8 MPa. A portion of the flow is diverted to a closed
condensate drains from the closed feedwater heater as satu- feedwater heater at 8 MPa, and the remainder is reheated to
rated liquid at the higher extraction pressure. Also, feedwater 560C before entering the second turbine stage. Expansion
leaves the heater at 8 MPa and a temperature equal to the sat- through the second turbine stage occurs to 1 MPa, where an-
uration temperature at the extraction pressure. Construct suit- other portion of the flow is diverted to a second closed feed-
able plots and discuss. Reconsider the analysis assuming that water heater at 1 MPa. The remainder of the flow expands
each turbine stage and the pump has an isentropic efficiency through the third turbine stage to 0.15 MPa, where a portion
of 80%. of the flow is diverted to an open feedwater heater operating
8.41 A power plant operates on a regenerative vapor power at 0.15 MPa, and the rest expands through the fourth turbine
cycle with two feedwater heaters. Steam enters the first tur- stage to the condenser pressure of 6 kPa. Condensate leaves
bine stage as 12 MPa, 520C and expands in three stages to each closed feedwater heater as saturated liquid at the respec-
the condenser pressure of 6 kPa. Between the first and sec- tive extraction pressure. The feedwater streams leave each
ond stages, some steam is diverted to a closed feedwater closed feedwater heater at a temperature equal to the satura-
heater at 1 MPa, with saturated liquid condenstate being tion temperature at the respective extraction pressure. The con-
pumped ahead into the boiler feedwater line. The feedwater densate streams from the closed heaters each pass through traps
leaves the closed heater at 12 MPa, 170C. Steam is extracted into the next lower-pressure feedwater heater. Saturated liquid
between the second and third turbine stages at 0.15 MPa and exiting the open heater is pumped to the steam generator
pressure. If each turbine stage has an isentropic efficiency of (c) the rate of heat transfer to the working fluid passing
85% and the pumps operate isentropically through the steam generator, in kJ/h.
(a) sketch the layout of the cycle and number the principal 8.51 Figure P8.51 shows the schematic diagram of a cogen-
state points. eration cycle. In the steam cycle, superheated vapor enters
(b) determine the thermal efficiency of the cycle. the turbine with a mass flow rate of 5 kg/s at 40 bar, 440C
(c) calculate the mass flow rate into the first turbine stage, in and expands isentropically to 1.5 bar. Half of the flow is ex-
kg/h, for a net power output of 500 MW. tracted at 1.5 bar and used for industrial process heating. The
rest of the steam passes through a heat exchanger, which
Considering Other Vapor Cycle Aspects serves as the boiler of the Refrigerant 134a cycle and the
condenser of the steam cycle. The condensate leaves the heat
8.48 A binary vapor power cycle consists of two ideal Rankine
exchanger as saturated liquid at 1 bar, where it is combined
cycles with steam and ammonia as the working fluids. In the
with the return flow from the process, at 60C and 1 bar, be-
steam cycle, superheated vapor enters the turbine at 6 MPa,
fore being pumped isentropically to the steam generator
640C, and saturated liquid exits the condenser at 60C. The
pressure. The Refrigerant 134a cycle is an ideal Rankine cy-
heat rejected from the steam cycle is provided to the ammo-
cle with refrigerant entering the turbine at 16 bar, 100C and
nia cycle, producing saturated vapor at 50C, which enters the
saturated liquid leaving the condenser at 9 bar. Determine,
ammonia turbine. Saturated liquid leaves the ammonia con-
in kW,
denser at 1 MPa. For a net power output of 20 MW from the
binary cycle, determine (a) the rate of heat transfer to the working fluid passing
through the steam generator of the steam cycle.
(a) the power output of the steam and ammonia turbines, (b) the net power output of the binary cycle.
respectively, in MW. (c) the rate of heat transfer to the industrial process.
(b) the rate of heat addition to the binary cycle, in MW.
8.49 Water is the working fluid in a cogeneration cycle that gen-
Q in
erates electricity and provides heat for campus buildings. Steam
Steam at 2 MPa, 320C, enters a two-stage turbine with a mass generator
flow rate of 0.82 kg/s. A fraction of the total flow, 0.141, is
extracted between the two stages at 0.15 MPa to provide for 1
building heating, and the remainder expands through the sec- Turbine Wt1
ond stage to the condenser pressure of 0.06 bar. Condensate
returns from the campus buildings at 0.1 MPa, 60C and passes
through a trap into the condenser, where it is reunited with the 1.5 bar
main feedwater flow. Saturated liquid leaves the condenser at 2
H2O cycle To industrial
0.06 bar. Each turbine stage has an isentropic efficiency of process
80%, and the pumping process can be considered isentropic. H2O/R-134a
Determine heat
exchanger a
(a) the rate of heat transfer to the working fluid passing Turbine Wt2
through the steam generator, in kJ / h.
(b) the net power developed, in kJ / h. 5 Refrigerant b
(c) the rate of heat transfer for building heating, in kJ/h. cycle
(d) the rate of heat transfer to the cooling water passing
Q out
through the condenser, in kJ / h. R-134a
cycle
8.50 Consider a cogeneration system operating as illustrated in Pump Condenser
3 d
Fig. 8.14. The steam generator provides a 106 kg/h of steam 4 Pump
at 8 MPa, 480C, of which 4 105 kg / h is extracted between c
the first and second turbine stages at 1 MPa and diverted to a 6
Wp1
process heating load. Condensate returns from the process
Return flow from Wp2
heating load at 0.95 MPa, 120C and is mixed with liquid ex- industrial process
iting the lower-pressure pump at 0.95 MPa. The entire flow is 1 bar, 60C
then pumped to the steam generator pressure. Saturated liquid
Figure P8.51
at 8 kPa leaves the condenser. The turbine stages and the pumps
operate with isentropic efficiencies of 86 and 80%, respec-
tively. Determine Vapor Cycle Exergy Analysis
(a) the heating load, in kJ / h. 8.52 The steam generator of a vapor power plant can be con-
(b) the power developed by the turbine, in kW. sidered for simplicity to consist of a combustor unit in which
fuel and air are burned to produce hot combustion gases, fol- 8.54 Determine the rate of exergy input, in MW, to the work-
lowed by a heat exchanger unit where the cycle working fluid ing fluid passing through the steam generator in Problem 8.47.
is vaporized and superheated as the hot gases cool. Consider Perform calculations to account for all outputs, losses, and de-
water as the working fluid undergoing the cycle of Problem structions of this exergy. Let T0 15C, p0 1 bar.
8.13. Hot combustion gases, which are assumed to have the 8.55 Determine the rate of exergy transfer, in MW, to the work-
properties of air, enter the heat exchanger portion of the steam ing fluid passing through the steam generator in Problem 8.31.
generator at 1200 K and exit at 500 K with a negligible change Perform calculations to account for all outputs, losses, and de-
in pressure. Determine for the heat exchanger unit structions of this exergy. Let T0 15C, p0 0.1 MPa.
(a) the net rate at which exergy is carried in by the gas stream, 8.56 Steam enters the turbine of a vapor power plant at 100 bar,
in kW. 520C and expands adiabatically, exiting at 0.08 bar with a
(b) the net rate at which exergy is carried out by the water quality of 90%. Condensate leaves the condenser as saturated
stream, in kW. liquid at 0.08 bar. Liquid exits the pump at 100 bar, 43C. The
(c) the rate of exergy destruction, in kW. specific exergy of the fuel entering the combustor unit of the
(d) the exergetic efficiency given by Eq. 7.45. steam generator is estimated to be 14,700 kJ/kg. No exergy is
carried in by the combustion air. The exergy of the stack gases
Let T0 15C, p0 0.1 MPa.
leaving the steam generator is estimated to be 150 kJ per kg
8.53 Determine the rate of exergy input, in MW, to the work- of fuel. The mass flow rate of the steam is 3.92 kg per kg of
ing fluid passing through the steam generator in Problem 8.13. fuel. Cooling water enters the condenser at T0 20C, p0
Perform calculations to account for all outputs, losses, and de- 1 atm and exits at 35C, 1 atm. Develop a full accounting of
structions of this exergy. Let T0 15C, p0 0.1 MPa. the exergy entering the plant with the fuel.
8.1D Vast quantities of water circulate through the condensers 8.4D Sunlight can be converted directly into electrical output
of large power plants, exiting at temperatures 10 to 15C above by photovoltaic cells. These cells have been used for auxiliary
the ambient temperature. What possible uses could be made of power generation in spaceflight applications as well as for ter-
the condenser cooling water? Does this warm water represent restrial applications in remote areas. Investigate the principle
a significant resource? What environmental concerns are as- of operation of photovoltaic cells for electric power genera-
sociated with cooling water? Discuss. tion. What efficiencies are achieved by present designs, and
8.2D Early commercial vapor power plants operated with tur- how are the efficiencies defined? What is the potential for more
bine inlet conditions of about 12 bar and 200C. Plants are widespread use of this technology? Summarize your findings
under development today that can operate at over 34 MPa, with in a memorandum.
turbine inlet temperatures of 650C or higher. How have steam 8.5D One way for power plants to meet peak demands is to use
generator and turbine designs changed over the years to allow excess generation capacity during off-peak hours to produce
for such increases in pressure and temperature? Discuss. ice, which can then be used as a low-temperature reservoir for
8.3D Among the options for meeting future power needs are condenser heat rejection during peak demand periods. Criti-
the use of biomass as a fuel and nuclear power. As assigned cally evaluate this concept for improved power plant utiliza-
by your instructor, complete one of the following: tion and write a report of your findings.
(a) Consider the feasibility of using biomass to fuel a 500-MW 8.6D Many hospitals, industrial facilities, college campuses,
electric power plant. Write a report discussing the advan- and towns employ cogeneration plants that provide district
tages and disadvantages of biomass in comparison to heating/cooling and generate electricity. Sketch the main com-
conventional fossil fuels for power plants. Include in your ponents and layout of such an existing cogeneration system in
analysis plant operations, environmental issues, and costs. your locale. Determine the heating and cooling loads served
(b) Many nuclear power plants are nearing the end of their by the system and its electrical generating capacity. Estimate
useful lives, and the construction of new nuclear the cost savings observed through the use of cogeneration com-
power plants is unlikely for the foreseeable future. What pared to meeting these loads individually. Discuss.
challenges are presented by the existing nuclear power 8.7D A significant supply of geothermal hot water at 12 bar,
plants as they age? What are the options for repowering 180C exists at a particular location. Develop the preliminary
existing plants? What concepts are under investigation for design of a 10-MW electric power plant using flash evaporation
future nuclear power plant technology? Will nuclear power to provide steam to the turbine-generator. Propose a way to dis-
play a significant role in the United States in the future? pose of the excess water and spent brine from the flashing
Write a paper discussing these issues. process.
8.8D Figure P8.8D shows a thermosyphon Rankine power plant

W
having one end immersed in a solar pond and the other ex-
posed to the ambient air. At the lower end, a working fluid is Ambient air
vaporized by heat transfer from the hot water of the solar pond.
The vapor flows upward through an axial-flow turbine to the
upper end, where condensation occurs by heat transfer to the
Q out
ambient air. The condensate drains to the lower end by grav-
Condensate
ity. Evaluate the feasibility of producing power in the 0.10.25 formation
kW range using such a device. What working fluids would be
suitable? Write a report of your findings. Condensate
Insulation
downpipe
8.9D Cleaner is Better (see box Sec. 8.2). Write a report
discussing the state-of-the-art of (a) fluidized bed combustion,
(b) IGCC plants. Include at least three references. Vapor
Solar pond
Working fluid

Q in
Vapor formation
Figure P8.8D
C
H
A
P
T
Gas Power
Systems R
E
9
E N G I N E E R I N G C O N T E X T The vapor power systems studied in
Chap. 8 use working fluids that are alternately vaporized and condensed. The objective of chapter objective
the present chapter is to study power systems utilizing working fluids that are always a gas.
Included in this group are gas turbines and internal combustion engines of the spark-ignition
and compression-ignition types. In the first part of the chapter, internal combustion engines
are considered. Gas turbine power plants are discussed in the second part of the chapter. The
chapter concludes with a brief study of compressible flow in nozzles and diffusers, which are
components in gas turbines for aircraft propulsion and other devices of practical importance.
INTERNAL COMBUSTION ENGINES
This part of the chapter deals with internal combustion engines. Although most gas turbines
are also internal combustion engines, the name is usually applied to reciprocating internal com-
bustion engines of the type commonly used in automobiles, trucks, and buses. These engines
differ from the power plants considered in Chap. 8 because the processes occur within recip-
rocating pistoncylinder arrangements and not in interconnected series of different components.
Two principal types of reciprocating internal combustion engines are the spark-ignition spark-ignition
engine and the compression-ignition engine. In a spark-ignition engine, a mixture of fuel
compression-ignition
and air is ignited by a spark plug. In a compression-ignition engine, air is compressed to a
high enough pressure and temperature that combustion occurs spontaneously when fuel is
injected. Spark-ignition engines have advantages for applications requiring power up to about
225 kW. Because they are relatively light and lower in cost, spark-ignition engines are par-
ticularly suited for use in automobiles. Compression-ignition engines are normally preferred
for applications when fuel economy and relatively large amounts of power are required (heavy
trucks and buses, locomotives and ships, auxiliary power units). In the middle range, spark-
ignition and compression-ignition engines are used.

9.1 Introducing Engine Terminology
Figure 9.1 is a sketch of a reciprocating internal combustion engine consisting of a piston that
moves within a cylinder fitted with two valves. The sketch is labeled with some special terms.
The bore of the cylinder is its diameter. The stroke is the distance the piston moves in one
373
374 Chapter 9 Gas Power Systems
Spark plug or
fuel injector
p
Valve
Po
Top Clearance
w
er
dead center volume
Bore
Cylinder
Stroke wall
Exhaust valve
X
Exhaust Co opens
m pre
Bottom valve ssi
dead center closes on
Reciprocating Piston Exhaust
motion Intake valve
X
closes
Intake
Crank mechanism
Top dead Bottom

Rotary center dead center
motion Volume
Figure 9.1 Nomenclature for reciprocating Figure 9.2 Pressurevolume diagram for
pistoncylinder engines. a reciprocating internal combustion engine.
direction. The piston is said to be at top dead center when it has moved to a position where
the cylinder volume is a minimum. This minimum volume is known as the clearance volume.
When the piston has moved to the position of maximum cylinder volume, the piston is at
bottom dead center. The volume swept out by the piston as it moves from the top dead center
compression ratio to the bottom dead center position is called the displacement volume. The compression ratio
r is defined as the volume at bottom dead center divided by the volume at top dead center.
The reciprocating motion of the piston is converted to rotary motion by a crank mechanism.
In a four-stroke internal combustion engine, the piston executes four distinct strokes within
the cylinder for every two revolutions of the crankshaft. Figure 9.2 gives a pressurevolume
diagram such as might be displayed electronically.
1. With the intake valve open, the piston makes an intake stroke to draw a fresh charge
into the cylinder. For spark-ignition engines, the charge is a combustible mixture of fuel
and air. Air alone is the charge in compression-ignition engines.
2. With both valves closed, the piston undergoes a compression stroke, raising the
temperature and pressure of the charge. This requires work input from the piston to the
cylinder contents. A combustion process is then initiated, resulting in a high-pressure,
high-temperature gas mixture. Combustion is induced near the end of the compression
stroke in spark-ignition engines by the spark plug. In compression-ignition engines,
combustion is initiated by injecting fuel into the hot compressed air, beginning near the
end of the compression stroke and continuing through the first part of the expansion.
3. A power stroke follows the compression stroke, during which the gas mixture expands
and work is done on the piston as it returns to bottom dead center.
4. The piston then executes an exhaust stroke in which the burned gases are purged from
the cylinder through the open exhaust valve.
Smaller engines operate on two-stroke cycles. In two-stroke engines, the intake, compression,
expansion, and exhaust operations are accomplished in one revolution of the crankshaft.
Although internal combustion engines undergo mechanical cycles, the cylinder contents
9.2 Air-Standard Otto Cycle 375
do not execute a thermodynamic cycle, for matter is introduced with one composition and is
later discharged at a different composition.
A parameter used to describe the performance of reciprocating piston engines is the mean
effective pressure, or mep. The mean effective pressure is the theoretical constant pressure
that, if it acted on the piston during the power stroke, would produce the same net work as
actually developed in one cycle. That is
net work for one cycle

mep (9.1) mean effective pressure
displacement volume
For two engines of equal displacement volume, the one with a higher mean effective pressure
would produce the greater net work and, if the engines run at the same speed, greater power.
AIR-STANDARD ANALYSIS. A detailed study of the performance of a reciprocating internal

combustion engine would take into account many features. These would include the combustion
process occurring within the cylinder and the effects of irreversibilities associated with friction
and with pressure and temperature gradients. Heat transfer between the gases in the cylinder and
the cylinder walls and the work required to charge the cylinder and exhaust the products of com-
bustion also would be considered. Owing to these complexities, accurate modeling of recipro-
cating internal combustion engines normally involves computer simulation. To conduct element-
ary thermodynamic analyses of internal combustion engines, considerable simplification is air-standard analysis:
required. One procedure is to employ an air-standard analysis having the following elements: internal combustion
A fixed amount of air modeled as an ideal gas is the working fluid. engines
The combustion process is replaced by a heat transfer from an external source.

There are no exhaust and intake processes as in an actual engine. The cycle is com-
pleted by a constant-volume heat transfer process taking place while the piston is at the
bottom dead center position.
All processes are internally reversible.
In addition, in a cold air-standard analysis, the specific heats are assumed constant at their cold air-standard analysis
ambient temperature values. With an air-standard analysis, we avoid dealing with the com-
plexities of the combustion process and the change of composition during combustion. A
comprehensive analysis requires that such complexities be considered, however. For a
discussion of combustion, see Chap. 13.
Although an air-standard analysis simplifies the study of internal combustion engines con-
siderably, values for the mean effective pressure and operating temperatures and pressures
calculated on this basis may depart significantly from those of actual engines. Accordingly,
air-standard analysis allows internal combustion engines to be examined only qualitatively.
Still, insights concerning actual performance can result with such an approach.
In the remainder of this part of the chapter, we consider three cycles that adhere to air-
standard cycle idealizations: the Otto, Diesel, and dual cycles. These cycles differ from each
other only in the way the heat addition process that replaces combustion in the actual cycle
is modeled.

9.2 Air-Standard Otto Cycle
The air-standard Otto cycle is an ideal cycle that assumes the heat addition occurs instanta-
neously while the piston is at top dead center. The Otto cycle is shown on the pv and Ts Otto cycle
p T
3
3
2 c 3
2
s= s= v=
c c
2
4
4 v=c
1
1
Figure 9.3 pv and Ts diagrams of
a b v b a s
the air-standard Otto cycle.
diagrams of Fig. 9.3. The cycle consists of four internally reversible processes in series:
Process 12 is an isentropic compression of the air as the piston moves from bottom
dead center to top dead center.
Process 23 is a constant-volume heat transfer to the air from an external source while
the piston is at top dead center. This process is intended to represent the ignition of the
fuelair mixture and the subsequent rapid burning.
Process 34 is an isentropic expansion (power stroke).
Process 41 completes the cycle by a constant-volume process in which heat is rejected
from the air while the piston is at bottom dead center.
Since the air-standard Otto cycle is composed of internally reversible processes, areas on
the Ts and pv diagrams of Fig. 9.3 can be interpreted as heat and work, respectively. On
the Ts diagram, area 23ab2 represents the heat added per unit of mass and area
14ab1 the heat rejected per unit of mass. On the pv diagram, area 12ab1 repre-
sents the work input per unit of mass during the compression process and area 34ba3
is the work done per unit of mass in the expansion process. The enclosed area of each fig-
ure can be interpreted as the net work output or, equivalently, the net heat added.
CYCLE ANALYSIS. The air-standard Otto cycle consists of two processes in which there is
work but no heat transfer, Processes 12 and 34, and two processes in which there is heat
transfer but no work, Processes 23 and 41. Expressions for these energy transfers are
obtained by reducing the closed system energy balance assuming that changes in kinetic and
potential energy can be ignored. The results are
W12 W34
u2 u1, u3 u4
m m
(9.2)
Q23 Q41
u3 u2, u4 u1
m m
METHODOLOGY
UPDATE
Carefully note that in writing Eqs. 9.2, we have departed from our usual sign convention for
heat and work. Thus, W12m is a positive number representing the work input during com-
When analyzing air-
pression and Q41m is a positive number representing the heat rejected in Process 41. The
standard cycles, it is
frequently convenient to net work of the cycle is expressed as
regard all work and heat Wcycle
1u3 u4 2 1u2 u1 2
W34 W12
transfers as positive quan-
tities and write the energy m m m
balance accordingly.
Alternatively, the net work can be evaluated as the net heat added
Wcycle
1u3 u2 2 1u4 u1 2
Q23 Q41

m m m
which, on rearrangement, can be placed in the same form as the previous expression for net
work.
The thermal efficiency is the ratio of the net work of the cycle to the heat added.
1u3 u2 2 1u4 u1 2 u4 u1
h 1 (9.3)
u3 u2 u3 u2
When air table data are used to conduct an analysis involving an air-standard Otto cycle,
the specific internal energy values required by Eq. 9.3 can be obtained from Table A-22 or
A-22E as appropriate. The following relationships based on Eq. 6.44 apply for the isentropic
processes 12 and 34
vr 2 vr1 a b
V2 vr1
(9.4)
V1 r
vr 4 vr3 a b rvr3
V4
(9.5)
V3
where r denotes the compression ratio. Note that since V3 V2 and V4 V1, r V1V2
V4V3. The parameter vr is tabulated versus temperature for air in Tables A-22.
When the Otto cycle is analyzed on a cold air-standard basis, the following expressions
based on Eq. 6.46 would be used for the isentropic processes in place of Eqs. 9.4 and 9.5,
respectively
V1 k1
a b 1constant k2
T2
r k1 (9.6)
T1 V2
V3 k1
a b 1constant k2
T4 1
k1 (9.7)
T3 V4 r
where k is the specific heat ratio, k cpcv.
EFFECT OF COMPRESSION RATIO ON PERFORMANCE. By referring to the Ts diagram

of Fig. 9.3, we can conclude that the Otto cycle thermal efficiency increases as the
compression ratio increases. An increase in the compression ratio changes the cycle from
12341 to 12341. Since the average temperature of heat addition is greater in the
latter cycle and both cycles have the same heat rejection process, cycle 12341 would
have the greater thermal efficiency. The increase in thermal efficiency with compression ratio
is also brought out simply by the following development on a cold air-standard basis. For
constant cv, Eq. 9.3 becomes
cv 1T4 T1 2
h1
cv 1T3 T2 2
On rearrangement
T1 T4 T1 1
h1 a b
T2 T3 T2 1
From Eqs. 9.6 and 9.7 above, T4T1 T3T2, so
T1
h1
T2
Finally, introducing Eq. 9.6
1constant k2
1
h1 k1
(9.8)
r

End of Cheap Oil in View, Experts Say Critical shortages, but not
higher prices, may be avoided by
Nature needed 500 million years to create the worlds stock of expensive methods of squeezing
readily accessible oil, but some observers predict we will con- more oil out of existing wells.
sume most of whats left within the next 50 years. Still, the im- Also, unconventional petroleum
portant issue, they say, is not when the world runs out of oil, but resources locked in oil shale and
when production will peak. After that, production must decline, tar sands could be tapped. Al-
and unless demand is reduced, oil prices will rise. This will end though vast in extent, the costs
the era of cheap oil we enjoy and pose challenges for society. of extracting these resources
The rate any well can produce oil typically rises to a max- would be great. Extensive envi-
imum and then, when about half the oil has been pumped out, ronmental damage may result,
begins to fall as the remaining oil becomes increasingly diffi- including the effects of air emis-
cult to extract. Using this model for the world oil supply as a sions, liquid effluents, and vast
whole, economists predict a peak in oil production by 2020, amounts of spent shale and sand that would remain after oil
or even as soon as 2010. That will lead to shortages and higher has been removed.
prices at the pump, which will have global economic and po-
litical repercussions.
70 Equation 9.8 indicates that the cold air-standard Otto cycle thermal efficiency is a function
60 of compression ratio and k. This relationship is shown in Fig. 9.4 for k 1.4, representing
50 ambient air.
40 The foregoing discussion suggests that it is advantageous for internal combustion en-
(%)
30 gines to have high compression ratios, and this is the case. The possibility of autoignition,
20 or knock, places an upper limit on the compression ratio of spark-ignition engines, how-
10 ever. After the spark has ignited a portion of the fuelair mixture, the rise in pressure ac-
0
companying combustion compresses the remaining charge. Autoignition can occur if the
0 2 4 6 8 10 temperature of the unburned mixture becomes too high before the mixture is consumed by
Compression ratio, r
the flame front. Since the temperature attained by the airfuel mixture during the com-
Figure 9.4 Thermal pression stroke increases as the compression ratio increases, the likelihood of autoignition
efficiency of the cold air-
occurring increases with the compression ratio. Autoignition may result in high-pressure
standard Otto cycle, k
waves in the cylinder (manifested by a knocking or pinging sound) that can lead to loss
1.4.
of power as well as engine damage. Fuels formulated with tetraethyl lead are resistant to
autoignition and thus allow relatively high compression ratios. The unleaded gasoline in
common use today because of environmental concerns over air pollution limits the com-
pression ratios of spark-ignition engines to approximately 9. Higher compression ratios
can be achieved in compression-ignition engines because air alone is compressed. Com-
pression ratios in the range of 12 to 20 are typical. Compression-ignition engines also can
use less refined fuels having higher ignition temperatures than the volatile fuels required
by spark-ignition engines.
In the next example, we illustrate the analysis of the air-standard Otto cycle. Results are
compared with those obtained on a cold air-standard basis.
EXAMPLE 9.1 Analyzing the Otto Cycle
The temperature at the beginning of the compression process of an air-standard Otto cycle with a compression ratio of 8 is
300K, the pressure is 1 bar, and the cylinder volume is 560 cm3. The maximum temperature during the cycle is 2000K.
Determine (a) the temperature and pressure at the end of each process of the cycle, (b) the thermal efficiency, and (c) the
mean effective pressure, in atm.
SOLUTION
Known: An air-standard Otto cycle with a given value of compression ratio is executed with specified conditions at the
beginning of the compression stroke and a specified maximum temperature during the cycle.
Find: Determine the temperature and pressure at the end of each process, the thermal efficiency, and mean effective pressure,
in atm.
p 3 T
T3 = 2000 3
T3 = 2000
c
s= v= 4
c
2 2
4 c
s= =
c v
V
1 = 8 T1 = 300
V2 1 1
v s
Figure E9.1
Assumptions:
1. The air in the pistoncylinder assembly is the closed system.

2. The compression and expansion processes are adiabatic.
3. All processes are internally reversible.
Analysis:
(a) The analysis begins by determining the temperature, pressure, and specific internal energy at each principal state of the
cycle. At T1 300 K, Table A-22 gives u1 214.07 kJ/kg and vr1 621.2.
For the isentropic compression Process 12
V2 vr1 621.2
vr2 vr1 77.65
V1 r 8
Interpolating with vr2 in Table A-22, we get T2 673 K and u2 491.2 kJ/kg. With the ideal gas equation of state
11 atm2 a b 8 17.95 bars

T2 V1 673K
p2 p1
T1 V2 300K
The pressure at state 2 can be evaluated alternatively by using the isentropic relationship, p2 p1( pr2pr1).
Since Process 23 occurs at constant volume, the ideal gas equation of state gives
117.95 bars2 a b 53.3 bars

T3 2000 K
p3 p2
T2 673 K
At T3 2000 K, Table A-22 gives u3 1678.7 kJ/kg and vr3 2.776.
For the isentropic expansion process 34
V4 V1
vr4 vr3 vr3 2.776182 22.21
V3 V2
Interpolating in Table A-22 with vr4 gives T4 1043 K, u4 795.8 kJ/kg. The pressure at state 4 can be found using the isen-
tropic relationship p4 p3(pr4 pr3) or the ideal gas equation of state applied at states 1 and 4. With V4 V1, the ideal gas
equation of state gives
11 bar2 a b 3.48 bars

T4 1043 K
p4 p1
T1 300 K
(b) The thermal efficiency is
Q41 m u4 u1
h1 1
Q23 m u3 u2
795.8 214.07
1 0.51 151% 2
1678.7 491.2
(c) To evaluate the mean effective pressure requires the net work per cycle. That is
Wcycle m 3 1u3 u4 2 1u2 u1 2 4
where m is the mass of the air, evaluated from the ideal gas equation of state as follows:
p1V1
m
1RM2T1
11 bar21560 cm3 2 1 m3 105 N/m2
a b a ba 3 # b
1 kJ
6 3
a b 1300 K2
8.314 kJ 10 cm 1 bar 10 N m
28.97 kg # K
6.5 104 kg
Inserting values into the expression for Wcycle

Wcycle 16.5 104 kg2 3 11678.7 795.82 1491.2 214.072 4 kJ/kg
0.394 kJ
The displacement volume is V1 V2, so the mean effective pressure is given by
Wcycle Wcycle
mep
V1 V2 V1 11 V2 V1 2

0.394 kJ
a
106 cm3 103 N . m
ba ba 5
1 bar
b
1560 cm 211 182
3
1m 3
1 kJ 10 N/m2
8.04 bars
This solution utilizes Table A-22 for air, which accounts explicitly for the variation of the specific heats with tem-
perature. A solution also can be developed on a cold air-standard basis in which constant specific heats are assumed.
This solution is left as an exercise, but for comparison the results are presented for the case k 1.4 in the following
table:
Cold Air-Standard Analysis,

Parameter Air-Standard Analysis k 1.4
T2 673 K 689 K
T3 2000 K 2000 K
T4 1043 K 871 K
0.51 (51%) 0.565 (56.5%)
mep 8.04 bars 7.05 bars
9.3 Air-Standard Diesel Cycle 381

9.3 Air-Standard Diesel Cycle
The air-standard Diesel cycle is an ideal cycle that assumes the heat addition occurs during
a constant-pressure process that starts with the piston at top dead center. The Diesel cycle is Diesel cycle
shown on pv and Ts diagrams in Fig. 9.5. The cycle consists of four internally reversible
processes in series. The first process from state 1 to state 2 is the same as in the Otto cycle:
an isentropic compression. Heat is not transferred to the working fluid at constant volume
as in the Otto cycle, however. In the Diesel cycle, heat is transferred to the working fluid at
constant pressure. Process 23 also makes up the first part of the power stroke. The isen-
tropic expansion from state 3 to state 4 is the remainder of the power stroke. As in the Otto
cycle, the cycle is completed by constant-volume Process 41 in which heat is rejected from
the air while the piston is at bottom dead center. This process replaces the exhaust and intake
processes of the actual engine.
Since the air-standard Diesel cycle is composed of internally reversible processes, ar-
eas on the Ts and pv diagrams of Fig. 9.5 can be interpreted as heat and work, respec-
tively. On the Ts diagram, area 23ab2 represents the heat added per unit of mass and
area 14ab1 is the heat rejected per unit of mass. On the pv diagram, area 12ab1
is the work input per unit of mass during the compression process. Area 234ba2 is
the work done per unit of mass as the piston moves from top dead center to bottom dead
center. The enclosed area of each figure is the net work output, which equals the net heat
added.
CYCLE ANALYSIS. In the Diesel cycle the heat addition takes place at constant pressure.
Accordingly, Process 23 involves both work and heat. The work is given by
p dv p2 1v3 v2 2
W23 3
(9.9)
m 2
The heat added in Process 23 can be found by applying the closed system energy balance
m1u3 u2 2 Q23 W23
Introducing Eq. 9.9 and solving for the heat transfer
1u3 u2 2
p1v3 v2 2 1u3
pv3 2 1u2
pv2 2
Q23
m
h3 h2 (9.10)
3
p T
2 3
c
2 p= 4
s=
c
c
s=
v=
c
1 1 Figure 9.5 pv and Ts

diagrams of the air-standard
a b v b a s Diesel cycle.
where the specific enthalpy is introduced to simplify the expression. As in the Otto cycle,
the heat rejected in Process 41 is given by
Q41
u4 u1
m
The thermal efficiency is the ratio of the net work of the cycle to the heat added
Wcycle m Q41 m u4 u1
h 1 1 (9.11)
Q23 m Q23 m h3 h2
As for the Otto cycle, the thermal efficiency of the Diesel cycle increases with the com-
pression ratio.
To evaluate the thermal efficiency from Eq. 9.11 requires values for u1, u4, h2, and h3 or
equivalently the temperatures at the principal states of the cycle. Let us consider next how
these temperatures are evaluated. For a given initial temperature T1 and compression ratio r,
the temperature at state 2 can be found using the following isentropic relationship and vr data
V2 1
vr2 vr1 vr1
V1 r
To find T3, note that the ideal gas equation of state reduces with p3 p2 to give
V3
T3 T rcT2
V2 2
cutoff ratio where rc V3V2, called the cutoff ratio, has been introduced.
Since V4 V1, the volume ratio for the isentropic process 34 can be expressed as
V4 V4 V2 V1 V2 r
(9.12)
V3 V2 V3 V2 V3 rc
where the compression ratio r and cutoff ratio rc have been introduced for conciseness.
Using Eq. 9.12 together with vr3 at T3, the temperature T4 can be determined by interpo-
lation once vr4 is found from the isentropic relationship
V4 r
vr4 v v
V3 r3 rc r3
In a cold air-standard analysis, the appropriate expression for evaluating T2 is provided
by
V1 k1
a b 1constant k2
T2
r k1
T1 V2
The temperature T4 is found similarly from
V3 k1 rc k1
a b a b 1constant k2
T4
T3 V4 r
where Eq. 9.12 has been used to replace the volume ratio.
EFFECT OF COMPRESSION RATIO ON PERFORMANCE. As for the Otto cycle, the ther-
mal efficiency of the Diesel cycle increases with increasing compression ratio. This can be
brought out simply using a cold air-standard analysis. On a cold air-standard basis, the ther-
mal efficiency of the Diesel cycle can be expressed as
r kc 1
c d 1constant k2
1
h1
k 1rc 12
(9.13)
r k1
9.3 Air-Standard Diesel Cycle 383
70 o cycle)
1 ( O tt
rc =
60
Thermal efficiency, (%)
50 Diesel
40 cycle
rc = 2
30 rc = 3
20
10
0
5 10 15 20 Figure 9.6 Thermal efficiency of the cold air-
Compression ratio, r standard Diesel cycle, k 1.4.
where r is the compression ratio and rc the cutoff ratio. The derivation is left as an exer-
cise. This relationship is shown in Fig. 9.6 for k 1.4. Equation 9.13 for the Diesel cycle
differs from Eq. 9.8 for the Otto cycle only by the term in brackets, which for rc 1 is
greater than unity. Thus, when the compression ratio is the same, the thermal efficiency of
the cold air-standard Diesel cycle would be less than that of the cold air-standard Otto
cycle.
In the next example, we illustrate the analysis of the air-standard Diesel cycle.
EXAMPLE 9.2 Analyzing the Diesel Cycle
At the beginning of the compression process of an air-standard Diesel cycle operating with a compression ratio of 18, the tem-
perature is 300 K and the pressure is 0.1 MPa. The cutoff ratio for the cycle is 2. Determine (a) the temperature and pressure
at the end of each process of the cycle, (b) the thermal efficiency, (c) the mean effective pressure, in MPa.
SOLUTION
Known: An air-standard Diesel cycle is executed with specified conditions at the beginning of the compression stroke. The
compression and cutoff ratios are given.
Find: Determine the temperature and pressure at the end of each process, the thermal efficiency, and mean effective
pressure.
p T 3
2 3
V
rc = 3 = 2 v2
V2
2 c 4
p=
s=
c
s=
c c
V 4 v=
1 = 18
V2
p1 = 0.1 MPa T1 = 300 K
1 1
v s
Figure E9.2
Assumptions:

Analysis:
(a) The analysis begins by determining properties at each principal state of the cycle. With T1 300 K, Table A-22 gives
u1 214.07 kJ/kg and vr1 621.2. For the isentropic compression process 12
V2 vr1 621.2
vr2 v 34.51
V1 r1 r 18
Interpolating in Table A-22, we get T2 898.3 K and h2 930.98 kJ/kg. With the ideal gas equation of state
10.12 a b 1182 5.39 MPa

T2 V1 898.3
p2 p1
T1 V2 300
The pressure at state 2 can be evaluated alternatively using the isentropic relationship, p2 p1( pr2pr1).
Since Process 23 occurs at constant pressure, the ideal gas equation of state gives
V3
T3 T
V2 2
Introducing the cutoff ratio, rc V3V2
T3 rcT2 21898.32 1796.6 K
From Table A-22, h3 1999.1 kJ/kg and vr3 3.97.
For the isentropic expansion process 34
V4 V4 V2
vr4 v v
V3 r3 V2 V3 r3
Introducing V4 V1, the compression ratio r, and the cutoff ratio rc, we have
13.972 35.73
r 18
vr4 v
rc r3 2
Interpolating in Table A-22 with vr4, we get u4 664.3 kJ/kg and T4 887.7 K. The pressure at state 4 can be found using
the isentropic relationship p4 p3(pr4pr3) or the ideal gas equation of state applied at states 1 and 4. With V4 V1, the ideal
gas equation of state gives
10.1 MPa2 a b 0.3 MPa

T4 887.7 K
p4 p1
T1 300 K
(b) The thermal efficiency is found using
Q41m u4 u1
h1 1
Q23m h3 h2
664.3 214.07
1 0.578 157.8% 2
1999.1 930.98
(c) The mean effective pressure written in terms of specific volumes is
Wcycle m Wcycle m
mep
v1 v2 v1 11 1r2
9.4 Air-Standard Dual Cycle 385
The net work of the cycle equals the net heat added
Wcycle
1h3 h2 2 1u4 u1 2
Q23 Q41

m m m
11999.1 930.982 1664.3 214.072
617.9 kJ/kg
The specific volume at state 1 is
a b 1300 K2
8314 N # m
1RM2T1 28.97 kg # K
v1 0.861 m3/kg
p1 105 N/m2
Inserting values
103 N # m
`` ` 6 `
617.9 kJ/kg 1 MPa
mep
0.86111 1182 m3/kg 1 kJ 10 N/m2
0.76 MPa
This solution uses the air tables, which account explicitly for the variation of the specific heats with temperature. Note
that Eq. 9.13 based on the assumption of constant specific heats has not been used to determine the thermal efficiency.
The cold air-standard solution of this example is left as an exercise.

9.4 Air-Standard Dual Cycle
The pressurevolume diagrams of actual internal combustion engines are not described
well by the Otto and Diesel cycles. An air-standard cycle that can be made to approximate
the pressure variations more closely is the air-standard dual cycle. The dual cycle is shown dual cycle
in Fig. 9.7. As in the Otto and Diesel cycles, Process 12 is an isentropic compression.
The heat addition occurs in two steps, however: Process 23 is a constant-volume heat ad-
dition; Process 3 4 is a constant-pressure heat addition. Process 3 4 also makes up the
first part of the power stroke. The isentropic expansion from state 4 to state 5 is the re-
mainder of the power stroke. As in the Otto and Diesel cycles, the cycle is completed by
a constant-volume heat rejection process, Process 5 1. Areas on the Ts and pv diagrams
can be interpreted as heat and work, respectively, as in the cases of the Otto and Diesel
cycles.
p 3 4 T
4
2 p=c
3
s=
s=
c
v=c
c
5
5 2
v=c
1
1
v s
Figure 9.7 pv and Ts diagrams of the air-standard dual cycle.
CYCLE ANALYSIS. Since the dual cycle is composed of the same types of processes as the
Otto and Diesel cycles, we can simply write down the appropriate work and heat transfer ex-
pressions by reference to the corresponding earlier developments. Thus, during the isentropic
compression process 12 there is no heat transfer, and the work is
W12
u2 u1
m
As for the corresponding process of the Otto cycle, in the constant-volume portion of the
heat addition process, Process 23, there is no work, and the heat transfer is
Q23
u3 u2
m
In the constant-pressure portion of the heat addition process, Process 34, there is both work
and heat transfer, as for the corresponding process of the Diesel cycle
p 1v4 v3 2
W34 Q34
and h4 h3
m m
During the isentropic expansion process 45 there is no heat transfer, and the work is
W45
u4 u5
m
Finally, the constant-volume heat rejection process 51 that completes the cycle involves
heat transfer but no work
Q51
u5 u1
m
The thermal efficiency is the ratio of the net work of the cycle to the total heat added
Wcyclem Q51 m
h 1
1Q23 m
Q34m2 1Q23 m
Q34 m2
1u5 u1 2
1
1u3 u2 2
1h4 h3 2
(9.14)
The example to follow provides an illustration of the analysis of an air-standard dual cycle.
The analysis exhibits many of the features found in the Otto and Diesel cycle examples
considered previously.
EXAMPLE 9.3 Analyzing the Dual Cycle
At the beginning of the compression process of an air-standard dual cycle with a compression ratio of 18, the temperature is
300 K and the pressure is 0.1 MPa. The pressure ratio for the constant volume part of the heating process is 1.5:1. The vol-
ume ratio for the constant pressure part of the heating process is 1.2:1. Determine (a) the thermal efficiency and (b) the mean
effective pressure, in MPa.
SOLUTION
Known: An air-standard dual cycle is executed in a pistoncylinder assembly. Conditions are known at the beginning of the
compression process, and necessary volume and pressure ratios are specified.
Find: Determine the thermal efficiency and the mep, in MPa.

9.4 Air-Standard Dual Cycle 387
p 3 4
p V
3 = 1.5, 4 = 1.2
p2 V3 T 4
p=c
2
c 3 5
v=
2
s=
c
v=
s=
c
c
V
1 = 18
V2
5 T1 = 300 K
1
p1 = 0.1 MPa
1
v s
Figure E9.3
Assumptions:

Analysis: The analysis begins by determining properties at each principal state of the cycle. States 1 and 2 are the same as
in Example 9.2, so u1 214.07 kJ/kg, T2 898.3 K, u2 673.2 kJ/kg. Since Process 23 occurs at constant volume, the
ideal gas equation of state reduces to give
T 11.521898.32 1347.5 K
p3
T3
p2 2
Interpolating in Table A-22, we get h3 1452.6 kJ/kg and u3 1065.8 kJ/kg.
Since Process 34 occurs at constant pressure, the ideal gas equation of state reduces to give
T 11.2211347.52 1617 K
V4
T4
V3 3
From Table A-22, h4 1778.3 kJ/kg and vr4 5.609.

Process 45 is an isentropic expansion, so
V5
vr5 vr4
V4
The volume ratio V5V4 required by this equation can be expressed as
V5 V5 V3

V4 V3 V4
With V5 V1, V2 V3, and given volume ratios
18 a b 15
V5 V1 V3 1

V4 V2 V4 1.2
Inserting this in the above expression for vr5
vr5 15.60921152 84.135
Interpolating in Table A-22, we get u5 475.96 kJ/kg.
(a) The thermal efficiency is
Q51m 1u5 u1 2
h1 1
1Q23 m
Q34 m2 1u3 u2 2
1h4 h3 2
1475.96 214.072
1
11065.8 673.22
11778.3 1452.62
0.635 163.5% 2
(b) The mean effective pressure is
Wcycle m Wcycle m
mep
v1 v2 v1 11 1r2
The net work of the cycle equals the net heat added, so
1u3 u2 2
1h4 h3 2 1u5 u1 2
mep
v1 11 1r2
The specific volume at state 1 is evaluated in Example 9.2 as v1 0.861 m3/kg. Inserting values into the above expres-
sion for mep
kJ 103 N # m
3 11065.8 673.22
11778.3 1452.62 1475.96 214.072 4 a b` ` ` 6 `
1 MPa
kg 1 kJ 10 N/m2
mep 0.56 MPa
0.86111 1182 m3/kg
GAS TURBINE POWER PLANTS
This part of the chapter deals with gas turbine power plants. Gas turbines tend to be lighter
and more compact than the vapor power plants studied in Chap. 8. The favorable power-
output-to-weight ratio of gas turbines makes them well suited for transportation applications
(aircraft propulsion, marine power plants, and so on). Gas turbines are also commonly used
for stationary power generation.
9.5 Modeling Gas Turbine Power Plants

Gas turbine power plants may operate on either an open or closed basis. The open mode pic-
tured in Fig. 9.8a is more common. This is an engine in which atmospheric air is continuously
drawn into the compressor, where it is compressed to a high pressure. The air then enters a
combustion chamber, or combustor, where it is mixed with fuel and combustion occurs, re-
sulting in combustion products at an elevated temperature. The combustion products expand
through the turbine and are subsequently discharged to the surroundings. Part of the turbine
work developed is used to drive the compressor; the remainder is available to generate elec-
tricity, to propel a vehicle, or for other purposes. In the system pictured in Fig. 9.8b, the
working fluid receives an energy input by heat transfer from an external source, for example
a gas-cooled nuclear reactor. The gas exiting the turbine is passed through a heat exchanger,
where it is cooled prior to reentering the compressor.
An idealization often used in the study of open gas turbine power plants is that of an
air-standard analysis: air-standard analysis. In an air-standard analysis two assumptions are always made:
gas turbines The working fluid is air, which behaves as an ideal gas.
The temperature rise that would be brought about by combustion is accomplished by a
heat transfer from an external source.
Fuel

Qin
Combustion Heat exchanger

chamber
Compressor Turbine Compressor Turbine

Net Net
work work
out out
Heat exchanger
Air Products

Qout
(a) (b)
Figure 9.8 Simple gas turbine. (a) Open to the atmosphere. (b) Closed.
With an air-standard analysis, we avoid dealing with the complexities of the combustion
process and the change of composition during combustion. An air-standard analysis simplifies
the study of gas turbine power plants considerably. However, numerical values calculated on
this basis may provide only qualitative indications of power plant performance. Sufficient in-
formation about combustion and the properties of products of combustion is known (Chap. 13)
that the study of gas turbines can be conducted without the foregoing assumptions. Still, we
can learn some important aspects of gas turbine operation by proceeding on the basis of an
air-standard analysis, as follows.

9.6 Air-Standard Brayton Cycle
A schematic diagram of an air-standard gas turbine is shown in Fig. 9.9. The directions of
the principal energy transfers are indicated on this figure by arrows. In accordance with the
assumptions of an air-standard analysis, the temperature rise that would be achieved in the

Qin
2 3
Heat exchanger

Wcycle
Compressor Turbine
Heat exchanger
1 4

Qout
Figure 9.9 Air-standard gas turbine
cycle.
combustion process is brought about by a heat transfer to the working fluid from an exter-
nal source and the working fluid is considered to be air as an ideal gas. With the air-standard
idealizations, air would be drawn into the compressor at state 1 from the surroundings and
later returned to the surroundings at state 4 with a temperature greater than the ambient tem-
perature. After interacting with the surroundings, each unit mass of discharged air would
eventually return to the same state as the air entering the compressor, so we may think of
the air passing through the components of the gas turbine as undergoing a thermodynamic
cycle. A simplified representation of the states visited by the air in such a cycle can be de-
vised by regarding the turbine exhaust air as restored to the compressor inlet state by pass-
ing through a heat exchanger where heat rejection to the surroundings occurs. The cycle that
Brayton cycle results with this further idealization is called the air-standard Brayton cycle.

The following expressions for the work and heat transfers of energy that occur at steady state
are readily derived by reduction of the control volume mass and energy rate balances. These
energy transfers are positive in the directions of the arrows in Fig. 9.9. Assuming the turbine
operates adiabatically and with negligible effects of kinetic and potential energy, the work
developed per unit of mass is
#
Wt
# h3 h4 (9.15)
m
#
where m denotes the mass flow rate. With the same assumptions, the compressor work per
unit of mass is
#
Wc
# h2 h1 (9.16)
m
#
The symbol Wc denotes work input and takes on a positive value. The heat added to the cy-
cle per unit of mass is
#
Qin
# h3 h2 (9.17)
m
The heat rejected per unit of mass is
#
Qout
# h4 h1 (9.18)
m
#
where Qout is positive in value.
The thermal efficiency of the cycle in Fig. 9.9 is
1h3 h4 2 1h2 h1 2
# # # #
Wt m Wcm
h # (9.19)
Qinm
#
h3 h2
The back work ratio for the cycle is
# #
Wcm h2 h1
bwr # # (9.20)
Wt m h3 h4
For the same pressure rise, a gas turbine compressor would require a much greater work in-
put per unit of mass flow than the pump of a vapor power plant because the average specific
volume of the gas flowing through the compressor would be many times greater than that of
the liquid passing through the pump (see discussion of Eq. 6.53b in Sec. 6.9). Hence, a
relatively large portion of the work developed by the turbine is required to drive the
compressor. Typical back work ratios of gas turbines range from 40 to 80%. In comparison,
the back work ratios of vapor power plants are normally only 1 or 2%.
If the temperatures at the numbered states of the cycle are known, the specific enthalpies
required by the foregoing equations are readily obtained from the ideal gas table for air,
Table A-22. Alternatively, with the sacrifice of some accuracy, the variation of the specific
heats with temperature can be ignored and the specific heats taken as constant. The air-
standard analysis is then referred to as a cold air-standard analysis. As illustrated by the
discussion of internal combustion engines given previously, the chief advantage of the
assumption of constant specific heats is that simple expressions for quantities such as thermal
efficiency can be derived, and these can be used to deduce qualitative indications of cycle
performance without involving tabular data.
Since Eqs. 9.15 through 9.20 have been developed from mass and energy rate balances,
they apply equally when irreversibilities are present and in the absence of irreversibilities.
Although irreversibilities and losses associated with the various power plant components have
a pronounced effect on overall performance, it is instructive to consider an idealized cycle
in which they are assumed absent. Such a cycle establishes an upper limit on the perform-
ance of the air-standard Brayton cycle. This is considered next.
9.6.2 Ideal Air-Standard Brayton Cycle

Ignoring irreversibilities as the air circulates through the various components of the Brayton
cycle, there are no frictional pressure drops, and the air flows at constant pressure through
the heat exchangers. If stray heat transfers to the surroundings are also ignored, the processes
through the turbine and compressor are isentropic. The ideal cycle shown on the pv and Ts
diagrams in Fig. 9.10 adheres to these idealizations.
Areas on the Ts and pv diagrams of Fig. 9.10 can be interpreted as heat and work, re-
spectively, per unit of mass flowing. On the Ts diagram, area 23ab2 represents the heat
added per unit of mass and area 14ab1 is the heat rejected per unit of mass. On the pv
diagram, area 12ab1 represents the compressor work input per unit of mass and area
34ba3 is the turbine work output per unit of mass (Sec. 6.9). The enclosed area on each
figure can be interpreted as the net work output or, equivalently, the net heat added.
When air table data are used to conduct an analysis involving the ideal Brayton cycle,
the following relationships, based on Eq. 6.43, apply for the isentropic processes 12
and 34
p2
pr2 pr1 (9.21)
p1
p4 p1
pr4 pr3 pr3 (9.22)
p3 p2
p 3
T
2 3 3
a
2
c 4
p=
s=
s= 2
c
c c
p=
b 1
1 4
v b a s
Figure 9.10 Air-standard ideal Brayton cycle.
Recall that pr is tabulated versus temperature in Tables A-22. Since the air flows through the
heat exchangers of the ideal cycle at constant pressure, it follows that p4p3 p1p2. This
relationship has been used in writing Eq. 9.22.
When an ideal Brayton cycle is analyzed on a cold air-standard basis, the specific heats
are taken as constant. Equations 9.21 and 9.22 are then replaced, respectively, by the fol-
lowing expressions, based on Eq. 6.45
p2 1k12k
T2 T1 a b (9.23)
p1
p4 1k12k p1 1k12k
T4 T3 a b T3 a b (9.24)
p3 p2
where k is the specific heat ratio, k cpcv.
In the next example, we illustrate the analysis of an ideal air-standard Brayton cycle and
compare results with those obtained on a cold air-standard basis.
EXAMPLE 9.4 Analyzing the Ideal Brayton Cycle
Air enters the compressor of an ideal air-standard Brayton cycle at 100 kPa, 300 K, with a volumetric flow rate of 5 m3/s.
The compressor pressure ratio is 10. The turbine inlet temperature is 1400 K. Determine (a) the thermal efficiency of the
cycle, (b) the back work ratio, (c) the net power developed, in kW.
SOLUTION
Known: An ideal air-standard Brayton cycle operates with given compressor inlet conditions, given turbine inlet tempera-
ture, and a known compressor pressure ratio.
Find: Determine the thermal efficiency, the back work ratio, and the net power developed, in kW.

Qin
T 3
p2 T3 = 1400 K

p1 = 10 T3 = 1400 K
Heat exchanger
2 3
a
kP
0
100
Wcycle =
p
Compressor Turbine
4
2
Pa
0k
10
p=
Heat exchanger
1 4 T1 = 300 K
1
p1 = 100 kPa
Qout
T1 = 300 K s
Figure E9.4
Assumptions:
1. Each component is analyzed as a control volume at steady state. The control volumes are shown on the accompanying
sketch by dashed lines.
2. The turbine and compressor processes are isentropic.
3. There are no pressure drops for flow through the heat exchangers.
5. The working fluid is air modeled as an ideal gas.
Analysis: The analysis begins by determining the specific enthalpy at each numbered state of the cycle. At state 1, the tem-
perature is 300 K. From Table A-22, h1 300.19 kJ/kg and pr1 1.386.
Since the compressor process is isentropic, the following relationship can be used to determine h2
p 110211.3862 13.86
p2
pr2
p1 r1
Then, interpolating in Table A-22, we obtain h2 579.9 kJ/kg.
The temperature at state 3 is given as T3 1400 K. With this temperature, the specific enthalpy at state 3 from Table A-22
is h3 1515.4 kJ/kg. Also, pr3 450.5.
The specific enthalpy at state 4 is found by using the isentropic relation
1450.5211102 45.05
p4
pr4 pr3
p3
Interpolating in Table A-22, we get h4 808.5 kJ/kg.
(a) The thermal efficiency is

1Wt m2 1Wc m2
# # # #
h #
Qin m
#
1h3 h4 2 1h2 h1 2 11515.4 808.52 1579.9 300.192

h3 h2 1515.4 579.9
706.9 279.7
0.457 145.7% 2
935.5
# #
Wc m h2 h1
0.396 139.6%2
279.7
bwr # #
Wt m h3 h4 706.9
(c) The net power developed is
Wcycle m 3 1h3 h4 2 1h2 h1 2 4
# #
#
To evaluate the net power requires the mass flow rate m , which can be determined from the volumetric flow rate and specific
volume at the compressor inlet as follows
# 1AV2 1
m
v1
Since v1 1RM2T1 p1, this becomes
# 1AV2 1p1 15 m3/s21100 103 N/m2 2

m
1RM2T1
a b 1300 K2
8314 N # m
28.97 kg # K
5.807 kg/s
Finally,
Wcycle 15.807 kg/s21706.9 279.72 a b ` ` 2481 kW

# kJ 1 kW
kg 1 kJ/s
The use of the ideal gas table for air is featured in this solution. A solution also can be developed on a cold air-standard
basis in which constant specific heats are assumed. The details are left as an exercise, but for comparison the results are
presented for the case k 1.4 in the following table:
Cold Air-Standard Analysis,

Parameter Air-Standard Analysis k 1.4
T2 574.1 K 579.2 K
T4 787.7 K 725.1 K
0.457 0.482
bwr
# 0.396 0.414
Wcycle 2481 kW 2308 kW
The value of the back work ratio in the present gas turbine case is significantly greater than the back work ratio of the
simple vapor power cycle of Example 8.1.
EFFECT OF PRESSURE RATIO ON PERFORMANCE. Conclusions that are qualitatively cor-

rect for actual gas turbines can be drawn from a study of the ideal Brayton cycle. The first
of these conclusions is that the thermal efficiency increases with increasing pressure ratio
across the compressor. for example. . . referring again to the Ts diagram of Fig. 9.10,
we see that an increase in the pressure ratio changes the cycle from 12341 to
12341. Since the average temperature of heat addition is greater in the latter cycle and
both cycles have the same heat rejection process, cycle 12341 would have the greater
thermal efficiency.
The increase in thermal efficiency with the pressure ratio across the compressor is also
brought out simply by the following development, in which the specific heat cp, and thus the
specific heat ratio k, is assumed constant. For constant cp, Eq. 9.19 becomes
cp 1T3 T4 2 cp 1T2 T1 2 1T4 T1 2
h 1
cp 1T3 T2 2 1T3 T2 2
Or, on further rearrangement
T1 T4T1 1
h1 a b
T2 T3T2 1
60 From Eqs. 9.23 and 9.24 above, T4T1 T3T2, so
T1
h1
(%)
T2
Finally, introducing Eq. 9.23
0
0 2 4 6 8 10
1k constant2
1
h1
1 p2 p1 2 1k12k
Compressor pressure ratio (9.25)
Figure 9.11 Ideal
Brayton cycle thermal By inspection of Eq. 9.25, it can be seen that the cold air-standard ideal Brayton cycle ther-
efficiency versus com- mal efficiency is a function of the pressure ratio across the compressor. This relationship is
pressor pressure ratio, shown in Fig. 9.11 for k 1.4.
k 1.4. There is a limit of about 1700 K imposed by metallurgical considerations on the maxi-
mum allowed temperature at the turbine inlet. It is instructive therefore to consider the ef-
fect of compressor pressure ratio on thermal efficiency when the turbine inlet temperature is
restricted to the maximum allowable temperature. The Ts diagrams of two ideal Brayton
cycles having the same turbine inlet temperature but different compressor pressure ratios are
shown in Fig. 9.12. Cycle A has a greater pressure ratio than cycle B and thus the greater
thermal efficiency. However, cycle B has a larger enclosed area and thus the greater net work
developed per unit of mass flow. Accordingly, for cycle A to develop the same net power
Cycle A: 1-2-3-4-1
larger thermal efficiency
T Turbine inlet
3 3 temperature
2
2 4
4 Cycle B: 1-2-3-4-1
1 larger net work per unit of mass flow
Figure 9.12 Ideal Brayton cycles with
different pressure ratios and the same turbine
s inlet temperature.
output as cycle B, a larger mass flow rate would be required, and this might dictate a larger
system. These considerations are important for gas turbines intended for use in vehicles where
engine weight must be kept small. For such applications, it is desirable to operate near the
compressor pressure ratio that yields the most work per unit of mass flow and not the pres-
sure ratio for the greatest thermal efficiency.
Example 9.5 provides an illustration of the determination of the compressor pressure ra-
tio for maximum net work per unit of mass flow for the cold air-standard Brayton cycle.
EXAMPLE 9.5 Compressor Pressure Ratio for Maximum Net Work
Determine the pressure ratio across the compressor of an ideal Brayton cycle for the maximum net work output per unit of
mass flow if the state at the compressor inlet and the temperature at the turbine inlet are fixed. Use a cold air-standard analysis
and ignore kinetic and potential energy effects. Discuss.
SOLUTION
Known: An ideal Brayton cycle operates with a specified state at the inlet to the compressor and a specified turbine inlet
temperature.
Find: Determine the pressure ratio across the compressor for the maximum net work output per unit of mass flow, and dis-
cuss the result.
T Turbine inlet
temperature fixed 3
Assumptions:
p2

p1 variable 1. Each component is analyzed as a control volume at steady state.
4
2 4. Kinetic and potential energy effects are negligible.
6. The specific heat cp and the specific heat ratio k are constant.
1 Compressor inlet state fixed
s
Figure E9.5
Analysis: The net work of the cycle per unit of mass flow is
#
Wcycle
# 1h3 h4 2 1h2 h1 2
m
Since cp is constant (assumption 6)
#
Wcycle
# cp 3 1T3 T4 2 1T2 T1 2 4
m
Or on rearrangement
#
Wcycle
# cpT1 a
T3 T4 T3 T2

1b
m T1 T3 T1 T1
Replacing the temperature ratios T2T1 and T4T3 by using Eqs. 9.23 and 9.24, respectively, gives
#
Wcycle T3 p1 1k12k p2 1k12k
# cpT1 c a b a b
1d
T3
m T1 T1 p2 p1
From this expression it can be concluded that for specified values of T1, T3, and cp, the value of the net work output per unit
of mass flow varies with the pressure ratio p2p1 only.
To determine the pressure ratio that maximizes the net work output per unit of mass flow, first form the derivative
01Wcycle m2
#
T3 p1 1k12k p2 1k12k
#
e cpT1 c a b a b
1d f
0 T3

0 1 p2 p1 2 0 1p2 p1 2 T1 T1 p2 p1
k1 T3 p1 1k p1 2 p2 1k
cpT1a bca b a b a b a b d
k T1 p2 p2 p1
k1 T3 p1 12k12k p2 1k
cpT1a bca b a b a b d
k T1 p2 p1
When the partial derivative is set to zero, the following relationship is obtained
T3 k 321k124
a b
p2
p1 T1
By checking the sign of the second derivative, we can verify that the net work per unit of mass flow is a maximum when this
relationship is satisfied.
For gas turbines intended for transportation, it is desirable to keep engine size small. Thus, the gas turbine should operate
near the compressor pressure ratio that yields the most work per unit of mass flow. The present example provides an elementary
illustration of how the compressor pressure ratio for maximum net work per unit of mass flow is affected by the constraint of
a fixed turbine inlet temperature.
9.6.3 Considering Gas Turbine Irreversibilities and Losses

The principal state points of an air-standard gas turbine might be shown more realisti-
cally as in Fig. 9.13a. Because of frictional effects within the compressor and turbine, the
working fluid would experience increases in specific entropy across these components.
Owing to friction, there also would be pressure drops as the working fluid passes through
the heat exchangers. However, because frictional pressure drops are less significant sources
of irreversibility, we ignore them in subsequent discussions and for simplicity show the
flow through the heat exchangers as occurring at constant pressure. This is illustrated by
Fig. 9.13b. Stray heat transfers from the power plant components to the surroundings rep-
resent losses, but these effects are usually of secondary importance and are also ignored
in subsequent discussions.
T T 3
3
p =c p =c
2 2s 2
4
4
4s
c
p= c
p=
1
1
s s
(a) (b)
Figure 9.13 Effects of irreversibilities on the air-standard gas turbine.
As the effect of irreversibilities in the turbine and compressor becomes more pronounced,
the work developed by the turbine decreases and the work input to the compressor increases,
resulting in a marked decrease in the net work of the power plant. Accordingly, if an appre-
ciable amount of net work is to be developed by the plant, relatively high turbine and com-
pressor efficiencies are required. After decades of developmental effort, efficiencies of 80 to
90% can now be achieved for the turbines and compressors in gas turbine power plants. Des-
ignating the states as in Fig. 9.13b, the isentropic turbine and compressor efficiencies are
given by
1Wt m2
# #
h3 h4
ht # #
1Wt m2 s h3 h4s
1Wcm2 s
# #
h2s h1
hc # #
1Wcm2 h2 h1
The effects of irreversibilities in the turbine and compressor are important. Still, among
the irreversibilities of actual gas turbine power plants, combustion irreversibility is the most
significant by far. An air-standard analysis does not allow this irreversibility to be evaluated,
however, and means introduced in Chap. 13 must be applied. Combustion irreversibility is
also briefly considered in Sec. 9.10.
Example 9.6 brings out the effect of turbine and compressor irreversibilities on plant
performance.
EXAMPLE 9.6 Brayton Cycle with Irreversibilities
Reconsider Example 9.4, but include in the analysis that the turbine and compressor each have an isentropic efficiency of
80%. Determine for the modified cycle (a) the thermal efficiency of the cycle, (b) the back work ratio, (c) the net power de-
veloped, in kW.
SOLUTION
Known: An air-standard Brayton cycle operates with given compressor inlet conditions, given turbine inlet temperature, and
known compressor pressure ratio. The compressor and turbine each have an isentropic efficiency of 80%.
Find: Determine the thermal efficiency, the back work ratio, and the net power developed, in kW.
3
T3 = 1400 K
T
a Assumptions:
kP
00
10 1. Each component is analyzed as a control volume at steady state.
= 4
p
2. The compressor and turbine are adiabatic.
2 4s 3. There are no pressure drops for flow through the heat exchangers.
2s a
0 kP
p=
T1 = 300 K
1
s
Figure E9.6
Analysis:
(a) The thermal efficiency is given by
1Wt m2 1Wc m2

# # # #
h #
Qin m
#
The work terms in the numerator of this expression are evaluated using the given values of the compressor and turbine isen-
tropic efficiencies as follows:
The turbine work per unit of mass is
# #
a # b
Wt Wt
# h t
m m s
# #
where t is the turbine efficiency. The value of (Wt m)s is determined in the solution to Example 9.4 as 706.9 kJ/kg. Thus
#
Wt
# 0.81706.92 565.5 kJ/kg
m
For the compressor, the work per unit of mass is
1Wc m2 s
# # #
Wc
#
m hc
# #
where c is the compressor efficiency. The value of (Wcm)s is determined in the solution to Example 9.4 as 279.7 kJ/kg, so
#
Wc 279.7
# 349.6 kJ/kg
m 0.8
The specific enthalpy at the compressor exit, h2, is required to evaluate the denominator of the thermal efficiency expres-
sion. This enthalpy can be determined by solving
#
Wc
# h2 h1
m
to obtain
# #
h2 h1
Wc m
9.7 Regenerative Gas Turbines 399
Inserting known values
h2 300.19
349.6 649.8 kJ/kg
The heat transfer to the working fluid per unit of mass flow is then
#
Qin
# h3 h2 1515.4 649.8 865.6 kJ/kg
m
where h3 is from the solution to Example 9.4.

Finally, the thermal efficiency is
565.5 349.6
h 0.249 124.9% 2
865.6

# #
Wc m
0.618 161.8%2
349.6
bwr # #
Wt m 565.5
(c) The mass flow rate is the same as in Example 9.4. The net power developed by the cycle is then
Wcycle a5.807 b 1565.5 349.62 ` ` 1254 kW

kg
# kJ 1 kW
s kg 1 kJ/s
The solution to this example on a cold air-standard basis is left as an exercise.

Irreversibilities within the turbine and compressor have a significant impact on the performance of gas turbines. This is
brought out by comparing the results of the present example with those of Example 9.4. Irreversibilities result in an in-
crease in the work of compression and a reduction in work output of the turbine. The back work ratio is greatly increased
and the thermal efficiency significantly decreased.

9.7 Regenerative Gas Turbines
The turbine exhaust temperature of a gas turbine is normally well above the ambient tem-
perature. Accordingly, the hot turbine exhaust gas has a potential for use (exergy) that would
be irrevocably lost were the gas discarded directly to the surroundings. One way of utilizing
this potential is by means of a heat exchanger called a regenerator, which allows the air ex- regenerator
iting the compressor to be preheated before entering the combustor, thereby reducing the
amount of fuel that must be burned in the combustor. The combined cycle arrangement con-
sidered in Sec. 9.10 is another way to utilize the hot turbine exhaust gas.
An air-standard Brayton cycle modified to include a regenerator is illustrated in Fig. 9.14.
The regenerator shown is a counterflow heat exchanger through which the hot turbine ex-
haust gas and the cooler air leaving the compressor pass in opposite directions. Ideally, no
frictional pressure drop occurs in either stream. The turbine exhaust gas is cooled from state 4
to state y, while the air exiting the compressor is heated from state 2 to state x. Hence, a heat
transfer from a source external to the cycle is required only to increase the air temperature
from state x to state 3, rather than from state 2 to state 3, as would be the case without
regeneration. The heat added per unit of mass is then given by
#
Qin
# h3 hx (9.26)
m
y Regenerator
3
Qin
T
Combustor
x
2 3 4
x 4
2 y
Compressor Turbine
Wcycle
1
1
s
Figure 9.14 Regenerative air-standard gas turbine cycle.
The net work developed per unit of mass flow is not altered by the addition of a regenera-
tor. Thus, since the heat added is reduced, the thermal efficiency increases.
REGENERATOR EFFECTIVENESS. From Eq. 9.26 it can be concluded that the external
heat transfer required by a gas turbine power plant decreases as the specific enthalpy
hx increases and thus as the temperature Tx increases. Evidently, there is an incentive in
terms of fuel saved for selecting a regenerator that provides the greatest practical value
for this temperature. To consider the maximum theoretical value for Tx, refer to Fig. 9.15,
which shows temperature variations of the hot and cold streams of a counterflow heat
exchanger.
z Hotter z Hotter
stream in stream in
Colder Colder
stream in stream in
t Thot, in Thot, in
Ho
Tcold, out Hot
d
Thot, out ld Col
Co
Tcold, in Tcold, in
T T 0
z z
(a) (b)
Figure 9.15 Temperature distributions in counterflow heat exchangers. (a) Actual.
(b) Reversible.
First, refer to Fig. 9.15a. Since a finite temperature difference between the streams is
required for heat transfer to occur, the temperature of the cold stream at each loca-
tion, denoted by the coordinate z, is less than that of the hot stream. In particular,
the temperature of the colder stream as it exits the heat exchanger is less than the
temperature of the incoming hot stream. If the heat transfer area were increased,
providing more opportunity for heat transfer between the two streams, there would be
a smaller temperature difference at each location.
In the limiting case of infinite heat transfer area, the temperature difference would
approach zero at all locations, as illustrated in Fig. 9.15b, and the heat transfer would
approach reversibility. In this limit, the exit temperature of the colder stream would
approach the temperature of the incoming hot stream. Thus, the highest possible
temperature that could be achieved by the colder stream is the temperature of the
incoming hot gas.
Referring again to the regenerator of Fig. 9.14, we can conclude from the discussion of
Fig. 9.15 that the maximum theoretical value for the temperature Tx is the turbine exhaust
temperature T4, obtained if the regenerator were operating reversibly. The regenerator effec-
tiveness, reg, is a parameter that gauges the departure of an actual regenerator from such an
ideal regenerator. The regenerator effectiveness is defined as the ratio of the actual enthalpy
increase of the air flowing through the compressor side of the regenerator to the maximum
theoretical enthalpy increase. That is,
hx h2
hreg (9.27) regenerator effectiveness
h4 h2
As heat transfer approaches reversibility, hx approaches h4 and hreg tends to unity (100%).
In practice, regenerator effectiveness values typically range from 60 to 80%, and thus the
temperature Tx of the air exiting on the compressor side of the regenerator is normally well
below the turbine exhaust temperature. To increase the effectiveness above this range would
require greater heat transfer area, resulting in equipment costs that might cancel any advan-
tage due to fuel savings. Moreover, the greater heat transfer area that would be required for
a larger effectiveness can result in a significant frictional pressure drop for flow through the
regenerator, thereby affecting overall performance. The decision to add a regenerator is in-
fluenced by considerations such as these, and the final decision is primarily an economic
one.
In Example 9.7, we analyze an air-standard Brayton cycle with regeneration and explore
the effect on thermal efficiency as the regenerator effectiveness varies.
EXAMPLE 9.7 Brayton Cycle with Regeneration
A regenerator is incorporated in the cycle of Example 9.4. (a) Determine the thermal efficiency for a regenerator effective-
ness of 80%. (b) Plot the thermal efficiency versus regenerator effectiveness ranging from 0 to 80%.
SOLUTION
Known: A regenerative gas turbine operates with air as the working fluid. The compressor inlet state, turbine inlet temper-
ature, and compressor pressure ratio are known.
Find: For a regenerator effectiveness of 80%, determine the thermal efficiency. Also plot the thermal efficiency versus the
regenerator effectiveness ranging from 0 to 80%.
Regenerator
T 3
y T3 = 1400 K

Qin
reg =
80% a
kP
Combustor 0
x 100
=
p
2 3 4
y 4
T3 = 1400 K 2 x
a
kP
100
Compressor Turbine p =
Wcycle
T1 = 300 K
1
T1 = 300 K
1 p1 = 100 kPa s
Figure E9.7a
Assumptions:
2. The compressor and turbine processes are isentropic.
4. The regenerator effectiveness is 80% in part (a).
Analysis:
(a) The specific enthalpy values at the numbered states on the Ts diagram are the same as those in Example 9.4: h1
300.19 kJ/ kg, h2 579.9 kJ/ kg, h3 1515.4 kJ/kg, h4 808.5 kJ/kg.
To find the specific enthalpy hx, the regenerator effectiveness is used as follows: By definition
hx h2
hreg
h4 h2
Solving for hx
hx hreg 1h4 h2 2
h2
10.82 1808.5 579.92
579.9 762.8 kJ/kg
With the specific enthalpy values determined above, the thermal efficiency is
1Wtm2 1Wcm2 1h3 h4 2 1h2 h1 2

# # # #
h
1Qinm2 1h3 hx 2
# #
11515.4 808.52 1579.9 300.192

11515.4 762.82
0.568 156.8% 2
#
(b) The IT code for the solution follows, where reg is denoted as etareg, is eta, Wcompm is Wcomp, and so on.
#
// Fix the states

T1 = 300 // K
p1 = 100 // kPa
h1 = h_T(Air, T1)
s1 = s_TP(Air, T1, p1)
p2 = 1000 // kPa
s2 = s1
h2 = h_T(Air, T2)
T3 = 1400 // K
p3 = p2
h3 = h_T(Air, T3)
p4 = p1
s4 = s3
h4 = h_T(Air, T4)
etareg = 0.8
hx = etareg * (h4 h2) + h2
// Thermal efficiency
Wcomp = h2 h1
Wturb = h3 h4
Qin = h3 hx
eta = (Wturb Wcomp) Qin
Using the Explore button, sweep etareg from 0 to 0.8 in steps of 0.01. Then, using the Graph button, obtain the following
plot:
0.6
0.5
Thermal efficiency
0.4
0.3
0.2
0.1
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Regenerator effectiveness
Figure E9.7b
From the computer data, we see that the cycle thermal efficiency increases from 0.456, which agrees closely with the result
of Example 9.4 (no regenerator), to 0.567 for a regenerator effectiveness of 80%, which agrees closely with the result of
part (a) This trend is also seen in the accompanying graph. Regenerator effectiveness is seen to have a significant effect on
cycle thermal efficiency.
The values for work per unit of mass flow of the compressor and turbine are unchanged by the addition of the regenera-
tor. Thus, the back work ratio and net work output are not affected by this modification.
Comparing the present thermal efficiency value with the one determined in Example 9.4, it should be evident that the ther-
mal efficiency can be increased significantly by means of regeneration.
The regenerator allows improved fuel utilization to be achieved by transferring a portion of the exergy in the hot turbine
exhaust gas to the cooler air flowing on the other side.
9.8 Regenerative Gas Turbines with

Reheat and Intercooling
Two modifications of the basic gas turbine that increase the net work developed are multi-
stage expansion with reheat and multistage compression with intercooling. When used in
conjunction with regeneration, these modifications can result in substantial increases in ther-
mal efficiency. The concepts of reheat and intercooling are introduced in this section.
9.8.1 Gas Turbines with Reheat

For metallurgical reasons, the temperature of the gaseous combustion products entering the tur-
bine must be limited. This temperature can be controlled by providing air in excess of the amount
required to burn the fuel in the combustor (see Chap. 13). As a consequence, the gases exiting
the combustor contain sufficient air to support the combustion of additional fuel. Some gas tur-
reheat bine power plants take advantage of the excess air by means of a multistage turbine with a reheat
combustor between the stages. With this arrangement the net work per unit of mass flow can
be increased. Let us consider reheat from the vantage point of an air-standard analysis.
The basic features of a two-stage gas turbine with reheat are brought out by considering
an ideal air-standard Brayton cycle modified as shown in Fig. 9.16. After expansion from
state 3 to state a in the first turbine, the gas is reheated at constant pressure from state a to
state b. The expansion is then completed in the second turbine from state b to state 4. The
ideal Brayton cycle without reheat, 12341, is shown on the same Ts diagram for com-
parison. Because lines of constant pressure on a Ts diagram diverge slightly with increas-
ing entropy, the total work of the two-stage turbine is greater than that of a single expansion
from state 3 to state 4. Thus, the net work for the reheat cycle is greater than that of the cy-
cle without reheat. Despite the increase in net work with reheat, the cycle thermal efficiency
would not necessarily increase because a greater total heat addition would be required. How-
ever, the temperature at the exit of the turbine is higher with reheat than without reheat, so
the potential for regeneration is enhanced.

Qin Qin
T 3
b
Combustor Reheat
combustor a
2 3 a b 4
2
4
Turbine Turbine
stage 1 stage 2
Wcycle
Compressor
1
1 4
s
Figure 9.16 Ideal gas turbine with reheat.

9.8 Regenerative Gas Turbines with Reheat and Intercooling 405
When reheat and regeneration are used together, the thermal efficiency can increase
significantly. The following example provides an illustration.
EXAMPLE 9.8 Brayton Cycle with Reheat and Regeneration
Consider a modification of the cycle of Example 9.4 involving reheat and regeneration. Air enters the compressor at 100 kPa,
300 K and is compressed to 1000 kPa. The temperature at the inlet to the first turbine stage is 1400 K. The expansion takes
place isentropically in two stages, with reheat to 1400 K between the stages at a constant pressure of 300 kPa. A regenerator
having an effectiveness of 100% is also incorporated in the cycle. Determine the thermal efficiency.
SOLUTION
Known: An ideal air-standard gas turbine cycle operates with reheat and regeneration. Temperatures and pressures at prin-
cipal states are specified.
Find: Determine the thermal efficiency.
T
T3 = 1400 K 3 b
Assumptions:
Regenerator
exit x 4 1. Each component of the power plant is analyzed as a control volume at
a
a a
steady state.
kP kP
0 0 2. The compressor and turbine processes are isentropic.
100 30
= =
p p 3. There are no pressure drops for flow through the heat exchangers.
2 P a
0k 4. The regenerator effectiveness is 100%.
10
p= 5. Kinetic and potential energy effects are negligible.
T1 = 300 K
1
s
Figure E9.8
Analysis: We begin by determining the specific enthalpies at each principal state of the cycle. States 1, 2, and 3 are the
same as in Example 9.4: h1 300.19 kJ/kg, h2 579.9 kJ/kg, h3 1515.4 kJ/kg. The temperature at state b is the same as
at state 3, so hb h3.
Since the first turbine process is isentropic, the enthalpy at state a can be determined using pr data from Table A-22 and
the relationship
1450.52
pa 300
pra pr3 135.15
p3 1000
Interpolating in Table A-22, we get ha 1095.9 kJ/kg.

The second turbine process is also isentropic, so the enthalpy at state 4 can be determined similarly. Thus
1450.52
p4 100
pr4 prb 150.17
pb 300
Interpolating in Table A-22, we obtain h4 1127.6 kJ/kg. Since the regenerator effectiveness is 100%, hx h4
1127.6 kJ/kg.
The thermal efficiency calculation must take into account the compressor work, the work of each turbine, and the total
heat added. Thus, on a unit mass basis
1h3 ha 2
1hb h4 2 1h2 h1 2
h
1h3 hx 2
1hb ha 2
11515.4 1095.92
11515.4 1127.62 1579.9 300.192

11515.4 1127.62
11515.4 1095.92
0.654 165.4% 2
Comparing the present value with the thermal efficiency determined in part (a) of Example 9.4, we can conclude that the
use of reheat coupled with regeneration can result in a substantial increase in thermal efficiency.
9.8.2 Compression with Intercooling

The net work output of a gas turbine also can be increased by reducing the compressor work
input. This can be accomplished by means of multistage compression with intercooling. The
present discussion provides an introduction to this subject.
Let us first consider the work input to compressors at steady state, assuming that irre-
versibilities are absent and changes in kinetic and potential energy from inlet to exit are
negligible. The pv diagram of Fig. 9.17 shows two possible compression paths from a
specified state 1 to a specified final pressure p2. Path 12 is for an adiabatic compression.
Path 12 corresponds to a compression with heat transfer from the working fluid to the sur-
roundings. The area to the left of each curve equals the magnitude of the work per unit mass
of the respective process (see Sec. 6.9). The smaller area to the left of Process 12 indi-
cates that the work of this process is less than for the adiabatic compression from 1 to 2.
This suggests that cooling a gas during compression is advantageous in terms of the work-
input requirement.
Although cooling a gas as it is compressed would reduce the work, a heat transfer rate
high enough to effect a significant reduction in work is difficult to achieve in practice. A
practical alternative is to separate the work and heat interactions into separate processes
intercooler by letting compression take place in stages with heat exchangers, called intercoolers, cool-
ing the gas between stages. Figure 9.18 illustrates a two-stage compressor with an
p
2 2
p2
Adiabatic compression
Compression with cooling

W_c 2
__ int = vdp
m
rev 1
p1
T1
Figure 9.17 Internally reversible compres-
v sion processes between two fixed pressures.
Compressor Compressor
stage 1 stage 2
Wc
1 c d
Intercooler

Qout
p T
2 2
a
p2
T=c d c
pi 2 2 pi
p1
c
s=c
d
b 1
1 Figure 9.18 Two-stage
v s compression with intercooling.
intercooler. The accompanying pv and Ts diagrams show the states for internally
reversible processes:
Process 1 c is an isentropic compression from state 1 to state c where the pressure

is pi.
Process cd is constant-pressure cooling from temperature Tc to Td.
Process d2 is an isentropic compression to state 2.
The work input per unit of mass flow is represented on the pv diagram by shaded area
1cd2ab1. Without intercooling the gas would be compressed isentropically in a sin-
gle stage from state 1 to state 2 and the work would be represented by enclosed area
12ab1. The crosshatched area on the pv diagram represents the reduction in work that
would be achieved with intercooling.
Some large compressors have several stages of compression with intercooling between
stages. The determination of the number of stages and the conditions at which to operate
the various intercoolers is a problem in optimization. The use of multistage compression
with intercooling in a gas turbine power plant increases the net work developed by reduc-
ing the compression work. By itself, though, compression with intercooling would not nec-
essarily increase the thermal efficiency of a gas turbine because the temperature of the air
entering the combustor would be reduced (compare temperatures at states 2 and 2 on the
Ts diagram of Fig. 9.18). A lower temperature at the combustor inlet would require addi-
tional heat transfer to achieve the desired turbine inlet temperature. The lower temperature
at the compressor exit enhances the potential for regeneration, however, so when intercooling
is used in conjunction with regeneration, an appreciable increase in thermal efficiency can
result.
In the next example, we analyze a two-stage compressor with intercooling between the
stages. Results are compared with those for a single stage of compression.
EXAMPLE 9.9 Compression with Intercooling
Air is compressed from 100 kPa, 300 K to 1000 kPa in a two-stage compressor with intercooling between stages. The inter-
cooler pressure is 300 kPa. The air is cooled back to 300 K in the intercooler before entering the second compressor stage.
Each compressor stage is isentropic. For steady-state operation and negligible changes in kinetic and potential energy from
inlet to exit, determine (a) the temperature at the exit of the second compressor stage and (b) the total compressor work input
per unit of mass flow. (c) Repeat for a single stage of compression from the given inlet state to the final pressure.
SOLUTION
Known: Air is compressed at steady state in a two-stage compressor with intercooling between stages. Operating pressures
and temperatures are given.
Find: Determine the temperature at the exit of the second compressor stage and the total work input per unit of mass flow.
Repeat for a single stage of compression.
p2 = 1000 kPa
2
p 2 3
p2 = 1000 kPa
Compressor Compressor
stage 1 stage 2
Wc
d c
pi = 300 kPa
T
1 c 1 =
d 30
T1 = 300 K Intercooler 0K
p1 = 100 kPa Td = 300 K
p1 = 100 kPa
1
v

Qout
Figure E9.9
Assumptions:
1. The compressor stages and intercooler are analyzed as control volumes at steady state. The control volumes are shown on
the accompanying sketch by dashed lines.
2. The compression processes are isentropic.
3. There is no pressure drop for flow through the intercooler.
Analysis:
(a) The temperature at the exit of the second compressor stage, T2, can be found using the following relationship for the isen-
tropic process d2
p2
pr2 pr d
pd
With prd at Td 300 K from Table A-22, p2 1000 kPa, and pd 300 kPa,
pr2 11.3862
1000
4.62
300
Interpolating in Table A-22, we get T2 422 K and h2 423.8 kJ/kg
(b) The total compressor work input per unit of mass is the sum of the work inputs for the two stages. That is
#
# 1hc h1 2
1h2 hd 2
Wc
m
From Table A-22 at T1 300 K, h1 300.19 kJ/kg. Since Td T1, hd 300.19 kJ/kg. To find hc, use pr data from
Table A-22 together with p1 100 kPa and pc 300 kPa to write
11.3862
pc 300
pr c pr1 4.158
p1 100
Interpolating in Table A-22, we obtain hc 411.3 kJ/kg. Hence, the total compressor work per unit of mass is
#
# 1411.3 300.192
1423.8 300.192 234.7 kJ/kg
Wc
m
(c) For a single isentropic stage of compression, the exit state would be state 3 located on the accompanying pv diagram.
The temperature at this state can be determined using
11.3862
p3 1000
pr3 pr1 13.86
p1 100
Interpolating in Table A-22, we get T3 574 K and h3 579.9 kJ/kg.
The work input for a single stage of compression is then
#
Wc
# h3 h1 579.9 300.19 279.7 kJ/kg
m
This calculation confirms that a smaller work input is required with two-stage compression and intercooling than with a single
stage of compression. With intercooling, however, a much lower gas temperature is achieved at the compressor exit.
Referring again to Fig. 9.18, the size of the crosshatched area on the pv diagram repre-
senting the reduction in work with intercooling depends on both the temperature Td at the
exit of the intercooler and the intercooler pressure pi. By properly selecting Td and pi, the
total work input to the compressor can be minimized. For example, if the pressure pi is spec-
ified, the work input would decrease (crosshatched area would increase) as the temperature
Td approaches T1, the temperature at the inlet to the compressor. For air entering the com-
pressor from the surroundings, T1 would be the limiting temperature that could be achieved
at state d through heat transfer with the surroundings only. Also, for a specified value of the
temperature Td, the pressure pi can be selected so that the total work input is a minimum
(crosshatched area is a maximum).
Example 9.10 provides an illustration of the determination of the intercooler pressure for
minimum total work using a cold air-standard analysis.
EXAMPLE 9.10 Intercooler Pressure for Minimum Compressor Work
If the inlet state and the exit pressure are specified for a two-stage compressor operating at steady state, show that the mini-
mum total work input is required when the pressure ratio is the same across each stage. Use a cold air-standard analysis
assuming that each compression process is isentropic, there is no pressure drop through the intercooler, and the temperature
at the inlet to each compressor stage is the same. Kinetic and potential energy effects can be ignored.
SOLUTION
Known: A two-stage compressor with intercooling operates at steady state under specified conditions.
Find: Show that the minimum total work input is required when the pressure ratio is the same across each stage.
p
2
p2 specified Assumptions:
1. The compressor stages and intercooler are analyzed as control volumes

at steady state.
s=
c
2. The compression processes are isentropic.

c 3. There is no pressure drop for flow through the intercooler.
pi variable
d
4. The temperature at the inlet to both compressor stages is the same.
s=
T
= 5. Kinetic and potential energy effects are negligible.
c
c
1 6. The working fluid is air modeled as an ideal gas.
7. The specific heat cp and the specific heat ratio k are constant.
Compressor inlet state specified
v
Figure E9.10
Analysis: The total compressor work input per unit of mass flow is
#
# 1hc h1 2
1h2 hd 2
Wc
m
Since cp is constant
#
# cp 1Tc T1 2
cp 1T2 Td 2
Wc
m
With Td T1 (assumption 4), this becomes on rearrangement
#
# cpT1 a
Wc Tc T2
2b
m T1 T1
Since the compression processes are isentropic and the specific heat ratio k is constant, the pressure and temperature ratios
across the compressor stages are related, respectively, by
pi 1k12k p2 1k12k
a b a b
Tc T2
and
T1 p1 Td pi
In the second of these equations, Td T1 by assumption 4.
Collecting results
pi 1k12k p2 1k12k
#
# cpT1 c a b
a b 2d
Wc
m p1 pi
Hence, for specified values of T1, p1, p2, and cp, the value of the total compressor work input varies with the intercooler pres-
sure only. To determine the pressure pi that minimizes the total work, form the derivative
0 1Wc m2 pi 1k12k p2 1k12k
# #
e cpT1 c a b
a b 2d f
0

0pi 0pi p1 pi
k1 pi 1k 1 p2 1k p2
cpT1 a b c a b a b
a b a 2 b d
k p1 p1 pi pi
k1 1 pi 1k12k p2 1k12k
cpT1 a b ca b a b d
k pi p1 pi
When the partial derivative is set to zero, the desired relationship is obtained
pi p2
p1

pi
By checking the sign of the second derivative, it can be verified that the total compressor work is a minimum.
This relationship is for a two-stage compressor. Appropriate relations can be obtained similarly for multistage compressors.
9.8.3 Reheat and Intercooling

Reheat between turbine stages and intercooling between compressor stages provide two im-
portant advantages: The net work output is increased, and the potential for regeneration is
enhanced. Accordingly, when reheat and intercooling are used together with regeneration,
a substantial improvement in performance can be realized. One arrangement incorporating
reheat, intercooling, and regeneration is shown in Fig. 9.19. This gas turbine has two stages
of compression and two turbine stages. The accompanying Ts diagram is drawn to indi-
cate irreversibilities in the compressor and turbine stages. The pressure drops that would
occur as the working fluid passes through the intercooler, regenerator, and combustors are
not shown.
10 Regenerator

Qin, 1 Qin, 2
Combustor 1 Combustor 2
5
4 6 7 8 9
Compressor Compressor Turbine Turbine

1 2 1 2
Wcycle
1 2 3
Intercooler
T 6
8
7
Qout 5 9
7s
9s
4s 4 10
2s 2
3
1
s
Figure 9.19 Regenerative gas turbine with intercooling and reheat.
Example 9.11 illustrates the analysis of a regenerative gas turbine with intercooling and
reheat.
EXAMPLE 9.11 Regenerative Gas Turbine with Intercooling and Reheat
A regenerative gas turbine with intercooling and reheat operates at steady state. Air enters the compressor at 100 kPa, 300 K
with a mass flow rate of 5.807 kg/s. The pressure ratio across the two-stage compressor is 10. The pressure ratio across the
two-stage turbine is also 10. The intercooler and reheater each operate at 300 kPa. At the inlets to the turbine stages, the tem-
perature is 1400 K. The temperature at the inlet to the second compressor stage is 300 K. The isentropic efficiency of each
compressor and turbine stage is 80%. The regenerator effectiveness is 80%. Determine (a) the thermal efficiency, (b) the back
work ratio, (c) the net power developed, in kW.
SOLUTION
Known: An air-standard regenerative gas turbine with intercooling and reheat operates at steady state. Operating pressures
and temperatures are specified. Turbine and compressor isentropic efficiencies are given and the regenerator effectiveness is
known.
Find: Determine the thermal efficiency, back work ratio, and net power developed, in kW.
10 Regenerator

Qin, 1 Qin, 2
Reheat
Combustor combustor
5
4 6 7 8 9
p4 = p5 = p6 =
1000 kPa
Compressor Compressor Turbine Turbine
1 2 1 2
Wcycle
T6 = T8 = 1400 K p7 = p8 = 300 kPa

1 2 3
Intercooler
6 8
T1 = 300 K T
p1 = 100 kPa
m = 5.807 kg/s p2 = p3 = 300 kPa 7
7s 9
Qout 5 9s
4s 4 10
2s 2
3 1
s
Figure E9.11
Assumptions:
3. The compressor and turbine are adiabatic.
Analysis: We begin by listing the specific enthalpies at the principal states of this cycle. The enthalpies at states 1, 2s, 3,
and 4s are obtained from the solution to Example 9.9 where these states are designated as 1, c, d, and 2, respectively. Thus,
h1 h3 300.19 kJ/kg, h2s 411.3 kJ/kg, h4s 423.8 kJ/kg.
The specific enthalpies at states 6, 7s, 8, and 9s are obtained from the solution to Example 9.8, where these states are des-
ignated as 3, a, b, and 4, respectively. Thus, h6 h8 1515.4 kJ/kg, h7s 1095.9 kJ/kg, h9s 1127.6 kJ/kg.
The specific enthalpy at state 4 can be determined using the isentropic efficiency of the second compressor stage
h4s h3
hc
h4 h3
Solving for h4
h4s h3 423.8 300.19
h4 h3
300.19
a b
hc 0.8
454.7 kJ/kg
Similarly, the specific enthalpy at state 2 is h2 439.1 kJ/kg.
The specific enthalpy at state 9 can be determined using the isentropic efficiency of the second turbine stage
h8 h9
ht
h8 h9s
Solving for h9
h9 h8 ht 1h8 h9s 2 1515.4 0.811515.4 1127.62
1205.2 kJ/kg
Similarly, the specific enthalpy at state 7 is h7 1179.8 kJ/kg.
The specific enthalpy at state 5 can be determined using the regenerator effectiveness
h5 h4
hreg
h9 h4
Solving for h5
h5 h4
hreg 1h9 h4 2 454.7
0.811205.2 454.72
1055.1 kJ/kg
(a) The thermal efficiency must take into account the work of both turbine stages, the work of both compressor stages, and
the total heat added. The total turbine work per unit of mass flow is
#
# 1h6 h7 2
1h8 h9 2
Wt
m
11515.4 1179.82
11515.4 1205.22 645.8 kJ/kg
The total compressor work input per unit of mass flow is

#
# 1h2 h1 2
1h4 h3 2
Wc
m
1439.1 300.192
1454.7 300.192 293.4 kJ/kg
The total heat added per unit of mass flow is

#
# 1h6 h5 2
1h8 h7 2
Qin
m
11515.4 1055.12
11515.4 1179.82 795.9 kJ/kg
Calculating the thermal efficiency
645.8 293.4
h 0.443 144.3% 2
795.9
# #
Wc m
0.454 145.4% 2
293.4
bwr # #
Wt m 645.8
(c) The net power developed is
Wcycle m 1Wt m Wc m2
# # # # # #
a5.807 b 1645.8 293.42 ` ` 2046 kW

kg kJ 1 kJ/s
s kg 1 kW
Comparing the thermal efficiency, back work ratio, and net power values of the current example with the corresponding
values of Example 9.6, it should be evident that gas turbine power plant performance can be increased significantly by
coupling reheat and intercooling with regeneration.
9.9 Gas Turbines for Aircraft Propulsion

Gas turbines are particularly suited for aircraft propulsion because of their favorable power-
turbojet engine to-weight ratios. The turbojet engine is commonly used for this purpose. As illustrated in
Fig. 9.20, this type of engine consists of three main sections: the diffuser, the gas generator,
and the nozzle. The diffuser placed before the compressor decelerates the incoming air rel-
ram effect ative to the engine. A pressure rise known as the ram effect is associated with this deceler-
ation. The gas generator section consists of a compressor, combustor, and turbine, with the
same functions as the corresponding components of a stationary gas turbine power plant. In
a turbojet engine, the turbine power output need only be sufficient to drive the compressor
T 3
Compressor Combustors Turbine
c
p=
4
2
Air Product 5
in gases out
1 c
p=
a 1 2 3 4 5
Diffuser Gas generator Nozzle s

(a) (b)
Figure 9.20 Turbojet engine schematic and accompanying ideal Ts diagram.
9.9 Gas Turbines for Aircraft Propulsion 415
Fuel-spray bars
Compressor Turbine
Combustors Flame holder
Air
in
Diffuser Gas generator Afterburner duct Adjustable

nozzle
Figure 9.21 Schematic of a turbojet engine with afterburner.
and auxiliary equipment, however. The gases leave the turbine at a pressure significantly
greater than atmospheric and expand through the nozzle to a high velocity before being dis-
charged to the surroundings. The overall change in the velocity of the gases relative to the
engine gives rise to the propulsive force, or thrust. Some turbojets are equipped with an
afterburner, as shown in Fig. 9.21. This is essentially a reheat device in which additional afterburner
fuel is injected into the gas exiting the turbine and burned, producing a higher temperature
at the nozzle inlet than would be achieved otherwise. As a consequence, a greater nozzle exit
velocity is attained, resulting in increased thrust.
TURBOJET ANALYSIS. The Ts diagram of the processes in an ideal turbojet engine is

shown in Fig. 9.20b. In accordance with the assumptions of an air-standard analysis, the
working fluid is air modeled as an ideal gas. The diffuser, compressor, turbine, and nozzle
processes are isentropic, and the combustor operates at constant pressure.
Process a1 shows the pressure rise that occurs in the diffuser as the air decelerates
isentropically through this component.
Process 12 is an isentropic compression.
Process 23 is a constant-pressure heat addition.
Process 34 is an isentropic expansion through the turbine during which work is
developed.
Process 45 is an isentropic expansion through the nozzle in which the air accelerates
and the pressure decreases.
Owing to irreversibilities in an actual engine, there would be increases in specific entropy
across the diffuser, compressor, turbine, and nozzle. In addition, there would be a pressure
drop through the combustor of the actual engine. Further details regarding flow through noz-
zles and diffusers are provided in Secs. 9.13 and 9.14. The subject of combustion is discussed
in Chap. 13.
In a typical thermodynamic analysis of a turbojet on an air-standard basis the following
quantities might be known: the velocity at the diffuser inlet, the compressor pressure ratio,
and the turbine inlet temperature. The objective of the analysis would be to determine the
velocity at the nozzle exit. Once the nozzle exit velocity is determined, the thrust is deter-
mined by applying Newtons second law of motion in a form suitable for a control volume
(Sec. 9.12). All principles required for the thermodynamic analysis of turbojet engines on an
air-standard basis have been introduced. Example 9.12 provides an illustration.
EXAMPLE 9.12 Analyzing a Turbojet Engine
Air enters a turbojet engine at 0.8 bar, 240K, and an inlet velocity of 1000 km/h (278 m/s). The pressure ratio across the
compressor is 8. The turbine inlet temperature is 1200K and the pressure at the nozzle exit is 0.8 bar. The work developed
by the turbine equals the compressor work input. The diffuser, compressor, turbine, and nozzle processes are isentropic, and
there is no pressure drop for flow through the combustor. For operation at steady state, determine the velocity at the nozzle
exit and the pressure at each principal state. Neglect kinetic energy at the exit of all components except the nozzle and neg-
lect potential energy throughout.
SOLUTION
Known: An ideal turbojet engine operates at steady state. Key operating conditions are specified.
Find: Determine the velocity at the nozzle exit, in ft/s, and the pressure, in lbf/in.2, at each principal state.
T T3 = 1200K
3

Q in 4
T3 = 1200K
Combustor 2 5
2 3
1
Ta = 240K
Compressor Turbine a
s
p2/p1 = 8
Diffuser Nozzle
a 4
V1 = 0 p5 = 0.8 bar
Ta = 240K 1 5
pa = 0.8 bar
Va = 1000 km/h
Figure E9.12
Assumptions:
2. The diffuser, compressor, turbine, and nozzle processes are isentropic.
3. There is no pressure drop for flow through the combustor.
4. The turbine work output equals the work required to drive the compressor.
5. Except at the inlet and exit of the engine, kinetic energy effects can be ignored. Potential energy effects are negligible
throughout.
Analysis: To determine the velocity at the exit to the nozzle, the mass and energy rate balances for a control volume en-
closing this component reduce at steady state to give
0
V24 V25
0 Qcv W cv
m c 1h4 h5 2
a b
g1z4 z5 2 d
#0 #0 # 0
2
9.9 Gas Turbines for Aircraft Propulsion 417
#
where m is the mass flow rate. The inlet kinetic energy is dropped by assumption 5. Solving for V5
V5 121h4 h5 2
This expression requires values for the specific enthalpies h4 and h5 at the nozzle inlet and exit, respectively. With the oper-
ating parameters specified, the determination of these enthalpy values is accomplished by analyzing each component in turn,
beginning with the diffuser. The pressure at each principal state can be evaluated as a part of the analyses required to find the
enthalpies h4 and h5.
Mass and energy rate balances for a control volume enclosing the diffuser reduce to give
V2a
h1 ha
2
With ha from Table A-22 and the given value of Va
12782 2 m2
h1 240.02 kJ /kg
c da b` ` ` `
1N 1 kJ
2 s2 1 kg # m /s2 103 N # m
278.7 kJ /kg
Interpolating in Table A-22 gives pr1 1.070. The flow through the diffuser is isentropic, so pressure p1 is
pr1
p1 p
pra a
With pr data from Table A-22 and the known value of pa
10.8 bar2 1.347 bars

1.070
p1
0.6355
Using the given compressor pressure ratio, the pressure at state 2 is p2 8(1.347 bars) 10.78 bars
The flow through the compressor is also isentropic. Thus
p2
pr2 pr1 1.07182 8.56
p1
Interpolating in Table A-22, we get h2 505.5 kJ/kg.
At state 3 the temperature is given as T3 1200 K. From Table A-22, h3 1277.79 kJ/kg. By assumption 3, p3 p2. The
work developed by the turbine is just sufficient to drive the compressor (assumption 4). That is
# #
Wt Wc
# #
m m
or
h3 h4 h2 h1
Solving for h4
h4 h3
h1 h2 1277.79
278.7 505.5
1051 kJ/kg
Interpolating in Table A-22 with h4, gives pr4 116.8
The expansion through the turbine is isentropic, so
pr4
p4 p3
pr3
With p3 p2 and pr data from Table A-22
p4 110.78 bars2
116.0
5.25 bars
238.0
The expansion through the nozzle is isentropic to p5 0.8 bars. Thus
1116.02
p5 0.8
pr5 pr4 17.68
p4 5.25
From Table A-22, h5 265.8 Btu / lb, which is the remaining specific enthalpy value required to determine the velocity at the
nozzle exit.
Using the values for h4 and h5 determined above, the velocity at the nozzle exit is
V5 121h4 h5 2
kJ 1 kg # m /s2 103 N # m
211051 621.32 a ba b
B kg 1N 1 kJ
927 m /s
Note the unit conversions required here and in the calculation of V5.
The increase in the velocity of the air as it passes through the engine gives rise to the thrust produced by the engine. A
detailed analysis of the forces acting on the engine requires Newtons second law of motion in a form suitable for control
volumes (See Sec. 9.12.1).
OTHER APPLICATIONS. Other related applications of the gas turbine include turboprop and
turbofan engines. The turboprop engine shown in Fig. 9.22a consists of a gas turbine in which
the gases are allowed to expand through the turbine to atmospheric pressure. The net power
developed is directed to a propeller, which provides thrust to the aircraft. Turboprops are ef-
ficient propulsion devices for speeds of up to about 600 km/h (400 miles/h). In the turbo-
fan shown in Fig. 9.22b, the core of the engine is much like a turbojet, and some thrust is
obtained from expansion through the nozzle. However, a set of large-diameter blades attached
to the front of the engine accelerates air around the core. This bypass flow provides addi-
tional thrust for takeoff, whereas the core of the engine provides the primary thrust for
cruising. Turbofan engines are commonly used for commercial aircraft with flight speeds of
up to about 1000 km/h (600 miles/h). A particularly simple type of engine known as a ram-
jet is shown in Fig. 9.22c. This engine requires neither a compressor nor a turbine. A suffi-
cient pressure rise is obtained by decelerating the high-speed incoming air in the diffuser
Fan By-pass flow
Basic engine-core
Propeller
(a) (b)
Diffuser Nozzle
Flame holder
(c)
Figure 9.22 Other examples of aircraft engines. (a) Turboprop. (b) Turbofan. (c) Ramjet.
9.10 Combined Gas TurbineVapor Power Cycle 419
(ram effect). For the ramjet to operate, therefore, the aircraft must already be in flight at high
speed. The combustion products exiting the combustor are expanded through the nozzle to
produce the thrust.
In each of the engines mentioned thus far, combustion of the fuel is supported by air
brought into the engines from the atmosphere. For very high-altitude flight and space travel,
where this is no longer possible, rockets may be employed. In these applications, both fuel
and an oxidizer (such as liquid oxygen) are carried on board the craft. Thrust is developed
when the high-pressure gases obtained on combustion are expanded through a nozzle and
discharged from the rocket.

9.10 Combined Gas TurbineVapor
Power Cycle
A combined power cycle couples two power cycles such that the energy discharged by heat combined cycle
transfer from one cycle is used partly or wholly as the input for the other cycle. The binary
vapor cycle introduced in Sec. 8.5 is an example of a combined power cycle. In the present
section, a combined gas turbinevapor power cycle is considered.
The stream exiting the turbine of a gas turbine is at a high temperature. One way the po-
tential (exergy) of this high-temperature gas stream can be used, thereby improving overall
fuel utilization, is by a regenerator that allows the turbine exhaust gas to preheat the air be-
tween the compressor and combustor (Sec. 9.7). Another method is provided by the com-
bined cycle shown in Fig. 9.23, involving a gas turbine cycle and a vapor power cycle. The
two power cycles are coupled so that the heat transfer to the vapor cycle is provided by the
gas turbine cycle, which may be called the topping cycle. topping cycle

Qin
Combustor
2
3
Gas turbine
Compressor Turbine
Wgas
Air inlet 1
4
Exhaust
5
7
Heat exchanger
Turbine
6 Vapor Wvap
cycle
8
Pump Condenser
9 Cooling Figure 9.23 Combined
water gas turbinevapor power
plant.

New Power Plant Breaks Imagined Barrier than before. Advanced
blade cooling meth-
The new General Electric H SystemTM is the first combined- ods, new alloys, and
cycle power plant to achieve 60% thermal efficiency, once the unique single crystal
four minute mile of power plant technology. The installa- blade construction al-
tion is in Wales, where the 480-megawatt system provides low the turbines to
power to adjacent chemical manufacturing plants and to the withstand higher tem-
energy grid. peratures. The high
Development efforts began in the early 1990s, when the thermal efficiency also
best available technology combining gas and steam turbines results in the lowest
achieved thermal efficiencies of only 50%. Each percentage in- carbon dioxide pro-
crease is estimated to save $1520 million dollars of natural duction per megawatt
gas over the life of a typical system, according to industry of electricity of any gas
sources. Electric rates with the H SystemTM are said to be 30% turbine in the world.
less than were previously available. Nitric oxide (NOX)
The efficiency gains are achieved because natural gas emission levels are
is burned at a temperature nearly 300F (167C) higher half the average of other turbines now in use.
The combined cycle has the gas turbines high average temperature of heat addition and
the vapor cycles low average temperature of heat rejection, and thus a thermal efficiency
greater than either cycle would have individually. For many applications combined cycles
are economical, and they are increasingly being used worldwide for electric power gener-
ation.
With reference to Fig. 9.23, the thermal efficiency of the combined cycle is
# #
Wgas
Wvap
h # (9.28)
Qin
# #
where Wgas is the net power # developed by the gas turbine and Wvap is the net power devel-
oped by the vapor cycle. Qin denotes the total rate of heat transfer to the combined cycle, in-
cluding additional heat transfer, if any, to superheat the vapor entering the vapor turbine. The
evaluation of the quantities appearing in Eq. 9.28 follows the procedures described in the
sections on vapor cycles and gas turbines.
The relation for the energy transferred from the gas cycle to the vapor cycle for the system
of Fig. 9.23 is obtained by applying the mass and energy rate balances to a control volume
enclosing the heat exchanger. For steady-state operation, negligible heat transfer with the sur-
roundings, and no significant changes in kinetic and potential energy, the result is
mv 1h7 h6 2 mg 1h4 h5 2
# #
(9.29)
# #
where mg and mv are the mass flow rates of the gas and vapor, respectively.
As witnessed by relations such as Eqs. 9.28 and 9.29, combined cycle performance can
be analyzed using mass and energy balances. To complete the analysis, however, the second
law is required to assess the impact of irreversibilities and the true magnitudes of losses.
Among the irreversibilities, the most significant is the exergy destroyed by combustion. About
30% of the exergy entering the combustor with the fuel is destroyed by combustion irre-
versibility. An analysis of the gas turbine on an air-standard basis does not allow this exergy
destruction to be evaluated, however, and means introduced in Chap. 13 must be applied for
this purpose.
The next example illustrates the use of mass and energy balances, the second law, and
property data to analyze combined cycle performance.
EXAMPLE 9.13 Combined Cycle Exergy Accounting
A combined gas turbinevapor power plant has a net power output of 45 MW. Air enters the compressor of the gas turbine
at 100 kPa, 300 K, and is compressed to 1200 kPa. The isentropic efficiency of the compressor is 84%. The condition at the
inlet to the turbine is 1200 kPa, 1400 K. Air expands through the turbine, which has an isentropic efficiency of 88%, to a
pressure of 100 kPa. The air then passes through the interconnecting heat exchanger and is finally discharged at 400 K. Steam
enters the turbine of the vapor power cycle at 8 MPa, 400C, and expands to the condenser pressure of 8 kPa. Water enters
the pump as saturated liquid at 8 kPa. The turbine and pump of the vapor cycle have isentropic efficiencies of 90 and 80%,
respectively.
(a) Determine the mass flow rates of the air and the steam, each in kg/s, and the net power developed by the gas turbine and
vapor power cycle, each in MW.
(b) Develop a full accounting of the net rate of exergy increase as the air passes through the gas turbine combustor. Discuss.
Let T0 300 K, p0 100 kPa.
SOLUTION
Known: A combined gas turbinevapor power plant operates at steady state with a known net power output. Operating pres-
sures and temperatures are specified. Turbine, compressor, and pump efficiencies are also given.
Find: Determine the mass flow rate of each working fluid, in kg/s, and the net power developed by each cycle, in MW.
Develop a full accounting of the exergy increase of the air passing through the gas turbine combustor and discuss the results.

Qin
Combustor T3 = 1400 K
2 3 p3 = p2 = 1200 kPa
Assumptions:
c = 84% t = 88%
Gas turbine 1. Each component on the accompanying
Compressor Turbine
sketch is analyzed as a control volume at steady
Wgas = state.

Wt Wc 2. The turbines, compressor, pump, and inter-
T1 = 300 K
1 p1 = 100 kPa connecting heat exchanger operate adiabati-
Air inlet 4 cally.
3. Kinetic and potential energy effects are neg-
Exhaust
5 ligible.
T5 = 400 K
p5 = p4 = 100 kPa 4. There are no pressure drops for flow through
T7 = 400C the combustor, interconnecting heat exchanger,
7 p7 = 8 MPa
and condenser.
Heat exchanger t = 90%
5. An air-standard analysis is used for the gas
Turbine turbine.

6 Vapor Wvap = 6. T0 300 K, p0 100 kPa.
cycle
8 Wt Wp

Pump Condenser Qout
9
p = 80% p9 = p8 = 8 kPa
Figure E9.13
Analysis: The property data given in the table below are determined using procedures illustrated in previous solved exam-
ples of Chaps. 8 and 9. The details are left as an exercise.
Gas Turbine Vapor Cycle

State h (kJ/kg) s (kJ/kg # K) State h (kJ/kg) s (kJ/kg # K)
1 300.19 1.7020 6 183.96 0.5975
2 669.79 2.5088 7 3138.30 6.3634
3 1515.42 3.3620 8 2104.74 6.7282
4 858.02 2.7620 9 173.88 0.5926
5 400.98 1.9919
# #
(a) To determine the mass flow rates of the vapor, mv, and the air, mg, begin by applying mass and energy rate balances to
the interconnecting heat exchanger to obtain
0 mg 1h4 h5 2
mv 1h6 h7 2
# #
or
#
mv h4 h5 858.02 400.98
# 0.1547
mg h7 h6 3138.3 183.96
Mass and energy rate balances applied to the gas turbine and vapor power cycles give the net power developed by each,
respectively
Wgas mg 3 1h3 h4 2 1h2 h1 2 4

# #
Wvap mv 3 1h7 h8 2 1h6 h9 2 4

# #
# # #
With Wnet Wgas
Wvap
#
Wnet mg e 3 1h3 h4 2 1h2 h1 2 4
# 3 1h7 h8 2 1h6 h9 2 4 f
# # mv
mg
#
Solving for mg, and inserting Wnet 45 MW 45,000 kJ/s and mv ma 0.1547, we get
# # #
# 45,000 kJ/s
mg
5 3 11515.42 858.022 1669.79 300.192 4
0.1547 3 13138.3 2104.742 1183.96 173.882 4 6 kJ/kg
100.87 kg/s
and
mv 10.15472mg 15.6 kg/s

# #
Using these mass flow rate values and specific enthalpies from the table above, the net power developed by the gas tur-
bine and vapor power cycles, respectively, is
Wgas a100.87 b a287.8 b ` 3 ` 29.03 MW

# kg kJ 1 MW
s kg 10 kJ/s
Wvap a15.6 b a1023.5 b ` 3 ` 15.97 MW

# kg kJ 1 MW
s kg 10 kJ/s
(b) The net rate of exergy increase of the air passing through the combustor is (Eq. 7.36)
Ef3 Ef2 mg 3h3 h2 T0 1s3 s2 2 4

# # #
mg 3h3 h2 T0 1s3 s2 R ln p3 p2 2 4

#
With assumption 4, we have

0
Ef3 Ef2 mg c h3 h2 T0 as3 s2 R ln b d

# # # p3
p2
a100.87 b c 11515.42 669.792 300 K13.3620 2.50882 # d

kJ kJ kJ
s kg kg K
` ` 59.48 MW
kJ 1 MW
59,480
s 103 kJ/s
The net rate exergy is carried out by the exhaust air stream at 5 is
0
Ef 5 Ef1 mg c h5 h1 T0 as5 s1 R ln b d
# # # p5
p1
a100.87 b3 1400.98 300.192 30011.9919 1.70202 4 a b ` 3 `

kg kJ 1 MW
s kg 10 kJ/s
1.39 MW
The net rate exergy is carried out as the water passes through the condenser is
Ef 8 Ef9 mv 3h8 h9 T0 1s8 s9 2 4
# # #
a15.6 b c 12104.74 173.882 300 K16.7282 0.59262 # d ` 3 `

kg kJ kJ 1 MW
s kg kg K 10 kJ/s
1.41 MW
The rates of exergy
# destruction for the air turbine, compressor, steam turbine, pump, and interconnecting heat exchanger
#
are evaluated using Ed T0scv, respectively, as follows:
Air turbine:
Ed mgT0 1s4 s3 2
# #
mgT0 1s4 s3 R ln p4 p3 2

#
a100.87 b 1300 K2 c 12.7620 3.36202 # a b ln a bd ` 3 `

kg kJ 8.314 kJ 100 1 MW
s kg K 28.97 kg K# 1200 10 kJ/s
3.42 MW
Compressor:
Ed mgT0 1s2 s1 2
# #
mgT0 1s2 s1 R ln p2 p1 2

#
1100.87213002 c 12.5088 1.70202 ln a bd ` 3 `

8.314 1200 1
28.97 100 10
2.83 MW
Steam turbine:
Ed mvT0 1s8 s7 2
# #
115.621300216.7282 6.36342 ` `
1
103
1.71 MW
Pump:
Ed mvT0 1s6 s9 2
# #
115.621300210.5975 0.59262 ` `
1
103
0.02 MW
Heat exchanger:
Ed T0 3mg 1s5 s4 2
mv 1s7 s6 2 4
# # #
1300 K2 c a100.87 b 11.9919 2.76202

a15.6 b 16.3634 0.59752 d ` `
kg kJ kg kJ 1 MW
s kg # K s kg # K 103 kJ/s
3.68 MW
The results are summarized by the following exergy rate balance sheet in terms of exergy magnitudes on a rate basis:
Net exergy increase of the gas passing

through the combustor: 59.48 MW 100% (70%)*
Net power developed
gas turbine cycle 29.03 MW 48.8% (34.2%)
vapor cycle 15.97 MW 26.8% (18.8%)
Subtotal 45.00 MW 75.6% (53.0%)
Net exergy lost
with exhaust gas at state 5 1.39 MW 2.3% (1.6%)
from water passing through condenser 1.41 MW 2.4% (1.7%)
Exergy destruction
air turbine 3.42 MW 5.7% (4.0%)
compressor 2.83 MW 4.8% (3.4%)
steam turbine 1.71 MW 2.9% (2.0%)
pump 0.02 MW
heat exchanger 3.68 MW 6.2% (4.3%)
*Estimation based on fuel exergy. For discussion, see note 2.
The subtotals given in the table under the net power developed heading indicate that the combined cycle is effective in
generating power from the exergy supplied. The table also indicates the relative significance of the exergy destructions in the
turbines, compressor, pump, and heat exchanger, as well as the relative significance of the exergy losses. Finally, the table
indicates that the total of the exergy destructions overshadows the losses.
The development of the appropriate expressions for the rates of entropy production in the turbines, compressor, pump, and
heat exchanger is left as an exercise.
In this exergy balance sheet, the percentages shown in parentheses are estimates based on the fuel exergy. Although com-
bustion is the most significant source of irreversibility, the exergy destruction due to combustion cannot be evaluated using
an air-standard analysis. Calculations of exergy destruction due to combustion (Chap. 13) reveal that approximately 30% of
the exergy entering the combustor with the fuel would be destroyed, leaving about 70% of the fuel exergy for subsequent
use. Accordingly, the value 59.48 MW for the net exergy increase of the air passing through the combustor is assumed to be
70% of the fuel exergy supplied. The other percentages in parentheses are obtained by multiplying the corresponding per-
centages, based on the exergy increase of the air passing through the combustor, by the factor 0.7. Since they account for
combustion irreversibility, the table values in parentheses give the more accurate picture of combined cycle performance.

9.11 Ericsson and Stirling Cycles
Significant increases in the thermal efficiency of gas turbine power plants can be achieved
through intercooling, reheat, and regeneration. There is an economic limit to the number of
stages that can be employed, and normally there would be no more than two or three. Nonethe-
less, it is instructive to consider the situation where the number of stages of both intercool-
ing and reheat becomes indefinitely large. Figure 9.24a shows an ideal closed regenerative
gas turbine cycle with several stages of compression and expansion and a regenerator whose
effectiveness is 100%. Each intercooler is assumed to return the working fluid to the
9.11 Ericsson and Stirling Cycles 425
T T
3 4 3 4
TH TH
p=c p=c
p=c p=c
TC TC
2 1 2 1
s s
(a) (b)
Figure 9.24 Ericsson cycle as a limit of ideal gas turbine operation using
multistage compression with intercooling, multistage expansion with reheating,
and regeneration.
temperature TC at the inlet to the first compression stage and each reheater restores the work-
ing fluid to the temperature TH at the inlet to the first turbine stage. The regenerator allows
the heat input for Process 23 to be obtained from the heat rejected in Process 41. Ac-
cordingly, all the heat added externally would occur in the reheaters, and all the heat rejected
to the surroundings would take place in the intercoolers.
In the limit, as an infinite number of reheat and intercooler stages is employed, all the heat
added would occur when the working fluid is at its highest temperature, TH, and all the heat
rejected would take place when the working fluid is at its lowest temperature, TC. The limiting
cycle, shown in Fig. 9.24b, is called the Ericsson cycle. Since irreversibilities are presumed Ericsson cycle
absent and all the heat is supplied and rejected isothermally, the thermal efficiency of the
Ericsson cycle equals that of any reversible power cycle operating with heat addition at the
temperature TH and heat rejection at the temperature TC: hmax 1 TC TH. This expression
was applied previously to evaluate the thermal efficiency of Carnot power cycles. Although the
details of the Ericsson cycle differ from those of the Carnot cycle, both cycles have the same
value of thermal efficiency when operating between the temperatures TH and TC.
STIRLING CYCLE. Another cycle that employs a regenerator is the Stirling cycle, shown on
the pv and Ts diagrams of Fig. 9.25. The cycle consists of four internally reversible processes
in series: isothermal compression from state 1 to state 2 at temperature TC, constant-volume
heating from state 2 to state 3, isothermal expansion from state 3 to state 4 at temperature TH,
and constant-volume cooling from state 4 to state 1 to complete the cycle. A regenerator whose
effectiveness is 100% allows the heat rejected during Process 41 to be used as the heat in-
put in Process 23. Accordingly, all the heat added to the working fluid externally would take
p 3 T
T=c 3 4
TH
4
2
T=c v=c v=c
TH
1 TC
TC 2 1
v s
Figure 9.25 pv and Ts diagrams of the Stirling cycle.
place in the isothermal process 34 and all the heat rejected to the surroundings would occur
in the isothermal process 12. It can be concluded, therefore, that the thermal efficiency of
the Stirling cycle is given by the same expression as for the Carnot and Ericsson cycles.
The Ericsson and Stirling cycles are principally of theoretical interest as examples of cy-
cles that exhibit the same thermal efficiency as the Carnot cycle. However, a practical en-
gine of the pistoncylinder type that operates on a closed regenerative cycle having features
in common with the Stirling cycle has been under study in recent years. This engine is known
Stirling engine as Stirling engine. The Stirling engine offers the opportunity for high efficiency together
with reduced emissions from combustion products because the combustion takes place ex-
ternally and not within the cylinder as for internal combustion engines. In the Stirling en-
gine, energy is transferred to the working fluid from products of combustion, which are kept
separate. It is an external combustion engine.
COMPRESSIBLE FLOW THROUGH

NOZZLES AND DIFFUSERS
In many applications of engineering interest, gases move at relatively high velocities and exhibit
appreciable changes in density. The flows through the nozzles and diffusers of jet engines dis-
cussed in Sec. 9.9 are important examples. Other examples are the flows through wind tunnels,
compressible flow shock tubes, and steam ejectors. These flows are known as compressible flows. In this part of
the chapter, we introduce some of the principles involved in analyzing compressible flows.

9.12 Compressible Flow Preliminaries
Concepts introduced in this section play important roles in the study of compressible flows.
The momentum equation is introduced in a form applicable to the analysis of control vol-
umes at steady state. The velocity of sound is also defined, and the concepts of Mach num-
ber and stagnation state are discussed.
9.12.1 Momentum Equation for Steady One-Dimensional Flow

The analysis of compressible flows requires the principles of conservation of mass and energy,
the second law of thermodynamics, and relations among the thermodynamic properties of the
flowing gas. In addition, Newtons second law of motion is required. Application of Newtons
second law of motion to systems of fixed mass (closed systems) involves the familiar form
F ma
where F is the resultant force acting on a system of mass m and a is the acceleration. The
object of the present discussion is to introduce Newtons second law of motion in a form ap-
propriate for the study of the control volumes considered in subsequent discussions.
Consider the control volume shown in Fig. 9.26, which has a single inlet, designated by 1,
and a single exit, designated by 2. The flow is assumed to be one-dimensional at these lo-
cations. The energy and entropy rate equations for such a control volume have terms that ac-
count for energy and entropy transfers, respectively, at the inlets and exits. Momentum also
can be carried into or out of the control volume at the inlets and exits, and such transfers can
be accounted for as
time rate of momentum
transfer into or #
D T mV (9.30)
out of a control volume
y
1

m V1 x
2

m V2
Figure 9.26 One-inlet, one-

exit control volume at steady state
no flow through this labeled with momentum transfers
portion of the boundary accompanying mass flow.
In this expression, the momentum per unit of mass flowing across the boundary of the con-
trol volume is given by the velocity vector V. In accordance with the one-dimensional flow
model, the vector is normal to the inlet or exit and oriented in the direction of flow
In words, Newtons second law of motion for control volumes is
time rate of change resultant force net rate at which momentum is
of momentum contained acting on the
transferred into the control
within the control volume control volume volume accompanying mass flow
At steady state, the total amount of momentum contained in the control volume is constant
with time. Accordingly, when applying Newtons second law of motion to control volumes
at steady state, it is necessary to consider only the momentum accompanying the incoming
and outgoing streams of matter and the forces acting on the control volume. Newtons law
then states that the resultant force F acting on the control volume equals the difference be-
tween the rates of momentum exiting and entering the control volume accompanying mass
flow. This is expressed by the following momentum equation
F m2V2 m1V1 m 1V2 V1 2

# # #
(9.31) momentum equation
# #
Since m1 m2 at steady state, the common mass flow is designated in this expression sim-
#
ply as m. The resultant force includes the forces due to pressure acting at the inlet and exit,
forces acting on the portion of the boundary through which there is no mass flow, and the
force of gravity. The expression of Newtons second law of motion given by Eq. 9.31 suf-
fices for subsequent discussions. More general control volume formulations are normally
provided in fluid mechanics texts.
9.12.2 Velocity of Sound and Mach Number

A sound wave is a small pressure disturbance that propagates through a gas, liquid, or solid
at a velocity c that depends on the properties of the medium. In this section we obtain an ex-
pression that relates the velocity of sound, or sonic velocity, to other properties. The veloc-
ity of sound is an important property in the study of compressible flows.
MODELING PRESSURE WAVES. Let us begin by referring to Fig. 9.27a, which shows a
pressure wave moving to the right with a velocity of magnitude c. The wave is generated by
a small displacement of the piston. As shown on the figure, the pressure, density, and tem-
perature in the region to the left of the wave depart from the respective values of the undis-
turbed fluid to the right of the wave, which are designated simply p, , and T. After the wave
has passed, the fluid to its left is in steady motion with a velocity of magnitude V.
Observer on
wave
Piston
V Undisturbed fluid
c V
p + p p + p
c V=0 + c
+ p, T,
T + T T + T p, , T
2 1
Stationary Control volume for an
observer observer moving with
the wave
(a) (b)
Figure 9.27 Illustrations used to analyze the propagation of a sound wave. (a) Propagation of a
pressure wave through a quiescent fluid, relative to a stationary observer. (b) Observer at rest relative
to the wave.
Figure 9.27a shows the wave from the point of view of a stationary observer. It is easier
to analyze this situation from the point of view of an observer at rest relative to the wave,
as shown in Fig. 9.27b. By adopting this viewpoint, a steady-state analysis can be applied to
the control volume identified on the figure. To an observer at rest relative to the wave, it ap-
pears as though the fluid is moving toward the stationary wave from the right with velocity
c, pressure p, density , and temperature T and moving away on the left with velocity c V,
pressure p
p, density
, and temperature T
T.
At steady state, the conservation of mass principle for the control volume reduces to
# #
m1 m2, or
rAc 1r
r2A1c V2
On rearrangement
0
0 c r rV rV (9.32)
If the disturbance is weak, the third term on the right of Eq. 9.32 can be neglected, leaving
V 1cr2 r (9.33)
Next, the momentum equation, Eq. 9.31, is applied to the control volume under con-
sideration. Since the thickness of the wave is small, shear forces at the wall are negligi-
ble. The effect of gravity is also ignored. Hence, the only significant forces acting on the
control volume in the direction of flow are the forces due to pressure at the inlet and exit.
With these idealizations, the component of the momentum equation in the direction of flow
reduces to
pA 1 p
p2 A m 1c V2 mc
# #
m 1c V c2
#
1rAc21V2
or
p rc V (9.34)
Combining Eqs. 9.33 and 9.34 and solving for c

p
c (9.35)
B r
SOUND WAVES. For all sound waves the differences in pressure, density, and temperature
across the wave are quite small. In particular, , justifying the neglect of the third
term of Eq. 9.32. Furthermore, the ratio p in Eq. 9.35 can be interpreted as the deriv-
ative of pressure with respect to density across the wave. Experiments also indicate that the
relation between pressure and density across a sound wave is nearly isentropic. The expres-
sion for the velocity of sound then becomes
a b
0p
c (9.36a) velocity of sound
B 0r s
or in terms of specific volume
v2 a b
0p
c (9.36b)
B 0v s
The velocity of sound is an intensive property whose value depends on the state of the medium
through which sound propagates. Although we have assumed that sound propagates isen-
tropically, the medium itself may be undergoing any process.
Means for evaluating the velocity of sound c for gases, liquids, and solids are introduced
in Sec. 11.5. The special case of an ideal gas will be considered here because it is used
extensively later in the chapter. For this case, the relationship between pressure and specific
volume of an ideal gas at fixed entropy is pvk constant, where k is the specific heat ratio
(Sec. 6.7). Thus, (0p0v)s kpv, and Eq. 9.36b gives c 1kpv. Or, with the ideal gas
equation of state
c 2kRT 1ideal gas2 (9.37)
for example. . . to illustrate the use of Eq. 9.37, let us calculate the velocity of
sound in air at 300 K and 650 K. From Table A-20 at 300 K, k 1.4. Thus
1 kg # m /s2
1.4 a b 1300 ` ` 347
8314 N # m m
c K2
B 28.97 kg # K 1N s
At 650 K, k 1.37, and c 506 m/s, as can be verified.
MACH NUMBER. In subsequent discussions, the ratio of the velocity V at a state in a flow-
ing fluid to the value of the sonic velocity c at the same state plays an important role. This
ratio is called the Mach number M
V
M (9.38) Mach number
c
When M 1, the flow is said to be supersonic; when M 1, the flow is subsonic; and supersonic
when M 1, the flow is sonic. The term hypersonic is used for flows with Mach numbers
subsonic
much greater than one, and the term transonic refers to flows where the Mach number is
close to unity.
9.12.3 Determining Stagnation State Properties

When dealing with compressible flows, it is often convenient to work with properties eval-
stagnation state uated at a reference state known as the stagnation state. The stagnation state is the state a
flowing fluid would attain if it were decelerated to zero velocity isentropically. We might
imagine this as taking place in a diffuser operating at steady state. By reducing an energy
balance for such a diffuser, it can be concluded that the enthalpy at the stagnation state as-
sociated with an actual state in the flow where the specific enthalpy is h and the velocity is
V is given by
V2
stagnation enthalpy ho h
(9.39)
2
The enthalpy designated here as ho is called the stagnation enthalpy. The pressure po and
stagnation pressure temperature To at a stagnation state are called the stagnation pressure and stagnation
and temperature temperature, respectively.

9.13 Analyzing One-Dimensional Steady
Flow in Nozzles and Diffusers
Although the subject of compressible flow arises in a great many important areas of engi-
neering application, the remainder of this presentation is concerned only with flow through
nozzles and diffusers. Texts dealing with compressible flow should be consulted for discus-
sion of other areas of application.
In the present section we determine the shapes required by nozzles and diffusers for sub-
sonic and supersonic flow. This is accomplished using mass, energy, entropy, and momen-
tum principles, together with property relationships. In addition, we study how the flow
through nozzles is affected as conditions at the nozzle exit are changed. The presentation
concludes with an analysis of normal shocks, which can exist in supersonic flows.
9.13.1 Exploring the Effects of Area Change in Subsonic and

Supersonic Flows
The objective of the present discussion is to establish criteria for determining whether a
nozzle or diffuser should have a converging, diverging, or convergingdiverging shape.
This is accomplished using differential equations relating the principal variables that are
obtained using mass and energy balances together with property relations, as considered
next.
GOVERNING DIFFERENTIAL EQUATIONS. Let us begin by considering a control volume
enclosing a nozzle or diffuser. At steady state, the mass flow rate is constant, so
rAV constant
In differential form
d1rAV2 0
AV dr
rA dV
rV dA 0
or on dividing each term by AV

dr dV dA

0 (9.40)
r V A
9.13 Analyzing One-Dimensional Steady Flow in Nozzles and Diffusers 431
# #
Assuming Qcv Wcv 0 and negligible potential energy effects, an energy rate balance
reduces to give
V22 V 21
h2
h1
2 2
Introducing Eq. 9.39, it follows that the stagnation enthalpies at states 1 and 2 are equal:
ho2 ho1. Since any state downstream of the inlet can be regarded as state 2, the following
relationship between the specific enthalpy and kinetic energy must be satisfied at each state
V2
h
ho1 (constant)
2
In differential form this becomes

dh V dV (9.41)
This equation shows that if the velocity increases (decreases) in the direction of flow, the
specific enthalpy must decrease (increase) in the direction of flow, and conversely.
In addition to Eqs. 9.40 and 9.41 expressing conservation of mass and energy, relation-
ships among properties must be taken into consideration. Assuming the flow occurs isen-
tropically, the property relation (Eq. 6.12b)
dp
T ds dh
r
reduces to give
1
dh dp (9.42)
r
This equation shows that when pressure increases or decreases in the direction of flow, the
specific enthalpy changes in the same way.
Forming the differential of the property relation p p(, s)
dp a b dr
a b ds
0p 0p
0r s 0s r
The second term vanishes in isentropic flow. Introducing Eq. 9.36a, we have
dp c2 dr (9.43)
which shows that when pressure increases or decreases in the direction of flow, density
changes in the same way.
Additional conclusions can be drawn by combining the above differential equations. Com-
bining Eqs. 9.41 and 9.42 results in
1
dp V dV (9.44)
r
which shows that if the velocity increases (decreases) in the direction of flow, the pressure
must decrease (increase) in the direction of flow, and conversely.
Eliminating dp between Eqs. 9.43 and 9.44 and combining the result with Eq. 9.40 gives
V 2
c1 a b d
dA dV

A V c
or with the Mach number M
11 M 2 2
dA dV
(9.45)
A V
VARIATION OF AREA WITH VELOCITY. Equation 9.45 shows how area must vary with ve-
locity. The following four cases can be identified:
Case 1: Subsonic nozzle. dV 0, M 1 1 dA 0: The duct converges in the direction
of flow.
Case 2: Supersonic nozzle. dV 0, M 1 1 dA 0: The duct diverges in the direction
of flow.
Case 3: Supersonic diffuser. dV 0, M 1 1 dA 0: The duct converges in the direction
of flow.
Case 4: Subsonic diffuser. dV 0, M 1 1 dA 0: The duct diverges in the direction
of flow.
The conclusions reached above concerning the nature of the flow in subsonic and super-
sonic nozzles and diffusers are summarized in Fig. 9.28. From Fig. 9.28a, we see that to ac-
celerate a fluid flowing subsonically, a converging nozzle must be used, but once M 1 is
achieved, further acceleration can occur only in a diverging nozzle. From Fig. 9.28b, we see
that a converging diffuser is required to decelerate a fluid flowing supersonically, but once
M 1 is achieved, further deceleration can occur only in a diverging diffuser. These findings
suggest that a Mach number of unity can occur only at the location in a nozzle or diffuser
where the cross-sectional area is a minimum. This location of minimum area is called the
throat throat.
The developments of this section have not required the specification of an equation of
state; thus, the conclusions hold for all gases. Moreover, although the conclusions have been
drawn under the restriction of isentropic flow through nozzles and diffusers, they are at least
qualitatively valid for actual flows because the flow through well-designed nozzles and dif-
fusers is nearly isentropic. Isentropic nozzle efficiencies (Sec. 6.8) in excess of 95% can be
attained in practice.
9.13.2 Effects of Back Pressure on Mass Flow Rate

In the present discussion we consider the effect of varying the back pressure on the rate of
back pressure mass flow through nozzles. The back pressure is the pressure in the exhaust region outside
the nozzle. The case of converging nozzles is taken up first and then convergingdiverging
nozzles are considered.
M<1 M>1 M>1 M<1

Subsonic Supersonic Supersonic Subsonic
Case 1 Case 2 Case 3 Case 4

(a) (b)
Figure 9.28 Effects of area change in subsonic and supersonic flows. (a) Nozzles:
V increases; h, p, and r decrease. (b) Diffusers: V decreases h, p, and increase.
CONVERGING NOZZLES. Figure 9.29 shows a converging duct with stagnation condi-
tions at the inlet, discharging into a region in which the back pressure pB can be varied.
#
For the series of cases labeled a through e, let us consider how the mass flow rate m and
nozzle exit pressure pE vary as the back pressure is decreased while keeping the inlet
conditions fixed.
#
When pB pE po, there is no flow, so m 0. This corresponds to case a of Fig. 9.29.
If the back pressure pB is decreased, as in cases b and c, there will be flow through the noz-
zle. As long as the flow is subsonic at the exit, information about changing conditions in the
exhaust region can be transmitted upstream. Decreases in back pressure thus result in greater
mass flow rates and new pressure variations within the nozzle. In each instance, the veloc-
ity is subsonic throughout the nozzle and the exit pressure equals the back pressure. The exit
Mach number increases as pB decreases, however, and eventually a Mach number of unity
will be attained at the nozzle exit. The corresponding pressure is denoted by p*, called the
critical pressure. This case is represented by d on Fig. 9.29.
Recalling that the Mach number cannot increase beyond unity in a converging section, let
us consider next what happens when the back pressure is reduced further to a value less than
p*, such as represented by case e. Since the velocity at the exit equals the velocity of sound,
information about changing conditions in the exhaust region no longer can be transmitted
upstream past the exit plane. Accordingly, reductions in pB below p* have no effect on flow
conditions in the nozzle. Neither the pressure variation within the nozzle nor the mass flow
rate is affected. Under these conditions, the nozzle is said to be choked. When a nozzle is choked flow:
choked, the mass flow rate is the maximum possible for the given stagnation conditions. For converging nozzle
pB less than p*, the flow expands outside the nozzle to match the lower back pressure, as
shown by case e of Fig. 9.29. The pressure variation outside the nozzle cannot be predicted
using the one-dimensional flow model.
Valve to adjust
back pressure
V0
pE pB
po, To
Exhaust region
a
b
c
p d
e
pE
po
m
e d 1.0
c a
b
c
p*
po e d
b
a Figure 9.29 Effect of
1.0 pB 1.0 pB back pressure on the operation
po po of a converging nozzle.
Throat Exhaust region
V0 pE pB
po, To
Valve to adjust
back pressure
a b
p c
d
e
p* f
M=1
Normal
shock g
h
Normal i
shock j
Figure 9.30 Effect of back pressure on the operation of a converging

diverging nozzle.
CONVERGINGDIVERGING NOZZLES. Figure 9.30 illustrates the effects of varying back

pressure on a convergingdiverging nozzle. The series of cases labeled a through j is con-
sidered next.
Let us first discuss the cases designated a, b, c, and d. Case a corresponds to pB
pE po for which there is no flow. When the back pressure is slightly less than po
(case b), there is some flow, and the flow is subsonic throughout the nozzle. In accor-
dance with the discussion of Fig. 9.28, the greatest velocity and lowest pressure occur at
the throat, and the diverging portion acts as a diffuser in which pressure increases and
velocity decreases in the direction of flow. If the back pressure is reduced further, corre-
sponding to case c, the mass flow rate and velocity at the throat are greater than before.
Still, the flow remains subsonic throughout and qualitatively the same as case b. As the
back pressure is reduced, the Mach number at the throat increases, and eventually a
Mach number of unity is attained there (case d). As before, the greatest velocity and
lowest pressure occur at the throat, and the diverging portion remains a subsonic
choked flow: diffuser. However, because the throat velocity is sonic, the nozzle is now choked: The
convergingdiverging maximum mass flow rate has been attained for the given stagnation conditions. Further
reductions in back pressure cannot result in an increase in the mass flow rate.
nozzle
When the back pressure is reduced below that corresponding to case d, the flow through
the converging portion and at the throat remains unchanged. Conditions within the di-
verging portion can be altered, however, as illustrated by cases e, f, and g. In case e, the
fluid passing the throat continues to expand and becomes supersonic in the diverging
portion just downstream of the throat; but at a certain location an abrupt change in
normal shock properties occurs. This is called a normal shock. Across the shock, there is a rapid and
irreversible increase in pressure, accompanied by a rapid decrease from supersonic to
subsonic flow. Downstream of the shock, the diverging duct acts as a subsonic diffuser
in which the fluid continues to decelerate and the pressure increases to match the back
pressure imposed at the exit. If the back pressure is reduced further (case f), the loca-
tion of the shock moves downstream, but the flow remains qualitatively the same as in
case e. With further reductions in back pressure, the shock location moves farther down-
stream of the throat until it stands at the exit (case g). In this case, the flow throughout
the nozzle is isentropic, with subsonic flow in the converging portion, M 1 at the
throat, and supersonic flow in the diverging portion. Since the fluid leaving the nozzle
passes through a shock, it is subsonic just downstream of the exit plane.
Finally, let us consider cases h, i, and j where the back pressure is less than that corre-
sponding to case g. In each of these cases, the flow through the nozzle is not affected.
The adjustment to changing back pressure occurs outside the nozzle. In case h, the pres-
sure decreases continuously as the fluid expands isentropically through the nozzle and
then increases to the back pressure outside the nozzle. The compression that occurs out-
side the nozzle involves oblique shock waves. In case i, the fluid expands isentropically
to the back pressure and no shocks occur within or outside the nozzle. In case j, the
fluid expands isentropically through the nozzle and then expands outside the nozzle to
the back pressure through oblique expansion waves. Once M 1 is achieved at the
throat, the mass flow rate is fixed at the maximum value for the given stagnation
conditions, so the mass flow rate is the same for back pressures corresponding to cases
d through j. The pressure variations outside the nozzle involving oblique waves cannot
be predicted using the one-dimensional flow model.
9.13.3 Flow Across a Normal Shock

We have seen that under certain conditions a rapid and abrupt change of state called a shock
takes place in the diverging portion of a supersonic nozzle. In a normal shock, this change
of state occurs across a plane normal to the direction of flow. The object of the present dis-
cussion is to develop means for determining the change of state across a normal shock.
MODELING NORMAL SHOCKS. A control volume enclosing a normal # shock is

# shown in
Fig. 9.31. The control volume is assumed to be at steady state with Wcv 0, Qcv 0 and
negligible effects of potential energy. The thickness of the shock is very small (on the order of
105 cm). Thus, there is no significant change in flow area across the shock, even though it may
occur in a diverging passage, and the forces acting at the wall can be neglected relative to the
pressure forces acting at the upstream and downstream locations denoted by x and y, respectively.
The upstream and downstream states are related by the following equations:
Mass:
rxVx ryVy (9.46)
Energy:
V2x V2y
hx
hy
(9.47a)
2 2
or
hox hoy (9.47b)
Momentum:
px py ryV2y rxV2x (9.48)
Entropy:
sy sx scvm
# #
(9.49)
When combined with property relations for the particular fluid under consideration,
Eqs. 9.46, 9.47, and 9.48 allow the downstream conditions to be determined for specified
upstream conditions. Equation 9.49, which corresponds to Eq. 6.41, leads to the important
h
hox hoy
hox = hoy
pox poy Vy2
2
b
y
Vx2 a
2
Rayleigh line
Normal shock
Fanno line
x y M = 1 at a and b
x M < 1 on upper branches
Vx, Mx, Tx, px Vy, My, Ty, py hx
M > 1 on lower branches
hx, sx hy, sy
s
Figure 9.32 Intersection of Fanno and
Figure 9.31 Control volume Rayleigh lines as a solution to the normal shock
enclosing a normal shock. equations.
conclusion that the downstream state must have greater specific entropy than the upstream
state, or sy sx.
FANNO AND RAYLEIGH LINES. The mass and energy equations, Eqs. 9.46 and 9.47, can
be combined with property relations for the particular fluid to give an equation that when
Fanno line plotted on an hs diagram is called a Fanno line. Similarly, the mass and momentum equa-
tions, Eqs. 9.46 and 9.48, can be combined to give an equation that when plotted on an hs
Rayleigh line diagram is called a Rayleigh line. Fanno and Rayleigh lines are sketched on hs coordinates
in Fig. 9.32. It can be shown that the point of maximum entropy on each line, points a and
b, corresponds to M 1. It also can be shown that the upper and lower branches of each
line correspond, respectively, to subsonic and supersonic velocities.
The downstream state y must satisfy the mass, energy, and momentum equations simul-
taneously, so state y is fixed by the intersection of the Fanno and Rayleigh lines passing
through state x. Since sy sx, it can be concluded that the flow across the shock can only
pass from x to y. Accordingly, the velocity changes from supersonic before the shock (Mx 1)
to subsonic after the shock (My 1). This conclusion is consistent with the discussion of
cases e, f, and g in Fig. 9.30. A significant increase in pressure across the shock accompa-
nies the decrease in velocity. Figure 9.32 also locates the stagnation states corresponding to
the states upstream and downstream of the shock. The stagnation enthalpy does not change
across the shock, but there is a marked decrease in stagnation pressure associated with the
irreversible process occurring in the normal shock region.

