AN INTRODUCTION TO COMBUSTION Concepts and ApplicationsMcGraw-Hill Series in Mechanical Engineering Consulting Editors Jack P. Holman, Southern Methodist University John Lloyd, Michigan State University Anderson: Computational Fluid Dynamies: The Basics with Applications Anderson: Modern Compressible Flow: With Historical Perspective ‘Arora: Introduction to Optimum Design Borman and Ragland: Combustion Engineering Cengel: Thermodynamics: An Engineering Approach Cengel: Heat Transfer: A Practical Approach Cengel: introduction to Thermodynamics & Heat Transfer Culp: Principles of Energy Conversion Dieter: Engincering Design: A Materials & Processing Approach Doebelin: Engincering Experimentation: Planning, Execution, Reporting Driels: Linear Control Systems Engineering Edwards and McKee: Fundamentals of Mechanical Component Design Gibson: Principles of Composite Material Mechanics Hamrock: Fundamentals of Fluid Film Lubrication Heywood: Internal Combustion Engine Fundamentals Histand and Alciatore: Introduction 10 Mechatronics and Measurement Systems Holman: Experimental Methods for Engineers Jaluria: Design and Optimization of Thermal Systems Kays and Crawford: Convective Heat and Mass TransferKelly: Fundamentals of Mechanical Vibrations Kimbrell: Kinematies Analysis and Synthesis Kreider and Rabl: Heating and Cooling of Buildings Martin: Kinematics and Dynamics of Machines Mattingly: Elements of Gas Turbine Propulsion Modest: Radiative Heat Transfer Norton: Design of Machinery Oosthuizen and Carseallen: Compressible Fluid Flow Oosthuizen and Naylor: Inroduction to Convective Heat Transfer Analysis Reddy: 4n Introduction 10 Finite Element Method Rosenberg and Karnopp: Introduction to Physical Systems Dynamics Schlichting: Boundary-Laver Theory Shames: Mechanies of Fluids Shigley: Kinematic Analysis of Mechanisms Shigley and Mischke: Mechanical Engineering Design Shigley and Uieker: Theory of Machines and Mechanisms Stoecker: Design of Thermal Systems Stoecker and Jones: Refrigeration and Air Conditioning ‘Turns: An Iniroduction to Combustion: Concepts and Applications Ullman: The Mechanical Design Process Wark: Advanced Thermodynamics for Engineers Wark and Richards: Thermedynamics White: Fluid Mecitanics White: Viscous Fluid Flow Zeid: CADICAM Theory and PracticeAN INTRODUCTION TO COMBUSTION Concepts and Applications SECOND EDITION Stephen R. Turns Propulsion Engineering Research Center and Department of Mechanical and Nuclear Engineering The Pennsylvania State University fae Boston * Burr Ridge, IL + Dubuque, IA + Madison, WI New York + San Francisco * St. Louis Bangkok * Bogoti + Caracas * Lisbon + London + Madrid + Mexico City Milan + New Delhi + Seoul * Singapore * Sydney * Taipei » TorontoMcGraw-Hill Higher Education A Diision of The McGraw-Hill Conpuariss AN INTRODUCTION TO COMBUSTION: CONCEPTS AND APPLICATIONS Tnxeratonal Eitons 2000, Exclusive rights by McGraw-Hill Book Co ~ Singapore, for manufacture and export. This book eannot be re-expored from the county to which itis consigned by MeGraw-Hil Copyright © 2000, 1996 by The McGraw-Hill Companies, Inc.All igh reserved. Except s permite under the United Sates Copyright Act of 1976, no part of this publication may be reproduce or distbuted in ny form or by any meas, o stored in a database o retrieval sytem, without he prior writen persson ofthe publisher BN 0.07-230006-5 (book) ISBN 0-07-230008-1 (disk) BN 0407-235044-X (book hound with disk) Library of Congress Catalogingin-Publcation Data Turns, Stephen R “An iaoduction to combustion : concepts and applications / Stephen R, Tums ~ 2nd ed cin ~ (McGrail series in mechanical engineering) ISBN 0-07-23000645, 1. Combustion enginczring, 1. Title, I. Series 2545188 2000 621.402'3-de21 99.25421 cP ‘worwambhe.com ‘When ordering this ttle, use ISBN 0-07-116910-5 Printed in SingaporeABOUT THE AUTHOR Stephen R. Turns received degrees in mechanical engineering from The Pennsylvania State University (BS., 1970), Wayne State University (M.S. 1974), and the University of Wisconsin at Madison (Ph.D., 1979). He was a research engineer at General Motors Research Laboratories from 1970 to 1975. He joined the Penn State faculty in 1979 and is currently Professor of Mechanical Engineering. Dr. Turns teaches a wide variety of courses in the thermal sciences and has received several awards for teaching excellence at Penn State, He is an active combustion researcher. publishing widely, and is an active member of The Combustion Institute, the American Society of Mechanical Engineers, and the Society of Automotive EngineersThis Book Is Dedicated to My Wife, Joan, and Our Sons, Matthew and Michael “SRTBy contrast, the fist fires fickering at a cave mouth are our own discovery, our own triumph. our grasp upon invisible chemical power. Fire contained, in that place of brutal darkness and leaping shadows, the crucible and the chemical retort, steam and industry. It contained the entire human future Loren Eiseley The Unexpected UniversePREFACE TO THE SECOND EDITION This second edition retains the same primary objectives as the original text first, to present basic combustion concepts using relatively simple and easy-to- understand analyses; and second, to introduce a wide variety of practical applications that motivate or relate to the various theoretical concepts. The overarching goal is to provide a textbook that is useful for both formal under- graduate study in mechanical engineering and related fields, and informal study by practicing engineers, The author, as well as many of his colleagues around the world, also have found the book to be useful in a first course in combustion at the graduate level. In this usage, however, the book alone did not suffice: more detailed treatments and advanced topics needed to be developed by the instructor to supplement the text. Nevertheless, many have reported success in using the book in this manner. The second edition specifically addresses this need for additional topics and greater depth in some areas. Chapter 7 now contains a section dealing with multicomponent diffusion, including thermal diffusion. The development of the one-dimensional energy conservation equation is expanded in Chapters 7 and & to include multicomponent and thermal diffu- sion in a form consistent with that used in the various flame codes developed at Sandia National Laboratories, Livermore, CA. This provides a good link for those instructors who use such codes in conjunction with CHEMKIN software in their courses. In the same spirit, Chapter 9 now includes a section on coun- terflow diffusion flames. None of these additions detract in any way from the ability to use the book at a lower level. The more advanced topics are arranged so that they can be skipped with no loss in continuity. Furthermore, these additions, in general, are not particularly lengthy—thus, the overall length of the text is not greatly increased, and the book retains its original comfortable, compact feel Changes to the basic text include a brief discussion of the molecular struc- ture of fuels in an appendix to Chapter 2. This appendix provides information useful for appreciating many of the thermochemical concepts of Chapter 2, as well as providing background information useful for understanding some of the chemical-kinetic concepts developed in Chapters 4 and 5. Chapter 4 now includes # section on partial equilibrium and a discusion of characteristic chemical time scales, while Chapter 5 has been updated to include the latest advances in methane kinetics (GRI-Mech). Reaction pathway diagrams for CHy-air combustion are also included to give a much clearer—and holis- tic—picture of methane combustion kinetics. Chapter 6 sees the addition of a well-stirred-reactor example that employs detailed kinetics, providing yet another link to CHEMKIN software, In Chapter 8, the discussion of premixedPreface to the Second Edition flame structure is expanded to give a much clearer, and detailed, view of this important subject. A chapter on detonations (Chapter 16) also has been added to meet the needs of those desiring to include this topic in their courses. Logically, this material could be included following Chapter 2or Chapter 8. New problems have been added to many chapters and several additional exam- ples are included. Those problems requiring, or benefiting from, the use of a computer for their solution are indicated. The computer software has been updated to be compatible with Windows. The author hopes that this new edition will continue to serve well those who desire 10 use the book at its most basic level and that the additional topics presented in this edition also will make the book more useful at a somewhat more advanced level. Stephen R. Turns University Park, PAPREFACE TO THE First EDITION High interest in combustion and combustion applications exists among many engineering students. Although undergraduate, senior-level courses in combus- tion and combustion-related areas are offered at many institutions, finding an appropriate textbook for such courses is difficult, at best. The need for an introductory text on combustion, specifically structured for an undergraduate readership, has served as the motivation for writing this book. The offering of an introductory course at Penn State and the development of an introductory textbook were conceived jointly, and this book is the result of those develop- ments Although the primary audience is intended to be senior-level students in ‘mechanical and related engineering majors, others may find the text useful as a bridge between the basic undergraduate thermal sciences and advanced treat- ments of combustion. Many examples and problems are presented to aid in understanding and to relate to practical applications, Thus, it is hoped that both first-year graduate students and practicing engineers can benefit from the ‘material presented here. In its organization, the text provides flexibility. The 15 chapters provide ‘much more material than can be covered in a single-semester course; this over kill makes it easy for an instructor to tailor a course to a particular theme or set of topics, while allowing the theme to evolve or change from one course offer ing to another. For example, a one-semester course providing a general ove view could cover Chapters 1-6, 15, 8, 9, and 14; while course with some emphasis on spark-ignition engines could cover Chapters 1-6, 8, 11, 12, 15, and 9, Located in Chapters 1-3 are topics considered essential for an undergrad uuate course. Chapter | defines combustion and the types of flames, and intro- duces the effects and control of combustion-generated air pollution, which is treated in greater detail in Chapter 15. The thermochemistry needed for a study of combustion is presented in Chapter 2. This chapter emphasizes the importance of chemical equilibrium to combustion, Software provided with this book provides students with a simple means of calculating complex equilibria for combustion gases: this soft- ware can be put to good use in many interesting and pedagogically helpful projects. Chapter.3 introduces mass transfer. The approach taken here, and throughout the book, is to simplify theoretical developments by treating all mass transfer within the context of simple binary systems, Except for a brief mention in Chapter 7, the treatment of multicomponent diffusion is left to more advanced texts. Such an approach allows students with no previous exposure to mass transfer to gain an appreciation of the subject without gettingPreface to the First Edition bogged down in its inherent complexities. Chapter 3 uses both the classical Stefan problem and simple droplet evaporation to illustrate mass-transfer theory. Onward to the subject of chemistry, Chapters 4 and 5 deal with chemical kinetics by presenting basic concepts (Chapter 4) and discussing chemical mechanisms of importance to combustion and combustion-generated air pol- lution (Chapter 5). In addition to showing the unavoidable complexity of hydrocarbon combustion chemistry, simple single- and multistep kinetics are presented that can be used to incorporate chemical kinetic effeets in simple analyses or models, recognizing, of course, the pitfalls of simplified kinetics. ‘The interrelation of chemical kinetics and thermodynamic modeling is the subject of Chapter 6. Here, models of constant-pressure and constant-volume reactors, and well-stirred and plug-flow reactors, are developed. These simple models allow a student to grasp clearly how chemical kinetics fits into the bigger picture. This chapter also offers many opportunities for projects involv- ing reactor analysis and/or design. Both the usefulness and uniqueness of this chapter make it a lot of fun. Having completed our study of thermochemistry, molecular transport, and chemical kinetics, we devote Chapter 7 to the development of the simplified conservation equations for reacting systems used in subsequent chapters. The conserved-scalar concept is introduced here. This chapter is intended to pro- vide a background from which more rigorous developments can be followed. For an undergraduate course, this chapter is clearly optional, and is probably best skipped; however, for an introductory graduate-level course, the chapter may be quite useful Elementary treatments of flames are presented in Chapters 8-13. Laminar premixed flames are discussed in Chapter 8, and laminar nonpremixed flames in Chapters 9 and 10; turbulent flames are dealt with in Chapter 12 (premixed) and Chapter 13 (nonpremixed). Topics treated include flame propagation, ignition and quenching, and flame stabilization. Simplified analyses are pre- sented wherever possible, and practical applications emphasized. In all cases, rigorous mathematical development is eschewed in favor of developing the most basic understanding. This approach has the shortcoming of not being able to deal with some phenomena at all, and others, incompletely at best. Usually in these areas, warnings are given and references cited to help the reader who seeks a more complete understanding. Because the wealth of mate- rial in these chapters, one can conveniently choose to cover only laminar flames (Chapters 8, 9, and 10) or to focus only on premixed flames (Chapters 8, 11, and 12) or nonpremixed flames (Chapters 9, 10, and 13). Particular emphases on specific applications might suggest which topics to cover. Linking droplet vaporization theory to practical devices is the subject of the second half of Chapter 10, where a mode! of a one-dimensional vaporiza- tion-controlled combustor is developed. The primary purposes of this section are to reinforce previous concepts of equilibrium and evaporation, help develop students’ powers of analysis, and provide ideas and concepts thatPreface to the First Edition ‘can be used in applications-oriented projects. Design projects can eas fitted into the framework of Chapter 10. Depending on course objectives. this section of Chapter 10 can be treated as optional, In Chapter 14, burning of solids is introduced, using carbon combustion as the archetypical system. Again, simplified analyses are presented to illuminate heterogeneous combustion concepts and to introduce the ideas of diffusionally and kinetically controlled combustion, This chapter also acquaints the student with coal combustion and its applications, Omitting a treatment of combustion-generated pollutants would be unthinkable in a modern book on combustion. Chapter 15 focuses on this topic, This chapter introduces the reader to the quantification of emissions land discusses the mechanisms of pollutant formation and their control. This chapter emphasizes applications and should be of particular interest to the intended readers of this book. The placement of this chapter does not suggest its relative importance. Depending on course objectives, the material here could be covered following Chapters 1-6. Now, in summary, this book attempts to present an introduction to com- bustion at a level easily comprehended by students nearing the completion of aan undergraduate study in mechanical engineering and related fields. Through the use of examples and homework problems, students can develop confidence in their understanding and go on to apply this to various projects and “real world” problems. It is hoped that this text will fit the needs of instructors, and ‘others, who desire simplified and appropriately structured materials for an introductory study of the fascinating field of combustion. Stephen R. Turns University Park, PAACKNOWLEDGMENTS Many people contributed their support, time, and psychic energy to either the first or second edition of this book. First, I would like to thank the many reviewers who contributed along the way; in particular, Jim Driscoll, The University of Michigan; Norm Laurendeau, Purdue University: John Lloyd. Michigan State University: Michel Louge, Cornell University; Jon Van Gerpen, Iowa State University; and Carl Wikstrom, University of Arkansas, all provided many useful comments on early drafts of the frst edition. Also, the detailed comments of Steve Goebel and Alan Feitelberg. who used various versions of the book in teaching a course at Rensselaer Polytechnic Institute, were extremely valuable. They also generously shared some interesting end-of- chapter problems, which have been incorporated into the second edition. My friend and colleague, Chuck Merkle, continually provided moral support and. served as a sounding board for ideas on both content and pedagogy in the first, edition. Many students at Penn State contributed in various ways, and I want to acknowledge the particular contributions of Jeff Brown, Jongguen Lee, and, Don Michael. Sankaran Venkateswaran deserves special thanks for providing the turbulent jet-flame model calculations, as does Dave Crandall for his assis- tance with the software for the second edition. A major debt of thanks is owed. to Donn Mueller, who painstakingly solved all of the first-edition end-of-chap- tet problems, Thanks are also due to my dear friend Kathy Wendland for her editorial help with the second edition. 1 would also like to thank the Gas Research Institute for their support of my research activities through the Years, as it was these activities that provided the initial inspiration and impetus to write this book. Invaluable to my efforts throughout was the unflagging support of my family. They tolerated amazingly well the time spent writing on weekends and holiday breaks—time that I could have spent with them. The last acknowledgment is reserved for Cheryl Adams. How either edition could have been completed without her is dificult to conceive. She typed and word-pro- cessed the many drafts and created many of the line drawings that appear in the text. Cheryl's skill and dependability contributed greatly to making the writing of this book an enjoyable experience.CONTENTS Preface to the Second Edition Preface to the First Edition x Acknowledgments _ xvii 1 Introduction | Motivation to Study Combustion 1 A Definition of Combustion 6 Combustion Modes and Flame Types 6 Approach to Our Study 8 References 8 2 Combustion and Thermochemistry 9 Overview 9 Review of Property Relations 9 Extensive and Intensive Properties. 