Combustion Science and Engineering Series
Series Editor Forman A. Williams Princeton University
Advising Editors Ronald Hanson, Stanford University David T. Pratt, University of Washington Daniel J. Seery, United Technologies
To Th. von Karman, the founder of aerothermochemistry
Combustion Theory
The Fundamental Theory of Chemically Reacting Flow Systems Second Edition
Forman A Williams
Princeton University
The Benjamin/Cummings Publishing Company, Inc. Menlo Park, California Reading, Massachusetts Don Mills, Ontario Wokingham, U.K. Amsterdam Sydney Singapore Tokyo Mexico City Bogota Santiago San Juan
Sponsoring Editor: Richard W. Mixter Production Coordinator : Kristina Montague Copyeditor : Linda Thompson Cover Design : Leigh McLellan
Copyright @ 1985 by The Benjamin/Cummings Publishing Company, Inc. All rights reserved. N o part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior written permission of the publisher. Printed in the United States of America. Published simultaneously in Canada.
Library of Congress Cataloging in Publication Data
Williams, F. A. (Forman Arthur), 1934Combustion theory. (Combustion, science, and engineering series) Bibliography: p. Includes index. 1. Combustion. I . Title. 11. Series. QD516.W5 1985 541.3’61 853902 ISBN 0805398015 ABCDEFGHIJMA8 98765 The Benjamin/Cummings Publishing Company, Inc 2727 Sand Hill Road Menlo Park, California 94025
Preface to the Second Edition
Truly remarkable progress has been achieved in combustion theory during the 20 years since the completion of the first edition of this book. Because of this progress, when the first edition went out of print about 5 years ago, it was clear that a reprinting could no longer serve to bring readers to the frontiers of the subject. Revision of the entire text was needed, and I undertook the revision without realizing that it would require as much time as writing the first edition. Although it is regrettable that the book has been unavailable during the preparation of the second edition, it seemed best to try to complete as good a revision as possible instead of rushing into print. Thus consideration has been given to changes throughout ; none of the chapters survived without modification, and outdated chapters have disappeared entirely and have been replaced by chapters devoted to new material of importance in the subject. Nevertheless, the general format of the book and the philosophy of the presentation remain the same. The necessary background material still appears in the same five appendixes. These appendixes needed less revision than the rest of the volume; a few of the sections survived intact. Among the specific changes in the appendixes are updating of the discussion of thermochemical equilibrium calculations to take account of the revolutionary advances in computational power of electronic computers, presentation of clarifications that have been achieved in the concepts of steadystate and partialequilibrium approximations in chemical kinetics, amplification of the discussions of branchedchain and thermal explosions on the basis of insights developed from ideas of asymptotic methods, presentation of newly available information on the chemical kinetics of hydrocarbon oxidation and of the production of oxides of nitrogen in flames, and augmentation of the treatment of transport processes to include additional aspects of radiant energy transfer. The first chapter, in which the basic mathematical formulations are presented, remains just as formidable to the fainthearted as it was in the first edition. There are still 12 chapters, but the later ones, especially, exhibit modifications in coverage as a consequence of the progress made in the field. The titles of the first six chapters remain essentially the same as in the first edition. Chapter 7 of the first edition, which was devoted mainly to a discussion of experiments on turbulent flames, has been deleted and replaced by a considerably more extensive chapter (Chapter 10) that develops turbulentflame theory from first principles; noteworthy advances in the theory during the past 20 years have made this possible. Presentation of material on turbulent combustion, formerly in Chapter 7, is postponed until Chapter 10 because the new knowledge relies in part on various results that have been obtained in studies of laminarflame instabilities (now
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covered in Chapter 9j and in investigations of ignition and extinction (included in Chapter 8j. Monopropellant droplet burning, which comprised the subject of Chapter 10 of the first edition, has assumed a somewhat less prominent role in combustion in the intervening years and therefore is covered only briefly now, specifically at the end of Chapter 3, the chapter that includes detailed discussions of the burning of fuel droplets. Chapter 9 of the first edition addressed both the theory of solidpropellant deflagration and theories of combustion instability; such substantial advances have been made in these subjects that two chapters are now needed to approach the material properly, Chapter 7 on combustion of solid propellants and Chapter 9 on combustion instabilities. The general topic of Chapter 8, ignition, extinction, and flammability limits, is the same as in the first edition, as is the subject of Chapter 11, spray combustion. Also, the general thrust of Chapter 12 remains approximately the same, notwithstanding the title change, from “Chemical Reactions in Boundary Layers” to “Flame Attachment and Flame Spread,” introduced to place emphasis on specific areas of application. To delineate more thoroughly the modifications that have been introduced, it seems desirable to discuss briefly the content chapter by chapter. The basic formulations in Chapter 1 and the derivation in Chapter 2 of jump conditions across combustion waves are largely unchanged from the first edition. Therefore, the following discussion focuses on the remaining chapters. Chapter 3, on diffusion flames and droplet burning, has been expanded considerably to include, for example, greater consideration of influences of buoyancy and turbulence on jet flames, discussion of kinetics of surface oxidation of carbon, consideration of combustion mechanisms of metal particles, and reference to treatment of a number of realities of droplet burning that were not addressed in the first edition, such as influences of radiant energy transfer, the occurrence of unsteady conditions in the gaseous and condensed phases, the role of momentum conservation, influences of variable properties and of Lewis numbers differing from unity, the selection of suitable reference states for the evaluation of effects of forced and natural convection, and identification of conditions for the occurrence of disruptive burning of droplets. In addition, sections on diffusionflame structure and on the burning of monopropellant droplets have been added to Chapter 3 , since these subjects, in which significant new progress in understanding has been made, fall within the realm of the title of the chapter; this more advanced material, which introduces the mixture fraction as an important variable and which makes use of asymptotic analysis for describing aspects such as flamesheet broadening, ignition, and extinction, pedagogically should be covered only after study of Chapter 5 , where the necessary background ideas are presented.
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The material in Chapter 4, on finiterate chemistry in flows with negligible molecular transport, has been amplified to a lesser extent beyond the presentation in the first edition. The discussions of ignition delay and of the wellstirred reactor have been expanded somewhat, and a treatment of twophase nozzle flow has been added, while elsewhere in the chapter modifications in the writing have been restricted to updating of ideas. The chapter on laminarflame theory, where molecular transport and finiterate chemistry first enter simultaneously, has been revised substantially in the light of advances in our conceptual foundations of the subject. Asymptotic methods in mathematical analysis, notably the socalled activationenergy asymptotics, have provided us with a greatly improved understanding of the elements of laminarflame propagation. Most of the ad hoc approaches that were detailed in the first edition are deleted and replaced by a systematic development of activationenergy asymptotics. The results obtained thereby are employed to explain many previously perplexing properties of laminarflame structure and fame speeds. In addition, new consideration is given to flames with multiplestep chemistry and to distributions of radicals in flames, on the basis of both asymptotic concepts and advances in computational abilities of electronic computers. Because of rapid progress in detonation theory in the 1960s, Chapter 6 of the first edition on detonations was obsolete in certain respects even before it appeared in print. In contrast, many of the revolutionary advances in this subject seem now to have been brought to fruition and appraised in reviews. Therefore, the extensive revision of this chapter needed for preparation of the second edition, appears likely to remain adequate for a longer period of time. The major changes and additions begin with the discussion of effects of threedimensional structures in detonation propagation. Consideration is given to the relevance of spin, to the mechanism of instability, to tripleshock interactions and to transverse spacings. In addition, new analyses of detonability limits and of failure of detonations are included, and criteria for direct initiation of detonations are presented along with a discussion of processes of transition from deflagration to detonation. Chapter 7, on solidpropellant combustion, focuses mostly on the deflagration of homogeneous solids. Consideration is given to deflagrations controlled by interface, condensedphase, gasphase, and dispersedphase reactions, now with utilization of concepts from asymptotics. Specific examples mentioned include the combustion of nitrocellulose and of ammonium perchlorate; attention is paid to both pressure and temperature sensitivities of burning rates of propellants. Appraisals are made of the current status of theories of combustion of heterogeneous propellants, and the combustion of black powder is addressed as an especially challenging theoretical problem involving the oldest propellant known to mankind. In
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addition, a discussion of erosive burning is given, including the equations for steady, frictionless, adiabatic flow in a constantarea channel with mass addition. The presentation in Chapter 8 of the subject of ignition, extinction and flammability limits is a revision in nearly all respects. The new approach to this subject relies strongly on activationenergy asymptotics and thereby, I believe, achieves both enhanced understanding and improved accuracy in the results. Topics that were not present in the first edition include a discussion of physical aspects of spark ignition and an introduction to the use of activationenergy asymptotics in more complicated ignition problems, through the vehicle of the problem of ignition of a semiinfinite reactive solid by a constant energy flux applied to its surface. Chapter 9 represents an effort to provide a unified and tutorial presentation of the broad field of the theory of combustion instabilities. The length of the chapter attests to the vastness of the field and to the progress that has been made therein in recent years. The final section of this chapter, on the theory of instabilities of premixed flames, is basic to analyses of premixed turbulent flame propagation and also has a bearing on aspects of flammability limits. Chapter 10 on turbulentflame theory also is long, as it must be because so many different viewpoints and approaches to the subject now are available. Included in this chapter are discussions of analyses of effects of strain on laminar flame sheets, topics of interest in themselves as well as in connection with turbulent combustion. Evolution equations for laminar flames in nonuniform flows also are given. The results outlined for turbulent burning velocities emphasize those aspects that have the strongest basic theoretical justifications. Since turbulentflame theory is a subject of continuing development, improvements of results presented herein might be anticipated to be available in the nottoodistant future. The presentation of the subject of spray combustion in Chapter 11 is not greatly different from that in the first edition. An updated outlook on the subject has been provided, and the formulation has been generalized to admit time dependences in the conservation equations. The analysis of spray deflagration has been abbreviated, and qualitative aspects of the results therefrom have been anticipated on the basis of simplified physical reasoning. In addition, brief discussions of the topics of spray penetration and of cloud combustion have been added. The final chapter again is devoted largely to the theory of chemical reactions in boundarylayer flows. A general formulation of timedependent, axisymmetric, boundarylayer equations has been added to provide the reader with a convenient point of departure for analyzing a variety of reacting boundarylayer flows. The problem of combustion of a fuel plate in an oxidizing stream then provides an illustration of the use of the general formulation, instead of standing independently. The analysis of the problem
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of premixed flame development in a mixing layer now is abbreviated and approached as part of the broader subject of mechanisms of flame stabilization by solid bodies and by fluid streams. The final section, addressing problems of flame spread through solid and liquid fuels from a simplified viewpoint, is new. The present volume inevitably is appreciably longer than the first edition. The increase in length is due mainly to the increase in the breadth of the coverage. Details of the mathematical development have not been amplified; on the contrary, in a number of respects fewer intermediate steps have been included, so that on the average the reader will have to invest more time per page to extract the same depth of understanding. I think that this is an unavoidable consequence of the growth of combustion theory. Even the first edition contained too much material to be covered properly in a single course. At Princeton University portions of the contents have been used in a number of graduate courses. By the time students reach the last of these, combustion theory, they have been exposed to the subjects of the appendices, of Chapters 1,2, and 4, and of most of Chapter 12, and they have studied the more qualitative aspects of Chapters 3 and 5; the students are then able to assimilate most of the rest of the book in one semester. Alternative orders of coverage would fit into differently designed curricula. It seems fair to say that at most universities courses do not cover all of the material in the text; in this respect, the presentation may serve as a reference for researchers specializing in the field. In the period since the appearance of the first edition, a number of related books on combustion have been published. Many of these are referenced throughout the new text. They are quite helpful in providing alternative viewpoints toward much of the material. The progress in the field has resulted in significantly more extensive citations to references in the second edition, even though the bibliographical information certainly is not complete. Where I have forgotten to cite an important reference, I hope that the author will recognize the magnitude of my task and accordingly will forgive my oversight. In an effort to achieve some economy in printing, three oftcited sources are abbreviated as follows: C & F for Combustion and Flame, C S T for Combustion Science and Technology, and n’th Symp. for the currently biennial international symposia on combustion, the full citations of which are:
Proceedings o f the First Symposium on Combustion and the Second Symposium on Combustion. The Combustion Institute, Pittsburg (19653, reprinted from Industrial and Engineering Chemistry (19283 and from Chemical Reviews (19373, Third Symposium on Combustion and Flame and Explosion Phenomena, Williams and Wilkins Co., Baltimore (1949),
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Fourth Symposium (International) on Combustion, Williams and Wilkins Co., Baltimore (1953), Fifth Symposium (International) on Combustion, Rienhold Publishing Corp., New York (1955), Sixth . . . , Reinhold Publishing Corp., New York (1957), Seventh.. . , Butterworths Scientific Publications, London (1959), Eighth . . . , Williams and Wilkins Co., Baltimore (1962), Ninth . . . , Academic Press, New York (1963), T e n t h . . . , The Combustion Institute, Pittsburgh (1965), Eleoenth . . . (1967), Twelfth . . . (1969), Thirteenth . . . (1971), Fourteenth . . . (1973), Fijteenth . . . (1975), Sixteenth . . . (1977), Seventeenth . . . (1979), Eighteenth . . . (1981), Nineteenth . . . (1982).
I am indebted to many people for aid in preparation of the second edition. The colleagues and scientists who contributed significant discussions of technical material are too numerous to name, for if I were to attempt to acknowledge them all, I would surely slight someone by inadvertently omitting his or her name from the list. Nevertheless, I cannot refrain from stating here that Amable Liiian has done more than any other individual in improving my understanding of combustion theory. Even with respect to specific helpful recommendations for changes in the text, I do not dare to try to acknowledge individuals, although I would like to say that observations made by the team of Japanese combustion scientists, who translated the book from the typewritten manuscript as I completed the writing, proved to be notably useful in prompting clarifications in the Englishlanguage presentation. Nearly all of the original manuscript was typed by Peggy Berger, for whose patient help over a 5year period I am greatly indebted. Finally, I wish to express my gratitude for the presence of mind encouraged by Elizabeth. Forman A. Williams Princeton, New Jersey June 1984
Preface to the First Edition
This book contains a systematic development of the theory of chemical reactions in fluid flow. It is intended to serve either as an advanced graduate text or as a reference for workers in the field of combustion. An attempt has been made to cover the entire field, not just those parts of the field in which the author has done research. However, the book does emphasize the theoretical aspects of the subject and discusses experiments only where absolutely necessary. This type of approach appears to be justified in view of the existence of a number of excellent treatises on the experimental aspects of combustion, such as B. Lewis and G. von Elbe’s classical work Combustion, Flames and Explosions of Gases (Academic Press, New York, 1st ed., 1951,2nd ed. 1961), the book by A. G. Gaydon and H. G. Wolfhard on Flames, Their Structure, Radiation and Temperature, (Chapman and Hall, Ltd., London, 1960), and W. Jost, Explosion and Combustion Processes in Gases (McGrawHill, New York, 1946). A familiarity with the material in these books will provide the reader with a proper perspective for beginning a study of combustion theory. Relevant experimental work may also be found in the mammoth biennial volumes containing the proceedings of the International Symposia on Combustion, sponsored by the Combustion Institute, and in the journal Combustion and Flame. The arrangement and the method of attack of the book require some explanation. In order to proceed with the development of the principal subject material as directly as possible, from the outset I assume that the reader has the scientific background necessary for understanding combustion theory. Thus, a knowledge of mathematics (principally, a thorough understanding of ordinary and partial differential equations), thermodynamics, statistical mechanics, chemical kinetics, and molecular transport theory is presupposed. To aid the reader who does not have a complete command of all of these subjects, and also as convenient places from which to draw specific background items used in the text, extended appendices are provided containing reviews on thermodynamics and statistical mechanics, on chemical kinetics, on the fundamental equations of fluid dynamics, and on transport properties. For courses in which students lack specific background topics, the appropriate appendices would be the best place to begin studying the book. However, some knowledge of elementary gas dynamics and thermodynamics and a thorough knowledge of applied mathematics are needed in any case, because no mathematical appendices are given, and topics such as heat engine cycle analysis, the meaning of Reynolds and Mach numbers, and the concept of turbulence are omitted. Although pedagogical considerations did go into the arrangement of the material, the subject matter itself dictates more of a whathasbeendone book than a howtodo book. I hope that by solving some problems and by pointing out related problems that have and have not been solved, 1
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will be able to indicate fruitful lines of research and to suggest useful methods of solution to the reader. Although no homework problems are provided explicitly, statements such as “it can be shown” and “the reader may prove” appear often in the text and can be treated as problems for the student. My style of presentation is generally concisely deductive rather than discursively inductive. Perhaps, by stripping the presentation to the barest essentials and by removing adornments commonly incorporated for pedagogical reasons, I may clarify some possible points of confusion for a few readers. The writing of this treatise was undertaken through the encouragement of Dr. S. S. Penner. Practically all of the book was completed while I was an Assistant Professor at Harvard University holding a National Science Foundation Grant for Fundamental Studies of Sprays. During this time I spent six months at Imperial College, University of London, on a National Science Foundation Postdoctoral Fellowship and devoted most of my time there to the writing. Thanks are due to many of my colleagues with whom I have talked about the book. Deserving of special mention are Dr. William Nachbar and Professor Howard W. Emmons for informative conversations. Professor D. B. Spalding contributed many helpful suggestions and kindly read the first draft of the manuscript, recommending many important changes. But, most of all, I wish to thank my teacher, Dr. S. S . Penner, who wrote the original drafts of a few of the chapters and provided constant encouragement and help thereafter. My family also deserves thanks for their patience. F. A . Williams La Jolla, California June 1964
Contents
Preface to the Second Edition Preface to the First Edition
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xi
1
1 SUMMARY OF RELEVANT ASPECTS OF FLUID DYNAMICS AND CHEMICAL KINETICS
1.I . The conservation equations for multicomponent, reacting, idealgas mixtures 1.2. Onedimensional flow 1.2.1. Unsteady flow 1.2.2. Steady flow 1.3. Coupling functions 1.4. Conservation conditions at an interface 1.5. Discussion of the approach adopted in the following development of combustion theory References
2 4 4 7
9
13 17 18 19 20 20 22 23 24 24 26 26 28 30 30 33 33 33 34 35 37
XI11
2 RANKINEHUGONIOT RELATIONS
2.1. General RankineHugoniot equations 2.1.1. Derivation of the equations 2.1.2. The coldboundary difficulty 2.1.3. Use of the RankineHugoniot equations 2.2. Analysis of a simplified system 2.2. I . Simplification of the RankineHugoniot equations 2.2.2. Dimensionless form 2.2.3. Properties of the Hugoniot curve 2.2.4. Analysis of the detonation branch 2.2.5. Analysis of the deflagration branch 2.2.6. Properties of ChapmanJouguet waves 2.3. Extension of the results to arbitrary systems 2.3.1. Range of validity of the results of Section 2.2 2.3.2. Frozen versus equilibrium sound speeds 2.3.3. Proof that u, = u,,, co at the ChapmanJouguet points 2.3.4. Summary of the properties of Hugoniot curves References
...
1.6. Structure of the flame sheet 3.5.2.2.6. Background and definition of the problem 3. Assumptions 3.2.2.1.1.1. Comments on the formulation and the analysis 3. The flame at the mouth of a tube in a duct 3. Discussion of the burningrate formula 3. Application to the reaction A P B with species A and B present in only trace amounts 4.1.2. Reactions in steady.2.6.3. Steadystate.2. The validity of the other approximations 3.4. Definition of the problem 3. The mixturefraction variable 3. Further realities of droplet burning 3.1.1.3.2.4.4. Assumptions 3.4. quasionedimensional conservation equations 4.4. quasionedimensional flow 4.2. Twophase nozzle flow .3.1. Activationenergy asymptotics 3. The flame shape and the flame height 3. The flame sheet approximation 3. Ignition and extinction 3.2.3.3. Specific impulse of rockets 4.4.4.3.2.1. Monopropellant droplet burning References 4 REACTIONS IN FLOWS WITH NEGLIGIBLE MOLECULAR TRANSPORT 38 39 39 40 41 42 44 45 46 48 48 48 50 52 52 54 56 59 61 62 69 69 73 76 80 84 86 92 92 96 96 99 100 103 105 106 4. Analysis predicting the burning rate 3.3.1.2.4. Analysis 3.1. Freezing of reactions 4.3.7. The nature of carbon combustion 3. Definition of the problem 3.5.2.3. Solution of the species conservation equation for the coupling function p 3.3.xiv Contents 3 DIFFUSION FLAMES AND DROPLET BURNING 3.1.3.1.4.2. The burning of a fuel particle in an oxidizing atmosphere 3.1.5. Predictions of other characteristics of burning droplets 3.3. Nearequilibrium and nearfrozen flows 4.5.2.2. Ignition delay and the wellstirred reactor 4. The oxidation of carbon at the walls of a duct 3. Approach to structure questions 3.
3.4.2. characteristic surfaces 4. reacting idealgas mixture for the reaction A P B 4. Description of laminar flames 5.3.4.4.3. Reduction to a single partial diferential equation 4.2.Contents xv 4. The approximations of Zel’dovich.2.3.4. Asymptotic analysis for strongly temperaturedependent rates 5.4.3.1.5.4.3. FrankKamenetskii. Preliminary assumptions and equations 5.7.1.2.6. Solution of the diffusion equation when Le = 1 5.4.3. Iterative procedures and variational methods 5. Governing equations 5.2.1.1.7. Bounds on the burningrate eigenvalue 5. An initialvalue problem 4.3. Introductory remarks 5. Generalizations to other flames .4.5. unsteady sound propagation in a binary.1. Preliminary relationships 4. The coldboundary difficulty 5.6.3. threedimensional flow 4.2.3. Experiments 5.2. and von Karman 5.5. Summary of the simplified mathematical problem 5.3.3.3.2.6. The unimolecular decomposition flame with Lewis number of unity 5.3. Reactions in unsteady. Mathematical formulation 5.2.3. Dispersion relations 4. The method of characteristics for steady.1. Linearization 4. unsteady flows 4.3. Onedimensional.2.3.3.3. Simplifications in the energy and diffusion equations for unimolecular reactions in binary mixtures 5.1.3.1. Phenomenological analysis of a deflagration wave 5.3. twodimensional (axially symmetrical and plane) flows 4.3. Dimensionless forms for the momentum equation and the species conservation equation 5. Approximations that further simplify the energy equation 5.4.2.2. The method of characteristics for onedimensional.3.4. Conservation equations .2. Related problems References 5 THEORY OF LAMINAR FLAMES 108 108 113 118 119 119 120 120 123 124 126 127 130 131 131 135 136 136 137 138 139 141 141 142 143 143 145 149 151 153 154 160 5.
6.1.4.1.4.1.4.2. Conservation equations for reaction intermediaries 5. Solutions in the neighborhoods of’ singular points 6.5.2.1. Propagation velocities for detonations traveling in tubes 6.2.6.1.4.2. Burningvelocity calculations 5.1.1.4.1. Location o f singularities 6.2.2. Flames with multiplestep chemistry 5. Chemical reactions behind a shock wave produced in a shock tube 182 183 183 183 184 187 188 190 191 192 194 197 197 199 199 20 1 203 204 . Planar detonation structure 6. A criterion for the applicability of the extended steadystate approximation 5. Discussion of detonation structure 6. The structure of ZND detonations 6.3. General properties of the integral curves 6.1. Observations on theories of flame structure References 165 165 165 167 167 170 172 173 174 175 177 179 6 DETONATION PHENOMENA 6.4. Remarks on deflagrations 6.4.4. Discussion of the background and the nature of the problem 5. Approximate solution for the structure of a detonation 6.xvi Contents 5. Effects of tube walls 6.5.2.1. Further comments on weak detonations 6.4.3.3. Basic considerations for planar waves 6.1. Literature 5.1.1.2.4.5. I .2. Objectives of’ analyses 5. Ambiguities associated with frozen and equilibrium sound speeds 6.1.3. Effects of threedimensional structures 6.4.4.2.2.2.1 . Properties of the governing equations 6.4. Governing equations 6.6. The extended steadystate approximation 5.2. Methods of analysis for testing steadystate approximations 5.2.1.3.4.1.1.2.4. Formulation 5.
Premixed flames with heat losses 8.2.1.3.3.3.4.2.2.3. Transverse structures for detonations 6. Methods of analysis 8.5. Minimum ignition energies and quenching distances 8. Conservation of acoustic energy . Spinning detonations and stability considerations 6.3. liquids.7. The existence of two flame speeds 8. Deflagration controlled by gasphase reaction rates 7.1. Pressure limits of flammability 8.2.1. Activationenergy asymptotics in ignition theory References 9 COMBUSTION INSTABILITIES 9.1.8.5.5. Deflagration controlled by condensedphase reaction rates 7. Estimates of heat loss 8. Dispersion phenomena and other influences 7.4. Erosive burning References 8 IGNITION.Contents xvii 6. Combustion of heterogeneous propellants 7. Theories of transverse structures 6. Detonations in solids.1.3.2.2. AND FLAMMABILITY LIMITS 8. The transition from deflagration to detonation 6. Detonability limits and quenching thickness 6.2.2.6.1.4. Standing detonations 6. and sprays References 204 204 208 212 212 217 219 22 1 229 230 232 235 238 243 249 25 1 258 26 1 265 268 27 1 27 1 277 277 279 279 284 29 1 294 295 295 298 7 COMBUSTION OF SOLID PROPELLANTS 7. Description of steady deflagration of a homogeneous solid 7. Concentration limits of flammability 8. Acoustic instabilities in solidpropellant rocket motors 9.1. Applications of transitionstate theory 7.2.1. Oscillation modes 9.4.3.3. Approach to interfacial equilibrium 7.3. EXTINCTION.3.2.
4.1.1. Par tide damping 9. Heterogeneity efects 9. DifSusivethermal instabilities References 10 THEORY OF TURBULENT FLAMES 10.4. Hydrodynamic instabilities 9. Damping mechanisms 9.5.2.2.5. The acoustic admittance 9.3.1. Probabilitydensity functionals 10. 2 .3.1.4.1. Probabilistic descriptions 10.1.1.1.5.5. AmpliJication criteria 9.1.5. Scales of turbulence 10.1. Wall damping 9. Homogeneous damping 9. Relative importance 9.5.1.2. Relaxation damping 9. Formulation through asymptotic methods 9.1.1.1. Properties of probabilitydensity functions 10. Turbulent diffusion flames 10. Combustion response 9.4.5.5.1.5.1. Averages 10. Nozzle damping 9.5.2.1 3 .2.6.2.2.4.2. Inherent oscillations of burning solids 9.3.4. Bodyforce instabilities 9. Relative importance 9.1.1.6.5.1. Cellular flames 9.1.1.1. Objectives of analyses 10.3. Effects of strain on flame sheets 30 1 304 304 305 308 309 309 311 312 315 315 315 318 319 323 324 328 336 339 341 34 1 349 350 352 357 365 373 375 375 377 38 1 385 388 392 392 394 402 405 408 .4.xviii Contents 9.5. Nonlinear effects 9. Oscillatory burning in liquidpropellant rocket motors 9. Average rates of heat release 10. Hydrodynamic and diffusive instabilities in premixed flames 9.2.1.2.4.4.2.1.4.4. System instabilities in combustion equipment 9. Use of coupling functions 10.1.2.2.5. Production of trace species 10. Solid vibrations 9.1. Fourier decompositions 10.1. Amplification mechanisms 9.5.3.5.2.7.3.4. Timelag theories 9.4.3.2.
3.3.4.3. The spray equation 11. Assumptions 11.1.4.Energy conservation 11.3. Comments on formulations 11.3.3.2.1.5.2. Species conservation 11.3. Overall continuity 11. Objectives of analysis 10.3. Momentum conservation 1.1.5. Particle size and shape 11.3. Momentum Conservation 11. The model 1 1. Solution of the spray equation 11.Contents XIX 10. The combustion efficiency and other spray properties 11.4.5.4.1.3.2. Effects of strain on laminar flames 10. Droplet vaporization rate 11.1.4.5. Droplet drag .4.2.3. Simplified conservation equations 11. Motivation 11. Simplified model of combustion in a liquidpropellant rocket motor 11.3.4.1. The conservation equations for dilute sprays 11.5.4.2. Extended model of combustion in a liquidpropellant rocket motor 11. Flames in turbulence of high intensity or small scale References 41 1 41 1 415 423 429 437 440 446 448 448 449 449 450 450 45 1 452 453 455 458 458 459 460 460 462 462 463 463 463 464 464 465 466 466 467 468 468 11 SPRAY COMBUSTION 11.2.5.3.3.2.3. Species conservation 11.3.3. Theory of wrinkled laminar flames 10.2. Simplified spray equation 11. Turbulent flame speeds 10.1.1.5. The distribution function 11. Energy conservation 11.4. The spray equation 11. The model 11.2.3. Droplet size distributions 11.1. Turbulent premixed flames 10.2.3.1.1.5.6.5. Spray statistics 1 1.4. Overall continuity 11.2.2.4.
3.5. Solution to the problem 11.2.2.1.3.1. Deflagrations in sprays 11.2.6.5.1.2.2.2. The laws of thermodynamics A. Processes of flame spread References 503 509 516 Appendix A SUMMARY OF APPLICABLE RESULTS OF THERMODYNAMICS AND STATISTICAL MECHANICS A. Momentum and energy conservation 1I . Mechanisms of flame stabilization 12.7.6. Combustion of a fuel plate in an oxidizing stream 12.5. Definition of the problem 12.2.6.2. Overall continuity and the spray equation 11. Spray penetration and cloud combustion References 12 FLAME ATTACHMENT AND FLAME SPREAD 12.1. General thermodynamical results A.xx Contents 11.3. The force on the plate 12.2. 1.1.6.5.2.1. Background A.6. Continuity 11. Relevance to other problems 12.7. Derivation of simplified governing equations 12. Description 11. Thermodynamic functions A.2.2. Summary of results A.3.2.4. 1.6.5.5.6. Pertinent results of statistical mechanics A. Evaluation of partition functions 52 1 522 522 523 524 524 526 527 . Generalizations 12.1.2.4. The chamber length for complete combustion 1 1. 1. The mathematical problem and boundary conditions 11. Species conservation 11.6.6. Solution 12.2. The burning rate 12. The boundarylayer approximation for laminar flows with chemical reactions 12.4.6. Solution to the problem 469 469 47 1 472 472 474 475 476 478 479 480 48 1 485 486 486 489 49 5 495 496 498 500 501 502 11. Boundary conditions 12.2.1.
Colligative properties of solutions References Appendix B REVIEW OF CHEMICAL KINETICS B.3. Higherorder reactions B. l . Condensed phases A.5.2.3.5. l .6.5. Catalysis 529 529 53 1 532 533 533 535 535 538 538 539 540 54 1 543 544 544 545 547 548 550 552 554 554 554 555 557 558 558 559 56 1 56 1 563 563 565 570 576 58 1 584 . Heterogeneous reactions A.2. Reactions in condensed phases A.2.2.5.3. 1. Opposing reactions B.1.3.3. Chain reactions and related processes B. Definition of heat of reaction A. General methods B.4.3.5.2.4.7. Calculation of equilibrium compositions A.2.5.1. Branchedchain explosions B.4. Firstorder reactions and unimolecular reactions B.2.2.2.5.3. The steadystate and partialequilibrium upproximat ions B. The law of mass action B .4.4. Differential heat of reaction A.5. propagation.4.1. Reaction order and molecularity B.2.3. Thermal explosions B. The equations of Kirchhoff and van’t Hoff A. Temperature dependence of vapor pressures of binary mixtures A. Boiling points of binary mixtures A.2.5. Initiution.2.2.2.4.5. The adiabatic flame temperature A.5.3. and termination steps B. Idealgas reactions A. Multiple reactions.6.2.4.1.4. 1. Vapor pressures of binary mixtures A.3. Nonidealgas reactions A.2. Heats of reaction A.5.5.3.2. General equilibrium condition A. Phase equilibria A.3.4.5. Kinetics o f hydrocarbon combustion B. Chemical equilibrium A.3.l. The phase rule A.1.4.3. equilibrium constant B. Heat of formation and other properties A.2. Reaction mechanisms B. Statement of the law B.Contents xxi A.5.5.
5. Surface reaction ratecontrolling References 585 585 585 587 589 59 1 593 593 595 595 595 595 598 60 1 Appendix C CONTINUUM DERIVATION OF THE CONSERVATION EQUATIONS C. Other applications of transitionstate theory B.3. Comparison between transitionstate theory and collisional theory B.5.3.4. Comparison between the conservation laws derived for independent coexistent continua and the kinetic theory results for multicomponent gas mixtures (2. Adsorption or desorption ratecontrolling B.3.4.3. Collision reactionrate theory B.1. Comparison of conservation equations (2. Gas transport ratecontrolling B. Transitionstate theory B.3.4.2. 1. The Arrhenius law B. Definitions of kinetic theory C. Description of the heterogeneous processes to be discussed B. The velocity distribution function and the Boltzmann equation 618 618 620 624 D.xxii Contents B.5.4. The activation energy B. The rates of heterogeneous processes B.5. The equation of change . Definitions of fluid dynamical variables D.4.4. Determination of the specific reactionrate constant B.4.6. Continuity equations C.2.3. 1.7. Definitions and basic mathematical relations C.3. Proof of equation (6) References 604 605 607 608 610 612 613 614 615 617 Appendix D MOLECULAR DERIVATION OF THE CONSERVATION EQUATIONS D.4. Modern developments in reactionrate theory B.2.3.1. Energy equation C. Momentum equation C.3.3.3.6.3.2.2.1.
5.2. Thermal diffusion coefficients E.2. Multicomponent diffusion coefficients E. Viscosity E.4. Simplified diffusion equations E.Contents xxiii D.2.5.1.5.4.3. 5. Summary References Appendix E TRANSPORT PROPERTIES 624 625 625 625 626 626 627 627 628 629 63 1 63 1 634 635 636 637 638 640 640 64 1 642 642 643 646 647 651 667 E. Summational invariants D.5.2.5. Unified elementary treatment of transport processes E.2.5.3.4. Heat flux E.1.1. Momentum conservation D.5.1.5. 1. Dimensionless ratios of transport coefficients References Subject Index Author Index .4. The pressure tensor E.3.5. Energy conservation D.2. Overall continuity D. Macroscopic conservation equations D.2.4.2.2. Diffusion E. Thermal conductivity E. Collision integrals E. Physical derivation of the multicomponent diffusion equation E.2. Coefficient of viscosity E.6. Binary diffusion coefficients E. Species conservation D. The heatflux vector E.5.4.
including transport properties and chemical kinetics. From the macroscopic viewpoint (Appendix C). the governing equations (excluding the equation of state and the caloric equation of state) are not restricted to ideal gases. Readers unfamiliar with any of the background subjects are advised to read the appropriate appendixes before beginning Chapter 1.CHAPTER 1 Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics Since combustion problems requiring theoretical analysis are primarily concerned with the flow of reacting and diffusing gases. The differential forms of the conservation equations derived in the appendixes for reacting mixtures of ideal gases are summarized in Section 1.2. Simplified forms of the conservation equations applicable to steadystate problems in three dimensions are discussed in Section 1. The specialized equations given in this chapter describe the flow for most of the combustion processes that have been analyzed satisfactorily.3. the student of combustion theory must understandin addition to chemical thermodynamics the conservation equations of fluid dynamics. 1 . curvilinear coordinate systems are derived in Section 1. Most of the topics considered in this book involve the solutions of these equations for special flows. Condensed but reasonably complete treatments of these background topics are given in the appendixes.1. where specializations accurate for a number of combustion problems are developed. The forms that the equations assume for (steadystate and unsteady) onedimensional flows in orthogonal.
equation (D37). for example.5. is p &/dt + pv. and energy balances at an interface often are of importance. i= 1 N (3) Conservation of species.1. (1) Momentum conservation.. REACTING.)(V * v)]U . is In equation (2). it is difficult to give general rules for stating them. is dp/dt +v * (pv) = 0. q . which may be written as . q is given by equation (E46). THE CONSERVATION EQUATIONS FOR MULTICOMPONENT.P : (VV) + p 1 y i f i . (D35).p[(Vv) + (VVy]. to be used repeatedly. 1. (5) In equation (3).Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics Boundary and interface conditions must be known if solutions to the conservation equations are to be obtained. vi. N i= 1 (2) Energy conservation. which may be combined to give P = [p + ($A . IDEALGAS MIXTURES The conservation equations. v u = . However. interface conditions are derived through introduction of integral forms of the conservation equations in Section 1. is svpt + v * vv = (V . are derived in Appendixes C and D and may be summarized as follows. The organization of the remaining chapters of the book is discussed in Section 1. For this reason. equation (D40). Overall continuity. they may require consideration of surface equilibria (discussed in Appendix A) or of surface rate processes (discussed in Appendix B).4. p is obtained from equations (E38)(E40). momentum.v . equation (D33). Since these conditions depend strongly on the model of the particular system under study. simple mass.p)/p + c Xfi.
