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C M Y CM MY CY CMY K
MECHANICAL ENGINEERING S E C O N D
E D I T I O N
Advanced Thermodynamics Engineering
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S E C O N D E D I T I O N
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Advanced Thermodynamics Engineering, Second Edition is designed for readers who
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need to understand and apply the engineering physics of thermodynamic concepts.
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It employs a self-teaching format that reinforces presentation of critical concepts,
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mathematical relationships, and equations with concrete physical examples and
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explanations of applications—to help readers apply principles to their own real-
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world problems.
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Less Mathematical/Theoretical Derivations—More Focus on Practical Application m
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Because both students and professionals must grasp theory almost immediately
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in this ever-changing electronic era, this book—now completely in decimal outline
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format—uses a phenomenological approach to problems, making advanced
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concepts easier to understand. After a decade teaching advanced thermodynamics,
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the authors infuse their own style and tailor content based on their observations m
as professional engineers, as well as feedback from their students. Condensing
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more esoteric material to focus on practical uses for this continuously evolving c
area of science, this book is filled with revised problems and extensive tables s
on thermodynamic properties and other useful information. E
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The authors include an abundance of examples, figures, and illustrations to g
clarify presented ideas, and additional material and software tools are available i
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for download. The result is a powerful, practical instructional tool that gives
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readers a strong conceptual foundation on which to build a solid, functional e
understanding of thermodynamics engineering. r
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Annamalai
Puri
Jog
K10287
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Advanced
Thermodynamics
Engineering
S E C O N D E D I T I O N
CRC Series in
COMPUTATIONAL MECHANICS
and APPLIED ANALYSIS
Series Editor: J.N. Reddy
Texas A&M University
Published Titles
ADVANCED THERMODYNAMICS ENGINEERING, Second Edition
Kalyan Annamalai, Ishwar K. Puri, and Miland Jog
APPLIED FUNCTIONAL ANALYSIS
J. Tinsley Oden and Leszek F. Demkowicz
COMBUSTION SCIENCE AND ENGINEERING
Kalyan Annamalai and Ishwar K. Puri
CONTINUUM MECHANICS FOR ENGINEERS, Third Edition
Thomas Mase, ROnald Smelser, and George E. Mase
DYNAMICS IN ENGINEERING PRACTICE, Tenth Edition
Dara W. Childs
EXACT SOLUTIONS FOR BUCKLING OF STRUCTURAL MEMBERS
C.M. Wang, C.Y. Wang, and J.N. Reddy
THE FINITE ELEMENT METHOD IN HEAT TRANSFER AND FLUID DYNAMICS,
Third Edition
J.N. Reddy and D.K. Gartling
MECHANICS OF LAMINATED COMPOSITE PLATES AND SHELLS: THEORY
AND ANALYSIS, Second Edition
J.N. Reddy
NUMERICAL AND ANALYTICAL METHODS WITH MATLAB®
William Bober, Chi-Tay Tsai, and Oren Masory
PRACTICAL ANALYSIS OF COMPOSITE LAMINATES
J.N. Reddy and Antonio Miravete
SOLVING ORDINARY AND PARTIAL BOUNDARY VALUE PROBLEMS
IN SCIENCE and ENGINEERING
Karel Rektorys
STRESSES IN BEAMS, PLATES, AND SHELLS, Third Edition
Ansel C. Ugural
Advanced
Thermodynamics
Engineering
S E C O N D E D I T I O N
Kalyan Annamalai
Ishwar K. Puri
Milind A. Jog
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
Cover Photo courtesy of Luminant Generation Company LLC, Dallas, Texas.
CRC Press
Taylor & Francis Group
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© 2011 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Version Date: 20110722
International Standard Book Number-13: 978-1-4398-0571-8 (eBook - PDF)
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Dr. Annamalai dedicates this text to his wife, Vasantha, who stood by
him during his cliff hanging journey of life, the grandchildren Rohen,
Ravi, and Sophie and to all his gurus during his education:
Professor Pandeli Durbetaki, Georgia Institute of Technology, Atlanta
Professor Gollahalli Subrahmanyam, University of Oklahoma, Norman
Late Professor Merwin Sibulkin, Brown University, Providence, Rhode Island
Dr. Puri thanks his wife, Beth, for pulling more than her load and acknowledges his debt
to his sons, Shivesh, Sunil, and Krishan, for allowing him to take time off from other
pressing responsibilities, such as playing catch. His career has been a journey during which
his entire family, including his parents, Krishan and Sushila Puri, have played a vital role.