9 Equation of State 10 Calorific Equations of State 11 Ideal-Gas Mixtures 13 Latent Heat of Vaporization 15 First Law of Thermodynamics 16 First Law—Fixed Mass 16 First Law-—-Control Volume 17 Reactant and Product Mixtures 18 Stoichiometry 18 Absolute (or Standardized) Enthalpy and Enthalpy of Formation 24 Enthalpy of Combustion and Heating Values 27 Adiabatic Flame Temperatures 32 Chemical Equilibrium 36 Second-Law Considerations 36 Gibbs Function 38 Complex Systems 44 Equilibrium Products of Combustion 45 Full Equilibrium 45 Water-Gas Equilibrium $7 Pressure Fifects SI Some Applications 52 Recuperation and Regeneration 52 Flue- (or Exhaust-) Gas Recirculation $8 Summary 66 Nomenclature 66 References 68 Review Questions 69 Problems 70 Appendix 2A — Some Fuel Chemistry 78 3. Introduction to Mass Transfer 83 Overview 83 Rudiments of Mass Transfer 83 Mass Transfer Rate Laws 84 Species Conservation 90 Some Applications of Mass Transfer 92 ‘The Stefan Problem 92 Liquié-Vapor Intertace Boundary Conditions 94 Droplet Evaporation 98 Summary 105 Nomenclature 105 References 107 Review Questions 107 Problems 108 4 Chemical Kinetics 111 Overview 111 Global versus Elementary Reactions 112 Elementary Reaction Rates 113 Bimolecular Reactions and Collision Theory 113 Other Elementary Reactions 118 Rates of Reaction for Multistep Mechanisms 119 Net Production Rates 119 Compact Notation 121 Relation between Rate Coefficients and Equilibrium Constants Steady-State Approximation 125 ‘The Mechanism for Unimolecular Reactions 126 Chain and Chain-Branching Reactions 127= Contents ‘Chemical Time Seales 133 Partial Equilibrium 138 Summary 140 Nomenclature 140 References 141 Questions and Problems 143 s Some Important Chemical Mechanisms 148 Overview 148 ‘The Hy-O2 System 148 Carbon Monoxide Oxidation 152 Oxidation of Higher Paraffins 153 General Scheme 153 Global and Quasi-global Mechanism 156 Methane Combustion 158 Complex Mechanism 158 High-Temperature Reaction Pathway Analysis 158 Low-Temperature Reaction Pathway Analysis 166 Oxides of Nitrogen Formation 168 Summary 171 References 172 Questions and Problems 174 @ Coupling Chemical and Thermal Analyses of Reacting Systems 178 Overview 178 Constant-Pressure, Fixed-Mass Reactor 179 Application of Conservation Laws 179 Reactor Model Summary 182 Constant-Volume, Fixed-Mass Reactor 182 Application of Conservation Laws 182 Reactor Model Summary 183 Well-Stirred Reactor 189 Application of Conservation Laws 190 Reactor Model Summary 192 Plug-Flow Reactor 200 ‘Assumptions 200 Application of Conservation Laws 201 Applications to Combustion System Modeling 205, Summary 206 Nomenclature 206 References 208 Problems and Projects 209 Appendix 6A—Some Useful Relationships among Mass Fractions, Mole Fractions, Molar Concentrations, and Mixture Molecular Weights 214 7 Simplified Conservation Equations for Reacting Flows 215 Overview 215 Overall Mass Conservation (Continuity) 216 Species Mass Conservation (Species Continuity) 218 Multicomponent Diffusion 221 General Formulations 222 Calculation of Multicomponent Diffusion Coefficients 223, Simplified Approach 226 Momentum Conservation 229 One-Dimensional Forms 229 Two-Dimensional Forms 230 Energy Conservation 234 General One-Dimensional Form 234 Shvab-Zeldovich Forms 236 Useful Form for Flame Calculations 240 ‘The Concept of a Conserved Scalar 241 Definition of Mixture Fraction 241 Conservation of Mixture Fraction 242 Conserved Scalar Energy Equation 246 Summary 247 Nomenclature 248 References 249 Review Questions 250 Problems 251 8 Laminar Premixed Flames 253 Overview 253 Physical Description 254 Definition 254 Principal Characteristics 254 Typical Laboratory Flames 256 Simplified Analysis 261 Assumptions 262 Conservation Laws 262 Solution 264 Detailed Analysis 269Governing Equations 269 Boundary Conditions 2 Structure of CHy-Air Flame 271 Factors Influencing Flame Velocity and Thickness 274 ‘Temperature 274 Pressure 277 Equivalence Ratio 278 Fuel Type 278 Fame Speed Correlations for Selected Fuels 278 Quenching, Flammability, and Ignition 283 Quenching by a Cold Wall 284 Flammability Limits 289 Tenition 291 Flame Stabilization 294 Summary 298 Nomenclature 299 References 300 Review Questions 302 Problems 302 9 Laminar Diffusion Flames 305 Overview 305 Nonreacting Constant-Density Laminar Jet 306 Physical Description 306 ‘Assumptions 307 Conservation Laws 308 Boundary Conditions 308 Solution 309 Jet Flame Physical Description 314 ‘Simplified Theoretical Descriptions 317 Primary Assumptions 318, Basic Conservation Equations 318 Additional Relations 319 Conserved Scalar Approach 320 ‘Various Solutions 327 Flame Lengths for Circular-Port and Slot Burners 331 Roper's Correlations 331 Flowrate and Geometry Effects 336 Factors Affecting Stoichiometry 336 Soot Formation and Destruction 343 Counterflow Flames 347 Mathematical Description 48 Contents xi Structure of CHy Air Flame 350 Summary 354 Nomenclature 354 References 356 Review Questions 359 Problems 359 10 Droplet Evaporation and Burning 362 Overview 362 Some Applications 362 Diesel Engines 363, fas-Turbine Engines 365 Liquid-Rocket Engines 367 Simple Model of Droplet Evaporation 367 Assumptions 370 Gas-Phase Analysis 372 Droplet Lifetimes 375 ‘Simple Model of Droplet Burning 378 ‘Assumptions 379 Problem Statement 380 Mass Conservation 381 Species Conservation 381 Energy Conservation 383 Summary and Solution 389 Burning Rate Constant and Droplet Lifetimes 391 Extension to Convective Environments 395 Additional Factors 398 One-Dimensional Vaporization-Controlled Combustion 399 Physical Model 399 Assumptions 401 ‘Mathematical Problem Statement 401 Analysis 402 Model Summary 410 Summary 410 Nomenclature 413 References 415 Problems 418 Projects 420 Appendix 10A—Sir Harry R. Ricardo’s Description of Combustion in Diesel Engines 421xii Contents 1 Introduction to Turbulent Flows 423 Overview 423 Definition of Turbulence 424 Length Scales in Turbulent Flows 427 Four Length Seales 427 Turbulence Reynolds Numbers 430 Analyzing Turbulent Flows 434 Reynolds Averaging and Turbulent Stresses 435, The Closure Problem 437 Axisymmetric Turbulent Jet 441 Beyond the Simplest Model 444 Summary 445 Nomenclature 446 References 447 Questions and Problems 449 12 Turbulent Premixed Flames 450 Overview 450 Some Applications 450 Spark-Ignition Engines 450 Gas-Turbine Engines 451 Industrial Gas Burners 452 Definition of Turbulent Flame Speed 454 Structure of Turbulent Premixed Flames 456 Experimental Observations 456 Three Flame Regimes 457 Wrinkled Laminar-Flame Regime 462 Distributed-Reaction Regime 466 Flamelets-in-Eddies Regime 468 Flame Stabilization 470 Bypass Ports 470 Burner Tiles 471 Bluif Bodies 471 ‘Swirl or Jet-Induced Recirculating Flows 473 Summary 474 Nomenclature 475 References 476 Problems 478 13 Turbulent Nonpremixed Flames 481 Overview 481 Jet Flames 484 General Observations 484 Simplified Analysis 489 Flame Length 495 Flame Radiation 501 Liftoff and Blowout $04 Other Configurations 509 Summary 512 Nomenclature 513 References 514 Review Questions 517 Problems 517 14 Burning of Solids 519 Overview 519 Coal-Fired Boilers 520 Heterogeneous Reactions 520 Burning of Carbon 522 Overview 523 One-Film Model 524 Two-Film Model $36 Particle Burning Times S42 Coal Combustion 544 Other Solids 545 Summary 545 Nomenclature $46 References 547 Questions and Problems 548 15 Pollutant Emissions 550 Overview 550 Effects of Pollutants 551 Quantification of Emissions 553 Emission Indices 553 Corrected Concentrations 555 Various Specific Emission Measures 558 Emissions from Premixed Combustion 559 Oxides of Nitrogen 559 Carbon Monoxide 567 Unburned Hydrocarbons 568 Catalytic Aftertreatment 569 Particulate Mater $71 Emissions from Nonpremixed Combustion 572 Oxides of Nitrogen $73 ‘Unburned Hydrocarbons and Carbon Monoxide 584Particulate Matter $86 Oxides of Sulfur 386 Summary 587 Nomenclature $88 References 589 Questions and Problems 594 1 Detonations 598 Overview 598 Physical Description 598 Definition 598 Principal Characteristics 599 One-Dimensional Analysis 600 Assumptions 600 Conservation Laws 601 Combined Relations 602 Detonation Velocities 609 Structure of Detonation Waves 613 Summary 617 Nomenclature 618 References 619 Problems 620 Appendix A Selected Thermodynamic Properties of Gases Comprising C-H-O-N System 621 Contents wai Appendix8 Fuel Properties 648 Appendix ¢ Selected Properties of Air, Nitrogen, and Oxygen 653 Appendix Binary Diffusion Coefficients and Methodology for their Estimation 656 Appendix € Generalized Newton’s Method for the Solution of Nonlinear Equations 659 Appendix # Computer Codes for Equilibrium Products of Hydrocarbon-Air Combustion 662 Index 665chapter 1 Introduction MOTIVATION TO STUDY COMBUSTION Combustion and its control are essential to our existence on this planet as we know it. In 1996, approximately 85 percent of the energy used in the United States came from combustion sources {1, 2] (Table 1.1). A quick glance around your local environment shows the importance of combustion in your daily life More than likely, the heat for your room or home comes directly from com- bustion (cither gas- or oilsired furnace or boiler), or, indirectly, through electricity that was generated by burning a fossil fuel. Our nation’s electrical needs are met primarily by combustion. Presently, only 32.7 percent of the electrical generating capability is nuclear or hydroelectric, while more than SOURCE: Oo tam et. “tlecriiy gnerote fr dirbuton irom woed and wat, geuhernal wind, phlowollc and solr thermal eneieyCHAPTER 1 «Introduction Table 1.2 1996 US. electiciy generation [1] Billion KW 17359) S64 ‘ona, 219 318 os 2633 86 619 22 4 a1 30779 1000 half is provided by burning coal, as shown in Table 1.2 [1], Our transportation system relies almost entirely on combustion. In the United States in 1989, ground vehicles and aircraft burned 3991 million barrels of various petroleum products annually (3), or approximately two-thirds of all of the petroleum imported or produced in the United States. Aircraft are entirely powered by on-board fuel burning, and most trains are diesel-engine powered. Recent times have also seen the rise of gasoline-engine driven appliances such as Jawn mowers, leaf blowers, chain saws, weed-whackers, and the like. Industrial processes rely heavily on combustion. Iron, steel, aluminum, and other metals-refining industries employ furnaces for producing the raw product, while heat-treating and annealing furnaces or ovens are used down- stream to add value to the raw material as it is converted into a finished product. Other industrial combustion devices include boilers, refinery and chemical fluid heaters, glass melters, solids dryers, surface-coating curing and drying ovens, and organic fume incinerators (4, to give just a few examples. ‘The cement manufacturing industry is a heavy user of heat energy delivered by combustion. Rotary kilns, in which the cement clinker is produced, use over 0.4 quads! of energy, or roughly 1.4 percent of the total industrial energy use in the United States in 1989. At present, rotary kilns are rather inefficient devices, and potentially great energy savings could be made by improving these devices [5] In addition to helping us make products, combustion is used at the other end of the product life eyele as a means of waste disposal. Incineration is an old method, but itis receiving renewed interest because of the limited availability of landfill sites in densely populated areas. Aiso, incineration is attractive for its ability to dispose of toxic wastes safely. Currently, siting of incinerators is a politically controversial and sensitive issue. Having briefly reviewed how combustion is beneficial, we now look at the downside issue associated with combustion—environmental pollution. The ‘major pollutants produced by combustion are unburned and partially burned hydrocarbons, nitrogen oxides (NO and NO:), carbon monoxide, sulfur oxides | Yavad = 1 qvdition BTU = 10° aruMotivation to Study Combustion Toble 1.3 Typicol pollutants of cancer from selected sources Pollutant Owides Carbon Particulate Sourse of Nitrogen Monoxide Solr Oxides Matter Sparkignition engines + + Diesel engines + Gas-turbine engines + + Coul-burming wlity boilers Gas-burning appliances : - - (SO, and $05), and particulate matter in various forms. Table 1.3 shows which pollutants are typically associated with various combustion devices and, in most cases, subjected to legislated controls. Primary pollution concerns relate to specific health hazards, smogs, acid rain, global warming, and ozone deple- tion. National trends for pollutant emissions from 1940-1996, showing the contributions from various sources, are presented in Figs. 1.1 to 1.5 [6]. The impact of the Clean Air Act Amendments of 1970 can be clearly seen in these figures. ToD 194519501955 19601965. 19701975 19801985 19901995, Yer EiMisc MAU Waste Comb Comb- MComb- No cher disp ind sled ind Figure 1.1 Trends in emissions of pariculote matter for the United States, 1940-1996, Reading lagend lf fo righ ceresponds to plotted series top to botom. SOURCE: Fram Ra. [6CHAPTER} © Introduction 3s x0 2s 1950 1960 1970 1980 1990 Yew WAL DNon Comb On Metals DComb- MI Comd- ‘ther road other road industry wil Figure 1.2 Trends in emiasions of sur oxides for the United Stales, 1940-1996. Reoding legend lef to right corresponds to ploted seres lop to betom, [*S0URCE: From Re. [6 1940 1950 1960 1970 1980 1950 Yeu BAI Mother CIchem ME Comb- EINon- MComb- CiComt- Monod ther ind ober rad ind Figure 1.3 Trends in emissions of nitrogen oxides for tha United Sites, 1940-1996. Reading legend lotto right corresponds 1 potted series top to bottom. [SOURCE From Ra. 61Motivation to Study Combustion lion short tons) too 1950 190 1980 1990) BAI MMisc Clhom MStor& EINon- MWaste C)Solv MOnroed cotter teens road disposal ail, Figure 1.4 Trends in emissions of eaile organic compounds for the United Sttes 1940-1996. Reading legend if fo ight corresponds to ploted series top to bottom [ SOURCE: From Ret {o. ol 19401945 19819851960 1965 1970-197 198019851990. 1995, Year BAN Mise Chem MMeals OMe Mion ON: ‘ber disposs! ther oad 1 MOnsoad Figure 1.5 Trends in emissions of corbon monoxide forthe United Stole, 1940-1996, Reoding egead lel right corresponds to pled series top to bottom, SOURCE. From Ret [6,CHAPTER? © Introduction Considering the importance of combustion in our society, it is somewhat surprising that very few engineers have more than a cursory knowledge of combustion phenomena, However, with an already demanding curriculum, it is unrealistic to expect the subject to be given more attention than it presently receives. Therefore, engineers with some background in combustion may find many opportunities to use their expertise, Aside from the purely practical motivations for studying combustion, the subject is in itself intellectually stimulating in that it integrates all of the thermal sciences nicely, as well as bringing chemistry into the practical realm of engineering. A DEFINITION OF COMBUSTION Webster's Dictionary provides a useful starting point for a definition of eom- bustion as “rapid oxidation generating heat, or both light and heat; also, slow oxidation accompanied by relatively ltile heat and no light.” For our purposes, ‘we will restrict the definition to include only the rapid oxidation portion, since ‘most practical combustion devices belong in this realm. This definition emphasizes the intrinsic importance of chemical reactions to combustion. It also emphasizes why combustion is so very important: com- bustion transforms energy stored in chemical bonds to heat that can be utilized in a variety of ways. Throughout this book, we illustrate the many practical applications of combustion COMBUSTION MODES AND FLAME TYPES Combustion can occur in either a flame or nonflame mode, and flames, in turn, are categorized as being either premixed flames or nonpremixed (diffusion) flames. The difference between flame and nonflame modes of combustion can be illustrated by the processes occurring in a knocking spark-ignition engine (Fig. 1.6). In Fig. 1.6a, we see a thin zone of intense chemical reaction propagating through the unburned fuel-air mixture. The thin reaction zone is what we commonly refer to as a flame. Behind the flame are the hot products of combustion, As the flame moves across the combustion space, the temperature and pressure rise in the unburned gas. Under certain conditions (Fig. 1.66), rapid oxidation reactions occur at many locations within the unburned gas, leading to very rapid combustion throughout the volume. This essentially volumetric heat release in an engine is called autoignition, and the very rapid pressure rise leads to the characteristic sound of engine knock. Knock is undesirable, and a recent challenge to engine designers has been how to mini- mize the occurrence of knock while operating with lead-free gasolines.? In lecoer tht east Ind reduces knack, mde by Thorns Midgley in 1921, cllowed eaginn cor proton soa abe creed, ond hareby impiovedefGany and power.Combustion Modes and Flame Types Propagating Name: jsp ple Burned gases Unbumed fiel-sir oO @ Autoigniting fel-sir mixture Sk ple © Figure 1.6 (e} Flome ond [b) nonflome mades of combustion in a spark-igntion engine compression-ignition or diesel engines, however, autoignition initiates the com- bustion process by design. The two classes of flames, premixed and nonpremixed (or diffusion), are related to the state of mixedness of the reactants, as suggested by their names. In a premixed flame, the fuel and the oxidizer are mixed at the molecular level prior to the occurrence of any significant chemical reaction, The spark-ignition engine is an example where premixed flames occur. Contrarily, in a diffusion flame, the reactants are initially separated, and reaction occurs only at the interface between the fuel and oxidizer, where mixing and reaction both take place. An example of a diffusion flame is a simple candle. In practical devices, both types of flames may be present in various degrees. Diesel-engine combus. tion is generally considered to have significant amounts of both premixed and nonpremixed or diffusion burning. The term “diffusion” applies strictly to the molecular diffusion of chemical species, ie.. fuel molecules diffuse toward theCHAPTER] + Introduction flame from one direction while oxidizer molecules diffuse toward the flame from the opposite direction. In turbulent nonpremixed flames, turbulent con- veetion mixes the fuel and air together on a macroscopic basis. Molecular mixing at the small scales, i., molecular diffusion, then completes the mixing process so that chemical reactions can take place. APPROACH TO OUR STUDY We begin our study of combustion by investigating the key physical processes, ot sciences, which form the fundamental framework of combustion science: thermochemistry in Chapter 2; molecular transport of mass (and heat) in Chapter 3; chemical kinetics in Chapters 4 and 5; and, in Chapters 6 and 7, the coupling of all of these with fluid mechanics. In subsequent chapters, we apply these fundamentals to develop an understanding of laminar premixed flames (Chapter 8) and laminar diffusion flames (Chapters 9 and 10). In these siti relatively easy to see how basic conservation principles can Most practical combustion devices operate with turbulent flows, hhowever, and the application of theoretical concepts to these is much more difficult. Chapters 11, 12, and 13 deal with turbulent flames and their practical applications. The final chapters concern the combustion of solids, as exempli- fied by carbon combustion (Chapter 14); pollutant emissions (Chapter 15); and detonations (Chapter 16). ‘A major goal of this book is to provide a treatment of combustion that is sulficienty simple so that students with no prior introduction to the subject can appreciate both the fundamental and practical aspects. It is hoped, moreover, that as a result, some may be motivated to learn more about this fascinating field, either through more advanced study, or as a practicing engineer. REFERENCES 1, US, Department of Energy, “1996 Annual Energy Review,” DOE/ELA-0384(96), 1996, (See also http://www eia doe gov/bookshelf html.) 2. Corporation for Public Access to Science and Technology, http://www epestore! 3. USS, Department of Energy, “State Energy Data Report, Consumption Estimates 1960-1989,” DOE/EIA-0714(89), May 1991 4. Bluestein, J., “NO, Controls for Gas-Fired Industrial Boilers and Combustion Equipment: A Survey of Current Practis,” Gas Research Institute, GRI-92/ 0374, October 1992. 5. Tresouthick, S. W., “The SUBJET\ Process for Portland Cement Clinker Production,” presented at the 1991''Air Products International Combustion Symposium, 24-27 March 1991. 6. US. Environmental Protection Agency,”*National Air Pollutant Emission Trends, 1940-1996,” EPA-454/R-97-011, December 1997.OVERVIEW chapter Combustion and Thermochemistry In this chapter, we examine several thermodynamic concepts that are impor- tant in the study of combustion. We first briefly review basic property relations for ideal gases and ideal-gas mixtures and the first law of thermodynamics. Although these concepts are likely to be familiar to you from a previous study of thermodynamics, we present them here since they are an integral part of our study of combustion. We next focus on thermodynamic to s related specii cally to combustion and reacting systems: concepts and definitions related to element conservation: definition of enthalpy that accounts for chemical bonds: and first-law concepts defining heat of reaction, heating values, etc., and adiabatic flame temperatures. Chemical equilibrium, a second-law con cept, is developed and applied to combustion-product mixtures. We emphasize equilibrium because, in many combustion devices, a knowledge of equilibrium states is sufficient to define many performance parameters of the device: for example, the temperature and major species at the outlet of a steady-flow combustor are likely to be governed by equilibrium considerations. Several examples are presented (o illustrate these principles. REVIEW OF PROPERTY RELATIONS Extensive and Intensive Properti The numerical value of an extensive property depends on the amount (mass or number o! les) of the substanc considered, Extensive properties are usually denoted with capital letters; for example, ¥ (m°) for volume, U (J) for internal °10 CHAPTER? «Combustion and Thermochemistry energy, H (J) (= U + PY) for enthalpy, ete, An intensive property, on the other hand, is expressed per unit mass (or per mole), and its numerical value is independent of the amount of substance present. Mass-based intensive proper- ties are generally denoted with lower-case letters; for example, v (m°/ke) for specific volume, u (J/kg) for specific internal energy, f (J/kg) (= w+ Po) for specific enthalpy, etc, Important exceptions to this lower-case convention are the intensive properties temperature T and pressure P, Molar-based intensive properties are indicated in this book with an overbar, e.g., i and hi (J/kmol). Extensive properties are obtained simply from the corresponding intensive properties by multiplying the property value per unit mass (or mole) by the amount of mass (or number of moles); ie. V = mo(or Nd) Qa) U=mu(orN H =mh(or Ni, etc In the following developments, we will use either mass- or molar-based inten- sive properties, depending on which is most appropriate to a particular situa- tion. Equation of State ‘An equation of state provides the relationship among the pressure, P, tempera- ture, T, and volume V (or specific volume v) of a substance. For ideal-gas behavior, ie., a gas that can be modeled by neglecting intermolecular forces ‘and the volume of the molecules, the following equivalent forms of the equa- tion of state apply: PV =NRT. (2.2a) PV =mRT, (2.26) Po= RT, (2.20) P= pRT, (2.24) where the specific gas constant R is related to the universal gas constant R, (= 8315 J/kmol-K) and the gas molecular weight MW by R=R/MW 3) The density p in Eqn. 2.2d is the reciprocal of the specific volume (p = 1/0 = ‘m/V). Throughout this book, we assume ideal-gas behavior for all gaseous species and gas mixtures. This assumption is appropriate for nearly all of the systems we wish to consider since the high temperatures associated with com- bustion generally result in sufficiently low densities for ideal-gas behavior to be a reasonable approximation,Review of Property Relations Calorific Equations of State Expr sions relating internal energy (or enthalpy) to pressure and temperature ions of state, ic, MT. v) (24a) h=WT,P), (2.4) The word “calorific” relates to expressing energy in units of calories, which has been superseded by the use of joules in the SI system, General expressions for a differential change in u or h can be expressed by differentiating Eqns. 2.4a and by au au) 7 uz (2) ar+(2) 25s 3 gr g(t i= (2) at > s ona (3) ar e(®) as) In the above, we recognize the partial derivatives with respect to temperature to be the constant-volume and constant-pressure specific heats, respectively, ie., ) (2.63) 2.66) For an ideal gas, the partial derivatives with respect to specific volume. (@u/20)p, and pressure, (h/aP)p, are zero. Using ths knowledge, We integrate Eqn. 