U is the unit tensor. The external forces fi are specified (not derived). .. V is the gradient operator. is also viewed here as specified. The radiant flux.~T ) Be ~(&/ROT) j=l fi () X. T.3k . and the identity In equations (1)(7). .1. . . qR. . and (B59). The reaction rates wi in equation (4) are determined by the phenomonological expressions of chemical kinetics. Reacting. i = l .. .1 The Conservation Equations for Multicomponent. the caloric equation of state. = j= 1 xixj (&Vj  Vi) + (X   Xi) + j$ = 1 [rz)r+ . N . vector notation is employed.(fi  N  fj) (7) i j = l i = 1..)?(I%  (T)  + 1I.. N the thermodynamic identity..1. (8) ROT which are combinations of equations (B6)(B8). two dots (:) imply that the tensors are to be contracted twice. The symbols appearing here are summarized in Table 1. it is found fundamentally through the integrodifferential equation of radiation transport (see Appendix E). and v. w i= k= 1 M 1 (vI:~ V. The N + 5 dependent variables in equations (1)(4) may be taken to be p. IdealGas Mixtures 3 In equations (3) and (4). (B58).p v. The transport coefficients appearing in equations (5)(7) are given in Appendix E. in which case the other variables may be related to these through the idealgas equation of state. Vi is determined by equation (E18) which is vx. x. N . and the superscript T denotes the transpose of the tensor.y.
standard reference temperature* Internal energy per unit mass for the gas mixturet Diffusion velocity of species it Massaverage velocity of the gas mixturet Molecular weight of species i* Rate of production of species i by chemical reactions (mass per unit volume per unit time)+ Mole fraction of species it Mass fraction of species it Exponent determining the temperature dependence of the frequency factor for the kth reaction* Bulk viscosity coefficient* Thermal conductivity* Coefficient of (shear) viscosity* Stoichiometric coefficient for species i appearing as a reactant in reaction k* Stoichiometric coefficient for species i appearing as a product in reaction k* Density' * Parameters that must be given in order to solve the conservation equations + Quantities determined by the equations given in this section. 1. the .1. ONEDIMENSIONAL FLOW 1.2. Since the complete form is complicated and will not be required in subsequent problems.2.4 Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics TABLE 1.1 Symbols Meaning A constant in the frequency factor for the kth reaction* Specific heat at constant pressure for species i* Binary diffusion coefficient for species i and j * Thermal diffusion coefficient for species i* Activation energy for the kth reaction* External force per unit mass on species i* Specific enthalpy of species it Standard heat of formation per unit mass for species i at temperature T o* Total number of chemical reactions occurring* Total number of chemical species present* Hydrostatic pressuret Stress tensor+ Heatflux vectort Radiant heatflux vector* Universal gas constant* Temperaturet A fixed. curvilinear coordinatesystems may easily be derived from equations (1)(4). Unsteady flow The conservation equations in orthogonal.
g 2 . N . (Note that the numbers in brackets refer to references at the end of each chapter. g3). for example. Here the subscripts 2 and 3 denote the corresponding components of the vectors. where a form valid in arbitrary (nonorthogonal) coordinate systems also is given. x2. 1 = 1. the (massaverage) velocity vector and the bodyforce vectors all are parallel to one of the three coordinates. andx. and the relation between the physical distances (sl. ds3 =93 dx3. in other words. and K2 = 0 and K3 = 0. .2. = 0. = dx and use x in place of x1 in the equations. v 3 = 0. ds2 = g2 dx2. = 0 and d/dx3 = 0 for all flow properties? and that v 2 = 0. Equation (6) then 0. g 2 and g3 may depend upon x2 and x 3 . the coordinate in the flow direction will be taken to be the actual physical distance in that direction (gl = 1). . . (13) which essentially defines (gl.) t Of course. and all properties are uniform along surfaces in the other two orthogonal directions.L2 = 0. These conditions appear to define the most general type of onedimensional flow.x3) will be taken as dsl = g1 dxl. however. yields q2 (14) = and also shows that q3 = 0.* Of special interest. are flows in which the radiant heatflux vector. The flow will be assumed to be in the x1 direction. From equation ( 5 ) it is found that the offdiagonal elements of p vanish (p12 = p Z 3 = p31 = 0) and that the diagonal elements of p are given by * See.1. Equation (7) now reduces to 1 aT j=1 . . Onedimensional flow is then defined by the hypotheses that dldx. s3) and the coordinates (xl. OneDimensional Flow 5 reader is referred to the literature for these equations. For brevity we shall assume that g1 dx. the components of the vectors in the 1 (x) direction will be identified by italic type without a subscript. [l]. . s2.
the 2 and 3 components of all vectors are zero. = 0.v 2t = ar.u.6 Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics and where use has been made of expressions for the divergence and the dyadic gradient in orthogonal. curvilinear coordinate systems. = 0. one can show that equation (2) reduces to Equation ( 3 ) becomes and equation (4) may be written as ar + .. A modified form of the energy equation may be derived from equation (21) by making the * There IS an error in equation (14) of [I].. the pressure tensor is diagonal.u. N . ax wi P I ~ 1 a P9293 ax ( ~ y i V & ~ g 3 ) . In Cartesian coordinate systems g 2 = g 3 = 1. . In combustion problems it is usually more convenient to work with the enthalpy h = u + p / p instead of the internal energy u...i = 1.) . (22) Equations (19)(22) may also be obtained by specializing the conservation equations given in [l]* to the case in which a/dx. and g1 = 1. a/ax. The simplified form of equation (1) is By utilizing the expression for the divergence of a diagonal tensor in orthogonal. curvilinear coordinate systems./h. in the present case. (pJJ/bJ) should be replaced by (p.
a relationship quite similar to equation (21a) may be derived from equations (1)(3) for general flows. in addition. yielding the simplified continuity equation (23) In many steadystate combustion problems. the additional term p/p. u 2 / ( p / p ) < 1. the leading term on the lefthand side in equations (19)(22) disappears. and d/ax . OneDimensional Flow I substitution u = h . If. may be explained as “displacement work.+ d/dx because only one independent variable remains. +q  ( p . considerable simplification in equations (19)(22) may be effected.2.” An integrated form of the momentum equation may be derived only under additional restrictive conditions. . if viscous forces are negligible. and utilizing equation (19) to eliminate a( l/p)/at. multiplying equation (20) by u. 1. the result is found to be N Actually. then Id In p/dx I < Id In u/dx I (that is. Here a/& = 0. Equation (19) may be integrated immediately. substituting the result into equation (21). Steady flow In certain steadyflow systems. When a/& = 0 and fi = 0. which appears when equation (24) is written in terms of u. body forces are negligible and a consequent simplification in the energy equation is possible. and kinetic energy.pll)u Equation (24) states that the sum* of the enthalpy flux and the ordered kineticenergy flux may change only because of heat flux (g2g3 q) or viscous dissipation [ g 2 g 3 ( p . After recombining terms in the appropriate manner. giving pug2g3 = constant.1.p/p in equation (21). Equation (24) also illustrates that the enthalpy is of more importance than the internal energy in steadyflow problems. chemical enthalpy.2. In steadystate flow with fi = 0.2. + * This sum often is called the stagnation enthalpy flux and includes thermal enthalpy.pll)v]. multiplying equation (21a) by pg2g3 and utilizing equation (23) shows that equation (21a) may be integrated once. then equation (20) reduces to pu du/dx dp/dx = 0. 1 = constant.
(30) Although ei need not lie between 0 and 1 (it may be negative or greater than ti = 1. . . Equation (26) therefore expresses a balance between dynamic (inertial) forces. onedimensional flow with no body forces. the species conservation equation is dei/dx = wi / ( pv g2g3) . Utilizing g 2 = g 3 = 1.8 Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics fractional changes in the pressure are negligibly small) and the solution of the momentum equation is p = constant. s = entropy]a measure of the ratio of the ordered kinetic energy to the random. the integral of which is pv2 p l l = constant. equation (20) reduces to pv du/dx + dpll/dx= 0. In these cases it is not necessary to use equation (20) (except to compute the actual small pressure change. ..f. and g 2 = g 3 = 1. When av/at = O. When equation (25) is an acceptable ap= 0) through (24) constitute an proximation. In steady onedimensional flows it is often useful to introduce the massflux fraction of chemical species i.($p + K ) dv/dx according to equation ( 16). (29) Equations (26)(29) are the conservation equations for steady. (26) + since equation (23) implies that (27) when g2 = g3 = 1.(. the square of the Mach number [v2/(ap/ap). onedimensional flow ( g 2 = g 3 = l). p1 = p . . thermal kinetic energy of the moleculesmust be small. N .. specifically. Multiplication of unity). In equation (26). In (steadystate) plane. . i = 1. the additional restrictions imposed in the preceding paragraph are not needed in order to integrate the momentum equation. = 0. equations (22) (with appropriate set of conservation equations. i 1. . ... and viscous forces. ei = pE. pressure forces. d / d t = 0 and the above results in equations (22) and (24). the definitions of yi and imply that equation (22) by p g 2 g 3 and utilization of equation (23) shows that when ajat = 0. after the rest of the problem has been solved with p = constant).N . (31) . we find that pv = constant pv h ( + Z) + . i = 1 ..(u + F)/pv. (25) The condition v 2 / ( p / p ) < 1 is valid for lowspeed flow.  q  p +K and  ): : = u . plane. . N .)] = wi.= constant d [pyi(v dx + V.
(32) Using these same assumptions and the (idealgas) condition h = hi one can show by substituting equation (15) into equation (24) that if radiant transfer is neglected. Body forces* (fi terms). is quite complicated. Bulk viscosity ( K ) .( p . 1. 2. and the only term from the heatflux vector that remains explicitly is that of heat conduction. the effect of diffusion on the enthalpy flux is included implicitly in the first term.. 3.Xi) V p / p ] . [ (i:l C hiti +  z)  A. is invalid. and consequently fi is not negligible. There are a number of combustion problems in which the neglect of q. + (x . Body forces disappear from equations (3) and (7) and remain only in the momentum equation. N . Although the general formof the equation of radiation transport.X i ) . Other radiative influences.. * In some lowspeed combustion problems natural convection is of importance.3. always appear to be negligible in combustion.. Pressuregradient diffusion [ ( y . f. 5.dP P dx i = 1.1.pll)v dx dT = constant. 4. then g2g3 p u x.3 Coupling Functions 9 In terms of ti. Since the acceleration due to gravity is the same for all species. radiation pressure and radiationenergy density. The fact that equations (31) and (33) appear to be less complicated than equations (22) (with = 0) and (24) often justifies this transformation. The above equations serve to eliminate completely the diffusion velocities from the governing equations. replacing them by the flux fractions. (33) In this form of equation (24). 5= dx j=1 (T)(x xixj to j).+ Reasons for neglecting these phenomena are discussed in Appendix E. These include: 1. The Soret and Dufour effects (terms involving DT. some combustion problems remain tractable when radiation is included because the effects of scattering and absorption often are negligible except at interfaces. is the same for all i in these problems. COUPLING FUNCTIONS A number of effects contained in equations (1)(7) are unimportant in a large class of combustion problems and will be neglected in nearly all of the applications to be considered subsequently and also in the equations to be derived in this section.i).1. whenh equation (14) becomes =0 and thermal diffusion is neglected (for brevity). Radiant heat flux (qR). .. from which qR is obtained.
equation (4). and the resulting formulation often is called the ShvabZel’dovich formulation. (36) When the binary diffusion coeflcients of all pairs of species are equal. approximately. N in the present approximation. the momentum equation implies that. . in this approximation. (34) For lowspeed. equation (l). may be rewritten as v . The objective of the following manipulations is to express the equations for conservation of energy and of chemical species in a common form. the resulting equations remain valid. steadyflow problems.i lV T i =1 1 = 0 (35) for the energy equation.(v + V .2. Since Y.reduces to v .h. There are many approaches to the derivation of equations for coupling functions. . viscous effects are often negligible and. The assumptions needed limit the range of applicability of the formulation to a considerably greater extent than do the approximations given in the preceding paragraph. (pv) = 0. . species conservation.. as pointed out in Section 1./X. . ) ] = w. Utilizing equations (10) and (34) in this expression. multiplying this equation by = 1. The substitution of equation (6) into equation (3) yields. i = 1. For s t e a d y j o w overall continuity. ) .[pY(v + V . and summing over i yields a relation for X j V j that may be . These linear combinations often are descriptively called coupling functions. p is a constant. .= Xi j= 1 cXjVj N  XiVi.10 Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics Introduction of additional restrictive assumptions is useful in analysis of many problems.Vi = 0. equation (7) reduces to D VX. and Y. in a reasonable approximation. X i = 1 by definition. In view of equation (34). In addition to providing significant simplifications in analysis. for many of the problems considered in later chapters.. where D = D i j . i = 1. we obtain Y. One involves equations given in early papers of Shvab [ 2 ] and Zel’dovich [ 3 ] . Nevertheless.. ) N . This enables the chemicalsource term to be removed from many equations by considering suitable linear combinations of dependent variables. the use of coupling functions often enhances understanding of the physical processes that occur.
. . Coupling Functions 11 substituted back into the equation. Equations (36) and (37) imply that V. Coupling functions may now be identified from equations (40) and (41). h.VlnXj j=1 [ N Substituting equation (12) for X i into all terms on the lefthand side of this expression. The derivation given for these equations required neither that any transport coefficient or the specific heat of the mixture is constant nor that the specific heats of all species are equal. not derived from fundamentals through explicit hypotheses..i i= 1 N (38) is the specific heat of the mixture. (37) a simple and wellknown diffusion equation that often is merely postulated.) = w i . 1 = Vi. This integral represents the thermal enthalpy. the integration is performed * Here.1..3. showing that D VlnXi. i = + If= 1. . (39) we may substitute equation (37) into the above form of the energy equation to show that since V JFoc p dT = c p VT [(Vyi) & cp. N. [ p v ( f T l c p d T ) pi:lyiVi + N N where cp = 1 yiCP.xE. that is. . 1''' Y. . Le = A/pDcp = 1. & cp. . By substituting equations (11) and (36) into equation (39.. obtained from the total enthalpy. (41) In view of equation (39). dT] according to equation (38). . precisely j& c p dT = at constant composition.hp. d T . we obtain Fick's law.and speciesconservation equations of Shvab and Zel'dovich. N. i = 1. i = 1. N . the similarity in the forms of equation (40) (for the thermal enthalpy iFo c p d T ) and equation (41) (for the mass fractions yi) is striking. Equations (40) and (41) are the energy. . .* Assuming that the Lewis number (Le) is unity. we find V . V i = DVlnyi. . by subtraction of the chemical enthalpy. ( P V ~ pDVY.
(44) (45) and *T for equation (40). E PT and P = ai .a. d(pa)/at. N ..(@]) = w (48) can be solved for a l . If the steadyflow approximation is relaxed.pD V a l . For species conservation. in the absence of the assumptions of lowspeed flow and of a Lewis with P = .. In the operator L. i= 1 N N i= 1 where mi is the symbol for chemical species i. . i = 1. (49) aT .this term represents accumulation of thermal energy or chemical species. . where the linear operator L is defined by L(a) E v * [pvGl .mi + 1v. and reactive effects. equations (48) and (49) may be derived with this generalized definition of L. . i = 1. the first term represents convection and the second diffusion. assume further that chemical changes occur by a single reaction step.v:) = o. if I.. Equation (44) therefore describes a balance of convective.a1 = ji( i # 1).12 Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics To emphasize more explicitly the similarity of equations (40) and (41).mi. Such balances are very common in combustion and often are employed as points of departure in theories that do not begin with derivations of conservation equations. (47) for equation (41). for example. . In this case. while = YI / W 1 ( V~ v:) ai. N . then an additional term. 1v.appears in L . then the other flow variables are determined by the linear equations for the coupling functions P L(P) = 0. (43) is the same for all species (see Appendixes A and B).. diffusive. The nonlinear rate term may be eliminated from all except one of the relations corresponding to equation (44) by subtraction. the quantity w i / w ( v i . and equations (40) and (41) may both be expressed as L(a) = 0.
However. The time rate of change of the integral of an arbitrary functionf(x. as well as replacement of the steadyflow approximation by an additional assumption. equation (A36). an equation of state with p = constant and in some cases an approximate form of the momentum equation] and p D may depend on pi or j T . Only the restrictions 1. Nevertheless. unless additional approximations are made. equation (39) and the approximation of lowspeed flow. n is the outwardpointing normal to this surface.4. To obtain equation (44) for energy conservation in timedependent problems necessitates. and the assumption of a onestep reaction are needed . and 3.4. momentum. For systems in which reactants initially are unmixed. It should. Although the onereaction approximation is sufficiently accurate for k? many purposes in combustion. 2. the equality of diffusion coefficients. burning rates often may be determined by solving equation (49). and the term involving d x l d t accounts for the changes associated with motion of the control volume. however.therefore. be pointed out that equation (49) is deceptively simple in appearance. 1. pv [which is determined by equation (34). coupling functions obeying equation (49) still may be derived through use of atom conservation. . the formulation is of reasonably wide applicability for species conservation. more than one rate equation of the type given in equation (48) remain to be solved. Integration of equation (1) over V and utilization of the divergence theorem and of equation (50) forf = p yields f ( J v p d V ) + Jdp(v  g) nd d = 0. and energy at an interface may be derived by writing equations (1)(4) in integral form and then passing to the limit in which the volume of integration approaches a surface. in addition. the retention of assumption 5.4.2). it is often important in detailed investigations to replace equation (42) by a kinetic scheme of greater complexity. thus the formulation is appreciably less general for energy conservation than for species conservation. a result like equation (49) often can be derived for the total enthalpy h through reasonable approximations (see Section 3. and equation (49) actually becomes nonlinear. Conservation Conditions at an Interface 13 number of unity. CONSERVATION CONDITIONS AT AN INTERFACE Relations expressing the conservation of mass.so that L depends implicitly on p [see equation (45)]. without attacking equation (48) [4]. to the effect that aplat is negligible in an expression like equation (21a). In such cases. t ) over a given volume V is where d is the surface bounding V.1.
the integral over d is composed of two parts. whichupon integration over V”reduces to (54) Equations (51)(54) are the integral forms of the conservation equations. then equation (1) may be used to obtain an equation which is essentially identical with equation (D36).14 Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics By multiplying equation (1) by v and adding the result to equation (2). We now let the control volume ^Y be a thin slab. In the limit. .1. integrals over each face of the slab. Integrating this result over Y. one obtains equation (D34). If equation (2) is dotted into v and substituted into equation (3).we find that The substitution of equation (I) into equation (4) yields equation (D39). Control volume for the derivation of interface conditions. the thickness of which is allowed to approach zero (see Figure 1. which may be integrated over Y to show that by the procedures described above. Let us arbitrarily choose one face as the “positive” side of the slab and identify quantities on this side by the subscript + and those on the other t nFIGURE 1. namely.1).
+I  PV[(V  3. and 6 is the Dirac 6function.q . y = y .4..n + I dd + q+ .dx)]n+ dt  d d = lim JYwi d V 770 ( JvpX d V ) .P .+ v + . if the interface is taken to be a solid surface at which chemical reactions are proceeding at a finite rate. It is clear that n..P. account for the possibility of surface forces. wi dd. then wi + wi 6 ( y . By substitution.. n+ at corresponding points on the two faces.v  ( + vi. The terms involving limY+oof volume integrals remaining in equations (55)(58)..1. limv+o is to be interpreted as the limit in which the thickness of the slab becomes infinitesimal (that is. n + d d 1 and [i’. which is we then find that in equation (58) limv+o Jy wi d V = SdI .v .) . . . n+] + (P+ . energy. the volume integral essentially approaches a surface integral). y is the coordinate normal to the surface.P + . surface reactions.. Conservation Conditions at an Interface 15 side by the subscript .y l ) . For example.yi. (58) from equations (51)(54). ... and in the limit the integral over the surface of V may be yielding replaced by an integral over the interface area d. or a chemical species at the interface.)I n+ d d = V lim +O [it J/  d 4 (55) Jd1{P+V+[(Y+ %). at the surface.N . In equations (55)(58). where wi is the surface reaction rate (mass of species i produced per unit area per unit time). momentum. respectively. yi+(v+ JdI + vi+  g) d  p .. JdI [p+(v+  g)  p(v. or a nonzero time rate of accumulation of mass. i = 1.
by Fick's law. which is the negative of the rate of accumulation of mass of species i on the surface. p + v+(v+ n + ) + P+ n+ (59) (60)  = P .y. the V i values are determined in terms of concentration gradients at the interface either by the form of equation (7) in which the last three terms are omitted or. for example. all terms in equations (55)(58) involving are zero.we find by passing to the limit of small d. n + . It is apparent that corresponding interpretations may also be given for equations (55)(57).. equations (59). then equations (55)(58) simplify considerably. Equation (58) therefore expresses the following physically obvious conservation condition.that the differential forms of equations (55)(58) reduce to p + v + n+ = p . The difference between the mass flux of species i leaving the surface and that entering the surface equals the mass rate of production of species i at the surface minus the mass rate of accumulation of species i on the surface.n .3 are valid.v(v.3). If pi is the mass of species i per unit surface area.16 Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics the mass rate of production of species i on the surface.) d V dt Y0 = .IdTpi d dt dd. In equations (61) and (62). In equation (61).v . In many problems. and respectively. that viscosity is negligible.yI). with additional approximations (see Section 1. (61). then p x + pf S(y . there is usually no excess mass at the surface so that limY+of p d V = 0 in equation (55). lim I V p . and that approximations 14 of Section 1. Although equation (60) will not be used explicitly in the subsequent applications. If it is also assumed that the interface is not moving (dx/dt = 0). S(y . Detailed discussions of the importance of . qR has been retained because radiative heat losses from surfaces often are substantial. and the remaining term on the righthand side of equation (58) is p yi d V =  d .n + >+ P . and (62) often will be needed as boundary conditions for equations (1)(4). . Using equations (5) and (6) and the identity h = u + ( p / p ) .
DISCUSSION OF THE APPROACH ADOPTED IN THE FOLLOWING DEVELOPMENT OF COMBUSTION THEORY In the following chapters we shall begin with problems that are. Approach Adopted in the Development of Combustion Theory 17 various terms in equations (59)(62) for particular systems may be found in the literature. onedimensional burning in liquidpropellant combustors and of deflagrations in sprays. the least complex and proceed to successively morecomplicated problems. to problems of steadystate. The study of combustion of solid propellants. where relations between the properties on the upstream and downstream sides of combustion waves are developed from overall (algebraic) conservation equations. The next three chapters address from a basic viewpoint three classes of combustion problems that are of high practical interest. fundamentally. presented in Chapter 7.3 is useful in these problems. the formulation developed in Section 1. None of the differential conservation equations discussed in this chapter are needed in Chapter 2. [6] and [7] for applications and generalizations of equations (61) and (62). The arrangement of the remaining chapters is less strongly dependent on pedagogic considerations. and [S] for an amplification relevant to equation (62). Chapter 12 concerns basic aspects * See. but the transport phenomena [the most highly differentiated terms appearing in equations (2)(4) after use is made of equations (5)(7)] all are negligible. developed therein. addresses a problem of engineering importance and also provides a vehicle for systematic amplification of basic concepts. Processes in which both transport phenomena and finite chemical reactionrates must be considered simultaneously even in the most elementary descriptions are encountered in Chapter 5 on laminar flame theory and also appear in the discussions of detonation phenomena given in Chapter 6. and spray combustion. The bases of theoretical descriptions of unsteady burniqg in a wide variety of combustion problems are given in Chapter 9. Chapter 3 is concerned with problems in which transport effects are of importance but the chemical reactionrate terms appearing in equation (4) and given by equation (8) need not be considered in obtaining first approximations for most of the information of interest.1. .5. turbulent combustion. combustion instability. namely.5. The analysis in Chapter 8 of classical aspects of flapmability emphasizes the influences of heat losses and of finiterate chemistry. [ 5 ] for an analysis of equation (61). The current status of our theoretical understanding of turbulent flames is reviewed in Chapter 10. for example.* 1. Chapter 4 deals with problems in which finite chemical reactionrates must be considered. Results of Chapter 3 are employed in Chapter 11 to apply the spraycombustion theory.
7. A. 18CL182. 1974. No. izd. MoscowLeningrad (1948). Blackshear. D. 1152 (1965).18 Summary of Relevant Aspects of Fluid Dynamics and Chemical Kinetics of problems of flame attachment in combustion devices and of flamespread processes such as those occurring in fires. Scala and G. DA04495Ord446. A . M. Spalding. Sutton. S. No. Economic Impact. Libby and F. Contract No. A. Williams. 141 (1959). ed. A. an attempt has been made to cite references that can be pursued in advancing to any frontier of the subject.. Y .. Zhur. 19. Aero. 4. A. 343 (1958). F. A. Gos. California Institute of Technology. chapter 3 of Heat Transjer in Fires: Therrnophysics. S. English translation. (1957). B. B. W. Williams. 8. Pasadena. AZAA Journal 3. Enery.. 2. Tech. Social Aspects. Fiz. 1 199 (1 949). Tekhn. 3. 1296 (1950). F. NACA Tech. J. . 5. Penner and F. A R S Journal29. S. Sci 25. 6. 847864. P. (1953). L. P. Zel’dovich. “CondensedPhase Mass and Energy Balances”. 19. Since a thorough presentation of every aspect of combustion theory cannot be included in a volume of this size. New York: Wiley. Shvab. Memo. Scripta Book Co. Williams. Williams. 4th Symp. V. REFERENCES 1. Rept.
The RankineHugoniot relations are the equations relating the properties on the upstream and downstream sides of these combustion waves. steadystate. nonreacting) fluid. In this chapter. onedimensional flows involving exothermic chemical reactions. Some other texts discussing the RankineHugoniot equations are listed in [1][5].2 and 6. The experimental conditions under which these waves appear are described in Chapters 5 and 6. Such a classification provides a framework within which plane deflagration and detonation waves may be investigated. except their speed of propagation. in many problems deflagration and detonation waves can be treated as discontinuities (at which heat addition occurs) in the flow equations for an “ideal (inviscid. In such problems. the equations derived in this chapter provide all of the information that is required concerning these waves.CHAPTER 2 RankineHugoniot Relations In this chapter we shall classify the various types of infinite. nondiffusive. then the Hugoniot curve for a simplified system is studied in detail in order to delineate explicitly the various burning regimes. plane. Since the major changes in the values of the flow variables in these systems usually take place over a very short distance (in nearly all cases less than a few centimeters.1). where detailed analyses of each type of wave are presented. general RankineHugoniot equations are derived and discussed first.1. nonheatconducting. ” 19 . see Sections 5. in which the properties become uniform as x + & co.
GENERAL RANKINEHUGONIOT EQUATIONS 2. = l .~=Oi . Upstream conditions (at x = . q . (3) where use has been made of equation (1). Since q is proportional to temperature gradients and concentration gradients.+ 0 as x . Equations (126)( 129) govern the system.20 RankineHugoniot Relations 2. The continuity equation [equation (127)] implies that + povo x = pmvm = m. Since dvldx approaches zero as + f 00.. The speciesconservation equations.1.00) will be identified by the subscript 0. provide the additional requirements W ~ .a) for which equations (1) and (2) are satisfied is often referred to as the Rayleigh line.1. reaction. N .. equation (126) reduces to Pod + Po = PWVW + Pm (2) (momentum conservation). N .1. and W~. The flow is illustrated schematically in Figure 2. diffusion. Derivation of the equations A coordinate system that is stationary with respect to the wave will be adopted.. equation (129). Schematic diagram of a deflagration or detonation wave .. + ~ $ 2 = hw + &/2.1. = l . . viscous effects FIGURE 2.. . and it will be assumed that the flow is in the +x direction and that properties are uniform in planes normal to the x axis.. and equation (128) (the energy equation) implies h. 2 (1) where m is the mass flow rate per unit area. (4) (5) The equation of state. while downstream conditions (at x = co) are denoted by the subscript co.1. The sequence of states at x = co (with fixed parameters at x = . and. Zone involving heat conduction.+ f 00. ~ = O i.
.. PO. k .(l/pm .l/po) plane. Using equation (1) to express u in terms of m and p in equation (3) yields when equation (8) is used to eliminate m2. for idealgas mixtures equations ( 6 ) and (7). The convention to be adopted here is slightly different from that for equation (18). and wi. Y. . respectively. N .2.1. General RankineHugoniot Equations 21 and the caloric equation of state. From equation (18) we see that the mass rate of production of species i by chemical reactions may be expressed as M . is a relationship among thermodynamic properties alone..p o ) .mL (7) constitute further relationships between the initial.k is the mass rate of production of species i in the kth reaction and there are M independent reactions. so that the present M is half of the previous M .._ w i = C w i . as velocities have been eliminated. Since equation (1) implies that equation (2) may be written as which defines a straight line (the Rayleigh line) with a negative slope in the ( p .. p m . The speciesconservation equations require further discussion because equations (4) and (5) may not all be independent. d h o . '0. reduce to equation (19) and the relation obtained by substituting equation (111) into equation (110) ( h = u + p / p ) . h= 1 where wi. From the stoichiometry of the kth reaction. forward and backward reactions will not be considered separately as is implied by equation (1S). i = l .and finalflow properties. and all of the information that can be obtained from equation (129) is not contained in equations (4) and (5). Equation (9).k is the difference of two terms of the type appearing inside the summation in equation (18). In future work it will be convenient to employ modified forms of equations (2) and (3). it follows that . which is called the Hugoniotequation.o) = d h m . K. T m .
co in Figure 2.. . [equation (l)] and + 0 as x + co (because diffusion velocities are proportional to gradients of the flow properties). Hence equations (12) and (15) provide a total of N independent relations among the flow properties at x = 0 0 . see Section B. where L is the total number of atoms in the system. Hence w . (which is independent of i) is the net rate of the kth reaction (that is.o/w= 1v ? x . are linearly independent. . .2..22 RankineHugoniot Relations where w. given by equation (15). then the fact that atoms are neither created nor destroyed by chemical reactions is expressed by the equation w. when M < N it is possible to derive additional (atomconservation) conditions from equation (129)... . The combustible mixture approaching from x = . there are M equilibrium conditions and N .2). but w .. The initial mixture is in a metastable state and therefore actually reacts at a small but finite rate. .=0. the difference between the forward rate and the backward rate.=O. into equation (14) and integrating from x = . .. If vy) denotes the number of atoms of kind j in a molecule of kind i.M of these relations are independent (compare Section A. .1. J Y . However. just as in the problem of computing equilibrium compositions in closed systems (Appendix A).. M . .M atomconservation conditions. ~ # 0. k = l . ~ . j i= 1 = I . (15) 1 I= 1 since po uo = p. Equations (10) and (11) imply that equations (4) and (5) are satisfied when 0. N l v ? ) w i / w = 0.1. u. . .00 to x = + oc yields 1vp)x. (12) and k = l . L. L. The coldboundary difficulty The restrictions given by equation (13) [or equation ( 5 ) ] are not fulfilled exactly in deflagration or detonation waves. I= N N j = 1. (13) which may constitute fewer relations than equations (4) and (5). 2.7). the stable condition is that in which the mixture is composed of products of combustion.. it will always be true that N .... .M .1 is not in stable chemical equilibrium. Although it may be found that not all of the L additional relations between the properties at x = +a and those at x = a. Substituting equation (129) for w.3. since M I N in general.
after m has been obtained from u. To. the intersection of the Hugoniot curve with the Rayleigh line defined by equation (8) determines the final therinodynamic state. then these N + 5 equations would determine the downstream flow variables u . p . As illustrated in Figure 2. and Y. in some sense. and y. for the particular experiment. (12). If all upstream conditions (including uo) were specified. in a typical experiment a given mixture in a tube will be ignited. because the same trouble necessarily arises in studies of detonation structure (Section 6. the values of T . (6)(9). the propagation velocity u. The value of v.. p . equation (13) would not even arise. l/pm) plane along which the solution must lie regardless of the value of 21. and (15) comprise the independent relations between upstream and downstream conditions. However. equation (13) is satisfied approximately. p . equation (13) will be satisfied approximately for any initial mixture composition for which the mixture can be contained long enough to support a detonation or deflagration wave. thus emphasizing how elementary it is. from equation (7). and (15). General RankineHugoniot Equations 23 is very small compared with its value in the reaction zone so that. (6)(9).3.. are solved for relations among flow properties downstream. called the Hugoniot curve. h .2.2) and of deflagration propagation velocities (Section 5.J * This calculation is similar to the equilibriumcomposition computations discussed in Appendix A. is investigated in the following section. the conditions that fix v o (to be defined in later sections) may be introduced to complete the solution.3. Therefore.=. . is not controlled directly but instead is determined by other experimental parameters. T. . After the equations that do not contain u. may then be evaluated for these same values of pa and pa. and (15) constitute the required forms since velocities appear only in equations (1) and (8) of this set. given. Furthermore. Equations (l).2.. If the problem were formulated in terms of wave propagation in a given combustible mixture. 2. (12). equation (13) actually provides no reasonable restriction on the initial conditions and will be omitted from the governing equations. .2.. With p o . may then ~ (x.. .1. and the chemical equilibrium composition can be calculated for various values of p4 and pa. equations (l). Therefore. and the result may finally be substituted into the Hugoniot equation.1. (12).h. Although the initial composition and thermodynamic properties are adjustable experimentally. from equations (6).* the enthalpy h. from as many equations as possible. study of combustion waves is facilitated by eliminating u.2).1. . Use of the RankineHugoniot equations In summary.. equation (9). it appears to be desirable to introduce this “coldboundary difficulty” at an early stage. The nature of this curve.. in order to determine a curve in the (pm. and the velocity at which the combustion wave propagates down the tube will be measured.
ANALYSIS OF A SIMPLIFIED SYSTEM 2.24 RankineHugoniot Relations Pm t I l/PO  l/Pm FIGURE 2. be calculated from equation (1). are all fixed).=~ 1 ~ .2. i= 1 C X . [ S ] ) . and so on). which provide accurate Hugoniot curves based on the best values available for thermochemical properties. p o . y. C ~ . ~ and (3) between the initial temperature To and any final temperature T. (2) the final average molecular weight equals the initial average molecular weight that is.2. the specific heat at constant pressure at the final composition equals the specific heat at constant pressure of the initial mixturethat is. . y. i = . (1) the final equilibrium composition along the Hugoniot curve is constant (that is. We shall consider an ideal gas mixture in order to assure that equations (19)(111) are valid.2. along the Hugoniot curve. o. o cp i= 1 N N (=constant) (17) for cp. Simplification of the RankineHugoniot equations The essential characteristics of the Hugoniot curve are most easily illustrated by studying a particular simple system. Variations of this procedure have been programmed in recent years for solution by electronic computers (for example. The determination of downstream flow properties from the Hugoniot curve. It will be assumed that for the given initial thermodynamic properties ( p o .1. 2. The simplest system for which . . in some T range including To and T. o c p .
q. Substituting equation (20) into equation (19). . p o . is the specificheat ratio for the final mixture. In view of equation (16).cc and at x = + cc yields =u + p/p. equation (19) reduces to (w Substituting equation (111) into equation (1lo). = 4 dT = 4 + cJT./(Ro/W)will enter into the result. and p m .  h. The temperatures To and T. Solving equation (18) for T. is the total chemical heat released per unit mass of combustible mixture. Analysis of a Simp!ified System 25 equations (16) and (17) are valid is one in which all species have equal = W for all i) and constant and equal heat capacities molecular weights (c. Ro/W for an idealgas mixture. which./(Ro/W) = c. The heat of reaction of the mixture may be defined as 4 i= 1 ? [(Y.2.) = y / ( y .2. and To and substituting these results into equation (21) therefore yields Equations (9) and (22) show that the Hugoniot equation may be written in the form which containsonly the known constants y. may be eliminated from equation (21) by using equation (18). in view of equation (17).idT)].c.)(ho + IT:cp. it follows that c. (21) where use has been made of equation (17) in obtaining the final equality. Equation (23) may also be obtained by considering a . Since the specific heat at constant volume is given by c. = c. and po in addition to the variables p . It can be seen that the ratio c..l)./(c..  To). we obtain h.o +  Y. = constant for all i). solving for h and evaluating the result at x = .~ = c. after subtraction. where y = CJC.
2.* All curves asymptotically 1) and p = . Equations (8) and (23) therefore determine the complete solution for the simplified system.2.2.3 and 2.l)/(y 1). . respectively.4 for y = 1. approach the lines u = (y .26 RankineHugoniot Relations onecomponent ideal gas to which an amount of heat q (per unit mass) is added externally. Multiplying equation (23) by po/po yields the solution of which is Dividing equation (8) by p o po gives 2. and p must all be positive for physically acceptable solutions. From equation (23) an explicit algebraic expression for p a as a function of p x along the Hugoniot curve may be obtained.( y . Properties of the Hugoniot curve The Hugoniot curves given by equation (24) are plotted in Figures 2. A dimensionless final specific volume is the density ratio 0 = Po/& > which is also equal to the velocity ratio u. A dimensionless heat of reaction is = 4Po/Po7 and a dimensionless massflow rate is P = m’lpo P o .Therefore.4 and y = 1. A dimensionless final pressure is the pressure ratio P =PXiPO.2. Dimensionless form The nature of the results will become more transparent if dimensionless variables are introduced.l)/(y + + * The curves for a = 0 are of significance in connection with ordinary shock waves. 2.3./uo according to equation (1). It will be observed that p . u.
l)/(y + 1) I v I 1. with the upper bound corresponding to the limit p + 0 [see equation (24)].4 the entire range of pressure ratio (0 I p I c o )may occur.4 are physically meaningless. Combustion waves are termed detonation waves or deflagration waves according to the branch of the Hugoniot curve upon which the final condition falls. an upper branch [l + ( y . Each Hugoniot curve is therefore divided into two nonoverlapping branches.3. 1 + (y . but the specificvolume (or velocity) ratio is restricted to the interval (Y .l)a/y I v I 2a + ( y + l)/(y . . Acceptable end states must lie on one of these two branches. ( y .1)a I p I 00. see equation (24)] called thedetonation branch and a lower branch [0 I p I 1.p [equation (25)] establishes the final state of the system.2. Hugoniot diagram from (24) with y = 1. The intersection between the appropriate Hugoniot curve and the straight line through the point (1. Analysis of a Simplified System 27 P=  r+l V 71 FIGURE 2. the slope of this straight line is negative. and end states lying in the two shaded quadrants in Figures 2.3 and 2. Since p > 0. 1)with slope .2.1). see equation (24)] called the deflagration branch.l)/(Y + 1) I v I 2a + [(r + l ) / ( Y  111.
1) is tangent to the detonation branch of the Hugoniot curve.2.4. Hugoniot diagram from (24) with y 1.28 RankineHugoniot Relations P V= P= .2. and its pressure and density increase. Other striking differences between the two types of waves will appear when we discuss wave structures in subsequent chapters (see Sections 5. in passing through a detonation wave the gas is slowed down.3 and 2. and its pressure decreases. an understanding of the difference between detonation and deflagration waves is best obtained by contrasting the characteristics of each. Analysis of the detonation branch It is easily seen from Figure 2.4 that a unique straight line through the point (1.Y. Thus (see Figures 2. Although this formal distinction is invaluable because of its unambiguity.3 or Figure 2.4. in going through a deflagration the gas speeds up and expands. This can be proven formally by considering the equation .1). however.3 and 6.YT 1 I 0 1 2 3 4 U 5 6 7 = 8 9 FIGURE 2.4). 2.
detonations are ChapmanJouguet waves. ) on the detonation branch is said to be the upper ChapmanJouguet point. l). u . equation (24). can be shown to possess only one solution. Under most experimental conditions. The experimental conditions determine whether a strong detonation.lying on the detonation branch. there are two possible end states for the detonation. 1) will not intersect the detonation branch anywhere if the magnitude of its slope is less than that of the tangent line. corresponding to the ChapmanJouguet end conditions (at point B in Figure 2. .2. which states that the slope of the Hugoniot curve equals the slope of the straight line from the Hugoniot curve to the point (1. u +).5. ( p + . since the reasoning involves concepts of the structure of the wave. and the wave with this end condition (point B on the Hugoniot curve illustrated in Figure 2. Schematic diagram depicting the various sections of the Hugoniot curve. this topic will be discussed more fully in Section 6. while it intersects the detonation branch at two points if the magnitude of its slope exceeds that of the tangent line. When p exceeds its minimum value p+ (that is. This is illustrated in Figure 2. Analysis of a Simplified System 29 where p(u) and dp/dv are evaluated from the Hugoniot equation. A straight line through the point (1.2. one lying on the line A B (a strong detonation) and the other lying on the line BC (a weak detonation).2. at higher wave speeds). or a weak detonation will be observed at a given value of p. Equation (25) therefore implies that there is a minimum value of p (that is. This point ( p + . a ChapmanJouguet wave. Equation (26). where typical solutions lying on the detonation branch ABC are indicated. P 11 FIGURE 2.5).5) is a ChapmanJouguet detonation.5. a minimum wave speed) for detonations.
v). A straight line through the point (1.5.< p + ) . It is therefore of interest to investigate the properties of the ChapmanJouguet points in greater detail.6. which propagates at zero velocity ( p = 0). which is called the lower ChapmanJouguet point (point E in Figure 2. Limiting cases are the strong deflagration with p = 0. shows that a unique straight line through the point (1. and the isobaric weak deflagration ( p = l).3 that strong deflagrations do not occur. Hence the ChapmanJouguet deflagration has the maximum wave speed ( p = p . represent unattainable limiting cases.3. From considerations of combustionwave structure. both of which propagate at infinite velocity ( p = a ) .) of all deflagrations. which has a finite (nonzero) propagation speed.30 RankineHugoniot Relations Figure 2.5) at a point ( p . A wave with endpoint E is a ChapmanJouguet deflagration. and it intersects the deflagration branch at two points (once on DE and once on E F ) if its slope is less than that of the tangent line. Properties of ChapmanJouguet waves ChapmanJouguet waves assume a special significance in many systems. Analysis of the deflagration branch Remarks precisely analogous to those given above for the detonation branch of the Hugoniot curve also apply to the deflagration branch. The strong detonation with p = co and the isochoric weak detonation (v = l). particularly those involving detonations.5 shows that as the nomenclature implies. 1) is tangent to the deflagration branch (DEF in Figure 2. nearly isobaric. hence the physically meaningful section of the deflagration branch of the Hugoniot curve is DE.2..4. Figure 2. The pressure and velocity changes across strong deflagrations exceed those across weak deflagrations. it will be indicated in Section 6. the pressure ratio and the velocity change across a strong detonation exceed those across a weak detonation. Differentiating equation (24) yields . 1) fails to intersect the deflagration branch if the magnitude of its slope exceeds that of the tangent line.5).5 clearly shows that this maximum deflagration velocity is less than the minimum detonation velocity ( p .2.1. 2. Waves with end states lying along line DE are weak deflagrations and those with end states on line EF are strong deflagrations. Most deflagrations are. this result can also be derived from equation (26). 2. Figure 2. in fact. Figure 2. or equation (26).