9.14 Flow in Nozzles and Diffusers of Ideal
Gases with Constant Specific Heats
The discussion of flow in nozzles and diffusers presented in Sec. 9.13 requires no
assumption regarding the equation of state, and therefore the results obtained hold gen-
erally. Attention is now restricted to ideal gases with constant specific heats. This case is
9.14 Flow in Nozzles and Diffusers of Ideal Gases with Constant Specific Heats 437
appropriate for many practical problems involving flow through nozzles and diffusers.
The assumption of constant specific heats also allows the derivation of relatively simple
closed-form equations.
ISENTROPIC FLOW FUNCTIONS. Let us begin by developing equations relating a state in

a compressible flow to the corresponding stagnation state. For the case of an ideal gas with
constant cp, Eq. 9.39 becomes
V2
To T
2cp
where To is the stagnation temperature. Introducing cp kR(k 1), together with Eqs. 9.37
and 9.38, the relation between the temperature T and the Mach number M of the flowing gas
and the corresponding stagnation temperature To is
To k1 2
1
M (9.50)
T 2
With Eq. 6.45, a relationship between the temperature T and pressure p of the flowing gas
and the corresponding stagnation temperature To and the stagnation pressure po is
To k 1k12
a b
po
p T
Introducing Eq. 9.50 into this expression gives
k 1 2 k 1k12
a1
M b
po
(9.51)
p 2
Although sonic conditions may not actually be attained in a particular flow, it is conven-
ient to have an expression relating the area A at a given section to the area A* that would be
required for sonic flow (M 1) at the same mass flow rate and stagnation state. These areas
are related through
rAV r*A*V*
where * and V* are the density and velocity, respectively, when M 1. Introducing the
ideal gas equation of state, together with Eqs. 9.37 and 9.38, and solving for AA*
1 p* T 1 2 1 p*po TTo 1 2
a b a b
A

A* M p T* M ppo T * To
where T* and p* are the temperature and pressure, respectively, when M 1. Then with
Eqs. 9.50 and 9.51
k 1 2 1k
12 21k12
ca b a1
M bd
A 1 2
(9.52)
A* M k
1 2
The variation of AA* with M is given in Fig. 9.33 for k 1.4. The figure shows that a
unique value of AA* corresponds to any choice of M. However, for a given value of AA*
other than unity, there are two possible values for the Mach number, one subsonic and one
supersonic. This is consistent with the discussion of Fig. 9.28, where it was found that a
convergingdiverging passage with a section of minimum area is required to accelerate a
flow from subsonic to supersonic velocity.
3.0 TABLE 9.1 Isentropic Flow Functions for an Ideal Gas

with k 1.4
2.5 M TTo ppo AA*
0 1.000 00 1.000 00
2.0 0.10 0.998 00 0.993 03 5.8218
0.20 0.992 06 0.972 50 2.9635
A
A*
1.5 0.30 0.982 32 0.939 47 2.0351
0.40 0.968 99 0.895 62 1.5901
1.0 0.50 0.952 38 0.843 02 1.3398
0.60 0.932 84 0.784 00 1.1882
0.70 0.910 75 0.720 92 1.094 37
0.5
0.80 0.886 52 0.656 02 1.038 23
0.90 0.860 58 0.591 26 1.008 86
0 1.00 0.833 33 0.528 28 1.000 00
0 0.5 1.0 1.5 2.0 2.5 3.0
M
1.10 0.805 15 0.468 35 1.007 93
1.20 0.776 40 0.412 38 1.030 44
Figure 9.33 Variation of AA* with Mach 1.30 0.747 38 0.360 92 1.066 31
number in isentropic flow for k 1.4. 1.40 0.718 39 0.314 24 1.1149
1.50 0.689 65 0.272 40 1.1762
1.60 0.661 38 0.235 27 1.2502
1.70 0.633 72 0.202 59 1.3376
1.80 0.606 80 0.174 04 1.4390
1.90 0.580 72 0.149 24 1.5552
2.00 0.555 56 0.127 80 1.6875
2.10 0.531 35 0.109 35 1.8369
2.20 0.508 13 0.093 52 2.0050
2.30 0.485 91 0.079 97 2.1931
2.40 0.464 68 0.068 40 2.4031
Equations 9.50, 9.51, and 9.52 allow the ratios TTo, ppo, and AA* to be computed
and tabulated with the Mach number as the single independent variable for a specified
value of k. Table 9.1 provides a tabulation of this kind for k 1.4. Such a table facili-
tates the analysis of flow through nozzles and diffusers. Equations 9.50, 9.51, and 9.52
also can be readily evaluated using calculators and computer software such as Interactive
Thermodynamics: IT.
In Example 9.14, we consider the effect of back pressure on flow in a converging nozzle.
The first step of the analysis is to check whether the flow is choked.
EXAMPLE 9.14 Effect of Back Pressure: Converging Nozzle
A converging nozzle has an exit area of 0.001 m2. Air enters the nozzle with negligible velocity at a pressure of 1.0 MPa and
a temperature of 360 K. For isentropic flow of an ideal gas with k 1.4, determine the mass flow rate, in kg/s, and the exit
Mach number for back pressures of (a) 500 kPa and (b) 784 kPa.
SOLUTION
Known: Air flows isentropically from specified stagnation conditions through a converging nozzle with a known exit area.
Find: For back pressures of 500 and 784 kPa, determine the mass flow rate, in kg/s, and the exit Mach number.
T T po
po
1 1 1
To To
2 p B = p2 =
784 kPa
2
V1 0 p 2 = p* = 528 kPa
2
A2 = 0.001 m2 p B = 500 kPa p* = 528 kPa
T1 = To = 360 K
p1 = po = 1.0 MPa s s
Figure E9.14
Assumptions:
1. The control volume shown in the accompanying sketch operates at steady state.
2. The air is modeled as an ideal gas with k 1.4.
3. Flow through the nozzle is isentropic.
Analysis: The first step is to check whether the flow is choked. With k 1.4 and M 1.0, Eq. 9.51 gives p*po 0.528.
Since po 1.0 MPa, the critical pressure is p* 528 kPa. Thus, for back pressures of 528 kPa or less, the Mach number is
unity at the exit and the nozzle is choked.
(a) From the above discussion, it follows that for a back pressure of 500 kPa, the nozzle is choked. At the exit, M2 1.0 and
the exit pressure equals the critical pressure, p2 528 kPa. The mass flow rate is the maximum value that can be attained for
the given stagnation properties. With the ideal gas equation of state, the mass flow rate is
# p2
m r2A2V2 AV
RT2 2 2
The exit area A2 required by this expression is specified as 103 m2. Since M 1 at the exit, the exit temperature T2 can be
found from Eq. 9.50, which on rearrangement gives
To 360 K
T2 300 K
k1 2 1.4 1
1
M 1
a b 112 2
2 2
Then, with Eq. 9.37, the exit velocity V2 is
V2 2kRT2
1 kg # m /s2
1.4 a b 1300 K2 ` ` 347.2 m /s
8314 N # m

B #
28.97 kg K 1N
Finally
# 1528 103 N/m2 2110 3 m2 21347.2 m /s2

m 2.13 kg /s
a b 1300
8314 N # m
K2
28.97 kg # K
(b) Since the back pressure of 784 kPa is greater than the critical pressure determined above, the flow throughout the nozzle
is subsonic and the exit pressure equals the back pressure, p2 784 kPa. The exit Mach number can be found by solving
Eq. 9.51 to obtain
po 1k12k 12
M2 e ca b 1d f
2
k 1 p2
Inserting values
12
1 106 0.286
M2 e ca b 1 d f 0.6
2
1.4 1 7.84 105
With the exit Mach number known, the exit temperature T2 can be found from Eq. 9.50 as 336 K. The exit velocity is then
1.4 a b 13362
8314
V2 M2c2 M2 2kRT2 0.6
B 28.97
220.5 m /s
The mass flow rate is
# p2 1784 103 21103 21220.52
m r2A2V2 A2V2
RT2 1831428.97213362
1.79 kg/s
The use of Table 9.1 reduces some of the computation required in the solution. It is left as an exercise to develop a
solution using this table. Also, observe that the first step of the analysis is to check whether the flow is choked.
NORMAL SHOCK FUNCTIONS. Next, let us develop closed-form equations for normal
shocks for the case of an ideal gas with constant specific heats. For this case, it follows from
the energy equation, Eq. 9.47b, that there is no change in stagnation temperature across the
shock, Tox Toy. Then, with Eq. 9.50, the following expression for the ratio of temperatures
across the shock is obtained
k1 2
1
Mx
Ty 2
(9.53)
Tx k1 2
1
My
2
Rearranging Eq. 9.48

px
rxV2x py
ryV2y
Introducing the ideal gas equation of state, together with Eqs. 9.37 and 9.38, the ratio of the
pressure downstream of the shock to the pressure upstream is
py 1
kM 2x
(9.54)
px 1
kM 2y
Similarly, Eq. 9.46 becomes

py Ty Mx

px B Tx My
The following equation relating the Mach numbers Mx and My across the shock can be ob-
tained when Eqs. 9.53 and 9.54 are introduced in this expression
2
M 2x
k1
M 2y (9.55)
2k
M 2x 1
k1
TABLE 9.2 Normal Shock Functions for an Ideal Gas with

k 1.4
Mx My pypx TyTx poypox
1.00 1.000 00 1.0000 1.0000 1.000 00

1.10 0.911 77 1.2450 1.0649 0.998 92
1.20 0.842 17 1.5133 1.1280 0.992 80
1.30 0.785 96 1.8050 1.1909 0.979 35
1.40 0.739 71 2.1200 1.2547 0.958 19
1.50 0.701 09 2.4583 1.3202 0.929 78
1.60 0.668 44 2.8201 1.3880 0.895 20
1.70 0.640 55 3.2050 1.4583 0.855 73
1.80 0.616 50 3.6133 1.5316 0.812 68
1.90 0.595 62 4.0450 1.6079 0.767 35
2.00 0.577 35 4.5000 1.6875 0.720 88
2.10 0.561 28 4.9784 1.7704 0.674 22
2.20 0.547 06 5.4800 1.8569 0.628 12
2.30 0.534 41 6.0050 1.9468 0.583 31
2.40 0.523 12 6.5533 2.0403 0.540 15
2.50 0.512 99 7.1250 2.1375 0.499 02
2.60 0.503 87 7.7200 2.2383 0.460 12
2.70 0.495 63 8.3383 2.3429 0.423 59
2.80 0.488 17 8.9800 2.4512 0.389 46
2.90 0.481 38 9.6450 2.5632 0.357 73
3.00 0.475 19 10.333 2.6790 0.328 34
4.00 0.434 96 18.500 4.0469 0.138 76
5.00 0.415 23 29.000 5.8000 0.061 72
10.00 0.387 57 116.50 20.388 0.003 04
0.377 96 0.0
The ratio of stagnation pressures across a shock poypox is often useful. It is left as an
exercise to show that
1k
12 21k12
k 1
1
M 2y
poy

Mx 2
(9.56)
pox My k 1
1
M 2x
2
Since there is no area change across a shock, Eqs. 9.52 and 9.56 combine to give
A*x poy
(9.57)
A*y pox
For specified values of Mx and specific heat ratio k, the Mach number downstream of a
shock can be found from Eq. 9.55. Then, with Mx, My, and k known, the ratios TyTx, pypx,
and poypox can be determined from Eqs. 9.53, 9.54, and 9.56. Accordingly, tables can be set
up giving My, TyTx, pypx, and poypox versus the Mach number Mx as the single independ-
ent variable for a specified value of k. Table 9.2 is a tabulation of this kind for k 1.4.
In the next example, we consider the effect of back pressure on flow in a
convergingdiverging nozzle. Key elements of the analysis include determining whether the
flow is choked and if a normal shock exists.
EXAMPLE 9.15 Effect of Back Pressure: ConvergingDiverging Nozzle
A convergingdiverging nozzle operating at steady state has a throat area of 6.25 cm2 and an exit area of 15 cm2. Air enters
the nozzle with a negligible velocity at a pressure of 6.8 bars and a temperature of 280 K. For air as an ideal gas with k
1.4, determine the mass flow rate, in kg/s, the exit pressure, in bars, and exit Mach number for each of the five following
cases. (a) Isentropic flow with M 0.7 at the throat. (b) Isentropic flow with M 1 at the throat and the diverging portion
acting as a diffuser. (c) Isentropic flow with M 1 at the throat and the diverging portion acting as a nozzle. (d) Isentropic
flow through the nozzle with a normal shock standing at the exit. (e) A normal shock stands in the diverging section at a
location where the area is 12.5 cm2. Elsewhere in the nozzle, the flow is isentropic.
SOLUTION
Known: Air flows from specified stagnation conditions through a convergingdiverging nozzle having a known throat and
exit area.
Find: The mass flow rate, exit pressure, and exit Mach number are to be determined for each of five cases.
V1 0 A2 = 15 cm2
p1 = po = 6.8 bars
T1 = To = 280 K
1 At = 6.25 cm3 2
T po = 6.8 bars T po = 6.8 bars

1 1
To = 280 K To = 280 K
2 p = 6.52 bars Assumptions:
2 2 p2 = 6.48 bars
1. The control volume shown in the accom-
pt
pt = p* panying sketch operates at steady state. The
Mt = 0.7
Mt = 1 Ts diagrams provided locate states within
the nozzle.
Case (a) s Case (b) s 2. The air is modeled as an ideal gas with
k 1.4.
Stagnation state Stagnation state 3. Flow through the nozzle is isentropic
T T associated with associated with
state x state y throughout, except for case e, where a shock
1 po = 6.8 bars stands in the diverging section.
To = 280 K poy p2
pox 1 2
y
pt = p*
Sonic state
associated
Mt = 1 with state y
x Normal shock
Sonic state
p2 = 0.465 bars associated
2 with state x
Cases (c) and (d) s Case (e) s
Figure E9.15
Analysis:
(a) The accompanying Ts diagram shows the states visited by the gas in this case. The following are known: the Mach num-
ber at the throat, Mt 0.7, the throat area, At 6.25 cm2, and the exit area, 15 cm2. The exit Mach number M2, exit tem-
perature T2, and exit pressure p2 can be determined using the identity
A2 A2 At

A* At A*
With Mt 0.7, Table 9.1 gives AtA* 1.09437. Thus
15 cm2
a b 11.094372 2.6265
A2
A* 6.25 cm2
The flow throughout the nozzle, including the exit, is subsonic. Accordingly, with this value for A2A*, Table 9.1 gives M2
0.24. For M2 0.24, T2To 0.988, and p2po 0.959. Since the stagnation temperature and pressure are 280 K and 6.8 bars,
respectively, it follows that T2 277K and p2 6.52 bars.
The velocity at the exit is
V2 M2c2 M2 2kRT2
1 kg # m /s2 103 N # m
1.4 a b 1277 ` ` ` `
8.314 kJ
v2 0.24 K2
B 28.97 kg # K 1N 1 kJ
v2 80.1 m /s
# p2
m r2A2V2 AV
RT2 2 2
16.52 bars2115 cm2 2180.1 m/s2
0.985 kg /s
a b 1277K2
8.314 kJ
28.97 kg # K
(b) The accompanying Ts diagram shows the states visited by the gas in this case. Since M 1 at the throat, we have At
A*, and thus A2A* 2.4. Table 9.1 gives two Mach numbers for this ratio: M 0.26 and M 2.4. The diverging portion
acts as a diffuser in the present part of the example; accordingly, the subsonic value is appropriate. The supersonic value is
appropriate in part (c).
Thus, from Table 9.1 we have at M2 0.26, T2To 0.986, and p2po 0.953. Since To 280 K and po 6.8 bars, it
follows that T2 276K and p2 6.48 bars.
The velocity at the exit is
V2 M2c2 M2 2kRT2
11.42 a b 127621103 2 86.58 m /s

8.314
0.26
B 28.97
# p2 16.4821152186.582
m AV 1.062 kg/s
RT2 2 2
a b 12762
8.314
28.97
This is the maximum mass flow rate for the specified geometry and stagnation conditions: the flow is choked.
(c) The accompanying Ts diagram shows the states visited by the gas in this case. As discussed in part (b), the exit Mach
number in the present part of the example is M2 2.4. Using this, Table 9.1 gives p2 po 0.0684. With po 6.8 bars, the
pressure at the exit is p2 0.465 bars. Since the nozzle is choked, the mass flow rate is the same as found in part (b).
(d) Since a normal shock stands at the exit and the flow upstream of the shock is isentropic, the Mach number Mx and the
pressure px correspond to the values found in part (c), Mx 2.4, px 0.465 bars. Then, from Table 9.2, My 0.52 and
pypx 6.5533. The pressure downstream of the shock is thus 3.047 bars. This is the exit pressure. The mass flow is the same
as found in part (b).
(e) The accompanying Ts diagram shows the states visited by the gas. It is known that a shock stands in the diverging por-
tion where the area is Ax 12.5 cm2 Since a shock occurs, the flow is sonic at the throat, so A*x At 6.25 cm2 The Mach
number Mx can then be found from Table 9.1, by using Ax A*x 2, as Mx 2.2.
The Mach number at the exit can be determined using the identity
a ba b
A2 A2 A*x
A*y A*x A*y
Introducing Eq. 9.57 to replace A*x A*y , this becomes
poy
a ba b
A2 A2
A*y A*x pox
where pox and poy are the stagnation pressures before and after the shock, respectively. With Mx 2.2, the ratio of stagnation
pressures is obtained from Table 9.2 as poypox 0.62812. Thus
15 cm2
a b 10.628122 1.51
A2
A*y 6.25 cm2
Using this ratio and noting that the flow is subsonic after the shock, Table 9.1 gives M2 0.43, for which p2poy 0.88.
The pressure at the exit can be determined using the identity
poy
p2 a b a b pox 10.88210.6282 16.8 bars2 3.76 bars
p2
poy pox
Since the flow is choked, the mass flow rate is the same as that found in part (b).
Part (a) of the present example corresponds to the cases labeled b and c on Fig. 9.30 Part (c) corresponds to case d of
Fig. 9.30. Part (d) corresponds to case g of Fig. 9.30 and part (e) corresponds to cases e and f.
In this chapter, we have studied the thermodynamic model- tions related to gas turbines are also considered, including
ing of internal combustion engines, gas turbine power plants, aircraft propulsion systems and combined gas turbinevapor
and compressible flow in nozzles and diffusers. The modeling power cycles. In addition, the Ericsson and Stirling cycles
of cycles is based on the use of air-standard analysis, where are introduced.
the working fluid is considered to be air as an ideal gas. The chapter concludes with the study of compressible flow
The processes in internal combustion engines are de- through nozzles and diffusers. We begin by introducing the
scribed in terms of three air-standard cycles: the Otto, Diesel, momentum equation for steady, one-dimensional flow, the
and dual cycles, which differ from each other only in the velocity of sound, and the stagnation state. We then consider
way the heat addition process is modeled. For these cycles, the effects of area change and back pressure on performance
we have evaluated the principal work and heat transfers in both subsonic and supersonic flows. Choked flow and the
along with two important performance parameters: the mean presence of normal shocks in such flows are investigated. Ta-
effective pressure and the thermal efficiency. The effect of bles are introduced to facilitate analysis for the case of ideal
varying compression ratio on cycle performance is also gases with constant specific heat ratio, k 1.4.
investigated. The following list provides a study guide for this chapter.
The performance of simple gas turbine power plants is When your study of the text and end-of-chapter exercises has
described in terms of the air-standard Brayton cycle. For this been completed, you should be able to
cycle, we evaluate the principal work and heat transfers
along with two important performance parameters: the back-
work ratio and the thermal efficiency. We also consider the throughout the chapter and understand each of the re-
effects on performance of irreversibilities and of varying lated concepts. The subset of key concepts listed below
compressor pressure ratio. Three modifications of the sim- is particularly important.
ple cycle to improve performance are introduced: regenera- sketch pv and Ts diagrams of the Otto, Diesel, and
tion, reheat, and compression with intercooling. Applica- dual cycles. Apply the closed system energy balance and
the second law along with property data to determine the analyze the performance of gas turbinerelated applica-
performance of these cycles, including mean effective tions involving aircraft propulsion and combined gas
pressure, thermal efficiency, and the effects of varying turbinevapor power plants. You also should be able to
compression ratio. apply the principles of this chapter to Ericsson and
sketch schematic diagrams and accompanying Ts dia- Stirling cycles.
grams of the Brayton cycle and modifications involving discuss for nozzles and diffusers the effects of area
regeneration, reheat, and compression with intercooling. change in subsonic and supersonic flows, the effects of
In each case, be able to apply mass and energy balances, back pressure on mass flow rate, and the appearance and
the second law, and property data to determine gas tur- consequences of choking and normal shocks.
bine power cycle performance, including thermal effi- analyze the flow in nozzles and diffusers of ideal gases
ciency, back-work ratio, net power output, and the effects with constant specific heats, as in Examples 9.14 and
of varying compressor pressure ratio. 9.15.
mean effective dual cycle p. 385 momentum stagnation state p. 430

pressure p. 375 Brayton cycle p. 390 equation p. 427 choked flow p. 433, 434
air-standard regenerator velocity of sound p. 429 normal shock p. 434
analysis p. 375, 388 effectiveness p. 401 Mach number p. 429
Otto cycle p. 375 turbojet engine p. 414 subsonic and supersonic
Diesel cycle p. 381 combined cycle p. 419 flow p. 429
1. How do the events occurring within the cylinders of actual in- 8. What is the overall thermal efficiency of the combined cycle
ternal combustion engines depart from the air-standard analysis of Example 9.13? What is the overall exergetic efficiency based
of Sec. 9.1? on exergy entering the combustor with the fuel?
2. In a brochure, you read that a car has a 2-liter engine. What 9. The air entering a turbojet engine experiences a pressure
does this mean? increase as it flows through the diffuser and another pressure
3. A car magazine says that your cars engine has more power increase as it flows through the compressor. How are these pres-
when the ambient temperature is low. Do you agree? sure increases achieved?
4. When operating at high elevations, cars can lose power. Why? 10. How would the Ts diagram of Fig. 9.20 appear if frictional
effects for flow through the diffuser, compressor, turbine, and
5. Why are the external surfaces of a lawn mower engine cov-
nozzle were considered?
ered with fins?
11. How do internal and external combustion engines differ?
6. Using Eq. 6.53b, show that for a given pressure rise a gas tur-
bine compressor would require a much greater work input per 12. In which of the following media is the sonic velocity the
unit of mass flow than would the pump of a vapor power plant. greatest: air, steel, or water? Does sound propagate in a vacuum?
7. The ideal Brayton and Rankine cycles are composed of the 13. Can a shock stand upstream of the throat of a converging
same four processes, yet look different when represented on a diverging nozzle?
Ts diagram. Explain.
Otto, Diesel and Dual Cycles (c) the mean effective pressure, in kPa.
(d) the maximum temperature in the cycle, in K.
9.1 An air-standard Otto cycle has a compression ratio of 8.5.
(e) To investigate the effects of varying compression ratio, plot
At the beginning of compression, p1 100 kPa and T1 300 K.
each of the quantities calculated in parts (a) through (d)
The heat addition per unit mass of air is 1400 kJ/kg. Determine
for compression ratios ranging from 1 to 12.
(a) the net work, in kJ per kg of air. 9.2 Solve Problem 9.1 on a cold air-standard basis with specific
(b) the thermal efficiency of the cycle. heats evaluated at 300 K.
9.3 At the beginning of the compression process of an air- p

3
standard Otto cycle, p1 1 bar, T1 290 K, V1 400 cm3.
The maximum temperature in the cycle is 2200 K and the com-
pression ratio is 8. Determine
(a) the heat addition, in kJ.
(b) the net work, in kJ. 2 s=c
(d) the mean effective pressure, in bar.
(e) Develop a full accounting of the exergy transferred to the
air during the heat addition, in kJ. s=c
(f) Devise and evaluate an exergetic efficiency for the cycle.
Let T0 290 K, p0 1 bar. 1 4
9.4 Plot each of the quantities specified in parts (a) through (d) v
of Problem 9.3 versus the compression ratio ranging from
2 to 12. Figure P9.11
9.5 Solve Problem 9.3 on a cold air-standard basis with spe-
cific heats evaluated at 300 K. particular Atkinson cycle, the compression ratio during
9.6 Consider the cycle in Problem 9.3 as a model of the isentropic compression is 8.5. At the beginning of this
processes in each cylinder of a spark-ignition engine. If the en- compression process, p1 100 kPa and T1 300 K. The con-
gine has four cylinders and the cycle is repeated 1200 times stant volume heat addition per unit mass of air is 1400 kJ/kg.
per min in each cylinder, determine the net power output, (a) Sketch the cycle on Ts coordinates. Determine (b) the net
in kW. work, in kJ per kg of air, (c) the thermal efficiency of the cy-
cle, and (d) the mean effective pressure, in kPa. Compare your
9.7 An air-standard Otto cycle has a compression ratio of 7.5.
answers with those obtained for the Otto cycle in Problem 9.1
At the beginning of compression, p1 85 kPa and T1 32C.
and discuss.
The mass of air is 2 g, and the maximum temperature in the
cycle is 960 K. Determine 9.12 On a cold air-standard basis, derive an expression for the
thermal efficiency of the Atkinson cycle (see Fig. P9.11)
(a) the heat rejection, in kJ.
in terms of the volume ratio during the isentropic compression,
(b) the net work, in kJ.
the pressure ratio for the constant volume process, and the spe-
cific heat ratio. Compare the thermal efficiencies of the cold
(d) the mean effective pressure, in kPa.
air-standard Atkinson and Otto cycles, each having the same
9.8 Consider a modification of the air-standard Otto cycle in compression ratio and maximum temperature. Discuss.
which the isentropic compression and expansion processes are
9.13 The pressure and temperature at the beginning of com-
each replaced with polytropic processes having n 1.3. The
pression of an air-standard Diesel cycle are 95 kPa and 300 K,
compression ratio is 9 for the modified cycle. At the beginning
respectively. At the end of the heat addition, the pressure is
of compression, p1 1 bar and T1 300 K. The maximum
7.2 MPa and the temperature is 2150 K. Determine
temperature during the cycle is 2000 K. Determine
(a) the compression ratio.
(a) the heat transfer and work per unit mass of air, in kJ/kg,
(b) the cutoff ratio.
for each process in the modified cycle.
(c) the thermal efficiency of the cycle.
(d) the mean effective pressure, in kPa.
(c) the mean effective pressure, in bar.
9.9 At the beginning of the compression process in an air- 9.14 Solve Problem 9.13 on a cold air-standard basis with spe-
standard Otto cycle, p1 1 bar and T1 300 K. The maximum cific heats evaluated at 300 K.
cycle temperature is 2000 K. Plot the net work per unit of mass, 9.15 The conditions at the beginning of compression in an air-
in kJ/kg, the thermal efficiency, and the mean effective pres- standard Diesel cycle are fixed by p1 200 kPa, T1 380 K.
sure, in bar, versus the compression ratio ranging from 2 to 14. The compression ratio is 20 and the heat addition per unit mass
9.10 Investigate the effect of maximum cycle temperature on is 900 kJ/kg. Determine
the net work per unit mass of air for air-standard Otto cycles (a) the maximum temperature, in K.
with compression ratios of 5, 8, and 11. At the beginning of (b) the cutoff ratio.
the compression process, p1 1 bar and T1 295 K. Let the (c) the net work per unit mass of air, in kJ/kg.
maximum temperature in each case vary from 1000 to 2200 K. (d) the thermal efficiency.
9.11 The pressure-specific volume diagram of the air-standard (e) the mean effective pressure, in kPa.
Atkinson cycle is shown in Fig. P9.11. The cycle consists of (f) To investigate the effects of varying compression ratio, plot
isentropic compression, constant volume heat addition, isen- each of the quantities calculated in parts (a) through (e) for
tropic expansion, and constant pressure compression. For a compression ratios ranging from 5 to 25.
9.16 For the Diesel cycle of Problem 9.15 with a compression 9.23 For the cycle in Problem 9.22, plot each of the quantities
ratio of 20 and a heat addition per unit mass of 900 kJ/kg calculated in parts (a) through (d) versus the ratio of constant-
volume heat addition to total heat addition varying from 0 to
(a) evaluate the exergy transfers accompanying heat and work
1. Discuss.
for each process, in kJ/kg.
(b) devise and evaluate an exergetic efficiency for the cycle. 9.24 Solve Problem 9.23 on a cold air-standard basis with spe-
Let T0 300 K, p0 100 kPa. cific heats evaluated at 300 K.
9.17 The displacement volume of an internal combustion en- 9.25 The thermal efficiency, , of a cold air-standard dual cy-
gine is 5.6 liters. The processes within each cylinder of the cle can be expressed as
engine are modeled as an air-standard Diesel cycle with a cut-
rpr kc 1
c d
off ratio of 2.4. The state of the air at the beginning of com- 1
h1
pression is fixed by p1 95 kPa, T1 27C, and V1 6.0 r k1 1rp 12
krp 1rc 12
liters. Determine the net work per cycle, in kJ, the power de-
veloped by the engine, in kW, and the thermal efficiency, if the where r is compression ratio, rc is cutoff ratio, and rp is the
cycle is executed 1500 times per min. pressure ratio for the constant volume heat addition. Derive
9.18 The state at the beginning of compression of an air- this expression.
standard Diesel cycle is fixed by p1 100 kPa and T1 310 K. 9.26 An air-standard dual cycle has a compression ratio of 16
The compression ratio is 15. For cutoff ratios ranging from and a cutoff ratio of 1.15. At the beginning of compression,
1.5 to 2.5, plot p1 95 kPa and T1 300 K. The pressure increases by a fac-
(a) the maximum temperature, in K. tor of 2.2 during the constant volume heat addition process. If
(b) the pressure at the end of the expansion, in kPa. the mass of air is 0.04 kg, determine
(c) the net work per unit mass of air, in kJ/kg. (a) the heat addition at constant volume and at constant pres-
(d) the thermal efficiency. sure, each in kJ.
9.19 An air-standard Diesel cycle has a maximum temperature (b) the net work of the cycle, in kJ.
of 1800 K. At the beginning of compression, p1 95 kPa and (c) the heat rejection, in kJ.
T1 300 K. The mass of air is 12 g. For compression ratios (d) the thermal efficiency.
ranging from 15 to 25, plot 9.27 At the beginning of the compression process in an air-
(a) the net work of the cycle, in kJ. standard dual cycle, p1 1 bar and T1 300 K. The total heat
(b) the thermal efficiency. addition is 1000 kJ/kg. Plot the net work per unit of mass, in
(c) the mean effective pressure, in kPa. kJ/kg, the mean effective pressure, in bar, and the thermal ef-
ficiency versus compression ratio for different fractions of con-
9.20 At the beginning of compression in an air-standard Diesel
stant volume and constant pressure heat addition. Consider
cycle, p1 96 kPa, V1 0.016 m3, and T1 290 K. The com-
compression ratio ranging from 10 to 20.
pression ratio is 15 and the maximum cycle temperature is
1290 K. Determine
(a) the mass of air, in kg. Brayton Cycle
(b) the heat addition and heat rejection per cycle, each in kJ. 9.28 Air enters the compressor of an ideal air-standard Brayton
(c) the net work, in kJ, and the thermal efficiency. cycle at 100 kPa, 300 K, with a volumetric flow rate of 5 m3/s.
9.21 At the beginning of the compression process in an air- The compressor pressure ratio is 10. For turbine inlet temper-
standard Diesel cycle, p1 1 bar and T1 300 K. For maximum atures ranging from 1000 to 1600 K, plot
cycle temperatures of 1200, 1500, 1800, and 2100 K, plot the (a) the thermal efficiency of the cycle.
heat addition per unit of mass, in kJ/kg, the net work per unit of (b) the back work ratio.
mass, in kJ/kg, the mean effective pressure, in bar, and the thermal (c) the net power developed, in kW.
efficiency, each versus compression ratio ranging from 5 to 20.
9.29 Air enters the compressor of an ideal air-standard Brayton
9.22 An air-standard dual cycle has a compression ratio of 9.
cycle at 100 kPa, 300 K, with a volumetric flow rate of 5 m3/s.
At the beginning of compression, p1 100 kPa and T1 300
The turbine inlet temperature is 1400 K. For compressor pres-
K. The heat addition per unit mass of air is 1400 kJ/kg, with
sure ratios ranging from 2 to 20, plot
one half added at constant volume and one half added at con-
stant pressure. Determine (a) the thermal efficiency of the cycle.
(b) the back work ratio.
(a) the temperatures at the end of each heat addition process,
(c) the net power developed, in kW.
in K.
(b) the net work of the cycle per unit mass of air, in kJ/kg. 9.30 Consider an ideal air-standard Brayton cycle with mini-
(c) the thermal efficiency. mum and maximum temperatures of 300 K and 1500 K, re-
(d) the mean effective pressure, in kPa. spectively. The pressure ratio is that which maximizes the net
work developed by the cycle per unit mass of air flow. On a (d) the rate of exergy destruction in the regenerator, in kW,
cold air-standard basis, calculate for T0 300 K.
(a) the compressor and turbine work per unit mass of air flow, 9.37 Reconsider Problem 9.34, but include a regenerator in the
each in kJ/kg. cycle. For regenerator effectiveness values ranging from 0 to
(b) the thermal efficiency of the cycle. 100%, plot
(c) Plot the thermal efficiency versus the maximum cycle tem- (a) the heat addition per unit mass of air flowing, in kJ/kg.
perature ranging from 1200 to 1800 K. (b) the thermal efficiency.
9.31 On the basis of a cold air-standard analysis, show that the 9.38 On the basis of a cold air-standard analysis, show that the
back work ratio of an ideal air-standard Brayton cycle equals thermal efficiency of an ideal regenerative gas turbine can be
the ratio of absolute temperatures at the compressor inlet and expressed as
the turbine outlet.
h1a b 1r2 1k12k
9.32 The compressor inlet temperature for an ideal Brayton cy- T1
cle is T1 and the turbine inlet temperature is T3. Using a cold T3
air-standard analysis, show that the temperature T2 at the com- where r is the compressor pressure ratio, and T1 and T3 denote
pressor exit that maximizes the net work developed per unit the temperatures at the compressor and turbine inlets, respectively.
mass of air flow is T2 (T1T3)12.
9.39 A regenerative gas turbine power plant is shown in Fig.
9.33 Reconsider Problem 9.29, but include in the analysis that P9.39. Air enters the compressor at 1 bar, 27C with a mass flow
the turbine and compressor each have isentropic efficiencies rate of 0.562 kg/s and is compressed to 4 bar. The isentropic
of 90, 80, and 70%. The compressor pressure ratio varies over efficiency of the compressor is 80%, and the regenerator effec-
the same range as in Problem 9.29. Plot, for each value of isen- tiveness is 90%. All the power developed by the high-pressure
tropic efficiency turbine is used to run the compressor. The low-pressure turbine
(a) the thermal efficiency. provides the net power output. Each turbine has an isentropic
(b) the back work ratio. efficiency of 87% and the temperature at the inlet to the high-
(c) the net power developed, in kW. pressure turbine is 1200 K. Determine
(d) the rates of exergy destruction in the compressor and tur- (a) the net power output, in kW.
bine, respectively, each in kW, for T0 300 K. (b) the thermal efficiency.
9.34 The compressor and turbine of a simple gas turbine each (c) the temperature of the air at states 2, 3, 5, 6, and 7, in K.
have isentropic efficiencies of 90%. The compressor pressure
ratio is 12. The minimum and maximum temperatures are 1 bar
290 K and 1400 K, respectively. On the basis of an air-standard
analysis, compare the values of (a) the net work per unit mass Regenerator
7
of air flowing, in kJ/kg, (b) the heat rejected per unit mass of
air flowing, in kJ/kg, and (c) the thermal efficiency to the same
quantities evaluated for an ideal cycle.
Qin
9.35 Air enters the compressor of a simple gas turbine at 100
kPa, 300 K, with a volumetric flow rate of 5 m3/s. The com-
T4 = 1200 K 3
pressor pressure ratio is 10 and its isentropic efficiency is 85%.
6
At the inlet to the turbine, the pressure is 950 kPa, and the tem-
perature is 1400 K. The turbine has an isentropic efficiency of
p2 = 4 bar 2
88% and the exit pressure is 100 kPa. On the basis of an air- 4 Combustor
standard analysis, Compressor
(a) develop a full accounting of the net exergy increase of the
air passing through the gas turbine combustor, in kW.
(b) devise and evaluate an exergetic efficiency for the gas tur-
bine cycle. High-pressure
turbine
Let T0 300 K, p0 100 kPa. 5
1
Regeneration, Reheat, and Compression

1 bar, 27C
with Intercooling
Wnet Low-pressure turbine
9.36 Reconsider Problem 9.33, but incorporate a regenerator
with an effectiveness of 80% into the cycle. Plot
Figure P9.39
(a) the thermal efficiency.
(b) the back work ratio. 9.40 Air enters the turbine of a gas turbine at 1200 kPa, 1200 K,
(c) the net power developed, in kW. and expands to 100 kPa in two stages. Between the stages, the
air is reheated at a constant pressure of 350 kPa to 1200 K. between the stages. The regenerator effectiveness is 80%, and
The expansion through each turbine stage is isentropic. De- the pressure ratios are the same across each compressor stage.
termine, in kJ per kg of air flowing The stages have equal isentropic efficiencies. Construct the
(a) the work developed by each stage. same plots as requested in parts (a) through (c) of Problem 9.36
(b) the heat transfer for the reheat process. for compressor stage isentropic efficiencies of 100%, 90%,
(c) the increase in net work as compared to a single stage of 80%, and 70%.
expansion with no reheat. 9.48 Referring to Example 9.10, show that if Td T1 the pres-
9.41 Reconsider Problem 9.40 and include in the analysis that sure ratios across the two compressor stages are related by
each turbine stage might have an isentropic efficiency less than
p2 Td k 1k12
a ba b
pi
100%. Plot each of the quantities calculated in parts (a) through
(c) of Problem 9.40 for values of the interstage pressure rang- p1 pi T1
ing from 100 to 1200 kPa and for isentropic efficiencies of
100%, 80%, and 60%. 9.49 Rework Example 9.10 for the case of a three-stage com-
pressor with intercooling between stages.
9.42 Consider a two-stage turbine operating at steady state with
reheat at constant pressure between the stages. Show that the 9.50 Modify the cycle of Problem 9.36 to include two-stage
maximum work is developed when the pressure ratio is the compression and expansion, with intercooling to 300 K and
same across each stage. Use a cold air-standard analysis, as- reheat to 1400 K, respectively, between the stages. The
suming the inlet state and the exit pressure are specified, each regenerator effectiveness is 80%, and the pressure ratios are
expansion process is isentropic, and the temperature at the inlet the same across each compressor stage. The intercooler and
to each turbine stage is the same. Kinetic and potential energy reheater both operate at the same pressure. The compressor
effects can be ignored. and turbine stages all have equal isentropic efficiencies. Con-
struct the same plots as requested in parts (a) through (c) of
9.43 Modify the cycle of Problem 9.36 to include a two-stage
Problem 9.36 for stage isentropic efficiencies of 100%, 90%,
turbine expansion with reheat to 1400 K at constant pressure be-
80%, and 70%.
tween the stages. The regenerator effectiveness is 80%, and the
pressure ratio is the same across each turbine stage. The stages 9.51 Air enters the compressor of a gas turbine at 100 kPa,
have equal isentropic efficiencies. Construct the same plots as 300 K. The air is compressed in two stages to 900 kPa, with
requested in parts (a) through (c) of Problem 9.36 for turbine intercooling to 300 K between the stages at a pressure of
stage isentropic efficiencies of 100%, 90%, 80%, and 70%. 300 kPa. The turbine inlet temperature is 1480 K and the ex-
9.44 If the inlet state and the exit pressure are specified for a two- pansion occurs in two stages, with reheat to 1420 K between
stage turbine with reheat between the stages and operating at the stages at a pressure of 300 kPa. The compressor and tur-
steady state, show that the maximum total work output is ob- bine stage efficiencies are 84 and 82%, respectively. The net
tained when the pressure ratio is the same across each stage. Use power developed is 1.8 MW. Determine
a cold air-standard analysis assuming that each compression (a) the volumetric flow rate, in m3/s, at the inlet of each com-
process is isentropic, there is no pressure drop through the re- pressor stage.
heater, and the temperature at the inlet to each turbine stage is (b) the thermal efficiency of the cycle.
the same. Kinetic and potential energy effects can be ignored. (c) the back work ratio.
9.45 A two-stage air compressor operates at steady state, com- 9.52 Reconsider Problem 9.51 but include a regenerator with
pressing 10 m3/min of air from 100 kPa, 300 K, to 1200 kPa. an effectiveness of 75%.
An intercooler between the two stages cools the air to 300 K
at a constant pressure of 350 kPa. The compression processes Other Gas Power System Applications
are isentropic. Calculate the power required to run the com- 9.53 Air at 22 kPa, 220 K, and 250 m/s enters a turbojet en-
pressor, in kW, and compare the result to the power required gine in flight at an altitude of 10,000 m. The pressure ratio
for isentropic compression from the same inlet state to the same across the compressor is 12. The turbine inlet temperature
final pressure. is 1400 K, and the pressure at the nozzle exit is 22 kPa. The
9.46 Reconsider Problem 9.45 and include in the analysis that diffuser and nozzle processes are isentropic, the compressor
each compressor stage might have an isentropic efficiency less and turbine have isentropic efficiencies of 85 and 88%,
than 100%. Plot, in kW, (a) the power input to each stage, respectively, and there is no pressure drop for flow through
(b) the heat transfer rate for the intercooler, and (c) the decrease the combustor. On the basis of an air-standard analysis,
in power input as compared to a single stage of compression determine
with no intercooling, for values of interstage pressure ranging (a) the pressures and temperatures at each principal state, in
from 100 to 1200 kPa and for isentropic efficiencies of 100%, kPa and K, respectively.
80%, and 60%. (b) the velocity at the nozzle exit, in m/s.
9.47 Modify the cycle of Problem 9.36 to include a two-stage Neglect kinetic energy except at the diffuser inlet and the
compressor with intercooling to 300 K at constant pressure nozzle exit.
9.54 For the turbojet in Problem 9.54, plot the velocity at the (e) the net rate at which exergy is carried out with the cool-
nozzle exit, in m/s, the pressure at the turbine exit, in kPa, and ing water, in MW.
the rate of heat input to the combustor, in kW, each as a func- Let T0 20C, p0 1 bar.
tion of compressor pressure ratio in the range of 6 to 14. Re-
peat for turbine inlet temperatures of 1200 K and 1000 K. 9.59 A combined gas turbinevapor power plant (Fig. 9.23) has
a net power output of 100 MW. Air enters the compressor of
9.55 Consider the addition of an afterburner to the turbojet in the gas turbine at 100 kPa, 300 K, and is compressed to
Problem 9.54 that raises the temperature at the inlet of the nozzle 1200 kPa. The isentropic efficiency of the compressor is 84%.
to 1300 K. Determine the velocity at the nozzle exit, in m/s. The conditions at the inlet to the turbine are 1200 kPa and
9.56 Air enters the diffuser of a ramjet engine at 40 kPa, 240 K, 1400 K. Air expands through the turbine, which has an
with a velocity of 2500 km/h and decelerates to negligible ve- isentropic efficiency of 88%, to a pressure of 100 kPa. The air
locity. On the basis of an air-standard analysis, the heat addition then passes through the interconnecting heat exchanger, and is
is 1080 kJ per kg of air passing through the engine. Air exits finally discharged at 480 K. Steam enters the turbine of the
the nozzle at 40 kPa. Determine vapor power cycle at 8 MPa, 400C, and expands to the con-
denser pressure of 8 kPa. Water enters the pump as saturated
(a) the pressure at the diffuser exit, in kPa. liquid at 8 kPa. The turbine and pump have isentropic effi-
(b) the velocity at the nozzle exit, in m/s. ciencies of 90 and 80%, respectively. Determine
Neglect kinetic energy except at the diffuser inlet and the noz- (a) the mass flow rates of air and steam, each in kg/s.
zle exit. (b) the thermal efficiency of the combined cycle.
9.57 A turboprop engine consists of a diffuser, compressor, (c) a full accounting of the net exergy increase of the air pass-
#
combustor, turbine, and nozzle. The turbine drives a propeller ing through the combustor of the gas turbine, mair ef3 ef2,
as well as the compressor. Air enters the diffuser with a volu- in MW. Discuss.
metric flow rate of 83.7 m3/s at 40 kPa, 240 K, and a velocity Let T0 300 K, p0 100 kPa.
of 180 m/s, and decelerates essentially to zero velocity. The
9.60 Air enters the compressor of an Ericsson cycle at 300 K,
compressor pressure ratio is 10 and the compressor has an
1 bar, with a mass flow rate of 5 kg/s. The pressure and tem-
isentropic efficiency of 85%. The turbine inlet temperature is
perature at the inlet to the turbine are 10 bar and 1400 K, re-
1140 K, and its isentropic efficiency is 85%. The turbine exit
spectively. Determine
pressure is 50 kPa. Flow through the diffuser and nozzle is
isentropic. Using an air-standard analysis, determine (a) the net power developed, in kW.
(a) the power delivered to the propeller, in MW.
(c) the back work ratio.
(b) the velocity at the nozzle exit, in m/s.
Neglect kinetic energy except at the diffuser inlet and the noz- 9.61 For the cycle in Problem 9.60, plot the net power devel-
zle exit. oped, in kW, for compressor pressure ratios ranging from 2
to 15. Repeat for turbine inlet temperatures of 1200 K and
9.58 Air enters the compressor of a combined gas turbinevapor 1000 K.
power plant (Fig. 9.23) at 1 bar, 25C. The isentropic com-
pressor efficiency is 85% and the compressor pressure ratio is 9.62 Nitrogen (N2) is the working fluid of a Stirling cycle with
14. The air passing through the combustor receives energy by a compression ratio of nine. At the beginning of the isother-
heat transfer at a rate of 50 MW with no significant decrease mal compression, the temperature, pressure, and volume are
in pressure. At the inlet to the turbine the air is at 1250C. The 310 K, 1 bar, and 0.008 m3, respectively. The temperature dur-
air expands through the turbine, which has an isentropic effi- ing the isothermal expansion is 1000 K. Determine
ciency of 87%, to a pressure of 1 bar. Then, the air passes (a) the net work, in kJ.
through the interconnecting heat exchanger and is finally dis- (b) the thermal efficiency.
charged at 200C, 1 bar. Steam enters the turbine of the vapor (c) the mean effective pressure, in bar.
cycle at 12.5 MPa, 500C, and expands to a condenser pres-
sure of 0.1 bar. Water enters the pump as a saturated liquid at Compressible Flow
0.1 bar. The turbine and pump have isentropic efficiencies of 9.63 If the mass flow rate of air for the cycle in Problem 9.54
90 and 100%, respectively. Cooling water enters the condenser is 50 kg/s, calculate the thrust developed by the engine, in kN.
at 20C and exits at 35C. Determine
9.64 Referring to the turbojet in Problem 9.54 and the modi-
(a) the mass flow rates of the air, steam, and cooling water,
fied turbojet in Problem 9.56, calculate the thrust developed
each in kg/s.
by each engine, in kN, if the mass flow rate of air is 50 kg/s.
(b) the net power developed by the gas turbine cycle and the
Discuss.
vapor cycle, respectively, each in MW.
(c) the thermal efficiency of the combined cycle. 9.65 Air enters the diffuser of a turbojet engine at 18 kPa,
(d) the net rate at which exergy is carried out with the exhaust 216 K, with a volumetric flow rate of 230 m3/s and a veloc-
#
air, mair ef5 ef1, in MW. ity of 265 m/s. The compressor pressure ratio is 15, and its
isentropic efficiency is 87%. Air enters the turbine at 1360 K 280C. The mass flow rate is 2 kg/s, the flow is choked, and
and the same pressure as at the exit of the compressor. The the exit plane pressure is 1 bar. Determine the diameter of the
turbine isentropic efficiency is 89%, and the nozzle isentropic nozzle, in cm, at locations where the pressure is 1.5 bar, and
efficiency is 97%. The pressure at the nozzle exit is 18 kPa. 1 bar, respectively.
On the basis of an air-standard analysis, calculate the thrust,
9.78 An ideal gas mixture with k 1.31 and a molecular weight
in kN.
of 23 is supplied to a converging nozzle at po 5 bar, To
9.67 Calculate the ratio of the thrust developed to the mass flow 700 K, which discharges into a region where the pressure is 1
rate of air, in N per kg/s, for the ramjet engine in Problem 9.57. bar. The exit area is 30 cm2. For steady isentropic flow through
9.68 Air flows at steady state through a horizontal, well-insulated, the nozzle, determine
constant-area duct of diameter 0.25 m. At the inlet, (a) the exit temperature of the gas, in K.
p1 2.4 bar, T1 430 K. The temperature of the air leaving (b) the exit velocity of the gas, in m/s.
the duct is 370 K. The mass flow rate is 600 kg/min. Determine (c) the mass flow rate, in kg/s.
the magnitude, in N, of the net horizontal force exerted by the 9.79 Air at po 1.4 bar, To 280 K expands isentropically
duct wall on the air. In which direction does the force act? through a converging nozzle and discharges to the atmosphere
9.69 Air flows at steady state through a horizontal, well- at 1 bar. The exit plane area is 0.0013 m2.
insulated duct of varying cross-sectional area, entering at (a) Determine the mass flow rate, in kg/s.
15 bar, 340 K, with a velocity of 20 m/s. At the exit, the pres- (b) If the supply region pressure, po, were increased to 2 bar,
sure is 9 bar and the temperature is 300 K. The diameter of what would be the mass flow rate, in kg/s.?
the exit is 1 cm. Determine
9.80 Air as an ideal gas with k 1.4 enters a diffuser operat-
(a) the net force, in N, exerted by the air on the duct in the ing at steady state at 4 bar, 290 K, with a velocity of 512 m/s.
direction of flow. Assuming isentropic flow, plot the velocity, in m/s, the Mach
(b) the rate of exergy destruction, in kW. Let T0 300 K and number, and the area ratio AA* for locations in the flow cor-
p0 1 bar. responding to pressures ranging from 4 to 14 bar.
9.70 A flash of lightning is sighted and 3 seconds later thun- 9.81 A convergingdiverging nozzle operating at steady state has
der is heard. Approximately how far away was the lightning a throat area of 3 cm2 and an exit area of 6 cm2. Air as an ideal
strike? gas with k 1.4 enters the nozzle at 8 bar, 400 K, and a Mach
9.71 Using data from Table A-4, estimate the sonic velocity, in number of 0.2, and flows isentropically throughout. If the noz-
m/s, of steam of 60 bar, 360C. Compare the result with the zle is choked, and the diverging portion acts as a supersonic
value predicted by the ideal gas model. nozzle, determine the mass flow rate, in kg/s, and the Mach
number, pressure, in bar, and temperature, in K, at the exit. Re-
9.72 Plot the Mach number of carbon dioxide at 1 bar, 460 m/s,
peat if the diverging portion acts as a supersonic diffuser.
as a function of temperature in the range 250 to 1000 K.
9.82 For the nozzle in Problem 9.81, determine the back pres-
9.73 For Problem 9.70, determine the values of the Mach num- sure, in bar, for which a normal shock would stand at the exit
ber, the stagnation temperature, in K, and the stagnation pres- plane.
sure, in bar, at the inlet and exit of the duct, respectively.
9.83 For the nozzle in Problem 9.81, a normal shock stands in
9.74 Steam flows through a passageway, and at a particular lo- the diverging section at a location where the pressure is 2 bar.
cation the pressure is 3 bar. The corresponding stagnation state The flow is isentropic, except where the shock stands. Deter-
is fixed by a stagnation pressure of 7 bar and a stagnation tem- mine the back pressure, in bar.
perature of 400C. Determine the specific enthalpy, in kJ/kg,
and the velocity, in m/s. 9.84 Air as an ideal gas with k 1.4 undergoes a normal shock.
The upstream conditions are px 0.5 bar, Tx 280 K, and
9.75 For the isentropic flow of an ideal gas with constant spe- Mx 1.8. Determine
cific heat ratio k, the ratio of the temperature T* to the stag-
nation temperature To is T*To 2(k
1). Develop this (a) the pressure py, in bar.
relationship. (b) the stagnation pressure pox, in bar.
(c) the stagnation temperature Tox, in K.
9.76 A gas expands isentropically through a converging nozzle (d) the change in specific entropy across the shock, in kJ/kg # K.
from a large tank at 8 bar, 500 K. Assuming ideal gas behavior, (e) Plot the quantities of parts (a)(d) versus Mx ranging from
determine the critical pressure p*, in bar, and the corresponding 1.0 to 2.0. All other upstream conditions remain the same.
temperature, in K, if the gas is
9.85 Air at 3.4 bar, 530 K, and a Mach number of 0.4 enters a
(a) air. convergingdiverging nozzle operating at steady state. A nor-
(b) carbon dioxide (CO2). mal shock stands in the diverging section at a location where
(c) water vapor. the Mach number is Mx 1.8. The flow is isentropic, except
9.77 Steam expands isentropically through a converging noz- where the shock stands. If the air behaves as an ideal gas with
zle operating at steady state from a large tank at 1.83 bar, k 1.4, determine
(a) the stagnation temperature Tox, in K. 9.86 Derive the following expressions: (a) Eq. 9.55, (b) Eq.
(b) the stagnation pressure pox, in bar. 9.56, (c) Eq. 9.57.
(c) the pressure px, in bar.
9.87 Using Interactive Thermodynamics: IT, generate tables of
(d) the pressure py, in bar.
the same isentropic flow functions as in Table 9.1 for specific
(e) the stagnation pressure poy, in bar.
heat ratios of 1.2, 1.3, 1.4, and 1.67 and Mach numbers
(f ) the stagnation temperature Toy, in K.
ranging from 0 to 5.
If the throat area is 7.6 104 m2, and the exit plane pressure 9.88 Using Interactive Thermodynamics: IT, generate tables of
is 2.4 bar, determine the mass flow rate, in kg/s, and the exit the same normal shock functions as in Table 9.2 for specific
area, in m2. heat ratios of 1.2, 1.3, 1.4, and 1.67 and Mach numbers ranging
from 1 to 5.
9.1D With the development of high-strength metalceramic

materials, internal combustion engines can now be built with High-pressure
steam
no cylinder wall cooling. These adiabatic engines operate with
cylinder wall temperatures as high as 930C. What are the im- Low-
portant considerations for adiabatic engine design? Are adia- Combustor pressure
batic engines likely to find widespread application? Discuss. steam
9.2D An important factor leading to the increase in perform-
ance of gas turbines over the years has been the use of turbine
blade cooling to allow higher turbine inlet temperatures. With
the aid of diagrams, explain the various methods of turbine
blade cooling that are commonly used. What are some of the
most important research issues in gas turbine blade technol- Air in
ogy today? Discuss.
9.3D Steam-injected gas turbines use hot turbine exhaust gases
to produce steam that is injected directly into the gas turbine
Heat
system. Figure P9.3D illustrates two possible approaches to recovery
steam injection. In one approach, steam is injected directly into boiler
the combustor. In the other approach, steam is injected into the
low-pressure turbine stages.
(a) What are the relative advantages and disadvantages of
these steam injection approaches? How does steam injec-
tion lead to better power cycle performance?
(b) Each of the steam injection approaches is inherently simpler Turbine
than combined cycles like the one illustrated in Fig. 9.23. exhaust Water
What are the other advantages and disadvantages of direct supply
steam injection compared to combined cycles? Figure P9.3D
9.4D Closed Brayton power systems, receiving their energy in-
put from radioisotopes, nuclear reactors, or solar collectors, 9.6D Inlet air temperature and pressure can have significant im-
have been suggested for meeting space vehicle power require- pact on gas turbine performance. Investigate the effect on the
ments. What are the advantages and disadvantages of closed power developed by a General Electric LM 6000 gas turbine
Brayton cycles for spaceflight applications? What mission- when the inlet air temperature and pressure vary about base-
specific design criteria might determine the selection of the line values of 10C and 1 bar, respectively. What are some ways
system and the energy source? that could be used to alter the inlet air temperature and pres-
9.5D Factories requiring compressed air and process heat com- sure, and what are the economic implications? Prepare a mem-
monly run electrically-driven air compressors and natural gas- orandum summarizing your findings.
fired boilers to meet these respective needs. As an alternative, 9.7D A manufacturing company currently purchases 2.4
commercially available natural gas-fueled engine-driven com- 105 MW # h of electricity annually from the local utility com-
pressor systems can simultaneously provide for both needs. pany. An aging boiler on the premises annually provides 4
Determine if utility rates in your locale are favorable for the 108 kg of process steam at 20 bar. Consider the feasibility of
adoption of such systems. Prepare a memorandum explaining acquiring a cogeneration system to meet these needs. The sys-
your conclusions. tem would employ a natural gasfueled gas turbine to produce
the electricity and a heat-recovery steam generator to produce subsonic and supersonic applications. Include a discussion of
the steam. Using thermoeconomic principles, investigate the how engine placement affects diffuser performance.
economic issues that should be considered in making a rec- 9.10D In what ways must the compressible flow analysis pre-
ommendation about the proposed cogeneration system. Write sented in this chapter be modified to model the flow through
a report of your findings. steam turbines? What special design considerations arise be-
9.8D The Stirling engine was first patented in 1816 but has not cause of the possibility of condensation occurring within the
been widely commercialized. Still, efforts continue to develop blade rows and nozzles of steam turbines?
Stirling engine technology for practical uses such as vehicle 9.11D End of Cheap Oil in View, Experts Say (see box
propulsion. Prepare a memorandum summarizing the status of Sec. 9.2). Considering the likelihood of oil scarcity in years
Stirling engine technology. Discuss the advantages and disad- ahead, investigate alternatives to conventional oil for meet-
vantages of Stirling engines and assess the likelihood that they ing our transportation needs without excessive costs or en-
will be more widely used in the future. vironmental impacts. Write a report including at least three
9.9D The inlet to a gas turbine aircraft engine must provide air references.
to the compressor with as little a drop in stagnation pressure 9.12D New Power Plant Breaks Imagined Barrier (see box
and with as small a drag force on the aircraft as possible. The Sec. 9.10). Investigate technical innovations that might allow
inlet also serves as a diffuser to raise the pressure of the air the thermal efficiency of future combined-cycle power plants
entering the compressor while reducing the air velocity. Write to exceed the 60% value of the H SystemTM. Write a report
a paper discussing the most common types of inlet designs for including at least three references.
C
H
A
P
T
Refrigeration and
10 E
R Heat Pump
Systems
E N G I N E E R I N G C O N T E X T Refrigeration systems for food preser-

vation and air conditioning play prominent roles in our everyday lives. Heat pumps also
are used for heating buildings and for producing industrial process heat. There are
many other examples of commercial and industrial uses of refrigeration, including air
separation to obtain liquid oxygen and liquid nitrogen, liquefaction of natural gas, and
production of ice.
chapter objective The objective of this chapter is to describe some of the common types of refrigeration
and heat pump systems presently in use and to illustrate how such systems can be mod-
eled thermodynamically. The three principal types described are the vapor-compression,
absorption, and reversed Brayton cycles. As for the power systems studied in Chaps. 8
and 9, both vapor and gas systems are considered. In vapor systems, the refrigerant is
alternately vaporized and condensed. In gas refrigeration systems, the refrigerant remains
a gas.

10.1 Vapor Refrigeration Systems
The purpose of a refrigeration system is to maintain a cold region at a temperature below
the temperature of its surroundings. This is commonly achieved using the vapor refrigera-
tion systems that are the subject of the present section.
CARNOT REFRIGERATION CYCLE
To introduce some important aspects of vapor refrigeration, let us begin by considering a

Carnot vapor refrigeration cycle. This cycle is obtained by reversing the Carnot vapor power
cycle introduced in Sec. 5.6. Figure 10.1 shows the schematic and accompanying Ts dia-
gram of a Carnot refrigeration cycle operating between a region at temperature TC and an-
other region at a higher temperature TH. The cycle is executed by a refrigerant circulating
steadily through a series of components. All processes are internally reversible. Also, since
heat transfers between the refrigerant and each region occur with no temperature differences,
there are no external irreversibilities. The energy transfers shown on the diagram are positive
in the directions indicated by the arrows.
454
10.1 Vapor Refrigeration Systems 455

Warm region at TH Qout
T
2
3 Condenser 3 2
TH
Turbine
Wt Wc
Compressor TC
4 1
Evaporator
4 1 b a s

Cold region at TC Qin
Figure 10.1 Carnot vapor refrigeration cycle.
Let us follow the refrigerant as it passes steadily through each of the components in
the cycle, beginning at the inlet to the evaporator. The refrigerant enters the evaporator
as a two-phase liquidvapor mixture at state 4. In the evaporator some of the refrigerant
changes phase from liquid to vapor as a result of heat transfer from the region at tem-
perature TC to the refrigerant. The temperature and pressure of the refrigerant remain
constant during the process from state 4 to state 1. The refrigerant is then compressed
adiabatically from state 1, where it is a two-phase liquidvapor mixture, to state 2, where
it is a saturated vapor. During this process, the temperature of the refrigerant increases
from TC to TH, and the pressure also increases. The refrigerant passes from the compres-
sor into the condenser, where it changes phase from saturated vapor to saturated liquid
as a result of heat transfer to the region at temperature TH. The temperature and pressure
remain constant in the process from state 2 to state 3. The refrigerant returns to the state
at the inlet of the evaporator by expanding adiabatically through a turbine. In this process,
from state 3 to state 4, the temperature decreases from TH to TC, and there is a decrease
in pressure.
Since the Carnot vapor refrigeration cycle is made up of internally reversible processes,
areas on the Ts diagram can be interpreted as heat transfers. Applying Eq. 6.51, area
1ab41 is the heat added to the refrigerant from the cold region per unit mass of refrig-
erant flowing. Area 2ab32 is the heat rejected from the refrigerant to the warm region
per unit mass of refrigerant flowing. The enclosed area 12341 is the net heat transfer
from the refrigerant. The net heat transfer from the refrigerant equals the net work done on
the refrigerant. The net work is the difference between the compressor work input and the
turbine work output.
The coefficient of performance of any refrigeration cycle is the ratio of the refrigera-
tion effect to the net work input required to achieve that effect. For the Carnot vapor refrig-
eration cycle shown in Fig. 10.1, the coefficient of performance is
#
Qinm
#
bmax # # # #
Wc m Wt m
area 1ab41 TC 1sa sb 2

area 12341 1TH TC 21sa sb 2
TC
(10.1)
TH TC
This equation, which corresponds to Eq. 5.9, represents the maximum theoretical coefficient
of performance of any refrigeration cycle operating between regions at TC and TH.
456 Chapter 10 Refrigeration and Heat Pump Systems
DEPARTURES FROM THE CARNOT CYCLE
Actual vapor refrigeration systems depart significantly from the Carnot cycle considered
above and have coefficients of performance lower than would be calculated from Eq. 10.1.
Three ways actual systems depart from the Carnot cycle are considered next.
One of the most significant departures is related to the heat transfers between the refrig-
erant and the two regions. In actual systems, these heat transfers are not accomplished
reversibly as presumed above. In particular, to achieve a rate of heat transfer sufficient
to maintain the temperature of the cold region at TC with a practical-sized evaporator
requires the temperature of the refrigerant in the evaporator, TC, to be several degrees
below TC. This is illustrated by the placement of the temperature TC on the Ts diagram
of Fig. 10.2. Similarly, to obtain a sufficient heat transfer rate from the refrigerant to the
warm region requires that the refrigerant temperature in the condenser, TH, be several
degrees above TH. This is illustrated by the placement of the temperature TH on the Ts
diagram of Fig. 10.2.
Maintaining the refrigerant temperatures in the heat exchangers at TC and TH rather
than at TC and TH, respectively, has the effect of reducing the coefficient of perform-
ance. This can be seen by expressing the coefficient of performance of the refrigeration
cycle designated by 12341 on Fig. 10.2 as
area 1ab41 T C
b (10.2)
area 12341 T H T C
Comparing the areas underlying the expressions for max and given above, we
conclude that the value of is less than max. This conclusion about the effect of
refrigerant temperature on the coefficient of performance also applies to other refrigera-
tion cycles considered in the chapter.
Even when the temperature differences between the refrigerant and warm and cold re-
gions are taken into consideration, there are other features that make the vapor refrigera-
tion cycle of Fig. 10.2 impractical as a prototype. Referring again to the figure, note
that the compression process from state 1 to state 2 occurs with the refrigerant as a
two-phase liquidvapor mixture. This is commonly referred to as wet compression. Wet
compression is normally avoided because the presence of liquid droplets in the flowing
liquidvapor mixture can damage the compressor. In actual systems, the compressor
handles vapor only. This is known as dry compression.
Another feature that makes the cycle of Fig. 10.2 impractical is the expansion
process from the saturated liquid state 3 to the low-quality, two-phase liquidvapor
mixture state 4. This expansion produces a relatively small amount of work com-
pared to the work input in the compression process. The work output achieved by
an actual turbine would be smaller yet because turbines operating under these
T Condenser
3 2 temperature, TH
TH
Temperature of warm
region, TH
Temperature of cold
region, TC
TC
4 1 Evaporator Figure 10.2 Comparison of the
temperature, TC
condenser and evaporator temperatures
b a s with those of the warm and cold regions.
10.2 Analyzing Vapor-Compression Refrigeration Systems 457

Qout
3 2
Condenser

Expansion Wc
Compressor
valve
Evaporator
4 1
Saturated or
superheated vapor
Figure 10.3 Components of a vapor-
Qin compression refrigeration system.
conditions typically have low efficiencies. Accordingly, the work output of the tur-
bine is normally sacrificed by substituting a simple throttling valve for the expansion
turbine, with consequent savings in initial and maintenance costs. The components of
the resulting cycle are illustrated in Fig. 10.3, where dry compression is presumed.
This cycle, known as the vapor-compression refrigeration cycle, is the subject of the
section to follow.

10.2 Analyzing Vapor-Compression
Refrigeration Systems
Vapor-compression refrigeration systems are the most common refrigeration systems in use vapor-compression
today. The object of this section is to introduce some important features of systems of this refrigeration
type and to illustrate how they are modeled thermodynamically.

Let us consider the steady-state operation of the vapor-compression system illustrated in
Fig. 10.3. Shown on the figure are the principal work and heat transfers, which are positive
in the directions of the arrows. Kinetic and potential energy changes are neglected in the
following analyses of the components. We begin with the evaporator, where the desired
refrigeration effect is achieved.
As the refrigerant passes through the evaporator, heat transfer from the refrigerated
space results in the vaporization of the refrigerant. For a control volume enclosing the
refrigerant side of the evaporator, the mass and energy rate balances reduce to give the
rate of heat transfer per unit mass of refrigerant flowing as
#
Qin
# h1 h4 (10.3)
m
# #
where m is the mass flow rate of the refrigerant. The heat transfer rate Qin is referred to
refrigeration capacity as the refrigeration capacity. In the SI unit system, the capacity is normally expressed
in kW. Another commonly used unit for the refrigeration capacity is the ton of refriger-
ton of refrigeration ation, which is equal to 211 kJ/min.
The refrigerant leaving the evaporator is compressed to a relatively high pressure and
temperature by the compressor. Assuming no heat transfer to or from the compressor,
the mass and energy rate balances for a control volume enclosing the compressor
give
#
Wc
# h2 h1 (10.4)
m
# #
where Wc m is the rate of power input per unit mass of refrigerant flowing.
Next, the refrigerant passes through the condenser, where the refrigerant condenses and
there is heat transfer from the refrigerant to the cooler surroundings. For a control vol-
ume enclosing the refrigerant side of the condenser, the rate of heat transfer from the
refrigerant per unit mass of refrigerant flowing is
#
Qout
# h2 h3 (10.5)
m
Finally, the refrigerant at state 3 enters the expansion valve and expands to the
evaporator pressure. This process is usually modeled as a throttling process for
which
h4 h3 (10.6)
The refrigerant pressure decreases in the irreversible adiabatic expansion, and there is an
accompanying increase in specific entropy. The refrigerant exits the valve at state 4 as a
two-phase liquidvapor mixture.
In the vapor-compression system, the net power input is equal to the compressor power,
since the expansion valve involves no power input or output. Using the quantities and ex-
pressions introduced above, the coefficient of performance of the vapor-compression refrig-
eration system of Fig. 10.3 is
#
Qin m
#
h1 h4
b # # (10.7)
Wc m h2 h1
Provided states 1 through 4 are fixed, Eqs. 10.3 through 10.7 can be used to evaluate the
principal work and heat transfers and the coefficient of performance of the vapor-
compression system shown in Fig. 10.3. Since these equations have been developed by
reducing mass and energy rate balances, they apply equally for actual performance when
irreversibilities are present in the evaporator, compressor, and condenser and for idealized
performance in the absence of such effects. Although irreversibilities in the evaporator,
compressor, and condenser can have a pronounced effect on overall performance, it is in-
structive to consider an idealized cycle in which they are assumed absent. Such a cycle
establishes an upper limit on the performance of the vapor-compression refrigeration cycle.
It is considered next.
10.2.2 Performance of Vapor-Compression Systems

IDEAL CYCLE. If irreversibilities within the evaporator and condenser are ignored, there are
no frictional pressure drops, and the refrigerant flows at constant pressure through the two
2s
1
4
Figure 10.4 Ts diagram of an ideal vapor-

s compression cycle.
heat exchangers. If compression occurs without irreversibilities, and stray heat transfer to the
surroundings is also ignored, the compression process is isentropic. With these considera-
tions, the vapor-compression refrigeration cycle labeled 12s341 on the Ts diagram of
Fig. 10.4 results. The cycle consists of the following series of processes:
Process 12s: Isentropic compression of the refrigerant from state 1 to the condenser pres-
sure at state 2s.
Process 2s3: Heat transfer from the refrigerant as it flows at constant pressure through the
condenser. The refrigerant exits as a liquid at state 3.
Process 34: Throttling process from state 3 to a two-phase liquidvapor mixture at 4.
Process 41: Heat transfer to the refrigerant as it flows at constant pressure through the
evaporator to complete the cycle.
All of the processes in the above cycle are internally reversible except for the throttling
process. Despite the inclusion of this irreversible process, the cycle is commonly referred to
as the ideal vapor-compression cycle. ideal vapor-
The following example illustrates the application of the first and second laws of thermo- compression cycle
dynamics along with property data to analyze an ideal vapor-compression cycle.
EXAMPLE 10.1 Ideal Vapor-Compression Refrigeration Cycle
Refrigerant 134a is the working fluid in an ideal vapor-compression refrigeration cycle that communicates thermally with a
cold region at 0C and a warm region at 26C. Saturated vapor enters the compressor at 0C and saturated liquid leaves the
condenser at 26C. The mass flow rate of the refrigerant is 0.08 kg/s. Determine (a) the compressor power, in kW, (b) the re-
frigeration capacity, in tons, (c) the coefficient of performance, and (d) the coefficient of performance of a Carnot refrigera-
tion cycle operating between warm and cold regions at 26 and 0C, respectively.
SOLUTION
Known: An ideal vapor-compression refrigeration cycle operates with Refrigerant 134a. The states of the refrigerant enter-
ing the compressor and leaving the condenser are specified, and the mass flow rate is given.
Find: Determine the compressor power, in kW, the refrigeration capacity, in tons, coefficient of performance, and the
coefficient of performance of a Carnot vapor refrigeration cycle operating between warm and cold regions at the specified
temperatures.
Warm region TH = 26C = 299 K

Qout
3 2s
Condenser
T
2s
Expansion Wc
Compressor
valve 3 Temperature of
26C a warm region
Temperature of
0C cold region
4 1
4 Evaporator 1
s

Qin
Cold region TC = 0C = 273 K
Figure E10.1
Assumptions:
1. Each component of the cycle is analyzed as a control volume at steady state. The control volumes are indicated by dashed
lines on the accompanying sketch.
2. Except for the expansion through the valve, which is a throttling process, all processes of the refrigerant are internally
reversible.
3. The compressor and expansion valve operate adiabatically.
5. Saturated vapor enters the compressor, and saturated liquid leaves the condenser.
Analysis: Let us begin by fixing each of the principal states located on the accompanying schematic and Ts diagrams.
At the inlet to the compressor, the refrigerant is a saturated vapor at 0C, so from Table A-10, h1 247.23 kJ/kg and s1
0.9190 kJ/kg # K.
The pressure at state 2s is the saturation pressure corresponding to 26C, or p2 6.853 bar. State 2s is fixed by p2 and the
fact that the specific entropy is constant for the adiabatic, internally reversible compression process. The refrigerant at state
2s is a superheated vapor with h2s 264.7 kJ/Kg.
State 3 is saturated liquid at 26C, so h3 85.75 kJ/kg. The expansion through the valve is a throttling process (assump-
tion 2), so h4 h3.
(a) The compressor work input is

Wc m 1h2s h1 2
# #
#
where m is the mass flow rate of refrigerant. Inserting values
Wc 10.08 kg/s21264.7 247.232 kJ/kg ` `

# 1 kW
1 kJ/s
1.4 kW
(b) The refrigeration capacity is the heat transfer rate to the refrigerant passing through the evaporator. This is given by
Qin m 1h1 h4 2
# #
10.08 kg/s2|60 s/min|1247.23 85.752 kJ/kg ` `

1 ton
211 kJ/min
3.67 ton
(c) The coefficient of performance is

#
Qin h1 h4 247.23 85.75
b # 9.24
Wc h2s h1 264.7 247.23
(d) For a Carnot vapor refrigeration cycle operating at TH 299 K and TC 273 K, the coefficient of performance deter-
mined from Eq. 10.1 is
TC
bmax
TH TC
10.5
The value for h2s can be obtained by double interpolation in Table A-12 or by using Interactive Thermodynamics: IT.
As expected, the ideal vapor-compression cycle has a lower coefficient of performance than a Cornot cycle operating
between the temperatures of the warm and cold regions. The smaller value can be attributed to the effects of the external
irreversibility associated with desuperheating the refrigerant in the condenser (Process 2sa on the Ts diagram) and the
internal irreversibility of the throttling process.
ACTUAL CYCLE. Figure 10.5 illustrates several features exhibited by actual vapor-
compression systems. As shown in the figure, the heat transfers between the refrigerant
and the warm and cold regions are not accomplished reversibly: the refrigerant tempera-
ture in the evaporator is less than the cold region temperature, TC, and the refrigerant
temperature in the condenser is greater than the warm region temperature, TH. Such irre-
versible heat transfers have a significant effect on performance. In particular, the coeffi-
cient of performance decreases as the average temperature of the refrigerant in the
evaporator decreases and as the average temperature of the refrigerant in the condenser
increases. Example 10.2 provides an illustration.
2
T 2s
3
Temperature of
warm region, TH
Temperature of
cold region, TC
1
4
Figure 10.5 Ts diagram of an
s actual vapor-compression cycle.
EXAMPLE 10.2 Effect of Irreversible Heat Transfer on Performance
Modify Example 10.1 to allow for temperature differences between the refrigerant and the warm and cold regions as follows.
Saturated vapor enters the compressor at 10C. Saturated liquid leaves the condenser at a pressure of 9 bar. Determine for
the modified vapor-compression refrigeration cycle (a) the compressor power, in kW, (b) the refrigeration capacity, in tons,
(c) the coefficient of performance. Compare results with those of Example 10.1.
SOLUTION
Known: An ideal vapor-compression refrigeration cycle operates with Refrigerant 134a as the working fluid. The evapora-
tor temperature and condenser pressure are specified, and the mass flow rate is given.
Find: Determine the compressor power, in kW, the refrigeration capacity, in tons, and the coefficient of performance. Com-
pare results with those of Example 10.1.
Assumptions:
T
2s
1. Each component of the cycle is analyzed as a control volume at steady
state. The control volumes are indicated by dashed lines on the sketch ac-
9 bar companying Example 10.1.
3
26C 2. Except for the process through the expansion valve, which is a throt-
tling process, all processes of the refrigerant are internally reversible.
3. The compressor and expansion valve operate adiabatically.
0C
10C 4. Kinetic and potential energy effects are negligible.
4 1
5. Saturated vapor enters the compressor, and saturated liquid exits the
condenser.
s
Figure E10.2
Analysis: Let us begin by fixing each of the principal sates located on the accompanying Ts diagram. Starting at the
inlet to the compressor, the refrigerant is a saturated vapor at 10C, so from Table A-10, h1 241.35 kJ/kg and s1
0.9253 kJ/kg # K.
The superheated vapor at state 2s is fixed by p2 9 bar and the fact that the specific entropy is constant for the adiabatic,
internally reversible compression process. Interpolating in Table A-12 gives h2s 272.39 kJ/kg.
State 3 is a saturated liquid at 9 bar, so h3 99.56 kJ/kg. The expansion through the valve is a throttling process; thus,
h4 h3.
(a) The compressor power input is

Wc m 1h2s h1 2
# #
#
where m is the mass flow rate of refrigerant. Inserting values
Wc 10.08 kg/s21272.39 241.352 kJ/kg ` `

# 1 kW
1 kJ/s
2.48 kW
(b) The refrigeration capacity is
Qin m 1h1 h4 2
# #
10.08 kg/s2 060 s/min 0 1241.35 99.562 kJ/kg ` `

1 ton
211 kJ/min
3.23 ton
(c) The coefficient or performance is

#
Qin h1 h4 241.35 99.56
b # 4.57
Wc h2s h1 272.39 241.35
Comparing the results of the present example with those of Example 10.1, we see that the power input required by the
compressor is greater in the present case. Furthermore, the refrigeration capacity and coefficient of performance are smaller
in this example than in Example 10.1. This illustrates the considerable influence on performance of irreversible heat transfer
between the refrigerant and the cold and warm regions.
Referring again to Fig. 10.5, we can identify another key feature of actual vapor-
compression system performance. This is the effect of irreversibilities during compression,
suggested by the use of a dashed line for the compression process from state 1 to state 2.
The dashed line is drawn to show the increase in specific entropy that would accompany an
adiabatic irreversible compression. Comparing cycle 12341 with cycle 12s341, the
refrigeration capacity would be the same for each, but the work input would be greater in
the case of irreversible compression than in the ideal cycle. Accordingly, the coefficient of
performance of cycle 12341 is less than that of cycle 12s341. The effect of irre-
versible compression can be accounted for by using the isentropic compressor efficiency,
which for states designated as in Fig. 10.5 is given by
1Wc m2 s
# #
h2s h1
hc # #
1Wc m2 h2 h1
Additional departures from ideality stem from frictional effects that result in pressure drops
as the refrigerant flows through the evaporator, condenser, and piping connecting the vari-
ous components. These pressure drops are not shown on the Ts diagram of Fig. 10.5 and
are ignored in subsequent discussions for simplicity.
Finally, two additional features exhibited by actual vapor-compression systems are shown
in Fig. 10.5. One is the superheated vapor condition at the evaporator exit (state 1), which
differs from the saturated vapor condition shown in Fig. 10.4. Another is the subcooling of
the condenser exit state (state 3), which differs from the saturated liquid condition shown in
Fig. 10.4.
Example 10.3 illustrates the effects of irreversible compression and condenser exit sub-
cooling on the performance of the vapor-compression refrigeration system.
EXAMPLE 10.3 Actual Vapor-Compression Refrigeration Cycle
Reconsider the vapor-compression refrigeration cycle of Example 10.2, but include in the analysis that the compressor has an
efficiency of 80%. Also, let the temperature of the liquid leaving the condenser be 30C. Determine for the modified cycle
(a) the compressor power, in kW, (b) the refrigeration capacity, in tons, (c) the coefficient of performance, and (d) the rates
of exergy destruction within the compressor and expansion valve, in kW, for T0 299 K (26C).
SOLUTION
Known: A vapor-compression refrigeration cycle has a compressor efficiency of 80%.
Find: Determine the compressor power, in kW, the refrigeration capacity, in tons, the coefficient of performance, and the
rates of exergy destruction within the compressor and expansion valve, in kW.
Assumptions:
T
p2 = 9 bar 1. Each component of the cycle is analyzed as a control vol-
2
2s
ume at steady state.
2. There are no pressure drops through the evaporator and
condenser.
3. The compressor operates adiabatically with an efficiency of
3 80%. The expansion through the valve is a throttling process.
30C
T0 = 26C = 299 K 4. Kinetic and potential energy effects are negligible.
5. Saturated vapor at 10C enters the compressor, and liquid
10C at 30C leaves the condenser.
4 1
6. The environment temperature for calculating exergy is T0
299 K (26C).
s
Figure E10.3
Analysis: Let us begin by fixing the principal states. State 1 is the same as in Example 10.2, so h1 241.35 kJ/kg and s1
0.9253 kJ/kg # K.
Owing to the presence of irreversibilities during the adiabatic compression process, there is an increase in specific entropy
from compressor inlet to exit. The state at the compressor exit, state 2, can be fixed using the compressor efficiency
1Wc m2 s 1h2s h1 2
# #
hc # #
Wc m 1h2 h1 2
where h2s is the specific enthalpy at state 2s, as indicated on the accompanying Ts diagram. From the solution to Example 10.2,
h2s 272.39 kJ/kg. Solving for h2 and inserting known values
h2s h1 1272.39 241.352
h2
h1
241.35 280.15 kJ/kg
hc 10.802
State 2 is fixed by the value of specific enthalpy h2 and the pressure, p2 9 bar. Interpolating in Table A-12, the specific en-
tropy is s2 0.9497 kJ/kg # K.
The state at the condenser exit, state 3, is in the liquid region. The specific enthalpy is approximated using Eq. 3.14, to-
gether with saturated liquid data at 30C, as follows: h3 hf 91.49 kJ/kg. Similarly, with Eq. 6.7, s3 sf 0.3396 kJ/kg # K.
The expansion through the valve is a throttling process; thus, h4 h3. The quality and specific entropy at state 4 are,
respectively
h4 hf4 91.49 36.97
x4 0.2667
hg4 hf4 204.39
and
s4 sf4
x4 1sg4 sf4 2
0.1486
10.2667210.9253 0.14862 0.3557 kJ/kg # K
(a) The compressor power is
Wc m 1h2 h1 2
# #
10.08 kg/s2 1280.15 241.352 kJ/kg ` ` 3.1 kW

1 kW
1 kJ/s
Qin m 1h1 h4 2
# #
10.08 kg/s2 0 60 s/min 0 1241.35 91.492 kJ/kg ` `

1 ton
211 kJ/min
3.41 ton
10.3 Refrigerant Properties 465

1h1 h4 2 1241.35 91.492
b
1h2 h1 2

1280.15 241.352
3.86
(d) The rates of exergy destruction

# in the compressor and expansion valve can be found by reducing the exergy rate balance
# #
or using the relationship Ed T0scv, where scv is the rate of entropy production from an entropy rate balance. With either ap-
proach, the rates or exergy destruction for the compressor and valve are, respectively
1Ed 2 c mT0 1s2 s1 2 1Ed 2 valve mT0 1s4 s3 2
# # # #
and
Substituting values
1Ed 2 c a0.08 b 1299 K210.9497 0.92532 # ` ` 0.58 kW

# kg kJ 1 kW
s kg K 1 kJ/s
and
1Ed 2 valve 10.0821299210.3557 0.33962 0.39 kW
#
Irreversibilities in the compressor result in an increased compressor power requirement compared to the isentropic com-
pression of Example 10.2. As a consequence, the coefficient of performance is lower.
The exergy destruction rates calculated in part (d) measure the effect of irreversibilities as the refrigerant flows through
the compressor and valve. The percentages of the power input (exergy input) to the compressor destroyed in the com-
pressor and valve are 18.7 and 12.6%, respectively.

10.3 Refrigerant Properties
From about 1940 to the early 1990s, the most common class of refrigerants used in vapor-
compression refrigeration systems was the chlorine-containing CFCs (chlorofluorocarbons).
Refrigerant 12 (CCl2F2) is one of these. Owing to concern about the effects of chlorine in
refrigerants on the earths protective ozone layer, international agreements have been imple-
mented to phase out the use of CFCs. Classes of refrigerants containing various amounts of
hydrogen in place of chlorine atoms have been developed that have less potential to deplete
atmospheric ozone than do more fully chlorinated ones, such as Refrigerant 12. One such
class, the HFCs, contain no chlorine. Refrigerant 134a (CF3CH2F) is the HFC considered by
many to be an environmentally acceptable substitute for Refrigerant 12, and Refrigerant 134a
has replaced Refrigerant 12 in many applications.
Refrigerant 22 (CHClF2) is in the class called HCFCs that contains some hydrogen in
place of the chlorine atoms. Although Refrigerant 22 and other HCFCs are widely used today,
discussions are under way that will likely result in phasing out their use at some time in the
future. Ammonia (NH3), which was widely used in the early development of vapor-
compression refrigeration, is again receiving some interest as an alternative to the CFCs
because it contains no chlorine. Ammonia is also important in the absorption refrigeration
systems discussed in Section 10.5. Hydrocarbons such as propane (C3H8) and methane (CH4)
are also under investigation for use as refrigerants.
Thermodynamic property data for ammonia, propane, and Refrigerants 22 and 134a are
included in the appendix tables. These data allow us to study refrigeration and heat pump
systems in common use and to investigate some of the effects on refrigeration cycles of us-
ing alternative working fluids.
A thermodynamic property diagram widely used in the refrigeration field is the
pressureenthalpy or ph diagram. Figure 10.6 shows the main features of such a property ph diagram

New Materials May Revive better thermoelectric
materials by alter-
Thermoelectric Cooling nately depositing 1- to
You can buy a thermoelectric cooler powered from the ciga- 4-nanometer films of
rette lighter outlet of your car. The same technology is used in different materials on
space applications. These simple coolers have no moving parts the same base. These
and use no ozone-depleting refrigerants. Despite such advan- nanoengineered ma-
tages, thermoelectric cooling has found only specialized ap- terials hold promise
plication because of low coefficients of performance that dont for cooling electronic
allow them to compete with commonplace vapor-compression circuits, and perhaps
systems. However, new materials and novel production meth- even for improved
ods involving engineering at a nanometer level may make thermoelectric coolers.
thermoelectrics more competitive, material scientists say. New materials are
The basis of thermoelectric cooling is two dissimilar semi- closing the perform-
conductors coming together in specially designed electric ance gap, but much re-
circuits. Effective materials for thermoelectric cooling must mains to be done be-
have low thermal conductivity and high electrical conductiv- fore thermoelectric refrigerators are commonplace. Still, a vast
ity, a rare combination in nature. One laboratory has produced market would be served if researchers succeed.
diagram. The principal states of the vapor-compression cycles of Fig. 10.5 are located on this
ph diagram. It is left as an exercise to sketch the cycles of Examples 10.1, 10.2, and 10.3
on ph diagrams. Property tables and ph diagrams for many refrigerants are given in hand-
books dealing with refrigeration.
SELECTING REFRIGERANTS. The temperatures of the refrigerant in the evaporator and

condenser are governed by the temperatures of the cold and warm regions, respectively, with
which the system interacts thermally. This, in turn, determines the operating pressures in
the evaporator and condenser. Consequently, the selection of a refrigerant is based partly
on the suitability of its pressuretemperature relationship in the range of the particular ap-
plication. It is generally desirable to avoid excessively low pressures in the evaporator and
excessively high pressures in the condenser. Other considerations in refrigerant selection in-
clude chemical stability, toxicity, corrosiveness, and cost. The type of compressor also af-
fects the choice of refrigerant. Centrifugal compressors are best suited for low evaporator
pressures and refrigerants with large specific volumes at low pressure. Reciprocating com-
pressors perform better over large pressure ranges and are better able to handle low specific
volume refrigerants.
s
nt
p
ta
ns
Co
Condenser
3 pressure 2s 2
Evaporator
pressure
Figure 10.6 Principal features of the
4 1
Constant T pressureenthalpy diagram for a typical
refrigerant, with vapor-compression cycles
h superimposed.
10.4 Cascade and Multistage Vapor-Compression Systems 467

10.4 Cascade and Multistage
Vapor-Compression Systems
Variations of the basic vapor-compression refrigeration cycle are used to improve perform-
ance or for special applications. Two variations are presented in this section. The first is a
combined cycle arrangement in which refrigeration at relatively low temperature is achieved
through a series of vapor-compression systems, with each normally employing a different re-
frigerant. In the second variation, the work of compression is reduced through multistage
compression with intercooling between the stages. These variations are analogous to power
cycle modifications considered in Chaps. 8 and 9.
10.4.1 Cascade Cycles

Combined cycle arrangements for refrigeration are called cascade cycles. In Fig. 10.7 a cas-
cade cycle is shown in which two vapor-compression refrigeration cycles, labeled A and B,
are arranged in series with a counterflow heat exchanger linking them. In the intermediate
heat exchanger, the energy rejected during condensation of the refrigerant in the lower-
temperature cycle A is used to evaporate the refrigerant in the higher-temperature cycle B.
The desired refrigeration effect occurs in the low-temperature evaporator, and heat rejection
from the overall cycle occurs in the high-temperature condenser. The coefficient of
performance is the ratio of the refrigeration effect to the total work input
#
Qin
b # #
WcA
WcB

Qout
High-temperature
condenser
7 6
Expansion

valve WcB
Compressor
Cycle B
8 Intermediate 5
heat exchanger
3 2

Cycle A WcA
Compressor
Expansion
valve
4 1
Low-temperature
evaporator
Figure 10.7 Example of a cascade

Qin vapor-compression refrigeration cycle.
The mass flow rates in cycles A and B normally would be different. However, the mass flow
rates are related by mass and energy rate balances on the interconnecting counterflow heat ex-
changer serving as the condenser for cycle A and the evaporator for cycle B. Although only two
cycles are shown in Fig. 10.7, cascade cycles may employ three or more individual cycles.
A significant feature of the cascade system illustrated in Fig. 10.7 is that the refrigerants
in the two or more stages can be selected to have reasonable evaporator and condenser pres-
sures in the two or more temperature ranges. In a double cascade system, a refrigerant would
be selected for cycle A that has a saturation pressuretemperature relationship that allows re-
frigeration at a relatively low temperature without excessively low evaporator pressures. The
refrigerant for cycle B would have saturation characteristics that permit condensation at the
required temperature without excessively high condenser pressures.
10.4.2 Multistage Compression with Intercooling

The advantages of multistage compression with intercooling between stages have been cited
in Sec. 9.8, dealing with gas power systems. Intercooling is achieved in gas power systems
by heat transfer to the lower-temperature surroundings. In refrigeration systems, the refrig-
erant temperature is below that of the surroundings for much of the cycle, so other means
must be employed to accomplish intercooling and achieve the attendant savings in the required
compressor work input. One arrangement for two-stage compression using the refrigerant
itself for intercooling is shown in Fig. 10.8. The principal states of the refrigerant for an ideal
cycle are shown on the accompanying Ts diagram.

Qout
(1)
Condenser
5 4
Expansion
valve
Wc2
Compressor
(1)
6 3 (1)
9 T a
Direct contact
(x) heat exchanger
Flash
chamber 4
2 (1 x) 5
(1 x) 2
7
Wc1 7
Compressor 3
6 9
Expansion
valve
8 1
8 1
Evaporator
(1 x)
s

Qin
Figure 10.8 Refrigeration cycle with two stages of compression and flash
intercooling.
10.5 Absorption Refrigeration 469
Intercooling is accomplished in this cycle by means of a direct contact heat exchanger.

Relatively low-temperature saturated vapor enters the heat exchanger at state 9, where it
mixes with higher-temperature refrigerant leaving the first compression stage at state 2. A
single mixed stream exits the heat exchanger at an intermediate temperature at state 3 and is
compressed in the second compressor stage to the condenser pressure at state 4. Less work
is required per unit of mass flow for compression from 1 to 2 followed by compression from
3 to 4 than for a single stage of compression 12a. Since the refrigerant temperature en-
tering the condenser at state 4 is lower than for a single stage of compression in which the
refrigerant would enter the condenser at state a, the external irreversibility associated with
heat transfer in the condenser is also reduced.
A central role is played in the cycle of Fig. 10.8 by a liquidvapor separator, called a flash flash chamber
chamber. Refrigerant exiting the condenser at state 5 expands through a valve and enters the
flash chamber at state 6 as a two-phase liquidvapor mixture with quality x. In the flash
chamber, the liquid and vapor components separate into two streams. Saturated vapor exit-
ing the flash chamber enters the heat exchanger at state 9, where intercooling is achieved as
discussed above. Saturated liquid exiting the flash chamber at state 7 expands through a sec-
ond valve into the evaporator. On the basis of a unit of mass flowing through the condenser,
the fraction of the vapor formed in the flash chamber equals the quality x of the refrigerant
at state 6. The fraction of the liquid formed is then (1 x). The fractions of the total flow
at various locations are shown in parentheses on Fig. 10.8.

10.5 Absorption Refrigeration
Absorption refrigeration cycles are the subject of this section. These cycles have some fea- absorption refrigeration
tures in common with the vapor-compression cycles considered previously but differ in two
important respects:
One is the nature of the compression process. Instead of compressing a vapor between
the evaporator and the condenser, the refrigerant of an absorption system is absorbed
by a secondary substance, called an absorbent, to form a liquid solution. The liquid
solution is then pumped to the higher pressure. Because the average specific volume of
the liquid solution is much less than that of the refrigerant vapor, significantly less work
is required (see the discussion of Eq. 6.53b in Sec. 6.9). Accordingly, absorption
refrigeration systems have the advantage of relatively small work input compared
to vapor-compression systems.
The other main difference between absorption and vapor-compression systems is that
some means must be introduced in absorption systems to retrieve the refrigerant vapor
from the liquid solution before the refrigerant enters the condenser. This involves heat
transfer from a relatively high-temperature source. Steam or waste heat that otherwise
would be discharged to the surroundings without use is particularly economical for this
purpose. Natural gas or some other fuel can be burned to provide the heat source, and
there have been practical applications of absorption refrigeration using alternative
energy sources such as solar and geothermal energy.
The principal components of an absorption refrigeration system are shown schematically
in Fig. 10.9. In this case, ammonia is the refrigerant and water is the absorbent. Ammonia
circulates through the condenser, expansion valve, and evaporator as in a vapor-compression
system. However, the compressor is replaced by the absorber, pump, generator, and valve
shown on the right side of the diagram.
In the absorber, ammonia vapor coming from the evaporator at state 1 is absorbed by absorber
liquid water. The formation of this liquid solution is exothermic. Since the amount of
High-
QG
temperature
Qout source
Generator
Condenser
2
Strong solution
b
Weak solution
c
Expansion
valve Valve
Pump
Absorber
Wp
4
Evaporator
1
a
Qin
Figure 10.9 Simple
Refrigerated Cooling ammoniawater absorption
region water refrigeration system.
ammonia that can be dissolved in water increases as the solution temperature decreases,
cooling water is circulated around the absorber to remove the energy released as ammo-
nia goes into solution and maintain the temperature in the absorber as low as possible.
The strong ammoniawater solution leaves the absorber at point a and enters the pump,
where its pressure is increased to that of the generator.
generator In the generator, heat transfer from a high-temperature source drives ammonia vapor
out of the solution (an endothermic process), leaving a weak ammoniawater solution in
the generator. The vapor liberated passes to the condenser at state 2, and the remaining
weak solution at c flows back to the absorber through a valve. The only work input is
the power required to operate the pump, and this is small in comparison to the work
that would be required to compress refrigerant vapor between the same pressure levels.
However, costs associated with the heat source and extra equipment not required by
vapor-compressor systems can cancel the advantage of a smaller work input.
Ammoniawater systems normally employ several modifications of the simple absorption
cycle considered above. Two common modifications are illustrated in Fig. 10.10. In this cy-
cle, a heat exchanger is included between the generator and the absorber that allows the
strong waterammonia solution entering the generator to be preheated by the weak solution
returning# from the generator to the absorber, thereby reducing the heat transfer to the gen-
rectifier erator, QG. The other modification shown on the figure is the rectifier placed between the
generator and the condenser. The function of the rectifier is to remove any traces of water
from the refrigerant before it enters the condenser. This eliminates the possibility of ice
formation in the expansion valve and the evaporator.
Another type of absorption system uses lithium bromide as the absorbent and water as the
refrigerant. The basic principle of operation is the same as for ammoniawater systems. To
achieve refrigeration at lower temperatures than are possible with water as the refrigerant, a
lithium bromidewater absorption system may be combined with another cycle using a re-
frigerant with good low-temperature characteristics, such as ammonia, to form a cascade
refrigeration system.
10.6 Heat Pump Systems 471

Qout
2
Condenser
3 Rectifier

QG
Generator
Expansion
valve
Heat
exchanger
4
Pump
Valve
Wp
1
Evaporator Absorber
Figure 10.10 Modified ammoniawater

Qin Qcw absorption system.

10.6 Heat Pump Systems
The objective of a heat pump is to maintain the temperature within a dwelling or other building
above the temperature of the surroundings or to provide a heat transfer for certain industrial
processes that occur at elevated temperatures. Heat pump systems have many features in
common with the refrigeration systems considered thus far and may be of the vapor-
compression or absorption type. Vapor-compression heat pumps are well suited for space
heating applications and are commonly used for this purpose. Absorption heat pumps
have been developed for industrial applications and are also increasingly being used for space
heating. To introduce some aspects of heat pump operation, let us begin by considering
the Carnot heat pump cycle.
CARNOT HEAT PUMP CYCLE
By simply changing our viewpoint, we can regard the cycle shown in Fig. # 10.1 as a heat
pump. The objective of the cycle now, however, is to deliver the heat transfer Qout to the warm
region, which is the space to be heated. At steady state, the rate at which energy is supplied
to the warm region by # heat transfer is the sum of the energy supplied to# the working fluid
from the cold region, Qin, and the net rate of work input to the cycle, Wnet. That is
# # #
Qout Qin
Wnet (10.8)
The coefficient of performance of any heat pump cycle is defined as the ratio of the heat-
ing effect to the net work required to achieve that effect. For the Carnot heat pump cycle of
Fig. 10.1
#
Qout m
#
gmax # # # #
Wc m Wt m
area 2ab32

area 12341
TH 1sa sb 2 TH

1TH TC 21sa sb 2
(10.9)
TH TC
This equation, which corresponds to Eq. 5.10, represents the maximum theoretical coefficient
of performance for any heat pump cycle operation between two regions at temperatures TC
and TH. Actual heat pump systems have coefficients of performance that are lower than would
be calculated from Eq. 10.9.
A study of Eq. 10.9 shows that as the temperature TC of the cold region decreases, the co-
efficient of performance of the Carnot heat pump decreases. This trait is also exhibited by ac-
tual heat pump systems and suggests why heat pumps in which the role of the cold region is
played by the local atmosphere (air-source heat pumps) normally require backup systems to
provide heating on days when the ambient temperature becomes very low. If sources such as
well water or the ground itself are used, relatively high coefficients of performance can be
achieve despite low ambient air temperatures, and backup systems may not be required.
VAPOR-COMPRESSION HEAT PUMPS
Actual heat pump systems depart significantly from the Carnot cycle model. Most systems
in common use today are of the vapor-compression type. The method of analysis of vapor-
compression heat pumps is the same as that of vapor-compression refrigeration cycles con-
sidered previously. Also, the previous discussions concerning the departure of actual systems
from ideality apply for vapor-compression heat pump systems as for vapor-compression
refrigeration cycles.
vapor-compression As illustrated by Fig. 10.11, a typical vapor-compression heat pump for space heating
heat pump has the same basic components as the vapor-compression refrigeration system: compressor,
Inside Outside
air air
Condenser Evaporator
3 4
Expansion
Qout Qin
valve Compressor

Wc
2 1
Figure 10.11 Air-source vapor-compression heat pump system.

10.7 Gas Refrigeration Systems 473
Expansion
valve
Inside Outside
heat exchanger heat exchanger
Reversing
valve
Heating mode
Cooling mode

Compressor Wc
Figure 10.12 Example of an air-to-air
reversing heat pump.
condenser, expansion valve, and # evaporator. The objective of the system

# is different, how-
ever. In a heat pump system, Qin comes from the surroundings, and Qout is directed to the
dwelling as the desired effect. A net work input is required to accomplish this effect.
The coefficient of performance of a simple vapor-compression heat pump with states as
designated on Fig. 10.11 is
#
Qout m
#
h2 h3
g # # (10.10)
Wc m h 2 h1
The value of can never be less than unity.

Many possible sources are available for heat transfer to the refrigerant passing through
the evaporator. These include the outside air, the ground, and lake, river, or well water. Liq-
uid circulated through a solar collector and stored in an insulated tank also can be used as a
source for a heat pump. Industrial heat pumps employ waste heat or warm liquid or gas
streams as the low-temperature source and are capable of achieving relatively high condenser
temperatures.
In the most common type of vapor-compression heat pump for space heating, the evapo-
rator communicates thermally with the outside air. Such air-source heat pumps also can be air-source heat pump
used to provide cooling in the summer with the use of a reversing valve, as illustrated in
Fig. 10.12. The solid lines show the flow path of the refrigerant in the heating mode, as de-
scribed previously. To use the same components as an air conditioner, the valve is actuated,
and the refrigerant follows the path indicated by the dashed line. In the cooling mode, the
outside heat exchanger becomes the condenser, and the inside heat exchanger becomes the
evaporator. Although heat pumps can be more costly to install and operate than other direct
heating systems, they can be competitive when the potential for dual use is considered.

10.7 Gas Refrigeration Systems
All refrigeration systems considered thus far involve changes in phase. Let us now turn to
gas refrigeration systems in which the working fluid remains a gas throughout. Gas refrig- gas refrigeration systems
eration systems have a number of important applications. They are used to achieve very low
temperatures for the liquefaction of air and other gases and for other specialized applications
Warm region
at TH
2
Qout T
2s
Heat exchanger Constant pressure
3 2
3
Wcycle =
TH
Wc Wt
Turbine Compressor TC
1
Constant pressure
Heat exchanger 4s 4
4 1
s
(b)
Qin
Cold region
at TC
(a)
Figure 10.13 Brayton refrigeration cycle.
such as aircraft cabin cooling. The Brayton refrigeration cycle illustrates an important type
of gas refrigeration system.
BRAYTON REFRIGERATION CYCLE
Brayton refrigeration The Brayton refrigeration cycle is the reverse of the closed Brayton power cycle introduced
cycle in Sec. 9.6. A schematic of the reversed Brayton cycle is provided in Fig. 10.13a. The re-
frigerant gas, which may be air, enters the compressor at state 1, where the temperature is
somewhat below the temperature of the cold region, TC, and is compressed to state 2. The
gas is then cooled to state 3, where the gas temperature approaches the temperature of the
warm region, TH. Next, the gas is expanded to state 4, where the temperature, T4, is well be-
low that of the cold region. Refrigeration is achieved through heat transfer from the cold re-
gion to the gas as it passes from state 4 to state 1, completing the cycle. The Ts diagram in
Fig. 10.13b shows an ideal Brayton refrigeration cycle, denoted by 12s34s1, in which
all processes are assumed to be internally reversible and the processes in the turbine and
compressor are adiabatic. Also shown is the cycle 12341, which suggests the effects of
irreversibilities during adiabatic compression and expansion. Frictional pressure drops have
been ignored.
CYCLE ANALYSIS. The method of analysis of the Brayton refrigeration cycle is similar to
that of the Brayton power cycle. Thus, at steady state the work of the compressor and the
turbine per unit of mass flow are, respectively
# #
Wc Wt
# h2 h1 and # h3 h4
m m
In obtaining these expressions, heat transfer with the surroundings and changes in kinetic and
potential energy have been ignored. In contrast to the vapor-compression cycle of Fig. 10.2,
the work developed by the turbine of a Brayton refrigeration cycle is significant relative to
the compressor work input.
The heat transfer from the cold region to the refrigerant gas circulating through the low-
pressure heat exchanger, the refrigeration effect, is
#
Qin
# h1 h4
m
The coefficient of performance is the ratio of the refrigeration effect to the net work input:
1h1 h4 2
#
Qinm
#
b # # # #
1h 1 2 1h3 h4 2
(10.11)
Wc m Wt m 2 h
In the next example, we illustrate the analysis of an ideal Brayton refrigeration cycle.
EXAMPLE 10.4 Ideal Brayton Refrigeration Cycle
Air enters the compressor of an ideal Brayton refrigeration cycle at 1 bar, 270K, with a volumetric flow rate of 1.4 m3/s. If
the compressor pressure ratio is 3 and the turbine inlet temperature is 300K, determine (a) the net power input, in kW,
(b) the refrigeration capacity, in kW, (c) the coefficient of performance.
SOLUTION
Known: An ideal Brayton refrigeration cycle operates with air. Compressor inlet conditions, the turbine inlet temperature,
and the compressor pressure ratio are given.
Find: Determine the net power input, in kW, the refrigeration capacity, in kW, and the coefficient of performance.

Qout
T3 =
300K
Heat exchanger T 2s
3 2s
p = 3 bars
Wcycle
Turbine Compressor T3 =
300K
3
1
T1 =
p = 1 bar 270K
Heat exchanger
4s 1
(AV)1 = 1.4 m3/s
T1 = 270K
Qin p1 = 1 bar 4s
s
Figure E10.4
Assumptions:
1. Each component of the cycle is analyzed as a control volume at steady state. The control volumes are indicated by dashed
lines on the accompanying sketch.
3. There are no pressure drops through the heat exchangers.

Analysis: The analysis begins by determining the specific enthalpy at each numbered state of the cycle. At state 1, the tem-
perature is 270 K. From Table A-22, h1 270.11 kJ/kg, pr1 0.9590. Since the compressor process is isentropic, h2s can be
determined by first evaluating pr at state 2s. That is
p 13210.95902 2.877
p2
pr2
p1 r1
Then, interpolating in Table A-22, we get h2s 370.1 kJ/kg.
The temperature at state 3 is given as T3 300 K. From Table A-22, h3 300.19 kJ/kg, pr3 1.3860. The specific en-
thalpy at state 4s is found by using the isentropic relation
11.38602 1132 0.462

p4
pr4 pr3
p3
Interpolating in Table A-22, we obtain h4s 219.0 kJ/kg.
(a) The net power input is
Wcycle m 3 1h2s h1 2 1h3 h4s 2 4
# #
#
This requires the mass flow rate m, which can be determined from the volumetric flow rate and the specific volume at the
compressor inlet:
# 1AV2 1
m
v1
Since v1 (RM )T1p1
# 1AV2 1p1
m
1RM2T1
11.4 m3/s2 11 bar2 105 N/m2
a ba 3 # b
1 kJ

a b 1270 K2
8.314 kJ 1 bar 10 N m
28.97
1.807 kg/s
Finally
Wcycle 11.807 kg/s2 3 1370.1 270.112 1300.19 219.02 4 kJ/kg a b

# 1 kW
1 kJ/s
33.97 kW
Qin m 1h1 h4s 2
# #
11.807 kg/s21270.11 2192 kJ/kg a b

1 kW
1 kJ/s
92.36 kW
#
Qin 92.36
b # 2.72
Wcycle 33.97
Irreversibilities within the compressor and turbine serve to decrease the coefficient of per-
formance significantly from that of the corresponding ideal cycle because the compressor
work requirement is increased and the turbine work output is decreased. This is illustrated
in the example to follow.
EXAMPLE 10.5 Brayton Refrigeration Cycle with Irreversibilities
Reconsider Example 10.4, but include in the analysis that the compressor and turbine each have an isentropic efficiency of
80%. Determine for the modified cycle (a) the net power input, in kW, (b) the refrigeration capacity, in kW, (c) the coefficient
of performance, and interpret its value.
SOLUTION
Known: A Brayton refrigeration cycle operates with air. Compressor inlet conditions, the turbine inlet temperature, and the
compressor pressure ration are given. The compressor and turbine each have an efficiency of 80%.
Find: Determine the net power input and the refrigeration capacity, each in kW. Also, determine the coefficient of per-
formance and interpret its value.
T 2
2s
Assumptions:
p = 3 bars
1. Each component of the cycle is analyzed as a control volume at
steady state.
3 2. The compressor and turbine are adiabatic.
T3 = 300 K
3. There are no pressure drops through the heat exchangers.
T1 = 270 K
p = 1 bar
4
4s
s
Figure E10.5
Analysis:
(a) The power input to the compressor is evaluated using the isentropic compressor efficiency, c. That is
1Wc m2 s
# # #
Wc
#
m hc
# #
The value of the work per unit mass for the isentropic compression, (Wcm)s, is determined with data from the solution in
Example 10.4 as 99.99 kJ/kg. The actual power required is then
m 1Wcm2 s 11.807 kg/s2199.99 kJ/kg2
# # #
#
Wc
hc 10.82
225.9 kW
# The turbine
# # power output is determined in a similar manner, using # # the turbine isentropic efficiency t. Thus,
Wt m ht(Wt m)s. Using data form the solution to Example 10.4 gives (Wt m)s 81.19 kJ /kg. The actual turbine work is
#
then
Wt m ht 1Wt m2 s 11.807 kg/s210.82181.19 kJ/kg2
# # # #
117.4 kW
The net power input to the cycle is
#
Wcycle 225.9 117.4 108.5 kW
(b) The specific enthalpy

# at the turbine exit, h4, is required
# to# evaluate the refrigeration capacity. This enthalpy can be deter-
mined by solving Wt m(h3 h4) to obtain h4 h3 Wt m. Inserting known values
#
h4 300.19 a b 235.2 kJ/kg

117.4
1.807
The refrigeration capacity is then
Qin m 1h1 h4 2 11.80721270.11 235.22 63.08 kW
# #

#
Qin 63.08
b # 0.581
Wcycle 108.5
The value of the coefficient of performance in this case is less than unity. This means that the refrigeration effect is smaller
than the net work required to achieve it. Additionally, note that irreversibilities in the compressor and turbine have a significant
effect on the performance of gas refrigeration systems. This is brought out by comparing the results of the present example
with those of Example 10.4. Irreversibilities result in an increase in the work of compression and a reduction in the work
output of the turbine. The refrigeration capacity is also reduced. The overall effect is that the coefficient of performance is
decreased significantly.
ADDITIONAL GAS REFRIGERATION APPLICATIONS
To obtain even moderate refrigeration capacities with the Brayton refrigeration cycle, equip-
ment capable of achieving relatively high pressures and volumetric flow rates is needed. For
most applications involving air conditioning and for ordinary refrigeration processes, vapor-
compression systems can be built more cheaply and can operate with higher coefficients of
performance than gas refrigeration systems. With suitable modifications, however, gas re-
frigeration systems can be used to achieve temperatures of about 150C, which are well
below the temperatures normally obtained with vapor systems.
Figure 10.14 shows the schematic and Ts diagram of an ideal Brayton cycle modified
by the introduction of a regenerative heat exchanger. The heat exchanger allows the air en-
tering the turbine at state 3 to be cooled below the warm region temperature TH. In the sub-
sequent expansion through the turbine, the air achieves a much lower temperature at state 4
than would have been possible without the regenerative heat exchanger. Accordingly, the
refrigeration effect, achieved from state 4 to state b, occurs at a correspondingly lower average
temperature.
T
2
Qin Heat
exchanger
b
1 a
a TH
4 3
1
3 2
Qout
b

Wcycle
4
Turbine Compressor s
Figure 10.14 Brayton refrigeration cycle with a regenerative heat exchanger.
Ambient To
air in combustor
Main jet
engine
compressor
Heat transfer
to ambient
Air extracted for

cabin cooling
Auxiliary Auxiliary
turbine power
Cool air
to cabin
Figure 10.15 An application of gas
refrigeration to aircraft cabin cooling.
An example of the application of gas refrigeration to cabin cooling in an aircraft is

illustrated in Fig. 10.15. As shown in the figure, a small amount of high-pressure air is
extracted from the main jet engine compressor and cooled by heat transfer to the ambi-
ent. The high-pressure air is then expanded through an auxiliary turbine to the pressure
maintained in the cabin. The air temperature is reduced in the expansion and thus is able
to fulfill its cabin cooling function. As an additional benefit, the turbine expansion can
provide some of the auxiliary power needs of the aircraft. Size and weight are important
considerations in the selection of equipment for use in aircraft. Open-cycle systems, like
the example given here, utilize compact high-speed rotary turbines and compressors. Fur-
thermore, since the air for cooling comes directly from the surroundings, there are fewer
heat exchangers than would be needed if a separate refrigerant were circulated in a closed
vapor-compression cycle.
In this chapter we have considered refrigeration and heat during the compression process and in the expansion across
pump systems, including vapor systems where the refrigerant the valve, as well as the effect of irreversible heat transfer be-
is alternately vaporized and condensed, and gas systems where tween the refrigerant and the warm and cold regions. Varia-
the refrigerant remains a gas. The three principal types of re- tions of the basic vapor-compression refrigeration cycle also
frigeration and heat pump systems discussed are the vapor- have been considered, including cascade cycles and multistage
compression, absorption, and reversed Brayton cycles. compression with intercooling.
The performance of simple vapor refrigeration systems is Qualitative discussions are presented of refrigerant prop-
described in terms of the vapor-compression cycle. For this erties and of considerations in selecting refrigerants. Absorp-
cycle, we have evaluated the principal work and heat trans- tion refrigeration and heat pump systems are also discussed
fers along with two important performance parameters: the qualitatively. A discussion of vapor-compression heat pump
coefficient of performance and the refrigeration capacity. We systems is provided, and the chapter concludes with a study
have considered the effect on performance of irreversibilities of gas refrigeration systems.
The following list provides a study guide for this chapter. apply the first and second laws along with property data
When your study of the text and end-of-chapter exercises has to determine the performance of vapor-compression
been completed, you should be able to refrigeration and heat pump cycles and of Brayton refrig-
eration cycles, including evaluation of the power re-
quired, the coefficient of performance, and the capacity.
throughout the chapter and understand each of the re-
lated concepts. The subset of key concepts listed below sketch schematic diagrams of vapor-compression cycle
is particularly important. modifications, including cascade cycles and multistage
compression with intercooling between the stages. In
sketch the Ts diagrams of vapor-compression refrigera-
each case be able to apply mass and energy balances,
tion and heat pump cycles and of Brayton refrigeration
the second law, and property data to determine
cycles, correctly showing the relationship of the refriger-
performance.
ant temperature to the temperatures of the warm and
cold regions. explain the operation of absorption refrigeration systems.
vapor-compression ton of vapor-compression Brayton refrigeration

refrigeration p. 457 refrigeration p. 458 heat pump p. 472 cycle p. 474
refrigeration absorption
capacity p. 458 refrigeration p. 469
1. What are the temperatures inside the fresh food and freezer 7. You recharge your automobile air conditioner with refrigerant
compartments of your refrigerator? Do you know what values are from time to time, yet seldom, if ever, your refrigerator. Why?
recommended for these temperatures? 8. Would water be a suitable working fluid for use in a refrigerator?
2. How might the variation in the local ambient temperature 9. Sketch the Ts diagram of an ideal vapor-compression refrig-
affect the thermal performance of an outdoor pop machine? eration cycle in which the heat transfer to the warm region occurs
3. Explain how a household refrigerator can be viewed as a heat with the working fluid at a supercritical pressure.
pump that heats the kitchen. If you knew the refrigerators coef- 10. Would you recommend a domestic heat pump for use in
ficient of performance, could you calculate its coefficient of per- Duluth, Minnesota? In San Diego, California?
formance when viewed as a heat pump? 11. What components are contained in the outside unit of a res-
4. If it takes about 335 kJ to freeze 1 kg of water, how much ice idential heat pump?
could an ice maker having a 1-ton refrigeration capacity produce 12. You see an advertisement for a natural gasfired absorption
in 24 hours? refrigeration system. How can burning natural gas play a role in
5. Using the Ts diagram of Fig. 10.1, an area interpretation of achieving cooling?
the Carnot vapor refrigeration cycle coefficient of performance 13. Referring to Fig. 10.13, why is the temperature TH the lim-
is provided in Sec. 10.1. Can a similar area interpretation be iting value for the temperature at state 3? What practical consid-
developed for the coefficient of performance of a vapor- erations might preclude this limit from being achieved?
compression refrigeration cycle? 14. When a regenerator is added to the ideal Brayton refrigera-
6. Would you recommend replacing the expansion valve of tion cycle, as in Fig. 10.14, does the coefficient of performance
Example 10.3 by a turbine? increase or decrease?
Vapor Refrigeration Systems (a) the work input to the compressor.

10.1 A Carnot vapor refrigeration cycle uses Refrigerant 134a (b) the work developed by the turbine.
as the working fluid. The refrigerant enters the condenser as (c) the heat transfer to the refrigerant passing through the
saturated vapor at 28C and leaves as saturated liquid. The evaporator.
evaporator operates at a temperature of 10C. Determine, in What is the coefficient of performance of the cycle?
kJ per kg of refrigerant flow,
10.2 Refrigerant 22 is the working fluid in a Carnot vapor re- liquid leaving the condenser be 32C. Determine, for the
frigeration cycle for which the evaporator temperature is 0C. modified cycle,
Saturated vapor enters the condenser at 40C, and saturated (a) the compressor power, in kW.
liquid exits at the same temperature. The mass flow rate of re- (b) the refrigerating capacity, in tons.
frigerant is 3 kg/min. Determine (c) the coefficient of performance.
(a) the rate of heat transfer to the refrigerant passing through (d) the rates of exergy destruction in the compressor and
the evaporator, in kW. expansion valve, each in kW, for T0 28C.
(b) the net power input to the cycle, in kW. 10.11 A vapor-compression refrigeration system circulates Re-
(c) the coefficient of performance. frigerant 134a at a rate of 6 kg/min. The refrigerant enters the
10.3 An ideal vapor-compression refrigeration cycle operates at compressor at 10C, 1.4 bar, and exits at 7 bar. The isen-
steady state with Refrigerant 134a as the working fluid. Satu- tropic compressor efficiency is 67%. There are no appreciable
rated vapor enters the compressor at 10C, and saturated liq- pressure drops as the refrigerant flows through the condenser
uid leaves the condenser at 28C. The mass flow rate of and evaporator. The refrigerant leaves the condenser at 7 bar,
refrigerant is 5 kg/min. Determine 24C. Ignoring heat transfer between the compressor and its
(a) the compressor power, in kW. surroundings, determine
(b) the refrigerating capacity, in tons. (a) the coefficient of performance.
(c) the coefficient of performance. (b) the refrigerating capacity, in tons.
10.4 Modify the cycle in Problem 10.3 to have saturated vapor (c) the rates of exergy destruction in the compressor and ex-
entering the compressor at 1.6 bar and saturated liquid leav- pansion valve, each in kW.
ing the condenser at 9 bar. Answer the same questions for the (d) the changes in specific flow exergy of the refrigerant pass-
modified cycle as in Problem 10.3. ing through the evaporator and condenser, respectively,
each in kJ/kg.
10.5 Plot each of the quantities calculated in Problem 10.4 ver-
sus evaporator pressure ranging from 0.6 to 4 bar, while the Let T0 21C, p0 1 bar.
condensor pressure remains fixed at 6, 9, and 12 bar. 10.12 If the minimum and maximum allowed refrigerant pres-
10.6 Refrigerant 22 enters the compressor of an ideal vapor- sures are 1 and 10 bar, respectively, which of the following
compression refrigeration system as saturated vapor at 40C can be used as the working fluid in a vapor-compression
with a volumetric flow rate of 15 m3/min. The refrigerant leaves refrigeration system that maintains a cold region at 0C,
the condenser at 32C, 9 bar. Determine while discharging energy by heat transfer to the surrounding
air at 30C: Refrigerant 22, Refrigerant 134a, ammonia,
(a) the compressor power, in kW. propane?
(b) the refrigerating capacity, in tons.
(c) the coefficient of performance. 10.13 In a vapor-compression refrigeration cycle, ammonia exits
the evaporator as saturated vapor at 22C. The refrigerant
10.7 An ideal vapor-compression refrigeration cycle, with am- enters the condenser at 16 bar and 160C, and saturated liquid
monia as the working fluid, has an evaporator temperature of exits at 16 bar. There is no significant heat transfer between the
20C and a condenser pressure of 12 bar. Saturated vapor compressor and its surroundings, and the refrigerant passes
enters the compressor, and saturated liquid exits the condenser. through the evaporator with a negligible change in pressure. If
The mass flow rate of the refrigerant is 3 kg/min. Determine the refrigerating capacity is 150 kW, determine
(a) the coefficient of performance. (a) the mass flow rate of refrigerant, in kg/s.
(b) the refrigerating capacity, in tons. (b) the power input to the compressor, in kW.
10.8 To determine the effect of changing the evaporator tem- (c) the coefficient of performance.
perature on the performance of an ideal vapor-compression re- (d) the isentropic compressor efficiency.
frigeration cycle, plot the coefficient of performance and the 10.14 A vapor-compression refrigeration system with a capac-
refrigerating capacity, in tons, for the cycle in Problem 10.7 ity of 10 tons has superheated Refrigerant 134a vapor enter-
for saturated vapor entering the compressor at temperatures ing the compressor at 15C, 4 bar, and exiting at 12 bar. The
ranging from 40 to 10C. All other conditions are the same compression process can be modeled by pv1.01 constant. At
as in Problem 10.7. the condenser exit, the pressure is 11.6 bar, and the tempera-
10.9 To determine the effect of changing condenser pressure ture is 44C. The condenser is water-cooled, with water enter-
on the performance of an ideal vapor-compression refrigera- ing at 20C and leaving at 30C with a negligible change in
tion cycle, plot the coefficient of performance and the refrig- pressure. Heat transfer from the outside of the condenser can
erating capacity, in tons, for the cycle in Problem 10.7 for be neglected. Determine
condenser pressures ranging from 8 to 16 bar. All other con-
(a) the mass flow rate of the refrigerant, in kg/s.
ditions are the same as in Problem 10.7.
(b) the power input and the heat transfer rate for the com-
10.10 Modify the cycle in Problem 10.4 to have an isentropic pressor, each in kW.
compressor efficiency of 80% and let the temperature of the (c) the coefficient of performance.
(d) the mass flow rate of the cooling water, in kg/s. 10.17 Figure P10.17 shows a Refrigerant 22 vapor-compression
(e) the rates of exergy destruction in the condenser and ex- refrigeration system with mechanical subcooling. A counter-
pansion valve, each expressed as a percentage of the power flow heat exchanger subcools a portion of the refrigerant leav-
input. Let T0 20C. ing the condenser below the ambient temperature as follows:
10.15 Figure P10.15 shows a steam jet refrigeration system that Saturated liquid exits the condenser at 12 bars. A portion of
produces chilled water in a flash chamber. The chamber is the flow exiting the condenser is diverted through an expan-
maintained at a vacuum pressure by the steam ejector, which sion valve and passes through the counterflow heat exchanger
removes the vapor generated by entraining it in the low- with no pressure drop, leaving as saturated vapor at 6C. The
pressure jet and discharging into the condenser. The vacuum diverted flow is then compressed isentropically to 12 bars and
pump removes air and other noncondensable gases from the reenters the condenser. The remainder of the flow exiting the
condenser shell. For the conditions shown on the figure, de- condenser passes through the other side of the heat exchanger
termine the make-up water and cooling water flow rates, each and exits at 40C, 12 bars. The evaporator has a capacity of
in kg/h. 50 tons and produces 28C saturated vapor at its exit. In the
main compressor, the refrigerant is compressed isentropically
to 12 bars. Determine at steady state
Air (a) the mass flow rate at the inlet to each compressor, in
Saturated vapor
at 200 kPa kg/s.
Vacuum (b) the power input to each compressor, in kW.
Ejector nozzle pump (c) the coefficient of performance.
Steam jet
Counterflow

Make-up heat exchanger Qout
water Saturated liquid
Sat p4 = 12 bars
at 15C p3 = 12 bars
vapor T4 = 4C 3
p = 4 kPa 4 Condenser
Compressor
Condenser
Expansion
5C valve
7 8 p2 = 12 bars
Saturated vapor p8 = 12 bars
T7 = 6C 2
Cooling
load Expansion Wc2
142 tons valve
Cooling Condensate
water in return Main
Pump at 15C to drain Wc1
compressor
5
25,000
kg/h 25C
1
Figure P10.15 Evaporator
Saturated vapor
T1 = 28C
Cascade and Multistage Systems

Qin
10.16 A vapor-compression refrigeration system uses the
Figure P10.17
arrangement shown in Fig. 10.8 for two-stage compression with
intercooling between the stages. Refrigerant 134a is the work-
ing fluid. Saturated vapor at 30C enters the first compressor 10.18 Figure P10.18 shows the schematic diagram of a vapor-
stage. The flash chamber and direct contact heat exchanger op- compression refrigeration system with two evaporators using
erate at 4 bar, and the condenser pressure is 12 bar. Saturated Refrigerant 134a as the working fluid. This arrangement is used
liquid streams at 12 and 4 bar enter the high- and low-pressure to achieve refrigeration at two different temperatures with a
expansion valves, respectively. If each compressor operates single compressor and a single condenser. The low-temperature
isentropically and the refrigerating capacity of the system is 10 evaporator operates at 18C with saturated vapor at its exit
tons, determine and has a refrigerating capacity of 3 tons. The higher-
(a) the power input to each compressor, in kW. temperature evaporator produces saturated vapor at 3.2 bar at
(b) the coefficient of performance. its exit and has a refrigerating capacity of 2 tons. Compression

Qout Qout
3 2 2
Condenser Condenser

Wc
Compressor Wc
Expansion Compressor
valve
4 1 3 1
Evaporator 7 8
2
Expansion
valve
Heat exchanger
Qin,2 = 2 tons
Expansion
valve
4
5 Evaporator 6
1
Expansion
valve

Qin,1 = 3 tons
5 6
Figure P10.18 Evaporator

Qin
is isentropic to the condenser pressure of 10 bar. There are no Figure P10.19
significant pressure drops in the flows through the condenser
and the two evaporators, and the refrigerant leaves the con-
denser as saturated liquid at 10 bar. Calculate evaporator, and saturated liquid at 8 bar leaves the condenser.
(a) the mass flow rate of refrigerant through each evaporator, Calculate
in kg/min. (a) the power input to the compressor, in kW.
(b) the compressor power input, in kW. (b) the coefficient of performance.
(c) the rate of heat transfer from the refrigerant passing (c) the coefficient of performance of a Carnot heat pump cycle
through the condenser, in kW. operating between thermal reservoirs at 20 and 5C.
10.19 An ideal vapor-compression refrigeration cycle is modi- 10.21 A vapor-compression heat pump system uses ammonia
fied to include a counterflow heat exchanger, as shown in as the working fluid. The refrigerant enters the compressor at
Fig. P10.19. Ammonia leaves the evaporator as saturated vapor 2.5 bar, 5C, with a volumetric flow rate of 0.6 m3/min.
at 1.0 bar and is heated at constant pressure to 5C before en- Compression is adiabatic to 14 bar, 140C, and saturated liquid
tering the compressor. Following isentropic compression to 18 exits the condenser at 14 bar. Determine
bar, the refrigerant passes through the condenser, exiting at
(a) the power input to the compressor, in kW.
40C, 18 bar. The liquid then passes through the heat ex-
(b) the heating capacity of the system, in kW and tons.
changer, entering the expansion valve at 18 bar. If the mass
(c) the coefficient of performance.
flow rate of refrigerant is 12 kg/min, determine
(d) the isentropic compressor efficiency.
(a) the refrigeration capacity, in tons of refrigeration. 10.22 On a particular day when the outside temperature is 5C,
(b) the compressor power input, in kW. a house requires a heat transfer rate of 12 kW to maintain the
(c) the coefficient of performance. inside temperature at 20C. A vapor-compression heat pump
Discuss possible advantages and disadvantages of this with Refrigerant 22 as the working fluid is to be used to pro-
arrangement. vide the necessary heating. Specify appropriate evaporator and
condenser pressures of a cycle for this purpose. Let the re-
Vapor-Compression Heat Pump Systems frigerant be saturated vapor at the evaporator exit and saturated
10.20 An ideal vapor-compression heat pump cycle with Re- liquid at the condenser exit. Calculate
frigerant 134a as the working fluid provides heating at a rate (a) the mass flow rate of refrigerant, in kg/min.
of 15 kW to maintain a building at 20C when the outside (b) the compressor power, in kW.
temperature is 5C. Saturated vapor at 2.4 bar leaves the (c) the coefficient of performance.
10.23 Repeat the calculations of Problem 10.22 for Refrigerant Gas Refrigeration Systems
134a as the working fluid. Compare the results with those of 10.26 Air enters the compressor of an ideal Brayton refrigera-
Problem 10.22 and discuss. tion cycle at 100 kPa, 270 K. The compressor pressure ratio is
10.24 A vapor-compression heat pump with a heating capacity 3, and the temperature at the turbine inlet is 310 K. Determine
of 500 kJ/min is driven by a power cycle with a thermal effi- (a) the net work input, per unit mass of air flow, in kJ/kg.
ciency of 25%. For the heat pump, Refrigerant 134a is com- (b) the refrigeration capacity, per unit mass of air flow, in kJ/kg.
pressed from saturated vapor at 10C to the condenser (c) the coefficient of performance.
pressure of 10 bar. The isentropic compressor efficiency is (d) the coefficient of performance of a Carnot refrigeration cy-
80%. Liquid enters the expansion valve at 9.6 bar, 34C. For cle operating between thermal reservoirs at TC 270 K
the power cycle, 80% of the heat rejected is transferred to the and TH 310 K, respectively.
heated space.
10.27 Reconsider Problem 10.26, but include in the analysis
(a) Determine the power input to the heat pump compressor, that the compressor and turbine have isentropic efficiencies of
in kW. 80 and 88%, respectively. For the modified cycle
(b) Evaluate the ratio of the total rate that heat is delivered to
(a) determine the coefficient of performance.
the heated space to the rate of heat input to the power cycle.
(b) develop an exergy accounting of the compressor power in-
Discuss.
put, in kJ per kg of air flowing. Discuss
10.25 A residential heat pump system operating at steady state Let T0 310 K.
is shown schematically in Fig. P10.25. Refrigerant 22 circu-
10.28 Plot the quantities calculated in parts (a) through (c) of
lates through the components of the system, and property data
Problem 10.26 versus the compressor pressure ratio ranging
at the numbered states are given on the figure. The compres-
from 2 to 6. Repeat for compressor and turbine isentropic
sor operates adiabatically. Kinetic and potential energy changes
efficiencies of 95%, 90%, and 80%.
are negligible as are changes in pressure of the streams pass-
ing through the condenser and evaporator. Let T0 273 K. 10.29 Air enters the compressor of an ideal Brayton refrigera-
Determine tion cycle at 140 kPa, 270 K, and is compressed to 420 kPa.
At the turbine inlet, the temperature is 320 K and the volu-
(a) the power required by the compressor, in kW, and the isen- metric flow rate is 0.4 m3/s. Determine
tropic compressor efficiency.
(b) the coefficient of performance. (a) the mass flow rate, in kg/s.
(c) Perform a full exergy accounting of the compressor power (b) the net power input, in kW.
input, in kW. Discuss. (c) the refrigerating capacity, in kW.
(d) Devise and evaluate an exergetic efficiency for the heat (d) the coefficient of performance.
pump system. 10.30 Air enters the compressor of a Brayton refrigeration cy-
cle at 100 kPa, 260 K, and is compressed adiabatically to 300
kPa. Air enters the turbine at 300 kPa, 300 K, and expands adi-
abatically to 100 kPa. For the cycle
Return air Heated air
from house to house (a) determine the net work per unit mass of air flow, in kJ/kg,
p5 = 1 bar 5 6 and the coefficient of performance if the compressor and
T5 = 20C T6 = 50C turbine isentropic efficiencies are both 100%.
3
(AV)5 = 0.42 m /s p2 = 14 bar (b) plot the net work per unit mass of air flow, in kJ/kg, and
T2 = 75C the coefficient of performance for equal compressor and
Condenser
2 turbine isentropic efficiencies ranging from 80 to 100%.
3
p3 = 14 bar 10.31 The Brayton refrigeration cycle of Problem 10.26 is mod-
T3 = 28C ified by the introduction of a regenerative heat exchanger. In

Expansion
Wc the modified cycle, compressed air enters the regenerative heat
Compressor exchanger at 310 K and is cooled to 280 K before entering the
valve
turbine. Determine, for the modified cycle,
(a) the lowest temperature, in K.
4
p4 = 3.5 bar Evaporator T1 = 5C (b) the net work input per unit mass of air flow, in kJ/kg.
1 p1 = 3.5 bar (c) the refrigeration capacity, per unit mass of air flow, in kJ/kg.
(d) the coefficient of performance.
8 7 10.32 Reconsider Problem 10.31, but include in the analysis
Air exits Outside air that the compressor and turbine have isentropic efficiencies of
at 12C enters at 0C 85 and 88% respectively. Answer the same questions as in
Figure P10.25 Problem 10.31.
10.33 Plot the quantities calculated in parts (a) through (d) of pression ratio is 6, and the temperature during the isothermal
Problem 10.31 versus the compressor pressure ratio ranging expansion is 100 K. Determine
from 3 to 7. Repeat for equal compressor and turbine isen- (a) the heat transfer during the isothermal expansion, in kJ per
tropic efficiencies of 95%, 90%, and 80%. kg of air.
10.34 Air at 2 bar, 380 K is extracted from a main jet engine (b) the net work for the cycle, in kJ per kg of air.
compressor for cabin cooling. The extracted air enters a heat (c) the coefficient of performance.
exchanger where it is cooled at constant pressure to 320 K 10.36 Air undergoes an Ericsson refrigeration cycle, which is
through heat transfer with the ambient. It then expands adia- the reverse of the Ericsson power cycle introduced in Sec. 9.11.
batically to 0.95 bar through a turbine and is discharged into At the beginning of the isothermal compression, the pressure
the cabin. The turbine has an isentropic efficiency of 75%. If and temperature are 100 kPa and 310 K, respectively. The pres-
the mass flow rate of the air is 1.0 kg/s, determine sure ratio during the isothermal compression is 3. During the
(a) the power developed by the turbine, in kW. isothermal expansion the temperature is 270 K. Determine
(b) the rate of heat transfer from the air to the ambient, in kW. (a) the heat transfer for the isothermal expansion, per unit
10.35 Air undergoes a Stirling refrigeration cycle, which is the mass of air flow, in kJ/kg.
reverse of the Stirling power cycle introduced in Sec. 9.11. At (b) the net work, per unit mass of air flow, in kJ/kg.
the beginning of the isothermal compression, the pressure and (c) the coefficient of performance.
temperature are 100 kPa and 300 K, respectively. The com-
10.1D A vapor-compression refrigeration system using Refrig- Base your strategy on the daynight electric rate structure of
erant 134a is being designed for a household food freezer. The your local electric utility company.
refrigeration system must maintain a temperature of 18C 10.5D A heat pump is under consideration for heating and cool-
within the freezer compartment when the temperature of the ing a 3600-ft2 camp lodge in rural Wisconsin. The lodge is
room is 32C. Under these conditions, the steady-state heat used continuously in the summer and on weekends in the
transfer rate from the room into the freezer compartment is winter. The system must provide adequate heating for winter
440 W. Specify operating pressures and temperatures at key temperatures as low as 23C, and an associated heating load
points within the refrigeration system and estimate the refrig- of 30 kW. In the summer, the maximum outside temperature
erant mass flow rate and compressor power required. is 38C, and the associated cooling load is 44 kW. The local
10.2D Design a bench-top-sized air-to-air vapor-compression water table is 30 M, and the ground water temperature is 14C.
refrigeration system to be used in a student laboratory. Include Compare the initial, operating, and maintenance costs of an
in your design the capability to utilize either of two expansion air-source heat pump to a vertical well ground-source heat
devices: a capillary tube or a thermostatic expansion valve. pump for this application, and make a recommendation as to
Provide sketches of the layout of your system, including ap- which is the best option.
propriate interconnecting piping. Specify the locations and 10.6D Investigate the economic feasibility of using a waste
types of sensors to allow students to measure the electrical heat-recovery heat pump for domestic water heating that
power consumption and refrigeration capacity, as well as per- employs ventilation air being discharged from a dwelling as
form energy balances on the evaporator and condenser. the source. Assume typical hot water use of a family of four
10.3D Refrigerant 22 is widely used as the working fluid in air living in a single-family dwelling in your locale. Write a report
conditioners and industrial chillers. However, its use is likely of your findings.
to be phased out in the future due to concerns about ozone de- 10.7D List the major design issues involved in using ammonia
pletion. Investigate which environmentally-acceptable working as the refrigerant in a system to provide chilled water at 4C
fluids are under consideration to replace Refrigerant 22 for for air conditioning a college campus in your locale. Develop
these uses. Determine the design issues for air conditioners and a layout of the equipment room and a schematic of the chilled
chillers that would result from changing refrigerants. Write a water distribution system. Label the diagrams with key tem-
report of your findings. peratures and make a list of capacities of each of the major
10.4D An air-conditioning system is under consideration that pieces of equipment.
will use a vapor-compression ice maker during the nighttime, 10.8D Carbon dioxide (CO2) is an inexpensive, nontoxic, and
when electric rates are lowest, to store ice for meeting the day- non-flammable candidate for use as a working fluid in vapor-
time air-conditioning load. The maximum loads are 100 tons compression systems. Investigate the suitability of using CO2
during the day and 50 tons at night. Is it best to size the sys- as the working fluid in a heat pump-water heater requiring a
tem to make enough ice at night to carry the entire daytime power input ranging from 50 to 100 kW and providing hot
load or to use a smaller chiller that runs both day and night? water ranging from 50 to 90C. Assume that ground water is
used as the source. Specify the typical operating pressures for 10.10D Determine the current status of magnetic refrigeration
such applications and estimate the variation in coefficient of technology for use in the 80 to 300 K range. Does this tech-
performance for the range of hot water temperature. Prepare a nology hold promise as an economical alternative to vapor-
memorandum summarizing your results. compression systems? Discuss.
10.9D Common cryogenic refrigeration applications include air 10.11D New Materials may Revive Thermoelectric Cooling
separation to obtain oxygen and nitrogen, large-scale produc- (see box Sec. 10.3). Investigate the current state-of-the-art of
tion of liquid hydrogen, and the liquefaction of natural gas. nanotechnology in an area of current interest. Write a report
Describe the equipment used to achieve the low temperatures including at least three references.
required in these applications. How do cryogenic systems dif-
fer from systems used for common refrigeration and air-
conditioning applications?
C
H
A
P
T
Thermodynamic
Relations
E
R 11
E N G I N E E R I N G C O N T E X T As seen in previous chapters, applica-
tion of thermodynamic principles to engineering systems requires data for specific internal
energy, enthalpy, entropy, and other properties. The objective of the present chapter is to chapter objective
introduce thermodynamic relations that allow u, h, s, and other thermodynamic properties
of simple compressible systems to be evaluated from data that are more readily measured.
Primary emphasis is on systems involving a single chemical species such as water or a
mixture such as air. An introduction to general property relations for mixtures and
solutions is also included.
Means are available for determining pressure, temperature, volume, and mass experi-
mentally. In addition, the relationships between the specific heats cv and cp and tempera-
ture at relatively low pressure are accessible experimentally. Values for certain other
thermodynamic properties also can be measured without great difficulty. However, specific
internal energy, enthalpy, and entropy are among those properties that are not easily
obtained experimentally, so we resort to computational procedures to determine values
for these.

11.1 Using Equations of State
An essential ingredient for the calculation of properties such as the specific internal energy,
enthalpy, and entropy of a substance is an accurate representation of the relationship among
pressure, specific volume, and temperature. The pvT relationship can be expressed alter-
natively: There are tabular representations, as exemplified by the steam tables. The rela-
tionship also can be expressed graphically, as in the pvT surface and compressibility factor
charts. Analytical formulations, called equations of state, constitute a third general way of equations of state
expressing the pvT relationship. Computer software such as Interactive Thermodynamics:
IT also can be used to retrieve pvT data.
The virial equation and the ideal gas equation are examples of analytical equations of state
introduced in previous sections of the book. Analytical formulations of the pvT relation-
ship are particularly convenient for performing the mathematical operations required to
calculate u, h, s, and other thermodynamic properties. The object of the present section is to
expand on the discussion of pvT relations for simple compressible substances presented
in Chap. 3 by introducing some commonly used equations of state.
487
488 Chapter 11 Thermodynamic Relations
11.1.1 Getting Started

Recall from Sec. 3.4 that the virial equation of state can be derived from the principles of
statistical mechanics to relate the pvT behavior of a gas to the forces between mole-
cules. In one form, the compressibility factor Z is expanded in inverse powers of specific
volume as
B1T 2 C 1T 2 D1T2
virial equation Z1

2

# # # (11.1)
v v v3
The coefficients B, C, D, etc. are called, respectively, the second, third, fourth, etc. virial co-
efficients. Each virial coefficient is a function of temperature alone. In principle, the virial
coefficients are calculable if a suitable model for describing the forces of interaction between
the molecules of the gas under consideration is known. Future advances in refining the theory
of molecular interactions may allow the virial coefficients to be predicted with considerable
accuracy from the fundamental properties of the molecules involved. However, at present,
just the first two or three coefficients can be calculated and only for gases consisting of rel-
atively simple molecules. Equation 11.1 also can be used in an empirical fashion in which
the coefficients become parameters whose magnitudes are determined by fitting pvT data
in particular realms of interest. Only the first few coefficients can be found this way, and the
result is a truncated equation valid only for certain states.
In the limiting case where the gas molecules are assumed not to interact in any way, the
second, third, and higher terms of Eq. 11.1 vanish and the equation reduces to Z 1. Since
Z pv RT, this gives the ideal gas equation of state pv RT. The ideal gas equation of
state provides an acceptable approximation at many states, including but not limited to states
where the pressure is low relative to the critical pressure and/or the temperature is high rel-
ative to the critical temperature of the substance under consideration. At many other states,
however, the ideal gas equation of state provides a poor approximation.
Over 100 equations of state have been developed in an attempt to improve on the ideal
gas equation of state and yet avoid the complexities inherent in a full virial series. In gen-
eral, these equations exhibit little in the way of fundamental physical significance and are
mainly empirical in character. Most are developed for gases, but some describe the pvT
behavior of the liquid phase, at least qualitatively. Every equation of state is restricted to par-
ticular states. This realm of applicability is often indicated by giving an interval of pressure,
or density, where the equation can be expected to represent the pvT behavior faithfully.
When it is not stated, the realm of applicability of a given equation can be approximated by
expressing the equation in terms of the compressibility factor Z and the reduced properties
pR, TR, vR and superimposing the result on a generalized compressibility chart or comparing
with tabulated compressibility data obtained from the literature.
11.1.2 Two-Constant Equations of State

Equations of state can be classified by the number of adjustable constants they include. Let
us consider some of the more commonly used equations of state in order of increasing
complexity, beginning with two-constant equations of state.
VAN DER WAALS EQUATION
An improvement over the ideal gas equation of state based on elementary molecular arguments
was suggested in 1873 by van der Waals, who noted that gas molecules actually occupy more
than the negligibly small volume presumed by the ideal gas model and also exert long-range
attractive forces on one another. Thus, not all of the volume of a container would be avail-
able to the gas molecules, and the force they exert on the container wall would be reduced
11.1 Using Equations of State 489
because of the attractive forces that exist between molecules. Based on these elementary
molecular arguments, the van der Waals equation of state is
RT a
p 2 (11.2) van der Waals equation
vb v
The constant b is intended to account for the finite volume occupied by the molecules, the
term av 2 accounts for the forces of attraction between molecules, and R is the universal gas
constant. Note than when a and b are set to zero, the ideal gas equation of state results.
The van der Waals equation gives pressure as a function of temperature and specific vol-
ume and thus is explicit in pressure. Since the equation can be solved for temperature as a
function of pressure and specific volume, it is also explicit in temperature. However, the
equation is cubic in specific volume, so it cannot generally be solved for specific volume
in terms of temperature and pressure. The van der Waals equation is not explicit in specific p
volume.
T > Tc
EVALUATING a AND b. The van der Waals equation is a two-constant equation of state. T = Tc
For a specified substance, values for the constants a and b can be found by fitting the equa- T < Tc
p
tion to pvT data. With this approach several sets of constants might be required to cover (
_(
v T = 0
all states of interest. Alternatively, a single set of constants for the van der Waals equation Critical
can be determined by noting that the critical isotherm passes through a point of inflection at point
the critical point, and the slope is zero there. Expressed mathematically, these conditions are,
respectively
0 2p
a 2 b 0, a b 0 1critical point2
0p
(11.3) v
0v T 0v T
Although less overall accuracy normally results when the constants a and b are determined
using critical point behavior than when they are determined by fitting pvT data in a par-
ticular region of interest, the advantage of this approach is that the van der Waals constants
can be expressed in terms of the critical pressure pc and critical temperature Tc, as demon-
strated next.
For the van der Waals equation at the critical point
RTc a
pc 2
vc b vc
Applying Eqs. 11.3 with the van der Waals equation gives
0 2p
a 2b
2RTc 6a
3 0
0v T 1vc b2 v 4c
a b
0p RTc 2a

30
0v T 1vc b2 2 vc
Solving the foregoing three equations for a, b, and vc in terms of the critical pressure and
critical temperature
27 R 2T 2c
a (11.4a)
64 pc
RTc
b (11.4b)
8pc
3 R Tc
vc (11.4c)
8 pc
Values of the van der Waals constants a and b determined from Eqs. 11.4a and 11.4b for
several common substances are given in Table A-24 for pressure in bar, specific volume in
m3/kmol, and temperature in K.
GENERALIZED FORM. Introducing the compressibility factor Z pv RT, the reduced tem-
perature TR TTc, the pseudoreduced specific volume vR pcvRTc, and the foregoing
expressions for a and b, the van der Waals equation can be written in terms of Z, vR, and
TR as
vR 2764
Z (11.5)
vR 18 TRvR
or alternatively in terms of Z, TR, and pR as

27p2R
Z3 a
1b Z 2
a b
pR 27pR
Z 0 (11.6)
8TR 64T 2R 512T 3R
The details of these developments are left as exercises. Equation 11.5 can be evaluated for
specified values of vR and TR and the resultant Z values located on a generalized compress-
ibility chart to show approximately where the equation performs satisfactorily. A similar ap-
proach can be taken with Eq. 11.6.
The compressibility factor at the critical point yielded by the van der Waals equation is
determined from Eq. 11.4c as
pcvc
Zc 0.375
R Tc
Actually, Zc varies from about 0.23 to 0.33 for most substances (see Tables A-1). Accord-
ingly, with the set of constants given by Eqs. 11.4, the van der Waals equation is inaccurate
in the vicinity of the critical point. Further study would show inaccuracy in other regions as
well, so this equation is not suitable for many thermodynamic evaluations. The van der Waals
equation is of interest to us primarily because it is the simplest model that accounts for the
departure of actual gas behavior from the ideal gas equation of state.
REDLICHKWONG EQUATION
Three other two-constant equations of state that have been widely used are the Berthelot, Di-
eterici, and RedlichKwong equations. The RedlichKwong equation, considered by many
to be the best of the two-constant equations of state, is
RT a
p
v 1v
b2T1 2
RedlichKwong equation (11.7)
vb
This equation, proposed in 1949, is mainly empirical in nature, with no rigorous justification
in terms of molecular arguments. The RedlichKwong equation is explicit in pressure but not
in specific volume or temperature. Like the van der Waals equation, the RedlichKwong equa-
tion is cubic in specific volume.
Although the RedlichKwong equation is somewhat more difficult to manipulate math-
ematically than the van der Waals equation, it is more accurate, particularly at higher pres-
sures. In recent years, several modified forms of this equation have been proposed to
achieve improved accuracy. The two-constant RedlichKwong equation performs better
than some equations of state having several adjustable constants; still, two-constant equa-
tions of state tend to be limited in accuracy as pressure (or density) increases. Increased
accuracy at such states normally requires equations with a greater number of adjustable
constants.
EVALUATING a AND b. As for the van der Waals equation, the constants a and b in Eq. 11.7
can be determined for a specified substance by fitting the equation to pvT data, with sev-
eral sets of constants required to represent accurately all states of interest. Alternatively, a
single set of constants in terms of the critical pressure and critical temperature can be eval-
uated using Eqs. 11.3, as for the van der Waals equation. The result is
R 2T c5 2 R Tc
a a and b b (11.8)
pc pc
where a 0.42748 and b 0.08664. Evaluation of these constants is left as an exercise.
Values of the RedlichKwong constants a and b determined from Eqs. 11.8 for several com-
mon substances are given in Table A-24 for pressure in bar, specific volume in m3/kmol, and
temperature in K.
GENERALIZED FORM. Introducing the compressibility factor Z, the reduced temperature

TR, the pseudoreduced specific volume vR, and the foregoing expressions for a and b, the
RedlichKwong equation can be written as
vR a
Z
1vR
b2 T R3 2
(11.9)
vR b
Equation 11.9 can be evaluated at specified values of vR and TR and the resultant Z values
located on a generalized compressibility chart to show the regions where the equation per-
forms satisfactorily. With the constants given by Eqs. 11.8, the compressibility factor at the
critical point yielded by the RedlichKwong equation is Zc 0.333, which is at the high end
of the range of values for most substances, indicating that inaccuracy in the vicinity of the
critical point should be expected.
In Example 11.1, the pressure of a gas is determined using three equations of state and
the generalized compressibility chart. The results are compared.
EXAMPLE 11.1 Comparing Equations of State
A cylindrical tank containing 4.0 kg of carbon monoxide gas at 50C has an inner diameter of 0.2 m and a length of
1 m. Determine the pressure, in bar, exerted by the gas using (a) the generalized compressibility chart, (b) the ideal gas
equation of state, (c) the van der Waals equation of state, (d) the RedlichKwong equation of state. Compare the results
obtained.
SOLUTION
Known: A cylindrical take of known dimensions contains 4.0 kg of CO gas at 50C.
Find: Determine the pressure exerted by the gas using four alternative methods.
D = 0.2 m
Assumptions:
1. As shown in the accompanying figure, the closed system is taken as the gas.
4 kg CO gas
L=1m 2. The system is at equilibrium.
at 50C
Figure E11.1
Analysis: The molar specific volume of the gas is required in each part of the solution. Let us begin by evaluating it. The
volume occupied by the gas is
pD2 p10.2 m2 2 11.0 m2
Va bL 0.0314 m3
4 4
The molar specific volume is then
0.0314 m3 m3
v Mv M a b a28 ba b 0.2198
V kg
m kmol 4.0 kg kmol
(a) From Table A-1 for CO, Tc 133 K, pc 35 bar. Thus, the reduced temperature TR and pseudoreduced specific volume
vR are, respectively
223 K
TR 1.68
133 K
vpc 10.2198 m3/kmol2 135 105 N/m2 2
vR 0.696
RTc 18314 N # m / kmol # K2 1133 K2
Turning to Fig. A-2, Z 0.9. Solving Z pvRT for pressure and inserting known values
0.918314 N # m / kmol # K2 1223 K2
` 5 ` 75.9 bar
ZRT 1 bar
p
v 10.2198 m3/kmol2 10 N/m2
(b) The ideal gas equation of state gives
18314 N # m/ kmol # K21223 K2
` 5 ` 84.4 bar
RT 1 bar
p
v 10.2198 m /kmol2
3
10 N/m2
(c) For carbon monoxide, the van der Waals constants a and b given by Eqs. 11.4 can be read directly from Table A-24. Thus
m3 2 m3
a 1.474 bar a b and b 0.0395
kmol kmol
Substituting into Eq. 11.2
RT a
p 2
vb v
18314 N # m / kmol # K2 1223 K2 1.474 bar 1m3/kmol2 2
` `
1 bar

10.2198 0.03952 1m /kmol2 10 N/m
3 5 2
10.2198 m3/kmol2 2
72.3 bar
Alternatively, the values for vR and TR obtained in the solution of part (a) can be substituted into Eq. 11.5, giving Z 0.86.
Then, with p ZRT v, p 72.5 bar. The slight difference is attributed to roundoff.
(d) For carbon monoxide, the RedlichKwong constants given by Eqs. 11.8 can be read directly from Table A-24. Thus
17.22 bar 1m6 21K2 12

a b 0.02737 m3/kmol
1kmol2 2
and
Substituting into Eq. 11.7
RT a
p
vb v 1v
b2T 1 2
18314 N m/kmol # K2 1223 K2
#
` `
1 bar 17.22 bar

10.2198 0.027372 m /kmol 10 N/m
3 5 2
10.21982 10.247172 12232 12
75.1 bar
Alternatively, the values for vR and TR obtained in the solution of part (a) can be substituted into Eq. 11.9, giving Z 0.89.
Then, with p ZRT v, p 75.1 bar.
In comparison to the value of part (a), the ideal gas equation of state predicts a pressure that is 11% higher and the van der
Waals equation gives a value that is 5% lower. The RedlichKwong value is about 1% less than the value obtained using the
compressibility chart.
11.1.3 Multiconstant Equations of State

To fit the pvT data of gases over a wide range of states, Beattie and Bridgeman
proposed in 1928 a pressure-explicit equation involving five constants in addition to the
gas constant. The BeattieBridgeman equation can be expressed in a truncated virial
form as
RT b g d BeattieBridgeman
p
2
3
4 (11.10) equation
v v v v
where
b BRT A cRT 2
g BbRT
Aa BcRT 2 (11.11)
d BbcRT 2
The five constants a, b, c, A, and B appearing in these equations are determined by curve fit-
ting to experimental data.
Benedict, Webb, and Rubin extended the BeattieBridgeman equation of state to cover a
broader range of states. The resulting equation, involving eight constants in addition to the
gas constant, has been particularly successful in predicting the pvT behavior of light
hydrocarbons. The BenedictWebbRubin equation is
1bR T a2

aBR T A 2 b 2

6
3 2 a1
2 b exp a 2 b
RT C 1 aa c g g
p BenedictWebbRubin
v T v v3 v v T v v equation
(11.12)
Values of the constants appearing in Eq. 11.12 for five common substances are given in
Table A-24 for pressure in bar, specific volume in m3/kmol, and temperature in K. Because
Eq. 11.12 has been so successful, its realm of applicability has been extended by introduc-
ing additional constants.
Equations 11.10 and 11.12 are merely representative of multiconstant equations of state.
Many other multiconstant equations have been proposed. With high-speed computers, equa-
tions having 50 or more constants have been developed for representing the pvT behavior
of different substances.

11.2 Important Mathematical Relations
Values of two independent intensive properties are sufficient to fix the state of a simple com-
pressible system of specified mass and composition (Sec. 3.1). All other intensive properties
can be determined as functions of the two independent properties: p p(T, v), u u(T, v),
h h(T, v), and so on. These are all functions of two independent variables of the form
z z(x, y), with x and y being the independent variables. It might also be recalled that the
differential of every property is exact (Sec. 2.2.1). The differentials of nonproperties such as
work and heat are inexact. Let us review briefly some concepts from calculus about functions
of two independent variables and their differentials.
exact differential The exact differential of a function z, continuous in the variables x and y, is
dz a b dx
a b dy
0z 0z
(11.13a)
0x y 0y x
This can be expressed alternatively as
dz M dx
N dy (11.13b)
where M (0z0x)y and N (0z0y)x. The coefficient M is the partial derivative of z with
respect to x (the variable y being held constant). Similarly, N is the partial derivative of z
with respect to y (the variable x being held constant).
If the coefficients M and N have continuous first partial derivatives, the order in which a
second partial derivative of the function z is taken is immaterial. That is
ca b d ca b d
0 0z 0 0z
(11.14a)
0y 0x y x 0x 0y x y
test for exactness or
a b a b
0M 0N
(11.14b)
0y x 0x y
which can be called the test for exactness, as discussed next.

In words, Eqs. 11.14 indicate that the mixed second partial derivatives of the function z
are equal. The relationship in Eq. 11.14 is both a necessary and sufficient condition for the
exactness of a differential expression, and it may therefore be used as a test for exactness.
When an expression such as M dx
N dy does not meet this test, no function z exists whose
differential is equal to this expression. In thermodynamics, Eq. 11.14 is not generally used
to test exactness but rather to develop additional property relations. This is illustrated in
Sec. 11.3 to follow.
11.2 Important Mathematical Relations 495
Two other relations among partial derivatives are listed next for which applications are
found in subsequent sections of this chapter. These are
a b a b 1
0x 0y
(11.15)
0y z 0x z
and
a b a b a b 1
0y 0z 0x
(11.16)
0z x 0x y 0y z
for example. . . consider the three quantities x, y, and z, any two of which may
be selected as the independent variables. Thus, we can write x x(y, z) and y y(x, z). The
differentials of these functions are, respectively
dx a b dy
a b dz dy a b dx
a b dz
0x 0x 0y 0y
and
0y z 0z y 0x z 0z x
Eliminating dy between these two equations results in
c1 a b a b d dx c a b a b
a b d dz
0x 0y 0x 0y 0x
(11.17)
0y z 0x z 0y z 0z x 0z y
Since x and z can be varied independently, let us hold z constant and vary x. That is, let
dz 0 and dx 0. It then follows from Eq. 11.17 that the coefficient of dx must vanish, so
Eq. 11.15 must be satisfied. Similarly, when dx 0 and dz 0, the coefficient of dz in
Eq. 11.17 must vanish. Introducing Eq. 11.15 into the resulting expression and rearranging
gives Eq. 11.16. The details are left as an exercise.
APPLICATION. An equation of state p p(T, v) provides a specific example of a function

of two independent variables. The partial derivatives (0p0T )v and (0p0v)T of p(T, v) are im-
portant for subsequent discussions. The quantity (0p0T )v is the partial derivative of p with
respect to T (the variable v being held constant). This partial derivative represents the slope
at a point on a line of constant specific volume (isometric) projected onto the pT plane.
Similarly, the partial derivative (0p0v)T is the partial derivative of p with respect to v (the
variable T being held constant). This partial derivative represents the slope at a point on
a line of constant temperature (isotherm) projected on the pv plane. The partial derivatives
(0p0T )v and (0p0v)T are themselves intensive properties because they have unique values
at each state.
The pvT surfaces given in Figs. 3.1 and 3.2 are graphical representations of func-
tions of the form p p(v, T ). Figure 11.1 shows the liquid, vapor, and two-phase regions
of a pvT surface projected onto the pv and pT planes. Referring first to Fig. 11.1a,
note that several isotherms are sketched. In the single-phase regions, the partial deriva-
tive (0p0v)T giving the slope is negative at each state along an isotherm except at the crit-
ical point, where the partial derivative vanishes. Since the isotherms are horizontal in the
two-phase liquidvapor region, the partial derivative (0p0v)T vanishes there as well. For
these states, pressure is independent of specific volume and is a function of temperature
only: p psat(T ).
Figure 11.1b shows the liquid and vapor regions with several isometrics (constant specific
volume lines) superimposed. In the single-phase regions, the isometrics are nearly straight
or are slightly curved and the partial derivative (0p0T )v is positive at each state along the
curves. For the two-phase liquidvapor states corresponding to a specified value of temper-
ature, the pressure is independent of specific volume and is determined by the temperature
p p
v < vc v = vc
p
T > Tc ( (
T v > 0
tric
T = Tc p
( ( p
( (
Isome
T < Tc v T < 0 T v > 0
p Critical
( (
v T = 0
point v > vc
c
etri
Iso Isom
Critical the
rm
p point
( (
< 0
v T
Liquid Vapor
(p/v)T = 0 dp
Iso
the ( (
dT sat
rm
Liquid-vapor
Locus of saturation states
Triple
point
v T
(a) (b)
Figure 11.1 Diagrams used to discuss (0p0v)T and (0p0T)v. (a) pv diagram.
(b) Phase diagram.
only. Hence, the slopes of the isometrics passing through the two-phase states corresponding
to a specified temperature are all equal, being given by the slope of the saturation curve at
that temperature, denoted simply as (dpdT )sat. For these two-phase states, ( 0 p 0 T )v
(dpdT )sat.
In this section, important aspects of functions of two variables have been introduced.
The following example illustrates some of these ideas using the van der Waals equation
of state.
EXAMPLE 11.2 Applying Mathematical Relations
For the van der Waals equation of state, (a) determine an expression for the exact differential dp, (b) show that the mixed sec-
ond partial derivatives of the result obtained in part (a) are equal, and (c) develop an expression for the partial derivative
(0v0T)p.
SOLUTION
Known: The equation of state is the van der Waals equation.
Find: Determine the differential dp, show that the mixed second partial derivatives of dp are equal, and develop an expres-
sion for (0v0T )p.
Analysis:
(a) By definition, the differential of a function p p(T, v) is
dp a b dT
a b dv
0p 0p
0T v 0v T
The partial derivatives appearing in this expression obtained from the van der Waals equation expressed as p
RT(v b) av2 are
Ma b Na b
0p R 0p RT 2a

3
1v b2
,
0T v v b 0v T 2
v
Accordingly, the differential takes the form

RT
dp a b dT
c
3 d dv
R 2a
vb 1v b2 2 v
(b) Calculating the mixed second partial derivatives
a b ca b d
0M 0 0p R
0v T 0v 0T v T 1v b2 2
a b ca b d
0N 0 0p R
0T v 0T 0v T v 1v b2 2
Thus, the mixed second partial derivatives are equal, as expected.
(c) An expression for (0v0T )p can be derived using Eqs. 11.15 and 11.16. Thus, with x p, y v, and z T, Eq. 11.16
gives
a b a b a b 1
0v 0p 0T
0T p 0v T 0p v
or
a b
0v 1
0T p 10p 0v2 T 10T 0p2 v
Then, with x T, y p, and z v, Eq. 11.15 gives
a b
0T 1
0p v 10p 0T 2 v
Combining these results
10p 0T 2 v
a b
0v
0T p 10p 0v2 T
The numerator and denominator of this expression have been evaluated in part (a), so
R 1v b2
a
0v
b
0T p 3 RT 1v b2 2
2av3 4
which is the desired result.
Since the van der Waals equation is cubic in specific volume, it can be solved for v (T, p) at only certain states. Part (c)
shows how the partial derivative (0v0T )p can be evaluated at states where it exists.

11.3 Developing Property Relations
In this section, several important property relations are developed, including the expressions
known as the Maxwell relations. The concept of a fundamental thermodynamic function is
also introduced. These results, which are important for subsequent discussions, are obtained
for simple compressible systems of fixed chemical composition using the concept of an exact
differential.
11.3.1 Principal Exact Differentials

The principal results of this section are obtained using Eqs. 11.18, 11.19, 11.22, and 11.23.
The first two of these equations are derived in Sec. 6.3.1, where they are referred to as the
T ds equations. For present purposes, it is convenient to express them as
du T ds p dv (11.18)
dh T ds
v dp (11.19)
The other two equations used to obtain the results of this section involve, respectively, the
Helmholtz function specific Helmholtz function defined by
c u Ts (11.20)
Gibbs function and the specific Gibbs function g defined by
g h Ts (11.21)
The Helmholtz and Gibbs functions are properties because each is defined in terms of
properties. From inspection of Eqs. 11.20 and 11.21, the units of and g are the same
as those of u and h. These two new properties are introduced solely because they con-
tribute to the present discussion, and no physical significance need be attached to them
at this point.
Forming the differential d
dc du d1Ts2 du T ds s dT
Substituting Eq. 11.18 into this gives
dc p dv s dT (11.22)
Similarly, forming the differential dg

dg dh d1Ts2 dh T ds s dT
Substituting Eq. 11.19 into this gives
dg v dp s dT (11.23)
11.3.2 Property Relations from Exact Differentials

The four differential equations introduced above, Eqs. 11.18, 11.19, 11.22, and 11.23, pro-
vide the basis for several important property relations. Since only properties are involved,
each is an exact differential exhibiting the general form dz M dx
N dy considered in
Sec. 11.2. Underlying these exact differentials are, respectively, functions of the form
u(s, v), h(s, p), (v, T), and g(T, p). Let us consider these functions in the order given.
The differential of the function u u(s, v) is
du a b ds
a b dv
0u 0u
0s v 0v s
By comparison with Eq. 11.18, we conclude that
Ta b
0u
(11.24)
0s v
p a b
0u
(11.25)
0v s
The differential of the function h h(s, p) is
dh a b ds
a b dp
0h 0h
0s p 0p s
By comparison with Eq. 11.19, we conclude that
Ta b
0h
(11.26)
0s p
va b
0h
(11.27)
0p s
Similarly, the coefficients p and s of Eq. 11.22 are partial derivatives of (v, T )
p a b
0c
(11.28)
0v T
s a b
0c
(11.29)
0T v
and the coefficients v and s of Eq. 11.23 are partial derivatives of g(T, p)
va b
0g
(11.30)
0p T
s a b
0g
(11.31)
0T p
As each of the four differentials introduced above is exact, the second mixed partial de-
rivatives are equal. Thus, in Eq. 11.18, T plays the role of M in Eq. 11.14b and p plays the
role of N in Eq. 11.14b, so
a b a b
0T 0p
(11.32)
0v s 0s v
In Eq. 11.19, T and v play the roles of M and N in Eq. 11.14b, respectively. Thus
a b a b
0T 0v
(11.33)
0p s 0s p
Similarly, from Eqs. 11.22 and 11.23 follow
a b a b
0p 0s
(11.34)
0T v 0v T
a b a b
0v 0s
(11.35)
0T p 0p T
Equations 11.32 through 11.35 are known as the Maxwell relations. Maxwell relations
TABLE 11.1 Summary of Property Relations from Exact Differentials

Basic relations:
from u u(s, v) from h h(s, p)
Ta b Ta b
0u 0h
(11.24) (11.26)
0s v 0s p
p a b va b
0u 0h
(11.25) (11.27)
0v s 0p s
from (v, T ) from g g(T, p)
p a b va b
0c 0g
(11.28) (11.30)
0v T 0p T
s a b s a b
0c 0g
(11.29) (11.31)
0T v 0T p
Maxwell relations:
a b a b a b a b
0T 0p 0p 0s
(11.32) (11.34)
0v s 0s v 0T v 0v T
a b a b a b a b
0T 0v 0v 0s
(11.33) (11.35)
0p s 0s p 0T p 0p T
Additional relations:
a b a b a b a b
0u 0h 0u 0c
0s v 0s p 0v s 0v T
(11.36)
a b a b a b a b
0h 0g 0c 0g
0p s 0p T 0T v 0T p
Since each of the properties T, p, v, s appears on the left side of two of the eight equa-
tions, Eqs. 11.24 through 11.31, four additional property relations can be obtained by equat-
ing such expressions. They are
a b a b, a b a b
0u 0h 0u 0c
0s v 0s p 0v s 0v T
(11.36)
a b a b, a b a b
0h 0g 0c 0g
0p s 0p T 0T v 0T p
Equations 11.24 through 11.36, which are listed in Table 11.1 for ease of reference, are
16 property relations obtained from Eqs. 11.18, 11.19, 11.22, and 11.23, using the concept
of an exact differential. Since Eqs. 11.19, 11.22, and 11.23 can themselves be derived from
Eq. 11.18, the important role of the first T dS equation in developing property relations is
apparent.
The utility of these 16 property relations is demonstrated in subsequent sections of this
chapter. However, to give a specific illustration at this point, suppose the partial deriva-
tive ( 0 s 0 v)T involving entropy is required for a certain purpose. The Maxwell relation
Eq. 11.34 would allow the derivative to be determined by evaluating the partial derivative
( 0 p 0 T)v, which can be obtained using pvT data only. Further elaboration is provided
in Example 11.3.
EXAMPLE 11.3 Applying the Maxwell Relations
Evaluate the partial derivative (0s0v)T for water vapor at a state fixed by a temperature of 240C and a specific volume of
0.4646 m3/kg. (a) Use the RedlichKwong equation of state and an appropriate Maxwell relation. (b) Check the value obtained
using steam table data.
SOLUTION
Known: The system consists of a fixed amount of water vapor at 240C and 0.4646 m3/kg.
Find: Determine the partial derivative (0s0v)T employing the RedlichKwong equation of state, together with a Maxwell
relation. Check the value obtained using steam table data.
Assumptions:
1. The system consists of a fixed amount of water at a known equilibrium state.

2. Accurate values for (0s0T )v in the neighborhood of the given state can be determined from the RedlichKwong equation
of state.
Analysis:
(a) The Maxwell relation given by Eq. 11.34 allows (0s0v)T to be determined from the pvT relationship. That is
a b a b
0s 0p
0v T 0T v
The partial derivative (0p0T )v obtained from the RedlichKwong equation, Eq. 11.7, is
a b
0p R a

0T v v b 2v 1v
b2T 32
At the specified state, the temperature is 513 K and the specific volume on a molar basis is
m3 18.02 kg m3
v 0.4646 a b 8.372
kg kmol kmol
From Table A-24
m3 2 1 2 m3
a 142.59 bar a b 1K2 , b 0.0211
kmol kmol
Substituting values into the expression for (0p0T )v
m3 2
a8314 b 142.59 bar a b 1K2 1 2
N#m
105 N/m2
a b ` `
0p #
kmol K kmol
3
2 3
18.372 0.02112 2 a8.372 b a8.3931 b 1513 K2 32
0T v m m m 1 bar
kmol kmol kmol
a1004.3 3 # b ` 3 # `
#
N m 1 kJ
m K 10 N m
kJ
1.0043 3
m #K
Accordingly
a b 1.0043 3 #
0s kJ
0v T m K
(b) A value for (0s0v)T can be estimated using a graphical approach with steam table data, as follows: At 240C, Table A-4
provides the values for specific entropy s and specific volume v tabulated below
T 240C
p (bar) s (kJ/ kg # K) (m3/kg)
1.0 7.9949 2.359
1.5 7.8052 1.570
3.0 7.4774 0.781
5.0 7.2307 0.4646
7.0 7.0641 0.3292
10.0 6.8817 0.2275
With the values for s and v listed in the table, the plot in Fig. E11.3a giving s versus v can be prepared. Note that a line repre-
senting the tangent to the curve at the given state is shown on the plot. The pressure at this state is 5 bar. The slope of the tan-
gent is (0s0v)T 1.0 kJ/m3 # K. Thus, the value of (0s0v)T obtained using the RedlichKwong equation agrees closely with
the result determined graphically using steam table data.
T = 240C 1.5 bar

Specific entropy, kJ/kgK
7.5
3 bar
5 bar
7 bar
7.0
0.5 1.0 1.5
Specific volume, m3/kg
Figure E11.3a
Alternative Solution:
Alternatively, the partial derivative (0s0v)T can be estimated using numerical methods and computer-generated data. The
following IT code illustrates one way the partial derivative, denoted dsdv, can be estimated:
v = 0.4646 // m3/kg
T = 240 // C
v2 = v + dv
v1 = v dv
dv = 0.2
v2 = v_PT(Water/Steam, p2, T)
v1 = v_PT(Water/Steam, p1, T)
s2 = s_PT(Water/Steam, p2, T)
s1 = s_PT(Water/Steam, p1, T)
dsdv = (s2 s1) / (v2 v1)
Using the Explore button, sweep dv from 0.0001 to 0.2 in steps of 0.001. Then, using the Graph button, the following graph
can be constructed:
1.12
1.10
T = 240C
1.08
dsdv
1.06
1.04
1.02
1.00
0.00 0.05 0.10 0.15 0.20
dv
Figure E11.3b
From the computer data, the y-intercept of the graph is
a b lim a b 1.033 3 #
0s s kJ
0v T vS0 v T m K
This answer is an estimate because it relies on a numerical approximation of the partial derivative based on the equation of
state that underlies the steam tables. The values obtained using the RedlichKwong equation of state and the graphical method
agree with this result.
It is left as an exercise to show that, in accordance with Eq. 11.34, the value of (0p0T )v estimated by a procedure like the
one used for (0s0v)T would agree with the value obtained here.
11.3.3 Fundamental Thermodynamic Functions

A fundamental thermodynamic function provides a complete description of the thermody-
namic state. In the case of a pure substance with two independent properties, the fundamental
thermodynamic function can take one of the following four forms:
u u1s, v2
h h1s, p2
(11.37) fundamental function
c c1T, v2
g g1T, p2
Of the four fundamental functions listed in Eqs. 11.37, the Helmholtz function and the
Gibbs function g have the greatest importance for subsequent discussions (see Sec. 11.6.2).
Accordingly, let us discuss the fundamental function concept with reference to and g.
In principle, all properties of interest can be determined from a fundamental thermody-
namic function by differentiation and combination. for example. . . consider a fun-
damental function of the form (T, v). The properties v and T, being the independent
variables, are specified to fix the state. The pressure p at this state can be determined from
Eq. 11.28 by differentiation of (T, v). Similarly, the specific entropy s at the state can be
found from Eq. 11.29 by differentiation. By definition, u Ts, so the specific internal
energy is obtained as
u c
Ts
With u, p, and v known, the specific enthalpy can be found from the definition h u
pv.
Similarly, the specific Gibbs function is found from the definition, g h Ts. The specific
heat cv can be determined by further differentiation, cv ( 0 u 0 T )v. Other properties can be
calculated with similar operations.
for example. . . consider a fundamental function of the form g(T, p). The proper-
ties T and p are specified to fix the state. The specific volume and specific entropy at this
state can be determined by differentiation from Eqs. 11.30 and 11.31, respectively. By defi-
nition, g h Ts, so the specific enthalpy is obtained as
h g
Ts
With h, p, and v known, the specific internal energy can be found from u h pv. The
specific heat cp can be determined by further differentiation, cp ( 0 h 0 T )p. Other proper-
ties can be calculated with similar operations.
Like considerations apply for functions of the form u(s, v) and h(s, p), as can readily be
verified. Note that a Mollier diagram provides a graphical representation of the fundamen-
tal function h(s, p).

11.4 Evaluating Changes in Entropy, Internal
Energy, and Enthalpy
With the introduction of the Maxwell relations, we are in a position to develop thermody-
namic relations that allow changes in entropy, internal energy, and enthalpy to be evaluated
from measured property data. The presentation begins by considering relations applicable to
phase changes and then turns to relations for use in single-phase regions.
11.4.1 Considering Phase Change

The object of this section is to develop relations for evaluating the changes in specific en-
tropy, internal energy, and enthalpy accompanying a change of phase at fixed temperature
and pressure. A principal role is played by the Clapeyron equation, which allows the change
in enthalpy during vaporization, sublimation, or melting at a constant temperature to be eval-
uated from pressure-specific volumetemperature data pertaining to the phase change. Thus,
the present discussion provides important examples of how pvT measurements can lead to
the determination of other property changes, namely s, u, and h for a change of phase.
Consider a change in phase from saturated liquid to saturated vapor at fixed temperature.
For an isothermal phase change, pressure also remains constant, so Eq. 11.19 reduces to
dh T ds
Integration of this expression gives
hg hf
sg sf (11.38)
T
11.4 Evaluating Changes in Entropy, Internal Energy, and Enthalpy 505
Hence, the change in specific entropy accompanying a phase change from saturated liquid
to saturated vapor at temperature T can be determined from the temperature and the change
in specific enthalpy.
The change in specific internal energy during the phase change can be determined using
the definition h u
pv.
ug uf hg hf p 1vg vf 2 (11.39)
Thus, the change in specific internal energy accompanying a phase change at temperature T
can be determined from the temperature and the changes in specific volume and enthalpy.
CLAPEYRON EQUATION. The change in specific enthalpy required by Eqs. 11.38 and 11.39
can be obtained using the Clapeyron equation. To derive the Clapeyron equation, begin with
the Maxwell relation
a b a b
0s 0p
(11.34)
0v T 0T v
During a phase change at fixed temperature, the pressure is independent of specific volume
and is determined by temperature alone. Thus, the quantity ( 0 p 0 T)v is determined by the
temperature and can be represented as
a b a b
0p dp
0T v dT sat
where sat indicates that the derivative is the slope of the saturation pressuretemperature
curve at the point determined by the temperature held constant during the phase change
(Sec. 11.2). Combining the last two equations gives
a b a b
0s dp
0v T dT sat
Since the right side of this equation is fixed when the temperature is specified, the equa-
tion can be integrated to give
sg sf a b 1v vf 2
dp
dT sat g
Introducing Eq. 11.38 into this expression results in the Clapeyron equation
hg hf
a b
dp
dT sat T 1vg vf 2
(11.40) Clapeyron equation
Equation 11.40 allows (hg hf) to be evaluated using only pvT data pertaining to the phase
change. In instances when the enthalpy change is also measured, the Clapeyron equation can
be used to check the consistency of the data. Once the specific enthalpy change is deter-
mined, the corresponding changes in specific entropy and specific internal energy can be
found from Eqs. 11.38 and 11.39, respectively.
Equations 11.38, 11.39, and 11.40 also can be written for sublimation or melting occur-
ring at constant temperature and pressure. In particular, the Clapeyron equation would take
the form
h h
a b
dp
dT sat T 1v v2
(11.41)
where and denote the respective phases, and (dpdT )sat is the slope of the relevant satu-
ration pressuretemperature curve.
The Clapeyron equation shows that the slope of a saturation line on a phase diagram de-
pends on the signs of the specific volume and enthalpy changes accompanying the phase
change. In most cases, when a phase change takes place with an increase in specific enthalpy,
the specific volume also increases, and (dpdT )sat is positive. However, in the case of the
melting of ice and a few other substances, the specific volume decreases on melting. The
slope of the saturated solidliquid curve for these few substances is negative, as was pointed
out in Sec. 3.2.2 in the discussion of phase diagrams.
An approximate form of Eq. 11.40 can be derived when the following two idealizations
are justified: (1) vf is negligible in comparison to vg, and (2) the pressure is low enough that
vg can be evaluated from the ideal gas equation of state as vg RTp. With these, Eq. 11.40
becomes
hg hf
a b
dp
dT sat RT 2 p
which can be rearranged to read
hg hf
a b
d ln p
(11.42)
dT sat RT 2
ClausiusClapeyron Equation 11.42 is called the ClausiusClapeyron equation. A similar expression applies for
equation the case of sublimation.
The use of the Clapeyron equation in any of the foregoing forms requires an accurate rep-
resentation for the relevant saturation pressuretemperature curve. This must not only depict
the pressuretemperature variation accurately but also enable accurate values of the deriva-
tive (dpdT)sat to be determined. Analytical representations in the form of equations are com-
monly used. Different equations for different portions of the pressuretemperature curves
may be required. These equations can involve several constants. One form that is used for
the vapor-pressure curves is the four-constant equation
B
ln psat A

C ln T
DT
T
in which the constants A, B, C, D are determined empirically.
The use of the Clapeyron equation for evaluating changes in specific entropy, internal en-
ergy, and enthalpy accompanying a phase change at fixed T and p is illustrated in the next
example.
EXAMPLE 11.4 Applying the Clapeyron Equation
Using pvT data for saturated water, calculate at 100C (a) hg hf, (b) ug uf, (c) sg sf. Compare with the respective
steam table value.
SOLUTION
Known: The system consists of a unit mass of saturated water at 100C.
Find: Using saturation data, determine at 100C the change on vaporization of the specific enthalpy, specific internal energy,
and specific entropy, and compare with the respective steam table value.
Analysis: For comparison, Table A-2 gives at 100C, hg hf 2257.0 kJ/kg, ug uf 2087.6 kg/kg, sg sf 6.048
kJ/kg # K.
(a) The value of hg hf can be determined from the Clapeyron equation, Eq. 11.40, expressed as
hg hf T 1vg vf 2 a b
dp
dT sat
This equation requires a value for the slope (dpdT)sat of the saturation pressuretemperature curve at the specified temperature.
The required value for (dpdT )sat at 100C can be estimated graphically as follows. Using saturation pressuretemperature
data from the steam tables, the accompanying plot can be prepared. Note that a line drawn tangent to the curve at 100C is
shown on the plot. The slope of this tangent line is about 3570 N/m2 # K. Accordingly, at 100C
a b 3570 2 #
dp N
dT sat m K
4
Saturation pressure (bar)
0
40 60 80 100 120 140
Temperature (C)
Figure E11.4
Inserting values into the above equation for hg hf gives

m3
hg hf 1373.15 K2 11.673 1.0435 103 2 a b a3570 2 # b ` 3 # `
N 1 kJ
kg m K 10 N m
2227 kJ/kg
This value is about 1% less than the value read from the steam tables.
Alternatively, the derivative (dpdT )sat can be estimated using numerical methods and computer-generated data. The fol-
lowing IT code illustrates one way the derivative, denoted dpdT, can be estimated:
T = 100 // C
dT = 0.001
T1 = T dT
T2 = T + dT
p1 = Psat(Water/Steam, T1) // bar
p2 = Psat(Water/Steam, T2) // bar
dpdT = ((p2 p1) / (T2 T1)) * 100000
Using the Explore button, sweep dT from 0.001 to 0.01 in steps of 0.001. Then, reading the limiting value from the computer
data
a b 3616 2 #
dp N
dT sat m K
When this value is used in the above expression for hg hf, the result is hg hf 2256 kJ/kg, which agrees very closely
with the value read from the steam tables.
(b) With Eq. 11.39

ug uf hg hf psat 1vg vf 2
Inserting the IT result for (hg hf) from part (a) together with saturation data at 100C
m3
a1.014 105 2 b a1.672 b ` 3 # `
kJ N 1 kJ
ug uf 2256
kg m kg 10 N m
kJ
2086.5
kg
which also agrees closely with the value from the steam tables.
(c) With Eq. 11.38 and the IT result for (hg hf) from part (a)
hg hf 2256 kJ/kg kJ
sg sf 6.046 #
T 373.15 K kg K
which again agrees very closely with the steam table value.
Also, (dpdT)sat might be obtained by differentiating an analytical expression for the vapor pressure curve, as discussed in
Sec. 11.4.1 above.
11.4.2 Considering Single-Phase Regions

The objective of the present section is to derive expressions for evaluating s, u, and h
between states in single-phase regions. These expressions require both pvT data and ap-
propriate specific heat data. Since single-phase regions are under present consideration, any
two of the properties pressure, specific volume, and temperature can be regarded as the in-
dependent properties that fix the state. Two convenient choices are T, v and T, p.
T AND v AS INDEPENDENT PROPERTIES. With temperature and specific volume as the

independent properties that fix the state, the specific entropy can be regarded as a function
of the form s s(T, v). The differential of this function is
ds a b dT
a b dv
0s 0s
0T v 0v T
The partial derivative ( 0 s 0 v)T appearing in this expression can be replaced using the Maxwell
relation, Eq. 11.34, giving
ds a b dT
a b dv
0s 0p
(11.43)
0T v 0T v
The specific internal energy also can be regarded as a function of T and v: u u(T, v).
The differential of this function is
du a b dT
a b dv
0u 0u
0T v 0v T
With cv ( 0 u 0 T)v
du cv dT
a b dv
0u
(11.44)
0v T
Substituting Eqs. 11.43 and 11.44 into du T ds p dv and collecting terms results in
ca b
p T a b d dv c T a b cv d dT
0u 0p 0s
(11.45)
0v T 0T v 0T v
Since specific volume and temperature can be varied independently, let us hold specific vol-
ume constant and vary temperature. That is, let dv 0 and dT 0. It then follows from
Eq. 11.45 that
a b
0s cv
(11.46)
0T v T
Similarly, suppose that dT 0 and dv 0. It then follows that
a b Ta b p
0u 0p
(11.47)
0v T 0T v
Equations 11.46 and 11.47 are additional examples of useful thermodynamic property
relations. for example. . . Equation 11.47, which expresses the dependence of the spe-
cific internal energy on specific volume at fixed temperature, allows us to demonstrate that the
internal energy of a gas whose equation of state is pv RT depends on temperature alone,
a result first discussed in Sec. 3.5. Equation 11.47 requires the partial derivative ( 0 p 0 T)v.
If p RTv, the derivative is ( 0 p 0 T )v Rv. Introducing this, Eq. 11.47 gives
a b Ta b pTa bppp0

0u 0p R
0v T 0T v v
This demonstrates that when pv RT, the specific internal energy is independent of specific
volume and depends on temperature alone.
Continuing the discussion, when Eq. 11.46 is inserted in Eq. 11.43, the following ex-
pression results
dT
a b dv
cv 0p
ds (11.48)
T 0T v
Inserting Eq. 11.47 into Eq. 11.44 gives
du cv dT
c T a b p d dv
0p
(11.49)
0T v
Observe that the right sides of Eqs. 11.48 and 11.49 are expressed solely in terms of p, v, T,
and cv.
Changes in specific entropy and internal energy between two states are determined by in-
tegration of Eqs. 11.48 and 11.49, respectively
a b dv
2 cv 2 0p
s2 s1 dT
(11.50)
1 T 1 0T v
cT a b p d dv
2 2 0p
u2 u1 cv dT
(11.51)
1 1 0T v
To integrate the first term on the right of each of these expressions, the variation of cv
with temperature at one fixed specific volume (isometric) is required. Integration of the
2
1 vx = vy
y
T2 = Ty
x
cv = cv(T, vx) T1 = Tx
Figure 11.2 Integration path between
v two vapor states.
second term requires knowledge of the pvT relation at the states of interest. An equa-
tion of state explicit in pressure would be particularly convenient for evaluating the inte-
grals involving ( 0 p 0 T )v. The accuracy of the resulting specific entropy and internal en-
ergy changes would depend on the accuracy of this derivative. In cases where the
integrands of Eqs. 11.50 and 11.51 are too complicated to be integrated in closed form
they may be evaluated numerically. Whether closed-form or numerical integration is used,
attention must be given to the path of integration.
for example. . . let us consider the evaluation of Eq. 11.51. Referring to Fig. 11.2,
if the specific heat cv is known as a function of temperature along the isometric (constant
specific volume) passing through the states x and y, one possible path of integration for de-
termining the change in specific internal energy between states 1 and 2 is 1xy2. The in-
tegration would be performed in three steps. Since the temperature is constant from state 1
to state x, the first integral of Eq. 11.51 would vanish, so
vx
cT a b p d dv
0p
ux u1
v1 0T v
From state x to y, the specific volume is constant and cv is known as a function of temper-
ature only, so

Ty
uy ux cv dT
Tx
where Tx T1 and Ty T2. From state y to state 2, the temperature is constant once again,
and
v2
cT a b p d dv
0p
u2 uy
vy vx 0T v
When these are added, the result is the change in specific internal energy between states 1
and 2.
T AND p AS INDEPENDENT PROPERTIES. In this section a presentation parallel to that

considered above is provided for the choice of temperature and pressure as the independent
properties. With this choice for the independent properties, the specific entropy can be re-
garded as a function of the form s s(T, p). The differential of this function is
ds a b dT
a b dp
0s 0s
0T p 0p T
The partial derivative ( 0s 0p)T appearing in this expression can be replaced using the Maxwell
relation, Eq. 11.35, giving
ds a b dT a b dp
0s 0v
(11.52)
0T p 0T p
The specific enthalpy also can be regarded as a function of T and p: h h(T, p). The dif-
ferential of this function is
dh a b dT
a b dp
0h 0h
0T p 0p T
With cp (0h 0T ) p
dh cp dT
a b dp
0h
(11.53)
0p T
Substituting Eqs. 11.52 and 11.53 into dh T ds
v dp and collecting terms results in
ca b
T a b v d dp c T a b cp d dT
0h 0v 0s
(11.54)
0p T 0T p 0T p
Since pressure and temperature can be varied independently, let us hold pressure constant
and vary temperature. That is, let dp 0 and dT 0. It then follows from Eq. 11.54 that
cp
a b
0s
(11.55)
0T p T
Similarly, when dT 0 and dp 0, Eq. 11.54 gives
a b vTa b
0h 0v
(11.56)
0p T 0T p
Equations 11.55 and 11.56, like Eqs. 11.46 and 11.47, are useful thermodynamic property
relations.
When Eq. 11.55 is inserted in Eq. 11.52, the following equation results:
cp
dT a b dp
0v
ds (11.57)
T 0T p
Introducing Eq. 11.56 into Eq. 11.53 gives
dh cp dT
c v T a b d dp
0v
(11.58)
0T p
Observe that the right sides of Eqs. 11.57 and 11.58 are expressed solely in terms of p, v, T,
and cp.
Changes in specific entropy and enthalpy between two states are found by integrating
Eqs. 11.57 and 11.58, respectively
cp
T a b dp
2 2 0v
s2 s1 dT (11.59)
1 1 0T p
c dT
cv T a b d dp
2 2 0v
h2 h1 p (11.60)
1 1 0T p
To integrate the first term on the right of each of these expressions, the variation of cp with
temperature at one fixed pressure (isobar) is required. Integration of the second term requires
knowledge of the pvT behavior at the states of interest. An equation of state explicit in v
would be particularly convenient for evaluating the integrals involving ( 0v 0T )p. The accu-
racy of the resulting specific entropy and enthalpy changes would depend on the accuracy
of this derivative.
Changes in specific enthalpy and internal energy are related through h u
pv by
h2 h1 1u2 u1 2
1 p2v2 p1v1 2 (11.61)
Hence, only one of h and u need be found by integration. Then, the other can be eval-
uated from Eq. 11.61. Which of the two property changes is found by integration depends
on the information available. h would be found using Eq. 11.60 when an equation of
state explicit in v and cp as a function of temperature at some fixed pressure are known.
u would be found from Eq. 11.51 when an equation of state explicit in p and cv as a
function of temperature at some specific volume are known. Such issues are considered
in Example 11.5.
EXAMPLE 11.5 Evaluating s, u, and h of a Gas
Using the RedlichKwong equation of state, develop expressions for the changes in specific entropy, internal energy, and en-
thalpy of a gas between two states where the temperature is the same, T1 T2, and the pressures are p1 and p2, respectively.
SOLUTION
Known: Two states of a unit mass of a gas as the system are fixed by p1 and T1 at state 1 and p2, T2 ( T1) at state 2.
Find: Determine the changes in specific entropy, internal energy, and enthalpy between these two states.
Assumption: The RedlichKwong equation of state represents the pvT

2
p2 behavior at these states and yields accurate values for (0p0T )v.
1
p1
Iso
the
rm
v2 v1 v
Figure E11.5
Analysis: The RedlichKwong equation of state is explicit in pressure, so Eqs. 11.50 and 11.51 are selected for determin-
ing s2 s1 and u2 u1. Since T1 T2, an isothermal path of integration between the two states is convenient. Thus, these
equations reduce to give
a b dv
2 0p
s2 s1
1 0T v
cT a b p d dv
2 0p
u2 u1
1 0T v
The limits for each of the foregoing integrals are the specific volumes v1 and v2 at the two states under consideration.
Using p1, p2, and the known temperature, these specific volumes would be determined from the RedlichKwong equation of
state. Since this equation is not explicit in specific volume, the use of an equation solver such as Interactive Thermodynamics:
IT is recommended.
The above integrals involve the partial derivative (0p0T )v, which can be determined from the RedlichKwong equation
of state as
a b
0p R a

0T v v b 2v1v
b2 T 32
Inserting this into the expression for (s2 s1) gives
v2
c d dv
R a
s2 s1
v1 vb 2v1v
b2 T 3 2
v2
c a b d dv
R a 1 1

v1 vb 2bT 32 v v

b
v2 b v2
b
R ln a b
c ln a b ln a bd
a v2
32
v1 b 2bT v1 v1
b
v2 b v2 1v1
b2
R ln a b
ln c d
a
1 1v2
b2
32
v1 b 2 bT v
With the RedlichKwong equation, the integrand of the expression for (u2 u1) becomes
cT a b pd T c d c d
0p R a RT a

0T v vb 2v1v
b2 T 32 vb v1v
b2 T 1 2
3a

2v1v
b2 T 12
Accordingly
v2 v2
a b dv
3a 3a 1 1
u2 u1 dv
v1 2v1v
b2 T 12 2 bT 12 v1 v v
b
v2
b v2 1v1
b2
c ln ln a bd ln c d
3a v2 3a

2 bT 12 v1 v1
b 2 bT 12 v1 1v2
b2
Finally, (h2 h1) would be determined using Eq. 11.61 together with the known values of (u2 u1), p1, v1, p2, and v2.