25, substituting Eqn, 2.6 (0 provide the following ideal-gas calorie equations of state tyne =f seat ars) r WT) hee =) opa (76) In a subsequent section, we will define an appropriate reference state that accounts for the different bond energies of various compounds. For both real and ideal gases, the specific heats ¢ and c, are generally functions of temperature. This is a consequence of the internal energy of a molecule consisting of three components: translational, vibrational, and rota- tional; and the fact that, as a consequence of quantum theory, the vibrational and rotational energy storage modes become increasingly active as temperature increases. Figure 2.1 schematically illustrates these three energy storage modes by contrasting a monatomic species, whose internal energy consists solely of translational kinetic energy, and a diatomic molecule, which stores energy in a2 CHAPTER? —« Combustion and Thermochemistry o au) (©) Diatomie species Figure 2.1 _{o) The internal energy of monatomic species conse only of translational (kine) enecgy, wile (oa ditomic specie’ intemol energy reall fom translation together wth energy fram vibration (potential and Knee} and rotohon [kinetic vibrating chemical bond, represented as a spring between the two nuclei, and by rotation about two orthogonal axes, as well as possessing kinetic enerey from translation. With these simple models (Fig. 2.1), we would expect the specific heats of diatomic molecules to be greater than monatomic species. In general, the more complex the molecule, the greater its molar specific heat. This can be seen clearly in Fig. 2.2, where molar specific heats for a number of combustion product species are shown as functions of temperature. As a group, the triatomics have the greatest specific heats, followed by the dia tomics, and, lastly, the monatomics. Note that the triatomie molecules also have a greater temperature dependence than the diatomics, a consequence of the greater number of vibrational and rotational modes that are available to become activated as temperature is increased. In comparison, the monatomic species have nearly constant specific heats over a wide range of temperatures; in fact, the H-atom specific heat is constant (é, = 20.786 kJ/kmol-K) from 200 K to 500K. Constant-pressure molar specific heats are tabulated as a function of tem- perature for various species in Tables A.1 to A.12 in Appendix A. Also pro- vided in Appendix A are the curvefit coefficients, taken from the Chemkin thermodynamic database [I], which were used to generate the tables. These coefficients can be easily used with spreadsheet software to obtain é, values at any temperature within the given temperature range.Review of Property Relations ” co; 60 1,0 NO; 0 Z | 0 Toco 2000 ——=3000 40005000 Temperate (K) Figure 2.2 Molar constant. pressure specifi heats as functions of temperature for ‘monatomic (H, N, and O}, ditomic (CO, Hz, and O3), and tatomic (Cz, HzO, ond NOz} Species, Voluee ar from Appendix. Ideal-Gas Mixtures ‘Two important and useful concepts used to characterize the composition of a mixture are the constituent mole fractions and mass fractions, Consider a multicomponent mixture of gases composed of N, moles of species 1, Ny moles of species 2, etc. The mole fraction of species i, zi, is defined as the fraction of the total number of moles in the system that are species i ie., N Ni NAN +. N+ 8) Similarly, the mass fraction of species i, ¥;, is the amount of mass of species i compared with the total mixture mass: 3“ CHAPTER? «Combustion and Thermochemistry my by +. my + Mot es) Note that, by definition, the sum of all the constitutent mole (or mass) fractions ‘must be unity, i, Duel (2.10a) (2.100) Mole fractions and mass fractions are readily converted from one to another using the molecular weights of the species of interest and of the mixture: Y= MW, MWe @.tlay (MW gig MW, Q.11by x The mixture molecular weight, MW, is easily calculated from a knowledge of either the species mole or mass fractions: MW ig = SOx (2.12a) L MMos = SF (MW) 2.126) Species mole fractions are also used to determine corresponding species partial pressures. The partial pressure of the ith species, P;, is the pressure of the ith species if it were isolated from the mixture at the same temperature and. volume as the mixture, For ideal gases, the mixture pressure is the sum of the constituent partial pressures: P=P, 2.13) ‘The partial pressure can be related to the mixture composition and total pressure as P= 0. 14) For ideal-gas mixtures, many mass- (or molar-) specific mixture properties are calculated simply as mass (or mole) fraction weighted sums of the individ- ual species-specific properties. For example, mixture enthalpies are calculated asReview of Property Relations hic = OYA (1s) Frnis = Yo xh (2.15) Other frequently used properties that can be treated in this same manner are internal energies, wand i. Note that, with our ideal-gas assumption, neither the pure-species properties (uj. iy. /h,) nor the mixture properties depend on pres- ‘The mixture entropy also is calculated as a weighted sum of the constitu: ents Swi P) = YP) (2.164) init? PY = x In this case, however, the pure-species entropies (4; and 5) depend on the species partial pressures as indicated in Eqn. 2.16, The constituent entropies in Eqn. 2.16 can be evaluated from standard-state (Pry = P’ = Latm) values as AT. P)). 2.166) WAP.) = (0. Pu)~ Rin Pe erm P, S(T. P) = 5AT, Pos) = Ryn 2 (T_P)= SAT, Pras) = Ret Standard-state molar specific entropies are tabulated in Appendix A for many species of interest to combustion, 2.17) Latent Heat of Vaporization In many combustion processes, a liquid-vapor phase change is important, For example, a liquid fuel droplet must first vaporize before it can burn; and, it cooled sufficiently, water vapor can condense from combustion products Formally, we define the latent heat vaporization, hg, a8 the heat required in a constant-pressure process to completely vaporize & unit mass of liquid at a given temperature, ie. hglT. P) = baapoe( Ts P) ~ Inguial Ts P) (2.18) where T and P are the corresponding saturation temperature and pressure, respectively. The latent heat of vaporization is also known as the enthalpy of vaporization. Latent heats of vaporization for various fuels at their normal (atm) boiling points are tabulated in Table B.1 (Appendix B). The latent heat of vaporization at a given saturation temperature and pressure is frequently used with the Clausius-Clapeyron equation to estimate saturation pressure variation with temperature: 516 CHAPTER 2 —¢ Combustion and Thermochemistry Pac _ yg Aan Par RT This equation assumes that the specific volume of the liquid phase is negligible compared with that of the vapor and that the vapor behaves as an ideal gas Assuming fy is constant, Eqn. 2.19 can be integrated from (Pay.1, Tat) tO (Poui2+ Tou2) in order to permit, for example, P.,2 to be estimated from a knowiedge of Par. Turis and Ty.2. We will employ this approach in our discussion of dropiet evaporation (Chapter 3) and combustion (Chapter 10). 2.19) FIRST LAW OF THERMODYNAMICS First Law—Fixed Mass Conservation of energy is the fundamental principle embodied in the first law of thermodynamics. For a fixed mass, ic., a system, (Fig. 23a), energy con- servation is expressed for a finite change between two states, 1 and 2, as 1Q2 = Wy 7 AEL2 2.20) Head added 10 Work done by sytem: Chang in tota system, qeaienmne, | sqarowing anne cane is Both ,Q2 and ; W are path functions and occur only at the system boundaries; AE, is the change in the total energy of the system, which is the sum of the internal, kinetic, and potential energies, ic. E=m( « + 4 + =). @21 Masespiic tem Maxespie tem Masoapsie em incre esc Wags en eal ory inten SM Ouner0 » Figure 2.3 (a) Schematic of fxed-mass system with moving boundary above piston, (b) Control volume wih fixed boundaries and steady fow.First Law of Thermodynamics ‘The system energy is a state variable and, as such, AE does not depend on the ath taken to execute a change in state. Equation 2.20 can be converted to unit ‘mass basis or expressed to represent an instant in time. These forms are Ma — 2 = Ae a =e —e, 2.22) and ° - Ww dE jar (2.23) Instantaneous rte Instantaneous rte of| Tasantaneous time thet wanted work dome ty sam tat of ching of or q- w= de/ar, 2.24) where lower-case letters are used to denote mass-specific quantities, 2. e=E/m. First Law—Control Volume We next consider a control volume, illustrated in Fig. 2.3b, in which fluid may flow across the boundaries. The steady-state, steady-flow (SSSF) form of the first law is particularly useful for our purposes and should be reasonably familiar to you from previous studies of thermodynamics [2-4]. Because of its importance, however, we present a brief discussion here. The SSSF first law is expressed as On We fie, ties a, Pa (2.25) Where the subscripts o and i denote the outlet and inlet, respectively, and sis the mass flowrate. Before rewriting Eqn. 2.25 in a more convenient form, it is appropriate to lst the principal assumptions embodied in this relation The control volume is fixed relative to the coordinate system. This eliminates ‘any work interactions associated with a moving boundary, as well as eliminating the need to consider changes in the kinetic and potential energies of the control volume itself. 2. The properties of the fluid at each point within the control volume, or on the control surface, do not vary with time. This assumption allows us to treat all processes as steady. v7CHAPTER? + Combustion and Thermochemistry 3. Fluid properties are uniform over the inlet and outlet flow areas. This allows us to use single values, rather than integrating over the area, for the inlet and exit stream properties, 4. There is only one inlet and one exit stream. This assumption is invoked to keep the final result in a simple form and can be easily relaxed to allow ‘multiple inlet/exit streams. ‘The specific energy ¢ of the inlet and outlet streams consists of the specific internal, kinetic, and potential energies, ic., eter lees meee nee tee eee 2.26) Touleneay — Unemalnersy Kinin nyt ey praise, SEUSS SESE "re where v and z are the velocity and elevation, respectively, of the stream where it crosses the control surface. ‘The pressure-specific volume product terms associated with the flow work in Eq. 2.25 can be combined with the specific internal energy of Eqn. 2.26, which we recongize as the useful property, enthalpy: hs ut Posut Pie. 27 Combining Eqns. 2.25-2.27, and rearranging, yields our final form of energy conservation for a control volume: Gen — We V+ alo =) (2.28) The first law can also be expressed on a mass-specific basis by dividing Eqn. 2.28 by the mass flowrate i, i., alg — hi) +405 — Geo ~ Wes = ho = hi +405 — 99) + 82 (2.29) In Chapter 7, we present more complete expressions of energy conservation that are subsequently simplified for our objectives in this book. For the time being, however, Eqn. 2.28 suits our needs. REACTANT AND PRODUCT MIXTURES Stoichiometry The stoichiomettic quantity of oxidizer is just that amount needed to com- pletely burn a quantity of fuel. If more than a stoichiometric quantity of oxidizer is supplied, the mixture is said to be fuel lean, or just lean; while supplying less than the stoichiometric oxidizer results in a fuel-rich, or rich mixture. The stoichiometric oxidizer— (or air-) fuel ratio (mass) is determined by writing simple atom balances, assuming that the fuel reacts to form an idealReactant and Product Mixtures set of products, For a hydrocarbon fuel given by C,H, the stoichiometric relation can be expressed as C\Hy + a(O: + 3.76N:) > xCO, + (9/2)H,0 + 3.76aN3, 2.30) where + 9/4, eat) For simplicity, we assume throughout this book that the simplified composi- tion for air is 21 percent ©, and 79 percent Np (by volume), ie., that for each mole of Oy in air, there are 3.76 moles of No. The stoichiometric air-fuel ratio can be found as msc 4.16a MWe Prise) goxe 1 MWe” (A/Phavic 2.32) where MW, and MWigg are the molecular weights of the air and fuel, respee- tively. Table 2.1 shows stoichiometric air-fuel ratios for methane and solid carbon. Also shown is the oxygen-fuel ratio for combusion of Hy in pure ;. For all of these systems, we see that there is many times more oxidizer than fuel, Table 2.1 Some combustion properties of methane, hydrogen, and solid arkon for eodionts at 298 K An ‘Ady (OFF? Tages (hg) (1 han) (sik) CH air 55.508 —3,066 rman H+ 0: 12919 15880 80 3079 is) + air 32.794 =2.645 ua 301 SO /F ithe xine fel aio, where or combustion wth ait, the ie he oud rot tha oxygen in The equivalence ratio, ®, is commonly used to indicate quantitatively whether a fuel-oxidizer mixture is rich, lean, or stoichometric. The equivalence ratio is defined as AIP (iF) (2.33a) From this definition, we see that for fuel-rich mixtures, ® > 1, and for fuel~ lean mixtures, © < |, For a stoichiometric mixture, equals unity, In many combustion applications, the equivalence ratio is the single most important factor in determining a system’s performance. Other parameters frequently uused to define relative stoichiometry are percent stoichiometric air, which relates to the equivalence ratio as ”20 CHAPTER 2 » Combustion and Thermochemistry 100% ° % stoichometric air (2.336) and percent excess air, or a-* o % excess ai 100 (2.330) Example 2.1 AA small, Jow-emission, stationary gus-turbine engine (see Fig. 2.4) operates at full load (2950 kW) at an equivalence ratio of 0.286 with an air lowrate of 15,9 kgs. The equiva lent composition of the fuel (natural gas) is C, Hao. Determine the fuel mass flowrate and the operating air-fuel ratio for the engine. Solution Given: @ = 0.286, MWg = 28.85, gy = 15.9kg/s, — MWgqi = 1.16(12.01) +4.32(1.008) = 18.286 Find: gas and (A/F), We will proceed by first finding (4/F) and then rg. The solution requires only the application of definitions expressed in Eqns, 2.32 and 2.33, ic., MWe MW” 116 +4.32/4 = 2.24, Thus, ro29 285-5, APP, = 4.160 where a= x+y/ (AIP cic = and, from Eqn. 2.33, _(AlPhacic _ 1682 amit emat zc) Since (A/F) is the ratio of the air flowrate to the fuel flowrate, Tig _ 159 kes “G/F ~ 88 GP =a (0270 kei Comment Note that even at full power, a large quantity of excess air is supplied to the engine Example 2.2 A natural gas-fired industrial boiler (see Fig. 2.5) operates with an oxygen concentration of 3 mole percent in the flue gases. Determine the operating air-fuel ratio and the ‘equivalence ratio. Treat the natural gas as methane. Solution Given: xo, 3, MWe MWg = 28.85. Find: (4/F) and ©, We can use the given O; mole fraction to find the air-fuel ratio by writing an overall combustion equation assuming “complete combustion,” ie, no dissociation (al fuel C is found in CO, and all fuel H is found in HO):2 Chant injection fie Swifer injection ful spoke (18) Combustion and Thermochemistry Channel fel 5 injection cnifice 7 CCombior dome Primary airflow © Pilot fuel injctionReactant and Product Mixtures 23 Figure 2.5 Two 10-MW (24 milion BTU/fv} natural-ges burners fie into boiler combustion chamber 3m dap. Air enters the burners twaugh the lorge vertical pipes, while the naturel gos entrs through the horizontal pipe onthe lk SOURCE: Courtesy of Nor Amero Manuataing Co (CH, -+a(0; + 3.76N2) COs +2H:0 + bOs +3.76a No where a and # are seated from conservation of O atoms 2a= 242426 baa-2 From the definition of a mole fraction (Eqn. 28) No, f Ninn TE24O4 3160” 144.760 Substituting the known value of Zo, (= 0,03) and then solving for a yields 0.03 = #2 Tae = 2.368,CHAPTER? © Combustion and Thermochemistry ‘The mass air-fuel ratio, in general, is expressed as Nu Ma apr) = ft a 4760 MMs (apy =A Mie 4760236912885) _ 88232089 Fog To find &, we need to determine (4/Fge- From Bq, 231, = 2: hence, 476092885 (A/Phage = OPES 174 Applying the definition of @ (Eqn. 2.33), (ALP goie _ 17.1 ay ~ 203 = OS Comment In the solution, we assumed that the O, mole fraction was on a “wet basis,” i.e, moles of O; per mole of moisture-containing flue gases. Frequently, in the measurement of exhaust species, moisture is removed to prevent condensation in the analyzers; thus, Xo, can also be reported on a “dry basis” (see Chapter 15). Absolute (or Standardized) Enthalpy and Enthalpy of Formation In dealing with chemically reacting systems, the concept of absolute enthalpies is extremely valuable. For any species, we can define an absolute (or standar- ized) enthalpy that isthe sum of an enthalpy that takes into account the energy associated with chemical bonds (or lack thereof), the enthalpy of formation, fy, and an enthalpy that is associated only with the temperature, the sensible enthalpy change, AA,. Thus, we can write the molar absolute enthalpy for species fas AAT) = Tas) + Mhn(Tet)> (2.34) Abst ently Entaiy of foration Sense etalpy sempre nia ree cose ig on where Ah, = hi(T) ~ hi. (Trat To make practical use of Eqn. 2.34, it is necessary to define a standard reference state. We employ a standard-state temperature, Tyy = 25°C (298.15K), and. standard-state pressure, Pap = P? = atm (101,325 a), con- sistent with the Chemkin [1] and NASA [5] thermodynamic databases. Furthermore, we adopt the convention that enthalpies of formation are zero for the elements in their naturally occurring state at the reference stateReactant and Product Mixtures temperature and pressure. For example, at 25°C and Iatm, oxygen exists as diatomic molecules; hence, Wio:)an= 0 where the superscript 0 is used to denote that the value is for the standard-state pressure, To form oxygen atoms at the standard state requires the breaking of a rather strong chemical bond. The bond dissociation energy for Os at 298 K is 498,390 kJ/kmolo,. Breaking this bond creates two O atoms; thus, the enthalpy of formation for atomic oxygen is half the value of the O; bond dissociation energy, ie. 249,195 kJ/kmolo, Thus, enthalpies of formation have a clear physical interpretation as the net change in enthalpy associated with breaking the chemical bonds of the stan- dard state elements and forming new bonds to create the compound of interest. Representing the absolute enthalpy graphically provides a useful way to understand and use this concept. In Fig. 2.6, the absolute enthalpies of atomic oxygen (O) and diatomic oxygen (O,) are plotted versus temperature starting from absolute zero. At 298.15K, we see that fi, is zero (by definition of the standard-state reference condition) and the absolute enthalpy of atomic oxygen ‘equals its enthalpy of formation, since the sensible enthalpy at 298.15 K is zero. At the temperature indicated (4000 K), we see the additional sensible enthalpy contribution to the absolute enthalpy. In Appendix A, enthalpies of formation 400,000 300,00] 0 atoms ah, oc4000) 7 | | Fi (4000 K) 0; molecules lite ee eens | essere |e 100,00 ‘0 —¥000 2000 3000 a000 060 do0 Temperature (K) Figure 2.6 Grophicl interprettion of cbsolute enthalpy, heot of formation, and sensible enthalpy. 