2. and lower signs correspond to the deflagration branch.rl P = YPIV (27) at either ChapmanJouguet point. then a quadratic equation for p is obtained. < 1) for strong detonations and weak deflagrations. From the definitions of the dimensionless variables p ./a. the dimensional form of equation (28) is seen to be m 2 = y p z p . Jyp. and this result is substituted into equation (24)./Pm (29) [see equation (l)]. = (s = entropy per unit mass)./p.which implies that urn = JYP. By using this relation in equation (25). .. A more thorough analysis shows that the downstream gas velocity relative to the wave exceeds the sound velocity ( M .2. > 1) for weak detonations and strong deflagrations and is less than the sound velocity ( M . the solution to which is Upper signs correspond to the detonation branch. It is also possible to prove that along the Hugoniot curve. For example. the entropy assumes a local minimum value only at the upper ChapmanJouguet point and a local maximum value only at the lower ChapmanJouguet point [7] and that along each tangent line given by equation (25) (the Rayleigh line). is unity at both ChapmanJouguet points. = o. giving C81. if equation (27) is solved for u. the entropy assumes a local maximum value at the ChapmanJouguet point Explicit expressions for the dimensionless downstream properties (in terms of CI and y) are easily derived for ChapmanJouguet waves. and 0. it can be shown that (28) at the ChapmanJouguet points.Analysis of a Simplified System 31 which may be substituted into equation (26) to obtain P = m r + 1)u . p . we see that equation (29) implies that the downstream Mach number M . Recalling that the speed of sound in an ideal gas is a m = Jm. Substitution of equation (31) into equation (30) yields .
3. The result is = from equation (1) and the definisince M. uo/dyz f i 1. Equation (33) may be used to compute the initial Mach number for ChapmanJouguet waves. as determined by equations (31)(34) with y = 1..32 RankineHugoniot Relations By using equations (31) and (32) in equation (25). we conclude that all detonations propagate at supersonic velocities and all deflagrations propagate at subsonic velocities. . Equation (34) shows that both M o + and M. the downstream temperature is found to exceed the upstream temperature at both ChapmanJouguet points./T. the initial Mach number always exceeds unity for ChapmanJouguet detonations and lies between zero and unity for ChapmanJouguet deflagrations..6. = p u [see equation (IS)] . we find that The temperature ratio may be computed from T.approach unity o and M.00 I 3.50 0.25 D a d ~ $ 7 $ 2 R I FIGURE 2. According to equation (34).75 3. while M o + + c as c( r 00. Since the ChapmanJouguet waves correspond to the minimum propagation speed for detonations and the maximum propagation speed for deflagrations.+ 0 as the heatrelease parameter a goes to zero. = uo/uo = tion of p. The dependence of the properties of ChapmanJouguet waves upon the dimensionless heatrelease parameter 3.
N parameters besides s must be specified as constants in computing a p / d p to evaluate a’. a possible source of ambiguity for multicomponent systems is the fact that more than one sound speed a can be defined.4.2.= 0. .2 remain valid for all the systems that fall within the framework of the equations presented in Section 2.1 independent intensive parameters must be specified because p .3. We shall briefly discuss the most important complication that arises in attempting to extend our results. p. Frozen versus equilibrium sound speeds It was shown in Section 2. In accordance with our earlier discussion. The expressions which must be changed are those that involve c1 explicitly.2. since the single parameter c1 is not sufficient to characterize the behavior of arbitrary multicomponent mixtures. Many quantitative results obtained in Section 2.3. EXTENSION OF THE RESULTS TO ARBITRARY SYSTEMS 2. and M o + = 5. u.* Since there are N + 2 independent thermodynamic variables in an Ncomponent gas mixture. 2. If s is the entropy per unit mass. and then we shall summarize most of the properties of arbitrary Hugoniot curves by means of a table. then actually only N . and M. this result applies to any combustible gas mixture.. It is understood that we are always referring to downstream conditions here. and a are intensive properties that are independent of the size of the system. (Tm/To)+ = 12.2 Moregeneral analyses than those given in the preceding section show that the qualitative properties of the Hugoniot curve derived in Section 2. approximately.2 are also of general validity.3.6 as functions of the dimensionless heatrelease parameter a for y = 1. these numbers are typical of experimentally observed detonations but unrealistic for deflagrations.= 15. only some equations and certain limits on inequalities will require modification.3.= 0. When interpreted correctly.2 that the downstream Mach number is unity for ChapmanJouguet waves. Extensions of the Results to Arbitrary Systems 33 Numerical values of the parameters for ChapmanJouguet waves are plotted in Figure 2.8 (giving uo % 1000m/s) at the upper ChapmanJouguet point. while p . p + = 20.+ A frozen (constantcomposition) sound speed may be defined as * The subscript cc is suppressed in this section for the sake of clarity in notation.6 shows that.46.1. u+ = 0.3.17 at the lower ChapmanJouguet point. A representative value of a is a = 30. for which Figure 2.1. 2. (Tm/To)= 7. Range of validity of the results of Section 2.5. However.58.
and the partial derivatives are taken in a closed system (of entropy S and volume V ) . e ( p . and an equilibrium sound speed may be defined as ae = [ ( a P / m s . in general. c .+Further information on this topic may be found in [9] and in some of the references quoted therein (see also Section 6. Y.2. which are comparable with the errors in the most accurate experimental measurements of this parameter (about one part in lo3). may lead to overestimates of the computed ChapmanJouguet detonationpropagation velocities. .. [which equals (a2U/2t2). Since af 2 a.. Proof that = ae. then straightforward thermodynamic calculations show that where t is the reaction progress variable defined in equation (A19).. Since the factors preceding the brace on the righthand side of this relation are intrinsically positive. The subscript notation is to = y .3. The rigorous analysis given in the following paragraph supports this guess. [6]. S K I = 1.. Methods for computing ChapmanJouguet detonation velocities are given in [l]. ..uz is the same as the sign of the last factor. [lo]. s) means that be set equal to its equilibrium function of p and s [which is determined by equation (12)] in computing the partial derivative. it might be expected that the ChapmanJouguet tangency condition would lead to M = 1 with M defined in terms of a.NJ 1/2. and [ll]. the downstream gas velocity relative to the wave equals the equilibrium sound speed at the ChapmanJouguet points.. .. = Y. Since the Hugoniot curve is an equilibrium curve.s ) represents the equilibrium mass fraction of species i at the given p and s in a mixture at the specified overall atomic composition [equation (15)]. e ( p . for example. Using M = 1 to define the ChapmanJouguet point.* the problem is to determine which (if either) of these appears in the definition of M for which M = 1 at the ChapmanJouguet points. if only one chemical reaction can occur in the system under consideration. 2. For example. at the ChapmanJouguet points Ixl For a small change along the general Hugoniot curve [equation (9)]. the sign of u.4). (V = internal energy)]. we find by differentiation that * This is a consequence of the fact that thermodynamically unstable equilibria are not attainable in natural processes.34 RankineHugoniot Relations (Y. = mass fraction of chemical species i). where y .3. [2]. other symbols are defined in Appendix A. ( p .instead of a. with the M based on a/. The reasoning following equation (A20) implies that a small disturbance will cause the system to move away from the equilibrium point if this last factor is negative.
3. . Extensions of the Results to Arbitrary Systems 35 The tangent to the Hugoniot curve is a straight line through the point ( p o .s w ) for i = 1. = 0 (39) at the ChapmanJouguet points along the Hugoniot curve. Since the entropy change along the Hugoniot curve [at Y. Summary of the properties of Hugoniot curves Table 2.. max. l / p o ) provided that. .. 1.. In the table.4. . xy=. S m ) ( I = l ...2 are inapplicable. This analysis is illustrative of the type of reasoning required when the assumptions of Section 2. The quantities * Terms corresponding to pLd N . Using equation (36) to eliminate d ( l / p a ) from equation (39. in equation (A5) do not appear in equation (38) because the condition of chemical equilibrium [equation (A1 6) with the equality sign] implies that these terms are zero in the present case... w ( p w ..Y. = Y. Hence. in equation (39.. in equation (36). Equations (8) and (36) show that where the last equality follows from equation (1). at the ChapmanJouguet points as desired.=Y m ( p m ..2. determined by the initial state of the mixture. Equations (40) and (41) finally yield (42) v : = (aPa/aPm). and min are fixed constants.=.1 summarizes many of the properties of Hugoniot curves. . I..3. N ] is given by the thermodynamic relationship* equation (37) implies that ds. which states that v. . quantities identified by the subscripts +. 2.. = a?..N ) . we obtain the expression 1 (37) d h . CD. = d p Pa.
requires very special gas mixtures.) umin (Omin (Pm/PO) = (u. 1 Strong detonations m Line AB < u < u+ > 0) Mo+ < Mo < < Seldom observed. 25 Pressure ratio Velocity and density ratios P= = (PO/P. Upper ChapmanJouguet point 1M.TABLE 2. > 1 Not observed.> 1) Lower ChapmanJouguet point Point E M.1. Seldom observed. . p = 1 in most ex periments. > 1 Weak leflagrations 0 Line DE p ..) M.< p < l < Mo < Mo hi. Usually observed for waves propagating in tubes. Properties of Hugoniot Curves Downstream Mach number Remarks M m Section in Fig. requires special experimental arrangement. Point B = 1 Weak detonations Line BC u + < u < l Mo+ m < Mo < M. < 1 Often observed. Strong leflagrations Line EF 11. forbidden by considerations of wave structure. = 1 Not observed.o) = (udae. u = u(u./uo) Propagation Mach number M o = (uo/a/.
Z . Hirschfelder. 797814. The quantity M . B. A R S Journal 29. R. Z . J . 5. S. Edse. S. New York: Wiley. Curtiss. 42. 11. Zel’dovichand A. .4172. Chem. Scranton. B. and M . P. No. Oppenheim. 1968. Gordon. 0. and R. B. 1957. F. 1954. R. 1960. Detonations. R.2.” Tech. Penner. L.are given by equations (31)(34) only under the restrictive conditions imposed in Section 2. 173 (1959). J. Y. S. The limits for all of the inequalities except those in parentheses are intended to represent greatest lower bounds or least upper bounds. Scorah. Wright Air Development Center. “Calculation of Detonation Velocities in Gases. J. 6. Physik. 4. 8. 9. is based on the equilibrium sound speed in the final mixture. Gordon and B. Zeleznik and S. Gross and A. 10. New York: Pergamon Press. Explosions. S. Kompaneets. Chemistry Problems in Jet Propulsion. A R S Journal32. New York: Pergamon Press. With this information. 3. 54416. 425 (1935). F. C. is based on the chemically frozen sound speed in the initial mixture. S. A. Penner. McBride. Molecular Theory of Gases and Liquids. 1959. Strehlow. Penn. Mullins and S. Dayton (March 1956). 7. TheoryofDetonation. Fundamentals of Combustion.1 should become selfexplanatory. Phjx 3. Elektrochem. J. R. Bird. Flammability and Ignition. K.457 (1936). : International Textbook. 606 (1962). 321 (1922).References 37 with subscripts and . + REFERENCES 1. R. Table 2.New York: Academic Press. NASA SP273 (1971). Rept. 8. 149155. 68108. 2.258266. Becker.
and highly turbulent motion. a pan of oil burning in air. Included here are processes involving unsteady flow. The broad definition encompasses a wide variety of processesfor example.3). nearly isobaric flame in which most of the reaction occurs in a narrow zone that can be approximated as a surface. so many diffusionflame problems exist that we do not have enough space to consider them all. In a restricted sense. a lighted candle. The couplingfunction formulation (Section 1. highspeed flow. a diffusion flame may be defined as a nonpremixed.CHAPTER 3 Diffusion Flames and Droplet Burning In the broadest sense. Therefore. This is the class of flame problems that will be discussed in the present chapter. we shall merely illustrate the analytical procedure by means of three examples (Sections 3. a diffusion flame may be defined as any flame in which the fuel and oxidizer initially are separated. The problem of droplet burning (Section 38 . With this usage. quasisteady. Therefore. as we shall see. it is unreasonable to attempt to discuss all of these processes from a unified viewpoint.3) provides a convenient framework within which these problems can be studied. Even within our restricted definition. the term is synonymous with nonpremixed combustion. a forest fire. Coupling functions usually are more useful for initially unmixed systems than for initially premixed systems because. and a fuel droplet burning in oxygen in a rocket engine. the chemical reaction rate is often of negligible importance in answering certain questions raised for diffusion flames.1 3. an aluminum sheet burning in a supersonic air stream.
1. 3. also involves consideration of finiterate chemistry but is related to the burning of a fuel droplet in an oxidizing atmosphere (Section 3.fuel (or oxidizer) issues from a cylindrical Z . .1 . Diagram of the BurkeSchumann problem. treated in Section 3. liquidfueled engine combustion) and therefore will be considered in somewhat greater detail.4. In recent years appreciable clarification of structures of the thin sheets at which reactions occur has been obtained through asymptotic methods. The BurkeSchumann problem is illustrated in Figure 3.0 Y F = YF.1. For this reason.1. The Flame at the Mouth of a Tube In a Duct 39 3.3).O Underventilated f' Overventilated f u r FIGURE 3. Most of these topics are also treated in [1][3].3) is of importance in other contexts (for example. Flame r I V / I Y . Monopropellant droplet burning. the relevance to diffusion flames dictates coverage here.5.5 after completing Chapter 5. the reader may return to Sections 3. Although study of these structures necessitates simultaneous consideration of both finiterate chemistry and diffusion processes and therefore pedagogically belongs after Chapter 4. Definition of the problem The first successful detailed analysis of a diffusionflame problem was given by Burke and Schumann in 1928 [4]. the reactionsheet structure is analyzed in Section 3.1.O Yo = Yo.3. In a pedagogic approach. THE FLAME AT THE MOUTH OF A TUBE IN A DUCT 3.4 and 3.1. = Yo.
pD = constant. the following approximations will be made. respectively. particularly. (2) where e. N .3. The product pD is constant throughout the duct.40 Diffusion Flames and Droplet Burning tube into a concentric cylindrical duct through which oxidizer (or fuel) is flowing. Conditions at z = 0 will be identified by the subscript 0. 8 = azimuthal angle) and set the origin on the tube axis at the mouth of the inner tube (see Figure 3. respectively. Burke and Schumann obtained fairly accurate predictions of the flame height and the shape of the flame for laminar flow. Axial diffusion is negligible in comparison with radial diffusion. To investigate this problem. let the radii of the inner and outer tubes be a and b. (4) 4. A flame is established at the mouth of the tube and either extends to the wall of the duct (the underventilated case) or converges to the axis (the overventilated case). Y = radial distance from the axis. . that is.laz + a r .2. that is. We shall denote the species in the inner and outer tubes by the subscripts F and 0.1).2) identifies the various product species [compare equation (142)]. Section 1.. 2. v = ve. (5) . The total mass flux in the z direction is constant everywhere in the duct. that is.2. . is required for the design of burners of this type. Let us employ a cylindrical coordinate system ( z = distance along the axis.3. 3. that is. ar. The notation will be the same as in Chapter 1. p . and shall consider the onestep overall chemical reaction where the subscript i ( i = 1. 1.. Assumptions In addition to all of the assumptions introduced in Section 1. defined as the axial distance from the mouth of t h m d k e point at which the flame reaches either the wall of the duct or the axis. The massaverage velocity is parallel to the axis of the tube everywhere.1. (3) 3. is a unit vector in the z direction. . ThAflame height. pv = constant.
=b = [D(d&/dr)].1. z > 0.1. The way in which approximation 5 is used will be explained in Section 3. a < r < b. because of the symmetry of the problem. l~=~ where e. according to and a0 = .o in the outer duct. and the validity of the approximations will be discussed after the solution is obtained.3.1. By using equations (2)(5) in the definition given in equation (145). ..3. (10) (1 1) (12) p = . since YF = Y. Solution of the species conservation equation for the coupling function p The only differential equation that we shall be obliged to consider is equation (149) with where. Equations (10) and (11) follow from equations (6)(8).e. we find that equation (149) becomes where the Laplacian has been written in cylindrical coordinates and terms involving a/ae have been set equal to zero.). The entire reaction occurs at a surface called the flame sheet.ro.4. or reaction sheet.=b and = 0 ( y o v O . 0 5 r < a. 3. The Flame at the Mouth of a Tube in a Duct 41 5.. The boundary conditions for equation (9) are that p is bounded everywhere and that p = YF.Yo/W0v. = 0 and Yo = Yo. is a unit vector in the r direction. while Y . = [~(a~~/a~ = )0.=. 0.o/w and z r aglar = o = b.O/wFvF at at at z = = 0.o and Yo = 0 in the central pipe. Equation (12) is a consequence of the physical requirement that neither fuel nor oxidizer can diffuse into the outer wall (at r = b): (YFvF'er).
< ) e . it can be shown (through the use of recurrence formulae and other known properties of Bessel functions of the first kind) that y = (1 + v)c'  v + 2(1 + v)c n = l (Pn c m  CJO((Pn)l2 J1(ccpn) J . To solve equation (18).cpo = 0). By the method of separation of variables. no oxidizer is present (Yo+ = 0).42 Diffusion Flames and Droplet Burning It is convenient to introduce the dimensionless coordinates i" = r/b and y E zDfvb2 and to define the reduced parameters and and the reduced variable y PwFvF/yF. In terms of these quantities. 3. In one region (which will be identified by the subscript +).~ ~ q . ( ( P )= 0 (with ordering convention (P. (19) (20) (21) at y = O . and therefore P+ = YF/WFVF (23) . subject to the boundary conditions given in equations (19)(21) and to the additional requirement that y be bounded. respectivelyand the cpn represent successive roots of the equation J .O.4. and dy/d( = 0 i" = 1. (22) where J .1. is a straightforward mathematical problem. q > 0. The flame shape and the flame height In order to obtain the shape of the flame and the flame height from equation (22). and J 1 are Bessel functions of the first kindof order 0 and 1. then this surface must divide the flow field into two regions. for example. If the entire reaction is to occur at a flame sheet. OI{<C. ( ( P . Equation (22) provides the solution to equation (149) for in the present problem. at c<(<l. we must introduce approximation 5. equations (9)( 12) become y = l y=v at y=O. > qn.
and equation (24) shows that P. The Flame at the Mouth of a Tube in a Duct 43 from equations (6)(8).2 for c = and for two different values of v. equation (23) shows that P + 2 0 in the fuel region. This condition is compatible with the preceding inequalities only if P=O (25) at the flame sheet. Hence. (24) Equations (23) and (24) actually imply that equation (22) gives the concentration fields for both the fuel and the oxidizer. no fuel is present (YF.= 0).Y ol w o vo . in the other region (identified by the subscript ). 2 v = 0. . Since equation (22) implies that P is continuous in the interior of the duct [see equation (17)].3. in their respective regions.1. In view of the fact that the mass fractions YFand Yo are nonnegative. setting y = 0 in equation (22) provides a relation between 4 and y that defines the locus of the flame. The flame height is obtained by solving equation (22) for y after setting 5 = 0 for overventilated flames or 5 = 1 for underventilated flames 0 . P+ = P at the flame surface. The shape of the surface obtained in this manner is shown in Figure 3. and therefore P = .2.I 0 in the oxidizer region. Flame shapes for the BurkeSchumann problem (c = $).5 (Overventilated) FIGURE 3.
yo+ Vo+) + Pw o vo ~ in the steady state.vF = wo/Wo vo . considering the drastic nature of some of the approximations. the differential form of this equation is Equation (27) states formally that fuel and oxidizer must flow into the flame sheet from opposite sides in stoichiometric proportions. Neglecting all the terms except n = 1. it is of interest to study the character of this approximation in greater detail.. The first zero of J. The significance of the approximation can be addressed from the viewpoint of the general interface conservation condition given in equation (158). the agreement is surprisingly good. In view of equation (l). wi d Y # 0 [that is.13. it usually suffices to retain only the first few terms of the sum in equation (22) for this calculation. then lim. we find that ~ p + yo+ (v.41. 3. wi + wi S ( y .(cp) is cpl = 3. * These operations are necessary because if all of the reactants are to be consumed at the interface.* (158) with i = F by WFvF. have the same meaning as in Section 1.o f. . equation (143) implies wF/ W.83. y = 0 in either case). of course. dividing equation (158) with i = 0 by Wove. Here the unit vector normal to the flame sheet (n. dividing equation and subtracting the second result from the first.4.). The flame shapes and flame heights obtained from equation (26) by Burke and Schumann are in fairly good agreement with experiments. w o vo .3. which we shall now discuss. we obtain the rough approximation for the dimensionless flame height of an underventilated flame.1. Since flame heights are generally large enough to cause the factor eqftq to decrease rapidly as n increases at these values of q.44 Diffusion F l a w s and Droplet Burning (and. as well as all of the other symbols.y r )in the notation of Section 1. The flamesheet approximation Since the flamesheet approximation is common to all of the problems considered in Sections 3. When there is no fuel on one side of the surface (YFE 0) and no oxidizer on the other side (Yo+ = 0).5. Hence.
although uncertainties arise for strongly sooting flames.= 0. violating assumption 1. for a diffusion flame. there is no fuel or oxidizer present at the flame sheet. the heat release in the flame increases the temperature and therefore decreases the density of the isobaric stream.D V F . Assumption 4 is acceptable when the flame heigdt i$ large enough (in comparison with the tube diameter) . but it does not imply that the terms involving VF+ and Vo. uncertainties in the temperature and composition at which p D is best evaluated arise from the difficulties associated with assumptions 1 and 2 and are particularly severe if the values of p D for fuel and oxidizer differ appreciably.4). equation (27) reduces to the condition that the diffusion rates (which are now equal to the total rates) of transport of fuel and oxidizer to the flame sheet must be in stoichiometric proportions. However. the density decrease will also cause the flow to expand. thus causing the velocity to increase according to equation (3). Criteria for the validity of the flamesheet approximation may be developed by analyzing the structure of the sheet (see Section 3.3. Assumptions 1 and 2 appear to constitute the most unrealistic approximations in the present analysis. Thus. but the initial velocity profile will not be uniform (unless special experimental precautions are taken) because the velocity must approach zero at the walls. and the streamlines will diverge from the hot regions (compare Figure 5.(the convective terms) in equation (27) vanish.1. 3. Assumptions 1 and 2 are mutually inconsistent in this problem. In the couplingfunction formulation.6. and the concentration gradients remain nonzero at the flame sheet.. Furthermore. This implies that the terms involving v.vanish because FV. 0 [see equation (137)]. and this would invalidate assumption 2 in the approach stream. The Flame at the Mouth of a Tube in a Duct 45 Since equations (23)(25) imply that Y.2). A velocity profile corresponding to fully developed pipe flow would be more reasonable. For calculation of flame shapes in the BurkeSchumann problem. The approach flow in the inner and outer pipes will be parallel to the axis (assumption 1) and will have constant density. i = F + . the flame produces nononedimensional flow. Assumption 3 has previously been shown to constitute a reasonably accurate approximation. and v .1.1.2. The validity of the other approximations Let us finally consider the validity of assumptions 14 of Section 3. this condition is an automatic consequence of the continuity of the gradient of p at the flame. the approximation usually is well justified. since the heat release is not uniform in planes perpendicular to the axis of the tube. some consideration has been given to influences of inlet velocity profiles [581. Therefore. = 0 and Yo. they are best justified by the analytical simplifications that they produce. = . However.
3 underlie the formulation. The estimate might be thought to be usable directly for smallscale. This estimate is not immediately applicable for deriving the correlations [9][l l] because they pertain to largescale regimes. instead. further complicating the algebra .1. and Fr. h/a ua/D = Pe. less dense gas in the region of the flame often distort the shape of the flame sheet. Roper. in which D here must be viewed as an effective diffusivity that depends on v. so that the characteristic transverse length for diffusion becomes an average value si. Cunningham. different from a. Smith. this can be shown to be true if the dimensionless parameter ub/D is sufficiently large. * If t is the time for a fuel element to travel from the burner port to the flame tip. cancellation ofg from the estimate for h and therefore fortuitously produces a result in agreement with equation (26) concerning the dependence of h on v. Other refinements can also be introduced. A Froude number. C. There is evidence that the latter estimate is better under typical laboratorv conditions and that buoyancy ceases to dominate only at burner dimensions below about 1 mm if v 10 cmjs (that is. Fr = u’/(ag) (where g denotes the acceleration of gravity). The analysis leading to equation (26) corresponds to setting 6 equal to the exit velocity v. If Fr is sufficiently small (for example. typically strongly turbulent.* The result of equation (26). buoyancycontrolled flames. then we obtain t Jh/g and h ga4/DZfrom the starting expressions for h and D. a. Roper. Assumption 1 deserves special mention because buoyancy forces on the hotter. are available for b + co under buoyancyinfluenced conditions with negligible viscous forces [9][11]. where A p is a representative density difference and p a mean density). C & F 29. is a Pecletnumber (Pe) dependence that cannot be correlated with Fr and that N  holds in a “momentumcontrolled’’ regime that occurs for sufficiently large values of Frfor example. for a planar. 3. I7 gt A p / p g t (roughly). For these situations. and A.219 (1977) and F.          . where I7 is an average velocity of the element. then the flame heights are controlled by buoyancy. twodimensional slot burner of width a in the open atmosphere. where h is the flame height and 3 IIZ 5 *. C. 227 (1977)l that one further aspect of the physics must be considered. it has been suggested by Roper [see F. If. an estimate for domination by buoyancy is applied. G. G. then surprisingly results in for conservation of fuel mass in axisymmetric flow. Thus buoyancy usually plays a significant role in coflow laminar diffusion flames in the laboratory. Associated with the change in v is a change in flame width. and D .7. namely. however.46 Diffusion Flames and Droplet Burning for the transport of fuel and oxidant to the flame to occur principally through radial diffusion. a. measures the relative importance of inertial and buoyant forces. roughly. then dimensionally D a2/t and h fit. Fr 2 1). For example.Imposition of a condition a%. In other configurations the cancellation does not occur. Comments on the formulation and the analysis All the assumptions of Section 1. Fr < A p / p . the reader may use these methods to derive h vaZ/Dfor the planar for D the ~)” buoyancy~ analog of the analysis underlying equation (22) but h ( v ~ ) ~ ~ ~ / ( g dominated flow. C & F 29. for example. at sufficiently large u. the product pD may be assigned different values in the fuel and oxidizer regions. Correlations of measured flame heights in the form h/a Fr”. Assumption 4 can be eliminated at the expense of additional analytical complexity. laminar. giving D ii2/t.
The result. there are many properties of turbulent diffusion flames that cannot be predicted well by a simple approach of this kind (see Section 10. is the critical value of Re above which the flow becomes turbulent (a geometrydependent value perhaps on the order of 2000). with h/a approximately independent of o or a [12]. The Flame at the Mouth of a Tube in a Duct 47 If u becomes too large. a situation that often is encountered in practice). This flameheight behavior may be obtained from the present analysis by replacing D by a turbulent diffusivity that is assumed to be proportional to the product ua. If temperature or product concentrations are desired. Since increasing a increases Re and decreases Fr. which becomes h/a = (ua/D)(l + v)/4v if hD/ua2 is large (that is. By putting y = 0 and 5 = 0 in this formula. The nature of the boundary conditions makes it unnecessary to study the temperature. and c(cp. the flame fluctuates rapidly and on the average is thicker. a range that vanishes if a 2 (Re:ji2/gpAp)’13. The burning of a fuel jet issuing into an infinite oxidizing atmosphere may be viewed as the limit as b + 00 of the problem formulated here. 4’C’ 0 obtained with co = ccp. Many experiments and some analyses [13] apply to this limit.4).+ . / 5u5 Re.for example. by solving equation (149) for PT and Pi with a1 = aF. there is a critical value of a above which the flow in the momentumcontrolled regime always is turbulent. If Re. The laminar analysis is justified best for relatively small laboratory flames. (? + v)/(l + v) = J nu ~J. in terms of the known fuel or oxidizer fields. Turbulence occurs in most practical burners and introduces qualitative differences from the present predictions. However.1. to derive the solution from equation (22) by investigating the limit in which c + 0 with </c and q/c2 held fixed. then the ratio of inertial to viscous forces (characterized by a Reynolds number.(o)Jo(w~/c)eW2 do.p/pa.and productconcentration fields when the stated assumptions are adopted. Although the it is an interesting exercise problem may be formulated directly with b = a.3.) + nc + do. then the analysis that has been given here is justified roughtly for .2). Large flames often encounter turbulence already in the buoyancycontrolled regime and pass into the momentumcontrolled regime under fully turbulent conditions. we obtain an integral expression for the flame height. Re = pva/.ii. Temperatures at the flame sheet calculated in this way usually are too high (see Section 3. where ji is a representative average value of the coefficient of viscosity) becomes large enough to cause the flow to be turbulent. .cp. It may be observed that only the fuel and oxidizer concentration fields have been considered in finding the flame shape. if v 4 1. is the same representation that would be found by applying a Hankel transform to the directly formulated problem with b = a. they may be calculated a posteriori.
the walls of which are coated with carbon.1 Definition of the problem There are many chemically reacting flow processes in which. analyzing more complex surface reactions.3. fall within this category.2. Present research is directed toward enlarging the class of soluble flow configurations. processes of this type represent a degenerate kind of diffusion “flame” that is comparatively easy to analyze because the location of the “flame sheet” is known in advance. Similar problems are treated in [14][23].2. 3. oxygen . as well as all heterogeneous processes whose basic mechanisms are treated in Section B. oxygen). Let us consider a rectangular duct (with sides of lengths a and b in the x and y directions. The nature of carbon combustion Carbon combustion is an interesting illustration of gassolid reactions [24] and also is relevant to the practical subject of the combustion of coal [ZS]. For carbon there are a number of complexities that affect the simplifications applicable in models and.2.6).48 Diffusion Flames and Droplet Burning 3. since later stages of coal combustion. and through which oxygen is passed with velocity u (in the z direction). THE OXIDATION OF CARBON AT THE WALLS OF A DUCT 3. following devolatilization. (28) We wish to determine the distribution of the mass fraction of oxygen ( Y ) through the tube when the mass fraction at the inlet (z = 0) is Y = Yo. limit the range of utility of equation (28). In one sense. sublimation of solid carbon becomes nonnegligible at atmospheric pressure. At temperatures above 4000K. + 2co. For illustrative purposes. At lower temperatures. we shall briefly discuss a very simple example. Detailed studies of the burning of solid fuels often reveal complexities peculiar to the fuel. the last four of which constitute fairly comprehensive reviews of the subject. the reaction takes place only at interfaces and no flame appears in the gas. The oxygen will be assumed to react instantaneously at the walls according to the process 2 c + 0 . respectively). mainly involve carbon burning.2. including effects of simple homogeneous reactions and exploring peculiarities of convectivediffusive interactions. carbon) and the surface recombination of various dissociated species (for example. The nature of carbon combustion depends strongly on the temperature of the fuel. for example. Specific examples include the oxidation of some solid fuels (for example. as illustrated in Figure 3. under certain circumstances.4. The entire field of heterogeneous catalysis (see Section B.2. and gasphase combustion processes may be important.
but data obtained by different authors differ. and the other CO. one of these reactions produces CO. A number of complications lead to differences in experimental results. One viable alternative (developed by Ubhayakar in unpublished work) involves only one type of adsorption site. + 02. A number of different theories have been qualitatively successful [27][31].2..3.) at a finite rate. with the sites being interconvertible ( S l f S. Diagram of a rectangular duct with carbon oxidation occurring at its walls. a different finiterate reaction occurring subsequent to each type of adsorption. there are different structural types of carbon that have been studied. but it is unclear that any of them are fundamentally correct. S. The Oxidation of Carbon at the Walls of a Duct 49 c Velocity=v IInss fraction of o2 = Yo FIGURE 3. These include amorphous carbon (typically randomly oriented graphite crystals) . There are other alternatives (for example [30] and [31]). followed by a minimum at a temperature a few hundred degrees above that of the maximum. be adsorbed. but two types of equilibrium adsorption with of oxygen. [32]. the overall rates obtained are not of the simple Arrhenius form but instead usually exhibit a maximum in the rate of carbon removal at a surface temperature between 1200K and 2500K. The surface chemistry responsible for the interchange between C 0 2 and CO as products is uncertain. The rate constants and activation energies for the elementary steps differ for the different schemes.. and S.3. at temperatures below about 800K and CO at higher temperatures [26]. S. The primary product of this surface reaction is CO. [33] seems popular. one corresponding to S. it involves two types of adsorption sites. Each of the predictive schemes agrees with at least one set of experimental data. Aside from possible catalytic influences of impurities in the carbon. + O2 and the other to 2S. on which equilibrium adsorption and finiterate reaction of oxygen occur (at different rates). and react there. Thus equation (28) can be a good approximation only if the surface temperature of the carbon is between about 800K and 4000K (we shall see that there are additional restrictions). may diffuse to the carbon surface. The StricklandConstable scheme [29].
chemical kinetics in the gas can influence the carbonburning rate. composition. there are a variety of different regimes of carbon combustion. geometrical configuration. at a flame sheet in the gas and CO.3. The occurrence of this diffusioncontrolled regime is well established for carbon combustion [3 11. Analysis For simplicity. The following analysis applies in a particular regime. from occurring before oxygen reaches the solid surface. + 3. and oxygenrich atmospheres at pressures on the order of atmospheric. From this discussion it may be seen that. + CO. [41]. [44]. may occur [39]. if the reaction rate at the surface and the gas pressure are high enough.50 Diffusion Flames and Droplet Burning and pyrolytic graphite (a highdensity. An alternative to equation (28) is a model in which CO )O. [41].3 are not necessary here because we are studying a binary. At lower temperatures. but 0. lowspeed flow. nonreacting gas mixture and are not considering . [40]. pressure. The following analysis will be restricted to this limit. The rate of oxidation of carbon by COz is so slow that this alternative seems reasonable only for fairly high surface temperatures and fairly low oxygen concentrations in the gas [41]. for laminar flows with relatively short residence times in small ducts with dimensions on the order of centimeters.4. Pore diffusion is seldom ever significant for pyrolytic graphite. typically with surface temperatures on the order of 2000K. There are models that show how pore diffusion tends to reduce measured values of overall activation energies [26].2. rates of diffusion of oxygen into pores can influence burning rates of porous materials. Amorphous carbon often tends to be porous. and assumptions 14 of Section 3. Uncertainties remain concerning influences of gasphase chemistry [44]. [43]. At sufficiently high temperaturesfor example.2. appreciably lower gas temperatures. may react with CO in the gas to form CO. 0 atoms are appreciably more reactive than 0. Equation (28) requires that residence times in the gas are short enough to prevent chemical depletion of 0.3. Even when the reaction rate at the surface is effectively infinite. [34].1. The other assumptions in Section 1. the hypotheses of steady. which ceases to apply if the dimensions of the carbon materials become too small [39]. [36]. if the residence time is long enough [43]. depending on the conditions of temperature. anisotropic carbon with distinctly different characteristics of base and edge planes). above about 3500Ka substantial amount of dissociation of 0. + C + 2CO at the carbon surface [39]. and gas velocity. then the burning rate is controlled by the rate of diffusion in the gas. An average of these rates would be relevant for most combustion processes. [45]. we shall again employ assumptions 15 of Section 1. but oxidation rates differ appreciably on the base and edge surfaces [35]. [37][39]. molecules on carbon surfaces [42]. As is seen in Section B. oxygen dissociation is unimportant.
)I. at the walls of the duct). [23]. This last condition follows directly from an analysis in the spirit of Section B. . It is also found that the most severe approximations of Section 3.2 (that is.2). assumptions 1 and 2) can be avoided in these relatively elementary problems [16]. equation (144) is valid for CI = Y and with w = 0. and that Y = 0 at x = 0. for example. subject to the given boundary conditions.3 (and with assumptions 14 of Section 3. In the Cartesian coordinate system shown in Figure 3. At large distances from the entrance to the duct ( z + co). we shall not introduce such refinements in the present illustrative treatment.+ By the method of separation of variables.2.1. .3. The reader is referred to cited reviews for interesting fluidmechanical ramifications. For recombination processes.* however. the concentrations of the reactant on the surface and in the gas phase adjacent to the surface both approach zero. and y = b (that is. In general. equation (30) becomes Y = (:)2Yo sin(:)sin(y)exp[  ($ + (31) which shows that the initially uniform concentration profile assumes the shape of a half of a cycle of a sine wave and decays exponentially with the decay length . is found to be (2m m=O + 1 1)(2n x sin[ (2n + 1)ny ]exp{  [ + 1) 2m + 1 ( y ) 2 + ("b+l)2]~2(:)z}. Systems with finite surface reaction rates have been studied in [19] and [20].)( . the solution to equation (29).1. x = a. The Oxidation of Carbon at the Walls of a Duct 51 the temperature field. that Y = Yo at z = 0. [20]. (30) Equation (30) gives the desired oxygen concentration field. Under the stated assumptions.4. * Boundarylayer theory (see Chapter 12) can profitably be utilized to provide more accurate results in many of these problems. the boundary conditions for equation (29) become nonlinear in Y when the surface rates are finite. and steps 1 and 5 of Section B. as the specific rate constant for the surface reaction approaches infinity. y = 0. the limit of an infinite surface rate constant is usually referred to as the case of a perfectly catalytic wall. ) R ' ( . ) Z ] .( + . in the steady state. this governing equation reduces to The boundary cdnditions for equation (29) are that Y is bounded.4 (the diffusion transport steps) become rate controlling.
[61] of different . Condensed products may accumulate on the surface of the particle. practically always exhibit burning mechanisms influenced by product condensation. at the outset it is of interest to indicate some of the complexities that may arise in other situations. Carbon is an example of a nonvolatile solid fuel with volatilein fact gaseousreaction products. The last of these processes may be enhanced by thermophoretic motion (see Section E. although boron is less volatile than B. Here we shall consider one of the simplest situations. producing gaseous products that flow and diffuse to infinity.1. this oxide is sufficiently nonvolatile for its liquid phase to play a role in the combustion of boron particles under many circumstances [54]. To present analyses of these phenomena is beyond the scope of the discussion here.03. [48][53] are analyses of extinctions that occur in cool ambient atmospheres when the particle becomes sufficiently small [49]. Relatively volatile fuels with nonvolatile combustion products.5) of fine particles away from the hottest reaction zone under the influence of the temperature gradient [SS]. reactions tend to occur on the surface of a carbon particle during combustion. If reaction products are less volatile.3. In the presence of product condensation. [52].3. [Sl]. Background and definition of the problem A variety of phenomena are exhibited by the burning of a spherical fuel particle in an infinite oxidizing atmosphere. The relative volatility of the fuel and its oxide has an important influence on the combustion mechanism of the particle [47]. investigations of conditions for ignition of a particle by a hot gas [Sl]. may accumulate in a shell at a reaction sheet located at some distance from the surface of the particle. [41]. [53] and calculation of combustion oscillations associated with diffusion of oxidizing gas into the interior of the particle. the quasisteady.2. However. THE BURNING OF A FUEL PARTICLE IN AN OXIDIZING ATMOSPHERE 3. there are a number of possible modes of quasisteady burning. such as magnesium and aluminum. Law’s models [60]. Many theoretical analyses of the various types of combustion processes have been published [55][62].52 Diffusion Flames and Droplet Burning 3. as indicated in the previous section. spherically symmetrical burning of a liquid fuel that vaporizes and reacts in a gasphase flame. Because of the diversity of hightemperature oxidation mecanisms of solids [24]. may accumulate in a shell at a condensation sheet located outside a thin primary gasphase reaction sheet. [46]. followed by internal chemical reactions [48]. then their condensation can influence the combustion mechanism. Among the recent theoretical studies on the burning of carbon particles that go beyond the computation of steady rates of burning [39]. For example. these complexities often are associated with the burning of solid fuels. or may flow and diffuse to infinity in the form of fine particles. therefore.
