Modern Engineering Thermodynamics

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CHAPTER 7 Second Law of Thermodynamics and Entropy Transport and Production Mechanisms CONTENTS 7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205 7.2 What Is Entropy? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206 7.3 The Second Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207 7.4 Carnot’s Heat Engine and the Second Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . 208 7.5 The Absolute Temperature Scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212 7.6 Heat Engines Running Backward. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216 7.7 Clausius’s Definition of Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 7.8 Numerical Values for Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221 7.9 Entropy Transport Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227 7.10 Differential Entropy Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227 7.11 Heat Transport of Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229 7.12 Work Mode Transport of Entropy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231 7.13 Entropy Production Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231 7.14 Heat Transfer Production of Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232 7.15 Work Mode Production of Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235 7.16 Phase Change Entropy Production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239 7.17 Entropy Balance and Entropy Rate Balance Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241 7.1 INTRODUCTION In this chapter, we introduce the second law of thermodynamics and an important new thermodynamic property called entropy. The theory is presented first then applied to a variety of closed and open systems of engineering interest in the following chapters. The details of the second law of thermodynamics and its associated entropy balance are presented, along with a detailed discussion of the entropy transport mechanisms associated with the energy transports of heat and work. Unlike mass, energy, and momentum, entropy is not conserved. Consequently, the mechanisms of entropy production must be well understood to produce an effective entropy balance equation. In Chapter 8, the focus is on applying the theory presented in this chapter to the same steady state closed systems considered in Chapter 5. The second law of thermodynamics is expanded in Chapter 9 to cover open Modern Engineering Thermodynamics. DOI: 10.1016/B978-0-12-374996-3.00007-5 © 2011 Elsevier Inc. All rights reserved. 205
206 CHAPTER 7: Second Law of Thermodynamics and Entropy Transport and Production Mechanisms systems, as in Chapter 6. Then appropriate applications are presented, dealing with a variety of common open systems of engineering interest, such as nozzles, diffusers, throttling devices, heat exchangers, and mixing. Chapter 9 ends with a brief discussion of shaft work machines and unsteady state processes. 7.2 WHAT IS ENTROPY? When we discussed the first law of thermodynamics in Chapter 4, it was fairly easy to apply the general balance equations to the energy concept and to invoke the conservation of energy principle to obtain a workable energy balance equation. Energy is a common English word, and it is also a well-accepted technical term. Everyone has a basic understanding of what the word means, though we would all have a difficult time defining it precisely. Thesamecanbesaidforthewordsforce and momentum. They are such familiar words that we easily accept mathematical formulae and logical arguments structured around them. Most people are intrigued by seeing a movie run backward because it produces images of things never observed in the real world. What they do not realize is that they are seeing the effects of the second law of thermodynamics in action. The second law dictates the direction of the arrow of time. That is, things occur only in a certain way in the real world; and by applying the second law to an observation (like the screening of a movie), we can determine whether the event is running forwardorbackwardintime.Thesecondlawofthermodynamics is what prohibits us from actually traveling backward in time. Curiously, it is the only law of nature that has such a restriction. All the other laws of mechanics and thermodynamics are valid regardless of whether time is moving forward or backward. Only the second law of thermodynamics is violated when time is reversed. At this point we need to introduce a new thermodynamic property that is simply a measure of the amount of molecular disorder within a system. The name of this new property is entropy. The meaning of this particular name is explained later, but note that a system that has a high degree of molecular disorder (such as a hightemperature gas) has a very high entropy value and, conversely, a system that has a very low degree of molecular disorder (such as a crystalline solid) has a very low entropy value. This new property is very important because entropy is at the core of the second law of thermodynamics. A system that has all its atoms arranged in some perfectly ordered manner has an entropy value of zero. This is the substance of the third law of thermodynamics. This law, introduced in 1906 by Walter H. Nernst (1864–1941), states that the entropy of a pure substance is a constant at absolute zero temperature. In 1911, Max Planck modified this law by setting the entropies of all pure substances equal to zero at absolute zero temperature. This had the effect of normalizing entropy values and thus creating a uniform absolute entropy scale for all substances. Therefore, we can write the following simple mathematical statement of the third law of thermodynamics: The third law of thermodynamics: The entropy of a pure substance is zero at absolute zero temperature, or lim ð Entropy of a pure substance Þ = 0 (7.1) T!0 With this simple entropy-disorder concept in mind, we would expect that the entropy of solid water (ice), with its highly ordered molecular structure, would be less than that of liquid water with its amorphous molecular structure, which in turn would be less than that of water vapor with its highly random molecular order. This is in fact true, for at the triple point of water (the only point where the solid, liquid, and vapor phases coexist in equilibrium), the values of the specific entropies of these phases are Specific entropy of ice at the triple point = −1:221 kJ/ ðkg.KÞ = −0:292 Btu/ ðlbm.RÞ Specific entropy of liquid water at the triple point = 