5%6 CHAPTER? + Combustion and Thermochemistry at the reference state are given, and sensible enthalpies are tabulated as a function of temperature for a number of species of importance in combustion. Enthalpies of formation for reference temperatures other than the standard state 298.15K are also tabulated Example 2.3 ‘A gas stream at I atm contains a mixture of CO, COs, and Nz in which the CO mole fraction is 0.10 and the CO; mole fraction is 0.20. The gas-siream temperature is 1200K. Determine the absolute enthalpy of the mixture on both a mole basis (KI) skmol) and a mass basis (kJ/kg). Also determine the mass fractions of the three compo- nent gases. Solution Given: xco = 0.10, T = 120K, Xeo, = 0.20, P=tatm, Find: nu tics Yeor Yoo, 898 Ye, Finding figix requires the straightforward application of the ideal-gas mixture law, Eqn. 2.15, and, fo find 9, the knowledge that Ex, = 1 (Eqn. 2.10). Thus, Xx, = 1 = xe0, = 0.70 and a = Each = 100[fi.c0 + Vi) ~ F209) co] + xeo,[iico, + (Ht) —f-2m)co,] + 10 [las + GT) ~Htan)} ‘Substituting values from Appendix A (Table A.1 for CO, Table A.2 for CO3, and Table AT for Na): 0.10~110,541 + 28,440) +0.20{-393,546 + 44,488] +0,70(0 + 28,118 Liss, = —$8,339.1 ky kmoln To find nc, WE need to determine the molecular weight of the mixture: KM W, 10(28.01) + 0.20(44.01) + 0.70(28.013) 1.212. MB ain Then, re ae ma] = iat = S38 Pree 2a] Since we have previously found MW, calculation of the individual mass fractions follows simply from their definitions (Eqn. 2.11)Reactant and Product Mixtures [As a check, we see that 0.0897 + 0.2820 + 0.6282 = 1.000, as required Comment Both molar and mass units are frequently used in combustion, Because of this, you should be quite comfortable with their interconversions. Enthalpy of Combustion and Heating Values Knowing how to express the enthalpy for mixtures of reactants and mixtures of products allows us to define the enthalpy of reaction, or, when dealing specif- ically with combustion reactions, the enthalpy of combustion. Consider the steady-flow reactor, shown in Fig. 2.7, in which a stoichiometric mixture of reactants enters and products exits, both at standard-state conditions (25°C, | atm). The combustion process is assumed to be complete, ic. all of the fuel carbon is converted to COs and all of the fuel hydrogen is converted to H,0. For the products to exit at the same temperature as the entering reactants, heat ‘must be removed from the reactor. The amount of heat removed can be related to the reactant and product absolute enthalpies by applying the steady-flow form of the first law (Eqn. 2.29 en = hig — I = eas — Fs (2.35) The definition of the enthalpy of reaction, or the enthalpy of combustion, Alp (per mass of mixture), is hie = deo = Igros ~ Brees (2.36a) ex L Reaciants —>! i Produc: (ichiometic” pt” (complete combustion flea mixture Setandaed sate ft standard state tonditions) conditions) Figure 2.7 Steady low reactor used to determine enthalpy of combustion 728 CHAPTER? + Combustion and Thermochemistry or, in terms of extensive properties, SHg = Hpros ~ Hee: (2.366) ‘The enthalpy of combustion can be illustrated graphically, as shown in Fig 2.8. Consistent with the heat transfer being negative, the absolute enthalpy of the products lies below that of the reactants. For example, at 25°C and { atm, the reactants enthalpy of a stoichiometric mixture of CH, and air, where | kmol of fuel reacts, is 74,831 kJ. At the same conditions (25°C, Latm), the combustion products have an absolute enthalpy of —877,236KJ. Thus, AHp = -877,236 — (—74,831) = 802,405 KI, ‘This value can be adjusted to a per-mass-of-fuel basis: u ne er ean or (-802,405/16.043) 0 Hyg 98) =—74,831 bly > (-87.236)~(-74831) = 800,405 Hyg 298) = 877.236 igure 2.8 Entholpy of reaction using representative values for @ ‘ir madure, The waler in the products is ossumed fo be in the vapor ichiometie methaneReactant and Product Mixtures ‘This value can, in turn, be converted to 4 per-unit-mass-of-mixture basis: KL) gg (EL) mas oa(Gis) = (GE) a where ‘mast Mat 1 ‘main Plaa + Mica” ATEYET C From Table 2.1, we see that the stoichiometric air-fuel ratio for CHa thus, kd 50,016 an( ip) ant nn: 7161.8. Note that the value of the enthalpy of combustion depends on the temperature chosen for its evaluation since the enthalpies of both the reactants and products vary with temperature; ie. the distance between the Hyeog and Hc lines in Fig. 2.8 is not constant ‘The heat of combustion, A/, (known also as the heating value). is numeri- cally equal to the enthalpy of reaction, but with opposite sign. ‘The upper oF hhigher heating value, HHY. is the heat of combustion calculated assuming that all of the water in the products has condensed to liquid. This scenario liberates the most amount of energy, hence the designation “upper.” The lower heating value, LV, corresponds to the case where none of the water is assumed to condense. For CHa, the upper heating value is approximately 11 percent larger than the lower. Standard-state heating values for a variety of hydrocarbon fuels are given in Appendix B. » A. Determine the upper and lower heating values at 298K of gaseous mdecane, CjoHz, per kilomole of fuel and per kilogram of fuel. The molecular weight of deca is 142.284, B. IF the enthalpy of vaporization of n-decane is 359KJ/Kgjuy at 298K, what are the upper and lower heating values of liquid n-decane? Solution A. For 1 mole of CHa», the combustion equation can be written as CyoHnale) + 15.510) + 3.76N;) > 10CO; + LIH;OU or g) + 15.513.76)N> For either the upper or lower heating value, AH, =~ BH = Hens ~ Hoi where the numerical value of Hyg depends on whether the HO in the products is liquid (determining higher heating value) or gaseous (determining lower heating value). The sensible enthalpies for all species involved are zero since we desire AM, at the reference state (298 K). Furthermore, the enthalpies of formation of the (Oy and Nz are also zero at 298K. Recognizing that Example 2.430 CHAPTER? © Combustion and Thermochemistry Hye = Niky and wwe obtain AML ,09 = HAY = (hi cy ~ [10 Table A.6 (Appendix A) gives the enthalpy of formation for gaseous water and the enthalpy of vaporization. With these values, we can ealculate the enthalpy of Formation for the liquid water (Eqn. 2.18): Fi. xsouy = hase ~ hg = ~241 847 ~ 44,010 = 285,857 kro Using this value, together with enthalpies of formation given in Appendices A and 1B, we obtain the higher heating value: AH. 1400 = «n(-249659 8) ei [10(s9.ss6 &) + u(-2esas7 a] 6.830.096k3 and ai. a 6.830.096 KI/kinolo a, or Ahi, _ 6,830,096 py _ 8h = args = TE B= e000 hac For the lower heating value, we use f/j,o) = —241,847k3/kmol in place of Fi yoy = ~285857 KJ /krmol. Thus, 345 986KI Ol, or ‘Bh, = 4.601 Kena] B. For CjgHza in the lig iid), cess an) = (EM) hgReactant and Product Mixtures 31 2 2 2 Meno (teri ct) “Temperature Figure 2.9 Entholpy-temperature plot illustrating calculation of heating values in Exemple 24. Thus, = 47.644 10 /kge yt 44,601 — 359) 44.242 kde, Comment Graphical representations of the various definitions and/or thermodynamic processes are valuable aids in setting up problems or in checking their solutions. Figure 2.9 illustrates, on fi-T’ coordinates, the important quantities used in this example. Note that the enthalpy of vaporization given for n-decane is for the standard-state tempera ture (298,15), while the value given in Appendix BB is at the boiling point (447.4 K).2 CHAPTER 2? © Combustion and Thermochemistry ADIABATIC FLAME TEMPERATURES We define two adiabatic flame temperatures: one for constant-pressure com- bustion and one for constant-volume. If a fuel-air mixture burns adiabatically aa constant pressure, the absolute enthalpy of the reactants at the initial state Gay, T = 298K, P = 1 atm) equals the absolute enthalpy of the products at the final state (T = T,q, P = atm), ie., application of Eqn. 2.28 results in Heeac(Ti, P) = Hoa Tats Ps (2.40a) or, equivalently, on a per-mass-of-mixture basis, Ira P) = hypo Tats P) 240b) ‘This first-law statement, Eqn. 2.40, defines what is called the constant-pressure adiabatic flame temperature, This definition is illustrated graphically in Fig. 2.10. Conceptually, the adiabatic flame temperature is simple; however, eval- uating this quantity requires knowledge of the composition of the combustion products, At typical flame temperatures, the products dissociate and the AaB) Figure 2.10 tllsration of conslant-pressure adiabatic fame temperature on h-T coordinates.Adiabatic Flame Temperatures, 33 ‘mixture comprises many species. As shown in Table 2.1 and Table B.I in Appendix B, flame temperatures are typically several thousand kelvins. Calculating the complex composition by invoking chemical equilibrium is the subject of the next section. The following example illustrates the fundamental concept of constant-pressure adiabatic flame temperatures, while making crude assumptions regarding the product mixture composition and evaluation of the product mixture enthalpy. Estimate the constant-pressure adiabatic flame temperature for the combustion of a Example 2.5 | stoichiometric CH,-air mixture, The pressure is | atm and the inital reactant tempera. ture is 298K Use the following assumptions “Complete combustion” (no dissoeiation), ic. the product mixture consists of only CO;, HzO, and Ns. 2. The product mixture enthalpy i estimated using constant specifi heats evaluated at 1200 K (&0.5(7; + Tyo), whete Tyy is guessed to be about 2100 Ki. Solution Mixture composition: a 1s +203 +3.76N2) > 1 CO, + 2H:0 4+ 7.52N; Neo, = 1 Nino = 2. Ny, = 7.52. Properties (Appendices A and Bi; Enthalpy of Formation @ 298K Specific Heat @ 1200K Species Heel) “ga (kha) oa 74831 cos 93,546 021 10 alas a7 N ° ual °: ° First law (Eqn. 2.40) Heys = ON=TAS31) + 2(0) + 7.5210) 14831 KI Heo = > Nils + bh Tae ~ 298) Df. -393,546 4 $6.21 Ts — 298) + (2-241,845 + 43.8717, ~ 298)] + (7.52404 33.71(Tyy — 298) Equating Hage © Meog and Solving for Ty yields Tay = 2318K]CHAPTER? © Combustion and Thermochemistry Comments Comparing the above result with the equlirium-composition based computation Shown in Table 21 (Tuy = 2226K) shows that the simplified approach overestimates Tray by slightly kes than’ 100K. Considering the erodeness of the assumptions. this appeats to be rather surprisingly good agreement. Removing assumption 2 and re- caleulating Tay using variable specific heats, i. fmt | iar, yields Tyy = 2328K. (Note that Appendix A provides tabulations of these integrated ‘quantities, Similar tabulations are found in the JANAF tables (6}) Since this result is ‘uit close to our constant-c, solution, we conclude that the ~ 100K difference is the result of neglecting dissociation, Note that dissociation causes a lowering of Tyy since ‘more energy is ted up in chemical bonds (enthalpies of formation) at the expense of the sensible enthalpy. In the above, we dealt with a constant-pressure system, which would be appropriate in dealing with a gas-turbine combustor, or a furnace. Let us look ‘now at constant-volume adiabatic lame temperatures, which we might require in aan ideal Otto-cycle analysis, for example. The first law of thermodynamics (Ean, 2.20) requires Ureac(Teite Pat) Uproa(Toas Pps aly where U is the absolute (or standardized) internal energy of the mixture. Graphically, Eqn. 2.41 resembles the sketch (Fig. 2.10) used to illustrate the constant-pressure adiabatic flame temperature, except the internal energy replaces the enthalpy. Since most compilations or calculations of thermo- dynamic properties provide values for H (or h) rather than U (or 1) (1, 6}, wwe can rearrange Eqn. 2.41 to the following form: Hresc ~ Hproa ~ V(Pan ~ Pp) = 0- (2.42) ‘We can apply the ideal-gas law to eliminate the PY terms: Pra Y = YO NRyTinit = Nreve RuTrnit PAV = ON RT at = Norco RuTot Thus, Heese ~ Hyrog ~ Ru NreseTinit — Npros Tad) = 0. 2.43) An alternative form of Eqn. 2.43, on a per-mass-of-mixture basis, can be obtained by dividing Eqn. 2.43 by the mass of mixture, mgjq, and recognizing that mic! Noeas = M WeeAdiabatic Flame Temperatures or Maria! Noros = MW prog We thus obtain Tip Tu \_ teat Ro =~ reg) ~° a Since the equilibrium composition of the product mixture depends upon both temperature and pressure, as we will see in the next section, utilizing Eqn. 2.43 or 2.44 with the ideal-gas law and appropriate calorific equations of state, e h=MMT,P)=h (T only, ideal gas), to find Tay is straightforward, but non. trivial 35 Estimate the constant-volume adiabatic ame temperature for a stoichiometric CH,_air mixture using the same assumtions as in Example 25 Initial conditions are 7; = 298 K, atm (= 101,325 a). Solution ‘The same composition and properties used in Example 2.5 apply here, We note, how= ever, that the ¢,, values should be evaluated at a temperature somewhat greater than 1200. since the constant-volume Tyg will be higher than the constant-pressure Tyg Nonetheless, we will use the sume values as before, ist law (Eqn. 2.43): Hoa Hyess ~ RNa Tin Noosa SONA DN — RMT ~ Nyt Tal Substituting numerical values, we have Heat = (INTASSI) + 240) + 7.5210) TAS31KI 1-399 546 + 56.21(T yy — 298) + Q)H241,845 + 43.8717 ~ 298)] $7,520 4 33.71(Tay ~ 298)] 877,236 + 397.5(Ty — 298) KI and RulNeea Po — os Ta) = 8.315(10.52298 ~ Ty), where Nas = Ngee = 10.52 kmol Reassembling Eqn. 2.43 and solving for Ty yields 2889K) Toe Example 2.636 CHAPTER? © Combustion and Thermochemistry Comments (i) For the same initial conditions, constant-volume combustion results in much higher temperatures (S71 K higher in this example) than for constant-pressure combustion, This is a consequence of the pressute forces doing no work winen the volume is fixed (i) Note, aso, that the number of moles was conserved in going from th inital to final State. Thisis a fortuitous result for CH, and does not oecur for other fuels. i) The final pressure is well above the inital pressure: Py = Pa(Ta/ Tt) = 9.69atm CHEMICAL EQUILIBRIUM In high-temperature combustion processes, the products of combustion are not a simple mixture of ideal products, as may be suggested by the simple atom- balance used to determine stoichiometry (ef. Eqn. 2.30). Rather, the major species dissociate, producing a host of minor species. Under some conditions, what ordinarily might be considered a minor species is actually present in rather large quantities. For example, the ideal combustion products for burn- ing a hydrocarbon with air are CO, HO, O;, and No, Dissociation of these species and reactions among the dissociation products yields the following species: Hp, OH, CO, H, O, N, NO, and possibly others. The problem we address in this section is the calculation of the mole fractions of all of the product species at a given temperature and pressure, subject to the constraint ‘of conserving the number of moles of each of the elements present in the initial mixture. This element constraint merely says that the number of C, H, O, and N atoms is constant, regardless of how they are combined in the various species. There are several ways to approach the calculation of equilibrium compo- sition. To be consistent with the treatment of equilibrium in most undergrad- uate thermodynamics courses, we focus on the equilibrium-constant approach and limit our discussion to the application of ideal gases. For descriptions of other methods, the interested reader is referred to the literature [5, 7 Second-Law Considerations The concept of chemical equilibrium has its roots in the second law of thermo- dynamics. Consider a fixed-volume, adiabatic reaction vessel in which a fixed mass of reactants form products. As the reactions proceed, both the tempei ture and pressure rise until a final equilibrium condition is reached. This final state (temperature, pressure, and composition) is not governed solely by first- law considerations, but necessitates invoking the second law. Consider the combustion reaction C0 +40; > CO, 2.45)Chemical Equilibrium If the final temperature is high enough, the CO, will dissociate, Assuming the products to consist only of CO>, CO, and Os, we can write [corso], —[a-aco.+aco+Zo},, easy where a isthe fraction of the CO, dissociated. We can caleulate the adiabatic flame temperature as a function of the dissociation fraction, a, using Eqn. 2.42. For example, with a= 1, no heat is released and the mixture temperature, Pressure, and composition remain unchanged; while with f = 0, the maximum amount of heat release occurs and the temperature and pressure would be the highest possible allowed by the first law. This variation in temperature with a is plotted in Fig. 2.11 What constraints are imposed by the second law on this thought experi ment where we vary a? The entropy of the product mixture can be calculated by summing the product species entropies, ie. Swais(Tys P) = YON 5(Ty. Pi (1 = aco, +45c0 + $50, (2.47) where Nj is the number of moles of species / in the mixture, The individual species entropies are obtained from 2.48) tar 5 =5Twa+ [Gy 2 Rin vira+[ ek 000 San 3000 T(K) ofS (IK) 2000 000 02 0a 06 or To Fraction of CO, undissociated, I~ Figure 2.11 tusrotion of chemical equilbrium for fixed: oss izolated sytem. 3738 CHAPTER? — Combustion and Thermochemistry where ideal-gas behavior is assumed, and P; is the partial pressure of the ith species. Plotting the mixture entropy (Eqn. 2.47) as function ofthe dissocia- tion fraction, we see that a maximum value is reached at some intermediate value of a. For the reaction chosen, CO +40, > COs, the maximum entropy occurs near 1a = 0.5 For our choice of conditions (constant U, V, and m, which implies no heat or work interactions), the second law requires that the entropy change internal to the system ds > 0. (2.49) Thus, we see that the composition of the system will spontaneously shift toward the point of maximum entropy when approaching from either side, since dS is positive. Once the maximum entropy is reached, no further change in composition is allowed, since this would require the system entropy to decrease in violation of the second law (Eqn. 2.49). Formally, the condition for equilibrium can be written Che (2.50) In summary, if we fix the internal energy, volume, and mass of an isolated system, the application of Eqn. 2.49 (second law), Eqn. 2.41 (first law), and Eqn. 2.2 (equation of state) define the equilibrium temperature, pressure, and chemical composition. Gibbs Function Although the foregoing was useful in illustrating how the second law comes into play in establishing chemical equilibirum, the use of an isolated (fixed- energy) system of fixed mass and volume is not particularly useful for many of the (ypical problems involving chemical equilibrium. For example, there is frequently a need (0 calculate the composition of a mixture at a give tempera- ture, pressure, and stoichiometry. For this problem, the Gibbs free energy, G, replaces the entropy as the important thermodynamic property. ‘As you may recall from your previous study of thermodynamics, the Gibbs free energy is defined in terms of other thermodynamic properties as G=H-TSs. 1) ‘The second law can then be expressed as €O)r,pm <0. (2.52) Which states that the Gibbs function always decreases for a spontaneous, iso- thermal, isobaric change of a fixed-mass system in the absence of all work effects except boundary (P-dV) work. This principle allows us to calculate the equilibrium composition of a mixture at a given temperature and pressure The Gibbs function attains @ minimum in equilibrium, in contrast to the max-‘Chemical Equilibrium imum in entropy we saw for the fixed-energy and fixed-volume case (Fig. 2.11), Thus, at equilibrium, (Gp, py = 0. 2.53) For a mixture of ideal gases, the Gibbs function for the ith species is given by Bur = Sir + RT IMP’) 2.54) where gj is the Gibbs function of the pure species at the standard-state pressure (i.e., P; = #”) and P, is the partial pressure, The standard-state pres- sure, P’, by convention taken to be I atm, appears in the denominator of the logarithm term. In dealing with reacting systems, « Gibbs function of formation, Ga» is frequently employed: FAD =BT)- YY var, (2.55) where the v/ are the stoichiometric coefficients of the elements required to form ‘one mole of the compound of interest. For example, the coefficients are v6, = | and vé = 1 for forming a mole of CO from Oy and C, respectively. As with enthalpies, the Gibbs functions of formation of the naturally occurring ele- ‘ments are assigned values of zero at the reference state. Appendix A provides tabulations of Gibbs function of formation over a range of temperatures for selected species, Having tabulations of g/,(T) as a function of temperature is quite useful. In later calculations, we will need to evaluate differences in &p between different species at the same temperature. These differences can be obtained easily by using the Gibbs function of formation at the temperature of interest, values of which are provided in Appendix A. Tabulations for over 1,000 species can be found in the JANAF tables (6) ‘The Gibbs function for a mixture of ideal gases can be expressed as Grae =O NiBir = ONE + RT IPP) (2.56) where N; is the number of moles of the th species. For fixed temperature and pressure, the equilibrium condition becomes IG ain = 0 (2.57) DLANatr + RT IPP] + YON dla + R,TIn(P,/ PY] = 0. 2.58) The second term in Eqn, 2.58 can be shown to be zero by recognizing that dln P,) = dP,/P; and that > dP; = 0, since all changes in the partial pressures ‘must sum to zero because the total pressure is constant. Thus AGuix = 0 = AN fair + RT InP PY) (2.59) For the general system, where A+B... cE +/F + (2.60) 39CHAPTER? © Combustion and Thermochemistry the change in the number of moles of each species is directly proportional to its stoichiometric coefficient, ic, dN, = -Ka 261) Ng = Kb Np = tee Np = +4f Substituting Eqn. 2.61 into Eqn. 2.59 and canceling the proportionality constant x, we obtain — alah. + RUT In(Pa/P?)] — b[z6,r + RT In(Pp/P")| — (2.62) + e[Be.r + RT in(Pe/P?)] +f [Ger + RT In(Pe/P)) + Equation 2.62 can be rearranged and the log terms grouped together to yield — (CBr +f RE7 +. — aR. — bia. — --) (2.63) (Pep PY (Pe/ PY te (Pa/ PY (Pp/ PY ete. The term in parentheses on the left-hand-side of Eqn. 2.63 is called the standard-state Gibbs function change AG, i.¢., AGy = (CBE .r + 86.7 +. — OBA 7 — beBT — or, alternately, =R,Tin (Q2.64a) (Bin + fife +. aBh.n — bi — 2.640) ‘The argument of the natural logarithm is defined as the equilibrium constant K, for the reaction expressed in Eqn. 2.60, ie. (Pej PY -(Pp/ PY ete. (Pal PY" (Pa/ PY etc. With these definitions, Eqn. 2.63, our statement of chemical equilibrium at constant temperature and pressure, is given by AG} = -R,T Ink, (2.66) K, (2.65) K, = exp(-AG4/R,T). (2.666) From the definition of K, (Eqn. 2.65) and its relation to AG} (Ean. 2.66), we can obtain a qualitative indication of whether a particular reaction favors products (goes strongly to completion) or reactants (very little reaction occurs)Chemical Equilibrium at equilibrium. If AG is positive, reactants will be favored since In K, is negative, which requires that A, itself is less than unity, Similarly, if AGF is negative, the reaction tends to favor products. Physical insight to this behavior can be obtained by appealing to the definition of AG in terms of the enthalpy and entropy changes associated with the reaction. From Egn. 2.51, we can write AG} = AH’ Tas’, which can be substituted into Eqn. 2.66b: AWTIRT (ASR, Kp For K, to be greater than unity, which favors products, the enthalpy change for the reaction, AH”, should be negative, i. the reaction is exothermic and the system energy is lowered, Also, positive changes in entropy, which indicate greater molecular chaos, lead to values of K, > | Consider the dissociation of CO, as a function of temperature and pressure, CO; # CO +505 Find the composition of the mixture, ic, the mole-fractions of COs, CO, and Os, that results from subjecting originally pure CO» to various temperatures (T = 1500, 2000, 2500, and 3000 K) and pressures (0.1, 1, 10, and 100m), Solution To find the three unknown mole fractions, xco,. Xco. and Xo,. we will need three equations. The first equation will be an equilibrium expression, Eqn. 2.66. The other ‘wo equations will come from element conservation expressions that state that the total amounts of C and © are constant, regardless of how they are distributed among the three species, since the original mixture was pure COs, ‘To implement Eqn. 2.66, we recognize that a= 1,= 1, and c C0, + (NCO+ Hos, ‘Thus, we can evaluate the standard-state Gibbs function change. For example, at 2500K, act (DEF. 0, + Mico — (BF-co:]p—s60 ()0 + (1X =327.285) — (396,152) 68,907 kI/kmol ‘The values above are taken from Appendix Tables A.1, A. and AT From the definition of K,, we have Example 2.7CHAPTER? © Combustion and Thermochemistry We can rewrite K, in terms of the mole fractions by recognizing that P, = x,P. Thus, xox! (pps Xeo, Substituting the above into Eqn. 2.666, we have e018; (P/PYY ef | 00% -ol gases) y= 0.03635, 0 eo; ‘We create a second equation to express conservation of elements: No. of carbon atoms 1 ___xco + co, No. of onygen atoms ~ 2 eo + 2x00, + 2X0, We can make the problem more general by defining the C/O ratio to be @ parameter Z that can take on different values depending on the initial composition of the mixture: (Z~ Vxco + OZ ~1)xc0, + 2Zr0, a To obtain a third and final equation, we require that all of the mole fractions sum to uty Due Xe0 + X00, + Xo, apy Simultaneous solution of Eqns. I, I and III for selected values of P, T, and Z. yield values for the mole fractions xco, xco,, and o,. Using Eqns. II and TIT to eliminate Xco, and xo,. Eqn. I becomes ool! = 22 + Zxco)"*(P/P YY" ~ [2Z ~ (1 + Z)xco) xP(—AGH/R,T) ‘The above expression is easily solved for xco by applying Newton-Raphson iteration, which can be implemented simply using spreadsheet software, The other unknowns, xco. and Zo,, are then recovered using Equations 1 and TE Resuits are shown in Table 2.2 for four levels each of temperature and pressure Figure 2.12 shows the CO mole fractions over the range of parameters investigated Comments Two general observations concerning these results can be made. First, at any fixed temperature, increasing the pressure suppresses the dissociation of CO; into CO and (©,: second, increasing the temperature at a fixed pressure promotes the dissociation, Both of these trends are consistent with the principle of Le Chaitelier that states that any(Chemical Equilibrium 43 Teble 2.2 Eauitsum compotion of varius empertues ond pete for C0; = CO+ Jor Potiam Patan am ios 7 150K, A} = 18268-10" ma ro D7ss-10* 60s Lot TA 10 tm aosse to 998 5 Serio torent Baers Sane 17= 000K, AG} = 110862 1fmal = costs es 696-10 aan tom osm bores asst ie totes soon Sato? ta 0 1 280, 26} = 6907-10 Sama fe 2% oto a2 ous ato oaies 9036 ose ie ounss ows xo sore ass oat ounss Noa oes oon oa ie oasis oan aor os 10} c0,=00+ 120, 10° — « a —— tw a 8 —, 10] 10 wl 0? 