Dr. Jog dedicates this text to his wife, Radhika, and son, Aditya, for
their encouragement and support and to his parents, Arun and Suman
Jog, from whom he inherited his love of engineering.
Contents
List of Tables in Appendix A .............................................................................................xxv
List of Figures in Appendix B ..........................................................................................xxix
Preface to Second Edition ................................................................................................xxxi
Nomenclature ..................................................................................................................xxxv
Thermolab Excel®-Based Software for Thermodynamic Properties, Flame
Temperatures of Fuels, Conversion Units, Math Functions and Other Properties ............xli
Four Important Equations in Analysis of Thermal Systems ...............................................xlv
1 Introduction .................................................................................................................1
Objectives ..........................................................................................................................1
1.1 Importance, Significance and Limitations ...............................................................1
1.2 Review of Thermodynamics ....................................................................................2
1.2.1 System and Boundary .................................................................................2
1.2.2 Simple System .............................................................................................2
1.2.3 Constraints and Restraints .........................................................................4
1.2.4 Composite System ......................................................................................4
1.2.5 Phase ..........................................................................................................4
1.2.6 Homogeneous .............................................................................................4
1.2.7 Pure Substance ...........................................................................................5
1.2.8 Amount of Matter and Avogadro Number .................................................5
1.2.9 Mixture ......................................................................................................6
1.2.10 Property ......................................................................................................7
1.2.11 State............................................................................................................8
1.2.12 Equation of State .......................................................................................10
1.2.13 Standard Temperature and Pressure ..........................................................10
1.2.14 Partial Pressure ..........................................................................................11
1.2.15 Process .......................................................................................................11
1.2.16 Vapor–Liquid Phase Equilibrium ..............................................................11
1.3 Mathematical Background .....................................................................................14
1.3.1 Explicit and Implicit Functions and Total Differentiation .........................14
1.3.2 Exact (Perfect) and Inexact (Imperfect) Differentials .................................16
1.3.2.1 Mathematical Criteria for an Exact Differential ........................18
ix
x ◾ Contents
1.3.3 Relevance to Thermodynamics .................................................................20
1.3.3.1 Work and Heat .........................................................................20
1.3.3.2 Integral over a Closed Path (Thermodynamic Cycle) .................21
1.3.4 Homogeneous Functions ..........................................................................22
1.3.4.1 Relevance of Homogeneous Functions to Thermodynamics .....24
1.3.5 LaGrange Multipliers ...............................................................................26
1.3.6 Composite Function .................................................................................28
1.4 Overview of Microscopic/Nanothermodynamics ..................................................29
1.4.1 Matter ......................................................................................................29
1.4.2 Intermolecular Forces and Potential Energy .............................................29
1.4.3 Collision Number, Mean Free Path, and Molecular Velocity .....................33
1.4.3.1 Collision Number and Mean Free Path .....................................33
1.4.3.2 Maxwellian Distribution of Molecular Velocity .........................35
1.4.3.3 Average, Root Mean Square (RMS), and Most Probable Speeds ....36
1.4.4 Thermal and Internal Energy ....................................................................37
1.4.4.1 Monatomic Gas ........................................................................38
1.4.4.2 Diatomic Gas ...........................................................................38
1.4.4.3 Triatomic and Polyatomic Gases ...............................................39
1.4.5 Temperature .............................................................................................39
1.4.6 Pressure ....................................................................................................40
1.4.6.1 Relation between Pressure and Temperature .............................40
1.4.7 Gas, Liquid, and Solid ..............................................................................42
1.4.8 Work .........................................................................................................45
1.4.9 Heat Transfer and Thermal Equilibrium ..................................................46
1.4.10 Chemical Potential ...................................................................................46
1.4.10.1 Multicomponent into Multicomponent .....................................47
1.4.10.2 Single Component into Multicomponent .................................48
1.4.11 Boiling/Phase Equilibrium .......................................................................49