0:0 kJ/ ðkg.KÞ = 0:0 Btu/ ðlbm.RÞ Specific entropy of water vapor at the triple point = 9:157 kJ/ ðkg.KÞ = 2:187 Btu/ ðlbm.RÞ So clearly the entropy of a solid < the entropy of a liquid < the entropy of a vapor or gas. IS ENTROPY LIMITED TO MOLECULES? Even though the physical concept of entropy is based on the behavior of molecular systems, order and disorder phenomena exist at all levels. For example, if entropy is a measure of disorder, then what is the entropy of your bedroom? If you have a messy room it is very disordered, so its entropy is high, but if you are a neat person and keep things picked up and put away, then it has a low entropy. Things seem to get messy easily, and to maintain cleanliness and order requires constant effort. This is a fundamental characteristic of the second law of thermodynamics. The natural progression of things is from ordered to disorganized and to keep it organized requires the input of energy. If entropy had been named disorder, perhaps it would not be so difficult to understand.
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Modern Engineering Thermodynamics
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Modern Engineering Thermodynamics R
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Dedication WHAT IS AN ENGINEER AND
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Contents PREFACE . . . . . . . . .
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Contents ix 7.6 Heat Engines Runnin
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Contents xi 14.13 Air Standard Gas
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Preface TEXT OBJECTIVES This textbo
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Preface xv Step 5. Write down the b
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Acknowledgments I wish to acknowled
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Resources That Accompany This Book
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List of Symbols A a B COP CR c c p
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Prologue PARIS FRANCE, 10:35 AM, AU
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CHAPTER 1 The Beginning CONTENTS 1.
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1.2 Why Is Thermodynamics Important
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1.3 Getting Answers: A Basic Proble
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1.5 How Do We Measure Things? 7 bei
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1.6 Temperature Units 9 THE DEVELOP
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1.7 Classical Mechanical and Electr
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1.7 Classical Mechanical and Electr
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1.9 Modern Units Systems 15 where M
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1.10 Significant Figures 17 CRITICA
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1.10 Significant Figures 19 WHAT AB
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1.11 Potential and Kinetic Energies
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1.11 Potential and Kinetic Energies
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Summary 25 FIGURE 1.19 Case study 1
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Problems 27 Problems (* indicates p
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Problems 29 14. Determine the mass
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Problems 31 49. Using the CGS units
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CHAPTER 2 Thermodynamic Concepts CO
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2.3 Phases of Matter 35 System boun
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2.4 System States and Thermodynamic
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2.6 Thermodynamic Processes 39 WHAT
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2.7 Pressure and Temperature Scales
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2.9 The Continuum Hypothesis 43 Sur
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2.10 The Balance Concept 45 Solutio
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2.11 The Conservation Concept 47 or
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2.11 The Conservation Concept 49 Th
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Summary 51 change in the mass of X
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Problems 53 Problems (* indicates p
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Problems 55 and Death rate = α 2 +
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CHAPTER 3 Thermodynamic Properties
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3.3 Fun with Mathematics 59 CRITICA
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3.4 Some Exciting New Thermodynamic
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3.6 Enthalpy 63 WHO WAS AMALIE EMMY
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3.7 Phase Diagrams 65 WHO WAS EMMY
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Pressure Vapor 3.7 Phase Diagrams 6
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3.7 Phase Diagrams 69 WHAT IS A “
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3.7 Phase Diagrams 71 considerable
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3.8 Quality 73 10 5 300 C Critical
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3.8 Quality 75 Although Eq. (3.26)
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3.9 Thermodynamic Equations of Stat
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3.10 Thermodynamic Tables 85 Critic
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3.12 Thermodynamic Charts 87 vð100
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3.13 Thermodynamic Property Softwar
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Summary 91 and e = E/m = u + V2 2g
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Problems 93 c. For a saturated mixt
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Problems 95 specific enthalpy of sa
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Problems 97 Table 3.23 Problem 65 M
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CHAPTER 4 The First Law of Thermody
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4.3 The First Law of Thermodynamics
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4.3 The First Law of Thermodynamics
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4.4 Energy Transport Mechanisms 105
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4.5 Point and Path Functions 107 4.