Diagrams of experiments on the burning of a fuel droplet in an oxidizing atmosphere. there is room for much additional work. droplet burning in freely falling chambers on the earlh has been studied [64][69].3. (a) Porous sphere.4).) FIGURE 3. their diameters do not attain quasisteady values during the testing time [67]. A method for performing this most ideal experiment has not yet been devised. fuel has been t (a) (b) motion (. toward ascertaining the physical reason for the occurrence of one burning mode rather than another or toward inclusion of thermophoretic effects. . The maximum test times achievable in these experiments are on the order of 2 s. The absence of gravity is significant because buoyant forces distort the shape of the flame significantly. Liquid fuels with gaseous products do not share these complexities in their combustion mechanisms. for example. directed. The most ideal experiment in liquiddroplet combustion would be the steadystate. insufficient for the complete burning of droplets with diameters on the order of 1 mm or larger. In part (a). unless the fuel particle is very small. Although this experiment has not yet been implemented.4. through a porous. (c) Falling droplet. Irrespective of whether a freely falling chamber is used. which have not yet been studied in the context of particle burning. internally supplied with fuelfor example. A conceptual design that most closely approximates this ideal involves the quasisteady burning of a free droplet in a laboratory in space [63]. Nevertheless. The Burning of a Fuel Particle in an Oxidizing Atmosphere 53 classes of combustion mechanisms provide a simplified but relatively accurate and useful framework within which many processes of combustion of metal particles can be placed and from which burning rates and flame locations may be obtained.3. although spherical flames have been established. (b) Suspended droplet. three different experimental techniques have been devised for studying the burning of a fuel droplet in an oxidizing atmosphere (see Figure 3. spherical support in a gravityfree environment. spherically symmetrical burning of a liquid sphere.
= riz d f o . freely falling fuel droplets have been ignited and observed during burning [82]. Spherical symmetry is the primary simplifying hypothesis that will be adopted in the following discussion. [Sl]. Successful analyses were first presented in [71]. as was observed by Sreznevsky [lo41 and explained by Langmuir [l05].3 will be adopted.3 that merits special mention for this problem at the outset is the hypothesis that steady conditions prevail. Each of the techniques possesses certain intrinsic advantages over the others. which is called the evaporation constant. and [107].54 Diffusion Flames and Droplet Burning supplied internally to a stationary porous sphere at a steady rate. [lOS]. There . In part (c). df. the square of the droplet diameter decreases linearly with time . (33) where df is the droplet diameter. for example. [72].o is the value of df at t = t o . An assumption of Section 1. 3. and K . [81][92]. (32) where rf is the radius of the sphere and K' is independent of r l . salient features other than the flame shape [for example. (a) is steady. these analyses are discussed in textbooks [l]. Later it will also be assumed for simplicity that the flow variables (in particular. The theoretical model of the burning droplet is illustrated in Figure 3. t is time. and (c) is applicable to very small droplets.3. and comprehensive reviews are available [l09][115]. In experiment (a) it is observed that the total mass per second that must be supplied to the sphere in order to maintain steady burning is K'rf. and the rate of decrease of the diameter of the droplet has been measured after ignition [65]. In experiments (b) and (c) it is found that after an initial unsteady period. and all the assumptions of Section 1. The dsquare law in equation (33) also expresses the relationship between diameter and time for vaporizing droplets in the absence of combustion. small.to). The chemical reaction will be assumed to be described by equation (l). namely.5. Some of the objectives of theoretical analyses of droplet combustion have been to derive equations (32) and (33) and to predict observed flame 'shapes and temperature and concentration profiles. In part (b). [106]. equations (32) and (33)] are found to be predicted with good accuracy by analyses that postulate spherical symmetry. [93][103].2 Assumptions Although the shape of the reaction zone surrounding a burning droplet is not spherical in most experiments. temperature) are constant inside the droplet. is independent of t. which is just sufficient to maintain a liquid film on the surface of the sphere during burning [70][80]. (b) yields accurate resultdor the diameter as a function of time.df = K ( t . Departures from the main assumptions will be discussed subsequent to the analysis. fuel droplets have been suspended on stationary quartz fibers.
5. at best quasisteady conditions can be attained. near critical conditions the strong dependence of the diffusion coefficient of the fuel on temperature can aid in establishing an approach to quasisteady conditions in the fuelrich zone for situations under which quasisteadiness otherwise would not be expected.a (pd * In highly supercritical regimes.3. however. A theoretical study of these two effects is presented in [I 161. The Burning of a Fuel Particle in an Oxidizing Atmosphere 55 cs Droplet FIGURE 3. the fractional error is somewhat less than the ratio of the gas density to pd. is required when the liquid is above the critical point [I 19][124]. [llS]. An entirely different treatment. . Model of the burning of a fuel droplet in an oxidizing atmosphere is little doubt of the validity of this assumption for experiment (a). = 2r.) of the droplet. in which steadystate conservation equations determine the mass per second leaving the droplet (h). in agreement with a number of experimental observations [93]. The theoretical predictions of [1191[124] are in qualitative agreement with experimental observations in [77].3. [SS]. the initial unsteady ignition period may conceivably occupy the entire lifetime of the droplet. in experiments (b) and (c). overall massconservation condition = liquid density = constant) determines the rate of change of diameter ( d . one which is basically unsteady.after which the simple. Conditions of criticality may be attained in diesel and rocket combustion. [117]. the combustion process resembles diffusion of a gas from a point or distributed source. the quasisteadystate approximation [employing equation (34)] leads to a slight overestimate of I dr. Second. During the remainder of the burning time. which becomes appreciable only as the liquid approaches its critical point./dt I . since the size of the droplet is continually decreasing with time. and [92] made near the critical point. First. The ignition period usually is predicted to occupy less than 20 % of the total burning time. there are two reasons for questioning the assumption.
3. and (35) can be used to express the evaporation constant K in terms of the proportionality factor K’. d: will vary linearly with t). which explicitly shows that if equation (32) is satisfied (that is. The burning rate rcZ is found to appear as an eigenvalue of equation (149) and will be obtained by applying equation (149) to PT with c( f C I ~ . namely. (33). In terms of the dimensionless independent variable equation (39) becomes the solution to which is . (37) where r is the radial coordinate and u is the radial velocity. K =  (35) 2m/Xpdrl = 2K’/~pd: (36) Equation (36) determines K from the results of the following steadystate analysis.3. the overall continuity equation. a steadystate theory that leads to equation (32) automatically yields equation ( 3 3 ) through the quasisteady hypothesis. Analysis predicting the burning rate In a onedimensional. Equations (32). 3. Employing the expression for the divergence in spherical coordinates. spherically symmetrical system. can be written as ri? = 4nr2pu = constant. Therefore. ri? rJ. we find that equations (1 45) and (149) give which reduces to dr dr (39) when use is made of equation (37). equation (123).56 Diffusion Flames and Droplet Burning Equation (34) can be written in the form d ( d f ) / d t = 2m/Xpdr[. then equation (33) will also be satisfied (that is.
The analysis requires modification for these systems (see Section 3. [4nr2A(dT/dr)] + = riZL. The explicit derivation of the interface condition on T from equation (161) is somewhat more lengthy. for the fuel.= 0). and product species. = . It is clear on physical grounds that when the temperature of the droplet is constant and uniform.3. Equation (42) is the solution for the profile of any coupling function p. and employ the massconservation conditions. and (l)]. The corresponding constants A T and BT in equation (42) with p = PT are determined by the boundary conditions for the temperature and for the mass fraction of oxidizer. . Using equations (139) and (40) in equation * Radiative heat transfer is not negligible for liquids with high boiling points or for opaque droplets with highly luminous flames.= 0.6). dT/qo + Yo/Wo~o. which must be discussed separately for each coupling function. Yo. use ( V T ) . oxidizer. that is. yields the boundary condition (GO/dO.. The values of A and B depend on the boundary conditions. 1 > (46) where use has been made of equations (37) and (40) and the subscript 1 identifies conditions in the gas at the droplet surface. (47) where L is the heat of vaporization per unit mass of the fuel at temperature ?. one must neglect the radiation* and kineticenergy terms. If the subscripts + and .pWdYo/dr)I+ = 0 7 (45) since there is no oxidizer inside the droplet (that is. Equations (161) and (162) provide conditions on T and Yo that must be satisfied at the surface of the droplet.refer to conditions outside and inside the droplet. equation (162).yo.3. the amount of heat conducted into the droplet must be just sufficient to vaporize the fuel leaving the droplet.3.= 0 and Vi. N2 (43) where the standard heat of reaction at temperature T o is 4 ' h i WFVF + h$ WoVo  hywvi i= 1 (44) [see equations (146). which merely states that the net mass flow rate of oxidizer at the surface of the droplet is zero. Equation (45). then equations (137) and (162) give [POYO .~10= 6 C . 51 where A and B are constants. The Burning of a Fuel Particle in an Oxidizing Atmosphere > . respectively. The coupling between the temperature and oxidizer concentration profiles is determined by the function PT c(T . In order to obtain equation (47) formally from equation (161). (147).
By eliminating A T between equations (52) and (53). wo voyo. appear in equation (48). m  1) (55) Hence. equation (43) implies that N i= 1 1yi. and taking the arbitrary standard reference temperature to be T o = 7. (54) In view of the meaning of cp dT (see Section 1. . then additional terms involving (d&'dr). An expression for the burning rate can now be obtained from equation (42). where (52) Evaluating the same equation at we find PT. it is found that BT = ( P T . we obtain PT.m < = 0 [see equation (40)]..f) + BTer'.1 (49) In view of equation (42).. utilizing equation (50) in equation (54) shows that * If this convention is not adopted. equation (49) shows that where a dimensionless burning rate is [see equation (40)]. (53) = AT + BT.58 Diffusion Flames and Droplet Burning (47). 4O i d~ PT. m lT?cp.3) and our convention T o = 7. co.  PT.* we obtain the boundary condition Equations (46) and (48) determine the gracfient of PT [equation (43)] at the surface of the droplet in the gas in terms of L and Yo. thus.f = + (Yo. m  PT.I . L Yo.I =AT Y = + B. for convenience. When equation (42) is applied to PT and evaluated at r = r l .e<'.
in the quasisteady state depends on the nature of the surface gasification process. through numerical integration of the conservation equations or through asymptotic analyses of the type indicated in Section 3. The Burning of a Fuel Particle in an Oxidizing Atmosphere 59 The fact that equation (56) is an expression for the burning rate can be seen from equation (5 1). forgaseous reactants per unit mass o are all fundamental thermodynamic properties of the system and therefore . The remaining parameters. The surface process may conceivably be a rate x. in general. at temperature 7. values of Yo. equation (57) is of more general validity than the burning rate expressions usually quoted because arbitrary temperature dependences of (pD) and c p are permitted in equation (57).(L)and the quantity 4O/WOvo.4. Discussion of the burningrate formula In many respects. . and the factor preceding the logarithm. since nearly all of the dropletburning studies it is assumed that Yo.l near extinction conditions (Section 3. The value of 7. and the flamesheet approximation has not been introduced. to prescribed values. = 0 (there are presumed to be known. The specific heat at constant pressure for each pure species i(cPJ the heat of vaporization per unit mass for the fuel at temperature T.l are found to be less than 1OP2. which is the heat of reaction f oxidizer consumed. all the oxidizer is consumed instantaneously at the spherical surface where the reaction rate (per unit volume) is infinite.. However.Jn the flamesheet approximation. In dropletburning experiments. In most = 0.3. It is generally quite accurate to put Yo. [126].4. 7. 3. The value of Yo. depends on the reaction rate and can be determined.3.3.l. equation (57) will be useful for computing rit only if all quantities appearing on the righthand side of this equation are known. Yo. in dimensional notation. is no fuel in the ambient atmosphere). oxidizer and products and the temperature T. Yo. The validity of this assumption has been investigated by numerical integrations [lo71 and by asymptotic expansions for small values of the ratio of a reaction time to a residence time [125]. YF.4). and Yo = 0 inside this surface (hence. in par= 0 except very ticular.! = 0). and an experimenter who controls the for the atmosphere in which the droplet burns can adjust the quantities .l oxidizer is expected to be consumed before diffusing to the surface of the droplet. require more detailed discussion. thus.
3 are so large (for example. showing that riz r l . except for fuels that undergo surface or condensedphase chemical reactions. 7. = % (% E boiling point of the fuel) is a good approximation.e. However. such as depolymerization of polymeric fuels. 7.* The application of this equilibrium condition entails obtaining the coupling between the fuel and oxidizer concentration profiles (i. for example. and the factor preceding the logarithm becomes 4npDrI.3 for a more complete discussion of surface conditions. . the heat flux to the droplet surface is large enough to lead to equilibrium droplet surface temperatures that are only slightly below the boiling temperature of the liquid (see. Often p D = constant is an acceptable approximation. is not immediately apparent. since Le = 1 [see equation (139)]. riz rJ(1 + arl).60 Diffusion Flames and Droplet Burning process. [116]). These approximations will be considered further in subsequent discussion. The results of the preceding discussion can be summarized by means of the approximate formula   This expression agrees with the empirical relationship given in equations (32) and (33) and can be used in equation (36) to determine the evaporation constant. Thus the surfacetensioneffects are purely mechanical. the rates at which molecules of fuel enter and leave the liquid are sufficiently i commonly rapid to maintain surface equilibrium for the low values of t encountered in droplet burning.’it can be shown from equation (57) that for small changes in r l . Therefore. the variation of m with T I . However. and 7.i= c p = constant is reasonably accurate. unless the heat of reaction is extremely low or the fuel is extremely nonvolatile. See Section 7.. aiding maintenance of spherical symmetry. and for many systems. The quantity p D can be replaced by A/cp. When p D is independent of r in the vicinity of r = rl. predicted by equation (57). Experimental observations of the burning of single droplets small enough to exhibit this type of influence of surface tension would be difficult to obtain and have not been reported.go). Since the factor preceding the logarithm in equation (57) is influenced by the dependence of p D on r. solving for /IF = uF . is determined by the thermodynamic (phase equilibrium) condition that the partial pressure of the fuel at the surface of the droplet must be equal to the equilibrium vapor pressure of the fuel. that riz depends logarithmically on the heat of reaction and the heat of vaporization and that riz is insensitive to the pressure and is not strongly influenced by the temperature. greater than 10 p in diameter) that effects of surface tension on phase equilibria are negligible.4 would be required in order to determine 7. Therefore. Equation (58) shows that the principal dependence of m on the properties of the fluid is expressed by ri2 A/cp. would be found to depend explicitly on yiz. the approximation cp. where a = constant and usually lurll 4 1.  * The droplets under consideration throughout Section 3. in which case an analysis analogous to that given in Section B..
m w F v F / w O v O ~ YF. cx0 = . From equation (61). the flamesheet approximation must generally be employed as a first approximation if numerical integrations. The Burning of a Fuel Particle in an Oxidizing Atmosphere 61 These results are in agreement with experiment.6 are in qualitative agreement with the results of numerical integrations for reasonable chemical reaction rates [1071and with experimental results [SO]. Theoretical and experimental values of the e4aporation constant K are roughly of the order of lo* cmz/s. 3. other results can be derived without explicitly invoking the flamesheet approximation. Predictions of other characteristics of burning droplets Since equation (42) is valid for any coupling function B. 7 (59) and by using equations (45) and (56) and the surface conservation condition for fuel.1.idT) +(~OyO.p F and aT = PT = PT + / j F for r > r c . are to be avoided. For example. which can be combined with equation (56) to show that + .3. a. by considering /3F c(F  =  YF/WFVF + Y~/Wovo. denotes the total mass fraction of products.~/wOvO)  provided that YF. = 0 and ctT = PT for r < rc. [ P v y F . WFvF/wo~o. Representative profiles are shown in Figure 3.6. then ctF = P F .3.PD(dYF/dr)l + = (Pv>+ it can be shown that the mass fraction of fuel in the gas at the surface of the droplet is L[l + yO. If quantities at the flame surface are identified by the subscript c.i = 1 > (60) + i = 1 ( x . = 0. where Y. (61) just as in Section 3. However. In many respects curves in Figure 3. it can be shown that the value of 5 at the flame sheet is determined by e<c = I Yo. while aF = 0. m JT:cp.3. In the flamesheet approximation. in order to obtain explicit temperature and concentration profiles and to locate the reaction zone.5. These observations serve to determine the fuel and oxidizer massfraction profiles and the temperature profile through equation (42). = 0 and Yo. the position of the flame is determined by B F = O.
in equation (58) the logarithmic term is ln(1 + B). This may be accomplished by introducing the transfer number B. qualitatively representing the ratio of an impetus for interphase transfer to a resistance opposing the transfer. in droplet burning the factor ln(1 + B) always appears in the expression for the burning rate. predicted by equation ( 6 2 ) is larger than that typically observed by roughly a factor of 2.2.6.62 Diffusion Flames and Droplet Burning 4 FIGURE 3. [127]) lead to the logarithmic term in equation (57) being identified as ln(1 + B).3. empirically. 3. Generalizations in the definition of B (for example. gasphase . Temperature and massfraction profiles for a burning fuel droplet in the flamesheet approximation. These phenomena ofen are too complex to be included in accurate theoretical burningrate analyses and necessitate semiempirical methods in deriving burningrate formulas. it is of interest to write the results that have been obtained in a simplified notation.l = 0 and pD = constant. From the viewpoint of energetics. First.3. such as for the problem discussed in Section 3. Because of the effects of natural convection in dropletburning experiments. the value of the flame radius r. Further realities of droplet burning A number of phenomena excluded by the assumptions given in Section 3. in fact.2 can modify the burning rate of a droplet.r l ) is more nearly independent of rl than is rc/rl for supported droplets with diameters on the order of a millimeter or more. For a vaporizing droplet.6. Hence. The most important of these additional phenomena will now be considered. the sum of the heat released per unit mass of oxidizer consumed and the difference in the thermal enthalpy per unit mass between the ambient gas and the gas at the surface of the droplet comprises the impetus for transfer. (r. The introduction of B can be useful not only in droplet burning but also for all problems involving interphase transfer. when Yo. . while the heat of vaporization L per unit mass of fuel vaporized is the resistance. and.
where Q is the additional energy per unit mass of fuel needed for gasification. then equation (A23) may be employed with p representing the partial pressure of the fuel vapor. for use in equations (63)(65). usually the fuel is not fed into the sphere at its boiling point. this causes equation (58) to become nonlinear in viz and to cease to possess a solution if rl is too large.then the additional requirement in thermal enthalpy is Q = c. Then equation (62) for the flamestandoff ratio becomes dJd. For suspended or free droplets that are not initially at the boiling where t)/h. the product of the stoichiometric mass ratio of fuel to oxidizer with the oxidizer mass fraction at infinity. . A practical concern with poroussphere experiments is that a significant amount of energy may be transferred to the liquid fuel from the flame that bathes the fine feed line [90] . and &. the quantity L in the denominator must then be replaced by L + Q.G). for example]. the mole fraction X F .3.value of 7. If itis of interest to account for the difference between 7. . then in view of equation (E5 l). = ln(1 + B)/ln(l + v). point. .If the fuel surface is at a sufficiently high temperature for the radiant energy lost from it to be of significance. an additional term u~T~/(viz/47tr~) appears in Q . this effectively decreases Q and may cause it to become negative in extreme circumstances. + (63) and it is found from equation (60) that the mass fraction of fuel at the droplet surface is ( B . times the specified hydrostatic pressure. there is a contribution to Q given by ( ~ ) 7 t r ~ p d c l ( d ~ / d [ I : = . F/WFwhere W is the average molecular weight (I7W3'.)/( YF. To write simple formulas it is useful to define v = (vFWF/vo Wo)Yo.v)/(l B). Substitution of equation (58) into equation (36) gives YF. Under these conditions gasification requires an energy L + Q instead of L.I = YF.YF.3. vaporization.I is given by equation (64).m . *).(7.YF.dis the mass fraction of fuel deep in the interior of the droplet (usually unity).I = (64) (65) K = (8/Pd)(&)W + B ) for the evaporation constant. or wetbulb temperature. obtained in this manner is a wetbulb temperature somewhat below &. The. In the definition of B. and a better definition of B is B = ( YF. X F . as is readily verified by a suitably modified energy balance [compare equation (47). X F . In the application to the burning of a porous sphere. where YF. and YF. The Burning of a Fuel Particle in an Oxidizing Atmosphere 63 diffusion of the fuel rather than heat conduction is the main driving force for d .I may be obtained from equation (ll2)namely. If the specific heat of the liquid fuel has the constant value cI and the feed temperature is G.
but there always is a short period. there is an initial period of unsteady behavior throughout the gas. are relatively small. during which d. and quasisteady conditions may prevail throughout the region of importance during most of the burning history. Theory predicts that d. in spherically symmetrical burning. accounting for aspects of gasphase unsteadiness [135] is 1 + [(2/n)(pm/p. The predicted tendency for dJd. the gasphase unsteadiness may be significant [134][136]. M. the flame may lie in the outer zone. there must be an outer region in which quasisteady conditions are not attained. causing d. The possible occurrence of unsteady conditions in the gas phase for free droplets has also received further consideration [1341[136]. in addition to the timedependent outer zone.64 Diffusion Flames and Droplet Burning is the average temperature of the liquid. There have been a number of studies of the heatup process [I 161. For burning in oxidizerrich atmospheres. Thus. Matalon and C. including consideration of influences of convective motions of the liquid within the droplet [131][133].219 (1983). If radiant transfer from the flame or from hot * Further considerations may be found in a more recent publication. If the droplet is moving with respect to the gas. to increase with time and equation (63) to be inapplicable. for burning in dilute atmospheres. Typically. during which there is a quasisteady inner zone and a timeClependent outer zone. subsequent to liquid heatup [135]. K. increases with time [135]. [128][130]. see Section 3. and the flame sheet is initially established closer to the droplet surface than a quasisteady analysis such as equation (63) would predict.4). equation (63) usually predicts relatively small values of d J d . as was indicated in Section 3. Except under somewhat special conditions [133]for example. It is evident physically that since a burning droplet exists only for a finite amount of time. such that the flame sheet lies in the quasisteady zone. under suitable circumstances it achieves a quasisteady value given by equation (63) during most of the burning history. This contribution decreases with increasing time at a rate that increases as the thermal conductivity of the liquid increases. to increase with time is in agreement with experiments [67] on the spherically symmetrical burning of free droplets in the absence of gravity. where pm is the density of the ambient atmosphere. for fuels with high boiling pointsthe heatup typically occurs sufficiently rapidly to be unimportant during most of the burning. However. then this outer zone is swept away from the droplet relatively quickly. This period is usually relatively short. .2. A correction factor to equation (65). Law. and effects of gasphase unsteadiness on d. approaches infinity (unless the flame is first extinguished.)ln(l + B)]'I2.3./d. when ignition occurs there is relatively little fuel vapor in the gas. as the droplet disappears.* The correction to K just cited remains consistent with the dsquare law for the total burning time. and the main influence of gasphase unsteadiness on the burning time and on the flamesheet location typically arises from the later period. However. C & F 50./d.
From equation (116) we see that this introduces a 6function in the divergence of the shearstress tensor at the flame sheet. gasphase [A(dT/dr)]+ in equation (47). and in view of equation (34). it follows from the idealgas law with constant pressure p that the density gradient is discontinuous. Since M is small. The analysis that has been given here relies on the assumption that the Lewis number is unity [equation (139)]. or r. the paradox concerns a small effect. Although there have been a number of theoretical studies that consider Le # 1 and that take into account variable transport properties and specific heats [106]. who showed that there is an adjustment region with thickness of order rcM2 (where M is. The more general theories also are more complex and therefore offer greater resistance to attempts at extracting generally valid conclusions.. [139][ 1421. The paradox has been resolved independently by Sepri [137] and by Cooper and Clarke [138].. except possibly a discontinuity in p at the flame sheet. Effects of variable properties and of Le # 1 are significant in that they can introduce uncertainties in excess of a factor of 2 in K and in dJd. influence fluid flows appreciably in configurations that are more complex (for example. (132) and (133) become good starting equations for an analysis. in turbulent flows)./dt = (qR/pd)/(L+ Q). If Le # 1.. This is evident from the fact that the radiant energy input per unit area at the droplet surface.2) is large compared with the droplet diameter.6 shows that the temperature gradient is discontinuous at the flame sheet. .a Mach number) just outside the flame sheet. The phenomenon provides one mechanism for combustion to affect the fluid dynamics.5. according to equation (37) the velocity gradient is discontinuous.is independent of d. this gives dr. which may. p experiences a discontinuity in its gradient at the flame sheet and then decreases by a fractional amount of order M2 through the adjustment region. say q R . however.2qR = yiz(L Q ) in a radiationdominated situation. which would contradict the original hypothesis of constant p . The dsquare law may be viewed as arising from the fact that the conductive input flux. A few relevant principles have been identified and deserve to be discussed here. such as hot chamber walls.3. a dlaw. since then the flux fractions t i remain constant on each side of the + . then the dsquare law becomes a dlaw for the usual situation in which the Planckmean absorption length of the gas (Section E. A simplified energy balance for the droplet is 47cr. Equations (131). Since Figure 3. An interesting paradox is posed by considering momentum conservation in connection with the flamesheet approximation. then a formulation on the basis of coupling functions is less convenient. especially if the flamesheet approximation is adopted. in fact. questions remain concerning these effects. is inversely proportional to Y gradients steepen as the droplet size decreases. therefore.3. and from equation (120) it is evident that there is nothing in momentum conservation that can balance this divergence. The Burning of a Fuel Particle in an Oxidizing Atmosphere 65 surroundings. becomes a dominant source of energy input to the droplet.
then in this formula the theoretical undissociated flame temperature is best used in calculating B . The arithmetic mean of the flame temperature and the boiling temperature may be used for this purpose [90]. and heat conduction merely provides a loss mechanism that decreases (or increases) the flame temperature.the energy of . [114]. a procedure that clearly burning in airto employ c is entirely unjustified if Le # 1. In contrast to the relevant heat capacity. reasonable agreement with experiment is achieved by use of the c.66 Diffusion Flames and Droplet Burning flame. if a formula for B is employed that explicitly contains a flame temperature instead of a standard heat of reaction qo. Inside the flame.4 times that of fuel . These equations. Since A and c perature must be selected at which these properties are to be evaluated for use in equation (65). equation (58). the largest effect. or simplifications thereof. The thermal conductivity outside the flame is of secondary importance and the diffusion coefficient of the fuel vapor is practically irrelevant. the only . 0. evident from equation (133) and also physically clear. typically species transported in that region. for fuel if suitable procedures are adopted for evaluation of transport properties [90]. in equation (65) should be that for portance in controlling burning. that of heat conduction between the flame and the droplet.6 times that of air [90]. for example. outside oxidizer diffusion is dominant. the c the fuel vapors (and possibly their gasphase pyrolysis products). [142]. vary with temperature. a templus 0. This conclusion would be correct only for Le = 1 and would tempt onefor example. As a first approximation. For burning in air. for . A result. have in fact been employed in a number of the theories [106]. would suggest that an average specific heat of all species present in the gas is more relevant. is that a species i must be transto play any role in the quasisteady ported (ti# 0) for its specific heat cp. depending on whether the Lewis number outside is greater (or less) than unity.. In calculating the flame temperature for this evaluation. Although the resulting value of c is larger by a factor of 2 than that obtained from other prescriptions. In this respect the couplingfunction theory can tend to be misleading. heat conduction is a dominant process and fuel diffusion is selfadjusting. all species present contribute to the thermal conductivity. When Le # 1 it is found [140] that the main transport properties affecting the burning rate are (1) the thermal conductivity in the region between the flame and the droplet surface and (2) the diffusion coefficient of oxidizer in the region outside the flame. equilibrium dissociation should be taken into account. for nitrogen in A/c. [142] with good results. O n the other hand. the A in equation (65) may be taken as an average of that of the fuel vapor and air. may be employed for evaluating the burning rate through use of equation (65). It has been reasoned [90] that since processes occurring between the flame and the droplet surface are of greatest im. These influences can be reasoned physically.i combustion. since the unrealistically high temperatures often obtained when dissociation is neglected are clearly irrelevant to realistic property evaluations.
relative to the droplet. Frossling studied vaporizing droplets without combustion and where Sc is the Schmidt number found that K / K o = 1 + 0. The prescriptions that have now been given enable equations (63) and (65) to be employed with reasonable accuracy for spherically symmetrical burning. (Appendix E). The Burning of a Fuel Particle in an Oxidizing Atmosphere 61 dissociation is largely recovered in the cooler parts of the flame and therefore is available for driving vaporization. Effects of forced convection at small convection velocities have been studied [143]. U P (66) where p and p are the density and viscosity of the gas and u. Re is the Reynolds number. equation (68) may be used with AT taken as the difference between the flame temperature (with dissociation) and the ambient temperature to calculate K . Forced and free convection introduce departures from spherical symmetry that modify burning rates and flame shapes. where KO is given by equation (65). Burningrate corrections for free convection depend on the Grashof number. [147] appear to remain as good as any currently available for forcedconvection corrections. [96]. Thorough theoretical analyses for nonspherical situations are not yet available because of the complexity of the problem. the ambient gas composition. With the prescription that has just been given for evaluation of the average temperature T and the average properties p and p. In equation (67). is the gas velocity far upstream. the range of practical interest. it seems reasonable [148] to replace Sc by the Prandtl number Pr (see Appendix E) in the Frossling formula to obtain K = KO(l + 0. and ideas for corrections extending to large convective velocities have been considered [72].276Re'i2Pr1i3) (67) for droplet burning in forced convection. Within the accuracy of the correlation thereby obtained. in . which may be taken to be the ambient pressure. Since heat transfer is usually more important than mass transfer in droplet burning. results adapted from the early analysis of Frossling [1461. [113].3. Pr = 1 may be employed in equation (67). [144]. (71453. and the arithmetic mean of the ambient temperature and the flame temperature (with dissociation taken into account) [90]. Pr and the properties p and p in Re may be evaluated at average conditions [148].276 Re1/2Sc1/3. (68) where g denotes the acceleration of gravity and AT denotes a temperature difference.3. equation (67) provides reasonable agreement with data on flameenveloped drops for Reynolds numbers from 1 to 2000. and KO is the value of K for evaporation in the same atmosphere without forced convection. Here Re = PU. Nevertheless. With these prescriptions. Gr = (SP2&/P2)(AT/T).
A pure fuel undergoing this type of fuel pyrolysis in the liquid phase gradually may become a multicomponent liquid during burning. The forced convection may induce circulation within the droplet [131][133]. In the combustion of droplets composed of binary or multicomponent miscible liquids.s2). (69) where KO is obtained from equation (65). Below or ahead of the droplet. Formulas that differ somewhat from equation (69) may be found in the literature. which in turn is extinguished at a higher velocity. For hydrocarbon droplets burning in air. it is increased significantly. opens and emits soot. under suitable conditions. with the lighter (more volatile) fuels vaporizing first and the heavier ends later. a topic considered in the following section. After vaporization of the lighter species from a thin outer layer. and above or behind. the elongated downstream flame yellows. Development of the diffusion layer is favored when liquidphase diffusion times are long compared with the droplet lifetime. [149]: K = KO(l + 0. Under these conditions. the surface temperature of the droplet consistent with interphase equilibrium may exceed the boiling point of the . with a diffusion layer at the surface. For fuels with high boiling points. but accurate theoretical results are unavailable. Free or forced convection strongly influences the flame shape. The phenomena of flame extinction are associated with finiterate gasphase chemistry.68 Diffusion Flames and Droplet Burning the presence of free convection with Gr < 1. A few correlations for corrections to K caused by finiterate combustion are available [90]. from the empirical formula [90]. a quasisteady concentration field may be established within the liquid. through which species are transported at relative rates proportional to their relative bulk concentrations in the interior. Liquidphase diffusion coefficients typically are sufficiently small that thorough mixing of the liquid is not anticipated theoretically. good theoretical bases for specific functional forms are lacking. then the burning may involve a batch distillation process. Estimates are available of the distance to the flame (for example. for example. for example. the flame ahead of the droplet is extinguished. If rapid mixing is maintained throughout the droplet. based. the distance to the flame is reduced. wake burning may ensue. on heattransfer analogies . Often the burning of initially multicomponent liquids is of interest . the fuel constituents need not enter the gas in the same proportion in which they are present in the liquid. Just prior to extinction there is a measurable decrease in the burning rate [90]. [65] and [66]). and. finiterate chemistry may occur in the liquid phase. At sufficiently high forcedconvective velocities. Fluidmechanical details may become complex. most practical fuels. are not pure compounds.533Gr0.
for example. Configurations studied include porous spheres [SO] and cylinders [1633. both experimental [98]. 3. [156][161]. by impurities like dustmay occur at somewhat lower temperatures that nevertheless still exceed the boiling point. Approaches to structure questions Concentration and temperature profiles like those shown in Figure 3. .4. and its description on the basis of a nucleation temperature is a simplification. Theoretical models for predicting the Occurrence of the phenomenon have been developed [114]. [loo]. [SO]. [ISO].6 are idealizations.4. since the concentration of the lowboiling constituent has been depleted to a large extent at the surface. [loll[103] for both miscible fuels and emulsified fuels. This interior temperature may exceed a nucleation temperature for the interior mixture*. depending on the circumstances [1511. Bubble nucleation is a rate process.1. * The nucleation temperature. heterogeneous nucleationaided. [1591for example. and on the overall stoichiometry.7. The topic has been considered to be of practical importance because the performance of combustors can be enhanced in various ways through disruptive burning [91]. interactions between quasisteadily burning droplets have been subjected to continuing study. thereby inducing a disruptive burning process in which internal vaporization of light fuel causes the liquid to expand rapidly and then disintegrate into many tiny droplets. Since practical combustors burn clouds of droplets. which exceeds the boiling point of the species. Homogeneous nucleation temperatures are substantially above the boiling point. [151][155] and theoretical [154]. Droplet interactions can be complex and can produce increases or decreases in burning or vaporization rates. Depending on the fuel. In the latter case droplet vaporization in a hot environment without combustion is relevant. Structure of the Flame Sheet 69 interior fuel mixture. conduction causes the interior temperature of the droplet to increase toward the boiling point of the heavier constituent. [162][168]). the possibility of disruptive vaporization of multicomponent droplets). Since thermal diffusivities of liquids are typically much higher than their diffusion coefficients. Further ideas on cloud combustion appear in Section 11. is the temperature at which bubbles spontaneously appear in the liquid. This process. flame sheets may surround either each individual droplet or entire clouds. increases by bringing flames closer to droplets (at large separations) in convective situations [I 511 and decreases by producing larger effective diameters [155]. Disruptive burning has been observed experimentally [91].3. In recent years a number of profile measurements have been made in laminar diffusion flames (for instance. on the convective environment. shares many attributes of droplet combustion (for example. STRUCTURE OF THE FLAME SHEET 3. of course.4.
lighter fuel species. The streamlines are made visible by seeding the gas with fine particles and illuminating it from the side. Concentration and temperature profiles measured in this flow are shown in Figure 3.7. The similarity of the profiles of temperature T. Photograph of a typical diffusion flame for heptane burning in air with streamlines revealed by a particletrack method [165]. In Figure 3. there is a stagnation point very near the liquid surface.) and oxidizer 0.6 may be seen in Figure 3. some fuel species also penetrate to the oxidizer side.8. and an oxidizing gas with oxygen mass fraction Yo. A rounding of the temperature profile in the reaction sheet is evident. counterflow diffusion flames with gaseous [162]. the flame in the mixing layer of two parallel streams [164].7. C. Also.. The particles are seen to pass through the luminous flame. H. such as C. and CH.70 Diffusion Flames and Droplet Burning through which fuel passes into initially stagnant or uniformly flowing oxidizer. A photograph of one such flame is shown in Figure 3. Results obtained are qualitatively similar. fuel (heptane. . For simplicity. but this is less evident because the downward convection quickly FIGURE 3.H. these are produced by finiterate pyrolysis of the fuel vapor as it is heated. flows out of a duct from above at a constant exit velocity U . are found on the fuel side of the reaction region. and the BurkeSchumann flame [1671.H. A small amount of oxygen penetrates the flame sheet and survives on the fuel side. or solid [166] fuels. .8. liquid [165]. attention here will be focused on the axisymmetric counterflow diffusion flame with a planar flame sheet. These profiles are invariant with distance along the flame sheet except near the edge of the liquid. A recent review [1681 summarizes observations made for various counterflow configurations.7 a pool of liquid fuel is supplied with liquid from below. . although behaviors are more complex in configurations that exhibit variations of profiles with distance along the flame sheet.. with the profiles of Figure 3.
a mixture fraction may be introduced as a coupling function.185 U=0.3. Concentration and temperature profiles above a flat surface of liquid heptane burning in a downwardly directed stream of a mixture of oxygen and nitrogen [165].3. The formulations of Sections 3. The flame is a sheet of finite thickness. not precisely a surface. reduces their concentrations in a convectivediffusive balance.8. Analyses by perturbation methods for equilibrium broadening of diffusion flames have been developed (for example.2 = 0..1 and 3. [I691 and [170]). Rounding of the temperature profile may occur by the former effect as a consequence of energy extracted chemically by dissociation. Structure of the Flame Sheet 71 Y.305 m/s Distance from Luminous Flame Zone (mm) FIGURE 3.3 in effect remain entirely applicable. leading to formulas for flame .O tend to peak in concentration at the flame sheet and to decrease in concentration more rapidly on the oxidizer side than on the fuel side. The questions to be addressed here concern the rounding of the profiles of temperature and of product concentrations at the reaction sheet and the leakage of fuel and oxidizer through the flame.7) may be employed to calculate the temperature and composition at each mixture fraction. Products such as C 0 2 and H.4. then in principle it is straightforward to account for equilibrium dissociation. There are two phenomena that can lead to this reactionzone broadening: equilibrium dissociation and finiterate chemistry. and an equilibrium chemistry program (Section A. again because of convective effects. If all Lewis numbers are unity.