11.5 Other Thermodynamic Relations
The presentation to this point has been directed mainly at developing thermodynamic relations
that allow changes in u, h, and s to be evaluated from measured property data. The object of
the present section is to introduce several other thermodynamic relations that are useful for
thermodynamic analysis. Each of the properties considered has a common attribute: it is de-
fined in terms of a partial derivative of some other property. The specific heats cv and cp are
examples of this type of property.
11.5.1 Volume Expansivity, Isothermal and

Isentropic Compressibility
In single-phase regions, pressure and temperature are independent, and we can think of the spe-
cific volume as being a function of these two, v v(T, p). The differential of such a function is
dv a b dT
a b dp
0v 0v
0T p 0p T
Two thermodynamic properties related to the partial derivatives appearing in this differ-
ential are the volume expansivity , also called the coefficient of volume expansion
a b
1 0v
volume expansivity b (11.62)
v 0T p
and the isothermal compressibility
k a b
isothermal 1 0v
(11.63)
compressibility v 0p T
By inspection, the unit for is seen to be the reciprocal of that for temperature and the unit
for
is the reciprocal of that for pressure. The volume expansivity is an indication of the
change in volume that occurs when temperature changes while pressure remains constant.
The isothermal compressibility is an indication of the change in volume that takes place when
pressure changes while temperature remains constant. The value of
is positive for all sub-
stances in all phases.
The volume expansivity and isothermal compressibility are thermodynamic properties,
and like specific volume are functions of T and p. Values for and
are provided in hand-
books of engineering data. Table 11.2 gives values of these properties for liquid water at a
pressure of 1 atm versus temperature. For a pressure of 1 atm, water has a state of maximum
density at about 4C. At this state, the value of is zero.
The isentropic compressibility is an indication of the change in volume that occurs
when pressure changes while entropy remains constant
a a b
1 0v
isentropic compressibility (11.64)
v 0p s
The unit for is the reciprocal of that for pressure.

The isentropic compressibility is related to the speed at which sound travels in the sub-
stance, and such speed measurements can be used to determine . In Sec. 9.12, the velocity
of sound, or sonic velocity, is introduced as
v2 a b
0p
velocity of sound c (9.36b)
B 0v s
TABLE 11.2 Volume Expansivity and Isothermal Compressibility

of Liquid Water at 1 atm versus Temperature
T Density 106
106
(C) (kg/m3) (K)1 (bar)1
0 999.84 68.14 50.89
10 999.70 87.90 47.81
20 998.21 206.6 45.90
30 995.65 303.1 44.77
40 992.22 385.4 44.24
50 988.04 457.8 44.18
The relationship of the isentropic compressibility and the velocity of sound can be obtained
using the relation between partial derivatives expressed by Eq. 11.15. Identifying p with x, v
with y, and s with z, we have
a b
0p 1
0v s 1 0v 0p2 s
With this, the previous two equations can be combined to give
c 1va (11.65)
The details are left as an exercise.
11.5.2 Relations Involving Specific Heats

In this section, general relations are obtained for the difference between specific heats (cp cv)
and the ratio of specific heats cpcv.
EVALUATING (cp cv). An expression for the difference between cp and cv can be obtained
by equating the two differentials for entropy given by Eqs. 11.48 and 11.57 and rearranging
to obtain
1cp cv 2 dT T a b dv
T a b dp
0p 0v
0T v 0T p
Considering the equation of state p p(T, v), the differential dp can be expressed as
b dT
b dv
0p 0p
dp
0T v 0v T
Eliminating dp between the last two equations and collecting terms gives
c 1cp cv 2 T a b a b d dT T c a b a b
a b d dv
0v 0p 0v 0p 0p
0T p 0T v 0T p 0v T 0T v
Since temperature and specific volume can be varied independently, the coefficients of the
differentials in this expression must vanish, so
cp cv T a b a b
0v 0p
(11.66)
0T p 0T v
a b a b a b
0p 0v 0p
(11.67)
0T v 0T p 0v T
Introducing Eq. 11.67 into Eq. 11.66 gives
0v 2 0p
cp cv T a b a b (11.68)
0T p 0v T
This equation allows cv to be calculated from observed values of cp, or conversely, knowing
only pvT data. for example. . . for the special case of an ideal gas, Eq. 11.68 re-
duces to Eq. 3.44, as can readily be shown.
The right side of Eq. 11.68 can be expressed in terms of the volume expansivity and
the isothermal compressibility
. Introducing Eqs. 11.62 and 11.63, we get
Tb2
cp cv v (11.69)
k
In developing this result, the relationship between partial derivatives expressed by Eq. 11.15
has been used.
Several important conclusions about the specific heats cp and cv can be drawn from
Eq. 11.69. for example. . . since the factor 2 cannot be negative and
is positive
for all substances in all phases, the value of cp is always greater than, or equal to, cv.
The specific heats would be equal when 0, as occurs in the case of water at 1 atmos-
phere and 4C, where water is at its state of maximum density. The two specific heats also
become equal as the temperature approaches absolute zero. For some liquids and solids at
certain states, cp and cv differ only slightly. For this reason, tables often give the specific heat
of a liquid or solid without specifying whether it is cp or cv. The data reported are normally
cp values, since these are more easily determined for liquids and solids.
EVALUATING cpcv. Next, let us obtain expressions for the ratio of specific heats. Em-
ploying Eq. 11.16, we can rewrite Eqs. 11.46 and 11.55, respectively, as
1
a b
cv 0s
T 0T v 10v 0s2 T 1 0T 0v2 s
cp 1
a b
0s
T 0T p 10p 0s2 T 10T 0p2 s
Forming the ratio of these equations gives
cp 1 0v 0s2 T 1 0T 0v2 s

1 0p 0s2 T 1 0T 0p2 s
(11.70)
cv
Since ( 0 s 0 p)T 1( 0 p 0 s)T and ( 0 p 0 T )s 1( 0 T 0 p)s, Eq. 11.70 can be expressed as
cp
ca b a b d ca b a b d
0v 0s 0p 0T
(11.71)
cv 0s T 0p T 0T s 0v s
Finally, the chain rule from calculus allows us to write ( 0 v 0 p)T ( 0 v 0 s)T ( 0 s 0 p)T and
( 0 p 0 v)s ( 0 p 0 T )s ( 0 T 0 v)s, so Eq. 11.71 becomes
cp
a b a b
0v 0p
k (11.72)
cv 0p T 0v s
This can be expressed alternatively in terms of the isothermal and isentropic compressibilities as
k
k (11.73)
a
Solving Eq. 11.72 for ( 0p 0v)s and substituting the resulting expression into Eq. 9.36b
gives the following relationship involving the velocity of sound c and the specific heat ratio k
c 2kv2 10p 0v2 T (11.74)
Equation 11.74 can be used to determine c knowing the specific heat ratio and pvT data,
or to evaluate k knowing c and ( 0 p 0 v)T . for example. . . in the special case of an
ideal gas, Eq. 11.74 reduces to
c 1kRT 1ideal gas2 (9.37)
as can easily be verified.
In the next example we illustrate the use of specific heat relations introduced above.
EXAMPLE 11.6 Using Specific Heat Relations
For liquid water at 1 atm and 20C, estimate (a) the percent error in cv that would result if it were assumed that cp cv,
(b) the velocity of sound, in m /s.
SOLUTION
Known: The system consists of a fixed amount of liquid water at 1 atm and 20C.
Find: Estimate the percent error in cv that would result if cv were approximated by cp, and the velocity of sound,
in m/s.
Analysis:
(a) Equation 11.69 gives the difference between cp and cv. Table 11.2 provides the required values for the volume expansiv-
ity , the isothermal compressibility
, and the specific volume. Thus
Tb2
cp cv v
k
206.6 106 2
a b 1293 K2 a b a b
1 bar
998.21 kg/m3
K 45.90 106
bar # m3 105 N/m2
a272.96 106 b` ` ` 3 # `
1 kJ
kg # K 1 bar 10 N m
kJ
0.027
kg # K
Interpolating in Table A-19 at 20C gives cp 4.188 kJ/kg # K. Thus, the value of cv is
cv 4.188 0.027 4.161 kJ/kg # K
Using these values, the percent error in approximating cv by cp is
cp cv
a b 11002 a b 11002 0.6%
0.027
cv 4.161
(b) The velocity of sound at this state can be determined using Eq. 11.65. The required value for the isentropic compressibility
is calculable in terms of the specific heat ratio k and the isothermal compressibility
. With Eq. 11.73,
k. Inserting
this into Eq. 11.65 results in the following expression for the velocity of sound
kv
c
A k
The values of v and

required by this expression are the same as used in part (a). Also, with the values of cp and cv from
part (a), the specific heat ratio is k 1.006. Accordingly
11.00621106 2 bar 105 N/m2 1 kg # m /s2

c `` ` ` 1482 m/s
B 1998.21 kg/m 2 145.902
3
1 bar 1N
Consistent with the discussion of Sec. 3.3.6, we take cp at 1 atm and 20C as the saturated liquid value at 20C.
The result of part (a) shows that for liquid water at the given state, cp and cv are closely equal.
For comparison, the velocity of sound in air at 1 atm, 20C is about 343 m/s, which can be checked using Eq. 9.37.
11.5.3 JouleThomson Coefficient

The value of the specific heat cp can be determined from pvT data and the JouleThomson
coefficient. The JouleThomson coefficient J is defined as
mJ a b
JouleThomson 0T
(11.75)
coefficient 0p h
Like other partial differential coefficients introduced in this section, the JouleThomson co-
efficient is defined in terms of thermodynamic properties only and thus is itself a property.
The units of J are those of temperature divided by pressure.
A relationship between the specific heat cp and the JouleThomson coefficient J can be
established by using Eq. 11.16 to write
a b a b a b 1
0T 0p 0h
0p h 0h T 0T p
The first factor in this expression is the JouleThomson coefficient and the third is cp. Thus
1
cp
mJ 1 0p 0h2 T
With ( 0h 0p)T 1( 0p 0h)T from Eq. 11.15, this can be written as
a b
1 0h
cp (11.76)
mJ 0p T
The partial derivative ( 0d 0p)T, called the constant-temperature coefficient, can be eliminated
from Eq. 11.76 by use of Eq. 11.56. The following expression results:
cT a b vd
1 0v
cp (11.77)
mJ 0T p
Equation 11.77 allows the value of cp at a state to be determined using pvT data and the
value of the JouleThomson coefficient at that state. Let us consider next how the
JouleThomson coefficient can be found experimentally.
EXPERIMENTAL EVALUATION. The JouleThomson coefficient can be evaluated experi-

mentally using an apparatus like that pictured in Fig. 11.3. Consider first Fig. 11.3a, which
shows a porous plug through which a gas (or liquid) may pass. During operation at steady
state, the gas enters the apparatus at a specified temperature T1 and pressure p1 and expands
through the plug to a lower pressure p2, which is controlled by an outlet valve. The temper-
ature T2 at the exit is measured. The apparatus is designed so that the gas undergoes a
throttling process (Sec. 4.3) as it expands from 1 to 2. Accordingly, the exit state fixed by
p2 and T2 has the same value for the specific enthalpy as at the inlet, h2 h1. By progres-
sively lowering the outlet pressure, a finite sequence of such exit states can be visited, as in-
dicated on Fig. 11.3b. A curve may be drawn through the set of data points. Such a curve is
called an isenthalpic (constant enthalpy) curve. An isenthalpic curve is the locus of all points
representing equilibrium states of the same specific enthalpy.
The slope of an isenthalpic curve at any state is the JouleThomson coefficient at that state.
The slope may be positive, negative, or zero in value. States where the coefficient has a zero
inversion states value are called inversion states. Notice that not all lines of constant h have an inversion state.
The uppermost curve of Fig. 11.3b, for example, always has a negative slope. Throttling a gas

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from an initial state on this curve would result in an increase in temperature. However, for
isenthalpic curves having an inversion state, the temperature at the exit of the apparatus may
be greater than, equal to, or less than the initial temperature, depending on the exit pressure
specified. For states to the right of an inversion state, the value of the JouleThomson coef-
ficient would be negative. For these states, the temperature would increase as the pressure at
the exit of the apparatus is reduced. At states to the left of an inversion state, the value of the
JouleThomson coefficient would be positive. For these states, the temperature would decrease
as the pressure at the exit of the device is reduced. This can be used to advantage in systems
designed to liquefy gases.
Inversion state
Inlet Inversion
T1, p1 state
Porous plug Inversion Inlet state

state (T1, p1)
Critical T
point
( )
h
p
T2, p2 Vapor
Liquid
Triple Solid
Valve point
p
(a) (b)
Figure 11.3 JouleThomson expansion. (a) Apparatus. (b) Isenthalpics on a Tp diagram.

11.6 Constructing Tables of
Thermodynamic Properties
The objective of this section is to utilize the thermodynamic relations introduced thus far to
describe how tables of thermodynamic properties can be constructed. The characteristics of
the tables under consideration are embodied in the tables for water and the refrigerants pre-
sented in the Appendix. The methods introduced in this section are extended in Chap. 13 for
the analysis of reactive systems, such as gas turbine and vapor power systems involving com-
bustion. The methods of this section also provide the basis for computer retrieval of ther-
modynamic property data.
Two different approaches for constructing property tables are considered:
The presentation of Sec. 11.6.1 employs the methods introduced in Sec. 11.4 for assign-
ing specific enthalpy, specific internal energy, and specific entropy to states of pure,
simple compressible substances using pvT data, together with a limited amount of
specific heat data. The principal mathematical operation of this approach is integration.
The approach of Sec. 11.6.2 utilizes the fundamental thermodynamic function concept
introduced in Sec. 11.3.3. Once such a function has been constructed, the principal
mathematical operation required to determine all other properties is differentiation.
11.6.1 Developing Tables by Integration Using pvT and

Specific Heat Data
In principle, all properties of present interest can be determined using
cp cp0 1T 2
p p1v, T 2, v v1 p, T 2
(11.78)
In Eqs. 11.78, cp0(T ) is the specific heat cp for the substance under consideration extrapo-
lated to zero pressure. This function might be determined from data obtained calorimetrically
or from spectroscopic data, using equations supplied by statistical mechanics. Specific heat
expressions for several gases are given in Tables A-21. The expressions p(v, T ) and v(p, T)
represent functions that describe the saturation pressuretemperature curves, as well as the
pvT relations for the single-phase regions. These functions may be tabular, graphical, or
analytical in character. Whatever their forms, however, the functions must not only represent
the pvT data accurately but also yield accurate values for derivatives such as ( 0v 0T )p and
(dpdT)sat.
Figure 11.4 shows eight states of a substance. Let us consider how values can be assigned
to specific enthalpy and specific entropy at these states. The same procedures can be used to
assign property values at other states of interest. Note that when h has been assigned to a
state, the specific internal energy at that state can be found from u h pv.
Let the state denoted by 1 on Fig. 11.4 be selected as the datum state for enthalpy and
entropy. Any value can be assigned to h and s at this state, but a value of zero would be
usual. It should be noted that the use of an arbitrary datum state and arbitrary reference
values for specific enthalpy and specific entropy suffices only for evaluations involving
differences in property values between states of the same composition, for then datums
cancel.
Once a value is assigned to enthalpy at state 1, the enthalpy at the saturated vapor state,
state 2, can be determined using the Clapeyron equation, Eq. 11.40
h2 h1 T1 1v2 v1 2 a b
dp
dT sat
11.6 Constructing Tables of Thermodynamic Properties 521
Isobar
reduced pressure
pR low enough
for the ideal gas
T model to be
appropriate
8
7 6 5
1
Arbitrary datum 2 3 4
state h1 = s1 = 0
Figure 11.4 Tv diagram used to dis-

cuss how h and s can be assigned to liquid
v and vapor states.
where the derivative (dpdT )sat and the specific volumes v1 and v2 are obtained from
appropriate representations of the pvT data for the substance under consideration.
The specific entropy at state 2 is found using Eq. 11.38 in the form
h2 h1
s2 s1
T1
Proceeding at constant temperature from state 2 to state 3, the entropy and enthalpy are
found by means of Eqs. 11.59 and 11.60, respectively. Since temperature is fixed, these
equations reduce to give
a b dp cv T a b d dp
p3 0v p3 0v
s3 s2 and h3 h2
p2 0T p p2 0T p
With the same procedure, s4 and h4 can be determined.
The isobar (constant-pressure line) passing through state 4 is assumed to be at a low
enough pressure for the ideal gas model to be appropriate. Accordingly, to evaluate
s and h at states such as 5 on this isobar, the only required information would be cp0 (T )
and the temperatures at these states. Thus, since pressure if fixed, Eqs. 11.59 and 11.60
give, respectively

T5 dT T5
s5 s4 cp0 and h5 h4 cp0 dT
T4 T T4
Specific entropy and enthalpy values at states 6 and 7 are found from those at state 5
by the same procedure used in assigning values at states 3 and 4 from those at state 2.
Finally, s8 and h8 are obtained from the values at state 7 using the Clapeyron equation.
11.6.2 Developing Tables by Differentiating a Fundamental

Thermodynamic Function
Property tables also can be developed using a fundamental thermodynamic function. It is con-
venient for this purpose to select the independent variables of the fundamental function from
among pressure, specific volume (density), and temperature. This indicates the use of the
Helmholtz function (T, v) or the Gibbs function g(T, p). The properties of water tabulated
in Tables A-2 through A-6 have been calculated using the Helmholtz function. Fundamental
functions also have been employed successfully to evaluate the properties of other substances.
The development of a fundamental function requires considerable mathematical manipu-
lation and numerical evaluation. Prior to the advent of high-speed computers, the evaluation
of properties by this means was not feasible, and the approach described in Sec. 11.6.1 was
used exclusively. The fundamental function approach involves three steps:
1. The first step is the selection of a functional form in terms of the appropriate pair of
independent properties and a set of adjustable coefficients, which may number 50 or more.
The functional form is specified on the basis of both theoretical and practical considerations.
2. Next, the coefficients in the fundamental function are determined by requiring that a set of
carefully selected property values and/or observed conditions be satisfied in a least-squares
sense. This generally involves the use of property data requiring the assumed functional
form to be differentiated one or more times, such as pvT and specific heat data.
3. When all coefficients have been evaluated, the function is carefully tested for accuracy
by using it to evaluate properties for which accepted values are known. These may
include properties requiring differentiation of the fundamental function two or more
times. For example, velocity of sound and JouleThomson data might be used.
This procedure for developing a fundamental function is not routine and can be accomplished
only with a computer. However, once a suitable fundamental function is established, extreme
accuracy in and consistency among the thermodynamic properties is possible.
The form of the Helmholtz function used in constructing the steam tables from which
Tables A-2 through A-6 have been extracted is
c1r, T 2 c0 1T 2
RT 3ln r
rQ1r, t2 4 (11.79)
where 0 and Q are given as the sums listed in Table 11.3. The independent variables are
density and temperature. The variable denotes 1000T. Values for pressure, specific internal
TABLE 11.3 Fundamental Equation Used to Construct the Steam Tablesa,b
c c0 1T 2
RT 3 ln r
rQ 1r, t2 4 (1)
where
6
c0 a Citi1
C7 ln T
C8 ln Tt (2)
i1
and
7 8 10
Q 1t tc 2 a 1t taj 2 j2 c a Aij 1r raj 2 i1
eEr a Aijri9 d (3)
j1 i1 i9
In (1), (2), and (3), T denotes temperature on the Kelvin scale, denotes 1000T, denotes
density in g/cm3, R 4.6151 bar # cm3 / g # K or 0.46151 J/g # K, tc
1000Tc 1.544912,
E 4.8, and
taj tc 1 j 12 raj 0.634 1 j 12
2.5 1 j 7 12 1.0 1 j 7 12
The coefficients for 0 in J/g are given as follows:
C1 1857.065 C4 36.6649 C7 46.0
C2 3229.12 C5 20.5516 C8 1011.249
C3 419.465 C6 4.85233
Values for the coefficients Aij are listed in the original source.a
a
J. H. Keenan, F. G. Keyes, P. G. Hill, and J. G. Moore, Steam Tables, Wiley, New York, 1969.
b
Also see L. Haar, J. S. Gallagher, and G. S. Kell, NBS / NRC Steam Tables, Hemisphere, Washington, D.C.,
1984. The properties of water are determined in this reference using a different functional form for the
Helmholtz function than given by Eqs. (1)(3).
11.6 Constructing Tables of Thermodynamic Properties 523
energy, and specific entropy can be determined by differentiation of Eq. 11.79. Values for
the specific enthalpy and Gibbs function are found from h u
pv and g
pv, re-
spectively. The specific heat cv is evaluated by further differentiation, cv ( 0 u 0 T)v. With
similar operations, other properties can be evaluated. Property values for water calculated
from Eq. 11.79 are in excellent agreement with experimental data over a wide range of con-
ditions. Example 11.7 illustrates this approach for developing tables.
EXAMPLE 11.7 Determining Properties Using a Fundamental Function
The following expression for the Helmholtz function has been used to determine the properties of water:
c1 r, T 2 c0 1T 2
RT 3 ln r
rQ 1r, t2 4
where denotes density and denotes 1000T. The functions 0 and Q are sums involving the indicated independent vari-
ables and a number of adjustable constants (see Table 11.3). Obtain expressions for (a) pressure, (b) specific entropy, and
(c) specific internal energy resulting from this fundamental function.
SOLUTION
Known: An expression for the Helmholtz function is given.
Find: Determine the expressions for pressure, specific entropy, and specific internal energy that result from this fundamen-
tal function.
Analysis: The expressions developed below for p, s, and u require only the functions 0(T ) and Q(, ). Once these func-
tions are determined, p, s, and u can each be determined as a function of density and temperature using elementary mathe-
matical operations.
(a) When expressed in terms of density instead of specific volume, Eq. 11.28 becomes
p r2 a b
0c
0r T
as can easily be verified. When T is held constant is also constant. Accordingly, the following is obtained on differentiation
of the given function:
a b RT c
Q 1r, t2
r a b d
0c 1 0Q
0r T r 0r t
Combining these equations gives an expression for pressure
p rRT c 1
rQ
r2 a b d
0Q
0r t
(b) From Eq. 11.29
b
0c
s a
0T r
Differentiation of the given expression for yields
a b
c R1ln r
rQ2
RTr a b d
0c dc0 0Q dt
0T r dT 0t r dT

c R1ln r
rQ2
RTr a b a 2 b d
dc0 0Q 1000

dT 0t r T

R c ln r
rQ rt a b d
dc0 0Q

dT 0t r
Combining results gives
R c ln r
rQ rt a b d
dc0 0Q
s
dT 0t r
(c) By definition, u Ts. Thus, u
Ts. Introducing the given expression for together with the expression for
s from part (b) results in
u 3c0
RT 1ln r
rQ2 4
T e R c ln r
rQ rt a b d f
dc0 0Q
dT 0t r

RTrt a b
dc0 0Q
c0 T
dT 0t r
This can be written more compactly by noting that
a 2 b t
dc0 dc0 dt dc0 1000 dc0
T T T
dT dt dT dt T dt
Thus,
dc0 dc0 d1c0t2
c0 T c0
t
dT dt dt
Finally, the expression for u becomes

RTrt a b
d1c0t2 0Q
u
dt 0t r

11.7 Generalized Charts for
Enthalpy and Entropy
Generalized charts giving the compressibility factor Z in terms of the reduced properties pR,
TR, and vR are introduced in Sec. 3.4. With such charts, estimates of pvT data can be ob-
tained rapidly knowing only the critical pressure and critical temperature for the substance
of interest. The objective of the present section is to introduce generalized charts that allow
changes in enthalpy and entropy to be estimated.
GENERALIZED ENTHALPY DEPARTURE CHART
The change in specific enthalpy of a gas (or liquid) between two states fixed by temperature
and pressure can be evaluated using the identity
h1T2, p2 2 h1T1, p1 2 3h*1T2 2 h*1T1 2 4

5 3h1T2, p2 2 h*1T2 2 4 3h1T1, p1 2 h*1T1 2 4 6 (11.80)
The term [h(T, p) h*(T)] denotes the specific enthalpy of the substance relative to that of
its ideal gas model when both are at the same temperature. The superscript * is used in this
section to identify ideal gas property values. Thus, Eq. 11.80 indicates that the change in
specific enthalpy between the two states equals the enthalpy change determined using the
ideal gas model plus a correction that accounts for the departure from ideal gas behavior.
The correction is shown underlined in Eq. 11.80. The ideal gas term can be evaluated using
methods introduced in Chap. 3. Next, we show how the correction term is evaluated in terms
of the enthalpy departure.
11.7 Generalized Charts for Enthalpy and Entropy 525
DEVELOPING THE ENTHALPY DEPARTURE. The variation of enthalpy with pressure at

fixed temperature is given by Eq. 11.56 as
a b vTa b
0h 0v
0p T 0T p
Integrating from pressure p to pressure p at fixed temperature T
p
h1T, p2 h1T, p 2 cv T a b d dp
0v
p 0T p
This equation is not altered fundamentally by adding and subtracting h*(T ) on the left side.
That is
p
3h1T, p2 h*1T 2 4 3h1T, p2 h*1T 2 4 cv T a b d dp
0v
(11.81)
p 0T p
As pressure tends to zero at fixed temperature, the enthalpy of the substance approaches
that of its ideal gas model. Accordingly, as p tends to zero
lim 3h1T, p 2 h*1T 2 4 0
p S0
In this limit, the following expression is obtained from Eq. 11.81 for the specific enthalpy
of a substance relative to that of its ideal gas model when both are at the same temperature:
p
h1T, p2 h*1T 2 cv T a b d dp
0v
(11.82)
0 0T p
This also can be thought of as the change in enthalpy as the pressure is increased from zero
to the given pressure while temperature is held constant. Using pvT data only, Eq. 11.82
can be evaluated at states 1 and 2 and thus the correction term of Eq. 11.80 evaluated. Let
us consider next how this procedure can be conducted in terms of compressibility factor data
and the reduced properties TR and pR.
The integral of Eq. 11.82 can be expressed in terms of the compressibility factor Z and
the reduced properties TR and pR as follows. Solving Z pvRT gives
ZRT
v
p
On differentiation
a b a b
0v RZ RT 0Z

0T p p p 0T p
With the previous two expressions, the integrand of Eq. 11.82 becomes
RT 2 0Z
vTa b Tc a b d a b
0v ZRT RZ RT 0Z

(11.83)
0T p p p p 0T p p 0T p
Equation 11.83 can be written in terms of reduced properties as

RTc # T 2R 0Z
vTa b a b
0v
0T p pc pR 0TR pR
Introducing this into Eq. 11.82 gives on rearrangement
h*1T 2 h1T, p2 pR
a b
0Z dpR
T 2R
RTc 0 0TR pR pR
Or, on a per mole basis, the enthalpy departure is
h*1T 2 h1T, p2 pR
a b
0Z dpR
enthalpy departure T 2R (11.84)
RTc 0 0TR pR pR
The right side of Eq. 11.84 depends only on the reduced temperature TR and reduced pres-
sure pR. Accordingly, the quantity (h* h) RTc, the enthalpy departure, is a function only
of these two reduced properties. Using a generalized equation of state giving Z as a function
of TR and pR, the enthalpy departure can readily be evaluated with a computer. Tabular rep-
resentations are also found in the literature. Alternatively, the graphical representation pro-
vided in Fig. A-4 can be employed.
EVALUATING ENTHALPY CHANGE. The change in specific enthalpy between two states
can be evaluated by expressing Eq. 11.80 in terms of the enthalpy departure as
h* h h* h
h2 h1 h*2 h*1 RTc c a b a b d (11.85)
RTc 2 RTc 1
The first underlined term in Eq. 11.85 represents the change in specific enthalpy between the
two states assuming ideal gas behavior. The second underlined term is the correction that must
be applied to the ideal gas value for the enthalpy change to obtain the actual value for the en-
thalpy change. The quantity (h* h) RTc at state 1 would be calculated with an equation giving
Z(TR, pR) or obtained from tables or the generalized enthalpy departure chart, Fig. A-4, using
the reduced temperature TR1 and reduced pressure pR1 corresponding to the temperature T1 and
pressure p1 at the initial state, respectively. Similarly, (h* h) RTc at state 2 would be evaluated
using TR2 and pR2. The use of Eq. 11.85 is illustrated in the next example.
EXAMPLE 11.8 Using the Generalized Enthalpy Departure Chart
Nitrogen enters a turbine operating at steady state at 100 bar and 300 K and exits at 40 bar and 245 K. Using the enthalpy
departure chart, determine the work developed, in kJ per kg of nitrogen flowing, if heat transfer with the surroundings can be
ignored. Changes in kinetic and potential energy from inlet to exit also can be neglected.
SOLUTION
Known: A turbine operating at steady state has nitrogen entering at 100 bar and 300 K and exiting at 40 bar and 245 K.
Find: Using the enthalpy departure chart, determine the work developed.
T
1
Wcv

m
1 2
N2
p1 = 100 bar p2 = 40 bar
T1 = 300 K T2 = 245 K
2
2s
s
Figure E11.8
Assumptions:
1. The control volume shown on the accompanying figure operates at steady state.
2. There is no significant heat transfer between the control volume and its surroundings.
3. Changes in kinetic and potential energy between inlet and exit can be neglected.
4. Equilibrium property relations apply at the inlet and exit.
Analysis: The mass and energy rate balances reduce at steady state to give
# #
V21 V22
0 # #
c h1 h2

g1z1 z2 2 d
Qcv Wcv
m m 2
#
where m is the mass flow rate. Dropping the heat transfer term by assumption 2 and the kinetic and potential energy terms
by assumption 3 gives on rearrangement
#
Wcv
# h1 h2
m
The term h1 h2 can be evaluated as follows:
h* h h* h
e h* h *2 RTc c a b a b df
1
h1 h2
M 1 RTc 1 RTc 2
In this expression, M is the molecular weight of nitrogen and the other terms have the same significance as in Eq. 11.85.
With specific enthalpy values from Table A-23 at T1 300 K and T2 245 K, respectively
h*1 h*2 8723 7121 1602 kJ/kmol
The terms (h* h) RTc at states 1 and 2 required by the above expression for h1 h2 can be determined from Fig. A-4.
First, the reduced temperature and reduced pressure at the inlet and exit must be determined. From Tables A-1, Tc 126 K,
pc 33.9 bar. Thus, at the inlet
300 100
TR1 2.38, pR1 2.95
126 33.9
At the exit
245 40
TR2 1.94, pR2 1.18
126 33.9
By inspection of Fig. A-4
h* h h* h
a b 0.5, a b 0.31
RTc 1 RTc 2
Substituting values
#
c 1602 a8.314 b 1126 K2 10.5 0.312 d 50.1 kJ/kg
Wcv 1 kJ kJ
m
#
kg kmol kmol # K
28
kmol
Due to inaccuracy in reading values from a graph such as Fig. A-4, we cannot expect extreme accuracy in the final cal-
culated result.
If the ideal gas model were used, the work would be determined as 1602 kJ/kmol, or 57.2 kJ/kg. These values are over
14% greater than the respective values determined by including the enthalpy departure.
GENERALIZED ENTROPY DEPARTURE CHART
A generalized chart that allows changes in specific entropy to be evaluated can be developed
in a similar manner to the generalized enthalpy departure chart introduced above. The dif-
ference in specific entropy between states 1 and 2 of a gas (or liquid) can be expressed as
the identity
s1T2, p2 2 s1T1, p1 2 s*1T2, p2 2 s*1T1, p1 2

5 3s1T2, p2 2 s*1T2, p2 2 4 3s1T1, p1 2 s*1T1, p1 2 4 6 (11.86)
where [s(T, p) s*(T, p)] denotes the specific entropy of the substance relative to that of its
ideal gas model when both are at the same temperature and pressure. Equation 11.86 indi-
cates that the change in specific entropy between the two states equals the entropy change
determined using the ideal gas model plus a correction (shown underlined) that accounts for
the departure from ideal gas behavior. The ideal gas term can be evaluated using methods
introduced in Sec. 6.3.2. Let us consider next how the correction term is evaluated in terms
of the entropy departure.
DEVELOPING THE ENTROPY DEPARTURE. The following Maxwell relation gives the vari-
ation of entropy with pressure at fixed temperature:
a b a b
0s 0v
(11.35)
0p T 0T p
Integrating from pressure p to pressure p at fixed temperature T gives
p
a b dp
0v
s1T, p2 s1T, p2 (11.87)
p 0T p
For an ideal gas, v RTp, so ( 0 v 0 T)p Rp. Using this in Eq. 11.87, the change in
specific entropy assuming ideal gas behavior is
p

R
s*1T, p2 s*1T, p2 dp (11.88)
p p
Subtracting Eq. 11.88 from Eq. 11.87 gives
p
3s1T, p2 s*1T, p2 4 3s1T, p2 s*1T, p2 4 c a b d dp
R 0v
(11.89)
p p 0T p
Since the properties of a substance tend to merge into those of its ideal gas model as pres-
sure tends to zero at fixed temperature, we have
lim 3s1T, p2 s*1T, p2 4 0
pS0
Thus, in the limit as p tends to zero, Eq. 11.89 becomes

p
c a b d dp
R 0v
s1T, p2 s*1T, p2 (11.90)
0 p 0T p
Using pvT data only, Eq. 11.90 can be evaluated at states 1 and 2 and thus the correction
term of Eq. 11.86 evaluated.
Equation 11.90 can be expressed in terms of the compressibility factor Z and the reduced
properties TR and pR. The result, on a per mole basis, is the entropy departure
s*1T, p2 s 1T, p2 h*1T 2 h1T, p2 pR
1Z 12
dpR
entropy departure
(11.91)
R RTRTc 0 pR
The right side of Eq. 11.91 depends only on the reduced temperature TR and reduced pres-
sure pR. Accordingly, the quantity (s* s ) R, the entropy departure, is a function only of
these two reduced properties. As for the enthalpy departure, the entropy departure can be
evaluated with a computer using a generalized equation of state giving Z as a function of TR
and pR. Alternatively, tabular data from the literature or the graphical representation provided
in Fig. A-5 can be employed.
EVALUATING ENTROPY CHANGE. The change in specific entropy between two states can
be evaluated by expressing Eq. 11.86 in terms of the entropy departure as
s* s s* s
s2 s1 s *2 s *1 R c a b a b d (11.92)
R 2 R 1
The first underlined term in Eq. 11.92 represents the change in specific entropy between the
two states assuming ideal gas behavior. The second underlined term is the correction that must
be applied to the ideal gas value for entropy change to obtain the actual value for the entropy
change. The quantity ( s* s )1 R, appearing in Eq. 11.92 would be calculated with an equa-
tion giving Z(TR, pR) or obtained from the generalized entropy departure chart, Fig. A-5, using
the reduced temperature TR1 and reduced pressure pR1 corresponding to the temperature T1 and
pressure p1 at the initial state, respectively. Similarly, ( s* s )2 R, would be evaluated using
TR2 and pR2. The use of Eq. 11.92 is illustrated in the next example.
EXAMPLE 11.9 Using the Generalized Entropy Departure Chart
For the case of Example 11.8, determine (a) the rate of entropy production, in kJ/kg # K, and (b) the isentropic turbine
efficiency.
SOLUTION
Known: A turbine operating at steady state has nitrogen entering at 100 bar and 300 K and exiting at 40 bar and 245 K.
Find: Determine the rate of entropy production, in kJ/kg # K, and the isentropic turbine efficiency.
Assumptions: See Example 11.8.

Analysis:
(a) At steady state, the control volume form of the entropy rate equation reduces to give
#
scv
# s2 s1
m
The change in specific entropy required by this expression can be written as
s* s s* s
e s* s*1 R c a b a b df
1
s2 s1
M 2 R 2 R 1
where M is the molecular weight of nitrogen and the other terms have the same significance as in Eq. 11.92.
The change in specific entropy s*2 s*1 can be evaluated using
s*2 s*1 s1T2 2 s1T1 2 R ln

p2
p1

40 kJ
s*2 s*1 185.775 191.682 8.314 ln 1.711
100 kmol # K
The terms ( s* s ) R at the inlet and exit can be determined from Fig. A-5. Using the reduced temperature and reduced
pressure values calculated in the solution to Example 11.8, inspection of Fig. A-5 gives
s* s s* s
a b 0.21, a b 0.14
R 1 R 2
Substituting values
#
c 1.711 10.14 0.212 d
scv 1 kJ kJ
# 8.314
m 128 kg/ kmol2 kmol # K kmol # K
kJ
0.082
kg # K
(b) The isentropic turbine efficiency is defined in Sec. 6.8 as
1Wcvm2
# #
ht
1Wcvm2 s
# #
where the denominator is the work that would be developed by the turbine if the nitrogen expanded isentropically from the
specified inlet state to the specified exit pressure. Thus, it is necessary to fix the state, call it 2s, at the turbine exit for an ex-
pansion in which there is no change in specific entropy from inlet to exit. With ( s2s s1) 0 and procedures similar to those
used in part (a)
s* s s* s
* s*1 R c a
0 s2s b a b d
R 2s R 1
s* s s* s
0 c s1T2s 2 s1T1 2 R ln a b d R c a b a b d
p2
p1 R 2s R 1
Using values from part (a), the last equation becomes

s* s
0 s1T2s 2 191.682 8.314 ln Ra b
1.746
40
100 R 2s
or
s* s
s1T2s 2 R a b 182.3
R 2s
The temperature T2s can be determined in an iterative procedure using s data from Table A-23 and 1s* s2 R from
Fig. A-5 as follows: First, a value for the temperature T2s is assumed. The corresponding value of s can then be obtained
from Table A-23. The reduced temperature (TR)2s T2sTc, together with pR2 1.18, allows a value for 1s* s2 R to be
obtained from Fig. A-5. The procedure continues until agreement with the value on the right side of the above equation is
obtained. Using this procedure, T2s is found to be closely 228 K.
With the temperature T2s known, the work that would be developed by the turbine if the nitrogen expanded isentropically
from the specified inlet state to the specified exit pressure can be evaluated from
#
a # b h1 h2s
Wcv
m s
h* h h* h
e 1h*1 h*2s 2 RTc c a b a b df
1

M RTc 1 RTc 2s
From Table A-23, h*2s 6654 kJ/kmol. From Fig. A-4 at pR2 1.18 and (TR)2s 228126 1.81
h* h
a b 0.36
RTc 2s
11.8 pvT Relations for Gas Mixtures 531
Values for the other terms in the expression for 1Wcvm2 s are obtained in the solution to Example 11.8. Finally
# #
#
a # b 38723 6654 18.31421126210.5 0.362 4 68.66 kJ/kg
Wcv 1
m s 28
With the work value from Example 11.8, the turbine efficiency is
1Wcvm2
# #
# 68.66 0.73 173% 2
50.1
ht #
1Wcvm2 s
We cannot expect extreme accuracy when reading data from a generalized chart such as Fig. A-5, which affects the final
calculated result.

11.8 pvT Relations for Gas Mixtures
Many systems of interest involve mixtures of two or more components. The principles of
thermodynamics introduced thus far are applicable to systems involving mixtures, but to ap-
ply them requires that the properties of mixtures be evaluated. Since an unlimited variety
of mixtures can be formed from a given set of pure components by varying the relative
amounts present, the properties of mixtures are available in tabular, graphical, or equation
forms only in particular cases such as air. Generally, special means are required for deter-
mining the properties of mixtures. In this section, methods for evaluating the pvT rela-
tions for pure components introduced in previous sections of the book are adapted to ob-
tain plausible estimates for gas mixtures. In Sec. 11.9 some general aspects of property
evaluation for multicomponent systems are introduced. The case of ideal gas mixtures is
taken up in Chap. 12.
To evaluate the properties of a mixture requires knowledge of the composition. The com-
position can be described by giving the number of moles (kmol or lbmol) of each compo-
nent present. The total number of moles, n, is the sum of the number of moles of each of
the components
j
n n1
n2
# # #
nj a ni (11.93)
i1
The relative amounts of the components present can be described in terms of mole fractions.
The mole fraction yi of component i is defined as
ni
yi (11.94)
n
Dividing each term of Eq. 11.93 by the total number of moles and using Eq. 11.94
j
1 a yi (11.95)
i1
That is, the sum of the mole fractions of all components present is equal to unity.
Most techniques for estimating mixture properties are empirical in character and are not
derived from fundamental principles. The realm of validity of any particular technique can
be established only by comparing predicted property values with empirical data. The brief
discussion to follow is intended only to show how certain of the procedures for evaluating
the pvT relations of pure components introduced previously can be extended to gas
mixtures.
MIXTURE EQUATION OF STATE. One way the pvT relation for a gas mixture can be
estimated is by applying to the overall mixture an equation of state such as introduced in
Sec. 11.1. The constants appearing in the equation selected would be mixture values
determined with empirical combining rules developed for the equation. For example, mixture
values of the constants a and b for use in the van der Waals and RedlichKwong equations
would be obtained using relations of the form
j 2 j
a a a yiai12 b , b a a yibi b (11.96)
i1 i1
where ai and bi are the values of the constants for component i and yi is the mole fraction.
Combination rules for obtaining mixture values for the constants in other equations of state
also have been suggested.
KAYS RULE. The principle of corresponding states method for single components intro-
duced in Sec. 3.4 can be extended to mixtures by regarding the mixture as if it were a single
pure component having critical properties calculated by one of several mixture rules. Perhaps
the simplest of these, requiring only the determination of a mole fraction averaged critical
temperature Tc and critical pressure pc, is Kays rule
j j
Kays rule Tc a yiTc,i, pc a yi pc,i (11.97)
i1 i1
where Tc,i, pc,i, and yi are the critical temperature, critical pressure, and mole fraction of com-
ponent i, respectively. Using Tc and pc, the mixture compressibility factor Z is obtained as
for a single pure component. The unknown quantity from among the pressure p, volume V,
temperature T, and total number of moles n of the gas mixture can then be obtained by solving
pV
Z (11.98)
nRT
Mixture values for Tc and pc also can be used to enter the generalized enthalpy departure and
entropy departure charts introduced in Sec. 11.7.
ADDITIVE PRESSURE RULE. Additional means for estimating pvT relations for mixtures
are provided by empirical mixture rules, of which several are found in the engineering liter-
ature. Among these are the additive pressure and additive volume rules. According to the
additive pressure rule, the pressure of a gas mixture occupying volume V at temperature T
is expressible as a sum of pressures exerted by the individual components
additive pressure rule p p1

p2
p3
# # # 4 T,V (11.99a)
where the pressures p1, p2, etc. are evaluated by considering the respective components to be
at the volume and temperature of the mixture. These pressures would be determined using
tabular or graphical pvT data or a suitable equation of state.
An alternative expression of the additive pressure rule in terms of compressibility factors
can be obtained. Since component i is considered to be at the volume and temperature of the
mixture, the compressibility factor Zi for this component is Zi piVniRT, so the pressure
pi is
ZiniRT
pi
V
Similarly, for the mixture

ZnRT
p
V
Substituting these expressions into Eq. 11.99a and reducing gives the following relationship
between the compressibility factors for the mixture Z and the mixture components Zi
j
Z a yiZi 4 T,V (11.99b)
i1
The compressibility factors Zi are determined assuming that component i occupies the entire
volume of the mixture at the temperature T.
ADDITIVE VOLUME RULE. The underlying assumption of the additive volume rule is that
the volume V of a gas mixture at temperature T and pressure p is expressible as the sum of
volumes occupied by the individual components
V V1
V2
V3
# # # 4 p,T (11.100a) additive volume rule
where the volumes V1, V2, etc. are evaluated by considering the respective components to be
at the pressure and temperature of the mixture. These volumes would be determined from
tabular or graphical pvT data or a suitable equation of state.
An alternative expression of the additive volume rule in terms of compressibility factors can
be obtained. Since component i is considered to be at the pressure and temperature of the mix-
ture, the compressibility factor Zi for this component is Zi pVi ni RT, so the volume Vi is
ZiniRT
Vi
p
Similarly, for the mixture
ZnRT
V
p
Substituting these expressions into Eq. 11.100a and reducing gives
j
Z a yi Zi 4 p,T (11.100b)
i1
The compressibility factors Zi are determined assuming that component i exists at the
temperature T and pressure p of the mixture.
The next example illustrates alternative means for estimating the pressure of a gas mixture.
EXAMPLE 11.10 Estimating Mixture Pressure by Alternative Means
A mixture consisting of 0.18 kmol of methane (CH4) and 0.274 kmol of butane (C4H10) occupies a volume of 0.241 m3 at a
temperature of 238C. The experimental value for the pressure is 68.9 bar. Calculate the pressure, in bar, exerted by the mix-
ture by using (a) the ideal gas equation of state, (b) Kays rule together with the generalized compressibility chart, (c) the van
der Waals equation, and (d) the rule of additive pressures employing the generalized compressibility chart. Compare the cal-
culated values with the known experimental value.
SOLUTION
Known: A mixture of two specified hydrocarbons with known molar amounts occupies a known volume at a specified
temperature.
Find: Determine the pressure, in bar, using four alternative methods, and compare the results with the experimental value.
T = 238C
p=?
Assumption: As shown in the accompanying figure, the system is the mixture.

0.18 kmol CH4
0.274 kmol C4H10
V = 0.241 m3
Figure E.11.10
Analysis: The total number of moles of mixture n is

n 0.18
0.274 0.454 kmol
Thus, the mole fractions of the methane and butane are, respectively
y1 0.396 and y2 0.604
The specific volume of the mixture on a molar basis is
0.241 m3 m3
v 0.531
10.18
0.2742 kmol kmol
(a) Substituting values into the ideal gas equation of state
18314 N # m/ kmol # K21511 K2
` 5 `
RT 1 bar
p
v 10.531 m3/kmol2 10 N/m2
80.01 bar
(b) To apply Kays rule, the critical temperature and pressure for each component are required. From Table A-1, for methane
Tc1 191 K, pc1 46.4 bar
and for butane
Tc2 425 K, pc2 38.0 bar
Thus, with Eqs. 11.97
Tc y1Tc1
y2Tc2 10.3962 11912
10.6042 14252 332.3 K
pc y1 pc1
y2 pc2 10.3962 146.42
10.6042 138.02 41.33 bar
Treating the mixture as a pure component having the above values for the critical temperature and pressure, the following
reduced properties are determined for the mixture:
T 511
TR 1.54
Tc 332.3
vpc 10.5312 141.332 0 105 0
vR
RTc 183142 1332.32
0.794
Turning to Fig. A-2, Z 0.88. The mixture pressure is then found from
ZnRT RT 18314215112
p Z 0.88
V v 10.5312 0 105 0
70.4 bar
(c) Mixture values for the van der Waals constants can be obtained using Eqs. 11.96. This requires values of the van der Waals
constants for each of the two mixture components. Table A-24 gives the following values for methane:
m3 2 m3
a1 2.293 bar a b, b1 0.0428
kmol kmol
Similarly, from Table A-24 for butane
m3 2 m3
a2 13.86 bar a b, b2 0.1162
kmol kmol
Then, the first of Eqs. 11.96 gives a mixture value for the constant a as
a 1y1a11 2
y2a12 2 2 2 3 0.396 12.2932 1 2
0.604 113.862 1 2 4 2
m3 2
8.113 bar a b
kmol
Substituting into the second of Eqs. 11.96 gives a mixture value for the constant b
b y1b1
y2b2 10.3962 10.04282
10.6042 10.11622
m3
0.087
kmol
Inserting the mixture values for a and b into the van der Waals equation together with known data
RT a
p 2
vb v
18314 N # m/kmol # K2 1511 K2 8.113 bar 1m3/kmol2 2
` `
1 bar

10.531 0.0872 1m /kmol2
3 5
10 N/m 2
10.531 m3/kmol2 2
66.91 bar
(d) To apply the additive pressure rule with the generalized compressibility chart requires that the compressibility factor for
each component be determined assuming that the component occupies the entire volume at the mixture temperature. With this
assumption, the following reduced properties are obtained for methane
T 511
TR1 2.69
Tc1 191
10.241 m30.18 kmol2 146.4 bar2 105 N/m2
` ` 3.91
v1pc1
vR1
RTc1 18314 N # m / kmol # K2 1191 K2 1 bar
With these reduced properties, Fig. A-2 gives Z1 1.0.
Similarly, for butane
T 511
TR2 1.2
Tc2 425
v2 pc2 10.882 1382 0105 0
vR2 0.95
RTc2 183142 14252
From Fig. A-2, Z2 0.8.
The compressibility factor for the mixture determined from Eq. 11.99b is
Z y1Z1
y2Z2 10.3962 11.02
10.6042 10.82 0.88.
Accordingly, the same value for pressure as determined in part (b) using Kays rule results: p 70.4 bar.
In this particular example, the ideal gas equation of state gives a value for pressure that exceeds the experimental value by
nearly 16%. Kays rule and the rule of additive pressures give pressure values about 3% greater than the experimental value.
The van der Waals equation with mixture values for the constants gives a pressure value about 3% less than the experimen-
tal value.

11.9 Analyzing Multicomponent Systems1
In the preceding section we considered means for evaluating the pvT relation of gas mix-
tures by extending methods developed for pure components. The current section is devoted
to the development of some general aspects of the properties of systems with two or more
components. Primary emphasis is on the case of gas mixtures, but the methods developed
solution also apply to solutions. When liquids and solids are under consideration, the term solution
is sometimes used in place of mixture. The present discussion is limited to nonreacting mix-
tures or solutions in a single phase. The effects of chemical reactions and equilibrium be-
tween different phases are taken up in Chaps. 13 and 14.
To describe multicomponent systems, composition must be included in our thermody-
namic relations. This leads to the definition and development of several new concepts, in-
cluding the partial molal property, the chemical potential, and the fugacity.
11.9.1 Partial Molal Properties

In the present discussion we introduce the concept of a partial molal property and illustrate
its use. This concept plays an important role in subsequent discussions of multicomponent
systems.
DEFINING PARTIAL MOLAL PROPERTIES. Any extensive thermodynamic property X of

a single-phase, single-component system is a function of two independent intensive prop-
erties and the size of the system. Selecting temperature and pressure as the independent
properties and the number of moles n as the measure of size, we have X X(T, p, n). For
a single-phase, multicomponent system, the extensive property X must then be a function
of temperature, pressure, and the number of moles of each component present, X X(T, p,
n1, n2, . . . , nj).
If each mole number is increased by a factor , the size of the system increases by the
same factor, and so does the value of the extensive property X. That is
aX1T, p, n1, n2, . . . , nj 2 X1T, p, an1, an2, . . . , anj 2

Differentiating with respect to while holding temperature, pressure, and the mole numbers
fixed and using the chain rule on the right side gives
0X 0X 0X
X n1
n2
# # #
0 1an1 2 01an2 2 01anj 2 j

n
This equation holds for all values of . In particular, it holds for 1. Setting 1
j
b
0X
X a ni (11.101)
i1 0ni T, p, nl
where the subscript nl denotes that all ns except ni are held fixed during differentiation.
1
This section may be deferred until Secs. 12.112.4 have been studied.
The partial molal property Xi is by definition
b
0X
Xi (11.102) partial molal property
0ni T, p, nl
The partial molal property Xi is a property of the mixture and not simply a property of
component i, for Xi depends in general on temperature, pressure, and mixture composition:
Xi(T, p, n1, n2, . . . , nj). Partial molal properties are intensive properties of the mixture.
Introducing Eq. 11.102, Eq. 11.101 becomes
j
X a niXi (11.103)
i1
This equation shows that the extensive property X can be expressed as a weighted sum of
the partial molal properties Xi.
Selecting the extensive property X in Eq. 11.103 to be volume, internal energy, enthalpy,
and entropy, respectively, gives
j j j j
V a niVi, U a niUi, H a niHi, S a niSi (11.104)
i1 i1 i1 i1
where Vi, Ui, Hi, Si denote the partial molal volume, internal energy, enthalpy, and entropy.
Similar expressions can be written for the Gibbs function G and the Helmholtz function .
Moreover, the relations between these extensive properties: H U
pV, G H TS,
U TS can be differentiated with respect to ni while holding temperature, pressure, and the
remaining ns constant to produce corresponding relations among partial molal properties:
Hi Ui
pVi, Gi Hi TSi, i Ui TSi, where Gi and i are the partial molal Gibbs
function and Helmholtz function, respectively. Several additional relations involving partial mo-
lal properties are developed later in this section.
EVALUATING PARTIAL MOLAL PROPERTIES. Partial molal properties can be evaluated by

several methods, including the following:
If the property X can be measured, Xi can be found by extrapolating a plot giving
(Xni)T, p, nl versus ni. That is
Xi a b lim a b
0X X
0ni T, p, nl ni S 0 ni T, p, nl
If an expression for X in terms of its independent variables is known, Xi can be evalu-
ated by differentiation. The derivative can be determined analytically if the function is
expressed analytically or found numerically if the function is in tabular form.
When suitable data are available, a simple graphical procedure known as the method of
intercepts can be used to evaluate partial molal properties. In principle, the method can method of intercepts
be applied for any extensive property. To introduce this method, let us consider the vol-
ume of a system consisting of two components, A and B. For this system, Eq. 11.103
takes the form
V nAVA
nBVB
where VA and VB are the partial molal volumes of A and B, respectively. Dividing by the
number of moles of mixture n
V
yAVA
yBVB
n
V T and p constant

n
V as a function of y
B vB(T, p)
n
VB(T, p, yB)
vA(T, p) Tangent
line
VA(T, p, yB)
Figure 11.5 Illustration of the evaluation

0 yB 1.0
(pure A) (pure B) of partial molal volumes by the method of in-
Mole fraction of B tercepts.
where yA and yB denote the mole fractions of A and B, respectively. Since yA

yB 1,
this becomes
11 yB 2VA
yBVB VA
yB 1VB VA 2
V
n
This equation provides the basis for the method of intercepts. For example, refer to
Fig. 11.5, in which Vn is plotted as a function of yB at constant T and p. At a speci-
fied value for yB, a tangent to the curve is shown on the figure. When extrapolated,
the tangent line intersects the axis on the left at VA and the axis on the right at VB.
These values for the partial molal volumes correspond to the particular specifications
for T, p, and yB. At fixed temperature and pressure, VA and VB vary with yB and are
not equal to the molar specific volumes of pure A and pure B, denoted on the figure
as vA and vB, respectively. The values of vA and vB are fixed by temperature and
pressure only.
EXTENSIVE PROPERTY CHANGES ON MIXING. Let us conclude the present discussion

by evaluating the change in volume on mixing of pure components at the same temperature
and pressure, a result for which an application is given later in the section. The total volume
of the pure components before mixing is
j
Vcomponents a nivi
i1
where vi is the molar specific volume of pure component i. The volume of the mixture is
j
Vmixture a niVi
i1
where Vi is the partial molal volume of component i in the mixture. The volume change on
mixing is
j j
Vmixing Vmixture Vcomponents a niVi a nivi
i1 i1
or
j
Vmixing a ni 1Vi vi 2 (11.105)
i1
Similar results can be obtained for other extensive properties, for example,
j
Umixing a ni 1Ui ui 2
i1
j
Hmixing a ni 1Hi hi 2 (11.106)
i1
j
Smixing a ni 1Si si 2
i1
In Eqs. 11.106, ui, hi, and si denote the molar internal energy, enthalpy, and entropy
of pure component i. The symbols Ui, Hi, and Si denote the respective partial molal
properties.
11.9.2 Chemical Potential

Of the partial molal properties, the partial molal Gibbs function is particularly useful in de-
scribing the behavior of mixtures and solutions. This quantity plays a central role in the cri-
teria for both chemical and phase equilibrium (Chap. 14). Because of its importance in the
study of multicomponent systems, the partial molal Gibbs function of component i is given
a special name and symbol. It is called the chemical potential of component i and sym-
bolized by i
b
0G
mi Gi (11.107) chemical potential
0ni T, p, nl
Like temperature and pressure, the chemical potential i is an intensive property.

Applying Eq. 11.103 together with Eq. 11.107, the following expression can be written:
j
G a ni mi (11.108)
i1
Expressions for the internal energy, enthalpy, and Helmholtz function can be obtained
from Eq. 11.108, using the definitions H U
pV, G H TS, and U TS.
They are
j
U TS pV
a ni mi
i1
j
H TS
a ni mi (11.109)
i1
j
pV
a ni mi
i1
Other useful relations can be obtained as well. Forming the differential of G(T, p,
n1, n2, . . . , nj)
j
b dp
b dT
a a b
0G 0G 0G
dG dni (11.110)
0p T, n 0T p, n i1 0ni T, p, nl
The subscripts n in the first two terms indicate that all ns are held fixed during differentia-
tion. Since this implies fixed composition, it follows from Eqs. 11.30 and 11.31 that
Va b S a b
0G 0G
and (11.111)
0p T, n 0T p, n
With Eqs. 11.107 and 11.111, Eq. 11.110 becomes
j
dG V dp S dT
a mi dni (11.112)
i1
which for a multicomponent system is the counterpart of Eq. 11.23.

Another expression for dG is obtained by forming the differential of Eq. 11.108. That is
j j
dG a ni dmi
a mi dni
i1 i1
Combining this equation with Eq. 11.112 gives the GibbsDuhem equation
j
GibbsDuhem equation a ni dmi V dp S dT (11.113)
i1
11.9.3 Fundamental Thermodynamic Functions for

Multicomponent Systems
A fundamental thermodynamic function provides a complete description of the thermody-
namic state of a system. In principle, all properties of interest can be determined from such
a function by differentiation and/or combination. Reviewing the developments of Sec. 11.9.2,
we see that a function G(T, p, n1, n2, . . . , nj) is a fundamental thermodynamic function for
a multicomponent system.
Functions of the form U(S, V, n1, n2, . . . , nj), H(S, p, n1, n2, . . . , nj), and (T, V,
n1, n2, . . . , nj) also can serve as fundamental thermodynamic functions for multicomponent
systems. To demonstrate this, first form the differential of each of Eqs. 11.109 and use the
GibbsDuhem equation, Eq. 11.113, to reduce the resultant expressions to obtain
j
dU T dS p dV
a mi dni (11.114a)
i1
j
dH T dS
V dp
a mi dni (11.114b)
i1
j
d p dV S dT
a mi dni (11.114c)
i1
For multicomponent systems, these are the counterparts of Eqs. 11.18, 11.19, and 11.22,
respectively.
The differential of U(S, V, n1, n2, . . . , nj) is
j
b dS
b dV
a a b
0U 0U 0U
dU dni
0S V, n 0V S, n i1 0ni S,V, nl
Comparing this expression term by term with Eq. 11.114a, we have
b , b , b
0U 0U 0U
T p mi (11.115a)
0S V, n 0V S, n 0ni S,V, nl
That is, the temperature, pressure, and chemical potentials can be obtained by differentiation
of U(S, V, n1, n2, . . . , nj). The first two of Eqs. 11.115a are the counterparts of Eqs. 11.24
and 11.25.
A similar procedure using a function of the form H(S, p, n1, n2, . . . , nj) together with
Eq. 11.114b gives
b , b , b
0H 0H 0H
T V mi (11.115b)
0S p, n 0p S, n 0ni S, p, nl
where the first two of these are the counterparts of Eqs. 11.26 and 11.27. Finally, with
(S, V, n1, n2, . . . , nj) and Eq. 11.114c
b , b , b
0 0 0
p S mi (11.115c)
0V T, n 0T V, n 0ni T,V, nl
The first two of these are the counterparts of Eqs. 11.28 and 11.29. With each choice of fun-
damental function, the remaining extensive properties can be found by combination using
the definitions H U
pV, G H TS, U TS.
The foregoing discussion of fundamental thermodynamic functions has led to several prop-
erty relations for multicomponent systems that correspond to relations obtained previously.
In addition, counterparts of the Maxwell relations can be obtained by equating mixed sec-
ond partial derivatives. For example, the first two terms on the right of Eq. 11.112 give
b b
0V 0S
(11.116)
0T p, n 0p T, n
which corresponds to Eq. 11.35. Numerous relationships involving chemical potentials can
be derived similarly by equating mixed second partial derivatives. An important example
from Eq. 11.112 is
b b
0mi 0V
0p T, n 0ni T, p, nl
Recognizing the right side of this equation as the partial molal volume, we have
b Vi
0mi
(11.117)
0p T, n
This relationship is applied later in the section.

The present discussion concludes by listing four different expressions derived above for
the chemical potential in terms of other properties. In the order obtained, they are
b b b b
0G 0U 0H 0
mi (11.118)
0ni T, p, nl 0ni S,V, nl 0ni S, p, nl 0ni T,V, nl
Only the first of these partial derivatives is a partial molal property, however, for the term
partial molal applies only to partial derivatives where the independent variables are temper-
ature, pressure, and the number of moles of each component present.
11.9.4 Fugacity
The chemical potential plays an important role in describing multicomponent systems. In
some instances, however, it is more convenient to work in terms of a related property, the
fugacity. The fugacity is introduced in the present discussion.
SINGLE-COMPONENT SYSTEMS
Let us begin by taking up the case of a system consisting of a single component. For this
case, Eq. 11.108 reduces to give
G
G nm or m g
n
That is, for a pure component the chemical potential equals the Gibbs function per mole.
With this equation, Eq. 11.30 written on a per mole basis becomes
b v
0m
(11.119)
0p T
For the special case of an ideal gas, v RTp, and Eq. 11.119 assumes the form
b
0m* RT
0p T p
where the asterisk denotes ideal gas. Integrating at constant temperature

m* RT ln p
C 1T 2 (11.120)
where C(T) is a function of integration. Since the pressure p can take on values from zero
to plus infinity, the ln p term of this expression, and thus the chemical potential, has an in-
convenient range of values from minus infinity to plus infinity. Equation 11.120 also shows
that the chemical potential can be determined only to within an arbitrary constant.
INTRODUCING FUGACITY. Because of the above considerations, it is advantageous for

many types of thermodynamic analyses to use fugacity in place of the chemical potential,
for it is a well-behaved function that can be more conveniently evaluated. We introduce the
fugacity fugacity f by the expression
m RT ln f
C 1T 2 (11.121)
Comparing Eq. 11.121 with Eq. 11.120, the fugacity is seen to play the same role in the gen-
eral case as pressure plays in the ideal gas case. Fugacity has the same units as pressure.
Substituting Eq. 11.121 into Eq. 11.119 gives
RT a b v
0 ln f
(11.122)
0p T
Integration of Eq. 11.122 while holding temperature constant can determine the fugacity only
to within a constant term. However, since ideal gas behavior is approached as pressure tends
to zero, the constant term can be fixed by requiring that the fugacity of a pure component
equals the pressure in the limit of zero pressure. That is
f
lim 1 (11.123)
pS0 p
Equations 11.122 and 11.123 then completely determine the fugacity function.
EVALUATING FUGACITY. Let us consider next how the fugacity can be evaluated. With
Z pv RT, Eq. 11.122 becomes
RT a b
0 ln f RTZ
0p T p
or
a b
0 ln f Z
0p T p
Subtracting 1p from both sides and integrating from pressure p to pressure p at fixed tem-
perature T
p
3ln f ln p4 pp 1Z 12 d ln p
p
or
f p p
c ln d 1Z 12 d ln p
p p p
Taking the limit as p tends to zero and applying Eq. 11.123 results in
p
1Z 12 d ln p
f
ln
p 0
When expressed in terms of the reduced pressure, pR ppc, the above equation is
pR
1Z 12 d ln pR
f
ln (11.124)
p 0
Since the compressibility factor Z depends on the reduced temperature TR and reduced pres-
sure pR, it follows that the right side of Eq. 11.124 depends on these properties only. Ac-
cordingly, the quantity ln fp is a function only of these two reduced properties. Using a gen-
eralized equation of state giving Z as a function of TR and pR, ln fp can readily be evaluated
with a computer. Tabular representations are also found in the literature. Alternatively, the
graphical representation presented in Fig. A-6 can be employed.
for example. . . to illustrate the use of Fig. A-6, consider two states of water vapor
at the same temperature, 400C. At state 1 the pressure is 200 bar, and at state 2 the pres-
sure is 240 bar. The change in the chemical potential between these states can be determined
using Eq. 11.121 as
RT ln a b
f2 f2 p2 p1
m2 m1 RT ln
f1 p2 p1 f1
Using the critical temperature and pressure of water from Table A-1, at state 1 pR1 0.91,
TR1 1.04, and at state 2 pR2 1.09, TR2 1.04. By inspection of Fig. A-6, f1p1 0.755
and f2p2 0.7. Inserting values in the above equation
m2 m1 18.31421673.152 ln c 10.72 a ba b d 597 kJ/kmol

240 1
200 0.755
For a pure component, the chemical potential equals the Gibbs function per mole,
g h T s. Since the temperature is the same at states 1 and 2, the change in the chemi-
cal potential can be expressed as m2 m1 h2 h1 T 1s2 s1 2. Using steam table data,
the value obtained with this expression is 597 kJ/kmol, which agrees with the value deter-
mined from the generalized fugacity coefficient chart.
MULTICOMPONENT SYSTEMS
The fugacity of a component i in a mixture can be defined by a procedure that parallels the
definition for a pure component. For a pure component, the development begins with
Eq. 11.119, and the fugacity is introduced by Eq. 11.121. These are then used to write the
pair of equations, Eqs. 11.122 and 11.123, from which the fugacity can be evaluated. For a
mixture, the development begins with Eq. 11.117, the counterpart of Eq. 11.119, and the
fugacity f i of component i is introduced by
mi RT ln f i
Ci 1T 2 (11.125)
which parallels Eq. 11.121. The pair of equations that allow the fugacity of a mixture
component, f i, to be evaluated are
RT a b Vi
0 ln f i
(11.126a)
0p T, n
fugacity of a mixture
lim a b1
component fi
(11.126b)
pS0 yi p
The symbol f i denotes the fugacity of component i in the mixture and should be carefully
distinguished in the presentation to follow from fi, which denotes the fugacity of pure i.
DISCUSSION. Referring to Eq. 11.126b, note that in the ideal gas limit the fugacity f i is
not required to equal the pressure p as for the case of a pure component, but to equal the
quantity yi p. To see that this is the appropriate limiting quantity, consider a system consist-
ing of a mixture of gases occupying a volume V at pressure p and temperature T. If the over-
all mixture behaves as an ideal gas, we can write
nRT
p (11.127)
V
where n is the total number of moles of mixture. Recalling from Sec. 3.5 that an ideal gas can
be regarded as composed of molecules that exert negligible forces on one another and whose
volume is negligible relative to the total volume, we can think of each component i as be-
having as if it were an ideal gas alone at the temperature T and volume V. Thus, the pressure
exerted by component i would not be the mixture pressure p but the pressure pi given by
niRT
pi (11.128)
V
where ni is the number of moles of component i. Dividing Eq. 11.128 by Eq. 11.127
pi ni RTV ni
yi
p nRTV n
On rearrangement
pi yi p (11.129)
Accordingly, the quantity yi p appearing in Eq. 11.126b corresponds to the pressure pi.
Summing both sides of Eq. 11.129, we obtain
j j j
a pi a yi p p a yi
i1 i1 i1
Or, since the sum of the mole fractions equals unity

j
p a pi (11.130)
i1
In words, Eq. 11.130 states that the sum of the pressures pi equals the mixture pressure. This
gives rise to the designation partial pressure for pi. With this background, we now see that
Eq. 11.126b requires the fugacity of component i to approach the partial pressure of com-
ponent i as pressure p tends to zero. Comparing Eqs. 11.130 and 11.99a, we also see that
the additive pressure rule is exact for ideal gas mixtures. This special case is considered fur-
ther in Sec. 12.2 under the heading Dalton model.
EVALUATING FUGACITY IN A MIXTURE. Let us consider next how the fugacity of com-
ponent i in a mixture can be expressed in terms of quantities that can be evaluated. For a
pure component i, Eq. 11.122 gives
RT a b vi
0 ln fi
(11.131)
0p T
where vi is the molar specific volume of pure i. Subtracting Eq. 11.131 from Eq. 11.126a
0 ln 1 f i fi 2
RT c d Vi vi (11.132)
0p T, n
Integrating from pressure p to pressure p at fixed temperature and mixture composition

fi p p
RT c ln a b d 1Vi vi 2 dp
fi p p
In the limit as p tends to zero, this becomes

p
RT c ln a b lim ln a b d 1Vi vi 2 dp
fi fi
fi p S 0 fi 0
Since fi S p and f i S yi p as pressure p tends to zero
lim ln a b S ln a b ln yi
fi yi p
p S 0 fi p
Therefore, we can write
p
RT c ln a b ln yi d 1Vi vi 2 dp
fi
fi 0
or
p
RT ln a b 1Vi vi 2 dp
fi
(11.133)
yi fi 0
in which f i is the fugacity of component i at pressure p in a mixture of given composition

at a given temperature, and fi is the fugacity of pure i at the same temperature and pressure.
Equation 11.133 expresses the relation between f i and fi in terms of the difference between
Vi and vi, a measurable quantity.
11.9.5 Ideal Solution

The task of evaluating the fugacities of the components in a mixture is considerably simpli-
fied when the mixture can be modeled as an ideal solution. An ideal solution is a mixture ideal solution
for which
f i yi fi 1ideal solution2 (11.134) LewisRandall rule

Equation 11.134, known as the LewisRandall rule, states that the fugacity of each compo-
nent in an ideal solution is equal to the product of its mole fraction and the fugacity of the
pure component at the same temperature, pressure, and state of aggregation (gas, liquid, or
solid) as the mixture. Many gaseous mixtures at low to moderate pressures are adequately
modeled by the LewisRandall rule. The ideal gas mixtures considered in Chap. 12 are an
important special class of such mixtures. Some liquid solutions also can be modeled with
the LewisRandall rule.
As consequences of the definition of an ideal solution, the following characteristics are
exhibited:
Introducing Eq. 11.134 into Eq. 11.132, the left side vanishes, giving Vi vi 0, or
Vi vi (11.135)
Thus, the partial molal volume of each component in an ideal solution is equal to the
molar specific volume of the corresponding pure component at the same temperature
and pressure. When Eq. 11.135 is introduced in Eq. 11.105, it can be concluded that
there is no volume change on mixing pure components to form an ideal solution.
With Eq. 11.135, the volume of an ideal solution is
j j j
V a niVi a nivi a Vi 1ideal solution2 (11.136)
i1 i1 i1
where Vi is the volume that pure component i would occupy when at the temperature
and pressure of the mixture. Comparing Eqs. 11.136 and 11.100a, the additive volume
rule is seen to be exact for ideal solutions.
It also can be shown that the partial molal internal energy of each component in an
ideal solution is equal to the molar internal energy of the corresponding pure compo-
nent at the same temperature and pressure. A similar result applies for enthalpy. In
symbols
Ui ui, Hi hi (11.137)
With these expressions, it can be concluded from Eqs. 11.106 that there is no change in
internal energy or enthalpy on mixing pure components to form an ideal solution.
With Eqs. 11.137, the internal energy and enthalpy of an ideal solution are
j j
U a niui and H a nihi 1ideal solution2 (11.138)
i1 i1
where ui and hi denote, respectively, the molar internal energy and enthalpy of pure
component i at the temperature and pressure of the mixture.
Although there is no change in V, U, or H on mixing pure components to form an ideal
solution, we expect an entropy increase to result from the adiabatic mixing of different pure
components because such a process is irreversible: The separation of the mixture into the
pure components would never occur spontaneously. The entropy change on adiabatic mix-
ing is considered further for the special case of ideal gas mixtures in Sec. 12.4.
The LewisRandall rule requires that the fugacity of mixture component i be evaluated
in terms of the fugacity of pure component i at the same temperature and pressure as the
mixture and in the same state of aggregation. For example, if the mixture were a gas at
T, p, then fi would be determined for pure i at T, p and as a gas. However, at certain tem-
peratures and pressures of interest a component of a gaseous mixture may, as a pure sub-
stance, be a liquid or solid. An example is an airwater vapor mixture at 20C (68F) and
1 atm. At this temperature and pressure, water exists not as a vapor but as a liquid. Although
not considered here, means have been developed that allow the ideal solution model to be
useful in such cases.
11.9.6 Chemical Potential for Ideal Solutions

The discussion of multicomponent systems concludes with the introduction of expressions for
evaluating the chemical potential for ideal solutions used in subsequent sections of the book.
Consider a reference state where component i of a multicomponent system is pure at the
temperature T of the system and a reference-state pressure pref. The difference in the chem-
ical potential of i between a specified state of the multicomponent system and the reference
state is obtained with Eq. 11.125 as
fi
mi mi RT ln (11.139)
f i
where the superscript denotes property values at the reference state. The fugacity ratio appearing
in the logarithmic term is known as the activity, ai, of component i in the mixture. That is
fi
ai (11.140) activity
f i
For subsequent applications, it suffices to consider the case of gaseous mixtures. For gaseous
mixtures, pref is specified as 1 atm, so mi and f i in Eq. 11.140 are, respectively, the chem-
ical potential and fugacity of pure i at temperature T and 1 atm.
Since the chemical potential of a pure component equals the Gibbs function per mole,
Eq. 11.139 can be written as
mi gi
RT ln ai (11.141)
where gi is the Gibbs function per mole of pure component i evaluated at temperature T and
1 atm: gi gi(T, 1 atm).
For an ideal solution, the LewisRandall rule applies and the activity is
yi fi
ai (11.142)
f i
where fi is the fugacity of pure component i at temperature T and pressure p. Introducing
Eq. 11.142 into Eq. 11.141
yi fi
mi gi
RT ln
f i
or
mi g i
RT ln c a b a b d 1ideal solution2
fi pref yi p
(11.143)
p f i pref
In principle, the ratios of fugacity to pressure shown underlined in this equation can be eval-
uated from Eq. 11.124 or the generalized fugacity chart, Fig. A-6, developed from it. If com-
ponent i behaves as an ideal gas at both T, p and T, pref, fi p f i pref 1, and Eq. 11.143
reduces to
1ideal gas2
yi p
mi g i
RT ln (11.144)
pref
In this chapter, we introduce thermodynamic relations that al- the chapter and understand each of the related concepts. The
low u, h, and s as well as other properties of simple com- subset of key concepts listed below is particularly important.
pressible systems to be evaluated using property data that are Additionally, for systems involving a single species you
more readily measured. The emphasis is on systems involv- should be able to
ing a single chemical species such as water or a mixture such
calculate pvT data using equations of state such
as air. An introduction to general property relations for mix-
as the RedlichKwong and BenedictWebbRubin
tures and solutions is also included.
equations.
Equations of state relating p, v, and T are considered, in-
cluding the virial equation and examples of two-constant and use the 16 property relations summarized in Table 11.1
multiconstant equations. Several important property rela- and explain how the relations are obtained.
tions based on the mathematical characteristics of exact dif- evaluate s, u, and h, using the Clapeyron equation
ferentials are developed, including the Maxwell relations. when considering phase change, and using equations of
The concept of a fundamental thermodynamic function is state and specific heat relations when considering single
discussed. Means for evaluating changes in specific internal phases.
energy, enthalpy, and entropy are developed and applied to
use the property relations introduced in Sec. 11.5 such as
phase change and to single-phase processes. Property
those involving the specific heats, the volume expansiv-
relations are introduced involving the volume expansivity,
ity, and the JouleThomson coefficient.
isothermal and isentropic compressibilities, velocity of
sound, specific heats and specific heat ratio, and the explain how tables of thermodynamic properties, such as
JouleThomson coefficient. Tables A-2 through A-18, are constructed.
Additionally, we describe how tables of thermodynamic use the generalized enthalpy and entropy departure
properties are constructed using the property relations and charts, Figs. A-4 and A-5, to evaluate h and s.
methods developed in this chapter. Such procedures also pro-
vide the basis for data retrieval by computer software. Also For a gas mixture of known composition, you should be
described are means for using the generalized enthalpy and able to
entropy departure charts and the generalized fugacity coeffi- apply the methods introduced in Sec. 11.8 for relating
cient chart to evaluate enthalpy, entropy, and fugacity, pressure, specific volume, and temperatureKays rule,
respectively. for example.
We also consider pvT relations for gas mixtures of
known composition, including Kays rule. The chapter con- For multicomponent systems, you should be able to
cludes with a discussion of property relations for multi- evaluate extensive properties in terms of the respective
component systems, including partial molal properties, partial molal properties.
chemical potential, fugacity, and activity. Ideal solutions
and the LewisRandall rule are introduced as a part of that evaluate partial molal volumes using the method of
presentation. intercepts.
The following checklist provides a study guide for this evaluate fugacity using data from the generalized fugac-
chapter. When your study of the text and end-of-chapter ex- ity coefficient chart, Fig. A-6.
ercises has been completed you should be able to write out apply the ideal solution model.
the meanings of the terms listed in the margins throughout
equation of Gibbs function p. 498 Joule-Thomson method of

state p. 487 Maxwell relations p. 499 coefficient p. 518 intercepts p. 537
exact differential p. 494 fundamental enthalpy and entropy chemical potential p. 539
test for exactness p. 494 function p. 503 departures p. 526, 528 fugacity p. 542
Helmholtz Clapeyron Kays rule p. 532 LewisRandall rule p. 545
function p. 498 equation p. 505
1. What is an advantage of using the RedlichKwong equation 9. Can you devise a way to determine the specific heat cp of a
of state in the generalized form given by Eq. 11.9 instead of gas by direct measurement? Indirectly, using other measured
Eq. 11.7? A disadvantage? data?
2. To determine the specific volume of superheated water vapor 10. For an ideal gas, what is the value of the JouleThomson
at a known pressure and temperature, when would you use each coefficient?
of the following: the steam tables, the generalized compressibility 11. At what states is the entropy departure negligible? The
chart, an equation of state, the ideal gas model? fugacity coefficient, fp, closely equal to unity?
3. If the function p p(T, v) is an equation of state, is ( 0p 0T )v 12. In Eq. 11.107, what do the subscripts T, p, and nl signify?
a property? What are the independent variables of ( 0p 0T )v? What does i denote?
4. In the expression ( 0u 0T )v, what does the subscript v signify? 13. How does Eq. 11.108 reduce for a system consisting of a
5. Explain how a Mollier diagram provides a graphical repre- pure substance? Repeat for an ideal gas mixture.
sentation of the fundamental function h(s, p). 14. If two different liquids of known volumes are mixed, is the
6. How is the Clapeyron equation used? final volume necessarily equal to the sum of the original
7. For a gas whose equation of state is pv RT, are the specific volumes?
heats cp and cv necessarily functions of temperature alone? 15. For a binary solution at temperature T and pressure p, how
8. Referring to the pT diagram for water, explain why ice melts would you determine the specific heat cp? Repeat for an ideal
under the blade of an ice skate. solution and for an ideal gas mixture.
Using Equations of State methane should not exceed 12 MPa. Check the pressure using
11.1 The pressure within a 23.3-m3 tank should not exceed 105 the
bar. Check the pressure within the tank if filled with 1000 kg (a) ideal gas equation of state.
of water vapor maintained at 360C using the (b) RedlichKwong equation.
(a) ideal gas equation of state. (c) BenedictWebbRubin equation.
(b) van der Waals equation. 11.5 Methane gas at 100 atm and 18C is stored in a 10-m3
(c) RedlichKwong equation. tank. Determine the mass of methane contained in the tank, in
(d) compressibility chart. kg, using the
(e) steam tables. (a) ideal gas equation of state.
11.2 Estimate the pressure of water vapor at a temperature of (b) van der Waals equation.
500C and a density of 24 kg/m3 using the (c) BenedictWebbRubin equation.
(a) steam tables. 11.6 Using the BenedictWebbRubin equation of state, deter-
(b) compressibility chart. mine the volume, in m3 occupied by 165 kg of methane at a
(c) RedlichKwong equation. pressure of 200 atm and temperature of 400 K. Compare with
(d) van der Waals equation. the results obtained using the ideal gas equation of state and
(e) ideal gas equation of state. the generalized compressibility chart.
11.3 Determine the specific volume of water vapor at 20 MPa 11.7 A rigid tank contains 1 kg of oxygen (O2) at p1 40 bar,
and 400C, in m3/kg, using the T1 180 K. The gas is cooled until the temperature drops to
(a) steam tables. 150 K. Determine the volume of the tank, in m3, and the final
(b) compressibility chart. pressure, in bar, using the
(c) RedlichKwong equation. (a) ideal gas equation of state.
(d) van der Waal equation. (b) RedlichKwong equation.
(e) ideal gas equation of state. (c) compressibility chart.
11.4 A vessel whose volume is 1 m3 contains 4 kmol of methane 11.8 Water vapor initially at 240C, 1 MPa expands in a piston
at 100C. Owing to safety requirements, the pressure of the cylinder assembly isothermally and without internal irreversibil-
ities to a final pressure of 0.1 MPa. Evaluate the work done, in ture, TR, pseudoreduced specific volume, vR, and appropriate
kJ/kg. Use a truncated virial equation of state with the form dimensionless constants.
B C
Z1

2 11.13 The Dieterici equation of state is
v v
a
pa b exp a b
RT
where B and C are evaluated from steam table data at 240C vb RTv
and pressures ranging from 0 to 1 MPa.
(a) Using Eqs. 11.3, show that
11.9 Referring to the virial series, Eqs. 3.29 and 3.30, show
that B BRT, C (C B2)R 2T 2. 4R2T 2c RTc
a 2
, b
pce pce2
11.10 Express Eq. 11.5, the van der Waals equation in terms of
the compressibility factor Z (b) Show that the equation of state can be expressed in terms
(a) as a virial series in vR. [Hint: Expand the (vR 18) 1 of compressibility chart variables as
4
Za b exp a b
term of Eq. 11.5 in a series.] vR
(b) as a virial series in pR. vR 1e2 TRvRe2
(c) Dropping terms involving ( pR)2 and higher in the virial
series of part (b), obtain the following approximate form: (c) Convert the result of part (b) to a virial series in vR. (Hint:
Expand the (vR 1e2)1 term in a series. Also expand
2764 pR
Z1
a b
1 the exponential term in a series.)
8 TR TR
11.14 The PengRobinson equation of state has the form
(d) Compare the compressibility factors determined from the
equation of part (c) with tabulated compressibility factors RT a
p 2
from the literature for 0 pR 0.6 and each of TR 1.0, vb v c2
1.2, 1.4, 1.6, 1.8, 2.0. Comment on the realm of validity Using Eqs. 11.3, evaluate the constants a, b, c in terms of the
of the approximate form. critical pressure pc, critical temperature Tc, and critical com-
11.11 The Berthelot equation of state has the form pressibility factor Zc.
RT a 11.15 The pvT relation for chlorofluorinated hydrocarbons
p
vb T v2 can be described by the CarnahanStarlingDeSantis equation
of state
(a) Using Eqs. 11.3, show that
pv 1
b
b2 b3 a
27 R 2T 3c
11
b2 3 RT 1v
b2
1 RTc
a , b RT
64 pc 8 pc
(b) Express the equation in terms of the compressibility fac- where b b4v, a a0 exp (a1T
a2T 2), and b b0
tor Z, the reduced temperature TR, and the pseudoreduced b1T

b2T 2. For Refrigerants 12 and 13, the required coeffi-
specific volume, vR. cients for T in K, a in J # L/(mol)2, and b in L/mol are given
in Table P11.15. Specify which of the two refrigerants would
11.12 The BeattieBridgeman equation of state can be ex-
allow the smaller amount of mass to be stored in a 10-m3
pressed as
vessel at 0.2 MPa, 80C.
RT 11 e2 1v
B2 A
p 2

v v2 Using Relations from Exact Differentials
where 11.16 The differential of pressure obtained from a certain equa-
tion of state is given by one of the following expressions. De-
A A0 a1 b , B B0 a1 b
a b
termine the equation of state.
v v
c 21v b2 1v b2 2
e dp dv
dT
vT 3 RT RT 2
and A0, B0, a, b, and c are constants. Express this equation of RT R
dp dv
1v b2 2
dT
state in terms of the reduced pressure, pR, reduced tempera- vb
a0 103 a1 103 a2 106 b0 b1 104 b2 108

R-12 3.52412 2.77230 0.67318 0.15376 1.84195 5.03644
R-13 2.29813 3.41828 1.52430 0.12814 1.84474 10.7951
Table P11.15
11.17 Introducing dQint T dS into Eq. 6.10 gives on freezing (Sec. 3.2.2). Verify this for the cases of lead that
rev
contracts on freezing and bismuth that expands on freezing.
dQint dU
p dV 11.29 Consider a four-legged chair at rest on an ice rink. The
rev
total mass of the chair and a person sitting on it is 80 kg. If
Using this expression together with the test for exactness,
the ice temperature is 2C, determine the minimum total area,
demonstrate that Qint is not a property.
rev in cm2, the tips of the chair legs can have before the ice in con-
11.18 Using Eq. 11.35, check the consistency of tact with the legs would melt. Use data from Problem 11.27
(a) the steam tables at 2 MPa, 400C. and let the local acceleration of gravity be 9.8 m/s2.
(b) the Refrigerant 134a tables at 2 bar, 50C. 11.30 Over a certain temperature interval, the saturation pres-
11.19 At a pressure of 1 atm, liquid water has a state of maxi- suretemperature curve of a substance is represented by an
mum density at about 4C. What can be concluded about equation of the form ln psat A BT, where A and B are
( 0 s 0 p)T at empirically determined constants.
(a) 3C? (a) Obtain expressions for hg hf and sg sf in terms of
(b) 4C? pvT data and the constant B.
(c) 5C? (b) Using the results of part (a), calculate hg hf and sg sf
11.20 A gas enters a compressor operating at steady state and for water vapor at 25C and compare with steam table data.
is compressed isentropically. Does the specific enthalpy in- 11.31 Using data for water from Table A-2, determine the con-
crease or decrease as the gas passes from the inlet to the exit? stants A and B to give the best fit in a least-squares sense to
11.21 Show that T, p, h, , and g can each be determined from a the saturation pressure in the interval from 20 to 30C by the
fundamental thermodynamic function of the form u u(s, v). equation ln psat A BT. Using this equation, determine
dpsatdT at 25C. Calculate hg hf at 25C and compare with
11.22 Evaluate p, s, u, h, cv, and cp for a substance for which
the steam table value.
the Helmholtz function has the form
11.32 Over limited intervals of temperature, the saturation pres-
cT c 1
ln d
v T T T
c RT ln suretemperature curve for two-phase liquidvapor states can
v T T T be represented by an equation of the form ln psat A BT,
where v and T denote specific volume and temperature, re- where A and B are constants. Derive the following expression
spectively, at a reference state, and c is a constant. relating any three states on such a portion of the curve:
psat, 3 psat, 2 t
a b
11.23 The Mollier diagram provides a graphical representation
of the fundamental thermodynamic function h h(s, p). Show psat, 1 psat,1
that at any state fixed by s and p the properties T, v, u, , and
g can be evaluated using data obtained from the diagram. where T2(T3 T1)T3(T2 T1).
11.24 Derive the relation cp T( 0 g 0T )p.
2 2
11.33 Use the result of Problem 11.42 to determine
(a) the saturation pressure at 30C using saturation
Evaluating s, u, and h pressuretemperature data at 20 and 40C from Table
A-2. Compare with the table value for saturation pressure
11.25 Using pvT data for saturated water from the steam
at 30C.
tables, calculate at 50C
(b) the saturation temperature at 0.006 MPa using saturation
(a) hg hf. pressuretemperature data at 20 to 40C from Table A-2.
(b) ug uf. Compare with the saturation temperature at 0.006 MPa
(c) sg sf. given in Table A-3.
Compare with the values obtained using steam table data. 11.34 Complete the following exercises dealing with slopes:
11.26 Using hfg, vfg, and psat at 26C from the ammonia tables,
(a) At the triple point of water, evaluate the ratio of the slope
estimate the saturation pressure at 30C. Comment on the
of the vaporization line to the slope of the sublimation line.
accuracy of your estimate.
Use steam table data to obtain a numerical value for the
11.27 At 0C, the specific volumes of saturated solid water (ice) ratio.
and saturated liquid water are, respectively, vi 1.0911 (b) Consider the superheated vapor region of a
103 m3/kg and vf 1.0002 103 m3/kg, and the change in temperatureentropy diagram. Show that the slope of a
specific enthalpy on melting is hif 333.4 kJ/kg. Calculate the constant specific volume line is greater than the slope of
melting temperature of ice at (a) 250 bar, (b) 500 bar. Locate a constant pressure line through the same state.
your answers on a sketch of the pT diagram for water. (c) An enthalpyentropy diagram (Mollier diagram) is often
11.28 The line representing the two-phase solidliquid region used in analyzing steam turbines. Obtain an expression for
on the phase diagram slopes to the left for substances that ex- the slope of a constant-pressure line on such a diagram in
pand on freezing and to the right for substances that contract terms of pvT data only.
(d) A pressureenthalpy diagram is often used in the refrig- 11.44 Derive expressions for the volume expansivity and the
eration industry. Obtain an expression for the slope of an isothermal compressibility
in terms of T, p, Z, and the first
isentropic line on such a diagram in terms of pvT data partial derivatives of Z. For gas states with pR 3, TR 2,
only. determine the sign of k. Discuss.
11.35 One kmol of argon at 300 K is initially confined to one 11.45 Show that the isothermal compressibility
is always
side of a rigid, insulated container divided into equal volumes greater than or equal to the isentropic compressibility .
of 0.2 m3 by a partition. The other side is initially evacuated.
11.46 Prove that ( 0 0 p)T ( 0
0 T)p.
The partition is removed and the argon expands to fill the en-
tire container. Using the van der Waals equation of state, de- 11.47 For aluminum at 0C, 2700 kg/m3, 71.4 108
termine the final temperature of the argon, in K. Repeat using (K)1,
1.34 1013 m2/N, and cp 0.9211 kJ/kg # K. De-
the ideal gas equation of state. termine the percent error in cv that would result if it were as-
sumed that cp cv.
11.36 Obtain the relationship between cp and cv for a gas that
obeys the equation of state p(v b) RT. 11.48 Estimate the temperature rise, in C, of mercury, initially
11.37 The pvT relation for a certain gas is represented closely at 0C and 1 bar if its pressure were raised to 1000 bar isen-
by v RTp
B ART, where R is the gas constant and A tropically. For mercury at 0C, cp 28.0 kJ/kmol # K,
and B are constants. Determine expressions for the changes in v 0.0147 m3/kmol, and 17.8 105 (K)1.
specific enthalpy, internal energy, and entropy, [h(p2, T ) 11.49 At certain states, the pvT data for a particular gas can be
h( p1, T)], [u(p2, T ) u(p1, T )], and [s(p2, T ) s( p1, T)], represented as Z 1 ApT 4, where Z is the compressibility
respectively. factor and A is a constant. Obtain an expression for the specific
11.38 Develop expressions for the specific enthalpy, internal heat cp in terms of the gas constant R, specific heat ratio k, and
energy, and entropy changes [h(v2, T ) h(v1, T )], [u(v2, T) Z. Verify that your expression reduces to Eq. 3.47a when Z 1.
u(v1, T)], [s(v2, T) s(v1, T )], using the 11.50 For a gas obeying the van der Waals equation of state,
(a) van der Waals equation of state.
(a) show that ( 0cv 0v)T 0.
(b) RedlichKwong equation of state.
(b) develop an expression for cp cv.
11.39 At certain states, the pvT data of a gas can be expressed (c) develop expressions for [u(T2, v2) u(T1, v1)] and
as Z 1 ApT 4, where Z is the compressibility factor and [s(T2, v2) s(T1, v1)].
A is a constant. (d) complete the u and s evaluations if cv a
bT, where
(a) Obtain an expression for ( 0p 0T )v in terms of p, T, A, and a and b are constants.
the gas constant R. 11.51 Show that the specific heat ratio k can be expressed as k
(b) Obtain an expression for the change in specific entropy, cp
(cp
Tv2). Using this expression together with data from
[s(p2, T) s(p1, T )]. the steam tables, evaluate k for water vapor at 200 lbf/in.2, 500F.
(c) Obtain an expression for the change in specific enthalpy,
[h( p2, T) h(p1, T )]. 11.52 For liquid water at 40C, 1 atm estimate
11.40 For a gas whose pvT behavior is described by Z 1
(a) cv, in kJ/kg # K
BpRT, where B is a function of temperature, derive expres- (b) the velocity of sound, in m/s.
sions for the specific enthalpy, internal energy, and entropy Use Data from Table 11.2, as required.
changes, [h(p2, T) h(p1, T )], [u(p2, T ) u(p1, T )], and
11.53 Using steam table data, estimate the velocity of sound in
[s(p2, T) s(p1, T)].
liquid water at 20C, 50 bar.
11.41 For a gas whose pvT behavior is described by Z 1
Bv
Cv2, where B and C are functions of temperature, de- 11.54 For a gas obeying the equation of state p(v b) RT,
rive an expression for the specific entropy change, [s(v2, T) where b is a positive constant, can the temperature be reduced
s(v1, T)]. in a JouleThomson expansion?
11.55 A gas is described by v RTp AT
B, where A
Using Other Thermodynamic Relations
and B are constants. For the gas
11.42 The volume of a 1-kg copper sphere is not allowed to
(a) obtain an expression for the temperatures at the
vary by more than 0.1%. If the pressure exerted on the sphere
JouleThomson inversion states.
is increased from 10 bar while the temperature remains con-
(b) obtain an expression for cp cv.
stant at 300 K, determine the maximum allowed pressure, in
bar. Average values of , , and
are 8888 kg/m3, 49.2 106 11.56 Determine the maximum JouleThomson inversion tem-
(K)1, and 0.776 1011 m2/N, respectively. perature in terms of the critical temperature Tc predicted by the
11.43 Develop expressions for the volume expansivity and (a) van der Waals equation.
the isothermal compressibility
for (b) RedlichKwong equation.
(a) an ideal gas. (c) Dieterici equation given in Problem 11.13.
(b) a gas whose equation of state is p(v b) RT. 11.57 Derive an equation for the JouleThomson coefficient as
(c) a gas obeying the van der Waals equation. a function of T and v for a gas that obeys the van der Waals
equation of state and whose specific heat cv is given by cv 11.66 Derive expressions for the enthalpy and entropy depar-
A
BT
CT 2, where A, B, C are constants. Evaluate the tem- tures using an equation of state with the form Z 1
BpR,
peratures at the inversion states in terms of R, v, and the van where B is a function of the reduced temperature, TR.
der Waals constants a and b. 11.67 The following expression for the enthalpy departure is
11.58 Show that Eq. 11.63 can be written as convenient for use with equations of state that are explicit in
T 2 0 1vT 2
pressure:
mJ a b
cp 0T p h*1T 2 h1T, v2
TR c 1 Z cT a b pddvd
1 v 0p
(a) Using this result, obtain an expression for the JouleThomson RTc RT 0T v
coefficient for a gas obeying the equation of state
Ap (a) Derive this expression.
RT
v 2 (b) Using the given expression, evaluate the enthalpy depar-
p T ture for a gas obeying the RedlichKwong equation of
where A is a constant. state.
(b) Using the result of part (a), determine cp, in kJ/kg # K, for (c) Using the result of part (b), determine the change in spe-
CO2 at 400 K, 1 atm, where J 0.57 K/atm. For CO2, cific enthalpy, in kJ/kmol, for CO2 undergoing an isother-
A 2.78 103 m5 # K2/kg # N. mal process at 300 K from 50 to 20 bar.
11.68 Using the equation of state of Problem 11.10 (c), evalu-
ate v and cp for water vapor at 550C, 20 MPa and compare
Developing Property Data
with data from Table A-4 and Fig. 3.9, respectively. Discuss.
11.59 If the specific heat cv of a gas obeying the van der Waals
equation is given at a particular pressure, p, by cv A
BT, 11.69 Ethylene at 67C, 10 bar enters a compressor operating
where A and B are constants, develop an expression for the a steady state and is compressed isothermally without internal
change in specific entropy between any two states 1 and 2: irreversibilities to 100 bar. Kinetic and potential energy
[s(T2, p2) s(T1, p1)]. changes are negligible. Evaluate in kJ per kg of ethylene flow-
ing through the compressor
11.60 For air, write a computer program that evaluates the
(a) the work required.
change in specific enthalpy from a state where the temperature
(b) the heat transfer.
is 25C and the pressure is 1 atm to a state where the temper-
ature is T and the pressure is p. Use the van der Waals equa- 11.70 Methane at 27C, 10 MPa enters a turbine operating at
tion of state and account for the variation of the ideal gas spe- steady state, expands adiabatically through a 5 : 1 pressure ra-
cific heat as in Table A-21. tio, and exits at 48C. Kinetic and potential energy effects
11.61 Using the RedlichKwong equation of state, determine are negligible. If cpo 35 kJ/kmol # K, determine the work de-
the changes in specific enthalpy, in kJ/kmol, and entropy, in veloped per kg of methane flowing through the turbine. Com-
kJ/kmol # K, for ethylene between 400 K, 1 bar and 400 K, pare with the value obtained using the ideal gas model.
100 bar. 11.71 Nitrogen (N2) enters a compressor operating at steady
11.62 Using the BenedictWebbRubin equation of state to- state at 1.5 MPa, 300 K and exits at 8 MPa, 500 K. If the work
gether with a specific heat relation from Table A-21, determine input is 240 kJ per kg of nitrogen flowing, determine the heat
the change in specific enthalpy, in kJ/kmol, for methane be- transfer, in kJ per kg of nitrogen flowing. Ignore kinetic and
tween 300 K, 1 atm and 400 K, 200 atm. potential energy effects.
11.63 Using the RedlichKwong equation of state together with 11.72 Oxygen (O2) enters a control volume operating at steady
an appropriate specific heat relation, determine the final tem- state with a mass flow rate of 9 kg/min at 100 bar, 287 K and
perature for an isentropic expansion of nitrogen from 400 K, is compressed adiabatically to 150 bar, 400 K. Determine the
250 atm to 5 atm. power required, in kW, and the rate of entropy production, in
kW/K. Ignore kinetic and potential energy effects.
11.73 Argon gas enters a turbine operating at steady state at
Using Enthalpy and Entropy Departures 100 bar, 325 K and expands adiabatically to 40 bar, 235 K with
11.64 Beginning with Eq. 11.90, derive Eq. 11.91. no significant changes in kinetic or potential energy. Determine
11.65 Derive an expression giving (a) the work developed, in kJ per kg of argon flowing through
the turbine.
(a) the internal energy of a substance relative to that of its
(b) the amount of entropy produced, in kJ/K per kg of argon
ideal gas model at the same temperature: [u(T, v) u*(T )].
flowing.
(b) the entropy of a substance relative to that of its ideal gas
model at the same temperature and specific volume: 11.74 Oxygen (O2) undergoes a throttling process from 100 bar,
[s(T, v) s*(T, v)]. 300 K to 20 bar. Determine the temperature after throttling, in
K, and compare with the value obtained using the ideal gas (c) the van der Waals equation together with mixture values
model. for the constants a and b.
11.75 Water vapor enters a turbine operating at steady state at (d) the rule of additive pressure together with the generalized
30 MPa, 600C and expands adiabatically to 6 MPa with no sig- compressibility chart.
nificant change in kinetic or potential energy. If the isentropic tur- 11.82 Air having an approximate molar composition of 79%
bine efficiency is 80%, determine the work developed, in kJ per N2 and 21% O2 fills a 0.36-m3 vessel. The mass of mixture is
kg of steam flowing, using the generalized property charts. Com- 100 kg. The measured pressure and temperature are 101 bar
pare with the result obtained using steam table data. Discuss. and 180 K, respectively. Compare the measured pressure with
11.76 Oxygen (O2) enters a nozzle operating at steady state at the pressure predicted using
60 bar, 300 K, 1 m /s and expands isentropically to 30 bar. De- (a) the ideal gas equation of state.
termine the velocity at the nozzle exit, in m /s. (b) Kays rule.
11.77 A quantity of nitrogen gas undergoes a process at a con- (c) the additive pressure rule with the RedlichKwong equation.
stant pressure of 80 bar from 220 to 300 K. Determine the (d) the additive volume rule with the RedlichKwong equation.
work and heat transfer for the process, each in kJ per kmol of
11.83 Using the CarnahanStarlingDeSantis equation of
nitrogen.
state introduced in Problem 11.15, together with the following
11.78 A closed, rigid, insulated vessel having a volume of expressions for the mixture values of a and b:
0.142 m3 contains oxygen (O2) initially at 100 bar, 7C. The
oxygen is stirred by a paddle wheel until the pressure becomes a y21a1
2y1y2 11 f12 21a1a2 2 1 2
y22a2
150 bar. Determine the b y1b1
y2b2
(a) final temperature, in C. where f12 is an empirical interaction parameter, determine the
(b) work, in kJ. pressure, in kPa, at v 0.005 m3/kg, T 180C for a mix-
(c) amount of exergy destroyed in the process, in kJ. ture of Refrigerants 12 and 13, in which Refrigerant 12 is 40%
Let T0 7C. by mass. For a mixture of Refrigerants 12 and 13, f12 0.035.
11.84 A rigid vessel initially contains carbon dioxide gas at
32C and pressure p. Ethylene gas is allowed to flow into the
Evaluating pvT for Gas Mixtures
tank until a mixture consisting of 20% carbon dioxide and 80%
11.79 A preliminary design calls for a 1 kmol mixture of CO2 ethylene (molar basis) exists within the tank at a temperature
and C2H6 (ethane) to occupy a volume of 0.15 m3 at a tem- of 43C and a pressure of 110 bar. Determine the pressure p,
perature of 400 K. The mole fraction of CO2 is 0.3. Owing to in bar, using Kays rule together with the generalized com-
safety requirements, the pressure should not exceed 180 bar. pressibility chart.
Check the pressure using
(a) the ideal gas equation of state.
(b) Kays rule together with the generalized compressibility Analyzing Multicomponent Systems
chart. 11.85 A binary solution at 25C consists of 59 kg of ethyl
(c) the additive pressure rule together with the generalized alcohol (C2H5OH) and 41 kg of water. The respective partial
compressibility chart. molal volumes are 0.0573 and 0.0172 m3/kmol. Determine the
Compare and discuss these results. total volume, in m3. Compare with the volume calculated us-
ing the molar specific volumes of the pure components, each
11.80 A 0.1-m3 cylinder contains a gaseous mixture with a mo-
a liquid at 25C, in the place of the partial molal volumes.
lar composition of 97% CO and 3% CO2 initially at 138 bar. Due
to a leak, the pressure of the mixture drops to 129 bar while the 11.86 The following data are for a binary solution of ethane
temperature remains constant at 30C. Using Kays rule, estimate (C2H6) and pentane (C5H12) at a certain temperature and
the amount of mixture, in kmol, that leaks from the cylinder. pressure:
mole fraction of ethane 0.2 0.3 0.4 0.5 0.6 0.7 0.8
volume (in m3) per kmol of solution 0.119 0.116 0.112 0.109 0.107 0.107 0.11
11.81 A gaseous mixture consisting of 0.75 kmol of hydrogen Estimate

(H2) and 0.25 kmol of nitrogen (N2) occupies 0.085 m3 at 25C. (a) the specific volumes of pure ethane and pure pentane, each
Estimate the pressure, in bar, using in m3/kmol.
(a) the ideal gas equation of state. (b) the partial molal volumes of ethane and pentane for an
(b) Kays rule together with the generalized compressibility equimolar solution, each in m3/kmol.
chart.
11.87 Using pvT data from the steam tables, determine the fu- 11.96 Methane enters a turbine operating at steady state at
gacity of water as a saturated vapor at 280C, Compare with the 100 bar, 275 K and expands isothermally without irre-
value obtained from the generalized fugacity chart. versibilities to 15 bar. There are no significant changes in
11.88 Using the equation of state of Problem 11.10 (c), eval- kinetic or potential energy. Using data from the generalized
uate the fugacity of ammonia at 750 K, 100 atm and compare fugacity and enthalpy departure charts, determine the power
with the value obtained from Fig. A-6. developed and heat transfer, each in kW, for a mass flow rate
of 0.5 kg/s.
11.89 Using tabulated compressibility data from the literature,
11.97 Methane flows isothermally and without irreversibilities
evaluate fp at TR 1.40 and pR 2.0. Compare with the
through a horizontal pipe operating at steady state, entering at
value obtained from Fig. A-6.
50 bar, 300 K, 10 m /s and exiting at 40 bar. Using data from
11.90 Consider the truncated virial expansion the generalized fugacity chart, determine the velocity at the
Z 1
B1TR 2pR
C1TR 2p2R
D1TR 2p3R exit, in m /s.
11.98 Determine the fugacity, in atm, for pure ethane at 310
(a) Using tabulated compressibility data from the literature, K, 20.4 atm and as a component with a mole fraction of 0.35
evaluate the coefficients B, C, and D for 0 pR 1.0 and in an ideal solution at the same temperature and pressure.
each of TR 1.0, 1.2, 1.4, 1.6, 1.8, 2.0.
11.99 Denoting the solvent and solute in a dilute binary liq-
(b) Obtain an expression for ln ( fp) in terms of TR and pR. Us-
uid solution at temperature T and pressure p by the subscripts
ing the coefficients of part (a), evaluate fp at selected states
1 and 2, respectively, show that if the fugacity of the solute is
and compare with tabulated values from the literature.
proportional to its mole fraction in the solution: f 2 ky2,
11.91 Derive the following approximation for the fugacity of where
is a constant (Henrys rule), then the fugacity of the
a liquid at temperature T and pressure p: solvent is f 1 y1 f1, where y1 is the solvent mole fraction and
vf 1T 2 f1 is the fugacity of pure 1 at T, p.
f 1T, p2 f Lsat 1T 2 exp e 3p psat 1T 2 4 f 11.100 A tank contains 310 kg of a gaseous mixture of 70%
RT
ethane and 30% nitrogen (molar basis) at 311 K and 170 atm.
L
where fsat (T) is the fugacity of the saturated liquid at temper- Determine the volume of the tank, in m3, using data from the
ature T. For what range of pressures might the approximation generalized compressibility chart together with (a) Kays rule,
f (T, p) fsat
L
(T) apply? (b) the ideal solution model. Compare with the measured tank
11.92 Beginning with Eq. 11.122, volume of 1 m3.
(a) evaluate ln f for a gas obeying the RedlichKwong equa- 11.101 A tank contains a mixture of 70% ethane and 30%
tion of state. nitrogen (N2) on a molar basis at 400 K, 200 atm. For 2130
(b) Using the result of part (a), evaluate the fugacity, in kg of mixture, estimate the tank volume, in m3, using
bar, for Refrigerant 134a at 90C, 10 bar. Compare with (a) the ideal gas equation of state.
the fugacity value obtained from the generalized fugacity (b) Kays rule together with data from the generalized com-
chart. pressibility chart.
11.93 Consider a one-inlet, one-exit control volume at steady (c) the ideal solution model together with data from the gen-
state through which the flow is internally reversible and eralized compressibility chart.
isothermal. Show that the work per unit of mass flowing can 11.102 An equimolar mixture of O2 and N2 enters a compres-
be expressed in terms of the fugacity f as sor operating at steady state at 10 bar, 220 K with a mass flow
# rate of 1 kg/s. The mixture exits at 60 bar, 400 K with no
V21 V22
a # b RT ln a b

g1z1 z2 2
Wcv f2 significant change in kinetic or potential energy. Stray heat
m int f1 2 transfer from the compressor can be ignored. Determine for
rev
the compressor
11.94 Propane (C3H8) enters a turbine operating at steady state
(a) the power required, in kW.
at 100 bar, 400 K and expands isothermally without irre-
(b) the rate of entropy production, in kW/K.
versibilities to 10 bar. There are no significant changes in ki-
netic or potential energy. Using data from the generalized fu- Assume the mixture is modeled as an ideal solution. For the
gacity chart, determine the power developed, in kW, for a mass pure components:
flow rate of 50 kg/min.
10 bar, 220 K 60 bar, 400 K
11.95 Ethane (C2H6) is compressed isothermally without ir-
h (kJ/kg) s (kJ/kg # K) h (kJ/kg) s (kJ/kg # K)
reversibilities at a temperature of 320 K from 5 to 40 bar.
Using data from the generalized fugacity and enthalpy de- Oxygen 195.6 5.521 358.2 5.601
parture charts, determine the work of compression and the Nitrogen 224.1 5.826 409.8 5.911
heat transfer, each in kJ per kg of ethane flowing. Assume
steady-state operation and neglect kinetic and potential 11.103 A gaseous mixture with a molar analysis of 70% CH4
energy effects. and 30% N2 enters a compressor operating at steady state at
10 bar, 250 K and a molar flow rate of 6 kmol/h. The mixture 11.104 The departure of a binary solution from ideal solution
exits the compressor at 100 bar. During compression, the tem- behavior is gauged by the activity coefficient, i aiyi, where
perature of the mixture departs from 250 K by no more than ai is the activity of component i and yi is its mole fraction in
0.1 K. The power required by the compressor is reported to be the solution (i 1, 2). Introducing Eq. 11.140, the activity coef-
6 kW. Can this value be correct? Explain. Ignore kinetic and ficient can be expressed alternatively as gi fi yi f i. Using this
potential energy effects. Assume the mixture is modeled as an expression together with the GibbsDuhem equation, derive the
ideal solution. For the pure components at 250 K: following relation among the activity coefficients and the mole
fractions for a solution at temperature T and pressure p:
h (kJ/kg) s (kJ/kg # K)
ay1 b ay2 b
10 bar 100 bar 10 bar 100 bar 0 ln g1 0 ln g2
Methane 506.0 358.6 10.003 8.3716 0y1 p, T 0y2 p, T
Nitrogen 256.18 229.68 5.962 5.188
How might this expression be used?
11.1D Compressed natural gas (CNG) is being used as a fuel exergy is stored by compressing the nitrogen. When the vehi-
to replace gasoline for automobile engines. Aluminum cylin- cle accelerates again, the gas expands and returns some exergy
ders wrapped in a fibrous composite can provide lightweight, to the hydraulic fluid which is in communication with the ve-
economical, and safe on-board storage. The storage vessels hicles drive train, thereby assisting the vehicle to accelerate.
should hold enough CNG for 100 to 125 miles of urban travel, In a proposal for one such device, the nitrogen operates in the
at storage pressures up to 20 Mpa, and with a maximum total range 50150 bar and 200350 K. Develop a thermodynamic
mass of 70 kg. Adhering to applicable standards, specify both model of the accumulator and use the model to assess its suit-
the size and number of cylinders that would meet the above ability for vehicle deceleration/acceleration.
design constraints. 11.4D To investigate liquidvapor phase transition behavior,
11.2D Develop the preliminary design of a thermal storage sys- construct a pv diagram for water showing isotherms in the
tem that would recover automobile engine waste heat for later range 0.7 TR 1.2 by solving the van der Waals equation
use in improving the engine cold-start performance. Among of state for pressure and specific volume at constant tempera-
the specifications are: Reliable operation down to an ambient ture. Superimpose the vapor dome on the diagram using satu-
temperature of 30C, a storage duration of 16 hours, and no rated liquid and saturated vapor data from the steam tables. In-
more than 15 minutes of urban driving to return the storage terpret the behavior of the various isotherms in the liquid and
medium to its maximum temperature of 200C. Specify the vapor regions on the diagram. Referring to the literature as nec-
storage medium and determine whether the medium should be essary, explain the behavior of the isotherms in the two-phase,
charged by the engine exhaust gases, the engine coolant, or liquidvapor region, carefully distinguishing among stable,
some combination. Explain how the system would be config- metastable, and unstable states. Write a paper discussing the
ured and where it would be located in the automobile. plot and summarizing your findings.
11.3D Figure P11.3D shows the schematic of a hydraulic ac- 11.5D In the experiment for the regelation of ice, a small-
cumulator in the form of a cylindrical pressure vessel with a diameter wire weighted at each end is draped over a block of
piston separating a hydraulic fluid from a charge of nitrogen ice. The loaded wire is observed to cut slowly through the ice
gas. The device has been proposed as a means for storing some without leaving a trace. In one such set of experiments, a
of the exergy of a decelerating vehicle as it comes to rest. The weighted 1.00-mm diameter wire is reported to have passed
through 0C ice at a rate of 54 mm /h. Perform the regelation
experiment and propose a plausible explanation for this
phenomenon.
11.6D During a phase change from liquid to vapor at fixed
Piston
pressure, the temperature of a binary nonazeotropic solution
Hydraulic Nitrogen such as an ammoniawater solution increases rather than re-
fluid gas mains constant as for a pure substance. This attribute is ex-
ploited in both the Kalina power cycle and in the Lorenz re-
frigeration cycle. Write a report assessing the status of
technologies based on these cycles. Discuss the principal ad-
Figure P11.3D vantages of using binary nonazeotropic solutions. What are
some of the main design issues related to their use in power 11.8D An inventor has proposed a new type of marine engine
and refrigeration systems? fueled by fresh water stored on board and seawater drawn in
11.7D The Servel refrigerator works on an absorption principle from the surrounding ocean. At steady state, the engine would
and requires no moving parts. An energy input by heat trans- develop power from freshwater and seawater streams, each en-
fer is used to drive the cycle, and the refrigerant circulates due tering the engine at the ambient temperature and pressure. A
to its natural buoyancy. This type of refrigerator is commonly single mixed stream would be discharged at the ambient tem-
employed in mobile applications, such as recreational vehicles. perature and pressure. Critically evaluate this proposal.
Liquid propane is burned to provide the required energy input 11.9D Small Power Plants Pack Punch (see box Sec. 11.5).
during mobile operation, and electric power is used when the Using manufacturers data, specify a natural gas-fueled mi-
vehicle is parked and can be connected to an electrical outlet. croturbine cogeneration system to provide for the needs of a
Investigate the principles of operation of commercially avail- hospital in your locale. Write a report including at least three
able Servel-type systems, and study their feasibility for solar- references.
activated operation. Consider applications in remote locations
where electricity or gas is not available. Write a report sum-
marizing your findings.
C
H
A
P Ideal Gas
T
Mixture and
12 E
R Psychrometric
Applications
E N G I N E E R I N G C O N T E X T Many systems of interest involve gas
mixtures of two or more components. To apply the principles of thermodynamics introduced
thus far to these systems requires that we evaluate properties of the mixtures. Means are
available for determining the properties of mixtures from the mixture composition and the
properties of the individual pure components from which the mixtures are formed. Methods
for this purpose are discussed both in Chap. 11 and in the present chapter.
chapter objective The objective of the present chapter is to study mixtures where the overall mixture
and each of its components can be modeled as ideal gases. General ideal gas mixture
considerations are provided in the first part of the chapter. Understanding the behavior of
ideal gas mixtures of air and water vapor is prerequisite to considering air-conditioning
processes in the second part of the chapter. In those processes, we sometimes must con-
sider the presence of liquid water as well. We will also need to know how to handle ideal
gas mixtures when we study the subjects of combustion and chemical equilibrium in
Chapters 13 and 14, respectively.
IDEAL GAS MIXTURES:

GENERAL CONSIDERATIONS

12.1 Describing Mixture Composition
To specify the state of a mixture requires the composition and the values of two independ-
ent intensive properties such as temperature and pressure. The object of the present section
is to consider ways for describing mixture composition. In subsequent sections, we show
how mixture properties other than composition can be evaluated.
Consider a closed system consisting of a gaseous mixture of two or more components.
The composition of the mixture can be described by giving the mass or the number of moles
of each component present. With Eq. 1.10, the mass, the number of moles, and the molecu-
lar weight of a component i are related by
mi
ni (12.1)
Mi
558
12.1 Describing Mixture Composition 559
where mi is the mass, ni is the number of moles, and Mi is the molecular weight of compo-
nent i, respectively. When mi is expressed in terms of the kilogram, ni is in kmol. However,
any unit of mass can be used in this relationship.
The total mass of the mixture, m, is the sum of the masses of its components
j
m m1
m2
# # #
mj a mi (12.2)
i1
The relative amounts of the components present in the mixture can be specified in terms
of mass fractions. The mass fraction mfi of component i is defined as
mi
mfi (12.3) mass fractions
m
A listing of the mass fractions of the components of a mixture is sometimes referred to as

a gravimetric analysis. gravimetric analysis
Dividing each term of Eq. 12.2 by the total mass of mixture m and using Eq. 12.3
j
1 a mfi (12.4)
i1
That is, the sum of the mass fractions of all the components in a mixture is equal to unity.
The total number of moles in a mixture, n, is the sum of the number of moles of each of
its components
j
n n1
n2
# # #
nj a ni (12.5)
i1
The relative amounts of the components present in the mixture also can be described in
terms of mole fractions. The mole fraction yi of component i is defined as
ni
yi (12.6) mole fractions
n
A listing of the mole fractions of the components of a mixture may be called a molar analysis. molar analysis
An analysis of a mixture in terms of mole fractions is also called a volumetric analysis.
volumetric analysis
Dividing each term of Eq. 12.5 by the total number of moles of mixture n and using
Eq. 12.6
j
1 a yi (12.7)
i1
That is, the sum of the mole fractions of all the components in a mixture is equal to unity.
The apparent (or average) molecular weight of the mixture, M, is defined as the ratio of
the total mass of the mixture, m, to the total number of moles of mixture, n
m apparent molecular
M (12.8)
n weight
560 Chapter 12 Ideal Gas Mixture and Psychrometric Applications
TABLE 12.1 Approximate Composition of Dry Air

Mole Fraction
Component (%)
Nitrogen 78.08
Oxygen 20.95
Argon 0.93
Carbon dioxide 0.03
Neon, helium, methane, and others 0.01
Equation 12.8 can be expressed in a convenient alternative form. With Eq. 12.2, it
becomes
m1
m2
# # #
mj
M
n
Introducing mi niMi from Eq. 12.1
n1M1
n2M2
# # #
nj Mj
M
n
Finally, with Eq. 12.6, the apparent molecular weight of the mixture can be calculated as a
mole-fraction average of the component molecular weights
j
M a yi Mi (12.9)
i1
for example. . . consider the case of air. A sample of atmospheric air contains sev-
eral gaseous components including water vapor and contaminants such as dust, pollen, and
dry air pollutants. The term dry air refers only to the gaseous components when all water vapor and
contaminants have been removed. The molar analysis of a typical sample of dry air is given
in Table 12.1. Selecting molecular weights for nitrogen, oxygen, argon, and carbon dioxide
from Table A-1, and neglecting the trace substances neon, helium, etc., the apparent molec-
ular weight of dry air obtained from Eq. 12.9 is
M 0.7808128.022
0.2095132.002
0.0093139.942
0.0003144.012
28.97 kg/kmol
This value, which is the entry for air in Tables A-1, would not be altered significantly if the
trace substances were also included in the calculation.
Next, we consider two examples illustrating, respectively, the conversion from an analy-
sis in terms of mole fractions to an analysis in terms of mass fractions, and conversely.
EXAMPLE 12.1 Converting Mole Fractions to Mass Fractions
The molar analysis of the gaseous products of combustion of a certain hydrocarbon fuel is CO2, 0.08; H2O, 0.11; O2, 0.07;
N2, 0.74. (a) Determine the apparent molecular weight of the mixture. (b) Determine the composition in terms of mass frac-
tions (gravimetric analysis).
12.1 Describing Mixture Composition 561
SOLUTION
Known: The molar analysis of the gaseous products of combustion of a hydrocarbon fuel is given.
Find: Determine (a) the apparent molecular weight of the mixture, (b) the composition in terms of mass fractions.
Analysis:
(a) Using Eq. 12.9 and approximate molecular weights from Table A-1
M 0.081442
0.111182
0.071322
0.741282
28.46 kg/kmol
(b) Equations 12.1, 12.3, and 12.6 are the key relations required to determine the composition in terms of mass fractions.
Although the actual amount of mixture is not known, the calculations can be based on any convenient amount. Let us base
the solution on 1 kmol of mixture. Then, with Eq. 12.6 the amount ni of each component present in kmol is numerically equal
to the mole fraction, as listed in column (ii) of the accompanying table. Column (iii) of the table gives the respective molec-
ular weights of the components.
Column (iv) of the table gives the mass mi of each component, in kg per kmol of mixture, obtained with Eq. 12.1 in the
form mi Mini. The values of column (iv) are obtained by multiplying each value of column (ii) by the corresponding value
of column (iii). The sum of the values in column (iv) is the mass of the mixture: kg of mixture per kmol of mixture. Note
that this sum is just the apparent mixture molecular weight determined in part (a). Finally, using Eq. 12.3, column (v) gives
the mass fractions as a percentage. The values of column (v) are obtained by dividing the values of column (iv) by the column
(iv) total and multiplying by 100.
(i) (ii)a (iii) (iv)b (v)

Component ni Mi mi m fi (%)
CO2 0.08 44 3.52 12.37
H2O 0.11 18 1.98 6.96
O2 0.07 32 2.24 7.87
N2 0.74 28 20.72 72.80
1.00 28.46 100.00
a
Entries in this column have units of kmol per kmol of mixture. For example,
the first entry is 0.08 kmol of CO2 per kmol of mixture.
b
Entries in this column have units of kg per kmol of mixture. For example, the
first entry is 3.52 kg of CO2 per kmol of mixture. The column sum, 28.46, has
units of kg of mixture per kmol of mixture.
If the solution to part (b) were conducted on the basis of some other assumed amount of mixturefor example, 100 kmol
the same result for the mass fractions would be obtained, as can be verified.
EXAMPLE 12.2 Converting Mass Fractions to Mole Fractions
A gas mixture has the following composition in terms of mass fractions: H2, 0.10; N2, 0.60; CO2, 0.30. Determine (a) the
composition in terms of mole fractions and (b) the apparent molecular weight of the mixture.
SOLUTION
Known: The gravimetric analysis of a gas mixture is known.
Find: Determine the analysis of the mixture in terms of mole fractions (molar analysis) and the apparent molecular weight
of the mixture.
Analysis:
(a) Equations 12.1, 12.3, and 12.6 are the key relations required to determine the composition in terms of mole fractions.
Although the actual amount of mixture is not known, the calculation can be based on any convenient amount. Let us base
the solution on 100 kg. Then, with Eq. 12.3, the amount mi of each component present, in kg, is equal to the mass fraction
multiplied by 100 kg. The values are listed in column (ii) of the accompanying table. Column (iii) of the table gives the
respective molecular weights of the components.
Column (iv) of the table gives the amount ni of each component, in kmol per 100 kg of mixture, obtained using Eq. 12.1.
The values of column (iv) are obtained by dividing each value of column (ii) by the corresponding value of column (iii). The
sum of the values of column (iv) is the total amount of mixture, in kmol per 100 kg of mixture. Finally, using Eq. 12.6, column
(v) gives the mole fractions as a percentage. The values of column (v) are obtained by dividing the values of column (iv) by
the column (iv) total and multiplying by 100.
(i) (ii)a (iii) (iv)b (v)

Component mi Mi ni yi (%)
H2 10 2 5.00 63.9
N2 60 28 2.14 27.4
CO2 30 44 0.68 8.7
100 7.82 100.0
a
Entries in this column have units of kg per 100 kg of mixture. For example, the
first entry is 10 kg of H2 per 100 kg of mixture.
b
Entries in this column have units of kmol per 100 kg of mixture. For example,
the first entry is 5.00 kmol of H2 per 100 kg of mixture. The column sum, 7.82,
has units of kmol of mixture per 100 kg of mixture.
(b) The apparent molecular weight of the mixture can be found by using Eq. 12.9 and the calculated mole fractions. The
value can be determined alternatively by using the column (iv) total giving the total amount of mixture in kmol per 100 kg
of mixture. Thus, with Eq. 12.8
m 100 kg kg
M 12.79
n 7 .82 kmol kmol
If the solution to part (a) were conducted on the basis of some other assumed amount of mixture, the same result for the
mass fractions would be obtained, as can be verified.
Although H2 has the smallest mass fraction, its mole fraction is the largest.

12.2 Relating p, V, and T for
Ideal Gas Mixtures
The definitions given in Sec. 12.1 apply generally to mixtures. In the present section we are
concerned only with ideal gas mixtures and introduce two models used in conjunction with
this idealization: the Dalton model and the Amagat model.
Consider a system consisting of a number of gases contained within a closed vessel of
volume V as shown in Fig. 12.1. The temperature of the gas mixture is T and the pressure is
p. The overall mixture is considered an ideal gas, so p, V, T, and the total number of moles
of mixture n are related by the ideal gas equation of state
RT
pn (12.10)
V
With reference to this system, let us consider in turn the Dalton and Amagat models.
12.2 Relating p, V, and T for Ideal Gas Mixtures 563
Temperature = T
Pressure = p
Gas 1 : n1
Gas 2 : n2
n moles
mixture
Gas j : nj
Boundary Volume = V Figure 12.1 Mixture of several gases.
DALTON MODEL. The Dalton model is consistent with the concept of an ideal gas as be-
ing made up of molecules that exert negligible forces on one another and whose volume is
negligible relative to the volume occupied by the gas (Sec. 3.5). In the absence of signifi-
cant intermolecular forces, the behavior of each component would be unaffected by the pres-
ence of the other components. Moreover, if the volume occupied by the molecules is a very
small fraction of the total volume, the molecules of each gas present may be regarded as free
to roam throughout the full volume. In keeping with this simple picture, the Dalton model Dalton model
assumes that each mixture component behaves as an ideal gas as if it were alone at the
temperature T and volume V of the mixture.
It follows from the Dalton model that the individual components would not exert the mix-
ture pressure p but rather a partial pressure. As shown below, the sum of the partial pressures
equals the mixture pressure. The partial pressure of component i, pi, is the pressure that ni moles partial pressure
of component i would exert if the component were alone in the volume V at the mixture tem-
perature T. The partial pressure can be evaluated using the ideal gas equation of state
ni RT
pi (12.11)
V
Dividing Eq. 12.11 by Eq. 12.10
pi ni RTV ni
yi
p nRTV n
Thus, the partial pressure of component i can be evaluated in terms of its mole fraction yi
and the mixture pressure p
pi yi p (12.12)
To show that the sum of partial pressures equals the mixture pressure, sum both sides of
Eq. 12.12 to obtain
j j j
a pi a yi p p a yi
i1 i1 i1
Since the sum of the mole fractions is unity (Eq. 12.7), this becomes
j
p a pi (12.13)
i1
Amagat model AMAGAT MODEL. The underlying assumption of the Amagat model is that each mixture
component behaves as an ideal gas as if it existed separately at the pressure p and tempera-
ture T of the mixture. The volume that ni moles of component i would occupy if the com-
partial volume ponent existed at p and T is called the partial volume, Vi, of component i. As shown below,
the sum of the partial volumes equals the total volume. The partial volume can be evaluated
using the ideal gas equation of state
ni RT
Vi (12.14)
p
Dividing Eq. 12.14 by the total volume V
Vi ni RTp ni
yi
V nRTp n
Thus, the partial volume of component i also can be evaluated in terms of its mole fraction
yi and the total volume
Vi yiV (12.15)
This relationship between volume fraction and mole fraction underlies the use of the term
volumetric analysis as signifying an analysis of a mixture in terms of mole fractions.
To show that the sum of partial volumes equals the total volume, sum both sides of
Eq. 12.15 to obtain
j j j
a Vi a yiV V a yi
i1 i1 i1
Since the sum of the mole fractions equals unity, this becomes
j
V a Vi (12.16)
i1
CLOSING COMMENT. The Dalton and Amagat models are special cases, respectively, of
the additive pressure and additive volume rules introduced in Sec. 11.8, which do not require
the assumption of the ideal gas model. The concept of an ideal gas mixture is a special case
of the ideal solution concept introduced in Sec. 11.9.

12.3 Evaluating U, H, S, and Specific Heats
To apply the conservation of energy principle to a system involving an ideal gas mixture re-
quires evaluation of the internal energy, enthalpy, or specific heats of the mixture at various
states. Similarly, to conduct an analysis using the second law normally requires the entropy
of the mixture. The objective of the present section is to develop means to evaluate these
properties for ideal gas mixtures.
EVALUATING U AND H. Consider a closed system consisting of an ideal gas mixture. Ex-
tensive properties of the mixture, such as U, H, or S, can be found by adding the contribu-
tion of each component at the condition at which the component exists in the mixture. Let
us apply this model to internal energy and enthalpy.
12.3 Evaluating U, H, S, and Specific Heats 565
Since the internal energy and enthalpy of ideal gases are functions of temperature only,
the values of these properties for each component present in the mixture are determined by
the mixture temperature alone. Accordingly
j
U U1
U2
# # #
Uj a Ui (12.17)
i1
j
H H1
H2
# # #
Hj a Hi (12.18)
i1
where Ui and Hi are the internal energy and enthalpy, respectively, of component i evaluated
at the mixture temperature.
Equations 12.17 and 12.18 can be rewritten on a molar basis as
j
nu n1u1
n2u2
# # #
njuj a niui (12.19)
i1
and
j
nh n1h1
n2h2
# # #
nj hj a ni hi (12.20)
i1
where u and h are the specific internal energy and enthalpy of the mixture per mole of mixture,
and ui and hi are the specific internal energy and enthalpy of component i per mole of i.
Dividing by the total number of moles of mixture n gives expressions for the specific inter-
nal energy and enthalpy of the mixture per mole of mixture, respectively
j
u a yi ui (12.21)
i1
j
h a yi hi (12.22)
i1
Each of the molar internal energy and enthalpy terms appearing in Eqs. 12.19 through 12.22
is evaluated at the mixture temperature only.
EVALUATING cv AND c P . Differentiation of Eqs. 12.21 and 12.22 with respect to temper-
ature results, respectively, in the following expressions for the specific heats cv and cp of the
mixture on a molar basis
j
cv a yi cv,i (12.23)
i1
j
cp a yi cp,i (12.24)
i1
That is, the mixture specific heats cp and cv are mole-fraction averages of the respective com-
ponent specific heats. The specific heat ratio for the mixture is k cp cv.
EVALUATING S. The entropy of a mixture can be found, as for U and H, by adding the
contribution of each component at the condition at which the component exists in the mix-
ture. The entropy of an ideal gas depends on two properties, not on temperature alone as for
internal energy and enthalpy. Accordingly, for the mixture
j
S S1
S2
# # #
Sj a Si (12.25)
i1
where Si is the entropy of component i evaluated at the mixture temperature T and partial
pressure pi (or at temperature T and total volume V ).
Equation 12.25 can be written on a molar basis as
j
ns n1s1
n2s2
# # #
nj sj a ni si (12.26)
i1
where s is the entropy of the mixture per mole of mixture and si is the entropy of component i
per mole of i. Dividing by the total number of moles of mixture gives an expression for the
entropy of the mixture per mole of mixture
j
s a yi si (12.27)
i1
The specific entropies si of Eqs. 12.26 and 12.27 are evaluated at the mixture temperature T
and the partial pressure pi.
WORKING ON A MASS BASIS. In cases where it is convenient to work on a mass basis,

the foregoing expressions would be written with the mass of the mixture, m, and the mass
of component i in the mixture, mi, replacing, respectively, the number of moles of mixture,
n, and the number of moles of component i, ni. Similarly, the mass fraction of component
i, mfi, would replace the mole fraction, yi. All specific internal energies, enthalpies, and en-
tropies would be evaluated on a unit mass basis rather than on a per mole basis as above.
The development of the appropriate expressions is left as an exercise. By using the molecu-
lar weight of the mixture or of component i, as appropriate, data can be converted from a
mass basis to a molar basis, or conversely, with relations of the form
u Mu, h Mh, cp Mcp, cv Mcv, s Ms (12.28)
for the mixture, and

ui Miui, h Mihi, cp,i Micp,i, cv,i Micv,i, si Misi (12.29)
for component i.

12.4 Analyzing Systems Involving Mixtures
To perform thermodynamic analyses of systems involving nonreacting ideal gas mixtures re-
quires no new fundamental principles. The conservation of mass and energy principles and
the second law of thermodynamics are applicable in the forms previously introduced. The
only new aspect is the proper evaluation of the required property data for the mixtures in-
volved. This is illustrated in the present section, which deals with two classes of problems
involving mixtures. In Sec. 12.4.1 the mixture is already formed, and we study processes in
which there is no change in composition. Section 12.4.2 considers the formation of mixtures
from individual components that are initially separate.
12.4.1 Mixture Processes at Constant Composition

In the present section we are concerned with the case of ideal gas mixtures undergoing
processes during which the composition remains constant. The number of moles of each com-
ponent present, and thus the total number of moles of mixture, remain the same throughout
the process. This case is shown schematically in Fig. 12.2, which is labeled with expressions
for U, H, and S of a mixture at the initial and final states of a process undergone by the
mixture. In accordance with the discussion of Sec. 12.3, the specific internal energies and
State 1 State 2
(n1, n2, , nj) (n1, n2, , nj)

at at
T1, p1 T2, p2
j _ j _
U1 = niui(T1) U2 = niui(T2)
i=1 i=1
j _ j _
H1 = nih i(T1) H2 = nih i(T2 )
i=1 i=1
j _ j _ Figure 12.2 Process of an ideal gas
S1 = ni si(T1, pi1) S2 = ni si(T2, pi2)
i=1 i=1 mixture.
enthalpies of the components are evaluated at the temperature of the mixture. The specific
entropy of each component is evaluated at the mixture temperature and the partial pressure
of the component in the mixture.
The changes in the internal energy and enthalpy of the mixture during the process are
given, respectively, by
j
U2 U1 a ni 3ui 1T2 2 ui 1T1 2 4 (12.30)
i1
j
H2 H1 a ni 3hi 1T2 2 hi 1T1 2 4 (12.31)
i1
where T1 and T2 denote the temperature at the initial and final states. Dividing by the num-
ber of moles of mixture, n, expressions for the change in internal energy and enthalpy of the
mixture per mole of mixture result
j
u a yi 3ui 1T2 2 ui 1T1 2 4 (12.32)
i1
j
h a yi 3hi 1T2 2 hi 1T1 2 4 (12.33)
i1
Similarly, the change in entropy for the mixture is

j
S2 S1 a ni 3si 1T2, pi2 2 si 1T1, pi1 2 4 (12.34)
i1
where pi1 and pi2 denote, respectively, the initial and final partial pressures of component i.
Dividing by the total moles of mixture, Eq. 12.34 becomes
j
s a yi 3si 1T2, pi2 2 si 1T1, pi1 2 4 (12.35)
i1
Companion expressions for Eqs. 12.30 through 12.35 on a mass basis also can be written.
This is left as an exercise.
The foregoing expressions giving the changes in internal energy, enthalpy, and entropy of
the mixture are written in terms of the respective property changes of the components.
Accordingly, different datums might be used to assign specific enthalpy values to the various
components because the datums would cancel when the component enthalpy changes are cal-
culated. Similar remarks apply to the cases of internal energy and entropy.
USING IDEAL GAS TABLES. For several common gases modeled as ideal gases, the quan-
tities ui and hi appearing in the foregoing expressions can be evaluated as functions of tem-
perature only from Tables A-22 and A-23. Table A-22 for air gives these quantities on a mass
basis. Table A-23 gives them on a molar basis. The ideal gas tables also can be used to eval-
uate the entropy change. The change in specific entropy of component i required by Eqs. 12.34
and 12.35 can be determined with Eq. 6.21b as
si si 1T2 2 si 1T1 2 R ln
pi2
pi1
Since the mixture composition remains constant, the ratio of the partial pressures in this
expression is the same as the ratio of the mixture pressures, as can be shown by using
Eq. 12.12 to write
pi2 yi p2 p2

pi1 yi p1 p1
Accordingly, when the composition is constant, the change in the specific entropy of com-
ponent i is simply
si si 1T2 2 si 1T1 2 R ln
p2
(12.36)
p1
where p1 and p2 denote, respectively, the initial and final mixture pressures. The terms si
of Eq. 12.36 can be obtained as functions of temperature for several common gases from
Table A-23. Table A-22 for air gives s versus temperature.
ASSUMING CONSTANT SPECIFIC HEATS. When the component specific heats cv,i and cp,i
are taken as constants, the specific internal energy, enthalpy, and entropy changes of the mix-
ture and the components of the mixture are given by
u cv 1T2 T1 2, ui cv,i 1T2 T1 2 (12.37)

h cp 1T2 T1 2, hi cp,i 1T2 T1 2 (12.38)
T2 p2 T2 p2
s cp ln R ln , si cp,i ln R ln (12.39)
T1 p 1 T1 p 1
where the mixture specific heats cv and cp are evaluated from Eqs. 12.23 and 12.24, respec-
tively, using data from Tables A-20 or the literature, as required. The expression for u can
be obtained formally by substituting the above expression for ui into Eq. 12.32 and using
Eq. 12.23 to simplify the result. Similarly, the expressions for h and s can be obtained by
inserting hi and si into Eqs. 12.33 and 12.35, respectively, and using Eq. 12.24 to simplify.
In the equations for entropy change, the ratio of mixture pressures replaces the ratio of par-
tial pressures as discussed above. Similar expressions can be written for the mixture specific
internal energy, enthalpy, and entropy changes on a mass basis. This is left as an exercise.
USING COMPUTER SOFTWARE. The changes in internal energy, enthalpy, and entropy
required in Eqs. 12.32, 12.33, and 12.35, respectively, also can be evaluated using computer
software. Interactive Thermodynamics: IT provides data for a large number of gases mod-
eled as ideal gases, and its use is illustrated in Example 12.4 below.
The next example illustrates the use of ideal gas mixture relations for analyzing a com-
pression process.
EXAMPLE 12.3 Compressing an Ideal Gas Mixture
A mixture of 0.3 kg of carbon dioxide and 0.2 kg of nitrogen is compressed from p1 1 bar, T1 300 K to p2 3 bars in
a polytropic process for which n 1.25. Determine (a) the final temperature, in K, (b) the work, in kJ, (c) the heat transfer,
in kJ, (d) the change in entropy of the mixture, in kJ/K.
SOLUTION
Known: A mixture of 0.3 kg of CO2 and 0.2 kg of N2 is compressed in a polytropic process for which n 1.25. At the
initial state, p1 1 bar, T1 300K. At the final state, p2 3 bar.
Find: Determine the final temperature, in K, the work, in kJ, the heat transfer, kJ, and the entropy change of the mixture in,
kJ/K.
p
Boundary 2
n = 1.25
0.3 kg CO2
0.2 kg N2
States of the
mixture
p1 = 1 bar, T1 = 300 K, 1
p2 = 3 bars
v
Figure E12.3
Assumptions:
1. As shown in the accompanying figure, the system is the mixture of CO2 and N2. The mixture composition remains con-
stant during the compression.
2. Each mixture component behaves as if it were an ideal gas occupying the entire system volume at the mixture tempera-
ture. The overall mixture acts as an ideal gas.
3. The compression process is a polytropic process for which n 1.25.
4. The changes in kinetic and potential energy between the initial and final states can be ignored.
Analysis:
(a) For an ideal gas, the temperatures and pressures at the end states of a polytropic process are related by Eq. 3.56
p2 1n12n
T2 T1a b
p1
Inserting values
3 0.2
T2 300 a b 374 K
1
(b) The work for the compression process is given by

2
W p dV
1
Introducing pV n constant and performing the integration

p2V2 p1V1
W
1n
With the ideal gas equation of state, this reduces to
m1RM21T2 T1 2
W
1n
The mass of the mixture is m 0.3

0.2 0.5 kg. The apparent molecular weight of the mixture can be calculated
using M mn, where n is the total number of moles of mixture. With Eq. 12.1, the numbers of moles of CO2 and N2 are,
respectively
0.3 0.2
nCO2 0.0068 kmol, nN2 0.0071 kmol
44 28
The total number of moles of mixture is then n 0.0139 kmol. The apparent molecular weight of the mixture is M
0.50.0139 35.97.
Calculating the work
10.5 kg2 a b 1374 K 300 K2

8.314 kJ
35.97 kg # K
W
1 1.25
34.21 kJ
where the minus sign indicates that work is done on the mixture, as expected.
(c) With assumption 4, the closed system energy balance can be placed in the form
Q U
W
where U is the change in internal energy of the mixture.
The change in internal energy of the mixture equals the sum of the internal energy changes of the components. With
Eq. 12.30
U nCO2 3uCO2 1T2 2 uCO2 1T1 2 4

nN2 3uN2 1T2 2 uN2 1T1 2 4
This form is convenient because Table A-23 gives internal energy values for N2 and CO2, respectively, on a molar basis. With
values from this table
U 10.0068219198 69392
10.0071217770 62292
26.3 kJ
Inserting values for U and W into the expression for Q
Q
26.3 34.21 7.91 kJ
where the minus sign signifies a heat transfer from the system.
(d) The change in entropy of the mixture equals the sum of the entropy changes of the components. With Eq. 12.34
S nCO2 sCO2
nN2 sN2
where sN2 and sCO2 are evaluated using Eq. 12.36 and values of s for N2 and CO2 from Table A-23. That is
S 0.0068 a222.475 213.915 8.314 b

3

0.0071 a198.105 191.682 8.314 b
3
1
.0231 kJ/K
Entropy decreases in the process because entropy is transferred from the system accompanying heat transfer.
In view of the relatively small temperature change, the changes in the internal energy and entropy of the mixture can be
evaluated alternatively using the constant specific heat relations, Eqs. 12.37 and 12.39, respectively. In these equations, cv
and cp are specific heats for the mixture determined using Eqs. 12.23 and 12.24 together with appropriate specific heat
values for the components chosen from Table A-20.
Since the composition remains constant, the ratio of mixture pressures equals the ratio of partial pressures, so Eq. 12.36
can be used to evaluate the component specific entropy changes required here.
The next example illustrates the application of ideal gas mixture principles for the analy-
sis of a mixture expanding isentropically through a nozzle. The solution features the use of
table data and IT as an alternative.
EXAMPLE 12.4 Gas Mixture Expanding Isentropically through a Nozzle
A gas mixture consisting of CO2 and O2 with mole fractions 0.8 and 0.2, respectively, expands isentropically and at steady
state through a nozzle from 700 K, 5 bars, 3 m/s to an exit pressure of 1 bar. Determine (a) the temperature at the nozzle exit,
in K, (b) the entropy changes of the CO2 and O2 from inlet to exit, in kJ/kmol # K, (c) the exit velocity, in m/s.
SOLUTION
Known: A gas mixture consisting of CO2 and O2 in specified proportions expands isentropically through a nozzle from spec-
ified inlet conditions to a given exit pressure.
Find: Determine the temperature at the nozzle exit, in K, the entropy changes of the CO2 and O2 from inlet to exit, in
kJ/kmol # K, and the exit velocity, in m/s.
T p1 = 5 bars
V1 = 3 m/s 1
p2 = T1 = 700 K
p1 = 5 bars
T1 = 700 K 1 bar
States of the mixture
1
2 p2 = 1 bar
T2 = ?
2
s
Figure E12.4
Assumptions:
1. The control volume shown by the dashed line on the accompanying figure operates at steady state.
2. The mixture composition remains constant as the mixture expands isentropically through the nozzle. The overall mixture
and each mixture component act as ideal gases. The state of each component is defined by the temperature and the partial
pressure of the component.
3. The change in potential energy between inlet and exit can be ignored.
Analysis:
(a) The temperature at the exit can be determined using the fact that the expansion occurs isentropically: s2 s1 0. As
there is no change in the specific entropy of the mixture between inlet and exit, Eq. 12.35 can be used to write
s2 s1 yO2 sO2
yCO2 sCO2 0 (a)
The change in specific entropy of each component can be determined using Eq. 12.36. Thus, Eq. (a) becomes
yO2 c sO2 1T2 2 sO2 1T1 2 R ln d

yCO2 c sCO2 1T2 2 sCO2 1T1 2 R ln d 0
p2 p2
p1 p1
On rearrangement
yO2 sO2 1T2 2

yCO2 sCO2 1T2 2 yO2 sO2 1T1 2
yCO2 sCO2 1T1 2
1yO2
yCO2 2 R ln
p2
p1
The sum of mole fractions equals unity, so the coefficient of the last term on the right side is 1 yO2
yCO2 2 1.
Introducing given data, and values of s for O2 and CO2 at T1 700 K from Table A-23
0.2sO2 1T2 2
0.8sCO2 1T2 2 0.21231.3582
0.81250.6632
8.314 ln
1
5
or
0.2sO2 1T2 2
0.8sCO2 1T2 2 233.42 kJ/kmol # K
To determine the temperature T2 requires an iterative approach with the above equation: A final temperature T2 is assumed,
and the s values for O2 and CO2 are found from Table A-23. If these two values do not satisfy the equation, another tem-
perature is assumed. The procedure continues until the desired agreement is attained. In the present case
at T 510 K: 0.21221.2062
0.81235.7002 232.80
at T 520 K: 0.21221.8122
0.81236.5752 233.62
Linear interpolation between these values gives T2 517.6 K.
Alternatively, the following IT program can be used to evaluate T2 without resorting to iteration with table data. In the pro-
gram, yO2 denotes the mole fraction of O2, p1_O2 denotes the partial pressure of O2 at state 1, s1_O2 denotes the entropy
per mole of O2 at state 1, and so on.
T1 = 700 // K
p1 = 5 // bar
p2 = 1 // bar
yO2 = 0.2
yCO2 = 0.8
p1_O2 = yO2 * p1
p1_CO2 = yCO2 * p1
p2_O2 = yO2 * p2
p2_CO2 = yCO2 * p2
s1_O2 = s_TP(O2,T1,p1_O2)
s1_CO2 = s_TP(CO2,T1,p1_CO2)
s2_O2 = s_TP(O2, T2,p2_O2)
s2_CO2 = s_TP(CO2, T2,p2_CO2)
// When expressed in terms of these quantities, Eq. (a) takes the form
yO2 * (s2_O2 s1_O2) + yCO2 * (s2_CO2 s1_CO2) = 0
Using the Solve button, the result is T2 517.6 K, which agrees with the value obtained using table data. Note that IT provides
the value of specific entropy for each component directly and does not return s of the ideal gas tables.
(b) The change in the specific entropy for each of the components can be determined using Eq. 12.36. For O2
sO2 sO2 1T2 2 sO2 1T1 2 R ln

p2
p1
Inserting s values for O2 from Table A-23
sO2 221.667 231.358 8.314 ln 10.22 3.69 kJ/kmol # K
Similarly, with CO2 data from Table A-23
sCO2 sCO2 1T2 2 sCO2 1T1 2 R ln

p2
p1
236.365 250.663 8.314 ln 10.22
0.92 kJ/kmol # K
(c) Reducing the energy rate balance for the one-inlet, one-exit control volume at steady state
V21 V22
0 h1 h2
where h1 and h2 are the enthalpy of the mixture, per unit mass of mixture, at the inlet and exit, respectively. Solving for V2
V2 2V21
21h1 h2 2
The term (h1 h2) in the expression for V2 can be evaluated as
h1 h2
3yO2 1h1 h2 2 O2
yCO2 1h1 h2 2 CO2 4
1
h1 h2
M M
where M is the apparent molecular weight of mixture, and the molar specific enthalpies of O2 and CO2 are from Table A-23.
With Eq. 12.9, the apparent molecular weight of the mixture is
M 0.81442
0.21322 41.6 kg/kmol
Then, with enthalpy values at T1 700 K and T2 517.6 K from Table A-23
30.2121,184 15,3202
0.8127,125 18,4682 4
1
h1 h2
41.6
194.7 kJ/kg
Finally,
m 2 kJ 1 kg # m/s2 103 N # m
V2 a3 b
2 a194.7 b ` ` ` ` 624 m/s
B s kg 1N 1 kJ
Parts (b) and (c) can be solved alternatively using IT. These parts also can be solved using a constant cp together with
Eqs. 12.38 and 12.39. Inspection of Table A-20 shows that the specific heats of CO2 and O2 increase only slightly with
temperature over the interval from 518 to 700 K, and so suitable constant values of cp for the components and the overall
mixture can be readily determined. These alternative solutions are left as exercises.
Each component experiences an entropy change as it passes from inlet to exit. The increase in entropy of the oxygen and
the decrease in entropy of the carbon dioxide are due to an entropy transfer accompanying heat transfer from the CO2 to
the O2 as they expand through the nozzle. However, as indicated by Eq. (a), there is no change in the entropy of the mixture
as it expands through the nozzle.
Note the use of unit conversion factors in the calculation of V2.
12.4.2 Mixing of Ideal Gases

Thus far, we have considered only mixtures that have already been formed. Now let us take
up cases where ideal gas mixtures are formed by mixing gases that are initially separate.
Such mixing is irreversible because the mixture forms spontaneously, and a work input from
the surroundings would be required to separate the gases and return them to their respective
initial states. In this section, the irreversibility of mixing is demonstrated through calcula-
tions of the entropy production.
Three factors contribute to the production of entropy in mixing processes:
1. The gases are initially at different temperatures.
2. The gases are initially at different pressures.
3. The gases are distinguishable from one another.

Is Stale Airplane Air Making Us Sick? rates are higher, and
the proportion of out-
About half the air we breathe on some airplanes is fresh air, side air is greater than
and the rest is recirculated. This has some passengers and provided in the build-
flight attendants worried that recycled air is making them sick. ings where the travel-
The debate rages, and the Federal Aviation Agency is listen- ers live and work. Still,
ing closely as engineers, scientists, and health professionals the National Academy
try to sort out the facts. of Sciences and the
According to a study reported in the Journal of the American Society of
American Medical Society, while people on airplanes seem to Heating, Refrigerating,
get more colds, recirculating cabin air doesnt appear to make and Air Conditioning
the situation worse. Surveys show that travelers on flights with Engineers are calling
recirculated air or on flights with fresh air report about the for greater use of high-
same incidence of colds within a week of flying. In both cases, grade filters that can remove virtually all of the bacteria and
cold incidence is much greater than among those who have fungus from the air. Such filters are already used in hospital
not flown recently. operating room ventilation systems.
Aircraft industry sources point out that airplane air is filtered.
They claim that airplane filtration systems are better, air change
Entropy is produced when any of these factors is present during a mixing process. This is
illustrated in the next example, where different gases, initially at different temperatures and
pressures, are mixed.
EXAMPLE 12.5 Adiabatic Mixing at Constant Total Volume
Two rigid, insulated tanks are interconnected by a valve. Initially 0.79 kmol of nitrogen at 2 bars and 250 K fills one tank.
The other tank contains 0.21 kmol of oxygen at 1 bar and 300 K. The valve is opened and the gases are allowed to mix until
a final equilibrium state is attained. During this process, there are no heat or work interactions between the tank contents and
the surroundings. Determine (a) the final temperature of the mixture, in K, (b) the final pressure of the mixture, in atm, (c) the
amount of entropy produced in the mixing process, in kJ/K.
SOLUTION
Known: Nitrogen and oxygen, initially separate at different temperatures and pressures, are allowed to mix without heat or
work interactions with the surroundings until a final equilibrium state is attained.
Find: Determine the final temperature of the mixture, in K, the final pressure of the mixture, in bars, and the amount of
entropy produced in the mixing process, in kJ/K.
Insulation
Assumptions:
1. The system is taken to be the nitrogen and the oxygen together.