10 10” 10 10° 10° Pressure) Figure 2.12. The CO male acon ulin om dstedaton of pe COs out Pressures and temperctures,CHAPTER 2 «Combustion and Thermochemistry system intaly in a state of equilibrium when subjected to a change (increasing pressure or temperature) wil shit in composition in such @ way as to minimize the Change. Foran increase in pressure, this translates to the equilibrium shifting in the direction to produce fewer moles. For the CO, « CO + 40, reaction, this means a Shift tothe let, o the COs side For equimolar reactions, pressure has no effet. When the temperature i increased, the composition shifts in the endothermic dretion, Since heat is absorbed when CO, breaks down into CO and O, increasing the temperature produces a shft co the right, to the CO+ 40, side Complex Systems The preceding sections focused on simple situations involving a single equilib- rium reaction; however, in most combustion systems, many species and several simultaneous equilibrium reactions are important. In principle, the previous example could be extended to include additional reactions. For exam- ple, the reaction O, 20 is likely to be important at the temperatures con- sidered. Including this reaction introduces only one additional unknown, xo ‘We easily add an additional equation to account for the O» dissociation: (0 /x0,)P/P? = exp(—AGF/R,T), where AG* is the appropriate standard-state Gibbs function change for the O> +4 20 reaction. The element-conservation expression (Eqn. Il) is modified to account for the additional O-containing species, No.of Catoms____xco-+ X00, No. of O atoms ~ xco + 2xco, + 2x0, + Xo" and Eqn. Il becomes Xco + Xc0, + Xo, + Xo = | We now have a new set of four equations with four unknowns to solve. Since ‘two of the four equations are nonlinear, it is likely that some method of simultaneously solving nonlinear equations would be applied. Appendix E presents the generalized Newton’s method, which is easily applied to such systems, ‘An example of the above approach being applied to the C, H, N, O system is the computer code developed by Olikara and Borman (8). This code solves. for 12 species, invoking seven equilibrium reactions and four atom-conserva- tion relations, one each for C, O, H, and N. This code was developed specifi- cally for internal combustion engine simulations and is readily imbedded as a subroutine in simulation codes. This code is used in the software provided with this book, as explained in Appendix F. ‘One of the most frequently used general equilibrium codes is the powerful NASA Chemical Equilibrium Code [5], designated CEC86. The code is fre- quently updated so the “86” represents the update year. This code is capable of hhandling over 400 different species, and many special problem features areEquilibrium Products of Combustion built into it. For example, rocket nozzle performance and shock calculations can be performed. The theoretical approach to the equilibrium calculation does not employ equilibrium constants, but rather techniques are applied to mini- mize cither the Gibbs or Helmholz energies, subject to atom-balance con- straints. ‘A more recent arrival on the equilibrium-calculation scene is the PC-based STANJAN code [7]. This is an efficient, user-friendly code available as freeware through Stanford University. This robust and flexible code uses the element potential method to caleulate equilibrium compositions EQUILIBRIUM PRODUCTS OF COMBUSTION Full Equilibrium When we combine the first law with complex chemical equilibrium principles, the adiabatic flame temperature and the detailed composition of the products of combustion can be obtained by solving Eqns. 2.40 (or 241) and 2.66 simmul- taneously, with appropriate atom-conservation constants. An example of such a calculation for constant-pressure (1.atm) combustion of propane with air is shown in Figs, 2.13 and 2.14, where it has been assumed that the only products ‘occurring are CO», CO, HzO, Ha, H, OH, O2, 0, NO, Nz, and N. In Fig. 2.13, we see the adiabatic flame temperature and the major species as funetions of equivalence ratio. Major products of lean combustion are H0, COs, Os, and Ny; while for rich combustion, they are HO, CO. CO, Hy, and N>. It is interesting to note that the maximum flame tempera~ ture, 2278.4K, occurs not at stoichiometric, but, rather, at a slightly rich equivalence ratio ( * 1,05), as does the water mole fraction (4 ~ 1.15) That the maximum temperature is at a slightly rich equivalence ratio is a consequence of both the heat combustion and heat capacity of the products (Wpood Epp) declining beyond & = I. For equivalence ratios between @ and (Tg), the heat capacity decreases more rapidly with than AH; while beyond ®(Tiu,). 4H. falls more rapidly than does the heat capacity The decrease in heat capacity is dominated by the decrease in number of product moles formed per mole of fuel burned, with the decrease in the mean specific heat being less significant. Also in Fig. 2.13, we see, as a result of dissociation, the simultaneous presence of Or, CO, and Hz at sto conditions ( = 1). Under conditions of “complete combustion,” ie., n0 dissociation, all three of these species would be zero; thus, we expose the approximate nature of the “complete-combustion" assumption. Later, we will quantity this effect. Some of the minor species of equilibrium combustion of hydrocarbons in air are shown in Fig. 2.14. Here, we see the atoms O and H and the diatomic species OH and NO, all below the 4000 ppm level, and we see that CO is a 4546 CHAPTER? 6 Combustion and Thermochemistry @= 105 a ly ir I ea) Polam Trg, 2278 K feoee 2200 Ty 20 2000 1800 1600 7 0, 1400 gw! 2 5 0 os a To 12 14 Equivalence ratio, ® Figure 2.13 Equilibrium adiabatic fame temperatures end moor product species For propene-oir combustion a! T ot minor species in lean products, and, conversely, that O, is a minor product of rich combustion. The CO and O; concentrations, however, head through the top of the graph on their way to becoming major species in rich and lean products, respectively. It is interesting to note that the level of the hydroxyl radical OH is more than an order of magnitude greater than the O atom, and that both peak slightly lean of stoichiometric conditions. Furthermore, although not shown, N-atom concentrations are several orders of magnitude less than those of the O atom. The lack of dissociation of the Nz molecule is a result of the strong triple covalent bond. The © and OH maxima in the lean region have implications for the kinetics of NO formation. Equilibrium NO concentrations are rather flat and peak in the lean region, falling rapidly in the rich region, In most combustion systems, NO levels are well below the equilib- rium concentrations shown, because of the relatively slow formation reactions, as we will see in Chapters 4 and 5Equilibrium Products of Combustion a7 2000] 1000 soo | 8 on = 20 § 5 100 é 2 NO. 2 0 ‘o ‘o 070808 oa Equivalence ai, Figure 2.14 Minor species distributions for propene-cir combustion ot 1 etm, ‘as Equilibrium In this section, we will develop simple relations that allow the calculation of the ideal products of combustion (no dissociation producing minor species) for both lean and rich conditions. For lean combustion, nothing new is involved as we need employ only atom balances; for rich combustion, however, we employ a single equilibrium reaction, CO + HzO < CO; + Hp, the so-called Water-gas shift reaction, to account for the simultancous presence of the48 CHAPTER? + Combustion and Thermochemistry incomplete products of combustion, CO and Hp. This water-gas equilibrium is central to steam reforming of CO in the petroleum industry. ‘Assuming no dissociation, the combustion of an arbitrary hydrocarbon with our simplified air can be represented as C,H, + (03 + 3.762) -> CO) + CO + dH20 + eH; +/02 +3.760N;, 2.672) which for lean or stoichiometric conditions (® = 1) becomes C\H, + a0» +3.76N3) > BCO; + dH;0 +f02 +3.76aNz, (2.67) or for rich conditions (® > 1) becomes CyH, + a(02 +3.76N;) + CO, + CO + dH,0 + eH, + 3.76aN3, (2.670) Since the coefficient a represents the ratio of the number of moles of O, in the reactants to the number of moles of fuel, we can relate a to the equivalence ratio by using Eqn. 231, ie. xb y/4 oo 2.68) thus, given the fuel type and ®, a is a known quantity. Our objective is to find the mole fractions of all of the product species. For lean or stoichiometric combustion, the coefficients ¢ and e are zero because there is sufficient O> to have all the fuel C and Hereact to form CO, and H,O, respectively, The coefficients 6, d, and f can be found by C-, H-, and O-atom balances, respectively; thus, bes, 2.652) =0, (2.696) d=yf, (2.656) 2.698) 1-0 . e+ v19 (2.608) The total number of moles of products (per mole of fuel burned) can be found by summing the above coefficients-together with the 3.76a moles of Nz’ worscree(Sz4)a-e437. a0Equilibrium Products of Combustion ‘The mole fractions are then determined by dividing each of the coefficients above by Nror Lean or stoichiometric (® < 1) Xeo, = x/Nrots (2.7la) Xco = 0, (2.71b) x10 = 0/21 Nror- (2.7le), Xu, = 0, (271d) ro. = (GP) +1100 rte) 2s, = 3.16 y/4)/ON sor) enn For rich combustion (@ > 1), no oxygen appears, so the coefficient f is zero. That leaves us with four unknowns (b, c,d, and ¢). To solve for these, we employ the three element balances (C,H, and O) and the water-gas shift equilibrium, (Peo,/P')(Pus/P') _ b-€ = Peo/P)- Puyol) 2.72) ‘The use of Eqn. 2.72 causes the system of equations for b, ¢, d, and e to be nonlinear (quadratic) Solving the element balances in terms of the unknown coefficient b results in b (2.73a) d=la-b-x 2.73b) lat btxty/2 (2.730) Substituting Eqns. 2.73a-c into Eqn. 2.72 yields a quadratic equation in b, the solution of which is Dat, = N+xty/2 = be aK, - (2.74) 1 aye “RD [(2a(K, = 1) +x + 9/27 -4K,(K, - DQax - xy)", where the negative root is selected to yield physically realistic (positive) values of b. Again, Nror = b+ etd e+ 3.16a=x-+ y/2+3.%6a, 2.75) “a50 CHAPTER? + Combustion and Thermochemistry and the various mole fractions are expressed in terms of b (Eqn. 2.74): Rich (® > 1) Xco, = /Nrors (2.76a) Xco = ¢/ Nror = (— BY/Nror. (2.760) XH, = d/Nror = Qa —b — x)/Nror. (2.16) Xn, = €/Nror = (—2a +b +.x+9/2)/Nrors (2.76d) Xo, = 0, (2.16e) An, = 3.16a/Nror. (2.768) where a is evaluated from Eqn. 2.68. Spreadsheet software can be used con- veniently to solve Eqns. 2.76a-f and their ancillary relations for the mole fractions for various fuels (values of x and y) and equivalence ratios. Since K, is a function of temperature, an appropriate temperature must be selected; however, at typical combustion temperatures, say 2000-2400 K, the mole frac tions are not strongly dependent on the choice of temperature, Selected values of K, are shown in Table 2.3 ble 2.3 Selected values of equilibrium constant Ke for water. gas shift reaction, CO+H;O%+COn+ Hy Tw s Tw & 28 105.10" 2,00 0.2200 500 1383 2,500 oes 1000 148s 3,000 oss 1,300 03887 3.500 ona Table 24 shows comparisons between the fullequilibrium calculations and the approximate method above for CO and H mole fractions for propane-air combustion products. The equilibrium constant for the water-gas shift was evaluated at 2200K for all equivalence ratios. Here, we see that for $1.2, the fall-equilibrium and approximate methods yield concentrations that differ by only a few percent. AS @ approaches unity, the simple method becomes increasingly inaccurate, because dissociation was neglected ‘To quantify the degree of dissociation at © = 1, Table 2. shows CO; and 0 mole fractions calculated using both full equilibrium and the assumption of no dissociation. Here, we se that at l atm, approximately 12 percent of the CO, dissociates, while just over 4 percent of the HzO dissociates.Equilibrium Products of Combustion Table 2.4 CO and H» mole fractions for rch combustion, CaHs-oir, P= 1 atm 10 Fs Water-Gas ° Equilibrium Eguiibviam” —% Difference (00s17 00287 “95 0.0837 009533, 05 Bb oons ovat 408 a 0.0003, 0.0800 419) | Foe k= 0199 (T= 22008). Toble 2.5 Degree of dissociation for propone-cit combustion products (P om, @=1) Mole Fraction Species Fall Eguiiriam No Dissoclation % Dissacated co; 0.027 O16 a 140 oss 0.1380 43 Pressure Effects Pressure has a significant effect on dissociation, Table 2.6 shows the decreasing degree of CO» dissociation with pressure. Since the only other carbon-contain- ing species allowed in the product mixture is CO, the effect shown in Table 2.5 results from the equilibrium reaction CO, « CO +40p. Since the dissociation of CO; results in an increase in the total number of moles present, the pressure effect shown is consistent with the principle of Le Chatelier discussed pre- viously. The H:O dissociation is more complex in that, in addition to H;0, elemental hydrogen is present as OH, Hy, and H; thus, we cannot isolate the pressure effect on HO in a single equilibrium expression, but need to simulta- neously consider other reactions. The net effect of pressure results in a decrease in the HO dissociation, as expected. We note also that the temperature increases as the dissociation is suppressed by increased pressure in accord with Le Chitelier’s principle. Toble 2.6 Effect of pressure on disocition of propane-cir combustion products (# = 1] Pressure (atm) Ta) tco,__% Dissociation mo 31 *% Diterence 42 405 a8 = % Dissociation on 2198 0.0961 a oes 10 2268 0.1077 M7 0.1484 0 2319 0.1080 m1 oasi2 100 2353 ons 40 0.1530 oe 43 2s 1352 CHAPTER? —¢ Combustion and Thermochemistry SOME APPLICATIONS In this section, we present two practical applications: the use of recuperation or regeneration to improve energy utilization and/or increase flame temperatures, and the use of fue (or exhaust) gas recirculation to lower flame temperatures. Our intent here is to apply to “real-world” examples the concepts previously developed in this chapter and to illustrate the use of some of the software included with this book. Recuperation and Regeneration A recuperator is a heat exchanger in which energy from a steady flow of hot combustion products, i., flue gases, is transferred to the air supplied to the combustion process. A general flow diagram is shown in Fig. 2.15. A wide variety of recuperators is used in practice, many of which employ radiation heat transfer from the flue gases, as well as convection, An example of @ recuperator for an indirect-fired application is illustrated in Fig. 2.16, ‘A regenerator also transfers energy from the flue gases to the incoming combustion air, but, in this case, an energy storage medium, such as a corru- gated steel or ceramic matrix, is alternately heated by the hot gases and cooled by the air. Figure 2.17 illustrates the application of a spinning-disk regenerator to an automotive gas-turbine engine, and Fig. 2.18 shows a similar concept applied to an industrial furnace. In other regenerator concepts, the flow paths are switched alternately to heat and cool the thermal storage medium. Fioeguen Cold vel Phobeated it Figure 2.15 Schematic of furnace with oir preheated by recuperation or regeneration. Dashed in indicates the contol volume employed in Example 2.8.Some Applications Figure 2.16 _Rodiant-tube burner with coupled recuperator for indivect firing. Note thot ol the flue gases passthrough the recuperate. | SOURCE: Courtesy of Eclse Combustion ‘A recuperator, such as shown in Fig. 2.16, is employed in a natural-gas-fired heat- Example 2.8 treating furnace. The furnace operates at atmospheric pressure with an equivalence ratio of 0.9. The fuel gas enters the burner at 298 K, while the air is preheated. A. Determine the effect of air preheat on the adiabatic temperature of the flame zone for a range of inlet air temperatures from 298 K to 100K. B. What fuel savings result from preheating the air from 298 K to 600K? Assume that the temperature of the fue gases at the furnace exit, prior to entering the recu: perator, is 1700K, both with and without air preheat Solution (Part A) We will employ the Fortran program HPFLAME, which incorporates the Olikara and Borman equilibrium routines {8}, t0 solve the frst-law problem, Hise = Hyros- The input file For the program requires the definition of the fuel by providing the number of carbon, hydrogen, oxygen, and nitrogen atoms constituting the fuel molecule, the ‘equivalence ratio, a guess for the adiabatic Name temperature, the pressure, and the reactants’ enthalpy. The input file for this example, treating natural gas as methane, is shown below: Adiabatic Flame Calculation for Specified Fuel, Phi, P, & Reactant Enthalpy Using Olikara & Borman Equilibrium Routines 5354 CHAPTER? — © Combustion and Thermochemistry Exhaust Turbines Regenerator Combustor Figure 2.17 Flow schematic for automotive gas-urbine engine wih sinning dik regeneraior. Ambion! oi is compressed 10 46 psi ond 43°F betore passing trough the regenerator. The thermal energy given up by the regenerator heos the ait fo 1276'F prior to combustion. Afer the products of combustion expand through the two Wurbines, they enter the ‘opposite side ofthe regenerctor of 1370°F, returning energy to the spinning disk, an exhaust of 548° [PSOURCE: Cauresy of Chyler CorporationSome Applications & 12ce epplications (b) FlowCHAPTER? © Combustion and Thermochemistry Problem Title: EXAMPLE 2.8 Air Preheat at 1000 oO /CARBON ATOMS IN FUEL 04 /HYDROGEN ATOMS IN FUEL 00 XYGEN ATOMS IN FUEL 00 ITROGEN ATOMS IN FUEL 0.900 EQUIVALENCE RATIO 2000. TEMPERATURE (K) ({nitial Guess) 1013250 /PRESSURE (Pa) 185037.0_ /ENTHALPY OF REACTANTS PER KMOL FUEL (kl/kmol-fuel) The only quantity requiring calculation is the reactants’ enthalpy, expressed as ki/kmol of fuel. To find the number of moles of O; and N; supplied per mole of fuel, we write ur combustion equation as CH, + a(02 + 3.70Ny) + products, where (Eqn. 2.68) xty/4_ (44/4) _ ° 09 = 322 Thus, CH, + 2.220; +8.35N; + products The reactants’ enthalpy (per mole of fuel) is then Hoses ity +2.226h,0, +835Ahay, Using Tables A.7, A.11, and B.1, the above expression can be evaluated for various air temperatures, as shown in the following table. T He wo (esfhanon) 298 TAT 400 45256 600 4+20,140 800 486082 1.000 4155037 Using the Hien values from the table, the constant-pressure adiabatic lame tempera tures are caloulated using HPFLAME. These results also are given in the table and plotted in Fig. 2.19, ‘Comment (Part A) We note from Fig. 2.19 that, for the range of preheat temperatures investigated, 2 100 K increase in air temperature results in about 2 SOK increase inflame temperature. This effect can be attributed to dissociation and to the larger specific heat of the product ‘gases compared with the ar.‘Some Applications 37 2600 9 Tey, = 298K P= iam 200) g g i Slope =0.5 E 2200 2000) 298 o 200 400, 00, 300 1000 Air temperature (K) Figure 2.19 _Elfect of combustion ai preheo! on adiabatic lame temperature for methone combustion (@ = 0.9, P= lat, Solution (Port B) ‘To determine the amount of fuel saved as a result of preheating the air to 600K, we will write an energy balance forthe control volume indicated in Fig. 2.15, assuming both the heat transferred to the load and the heat losses are the same, with and without preheat. Assuming steady flow, we apply Eqn. 2.28, recognizing that heat is transferred out of the control volume: =Qout ~ Dios = Fllpg ~ Pred = (rig + HteVhgos — Fee — tthe For convenience, we define a fuel utilization efficiency as @ _~WA/F) + Wipeos = (A/PIa ~ hr) ‘7LAW LHV To evaluate the above, we require: itl MW, 46644 kg 923KJ/ke (calculated by TPEQUIL code; see Appendix F) Fawr58 CHAPTER? © Combustion and Thermochemistry Ayaunk =(021Bhy0, +0.794h,9,) MWg 0216288) + 0.736905) 28a =a112ki/kg ‘Thus, with air entering at 298K, and, for air entering at 600K, H(A + 14-923) — 1981.2) ~ (4664.4) 30,016 = 0.394. We now calculate the fuel savings, defined as or, expressed as a percentage, Comment (Part B) ‘We see that substantial fuel savings can be realized by using recuperators to return some of the energy that would normally go up the stack. Note that the nitric oxide emissions may be affected, since peak temperatures will increase as a result of preheat. With air entering at 600K, the adiabatic flame temperature inereases 150K (7.1 percent) above the 298K air case, Flue- (or Exhaust-) Gas Recirculation In one strategy to decrease the amount of oxides of nitrogen (NO,.) formed and emitted from certain combustion devices, a portion of the burned product ‘gases is recirculated and introduced with the air and fuel. This emission control strategy, and others, is discussed in Chapter 15. The effect of the recirculated {gases is to decrease the maximum temperatures in the flame zone. Decreased flame temperatures result in less NO, being formed. Figure 2.20a schematically illustrates the application of flue-gas recirculation (FGR) ina boiler or furnace, while Fig. 2.20b shows the exhaust-gas recirculation (EGR) system used in automotive engines, The following example shows how the principle of con- servation of energy can be applied to determine the effect of product gas recirculation on flame temperatures.Some Applications ren Tron 4 Tt Loy Fuel —>—>] p+ $e Five gases Tre EVR VPWR circuit EVR driver cree, > | QI Figure 2.20 _ (a) Schematic of flue-gos reciculetion applied to boiler or furnace. Eshoust-gos recculation system for sparkeigniton engine. "SOURCE: tb} Courtesy of Ford Meter Company. 