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4.6 Mechanical Work Modes of Energy
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4.7 Nonmechanical Work Modes of Ene
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4.9 Work Efficiency 125 In the case
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4.12 Heat Modes of Energy Transport
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4.13 Heat Transfer Modes 129 Table
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4.14 A Thermodynamic Problem Solvin
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4.14 A Thermodynamic Problem Solvin
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4.15 How to Write a Thermodynamics
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4.15 How to Write a Thermodynamics
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Summary 139 The general open system
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Problems 141 11.* Determine the hea
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Problems 143 where K = 0.810 lbf. D
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Problems 145 Table 4.12 Problem 67
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CHAPTER 5 First Law Closed System A
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5.2 Sealed, Rigid Containers 149 In
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5.4 Power Plants 151 Step 7. Calcul
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5.5 Incompressible Liquids 153 The
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Page 196 and 197: 6.3 Conservation of Energy and Cons
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8.2 Systems Undergoing Reversible P
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8.3 Systems Undergoing Irreversible
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8.4 Diffusional Mixing 271 Exercise
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Summary 273 Note that this example
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Problems 275 15. A 20.0 ft 3 tank c
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Problems 277 46. a. Determine a for
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CHAPTER 9 Second Law Open System Ap
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9.4 Open System Entropy Balance Equ
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9.4 Open System Entropy Balance Equ
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9.5 Nozzles, Diffusers, and Throttl
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9.5 Nozzles, Diffusers, and Throttl
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9.6 Heat Exchangers 289 Exercises 1
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9.6 Heat Exchangers 291 (T H ) (T H
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9.7 Mixing 293 Now, _m air is given
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9.7 Mixing 295 Critical value of y,
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9.9 Unsteady State Processes in Ope
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Problems 309 Multiplying this equat
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Problems 311 entropy production rat
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Problems 313 heat is added to the b
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Problems 315 55.* Determine the max
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Problems 317 The cavitation process
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CHAPTER 10 Availability Analysis CO
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10.3 What Are Conservative Forces?
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10.6 Availability 323 WHAT IS A SYS
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10.6 Availability 325 and the total
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10.7 Closed System Availability Bal
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10.7 Closed System Availability Bal
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10.8 Flow Availability 331 EXAMPLE
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s − s 0 = c ln T T 0 10.8 Flow Av
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10.10 Modified Availability Rate Ba
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10.10 Modified Availability Rate Ba
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10.11 Energy Efficiency Based on th
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Summary 351 In this problem, we hav
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Summary 353 7. The general open sys
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Problems 355 12.5 Btu/hr·ft ·R. I
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Problems 357 flow rate of 15.0 lbm/
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Problems 359 85. Create a specific
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CHAPTER 11 More Thermodynamic Relat
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11.2 Two New Properties: Helmholtz
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11.2 Two New Properties: Helmholtz
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11.4 Maxwell Equations 367 11.4 MAX
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11.4 Maxwell Equations 369 then,
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11.5 The Clapeyron Equation 371 and
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11.6 Determining u, h, and s from p
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11.7 Constructing Tables and Charts
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11.8 Thermodynamic Charts 381 so th
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11.9 Gas Tables 383 where p r is th
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11.10 Compressibility Factor and Ge
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11.11 Is Steam Ever an Ideal Gas? 3
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Summary 399 equation, and a series
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Problems 401 20.* Estimate h fg for
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Problems 403 Design Problems The fo
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CHAPTER 12 Mixtures of Gases and Va
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12.2 Thermodynamic Properties of Ga
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12.3 Mixtures of Ideal Gases 413 Th
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12.3 Mixtures of Ideal Gases 415 Co
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12.4 Psychrometrics 417 Finally, th
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12.4 Psychrometrics 419 EXAMPLE 12.
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12.6 The Sling Psychrometer 421 The
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12.6 The Sling Psychrometer 423 p w
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12.7 Air Conditioning 425 WHAT ENVI
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12.8 Psychrometric Enthalpies 427 E
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12.8 Psychrometric Enthalpies 429 o
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12.9 Mixtures of Real Gases 431 Whe
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12.9 Mixtures of Real Gases 433 and
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12.9 Mixtures of Real Gases 435 The
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12.9 Mixtures of Real Gases 437 Sol
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Summary 439 Last, we combine Dalton
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Problems 441 Problems (* indicates
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Problems 443 exhaust gas is an idea
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Problems 445 57.* Cooling towers ar
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CHAPTER 13 Vapor and Gas Power Cycl
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13.2 Part I. Engines and Vapor Powe
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13.4 Rankine Cycle 457 A B Reversib
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13.5 Operating Efficiencies 459 For
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13.5 Operating Efficiencies 461 13.
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13.5 Operating Efficiencies 463 b.
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13.5 Operating Efficiencies 465 Sta
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13.6 Rankine Cycle with Superheat 4
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13.7 Rankine Cycle with Regeneratio
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13.8 The Development of the Steam T
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13.9 Rankine Cycle with Reheat 477
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13.9 Rankine Cycle with Reheat 479
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13.10 Modern Steam Power Plants 481
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13.12 Air Standard Power Cycles 487
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13.13 Stirling Cycle 489 Q H 4 1 4
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13.14 Ericsson Cycle 491 Q H 4 1 3
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13.15 Lenoir Cycle 493 Exercises 28
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13.16 Brayton Cycle 495 Solution Us
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13.16 Brayton Cycle 497 Equation (7
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13.17 Aircraft Gas Turbine Engines
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13.17 Aircraft Gas Turbine Engines
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13.18 Otto Cycle 503 T Q H 1 1 1 v
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13.18 Otto Cycle 505 Exercises 40.
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13.18 Otto Cycle 507 and, since the
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13.20 Miller Cycle 509 13.19.1 Mode
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13.20 Miller Cycle 511 Then, from F
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13.21 Diesel Cycle 513 to stroll on
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13.21 Diesel Cycle 515 Solution a.
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13.22 Modern Prime Mover Developmen
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13.23 Second Law Analysis of Vapor
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Summary 525 Fill port 160 mm End of
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Problems 527 7. The thermal efficie
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efficiency increase if the condense
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Problems 531 horsepower hour. Assum
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Problems 533 72. Determine the valu
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CHAPTER 14 Vapor and Gas Refrigerat
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14.3 Carnot Refrigeration Cycle 537
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14.4 In the Beginning There Was Ice
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14.4 In the Beginning There Was Ice
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14.5 Vapor-Compression Refrigeratio
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14.5 Vapor-Compression Refrigeratio
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14.6 Refrigerants 547 T 3 2s 2 p 3
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14.7 Refrigerant Numbers 549 14.7 R
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14.7 Refrigerant Numbers 551 R-110
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14.8 CFCs and the Ozone Layer 553 H
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14.9 Cascade and Multistage Vapor-C
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14.10 Absorption Refrigeration 561
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14.11 Commercial and Household Refr
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14.14 Reversed Brayton Cycle Refrig
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14.14 Reversed Brayton Cycle Refrig
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14.15 Reversed Stirling Cycle Refri
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14.16 Miscellaneous Refrigeration T
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14.16 Miscellaneous Refrigeration T
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14.18 Second Law Analysis of Refrig
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14.18 Second Law Analysis of Refrig
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2. The coefficient of performance o
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Problems 585 13.* A refrigeration u
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Problems 587 Loop B Station 1B Stat
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Problems 589 under these conditions
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CHAPTER 15 Chemical Thermodynamics
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15.2 Stoichiometric Equations 593 1
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15.2 Stoichiometric Equations 595 C
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15.3 Organic Fuels 597 ANSWERS SOME
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15.4 Fuel Modeling 599 Hydrocarbon
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15.4 Fuel Modeling 601 equation, si
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15.5 Standard Reference State 603 I
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15.6 Heat of Formation 605 and H 2
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15.7 Heat of Reaction 607 EXAMPLE 1
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15.7 Heat of Reaction 609 CRITICAL
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15.7 Heat of Reaction 611 Then, h P
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15.8 Adiabatic Flame Temperature 61
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15.9 Maximum Explosion Pressure 619
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15.10 Entropy Production in Chemica
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15.10 Entropy Production in Chemica
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15.11 Entropy of Formation and Gibb
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15.12 Chemical Equilibrium and Diss
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H 2 O !ð1 − yÞH 2 O + yðv H2
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15.14 The van’t Hoff Equation 635
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15.15 Fuel Cells 637 Anode Electrol
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15.15 Fuel Cells 639 The maximum po
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15.16 Chemical Availability 641 and
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ðn i /n fuel Þðc pi Þ E system
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Problems 645 where j = 4n + m kgmol
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Problems 647 c. The percent excess
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Problems 649 77. Determine the mola
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CHAPTER 16 Compressible Fluid Flow
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16.3 Isentropic Stagnation Properti
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16.4 The Mach Number 655 Note that
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16.4 The Mach Number 657 Table 16.1
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16.4 The Mach Number 659 Since for
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16.5 Converging-Diverging Flows 661
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16.5 Converging-Diverging Flows 663
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16.6 Choked Flow 665 T a a p a = co
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16.6 Choked Flow 667 Exercises 16.