Peters and F. Two types of perturbation approaches have been developed. being restricted mainly to dissociation of products into reactants rather than into radicals. “Effects of Chemical Equilibrium on the Structure and Extinction of Laminar Diffusion Flames. B. With simplified chemical kinetics. B. I. and one of the major currently outstanding diffusionflame problems is to develop better simplified kinetic models for hydrocarbon diffusion flames that are capable of predicting results such as observed correlations [172] for concentration profiles of nonequilibrium species.1199 (1949) [English translation.* and the results could be of interest for largescale. secondorder. New York: American Institute of Aeronautics and Astronautics. Damkohlernumber asymptotics and activationenergy asymptotics. No. Soloukhin. Memo. Librovich. sootconcentration profiles) that cannot be described by onestep. eds. treats the question of diffusionflame structure for a onestep. It would be relatively straightforward to extend the perturbation methods to include realistic types of dissociation. V. Barenblatt. hightemperature. Known rates of elementary reaction steps may be employed in the full set of conservation equations. Bowen. 1. Numerical integrations that have been performed mainly employ onestep (first in [107]) or twostep [173] approximations to the kinetics. J. NACA Tech. Fuel 33.G. Fiz. perturbation methods are attractive for improving understanding and also for seeking quantitative comparisons with experimental results.255 (1954). 1980.8since the broadening shown is caused mainly by finiterate chemistry. A. lowvelocity. with solutions sought by numerical integration (for example. There are a number of possible approaches to the calculation of influences of finiterate chemistry on diffusion flames.72 Diffusion Flames and Droplet Burning thicknesses in terms of equilibrium constants. Zel’dovich. vol. and G. B. they would not be relevant for many of the applicationsfor example. Tekhn. In the former the ratio of a diffusion time to a reaction time. M. kinetic schemes. Manson. Spalding. Complexities of diffusionflame problems cause this approach to be difficult to pursue and motivate searches for simplifications of the chemical kinetics [172]. Moscow: Nauka. Leakage of reactants through the flame is a finiterate effect that cannot be found from analyses of equilibrium broadening. Chapter 7 of The Mathematical Theory of Combustion and Explosion by Y. Zel’dovich. ’ Among the earliest works employing simplified kinetics and obtaining analytical approximations are those of Y. B. 1984. Zhur. and in the latter the ratio of the energy of activation to the thermal * Recently some progress has been made along these lines (N. there are important aspects of flame structure (for example.” DynamicsofFIamesand Reactive Systems. 3760). one of the similarity groups introduced by Damkohler [174]. 95 of Progress in Astronautics and Aeronautics. . laminar diffusion flames. for the profiles appearing in Figure 3. However. Appropriate onestep approximations are realistic+ for limited purposes over restricted ranges of conditions. However. Oppenheim and R. Williams. [171]). Makhviladze. A . but the types of dissociation thus far included in the simplified formulas are not entirely realistic. 19. Arrhenius reaction in a clear fashion. overall. is treated as a large parameter. K. 1296 (1950)l and of D. R. N.
to be the more useful of the two types of perturbation approaches. and from equation (14) it is readily found that p  a z at + PV * V Z = V * (pDVZ). and 3 of Section 1. regimes of small Damkohler numbersand they are extendable beyond onestep chemistry [177][I811 more easily than are activationenergy asymptotics. is taken to be large. the mixture fraction may then be defined as in equation (70) with p replaced by Z j for a selected atom j that does not have the same value of Z j in each stream. is the number of atoms of kind j in molecule i. Alternatively. the form given in equation (1) may be adopted. and in terms of the oxidizerfuel coupling function /3. O  B O .3. However analyses of phenomena such as sharp ignition and extinction events cannot be performed on the basis of Damkohlernumber asymptotics. For a onestep reaction. (71) . if the binary diffusion coefficients are equal then equation (137) is obtained. Activationenergy asymptotics appear. 0. but they can be treated by activationenergy asymptotics. consider a twostream problem having uniform properties over one portion of the boundary. A book is available devoted largely to activationenergy asymptotics [1831. [175][181].3.2. is the molecular weight of molecule i. To introduce a general approach of this type. appearing in equation (6).)vv)x. called the oxidizer stream (subscript 0. in general. They also afford possibilities of investigating other reaction regimes [176].B O .O ) > (70) so that Z = 1 in the fuel stream and Z = 0 in the oxidizer stream. 3. and vv). and different uniform properties over the rest of the boundary. activationenergy asymptotics may lead to results valid for all Damkohler numbers. possibly at infinity).4.4. A conservation equation for Z may be derived from the general conservation equations. Moreover. the mixture fraction may be defined as z = (B . called the fuel stream (subscript F ./W. O ) / ( B F . assume that there is no oxidizer in the fuel stream and no fuel in the oxidizer stream. 0. most of the analysis of its structure can be performed without reference to a particular configuration. emphasized as important by FrankKamenetskii [37]. where W. which appears in equation (A36). The mixturefraction variable Since the reaction zone is thin. is the atomic weight of atom j . Damkohlernumber asymptotics can provide estimates of reactionzone broadening in nearequilibrium situations [125]. [182]for example. Under assumptions 1. also possibly at infinity). [126]. for general chemistry the local mass fraction of an atom of typej may be defined as Z j = (K.2. the application to diffusionflame structure was made by Liiian [184]. and therefore results of Damkohlernumber asymptotics may be extracted from those of activationenergy asymptotics. Structure of the Flame Sheet 73 energy.
= . The sum of the thermal and chemical enthalpies is h = hiY.mF = x/yvi Y F I W F v F . pat at Evidently. provided that this form is consistent with initial and boundary conditions. = v * * (pDVPJ. it is readily shown that = hO. a scalar quantity that is neither created nor destroyed by chemical reactions. 0 . 0 Olz + ( h F . all conserved scalars are expressible in terms of 2. the mass fractions may be expressed explicitly in terms of Z and YF. Energy conservation warrants special consideration.mi .i = cp = constant and if the chemistry is described by equation (1). which were needed in Section 1. Simplified. replaced by Z j .. For example. + p  ab’i at + pv vg.q. that equation (72) may be written as a+ h+v. = pD) and negligible dp/& reduce equation (73) to the same form as equation (71). Substitution of this into equation (110) and the result into equation (13) may be shown by use of equations (11) and (12) to provide as a general form of energy conservation cr=l +v * [(pU  P)* v] +p i= 1 c Yf. solutions in a form like equation (74) exist. thereby giving (74) as a solution for h in terms of Z . explicit expressions for concentrations and temperature in terms of Z and one other variable can be written if cp. This development has the important attribute of not invoking the assumptions of steady flow and of onestep chemistry.Vh=+V aP.14 Diffusion Flames and Droplet Burning The chemicalsource term does not appear in equation (71) because (like p or Z j ) Z is a conserved scalar. From these solutions.namely. . (75) whence in view of equation (71). then formulas for all Zj in terms of Z are obtained by solving equation (70) for p. it may be shown from equation (16) under the assumptions introduced above. if initial conditions and boundary conditions are appropriate. the further assumptions of a Lewis number of unity (Yc.hO. Under additional assumptions. For the coupling functions p.  (72) For flows at low Mach numbers with negligible radiant heat flux.3. N * (v + Vi) v . .
= yo. Note that by putting Z = Zcin equation (84) the appropriate adiabatic flame temperature is obtained : + YF. and equation (77) gives (83) yo = YO.i= c p = constant.O(l .oqo/cp T .0 WFvFIFor Z > Z. Structure of the Flame Sheet 75 The similar expression is obtained directly from equation (70). and the first two terms.o . and according to equation (77). a flame surface exists where YF = Yo = 0. without chemical reactions. and (77) in the formula h = h:YF f hgY0 + N2 hpx i= 1 + c. (80) give the “frozen” temperature profile that would be obtained for pure mixing. The temperature is expressed in terms of 2 and YFthrough use of equations (74).3. + YF. it is found that where 7 ’ is given by equation (SO).0 wovo/Yo. O(z  2c)/(1  zc>. (78) obtained from equation (111) with cp. ‘F. From equation (77) it is seen that at YF = Yo = 0 the corresponding (stoichiometric) value of the mixture fraction is YF.f = yO.(T To). In the BurkeSchumann limit.Oz? yO.4.OWFVF (85) . the quantity qo/wFvF is the heat released per unit mass of fuel consumed. = ( 1 + (81) = yF. yF 2..O(l  z>.oWo~oTo.no fuel is present.f = yF. 0 + (TF.OWOVO YO.Z / Z J The temperature may be obtained as a function of Z in the BurkeSchumann limit by use of these results in equation (79). 0 I z . After algebraic reduction it is found that where qo is defined by equation (44). The frozen concentration profiles of fuel and oxidizer would be Tf = TO.oWFvFTiF. no oxidizer is present. and all concentrations and temperatures may be written explicitly in terms of Z.o + YF. 0  TO.oYo. (82) for Z < Zc. (76). In equation (79).
and (79) relate the other variables to this quantity and YF.6. fl = 0.)' with Z . (77).BT". = v. and equations (76). it could have been introduced in Section 1. and (79) may be employed.. For the dropletburning problem. In fact. under the present assumptions. where B is defined at the beginning of Section 3. y e . and the overall frequency factor for the rate of fuel consumption is A . becomes 2 = Z. the empirical reaction orders nF and no have been introduced. since the overall stoichiometry seldom provides the correct dependence of the rate on concentrations. (19) and (112) we find that.3. The overall activation energy is E . Although such selections of variables basically are matters of personal taste.(1 + B)rl'r. to replace fi in equation (149). it is found that equation (42). The equivalence of equation (63) with the expression for r. as discussed in Section B. that for fuel.3. (18). From equations (14). given by equation (81). in equation (25) the flamesheet condition.Z. this additional equation can be written as where W F V F BT" P n + ~n o y p y . but equations (76). Since it is a coupling function. obtaining a qualitatively correct variation of the overall rate with the mass fractions of reactants. the twostream problem most simply relevant to droplet burning has pure liquid = l). To study the structure of the reaction sheet. the replacement of /? by 2 achieves a convenient normalization and also can help to clarify aspects of physical interpretations. that is obtained from this solution can be derived from the fact that 1 + v = (1 . interpreted for 2. For simplicity here we put nF = no = 1. we therefore need an additional conservation equationfor example. equations (82). Activationenergy asymptotics Equation (71) is a conservation equation for the mixture fraction. and (84) cannot be taken as generally valid relationships. (83). 3. For example. (77).76 Diffusion Flames and Droplet Burning In studying the structure of the flame sheet. .l < 1 according to fuel in one of the streams (YF. a condition of mixturefraction stoichiometry.1.3.o equation (64). becomes simply 2 = 1 .3. it could have been used in place of b in equations (9) and (38). with equation (70) employed to recover b from the solution for 2. even though YF. when all the assumptions that underlie equation (58) are introduced.4./r. The mixture fraction 2 could have been introduced and employed directly in earlier examples.EIRoT (87) In this onestep approximation.
through equations (11) and (12). as the variable to be considered in addition to Z .(pDVT) + WT. We can. and (86) it is readily shown that p aT at + pv. define the flamestructure problem to be investigated. Since v appears in these equations. x and y. Otherwise it is only a conceptual aid. Equations (71) and (88)(91). T (92) . it is convenient to employ T instead of Y.(pDV. investigate the variation of T with Z and study the influence of finiterate chemistry on this variation.4. where The quantities YF and Yo in equation (89) may be expressed in terms of Z and T by use of equations (77) and (79). and where Tf is given by equation (80). in a manner analogous to that of Crocco [l85]. When use is made of equation (71) it is found that a formal transformation of (88) into the new coordinate system yields dT pat + PVl.(ln 1 V Z I ) V .T = WT T + p D I V Z 1d2 2 y + V. respectively. in this new reference frame. however. in general it is necessary to consider the fluid dynamics as well. Let u and v be velocity components in the x and y directions. (79).VT= V. along with boundary and initial conditions.T) az  pDV. From equations (71). This may be done in principle if pD is independent of T and if changes in the solution T have a negligible influence on the fluid dynamics. This type of investigation is facilitated by introducing into (88) the variable 2 as an independent variable. and we cannot investigate directly the variation of T with space and time. Structure of the Flame Sheet I1 Since T appears inside the exponential. Consider an orthogonal coordinate system in which 2 is one of the coordinates and the other two. namely. We consider that equation (71) is solved first.3. are distances along surfaces of constant 2. in seeking solutions.V. prior to the study of equation (88).
be exact solutions of equation (92) as well. The details of . in fact. and (91)equation (93) possesses solutions in which T varies only with Z . to the total chemical heat released at the flame.. and (91)in the first approximation the differential equation d2cp/dy2 = d ( q 2 .2Z.ZC)(TF. thenin view of equations (89). treating these variables as being of order unity. is a large parameter. because of the Arrhenius factor. Therefore values of the reaction rate some distance away from the stoichiometric surface ( Z = Z.q2)e(4'+)'$) (96) is obtained. defined in Section 5.)/[E(T. and that w T will decrease rapidly. describes T(2) To carry out an analysis of the reaction zone by activationenergy asymptotics.y is twice the ratio of the heat conducted from the flame toward negative values of Z .. is the twodimensional gradient operator in x and y . cp = (T .).6.yq. Z may be stretched about Z . and T about T. In activationenergy asymptotics. y .. Thus equation (93) viewed as an ordinary differential equation exactly for many problems. where E = 2R0T. It can be shown that t is the formal small parameter of expansion for activationenergy asymptotics applied to the diffusion flame and that 1 .. and therefore equation (92) becomes.Z. is Tf evaluated from equation (80) at 2 = Z. As an independent variable. where a reduced Damkohler number is with A.Z. and where V.Z .. (93) If AFp/(DIVZI2) is independent of x. Equation (89) then suggests that w T will be largest near the maximum temperature T.2zc(1 .To.(1 .T'. E/RoT...T)E/RoTf.)/t and as a dependent variable.p/(DIVZIZ) understood to be evaluated at Z = 2.Tf. and t. (90). as T decreases appreciably below T.O . approximately. (95) in which Ts. . (90). A stretching of this kind causes the terms involving the highest Z derivative to be dominant.)] (94) and "? = 2 2 .. and expanding in €with use made of equations (89) (which has nF = no = l).it is helpful to stretch the 2 variable in equation (92) about Z = 2.1 . a2T/az2= .78 Diffusion Flames and Droplet Burning where vL is a twodimensional vector with x and y components being u and v.o)/(K . The quantity l/t is closely related to the Zel'dovich number. By introducing cp and 9 into equation (93).. and those solutions will.3. introduce q = (2 . This implies that to analyze the effect of w T .w ~ / ( ~ D I v z I ~ ) .) will be very small in comparison with the values near Z = Z..
In typical combustion applications.. The difference T. [176]. d[/d( + f 1 as ( + fm. The large4 solution to the above equation has [ T ( + 0 as + k rx. then smaller values of E still yield a small value o f t . From equation (84) and the definitions of cp and q.t2. that increases as 6 decreases.Tf. with [ = cp6”3 and = q d l i 3 treated as being of order unity. by a fractional amount. As is usually true (Chapter 5). the fractional decrease of the maximum temperature below T. if the heat release is large..3. . scalings vary BurkeSchumann solution occur also is of order ~ / d ’ / ~ with the reaction order [125]./E. defined in equation (94). The advent of activationenergy asymptotics has helped greatly in clarifying criteria for the validity of the flamesheet approximation. is the local temperature increase. associated with complete combustion occurring at the flame sheet ( Z = 2.). To have t small. The thickness of the reaction zone is seen to correspond to 2 . matching to the BurkeSchumann solution given by equation (84) may be imposed for q + f co. Liiian’s paper [1841 may be consulted for methodology.4.2. [126]. results in the ’ . being of order E . enparameterfree problem d’[/d(’ = 1 countered in Damkohlernumber asymptotics and integrated numerically [175].. t lies between 0. if the heat released in complete combustion is too smallthen t is not small enough for w T to vary rapidly enough with temperature near the flame sheet to justify use of activationenergy asymptotics.(cp either fuel or oxidizer or both leak through the reaction zone in a fractional amount of order t that increases as 6 decreases [184]. a rescaling of variables in equation (96). They also show. that of lim. proportional to E. and therefore no leakage of fuel or oxidizer in the first approximation. is the best formal parameter of expansion instead of simply RT. These solutions show that the maximum temperature is reduced below T. [126]. but there must be some heat release.1.01 and 0. it may be shown that the matching requires dcp/dq t t. the heat release need not be very large if E is large.If this temperature increase is too smallthat is. the range of 2 . Solutions to equation (96) that satisfy these boundary conditions exist for a range of values of 6 [184].2. The < . This development shows that Damkohlernumber asymptotics can be obtained as a limiting case of activationenergy asymptotics. As 6 becomes large. and results of expansions to the lowest order in activationenergy asymptotics are reasonably accurate. In the large4 limit.. over which departures from the These . Structure of the Flame Sheet 19 deriving equation (96) are not shown here but parallel the development of activationenergy asymptotics given in Chapter 5. over its frozen value. It is significant that E . through evaluation T y ~ ) from the numerical integration of equation (96). in the first approximation this matching requires the slopes dT/dZ to agree. To obtain boundary conditions for equation (96). 1 as q + fco. a reactant having an overall reaction order greater than unity experiences leakage in the first approximation in Damkohlernumber asymptotics [125]. is of order ~ / 6 ” and ~ .
the analysis shows that equilibrium prevails to all algebraic orders in t between the hot boundary and the flame sheet. Therefore. so that y is near . where T is lower.(1 . Damkohlernumber asymptotics apply.l y l ) . Ignition and extinction Analysis [184] shows that the minimum value of 6 below which solutions to equation (96) cease to exist is & = [(I . For the more common problems in which the peak temperature occurs at the flame sheet. The reactant that leaks is described outside the reaction zone by an equation like equation (93) with wT = 0. then extinction of the diffusion flame occurs.4. This suggests that equation (84).2. typically 0. For large values of 6. For (y(> 1. As extinction is approached (through decreasing S). and solutions linear in Z are obtained. and in fact there are reaction regimes in which these equations do not apply [184]. where 2 .055(1 . The result is a modification to equation (82) or equation (83). the chemistry is frozen to all algebraic orders in E on both sides of the reaction zone. The extent of leakage at extinction is proportional to t. the extinction formula can be inaccurate if (y(is too close to unity. 3. the value of 2. by a correction term proportional to E. and the chemistry is frozen between the flame sheet and the cold boundary. leakage of one of the reactants through the reaction zone increases.4.Iyl)' + 0.05. the BurkeSchumann solution. As I y I approaches unity. defines only one of many possible solutions that may apply outside the flame sheet. For problems in which the peak temperature occurs at a boundary instead of at the flame sheet.1 ~ 1 + ) ~ 0. and an abrupt extinction event does not exist for the diffusion flame.1. This situation sometimes tends to be encountered in practice for the burning of hydrocarbon fuels in air. These regimes will be discussed in the Section 3. by turning off the chemistry outside this sheet. The nonexistence of solutions to equation (96) when 6 is too small means that if reaction rates are not sufficiently high. in equation (95) can be small.4. Use of equation (98) in equation (97) provides an explicit expression for conditions of extinction of the diffusion flame. The extinction phenomenon will be addressed next.80 Diffusion Flames and Droplet Burning strong dependence of wT on T for large E helps to confine the combustion reactions to a thin sheet.Iyl)"]e (98) within 1 % for IyI < 1.26(1 . and appreciable leakage of fuel into the oxidizer stream is calculated to occur at extinction.4. and the thickness of the reaction zone decreases with increasing 6. one of the two boundary temperatures exceeds the flame temperature. the proportionality factor at extinction between the leakage correction to the reactant mass fraction and t becomes large. . Large values of the magnitude of the reaction rate in the reaction zone help to improve the validity of the flamesheet approximation. is of order E. and also to equation (84).
as 6 increases from zero with t fixed. One of these two factors tends to become constant. extinction of the diffusion flame occurs subsequent to its passage into the premixedflame region. Structure of the Flame Sheet 81 When leakage of one reactant becomes sufficiently large.. then these.5. but they tend to become inaccurate if 6 is too large. In this regime. or ignition regime [184].exceeds both boundary temperatures. This has been termed the nearly frozen. then as 6 decreases.4. The method of analysis bears some relationship to the methods discussed in Section B.and T ( Z ) is given by the frozen solutions.q)(cp + q ) of fuel and oxidizer concentrations in the reaction zone. There is a fourth regime in which the first approximation to YF(Z). solutions are found to exist only for values of a Damkohler number.. Qualitatively.The asymptotic analysis of this regime is due to Liiian [184]. is less than a boundary temperature (Iyl > l). .. lose accuracy at larger 6. that are less than a maximum value 61.. Yo. An asymptotic analysis may be developed for which.3. In this case. in the reaction zone. who terms it thepremixedflame regime of the diffusion flame. depletion of only one reactant occurs. Yo(Z). and even in lowest order the flame temperature becomes a premixedJame temperature less than T.q2 is the scaled product (cp .. or nearequilibrium regime considered in the previous section. to distinguish it from the diffusionflame. If I y I is near enough to unity and t is not too small. all of which have a thin reaction zone of elevated temperature. When T. This regime has been termed the partialburning regime [184]. A modification to the BurkeSchumann solution of order unity is needed on the side of the flame sheet to which reactant has leaked. the situation in the vicinity of the reaction zone tends to begin to resemble that for a premixed flame. nearly frozen solution exist for all values of 6. then the solution must lie in one of the other regimes. and diffusionflame solutions become accurate.4. if 6 > 6. Departures from equations (82). There are no partialburning solutions when T. as in a premixed flame. conditions may be calculated for which the second reactant also begins to leak through the reaction zone in appreciable quantities. Provided that T.. hence. and modification of scaling for the asymptotic analysis becomes warranted. is less than a boundary temperature.2. in equation (96) the factor cp2 . Since nearly frozen solutions do not exist for 6 > 61. activationenergy asymptotics show that the reaction tends to occur in a region near the hotter of the two boundaries [184]. related to 6. the factor cp2 . and T ’ [see equation (80) and the sentence following it].q2 remains effectively constant [184]. although there are significant differences because of the absence of spatial homogeneity. in turn. (83). nearly frozen solutions lose accuracy anL premixedflame solutions gain accuracy. the value 61 may be interpreted as a critical Damkohler number for ignition. YF. and (84) then occur even in lowest order on both sides of the flame sheet. As the premixedflame temperature decreases.
then at least when 6 Eis passed. A suitable partialburning analysis can give the middle branch and both bends.Lower branch I 0 % * 6 81 FIGURE 3. flames on this branch have not been obtained experimentally.82 Diffusion Flames and Droplet Burning . . which is a sketch of the maximum temperature T. at which point the solution must jump discontinuously to a vigorously burning state on the upper branch. and the lower branch and part of the middle branch by analysis of the ignition regime. much of the middle branch and part of the upper branch by analysis of the premixedflame regime. prior to the vertical tangent.o and To. Schematic illustration of the dependence of the maximum temperature on the reduced DamkBhler number for diffusion flames. TF. If 6 is gradually increased for a mixing flow with negligible chemical reaction. an ignition or extinction jump itself is not instantaneous. the few studies that have been performed (for example.. If 6 is gradually decreased for a vigorously burning diffusion flame on the upper branch. exceeds the boundary temperatures. timedependent process that would .  Middle branch I 1 I I . . [187] and [l88]) indicate that instability begins at or very near the extrema. where generally there is negligible reaction. then the system may be expected to move along the lower branch until it reaches d l . Of course. leading to an ignition or extinction jump. as obtained both by numerical integration of the full equations [I1861 and by activationenergy asymptotics [1841.9. The upper branch and part of the middle branch are predicted by analysis of the diffusionflame regime. usually in the diffusionflame regime. it is a very rapid. It is conceivable that the upper or lower branches experience instability. It is believed that the middle branch is unstable. the solution must jump discontinuously to the lower branch. as a function of the Damkohler parameter 6. Although entirely thorough stability analyses have not been completed.9. but it is likely that the entire partialburning regime is unstable and therefore not significant for diffusion flames. The most common situation is summarized qualitatively in Figure 3. This figure applies for small 6 and only if T.
Since the possible simultaneous presence of three phenomenaconvection. timedependent mixing and reaction of initially separated fuel and oxidizer by activationenergy asymptotics [193] encounters many of the aspects that have been discussed here. it will prove useful later. and reactioncomplicate analyses. it is evident that outside the reaction zone there must be a balance between diffusion and convection. as 6 decreases solutions on the upper branch in the diffusionflame regime become less accurate than those in the premixedflame regime prior to extinction. since no other terms occur in the equation for species conservation. notably in connection with turbulent flames (Chapter 10). and Z therefore may be interpreted directly as a normalized physical coordinate. spherically symmetrical burning of a droplet [1923. instability occurs near (not precisely at) the extremum. in this event the premixedflame regime is relevant to Figure 3. then only solutions in the diffusionflame and ignition regimes are significant with respect to Figure 3. Analysis of onedimensional. it can be helpful to eliminate one of the three formally by means of a transformation. Structure of the Flame Sheet 83 not be described by Figure 3. by finding a transformation to a new spatial variable such that the convective and diffusive terms coalesce into a . Thus these flames consist of convectivediffusivezones separated by thin reaction zones. personal communication) that in the premixedflame regime. 2 equals the normal distance (measured from the oxidizer side of the layer) divided by the thickness of the layer. stagnant diffusion layer.3. If this regime is unstable. It also has been applied to the quasisteady. The possibility of using the Crocco transformation to achieve this generality was suggested by Peters [190]. if IyI is near unity and t is not too small. This is achieved in the analysis of the counterflow flame [184] by writing the equations in a convectionfree form.9.4.9 in that. The analysis exposing activationenergy asymptotics originally was developed within the context of the problem of the steady counterflow diffusion flame [184]. The presentation here has not been cast within the framework of any particular configuration for the diffusion flame. It seems more likely (A.9 or equation (93) but instead would require retention of p aT/& in equation (92). Liiian. that is. For steadystate diffusion flames with thin reaction sheets. I VZ I is the reciprocal of the thickness Gf the layer. greater than the boundary temperatures has been questioned [189]. diffusion. Thus the BurkeSchumann flame consists of two convectivediffusive zones separated by a reactivediffusive zone. [191]. in the first approximation these reaction zones maintain a balance between diffusion and reaction and may be more descriptively termed reactivediflusive zones. Since the stretching needed to describe the reaction zone by activationenergy asymptotics increases the magnitude of the diffusion terms with respect to the (less highly differentiated) convection terms. For this problem with p D constant. The simplest configuration to which the formulation may be applied is the steady. The stability of solutions in the premixedflame regime for systems having T.
84
Diffusion Flames and Droplet Burning
single term that resembles a purely diffusive term in the new variable. The transformation to convectionfree form is especially useful for analyzing the ignition regime, for which the reaction zone is not thin in the original spatial variable but instead extends an infinite distance into the hotter of the two streams, causing convection, diffusion, and reaction all to be important in the reaction zone. For any diffusion flame having a symmetry that eliminates the transverse gradient from equation (92), it is evident from equation (92) that the transformation to the mixture fraction as an independent variable achieves' a convectionfree form. Thus a diffusionflame prescription for transformation to convectionfree form is to introduce a mixture fraction as an independent variable. Overall rate parameters for diffusion flames, needed in applying the analysis given here, often are not available. The analysis itself may be employed to design an experimental technique for obtaining these parameters from measurements of diffusionflame extinction [194]. The counterflow configuration is convenient ; the analysis addresses experiments with liquid fuels, shown in Figure 3.7. The quantity D I VZI2 is proportional to the exit velocity U of gases leaving the oxidizer duct [195] if the experiment is carefully designed to establish a radial channel flow with a uniform rate of injection from above. To achieve reasonable accuracy in calculating D I VZ 12, it is necessary to take into account variable properties ( p and D) and the influence of the presence of the condensed phase (through parameters such as the transfer number B ) [194]. O n the basis of the theory, an Arrhenius graph can be defined from equations (97) and (98), in which a semilog plot of a quantity proportional to the measured value of U at flame extinction, as a function of l/T, provides E from the slope and AF from a value. Rate parameters obtained in this manner may be employed for calculating diffusionflame structure and extinction in other configurations. Overall rate parameters for a number of fuels have been found in this way; a critical review is available [196]. 3.5. MONOPROPELLANT DROPLET BURNING
A monopropellant is a fuel that is capable of reacting exothermically without an oxidizer. Numerous such fuels are known; many are liquids. A droplet of liquid monopropellant can burn in an inert atmosphere without an oxidizer. There are rockets that employ liquid monopropellants as fuels for propulsion ; in some applications these are better suited than bipropellant rockets that employ a liquid fuel and a liquid oxidizer. The relevance of monopropellant droplet combustion to the operation of monopropellant rockets and fundamental curiosity have prompted studies of the subject. Burning monopropellant droplets have the spherical configuration shared by burning fuel droplets in an oxidizing atmosphere and the pre
3.5. Monopropellant Droplet Burning
85
mixedness of ordinary laminar flames (Chapter 5). Consequently, it may be expected that monopropellant droplets exhibit some characteristics of each of these systems. As is often true in intermediate cases, the analysis of monopropellant droplet combustion in certain respects is more complicated than that of either the planar premixed flame or the fuel droplet. A number of theoretical studies of the quasisteady, spherically symmetrical burning of monopropellant droplets have been published. These include work involving numerical integration of the conservation equations or of approximations thereto [197], [1981, analytical approaches involving ad hoc approximations [85], [199][201], methods employing Damkohlernumber asymptotics [202][206] and procedures based on activationenergy asymptotics [207][210]. Reviews may be found in the literature [lll], [183]. Consideration has been given to burning in inert atmospheres under both adiabatic and nonadiabatic conditions, as well as to burning in reactive atmospheres containing an oxidizer that can react with the fuel or its decomposition products [SS], [205], [206]. The general character of results of these analyses may be understood on the basis of physical reasoning. Consider first the burning in an inert atmosphere, the temperature of which is at or above the adiabatic flame temperature for decomposition of the monopropellant. If the reaction rate is sufficiently low, then the combustion will have a negligible influence on the rate of mass loss of the droplet, and the dominant process will be inert vaporization in a hot atmosphere. We have seen that this process has a dsquare law, and we know how to calculate the burning rate (for example, from equation (58) with Yo,m = 0; see Section 3.3.6). The reaction occurs far from the droplet surface, in a region of large extent, whose location depends on a nondimensional activation energy and/or on a Damkohler number, D,, = rfW/pD, where W is a representative value for the mass rate of consumption of fuel. A decrease in D,, or an increase in the activation energy moves the reaction region farther from the droplet. The burningrate constant, K , is given by equation (65) and does not depend on DII. If the reaction rate is larger, then the combustion influences the rate of mass loss. For sufficiently large values of D,,, the reaction occurs in a narrow zone whose thickness is small enough for curvature effects to be negligible within it. If a nondimensional activation energy is large, then this zone is separated from the droplet surface by a convectivediffusive zone. In this case the structure of the reaction zone resembles that of the reaction zone of a premixed laminar flame (Chapter 5), with heat addition from superadiabatic products if the ambient temperature exceeds the adiabatic flame temperature. Qualitatively, the speed of propagation of the planar laminar flame begins to control the rate of mass loss of the droplet, and K becomes proportional to (see Chapter 5). Since K drf/dt and r l , the dsquare law is replaced by a dlaw in which the first power of the droplet diameter decreases linearly with time.
fi

fi
86
DiffusionFlames and Droplet Burning
The transition between these two limiting regimes occurs roughly Asymptotic where K , as given by equation (65) is of the same order as analyses give sharper criteria for the transition [207]. Over any limited range of conditions, drk/dt is approximately constant, where 1 < k I 2. In view of the dependence of D,, on rI, for large droplets the &law tends to hold; for small droplets the dsquare law holds. Additional phenomena occur if the temperature of the inert atmosphere is less than the adiabatic flame temperature. As might be expected from the discussion in the previous section, ignition and extinction events may be encountered [207]. Formulas for extinction conditions, obtained on the basis of activationenergy asymptotics, are available [207]. Within the context of activationenergy asymptotics, a partialburning regime of the type discussed in the preceding section is found to arise [207]. A diffusionflame regime, of course, does not exist for burning in an inert atmosphere; in this respect the problem of the monopropellant droplet is simpler than that of a fuel droplet in an oxidizing atmosphere. For burning in a reactive atmosphere, conditions may be encountered for which the analysis of the diffusionflame regime is relevant. Under suitable conditions there are two thin reaction sheets, an inner one at which premixed decomposition of the monopropellant occurs and an outer one having a diffusionflame character. Categorizations are available for potential limiting behaviors at large Damkohler numbers in reactive environments [206]. There are many flamestructure possibilities, not all of which have been analyzed thoroughly.
JE.
REFERENCES
1. S. S. Penner, Chemistry in Jet Propulsion, New York: Pergamon Press, 1957, Chapter XXII. 2. A. M. Kanury, Introduction to Combustion Phenomena, New York Gordon and Breach, 1975, 142269. 3. I. Glassman, Combustion, New York: Academic Press, 1977, 158193. 4. S. P. Burke and T. E. W. Schumann, Znd. Eng. Chem. 20,998 (1928). 5. J. A. Fay, J. Aero. Sci. 21, 681 (1954). 6. A. Goldburg and S. I. Cheng, C & F 9, 259 (1965). 7. J. B. Haggard, Jr. and T. H. Cochran, CST 5,291 (1972). 8. T. M . Liu, C S T 7 , 283 (1973). 9. P. H. Thomas, 9th Symp. (1963), 844859. 10. F. J . Kosdon, F. A. Williams and C. Buman, Z2th Symp. (1969), 253264. 11. F. A. Williams, Prqg. Energy Combust. Sci. 8, 317 (1982). 12. H. C. Hottel and W. R. Hawthorne, 3rd Symp. (1949), 254266. 13. M. Klajn and A. K. Oppenheim, 19th Symp. (1982), 223235. 14. 0. A. Tsukhanova, 6th Symp. (1957), 573577.
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‘I
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169. 170. 171. 172. 173. 174. 175. 176. 177. 178. 179. 180. 181. 182. 183.
CHAPTER 4
Reactions in Flows with Negligible Molecular Transport
There are a number of combustion problems in which transport phenomena (which were of dominant importance in the preceding chapter) are negligible. Since the transport effects give rise to the most highly differentiated terms in the conservation equations, these effects will generally be unimportant provided that the gradients of the flow variables are sufficiently small. How small these gradients must be depends, of course, on the sizes of the other terms appearing in the conservation equations. Large values of the convective and timedependent terms help to make the transport processes negligible. For example, in flows at high subsonic or supersonic speeds, transport effects are usually unimportant except in thin regions, such as shock waves and boundary layers, where the flow variables change very rapidly with position. The present chapter deals with systems involving negligible transport but finite reaction rates and focuses on methods of analysis, giving a few illustrative examples; textbooks [l] and [2] delve more deeply into details of some of the material to be covered here.
4.1. IGNITION DELAY AND THE WELLSTIRRED REACTOR
One simple example of an experiment in which transport effects are considered to be negligible is illustrated in Figure 4.1 and is described in detail in [3]. An oxidizing stream at an elevated temperature and traveling with
92
4.1. Ignition Delay and the WellStirred Reactor
93
._
V
Oxidizer
4
1 tv
Fuel FIGURE 4.1.
7
Schematic diagram of spontaneous ignition experiment
velocity V is brought into contact with a small amount of fuel which rapidly achieves this same temperature and velocity. An ignition delay z may be defined as the ratio of the distance L downstream at which detectable luminous emissions begin to the convective velocity V. If it can be assumed that mixing occurs very rapidly in comparison with the rate of the gaseous chemical reaction, then transport terms can be neglected, and equation (14) for the fuel implies that, approximately,
where p is the density of the reacting mixture at the temperature and pressure of the approaching stream, wF is the rate of production of fuel (mass per unit volume per second), evaluated at the temperature and pressure of the oxidizing stream and at a mean composition of the ignition zone, and AYF is the change in the fuel mass fraction that occurs prior to ignition. An estimate of the overall reaction rate during ignition can therefore be obtained by measuring V and L. Values of the ignition delay, obtained in experiments of this type that were performed at different temperatures, have been used in conjunction with equation (1) to deduce overall activation energies for the ignition of numerous fuels in air [3]. Various aspects of these ignitiondelay experiments deserve further discussion. As explained in Section B.2.5, the chemical kinetics occurring during the ignition delay are complex and generally involve significant chain branching. Implicit in the writing of equation (1) is the idea that however complex the chemistry is, it can be related approximately to the disappearance of fuel, possibly to a small extent, prior to ignition. This interpretation is not essential to the use of z;for example, it would be equally possible to interpret l/z as the ratio of the rate of production of a critical chain carrier to the concentration of that carrier needed for ignition. The key aspect is that it must be possible to identify, in principle, a single variable that describes the progress of the ignition reactions. When this variable is normalized so that it begins at zero and achieves a value of unity at ignition, then the time rate of increase of the normalized progress variable Y is
dY/dt
=
l/z.
(2)
94
Reactions in Flows with Negligible Molecular Transport
Use of z = L/V in equation (2) involves an approximation of relatively small changes in properties throughout the ignition region in Figure 4.1. Equation (2) affords the possibility of employing ignitiondelay data to calculate ignition processes in nonuniform flows [4]. Elements of gas containing fuel are identified and followed in a Lagrangian sense. For any such element, integration of equation (2) implies that ignition will occur at a time tI defined by
Jr(dt/~) = 1.
(3)
Application of equation (3) to different elements provides a value of t , for each element; the minimum of these values is the shortest time for ignition to occur in the nonuniform system. Approaches of this type have been employed for estimating the chamber length required for combustion of a liquid injected into a supersonic stream [4] and for identifying conditions for ignition of streams of droplets of liquid fuels in oxidizing gases [S]. These approaches inherently lack accuracy because of their neglect of interdiffusional effects but often are convenient approximations, particularly for configurations that are too complex to be amenable to analyses that are more precise. Another example of a system in which attention is focused primarily upon the rate of the chemical reaction is the conceptual wellstirred reactor [6]. It is supposed that by introducing extremely highintensity ' ; the thermodynamic properties can turbulence into a reactor of volume 9 be made to be practically uniform throughout the reactor. The rate of consumption (mass per second) of fuel in the reactor will then be given by  w F^y; where the thermodynamic variables appearing in the expression for wF [equation (1S)] are the average values of these variables in the reactor. For steady flow, the mass per second tizF of fuel entering the reactor would therefore have to be
riz~ = WFv/AYF,
(4)
where AY, is the difference between the inlet and outlet mass fractions of fuel. This is the fundamental equation of the wellstirred reactor; it is sometimes coupled with an overall energy balance in order to determine the heatrelease rate. The difficult problem in the analysis of any given system of this type is to ascertain the appropriate average properties within the reactor for computing wF. A considerable amount of attention has been devoted to this problem, and a number of results have been obtained [ 6 ] , c71, CSI.*
* The earliest detailed theoretical analysis of the behavior of the wellstirred reactor appears to be that of Y. B. Zel'dovich and Y. A. Zysin, Zhur. Tekhn. Fiz. 11,493 (1941); see [7].