1.4.11.1 Single Component Fluid ...........................................................49
1.4.11.2 Multiple Components ...............................................................50
1.4.12 Entropy .....................................................................................................51
1.4.12.1 Overview ...................................................................................51
1.4.12.2 Energy Levels or Quantum Numbers ........................................52
1.4.12.3 Macro- and Microstates and Entropy ........................................53
1.4.12.4 Entropy of a Solid, a Liquid and a Gas ......................................55
1.4.12.5 Relation between Entropy, Energy and Volume .........................55
1.4.13 Properties in Mixtures: Partial Molal Property ..........................................57
1.5 Summary ................................................................................................................57
1.6 Appendix: Stokes and Gauss Theorems...................................................................57
1.6.1 Stokes Theorem ........................................................................................58
1.6.2 Gauss–Ostrogradskii Divergence Theorem ...............................................58
1.6.3 The Leibnitz Formula ................................................................................59
2 First Law of Thermodynamics ....................................................................................61
Objectives .........................................................................................................................61
2.1 Introduction ...........................................................................................................61
2.2 Zeroth Law ............................................................................................................62
Contents ◾ xi
2.3 First Law for a Closed System ................................................................................62
2.3.1 Energy Conservation Equation in Various Forms .....................................63
2.3.1.1 Elemental Process .....................................................................63
2.3.1.2 Integrated Form ........................................................................66
2.3.1.3 Uncoupled (Conservative) and Coupled
(Nonconservative) Systems ......................................................66
2.3.1.4 Adiabatic Form and Caratheodary Axiom I..............................69
2.3.1.5 Cyclical Form and Poincare Theorem .......................................69
2.3.1.6 First Law in Rate Form .............................................................70
2.4 Quasi-Equilibrium (QE) and Nonquasi-Equilibrium (NQE) Processes .................70
2.4.1 Quasi-Equilibrium and Nonequilibrium Heat Transfer............................70
2.4.2 Quasi-Equilibrium and Nonequilibrium Work Transfer ..........................71
2.4.2.1 Quasi-Equilibrium Work Transfer ............................................71
2.4.2.2 Nonquasi-Equilibrium Work Transfer .......................................74
2.5 Enthalpy and First Law .........................................................................................79
2.5.1 First Law in Enthalpy Form ......................................................................79
2.5.2 Reference Conditions for Enthalpy and Internal Energy ..........................80
2.5.3 Specific Heats at Constant Pressure and Volume ......................................82
2.5.3.1 Any Substance ..........................................................................82
2.5.3.2 Ideal Gas ..................................................................................83
2.6 Adiabatic Reversible Process for Ideal Gas with Constant Specific Heats ...............85
2.7 First Law for an Open System ...............................................................................87
2.7.1 Conservation of Mass ...............................................................................88
2.7.1.1 Nonsteady State ........................................................................88
2.7.1.2 Elemental Form ........................................................................90
2.7.1.3 Steady State ..............................................................................90
2.7.1.4 Closed System Elemental Form ................................................91
2.7.2 Conservation of Energy for a Simple Open System ....................................91
2.7.2.1 Nonsteady State .........................................................................91
2.7.2.2 Steady State ..............................................................................94
2.7.3 Conservation of Energy for Complex Open System ..................................98
2.7.3.1 Multiple Inlets and Exits ..........................................................98
2.7.3.2 Nonreacting Multicomponent System ......................................98
2.8 Applications of First Law for an Open System ......................................................99
2.8.1 Heating of a Residence in Winter .............................................................99
2.8.2 Charging of Gas into a Cylinder ..............................................................101
2.8.3 Discharging Gas from Cylinders .............................................................104
2.8.4 Systems Involving Boundary Work ..........................................................105
2.8.5 Charging Cavern with CO Work Input .................................................108
2
2.9 Integral and Differential Forms of Conservation Equations .................................111
2.9.1 Mass Conservation ..................................................................................111
2.9.1.1 Integral Form ..........................................................................111
2.9.1.2 Differential Form .....................................................................112
2.9.2 Energy Conservation ...............................................................................113
2.9.2.1 Integral Form ..........................................................................113
2.9.2.2 Differential Form .....................................................................113
2.9.2.3 Deformable Boundary .............................................................114