Valve
2. When separate, each of the gases behaves as an ideal gas. The final mix-
ture also acts as an ideal gas. Each mixture component occupies the total
Initially 0.79 kgmol Initially 0.21 kgmol
of N2 at 2 bars of O2 at 1 bar volume and exhibits the mixture temperature.
and 250K and 300K 3. No heat or work interactions occur with the surroundings, and there are
no changes in kinetic and potential energy.
Figure E12.5
Analysis:
(a) The final temperature of the mixture can be determined from an energy balance. With assumption 3, the closed system
energy balance reduces to
0 0
U Q W or U2 U1 0
The initial internal energy of the system, U1, equals the sum of the internal energies of the two gases when separate
U1 nN2uN2 1TN2 2
nO2uO2 1TO2 2
where TN2 250K is the initial temperature of the nitrogen and TO2 300K is the initial temperature of the oxygen. The
final internal energy of the system, U2, equals the sum of the internal energies of the two gases evaluated at the final mixture
temperature T2
U2 nN2uN2 1T2 2
nO2uO2 1T2 2
Collecting the last three equations
nN2 3 uN2 1T2 2 uN2 1TN2 2 4

nO2 3 uO2 1T2 2 uO2 1TO2 2 4 0
The temperature T2 can be determined using specific internal energy data from Table A-23 and an iterative procedure like
that employed in part (a) of Example 12.4. However, since the specific heats of N2 and O2 vary little over the temperature in-
terval from 250 to 300K, the solution can be conducted accurately on the basis of constant specific heats. Hence, the fore-
going equation becomes
nN2cv,N2 1T2 TN2 2

nO2cv,O2 1T2 TO2 2 0
Solving for T2
nN2cv,N2TN2
nO2cv,O2TO2
T2
nN2cv,N2
nO2cv,O2
Selecting cv values for N2 and O2 from Table A-20 at the average of the initial temperatures of the gases, 275 K, and us-
ing the respective molecular weights to convert to a molar basis
cv,N2 a28.01 ba b 20.82

kg .743 kJ kJ
kmol kg K# kmol # K
a32.0 ba b 20.99
kg .656 kJ kJ
cv,O2
kmol kg # K kmol # K
Substituting values into the expression for T2
10.79 kmol2 a b 1250 K2

10.21 kmol2 a b 1300 K2
20.82 kJ 20.99 kJ
kmol # K kmol # K
T2
10 .79 kmol2 a20.82 b
10.21 kmol2 a20.99 b
kJ kJ
kmol # K kmol # K
261K
(b) The final mixture pressure p2 can be determined using the ideal gas equation of state, p2 nRT2V, where n is the total
number of moles of mixture and V is the total volume occupied by the mixture. The volume V is the sum of the volumes of
the two tanks, obtained with the ideal gas equation of state as follows
nN2RTN2 nO2RTO2
V
pN2 pO2
where pN2 2 atm is the initial pressure of the nitrogen and pO2 1 atm is the initial pressure of the oxygen. Combining
results and reducing
1nN2
nO2 2 T2
p2
nN2TN2 nO2TO2
a
b
pN2 pO2
Substituting values
11.0 kmol2 1261K2

p2
10.79 kmol2 1250K2 10.21 kmol2 1300K2
c
d
2 bars 1 bar
1.62 bars
(c) Reducing the closed system form of the entropy balance
0
2
a b
s
dQ
S2 S1
1 T b
where the entropy transfer term drops out for the adiabatic mixing process. The initial entropy of the system, S1, is the sum
of the entropies of the gases at the respective initial states
S1 nN2sN2 1TN2, pN2 2

nO2sO2 1TO2, pO2 2
The final entropy of the system, S2, is the sum of the entropies of the individual components, each evaluated at the final mix-
ture temperature and the partial pressure of the component in the mixture
S2 nN2sN2 1T2, yN2 p2 2

nO2sO2 1T2, yO2 p2 2

s nN2 3sN2 1T2, yN2 p2 2 sN2 1TN2, pN2 2 4

nO2 3sO2 1T2, yO2 p2 2 sO2 1TO2, pO2 2 4
Evaluating the change in specific entropy of each gas in terms of a constant specific heat cp, this becomes
yN2 p2
s nN2 acp,N2 ln b
T2
R ln
TN2 pN2
yO2 p2

nO2acp,O2 ln b
T2
R ln
TO2 pO2
The required values for cp can be found by adding R to the cv values found previously (Eq. 3.45)
kJ kJ
cp,N2 29.13 cp,O2 29.30
kmol # K kmol # K
Since the total number of moles of mixture n 0.79
0.21 1.0, the mole fractions of the two gases are yN2 0.79 and
yO2 0.21.
Substituting values into the expression for gives
10.792 11.62 bars2

s 0.79 kmol c 29.13 ln a b 8.314 ln a bd
kJ 261K kJ
kmol K # 250K kmol K# 2 bars
10.212 11.62 bars2

0.21 kmol c 29.30 ln a b 8.314 ln a bd
kJ 261K kJ
kmol # K 300K kmol # K 1 bar
5.0 kJ/ K
Entropy is produced when different gases, initially at different temperatures and pressures, are followed to mix.
In the next example, we consider a control volume at steady state where two incoming
streams form a mixture. A single stream exits.
EXAMPLE 12.6 Adiabatic Mixing of Two Streams
At steady state, 100 m3/min of dry air at 32C and 1 bar is mixed adiabatically with a stream of oxygen (O2) at 127C and
1 bar to form a mixed stream at 47C and 1 bar. Kinetic and potential energy effects can be ignored. Determine (a) the mass
flow rates of the dry air and oxygen, in kg/min, (b) the mole fractions of the dry air and oxygen in the exiting mixture, and
(c) the time rate of entropy production, in kJ/K # min.
SOLUTION
Known: At steady state, 100 m3/min of dry air at 32C and 1 bar is mixed adiabatically with an oxygen stream at 127C
and 1 bar to form a mixed stream at 47C and 1 bar.
Find: Determine the mass flow rates of the dry air and oxygen, in kg/min, the mole fractions of the dry air and oxygen in
the exiting mixture, and the time rate of entropy production, in kJ/K # min.
Air 1
Insulation
T1 = 32C 3
p1 = 1 bar
(AV)1 = 100 m3/min
Mixed stream
T2 = 127C
p2 = 1 bar
T3 = 47C
Oxygen p3 = 1 bar
2
Figure E12.6
Assumptions:
1. The control volume identified by the dashed line on the accompanying figure operates at steady state.
2. No heat transfer occurs with the surroundings.
#
3. Kinetic and potential energy effects can be ignored, and Wcv 0.
4. The entering gases can be regarded as ideal gases. The exiting mixture can be regarded as an ideal gas mixture.
5. The dry air is treated as a pure component.
Analysis:
(a) The mass flow rate of the dry air entering the control volume can be determined from the given volumetric flow rate (AV)1
# 1AV2 1
ma1
va1
where va1 is the specific volume of the air at 1. Using the ideal gas equation of state
a b 1305 K2
8314 N # m
1R Ma 2T1 28.97 kg # K m3
va1 0.875
p1 105 N/m2 kg
The mass flow rate of the dry air is then
# 100 m3/min kg
ma1 114.29
0.875 m3/kg min
The mass flow rate of the oxygen can be determined using mass and energy rate balances. At steady state, the amounts of
dry air and oxygen contained within the control volume do not vary. Thus, for each component individually it is necessary
for the incoming and outgoing mass flow rates to be equal. That is
1dry air2
# #
ma1 ma3
1oxygen2
# #
mo2 mo3
Using assumptions 13 together with the foregoing mass flow rate relations, the energy rate balance reduces to
0 maha 1T1 2
mo ho 1T2 2 3 ma ha 1T3 2
mo ho 1T3 2 4
# # # #
# #
where ma and mo denote the mass flow rates of the dry air and oxygen, respectively. The enthalpy of the mixture at the exit
#
is evaluated by summing the contributions of the air and oxygen, each at the mixture temperature. Solving for mo
# ha 1T3 2 ha 1T1 2
mo ma c d
#
ho 1T2 2 ho 1T3 2
The specific enthalpies can be obtained from Tables A-22 and A-23. Since Table A-23 gives enthalpy values on a molar
basis, the molecular weight of oxygen is introduced into the denominator to convert the molar enthalpy values to a mass
basis
# 1114.29 kg /min21320.29 kJ/kg 305.22 kJ/kg2

mo
a b 111,711 kJ/kmol 9,325 kJ/kmol2
1
32 kg/kmol
kg
23.1
min
(b) To obtain the mole fractions of the dry air and oxygen in the exiting mixture, first convert the mass flow rates to molar
flow rates using the respective molecular weights
#
# ma 114.29 kg/min
na 3.95 kmol /min
Ma 28.97 kg/kmol
#
# mo 23.1 kg/min
no 0.72 kmol/min
Mo 32 kg/kmol
# #
where n denotes molar flow rate. The molar flow rate of the mixture n is the sum
# # #
n na
no 3.95
0.72 4.67 kmol/min
The mole fractions of the air and oxygen are, respectively

# #
na 3.95 no 0.72
ya #
n 4.67
0.846 and yo #
n 4.67
0.154
(c) For the control volume at steady state, the entropy rate balance reduces to
0 masa 1T1, p1 2
moso 1T2, p2 2 3 masa 1T3, ya p3 2
mo so 1T3, yo p3 2 4
s
# # # # #
The specific entropy of each component in the exiting ideal gas mixture is evaluated at its partial pressure in the mixture and
#
at the mixture temperature. Solving for s
s ma 3sa 1T3, ya p3 2 sa 1T1, p1 2 4

mo 3so 1T3, yo p3 2 so 1T2, p2 2 4
# # #
12.5 Introducing Psychrometric Principles 579
Since p1 p3, the specific entropy change of the dry air is
sa 1T3, ya p3 2 sa 1T1, p1 2 sa 1T3 2 sa 1T1 2

R ya p3
ln
Ma p1
sa 1T3 2 sa 1T1 2
R
ln ya
Ma
The sa terms are evaluated from Table A-22. Similarly, since p2 p3, the specific entropy change of the oxygen is
so 1T3, yo p3 2 so 1T2, p2 2 3 s1T 2 so 1T2 2 R ln yo 4

1
Mo o 3
The so terms are evaluated from Table A-23. Note the use of the molecular weights Ma and Mo in the last two equations to
obtain the respective entropy changes on a mass basis.
The expression for the rate of entropy production becomes
#
s ma c sa 1T3 2 sa 1T1 2 ln ya d
3s1T 2 so 1T2 2 R ln yo 4
# # R mo
Ma Mo o 3
Substituting values
s a114.29 b c 1.7669 a b ln 0.846 d

# kg kJ kJ 8.314 kJ
1.71865
min kg # K kg # K 28.97 kg # K

a b c 207.112 a8.314 b ln 0.154 d
23.1 kg/min kJ kJ kJ
# 213.765 #
32 kg/kmol kmol K kmol K kmol # K
kJ
17.42
K # min
This calculation is based on dry air modeled as a pure component (assumption 5). However, since O2 is a component of
dry air (Table 12.1), the actual mole fraction of O2 in the exiting mixture is greater than given here.
Entropy is produced when different gases, initially at different temperatures, are allowed to mix.
PSYCHROMETRIC APPLICATIONS
The remainder of this chapter is concerned with the study of systems involving mixtures of
dry air and water vapor. A condensed water phase also may be present. Knowledge of the
behavior of such systems is essential for the analysis and design of air-conditioning devices,
cooling towers, and industrial processes requiring close control of the vapor content in air.
The study of systems involving dry air and water is known as psychrometrics. psychrometrics

12.5 Introducing Psychrometric Principles
The object of the present section is to introduce some important definitions and principles
used in the study of systems involving of dry air and water.
12.5.1 Moist Air

The term moist air refers to a mixture of dry air and water vapor in which the dry air is moist air
treated as if it were a pure component. As can be verified by reference to appropriate property
Temperature = T
Pressure = p
na, ma: dry air

nv, mv: water vapor
n, m: mixture
Boundary Volume = V Figure 12.3 Mixture of dry air and water vapor.
data, the overall mixture and each mixture component behave as ideal gases at the states un-
der present consideration. Accordingly, for the applications to be considered, the ideal gas
mixture concepts introduced previously apply directly.
Shown in Fig. 12.3 is a closed system consisting of moist air occupying a volume V at
mixture pressure p and mixture temperature T. The overall mixture is assumed to obey the
ideal gas equation of state. Thus
nRT m1RM2T
p (12.40)
V V
where n, m, and M denote the moles, mass, and molecular weight of the mixture,
respectively, and n mM. Each mixture component is considered to act as if it existed
alone in the volume V at the mixture temperature T while exerting a part of the pressure.
The mixture pressure is the sum of the partial pressures of the dry air and the water vapor:
p pa
pv.
Using the ideal gas equation of state, the partial pressures pa and pv of the dry air and
water vapor are, respectively
naRT ma 1RMa 2T nvRT mv 1RMv 2T

pa , pv (12.41a)
V V V V
where na and nv denote the moles of dry air and water vapor, respectively; ma, mv, Ma, and
Mv are the respective masses and molecular weights. The amount of water vapor present is
normally much less than the amount of dry air. Accordingly, the values of nv, mv, and pv are
small relative to the corresponding values of na, ma, and pa.
Forming ratios with Eqs. 12.40 and 12.41a, we get the following alternative expressions
for pa and pv
pa ya p, pv yv p (12.41b)
where ya and yv are the mole fractions of the dry air and water vapor, respectively.
A typical state of water vapor in moist air is shown in Fig. 12.4. At this state, fixed by
the partial pressure pv and the mixture temperature T, the vapor is superheated. When the
partial pressure of the water vapor corresponds to the saturation pressure of water at the mix-
saturated air ture temperature, pg of Fig. 12.4, the mixture is said to be saturated. Saturated air is a mixture
of dry air and saturated water vapor. The amount of water vapor in moist air varies from zero
in dry air to a maximum, depending on the pressure and temperature, when the mixture is
saturated.
T pg pv
Mixture
temperature
State of the
water vapor in a
saturated mixture Typical state of the
water vapor in moist air
Figure 12.4 Tv diagram for water

v vapor in an airwater mixture.
12.5.2 Humidity Ratio, Relative Humidity, and

Mixture Enthalpy
A given moist air sample can be described in a number of ways. The mixture can be described
in terms of the moles of dry air and water vapor present or in terms of the respective mole
fractions. Alternatively, the mass of dry air and water vapor, or the respective mass fractions,
can be specified. The composition also can be indicated by means of the humidity ratio ,
defined as the ratio of the mass of the water vapor to the mass of dry air
mv
v (12.42) humidity ratio
ma
The humidity ratio is sometimes referred to as the specific humidity.

The humidity ratio can be expressed in terms of partial pressures and molecular weights
by solving Eqs. 12.41a for ma and mv, respectively, and substituting the resulting expressions
into Eq. 12.42 to obtain
mv Mv pvVRT Mvpv
v
ma Ma paVRT Ma pa
Introducing pa p pv and noting that the ratio of the molecular weight of water to that
of dry air is approximately 0.622, this expression can be written as
pv
v 0.622 (12.43)
p pv
Moist air also can be described in terms of the relative humidity , defined as the ratio
of the mole fraction of water vapor yv in a given moist air sample to the mole fraction yv,sat
in a saturated moist air sample at the same mixture temperature and pressure
b
yv
f
yv,sat T, p
Since pv yvp and pg yv,sat p, the relative humidity can be expressed as
b
pv
f (12.44) relative humidity
pg T, p
The pressures in this expression for the relative humidity are labeled on Fig. 12.4.
Relative The humidity ratio and relative humidity can be measured. For laboratory measurements
humidity of humidity ratio, a hygrometer can be used in which a moist air sample is exposed to suit-
able chemicals until the moisture present is absorbed. The amount of water vapor is deter-
mined by weighing the chemicals. Continuous recording of the relative humidity can be
accomplished by means of transducers consisting of resistance- or capacitance-type sensors
whose electrical characteristics change with relative humidity.
Temperature
EVALUATING H, U, AND S. The values of H, U, and S for moist air modeled as an ideal
Sensing element gas mixture can be found by adding the contribution of each component at the condition at
which the component exists in the mixture. For example, the enthalpy H of a given moist air
sample is
H Ha
Hv maha
mvhv (12.45)
Dividing by ma and introducing the humidity ratio gives the mixture enthalpy per unit mass
of dry air
H mv
mixture enthalpy ha
h ha
vhv (12.46)
ma ma v
The enthalpies of the dry air and water vapor appearing in Eq. 12.46 are evaluated at the
mixture temperature. An approach similar to that for enthalpy also applies to the evaluation
of the internal energy of moist air.
Reference to steam table data or a Mollier diagram for water shows that the enthalpy of
superheated water vapor at low vapor pressures is very closely given by the saturated vapor
value corresponding to the given temperature. Hence, the enthalpy of the water vapor hv in
Eq. 12.46 can be taken as hg at the mixture temperature. That is
hv hg 1T 2 (12.47)
This approach is used in the remainder of the chapter. Enthalpy data for water vapor as an
ideal gas from Table A-23 are not used for hv because the enthalpy datum of the ideal gas
tables differs from that of the steam tables. These different datums can lead to error when
studying systems that contain both water vapor and a liquid or solid phase of water. The
enthalpy of dry air, ha, can be obtained from Table A-22, however, because air is a
gas at all states under present consideration and is closely modeled as an ideal gas at
these states.
When evaluating the entropy of moist air, the contribution of each component is deter-
mined at the mixture temperature and the partial pressure of the component in the mixture.
Using Eq. 6.19, it can be shown that the specific entropy of the water vapor is given by
sv(T, pv) sg(T ) R ln , where sg is the specific entropy of saturated vapor at temperature
T from the steam tables and is the relative humidity.
USING COMPUTER SOFTWARE. Property functions for moist air are listed under the
Properties menu of Interactive Thermodynamics: IT. Functions are included for humidity ra-
tio, relative humidity, specific enthalpy and entropy as well as other psychrometric properties
introduced later. The methods used for evaluating these functions correspond to the methods
discussed in this chapter, and the values returned by the computer software agree closely with
those obtained by hand calculations with table data. The use of IT for psychrometric evaluations
is illustrated in examples later in the chapter.
System boundary
Gas phase: Dry air and

water vapor
Figure 12.5 System consisting of moist air in contact

Liquid water with liquid water.
12.5.3 Modeling Moist Air in Equilibrium with Liquid Water

Thus far, our study of psychrometrics has been conducted as an application of the ideal gas
mixture principles introduced in the first part of this chapter. However, many systems of in-
terest are composed of a mixture of dry air and water vapor in contact with a liquid (or solid)
water phase. To study these systems requires additional considerations.
Shown in Fig. 12.5 is a vessel containing liquid water, above which is a mixture of water
vapor and dry air. If no interactions with the surroundings are allowed, liquid will evaporate
until eventually the gas phase becomes saturated and the system attains an equilibrium state.
For many engineering applications, systems consisting of moist air in equilibrium with a
liquid water phase can be described simply and accurately with the following idealizations:
The dry air and water vapor behave as independent ideal gases.
The equilibrium between the liquid phase and the water vapor is not significantly
disturbed by the presence of the air.
The partial pressure of the water vapor equals the saturation pressure of water
corresponding to the temperature of the mixture: pv pg(T ).
Similar considerations apply for systems consisting of moist air in equilibrium with a solid
water phase. The presence of the air actually alters the partial pressure of the vapor from the
saturation pressure by a small amount whose magnitude is calculated in Sec. 14.6.
12.5.4 Evaluating the Dew Point Temperature

A significant aspect of the behavior of moist air is that partial condensation of the water va-
por can occur when the temperature is reduced. This type of phenomenon is commonly en-
countered in the condensation of vapor on windowpanes and on pipes carrying cold water.
The formation of dew on grass is another familiar example.
To study such condensation, consider a closed system consisting of a sample of moist air
that is cooled at constant pressure, as shown in Fig. 12.6. The property diagram given on
this figure locates states of the water vapor. Initially, the water vapor is superheated at state 1.
In the first part of the cooling process, both the system pressure and the composition of the
moist air would remain constant. Accordingly, since pv yvp, the partial pressure of the wa-
ter vapor would remain constant, and the water vapor would cool at constant pv from state 1
to state d, called the dew point. The saturation temperature corresponding to pv is called the
dew point temperature. This temperature is labeled on Fig. 12.6. dew point temperature
In the next part of the cooling process, the system would be cooled below the dew point
temperature and some of the water vapor initially present would condense. At the final state,
the system would consist of a gas phase of dry air and water vapor in equilibrium with a liq-
uid water phase. The vapor that remains can be regarded as saturated at the final temperature,
T pg1
pv1 < pg1
1 Dry air and
Initial temperature p
Initial state superheated vapor
of the water vapor at the initial temper-
d ature p
Dew point temperature
Dew point pg2 < pv1
3
Final temperature Air and saturated vapor
Condensate Final state 2 at final temperature
of the water vapor Condensate:
saturated liquid
v Initial at final temperature Final
state state
Figure 12.6 States of water for moist air cooled at constant mixture pressure.
state 2 of Fig. 12.6, with a partial pressure equal to the saturation pressure pg2 corresponding
to this temperature. The condensate would be a saturated liquid at the final temperature, state 3
of Fig. 12.6. Note that the partial pressure of the water vapor at the final state, pg2, is less than
the initial value, pv1. Owing to condensation, the partial pressure decreases because the amount
of water vapor present at the final state is less than at the initial state. Since the amount of
dry air is unchanged, the mole fraction of water vapor in the moist air also decreases.
In the next two examples, we illustrate the use of psychrometric properties introduced
thus far. The examples consider, respectively, cooling moist air at constant pressure and at
constant volume.
EXAMPLE 12.7 Cooling Moist Air at Constant Pressure
A 1 kg sample of moist air initially at 21C, 1 bar, and 70% relative humidity is cooled to 5C while keeping the pressure
constant. Determine (a) the initial humidity ratio, (b) the dew point temperature, in C, and (c) the amount of water vapor that
condenses, in kg.
SOLUTION
Known: A 1 kg sample of moist air is cooled at a constant mixture pressure of 1 bar from 21 to 5C. The initial relative
humidity is 70%.
Find: Determine the initial humidity ratio, the dew point temperature, in C, and the amount of water vapor that condenses,
in kg.
T pg1 = 0.02487 bar

pv1 = 0.01741 bar
21C
Initial state of vapor
m = 1 kg Dewpoint temperature = 15.3C
T1 = 21C pg2 = .00872 bar
1 = 70% 5C
T2 = 5C
Condensate
Final state
of vapor
v
Figure E12.7
Assumptions:
1. The 1-kg sample of moist air is taken as the closed system. The system pressure remains constant at 1 bar.
2. The gas phase can be treated as an ideal gas mixture. Each mixture component acts as an ideal gas existing alone in the
volume occupied by the gas phase at the mixture temperature.
3. When a liquid water phase is present, the water vapor exists as a saturated vapor at the system temperature. The liquid
present is a saturated liquid at the system temperature.
Analysis:
(a) The initial humidity ratio can be evaluated from Eq. 12.43. This requires the partial pressure of the water vapor, pv1, which
can be found from the given relative humidity and pg from Table A-2 at 70F as follows
pv1 fpg 10.72 10.02487 bar2 0.01741 bar
Inserting values in Eq. 12.43

kg 1vapor2
v1 0.622 a b 0.011
0.2542
14.7 0.2542 kg 1dry air2
(b) The dew point temperature is the saturation temperature corresponding to the partial pressure, pv1. Interpolation in
Table A-2 gives T 15.3C. The dew point temperature is labeled on the accompanying property diagram.
(c) The amount of condensate, mw, equals the difference between the initial amount of water vapor in the sample, mv1, and
the final amount of water vapor, mv2. That is
mw mv1 mv2
To evaluate mv1, note that the system initially consists of 1 lb of dry air and water vapor, so 1 lb ma
mv1, where ma
is the mass of dry air present in the sample. Since 1 mv1ma, ma mv1 1. With this we get

mv1 mv1 a
1b
mv1 1
1 kg
v1 v1
Solving for mv1
1 kg
mv1
11v1 2
1
Inserting the value of 1 determined in part (a)
0.0109 kg 1vapor2
1 kg
mv1
11 0.0112
1
The mass of dry air present is then ma 1 0.0109 0.9891 kg (dry air).
Next, let us evaluate mv2. With assumption 3, the partial pressure of the water vapor remaining in the system at the final
state is the saturation pressure corresponding to 5C: pg 0.00872 bar. Accordingly, the humidity ratio after cooling is found
from Eq. 12.43 as
kg 1vapor2
v2 0.622 a b 0.0054
.00872
1.01325 .00872 kg 1dry air2
The mass of the water vapor present at the final state is then
mv2 v2ma 10.00542 10.98912 0.0053 kg 1vapor2
Finally, the amount of water vapor that condenses is
mw mv1 mv2 0.0109 0.0053 0.0056 kg 1condensate2
The amount of water vapor present in a typical moist air mixture is considerably less than the amount of dry air present.
At the final state, the quality of the two-phase liquidvapor mixture of water is x 0.00530.0109 0.47 (47%). The
relative humidity of the gas phase is 100%.
EXAMPLE 12.8 Cooling Moist Air at Constant Volume
An airwater vapor mixture is contained in a rigid, closed vessel with a volume of 35 m3 at 1.5 bar, 120C, and 10%.
The mixture is cooled at constant volume until its temperature is reduced to 22C. Determine (a) the dew point temperature
corresponding to the initial state, in C, (b) the temperature at which condensation actually begins, in C, and (c) the amount
of water condensed, in kg.
SOLUTION
Known: A rigid, closed tank with a volume of 35 m3 containing moist air initially at 1.5 bar, 120C, and 10% is cooled
to 22C.
Find: Determine the dew point temperature at the initial state, in C, the temperature at which condensation actually begins,
in C, and the amount of water condensed, in kg.
T
pv1
V = 35 m3
Dew point 1
T1
temperature
Initially moist air Condensation
at 1.5 bar, 120C 1 begins
= 10%
f2 2 g2
Boundary
v
Figure E12.8
Assumptions:
1. The contents of the tank are taken as a closed system. The system volume remains constant.
2. The gas phase can be treated as an ideal gas mixture. Each mixture component acts as an ideal gas existing alone in the
volume occupied by the gas phase at the mixture temperature.
3. When a liquid water phase is present, the water vapor exists as a saturated vapor at the system temperature. The liquid is
a saturated liquid at the system temperature.
Analysis:
(a) The dew point temperature at the initial state is the saturation temperature corresponding to the partial pressure pv1. With
the given relative humidity and the saturation pressure at 120C from Table A-2
pv1 f1 pg1 10.102 11.9852 0.1985 bar

Interpolating in Table A-2 gives the dew point temperature as 60C, which is the temperature condensation would begin if the
moist air were cooled at constant pressure.
(b) Whether the water exists as a vapor only, or as liquid and vapor, it occupies the full volume, which remains constant. Ac-
cordingly, since the total mass of the water present is also constant, the water undergoes the constant specific volume process
illustrated on the accompanying Tv diagram. In the process from state 1 to state 1, the water exists as a vapor only. For the
process from state 1 to state 2, the water exists as a two-phase liquidvapor mixture. Note that pressure does not remain con-
stant during the cooling process from state 1 to state 2.
State 1 on the Tv diagram denotes the state where the water vapor first becomes saturated. The saturation temperature
at this state is denoted as T . Cooling to a temperature less than T would result in condensation of some of the water vapor
present. Since state 1 is a saturated vapor state, the temperature T can be found by interpolating in Table A-2 with the specific
volume of the water at this state. The specific volume of the vapor at state 1 equals the specific volume of the vapor at state 1,
which can be evaluated from the ideal gas equation
1RMv 2T1
a ba b
8314 N # m 393 K
vv1
pv1 18 kg # K 0.1985 105 N/m2
m3
9.145
kg
Interpolation in Table A-2 with vv1 vg gives T 56C. This is the temperature at which condensation begins.
(c) The amount of condensate equals the difference between the initial and final amounts of water vapor present. The mass
of the water vapor present initially is
V 35 m3
mv1 3.827 kg
vv1 9.145 m3/kg
The mass of water vapor present finally can be determined from the quality. At the final state, the water forms a two-phase
liquidvapor mixture having a specific volume of 9.145 m3/kg. Using this specific volume value, the quality x2 of the
liquidvapor mixture can be found as
vv2 vf2 9.145 1.0022 103
x2 0.178
vg2 vf2 51.447 1.0022 103
where vf2 and vg2 are the saturated liquid and saturated vapor specific volumes at T2 22C, respectively.
Using the quality together with the known total amount of water present, 3.827 kg, the mass of the water vapor contained
in the system at the final state is
mv2 10.1782 13.8272 0.681 kg
The mass of the condensate, mw2, is then
mw2 mv1 mv2 3.827 0.681 3.146 kg
When a moist air mixture is cooled at constant mixture volume, the temperature at which condensation begins is not the
dew point temperature corresponding to the initial state. In this case, condensation begins at 56C, but the dew point tem-
perature at the initial state, determined in part (a), is 60C.
No additional fundamental concepts are required for the study of closed systems involv-
ing mixtures of dry air and water vapor. Example 12.9, which builds on Example 12.8, brings
out some special features of the use of conservation of mass and conservation of energy in
analyzing this kind of system. Similar considerations can be used to study other closed systems
involving moist air.
EXAMPLE 12.9 Evaluating Heat Transfer for Moist Air Cooling at Constant Volume
An airwater vapor mixture is contained in a rigid, closed vessel with a volume of 35 m3 at 1.5 bar, 120C, and 10%.
The mixture is cooled until its temperature is reduced to 22C. Determine the heat transfer during the process, in kJ.
SOLUTION
Known: A rigid, closed tank with a volume of 35 m3 containing moist air initially at 1.5 bar, 120C, and 10% is cooled
to 22C.
Find: Determine the heat transfer for the process, in kJ.
Schematic and Given Data: See the figure for Example 12.8.
Assumptions:
1. The contents of the tank are taken as a closed system. The system volume remains constant.
2. The gas phase can be treated as an ideal gas mixture. Each component acts as an ideal gas existing alone in the volume
occupied by the gas phase at the mixture temperature.
3. When a liquid water phase is present, the water vapor exists as a saturated vapor and the liquid is a saturated liquid, each
at the system temperature.
4. There is no work during the cooling process and no change in kinetic or potential energy.
Analysis: Reduction of the closed system energy balance using assumption 4 results in
0
U Q W
or
Q U2 U1
where
U1 maua1
mv1uv1 maua1
mv1ug1
and
U2 maua2
mv2uv2
mw2uw2 maua2
mv2ug2
mw2uf 2
In these equations, the subscripts a, v, and w denote, respectively, dry air, water vapor, and liquid water. The specific internal
energy of the water vapor at the initial state can be approximated as the saturated vapor value at T1. At the final state, the wa-
ter vapor is assumed to exist as a saturated vapor, so its specific internal energy is ug at T2. The liquid water at the final state
is saturated, so its specific internal energy is uf at T2.
Q ma 1ua2 ua1 2
mv2ug2
mw2uf 2 mv1ug1
The mass of dry air, ma, can be found using the ideal gas equation of state together with the partial pressure of the dry air
at the initial state obtained using pv1 0.1985 bar from the solution to Example 12.8
pa1V 3 11.5 0.19852 105 N/m2 4 135 m3 2
ma
1RMa 2 T1 1831428.97 N # m/kg # K2 1393 K2
40.389 kg
Then, evaluating internal energies of dry air and water from Tables A-22 and A-2, respectively
Q 40.389 1210.49 281.12
0.681 12405.72
3.146 192.322 3.827 12529.32
2851.87
1638.28
290.44 9679.63 10,603 kJ
The values for mv1, mv2, and mw2 are from the solution to Example 12.8.
The first underlined term in this equation for Q is evaluated with specific internal energies from the ideal gas table for air,
Table A-22. Steam table data are used to evaluate the second underlined term. The different datums for internal energy un-
derlying these tables cancel because each of these two terms involves internal energy differences. Since the specific heat
cva for dry air varies only slightly over the interval from 120 to 22C (Table A-20), the specific internal energy change of
the dry air could be evaluated alternatively using a constant cva value. This is left as an exercise.
12.5.5 Evaluating Humidity Ratio Using the

Adiabatic-Saturation Temperature
The humidity ratio of an airwater vapor mixture can be determined, in principle, knowing
adiabatic-saturation the values of three mixture properties: the pressure p, the temperature T, and the adiabatic-
temperature saturation temperature Tas introduced in this section. The relationship among these quantities
State of the water vapor

Moist air in the incoming moist air stream
Saturated mixture
p, T, Tas, , p State of the water
vapor in the
ma ma exiting moist air
stream
mv mv
T pg (Tas)
Tas
Insulation
State of the
Makeup water makeup water
saturated liquid at Tas,
mass flow rate = mv mv
v
(a) (b)
Figure 12.7 Adiabatic saturator. (a) Schematic. (b) Process representation.
is obtained by applying conservation of mass and conservation of energy to an adiabatic sat-

uration process (see box).
Equations 12.48 and 12.49 give the humidity ratio in terms of the adiabatic-saturation
temperature and other quantities:
ha 1Tas 2 ha 1T 2
v 3hg 1Tas 2 hf 1Tas 2 4
v
hg 1T 2 hf 1Tas 2
(12.48)
where hf and hg denote the enthalpies of saturated liquid water and saturated water vapor, re-
spectively, obtained from the steam tables at the indicated temperatures. The enthalpies of
the dry air ha can be obtained from the ideal gas table for air. Alternatively, ha(Tas) ha(T )
cpa(Tas T ), where cpa is an appropriate constant value for the specific heat of dry air. The
humidity ratio appearing in Eq. 12.48 is
pg 1Tas 2
v 0.622
p pg 1Tas 2
(12.49)
where pg(Tas) is the saturation pressure at the adiabatic-saturation temperature and p is the
mixture pressure.
M O D E L I N G A N A D I A B AT I C S AT U R AT I O N P R O C E S S
Figure 12.7 shows the schematic and process representations of an adiabatic saturator,
which is a two-inlet, single-exit device through which moist air passes. The device is
assumed to operate at steady state and without significant heat transfer with its sur-
roundings. An airwater vapor mixture of unknown humidity ratio enters the adia-
batic saturator at a known pressure p and temperature T. As the mixture passes through
the device, it comes into contact with a pool of water. If the entering mixture is not
saturated ( 100%), some of the water would evaporate. The energy required to
evaporate the water would come from the moist air, so the mixture temperature would
decrease as the air passes through the duct. For a sufficiently long duct, the mixture
would be saturated as it exits ( 100%). Since a saturated mixture would be achieved
without heat transfer with the surroundings, the temperature of the exiting mixture is
the adiabatic-saturation temperature. As indicated on Fig. 12.7, a steady flow of
makeup water at temperature Tas is added at the same rate at which water is evapo-
rated. The pressure of the mixture is assumed to remain constant as it passes through
the device. Equation 12.48 giving the humidity ratio of the entering moist air in terms
of p, T, and Tas can be obtained by applying conservation of mass and conservation of
energy to the adiabatic saturator, as follows.
#
At steady state, the mass flow rate of the dry air entering the device, ma, must equal
the mass flow rate of the dry air exiting. The mass flow rate of the makeup water is
# #
the difference between the exiting and entering vapor flow rates denoted by mv and mv,
respectively. These flow rates are labeled on Fig. 12.7a. At steady state, the energy rate
balance reduces to
1maha
mvhv 2 moist air
3 1mv mv 2hw 4 makeup 1maha
mv hv 2 moist air
# # # # # #
entering water exiting
Several assumptions underlie this expression: Each of the two moist air streams is mod-
eled as an ideal gas mixture of dry air and water vapor. Heat
# transfer with the sur-
roundings is assumed to be negligible. There is no work Wcv, and changes in kinetic
and potential energy are ignored.
#
Dividing by the mass flow rate of the dry air, ma, the energy rate balance can be
written on the basis of a unit mass of dry air passing through the device as
1ha
vhg 2 moist air
3 1v v2hf 4 makeup 1ha
vhg 2 moist air (12.50)
entering water exiting
where v mvma and v mv ma.

# # # #
For the exiting saturated mixture, the partial pressure of the water vapor is the satu-
ration pressure corresponding to the adiabatic-saturation temperature, pg(Tas). Accord-
ingly, the humidity ratio can be evaluated knowing Tas and the mixture pressure p, as
indicated by Eq. 12.49. In writing Eq. 12.50, the specific enthalpy of the entering water
vapor has been evaluated as that of saturated water vapor at the temperature of the
incoming mixture, in accordance with Eq. 12.47. Since the exiting mixture is saturated,
the enthalpy of the water vapor at the exit is given by the saturated vapor value at Tas.
The enthalpy of the makeup water is evaluated as that of saturated liquid at Tas.
When Eq. 12.50 is solved for , Eq. 12.48 results. The details of the solution are
left as an exercise. Although derived with reference to an adiabatic saturator, the rela-
tionship provided by Eq. 12.48 applies generally to moist air mixtures and is not re-
stricted to this type of system or even to control volumes. The relationship allows the
humidity ratio to be determined for any moist air mixture for which the pressure p,
temperature T, and adiabatic-saturation temperature Tas are known.

12.6 Psychrometers: Measuring the Wet-Bulb
and Dry-Bulb Temperatures
For moist air mixtures in the normal pressure and temperature ranges of psychrometrics, the
readily-measured wet-bulb temperature is an important parameter.
wet-bulb temperature The wet-bulb temperature is read from a wet-bulb thermometer, which is an ordinary
liquid-in-glass thermometer whose bulb is enclosed by a wick moistened with water. The
dry-bulb temperature term dry-bulb temperature refers simply to the temperature that would be measured by a
thermometer placed in the mixture. Often a wet-bulb thermometer is mounted together with
psychrometer a dry-bulb thermometer to form an instrument called a psychrometer.
12.6 Psychrometers: Measuring the Wet-Bulb and Dry-Bulb Temperatures 591

How Cold is Cold? are better armed to
avoid exposure that
The National Weather Service is finding better ways to help can lead to such seri-
measure our misery during cold snaps so we can avoid ous medical problems
weather dangers. The wind chill index, for many years based as frostbite.
on a single 1945 study, was recently upgraded using new phys- The improved
iological data and computer modeling to better reflect the measure was devel-
perils of cold winds and freezing temperatures. oped by universities,
The new wind chill index is a standardized temperature international scientific
that accounts for both the actual air temperature and the wind societies, and govern-
speed. The formula on which it is based uses measurements of ment in a two-year
skin tissue thermal resistance and computer models of the wind effort that led to the
patterns over the human face, together with principles of heat new standard being
transfer. Using the new index, an air temperature of 5F and a adopted in the United States and Canada. Further upgrades
wind speed of 25 miles per hour correspond to a wind chill tem- are in the works to include the amount of cloud cover in the
perature of 40F. The old index assigned a wind chill of only formula, since solar radiation is also an important factor in
20F to the same conditions. With the new information, people how cold it feels.
The psychrometer of Fig. 12.8a is whirled in the air whose wet- and dry-bulb temperatures
are to be determined. This induces air flow over the two thermometers. For the psychrometer
of Fig. 12.8b, the air flow is induced by a battery-operated fan. In each type of psychrome-
ter, if the surrounding air is not saturated, water in the wick of the wet-bulb thermometer evap-
orates and the temperature of the remaining water falls below the dry-bulb temperature. Even-
tually a steady-state condition is attained by the wet-bulb thermometer. The wet- and dry-bulb
temperatures are then read from the respective thermometers. The wet-bulb temperature de-
pends on the rates of heat and mass transfer between the moistened wick and the air. Since
these depend in turn on the geometry of the thermometer, air velocity, supply water temper-
ature, and other factors, the wet-bulb temperature is not a mixture property.
For moist air mixtures in the normal pressure and temperature ranges of psychrometric ap-
plications, the adiabatic saturation temperature introduced in Sec. 12.5.5 is closely approximated
by the wet-bulb temperature. Accordingly, the humidity ratio for any such mixture can be
calculated by using the wet-bulb temperature in Eqs. 12.48 and 12.49 in place of the adiabatic-
saturation temperature. Close agreement between the adiabatic-saturation and wet-bulb temper-
atures is not generally found for moist air departing from normal psychrometric conditions.
Dry-bulb
thermometer
Bearing Wet-bulb
Handle thermometer
Wet-bulb Air in
thermometer
Dry-bulb
thermometer Battery-
operated
fan
Switch
Air out
Wick (a) (b)

Figure 12.8 Psychrometers. (a) Sling psychrometer. (b) Aspirating psychrometer.

12.7 Psychrometric Charts
Graphical representations of several important properties of moist air are provided by
psychrometric chart psychrometric charts. The main features of one form of chart are shown in Fig. 12.9. A
complete chart in SI units is given in Fig. A-9. This chart is constructed for a mixture
pressure of 1 atm, but charts for other mixture pressures are also available. When the mix-
ture pressure differs only slightly from 1 atm, Figs. A-9 remain sufficiently accurate for
engineering analyses. In this text, such differences are ignored.
Let us consider several features of the psychrometric chart:
Referring to Fig. 12.9, note that the abscissa gives the dry-bulb temperature and the
ordinate provides the humidity ratio. For charts in SI, the temperature is in C and
is expressed in kg, or g, of water vapor per kg of dry air.
Equation 12.43 shows that for fixed mixture pressure there is a direct correspondence
between the partial pressure of the water vapor and the humidity ratio. Accordingly, the
vapor pressure also can be shown on the ordinate, as illustrated on Fig. 12.9.
Curves of constant relative humidity are shown on psychrometric charts. On
Fig. 12.9, curves labeled 100, 50, and 10% are indicated. Since the dew point
is the state where the mixture becomes saturated when cooled at constant vapor
pressure, the dew point temperature corresponding to a given moist air state can be
determined by following a line of constant (constant pv) to the saturation line,
100%. The dew point temperature and dry-bulb temperature are identical for
states on the saturation curve.
Psychrometric charts also give values of the mixture enthalpy per unit mass of dry air
in the mixture: ha
hv. In Fig. A-9, the mixture enthalpy has units of kJ per kg of
dry air. The numerical values provided on these charts are determined relative to the
following special reference states and reference values. In Fig. A-9, the enthalpy of the
dry air ha is determined relative to a zero value at 0C, and not 0 K as in Table A-22.
Accordingly, in place of Eq. 3.49 used to develop the enthalpy data of Tables A-22,
the following expression is employed to evaluate the enthalpy of the dry air for use
Barometric pressure = 1 atm

%
00
=1

Scale for the Wet-bulb and

mixture enthalpy dew point
per unit mass of temperature
dry air % pv
scales Twb 50
=

Twb Volume
per unit
Twb mass of
dry air
= 10%
Dry-bulb temperature
Figure 12.9 Psychrometric chart.
12.8 Analyzing Air-Conditioning Processes 593
on the psychrometric chart:
cpa dT cpaT 1C2

T
ha (12.51)
273.15 K
where cpa is a constant value for the specific heat cp of dry air and T(C) denotes
the temperature in C. In the temperature range of Fig. A-9, cpa can be taken as
1.005 kJ/kg K. On Figs. A-9 the enthalpy of the water vapor hv is evaluated as hg at
the dry-bulb temperature of the mixture from Table A-2.
Another important parameter on psychrometer charts is the wet-bulb temperature. As
illustrated by Figs. A-9, constant Twb lines run from the upper left to the lower right of
the chart. The relationship between the wet-bulb temperature and other chart quantities
is provided by Eq. 12.48. The wet-bulb temperature can be used in this equation in
place of the adiabatic-saturation temperature for the states of moist air located on
Figs. A-9.
Lines of constant wet-bulb temperature are approximately lines of constant mixture
enthalpy per unit mass of dry air. This feature can be brought out by study of the
energy balance for the adiabatic saturator, Eq. 12.50. Since the contribution of the
energy entering the adiabatic saturator with the makeup water is normally much
smaller than that of the moist air, the enthalpy of the entering moist air is very
nearly equal to the enthalpy of the saturated mixture exiting. Accordingly, all states
with the same value of the wet-bulb temperature (adiabatic-saturation temperature)
have nearly the same value for the mixture enthalpy per unit mass of dry air. Al-
though Figs. A-9 ignore this slight effect, some psychrometric charts are drawn to
show the departure of lines of constant wet-bulb temperature from lines of constant
mixture enthalpy.
As shown on Fig. 12.9, psychrometric charts also provide lines representing volume per
unit mass of dry air, Vma. Figure A-9 gives this quantity in units of m3/kg. These spe-
cific volume lines can be interpreted as giving the volume of dry air or of water vapor,
per unit mass of dry air, since each mixture component is considered to fill the entire
volume.
The psychrometric chart is easily used. for example. . . a psychrometer indicates
that in a classroom the dry-bulb temperature is 20C and the wet-bulb temperature is 15C.
Locating the mixture state on Fig. A-9 corresponding to the intersection of these tempera-
tures, we read 0.0086 kg(vapor)/kg(dry air) and 60%.

12.8 Analyzing Air-Conditioning Processes
The purpose of the present section is to study typical air-conditioning processes using
the psychrometric principles developed in this chapter. Specific illustrations are pro-
vided in the form of solved examples involving control volumes at steady state. In
each case, the methodology introduced in Sec. 12.8.1 is employed to arrive at the solu-
tion. To reinforce the psychrometric principles developed in the present chapter, the re-
quired psychrometric parameters are determined in most cases using tabular data provided
in the appendix. It is left as an exercise to check these values by means of a psychro-
metric chart.
12.8.1 Applying Mass and Energy Balances to

Air-Conditioning Systems
The object of this section is to illustrate the use of the conservation of mass and conserva-
tion of energy principles in analyzing systems involving mixtures of dry air and water vapor
in which a condensed water phase may be present. The same basic solution approach that
has been used in thermodynamic analyses considered thus far is applicable. The only new
aspect is the use of the special vocabulary and parameters of psychrometrics.
Systems that accomplish air-conditioning processes such as heating, cooling, humidifica-
tion, or dehumidification are normally analyzed on a control volume basis. To consider a typ-
ical analysis, refer to Fig. 12.10, which shows a two-inlet, single-exit control volume at steady
state. A moist air stream enters at 1, a moist air stream exits at 2, and a water-only stream #
enters at 3. The water-only stream may be a liquid or a vapor. Heat transfer at the rate Qcv
can occur between
# the control volume and its surroundings. Depending on the application,
the value of Qcv might be positive, negative, or zero.
MASS BALANCE. At steady state, the amounts of dry air and water vapor contained within
the control volume cannot vary. Thus, for each component individually it is necessary for the
total incoming and outgoing mass flow rates to be equal. That is
1dry air2
# #
ma1 ma2
1water2
# # #
mv1
mw mv2
#
For simplicity, the constant mass flow rate of the dry air is denoted by ma. The mass flow
rates of the water vapor can be expressed conveniently in terms of humidity ratios as
# # # #
mv1 v1ma and mv2 v2ma. With these expressions, the mass balance for water becomes
mw ma 1v2 v1 2 1water2
# #
(12.52)
When water is added at 3, 2 is greater than 1.
#
ENERGY BALANCE. Assuming Wcv 0 and ignoring all kinetic and potential energy ef-
fects, the energy rate balance reduces at steady state to
0 Qcv
1maha1
mv1hv1 2
mwhw 1maha2
mv2hv2 2
# # # # # #
(12.53)
In this equation, the entering and exiting moist air streams are regarded as ideal gas mixtures
of dry air and water vapor.
Equation 12.53 can be cast into a form that is particularly convenient for the analysis of
air-conditioning systems. First, with Eq. 12.47 the enthalpies of the entering and exiting water
vapor can be evaluated as the saturated vapor enthalpies corresponding to the temperatures
T1 and T2, respectively, giving
0 Qcv
1maha1
mv1hg1 2
mwhw 1maha2
mv2hg2 2
# # # # # #
# # # #
Then, with mv1 v1ma and mv2 v2ma, the equation can be expressed as
0 Qcv
ma 1ha1
v1hg1 2
mwhw ma 1ha2
v2hg2 2
# # # #
(12.54)

Q cv Boundary
Moist air 2
1
m a, Moist air

m v1 m a, m v2
3 Figure 12.10 System for conditioning

Liquid or vapor, m w moist air.
Finally, introducing Eq. 12.52, the energy rate balance becomes

0 Qcv
ma 3 1ha1 ha2 2
v1hg1
1v2 v1 2hw v2hg2 4
# #
(12.55)
The first underlined term of Eq. 12.55 can be evaluated from Tables A-22 giving the ideal
gas properties of air. Alternatively, since relatively small temperature differences are nor-
mally encountered in the class of systems under present consideration, this term can be eval-
uated as ha1 ha2 cpa(T1 T2), where cpa is a constant value for the specific heat of dry
air. The second underlined term of Eq. 12.55 can be evaluated using steam table data to-
gether with known values for 1 and 2.
MODELING SUMMARY. As suggested by the foregoing development, several simplifying

assumptions are commonly used when analyzing the air-conditioning systems under present
consideration. In addition to the assumption of steady-state operation, one-dimensional flow
is assumed to apply at locations where matter crosses the boundary of the control volume,
and the effects of kinetic and potential energy at these locations are neglected. In most cases
there is no work, except for flow work where matter crosses the boundary. Further simplifi-
cations also may be required in particular cases.
12.8.2 Conditioning Moist Air at Constant Composition

Building air-conditioning systems frequently heat or cool a moist air stream with no change
in the amount of water vapor present. In such cases the humidity ratio remains constant,
while relative humidity and other moist air parameters vary. Example 12.10 gives an ele-
mentary illustration using the methodology of Sec. 12.8.1.
EXAMPLE 12.10 Heating Moist Air in a Duct
Moist air enters a duct at 10C, 80% relative humidity, and a volumetric flow rate of 150 m3/min. The mixture is heated as it
flows through the duct and exits at 30C. No moisture is added or removed, and the mixture pressure remains approximately
constant at 1 bar. For steady-state operation, determine (a) the rate of heat transfer, in kJ/min, and (b) the relative humidity
at the exit. Changes in kinetic and potential energy can be ignored.
SOLUTION
Known: Moist air that enters a duct at 10C and 80% with a volumetric flow rate of 150 m3/min is heated at constant
pressure and exits at 30C. No moisture is added or removed.
Find: Determine the rate of heat transfer, in kJ/min, and the relative humidity at the exit.
T
m3
___ pg (T2 )
(AV)1 = 150 min Qcv pv
T1 = 10C
1 = 80% T2
T2 = 30C 2
pg (T1)
T1
1 Boundary 2 1
v
Figure E12.10a
Assumptions:
1. The control volume shown in the accompanying figure operates at steady state.
#
2. The changes in kinetic and potential energy between inlet and exit can be ignored and Wcv 0.
3. The entering and exiting moist air streams can be regarded as ideal gas mixtures.
Analysis:
#
(a) The heat transfer rate Qcv can be determined from the mass and energy rate balances. At steady state, the amounts of dry
air and water vapor contained within the control volume cannot vary. Thus, for each component individually it is necessary
for the incoming and outgoing mass flow rates to be equal. That is
1dry air2
# #
ma1 ma2
1water2
# #
mv1 mv2
# #
For simplicity, the constant mass flow rates of the dry air and water vapor are denoted, respectively, by ma and mv. From these
considerations, it can be concluded that the humidity ratio is the same at the inlet and exit: 1 2.
The steady-state form of the energy rate balance reduces with assumption 2 to
0 Qcv Wcv
1mah a1
mvh v1 2 1mah a2
mvh v2 2
# # 0 # # # #
In writing this equation, the incoming and outgoing moist air streams are regarded as ideal gas mixtures of dry air and water
vapor. #
Solving for Qcv
Qcv ma 1ha2 ha1 2

mv 1h v2 h v1 2
# # #
# # #
Noting that mv vma, where is the humidity ratio, the expression for Qcv can be written in the form
Qcv ma 3 1ha2 ha1 2

v 1hv2 hv1 2 4
#
#
(1)
#
To evaluate Qcv from this expression requires the specific enthalpies of the dry air and water vapor at the inlet and exit, the
mass flow rate of the dry air, and the humidity ratio.
The specific enthalpies of the dry air are obtained from Table A-22 at the inlet and exit temperatures T1 and T2, respec-
tively: ha1 283.1 kJ/kg, ha2 303.2 kJ/kg. The specific enthalpies of the water vapor are found using hv hg and data from
Table A-2 at T1 and T2, respectively: hg1 2519.8 kJ/kg, hg2 2556.3 kJ/kg.
The mass flow rate of the dry air can be determined from the volumetric flow rate at the inlet (AV)1
# 1AV2 1
ma
va1
In this equation, va1 is the specific volume of the dry air evaluated at T1 and the partial pressure of the dry air pa1. Using the
ideal gas equation of state
1RM2 T1
va1
pa1
The partial pressure pa1 can be determined from the mixture pressure p and the partial pressure of the water vapor pv1: pa1
p pv1. To find pv1, use the given inlet relative humidity and the saturation pressure at 10C from Table A-2
pv1 f1 pg1 10.82 10.01228 bar2 0.0098 bar
Since the mixture pressure is 1 bar, it follows that pa1 0.9902 bar. The specific volume of the dry air is then
a b 1283 K2
8314 N # m
28.97 kg # K
va1 0.82 m3/kg
10 .9902 105 N/m2 2
Using this value, the mass flow rate of the dry air is
# 150 m3/min
ma 182.9 kg/min
0 .82 m3/kg
The humidity ratio can be found from
v 0.622 a b 0.622 a b
pv1 0.0098
p pv1 1 0.0098
kg 1vapor2
0.00616
kg 1dry air2
Finally, substituting values into Eq. (1) we get
Qcv 182.9 3 1303.2 283.12

10.006162 12556.3 2519.82 4
#
3717 kJ/min
(b) The states of the water vapor at the duct inlet and exit are located on the accompanying Tv diagram. Both the
composition of the moist air and the mixture pressure remain constant, so the partial pressure of the water vapor at the
exit equals the partial pressure of the water vapor at the inlet: pv2 pv1 0.0098 bar. The relative humidity at the exit
is then
0.231 123.1% 2
pv2 0.0098
f2
pg2

0.04246
where pg2 is from Table A-2 at 30C.
Alternative Psychrometric Chart Solution: Let us consider an alternative solution using the psychrometric chart. As shown
on the sketch of the psychrometric chart, Fig. E12.10b, the state of the moist air at the inlet is defined by 1 80% and a
dry-bulb temperature of 10C. From the solution to part (a), we know that the humidity ratio has the same value at the exit
as at the inlet. Accordingly, the state of the moist air at the exit is fixed by 2 1 and a dry-bulb temperature of 30C. By
inspection of Fig. A-9, the relative humidity at the duct exit is about 23%, and thus in agreement with the result of part (b).
The rate of heat transfer can be evaluated from the psychrometric chart using the following expression obtained by rear-
ranging Eq. (1) of part (a) to read
Qcv ma 3 1ha
vhv 2 2 1ha
vhv 2 1 4
# #
(2)
#
To evaluate Qcv from this expression requires values for the mixture enthalpy per unit mass of dry air (ha
hv) at the in-
let and exit. These can be determined by inspection of the psychrometric chart, Fig. A-9, as (ha
hv)1 25.7 kJ/kg (dry
air), (ha
hv)2 45.9 kJ/kg (dry air).
Using the specific volume value va1 from the chart at the inlet state together with the given volumetric flow rate at the in-
let, the mass flow rate of the dry air is found as
# 150 m3/min kg1dry air2

ma 3
185
0.81 m /kg1dry air2 min
Substituting values into the energy rate balance, Eq. (2), we get
145.9 25.72
# kg1dry air2 kJ
Qcv 185
min kg1dry air2
kJ
3737
min
which agrees closely with the result obtained in part (a), as expected.
lpy
n tha
r ee
xtu 0%
Mi 10
= %
80
=

2 = 1
1 2
10C 30C
Dry-bulb temperature
Figure E12.10b
#
The first underlined term in this equation for Qcv is evaluated with specific enthalpies from the ideal gas table for air,
Table A-22. Steam table data are used to evaluate the second underlined term. Note that the different datums for enthalpy
underlying these tables cancel because each of the two terms involves enthalpy differences only. Since the specific heat
cpa for dry air varies only slightly over the interval from 10 to 30C (Table A-20), the specific enthalpy change of the dry
air could be evaluated alternatively with cpa 1.005 kJ/kg # K.
No water is added or removed as the moist air passes through the duct at constant pressure; accordingly, the humidity ra-
tio and the partial pressures pv and pa remain constant. However, because the saturation pressure increases as the tem-
perature increases from inlet to exit, the relative humidity decreases: 2 1.
The mixture pressure, 1 bar, differs slightly from the pressure used to construct the psychrometric chart, 1 atm. This dif-
ference is ignored.
12.8.3 Dehumidification
When a moist air stream is cooled at constant mixture pressure to a temperature below its
dew point temperature, some condensation of the water vapor initially present would occur.
Figure 12.11 shows the schematic of a dehumidifier using this principle. Moist air enters at
state 1 and flows across a cooling coil through which a refrigerant or chilled water circu-
lates. Some of the water vapor initially present in the moist air condenses, and a saturated
moist air mixture exits the dehumidifier section at state 2. Although water would condense
at various temperatures, the condensed water is assumed to be cooled to T2 before it exits
the dehumidifier. Since the moist air leaving the humidifier is saturated at a temperature lower
than the temperature of the moist air entering, the moist air stream might be unsuitable for
direct use in occupied spaces. However, by passing the stream through a following heating
section, it can be brought to a condition most occupants would regard as comfortable. Let
us sketch the procedure for evaluating the rates at which condensate exits and refrigerant
circulates.
#
MASS BALANCE. The mass flow rate of the condensate mw can be related to the mass flow
#
rate of the dry air ma by applying conservation of mass separately for the dry air and water
passing through the dehumidifier section. At steady state
1dry air2
# #
ma1 ma2
1water2
# # #
mv1 mw
mv2
Cooling
coil
Heating

mr coil
1 i e 2 3
Moist air
m a, 2 = 100%
T1, 1, T 2 < T1 T3 > T2
p = 1 atm 2 < 1 3 = 2
Initial dew
point 1
2 3
%
100 3
=
m w
Condensate
saturated at T2 T2 T3 T1
(Dehumidifier section) (Heating section) Dry-bulb temperature
(a) (b)
Figure 12.11 Dehumidification. (a) Equipment schematic. (b) Psychrometric chart
representation.
#
The common mass flow rate of the dry air is denoted as ma. Solving for the mass flow rate
of the condensate
# # #
mw mv1 mv2
# # # #
Introducing mv1 v1ma and mv2 v2ma, the amount of water condensed per unit mass of
dry air passing through the device is
#
mw
# v1 v2
ma
This expression requires the humidity ratios 1 and 2. Because no moisture is added or re-
moved in the heating section, it can be concluded from conservation of mass that 2 3,
so 3 can be used in the above equation in place of 2.
#
ENERGY BALANCE. The mass flow rate of the refrigerant through the cooling coil mr can
#
be related to the mass flow rate of the# dry air ma by means of an energy rate balance applied
to the dehumidifier section. With Wcv 0, negligible heat transfer with the surroundings,
and no significant kinetic and potential energy changes, the energy rate balance reduces at
steady state to
0 mr 1hi he 2
1maha1
mv1hv1 2 mwhw 1maha2
mv2hv2 2
# # # # # #
where hi and he denote the specific enthalpy values of the refrigerant entering and exiting the
# # # # # #
dehumidifier section, respectively. Introducing mv1 v1ma, mv2 v2ma, and mw ( 1 2) ma
0 mr 1hi he 2
ma 3 1ha1 ha2 2
v1hg1 v2hg2 1v1 v2 2hf2 4
# #
where the specific enthalpies of the water vapor at 1 and 2 are evaluated at the saturated va-
por values corresponding to T1 and T2, respectively. Since the condensate is assumed to exit
as a saturated liquid at T2, hw hf2. Solving for the refrigerant mass flow rate per unit mass
of dry air flowing through the device
#
mr 1ha1 ha2 2
v1hg1 v2hg2 1v1 v2 2hf 2
#
ma he hi
The accompanying psychrometric chart, Fig. 12.11b, illustrates important features of the
processes involved. As indicated by the chart, the moist air first cools from state 1, where
the temperature is T1 and the humidity ratio is 1, to state 2, where the mixture is saturated
(2 100%), the temperature is T2 T1, and the humidity ratio is 2 1. During the
subsequent heating process, the humidity ratio would remain constant, 2 3, and the
temperature would increase to T3. Since the states visited would not be equilibrium states,
these processes are indicated on the psychrometric chart by dashed lines. The example to
follow provides a specific illustration.
EXAMPLE 12.11 Dehumidifier
Moist air at 30C and 50% relative humidity enters a dehumidifier operating at steady state with a volumetric flow rate of
280 m3/min. The moist air passes over a cooling coil and water vapor condenses. Condensate exits the dehumidifier saturated
at 10C. Saturated moist air exits in a separate stream at the same temperature. There is no significant loss of energy by heat
transfer to the surroundings and pressure remains constant at 1.013 bar. Determine (a) the mass flow rate of the dry air, in
kg/min, (b) the rate at which water is condensed, in kg per kg of dry air flowing through the control volume, and (c) the
required refrigerating capacity, in tons.
SOLUTION
Known: Moist air enters a dehumidifier at 30C and 50% relative humidity with a volumetric flow rate of 280 m3/min. Con-
densate and moist air exit in separate streams at 10C.
Determine: Find the mass flow rate of the dry air, in kg/min, the rate at which water is condensed, in kg per kg of dry air,
and the required refrigerating capacity, in tons.
Cooling coil Heating coil
Assumptions:
Saturated
1. The control volume shown in the accompanying
mixture figure operates at steady state. Changes in# kinetic and
(AV)1 = 280 m3/min 10C potential energy can be neglected, and Wcv 0.
T1 = 30C
1 = 50% 2. There is no significant heat transfer to the
surroundings.
3. The pressure remains constant throughout at
1.013 bar.
1 3 2 4. At location 2, the moist air is saturated. The con-
Control volume densate exits at location 3 as a saturated liquid at tem-
perature T2.
Condensate,
saturated at
T2 = 10C
Figure E12.11
Analysis:
(a) At steady state, the mass flow rates of the dry air entering and exiting are equal. The common mass flow rate of the dry
air can be determined from the volumetric flow rate at the inlet
# 1AV2 1
ma
va1
The specific volume of the dry air at inlet 1, va1, can be evaluated using the ideal gas equation of state, so
# 1AV2 1
ma
1RMa 2 1T1 pa1 2
The partial pressure of the dry air pa1 can be determined from pa1 p1 pv1. Using the relative humidity at the inlet 1 and
the saturation pressure at 30C from Table A-2
pv1 f1 pg1 10.52 10.042462 0.02123 bar
#
Thus, pa1 1.013 0.02123 0.99177 bar. Inserting values into the expression for ma gives
# 1280 m3/min2 10.99177 105 N/m2 2
ma 319.35 kg/min
1831428.97 N # m/kg # K2 1303 K2
# # # # # # #
(b) Conservation of mass for the water requires mv1 mv2
mw. With mv1 v1ma and mv2 v2ma, the rate at which water
is condensed per unit mass of dry air is
#
mw
# v1 v2
ma
The humidity ratios 1 and 2 can be evaluated using Eq. 12.43. Thus, 1 is
v1 0.622 a b 0.622 a b 0.0133

pv1 0.02123 kg1vapor2
p1 pv1 0.99177 kg1dry air2
Since the moist air is saturated at 10C, pv2 equals the saturation pressure at 10C: pg 0.01228 bar from Table A-2. Equa-
tion 12.43 then gives 2 0.0076 kg(vapor)kg(dry air). With these values for 1 and 2
#
mw kg1condensate2
# 0.0133 0.0076 0.0057
ma kg1dry air2
#
(c) The rate of heat transfer Qcv between the moist air stream and the refrigerant coil can be determined using an energy rate
balance. With assumptions 1 and 2, the steady-state form of the energy rate balance reduces to
0 Qcv
1maha1
mv1hv1 2 mwhw 1maha2
mv2hv2 2
#
# # # # #
With mv1 v1ma, mv2 v2ma, and mw 1v1 v2 2 ma, this becomes
# # # # # #
Qcv ma 3 1ha2 ha1 2 v1hg1

v2hg2
1v1 v2 2 hf2 4
# #
where the specific enthalpies of the water vapor at 1 and 2 are evaluated at the saturated vapor values corresponding to T1 and
T2, respectively, and the specific enthalpy of the exiting condensate is evaluated as hf at T2. Selecting enthalpies from Tables A-2
and A-22, as appropriate
Qcv 1319.352 3 1283.1 303.22 0.0133 12556.32
#

0.0076 12519.82
0.0057 142.012 4
11,084 kJ/min
Since 1 ton of refrigeration equals a heat transfer rate of 211 kJ/min (Sec. 10.2), the required refrigerating capacity is 52.5 tons.
#
If a psychrometric chart were used to obtain data, this expression for Qcv would be rearranged to read
Qcv ma 3 1ha
vhv 2 2 1ha
vhv 2 1
1v1 v2 2 hw 4
# #
The underlined terms and humidity ratios 1 and 2 would be read directly from the chart; the specific enthalpy hw would
be obtained from Table A-2 as hf at T2.
12.8.4 Humidification
It is often necessary to increase the moisture content of the air circulated through occupied
spaces. One way to accomplish this is to inject steam. Alternatively, liquid water can be
sprayed into the air. Both cases are shown schematically in Fig. 12.12a. The temperature of
1 2
2 T2 > T1 T2 < T1
2 > 1 2 2 > 1
Moist air Moist air
T 1, 1 T2, 2 > 1
1
1
Water injected
(vapor or liquid) Dry-bulb temperature Dry-bulb temperature
(a) (b) (c)
Figure 12.12 Humidification. (a) Control volume. (b) Steam injected. (c) Liquid injected.
the moist air as it exits the humidifier depends on the condition of the water introduced.
When relatively high-temperature steam is injected, both the humidity ratio and the dry-bulb
temperature would be increased. This is illustrated by the accompanying psychrometric chart
of Fig. 12.12b. If liquid water was injected instead of steam, the moist air may exit the
humidifier with a lower temperature than at the inlet. This is illustrated in Fig. 12.12c. The
example to follow illustrates the case of steam injection. The case of liquid water injection
is considered further in the next section.
EXAMPLE 12.12 Steam-Spray Humidifier
Moist air with a temperature of 22C and a wet-bulb temperature of 9C enters a steam-spray humidifier. The mass flow rate
of the dry air is 90 kg/min. Saturated water vapor at 110C is injected into the mixture at a rate of 52 kg/h. There is no heat
transfer with the surroundings, and the pressure is constant throughout at 1 bar. Using the psychrometric chart, determine at
the exit (a) the humidity ratio and (b) the temperature, in C.
SOLUTION
Known: Moist air enters a humidifier at a temperature of 22C and a wet-bulb temperature of 9C. The mass flow rate of
the dry air is 90 kg/min. Saturated water vapor at 110C is injected into the mixture at a rate of 52 kg/h.
Find: Using the psychrometric chart, determine at the exit the humidity ratio and the temperature, in C.
1 2
Moist air Assumptions:
m a = T2 = ?
2 = ? 1. The control volume shown in the accompanying figure operates
90 kg/min
at steady state.
# Changes in kinetic and potential energy can be neg-
T1 = 22C
Twb = 9C
lected and Wcv 0.
3 Boundary 3. The pressure remains constant throughout at 1 bar. Figure A-9
Saturated water vapor remains valid at this pressure.
at 110C, m st = 52 kg/h
Figure E12.12
Analysis: (a) The humidity ratio at the exit 2 can be found from mass rate balances on the dry air and water individually. Thus
1dry air2
# #
ma1 ma2
1water2
# # #
mv1
mst mv2
# # # # #
With mv1 v1ma, and mv2 v2ma, where ma is the mass flow rate of the air, the second of these becomes
#
mst
v2 v1
#
ma
Using the inlet dry-bulb temperature, 22C, and the inlet wet-bulb temperature, 9C, the value of the humidity ratio 1 can be
found by inspection of the psychrometric chart, Fig. A-9. The result is 1 0.002 kg(vapor)kg(dry air). This value should
be verified as an exercise. Inserting values into the expression for 2
152 kg/h2 0 1 h60 min 0 kg1vapor2
v2 0.002
0.0116
90 kg/min kg1dry air2
(b) The temperature at the exit can be determined using an energy rate balance. With assumptions 1 and 2, the steady-state
form of the energy rate balance reduces to a special case of Eq. 12.55. Namely
0 ha1 ha2
v1hg1
1v2 v1 2 hg3 v2hg2 (1)
In writing this, the specific enthalpies of the water vapor at 1 and 2 are evaluated as the respective saturated vapor values, and
hg3 denotes the enthalpy of the saturated vapor injected into the moist air.
Equation (1) can be rearranged in the following form suitable for use with the psychrometric chart.
1ha
vhg 2 2 1ha
vhg 2 1
1v2 v1 2 hg3 (2)
The first term on the right can be obtained from Fig. A-9 at the state defined by the intersection of the inlet dry-bulb tem-
perature, 22C, and the inlet wet-bulb temperature, 9C: 27.2 kJ/kg(dry air). The second term on the right can be evaluated
with the known humidity ratios 1 and 2 and the value of hg3 from Table A-2: 2691.5 kJ/kg(vapor). The state at the exit is
fixed by 2 and (ha
hg)2 53 kJ/kg(dry air). The temperature at the exit can then be read directly from the chart. The
result is T2 23.5C.
# #
The following program allows T2 to be determined using IT, where ma is denoted as mdota, mst is denoted as mdotst, w1
and w2 denote 1 and 2, respectively, and so on.
// Given data
T1 = 22 // C
Twb1 = 9 // C
mdota = 90 // kg/min
p = 1 // bar
Tst = 110 // C
mdotst = (52 / 60) // converting kg/h to kg/min
// Evaluate humidity ratios
w1 = w_TTwb(T1,Twb1,p)
w2 = w1 + (mdotst / mdota)
// Denoting the enthalpy of moist air at state 1 by
// h1, etc., the energy balance, Eq. (1), becomes
0 = h1 h2 + (w2 w1)*hst
// Evaluate enthalpies
h1 = ha_Tw(T1,w1)
h2 = ha_Tw(T2,w2)
hst = hsat_Px(Water/Steam,psat,1)
psat = Psat_T(Water/Steam, Tst)
Using the Solve button, the result is T2 23.4C, which agrees closely with the values obtained above, as expected.
A solution of Eq. (2) using data from Tables A-2 and A-22 requires an iterative (trial) procedure. The result is T2 24C,
as can be verified.
Note the use of special Moist Air functions listed in the Properties menu of IT.
Water at Tw Mixture enthalpy

1 2 per unit mass
of dry air
2 2
Moist air T2 < T1
m a, T1, 1 2 > 1
1 1
Soaked T2 T1
pad Dry-bulb temperature
(a) (b)
Figure 12.13 Evaporative cooling. (a) Equipment schematic. (b) Psychrometric chart
representation.
12.8.5 Evaporative Cooling

Cooling in hot, relatively dry climates can be accomplished by evaporative cooling. This in-
volves either spraying liquid water into air or forcing air through a soaked pad that is kept
replenished with water, as shown in Fig. 12.13. Owing to the low humidity of the moist air
entering at state 1, part of the injected water evaporates. The energy for evaporation is pro-
vided by the air stream, which is reduced in temperature and exits at state 2 with a lower
temperature than the entering stream. Because the incoming air is relatively dry, the addi-
tional moisture carried by the exiting moist air stream is normally
# beneficial.
For negligible heat transfer with the surroundings, no work Wcv, and no significant changes
in kinetic and potential energy, the steady-state forms of the mass and energy rate balances
reduce for the control volume of Fig. 12.13a to
1ha2
v2hg2 2 1v2 v1 2hf
1ha1
v1hg1 2
where hf denotes the specific enthalpy of the liquid stream entering the control volume. All
the injected water is assumed to evaporate into the moist air stream. The underlined term
accounts for the energy carried in with the injected liquid water. This term is normally much
smaller in magnitude than either of the two moist air enthalpy terms. Accordingly, the enthalpy
of the moist air varies only slightly, as illustrated on the psychrometric chart of Fig. 12.13b.
Recalling that lines of constant mixture enthalpy are closely lines of constant wet-bulb tem-
perature (Sec. 12.7), it follows that evaporative cooling takes place at a nearly constant wet-
bulb temperature.
In the next example, we consider the analysis of an evaporative cooler.
EXAMPLE 12.13 Evaporative Cooler
Air at 38C and 10% relative humidity enters an evaporative cooler with a volumetric flow rate of 140 m3/min. Moist air exits
the cooler at 21C. Water is added to the soaked pad of the cooler as a liquid at 21C and evaporates fully into the moist air.
There is no heat transfer with the surroundings and the pressure is constant throughout at 1 atm. Determine (a) the mass flow
rate of the water to the soaked pad, in lb/h, and (b) the relative humidity of the moist air at the exit to the evaporative cooler.
SOLUTION
Known: Air at 38C and 10% enters an evaporative cooler with a volumetric flow rate of 140 m3/min. Moist air exits
the cooler at 21C. Water is added to the soaked pad of the cooler at 21C.
Find: Determine the mass flow rate of the water to the soaked pad, in lb/h, and the relative humidity of the moist air at the
exit of the cooler.
Water at 21C
Assumptions:
1. The control volume shown in the accompanying figure oper-

ates at steady state.# Changes in kinetic and potential energy can
T1 = 38C T2 = 21C be neglected and Wcv 0.
1 = 10% 3
m
(AV)1 = 140 ___ 2. There is no heat transfer with the surroundings.
min
3. The water added to the soaked pad enters as a liquid and evap-
orates fully into the moist air.
1 2
4. The pressure remains constant throughout at 1 atm.
Soaked pad Boundary
Figure E12.13
Analysis:
(a) Applying conservation of mass to the dry air and water individually as in previous examples gives
mw ma 1v2 v1 2
# #
# # #
where mw is the mass flow rate of the water to the soaked pad. To find mw requires 1, ma, and 2. These will now be evalu-
ated in turn.
The humidity ratio 1 can be found from Eq. 12.43, which requires pv1, the partial pressure of the moist air entering the
control volume. Using the given relative humidity 1 and pg at T1 from Table A-2, we have pv1 1pg1 0.0066 bar. With
this, 1 0.00408 kg(vapor)kg(dry air).
#
The mass flow rate of the dry air ma can be found as in previous examples using the volumetric flow rate and specific vol-
ume of the dry air. Thus
# 1AV2 1
ma
va1
The specific volume of the dry air can be evaluated from the ideal gas equation of state. The result is va1 0.887 m3/kg(dry air).
Inserting values, the mass flow rate of the dry air is
# 140 m3/min kg1dry air2
ma 157.8
0.887 m3/kg1dry air2 min
To find the humidity ratio 2, reduce the steady-state forms of the mass and energy rate balances using assumption 1 to
obtain
0 1maha1
mv1hv1 2
mwhw 1maha2
mv2hv2 2
# # # # #
With the same reasoning as in previous examples, this can be expressed as

0 1ha
vhg 2 1
1v2 v1 2hf 1ha
vhg 2 2
where hf denotes the specific enthalpy of the water entering the control volume at 21C. Solving for 2
ha1 ha2
v1 1hg1 hf 2 cpa 1T1 T2 2
v1 1hg1 hf 2
v2
hg2 hf hg2 hf
where cpa 1.005 kJ/ kg # K. With hf, hg1, and hg2 from Table A-2
11.0052 138 212
0.00408 12570.7 88.142
v2
2451.8
kg1vapor2
.011
kg1dry air2
# #
Substituting values for ma, 1, and 2 into the expression for mw
mw c 157.8 ` ` d 10.011 0.004082

# kg1dry air2 60 min kg1water2
min 1h kg1dry air2
kg1water2
65.5
h
(b) The relative humidity of the moist air at the exit can be determined using Eq. 12.44. The partial pressure of the water va-
por required by this expression can be found by solving Eq. 12.43 to obtain
v 2p
pv2
v2
0.622
Inserting values
10.0112 11.01325 bars2
pv2 0.0176 bar
1.011
0.6222
At 21C, the saturation pressure is 0.02487 bar. Thus, the relative humidity at the exit is
0.708 170.8% 2
0.0176
f2
0.02487
Since the underlined term in this equation is much smaller than either of the moist air enthalpies, the enthalpy of the moist
air remains nearly constant, and thus evaporative cooling takes place at nearly constant wet-bulb temperature. This can be
verified by locating the incoming and outgoing moist air states on the psychrometric chart.
A constant value of the specific heat cpa has been used here to evaluate the term (ha1 ha2). As shown in previous exam-
ples, this term can be evaluated alternatively using the ideal gas table for air.
12.8.6 Adiabatic Mixing of Two Moist Air Streams

A common process in air-conditioning systems is the mixing of moist air streams, as shown
in Fig. 12.14. The objective of the thermodynamic analysis of such a process is normally
to fix the flow rate and state of the exiting stream for specified flow rates and states of
each of the two inlet streams. The case of adiabatic mixing is governed by Eqs. 12.56
to follow.
The mass rate balances for the dry air and water vapor at steady state are, respectively,
1dry air2
# # #
ma1
ma2 ma3
1water vapor2
# # # (12.56a)
mv1
mv2 mv3
# #
With mv vma, the water vapor mass balance becomes
1water vapor2
# # #
v1ma1
v2ma2 v3ma3 (12.56b)
1 m a1, T1, 1
3
m a3
T3
3
Figure 12.14 Adiabatic mixing of two

Insulation
2 m a2, T2, 2 moist air streams.
# #
Assuming Qcv Wcv 0 and ignoring the effects of kinetic and potential energy, the
energy rate balance reduces at steady state to
ma1 1ha1
v1hg1 2
ma2 1ha2
v2hg2 2 ma3 1ha3
v3hg3 2
# # #
(12.56c)
where the enthalpies of the entering and exiting water vapor are evaluated as the saturated
vapor values at the respective dry-bulb temperatures.
If the inlet flow rates and states are known, Eqs. 12.56 are three equations in three unknowns:
#
ma3, v3, and (ha3
3hg3). The solution of these equations is illustrated by the next example.
EXAMPLE 12.14 Adiabatic Mixing of Moist Streams
A stream consisting of 142 m3/min of moist air at a temperature of 5C and a humidity ratio of 0.002 kg(vapor)kg(dry air)
is mixed adiabatically with a second stream consisting of 425 m3/min of moist air at 24C and 50% relative humidity. The
pressure is constant throughout at 1 bar. Using the psychrometric chart, determine (a) the humidity ratio and (b) the temper-
ature of the exiting mixed stream, in C.
SOLUTION
Known: A moist air stream at 5C, 0.002 kg(vapor)kg(dry air), and a volumetric flow rate of 142 m3/min is mixed
adiabatically with a stream consisting of 425 m3/min of moist air at 24C and 50%.
Find: Determine the humidity ratio and the temperature, in C, of the mixed stream exiting the control volume.
1
Insulation Assumptions:
3
(AV)1 = 142 m3/min
T1 = 5C kg (vapor) 3=? 1. The control volume shown in the accompany-
1 = 0.002 ________ __
kg (dry air) ing figure operates at steady state. Changes in ki-
T3 = ? netic and potential energy can be neglected and
#
Wcv 0.
2
(AV)2 = 425 m3/min 3. The pressure remains constant throughout at
T2 = 24C 1 bar.
2 = 50%
Figure E12.14
Analysis:
(a) The humidity ratio 3 can be found by means of mass rate balances for the dry air and water vapor, respectively
1dry air2
# # #
ma1
ma2 ma3
1water vapor2
# # #
mv1
mv2 mv3
# # # # # #
With mv1 v1ma1, mv2 v2ma2, and mv3 v3ma3, the second of these balances becomes
# # #
v1ma1
v2ma2 v3ma3
Solving
# #
v1ma1
v2ma2
v3 #
ma3
# # #
Since ma3 ma1
ma2, this can be expressed as
# #
v1ma1
v2ma2
v3 # #
ma1
ma2
# # # #
To determine 3 requires values for 2, ma1, and ma2. The mass flow rates of the dry air, ma1 and ma2, can be found as in
previous examples using the given volumetric flow rates
# 1AV2 1 # 1AV2 2
ma1 , ma2
va1 va2
The values of va1, and va2, and 2 are readily found from the psychrometric chart, Fig. A-9. Thus, at 1 0.002 and T1
5C, va1 0.79 m3/kg(dry air). At 2 50% and T2 24C, va2 0.855 m3/kg(dry air) and 2 0.0094. The mass flow
# #
rates of the dry air are then ma1 180 kg(dry air)/min and ma2 497 kg(dry air)/min. Inserting values into the expression
for 3
10.0022 11802
10.00942 14972 kg1vapor2
v3 0.0074
180
497 kg1dry air2
(b) The temperature T3 of the exiting mixed stream can be found from an energy rate balance. Reduction of the energy rate
balance using assumptions 1 and 2 gives
ma1 1ha
vhv 2 1
ma2 1ha
vhv 2 2 ma3 1ha
vhv 2 3
# # #
(1)
Solving
ma1 1ha
vhv 2 1
ma2 1ha
vhv 2 2
# #
1ha
vhv 2 3 # # (2)
ma1
ma2
With (ha
hv)1 10 kJ/kg(dry air) and (ha
hv)2 47.8 kJ/kg(dry air) from Fig. A-9 and other known values
1801102
497147.82
1ha
vhv 2 3
kJ
37.7
180
497 kg1dry air2
This value for the enthalpy of the moist air at the exit, together with the previously determined value for 3, fixes the state of
the exiting moist air. From inspection of Fig. A-9, T3 19C.
Alternative Solutions:
The use of the psychrometric chart facilitates the solution for T3. Without the chart, an iterative solution of Eq. (2) using
table data could be used as noted in the solution to Example 12.12. Alternatively, T3 can be determined using the following
IT program, where 2 is denoted as phi2, the volumetric flow rates at 1 and 2 are denoted as AV1 and AV2, respectively,
and so on.
// Given data
T1 = 5 // C
w1 = 0.002 // kg(vapor) / kg(dry air)
AV1 = 142 // m3/min
T2 = 24 // C
phi2 = 0.5
AV2 = 425 // m3/min
p = 1 // bar
// Mass balances for water vapor and dry air:

w1 * mdota1 + w2 * mdota2 = w3 * mdota3
mdota1 + mdota2 = mdota3
// Evaluate mass flow rates of dry air
mdota1 = AV1 / va1
va1 = va_Tw(T1, w1, p)
mdota2 = AV2 / va2
va2 = va_Tphi(T2, phi2, p)
// Determine w2
w2 = w_Tphi(T2, phi2, p)
12.9 Cooling Towers 609
// The energy balance, Eq. (1), reads

mdota1 * h1 + mdota2 * h2 = mdota3 * h3
h1 = ha_Tw(T1, w1)
h2 = ha_Tphi(T2, phi2, p)
h3 = ha_Tw(T3, w3)
Using the Solve button, the result is T3 19.01C and 3 0.00745 kg (vapor)kg (dry air), which agree with the psychro-
metric chart solution.
Note the use here of special Moist Air functions listed in the Properties menu of IT.

12.9 Cooling Towers
Power plants invariably discharge considerable energy to their surroundings by heat transfer
(Chap. 8). Although water drawn from a nearby river or lake can be employed to carry away
this energy, cooling towers provide an alternative in locations where sufficient cooling water
cannot be obtained from natural sources or where concerns for the environment place a limit
on the temperature at which cooling water can be returned to the surroundings. Cooling tow-
ers also are frequently employed to provide chilled water for applications other than those
involving power plants.
Cooling towers can operate by natural or forced convection. Also they may be counterflow,
cross-flow, or a combination of these. A schematic diagram of a forced-convection, coun-
terflow cooling tower is shown in Fig. 12.15. The warm water to be cooled enters at 1 and
is sprayed from the top of the tower. The falling water usually passes through a series of baf-
fles intended to keep it broken up into fine drops to promote evaporation. Atmospheric air
drawn in at 3 by the fan flows upward, counter to the direction of the falling water droplets.
Discharged moist air

m a, T4, 4 > 3
Fan Warm water inlet

T1, m w
1
Atmospheric air
m a, T3, 3
2 Return water
Liquid m w
T2 < T1
5 Makeup Figure 12.15 Schematic of a

water cooling tower.
As the two streams interact, a small fraction of the water stream evaporates into the moist
air, which exits at 4 with a greater humidity ratio than the incoming moist air at 3. The en-
ergy required for evaporation is provided mainly by the portion of the incoming water stream
that does not evaporate, with the result that the water exiting at 2 is at a lower temperature
than the water entering at 1. Since some of the incoming water is evaporated into the moist
air stream, an equivalent amount of makeup water is added at 5 so that the return mass flow
rate of the cool water equals the mass flow rate of the warm water entering at 1.
For operation at steady state, mass balances for the dry air and water and an energy bal-
ance on the overall cooling tower provide information about cooling tower performance. In
applying the energy balance, heat transfer with the surroundings is usually neglected. The
power input to the fan of forced-convection towers also may be negligible relative to other
energy rates involved. The example to follow illustrates the analysis of a cooling tower us-
ing conservation of mass and energy together with property data for the dry air and water.
EXAMPLE 12.15 Power Plant Cooling Tower
Water exiting the condenser of a power plant at 38C enters a cooling tower with a mass flow rate of 4.5 107 kg/h. A stream
of cooled water is returned to the condenser from a cooling tower with a temperature of 30C and the same flow rate. Makeup
water is added in a separate stream at 20C. Atmospheric air enters the cooling tower at 25C and 35% relative humidity.
Moist air exits the tower at 35C and 90% relative humidity. Determine the mass flow rates of the dry air and the makeup
water, in kg/h. The cooling tower operates at steady state. Heat transfer with the surroundings and the fan power can each be
neglected, as can changes in kinetic and potential energy. The pressure remains constant throughout at 1 atm.
SOLUTION
Known: A liquid water stream enters a cooling tower from a condenser at 38C with a known mass flow rate. A stream of
cooled water is returned to the condenser at 30C and the same flow rate. Makeup water is added at 20C. Atmospheric air
enters the tower at 25C and 35%. Moist air exits the tower at 35C and 90%.
Find: Determine the mass flow rates of the dry air and the makeup water, in kg/h.
Moist air
T4 = 35C
4 4 = 90% Assumptions:
1 Liquid water, T1 = 38C
m 1 = 4.5 107 kg/h 1. The control volume shown in the accompanying figure op-
erates at steady state. Heat transfer with the surroundings can
be neglected,
# as can changes in kinetic and potential energy;
Atmospheric air
3
T3 = 25C, 3 = 35%
also Wcv 0.
2. To evaluate specific enthalpies, each liquid stream is
regarded as a saturated liquid at the corresponding specified
2 Liquid water, T2 = 30C temperature.
m 2 = 4.5 107 kg/h
3. The pressure is constant throughout at 1 atm.
5
Makeup water
T5 = 20C
Figure E12.15
Analysis: The required mass flow rates can be found from mass and energy rate balances. Mass balances for the dry air and
water individually reduce at steady state to
1dry air2
# #
ma3 ma4
1water2
# # # # #
m1
m5
mv3 m2
mv4
# # #
The common mass flow rate of the dry air is denoted as ma. Since m1 m2, the second of these equations becomes
# # #
m5 mv4 mv3
# # # #
With mv3 v3ma and mv4 v4ma
m5 ma 1v4 v3 2
# #
# #
Accordingly, the two required mass flow rates, ma and m5, are related by this equation. Another equation relating the flow rates
is provided by the energy rate balance.
Reducing the energy rate balance with assumption 1 results in
0 m1hw1
1maha3
mv3hv3 2
m5hw5 m2hw2 1maha4
mv4hv4 2
# # # # # # #
Evaluating the enthalpies of the water vapor as the saturated vapor values at the respective temperatures and the enthalpy of
each liquid stream as the saturated liquid enthalpy at the respective temperature, the energy rate equation becomes
0 m1hf1
1maha3
mv3hg3 2
m5hf5 m2hf2 1maha4
mv4hg4 2
# # # # # # #
Introducing m1 m2, m5 ma 1v4 v3 2, mv3 v3ma, and mv4 v4ma and solving for ma
# # # # # # # # #
m1 1hf1 hf 2 2
#
#
ma
ha4 ha3
v4hg4 v3hg3 1v4 v3 2 hf5
The humidity ratios 3 and 4 required by this expression can be determined from Eq. 12.43, using the partial pressure of
the water vapor obtained with the respective relative humidity. Thus, 3 0.00688 kg(vapor)kg(dry air) and 4 0.0327
kg(vapor)kg(dry air).
# #
With enthalpies from Tables A-2 and A-22, as appropriate, and the known values for 3, 4, and m1, the expression for ma
becomes
# 14.5 107 2 1159.21 125.792
ma
1308.2 298.22
10.03272 12565.32 10.006882 12547.22 10.02582 183.962
2.03 107 kg/h
#
Finally, inserting known values into the expression for m5 results in
m5 12.03 107 210.0327 0.006882 5.24 105 kg/h
#

#
This expression for ma can be rearranged to read
m1 1hf1 hf 2 2
#
#
ma
1ha4
v4hg4 2 1ha3
v3hg3 2 1v4 v3 2 hf5
The underlined terms and 3 and 4 can be obtained by inspection of the psychrometric chart.
In this chapter we have applied the principles of thermody- introduced for evaluating the enthalpy, internal energy, and
namics to systems involving ideal gas mixtures, including the entropy of a mixture by adding the contribution of each
special case of psychrometric applications involving airwater component at its condition in the mixture. Applications are
vapor mixtures, possibly in the presence of liquid water. Both considered where ideal gas mixtures undergo processes at
closed system and control volume applications are presented. constant composition as well as where ideal gas mixtures are
The first part of the chapter deals with general ideal gas formed from their component gases.
mixture considerations and begins by describing mixture In the second part of the chapter, we study psychrometrics.
composition in terms of the mass fractions or mole fractions. Special terms commonly used in psychrometrics are
Two models are then introduced for the pvT relation of ideal introduced, including moist air, humidity ratio, relative
gas mixtures: the Dalton model, which includes the partial humidity, mixture enthalpy, and the dew point, dry-bulb, and
pressure concept, and the Amagat model. Means are also wet-bulb temperatures. The psychrometric chart, which gives
a graphical representation of important moist air properties, relate pressure, volume, and temperature of ideal gas
is introduced. The principles of conservation of mass and en- mixtures using the Dalton model, and evaluate U, H, cv,
ergy are formulated in terms of psychrometric quantities, and cp, and S of ideal gas mixtures in terms of the mixture
typical air-conditioning applications are considered, includ- composition and the respective contribution of each
ing dehumidification and humidification, evaporative cooling, component.
and mixing of moist air streams. A discussion of cooling tow- apply the conservation of mass and energy principles and
ers is also provided. the second law of thermodynamics to systems involving
The following list provides a study guide for this chapter. ideal gas mixtures.
When your study of the text and end-of-chapter exercises has
been completed, you should be able to For psychrometric applications, you should be able to
write out the meanings of the terms listed in the margin evaluate the humidity ratio, relative humidity, mixture
throughout the chapter and understand each of the enthalpy, and dew point temperature.
related concepts. The subset of key concepts listed below use the psychrometric chart.
is particularly important. apply the conservation of mass and energy principles
describe mixture composition in terms of mass fractions and the second law of thermodynamics to analyze air-
or mole fractions. conditioning processes and cooling towers.
mass fraction p. 559 partial pressure p. 563 mixture enthalpy p. 582 wet-bulb temperature
mole fraction p. 559 psychrometrics p. 579 dew point temperature p. 590
apparent molecular moist air p. 579 p. 583 psychrometric chart
weight p. 559 humidity ratio p. 581 dry-bulb temperature p. 592
Dalton model p. 563 relative humidity p. 581 p. 590
1. In an equimolar mixture of O2 and N2, are the mass fractions 8. Which do you think is most closely related to human comfort,
equal? the humidity ratio or the relative humidity?
2. Is it possible to have a two-component mixture in which the 9. How do you explain the different rates of evaporation from a
mass and mole fractions are equal? dish of water in winter and summer?
3. How would you calculate the specific heat ratio, k, at 300 K 10. Why does your bathroom mirror often fog up when you
of a mixture of N2, O2, and CO2 if the molar analysis were known? shower?
4. How would you evaluate the entropy change of a component 11. Although water vapor in air is typically a superheated vapor,
in an ideal gas mixture undergoing a process between states where why can we use the saturated vapor value, hg(T ), to represent its
the temperature and pressure are T1, p1 and T2, p2, respectively? enthalpy?
5. If two samples of the same gas at the same temperature and 12. Can the dry-bulb and wet-bulb temperatures be equal?
pressure were mixed adiabatically, would entropy be produced?
13. How do you explain the water dripping from the tailpipe of
6. Which component of the fuelair mixture in a cylinder of an
an automobile on a cold morning?
automobile engine would have the greater mass fraction?
14. How does an automobiles windshield defroster achieve its
7. Is it# possible
# for a control volume operating at steady state
purpose?
with Wcv Qcv 0 to take in a binary ideal gas mixture at tem-
perature T and pressure p and separate the mixture into compo- 15. Would you recommend an evaporative cooling system for
nents, each at T and p? use in Florida? In Arizona?
Determining Mixture Composition Considering Constant-Composition Processes

12.1 Answer the following questions involving a mixture of two 12.8 A gas mixture consists of 2 kg of N2 and 3 kg of He
gases: Determine
(a) When would the analysis of the mixture in terms of mass (a) the composition in terms of mass fractions.
fractions be identical to the analysis in terms of mole (b) the composition in terms of mole fractions.
fractions? (c) the heat transfer, in kJ, required to increase the mixture
(b) When would the apparent molecular weight of the mix- temperature from 21 to 66C, while keeping the pressure
ture equal the average of the molecular weights of the constant.
two gases? (d) the change in entropy of the mixture for the process of part
(c), in kJ/K.
12.2 The molar analysis of a gas mixture at 30C, 2 bar is 40%
N2, 50% CO2, 10% CH4. Determine For parts (c) and (d), use the ideal gas model with constant
specific heats.
(a) the analysis in terms of mass fractions.
(b) the partial pressure of each component, in bar. 12.9 Two kg of a mixture having an analysis on a mass basis
(c) the volume occupied by 10 kg of mixture, in m3. of 30% N2, 40% CO2, 30% O2 is compressed adiabatically
from 1 bar, 300 K to 4 bar, 500 K. Determine
12.3 The molar analysis of a gas mixture at 25C, 0.1 MPa is
(a) the work, in kJ.
60% N2, 30% CO2, 10% O2. Determine
(b) the amount of entropy produced, in kJ/K.
(a) the analysis in terms of mass fractions.
12.10 A mixture having a molar analysis of 50% CO2, 33.3%
(b) the partial pressure of each component, in MPa.
CO, and 16.7% O2 enters a compressor operating at steady
(c) the volume occupied by 50 kg of the mixture, in m3.
state at 37C, 1 bar, 40 m/s with a mass flow rate of 1 kg/s
12.4 Natural gas at 23C, 1 bar enters a furnace with the and exits at 237C, 30 m/s. The rate of heat transfer from the
following molar analysis: 40% propane (C3H8), 40% ethane compressor to its surroundings is 5% of the power input.
(C2H6), 20% methane (CH4). Determine (a) Neglecting potential energy effects, determine the power
(a) the analysis in terms of mass fractions. input to the compressor, in kW.
(b) the partial pressure of each component, in bar. (b) If the compression is polytropic, evaluate the polytropic
(c) the mass flow rate, in kg/s, for a volumetric flow rate of exponent n and the exit pressure, in bar.
20 m3/s. 12.11 A mixture of 2 kg of H2 and 4 kg of N2 is compressed
12.5 A rigid vessel having a volume of 3 m3 initially contains in a pistoncylinder assembly in a polytropic process for which
a mixture at 21C, 1 bar consisting of 79% N2 and 21% O2 on n 1.2. The temperature increases from 22 to 150C. Using
a molar basis. Helium is allowed to flow into the vessel until constant values for the specific heats, determine
the pressure is 2 bar. If the final temperature of the mixture (a) the heat transfer, in kJ.
within the vessel is 27C, determine the mass, in kg, of each (b) the entropy change, in kJ/K.
component present.
12.12 A gas turbine receives a mixture having the following
12.6 A vessel having a volume of 0.3 m3 contains a mixture at molar analysis: 10% CO2, 19% H2O, 71% N2 at 720 K,
40C, 6.9 bar with a molar analysis of 75% O2, 25% CH4. De- 0.35 MPa and a volumetric flow rate of 3.2 m3/s. Products exit
termine the mass of methane that would have to be added and the turbine at 380 K, 0.11 MPa. For adiabatic operation with
the mass of oxygen that would have to be removed, each in negligible kinetic and potential energy effects, determine the
kg, to obtain a mixture having a molar analysis of 30% O2, power developed at steady state, in kW.
70% CH4 at the same temperature and pressure.
12.13 A gas mixture at 1500 K with the molar analysis 10%
12.7 A control volume operating at steady state has two en- CO2, 20% H2O, 70% N2 enters a waste-heat boiler operating
tering streams and a single exiting stream. A mixture with a at steady state, and exits the boiler at 600 K. A separate stream
mass flow rate of 11.67 kg/min and a molar analysis 9% CH4, of saturated liquid water enters at 25 bar and exits as saturated
91% air enters at one location and is diluted by a separate vapor with a negligible pressure drop. Ignoring stray heat trans-
stream of air entering at another location. The molar analysis fer and kinetic and potential energy changes, determine the
of the air is 21% O2, 79% N2. If the mole fraction of CH4 in mass flow rate of the exiting saturated vapor, in kg per kmol
the exiting stream is required to be 5%, determine of gas mixture.
(a) the molar flow rate of the entering air, in kmol/min. 12.14 A gas mixture having a molar analysis of 60% O2 and
(b) the mass flow rate of oxygen in the exiting stream, in 40% N2 enters an insulated compressor operating at steady
kg/min. state at 1 bar, 20C with a mass flow rate of 0.5 kg/s and is
compressed to 5.4 bar. Kinetic and potential energy effects are sel. The partition is removed and the gases mix to obtain
negligible. For an isentropic compressor efficiency of 78%, a final equilibrium state.
determine (b) Oxygen (O2) at 500 K and a molar flow rate of 0.6 kmol/s
(a) the temperature at the exit, in C. enters an insulated control volume operating at steady state
(b) the power required, in kW. and mixes with H2 entering as a separate stream at 300 K
(c) the rate of entropy production, in kW/K. and a molar flow rate of 0.4 kmol/s. A single mixed stream
exits. Kinetic and potential energy effects can be ignored.
12.15 A mixture having an analysis on a mass basis of 80% N2,
20% CO2 enters a nozzle operating at steady state at 1000 K 12.20 A system consists initially of nA moles of gas A at pres-
with a velocity of 5 m/s and expands adiabatically through a sure p and temperature T and nB moles of gas B separate from
7.5 :1 pressure ratio, exiting with a velocity of 900 m/s. De- gas A but at the same pressure and temperature. The gases are
termine the isentropic nozzle efficiency. allowed to mix with no heat or work interactions with the sur-
roundings. The final equilibrium pressure and temperature are
12.16 A mixture having a molar analysis of 60% N2 and 40% p and T, respectively, and the mixing occurs with no change
CO2 enters an insulated compressor operating at steady state in total volume.
at 1 bar, 30C with a mass flow rate of 1 kg/s and is compressed
to 3 bar, 147C. Neglecting kinetic and potential energy effects, (a) Assuming ideal gas behavior, obtain an expression for the
determine entropy produced in terms of R, nA, and nB.
(b) Using the result of part (a), demonstrate that the entropy
(a) the power required, in kW. produced has a positive value.
(b) the isentropic compressor efficiency. (c) Would entropy be produced when samples of the same gas
(c) the rate of exergy destruction, in kW, for T0 300 K. at the same temperature and pressure mix? Explain.
12.17 Natural gas having a molar analysis of 60% methane
12.21 An insulated tank has two compartments connected by a
(CH4) and 40% ethane (C2H6) enters a compressor at 340 K,
valve. Initially, one compartment contains 0.7 kg of CO2 at
6 bar and is compressed isothermally without internal irre-
500 K, 6.0 bar and the other contains 0.3 kg of N2 at 300 K,
versibilities to 20 bar. The compressor operates at steady state,
6.0 bar. The valve is opened and the gases are allowed to mix
and kinetic and potential energy effects are negligible.
until equilibrium is achieved. Determine
(a) Assuming ideal gas behavior, determine for the compres-
(a) the final temperature, in K.
sor the work and heat transfer, each in kJ per kmol of mix-
(b) the final pressure, in bar.
ture flowing.
(c) the amount of entropy produced, in kJ/K.
(b) Compare with the values for work and heat transfer, re-
spectively, determined assuming ideal solution behavior 12.22 A rigid insulated tank has two compartments. Initially
(Sec. 11.9.5). For the pure components at 340 K: one contains 0.5 kmol of carbon dioxide (CO2) at 27C, 2 bar
and the other contains 1 kmol of oxygen (O2) at 152C, 5 bar.
The gases are allowed to mix while 500 kJ of energy are added
h (kJ/kg) s (kJ/kg # K)
by electrical work. Determine
6 bar 20 bar 6 bar 20 bar (a) the final temperature, in C.
Methane 715.33 704.40 10.9763 10.3275 (b) the final pressure, in bar.
Ethane 462.39 439.13 7.3493 6.9680 (c) the change in exergy, in kJ, for T0 20C.
(d) the exergy destruction, in kJ.
12.23 Air at 40C, 1 atm and a volumetric flow rate of
Forming Mixtures 50 m3/min enters an insulated control volume operating at
12.18 One kilogram of argon at 27C, 1 bar is contained in a steady state and mixes with helium entering as a separate
rigid tank connected by a valve to another rigid tank contain- stream at 100C, 1 atm and a volumetric flow rate of 20 m3/min.
ing 0.8 kg of O2 at 127C, 5 bar. The valve is opened, and the A single mixed stream exits at 1 atm. Ignoring kinetic and po-
gases are allowed to mix, achieving an equilibrium state at tential energy effects, determine for the control volume
87C. Determine (a) the temperature of the exiting mixture, in C.
(a) the volume of each tank, in m3. (b) the rate of entropy production, in kW/K.
(b) the final pressure, in bar. 12.24 Air at 77C, 1 bar, and a molar flow rate of 0.1 kmol/s
(c) the heat transfer to or from the gases during the process, enters an insulated mixing chamber operating at steady state
in kJ. and mixes with water vapor entering at 277C, 1 bar, and a
(d) the entropy change of each gas, in kJ/K. molar flow rate of 0.3 kmol/s. The mixture exits at 1 bar.
12.19 Using the ideal gas model with constant specific heats, Kinetic and potential energy effects can be ignored. For the
determine the mixture temperature, in K, for each of two cases: chamber, determine
(a) Initially, 0.6 kmol of O2 at 500 K is separated by a parti- (a) the temperature of the exiting mixture, in C.
tion from 0.4 kmol of H2 at 300 K in a rigid insulated ves- (b) the rate of entropy production, in kW/K.
12.25 Helium at 400 K, 1 bar enters an insulated mixing cham- 12.33 Wet grain at 20C containing 40% moisture by mass en-
ber operating at steady state, where it mixes with argon enter- ters a dryer operating at steady state. Dry air enters the dryer
ing at 300 K, 1 bar. The mixture exits at a pressure of 1 bar. at 90C, 1 atm at a rate of 15 kg per kg of wet grain entering.
If the argon mass flow rate is x times that of helium, plot Moist air exits the dryer at 38C, 1 atm, and 52% relative hu-
versus x midity. For the grain exiting the dryer, determine the percent
(a) the exit temperature, in K. moisture by mass.
(b) the rate of exergy destruction within the chamber, in kJ 12.34 Figure P12.34 shows a spray dryer operating at steady
per kg of helium entering. state. The mixture of liquid water and suspended solid parti-
Kinetic and potential energy effects can be ignored. Let T0 cles entering through the spray head contains 30% solid matter
300 K. by mass. Dry air enters at 177C, 1 atm, and moist air exits
at 85C, 1 atm, and 21% relative humidity with a volumetric
12.26 An insulated, rigid tank initially contains 1 kmol of argon
flow rate of 310 m3/min. The dried particles exit separately.
(Ar) at 300 K, 1 bar. The tank is connected by a valve to a
Determine
large vessel containing nitrogen (N2) at 500 K, 4 bar. A quan-
tity of nitrogen flows into the tank, forming an argon-nitrogen (a) the volumetric flow rate of the entering dry air, in m3/min.
mixture at temperature T and pressure p. Plot T, in K, and p, (b) the rate that dried particles exit, in kg/min.
in bar, versus the amount of N2 within the tank, in kmol.
12.27 A stream of air (21% O2 and 79% N2 on a molar basis) Solid-liquid
at 300 K and 0.1 MPa is to be separated into pure oxygen and mixture
nitrogen streams, each at 300 K and 0.1 MPa. A device to 70% liquid
30% solid Moist air
achieve the separation is claimed to require a work input at
310 m3/min,
steady state of 1200 kJ per kmol of air. Heat transfer between 85C,
the device and its surroundings occurs at 300 K. Ignoring ki- 1 atm,
netic and potential energy effects, evaluate whether the work = 21%
value can be as claimed.
12.28 A device is being designed to separate into components Dry air,
Dried
a natural gas consisting of CH4 and C2H6 in which the mole 177C,
particles
fraction of C2H6, denoted by y, may vary from 0.05 to 0.50. 1 atm
The device will receive natural gas at 20C, 1 atm with a vol- Figure P12.34
umetric flow rate of 100 m3/s. Separate streams of CH4 and
C2H6 will exit, each at 20C, 1 atm. Heat transfer between the
device and its surroundings occurs at 20C. Ignoring kinetic 12.35 A system consisting initially of 0.5 m3 of air at 35C,
and potential energy effects, plot versus y the minimum theo- 1 bar, and 70% relative humidity is cooled at constant pres-
retical work input required at steady state, in kW. sure to 29C. Determine the work and heat transfer for the
process, each in kJ.
Exploring Psychrometric Principles 12.36 A closed, rigid tank having a volume of 3 m3 initially
12.29 A water pipe at 5C runs above ground between two contains air at 100C, 4.4 bar, and 40% relative humidity. De-
buildings. The surrounding air is at 35C. What is the maxi- termine the heat transfer, in kJ, if the tank contents are cooled
mum relative humidity the air can have before condensation to (a) 80C, (b) 20C.
occurs on the pipe? 12.37 A closed, rigid tank initially contains 0.5 m3 of moist air
12.30 On entering a dwelling maintained at 20C from the out- in equilibrium with 0.1 m3 of liquid water at 80C and 0.1 MPa.
doors where the temperature is 10C, a persons eye-glasses If the tank contents are heated to 200C, determine
are observed not to become fogged. A humidity gauge indi- (a) the final pressure, in MPa.
cates that the relative humidity in the dwelling is 55%. Can (b) the heat transfer, in kJ.
this reading be correct? Provide supporting calculations.
12.38 Combustion products with the molar analysis of 10%
12.31 A fixed amount of moist air initially at 1 bar and a relative CO2, 20% H2O, 70% N2 enter an engines exhaust pipe at
humidity of 60% is compressed isothermally until condensa- 1000F, 1 atm and are cooled as they pass through the pipe,
tion of water begins. Determine the pressure of the mixture at exiting at 100F, 1 atm. Determine the heat transfer at steady
the onset of condensation, in bar. Repeat if the initial relative state, in Btu per lb of entering mixture.
humidity is 90%.
12.39 Air at 35C, 3 bar, 30% relative humidity, and a velocity
12.32 A vessel whose volume is 0.5 m3 initially contains dry of 50 m /s expands isentropically through a nozzle. Determine
air at 0.2 MPa and 20C. Water is added to the vessel until the the lowest exit pressure, in bar, that can be attained without
air is saturated at 20C. Determine the condensation. For this exit pressure, determine the exit veloc-
(a) mass of water added, in kg. ity, in m/s. The nozzle operates at steady state and without sig-
(b) final pressure in the vessel, in bar. nificant potential energy effects.
12.40 A closed, rigid tank having a volume of 1 m3 contains a Considering Air-Conditioning Applications
mixture of carbon dioxide (CO2) and water vapor at 75C. The 12.47 Each case listed gives the dry-bulb temperature and
respective masses are 12.3 kg of carbon dioxide and 0.5 kg of relative humidity of the moist-air stream entering an air-
water vapor. If the tank contents are cooled to 20C, determine conditioning system: (a) 30C, 40%, (b) 17C, 60%, (c) 25C,
the heat transfer, in kJ, assuming ideal gas behavior. 70%, (d) 15C, 40%, (e) 27C, 30%. The condition of the
12.41 Moist air at 20C, 1.05 bar, 85% relative humidity and a moist-air stream exiting the system must satisfy these cons-
volumetric flow rate of 0.3 m3/s enters a well-insulated com- traints: 22 Tdb 27C, 40 60%. In each case, de-
pressor operating at steady state. If moist air exits at 100C, velop a schematic of equipment and processes from Sec. 12.9
2.0 bar, determine that would achieve the desired result. Sketch the processes on
a psychrometric chart.
(a) the relative humidity at the exit.
(b) the power input, in kW. 12.48 Moist air enters an air-conditioning system as shown in
(c) the rate of entropy production, in kW/K. Fig. 12.11 at 26C, 80% and a volumetric flow rate of
0.47 m3/s. At the exit of the heating section the moist air is at
12.42 Moist air at 20C, 1 atm, 43% relative humidity and a 26C, 50%. For operation at steady state, and neglecting
volumetric flow rate of 900 m3/h enters a control volume at kinetic and potential energy effects, determine
steady state and flows along a surface maintained at 65C,
(a) the rate energy is removed by heat transfer in the dehu-
through which heat transfer occurs. Liquid water at 20C is in-
midifier section, in tons.
jected at a rate of 5 kg/h and# evaporates into the flowing stream.
(b) the rate energy is added by heat transfer in the heating sec-
For the control volume, Wcv 0, and kinetic and potential
tion, in kW.
energy effects are negligible. Moist air exits at 32C, 1 atm.
Determine 12.49 Air at 35C, 1 atm, and 50% relative humidity enters a
dehumidifier operating at steady state. Saturated moist air and
(a) the rate of heat transfer, in kW. condensate exit in separate streams, each at 15C. Neglecting
(b) the rate of entropy production, in kW/K. kinetic and potential energy effects, determine
12.43 Using the psychrometric chart, Fig. A-9, determine (a) the heat transfer from the moist air, in kJ per kg of dry air.
(a) the relative humidity, the humidity ratio, and the specific (b) the amount of water condensed, in kg per kg of dry air.
enthalpy of the mixture, in kJ per kg of dry air, corre- (c) Check your answers using data from the psychrometric chart.
sponding to dry-bulb and wet-bulb temperatures of 30 and (d) Check your answers using Interactive Thermodynamics: IT.
25C, respectively. 12.50 An air conditioner operating at steady state takes in moist
(b) the humidity ratio, mixture specific enthalpy, and wet-bulb air at 28C, 1 bar, and 70% relative humidity. The moist air
temperature corresponding to a dry-bulb temperature of first passes over a cooling coil in the dehumidifier unit and
30C and 60% relative humidity. some water vapor is condensed. The rate of heat transfer be-
(c) the dew point temperature corresponding to dry-bulb and tween the moist air and the cooling coil is 11 tons. Saturated
wet-bulb temperatures of 30 and 20C, respectively. moist air and condensate streams exit the dehumidifier unit at
(d) Repeat parts (a)(c) using Interactive Thermodynamics: the same temperature. The moist air then passes through a heat-
IT. ing unit, exiting at 24C, 1 bar, and 40% relative humidity. Ne-
12.44 A fixed amount of air initially at 52C, 1 atm, and 10% glecting kinetic and potential energy effects, determine
relative humidity is cooled at constant pressure to 15C. Us- (a) the temperature of the moist air exiting the dehumidifer
ing the psychrometric chart, determine whether condensation unit, in C.
occurs. If so, evaluate the amount of water condensed, in kg (b) the volumetric flow rate of the air entering the air condi-
per kg of dry air. If there is no condensation, determine the tioner, in m3/min.
relative humidity at the final state. (c) the rate water is condensed, in kg/min.
(d) the rate of heat transfer to the air passing through the heat-
12.45 A fan within an insulated duct delivers moist air at the
ing unit, in kW.
duct exit at 22C, 60% relative humidity, and a volumetric flow
rate of 0.5 m3/s. At steady state, the power input to the fan is 12.51 An air-conditioning system consists of a spray section
1.3 kW. Using the psychrometric chart, determine the temper- followed by a reheater. Moist air at 32C and 77% enters
ature and relative humidity at the duct inlet. the system and passes through a water spray, leaving the spray
section cooled and saturated with water. The moist air is then
12.46 The mixture enthalpy per unit mass of dry air, in kJ/kg(a), heated to 25C and 45% with no change in the amount
represented on Fig. A-9 can be approximated closely from the of water vapor present. For operation at steady state, determine
expression
(a) the temperature of the moist air leaving the spray section,
in C.
1.005 T 1C2
v3 2501.7
1.82 T 1C2 4
H
ma (b) the change the amount of water vapor contained in the moist
air passing through the system, in kg per kg of dry air.
Noting all significant assumptions, develop the expression. Locate the principal states on a psychrometric chart.
12.52 At steady state, moist air is to be supplied to a classroom 12.57 Atmospheric air having dry-bulb and wet-bulb tempera-
at a specified volumetric flow rate and temperature T. Air is tures of 33 and 29C, respectively, enters a well-insulated
removed from the classroom in a separate stream at a temper- chamber operating at steady state and mixes with air entering
ature of 27C and 50% relative humidity. Moisture is added to with dry-bulb and wet-bulb temperatures of 16 and 12C,
the air in the room from the occupants at a rate of 4.5 kg/h. respectively. The volumetric flow rate of the lower tempera-
The moisture can be regarded as saturated vapor at 33C. Heat ture stream is three times that of the other stream. A single
transfer into the occupied space from all sources is estimated mixed stream exits. The pressure is constant throughout at
to occur at a rate of 34,000 kJ/h. The pressure remains uni- 1 atm. Neglecting kinetic and potential energy effects, deter-
form at 1 atm. mine for the exiting stream
(a) For a supply air volumetric flow rate of 40 m3/min, deter- (a) the relative humidity.
mine the supply air temperature T, in C, and the relative (b) the temperature, in C.
humidity. 12.58 Air at 30C, 1 bar, 50% relative humidity enters an in-
(b) Plot the supply air temperature, in C, and relative hu- sulated chamber operating at steady state with a mass flow rate
midity, each versus the supply air volumetric flow rate of 3 kg/min and mixes with a saturated moist air stream en-
ranging from 35 to 90 m3/min. tering at 5C, 1 bar with a mass flow rate of 5 kg/min. A sin-
12.53 Air at 35C, 1 bar, and 10% relative humidity enters gle mixed stream exits at 1 bar. Determine
an evaporative cooler operating at steady state. The volu- (a) the relative humidity and temperature, in C, of the exit-
metric flow rate of the incoming air is 50 m3/min. Liquid ing stream.
water at 20C enters the cooler and fully evaporates. Moist (b) the rate of exergy destruction, in kW, for T0 20C.
air exits the cooler at 25C, 1 bar. If there is no significant Neglect kinetic and potential energy effects.
heat transfer between the device and its surroundings,
determine
Analyzing Cooling Towers
(a) the rate at which liquid enters, in kg/min.
(b) the relative humidity at the exit. 12.59 In the condenser of a power plant, energy is discharged
(c) the rate of exergy destruction, in kJ/min, for T0 20C. by heat transfer at a rate of 836 MW to cooling water that ex-
its the condenser at 40C into a cooling tower. Cooled water
Neglect kinetic and potential energy effects.
at 20C is returned to the condenser. Atmospheric air enters
12.54 Using Eqs. 12.56b and 12.56c, show that the tower at 25C, 1 atm, 35% relative humidity. Moist air ex-
1ha3
v3hg3 2 1ha2
v2hg2 2
# its at 35C, 1 atm, 90% relative humidity. Makeup water is
ma1 v3 v2
# supplied at 20C. For operation at steady state, determine the
ma2 v1 v3 1ha1
v1hg1 2 1ha3
v3hg3 2 mass flow rate, in kg/s, of
Employ this relation to demonstrate on a psychrometric chart (a) the entering atmospheric air.
that state 3 of the mixture lies on a straight line connecting the (b) the makeup water.
initial states of the two streams before mixing. Ignore kinetic and potential energy effects.
12.55 For the adiabatic mixing process in Example 12.14, plot 12.60 Liquid water at 50C enters a forced draft cooling tower
the exit temperature, in C, versus the volumetric flow rate of operating at steady state. Cooled water exits the tower with a
stream 2 ranging from 0 to 1400 m3/min. Discuss the plot as mass flow rate of 80 kg/min. No makeup water is provided. A
(AV)2 goes to zero and as (AV)2 becomes large. fan located within the tower draws in atmospheric air at 17C,
12.56 A stream consisting of 35 m3/min of moist air at 14C, 0.098 MPa, 60% relative humidity with a volumetric flow rate
1 atm, 80% relative humidity mixes adiabatically with a of 110 m3/min. Saturated air exits the tower at 30C, 0.098
stream consisting of 80 m3/min of moist air at 40C, 1 atm, MPa. The power input to the fan is 8 kW. Ignoring kinetic and
40% relative humidity, giving a single mixed stream at 1 atm. potential energy effects, determine
Using the psychrometric chart together with the procedure of (a) the mass flow rate of the liquid stream entering, in kg/min.
Prob. 12.58, determine the relative humidity and temperature, (b) the temperature of the cooled liquid stream exiting, in C.
in C, of the exiting stream.
12.1D For comfort in indoor natatoriums, air and water tem- the pool surface. At 30C, an olympic-size pool can evaporate
peratures should be between 24 and 30C, and the relative hu- up to 90 kg/h. The airborne water vapor has energy that can
midity in the range 50 to 60%. A major contributor to dis- be extracted during dehumidification and used to heat the pool
comfort and inefficient energy use is water evaporating from water. Devise a practical means for accomplishing this energy-
saving measure. Also propose means for preventing conden- 12.4D Biosphere 2, located near Tucson, Arizona, is the worlds
sation on the natatorium windows for outdoor temperatures as largest enclosed ecosystem project. Drawing on what has been
low as 23C. For each case, provide an equipment schematic learned from the project, develop a plan for the air-condition-
and appropriate supporting calculations. ing systems required to maintain a healthy environment for a
12.2D Figure P12.2D shows a spray cooler included on the 12-person biosphere on Mars. Estimate the total power required
schematic of a plant layout. Arguing that it can only be the by the systems of your plan.
addition of makeup water at location 3 that is intended, an en- 12.5D Figure P12.5D shows a system for supplying a space
gineer orders the direction of the arrow at this location on the with 2100 m3/min of conditioned air at a dry-bulb tempera-
schematic to be reversed. Evaluate the engineers order and ture of 22C and a relative humidity of 60% when the outside
write a memorandum explaining your evaluation. air is at a dry-bulb temperature of 35C and a relative humid-
ity of 55%. Dampers A and B can be set to give three alter-
Water native operating modes: (1) Both dampers closed (no use of
circulation recirculated air). (2) Damper A open and damper B closed.
piping One-third of the conditioned air comes from outside air.
2
Spray (3) Both dampers open. One-third of the conditioned air comes
Exit moist air, head Water
chiller from outside air. One-third of the recirculated air bypasses the
T2 < T1
dehumidifier via open damper B, and the rest flows through
the damper A. Which of the three operating modes should be
1
used? Discuss.
Inlet moist air,

T1 3 Recirculated air 27C, = 49%
Figure P12.2D
Damper Cooling coil Damper
A B
12.3D Control of microbial contaminants is crucial in hospital Heating coil
operating rooms. Figure P12.3D illustrates the proposed design
of a hospital air-handling system aimed at effective infection
control. Write a critique of this design, taking into considera-
tion issues including, but not necessarily limited to the
Moist air:
following: Why is 100% outside air specified rather than a 2100 m3/min at
recirculated air-filtration arrangement requiring minimum out- Outside air 22C, = 60%
at 35C,
side air? Why is steam humidification used rather than the more
= 55%
common water-spray method? Why are three filters with
increasing efficiency specified, and why are they located as Air-conditioned
shown? What additional features might be incorporated to pro- space
mote air quality? Condensate
Intermediate To other zones

filter
Supply Figure P12.5D
fan
Humidifier-
steam 12.6D Savings can be realized on domestic water heating bills
injector by using a heat pump that exhausts to the hot water storage
Cooling tank of a conventional water heater. When the heat pump evap-
coil orator is located within the dwelling living space, cooling and
Preheat dehumidification of the room air also result. For a hot water
coil Terminal
(60C) requirement of 0.25 m3 per day, compare the annual
Prefilter reheat
unit cost of electricity for a heat-pump water heater with the an-
Terminal nual cost for a conventional electrical water heater. Provide a
filter
schematic showing how the heat-pump water heater might be
configured. Where might the heat pump evaporator be located
100% during periods of the year when cooling and dehumidifying
outside Operating are not required?
air room 12.7D A laboratory test facility requires 1.4 m3/s of condi-
Figure P12.3D tioned air at 38C and relative humidities ranging from 20
to 50%. As shown in Fig. P12.7D, the supply system takes Return Process
6 8
in ambient air at temperatures ranging from 21 to 32C and water steam
relative humidities ranging from 50 to 100%. As some de-
humidification is needed to achieve the temperature and hu- Heat-recovery
midity control required by the test facility, two strategies are 5 steam generator
under consideration: (1) Use a conventional refrigeration sys- 4
tem to cool the incoming air below its dew point tempera-
ture. (2) Use a rotary desiccant dehumidification unit. Injection
7
Develop schematics and design specifications, based on each steam
of these strategies, that would allow the supply system to pro- Net
Power
vide the required temperature and humidity control for this Compressor Combustor Turbine
application. 2 3
Ambient
air Supply Laboratory Exhaust 1
system test
21 Tamb 32C 1.4 m3/s, facility Air
Fuel
50 amb 100% 38C,
20 50% Figure P12.9D
Figure P12.7D
12.8D As a consulting engineer, you have been retained to 12.10D Most supermarkets use air-conditioning systems de-
recommend means for providing condenser cooling for a signed primarily to control temperature, and these typically
proposed 25% expansion of an electrical-generating plant in produce a relative humidity of about 55%. At this relative hu-
your locale. Consider the use of wet cooling towers, dry cool- midity a substantial amount of energy must be used to keep
ing towers, and cooling lakes. Also, consider relevant envi- frost and condensation from forming inside refrigerated dis-
ronmental issues, the effect on power plant thermodynamic play cases. Investigate technologies available for reducing the
performance, and costs. Write a report detailing your recom- overall humidity levels to 4045% and thereby reducing prob-
mendations. lems associated with frost and condensation. Estimate the po-
tential cost savings associated with such a strategy for a
12.9D Figure P12.9D shows a steam-injected gas-turbine
supermarket in your locale.
cogeneration system that produces power and process steam:
a simplified Cheng cycle. The steam is generated by a heat- 12.11D Is Stale Airplane Air Making Us Sick? (see box
recovery steam generator (HRSG) in which the hot gas exit- Sec. 12.4). Investigate typical equipment schematics providing
ing the turbine at state 4 is cooled and discharged at state 5. A a blend of fresh and recirculated filtered air to the passenger
separate stream of return water enters the HRSG at state 6 and cabin of a commercial airplane. Write a report including at
steam exits at states 7 and 8. The superheated steam exiting at least three references.
7 is injected into the combustor. In what ways does the steam- 12.12D How Cold Is Cold? (see box Sec. 12.6). Investigate
injected system shown in the figure differ from the humid air the development of the heat index used to alert us to possible
turbine (HAT) cycle? Draw the schematic of a HAT cycle. hot weather health dangers. Write a report including at least
Discuss appropriate applications of each cycle. three references.
C
H
A
P
T
Reacting
13 R
E
Mixtures and
Combustion
chapter objective E N G I N E E R I N G C O N T E X T The objective of this chapter is to
study systems involving chemical reactions. Since the combustion of hydrocarbon fuels
occurs in most power-producing devices (Chaps. 8 and 9), combustion is emphasized.
The thermodynamic analysis of reacting systems is primarily an extension of principles
introduced thus far. The concepts applied in the first part of the chapter dealing with com-
bustion fundamentals remain the same: conservation of mass, conservation of energy, and
the second law. It is necessary, though, to modify the methods used to evaluate specific
enthalpy, internal energy, and entropy, by accounting for changing chemical composition.
Only the manner in which these properties are evaluated represents a departure from
previous practice, for once appropriate values are determined they are used as in earlier
chapters in the energy and entropy balances for the system under consideration. In the
second part of the chapter, the exergy concept of Chap. 7 is extended by introducing
chemical exergy.
The principles developed in this chapter allow the equilibrium composition of a mixture
of chemical substances to be determined. This topic is studied in the next chapter. The
subject of dissociation is also deferred until then. Prediction of reaction rates is not within
the scope of classical thermodynamics, so the topic of chemical kinetics, which deals with
reaction rates, is not discussed in this text.
COMBUSTION FUNDAMENTALS
reactants

13.1 Introducing Combustion
When a chemical reaction occurs, the bonds within molecules of the reactants are broken,
and atoms and electrons rearrange to form products. In combustion reactions, rapid
products
oxidation of combustible elements of the fuel results in energy release as combustion prod-
ucts are formed. The three major combustible chemical elements in most common fuels
are carbon, hydrogen, and sulfur. Sulfur is usually a relatively unimportant contributor to
the energy released, but it can be a significant cause of pollution and corrosion problems.
complete combustion Combustion is complete when all the carbon present in the fuel is burned to carbon dioxide,
all the hydrogen is burned to water, all the sulfur is burned to sulfur dioxide, and all other
620
combustible elements are fully oxidized. When these conditions are not fulfilled, combus-
tion is incomplete.
In this chapter, we deal with combustion reactions expressed by chemical equations of
the form
reactants S products
or
fuel
oxidizer S products
When dealing with chemical reactions, it is necessary to remember that mass is conserved,
so the mass of the products equals the mass of the reactants. The total mass of each chemi-
cal element must be the same on both sides of the equation, even though the elements exist
in different chemical compounds in the reactants and products. However, the number of moles
of products may differ from the number of moles of reactants.
for example. . . consider the complete combustion of hydrogen with oxygen

1H2
12 O2 S 1H2O (13.1)
In this case, the reactants are hydrogen and oxygen. Hydrogen is the fuel and oxygen is
the oxidizer. Water is the only product of the reaction. The numerical coefficients in the
equation, which precede the chemical symbols to give equal amounts of each chemical
element on both sides of the equation, are called stoichiometric coefficients. In words, stoichiometric coefficients
Eq. 13.1 states
1 kmol H2
12 kmol O2 S 1 kmol H2O
Note that the total numbers of moles on the left and right sides of Eq. 13.1 are not equal.
However, because mass is conserved, the total mass of reactants must equal the total mass
of products. Since 1 kmol of H2 equals 2 kg, 12 kmol of O2 equals 16 kg, and 1 kmol of H2O
equals 18 kg, Eq. 13.1 can be interpreted as stating
2 kg H2
16 kg O2 S 18 kg H2O
In the remainder of this section, consideration is given to the makeup of the fuel, oxidizer,
and combustion products typically involved in engineering combustion applications.
FUELS
A fuel is simply a combustible substance. In this chapter emphasis is on hydrocarbon fuels,

which contain hydrogen and carbon. Sulfur and other chemical substances also may be pres-
ent. Hydrocarbon fuels can exist as liquids, gases, and solids.
Liquid hydrocarbon fuels are commonly derived from crude oil through distillation and
cracking processes. Examples are gasoline, diesel fuel, kerosene, and other types of fuel oils.
Most liquid fuels are mixtures of hydrocarbons for which compositions are usually given in
terms of mass fractions. For simplicity in combustion calculations, gasoline is often mod-
eled as octane, C8H18, and diesel fuel as dodecane, C12H26.
Gaseous hydrocarbon fuels are obtained from natural gas wells or are produced in certain
chemical processes. Natural gas normally consists of several different hydrocarbons, with the
major constituent being methane, CH4. The compositions of gaseous fuels are usually given
in terms of mole fractions. Both gaseous and liquid hydrocarbon fuels can be synthesized
from coal, oil shale, and tar sands.
Coal is a familiar solid fuel. Its composition varies considerably with the location from
which it is mined. For combustion calculations, the composition of coal is usually expressed
as an ultimate analysis. The ultimate analysis gives the composition on a mass basis in terms ultimate analysis
622 Chapter 13 Reacting Mixtures and Combustion
of the relative amounts of chemical elements (carbon, sulfur, hydrogen, nitrogen, oxygen)
and ash.
MODELING COMBUSTION AIR
Oxygen is required in every combustion reaction. Pure oxygen is used only in special
applications such as cutting and welding. In most combustion applications, air provides
the needed oxygen. The composition of a typical sample of dry air is given in Table 12.1.
For the combustion calculations of this book, however, the following model is used for
simplicity:
METHODOLOGY All components of air other than oxygen are lumped together with nitrogen. Accord-
UPDATE ingly, air is considered to be 21% oxygen and 79% nitrogen on a molar basis. With this
In this model, air is as- idealization the molar ratio of the nitrogen to the oxygen is 0.790.21 3.76. When
sumed to contain no water air supplies the oxygen in a combustion reaction, therefore, every mole of oxygen is
vapor. When moist air is accompanied by 3.76 moles of nitrogen.
involved in combustion,
the water vapor present We also assume that the nitrogen present in the combustion air does not undergo chemi-
must be considered in cal reaction. That is, nitrogen is regarded as inert. The nitrogen in the products is at the
writing the combustion same temperature as the other products, however, so the nitrogen undergoes a change of
equation. state if the products are at a temperature other than the air temperature before combus-
tion. If high enough temperatures are attained, nitrogen can form compounds such as
nitric oxide and nitrogen dioxide. Even trace amounts of oxides of nitrogen appearing
in the exhaust of internal combustion engines can be a source of air pollution.
AIRFUEL RATIO. Two parameters that are frequently used to quantify the amounts of fuel
and air in a particular combustion process are the airfuel ratio and its reciprocal, the fuelair
airfuel ratio ratio. The airfuel ratio is simply the ratio of the amount of air in a reaction to the amount
of fuel. The ratio can be written on a molar basis (moles of air divided by moles of fuel) or
on a mass basis (mass of air divided by mass of fuel). Conversion between these values is
accomplished using the molecular weights of the air, Mair, and fuel, Mfuel,
mass of air moles of air Mair

mass of fuel moles of fuel Mfuel
a b
moles of air Mair

moles of fuel Mfuel
or
AF AF a b
Mair
(13.2)
Mfuel
where AF is the airfuel ratio on a molar basis and AF is the ratio on a mass basis. For
the combustion calculations of this book the molecular weight of air is taken as 28.97.
Table A-1 provide the molecular weights of several important hydrocarbons.
THEORETICAL AIR. The minimum amount of air that supplies sufficient oxygen for the
complete combustion of all the carbon, hydrogen, and sulfur present in the fuel is called
theoretical air the theoretical amount of air. For complete combustion with the theoretical amount of air,
the products would consist of carbon dioxide, water, sulfur dioxide, the nitrogen accompa-
nying the oxygen in the air, and any nitrogen contained in the fuel. No free oxygen would
appear in the products.
for example. . . let us determine the theoretical amount of air for the complete
combustion of methane. For this reaction, the products contain only carbon dioxide, water,
and nitrogen. The reaction is
CH4
a1O2
3.76N2 2 S bCO2
cH2O
dN2 (13.3)
where a, b, c, and d represent the numbers of moles of oxygen, carbon dioxide, water, and
nitrogen. In writing the left side of Eq. 13.3, 3.76 moles of nitrogen are considered to ac-
company each mole of oxygen. Applying the conservation of mass principle to the carbon,
hydrogen, oxygen, and nitrogen, respectively, results in four equations among the four
unknowns
C: b1
H: 2c 4
O: 2b
c 2a
N: d 3.76a
Solving these equations, the balanced chemical equation is
CH4
21O2
3.76N2 2 S CO2
2H2O
7.52N2 (13.4)
The coefficient 2 before the term (O2

3.76N2) in Eq. 13.4 is the number of moles of
oxygen in the combustion air, per mole of fuel, and not the amount of air. The amount
of combustion air is 2 moles of oxygen plus 2 3.76 moles of nitrogen, giving a total of
9.52 moles of air per mole of fuel. Thus, for the reaction given by Eq. 13.4 the airfuel
ratio on a molar basis is 9.52. To calculate the airfuel ratio on a mass basis, use Eq. 13.2
to write
AF AF a b 9.52 a b 17.19
Mair 28.97
Mfuel 16.04
Normally the amount of air supplied is either greater or less than the theoretical amount.
The amount of air actually supplied is commonly expressed in terms of the percent of percent of theoretical air
theoretical air. For example, 150% of theoretical air means that the air actually supplied
is 1.5 times the theoretical amount of air. The amount of air supplied can be expressed al-
ternatively as a percent excess or a percent deficiency of air. Thus, 150% of theoretical air percent excess air
is equivalent to 50% excess air, and 80% of theoretical air is the same as a 20% deficiency
of air.
for example. . . consider the complete combustion of methane with 150% theo-
retical air (50% excess air). The balanced chemical reaction equation is
CH4
11.521221O2
3.76N2 2 S CO2
2H2O
O2
11.28N2 (13.5)
In this equation, the amount of air per mole of fuel is 1.5 times the theoretical amount
determined by Eq. 13.4. Accordingly, the airfuel ratio is 1.5 times the airfuel ratio
determined for Eq. 13.4. Since complete combustion is assumed, the products contain only
carbon dioxide, water, nitrogen, and oxygen. The excess air supplied appears in the products
as uncombined oxygen and a greater amount of nitrogen than in Eq. 13.4, based on the
theoretical amount of air.
The equivalence ratio is the ratio of the actual fuelair ratio to the fuelair ratio for com- equivalence ratio
plete combustion with the theoretical amount of air. The reactants are said to form a lean
mixture when the equivalence ratio is less than unity. When the ratio is greater than unity,
the reactants are said to form a rich mixture.
In Example 13.1, we use conservation of mass to obtain balanced chemical reactions. The
airfuel ratio for each of the reactions is also calculated.
EXAMPLE 13.1 Determining the AirFuel Ratio
Determine the airfuel ratio on both a molar and mass basis for the complete combustion of octane, C8H18, with (a) the the-
oretical amount of air, (b) 150% theoretical air (50% excess air).
SOLUTION
Known: Octane, C8H18, is burned completely with (a) the theoretical amount of air, (b) 150% theoretical air.
Find: Determine the airfuel ratio on a molar and a mass basis.
Assumptions:
1. Each mole of oxygen in the combustion air is accompanied by 3.76 moles of nitrogen.
2. The nitrogen is inert.
3. Combustion is complete.
Analysis:
(a) For complete combustion of C8H18 with the theoretical amount of air, the products contain carbon dioxide, water, and
nitrogen only. That is
C8H18
a1O2
3.76N2 2 S bCO2
cH2O
dN2
Applying the conservation of mass principle to the carbon, hydrogen, oxygen, and nitrogen, respectively, gives
C: b8
H: 2c 18
O: 2b
c 2a
N: d 3.76a
Solving these equations, a 12.5, b 8, c 9, d 47. The balanced chemical equation is
C8H18
12.51O2
3.76N2 2 S 8CO2
9H2O
47N2
The airfuel ratio on a molar basis is
12.5
12.513.762 12.514.762 kmol 1air2
AF 59.5
1 1 kmol 1fuel2
The airfuel ratio expressed on a mass basis is
kg 1air2
kmol 1air2 kmol 1air2 kg 1air2
28.97
AF c 59.5 d 15.1
kmol 1fuel2 kg 1fuel2 kg 1fuel2
kmol 1fuel2
114.22
(b) For 150% theoretical air, the chemical equation for complete combustion takes the form
C8H18
1.5112.521O2
3.76N2 2 S bCO2
cH2O
d N2
eO2
Applying conservation of mass
C: b8
H: 2c 18
O: 2b
c
2e 11.52112.52122
N: d 11.52112.5213.762
Solving this set of equations, b 8, c 9, d 70.5, e 6.25, giving a balanced chemical equation
C8H18
18.751O2
3.76N2 2 S 8CO2
9H2O
70.5N2
6.25O2
18.7514.762 kmol 1air2
AF 89.25
1 kmol 1fuel2
On a mass basis, the airfuel ratio is 22.6 kg (air)kg (fuel), as can be verified.
When complete combustion occurs with excess air, oxygen appears in the products, in addition to carbon dioxide, water,
and nitrogen.
DETERMINING PRODUCTS OF COMBUSTION
In each of the illustrations given above, complete combustion is assumed. For a hydro-
carbon fuel, this means that the only allowed products are CO2, H2O, and N2, with O2
also present when excess air is supplied. If the fuel is specified and combustion is complete,
the respective amounts of the products can be determined by applying the conservation
of mass principle to the chemical equation. The procedure for obtaining the balanced re-
action equation of an actual reaction where combustion is incomplete is not always so
straightforward.
Combustion is the result of a series of very complicated and rapid chemical reactions, and
the products formed depend on many factors. When fuel is burned in the cylinder of an in-
ternal combustion engine, the products of the reaction vary with the temperature and pres-
sure in the cylinder. In combustion equipment of all kinds, the degree of mixing of the fuel
and air is a controlling factor in the reactions that occur once the fuel and air mixture is
ignited. Although the amount of air supplied in an actual combustion process may exceed
the theoretical amount, it is not uncommon for some carbon monoxide and unburned oxygen
to appear in the products. This can be due to incomplete mixing, insufficient time for com-
plete combustion, and other factors. When the amount of air supplied is less than the theo-
retical amount of air, the products may include both CO2 and CO, and there also may be
unburned fuel in the products. Unlike the complete combustion cases considered above, the
products of combustion of an actual combustion process and their relative amounts can be
determined only by measurement.
Among several devices for measuring the composition of products of combustion are the
Orsat analyzer, gas chromatograph, infrared analyzer, and flame ionization detector. Data
from these devices can be used to determine the mole fractions of the gaseous products of
combustion. The analyses are often reported on a dry basis. In a dry product analysis, the dry product analysis
mole fractions are given for all gaseous products except the water vapor. In Examples 13.2
and 13.3, we show how analyses of the products of combustion on a dry basis can be used
to determine the balanced chemical reaction equations.
Since water is formed when hydrocarbon fuels are burned, the mole fraction of water va-
por in the gaseous products of combustion can be significant. If the gaseous products of com-
bustion are cooled at constant mixture pressure, the dew point temperature is reached when
water vapor begins to condense. Since water deposited on duct work, mufflers, and other
metal parts can cause corrosion, knowledge of the dew point temperature is important. De-
termination of the dew point temperature is illustrated in Example 13.2, which also features
a dry product analysis.

Airborne Soot Adds to Weather Woes, patterns indicate that
Some Say this leads to heavy
rainfall and flooding
According to a new study, the weather in northern Africa, India, in some areas, while
China, and the southern United States is being affected by soot dry conditions and
from cooking fires and diesel engines. Like global warming dust storms occur in
associated with carbon dioxide, researchers believe that soot other areas.
may contribute significantly to climate change. Soot is turning out to be more significant than previously
Widespread use of fuels such as coal, cow dung, crop thought, experts say. Based on the computer models, soot
residue, and wood in developing countries produces vast seems to have as much of an effect on climate as carbon
amounts of unburned black carbon, or soot. Diesel engine dioxide, although the atmospheric mechanisms are different.
exhaust also contains soot. The sooty carbon particles are Industrialized nations produce the most carbon dioxide,
thought to increase the absorption of sunlight in the upper whereas developing nations tend to emit more soot into the
atmosphere, causing hotter upper air and less sunlight to atmosphere. These new findings suggest that curbing both
reach the ground. With uneven warming, the air becomes un- sources of atmospheric emission might be needed to address
stable and more clouds form. Computer models of weather climate change concerns.
EXAMPLE 13.2 Using a Dry Product Analysis
Methane, CH4, is burned with dry air. The molar analysis of the products on a dry basis is CO2, 9.7%; CO, 0.5%; O2, 2.95%;
and N2, 86.85%. Determine (a) the airfuel ratio on both a molar and a mass basis, (b) the percent theoretical air, (c) the dew
point temperature of the products, in C, if the mixture were cooled at 1 atm.
SOLUTION
Known: Methane is burned with dry air. The molar analysis of the products on a dry basis is provided.
Find: Determine (a) the airfuel ratio on both a molar and a mass basis, (b) the percent theoretical air, and (c) the dew point
temperature of the products, in C, if cooled at 1 atm.
Assumptions:
1. Each mole of oxygen in the combustion air is accompanied by 3.76 moles of nitrogen, which is inert.
2. The products form an ideal gas mixture.
Analysis:
(a) The solution is conveniently conducted on the basis of 100 kmol of dry products. The chemical equation then reads
aCH4
b1O2
3.76N2 2 S 9.7CO2
0.5CO
2.95O2
86.85N2
cH2O
In addition to the assumed 100 lbmol of dry products, water must be included as a product.
Applying conservation of mass to carbon, hydrogen, and oxygen, respectively
C: 9.7
0.5 a
H: 2c 4a
O: 19.72122
0.5
212.952
c 2b
Solving this set of equations gives a 10.2, b 23.1, c 20.4. The balanced chemical equation is
10.2CH4
23.11O2
3.76N2 2 S 9.7CO2
0.5CO
2.95O2
86.85N2
20.4H2O
On a molar basis, the airfuel ratio is
23.114.762 kmol 1air2

AF 10.78
10.2 kmol 1fuel2
On a mass basis
kg 1air2
AF 110.782 a b 19.47
28.97
16.04 kg 1fuel2
(b) The balanced chemical equation for the complete combustion of methane with the theoretical amount of air is
CH4
21O2
3.76N2 2 S CO2
2H2O
7.52N2
The theoretical airfuel ratio on a molar basis is
kmol 1air2
1AF2 theo
214.762
9.52
1 kmol 1fuel2
The percent theoretical air is then found from
1AF2
% theoretical air
1AF2 theo
10.78 kmol 1air2 kmol 1fuel2

1.13 1113% 2
(c) To determine the dew point temperature requires the partial pressure of the water vapor pv. The partial pressure pv is found
from pv yvp, where yv is the mole fraction of the water vapor in the combustion products and p is 1 atm.
Referring to the balanced chemical equation of part (a), the mole fraction of the water vapor is
20.4
yv 0.169
100
20.4
Thus, pv 0.169 atm 0.1712 bar. Interpolating in Table A-2, T 57C.
The solution could be obtained on the basis of any assumed amount of dry productsfor example, 1 lbmol. With some
other assumed amount, the values of the coefficients of the balanced chemical equation would differ from those obtained
in the solution, but the airfuel ratio, the value for the percent of theoretical air, and the dew point temperature would be
unchanged.
The three unknown coefficients, a, b, and c, are evaluated here by application of conservation of mass to carbon, hydro-
gen, and oxygen. As a check, note that the nitrogen also balances
N: b13.762 86.85
This confirms the accuracy of both the given product analysis and the calculations conducted to determine the unknown
coefficients.
If the products of combustion were cooled at constant pressure below the dew point temperature of 134F, some conden-
sation of the water vapor would occur.
In Example 13.3, a fuel mixture having a known molar analysis is burned with air, giv-
ing products with a known dry analysis.
EXAMPLE 13.3 Burning Natural Gas with Excess Air
A natural gas has the following molar analysis: CH4, 80.62%; C2H6, 5.41%; C3H8, 1.87%; C4H10, 1.60%; N2, 10.50%. The gas is
burned with dry air, giving products having a molar analysis on a dry basis: CO2, 7.8%; CO, 0.2%; O2, 7%; N2, 85%. (a) Deter-
mine the airfuel ratio on a molar basis. (b) Assuming ideal gas behavior for the fuel mixture, determine the amount of products
in kmol that would be formed from 100 m3 of fuel mixture at 300 K and 1 bar. (c) Determine the percent of theoretical air.
SOLUTION
Known: A natural gas with a specified molar analysis burns with dry air giving products having a known molar analysis on
a dry basis.
Find: Determine the airfuel ratio on a molar basis, the amount of products in kmol that would be formed from 100 m3 of
natural gas at 300 K and 1 bar, and the percent of theoretical air.
Assumptions:
2. The fuel mixture can be modeled as an ideal gas.
Analysis:
(a) The solution can be conducted on the basis of an assumed amount of fuel mixture or on the basis of an assumed amount
of dry products. Let us illustrate the first procedure, basing the solution on 1 kmol of fuel mixture. The chemical equation
then takes the form
10.8062CH4
0.0541C2H6
0.0187C3H8
0.0160C4H10
0.1050N2 2

a1O2
3.76N2 2 S b10.078CO2
0.002CO
0.07O2
0.85N2 2
cH2O
The products consist of b kmol of dry products and c kmol of water vapor, each per kmol of fuel mixture.
Applying conservation of mass to carbon
b10.078
0.0022 0.8062
210.05412
310.01872
410.01602
Solving gives b 12.931. Conservation of mass for hydrogen results in
2c 410.80622
610.05412
810.01872
1010.01602
which gives c 1.93. The unknown coefficient a can be found from either an oxygen balance or a nitrogen balance. Apply-
ing conservation of mass to oxygen
12.931 3210.0782
0.002
210.072 4
1.93 2a
giving a 2.892.
The balanced chemical equation is then
10.8062CH4
0.0541C2H6
0.0187C3H8
0.0160C4H10
0.1050N2 2

2.8921O2
3.76N2 2 S 12.93110.078CO2
0.002CO
0.07O2
0.85N2 2

1.93H2O
12.892214.762 kmol 1air2
AF 13.77
1 kmol 1fuel2
(b) By inspection of the chemical reaction equation, the total amount of products is b
c 12.931
1.93 14.861 kmol
of products per kmol of fuel. The amount of fuel in kmol, nF, present in 100 m3 of fuel mixture at 300 K and 1 bar can be
determined from the ideal gas equation of state as
pV
nF
RT
1105 N/m2 21100 m3 2
4.01 kmol 1fuel2
18314 N # m/ kmol # K21300 K2
13.2 Conservation of EnergyReacting Systems 629
Accordingly, the amount of product mixture that would be formed from 100 m3 of fuel mixture is (14.861)(4.01) 59.59
kmol of product gas.
(c) The balanced chemical equation for the complete combustion of the fuel mixture with the theoretical amount of air is
10.8062CH4
0.0541C2H6
0.0187C3H8
0.0160C4H10
0.1050N2 2

21O2
3.76N2 2 S 1.0345CO2
1.93H2O
7.625N2
The theoretical airfuel ratio on a molar basis is
kmol 1air2
1AF2 theo
214.762
9.52
1 kmol 1fuel2
The percent theoretical air is then
% theoretical air 1.45 1145% 2
A check on both the accuracy of the given molar analyses and the calculations conducted to determine the unknown co-
efficients is obtained by applying conservation of mass to nitrogen. The amount of nitrogen in the reactants is
0.105
13.76212.8922 10.98 kmolkmol of fuel
The amount of nitrogen in the products is (0.85)(12.931) 10.99 kmolkmol of fuel. The difference can be attributed to
round-off.

13.2 Conservation of Energy
Reacting Systems
The objective of the present section is to illustrate the application of the conservation of en-
ergy principle to reacting systems. The forms of the conservation of energy principle intro-
duced previously remain valid whether or not a chemical reaction occurs within the system.
However, the methods used for evaluating the properties of reacting systems differ somewhat
from the practices used to this point.
13.2.1 Evaluating Enthalpy for Reacting Systems

In each of the tables of thermodynamic properties used thus far, values for the specific in-
ternal energy, enthalpy, and entropy are given relative to some arbitrary datum state where
the enthalpy (or alternatively the internal energy) and entropy are set to zero. This approach
is satisfactory for evaluations involving differences in property values between states of the
same composition, for then arbitrary datums cancel. However, when a chemical reaction oc-
curs, reactants disappear and products are formed, so differences cannot be calculated for all
substances involved. For reacting systems, it is necessary to evaluate h, u, and s in such a
way that there are no subsequent ambiguities or inconsistencies in evaluating properties. In
this section, we will consider how this is accomplished for h and u. The case of entropy is
handled differently and is taken up in Sec. 13.5.
An enthalpy datum for the study of reacting systems can be established by assigning
arbitrarily a value of zero to the enthalpy of the stable elements at a state called the
standard reference state and defined by Tref 298.15 K (25C) and pref 1 atm. Note standard reference state
that only stable elements are assigned a value of zero enthalpy at the standard state. The
term stable simply means that the particular element is in a chemically stable form. For
example, at the standard state the stable forms of hydrogen, oxygen, and nitrogen are H2,
O2, and N2 and not the monatomic H, O, and N. No ambiguities or conflicts result with
this choice of datum.
ENTHALPY OF FORMATION. Using the datum introduced above, enthalpy values can be
assigned to compounds for use in the study of reacting systems. The enthalpy of a compound
enthalpy of formation at the standard state equals its enthalpy of formation, symbolized hf. The enthalpy of
formation is the energy released or absorbed when the compound is formed from its elements,
the compound and elements all being at Tref and pref. The enthalpy of formation is usually
determined by application of procedures from statistical thermodynamics using observed
spectroscopic data.
The enthalpy of formation also can be found in principle by measuring the heat transfer
C in a reaction in which the compound is formed from the elements. for example . . .
Tref, pref CO2
Tref, pref
consider the simple reactor shown in Fig. 13.1, in which carbon and oxygen each enter at
O2 Tref and pref and react completely at steady state to form carbon dioxide at the same temperature
Tref, pref
and pressure. Carbon dioxide is formed from carbon and oxygen according to
Figure 13.1 Reactor
C
O2 S CO2 (13.6)
used to discuss the
enthalpy of formation This reaction would be exothermic, so for the carbon dioxide to exit at the same tempera-
concept. ture as the entering elements, there would be a heat transfer from the reactor to its sur-
roundings. The rate of heat transfer and the enthalpies of the incoming and exiting streams
are related by the energy rate balance
# # # #
0 Qcv
mC hC
mO2hO2 m CO2hCO2
#
where m and h denote, respectively, mass # flow rate and specific enthalpy. In writing this
equation, we have assumed no work Wcv and negligible effects of kinetic and potential en-
ergy. For enthalpies on a molar basis, the energy rate balance appears as
# # # #
0 Qcv
n ChC
n O2hO2 n CO2h CO2
#
where n and h denote, respectively, the molar flow rate and enthalpy per mole. Solving for
the specific enthalpy of carbon dioxide and noting from Eq. 13.6 that all molar flow rates
are equal
# # # #
Qcv nC n O2 Qcv
hCO2 #
# h
# h #
hC
hO2 (13.7)
n CO2 n CO2 C n CO2 O2 n CO2
Since carbon and oxygen are stable elements at the standard state, hC hO2 0, and Eq. 13.7
becomes
#
Qcv
h CO2 # (13.8)
n CO2
Accordingly, the value assigned to the specific enthalpy of carbon dioxide at the standard
state, the enthalpy of formation, equals the heat transfer, per mole of CO2, between the re-
actor and its surroundings. If the heat transfer could be measured accurately, it would be
found to equal 393,520 kJ per kmol of carbon dioxide formed.
Table A-25 give values of the enthalpy of formation for several compounds in units of
kJ/kmol. In this text, the superscript is used to denote properties at 1 atm. For the case
of the enthalpy of formation, the reference temperature Tref is also intended by this symbol.
The values of hf listed in Table A-25 for CO2 correspond to those given in the previous
example.
The sign associated with the enthalpy of formation values appearing in Tables A-25 cor-
responds to the sign convention for heat transfer. If there is heat transfer from a reactor in
which a compound is formed from its elements (an exothermic reaction as in the previous
example), the enthalpy of formation has a negative sign. If a heat transfer to the reactor is
required (an endothermic reaction), the enthalpy of formation is positive.
EVALUATING ENTHALPY. The specific enthalpy of a compound at a state other than the
standard state is found by adding the specific enthalpy change h between the standard state
and the state of interest to the enthalpy of formation
h1T, p2 hf
3h1T, p2 h1Tref , pref 2 4 hf
h (13.9)
That is, the enthalpy of a compound is composed of hf, associated with the formation of the
compound from its elements, and h, associated with a change of state at constant compo-
sition. An arbitrary choice of datum can be used to determine h, since it is a difference at
constant composition. Accordingly, h can be evaluated from tabular sources such as the
steam tables, the ideal gas tables when appropriate, and so on. Note that as a consequence
of the enthalpy datum adopted for the stable elements, the specific enthalpy determined from
Eq. 13.9 is often negative.
Tables A-25 provide two values of the enthalpy of formation of water. One is for liq-
uid water and the other is for water vapor. Under equilibrium conditions, water exists only METHODOLOGY
as a liquid at 25C and 1 atm. The vapor value listed is for a hypothetical ideal gas state UPDATE
in which water is a vapor at 25C and 1 atm. The difference between the two enthalpy of When applying Eq. 13.9 to
formation values is given closely by the enthalpy of vaporization hfg at Tref water vapor, we use the
vapor value of the en-
hf 1g2 hf 1l2 hfg (13.10) thalpy of formation of wa-
ter, hf 1g2, from Table A-25

together with h for water
Similar considerations apply to other substances for which liquid and vapor values for hof are vapor from the ideal gas
listed in Tables A-25. table, Table A-23.
13.2.2 Energy Balances for Reacting Systems

Several considerations enter when writing energy balances for systems involving combus-
tion. Some of these apply generally, without regard for whether combustion takes place. For
example, it is necessary to consider if significant work and heat transfers take place and if
the respective values are known or unknown. Also, the effects of kinetic and potential en-
ergy must be assessed. Other considerations are related directly to the occurrence of com-
bustion. For example, it is important to know the state of the fuel before combustion occurs.
Whether the fuel is a liquid, a gas, or a solid is important. It is necessary to consider whether
the fuel is premixed with the combustion air or the fuel and air enter a reactor separately. The
state of the combustion products also must be assessed. It is important to know whether the
products of combustion are a gaseous mixture or whether some of the water formed on
combustion has condensed.
CONTROL VOLUMES AT STEADY STATE
To illustrate the many considerations involved when writing energy balances for reacting
systems, we consider special cases of broad interest, highlighting the underlying as-
sumptions. Let us begin by considering the steady-state reactor shown in Fig. 13.2, in
CaHb at
TF

Wcv

Qcv
Air at Combustion products

TA at TP
Figure 13.2 Reactor at

steady state.
which a hydrocarbon fuel CaHb burns completely with the theoretical amount of air
according to
CaHb
aa
b 1O2
3.76N2 2 S aCO2
H2O
aa
b 3.76N2
b b b
(13.11)
4 2 4
The fuel enters the reactor in a stream separate from the combustion air, which is regarded
as an ideal gas mixture. The products of combustion also are assumed to form an ideal gas
mixture. Kinetic and potential energy effects are ignored.
With the foregoing idealizations, the mass and energy rate balances for the two-inlet,
single-exit reactor can be used to obtain the following equation on a per mole of fuel
basis:
# #
# # c ahCO2
hH2O
aa
b 3.76hN2 d
Qcv Wcv b b
nF nF 2 4
hF c aa
b hO2
aa
b 3.76hN2 d
b b
(13.12a)
4 4
#
where nF denotes the molar flow rate of the fuel. Note that each coefficient on the right side
of this equation is the same as the coefficient of the corresponding substance in the reaction
equation.
The first underlined term on the right side of Eq. 13.12a is the enthalpy of the exiting
gaseous products of combustion per mole of fuel. The second underlined term on the right
side is the enthalpy of the combustion air per mole of fuel. Note that the enthalpies of the
combustion products and the air have been evaluated by adding the contribution of each com-
ponent present in the respective ideal gas mixtures. The symbol hF denotes the molar en-
thalpy of the fuel. Equation 13.12a can be expressed more concisely as
# #
Qcv Wcv
# # hP hR (13.12b)
nF nF
where hP and hR denote, respectively, the enthalpies of the products and reactants per mole
of fuel.
EVALUATING ENTHALPY TERMS. Once the energy balance has been written, the next step
is to evaluate the individual enthalpy terms. Since each component of the combustion prod-
ucts is assumed to behave as an ideal gas, its contribution to the enthalpy of the products de-
pends solely on the temperature of the products, TP. Accordingly, for each component of the
products, Eq. 13.9 takes the form
h hf
3h1TP 2 h1Tref 2 4 (13.13)
In Eq. 13.13, hf is the enthalpy of formation from Table A-25. The second term accounts
for the change in enthalpy from the temperature Tref to the temperature TP. For several com-
mon gases, this term can be evaluated from tabulated values of enthalpy versus temperature
in Tables A-23. Alternatively, the term can be obtained by integration of the ideal gas spe-
cific heat cp obtained from Tables A-21 or some other source of data. A similar approach
would be employed to evaluate the enthalpies of the oxygen and nitrogen in the combus-
tion air. For these
0
h hf
3h1TA 2 h1Tref 2 4 (13.14)
where TA is the temperature of the air entering the reactor. Note that the enthalpy of forma-
tion for oxygen and nitrogen is zero by definition and thus drops out of Eq. 13.14 as indi-
cated. The evaluation of the enthalpy of the fuel is also based on Eq. 13.9. If the fuel can be
modeled as an ideal gas, the fuel enthalpy is obtained using an expression of the same form
as Eq. 13.13 with the temperature of the incoming fuel replacing TP.
With the foregoing considerations, Eq. 13.12a takes the form
# # 0
# # a1hf
h2 CO2
1hf
h2 H2O
aa
b 3.761hf
h2 N2
Qcv Wcv b b
nF nF 2 4
0 0
1hf
h2 F aa
b 1hf
h2 O2 aa
b 3.761hf
h2 N2
b b
(13.15a)
4 4
The terms set to zero in this expression are the enthalpies of formation of oxygen and
nitrogen.
Equation 13.15a can be written more concisely as
# #
# # a ne 1hf
h2 e a ni 1hf
h2 i
Qcv Wcv
(13.15b)
nF nF P R
where i denotes the incoming fuel and air streams and e the exiting combustion products.
The coefficients ni and ne correspond to the respective coefficients of the reaction equation
giving the moles of reactants and products per mole of fuel, respectively. Although Eqs. 13.15
have been developed with reference to the reaction of Eq. 13.11, equations having the same
general forms would be obtained for other combustion reactions.
In Examples 13.4 and 13.5, the energy balance is applied together with tabular property
data to analyze control volumes at steady state involving combustion.
EXAMPLE 13.4 Analyzing an Internal Combustion Engine
Liquid octane enters an internal combustion engine operating at steady state with a mass flow rate of 1.8 103 kg/s and is
mixed with the theoretical amount of air. The fuel and air enter the engine at 25C and 1 atm. The mixture burns completely
and combustion products leave the engine at 890 K. The engine develops a power output of 37 kW. Determine the rate of heat
transfer from the engine, in kW, neglecting kinetic and potential energy effects.
SOLUTION
Known: Liquid octane and the theoretical amount of air enter an internal combustion engine operating at steady state in sep-
arate streams at 25C, 1 atm. Combustion is complete and the products exit at 890 K. The power developed by the engine and
fuel mass flow rate are specified.
Find: Determine the rate of heat transfer from the engine, in kW.
Drive
Air at 77F, 1 atm shaft 50 hp
Assumptions:
Combustion products 1. The control volume identified by a dashed line on
at 1140F the accompanying figure operates at steady state.
Fuel at 77F, 1 atm 2. Kinetic and potential energy effects can be ignored.
3. The combustion air and the products of combus-
tion each form ideal gas mixtures.
4. Each mole of oxygen in the combustion air is ac-
companied by 3.76 moles of nitrogen. The nitrogen is
inert and combustion is complete.
Figure E13.4
Analysis: The balanced chemical equation for complete combustion with the theoretical amount of air is obtained from the
solution to Example 13.1 as
C8H18
12.5O2
47N2 S 8CO2
9H2O
47N2
The energy rate balance reduces, with assumptions 13, to give
# #
Qcv Wcv
# #
hP hR
nF nF
# 0
#
583 hf
h4 CO2
93 hf
h4 H2O1g2
473 hf
h4 N2 6
Wcv
nF
0 0 0 0 0
5 3 hf
h4 C8H181l2
12.53 hf
h4 O 2
473 hf
h4 N2 6
where each coefficient is the same as the corresponding term of the balanced chemical equation and Eq. 13.9 has been used
to evaluate enthalpy terms. The enthalpy of formation terms for oxygen and nitrogen are zero, and h 0 for each of the
reactants, because the fuel and combustion air enter at 25C.
With the enthalpy of formation for C8H18(l) from Table A-25
hR 1hf 2 C8H181l2 249,910 kJ/kmol 1fuel2
With enthalpy of formation values for CO2 and H2O(g) from Table A-25, and enthalpy values for N2, H2O, and CO2 from
Table A-23
hP 8 3393,520
136,876 93642 4
9 3241,820
131,429 9,9042 4

47 326,568 8,669 4
4,069,466 kJ/kmol
Using the molecular weight of the fuel from Table A-1, the molar flow rate of the fuel is
# 1.8 10 3 kg 1fuel2/s
nF 1.58 105 kmol1fuel2/s
114.22 lb1fuel2 kmol1fuel2
Inserting values into the expression for the rate of heat transfer
Qcv Wcv
nF 1hP hR 2
# # #
kmol 1fuel2
37 kW
c 1.58 10 5 d 3 4,069,466 1249,9102 4 a ba b
kJ 1 kW
s kmol 1fuel2 1 kJ/s
23.3 kW
EXAMPLE 13.5 Analyzing a Combustion Chamber
Methane gas at 400 K and 1 atm enters a combustion chamber, where it is mixed with air entering at 500 K and 1 atm. The
products of combustion exit at 1800 K and 1 atm with the product analysis given in Example 13.2. For operation at steady
state, determine the rate of heat transfer from the combustion chamber in kJ per kmol of fuel. Neglect kinetic and potential
energy effects. The average value for the specific heat cp of methane between 298 and 400 K is 38 kJ/kmol # K.
SOLUTION
Known: Methane gas, air, and combustion products enter and exit a combustion chamber at steady state in separate streams
with specified temperatures and a pressure of 1 atm. An analysis of the dry products of combustion is provided.
Find: Determine the rate of heat transfer, in kJ per kmol of fuel.
CH4(g)
400 K, 1 atm
Air at Combustion products

500 K, 1 atm 1800 K, 1 atm
Figure E13.5
Assumptions:
#
1. The control volume identified by a dashed line on the accompanying figure operates at steady state with Wcv 0.
3. The fuel is modeled as an ideal gas with cp 38 kJ/kmol # K. The combustion air and the products of combustion each
form ideal gas mixtures.
Analysis: When expressed on a per mole of fuel basis, the balanced chemical equation obtained in the solution to Example 13.2
takes the form
CH4
2.265O2
8.515N2 S 0.951CO2
0.049CO
0.289O2
8.515N2
2H2O
The energy rate balance reduces with assumptions 13 to give
#
Qcv
# hP hR
nF
0
30.9511hf
h2 CO2
0.0491hf
h2 CO
0.2891hf
h2 O2
0

8.5151hf
h2 N2
21hf
h2 H2O1g2 4 3 1hf
h2 CH4
0 0

2.2651hf
h2 O2
8.5151hf
h2 N2 4
where each coefficient in the equation is the same as the coefficient of the corresponding term of the balanced chemical equa-
tion and Eq. 13.9 has been used to evaluate the enthalpy terms. The enthalpies of formation for oxygen and nitrogen are set
to zero.
Consider first the reactants. With the enthalpy of formation for methane from Table A-25, the given cp value for methane,
and enthalpy values for nitrogen and oxygen from Table A-23
hR 1hf
cp T 2 CH4
2.2651 h2 O2
8.5151h2 N2
3 74,850
381400 2982 4
2.2653 14,770 86824
8.515314,581 86694
6844 kJ/kmol 1CH4 2
Next consider the products. With enthalpy of formation values for CO2, CO, and H2O(g) from Table A-25 and enthalpy
values from Table A-23
hP 0.951 3393,520
188,806 93642 4

0.0493110,530
158,191 86692 4

0.289160,371 86822
8.515157,651 86692

2 3 241,820
172,513 99042 4
228,079 kJ/kmol 1CH4 2
Inserting values into the expression for the rate of heat transfer
#
# hP hR 228,079 168442 221,235 kJ/kmol 1CH4 2
Qcv
nF
CONDENSATION OF COMBUSTION PRODUCTS. When the combustion products of a hy-

drocarbon fuel are cooled sufficiently, condensation of a portion of the water formed will
occur. The energy balance must then be written to account for the presence of water in the
products as both a liquid and a vapor. For cooling of combustion products at constant pressure,
the dew point temperature method of Example 13.2 is used to determine the temperature at
the onset of condensation.
CLOSED SYSTEMS
Let us consider next a closed system involving a combustion process. In the absence of ki-
netic and potential energy effects, the appropriate form of the energy balance is
UP UR Q W
where UR denotes the internal energy of the reactants and UP denotes the internal energy of
the products. If the reactants and products form ideal gas mixtures, the energy balance can
be expressed as
a nu a nu Q W (13.16)
P R
where the coefficients n on the left side are the coefficients of the reaction equation giving
the moles of each reactant or product.
Since each component of the reactants and products behaves as an ideal gas, the respec-
tive specific internal energies of Eq. 13.16 can be evaluated as u h RT, so the equation
becomes
Q W a n1h RTP 2 a n1h RTR 2 (13.17a)

P R
where TP and TR denote the temperature of the products and reactants, respectively. With ex-
pressions of the form of Eq. 13.13 for each of the reactants and products, Eq. 13.17a can be
written alternatively as
Q W a n1hf
h RTP 2 a n1hf
h RTR 2
P R
a n1hf
h2 a n1hf
h2 RTP a n
RTR a n (13.17b)
P R P R
The enthalpy of formation terms are obtained from Table A-25. The h terms are evaluated
as discussed above.
The foregoing concepts are illustrated in Example 13.6, where a gaseous mixture burns
in a closed, rigid container.
EXAMPLE 13.6 Analyzing Combustion at Constant Volume
A mixture of 1 kmol of gaseous methane and 2 kmol of oxygen initially at 25C and 1 atm burns completely in a closed, rigid
container. Heat transfer occurs until the products are cooled to 900 K. If the reactants and products each form ideal gas mix-
tures, determine (a) the amount of heat transfer, in kJ, and (b) the final pressure, in atm.
SOLUTION
Known: A mixture of gaseous methane and oxygen, initially at 25C and 1 atm, burns completely within a closed rigid con-
tainer. The products are cooled to 900 K.
Find: Determine the amount of heat transfer, in kJ, and the final pressure of the combustion products, in atm.
1kmol CH4(g) Products of

2 kmol O2 combustion
T1 = 25C T2
p1 = 1 atm p2
State 1 State 2
Figure E13.6
Assumptions:
1. The contents of the closed, rigid container are taken as the system.
2. Kinetic and potential energy effects are absent, and W 0.
4. The initial mixture and the products of combustion each form ideal gas mixtures.
5. The initial and final states are equilibrium states.
Analysis: The chemical reaction equation for the complete combustion of methane with oxygen is
CH4
2O2 S CO2
2H2O
(a) With assumptions 2 and 3, the closed system energy balance takes the form
0
UP UR Q W
or
Q UP UR 11uCO2
2uH2O 1 g2 2 11uCH4 1 g2
2uO2 2
Each coefficient in this equation is the same as the corresponding term of the balanced chemical equation.
Since each reactant and product behaves as an ideal gas, the respective specific internal energies can be evaluated as
u h RT . The energy balance then becomes
Q 311hCO2 RT2 2
21hH2O 1g2 RT2 2 4 3 11hCH4 1g2 RT1 2
21hO2 RT1 2 4
where T1 and T2 denote, respectively, the initial and final temperatures. Collecting like terms
Q 1hCO2
2hH2O 1 g2 hCH4 1 g2 2hO2 2
3R1T1 T2 2
The specific enthalpies are evaluated in terms of the respective enthalpies of formation to give
Q 3 1hf
h2 CO2
21hf
h2 H2O 1 g2
0 0 0
1hf
h 2 CH4 1 g2 21hf
h 2 O2 4
3R1T1 T2 2
Since the methane and oxygen are initially at 25C, h 0 for each of these reactants. Also, hf 0 for oxygen.
With enthalpy of formation values for CO2, H2O(g), and CH4(g) from Table A-25 and enthalpy values for H2O and CO2
from Table A-23
Q 3 393,520
137,405 93642 4
23 241,820
131,828 99042 4
174,8502
318.31421298 9002
745,436 kJ
(b) By assumption 3, the initial mixture and the products of combustion each form ideal gas mixtures. Thus, for the
reactants
p1V nR RT1
where nR is the total number of moles of reactants and p1 is the initial pressure. Similarly, for the products
p2V nP RT2
where nP is the total number of moles of products and p2 is the final pressure.
Since nR nP 3 and volume is constant, these equations combine to give
p1 a b 11 atm2 3.02 atm

T2 900 K
p2
T1 298 K
13.2.3 Enthalpy of Combustion and Heating Values

Although the enthalpy of formation concept underlies the formulations of the energy bal-
ances for reactive systems presented thus far, the enthalpy of formation of fuels is not always
tabulated. for example. . . fuel oil and coal are normally composed of several indi-
vidual chemical substances, the relative amounts of which may vary considerably, depend-
ing on the source. Owing to the wide variation in composition that these fuels can exhibit,
we do not find their enthalpies of formation listed in Tables A-25 or similar compilations of
thermophysical data. In many cases of practical interest, however, the enthalpy of com-
bustion, which is accessible experimentally, can be used to conduct an energy analysis when
enthalpy of formation data are lacking.
The enthalpy of combustion hRP is defined as the difference between the enthalpy of the enthalpy of combustion
products and the enthalpy of the reactants when complete combustion occurs at a given tem-
perature and pressure. That is
hRP a ne he a ni hi (13.18)
P R
where the ns correspond to the respective coefficients of the reaction equation giving the
moles of reactants and products per mole of fuel. When the enthalpy of combustion is ex-
pressed on a unit mass of fuel basis, it is designated hRP. Tabulated values are usually given
at the standard temperature Tref and pressure pref introduced in Sec. 13.2.1. The symbol hRP
or hRP is used for data at this temperature and pressure.
The heating value of a fuel is a positive number equal to the magnitude of the enthalpy
of combustion. Two heating values are recognized by name: the higher heating value (HHV) higher and lower
and the lower heating value (LHV). The higher heating value is obtained when all the wa- heating values
ter formed by combustion is a liquid; the lower heating value is obtained when all the water
formed by combustion is a vapor. The higher heating value exceeds the lower heating value
by the energy that would be required to vaporize the liquid formed. Values for the HHV and
LHV also depend on whether the fuel is a liquid or a gas. Heating value data for several
hydrocarbons are provided in Tables A-25.
The calculation of the enthalpy of combustion, and the associated heating value, using
table data is illustrated in the next example.
EXAMPLE 13.7 Calculating Enthalpy of Combustion
Calculate the enthalpy of combustion of gaseous methane, in kJ per kg of fuel, (a) at 25C, 1 atm with liquid water in the
products, (b) at 25C, 1 atm with water vapor in the products. (c) Repeat part (b) at 1000 K, 1 atm.
SOLUTION
Known: The fuel is gaseous methane.
Find: Determine the enthalpy of combustion, in kJ per kg of fuel, (a) at 25C, 1 atm with liquid water in the products,
(b) at 25C, 1 atm with water vapor in the products, (c) at 1000 K, 1 atm with water vapor in the products.
Assumptions:
2. Combustion is complete, and both reactants and products are at the same temperature and pressure.
3. The ideal gas model applies for methane, the combustion air, and the gaseous products of combustion.
Analysis: The combustion equation is

CH4
2O2
7.52N2 S CO2
2H2O
7.52N2
The enthalpy of combustion is, from Eq. 13.18
hRP a ne 1hf
h2 e a ni 1hf
h2 i
P R
Introducing the coefficients of the combustion equation and evaluating the specific enthalpies in terms of the respective
enthalpies of formation
hRP hCO2
2hH2O hCH4 1 g2 2hO2
0
1hf
h2 CO2
21hf
h2 H2O 1hf
h2 CH4 1g2 21hf
h2 O2
For nitrogen, the enthalpy terms of the reactants and products cancel. Also, the enthalpy of formation of oxygen is zero by
definition. On rearrangement, the enthalpy of combustion expression becomes
hRP 1hf 2 CO2

21hf 2 H2O 1hf 2 CH4 1g2
3 1 h2 CO2
21h2 H2O 1h2 CH4 1g2 21 h2 O2 4
hRP
3 1h2 CO2
21 h2 H2O 1h2 CH4 1g2 21h2 O2 4
The values for hRP and ( h)H2O depend on whether the water in the products is a liquid or a vapor.
(a) Since the reactants and products are at 25C, 1 atm in this case, the h terms drop out of the above expression for hRP.
Thus, for liquid water in the products, the enthalpy of combustion is
hRP 1hf 2 CO2

21hf 2 H2O1l2 1hf 2 CH4 1g2
With enthalpy of formation values from Table A-25
hRP 393,520
21285,8302 174,8502 890,330 kJ/kmol 1fuel2
Dividing by the molecular weight of methane places this result on a unit mass of fuel basis
890,330 kJ/kmol 1fuel2
hRP 55,507 kJ/kg 1fuel2
16.04 kg 1fuel2 kmol 1fuel2
which agrees with the higher heating value of methane given in Table A-25.
(b) As in part (a), the h terms drop out of the above expression for hRP, which for water vapor in the products reduces to
hRP, where
hRP 1hf 2 CO2

21hf 2 H2O1 g2 1hf 2 CH4 1 g2
With enthalpy of formation values from Table A-25
hRP 393,520
21241,8202 174,8502 802,310 kJ/kmol 1fuel2
On a unit of mass of fuel basis, the enthalpy of combustion for this case is
802,310
hRP 50,019 kJ/kg fuel
16.04
which agrees with the lower heating value of methane given in Table A-25.
(c) For the case where the reactants and products are at 1000 K, 1 atm, the term hRP in the above expression for hRP has the
value determined in part (b): hRP 802,310 kJ/kmol (fuel), and the h terms for O2, H2O(g), and CO2 can be evaluated
using specific enthalpies at 298 and 1000 K from Table A-23. The results are
1 h2 O2 31,389 8682 22,707 kJ/kmol

1 h2 H2O 1 g2 35,882 9904 25,978 kJ/kmol
1 h2 CO2 42,769 9364 33,405 kJ/kmol
For methane, the cp expression of Table A-21 can be used to obtain
1 h2 CH4 1 g2
1000
cp dT
298
3.979 T 2 24.558 T 3 22.733 T 4 6.963 T 5 1000

R a3.826 T 3

9

b
10 2 10 6
3 10 4 1012 5 298
Substituting values into the expression for the enthalpy of combustion
hRP 802,310
333,405
2125,9782 38,189 2122,7072 4
13.3 Determining the Adiabatic Flame Temperature 641
On a unit mass basis

800,552
hRP 49,910 kJ/kg 1fuel2
16.04
Using Interactive Thermodynamics: IT, we get 38,180 kJ/kmol (fuel).