4.1. Ignition Delay and the WellStirred Reactor
95
An experimental apparatus that under certain conditions approximates closely a wellstirred reactor is a spherical chamber into which premixed reactants are injected centrally through a perforated tube and out of which the reaction products flow through a number of ports located at various positions in the outer shell. The mixing is driven by the fuelinjection jets that are formed at the tube perforations, and the apparatus has been called the jetstirred reactor. The average residence time of an element of gas in the reactor is
TR =
pv/mF>
(5)
where p is the average density inside. Measurement of the average temperature and pressure inside and of the flow rate and inlet and outlet compositions for various values of riz, enables z R and W , to be obtained as functions of temperature, for example. In this manner, overall rates of reaction are derived. The overall rate of consumption of fuel obtained in a wellstirred reactor differs from that of an ignitiondelay experiment because the combustion rather than the ignition of the fuel is investigated. Overall rates of other processes, such as pollutant production, also have been obtained in experiments with jetstirred reactors by measuring levels of the appropriate products in the outlet streams. Results of some experiments on jetstirred reactors are consistent with the concept of the wellstirred reactor [6], [9][17]. Some of the more recent work cited has endeavored to account for influences of imperfect mixing. Theoretical aspects of the wellstirred reactor have been presented in a recent book.* Questions of the degree of perfection of mixing have plagued the use of the concept of the wellstirred reactor. In general, high turbulence intensities, small turbulence scales, slow rates of reaction, high reactor temperatures, small amounts of heat release, and relatively weak dependences of rates on temperature favor achievement of experimental results to which the concept can be applied, since under these conditions mixing rates are enhanced in comparison with reaction rates, and influences of nonuniformities within the reactor are minimized. Further information on favorable conditions may be found in Chapter 10. In the applications that have been discussed here, high rates of transport have, somewhat paradoxically, favored attainment of conditions under which analyses neglecting transport effects can be applied. The rapid transport helps to achieve conditions of uniformity, under which transport no longer is significant, and effects of finiterate chemistry can be studied. This same kind of situation prevails in various other experiments, such as those employing a suitably designed turbulentflow reactor [18], [19], [20]. In
* Y. B. ZePdovich, G. I. Barenblatt, V. B. Librovich and G. M. Makhviladze, The Mathematical Theory of Combustion and Explosion, Moscow: Nauka, 1980.
96
Reactions in Flows with Negligible Molecular Transport
contrast, for the problems considered in the rest of this chapter, low rates of transport (in comparison with rates of convection and of reaction) favor attainment of conditions under which transport phenomena are negligible.
4.2. REACTIONS IN STEADY, QUASIONEDIMENSIONAL FLOW
4.2.1. Steadystate, quasionedimensional conservation equations
The equations governing the steadystate, quasionedimensional flow of a reacting gas with negligible transport properties can easily be obtained from equations (119)(122). When transport by diffusion is negligible ( D i j + 0 and DT, t 0 for i, j = 1, . . . , N ) , the diffusion velocities, of course, vanish [K + 0 for i = 1 ,. . . , N , see equation (114)]. If, in addition, transport by heat conduction is negligible (1 + 0) and qR = 0, then the heat flux q vanishes [see equation (115)]. Finally, in inviscid flow ( p + 0 and K + 0), equations (116)(118) show that all diagonal elements of the pressure tensor reduce to the hydrostatic pressure, p I 1 = p 2 2 = p33 = p . The steadystate forms of equations (120), (121a), and (122) then become
u dujdx
dx (h
and
=  (ljp)
dpjdx,
(6)
+
);
dY
= 0,
(7)
l ., ..,N , dx P respectively. In obtaining equations (6) and (7) body forces have been neglected (fi = 0); this assumption, which will be retained throughout this chapter, is an excellent approximation for practically all problems of the present type. On the other hand, the use of qR = 0 excludes many problems in radiation gas dynamics [2], [21]. The form assumed by the continuity equation, equation (119), can be derived formally by integration over the total crosssectional area of the flow. The limits of the coordinates x 2 and x 3 [which appear in equation (113)] in such an integration must be independent of x because the boundaries of the cross section are streamlines and must therefore be parallel to the local x coordinate (that is, parallel to the local velocity vector). Thus, since the flow variables are independent of the coordinates x 2 and x 3 ,multiplication of equation (119) by g2g3 followed by integration over the crosssectional area shows that
u'=l ~ . =
w. ,
then we obtain dh = T ds + (l/p) d p + C (pi/WJ dY.2. Therefore. . In view of equation (113). equation (19)] and the caloric equation of state [for example. . the double integral appearing here is simply ds. For a number of purposes it is convenient to replace equation (6) by an alternative expression. Although computational difficulties arise in forward integration procedures if some of the reactions approach equilibrium too closely.2. in steady flow. p. (9) Since the equation of state [for example. finiterate processes influence the choking behavior in the vicinity of the throat in a manner that is explained in [l] and [2].* numerical solutions for property profiles have been obtained (for example. equations (110) and (111) combined with the definition h = u + p / p ] relate the thermodynamic properties h and p to p. . and v. . . T. The formalism involved in * These problems and approaches to their resolution are discussed in Section B.. if all flow variables are specified at some point in the flow (for example. thenin principlea stepwise forward integration of equations (6)(9) [employing the subsidiary relations given in equations (18)(112)] will yield all flow variables at any other point (x) in the channel.2 2 Schematic diagram of nozzle flow. Hence the continuity equation is 11 d(pvA)/dx = 0.4. [22][26]). and Wi is the molecular weight of species i. T. d s ..which is the total crosssectional area of the flow.2. Reactions in Steady. N ) ... the regions where effects of finiterate chemistry are greatest . . equations (6)(9) constitute N + 3 firstorder ordinary differential equations for the N + 3 unknowns (i = 1. E A ( x ) . at point 1 in Figure 4. If equation (A5) is applied to a closed system consisting of a unit mass of the reacting fluid. QuasiOneDimensional Flow 97 I I I I I I I 1 FIGURE 4. and (i = 1. i= 1 N where s is the entropy per unit mass.5. N ) .2) and if the area A ( x ) is given as a function of x. These solutions are restricted primarily to supersonic. diverging portions of nozzles. pi is the chemical potential of species i.
1). For frozen flow. + v2/2 = ho pvA = (1 1) = total stagnation enthalpy) and vc1 (12) (riz 5 mass per second flowing through the channel). h (h. equation (8) simply reduces to y.3. and use is made of Equation (112) in obtaining the nexttolast equality. 1 while for equilibrium flow. W = M/N = X i q= is the average molecular weight. s = so (13) (so = initial entropy). for example.1. i=1 N N ~ds/dx = (pT)' i= 1 1 (pi/W. in which the chemical reaction rates wi all vanish. equation (8) can be replaced by an appropriate set of atom conservation and chemical equilibrium equations (see Section A.7 and the last part of Section 2.)wi (10) in view of equation (8). Since zr= X/w./N)/(M/N)] = d ( X i / F ) = d(&'K) = dx/vc/. impling that zr= i= 1 1(pi/wT.)dX = 0 N by the argument indicated above. for either frozen or equili .98 Reactions in Flows with Negligible Molecular Transport deriving the form given for the last term in this expression is as follows: dNJM = d ( N i / M ) = d[(N. The righthand side of equation (10) vanishes in two important limiting cases: (1) frozen flow. in which pi d N i = 0 in a closed system by definition [see equation (Al6)]. Equation (10) can also be expressed in an integrated form. where M is the mass of the closed element. For either frozen or equilibrium flow. Equations (7) and (9) can always be written in integrated forms. = y1 . and (2) equilibrium flow. N = N i is the total number of moles in this closed element.)' dv equations (6) and (7) and the preceding thermodynamic relationship yield T ds/dx which can be written as + C ( p i / w )dYJdx = 0.. 0 .Therefore.
TJT.' Propellant combinations with large values of I. for example. and (19) that T2/T. 4. where the ratio of specific heats is y = cp/c. A force balance on the rocket motort shows that provided the gas is expanded to the local atmospheric pressure at the nozzle exit (station 2). it is generally more convenient to use p . [29]. . the impulse delivered to the rocket per unit weight of propellant ejected. Specific impulse of rockets One practical reason for studying chemical reactions in nozzle flow is to obtain accurate predictions of the thrust of a rocket motor. through equation (1 1) which may be rewritten as From equation (14) a simple and explicit formula for v. and therefore u2 is divided by the standard gravitational acceleration in obtaining Isp. . followed by a nozzle (see Figure 2) in which the hot products of combustion are expanded to a high velocity./riz = v 2 .h. for example. The quantity I . h. See. Reactions in Steady. is conventionally expressed in units of seconds. (c. QuasiOneDimensional Flow 99 brium flow. = mv. + Ro/W). because the atmospheric pressure (to which p 2 has been equated above) is usually specified in discussing propellant performance.2. that is. Hence. For isentropic flow [equation (13)] of a onecomponent ideal gas with c p = constant. . the thrust (force in the x direction) acting on the motor is rizv. equation (14) yields * This same simplification also occurs. Since h = constant + c.).. (7). An important rocket performance parameter is the specific impulse I.4. Since (from cp = c. of course. are desirable. the value of u2 is relevant. it is well known and readily derived from equations (6). = (p2/po)(y1)/y. * . this value can be related to h . = specific heat at constant volume).* and all property profiles can be determined without solving any differential equations. where Ro is the universal gas constant and W is the molecular weight.T in this case. when some of the reactions are frozen and the rest are in equilibrium. Useful methods for computing the flow variables in these limiting cases are given in [27] and [28]. equations (6)(9) reduce to entirely algebraic relations.. apart from a dimensional constant.2. In place of the parameter T2.(1 . = c pT. which is seen to be given by I. ..2. (and therefore for ISp) can be derived if a onecomponent gas with a constant specific heat flows through the nozzle. A rocket motor consists of a chamber in which propellants burn.
and [30] are available for determining Zsp. when p 2 differs from the local atmospheric pressure). which shows that a high stagnation temperature To (To = the adiabatic flame temperature of the propellants). T. We have not considered ‘‘offdesign performance” (that is. formulas for I . wall friction in the nozzle flow. For frozen or equilibrium nozzle flow of a multicomponent idealgas mixture with variable heat capacities. then differential equations must be solved. The occurrence and consequences of shock waves in the nozzle under certain conditions has been neglected. I. or effort may be placed on developing computer programs for solving the appropriate set ofalgebraic equations. Thus a tool for measuring chemical reaction rates emerges [31]. which are unknown for many reactions. caused by the divergence of the flow streamlines at the nozzle exit. It may be worth emphasizing first that variable specific heats and chemical reactions in the nozzle are not the only causes of departures from equation (15) in real rocket motors.3.2. . For background material and for discussions of these additional phenomena. We have not mentioned the modification to I. 4. We have also neglected the effects of incomplete combustion in the chamber (a nonequilibrium. attention may be focused on obtaining effective mean molecular weights and specificheat ratios that will again make equation (15) approximately valid [27]. in general. v. regenerative cooling of the walls by liquid propellants. and so on. The latter approach has given the results that can be used with greatest accuracy [28]. Nearequilibrium and nearfrozen flows Let f j represent any flow variable (for example. [28].100 Reactions in Flows with Negligible Molecular Transport (aside from conversion factors). nonzero rates in the nozzle. the reader is referred to textbooks [32361. these criteria must depend on the reactionrate constants. It is important to discover how equation (15) is modified when the many simplifying assumptions introduced in its derivation are removed. heat transfer to the walls of the nozzle. there has been interest in deriving simple criteria for determining whether frozen or equilibrium flow is a good approximation for any given reactiont and in developing approximate methods to account for small departures from either of these limiting cases. a low molecular weight a high pressure ratio p o / p 2 (Po % the pressure in the combustion chamber of the rocket) and a low ratio of specific heats y all favor high motor performance.).and consider situations in which the initial conditions at a selected position in the diverging * In deriving these procedures. Since the computational procedures then become more complex. procedures such as those discussed in [27]. [30].. the comparison of measured composition profiles with profiles calculated for frozen and equilibrium flow provides information concerning the reactionrate constants through the use of these criteria.p . to find Zsp. burning mixture entering the nozzle). In such cases.* If reactions proceed at finite.2. This topic will be considered in the rest of Section 4. Clearly.
possesses special properties. QuasiOneDimensional Flow 101 portion of the nozzle shown in Figure 4. and (12) (along with state and rate equations) for describing the flow because the expansion of the entropy s.el G 1. expressions of the form d (%) = (1dA F j ) . and the corresponding G j is found to be of higher order than G j for other variables when an expansion is made for small values of Ah/&. > 0 in this form.* The solutions to the equilibriumflow equations are denoted by f j . while the area function A ( x ) is specified. It is most convenient to employ equations (8). under the influence of the finite reaction rate.Gj dx fj. The magnitude of the difference A h = f. . From the conservation equations. often only one independent reaction is neither frozen nor in equilibrium. (lo). For brevity of notation let us now suppress the subscript j . in order to define nearequilibrium flow. This effect is not addressed here. F j = 0 for the entropy. e. enow ) be introduced in equation (16). . thereby deriving for the new variables where Fe. finiterate chemistry may influence rn by modifying throat conditions.i is a function of the local equilibrium and nonequilibrium flow variables (but not of the rates).4. and the last term accounts for the tendency of f j to approach h. where F.e A dx may then be derived. Since s is constant in equilibrium. Reactions in Steady. the only remaining differential equations are those in equation (S). and construct linear combinations of the A yi that serve to diagonalize the coefficient matrix. are held fixed.2 are given. Therefore. The form of the expanded equation depends on the flow variable selected. are evaluated from the local equilibriumflow variables. The oneterm expansions F j = Fe. (ll). and the deviations in all other flow variables are related algebraically to A X . caused by the area change. and G j is a function of these properties and of the reaction rates as well. and Gi = ~ i G e .. as given by equation (lo). and correspond to chemical equilibrium.2. The differential * With upstream stagnation conditions and A ( x ) given. The general equation that has been given symbolically here can be expanded for lAh/fj. General thermodynamic stability conditions require that Ge. the first term on the righthand side of this equation results from the rate of change of f j . i j ( A ~ /may ~ . s is constant in the first approximation. Let M be the number of independent linear differential equations thereby obtained.is assumed to be small compared with the magnitude offj. Qualitatively.e ( x ) and are presumed known. consistent with the fact that each G j = 0 if all Afj = 0. and Ge.
d x ) Jo A F.I/dxbe negative whenever 1 A f J f . equation (17). . since integrals over x appear. a sufficient condition for these two inequalities to hold is that that is. is much simpler. One obtains and where f is again an arbitrary flow variable. and G. even for simple reactions. and A f 3 f . we require d(Af /J.] 2 t everywhere. parallel to that just discussed for nearequilibrium flows. This equation explicitly gives the fractional deviation of a property f from its local equilibrium value f. Thus at A f /f. dependent only on local properties.c. but unfortunately this criterion for nearequilibrium flow depends on the history. can be obtained from the differential equation for A f / f .:)Jdx2 0. ] exceeds its maximum permissible value t. and G. Thus the deviation from frozen conditions does not depend principally . > 0 and t > 0.6 . However. whichif satisfied everywhereis sufficient (but not. These conditions can be written as (F. from the prescription indicated above is complicated. Since G. t at A f Jf . = . for nearequilibrium flow. in general. dx’) d x (18) if A f / f e = 0 at x = 0. ) / d x I 0.f’. IAf/fel I t if and only if the magnitude of the righthand side is I t. f ./A)dA/dx I G .102 Reactions in Flows with Negligible Molecular Transport equation for A f / h given in equation (17) is linear and possesses the solution f= exp( f e J o x G.c at A f l f . and at A f If. It may be emphasized that the functional forms of F . G is proportional to the reaction rate. Equation (18) shows that given a small positive number t. d dx A ex. and therefore the criterion given in equation (19). An approximate condition for the occurrence of nearequilibrium flow.f.f/. = t and ( F J A ) dA/dx L G.. A development for nearfrozen flows. Equation (19) constitutes an upper bound on the fractional rate of change of area. = c. to find the functions F. depend on the flow variable that f is taken to represent. we require d ( Af / . A reasonable condition is the requirement that d 1 A. = . the subscript f identifies quantities in the frozen flow.( 1 : G. necessary) to ensure that IAfif.
For the reaction under consideration. let us consider the reaction A e B. identifying species A and B by the subscripts 1 and 2. . N ) and K.4.(n = YJYl (24) for this reaction [see equation (A27)].(T) are known functions of x and are the same in equilibrium and nonequilibrium flows (since only trace amounts of A and B are present). Reactions in Steady. enthalpy. = W. respectively. The other flow variables may then be considered to be known functions of x in investigating the effect of the reaction rates on the trace concentrations.2. equations (8) and (21 1) yield We need not consider dY. .). . The equilibrium condition is x.+ 3. because the reaction then has a negligible effect on the pressure. equations (18). is the equilibrium constant for partial pressures. QuasiOneDimensional Flow 103 on how rapidly the frozen flow variables change with x. it can be inferred that where the rate constants refer to the forward reaction A . .= K. From rate formulas [for example. As an explicit illustration. Here K . since Y2=lY1i= 3 cx N and are known for the species not entering the reaction. and the last equality follows from the fact that W. Equations (22). Only the concentrations of the trace species involved in the reaction are affected appreciably by the rate of the reaction.4 Application to the reaction A in only trace amounts $B with species A and B present The calculations discussed in the preceding section are particularly simple for reactions involving species that are present only in trace amounts.2. (25). (23). 4. but instead is roughly proportional to the distance (or time) available for a departure from frozen conditions to occur. the value of Y. and (26) yield .Jx) = ( c x)/(1 + K. (B1 l)./dx. density. and other variables./x. for this reaction. 1i=3 N Here (i = 3. is given by equations (23) and (24) : Y1. and (Bl3)]. velocity. For equilibrium flow.
l 4 1.f.Y.Yl./Y. In particular.d In Y. For frozen flow.. The equivalence of equations (29) and (16) is apparent. Y.. For nearfrozen flow. f is the initial value of Y. = . equation (27) becomes . where now AY. Thus the transcription of the results of the preceding section for nearequilibrium flow becomes obvious.. = Yl. = Y. For nearequilibrium conditions. Equation (27) shows that When lAYl/Yl. .f = constant. brium flows.. in equation (30) define F. = Y. we are interested in AY.. . to retrieve the previous notation. where is a known function of x and is the same in equilibrium and in nonequili. the terms on the righthand side of equation (29) will be of the same order if whence equation (29) becomes approximately for nearequilibrium flow../Y.104 Reactions in Flows with Negligible Molecular Transport for nonequilibrium flow. .. .. the criterion for near equilibrium [equation (19)] is for the present reaction.. where Y l . where AY. In terms of this variable.. we are interested in AY./dx/d In Aldx.
)wb/p. that is.2. On the other hand.. either wF 4 wE or wE G w F .5. QuasiOneDimensional Flow 105 is a known function of x.)wk/p. the composition profiles in a supersonic nozzle follow equilibrium curves very closely until a point is reached at which a relatively rapid transition to frozen flow occurs. it is sufficient to obtain a condition specifying the location of the freezing point . . The intermediate freezingpoint condition is therefore determined by either 1 v dYJdx 1 % wF or 1 v d Y. we can write equation (36) as v dY. 4.v./dx / 2 w E . When rate data are available. combining equations (8) and (211) yields vdx/dx = W(V’. Reactions in Steady. it is straightforward to estimate freezing points of this type [24].(vl. These criteria play roles in design criteria to maximize nozzle performance.v. (36) where w‘ is the difference between the forward and backward rates of the reaction. A criterion for nearfrozen flow can be written as for this reaction.2. . after which the remaining portions of the composition profiles are practically frozen [24]. wE = W. wF z wE.4.depending on whether oFor wB becomes small in frozen flow./dx = WF  WE. ./dx( % oE.2.3 and illustrated in Section 4. Thus equation (20) and the corresponding results of the preceding section are obtained.2. .(vl. When only one reaction occurs. i = 1. (37) where wF = W. N .’ . when the flow is near frozen. In order to determine the flow variables for flows that exhibit this “suddenfreezing’’ character. It has been found that for threebody atomic recombination reactions (primarily due to the cubic pressure dependence of the recombination rate). When freezing occurs . that is. see equation (B1 l)]. nearequilibrium and nearfrozen criteria are unimportant. Freezing of reactions The reasoning outlined in Section 4. 1 v dY.and ( v dYJdxl is of the same order of magnitude as the larger of the two rate terms according to equation (37).v:)o’/~. either I v d YJdx 1 % wF or lvdY. and wk and wk are the forward and backward rate terms in w‘. ./dx I < wF and I v dY. Letting species 1 represent a product of the reaction./dx I < according to equation (37).4 was preceded by many approximate criteria that are less precise for the attainment of nearequilibrium flow [37][40]. When the flow is near equilibrium. respectively [for the forms of these terms.
All the quantities appearing in equation (38) can be evaluated from the equilibrium flow variables and the chemical kinetic formulas for mF and 0. This condensation tends to improve rocket performance by releasing heat but introduces the complications of twophase flow in the nozzle. directed toward predicting the increase in entropy that occurs during freezing. K . A I A A Journal 6. the quantities may all be evaluated in nearequilibrium flow. This approach has not yet been pursued. containing solid or liquid particles with constant * See P. Blythe. and the freezing condition then becomes. 17. ranging from fully equilibrium to fully frozen flows. This observation suggests an approach to obtaining an improved description of influences of finiterate chemistry on nozzle flow. aerodynamic drag on the particles and heat transfer from the particles increase entropy. 831 (1968). J . approximately. . 4. Twophase nozzle flow Many rocket propellants form solid or liquid products of combustion either in the combustion chamber or in the nozzle. Lee.6. 126 (1963). Therefore. (38) where the subscript e identifies equilibrium flow. As a first step consider a onecomponent ideal gas with constant specific heats. in the first approximation sudden freezing occurs at the point where equilibrium calculations predict that the first term in equation (38) equals the second or the third. in precise analogy with the effects of finiterate chemistry. the location of the freezing point parameterizes the continuum. with regions of equilibrium and frozen flow separated by a transition region. There is a continuum of isentropic nozzle flows. This is evident from the fact that equation (13) applies in both equilibrium and frozen flow and is a further manifestation of the exceptional attributes of entropy in nozzle flow. 823..* IUe(dY1dx)el % m F .2. Gasparticle flows have much in common with reacting flows. A curious consequence of the suddenfreezing approximation is that the flow remains isentropic. A. c p and c. for example. Good agreement of suddenfreezing predictions with experiment has been obtained for NO. e . S. e % W B . although detailed analyses that treat the ratio of the thermal energy to the heat of dissociation as a small parameter provide important ideas that would be helpful in beginning the study. 243 (1964) and H. it appears to be of interest to discuss twophase flows briefly. Nuid Mech.. In the vicinity of the freezing point a perturbation may be sought in the time interval needed for freezing to occur. 20. the twophase effects are numerically larger and often of greater practical significance in contributing to losses in performance. recombination [41] but not for ion recombination [25]. at the freezing point. The result would be a more accurate description of the property profiles. Moreover. Cheng and R.106 Reactions in Flows with Negligible Molecular Transport suddenly.
different from that of the gas. n.Z)(e. The enthalpy per unit mass of this gasparticle system is h = constant + Zc. (42) . as may be seen by algebraic manipulation.us). The penalty is greater if the particles cannot follow the changes in gas properties.. that are sufficiently small to maintain the same velocity and temperature as the gas and that do not exchange mass with the gas through condensation or evaporation [28]. cs. from equation (19) we may write p = psTRo/W. while retaining all the other approximations indicated above. This relationship may be used in equation (14) for v 2 . T. (6). v.dv./dx = 6nr.Z)(c. Equation (39) states that the total volume per unit mass is the sum of that of the condensed and gaseous phases.Z)c. = constant. where ps is the gas density. in accordance with the expression for h. and the Stokes law of drag applies. a performance penalty is associated with the twophase flow. (40) where p is the gas viscosity.Z)c. respectively. and the equation of state in terms of p becomes the same as that for an ideal gas with molecular weight W/Z.2. For illustrative purposes let us assume that thermal equilibration occurs but allow for a particle velocity. but the consequent increase in I. = constant. momentum.. Reactions in Steady. Neglecting the contribution of Brownian motion of the particles to the pressure. the mass flow rate of particles is n s ( $ n r ~ p s ) u s= A viz. for the twophase system. which is related to the total mass per unit volume P by (1  ZYP. QuasiOneDimensional Flow 107 specific heat. generally is less than the decrease associated with that arises from the replacement of W. is the specific gravity of the condensed phase./c. = l/P> (39) where p. as the effective specific heat at constant pressure.. and (7) express appropriate mass. but the altered equation of state modifies equation (15).A = viz. Therefore. so that ps x Zp. [33].Z)p/ps4 1.)]/[Z+ (1 . subject to the indicated replacement of molecular weight and to the use of Zc. If the particles are spherical. + Z/P. v. even in this the factor most ideal situation. then a force balance on a particle gives + fi $nr3psu. T + (1 .p(vq . [36].)]. + (1 . (41) The mass flow rate of the gas is (pW/RoT)v. Thus in equation (15) W is replaced by W/Z and y by [Zy (1 .4../c. and energy balances. all with radius r.. Since equations (9). Generally (1 . in this approximation the derivation of equation (15) remains valid. the gas is excluded from the volume occupied by the solid or liquid. This effective y decreases as l . In terms of the number density of particles.Z increases. where Z is the mass of gas per unit mass of the system.
pDv/Dt pDu/Dt = = (47) . [Sl]. characteristic surfaces Let us now consider the unsteady.(c. p . threedimensional flow of a homogeneous reacting fluid with negligible transport properties. in the first approximation.T + u.2. If the former is much larger./dx = Adp/dx (43) (44) and k.4) and many other problems [53][55]./dx + kgdu..u. [28]. + h.T + $12) = constant.3.2pS/9..1.1. is sufficiently largethen in the first approximation us is approximately constant through. and generalizations of the characteristic methods discussed below become useful. and I may be developed [28]. We shall return to twophase flows in connection with spray combustion (Chapter 11) to give a more systematic development. If the former is much smaller. n.2/2) + kg(c. Among additional topics of interest in twophase flows are questions of sound propagation in twophase media [28]. and T. ug. If the lag is neither large nor small.1). THREEDIMENSIONAL FLOW 4. [43] and have been considered in connection with optimized nozzle design [44]. if Y. REACTIONS IN UNSTEADY. axisymmetric flows must be considered in analyzing these processes [47][50]. Vp. then numerical integration is generally needed [45]. Conservation equations. This time lag can be compared with a representative residence time in the nozzle.3. and the results described after equation (39) apply. Perturbations about this smalllag limit have been studied because of potential practical importance [42]. [52] (see Section 9. From equation (40) a characteristic time lag or response time for velocity equilibration can be identified as 2r. Particles may fail to follow streamlines and produce undesirable effects by impinging on walls.108 Reactions in Flows with Negligible Molecular Transport and the total rate of mass flow is m = viz.dv. The generalizations of equations (6) and (7) for overall momentum and energy conservation are viz. p(V * (45) (46) v). Equations (40)(44) serve to determine the five unknown variables us. 4. such as riq'(Adp/dx).for example. is low [28]. equations (11)(14) become DplDt + pV * v = 0. Effects of temperature lags are similar to those of velocity lags. Condensation and agglomeration processes also may be important [46]. Perturbations about this largelag limit out the nozzle. In view of the simplifications that arise when transport effects are absent (see Section 4. then us = v.
Yi? (52) * Here and in what follows.yi% + (%)p. we find N Substituting this relationship and equation (45) into equation (47) gives where use has been made of equation (48) in the last equality. employed in obtaining equation (10) in Section 4.yj(j+ + one can show through straightforward thermodynamic arguments that where the frozen sound speed af is determined by a. i = 1 . Reactions in Unsteady./Dt = wi.. at constant r.yiE jl(%)s. . all N of the K’s are independently variable in the differentiation. By substituting equation (49) into the mathematical identity* DT Dt = ($)s. (48) respectively. When the same kind of reasoning used in deriving the expression for dh. is applied to equation (A3). The righthand member of equation (49) is the rate of production of entropy by the irreversible chemical reaction.v. ThreeDimensional Flow 109 and pDY.(j # i ) are meant to be proportional to derivatives with respect to the mass of species i in the system at constant values of the masses of a11 other species in the system. = 1 is not to be imposed in evaluating such derivatives.p.2.4. where the substantial derivative is defined as opt = a/at + v . it is convenient to write equations (45) and (47) in alternative forms.. . With this interpretation.3. and the restriction CF=.N . In order to illustrate most easily the mathematical properties of (45)(48). derivatives with respect to rl. . . = (aP/aPlS. Equation (49) is a useful replacement for equation (47).Yi> (51) the frozen volumetric thermal expansion coefficient (which equals 1/T for an ideal gas mixture) is given by Pf = PCa(l/P)/aTI.
.. ax. x aY)ko (ax... + terms in lowerorder derivatives +f.f = (ah/aT). . defined by the equation x1. . ' . Equation (54) is a useful replacement for equation (45) in studies of the characteristic surfaces of the governing equations.  = 0. and (54) may be taken to be the governing differential conservation equations. Equations (48) and (49) are already in characteristic form. y j ( j + i ) appearing in equation (55) is simply the (total) term (ah/aYi)p. Y. u ~ . . Equations (46) and (54) involve derivatives only of p and v.thus the term o i w i is a measure of the rate of liberation of heat by the chemical reaction. the quantity hi given in equation (1 . has a characteristic surface.... 2..).' the characteristics of these equations require further study.. ax. and the dimensionless parameter oi becomes oi = T ) .)=O..ll)]. (58) * For a general discussion of characteristics and for the definition of characteristic surfaces with an arbitrary number of dependent and independent variables. [56]. for example. u ~ u. ~ . x . specific enthalpy of species i [that is. Equations (46). i = 1 . ..* they show that composition and entropy changes propagate only along streamlines.(xo. The use of the method of characteristics in solving equations is considered in [57]. . (a. .. the p . (56) (57) w%.. This is the reason that equation (54) is more useful than equation (45) in the present context. (49).110 Reactions in Flows with Negligible Molecular Transport and the frozen specific heat at constant pressure is (53) Substituting equations (45) and (48) into equation (50) yields the expression c p . (48).. see.) = 0. N _ where i= 1 (54) (55) For an idealgas mixture with a constant average molecular weight. N . It is known [56] that an arbitrary system of quasilinear partial differential equations which may be written in the form xr=. . x.x.
+v 2 ax. u N ) are the coefficients of the highest order ( n j ) derivatives of u j in the ith partial differential equation. (59) which is a firstorder partial differential equation for the characteristic surface. . t i 2 . . .+ v1 __ + v2at ax. in that term must be zero. x. . ax. x l . . . . + f = 0. av. . at 3 _  and + a ( . Reactions in Unsteady. . . . . ul.+ aP ax. In equation (56) there are n + 1 independent variables denoted by x . aP ax.  av. . u 2 . u.. av. P a x . uN) represents the terms in the ith equation that involve no derivatives at all. av. . + vlax.. while fi(xo. 1. ThreeDimensional Flow 111 where vertical lines represent the determinant of the matrix within them. + 213 2) +++av.x l . the integers k. ax. : ( x ~ . When there are no derivatives of order higher than the first (nj I 1 for all j ) .. x i .. ax. We may then use a new notation which is obtained by letting k. equation (56) may be written as (ko.N . ax..xn . . if one k. In equations (46) and (54). ~ I . a ~ .ax.n) and N dependent variables denoted by u j . . n and is equal to the 1 value of the only nonzero k l . Equations (46) and (54) may be written in full in Cartesian order ( n j I coordinates as follows: av. The quantities A $ C J . + . . d (xo. . 1 aP v. . In this case. x. kn) + J .. u1. (64) . is unity in a term of the summation in equation (56).1. . ul. and equation (58) becomes i = 1 . . . + v 3 av 1 ap 2+ = 0. . . . . 2 . a ~ . . Pax. (1 = 0.. then every other k . may assume only the values 0 or 1. . .k . where k takes on the values 0. av3 ax.4. . . .. . .3. + v2. av + 1 a p = 0.. In this simple case. k. . . u.. .u N ) = 0. the highest derivatives are all of the first 1).
. x 2 . Y(t. while u4 = p then a table of the Afj may be constructed (Table 4. and 3 on x represent the various coordinates. 3. u. By comparing equations (61)(64) with equation (59). It is seen from equations (64) and (54) that f = oiwi/p. . respectively.1 j = 1 k=O k = l 01 j = 2 k = 2 02 k = 3 03 k=O k = l k = 2 k = 3 i= 1 i=2 i = 3 i=4 1 0 0 0 0 1 0 01 0 02 0 1’3 0 0 1 j = 3 0 0 0 0 0 0 0 0 0 0 j = 4 0 1 0 0 Ik=O k = l k = 2 k = 3 I k=O k = l k = 2 k = 3 i= 1 i=2 i=3 i=4 0 0 1 0 0 0 02 0 0 03 0 0 0 1   1 0 1 ~ P 0 0 1 P 03 Pa.. i = 1 through 4 is allowed to correspond to equations (61)(64).x. and u j = vj for j = 1.1). and the subscripts on v denote the components of v in the corresponding directions. . . . u 2 . ..112 Reactions in Flows with Negligible Molecular Transport TABLE 4. we obtain the following relationship defining the characteristic surface. Dt P ax. 0 L’l 0 0 01  P 0 1’2  0 0 0 1 Pa: Pa: Pa: Here the subscripts 1.x l .1 into equation (60). . .xl. By substituting the values of AfJ(xo. 2. If xo = t . 2. uN) given in Table 4. the A f j may easily be determined. x..): z=.
2. z 0. twodimensional (axially symmetrical and plane) flows For steady flows. and (54) as the governing differential conservation equations.* This last result has been emphasized by Wood and Kirkwood [SS] and by Chu [59]. (67) which shows that streamlines are characteristic lines of the equations. adopting equation (70) and the steadystate forms of equations (46). equation (69) reduces to the relationship + v 2 / 2 ) = 0. equation (49) may be replaced by an expression that is both simpler and generally more useful. (68) which defines characteristic surfaces that propagate normal to themselves with the frozen sound velocity af relative to the local massaverage velocity of the fluid.3.3. + ax.( V Y ) * ( V Y ) = 0. Since equation (70) is simpler than the steadystate form of equation (49). . equation ( 6 8 ) then reduces to (P)* a. The other solution to equation (66) may be written as (DY/Dt)’/a? . and since enthalpies are usually easier to compute than are entropies. it is generally convenient to employ h + v2/2 in place of s as a new dependent variable. That this choice is not convenient for unsteady flow is apparent from the fact that equation (69) involves ap/ & and therefore would have to be * This result becomes more transparent if the coordinates are transformed in such a way that the fluid is brought locally to rest. (48). (70) which states that the total stagnation enthalpy ( h + v2/2) is constant along streamlines. ThreeDimensional Flow 113 Evaluation of the determinant yields One solution of equation (66) is DY/Dt = 0. By substituting equation (45) and the identity h = u + p / p into equation (47). The method of characteristics for steady.[(”)z  ax.( l / p ) a p / a t = 0. 4. + (q(?)’I ax. v * V(h (69) For steady flow. in which equation (46) may be employed to show that D(h + v2/2)/Dt .4. we obtain the expression Dh/Dt . Reactions in Unsteady.(l/p)Dp/Dt = 0.
P i = l . w. we find d[ = d x cos 8 + dr sin 8. In view of equations (75) and (76). 8 = tan’(u. respectively. (73) It is convenient to use the distance in the streamline direction. r be the radial coordinate normal to the axis of symmetry. v = (of + v . and the distance normal to streamlines. (see Figure 4. (48). ) l i 2 . let x be the axis of symmetry. the result is . and (54) become.. ar ar..3). and ax ar./u. Then equation (70) and the steadystate forms of equations (46). v1 be the component of velocity in the x direction. = u cos 8. 5. and the angle between the flow direction and the x axis. For steady flow with axial symmetry. dv] = . The first relation in equation (78) may be used to eliminate the velocity derivative from equation (80). In terms of the magnitude of the velocity. and u2 be the component of velocity in the r direction. q. equations (71)(74) can be shown to reduce to respectively. vl+v2=~.).N .d x sin 8 v2 = v sin 8 + dr cos 8.114 Reactions in Flows with Negligible Molecular Transport included along with equations (46) and (54) in calculating the characteristic surfaces for the pressure and velocity equations. in place of x and r as independent variables. .. (75) (76) and U.
3. (78). (x. (78). Their characteristic lines may easily be obtained by the methods of the preceding section.y). and (81) may be taken as the governing set of differential conservation equations for steady.. Equations (77). ThreeDimensional Flow 115 r'yl \ FIGURE 4.1 0 = 0. respectively. q) coordinate where M = u/a.4. . for Aq = 0. axially symmetrical flow.r ) . . (82) (83) (84) i = 1. Reactions in Unsteady. Along a streamline (Aq = 0). The finitedifference forms of equations (77).3. (79). N .[ l / ( p u ) ] Ap (where the symbol A indicates a small increment). (79). is the Mach number referred to the frozen speed of sound. . for Aq = 0 and Av = . . + u2/2) = 0 for Aq = 0. equations (77) and (79) and the first relation in equation (78) reduce to total differential expressions and become. and (5. V X Schematic illustration of the definitions of the (x. Equation (81) and the last relation in equation (78) constitute two independent equations for the derivatives of 6 and p and have characteristic lines [57] given by 1 0 0  1 PV2 0 1  M2 . systems. and (81) are useful for obtaining numerical solutions by the method of characteristics for supersonic flows. A(h A T = [ w i / ( p v ) ]A t .
A total of N dependent variables ( p . which cannot be connected by a single streamline or Mach line. and (86) is very similar to the method of characteristics for nonreacting rotational flows [60]. These Mach lines will intersect at a point C .116 Reactions in Flows with Negligible Molecular Transport that is. All properties at the point C are now known. the properties p D . Along these lines. uD. is given by Al* = 4 M Aq along the lines Av] = A < / J m . there are no novel basic differences in the refined methods.4. In this manner. By computing the length Atc of the line DC. All properties must be known at two neighboring points. equations (82). and one may proceed to the next step.By a linear interpolation along the line AB.) is then found to cross the line AB at a point D. hD. which defines the Mach lines based on the frozen sound speed. Briefly. one may then determine vc from equation (84). (83). . the principal difference is that here entropy varies along streamlines as well as normal to them. one obtained by reading the upper signs and the other obtained by reading the lower signs. While many refinements of the procedure outlined above yield better accuracy [60]. (78). that the relationship must hold. (the pressure and the flow angle at point C). and y) appear in these equations. one finds by substituting equation (85) into the finitedifference forms of equation (81) and of the last expression in equation (78). (84). the new point at which all properties are to be computed. 8. Since the distances AC and BC are known.which is the geometric distance along the Mach lines.* Here Al* . One may then construct Mach lines of opposite families at points A and B. and (81). The explicit numerical calculation procedure for solving equations (82). h. A and B in Figure 4. & from equation (83). properties throughout a region of the shape indicated in Figure 4 3 a ) may be obtained. When M > 1 [so that the values of Aq given by equation (85) are real]. It is worthwhile to consider what kinds of boundaryvalue problems 4 are correctly set for equations (77). the basic step in the method of computation is as follows. by Au = fA C I J F T . (79). The extension of the streamline through the point C in the upstream direction (at angle 8. u. and (86) can be used to obtain a stepwise solution to the conservation equations. and h. equation (86) determines the values of pc and 8. (83). (84). from equation (82). subsidiary + * Expressions such as equation (86) are intended to represent two equations.and so on may be found approximately at point D.
It follows that a correctly set 4 dependent Cauchy initial value problem [57] is one in which the N variables are given along a noncharacteristic curve [that is. relations (such as the equation of state) enable us to express all other quantiand wi) in terms of these dependent variables. M . We have ties (namely. (b) Variables specified along streamlines and Mach lines. Reactions in Unsteady. see Figure 4. Mach lines Streamlines  FIGURE 4.5.3. and are determined along streamlines. 0 given . (c) Variables specified along intersecting Mach lines. Elementary step of the characteristic calculation. all given (b) _ _ _ _ _ Mach lines Streamlines Boundary of region of solution all given (c) FIGURE 4.4. shown [equations (82). in many practical + / / /’ // / 1 p . (a) Variables specified along a noncharacteristic line. neither a Mach line nor a streamline. h. p. . (83). Unfortunately. (84).4. and (86)] that relationships between the differentials of p and 0 exist along Mach lines and that the differentials of u.5(a)]. oi. ThreeDimensional Flow 117 ___.
t plane. Throughout this section we have been discussing steady. . C oiwi. our equations and results can be made to apply to steady. unsteady flows Let us next consider onedimensional. axially symmetrical flow. The method of characteristics for onedimensional. Along the streamlines. (89). unsteady flows with velocity u in the x direction. (92) . 4. . and we do not have a simple Cauchy problem. Thus if the radial coordinate r everywhere is replaced by y . we obtain the following pair of differential equations : + (U +_ ax = u. and sin e / r in equations (81) and (86). plane. . .118 Reactions in Flows with Negligible Molecular Transport problems data are given along characteristics. u sin B/r in equation (80). and (54) reduce to p aqat + p u aqax + aplax = 0. The discussion is not modified in any way by these changes. and (91) are used in obtaining numerical solutions by applying the method of characteristics in the x . and equations (88) and (89) become Ayi = (wi/p)At/2. If we multiply equation (90) by a.3). The finitedifference forms of equations (88). also determine solutions in finite regions. for Ax = v At. Explicitly. equations (46)./r in equation (74). In this case. unsteady flows. of course. . i= 1 (87) (88) (89) and respectively. Data of this last type can. .3. i = 1 . N . the Cartesian coordinate perpendicular to x (see Figure 4. Procedures slightly different from that described in the preceding paragraph are required in solving such problems numerically. then we need only neglect the curvature terms in order to obtain equations that are valid in plane flows. twodimensional flows. . axlat + u ayilax = wi/p. we delete the terms pu. (48). . N . N aspt + u aslax = (PT)' 1 (pily)wi.5(b) and (c). as is illustrated in Figure 4.3. With only a few minor modifications in the formulas. (89). and (91) constitute a useful set of governing conservation equations for characteristic analyses of one dimensional. and equation (87) by af and then add and subtract the resulting equations. Ax = u At. (49). i = 1. i= 1 N (91) Equations (88).
e/Pl. ThreeDimensional Flow 119 and As = (l/pT) i= 1 c (pi/K)wiAt/2 1 oiwi At/2. 1 . and the equilibrium constant for partial = x2. which are defined by Ax equation (9 1) assumes the totaldifferential form N Ap f p a f Av = u? for Ax = (v k a. Preliminary relationships Much information can be gleaned from the linearized forms of equations (87)(90) that are applicable for small departures from a uniform quiescent state of chemical equilibrium. and [from equation (18)] w2 = . (94) Thus the streamlines and Mach lines again take on special physical significance. we shall consider here only a binary ideal gas mixture experiencing the reaction A B.3. Wl = W (i = 1. = X 2 . . The reader may consult [61] for details of procedures in which equations (92)(94) are employed in obtaining numerical solutions and for discussions of correctly set initialvalue problems. Similarly. i= 1 N for Ax = v At.e [see equation (A26)]. For simplicity. = P2.3.4. that is. reacting idealgas mixture for the reaction A B 4. respectively. = (93) (v k a.e = K .4.3.4. (96) + where Y = Y.e/xl. changes in entropy and composition propagate only along streamlines. and changes in pressure and velocity propagate only along Mach lines.) At. Analyses are greatly facilitated by utilizing the special properties [equations (92)(94)] of the differential equations along the characteristic lines [61]. unsteady sound propagation in a binary.1. Onedimensional. 2). = W (equal molecular weights).Y) . Corresponding analyses for a simple dissociating diatomic gas [62] and for a gas experiencing an arbitrary onestep reaction [59] may be found in the literature. Reactions in Unsteady.. Letting the subscripts 1 and 2 identify species A and B.Y pressures is given by = X. = + KJ.(Y/Kp)1. All the essential physical phenomena can be exhibited in this special case. 4. .w l = WBITa'l(p/Ro)eE'IRoT [ ( I . along the Mach lines. KA1  r. X i = we then have N = 2. P = P(R0/W)T (95) [from equation (19)].) (97) r.)At.
3. Since ci = h .3.s10? w p = c(aw2/~P)Y.3. = 0 for chemical equilibrium [see equation (A21)]. we shall set f = fo + f ' . In obtaining equations (100) and (102). for any dependent variable f appearing in these equations.is s' = 0. wheref.and w... and (90) become. Since the quiescent value uo of the velocity u is u. 4. 'Ow2 5 (98) where use has been made of equation (96) and the heat of reaction (per unit mass) has been defined as q = h .h Z . r ~ ) . ~for . is aconstant (independent of x and t ) that corresponds to quiescent chemical equilibrium conditions and f ' is small. use has been made of the fact that the unperturbed state is one of chemical equilibrium (w2. = 0). 4.120 Reactions in Flows with Negligible Molecular Transport in which the subscript e identifies chemical equilibrium conditions. Neglecting terms of order higher than the first in f ' and in each of its derivatives. = 0 and ( p z . Linearization In order to linearize equations (87)(90). In deriving equation (101).4. 7 ideal ' ) gases with constant molecular weights [see equation (55)Q. this result has already been emphasized in Section 4. ar'lat asilat = (99) ( w y Y' 0.4. Po avlat + ap//ax = 0. respectively.p1). ( w . (102) where WY = C(aw2/ay>.) ap'iat = (qlc. (100) (101) = and po av/ax + (ila.SO. (89).ylO. the righthand side of equation (90) becomes N  i= 1 1 ciwi = (q/cp.slo. Equation (98) has also been employed in equation (102).2.3. = 0. use is made of the fact that the righthand side of equation (89) is of order higher than the first since w2. + wppl + wssypo. (88) for i = 2. = 0 at (103) . / ( ~ ~ . Reduction to a single partial differential equation t = The solution to equation (101).. and we shall therefore omit the prime on the small quantity u._= C(aw2/as>. we then find that equations (87). . subject to the condition s' 0 for all x. ~ ' wpp' + + W. we have u = u'. Equations (95)(98) comprise subsidiary relationships that are required in the analysis.2..
T"l'(p/Ro)eE1'RoT]o x {[I + (l/Kpo)IY' + (Yo/K%o)(dKp/dT)o T'I. depends only on temperature. we find that the last term in the braces in this expression reduces to .Y = Ye( 8 P P u s . By solving equation (105) for T' and substituting the result into equation (104). present gas. and p'. and the frozen sound speed a f .4. respectively.[1/(1 + K .w20 = [WB. 1/d = 1/4 + ( 8Y / @ ) . let us compute l/a. we can then easily identify the coefficients of Y' and p' and can thereby obtain wy and w p . the only derivatives of w 2 that we need to evaluate for use in equations (100) and (102) are wy and w. that 40 dY + C. we find [in view of equation (95)].we find by differentiation that dh 4 dY + ~. for our present purpose. and d p appearing in equation (105) may be identified with Y'. when equation (A5) is applied to a unit mass of the gas near equilibrium.. In order to relate 6 to the equilibrium sound speed a. (104) where use has been made of the fact that K .3. ThreeDimensional Flow 1 121 Therefore.In this way. we obtain dT = (l/PO) dP. w2 . 0)1(4~/R0T2)0T'.h. and.fdT. In view of equation (51). and 6 will now be shown to be simply related to the difference between the frozen and equilibrium sound speeds. = ( 8 ~ / 8 p ) ~ .. (105) where use has been made of equation (103) (ds = 0) and of the fact that the coefficient of dY arising from the last term in equation (A5) is zero at chemical equilibrium.. T'. for ~ = the ~ . Employing equation (97) and the van't Hoff equation [equation (A49)].p ' (108) . + Y2h2. Reactions in Unsteady. The quantities dY. Since the quantity in brackets in equation (96) is zero in equilibrium. = Since h = Y. dT. therefore. we find from equation (96) that for small departures from equilibrium.fO and that (107) The quantity z is clearly a representative reaction time.
u satisfies the simple wave equation __ 1 aZv  a2v ~ u. Since equation (105) is valid at constant s a n d a t Y = x. we obtain 1 1 aZv a2v (113) where use has been made of the definitions of z and 6 [equations (106) and (107)] and of equation (112). (1 11) The substitution of equations (109)(111) into equation (108) yields the required relationship l/UZo = l/u. In view of equation (103) after differentiating equation (102) with respect to t and subtracting the result (multiplied by po) from the undifferentiated form of equation (102) (multiplied by wy)..Y=. (97).we may make use of equation (100) to show that By differentiating this expression with respect to x and then using the first and second t derivatives of equation (99) to eliminate a2p'/axdt and a3p'/ax at2.fdT/dY. [ ( a m u s ... = (aT/aY).f~o~'>/(~42>1~1.(aP/an.)2/K..IC(~... . The only dependent variable appearing in equation (1 13) is the velocity v.4) (R0T/WP4){(c. Equation (1 13) implies that for very slow reactions (l/z + 0).@W/RO T 2 ) ..f/4)(d[Kp/(l + Kp)l/dT)'  (R0T/WP4){1 + C(1 + ~.o + 6.o at2 ax2 = O . = = = (l/P)/(cp. thus. (110) where use has been made of equations (99. . Equation (105) may also be used to evaluate the remaining partial derivative in equation (109) at chemical equilibrium (the state of present interest). (112) where 6 is given by equation (107).lo = (4/c. f)O. (109) where use has been made of equation (95). It is instructive [62] to reduce equations (99)(102) to a single partial differential equation. (ay/aP>s. = (aT/ay)s.122 Reactions in Flows with Negligible Molecular Transport Here (aPlay). and (A49) (the van? Hoff equation)..
Generation of sound waves in a reacting gas.o/aed4 + ( ~ z > ~ 1 /+ [ 1( ~ z ) ~ I l ) " " and CP (115) +tan. t ) = V(x)eiW'. . On the other hand. 4. Reactions in Unsteady. (the equilibrium sound speed).o/aeo>2.3.4. by substitution into equation (113).'{C(a. where.1I~z/"(a~o/aeo>' + ( ~ 0 z ) ~ I ) .) v(x. (1 14) = CC(a. Harmonic solutions to equation (1 13) will then be given by (the real part of. Suppose one generates sound waves in a gas occupying the region x > 0 by oscillating a piston harmonically about the point x = 0 (see Figure 4. where V(0) is the constant (small) amplitude of the piston velocity perturbation and o is the (angular) vibrational frequency.4. for very fast reactions (z + 0).)x cos cp]}. v = V(O)e'mt or v = ( 0 for t < O V for t > O FIGURE 4. v satisfies the wave equation 1 a2v a2v a:. t ) = V(O)exp[ (wcc/afo)x sin cp]exp{io[t where (a/a. The velocity of the piston can be represented by the real part of v(O.. ThreeDimensional Flow 123 with a propagation speed equal to the frozen sound velocity. (116) Ex f Reacting gas T' Piston.6..3. t ) = V(0)eiw'. / a ~ =~ 0. for which Vremains bounded as x + 00. since they illustrate sound dispersion resulting from finite reaction rates.4. we obtain v(x. Dispersion relations [62] Solutions to equation (113) with a sinusoidal time dependence are of interest.)  From the solution to this equation.6). (1 + i o z ) d 2 V / d x 2+ ( w / ~ ~ ~ ) ~ [ ( a + ~icoz]T/ . at2 ax2  0 with the propagation speed a.
As w + 0.5. where s is now the Laplace transform variable. afo and 1 + 2af0 ~/[(afo/aeo)2 . the solution to equation (117) is Jr  + u = (V/s)exp[(sx/aro){l [l . Since no disturbance is imposed at x = a. the gas is entirely quiescent and is in chemical equilibrium.” e%(x.I] .o/afo)2]/(1 + SZ’)”’’~]. t ) to equation (113).124 Reactions in Flows with Negligible Molecular Transport This result shows that the phase velocity of the disturbance is a = ufo/(a cos cp) and that the disturbance attenuates as x increases with a characteristic decay length given by I = afo/(wa sin cp). (no attenuation). An initialvalue problem [59] A more thorough insight into the physical significance and implications of equation (1 13) is best obtained by solving an initialvalue problem instead of by studying the dispersion relations further. then by taking the transform of equation ( 1 13). (118) . The product (07 appears in equations (1 15) and (1 16) as a dimensionless parameter. The piston is given an impulse at t = 0. and the attenuation illustrates sound absorption. Various specific results follow directly from equations (1 14)(116). If the Laplace transform of the velocity isdefined as u(x. which. as w + 30. (1 17) where = (a. a .4.o/afo)27 is a slightly modified representative reaction time. reduces to (1 . These initial and boundary conditions determine a unique solution u(x. Since the boundary conditions on u become u = I/ e”‘dt = V/s at x = 0 and u + 0 as x x. causing the velocity at x = 0 to assume the constant value V for t > 0 (see Figure 4.6). ~ / u ~ ~ ) ~ ] ST’)} / ( I aZu/ax27’ + = 0. a + aeo and 1 + rx. The solution may easily be obtained by the Laplace transform method.3. s) = s. we obtain s[(s/afo)2u . For t 5 0.a 2 U / d X 2 ] + (l/7)[(s/ae0)2u  a2U/dX2] = 0. The consequent dependence of the phase velocity on the frequency [see equations (1 15) and (1 16)] represents sound dispersion.for intermediate values of w. aeo < a < afo .(a. upon rearrangement.[I  ( u . t ) dt. Suppose again that the gas occupies the region x > 0 and that a piston is located at x = 0. we require u + 0 as x + m for all (finite) values oft. thus indicating that nearequilibrium sound propagation will occur for frequencies such that 07 < 1 and that nearfrozen conditions will prevail if wz $ 1. 4.
1 and at s’ = . the asymptotic shape given by equation (120) is attained earlier (at smaller values o f t and x ) for smaller values of the reaction time z. It is now clear that the time development of the sound wave behaves as illustrated in Figure 4. The intermediate transition .3. ~ / U ~ ~ will ) ~ provide a nonzero contribution to v. and the width of the signal broadens (as x and t increase) in proportion to 1/&. the spreading equilibrium wave closely represents the true wave pattern.7. When x’ < t’.Here y is a positive constant such that there are no singularities of the integrand to the right of the line s’ = y in the complex s’ plane.~ dy. the reader may show that where erf denotes the error function * erf(z) = ( 2 / ~ i ) e . and the contribution from the semicircular arc along which Is’/ + m vanishes.[I  (U. Therefore. The magnitude of the pulse at x = a f o t decreases as t increases. Thus some disturbance always propagates with the velocity afo. the sign of the real part of the argument of the exponential in equation (119) is negative when ls’l + co with Re{s’) > 0. no disturbance propagates faster than the frozen sound speed x/t = afo. Since t’ is the dimensionless time variable appearing in equation (119). ThreeDimensional Flow 125 By taking the inverse transform. the main part of the signal travels with the equilibrium sound speed x/t = aeo. while at large values of t/z. The contour of integration may then be closed to the right. 0 [ Equation (120) shows that at large values of x‘ and t’.SIX’{ I .( U .4. (1 19) where s’ = sz‘. analogous reasoning shows that the contour of integration must be closed to the left. and the simple pole at s‘ = 0 and branch points at s‘ = . the dimensionless time is t’ = t/z‘. By means of an interesting application of the method of steepest descents. Reactions in Unsteady. For x‘ > t’ (that is. the sharp frozen wave is a close approximation to reality.~/U~~)~]/ s ’ ( ) ) ~ + ~ 1’23 ds‘ls‘. thus showing that u = 0 for x’ > t‘. In order to find the shape of the wave front at large values of x and t . we then find that the velocity is given by x exprs’t‘ . one may perform an asymptotic expansion of the integral in equation (1 19) for t‘ and x‘ approaching infinity with the ratio x‘/t’ fixed. and the dimensionless distance is x’ = x/afoz‘. for x > afot). At small values of t / z .
many related problems can be solved. twodimensional system. For example.4.126 Reactions in Flows with Negligible Molecular Transport t" OO a. The essential characteristics of the results of such an analysis can be inferred by interpreting the time t of Section 4.7. and [66]~711.4. Related problems By analyses that are similar to those presented above. This behavior is consistent with the picture developed in Section 4. .8) can be obtained by the methods of Section 4. Lick [65] has obtained solutions to the nonlinear. A decaying wave propagates at an angle determined by the frozen sound speed a f o . Reviews of these and other studies may be found in [l].3.ot FIGURE 4. The wave field produced in the steady. region occurs when t z z. and a spreading wave develops at some distance from the wall and propagates at an angle determined by the equilibrium sound speed aeo.4.4. twodimensional flow of a reacting gas past a wavy wall has been treated in [63] and [64]. steady. twodimensional sound wave produced when a supersonic reacting gas stream is turned through an infinitesimally small angle (see Figure 4. 4. [a]..4. unsteady propagation of a sound pulse into a reacting gas. Schematic diagram of the onedimensional.5. the structure of the steady.5 as the distance measured along the sound wave in the steady.3. \LI' \LI' t>>T t>>>T c . ~ OO amt afot u .6.3.3. twodimensional conservation equations governing the flow of a reacting gas mixture about a blunt body.
Eng. C S T 2 1 . Note No. R. 18.8. Kestin. H. 19. Fuel 32. 20. Yumlu. 4144 (1958). Pratt. C. Miles.‘I 127 FIGURE 4. 17th Symp. L. Eberstein and I. 5. 1965. R. Glassman.References Equilibrium sound wave . D. 11th Symp. R. J. 819830. The Dynamics o f Real Gases. New York: McGrawHill. B. (1977). (1967).451 (1953). 10th Symp. Jr. A. (1962). 970982. Introduction to Physical Gas Dynamics. (1967). 10. J. S. C . A. and I. 15. Rocket SOC. (1957). 8th Symp. and D. F. Blichner. 8th Symp. 1634 (1955). Chem. 13. Hottel. and P. 6th Symp.257 (1958). Herbert. R. (1979). Bowman. Spalding. twodimensional sound wave in a supersonic reacting gas stream. D. 14. J. Williams. 0. Penner and D. Longwell and M. S. Odgers. G. D. Dryer. Dryer and I. 21. Santoro. 14th Symp. 87 (1980).21. Blazowski. L. B. A. 22. Aronowitz. Clarke. Schematic diagram of a steady. Eng. A. Astronautica Acta 15. G. 14th Symp. 398411. 1968. Chapter 2. F. 50. P. 37 (1965). C & F 9. W. Baker. 7. Am. J. 365374. M. REFERENCES 1. G. W. Thermal Regimes of Combustion. T. L. Glassman. Mullins. 11. A. 9871003. 16th Symp. Glassman. Clarke and M. 9. V. 2. 9951002. (1962). 6. McChesney. 771778. Weiss. (1962). Williams. . C. 547 (1970). S. 8. 1961. and M. J. New York: Academic Press. L. Vincenti and C. T. P. V. 779790. Spalding. 327. B. Hottel. Krieger. 577592. F. 982994. C. S. J. F. (1973). Jenkins. E. 633644. J. Kruger. S . P. 8th Symp. K. 179 (1951). (1973). Lang. New York: Wiley. 23. Sangiovanni and A. 11th Symp. Ind. Vulis. Ryan. S. 3. V. Chem. (1965). J. Olfe. and G. Weiss. A. 1964.. and C. B. Crowe. F. M. Williams. NACA Tech. B. 16. 17. 4. H. 12. 47. London: Butterworths. Jain and D. Ind. Heims. Radiation and Reentry. H. P. Longwell. J. and J. I.
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the idea that the overall activation energy is large in comparison with the thermal enthalpy has led to the development 130 . knowledge of the concepts developed and results obtained in laminarflame theory is essential for many other studies in combustion. constitute the central problem of combustion theory in at least two respects. In more recent years. planar laminar flame. Timedependent and multidimensional effects are considered in Chapter 9. Deflagrations. whose work has been discussed in more recent literature [3]. the earliest combustion problem to require the simultaneous consideration of transport phenomena and of chemical kinetics was the deflagration problem. who considered heat loss to be of predominant importance and rates of chemical reactions to be secondary. Attention here is restricted to the steadily propagating. First. improved basic equations became available for use in theoretical analyses. Subsequently. [4]. The essential result that the burning velocity is proportional to the square root of the reaction rate and to the square root of the ratio of the thermal conductivity to the specific heat at constant pressure was first demonstrated by Mikhel'son [2].CHAPTER 5 Theory of Laminar Flames This chapter concerns the structures and propagation velocities of the deflagration waves defined in Chapter 2. Second. or laminar flames. The problem of determining the propagation velocity of a deflagration wave was first studied by Mallard and le Chatelier [l]. Independent investigations by Mallard's student Taffanel [S] and by Daniel1 [6] based on simplified models of the combustion wave reached the same conclusion.
1. a combustion wave spreads through the gas. Therefore. and propagation velocity. Next. Description of Laminar Flames 131 of asymptotic analyses that lend further clarification to the wave structure and that provide formulas with improved accuracy for the burning velocity. a criterion for the validity of the steadystate approximation for reaction intermediaries is described. Many ad hoc approximations that rest in varying measure on the concept of large activation energy are reviewed in [S]. Systematization of the concept through formal introduction of the method of matched asymptotic expansions was achieved first by Bush and Fendell [9]. DESCRIPTION OF LAMINAR FLAMES 5. The essential features of the mathematical problem of predicting the propagation speed of a onedimensional laminar deflagration wave will then be presented by examining in detail the unimolecular process R .3 emphasizes the utility of asymptotic concepts. which is characteristic of the combustible mixture. . This choice may be justified by the fact that morecomplicated processes may be treated by extensions of the approaches developed.1. many outstanding questions remain concerning deflagration structure. the combustion wave often is observed to be nearly planar and to travel at approximately a constant speed between (very roughly) two and ten tube diameters from the spark. It will be seen that although useful approaches to the theoretical analysis are available. The development of laminarflame theory to be given in Section 5. The necessary modifications caused by the presence of chain reactions are discussed in the final section. P (R = reactant. They all refer to velocities measured with respect to the gas ahead of the wave. Much of the recent work is covered in [lo]. We shall begin with a brief discussion of experiments and a simple indication of the primary physical phenomena involved. This constant speed is an empirical laminar burning velocity or flame speed. A number of recent studies of deflagration structure have been based on asymptotic methods of this type. appropriate basic differential equations are derived for describing the structures of combustion waves. wave speed. as synonyms for such terms as dejlagration velocity.1. in particular. the terms are used interchangeably here.1. Provided that the tube is not too short and the electrical energy released by the spark is not too much larger than the minimum energy required for ignition. Experiments When a quiescent combustible gas mixture contained in an open tube is ignited by a spark at one end of the tube. P = product). The implications of this idea were first derived heuristically by Zel'dovich and FrankKamenetskii [7].5.* * Recent efforts to distinguish between the terms burning velocity and pame speed on the basis of Eulerian and Lagrangian coordinate systems appear to introduce confusion. 5.
just upstream from the flame. . but the component of velocity normal to the flame increases. as is illustrated by the vector diagrams in Figure 5.1. is the velocity of propagation (burning velocity) of the flame. the curvature can be eliminated by use of a slot burner. The component of velocity normal to the flame surface. This propagation velocity can be determined from measurements of the flow velocity at the exit of the burner tube. a Bunsentype burner with an elongated rectangular outlet. conical flame sits at the mouth of the cylindrical burner if the exit velocity exceeds the flame speed.1. The component of velocity tangent to the flame surface remains constant across the flame. the experiment just described does not yield accurate burning velocities. the apex angle of the flame cone). and various Laminar flame Fuel Oxidizer experiment. typically photographic. of the geometry of the flame surface (for example. and a steady. An alternative apparatus that provides burningvelocity data of greater accuracy is the Bunsentype burner schematically illustrated in Figure 5. The mixture composition is determined by adjusting the flow rates of the fuel and oxidizer (often air). The radius of curvature of the flame cone is generally so large compared with the width of the flame that the flame structure is the same as the structure of a plane flame except at the tip of the cone and at the burner port.132 Theory of Laminar Flames Because of various inherent difficulties. Numerous experiments of this type have been performed. accompanied by measurements.
and one or more stabilizing rods are employed. with very small magnesium oxide particles introduced into the flow and illuminated stroboscopically in order to make the gas streamlines visible (from [l 11. the steady flow is contained within a duct. . Photograph of a natural gasair flame on a rectangular burner. Description of Laminar Flames 133 FIGURE 5. a steady deflagration may be stabilized in a combustible mixture.2. I] for a discussion of the techniques and the accuracy of each. by a wire or rod inserted perpendicular to the flow direction.2. procedures for calculating burning velocities from the measurements have been developed [11].1. In ramjet combustors. Lewis and of Academic Press). flowing steadily at a velocity greater than the burning velocityt.* A photograph of a typical laminar flame produced in this way is shown in Figure 5. For example. Laminar deflagration waves may be produced in a number of other experiments. courtesy of B.5. the propagation velocity of the wedgeshaped flame determines the minimum chamber length required for the * See [l t At a velocity below the burning velocity the flame would move upstream andjushbuck would be said to occur.
and horizontally in chambers usually behave differently from each other because of buoyant effects. Variants of the flatflame burner that also are useful in the laboratory are stagnationflow devices.. In using this technique. . A configuration useful for studying laminar flames in the laboratory is the flatflame burner. Flames propagating upward. and stagnationflow burners are their tendencies to minimize these effects. in which the combustible mixture.* Nevertheless. Even in the absence of both gravity and instabilities. in which a planar flame is stabilized above one or between two porous plates in a flow that is essentially onedimensional. if po is the density of the unburnt mixture and v o is the flame speed. Motions of propagating laminar flames and shapes of steady flames often are influenced by buoyancy and by various instabilities (Chapter 9). it is best to verify by observation that the flame is nearly spherical. * A simple solution exists only for spherical symmetry. the flame speed is vo = (p. The curvature of the streamlines in the upper part of Figure 5. a constant fraction of the observed growth rate of the spherical flame. with data reduction performed on the basis of an assumed spherical shape of a flame of negligible thickness. the turbulent burning velocity (Chapter 10) must be employed. is ignited in the open or in a very large chamber. and since the mass of burnt gas is 47cr3pm. or “bomb” (typically spherical).2 is produced by buoyancy. This arrangement affords a good research tool because it offers the experimenter a relatively large number of variable parameters and facilitates analysis and interpretation of measurements by virtue of the plane.134 Theory of Laminar Flames combustion to be completed inside the duct. to calculate histories of flame shapes for slow propagation of a flame sheet at a specified flame speed from an initially uniform and quiescent state in a closed chamber with fixed walls is a nontrivial. In this experiment. the flame produced near the stagnation point is flat locally and can be arranged to have negligible heat loss but is “stretched” in that streamlines diverge in the vicinity of the flame. but heat loss to the porous plate generally is significant and must be taken into account./po) dr/dt. in which a flow with a stagnation point is established by directing a uniform combustible stream either normally onto a flat plate or counter to the flow of a uniform. but since the flow in practical ramjets is turbulent. Advantages of some Bunsen. walls influence flame motions in chambers. inert stream. where pm is the density of the burnt gas. downward. onedimensional geometry. elliptic problem even with inviscid fluid mechanics if there is an appreciable change in density across the sheet. then the rate of increase of the mass of burnt gas inside a spherical flame of radius r is 47cr2p0v. The complication of pressure variation with time can be eliminated by the soapbubble method. flatflame. approximate values of flame speeds often are obtained by monitoring the pressure histories in a closed chamber. possibly enclosed within a soap bubble.
leading to a crude estimate of the burning velocity. Our primary objective in this chapter is to predict this burning velocity. where El is an activation energy. that is. x is the distance normal to the wave. The factor on the righthand side of equation (2) with the strongest temperature dependence is usually w. temperature. where p o is the density of the initial combustible gas mixture. At constant temperature. 5.To)w6 z A(T. . which implies that the thickness of the wave is The burning velocity uo can be related to this wave thickness as follows. into which a combustible gas mixture flows at velocity uo (the laminar burning velocity). the combustion wave propagates at a definite velocity that empirically depends on the pressure.2 a simple physical picture of the deflagration wave is presented. yields Equation (2) shows that the burning velocity is proportional to the square root of a reaction rate and to the square root of the ratio of the thermal conductivity to the specific heat. and the subscripts 0 and co identify conditions upstream and downstream of the wave.1. The mass of combustible material per unit area per second flowing into the wave is p o u o .To)/&These results lead to the equation c.1. In Section 5. illustrates the essential mechanism involved. qw6 z A ( T .TJ6. The cold incoming gas is heated to a temperature at which it reacts at an appreciable rate by means of heat conduction from the reaction zone. Hence mass conservation implies that pouo = w6.2.(T. . The deflagration wave consumes these reactants at a rate w6 (mass per unit area per second). which is similar to that of Landau and Lifshitz [3]. then energy conservation implies that q = cp(Tm. . and composition of the initial combustible mixture. T is the temperature.To)(where c p is an average specific heat of the mixture) and that the entire heat released must be conducted upstream. where A is the mean thermal conductivity of the gas.which. which varies roughly as eE1’RoTm. respectively. in conjunction with equation (l).5.1. The discussion.To)/6 (energy per unit area per second). If the wave is adiabatic so that no energy is lost downstream or from the sides of the wave. and Ro is the universal gas constant [see equation (18)]. Description of Laminar Flames 135 In all these laminarflame experiments. . Phenomenological analysis of a deflagration wave Consider a stationary plane deflagration wave of thickness 6. The rate at which heat is conducted upstream is roughly A dT/dx = A(Tm . If q is the heat of reaction (energy released per unit mass of the reactant mixture) and w is the reaction rate (mass of the reactant mixture converted per unit volume per second). then qw 6 is the energy released per unit area of the wave per second.
and the quantity c . equation (2) should provide a numerical estimate for uo . Thus laminar flames are nearly isobaric. The remainder of this chapter is devoted mainly to a mathematical amplification of the concepts introduced in this section. A useful way to deduce an overall order and an overall activation energy for a reaction is to measure the T and p dependences of uo and to correlate these empirically with equation (3) by adjusting n and El. Since equations (3) and (4) imply that 6 p("/') at constant temperature.2. and w p". Empirical laminar burning velocities lie between 1 and 1000 cm/s. it will be seen that the burning velocity is an eigenvalue of the conservation equations. equation (125) is valid for laminar flames. Since these velocities are small compared with the speed of sound.and with vo 50 cmls.pouo. Eliminating w between equations (1) and (2) leads to the relation 6 = A/c. Equations (1) and (2) enable us to estimate the flame thickness 6 from measured values of uo . and po . However. c.. Introductory remarks In this section we shall develop equations capable of describing the structures of both deflagrations and detonations. (4) With representative values for A.E ~ / 2 R o T m (3) In principle. Hence the pressure and temperature dependences of uo are given approximately by uo    p(n/z)l e . and hence the radius of curvature of the flame cone. for experiments with Bunsentype burners). experimental studies of the interiors of laminar flames are often performed at subatmospheric pressures. Thus the approximation p = constant. appearing above is the specific heat at constant pressure. the diameter of the burner mouth. and the continum equations of fluid dynamics are valid within the deflagration wave. and laminar deflagration waves may be approximated as discontinuities in many experiments. values of w are so uncertain (see Appendix B) that equation (2) is more useful for estimating w from experimental values of uo . equation (4) gives 6 lo' cm.    5. we were justified in not attaching a subscript to p in equation (3).1. MATHEMATICAL FORMULATION 5. Many questionable aspects of the reasoning employed in this section will have been remedied before the end of this chapter. In particular. but 6 is small compared with typical dimensions of experimental equipment (for example. which was shown in the preceding section to be valid for . are independent of the pressure p . Therefore 6 is large compared with a molecular mean free path (about lo' cm). in practice. where n is the order of the reaction [see equation (141.2.136 Theory of Laminar Flames A and c. po p according to the ideal gas law [equation (19)].
(127). pv (5) = m = constant. The flow is steady. then equations (126). Thus pu2 + p . 3. 5. Mathematical Formulation 137 ordinary deflagrations but which is invalid for detonations (see Chapter 2). (131). In view of assumptions 16. External forces are negligible. . These disadvantages appear to be insignificant in view of the greater generality of some of the results [for example. . The approach is unnecessarily complicated for deflagrations only in that the momentum conservation equation must be considered and one additional approximation [assumption 8 below] must be made. it will obviously be expedient to adopt a coordinate system which is at rest with respect to the wave. 6. The approximate validity of these assumptions and of others to be made subsequently can be justified by orderofmagnitude considerations for many systems. and (133) are valid with g 2 = g3 = 1 and with the last term in equation (132) omitted. see [l2] or [13]. (7) dtJdx wi/m. Equations (18). . 5. 2.2. . The Soret and Dufour effects are negligible. (132).($p + K ) dvldx = constant. Radiative heat transfer is negligible.2. equation (24)]. and onedimensional in the adopted frame of reference. Our principal reason for adopting this approach is to avoid repetition in Chapter 6. For a detailed derivation of the basic relations for deflagrations alone. (19).. if x is the coordinate normal to the combustion wave. The following assumptions will then be made: 1. i = and (9) where the notation was defined in Chapter 1.2. (111). Preliminary assumptions and equations In order to analyze the structure of a combustion wave. 4. The gas mixture is ideal. Diffusion caused by pressure gradients is negligible. plane.12) are necessary subsidiary relationships among the variables appearing in equations (5)(9). N . and (1. will not be made here.5. = (6) 1.
T. 8.1) it was shown that these conditions imply that relationships exist between the properties at x = +a and those at x = . + u2/2) . it enables the analysis to be simplified considerably and. Assumption 8 states that which is a relation between transport properties. Appendix E or [14].2. 5. this assumption leads to a considerable simplification in the analysis for detonations and for flames with nonnegligible kinetic energy. equation (111) reduces to hi = hP + c. All chemical species may be considered to have constant and equal average specific heats at constant pressure cp.1. Nevertheless.).3. Assumption 7 is not essential because the important qualitative results to be obtained do not depend on this assumption. p.co.TO). When bulk viscosity is negligible ( K = 0). At x = + m. for p % constant) because the terms involving the viscosity are negligibly small.& + u&Q) + &/2) .2) and the values of all variables except uo are known (compare Section 2. As was pointed out by Spalding [lS]. However. Section 2. In view of assumption 7. The effective coefficient of viscosity ($p + K ) equals the ratio of the thermal conductivity to the average specific heat (Ale.T (c. in some respects.T + u2/2) as a variable. Approximations that further simplify the energy equation Equation (9) can be simplified by making two additional assumptions : 7. 16). clarifies the physical significance of the results. we reemphasize that assumption 8 will not be present in subsequent sections of this chapter. all properties are uniform (d/dx = 0) (see.(cpT0 + ~&'2)' (12) .c c (where properties will be identified by the subscript 0) and at x = + c c (where properties will be identified by the subscript a ) . equation (1 1) implies that the Prandtl number is 2 (see Appendix E). At x = rx. A normalized dimensionless measure of the stagnation enthalpy is Z E (c. properties again become uniform (dldx = 0) and chemical equilibrium is reached. However.(T .138 Theory of Laminar Flames The boundary conditions for these differential equations are to be applied at x = . some aspects of the analysis of combustion waves in which kinetic energy is of importance can be simplified by using the stagnation enthalpy (c. which is a good approximation for many gases (see.1. In Chapter 2 (Section 2. for example. (10) Assumption 8 is entirely unnecessary for ordinary deflagrations (that is.3). however.(c.
) . By using equations (lo)( 12) (along with the boundary conditions d/dx = 0 at x = c o and the identity ti= l). + &/2) . which is simply the statement of overall energy conservation for the wave. Mathematical Formulation I39 which varies (monotonically for purely exothermic reactions) from 0 at x = . = (cPT. Assumption 9 automatically reduces the number of independent relations in each of the equations (7) and (8) to one.2. follows directly from equations (9) and (10) and the boundary conditions.5 .(c. when the analysis is extended to include multicomponent systems in which any onestep reaction occurs ( M = 1) and for which the binary diffusion coefficients . T O + ~&'2). To + U&2 ') ] / q . equation (7) reduces to a single differential equation. general conclusions regarding the wave structure are difficult to obtain. Simplifications in the energy and diffusion equations for unimolecular reactions in binary mixtures Since equations (7) and (8) constitute 2N differential equations. 0 . Thus N 4 1 i= 1 h?(ti. even in this case.m t o l a t x = +a. 2 . T + u2/2)  ( c .and a single flux fraction is sufficient to characterize the progress of the reaction.1 simple relations among the N flux fractions ti. the reader can prove that equation (9) reduces to + The denominator inside the brackets in equation (13) is the total heat release per unit mass of mixture. In order to avoid all these complications while retaining the essential physical aspects of the problem. In view of equation (14). (14) where the last equality. Furthermore. simplifying assumptions regarding the diffusion coefficients (usually that all binary diffusion coefficients are approximately equal) must be made in order to decrease the number of independent relations in equation (8). (124 5. This case has been treated in most analyses of combustion waves .ti. If only one chemical reaction occurs [ M = 1 in equation ( 1 4 1 . q. we shall consider the following system: 9. The gas is a binary mixture in which the unimolecular reaction R + P occurs. the definition of T [equation (12)] reduces to T = [(c. then equation (7) provides N .4. But.
Equation (19) then reduces to p = pRoT/W. [from equation (112)]. Since the boundary conditions require that dK/dx = 0 at x = fa. . . in terms of the normalized mass fraction x.0>7 5= Jo(mc. X i = Y.140 Theory of Laminar Flames of the pairs of principal species d o not differ appreciably. v .Y2)eEI/RoT.t 2 .m y = (Y2  Y2.E ~ / R 0 T ROT = pBITa'(l .m (the diffusion velocities vanish far upstream and downstream)./A) dx (19) is also introduced. (15) and equation (18) becomes w1 = ..If the dimensionless distance m  '2.co to 1 at x = (17) + co.O) (21) . i = 1.m  Y2. 2. we find that v . Hence. However. assumption 9 will have to be omitted in the final section of this chapter because the distribution of reaction intermediaries obviously cannot be studied on the basis of a onestep process.WpB1 Ta' x l e . . ~ = v . reaction progress variable) has been defined as (€2  '2. The addition of assumption 9 to assumptions 17 also renders valid all of the results of Section 2.€ 2 .ti). equation (20) implies that X . . .Y2. Yl = 1 . 0  € 2 . (20) which is Fick's law. = W2 = W [since mass is conserved in chemical reactions. ~ = v .)l(t2. (16) where use has been made of equation (15). Since t1 = 1 . ~= 1. equation (8) reduces to d & d 'x = (m/pD12)(X .t 2 . or formally by summing equation (7) over i]. M = 1 and N = 2.w 2 = . According to assumption 9.0)/(€2.O)/(Y2. m) = 1 . For the present twocomponent mixture.2. then equation (13) reduces to dz/d< = z . Assumption 9 enables us to simplify equation (13) further. the quantity in the brackets in equation (13) is (€2 . and t1 = 1 . W.€7 where the normalized flux fraction (or.6. respectively. Letting the subscripts 1 and 2 identify the properties of species R and P. = 0.O and = ti. which goes from 0 at x variable = . o = ti. there is virtually no change in the results.
5. 5. .5. which.6. Equation (24) provides an explicit relationship between the composition and the stagnation enthalpy throughout the wave. From equations (19) and (22) it can be seen that Y is simply related to z provided that the next assumption is allowed: 10.Y must remain bounded as x + co.m = 1 (Yl. (24) which also satisfies the correct boundary conditions at x = f c o [see equations (12) and (21)]. then equation (5) becomes dv A convenient dimensionless velocity variable is (26) which approaches unity as x + .the only acceptable value of A is A = 0. where use has been made of equations (17) and (18) and the Lewis number is Le = 3L/pDI2c.. where A is an arbitrary constant. Actually. and (18). implying that Y=z. = 0). (19. = 1 ( t i . It is shown in Appendix E that Le = 1 is a reasonable approximation. the result is rp = v/vo. Since z . and therefore also t2. has the general solution (T  Y) = Ae’. (1 l). Equation (12a) can be used to express the temperature T in terms of rp and z.2.2.2. since the reaction goes to completion at x = co [dtJdx + 0.(l/Le)(dY/d() = z . Solution of the diffusion equation when Le = + 1. when Le = 1.5. Mathematical Formulation 141 (which goes from 0 at x = c c to 1 at x = + co). The difference of equations (19) and (22) is dz/d< .m= 0).Y . equation (20) becomes (22) (23) (l/Le) dY/d( = Y .co.6. Dimensionless forms for the momentum equation and the speciesconservationequation If the constant in equation ( 5 ) is evaluated at x = co and use is made of equations (6). The Lewis number is unity. see equation (7)]. equation (16) implies that Y2.
and E (dimensionless measures of the stagnation temperature.I)]  1). 5. which appear on the righthand side of equation (34). = 1 and equations (16)(18). We are entitled to indicate that F. cp). and it equals zero only at z = I. cp) is non1.2.2.cp. cp) depends only on z. and (24) to show that Equation (33) is a dimensionless form of the speciesconservation equation.cp.(t. is a function of z and cp. we obtain the dimensionless form of the momentum conservation equation. Summary of the simplified mathematical problem Equations (19). (27).cp..(z. are easily expressed in terms of z. in the physically acceptable range negative over the entire range 0 I T I of cp. and the progress of . as defined in equation (34). use may be made of Y. cp) = (cp  1) + 4 {' [1 + d z YMo cp  ( q ) M b ( c p 2 . and (33) are three firstorder differential equations. The relation between a' and the dimensionless heat release c1 used in Section 2. The function F. and (30) into equation (25). the velocity.(z. and constants through equations (6) and (27). although it becomes very small (because of the exponential factor involving T ) near z = 0 where T is small.7. (32) The function F.142 Theory of Laminar Flames where the ratio of specific heats is the dimensionless heat release is and the initial Mach number is Mo =V O l J r n . (31). and constants. In equation (7) with i = 2. which determine the variations of the variables z.(z. F. because the additional variables p and T. (21).2 is By substituting equations (26).
The Unimolecular Decomposition Flame with Lewis Number of Unity 143 the reaction. 4 1.5. given by equation (32)] imply that (38) and (39) In view of equation (29). thereby reducing the total number of differential equations from three to two. (40) that is. retaining all of the assumptions of the preceding section. [which is determined either by setting F. Boundary conditions for equations (35) and (36) are 6 = 0 and cp = 1 at T = 0. ) been obtained from equations (35) and After solutions for V ( T )and t ( ~have (36). (26).(T. since ordered kinetic energy is negligible. Since the distance variable t appears only as d/dc in these equations. then equations (27) and (31) [with F . T is a measure of the static temperature. THE UNIMOLECULAR DECOMPOSITION FLAME WITH LEWIS NUMBER OF UNITY 5. it is easily eliminated. equation (38) states that T = c. found to be true from the deflagration solution). Using equations (6). and (38) in equation (39).3.3. q) = 0 and T = 1 in equation (32) or by consulting Section 2. 5. where T~ is the value of 7 at x = 0.21 at T = 1. it is seen that the two governing equations can be taken to be and over the range 0 I T I 1.(T  m/q.1. If q and dcp/d5 remain small compared with 1/Mi (as is. Through division of equations (31) and (33) by equation (19). the profiles in the physical coordinate can be found by integrating equation (19). namely. (41) . the boundary conditions alone do not enable us to draw any conclusions concerning the existence or uniqueness of solutions. and 6 = 1 and cp = (pa.3. one obtains p T = po To = constant. in fact. respectively) through the combustion wave. Since both of these endpoints are singular points of equations (35) and (36). Governing equatiow Let us now restrict our attention to deflagrations with M .
Three constants a'. 3. cp) = F. kinetic. enter into equation (42)./RoT.144 Theory of Laminar Flames which implies that p = constant.(T. thus the results do not depend on assumption 8. b'. we find that d€/dT = I\W/(T . cp(~)) depends only on T .  8 . 3. A is called the burningrate eigenvalue.1.T)eXp[P'(l  T)/(l/a' k T)]. all of which are presumed to be known. = Two realistic cases in which the nonessential assumption 11 is valid are T and a1 = f. Ta1/m2cp)eB'. and the dimensionless factor A has been defined as (44) A = (ApB. The first two of these constants are determined by the initial thermodynamic properties of the system.(T. explicitly.t). Thus A is considered to be an eigenvalue of the nonlinear equation (42) with the boundary conditions stated above. When this result is substituted into equation (36). AT"'' a.. The temperature dependence of A is given by constant. we can obtain the T dependence of F . (45) So that A may be treated as a constant without complicating the definition we shall (solely for simplicity) employ a final assumption: of o. In addition to depending on known thermodynamic. according to the discussion in Section 5. By utilizing equations (38) and (41) in equation (34). is an unknown parameter that is to be determined by the structure of the wave. in which F. = 0. (43) the dimensionless activation energy is p' = E. the total heat release. Since equation (42) is a firstorder equation with two boundary conditions. (42) where the dimensionless reactionrate function o = W ( T ) is defined as W (1 . we may hope that a solution will exist only for a particular value of the constant A. and the activation energy. The twopoint boundary conditions for equation (42) are t = 0 at T = 0 and E = 1 at T = 1. in view of equation (15). This latter derivation rests only on the assumptions that the Mach number is small compared with unity throughout the wave and that the coefficient of viscosity is not abnormally large.1. and A. These formal results were anticipated in Section 5. 11. the third constant A depends on the mass burning velocity m. the only differential equation that remains to be solved is equation (36). and transport properties. Since equation (39) represents an approximate solution to equation (39. they can be derived more directly by estimating the magnitudes of the terms in equations (5) and (9). which.
for example. the reaction proceeds rapidly and heat is conducted downstream. = 01 for realistic* values of A. The problem identified here is the one in which the coldboundary dificulty. equation (42) implies that (dzldt). It is clear that the trouble lies not in the mathematics but instead in the mathematical model of the physical situation .2.0= 0. when ~ ( z ) given by equation (43)./C. in the case Y2. The Unimolecular Decomposition Flame with Lewis Number of Unity 145 From equations (6).3. which implies that z becomes negative as t increases [since (dzldt). then rn would have to be imaginary according to equation (45).1. then the point (z = 0. Thus A itself should not depend strongly on the properties of the system. t = 0. and wz(l. We thereby see that d 2 z / d t 2 .)(1/JA)> where A. ( l / f i ) 0. is the value of A at T = T. (44). It is physically unacceptable for z to decrease as c increases near z = 0. .)W2(L T.2. The coldboundary difficulty [ 161. it can depend only on the two dimensionless groups CI'and p. z becomes negative (the temperature drops) as t increases near the cold boundary.5. derived from equations (42) and (19). introduced in Section 2..l/Ao(O). this implies that the mass fraction of products becomes negative [see equations (21) and (24)]. This can be seen more directly by difis ferentiating the reciprocal of equation (42) with respect to E .) denotes the reaction rate [appearing in equation (16)] evaluated at X I = 1 and T = T. With t = 0 at z = 0 and o(0) # 0. whence t 4 t near z = 0. T. and it is a simple matter to determine the behavior of the solution in the neighborhood of this point. the mathematical problem defined by equations (42) and (43) with the stated boundary conditions is illposed. for A > 0. = 0. If o(z) does not go to zero at z = 0 [as is implied by equation (43)]. [ 171. 6 = 0.2. first arose.3. The comparison of this expression with equation (2) shows that the expected primary dependence of vo on the properties of the system has been included in the definition of A. For typical activation energies. = . and (45) it can be seen that 00 = (liPo)J(~. t = 0) is not a singular point of equation (42). A further indication of this fact may be obtained by differentiating equation (19) with respect to 5 and using the result dt/d( = ( d t / d z ) ( d z / d t ) = A o . Equation (42) is then easily integrated to show that = t2/2Aw(0) near z = 0. (16). [IS] The coldboundary condition is z = 0 at E = 0. and hence z may be neglected in comparison to t on the righthand side.  5. Hence.dz/d< =  Aq (46) * If A were negative. the result is (d2z/dc2). indeed.
An alternative procedure for determining a finite. respectively. von Karman and Millan [17] replace T = 0 by z = zi (where 0 < zi < 1) as the position at which to apply the coldboundary condition t = 0. even though o # 0. It cannot do so.(T. where e' is the value o f t at z = T' (near zero). t approaches zero much more rapidly than z at the cold boundary (see the inset in Figure 5. or the heat loss to the flame holder. It is reasonable to identify the pseudostationary value as the . Since the integral in the denominator diverges at z = 0 if cc) > 0 and w(0) # 0. there is no reaction upstream).we expect z to approach zero smoothly. but this is impossible according to equation (46) if w does not approach zero as z + 0. the combustible mixture has been asked to flow from x = . convection.'. whence equation (42) may be integrated to show that A = rd 0e/[:(w/z) dz.146 Theory of Laminar Flames the three terms of which nondimensionally represent diffusion. we then see that A = 0. where the dashed line indicates the pseudostationary value of A. on the chosen value of zi. Avoidance of the appearance of the coldboundary difficulty can be achieved only by revision of the physical model on which the mathematical formulation is based. it is therefore reasonable to neglect t in comparison with z in the denominator of equation (42). . There are many ways in which this can be done. and reaction. for an infinite time) without reacting appreciably.3. The equations attempt to demonstrate this result by suggesting that A = 0. Since t = 0 at the flame holder (that is. for example. This conclusion depends directly on the strong temperature dependence of the reactionrate function. below which the chemical reaction rate vanishes [see equations (19) and (33)].3).co.)(dz/dOi. of course.7'. 5 + . It is found that the calculated estimate for A assumes a pseudostationary value as zi. removing an amount of heat per unit area per second equal to (1d T / d x ) i = mc. so that both m and uo are infinite [see equations (45) and (6)] if w(0) # 0. is allowed to vary between reasonable limits [16]. The pseudostationary behavior is illustrated in Figure 5. by starting an integration from the hot boundary and finding that. for reasonable functions w(z). In one approach. In the formulation of the problem. At the cold boundary. whence the heatsink concept is seen to be mathematically equivalent to the ignitiontemperature concept at the cold boundary. it will have to have reacted before it arrived. so that dz/d< and d2Tldt2 should both approach zero. nonzero value for A involves the assumption that a flame holder serves as a weak heat sink [lS]. This may be seen.00 at a finite velocity (that is. With either of these methods of remedying the coldboundary difficulty. The introduction of this artifice is equivalent to employing the physical concept of an ignition temperature Ti. the value of A depends. equation (19) implies that (dz/d5)i = z i . In the vicinity of the cold boundary.
by arbitrarily defining A as the value corresponding to the inflection point of the curve in Figure 5.3. it is a modification that extends over the entire range of z and.The nondimensional ignition temperature zi is small. this dependence may be eliminated entirelyfor example. in an exponential fashion as z + 0 and results in a graph of ~ ( z that ) is not very different from that for reasonable values of l/a’ # 0.3. one which can lead to somewhat laborious computations if solutions are to be generated for a range of values of zi in search of pseudostationarity. Thus a burning rate that depends only weakly on zi is obtained. for example. These early approaches to the elimination of the coldboundary difficulty are mathematically equivalent to reformulation of the physical model through modification of o(z) by putting o = 0 for < zi. changes the slope d o / d z at z = 1. 3 . Schematic representation of the solution profiles and of the pseudostationary behavior of the burningrate eigenvalue as a function of the nondimensional ignition temperature. One alternative that has enjoyed some popularity is that of Friedman and Burke [19] in which l/a’ is set equal to zero in equation (43). However.5. Instead. For this reason alternative modifications to o(z) have been sought. This avoids the coldboundary difficulty by causing w(z) to approach zero rapidly. and the corresponding is not to be associated in any way with a physical ignition temperature to be found experimentally. . ziis a purely computational device. The Unimolecular Decomposition Flame with Lewis Number of Unity 147 FIGURE 5 . physically significant value. since values of zi very near zero or unity seem unrealistic.
In contrast.Z)~Z". [24]. For rate functions in this class. only one of the two integral curves from the saddle enters the physically acceptable region z < 0.. For nonnegative functions w(z). z = 0 . If w(z) is positive except at z = 0 and z = 1. then A is unique [21]. and moreover the cold boundary is found to exhibit a nodal type of behavior when A does not exceed the maximum. which is not a singularity of equation (42). changes are permissible in o(z) only near z = 0. [25]. then the problem remains illposed. An understanding of the special characteristics of the ignitiontemperature method may be obtained from a phaseplane analysis of equation (42). with an the solution t = 0 for z < zicauses the relevant coldignition temperature zi. Multiplying equation (42) by (1 . In this case. If w/z approached infinity as z + 0. then this formula gives two directions of integral curves at the cold boundary for A less than a maximum value. we obtain a quadratic equation for (dE/dz). then the only other singularity in the region of interest (0 s z I 1. [22]. E + 0. If such an analysis is pursued [26] by standard methods (for example. . t = 0. where m and n are positive integers. A certain amount of rigorous study has been given to the mathematical form of o(z) near z = 0 that renders the problem wellposed [20]. [Zl]. If w vanishes in a finite neighborhood of the point t = 0. for these rate functions. this particular modification is not recommended. have been studied [23]. the solution to which is 1 f$ I 412 lim (w/z) g)o = 1n 2 If o / z approaches a finite limit as z + 0. [27]) it is found that the singular point (or critical point) at z = t = 1 is a saddle point. the maximum value of A appears physically to be the most realistic [26] and is the value that has been obtained [23]. then solutions satisfying the given boundary conditions exist for all values of A less than or equal to a certain maximum value [22]. t < 1. Modifications to w of the form o = constant (1 . the behavior of w/z as z + 0 is relevant. boundary point to be z = z i .. and it does so with < z. Therefore. . Much of the work has been concerned with continuous functions w(z) that are positive for 0 < z < 1 and that vanish at z = 0 and at z = 1 [22].0 I t I1) is the cold boundary. This attribute of the ignitiontemperature approach to the correction of the coldboundary difficulty helps to make it more attractive than other approaches that involve modification of o.t/z) and passing to the limit 7 0. the requirement that the integral curve must pass through both the nonsingular point (5 = zi. As might be expected from the above discussion.(w/z) is finite (either positive or zero).t = 0) and the hotboundary saddle serves to select a unique value of A. if lim. It is because of this nodal character that one integral curve from the saddle passes through the cold boundary for each value of A less than or equal to the maximum.148 Theory of Laminar Flames thereby affecting the value of A obtained and providing an incorrect dependence of A on a'. E = 0.
The analysis employs a form of equation (46) obtained by defining g = dz/d< and by treating z as the independent variable and g as the dependent variable. If the asymptotic approach becomes inappropriate. [29] for the formulation based on the ignition temperature. upper and lower bounds may be established rigorously for A. Unlike the steadyflow probIem in the infinite domain considered here.then successive orders of the asymptotic expansion yield. From equation (46) we see that 9  g dg1d. The Unimolecular Decomposition Flame with Lewis Number of Unity 149 Asymptotic analysis for large nondimensional activation energies (p’ appreciably greater than unity. In this respect. If the problem is rendered wellposed by introduction of zi. see Section 5. In a very real sense. that at the cold boundary (originally g = 0 at z = 0) becomes g = zi at z = zi(O < zi < 1) in the ignitiontemperature formulation. When the asymptotic method is adopted. This has been accomplished by Johnson and Nachbar [21]. and artifices of ignition temperatures.3.r = ACO. Bounds on the burningrate eigenvalue When the problem is formulated in a wellposed manner.3. The asymptotic approach in effect determines A through an expansion dominated by the behavior of the solution in the hotter portions of the flame. 5. The asymptotic method thereby provides a physically correct solution to the illposed problem. the idea of a steadily propagating premixed laminar flame is an asymptotic concept. or ratefunction modifications become superfluous. Further clarification of the situation has been achieved recently [28] on the basis of analysis of an initialvalue problem in which the initial rate of reaction is not negligible.6) occupies a unique position with respect to the coldboundary difficulty.3. Integrating equation (47) from z to z = 1 gives g2/2 = A [ 1 o dz  [g dz. The specific form of w(z) in the vicinity of z = 0 plays no role in generating any of the terms in the expansion. (48) which reduces to (49) . (47) The boundary condition at the hot boundary for equation (47) is g = 0 at z = 1. it is permissible but unnecessary to state the problem in a wellposed fashion. successively improved approximations to the pseudostationary value of A.3. flame holders.5. in an asymptotic sense. the coldboundary difficulty simply does not appear within the context of the asymptotic expansion. the initialvalue problem in the infinite domain (or the steadyflow problem in the semiinfinite domain) is wellposed. then the initial metastable mixture of reactants is insufficiently stable for a flame to propagate through it at an identifiable quasisteady speed.
~ A w .z ) . then. Why.2 (I/g) dz] in fact shows that It.  d {g2 exp[ 2 dz [( ) : d z ] } = 2Aw exp[ 2 I(): dr]. (53) as can be seen explicitly by expanding the derivative on the lefthand side of equation (53) by parts. substituting this same upper * The observant reader may have noticed that by setting T = 1 (and therefore g = 0) in equation (50).150 Theory of Laminar Flames when evaluated at z = zi.” Multiplying equation (52) by exp[ . Equation (51) will be used shortly to determine an upper bound for A. Integrating equation (53) from z = zito z = 1 and utilizing the boundary conditions on g yields after dividing by 7’.* On the other hand. Equation (54) will be used to determine a lower bound for A. which also yields an upper bound for A when an upper bound for g ( r ) is used to evaluate the integral. This is readily seen with the upper bound g(r) = T . Dividing equation (47) by g and integrating from z = zi to z yields 9 = 5  A By substituting equation (50) into the integral on the righthand side of equation (49). (1 . it is clear that by substituting an upper bound for g(z) into equation (51) a lower bound for the integral is obtained. (52) which resembles a linear equation for g2 and therefore suggests obtaining a “solution” by means of an “integrating factor. equation (51) yields a lower upper bound for A (a value closer to the correct value of A) than does the simpler equation. whence the resulting value of A given by equation (51) will be an upper bound. and g are all nonnegative. Equation (47) may also be written in the form d(g2)/dz = 2(g2)/9 . (o/g) d T = 1. for which the value of A given by the simpler equation is twice the value given by equation (51). (50) which becomes when the double integral is reduced to a single integral through integration by parts. . Since u. should we employ the more complicated expression given in equation (51)? The reason is that for most upperbound trial functions g(r). one obtains A l:. it is found that s: (w/g ) dz.
rigorous bounds for the burning rate eigenvalue A. and equation (56) or the average of equations (56) and (57) provides a closer estimate for A than that obtained by many approximate methods. Integrating equation (47) from z = zi to T gives g2/2 = z?/2 . (56) after the inner integration over T is performed. 5. implying that the exponential and therefore the outer integral assume upper bounds.A [ w dz ri + [y ri dz. and the present method constitutes a truly rigorous procedure for obtaining solutions of any desired accuracy.3. (55) Hence T may be used for the upper bound of g in equations (51) and (54). Integrating equation (50) from T = zi to T yields where the last equality is obtained through integrating the last term by parts.4. because the inner integral will be a lower bound. Equations (56) and (57) constitute explicit. it follows from equation (50) that 95 T.3. Since they have proven that this procedure converges and that g(z) monotonically approaches the solution of equation (47). Since A (wig) d z 2 0. Iterative procedures and variational methods An iterative technique for obtaining successively narrower upper and lower bounds for the eigenvalue A and successively lower upper bounds for the function g(z) has been developed by Johnson and Nachbar [21]. These bounds typically are reasonably narrow. (59) . the oscillating divergence sometimes observed with other iterative schemes cannot appear here.5. Equations (51) and (54) can therefore be used to provide limits between which the eigenvalue must lie. Equation (51) then implies that A I and equation (54) shows that [2 [:(WT) dT]'. The Unimolecular Decomposition Flame with Lewis Number of Unity 151 bound for g(r) into equation (54) will yield a lower bound for A.
convergence is usually slower when equation (50) is used instead of equation (60) (see the preceding footnote).1)st approximation to prove that the (n + 1)st approximation is a lower upper bound than the nth approximation. gml(z) approaches the correct solution from above and Alnlapproaches the correct eigenvalue from below. Since the first estimates for the bounds of A given in equations (56) and (57) are so close together. The induction proof is then completed by using the assumption that the nth approximation for g is a lower upper bound than is the (n . Throughout this reasoning. .3 it is seen that for each grnl(z) a value of A may also be computed from equation (51). however. since the fact that the nth approximation for g is lower than the (n . then the second approximation obtained from equation (60) will be a lower upper bound. Equations (54) and (60) provide the basis for the iterative procedure. This last proof is obtained quite simply from equations (54) and (60). An upper bound for g(z) is substituted into equation (54) in order to obtain a lower bound for A. the righthand side of equation (60) will assume an upper bound.1)st approximation immediately shows [via equations (54) and (60)] that the righthand side of equation (60) used in obtaining the ( n + 1)st approximation is smaller than the righthand side of equation (60) used in obtaining the nth approximation. since the integral in equation (60) will clearly assume a lower bound.152 Theory of Laminar Flames which becomes when equation (58) is substituted into the last term. then. Thus successively narrower bounds for the burning rate and successively smaller upper bounds for g = dz/dt are obtained. it appears likely that few iterations would be * It is obvious that if g = 5 is used as the first approximation. and that the resulting sequence of values will approach the correct eigenvalue from above.3.* The nth approximation for g is then given by [see equations (60) and (5411 where In accordance with the preceding discussion. as n + m. From the discussion in Section 5. If this value of A and the upper bound for g(z) are substituted into the righthand side of equation (60). The fact that the resulting new upper bound for g(z) is lower than the previous upper bound requires proof by mathematical induction. whence equation (60) implies that the ( n + 1)st approximation is smaller than the nth approximation. equation (60) could have been replaced by the simpler expression given in equation (50). and hence a new upper bound for g2(z) will be given by equation (60).
However. which is easily evaluated in terms of exponential integrals [33] when w is given by equation (43). and the coldboundary difficulty thereby disappears. Other iterative methods have been proposed that are less well justified.5 and 5. based on the introduction of q = ec as a new variable. von Karman suggests that an approximation to A can be obtained from equation (63) by approximating the integral therein on the basis of the behavior of z ( t ) in the vicinity of the hot boundary. It may be noted that if the present methods are employed.  (63) I = IO1w dz.z) and integrating from 0 to 1 yields AI where = 9 . 1 .6 will be sufficiently accurate. for example. ds/dt = c. d 2 t / d q 2 = . For the purpose of burningvelocity calculations. [S].3. from . may be employed.z = c(l . The Unimolecular Decomposition Flame with Lewis Number of Unity 153 required to obtain an exceedingly high degree of accuracy. by the introduction of zi # 0.5.t).Aw/q2. [31]). 5.(1 .3.5.t) . for most applications. so that equation (46) can be written in a standard form. A variational approach also has been developed [25]. The approximations of Zel’dovich. one approach [30] employs equations (48) and (49) directly.jol(lz) dt. A linear relationship. either equations (56) and (57) or one of the other approximate formulas to be given in Sections 5. and von Karman Many approximate formulas for A have been developed on the basis of the physical idea that conditions in the vicinity of the hot boundary control the burning rate (for example. For example. None of these approaches circumvent the coldboundary difficulty unless o(z) is modified suitably. The approximations to be discussed next bypass the coldboundary difficulty in a natural way. From equations (61) and (62) it is seen that the integrations that must be performed in carrying out the present technique are not excessively complicated. with the constant c obtained in terms of A by evaluating the slope. with the nth approximation for g(z) substituted into the integrals to obtain the ( n + 1)st approximations for A and g(z). One way to see how these formulas may be obtained is to follow the approach of von Karman [32]. then calculations must be performed for various values of zi to find conditions of pseudostationarit y.3. the integral is convergent. and it will be unnecessary to employ the method described here. FrankKarnenetskii.3. In this approximate evaluation. Multiplying equation (42) by (1 .
we obtain. we find that The activation energy and the heat of reaction are usually sufficiently large that a negligible error in this integral is produced by extending the upper ~ the integrand of the limit to infinity (l/fi’a’ = 0).@)/(21). For later convenience in analysis. These formulas of von Karman [32] become increasingly accurate as p‘ increases.6. by transforming from the variable z to z = p’(1 . A simpler approximation is to put c = 0. which is proportional to m or u. Asymptotic analysis for strongly temperaturedependent rates Although the asymptotic analysis was developed first on the basis of a formulation in the variables appearing in equation (42) [9]. The formula of Zel’dovich and FrankKamenetskii [7]. it is more instructive to begin with equation (46). This formula is nearly as accurate as the von Karman expression from which it was derived and is exactly the same as the first approximation obtained by the asymptotic analysis to be presented next. then the error in u. the combinations a = a’/( 1 + a’) (not to be confused with the a of Chapter 2) .154 Theory of Laminar Flames the limiting form taken by equation (42) at the hot boundary. The factor (1 + ~ / p ’ ) in resulting expression for I may be expanded in powers z/p’ to obtain an asymptotic expression for I useful for large values of 8’. obtaining A = (21)’ directly from equation (63).z)/(l/a’ + z) in equation (64).. if p’ > 2. 5.. The significance of this result and of the appearance of the nonnegligible factor 1/p’ on the righthand side will become clear after the activationenergy asymptotics have been developed. This may be shown to give A = (1 . for the second. [34] may be obtained from the simplest result of von Karman by performing an asymptotic expansion of the integral’I for large values of fi‘ and retaining only the first term in the expansion. Keeping only the first term in the expansion. with 0 meaning terms of order.. typically is less than 10% when the first formula is used and less than 300.3. The introduction of this result into the formula l/A= f l yields 5 I/& = + l/a’) p’ which is the expression of Zel’dovich and FrankKamentskii for the nondimensional quantity l/&.. 1% ( +B’ )’ 1 lja’ ~ J : z e K 2 dz + 0($) JZ(1 = (y)2 + O($). In view of equation (43).
. following the formalism of matched asymptotic expansions [35]. .2.(p). dividing by H. it seems appropriate to call p the Zel’dovich number. subtracting the result from equation (46). an outer expansion of the form z = zo(5) H1(p)z1(5) H 2 ( p ) z 2 ( 5 ) . Because of the many important contributions of Zel’dovich to our physical understanding of the theory. in addition to p’ being large.8 and seldom are less than 0.z)exp{p(l  z)/[1  a(l  z)]}.5.” since p appears inside the exponential) unless z is near unity. .and so on. = (1 . 1. . the analysis will be developed on the basis of the rate expression given specifically in equation (66) by considering the parametric limit in which /? + 00 with a of order unity and held fixed and with A required to vary with fl in such a way that a nontrivial result is obtained. From equation (66) it is seen that as p becomes large the reaction term in equation (46) becomes very small (“exponentially small. and p is the product of a with the nondimensional activation energy E1/RoT. In describing this convectivediffusive zone. and large activation energy and large heat release both favor large p. It may be emphasized.T’. In terms of a and the rate expression in equation (43) becomes LC) 0.5. Therefore. Hence for 1 . Representative values of p in fact lie between 5 and 15. The Zel’dovich number is a nondimensional measure of the temperature sensitivity of the overall reaction rate. there is a zone in which the reaction rate is negligible and in which the convective and diffusiveterms in equation (46) must be in balance. Here f + + + lim CHn+ l(P)/ffn(P)I B. that other rate expressions can be treated in a similar way. produces the sequence of outer equations d 2 z n / d t 2= dzn/d<.. qualitatively a measure of the strength of the dependence of the reaction rate on the extent of reaction completed. thus /? generally is large if p’ is large. (0 < a < l). f Substitution of this expansion into equation (46).z of order unity. The Unimolecular Decomposition Flame with Lewis Number of Unity 155 and /? = alp’/( 1 + a‘)are employed in place of a ‘ and p‘. n = 0. numbers that are sufficiently large for asymptotic results to be reasonably accurate. (T. Values of a typically are 0. (67) . Thus fl < p‘.3.. . For the sake of being definite. however. is the appropriate large parameter of expansion. The attribute that is essential to the asymptotic approach is that the nonnegative singlepeaked rate function possesses a maximum that narrows and increases in magnitude and that occurs at a location progressively closer to the fully burnt condition as p co. the heat release cannot be too small if the asymptotic results are to be accurate. again passing to the limit /3 + 00.m = 0. It will be found that j. (66) Note that a is the temperature rise divided by the final temperature. . with HOW) = 1.)/T. passing to the limit /3 co. may be introduced.rather than p’.
. To ascertain formally a suitable independent variable for use with y necessitates investigating various possibilities. then matching again cannot be achieved. If this dependent variable is denoted by q. the expansion Y = A = (llS2>CAo+ Sl(PIA1 + s2(P)A2 + . = A. may be introduced.(p) p". the reactionrate term is no longer exponentially small. (69) where use has been made of equation (66). Thus the downstream zone cannot be thicker than the upstream zone.(o)/s(p). With the stretching q = (5 . the necessary reactivediffusive balance with y and q of order unity will be maintained only if s2A is finite and nonzero in the limit. n = 0. Study also shows that if dq/d( is of order unity in the limit. from equation (66) it is seen that when 1 . Any stretching of this type causes the convective term in equation (46) to become small compared with the diffusive term.e5. . From equation (69) it is seen that in the limit p + co (s + 0). . are constants to be determined by matching conditions.(fi)] = 0 for any fixed a > 0 of order unity. so is introduced as well. The inner zone therefore is reasonably termed a reactivediffusive zone.z becomes of order b'.. where limB.. for H. Following a ..+l/sn) 1.I = = 0.[h. This observation indicates the need for a downstream zone in which 1 . . where lim~~m(s. The solutions to equation (67) satisfying the boundary condition that z = 0 at ( = co are   T. m[Aeup/H. where s + 0 as p + so. in fact. the reactionrate term can contribute to equation (67) only at exponentially small ordersfor example. Therefore. Therefore. and since at least two terms are needed to satisfy the matching and boundary conditions successfully.T). for H. then any selection having limp. equation (46) written in inner variables is d2YldV2.(p) CUB.(dq/d() = co .z is or order p'. 2. . This last restriction is satisfied by all algebraic (powertype) ordering functionsfor example.156 Theory of Laminar Flames so long as limp.s dYl4 = S2AY expCyl(1  aY/P>I. limB+. . Equation (68) must fail if ( becomes sufficiently large.the downstream zone is thinner than the upstream zone and may reasonably be viewed as an inner zone. An appropriate stretched dependent variable for this zone apparently is y = p(l . there must be a reactivediffusive balance in the inner zone to the lowest order. (68) where the A . In equation (69) an inner expansion of the form YO(V> + hl(P)Yl(V) + hz(B)Yz(rl) + . . with h&?) = 1.(dq/d() = 0 produces in the lowest order a firstorder equation that expresses a convectivereactive balance and that lacks the flexibility needed to satisfy the downstream boundary condition and simultaneously match with equation (68).+ l(fi)/hn(P)] = 0.. 1.
(1 + y. + . as may be anticipated from the fact that z decreases (y increases) as v] decreases.3440. s. ~ . . .may be applied to the inner equations. + H . Completion of a solution by matched asymptotic expansions entails employing matching conditions. Y . .00./s)y.s. if desired. the differential equations for y. e c o + . = P". a twoterm expansion for A is available. + . and a composite expansion for T ( < ) may be constructed by standard methods [35].y. = s(P)v]/t(P) = (5 .[l ..y.5. From equations (68) and (72). (n = 1 . Unlike equation (70). held fixed. l(y.) + H . where v]. A further integration then gives An expansion of this formula for large negative values of v] produces yo = &v] + constant + e. Although there are many ways to effect matching. /:yfeCy' dy' = Ao[l ..'. 2 . in agreement with equation (65).t. The first integral of equation (70) then is +(dy. .) are linear. = 1..s. the two asymptotic expansions must agree. the most infallible approach currently available is to investigate a parametric limit in an intermediate variable [35]. + . it may be shown that H .p + h.. . With these results. A N Ao/s2 = p2/2.hence we may put s = p.t. z . [36]). is introduced on both sides. Thus we consider P + co with v ] . y. = 3c( . we then generate a sequence of inner equations./dv])' = A. (72) where e.). and methods for solving them are available (for example. equation (73) may be written as 7..)/t(P). (74) Equation (74) is used repeatedly at successively higher orders to evaluate constants and ordering functions.. . The Unimolecular Decomposition Flame with Lewis Number of Unity 157 procedure analogous to that described for the outer expansion. . + . = P". A . where y = f : (1 .(1 yo)eyo]'i2} d y .3.)eCYo]./dv]. (71) It is found. h. that to achieve matching the negative square root must be taken in equation (71) in obtaining dy. and A. the first of which is d2yO/dy2= A. . 0 as v] co. The general matching condition is then written as (73) where 7 implies that when v]. Thus we first find that Aoe50= 1 and next find that s must be of order p.thereby obtaining = 1. = p".. . stands for terms that go to zero exponentially in v] as v] + .(. 7 1 . with t ( p ) + 0 and t ( P ) / s ( P ) + m in the limit. 7 1 + p'&(t. A0e5"(1 + tqt + . + (70) + The downstream boundary conditions. These last results provide the the further matching requirement first approximation to the burningrate eigenvalue. By proceeding further with the expansion and matching.~ O .
. There are two zones through which the temperature varies: a thicker upstream zone in which the reaction rate is negligible to all algebraic orders in p'. followed by a thinner reaction zone in which convection is negligible to the lowest order in P'. . Analyses at the depth indicated here underlie applications of activationenergy asymptotics.3). could have been guessed in advance and later verified to work.4. the expansions A = P2Ao + PA. as well as elsewhere in this volume (for example. = i. Schematic illustration of deflagration structure obtained by activationenergy asymptotics.' y . Because of the translational invariance of the original problem. . + . the value of to. .rn ( y o + co) to obtain A. simplification can be achieved by employing this fact to demand at the outset that the reaction occur at r = 0.4. the entire analysis can be completed in a few equations [38]. where the reaction is occurring. In most publications. and y = yo + P . the reactant concentration has been depleted by diffusion so that it is of order B' times the initial reactant concentration. The flame structure that has been calculated here is illustrated schematically in Figure 5. at least in principle. although much thought underlies the equations. matching conditions such as equation (73) seldom are written. often physical understanding allows shortcuts to be taken. abbreviated presentations are made. the expansion in terms of H. .which specifies the first approximation to the location of the inner zone. Suitably imposing this stipulation at all algebraic orders allows the outer solution to be written in advance as z = e5 for 5 < 0. where t ( ~ )is sought. giving the first approximation for the burning rate. For example. Section 3.4. In the formulation based on equation (42). z = 1 for 5 > 0. the convectivediffusive zone need not be mentioned Slopes match I 1 FIGURE 5. With these simplifications. matching of the slopes of the inner and outer solutions [37]may then be employed directly in equation (71) for q + . + A2 + . for example. The reaction occurs in the thin downstream zone because the temperature is too low for it to occur appreciably upstream. A simpler matching criterionnamely. However.158 Theory of Laminar Flames The extended discussion of activationenergy asymptotics that has been given here was included to illustrate details of the technique that sometimes are needed in analyzing difficult problems.(a) then need not be introduced at all. cannot be calculated.
where it can produce corrections to uo approaching 50% in extreme cases. The value of vo obtained from the twoterm expansion typically is 10% below that given by the first term. notably the strongest dependences on L/cP. It is at least as accurate as the best results obtained by ad hoc methods prior to its derivation.To)/RoT:.3. the burning velocity given by the twoterm expansion A = +/I2 + P(3a .. if w in equation (2) is evaluated at the initial concentration and at the final temperature. Retention of the second term in equation (75) is especially important at the lower values of p. . and /J = E.y)..To)/T. no change occurs in ~ ( z )until z is within B. the reactant concentration has * Here 0 means terms of order. the difference is an order of magnitude. The reaction zone is sufficiently narrow in the coordinate to allow the reactionrate function to be approximated. This result has come formally from the matching condition and represents the only burning velocity for which an internally consistent asymptotic structure for the deflagration can be obtained. the latter two controlled by the Arrhenius exponential.or higher. if accurate results are wanted. then the numerical value of uo obtained from equation (2) is roughly p times that of equation (75). In the reaction zone. In dimensional form [see equation (45)].(T. However.5. for many purposes. The principal functional dependences of uo agree in equations (2) and (79. .of unity (see Figure 5.B. is* where o! = (T.4 shows the physics that have been overlooked in deriving equation (2). In making this comparison. . The Unimolecular Decomposition Flame with Lewis Number of Unity 159 since the solution therein is t = 0.p. [34]. but no physical basis exists for selecting this temperature. T. Thus Zel'dovich numbers for real flames lie in a range that is both appropriate for application of asymptotic methods and sufficientlyfar from the limit to require a formalism capable of generating the second term in the expansion. The twoterm result in equation (75) lies within a few percent of the pseudostationary burning velocity calculated numerically over the entire range of values of p that could be of practical interest (fi 2 2. This deltafunction idea underlies the early development of equation (65) [7]. Figure 5.3). see [9]). for simplicity let us ignore the correction terms in equation (75)of order 8. The results could be made to agree by evaluating w in equation (2) at a suitable lower temperature. It is of interest to compare equation (75) with equations (2) and (3). At representative values of B. and El. as a delta function in 5 that describes appropriate jump conditions across a reaction sheet [39]. the twoterm asymptotic expansion for uo is significantly better than the corresponding oneterm expansion of Zel'dovich and FrankKamenetskii obtained from equation (65) and given by the first term in equation (75).
profile is easily computed from equation (5) by using the velocity profiles obtained from the equations in this section.5. however. in equation (2) w should be evaluated at p. the total pressure drop seldom exceeds 1 mm of mercury.4 to obtain correct fi factors in equation (2). because of the strong temperature dependence of w.3. Increasing the activation energy makes the reactionrate curve more sharply peaked toward the hot boundary but has relatively little effect on the shapes t FIGURE 5. Generalizations to other flames Some additional aspects of the deflagration structure are illustrated qualitatively in Figure 5. therefore. . it is for example.160 Theory of Laminar Flames been depleted through diffusion by the factor p . The small pressure drop shown is not predicted by the equations in this section (since p = constant here).7. The reader may be interested in doing this to test his or her understanding. . that cannot be obtained from equation (2) without introducing these modifications. ' 5.5 in the physical (x) coordinate. It would not be difficult to modify the physical reasoning given in Section 5. since the reaction does indeed occur at the downstream side of the deflagration). that p must decrease. the reaction rate). since v increases through the wave. The actual pressure clear from equation (9. the reaction proceeds not in a zone of thickness 6. There are evident secondary dependences of uo on the overall activation energy and on the heat release.2 on the basis of considerations derived from a structure like that shown in Figure 5. as given by equation (4). appearing through p in equation (79.times the initial concentration (and at T. Representative variation of flow properties in a deflagration wave. These two factors of p' produce the p' in equation (75). All properties vary monotonically through the wave (except.' . Furthermore. Mach numbers are sufficiently small for this fundamentally perturbative approach for obtaining p(x) to be well justified. but rather in a thinner zone of thickness 6/p. of course.1.
The type of reasoning that has been given here can be extended to take into account reaction orders different from unijy and multiplereactant. spreads all curves over a larger range of x. equation (1) yields 6 &.Y). and p curves) over a somewhat larger x range.)/=. and solutions to equations (19) and (22) are z = eT and Y = eLeC. independent of A/cp..1.3. = Yl.. respectively. