Modern Engineering Thermodynamics

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CHAPTER 15 Chemical Thermodynamics CONTENTS 15.1 Einführung (Introduction) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591 15.2 Stoichiometric Equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 593 15.3 Organic Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 596 15.4 Fuel Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599 15.5 Standard Reference State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603 15.6 Heat of Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604 15.7 Heat of Reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 607 15.8 Adiabatic Flame Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 613 15.9 Maximum Explosion Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619 15.10 Entropy Production in Chemical Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 621 15.11 Entropy of Formation and Gibbs Function of Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 625 15.12 Chemical Equilibrium and Dissociation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 626 15.13 Rules for Chemical Equilibrium Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634 15.14 The van’t Hoff Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635 15.15 Fuel Cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636 15.16 Chemical Availability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642 15.1 EINFÜHRUNG (INTRODUCTION) This chapter deals with an application of the laws of thermodynamics on which entire textbooks have been written. Chemists call this topic physical chemistry, and it forms the basis of much of applied chemistry. It is important to engineers, because it provides a fundamental understanding of the combustion process in engines, power plants, fuel cells, and other chemically based energy conversion processes. This chapter has three main goals. Our first goal is to be able to calculate the amount of heat produced in the combustion of an organic fuel. The second is to understand the basic elements of chemical equilibrium and dissociation, and the third is to look at the emerging field of fuel cell technology. To be able to discuss these subjects adequately, we need to define what we mean by the term fuel, weneedtodecidehowthethermodynamic properties of the products and the reactants are related through a standard reference state, andweneed to lay the foundations for discussing chemical reaction energy conversion efficiency. Modern Engineering Thermodynamics. DOI: 10.1016/B978-0-12-374996-3.00015-4 © 2011 Elsevier Inc. All rights reserved. 591
592 CHAPTER 15: Chemical Thermodynamics IS IT CHEMISTRY OR ALCHEMY? A practical chemical technology can be traced to prehistoric times. Primitive metallurgy, medicine, and food preparation are typical examples. They were purely empirical “recipe” driven processes with no form of chemical theory to explain their results. Before the sixth century BC, it was generally believed that all things were composed of a single primitive element. The Greek philosophers Heraclitus (540–480 BC) and Empedocles (490–430 BC) began a new era when they proposed that, instead of a single element, all matter was made up of four elements—air, earth, fire, and water—and that the continual mixing of these elements formed all the objects of the real world. The Greek philosopher Pythagoras (580–500 BC) is generally credited with recognizing the functional significance of numbers in quantifying the processes of the real world. Pythagoras established an academy of learning in Crotona, Italy, in about 532 BC. The academy prospered long after his death until its destruction in about 390 BC. It is believed that his disciples (known as Pythagoreans) working at the academy during this time developed many of the mathematical discoveries now attributed to him (e.g., the Pythagorean theorem for right triangles). Empedocles adopted Pythagoras’ numerology technique in an attempt to quantify the chemistry of his four elements. For example, according to Empedocles, animal bone consisted of two parts water, two parts earth, and four parts fire. Because he believed that all of his four elements were most thoroughly mixed in blood, he concluded that people think mainly with their blood. From about the second century AD until nearly the 19th century, the world embraced what is considered today to be a scientific and chemical curiosity, alchemy. Alchemy was a combination of the occult, astrology, and primitive chemistry. Even its name, derived from Arabic and introduced in the 12th century, is obscure because the root chem seems to have no relevant etymological meaning. The basic function of alchemy was transmutation, which was concerned with transmuting age to youth, sickness to health, death to immortality. More notorious was its preoccupation with the physical transmutation of base metals into gold (i.e., transmuting poverty to wealth). Its central elements were mercury (quicksilver, the liquid metal), sulfur (the stone that burns), and ammonium chloride (sal ammoniac, a source of hydrochloric acid). Successful alchemists tended to be charlatans whose work was shrouded in mystery. From the Medieval period forward, the central focus of alchemy was the making of gold (religion had successfully taken over the immortality issue), and many prominent scientists, including Isaac Newton (1643–1726), experimented with it seriously. (Newton is thought to have contracted mercury poisoning in about 1690 as a result of his alchemy experiments.) The false science of alchemy, which appealed primarily to the human weakness of greed, went without serious intellectual challenge for nearly 2000 years. In the 17th century, Johann Jochim Becher (1635–1682), an established alchemist at one time engaged in attempting to transmute Danube River sand into gold, proposed that all substances were made up of the classical alchemical elements of mercury, sulfur, and corrosive salts, plus a new fourth weightless element that was produced by combustion. In 1697, the German physician Georg Ernst Stahl (1660–1734) named this supposed fourth element phlogiston and used it to develop a coherent theory of combustion, respiration, and corrosion. His phlogiston theory quickly won universal scientific approval and was the only scientifically accepted theory of matter for nearly 100 years afterward. In 1774, the