39CHAPTER 2 —» Combustion and Thermochemistry Example 2.9 Consider a spark-ignition engine whose compression and combustion processes have been idealized as a polytropic compression from bottom-dead-center (state 1) to top- dead-center (state 2) and constant-volume combustion (state 2 to state 3), respectively, as shown inthe sketch below. Determine the effect of EGR (0-20 percent, expressed as a volume percentage ofthe air and fuel) on the adiabatic Rame temperature and pressure atstate 3. The engine compression ratio (CR = ¥,/V>) is 80, the polytropic exponent is 1.3, and the initial pressure and temperature (state 1) are fixed at 0,Satm and 298 K, respectively, regardless of the quantity of recirculated gas. The fuel is isooctane and the equivalence ratio is unity Pe o-10 Py=05 aim 7 1-298 2 Solution To determine the initial temperature and pressure for the start of combustion (state 2), we apply the polytropic relations: T= T(V/VaY1 = 2988)" = 556K Py(V,/ Va)" = 0.5(8)!? = 7.46 atm (755,885 Pa). A To analyze the combustion process, we will employ the code UVFLAME, Inputs required for the code that need to be calculated are Hye (kI/kmol—fuel), Nac/ Nils and MWe. Each ofthese quantities will vary as peroent EGR is changed, although the {emperature and pressure remain fixed. To determine these inputs, we first determine the ‘composition of the recycled gases, assuming that they consist of undissociated products of the reaction CgHix + 12.5(03 + 3.76N2) > 8CO; +910 4 47N;, Thus, Using Tables A.2, A.6, and A.7, we evaluate the molar specific enthalpy of the recycled ‘bases at T (= 556K); fear 1250(-~-382,707) + 0,1406(232,906) + 0.7344(7588) 75 0123kS/kmoleae ‘The molar specific enthalpy of the air at T3(= $56K) is Jig = 0.21(7853) + 0.79(7588) = 7643.7 I keno,‘Some Applications ‘ ‘The fuel enthalpy at 73 is calculated from the curvefit coefficients given in Table B.2 ‘Note that the enthalpy generated from these coefliients isthe sum of both the enthalpy ‘of formation and sensible enthalpy: dip = 61,221 19 kong. ‘The enthalpy of the reactants at state 2 can now be calculated: HH = Mele + Nala + Neonlieor: where, by definition, N+ NP)%EGR/100%. 12,514.76) Neos From the stoichiometry given, N, 59,5 kmol; thus, Hl Vig + (59.)h + 60.5%EGRYhgon io Values of He for various percent EGR are shown in the following table. ‘The reactant mixture molecular weight is Np MW 4 NAMI + NeouMWron MW reac = Net Na+ Mecr . where Mi con= uM, i 0.1250(44.011) + 0.1406(18.016) + 0.7348(28.013) 29.607 ke/kmolcon Values for MWg and Nug(= Np-+ Ng + Neg) are also shown in the following table. *4PGR Nec Na MW a) 0 7 60.50 30261 $293,599 5 ams 25 sos $66,667 w 6.050 66.88 30111 160,248 1s 97s wats so.04s 2» 12.100 Ed 29.98 =614070 Using the above information, we exctcise the code UVFLAME and calculate the following adiabatic temperatures and the corresponding pressures at state 3. EGR Py (atm) 0 ‘ost 5 wal 0 3838 wm 2» 363i ‘These results are plotted in Fig. 2.21a CHAPTER? © Combustion and Thermochemistry = 4 § i a Ppa 746 a0m TossoR 200 pe é i #200 3 a 2 asm ° 5 1 5 30 ‘exhaust gas eireulation igure 2.21 Calculated adiabatic lame temperatures and peok pressues for const volume combustion, wth combustion products regyced withthe frth air ond fuel (Example 29}, Comments From the table and the graph, we see that EGR can have a pronounced effeet on peak temperatures, with 20 percent EGR resulting in a drop of about 275K from the zero recycle condition, As we shall see in Chapters 4, 5, and 15, such temperature decreases ‘can have a dramatic effect on NO, formation We should note that in real applications, the temperature of the recycled gases is likely to vary with the amount reeyeled, which, in turn, affects the final peak tempera ture, Furthermore, we did not check to see ifthe initial (state 1) temperature was below the dew point of the recycled gases, as condensed water would be undesirable ina real EGR system, Example 2.10 ‘A package boiler, fueled by natural gas (CH,), operates witha stack-gas O, concentra: tion of 1.5 percent (by volume). The fuel gas is supplied at 298K, while the air is preheated to 400K. Determine the adiabatic flame temperature and the equilibriam NO concentration for operation with 15 percent FGR, where the FGR is expressedSome Applications oa ‘a5 a volume percentage ofthe fuel and air. The recirculated gases enter the combustion ‘chamber at 600K. Compare these results with those for operation without FGR. Solution ‘We start by determining the equivalence ratio, For both eases, the overall stoichiometry is the same and can be written as CH, + a(Q2 + 3.76Ng) + COs +20 +20} + 3.76aN; ‘An Onatom balance yields 2a=242420 O15, then 008 = ape 36a Solving the above two relationships simultaneously yields ¥=0169 and g=2:1699, For stoichiometric (® = 1) conditions, a2; thus, the operating equivalence ratio is simply = 09217, a T1698 Which follows from Eqns. 2.32 and 2.33a, ‘We consider first the case without FGR and employ the code HPFLAME to ealeulate the adiabatic fame temperature and the equilibrium yy. To use this code requites the reactants’ enthalpy per mole of fuel: Here = Nelig + Nobo, + Nici. where Np =1 (required by kmol-of-fuel basis), No, 2.1699, Ny, = 3.760 = 8.1589, Using Appendix Tables B.1, A.I1,and A.7, we evaluate the specific motar enthalpies of the CHy, Os, and Ny at their respective temperatures to obtain the reactant mixture enthalpy: Hoa (=74.831) + 2.1699(3031) + 8.1589(2973) = ~43,97 kd Since the boiler operates at essentially atmospheric pressure, the required input file for HPELAME is then Adiabatic Flame Calculation for Specified Fuel, Phi, P, & Reactant Enthalpy Using Olikara & Borman Equilibrium Routines Problem Title: EXAMPLE 2.10 Case without FGRCMAPTER? © Combustion and Thermochemistry o JCARBON ATOMS IN FUEL of /HYDROGEN ATOMS IN FUEL 0 /OXYGEN ATOMS IN FUEL co) JNITROGEN ATOMS IN FUEL 09217 EQUIVALENCE RATIO 2000, /TEMPERATURE (K) (Initial Guess) 1013280 /PRESSURE (Pe) 4997.0 /ENTHALPY OF REACTANTS PER KMOL FUEL (ki/kmol-fuel) Running HPFLAME yields 2209.8K 0.003497 or 3497 ppm, Tos xo For the 15 percent FGR case, there are several ways to calculate the adiabatic flame temperature using the codes supplied with this book. Our approach will be frst to determine the reactant mixture enthalpy (fuel, air, and FGR) per unit mass of mixture and then to employ Eqn. 2.40: pca(Ted). We will use TPEQUIL to calculate hyjog(Tas) for assumed values of Tyy and iterate to obtain a final result. ‘As we have previously calculated the reactant fuel and air enthalpies, we need only to add to these the FGR enthalpy to obtain the total reactants’ enthalpy: ie, Hse Vrlig + Nolo, + Nxcfin, + Neowliran: Rather than calculating fipga by hand, we employ TPEQUIL with T= 600K, © =0.9217, and P = 101,325Pa. This yields Igo = ~2.499- 10° KI kg with MWecq = 27.72kg/ktmol, Thus, freon = hronM Wear = ~67,886 I /kmolron We obtain the number of moles of FGR from the definition Neck = (Nr +N,)%FGR/100% = [1 + @.1699)4.76]0.15 = 1.6993 kmol. ‘The reactant mixture enthalpy is Hage = ~43,99T + 1.6993( 67,886) = 159,356),Some Applications and the mass-speciie enthalpy is © TOB.UFR) + 1032928.85) + 1.6993527.73) = 441 3k kg, We now employ Eqn. 2.40b using TPEQUIL, Knowing that Tyy must be less than the zer0-FGR value of 2209.8K, we guess at 210K. With this temperature as input t0 TPEQUIL, the output value for fy (2100K) is ~348.0KI/kg. A. second guess of 2000K yields Fy (200K) = ~SI9.2ki/kg. With these two Values bracketing the desired value, we linearly interpolate to obtain Ty) = 2045,5K. Further iteration using TPEQUIL. yields the final value: Ty = 2046.5K with x0 = 0.002297 or 2297 ppm. ‘Comparing these results with those without FGR, we see that 15 pereent FGR results in aan adiabatic flame temperature drop of approximately 163K, while equilibrium NO ‘mole fractions decrease by 34 percent Comments This problem can be solved directly using HPFLAME, provided the correet value of reactants’ enthalpy is used. Since the code assumes that the reactants consist only of fuel and air, the FGR must be treated, on an element basis, to be fuel and air; thus, the ‘number of moles of fuel in the reactants exceeds unity, The number of moles of “fuel” from the FGR is the number of moles of FGR divided by the number of moles of products formed per mole of CHy burned, as determined by the combustion equation sven at the start of the solution; ie, Nepue tom FOR gee (KI /KMOl ju TH Neer fom FoR For our specific problem, Neto tar = 1-6993(0,0883) = 0.15 and ime = ~159,356/1.15 = 138,571 ki/kmoljg Using this value with HPFLAME yields the same result for Ty as obtained above, but without iteration. For the constant-volume ‘combustion process (see Example 2.9), the code UVFLAME works directly on a mass basis using the values input for the total number of moles and the molecular weight of the reactants; therefore, no correction to the reactant enthalpy is required when dealing with FGR or EGR when using UVFLAME. We note that the NO mole fractions calculated are equilibrium values. In a practical application, the NO concentrations in the combustion chamber and the flue are deter- ‘mined by chemical kinetics (Chapters 4 and 5) as, in most cases, insufficient time is available to achieve equilibrium; nevertheless, the differences between the equilibrium66 CHAPTER? «Combustion and Thermochemistry [NO values with and without FGR indicate the potential for the reduction of kinetically determined NO by FGR (see Chapter 15). SUMMARY lll of the concepts presented in this chapter are of fundamental importance to a study of combustion. We began this chapter with a brief review of basic thermodynamic properties of simple substances and ideal-gas mixtures. We also reviewed the conservation of energy principle, the first law of thermody- ‘namics. The first law in its various forms should be an old friend by now. You should be familiar with the equivalence ratio and how it is used to define rich, lean, and stoichiometric mixtures. Other important thermodynamic properties defined include absolute (or standardized) enthalpies, which are used with the first law to define enthalpies of reaction, heating values, and constant-pressure ‘and constant-volume adiabatic flame temperatures. You should be able to illustrate all of these properties graphically on appropriate thermodynamic ‘coordinates (AT or wT). In our discussion of chemical equilibrium, we intro- duced the Gibbs function and demonstrated its utility in calculating the equilib rium composition of ideal-gas mixtures. You should be able to calculate equilibrium compositions for simple mixtures using equilibrium-constants (K,). together with element conservation. You should also be able to formulate the more complex problems; however, a familiarity with one or more equilib rium computer codes is useful for their solution. The final topics in this chapter dealt with the variation of combustion product mixture composition with equivalence ratio and the importance of dissociation. You should understand which species may be considered major and which minor, and have an appre- ciation for the order of magnitude of the mole fractions of the 11 important species we considered. Also shown was the usefulness of water-gas equilibrium for dealing with rich product mixtures in a simplified way. You should be able to calculate the composition of combustion product mixtures assuming no dissociation. Although many seemingly diverse topics were discussed, you should appreciate how the principles of the first and second laws of thermo- dynamics underpin these topics. NOMENCLATURE a Molar oxygen-fuel ratio (kmol/kmol) AIE Mass air-fuel ratio (kg/ke) onde Constant-pressure specific heat (J/kg-K or J/kmol-K) enee Constant-volume specific heat (J/kg-K or J/kmol-K) Ee Total energy (J or J/kg) FIA Mass fuel-air ratio (kg/kg)8 & e Gz AG? Hii Ah MHe, he, Alc AHg, Ah Dlg HHV Ky Lv NST BENT ONT ER Greek Symbols x errr Subscripts ad 4 Nomenclature a Gravitational acceleration (m/s?) Pure-species Gibbs function (J/kmol) Gibbs function of formation (1/kmol) Gibbs function or free energy (J ot J/kmol) Standard-state Gibbs funetion change, Eqn. 2.64 (J/kmol) Enthalpy of formation (J/kg or J/kmol) Enthalpy (J or J/kg or J/kmol) Heat of combustion (heating value) (J or J/kg or J/kmol) Enthalpy of reaction (J or J/kg or J/kmol) Higher heating value (J/ka) Equilibrium constant, Eqn, 2.65 (dimensionless) Lover heating valve (J/kg) Mass (ke) Mass flowrate (kg/s) Molecular weight (ke/kmol) Number of motes (kmol) Pressure (Pa) Heat (J or J/kg) Heat-transfer rate (J/s = W or Wike) Specific gas constant (J/kg-K) Universal gas constant (J/kmol-K) Entropy (J/K or J/ka-K or J/kmol-K) Time (s) ‘Temperature (K) Internal energy (Jor J/kg or J/kmol) Velocity (ans) ‘Volume (m? or m°/kg) Work (J or J/kg) Rate of work or power (J/s = W or W/kg) ‘Number of carbon atoms in fuel Number of hydrogen atoms in fuel ‘Mass fraction (kg/ke) Elevation (m) Element ratio Fraction dissociated Proportionaity constant, Eqn, 2.61 Density (kgim’) Equivalence ratio Mole fraction Adiabatic AirCHAPTER? —« Combustion and Thermochemistry oo Control volume fi Final or formation F Fuel 8 Gas i ith species o inlet init Initial 1 Liquid mix Mixture ° Outlet prod Product reac Reactant ref Reference s Sensible sat Saturation state stoic Stoichiometric T At temperature T Superscripts ° Denotes standard-state pressure (P? = | atm) REFERENCES 1. Kee, R. J. Rupley, F. M., and Miller, J. A., “The Chemkin Thermodynamic Data Base,” Sandia National Laboratories Report SANDS7-8215 B, March 1991 2. Moran, M. J., and Shapiro, H. N., Fundamentals of Engineering Thermodynamics, Wiley, New York, 1988, 3. Wark, K. Jr., Thermodynamics, Sth Ed., McGraw-Hill, New York, 1988. 4. Gengel, Y. A., and Boles, M. A., Thermodynamics: An Engineering Approach, McGraw-Hill, New York, 1989. 5. Gordon, S., and McBride, B. J., “Computer Program for Calculation of Complex Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected Shocks, and Chapman-Jouguet Detonations,” NASA SP-273, 1976. 6. Stull, D. R., and Prophet, H., “JANAF Thermochemical Tables,” 2nd Ed., NSRDS-NBS 37, National Bureau of Standards, June 1971. (The 3rd Ed. is avail able from NIST.) 7. Reynolds, W. C., “The Element Potential Method for Chemical Equilibrium ‘Analysis: Implementation in the Interactive Program STANIAN,” Department of Mechanical Engineering, Stanford University, January 1986. 8. Olikara, C., and Borman, G. L., “A Computer Program for Calculating Properties (of Equilibrium Combustion Products with Some Applications to 1. C. Engines,” SAE Paper 750468, 1975.n 12, Review Questions 9. Industrial Heating Equipment Association, Combustion Technology Manual, 4th Ed,, IHEA, Arlington, VA, 1988. 10, Obert, E. F., Internal Combustion Engines and Air Pollution, Harper & Row. New York, 1973 IL. Lefebvre, A. H., Gas Turbine Combustion, Taylor & Francis, Bristol, PA, 1983. 69 REVIEW QUESTIONS Make a list of all of the bold faced words in Chapter 2. Make sure you under= stand the meaning of each, Describe the temperature dependence of the specific heats of monatomic and polyatomic gases. What is the underlying cause of this dependence? What implications does the temperature dependence have for combustion? Why is the equivalence ratio frequently more meanginful than the air-fuel (or fuel-air) ratio when comparing different fuels? What three conditions define the standard reference state? Sketch a graph showing Hyaye and Hog a8 functions of temperature, taking into account nonconstant specific heats Using your sketch from question 5, illustrate the effect of preheating the reac- tants on the constant-pressure adiabatic flame temperature, Describe the effect of pressure on the equilibrium mole fractions forthe follow. ing reactions 0) 620 Ny +0) 2NO C0440» @ CO» What is the effect of temperature? Make a list of the major and minor species associated with combustion products at high temperature, ranking them from the highest to the lowest, concentrations (mole fraction) and giving an approximate numerical value for each at = 0.7. Repeat for = 1.3. Compare your lists What is the significance of the water-gas shift reaction? Describe the effect of increasing temperature on the equilibrium composition of combustion products, Describe the effect of increasing pressure on the equilibrium composition of combustion products, Why does flue-gas recirculation decrease flame temperatures? What happens if the flue gas recirculated is at the flame temperature?CHAPTER? —« Combustion and Thermochemistry 241 22 23 2.4 25 2.6 27 28 29 2.10 2u PROBLEMS Determine the mass fraction of O; and N; in air, assuming the molar composi- tion is 21 percent Oy and 79 percent No. A mixture is composed of the following number of moles of various species: Species No. of moles co. 0.095 co, 6 H,0 7 Nr 4 NO 0.005 ‘A. Determine the mole fraction of nitric oxide (NO) in the mixture. Also, express your result as mole pervent, and as parts-per-million B. Determine the molecular weight of the mixture C. Determine the mass fraction of each constituent. Consider a gaseous mixture consisting of 5 kmol of Hy and 3 kmol of > Determine the Hz and O» mole fractions, the molecular weight of the mixture, and the Hy and Oy mass fractions. Consider a binary mixture of oxygen and methane. The methane mole fraction is 0.2. The mixture is at 300K and 100kPa. Determine the methane mass fraction in the mixture and the methane molar concentration in kmol of ‘methane per m? of mixture, Consider a mixture of Nz and Ar in which there are three times as many moles of N as there are moles of Ar. Determine the mole fractions of Nz and Ar, the ‘molecular weight of the mixture, the mass fractions of Nz and Ar, and the molar concentration of Nz in kmol/m? for a temperature of 500K and pressure of 250 kPa Determine the absolute (standardized) enthalpy in J/kmol,ix of a mixture of CO, and O, where xco, = 0.10 and xo, = 0.90 at a temperature of 400 K. Determine the molecular weight of @ stoichiometric (® = 1.0) methane-air mixture. Determine the stoichiometric air-fuel ratio (mass) for propane (CyHs). Propane burns in a premixed flame at an air-fuel ratio (mass) of 18:1 Determine the equivalence ratio ©. For an equivalence ratio of = 0.6, determine the associated air-fuel ratios (mass) for methane, propane, and decane (CipHz2) In a propane-fueled truck, 3 percent (by volume) oxygen is measured in the exhaust stream of the running engine. Assuming “complete” combustion with- out dissociation, determine the air-fuel ratio (mass) supplied to the engine.242 213 214 215 16 217 2.18 219 2.20 2.21 2.22 Problems Assuming “complete” combustion, write out at stoichiometric balance equa- tion, tike Eqn, 2.30, for 1 mol of an arbitrary alcohol C.H,O.. Determine the number of moles of air required to burn 1 mol of fuel, Using the results of problem 2.12, determine the stoichiometric air-fuel rat (mass) for methanol (CH;OH). Compare your result with the stoichiometric ratio for methane (CH,). What implications does this comparison have? Consider a stoichiometric mixture of isooctane and air. Calculate the enthalpy of the mixture at the standard-state temperature (298.15 K) on a per-kmol-of- fuel basis (kJ/kmoly,y), on a per-kmol-of-mixture basis (kJ/kmolp,«)- and on a per-mass-of-mixture basis (kJ/kg) Repeat problem 2.14 for a temperature of 500K. Repeat problem 2.15, but now let the equivalence ratio = 0,7, How do these results compare with those of problem 2.15? Consider a fuel which is an equimolar mixture of propane (CsHy) and natural gas (CH,). Write out the complete stoichiometric combustion reaction for this fuel burning with air and determine the stoichiometric fuel-air ratio on a mola basis. Also, determine the molar air-fuel ratio for combustion at an equiv lence ratio, ©, of 0.8. Determine the enthalpy of the products of “ideal” combustion. ic.. no disso- ciation, resulting from the combustion of an isooctane-ait mixture for an equivalence ratio of 0.7. The products are at 1000K and 1 atm, Express your result using the following three bases: per kmoF-of-ful. per kg-of-fuel. and per kg-of-mixture. Hint: You may find Eqns. 2.68 and 2.69 useful; however. you should be able to derive these from atom-conservation considerations. Butane (C,Hj9) burns with air at an equivalence ratio of 0,75, Determine the umber of moles of air required per mole of fuel, A glass melting furnace is burning ethene (C)H,) in pure oxygen (not air). The furnace operates at an equivalence ratio of 0.9 and consumes 30 kmol/hr of ethene. ‘A. Determine the energy input rate based on the LHV of the fuel, Express your result in both kW and Biu/br. B. Determine the O; consumption rate in kmol/hr and keys. Methyl aleohol (CHsOH) burns with excess air at an air-fuel ratio (mass) of 8.0. Determine the equivalence ratio, ®, and the mole fraction of COs in the Product mixture assuming complete combustion, ive., no dissociation, The lower heating value of vapor n-decane is 44,597 kJ/kg at T= 298K. The enthalpy of vaporization of n-decane is 276.8 kl kg of n-decane. The enthalpy of vaporization of water at 298K is 2442.2 kJ ke of water, nn 2.23 2.24 2.25 2.26 2.27 2.28 2.29 2.30 2.31 2.32 2.33" CHAPTER? + Combustion and Thermochemistry |A. Determine the lower heating value of liquid n-decane. Use units of kd/kg decane to express your result B. Determine the higher heating value of vapor n-decane at 298 K. Determine the enthalpy of formation in ki/kmol for methane, given the lower heating value of 50,016 ki/kg at 298K. Determine the absolute enthalpy of the