Comparing the values of parts (b) and (c), the enthalpy of combustion of methane is seen to vary little with temperature.
The same is true for many hydrocarbon fuels. This fact is sometimes used to simplify combustion calculations.
When enthalpy of formation data are available for all the reactants and products, the enthalpy
of combustion can be calculated directly from Eq. 13.18, as illustrated in Example 13.7. Other-
wise, it must be obtained experimentally using devices known as calorimeters. Both constant-
volume (bomb calorimeters) and flow-through devices are employed for this purpose. Consider
as an illustration a reactor operating at steady state in which the fuel is burned completely with
air. For the products to be returned to the same temperature as the reactants, a heat transfer from
the reactor would be required. From an energy rate balance, the required heat transfer is
#
Qcv
# a ne he a ni hi (13.19)
nF P R
where the symbols # have the same significance as in previous discussions. The heat transfer
per mole of fuel, QcvnF, would be determined from measured
#
# # data. Comparing Eq. 13.19
with the defining equation, Eq. 13.18, we have hRP QcvnF. In accord with the usual sign
convention for heat transfer, the enthalpy of combustion would be negative.
As noted previously, the enthalpy of combustion can be used for energy analyses of re-
acting systems. for example. . . consider a control volume at steady state for which
the energy rate balance takes the form
# #
# # a ne 1hf
h2 e a ni 1hf
h2 i
Qcv Wcv
nF nF P R
All symbols have the same significance as in previous discussions. This equation can be re-
arranged to read
# #
# # a ne 1hf 2 e a ni 1hf 2 i
a ne 1 h2 e a ni 1 h2 i
Qcv Wcv
nF nF P R P R
For a complete reaction, the underlined term is just the enthalpy of combustion hRP, at Tref
and pref. Thus, the equation becomes
# #
# # hRP
a ne 1 h2 e a ni 1h2 i
Qcv Wcv
(13.20)
nF nF P R
The right side of Eq. 13.20 can be evaluated with an experimentally determined value for
hRP and h values for the reactants and products determined as discussed previously.

13.3 Determining the Adiabatic
Flame Temperature
#
Let us reconsider the reactor at steady state pictured in Fig. 13.2. In the absence of work Wcv
and appreciable kinetic and potential energy effects, the energy liberated on combustion is trans-
ferred from the reactor in two ways only: by energy accompanying the exiting combustion
products and by heat transfer to the surroundings. The smaller the heat transfer, the greater the
energy carried out with the combustion products and thus the greater the temperature of the prod-
ucts. The temperature that would be achieved by the products in the limit of adiabatic operation
adiabatic flame of the reactor is called the adiabatic flame temperature or adiabatic combustion temperature.
temperature The adiabatic flame temperature can be determined by use of the conservation of mass
and conservation of energy principles. To illustrate the procedure, let us suppose that the
combustion air and the combustion products each form ideal gas mixtures. Then, with the
other assumptions stated above, the energy rate balance on a per mole of fuel basis, Eq. 13.12b,
reduces to the form hP hRthat is
a ne he a ni hi (13.21a)
P R
where i denotes the incoming fuel and air streams and e the exiting combustion products.
With this expression, the adiabatic flame temperature can be determined using table data or
computer software, as follows.
USING TABLE DATA. When using Eq. 13.9 with table data to evaluate enthalpy terms,
Eq. 13.21a takes the form
a ne 1hf
h2 e a ni 1hf
h2 i
P R
or
a ne 1 h2 e a ni 1 h2 i
a ni hfi a ne hfe (13.21b)
P R R P
The ns are obtained on a per mole of fuel basis from the balanced chemical reaction equation.
The enthalpies of formation of the reactants and products are obtained from Table A-25 or
A-25E. Enthalpy of combustion data might be employed in situations where the enthalpy of
formation for the fuel is not available. Knowing the states of the reactants as they enter the re-
actor, the h terms for the reactants can be evaluated as discussed previously. Thus, all terms
on the right side of Eq. 13.21b can be evaluated. The terms (h) e on the left side account for
the changes in enthalpy of the products from Tref to the unknown adiabatic flame temperature.
Since the unknown temperature appears in each term of the sum on the left side of the equa-
tion, determination of the adiabatic flame temperature requires iteration: A temperature for the
products is assumed and used to evaluate the left side of Eq. 13.21b. The value obtained is
compared with the previously determined value for the right side of the equation. The proce-
dure continues until satisfactory agreement is attained. Example 13.8 gives an illustration.
USING COMPUTER SOFTWARE. Thus far we have emphasized the use of Eq. 13.9 together
with table data when evaluating the specific enthalpies required by energy balances for re-
acting systems. Such enthalpy values also can be retrieved using Interactive Thermodynam-
ics: IT. With IT, the quantities on the right side of Eq. 13.9 are evaluated by software, and
h data are returned directly. for example. . . consider CO2 at 500 K modeled as an
ideal gas. The specific enthalpy is obtained from IT as follows:
T = 500 // K
h = h_T(CO2, T)
Choosing K for the temperature unit and moles for the amount under the Units menu, IT re-
turns h 3.852 105 kJ/kmol.
This value agrees with the value calculated from Eq. 13.9 using enthalpy data for CO2
from Table A-23, as follows
h hf
3h1500 K2 h1298 K2 4
393,520
317,678 93644
3.852 105 kJ/kmol
13.3 Determining the Adiabatic Flame Temperature 643
As suggested by this discussion, IT is also useful for analyzing reacting systems. In par-
ticular, the equation solver and property retrieval features of IT allow the adiabatic flame
temperature to be determined without the iteration required when using table data. This is
illustrated in Example 13.8.
EXAMPLE 13.8 Determining the Adiabatic Flame Temperature
Liquid octane at 25C, 1 atm enters a well-insulated reactor and reacts with air entering at the same temperature and pressure.
For steady-state operation and negligible effects of kinetic and potential energy, determine the temperature of the combustion
products for complete combustion with (a) the theoretical amount of air, (b) 400% theoretical air.
SOLUTION
Known: Liquid octane and air, each at 25C and 1 atm, burn completely within a well-insulated reactor operating at steady
state.
Find: Determine the temperature of the combustion products for (a) the theoretical amount of air and (b) 400% theoretical
air.
C8H18(l)
25C, 1 atm
Insulation
Air Combustion products,

25C, 1 atm TP
Figure E13.8
Assumptions:
1. The control volume indicated on the accompanying figure by a dashed line operates at steady state.
# #
2. For the control volume, Qcv 0, Wcv 0, and kinetic and potential effects are negligible.
3. The combustion air and the products of combustion each form ideal gas mixtures.
Analysis: At steady state, the control volume energy rate balance Eq. 13.12b reduces with assumptions 2 and 3 to give
Eq. 13.21a
a ne he a ni hi (1)
P R
When Eq. 13.9 and table data are used to evaluate the enthalpy terms, Eq. (1) is written as
a ne 1hf
h2 e a ni 1hf
h2 i
P R
On rearrangement, this becomes
a ne 1h2 e a ni 1h2 i
a ni hfi a ne hfe
P R R P
which corresponds to Eq. 13.21b. Since the reactants enter at 25C, the ( h)i terms on the right side vanish, and the energy
rate equation becomes
a ne 1h2 e a ni hfi a ne hfe (2)

P R P
(a) For combustion of liquid octane with the theoretical amount of air, the chemical equation is
C8H18 1l2
12.5O2
47N2 S 8CO2
9H2O1g2
47N2
Introducing the coefficients of this equation, Eq. (2) takes the form
81 h2 CO2
91 h2 H2O1g2
471h2 N2
3 1hf 2 C8H181l2
12.51hf 2 O2
471hf 2 N2 4
0 0
381hf 2 CO2
91hf 2 H2O1g2
471hf 2 N2 4
0
The right side of the above equation can be evaluated with enthalpy of formation data from Table A-25, giving
81 h2 CO2
91 h2 H2O1g2
471 h2 N2 5,074,630 kJ/kmol 1fuel2
Each h term on the left side of this equation depends on the temperature of the products, TP. This temperature can be de-
termined by an iterative procedure.
The following table gives a summary of the iterative procedure for three trial values of TP. Since the summation of the en-
thalpies of the products equals 5,074,630 kJ/kmol, the actual value of TP is in the interval from 2350 to 2400 K. Interpolation
between these temperatures gives TP 2395 K.
2500 K 2400 K 2350 K

81 h2 CO2 975,408 926,304 901,816
91 h2 H2O1g2 890,676 842,436 818,478
471 h2 N2 3,492,664 3,320,597 3,234,869
a ne 1 h2 e 5,358,748 5,089,337 4,955,163

P
The following IT code can be used as an alternative to iteration with table data, where hN2_R and hN2_P denote the enthalpy
of N2 in the reactants and products, respectively, and so on. In the Units menu, select temperature in K and amount of substance
in moles.
TR = 25 + 273.15 // K
// Evaluate reactant and product enthalpies, hR and hP, respectively

hR = hC8H18 + 12.5 * hO2_R + 47 * hN2_R
hP = 8 * hCO2_P + 9 * hH2O_P + 47 * hN2_P
hC8H18 = 249910 // kJ/kmol (Value from Table A-25)

hO2_R = h_T(O2,TR)
hN2_R = h_T(N2,TR)
hCO2_P = h_T(CO2,TP)
hH2O_P = h_T(H2O,TP)
hN2_P = h_T(N2,TP)
// Energy balance
hP = hR
Using the Solve button, the result is TP = 2394 K, which agrees closely with the result obtained above.
(b) For complete combustion of liquid octane with 400% theoretical air, the chemical equation is
C8H18 1l2
50O2
188N2 S 8CO2
9H2O
37.5O2
188N2
13.4 Fuel Cells 645
Equation (2), the energy rate balance, reduces for this case to
81 h2 CO2
91 h2 H2O1g2
37.51h2 O2
1881h2 N2 5,074,630 kJ/kmol 1fuel2
Observe that the right side has the same value as in part (a). Proceeding iteratively as above, the temperature of the products
is TP 962 K. The use of IT to solve part (b) is left as an exercise.
The temperature determined in part (b) is considerably lower than the value found in part (a). This shows that once enough
oxygen has been provided for complete combustion, bringing in more air dilutes the combustion products, lowering their
temperature.
CLOSING COMMENTS. For a specified fuel and specified temperature and pressure of the
reactants, the maximum adiabatic flame temperature is for complete combustion with the the-
oretical amount of air. The measured value of the temperature of the combustion products
may be several hundred degrees below the calculated maximum adiabatic flame temperature,
however, for several reasons:
Once adequate oxygen has been provided to permit complete combustion, bringing in
more air dilutes the combustion products, lowering their temperature.
Incomplete combustion also tends to reduce the temperature of the products, and com-
bustion is seldom complete (see Sec. 14.4).
Heat losses can be reduced but not altogether eliminated.
As a result of the high temperatures achieved, some of the combustion products may
dissociate. Endothermic dissociation reactions lower the product temperature. The effect
of dissociation on the adiabatic flame temperature is considered in Sec. 14.4.

13.4 Fuel Cells
A fuel cell is an electrochemical device in which fuel and an oxidizer (normally oxygen from fuel cell
air) undergo a chemical reaction, providing electrical current to an external circuit and pro-
ducing products. The fuel and oxidizer react catalytically in stages on separate electrodes:
the anode and the cathode. An electrolyte separating the two electrodes allows passage of
ions formed by reaction. Depending on the type of fuel cell, the ions may be positively or
negatively charged. The reaction is not a combustion process.
Rates of reaction in fuel cells are limited by the time it takes for diffusion of chemical
species through the electrodes and the electrolyte and by the speed of the chemical reactions
themselves. These features, together with other aspects of fuel cell operation, result in in-
ternal irreversibilities that are inherently less significant than encountered in power producing
devices relying on combustion.
By avoiding highly irreversible combustion, fuel cells have the potential of providing more
power from a given supply of fuel and oxidizer, while forming fewer undesirable products,
than internal combustion engines and gas turbines. In contrast to power plants studied in pre-
vious chapters, fuel cells can produce electric power without moving parts or utilizing
intermediate heat exchangers. Fuel cells do not operate as thermodynamic power cycles, and
thus the notion of a limiting thermal efficiency imposed by the second law is not applicable.
Despite these thermodynamic advantages, widespread use of fuel cells has not occurred thus
far owing primarily to cost.
For scale, Fig. 13.3a shows a solid oxide fuel cell module. Figure 13.3b gives the
schematic of a proton exchange membrane fuel cell, which is discussed next as a repre-
sentative case.
External electric circuit
2e
Fuel Oxidizer
H2 1
2e
2e
O
2 2
1
H2 2H+ + 2e 1
O
2 2 + 2H+ + 2e H2O
H2 2H+ O
2 2
H2O
Electrolyte
Cathode
Product
Anode
H 2O
Overall cell reaction: H2 + 12 O2 H2O

(a) (b)
Figure 13.3 Fuel cell power systems. (a) 25-kW solid oxide fuel cell module. (b) Schematic of
a proton exchange membrane fuel cell.
PROTON EXCHANGE MEMBRANE FUEL CELL. The fuel cell shown in Fig. 13.3b operates
with hydrogen (H2) as the fuel and oxygen (O2) as the oxidizer. This type of cell is known
as a proton exchange membrane cell (PEMFC). At the anode, hydrogen ions (H
) and elec-
trons are produced. At the cathode, ions and electrons are consumed. The reactions at these
electrodes and the overall cell reaction are labeled on the figure. The only products of this
fuel cell are water and the power generated.
Charge-carrying hydrogen ions are conducted through the electrolytic membrane. For ac-
ceptable ion conductivity, a high membrane water content is required. This requirement restricts
the fuel cell to operating in the range 60100C, which is below the boiling point of water.
Cooling is generally needed to maintain the fuel cell at the operating temperature. Due to such
relatively low temperature operation, costly platinum catalysts are required at both the anode
and cathode to increase ionization reaction rates. Catalytic activity is more important in lower
temperature fuel cells because reaction rates tend to decrease with decreasing temperature.
Major automakers are beginning to introduce vehicles powered by proton exchange mem-
brane fuel cells. Fuel cell stacks formed from several hundred individual fuel cells are required
to meet automotive needs. These fuel cell stacks are integrated with several components
necessary to support fuel cell operation, including components that provide fuel, oxidizer,
and coolant. Power requirements, irreversibilities, and losses associated with the support
components conspire to give a much lower net power output for a given fuel input than
obtainable from the stand-alone fuel cell.
Proton exchange membrane fuel cells also have potential to replace batteries in portable
devices such as cellular phones, laptop computers, and video players.
FUELS. With todays technology, hydrogen is preferred for fuel cell applications because of its
exceptional ability to produce electrons when suitable catalysts are used, while in principle pro-
ducing no harmful emissions from the fuel cell itself. Methanol (CH3OH) and carbon monoxide
can be used directly as fuels in some applications, but often with performance penalties.
Since hydrogen is not naturally occurring, it must be produced chemically from hydro-
carbons, including natural gas, by electrolysis of water, or by other means. Hydrogen pro-
duction technologies involving chemical processes can generate undesirable emissions.
Irreversibilities and losses inherent in hydrogen production also result in a lower overall con-
version of primary input to fuel cell-generated power than reported for fuel cells directly
fueled with hydrogen.
In some applications, hydrogen is provided directly to the fuel cell from storage as a com-
pressed gas, a cryogenic liquid, or atoms absorbed within metallic structures. Hydrogen also
13.4 Fuel Cells 647

Goodbye Batteries, Hello Fuel Cells? stakes are high in the
consumer electronics
Power needs of cellular phones, laptops, and other portable market.
electronic devices are increasing so rapidly that the battery in- Like the fuel cells
dustry is struggling to keep up. Some observers say that being developed to
todays batteries wont be able to provide enough power, are power cars and gen-
too heavy, and dont last long enough to meet the needs of erate electricity for
quickly evolving electronics. Pocket-size fuel cells might prove homes and offices, the
to be a viable alternative. pocket-size versions
To meet consumer needs, companies are rushing to develop face stiff challenges
small fuel cells that promise to provide power up to 10 times on the way to market.
longer on a single charge than conventional batteries.These cells They rely on costly
can be charged instantly just by adding more fuel. Battery com- precious-metal cata-
panies are fighting back with a new generation of batteries, lysts to operate and are difficult to manufacture. They run on
known as lithium ion batteries, already used in watches, flash combustible fuels, typically hydrogen or methanol, and this
cameras, and rechargeable power packs. Lithium ion batteries brings concerns over safety. Still, many think fuel cells for
provide several times the output of similar-size alkaline batter- portable electronics will be the first fuel cells most of us will
ies and can be recharged numerous times. To compete, fuel cells see because of strong consumer demand for cost-competitive,
must prove themselves as reliable and versatile as batteries, and longer lasting, instantly rechargeable power.
can be produced at the point of use. Internal reforming refers to applications where hydrogen
production is integrated with the fuel cell. When hydrogen is produced separately from the
fuel cell itself, this is known as external reforming. Owing to thermal limitations of current
technology, internal reforming is feasible only in higher-temperature molten carbonate and
solid oxide fuel cells.
Table 13.1 summarizes the most promising fuel cell technologies currently under investi-
gation. Included are potential applications and other characteristics. For more detailed
discussions, see the sources listed in Table 13.1.
TABLE 13.1 Characteristics of Major Fuel Cell Types

Proton Phosphoric Acid Molten Solid Oxide Fuel
Exchange Fuel Cell (PAFC) Carbonate Fuel Cell (SOFC)
Membrane Fuel Cell (MCFC)
Cell (PEMFC)
Transportation - automotive power - large vehicle power - vehicle auxiliary
application power
- heavy vehicle
propulsion
Other applications - portable power - on-site cogeneration - on-site cogeneration - on-site cogeneration
- small-scale - electric power - electric power - electric power
stationary power generation generation generation
Electrolyte ion exchange membrane liquid phosphoric acid liquid molten carbonate solid oxide ceramic
Charge carrier H
H
CO3 O
Operating 60 100C 150220C 600700C 8001000C
temperature
Fuel reforming external external internal or external internal or external
Source: Appleby, A. J., and Foulkes, F. R., 1993, Fuel Cell Handbook, Krieger Publishing Company, Malabar, Florida. Hirschenhofer, J. H.,
Stauffer, D. B., Engleman, R. R., and Klett, M. G., 1998, Fuel Cell Handbook, Fourth Edition, DOE/FETC-99/1076.

13.5 Absolute Entropy and the
Third Law of Thermodynamics
Thus far our analyses of reacting systems have been conducted using the conservation of
mass and conservation of energy principles. In the present section some of the implications
of the second law of thermodynamics for reacting systems are considered. The discussion
continues in the second part of this chapter dealing with the exergy concept, and in the next
chapter where the subject of chemical equilibrium is taken up.
13.5.1 Evaluating Entropy for Reacting Systems

The property entropy plays an important part in quantitative evaluations using the second law
of thermodynamics. When reacting systems are under consideration, the same problem arises
for entropy as for enthalpy and internal energy: A common datum must be used to assign
entropy values for each substance involved in the reaction. This is accomplished using the
third law of thermodynamics and the absolute entropy concept.
third law of The third law deals with the entropy of substances at the absolute zero of temperature. Based
thermodynamics on empirical evidence, this law states that the entropy of a pure crystalline substance is zero at
the absolute zero of temperature, 0 K. Substances not having a pure crystalline structure at
absolute zero have a nonzero value of entropy at absolute zero. The experimental evidence
on which the third law is based is obtained primarily from studies of chemical reactions at low
temperatures and specific heat measurements at temperatures approaching absolute zero.
ABSOLUTE ENTROPY. For present considerations, the importance of the third law is that it
provides a datum relative to which the entropy of each substance participating in a reaction can
be evaluated so that no ambiguities or conflicts arise. The entropy relative to this datum is called
absolute entropy the absolute entropy. The change in entropy of a substance between absolute zero and any
given state can be determined from precise measurements of energy transfers and specific heat
data or from procedures based on statistical thermodynamics and observed molecular data.
Table A-25 give the value of the absolute entropy for selected substances at the
standard reference state, Tref 298.15 K, pref 1 atm. Two values of absolute entropy for
water are provided. One is for liquid water and the other is for water vapor. As for the
case of the enthalpy of formation of water considered previously, the vapor value listed
is for a hypothetical ideal gas state in which water is a vapor at 25C and 1 atm.
Tables A-22 and A-23 give tabulations of absolute entropy versus temperature at a pressure
of 1 atm for selected gases. The absolute entropy at 1 atm and temperature T is designated
as s(T) or s(T ), depending on whether the value is on a unit mass or per mole basis. In
all these tables, ideal gas behavior is assumed for the gases.
When the absolute entropy is known at the standard state, the specific entropy at any other
state can be found by adding the specific entropy change between the two states to the absolute
entropy at the standard state. Similarly, when the absolute entropy is known at the pressure
pref and temperature T, the absolute entropy at the same temperature and any pressure p can
be found from
s 1T, p2 s 1T, pref 2
3s 1T, p2 s 1T, pref 2 4
The second term on the right side of this equation can be evaluated for an ideal gas by
using Eq. 6.21b, giving
s 1T, p2 s1T 2 R ln 1ideal gas2

p
(13.22)
pref
where s (T ) is the absolute entropy at temperature T and pressure pref.

13.5 Absolute Entropy and the Third Law of Thermodynamics 649
The entropy of the ith component of an ideal gas mixture is evaluated at the mixture tem-
perature T and the partial pressure pi: si (T, pi ). The partial pressure is given by pi yi p,
where yi is the mole fraction of component i and p is the mixture pressure. Thus, Eq. 13.22
takes the form
si 1T, pi 2 s
i 1T 2 R ln
pi
pref
or
si 1T, pi 2 si1T 2 R ln a b
yi p component i of an
(13.23)
pref ideal gas mixture
where si(T) is the absolute entropy of component i at temperature T and pref.
13.5.2 Entropy Balances for Reacting Systems

Many of the considerations that enter when energy balances are written for reacting systems
also apply to entropy balances. The writing of entropy balances for reacting systems will be
illustrated by referring to special cases of broad interest.
CONTROL VOLUMES AT STEADY STATE. Let us begin by reconsidering the steady-state re-
actor of Fig. 13.2, for which the combustion reaction is given by Eq. 13.11. The combustion air
and the products of combustion are each assumed to form ideal gas mixtures. The entropy rate
balance for the two-inlet, single-exit reactor can be expressed on a per mole of fuel basis as
#
QjTj

sF
c aa
b sO2
aa
b 3.76 sN2 d
b b
0a #
j nF 4 4
#
c asCO2
sH2O
aa
b 3.76 sN2 d
#
b b scv
(13.24)
2 4 nF
#
where nF is the molar flow rate of the fuel and the coefficients appearing in the underlined
terms are the same as those for the corresponding substances in the reaction equation.
The specific entropies of Eq. 13.24 are absolute entropies. Let us consider how the en-
tropies are evaluated for the combustion products and the combustion air. The entropies of
the combustion products would be evaluated from Eq. 13.23, using the temperature, pres-
sure, and composition of the products. The entropies of the entering oxygen and nitrogen
would be evaluated similarly, using the temperature, pressure, and composition of the com-
bustion air. If the fuel and air entered the reactor as an ideal gas mixture, the entropies of
the mixture components would be evaluated from Eq. 13.23 using the appropriate partial
pressures. Such considerations are illustrated in Example 13.9.
EXAMPLE 13.9 Evaluating Entropy Production for a Reactor
Liquid octane at 25C, 1 atm enters a well-insulated reactor and reacts with air entering at the same temperature and pressure.
The products of combustion exit at 1 atm pressure. For steady-state operation and negligible effects of kinetic and potential
energy, determine the rate of entropy production, in kJ/K per kmol of fuel, for complete combustion with (a) the theoretical
amount of air, (b) 400% theoretical air.
SOLUTION
Known: Liquid octane and air, each at 25C and 1 atm, burn completely within a well-insulated reactor operating at steady
state. The products of combustion exit at 1 atm pressure.
Find: Determine the rate of entropy production, in kJ/K per kmol of fuel, for combustion with (a) the theoretical amount of
air, (b) 400% theoretical air.
C8H18(l)
25C, 1 atm
Insulation
Air Combustion products,

25C, 1 atm 1 atm
TP = 2395 K (part a)
TP = 962 K (part b)
Figure E13.9
Assumptions:
1. The control volume shown on the accompanying figure by a dashed line operates at steady state and without heat transfer
with its surroundings.
2. Combustion is complete. Each mole of oxygen in the combustion air is accompanied by 3.76 moles of nitrogen, which is
inert.
3. The combustion air can be modeled as an ideal gas mixture, as can the products of combustion.
4. The reactants enter at 25C, 1 atm. The products exit at a pressure of 1 atm.
Analysis: The temperature of the exiting products of combustion TP was evaluated in Example 13.8 for each of the two cases.
For combustion with the theoretical amount of air, TP 2395 K. For complete combustion with 400% theoretical air, TP 962 K.
(a) For combustion of liquid octane with the theoretical amount of air, the chemical equation is
C8H18 1l2
12.5O2
47N2 S 8CO2
9H2O1g2
47N2
With assumptions 1 and 3, the entropy rate balance on a per mole of fuel basis, Eq. 13.24, takes the form
# 0
QjTj #

sF
112.5 sO2
47 sN2 2 18 sCO2
9 sH2O1g2
47 sN2 2
#
scv
0 a #
j nF nF
or on rearrangement
#
# 18 sCO2
9 sH2O1g2
47 sN2 2 sF 112.5 sO2
47 sN2 2
scv
(1)
nF
Each coefficient of this equation is the same as for the corresponding term of the balanced chemical equation.
The fuel enters the reactor separately at Tref, pref. The absolute entropy of liquid octane required by the entropy balance is
obtained from Table A-25 as 360.79 kJ/kmol # K.
The oxygen and nitrogen in the combustion air enter the reactor as components of an ideal gas mixture at Tref, pref. With
Eq. 13.23 and absolute entropy data from Table A-23
yO2 pref
sO2 s O2 1Tref 2 R ln
pref
205.03 8.314 ln 0.21 218.01 kJ/kmol # K
yN2 pref
sN2 s N2 1Tref 2 R ln
pref
191.5 8.314 ln 0.79 193.46 kJ/kmol # K
The product gas exits as an ideal gas mixture at 1 atm, 2395 K with the following composition: yCO2 864 0.125,
yH2O 1g2 964 0.1406, yN2 4764 0.7344. With Eq. 13.23 and absolute entropy data at 2395 K from Tables A-23
sCO2 s CO2 R ln yCO2

320.173 8.314 ln 0.125 337.46 kJ/kmol # K
sH2O 273.986 8.314 ln 0.1406 290.30 kJ/kmol # K
sN2 258.503 8.314 ln 0.7344 261.07 kJ/kmol # K
Inserting values into Eq.1, the expression for the rate of entropy production
#
scv
# 81337.462
91290.302
471261.072
nF
360.79 12.51218.012 471193.462
5404 kJ/kmol 1octane2 # K
As an alternative, the following IT code can be used to determine the entropy production per mole of fuel entering, where
sigma denotes scvnF, and sN2_R and sN2_P denote the entropy of N2 in the reactants and products, respectively, and so
# #
on. In the Units menu, select temperature in K, pressure in bar, and amount of substance in moles.
TR = 25 + 273.15 // K
p = 1.01325 // bar
TP = 2394 // K (Value from the IT alternative solution to Example 13.8)
// Determine the partial pressures

pO2_R = 0.21 * p
pN2_R = 0.79 * p
pCO2_P = (8/64) * p
pH2O_P = (9/64) * p
pN2_P = (47/64) * p
// Evaluate the absolute entropies

sC8H18 = 360.79 // kJ/kmol K (from Table A-25)
sO2_R = s_TP(O2, TR, pO2_R)
sN2_R = s_TP(N2, TR, pN2_R)
sCO2_P = s_TP(CO2, TP, pCO2_P)
sH2O_P = s_TP(H2O, TP, pH2O_P)
sN2_P = s_TP(N2, TP, pN2_P)
// Evaluate the reactant and product entropies, sR and sP, respectively

sR = sC8H18 + 12.5 * sO2_R + 47 * sN2_R
sP = 8 * sCO2_P + 9 * sH2O_P + 47 * sN2_P
// Entropy balance, Eq. (1)

sigma = sP sR
Using the Solve button, the result is sigma = 5404 kJ/kmol (octane) # K, which agrees with the result obtained above.
(b) The complete combustion of liquid octane with 400% theoretical air is described by the following chemical equation:
C8H18 1l2
50O2
188N2 S 8CO2
9H2O1g2
37.5O2
188N2
The entropy rate balance on a per mole of fuel basis takes the form
#
# 18 sCO2
9 sH2O 1g2
37.5 sO2
188 sN2 2 sF 150 sO2
188 sN2 2
scv
nF
The specific entropies of the reactants have the same values as in part (a). The product gas exits as an ideal gas mixture at 1 atm,
962 K with the following composition: yCO2 8242.5 0.033, yH2O 1g2 9242.5 0.0371, yO2 37.5242.5 0.1546,
yN2 0.7753. With the same approach as in part (a)
sCO2 267.12 8.314 ln 0.033 295.481 kJ/kmol # K

sH O 231.01 8.314 ln 0.0371 258.397 kJ/kmol # K
2
sO2 242.12 8.314 ln 0.1546 257.642 kJ/kmol # K

sN 226.795 8.314 ln 0.7753 228.911 kJ/kmol # K
2
Inserting values into the expression for the rate of entropy production
#
scv
# 81295.4812
91258.3972
37.51257.6422
1881228.9112
nF
360.79 501218.012 1881193.462
9754 kJ/kmol 1octane2 # K
The use of IT to solve part (b) is left as an exercise.
For several gases modeled as ideal gases, IT directly returns the absolute entropies required by entropy balances for re-
acting systems. The entropy data obtained from IT agree with values calculated from Eq. 13.23 using table data.
Comparing the results of parts (a) and (b), note that once enough oxygen has been provided for complete combustion,
mixing a greater amount of air with the fuel prior to combustion results in a lower product gas temperature and a greater
rate of entropy production.
Although the rates of entropy production calculated in this example are positive, as required by the second law, this does
not mean that the proposed reactions necessarily would occur, for the results are based on the assumption of complete
combustion. The possibility of achieving complete combustion with specified reactants at a given temperature and pres-
sure can be investigated with the methods of Chap. 14, dealing with chemical equilibrium. For further discussion, see
Sec. 14.4.1.
CLOSED SYSTEMS. Next consider an entropy balance for a process of a closed system dur-
ing which a chemical reaction occurs
aTb
dQ
SP SR
s (13.25)
b
SR and SP denote, respectively, the entropy of the reactants and the entropy of the products.
When the reactants and products form ideal gas mixtures, the entropy balance can be ex-
pressed on a per mole of fuel basis as
aTb
1 dQ s
a ns a ns n
nF
(13.26)
P R F b
where the coefficients n on the left are the coefficients of the reaction equation giving the
moles of each reactant or product per mole of fuel. The entropy terms would be evalu-
ated from Eq. 13.23 using the temperature, pressure, and composition of the reactants or
products, as appropriate. The fuel would be mixed with the oxidizer, so this must be taken
into account when determining the partial pressures of the reactants. Example 13.10
provides an illustration of the evaluation of entropy change for combustion at constant
volume.
EXAMPLE 13.10 Entropy Change for Combustion at Constant Volume
Determine the change in entropy of the system of Example 13.6 in kJ/K.
SOLUTION
Known: A mixture of gaseous methane and oxygen, initially at 25C and 1 atm, burns completely within a closed rigid con-
tainer. The products are cooled to 900 K, 3.02 atm.
Find: Determine the change in entropy for the process in kJ/K.
Assumptions:
1. The contents of the container are taken as the system.
2. The initial mixture can be modeled as an ideal gas mixture, as can the products of combustion.
Analysis: The chemical equation for the complete combustion of methane with oxygen is
CH4
2O2 S CO2
2H2O
The change in entropy for the process of the closed system is S SP SR, where SR and SP denote, respectively, the
initial and final entropies of the system. Since the initial mixture forms an ideal gas mixture (assumption 2), the entropy of
the reactants can be expressed as the sum of the contributions of the components, each evaluated at the mixture temperature
and the partial pressure of the component. That is
SR 1 sCH4 1T1, yCH4 p1 2
2 sO2 1T1, yO2 p1 2
where yCH4 13 and yO2 23 denote, respectively, the mole fractions of the methane and oxygen in the initial mixture. Sim-
ilarly, since the products of combustion form an ideal gas mixture (assumption 2)
Sp 1 sCO2 1T2, yCO2 p2 2
2 sH2O 1T2, yH2O p2 2
where yCO2 13 and yH2O 23 denote, respectively, the mole fractions of the carbon dioxide and water vapor in the prod-
ucts of combustion. In these equations, p1 and p2 denote the pressure at the initial and final states, respectively.
The specific entropies required to determine SR can be calculated from Eq. 13.23. Since T1 Tref and p1 pref, absolute
entropy data from Table A-25 can be used as follows
yCH4 pref
sCH4 1T1, yCH4 p1 2 sCH4 1Tref 2 R ln
pref
1
186.16 8.314 ln 195.294 kJ/kmol # K
3
Similarly
yO2 pref
sO2 1T1, yO2 p1 2 sO2 1Tref 2 R ln
pref
2
205.03 8.314 ln 208.401 kJ/kmol # K
3
At the final state, the products are at T2 900 K and p2 3.02 atm. With Eq. 13.23 and absolute entropy data from
Tables A-23
yCO2 p2
sCO2 1T2, yCO2 p2 2 sCO2 1T2 2 R ln
pref
1132 13.022
263.559 8.314 ln 263.504 kJ/kmol # K
1
yH2O p2
sH2O 1T2, yH2O p2 2 sH2O 1T2 2 R ln
pref
1232 13.022
228.321 8.314 ln 222.503 kJ/kmol # K
1
Finally, the entropy change for the process is

S SP SR
3263.504
21222.5032 4 3 195.294
21208.4012 4
96.414 kJ/K
13.5.3 Evaluating Gibbs Function for Reacting Systems

The thermodynamic property known as the Gibbs function plays a role in the second part of this
chapter dealing with exergy analysis. The specific Gibbs function g, introduced in Sec. 11.3, is
g h Ts (13.27)
The procedure followed in setting a datum for the Gibbs function closely parallels that used
in defining the enthalpy of formation: To each stable element at the standard state is assigned
Gibbs function of a zero value of the Gibbs function. The Gibbs function of formation of a compound equals
formation the change in the Gibbs function for the reaction in which the compound is formed from its
elements, the compound and the elements all being at Tref and pref. Table A-25 gives the Gibbs
function of formation, g f , at 25C and 1 atm for selected substances.
The Gibbs function at a state other than the standard state is found by adding to the Gibbs
function of formation the change in the specific Gibbs function g between the standard
state and the state of interest
g1T, p2 g f
3g1T, p2 g1Tref, pref 2 4 g f
g (13.28)
With Eq. 13.27, g can be written as

g 3h1T, p2 h1Tref, pref 2 4 3T s 1T, p2 Tref s 1Tref, pref 2 4
The Gibbs function of component i in an ideal gas mixture is evaluated at the partial pres-
sure of component i and the mixture temperature.
The procedure for determining the Gibbs function of formation is illustrated in the next
example.
EXAMPLE 13.11 Determining the Gibbs Function of Formation
Determine the Gibbs function of formation of methane at the standard state, 25C and 1 atm, in kJ/kmol, and compare with
the value given in Table A-25.
SOLUTION
Known: The compound is methane.

Find: Determine the Gibbs function of formation at the standard state, in kJ/kmol, and compare with the Table A-25 value.
Assumptions: In the formation of methane from carbon and hydrogen (H2), the carbon and hydrogen are each initially at
25C and 1 atm. The methane formed is also at 25C and 1 atm.
Analysis: Methane is formed from carbon and hydrogen according to C
2H2 S CH4. The change in the Gibbs function
for this reaction is
gP gR 1h T s2 CH4 1h T s2 C 21h T s2 H2
1hCH4 hC 2hH2 2 T 1sCH4 sC 2sH2 2
where gP and gR denote, respectively, the Gibbs functions of the reactants and products, each per kmol of methane.
In the present case, all substances are at the same temperature and pressure, 25C and 1 atm, which correspond to the stan-
dard reference state values. At the standard reference state, the enthalpies and Gibbs functions for carbon and hydrogen are
zero by definition. Thus, in the above equation gR hC hH2 0. Also, gP 1gf 2 CH4, giving
1gf 2 CH4 1hf 2 CH4 Tref 1sCH4 sC 2 sH2 2

where the superscript denotes properties at Tref, pref. With enthalpy of formation and absolute entropy data from Table A-25
1gf 2 CH4 74,850 298.15 3186.16 5.74 21130.572 4 50,783 kJ/kmol
The slight difference between the calculated value for the Gibbs function of formation of methane and the value from Table A-25
can be attributed to round-off.
CHEMICAL EXERGY1
The objective of this part of the chapter is to extend the exergy concept introduced in Chap. 7
by considering the role of chemical composition. To distinguish the current considerations
from those introduced previously, let the system be a specified amount of a hydrocarbon fuel
CaHb at temperature T0 and pressure p0 and let the exergy reference environment consist of
a gas phase at T0, p0 involving nitrogen, oxygen, water vapor, and carbon dioxide. Since the
system is in thermal and mechanical equilibrium with the environment, the value of exergy as
defined in Sec. 7.2 would be zero. More precisely, we should say that the thermomechanical
contribution to the exergy magnitude has a value of zero, for a chemical contribution related
to composition can be defined that has a nonzero value. This aspect of the exergy concept is
the subject of the present section.

13.6 Introducing Chemical Exergy
Exergy is introduced in Chap. 7 through study of a combined system consisting of a system
of interest and an exergy reference environment. The object of the development of Sec. 7.2.3
is an expression for the maximum theoretical work obtainable from the combined system
as the system comes into thermal and mechanical equilibrium with the environment. The
thermomechanical exergy is this value for work. We begin the present section by studying thermomechanical
a combined system formed by an environment and an amount of a hydrocarbon fuel at T0, exergy
p0. The object is to evaluate the work obtainable by allowing the fuel to react with oxygen
from the environment to produce the environmental components carbon dioxide and water,
each at its respective state in the environment. The chemical exergy is, by definition, the chemical exergy
maximum theoretical work that could be developed by the combined system. The sum of the
thermomechanical and chemical exergies is the total exergy associated with a given system
at a specified state, relative to a specified exergy reference environment.
CHEMICAL EXERGY OF A HYDROCARBON: CaHb
Consider a combined system formed by an environment and an amount of a hydrocarbon

fuel, CaHb. To help us visualize how work might be obtained through the reaction of the fuel
with environmental components, a fuel cell operating at steady state is included in the
combined system, as shown in Fig. 13.4. Referring to this figure, fuel enters the cell at tem-
perature T0 and pressure p0. At another location, oxygen enters from the environment.
1
Study of Chap. 7 is a prerequisite for this part of the chapter.
Work Boundary of
combined system
Boundary of the cell
CaHb
at
T0, p0
e
CO2 at T0, yCO p
2 0
e p
O2 at T0, yO 2 0 H2O at T0, yHe 2O p0
T0
Heat transfer
with environment
Environment at T0, p0
Figure 13.4 Illustration used to intro-

duce the fuel chemical exergy concept.
Assuming the environment consists of an ideal gas mixture, the oxygen would enter at its
condition within the environment: temperature T0 and partial pressure yeO2 p0, where yeO2 is the
mole fraction of the oxygen in the exergy reference environment. The fuel and oxygen react
completely within the cell to produce carbon dioxide and water vapor, which exit in sepa-
rate streams at their conditions within the environment: temperature T0 and the partial pres-
sures yeCO2 p0 and yeH2O p0, respectively. The reaction is given by
CaHb
aa
b O2 S aCO2
H2O
b b
(13.29)
4 2
For steady-state operation, the energy rate balance for a control volume enclosing the fuel
cell reduces to give
# #
# #
hF
aa
b hO2 ahCO2 hH2O
Wcv Qcv b b
(13.30)
nF nF 4 2
Kinetic and potential energy effects are regarded as negligible. Since
# the fuel cell is at steady
state, its volume does not change with time, so no portion of Wcv is required to displace the
environment. Thus, Eq. 13.30 gives the work developed by the combined system of system
plus environment. Heat transfer is assumed to occur with the environment only at tempera-
ture T0. An entropy rate balance for the control volume enclosing the fuel cell takes the form
# #
QcvnF
#

sF
aa
b sO2 asCO2 sH2O
#
b b scv
0 (13.31)
T0 4 2 nF
Eliminating the heat transfer rate between Eqs. 13.30 and 13.31 results in
#
# c hF
aa
b hO2 ahCO2 hH2O d
Wcv b b
nF 4 2
#
T0 c sF
aa
b sO2 asCO2 sH2O d T0 #
b b scv
(13.32)
4 2 nF
In Eq. 13.32, the specific enthalpy and entropy of the fuel are evaluated at T0 and p0.
The values of the specific enthalpies in the first underlined term can be determined know-
ing only the temperature T0. The specific entropies in the second underlined term can be
determined knowing the temperature, pressure, and composition of the environment. Ac-
cordingly, once the environment is specified, all enthalpy and entropy terms of Eq. 13.32
can be regarded as known and independent of the nature of the processes occurring within
#
the control volume. The term T0scv depends explicity on the nature of such processes,
#
however. In accordance with the second law, T0scv is positive whenever internal irre-
versibilities are present, vanishes in the limiting case of no irreversibilities, and is never
negative. The maximum theoretical value for the work developed is obtained when no
#
irreversibilities are present. Setting T0scv to zero in Eq. 13.32, the following expression
for the chemical exergy results
e ch c hF
aa
b hO2 ahCO2 hH2O d
b b
4 2
T0 c sF
aa
b sO2 asCO2 sH2O d
b b
(13.33)
4 2
The superscript ch is used to distinguish this contribution to the exergy magnitude from the
thermomechanical exergy introduced in Chap. 7.
WORKING EQUATIONS. For computational convenience, the chemical exergy given by

Eq. 13.33 can be written as Eq. 13.35 by replacing the specific entropy terms for O2, CO2,
and H2O using the following expression obtained by reduction of Eq. 6.21b
si 1T0, yei p0 2 si 1T0, p0 2 R ln yei (13.34)
The first term on the right is the absolute entropy at T0 and p0, and yei is the mole fraction of
component i in the environment.
Applying Eq. 13.34, Eq. 13.33 becomes
e ch c hF
aa
b hO2 ahCO2 hH2O1g2 d 1T0, p0 2
b b
4 2
T0 c sF
aa
b sO2 asCO2 sH2O1g2 d 1T0, p0 2
b b
4 2
(13.35)
1yeO2 2 a
b4

RT0 ln c d
1yeCO2 2 a 1yeH2O 2 b2
The specific enthalpy terms are determined using the enthalpies of formation for the re-
spective substances. The specific entropies appearing in the equation are absolute entropies
determined as described in Sec. 13.5. The logarithmic term normally contributes only a few
percent to the chemical exergy magnitude.
Equation 13.35 can be expressed alternatively in terms of the Gibbs functions of the re-
spective substances as
e ch c gF
aa
b gO2 agCO2 gH2O1g2 d 1T0, p0 2
b b
4 2

1y eO2 2 a
b4
(13.36)

RT0 ln c d
1y eCO2 2 a 1y eH2O 2 b2
The specific Gibbs functions are evaluated at the temperature T0 and pressure p0 of the en-
vironment. These terms can be determined with Eq. 13.28 as
g 1T0, p0 2 g f
3g 1T0, p0 2 g 1Tref , pref 2 4 (13.37)
where g of is the Gibbs function of formation. For the special case where T0 and p0 are the
same as Tref and pref, respectively, the second term on the right of Eq. 13.37 vanishes and the
specific Gibbs function is just the Gibbs function of formation. Finally, note that the under-
lined term of Eq. 13.36 can be written more compactly as G: the negative of the change
in Gibbs function for the reaction, Eq. 13.29, regarding each substance as separate at tem-
perature T0 and pressure p0.
CHEMICAL EXERGY OF OTHER SUBSTANCES
The method introduced above for evaluating the chemical exergy of pure hydrocarbons
also can be used in principle for substances other than hydrocarbons: The chemical exergy
is the maximum theoretical work that could be developed by a fuel cell into which a sub-
stance of interest enters at T0, p0 and reacts completely with environmental components to
produce environmental components. All environmental components involved enter and exit
the cell at their conditions within the environment. By describing the environment appro-
priately, this method can be applied to all substances of practical interest.2 In the follow-
ing discussion, we limit consideration to the compounds CO, H2O, N2, O2, and CO2, for
these participate in the elementary combustion reactions serving as the focus of the pres-
ent chapter. Of these five compounds, only carbon monoxide is not among the substances
present in the environment we have been considering. Let us take up the compounds in the
order listed.
Paralleling the development of Eq. 13.36 for the case of pure carbon monoxide, at
T0, p0, the reaction within the cell is CO
12 O2 S CO2, and the chemical exergy is
given by
1yeO2 2 12
CO 3gCO
2 gO2 gCO2 4 1T0, p0 2
RT0 ln c d
1
e ch (13.38)
yeCO2
If carbon monoxide is not pure but a component of an ideal gas mixture at T0, p0, each
component i of the mixture would enter the cell at temperature T0 and the respective
partial pressure yi p0. The contribution of carbon monoxide to the chemical exergy of
the mixture, per mole of CO, is then given by Eq. 13.38 with the mole fraction of car-
bon monoxide in the mixture, yCO, appearing in the numerator of the logarithmic term
that then reads ln 3yCO 1yeO2 2 12yeCO2 4. This consideration is important when evaluating the
exergy of combustion products involving carbon monoxide.
Next, consider the case of pure water at T0, p0. Water is present as a vapor within the
environment under present consideration but normally is a liquid when at T0, p0. Thus,
H2O (l) H2O(g)
water would enter the cell as a liquid at T0, p0 and exit as a vapor at T0, y eH2Op0, with no
at at cell reaction occurring. The chemical exergy is
T0, p0 T0, yHe 2O p0
H2O 3gH2O1l2 gH2O1g2 4 1T0, p0 2

RT0 ln a b
1
e ch (13.39)
yeH2O
T0
2
For further discussion see M. J. Moran, Availability Analysis: A Guide to Efficient Energy Use, ASME Press,
New York, 1989, pp. 169170.
13.7 Standard Chemical Exergy 659
Next, consider N2, O2, CO2, each pure at T0, p0. Nitrogen, oxygen, and carbon dioxide N2 N2
are present within the environment, and normally are gases when at T0, p0. For each at at
T0, p0 T0, yeN2 p0
case, the gas would enter the cell at T0, p0 and exit at T0, yep0, where ye is the mole
fraction of N2, O2, or CO2 in the environment, as appropriate. No cell reaction would
occur. The chemical exergy is given simply by a logarithmic term of the form
T0
e ch RT0 ln a e b
1
(13.40)
y
Finally, for an ideal gas mixture at T0, p0 consisting only of substances present as gases
in the environment, the chemical exergy is obtained by summing the contributions of
each of the components. The result, per mole of mixture, is
e ch RT0 a yi ln a e b
yi
(13.41a)
i yi
where yi and y ei denote, respectively, the mole fraction of component i in the mixture at
T0, p0 and in the environment. Expressing the logarithmic term as 1ln11y ei 2
ln yi 2 and
introducing Eq. 13.40 for each gas, Eq. 13.41a can be written alternatively as
e ch a yi e ch
i
RT0 a yi ln yi (13.41b)
i i
The development of Eqs. 13.38 through 13.41 is left as an exercise. Subsequent examples
and end-of-chapter problems illustrate their use.

13.7 Standard Chemical Exergy
The exergy reference environments used thus far to calculate exergy values are adequate for
a wide range of practical applications, including combustion. However, for many cases of
interest the environment must be extended to include other substances. In applications in-
volving coal, for example, sulfur dioxide or some other sulfur-bearing compound would gen-
erally appear among the environmental components. Furthermore, once the environment is
determined, a series of calculations would be required to obtain exergy values for the sub-
stances of interest. These complexities can be sidestepped by using a table of standard
chemical exergies.
Standard chemical exergy values are based on a standard exergy reference environment standard chemical exergy
exhibiting standard values of the environmental temperature T0 and pressure p0 such as
298.15 K and 1 atm, respectively. The exergy reference environment also consists of a set
of reference substances with standard concentrations reflecting as closely as possible
the chemical makeup of the natural environment. To exclude the possibility of develop-
ing work from interactions among parts of the environment, these reference substances must
be in equilibrium mutually.
The reference substances generally fall into three groups: gaseous components of the
atmosphere, solid substances from the Earths crust, and ionic and nonionic substances
from the oceans. A common feature of standard exergy reference environments is a gas
phase, intended to represent air, that includes N2, O2, CO2, H2O(g), and other gases. The
ith gas present in this gas phase is assumed to be at temperature T0 and the partial pressure
pei y ei p0.
Two alternative standard exergy reference environments are commonly used, called here
Model I and Model II. For each of these models, Table A-26 gives values of the standard
chemical exergy for several substances, in units of kJ/kmol, together with a brief description
of the underlying rationale. The methods employed to determine the tabulated standard chem-
ical exergy values are detailed in the references accompanying the tables. Only one of the
two models should be used in a particular analysis.
The use of a table of standard chemical exergies often simplifies the application of ex-
ergy principles. However, the term standard is somewhat misleading, for there is no one
specification of the environment that suffices for all applications. Still, chemical exergies
calculated relative to alternative specifications of the environment are generally in good
agreement. For a broad range of engineering applications, the convenience of using stan-
dard values generally outweighs the slight lack of accuracy that might result. In particular,
the effect of slight variations in the values of T0 and p0 about their standard values can be
neglected.
STANDARD CHEMICAL EXERGY OF A HYDROCARBON: CaHb
In principle, the standard chemical exergy of a substance not present in the environment can
be evaluated by considering an idealized reaction of the substance involving other substances
for which the chemical exergies are known. To illustrate this for the case of a pure hydro-
carbon fuel CaHb at T0, p0, refer to the control volume at steady state shown in Fig. 13.5
where the fuel reacts with oxygen to form carbon dioxide and liquid water according to
Eq. 13.29. All substances are assumed to enter and exit at T0, p0 and heat transfer occurs only
at temperature T0.
Assuming no irreversibilities, an exergy rate balance reads
0 # #
Qj
0 a c 1 d a # b a # b int
e ch F
aa
b e O2
T0 Wcv b ch
j Tj n F n F rev 4
CO2 a b e H2O1l2 Ed
b # 0
ae ch ch
2
where, as before, the subscript F denotes the fuel. Solving for the fuel chemical exergy, we
obtain
#
e F a # b
ae ch CO2
a b e H2O1l2 aa
b e O2
ch
Wcv b ch b ch
(13.42)
n F rev
int 2 2

Wcv
CaHb CO2
at T0, p0 at T0, p0
O2 H2O (l)
at T0, p0 at T0, p0 Figure 13.5 Reactor
used to introduce the stan-

dard chemical exergy of
T0 Qcv CaHb.
Paralleling the development of Eq. 13.32 for the case of Fig. 13.5, we also have
#
a # b int c hF
aa
b hO2 ahCO2 hH2O1l2 d 1T0, p0 2
Wcv b b
n F rev 4 2
T0 c sF
aa
b sO2 asCO2 sH2O1l2 d 1T0, p0 2
b b
(13.43)
4 2
The underlined term in Eq. 13.43 is recognized from Sec. 13.2 as the molar higher heat-
ing value HHV (T0, p0). Introducing Eq. 13.43 into Eq. 13.42, we have
F HHV1T0, p0 2 T0 c sF
aa
b sO2 asCO2 d 1T , p 2
b b
e ch s
4 2 H2O1l2 0 0
CO2
a b e H2O1l2 aa
b e O2
b ch b ch

ae ch (13.44a)
2 4
Equations 13.42 and 13.43 can be expressed alternatively in terms of molar Gibbs functions
as follows
F c gF
aa
b gO2 agCO2 d 1T , p 2
b b
e ch g
4 2 H2O1l2 0 0
CO2
a b e H2O1l2 aa
b e O2
b b ch

ae ch ch
(13.44b)
2 4
With Eqs. 13.44, the standard chemical exergy of the hydrocarbon CaHb can be calcu-
lated using the standard chemical exergies of O2, CO2, and H2O(l), together with selected
property data: the higher heating value and absolute entropies, or Gibbs functions. for
example. . . consider the case of methane, CH4, and T0 298.15 K (25C), p0 1 atm.
For this application we can use Gibbs function data directly from Table A-25, and standard
chemical exergies for CO2, H2O(l), and O2 from Table A-26 (Model II), since each source
corresponds to 298 K, 1 atm. With a 1, b 4, Eq. 13.44b gives 831,680 kJ/kmol. This
agrees with the value listed for methane in Table A-26 for Model II.
We conclude the present discussion by noting special aspects of Eqs. 13.44:

First, Eq. 13.44a requires the higher heating value and the absolute entropy of the fuel.
When data from property compilations are lacking, as in the cases of coal, char, and
fuel oil, the approach of Eq. 13.44a can be invoked using a measured or estimated
heating value and an estimated value of the fuel absolute entropy determined with
procedures discussed in the literature.3
Next, note that the first term of Eq. 13.44b involving the Gibbs functions has the same
form as the first term of Eq. 13.36, except here liquid water appears. Also, the first term
of Eq. 13.44b can be written more compactly as G: the negative of the change in
Gibbs function for the reaction.
Finally, note that only the underlined terms of Eqs. 13.44 require chemical exergy data
relative to the model selected for the exergy reference environment.
In Example 13.12 we compare the use of Eq. 13.36 and Eq. 13.44b for evaluating the
chemical exergy of a pure hydrocarbon fuel.
3
See, for example, A. Bejan, G. Tsatsaronis, and M. J. Moran, Thermal Design and Optimization,Wiley,
New York, 1996, Sec. 3.4.3.
EXAMPLE 13.12 Evaluating the Chemical Exergy of Octane
Determine the chemical exergy of liquid octane at 25C, 1 atm, in kJ/kg. (a) Using Eq. 13.36, evaluate the chemical exergy
for an environment consisting of a gas phase at 25C, 1 atm obeying the ideal gas model with the following composition on
a molar basis: N2, 75.67%; O2, 20.35%; H2O, 3.12%; CO2, 0.03%; other, 0.83%. (b) Evaluate the chemical exergy using
Eq. 13.44b and standard chemical exergies from Table A-26 (Model II).
SOLUTION
Known: The fuel is liquid octane.
Find: Determine the chemical exergy (a) using Eq. 13.36 relative to an environment consisting of a gas phase at 25C, 1 atm
with a specified composition, (b) using Eq. 13.44b and standard chemical exergies.

ech = (Wcv n F)max
Boundary of
combined system
Boundary of the cell
C8H18
at
T0, p0
Assumptions: As shown in Fig. E13.12, the environment for
e part (a) consists of an ideal gas mixture with the molar analysis:
CO2 at T0, yCO p
2 0
N2, 75.67%; O2, 20.35%; H2O, 3.12%; CO2, 0.03%; other, 0.83%.
For part (b), Model II of Table A-26 applies.
e p
O2 at T0, yO 2 0 H2O at T0, yHe 2O p0
Environment:
T0 = 25C T0
p0 = 1 atm
e
yN2 = 0.7567
yOe
= 0.2035 Heat transfer
2
yHe 2O(g) = 0.0312 with environment
e
yCO 2
= 0.0003
Figure E13.12
Analysis: Complete combustion of liquid octane with O2 is described by

C8H18 1l2
12.5O2 S 8CO2
9H2O
(a) For this reaction equation, Eq. 13.36 takes the form
e ch 3gC8H181l2
12.5 gO2 8 gCO2 9 gH2O 1g2 4 1T0, p0 2
1yeO2 2 12.5

RT0 ln c d
1yeCO2 2 8 1yeH2O 1g2 2 9
Since T0 Tref and p0 pref, the required specific Gibbs functions are just the Gibbs functions of formation from Table
A-25. With the given composition of the environment and data from Table A-25, the above equation gives
e ch 36610
12.5102 81394,3802 91228,5902 4
10.20352 12.5

8.3141298.152 ln c d
10.00032 8 10.03122 9
5,218,960
188,883 5,407,843 kJ/kmol
Dividing by the molecular weight, the chemical exergy is obtained on a unit mass basis
5,407,843
ech 47,346 kJ/kg
114 .22
(b) Using coefficients from the reaction equation above, Eq. 13.44b reads
e ch 3 gC8H181l2
12.5 gO2 8 gCO2 9 gH2O1l2 4 1T0, p0 2

8 eCO
ch
2

9 eHch2O1l2 12.5 eOch2
With data from Table A-25 and Model II of Table A-26, the above equation gives
e ch 36610
12.5102 81394,3802 91237,1802 4

8119,8702
919002 12.5139702
5,296,270
117,435 5,413,705 kJ/kmol
As expected, this agrees closely with the value listed for octane in Table A-26 (Model II). Dividing by the molecular weight,
the chemical exergy is obtained on a unit mass basis
5,413,705
ech 47,397 kJ/kg
114.22
The chemical exergies determined with the two approaches used in parts (a) and (b) closely agree.
A molar analysis of the environment of part (a) on a dry basis reads, O2: 21%, N2, CO2 and the other dry components:
79%. This is consistent with the dry air analysis used throughout the chapter. The water vapor present in the assumed en-
vironment corresponds to the amount of vapor that would be present were the gas phase saturated with water at the spec-
ified temperature and pressure.
The value of the logarithmic term of Eq. 13.36 depends on the composition of the environment. In the present case, this
term contributes about 3% to the magnitude of the chemical exergy. The contribution of the logarithmic term is usually
small. In such instances, a satisfactory approximation to the chemical exergy can be obtained by omitting the term.
The terms of Eqs. 13.36 and 13.44b involving the Gibbs functions have the same form, except gH2O appears in Eq. 13.36
for water vapor and in Eq. 13.44b for liquid water.
STANDARD CHEMICAL EXERGY OF OTHER SUBSTANCES
By paralleling the development given above for hydrocarbon fuels leading to Eq. 13.44b, we
can in principle determine the standard chemical exergy of any substance not present in the
environment. With such a substance playing the role of the fuel in the previous development,
we consider a reaction of the substance involving other substances for which the standard
chemical exergies are known, and write
e ch G
a ne ch a ne ch (13.45)
P R
where G is the change in Gibbs function for the reaction, regarding each substance as sep-
arate at temperature T0 and pressure p0. The underlined term corresponds to the underlined
term of Eq. 13.44b and is evaluated using the known standard chemical exergies, together
with the ns giving the moles of these reactants and products per mole of the substance whose
chemical exergy is being evaluated.
for example. . . consider the case of ammonia, NH3, and T0 298.15 K (25C),
p0 1 atm. Letting NH3 play the role of the hydrocarbon in the development leading to
Eq. 13.44b, we can consider any reaction of NH3 involving other substances for which the
standard chemical exergies are known. For the reaction
NH3
34O2 S 12N2
32H2O
Eq. 13.45 takes the form
NH3 3gNH3
4 gO2 2 gN2 2 gH2O1l2 4 1T0, p0 2
3 1 3
e ch

12 e ch
N2
2 e H2O1l2 4 e O2
3 ch 3 ch
Using Gibbs function data from Table A-25, and standard chemical exergies for O2, N2, and
NH3 337,910 kJ/kmol. This agrees closely with the
H2O(l) from Table A-26 (Model II), e ch
value for ammonia listed in Table A-26 for Model II.
Finally, note that Eq. 13.41b is valid for mixtures containing gases other than those pres-
ent in the reference environment, for example gaseous fuels. This equation also can be applied
to mixtures (and solutions) that do not adhere to the ideal gas model. In all such applica-
tions, the terms e ch
i are selected from a table of standard chemical exergies.

13.8 Exergy Summary
The exergy associated with a specified state of a system is the sum of two contributions: the
thermomechanical contribution introduced in Chap. 7 and the chemical contribution intro-
duced in this chapter. On a unit mass basis, the total exergy is
V2
total exergy e 1u u0 2
p0 1v v0 2 T0 1s s0 2

gz
ech (13.46)
2
where the underlined term is the thermomechanical contribution (Eq. 7.9) and ech is the chem-
ical contribution evaluated as in Sec. 13.6 or 13.7. Similarly, the specific flow exergy asso-
ciated with a specified state is the sum
V2
ef h h0 T0 1s s0 2

gz
ech (13.47)
2
where the underlined term is the thermomechanical contribution (Eq. 7.20) and ech is the
chemical contribution.
When evaluating the thermomechanical contributions, we can think of bringing the system
without change in composition from the specified state to T0, p0, the condition where the sys-
tem is in thermal and mechanical equilibrium with the environment. Depending on the nature
of the system, this may be a hypothetical condition.
When a difference in exergy or flow exergy between states of the same composition is
evaluated, the chemical contribution cancels, leaving just the difference in the thermome-
chanical contributions. For such a calculation, it is unnecessary to evaluate the chemical ex-
ergy explicitly. However, for many evaluations it is necessary to account explicitly for the
chemical exergy contribution. This is brought out in subsequent examples.
ILLUSTRATIONS
The following two examples illustrate the exergy principles considered above. In Exam-
ple 13.13, Eq. 13.47 is applied to evaluate the specific flow exergy of a steam leak.
13.8 Exergy Summary 665
EXAMPLE 13.13 Evaluating the Flow Exergy of a Steam Leak
Steam at 5 bar, 240C leaks from a line in a vapor power plant. Evaluate the flow exergy of the steam, in kJ/kg, relative to
an environment at 25C, 1 atm in which the mole fraction of water vapor is yHe 2O 0.0303.
SOLUTION
Known: Water vapor at a known state is specified. The environment is also described.
Find: Determine the flow exergy of the water vapor, in kJ/kg.
Assumptions:
1. The environment consists of a gas phase that obeys the ideal gas model. The mole fraction of water vapor in the environ-
ment is 0.0303.
2. Neglect the effects of motion and gravity.
Analysis: With assumption 2, the specific flow exergy is given by Eq. 13.47 as
ef 1h h0 2 T0 1s s0 2
ech
The underlined term is the thermomechanical contribution to the flow exergy, evaluated as in Chap. 7. With data from the
steam tables, and noting that water is a liquid at T0, p0
h h0 T0 1s s0 2 12939.9 104.92 29817.2307 0.36742

789.7 kJ/kg
where h0 and s0 are approximated as the saturated liquid values at T0.

The chemical exergy contribution to the flow exergy relative to the specified environment is evaluated using Eq. 13.39.
With data from Table A-25
e 3 gH2O1l2 gH2O1g2 4 1T0, p0 2

RT0 ln a e b f
1 1
ech
M yH2O
e 3 237,180 1228,5902 4
18.314212982 ln a bf
1 1

18 0.0303
73.1 kJ/kmol
4.1 kJ/kg
18 kg/kmol
Adding the thermomechanical and chemical contributions, the flow exergy of steam at the specified state is
ef 789.7
4.1 793.8 kJ/kg
In this case, the chemical exergy contributes less than 1% to the total flow exergy magnitude.
In Example 13.14, we evaluate the flow exergy of combustion products.
EXAMPLE 13.14 Evaluating the Flow Exergy of Combustion Products
Methane gas enters a reactor and burns completely with 140% theoretical air. Combustion products exit as a mixture at tem-
perature T and a pressure of 1 atm. For T 480 and 1560 K, evaluate the flow exergy of the combustion products, in kJ per
kmol of fuel. Perform calculations relative to an environment consisting of an ideal gas mixture at 25C, 1 atm with the molar
analysis, y eN2 0.7567, y eO2 0.2035, y eH2O 0.0303, y eCO2 0.0003.
SOLUTION
Known: Methane gas reacts completely with 140% of the theoretical amount of air. Combustion products exit the reactor at
1 atm and a specified temperature. The environment is also specified.
Find: Determine the flow exergy of the combustion products, in Btu per lbmol of fuel, for each of two given temperatures.
Assumptions:
1. The combustion products are modeled as an ideal gas mixture at all states considered.
2. Neglect the effects of motion and gravity.
Analysis: For 140% theoretical air, the reaction equation for complete combustion of methane is
CH4
2.81O2
3.76N2 2 S CO2
2H2O
10.53N2
0.8O2
The flow exergy is given by Eq. 13.47, which involves chemical and thermomechanical contributions. Since the com-
bustion products form an ideal gas mixture when at T0, p0 (assumption 1) and each component is present within the en-
vironment, the chemical exergy contribution, per mole of fuel, is obtained from the following expression patterned after
Eq. 13.41a
yCO2 yH2O yN2 yO2
e ch RT0 c 1 ln a b
2 ln a b
10.53 ln a b
0.8 ln a bd
y eCO2 y eH2O y eN2 y eO2
From the reaction equation, the mole fractions of the components of the products are yCO2 0.0698, yH2O 0.1396, yN2
0.7348, yO2 0.0558. Substituting these values together with the respective environmental mole fractions, we obtain
e ch 17,750 kJ per kmol of fuel.
Applying ideal gas mixture principles, the thermomechanical contribution to the flow exergy, per mole of fuel, is
h h0 T0 1s s0 2 3h1T 2 h1T0 2 T0 1s1T 2 s1T0 2 R ln1yCO2 pyCO2 p0 22 4 CO2

2 3h1T 2 h1T0 2 T0 1s1T 2 s1T0 2 R ln1yH2O pyH2O p0 22 4 H2O

10.533h1T 2 h1T0 2 T0 1s1T 2 s1T0 2 R ln1yN2 pyN2 p0 22 4 N2

0.83h1T 2 h1T0 2 T0 1s1T 2 s1T0 2 R ln1yO2 pyO2 p0 22 4 O2
Since p p0, each of the logarithm terms drop out, and with h and s data at T0 from Table A-23, the thermomechanical
contribution reads
h h0 T0 1s s0 2 3h1T 2 9364 2981s1T 2 213.6852 4 CO2

2 3h1T 2 9904 2981s1T 2 188.722 4 H2O

10.533 h1T 2 8669 2981s1T 2 191.5022 4 N2

0.8 3h1T 2 8682 2981s1T 2 205.0332 4 O2
Then, with h and s from Table A-23 at T 480 and 1560K, respectively, the following results are obtained
T 480 K: h h0 T0 1s s0 2 17,712 kJ per kmol of fuel
T 1560 K: h h0 T0 1s s0 2 390, 853 kJ per kmol of fuel
Adding the two contributions, the flow exergy of the combustion products at each of the specified states is
T 480 K: ef 35,462 kJ per kmol of fuel
T 1560 K: ef 408,603 kJ per kmol of fuel
This is a hypothetical state for the combustion products because condensation of some of the water vapor present would
occur were the products brought to T0, p0. An exergy evaluation explicitly taking such condensation into account is con-
sidered in Bejan, Tsatsaronis and Moran, Thermal Design and Optimization, p. 129, p. 138.
The chemical contribution to the flow exergy is relatively unimportant in the higher-temperature case, amounting only
to about 4% of the flow exergy. Chemical exergy accounts for about half of the exergy in the lower-temperature case,
however.
13.9 Exergetic (Second Law) Efficiencies of Reacting Systems 667

13.9 Exergetic (Second Law) Efficiencies
of Reacting Systems
Devices designed to do work by utilization of a combustion process, such as vapor and gas
power plants and internal combustion engines, invariably have irreversibilities and losses as-
sociated with their operation. Accordingly, actual devices produce work equal to only a frac-
tion of the maximum theoretical value that might be obtained in idealized circumstances. The
vapor power plant exergy analysis of Sec. 8.6 and the combined cycle exergy analysis of
Example 9.13 provide illustrations.
The performance of devices intended to do work can be evaluated as the ratio of the actual
work developed to the maximum theoretical work. This ratio is a type of exergetic (second law)
efficiency. The relatively low exergetic efficiency exhibited by many common power-producing
devices suggests that thermodynamically more thrifty ways of utilizing the fuel to develop power
might be possible. However, efforts in this direction must be tempered by the economic imper-
atives that govern the practical application of all devices. The trade-off between fuel savings and
the additional costs required to achieve those savings must be carefully weighed.
The fuel cell provides an illustration of a relatively fuel-efficient device. We noted previ-
ously (Sec. 13.4) that the chemical reactions in fuel cells are more controlled than the rapidly
occurring, highly irreversible combustion reactions taking place in conventional power-
producing devices. In principle, fuel cells can achieve greater exergetic efficiencies than many
such devices.
The example to follow illustrates the evaluation of an exergetic efficiency for an internal
combustion engine.
EXAMPLE 13.15 Exergetic Efficiency of an Internal Combustion Engine
Devise and evaluate an exergetic efficiency for the internal combustion engine of Example 13.4. For the fuel, use the chemi-
cal exergy value determined in Example 13.12(a).
SOLUTION
Known: Liquid octane and the theoretical amount of air enter an internal combustion engine operating at steady state in sep-
arate streams at 25C, 1 atm, and burn completely. The combustion products exit at 890 K. The power developed by the en-
gine is 37 kW, and the fuel mass flow rate is 1.8 103 kg/s.
Find: Devise and evaluate an exergetic efficiency for the engine using the fuel chemical exergy value determined in Exam-
ple 13.12(a).
Assumptions:
1. See the assumptions listed in the solution to Example 13.4.

2. The environment is the same as used in Example 13.12(a).
3. The combustion air enters at the condition of the environment.
Analysis: An exergy balance can be used in formulating an exergetic efficiency for the engine: At steady state, the rate at
which exergy enters the engine equals the rate at which exergy exits plus the rate at which exergy is destroyed within the en-
gine. As the combustion air enters at the condition of the environment, and thus with zero exergy, exergy enters the engine
only with the fuel. Exergy exits the engine accompanying heat and work, and with the products of combustion.
If the power developed is taken to be the product of the engine, and the heat transfer and exiting product gas are regarded
as losses, an exergetic efficiency expression that gauges the extent to which the exergy entering the engine with the fuel is
converted to the product is
#
Wcv
e #
EF
#
where EF denotes the rate at which exergy enters with the fuel.
Since the fuel enters the engine at 25C and 1 atm, which correspond to the values of T0 and p0 of the environment,
and kinetic and potential energy effects are negligible, the exergy of the fuel is just the chemical exergy evaluated in
Example 13.12(a). There is no thermomechanical contribution. Thus
EF mF ech a1.8 10 3 b a47,346 b ` ` 85.2 kW

# # kg kJ 1 kW
s kg 1 kJ/s
The exergetic efficiency is then
ea b 0.434 143.4% 2

37 kW
85.2 kW
The waste heat from large engines may be utilizable by some other devicefor example, an absorption heat pump. In
such cases, some of the exergy accompanying heat transfer and the exiting product gas might be included in the numera-
tor of the exergetic efficiency expression. Since a greater portion of the entering fuel exergy would be utilized in such
arrangements, the value of would be greater than that evaluated in the solution.
In the next example, we evaluate an exergetic efficiency for a reactor.
EXAMPLE 13.16 Exergetic Efficiency of a Reactor
For the reactor of Example 13.9, determine the exergy destruction, in kJ per kmol of fuel, and devise and evaluate an exer-
getic efficiency. Consider (a) complete combustion with the theoretical amount of air (b) complete combustion with 400%
theoretical air. For the fuel, use the chemical exergy value determined in Example 13.12(a).
SOLUTION
Known: Liquid octane and air, each at 25C and 1 atm, burn completely in a well-insulated reactor operating at steady state.
The products of combustion exit at 1 atm pressure.
Find: Determine the exergy destruction, in kJ per kmol of fuel, and evaluate an exergetic efficiency for complete combus-
tion with (a) the theoretical amount of air, (b) 400% theoretical air.
Assumptions:
1. See assumptions listed in Example 13.9.

2. The environment is the same as that in Example 13.12(a).
3. The combustion air enters at the condition of the environment.
Analysis: An exergy balance can be used in formulating an exergetic efficiency: At steady state, the rate at which exergy
enters the reactor equals the rate at which exergy exits plus the rate at which exergy is destroyed within the reactor. Since the
combustion air enters at the condition of the environment, and thus with zero exergy, exergy enters the reactor only with the
#
fuel. The reactor is well insulated, so there is no exergy transfer accompanying heat transfer. There is also no work Wcv. Ac-
cordingly, exergy exits only with the combustion products. An exergetic efficiency can be written as
#
Eproducts
e #
EF
# #
where EF is the rate at which exergy enters with the fuel and Eproducts is the rate at which exergy exits with the combustion
products. Using the exergy balance for the reactor, given above in words, the exergetic efficiency expression can be written
alternatively as
# # #
EF Ed Ed
e # 1 #
EF EF
The exergy destruction term appearing in the last expression can be found from the relation
# #
Ed scv
# T0 #
nF nF
#
where T0 is the temperature of the environment and scv is the rate of entropy production. The rate of entropy production is
evaluated in the solution to Example 13.9 for each of the two cases. For the case of complete combustion with the theoretical
amount of air
#
# 1298 K2 a5404 b 1,610,392
Ed kJ kJ
nF #
kmol K kmol
Similarly, for the case of complete combustion with 400% of the theoretical amount of air
#
# 12982 197542 2,906,692
Ed kJ
nF kmol
Since the fuel enters the reactor at 25C, 1 atm, which correspond to the values of T0 and p0 of the environment, and ki-
netic and potential effects are negligible, the exergy of the fuel is just the chemical exergy evaluated in Example 13.12(a).
There is no thermomechanical contribution. Thus, for the case of complete combustion with the theoretical amount of air
0.702 170.2%2
1,610,392
e1
5,407,843
Similarly, for the case of complete combustion with 400% of the theoretical amount of air
0.463 146.3%2
2,906,692
e1
5,407,843
The calculated efficiency values show that a substantial portion of the fuel exergy is destroyed in the combustion process.
In the case of combustion with the theoretical amount of air, about 30% of the fuel exergy is destroyed. In the excess air
case, over 50% of the fuel exergy is destroyed. Further exergy destructions would take place as the hot gases are utilized.
It might be evident, therefore, that the overall conversion from fuel input to end use would have a relatively low exergetic
efficiency. The vapor power plant exergy analysis of Sec. 8.6 illustrates this point.
In this chapter we have applied the principles of thermody- products of combustion. The application of energy balances
namics to systems involving chemical reactions, with em- to reacting systems is then considered, including control vol-
phasis on systems involving the combustion of hydrocarbon umes at steady state and closed systems. To evaluate the spe-
fuels. We also have extended the notion of exergy to include cific enthalpies required in such applications, the enthalpy of
chemical exergy. formation concept is introduced and illustrated. The determi-
The first part of the chapter begins with a discussion of nation of the adiabatic flame temperature is considered as an
concepts and terminology related to fuels, combustion air, and application.
The use of the second law of thermodynamics is also dis- determine balanced reaction equations for the combus-
cussed. The absolute entropy concept is developed to provide tion of hydrocarbon fuels, including complete and
the specific entropies required by entropy balances for sys- incomplete combustion with various percentages of
tems involving chemical reactions. The related Gibbs func- theoretical air.
tion of formation concept is introduced. The first part of the apply energy balances to systems involving chemical
chapter also includes a discussion of fuel cells. reactions, including the evaluation of enthalpy using
In the second part of the chapter, we extend the exergy con- Eq. 13.9 and the evaluation of the adiabatic flame
cept of Chap. 7 by introducing chemical exergy. The standard temperature.
chemical exergy concept is also discussed. Means are developed
apply entropy balances to systems involving chemical
and illustrated for evaluating the chemical exergies of hydro-
reactions, including the evaluation of the entropy
carbon fuels and other substances. The presentation concludes
produced.
with a discussion of exergetic efficiencies of reacting systems.
The following list provides a study guide for this chapter. evaluate the chemical exergy of hydrocarbon fuels and
When your study of the text and end-of-chapter exercises has other substances using Eqs. 13.35 and 13.36, as well as
been completed, you should be able to the standard chemical exergy using Eqs. 13.44 and
13.45.
write out the meaning of the terms listed in the margin
apply exergy analysis, including chemical exergy and the
throughout the chapter and understand each of the re-
evaluation of exergetic efficiencies.
lated concepts. The subset of key concepts listed below
is particularly important.
complete dry product adiabatic flame chemical exergy p. 655

combustion p. 620 analysis p. 625 temperature p. 642 standard chemical
airfuel ratio p. 622 enthalpy of fuel cell p. 645 exergy p. 659
theoretical air p. 622 formation p. 630 absolute entropy p. 648
percent of theoretical heating values p. 639
air p. 623
1. In a balanced chemical reaction equation, is mass conserved? 10. Why are some high-efficiency, residential natural gas fur-
Are moles conserved? naces equipped with drain tubes?
2. If a hydrocarbon is burned with the theoretical amount of air, 11. For a given fuel, how would the adiabatic flame temperature
can the combustion be incomplete? vary if the percent of theoretical air were increased? Why?
3. If a hydrocarbon is burned with less than the theoretical 12. In which case would the adiabatic flame temperature be
amount of air, can the combustion be complete? higher, complete combustion of methane (CH4) with the theoret-
4. For the case of Example 13.1(b), is the airfuel mixture rich ical amount of oxygen (O2), or complete combustion with the
or lean? theoretical amount of air, all initially at 298 K, 1 atm?
5. What is the equivalence ratio for the reaction of Example 13.2? 13. Why is combustion inherently an irreversible process?
6. Why is the combustion of hydrocarbons considered a con- 14. What irreversibilities are present in the internal combustion
tributor to global warming? engine of Example 13.4? The combustion chamber of Example
7. When applying the energy balance to a reacting system, why 13.5?
is it essential that the enthalpies of each reactant and product be 15. What is an advantage of using standard chemical exergies?
evaluated relative to a common datum? A disadvantage?
8. Why are some enthalpy of formation values in Tables A-25 16. How might you define an exergetic efficiency for the
positive and others negative? hydrogenoxygen fuel cell of Fig. 13.3b
9. If you knew the higher heating value of a hydrocarbon, CaHb, 17. How might you define an exergetic efficiency for the reac-
how would you determine its lower heating value? tor of Example 13.5?
Working with Reaction Equations (O2), 1.4% nitrogen (N2), 5.8% sulfur, and the rest noncom-
13.1 A vessel contains a mixture of 60% O2 and 40% CO on a bustile ash. For complete combustion with the theoretical
mass basis. Determine the percent excess or percent deficiency amount of air, determine
of oxygen, as appropriate. (a) the amount of SO2 produced, in kg per kg of coal.
13.2 One hundred kmol of butane (C4H10) together with 4000 (b) the airfuel ratio on a mass basis.
kmol of air enter a furnace per unit of time. Carbon dioxide, 13.12 Octane (C8H18) burns completely with 120% of theoret-
carbon monoxide, and unburned fuel appear in the products of ical air. Determine
combustion exiting the furnace. Determine the percent excess
(a) the airfuel ratio on a molar and mass basis.
or percent deficiency of air, whichever is appropriate.
(b) the dew point temperature of the combustion products, in
13.3 Propane (C3H8) is burned with air. For each case, obtain C, when cooled at 1 atm.
the balanced reaction equation for complete combustion
13.13 Butane (C4H10) burns completely with 150% of theoret-
(a) with the theoretical amount of air. ical air. If the combustion products are cooled at 1 atm to tem-
(b) with 20% excess air. perature T, plot the amount of water vapor condensed, in kmol
(c) with 20% excess air, but only 90% of the propane being per kmol of fuel, versus T ranging from 20 to 60C.
consumed in the reaction.
13.14 A gaseous fuel mixture with a molar analysis of 72%
13.4 Methane (CH4) burns completely with the stiochiometric CH4, 9% H2, 14% N2, 2% O2, and 3% CO2 burns completely
amount of hydrogen peroxide (H2O2). Determine the balanced with moist air to form gaseous products at 1 atm consisting of
reaction equation. CO2, H2O, and N2 only. If the dew point temperature of the
13.5 A fuel mixture with the molar analysis 40% CH3OH, 50% products is 60C, determine the amount of water vapor pres-
C2H5OH, and 10% N2 burns completely with 33% excess air. ent in the combustion air, in kmol per kmol of fuel mixture.
Determine 13.15 Acetylene (C2H2) enters a torch and burns completely
(a) the balanced reaction equation. with 110% of theoretical air entering at 25C, 1 atm, 50%
(b) the airfuel ratio, both on a molar and mass basis. relative humidity. Obtain the balanced reaction equation, and
13.6 A natural gas with the molar analysis 78% CH4, 13% C2H6, determine the dew point temperature of the products, in C, at
6% C3H8, 1.7% C4H10, 1.3% N2 burns completely with 40% 1 atm.
excess air in a reactor operating at steady state. If the molar 13.16 Ethane (C2H6) enters a furnace and burns completely with
flow rate of the fuel is 0.5 kmol/h, determine the molar flow 130% of theoretical air entering at 25C, 85 kPa, 50% relative
rate of the air, in kmol/h. humidity. Determine
13.7 A fuel mixture with the molar analysis of 20% CH4, 40% (a) the balanced reaction equation.
H2, 40% NH3 burns completely with 150% of theoretical (b) the dew point temperature of the combustion products, in
oxygen. Determine the balanced reaction equation. C, at 85 kPa.
13.8 Coal with the mass analysis 77.54% C, 4.28% H, 1.46% S, 13.17 A liquid fuel mixture that is 40% octane (C8H18) and 60%
7.72% O, 1.34% N, 7.66% noncombustible ash burns com- decane (C10H22) by mass is burned completely with 10% ex-
pletely with 120% of theoretical air. Determine cess air at 25C, 1 atm, 80% relative humidity.
(a) the balanced reaction equation. (a) Determine the equivalent hydrocarbon composition, CaHb,
(b) the amount of SO2 produced, in kg per kg of coal. of a fuel that would have the same carbonhydrogen ratio
13.9 A coal sample has a mass analysis of 80.4% carbon, 3.9% on a mass basis as the fuel mixture.
hydrogen (H2), 5.0% oxygen (O2), 1.1% nitrogen (N2), 1.1% (b) If the combustion products are cooled to 25C at a pres-
sulfur, and the rest is noncombustible ash. For complete com- sure of 1 atm, determine the amount of water vapor that
bustion with 120% of the theoretical amount of air, determine condenses, in kg per kg of fuel mixture.
the airfuel ratio on a mass basis. 13.18 Carbon burns with 80% theoretical air yielding CO2, CO,
13.10 A sample of dried feedlot manure is being tested for use and N2 only. Determine
as a fuel. The mass analysis of the sample is 42.7% carbon, (a) the balanced reaction equation.
5.5% hydrogen (H2), 31.3% oxygen (O2), 2.4% nitrogen (N2), (b) the airfuel ratio on a mass basis.
0.3% sulfur, and 17.8% noncombustible ash. The sample is (c) the analysis of the products on a molar basis.
burned completely with 120% of theoretical air. Determine 13.19 Propane (C3H8) reacts with 80% of theoretical air to form
(a) the balanced reaction equation. products including CO2, CO, H2O, and N2 only. Determine
(b) the airfuel ratio on a mass basis. (a) the balanced reaction equation.
13.11 A sample of dried Appanoose County coal has a mass (b) the airfuel ratio on a mass basis.
analysis of 71.1% carbon, 5.1% hydrogen (H2), 9.0% oxygen (c) the analysis of the products on a dry molar basis.
13.20 Hexane (C6H14) burns with air to give products with the Applying the First Law to Reacting Systems
dry molar analysis of CO2, 11.5%; CO, 2.4%; O2, 2.0%; H2,
13.31 Propane (C3H8) at 25C, 1 atm enters a combustion cham-
1.6%; N2, 82.5%. Determine the airfuel ratio on a molar
ber operating at steady state and burns completely with the the-
basis.
oretical amount of air entering at the same conditions. If the
13.21 The components of the exhaust gas of a spark-ignition products exit at 25C, 1 atm, determine the rate of heat trans-
engine using a fuel mixture represented as C8H17 have a dry fer from the combustion chamber, in kJ per kmol of fuel.
molar analysis of 8.7% CO2, 8.9% CO, 0.3% O2, 3.7% H2, Kinetic and potential energy effects are negligible.
0.3% CH4, and 78.1% N2. Determine the equivalence ratio.
13.32 Methane gas (CH4) at 25C, 1 atm enters a steam gener-
13.22 Decane (C10H22) burns with 95% of theoretical air, pro- ator operating at steady state. The methane burns completely
ducing a gaseous mixture of CO2, CO, H2O, and N2. Determine with 140% of theoretical air entering at 127C, 1 atm. Prod-
(a) the airfuel ratio on a molar basis. ucts of combustion exit at 427C, 1 atm. In a separate stream,
(b) the analysis of the products on a dry molar basis. saturated liquid water enters at 8 MPa and exits as superheated
13.23 Butane (C4H10) burns with air, giving products having the vapor at 480C with a negligible pressure drop. If the vapor
dry molar analysis 11.0% CO2, 1.0% CO, 3.5% O2, 84.5% N2. mass flow rate is 3.7 105 kg/h, determine the volumetric
Determine flow rate of the methane, in m3/h.
13.33 Liquid ethanol (C2H5OH) at 25C, 1 atm enters a com-
(a) the percent theoretical air.
bustion chamber operating at steady state and burns with air
(b) the dew point temperature of the combustion products, in
entering at 227C, 1 atm. The fuel flow rate is 25 kg/s and
C, at 1 bar.
the equivalence ratio is 1.2. Heat transfer from the combus-
13.24 A fuel oil having an analysis on a mass basis of 85.7% tion chamber to the surroundings is at a rate of 3.75 105
C, 14.2% H, 0.1% inert matter burns with air to give products kJ/s. Products of combustion, consisting of CO2, CO, H2O(g),
with a dry molar analysis of 12.29% CO2; 3.76% O2; 83.95% and N2, exit. Ignoring kinetic and potential energy effects,
N2. Determine the airfuel ratio on a mass basis. determine
13.25 Ethyl alcohol (C2H5OH) burns with air. The product gas (a) the exit temperature, in K.
is analyzed and the laboratory report gives only the following (b) the airfuel ratio on a mass basis.
percentages on a dry molar basis: 6.9% CO2, 1.4% CO, 0.5%
C2H5OH. Assuming the remaining components consist of O2 13.34 Benzene gas (C6H6) at 25C, 1 atm enters a combustion
and N2, determine chamber operating at steady state and burns with 95%
theoretical air entering at 25C, 1 atm. The combustion prod-
(a) the percentages of O2 and N2 in the dry molar analysis. ucts exit at 1000 K and include only CO2, CO, H2O, and N2.
(b) the percent excess air. Determine the mass flow rate of the fuel, in kg/s, to provide
13.26 A fuel oil with the mass analysis 87% C, 11% H, 1.4% heat transfer at a rate of 1000 kW.
S, 0.6% inert matter burns with 120% of theoretical air. The 13.35 The energy required to vaporize the working fluid pass-
hydrogen and sulfur are completely oxidized, but 95% of the ing through the boiler of a simple vapor power plant is pro-
carbon is oxidized to CO2 and the remainder to CO. vided by the complete combustion of methane with 110% of
(a) Determine the balanced reaction equation. theoretical air. The fuel and air enter in separate streams at
(b) For the CO and SO2, determine the amount, in kmol per 25C, 1 atm. Products of combustion exit the stack at 150C,
106 kmol of combustion products (that is, the amount in 1 atm. Plot the mass flow rate of fuel required, in kg/h per MW
parts per million). of power developed by the plant versus the plant thermal effi-
13.27 Pentane (C5H12) burns with air so that a fraction x of the ciency, . Consider in the range 3040%. Kinetic and
carbon is converted to CO2. The remaining carbon appears as potential energy effects are negligible.
CO. There is no free O2 in the products. Develop plots of the 13.36 Methane (CH4) at 25C, enters the combustor of a sim-
airfuel ratio and the percent of theoretical air versus x, for x ple open gas turbine power plant and burns completely with
ranging from zero to unity. 400% of theoretical air entering the compressor at 25C, 1 atm.
13.28 For the following mixture, determine the equivalence Products of combustion exit the turbine at 577C, 1 atm. The
ratio and indicate if the mixture is lean or rich: rate of heat transfer from the gas turbine is estimated as 10%
of the net power developed. Determine the net power output,
1 kmol of butane (C4H10) and 32 kmol of air. in MW, if the fuel mass flow rate is 1200 kg/h. Kinetic and
13.29 Octane (C8H18) enters an engine and burns with air to potential energy effects are negligible.
give products with the dry molar analysis of CO2, 10.5%; CO, 13.37 Octane gas (C8H18) at 25C enters a jet engine and burns
5.8%; CH4, 0.9%; H2, 2.6%; O2, 0.3%; N2, 79.9%. Determine completely with 300% of theoretical air entering at 25C,
the equivalence ratio. 1 atm with a volumetric flow rate of 42 m3/s. Products of com-
13.30 Methane (CH4) burns with air to form products consist- bustion exit at 990 K, 1 atm. If the fuel and air enter with neg-
ing of CO2, CO, H2O, and N2 only. If the equivalence ratio is ligible velocities, determine the thrust produced by the engine
1.25, determine the balanced reaction equation. in kN.
13.38 Figure P13.38 provides data for a boiler and air preheater 13.45 For each of the following fuels, plot the adiabatic flame
operating at steady state. Methane (CH4) entering the boiler at temperature, in K, versus percent excess air for complete com-
25C, 1 atm is burned completely with 170% of theoretical air. bustion in a combustor operating at steady state. The reactants
Ignoring stray heat transfer and kinetic and potential energy enter at 25C, 1 atm.
effects, determine the temperature, in C, of the combustion (a) carbon.
air entering the boiler from the preheater. (b) hydrogen (H2).
(c) liquid octane (C8H18).
CH4 13.46 Propane gas (C3H8) at 25C, 1 atm enters an insulated re-
25C, 1 atm actor operating at steady state and burns completely with air
entering at 25C, 1 atm. Plot the adiabatic flame temperature
versus percent of theoretical air ranging from 100 to 400%.
T=? Why does the adiabatic flame temperature vary with increas-
Air ing combustion air?
25C, 1 atm
Preheater Boiler 13.47 Methane gas (CH4) at 25C, 1 atm enters an insulated re-
actor operating at steady state and burns completely with x%
Combustion 797C
gas at 662C
of theoretical air entering at 25C, 1 atm. Plot the adiabatic
flame temperature for x ranging from 100 to 400%.
13.48 Methane (CH4) at 25C, 1 atm, enters an insulated reac-
Feedwater Steam tor operating at steady state and burns with the theoretical
Figure P13.38 amount of air entering at 25C, 1 atm. The products contain
CO2, CO, H2O, O2, and N2, and exit at 2260 K. Determine the
13.39 A closed rigid vessel initially contains a gaseous mixture fractions of the entering carbon in the fuel that burn to CO2
at 25C, 1 atm with the molar analysis of 25% ethylene (C2H4), and CO, respectively.
75% oxygen (O2). The mixture burns completely and the prod- 13.49 Liquid methanol (CH3OH) at 25C, 1 atm enters an in-
ucts are cooled to 500 K. Determine the heat transfer between sulated reactor operating at steady state and burns completely
the vessel and its surroundings, in kJ per kmol of fuel present with air entering at 100C, 1 atm. If the combustion products
initially, and the final pressure, in atm. exit at 1256C, determine the percent excess air used. Neglect
13.40 A closed, rigid vessel initially contains a gaseous mix- kinetic and potential energy effects.
ture of 1 kmol of pentane (C5H12) and 150% of theoretical air
13.50 A mixture of gaseous octane (C8H18) and 200% of theo-
at 25C, 1 atm. If the mixture burns completely, determine the
retical air, initially at 25C, 1 atm, reacts completely in a rigid
heat transfer from the vessel, in kJ, and the final pressure, in
vessel.
atm, for a final temperature of 800 K.
13.41 Determine the enthalpy of combustion for gaseous bu- (a) If the vessel were well-insulated, determine the tempera-
tane (C4H10), in kJ per kmol of fuel and kJ per kg of fuel, at ture, in C, and the pressure, in atm, of the combustion
25C, 1 atm, assuming products.
(b) If the combustion products were cooled at constant vol-
(a) water vapor in the products. ume to 25C, determine the final pressure, in atm, and the
(b) liquid water in the products. heat transfer, in kJ per kmol of fuel.
13.42 Determine the higher heating value, in kJ per kmol of 13.51 A 5 103 kg sample of liquid benzene (C6H6) together
fuel and in kJ per kg of fuel, at 25C, 1 atm for with 20% excess air, initially at 25C and 1 atm, reacts com-
(a) liquid octane (C8H18). pletely in a rigid, insulated vessel. Determine the temperature,
(b) gaseous hydrogen (H2). in C, and the pressure, in atm, of the combustion products.
(c) liquid methanol (CH3OH).
(d) gaseous butane (C4H10). Applying the Second Law to Reacting Systems
Compare with the values listed in Table A-25. 13.52 Carbon monoxide (CO) at 25C, 1 atm enters an insu-
13.43 For a natural gas with a molar analysis of 86.5% CH4, 8% lated reactor operating at steady state and reacts completely
C2H6, 2% C3H8, 3.5% N2, determine the lower heating value, with the theoretical amount of air entering in a separate stream
in kJ per kmol of fuel and in kJ per kg of fuel, at 25C, 1 atm. at 25C, 1 atm. The products of combustion exit as a mixture
13.44 Liquid octane (C8H18) at 25C, 1 atm enters an insulated at 1 atm. For the reactor, determine the rate of entropy pro-
reactor operating at steady state and burns with 90% of theo- duction, in kJ/K per kmol of CO entering. Neglect kinetic and
retical air at 25C, 1 atm to form products consisting of CO2, potential energy effects.
CO, H2O, and N2 only. Determine the temperature of the ex- 13.53 Carbon monoxide (CO) reacts with water vapor in an
iting products, in K. Compare with the results of Example 13.8 insulated reactor operating at steady state to form hydrogen
and comment. (H2) and carbon dioxide (CO2). The products exit as a mixture
at 1 atm. For the reactor, determine the rate of entropy 13.59 Streams of methane (CH4) and oxygen (O2), each at 25C,
production, in kJ/K per kmol of carbon monoxide entering. 1 atm, enter a fuel cell operating at steady state. Streams of
Neglect kinetic and potential energy effects. Consider two carbon dioxide and water exit separately at 25C, 1 atm. If the
cases: fuel cell operates isothermally at 25C, 1 atm, determine the
(a) the carbon monoxide and water vapor enter the reactor is maximum theoretical work that it can develop, in kJ per kmol
separate streams, each at 400 K, 1 atm. of methane. Ignore kinetic and potential energy effects.
(b) the carbon monoxide and water vapor enter the reactor as 13.60 Streams of hydrogen (H2) and oxygen (O2), each at 1 atm,
a mixture at 400 K, 1 atm. enter a fuel cell operating at steady state and water vapor ex-
its at 1 atm. If the cell operates isothermally at (a) 300 K,
Explain why the answers in parts (a) and (b) differ. (b) 400 K, and (c) 500 K, determine the maximum theoretical
13.54 A gaseous mixture of butane (C4H10) and 80% excess air work that can be developed by the cell in each case, in kJ per
at 25C, 3 atm enters a reactor. Complete combustion occurs, kmol of hydrogen flowing, and comment. Heat transfer with
and the products exit as a mixture at 1200 K, 3 atm. Coolant the surroundings takes place at the cell temperature, and ki-
enters an outer jacket as a saturated liquid and saturated vapor netic and potential energy effects can be ignored.
exits at essentially the same pressure. No significant heat trans- 13.61 An inventor has developed a device that at steady state
fer occurs from the outer surface of the jacket, and kinetic and takes in liquid water at 25C, 1 atm with a mass flow rate of
potential energy effects are negligible. Determine for the jack- 4 kg/h and produces separate streams of hydrogen (H2) and
eted reactor oxygen (O2), each at 25C, 1 atm. The inventor claims that the
(a) the mass flow rate of the coolant, in kg per kmol of fuel. device requires an electrical power input of 14.6 kW when
(b) the rate of entropy production, in kJ/K per kmol of fuel. operating isothermally at 25C. Heat transfer with the sur-
(c) the rate of exergy destruction, in kJ per kmol of fuel, for roundings occurs, but kinetic and potential energy effects can
T0 25C. be ignored. Evaluate the inventors claim.
13.62 Coal with a mass analysis of 88% C, 6% H, 4% O, 1% N,
Consider each of two coolants: water at 1 bar and ammonia at
1% S burns completely with the theoretical amount of air.
10 bar.
Determine
13.55 Liquid ethanol (C2H5OH) at 25C, 1 atm enters a re-
(a) the amount of SO2 produced, in kg per kg of coal.
actor operating at steady state and burns completely with
(b) the airfuel ratio on a mass basis.
130% of theoretical air entering in a separate stream at 25C,
(c) For environmental reasons, it is desired to separate the SO2
1 atm. Combustion products exit at 227C, 1 atm. Heat trans-
from the combustion products by supplying the products
fer from the reactor takes place at an average surface tem-
at 340 K, 1 atm to a device operating isothermally at 340 K.
perature Tb. For Tb ranging from 25 to 200C, determine the
At steady state, a stream of SO2 and a stream of the re-
rate of exergy destruction within the reactor, in kJ per kmol
maining gases exit, each at 340 K, 1 atm. If the coal is
of fuel. Kinetic and potential energy effects are negligible.
burned at a rate of 10 kg/s, determine the minimum theo-
Let T0 25C.
retical power input required by the device, in kW. Heat
13.56 A gaseous mixture of ethane (C2H6) and the theoretical transfer with the surroundings occurs, but kinetic and
amount of air at 25C, 1 atm enters a reactor operating at steady potential energy effects can be ignored.
state and burns completely. Combustion products exit at 627C,
1 atm. Heat transfer from the reactor takes place at an average
Using Chemical Exergy
surface temperature Tb. For Tb ranging from 25 to 600C, de-
termine the rate of exergy destruction within the reactor, in kJ 13.63 For (a) carbon, (b) hydrogen (H2), (c) methane (CH4),
per kmol of fuel. Kinetic and potential energy effects are neg- (d) carbon monoxide, (e) liquid methanol (CH3OH), (f) nitro-
ligible. Let T0 25C. gen (N2), (g) oxygen (O2), (h) carbon dioxide, and (i) water,
determine the chemical exergy, in kJ/kg, relative to the fol-
13.57 Determine the change in the Gibbs function, in kJ per
lowing environment in which the gas phase obeys the ideal gas
kmol of methane, at 25C, 1 atm for CH4
2O2 S CO2
model:
2H2O, using
(a) Gibbs function of formation data.
(b) enthalpy of formation data, together with absolute entropy Environment
data. T0 298.15 K (25C), p0 1 atm
13.58 Separate streams of hydrogen (H2) and oxygen (O2) at Gas Phase: Component ye (%)
25C, 1 atm enter a fuel cell operating at steady state, and liquid
N2 75.67
water exits at 25C, 1 atm. The hydrogen flow rate is 2 104
O2 20.35
kmol/s. If the fuel cell operates isothermally at 25C, deter-
H2O(g) 3.12
mine the maximum theoretical power it can develop and the
CO2 0.03
accompanying rate of heat transfer, each in kW. Kinetic and
Other 0.83
potentially energy effects are negligible.
13.64 The accompanying table shows an environment consist- (a) relative to the environment of Problem 13.63.
ing of a gas phase and a condensed water phase. The gas phase (b) using data from Table A-26.
forms an ideal gas mixture. 13.70 A mixture having an analysis on a molar basis of 85%
dry air, 15% CO enters a device at 125C, 2.1 atm, and a ve-
Environment locity of 250 m/s. If the mass flow rate is 1.0 kg/s, determine
T0 298.15 K (25C), p0 1 atm the rate exergy enters, in kW. Neglect the effect of gravity. Per-
form calculations
Condensed Phase: H2O(l) at T0, p0
(a) relative to the environment of Problem 13.63.
Gas Phase: Component ye (%) (b) using data from Table A-26.
N2 75.67
Exergy Analysis of Reacting and
O2 20.35
Psychrometric Systems
H2O(g) 3.12
CO2 0.03 13.71 Carbon at 25C, 1 atm enters an insulated reactor oper-
Other 0.83 ating at steady state and reacts completely with the theoretical
amount of air entering separately at 25C, 1 atm. For the re-
actor, (a) determine the rate of exergy destruction, in kJ per
(a) Show that the chemical exergy of the hydrocarbon CaHb kmol of carbon, and (b) evaluate an exergetic efficiency. Per-
can be determined as form calculations relative to the environment of Problem 13.63.
Neglect the effects of motion and gravity.
e ch c gF
aa
b gO2 agCO2
b
13.72 Propane gas (C3H8) at 25C, 1 atm and a volumetric flow
4
1y eO2 2 a
b4
rate of 0.03 m3/min enters a furnace operating at steady state
gH2O 1l2 d
RT0 ln c d
b and burns completely with 200% of theoretical air entering at
2 1y eCO2 2 a 25C, 1 atm. Combustion products exit at 227C, 1 atm. The
furnace provides energy by heat transfer at 227C for an in-
(b) Using the result of part (a), repeat parts (a) through (c) of dustrial process. For the furnace, compare the rate of exergy
Problem 13.63. transfer accompanying heat transfer with the rate of exergy de-
13.65 Showing all important steps, derive (a) Eq. 13.38, struction, each in kJ/min. Let T0 25C and ignore kinetic
(b) Eq. 13.39 (c) Eq. 13.40, (d) Eqs. 13.41a, b (e) Eqs. and potential energy effects.
13.44 a, b. 13.73 Figure P13.73 shows a coal gasification reactor making
13.66 Using data from Tables A-25 and A-26, together with use of the carbonsteam process. The energy required for the
Eq. 13.45, determine the standard molar chemical exergy, in endothermic reaction is supplied by an electrical resistor. The
kJ/kmol, of reactor operates at steady state, with no stray heat transfers and
negligible kinetic and potential energy effects. Evaluate in Btu
(a) ammonia (NH3). per lbmol of carbon entering
(b) propane (C3H8).
(a) the required electrical input.
13.67 The chemical exergies of common hydrocarbons CaHb (b) the exergy entering with the carbon.
can be represented in terms of their respective lower heating (c) the exergy entering with the steam.
value, LHV, by an expression of the form (d) the exergy exiting with the product gas.
e ch (e) the exergy destruction within the reactor.
c1
c2 1ba2
c3a
1LHV2 Perform calculations relative to the environment of Problem
where c1, c2, and c3 are constants. Evaluate the constants rel- 13.63. Ignore kinetic and potential energy effects.
ative to the environment of Problem 13.63 to obtain an ex-
Electrical
pression valid for several selected (a) gaseous hydrocarbons, input
(b) liquid hydrocarbons.
13.68 Evaluate the specific flow exergy of water vapor, in kJ/kg,
at 200C, 1 bar. Neglect the effects of motion and gravity. Per- Carbon (T0, p0)
form calculations Product gas at
1700F, 1 atm
(a) relative to the environment of Problem 13.63. Water vapor at
(b) using data from Table A-26. 600F, 1 atm
13.69 Evaluate the specific flow exergy of an equimolar
mixture of oxygen (O2) and nitrogen (N2), in kJ/kg, at 20C,
C + 1.25H2O(g) CO + H2 + 0.25H2O(g)
1 atm. Neglect the effects of motion and gravity. Perform
calculations Figure P13.73
13.74 Carbon monoxide at 25C, 1 atm enters an insulated re- 13.78 Coal enters the combustor of a power plant with a mass
actor operating at steady state and reacts completely with the analysis of 49.8% C, 3.5% H, 6.8% O, 6.4% S, 14.1% H2O,
theoretical amount of air entering in a separate stream at 25C, and 19.4% noncombustible ash. The higher heating value of
1 atm. The products exit as a mixture at 1 atm. Determine in the coal is measured as 21,220 kJ/kg, and the lower heating
kJ per kmol of CO value on a dry basis, (LHV)d, is 20,450 kJ/kg. The following
expression can be used to estimate the chemical exergy of the
(a) the exergy entering with the carbon monoxide.
coal, in kJ/kg:
(b) the exergy exiting with the products.
(c) the rate of exergy destruction.
ech 1LHV2 d a1.0438
0.0013
0.1083
h o
Also, evaluate an exergetic efficiency for the reactor. Perform c c

0.0549 b
6740s
calculations relative to the environment of Problem 13.63. Ig- n
nore kinetic and potential energy effects. c
13.75 Liquid octane (C8H18) at 25C, 1 atm and a mass flow
where hc, oc, and nc denote, respectively, the mass ratio
rate of 0.57 kg/h enters a small internal combustion engine op-
of hydrogen to carbon, oxygen to carbon, and nitrogen to
erating at steady state. The fuel burns with air entering the en-
carbon, and s is the mass fraction of sulfur in kg per kg of
gine in a separate stream at 25C, 1 atm. Combustion products
fuel.4 The environment is closely the same as in Problem 13.64,
exit at 670 K, 1 atm with a dry molar analysis of 11.4% CO2,
but extended appropriately to account for the presence of sul-
2.9% CO, 1.6% O2, and 84.1% N2. If the engine develops
fur in the coal.
power at the rate of 1 kW, determine
(a) Using the above expression, calculate the chemical exergy
(a) the rate of heat transfer from the engine, in kW.
of the coal, in kJ/kg.
(b) an exergetic efficiency for the engine.
(b) Compare the answer of part (a) with the values that would
Use the environment of Problem 13.63 and neglect kinetic and result by approximating the chemical exergy with each of
potential energy effects. the measured heating values.
13.76 Evaluate an exergetic efficiency for the gas turbine power (c) What data would be required to determine the chemical
plant of Problem 13.36. Base exergy values on the environ- exergy in this case using the methodology of Sec. 13.6?
ment of Problem 13.63. Discuss.
13.77 Consider a furnace operating at steady state idealized as 13.79 For psychrometric applications such as those considered
shown in Fig. P13.77. The fuel is methane, which enters at in Chap. 12, the environment often can be modeled simply as
25C, 1 atm and burns completely with 200% theoretical air an ideal gas mixture of water vapor and dry air at temperature
entering at the same temperature and pressure. The furnace de- T0 and pressure p0. The composition of the environment is de-
livers energy by heat transfer at an average temperature of fined by the dry air and water vapor mole fractions yea, yev, re-
60C. Combustion products at 600 K, 1 atm are discharged to spectively. Show that relative to such an environment the flow
the surroundings. There are no stray heat transfers, and kinetic exergy of a moist air stream at temperature T and pressure p
and potential energy effects can be ignored. Determine in kJ with dry air and water vapor mole fractions ya and yv, re-
per kmol of fuel spectively, can be expressed on a molar basis as
ef T0 e 1yacpa
yvcpv 2 c a b
(a) the exergy entering the furnace with the fuel. T
(b) the exergy exiting with the products. T0
(c) the rate of exergy destruction.
1 ln a b d
R ln a b f
T p
Also, evaluate an exergetic efficiency for the furnace and com- T0 p0
ment. Perform calculations relative to the environment of

RT0 c ya ln a e b
yv ln a e b d
ya yv
Problem 13.63.
ya yv
where cpa and cpv denote the molar specific heats of dry air and
Combustion products water vapor, respectively. Neglect the effects of motion and
at 600 K, 1 atm gravity.
13.80 For each of the following, use the result of Problem 13.79
Methane to determine the specific flow exergy, in kJ/kg, relative to an
(T0, p0)
environment consisting of moist air at 20C, 1 atm, 100%
Heat transfer
Air Furnace (a) moist air at 20C, 1 atm, 100%.
(T0, p0) (b) moist air at 20C, 1 atm, 50%.
(c) dry air at 20C, 1 atm.
Temperature = 60C
Figure P13.77 4
Moran, Availability Analysis, pp. 192193.
13.1D The term acid rain is frequently used today. Define what Saturated mixture
is meant by the term. Discuss the origin and consequences of at 50C
acid rain. Also discuss options for its control.
13.2D Many observers have expressed concern that the release
of CO2 into the atmosphere due to the combustion of fossil fuels
is contributing to global warming. Write a paper reviewing the Liquid
scientific evidence regarding the contribution of fossil fuel water
combustion to global warming. Compare and contrast this ev- at
Spray heads 51C
idence with comparable data for the combustion of biomass fuel
derived from plant matter.
13.3D About 234 million tires are discarded in the U.S. annu- Direct-contact
condensing heat exchanger
ally, adding to a stockpile of two to three billion scrap tires
from previous years. Write a memorandum discussing the po- Feedwater Process steam
tential advantages and disadvantages of using scrap tires as a
fuel. How does the heating value of scrap tires compare with
the heating values of gasoline and commonly used coals? How
Baffles
does the ultimate analysis of scrap tires compare with the ul-
timate analysis of commonly used coals?
13.4D A coal with the following ultimate analysis: Natural gas,
3.85 m3/min Liquid
e f
75.8% C, 5.1% H, 8.2% O, 1.5% N, water
Boiler
1.6% S, 7.8% noncombustible ash at
16% 56C
is burned in a power plant boiler. If all of the sulfur present in Excess air
the combustible portion of the fuel forms SO2, determine if the
Combustion products
plant would be in compliance with regulations regarding sul- at 207C
fur emissions. Discuss options for removing SO2 from the stack
Figure P13.5D
gas. Assess the effectiveness of various technologies available
for this purpose and consider environmental problems
associated with them. 13.7D Figure P13.7D illustrates the schematic of an air preheater
13.5D Figure P13.5D shows a natural gasfired boiler for steam for the boiler of a coal-fired power plant. An alternative design
generation integrated with a direct-contact condensing heat ex- would eliminate the air preheater, supplying air to the furnace di-
changer that discharges warm water for tasks such as space rectly at 30C and discharging flue gas at 260C. All other fea-
heating, water heating, and combustion air preheating. For tures would remain unchanged. On the basis of thermodynamic
7200 h of operation annually, estimate the annual savings for and economic analyses, recommend one of the two options for
fuel, in dollars, by integrating these functions. What other cost further consideration. The analysis of the coal on a mass basis is
576% C, 5% H, 8% O, 11% noncombustible ash6
considerations would enter into the decision to install such a
condensing heat exchanger? Discuss.
13.6D A factory requires 3750 kW of electric power and high- The coal higher heating value is 26,000 kJ/kg. The molar analy-
quality steam at 107C with a mass flow rate of 2.2 kg/s. Two sis of the flue gas on a dry basis is
57.8% CO2, 1.2% CO, 11.4% O2, 79.6% N2 6
options are under consideration:
Option 1: A single boiler generates steam at 2.0 MPa, 320C,
13.8D Fuel or chemical leaks and spills can have catastrophic
supplying a turbine that exhausts to a condenser at 0.007
ramifications; thus the hazards associated with such events
MPa. Steam is extracted from the turbine at 107C, return-
must be well understood. Prepare a memorandum for one of
ing as a liquid to the boiler after use.
the following:
Option 2: A boiler generates steam at 2.0 MPa, 320C, sup-
(a) Experience with interstate pipelines shows that propane
plying a turbine that exhausts to a condenser at 0.007 MPa.
leaks are usually much more hazardous than leaks of nat-
A separate process steam boiler generates the required
ural gas or liquids such as gasoline. Why is this so?
steam at 107C, which is returned as a liquid to the boiler
(b) The most important parameter in determining the acciden-
after use.
tal rate of release from a fuel or chemical storage vessel is
The boilers are fired with natural gas and 20% excess air. For generally the size of the opening. Roughly how much faster
7200 h of operation annually, evaluate the two options on the would such a substance be released from a 1-cm hole than
basis of cost. from a 1-mm hole? What are the implications of this?
Saturated vapor, 30 bar,

m = 2 105 kg/h Feedwater, 50C
Flue gas, 260C

Flue gas,
Coal, 25C 150C
Air, 30C,
Boiler 1 atm, = 30%
Preheater
Ash, 450C,
cp = 1.0 kJ/kgK Figure P13.7D
13.9D By the year 2010, as much as 60,000 MW of electric tional power systems such as gas turbines, what should be
power could be generated worldwide by fuel cells. A step in the target installed cost for fuel cells? Discuss.
this direction has been taken at Santa Clara, California, where (d) What principal issues must be resolved for fuel cells to be
a 2-MW fuel cell demonstration power plant was installed un- widely used to power automobiles and trucks? Write a re-
der the auspices of a consortium of electric and gas utilities. port including at least three references.
Report on the Santa Clara demonstration project in a brief 13.10D Adapting procedures developed in the second part of
memorandum. Include a schematic of the system. For further this chapter, develop expressions for estimating the chemical
study of fuel cells: exergy for each of several common coal types in terms of the
(a) What are the principal features that make fuel cell tech- coal ultimate analysis and available thermodynamic data.
nology attractive for power generation? Is fuel cell per- 13.11D Airborne Soot Adds to Weather Woes, Some Say (see
formance limited by the Carnot efficiency? Discuss. box, Sec. 13.1). Investigate the underlying modeling assump-
(b) The types of fuel cells listed in Table 13.1 are considered tions and characteristics of computer simulations used to
to hold commercial promise. Investigate the specific predict global weather patterns. Write a report including at least
realms of application of these fuel cell types. Write a re- three references.
port including at least three references. 13.12D Goodbye Batteries, Hello Fuel Cells? (see box,
(c) Stack life and installed cost are two parameters considered Sec. 13.4). Investigate the advantages and disadvantages of
critical for fuel cell development. What is meant by stack hydrogen and methanol as fuels for fuel cell-powered
life and why is it important? What is the projected installed portable electronic devices. Write a report including at least
cost, in $ per kW, of current fuel cell technology for large- three references.
scale power generation? To be competitive with conven-
C
H
A
P
T
Chemical and
Phase Equilibrium R
E
14
E N G I N E E R I N G C O N T E X T The objective of the present chapter chapter objective
is to consider the concept of equilibrium in greater depth than has been done thus far. In
the first part of the chapter, we develop the fundamental concepts used to study chemical
and phase equilibrium. In the second part of the chapter, the study of reacting systems ini-
tiated in Chap. 13 is continued with a discussion of chemical equilibrium in a single phase.
Particular emphasis is placed on the case of reacting ideal gas mixtures. The third part of
the chapter concerns phase equilibrium. The equilibrium of multicomponent, multiphase,
nonreacting systems is considered and the phase rule is introduced.
EQUILIBRIUM FUNDAMENTALS
In this part of the chapter, fundamental concepts are developed that are useful in the study
of chemical and phase equilibrium. Among these are equilibrium criteria and the chemical
potential concept.

14.1 Introducing Equilibrium Criteria
A system is said to be in thermodynamic equilibrium if, when it is isolated from its sur- thermodynamic
roundings, there would be no macroscopically observable changes. An important requirement equilibrium
for equilibrium is that the temperature be uniform throughout the system or each part of the
system in thermal contact. If this condition were not met, spontaneous heat transfer from one
location to another could occur when the system was isolated. There must also be no un-
balanced forces between parts of the system. These conditions ensure that the system is in
thermal and mechanical equilibrium, but there is still the possibility that complete equilib-
rium does not exist. A process might occur involving a chemical reaction, a transfer of mass
between phases, or both. The object of this section is to introduce criteria that can be applied
to decide whether a system in a particular state is in equilibrium. These criteria are devel-
oped using the conservation of energy principle and the second law of thermodynamics as
discussed next.
679
680 Chapter 14 Chemical and Phase Equilibrium
Consider the case of a simple compressible system of fixed mass at which temperature
and pressure are uniform with position throughout. In the absence of overall system motion
and ignoring the influence of gravity, the energy balance in differential form (Eq. 2.36)
is
dU dQ dW
If volume change is the only work mode and pressure is uniform with position throughout
the system, W p dV. Introducing this in the energy balance and solving for Q gives
dQ dU
p dV
Since temperature is uniform with position throughout the system, the entropy balance in
differential form (Eq. 6.33) is
dQ
dS
ds
T
Eliminating Q between the last two equations
T dS dU p dV T ds (14.1)
Entropy is produced in all actual processes and conserved only in the absence of irre-
versibilities. Hence, Eq. 14.1 provides a constraint on the direction of processes. The only
processes allowed are those for which ds 0. Thus
T dS dU p dV 0 (14.2)
Equation 14.2 can be used to study equilibrium under various conditions. for
example. . . a process taking place in an insulated, constant-volume vessel, where dU
0 and dV 0, must be such that
S
Smax
dS4 U,V 0 (14.3)
Equation 14.3 suggests that changes of state of a closed system at constant internal energy
Fixed U, V
and volume can occur only in the direction of increasing entropy. The expression also im-
plies that entropy approaches a maximum as a state of equilibrium is approached. This is a
special case of the increase of entropy principle introduced in Sec. 6.5.5.
An important case for the study of chemical and phase equilibria is one in which tem-
Gibbs function perature and pressure are fixed. For this, it is convenient to employ the Gibbs function in
extensive form
G H TS U
pV TS
Forming the differential
dG dU
p dV
V dp T dS S dT
or on rearrangement
dG V dp
S dT 1T dS dU p dV 2
Except for the minus sign, the right side of this equation is the same as the expression ap-
pearing in Eq. 14.2. Accordingly, Eq. 14.2 can be written as
dG V dp
S dT 0 (14.4)
where the inequality reverses direction because of the minus sign noted above.
It can be concluded from Eq. 14.4 that any process taking place at a specified tempera- G Fixed T, p
ture and pressure (dT 0 and dp 0) must be such that
dG4 T,p 0 (14.5)

Gmin
This inequality indicates that the Gibbs function of a system at fixed T and p decreases dur-
ing an irreversible process. Each step of such a process results in a decrease in the Gibbs
function of the system and brings the system closer to equilibrium. The equilibrium state is
the one having the minimum value of the Gibbs function. Therefore, when
dG4 T,p 0 (14.6) equilibrium criterion
we have equilibrium. In subsequent discussions, we refer to Eq. 14.6 as the criterion for
equilibrium.
Equation 14.6 provides a relationship among the properties of a system when it is at an
equilibrium state. The manner in which the equilibrium state is reached is unimportant, how-
ever, for once an equilibrium state is obtained, a system exists at a particular T and p and no
further spontaneous changes can take place. When applying Eq. 14.6, therefore, we may spec-
ify the temperature T and pressure p, but it is unnecessary to require additionally that the
system actually achieves equilibrium at fixed T and fixed p.
14.1.1 Chemical Potential and Equilibrium

In the present discussion, the Gibbs function is considered further as a prerequisite for ap-
plication of the equilibrium criterion dG]T,p 0 introduced above. Let us begin by noting
that any extensive property of a single-phase, single-component system is a function of two
independent intensive properties and the size of the system. Selecting temperature and pres-
sure as the independent properties and the number of moles n as the measure of size, the
Gibbs function can be expressed in the form G G(T, p, n). For a single-phase, multicomp- multicomponent system
onent system, G may then be considered a function of temperature, pressure, and the num-
ber of moles of each component present, written G G(T, p, n1, n2, . . . , nj).
If each mole number is multiplied by , the size of the system changes by the same fac-
tor and so does the value of every extensive property. Thus, for the Gibbs function we may
write
aG 1T, p, n1, n2, . . . , nj 2 G 1T, p, an1, an2, . . . , anj 2
Differentiating with respect to while holding temperature, pressure, and the mole numbers
fixed and using the chain rule on the right side gives
0G 0G 0G
G n
n
# # #
01an1 2 1 0 1an2 2 2 0 1anj 2 j

n
This equation holds for all values of . In particular, it holds for 1. Setting 1, the
following expression results:
j
G a ni a b
0G
(14.7)
i1 0ni T, p,nl
where the subscript nl denotes that all ns except ni are held fixed during differentiation.
The partial derivatives appearing in Eq. 14.7 have such importance for our study of
chemical and phase equilibrium that they are given a special name and symbol. The
chemical potential of component i, symbolized by i, is defined as
mi a b
0G
chemical potential (14.8)
0ni T, p, nl
The chemical potential is an intensive property. With Eq. 14.8, Eq. 14.7 becomes
j
G a nimi (14.9)
i1
The equilibrium criterion given by Eq. 14.6 can be written in terms of chemical poten-
tials, providing an expression of fundamental importance for subsequent discussions of equi-
librium. Forming the differential of G(T, p, n1, . . . , nj) while holding temperature and pres-
sure fixed results in
j
dG4 T, p a a b
0G
dni
i1 0ni T, p, nl
The partial derivatives are recognized from Eq. 14.8 as the chemical potentials, so
j
dG4 T, p a mi dni (14.10)
i1
With Eq. 14.10, the equilibrium criterion dG]T,p 0 can be placed in the form
a mi dni 0 (14.11)
i1
Like Eq. 14.6, from which it is obtained, this equation provides a relationship among prop-
erties of a system when the system is at an equilibrium state where the temperature is T and
the pressure is p. Like Eq. 14.6, this equation applies to a particular state, and the manner
in which that state is attained is not important.
14.1.2 Evaluating Chemical Potentials

Means for evaluating the chemical potentials for two cases of interest are introduced in this
section: a single phase of a pure substance and an ideal gas mixture.
SINGLE PHASE OF A PURE SUBSTANCE. An elementary case considered later in this

chapter is that of equilibrium between two phases involving a pure substance. For a single
phase of a pure substance, Eq. 14.9 becomes simply
G nm
or
G
m g (14.12)
n
That is, the chemical potential is just the Gibbs function per mole.
IDEAL GAS MIXTURE. An important case for the study of chemical equilibrium is that of
an ideal gas mixture. The enthalpy and entropy of an ideal gas mixture are given by
j j
H a ni hi 1T 2 and S a ni si 1T, pi 2
i1 i1
where pi yi p is the partial pressure of component i. Accordingly, the Gibbs function takes
the form
j j
G H TS a ni hi 1T 2 T a ni si 1T, pi 2
i1 i1
j
a ni 3hi 1T 2 T si 1T, pi 2 4 1ideal gas2 (14.13)
i1
Introducing the molar Gibbs function of component i

gi 1T, pi 2 hi 1T 2 T si 1T, pi 2 1ideal gas2 (14.14)
Equation 14.13 can be expressed as
j
G a nigi 1T, pi 2 1ideal gas2 (14.15)
i1
Comparing Eq. 14.15 to Eq. 14.9 suggests that
mi gi 1T, pi 2 1ideal gas2 (14.16)
That is, the chemical potential of component i in an ideal gas mixture is equal to its Gibbs
function per mole of i, evaluated at the mixture temperature and the partial pressure of i in
the mixture. Equation 14.16 can be obtained formally by taking the partial derivative of
Eq. 14.15 with respect to ni, holding temperature, pressure, and the remaining ns constant,
and then applying the definition of chemical potential, Eq. 14.8.
The chemical potential of component i in an ideal gas mixture can be expressed in an
alternative form that is somewhat more convenient for subsequent applications. Using
Eq. 13.23, Eq. 14.14 becomes
mi hi 1T 2 T si 1T, pi 2
hi 1T 2 T as i 1T 2 R ln b
yi p
pref
hi 1T 2 T s i 1T 2
RT ln
yi p
pref
where pref is 1 atm and yi is the mole fraction of component i in a mixture at temperature T
and pressure p. The last equation can be written compactly as
1ideal gas2
yi p
mi g i
RT ln (14.17)
pref
where g i is the Gibbs function of component i evaluated at temperature T and a pressure of

1 atm. Additional details concerning the chemical potential concept are provided in Sec. 11.9.
Equation 14.17 is the same as Eq. 11.144 developed there.
CHEMICAL EQUILIBRIUM
In this part of the chapter, the equilibrium criterion dG]T,p 0 introduced in Sec. 14.1 is
used to study the equilibrium of reacting mixtures. The objective is to establish the
composition present at equilibrium for a specified temperature and pressure. An important
parameter for determining the equilibrium composition is the equilibrium constant. The equi-
librium constant is introduced and its use illustrated by several solved examples. The
discussion is concerned only with equilibrium states of reacting systems, and no information
can be deduced about the rates of reaction. Whether an equilibrium mixture would form
quickly or slowly can be determined only by considering the chemical kinetics, a topic that
is not treated in this text.

14.2 Equation of Reaction Equilibrium
In Chap. 13 the conservation of mass and conservation of energy principles are applied to
reacting systems by assuming that the reactions can occur as written. However, the extent to
which a chemical reaction proceeds is limited by many factors. In general, the composition
of the products actually formed from a given set of reactants, and the relative amounts of the
products, can be determined only from experiment. Knowledge of the composition that would
be present were a reaction to proceed to equilibrium is frequently useful, however. The equat-
ion of reaction equilibrium introduced in the present section provides the basis for determining
the equilibrium composition of a reacting mixture.
INTRODUCTORY CASE. Consider a closed system consisting initially of a gaseous mixture

of hydrogen and oxygen. A number of reactions might take place, including
1H2
12O2 S
d 1H2O (14.18)
1H2 S
d 2H (14.19)
1O2 S
d 2O (14.20)
Let us consider for illustration purposes only the first of the reactions given above, in
which hydrogen and oxygen combine to form water. At equilibrium, the system will consist
in general of three components: H2, O2, and H2O, for not all of the hydrogen and oxygen ini-
tially present need be reacted. Changes in the amounts of these components during each dif-
ferential step of the reaction leading to the formation of an equilibrium mixture are governed
by Eq. 14.18. That is
dnH2 dnH2O, dnO2 12 dnH2O (14.21a)
where dn denotes a differential change in the respective component. The minus signs signal
that the amounts of hydrogen and oxygen present decrease when the reaction proceeds to-
ward the right. Equations 14.21a can be expressed alternatively as
dnH2 dnO2 dnH2O
1 (14.21b)
1 2 1
which emphasizes that increases and decreases in the components are proportional to the sto-
ichiometric coefficients of Eq. 14.18.
Equilibrium is a condition of balance. Accordingly, as suggested by the direction of the
arrows in Eq. 14.18, when the system is at equilibrium, the tendency of the hydrogen and
oxygen to form water is just balanced by the tendency of water to dissociate into oxygen and
hydrogen. The equilibrium criterion dG]T,p 0 can be used to determine the composition at
14.2 Equation of Reaction Equilibrium 685

Iceland Aims to Be Fossil-Fuel Free hydrogen fuel cells.
The fuels cells will
The island nation of Iceland dares to dream about a future emit only water, and
in which all energy needs are met domestically from their thus also contribute to
abundant renewable hydroelectric and geothermal sources. Icelands societal goal
The key, Icelandic engineers say, is to take advantage of ex- of reducing green-
tra renewable capacity to make hydrogen that can be used house gas emissions.
to power cars, busses, and Icelands large fishing fleet, all While cars and
presently using petroleum-based fuels. This will free Iceland busses can store hy-
completely from the need to import fossil fuels and make this drogen fuel in special
nation of 276,000 people energy self-sufficient. Iceland then pressurized cylinders,
will be able to claim the title of being the worlds first storage on board fish-
hydrogen economy. ing vessels for cruises
Icelands fertilizer industry has long produced hydrogen lasting up to six weeks presents unique challenges. The best
on a large scale using electricity generated from renewable near-term solution, engineers say, is to use fuel cells running
sources to break down water through the process of on liquid methanol instead of hydrogen. They propose to syn-
electrolysis. By ramping up production, planners see all of the thesize methanol from hydrogen and the carbon dioxide and
countrys transportation needs eventually being met by carbon monoxide emitted from industrial plants.
an equilibrium state where the temperature is T and the pressure is p. This requires evalua-
tion of the differential dG]T,p in terms of system properties.
For the present case, Eq. 14.10 giving the difference in the Gibbs function of the mixture
between two states having the same temperature and pressure, but compositions that differ
infinitesimally, takes the following form:
dG4 T, p mH2 dnH2
mO2 dnO2
mH2O dnH2O (14.22)
The changes in the mole numbers are related by Eqs. 14.21. Hence
dG4 T, p 11mH2 12mO2
1mH2O 2 dnH2O
At equilibrium, dG]T,p 0, so the term in parentheses must be zero. That is
1mH2 12mO2
1mH2O 0
When expressed in a form that resembles Eq. 14.18, this becomes
1mH2
12mO2 1mH2O (14.23)
Equation 14.23 is the equation of reaction equilibrium for the case under consideration. The
chemical potentials are functions of temperature, pressure, and composition. Thus, the com-
position that would be present at equilibrium for a given temperature and pressure can be
determined, in principle, by solving this equation. The solution procedure is described in the
next section.
GENERAL CASE. The foregoing development can be repeated for reactions involving
any number of components. Consider a closed system containing five components, A, B,
C, D, and E, at a given temperature and pressure, subject to a single chemical reaction of
the form
nAA
nBB S
d nCC
nDD (14.24)
where the s are stoichiometric coefficients. Component E is assumed to be inert and thus
does not appear in the reaction equation. As we will see, component E does influence the
equilibrium composition even though it is not involved in the chemical reaction. The form
of Eq. 14.24 suggests that at equilibrium the tendency of A and B to form C and D is just
balanced by the tendency of C and D to form A and B.
The stoichiometric coefficients A, B, C, and D do not correspond to the respective
number of moles of the components present. The amounts of the components present are
designated nA, nB, nC, nD, and nE. However, changes in the amounts of the components
present do bear a definite relationship to the values of the stoichiometric coefficients.
That is
dnA dnB dnC dnD

(14.25a)
nA nB nC nD
where the minus signs indicate that A and B would be consumed when C and D are pro-
duced. Since E is inert, the amount of this component remains constant, so dnE 0.
Introducing a proportionality factor de, Eqs. 14.25a take the form
dnA dnB dnC dnD
de
nA nB nC nD
from which the following expressions are obtained:
dnA nA de, dnB nB de

(14.25b)
dnC nC de, dnD nD de
extent of reaction The parameter e is sometimes referred to as the extent of reaction.

For the system under present consideration, Eq. 14.10 takes the form
dG 4 T, p mA dnA
mB dnB
mC dnC
mD dnD
mE dnE
Introducing Eqs. 14.25b and noting that dnE 0, this becomes
dG 4 T, p 1nAmA nBmB
nC mC
nD mD 2 de
At equilibrium, dG]T,p 0, so the term in parentheses must be zero. That is
nAmA nBmB
nC mC
nDmD 0
or when written in a form resembling Eq. 14.24
equation of reaction
nAmA
nBmB nCmC
nDmD (14.26)
equilibrium
For the present case, Eq. 14.26 is the equation of reaction equilibrium. In principle, the
composition that would be present at equilibrium for a given temperature and pressure can
be determined by solving this equation. The solution procedure is simplified through the
equilibrium constant concept introduced in the next section.

14.3 Calculating Equilibrium Compositions
The objective of the present section is to show how the equilibrium composition of a system
at a specified temperature and pressure can be determined by solving the equation of reac-
tion equilibrium. An important part is played in this by the equilibrium constant.
14.3 Calculating Equilibrium Compositions 687
14.3.1 Equilibrium Constant for Ideal Gas Mixtures

The first step in solving the equation of reaction equilibrium, Eq. 14.26, for the equilibrium
composition is to introduce expressions for the chemical potentials in terms of temperature,
pressure, and composition. For an ideal gas mixture, Eq. 14.17 can be used for this purpose.
When this expression is introduced for each of the components A, B, C, and D, Eq. 14.26
becomes
nA ag A
RT ln b
nB ag B
RT ln b
yA p yB p
pref pref
nC ag C
RT ln b
nD ag D
RT ln b
yC p yD p
(14.27)
pref pref
where g i is the Gibbs function of component i evaluated at temperature T and the pressure
pref 1 atm. Equation 14.27 is the basic working relation for chemical equilibrium in a mix-
ture of ideal gases. However, subsequent calculations are facilitated if it is written in an
alternative form, as follows.
Collect like terms and rearrange Eq. 14.27 as
1nC g C
nD g D nAg A nBg B 2
RT anC ln b
yC p yD p yA p yB p

nD ln nA ln nB ln (14.28)
pref pref pref pref
The term on the left side of Eq. 14.28 can be expressed concisely as G. That is
G nC g C
nD g D nA g A nB g B (14.29a)
which is the change in the Gibbs function for the reaction given by Eq. 14.24 if each reac-
tant and product were separate at temperature T and a pressure of 1 atm. This expression can
be written alternatively in terms of specific enthalpies and entropies as
G nC 1hC T s C 2
nD 1hD T s D 2 nA 1hA T s A 2 nB 1hB T s B 2
1nChC
nDhD nAhA nBhB 2 T 1nC s C
nD s D nAs A nBs B 2 (14.29b)
Since the enthalpy of an ideal gas depends on temperature only, the hs of Eq. 14.29b are
evaluated at temperature T. As indicated by the superscript , each of the entropies is evalu-
ated at temperature T and a pressure of 1 atm.
Introducing Eq. 14.29a into Eq. 14.28 and combining the terms involving logarithms into
a single expression gives
n n
y CC y DD p nC
nD nA nB
ln c nA nB a b d
G
(14.30)
RT y A y B pref
Equation 14.30 is simply the form taken by the equation of reaction equilibrium, Eq. 14.26,
for an ideal gas mixture subject to the reaction Eq. 14.24. As illustrated by subsequent ex-
amples, similar expressions can be written for other reactions.
Equation 14.30 can be expressed concisely as
ln K1T 2
G
(14.31)
RT
where K is the equilibrium constant defined by
n n
y CC y DD p nC
nD nAnB
equilibrium constant K1T2 a b (14.32)
y nAA y nBB pref
Given the values of the stoichiometric coefficients, A, B, C, and D and the temperature
T, the left side of Eq. 14.31 can be evaluated using either of Eqs. 14.29 together with the ap-
propriate property data. The equation can then be solved for the value of the equilibrium con-
stant K. Accordingly, for selected reactions K can be evaluated and tabulated against temper-
ature. It is common to tabulate log10K or ln K versus temperature, however. A tabulation of
log10K values over a range of temperatures for several reactions is provided in Table A-27,
which is extracted from a more extensive compilation.
The terms in the numerator and denominator of Eq. 14.32 correspond, respectively, to the
products and reactants of the reaction given by Eq. 14.24 as it proceeds from left to right as
written. For the inverse reaction nCC
nDD S d nAA
nBB, the equilibrium constant takes
the form
y nAA y nBB p nA
nBnC nD
K* nC nD a b (14.33)
y C yD pref
Comparing Eqs. 14.32 and 14.33, it follows that the value of K* is just the reciprocal of K:
K* 1K. Accordingly,
log10 K* log10 K (14.34)
Hence, Table A-27 can be used both to evaluate K for the reactions listed proceeding in the
direction left to right and to evaluate K* for the inverse reactions proceeding in the direction
right to left.
Example 14.1 illustrates how the log10K values of Table A-27 are determined. Subsequent
examples show how the log10K values can be used to evaluate equilibrium compositions.
EXAMPLE 14.1 Evaluating the Equilibrium Constant at a Specified Temperature
Evaluate the equilibrium constant, expressed as log10K, for the reaction CO

12 O2 d
S CO2 at (a) 298 K and (b) 2000 K. Com-
pare with the value obtained from Table A-27.
SOLUTION
Known: The reaction is CO

12 O2 S
d CO2.
Find: Determine the equilibrium constant for T 298 K (25C) and T 2000 K.
Assumption: The ideal gas model applies.
Analysis: The equilibrium constant requires the evaluation of G for the reaction. Invoking Eq. 14.29b for this purpose,
we have
G 1hCO2 hCO 12 hO2 2 T 1s CO2 s CO 12 s O2 2
where the enthalpies are evaluated at temperature T and the absolute entropies are evaluated at temperature T and a pressure
of 1 atm. Using Eq. 13.13, the enthalpies are evaluated in terms of the respective enthalpies of formation, giving
0
G 3 1hf 2 CO2 1hf 2 CO 12 1hf 2 O2 4
3 1 h2 CO2 1 h2 CO 12 1h2 O2 4 T 1s CO2 s CO 12 s O2 2
where the h terms account for the change in specific enthalpy from Tref 298 K to the specified temperature T. The en-
thalpy of formation of oxygen is zero by definition.
(a) When T 298 K, the h terms of the above expression for G vanish. The required enthalpy of formation and absolute
entropy values can be read from Table A-25, giving
G 3 1393,5202 1110,5302 12 102 4 298 3213.69 197.54 12 1205.032 4
257,253 kJ/kmol
With this value for G, Eq. 14.31 gives
1257,253 kJ/kmol2
ln K 103.83
18.314 kJ/kmol # K2 1298 K2
which corresponds to log10K 45.093.
d CO
2 O2. That
1
Table A-27 gives the logarithm to the base 10 of the equilibrium constant for the inverse reaction: CO2 S
is, log10K* 45.066. Thus, with Eq. 14.34, log10K 45.066, which agrees closely with the calculated value.
(b) When T 2000 K, the h and s terms for O2, CO, and CO2 required by the above expression for G are evaluated
from Tables A-23. The enthalpy of formation values are the same as in part (a). Thus
G 3 1393,5202 1110,5302 12 102 4
3 1100,804 93642 165408 86692
12 167,881 86822 4 20003 309.210 258.600 12 1268.6552 4
282,990
5102
167,435 110,453 kJ/kmol
With this value, Eq. 14.31 gives
1110,4532
ln K 6.643
18.3142 120002
which corresponds to log10K 2.885.
At 2000 K, Table A-27 gives log10K* 2.884. With Eq. 14.34, log10K 2.884, which is in agreement with the calculated
value.
Using the procedures described above, it is straightforward to determine log10K versus temperature for each of several specified
reactions and tabulate the results as in Table A-27.
14.3.2 Illustrations of the Calculation of Equilibrium

Compositions for Reacting Ideal Gas Mixtures
It is often convenient to express Eq. 14.32 explicitly in terms of the number of moles that
would be present at equilibrium. Each mole fraction appearing in the equation has the form
yi nin, where ni is the amount of component i in the equilibrium mixture and n is the
total number of moles of mixture. Hence, Eq. 14.32 can be rewritten as
n CC n DD p pref nC
nDnAnB
n n
K a b (14.35)
n nAA n nBB n
The value of n must include not only the reacting components A, B, C, and D but also all
inert components present. Since inert component E has been assumed present, we would
write n nA
nB
nC
nD
nE.
Equation 14.35 provides a relationship among the temperature, pressure, and composition
of an ideal gas mixture at equilibrium. Accordingly, if any two of temperature, pressure, and
composition are known, the third can be found by solving this equation. for
example. . . suppose that the temperature T and pressure p are known and the object is
the equilibrium composition. With temperature known, the value of K can be obtained from
Table A-27. The ns of the reacting components A, B, C, and D can be expressed in terms
of a single unknown variable through application of the conservation of mass principle to
the various chemical species present. Then, since the pressure is known, Eq. 14.35 consti-
tutes a single equation in a single unknown, which can be solved using an equation solver
or iteratively with a hand calculator.
In Example 14.2, we apply Eq. 14.35 to study the effect of pressure on the equilibrium
composition of a mixture of CO2, CO, and O2.
EXAMPLE 14.2 Determining Equilibrium Composition Given Temperature and Pressure
One kilomole of carbon monoxide, CO, reacts with 12 kmol of oxygen, O2, to form an equilibrium mixture of CO2, CO, and
O2 at 2500 K and (a) 1 atm, (b) 10 atm. Determine the equilibrium composition in terms of mole fractions.
SOLUTION
Known: A system initially consisting of 1 kmol of CO and 12 kmol of O2 reacts to form an equilibrium mixture of CO2, CO,
and O2. The temperature of the mixture is 2500 K and the pressure is (a) 1 atm, (b) 10 atm.
Find: Determine the equilibrium composition in terms of mole fractions.
Assumption: The equilibrium mixture is modeled as an ideal gas mixture.
Analysis: Equation 14.35 relates temperature, pressure, and composition for an ideal gas mixture at equilibrium. If any two
are known, the third can be determined using this equation. In the present case, T and p are known, and the composition is
unknown.
Applying conservation of mass, the overall balanced chemical reaction equation is
O S zCO
O2
11 z2CO2
1 z
1CO
2 2 2
where z is the amount of CO, in kmol, present in the equilibrium mixture. Note that 0 z 1.
The total number of moles n in the equilibrium mixture is
2
z

11 z2
z
nz
2 2
Accordingly, the molar analysis of the equilibrium mixture is
2z z 211 z2
yCO , yO2 , yCO2
2
z 2
z 2
z
At equilibrium, the tendency of CO and O2 to form CO2 is just balanced by the tendency of CO2 to form CO and O2, so
d CO
2 O2. Accordingly, Eq. 14.35 takes the form
1
we have CO2 S
z1z22 1 2 ppref 1
1 21 1 2 p 1 2
c d a b a b
z z
K
11 z2 12
z2 2 1z 2
z pref
At 2500 K, Table A-27 gives log10K 1.44. Thus, K 0.0363. Inserting this value into the last expression
1 2 p 1 2
a b a b
z z
0.0363 (a)
1z 2
z pref
(a) When p 1 atm, Eq. (a) becomes
1 2
a b
z z
0.0363
1z 2
z
Using an equation solver or iteration with a hand calculator, z 0.129. The equilibrium composition in terms of mole fractions
is then
210.1292 0.129 211 0.1292
yCO 0.121, yO2 0.061, yCO2 0.818
2.129 2.129 2.129
(b) When p 10 atm, Eq. (a) becomes

1 2
a b 1102 12
z z
0.0363
1z 2
z
Solving, z 0.062. The corresponding equilibrium composition in terms of mole fractions is yCO 0.06, yO2 0.03,
yCO2 0.91.
Comparing the results of parts (a) and (b) we conclude that the extent to which the reaction proceeds toward completion
(the extent to which CO2 is formed) is increased by increasing the pressure.
It is left as an exercise to show that if the mole fraction of CO2 in the equilibrium mixture at 2500 K were 0.93, the cor-
responding pressure would be closely 22.4 atm.
In Example 14.3, we determine the temperature of an equilibrium mixture when the pres-
sure and composition are known.
EXAMPLE 14.3 Determining Equilibrium Temperature Given Pressure and Composition
Measurements show that at a temperature T and a pressure of 1 atm, the equilibrium mixture for the system of Example 14.2
has the composition yCO 0.298, yO2 0.149, yCO2 0.553. Determine the temperature T of the mixture, in K.
SOLUTION
Known: The pressure and composition of an equilibrium mixture of CO, O2, and CO2 are specified.
Find: Determine the temperature of the mixture, in K.
Assumption: The mixture can be modeled as an ideal gas mixture.
Analysis: Equation 14.35 relates temperature, pressure, and composition for an ideal gas mixture at equilibrium. If any two
are known, the third can be found using this equation. In the present case, composition and pressure are known, and the tem-
perature is the unknown.
Equation 14.35 takes the same form here as in Example 14.2. Thus, when p 1 atm, we have
1 2
K 1T 2 a b
z z
1z 2
z
where z is the amount of CO, in kmol, present in the equilibrium mixture and T is the temperature of the mixture.
The solution to Example 14.2 gives the following expression for the mole fraction of the CO in the mixture: yCO
2z(2
z). Since yCO 0.298, z 0.35.
Inserting this value for z into the expression for the equilibrium constant gives K 0.2078. Thus, log10K 0.6824.
Interpolation in Table A-27 then gives T 2881 K.
Comparing this example with part (a) of Example 14.2, we conclude that the extent to which the reaction proceeds to
completion (the extent to which CO2 is formed) is decreased by increasing the temperature.
In Example 14.4, we consider the effect of an inert component on the equilibrium

composition.
EXAMPLE 14.4 Considering the Effect of an Inert Component
One kilomole of carbon monoxide reacts with the theoretical amount of air to form an equilibrium mixture of CO2, CO, O2,
and N2 at 2500 K and 1 atm. Determine the equilibrium composition in terms of mole fractions, and compare with the result
of Example 14.2.
SOLUTION
Known: A system initially consisting of 1 kmol of CO and the theoretical amount of air reacts to form an equilibrium mix-
ture of CO2, CO, O2, and N2. The temperature and pressure of the mixture are 2500 K and 1 atm.
Find: Determine the equilibrium composition in terms of mole fractions, and compare with the result of Example 14.2.
Assumption: The equilibrium mixture can be modeled as an ideal gas mixture.
Analysis: For a complete reaction of CO with the theoretical amount of air

CO
12 O2
1.88N2 S CO2
1.88N2
Accordingly, the reaction of CO with the theoretical amount of air to form CO2, CO, O2, and N2 is
O
11 z2CO2
1.88N2
z
CO
12 O2
1.88N2 S zCO
2 2
where z is the amount of CO, in kmol, present in the equilibrium mixture.
The total number of moles n in the equilibrium mixture is
5.76
z

11 z2
1.88
z
nz
2 2
The composition of the equilibrium mixture in terms of mole fractions is
2z z 211 z2 3.76
yCO , yO2 , yCO2 , yN2
5.76
z 5.76
z 5.76
z 5.76
z
At equilibrium we have CO2 S
d CO
12 O2. So Eq. 14.35 takes the form
z1z22 1 2 p pref 1 2
K c d
11 z2 15.76
z2 2
The value of K is the same as in the solution to Example 14.2, K 0.0363. Thus, since p 1 atm, we have
1 2
a b
z z
0.0363
1 z 5.76
z
Solving, z 0.175. The corresponding equilibrium composition is yCO 0.059, yCO2 0.278, yO2 0.029, yN2 0.634.
Comparing this example with Example 14.2, we conclude that the presence of the inert component nitrogen reduces the
extent to which the reaction proceeds toward completion at the specified temperature and pressure (reduces the extent to which
CO2 is formed).
In the next example, the equilibrium concepts of this chapter are applied together with
the energy balance for reacting systems developed in Chap. 13.
EXAMPLE 14.5 Using Equilibrium Concepts and the Energy Balance
Carbon dioxide at 25C, 1 atm enters a reactor operating at steady state and dissociates, giving an equilibrium mixture of CO2,
CO, and O2 that exits at 3200 K, 1 atm. Determine the# heat transfer to the reactor, in kJ per kmol of CO2 entering. The effects
of kinetic and potential energy can be ignored and Wcv 0.
SOLUTION
Known: Carbon dioxide at 25C, 1 atm enters a reactor at steady state. An equilibrium mixture of CO2, CO, and O2 exits at
3200 K, 1 atm.
Find: Determine the heat transfer to the reactor, in kJ per kmol of CO2 entering.

Assumptions:

Qcv 1. The control volume shown on the accompanying sketch by a
#
dashed line operates at steady state with Wcv 0. Kinetic energy
and potential energy effects can be ignored.
CO2 (CO2, CO, O2) 2. The entering CO2 is modeled as an ideal gas.
25C, 1 atm 3200 K, 1 atm
3. The exiting mixture of CO2, CO, and O2 is an equilibrium ideal
gas mixture.
Figure E14.5
Analysis: The required heat transfer can be determined from an energy rate balance for the control volume, but first the
composition of the exiting equilibrium mixture must be determined.
Applying the conservation of mass principle, the overall dissociation reaction is described by
1z
CO2 S zCO2
11 z2 CO
a b O2
2
where z is the amount of CO2, in kmol, present in the mixture exiting the control volume, per kmol of CO2 entering. The total
number of moles n in the mixture is then
1z 3z
n z
11 z2
a b
2 2
The exiting mixture is assumed to be an equilibrium mixture (assumption 3). Thus, for the mixture we have
d CO
2 O2. Equation 14.35 takes the form
1
CO 2 S
11 z2 3 11 z2 24 1 2 p pref 1
1 21
K c d
z 13 z2 2
Rearranging and noting that p 1 atm
1 z 1 z 1 2
Ka ba b
z 3z
At 3200 K, Table A-27 gives log10K 0.189. Thus, K 0.647, and the equilibrium constant expression becomes
1 z 1 z 1 2
0.647 a ba b
z 3z
Solving, z 0.422. The composition of the exiting equilibrium mixture, in kmol per kmol of CO2 entering, is then (0.422CO2,
0.578CO, 0.289O2).
When expressed per kmol of CO2 entering the control volume, the energy rate balance reduces by assumption 1 to
# # 0

hCO2 10.422hCO2
0.578hCO
0.289hO2 2
Qcv Wcv
0 # #
nCO2 nCO2
Solving for the heat transfer per kmol of CO2 entering, and evaluating each enthalpy in terms of the respective enthalpy
of formation
# 0 0
0.4221hf
h2 CO2
0.5781hf
h2 CO
0.2891hf
h2 O2 1hf
h2 CO2
Qcv
#
nCO2
The enthalpy of formation of O2 is zero by definition; h for the CO2 at the inlet vanishes because CO2 enters at 25C.
With enthalpy of formation values from Tables A-25 and h values for O2, CO, and CO2, from Table A-23
#
0.422 3393,520
1174,695 93642 4
0.5783110,530
1109,667 86692 4
Qcv
#
nCO2

0.2891114,809 86822 1393,5202
322,385 kJ/kmol 1CO2 2
For comparison, let us determine the heat transfer if we assume no dissociationnamely, when CO2 alone exits the re-
actor. With data from Table A-23, the heat transfer is
#
hCO2 13200 K2 hCO2 1298 K2
Qcv
#
n CO2
174,695 9364 165,331 kJ/kmol 1CO2 2
The value is much less than the value obtained in the solution above because the dissociation of CO2 requires more energy
input (an endothermic reaction).
14.3.3 Equilibrium Constant for Mixtures and Solutions1

The procedures that led to the equilibrium constant for reacting ideal gas mixtures can be
followed for the general case of reacting mixtures by using the fugacity and activity con-
cepts introduced in Sec. 11.9. In principle, equilibrium compositions of such mixtures can
be determined with an approach paralleling the one for ideal gas mixtures.
Equation 11.141 can be used to evaluate the chemical potentials appearing in the equa-
tion of reaction equilibrium (Eq. 14.26). The result is
nA 1g A
RT ln aA 2
nB 1g B
RT ln aB 2 nC 1g C
RT ln aC 2
nD 1g D
RT ln aD 2
(14.36)
where g i is the Gibbs function of pure component i at temperature T and the pressure pref
1 atm, and ai is the activity of that component.
Collecting terms and employing Eq. 14.29a, Eq. 14.36 becomes
n n
ln a nA nB b
G a CC a DD
(14.37)
RT aA aB
This equation can be expressed in the same form as Eq. 14.31 by defining the equilibrium
constant as
n n
a CC a DD
K (14.38)
a nAA a nBB
Since Table A-27 and similar compilations are constructed simply by evaluating G RT
for specified reactions at several temperatures, such tables can be employed to evaluate the
more general equilibrium constant given by Eq. 14.38. However, before Eq. 14.38 can be
used to determine the equilibrium composition for a known value of K, it is necessary to
evaluate the activity of the various mixture components. Let us illustrate this for the case of
mixtures that can be modeled as ideal solutions.
1
This section requires study of Sec. 11.9.
14.4 Further Examples of the Use of the Equilibrium Constant 695
IDEAL SOLUTIONS. For an ideal solution, the activity of component i is given by

yi fi
ai (11.142)
f i
where fi is the fugacity of pure i at the temperature T and pressure p of the mixture, and f i
is the fugacity of pure i at temperature T and the pressure pref. Using this expression to eval-
uate aA, aB, aC, and aD, Eq. 14.38 becomes
1yC fC f C 2 nC 1yD fD f D 2 nD
K
1yA fA f A 2 nA 1yB fB f B 2 nB
(14.39a)
which can be expressed alternatively as

1 fC p2 nC 1 fDp2 nD 1 f Apref 2 nA 1 f B pref 2 nB y nCC y nDD p nC
nD nA nB
K c d c d c a b d
1 fAp2 nA 1 fBp2 nB 1 f C pref 2 nC 1 f Dpref 2 nD y nAA y nBB pref
(14.39b)
The ratios of fugacity to pressure in this equation can be evaluated, in principle, from
Eq. 11.124 or the generalized fugacity chart, Fig. A-6, developed from it. In the special case
when each component behaves as an ideal gas at both T, p and T, pref, these ratios equal unity
and Eq. 14.39b reduces to the underlined term, which is just Eq. 14.32.

14.4 Further Examples of the Use of the
Equilibrium Constant
Some additional aspects of the use of the equilibrium constant are introduced in this section:
the equilibrium flame temperature, the vant Hoff equation, and chemical equilibrium for
ionization reactions and simultaneous reactions. To keep the presentation at an introductory
level, only the case of ideal gas mixtures is considered.
14.4.1 Determining Equilibrium Flame Temperature

In this section, the effect of incomplete combustion on the adiabatic flame temperature, intro-
duced in Sec. 13.3, is considered using concepts developed in the present chapter. We begin with
a review of some ideas related to the adiabatic flame temperature by considering a reactor
operating at steady state for which no significant heat transfer with the surroundings takes place.
Let carbon monoxide gas entering at one location react completely with the theoretical
amount of air entering at another location as follows:
CO
12O2
1.88N2 S CO2
1.88N2
As discussed in Sec. 13.3, the products would exit the reactor at a temperature we have
designated the maximum adiabatic flame temperature. This temperature can be determined
by solving a single equation, the energy equation. At such an elevated temperature, however,
there would be a tendency for CO2 to dissociate
CO2 S CO
12O2
Since dissociation requires energy (an endothermic reaction), the temperature of the prod-
ucts would be less than the maximum adiabatic temperature found under the assumption of
complete combustion.
When dissociation takes place, the gaseous products exiting the reactor would not be CO2 and
N2, but a mixture of CO2, CO, O2, and N2. The balanced chemical reaction equation would read
CO
12 O2
1.88N2 S z CO
11 z2CO2
O2
1.88N2
z
(14.40)
2
where z is the amount of CO, in kmol, present in the exiting mixture for each kmol of CO
entering the reactor.
Accordingly, there are two unknowns: z and the temperature of the exiting stream. To
solve a problem with two unknowns requires two equations. One is provided by an energy
equation. If the exiting gas mixture is in equilibrium, the other equation is provided by the
equilibrium constant, Eq. 14.35. The temperature of the products may then be called the
equilibrium flame equilibrium flame temperature. The equilibrium constant used to evaluate the equilibrium
d CO
2 O2.
1
temperature flame temperature would be determined with respect to CO2 S
Although only the dissociation of CO2 has been discussed, other products of combustion
may dissociate, for example
H2O S
d H2
12 O2
H2O S
d OH
12H2
O2 S
d 2O
N2 S
d 2H
N2 S
d 2N
When there are many dissociation reactions, the study of chemical equilibrium is facilitated
by the use of computers to solve the simultaneous equations that result. Simultaneous reac-
tions are considered in Sec. 14.4.4. The following example illustrates how the equilibrium
flame temperature is determined when one dissociation reaction occurs.
EXAMPLE 14.6 Determining the Equilibrium Flame Temperature
Carbon monoxide at 25C, 1 atm enters a well-insulated reactor and reacts with the theoretical amount of air entering at the
same temperature and pressure. An equilibrium mixture of CO2, CO, O2, and N2 exits the reactor at a pressure of 1 atm. For
steady-state operation and negligible effects of kinetic and potential energy, determine the composition and temperature of the
exiting mixture in K.
SOLUTION
Known: Carbon monoxide at 25C, 1 atm reacts with the theoretical amount of air at 25C, 1 atm to form an equilibrium
mixture of CO2, CO, O2, and N2 at temperature T and a pressure of 1 atm.
Find: Determine the composition and temperature of the exiting mixture.

CO
25C, 1 atm Assumptions:
Insulation 1. The control volume shown on the accompany-
ing sketch
# by a dashed
# line operates at steady state
with Qcv 0, Wcv 0, and negligible effects of
Air (CO2, CO, O2, N2) kinetic and potential energy.
25C, 1 atm T, 1 atm 2. The entering gases are modeled as ideal gases.
3. The exiting mixture is an ideal gas mixture at
equilibrium.
Figure E14.6
Analysis: The overall reaction is the same as in the solution to Example 14.4
CO
12 O2
1.88N2 S z CO
O2
11 z2 CO2
1.88N2
z
2
By assumption 3, the exiting mixture is an equilibrium mixture. The equilibrium constant expression developed in the solu-
tion to Example 14.4 is
z1z 22 1 2 p pref 1 2

K1T 2 a b
11 z2 15.76
z2 2
(a)
Since p 1 atm, Eq. (a) reduces to

1 2
K1T 2 a b
z z
11 z2 5.76
z
(b)
This equation involves two unknowns: z and the temperature T of the exiting equilibrium mixture.
Another equation involving the two unknowns is obtained from the energy rate balance, Eq. 13.12b, which reduces with
assumption 1 to
hR hP (c)
where
0
1 0 0 0 0
hR 1hf
h 2 CO
1hf
h 2 O2
1.881hf
h 2 N2
2
and
0 0
1hf
h2 O2
11 z2 1hf
h2 CO2
1.881hf
h2 N2
z
hP z1hf
h2 CO
2
The enthalpy of formation terms set to zero are those for oxygen and nitrogen. Since the reactants enter at 25C, the corre-
sponding h terms also vanish. Collecting and rearranging, we get
z 1 h2 CO
1 h2 O2
11 z2 1h2 CO2
1.881h2 N2
11 z2 3 1hf 2 CO2 1hf 2 CO 4 0
z
(d)
2
Equations (b) and (d) are simultaneous equations involving the unknowns z and T. When solved iteratively using tabular data,
the results are z 0.125 and T 2399 K, as can be verified. The composition of the equilibrium mixture, in kmol per kmol
of CO entering the reactor, is then 0.125CO, 0.0625O2, 0.875CO2, 1.88N2.
As illustrated by Example 14.7, the equation solver and property retrieval features of
Interactive Thermodynamics: IT allow the equilibrium flame temperature and composition
to be determined without the iteration required when using table data.
EXAMPLE 14.7 Determining the Equilibrium Flame Temperature Using Software
Solve Example 14.6 using Interactive Thermodynamics: IT and plot equilibrium flame temperature and z, the amount of CO
present in the exiting mixture, each versus pressure ranging from 1 to 10 atm.
SOLUTION
Known: See Example 14.6.

Find: Using IT, plot the equilibrium flame temperature and the amount of CO present in the exiting mixture of Example 14.6,
each versus pressure ranging from 1 to 10 atm.
Assumptions: See Example 14.6.
Analysis: Equation (a) of Example 14.6 provides the point of departure for the IT solution
z1z 22 1 2 ppref 1 2

K1T 2 c d
11 z2 15.76
z2 2
(a)
For a given pressure, this expression involves two unknowns: z and T.

Also, from Example 14.6, we use the energy balance, Eq. (c)
hR hP (c)
where
hR 1hCO 2 R
12 1hO2 2 R
1.881hN2 2 R
and
hP z1hCO 2 P
1z 22 1hO2 2 P
11 z2 1hCO2 2 P
1.881hN2 2 P
where the subscripts R and P denote reactants and products, respectively, and z denotes the amount of CO in the products, in
kmol per kmol of CO entering.
With pressure known, Eqs. (a) and (c) can be solved for T and z using the following IT code. Choosing SI from the Units
menu and amount of substance in moles, and letting hCO_R denote the specific enthalpy of CO in the reactants, and so on,
we have
// Given data
TR = 25 + 273.15 // K
p = 1 // atm
pref = 1 // atm
// Evaluating the equilibrium constant using Eq. (a)

K = ((z * (z/2)^0.5) / (1 z)) * ((p / pref) / ((5.76 + z) / 2))^0.5
// Energy balance: Eq. (c)

hR = hP
hR = hCO_R + (1/2) * hO2_R + 1.88 * hN2_R
hP = z * hCO_P + (z / 2) * hO2_P + (1 z) * hCO2_P + 1.88 * hN2_P
hCO_R = h_T(CO,TR)
hO2_R = h_T(O2,TR)
hN2_R = h_T(N2,TR)
hCO_P = h_T(CO,T)
hO2_P = h_T(O2,T)
hCO2_P = h_T(CO2,T)
hN2_P = h_T(N2,T)
/* To obtain data for the equilibrium constant use the Lookup Table
option under the Edit menu. Load the file eqco2.lut. Data for
CO2 S d CO + 1/2 O2 from Table A-27 are stored in the look-up table
as T in column 1 and log10(K) in column 2. To retrieve the data use
*/
log(K) = lookupval(eqco2,1,T,2)
Obtain a solution for p 1 using the Solve button. To ensure rapid convergence, restrict T and K to positive values, and set
a lower limit of 0.001 and an upper limit of 0.999 for z. The results are T 2399 K and z 0.1249, which agree with the
values obtained in Example 14.6.
Now, use the Explore button and sweep p from 1 to 10 atm in steps of 0.01. Using the Graph button, construct the
following plots:
2500 0.2
2450 0.15
T (K)
2400 0.1
z
2350 0.05
2300 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
p (atm) p (atm)
Figure E14.7
From Fig. E14.7, we see that as pressure increases more CO is oxidized to CO2 (z decreases) and temperature increases.
Similar files are included in IT for each of the reactions in Table A-27.
14.4.2 Vant Hoff Equation

The dependence of the equilibrium constant on temperature exhibited by the values of
Table A-27 follows from Eq. 14.31. An alternative way to express this dependence is given
by the vant Hoff equation, Eq. 14.43b.
The development of this equation begins by introducing Eq. 14.29b into Eq. 14.31 to
obtain on rearrangement
RT ln K 3 1nChC
nDhD nAhA nBhB 2 T 1nC s C
nD s D nAs A nBs B 2 4
(14.41)
Each of the specific enthalpies and entropies in this equation depends on temperature alone.
Differentiating with respect to temperature

R ln K c nC a b
nD a b
d ln K d hC d s C d hD d s D
RT T T
dT dT dT dT dT
nA a b nB a bd
d hA d s A d hB d s B
T T
dT dT dT dT

1nC s C
nD s D nA s A nB s B 2
From the definition of s (T ) (Eq. 6.20), we have d s dT cpT. Moreover, dhdT cp.
Accordingly, each of the underlined terms in the above equation vanishes identically, leaving

R ln K 1nCs C
nDs D nAs A nBs B 2
d ln K
RT (14.42)
dT
Using Eq. 14.41 to evaluate the second term on the left and simplifying the resulting ex-
pression, Eq. 14.42 becomes
d ln K 1nC hC
nD hD nAhA nB hB 2
(14.43a)
dT RT 2
or, expressed more concisely
d ln K H
vant Hoff equation (14.43b)
dT RT 2
which is the vant Hoff equation.

In Eq. 14.43b, H is the enthalpy of reaction at temperature T. The vant Hoff equation
shows that when H is negative (exothermic reaction), K decreases with temperature, whereas
for H positive (endothermic reaction), K increases with temperature.
The enthalpy of reaction H is often very nearly constant over a rather wide interval of
temperature. In such cases, Eq. 14.43b can be integrated to yield
a b
K2 H 1 1
ln (14.44)
K1 R T2 T1
where K1 and K2 denote the equilibrium constants at temperatures T1 and T2, respectively.
This equation shows that ln K is linear in 1T. Accordingly, plots of ln K versus 1T can be
used to determine H from experimental equilibrium composition data. Alternatively, the
equilibrium constant can be determined using enthalpy data.
14.4.3 Ionization
The methods developed for determining the equilibrium composition of a reactive ideal gas
mixture can be applied to systems involving ionized gases, also known as plasmas. In pre-
vious sections we considered the chemical equilibrium of systems where dissociation is a
factor. For example, the dissociation reaction of diatomic nitrogen
N2 S
d 2N
can occur at elevated temperatures. At still higher temperatures, ionization may take place
according to
N S
d N

e (14.45)
That is, a nitrogen atom loses an electron, yielding a singly ionized nitrogen atom N
and a
free electron e. Further heating can result in the loss of additional electrons until all elec-
trons have been removed from the atom.
For some cases of practical interest, it is reasonable to think of the neutral atoms,
positive ions, and electrons as forming an ideal gas mixture. With this idealization, ion-
ization equilibrium can be treated in the same manner as the chemical equilibrium of re-
acting ideal gas mixtures. The change in the Gibbs function for the equilibrium ioniza-
tion reaction required to evaluate the ionization-equilibrium constant can be calculated as
a function of temperature by using the procedures of statistical thermodynamics. In
general, the extent of ionization increases as the temperature is raised and the pressure is
lowered.
Example 14.8 illustrates the analysis of ionization equilibrium.
EXAMPLE 14.8 Considering Ionization Equilibrium
Consider an equilibrium mixture at 2000K consisting of Cs, Cs

, and e, where Cs denotes neutral cesium atoms, Cs
singly
ionized cesium ions, and e free electrons. The ionization-equilibrium constant at this temperature for
Cs S
d Cs

e
is K 15.63. Determine the pressure, in atmospheres, if the ionization of Cs is 95% complete, and plot percent completion
of ionization versus pressure ranging from 0 to 10 atm.
SOLUTION
Known: An equilibrium mixture of Cs, Cs

, e is at 2000K. The value of the equilibrium constant at this temperature is
known.
Find: Determine the pressure of the mixture if the ionization of Cs is 95% complete. Plot percent completion versus pressure.
Assumption: Equilibrium can be treated in this case using ideal gas mixture equilibrium considerations.
Analysis: The ionization of cesium to form a mixture of Cs, Cs
, and e is described by
Cs S 11 z2Cs
z Cs

ze
where z denotes the extent of ionization, ranging from 0 to 1. The total number of moles of mixture n is
n 11 z2
z
z 1
z

At equilibrium, we have Cs S
d Cs
e , so Eq. 14.35 takes the form
1z2 1z2 ppref 1
11 z2
c d a ba b
p
K
11 z2 11
z2 1z 2
p ref
Solving for the ratio ppref and introducing the known value of K
1 z2
115.632 a b
p
pref z2
For pref 1 atm and z 0.95 (95%), p 1.69 atm. Using an equation-solver and plotting package, the following plot can
be constructed:
100
95
90
z (%)
85
80
75
70
0 2 4 6 8 10
p (atm)
Figure E14.8
Figure E14.8 shows that ionization tends to occur to a lesser extent as pressure is raised. Ionization also tends to occur to
a greater extent as temperature is raised at fixed pressure.
14.4.4 Simultaneous Reactions

Let us return to the discussion of Sec. 14.2 and consider the possibility of more than one re-
action among the substances present within a system. For the present application, the closed
system is assumed to contain a mixture of eight components A, B, C, D, E, L, M, and N,
subject to two independent reactions
112 nAA
nBB S
d nCC
nDD (14.24)
122 nAA
nLL S
d nMM
nNN (14.46)
As in Sec. 14.2, component E is inert. Also, note that component A has been taken as com-
mon to both reactions but with a possibly different stoichiometric coefficient (nA is not nec-
essarily equal to nA).
The stoichiometric coefficients of the above equations do not correspond to the numbers
of moles of the respective components present within the system, but changes in the amounts
of the components are related to the stoichiometric coefficients by
dnA dnB dnC dnD
(14.25a)
nA nB nC nD
following from Eq. 14.24, and

dnA dnL dnM dnN
(14.47a)
nA nL nM nN
following from Eq. 14.46. Introducing a proportionality factor de1, Eqs. 14.25a may be rep-
resented by
dnA nA de1, dnB nB de1
(14.25b)
dnC nC de1, dnD nD de1
Similarly, with the proportionality factor de2, Eqs. 14.47a may be represented by
dnA nA de2, dnL nL de2
(14.47b)
dnM nM de2, dnN nN de2
Component A is involved in both reactions, so the total change in A is given by
dnA nA de1 nA de2 (14.48)
Also, we have dnE 0 because component E is inert.

For the system under present consideration, Eq. 14.10 is
dG 4 T,p mA dnA
mB dnB
mC dnC
mD dnD

mE dnE
mL dnL
mM dnM
mN dnN (14.49)
Introducing the above expressions giving the changes in the ns, this becomes
dG 4 T,p 1nAmA nBmB
nCmC
nDmD 2 de1

1nAmA nLmL
nMmM
nNmN 2 de2 (14.50)
Since the two reactions are independent, de1 and de2 can be independently varied. Accord-
ingly, when dG]T,p 0, the terms in parentheses must be zero and two equations of reaction
equilibrium result, one corresponding to each of the foregoing reactions
nAmA
nBmB nCmC
nDmD (14.26b)
nAmA
nLmL nMmM
nNmN (14.51)
The first of these equations is exactly the same as that obtained in Sec. 14.2. For the case
of reacting ideal gas mixtures, this equation can be expressed as
n
y CC y nD p nC
nD nA nB
b ln c nA DnB a b d
G
a (14.52)
RT 1 y A y B pref
Similarly, Eq. 14.51 can be expressed as
n n
y MM y NN p nM
nN nA nL
b ln c nA nL a b d
G
a (14.53)
RT 2 y A y L pref
In each of these equations, the G term is evaluated as the change in Gibbs function for the
respective reaction, regarding each reactant and product as separate at temperature T and a
pressure of 1 atm.
From Eq. 14.52 follows the equilibrium constant
n n
y CC y DD p nC
nD nA nB
K1 a b (14.54)
y nAA y nBB pref
and from Eq. 14.53 follows
n n
y MM y NN p nM
nN nA nL
K2 a b (14.55)
y nAA y nLL pref
The equilibrium constants K1 and K2 can be determined from Table A-27 or a similar com-
pilation. The mole fractions appearing in these expressions must be evaluated by consider-
ing all the substances present within the system, including the inert substance E. Each mole
fraction has the form yi nin, where ni is the amount of component i in the equilibrium
mixture and
n nA
nB
nC
nD
nE
nL
nM
nN (14.56)
The ns appearing in Eq. 14.56 can be expressed in terms of two unknown variables through
application of the conservation of mass principle to the various chemical species present.
Accordingly, for a specified temperature and pressure, Eqs. 14.54 and 14.55 give two
equations in two unknowns. The composition of the system at equilibrium can be
determined by solving these equations simultaneously. This procedure is illustrated by
Example 14.9.
The procedure discussed in this section can be extended to systems involving several
simultaneous independent reactions. The number of simultaneous equilibrium constant ex-
pressions that results equals the number of independent reactions. As these equations are non-
linear and require simultaneous solution, the use of a computer is usually required.
EXAMPLE 14.9 Considering Equilibrium with Simultaneous Reactions
As a result of heating, a system consisting initially of 1 kmol of CO2, 21 kmol of O2, and 12 kmol of N2 forms an equilibrium
mixture of CO2, CO, O2, N2, and NO at 3000 K, 1 atm. Determine the composition of the equilibrium mixture.
SOLUTION
Known: A system consisting of specified amounts of CO2, O2, and N2 is heated to 3000 K, 1 atm, forming an equilibrium
mixture of CO2, CO, O2, N2, and NO.
Find: Determine the equilibrium composition.
Assumption: The final mixture is an equilibrium mixture of ideal gases.
Analysis: The overall reaction has the form
1 CO2
12 O2
12N2 S a CO
bNO
c CO2
d O2
eN2
Applying conservation of mass to carbon, oxygen, and nitrogen, the five unknown coefficients can be expressed in terms of
any two of the coefficients. Selecting a and b as the unknowns, the following balanced equation results:
1 CO2
12 O2
12N2 S a CO
bNO
11 a2 CO2
12 11
a b2 O2
12 11 b2N2
The total number of moles n in the mixture formed by the products is
4
a
n a
b
11 a2
12 11
a b2
12 11 b2
2
At equilibrium, two independent reactions relate the components of the product mixture:
1. CO2 S
d CO
12 O2
2. 1
2 O2
1
2 N2 d
S NO
For the first of these reactions, the form taken by the equilibrium constant when p 1 atm is
a 3 12 11
a b2 4 1 2 1
121
1
a b 1 2
c d a b
1 a
K1
11 a2 14
a2 2 1a 4
a
Similarly, the equilibrium constant for the second of the reactions is

11 21 2
c d
b 1 2b
K2
3 12 11
a b2 4 3 2 11 b2 4
1 2 1 1 2 14
a2 2 3 11
a b2 11 b2 4 1 2
At 3000 K, Table A-27 provides log10K1 0.485 and log10K2 0.913, giving K1 0.3273 and K2 0.1222.
Accordingly, the two equations that must be solved simultaneously for the two unknowns a and b are
1
a b 1 2
a b ,
a 2b
0.3273 0.1222
1a 4
a 3 11
a b2 11 b2 4 1 2
The solution is a 0.3745, b 0.0675, as can be verified. The composition of the equilibrium mixture, in kmol per kmol
of CO2 present initially, is then 0.3745CO, 0.0675NO, 0.6255CO2, 0.6535O2, 0.4663N2.
If high enough temperatures are attained, nitrogen can combine with oxygen to form components such as nitric oxide.
Even trace amounts of oxides of nitrogen in products of combustion can be a source of air pollution.
PHASE EQUILIBRIUM
In this part of the chapter the equilibrium condition dG]T,p 0 introduced in Sec. 14.1
is used to study the equilibrium of multicomponent, multiphase, nonreacting systems. The
discussion begins with the elementary case of equilibrium between two phases of a pure
substance and then turns to the general case of several components present in several
phases.
14.5 Equilibrium Between Two Phases of a Pure Substance 705

14.5 Equilibrium Between Two Phases of a
Pure Substance
Consider the case of a system consisting of two phases of a pure substance at equilibrium.
Since the system is at equilibrium, each phase is at the same temperature and pressure. The
Gibbs function for the system is
G ng 1T, p2
ng1T, p2 (14.57)
where the primes and denote phases 1 and 2, respectively.
Forming the differential of G at fixed T and p
dG 4 T, p g dn
g dn (14.58)
Since the total amount of the pure substance remains constant, an increase in the amount
present in one of the phases must be compensated by an equivalent decrease in the amount
present in the other phase. Thus, we have dn dn, and Eq. 14.58 becomes
dG4 T,p 1g g 2 dn
At equilibrium, dG]T,p 0, so
g g (14.59)
At equilibrium, the molar Gibbs functions of the phases are equal.
CLAPEYRON EQUATION. Equation 14.59 can be used to derive the Clapeyron equation, ob-
tained by other means in Sec. 11.4. For two phases at equilibrium, variations in pressure are
uniquely related to variations in temperature: p psat (T ); thus, differentiation of Eq. 14.59
with respect to temperature gives
b
b b
b
0g 0g dpsat 0g 0g dpsat

0T p 0p T dT 0T p 0p T dT
With Eqs. 11.30 and 11.31, this becomes
dpsat dpsat
s
v s
v
dT dT
Or on rearrangement
dpsat s s

dT v v
This can be expressed alternatively by noting that, with g h T s, Eq. 14.59 becomes
h T s h T s
or
h h
s s (14.60)
T
Combining results, the Clapeyron equation is obtained
1 h h
a b
dpsat
(14.61) Clapeyron equation
dT T v v
Applications of the Clapeyron equation are provided in Chap. 11.

A special form of Eq. 14.61 for a system at equilibrium consisting of a liquid or solid
phase and a vapor phase can be obtained simply. If the specific volume of the liquid or solid,
v, is negligible compared with the specific volume of the vapor, v, and the vapor can be
treated as an ideal gas, v R Tpsat, Eq. 14.61 becomes
dpsat h h

dT RT 2psat
or
ClausiusClapeyron d ln psat h h
(14.62)
equation dT RT 2
which is the ClausiusClapeyron equation. The similarity in form of Eq. 14.62 and the vant
Hoff equation, Eq. 14.43b, may be noted. The vant Hoff equation for chemical equilibrium
is the counterpart of the ClausiusClapeyron equation for phase equilibrium.

14.6 Equilibrium of Multicomponent,
Multiphase Systems
The equilibrium of systems that may involve several phases, each having a number of compo-
nents present, is considered in this section. The principal result is the Gibbs phase rule, which
summarizes important limitations on multicomponent, multiphase systems at equilibrium.
14.6.1 Chemical Potential and Phase Equilibrium

Figure 14.1 shows a system consisting of two components A and B in two phases 1 and 2
that are at the same temperature and pressure. Applying Eq. 14.10 to each of the phases
dG 4 T,p mA dnA
mB dnB
dG 4 T,p mA dnA
mB dnB
(14.63)
where as before the primes identify the two phases.

When matter is transferred between the two phases in the absence of chemical reaction,
the total amounts of A and B must remain constant. Thus, the increase in the amount present
in one of the phases must be compensated by an equivalent decrease in the amount present
in the other phase. That is
dnA dnA, dnB dnB (14.64)
Phase 1
Component A, nA, A
Component B, nB, B
Phase 2
Component A, nA, A Figure 14.1 System consisting of two components in two
Component B, nB, B phases.
14.6 Equilibrium of Multicomponent, Multiphase Systems 707
With Eqs. 14.63 and 14.64, the change in the Gibbs function for the system is
dG4 T,p dG 4 T,p
dG 4 T,p
1mA mA 2 dnA
1mB mB 2 dnB (14.65)
Since nA and nB can be varied independently, it follows that when dG]T,p 0, the terms in
parentheses are zero, resulting in
mA mA and mB mB (14.66)
At equilibrium, the chemical potential of each component is the same in each phase.
The significance of the chemical potential for phase equilibrium can be brought out sim-
ply by reconsidering the system of Fig. 14.1 in the special case when the chemical potential
of component B is the same in both phases: mB mB. With this constraint, Eq. 14.65 reduces
to
dG4 T,p 1mA mA 2 dnA
Any spontaneous process of the system taking place at a fixed temperature and pressure must
be such that the Gibbs function decreases: dG]T,p 0. Thus, with the above expression we
have
1mA mA 2 dnA 6 0
Accordingly,
when the chemical potential of A is greater in phase 1 than in phase 2 (mA 7 mA ), it
follows that dnA 6 0. That is, substance A passes from phase 1 to phase 2.
when the chemical potential of A is greater in phase 2 than in phase 1 (mA 7 mA ), it
follows that dnA 7 0. That is, substance A passes from phase 2 to phase 1.
At equilibrium, the chemical potentials are equal (mA mA ), and there is no net transfer of
A between the phases.
With this reasoning, we see that the chemical potential can be regarded as a measure of
the escaping tendency of a component. If the chemical potential of a component is not the
same in each phase, there will be a tendency for that component to pass from the phase hav-
ing the higher chemical potential for that component to the phase having the lower chemi-
cal potential. When the chemical potential is the same in both phases, there is no tendency
for a net transfer to occur from one phase to the other.
In Example 14.10, we apply phase equilibrium principles to provide a rationale for the
model introduced in Sec. 12.5.3 for moist air in contact with liquid water.
EXAMPLE 14.10 Equilibrium of Moist Air in Contact with Liquid Water
A closed system at a temperature of 20C and a pressure of 1 bar consists of a pure liquid water phase in equilibrium with a
vapor phase composed of water vapor and dry air. Determine the departure, in percent, of the partial pressure of the water
vapor from the saturation pressure of water at 20C.
SOLUTION
Known: A phase of liquid water only is in equilibrium with moist air at 20C and 1 bar.
Find: Determine the percentage departure of the partial pressure of the water vapor in the moist air from the saturation
pressure of water at 20C.
pv
id
Sat.
psat
Sat. liqu
vap
bar
Gas phase of Assumptions:
or
water vapor
and dry air p=1 1. The gas phase can be modeled as an ideal gas
20C g mixture.
f
State of
the water
2. The liquid phase is pure water only.
vapor
State of
the liquid
v
Liquid water
Figure E14.10
Analysis: For phase equilibrium, the chemical potential of the water must have the same value in both phases: 1 v,
where 1 and v denote, respectively, the chemical potentials of the pure liquid water in the liquid phase and the water vapor
in the vapor phase.
The chemical potential 1 is the Gibbs function per mole of pure liquid water (Eq. 14.12)
m1 g 1T, p2
Since the vapor phase is assumed to form an ideal gas mixture, the chemical potential v equals the Gibbs function per mole
evaluated at temperature T and the partial pressure pv of the water vapor (Eq. 14.16)
mv g 1T, pv 2
For phase equilibrium, 1 v, or
g 1T, pv 2 g 1T, p2
With g h T s, this can be expressed alternatively as
h 1T, pv 2 T s 1T, pv 2 h 1T, p2 T s 1T, p2
The water vapor is modeled as an ideal gas. Thus, the enthalpy is given closely by the saturated vapor value at tempera-
ture T
h 1T, pv 2 hg
Furthermore, with Eq. 6.21b, the difference between the specific entropy of the water vapor and the specific entropy at the
corresponding saturated vapor state is
s 1T, pv 2 sg 1T 2 R ln
pv
psat
or
s 1T, pv 2 sg 1T 2 R ln
pv
psat
where psat is the saturation pressure at temperature T.
With Eq. 3.13, the enthalpy of the liquid is closely
h 1T, p2 hf
vf 1 p psat 2
where vf and hf are the saturated liquid specific volume and enthalpy at temperature T. Furthermore, with Eq. 6.7
s 1T, p2 sf 1T 2
where sf is the saturated liquid specific entropy at temperature T.
Collecting the foregoing expressions, we have
hg T asg R ln b hf
vf 1 p psat 2 T sf
pv
psat
or
vf 1 p psat 2 3 1hg hf 2 T 1sg sf 2 4

pv
RT ln
psat
The underlined term vanishes by Eq. 14.60, leaving
pv vf 1 p psat 2 pv vf 1 p psat 2
ln or exp
psat RT psat RT
With data from Table A-2 at 20C, vf 1.0018 103 m3/kg and psat 0.0239 bar, we have
vf 1 p psat 2 1.0018 103 m3/kg 11 0.02392 105 N/m2

a b 1293.15 K2
RT 8314 N # m
18.02 kg # K
7.23 104
Finally
exp 17.23 104 2 1.00072

pv
psat
When expressed as a percentage, the departure of pv from psat is

pv psat
a b 11002 11.00073 12 11002 0.072%
psat
For phase equilibrium, there would be a small, but finite, concentration of air in the liquid water phase. However, this
small amount of dissolved air is ignored in the present development.
The departure of pv from psat is negligible at the specified conditions. This suggests that at normal temperatures and pressures
the equilibrium between the liquid water phase and the water vapor is not significantly disturbed by the presence of the
dry air. Accordingly, the partial pressure of the water vapor can be taken as equal to the saturation pressure of the water
at the system temperature. This model, introduced in Sec. 12.5.3, is used extensively in Chap. 12.
14.6.2 Gibbs Phase Rule

The requirement for equilibrium of a system consisting of two components and two phases,
given by Eqs. 14.66, can be extended with similar reasoning to nonreacting multicomponent,
multiphase systems. At equilibrium, the chemical potential of each component must be the
same in all phases. For the case of N components that are present in P phases we have, there-
fore, the following set of N(P 1) equations:
P1
w
m11 m21 m31 # # # mP1

m12 m22 m32 # # # mP2
N e ## (14.67)
#
m1N m2N m3N # # # mPN
where mji denotes the chemical potential of the ith component in the jth phase. This set of
equations provides the basis for the Gibbs phase rule, which allows the determination of the
number of independent intensive properties that may be arbitrarily specified in order to fix
the intensive state of the system. The number of independent intensive properties is called
degrees of freedom the degrees of freedom (or the variance).
Since the chemical potential is an intensive property, its value depends on the relative
proportions of the components present and not on the amounts of the components. In other
words, in a given phase involving N components at temperature T and pressure p, the chem-
ical potential is determined by the mole fractions of the components present and not the re-
spective ns. However, as the mole fractions add to unity, at most N 1 of the mole fractions
can be independent. Thus, for a system involving N components, there are at most N 1
independently variable mole fractions for each phase. For P phases, therefore, there are at
most P(N 1) independently variable mole fractions. In addition, the temperature and pres-
sure, which are the same in each phase, are two further intensive properties, giving a max-
imum of P(N 1)
2 independently variable intensive properties for the system. But
because of the N(P 1) equilibrium conditions represented by Eqs. 14.67 among these
properties, the number of intensive properties that are freely variable, the degrees of free-
dom F, is
Gibbs phase rule F 3P1N 12

24 N1P 12 2
N P (14.68)
which is the Gibbs phase rule.

In Eq. 14.68, F is the number of intensive properties that may be arbitrarily specified and
that must be specified to fix the intensive state of a nonreacting system at equilibrium.
for example... let us apply the Gibbs phase rule to a liquid solution consisting of
water and ammonia such as considered in the discussion of absorption refrigeration (Sec. 10.5).
This solution involves two components and a single phase: N 2 and P 1. Equation 14.68
then gives F 3, so the intensive state is fixed by giving the values of three intensive properties,
such as temperature, pressure, and the ammonia (or water) mole fraction.
The phase rule summarizes important limitations on various types of systems. For ex-
ample, for a system involving a single component such as water, N 1 and Eq. 14.68
becomes
F3P (14.69)
The minimum number of phases is one, corresponding to P 1. For this case,

Eq. 14.69 gives F 2. That is, two intensive properties must be specified to fix the
intensive state of the system. This requirement is familiar from our use of the steam
tables and similar property tables. To obtain properties of superheated vapor, say, from
such tables requires that we give values for any two of the tabulated properties, for
example, T and p.
When two phases are present in a system involving a single component, N 1 and
P 2. Equation 14.69 then gives F 1. That is, the intensive state is determined by a
single intensive property value. For example, the intensive states of the separate phases
of an equilibrium mixture of liquid water and water vapor are completely determined
by specifying the temperature.
The minimum allowable value for the degrees of freedom is zero: F 0. For a single-
component system, Eq. 14.69 shows that this corresponds to P 3, a three-phase
system. Thus, three is the maximum number of different phases of a pure component
that can coexist in equilibrium. Since there are no degrees of freedom, both temperature
and pressure are fixed at equilibrium. For example, there is only a single temperature
0.01C and a single pressure 0.6113 kPa for which ice, liquid water, and water vapor
are in equilibrium.
The phase rule given here must be modified for application to systems in which chemical
reactions occur. Furthermore, the system of equations, Eqs. 14.67, giving the requirements for
phase equilibrium at a specified temperature and pressure can be expressed alternatively in
terms of partial molal Gibbs functions, fugacities, and activities, all of which are introduced in
Sec. 11.9. To use any such expression to determine the equilibrium composition of the differ-
ent phases present within a system at equilibrium requires a model for each phase that allows
the relevant quantitiesthe chemical potentials, fugacities, and so onto be evaluated for the
components present in terms of system properties that can be determined. For example, a gas
phase might be modeled as an ideal gas mixture or, at higher pressures, as an ideal solution.
In this chapter, we have studied chemical equilibrium and apply the equilibrium constant relationship, Eq. 14.35, to
phase equilibrium. The chapter opens by developing criteria determine the third quantity when any two of tempera-
for equilibrium and introducing the chemical potential. In the ture, pressure, and equilibrium composition of an ideal
second part of the chapter, we study the chemical equilibrium gas mixture are known. Special cases include applica-
of ideal gas mixtures using the equilibrium constant concept. tions with simultaneous reactions and systems involving
We also utilize the energy balance and determine the equi- ionized gases.
librium flame temperature as an application. The final part of use chemical equilibrium concepts with the energy bal-
the chapter concerns phase equilibrium, including multicom- ance, including determination of the equilibrium flame
ponent, multiphase systems and the Gibbs phase rule. temperature.
The following list provides a study guide for this chapter.
apply Eq. 14.43b, the vant Hoff equation, to determine
When your study of the text and end-of-chapter exercises has
been completed, you should be able to the enthalpy of reaction when the equilibrium constant is
known, and conversely.
write out the meaning of the terms listed in the margin
apply the Gibbs phase rule, Eq. 14.68.
concepts. The subset of key concepts listed below is
particularly important.
Gibbs function p. 719 equation of reaction equilibrium Gibbs phase rule p. 749
equilibrium equilibrium p. 725 constant p. 727
criterion p. 720
chemical
potential p. 721
1. Why is using the Gibbs function advantageous when study- 6. For CO2
H2 Sd CO
H2O, how does pressure affect the
ing chemical and phase equilibrium? equilibrium composition?
2. For Eq. 14.6 to apply at equilibrium, must a system attain 7. For each of the reactions listed in Table A-27, the value of log10K
equilibrium at fixed T and p? increases with increasing temperature. What does this imply?
3. Show that (dA)T,V 0 is a valid equilibrium criterion, where 8. For each of the reactions listed in Table A-27, the value of the
A U TS is the Helmholtz function. equilibrium constant K at 298 K is relatively small. What does
4. A mixture of 1 kmol of CO and 12 kmol of O2 is held at am- this imply?
bient temperature and pressure. After 100 hours only an 9. If a system initially containing CO2 and H2O were held at fixed
insignificant amount of CO2 has formed. Why? T, p, list chemical species that might be present at equilibrium.
5. Why might oxygen contained in an iron tank be treated as 10. Using Eq. 14.12 together with phase equilibrium considera-
inert in a thermodynamic analysis even though iron oxidizes in tions, suggest how the chemical potential of a mixture compo-
the presence of oxygen? nent could be evaluated.
11. Note 1 of Example 14.10 refers to the small amount of air 12. Water can exist in a number of different solid phases. Can
that would be dissolved in the liquid phase. For equilibrium, what liquid water, water vapor, and two phases of ice exist in
must be true of the chemical potentials of air in the liquid and equilibrium?
gas phases?
Working with the Equilibrium Constant (a) Show that K1 K2K3.

14.1 Determine the change in the Gibbs function G at 25C, (b) Evaluate log10K1 at 298 K, 1 atm using the expression from
in kJ/kmol, for the reaction part (a), together with log10K data from Table A-27.
CH4 1g2
2O2 CO2
2H2O 1g2
(c) Check the value for log10K1 obtained in part (b) by apply-
S
d
ing Eq. 14.31 to reaction 1.
using 14.10 Evaluate the equilibrium constant at 2000 K for
(a) Gibbs function of formation data. CH4
H2O Sd 3H2
CO. At 2000 K, log10K 7.469 for
(b) enthalpy of formation and absolute entropy data. C
12O2 S
d CO, and log10K 3.408 for C
2H2 S
d CH4.
14.2 Calculate the equilibrium constant, expressed as log10K, 14.11 For each of the following dissociation reactions, deter-
d CO
2 O2 at (a) 500 K, (b) 1800R. Compare with
1
for CO2 S mine the equilibrium compositions:
values from Table A-27.
(a) One kmol of N2O4 dissociates to form an equilibrium ideal
14.3 Calculate the equilibrium constant, expressed as log10K, gas mixture of N2O4 and NO2 at 25C, 2 atm. For
for the water-gas reaction CO
H2O(g) S d CO2
H2 at d 2NO2, G 5400 kJ/kmol at 25C.
N2O4 S
(a) 298 K, (b) 1000 K. Compare with values from Table A-27. (b) One kmol of CH4 dissociates to form an equilibrium ideal
14.4 Calculate the equilibrium constant, expressed as log10K, gas mixture of CH4, H2, and C at 1000 K, 5 atm. For
for H2O Sd H2
2 O2 at (a) 298 K, (b) 2000K. Compare with
1 C
2H2 Sd CH4, log10K 1.011 at 1000 K.
values from Table A-27. 14.12 The following exercises involve oxides of nitrogen:
14.5 Using data from Table A-27, determine log10K at 2500 K (a) One kmol of N2O4 dissociates at 25C, 1 atm to form an
for equilibrium ideal gas mixture of N2O4 and NO2 in which
d H2
2 O2.
1
(a) H2O S the amount of N2O4 present is 0.8154 kmol. Determine the
(b) H2
2O2 d H2O.
1 S amount of N2O4 that would be present in an equilibrium
d 2H2
O2.
(c) 2H2O S mixture at 25C, 0.5 atm.
14.6 In Table A-27, log10K is nearly linear in 1T: log10K (b) A gaseous mixture consisting of 1 kmol of NO, 10 kmol
C1
C2T, where C1 and C2 are constants. For selected of O2, and 40 kmol of N2 reacts to form an equilibrium
reactions listed in the table ideal gas mixture of NO2, NO, and O2 at 500 K, 0.1 atm.
Determine the composition of the equilibrium mixture. For
(a) verify this by plotting log10K versus 1T temperature rang- NO
12O2 S d NO2, K 120 at 500 K.
ing from 2100 to 2500 K. (c) An equimolar mixture of O2 and N2 reacts to form an equi-
(b) evaluate C1 and C2 for any pair of adjacent table entries in librium ideal gas mixture of O2, N2, and NO. Plot the mole
the temperature range of part (a). fraction of NO in the equilibrium mixture versus equilib-
14.7 Determine the relationship between the ideal gas equilibrium temperature ranging from 1200 to 2000 K.
rium constants K1 and K2 for the following two alternative ways Why are oxides of nitrogen of concern?
of expressing the ammonia synthesis reaction:
14.13 One kmol of CO2 dissociates to form an equilibrium
1. 12N2
32H2 S
d NH3
ideal gas mixture of CO2, CO, and O2 at temperature T and
2. N2
3H2 S d 2NH3
pressure p.
14.8 Consider the reactions
(a) For T 3000 K, plot the amount of CO present, in kmol,
1. CO
H2O S
d H2
CO2 versus pressure for 1 p 10 atm.
d 2CO
O2
2. 2CO2 S (b) For p 1 atm, plot the amount of CO present, in kmol,
d 2H2
O2
3. 2H2O S versus temperature for 2000 T 3500 K.
Show that K1 (K3K2)12. 14.14 One kgmol of H2O dissociates to form an equilibrium
14.9 Consider the reactions ideal gas mixture of H2O, H2, and O2 at temperature T and
1. CO2
H2 S
d CO
H2O pressure p.
d CO
2 O2
1
2. CO2 S (a) For T 3000K, plot the amount of H2 present, in kgmol,
3. H2O d H2
2 O2
S 1
versus pressure ranging from 1 to 10 atm.
(b) For p 1 atm, plot the amount of H2 present, in kgmol, 14.25 A gaseous mixture with a molar analysis of 20% CO2,
versus temperature ranging from 2000 to 3500K. 40% CO, and 40% O2 enters a heat exchanger and is heated
at constant pressure. An equilibrium mixture of CO2, CO, and
14.15 An equimolar mixture of CO and O2 reacts to form an
O2 exits at 3000 K, 1.5 bar. Determine the molar analysis of
equilibrium mixture of CO2, CO, and O2 at 3000 K. Determine
the exiting mixture.
the effect of pressure on the composition of the equilibrium
mixture. Will lowering the pressure while keeping the tem- 14.26 An ideal gas mixture with the molar analysis 30% CO,
perature fixed increase or decrease the amount of CO2 pres- 10% CO2, 40% H2O, 20% inert gas enters a reactor operating
ent? Explain. at steady state. An equilibrium mixture of CO, CO2, H2O, H2,
and the inert gas exits at 1 atm.
14.16 An equimolar mixture of CO and H2O(g) reacts to form
an equilibrium mixture of CO2, CO, H2O, and H2 at 1727C, (a) If the equilibrium mixture exits at 1200 K, determine on
1 atm. a molar basis the ratio of the H2 in the equilibrium mix-
(a) Will lowering the temperature increase or decrease the ture to the H2O in the entering mixture.
amount of H2 present? Explain. (b) If the mole fraction of CO present in the equilibrium mix-
(b) Will decreasing the pressure while keeping the temperature is 7.5%, determine the temperature of the equilibrium
ture constant increase or decrease the amount of H2 pres- mixture, in K.
ent? Explain. 14.27 A mixture of 1 kmol CO and 0.5 kmol O2 in a closed
14.17 Determine the temperature, in K, at which 9% of diatomic vessel, initially at 1 atm and 300 K, reacts to form an equilib-
hydrogen (H2) dissociates into monatomic hydrogen (H) at a rium mixture of CO2, CO, and O2 at 2500 K. Determine the
pressure of 10 atm. For a greater percentage of H2 at the same final pressure, in atm.
pressure, would the temperature be higher or lower? Explain. 14.28 Methane burns with 90% of theoretical air to form an
14.18 Two kmol of CO2 dissociate to form an equilibrium mix- equilibrium mixture of CO2, CO, H2O(g), H2, and N2 at 1000 K,
ture of CO2, CO, and O2 in which 1.8 kmol of CO2 is present. 1 atm. Determine the composition of the equilibrium mixture,
Plot the temperature of the equilibrium mixture, in K, versus per kmol of mixture.
the pressure p for 0.5 p 10 atm. 14.29 Octane (C8H18) burns with air to form an equilibrium
14.19 One kmol of H2O(g) dissociates to form an equilibrium mixture of CO2, H2, CO, H2O(g), and N2 at 1700 K, 1 atm.
mixture of H2O(g), H2, and O2 in which the amount of water Determine the composition of the products, in kmol per kmol
vapor present is 0.95 kmol. Plot the temperature of the equi- of fuel, for an equivalence ratio of 1.2.
librium mixture, in K, versus the pressure p for 1 p 14.30 Acetylene gas (C2H2) at 25C, 1 atm enters a reactor op-
10 atm. erating at steady state and burns with 40% excess air entering
14.20 A vessel initially containing 1 kmol of H2O(g) and x kmol at 25C, 1 atm, 80% relative humidity. An equilibrium mixture
of N2 forms an equilibrium mixture at 1 atm consisting of of CO2, H2O, O2, NO, and N2 exits at 2200 K, 0.9 atm.
H2O(g), H2, O2, and N2 in which 0.5 kmol of H2O(g) is pres- Determine, per kmol of C2H2 entering, the composition of
ent. Plot x versus the temperature T for 3000 T 3600 K. exiting mixture.
14.21 A vessel initially containing 1 kmol of CO and 4.76 kmol

of dry air forms an equilibrium mixture of CO2, CO, O2, and Chemical Equilibrium and the Energy Balance
N2 at 3000 K, 1 atm. Determine the equilibrium composition. 14.31 Carbon dioxide gas at 25C, 5.1 atm enters a heat ex-
14.22 A vessel initially containing 1 kmol of O2, 2 kmol of changer operating at steady state. An equilibrium mixture of
N2, and 1 kmol of Ar forms an equilibrium mixture of O2, CO2, CO, and O2 exits at 2527C, 5 atm. Determine, per kmol
N2, NO, and Ar at 2727C, 1 atm. Determine the equilibrium of CO2 entering,
composition. (a) the composition of the exiting mixture.
14.23 One kmol of CO and 0.5 kmol of O2 react to form a (b) the heat transfer to the gas stream, in kJ.
mixture at temperature T and pressure p consisting of CO2, Neglect kinetic and potential energy effects.
CO, and O2. If 0.35 kmol of CO is present in an equilibrium
mixture when the pressure is 1 atm, determine the amount of 14.32 Carbon at 25C, 1 atm enters a reactor operating at steady
CO present in an equilibrium mixture at the same temperature state and burns with oxygen entering at 127C, 1 atm. The
if the pressure were 10 atm. entering streams have equal molar flow rates. An equilibrium
mixture of CO2, CO, and O2 exits at 2727C, 1 atm. Deter-
14.24 A vessel initially contains 1 kmol of H2 and 4 kmol of mine, per kmol of carbon,
N2. An equilibrium mixture of H2, H, and N2 forms at 3000 K,
1 atm. Determine the equilibrium composition. If the pressure (a) the composition of the exiting mixture.
were increased while keeping the temperature fixed, would (b) the heat transfer between the reactor and its surroundings,
the amount of monatomic hydrogen in the equilibrium mixture in kJ.
increase or decrease? Explain. Neglect kinetic and potential energy effects.
14.33 Methane gas at 25C, 1 atm enters a reactor operating at oretical amount of air entering at 25C, 1 atm. An equilibrium
steady state and burns with 80% of theoretical air entering at mixture of CO2, CO, O2, and N2 exits at 1 atm. For selected
227C, 1 atm. An equilibrium mixture of CO2, CO, H2O(g), values of x ranging from 1 to 4, determine the temperature of
H2, and N2 exits at 1427C, 1 atm. Determine, per kmol of the exiting equilibrium mixture, in K. Kinetic and potential en-
methane entering, ergy effects are negligible.
(a) the composition of the exiting mixture. 14.42 A mixture consisting of 1 kmol of carbon monoxide
(b) the heat transfer between the reactor and its surroundings, (CO), 0.5 kmol of oxygen (O2), and 1.88 kmol of nitrogen (N2),
in kJ. initially at 227C, 1 atm, reacts in a closed, rigid, insulated ves-
sel, forming an equilibrium mixture of CO2, CO, O2, and N2.
Neglect kinetic and potential energy effects.
Determine the final equilibrium pressure, in atm.
14.34 Gaseous propane (C3H8) at 25C, 1 atm enters a reactor
14.43 A mixture consisting of 1 kmol of CO and the theoreti-
operating at steady state and burns with 80% of theoretical air
cal amount of air, initially at 60C, 1 atm, reacts in a closed,
entering separately at 25C, 1 atm. An equilibrium mixture of
rigid, insulated vessel to form an equilibrium mixture. An
CO2, CO, H2O(g), H2, and N2 exits at 1227C, 1 atm. Determine
analysis of the products shows that there are 0.808 kmol of
the heat transfer between the reactor and its surroundings, in
CO2, 0.192 kmol of CO, and 0.096 kmol of O2 present. The
kJ per kmol of propane entering. Neglect kinetic and potential
temperature of the final mixture is measured as 2465C. Check
energy effects.
the consistency of these data.
14.35 One kmol of CO2 initially at temperature T and 1 atm is
heated at constant pressure until a final state is attained con-
sisting of an equilibrium mixture of CO2, CO, and O2 in which Using the vant Hoff Equation, Ionization
the amount of CO2 present is 0.422 kmol. Determine the heat 14.44 Estimate the enthalpy of reaction at 2000 K, in kJ/kmol,
transfer and the work, each in kJ, if T is (a) 298 K, (b) 400 K. for CO2 Sd CO
2 O2 using the vant Hoff equation and equi-
1
14.36 Hydrogen gas (H2) at 25C, 1 atm enters an insulated re- librium constant data. Compare with the value obtained for the
actor operating at steady state and reacts with 250% excess oxy- enthalpy of reaction using enthalpy data.
gen entering at 227C, 1 atm. The products of combustion exit 14.45 Estimate the enthalpy of reaction at 2000 K, in kJ/kmol,
d H2
2 O2, using the vant Hoff equation and equi-
at 1 atm. Determine the temperature of the products, in K, if 1
for H2O S
(a) combustion is complete. librium constant data. Compare with the value obtained for the
(b) an equilibrium mixture of H2O, H2, and O2 exits. enthalpy of reaction using enthalpy data.
Kinetic and potential energy effects are negligible. 14.46 Estimate the equilibrium constant at 2800 K for
d CO
2 O2 using the equilibrium constant at 2000 K
1
CO2 S
14.37 For each case of Problem 14.45, determine the rate of from Table A-27, together with the vant Hoff equation and en-
entropy production, in kJ/K per kmol of H2 entering. What can thalpy data. Compare with the value for the equilibrium con-
be concluded about the possibility of achieving complete stant obtained from Table A-27.
combustion?
14.47 Estimate the equilibrium constant at 2800 K for the
14.38 Hydrogen (H2) at 25C, 1 atm enters an insulated reac- reaction H2O Sd H2
2 O2 using the equilibrium constant at
1
tor operating at steady state and reacts with 100% of theoret- 2500 K from Table A-27, together with the vant Hoff equa-
ical air entering at 25C, 1 atm. The products of combustion tion and enthalpy data. Compare with the value for the equi-
exit at temperature T and 1 atm. Determine T, in K, if librium constant obtained from Table A-27.
(a) combustion is complete. 14.48 At 25C, log10 K 8.9 for C
2H2 S d CH4. Assuming
(b) an equilibrium mixture of H2O, H2, O2, and N2 exits. that the enthalpy of reaction does not vary much with temper-
14.39 Carbon monoxide at 25C, 1 atm enters an insulated re- ature, estimate the value of log10K at 500C.

actor operating at steady state and burns with excess oxygen 14.49 If the ionization-equilibrium constants for Cs Sd Cs
e
(O2) entering at 25C, 1 atm. The products exit at 2950 K, at 1600 and 2000 K are K 0.78 and K 15.63, respectively,
1 atm as an equilibrium mixture of CO2, CO, and O2. estimate the enthalpy of ionization, in kJ/kmol, at 1800 K using
Determine the percent excess oxygen. Kinetic and potential en- the vant Hoff equation.
ergy effects are negligible.
14.50 An equilibrium mixture at 2000 K, 1 atm consists of Cs,
14.40 Methane at 25C, 1 atm enters an insulated reactor op- Cs
, and e. Based on 1 kmol of Cs present initially, determine
erating at steady state and burns with oxygen entering at 127C, the percent ionization of cesium. At 2000 K, the ionization-

1 atm. An equilibrium mixture of CO2, CO, O2, and H2O(g) d Cs
e is K 15.63.
equilibrium constant for Cs S
exits at 3250 K, 1 atm. Determine the rate at which oxygen 14.51 At 2000 K and pressure p, 1 kmol of Na ionizes to form
enters the reactor, in kmol per kmol of methane. Kinetic and an equilibrium mixture of Na, Na
, and e in which the amount
potential energy effects are negligible. of Na present is x kmol. Plot the pressure, in atm, versus x for
14.41 Methane gas at 25C, 1 atm enters an insulated reactor 0.2 x 0.3 kmol. At 2000 K, the ionization-equilibrium

operating at steady state, where it burns with x times the the- constant for Na Sd Na
e is K 0.668.
14.52 At 12,000 K and 6 atm, 1 kmol of N ionizes to form an 14.62 An isolated system has two phases, denoted by A and B,
equilibrium mixture of N, N
, and e in which the amount of each of which consists of the same two substances, denoted by
N present is 0.95 kmol. Determine the ionization-equilibrium 1 and 2. The phases are separated by a freely moving, thin wall

d N
e .
constant at this temperature for N S permeable only by substance 2. Determine the necessary con-
ditions for equilibrium.
Considering Simultaneous Reactions 14.63 Referring to Problem 14.63, let each phase be a binary
mixture of argon and helium and the wall be permeable only
14.53 Carbon dioxide (CO2), oxygen (O2), and nitrogen (N2)
to argon. If the phases initially are at the conditions tabulated
enter a reactor operating at steady state with equal molar flow
below, determine the final equilibrium temperature, pressure,
rates. An equilibrium mixture of CO2, O2, N2, CO, and NO
and composition in the two phases.
exits at 3000 K, 5 atm. Determine the molar analysis of the
equilibrium mixture.
14.54 An equimolar mixture of carbon monoxide and water va- T (K) p(MPa) n (kmol) yAr yHe
por enters a heat exchanger operating at steady state. An equi- Phase A 300 0.2 6 0.5 0.5
librium mixture of CO, CO2, O2, H2O(g), and H2 exits at Phase B 400 0.1 5 0.8 0.2
2227C, 1 atm. Determine the molar analysis of the exiting
equilibrium mixture. 14.64 Figure P14.65 shows an ideal gas mixture at temperature
14.55 Butane (C4H10) burns with 100% excess air to form an T and pressure p containing substance k, separated from a gas
equilibrium mixture at 1400 K, 20 atm consisting of CO2, O2, phase of pure k at temperature T and pressure p by a semi-
H2O(g), N2, NO, and NO2. Determine the balanced reaction permeable membrane that allows only k to pass through. As-
10
equation. For N2
2O2 Sd 2NO2 at 1400 K, K 8.4 10 . suming the ideal gas model also applies to the pure gas phase,
14.56 Steam enters a heat exchanger operating at steady state. determine the relationship between p and p for there to be no
An equilibrium mixture of H2O, H2, O2, H, and OH exits at net transfer of k through the membrane.
temperature T, 1 atm. Determine the molar analysis of the
exiting equilibrium mixture for Membrane permeable
only to k
(a) T 2800 K. Ideal gas mixture
(b) T 3000 K. at T, p. Mole
Ideal gas k
fraction of substance
at, T, p
k is yk, partial
Considering Phase Equilibrium pressure pk = yk p
14.57 For a two-phase liquidvapor mixture of water at 100C,
use tabulated property data to show that the specific Gibbs
Figure P14.64
functions of the saturated liquid and saturated vapor are equal.
Repeat for a two-phase liquidvapor mixture of Refrigerant
134a at 20C. 14.65 What is the maximum number of homogeneous phases
14.58 Using the Clapeyron equation, solve the following prob- that can exist at equilibrium for a system involving
lems from Chap. 11: (a) 11.32, (b) 11.33, (c) 11.34, (d) 11.35, (a) one component?
(e) 11.40. (b) two components?
14.59 A closed system at 20C, 1 bar consists of a pure liquid (c) three components?
water phase in equilibrium with a vapor phase composed of 14.66 Determine the number of degrees of freedom for systems
water vapor and dry air. Determine the departure, in percent, composed of
of the partial pressure of the water vapor from the saturation
(a) ice and liquid water.
pressure of pure water at 20C.
(b) ice, liquid water, and water vapor.
14.60 Derive an expression for estimating the pressure at which (c) liquid water and water vapor.
graphite and diamond exist in equilibrium at 25C in terms of (d) water vapor only.
the specific volume, specific Gibbs function, and isothermal (e) water vapor and dry air.
compressibility of each phase at 25C, 1 atm. Discuss. (f) liquid water, water vapor, and dry air.
14.61 An isolated system has two phases, denoted by A and (g) ice, water vapor, and dry air.
B, each of which consists of the same two substances, de- (h) N2 and O2 at 20C, 1 atm.
noted by 1 and 2. Show that necessary conditions for equi- (i) a liquid phase and a vapor phase, each of which contains
librium are ammonia and water.
1. the temperature of each phase is the same, TA TB. (j) liquid mercury, liquid water, and a vapor phase of mercury
2. the pressure of each phase is the same, pA pB. and water.
3. the chemical potential of each component has the same (k) liquid acetone and a vapor phase of acetone and N2.
value in each phase, mA1 mB1, mA2 mB2. 14.67 Develop the phase rule for chemically reacting systems.
14.68 Apply the result of Problem 14.84 to determine the num- thus, pi xi p where xi is the mole fraction of i in the gas phase.
ber of degrees of freedom for the gas phase reaction: Apply Raoults law to the following cases, which are
representative of conditions that might be encountered in
CH4
H2O S
d CO
3H2 ammoniawater absorption systems (Sec. 10.5):
14.69 For a gasliquid system in equilibrium at temperature T (a) Consider a two-phase, liquidvapor ammoniawater
and pressure p, Raoults law models the relation between the system in equilibrium at 20C. The mole fraction of
partial pressure of substance i in the gas phase, pi, and the mole ammonia in the liquid phase is 80%. Determine the
fraction of substance i in the liquid phase, yi, as follows: pressure, in bar, and the mole fraction of ammonia in the
vapor phase.
pi yi psat,i 1T 2 (b) Determine the mole fractions of ammonia in the liquid and
vapor phases of a two-phase ammoniawater system in
where psat,i(T ) is the saturation pressure of pure i at tempera-
equilibrium at 40C, 12 bar.
ture T. The gas phase is assumed to form an ideal gas mixture;
14.1D Using appropriate software, develop plots giving the 14.4D The amount of sulfur dioxide (SO2) present in off gases
variation with equivalence ratio of the equilibrium products of from industrial processes can be reduced by oxidizing the SO2
octaneair mixtures at 30 atm and selected temperatures rang- to SO3 at an elevated temperature in a catalytic reactor. The
ing from 1700 to 2800 K. Consider equivalence ratios in the SO3 can be reacted in turn with water to form sulfuric acid that
interval from 0.2 to 1.4 and equilibrium products including, has economic value. For an off gas at 1 atm having the molar
but not necessarily limited to, CO2, CO, H2O, O2, O, H2, N2, analysis of 12% SO2, 8% O2, 80% N2, estimate the range of
NO, OH. Under what conditions is the formation of nitric oxide temperatures at which a substantial conversion of SO2 to SO3
(NO) and carbon monoxide (CO) most significant? Discuss. might be realized.
14.2D Spark-ignition engine exhaust gases contain several air 14.5D A gaseous mixture of hydrogen (H2) and carbon monox-
pollutants including the oxides of nitrogen, NO and NO2, col- ide (CO) enters a catalytic reactor and a gaseous mixture of
lectively known as NOx. Additionally, the exhaust gases may methanol (CH3OH), hydrogen, and carbon monoxide exits. At
contain carbon monoxide (CO) and unburned or partially the preliminary process design stage, a plausible estimate is
burned hydrocarbons (HC). required of the inlet hydrogen mole fraction, yH2, the temper-
(a) The pollutant amounts actually present depend on engine ature of the exiting mixture, Te, and the pressure of the exiting
design and operating conditions, and typically differ sig- mixture, pe, subject to the following four constraints: (1)
nificantly from values calculated on the basis of chemical 0.5 yH2 0.75, (2) 300 Te 400 K, (3) 1 pe 10
equilibrium. Discuss both the reasons for these discrepan- atm, and (4) the exiting mixture contains at least 75% methanol
cies and possible mechanisms by which such pollutants are on a molar basis. Obtain this estimate.
formed in an actual engine. 14.6D When systems in thermal, mechanical, and chemical equi-
(b) For spark-ignition engines, the average production of pol- librium are perturbed, changes within the systems can occur
lutants upstream of the catalyst, in g per mile of vehicle leading to a new equilibrium state. The effects of perturbing the
travel, are nitric oxides, 1.5; hydrocarbons, 2; and carbon system considered in developing Eqs. 14.32 and 14.33 can be
monoxide, 20. For a city in your locale having a popula- determined by study of these equations. For example, at fixed
tion of 100,000 or more, estimate the annual amount, in pressure and temperature it can be concluded that an increase in
kg, of each pollutant that would be discharged if automo- the amount of the inert component E would lead to increases in
biles had no emission control devices. Repeat if the nC and nD when (C
D A B) is positive, to
vehicles adhere to current U.S. government emissions decreases in nC and nD when is negative, and no change when
standards. 0.
14.3D The Federal Clean Air Act of 1970 and succeeding Clean
(a) For a system consisting of NH3, N2, and H2 at fixed pres-
Air Act Amendments target the oxides of nitrogen NO and
sure and temperature, subject to the reaction
NO2, collectively known as NOx, as significant air pollutants.
NOx is formed in combustion via three primary mechanisms: 2NH3 1g2 N2 1g2
3H2 1g2
thermal NOx formation, prompt NOx formation, and fuel NOx
formation. Discuss these formation mechanisms, including a investigate the effects, in turn, of additions in the amounts
discussion of thermal NOx formation by the Zeldovich mech- present of NH3, H2, and N2.
anism. What is the role of NOx in the formation of ozone? What (b) For the general case of Eqs. 14.32 and 14.33, investigate
are some NOx reduction strategies? the effects, in turn, of additions of A, B, C, and D.
14.7D With reference to the equilibrium constant data of (b) For the synthesis of ammonia by
Table A-27: 1

32H2 S NH3
2 N2
(a) For each of the tabulated reactions plot log10K versus 1T provide a recommendation for the ranges of temperature and
and determine the slope of the line of best fit. What is pressure for which the mole fraction of ammonia in the mix-
the thermodynamic significance of the slope? Check your ture is at least 0.5.
conclusion about the slope using data from the JANAF 14.9D U.S. Patent 5,298,233 describes a means for converting
tables.2 industrial wastes to carbon dioxide and water vapor. Hydrogen-
(b) A text states that the magnitude of the equilibrium con- and carbon-containing feed, such as organic or inorganic
stant often signals the importance of a reaction, and offers sludge, low-grade fuel oil, or municipal garbage, is introduced
this rule of thumb: When K 103, the extent of the re- into a molten bath consisting of two immiscible molten metal
action is usually not significant, whereas when K 103 phases. The carbon and hydrogen of the feed are converted,
the reaction generally proceeds closely to equilibrium. respectively, to dissolved carbon and dissolved hydrogen. The
Confirm or deny this rule. dissolved carbon is oxidized in the first molten metal phase to
14.8D (a) For an equilibrium ideal gas mixture of N2, H2, and carbon dioxide, which is released to the atmosphere. The dis-
NH3, evaluate the equilibrium constant from an expression you solved hydrogen migrates to the second molten metal phase,
derive from the vant Hoff equation that requires only standard where it is oxidized to form water vapor, which is also released
state enthalpy of formation and Gibbs function of formation from the bath. Critically evaluate this technology for waste dis-
data together with suitable analytical expressions in terms of posal. Is the technology promising commercially? Compare
temperature for the ideal gas specific heats of N2, H2, NH3. with alternative waste management practices such as pyroly-
sis and incineration.
14.10D Iceland Aims to be Fossil-fuel Free (see box
Sec. 14.2). Investigate the feasibility of large-scale production
2
Stull, D. R., and H. Prophet, JANAF Thermochemical Tables, 2nd ed., of hydrogen using solar energy and windpower, considering
NSRDS-NBS 37, National Bureau of Standards, Washington, DC, June technical and economical aspects. Write a report including at
1971. least three references.
Index to Tables in SI Units
TABLE A-1 Atomic or Molecular Weights and Critical Properties of Selected Elements and Compounds 719
TABLE A-2 Properties of Saturated Water (LiquidVapor): Temperature Table 720
TABLE A-3 Properties of Saturated Water (LiquidVapor): Pressure Table 722
TABLE A-4 Properties of Superheated Water Vapor 724
TABLE A-5 Properties of Compressed Liquid Water 728
TABLE A-6 Properties of Saturated Water (SolidVapor): Temperature Table 729
TABLE A-7 Properties of Saturated Refrigerant 22 (LiquidVapor): Temperature Table 730
TABLE A-8 Properties of Saturated Refrigerant 22 (LiquidVapor): Pressure Table 731
TABLE A-9 Properties of Superheated Refrigerant 22 Vapor 732
TABLE A-10 Properties of Saturated Refrigerant 134a (LiquidVapor): Temperature Table 736
TABLE A-11 Properties of Saturated Refrigerant 134a (LiquidVapor): Pressure Table 737
TABLE A-12 Properties of Superheated Refrigerant 134a Vapor 738
TABLE A-13 Properties of Saturated Ammonia (LiquidVapor): Temperature Table 741
TABLE A-14 Properties of Saturated Ammonia (LiquidVapor): Pressure Table 742
TABLE A-15 Properties of Superheated Ammonia Vapor 743
TABLE A-16 Properties of Saturated Propane (LiquidVapor): Temperature Table 747
TABLE A-17 Properties of Saturated Propane (LiquidVapor): Pressure Table 748
TABLE A-18 Properties of Superheated Propane Vapor 749
TABLE A-19 Properties of Selected Solids and Liquids: cp, , and
. 753
TABLE A-20 Ideal Gas Specific Heats of Some Common Gases 754
TABLE A-21 Variation of cp with Temperature for Selected Ideal Gases 755
TABLE A-22 Ideal Gas Properties of Air 756
TABLE A-23 Ideal Gas Properties of Selected Gases 758
TABLE A-24 Constants for the van der Waals, RedlichKwong, and BenedictWebbRubin Equations
of State 762
TABLE A-25 Thermochemical Properties of Selected Substances at 298 K and 1 atm 763
TABLE A-26 Standard Molar Chemical Exergy, e ch (kJ/kmol), of Selected Substances at 298 K and p0 764
TABLE A-27 Logarithms to the Base 10 of the Equilibrium Constant K 765
718
Tables in SI Units 719
Table A-1
TABLE A-1 Atomic or Molecular Weights and Critical Properties of Selected
Elements and Compounds
Chemical M Tc pc pcvc
Substance Formula (kg/kmol) (K) (bar) Zc
RTc
Acetylene C2H2 26.04 309 62.8 0.274
Air (equivalent) 28.97 133 37.7 0.284
Ammonia NH3 17.03 406 112.8 0.242
Argon Ar 39.94 151 48.6 0.290
Benzene C6H6 78.11 563 49.3 0.274
Butane C4H10 58.12 425 38.0 0.274
Carbon C 12.01
Carbon dioxide CO2 44.01 304 73.9 0.276
Carbon monoxide CO 28.01 133 35.0 0.294
Copper Cu 63.54
Ethane C2H6 30.07 305 48.8 0.285
Ethyl alcohol C2H5OH 46.07 516 63.8 0.249
Ethylene C2H4 28.05 283 51.2 0.270
Helium He 4.003 5.2 2.3 0.300
Hydrogen H2 2.016 33.2 13.0 0.304
Methane CH4 16.04 191 46.4 0.290
Methyl alcohol CH3OH 32.04 513 79.5 0.220
Nitrogen N2 28.01 126 33.9 0.291
Octane C8H18 114.22 569 24.9 0.258
Oxygen O2 32.00 154 50.5 0.290
Propane C3H8 44.09 370 42.7 0.276
Propylene C3H6 42.08 365 46.2 0.276
Refrigerant 12 CCl2F2 120.92 385 41.2 0.278
Refrigerant 22 CHClF2 86.48 369 49.8 0.267
Refrigerant 134a CF3CH2F 102.03 374 40.7 0.260
Sulfur dioxide SO2 64.06 431 78.7 0.268
Water H2O 18.02 647.3 220.9 0.233
Sources: Adapted from International Critical Tables and L. C. Nelson and E. F. Obert, Generalized Compressibility
Charts, Chem. Eng., 61: 203 (1954).
720 Tables in SI Units
TABLE A-2 Properties of Saturated Water (LiquidVapor): Temperature Table

Specific Volume Internal Energy Enthalpy Entropy
m3/kg kJ/kg kJ/kg kJ/kg # K
Sat. Sat. Sat. Sat. Sat. Sat. Sat. Sat.
Temp. Press. Liquid Vapor Liquid Vapor Liquid Evap. Vapor Liquid Vapor Temp.
C bar vf 103 vg uf ug hf hfg hg sf sg C
H2O
.01 0.00611 1.0002 206.136 0.00 2375.3 0.01 2501.3 2501.4 0.0000 9.1562 .01
4 0.00813 1.0001 157.232 16.77 2380.9 16.78 2491.9 2508.7 0.0610 9.0514 4
5 0.00872 1.0001 147.120 20.97 2382.3 20.98 2489.6 2510.6 0.0761 9.0257 5
6 0.00935 1.0001 137.734 25.19 2383.6 25.20 2487.2 2512.4 0.0912 9.0003 6
8 0.01072 1.0002 120.917 33.59 2386.4 33.60 2482.5 2516.1 0.1212 8.9501 8
10 0.01228 1.0004 106.379 42.00 2389.2 42.01 2477.7 2519.8 0.1510 8.9008 10
11 0.01312 1.0004 99.857 46.20 2390.5 46.20 2475.4 2521.6 0.1658 8.8765 11
12 0.01402 1.0005 93.784 50.41 2391.9 50.41 2473.0 2523.4 0.1806 8.8524 12
13 0.01497 1.0007 88.124 54.60 2393.3 54.60 2470.7 2525.3 0.1953 8.8285 13
14 0.01598 1.0008 82.848 58.79 2394.7 58.80 2468.3 2527.1 0.2099 8.8048 14
15 0.01705 1.0009 77.926 62.99 2396.1 62.99 2465.9 2528.9 0.2245 8.7814 15
16 0.01818 1.0011 73.333 67.18 2397.4 67.19 2463.6 2530.8 0.2390 8.7582 16
17 0.01938 1.0012 69.044 71.38 2398.8 71.38 2461.2 2532.6 0.2535 8.7351 17
18 0.02064 1.0014 65.038 75.57 2400.2 75.58 2458.8 2534.4 0.2679 8.7123 18
19 0.02198 1.0016 61.293 79.76 2401.6 79.77 2456.5 2536.2 0.2823 8.6897 19
20 0.02339 1.0018 57.791 83.95 2402.9 83.96 2454.1 2538.1 0.2966 8.6672 20
21 0.02487 1.0020 54.514 88.14 2404.3 88.14 2451.8 2539.9 0.3109 8.6450 21
22 0.02645 1.0022 51.447 92.32 2405.7 92.33 2449.4 2541.7 0.3251 8.6229 22
23 0.02810 1.0024 48.574 96.51 2407.0 96.52 2447.0 2543.5 0.3393 8.6011 23
24 0.02985 1.0027 45.883 100.70 2408.4 100.70 2444.7 2545.4 0.3534 8.5794 24
25 0.03169 1.0029 43.360 104.88 2409.8 104.89 2442.3 2547.2 0.3674 8.5580 25
26 0.03363 1.0032 40.994 109.06 2411.1 109.07 2439.9 2549.0 0.3814 8.5367 26
27 0.03567 1.0035 38.774 113.25 2412.5 113.25 2437.6 2550.8 0.3954 8.5156 27
28 0.03782 1.0037 36.690 117.42 2413.9 117.43 2435.2 2552.6 0.4093 8.4946 28
29 0.04008 1.0040 34.733 121.60 2415.2 121.61 2432.8 2554.5 0.4231 8.4739 29
30 0.04246 1.0043 32.894 125.78 2416.6 125.79 2430.5 2556.3 0.4369 8.4533 30
31 0.04496 1.0046 31.165 129.96 2418.0 129.97 2428.1 2558.1 0.4507 8.4329 31
32 0.04759 1.0050 29.540 134.14 2419.3 134.15 2425.7 2559.9 0.4644 8.4127 32
33 0.05034 1.0053 28.011 138.32 2420.7 138.33 2423.4 2561.7 0.4781 8.3927 33
34 0.05324 1.0056 26.571 142.50 2422.0 142.50 2421.0 2563.5 0.4917 8.3728 34
35 0.05628 1.0060 25.216 146.67 2423.4 146.68 2418.6 2565.3 0.5053 8.3531 35
36 0.05947 1.0063 23.940 150.85 2424.7 150.86 2416.2 2567.1 0.5188 8.3336 36
38 0.06632 1.0071 21.602 159.20 2427.4 159.21 2411.5 2570.7 0.5458 8.2950 38
40 0.07384 1.0078 19.523 167.56 2430.1 167.57 2406.7 2574.3 0.5725 8.2570 40
45 0.09593 1.0099 15.258 188.44 2436.8 188.45 2394.8 2583.2 0.6387 8.1648 45
TABLE A-2 (Continued)

H2O
50 .1235 1.0121 12.032 209.32 2443.5 209.33 2382.7 2592.1 .7038 8.0763 50
55 .1576 1.0146 9.568 230.21 2450.1 230.23 2370.7 2600.9 .7679 7.9913 55
60 .1994 1.0172 7.671 251.11 2456.6 251.13 2358.5 2609.6 .8312 7.9096 60
65 .2503 1.0199 6.197 272.02 2463.1 272.06 2346.2 2618.3 .8935 7.8310 65
70 .3119 1.0228 5.042 292.95 2469.6 292.98 2333.8 2626.8 .9549 7.7553 70
75 .3858 1.0259 4.131 313.90 2475.9 313.93 2321.4 2635.3 1.0155 7.6824 75
80 .4739 1.0291 3.407 334.86 2482.2 334.91 2308.8 2643.7 1.0753 7.6122 80
85 .5783 1.0325 2.828 355.84 2488.4 355.90 2296.0 2651.9 1.1343 7.5445 85
90 .7014 1.0360 2.361 376.85 2494.5 376.92 2283.2 2660.1 1.1925 7.4791 90
95 .8455 1.0397 1.982 397.88 2500.6 397.96 2270.2 2668.1 1.2500 7.4159 95
100 1.014 1.0435 1.673 418.94 2506.5 419.04 2257.0 2676.1 1.3069 7.3549 100
110 1.433 1.0516 1.210 461.14 2518.1 461.30 2230.2 2691.5 1.4185 7.2387 110
120 1.985 1.0603 0.8919 503.50 2529.3 503.71 2202.6 2706.3 1.5276 7.1296 120
130 2.701 1.0697 0.6685 546.02 2539.9 546.31 2174.2 2720.5 1.6344 7.0269 130
140 3.613 1.0797 0.5089 588.74 2550.0 589.13 2144.7 2733.9 1.7391 6.9299 140
150 4.758 1.0905 0.3928 631.68 2559.5 632.20 2114.3 2746.5 1.8418 6.8379 150
160 6.178 1.1020 0.3071 674.86 2568.4 675.55 2082.6 2758.1 1.9427 6.7502 160
170 7.917 1.1143 0.2428 718.33 2576.5 719.21 2049.5 2768.7 2.0419 6.6663 170
180 10.02 1.1274 0.1941 762.09 2583.7 763.22 2015.0 2778.2 2.1396 6.5857 180
190 12.54 1.1414 0.1565 806.19 2590.0 807.62 1978.8 2786.4 2.2359 6.5079 190
200 15.54 1.1565 0.1274 850.65 2595.3 852.45 1940.7 2793.2 2.3309 6.4323 200
210 19.06 1.1726 0.1044 895.53 2599.5 897.76 1900.7 2798.5 2.4248 6.3585 210
220 23.18 1.1900 0.08619 940.87 2602.4 943.62 1858.5 2802.1 2.5178 6.2861 220
230 27.95 1.2088 0.07158 986.74 2603.9 990.12 1813.8 2804.0 2.6099 6.2146 230
240 33.44 1.2291 0.05976 1033.2 2604.0 1037.3 1766.5 2803.8 2.7015 6.1437 240
250 39.73 1.2512 0.05013 1080.4 2602.4 1085.4 1716.2 2801.5 2.7927 6.0730 250
260 46.88 1.2755 0.04221 1128.4 2599.0 1134.4 1662.5 2796.6 2.8838 6.0019 260
270 54.99 1.3023 0.03564 1177.4 2593.7 1184.5 1605.2 2789.7 2.9751 5.9301 270
280 64.12 1.3321 0.03017 1227.5 2586.1 1236.0 1543.6 2779.6 3.0668 5.8571 280
290 74.36 1.3656 0.02557 1278.9 2576.0 1289.1 1477.1 2766.2 3.1594 5.7821 290
300 85.81 1.4036 0.02167 1332.0 2563.0 1344.0 1404.9 2749.0 3.2534 5.7045 300
320 112.7 1.4988 0.01549 1444.6 2525.5 1461.5 1238.6 2700.1 3.4480 5.5362 320
340 145.9 1.6379 0.01080 1570.3 2464.6 1594.2 1027.9 2622.0 3.6594 5.3357 340
360 186.5 1.8925 0.006945 1725.2 2351.5 1760.5 720.5 2481.0 3.9147 5.0526 360
374.14 220.9 3.155 0.003155 2029.6 2029.6 2099.3 0 2099.3 4.4298 4.4298 374.14
Source: Tables A-2 through A-5 are extracted from J. H. Keenan, F. G. Keyes, P. G. Hill, and J. G. Moore, Steam Tables, Wiley, New York, 1969.
TABLE A-3 Properties of Saturated Water (LiquidVapor): Pressure Table

Press. Temp. Liquid Vapor Liquid Vapor Liquid Evap. Vapor Liquid Vapor Press.
bar C vf 103 vg uf ug hf hfg hg sf sg bar
H2O
0.04 28.96 1.0040 34.800 121.45 2415.2 121.46 2432.9 2554.4 0.4226 8.4746 0.04
0.06 36.16 1.0064 23.739 151.53 2425.0 151.53 2415.9 2567.4 0.5210 8.3304 0.06
0.08 41.51 1.0084 18.103 173.87 2432.2 173.88 2403.1 2577.0 0.5926 8.2287 0.08
0.10 45.81 1.0102 14.674 191.82 2437.9 191.83 2392.8 2584.7 0.6493 8.1502 0.10
0.20 60.06 1.0172 7.649 251.38 2456.7 251.40 2358.3 2609.7 0.8320 7.9085 0.20
0.30 69.10 1.0223 5.229 289.20 2468.4 289.23 2336.1 2625.3 0.9439 7.7686 0.30
0.40 75.87 1.0265 3.993 317.53 2477.0 317.58 2319.2 2636.8 1.0259 7.6700 0.40
0.50 81.33 1.0300 3.240 340.44 2483.9 340.49 2305.4 2645.9 1.0910 7.5939 0.50
0.60 85.94 1.0331 2.732 359.79 2489.6 359.86 2293.6 2653.5 1.1453 7.5320 0.60
0.70 89.95 1.0360 2.365 376.63 2494.5 376.70 2283.3 2660.0 1.1919 7.4797 0.70
0.80 93.50 1.0380 2.087 391.58 2498.8 391.66 2274.1 2665.8 1.2329 7.4346 0.80
0.90 96.71 1.0410 1.869 405.06 2502.6 405.15 2265.7 2670.9 1.2695 7.3949 0.90
1.00 99.63 1.0432 1.694 417.36 2506.1 417.46 2258.0 2675.5 1.3026 7.3594 1.00
1.50 111.4 1.0528 1.159 466.94 2519.7 467.11 2226.5 2693.6 1.4336 7.2233 1.50
2.00 120.2 1.0605 0.8857 504.49 2529.5 504.70 2201.9 2706.7 1.5301 7.1271 2.00
2.50 127.4 1.0672 0.7187 535.10 2537.2 535.37 2181.5 2716.9 1.6072 7.0527 2.50
3.00 133.6 1.0732 0.6058 561.15 2543.6 561.47 2163.8 2725.3 1.6718 6.9919 3.00
3.50 138.9 1.0786 0.5243 583.95 2546.9 584.33 2148.1 2732.4 1.7275 6.9405 3.50
4.00 143.6 1.0836 0.4625 604.31 2553.6 604.74 2133.8 2738.6 1.7766 6.8959 4.00
4.50 147.9 1.0882 0.4140 622.25 2557.6 623.25 2120.7 2743.9 1.8207 6.8565 4.50
5.00 151.9 1.0926 0.3749 639.68 2561.2 640.23 2108.5 2748.7 1.8607 6.8212 5.00
6.00 158.9 1.1006 0.3157 669.90 2567.4 670.56 2086.3 2756.8 1.9312 6.7600 6.00
7.00 165.0 1.1080 0.2729 696.44 2572.5 697.22 2066.3 2763.5 1.9922 6.7080 7.00
8.00 170.4 1.1148 0.2404 720.22 2576.8 721.11 2048.0 2769.1 2.0462 6.6628 8.00
9.00 175.4 1.1212 0.2150 741.83 2580.5 742.83 2031.1 2773.9 2.0946 6.6226 9.00
10.0 179.9 1.1273 0.1944 761.68 2583.6 762.81 2015.3 2778.1 2.1387 6.5863 10.0
15.0 198.3 1.1539 0.1318 843.16 2594.5 844.84 1947.3 2792.2 2.3150 6.4448 15.0
20.0 212.4 1.1767 0.09963 906.44 2600.3 908.79 1890.7 2799.5 2.4474 6.3409 20.0
25.0 224.0 1.1973 0.07998 959.11 2603.1 962.11 1841.0 2803.1 2.5547 6.2575 25.0
30.0 233.9 1.2165 0.06668 1004.8 2604.1 1008.4 1795.7 2804.2 2.6457 6.1869 30.0
35.0 242.6 1.2347 0.05707 1045.4 2603.7 1049.8 1753.7 2803.4 2.7253 6.1253 35.0
40.0 250.4 1.2522 0.04978 1082.3 2602.3 1087.3 1714.1 2801.4 2.7964 6.0701 40.0
45.0 257.5 1.2692 0.04406 1116.2 2600.1 1121.9 1676.4 2798.3 2.8610 6.0199 45.0
50.0 264.0 1.2859 0.03944 1147.8 2597.1 1154.2 1640.1 2794.3 2.9202 5.9734 50.0
60.0 275.6 1.3187 0.03244 1205.4 2589.7 1213.4 1571.0 2784.3 3.0267 5.8892 60.0
70.0 285.9 1.3513 0.02737 1257.6 2580.5 1267.0 1505.1 2772.1 3.1211 5.8133 70.0
80.0 295.1 1.3842 0.02352 1305.6 2569.8 1316.6 1441.3 2758.0 3.2068 5.7432 80.0
90.0 303.4 1.4178 0.02048 1350.5 2557.8 1363.3 1378.9 2742.1 3.2858 5.6772 90.0
100. 311.1 1.4524 0.01803 1393.0 2544.4 1407.6 1317.1 2724.7 3.3596 5.6141 100.
110. 318.2 1.4886 0.01599 1433.7 2529.8 1450.1 1255.5 2705.6 3.4295 5.5527 110.

H2O
120. 324.8 1.5267 0.01426 1473.0 2513.7 1491.3 1193.6 2684.9 3.4962 5.4924 120.
130. 330.9 1.5671 0.01278 1511.1 2496.1 1531.5 1130.7 2662.2 3.5606 5.4323 130.
140. 336.8 1.6107 0.01149 1548.6 2476.8 1571.1 1066.5 2637.6 3.6232 5.3717 140.
150. 342.2 1.6581 0.01034 1585.6 2455.5 1610.5 1000.0 2610.5 3.6848 5.3098 150.
160. 347.4 1.7107 0.009306 1622.7 2431.7 1650.1 930.6 2580.6 3.7461 5.2455 160.
170. 352.4 1.7702 0.008364 1660.2 2405.0 1690.3 856.9 2547.2 3.8079 5.1777 170.
180. 357.1 1.8397 0.007489 1698.9 2374.3 1732.0 777.1 2509.1 3.8715 5.1044 180.
190. 361.5 1.9243 0.006657 1739.9 2338.1 1776.5 688.0 2464.5 3.9388 5.0228 190.
200. 365.8 2.036 0.005834 1785.6 2293.0 1826.3 583.4 2409.7 4.0139 4.9269 200.
220.9 374.1 3.155 0.003155 2029.6 2029.6 2099.3 0 2099.3 4.4298 4.4298 220.9
TABLE A-4 Properties of Superheated Water Vapor

T v u h s v u h s
C m3/kg kJ/kg kJ/kg kJ/kg # K m3/kg kJ/kg kJ/kg kJ/kg # K
p 0.06 bar 0.006 MPa p 0.35 bar 0.035 MPa
(Tsat 36.16C) (Tsat 72.69C)
Sat. 23.739 2425.0 2567.4 8.3304 4.526 2473.0 2631.4 7.7158
H2O
80 27.132 2487.3 2650.1 8.5804 4.625 2483.7 2645.6 7.7564

120 30.219 2544.7 2726.0 8.7840 5.163 2542.4 2723.1 7.9644
160 33.302 2602.7 2802.5 8.9693 5.696 2601.2 2800.6 8.1519
200 36.383 2661.4 2879.7 9.1398 6.228 2660.4 2878.4 8.3237
240 39.462 2721.0 2957.8 9.2982 6.758 2720.3 2956.8 8.4828
280 42.540 2781.5 3036.8 9.4464 7.287 2780.9 3036.0 8.6314
320 45.618 2843.0 3116.7 9.5859 7.815 2842.5 3116.1 8.7712
360 48.696 2905.5 3197.7 9.7180 8.344 2905.1 3197.1 8.9034
400 51.774 2969.0 3279.6 9.8435 8.872 2968.6 3279.2 9.0291
440 54.851 3033.5 3362.6 9.9633 9.400 3033.2 3362.2 9.1490
500 59.467 3132.3 3489.1 10.1336 10.192 3132.1 3488.8 9.3194
p 0.70 bar 0.07 MPa p 1.0 bar 0.10 MPa

(Tsat 89.95C) (Tsat 99.63C)
Sat. 2.365 2494.5 2660.0 7.4797 1.694 2506.1 2675.5 7.3594
100 2.434 2509.7 2680.0 7.5341 1.696 2506.7 2676.2 7.3614
120 2.571 2539.7 2719.6 7.6375 1.793 2537.3 2716.6 7.4668
160 2.841 2599.4 2798.2 7.8279 1.984 2597.8 2796.2 7.6597
200 3.108 2659.1 2876.7 8.0012 2.172 2658.1 2875.3 7.8343
240 3.374 2719.3 2955.5 8.1611 2.359 2718.5 2954.5 7.9949
280 3.640 2780.2 3035.0 8.3162 2.546 2779.6 3034.2 8.1445
320 3.905 2842.0 3115.3 8.4504 2.732 2841.5 3114.6 8.2849
360 4.170 2904.6 3196.5 8.5828 2.917 2904.2 3195.9 8.4175
400 4.434 2968.2 3278.6 8.7086 3.103 2967.9 3278.2 8.5435
440 4.698 3032.9 3361.8 8.8286 3.288 3032.6 3361.4 8.6636
500 5.095 3131.8 3488.5 8.9991 3.565 3131.6 3488.1 8.8342
p 1.5 bar 0.15 MPa p 3.0 bar 0.30 MPa

(Tsat 111.37C) (Tsat 133.55C)
Sat. 1.159 2519.7 2693.6 7.2233 0.606 2543.6 2725.3 6.9919
120 1.188 2533.3 2711.4 7.2693
160 1.317 2595.2 2792.8 7.4665 0.651 2587.1 2782.3 7.1276
200 1.444 2656.2 2872.9 7.6433 0.716 2650.7 2865.5 7.3115
240 1.570 2717.2 2952.7 7.8052 0.781 2713.1 2947.3 7.4774
280 1.695 2778.6 3032.8 7.9555 0.844 2775.4 3028.6 7.6299
320 1.819 2840.6 3113.5 8.0964 0.907 2838.1 3110.1 7.7722
360 1.943 2903.5 3195.0 8.2293 0.969 2901.4 3192.2 7.9061
400 2.067 2967.3 3277.4 8.3555 1.032 2965.6 3275.0 8.0330
440 2.191 3032.1 3360.7 8.4757 1.094 3030.6 3358.7 8.1538
500 2.376 3131.2 3487.6 8.6466 1.187 3130.0 3486.0 8.3251
600 2.685 3301.7 3704.3 8.9101 1.341 3300.8 3703.2 8.5892

T v u h s v u h s
p 5.0 bar 0.50 MPa p 7.0 bar 0.70 MPa
(Tsat 151.86C) (Tsat 164.97C)
Sat. 0.3749 2561.2 2748.7 6.8213 0.2729 2572.5 2763.5 6.7080
H2O
180 0.4045 2609.7 2812.0 6.9656 0.2847 2599.8 2799.1 6.7880
200 0.4249 2642.9 2855.4 7.0592 0.2999 2634.8 2844.8 6.8865
240 0.4646 2707.6 2939.9 7.2307 0.3292 2701.8 2932.2 7.0641
280 0.5034 2771.2 3022.9 7.3865 0.3574 2766.9 3017.1 7.2233
320 0.5416 2834.7 3105.6 7.5308 0.3852 2831.3 3100.9 7.3697
360 0.5796 2898.7 3188.4 7.6660 0.4126 2895.8 3184.7 7.5063
400 0.6173 2963.2 3271.9 7.7938 0.4397 2960.9 3268.7 7.6350
440 0.6548 3028.6 3356.0 7.9152 0.4667 3026.6 3353.3 7.7571
500 0.7109 3128.4 3483.9 8.0873 0.5070 3126.8 3481.7 7.9299
600 0.8041 3299.6 3701.7 8.3522 0.5738 3298.5 3700.2 8.1956
700 0.8969 3477.5 3925.9 8.5952 0.6403 3476.6 3924.8 8.4391
p 10.0 bar 1.0 MPa p 15.0 bar 1.5 MPa

(Tsat 179.91C) (Tsat 198.32C)
Sat. 0.1944 2583.6 2778.1 6.5865 0.1318 2594.5 2792.2 6.4448
200 0.2060 2621.9 2827.9 6.6940 0.1325 2598.1 2796.8 6.4546
240 0.2275 2692.9 2920.4 6.8817 0.1483 2676.9 2899.3 6.6628
280 0.2480 2760.2 3008.2 7.0465 0.1627 2748.6 2992.7 6.8381
320 0.2678 2826.1 3093.9 7.1962 0.1765 2817.1 3081.9 6.9938
360 0.2873 2891.6 3178.9 7.3349 0.1899 2884.4 3169.2 7.1363
400 0.3066 2957.3 3263.9 7.4651 0.2030 2951.3 3255.8 7.2690
440 0.3257 3023.6 3349.3 7.5883 0.2160 3018.5 3342.5 7.3940
500 0.3541 3124.4 3478.5 7.7622 0.2352 3120.3 3473.1 7.5698
540 0.3729 3192.6 3565.6 7.8720 0.2478 3189.1 3560.9 7.6805
600 0.4011 3296.8 3697.9 8.0290 0.2668 3293.9 3694.0 7.8385
640 0.4198 3367.4 3787.2 8.1290 0.2793 3364.8 3783.8 7.9391
p 20.0 bar 2.0 MPa p 30.0 bar 3.0 MPa

(Tsat 212.42C) (Tsat 233.90C)
Sat. 0.0996 2600.3 2799.5 6.3409 0.0667 2604.1 2804.2 6.1869
240 0.1085 2659.6 2876.5 6.4952 0.0682 2619.7 2824.3 6.2265
280 0.1200 2736.4 2976.4 6.6828 0.0771 2709.9 2941.3 6.4462
320 0.1308 2807.9 3069.5 6.8452 0.0850 2788.4 3043.4 6.6245
360 0.1411 2877.0 3159.3 6.9917 0.0923 2861.7 3138.7 6.7801
400 0.1512 2945.2 3247.6 7.1271 0.0994 2932.8 3230.9 6.9212
440 0.1611 3013.4 3335.5 7.2540 0.1062 3002.9 3321.5 7.0520
500 0.1757 3116.2 3467.6 7.4317 0.1162 3108.0 3456.5 7.2338
540 0.1853 3185.6 3556.1 7.5434 0.1227 3178.4 3546.6 7.3474
600 0.1996 3290.9 3690.1 7.7024 0.1324 3285.0 3682.3 7.5085
640 0.2091 3362.2 3780.4 7.8035 0.1388 3357.0 3773.5 7.6106
700 0.2232 3470.9 3917.4 7.9487 0.1484 3466.5 3911.7 7.7571

T v u h s v u h s
p 40 bar 4.0 MPa p 60 bar 6.0 MPa
(Tsat 250.4C) (Tsat 275.64C)
Sat. 0.04978 2602.3 2801.4 6.0701 0.03244 2589.7 2784.3 5.8892
H2O
280 0.05546 2680.0 2901.8 6.2568 0.03317 2605.2 2804.2 5.9252

320 0.06199 2767.4 3015.4 6.4553 0.03876 2720.0 2952.6 6.1846
360 0.06788 2845.7 3117.2 6.6215 0.04331 2811.2 3071.1 6.3782
400 0.07341 2919.9 3213.6 6.7690 0.04739 2892.9 3177.2 6.5408
440 0.07872 2992.2 3307.1 6.9041 0.05122 2970.0 3277.3 6.6853
500 0.08643 3099.5 3445.3 7.0901 0.05665 3082.2 3422.2 6.8803
540 0.09145 3171.1 3536.9 7.2056 0.06015 3156.1 3517.0 6.9999
600 0.09885 3279.1 3674.4 7.3688 0.06525 3266.9 3658.4 7.1677
640 0.1037 3351.8 3766.6 7.4720 0.06859 3341.0 3752.6 7.2731
700 0.1110 3462.1 3905.9 7.6198 0.07352 3453.1 3894.1 7.4234
740 0.1157 3536.6 3999.6 7.7141 0.07677 3528.3 3989.2 7.5190

(Tsat 295.06C) (Tsat 311.06C)
Sat. 0.02352 2569.8 2758.0 5.7432 0.01803 2544.4 2724.7 5.6141
320 0.02682 2662.7 2877.2 5.9489 0.01925 2588.8 2781.3 5.7103
360 0.03089 2772.7 3019.8 6.1819 0.02331 2729.1 2962.1 6.0060
400 0.03432 2863.8 3138.3 6.3634 0.02641 2832.4 3096.5 6.2120
440 0.03742 2946.7 3246.1 6.5190 0.02911 2922.1 3213.2 6.3805
480 0.04034 3025.7 3348.4 6.6586 0.03160 3005.4 3321.4 6.5282
520 0.04313 3102.7 3447.7 6.7871 0.03394 3085.6 3425.1 6.6622
560 0.04582 3178.7 3545.3 6.9072 0.03619 3164.1 3526.0 6.7864
600 0.04845 3254.4 3642.0 7.0206 0.03837 3241.7 3625.3 6.9029
640 0.05102 3330.1 3738.3 7.1283 0.04048 3318.9 3723.7 7.0131
700 0.05481 3443.9 3882.4 7.2812 0.04358 3434.7 3870.5 7.1687
740 0.05729 3520.4 3978.7 7.3782 0.04560 3512.1 3968.1 7.2670
p 120 bar 12.0 MPa p 140 bar 14.0 MPa

(Tsat 324.75C) (Tsat 336.75C)
Sat. 0.01426 2513.7 2684.9 5.4924 0.01149 2476.8 2637.6 5.3717
360 0.01811 2678.4 2895.7 5.8361 0.01422 2617.4 2816.5 5.6602
400 0.02108 2798.3 3051.3 6.0747 0.01722 2760.9 3001.9 5.9448
440 0.02355 2896.1 3178.7 6.2586 0.01954 2868.6 3142.2 6.1474
480 0.02576 2984.4 3293.5 6.4154 0.02157 2962.5 3264.5 6.3143
520 0.02781 3068.0 3401.8 6.5555 0.02343 3049.8 3377.8 6.4610
560 0.02977 3149.0 3506.2 6.6840 0.02517 3133.6 3486.0 6.5941
600 0.03164 3228.7 3608.3 6.8037 0.02683 3215.4 3591.1 6.7172
640 0.03345 3307.5 3709.0 6.9164 0.02843 3296.0 3694.1 6.8326
700 0.03610 3425.2 3858.4 7.0749 0.03075 3415.7 3846.2 6.9939
740 0.03781 3503.7 3957.4 7.1746 0.03225 3495.2 3946.7 7.0952

T v u h s v u h s
p 160 bar 16.0 MPa p 180 bar 18.0 MPa
(Tsat 347.44C) (Tsat 357.06C)
Sat. 0.00931 2431.7 2580.6 5.2455 0.00749 2374.3 2509.1 5.1044
H2O
360 0.01105 2539.0 2715.8 5.4614 0.00809 2418.9 2564.5 5.1922
400 0.01426 2719.4 2947.6 5.8175 0.01190 2672.8 2887.0 5.6887
440 0.01652 2839.4 3103.7 6.0429 0.01414 2808.2 3062.8 5.9428
480 0.01842 2939.7 3234.4 6.2215 0.01596 2915.9 3203.2 6.1345
520 0.02013 3031.1 3353.3 6.3752 0.01757 3011.8 3378.0 6.2960
560 0.02172 3117.8 3465.4 6.5132 0.01904 3101.7 3444.4 6.4392
600 0.02323 3201.8 3573.5 6.6399 0.02042 3188.0 3555.6 6.5696
640 0.02467 3284.2 3678.9 6.7580 0.02174 3272.3 3663.6 6.6905
700 0.02674 3406.0 3833.9 6.9224 0.02362 3396.3 3821.5 6.8580
740 0.02808 3486.7 3935.9 7.0251 0.02483 3478.0 3925.0 6.9623
p 200 bar 20.0 MPa p 240 bar 24.0 MPa

(Tsat 365.81C)
Sat. 0.00583 2293.0 2409.7 4.9269
400 0.00994 2619.3 2818.1 5.5540 0.00673 2477.8 2639.4 5.2393
440 0.01222 2774.9 3019.4 5.8450 0.00929 2700.6 2923.4 5.6506
480 0.01399 2891.2 3170.8 6.0518 0.01100 2838.3 3102.3 5.8950
520 0.01551 2992.0 3302.2 6.2218 0.01241 2950.5 3248.5 6.0842
560 0.01689 3085.2 3423.0 6.3705 0.01366 3051.1 3379.0 6.2448
600 0.01818 3174.0 3537.6 6.5048 0.01481 3145.2 3500.7 6.3875
640 0.01940 3260.2 3648.1 6.6286 0.01588 3235.5 3616.7 6.5174
700 0.02113 3386.4 3809.0 6.7993 0.01739 3366.4 3783.8 6.6947
740 0.02224 3469.3 3914.1 6.9052 0.01835 3451.7 3892.1 6.8038
800 0.02385 3592.7 4069.7 7.0544 0.01974 3578.0 4051.6 6.9567
p 280 bar 28.0 MPa p 320 bar 32.0 MPa

400 0.00383 2223.5 2330.7 4.7494 0.00236 1980.4 2055.9 4.3239
440 0.00712 2613.2 2812.6 5.4494 0.00544 2509.0 2683.0 5.2327
480 0.00885 2780.8 3028.5 5.7446 0.00722 2718.1 2949.2 5.5968
520 0.01020 2906.8 3192.3 5.9566 0.00853 2860.7 3133.7 5.8357
560 0.01136 3015.7 3333.7 6.1307 0.00963 2979.0 3287.2 6.0246
600 0.01241 3115.6 3463.0 6.2823 0.01061 3085.3 3424.6 6.1858
640 0.01338 3210.3 3584.8 6.4187 0.01150 3184.5 3552.5 6.3290
700 0.01473 3346.1 3758.4 6.6029 0.01273 3325.4 3732.8 6.5203
740 0.01558 3433.9 3870.0 6.7153 0.01350 3415.9 3847.8 6.6361
800 0.01680 3563.1 4033.4 6.8720 0.01460 3548.0 4015.1 6.7966
900 0.01873 3774.3 4298.8 7.1084 0.01633 3762.7 4285.1 7.0372
TABLE A-5 Properties of Compressed Liquid Water

T v 10 3
u h s v 103 u h s
(Tsat 223.99C) (Tsat 263.99C)
20 1.0006 83.80 86.30 .2961 .9995 83.65 88.65 .2956
H2O
40 1.0067 167.25 169.77 .5715 1.0056 166.95 171.97 .5705

80 1.0280 334.29 336.86 1.0737 1.0268 333.72 338.85 1.0720
100 1.0423 418.24 420.85 1.3050 1.0410 417.52 422.72 1.3030
140 1.0784 587.82 590.52 1.7369 1.0768 586.76 592.15 1.7343
180 1.1261 761.16 763.97 2.1375 1.1240 759.63 765.25 2.1341
200 1.1555 849.9 852.8 2.3294 1.1530 848.1 853.9 2.3255
220 1.1898 940.7 943.7 2.5174 1.1866 938.4 944.4 2.5128
Sat. 1.1973 959.1 962.1 2.5546 1.2859 1147.8 1154.2 2.9202

(Tsat 290.59C) (Tsat 311.06C)
20 .9984 83.50 90.99 .2950 .9972 83.36 93.33 .2945
40 1.0045 166.64 174.18 .5696 1.0034 166.35 176.38 .5686
80 1.0256 333.15 340.84 1.0704 1.0245 332.59 342.83 1.0688
100 1.0397 416.81 424.62 1.3011 1.0385 416.12 426.50 1.2992
140 1.0752 585.72 593.78 1.7317 1.0737 584.68 595.42 1.7292
180 1.1219 758.13 766.55 2.1308 1.1199 756.65 767.84 2.1275
220 1.1835 936.2 945.1 2.5083 1.1805 934.1 945.9 2.5039
260 1.2696 1124.4 1134.0 2.8763 1.2645 1121.1 1133.7 2.8699
Sat. 1.3677 1282.0 1292.2 3.1649 1.4524 1393.0 1407.6 3.3596
p 150 bar 15.0 MPa p 200 bar 20.0 MPa

(Tsat 342.24C) (Tsat 365.81C)
20 .9950 83.06 97.99 .2934 .9928 82.77 102.62 .2923
40 1.0013 165.76 180.78 .5666 .9992 165.17 185.16 .5646
80 1.0222 331.48 346.81 1.0656 1.0199 330.40 350.80 1.0624
100 1.0361 414.74 430.28 1.2955 1.0337 413.39 434.06 1.2917
140 1.0707 582.66 598.72 1.7242 1.0678 580.69 602.04 1.7193
180 1.1159 753.76 770.50 2.1210 1.1120 750.95 773.20 2.1147
220 1.1748 929.9 947.5 2.4953 1.1693 925.9 949.3 2.4870
260 1.2550 1114.6 1133.4 2.8576 1.2462 1108.6 1133.5 2.8459
300 1.3770 1316.6 1337.3 3.2260 1.3596 1306.1 1333.3 3.2071
Sat. 1.6581 1585.6 1610.5 3.6848 2.036 1785.6 1826.3 4.0139
p 250 bar 25 MPa p 300 bar 30.0 MPa

20 .9907 82.47 107.24 .2911 .9886 82.17 111.84 .2899
40 .9971 164.60 189.52 .5626 .9951 164.04 193.89 .5607
100 1.0313 412.08 437.85 1.2881 1.0290 410.78 441.66 1.2844
200 1.1344 834.5 862.8 2.2961 1.1302 831.4 865.3 2.2893
300 1.3442 1296.6 1330.2 3.1900 1.3304 1287.9 1327.8 3.1741
TABLE A-6 Properties of Saturated Water (SolidVapor): Temperature Table
Temp. Pressure Solid Vapor Solid Subl. Vapor Solid Subl. Vapor Solid Subl. Vapor
C kPa vi 103 vg ui uig ug hi hig hg si sig sg
.01 .6113 1.0908 206.1 333.40 2708.7 2375.3 333.40 2834.8 2501.4 1.221 10.378 9.156
0 .6108 1.0908 206.3 333.43 2708.8 2375.3 333.43 2834.8 2501.3 1.221 10.378 9.157
2 .5176 1.0904 241.7 337.62 2710.2 2372.6 337.62 2835.3 2497.7 1.237 10.456 9.219
4 .4375 1.0901 283.8 341.78 2711.6 2369.8 341.78 2835.7 2494.0 1.253 10.536 9.283
6 .3689 1.0898 334.2 345.91 2712.9 2367.0 345.91 2836.2 2490.3 1.268 10.616 9.348
8 .3102 1.0894 394.4 350.02 2714.2 2364.2 350.02 2836.6 2486.6 1.284 10.698 9.414
10 .2602 1.0891 466.7 354.09 2715.5 2361.4 354.09 2837.0 2482.9 1.299 10.781 9.481
12 .2176 1.0888 553.7 358.14 2716.8 2358.7 358.14 2837.3 2479.2 1.315 10.865 9.550
14 .1815 1.0884 658.8 362.15 2718.0 2355.9 362.15 2837.6 2475.5 1.331 10.950 9.619
16 .1510 1.0881 786.0 366.14 2719.2 2353.1 366.14 2837.9 2471.8 1.346 11.036 9.690
18 .1252 1.0878 940.5 370.10 2720.4 2350.3 370.10 2838.2 2468.1 1.362 11.123 9.762
20 .1035 1.0874 1128.6 374.03 2721.6 2347.5 374.03 2838.4 2464.3 1.377 11.212 9.835
22 .0853 1.0871 1358.4 377.93 2722.7 2344.7 377.93 2838.6 2460.6 1.393 11.302 9.909
24 .0701 1.0868 1640.1 381.80 2723.7 2342.0 381.80 2838.7 2456.9 1.408 11.394 9.985
26 .0574 1.0864 1986.4 385.64 2724.8 2339.2 385.64 2838.9 2453.2 1.424 11.486 10.062
28 .0469 1.0861 2413.7 389.45 2725.8 2336.4 389.45 2839.0 2449.5 1.439 11.580 10.141
30 .0381 1.0858 2943 393.23 2726.8 2333.6 393.23 2839.0 2445.8 1.455 11.676 10.221
32 .0309 1.0854 3600 396.98 2727.8 2330.8 396.98 2839.1 2442.1 1.471 11.773 10.303
34 .0250 1.0851 4419 400.71 2728.7 2328.0 400.71 2839.1 2438.4 1.486 11.872 10.386
36 .0201 1.0848 5444 404.40 2729.6 2325.2 404.40 2839.1 2434.7 1.501 11.972 10.470
38 .0161 1.0844 6731 408.06 2730.5 2322.4 408.06 2839.0 2430.9 1.517 12.073 10.556
40 .0129 1.0841 8354 411.70 2731.3 2319.6 411.70 2838.9 2427.2 1.532 12.176 10.644
Source: J. H. Keenan, F. G. Keyes, P. G. Hill, and J. G. Moore, Steam Tables, Wiley, New York, 1978.
729
H2O
TABLE A-7 Properties of Saturated Refrigerant 22 (LiquidVapor): Temperature Table

60 0.3749 0.6833 0.5370 21.57 203.67 21.55 245.35 223.81 0.0964 1.0547 60
50 0.6451 0.6966 0.3239 10.89 207.70 10.85 239.44 228.60 0.0474 1.0256 50
45 0.8290 0.7037 0.2564 5.50 209.70 5.44 236.39 230.95 0.0235 1.0126 45
40 1.0522 0.7109 0.2052 0.07 211.68 0.00 233.27 233.27 0.0000 1.0005 40
36 1.2627 0.7169 0.1730 4.29 213.25 4.38 230.71 235.09 0.0186 0.9914 36
32 1.5049 0.7231 0.1468 8.68 214.80 8.79 228.10 236.89 0.0369 0.9828 32
R-22
30 1.6389 0.7262 0.1355 10.88 215.58 11.00 226.77 237.78 0.0460 0.9787 30
28 1.7819 0.7294 0.1252 13.09 216.34 13.22 225.43 238.66 0.0551 0.9746 28
26 1.9345 0.7327 0.1159 15.31 217.11 15.45 224.08 239.53 0.0641 0.9707 26
22 2.2698 0.7393 0.0997 19.76 218.62 19.92 221.32 241.24 0.0819 0.9631 22
20 2.4534 0.7427 0.0926 21.99 219.37 22.17 219.91 242.09 0.0908 0.9595 20
18 2.6482 0.7462 0.0861 24.23 220.11 24.43 218.49 242.92 0.0996 0.9559 18
16 2.8547 0.7497 0.0802 26.48 220.85 26.69 217.05 243.74 0.1084 0.9525 16
14 3.0733 0.7533 0.0748 28.73 221.58 28.97 215.59 244.56 0.1171 0.9490 14
12 3.3044 0.7569 0.0698 31.00 222.30 31.25 214.11 245.36 0.1258 0.9457 12
10 3.5485 0.7606 0.0652 33.27 223.02 33.54 212.62 246.15 0.1345 0.9424 10
8 3.8062 0.7644 0.0610 35.54 223.73 35.83 211.10 246.93 0.1431 0.9392 8
6 4.0777 0.7683 0.0571 37.83 224.43 38.14 209.56 247.70 0.1517 0.9361 6
4 4.3638 0.7722 0.0535 40.12 225.13 40.46 208.00 248.45 0.1602 0.9330 4
2 4.6647 0.7762 0.0501 42.42 225.82 42.78 206.41 249.20 0.1688 0.9300 2
0 4.9811 0.7803 0.0470 44.73 226.50 45.12 204.81 249.92 0.1773 0.9271 0
2 5.3133 0.7844 0.0442 47.04 227.17 47.46 203.18 250.64 0.1857 0.9241 2
4 5.6619 0.7887 0.0415 49.37 227.83 49.82 201.52 251.34 0.1941 0.9213 4
6 6.0275 0.7930 0.0391 51.71 228.48 52.18 199.84 252.03 0.2025 0.9184 6
8 6.4105 0.7974 0.0368 54.05 229.13 54.56 198.14 252.70 0.2109 0.9157 8
10 6.8113 0.8020 0.0346 56.40 229.76 56.95 196.40 253.35 0.2193 0.9129 10
12 7.2307 0.8066 0.0326 58.77 230.38 59.35 194.64 253.99 0.2276 0.9102 12
16 8.1268 0.8162 0.0291 63.53 231.59 64.19 191.02 255.21 0.2442 0.9048 16
20 9.1030 0.8263 0.0259 68.33 232.76 69.09 187.28 256.37 0.2607 0.8996 20
24 10.164 0.8369 0.0232 73.19 233.87 74.04 183.40 257.44 0.2772 0.8944 24
28 11.313 0.8480 0.0208 78.09 234.92 79.05 179.37 258.43 0.2936 0.8893 28
32 12.556 0.8599 0.0186 83.06 235.91 84.14 175.18 259.32 0.3101 0.8842 32
36 13.897 0.8724 0.0168 88.08 236.83 89.29 170.82 260.11 0.3265 0.8790 36
40 15.341 0.8858 0.0151 93.18 237.66 94.53 166.25 260.79 0.3429 0.8738 40
45 17.298 0.9039 0.0132 99.65 238.59 101.21 160.24 261.46 0.3635 0.8672 45
50 19.433 0.9238 0.0116 106.26 239.34 108.06 153.84 261.90 0.3842 0.8603 50
60 24.281 0.9705 0.0089 120.00 240.24 122.35 139.61 261.96 0.4264 0.8455 60
Source: Tables A-7 through A-9 are calculated based on equations from A. Kamei and S. W. Beyerlein, A Fundamental Equation for
Chlorodifluoromethane (R-22), Fluid Phase Equilibria, Vol. 80, No. 11, 1992, pp. 7186.
TABLE A-8 Properties of Saturated Refrigerant 22 (LiquidVapor): Pressure Table

0.40 58.86 0.6847 0.5056 20.36 204.13 20.34 244.69 224.36 0.0907 1.0512 0.40
0.50 54.83 0.6901 0.4107 16.07 205.76 16.03 242.33 226.30 0.0709 1.0391 0.50
0.60 51.40 0.6947 0.3466 12.39 207.14 12.35 240.28 227.93 0.0542 1.0294 0.60
0.70 48.40 0.6989 0.3002 9.17 208.34 9.12 238.47 229.35 0.0397 1.0213 0.70
0.80 45.73 0.7026 0.2650 6.28 209.41 6.23 236.84 230.61 0.0270 1.0144 0.80
0.90 43.30 0.7061 0.2374 3.66 210.37 3.60 235.34 231.74 0.0155 1.0084 0.90
R-22
1.00 41.09 0.7093 0.2152 1.26 211.25 1.19 233.95 232.77 0.0051 1.0031 1.00
1.25 36.23 0.7166 0.1746 4.04 213.16 4.13 230.86 234.99 0.0175 0.9919 1.25
1.50 32.08 0.7230 0.1472 8.60 214.77 8.70 228.15 236.86 0.0366 0.9830 1.50
1.75 28.44 0.7287 0.1274 12.61 216.18 12.74 225.73 238.47 0.0531 0.9755 1.75
2.00 25.18 0.7340 0.1123 16.22 217.42 16.37 223.52 239.88 0.0678 0.9691 2.00
2.25 22.22 0.7389 0.1005 19.51 218.53 19.67 221.47 241.15 0.0809 0.9636 2.25
2.50 19.51 0.7436 0.0910 22.54 219.55 22.72 219.57 242.29 0.0930 0.9586 2.50
2.75 17.00 0.7479 0.0831 25.36 220.48 25.56 217.77 243.33 0.1040 0.9542 2.75
3.00 14.66 0.7521 0.0765 27.99 221.34 28.22 216.07 244.29 0.1143 0.9502 3.00
3.25 12.46 0.7561 0.0709 30.47 222.13 30.72 214.46 245.18 0.1238 0.9465 3.25
3.50 10.39 0.7599 0.0661 32.82 222.88 33.09 212.91 246.00 0.1328 0.9431 3.50
3.75 8.43 0.7636 0.0618 35.06 223.58 35.34 211.42 246.77 0.1413 0.9399 3.75
4.00 6.56 0.7672 0.0581 37.18 224.24 37.49 209.99 247.48 0.1493 0.9370 4.00
4.25 4.78 0.7706 0.0548 39.22 224.86 39.55 208.61 248.16 0.1569 0.9342 4.25
4.50 3.08 0.7740 0.0519 41.17 225.45 41.52 207.27 248.80 0.1642 0.9316 4.50
4.75 1.45 0.7773 0.0492 43.05 226.00 43.42 205.98 249.40 0.1711 0.9292 4.75
5.00 0.12 0.7805 0.0469 44.86 226.54 45.25 204.71 249.97 0.1777 0.9269 5.00
5.25 1.63 0.7836 0.0447 46.61 227.04 47.02 203.48 250.51 0.1841 0.9247 5.25
5.50 3.08 0.7867 0.0427 48.30 227.53 48.74 202.28 251.02 0.1903 0.9226 5.50
5.75 4.49 0.7897 0.0409 49.94 227.99 50.40 201.11 251.51 0.1962 0.9206 5.75
6.00 5.85 0.7927 0.0392 51.53 228.44 52.01 199.97 251.98 0.2019 0.9186 6.00
7.00 10.91 0.8041 0.0337 57.48 230.04 58.04 195.60 253.64 0.2231 0.9117 7.00
8.00 15.45 0.8149 0.0295 62.88 231.43 63.53 191.52 255.05 0.2419 0.9056 8.00
9.00 19.59 0.8252 0.0262 67.84 232.64 68.59 187.67 256.25 0.2591 0.9001 9.00
10.00 23.40 0.8352 0.0236 72.46 233.71 73.30 183.99 257.28 0.2748 0.8952 10.00
12.00 30.25 0.8546 0.0195 80.87 235.48 81.90 177.04 258.94 0.3029 0.8864 12.00
14.00 36.29 0.8734 0.0166 88.45 236.89 89.68 170.49 260.16 0.3277 0.8786 14.00
16.00 41.73 0.8919 0.0144 95.41 238.00 96.83 164.21 261.04 0.3500 0.8715 16.00
18.00 46.69 0.9104 0.0127 101.87 238.86 103.51 158.13 261.64 0.3705 0.8649 18.00
20.00 51.26 0.9291 0.0112 107.95 239.51 109.81 152.17 261.98 0.3895 0.8586 20.00
24.00 59.46 0.9677 0.0091 119.24 240.22 121.56 140.43 261.99 0.4241 0.8463 24.00
TABLE A-9 Properties of Superheated Refrigerant 22 Vapor

T v u h s v u h s
p 0.4 bar 0.04 MPa p 0.6 bar 0.06 MPa
(Tsat 58.86C) (Tsat 51.40C)
Sat. 0.50559 204.13 224.36 1.0512 0.34656 207.14 227.93 1.0294
55 0.51532 205.92 226.53 1.0612
50 0.52787 208.26 229.38 1.0741 0.34895 207.80 228.74 1.0330
45 0.54037 210.63 232.24 1.0868 0.35747 210.20 231.65 1.0459
40 0.55284 213.02 235.13 1.0993 0.36594 212.62 234.58 1.0586
35 0.56526 215.43 238.05 1.1117 0.37437 215.06 237.52 1.0711
30 0.57766 217.88 240.99 1.1239 0.38277 217.53 240.49 1.0835
R-22
25 0.59002 220.35 243.95 1.1360 0.39114 220.02 243.49 1.0956

20 0.60236 222.85 246.95 1.1479 0.39948 222.54 246.51 1.1077
15 0.61468 225.38 249.97 1.1597 0.40779 225.08 249.55 1.1196
10 0.62697 227.93 253.01 1.1714 0.41608 227.65 252.62 1.1314
5 0.63925 230.52 256.09 1.1830 0.42436 230.25 255.71 1.1430
0 0.65151 233.13 259.19 1.1944 0.43261 232.88 258.83 1.1545
p 0.8 bar 0.08 MPa p 1.0 bar 0.10 MPa

(Tsat 45.73C) (Tsat 41.09C)
Sat. 0.26503 209.41 230.61 1.0144 0.21518 211.25 232.77 1.0031
45 0.26597 209.76 231.04 1.0163
40 0.27245 212.21 234.01 1.0292 0.21633 211.79 233.42 1.0059
35 0.27890 214.68 236.99 1.0418 0.22158 214.29 236.44 1.0187
30 0.28530 217.17 239.99 1.0543 0.22679 216.80 239.48 1.0313
25 0.29167 219.68 243.02 1.0666 0.23197 219.34 242.54 1.0438
20 0.29801 222.22 246.06 1.0788 0.23712 221.90 245.61 1.0560
15 0.30433 224.78 249.13 1.0908 0.24224 224.48 248.70 1.0681
10 0.31062 227.37 252.22 1.1026 0.24734 227.08 251.82 1.0801
5 0.31690 229.98 255.34 1.1143 0.25241 229.71 254.95 1.0919
0 0.32315 232.62 258.47 1.1259 0.25747 232.36 258.11 1.1035
5 0.32939 235.29 261.64 1.1374 0.26251 235.04 261.29 1.1151
10 0.33561 237.98 264.83 1.1488 0.26753 237.74 264.50 1.1265
p 1.5 bar 0.15 MPa p 2.0 bar 0.20 MPa

(Tsat 32.08C) (Tsat 25.18C)
Sat. 0.14721 214.77 236.86 0.9830 0.11232 217.42 239.88 0.9691
30 0.14872 215.85 238.16 0.9883
25 0.15232 218.45 241.30 1.0011 0.11242 217.51 240.00 0.9696
20 0.15588 221.07 244.45 1.0137 0.11520 220.19 243.23 0.9825
15 0.15941 223.70 247.61 1.0260 0.11795 222.88 246.47 0.9952
10 0.16292 226.35 250.78 1.0382 0.12067 225.58 249.72 1.0076
5 0.16640 229.02 253.98 1.0502 0.12336 228.30 252.97 1.0199
0 0.16987 231.70 257.18 1.0621 0.12603 231.03 256.23 1.0310
5 0.17331 234.42 260.41 1.0738 0.12868 233.78 259.51 1.0438
10 0.17674 237.15 263.66 1.0854 0.13132 236.54 262.81 1.0555
15 0.18015 239.91 266.93 1.0968 0.13393 239.33 266.12 1.0671
20 0.18355 242.69 270.22 1.1081 0.13653 242.14 269.44 1.0786
25 0.18693 245.49 273.53 1.1193 0.13912 244.97 272.79 1.0899

T v u h s v u h s
p 2.5 bar 0.25 MPa p 3.0 bar 0.30 MPa
(Tsat 19.51C) (Tsat 14.66C)
Sat. 0.09097 219.55 242.29 0.9586 0.07651 221.34 244.29 0.9502
15 0.09303 222.03 245.29 0.9703
10 0.09528 224.79 248.61 0.9831 0.07833 223.96 247.46 0.9623
5 0.09751 227.55 251.93 0.9956 0.08025 226.78 250.86 0.9751
0 0.09971 230.33 255.26 1.0078 0.08214 229.61 254.25 0.9876
5 0.10189 233.12 258.59 1.0199 0.08400 232.44 257.64 0.9999
10 0.10405 235.92 261.93 1.0318 0.08585 235.28 261.04 1.0120
R-22
15 0.10619 238.74 265.29 1.0436 0.08767 238.14 264.44 1.0239
20 0.10831 241.58 268.66 1.0552 0.08949 241.01 267.85 1.0357
25 0.11043 244.44 272.04 1.0666 0.09128 243.89 271.28 1.0472
30 0.11253 247.31 275.44 1.0779 0.09307 246.80 274.72 1.0587
35 0.11461 250.21 278.86 1.0891 0.09484 249.72 278.17 1.0700
40 0.11669 253.13 282.30 1.1002 0.09660 252.66 281.64 1.0811
p 3.5 bar 0.35 MPa p 4.0 bar 0.40 MPa

(Tsat 10.39C) (Tsat 6.56C)
Sat. 0.06605 222.88 246.00 0.9431 0.05812 224.24 247.48 0.9370
10 0.06619 223.10 246.27 0.9441
5 0.06789 225.99 249.75 0.9572 0.05860 225.16 248.60 0.9411
0 0.06956 228.86 253.21 0.9700 0.06011 228.09 252.14 0.9542
5 0.07121 231.74 256.67 0.9825 0.06160 231.02 225.66 0.9670
10 0.07284 234.63 260.12 0.9948 0.06306 233.95 259.18 0.9795
15 0.07444 237.52 263.57 1.0069 0.06450 236.89 262.69 0.9918
20 0.07603 240.42 267.03 1.0188 0.06592 239.83 266.19 1.0039
25 0.07760 243.34 270.50 1.0305 0.06733 242.77 269.71 1.0158
30 0.07916 246.27 273.97 1.0421 0.06872 245.73 273.22 1.0274
35 0.08070 249.22 227.46 1.0535 0.07010 248.71 276.75 1.0390
40 0.08224 252.18 280.97 1.0648 0.07146 251.70 280.28 1.0504
45 0.08376 255.17 284.48 1.0759 0.07282 254.70 283.83 1.0616
p 4.5 bar 0.45 MPa p 5.0 bar 0.50 MPa

(Tsat 3.08C) (Tsat 0.12C)
Sat. 0.05189 225.45 248.80 0.9316 0.04686 226.54 249.97 0.9269
0 0.05275 227.29 251.03 0.9399
5 0.05411 230.28 254.63 0.9529 0.04810 229.52 253.57 0.9399
10 0.05545 233.26 258.21 0.9657 0.04934 232.55 257.22 0.9530
15 0.05676 236.24 261.78 0.9782 0.05056 235.57 260.85 0.9657
20 0.05805 239.22 265.34 0.9904 0.05175 238.59 264.47 0.9781
25 0.05933 242.20 268.90 1.0025 0.05293 241.61 268.07 0.9903
30 0.06059 245.19 272.46 1.0143 0.05409 244.63 271.68 1.0023
35 0.06184 248.19 276.02 1.0259 0.05523 247.66 275.28 1.0141
40 0.06308 251.20 279.59 1.0374 0.05636 250.70 278.89 1.0257
45 0.06430 254.23 283.17 1.0488 0.05748 253.76 282.50 1.0371
50 0.06552 257.28 286.76 1.0600 0.05859 256.82 286.12 1.0484
55 0.06672 260.34 290.36 1.0710 0.05969 259.90 289.75 1.0595

T v u h s v u h s
p 5.5 bar 0.55 MPa p 6.0 bar 0.60 MPa
Sat. 0.04271 227.53 251.02 0.9226 0.03923 228.44 251.98 0.9186
5 0.04317 228.72 252.46 0.9278
10 0.04433 231.81 256.20 0.9411 0.04015 231.05 255.14 0.9299
15 0.04547 234.89 259.90 0.9540 0.04122 234.18 258.91 0.9431
20 0.04658 237.95 263.57 0.9667 0.04227 237.29 262.65 0.9560
25 0.04768 241.01 267.23 0.9790 0.04330 240.39 266.37 0.9685
30 0.04875 244.07 270.88 0.9912 0.04431 243.49 270.07 0.9808
R-22
35 0.04982 247.13 274.53 1.0031 0.04530 246.58 273.76 0.9929

40 0.05086 250.20 278.17 1.0148 0.04628 249.68 277.45 1.0048
45 0.05190 253.27 281.82 1.0264 0.04724 252.78 281.13 1.0164
50 0.05293 256.36 285.47 1.0378 0.04820 255.90 284.82 1.0279
55 0.05394 259.46 289.13 1.0490 0.04914 259.02 288.51 1.0393
60 0.05495 262.58 292.80 1.0601 0.05008 262.15 292.20 1.0504
p 7.0 bar 0.70 MPa p 8.0 bar 0.80 MPa

(Tsat 10.91C) (Tsat 15.45C)
Sat. 0.03371 230.04 253.64 0.9117 0.02953 231.43 255.05 0.9056
15 0.03451 232.70 256.86 0.9229
20 0.03547 235.92 260.75 0.9363 0.03033 234.47 258.74 0.9182
25 0.03639 239.12 264.59 0.9493 0.03118 237.76 262.70 0.9315
30 0.03730 242.29 268.40 0.9619 0.03202 241.04 266.66 0.9448
35 0.03819 245.46 272.19 0.9743 0.03283 244.28 270.54 0.9574
40 0.03906 248.62 275.96 0.9865 0.03363 247.52 274.42 0.9700
45 0.03992 251.78 279.72 0.9984 0.03440 250.74 278.26 0.9821
50 0.04076 254.94 283.48 1.0101 0.03517 253.96 282.10 0.9941
55 0.04160 258.11 287.23 1.0216 0.03592 257.18 285.92 1.0058
60 0.04242 261.29 290.99 1.0330 0.03667 260.40 289.74 1.0174
65 0.04324 264.48 294.75 1.0442 0.03741 263.64 293.56 1.0287
70 0.04405 267.68 298.51 1.0552 0.03814 266.87 297.38 1.0400
p 9.0 bar 0.90 MPa p 10.0 bar 1.00 MPa

(Tsat 19.59C) (Tsat 23.40C)
Sat. 0.02623 232.64 256.25 0.9001 0.02358 233.71 257.28 0.8952
20 0.02630 232.92 256.59 0.9013
30 0.02789 239.73 264.83 0.9289 0.02457 238.34 262.91 0.9139
40 0.02939 246.37 272.82 0.9549 0.02598 245.18 271.17 0.9407
50 0.03082 252.95 280.68 0.9795 0.02732 251.90 279.22 0.9660
60 0.03219 259.49 288.46 1.0033 0.02860 258.56 287.15 0.9902
70 0.03353 266.04 296.21 1.0262 0.02984 265.19 295.03 1.0135
80 0.03483 272.62 303.96 1.0484 0.03104 271.84 302.88 1.0361
90 0.03611 279.23 311.73 1.0701 0.03221 278.52 310.74 1.0580
100 0.03736 285.90 319.53 1.0913 0.03337 285.24 318.61 1.0794
110 0.03860 292.63 327.37 1.1120 0.03450 292.02 326.52 1.1003
120 0.03982 299.42 335.26 1.1323 0.03562 298.85 334.46 1.1207
130 0.04103 306.28 343.21 1.1523 0.03672 305.74 342.46 1.1408
140 0.04223 313.21 351.22 1.1719 0.03781 312.70 350.51 1.1605
150 0.04342 320.21 359.29 1.1912 0.03889 319.74 358.63 1.1790
T v u h s v u h s
p 12.0 bar 1.20 MPa p 14.0 bar 1.40 MPa
(Tsat 30.25C) (Tsat 36.29C)
Sat. 0.01955 235.48 258.94 0.8864 0.01662 236.89 260.16 0.8786
40 0.02083 242.63 267.62 0.9146 0.01708 239.78 263.70 0.8900
50 0.02204 249.69 276.14 0.9413 0.01823 247.29 272.81 0.9186
60 0.02319 256.60 284.43 0.9666 0.01929 254.52 281.53 0.9452
70 0.02428 263.44 292.58 0.9907 0.02029 261.60 290.01 0.9703
80 0.02534 270.25 300.66 1.0139 0.02125 268.60 298.34 0.9942
90 0.02636 277.07 308.70 1.0363 0.02217 275.56 306.60 1.0172
100 0.02736 283.90 316.73 1.0582 0.02306 282.52 314.80 1.0395
110 0.02834 290.77 324.78 1.0794 0.02393 289.49 323.00 1.0612
R-22
120 0.02930 297.69 332.85 1.1002 0.02478 296.50 331.19 1.0823
130 0.03024 304.65 340.95 1.1205 0.02562 303.55 339.41 1.1029
140 0.03118 311.68 349.09 1.1405 0.02644 310.64 347.65 1.1231
150 0.03210 318.77 357.29 1.1601 0.02725 317.79 355.94 1.1429
160 0.03301 325.92 365.54 1.1793 0.02805 324.99 364.26 1.1624
170 0.03392 333.14 373.84 1.1983 0.02884 332.26 372.64 1.1815
p 16.0 bar 1.60 MPa p 18.0 bar 1.80 MPa

(Tsat 41.73C) (Tsat 46.69C)
Sat. 0.01440 238.00 261.04 0.8715 0.01265 238.86 261.64 0.8649
50 0.01533 244.66 269.18 0.8971 0.01301 241.72 265.14 0.8758
60 0.01634 252.29 278.43 0.9252 0.01401 249.86 275.09 0.9061
70 0.01728 259.65 287.30 0.9515 0.01492 257.57 284.43 0.9337
80 0.01817 266.86 295.93 0.9762 0.01576 265.04 293.40 0.9595
90 0.01901 274.00 304.42 0.9999 0.01655 272.37 302.16 0.9839
100 0.01983 281.09 312.82 1.0228 0.01731 279.62 310.77 1.0073
110 0.02062 288.18 321.17 1.0448 0.01804 286.83 319.30 1.0299
120 0.02139 295.28 329.51 1.0663 0.01874 294.04 327.78 1.0517
130 0.02214 302.41 337.84 1.0872 0.01943 301.26 336.24 1.0730
140 0.02288 309.58 346.19 1.1077 0.02011 308.50 344.70 1.0937
150 0.02361 316.79 354.56 1.1277 0.02077 315.78 353.17 1.1139
160 0.02432 324.05 362.97 1.1473 0.02142 323.10 361.66 1.1338
170 0.02503 331.37 371.42 1.1666 0.02207 330.47 370.19 1.1532
p 20.0 bar 2.00 MPa p 24.0 bar 2.4 MPa

(Tsat 51.26C) (Tsat 59.46C)
Sat. 0.01124 239.51 261.98 0.8586 0.00907 240.22 261.99 0.8463
60 0.01212 247.20 271.43 0.8873 0.00913 240.78 262.68 0.8484
70 0.01300 255.35 281.36 0.9167 0.01006 250.30 274.43 0.8831
80 0.01381 263.12 290.74 0.9436 0.01085 258.89 284.93 0.9133
90 0.01457 270.67 299.80 0.9689 0.01156 267.01 294.75 0.9407
100 0.01528 278.09 308.65 0.9929 0.01222 274.85 304.18 0.9663
110 0.01596 285.44 317.37 1.0160 0.01284 282.53 313.35 0.9906
120 0.01663 292.76 326.01 1.0383 0.01343 290.11 322.35 1.0137
130 0.01727 300.08 334.61 1.0598 0.01400 297.64 331.25 1.0361
140 0.01789 307.40 343.19 1.0808 0.01456 305.14 340.08 1.0577
150 0.01850 314.75 351.76 1.1013 0.01509 312.64 348.87 1.0787
160 0.01910 322.14 360.34 1.1214 0.01562 320.16 357.64 1.0992
170 0.01969 329.56 368.95 1.1410 0.01613 327.70 366.41 1.1192
180 0.02027 337.03 377.58 1.1603 0.01663 335.27 375.20 1.1388
735
TABLE A-10 Properties of Saturated Refrigerant 134a (LiquidVapor): Temperature Table

40 0.5164 0.7055 0.3569 0.04 204.45 0.00 222.88 222.88 0.0000 0.9560 40
36 0.6332 0.7113 0.2947 4.68 206.73 4.73 220.67 225.40 0.0201 0.9506 36
32 0.7704 0.7172 0.2451 9.47 209.01 9.52 218.37 227.90 0.0401 0.9456 32
28 0.9305 0.7233 0.2052 14.31 211.29 14.37 216.01 230.38 0.0600 0.9411 28
26 1.0199 0.7265 0.1882 16.75 212.43 16.82 214.80 231.62 0.0699 0.9390 26
24 1.1160 0.7296 0.1728 19.21 213.57 19.29 213.57 232.85 0.0798 0.9370 24
22 1.2192 0.7328 0.1590 21.68 214.70 21.77 212.32 234.08 0.0897 0.9351 22
20 1.3299 0.7361 0.1464 24.17 215.84 24.26 211.05 235.31 0.0996 0.9332 20
18 1.4483 0.7395 0.1350 26.67 216.97 26.77 209.76 236.53 0.1094 0.9315 18
16 1.5748 0.7428 0.1247 29.18 218.10 29.30 208.45 237.74 0.1192 0.9298 16
12 1.8540 0.7498 0.1068 34.25 220.36 34.39 205.77 240.15 0.1388 0.9267 12
R-134a
8 2.1704 0.7569 0.0919 39.38 222.60 39.54 203.00 242.54 0.1583 0.9239 8
4 2.5274 0.7644 0.0794 44.56 224.84 44.75 200.15 244.90 0.1777 0.9213 4
0 2.9282 0.7721 0.0689 49.79 227.06 50.02 197.21 247.23 0.1970 0.9190 0
4 3.3765 0.7801 0.0600 55.08 229.27 55.35 194.19 249.53 0.2162 0.9169 4
8 3.8756 0.7884 0.0525 60.43 231.46 60.73 191.07 251.80 0.2354 0.9150 8
12 4.4294 0.7971 0.0460 65.83 233.63 66.18 187.85 254.03 0.2545 0.9132 12
16 5.0416 0.8062 0.0405 71.29 235.78 71.69 184.52 256.22 0.2735 0.9116 16
20 5.7160 0.8157 0.0358 76.80 237.91 77.26 181.09 258.36 0.2924 0.9102 20
24 6.4566 0.8257 0.0317 82.37 240.01 82.90 177.55 260.45 0.3113 0.9089 24
26 6.8530 0.8309 0.0298 85.18 241.05 85.75 175.73 261.48 0.3208 0.9082 26
28 7.2675 0.8362 0.0281 88.00 242.08 88.61 173.89 262.50 0.3302 0.9076 28
30 7.7006 0.8417 0.0265 90.84 243.10 91.49 172.00 263.50 0.3396 0.9070 30
32 8.1528 0.8473 0.0250 93.70 244.12 94.39 170.09 264.48 0.3490 0.9064 32
34 8.6247 0.8530 0.0236 96.58 245.12 97.31 168.14 265.45 0.3584 0.9058 34
36 9.1168 0.8590 0.0223 99.47 246.11 100.25 166.15 266.40 0.3678 0.9053 36
38 9.6298 0.8651 0.0210 102.38 247.09 103.21 164.12 267.33 0.3772 0.9047 38
40 10.164 0.8714 0.0199 105.30 248.06 106.19 162.05 268.24 0.3866 0.9041 40
42 10.720 0.8780 0.0188 108.25 249.02 109.19 159.94 269.14 0.3960 0.9035 42
44 11.299 0.8847 0.0177 111.22 249.96 112.22 157.79 270.01 0.4054 0.9030 44
48 12.526 0.8989 0.0159 117.22 251.79 118.35 153.33 271.68 0.4243 0.9017 48
52 13.851 0.9142 0.0142 123.31 253.55 124.58 148.66 273.24 0.4432 0.9004 52
56 15.278 0.9308 0.0127 129.51 255.23 130.93 143.75 274.68 0.4622 0.8990 56
60 16.813 0.9488 0.0114 135.82 256.81 137.42 138.57 275.99 0.4814 0.8973 60
70 21.162 1.0027 0.0086 152.22 260.15 154.34 124.08 278.43 0.5302 0.8918 70
80 26.324 1.0766 0.0064 169.88 262.14 172.71 106.41 279.12 0.5814 0.8827 80
90 32.435 1.1949 0.0046 189.82 261.34 193.69 82.63 276.32 0.6380 0.8655 90
100 39.742 1.5443 0.0027 218.60 248.49 224.74 34.40 259.13 0.7196 0.8117 100
Source: Tables A-10 through A-12 are calculated based on equations from D. P. Wilson and R. S. Basu, Thermodynamic Properties of a New
Stratospherically Safe Working FluidRefrigerant 134a, ASHRAE Trans., Vol. 94, Pt. 2, 1988, pp. 20952118.
TABLE A-11 Properties of Saturated Refrigerant 134a (LiquidVapor): Pressure Table

0.6 37.07 0.7097 0.3100 3.41 206.12 3.46 221.27 224.72 0.0147 0.9520 0.6
0.8 31.21 0.7184 0.2366 10.41 209.46 10.47 217.92 228.39 0.0440 0.9447 0.8
1.0 26.43 0.7258 0.1917 16.22 212.18 16.29 215.06 231.35 0.0678 0.9395 1.0
1.2 22.36 0.7323 0.1614 21.23 214.50 21.32 212.54 233.86 0.0879 0.9354 1.2
1.4 18.80 0.7381 0.1395 25.66 216.52 25.77 210.27 236.04 0.1055 0.9322 1.4
1.6 15.62 0.7435 0.1229 29.66 218.32 29.78 208.19 237.97 0.1211 0.9295 1.6
1.8 12.73 0.7485 0.1098 33.31 219.94 33.45 206.26 239.71 0.1352 0.9273 1.8
2.0 10.09 0.7532 0.0993 36.69 221.43 36.84 204.46 241.30 0.1481 0.9253 2.0
2.4 5.37 0.7618 0.0834 42.77 224.07 42.95 201.14 244.09 0.1710 0.9222 2.4
2.8 1.23 0.7697 0.0719 48.18 226.38 48.39 198.13 246.52 0.1911 0.9197 2.8
3.2 2.48 0.7770 0.0632 53.06 228.43 53.31 195.35 248.66 0.2089 0.9177 3.2
R-134a
3.6 5.84 0.7839 0.0564 57.54 230.28 57.82 192.76 250.58 0.2251 0.9160 3.6
4.0 8.93 0.7904 0.0509 61.69 231.97 62.00 190.32 252.32 0.2399 0.9145 4.0
5.0 15.74 0.8056 0.0409 70.93 235.64 71.33 184.74 256.07 0.2723 0.9117 5.0
6.0 21.58 0.8196 0.0341 78.99 238.74 79.48 179.71 259.19 0.2999 0.9097 6.0
7.0 26.72 0.8328 0.0292 86.19 241.42 86.78 175.07 261.85 0.3242 0.9080 7.0
8.0 31.33 0.8454 0.0255 92.75 243.78 93.42 170.73 264.15 0.3459 0.9066 8.0
9.0 35.53 0.8576 0.0226 98.79 245.88 99.56 166.62 266.18 0.3656 0.9054 9.0
10.0 39.39 0.8695 0.0202 104.42 247.77 105.29 162.68 267.97 0.3838 0.9043 10.0
12.0 46.32 0.8928 0.0166 114.69 251.03 115.76 155.23 270.99 0.4164 0.9023 12.0
14.0 52.43 0.9159 0.0140 123.98 253.74 125.26 148.14 273.40 0.4453 0.9003 14.0
16.0 57.92 0.9392 0.0121 132.52 256.00 134.02 141.31 275.33 0.4714 0.8982 16.0
18.0 62.91 0.9631 0.0105 140.49 257.88 142.22 134.60 276.83 0.4954 0.8959 18.0
20.0 67.49 0.9878 0.0093 148.02 259.41 149.99 127.95 277.94 0.5178 0.8934 20.0
25.0 77.59 1.0562 0.0069 165.48 261.84 168.12 111.06 279.17 0.5687 0.8854 25.0
30.0 86.22 1.1416 0.0053 181.88 262.16 185.30 92.71 278.01 0.6156 0.8735 30.0
TABLE A-12 Properties of Superheated Refrigerant 134a Vapor

T v u h s v u h s
p 0.6 bar 0.06 MPa p 1.0 bar 0.10 MPa
(Tsat 37.07C) (Tsat 26.43C)
Sat. 0.31003 206.12 224.72 0.9520 0.19170 212.18 231.35 0.9395
20 0.33536 217.86 237.98 1.0062 0.19770 216.77 236.54 0.9602
10 0.34992 224.97 245.96 1.0371 0.20686 224.01 244.70 0.9918
0 0.36433 232.24 254.10 1.0675 0.21587 231.41 252.99 1.0227
10 0.37861 239.69 262.41 1.0973 0.22473 238.96 261.43 1.0531
20 0.39279 247.32 270.89 1.1267 0.23349 246.67 270.02 1.0829
30 0.40688 255.12 279.53 1.1557 0.24216 254.54 278.76 1.1122
40 0.42091 263.10 288.35 1.1844 0.25076 262.58 287.66 1.1411
50 0.43487 271.25 297.34 1.2126 0.25930 270.79 296.72 1.1696
60 0.44879 279.58 306.51 1.2405 0.26779 279.16 305.94 1.1977
70 0.46266 288.08 315.84 1.2681 0.27623 287.70 315.32 1.2254
80 0.47650 296.75 325.34 1.2954 0.28464 296.40 324.87 1.2528
90 0.49031 305.58 335.00 1.3224 0.29302 305.27 334.57 1.2799
R-134a
p 1.4 bar 0.14 MPa p 1.8 bar 0.18 MPa

(Tsat 18.80C) (Tsat 12.73C)
Sat. 0.13945 216.52 236.04 0.9322 0.10983 219.94 239.71 0.9273
10 0.14549 223.03 243.40 0.9606 0.11135 222.02 242.06 0.9362
0 0.15219 230.55 251.86 0.9922 0.11678 229.67 250.69 0.9684
10 0.15875 238.21 260.43 1.0230 0.12207 237.44 259.41 0.9998
20 0.16520 246.01 269.13 1.0532 0.12723 245.33 268.23 1.0304
30 0.17155 253.96 277.97 1.0828 0.13230 253.36 277.17 1.0604
40 0.17783 262.06 286.96 1.1120 0.13730 261.53 286.24 1.0898
50 0.18404 270.32 296.09 1.1407 0.14222 269.85 295.45 1.1187
60 0.19020 278.74 305.37 1.1690 0.14710 278.31 304.79 1.1472
70 0.19633 287.32 314.80 1.1969 0.15193 286.93 314.28 1.1753
80 0.20241 296.06 324.39 1.2244 0.15672 295.71 323.92 1.2030
90 0.20846 304.95 334.14 1.2516 0.16148 304.63 333.70 1.2303
100 0.21449 314.01 344.04 1.2785 0.16622 313.72 343.63 1.2573
p 2.0 bar 0.20 MPa p 2.4 bar 0.24 MPa

(Tsat 10.09C) (Tsat 5.37C)
Sat. 0.09933 221.43 241.30 0.9253 0.08343 224.07 244.09 0.9222
10 0.09938 221.50 241.38 0.9256
0 0.10438 229.23 250.10 0.9582 0.08574 228.31 248.89 0.9399
10 0.10922 237.05 258.89 0.9898 0.08993 236.26 257.84 0.9721
20 0.11394 244.99 267.78 1.0206 0.09399 244.30 266.85 1.0034
30 0.11856 253.06 276.77 1.0508 0.09794 252.45 275.95 1.0339
40 0.12311 261.26 285.88 1.0804 0.10181 260.72 285.16 1.0637
50 0.12758 269.61 295.12 1.1094 0.10562 269.12 294.47 1.0930
60 0.13201 278.10 304.50 1.1380 0.10937 277.67 303.91 1.1218
70 0.13639 286.74 314.02 1.1661 0.11307 286.35 313.49 1.1501
80 0.14073 295.53 323.68 1.1939 0.11674 295.18 323.19 1.1780
90 0.14504 304.47 333.48 1.2212 0.12037 304.15 333.04 1.2055
100 0.14932 313.57 343.43 1.2483 0.12398 313.27 343.03 1.2326
T v u h s v u h s
p 2.8 bar 0.28 MPa p 3.2 bar 0.32 MPa
Sat. 0.07193 226.38 246.52 0.9197 0.06322 228.43 248.66 0.9177
0 0.07240 227.37 247.64 0.9238
10 0.07613 235.44 256.76 0.9566 0.06576 234.61 255.65 0.9427
20 0.07972 243.59 265.91 0.9883 0.06901 242.87 264.95 0.9749
30 0.08320 251.83 275.12 1.0192 0.07214 251.19 274.28 1.0062
40 0.08660 260.17 284.42 1.0494 0.07518 259.61 283.67 1.0367
50 0.08992 268.64 293.81 1.0789 0.07815 268.14 293.15 1.0665
60 0.09319 277.23 303.32 1.1079 0.08106 276.79 302.72 1.0957
70 0.09641 285.96 312.95 1.1364 0.08392 285.56 312.41 1.1243
80 0.09960 294.82 322.71 1.1644 0.08674 294.46 322.22 1.1525
90 0.10275 303.83 332.60 1.1920 0.08953 303.50 332.15 1.1802
100 0.10587 312.98 342.62 1.2193 0.09229 312.68 342.21 1.2076
110 0.10897 322.27 352.78 1.2461 0.09503 322.00 352.40 1.2345
120 0.11205 331.71 363.08 1.2727 0.09774 331.45 362.73 1.2611
R-134a
p 4.0 bar 0.40 MPa p 5.0 bar 0.50 MPa
(Tsat 8.93C) (Tsat 15.74C)
Sat. 0.05089 231.97 252.32 0.9145 0.04086 235.64 256.07 0.9117
10 0.05119 232.87 253.35 0.9182
20 0.05397 241.37 262.96 0.9515 0.04188 239.40 260.34 0.9264
30 0.05662 249.89 272.54 0.9837 0.04416 248.20 270.28 0.9597
40 0.05917 258.47 282.14 1.0148 0.04633 256.99 280.16 0.9918
50 0.06164 267.13 291.79 1.0452 0.04842 265.83 290.04 1.0229
60 0.06405 275.89 301.51 1.0748 0.05043 274.73 299.95 1.0531
70 0.06641 284.75 311.32 1.1038 0.05240 283.72 309.92 1.0825
80 0.06873 293.73 321.23 1.1322 0.05432 292.80 319.96 1.1114
90 0.07102 302.84 331.25 1.1602 0.05620 302.00 330.10 1.1397
100 0.07327 312.07 341.38 1.1878 0.05805 311.31 340.33 1.1675
110 0.07550 321.44 351.64 1.2149 0.05988 320.74 350.68 1.1949
120 0.07771 330.94 362.03 1.2417 0.06168 330.30 361.14 1.2218
130 0.07991 340.58 372.54 1.2681 0.06347 339.98 371.72 1.2484
140 0.08208 350.35 383.18 1.2941 0.06524 349.79 382.42 1.2746
p 6.0 bar 0.60 MPa p 7.0 bar 0.70 MPa

(Tsat 21.58C) (Tsat 26.72C)
Sat. 0.03408 238.74 259.19 0.9097 0.02918 241.42 261.85 0.9080
30 0.03581 246.41 267.89 0.9388 0.02979 244.51 265.37 0.9197
40 0.03774 255.45 278.09 0.9719 0.03157 253.83 275.93 0.9539
50 0.03958 264.48 288.23 1.0037 0.03324 263.08 286.35 0.9867
60 0.04134 273.54 298.35 1.0346 0.03482 272.31 296.69 1.0182
70 0.04304 282.66 308.48 1.0645 0.03634 281.57 307.01 1.0487
80 0.04469 291.86 318.67 1.0938 0.03781 290.88 317.35 1.0784
90 0.04631 301.14 328.93 1.1225 0.03924 300.27 327.74 1.1074
100 0.04790 310.53 339.27 1.1505 0.04064 309.74 338.19 1.1358
110 0.04946 320.03 349.70 1.1781 0.04201 319.31 348.71 1.1637
120 0.05099 329.64 360.24 1.2053 0.04335 328.98 359.33 1.1910
130 0.05251 339.38 370.88 1.2320 0.04468 338.76 370.04 1.2179
140 0.05402 349.23 381.64 1.2584 0.04599 348.66 380.86 1.2444
150 0.05550 359.21 392.52 1.2844 0.04729 358.68 391.79 1.2706
160 0.05698 369.32 403.51 1.3100 0.04857 368.82 402.82 1.2963
739
T v u h s v u h s
p 8.0 bar 0.80 MPa p 9.0 bar 0.90 MPa
(Tsat 31.33C) (Tsat 35.53C)
Sat. 0.02547 243.78 264.15 0.9066 0.02255 245.88 266.18 0.9054
40 0.02691 252.13 273.66 0.9374 0.02325 250.32 271.25 0.9217
50 0.02846 261.62 284.39 0.9711 0.02472 260.09 282.34 0.9566
60 0.02992 271.04 294.98 1.0034 0.02609 269.72 293.21 0.9897
70 0.03131 280.45 305.50 1.0345 0.02738 279.30 303.94 1.0214
80 0.03264 289.89 316.00 1.0647 0.02861 288.87 314.62 1.0521
90 0.03393 299.37 326.52 1.0940 0.02980 298.46 325.28 1.0819
100 0.03519 308.93 337.08 1.1227 0.03095 308.11 335.96 1.1109
110 0.03642 318.57 347.71 1.1508 0.03207 317.82 346.68 1.1392
120 0.03762 328.31 358.40 1.1784 0.03316 327.62 357.47 1.1670
130 0.03881 338.14 369.19 1.2055 0.03423 337.52 368.33 1.1943
140 0.03997 348.09 380.07 1.2321 0.03529 347.51 379.27 1.2211
150 0.04113 358.15 391.05 1.2584 0.03633 357.61 390.31 1.2475
160 0.04227 368.32 402.14 1.2843 0.03736 367.82 401.44 1.2735
170 0.04340 378.61 413.33 1.3098 0.03838 378.14 412.68 1.2992
180 0.04452 389.02 424.63 1.3351 0.03939 388.57 424.02 1.3245
R-134a
p 10.0 bar 1.00 MPa p 12.0 bar 1.20 MPa

(Tsat 39.39C) (Tsat 46.32C)
Sat. 0.02020 247.77 267.97 0.9043 0.01663 251.03 270.99 0.9023
40 0.02029 248.39 268.68 0.9066
50 0.02171 258.48 280.19 0.9428 0.01712 254.98 275.52 0.9164
60 0.02301 268.35 291.36 0.9768 0.01835 265.42 287.44 0.9527
70 0.02423 278.11 302.34 1.0093 0.01947 275.59 298.96 0.9868
80 0.02538 287.82 313.20 1.0405 0.02051 285.62 310.24 1.0192
90 0.02649 297.53 324.01 1.0707 0.02150 295.59 321.39 1.0503
100 0.02755 307.27 334.82 1.1000 0.02244 305.54 332.47 1.0804
110 0.02858 317.06 345.65 1.1286 0.02335 315.50 343.52 1.1096
120 0.02959 326.93 356.52 1.1567 0.02423 325.51 354.58 1.1381
130 0.03058 336.88 367.46 1.1841 0.02508 335.58 365.68 1.1660
140 0.03154 346.92 378.46 1.2111 0.02592 345.73 376.83 1.1933
150 0.03250 357.06 389.56 1.2376 0.02674 355.95 388.04 1.2201
160 0.03344 367.31 400.74 1.2638 0.02754 366.27 399.33 1.2465
170 0.03436 377.66 412.02 1.2895 0.02834 376.69 410.70 1.2724
180 0.03528 388.12 423.40 1.3149 0.02912 387.21 422.16 1.2980
p 14.0 bar 1.40 MPa p 16.0 bar 1.60 MPa

(Tsat 52.43C) (Tsat 57.92C)
Sat. 0.01405 253.74 273.40 0.9003 0.01208 256.00 275.33 0.8982
60 0.01495 262.17 283.10 0.9297 0.01233 258.48 278.20 0.9069
70 0.01603 272.87 295.31 0.9658 0.01340 269.89 291.33 0.9457
80 0.01701 283.29 307.10 0.9997 0.01435 280.78 303.74 0.9813
90 0.01792 293.55 318.63 1.0319 0.01521 291.39 315.72 1.0148
100 0.01878 303.73 330.02 1.0628 0.01601 301.84 327.46 1.0467
110 0.01960 313.88 341.32 1.0927 0.01677 312.20 339.04 1.0773
120 0.02039 324.05 352.59 1.1218 0.01750 322.53 350.53 1.1069
130 0.02115 334.25 363.86 1.1501 0.01820 332.87 361.99 1.1357
140 0.02189 344.50 375.15 1.1777 0.01887 343.24 373.44 1.1638
150 0.02262 354.82 386.49 1.2048 0.01953 353.66 384.91 1.1912
160 0.02333 365.22 397.89 1.2315 0.02017 364.15 396.43 1.2181
170 0.02403 375.71 409.36 1.2576 0.02080 374.71 407.99 1.2445
180 0.02472 386.29 420.90 1.2834 0.02142 385.35 419.62 1.2704
190 0.02541 396.96 432.53 1.3088 0.02203 396.08 431.33 1.2960
200 0.02608 407.73 444.24 1.3338 0.02263 406.90 443.11 1.3212
740
TABLE A-13 Properties of Saturated Ammonia (LiquidVapor): Temperature Table

50 0.4086 1.4245 2.6265 43.94 1264.99 43.88 1416.20 1372.32 0.1922 6.1543 50
45 0.5453 1.4367 2.0060 22.03 1271.19 21.95 1402.52 1380.57 0.0951 6.0523 45
40 0.7174 1.4493 1.5524 0.10 1277.20 0.00 1388.56 1388.56 0.0000 5.9557 40
36 0.8850 1.4597 1.2757 17.47 1281.87 17.60 1377.17 1394.77 0.0747 5.8819 36
32 1.0832 1.4703 1.0561 35.09 1286.41 35.25 1365.55 1400.81 0.1484 5.8111 32
30 1.1950 1.4757 0.9634 43.93 1288.63 44.10 1359.65 1403.75 0.1849 5.7767 30
28 1.3159 1.4812 0.8803 52.78 1290.82 52.97 1353.68 1406.66 0.2212 5.7430 28
26 1.4465 1.4867 0.8056 61.65 1292.97 61.86 1347.65 1409.51 0.2572 5.7100 26
22 1.7390 1.4980 0.6780 79.46 1297.18 79.72 1335.36 1415.08 0.3287 5.6457 22
20 1.9019 1.5038 0.6233 88.40 1299.23 88.68 1329.10 1417.79 0.3642 5.6144 20
18 2.0769 1.5096 0.5739 97.36 1301.25 97.68 1322.77 1420.45 0.3994 5.5837 18
16 2.2644 1.5155 0.5291 106.36 1303.23 106.70 1316.35 1423.05 0.4346 5.5536 16
14 2.4652 1.5215 0.4885 115.37 1305.17 115.75 1309.86 1425.61 0.4695 5.5239 14
12 2.6798 1.5276 0.4516 124.42 1307.08 124.83 1303.28 1428.11 0.5043 5.4948 12
10 2.9089 1.5338 0.4180 133.50 1308.95 133.94 1296.61 1430.55 0.5389 5.4662 10
8 3.1532 1.5400 0.3874 142.60 1310.78 143.09 1289.86 1432.95 0.5734 5.4380 8
6 3.4134 1.5464 0.3595 151.74 1312.57 152.26 1283.02 1435.28 0.6077 5.4103 6
Ammonia
4 3.6901 1.5528 0.3340 160.88 1314.32 161.46 1276.10 1437.56 0.6418 5.3831 4
2 3.9842 1.5594 0.3106 170.07 1316.04 170.69 1269.08 1439.78 0.6759 5.3562 2
0 4.2962 1.5660 0.2892 179.29 1317.71 179.96 1261.97 1441.94 0.7097 5.3298 0
2 4.6270 1.5727 0.2695 188.53 1319.34 189.26 1254.77 1444.03 0.7435 5.3038 2
4 4.9773 1.5796 0.2514 197.80 1320.92 198.59 1247.48 1446.07 0.7770 5.2781 4
6 5.3479 1.5866 0.2348 207.10 1322.47 207.95 1240.09 1448.04 0.8105 5.2529 6
8 5.7395 1.5936 0.2195 216.42 1323.96 217.34 1232.61 1449.94 0.8438 5.2279 8
10 6.1529 1.6008 0.2054 225.77 1325.42 226.75 1225.03 1451.78 0.8769 5.2033 10
12 6.5890 1.6081 0.1923 235.14 1326.82 236.20 1217.35 1453.55 0.9099 5.1791 12
16 7.5324 1.6231 0.1691 253.95 1329.48 255.18 1201.70 1456.87 0.9755 5.1314 16
20 8.5762 1.6386 0.1492 272.86 1331.94 274.26 1185.64 1459.90 1.0404 5.0849 20
24 9.7274 1.6547 0.1320 291.84 1334.19 293.45 1169.16 1462.61 1.1048 5.0394 24
28 10.993 1.6714 0.1172 310.92 1336.20 312.75 1152.24 1465.00 1.1686 4.9948 28
32 12.380 1.6887 0.1043 330.07 1337.97 332.17 1134.87 1467.03 1.2319 4.9509 32
36 13.896 1.7068 0.0930 349.32 1339.47 351.69 1117.00 1468.70 1.2946 4.9078 36
40 15.549 1.7256 0.0831 368.67 1340.70 371.35 1098.62 1469.97 1.3569 4.8652 40
45 17.819 1.7503 0.0725 393.01 1341.81 396.13 1074.84 1470.96 1.4341 4.8125 45
50 20.331 1.7765 0.0634 417.56 1342.42 421.17 1050.09 1471.26 1.5109 4.7604 50
Source: Tables A-13 through A-15 are calculated based on equations from L. Haar and J. S. Gallagher, Thermodynamic Properties of Ammonia,
J. Phys. Chem. Reference Data, Vol. 7, 1978, pp. 635792.
TABLE A-14 Properties of Saturated Ammonia (LiquidVapor): Pressure Table

0.40 50.36 1.4236 2.6795 45.52 1264.54 45.46 1417.18 1371.72 0.1992 6.1618 0.40
0.50 46.53 1.4330 2.1752 28.73 1269.31 28.66 1406.73 1378.07 0.1245 6.0829 0.50
0.60 43.28 1.4410 1.8345 14.51 1273.27 14.42 1397.76 1383.34 0.0622 6.0186 0.60
0.70 40.46 1.4482 1.5884 2.11 1276.66 2.01 1389.85 1387.84 0.0086 5.9643 0.70
0.80 37.94 1.4546 1.4020 8.93 1279.61 9.04 1382.73 1391.78 0.0386 5.9174 0.80
0.90 35.67 1.4605 1.2559 18.91 1282.24 19.04 1376.23 1395.27 0.0808 5.8760 0.90
1.00 33.60 1.4660 1.1381 28.03 1284.61 28.18 1370.23 1398.41 0.1191 5.8391 1.00
1.25 29.07 1.4782 0.9237 48.03 1289.65 48.22 1356.89 1405.11 0.2018 5.7610 1.25
1.50 25.22 1.4889 0.7787 65.10 1293.80 65.32 1345.28 1410.61 0.2712 5.6973 1.50
1.75 21.86 1.4984 0.6740 80.08 1297.33 80.35 1334.92 1415.27 0.3312 5.6435 1.75
2.00 18.86 1.5071 0.5946 93.50 1300.39 93.80 1325.51 1419.31 0.3843 5.5969 2.00
2.25 16.15 1.5151 0.5323 105.68 1303.08 106.03 1316.83 1422.86 0.4319 5.5558 2.25
2.50 13.67 1.5225 0.4821 116.88 1305.49 117.26 1308.76 1426.03 0.4753 5.5190 2.50
2.75 11.37 1.5295 0.4408 127.26 1307.67 127.68 1301.20 1428.88 0.5152 5.4858 2.75
3.00 9.24 1.5361 0.4061 136.96 1309.65 137.42 1294.05 1431.47 0.5520 5.4554 3.00
3.25 7.24 1.5424 0.3765 146.06 1311.46 146.57 1287.27 1433.84 0.5864 5.4275 3.25
3.50 5.36 1.5484 0.3511 154.66 1313.14 155.20 1280.81 1436.01 0.6186 5.4016 3.50
Ammonia
3.75 3.58 1.5542 0.3289 162.80 1314.68 163.38 1274.64 1438.03 0.6489 5.3774 3.75
4.00 1.90 1.5597 0.3094 170.55 1316.12 171.18 1268.71 1439.89 0.6776 5.3548 4.00
4.25 0.29 1.5650 0.2921 177.96 1317.47 178.62 1263.01 1441.63 0.7048 5.3336 4.25
4.50 1.25 1.5702 0.2767 185.04 1318.73 185.75 1257.50 1443.25 0.7308 5.3135 4.50
4.75 2.72 1.5752 0.2629 191.84 1319.91 192.59 1252.18 1444.77 0.7555 5.2946 4.75
5.00 4.13 1.5800 0.2503 198.39 1321.02 199.18 1247.02 1446.19 0.7791 5.2765 5.00
5.25 5.48 1.5847 0.2390 204.69 1322.07 205.52 1242.01 1447.53 0.8018 5.2594 5.25
5.50 6.79 1.5893 0.2286 210.78 1323.06 211.65 1237.15 1448.80 0.8236 5.2430 5.50
5.75 8.05 1.5938 0.2191 216.66 1324.00 217.58 1232.41 1449.99 0.8446 5.2273 5.75
6.00 9.27 1.5982 0.2104 222.37 1324.89 223.32 1227.79 1451.12 0.8649 5.2122 6.00
7.00 13.79 1.6148 0.1815 243.56 1328.04 244.69 1210.38 1455.07 0.9394 5.1576 7.00
8.00 17.84 1.6302 0.1596 262.64 1330.64 263.95 1194.36 1458.30 1.0054 5.1099 8.00
9.00 21.52 1.6446 0.1424 280.05 1332.82 281.53 1179.44 1460.97 1.0649 5.0675 9.00
10.00 24.89 1.6584 0.1285 296.10 1334.66 297.76 1165.42 1463.18 1.1191 5.0294 10.00
12.00 30.94 1.6841 0.1075 324.99 1337.52 327.01 1139.52 1466.53 1.2152 4.9625 12.00
14.00 36.26 1.7080 0.0923 350.58 1339.56 352.97 1115.82 1468.79 1.2987 4.9050 14.00
16.00 41.03 1.7306 0.0808 373.69 1340.97 376.46 1093.77 1470.23 1.3729 4.8542 16.00
18.00 45.38 1.7522 0.0717 394.85 1341.88 398.00 1073.01 1471.01 1.4399 4.8086 18.00
20.00 49.37 1.7731 0.0644 414.44 1342.37 417.99 1053.27 1471.26 1.5012 4.7670 20.00
TABLE A-15 Properties of Superheated Ammonia Vapor

T v u h s v u h s
p 0.4 bar 0.04 MPa p 0.6 bar 0.06 MPa
(Tsat 50.36C) (Tsat 43.28C)
Sat. 2.6795 1264.54 1371.72 6.1618 1.8345 1273.27 1383.34 6.0186
50 2.6841 1265.11 1372.48 6.1652
45 2.7481 1273.05 1382.98 6.2118
40 2.8118 1281.01 1393.48 6.2573 1.8630 1278.62 1390.40 6.0490
35 2.8753 1288.96 1403.98 6.3018 1.9061 1286.75 1401.12 6.0946
30 2.9385 1296.93 1414.47 6.3455 1.9491 1294.88 1411.83 6.1390
25 3.0015 1304.90 1424.96 6.3882 1.9918 1303.01 1422.52 6.1826
20 3.0644 1312.88 1435.46 6.4300 2.0343 1311.13 1433.19 6.2251
15 3.1271 1320.87 1445.95 6.4711 2.0766 1319.25 1443.85 6.2668
10 3.1896 1328.87 1456.45 6.5114 2.1188 1327.37 1454.50 6.3077
5 3.2520 1336.88 1466.95 6.5509 2.1609 1335.49 1465.14 6.3478
0 3.3142 1344.90 1477.47 6.5898 2.2028 1343.61 1475.78 6.3871
5 3.3764 1352.95 1488.00 6.6280 2.2446 1351.75 1486.43 6.4257
p 0.8 bar 0.08 MPa p 1.0 bar 0.10 MPa

(Tsat 37.94C) (Tsat 33.60C)
Sat. 1.4021 1279.61 1391.78 5.9174 1.1381 1284.61 1398.41 5.8391
Ammonia
35 1.4215 1284.51 1398.23 5.9446
30 1.4543 1292.81 1409.15 5.9900 1.1573 1290.71 1406.44 5.8723
25 1.4868 1301.09 1420.04 6.0343 1.1838 1299.15 1417.53 5.9175
20 1.5192 1309.36 1430.90 6.0777 1.2101 1307.57 1428.58 5.9616
15 1.5514 1317.61 1441.72 6.1200 1.2362 1315.96 1439.58 6.0046
10 1.5834 1325.85 1452.53 6.1615 1.2621 1324.33 1450.54 6.0467
5 1.6153 1334.09 1463.31 6.2021 1.2880 1332.67 1461.47 6.0878
0 1.6471 1342.31 1474.08 6.2419 1.3136 1341.00 1472.37 6.1281
5 1.6788 1350.54 1484.84 6.2809 1.3392 1349.33 1483.25 6.1676
10 1.7103 1358.77 1495.60 6.3192 1.3647 1357.64 1494.11 6.2063
15 1.7418 1367.01 1506.35 6.3568 1.3900 1365.95 1504.96 6.2442
20 1.7732 1375.25 1517.10 6.3939 1.4153 1374.27 1515.80 6.2816
p 1.5 bar 0.15 MPa p 2.0 bar 0.20 MPa

(Tsat 25.22C) (Tsat 18.86C)
Sat. 0.7787 1293.80 1410.61 5.6973 0.59460 1300.39 1419.31 5.5969
25 0.7795 1294.20 1411.13 5.6994
20 0.7978 1303.00 1422.67 5.7454
15 0.8158 1311.75 1434.12 5.7902 0.60542 1307.43 1428.51 5.6328
10 0.8336 1320.44 1445.49 5.8338 0.61926 1316.46 1440.31 5.6781
5 0.8514 1329.08 1456.79 5.8764 0.63294 1325.41 1452.00 5.7221
0 0.8689 1337.68 1468.02 5.9179 0.64648 1334.29 1463.59 5.7649
5 0.8864 1346.25 1479.20 5.9585 0.65989 1343.11 1475.09 5.8066
10 0.9037 1354.78 1490.34 5.9981 0.67320 1351.87 1486.51 5.8473
15 0.9210 1363.29 1501.44 6.0370 0.68640 1360.59 1497.87 5.8871
20 0.9382 1371.79 1512.51 6.0751 0.69952 1369.28 1509.18 5.9260
25 0.9553 1380.28 1523.56 6.1125 0.71256 1377.93 1520.44 5.9641
30 0.9723 1388.76 1534.60 6.1492 0.72553 1386.56 1531.67 6.0014

T v u h s v u h s
p 2.5 bar 0.25 MPa p 3.0 bar 0.30 MPa
(Tsat 13.67C) (Tsat 9.24C)
Sat. 0.48213 1305.49 1426.03 5.5190 0.40607 1309.65 1431.47 5.4554
10 0.49051 1312.37 1435.00 5.5534
5 0.50180 1321.65 1447.10 5.5989 0.41428 1317.80 1442.08 5.4953
0 0.51293 1330.83 1459.06 5.6431 0.42382 1327.28 1454.43 5.5409
5 0.52393 1339.91 1470.89 5.6860 0.43323 1336.64 1466.61 5.5851
10 0.53482 1348.91 1482.61 5.7278 0.44251 1345.89 1478.65 5.6280
15 0.54560 1357.84 1494.25 5.7685 0.45169 1355.05 1490.56 5.6697
20 0.55630 1366.72 1505.80 5.8083 0.46078 1364.13 1502.36 5.7103
25 0.56691 1375.55 1517.28 5.8471 0.46978 1373.14 1514.07 5.7499
30 0.57745 1384.34 1528.70 5.8851 0.47870 1382.09 1525.70 5.7886
35 0.58793 1393.10 1540.08 5.9223 0.48756 1391.00 1537.26 5.8264
40 0.59835 1401.84 1551.42 5.9589 0.49637 1399.86 1548.77 5.8635
45 0.60872 1410.56 1562.74 5.9947 0.50512 1408.70 1560.24 5.8998
p 3.5 bar 0.35 MPa p 4.0 bar 0.40 MPa

Sat. 0.35108 1313.14 1436.01 5.4016 0.30942 1316.12 1439.89 5.3548
Ammonia
0 0.36011 1323.66 1449.70 5.4522 0.31227 1319.95 1444.86 5.3731

10 0.37654 1342.82 1474.61 5.5417 0.32701 1339.68 1470.49 5.4652
20 0.39251 1361.49 1498.87 5.6259 0.34129 1358.81 1495.33 5.5515
30 0.40814 1379.81 1522.66 5.7057 0.35520 1377.49 1519.57 5.6328
40 0.42350 1397.87 1546.09 5.7818 0.36884 1395.85 1543.38 5.7101
60 0.45363 1433.55 1592.32 5.9249 0.39550 1431.97 1590.17 5.8549
80 0.48320 1469.06 1638.18 6.0586 0.42160 1467.77 1636.41 5.9897
100 0.51240 1504.73 1684.07 6.1850 0.44733 1503.64 1682.58 6.1169
120 0.54136 1540.79 1730.26 6.3056 0.47280 1539.85 1728.97 6.2380
140 0.57013 1577.38 1776.92 6.4213 0.49808 1576.55 1775.79 6.3541
160 0.59876 1614.60 1824.16 6.5330 0.52323 1613.86 1823.16 6.4661
180 0.62728 1652.51 1872.06 6.6411 0.54827 1651.85 1871.16 6.5744
200 0.65572 1691.15 1920.65 6.7460 0.57322 1690.56 1919.85 6.6796
p 4.5 bar 0.45 MPa p 5.0 bar 0.50 MPa

Sat. 0.27671 1318.73 1443.25 5.3135 0.25034 1321.02 1446.19 5.2765
10 0.28846 1336.48 1466.29 5.3962 0.25757 1333.22 1462.00 5.3330
20 0.30142 1356.09 1491.72 5.4845 0.26949 1353.32 1488.06 5.4234
30 0.31401 1375.15 1516.45 5.5674 0.28103 1372.76 1513.28 5.5080
40 0.32631 1393.80 1540.64 5.6460 0.29227 1391.74 1537.87 5.5878
60 0.35029 1430.37 1588.00 5.7926 0.31410 1428.76 1585.81 5.7362
80 0.37369 1466.47 1634.63 5.9285 0.33535 1465.16 1632.84 5.8733
100 0.39671 1502.55 1681.07 6.0564 0.35621 1501.46 1679.56 6.0020
120 0.41947 1538.91 1727.67 6.1781 0.37681 1537.97 1726.37 6.1242
140 0.44205 1575.73 1774.65 6.2946 0.39722 1574.90 1773.51 6.2412
160 0.46448 1613.13 1822.15 6.4069 0.41749 1612.40 1821.14 6.3537
180 0.48681 1651.20 1870.26 6.5155 0.43765 1650.54 1869.36 6.4626
200 0.50905 1689.97 1919.04 6.6208 0.45771 1689.38 1918.24 6.5681

T v u h s v u h s
p 5.5 bar 0.55 MPa p 6.0 bar 0.60 MPa
Sat. 0.22861 1323.06 1448.80 5.2430 0.21038 1324.89 1451.12 5.2122
10 0.23227 1329.88 1457.63 5.2743 0.21115 1326.47 1453.16 5.2195
20 0.24335 1350.50 1484.34 5.3671 0.22155 1347.62 1480.55 5.3145
30 0.25403 1370.35 1510.07 5.4534 0.23152 1367.90 1506.81 5.4026
40 0.26441 1389.64 1535.07 5.5345 0.24118 1387.52 1532.23 5.4851
50 0.27454 1408.53 1559.53 5.6114 0.25059 1406.67 1557.03 5.5631
60 0.28449 1427.13 1583.60 5.6848 0.25981 1425.49 1581.38 5.6373
80 0.30398 1463.85 1631.04 5.8230 0.27783 1462.52 1629.22 5.7768
100 0.32307 1500.36 1678.05 5.9525 0.29546 1499.25 1676.52 5.9071
120 0.34190 1537.02 1725.07 6.0753 0.31281 1536.07 1723.76 6.0304
140 0.36054 1574.07 1772.37 6.1926 0.32997 1573.24 1771.22 6.1481
160 0.37903 1611.66 1820.13 6.3055 0.34699 1610.92 1819.12 6.2613
180 0.39742 1649.88 1868.46 6.4146 0.36390 1649.22 1867.56 6.3707
200 0.41571 1688.79 1917.43 6.5203 0.38071 1688.20 1916.63 6.4766
p 7.0 bar 0.70 MPa p 8.0 bar 0.80 MPa

(Tsat 13.79C) (Tsat 17.84C)
Ammonia
Sat. 0.18148 1328.04 1455.07 5.1576 0.15958 1330.64 1458.30 5.1099
20 0.18721 1341.72 1472.77 5.2186 0.16138 1335.59 1464.70 5.1318
30 0.19610 1362.88 1500.15 5.3104 0.16948 1357.71 1493.29 5.2277
40 0.20464 1383.20 1526.45 5.3958 0.17720 1378.77 1520.53 5.3161
50 0.21293 1402.90 1551.95 5.4760 0.18465 1399.05 1546.77 5.3986
60 0.22101 1422.16 1576.87 5.5519 0.19189 1418.77 1572.28 5.4763
80 0.23674 1459.85 1625.56 5.6939 0.20590 1457.14 1621.86 5.6209
100 0.25205 1497.02 1673.46 5.8258 0.21949 1494.77 1670.37 5.7545
120 0.26709 1534.16 1721.12 5.9502 0.23280 1532.24 1718.48 5.8801
140 0.28193 1571.57 1768.92 6.0688 0.24590 1569.89 1766.61 5.9995
160 0.29663 1609.44 1817.08 6.1826 0.25886 1607.96 1815.04 6.1140
180 0.31121 1647.90 1865.75 6.2925 0.27170 1646.57 1863.94 6.2243
200 0.32571 1687.02 1915.01 6.3988 0.28445 1685.83 1913.39 6.3311
p 9.0 bar 0.90 MPa p 10.0 bar 1.00 MPa

(Tsat 21.52C) (Tsat 24.89C)
Sat. 0.14239 1332.82 1460.97 5.0675 0.12852 1334.66 1463.18 5.0294
30 0.14872 1352.36 1486.20 5.1520 0.13206 1346.82 1478.88 5.0816
40 0.15582 1374.21 1514.45 5.2436 0.13868 1369.52 1508.20 5.1768
50 0.16263 1395.11 1541.47 5.3286 0.14499 1391.07 1536.06 5.2644
60 0.16922 1415.32 1567.61 5.4083 0.15106 1411.79 1562.86 5.3460
80 0.18191 1454.39 1618.11 5.5555 0.16270 1451.60 1614.31 5.4960
100 0.19416 1492.50 1667.24 5.6908 0.17389 1490.20 1664.10 5.6332
120 0.20612 1530.30 1715.81 5.8176 0.18478 1528.35 1713.13 5.7612
140 0.21788 1568.20 1764.29 5.9379 0.19545 1566.51 1761.96 5.8823
160 0.22948 1606.46 1813.00 6.0530 0.20598 1604.97 1810.94 5.9981
180 0.24097 1645.24 1862.12 6.1639 0.21638 1643.91 1860.29 6.1095
200 0.25237 1684.64 1911.77 6.2711 0.22670 1683.44 1910.14 6.2171

T v u h s v u h s
p 12.0 bar 1.20 MPa p 14.0 bar 1.40 MPa
(Tsat 30.94C) (Tsat 36.26C)
Sat. 0.10751 1337.52 1466.53 4.9625 0.09231 1339.56 1468.79 4.9050
40 0.11287 1359.73 1495.18 5.0553 0.09432 1349.29 1481.33 4.9453
60 0.12378 1404.54 1553.07 5.2347 0.10423 1396.97 1542.89 5.1360
80 0.13387 1445.91 1606.56 5.3906 0.11324 1440.06 1598.59 5.2984
100 0.14347 1485.55 1657.71 5.5315 0.12172 1480.79 1651.20 5.4433
120 0.15275 1524.41 1707.71 5.6620 0.12986 1520.41 1702.21 5.5765
140 0.16181 1563.09 1757.26 5.7850 0.13777 1559.63 1752.52 5.7013
160 0.17072 1601.95 1806.81 5.9021 0.14552 1598.92 1802.65 5.8198
180 0.17950 1641.23 1856.63 6.0145 0.15315 1638.53 1852.94 5.9333
200 0.18819 1681.05 1906.87 6.1230 0.16068 1678.64 1903.59 6.0427
220 0.19680 1721.50 1957.66 6.2282 0.16813 1719.35 1954.73 6.1485
240 0.20534 1762.63 2009.04 6.3303 0.17551 1760.72 2006.43 6.2513
260 0.21382 1804.48 2061.06 6.4297 0.18283 1802.78 2058.75 6.3513
280 0.22225 1847.04 2113.74 6.5267 0.19010 1845.55 2111.69 6.4488
p 16.0 bar 1.60 MPa p 18.0 bar 1.80 MPa

(Tsat 41.03C) (Tsat 45.38C)
Ammonia
Sat. 0.08079 1340.97 1470.23 4.8542 0.07174 1341.88 1471.01 4.8086

60 0.08951 1389.06 1532.28 5.0461 0.07801 1380.77 1521.19 4.9627
80 0.09774 1434.02 1590.40 5.2156 0.08565 1427.79 1581.97 5.1399
100 0.10539 1475.93 1644.56 5.3648 0.09267 1470.97 1637.78 5.2937
120 0.11268 1516.34 1696.64 5.5008 0.09931 1512.22 1690.98 5.4326
140 0.11974 1556.14 1747.72 5.6276 0.10570 1552.61 1742.88 5.5614
160 0.12663 1595.85 1798.45 5.7475 0.11192 1592.76 1794.23 5.6828
180 0.13339 1635.81 1849.23 5.8621 0.11801 1633.08 1845.50 5.7985
200 0.14005 1676.21 1900.29 5.9723 0.12400 1673.78 1896.98 5.9096
220 0.14663 1717.18 1951.79 6.0789 0.12991 1715.00 1948.83 6.0170
240 0.15314 1758.79 2003.81 6.1823 0.13574 1756.85 2001.18 6.1210
260 0.15959 1801.07 2056.42 6.2829 0.14152 1799.35 2054.08 6.2222
280 0.16599 1844.05 2109.64 6.3809 0.14724 1842.55 2107.58 6.3207
p 20.0 bar 2.00 MPa

(Tsat 49.37C)
Sat. 0.06445 1342.37 1471.26 4.7670
60 0.06875 1372.05 1509.54 4.8838
80 0.07596 1421.36 1573.27 5.0696
100 0.08248 1465.89 1630.86 5.2283
120 0.08861 1508.03 1685.24 5.3703
140 0.09447 1549.03 1737.98 5.5012
160 0.10016 1589.65 1789.97 5.6241
180 0.10571 1630.32 1841.74 5.7409
200 0.11116 1671.33 1893.64 5.8530
220 0.11652 1712.82 1945.87 5.9611
240 0.12182 1754.90 1998.54 6.0658
260 0.12706 1797.63 2051.74 6.1675
280 0.13224 1841.03 2105.50 6.2665
TABLE A-16 Properties of Saturated Propane (LiquidVapor): Temperature Table

100 0.02888 1.553 11.27 128.4 319.5 128.4 480.4 352.0 0.634 2.140 100
90 0.06426 1.578 5.345 107.8 329.3 107.8 471.4 363.6 0.519 2.055 90
80 0.1301 1.605 2.774 87.0 339.3 87.0 462.4 375.4 0.408 1.986 80
70 0.2434 1.633 1.551 65.8 349.5 65.8 453.1 387.3 0.301 1.929 70
60 0.4261 1.663 0.9234 44.4 359.9 44.3 443.5 399.2 0.198 1.883 60
50 0.7046 1.694 0.5793 22.5 370.4 22.4 433.6 411.2 0.098 1.845 50
40 1.110 1.728 0.3798 0.2 381.0 0.0 423.2 423.2 0.000 1.815 40
30 1.677 1.763 0.2585 22.6 391.6 22.9 412.1 435.0 0.096 1.791 30
20 2.444 1.802 0.1815 45.9 402.4 46.3 400.5 446.8 0.190 1.772 20
10 3.451 1.844 0.1309 69.8 413.2 70.4 388.0 458.4 0.282 1.757 10
0 4.743 1.890 0.09653 94.2 423.8 95.1 374.5 469.6 0.374 1.745 0
4 5.349 1.910 0.08591 104.2 428.1 105.3 368.8 474.1 0.410 1.741 4
8 6.011 1.931 0.07666 114.3 432.3 115.5 362.9 478.4 0.446 1.737 8
12 6.732 1.952 0.06858 124.6 436.5 125.9 356.8 482.7 0.482 1.734 12
16 7.515 1.975 0.06149 135.0 440.7 136.4 350.5 486.9 0.519 1.731 16
20 8.362 1.999 0.05525 145.4 444.8 147.1 343.9 491.0 0.555 1.728 20
24 9.278 2.024 0.04973 156.1 448.9 158.0 337.0 495.0 0.591 1.725 24
28 10.27 2.050 0.04483 166.9 452.9 169.0 329.9 498.9 0.627 1.722 28
32 11.33 2.078 0.04048 177.8 456.7 180.2 322.4 502.6 0.663 1.720 32
36 12.47 2.108 0.03659 188.9 460.6 191.6 314.6 506.2 0.699 1.717 36
40 13.69 2.140 0.03310 200.2 464.3 203.1 306.5 509.6 0.736 1.715 40
44 15.00 2.174 0.02997 211.7 467.9 214.9 298.0 512.9 0.772 1.712 44
48 16.40 2.211 0.02714 223.4 471.4 227.0 288.9 515.9 0.809 1.709 48
Propane
52 17.89 2.250 0.02459 235.3 474.6 239.3 279.3 518.6 0.846 1.705 52
56 19.47 2.293 0.02227 247.4 477.7 251.9 269.2 521.1 0.884 1.701 56
60 21.16 2.340 0.02015 259.8 480.6 264.8 258.4 523.2 0.921 1.697 60
65 23.42 2.406 0.01776 275.7 483.6 281.4 243.8 525.2 0.969 1.690 65
70 25.86 2.483 0.01560 292.3 486.1 298.7 227.7 526.4 1.018 1.682 70
75 28.49 2.573 0.01363 309.5 487.8 316.8 209.8 526.6 1.069 1.671 75
80 31.31 2.683 0.01182 327.6 488.2 336.0 189.2 525.2 1.122 1.657 80
85 34.36 2.827 0.01011 347.2 486.9 356.9 164.7 521.6 1.178 1.638 85
90 37.64 3.038 0.008415 369.4 482.2 380.8 133.1 513.9 1.242 1.608 90
95 41.19 3.488 0.006395 399.8 467.4 414.2 79.5 493.7 1.330 1.546 95
96.7 42.48 4.535 0.004535 434.9 434.9 454.2 0.0 457.2 1.437 1.437 96.7
Source: Tables A-16 through A-18 are calculated based on B. A. Younglove and J. F. Ely, Thermophysical Properties of Fluids. II. Methane,
Ethane, Propane, Isobutane and Normal Butane, J. Phys. Chem. Ref. Data, Vol. 16, No. 4, 1987, pp. 577598.
TABLE A-17 Properties of Saturated Propane (LiquidVapor): Pressure Table

0.05 93.28 1.570 6.752 114.6 326.0 114.6 474.4 359.8 0.556 2.081 0.05
0.10 83.87 1.594 3.542 95.1 335.4 95.1 465.9 370.8 0.450 2.011 0.10
0.25 69.55 1.634 1.513 64.9 350.0 64.9 452.7 387.8 0.297 1.927 0.25
0.50 56.93 1.672 0.7962 37.7 363.1 37.6 440.5 402.9 0.167 1.871 0.50
0.75 48.68 1.698 0.5467 19.6 371.8 19.5 432.3 412.8 0.085 1.841 0.75
1.00 42.38 1.719 0.4185 5.6 378.5 5.4 425.7 420.3 0.023 1.822 1.00
2.00 25.43 1.781 0.2192 33.1 396.6 33.5 406.9 440.4 0.139 1.782 2.00
3.00 14.16 1.826 0.1496 59.8 408.7 60.3 393.3 453.6 0.244 1.762 3.00
4.00 5.46 1.865 0.1137 80.8 418.0 81.5 382.0 463.5 0.324 1.751 4.00
5.00 1.74 1.899 0.09172 98.6 425.7 99.5 372.1 471.6 0.389 1.743 5.00
6.00 7.93 1.931 0.07680 114.2 432.2 115.3 363.0 478.3 0.446 1.737 6.00
7.00 13.41 1.960 0.06598 128.2 438.0 129.6 354.6 484.2 0.495 1.733 7.00
8.00 18.33 1.989 0.05776 141.0 443.1 142.6 346.7 489.3 0.540 1.729 8.00
9.00 22.82 2.016 0.05129 152.9 447.6 154.7 339.1 493.8 0.580 1.726 9.00
10.00 26.95 2.043 0.04606 164.0 451.8 166.1 331.8 497.9 0.618 1.723 10.00
11.00 30.80 2.070 0.04174 174.5 455.6 176.8 324.7 501.5 0.652 1.721 11.00
12.00 34.39 2.096 0.03810 184.4 459.1 187.0 317.8 504.8 0.685 1.718 12.00
13.00 37.77 2.122 0.03499 193.9 462.2 196.7 311.0 507.7 0.716 1.716 13.00
14.00 40.97 2.148 0.03231 203.0 465.2 206.0 304.4 510.4 0.745 1.714 14.00
15.00 44.01 2.174 0.02997 211.7 467.9 215.0 297.9 512.9 0.772 1.712 15.00
16.00 46.89 2.200 0.02790 220.1 470.4 223.6 291.4 515.0 0.799 1.710 16.00
17.00 49.65 2.227 0.02606 228.3 472.7 232.0 285.0 517.0 0.824 1.707 17.00
18.00 52.30 2.253 0.02441 236.2 474.9 240.2 278.6 518.8 0.849 1.705 18.00
Propane
19.00 54.83 2.280 0.02292 243.8 476.9 248.2 272.2 520.4 0.873 1.703 19.00
20.00 57.27 2.308 0.02157 251.3 478.7 255.9 265.9 521.8 0.896 1.700 20.00
22.00 61.90 2.364 0.01921 265.8 481.7 271.0 253.0 524.0 0.939 1.695 22.00
24.00 66.21 2.424 0.01721 279.7 484.3 285.5 240.1 525.6 0.981 1.688 24.00
26.00 70.27 2.487 0.01549 293.1 486.2 299.6 226.9 526.5 1.021 1.681 26.00
28.00 74.10 2.555 0.01398 306.2 487.5 313.4 213.2 526.6 1.060 1.673 28.00
30.00 77.72 2.630 0.01263 319.2 488.1 327.1 198.9 526.0 1.097 1.664 30.00
35.00 86.01 2.862 0.009771 351.4 486.3 361.4 159.1 520.5 1.190 1.633 35.00
40.00 93.38 3.279 0.007151 387.9 474.7 401.0 102.3 503.3 1.295 1.574 40.00
42.48 96.70 4.535 0.004535 434.9 434.9 454.2 0.0 454.2 1.437 1.437 42.48
TABLE A-18 Properties of Superheated Propane

T v u h s v u h s
p 0.05 bar 0.005 MPa p 0.1 bar 0.01 MPa
(Tsat 93.28C) (Tsat 83.87C)
Sat. 6.752 326.0 359.8 2.081 3.542 367.3 370.8 2.011
90 6.877 329.4 363.8 2.103
80 7.258 339.8 376.1 2.169 3.617 339.5 375.7 2.037
70 7.639 350.6 388.8 2.233 3.808 350.3 388.4 2.101
60 8.018 361.8 401.9 2.296 3.999 361.5 401.5 2.164
50 8.397 373.3 415.3 2.357 4.190 373.1 415.0 2.226
40 8.776 385.1 429.0 2.418 4.380 385.0 428.8 2.286
30 9.155 397.4 443.2 2.477 4.570 397.3 443.0 2.346
20 9.533 410.1 457.8 2.536 4.760 410.0 457.6 2.405
10 9.911 423.2 472.8 2.594 4.950 423.1 472.6 2.463
0 10.29 436.8 488.2 2.652 5.139 436.7 488.1 2.520
10 10.67 450.8 504.1 2.709 5.329 450.6 503.9 2.578
20 11.05 270.6 520.4 2.765 5.518 465.1 520.3 2.634
p 0.5 bar 0.05 MPa p 1.0 bar 0.1 MPa

(Tsat 56.93C) (Tsat 42.38C)
Sat. 0.796 363.1 402.9 1.871 0.4185 378.5 420.3 1.822
50 0.824 371.3 412.5 1.914
40 0.863 383.4 426.6 1.976 0.4234 381.5 423.8 1.837
30 0.903 396.0 441.1 2.037 0.4439 394.2 438.6 1.899
20 0.942 408.8 455.9 2.096 0.4641 407.3 453.7 1.960
10 0.981 422.1 471.1 2.155 0.4842 420.7 469.1 2.019
0 1.019 435.8 486.7 2.213 0.5040 434.4 484.8 2.078
Propane
10 1.058 449.8 502.7 2.271 0.5238 448.6 501.0 2.136
20 1.096 464.3 519.1 2.328 0.5434 463.3 517.6 2.194
30 1.135 479.2 535.9 2.384 0.5629 478.2 534.5 2.251
40 1.173 494.6 553.2 2.440 0.5824 493.7 551.9 2.307
50 1.211 510.4 570.9 2.496 0.6018 509.5 569.7 2.363
60 1.249 526.7 589.1 2.551 0.6211 525.8 587.9 2.419
p 2.0 bar 0.2 MPa p 3.0 bar 0.3 MPa

(Tsat 25.43C) (Tsat 14.16C)
Sat. 0.2192 396.6 440.4 1.782 0.1496 408.7 453.6 1.762
20 0.2251 404.0 449.0 1.816
10 0.2358 417.7 464.9 1.877 0.1527 414.7 460.5 1.789
0 0.2463 431.8 481.1 1.938 0.1602 429.0 477.1 1.851
10 0.2566 446.3 497.6 1.997 0.1674 443.8 494.0 1.912
20 0.2669 461.1 514.5 2.056 0.1746 458.8 511.2 1.971
30 0.2770 476.3 531.7 2.113 0.1816 474.2 528.7 2.030
40 0.2871 491.9 549.3 2.170 0.1885 490.1 546.6 2.088
50 0.2970 507.9 567.3 2.227 0.1954 506.2 564.8 2.145
60 0.3070 524.3 585.7 2.283 0.2022 522.7 583.4 2.202
70 0.3169 541.1 604.5 2.339 0.2090 539.6 602.3 2.258
80 0.3267 558.4 623.7 2.394 0.2157 557.0 621.7 2.314
90 0.3365 576.1 643.4 2.449 0.2223 574.8 641.5 2.369

T v u h s v u h s
Sat. 0.1137 418.0 463.5 1.751 0.09172 425.7 471.6 1.743
0 0.1169 426.1 472.9 1.786
10 0.1227 441.2 490.3 1.848 0.09577 438.4 486.3 1.796
20 0.1283 456.6 507.9 1.909 0.1005 454.1 504.3 1.858
30 0.1338 472.2 525.7 1.969 0.1051 470.0 522.5 1.919
40 0.1392 488.1 543.8 2.027 0.1096 486.1 540.9 1.979
50 0.1445 504.4 562.2 2.085 0.1140 502.5 559.5 2.038
60 0.1498 521.1 581.0 2.143 0.1183 519.4 578.5 2.095
70 0.1550 538.1 600.1 2.199 0.1226 536.6 597.9 2.153
80 0.1601 555.7 619.7 2.255 0.1268 554.1 617.5 2.209
90 0.1652 573.5 639.6 2.311 0.1310 572.1 637.6 2.265
100 0.1703 591.8 659.9 2.366 0.1351 590.5 658.0 2.321
110 0.1754 610.4 680.6 2.421 0.1392 609.3 678.9 2.376

(Tsat 7.93C) (Tsat 13.41C)
Sat. 0.07680 432.2 478.3 1.737 0.06598 438.0 484.2 1.733
10 0.07769 435.6 482.2 1.751
20 0.08187 451.5 500.6 1.815 0.06847 448.8 496.7 1.776
30 0.08588 467.7 519.2 1.877 0.07210 465.2 515.7 1.840
40 0.08978 484.0 537.9 1.938 0.07558 481.9 534.8 1.901
50 0.09357 500.7 556.8 1.997 0.07896 498.7 554.0 1.962
60 0.09729 517.6 576.0 2.056 0.08225 515.9 573.5 2.021
70 0.1009 535.0 595.5 2.113 0.08547 533.4 593.2 2.079
Propane
80 0.1045 552.7 615.4 2.170 0.08863 551.2 613.2 2.137

90 0.1081 570.7 635.6 2.227 0.09175 569.4 633.6 2.194
100 0.1116 589.2 656.2 2.283 0.09482 587.9 654.3 2.250
110 0.1151 608.0 677.1 2.338 0.09786 606.8 675.3 2.306
120 0.1185 627.3 698.4 2.393 0.1009 626.2 696.8 2.361

(Tsat 18.33C) (Tsat 22.82C)
Sat. 0.05776 443.1 489.3 1.729 0.05129 447.2 493.8 1.726
20 0.05834 445.9 492.6 1.740
30 0.06170 462.7 512.1 1.806 0.05355 460.0 508.2 1.774
40 0.06489 479.6 531.5 1.869 0.05653 477.2 528.1 1.839
50 0.06796 496.7 551.1 1.930 0.05938 494.7 548.1 1.901
60 0.07094 514.0 570.8 1.990 0.06213 512.2 568.1 1.962
70 0.07385 531.6 590.7 2.049 0.06479 530.0 588.3 2.022
80 0.07669 549.6 611.0 2.107 0.06738 548.1 608.7 2.081
90 0.07948 567.9 631.5 2.165 0.06992 566.5 629.4 2.138
100 0.08222 586.5 652.3 2.221 0.07241 585.2 650.4 2.195
110 0.08493 605.6 673.5 2.277 0.07487 604.3 671.7 2.252
120 0.08761 625.0 695.1 2.333 0.07729 623.7 693.3 2.307
130 0.09026 644.8 717.0 2.388 0.07969 643.6 715.3 2.363
140 0.09289 665.0 739.3 2.442 0.08206 663.8 737.7 2.418

T v u h s v u h s
p 10.0 bar 1.0 MPa p 12.0 bar 1.2 MPa
(Tsat 26.95C) (Tsat 34.39C)
Sat. 0.04606 451.8 497.9 1.723 0.03810 459.1 504.8 1.718
30 0.04696 457.1 504.1 1.744
40 0.04980 474.8 524.6 1.810 0.03957 469.4 516.9 1.757
50 0.05248 492.4 544.9 1.874 0.04204 487.8 538.2 1.824
60 0.05505 510.2 565.2 1.936 0.04436 506.1 559.3 1.889
70 0.05752 528.2 585.7 1.997 0.04657 524.4 580.3 1.951
80 0.05992 546.4 606.3 2.056 0.04869 543.1 601.5 2.012
90 0.06226 564.9 627.2 2.114 0.05075 561.8 622.7 2.071
100 0.06456 583.7 648.3 2.172 0.05275 580.9 644.2 2.129
110 0.06681 603.0 669.8 2.228 0.05470 600.4 666.0 2.187
120 0.06903 622.6 691.6 2.284 0.05662 620.1 688.0 2.244
130 0.07122 642.5 713.7 2.340 0.05851 640.1 710.3 2.300
140 0.07338 662.8 736.2 2.395 0.06037 660.6 733.0 2.355
p 14.0 bar 1.4 MPa p 16.0 bar 1.6 MPa

(Tsat 40.97C) (Tsat 46.89C)
Sat. 0.03231 465.2 510.4 1.714 0.02790 470.4 515.0 1.710
50 0.03446 482.6 530.8 1.778 0.02861 476.7 522.5 1.733
60 0.03664 501.6 552.9 1.845 0.03075 496.6 545.8 1.804
70 0.03869 520.4 574.6 1.909 0.03270 516.2 568.5 1.871
80 0.04063 539.4 596.3 1.972 0.03453 535.7 590.9 1.935
90 0.04249 558.6 618.1 2.033 0.03626 555.2 613.2 1.997
100 0.04429 577.9 639.9 2.092 0.03792 574.8 635.5 2.058
110 0.04604 597.5 662.0 2.150 0.03952 594.7 657.9 2.117
Propane
120 0.04774 617.5 684.3 2.208 0.04107 614.8 680.5 2.176
130 0.04942 637.7 706.9 2.265 0.04259 635.3 703.4 2.233
140 0.05106 658.3 729.8 2.321 0.04407 656.0 726.5 2.290
150 0.05268 679.2 753.0 2.376 0.04553 677.1 749.9 2.346
160 0.05428 700.5 776.5 2.431 0.04696 698.5 773.6 2.401
p 18.0 bar 1.8 MPa p 20.0 bar 2.0 MPa

(Tsat 52.30C) (Tsat 57.27C)
Sat. 0.02441 474.9 518.8 1.705 0.02157 478.7 521.8 1.700
60 0.02606 491.1 538.0 1.763 0.02216 484.8 529.1 1.722
70 0.02798 511.4 561.8 1.834 0.02412 506.3 554.5 1.797
80 0.02974 531.6 585.1 1.901 0.02585 527.1 578.8 1.867
90 0.03138 551.5 608.0 1.965 0.02744 547.6 602.5 1.933
100 0.03293 571.5 630.8 2.027 0.02892 568.1 625.9 1.997
110 0.03443 591.7 653.7 2.087 0.03033 588.5 649.2 2.059
120 0.03586 612.1 676.6 2.146 0.03169 609.2 672.6 2.119
130 0.03726 632.7 699.8 2.204 0.03299 630.0 696.0 2.178
140 0.03863 653.6 723.1 2.262 0.03426 651.2 719.7 2.236
150 0.03996 674.8 746.7 2.318 0.03550 672.5 743.5 2.293
160 0.04127 696.3 770.6 2.374 0.03671 694.2 767.6 2.349
170 0.04256 718.2 794.8 2.429 0.03790 716.2 792.0 2.404
180 0.04383 740.4 819.3 2.484 0.03907 738.5 816.6 2.459

T v u h s v u h s
p 22.0 bar 2.2 MPa p 24.0 bar 2.4 MPa
(Tsat 61.90C) (Tsat 66.21C)
Sat. 0.01921 481.8 524.0 1.695 0.01721 484.3 525.6 1.688
70 0.02086 500.5 546.4 1.761 0.01802 493.7 536.9 1.722
80 0.02261 522.4 572.1 1.834 0.01984 517.0 564.6 1.801
90 0.02417 543.5 596.7 1.903 0.02141 539.0 590.4 1.873
100 0.02561 564.5 620.8 1.969 0.02283 560.6 615.4 1.941
110 0.02697 585.3 644.6 2.032 0.02414 581.9 639.8 2.006
120 0.02826 606.2 668.4 2.093 0.02538 603.2 664.1 2.068
130 0.02949 627.3 692.2 2.153 0.02656 624.6 688.3 2.129
140 0.03069 648.6 716.1 2.211 0.02770 646.0 712.5 2.188
150 0.03185 670.1 740.2 2.269 0.02880 667.8 736.9 2.247
160 0.03298 691.9 764.5 2.326 0.02986 689.7 761.4 2.304
170 0.03409 714.1 789.1 2.382 0.03091 711.9 786.1 2.360
180 0.03517 736.5 813.9 2.437 0.03193 734.5 811.1 2.416
p 26.0 bar 2.6 MPa p 30.0 bar 3.0 MPa

(Tsat 70.27C) (Tsat 77.72C)
Sat. 0.01549 486.2 526.5 1.681 0.01263 488.2 526.0 1.664
80 0.01742 511.0 556.3 1.767 0.01318 495.4 534.9 1.689
90 0.01903 534.2 583.7 1.844 0.01506 522.8 568.0 1.782
100 0.02045 556.4 609.6 1.914 0.01654 547.2 596.8 1.860
110 0.02174 578.3 634.8 1.981 0.01783 570.4 623.9 1.932
120 0.02294 600.0 659.6 2.045 0.01899 593.0 650.0 1.999
130 0.02408 621.6 684.2 2.106 0.02007 615.4 675.6 2.063
Propane
140 0.02516 643.4 708.8 2.167 0.02109 637.7 701.0 2.126

150 0.02621 665.3 733.4 2.226 0.02206 660.1 726.3 2.186
160 0.02723 687.4 758.2 2.283 0.02300 682.6 751.6 2.245
170 0.02821 709.9 783.2 2.340 0.02390 705.4 777.1 2.303
180 0.02918 732.5 808.4 2.397 0.02478 728.3 802.6 2.360
190 0.03012 755.5 833.8 2.452 0.02563 751.5 828.4 2.417
p 35.0 bar 3.5 MPa p 40.0 bar 4.0 MPa

(Tsat 86.01C) (Tsat 93.38C)
Sat. 0.00977 486.3 520.5 1.633 0.00715 474.7 503.3 1.574
90 0.01086 502.4 540.5 1.688
100 0.01270 532.9 577.3 1.788 0.00940 512.1 549.7 1.700
110 0.01408 558.9 608.2 1.870 0.01110 544.7 589.1 1.804
120 0.01526 583.4 636.8 1.944 0.01237 572.1 621.6 1.887
130 0.01631 607.0 664.1 2.012 0.01344 597.4 651.2 1.962
140 0.01728 630.2 690.7 2.077 0.01439 621.9 679.5 2.031
150 0.01819 653.3 717.0 2.140 0.01527 645.9 707.0 2.097
160 0.01906 676.4 743.1 2.201 0.01609 669.7 734.1 2.160
170 0.01989 699.6 769.2 2.261 0.01687 693.4 760.9 2.222
180 0.02068 722.9 795.3 2.319 0.01761 717.3 787.7 2.281
190 0.02146 746.5 821.6 2.376 0.01833 741.2 814.5 2.340
200 0.02221 770.3 848.0 2.433 0.01902 765.3 841.4 2.397
TABLE A-19 Properties of Selected Solids and Liquids: cp, , and
Specific Density, Thermal

Heat, cp Conductivity,
Substance (kJ/kg # K) (kg/m3) (W/m # K)

Selected Solids, 300K
Aluminium 0.903 2700 237
Coal, anthracite 1.260 1350 0.26
Copper 0.385 8930 401
Granite 0.775 2630 2.79
Iron 0.447 7870 80.2
Lead 0.129 11300 35.3
Sand 0.800 1520 0.27
Silver 0.235 10500 429
Soil 1.840 2050 0.52
Steel (AISI 302) 0.480 8060 15.1
Tin 0.227 7310 66.6
Building Materials, 300K
Brick, common 0.835 1920 0.72
Concrete (stone mix) 0.880 2300 1.4
Glass, plate 0.750 2500 1.4
Hardboard, siding 1.170 640 0.094
Limestone 0.810 2320 2.15
Plywood 1.220 545 0.12
Softwoods (fir, pine) 1.380 510 0.12
Insulating Materials, 300K
Blanket (glass fiber) 16 0.046
Cork 1.800 120 0.039
Duct liner (glass fiber, coated) 0.835 32 0.038
Polystyrene (extruded) 1.210 55 0.027
Vermiculite fill (flakes) 0.835 80 0.068
Saturated Liquids
Ammonia, 300K 4.818 599.8 0.465
Mercury, 300K 0.139 13529 8.540
Refrigerant 22, 300K 1.267 1183.1 0.085
Refrigerant 134a, 300K 1.434 1199.7 0.081
Table A-19
Unused Engine Oil, 300K 1.909 884.1 0.145
Water, 275K 4.211 999.9 0.574
300K 4.179 996.5 0.613
325K 4.182 987.1 0.645
350K 4.195 973.5 0.668
375K 4.220 956.8 0.681
400K 4.256 937.4 0.688
Source: Drawn from several sources, these data are only representative. Values can vary depending on
temperature, purity, moisture content, and other factors.
TABLE A-20 Ideal Gas Specific Heats of Some Common Gases (kJ/kg # K)
cp cv k cp cv k cp cv k
Temp. Temp.
K Air Nitrogen, N2 Oxygen, O2 K
250 1.003 0.716 1.401 1.039 0.742 1.400 0.913 0.653 1.398 250
300 1.005 0.718 1.400 1.039 0.743 1.400 0.918 0.658 1.395 300
350 1.008 0.721 1.398 1.041 0.744 1.399 0.928 0.668 1.389 350
400 1.013 0.726 1.395 1.044 0.747 1.397 0.941 0.681 1.382 400
450 1.020 0.733 1.391 1.049 0.752 1.395 0.956 0.696 1.373 450
500 1.029 0.742 1.387 1.056 0.759 1.391 0.972 0.712 1.365 500
550 1.040 0.753 1.381 1.065 0.768 1.387 0.988 0.728 1.358 550
600 1.051 0.764 1.376 1.075 0.778 1.382 1.003 0.743 1.350 600
650 1.063 0.776 1.370 1.086 0.789 1.376 1.017 0.758 1.343 650
700 1.075 0.788 1.364 1.098 0.801 1.371 1.031 0.771 1.337 700
750 1.087 0.800 1.359 1.110 0.813 1.365 1.043 0.783 1.332 750
800 1.099 0.812 1.354 1.121 0.825 1.360 1.054 0.794 1.327 800
900 1.121 0.834 1.344 1.145 0.849 1.349 1.074 0.814 1.319 900
1000 1.142 0.855 1.336 1.167 0.870 1.341 1.090 0.830 1.313 1000
Temp. Carbon Carbon Temp.
K Dioxide, CO2 Monoxide, CO Hydrogen, H2 K
250 0.791 0.602 1.314 1.039 0.743 1.400 14.051 9.927 1.416 250
300 0.846 0.657 1.288 1.040 0.744 1.399 14.307 10.183 1.405 300
350 0.895 0.706 1.268 1.043 0.746 1.398 14.427 10.302 1.400 350
400 0.939 0.750 1.252 1.047 0.751 1.395 14.476 10.352 1.398 400
450 0.978 0.790 1.239 1.054 0.757 1.392 14.501 10.377 1.398 450
500 1.014 0.825 1.229 1.063 0.767 1.387 14.513 10.389 1.397 500
550 1.046 0.857 1.220 1.075 0.778 1.382 14.530 10.405 1.396 550
600 1.075 0.886 1.213 1.087 0.790 1.376 14.546 10.422 1.396 600
650 1.102 0.913 1.207 1.100 0.803 1.370 14.571 10.447 1.395 650
700 1.126 0.937 1.202 1.113 0.816 1.364 14.604 10.480 1.394 700
750 1.148 0.959 1.197 1.126 0.829 1.358 14.645 10.521 1.392 750
800 1.169 0.980 1.193 1.139 0.842 1.353 14.695 10.570 1.390 800
900 1.204 1.015 1.186 1.163 0.866 1.343 14.822 10.698 1.385 900
1000 1.234 1.045 1.181 1.185 0.888 1.335 14.983 10.859 1.380 1000
Source: Adapted from K. Wark, Thermodynamics, 4th ed., McGraw-Hill, New York, 1983, as based on Tables
of Thermal Properties of Gases, NBS Circular 564, 1955.
Table A-20
TABLE A-21 Variation of cp with Temperature for Selected Ideal Gases

cp
a
bT
gT 2
dT 3
eT 4
R
T is in K, equations valid from 300 to 1000 K
Gas 103 106 109 1012
CO 3.710 1.619 3.692 2.032 0.240
CO2 2.401 8.735 6.607 2.002 0
H2 3.057 2.677 5.810 5.521 1.812
H2O 4.070 1.108 4.152 2.964 0.807
O2 3.626 1.878 7.055 6.764 2.156
N2 3.675 1.208 2.324 0.632 0.226
Air 3.653 1.337 3.294 1.913 0.2763
SO2 3.267 5.324 0.684 5.281 2.559
CH4 3.826 3.979 24.558 22.733 6.963
C2H2 1.410 19.057 24.501 16.391 4.135
C2H4 1.426 11.383 7.989 16.254 6.749
Monatomic
gasesa 2.5 0 0 0 0
a
For monatomic gases, such as He, Ne, and Ar, cp is constant over a wide temperature range and is very nearly
equal to 52 R.
Source: Adapted from K. Wark, Thermodynamics, 4th ed., McGraw-Hill, New York, 1983, as based on NASA
SP-273, U.S. Government Printing Office, Washington, DC, 1971.
Table A-21
Table A-22
TABLE A-22 Ideal Gas Properties of Air

T(K), h and u(kJ/kg), s (kJ/kg # K)
when s 01 when s 0
T h u s pr vr T h u s pr vr
200 199.97 142.56 1.29559 0.3363 1707. 450 451.80 322.62 2.11161 5.775 223.6
210 209.97 149.69 1.34444 0.3987 1512. 460 462.02 329.97 2.13407 6.245 211.4
220 219.97 156.82 1.39105 0.4690 1346. 470 472.24 337.32 2.15604 6.742 200.1
230 230.02 164.00 1.43557 0.5477 1205. 480 482.49 344.70 2.17760 7.268 189.5
240 240.02 171.13 1.47824 0.6355 1084. 490 492.74 352.08 2.19876 7.824 179.7
250 250.05 178.28 1.51917 0.7329 979. 500 503.02 359.49 2.21952 8.411 170.6
260 260.09 185.45 1.55848 0.8405 887.8 510 513.32 366.92 2.23993 9.031 162.1
270 270.11 192.60 1.59634 0.9590 808.0 520 523.63 374.36 2.25997 9.684 154.1
280 280.13 199.75 1.63279 1.0889 738.0 530 533.98 381.84 2.27967 10.37 146.7
285 285.14 203.33 1.65055 1.1584 706.1 540 544.35 389.34 2.29906 11.10 139.7
290 290.16 206.91 1.66802 1.2311 676.1 550 554.74 396.86 2.31809 11.86 133.1
295 295.17 210.49 1.68515 1.3068 647.9 560 565.17 404.42 2.33685 12.66 127.0
300 300.19 214.07 1.70203 1.3860 621.2 570 575.59 411.97 2.35531 13.50 121.2
305 305.22 217.67 1.71865 1.4686 596.0 580 586.04 419.55 2.37348 14.38 115.7
310 310.24 221.25 1.73498 1.5546 572.3 590 596.52 427.15 2.39140 15.31 110.6
315 315.27 224.85 1.75106 1.6442 549.8 600 607.02 434.78 2.40902 16.28 105.8
320 320.29 228.42 1.76690 1.7375 528.6 610 617.53 442.42 2.42644 17.30 101.2
325 325.31 232.02 1.78249 1.8345 508.4 620 628.07 450.09 2.44356 18.36 96.92
330 330.34 235.61 1.79783 1.9352 489.4 630 638.63 457.78 2.46048 19.84 92.84
340 340.42 242.82 1.82790 2.149 454.1 640 649.22 465.50 2.47716 20.64 88.99
350 350.49 250.02 1.85708 2.379 422.2 650 659.84 473.25 2.49364 21.86 85.34
360 360.58 257.24 1.88543 2.626 393.4 660 670.47 481.01 2.50985 23.13 81.89
370 370.67 264.46 1.91313 2.892 367.2 670 681.14 488.81 2.52589 24.46 78.61
380 380.77 271.69 1.94001 3.176 343.4 680 691.82 496.62 2.54175 25.85 75.50
390 390.88 278.93 1.96633 3.481 321.5 690 702.52 504.45 2.55731 27.29 72.56
400 400.98 286.16 1.99194 3.806 301.6 700 713.27 512.33 2.57277 28.80 69.76
410 411.12 293.43 2.01699 4.153 283.3 710 724.04 520.23 2.58810 30.38 67.07
420 421.26 300.69 2.04142 4.522 266.6 720 734.82 528.14 2.60319 32.02 64.53
430 431.43 307.99 2.06533 4.915 251.1 730 745.62 536.07 2.61803 33.72 62.13
440 441.61 315.30 2.08870 5.332 236.8 740 756.44 544.02 2.63280 35.50 59.82
1. pr and vr data for use with Eqs. 6.43 and 6.44, respectively.
Table A-22
T(K), h and u(kJ/kg), s (kJ/kg # K)
when s 01 when s 0
750 767.29 551.99 2.64737 37.35 57.63 1300 1395.97 1022.82 3.27345 330.9 11.275
760 778.18 560.01 2.66176 39.27 55.54 1320 1419.76 1040.88 3.29160 352.5 10.747
770 789.11 568.07 2.67595 41.31 53.39 1340 1443.60 1058.94 3.30959 375.3 10.247
780 800.03 576.12 2.69013 43.35 51.64 1360 1467.49 1077.10 3.32724 399.1 9.780
790 810.99 584.21 2.70400 45.55 49.86 1380 1491.44 1095.26 3.34474 424.2 9.337
800 821.95 592.30 2.71787 47.75 48.08 1400 1515.42 1113.52 3.36200 450.5 8.919
820 843.98 608.59 2.74504 52.59 44.84 1420 1539.44 1131.77 3.37901 478.0 8.526
840 866.08 624.95 2.77170 57.60 41.85 1440 1563.51 1150.13 3.39586 506.9 8.153
860 888.27 641.40 2.79783 63.09 39.12 1460 1587.63 1168.49 3.41247 537.1 7.801
880 910.56 657.95 2.82344 68.98 36.61 1480 1611.79 1186.95 3.42892 568.8 7.468
900 932.93 674.58 2.84856 75.29 34.31 1500 1635.97 1205.41 3.44516 601.9 7.152
920 955.38 691.28 2.87324 82.05 32.18 1520 1660.23 1223.87 3.46120 636.5 6.854
940 977.92 708.08 2.89748 89.28 30.22 1540 1684.51 1242.43 3.47712 672.8 6.569
960 1000.55 725.02 2.92128 97.00 28.40 1560 1708.82 1260.99 3.49276 710.5 6.301
980 1023.25 741.98 2.94468 105.2 26.73 1580 1733.17 1279.65 3.50829 750.0 6.046
1000 1046.04 758.94 2.96770 114.0 25.17 1600 1757.57 1298.30 3.52364 791.2 5.804
1020 1068.89 776.10 2.99034 123.4 23.72 1620 1782.00 1316.96 3.53879 834.1 5.574
1040 1091.85 793.36 3.01260 133.3 22.39 1640 1806.46 1335.72 3.55381 878.9 5.355
1060 1114.86 810.62 3.03449 143.9 21.14 1660 1830.96 1354.48 3.56867 925.6 5.147
1080 1137.89 827.88 3.05608 155.2 19.98 1680 1855.50 1373.24 3.58335 974.2 4.949
1100 1161.07 845.33 3.07732 167.1 18.896 1700 1880.1 1392.7 3.5979 1025 4.761
1120 1184.28 862.79 3.09825 179.7 17.886 1750 1941.6 1439.8 3.6336 1161 4.328
1140 1207.57 880.35 3.11883 193.1 16.946 1800 2003.3 1487.2 3.6684 1310 3.944
1160 1230.92 897.91 3.13916 207.2 16.064 1850 2065.3 1534.9 3.7023 1475 3.601
1180 1254.34 915.57 3.15916 222.2 15.241 1900 2127.4 1582.6 3.7354 1655 3.295
1200 1277.79 933.33 3.17888 238.0 14.470 1950 2189.7 1630.6 3.7677 1852 3.022
1220 1301.31 951.09 3.19834 254.7 13.747 2000 2252.1 1678.7 3.7994 2068 2.776
1240 1324.93 968.95 3.21751 272.3 13.069 2050 2314.6 1726.8 3.8303 2303 2.555
1260 1348.55 986.90 3.23638 290.8 12.435 2100 2377.4 1775.3 3.8605 2559 2.356
1280 1372.24 1004.76 3.25510 310.4 11.835 2150 2440.3 1823.8 3.8901 2837 2.175
2200 2503.2 1872.4 3.9191 3138 2.012
2250 2566.4 1921.3 3.9474 3464 1.864
Source: Tables A-22 are based on J. H. Keenan and J. Kaye, Gas Tables, Wiley, New York, 1945.
Table A-23
TABLE A-23 Ideal Gas Properties of Selected Gases
758
T(K), h and u(kJ/kmol), s(kJ/kmol # K)
Carbon Dioxide, CO2 Carbon Monoxide, CO Water Vapor, H2O Oxygen, O2 Nitrogen, N2
(hf 393,520 kJ/kmol) (hf 110,530 kJ/kmol) (hf 241,820 kJ/kmol) (hf 0 kJ/kmol) (hf 0 kJ/kmol)
T h u s h u s h u s h u s h u s T
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
220 6,601 4,772 202.966 6,391 4,562 188.683 7,295 5,466 178.576 6,404 4,575 196.171 6,391 4,562 182.638 220
230 6,938 5,026 204.464 6,683 4,771 189.980 7,628 5,715 180.054 6,694 4,782 197.461 6,683 4,770 183.938 230
240 7,280 5,285 205.920 6,975 4,979 191.221 7,961 5,965 181.471 6,984 4,989 198.696 6,975 4,979 185.180 240
250 7,627 5,548 207.337 7,266 5,188 192.411 8,294 6,215 182.831 7,275 5,197 199.885 7,266 5,188 186.370 250
260 7,979 5,817 208.717 7,558 5,396 193.554 8,627 6,466 184.139 7,566 5,405 201.027 7,558 5,396 187.514 260
270 8,335 6,091 210.062 7,849 5,604 194.654 8,961 6,716 185.399 7,858 5,613 202.128 7,849 5,604 188.614 270
280 8,697 6,369 211.376 8,140 5,812 195.173 9,296 6,968 186.616 8,150 5,822 203.191 8,141 5,813 189.673 280
290 9,063 6,651 212.660 8,432 6,020 196.735 9,631 7,219 187.791 8,443 6,032 204.218 8,432 6,021 190.695 290
298 9,364 6,885 213.685 8,669 6,190 197.543 9,904 7,425 188.720 8,682 6,203 205.033 8,669 6,190 191.502 298
300 9,431 6,939 213.915 8,723 6,229 197.723 9,966 7,472 188.928 8,736 6,242 205.213 8,723 6,229 191.682 300
310 9,807 7,230 215.146 9,014 6,437 198.678 10,302 7,725 190.030 9,030 6,453 206.177 9,014 6,437 192.638 310
320 10,186 7,526 216.351 9,306 6,645 199.603 10,639 7,978 191.098 9,325 6,664 207.112 9,306 6,645 193.562 320
330 10,570 7,826 217.534 9,597 6,854 200.500 10,976 8,232 192.136 9,620 6,877 208.020 9,597 6,853 194.459 330
340 10,959 8,131 218.694 9,889 7,062 201.371 11,314 8,487 193.144 9,916 7,090 208.904 9,888 7,061 195.328 340
350 11,351 8,439 219.831 10,181 7,271 202.217 11,652 8,742 194.125 10,213 7,303 209.765 10,180 7,270 196.173 350
360 11,748 8,752 220.948 10,473 7,480 203.040 11,992 8,998 195.081 10,511 7,518 210.604 10,471 7,478 196.995 360
370 12,148 9,068 222.044 10,765 7,689 203.842 12,331 9,255 196.012 10,809 7,733 211.423 10,763 7,687 197.794 370
380 12,552 9,392 223.122 11,058 7,899 204.622 12,672 9,513 196.920 11,109 7,949 212.222 11,055 7,895 198.572 380
390 12,960 9,718 224.182 11,351 8,108 205.383 13,014 9,771 197.807 11,409 8,166 213.002 11,347 8,104 199.331 390
400 13,372 10,046 225.225 11,644 8,319 206.125 13,356 10,030 198.673 11,711 8,384 213.765 11,640 8,314 200.071 400
410 13,787 10,378 226.250 11,938 8,529 206.850 13,699 10,290 199.521 12,012 8,603 214.510 11,932 8,523 200,794 410
420 14,206 10,714 227.258 12,232 8,740 207.549 14,043 10,551 200.350 12,314 8,822 215.241 12,225 8,733 201.499 420
430 14,628 11,053 228.252 12,526 8,951 208.252 14,388 10,813 201.160 12,618 9,043 215.955 12,518 8,943 202.189 430
440 15,054 11,393 229.230 12,821 9,163 208.929 14,734 11,075 201.955 12,923 9,264 216.656 12,811 9,153 202.863 440
450 15,483 11,742 230.194 13,116 9,375 209.593 15,080 11,339 202.734 13,228 9,487 217.342 13,105 9,363 203.523 450
460 15,916 12,091 231.144 13,412 9,587 210.243 15,428 11,603 203.497 13,535 9,710 218.016 13,399 9,574 204.170 460
470 16,351 12,444 232.080 13,708 9,800 210.880 15,777 11,869 204.247 13,842 9,935 218.676 13,693 9,786 204.803 470
480 16,791 12,800 233.004 14,005 10,014 211.504 16,126 12,135 204.982 14,151 10,160 219.326 13,988 9,997 205.424 480
490 17,232 13,158 233.916 14,302 10,228 212.117 16,477 12,403 205.705 14,460 10,386 219.963 14,285 10,210 206.033 490
500 17,678 13,521 234.814 14,600 10,443 212.719 16,828 12,671 206.413 14,770 10,614 220.589 14,581 10,423 206.630 500
510 18,126 13,885 235.700 14,898 10,658 213.310 17,181 12,940 207.112 15,082 10,842 221.206 14,876 10,635 207.216 510
520 18,576 14,253 236.575 15,197 10,874 213.890 17,534 13,211 207.799 15,395 11,071 221.812 15,172 10,848 207.792 520
530 19,029 14,622 237.439 15,497 11,090 214.460 17,889 13,482 208.475 15,708 11,301 222.409 15,469 11,062 208.358 530
540 19,485 14,996 238.292 15,797 11,307 215.020 18,245 13,755 209.139 16,022 11,533 222.997 15,766 11,277 208.914 540
550 19,945 15,372 239.135 16,097 11,524 215.572 18,601 14,028 209.795 16,338 11,765 223.576 16,064 11,492 209.461 550
560 20,407 15,751 239.962 16,399 11,743 216.115 18,959 14,303 210.440 16,654 11,998 224.146 16,363 11,707 209.999 560
570 20,870 16,131 240.789 16,701 11,961 216.649 19,318 14,579 211.075 16,971 12,232 224.708 16,662 11,923 210.528 570
580 21,337 16,515 241.602 17,003 12,181 217.175 19.678 14,856 211.702 17,290 12,467 225.262 16,962 12,139 211.049 580
590 21,807 16,902 242.405 17,307 12,401 217.693 20,039 15,134 212.320 17,609 12,703 225.808 17,262 12,356 211.562 590
600 22,280 17,291 243.199 17,611 12,622 218.204 20,402 15,413 212.920 17,929 12,940 226.346 17,563 12,574 212.066 600
610 22,754 17,683 243.983 17,915 12,843 218.708 20,765 15,693 213.529 18,250 13,178 226.877 17,864 12,792 212.564 610
620 23,231 18,076 244.758 18,221 13,066 219.205 21,130 15,975 214.122 18,572 13,417 227.400 18,166 13,011 213.055 620
630 23,709 18,471 245.524 18,527 13,289 219.695 21,495 16,257 214.707 18,895 13,657 227.918 18,468 13,230 213.541 630
640 24,190 18,869 246.282 18,833 13,512 220.179 21,862 16,541 215.285 19,219 13,898 228.429 18,772 13,450 214.018 640
650 24,674 19,270 247.032 19,141 13,736 220.656 22,230 16,826 215.856 19,544 14,140 228.932 19,075 13,671 214.489 650
660 25,160 19,672 247,773 19,449 13,962 221.127 22,600 17,112 216.419 19,870 14,383 229.430 19,380 13,892 214.954 660
670 25,648 20,078 248.507 19,758 14,187 221.592 22,970 17,399 216.976 20,197 14,626 229.920 19,685 14,114 215.413 670
680 26,138 20,484 249.233 20,068 14,414 222.052 23,342 17,688 217.527 20,524 14,871 230.405 19,991 14,337 215.866 680
690 26,631 20,894 249.952 20,378 14,641 222.505 23,714 17,978 218.071 20,854 15,116 230.885 20,297 14,560 216.314 690
700 27,125 21,305 250.663 20,690 14,870 222.953 24,088 18,268 218.610 21,184 15,364 231.358 20,604 14,784 216.756 700
710 27,622 21,719 251.368 21,002 15,099 223.396 24,464 18,561 219.142 21,514 15,611 231.827 20,912 15,008 217.192 710
720 28,121 22,134 252.065 21,315 15,328 223.833 24,840 18,854 219.668 21,845 15,859 232.291 21,220 15,234 217.624 720
730 28,622 22,552 252.755 21,628 15,558 224.265 25,218 19,148 220.189 22,177 16,107 232.748 21,529 15,460 218.059 730
740 29,124 22,972 253.439 21,943 15,789 224.692 25,597 19,444 220.707 22,510 16,357 233.201 21,839 15,686 218.472 740
750 29,629 23,393 254.117 22,258 16,022 225.115 25,977 19,741 221.215 22,844 16,607 233.649 22,149 15,913 218.889 750
760 30,135 23,817 254.787 22,573 16,255 225.533 26,358 20,039 221.720 23,178 16,859 234.091 22,460 16,141 219.301 760
770 30,644 24,242 255,452 22,890 16,488 225.947 26,741 20,339 222.221 23,513 17,111 234.528 22,772 16,370 219.709 770
780 31,154 24,669 256.110 23,208 16,723 226.357 27,125 20,639 222.717 23,850 17,364 234.960 23,085 16,599 220.113 780
790 31,665 25,097 256.762 23,526 16,957 226.762 27,510 20,941 223.207 24,186 17,618 235.387 23,398 16,830 220.512 790
800 32,179 25,527 257.408 23,844 17,193 227.162 27,896 21,245 223.693 24,523 17,872 235.810 23,714 17,061 220.907 800
810 32,694 25,959 258.048 24,164 17,429 227.559 28,284 21,549 224.174 24,861 18,126 236.230 24,027 17,292 221.298 810
820 33,212 26,394 258.682 24,483 17,665 227.952 28,672 21,855 224.651 25,199 18,382 236.644 24,342 17,524 221.684 820
830 33,730 26,829 259.311 24,803 17,902 228.339 29,062 22,162 225.123 25,537 18,637 237.055 24,658 17,757 222.067 830
840 34,251 27,267 259.934 25,124 18,140 228.724 29,454 22,470 225.592 25,877 18,893 237.462 24,974 17,990 222.447 840
850 34,773 27,706 260.551 25,446 18,379 229,106 29,846 22,779 226.057 26,218 19,150 237.864 25,292 18,224 222.822 850
860 35,296 28,125 261.164 25,768 18,617 229,482 30,240 23,090 226.517 26,559 19,408 238.264 25,610 18,459 223.194 860
870 35,821 28,588 261.770 26.091 18,858 229.856 30,635 23,402 226.973 26,899 19,666 238.660 25,928 18,695 223.562 870
880 36,347 29,031 262.371 26,415 19,099 230.227 31,032 23,715 227.426 27,242 19,925 239.051 26,248 18,931 223.927 880
890 36,876 29,476 262.968 26,740 19,341 230.593 31,429 24,029 227.875 27,584 20,185 239.439 26,568 19,168 224.288 890
900 37,405 29,922 263.559 27,066 19,583 230.957 31,828 24,345 228.321 27,928 20,445 239.823 26,890 19,407 224.647 900
910 37,935 30,369 264.146 27,392 19,826 231.317 32,228 24,662 228.763 28,272 20,706 240.203 27,210 19,644 225.002 910
920 38,467 30,818 264.728 27,719 20,070 231.674 32,629 24,980 229.202 28,616 20,967 240.580 27,532 19,883 225.353 920
930 39,000 31,268 265.304 28,046 20,314 232.028 33,032 25,300 229.637 28,960 21,228 240.953 27,854 20,122 225.701 930
940 39,535 31,719 265.877 28,375 20,559 232.379 33,436 25,621 230.070 29,306 21,491 241.323 28,178 20,362 226.047 940
950 40,070 32,171 266.444 28,703 20,805 232.727 33,841 25,943 230.499 29,652 21,754 241.689 28,501 20,603 226.389 950
960 40,607 32,625 267.007 29,033 21,051 233.072 34,247 26,265 230.924 29,999 22,017 242.052 28,826 20,844 226.728 960
970 41,145 33,081 267.566 29,362 21,298 233.413 34,653 26,588 231.347 30,345 22,280 242.411 29,151 21,086 227.064 970
980 41,685 33,537 268.119 29,693 21,545 233.752 35,061 26,913 231.767 30,692 22,544 242.768 29,476 21,328 227.398 980
990 42,226 33,995 268.670 30,024 21,793 234.088 35,472 27,240 232.184 31.041 22,809 243.120 29,803 21,571 227.728 990
759
Table A-23
Table A-23
760
1000 42,769 34,455 269.215 30,355 22,041 234.421 35,882 27,568 232.597 31,389 23,075 243.471 30,129 21,815 228.057 1000
1020 43,859 35,378 270.293 31,020 22,540 235.079 36,709 28,228 233.415 32,088 23,607 244.164 30,784 22,304 228.706 1020
1040 44,953 36,306 271.354 31,688 23,041 235.728 37,542 28,895 234.223 32,789 24,142 244.844 31,442 22,795 229.344 1040
1060 46,051 37,238 272.400 32,357 23,544 236.364 38,380 29,567 235.020 33,490 24,677 245.513 32,101 23,288 229.973 1060
1080 47,153 38,174 273.430 33,029 24,049 236.992 39,223 30,243 235.806 34,194 25,214 246.171 32,762 23,782 230.591 1080
1100 48,258 39,112 274.445 33,702 24,557 237.609 40,071 30,925 236.584 34,899 25,753 246.818 33,426 24,280 231.199 1100
1120 49,369 40,057 275.444 34,377 25,065 238.217 40,923 31,611 237.352 35,606 26,294 247.454 34,092 24,780 231.799 1120
1140 50,484 41,006 276.430 35,054 25,575 238.817 41,780 32,301 238.110 36,314 26,836 248.081 34,760 25,282 232.391 1140
1160 51,602 41,957 277.403 35,733 26,088 239.407 42,642 32,997 238.859 37,023 27,379 248.698 35,430 25,786 232.973 1160
1180 52,724 42,913 278.362 36,406 26,602 239.989 43,509 33,698 239.600 37,734 27,923 249.307 36,104 26,291 233.549 1180
1200 53,848 43,871 279.307 37,095 27,118 240.663 44,380 34,403 240.333 38,447 28,469 249.906 36,777 26,799 234.115 1200
1220 54,977 44,834 280.238 37,780 27,637 241.128 45,256 35,112 241.057 39,162 29,018 250.497 37,452 27,308 234.673 1220
1240 56,108 45,799 281.158 38,466 28,426 241.686 46,137 35,827 241.773 39,877 29,568 251.079 38,129 27,819 235.223 1240
1260 57,244 46,768 282.066 39,154 28,678 242.236 47,022 36,546 242.482 40,594 30,118 251.653 38,807 28,331 235.766 1260
1280 58,381 47,739 282.962 39,884 29,201 242.780 47,912 37,270 243.183 41,312 30,670 252.219 39,488 28,845 236.302 1280
1300 59,522 48,713 283.847 40,534 29,725 243.316 48,807 38,000 243.877 42,033 31,224 252.776 40,170 29,361 236.831 1300
1320 60,666 49,691 284.722 41,266 30,251 243.844 49,707 38,732 244.564 42,753 31,778 253.325 40,853 29,878 237.353 1320
1340 61,813 50,672 285.586 41,919 30,778 244.366 50,612 39,470 245.243 43,475 32,334 253.868 41,539 30,398 237.867 1340
1360 62,963 51,656 286.439 42,613 31,306 244.880 51,521 40,213 245.915 44,198 32,891 254.404 42,227 30,919 238.376 1360
1380 64,116 52,643 287.283 43,309 31,836 245.388 52,434 40,960 246.582 44,923 33,449 254.932 42,915 31,441 238.878 1380
1400 65,271 53,631 288.106 44,007 32,367 245.889 53,351 41,711 247.241 45,648 34,008 255.454 43,605 31,964 239.375 1400
1420 66,427 54,621 288.934 44,707 32,900 246.385 54,273 42,466 247.895 46,374 34,567 255.968 44,295 32,489 239.865 1420
1440 67,586 55,614 289.743 45,408 33,434 246.876 55,198 43,226 248.543 47,102 35,129 256.475 44,988 33,014 240.350 1440
1460 68,748 56,609 290.542 46,110 33,971 247.360 56,128 43,989 249.185 47,831 35,692 256.978 45,682 33,543 240.827 1460
1480 69,911 57,606 291.333 46,813 34,508 247.839 57,062 44,756 249.820 48,561 36,256 257.474 46,377 34,071 241.301 1480
1500 71,078 58,606 292.114 47,517 35,046 248.312 57,999 45,528 250.450 49,292 36,821 257.965 47,073 34,601 241.768 1500
1520 72,246 59,609 292.888 48,222 35,584 248.778 58,942 46,304 251.074 50,024 37,387 258.450 47,771 35,133 242.228 1520
1540 73,417 60,613 292.654 48,928 36,124 249.240 59,888 47,084 251.693 50,756 37,952 258.928 48,470 35,665 242.685 1540
1560 74,590 61,620 294.411 49,635 36,665 249.695 60,838 47,868 252.305 51,490 38,520 259.402 49,168 36,197 243.137 1560
1580 76,767 62,630 295.161 50,344 37,207 250.147 61,792 48,655 252.912 52,224 39,088 259.870 49,869 36,732 243.585 1580
1600 76,944 63,741 295.901 51,053 37,750 250.592 62,748 49,445 253.513 52,961 39,658 260.333 50,571 37,268 244.028 1600
1620 78,123 64,653 296.632 51,763 38,293 251.033 63,709 52,240 254.111 53,696 40,227 260.791 51,275 37,806 244.464 1620
1640 79,303 65,668 297.356 52,472 38,837 251.470 64,675 51,039 254.703 54,434 40,799 261.242 51,980 38,344 244.896 1640
1660 80,486 66,592 298.072 53,184 39,382 251.901 65,643 51,841 255.290 55,172 41,370 261.690 52,686 38,884 245.324 1660
1680 81,670 67,702 298.781 53,895 39,927 252.329 66,614 52,646 255.873 55,912 41,944 262.132 53,393 39,424 245.747 1680
1700 82,856 68,721 299.482 54,609 40,474 252.751 67,589 53,455 256.450 56,652 42,517 262.571 54,099 39,965 246.166 1700
1720 84,043 69,742 300.177 55,323 41,023 253.169 68,567 54,267 257.022 57,394 43,093 263.005 54,807 40,507 246.580 1720
1740 85,231 70,764 300.863 56,039 41,572 253.582 69,550 55,083 257.589 58,136 43,669 263.435 55,516 41,049 246.990 1740
1760 86,420 71,787 301.543 56,756 42,123 253.991 70,535 55,902 258.151 58,800 44,247 263.861 56,227 41,594 247.396 1760
1780 87,612 72,812 302.271 57,473 42,673 254.398 71,523 56,723 258.708 59,624 44,825 264.283 56,938 42,139 247.798 1780
1800 88,806 73,840 302.884 58,191 43,225 254.797 72,513 57,547 259.262 60,371 45,405 264.701 57,651 42,685 248.195 1800
1820 90,000 74,868 303.544 58,910 43,778 255.194 73,507 58,375 259.811 61,118 45,986 265.113 58,363 43,231 248.589 1820
1840 91,196 75,897 304.198 59,629 44,331 255.587 74,506 59,207 260.357 61,866 46,568 265.521 59,075 43,777 248.979 1840
1860 92,394 76,929 304.845 60,351 44,886 255.976 75,506 60,042 260.898 62,616 47,151 265.925 59,790 44,324 249.365 1860
1880 93,593 77,962 305.487 61,072 45,441 256.361 76,511 60,880 261.436 63,365 47,734 266.326 60,504 44,873 249.748 1880
1900 94,793 78,996 306.122 61,794 45,997 256.743 77,517 61,720 261.969 64,116 48,319 266.722 61,220 45,423 250.128 1900
1920 95,995 80,031 306.751 62,516 46,552 257.122 78,527 62,564 262.497 64,868 48,904 267.115 61,936 45,973 250.502 1920
1940 97,197 81,067 307.374 63,238 47,108 257.497 79,540 63,411 263.022 65,620 49,490 267.505 62,654 46,524 250.874 1940
1960 98,401 82,105 307.992 63,961 47,665 257.868 80,555 64,259 263.542 66,374 50,078 267.891 63,381 47,075 251.242 1960
1980 99,606 83,144 308.604 64,684 48,221 258.236 81,573 65,111 264.059 67,127 50,665 268.275 64,090 47,627 251.607 1980
2000 100,804 84,185 309.210 65,408 48,780 258.600 82,593 65,965 264.571 67,881 51,253 268.655 64,810 48,181 251.969 2000
2050 103,835 86,791 310.701 67,224 50,179 259.494 85,156 68,111 265.838 69,772 52,727 269.588 66,612 49,567 252.858 2050
2100 106,864 89,404 312.160 69,044 51,584 260.370 87,735 70,275 267.081 71,668 54,208 270.504 68,417 50,957 253.726 2100
2150 109,898 92,023 313.589 70,864 52,988 261.226 90,330 72,454 268.301 73,573 55,697 271.399 70,226 52,351 254.578 2150
2200 112,939 94,648 314.988 72,688 54,396 262.065 92,940 74,649 269.500 75,484 57,192 272.278 72,040 53,749 255.412 2200
2250 115,984 97,277 316.356 74,516 55,809 262.887 95,562 76,855 270.679 77,397 58,690 273.136 73,856 55,149 256.227 2250
2300 119,035 99,912 317.695 76,345 57,222 263.692 98,199 79,076 271.839 79,316 60,193 273.981 75,676 56,553 257.027 2300
2350 122,091 102,552 319.011 78,178 58,640 264.480 100,846 81,308 272.978 81,243 61,704 274.809 77,496 57,958 257.810 2350
2400 125,152 105,197 320.302 80,015 60,060 265.253 103,508 83,553 274.098 83,174 63,219 275.625 79,320 59,366 258.580 2400
2450 128,219 107,849 321.566 81,852 61,482 266.012 106,183 85,811 275.201 85,112 64,742 276.424 81,149 60,779 259.332 2450
2500 131,290 110,504 322.808 83,692 62,906 266.755 108,868 88,082 276.286 87,057 66,271 277.207 82,981 62,195 260.073 2500
2550 134,368 113,166 324.026 85,537 64,335 267.485 111,565 90,364 277.354 89,004 67,802 277.979 84,814 63,613 260.799 2550
2600 137,449 115,832 325.222 87,383 65,766 268.202 114,273 92,656 278.407 90,956 69,339 278.738 86,650 65,033 261.512 2600
2650 140,533 118,500 326.396 89,230 67,197 268.905 116,991 94,958 279,441 92,916 70,883 279.485 88,488 66,455 262.213 2650
2700 143,620 121,172 327.549 91,077 68,628 269.596 119,717 97,269 280.462 94,881 72,433 280.219 90,328 67,880 262.902 2700
2750 146,713 123,849 328.684 92,930 70,066 270.285 122,453 99,588 281.464 96,852 73,987 280.942 92,171 69,306 263.577 2750
2800 149,808 126,528 329.800 94,784 71,504 270.943 125,198 101,917 282.453 98,826 75,546 281.654 94,014 70,734 264.241 2800
2850 152,908 129,212 330.896 96,639 72,945 271.602 127,952 104,256 283.429 100,808 77,112 282.357 95,859 72,163 264.895 2850
2900 156,009 131,898 331.975 98,495 74,383 272.249 130,717 106,605 284.390 102,793 78,682 283.048 97,705 73,593 265.538 2900
2950 159,117 134,589 333.037 100,352 75,825 272.884 133,486 108,959 285.338 104,785 80,258 283.728 99,556 75,028 266.170 2950
3000 162,226 137,283 334.084 102,210 77,267 273.508 136,264 111,321 286.273 106,780 81,837 284.399 101,407 76,464 266.793 3000
3050 165,341 139,982 335.114 104,073 78,715 274.123 139,051 113,692 287.194 108,778 83,419 285.060 103,260 77,902 267.404 3050
3100 168,456 142,681 336.126 105,939 80,164 274.730 141,846 116,072 288.102 110,784 85,009 285.713 105,115 79,341 268.007 3100
3150 171,576 145,385 337.124 107,802 81,612 275.326 144,648 118,458 288.999 112,795 86,601 286.355 106,972 80,782 268.601 3150
3200 174,695 148,089 338.109 109,667 83,061 275.914 147,457 120,851 289.884 114,809 88,203 286.989 108,830 82,224 269.186 3200
3250 177,822 150,801 339.069 111,534 84,513 276.494 150,272 123,250 290.756 116,827 89,804 287.614 110,690 83,668 269.763 3250
Source: Tables A-23 are based on the JANAF Thermochemical Tables, NSRDS-NBS-37, 1971.
761
Table A-23
TABLE A-24 Constants for the van der Waals, RedlichKwong, and BenedictWebbRubin Equations of State
1. van der Waals and RedlichKwong: Constants for pressure in bar, specific volume in m3/kmol, and temperature in K
van der Waals RedlichKwong
a b a b
m3 2 m3 m3 2 12 m3
Substance bar a b bar a b K
kmol kmol kmol kmol
Air 1.368 0.0367 15.989 0.02541
Butane (C4H10) 13.86 0.1162 289.55 0.08060
Carbon dioxide (CO2) 3.647 0.0428 64.43 0.02963
Carbon monoxide (CO) 1.474 0.0395 17.22 0.02737
Table A-24
Methane (CH4) 2.293 0.0428 32.11 0.02965

Nitrogen (N2) 1.366 0.0386 15.53 0.02677
Oxygen (O2) 1.369 0.0317 17.22 0.02197
Propane (C3H8) 9.349 0.0901 182.23 0.06242
Refrigerant 12 10.49 0.0971 208.59 0.06731
Sulfur dioxide (SO2) 6.883 0.0569 144.80 0.03945
Water (H2O) 5.531 0.0305 142.59 0.02111
Source: Calculated from critical data.
2. BenedictWebbRubin: Constants for pressure in bar, specific volume in m3/kmol, and temperature in K
Substance a A b B c C
C4H10 1.9073 10.218 0.039998 0.12436 3.206 105 1.006 106 1.101 103 0.0340
CO2 0.1386 2.7737 0.007210 0.04991 1.512 104 1.404 105 8.47 105 0.00539
CO 0.0371 1.3590 0.002632 0.05454 1.054 103 8.676 103 1.350 104 0.0060
CH4 0.0501 1.8796 0.003380 0.04260 2.579 103 2.287 104 1.244 104 0.0060
N2 0.0254 1.0676 0.002328 0.04074 7.381 102 8.166 103 1.272 104 0.0053
Source: H. W. Cooper and J. C. Goldfrank, Hydrocarbon Processing, 46 (12): 141 (1967).
TABLE A-25 Thermochemical Properties of Selected Substances at 298K and 1 atm

Heating Values
Enthalpy of Gibbs Function Absolute Higher, Lower,
Molar Mass, Formation, hf of Formation, Entropy, s HHV LHV
Substance Formula M (kg/kmol) (kJ/kmol) gf (kJ/kmol) (kJ/kmol # K) (kJ/kg) (kJ/kg)
Carbon C(s) 12.01 0 0 5.74 32,770 32,770
Hydrogen H2(g) 2.016 0 0 130.57 141,780 119,950
Nitrogen N2(g) 28.01 0 0 191.50
Oxygen O2(g) 32.00 0 0 205.03
Carbon monoxide CO(g) 28.01 110,530 137,150 197.54
Carbon dioxide CO2(g) 44.01 393,520 394,380 213.69
Water H2O(g) 18.02 241,820 228,590 188.72
Water H2O(l) 18.02 285,830 237,180 69.95
Hydrogen peroxide H2O2(g) 34.02 136,310 105,600 232.63
Ammonia NH3(g) 17.03 46,190 16,590 192.33
Oxygen O(g) 16.00 249,170 231,770 160.95
Table A-25
Hydrogen H(g) 1.008 218,000 203,290 114.61
Nitrogen N(g) 14.01 472,680 455,510 153.19
Hydroxyl OH(g) 17.01 39,460 34,280 183.75
Methane CH4(g) 16.04 74,850 50,790 186.16 55,510 50,020
Acetylene C2H2(g) 26.04 226,730 209,170 200.85 49,910 48,220
Ethylene C2H2(g) 28.05 52,280 68,120 219.83 50,300 47,160
Ethane C2H6(g) 30.07 84,680 32,890 229.49 51,870 47,480
Propylene C3H6(g) 42.08 20,410 62,720 266.94 48,920 45,780
Propane C3H8(g) 44.09 103,850 23,490 269.91 50,350 46,360
Butane C4H10(g) 58.12 126,150 15,710 310.03 49,500 45,720
Pentane C5H12(g) 72.15 146,440 8,200 348.40 49,010 45,350
Octane C8H18(g) 114.22 208,450 17,320 463.67 48,260 44,790
Octane C8H18(l) 114.22 249,910 6,610 360.79 47,900 44,430
Benzene C6H6(g) 78.11 82,930 129,660 269.20 42,270 40,580
Methyl alcohol CH3OH(g) 32.04 200,890 162,140 239.70 23,850 21,110
Methyl alcohol CH3OH(l) 32.04 238,810 166,290 126.80 22,670 19,920
Ethyl alcohol C2H5OH(g) 46.07 235,310 168,570 282.59 30,590 27,720
Ethyl alcohol C2H5OH(l) 46.07 277,690 174,890 160.70 29,670 26,800
Source: Based on JANAF Thermochemical Tables, NSRDS-NBS-37, 1971; Selected Values of Chemical Thermodynamic Properties, NBS Tech.
Note 270-3, 1968; and API Research Project 44, Carnegie Press, 1953. Heating values calculated.
TABLE A-26 Standard Molar Chemical Exergy, e ch (kJ/kmol), of

Selected Substances at 298 K and p0
Substance Formula Model Ia Model IIb
Nitrogen N2(g) 640 720
Oxygen O2(g) 3,950 3,970
Carbon dioxide CO2(g) 14,175 19,870
Water H2O(g) 8,635 9,500
Water H2O(l) 45 900
Carbon (graphite) C(s) 404,590 410,260
Hydrogen H2(g) 235,250 236,100
Sulfur S(s) 598,160 609,600
Carbon monoxide CO(g) 269,410 275,100
Sulfur dioxide SO2(g) 301,940 313,400
Nitrogen monoxide NO(g) 88,850 88,900
Nitrogen dioxide NO2(g) 55,565 55,600
Hydrogen sulfide H2S(g) 799,890 812,000
Ammonia NH3(g) 336,685 337,900
Methane CH4(g) 824,350 831,650
Ethane C2H6(g) 1,482,035 1,495,840
Methyl alcohol CH3OH(g) 715,070 722,300
Methyl alcohol CH3OH(l) 710,745 718,000
Ethyl alcohol C2H5OH(g) 1,348,330 1,363,900
Ethyl alcohol C2H5OH(l) 1,342,085 1,357,700
Table A-26
a
J. Ahrendts, Die Exergie Chemisch Reaktionsfhiger Systeme, VDI-
Forschungsheft, VDI-Verlag, Dusseldorf, 579, 1977. Also see Reference
States, EnergyThe International Journal, 5: 667677, 1980. In Model I,
p0 1.019 atm. This model attempts to impose a criterion that the reference
environment be in equilibrium. The reference substances are determined
assuming restricted chemical equilibrium for nitric acid and nitrates and
unrestricted thermodynamic equilibrium for all other chemical components of
the atmosphere, the oceans, and a portion of the Earths crust. The chemical
composition of the gas phase of this model approximates the composition of
the natural atmosphere.
b
J. Szargut, D. R. Morris, and F. R. Steward, Exergy Analysis of Thermal,
Chemical, and Metallurgical Processes, Hemisphere, New York, 1988. In Model
II, p0 1.0 atm. In developing this model a reference substance is selected for
each chemical element from among substances that contain the element being
considered and that are abundantly present in the natural environment, even
though the substances are not in completely mutual stable equilibrium. An
underlying rationale for this approach is that substances found abundantly in
nature have little economic value. On an overall basis, the chemical composition
of the exergy reference environment of Model II is closer than Model I to the
composition of the natural environment, but the equilibrium criterion is not
always satisfied.
TABLE A-27 Logarithms to the Base 10 of the Equilibrium Constant K

log10 K
Temp. 1
2 O2
1
2 N2 H2O wx H2O w
x CO2 w
x CO2
H2 w
x Temp.
K H2 w
x 2H O2 w
x 2O N2 w
x 2N w
x NO H2
21O2 OH
21H2 CO
12O2 CO
H2O R
298 71.224 81.208 159.600 15.171 40.048 46.054 45.066 5.018 537
500 40.316 45.880 92.672 8.783 22.886 26.130 25.025 2.139 900
1000 17.292 19.614 43.056 4.062 10.062 11.280 10.221 0.159 1800
1200 13.414 15.208 34.754 3.275 7.899 8.811 7.764
0.135 2160
1400 10.630 12.054 28.812 2.712 6.347 7.021 6.014
0.333 2520
1600 8.532 9.684 24.350 2.290 5.180 5.677 4.706
0.474 2880
1700 7.666 8.706 22.512 2.116 4.699 5.124 4.169
0.530 3060
1800 6.896 7.836 20.874 1.962 4.270 4.613 3.693
0.577 3240
1900 6.204 7.058 19.410 1.823 3.886 4.190 3.267
0.619 3420
2000 5.580 6.356 18.092 1.699 3.540 3.776 2.884
0.656 3600
2100 5.016 5.720 16.898 1.586 3.227 3.434 2.539
0.688 3780
2200 4.502 5.142 15.810 1.484 2.942 3.091 2.226
0.716 3960
2300 4.032 4.614 14.818 1.391 2.682 2.809 1.940
0.742 4140
2400 3.600 4.130 13.908 1.305 2.443 2.520 1.679
0.764 4320
2500 3.202 3.684 13.070 1.227 2.224 2.270 1.440
0.784 4500
2600 2.836 3.272 12.298 1.154 2.021 2.038 1.219
0.802 4680
2700 2.494 2.892 11.580 1.087 1.833 1.823 1.015
0.818 4860
2800 2.178 2.536 10.914 1.025 1.658 1.624 0.825
0.833 5040
2900 1.882 2.206 10.294 0.967 1.495 1.438 0.649
0.846 5220
3000 1.606 1.898 9.716 0.913 1.343 1.265 0.485
0.858 5400
3100 1.348 1.610 9.174 0.863 1.201 1.103 0.332
0.869 5580
3200 1.106 1.340 8.664 0.815 1.067 0.951 0.189
0.878 5760
3300 0.878 1.086 8.186 0.771 0.942 0.809 0.054
0.888 5940
3400 0.664 0.846 7.736 0.729 0.824 0.674
0.071
0.895 6120
0.462 0.620 7.312 0.690 0.712 0.547
0.190
0.902
Table A-27
3500 6300
Source: Based on data from the JANAF Thermochemical Tables, NSRDS-NBS-37, 1971.
Index to Tables in English Units
TABLE A-1E Atomic or Molecular Weights and Critical Properties of Selected Elements and Compounds 767
TABLE A-2E Properties of Saturated Water (LiquidVapor): Temperature Table 768
TABLE A-3E Properties of Saturated Water (LiquidVapor): Pressure Table 770
TABLE A-4E Properties of Superheated Water Vapor 772
TABLE A-5E Properties of Compressed Liquid Water 778
TABLE A-6E Properties of Saturated Water (SolidVapor): Temperature Table 779
TABLE A-7E Properties of Saturated Refrigerant 22 (LiquidVapor): Temperature Table 780
TABLE A-8E Properties of Saturated Refrigerant 22 (LiquidVapor): Pressure Table 781
TABLE A-9E Properties of Superheated Refrigerant 22 Vapor 782
TABLE A-10E Properties of Saturated Refrigerant 134a (LiquidVapor): Temperature Table 786
TABLE A-11E Properties of Saturated Refrigerant 134a (LiquidVapor): Pressure Table 787
TABLE A-12E Properties of Superheated Refrigerant 134a Vapor 788
TABLE A-13E Properties of Saturated Ammonia (LiquidVapor): Temperature Table 791
TABLE A-14E Properties of Saturated Ammonia (LiquidVapor): Pressure Table 792
TABLE A-15E Properties of Superheated Ammonia Vapor 793
TABLE A-16E Properties of Saturated Propane (LiquidVapor): Temperature Table 797
TABLE A-17E Properties of Saturated Propane (LiquidVapor): Pressure Table 798
TABLE A-18E Properties of Superheated Propane Vapor 799
TABLE A-19E Properties of Selected Solids and Liquids: cp, r, and k 803
TABLE A-20E Ideal Gas Specific Heats of Some Common Gases 804
TABLE A-21E Variation of cp with Temperature for Selected Ideal Gases 805
TABLE A-22E Ideal Gas Properties of Air 806
TABLE A-23E Ideal Gas Properties of Selected Gases 808
TABLE A-24E Constants for the van der Waals, RedlichKwong, and BenedictWebbRubin Equations
of State 812
TABLE A-25E Thermochemical Properties of Selected Substances at 537R and 1 atm. 813
766
Tables in English Units 767
Table A-1E
TABLE A-1E Atomic or Molecular Weights and Critical Properties of Some Selected Elements and
Compounds
Chemical M Tc pc pcvc
Substance Formula (lb/lbmol) (R) (atm) Zc
RTc
Acetylene C2H2 26.04 556 62 0.274
Air (equivalent) 28.97 239 37.2 0.284
Ammonia NH3 17.03 730 111.3 0.242
Argon Ar 39.94 272 47.97 0.290
Benzene C6H6 78.11 1013 48.7 0.274
Butane C4H10 58.12 765 37.5 0.274
Carbon C 12.01
Carbon dioxide CO2 44.01 548 72.9 0.276
Carbon monoxide CO 28.01 239 34.5 0.294
Copper Cu 63.54
Ethane C2H6 30.07 549 48.2 0.285
Ethyl alcohol C2H5OH 46.07 929 63.0 0.249
Ethylene C2H4 28.05 510 50.5 0.270
Helium He 4.003 9.33 2.26 0.300
Hydrogen H2 2.016 59.8 12.8 0.304
Methane CH4 16.04 344 45.8 0.290
Methyl alcohol CH3OH 32.04 924 78.5 0.220
Nitrogen N2 28.01 227 33.5 0.291
Octane C8H18 114.22 1025 24.6 0.258
Oxygen O2 32.00 278 49.8 0.290
Propane C3H8 44.09 666 42.1 0.276
Propylene C3H6 42.08 657 45.6 0.276
Refrigerant 12 CCl2F2 120.92 693 40.6 0.278
Refrigerant 22 CHClF2 86.48 665 49.1 0.267
Refrigerant 134a CF3CH2F 102.03 673 40.2 0.260
Sulfur dioxide SO2 64.06 775 77.7 0.268
Water H2O 18.02 1165 218.0 0.233
Sources: Adapted from International Critical Tables and L. C. Nelson and E. F. Obert, Generalized
Compressibility Charts, Chem. Eng., 617: 203 (1954).
768 Tables in English Units
TABLE A-2E Properties of Saturated Water (LiquidVapor): Temperature Table

ft3/lb Btu/lb Btu/lb Btu/lb # R
F lbf/in.2 vf vg uf ug hf hfg hg sf sg F
H2O
32 0.0886 0.01602 3305 .01 1021.2 .01 1075.4 1075.4 .00003 2.1870 32
35 0.0999 0.01602 2948 2.99 1022.2 3.00 1073.7 1076.7 0.00607 2.1764 35
40 0.1217 0.01602 2445 8.02 1023.9 8.02 1070.9 1078.9 0.01617 2.1592 40
45 0.1475 0.01602 2037 13.04 1025.5 13.04 1068.1 1081.1 0.02618 2.1423 45
50 0.1780 0.01602 1704 18.06 1027.2 18.06 1065.2 1083.3 0.03607 2.1259 50
52 0.1917 0.01603 1589 20.06 1027.8 20.07 1064.1 1084.2 0.04000 2.1195 52
54 0.2064 0.01603 1482 22.07 1028.5 22.07 1063.0 1085.1 0.04391 2.1131 54
56 0.2219 0.01603 1383 24.08 1029.1 24.08 1061.9 1085.9 0.04781 2.1068 56
58 0.2386 0.01603 1292 26.08 1029.8 26.08 1060.7 1086.8 0.05159 2.1005 58
60 0.2563 0.01604 1207 28.08 1030.4 28.08 1059.6 1087.7 0.05555 2.0943 60
62 0.2751 0.01604 1129 30.09 1031.1 30.09 1058.5 1088.6 0.05940 2.0882 62
64 0.2952 0.01604 1056 32.09 1031.8 32.09 1057.3 1089.4 0.06323 2.0821 64
66 0.3165 0.01604 988.4 34.09 1032.4 34.09 1056.2 1090.3 0.06704 2.0761 66
68 0.3391 0.01605 925.8 36.09 1033.1 36.09 1055.1 1091.2 0.07084 2.0701 68
70 0.3632 0.01605 867.7 38.09 1033.7 38.09 1054.0 1092.0 0.07463 2.0642 70
72 0.3887 0.01606 813.7 40.09 1034.4 40.09 1052.8 1092.9 0.07839 2.0584 72
74 0.4158 0.01606 763.5 42.09 1035.0 42.09 1051.7 1093.8 0.08215 2.0526 74
76 0.4446 0.01606 716.8 44.09 1035.7 44.09 1050.6 1094.7 0.08589 2.0469 76
78 0.4750 0.01607 673.3 46.09 1036.3 46.09 1049.4 1095.5 0.08961 2.0412 78
80 0.5073 0.01607 632.8 48.08 1037.0 48.09 1048.3 1096.4 0.09332 2.0356 80
82 0.5414 0.01608 595.0 50.08 1037.6 50.08 1047.2 1097.3 0.09701 2.0300 82
84 0.5776 0.01608 559.8 52.08 1038.3 52.08 1046.0 1098.1 0.1007 2.0245 84
86 0.6158 0.01609 527.0 54.08 1038.9 54.08 1044.9 1099.0 0.1044 2.0190 86
88 0.6562 0.01609 496.3 56.07 1039.6 56.07 1043.8 1099.9 0.1080 2.0136 88
90 0.6988 0.01610 467.7 58.07 1040.2 58.07 1042.7 1100.7 0.1117 2.0083 90
92 0.7439 0.01611 440.9 60.06 1040.9 60.06 1041.5 1101.6 0.1153 2.0030 92
94 0.7914 0.01611 415.9 62.06 1041.5 62.06 1040.4 1102.4 0.1189 1.9977 94
96 0.8416 0.01612 392.4 64.05 1041.2 64.06 1039.2 1103.3 0.1225 1.9925 96
98 0.8945 0.01612 370.5 66.05 1042.8 66.05 1038.1 1104.2 0.1261 1.9874 98
100 0.9503 0.01613 350.0 68.04 1043.5 68.05 1037.0 1105.0 0.1296 1.9822 100
110 1.276 0.01617 265.1 78.02 1046.7 78.02 1031.3 1109.3 0.1473 1.9574 110
120 1.695 0.01621 203.0 87.99 1049.9 88.00 1025.5 1113.5 0.1647 1.9336 120
130 2.225 0.01625 157.2 97.97 1053.0 97.98 1019.8 1117.8 0.1817 1.9109 130
140 2.892 0.01629 122.9 107.95 1056.2 107.96 1014.0 1121.9 0.1985 1.8892 140
150 3.722 0.01634 97.0 117.95 1059.3 117.96 1008.1 1126.1 0.2150 1.8684 150
160 4.745 0.01640 77.2 127.94 1062.3 127.96 1002.2 1130.1 0.2313 1.8484 160
170 5.996 0.01645 62.0 137.95 1065.4 137.97 996.2 1134.2 0.2473 1.8293 170
180 7.515 0.01651 50.2 147.97 1068.3 147.99 990.2 1138.2 0.2631 1.8109 180
190 9.343 0.01657 41.0 158.00 1071.3 158.03 984.1 1142.1 0.2787 1.7932 190
200 11.529 0.01663 33.6 168.04 1074.2 168.07 977.9 1145.9 0.2940 1.7762 200
TABLE A-2E (Continued )

H2O
210 14.13 0.01670 27.82 178.1 1077.0 178.1 971.6 1149.7 0.3091 1.7599 210
212 14.70 0.01672 26.80 180.1 1077.6 180.2 970.3 1150.5 0.3121 1.7567 212
220 17.19 0.01677 23.15 188.2 1079.8 188.2 965.3 1153.5 0.3241 1.7441 220
230 20.78 0.01685 19.39 198.3 1082.6 198.3 958.8 1157.1 0.3388 1.7289 230
240 24.97 0.01692 16.33 208.4 1085.3 208.4 952.3 1160.7 0.3534 1.7143 240
250 29.82 0.01700 13.83 218.5 1087.9 218.6 945.6 1164.2 0.3677 1.7001 250
260 35.42 0.01708 11.77 228.6 1090.5 228.8 938.8 1167.6 0.3819 1.6864 260
270 41.85 0.01717 10.07 238.8 1093.0 239.0 932.0 1170.9 0.3960 1.6731 270
280 49.18 0.01726 8.65 249.0 1095.4 249.2 924.9 1174.1 0.4099 1.6602 280
290 57.53 0.01735 7.47 259.3 1097.7 259.4 917.8 1177.2 0.4236 1.6477 290
300 66.98 0.01745 6.472 269.5 1100.0 269.7 910.4 1180.2 0.4372 1.6356 300
310 77.64 0.01755 5.632 279.8 1102.1 280.1 903.0 1183.0 0.4507 1.6238 310
320 89.60 0.01765 4.919 290.1 1104.2 290.4 895.3 1185.8 0.4640 1.6123 320
330 103.00 0.01776 4.312 300.5 1106.2 300.8 887.5 1188.4 0.4772 1.6010 330
340 117.93 0.01787 3.792 310.9 1108.0 311.3 879.5 1190.8 0.4903 1.5901 340
350 134.53 0.01799 3.346 321.4 1109.8 321.8 871.3 1193.1 0.5033 1.5793 350
360 152.92 0.01811 2.961 331.8 1111.4 332.4 862.9 1195.2 0.5162 1.5688 360
370 173.23 0.01823 2.628 342.4 1112.9 343.0 854.2 1197.2 0.5289 1.5585 370
380 195.60 0.01836 2.339 353.0 1114.3 353.6 845.4 1199.0 0.5416 1.5483 380
390 220.2 0.01850 2.087 363.6 1115.6 364.3 836.2 1200.6 0.5542 1.5383 390
400 247.1 0.01864 1.866 374.3 1116.6 375.1 826.8 1202.0 0.5667 1.5284 400
410 276.5 0.01878 1.673 385.0 1117.6 386.0 817.2 1203.1 0.5792 1.5187 410
420 308.5 0.01894 1.502 395.8 1118.3 396.9 807.2 1204.1 0.5915 1.5091 420
430 343.3 0.01909 1.352 406.7 1118.9 407.9 796.9 1204.8 0.6038 1.4995 430
440 381.2 0.01926 1.219 417.6 1119.3 419.0 786.3 1205.3 0.6161 1.4900 440
450 422.1 0.01943 1.1011 428.6 1119.5 430.2 775.4 1205.6 0.6282 1.4806 450
460 466.3 0.01961 0.9961 439.7 1119.6 441.4 764.1 1205.5 0.6404 1.4712 460
470 514.1 0.01980 0.9025 450.9 1119.4 452.8 752.4 1205.2 0.6525 1.4618 470
480 565.5 0.02000 0.8187 462.2 1118.9 464.3 740.3 1204.6 0.6646 1.4524 480
490 620.7 0.02021 0.7436 473.6 1118.3 475.9 727.8 1203.7 0.6767 1.4430 490
500 680.0 0.02043 0.6761 485.1 1117.4 487.7 714.8 1202.5 0.6888 1.4335 500
520 811.4 0.02091 0.5605 508.5 1114.8 511.7 687.3 1198.9 0.7130 1.4145 520
540 961.5 0.02145 0.4658 532.6 1111.0 536.4 657.5 1193.8 0.7374 1.3950 540
560 1131.8 0.02207 0.3877 548.4 1105.8 562.0 625.0 1187.0 0.7620 1.3749 560
580 1324.3 0.02278 0.3225 583.1 1098.9 588.6 589.3 1178.0 0.7872 1.3540 580
600 1541.0 0.02363 0.2677 609.9 1090.0 616.7 549.7 1166.4 0.8130 1.3317 600
620 1784.4 0.02465 0.2209 638.3 1078.5 646.4 505.0 1151.4 0.8398 1.3075 620
640 2057.1 0.02593 0.1805 668.7 1063.2 678.6 453.4 1131.9 0.8681 1.2803 640
660 2362 0.02767 0.1446 702.3 1042.3 714.4 391.1 1105.5 0.8990 1.2483 660
680 2705 0.03032 0.1113 741.7 1011.0 756.9 309.8 1066.7 0.9350 1.2068 680
700 3090 0.03666 0.0744 801.7 947.7 822.7 167.5 990.2 0.9902 1.1346 700
705.4 3204 0.05053 0.05053 872.6 872.6 902.5 0 902.5 1.0580 1.0580 705.4
Source: Tables A-2E through A-6E are extracted from J. H. Keenan, F. G. Keyes, P. G. Hill, and J. G. Moore, Steam Tables, Wiley, New York,
1969.
TABLE A-3E Properties of Saturated Water (LiquidVapor): Pressure Table

Press. Temp. Liquid Vapor Liquid Vapor Liquid Evap. Vapor Liquid Evap. Vapor Press.
lbf/in.2 F vf vg uf ug hf hfg hg sf sfg sg lbf/in.2
H2O
0.4 72.84 0.01606 792.0 40.94 1034.7 40.94 1052.3 1093.3 0.0800 1.9760 2.0559 0.4
0.6 85.19 0.01609 540.0 53.26 1038.7 53.27 1045.4 1098.6 0.1029 1.9184 2.0213 0.6
0.8 94.35 0.01611 411.7 62.41 1041.7 62.41 1040.2 1102.6 0.1195 1.8773 1.9968 0.8
1.0 101.70 0.01614 333.6 69.74 1044.0 69.74 1036.0 1105.8 0.1327 1.8453 1.9779 1.0
1.2 107.88 0.01616 280.9 75.90 1046.0 75.90 1032.5 1108.4 0.1436 1.8190 1.9626 1.2
1.5 115.65 0.01619 227.7 83.65 1048.5 83.65 1028.0 1111.7 0.1571 1.7867 1.9438 1.5
2.0 126.04 0.01623 173.75 94.02 1051.8 94.02 1022.1 1116.1 0.1750 1.7448 1.9198 2.0
3.0 141.43 0.01630 118.72 109.38 1056.6 109.39 1013.1 1122.5 0.2009 1.6852 1.8861 3.0
4.0 152.93 0.01636 90.64 120.88 1060.2 120.89 1006.4 1127.3 0.2198 1.6426 1.8624 4.0
5.0 162.21 0.01641 73.53 130.15 1063.0 130.17 1000.9 1131.0 0.2349 1.6093 1.8441 5.0
6.0 170.03 0.01645 61.98 137.98 1065.4 138.00 996.2 1134.2 0.2474 1.5819 1.8292 6.0
7.0 176.82 0.01649 53.65 144.78 1067.4 144.80 992.1 1136.9 0.2581 1.5585 1.8167 7.0
8.0 182.84 0.01653 47.35 150.81 1069.2 150.84 988.4 1139.3 0.2675 1.5383 1.8058 8.0
9.0 188.26 0.01656 42.41 156.25 1070.8 156.27 985.1 1141.4 0.2760 1.5203 1.7963 9.0
10 193.19 0.01659 38.42 161.20 1072.2 161.23 982.1 1143.3 0.2836 1.5041 1.7877 10
14.696 211.99 0.01672 26.80 180.10 1077.6 180.15 970.4 1150.5 0.3121 1.4446 1.7567 14.696
15 213.03 0.01672 26.29 181.14 1077.9 181.19 969.7 1150.9 0.3137 1.4414 1.7551 15
20 227.96 0.01683 20.09 196.19 1082.0 196.26 960.1 1156.4 0.3358 1.3962 1.7320 20
25 240.08 0.01692 16.31 208.44 1085.3 208.52 952.2 1160.7 0.3535 1.3607 1.7142 25
30 250.34 0.01700 13.75 218.84 1088.0 218.93 945.4 1164.3 0.3682 1.3314 1.6996 30
35 259.30 0.01708 11.90 227.93 1090.3 228.04 939.3 1167.4 0.3809 1.3064 1.6873 35
40 267.26 0.01715 10.50 236.03 1092.3 236.16 933.8 1170.0 0.3921 1.2845 1.6767 40
45 274.46 0.01721 9.40 243.37 1094.0 243.51 928.8 1172.3 0.4022 1.2651 1.6673 45
50 281.03 0.01727 8.52 250.08 1095.6 250.24 924.2 1174.4 0.4113 1.2476 1.6589 50
55 287.10 0.01733 7.79 256.28 1097.0 256.46 919.9 1176.3 0.4196 1.2317 1.6513 55
60 292.73 0.01738 7.177 262.1 1098.3 262.2 915.8 1178.0 0.4273 1.2170 1.6443 60
65 298.00 0.01743 6.647 267.5 1099.5 267.7 911.9 1179.6 0.4345 1.2035 1.6380 65
70 302.96 0.01748 6.209 272.6 1100.6 272.8 908.3 1181.0 0.4412 1.1909 1.6321 70
75 307.63 0.01752 5.818 277.4 1101.6 277.6 904.8 1182.4 0.4475 1.1790 1.6265 75
80 312.07 0.01757 5.474 282.0 1102.6 282.2 901.4 1183.6 0.4534 1.1679 1.6213 80
85 316.29 0.01761 5.170 286.3 1103.5 286.6 898.2 1184.8 0.4591 1.1574 1.6165 85
90 320.31 0.01766 4.898 290.5 1104.3 290.8 895.1 1185.9 0.4644 1.1475 1.6119 90
95 324.16 0.01770 4.654 294.5 1105.0 294.8 892.1 1186.9 0.4695 1.1380 1.6075 95
100 327.86 0.01774 4.434 298.3 1105.8 298.6 889.2 1187.8 0.4744 1.1290 1.6034 100
110 334.82 0.01781 4.051 305.5 1107.1 305.9 883.7 1189.6 0.4836 1.1122 1.5958 110
120 341.30 0.01789 3.730 312.3 1108.3 312.7 878.5 1191.1 0.4920 1.0966 1.5886 120
130 347.37 0.01796 3.457 318.6 1109.4 319.0 873.5 1192.5 0.4999 1.0822 1.5821 130
140 353.08 0.01802 3.221 324.6 1110.3 325.1 868.7 1193.8 0.5073 1.0688 1.5761 140
150 358.48 0.01809 3.016 330.2 1111.2 330.8 864.2 1194.9 0.5142 1.0562 1.5704 150
160 363.60 0.01815 2.836 335.6 1112.0 336.2 859.8 1196.0 0.5208 1.0443 1.5651 160

Press. Temp. Liquid Vapor Liquid Vapor Liquid Evap. Vapor Liquid Evap. Vapor Press.
lbf/in.2 F vf vg uf ug hf hfg hg sf sfg sg lbf/in.2
H2O
170 368.47 0.01821 2.676 340.8 1112.7 341.3 855.6 1196.9 0.5270 1.0330 1.5600 170
180 373.13 0.01827 2.553 345.7 1113.4 346.3 851.5 1197.8 0.5329 1.0223 1.5552 180
190 377.59 0.01833 2.405 350.4 1114.0 351.0 847.5 1198.6 0.5386 1.0122 1.5508 190
200 381.86 0.01839 2.289 354.9 1114.6 355.6 843.7 1199.3 0.5440 1.0025 1.5465 200
250 401.04 0.01865 1.845 375.4 1116.7 376.2 825.8 1202.1 0.5680 0.9594 1.5274 250
300 417.43 0.01890 1.544 393.0 1118.2 394.1 809.8 1203.9 0.5883 0.9232 1.5115 300
350 431.82 0.01912 1.327 408.7 1119.0 409.9 795.0 1204.9 0.6060 0.8917 1.4977 350
400 444.70 0.01934 1.162 422.8 1119.5 424.2 781.2 1205.5 0.6218 0.8638 1.4856 400
450 456.39 0.01955 1.033 435.7 1119.6 437.4 768.2 1205.6 0.6360 0.8385 1.4745 450
500 467.13 0.01975 0.928 447.7 1119.4 449.5 755.8 1205.3 0.6490 0.8154 1.4644 500
550 477.07 0.01994 0.842 458.9 1119.1 460.9 743.9 1204.8 0.6611 0.7941 1.4451 550
600 486.33 0.02013 0.770 469.4 1118.6 471.7 732.4 1204.1 0.6723 0.7742 1.4464 600
700 503.23 0.02051 0.656 488.9 1117.0 491.5 710.5 1202.0 0.6927 0.7378 1.4305 700
800 518.36 0.02087 0.569 506.6 1115.0 509.7 689.6 1199.3 0.7110 0.7050 1.4160 800
900 532.12 0.02123 0.501 523.0 1112.6 526.6 669.5 1196.0 0.7277 0.6750 1.4027 900
1000 544.75 0.02159 0.446 538.4 1109.9 542.4 650.0 1192.4 0.7432 0.6471 1.3903 1000
1100 556.45 0.02195 0.401 552.9 1106.8 557.4 631.0 1188.3 0.7576 0.6209 1.3786 1100
1200 567.37 0.02232 0.362 566.7 1103.5 571.7 612.3 1183.9 0.7712 0.5961 1.3673 1200
1300 577.60 0.02269 0.330 579.9 1099.8 585.4 593.8 1179.2 0.7841 0.5724 1.3565 1300
1400 587.25 0.02307 0.302 592.7 1096.0 598.6 575.5 1174.1 0.7964 0.5497 1.3461 1400
1500 596.39 0.02346 0.277 605.0 1091.8 611.5 557.2 1168.7 0.8082 0.5276 1.3359 1500
1600 605.06 0.02386 0.255 616.9 1087.4 624.0 538.9 1162.9 0.8196 0.5062 1.3258 1600
1700 613.32 0.02428 0.236 628.6 1082.7 636.2 520.6 1156.9 0.8307 0.4852 1.3159 1700
1800 621.21 0.02472 0.218 640.0 1077.7 648.3 502.1 1150.4 0.8414 0.4645 1.3060 1800
1900 628.76 0.02517 0.203 651.3 1072.3 660.1 483.4 1143.5 0.8519 0.4441 1.2961 1900
2000 636.00 0.02565 0.188 662.4 1066.6 671.9 464.4 1136.3 0.8623 0.4238 1.2861 2000
2250 652.90 0.02698 0.157 689.9 1050.6 701.1 414.8 1115.9 0.8876 0.3728 1.2604 2250
2500 668.31 0.02860 0.131 717.7 1031.0 730.9 360.5 1091.4 0.9131 0.3196 1.2327 2500
2750 682.46 0.03077 0.107 747.3 1005.9 763.0 297.4 1060.4 0.9401 0.2604 1.2005 2750
3000 695.52 0.03431 0.084 783.4 968.8 802.5 213.0 1015.5 0.9732 0.1843 1.1575 3000
3203.6 705.44 0.05053 0.0505 872.6 872.6 902.5 0 902.5 1.0580 0 1.0580 3203.6
TABLE A-4E Properties of Superheated Water Vapor

T v u h s v u h s
F ft3/lb Btu/lb Btu/lb Btu/lb # R ft3/lb Btu/lb Btu/lb Btu/lb # R
p 1 lbf/in.2 p 5 lbf/in.2
(Tsat 101.7F) (Tsat 162.2F)
Sat. 333.6 1044.0 1105.8 1.9779 73.53 1063.0 1131.0 1.8441
H2O
150 362.6 1060.4 1127.5 2.0151

200 392.5 1077.5 1150.1 2.0508 78.15 1076.0 1148.6 1.8715
250 422.4 1094.7 1172.8 2.0839 84.21 1093.8 1171.7 1.9052
300 452.3 1112.0 1195.7 2.1150 90.24 1111.3 1194.8 1.9367
400 511.9 1147.0 1241.8 2.1720 102.24 1146.6 1241.2 1.9941
500 571.5 1182.8 1288.5 2.2235 114.20 1182.5 1288.2 2.0458
600 631.1 1219.3 1336.1 2.2706 126.15 1219.1 1335.8 2.0930
700 690.7 1256.7 1384.5 2.3142 138.08 1256.5 1384.3 2.1367
800 750.3 1294.4 1433.7 2.3550 150.01 1294.7 1433.5 2.1775
900 809.9 1333.9 1483.8 2.3932 161.94 1333.8 1483.7 2.2158
1000 869.5 1373.9 1534.8 2.4294 173.86 1373.9 1534.7 2.2520
p 10 lbf/in.2 p 14.7 lbf/in.2

(Tsat 193.2F) (Tsat 212.0F)
Sat. 38.42 1072.2 1143.3 1.7877 26.80 1077.6 1150.5 1.7567
200 38.85 1074.7 1146.6 1.7927
250 41.95 1092.6 1170.2 1.8272 28.42 1091.5 1168.8 1.7832
300 44.99 1110.4 1193.7 1.8592 30.52 1109.6 1192.6 1.8157
400 51.03 1146.1 1240.5 1.9171 34.67 1145.6 1239.9 1.8741
500 57.04 1182.2 1287.7 1.9690 38.77 1181.8 1287.3 1.9263
600 63.03 1218.9 1335.5 2.0164 42.86 1218.6 1335.2 1.9737
700 69.01 1256.3 1384.0 2.0601 46.93 1256.1 1383.8 2.0175
800 74.98 1294.6 1433.3 2.1009 51.00 1294.4 1433.1 2.0584
900 80.95 1333.7 1483.5 2.1393 55.07 1333.6 1483.4 2.0967
1000 86.91 1373.8 1534.6 2.1755 59.13 1373.7 1534.5 2.1330
1100 92.88 1414.7 1586.6 2.2099 63.19 1414.6 1586.4 2.1674
(Tsat 228.0F) (Tsat 267.3F)
Sat. 20.09 1082.0 1156.4 1.7320 10.50 1093.3 1170.0 1.6767
250 20.79 1090.3 1167.2 1.7475
300 22.36 1108.7 1191.5 1.7805 11.04 1105.1 1186.8 1.6993
350 23.90 1126.9 1215.4 1.8110 11.84 1124.2 1211.8 1.7312
400 25.43 1145.1 1239.2 1.8395 12.62 1143.0 1236.4 1.7606
500 28.46 1181.5 1286.8 1.8919 14.16 1180.1 1284.9 1.8140
600 31.47 1218.4 1334.8 1.9395 15.69 1217.3 1333.4 1.8621
700 34.47 1255.9 1383.5 1.9834 17.20 1255.1 1382.4 1.9063
800 37.46 1294.3 1432.9 2.0243 18.70 1293.7 1432.1 1.9474
900 40.45 1333.5 1483.2 2.0627 20.20 1333.0 1482.5 1.9859
1000 43.44 1373.5 1534.3 2.0989 21.70 1373.1 1533.8 2.0223
1100 46.42 1414.5 1586.3 2.1334 23.20 1414.2 1585.9 2.0568
TABLE A-4E (Continued)

T v u h s v u h s
(Tsat 292.7F) (Tsat 312.1F)
Sat. 7.17 1098.3 1178.0 1.6444 5.47 1102.6 1183.6 1.6214
H2O
300 7.26 1101.3 1181.9 1.6496
350 7.82 1121.4 1208.2 1.6830 5.80 1118.5 1204.3 1.6476
400 8.35 1140.8 1233.5 1.7134 6.22 1138.5 1230.6 1.6790
500 9.40 1178.6 1283.0 1.7678 7.02 1177.2 1281.1 1.7346
600 10.43 1216.3 1332.1 1.8165 7.79 1215.3 1330.7 1.7838
700 11.44 1254.4 1381.4 1.8609 8.56 1253.6 1380.3 1.8285
800 12.45 1293.0 1431.2 1.9022 9.32 1292.4 1430.4 1.8700
900 13.45 1332.5 1481.8 1.9408 10.08 1332.0 1481.2 1.9087
1000 14.45 1372.7 1533.2 1.9773 10.83 1372.3 1532.6 1.9453
1100 15.45 1413.8 1585.4 2.0119 11.58 1413.5 1584.9 1.9799
1200 16.45 1455.8 1638.5 2.0448 12.33 1455.5 1638.1 2.0130

(Tsat 327.8F) (Tsat 341.3F)
Sat. 4.434 1105.8 1187.8 1.6034 3.730 1108.3 1191.1 1.5886
350 4.592 1115.4 1200.4 1.6191 3.783 1112.2 1196.2 1.5950
400 4.934 1136.2 1227.5 1.6517 4.079 1133.8 1224.4 1.6288
450 5.265 1156.2 1253.6 1.6812 4.360 1154.3 1251.2 1.6590
500 5.587 1175.7 1279.1 1.7085 4.633 1174.2 1277.1 1.6868
600 6.216 1214.2 1329.3 1.7582 5.164 1213.2 1327.8 1.7371
700 6.834 1252.8 1379.2 1.8033 5.682 1252.0 1378.2 1.7825
800 7.445 1291.8 1429.6 1.8449 6.195 1291.2 1428.7 1.8243
900 8.053 1331.5 1480.5 1.8838 6.703 1330.9 1479.8 1.8633
1000 8.657 1371.9 1532.1 1.9204 7.208 1371.5 1531.5 1.9000
1100 9.260 1413.1 1584.5 1.9551 7.711 1412.8 1584.0 1.9348
1200 9.861 1455.2 1637.7 1.9882 8.213 1454.9 1637.3 1.9679

(Tsat 353.1F) (Tsat 363.6F)
Sat. 3.221 1110.3 1193.8 1.5761 2.836 1112.0 1196.0 1.5651
400 3.466 1131.4 1221.2 1.6088 3.007 1128.8 1217.8 1.5911
450 3.713 1152.4 1248.6 1.6399 3.228 1150.5 1246.1 1.6230
500 3.952 1172.7 1275.1 1.6682 3.440 1171.2 1273.0 1.6518
550 4.184 1192.5 1300.9 1.6945 3.646 1191.3 1299.2 1.6785
600 4.412 1212.1 1326.4 1.7191 3.848 1211.1 1325.0 1.7034
700 4.860 1251.2 1377.1 1.7648 4.243 1250.4 1376.0 1.7494
800 5.301 1290.5 1427.9 1.8068 4.631 1289.9 1427.0 1.7916
900 5.739 1330.4 1479.1 1.8459 5.015 1329.9 1478.4 1.8308
1000 6.173 1371.0 1531.0 1.8827 5.397 1370.6 1530.4 1.8677
1100 6.605 1412.4 1583.6 1.9176 5.776 1412.1 1583.1 1.9026
1200 7.036 1454.6 1636.9 1.9507 6.154 1454.3 1636.5 1.9358

T v u h s v u h s
(Tsat 373.1F) (Tsat 381.8F)
Sat. 2.533 1113.4 1197.8 1.5553 2.289 1114.6 1199.3 1.5464
H2O
400 2.648 1126.2 1214.4 1.5749 2.361 1123.5 1210.8 1.5600

450 2.850 1148.5 1243.4 1.6078 2.548 1146.4 1240.7 1.5938
500 3.042 1169.6 1270.9 1.6372 2.724 1168.0 1268.8 1.6239
550 3.228 1190.0 1297.5 1.6642 2.893 1188.7 1295.7 1.6512
600 3.409 1210.0 1323.5 1.6893 3.058 1208.9 1322.1 1.6767
700 3.763 1249.6 1374.9 1.7357 3.379 1248.8 1373.8 1.7234
800 4.110 1289.3 1426.2 1.7781 3.693 1288.6 1425.3 1.7660
900 4.453 1329.4 1477.7 1.8174 4.003 1328.9 1477.1 1.8055
1000 4.793 1370.2 1529.8 1.8545 4.310 1369.8 1529.3 1.8425
1100 5.131 1411.7 1582.6 1.8894 4.615 1411.4 1582.2 1.8776
1200 5.467 1454.0 1636.1 1.9227 4.918 1453.7 1635.7 1.9109

(Tsat 401.0F) (Tsat 417.4F)
Sat. 1.845 1116.7 1202.1 1.5274 1.544 1118.2 1203.9 1.5115
450 2.002 1141.1 1233.7 1.5632 1.636 1135.4 1226.2 1.5365
500 2.150 1163.8 1263.3 1.5948 1.766 1159.5 1257.5 1.5701
550 2.290 1185.3 1291.3 1.6233 1.888 1181.9 1286.7 1.5997
600 2.426 1206.1 1318.3 1.6494 2.004 1203.2 1314.5 1.6266
700 2.688 1246.7 1371.1 1.6970 2.227 1244.0 1368.3 1.6751
800 2.943 1287.0 1423.2 1.7301 2.442 1285.4 1421.0 1.7187
900 3.193 1327.6 1475.3 1.7799 2.653 1326.3 1473.6 1.7589
1000 3.440 1368.7 1527.9 1.8172 2.860 1367.7 1526.5 1.7964
1100 3.685 1410.5 1581.0 1.8524 3.066 1409.6 1579.8 1.8317
1200 3.929 1453.0 1634.8 1.8858 3.270 1452.2 1633.8 1.8653
1300 4.172 1496.3 1689.3 1.9177 3.473 1495.6 1688.4 1.8973

(Tsat 431.8F) (Tsat 444.7F)
Sat. 1.327 1119.0 1204.9 1.4978 1.162 1119.5 1205.5 1.4856
450 1.373 1129.2 1218.2 1.5125 1.175 1122.6 1209.5 1.4901
500 1.491 1154.9 1251.5 1.5482 1.284 1150.1 1245.2 1.5282
550 1.600 1178.3 1281.9 1.5790 1.383 1174.6 1277.0 1.5605
600 1.703 1200.3 1310.6 1.6068 1.476 1197.3 1306.6 1.5892
700 1.898 1242.5 1365.4 1.6562 1.650 1240.4 1362.5 1.6397
800 2.085 1283.8 1418.8 1.7004 1.816 1282.1 1416.6 1.6844
900 2.267 1325.0 1471.8 1.7409 1.978 1323.7 1470.1 1.7252
1000 2.446 1366.6 1525.0 1.7787 2.136 1365.5 1523.6 1.7632
1100 2.624 1408.7 1578.6 1.8142 2.292 1407.8 1577.4 1.7989
1200 2.799 1451.5 1632.8 1.8478 2.446 1450.7 1621.8 1.8327
1300 2.974 1495.0 1687.6 1.8799 2.599 1494.3 1686.8 1.8648

T v u h s v u h s
(Tsat 456.4F) (Tsat 467.1F)
Sat. 1.033 1119.6 1205.6 1.4746 0.928 1119.4 1205.3 1.4645
H2O
500 1.123 1145.1 1238.5 1.5097 0.992 1139.7 1231.5 1.4923
550 1.215 1170.7 1271.9 1.5436 1.079 1166.7 1266.6 1.5279
600 1.300 1194.3 1302.5 1.5732 1.158 1191.1 1298.3 1.5585
700 1.458 1238.2 1359.6 1.6248 1.304 1236.0 1356.7 1.6112
800 1.608 1280.5 1414.4 1.6701 1.441 1278.8 1412.1 1.6571
900 1.752 1322.4 1468.3 1.7113 1.572 1321.0 1466.5 1.6987
1000 1.894 1364.4 1522.2 1.7495 1.701 1363.3 1520.7 1.7371
1100 2.034 1406.9 1576.3 1.7853 1.827 1406.0 1575.1 1.7731
1200 2.172 1450.0 1630.8 1.8192 1.952 1449.2 1629.8 1.8072
1300 2.308 1493.7 1685.9 1.8515 2.075 1493.1 1685.1 1.8395
1400 2.444 1538.1 1741.7 1.8823 2.198 1537.6 1741.0 1.8704

(Tsat 486.3F) (Tsat 503.2F)
Sat. 0.770 1118.6 1204.1 1.4464 0.656 1117.0 1202.0 1.4305
500 0.795 1128.0 1216.2 1.4592
550 0.875 1158.2 1255.4 1.4990 0.728 1149.0 1243.2 1.4723
600 0.946 1184.5 1289.5 1.5320 0.793 1177.5 1280.2 1.5081
700 1.073 1231.5 1350.6 1.5872 0.907 1226.9 1344.4 1.5661
800 1.190 1275.4 1407.6 1.6343 1.011 1272.0 1402.9 1.6145
900 1.302 1318.4 1462.9 1.6766 1.109 1315.6 1459.3 1.6576
1000 1.411 1361.2 1517.8 1.7155 1.204 1358.9 1514.9 1.6970
1100 1.517 1404.2 1572.7 1.7519 1.296 1402.4 1570.2 1.7337
1200 1.622 1447.7 1627.8 1.7861 1.387 1446.2 1625.8 1.7682
1300 1.726 1491.7 1683.4 1.8186 1.476 1490.4 1681.7 1.8009
1400 1.829 1536.5 1739.5 1.8497 1.565 1535.3 1738.1 1.8321

(Tsat 518.3F) (Tsat 532.1F)
Sat. 0.569 1115.0 1199.3 1.4160 0.501 1112.6 1196.0 1.4027
550 0.615 1138.8 1229.9 1.4469 0.527 1127.5 1215.2 1.4219
600 0.677 1170.1 1270.4 1.4861 0.587 1162.2 1260.0 1.4652
650 0.732 1197.2 1305.6 1.5186 0.639 1191.1 1297.5 1.4999
700 0.783 1222.1 1338.0 1.5471 0.686 1217.1 1331.4 1.5297
800 0.876 1268.5 1398.2 1.5969 0.772 1264.9 1393.4 1.5810
900 0.964 1312.9 1455.6 1.6408 0.851 1310.1 1451.9 1.6257
1000 1.048 1356.7 1511.9 1.6807 0.927 1354.5 1508.9 1.6662
1100 1.130 1400.5 1567.8 1.7178 1.001 1398.7 1565.4 1.7036
1200 1.210 1444.6 1623.8 1.7526 1.073 1443.0 1621.7 1.7386
1300 1.289 1489.1 1680.0 1.7854 1.144 1487.8 1687.3 1.7717
1400 1.367 1534.2 1736.6 1.8167 1.214 1533.0 1735.1 1.8031

T v u h s v u h s
p 1000 lbf/in.2 p 1200 lbf/in.2
(Tsat 544.7F) (Tsat 567.4F)
Sat. 0.446 1109.0 1192.4 1.3903 0.362 1103.5 1183.9 1.3673
H2O
600 0.514 1153.7 1248.8 1.4450 0.402 1134.4 1223.6 1.4054

650 0.564 1184.7 1289.1 1.4822 0.450 1170.9 1270.8 1.4490
700 0.608 1212.0 1324.6 1.5135 0.491 1201.3 1310.2 1.4837
800 0.688 1261.2 1388.5 1.5665 0.562 1253.7 1378.4 1.5402
900 0.761 1307.3 1448.1 1.6120 0.626 1301.5 1440.4 1.5876
1000 0.831 1352.2 1505.9 1.6530 0.685 1347.5 1499.7 1.6297
1100 0.898 1396.8 1562.9 1.6908 0.743 1393.0 1557.9 1.6682
1200 0.963 1441.5 1619.7 1.7261 0.798 1438.3 1615.5 1.7040
1300 1.027 1486.5 1676.5 1.7593 0.853 1483.8 1673.1 1.7377
1400 1.091 1531.9 1733.7 1.7909 0.906 1529.6 1730.7 1.7696
1600 1.215 1624.4 1849.3 1.8499 1.011 1622.6 1847.1 1.8290
p 1400 lbf/in.2 p 1600 lbf/in.2

(Tsat 587.2F) (Tsat 605.1F)
Sat. 0.302 1096.0 1174.1 1.3461 0.255 1087.4 1162.9 1.3258
600 0.318 1110.9 1193.1 1.3641
650 0.367 1155.5 1250.5 1.4171 0.303 1137.8 1227.4 1.3852
700 0.406 1189.6 1294.8 1.4562 0.342 1177.0 1278.1 1.4299
800 0.471 1245.8 1367.9 1.5168 0.403 1237.7 1357.0 1.4953
900 0.529 1295.6 1432.5 1.5661 0.466 1289.5 1424.4 1.5468
1000 0.582 1342.8 1493.5 1.6094 0.504 1338.0 1487.1 1.5913
1100 0.632 1389.1 1552.8 1.6487 0.549 1385.2 1547.7 1.6315
1200 0.681 1435.1 1611.4 1.6851 0.592 1431.8 1607.1 1.6684
1300 0.728 1481.1 1669.6 1.7192 0.634 1478.3 1666.1 1.7029
1400 0.774 1527.2 1727.8 1.7513 0.675 1524.9 1724.8 1.7354
1600 0.865 1620.8 1844.8 1.8111 0.755 1619.0 1842.6 1.7955
p 1800 lbf/in.2 p 2000 lbf/in.2

(Tsat 621.2F) (Tsat 636.0F)
Sat. 0.218 1077.7 1150.4 1.3060 0.188 1066.6 1136.3 1.2861
650 0.251 1117.0 1200.4 1.3517 0.206 1091.1 1167.2 1.3141
700 0.291 1163.1 1259.9 1.4042 0.249 1147.7 1239.8 1.3782
750 0.322 1198.6 1305.9 1.4430 0.280 1187.3 1291.1 1.4216
800 0.350 1229.1 1345.7 1.4753 0.307 1220.1 1333.8 1.4562
900 0.399 1283.2 1416.1 1.5291 0.353 1276.8 1407.6 1.5126
1000 0.443 1333.1 1480.7 1.5749 0.395 1328.1 1474.1 1.5598
1100 0.484 1381.2 1542.5 1.6159 0.433 1377.2 1537.2 1.6017
1200 0.524 1428.5 1602.9 1.6534 0.469 1425.2 1598.6 1.6398
1300 0.561 1475.5 1662.5 1.6883 0.503 1472.7 1659.0 1.6751
1400 0.598 1522.5 1721.8 1.7211 0.537 1520.2 1718.8 1.7082
1600 0.670 1617.2 1840.4 1.7817 0.602 1615.4 1838.2 1.7692

T v u h s v u h s
p 2500 lbf/in.2 p 3000 lbf/in.2
(Tsat 668.3F) (Tsat 695.5F)
Sat. 0.1306 1031.0 1091.4 1.2327 0.0840 968.8 1015.5 1.1575
H2O
700 0.1684 1098.7 1176.6 1.3073 0.0977 1003.9 1058.1 1.1944
750 0.2030 1155.2 1249.1 1.3686 0.1483 1114.7 1197.1 1.3122
800 0.2291 1195.7 1301.7 1.4112 0.1757 1167.6 1265.2 1.3675
900 0.2712 1259.9 1385.4 1.4752 0.2160 1241.8 1361.7 1.4414
1000 0.3069 1315.2 1457.2 1.5262 0.2485 1301.7 1439.6 1.4967
1100 0.3393 1366.8 1523.8 1.5704 0.2772 1356.2 1510.1 1.5434
1200 0.3696 1416.7 1587.7 1.6101 0.3086 1408.0 1576.6 1.5848
1300 0.3984 1465.7 1650.0 1.6465 0.3285 1458.5 1640.9 1.6224
1400 0.4261 1514.2 1711.3 1.6804 0.3524 1508.1 1703.7 1.6571
1500 0.4531 1562.5 1772.1 1.7123 0.3754 1557.3 1765.7 1.6896
1600 0.4795 1610.8 1832.6 1.7424 0.3978 1606.3 1827.1 1.7201
p 3500 lbf/in.2 p 4000 lbf/in.2

650 0.0249 663.5 679.7 0.8630 0.0245 657.7 675.8 0.8574
700 0.0306 759.5 779.3 0.9506 0.0287 742.1 763.4 0.9345
750 0.1046 1058.4 1126.1 1.2440 0.0633 960.7 1007.5 1.1395
800 0.1363 1134.7 1223.0 1.3226 0.1052 1095.0 1172.9 1.2740
900 0.1763 1222.4 1336.5 1.4096 0.1462 1201.5 1309.7 1.3789
1000 0.2066 1287.6 1421.4 1.4699 0.1752 1272.9 1402.6 1.4449
1100 0.2328 1345.2 1496.0 1.5193 0.1995 1333.9 1481.6 1.4973
1200 0.2566 1399.2 1565.3 1.5624 0.2213 1390.1 1553.9 1.5423
1300 0.2787 1451.1 1631.7 1.6012 0.2414 1443.7 1622.4 1.5823
1400 0.2997 1501.9 1696.1 1.6368 0.2603 1495.7 1688.4 1.6188
1500 0.3199 1552.0 1759.2 1.6699 0.2784 1546.7 1752.8 1.6526
1600 0.3395 1601.7 1831.6 1.7010 0.2959 1597.1 1816.1 1.6841
p 4400 lbf/in.2 p 4800 lbf/in.2

650 0.0242 653.6 673.3 0.8535 0.0237 649.8 671.0 0.8499
700 0.0278 732.7 755.3 0.9257 0.0271 725.1 749.1 0.9187
750 0.0415 870.8 904.6 1.0513 0.0352 832.6 863.9 1.0154
800 0.0844 1056.5 1125.3 1.2306 0.0668 1011.2 1070.5 1.1827
900 0.1270 1183.7 1287.1 1.3548 0.1109 1164.8 1263.4 1.3310
1000 0.1552 1260.8 1387.2 1.4260 0.1385 1248.3 1317.4 1.4078
1100 0.1784 1324.7 1469.9 1.4809 0.1608 1315.3 1458.1 1.4653
1200 0.1989 1382.8 1544.7 1.5274 0.1802 1375.4 1535.4 1.5133
1300 0.2176 1437.7 1614.9 1.5685 0.1979 1431.7 1607.4 1.5555
1400 0.2352 1490.7 1682.3 1.6057 0.2143 1485.7 1676.1 1.5934
1500 0.2520 1542.7 1747.6 1.6399 0.2300 1538.2 1742.5 1.6282
1600 0.2681 1593.4 1811.7 1.6718 0.2450 1589.8 1807.4 1.6605
TABLE A-5E Properties of Compressed Liquid Water

T v u h s v u h s
(Tsat 467.1F) (Tsat 544.7F)
32 0.015994 0.00 1.49 0.00000 0.015967 0.03 2.99 0.00005
H2O
50 0.015998 18.02 19.50 0.03599 0.015972 17.99 20.94 0.03592

100 0.016106 67.87 69.36 0.12932 0.016082 67.70 70.68 0.12901
150 0.016318 117.66 119.17 0.21457 0.016293 117.38 120.40 0.21410
200 0.016608 167.65 169.19 0.29341 0.016580 167.26 170.32 0.29281
300 0.017416 268.92 270.53 0.43641 0.017379 268.24 271.46 0.43552
400 0.018608 373.68 375.40 0.56604 0.018550 372.55 375.98 0.56472
Sat. 0.019748 447.70 449.53 0.64904 0.021591 538.39 542.38 0.74320
p 1500 lbf/in.2 p 2000 lbf/in.2

(Tsat 596.4F) (Tsat 636.0F)
32 0.015939 0.05 4.47 0.00007 0.015912 0.06 5.95 0.00008
50 0.015946 17.95 22.38 0.03584 0.015920 17.91 23.81 0.03575
100 0.016058 67.53 71.99 0.12870 0.016034 67.37 73.30 0.12839
150 0.016268 117.10 121.62 0.21364 0.016244 116.83 122.84 0.21318
200 0.016554 166.87 171.46 0.29221 0.016527 166.49 172.60 0.29162
300 0.017343 267.58 272.39 0.43463 0.017308 266.93 273.33 0.43376
400 0.018493 371.45 376.59 0.56343 0.018439 370.38 377.21 0.56216
500 0.02024 481.8 487.4 0.6853 0.02014 479.8 487.3 0.6832
Sat. 0.02346 605.0 611.5 0.8082 0.02565 662.4 671.9 0.8623
p 3000 lbf/in.2 p 4000 lbf/in.2

(Tsat 695.5F)
32 0.015859 0.09 8.90 0.00009 0.015807 0.10 11.80 0.00005
50 0.015870 17.84 26.65 0.03555 0.015821 17.76 29.47 0.03534
100 0.015987 67.04 75.91 0.12777 0.015942 66.72 78.52 0.12714
150 0.016196 116.30 125.29 0.21226 0.016150 115.77 127.73 0.21136
200 0.016476 165.74 174.89 0.29046 0.016425 165.02 177.18 0.28931
300 0.017240 265.66 275.23 0.43205 0.017174 264.43 277.15 0.43038
400 0.018334 368.32 378.50 0.55970 0.018235 366.35 379.85 0.55734
500 0.019944 476.2 487.3 0.6794 0.019766 472.9 487.5 0.6758
Sat. 0.034310 783.5 802.5 0.9732
TABLE A-6E Properties of Saturated Water (SolidVapor): Temperature Table

Temp. Press. Solid Vapor Solid Subl. Vapor Solid Subl. Vapor Solid Subl. Vapor
F lbf/in.2 vi vg 103 ui uig ug hi hig hg si sig sg
H2O
32.018 .0887 .01747 3.302 143.34 1164.6 1021.2 143.34 1218.7 1075.4 .292 2.479 2.187
32 .0886 .01747 3.305 143.35 1164.6 1021.2 143.35 1218.7 1075.4 .292 2.479 2.187
30 .0808 .01747 3.607 144.35 1164.9 1020.5 144.35 1218.9 1074.5 .294 2.489 2.195
25 .0641 .01746 4.506 146.84 1165.7 1018.9 146.84 1219.1 1072.3 .299 2.515 2.216
20 .0505 .01745 5.655 149.31 1166.5 1017.2 149.31 1219.4 1070.1 .304 2.542 2.238
15 .0396 .01745 7.13 151.75 1167.3 1015.5 151.75 1219.7 1067.9 .309 2.569 2.260
10 .0309 .01744 9.04 154.17 1168.1 1013.9 154.17 1219.9 1065.7 .314 2.597 2.283
5 .0240 .01743 11.52 156.56 1168.8 1012.2 156.56 1220.1 1063.5 .320 2.626 2.306
0 .0185 .01743 14.77 158.93 1169.5 1010.6 158.93 1220.2 1061.2 .325 2.655 2.330
5 .0142 .01742 19.03 161.27 1170.2 1008.9 161.27 1220.3 1059.0 .330 2.684 2.354
10 .0109 .01741 24.66 163.59 1170.9 1007.3 163.59 1220.4 1056.8 .335 2.714 2.379
15 .0082 .01740 32.2 165.89 1171.5 1005.6 165.89 1220.5 1054.6 .340 2.745 2.405
20 .0062 .01740 42.2 168.16 1172.1 1003.9 168.16 1220.6 1052.4 .345 2.776 2.431
25 .0046 .01739 55.7 170.40 1172.7 1002.3 170.40 1220.6 1050.2 .351 2.808 2.457
30 .0035 .01738 74.1 172.63 1173.2 1000.6 172.63 1220.6 1048.0 .356 2.841 2.485
35 .0026 .01737 99.2 174.82 1173.8 998.9 174.82 1220.6 1045.8 .361 2.874 2.513
40 .0019 .01737 133.8 177.00 1174.3 997.3 177.00 1220.6 1043.6 .366 2.908 2.542
TABLE A-7E Properties of Saturated Refrigerant 22 (LiquidVapor): Temperature Table

80 4.781 0.01090 9.6984 10.30 87.24 10.29 106.11 95.82 0.0257 0.2538 80
60 8.834 0.01113 5.4744 5.20 89.16 5.18 103.30 98.12 0.0126 0.2458 60
55 10.187 0.01120 4.7933 3.91 89.64 3.89 102.58 98.68 0.0094 0.2441 55
50 11.701 0.01126 4.2123 2.62 90.12 2.60 101.84 99.24 0.0063 0.2424 50
45 13.387 0.01132 3.7147 1.33 90.59 1.30 101.10 99.80 0.0031 0.2407 45
40 15.261 0.01139 3.2869 0.03 91.07 0.00 100.35 100.35 0.0000 0.2391 40
R-22
35 17.335 0.01145 2.9176 1.27 91.54 1.31 99.59 100.90 0.0031 0.2376 35
30 19.624 0.01152 2.5976 2.58 92.00 2.62 98.82 101.44 0.0061 0.2361 30
25 22.142 0.01159 2.3195 3.89 92.47 3.94 98.04 101.98 0.0092 0.2347 25
20 24.906 0.01166 2.0768 5.21 92.93 5.26 97.24 102.50 0.0122 0.2334 20
15 27.931 0.01173 1.8644 6.53 93.38 6.59 96.43 103.03 0.0152 0.2321 15
10 31.233 0.01181 1.6780 7.86 93.84 7.93 95.61 103.54 0.0182 0.2308 10
5 34.829 0.01188 1.5138 9.19 94.28 9.27 94.78 104.05 0.0211 0.2296 5
0 38.734 0.01196 1.3688 10.53 94.73 10.62 93.93 104.55 0.0240 0.2284 0
5 42.967 0.01204 1.2404 11.88 95.17 11.97 93.06 105.04 0.0270 0.2272 5
10 47.545 0.01212 1.1264 13.23 95.60 13.33 92.18 105.52 0.0298 0.2261 10
15 52.486 0.01220 1.0248 14.58 96.03 14.70 91.29 105.99 0.0327 0.2250 15
20 57.808 0.01229 0.9342 15.95 96.45 16.08 90.38 106.45 0.0356 0.2240 20
25 63.529 0.01237 0.8531 17.31 96.87 17.46 89.45 106.90 0.0384 0.2230 25
30 69.668 0.01246 0.7804 18.69 97.28 18.85 88.50 107.35 0.0412 0.2220 30
35 76.245 0.01255 0.7150 20.07 97.68 20.25 87.53 107.78 0.0441 0.2210 35
40 83.278 0.01265 0.6561 21.46 98.08 21.66 86.54 108.20 0.0468 0.2200 40
45 90.787 0.01275 0.6029 22.86 98.47 23.07 85.53 108.60 0.0496 0.2191 45
50 98.792 0.01285 0.5548 24.27 98.84 24.50 84.49 108.99 0.0524 0.2182 50
55 107.31 0.01295 0.5112 25.68 99.22 25.94 83.44 109.37 0.0552 0.2173 55
60 116.37 0.01306 0.4716 27.10 99.58 27.38 82.36 109.74 0.0579 0.2164 60
65 125.98 0.01317 0.4355 28.53 99.93 28.84 81.25 110.09 0.0607 0.2155 65
70 136.18 0.01328 0.4027 29.98 100.27 30.31 80.11 110.42 0.0634 0.2147 70
75 146.97 0.01340 0.3726 31.43 100.60 31.79 78.95 110.74 0.0661 0.2138 75
80 158.38 0.01352 0.3452 32.89 100.92 33.29 77.75 111.04 0.0689 0.2130 80
85 170.44 0.01365 0.3200 34.36 101.22 34.80 76.53 111.32 0.0716 0.2121 85
90 183.16 0.01378 0.2969 35.85 101.51 36.32 75.26 111.58 0.0743 0.2113 90
95 196.57 0.01392 0.2756 37.35 101.79 37.86 73.96 111.82 0.0771 0.2104 95
100 210.69 0.01407 0.2560 38.86 102.05 39.41 72.63 112.04 0.0798 0.2095 100
105 225.54 0.01422 0.2379 40.39 102.29 40.99 71.24 112.23 0.0825 0.2087 105
110 241.15 0.01438 0.2212 41.94 102.52 42.58 69.82 112.40 0.0852 0.2078 110
115 257.55 0.01455 0.2058 43.50 102.72 44.19 68.34 112.53 0.0880 0.2069 115
120 274.75 0.01472 0.1914 45.08 102.90 45.83 66.81 112.64 0.0907 0.2060 120
140 352.17 0.01555 0.1433 51.62 103.36 52.64 60.06 112.70 0.1019 0.2021 140
Source: Tables A-7E through A-9E are calculated based on equations from A. Kamei and S. W. Beyerlein, A Fundamental Equation for
Chlorodifluoromethane (R-22), Fluid Phase Equilibria, Vol. 80, No. 11, 1992, pp. 7186.
TABLE A-8E Properties of Saturated Refrigerant 22 (LiquidVapor): Pressure Table

lbf/in.2 F vf vg uf ug hf hfg hg sf sg lbf/in.2
5 78.62 0.01091 9.3014 9.95 87.37 9.93 105.92 95.98 0.0248 0.2532 5
10 55.66 0.01119 4.8769 4.08 89.58 4.06 102.67 98.61 0.0098 0.2443 10
15 40.67 0.01138 3.3402 0.21 91.00 0.17 100.45 100.28 0.0004 0.2393 15
20 29.22 0.01153 2.5518 2.78 92.07 2.83 98.70 101.52 0.0066 0.2359 20
25 19.84 0.01166 2.0695 5.25 92.94 5.31 97.22 102.52 0.0123 0.2333 25
30 11.82 0.01178 1.7430 7.38 93.67 7.44 95.91 103.35 0.0171 0.2313 30
R-22
35 4.77 0.01189 1.5068 9.25 94.30 9.33 94.74 104.07 0.0212 0.2295 35
40 1.54 0.01198 1.3277 10.94 94.86 11.03 93.66 104.70 0.0249 0.2280 40
45 7.27 0.01207 1.1870 12.49 95.37 12.59 92.67 105.26 0.0283 0.2267 45
50 12.53 0.01216 1.0735 13.91 95.82 14.03 91.73 105.76 0.0313 0.2256 50
55 17.41 0.01224 0.9799 15.24 96.23 15.36 90.85 106.21 0.0341 0.2245 55
60 21.96 0.01232 0.9014 16.48 96.62 16.62 90.01 106.63 0.0367 0.2236 60
65 26.23 0.01239 0.8345 17.65 96.97 17.80 89.21 107.01 0.0391 0.2227 65
70 30.26 0.01247 0.7768 18.76 97.30 18.92 88.45 107.37 0.0414 0.2219 70
75 34.08 0.01254 0.7265 19.82 97.61 19.99 87.71 107.70 0.0435 0.2212 75
80 37.71 0.01260 0.6823 20.83 97.90 21.01 86.99 108.00 0.0456 0.2205 80
85 41.18 0.01267 0.6431 21.79 98.17 21.99 86.30 108.29 0.0475 0.2198 85
90 44.49 0.01274 0.6081 22.72 98.43 22.93 85.63 108.56 0.0494 0.2192 90
95 47.67 0.01280 0.5766 23.61 98.67 23.84 84.98 108.81 0.0511 0.2186 95
100 50.73 0.01286 0.5482 24.47 98.90 24.71 84.34 109.05 0.0528 0.2181 100
110 56.52 0.01298 0.4988 26.11 99.33 26.37 83.11 109.49 0.0560 0.2170 110
120 61.92 0.01310 0.4573 27.65 99.71 27.94 81.93 109.88 0.0590 0.2161 120
130 67.00 0.01321 0.4220 29.11 100.07 29.43 80.80 110.22 0.0618 0.2152 130
140 71.80 0.01332 0.3915 30.50 100.39 30.84 79.70 110.54 0.0644 0.2144 140
150 76.36 0.01343 0.3649 31.82 100.69 32.20 78.63 110.82 0.0669 0.2136 150
160 80.69 0.01354 0.3416 33.09 100.96 33.49 77.59 111.08 0.0693 0.2128 160
170 84.82 0.01365 0.3208 34.31 101.21 34.74 76.57 111.31 0.0715 0.2121 170
180 88.78 0.01375 0.3023 35.49 101.44 35.95 75.57 111.52 0.0737 0.2115 180
190 92.58 0.01386 0.2857 36.62 101.66 37.11 74.60 111.71 0.0757 0.2108 190
200 96.24 0.01396 0.2706 37.72 101.86 38.24 73.64 111.88 0.0777 0.2102 200
225 104.82 0.01422 0.2386 40.34 102.28 40.93 71.29 112.22 0.0824 0.2087 225
250 112.73 0.01447 0.2126 42.79 102.63 43.46 69.02 112.47 0.0867 0.2073 250
275 120.07 0.01473 0.1912 45.10 102.91 45.85 66.79 112.64 0.0908 0.2060 275
300 126.94 0.01499 0.1732 47.30 103.11 48.14 64.60 112.73 0.0946 0.2047 300
325 133.39 0.01525 0.1577 49.42 103.26 50.33 62.42 112.75 0.0982 0.2034 325
350 139.49 0.01552 0.1444 51.45 103.35 52.46 60.25 112.71 0.1016 0.2022 350
TABLE A-9E Properties of Superheated Refrigerant 22 Vapor

T v u h s v u h s
(Tsat 78.62F) (Tsat 55.66F)
Sat. 9.3014 87.37 95.98 0.2532 4.8769 89.58 98.61 0.2443
70 9.5244 88.31 97.13 0.2562
60 9.7823 89.43 98.48 0.2596
50 10.0391 90.55 99.84 0.2630 4.9522 90.23 99.40 0.2462
40 10.2952 91.69 101.22 0.2663 5.0846 91.39 100.81 0.2496
30 10.5506 92.84 102.61 0.2696 5.2163 92.57 102.23 0.2530
20 10.8054 94.01 104.01 0.2728 5.3472 93.75 103.65 0.2563
R-22
10 11.0596 95.19 105.43 0.2760 5.4775 94.95 105.09 0.2595

0 11.3133 96.39 106.87 0.2791 5.6073 96.16 106.55 0.2627
10 11.5666 97.60 108.31 0.2822 5.7366 97.39 108.01 0.2658
20 11.8195 98.83 109.77 0.2853 5.8655 98.63 109.49 0.2690
30 12.0720 100.07 111.25 0.2884 5.9941 99.88 110.98 0.2720
40 12.3242 101.33 112.74 0.2914 6.1223 101.15 112.49 0.2751
(Tsat 40.67F) (Tsat 29.22F)
Sat. 3.3402 91.00 100.28 0.2393 2.5518 92.07 101.52 0.2359
40 3.3463 91.08 100.38 0.2396
30 3.4370 92.28 101.83 0.2430
20 3.5268 93.49 103.28 0.2463 2.6158 93.21 102.90 0.2391
10 3.6160 94.70 104.75 0.2496 2.6846 94.45 104.39 0.2424
0 3.7046 95.93 106.22 0.2529 2.7528 95.69 105.89 0.2457
10 3.7927 97.17 107.71 0.2561 2.8204 96.95 107.39 0.2490
20 3.8804 98.43 109.20 0.2592 2.8875 98.22 108.91 0.2522
30 3.9677 99.69 110.71 0.2623 2.9542 99.49 110.43 0.2553
40 4.0546 100.97 112.23 0.2654 3.0205 100.78 111.97 0.2584
50 4.1412 102.26 113.76 0.2684 3.0865 102.09 113.52 0.2615
60 4.2275 103.57 115.31 0.2714 3.1522 103.40 115.08 0.2645
70 4.3136 104.89 116.87 0.2744 3.2176 104.73 116.65 0.2675
(Tsat 19.84F) (Tsat 11.82F)
Sat. 2.0695 92.94 102.52 0.2333 1.7430 93.67 103.35 0.2313
10 2.1252 94.18 104.02 0.2367 1.7518 93.91 103.64 0.2319
0 2.1812 95.45 105.54 0.2400 1.7997 95.19 105.19 0.2353
10 2.2365 96.72 107.07 0.2433 1.8470 96.48 106.74 0.2386
20 2.2914 98.00 108.61 0.2466 1.8937 97.78 108.30 0.2419
30 2.3458 99.29 110.15 0.2498 1.9400 99.09 109.86 0.2451
40 2.3998 100.59 111.70 0.2529 1.9858 100.40 111.43 0.2483
50 2.4535 101.91 113.27 0.2560 2.0313 101.73 113.01 0.2514
60 2.5068 103.23 114.84 0.2590 2.0764 103.06 114.60 0.2545
70 2.5599 104.57 116.42 0.2621 2.1213 104.41 116.19 0.2576
80 2.6127 105.92 118.01 0.2650 2.1659 105.77 117.80 0.2606
90 2.6654 107.28 119.62 0.2680 2.2103 107.13 119.41 0.2635
100 2.7178 108.65 121.24 0.2709 2.2545 108.52 121.04 0.2665

T v u h s v u h s
(Tsat 1.54F) (Tsat 12.53F)
Sat. 1.3277 94.86 104.70 0.2280 1.0735 95.82 105.76 0.2256
10 1.3593 95.99 106.06 0.2310
20 1.3960 97.33 107.67 0.2343 1.0965 96.85 107.00 0.2282
30 1.4321 98.66 109.27 0.2376 1.1268 98.22 108.65 0.2316
40 1.4678 100.01 110.88 0.2409 1.1565 99.59 110.30 0.2349
50 1.5032 101.35 112.49 0.2441 1.1858 100.97 111.95 0.2382
60 1.5381 102.71 114.10 0.2472 1.2147 102.35 113.60 0.2414
R-22
70 1.5728 104.08 115.73 0.2503 1.2433 103.74 115.25 0.2445
80 1.6071 105.45 117.36 0.2534 1.2716 105.13 116.90 0.2476
90 1.6413 106.84 118.99 0.2564 1.2996 106.53 118.57 0.2507
100 1.6752 108.23 120.64 0.2593 1.3274 107.95 120.24 0.2537
110 1.7089 109.64 122.30 0.2623 1.3549 109.37 121.91 0.2567
120 1.7424 111.06 123.97 0.2652 1.3823 110.80 123.60 0.2596
(Tsat 21.96F) (Tsat 30.26F)
Sat. 0.9014 96.62 106.63 0.2236 0.7768 97.30 107.37 0.2219
30 0.9226 97.75 108.00 0.2264
40 0.9485 99.16 109.70 0.2298 0.7994 98.71 109.07 0.2254
50 0.9739 100.57 111.39 0.2332 0.8221 100.15 110.81 0.2288
60 0.9988 101.98 113.07 0.2365 0.8443 101.59 112.53 0.2321
70 1.0234 103.39 114.76 0.2397 0.8660 103.03 114.25 0.2354
80 1.0476 104.80 116.44 0.2428 0.8874 104.46 115.97 0.2386
90 1.0716 106.22 118.13 0.2459 0.9086 105.90 117.68 0.2418
100 1.0953 107.65 119.82 0.2490 0.9294 107.35 119.40 0.2449
110 1.1188 109.09 121.52 0.2520 0.9500 108.80 121.12 0.2479
120 1.1421 110.53 123.22 0.2549 0.9704 110.26 122.84 0.2509
130 1.1653 111.99 124.93 0.2579 0.9907 111.73 124.57 0.2539
140 1.1883 113.45 126.65 0.2608 1.0107 113.21 126.31 0.2568
(Tsat 37.71F) (Tsat 44.49F)
Sat. 0.6823 97.90 108.00 0.2205 0.6081 98.43 108.56 0.2192
40 0.6871 98.24 108.42 0.2213
50 0.7079 99.72 110.20 0.2248 0.6186 99.26 109.57 0.2212
60 0.7280 101.19 111.97 0.2283 0.6373 100.77 111.39 0.2247
70 0.7478 102.65 113.73 0.2316 0.6555 102.27 113.19 0.2282
80 0.7671 104.11 115.48 0.2349 0.6733 103.76 114.98 0.2315
90 0.7861 105.58 117.22 0.2381 0.6907 105.24 116.75 0.2348
100 0.8048 107.04 118.97 0.2412 0.7078 106.73 118.52 0.2380
110 0.8233 108.51 120.71 0.2443 0.7246 108.22 120.29 0.2411
120 0.8416 109.99 122.45 0.2474 0.7412 109.71 122.06 0.2442
130 0.8596 111.47 124.20 0.2504 0.7576 111.20 123.83 0.2472
140 0.8775 112.96 125.96 0.2533 0.7739 112.71 125.60 0.2502
150 0.8953 114.46 127.72 0.2562 0.7899 114.22 127.38 0.2531

T v u h s v u h s
(Tsat 50.73F) (Tsat 61.92F)
Sat. 0.5482 98.90 109.05 0.2181 0.4573 99.71 109.88 0.2161
60 0.5645 100.33 110.79 0.2214
80 0.5980 103.38 114.46 0.2284 0.4846 102.60 113.37 0.2227
100 0.6300 106.40 118.07 0.2349 0.5130 105.73 117.13 0.2295
120 0.6609 109.42 121.66 0.2412 0.5400 108.83 120.83 0.2360
140 0.6908 112.45 125.24 0.2473 0.5661 111.92 124.50 0.2422
160 0.7201 115.50 128.83 0.2532 0.5914 115.02 128.16 0.2482
R-22
180 0.7489 118.58 132.45 0.2589 0.6161 118.15 131.84 0.2541

200 0.7771 121.69 136.08 0.2645 0.6404 121.30 135.53 0.2597
220 0.8051 124.84 139.75 0.2700 0.6642 124.48 139.24 0.2653
240 0.8327 128.04 143.45 0.2754 0.6878 127.69 142.98 0.2707
260 0.8600 131.27 147.19 0.2806 0.7110 130.95 146.75 0.2760
280 0.8871 134.54 150.97 0.2858 0.7340 134.24 150.55 0.2812
300 0.9140 137.85 154.78 0.2909 0.7568 137.57 154.39 0.2863

(Tsat 71.80F) (Tsat 80.69F)
Sat. 0.3915 100.39 110.54 0.2144 0.3416 100.96 111.08 0.2128
80 0.4028 101.76 112.20 0.2175
100 0.4289 105.02 116.14 0.2246 0.3653 104.26 115.08 0.2201
120 0.4534 108.21 119.96 0.2313 0.3881 107.56 119.06 0.2271
140 0.4768 111.37 123.73 0.2377 0.4095 110.81 122.94 0.2337
160 0.4993 114.53 127.48 0.2439 0.4301 114.03 126.77 0.2400
180 0.5212 117.70 131.21 0.2498 0.4499 117.25 130.57 0.2460
200 0.5426 120.89 134.96 0.2556 0.4692 120.47 134.37 0.2518
220 0.5636 124.10 138.71 0.2612 0.4880 123.72 138.18 0.2575
240 0.5842 127.35 142.49 0.2666 0.5065 126.99 142.00 0.2631
260 0.6045 130.62 146.30 0.2720 0.5246 130.30 145.84 0.2685
280 0.6246 133.94 150.13 0.2773 0.5425 133.63 149.70 0.2738
300 0.6445 137.29 154.00 0.2824 0.5602 137.00 153.60 0.2790
320 0.6642 140.68 157.89 0.2875 0.5777 140.41 157.62 0.2841

(Tsat 88.78F) (Tsat 96.24F)
Sat. 0.3023 101.44 111.52 0.2115 0.2706 101.86 111.88 0.2102
100 0.3154 103.44 113.95 0.2159 0.2748 102.56 112.73 0.2117
120 0.3369 106.88 118.11 0.2231 0.2957 106.15 117.10 0.2194
140 0.3570 110.21 122.11 0.2299 0.3148 109.59 121.25 0.2264
160 0.3761 113.50 126.04 0.2364 0.3327 112.96 125.28 0.2330
180 0.3943 116.78 129.92 0.2425 0.3497 116.29 129.25 0.2393
200 0.4120 120.05 133.78 0.2485 0.3661 119.61 133.17 0.2454
220 0.4292 123.33 137.64 0.2542 0.3820 122.94 137.08 0.2512
240 0.4459 126.64 141.50 0.2598 0.3975 126.27 140.99 0.2569
260 0.4624 129.96 145.38 0.2653 0.4126 129.63 144.91 0.2624
280 0.4786 133.32 149.28 0.2706 0.4275 133.01 148.84 0.2678
300 0.4946 136.71 153.20 0.2759 0.4422 136.42 152.79 0.2731
320 0.5104 140.13 157.15 0.2810 0.4566 139.86 156.77 0.2782
340 0.5260 143.59 161.12 0.2860 0.4709 143.33 160.77 0.2833

T v u h s v u h s
(Tsat 104.82F) (Tsat 112.73F)
Sat. 0.2386 102.28 112.22 0.2087 0.2126 102.63 112.47 0.2073
120 0.2539 105.17 115.75 0.2149 0.2198 104.10 114.27 0.2104
140 0.2722 108.78 120.12 0.2223 0.2378 107.90 118.91 0.2183
160 0.2891 112.26 124.30 0.2291 0.2540 111.51 123.27 0.2255
180 0.3050 115.67 128.38 0.2356 0.2690 115.02 127.48 0.2321
200 0.3202 119.06 132.40 0.2418 0.2833 118.48 131.59 0.2385
220 0.3348 122.43 136.38 0.2477 0.2969 121.91 135.66 0.2445
R-22
240 0.3490 125.81 140.35 0.2535 0.3101 125.33 139.69 0.2504
260 0.3628 129.20 144.32 0.2591 0.3229 128.76 143.71 0.2560
280 0.3764 132.61 148.29 0.2645 0.3354 132.21 147.73 0.2616
300 0.3896 136.05 152.28 0.2699 0.3476 135.67 151.76 0.2669
320 0.4027 139.51 156.29 0.2751 0.3596 139.16 155.81 0.2722
340 0.4156 143.00 160.32 0.2802 0.3715 142.67 159.87 0.2773
360 0.4284 146.33 164.38 0.2852 0.3831 146.22 163.95 0.2824

(Tsat 120.07F) (Tsat 126.94F)
Sat. 0.1912 102.91 112.64 0.2060 0.1732 103.11 112.73 0.2047
140 0.2092 106.96 117.61 0.2144 0.1849 105.93 116.20 0.2105
160 0.2250 110.73 122.19 0.2219 0.2006 109.89 121.04 0.2185
180 0.2395 144.35 126.54 0.2288 0.2146 133.64 125.56 0.2257
200 0.2530 117.88 130.77 0.2353 0.2276 117.26 129.91 0.2324
220 0.2659 121.38 134.91 0.2415 0.2399 120.83 134.15 0.2387
240 0.2782 124.85 139.02 0.2475 0.2516 124.35 138.33 0.2447
260 0.2902 128.32 143.10 0.2532 0.2629 127.87 142.47 0.2506
280 0.3018 131.80 147.17 0.2588 0.2739 131.38 146.59 0.2562
300 0.3132 135.29 151.24 0.2642 0.2845 134.90 150.71 0.2617
320 0.3243 138.80 155.32 0.2695 0.2949 138.44 154.83 0.2671
340 0.3353 142.34 159.41 0.2747 0.3051 142.00 158.95 0.2723
360 0.3461 145.90 163.53 0.2798 0.3152 145.58 163.09 0.2774

(Tsat 133.39F) (Tsat 139.49F)
Sat. 0.1577 103.26 112.75 0.2034 0.1444 103.35 112.71 0.2022
140 0.1637 104.78 114.63 0.2066 0.1448 103.48 112.86 0.2024
160 0.1796 109.00 119.81 0.2151 0.1605 107.90 118.30 0.2113
180 0.1934 112.89 124.53 0.2226 0.1747 112.06 123.38 0.2194
200 0.2061 116.62 129.02 0.2295 0.1874 115.95 128.10 0.2267
220 0.2179 120.26 133.37 0.2360 0.1987 119.65 132.53 0.2333
240 0.2291 123.84 137.63 0.2422 0.2095 123.31 136.89 0.2396
260 0.2398 127.40 141.83 0.2481 0.2199 126.93 141.18 0.2457
280 0.2501 130.96 146.01 0.2538 0.2297 130.52 145.41 0.2514
300 0.2602 134.51 150.17 0.2593 0.2393 134.12 149.62 0.2571
320 0.2700 138.08 154.33 0.2647 0.2486 137.71 153.82 0.2626
340 0.2796 141.66 158.49 0.2700 0.2577 141.32 158.02 0.2679
360 0.2891 145.26 162.66 0.2752 0.2666 144.95 162.23 0.2730
380 0.2983 148.89 166.85 0.2802 0.2754 148.59 166.43 0.2781
TABLE A-10E Properties of Saturated Refrigerant 134a (LiquidVapor): Temperature Table

40 7.490 0.01130 5.7173 0.02 87.90 0.00 95.82 95.82 0.0000 0.2283 40
30 9.920 0.01143 4.3911 2.81 89.26 2.83 94.49 97.32 0.0067 0.2266 30
20 12.949 0.01156 3.4173 5.69 90.62 5.71 93.10 98.81 0.0133 0.2250 20
15 14.718 0.01163 3.0286 7.14 91.30 7.17 92.38 99.55 0.0166 0.2243 15
10 16.674 0.01170 2.6918 8.61 91.98 8.65 91.64 100.29 0.0199 0.2236 10
5 18.831 0.01178 2.3992 10.09 92.66 10.13 90.89 101.02 0.0231 0.2230 5
0 21.203 0.01185 2.1440 11.58 93.33 11.63 90.12 101.75 0.0264 0.2224 0
5 23.805 0.01193 1.9208 13.09 94.01 13.14 89.33 102.47 0.0296 0.2219 5
10 26.651 0.01200 1.7251 14.60 94.68 14.66 88.53 103.19 0.0329 0.2214 10
15 29.756 0.01208 1.5529 16.13 95.35 16.20 87.71 103.90 0.0361 0.2209 15
20 33.137 0.01216 1.4009 17.67 96.02 17.74 86.87 104.61 0.0393 0.2205 20
R-134a
25 36.809 0.01225 1.2666 19.22 96.69 19.30 86.02 105.32 0.0426 0.2200 25
30 40.788 0.01233 1.1474 20.78 97.35 20.87 85.14 106.01 0.0458 0.2196 30
40 49.738 0.01251 0.9470 23.94 98.67 24.05 83.34 107.39 0.0522 0.2189 40
50 60.125 0.01270 0.7871 27.14 99.98 27.28 81.46 108.74 0.0585 0.2183 50
60 72.092 0.01290 0.6584 30.39 101.27 30.56 79.49 110.05 0.0648 0.2178 60
70 85.788 0.01311 0.5538 33.68 102.54 33.89 77.44 111.33 0.0711 0.2173 70
80 101.37 0.01334 0.4682 37.02 103.78 37.27 75.29 112.56 0.0774 0.2169 80
85 109.92 0.01346 0.4312 38.72 104.39 38.99 74.17 113.16 0.0805 0.2167 85
90 118.99 0.01358 0.3975 40.42 105.00 40.72 73.03 113.75 0.0836 0.2165 90
95 128.62 0.01371 0.3668 42.14 105.60 42.47 71.86 114.33 0.0867 0.2163 95
100 138.83 0.01385 0.3388 43.87 106.18 44.23 70.66 114.89 0.0898 0.2161 100
105 149.63 0.01399 0.3131 45.62 106.76 46.01 69.42 115.43 0.0930 0.2159 105
110 161.04 0.01414 0.2896 47.39 107.33 47.81 68.15 115.96 0.0961 0.2157 110
115 173.10 0.01429 0.2680 49.17 107.88 49.63 66.84 116.47 0.0992 0.2155 115
120 185.82 0.01445 0.2481 50.97 108.42 51.47 65.48 116.95 0.1023 0.2153 120
140 243.86 0.01520 0.1827 58.39 110.41 59.08 59.57 118.65 0.1150 0.2143 140
160 314.63 0.01617 0.1341 66.26 111.97 67.20 52.58 119.78 0.1280 0.2128 160
180 400.22 0.01758 0.0964 74.83 112.77 76.13 43.78 119.91 0.1417 0.2101 180
200 503.52 0.02014 0.0647 84.90 111.66 86.77 30.92 117.69 0.1575 0.2044 200
210 563.51 0.02329 0.0476 91.84 108.48 94.27 19.18 113.45 0.1684 0.1971 210
Source: Tables A-10E through A-12E are calculated based on equations from D. P. Wilson and R. S. Basu, Thermodynamic Properties of a New
Stratospherically Safe Working FluidRefrigerant 134a, ASHRAE Trans., Vol. 94, Pt. 2, 1988, pp. 20952118.
TABLE A-11E Properties of Saturated Refrigerant 134a (LiquidVapor): Pressure Table

5 53.48 0.01113 8.3508 3.74 86.07 3.73 97.53 93.79 0.0090 0.2311 5
10 29.71 0.01143 4.3581 2.89 89.30 2.91 94.45 97.37 0.0068 0.2265 10
15 14.25 0.01164 2.9747 7.36 91.40 7.40 92.27 99.66 0.0171 0.2242 15
20 2.48 0.01181 2.2661 10.84 93.00 10.89 90.50 101.39 0.0248 0.2227 20
30 15.38 0.01209 1.5408 16.24 95.40 16.31 87.65 103.96 0.0364 0.2209 30
40 29.04 0.01232 1.1692 20.48 97.23 20.57 85.31 105.88 0.0452 0.2197 40
50 40.27 0.01252 0.9422 24.02 98.71 24.14 83.29 107.43 0.0523 0.2189 50
60 49.89 0.01270 0.7887 27.10 99.96 27.24 81.48 108.72 0.0584 0.2183 60
70 58.35 0.01286 0.6778 29.85 101.05 30.01 79.82 109.83 0.0638 0.2179 70
80 65.93 0.01302 0.5938 32.33 102.02 32.53 78.28 110.81 0.0686 0.2175 80
90 72.83 0.01317 0.5278 34.62 102.89 34.84 76.84 111.68 0.0729 0.2172 90
R-134a
100 79.17 0.01332 0.4747 36.75 103.68 36.99 75.47 112.46 0.0768 0.2169 100
120 90.54 0.01360 0.3941 40.61 105.06 40.91 72.91 113.82 0.0839 0.2165 120
140 100.56 0.01386 0.3358 44.07 106.25 44.43 70.52 114.95 0.0902 0.2161 140
160 109.56 0.01412 0.2916 47.23 107.28 47.65 68.26 115.91 0.0958 0.2157 160
180 117.74 0.01438 0.2569 50.16 108.18 50.64 66.10 116.74 0.1009 0.2154 180
200 125.28 0.01463 0.2288 52.90 108.98 53.44 64.01 117.44 0.1057 0.2151 200
220 132.27 0.01489 0.2056 55.48 109.68 56.09 61.96 118.05 0.1101 0.2147 220
240 138.79 0.01515 0.1861 57.93 110.30 58.61 59.96 118.56 0.1142 0.2144 240
260 144.92 0.01541 0.1695 60.28 110.84 61.02 57.97 118.99 0.1181 0.2140 260
280 150.70 0.01568 0.1550 62.53 111.31 63.34 56.00 119.35 0.1219 0.2136 280
300 156.17 0.01596 0.1424 64.71 111.72 65.59 54.03 119.62 0.1254 0.2132 300
350 168.72 0.01671 0.1166 69.88 112.45 70.97 49.03 120.00 0.1338 0.2118 350
400 179.95 0.01758 0.0965 74.81 112.77 76.11 43.80 119.91 0.1417 0.2102 400
450 190.12 0.01863 0.0800 79.63 112.60 81.18 38.08 119.26 0.1493 0.2079 450
500 199.38 0.02002 0.0657 84.54 111.76 86.39 31.44 117.83 0.1570 0.2047 500
TABLE A-12E Properties of Superheated Refrigerant 134a Vapor

T v u h s v u h s
(Tsat 29.71F) (Tsat 14.25F)
Sat. 4.3581 89.30 97.37 0.2265 2.9747 91.40 99.66 0.2242
20 4.4718 90.89 99.17 0.2307
0 4.7026 94.24 102.94 0.2391 3.0893 93.84 102.42 0.2303
20 4.9297 97.67 106.79 0.2472 3.2468 97.33 106.34 0.2386
40 5.1539 101.19 110.72 0.2553 3.4012 100.89 110.33 0.2468
60 5.3758 104.80 114.74 0.2632 3.5533 104.54 114.40 0.2548
80 5.5959 108.50 118.85 0.2709 3.7034 108.28 118.56 0.2626
100 5.8145 112.29 123.05 0.2786 3.8520 112.10 122.79 0.2703
120 6.0318 116.18 127.34 0.2861 3.9993 116.01 127.11 0.2779
140 6.2482 120.16 131.72 0.2935 4.1456 120.00 131.51 0.2854
160 6.4638 124.23 136.19 0.3009 4.2911 124.09 136.00 0.2927
180 6.6786 128.38 140.74 0.3081 4.4359 128.26 140.57 0.3000
200 6.8929 132.63 145.39 0.3152 4.5801 132.52 145.23 0.3072
R-134a
(Tsat 2.48F) (Tsat 15.38F)
Sat. 2.2661 93.00 101.39 0.2227 1.5408 95.40 103.96 0.2209
0 2.2816 93.43 101.88 0.2238
20 2.4046 96.98 105.88 0.2323 1.5611 96.26 104.92 0.2229
40 2.5244 100.59 109.94 0.2406 1.6465 99.98 109.12 0.2315
60 2.6416 104.28 114.06 0.2487 1.7293 103.75 113.35 0.2398
80 2.7569 108.05 118.25 0.2566 1.8098 107.59 117.63 0.2478
100 2.8705 111.90 122.52 0.2644 1.8887 111.49 121.98 0.2558
120 2.9829 115.83 126.87 0.2720 1.9662 115.47 126.39 0.2635
140 3.0942 119.85 131.30 0.2795 2.0426 119.53 130.87 0.2711
160 3.2047 123.95 135.81 0.2869 2.1181 123.66 135.42 0.2786
180 3.3144 128.13 140.40 0.2922 2.1929 127.88 140.05 0.2859
200 3.4236 132.40 145.07 0.3014 2.2671 132.17 144.76 0.2932
220 3.5323 136.76 149.83 0.3085 2.3407 136.55 149.54 0.3003
(Tsat 29.04F) (Tsat 40.27F)
Sat. 1.1692 97.23 105.88 0.2197 0.9422 98.71 107.43 0.2189
40 1.2065 99.33 108.26 0.2245
60 1.2723 103.20 112.62 0.2331 0.9974 102.62 111.85 0.2276
80 1.3357 107.11 117.00 0.2414 1.0508 106.62 116.34 0.2361
100 1.3973 111.08 121.42 0.2494 1.1022 110.65 120.85 0.2443
120 1.4575 115.11 125.90 0.2573 1.1520 114.74 125.39 0.2523
140 1.5165 119.21 130.43 0.2650 1.2007 118.88 129.99 0.2601
160 1.5746 123.38 135.03 0.2725 1.2484 123.08 134.64 0.2677
180 1.6319 127.62 139.70 0.2799 1.2953 127.36 139.34 0.2752
200 1.6887 131.94 144.44 0.2872 1.3415 131.71 144.12 0.2825
220 1.7449 136.34 149.25 0.2944 1.3873 136.12 148.96 0.2897
240 1.8006 140.81 154.14 0.3015 1.4326 140.61 153.87 0.2969
260 1.8561 145.36 159.10 0.3085 1.4775 145.18 158.85 0.3039
280 1.9112 149.98 164.13 0.3154 1.5221 149.82 163.90 0.3108

T v u h s v u h s
(Tsat 49.89F) (Tsat 58.35F)
Sat. 0.7887 99.96 108.72 0.2183 0.6778 101.05 109.83 0.2179
60 0.8135 102.03 111.06 0.2229 0.6814 101.40 110.23 0.2186
80 0.8604 106.11 115.66 0.2316 0.7239 105.58 114.96 0.2276
100 0.9051 110.21 120.26 0.2399 0.7640 109.76 119.66 0.2361
120 0.9482 114.35 124.88 0.2480 0.8023 113.96 124.36 0.2444
140 0.9900 118.54 129.53 0.2559 0.8393 118.20 129.07 0.2524
160 1.0308 122.79 134.23 0.2636 0.8752 122.49 133.82 0.2601
180 1.0707 127.10 138.98 0.2712 0.9103 126.83 138.62 0.2678
200 1.1100 131.47 143.79 0.2786 0.9446 131.23 143.46 0.2752
220 1.1488 135.91 148.66 0.2859 0.9784 135.69 148.36 0.2825
240 1.1871 140.42 153.60 0.2930 1.0118 140.22 153.33 0.2897
260 1.2251 145.00 158.60 0.3001 1.0448 144.82 158.35 0.2968
280 1.2627 149.65 163.67 0.3070 1.0774 149.48 163.44 0.3038
R-134a
300 1.3001 154.38 168.81 0.3139 1.1098 154.22 168.60 0.3107
(Tsat 65.93F) (Tsat 72.83F)
Sat. 0.5938 102.02 110.81 0.2175 0.5278 102.89 111.68 0.2172
80 0.6211 105.03 114.23 0.2239 0.5408 104.46 113.47 0.2205
100 0.6579 109.30 119.04 0.2327 0.5751 108.82 118.39 0.2295
120 0.6927 113.56 123.82 0.2411 0.6073 113.15 123.27 0.2380
140 0.7261 117.85 128.60 0.2492 0.6380 117.50 128.12 0.2463
160 0.7584 122.18 133.41 0.2570 0.6675 121.87 132.98 0.2542
180 0.7898 126.55 138.25 0.2647 0.6961 126.28 137.87 0.2620
200 0.8205 130.98 143.13 0.2722 0.7239 130.73 142.79 0.2696
220 0.8506 135.47 148.06 0.2796 0.7512 135.25 147.76 0.2770
240 0.8803 140.02 153.05 0.2868 0.7779 139.82 152.77 0.2843
260 0.9095 144.63 158.10 0.2940 0.8043 144.45 157.84 0.2914
280 0.9384 149.32 163.21 0.3010 0.8303 149.15 162.97 0.2984
300 0.9671 154.06 168.38 0.3079 0.8561 153.91 168.16 0.3054
320 0.9955 158.88 173.62 0.3147 0.8816 158.73 173.42 0.3122

(Tsat 79.17F) (Tsat 90.54F)
Sat. 0.4747 103.68 112.46 0.2169 0.3941 105.06 113.82 0.2165
80 0.4761 103.87 112.68 0.2173
100 0.5086 108.32 117.73 0.2265 0.4080 107.26 116.32 0.2210
120 0.5388 112.73 122.70 0.2352 0.4355 111.84 121.52 0.2301
140 0.5674 117.13 127.63 0.2436 0.4610 116.37 126.61 0.2387
160 0.5947 121.55 132.55 0.2517 0.4852 120.89 131.66 0.2470
180 0.6210 125.99 137.49 0.2595 0.5082 125.42 136.70 0.2550
200 0.6466 130.48 142.45 0.2671 0.5305 129.97 141.75 0.2628
220 0.6716 135.02 147.45 0.2746 0.5520 134.56 146.82 0.2704
240 0.6960 139.61 152.49 0.2819 0.5731 139.20 151.92 0.2778
260 0.7201 144.26 157.59 0.2891 0.5937 143.89 157.07 0.2850
280 0.7438 148.98 162.74 0.2962 0.6140 148.63 162.26 0.2921
300 0.7672 153.75 167.95 0.3031 0.6339 153.43 167.51 0.2991
320 0.7904 158.59 173.21 0.3099 0.6537 158.29 172.81 0.3060

T v u h s v u h s
(Tsat 100.56F) (Tsat 109.55F)
Sat. 0.3358 106.25 114.95 0.2161 0.2916 107.28 115.91 0.2157
120 0.3610 110.90 120.25 0.2254 0.3044 109.88 118.89 0.2209
140 0.3846 115.58 125.54 0.2344 0.3269 114.73 124.41 0.2303
160 0.4066 120.21 130.74 0.2429 0.3474 119.49 129.78 0.2391
180 0.4274 124.82 135.89 0.2511 0.3666 124.20 135.06 0.2475
200 0.4474 129.44 141.03 0.2590 0.3849 128.90 140.29 0.2555
220 0.4666 134.09 146.18 0.2667 0.4023 133.61 145.52 0.2633
240 0.4852 138.77 151.34 0.2742 0.4192 138.34 150.75 0.2709
260 0.5034 143.50 156.54 0.2815 0.4356 143.11 156.00 0.2783
280 0.5212 148.28 161.78 0.2887 0.4516 147.92 161.29 0.2856
300 0.5387 153.11 167.06 0.2957 0.4672 152.78 166.61 0.2927
320 0.5559 157.99 172.39 0.3026 0.4826 157.69 171.98 0.2996
340 0.5730 162.93 177.78 0.3094 0.4978 162.65 177.39 0.3065
R-134a
360 0.5898 167.93 183.21 0.3162 0.5128 167.67 182.85 0.3132

(Tsat 117.74F) (Tsat 125.28F)
Sat. 0.2569 108.18 116.74 0.2154 0.2288 108.98 117.44 0.2151
120 0.2595 108.77 117.41 0.2166
140 0.2814 113.83 123.21 0.2264 0.2446 112.87 121.92 0.2226
160 0.3011 118.74 128.77 0.2355 0.2636 117.94 127.70 0.2321
180 0.3191 123.56 134.19 0.2441 0.2809 122.88 133.28 0.2410
200 0.3361 128.34 139.53 0.2524 0.2970 127.76 138.75 0.2494
220 0.3523 133.11 144.84 0.2603 0.3121 132.60 144.15 0.2575
240 0.3678 137.90 150.15 0.2680 0.3266 137.44 149.53 0.2653
260 0.3828 142.71 155.46 0.2755 0.3405 142.30 154.90 0.2728
280 0.3974 147.55 160.79 0.2828 0.3540 147.18 160.28 0.2802
300 0.4116 152.44 166.15 0.2899 0.3671 152.10 165.69 0.2874
320 0.4256 157.38 171.55 0.2969 0.3799 157.07 171.13 0.2945
340 0.4393 162.36 177.00 0.3038 0.3926 162.07 176.60 0.3014
360 0.4529 167.40 182.49 0.3106 0.4050 167.13 182.12 0.3082

(Tsat 156.17F) (Tsat 179.95F)
Sat. 0.1424 111.72 119.62 0.2132 0.0965 112.77 119.91 0.2102
160 0.1462 112.95 121.07 0.2155
180 0.1633 118.93 128.00 0.2265 0.0965 112.79 119.93 0.2102
200 0.1777 124.47 134.34 0.2363 0.1143 120.14 128.60 0.2235
220 0.1905 129.79 140.36 0.2453 0.1275 126.35 135.79 0.2343
240 0.2021 134.99 146.21 0.2537 0.1386 132.12 142.38 0.2438
260 0.2130 140.12 151.95 0.2618 0.1484 137.65 148.64 0.2527
280 0.2234 145.23 157.63 0.2696 0.1575 143.06 154.72 0.2610
300 0.2333 150.33 163.28 0.2772 0.1660 148.39 160.67 0.2689
320 0.2428 155.44 168.92 0.2845 0.1740 153.69 166.57 0.2766
340 0.2521 160.57 174.56 0.2916 0.1816 158.97 172.42 0.2840
360 0.2611 165.74 180.23 0.2986 0.1890 164.26 178.26 0.2912
380 0.2699 170.94 185.92 0.3055 0.1962 169.57 184.09 0.2983
400 0.2786 176.18 191.64 0.3122 0.2032 174.90 189.94 0.3051
TABLE A-13E Properties of Saturated Ammonia (LiquidVapor): Temperature Table

60 5.548 0.02278 44.7537 21.005 543.61 20.97 610.56 589.58 0.0512 1.4765 60
55 6.536 0.02288 38.3991 15.765 545.11 15.73 607.31 591.58 0.0381 1.4627 55
50 7.664 0.02299 33.0880 10.525 546.59 10.49 604.04 593.54 0.0253 1.4492 50
45 8.949 0.02310 28.6284 5.295 548.04 5.25 600.72 595.48 0.0126 1.4361 45
40 10.405 0.02322 24.8672 0.045 549.46 0.00 597.37 597.37 0.0000 1.4235 40
35 12.049 0.02333 21.6812 5.20 550.86 5.26 593.98 599.24 0.0124 1.4111 35
30 13.899 0.02345 18.9715 10.46 552.24 10.52 590.54 601.06 0.0247 1.3992 30
25 15.972 0.02357 16.6577 15.73 553.59 15.80 587.05 602.85 0.0369 1.3875 25
20 18.290 0.02369 14.6744 21.01 554.91 21.09 583.51 604.61 0.0490 1.3762 20
15 20.871 0.02381 12.9682 26.31 556.20 26.40 579.92 606.32 0.0610 1.3652 15
10 23.738 0.02393 11.4951 31.63 557.46 31.73 576.26 607.99 0.0729 1.3544 10
5 26.912 0.02406 10.2190 36.96 558.70 37.08 572.54 609.62 0.0847 1.3440 5
0 30.416 0.02419 9.1100 42.32 559.91 42.45 568.76 611.22 0.0964 1.3338 0
5 34.275 0.02432 8.1430 47.69 561.08 47.85 564.92 612.76 0.1080 1.3238 5
10 38.512 0.02446 7.2974 53.09 562.23 53.27 561.00 614.27 0.1196 1.3141 10
15 43.153 0.02460 6.5556 58.52 563.34 58.72 557.01 615.73 0.1311 1.3046 15
20 48.224 0.02474 5.9032 63.97 564.43 64.19 552.95 617.14 0.1425 1.2953 20
Ammonia
25 53.752 0.02488 5.3278 69.43 565.48 69.68 548.82 618.51 0.1539 1.2862 25
30 59.765 0.02503 4.8188 74.93 566.49 75.20 544.62 619.82 0.1651 1.2774 30
35 66.291 0.02517 4.3675 80.44 567.48 80.75 540.34 621.09 0.1764 1.2687 35
40 73.359 0.02533 3.9664 85.98 568.42 86.33 535.97 622.30 0.1875 1.2602 40
45 81.000 0.02548 3.6090 91.55 569.33 91.93 531.54 623.46 0.1986 1.2518 45
50 89.242 0.02564 3.2897 97.13 570.21 97.55 527.02 624.57 0.2096 1.2436 50
55 98.118 0.02581 3.0040 102.73 571.04 103.20 522.42 625.62 0.2205 1.2356 55
60 107.66 0.02597 2.7476 108.35 571.83 108.87 517.74 626.61 0.2314 1.2277 60
65 117.90 0.02614 2.5171 113.99 572.59 114.56 512.97 627.54 0.2422 1.2199 65
70 128.87 0.02632 2.3095 119.65 573.29 120.28 508.12 628.40 0.2530 1.2123 70
75 140.60 0.02650 2.1220 125.33 573.95 126.02 503.18 629.20 0.2636 1.2048 75
80 153.13 0.02668 1.9524 131.02 574.57 131.78 498.15 629.93 0.2742 1.1973 80
85 166.50 0.02687 1.7988 136.73 575.13 137.56 493.03 630.59 0.2848 1.1900 85
90 180.73 0.02707 1.6593 142.46 575.65 143.37 487.81 631.18 0.2953 1.1827 90
95 195.87 0.02727 1.5324 148.21 576.10 149.20 482.49 631.68 0.3057 1.1756 95
100 211.96 0.02747 1.4168 153.98 576.51 155.05 477.06 632.11 0.3161 1.1685 100
105 229.02 0.02768 1.3113 159.76 576.85 160.94 471.52 632.46 0.3264 1.1614 105
110 247.10 0.02790 1.2149 165.58 577.13 166.85 465.86 632.71 0.3366 1.1544 110
115 266.24 0.02813 1.1266 171.41 577.34 172.80 460.08 632.88 0.3469 1.1475 115
120 286.47 0.02836 1.0456 177.28 577.48 178.79 454.16 632.95 0.3570 1.1405 120
Source: Tables A-13E through A-15E are calculated based on equations from L. Haar and J. S. Gallagher, Thermodynamic Properties of
Ammonia, J. Phys. Chem. Reference Data, Vol. 7, 1978, pp. 635792.
TABLE A-14E Properties of Saturated Ammonia (LiquidVapor): Pressure Table

5 63.10 0.02271 49.320 24.24 542.67 24.22 612.56 588.33 0.0593 1.4853 5
6 57.63 0.02283 41.594 18.51 544.32 18.49 609.02 590.54 0.0450 1.4699 6
7 52.86 0.02293 36.014 13.52 545.74 13.49 605.92 592.42 0.0326 1.4569 7
8 48.63 0.02302 31.790 9.09 546.98 9.06 603.13 594.08 0.0218 1.4456 8
9 44.81 0.02311 28.477 5.09 548.09 5.05 600.60 595.55 0.0121 1.4357 9
10 41.33 0.02319 25.807 1.44 549.09 1.40 598.27 596.87 0.0033 1.4268 10
12 35.14 0.02333 21.764 5.06 550.82 5.11 594.08 599.18 0.0121 1.4115 12
14 29.74 0.02345 18.843 10.73 552.31 10.79 590.36 601.16 0.0254 1.3986 14
16 24.94 0.02357 16.631 15.80 553.60 15.87 587.01 602.88 0.0371 1.3874 16
18 20.60 0.02367 14.896 20.38 554.75 20.46 583.94 604.40 0.0476 1.3775 18
20 16.63 0.02377 13.497 24.58 555.78 24.67 581.10 605.76 0.0571 1.3687 20
25 7.95 0.02399 10.950 33.81 557.97 33.92 574.75 608.67 0.0777 1.3501 25
30 0.57 0.02418 9.229 41.71 559.77 41.84 569.20 611.04 0.0951 1.3349 30
35 5.89 0.02435 7.984 48.65 561.29 48.81 564.22 613.03 0.1101 1.3221 35
40 11.65 0.02450 7.041 54.89 562.60 55.07 559.69 614.76 0.1234 1.3109 40
45 16.87 0.02465 6.302 60.56 563.75 60.76 555.50 616.26 0.1354 1.3011 45
50 21.65 0.02478 5.705 65.77 564.78 66.00 551.59 617.60 0.1463 1.2923 50
Ammonia
55 26.07 0.02491 5.213 70.61 565.70 70.86 547.93 618.79 0.1563 1.2843 55
60 30.19 0.02503 4.801 75.13 566.53 75.41 544.46 619.87 0.1656 1.2770 60
65 34.04 0.02515 4.450 79.39 567.29 79.69 541.16 620.85 0.1742 1.2703 65
70 37.67 0.02526 4.1473 83.40 567.99 83.73 538.01 621.74 0.1823 1.2641 70
75 41.11 0.02536 3.8837 87.21 568.63 87.57 535.00 622.56 0.1900 1.2583 75
80 44.37 0.02546 3.6520 90.84 569.22 91.22 532.10 623.32 0.1972 1.2529 80
85 47.47 0.02556 3.4466 94.30 569.77 94.71 529.31 624.02 0.2040 1.2478 85
90 50.44 0.02566 3.2632 97.62 570.28 98.05 526.62 624.66 0.2106 1.2429 90
100 56.01 0.02584 2.9497 103.87 571.21 104.35 521.48 625.82 0.2227 1.2340 100
110 61.17 0.02601 2.6913 109.68 572.01 110.20 516.63 626.83 0.2340 1.2259 110
120 65.98 0.02618 2.4745 115.11 572.73 115.69 512.02 627.71 0.2443 1.2184 120
130 70.50 0.02634 2.2899 120.21 573.36 120.85 507.64 628.48 0.2540 1.2115 130
140 74.75 0.02649 2.1309 125.04 573.92 125.73 503.43 629.16 0.2631 1.2051 140
150 78.78 0.02664 1.9923 129.63 574.42 130.37 499.39 629.76 0.2717 1.1991 150
175 88.02 0.02699 1.7128 140.19 575.45 141.07 489.89 630.95 0.2911 1.1856 175
200 96.31 0.02732 1.5010 149.72 576.21 150.73 481.07 631.80 0.3084 1.1737 200
225 103.85 0.02764 1.3348 158.43 576.77 159.58 472.80 632.38 0.3240 1.1630 225
250 110.78 0.02794 1.2007 166.48 577.16 167.77 464.97 632.74 0.3382 1.1533 250
275 117.20 0.02823 1.0901 173.99 577.41 175.43 457.49 632.92 0.3513 1.1444 275
300 123.20 0.02851 0.9974 181.05 577.54 182.63 450.31 632.94 0.3635 1.1361 300
TABLE A-15E Properties of Superheated Ammonia Vapor

T v u h s v u h s
(Tsat 57.63F) (Tsat 48.63F)
Sat. 41.594 544.32 590.54 1.4699 31.790 546.98 594.08 1.4456
50 42.435 547.22 594.37 1.4793
40 43.533 551.03 599.40 1.4915 32.511 550.32 598.49 1.4562
30 44.627 554.84 604.42 1.5033 33.342 554.19 603.58 1.4682
20 45.715 558.66 609.45 1.5149 34.169 558.06 608.68 1.4799
10 46.800 562.47 614.47 1.5261 34.992 561.93 613.76 1.4914
0 47.882 566.29 619.49 1.5372 35.811 565.79 618.84 1.5025
10 48.960 570.12 624.51 1.5480 36.627 569.66 623.91 1.5135
20 50.035 573.95 629.54 1.5586 37.440 573.52 628.99 1.5241
30 51.108 577.78 634.57 1.5690 38.250 577.40 634.06 1.5346
40 52.179 581.63 639.60 1.5791 39.058 581.27 639.13 1.5449
50 53.247 585.49 644.64 1.5891 39.865 585.16 644.21 1.5549
60 54.314 589.35 649.70 1.5990 40.669 589.05 649.29 1.5648
(Tsat 41.33F) (Tsat 35.14F)
Sat. 25.807 549.09 596.87 1.4268 21.764 550.82 599.18 1.4115
40 25.897 549.61 597.56 1.4284
Ammonia
30 26.571 553.54 602.74 1.4406 22.056 552.87 601.88 1.4178
20 27.241 557.46 607.90 1.4525 22.621 556.85 607.12 1.4298
10 27.906 561.37 613.05 1.4641 23.182 560.82 612.33 1.4416
0 28.568 565.29 618.19 1.4754 23.739 564.78 617.53 1.4530
10 29.227 569.19 623.31 1.4864 24.293 568.73 622.71 1.4642
20 29.882 573.10 628.43 1.4972 24.843 572.67 627.88 1.4750
30 30.535 577.01 633.55 1.5078 25.392 576.61 633.03 1.4857
40 31.186 580.91 638.66 1.5181 25.937 580.55 638.19 1.4961
50 31.835 584.82 643.77 1.5282 26.481 584.49 643.33 1.5063
60 32.482 588.74 648.89 1.5382 27.023 588.43 648.48 1.5163
70 33.127 592.66 654.01 1.5479 27.564 592.38 653.63 1.5261
(Tsat 29.74F) (Tsat 24.94F)
Sat. 18.843 552.31 601.16 1.3986 16.631 553.60 602.88 1.3874
20 19.321 556.24 606.33 1.4105 16.845 555.62 605.53 1.3935
10 19.807 560.26 611.61 1.4223 17.275 559.69 610.88 1.4055
0 20.289 564.27 616.86 1.4339 17.701 563.75 616.19 1.4172
10 20.768 568.26 622.10 1.4452 18.124 567.79 621.48 1.4286
20 21.244 572.24 627.31 1.4562 18.544 571.81 626.75 1.4397
30 21.717 576.22 632.52 1.4669 18.961 575.82 632.00 1.4505
40 22.188 580.19 637.71 1.4774 19.376 579.82 637.23 1.4611
50 22.657 584.16 642.89 1.4877 19.789 583.82 642.45 1.4714
60 23.124 588.12 648.07 1.4977 20.200 587.81 647.66 1.4815
70 23.590 592.09 653.25 1.5076 20.609 591.80 652.86 1.4915
80 24.054 596.07 658.42 1.5173 21.017 595.80 658.07 1.5012
90 24.517 600.04 663.60 1.5268 21.424 599.80 663.27 1.5107

T v u h s v u h s
(Tsat 20.60F) (Tsat 16.63F)
Sat. 14.896 554.75 604.40 1.3775 13.497 555.78 605.76 1.3687
20 14.919 555.00 604.72 1.3783
10 15.306 559.13 610.14 1.3905 13.730 558.55 609.40 1.3769
0 15.688 563.23 615.52 1.4023 14.078 562.70 614.84 1.3888
10 16.068 567.31 620.87 1.4138 14.422 566.83 620.24 1.4005
20 16.444 571.37 626.18 1.4250 14.764 570.94 625.61 1.4118
30 16.818 575.42 631.47 1.4359 15.103 575.02 630.95 1.4228
40 17.189 579.46 636.75 1.4466 15.439 579.09 636.26 1.4335
50 17.558 583.48 642.00 1.4570 15.773 583.14 641.55 1.4440
60 17.925 587.50 647.25 1.4672 16.105 587.19 646.83 1.4543
70 18.291 591.52 652.48 1.4772 16.436 591.23 652.10 1.4643
80 18.655 595.53 657.71 1.4869 16.765 595.26 657.35 1.4741
90 19.018 599.55 662.94 1.4965 17.094 599.30 662.60 1.4838
(Tsat 0.57F) (Tsat 11.65F)
Sat. 9.2286 559.77 611.04 1.3349 7.0414 562.60 614.76 1.3109
0 9.2425 560.02 611.36 1.3356
Ammonia
10 9.4834 564.38 617.07 1.3479

20 9.7209 568.70 622.70 1.3598 7.1965 566.39 619.69 1.3213
30 9.9554 572.97 628.28 1.3713 7.3795 570.86 625.52 1.3333
40 10.187 577.21 633.80 1.3824 7.5597 575.28 631.28 1.3450
50 10.417 581.42 639.28 1.3933 7.7376 579.65 636.96 1.3562
60 10.645 585.60 644.73 1.4039 7.9134 583.97 642.58 1.3672
70 10.871 589.76 650.15 1.4142 8.0874 588.26 648.16 1.3778
80 11.096 593.90 655.54 1.4243 8.2598 592.52 653.69 1.3881
90 11.319 598.04 660.91 1.4342 8.4308 596.75 659.20 1.3982
100 11.541 602.16 666.27 1.4438 8.6006 600.97 664.67 1.4081
110 11.762 606.28 671.62 1.4533 8.7694 605.17 670.12 1.4178
(Tsat 21.65F) (Tsat 30.19F)
Sat. 5.7049 564.78 617.60 1.2923 4.8009 566.53 619.87 1.2770
40 5.9815 573.30 628.68 1.3149 4.9278 571.25 626.00 1.2894
60 6.2733 582.31 640.39 1.3379 5.1788 580.60 638.14 1.3133
80 6.5574 591.10 651.82 1.3595 5.4218 589.66 649.90 1.3355
100 6.8358 599.75 663.04 1.3799 5.6587 598.52 661.39 1.3564
120 7.1097 608.30 674.13 1.3993 5.8910 607.23 672.68 1.3762
140 7.3802 616.80 685.13 1.4180 6.1198 615.86 683.85 1.3951
160 7.6480 625.28 696.09 1.4360 6.3458 624.44 694.95 1.4133
200 8.1776 642.27 717.99 1.4702 6.7916 641.59 717.05 1.4479
240 8.7016 659.44 740.00 1.5026 7.2318 658.87 739.21 1.4805
280 9.2218 676.88 762.26 1.5336 7.6679 676.38 761.58 1.5116
320 9.7391 694.65 784.82 1.5633 8.1013 694.21 784.22 1.5414
360 10.254 712.79 807.73 1.5919 8.5325 712.40 807.20 1.5702

T v u h s v u h s
(Tsat 37.67F) (Tsat 44.37F)
Sat. 4.1473 567.99 621.74 1.2641 3.6520 569.22 623.32 1.2529
40 4.1739 569.15 623.25 1.2671
60 4.3962 578.85 635.84 1.2918 3.8084 577.06 633.48 1.2727
80 4.6100 588.19 647.95 1.3147 4.0006 586.69 645.95 1.2963
100 4.8175 597.26 659.70 1.3361 4.1862 595.98 657.99 1.3182
120 5.0202 606.14 671.22 1.3563 4.3668 605.04 669.73 1.3388
140 5.2193 614.91 682.56 1.3756 4.5436 613.94 681.25 1.3583
160 5.4154 623.60 693.79 1.3940 4.7175 622.74 692.63 1.3770
200 5.8015 640.91 716.11 1.4289 5.0589 640.22 715.16 1.4122
240 6.1818 658.29 738.42 1.4617 5.3942 657.71 737.62 1.4453
280 6.5580 675.89 760.89 1.4929 5.7256 675.39 760.20 1.4767
320 6.9314 693.78 783.62 1.5229 6.0540 693.34 783.02 1.5067
360 7.3026 712.02 806.67 1.5517 6.3802 711.63 806.15 1.5357
400 7.6721 730.63 830.08 1.5796 6.7047 730.29 829.61 1.5636

(Tsat 50.44F) (Tsat 56.01F)
Ammonia
Sat. 3.2632 570.28 624.66 1.2429 2.9497 571.21 625.82 1.2340
60 3.3504 575.22 631.05 1.2553 2.9832 573.32 628.56 1.2393
80 3.5261 585.15 643.91 1.2796 3.1460 583.58 641.83 1.2644
100 3.6948 594.68 656.26 1.3021 3.3014 593.35 654.49 1.2874
120 3.8584 603.92 668.22 1.3231 3.4513 602.79 666.70 1.3088
140 4.0180 612.97 679.93 1.3430 3.5972 611.98 678.59 1.3290
160 4.1746 621.88 691.45 1.3619 3.7401 621.01 690.27 1.3481
200 4.4812 639.52 714.20 1.3974 4.0189 638.82 713.24 1.3841
240 4.7817 657.13 736.82 1.4307 4.2916 656.54 736.01 1.4176
280 5.0781 674.89 759.52 1.4623 4.5600 674.39 758.82 1.4493
320 5.3715 692.90 782.42 1.4924 4.8255 692.47 781.82 1.4796
360 5.6628 711.24 805.62 1.5214 5.0888 710.86 805.09 1.5087
400 5.9522 729.95 829.14 1.5495 5.3503 729.60 828.68 1.5368

(Tsat 61.17F) (Tsat 65.98F)
Sat. 2.6913 572.01 626.83 1.2259 2.4745 572.73 627.71 1.2184
80 2.8344 581.97 639.71 1.2502 2.5744 580.33 637.53 1.2369
100 2.9791 592.00 652.69 1.2738 2.7102 590.63 650.85 1.2611
120 3.1181 601.63 665.14 1.2957 2.8401 600.46 663.57 1.2834
140 3.2528 610.98 677.24 1.3162 2.9657 609.97 675.86 1.3043
160 3.3844 620.13 689.07 1.3356 3.0879 619.24 687.86 1.3240
200 3.6406 638.11 712.27 1.3719 3.3254 637.40 711.29 1.3606
240 3.8905 655.96 735.20 1.4056 3.5563 655.36 734.39 1.3946
280 4.1362 673.88 758.13 1.4375 3.7829 673.37 757.43 1.4266
320 4.3788 692.02 781.22 1.4679 4.0065 691.58 780.61 1.4572
360 4.6192 710.47 804.56 1.4971 4.2278 710.08 804.02 1.4864
400 4.8578 729.26 828.21 1.5252 4.4473 728.92 827.74 1.5147

T v u h s v u h s
(Tsat 70.50F) (Tsat 74.75F)
Sat. 2.2899 573.36 628.48 1.2115 2.1309 573.92 629.16 1.2051
80 2.3539 578.64 635.30 1.2243 2.1633 576.80 632.89 1.2119
100 2.4824 589.23 648.98 1.2492 2.2868 587.79 647.08 1.2379
120 2.6048 599.27 661.97 1.2720 2.4004 597.85 660.08 1.2604
140 2.7226 608.94 674.48 1.2932 2.5140 607.90 673.07 1.2828
160 2.8370 618.34 686.64 1.3132 2.6204 617.34 685.27 1.3025
180 2.9488 627.57 698.55 1.3321 2.7268 626.77 697.46 1.3222
200 3.0585 636.69 710.31 1.3502 2.8289 635.93 709.27 1.3401
240 3.2734 654.77 733.57 1.3844 3.0304 654.17 732.73 1.3747
280 3.4840 672.87 756.73 1.4166 3.2274 672.38 756.04 1.4071
320 3.6915 691.14 780.00 1.4472 3.4212 690.73 779.42 1.4379
360 3.8966 709.69 803.49 1.4766 3.6126 709.34 802.99 1.4674
400 4.1000 728.57 827.27 1.5049 3.8022 728.27 826.84 1.4958

(Tsat 78.78F) (Tsat 96.31F)
Sat. 1.9923 574.42 629.76 1.1991 1.5010 576.21 631.80 1.1737
100 2.1170 586.33 645.13 1.2271 1.5190 578.52 634.77 1.1790
Ammonia
140 2.3332 606.84 671.65 1.2729 1.6984 601.34 664.24 1.2299

180 2.5343 625.95 696.35 1.3128 1.8599 621.77 690.65 1.2726
220 2.7268 644.43 720.17 1.3489 2.0114 641.07 715.57 1.3104
260 2.9137 662.70 743.63 1.3825 2.1569 659.90 739.78 1.3450
300 3.0968 681.02 767.04 1.4141 2.2984 678.62 763.74 1.3774
340 3.2773 699.54 790.57 1.4443 2.4371 697.44 787.70 1.4081
380 3.4558 718.35 814.34 1.4733 2.5736 716.50 811.81 1.4375
420 3.6325 737.50 838.39 1.5013 2.7085 735.86 836.17 1.4659
460 3.8079 757.01 862.78 1.5284 2.8420 755.57 860.82 1.4933
500 3.9821 776.91 887.51 1.5548 2.9742 775.65 885.80 1.5199
540 4.1553 797.19 912.60 1.5804 3.1054 796.10 911.11 1.5457
580 4.3275 817.85 938.05 1.6053 3.2357 816.94 936.77 1.5709

(Tsat 110.78F) (Tsat 123.20F)
Sat. 1.2007 577.16 632.74 1.1533 0.9974 577.54 632.94 1.1361
140 1.3150 595.40 656.28 1.1936 1.0568 588.94 647.65 1.1610
180 1.4539 617.38 684.69 1.2395 1.1822 612.75 678.42 1.2107
220 1.5816 637.61 710.82 1.2791 1.2944 634.01 705.91 1.2524
260 1.7025 657.03 735.85 1.3149 1.3992 654.09 731.82 1.2895
300 1.8191 676.17 760.39 1.3481 1.4994 673.69 756.98 1.3235
340 1.9328 695.32 784.79 1.3794 1.5965 693.16 781.85 1.3554
380 2.0443 714.63 809.27 1.4093 1.6913 712.74 806.70 1.3857
420 2.1540 734.22 833.93 1.4380 1.7843 732.55 831.67 1.4148
460 2.2624 754.12 858.85 1.4657 1.8759 752.66 856.87 1.4428
500 2.3695 774.38 884.07 1.4925 1.9663 773.10 882.33 1.4699
540 2.4755 795.01 909.61 1.5186 2.0556 793.90 908.09 1.4962
580 2.5807 816.01 935.47 1.5440 2.1440 815.07 934.17 1.5218
TABLE A-16E Properties of Saturated Propane (LiquidVapor): Temperature Table

F lbf/in2 vf vg uf ug hf hfg hg sf sg F
140 0.6053 0.02505 128.00 51.33 139.22 51.33 204.9 153.6 0.139 0.501 140
120 1.394 0.02551 58.88 41.44 143.95 41.43 200.6 159.1 0.109 0.481 120
100 2.888 0.02601 29.93 31.34 148.80 31.33 196.1 164.8 0.080 0.465 100
80 5.485 0.02653 16.52 21.16 153.73 21.13 191.6 170.5 0.053 0.452 80
60 9.688 0.02708 9.75 10.73 158.74 10.68 186.9 176.2 0.026 0.441 60
40 16.1 0.02767 6.08 0.08 163.80 0.00 181.9 181.9 0.000 0.433 40
20 25.4 0.02831 3.98 10.81 168.88 10.94 176.6 187.6 0.025 0.427 20
0 38.4 0.02901 2.70 21.98 174.01 22.19 171.0 193.2 0.050 0.422 0
10 46.5 0.02939 2.25 27.69 176.61 27.94 168.0 196.0 0.063 0.420 10
20 55.8 0.02978 1.89 33.47 179.15 33.78 164.9 198.7 0.074 0.418 20
30 66.5 0.03020 1.598 39.34 181.71 39.71 161.7 201.4 0.087 0.417 30
40 78.6 0.03063 1.359 45.30 184.30 45.75 158.3 204.1 0.099 0.415 40
50 92.3 0.03110 1.161 51.36 186.74 51.89 154.7 206.6 0.111 0.414 50
60 107.7 0.03160 0.9969 57.53 189.30 58.16 151.0 209.2 0.123 0.413 60
70 124.9 0.03213 0.8593 63.81 191.71 64.55 147.0 211.6 0.135 0.412 70
80 144.0 0.03270 0.7433 70.20 194.16 71.07 142.9 214.0 0.147 0.411 80
90 165.2 0.03332 0.6447 76.72 196.46 77.74 138.4 216.2 0.159 0.410 90
100 188.6 0.03399 0.5605 83.38 198.71 84.56 133.7 218.3 0.171 0.410 100
110 214.3 0.03473 0.4881 90.19 200.91 91.56 128.7 220.3 0.183 0.409 110
120 242.5 0.03555 0.4254 97.16 202.98 98.76 123.3 222.1 0.195 0.408 120
130 273.3 0.03646 0.3707 104.33 204.92 106.17 117.5 223.7 0.207 0.406 130
140 306.9 0.03749 0.3228 111.70 206.64 113.83 111.1 225.0 0.220 0.405 140
150 343.5 0.03867 0.2804 119.33 208.05 121.79 104.1 225.9 0.233 0.403 150
Propane
160 383.3 0.04006 0.2426 127.27 209.16 130.11 96.3 226.4 0.246 0.401 160
170 426.5 0.04176 0.2085 135.60 209.81 138.90 87.4 226.3 0.259 0.398 170
180 473.4 0.04392 0.1771 144.50 209.76 148.35 76.9 225.3 0.273 0.394 180
190 524.3 0.04696 0.1470 154.38 208.51 158.94 63.8 222.8 0.289 0.387 190
200 579.7 0.05246 0.1148 166.65 204.16 172.28 44.2 216.5 0.309 0.376 200
206.1 616.1 0.07265 0.07265 186.99 186.99 195.27 0.0 195.27 0.343 0.343 206.1
TABLE A-17E Properties of Saturated Propane (LiquidVapor): Pressure Table

lbf/in2 F vf vg uf ug hf hfg hg sf sg lbf/in2
0.75 135.1 0.02516 104.8 48.93 140.36 48.93 203.8 154.9 0.132 0.496 0.75
1.5 118.1 0.02556 54.99 40.44 144.40 40.43 200.1 159.7 0.106 0.479 1.5
3 98.9 0.02603 28.9 30.84 149.06 30.83 196.0 165.1 0.079 0.464 3
5 83.0 0.02644 18.00 22.75 152.96 22.73 192.4 169.6 0.057 0.454 5
7.5 69.3 0.02682 12.36 15.60 156.40 15.56 189.1 173.6 0.038 0.446 7.5
10 58.8 0.02711 9.468 10.10 159.04 10.05 186.6 176.6 0.024 0.441 10
20 30.7 0.02796 4.971 4.93 166.18 5.03 179.5 184.6 0.012 0.430 20
30 12.1 0.02858 3.402 15.15 170.93 15.31 174.5 189.8 0.035 0.425 30
40 2.1 0.02909 2.594 23.19 174.60 23.41 170.4 193.8 0.053 0.422 40
50 13.9 0.02954 2.099 29.96 177.63 30.23 166.8 197.1 0.067 0.419 50
60 24.1 0.02995 1.764 35.86 180.23 36.19 163.6 199.8 0.079 0.418 60
70 33.0 0.03033 1.520 41.14 182.50 41.53 160.6 202.2 0.090 0.416 70
80 41.1 0.03068 1.336 45.95 184.57 46.40 157.9 204.3 0.100 0.415 80
90 48.4 0.03102 1.190 50.38 186.36 50.90 155.3 206.2 0.109 0.414 90
100 55.1 0.03135 1.073 54.52 188.07 55.10 152.8 207.9 0.117 0.414 100
120 67.2 0.03198 0.8945 62.08 191.07 62.79 148.1 210.9 0.131 0.412 120
140 78.0 0.03258 0.7650 68.91 193.68 69.75 143.7 213.5 0.144 0.412 140
160 87.6 0.03317 0.6665 75.17 195.97 76.15 139.5 215.7 0.156 0.411 160
180 96.5 0.03375 0.5890 80.99 197.97 82.12 135.5 217.6 0.166 0.410 180
200 104.6 0.03432 0.5261 86.46 199.77 87.73 131.4 219.2 0.176 0.409 200
220 112.1 0.03489 0.4741 91.64 201.37 93.06 127.6 220.7 0.185 0.408 220
240 119.2 0.03547 0.4303 96.56 202.76 98.14 123.7 221.9 0.194 0.408 240
260 125.8 0.03606 0.3928 101.29 204.07 103.0 120.0 223.0 0.202 0.407 260
Propane
280 132.1 0.03666 0.3604 105.83 205.27 107.7 116.1 223.9 0.210 0.406 280
300 138.0 0.03727 0.3319 110.21 206.27 112.3 112.4 224.7 0.217 0.405 300
320 143.7 0.03790 0.3067 114.47 207.17 116.7 108.6 225.3 0.224 0.404 320
340 149.1 0.03855 0.2842 118.60 207.96 121.0 104.7 225.8 0.231 0.403 340
360 154.2 0.03923 0.2639 122.66 208.58 125.3 100.9 226.2 0.238 0.402 360
380 159.2 0.03994 0.2455 126.61 209.07 129.4 97.0 226.4 0.245 0.401 380
400 164.0 0.04069 0.2287 130.51 209.47 133.5 93.0 226.5 0.251 0.400 400
450 175.1 0.04278 0.1921 140.07 209.87 143.6 82.2 225.9 0.266 0.396 450
500 185.3 0.04538 0.1610 149.61 209.27 153.8 70.4 224.2 0.282 0.391 500
600 203.4 0.05659 0.1003 172.85 200.27 179.1 32.2 211.4 0.319 0.367 600
616.1 206.1 0.07265 0.07265 186.99 186.99 195.3 0.0 195.3 0.343 0.343 616.1
TABLE A-18E Properties of Superheated Propane

T v u h s v u h s
p 0.75 lbf/in2 p 1.5 lbf/in2
(Tsat 135.1F) (Tsat 118.1F)
Sat. 104.8 140.4 154.9 0.496 54.99 144.4 159.7 0.479
130 106.5 141.6 156.4 0.501
110 113.1 146.6 162.3 0.518 56.33 146.5 162.1 0.486
90 119.6 151.8 168.4 0.535 59.63 151.7 168.2 0.503
70 126.1 157.2 174.7 0.551 62.92 157.1 174.5 0.520
50 132.7 162.7 181.2 0.568 66.20 162.6 181.0 0.536
30 139.2 168.6 187.9 0.584 69.47 168.4 187.7 0.552
10 145.7 174.4 194.7 0.599 72.74 174.4 194.6 0.568
10 152.2 180.7 201.9 0.615 76.01 180.7 201.8 0.583
30 158.7 187.1 209.2 0.630 79.27 187.1 209.1 0.599
50 165.2 193.8 216.8 0.645 82.53 193.8 216.7 0.614
70 171.7 200.7 224.6 0.660 85.79 200.7 224.5 0.629
90 178.2 207.8 232.6 0.675 89.04 207.8 232.5 0.644

(Tsat 83.0F) (Tsat 58.8F)
Sat. 18.00 153.0 169.6 0.454 9.468 159.0 176.6 0.441
80 18.15 153.8 170.6 0.456
60 19.17 159.4 177.1 0.473
40 20.17 165.1 183.8 0.489 9.957 80.9 99.3 1.388
20 21.17 171.1 190.7 0.505 10.47 86.9 106.3 1.405
0 22.17 177.2 197.7 0.521 10.98 93.1 113.4 1.421
20 23.16 183.5 205.0 0.536 11.49 99.5 120.8 1.436
40 24.15 190.1 212.5 0.552 11.99 106.1 128.3 1.452
Propane
60 25.14 196.9 220.2 0.567 12.49 113.0 136.1 1.467
80 26.13 204.0 228.2 0.582 12.99 120.0 144.1 1.482
100 27.11 211.3 236.4 0.597 13.49 127.3 152.3 1.497
120 28.09 218.8 244.8 0.611 13.99 134.9 160.7 1.512
140 29.07 226.5 253.4 0.626 14.48 142.6 169.4 1.526

Sat. 4.971 166.2 184.6 0.430 2.594 174.6 193.8 0.422
20 5.117 169.5 188.5 0.439
0 5.385 175.8 195.8 0.455
20 5.648 182.4 203.3 0.471 2.723 180.6 200.8 0.436
40 5.909 189.1 211.0 0.487 2.864 187.6 208.8 0.453
60 6.167 195.9 218.8 0.502 3.002 194.6 216.9 0.469
80 6.424 203.1 226.9 0.518 3.137 201.8 225.1 0.484
100 6.678 210.5 235.2 0.533 3.271 209.4 233.6 0.500
120 6.932 218.0 243.7 0.548 3.403 217.0 242.2 0.515
140 7.184 225.8 252.4 0.562 3.534 224.9 251.1 0.530
160 7.435 233.9 261.4 0.577 3.664 232.9 260.1 0.545
180 7.685 242.1 270.6 0.592 3.793 241.3 269.4 0.559
200 7.935 250.6 280.0 0.606 3.921 249.8 278.9 0.574

T v u h s v u h s
Sat. 1.764 180.2 199.8 0.418 1.336 184.6 204.3 0.415
30 1.794 182.4 202.3 0.384
50 1.894 189.5 210.6 0.400 1.372 187.9 208.2 0.423
70 1.992 196.9 219.0 0.417 1.450 195.4 216.9 0.440
90 2.087 204.4 227.6 0.432 1.526 203.1 225.7 0.456
110 2.179 212.1 236.3 0.448 1.599 210.9 234.6 0.472
130 2.271 220.0 245.2 0.463 1.671 218.8 243.6 0.487
150 2.361 228.0 254.2 0.478 1.741 227.0 252.8 0.503
170 2.450 236.3 263.5 0.493 1.810 235.4 262.2 0.518
190 2.539 244.8 273.0 0.508 1.879 244.0 271.8 0.533
210 2.626 253.5 282.7 0.523 1.946 252.7 281.5 0.548
230 2.713 262.3 292.5 0.537 2.013 261.7 291.5 0.562
250 2.800 271.6 302.7 0.552 2.079 270.9 301.7 0.577
p 100 lbf/in2 p 120 lbf/in2

Sat. 1.073 188.1 207.9 0.414 0.8945 191.1 210.9 0.412
60 1.090 189.9 210.1 0.418
80 1.156 197.8 219.2 0.435 0.9323 196.2 216.9 0.424
100 1.219 205.7 228.3 0.452 0.9887 204.3 226.3 0.441
120 1.280 213.7 237.4 0.468 1.043 212.5 235.7 0.457
140 1.340 221.9 246.7 0.483 1.094 220.8 245.1 0.473
160 1.398 230.2 256.1 0.499 1.145 229.2 254.7 0.489
180 1.454 238.8 265.7 0.514 1.194 237.9 264.4 0.504
Propane
200 1.510 247.5 275.5 0.529 1.242 246.7 274.3 0.520

220 1.566 256.4 285.4 0.544 1.289 255.6 284.3 0.534
240 1.620 265.6 295.6 0.559 1.336 264.8 294.5 0.549
260 1.674 274.9 305.9 0.573 1.382 274.2 304.9 0.564
280 1.728 284.4 316.4 0.588 1.427 283.8 315.5 0.579

Sat. 0.7650 193.7 213.5 0.412 0.6665 196.0 215.7 0.411
80 0.7705 213.3 214.5 0.413
100 0.8227 222.9 224.2 0.431 0.6968 201.2 221.9 0.422
120 0.8718 232.4 233.8 0.448 0.7427 209.9 231.9 0.439
140 0.9185 242.1 243.5 0.464 0.7859 218.4 241.7 0.456
160 0.9635 251.7 253.2 0.480 0.8272 227.2 251.7 0.472
180 1.007 261.4 263.0 0.496 0.8669 235.9 261.6 0.488
200 1.050 271.4 273.0 0.511 0.9054 244.9 271.7 0.504
220 1.091 281.5 283.2 0.526 0.9430 254.0 282.0 0.519
240 1.132 291.7 293.5 0.541 0.9797 263.4 292.4 0.534
260 1.173 302.1 303.9 0.556 1.016 272.8 302.9 0.549
280 1.213 312.7 314.6 0.571 1.051 282.6 313.7 0.564
300 1.252 323.6 325.5 0.585 1.087 292.4 324.6 0.578

T v u h s v u h s
(Tsat 96.5F) (Tsat 104.6F)
Sat. 0.5890 198.0 217.6 0.410 0.5261 199.8 219.2 0.409
100 0.5972 199.6 219.5 0.413
120 0.6413 208.4 229.8 0.431 0.5591 206.8 227.5 0.424
140 0.6821 217.1 239.9 0.449 0.5983 215.8 238.0 0.441
160 0.7206 226.1 250.1 0.465 0.6349 224.9 248.4 0.458
180 0.7574 234.9 260.2 0.481 0.6694 233.9 258.7 0.475
200 0.7928 244.0 270.4 0.497 0.7025 243.1 269.1 0.491
220 0.8273 253.2 280.8 0.513 0.7345 252.4 279.6 0.506
240 0.8609 262.6 291.3 0.528 0.7656 261.7 290.1 0.522
260 0.8938 272.1 301.9 0.543 0.7960 271.4 300.9 0.537
280 0.9261 281.8 312.7 0.558 0.8257 281.1 311.7 0.552
300 0.9579 291.8 323.7 0.572 0.8549 291.1 322.8 0.567
320 0.9894 301.9 334.9 0.587 0.8837 301.3 334.0 0.581

(Tsat 112.1F) (Tsat 119.2F)
Sat. 0.4741 201.4 220.7 0.408 0.4303 202.8 221.9 0.408
120 0.4906 205.1 225.1 0.416 0.4321 203.2 222.4 0.409
140 0.5290 214.4 236.0 0.435 0.4704 212.9 233.8 0.428
160 0.5642 223.6 246.6 0.452 0.5048 222.4 244.8 0.446
180 0.5971 232.9 257.2 0.469 0.5365 231.6 255.5 0.463
200 0.6284 242.1 267.7 0.485 0.5664 241.1 266.3 0.480
220 0.6585 251.5 278.3 0.501 0.5949 250.5 277.0 0.496
240 0.6875 261.0 289.0 0.516 0.6223 260.1 287.8 0.511
Propane
260 0.7158 270.6 299.8 0.532 0.6490 269.8 298.7 0.527
280 0.7435 280.5 310.8 0.547 0.6749 279.8 309.8 0.542
300 0.7706 290.5 321.9 0.561 0.7002 289.8 320.9 0.557
320 0.7972 300.6 333.1 0.576 0.7251 300.1 332.3 0.571
340 0.8235 311.0 344.6 0.591 0.7496 310.5 343.8 0.586

(Tsat 125.8F) (Tsat 132.1F)
Sat. 0.3928 204.1 223.0 0.407 0.3604 205.3 223.9 0.406
130 0.4012 206.3 225.6 0.411
150 0.4374 216.1 237.2 0.431 0.3932 214.5 234.9 0.424
170 0.4697 225.8 248.4 0.449 0.4253 224.4 246.5 0.443
190 0.4995 235.2 259.3 0.466 0.4544 234.1 257.7 0.461
210 0.5275 244.8 270.2 0.482 0.4815 243.8 268.8 0.477
230 0.5541 254.4 281.1 0.498 0.5072 253.5 279.8 0.494
250 0.5798 264.2 292.1 0.514 0.5317 263.3 290.9 0.510
270 0.6046 274.1 303.2 0.530 0.5553 273.3 302.1 0.525
290 0.6288 284.0 314.3 0.545 0.5783 283.4 313.4 0.540
310 0.6524 294.3 325.7 0.560 0.6007 293.5 324.7 0.555
330 0.6756 304.7 337.2 0.574 0.6226 304.0 336.3 0.570
350 0.6984 315.2 348.8 0.589 0.6441 314.6 348.0 0.585

T v u h s v u h s
(Tsat 143.7F) (Tsat 154.2F)
Sat. 0.3067 207.2 225.3 0.404 0.2639 208.6 226.2 0.402
150 0.3187 210.7 229.6 0.412
170 0.3517 221.4 242.3 0.432 0.2920 217.9 237.4 0.420
190 0.3803 231.7 254.2 0.450 0.3213 228.8 250.2 0.440
210 0.4063 241.6 265.7 0.468 0.3469 239.3 262.4 0.459
230 0.4304 251.6 277.1 0.485 0.3702 249.5 274.2 0.476
250 0.4533 261.6 288.5 0.501 0.3919 259.8 285.9 0.493
270 0.4751 271.7 299.9 0.517 0.4124 270.1 297.6 0.509
290 0.4961 281.9 311.3 0.532 0.4320 280.4 309.2 0.525
310 0.5165 292.3 322.9 0.548 0.4510 290.8 320.9 0.540
330 0.5364 302.7 334.5 0.563 0.4693 301.4 332.7 0.556
350 0.5559 313.4 346.3 0.577 0.4872 312.2 344.7 0.570
370 0.5750 324.2 358.3 0.592 0.5047 323.0 356.7 0.585

(Tsat 164.0F) (Tsat 175.1F)
Sat. 0.2287 209.5 226.5 0.400 0.1921 209.9 225.9 0.396
170 0.2406 213.6 231.4 0.408
190 0.2725 225.6 245.8 0.430 0.2205 220.7 239.1 0.416
210 0.2985 236.7 258.8 0.450 0.2486 233.0 253.7 0.439
230 0.3215 247.4 271.2 0.468 0.2719 244.3 267.0 0.458
250 0.3424 257.8 283.2 0.485 0.2925 255.2 279.6 0.476
270 0.3620 268.3 295.1 0.502 0.3113 266.0 292.0 0.493
290 0.3806 278.8 307.0 0.518 0.3290 276.8 304.2 0.510
Propane
310 0.3984 289.4 318.9 0.534 0.3457 287.6 316.4 0.526

330 0.4156 300.1 330.9 0.549 0.3617 298.4 328.5 0.542
350 0.4322 311.0 343.0 0.564 0.3772 309.4 340.8 0.557
370 0.4484 321.9 355.1 0.579 0.3922 320.4 353.1 0.572
390 0.4643 333.1 367.5 0.594 0.4068 331.7 365.6 0.587

(Tsat 185.3F) (Tsat 203.4F)
Sat. 0.1610 209.3 224.2 0.391 0.1003 200.3 211.4 0.367
190 0.1727 213.8 229.8 0.399
210 0.2066 228.6 247.7 0.426 0.1307 214.3 228.8 0.394
230 0.2312 240.9 262.3 0.448 0.1661 232.2 250.7 0.426
250 0.2519 252.4 275.7 0.467 0.1892 245.8 266.8 0.449
270 0.2704 263.6 288.6 0.485 0.2080 258.1 281.2 0.469
290 0.2874 274.6 301.2 0.502 0.2245 269.8 294.8 0.487
310 0.3034 285.6 313.7 0.519 0.2396 281.4 308.0 0.505
330 0.3186 296.6 326.1 0.534 0.2536 292.8 321.0 0.521
350 0.3331 307.7 338.6 0.550 0.2669 304.2 333.9 0.538
370 0.3471 318.9 351.0 0.565 0.2796 315.7 346.8 0.553
390 0.3607 330.2 363.6 0.580 0.2917 327.3 359.7 0.569
410 0.3740 341.7 376.3 0.595 0.3035 338.9 372.6 0.584
TABLE A-19E Properties of Selected Solids and Liquids: cp, , and
Specific Density, Thermal

Heat, cp Conductivity,
Substance (Btu/lb # R) (lb/ft3) (Btu/h # ft # R)

Selected Solids, 540R
Aluminum 0.216 169 137
Coal, anthracite 0.301 84.3 0.15
Copper 0.092 557 232
Granite 0.185 164 1.61
Iron 0.107 491 46.4
Lead 0.031 705 20.4
Sand 0.191 94.9 0.16
Silver 0.056 656 248
Soil 0.439 128 0.30
Steel (AISI 302) 0.115 503 8.7
Tin 0.054 456 38.5
Building Materials, 540R
Brick, common 0.199 120 0.42
Concrete (stone mix) 0.210 144 0.81
Glass, plate 0.179 156 0.81
Hardboard, siding 0.279 40 0.054
Limestone 0.193 145 1.24
Plywood 0.291 34 0.069
Softwoods (fir, pine) 0.330 31.8 0.069
Insulating Materials, 540R
Blanket (glass fiber) 1.0 0.027
Cork 0.43 7.5 0.023
Duct liner (glass fiber, coated) 0.199 2.0 0.022
Polystyrene (extruded) 0.289 3.4 0.016
Vermiculite fill (flakes) 0.199 5.0 0.039
Saturated Liquids
Ammonia, 540R 1.151 37.5 0.269
Mercury, 540R 0.033 845 4.94
Refrigerant 22, 540R 0.303 74.0 0.049
Refrigerant 134a, 540R 0.343 75.0 0.047
Table A-19E
Unused Engine Oil, 540R 0.456 55.2 0.084
Water, 495R 1.006 62.42 0.332
540R 0.998 62.23 0.354
585R 0.999 61.61 0.373
630R 1.002 60.79 0.386
675R 1.008 59.76 0.394
720R 1.017 58.55 0.398
Source: Drawn from several sources, these data are only representative. Values can vary depending on
temperature, purity, moisture content, and other factors.
TABLE A-20E Ideal Gas Specific Heats of Some Common Gases (Btu/lb # R)
cp cv k cp cv k cp cv k
Temp. Temp.
F Air Nitrogen, N2 Oxygen, O2 F
40 0.240 0.171 1.401 0.248 0.177 1.400 0.219 0.156 1.397 40
100 0.240 0.172 1.400 0.248 0.178 1.399 0.220 0.158 1.394 100
200 0.241 0.173 1.397 0.249 0.178 1.398 0.223 0.161 1.387 200
300 0.243 0.174 1.394 0.250 0.179 1.396 0.226 0.164 1.378 300
400 0.245 0.176 1.389 0.251 0.180 1.393 0.230 0.168 1.368 400
500 0.248 0.179 1.383 0.254 0.183 1.388 0.235 0.173 1.360 500
600 0.250 0.182 1.377 0.256 0.185 1.383 0.239 0.177 1.352 600
700 0.254 0.185 1.371 0.260 0.189 1.377 0.242 0.181 1.344 700
800 0.257 0.188 1.365 0.262 0.191 1.371 0.246 0.184 1.337 800
900 0.259 0.191 1.358 0.265 0.194 1.364 0.249 0.187 1.331 900
1000 0.263 0.195 1.353 0.269 0.198 1.359 0.252 0.190 1.326 1000
1500 0.276 0.208 1.330 0.283 0.212 1.334 0.263 0.201 1.309 1500
2000 0.286 0.217 1.312 0.293 0.222 1.319 0.270 0.208 1.298 2000
Temp. Carbon Carbon Temp.
F Dioxide, CO2 Monoxide, CO Hydrogen, H2 F
40 0.195 0.150 1.300 0.248 0.177 1.400 3.397 2.412 1.409 40
100 0.205 0.160 1.283 0.249 0.178 1.399 3.426 2.441 1.404 100
200 0.217 0.172 1.262 0.249 0.179 1.397 3.451 2.466 1.399 200
300 0.229 0.184 1.246 0.251 0.180 1.394 3.461 2.476 1.398 300
400 0.239 0.193 1.233 0.253 0.182 1.389 3.466 2.480 1.397 400
500 0.247 0.202 1.223 0.256 0.185 1.384 3.469 2.484 1.397 500
600 0.255 0.210 1.215 0.259 0.188 1.377 3.473 2.488 1.396 600
700 0.262 0.217 1.208 0.262 0.191 1.371 3.477 2.492 1.395 700
800 0.269 0.224 1.202 0.266 0.195 1.364 3.494 2.509 1.393 800
900 0.275 0.230 1.197 0.269 0.198 1.357 3.502 2.519 1.392 900
1000 0.280 0.235 1.192 0.273 0.202 1.351 3.513 2.528 1.390 1000
1500 0.298 0.253 1.178 0.287 0.216 1.328 3.618 2.633 1.374 1500
2000 0.312 0.267 1.169 0.297 0.226 1.314 3.758 2.773 1.355 2000
Source: Adapted from K. Wark, Thermodynamics, 4th ed., McGraw-Hill, New York, 1983, as based on Tables
of Thermal Properties of Gases, NBS Circular 564, 1955.
Table A-20E
TABLE A-21E Variation of cp with Temperature for Selected Ideal Gases

cp
a
bT
gT 2
dT 3
eT 4
R
T is in R, equations valid from 540 to 1800 R
Gas 103 106 109 1012
CO 3.710 0.899 1.140 0.348 0.0228
CO2 2.401 4.853 2.039 0.343 0
H2 3.057 1.487 1.793 0.947 0.1726
H2O 4.070 0.616 1.281 0.508 0.0769
O2 3.626 1.043 2.178 1.160 0.2053
N2 3.675 0.671 0.717 0.108 0.0215
Air 3.653 0.7428 1.017 0.328 0.02632
NH3 3.591 0.274 2.576 1.437 0.2601
NO 4.046 1.899 2.464 1.048 0.1517
NO2 3.459 1.147 2.064 1.639 0.3448
SO2 3.267 2.958 0.211 0.906 0.2438
SO3 2.578 8.087 2.832 0.136 0.1878
CH4 3.826 2.211 7.580 3.898 0.6633
C2H2 1.410 10.587 7.562 2.811 0.3939
C2H4 1.426 6.324 2.466 2.787 0.6429
Monatomic
gasesa 2.5 0 0 0 0
a
For monatomic gases, such as He, Ne, and Ar, cp is constant over a wide temperature range and is very nearly
equal to 52 R.
Source: Adapted from K. Wark, Thermodynamics, 4th ed., McGraw-Hill, New York, 1983, as based on NASA
SP-273, U.S. Government Printing Office, Washington, DC, 1971.
Table A-21E
Table A-22E
TABLE A-22E Ideal Gas Properties of Air

T(R), h and u(Btu/lb), s(Btu/lb # R)
when s 01 when s 0
360 85.97 61.29 0.50369 0.3363 396.6 940 226.11 161.68 0.73509 9.834 35.41
380 90.75 64.70 0.51663 0.4061 346.6 960 231.06 165.26 0.74030 10.61 33.52
400 95.53 68.11 0.52890 0.4858 305.0 980 236.02 168.83 0.74540 11.43 31.76
420 100.32 71.52 0.54058 0.5760 270.1 1000 240.98 172.43 0.75042 12.30 30.12
440 105.11 74.93 0.55172 0.6776 240.6 1040 250.95 179.66 0.76019 14.18 27.17
460 109.90 78.36 0.56235 0.7913 215.33 1080 260.97 186.93 0.76964 16.28 24.58
480 114.69 81.77 0.57255 0.9182 193.65 1120 271.03 194.25 0.77880 18.60 22.30
500 119.48 85.20 0.58233 1.0590 174.90 1160 281.14 201.63 0.78767 21.18 20.29
520 124.27 88.62 0.59172 1.2147 158.58 1200 291.30 209.05 0.79628 24.01 18.51
537 128.34 91.53 0.59945 1.3593 146.34 1240 301.52 216.53 0.80466 27.13 16.93
540 129.06 92.04 0.60078 1.3860 144.32 1280 311.79 224.05 0.81280 30.55 15.52
560 133.86 95.47 0.60950 1.5742 131.78 1320 322.11 231.63 0.82075 34.31 14.25
580 138.66 98.90 0.61793 1.7800 120.70 1360 332.48 239.25 0.82848 38.41 13.12
600 143.47 102.34 0.62607 2.005 110.88 1400 342.90 246.93 0.83604 42.88 12.10
620 148.28 105.78 0.63395 2.249 102.12 1440 353.37 254.66 0.84341 47.75 11.17
640 153.09 109.21 0.64159 2.514 94.30 1480 363.89 262.44 0.85062 53.04 10.34
660 157.92 112.67 0.64902 2.801 87.27 1520 374.47 270.26 0.85767 58.78 9.578
680 162.73 116.12 0.65621 3.111 80.96 1560 385.08 278.13 0.86456 65.00 8.890
700 167.56 119.58 0.66321 3.446 75.25 1600 395.74 286.06 0.87130 71.73 8.263
720 172.39 123.04 0.67002 3.806 70.07 1650 409.13 296.03 0.87954 80.89 7.556
740 177.23 126.51 0.67665 4.193 65.38 1700 422.59 306.06 0.88758 90.95 6.924
760 182.08 129.99 0.68312 4.607 61.10 1750 436.12 316.16 0.89542 101.98 6.357
780 186.94 133.47 0.68942 5.051 57.20 1800 449.71 326.32 0.90308 114.0 5.847
800 191.81 136.97 0.69558 5.526 53.63 1850 463.37 336.55 0.91056 127.2 5.388
820 196.69 140.47 0.70160 6.033 50.35 1900 477.09 346.85 0.91788 141.5 4.974
840 201.56 143.98 0.70747 6.573 47.34 1950 490.88 357.20 0.92504 157.1 4.598
860 206.46 147.50 0.71323 7.149 44.57 2000 504.71 367.61 0.93205 174.0 4.258
880 211.35 151.02 0.71886 7.761 42.01 2050 518.61 378.08 0.93891 192.3 3.949
900 216.26 154.57 0.72438 8.411 39.64 2100 532.55 388.60 0.94564 212.1 3.667
920 221.18 158.12 0.72979 9.102 37.44 2150 546.54 399.17 0.95222 233.5 3.410
1. pr and vr data for use with Eqs. 6.43 and 6.44, respectively.
Table A-22E
T(R), h and u(Btu/lb), s(Btu/lb # R)
when s 01 when s 0
2200 560.59 409.78 0.95868 256.6 3.176 3700 998.11 744.48 1.10991 2330 .5882
2250 574.69 420.46 0.96501 281.4 2.961 3750 1013.1 756.04 1.11393 2471 .5621
2300 588.82 431.16 0.97123 308.1 2.765 3800 1028.1 767.60 1.11791 2618 .5376
2350 603.00 441.91 0.97732 336.8 2.585 3850 1043.1 779.19 1.12183 2773 .5143
2400 617.22 452.70 0.98331 367.6 2.419 3900 1058.1 790.80 1.12571 2934 .4923
2450 631.48 463.54 0.98919 400.5 2.266 3950 1073.2 802.43 1.12955 3103 .4715
2500 645.78 474.40 0.99497 435.7 2.125 4000 1088.3 814.06 1.13334 3280 .4518
2550 660.12 485.31 1.00064 473.3 1.996 4050 1103.4 825.72 1.13709 3464 .4331
2600 674.49 496.26 1.00623 513.5 1.876 4100 1118.5 837.40 1.14079 3656 .4154
2650 688.90 507.25 1.01172 556.3 1.765 4150 1133.6 849.09 1.14446 3858 .3985
2700 703.35 518.26 1.01712 601.9 1.662 4200 1148.7 860.81 1.14809 4067 .3826
2750 717.83 529.31 1.02244 650.4 1.566 4300 1179.0 884.28 1.15522 4513 .3529
2800 732.33 540.40 1.02767 702.0 1.478 4400 1209.4 907.81 1.16221 4997 .3262
2850 746.88 551.52 1.03282 756.7 1.395 4500 1239.9 931.39 1.16905 5521 .3019
2900 761.45 562.66 1.03788 814.8 1.318 4600 1270.4 955.04 1.17575 6089 .2799
2950 776.05 573.84 1.04288 876.4 1.247 4700 1300.9 978.73 1.18232 6701 .2598
3000 790.68 585.04 1.04779 941.4 1.180 4800 1331.5 1002.5 1.18876 7362 .2415
3050 805.34 596.28 1.05264 1011 1.118 4900 1362.2 1026.3 1.19508 8073 .2248
3100 820.03 607.53 1.05741 1083 1.060 5000 1392.9 1050.1 1.20129 8837 .2096
3150 834.75 618.82 1.06212 1161 1.006 5100 1423.6 1074.0 1.20738 9658 .1956
3200 849.48 630.12 1.06676 1242 0.9546 5200 1454.4 1098.0 1.21336 10539 .1828
3250 864.24 641.46 1.07134 1328 0.9069 5300 1485.3 1122.0 1.21923 11481 .1710
3300 879.02 652.81 1.07585 1418 0.8621
3350 893.83 664.20 1.08031 1513 0.8202
3400 908.66 675.60 1.08470 1613 0.7807
3450 923.52 687.04 1.08904 1719 0.7436
3500 938.40 698.48 1.09332 1829 0.7087
3550 953.30 709.95 1.09755 1946 0.6759
3600 968.21 721.44 1.10172 2068 0.6449
3650 983.15 732.95 1.10584 2196 0.6157
Table A-23E
TABLE A-23E Ideal Gas Properties of Selected Gases
808
T(R), h and u(Btu/lbmol), s(Btu/lbmol # R)
(hf 169,300 Btu/lbmol) (hf 47,540 Btu/lbmol) (hf 104,040 Btu/lbmol) (hf 0 Btu/lbmol) (hf 0 Btu/lbmol)
300 2108.2 1512.4 46.353 2081.9 1486.1 43.223 2367.6 1771.8 40.439 2073.5 1477.8 44.927 2082.0 1486.2 41.695 300
320 2256.6 1621.1 46.832 2220.9 1585.4 43.672 2526.8 1891.3 40.952 2212.6 1577.1 45.375 2221.0 1585.5 42.143 320
340 2407.3 1732.1 47.289 2359.9 1684.7 44.093 2686.0 2010.8 41.435 2351.7 1676.5 45.797 2360.0 1684.4 42.564 340
360 2560.5 1845.6 47.728 2498.8 1783.9 44.490 2845.1 2130.2 41.889 2490.8 1775.9 46.195 2498.9 1784.0 42.962 360
380 2716.4 1961.8 48.148 2637.9 1883.3 44.866 3004.4 2249.8 42.320 2630.0 1875.3 46.571 2638.0 1883.4 43.337 380
400 2874.7 2080.4 48.555 2776.9 1982.6 45.223 3163.8 2369.4 42.728 2769.1 1974.8 46.927 2777.0 1982.6 43.694 400
420 3035.7 2201.7 48.947 2916.0 2081.9 45.563 3323.2 2489.1 43.117 2908.3 2074.3 47.267 2916.1 2082.0 44.034 420
440 3199.4 2325.6 49.329 3055.0 2181.2 45.886 3482.7 2608.9 43.487 3047.5 2173.8 47.591 3055.1 2181.3 44.357 440
460 3365.7 2452.2 49.698 3194.0 2280.5 46.194 3642.3 2728.8 43.841 3186.9 2273.4 47.900 3194.1 2280.6 44.665 460
480 3534.7 2581.5 50.058 3333.0 2379.8 46.491 3802.0 2848.8 44.182 3326.5 2373.3 48.198 3333.1 2379.9 44.962 480
500 3706.2 2713.3 50.408 3472.1 2479.2 46.775 3962.0 2969.1 44.508 3466.2 2473.2 48.483 3472.2 2479.3 45.246 500
520 3880.3 2847.7 50.750 3611.2 2578.6 47.048 4122.0 3089.4 44.821 3606.1 2573.4 48.757 3611.3 2578.6 45.519 520
537 4027.5 2963.8 51.032 3725.1 2663.1 47.272 4258.0 3191.9 45.079 3725.1 2658.7 48.982 3729.5 2663.1 45.743 537
540 4056.8 2984.4 51.082 3750.3 2677.9 47.310 4282.4 3210.0 45.124 3746.2 2673.8 49.021 3750.3 2678.0 45.781 540
560 4235.8 3123.7 51.408 3889.5 2777.4 47.563 4442.8 3330.7 45.415 3886.6 2774.5 49.276 3889.5 2777.4 46.034 560
580 4417.2 3265.4 51.726 4028.7 2876.9 47.807 4603.7 3451.9 45.696 4027.3 2875.5 49.522 4028.7 2876.9 46.278 580
600 4600.9 3409.4 52.038 4168.0 2976.5 48.044 4764.7 3573.2 45.970 4168.3 2976.8 49.762 4167.9 2976.4 46.514 600
620 4786.6 3555.6 52.343 4307.4 3076.2 48.272 4926.1 3694.9 46.235 4309.7 3078.4 49.993 4307.1 3075.9 46.742 620
640 4974.9 3704.0 52.641 4446.9 3175.9 48.494 5087.8 3816.8 46.492 4451.4 3180.4 50.218 4446.4 3175.5 46.964 640
660 5165.2 3854.6 52.934 4586.6 3275.8 48.709 5250.0 3939.3 46.741 4593.5 3282.9 50.437 4585.8 3275.2 47.178 660
680 5357.6 4007.2 53.225 4726.2 3375.8 48.917 5412.5 4062.1 46.984 4736.2 3385.8 50.650 4725.3 3374.9 47.386 680
700 5552.0 4161.9 53.503 4866.0 3475.9 49.120 5575.4 4185.3 47.219 4879.3 3489.2 50.858 4864.9 3474.8 47.588 700
720 5748.4 4318.6 53.780 5006.1 3576.3 49.317 5738.8 4309.0 47.450 5022.9 3593.1 51.059 5004.5 3574.7 47.785 720
740 5946.8 4477.3 54.051 5146.4 3676.9 49.509 5902.6 4433.1 47.673 5167.0 3697.4 51.257 5144.3 3674.7 47.977 740
760 6147.0 4637.9 54.319 5286.8 3777.5 49.697 6066.9 4557.6 47.893 5311.4 3802.2 51.450 5284.1 3774.9 48.164 760
780 6349.1 4800.1 54.582 5427.4 3878.4 49.880 6231.7 4682.7 48.106 5456.4 3907.5 51.638 5424.2 3875.2 48.345 780
800 6552.9 4964.2 54.839 5568.2 3979.5 50.058 6396.9 4808.2 48.316 5602.0 4013.3 51.821 5564.4 3975.7 48.522 800
820 6758.3 5129.9 55.093 5709.4 4081.0 50.232 6562.6 4934.2 48.520 5748.1 4119.7 52.002 5704.7 4076.3 48.696 820
840 6965.7 5297.6 55.343 5850.7 4182.6 50.402 6728.9 5060.8 48.721 5894.8 4226.6 52.179 5845.3 4177.1 48.865 840
860 7174.7 5466.9 55.589 5992.3 4284.5 50.569 6895.6 5187.8 48.916 6041.9 4334.1 52.352 5985.9 4278.1 49.031 860
880 7385.3 5637.7 55.831 6134.2 4386.6 50.732 7062.9 5315.3 49.109 6189.6 4442.0 52.522 6126.9 4379.4 49.193 880
900 7597.6 5810.3 56.070 6276.4 4489.1 50.892 7230.9 5443.6 49.298 6337.9 4550.6 52.688 6268.1 4480.8 49.352 900
920 7811.4 5984.4 56.305 6419.0 4592.0 51.048 7399.4 5572.4 49.483 6486.7 4659.7 52.852 6409.6 4582.6 49.507 920
940 8026.8 6160.1 56.536 6561.7 4695.0 51.202 7568.4 5701.7 49.665 6636.1 4769.4 53.012 6551.2 4684.5 49.659 940
960 8243.8 6337.4 56.765 6704.9 4798.5 51.353 7738.0 5831.6 49.843 6786.0 4879.5 53.170 6693.1 4786.7 49.808 960
980 8462.2 6516.1 56.990 6848.4 4902.3 51.501 7908.2 5962.0 50.019 6936.4 4990.3 53.326 6835.4 4889.3 49.955 980
1000 8682.1 6696.2 57.212 6992.2 5006.3 51.646 8078.9 6093.0 50.191 7087.5 5101.6 53.477 6977.9 4992.0 50.099 1000
1020 8903.4 6877.8 57.432 7136.4 5110.8 51.788 8250.4 6224.8 50.360 7238.9 5213.3 53.628 7120.7 5095.1 50.241 1020
1040 9126.2 7060.9 57.647 7281.0 5215.7 51.929 8422.4 6357.1 50.528 7391.0 5325.7 53.775 7263.8 5198.5 50.380 1040
1060 9350.3 7245.3 57.861 7425.9 5320.9 52.067 8595.0 6490.0 50.693 7543.6 5438.6 53.921 7407.2 5302.2 50.516 1060
1080 9575.8 7431.1 58.072 7571.1 5426.4 52.203 8768.2 6623.5 50.854 7696.8 5552.1 54.064 7551.0 5406.2 50.651 1080
1100 9802.6 7618.1 58.281 7716.8 5532.3 52.337 8942.0 6757.5 51.013 7850.4 5665.9 54.204 7695.0 5510.5 50.783 1100
1120 10030.6 7806.4 58.485 7862.9 5638.7 52.468 9116.4 6892.2 51.171 8004.5 5780.3 54.343 7839.3 5615.2 50.912 1120
1140 10260.1 7996.2 58.689 8009.2 5745.4 52.598 9291.4 7027.5 51.325 8159.1 5895.2 54.480 7984.0 5720.1 51.040 1140
1160 10490.6 8187.0 58.889 8156.1 5851.5 52.726 9467.1 7163.5 51.478 8314.2 6010.6 54.614 8129.0 5825.4 51.167 1160
1180 10722.3 8379.0 59.088 8303.3 5960.0 52.852 9643.4 7300.1 51.630 8469.8 6126.5 54.748 8274.4 5931.0 51.291 1180
1200 10955.3 8572.3 59.283 8450.8 6067.8 52.976 9820.4 7437.4 51.777 8625.8 6242.8 54.879 8420.0 6037.0 51.413 1200
1220 11189.4 8766.6 59.477 8598.8 6176.0 53.098 9998.0 7575.2 51.925 8782.4 6359.6 55.008 8566.1 6143.4 51.534 1220
1240 11424.6 8962.1 59.668 8747.2 6284.7 53.218 10176.1 7713.6 52.070 8939.4 6476.9 55.136 8712.6 6250.1 51.653 1240
1260 11661.0 9158.8 59.858 8896.0 6393.8 53.337 10354.9 7852.7 52.212 9096.7 6594.5 55.262 8859.3 6357.2 51.771 1260
1280 11898.4 9356.5 60.044 9045.0 6503.1 53.455 10534.4 7992.5 52.354 9254.6 6712.7 55.386 9006.4 6464.5 51.887 1280
1300 12136.9 9555.3 60.229 9194.6 6613.0 53.571 10714.5 8132.9 52.494 9412.9 6831.3 55.508 9153.9 6572.3 51.001 1300
1320 12376.4 9755.0 60.412 9344.6 6723.2 53.685 10895.3 8274.0 52.631 9571.6 6950.2 55.630 9301.8 6680.4 52.114 1320
1340 12617.0 9955.9 60.593 9494.8 6833.7 53.799 11076.6 8415.5 52.768 9730.7 7069.6 55.750 9450.0 6788.9 52.225 1340
1360 12858.5 10157.7 60.772 9645.5 6944.7 53.910 11258.7 8557.9 52.903 9890.2 7189.4 55.867 9598.6 6897.8 52.335 1360
1380 13101.0 10360.5 60.949 9796.6 7056.1 54.021 11441.4 8700.9 53.037 10050.1 7309.6 55.984 9747.5 7007.0 52.444 1380
1400 13344.7 10564.5 61.124 9948.1 7167.9 54.129 11624.8 8844.6 53.168 10210.4 7430.1 56.099 9896.9 7116.7 52.551 1400
1420 13589.1 10769.2 61.298 10100.0 7280.1 54.237 11808.8 8988.9 53.299 10371.0 7551.1 56.213 10046.6 7226.7 52.658 1420
1440 13834.5 10974.8 61.469 10252.2 7392.6 54.344 11993.4 9133.8 53.428 10532.0 7672.4 56.326 10196.6 7337.0 52.763 1440
1460 14080.8 11181.4 61.639 10404.8 7505.4 54.448 12178.8 9279.4 53.556 10693.3 7793.9 56.437 10347.0 7447.6 52.867 1460
1480 14328.0 11388.9 61.800 10557.8 7618.7 54.522 12364.8 9425.7 53.682 10855.1 7916.0 56.547 10497.8 7558.7 52.969 1480
1500 14576.0 11597.2 61.974 10711.1 7732.3 54.665 12551.4 9572.7 53.808 11017.1 8038.3 56.656 10648.0 7670.1 53.071 1500
1520 14824.9 11806.4 62.138 10864.9 7846.4 54.757 12738.8 9720.3 53.932 11179.6 8161.1 56.763 10800.4 7781.9 53.171 1520
1540 15074.7 12016.5 62.302 11019.0 7960.8 54.858 12926.8 9868.6 54.055 11342.4 8284.2 56.869 10952.2 7893.9 53.271 1540
1560 15325.3 12227.3 62.464 11173.4 8075.4 54.958 13115.6 10017.6 54.117 11505.4 8407.4 56.975 11104.3 8006.4 53.369 1560
1580 15576.7 12439.0 62.624 11328.2 8190.5 55.056 13305.0 10167.3 54.298 11668.8 8531.1 57.079 11256.9 8119.2 53.465 1580
1600 15829.0 12651.6 62.783 11483.4 8306.0 55.154 13494.4 10317.6 54.418 11832.5 8655.1 57.182 11409.7 8232.3 53.561 1600
1620 16081.9 12864.8 62.939 11638.9 8421.8 55.251 13685.7 10468.6 54.535 11996.6 8779.5 57.284 11562.8 8345.7 53.656 1620
1640 16335.7 13078.9 63.095 11794.7 8537.9 55.347 13877.0 10620.2 54.653 12160.9 8904.1 57.385 11716.4 8459.6 53.751 1640
1660 16590.2 13293.7 63.250 11950.9 8654.4 55.411 14069.2 10772.7 54.770 12325.5 9029.0 57.484 11870.2 8573.6 53.844 1660
1680 16845.5 13509.2 63.403 12107.5 8771.2 55.535 14261.9 10925.6 54.886 12490.4 9154.1 57.582 12024.3 8688.1 53.936 1680
1700 17101.4 13725.4 63.555 12264.3 8888.3 55.628 14455.4 11079.4 54.999 12655.6 9279.6 57.680 12178.9 8802.9 54.028 1700
1720 17358.1 13942.4 63.704 12421.4 9005.7 55.720 14649.5 11233.8 55.113 12821.1 9405.4 57.777 12333.7 8918.0 54.118 1720
1740 17615.5 14160.1 63.853 12579.0 9123.6 55.811 14844.3 11388.9 55.226 12986.9 9531.5 57.873 12488.8 9033.4 54.208 1740
1760 17873.5 14378.4 64.001 12736.7 9241.6 55.900 15039.8 11544.7 55.339 13153.0 9657.9 57.968 12644.3 9149.2 54.297 1760
1780 18132.2 14597.4 64.147 12894.9 9360.0 55.990 15236.1 11701.2 55.449 13319.2 9784.4 58.062 12800.2 9265.3 54.385 1780
1800 18391.5 14816.9 64.292 13053.2 9478.6 56.078 15433.0 11858.4 55.559 13485.8 9911.2 58.155 12956.3 9381.7 54.472 1800
1820 18651.5 15037.2 64.435 13212.0 9597.7 56.166 15630.6 12016.3 55.668 13652.5 10038.2 58.247 13112.7 9498.4 54.559 1820
1840 18912.2 15258.2 64.578 13371.0 9717.0 56.253 15828.7 12174.7 55.777 13819.6 10165.6 58.339 13269.5 9615.5 54.645 1840
1860 19173.4 15479.7 64.719 13530.2 9836.5 56.339 16027.6 12333.9 55.884 13986.8 10293.1 58.428 13426.5 9732.8 54.729 1860
809
Table A-23E
Table A-23E
810
1900 19,698 15,925 64.999 13,850 10,077 56.509 16,428 12,654 56.097 14,322 10,549 58.607 13,742 9,968 54.896 1900
1940 20,224 16,372 65.272 14,170 10,318 56.677 16,830 12,977 56.307 14,658 10,806 58.782 14,058 10,205 55.061 1940
1980 20,753 16,821 65.543 14,492 10,560 56.841 17,235 13,303 56.514 14,995 11,063 58.954 14,375 10,443 55.223 1980
2020 21,284 17,273 65.809 14,815 10,803 57.007 17,643 13,632 56.719 15,333 11,321 59.123 14,694 10,682 55.383 2020
2060 21,818 17,727 66.069 15,139 11,048 57.161 18,054 13,963 56.920 15,672 11,581 59.289 15,013 10,923 55.540 2060
2100 22,353 18,182 66.327 15,463 11,293 57.317 18,467 14,297 57.119 16,011 11,841 59.451 15,334 11,164 55.694 2100
2140 22,890 18,640 66.581 15,789 11,539 57.470 18,883 14,633 57.315 16,351 12,101 59.612 15,656 11,406 55.846 2140
2180 23,429 19,101 66.830 16,116 11,787 57.621 19,301 14,972 57.509 16,692 12,363 59.770 15,978 11,649 55.995 2180
2220 23,970 19,561 67.076 16,443 12,035 57.770 19,722 15,313 57.701 17,036 12,625 59.926 16,302 11,893 56.141 2220
2260 24,512 20,024 67.319 16,722 12,284 57.917 20,145 15,657 57.889 17,376 12,888 60.077 16,626 12,138 56.286 2260
2300 25,056 20,489 67.557 17,101 12,534 58.062 20,571 16,003 58.077 17,719 13,151 60.228 16,951 12,384 56.429 2300
2340 25,602 20,955 67.792 17,431 12,784 58.204 20,999 16,352 58.261 18,062 13,416 60.376 17,277 12,630 56.570 2340
2380 26,150 21,423 68.025 17,762 13,035 58.344 21,429 16,703 58.445 18,407 13,680 60.522 17,604 12,878 56.708 2380
2420 26,699 21,893 68.253 18,093 13,287 58.482 21,862 17,057 58.625 18,572 13,946 60.666 17,932 13,126 56.845 2420
2460 27,249 22,364 68.479 18,426 13,541 58.619 22,298 17,413 58.803 19,097 14,212 60.808 18,260 13,375 56.980 2460
2500 27,801 22,837 68.702 18,759 13,794 58.754 22,735 17,771 58.980 19,443 14,479 60.946 18,590 13,625 57.112 2500
2540 28,355 23,310 68.921 19,093 14,048 58.885 23,175 18,131 59.155 19,790 14,746 61.084 18,919 13,875 57.243 2540
2580 28,910 23,786 69.138 19,427 14,303 59.016 23,618 18,494 59.328 20,138 15,014 61.220 19,250 14,127 57.372 2580
2620 29,465 24,262 69.352 19,762 14,559 59.145 24,062 18,859 59.500 20,485 15,282 61.354 19,582 14,379 57.499 2620
2660 30,023 24,740 69.563 20,098 14,815 59.272 24,508 19,226 59.669 20,834 15,551 61.486 19,914 14,631 57.625 2660
2700 30,581 25,220 69.771 20,434 15,072 59.398 24,957 19,595 59.837 21,183 15,821 61.616 20,246 14,885 57.750 2700
2740 31,141 25,701 69.977 20,771 15,330 59.521 25,408 19,967 60.003 21,533 16,091 61.744 20,580 15,139 57.872 2740
2780 31,702 26,181 70.181 21,108 15,588 59.644 25,861 20,340 60.167 21,883 16,362 61.871 20,914 15,393 57.993 2780
2820 32,264 26,664 70.382 21,446 15,846 59.765 26,316 20,715 60.330 22,232 16,633 61.996 21,248 15,648 58.113 2820
2860 32,827 27,148 70.580 21,785 16,105 59.884 26,773 21,093 60.490 22,584 16,905 62.120 21,584 15,905 58.231 2860
2900 33,392 27,633 70.776 22,124 16,365 60.002 27,231 21,472 60.650 22,936 17,177 62.242 21,920 16,161 58.348 2900
2940 33,957 28,118 70.970 22,463 16,625 60.118 27,692 21,853 60.809 23,288 17,450 62.363 22,256 16,417 58.463 2940
2980 34,523 28,605 71.160 22,803 16,885 60.232 28,154 22,237 60.965 23,641 17,723 62.483 22,593 16,675 58.576 2980
3020 35,090 29,093 71.350 23,144 17,146 60.346 28,619 22,621 61.120 23,994 17,997 62.599 22,930 16,933 58.688 3020
3060 35,659 29,582 71.537 23,485 17,408 60.458 29,085 23,085 61.274 24,348 18,271 62.716 23,268 17,192 58.800 3060
3100 36,228 30,072 71.722 23,826 17,670 60.569 29,553 23,397 61.426 24,703 18,546 62.831 23,607 17,451 58.910 3100
3140 36,798 30,562 71.904 24,168 17,932 60.679 30,023 23,787 61.577 25,057 18,822 62.945 23,946 17,710 59.019 3140
3180 37,369 31,054 72.085 24,510 18,195 60.787 30,494 24,179 61.727 25,413 19,098 63.057 24,285 17,970 59.126 3180
3220 37,941 31,546 72.264 24,853 18,458 60.894 30,967 24,572 61.874 25,769 19,374 63.169 24,625 18,231 59.232 3220
3260 38,513 32,039 72.441 25,196 18,722 61.000 31,442 24,968 62.022 26,175 19,651 63.279 24,965 18,491 59.338 3260
3300 39,087 32,533 72.616 25,539 18,986 61.105 31,918 25,365 62.167 26,412 19,928 63.386 25,306 18,753 59.442 3300
3340 39,661 33,028 72.788 25,883 19,250 61.209 32,396 25,763 62.312 26,839 20,206 63.494 25,647 19,014 59.544 3340
3380 40,236 33,524 72.960 26,227 19,515 61.311 32,876 26,164 62.454 27,197 20,485 63.601 25,989 19,277 59.646 3380
3420 40,812 34,020 73.129 26,572 19,780 61.412 33,357 26,565 62.597 27,555 20,763 63.706 26,331 19,539 59.747 3420
3460 41,338 34,517 73.297 26,917 20,045 61.513 33,839 26,968 62.738 27,914 21,043 63.811 26,673 19,802 59.846 3460
3500 41,965 35,015 73.462 27,262 20,311 61.612 34,324 27,373 62.875 28,273 21,323 63.914 27,016 20,065 59.944 3500
3540 42,543 35,513 73.627 27,608 20,576 61.710 34,809 27,779 63.015 28,633 21,603 64.016 27,359 20,329 60.041 3540
3580 43,121 36,012 73.789 27,954 20,844 61.807 35,296 28,187 63.153 28,994 21,884 64.114 27,703 20,593 60.138 3580
3620 43,701 36,512 73.951 28,300 21,111 61.903 35,785 28,596 63.288 29,354 22,165 64.217 28,046 20,858 60.234 3620
3660 44,280 37,012 74.110 28,647 21,378 61.998 36,274 29,006 63.423 29,716 22,447 64.316 28,391 21,122 60.328 3660
3700 44,861 37,513 74.267 28,994 21,646 62.093 36,765 29,418 63.557 30,078 22,730 64.415 28,735 21,387 60.422 3700
3740 45,442 38,014 74.423 29,341 21,914 62.186 37,258 29,831 63.690 30,440 23,013 64.512 29,080 21,653 60.515 3740
3780 46,023 38,517 74.578 29,688 22,182 62.279 37,752 30,245 63.821 30,803 23,296 64.609 29,425 21,919 60.607 3780
3820 46,605 39,019 74.732 30,036 22,450 62.370 38,247 30,661 63.952 31,166 23,580 64.704 29,771 22,185 60.698 3820
3860 47,188 39,522 74.884 30,384 22,719 62.461 38,743 31,077 64.082 31,529 23,864 64.800 30,117 22,451 60.788 3860
3900 47,771 40,026 75.033 30,733 22,988 61.511 39,240 31,495 64.210 31,894 24,149 64.893 30,463 22,718 60.877 3900
3940 48,355 40,531 75.182 31,082 23,257 62.640 39,739 31,915 64.338 32,258 24,434 64.986 30,809 22,985 60.966 3940
3980 48,939 41,035 75.330 31,431 23,527 62.728 40,239 32,335 64.465 32,623 24,720 65.078 31,156 23,252 61.053 3980
4020 49,524 41,541 75.477 31,780 23,797 62.816 40,740 32,757 64.591 32,989 25,006 65.169 31,503 23,520 61.139 4020
4060 50,109 42,047 75.622 32,129 24,067 62.902 41,242 33,179 64.715 33,355 25,292 65.260 31,850 23,788 61.225 4060
4100 50,695 42,553 75.765 32,479 24,337 62.988 41,745 33,603 64.839 33,722 25,580 65.350 32,198 24,056 61.310 4100
4140 51,282 43,060 75.907 32,829 24,608 63.072 42,250 34,028 64.962 34,089 25,867 64.439 32,546 24,324 61.395 4140
4180 51,868 43,568 76.048 33,179 24,878 63.156 42,755 34,454 65.084 34,456 26,155 65.527 32,894 24,593 61.479 4180
4220 52,456 44,075 76.188 33,530 25,149 63.240 43,267 34,881 65.204 34,824 26,444 65.615 33,242 24,862 61.562 4220
4260 53,044 44,584 76.327 33,880 25,421 63.323 43,769 35,310 65.325 35,192 26,733 65.702 33,591 25,131 61.644 4260
4300 53,632 45,093 76.464 34,231 25,692 63.405 44,278 35,739 65.444 35,561 27,022 65.788 33,940 25,401 61.726 4300
4340 54,221 45,602 76.601 34,582 25,934 63.486 44,788 36,169 65.563 35,930 27,312 65.873 34,289 25,670 61.806 4340
4380 54,810 46,112 76.736 34,934 26,235 63.567 45,298 36,600 65.680 36,300 27,602 65.958 34,638 25,940 61.887 4380
4420 55,400 46,622 76.870 35,285 26,508 63.647 45,810 37,032 65.797 36,670 27,823 66.042 34,988 26,210 61.966 4420
4460 55,990 47,133 77.003 35,637 26,780 63.726 46,322 37,465 65.913 37,041 28,184 66.125 35,338 26,481 62.045 4460
4500 56,581 47,645 77.135 35,989 27,052 63.805 46,836 37,900 66.028 37,412 28,475 66.208 35,688 26,751 62.123 4500
4540 57,172 48,156 77.266 36,341 27,325 63.883 47,350 38,334 66.142 37,783 28,768 66.290 36,038 27,022 62.201 4540
4580 57,764 48,668 77.395 36,693 27,598 63.960 47,866 38,770 66.255 38,155 29,060 66.372 36,389 27,293 62.278 4580
4620 58,356 49,181 77.581 37,046 27,871 64.036 48,382 39,207 66.368 38,528 29,353 66.453 36,739 27,565 62.354 4620
4660 58,948 49,694 77.652 37,398 28,144 64.113 48,899 39,645 66.480 38,900 29,646 66.533 37,090 27,836 62.429 4660
4700 59,541 50,208 77.779 37,751 28,417 64.188 49,417 40,083 66.591 39,274 29,940 66.613 37,441 28,108 62.504 4700
4740 60,134 50,721 77.905 38,104 28,691 64.263 49,936 40,523 66.701 39,647 30,234 66.691 37,792 28,379 62.578 4740
4780 60,728 51,236 78.029 38,457 28,965 64.337 50,455 40,963 66.811 40,021 30,529 66.770 38,144 28,651 62.652 4780
4820 61,322 51,750 78.153 38,811 29,239 64.411 50,976 41,404 66.920 40,396 30,824 66.848 38,495 28,924 62.725 4820
4860 61,916 52,265 78.276 39,164 29,513 64.484 51,497 41,856 67.028 40,771 31,120 66.925 38,847 29,196 62.798 4860
4900 62,511 52,781 78.398 39,518 29,787 64.556 52,019 42,288 67.135 41,146 31,415 67.003 39,199 29,468 62.870 4900
5000 64,000 54,071 78.698 40,403 30,473 64.735 53,327 43,398 67.401 42,086 32,157 67.193 40,080 30,151 63.049 5000
5100 65,491 55,363 78.994 41,289 31,161 64.910 54,640 44,512 67.662 43,021 32,901 67.380 40,962 30,834 63.223 5100
5200 66,984 56,658 79.284 42,176 31,849 65.082 55,957 45,631 67.918 43,974 33,648 67.562 41,844 31,518 63.395 5200
5300 68,471 57,954 79.569 43,063 32,538 65.252 57,279 46,754 68.172 44,922 34,397 67.743 42,728 32,203 63.563 5300
811
Table A-23E
TABLE A-24E Constants for the van der Waals, RedlichKwong, and BenedictWebbRubin Equations of State
1. van der Waals and RedlichKwong: Constants for pressure in atm, specific volume in ft3/lbmol, and temperature in R
van der Waals RedlichKwong
a b a b
ft3 2 ft3 ft3 2 ft3
Substance atm a b atm a b 1R2 12
lbmol lbmol lbmol lbmol
Air 345 0.586 5,409 0.4064
Butane (C4H10) 3,509 1.862 98,349 1.2903
Carbon dioxide (CO2) 926 0.686 21,972 0.4755
Carbon monoxide (CO) 372 0.632 5,832 0.4382
Table A-24E
Methane (CH4) 581 0.685 10,919 0.4751

Nitrogen (N2) 346 0.618 5,280 0.4286
Oxygen (O2) 349 0.509 5,896 0.3531
Propane (C3H8) 2,369 1.444 61,952 1.0006
Refrigerant 12 2,660 1.558 70,951 1.0796
Sulfur dioxide (SO2) 1,738 0.910 49,032 0.6309
Water (H2O) 1,400 0.488 48,418 0.3380
Source: Calculated from critical data.
2. BenedictWebbRubin: Constants for pressure in atm, specific volume in ft3/lbmol, and temperature in R
Substance a A b B c C
C4H10 7736.7 2587.6 10.26 1.9921 4.214 109
8.254 10 8
4.527 8.724
CO2 562.3 702.4 1.850 0.7995 1.987 108 1.152 108 0.348 1.384
CO 150.6 344.1 0.675 0.8737 1.385 107 7.118 106 0.555 1.540
CH4 203.0 476.0 0.867 0.6824 3.389 107 1.876 107 0.511 1.540
N2 103.2 270.4 0.597 0.6526 9.700 106 6.700 106 0.523 1.360
Source: H. W. Cooper and J. C. Goldfrank, Hydrocarbon Processing, 46 (12): 141 (1967).
TABLE A-25E Thermochemical Properties of Selected Substances at 537R and 1 atm

Heating Values
Enthalpy of Gibbs Function Absolute Higher, Lower,
Molar Mass, Formation, hf of Formation, Entropy, s HHV LHV
Substance Formula M (lb/lbmol) (Btu/lbmol) gf (Btu/lbmol) (Btu/lbmol # R) (Btu/lb) (Btu/lb)
Carbon C(s) 12.01 0 0 1.36 14,100 14,100
Hydrogen H2(g) 2.016 0 0 31.19 61,000 51,610
Nitrogen N2(g) 28.01 0 0 45.74
Oxygen O2(g) 32.00 0 0 48.98
Carbon monoxide CO(g) 28.01 47,540 59,010 47.27
Carbon dioxide CO2(g) 44.01 169,300 169,680 51.03
Water H2O(g) 18.02 104,040 98,350 45.08
Water H2O(l) 18.02 122,970 102,040 16.71
Hydrogen peroxide H2O2(g) 34.02 58,640 45,430 55.60
Ammonia NH3(g) 17.03 19,750 7,140 45.97
Oxygen O(g) 16.00 107,210 99,710 38.47
Table A-25E
Hydrogen H(g) 1.008 93,780 87,460 27.39
Nitrogen N(g) 14.01 203,340 195,970 36.61
Hydroxyl OH(g) 17.01 16,790 14,750 43.92
Methane CH4(g) 16.04 32,210 21,860 44.49 23,880 21,520
Acetylene C2H2(g) 26.04 97,540 87,990 48.00 21,470 20,740
Ethylene C2H4(g) 28.05 22,490 29,306 52.54 21,640 20,290
Ethane C2H6(g) 30.07 36,420 14,150 54.85 22,320 20,430
Propylene C3H6(g) 42.08 8,790 26,980 63.80 21,050 19,700
Propane C3H8(g) 44.09 44,680 10,105 64.51 21,660 19,950
Butane C4H10(g) 58.12 54,270 6,760 74.11 21,300 19,670
Pentane C5H12(g) 72.15 62,960 3,530 83.21 21,090 19,510
Octane C8H18(g) 114.22 89,680 7,110 111.55 20,760 19,270
Octane C8H18(l) 114.22 107,530 2,840 86.23 20,610 19,110
Benzene C6H6(g) 78.11 35,680 55,780 64.34 18,180 17,460
Methyl alcohol CH3OH(g) 32.04 86,540 69,700 57.29 10,260 9,080
Methyl alcohol CH3OH(l) 32.04 102,670 71,570 30.30 9,760 8,570
Ethyl alcohol C2H5OH(g) 46.07 101,230 72,520 67.54 13,160 11,930
Ethyl alcohol C2H5OH(l) 46.07 119,470 75,240 38.40 12,760 11,530
Source: Based on JANAF Thermochemical Tables, NSRDS-NBS-37, 1971; Selected Values of Chemical Thermodynamic Properties, NBS Tech.
Note 270-3, 1968; and API Research Project 44, Carnegie Press, 1953. Heating values calculated.
Index to Figures and Charts
Figure A-1 Generalized compressibility chart, pR 1.0 814

Figure A-2 Generalized compressibility chart, pR 10.0 815
Figure A-3 Generalized compressibility chart, 10 pR 40 815
Figure A-4 Generalized enthalpy correction chart 816
Figure A-5 Generalized entropy correction chart 817
Figure A-6 Generalized fugacity coefficient chart 818
Figure A-7 Temperatureentropy diagram for water (SI units) 819
Figure A-8 Enthalpyentropy diagram for water (SI units) 820
Figure A-9 Psychrometric chart for 1 atm (SI units) 821
Figure A-1 Generalized compressibility chart, pR 1.0. Source: E. F. Obert, Concepts of

Thermodynamics, McGraw-Hill, New York, 1960.
814
Figures and Charts 815
Figure A-2 Generalized compressibility chart, pR 10.0. Source: E. F. Obert, Concepts of

Figure A-3 Generalized compressibility chart, 10 pR 40. Source: E. F. Obert. Concepts of

816 Figures and Charts
Figure A-4 Generalized enthalpy correction chart. Source: Adapted from G. J. Van Wylen
and R. E. Sonntag, Fundamentals of Classical Thermodynamics, 3rd. ed., English/SI, Wiley,
New York, 1986.
Figure A-5 Generalized entropy correction chart. Source: Adapted from G. J. Van
Wylen and R. E. Sonntag, Fundamentals of Classical Thermodynamics, 3rd. ed.,
English/SI, Wiley, New York, 1986.
Figure A-6 Generalized fugacity coefficient chart. Source: G. J. Van Wylen and R. E. Sonntag,
Fundamentals of Classical Thermodynamics, 3rd. ed., English/SI, Wiley, New York, 1986.
Figure A-7 Temperatureentropy diagram for water (SI units). Source: J. H. Keenan, F. G. Keyes,
P. G. Hill, and J. G. Moore, Steam Tables, Wiley, New York, 1978.
Figure A-8 Enthalpyentropy diagram for water (SI units). Source: J. B. Jones and G. A.
Hawkins, Engineering Thermodynamics, 2nd ed., Wiley, New York, 1986.
Figure A-9 Psychrometric chart for 1 atm (SI units). Source: Z. Zhang and M. B. Pate, A
Methodology for Implementing a Psychrometric Chart in a Computer Graphics System, ASHRAE
Transactions, Vol. 94, Pt. 1, 1988.
Answer to Selected Problems
1.10 2551 (c) subcooled (compressed) 4.25 25 bars

1.11 9.5, 98.1 liquid, (d) superheated vapor, 4.28 10,400
(e) solid
1.13 6.131 4.31 14.08 kW
3.8 1.36
1.14 3.92, 0.125 4.32 0.14
3.9 23.4
1.16 29.62 4.36 15.98
3.10 6.189
1.18 68.67
3.11 0.025 4.40 56.1
1.21 (a) 1.33, 0.67
3.14 0.188, 10.5 4.42 (a) 3.673 kg/min
1.26 (a) 0.2, 2.67 (b) 615.3 kJ/min
3.16 140, 0.8520, 0.002
1.27 58 (vacuum) 4.46 18
3.18 33.86, 153.13
1.28 decreases
3.19 0.0296 4.53 54.7
1.29 A: 2.68, B: 1.28
3.24 73.4 4.61 143.5
1.30 0.8
3.27 10.4, 32.31 4.64 (a) 47.4 kg
1.32 1.893 Mpa, 14.73
3
3.30 1.6386 10 3
m /kg, 4.66 83.39
1.40 71.6
274.26 kJ/kg 4.69 2.9, 1043
1.41 33.33, 166.67, 1.5
3.32 1751.1 5.15 decrease TC
1.42 no
3.34 2.392 kJ/kg, 20.23
2.2 97.8 5.16 (a) (TH
TC)2,
3.37 52.1, 42.0 (b) (THTC)12
2.3 4800
3.41 24, 239.8 5.17 (a) (1max) 1, (b) 1max
2.4 (a) 56,520, 489,000 (b) 162.8
3.42 66.7, 105 TC TH T0
2.6 210 kJ 5.20 (a)
3.45 49.3
(b) 32.57 10 , 91.4 THT0 TC
# 0 T2 W ,
4
2.7 #
3.47 mc1dTdt2 hA1T THTH TC
T 1t2 T0 1W hA2
(c) 0.5 m, 53.01 TC TH
5.21 (a) , (b) 6
51 exp 31hA mc2t4 6 THTH TC
2.16 0.02 TC TH
2.19 150, 100 k, 0.125 3.48 (a) 0.79 (b) 0.791 5.23 952
2.17 40 3.49 0.103 5.27 75
2.18 80.47 3.50 3
7.88 10 , 148 5.29 (a) 6.7%
2.20 1.843 3.52 (a) 6.685 (b) 6.973 5.30 possible but uneconomical
2.22 300, 9.42 3.57 460 5.34 no
2.26 1.96 3.62 425.6, 2.462 5.36 900
2.31 0.842 3.64 297.9, 24.1, 1167.7, 0 5.39 3.33, 0.41
2.33 0.064 3.65 1.041 5.40 no
2.37
350 kJ 3.69 (a) 252.4, (b) 245 5.46 (b) 12: 2914, 330, 23: 0,
2.44 109.8 4.3 35.3, 4.17 983.0, 34: 2140.2, 167.1,
2.45 1.747 4.4 tf 15.36 41: 0, 373.0, (c) 26.5
2.46 (a) 112.6 Kpa 4.8 0.3717, 6.095 6.1 (a) 0.667, imp
(b) 68.89 J (b) 0, internally reversible
4.10 5.04, 0.65
(c) 131.39 J (c)
0.667, possible,
4.14 0.73, 0.042
2.49 (b) 8.28 kJ (c) 18.78 kJ and irreversible
(d) 36.9 kJ 4.17 44.6
WR W1
4.18 (a) 664.1, (b) 17, 6.2 6.2 (a):
2.50 15 kJ, 30% TC
Qs 11 T0 Ts 2 11 T0 Tu 2
#
2.56 300 kJ, 200 kJ 4.20 25.3 kJ/kg 6.6
2.57 1.34 kW 4.22 319.6 K 6.10 (a): W mp(vg vf), Q
3.1 (a) two-phase, liquidvapor 4.23 102.5 m(hg hf)
mixture, (b) superheated vapor, 4.24 7.53, 0.108 6.12 F, T, F, F
822
Answer to Selected Problems 823
(c): QH c 1 d
TC 7.17 411.2, 339.2 9.30 372.6, 833.3, 55.3
6.15
TH 7.19 40.14, 13.42 9.33 pressure ratio 8, t c
6.16 (b): mc 3TH
TC 21THTC 2 12 4 7.25 1.87 10 4 80%, (a) 24.1%, (b) 0.582,
(c) 1271.9, (d) 186.6, 255.1
6.19 4.9128, 0.4337, 0.97515, 7.28 0.481, 0.044
22.163 9.36 pressure ratio 8, t c
7.36 101.9 80%, (a) 36.4%, (b) 0.582,
6.22 6.9, 4.12, 0.188
7.43 21.6%, 0.9% (c) 1271.9, (d) 65.64
6.24 25.224
7.48 173.3, 2.8 9.40 (a) 365.68, 370.94, (b) 365.7,
6.28 471.5, 2391.8 (c) % increase 15.2
7.54 $40,900/year
6.29 (b): 153.81, 153.81 9.45 49.68, single stage: 60.11
7.56 25.06, 27.73
6.34 (b): 28.6, (c) 68.2% 9.53 (b) 1009 m/s
7.62 5.6%
6.36 18.1%, 26.5% 9.55 1080
7.67 (a) 1927, 340.8, (b) 85%
6.37
, 0, ,
,
, indeterminate 9.56 766.5, 1348
7.70 382.9, 8.94 104, 45.9%
6.39 0: 56.20 9.57 10, 296.4
7.77 (b): Capital, 75%
6.41 no 9.60 3635, 78.6, 0.214
7.80 (b): 0.59
6.45 no 9.62 (a) 4.19 (b) 69% (c) 5.89
8.1 (a) 4.01 10 , 258.4 10 ,
5 3
6.49 .057 W/K 158.4 103, 38.7 9.63 37.95 (opposite to direction of flow)
6.52 436.7, 1.189, 0.428, 0.762 8.6 921.6, 2339.5, 39.4, 1417.9 9.65 48.33
6.56 (a); 0.3709 8.10 25 9.69 1007 N, 1.452 kW
6.60 0.59 8.11 24, 59.7, 1304.2, 990.9 9.73 inlet: 0.054, 340.2, 15.01
6.62 equal, less, greater, 8.13 33.6, 3.38 10 , 8.48 10
5 6 exit: 0.819, 340.2, 9.67
indeterminate, greater 9.76 (a) 418.2, 4.238
8.18 44.2
6.66 from right to left, 1741 (b) 446.6, 4.456
8.23 235 10 , 42.5, 5.825 10
3 6
6.71 12.75 (c) 432, 4.344

8.29 1268.3, 47.6, 1394.1
6.74 1 9.79 (a) .4047, .5943
8.30 1100.7, 41.4, 1558.3
6.87 (a): 0.2223, 0.217 9.84 (a) 1.81, (b) 2.87, (c) 461,
8.31 2.43 105, 41.2, 6.14 106
6.91 0.8146, 1.3394 (d) 5.94 102
8.34 36.8, 1.17 10 6
(a) aV21
2kRT1 10.1 25.8, 3.85, 151.94, 6.92

6.96 8.36 1218.6, 45.6, 1453.8
k1 10.2 7.251, 1.062, 6.83
p2 1k12k 12 8.37 1062.2, 39.7, 1610.1
c1 a b db 8.39 43.18, 3.375 105
10.3 2.21, 3.62, 5.75
p1
10.7 4.05, 15.51
6.99 354.8 8.42 39.2, 1.1 106
10.10 3.73, 3.4, 3.21, 0.71, 0.58
6.101 1020.5, 89.8% 8.45 43.9
10.14 0.241, 5.647, 0.0606,
6.104 809.7 8.50 (a) 9.529 108, 236, 500,
6.227, 0.9743
3.032 109
6.108 (a): 207.9, 0.0698 10.16 6.61, 6.86, 2.61
8.52 (a) 191 103 kW (b) 133.2
6.111 (b): 162.17, 30.66 10.17 (a) 55.3, 10.7 (b) 44.66, 4.85
103 kW (c) 57.8 103 kW
6.114 (pump work/compressor work) (d) 69.7% (c) 3.57
0.34% 10.20 2.126, 7.055, 19.53
9.1 721.12, 51.5%, 949.2, 2331 K
6.119 no 10.24 1.868, 1.687
9.2 805.2, 57.5%, 1060 KPa, 2656 K
6.120 629.7, 81.7 10.26 16.0, 43.86, 2.74, 6.75
9.13 23.19, 2.19, 59.7%, 975
7.2 (a) 542.27, (b) 12.51, (c) 21.94 10.34 46.2, 60.48
9.14 22.01, 2.081, 65.7, 883
7.5 (a) 17.86 (b) 3.53 (c) 3.04 11.1 125.29, 80.1, 79.5, 79.2,
9.18 rc 1.5: 1301.5, 189.2, 297.5
(b) cpT0 c 1 ln d
T T 59.4 100
7.9
T0 T0 9.19 7.389, .543, 727.6 11.2 79.5, 80.1, 79.5, 79.2, 79.35, 85.53
7.10 CO2 9.26 37.47, 14.26, 31.44, 20.29, 60.8 11.5 767.5, 1145.7, 1076.5
7.14 51, 711 9.27 pressure ratio 6: 37.7%, vR 2764
11.11 b
7.16 0, 153.6, 29.53 0.345, 2218.6 vR 18 vRT 2R
824 Answer to Selected Problems
11.16 p
RT

cons tan t
(b) C3H8, C2H6: 0.4, CH4: 0.2, 13.39 1,299, 202, 1.68
vb (c) 26.71
13.41 45,720, 49,500
11.19 (a) positive, (b) zero, (c) negative 12.7 0.337, 4.84
13.43 849,100, 46,810
11.22 p RTv, s R ln(vv)
12.9 291.46, .3159
13.47 89.2%, 10.8%
c ln(TT) 12.11 3014, 8.485
13.50 (a) 1859, 6.42 (b) .9985,
11.27 271.3 K, 269.5 K 12.14 110.8, .0505 5.343 106
11.29 0.292 12.21 440.2, 6.295, 0.175 13.52 165.3
11.33 (a) 0.0424 bar, (b) 36.19C 12.22 387, 3.628, 2510.3, 3010.3 13.57 (a) 800, 770 (b) 800, 792
11.36 cp cv
R 12.24 234, 2.094 13.59 8.18 105
p2 R
c
4 d,
3AR 12.27 claim invalid 13.64 (b): (a) 34,212, (b) 116,554,
11.39 (a)
RT p T 12.29 15.5% (c) 51,756
(b) R ln
4 3p2 p1 4
p2 3AR 12.30 no 13.68 (a) 544.5, (b) 546 Model 1 546.7
p1 T 12.32 .00865, 2.0234 13.74 (a) 275,364, (b) 226,105,
(c) 49,259, (d) e 82.1%
11.44 b
a b ,
1 1 0Z 12.33 10.4
T Z 0T p 12.39 2.24, 228.1 13.80 (a) 0, (b) 0.31, (c) 1.97
k a b
1 1 0Z 12.40 537.3, 0.1774 14.3 (a) 5.018
p Z 0p T 14.5 (a) 2.224, (b) 2.224,
12.41 3.7%, 30.3, 0.022
kR 3 (c) 4.448
11.49 cp 4 3Z2 12.42 7.08, 3.3 10
k1 14.9 (b) 5.018
12.43 (a): 68%, 0.0182, 76.3
R 14.16 (a) increase, (b) no change
11.50 (b) , 12.45 20, 68%
1 2a1v b2 2RTv3 14.21 CO2: 0.528, CO: 0.472,
2 12.49 (a) 38.31, (b) .007.7
cv 1T 2dT
O2: 0.736, N2: 3.76
(c) u2 u1 12.51 12.3, 0.0144 (removed)
14.25 CO2: 45.54%, CO: 21.43%,
12.56 52%, 32 O2: 33.04%
ac d
1 1
v2 v1 12.58 (a) 81.8%, 14.4 (b) .048 14.30 CO2: 2, H2O: 1.428, NO: 0.1134,
11.54 no 12.59 290.8, 11338 O2: 0.9433, N2: 13.1033
b 2 12.60 82.65, 28 14.34 593,269
c1 a bd
2a
11.57 Tinv 13.1 162 14.35 (a) 322,386, 31,816
bR v
13.5 (b) 8.25, 12.05 14.37 (a) 139.18, (b) 139.66
11.66 T 2R a b pR, pR
dB d1TRB2
dTR dTR 13.8 SO2: 0.029 kg/kg(O2) 14.39 108%
11.71 29.7 13.11 0.116, 9.777 14.40 4.04
11.75 349.7 (table: 369.8) 13.14 0.038 14.42 4.89
11.79 221.7, 148.5, 166.9 13.17 C: 7.0322, H: 15.61, 1.361 14.44 Est.: 278,100
11.80 0.031 13.18 (b) 9.19, (c) CO2: .15, CO: 0.1, 14.48 0.84
N2: .75 14.52 0.015
11.85 0.1125, 0.1163
13.19 (c) CO2: 5.54%, CO: 11.09%,
11.88 95.1, 1.96 14.54 CO2: 0.28808, H2O: 0.71105,
N2: 83.37% CO: 0.71192, O2: 0.000435,
11.94 101.1
13.23 115%, 51 H2: 0.28895
11.98 18.2, 6.37
13.26 (b) CO: 5991, SO2: 666 14.59 0.072%
12.3 (a) N2: 50.61%, CO2: 39.76%;
13.29 1.269 (rich) 14.65 (a) 3, (b) 4, (c) 5
O2: 9.64%, (b) N2: 0.06, CO2:
0.03, O2: 0.01, (c) 37.3 13.31 2.19 106
12.4 (a) C3H8: 0.5365, C2H6: 0.3659, 13.34 0.037
CH4: 0.0976, 13.37 82,670
Index
Absolute entropy, 648651, 653, 655, 657, Base unit, 8, 9, 18, 41 Closed feedwater heaters, 350, 352
661, 670 Beattie-Bridgeman equation of state, 493 Closed system:
Absolute pressure, 12, 99, 102 Benedict-Webb-Rubin equation of state, 493 Definition, 3
Absolute temperature scale, 191 table of constants, 762, 812 energy balance for, 4858
Absorption refrigeration cycle, 469 Bernoulli equation, 255 entropy balance for, 220222, 652
Acid rain, 329 Berthelot equation of state, 490 exergy balance for, 283285
Activity, 547, 548, 646, 694, 695 Binary vapor power cycle, 356 Coefficient of performance:
Additive pressure, rule of, 532, 533, 535, Biomass, 371 heat pump cycle, 61, 184, 188,
536, 545, 564 Boiler, 149, 197, 198, 310, 311, 312, 313, 190, 192
Additive volume, rule of, 533, 546, 564 314, 325, 326, 327, 328, 329, 330, 331, maximum for two reservoirs, 192196
Adiabatic engine, 332, 333, 334, 335, 337, 338, 339, 340, refrigeration cycles, 60, 189, 456
Adiabatic Flame temperature, 641, 642, 343, 346, 352, 356, 357, 358, 359, 360, Coefficient of volume expansion, 514
643, 645, 669, 695 361, 362, 363 Cogeneration, 308, 310, 311, 312, 313, 315,
Adiabatic Process, 14, 45, 196, 197, 198, Boltzmanns constant, 231 356, 357, 358, 365, 519, 647
218, 224, 226 Bore (of cylinder), 373, 374 Combined cycle, 399, 419, 420, 421, 424,
Adiabatic-saturation temperature, 588, 589, Boundary, 4 467, 667
590, 593 Brayton cycle, 389, 390, 391, 392, 393, 394, Combustion,
Adiabatic wall, 14 395, 397, 399, 401, 404, 405, 444, 445, air for, 632, 633, 642
Afterburner, 415 454, 474, 478, 479 complete, 620, 649, 669
Air products of, 620, 645, 649, 669
atmospheric, 560, 609 Capacity, refrigeration, 458 Compressed liquids, see Liquids
for combustion, 272 Capillary tube, 15 Compressibility:
dry air, approximate composition of, 560 Carnahan-Starling-Desantis equation of state, isentropic, 513515
excess, 404, 623, 624, 625, 628, 669 550, 554 isothermal, 513515
ideal gas properties of, 756 Carnot corollaries, 186, 187, 190, 193 Compressibility chart, 94, 95, 96, 97, 98, 99,
moist air, 603, 604, 606 Carnot cycle, 196, 197, 198, 199, 218, 335, 101, 110, 141, 147, 488, 491, 493, 533,
percent of theoretical, 623, 627 336, 425, 426, 456, 472 535
saturated, 580 engine, 199 Compressibility factor, 94, 95, 96, 99, 100,
theoretical (stoichiometric), 622, 645 heat pump, 198, 199, 200, 201 102, 114, 487, 488, 490, 491, 524, 525,
Aircraft engines, 137, 418 power, 197, 198, 199 528, 532, 533, 535, 543
Air-fuel ratio, 622 refrigeration, 198, 199 Compressible flow, 373, 426, 427, 429, 430,
Air-standard analysis Carnot efficiency, 192, 193, 194, 196 437, 444
for gas turbines, 388 Cascade cycles, 467, 468, 479, 480 Compressible flow functions, table of, 437,
for internal combustion engines, 373 Cavitation, 271 438
Air-standard cycles: Celsius (Centigrade) temperature scale, 18, 19 Compression ratio, 374, 377, 378, 379, 382,
Brayton cycle, 389390 Chemical equilibrium, 7, 558, 648, 652, 679, 383, 384, 386, 444, 445
Diesel cycle, 381383 683, 684, 687, 695, 696, 700, 706, 711 Compression with intercooling, 404, 406,
dual cycle, 385388 Chemical exergy, 620, 655, 656, 657, 658, 407, 408, 425, 444, 445, 467, 468, 479,
Otto cycle, 375379 659, 660, 661, 662, 663, 664, 665, 666, 480
Air-water vapor mixtures, 558, 579580, 667, 668, 669, 670 Compressor, 247, 306, 389
587, 611 Chemical potential, 539, 540, 547, 548, 681, isentropic efficiency of, 247249, 252
Allotropic transformation, 120 682, 683, 685, 687, 694, 706, 707, 708, Condenser, 2, 144, 145, 148, 149, 198, 238,
Amagat model, 562, 564, 611 709, 710, 711 239, 240, 302, 303, 326, 327, 328, 329,
Ammonia, properties of, 76, 81, 82, 84, 85, as escaping tendency, 707 330, 331, 333, 334, 335, 337, 338, 340,
211, 356, 465, 469, 470, 471, 663, 664, for ideal gas mixtures, 547, 548 341, 342, 344, 346, 348, 349, 350, 351,
710 for ideal solutions, 547, 548 352, 353, 354, 356, 357, 358, 359, 360,
Area interpretation, 38, 218 for pure substance, 682, 683 363, 364, 365, 366, 419, 421, 423, 424,
Atkinson cycle, 446 Chlorofluorocarbon (CFC) compounds, 455, 456, 457, 458, 459, 460, 461, 462,
Atmospheric air, 175, 388, 560, 609, 610 120, 465 463, 464, 466, 467, 468, 469, 470, 471,
Atmospheric Pressure, standard, 12 Choked flow, 433, 434, 444 472, 473, 610
Atomic and molecular weights, table of, 719, Clapeyron equation, 504, 505, 506, 507, 520, Conduction, energy transfer by, 20, 45, 46,
767 521, 548, 705, 706 55, 62, 184
Availability, see Exergy Clausius, inequality of, 177, 206208, 220, Conservation of Energy, 18, 20, 29, 32, 33,
506, 706 49, 58, 59, 62, 121, 128, 129, 174, 175,
Back pressure, 432, 433, 434, 435, 438, 439, Clausius-Clapeyron equation, 706 187, 188, 228, 254, 326, 327, 351, 358,
441, 442, 444, 445 Clausius statement of the second law, 177 359, 564, 587, 589, 620, 629, 631,
Back work ratio, 329, 331, 332, 333, 356, 390, equivalence with Kelvin-Planck 633, 635, 637, 639, 642, 648, 679,
392, 393, 394, 397, 399, 403, 412, 414 statement, 200 684
825
826 Index
Conservation of mass, 20, 121, 122, 123, 124, Disorder, 230, 231 Enthalpy:
125, 127, 133, 153, 162, 174, 209, 232, Dissociation, 620, 645, 693, 694, 695, approximation using saturated liquid data,
236, 272, 327, 330, 347, 358, 361, 365, 696, 700 92, 93
426, 428, 431, 566, 587, 589, 590, 594, District heating, 358 change upon mixing, 568
598, 599, 601, 605, 610, 612, 620, 623, Dry-bulb temperature, 590, 591, 592, 593, of combustion, 638641
624, 626, 627, 628, 629, 642, 684, 689, 597, 598, 602, 603, 604, 607 definition, 83
690, 693, 703, 704 Dry compression, 456, 457 departure, 524526
Constant-pressure, specific heat, 74, 101, 110, Dry product analysis, 625, 626 of formation, 630, 631, 633, 636
112, 243, 336, 381, 385, 386, 407, 415, Dual cycle, 375, 385, 386, 387, 444, 468 of ideal gas, 103, 112
521 of ideal gas mixtures,
Constant-volume, specific heat, 16, 17, 18, Economics, engineering economics, 20, of ideal solutions,
112, 191, 243, 375, 376, 381, 385, 386, 28, 309 of incompressible substances, 93
425, 680 Effectiveness, 303, 306, 307, 308, 400, 401, of moist air, 603
Constraints, design, 19, 149, 178, 240 402, 403, 405, 412, 413, 425 of reaction, 700
Continuum hypothesis, 10 compressors, 307 reference states and reference values, 84,
Control mass, 3 heat exchanger, 308 85
Control surface, 3, 4, 130, 134 regenerator, 400 stagnation (total), 430, 431
Control volume: pumps, 308 Enthalpy correction chart, generalized,
definition, 3 turbine, 306 524526
energy balance for, 121, 128131, 162 Efficiency: Enthalpy-entropy diagram, 212, 240
entropy balance for, 231240 Carnot, 192 for water, 582
exergy balance for, 293303 exergetic, 302309 Entropy:
mass balance for, 123125 isentropic compressor, 246, 248 absolute, 210212, 648
momentum equation for, 426427 isentropic nozzle, 246 of air-water vapor mixtures, 582, 611
Convection, energy transfer by, 46 isentropic pump, 246, 248 approximation using saturated liquid data,
Cooling tower, 326, 579, 609, 610, 612 isentropic turbine, 246 211, 212
Corresponding states, principles of, 96, 97 rational, 324 Boltzmann relation for, 231
Cost: second law, 303307 change upon mixing, 546, 573
annualized, 28, 309 thermal, 60 definition, 209
capital, 309310 Elastic systems, simple, 70 departure, 528, 529
fuel, 309310 Electricity: and disorder, 230231
owning and operating, 310315 off-peak, 172, 371 general comments, 210
total, 310 peak demand, 172, 371 of ideal gas, 213215
unit, 196, 305 Electric power, expression for, 4, 41, 57, 146, of ideal gas mixtures, 546
Critical constants, 97 147, 293, 309, 329, 420, 645, 647 of incompressible substances, 213, 214
table of, 719 Electronic cooling, 2, 172 principle of increase of, 228229
Critical point, 71, 72, 73, 79, 212, 489, Emissivity, 46 production, 181, 221224
490, 491 Endothermic reactions, 645 of reacting systems, 648, 649
Critical Pressure in nozzel, 72, 74, 75, 96, 97, Energy: transfer, 218, 221223, 231233
100, 341, 433, 439, 488, 489, 491, conservation of, 18, 20, 32, 33, 49, 58, 59, Entropy balance:
524, 532 129, 679, 684 for closed systems, 220222, 652
Cryogenic refrigeration,2, 646 internal, 43 for control volumes, 231, 232,
Cutoff ratio, 382, 383, 384 kinetic, 29, 30, 43, 44, 48 for reacting systems, 649
Cycle, thermodynamic, 5 potential, 29, 31 Entropy correction chart, generalized,
solar, 67, 189, 202, 204 524526
Dalton model, 545, 562, 563, 611, 612 total, of a system, 43 Environment, exergy reference, 273275, 655,
Dead State, 275, 276, 277, 278, 282, 285, transfer, 143 656, 657, 659664
286, 290 Energy balance: Equations of state
Deaeration, 352 for closed systems, 4858 Beattie-Bridgeman, 493
Dehumidification, 594, 598, 599, 612 for control volumes, 121, 128131, Benedict-Webb-Rubin, 493
Density, 1013 162 table of constants, 762, 812
Design, 1, 5, 19, 20 for psychrometric systems, 579, Berthelot, 490
Dessicant dehumidification, 619 for reacting systems, 631635 Carnahan-Starling-Desantis, 550, 554
Dew point, 583, 584, 585, 586, 587, 592, 598, Engineering design, 18, 19, 22, 325 ideal gas, 100, 101, 113
611, 612, 625, 626, 627, 636 Engineering model, 20 Redlich-Kwong, 490-493
Differentials, exact vs. inexact,, 35, 49, 223, Engines: table of constants, 762, 812
494, 495, 497, 498, 499, 500, 515, 548 Adiabatic, 452 van der Waals, 488, 489
Diesel cycle, 381, 382, 383, 385, 386 Carnot, 205 table of constants, 762, 812
Diffuser, 134, 135, 183, 414, 415, 416, 417, internal combustion, 374, 375, virial, 99, 488
418, 430, 432, 434, 443 turbojet, 414, 415, 416 Equilibrium:
Dimensions, 8, 9, 56, 134, 491 Stirling, 426 chemical, 7, 648, 652, 679, 684686
Displacement volume, 374, 375, 380 English engineering units, 10 criteria for, 7, 679681, 711
Index 827
definition, 7 Flow work, 130, 135, 144, 152, 157, 290, Heat engine, see Power cycle
flame temperature, 695, 696 291, 292, 293, 294, 595 heat exchanger, 134, 143, 144, 162, 296, 297,
mechanical, 7, 655, 664, 679 Flowmeter, 172 298, 302, 307, 308, 309, 310, 326, 327,
multicomponent, multiphase, 679, 681 Fluidized bed combustion, 329 328, 340, 346, 356, 358, 359, 360, 361,
phase, 7, 679682, 704706 Fluid mechanics, 1, 11, 125, 162, 255, 309, 427 362, 388, 389, 390, 391, 392, 393, 395,
reaction, equation of, 684686 Flywheel, 185 396, 398, 399, 400, 401, 402, 405, 406,
state, 7 Fouriers law, 45, 46 413, 419, 420, 421, 422, 423, 424, 456,
test for, 7 Freon-12, see Refrigerant 459, 467, 468, 469, 470, 473, 474, 475,
thermal, 7, 655, 664 Friction, 52, 58, 176, 180, 181, 182, 183, 476, 477, 478, 479, 645
thermodynamic, 7, 679, 681 222, 225, 228, 240, 252, 298, 302, Heat index, 619
Equilibrium constant: 362, 375, 396 Heat islands, 189
for ideal gas mixtures, 687692 Fuel-air ratio, 622, 623 Heat pump, 6062, 471473
for ideal solutions, 694 Fuel cells, 2, 519, 645, 646, 647, 667, 670, 685 air source, 472, 473
table of, 765 Fuels, 646, 647 Carnot cycle, 472, 473
Equivalence ratio, 623 Fugacity vapor-compression, 472, 473
Ericsson cycle, 425, 426 of ideal solutions, 545, 546 Heat rate, 328
Evaporative cooling, 604, 606, 612 multicomponent systems, 541545 Heat recovery steam generator, 150,
Evaporator, 148, 238, 240, 455, 456, 457, Fundamental thermodynamic function, 497, 302, 309
458, 459, 460, 461, 462, 463, 464, 466, 503, 520, 521, 540, 541, 548 Heat transfer coefficient, 47, 54, 55, 56
467, 468, 469, 470, 471, 472, 473 use in developing property tables, 466, 710 table of typical values, 47
Exact differentials, 35, 497, 498, 500, 548 Heating values, 638, 639, 640, 661
test for exactness, 494 Gage pressure, 12 Helmholtz function, definition, 498
Excess air, 404, 623, 624, 625, 628, 669 Gas chromatograph, 625 use in developing steam tables, 522524
Exergy (Availability): Gas constant, universal, 94, 95, 215, 493 HFCs (hydrofluorocarbons), 465
analysis, general comments, 272, 273, 283 Gas turbine Higher Heating values, 638, 639, 640, 661
chemical, 620, 655659 air-standard analysis, 387, 389 Humid air turbine (HAT) cycle, 619
definition, 273 with intercooling, 404 406 Humidification, 594, 601, 602, 612
destruction, 273, 283, 284, 285 open to atmosphere, 389 Humidity ratio (specific humidity), 581
evaluation of, 295 for propulsion, 414 418 Hybrid electric vehicle, 31
flow exergy, 664666 regenerative, 399 402 Hydrocarbon fuels, 620, 621, 625, 641,
reference environment for, 273275, 278, with reheat, 404406 663, 670
655, 656, 659, 660 steam-injected, 452, 619 Hydroelectric, 293, 325, 685
standard chemical, 659664 Generalized charts Hydrogen economy, 685
thermomechanical, 278, 655657, 664 compressibility, 9497, 490, 491, 493, Hygrometer, 582
transfer, 283285, enthalpy correction, 524531 Hypersonic, 429
Exergy analysis: entropy correction, 524531
reacting systems, 667670 fugacity, 695 Ice point, 18, 19
vapor power plant, 359, 360 Gibbs-Duhem equation, 540, 541, 556 Ideal gas:
Exergy balance: Gibbs function: enthalpy, 103, 112
for closed systems, 283, 284 definition, 498 entropy, 213215
for control volumes, 293, 303 of formation, 654, 658 equation of state, 100, 101, 113
Exothermic reactions, 630, 631 of ideal gas mixture, 683, 684 internal energy, 100, 101, 105
Extensive Property, 6, 31, 32, 43, 62, 129, partial molal, 539, 711 model, definition of, 70, 91, 94
209, 228, 229, 230, 231, 257, 277, 278, Gibbs phase rule, 706, 709, 710, 711 polytropic process of, 243, 256
315, 536, 537, 538, 681 Global warming, 84, 626 specific heat relations, 103105
Extent of reaction, 686 Gravimetric analysis, 559, 560, 561 tables of properties of, 756, 758,
External combustion engines, 426 Gravitational potential energy, 32, 33, 43, 806, 808
External irreversibility, 469 48, 62 Ideal gas mixtures
chemical potential for, 547, 548
Fahrenheit temperature scale, 18 Head loss, 271 Ideal solutions, 546, 547, 548, 695
Fanno line, 436 Heat: Inclined manometer, 13, 27
Feedwater heater, 125, 143, 346, 347, 348, capacity, see Specific heat Incomplete combustion, 645, 670, 695
349, 350, 351, 352, 354, 356 definition, 14 Incompressible substance, 92, 93, 94, 213,
First law of Thermodynamics, 30, 32, 34, 36, energy transfer by, 4448 217, 230
38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, entropy transfer accompanying, 218, Increase of entropy, principle of, 228, 229,
60, 62, 64, 66, 68 221, 222 230, 285, 680
Flame temperature exergy transfer accompanying, 284, Independent Property, 70, 151
adiabatic, 641, 642, 643, 645 285, 286 Inequality of Clausius, 177, 206208, 220,
equilibrium, 695, 696 flux, 45 506, 706
Flash chamber, 469 sign convention, 45, 47 Inexact differential, 35
Flow exergy, 290, 291, 292, 293, 295, 296, transfer modes, 4547 Infrared analyzer, 625
297, 298, 306, 307, 315, 664, 665, 666 waste, 308 Intake stroke, 374
828 Index
Intensive Property, 6, 10, 14, 42, 43, 69, 75, Kays rule, 532, 533, 534, 535, 536, 548 Mole fraction, 559562
281, 429, 539, 682, 710 Kelvin-Planck statement of the second law, Mollier diagram,, 212, 246, 247, 504, 582
Intercepts, method of, 537, 538, 548 178, 179 for water, 582
Intercooling, compression with, 404, 405, analytical expression of, 184, 185 Momentum equation for control
406, 407, 408, 409, 410, 411, 412, 413, equivalence with Clausius statement, 188, volumes, 451452
414, 424, 425, 444, 445, 467, 468, 469, 189 Montreal Protocols, 120
479, 480 interpretation for cycles, 207, 218
internal combustion Engines, 280, 308, 325, Kelvin temperature scale, 190, 191, 199 Natural gas, 3, 272, 303, 313, 420, 454, 469,
373, 374, 375, 378, 385, 391, 426, 444, Kinetic energy, 22, 29, 30, 31, 32, 33, 43, 44, 621, 628, 646
622, 645, 667 48, 52, 132, 135, 137, 138, 139, 141, Natural Refrigerant, 84
nomenclature, 375 142, 143, 147, 148, 247, 251, 252, 276, Newtons law of cooling, 47, 56
internal Energy 416, 417, 431, 693 Newtons second law of motion, 30
approximation using saturated liquid Kinetic theory, 104 Normal shock, 430, 434, 435, 436, 440, 441,
data, 101 442, 443, 444, 445
change upon mixing, 43, 44 Laminar flow, 164 table of functions, 441
general comments, 43 Lewis-Randall rule, 545, 546 Normal stress, 11, 40, 42
of ideal gas, 100, 101, 105 Linear interpolation, 77, 78, 114, 572 Nozzle,
of incompressible substances, 93101 Liquids: choked flow,, 433, 434, 444
microscopic interpretation of, 44 compressed (subcooled), 74 converging,
Internal irreversibility, 337, 461 incompressible model for, 92 converging-diverging,
internally reversible Process, 184, 197, 198, saturated, 92, 93, 94 isentropic efficiency, 246
199, 208, 209, 213, 214, 217, 218, 219, Lithium bromide absorption cycle, 470 Nuclear power, 28, 68
220, 221, 225, 287, 330, 334, 354, 376, Log mean temperature difference, 68
381, 425, 455 Lower heating value, 639, 640 Ocean thermal energy conversion
International System of Units, see SI units Low-head dam, 172 (OTEC), 271
International Temperature Scale, 191, 192 One-dimensional flow, 121, 124, 125, 126,
Interpolation, 77, 78, 114, 191, 211, 241, 251, Mach number, 426, 427, 429, 432, 433, 434, 129, 162, 290, 292, 294, 426, 427, 433,
253, 281, 332, 362, 382, 461, 572, 585, 437, 438, 439, 440, 441, 442, 443, 444 435, 444, 595
587, 644, 691 Macroscopic viewpoint, 5 Open feedwater heater, 143, 346, 348, 349,
Inversion states, 518 Magnetic systems, simple, 70 352, 354
Ionization, 625, 646, 695, 700, 701 Manometer, 13, 16 Open system, see Control volume 4
Irreversibilities, 179, 180, 181, 183, 184, 185, Mass, Optical Pyrometer, 16
186, 189, 196, 199, 207, 208, 220, 221, units for, 810 Orsat analyzer, 625
222, 223, 224, 226, 227, 228, 232, 233, Mass balance, 123, 125, 131, 149, 152, 594, Otto cycle, 375, 376, 377, 378, 379, 381, 382,
234, 237, 240, 245, 246, 247, 249, 253, 598, 606, 608, 610 383, 386
254, 255, 257, 273, 274, 277, 283, 284, Mass flow rate, 122124 Optimization, 19, 310, 312, 407, 661, 666
285, 288, 289, 290, 294, 298, 302, 303, Mass flux, 125
304, 308, 311, 315, 327, 329, 330, 336, Mass fraction, 559, 560, 561, 562, 566, 581, Partial molal properties, 536, 537, 539, 548
337, 338, 340, 344, 345, 349, 358, 365, 611, 612, 621 Partial pressure, 544, 545, 563, 566, 567, 568,
375, 391, 396, 397, 399, 406, 411, 415, Maxwell relations, 497, 499, 500, 501, 504, 570, 572, 576, 578, 580, 581, 582, 583,
420, 425, 444, 454, 458, 459, 463, 464, 541, 548 584, 585, 586, 588, 590, 592, 596, 597,
465, 474, 476, 477, 478, 479, 645, 646, Mean effective pressure, 375, 379, 380, 383, 598, 601, 605, 606, 611, 627, 649, 651,
657, 660, 667, 680 384, 388 652, 653, 654, 656, 658, 660, 683, 707,
Irreversibility, see Exergy destruction Mechanical equilibrium, 278, 655, 664, 679 708, 709
Irreversible process, 180, 182, 184, 224, 436, Melting, 71, 75, 76, 192, 504, 505, 506 Partial volume, 564
459, 681 MEMS, (microelectromechanical systems), Peak demand, 172, 371
Isentropic compressibility, 513, 514, 515, 517 134 Peng-Robinson equation of state
Isentropic efficiency Method of intercepts, 537, 538 Perfect gas, see Ideal gas
compressor, 246, 248 Methodology for solving problems, 330, 333 Perpetual motion machine, 204, 205
nozzle, 246 Micromachines, 270 Phase
pump, 246, 248 Microscopic viewpoint, 41, 100, 230 change, 71, 73, 74, 75, 198, 214, 341, 504,
turbine, 246 Microturbines, 519 505, 506, 548
Isentropic process, 218, 240 Mixtures: diagram, 71, 72, 73, 76, 77, 496, 506
ideal gas relations for, 240245 ideal gas, 611, 683, 684 equilibrium, 708, 709, 711
Isolated system, 231, 280, 282, 285 ideal solutions, 536, 546 rule, Gibbs, 679, 706, 709, 710, 711
Isothermal compressibility, 514, 515, 517 p-v-T relations for, 611 Photovoltaic cell, 371
Isothermal process, 14, 196, 198, 218, 426 Model, engineering, 20 Piezoelectric effect, 13
Moist air, 603, 604 Pinch analysis (technology), 324
JANAF tables, 717, 761, 765 Molar (volumetric) analysis, 559, 564 Plancks equation, 191
Jet engine, 2, 414, 415, 416, 426, 479 Molar basis, 10, 11 Polytropic process, 41, 271
Joules experiments, 44, 48 Molecular weight, of an ideal gas, 112114, 243, 256
Joule-Thompson coefficient, 518, 519 table of values, 719, 767 Potential energy, 29, 31, 32
Index 829
Power, test for, 5, 38 gas systems, 454, 479

electrical, 3, 56 thermometric, 14, 15, 16 magnetic, 486
transmitted by a shaft, 41, 56 pseudoreduced specific volume, 97, 242, 490, multistage compression with intercooling,
Power cycle, 59, 60 491, 492 404, 406411
Pressure: Psychrometer, 590, 591, 593 steam jet, 482
absolute, 12, 99, 102 Psychrometric chart, 592, 593, 597, 598, 599, thermoelectric, 68
atmospheric, standard, 12 600, 601, 602, 603, 604, 606, 607, 608, ton of, 458
critical, 72, 74, 75, 96, 97, 100 611, 612 vapor-compression, 457, 458
critical, in nozzle, 341, 433, 439, 488, 489, Pump, Regelation of ice, 556
491, 524, 532 isentropic efficiency, 246, 248 Regeneration:
definition, 8, 11 Pure substance, 6, 7, 69, 70, 71, 73, 74, 503, Ericsson cycle, 425, 426
gage, 12 546, 682, 705 in gas refrigeration, 473, 474
mean effective, 375, 376 Pyrometer, optical, 16 in gas turbines, 399401
partial,, 544, 545, 563, 566, 567, 568, 570, Stirling cycles, 196, 424, 425, 426, 444, 445
572, 576, 578, 580, 581, 582, 583, Quality, definition, 14, 75, 78, 79, 80, 81, 83, Regenerator, 399, 400 405, 411413, 419, 425
584, 585, 586, 588, 590, 592, 596, 86, 89, 90, 91, 138, 139, 144, 145, 148, Effectiveness, 400404
597, 598, 601, 605, 606, 611, 627, 149, 150, 151, 153, 154, 210, 211, 212, Reheat:
649, 651, 652, 653, 654, 656, 658, 213, 238, 241, 331, 340, 342, 343, 349, in gas turbines, 404, 405
660, 683, 707, 708, 709 354, 456, 464, 469, 585, 587 in vapor power plants, 325, 329, 340, 341
reduced, 96, 97 Quasiequilibrium (quasistatic) processes, 7, Relative humidity, 581, 582, 584, 585, 586,
relative, 242 22, 42, 43, 70, 88 592, 59598, 600, 601, 604607, 610612
saturation, 7173 Relative pressure, 242
sensors, 13 Radiation, thermal, 8, 16, 45, 46, 60, 62, 191, Relative volume, 242
stagnation (total), 430, 437 326, 591 Reservoir, thermal, 16, 178, 179, 181, 182,
vacuum, 12 Radiation thermometer, 16 183, 184, 185, 186, 187, 188, 189, 190,
Pressure-enthalpy diagram, 466, 467 Ram effect, 414, 419 191, 192, 193, 196, 197, 198, 206, 207,
Pressure-temperature diagram (phase Ramjet, 418, 419 208, 222
diagram), 71, 72 Rankine cycle, 327, 329, 330, 331, 333, 334, Resistance temperature detector, 16
Pressure-volume diagram, 73, 74 335, 336, 337, 338, 339, 340, 341, 355, Reversible Process, 180184
Pressure-volume-temperature surface, 73, 74 356, 365, 366 internally reversible,184, 197, 198, 199,
Principle of increase of entropy, 228, 229, Rankine temperature scale, 18, 194, 198, 218 208, 209, 213, 214, 217, 218, 219,
230, 285, 680 Rayleigh line, 436 220, 221, 225, 287, 330, 334, 354,
Problem-solving methodology, 330, 333 Reacting systems, 620, 629, 630, 637, 639, 376, 381, 425, 455
Process: 643, 648, 649, 654, 667, 669, 670, 679,
adiabatic, 14, 45, 196, 197, 198, 218, 684, 692, 704 Saturated air, 580
224, 226 energy balances for, 631635 Saturated liquid, 7173
definition, 5 entropy balances for, 649 Saturated vapor,7173
internally reversible, 184, 197, 198, 199, exergy analysis of, 667670 Saturation pressure,7173
208, 209, 213, 214, 217, 218, 219, Reaction equilibrium, equation of, 684, 685, Saturation Temperature, 73, 74, 75, 77, 78,
220, 221, 225, 287, 330, 334, 354, 686, 687, 694 81, 83, 89, 210, 583, 585, 586, 588, 589,
376, 381, 425, 455 Reciprocating compressor, 139, 466 590, 591, 593
irreversible, 180, 182, 184, 224, 436, Rectifier, 470, 471 Second law efficiency, 303306
459, 681 Recuperator heat exchangers, 327
isentropic, 218, 240 Redlich-Kwong equation of state, 490493 turbines, compressors, pumps, 134
polytropic, 243, 256 table of constants, 762, 812 Second law of thermodynamics:
quasiequilibrium (quasistatic),, 7, 22, 42, Reduced property, 524526 Clausius statement, 177
43, 70, 88 Reference state, 84, 85, 106, 107, 210, 211, general remarks, 177180
reversible, 180184 215, 216, 430, 547, 592, 629, 648, 655 Kelvin-Planck statement, 178, 179
throttling, 148, 149, 238, 295, 296, 354, Refrigerant, 61, 76 Semiconductor, 16
458, 459, 460, 461, 462, 464, 518 Refrigerant 22, properties of, 22, 76, 85 Sign convention:
Propane,properties of 76, 84, 85, 97, 465 Refrigerant 134a, properties of, 76, 83, 85 for cycles, 376
Property: Refrigerant, natural, 84, 85 for heat, 45, 47
definition, 5 Refrigerants, 84, 85, 210, 211, 465, 466, 468, for work, 34, 35
extensive, 6, 31, 32, 43, 62, 129, 209, 228, 479, 520 Simple compressible system, 69, 70
229, 230, 231, 257, 277, 278, 315, Refrigeration, Simple system, 70
536, 537, 538, 681 absorption, 2 SI units, 8, 9, 10, 22, 86, 90, 91, 159, 212,
independent, 70, 151 Brayton cycle, 474, 478, 479 217, 592
intensive, 6, 10, 14, 42, 43, 69, 75, 281, capacity, 458 Solar energy, 189
429, 539, 682, 710 Carnot cycle, 196, 197, 198, 199, 218, 335, Solid oxide fuel cell, 645, 646, 647
reduced, 524526 336, 425, 426, 456, 472 Solutions:
relations from exact differentials, 35, 494, Cascade cycles, 467 468 equilibrium constant for, 694
497, 498, 500, 548 cryogenic, 646 ideal, 546
830 Index
Sound, velocity of, 427429 Superheated vapor, 75, 77, 79, 81, 82, 83, 84, Thermometric property, 14, 15, 16
Specific heat: 98, 99, 212, 213, 238, 240, 241, 340, Thermostatic expansion valve, 485
constant-pressure, 74, 101, 110, 112, 243, 342, 354, 457, 460, 462, 463, 584, 710 Thermosyphon, 372
336, 381, 385, 386, 407, 415, 521 Supersonic, 429, 430, 432, 434, 435, 436, Third law of thermodynamics, 210, 648, 649,
constant-volume, 16, 17, 18, 112, 191, 243, 437, 443, 444, 445 651, 653
375, 376, 381, 385, 386, 425, 680 Surface tension, 40, 42 Throat, 432, 434, 435, 443, 444
of ideal gases, 91, 103, 104, 105, 106, 565, Surroundings, 3, 173, 175 Throttling calorimeter, 148, 149
569 Sustainable development, 28 Throttling process, 148, 149, 238, 295, 296,
of ideal gas mixtures, 564, 566 System: 354, 458, 459, 460, 461, 462,
of monatomic ideal gases, 119 boundary, 3 464, 518
relations, 113 closed, 3 Thrust, 415, 418, 419
of solids and liquids, 92, 93 definition, 3 Ton of refrigeration, 458, 601
zero-pressure, 92, 105 isolated, 3, 228, 230, 273 Topping cycle, 356, 357, 419
Specific heat ratio, 91, 104, 243, 244, 377, open (control volume), 3 Transient analysis of control volumes, 153
392, 394, 395, 410, 429, 441, 444, 516, simple compressible, 69, 70, 213, 274 Transonic, 429
517, 548, 565 simple, 3,70 Triple point, 17, 18, 19, 71, 72, 73, 75, 76,
Specific humidity (humidity ratio), 581 System integration, 134, 149 84, 191, 192
Specific volume, 11 Turbine,
approximation using saturated liquid data, T dS equations, 213, 214, 498 effectiveness, 306
92, 93 Temperature: isentropic efficiency, 345, 477
critical, 71, 72, 77 absolute, 46, 49, 191, 206, 207 Turbofan engine, 418
molar, 12 adiabatic flame, 641645 Turbojet engine, 2, 414, 415, 416
pseudoreduced, 97 dew point, 583588 Turboprop engine, 418
reduced, 97 dry-bulb, 590, 591
Stagnation state, 426, 430, 436, 437, equality of, 14 Ulitmate analysis, 621622
442, 444 equilibrium flame, 695699 Units:
Standard state, 629, 630, 631, 648, 654 gas scale of, 17, 18 English engineering, 911
State: Kelvin scale of, 17, 18, 190, 191 SI (Systme Internationale dUnits), 89
dead, 275 reduced, 96 Universal gas constant, 95
definition, 5 saturation, 73 Urban heat islands, 189
equilibrium, 7 sensors, 15 U-tube manometer, 26
reference, 210, 211, 215 stagnation, 430
stagnation, 426 thermodynamic scale of, 190, 191 Vacuum pressure, 12
steady, 5, 125162, 233, 254 triple point, 18, 19, 71, 73, 76, 192 Valves, 3, 134, 373, 374
triple, 71, 73 various scales of, 18 Van der Waals equation of state, 489,
State principle, 69, 70, 79, 114 wet-bulb, 590, 591 491, 496
Statistical thermodynamics, 5, 230, 231, 630, Temperature-entropy diagram, 211, 212 table of constants, 762, 812
648, 700 for water, 581 vant Hoff equation, 695, 699, 700,
Steady state, 5, 125162, 233, 254 Temperature-specific volume diagram, 73, 74 706, 711
Steam generator, 2, 150, 151, 300, 301, 302, Theoretical air, for combustion,622, 623, 624, Vapor, saturated, 75, 77
309, 340, 341, 346, 348, 349, 351, 353, 626, 627, 628, 629, 643, 644, 649, 650, Vapor-compression heat pumps, 471473
354, 356, 358, 361, 366 651, 665, 666, 668, 670 Vapor-compression refrigeration, 148, 457,
Steam point, 18, 19 Thermal conductivity, 46, 466 458, 459, 461, 462, 463, 467, 472,
Stagnation Temperature, 437, 440, 443 Thermal efficiency, 60 479, 480
Steam-injected gas turbine, 452 of a Carnot cycle, 186 Vaporization, 71, 75, 76, 79, 83, 341, 457,
Steam jet refrigeration, 482 Thermal equilibrium, 14, 16 504, 506, 631
Steam rate, 271 Thermal pollution, 326 Vapor power cycle, 329, 336, 338, 340, 341,
Steam tables, 76, 349, 487, 503, 507, 508, Thermal radiation, energy transfer by,45, 46 346, 347, 348, 349, 350, 351, 352, 353,
522, 582, 589, 631, 665 Thermal reservoir, 178, 182, 184, 185, 186, 188, 355, 356, 358, 365, 394, 419, 421,
Stefan-Boltzmann law, 46, 47 189, 190, 191, 192, 193, 196, 199, 207 422, 423
Stirling cycles, 196, 424, 425, 426, Thermistor, 16 Velocity of sound, 426, 427, 429, 433, 444,
444, 445 Thermodynamics: 514, 515, 516, 517, 522
Stoichiometric coefficient, 621, 685, 686, first law of, 29 48 Virial equation of state, 488
688, 702 general comments, 1 Volume:
Stress, 11, 35, 40, 42, 114, 138 second law of, 18, 43, 58, 61, 84 change upon mixing, 538
Stroke (piston), 373376 statistical, 5, 230, 231 critical specific, 72
Subcooled liquids, see Liquids third law of, 210, 648, 649, 651, 653 partial, 564
Sublimation, 71, 75, 76, 504, 505, 506 zeroth law of, 14 pseudoreduced specific, 97
Subsonic, 429, 430, 432, 433, 434, 435, 436, Thermodynamic tables, Appendix reduced specific, 97
437, 439, 443, 444, 445 Thermoeconomics, 309, 310, 311, 313 relative, 242
Superheat, 89, 210, 211, 340, 341, 343, 345, Thermometer, 14, 15, 16, 17, 18, 148, 191, specific, 10
347, 356, 365, 420 590, 591 Volume expansivity, 513, 514, 515, 517, 548
Index 831
Volumetric analysis, 559, 564 Wind turbines, 293 Working fluid, 325, 326, 328, 329, 330, 331,
Volumetric flow rate, 124, 125, 126, 141, 142, Work: 332, 333, 334, 335, 336, 337, 338, 339,
392, 393, 475, 476, 478, 577, 595, 596, electrical, 56 341, 342, 343, 344, 346, 348, 349, 351,
597, 600, 604, 605, 607, 608 energy transfer by, 35, 41, 42, 130 352, 353, 354, 356, 358, 359, 365, 373,
Vortex tube, 237 exergy transfer accompanying, 284, 286, 375, 381, 388, 390, 393, 395, 396, 398,
289 399, 401, 402, 405, 406, 410, 411, 413,
Waste heat, 150, 300, 308, 469, 473, 668 expansion or compression, 3640 415, 416, 421, 425, 426, 444, 459, 462,
Water: extension of a solid bar, 33 465, 471, 473, 476, 477
steam tables, 76, 77, 582, 589, 631 flow work, 130, 131
Water-gas reaction, 712 in mechanics, definition of, 34 Youngs modulus, 64
Wet-bulb temperature, 590, 591, 593, 602, polarization and magnetization, 41 43
603, 604, 606, 611 in quasiequilibrium processes, 42, 70 Z-chart, see generalized compressibility chart
Wet compression, 456 sign convention for, 34 Zeldovich mechanism, 716
Wind chill index, 591 thermodynamic definition of, 34 Zero-pressure specific heat, 105
Wind tunnels, 426 transmitted by a shaft, 41, 42 Zeroth law of thermodynamics, 14

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5th Edition

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Typeset in 10/12 pt Times by Techbooks

Type of course Intended audience Chapter coverage

Further Study Aids

Standard Acceleration of Gravity Temperature Relations

9.12 Compressible Flow Preliminaries 426

12.3 Evaluating U, H, S and Specific Heats 564

TABLE 1.1 Selected Areas of Application of Engineering Thermodynamics

Air in Hot gases

Turbojet engine Biomedical applications

Air in Drive Air in

1.3 Describing Systems and Their Behavior

MACROSCOPIC AND MICROSCOPIC VIEWS OF THERMODYNAMICS

Figure 1.3 Air compressor and

The microscopic approach to thermodynamics, known as statistical thermodynamics, is

PROPERTY, STATE, AND PROCESS

EXTENSIVE AND INTENSIVE PROPERTIES

PHASE AND PURE SUBSTANCE

ACTUAL AND QUASIEQUILIBRIUM PROCESSES

There is no requirement that a system undergoing an actual process be in equilibrium during

1.4 Measuring Mass, Length, Time, and Force

TABLE 1.2 Units and dimensions for Mass, Length, Time

1 N 11 kg2 11 m/s2 2 1 kg # m/s2 (1.2)

Quantity Dimensions Units Symbol Name

1.5 Two Measurable Properties: Specific

1.5.1 Specific Volume

and not simply as the product of density and volume.

The number of kilomoles of a substance, n, is obtained by dividing the mass, m, in kilograms

where M is the molecular weight in kg/kmol or lb/lbmol, as appropriate.

The SI unit of pressure and stress is the pascal.

Zero pressure Zero pressure

PRESSURE MEASUREMENT patm

p  patm rgL (1.10)

Elliptical metal Pointer

1.6.1 Thermal Equilibrium

Thermodynamics in the News...

substance that exhibits changes in the thermometric property is known as a thermometric

OTHER TEMPERATURE SENSORS

Liquid Figure 1.9 Thermometers.

where is an arbitrary constant. The linear relationship is an arbitrary choice; other

Measured data for a

1.6.3 Kelvin Scale

In view of the limitations of empirical means for measuring temperature, it is desirable

1.6.4 Celsius Scale

T1C2 T1K2  273.15 (1.14)

Figure 1.12 Comparison of temperature scales.

Engineers frequently do analysis, whether explicitly as part of a design process or for

1.7.3 Methodology for Solving Thermodynamics Problems

Find: State concisely in your own words what is to be determined.

EXAMPLE 1.1 Identifying System Interactions

p patm rgL (1.10)

T1C2 T1K2 273.15 (1.14)

p 3 15.18 103 2T 1v 0.0026682 4 18.91 103 2 v2 3 in.

mV d V mV2 d m 1V22 V21 2

KE KE2 KE1 m 1V22 V21 2

PE PE2 PE1 mg 1z2 z1 2 (2.10)

11 kg2 a9.7 b 110 m2 ` ` ` `

m1u2 u1 2 4 kg a4.6 b 18.4 kJ