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16.7 Reynolds Transport Theorem 669
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16.7 Reynolds Transport Theorem 671
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16.8 Linear Momentum Rate Balance 6
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16.9 Shock Waves 675 16.9 SHOCK WAV
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16.9 Shock Waves 677 and, for an id
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16.9 Shock Waves 679 6 5 4 S P /(m
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16.10 Nozzle and Diffuser Efficienc
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16.10 Nozzle and Diffuser Efficienc
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Summary 685 Since for a diffuser, M
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Problems 687 Problems (* indicates
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43. 0.800 lbm/s of air passes throu
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Problems 691 A plot of this functio
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CHAPTER 17 Thermodynamics of Biolog
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17.3 Thermodynamics of Biological C
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17.3 Thermodynamics of Biological C
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17.4 Energy Conversion Efficiency o
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17.4 Energy Conversion Efficiency o
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17.5 Metabolism 703 Table 17.3 Brea
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17.6 Thermodynamics of Nutrition an
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17.7 Limits to Biological Growth 71
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17.7 Limits to Biological Growth 71
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17.8 Locomotion Transport Number 71
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17.9 Thermodynamics of Aging and De
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17.9 Thermodynamics of Aging and De
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1/3 V most efficient = P o ρAC D S
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Problems 723 a. If the monster cons
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Problems 725 the officer asks Paul
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CHAPTER 18 Introduction to Statisti
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18.3 Kinetic Theory of Gases 729 3.
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U trans = 3 2 NkT (Continued ) 18.3
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18.4 Intermolecular Collisions 733
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18.5 Molecular Velocity Distributio
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18.5 Molecular Velocity Distributio
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18.6 Equipartition of Energy 739 We
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18.7 Introduction to Mathematical P
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18.8 Quantum Statistical Thermodyna
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18.9 Three Classical Quantum Statis
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18.11 Monatomic Maxwell-Boltzmann G
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18.12 Diatomic Maxwell-Boltzmann Ga
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18.12 Diatomic Maxwell-Boltzmann Ga
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18.13 Polyatomic Maxwell-Boltzmann
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Summary 759 In this chapter, we sum
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Problems 761 4. Find the temperatur
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CHAPTER 19 Introduction to Coupled
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19.3 Linear Phenomenological Equati
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19.4 Thermoelectric Coupling 767 Eq
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19.4 Thermoelectric Coupling 769 Th
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19.4 Thermoelectric Coupling 771 wh
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19.4 Thermoelectric Coupling 773 Th
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19.4 Thermoelectric Coupling 775 b.
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19.5 Thermomechanical Coupling 777
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water), it seems reasonable that li
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Problems 785 b. For a Knudson gas,
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Appendix A: Physical Constants and
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Appendix B: Greek and Latin Origins
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Appendix B 791 Table B.4 Plural End
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Index Page numbers followed by f in
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Index 795 E e (specific energy), 10
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Index 797 Isobaric coefficient of v
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Index 799 Ranque, Georges Joseph, 3
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Index 801 William III, King of Engl
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Modern Engineering Thermodynamics

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