mixture given in problem 2.2 for a temperature of 1000 K. Express your result in kJ/kmol of mixture. ‘The lower heating value of methane is 50,016 kJ/kg. (of methane). Determine the heating value: A. per mass of mixture, B. per mole of air-fuel mixture. C. per cubic meter of air-fuel mixture. The higher heating value for liquid octane (CsHjs) at 298K is 47,893 kJ/kg and the heat of vaporization is 363 kJ/kg. Determine the enthalpy of formation at 298K for octane vapor. Verify the information in Table 2.1 under the headings Af (ki/kg of fuel), Aly (ki/kg. of mix), and (0/F)yie for the following: A. CHe-air B. HzO} C. CG)-air Note that any H,O in the product is assumed to be in the liquid state Generate the same information requested in problem 2.27 fora stoichiometric mixture of CsHy (propane) and air. Consider a liquid fuel. Draw a sketch on fT coordinates illustrating the following quantities: (7); h,(T'; heat of vaporization, hq heat of formation for fuel vapor; enthalpy of formation for fuel liquid; lower heating value; higher heating value Determine the adiabatic flame temperature for constant-pressure combustion ‘of a stoichiometric propane-air mixture assuming reactants at 298K, no dissociation of the products, and constant specific heats evaluated at 298 K. Repeat problem 2.30, but using constant specific heats evaluated at 2000K. Compare your result with that of problem 2.30 and discuss, Repeat problem 2.30, but now use property tables (Appendix A) to evaluate the sensible enthalpies. Once more, repeat problem 2.30, but eliminate the unrealistic assumptions, i, allow for dissociation of the products and variable specific heats. Use | “tits requied or optional use of compute.2.34 2.35 2.36" 2.37 2.38 2.39 2.40 Problems HPFLAME (Appendix F), or other appropriate software. Compare and con- trast the results of problems 2.30-2.33. Explain why they differ Using the data in Appendix A, calculate the adiabatic constant-pressure flame temperature for a boiler operating with the fuel blend and equivalence ratio given in problem 2.17. Assume complete combustion to CO; and HO and neglect any dissociation. Also, assume the heat capacity of the combustion products is constant at 1200K. The boiler operates at 1 atm, and both the air and fuel enter at 298K. Repeat problem 2.30, but for const the final pressure Use the condition given in problem 2.33. but calculate the constant-volume adiabatic flame temperature using UVFLAME (Appendix F), or other appto- priate software. Also, determine the final pressure, Compae your results with those of problem 2.35 and discuss. volume combustion. Also, determine Derive the equivalent system (fixed mass) form of the first aw corresponding to Eqn. 2.35, which is used to define the heat of reaction. Treat the system as constant pressure with initial and final temperatures equal A furnace, operating at 1 atm, uses preheated air to improve its fuel efficiency. Determine the adiabatic flame temperature when the furnace is run at a mass air-fuel ratio of 18 for air preheated to 800 K. The fuel enters at 450K. Assume the following simplified thermodynamic properties: Treg = 300K, MWg) = MWe = MWyyg = 29 K/t00, fe) = 3500 WREKS wot = 1200 J)ke-K, Ti ae = fi gua = 1.16 10° Jikmol, rod = 95 Consider the constant-pressure, adiabatic combustion of a stoichiometric ( 1) fuel-air mixture where (4/F)yc = 15. Assume the following simplified properties for the fuel, air, and products, with Tie = 300K: Fuel Air Products &, Wike-K) 3500 12001500 soo Gk) 2-107 0 =1.25- 108 ‘A. Determine the adiabatic flame temperature for a mixture initially at 600K. B, Determine the heating value of the fuel at 600K. Give units. Consider the combustion of hydrogen (H.) with oxygen (Os) in a steady-flow reactor as shown in the sketch. The heat loss through the reactor walls per unit ‘mass flow (Q/nt is 187 kI/kg. The equivalence ratio is 0.5 and the pressure is 5 atm, B“ 241 2.42 2.43, 2.44 2.45 CHAPTER? —« Combustion and Thermochemistry 8 For a zero-Kelvin reference state, approximate enthalpies-of-formation are if. 4,(0) = fif.0,(0) = 0 kS/kmol, iy —238,000 kJ/kmol, 38,600 kI/mol. ‘A. Determine the mean molecular weight of the combustion product gases in the outlet stream, assuming no dissociation B. For the same assumption as in part A, determine the mass fractions of the species in the outlet stream. C. Determine the temperature in the product stream at the reactor outlet, again assuming no dissociation. Furthermore, assume that all species have the same constant molar specific heats, é,,, equal to 40 ki/kmol-K. ‘The Hy enters at 300K and the O2 at 800K D. Now assume that dissociation occurs, but that the only minor product is OH. Write out all of the equations necessary to calculate the outlet tem- perature. List the unknowns in your equation set Verify that the results given in Table 2.2 satisfy Eqns. 2.64 and 2.65 for the following conditions A. T= 200K, P=0.1aim. B. T=2500K, P= 100atm. C. T=3000K, P Tatm, Consider the equilibrium reaction 0, ¢ 20 in a closed vessel. Assume the vessel contains 1 mol of Op when there is no dissociation. Calculate the mole fractions of O) and O for the following conditions: A. T=2500K, P= Lat, B. T= 2500K, P= 3atm, Repeat problem 2.42A, but add | mol of an inert diluent to the mixture, e.g., argon, What is the influence of the diluent? Discuss. Consider the equilibrium reaction COs ¢ CO +40>. At 10 atm and 300K, the equilibrium mole fractions of a particular mixture of CO>, CO, and O, are 0.6783, 0.2144, and 0.1072, respectively. Determine the equilibrium constant K, for this situation, Consider the equilibrium reaction HzO ¢ Hz +402. At 0.8 atm, the mole fractions are xx, = 0.9, x1, = 0.03, and xo, = 0.07. Determine the equilib- rium constant A, for this situation,2.46 2.47 2.48" 2.49" 2.50 251° 2.52" 2.53" Problems Consider the equilibrium reaction HO + CO 4 CO, + Hy at a particular tem: perature T. At T, the enthalpies-of-formation of each species are as follows iif. = -251,7000 kI/kmol, ijco = -118,700KI/kmol, i, 396,600 KS /kmol, A. What is the effect of pressure on the equilibrium? Explain, B. What is the effect of temperature on the equilibrium? Explain (calculation required) Calculate the equilibrium composition for the reaction Hy +40) <> HyO when the ratio of the number of moles of elemental hydrogen to elemental oxygen is, unity. The temperature is 2000 K, and the pressure is | atm. Calculate the equilibrium composition for the reaction HO <> Hy +40; when the ratio of the number of moles of elemental hydrogen to elemental oxygen, Z, is varied. Let Z = 0.5, 1.0, and 2,0, The temperature is 2000 K. and the pressure is 1 atm. Plot your results and discuss. Hint: Use spreadsheet software to per~ form your calculations Calculate the equilibrium composition for the reaction HzO < Hy +402 when the ratio of the number of moles of elemental hydrogen to clemental oxygen, Z, is fixed at Z = 2.0, while the pressure is varied. Let P = 0.5, 1.0, and 2.0 atm. ‘The temperature is 2000 K., Plot your results and discuss. Hint: Use spreadsheet software to perform your calculations Reformulute problem 2.47 to include the species OH, O, and H, Identify the ‘number of equations and the number of unknowns. They should, of course, be equal. Do not solve your system. Use STANJAN or other appropriate software to calculate the complete equi- librium for the H-O system using the conditions and atom constraints given in problem 2.47, For the conditions given below. list from highest to lowest the mole fractions of €O3, CO, HO, H;, OH, H. Os, 0, No, NO, and N. Abo, give approximate values. A. Propane-air constant-pressure combustion products at their adiabatic fame temperature for @ = 0.8, B. Asin part A, but for @ = 1.2. C. Indicate whi A and B. species may be considered major and which minor in parts Consider the adiabatic, constant-pressure combustion of n-decane (CioH2:) with air for reactants at 298.15K. Use HPFLAME (Appendix F) to calculate T,y and species mole fractions for O2, HO, CO>, No, CO, Hp, OH, and NO. Use equivalence ratios of 0.75, 1.00, and 1.25 and evaluate each condition for three pressure levels: 1, 10, and 100 atm, Construct a table showing your results 5% 258° 255° 2.56 2.57 CHAPTER? —« Combustion and Thermochemistry and discuss the effects of equivalence ratio and pressure on Tay and the product, mixture composition. Consider the combustion products of decane (CjoHsa) with air at an equiva- lence ratio of 1.25, pressure of 1 atm, and temperature of 2200 K. Estimate the mixture composition assuming no dissociation except for the water-gas shift ‘equilibrium. Compare with results of TPEQUIL, A natural gas-fired industrial boiler operates with excess air such that the 2 concentration in the flue gases is 2 percent (vol.), measured after removal of the moisture in the combustion products. The flue gas temperature is 700K. with: out air preheat, A. Determine the equivalence ratio for the system assuming that the proper- ties of natural gas are the same as methane. B. Determine the thermal efficiency of the boiler, assuming that both the air and fuel enter at 298 K. C. With air preheat, the flue gases are at 433 K (320°F) after passing through the air preheater. Again, determine the thermal efficiency of the boiler for both air and fuel entering at the preheater and burner, respectively, at 298K. D. Assuming premixed operation of the burners, estimate the maximum tem- perature in the combustion space (P= 1 atm) with air preheat, The equivalence ratio of a combustion process is often determined by extract- ing a sample of the exhaust gas and measuring the concentrations of major species. In a combustion experiment using isooctane (CsHs), continuous gas analyzers monitor the exhaust gas and measure a CO; concentration of 6 percent by volume and a CO concentration of | percent by volume. The sample «gas is not dried before the measurements are made, A. What is the equivalence ratio associated with this combustion process? Assume the process is overall lean. B. Ian Op analyzer was monitoring the exhaust gas, what would it be read- ing? An inventor has devised an atmospheric-pressure process to manufacture methanol. The inventor claims he has developed a catalyst that promotes the economical reaction of CO and H, to yield methanol; however, a cheap supply of CO and H; is needed. The inventor proposes burning natural gas (CH,) in ‘oxygen under fuel-rich conditions to yield a gas mixture of CO, CO;, HO, and. Hy A. If methane burns in oxygen at an equivalence ratio @ = 1.5, and the com- bustion reactions go to equilibrium, what will be the resulting gas compo- sition? Assume the combustion temperature is controlled to 1500K. B. What would be the composition if the temperature were controlled to 2500K?2.58" 2.59 2.60" 2.61 2.62" 2.63 Problems Consider the combustion of | kmol of propane with air at | atm. Construct a single graph using H-T coordinates that shows the following: ‘A. Reactants’ enthalpy, H, in kJ versus temperature, over the range of 298 800K for @ = 1.0, B. Repeat part A for & = 0.75, C. Repeat part A for @ = 1.25, D. Products’ enthalpy, H, for ideal combustion (no dissociation) versus tem- erature, over the range of 298-3500K for = 1.0. E. Repeat part D for @ = 0.75. F. Repeat part D for @ incomplete combustion. 25, using the water-gas equilibrium to account for Using the graph constructed in problem 2.58, estimate the constant-pressure adiabatic flame temperatures for the following conditions: A. For reactants at 298 K with © = 0.75, 1.0, and 1.25. B. For = 1.0 with reactants’ temperatures of 298 K, 600K, and 800K. C. Discuss your results from parts A and B. Repeat problem 2.58, but use the code TPEQUIL (Appendix F) to calculate the products’ H versus T curves, Use the same scales as you did in problem 2.58 so that the results can be overlaid for comparison. Discuss the differences associated with the product enthalpy curves for the ideal combustion case compared with the equilibrium case. Hint: Make sure the basis for all the enthalpies is per mole of methane, You will have to convert the results from TPEQUIL to this basis, Repeat parts A and B of problem 2.59 using the graph obtained in problem 2.60. Compare your results with those of problem 2.59 and discuss. Use the code HPFLAME (Appendix F) to determine the adiabatic flame tem= perature for the conditions given in parts A and B of problem 2.59 Compare your results with those of problems 2.59 and 2.61. Discuss. A furnace uses preheated air to improve its fuel efficiency. Determine the adiabatic flame temperature when the furnace is operating at a mass air-fuel ratio of 16 for air preheated to 600K. The fuel enters at 300K. Assume the following simplified thermodynamic properties: Trop = 300K, MWg = MW, MWg = 29 kg/kmol, €ptuat = Cpait = €pproa = 12005/ke-K, Wise = Ni proa = 0. Higa = 4-10" U/kg. ”2.64" CHAPTER? —« Combustion and Thermochemistry In one strategy to decrease the amount of oxides of nitrogen (NO,) formed and mitted from boilers, a portion of the flue gases is recirculated and introduced with the air and fuel, as shown in Fig, 2.20a, The effect of the recirculated gases is to decrease the maximum temperatures in the flame zone. Decreased flame temperatures result in less NO, being formed. To increase the effectiveness of a given amount of recycled gases, the gases may be cooled. Your job is to determine what combinations of percent FGR and Tyo result in maximum (adiabatic) flame temperatures of approximately 1950 K. Your design should be based on the following constraints and assumptions: the fuel enters the burner at 298 K and 1 atm; the air enters the burner at 325K and 1 atm; the oxygen (03) mole fraction in the cold, ic., undissociated, fue szases is Zo, = 0.02; the flue gas composition can be approximated as “eom- plete” combustion products for all conditions, with the equivalence ratio deter mined from the flue-gas O> content; the percent FGR is defined as the molar percentage of fuel and air supplied; the natural gas can be treated as methane; and the maximum flue-gas temperature is 1200 K. Use graphs and tables as appropriate to present your results. Also, discuss the practical ramifications of adding FGR (pumping requirements, capital equipment costs, etc.). How might these considerations affect the choice of operating conditions (%6FGR. Tacx)? APPENDIX 2A SOME FUEL CHEMISTRY The purpose of this appendix is to acquaint the reader with some of the common hydrocarbons and alcohols used as fuels or in fuel blends. Here, we present naming conventions, fuel molecular structures, and related information (on several fuel classes. For a more comprehensive treatment of fuels, particu- larly those used in engines, the reader is referred to the chapters in Obert [10] and Lefebvre {11} The various hydrocarbon families (Table 2A.1) are differentiated by whether the fuel molecules consist entirely of single carbon-carbon bonds (C-C) or contain one double (C=C) or one triple (C=C) bond, and whether the molecules are open chains (all chain ends unconnected) or form rings. The alkanes, alkenes, and alkynes arc all open-chain structures, while the eyetanes and aromaties exhibit ring structures For the open-chain families (alkanes, alkenes, and alkynes), the following, nomenclature is used to denote the number of carbon atoms contained in a particular family member: L-meth Spent 9—non eth 6—hex 10—dee 3—prop — 7—hep Hunde 4-but 8 oct 12-dodeeAppendix 2 eZ Table 20.1 Bosic hydrocarbon families Carhon-Carbon Primary Molecular Family Name Other Designations Formula Bonding Strcture Alkanes Parafine Cul Single bonds only Straight or branched ‘open chains Atkenes Oletins Ga One double bond, Straight or branched remainder singe open chaine Alkynes Actylenes GyHoy 2 One triple bond, Straight or branched remainder singe open chains Cyclones Cycloatkanes, CoH, or (CHa), Single honds only Closed ries Cycloparatins, Naphthenes Aromatics Benzene family Gl Resonance hybrid Closed rings ‘bonds (Arom: bonds) Using this nomenclature, and knowing that the word endings -ane, -ene, and -yne indicate how the carbon atoms are bound in the molecule, alkane, alkene, and alkyne family members containing three carbon atoms, for exam- ple, would be given as Propane Propene Propyne Hy Note that the older conventions can sometimes complicate fuel names for alkene and alkyne family members that have two, three, or four carbon atoms: Allkanes Alkenes. Alkynes c Methane G cs Ethane Propane Butane Ethene Propene —_—Butene Ethylene Propylene —_-Butylene Ethyne Propyne——_Butyne Acetylene. Methyl Ethyl acetylene acetyleneCHAPTER? + Combustion and Thermochemistry ‘The adjective saturated is used to denote hydrocarbon molecules in which the maximum number of hydrogen atoms is associated with the carbon atoms. Alkanes are saturated in that itis not possible to add another H atom without breaking a chain; on the other hand, both the alkenes and alkynes are unsatu- rated in that one or two additional H atoms could be added, respectively, by converting the double and triple carbon-carbon bonds to single bonds and using the valence electrons thus freed to form carbon-hydrogen bonds. Using the C; families above as examples, we see that propene can be saturated by the addition of two H atoms: CjH, +H, — C;Hs; while propyne is satu- rated with the addition of four H atoms: CsH, + 2H, > CsHs. Many of the higher hydrocarbons (carbon atom number > 3) appear as branched chains rather than simple straight chains. Compounds with straight chains are denoted as normal, or with the prefix »-. For example, normal- pentane, or n-pentane, is represented as n-Pentane CH Alternatively, compounds having the same number of carbon and hydro gen atoms can be formed using branched chains. Such compounds are referred to as isomers. For example, nH alu 2Metytbuane — H—C—C—CH Cay hnue is the branched-chain isomer of pentane: 2-methyl butane. The generic formula for both n-pentane and 2-methyl butane is CsH3. The "2" in 2-methyl butane refers to the carbon atom position (numbering from left to right) where the chain branch is attached. In this example, note that, by symmetry, the same ‘molecular structure obtains with the addition of the chain at either the second or the third carbon atom; thus, it makes no sense to refer to 3-methyl butane. One alkene isomer of particular engineering importance is 2,2,4-trimethyl pentane, which is often denoted simply as isooctane:Appendix 24 2,2.4-Trimethyl pentane ‘This compound is used as a reference fuel in the knock rating of spark-ignition ‘engines and is assigned an octane rating of 100. Fuels more prone to knock than isooctane thus have octane numbers les than 100, while fuels with greater knock resistance than isooctane have octane numbers greater than 100. The basic molecular structure of the eyelanes is a closed ring, with all carbon atoms singly bonded; for example, cyclopropane and cyclohexane have the following structures (hydrogen atoms not shown): od LL cH ded. Se&e Nf A RS 7 an Cyclopropane, CsHy, Cyclohexane, Cathy Note that the cyclanes are unsaturated; by breaking the ring, two additional hydrogen atoms could be added to saturate any cyclane, More complex cyelanes are formed by the substitution of paralfinic groups for H atoms The aromatic, or benzene derivative, family is based on a ring of six carbon atoms, but with only one hydrogen atom associated with each carbon atom. The resulting six free valence electrons form so-called resonance hybrid bonds among the six carbon atoms in the ring. The six carbon-carbon bonds are all equivalent, with the bonding electrons delocalized over several atoms. The following diagrams are frequently used to indicate this special kind of bonding:a CHAPTER? © Combustion and Thermochemistry Benzene rings can combine to form polycyclic aromaties, and side chains may be substituted for hydrogen atoms. Common alcohols are formed by the substitution of a hydroxyl group (OH) for an H atom in an alkane molecule, For example, the one-, two-, and three-carbon alcohols are given as H I Methanol . H—C—OH (Methyl alcohol) i CHjOH H wn Ethanol . H—C—C—OH (Ethyl alcohol) , f CH,OH HOH Propanol (Propyl alcohol) CyH,OH | HOH OH Alcohols are also generically designated as ROH, where R is the parent hydro- carbon radicalchapter 3 Introduction to Mass Transfer OVERVIEW As indicated in Chapter 1, understanding combustion requires a combined knowledge of thermodynamics (Chapter 2), heat and mass transfer, and chem- ieal reaction rate theory, or chemical kinetics (Chapter 4). Since most readers of this book are unlikely to have had much, if any, exposure to the subject of mass transfer, we present in this chapter a brief introduction to this topie. Mass transfer, a fundamental topic in chemical engineering. is quite complex, much more so than is suggested by the following discussion. We provide here only a rudimentary treatment of the fundamental rate laws and conservation princi- ples governing mass transfer, leaving a more comprehensive treatment of mass transfer until Chapter 7 and to other textbooks [1-4]. To develop some physical insight into mass transfer, we briefly examine the process from a molecular point of view. This has the added advantage of showing the fundamental similarity of mass transfer and heat conduction in gases. Lastly, we illustrate the application of mass transfer concepts to the mathematical descriptions of the evaporation of a liquid layer and a droplet RUDIMENTS OF MASS TRANSFER Imagine opening a bottle of perfume and placing the opened bottle in the center of a room. Using your nose as a sensor, the presence of perfume molecules in the immediate vicinity of the bottle can be detected shortly after the bottle is ‘opened. At later time, you will find the perfume odor everywhere in the room The processes whereby the perfume molecules are transported from a region of high concentration, near the bottle, to a region of low concentration, far from rya CHAPTER 3 «Introduction to Mass Transfer the bottle, are the subject of mass transfer. Like heat transfer and momentum transfer, mass may be transported by molecular processes (eg., collisions in an ideal gas) and/or turbulent processes. The molecular processes are relatively slow and operate on small spatial scales, while turbulent transport depends uupon the velocity and size of an eddy carrying the transported material. Our focus here is on molecular transport, while Chapters 11, 12, and 13 deal with the turbulent processes. Mass Transfer Rate Laws Fick’s Law of Diffusion Let us consider a nonreacting gas mixture comprising just two molecular species: species A and B. Fick’s law describes the rate at which one species diffuses through the other. For the case of one-dimensional binary diffusion, Fick's law on a mass basis is fing = Yai trig) = Pw, 3.1) Mas ow Mas ow of pci A Mat oof pecs 4 costa restated ib bk sued wh oar tw par ea ara Sec per a ee where rita is the mass flux of species A and ¥q is the mass fraction. In this book, the mass flux is defined as the mass flowrate of species A per unit area perpendicular to the flow: tity = rig A. @2) The units of ving are kg/s-m?. The idea of a “flux” should be familiar to you since the “heat flux” is the rate at which energy is transported per unit area ie, Q” = O/A with units of J/s-m? or W/m?, The binary diffusivity, Dap, is a property of the mixture and has units of m/s. Values for some binary diffusion coefficients ic. diffusivities, at 1 atm are provided in Appendix D. Equation 3.1 states that species A is transported by two means: the first term on the right-hand-side representing the transport of A resulting from the bulk motion of the fluid, and the second term representing the diffusion of A superimposed on the bulk flow. In the absence of diffusion, we obtain the obvious result that tik = Vali +g) = Yarn” = Bulk fx of species A, @.3a) Where ni” the mixture mass fux. The diffusional ux adds an additional component tothe fux of A —pDay TA = Ditfusional ux of species A. rian. 3) ‘This expression says that the diffusional fox of A,r ris proportional tothe gradient of the mass fraction, where the constant of proportionality is —pD,g. ‘Thus, we see that species A preferentially moves Irom a region of highRudiments of Mass Transler concentration to a region of low concentration, analogous to energy traveling. in the direction from high temperature to low. Note that the negative sign causes the flux.to be positive in the x-direction when the concentration gradient is negative. An analogy between the diffusion of mass and the diffusion of heat (conduction) can be drawn by comparing Fourier’s law of conduction, ar a or G4) with Fick's law of diffusion in the absence of bulk flow, Eqn, 3.3b. Both expressions indicate a flux (ig.gir oF OY) being proportional to the gradient of a scalar quantity (¥q/dx) or (dT /dx)). We will explore this analogy further when we discuss the physical significance of the transport properties pD and k, the proportionality constants in Eqns. 3.3b and 3.4, respectively. Equation 3.1 is the one-dimensional component of the more general expression tay = Yalting + ting) — pDawV¥ a, GBS) where the bold symbols represent vector quantities. In many instances, the molar form of Eqn. 3.5 is useful: Na = tal + Na) ~ Dao V0 66) where Ny is the molar fax ¢kmol/s-m*) of species A. xq is the mole fraction, and c is the mixture molar coneentration (kmOlyq/m) ‘The meanings of bulk flow and diffusional flux become clearer if we express the total mass flux for a binary mixture as the sum of the mass fux ‘of species A and the mass flux of species B. m= oak + vit. 37) Mixture Spaces A Species 8 sas a muss at sos as ‘The mixture mass flux on the left-hand-side of Eqn. 3.7 is the total mixture flowrate rt per unit of area perpendicular (o the flow. This is the rh that you are familiar with from previous studies in thermodynamics, etc. Assuming one- dimensional flow for convenience, we now substitute the appropriate expres sions for the individual species mass fluxes (Eqn. 3.1) into Eqn. 3.7 and obtain ay Yagi" ~ pDaa + Ypiit” — B.8a) or . . da ay ti” = (Yu Yay" — pDan “7 — pDan Ge (3.8b) 3586 CHAPTERS «Introduction to Mass Transfer For a binary mixture, ¥, + Yq = 1 (Eqn. 2.10); thus, d¥4 a¥p ~pPrwG® = pPax Tt =0, 89) Ditsin fox wont stipe ite ic., the sum of the diffusional fluxes of the species is zero. In general, overall mass conservation requires that 5° yur = 0. It is important at this point to emphasize that we are assuming a binary gas and that species diffusion is a result of concentration gradients only, which is termed ordinary diffusion, Real mixtures of interest in combustion contain ‘many components, not just two. Our binary gas assumption, however, allows us to understand the essential physics of many situations without the compli- cations inherent in an analysis of multicomponent diffusion. Also, gradients of temperature and pressure can produce species diffusion, ie. the thermal diffu- sion (Soret) and pressure diffusion effects, respectively. In’ many systems of interest, these effects are usually small, and, again, their neglect allows us to understand more clearly the essential physics of a problem. Molecular Basis of Diffusion To obtain insight into the molecular processes that result in the macroscopic laws of mass diffusion (Fick's law) and heat diffusion or conduction (Fourier's law), we apply some concepts from the kinetic theory of gases (g., (5, 6)). Consider a stationary (no bulk flow) plane layer of a binary gas mixture consisting of rigid, nonattracting molecules in which the molecular mass of each species A and B is essentially equal. A concentration (mass-fraction) gradient exists in the gas layer in the x-direction and is sufficiently small that the mass-fraction distribution can be considered linear over a distance of a few molecular mean free paths, 2, as illustrated in ig. 3.1. With these assumptions, we can define the following average molec- ular properties derived from kinetic theory [1, 5, 6]: Mean speed of _ (8kxT\'” species A molecules Gz . G02) Wall colision fequeney 1, * of A molecules per unit aya 7 4B) 106) i d= Mean fre path =—<—! (108 mans Dante Average perpendcilar distance 4 a= from plane of last collision to plane = 7 (3.104) where next collision occurs Where ky is Boltzmann's constant, ma the mass of a single A molecule, na/V the number of A molecules per unit Volume, nig,/V the total number of mole- cules per unit volume, and o the diameter of both A and B molecules.Rudiments of Mass Transfer noob hw nok necrak oh | ¢ 5 i “> a | i i a Y | Distane, Figure 3.1. Schematic diogrom illustrating mass difsion of species A molecvles from 0 region of high concentrtien to ow concentration. Mass ection ditbution is shown ofthe ‘ep. ‘Assuming no bulk flow for simplicity, the net flux of A molecules at the x-plane is the difference between the flux of A molecules in the positive x- direction and the flux of A molecules in the negative x-direction: TK = HIK ca ycntie — AK Cyeies GB.) which, when expressed in terms of the collision frequency, becomes aq = (Za)eatta - (Zp) cra 3.12) ymoccae) | "fom plane at c= | (moles per uni tne and ae 8788 CHAPTER 3 © Introduction to Mass Transfer We ean use the definition of density (p = myx/Via 10 relate ZK (Eqn. 3.108) to the mass fraction of A molecules: G.13) Substituting Eqn. 3.13 into Eqn. 3.12 and treating the mixture density and mean molecular speeds as constants yields ee 1k = ZH V a ca ~ Ya.nva) G.14) With our assumption of a linear concentration distribution, Ya _ Yate Yara ~ Yana dx 2a ap CY) Solving Eqn. 3.15 for the concentration difference and substituting into Eqn. 3.14, we obtain our final result: B.16) Comparing Eqn. 3.16 with Eqn. 3.3b, we identify the binary diffusivity Dag as 3 Using the definitions of the mean molecular speed (Eqn. 3.10a) and mean free path (Eqn. 3.10c), together with the ideal-gas equation of state PY = nkgT, the temperature and pressure dependence of Dag can easily be determined, ie., Pan G17) Dap x TP (3.18b) Tihus, we see that the diffusivity depends strongly on temperature (to the power) and inversely with pressure. The mass flux of species A, however, depends on the produet pDxp, which has a square-root temperature depen- dence and is independent of pressure: pay cc TOP? = 7? G.18e) In many simplified analyses of combustion processes, the weak temperature dependence is neglected and pD is treated as a constant, Comparison with Heat Conduction To see clearly the relationship between mass and heat transfer, we now apply kinetic theory to the transport of energy. We assume a homogeneous gas consisting of rigid nonattracting molecules in which a temperature gradient exists. Again, the gradient is sufficiently smallRudiments of Mass Transfer that the temperature distribution is essentially linear over several mean free paths, as illustrated in Fig. 3.2. The mean molecular speed and mean free path have the same definitions as given in Eqns. 3.10a and 3.10e, respectively; how- ever, the molecular collision frequency of interest is now based on the total number density of molecules, na/Vs Le. + Average wall colision _ 1 (my frequency per unit area ~ 4 G19) In our no-interaction-at-a-distance hard-sphere model of the gas, the only energy storage mode is molecular translational, Le, kinetic, energy. We write aan energy balance at the x-plane (see Fig. 3.2) where the net energy flow (per unit area) in the x-direction is the difference between the kinetic energy fux associated with molecules traveling from x —a to x and those traveling from xa to x: ZK yg — ZU (3.20) Tea} re Tet Tera Distance,» Figure 3.2. Schemotic diagram ilustrating energy ronster{heot conduction) associated wih molecular mation ine gos. The femperature distnbution is shown ath foo. 8990 CHAPTERS 6 Introduction to Mass Transfer Since the mean kinetic energy of a molecule is given by [5] ke= mi? = SkeT, G.21) the heat ux can be related to the temperature as Of = 3h2" Oona Tese 622) The temperature difference in Eqn. 3.22 relates to the temperature gradient following the same form as Eqn. 3.15, ie., OT _ Tess resem 2a G.23) Substituting Eqn. 3.23 into Eqn. 3.22, employing the definitions of 2” and a, ‘we obtain our final result for the heat flux: = 24) ‘Comparing the above with Fourier’s law of heat conduction (Eqn. 3.4), we can identify the thermal conductivity & as Lean aden()n. 625) Expressed in terms of 7° and molecular mass and size, the thermal conductivity 2 ke 2 ()"* The thermal conductivity is thus proportional to the square-root of tempera ture, koe T, 27) as is the Dag product. For real gases, the true temperature dependence is greater. Species Conservation In this section, we employ the rate law of species transport (Fick's law) to develop a basic species mass conservation expression. Consider the one-dimen- sional control volume of Fig. 3.3, a plane layer Ax thick. Species A flows into and out of the control volume as a result of the combined action of bulk flow and diffusion. Within the control of volume, species A may be created or destroyed as a result of chemical reaction, ‘The net rate of increase in the mass of A within the control volume relates to the mass fluxes and reaction rate as follows:Rudiments of Mass Transfer bial, Dike ae aw ar Figure 3.3 Control volume for one-dimensional enalss of conservation of species A, dines on = WRAL, = iA ag + AM, 3.28) Rate of increase Mas tow ofA Meow oA Mae pagan ‘otmasrot A inthe ‘uote eweof pens A wetin contl volume control volume contol solime by chem ection where the species mass flux vii is given by Egn. 3.1, and raf is the mass production rate of species A per unit volume (kgq/m"-s). In Chapter 5, we specifically deal with how to determine si/%. Recognizing that the mass of A Within the contro! volume i May = Yamo = YapVg and that the volume Vig AAX, Eqn. 3.28 can be rewritten: da HOY) a eer [a = Dap el 8.29) . [rie = pay 4] iid. Dividing through by AA. and taking the limit as Ax + 0, Eqn. 3.29 becomes A) ee 2 = — RL va oan Te] ig 30) or, for the case of steady flow where (o¥,4)/Ar wk [at — Pun SE] °. 631) Equation 3.31 is the steady-flow, one-dimensional form of species conservation for a binary gas mixture, assuming species diffusion occurs only as a result of concentration gradients; i.e., only ordinary diffusion is considered, For the92 CHAPTERS © Introduction to Mass Transfer ‘multidimensional case, Eqn. 3.31 can be generalized as vifg = Ve = 0. 332) Neate prouion Net Dow of species A tapas Ay cut of contol vlan chemi racon, ean wae In Chapter 7, we will employ Eqns. 3.31 and 3.32 to develop the conservation of energy principle for a reacting system. Chapter 7 also provides a more detailed treatment of mass transfer, extending the present development to multicomponent (nonbinary) mixtures and including thermal diffusion. SOME APPLICATIONS OF MASS TRANSFER The Stefan Problem Consider liquid A, maintained ata fixed height in a glass cylinder as illustrated in Fig. 3.4. A mixture of gas A and gas B flow across the top of the cylinder. If the concentration of A in the flowing gas is less than the concentration of A at the liquid-vapor interface, a driving force for mass transfer exists and species A ‘ill diffuse from the liquid-gas interface to the open end of the cylinder. If we assume a steady state exists (ie, the liquid is replenished at a rate to keep the liquid level constant, or the interface regresses so slowly that its movement can a sth imerface Liquid A Figure 3.4 Diffusion of vapor A through @ stagnont column of gos 8, i, the Stefon problem,Some Applications of Mass Transfer be neglected) and, furthermore, assume that B is insoluble in liquid A. then there will be no net transport of B in the (ube, producing a stagnant layer of B in the column. ‘Mathematically, the overall conservation of mass for this system can be expressed as ri") = constant = tk + rig. 6.33) rik =") constant (3.34) Equation 3.1 now becomes aY, tik = Yat ~ pan G*. (3.35) Rearranging and separating variables, we obtain rink — A ax 3.36 Paw 630) Assumding the product pDgg to be constant, Eqn. 3.36 can be integrated to yield rik = y= inl VAL +C. 3.37) oe 1 Yah 3p where C is the constant of integration. With the boundary condition Ya(x = 0) = Yay (3.38) we eliminate C and obtain the following mass-fraction distribution after removing the logarithm by exponentiation: Yate) = 1 = (1= Ya.den ae 3.39) c ( ‘aad oe (3.39) “The mass flux of A, if, can be found by letting Yar = L) = Yaw in Ean. 3.39. Thus, oy _ PDap | [1 = Yas’ ik = ABoe pf =a] 3.49) From Eqn, 3.40, we see that the mass flux is directly proportional to the product of the density, p, and the mass diffusivity, Daa. and inversely propor tional to the length, . Larger diffusivities thus produce larger mass fluxes. To see the effects of the concentrations atthe interface and at the top of the tube, let the mass fraction of A in the freestream flow be zero, while arbitrarily varying Yq, the interface mass fraction, from zero to unity. Physically, this couild correspond to an experiment in which dry nitrogen is blown across the tube outlet and the interface mass fraction is controlled by the partial pressure ‘of the liquid, which, in turn, is varied by changing the temperature, Table 3.1 93CHAPTERS 6 Introduction to Mass Transfer Table 3.1 Effect of inerfaca mass faction on mess fi Yar wih MPP aa) 0 ° 00s 0313 0.10 o.0ss 020 oma a0 ooo 090 2.303 0.999 6.908, shows that at small values of ¥q,, the dimensionless mass flux is essentially proportional to Yq,. For Yq, greater than about 0.5, the mass flux increases very rapidly Liquid-Vapor Interface Boundary Conditions In the example above, we treated the gas-phase mass fraction of the diffusing species at the liquid-vapor interface, Yq, as a known quantity. Unless this mass fraction is measured, which is unlikely, some means must be found to calculate or estimate its value, This can be done by assuming equilibrium exists between the liquid and vapor phases of species A. With this equilibrium assumption, and the assumption of ideal gases, the partial pressure of species A on the gas side of the interface must equal the saturation pressure associated. with the temperature of the liquid, i.e, Pai = Paa(Tigs) G41) ‘The partial pressure, P,,, can be related to the mole fraction of species A, Aaa = Par/P, and to the mass fraction: — PastTigs) MW Yau Po MWaixs’ 3.42) where the molecular weight of the mixture also depends on xq.».and, hence, on Pr The above analysis has transformed the problem of finding the vapor mas: fraction at the interface to the problem of finding the temperature at the inter- face. In some cases, the interface temperature may be given or known, but, in general, the interface temperature must be found by writing energy balances for the liquid and gas phases and solving them with appropriate boundary condi- tions, including that at the interface. In the following, we will establish this interface boundary condition, but leave the gas-phase and liquid-phase energy balances for later:Some Applications of Mass Transfer Gas phase n Ory tng Figure 3.5 Energy bolonce atthe surface of eoporating fhid In crossing the liquid-vapor boundary, we mai ture, ie. ‘ain continuity of tempera- Tig = 0°) = Trap A = 0°) = TO). 3.43) and energy is conserved at the interface as illustrated in Fig. 3.5. Heat is transferred from the gas to the liquid surface. Q,_,. Some of this energy goes into heating the liquid, Q,_,. while the remainder causes the phase change. This energy balance is expressed as Oe 0, i sap ~ tig) = Hit 3.44) or oer = til (3.45) Equation 3.45 can be used to calculate the net heat transferred to the interface if the evaporation rate, nt, is known, Conversely. if Oya is known, the evapor tion rate ean be determined 95 Liquid benzene (C,Hg). at 298 K. is contained in a [-cm-diameter glass tube and main- tained ata level 10cm below the top of the tube, which is open fo the atmosphere. The following properties of benzene are piven: Thon = 383K c@ Lat, Ig = 393KI/ Rg @ Tro MW =78.108kg/kimol f= 879 kg/m, Dert,-air = 0.88 10% m/s. 298K, ‘A. Determine the mass evaporation rate (kg's) of the benzene How long does it take to evaporate 1-em’ of benzene? ©. Compare the evaporation rate of benzene with that of water. Assume Dison = 2.6- 10 mJ, Example 3.1CHAPTERS © Introduction to Mass Transfor Solution A. Find rite, ‘Since the configuration given represents the Stefan problem, we ean apply Eqn. 3.40 nfictons] Yeates In the above, D, L, and Yeu, (= 0) are all known: however, we need to evaluate the benzene mass fraction at the'interface, Yen,» and an appropriate mean density, before proceeding From Eqn. 3.42, we know that MWe, Yeates = Het Spee where (t, reas = To evaluate P,../P, we integrate the Clausius-Clapeyron equation, Ean. 2.19, dP_ iy a P RUMWen, TF from the reference state (P = Latm, T= Thay = 353K) to the state at 298K, ie. 145, The interface mixture molecular weight is then So, Pay = 0.145 atm and xe,s, MWygs = 0.145(78.108) + (1 = 0.145)28.85 35.99kg/kmel, mn of ar is assumed. The interface benzene mass fraction where the simplified composi is then 78.108 35.99 For isothermal, isobaric conditions, we can estimate the mean gas density in the tube by using the ideal-gas law and the mean mixture molecular weight as follows: ee eee RMT Yeaye = 0.45 22108 — 9 3347,Some Applications of Mass Transfer ” where ‘Thos, 326ke/m' 1.326(0.88 «10 uf 1-0 or Tao, 167-10 In(1.459) 167 10-%(0.378) = 4.409 1 and cB /S+t Fa] = iy, 346-10 ker] + B. Find the time needed to evaporate Icm’ of benzene. Since the liquid level is maintained, the mass flux #8 con evaporate the Tem? thus, ant during the time to Moap _ Big 879¢kg/m')1 10-4") 3.46- 10" (kg/5) [2.34: 10°s oF 70.6% ©. Find mien no. Finding niyo follows the above; however, the problem is simplified since we ean use the steam tables (@., [7)}, to find Py, at 298K rather than invoking the Clausius~ CClapeyron approximation, From the steam tables, Pegg 298K) = 3.169 kPa 3160 ru0u= Foy gas — 203128 and MW os = 0.03128(18.016) + (1 ~0.03128)28.85 = 28.51. ‘Thus, Mino 18.016 = M0 Ee = 0.03128 Fer Yixou 0.01977.CHAPTERS — © Introduction to Mass Transfer The mean molecular weight and mean density in the tube are HW = 10851 +2885) = 28.68 101,328 3315 Gres)" where we assume the air outside ofthe tube is dry. ‘The evaporation flux is then ‘infgg = NBO 1 if 1-0 | oor T= 001977, £050.10 In(1.020) = 3.050 10%(0.01997) = 6.09 10~%ke/sem? L173 key. Tig, |_ 4409 -10-* ‘ino |~ 609-10 Comment Comparing the details ofthe calculations in parts A and C, we see that the higher vapor pressure of the benzene dominates over the higher diffusivity of the water, thus causing the benzene to evaporate more than seven times faster than the water Droplet Evaporation ‘The problem of the evaporation of a single liquid droplet in a quiescent envi- ronment is just the Stefan problem for a spherically symmetric coordinate system, Our treatment of droplet evaporation illustrates the application of mass-transfer concepts to a problem of practical interest. In Chapter 10, we will deal with the droplet evaporation/combustion problem in greater detail; however, we foreshadow the Chapter 10 development by introducing the concept of an evaporation constant and droplet lifetimes. Figure 3.6 defines the spherically symmetric coordinate system. The radius rris the only coordinate variable, It has its origin at the center of the droplet, and the droplet radius at the liquid-vapor interface is denoted r,, Very far from the droplet surface (r > 00), the mass fraction of droplet vapor is Yi. Physically, heat from the ambient environment supplies the energy neces- sary to vaporize the liquid, and the vapor then diffuses from the droplet surface into the ambient gas. The mass loss causes the droplet radius to shrink with time until the droplet is completely evaporated (r, = 0). The problem that we ‘wish to solve is the determination of the mass flowrate of the vapor from the surface at any instant in time. Knowledge of this will then enable us to calcu- late the droplet radius as a function of time and the droplet lifetime,Some Applications of Mass Transfer Evapoatng droplet Yee @ Figure 3.6 Evaporation of o liquid droplet in @ quiescent environment To mathematically describe this process completely, the following conser- vation laws are required: Droplet: mass conservation, energy conservation. Droplet vapor|ambient gas mixture (r,

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