English clergyman and scientist Joseph Priestley (1733–1804) described some of his experimental results in removing phlogiston from air (the “dephlogistication” of air) to the French chemist Antione Laurent Lavoisier (1743– 1794), who immediately recognized their importance and subsequently carried out similar experiments himself. Lavoisier soon realized that the dephlogiston that Priestley thought he had been working with was actually a unique chemical and, in 1777, he named it oxygen (from the Greek for acid forming). By the early 19th century Lavoisier’s oxidation theory completely replaced Stahl’s phlogiston theory and the era of modem chemistry had begun. Lavoisier had done for chemistry what a century earlier Newton had done for mechanics; he put the subject on a firm analytical foundation. The unfortunate Joseph Priestley was subsequently driven from his home in England because of his public support of the French Revolution, and he settled in America. WHO KILLED THE GREAT FRENCH CHEMIST LAVOISIER? Because Lavoisier maintained a career in the French government as well as science (he was on the original 1790 weights and measures committee that led to the development of the metric system we now use), he was caught up in the French Revolution and was accused of political crimes (such as stopping the circulation of air in Paris by a city wall erected at his suggestion in 1787). He was convicted and guillotined on the same day in 1794.
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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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1Q 2 − 1 W 2 = mðu 2 − u 1 Þ
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5.8 Closed System Unsteady State Pr
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5.9 The Explosive Energy of Pressur
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Problems 161 Problems (* indicates
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Problems 163 31. A thermoelectric g
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Problems 165 where v, T, and r are
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CHAPTER 6 First Law Open System App
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6.2 Mass Flow Energy Transport 169
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6.3 Conservation of Energy and Cons
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6.4 Flow Stream Specific Kinetic an
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6.5 Nozzles and Diffusers 175 m (a)
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6.5 Nozzles and Diffusers 177 We ar
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6.6 Throttling Devices 179 These as
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6.6 Throttling Devices 181 For an i
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6.7 Throttling Calorimeter 183 The
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6.8 Heat Exchangers 185 Convective
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6.9 Shaft Work Machines 187 6.9 SHA
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6.9 Shaft Work Machines 189 1 Basem
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6.10 Open System Unsteady State Pro
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Problems 197 we have _m R / _m D =
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Problems 201 32.* A commercial slid
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Summary 203 59. Incompressible liqu
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CHAPTER 7 Second Law of Thermodynam
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7.3 The Second Law of Thermodynamic
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7.4 Carnot’s Heat Engine and the
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7.4 Carnot’s Heat Engine and the
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7.5 The Absolute Temperature Scale
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7.5 The Absolute Temperature Scale
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7.6 Heat Engines Running Backward 2
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7.7 Clausius’s Definition of Entr
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7.8 Numerical Values for Entropy 22
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7.10 Differential Entropy Balance 2
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7.11 Heat Transport of Entropy 229
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7.13 Entropy Production Mechanisms
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7.14 Heat Transfer Production of En
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7.15 Work Mode Production of Entrop
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7.15 Work Mode Production of Entrop
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7.16 Phase Change Entropy Productio
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Summary 241 ■ Indirect method inv
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Problems 243 amount of work W irr i
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Problems 245 a. If the heat pump is
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Problems 247 51. Develop a program
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CHAPTER 8 Second Law Closed System
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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 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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Page 604 and 605: 14.18 Second Law Analysis of Refrig
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Page 608 and 609: 2. The coefficient of performance o
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Page 612 and 613: Problems 587 Loop B Station 1B Stat
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Page 620 and 621: 15.2 Stoichiometric Equations 595 C
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Page 624 and 625: 15.4 Fuel Modeling 599 Hydrocarbon
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Page 632 and 633: 15.7 Heat of Reaction 607 EXAMPLE 1
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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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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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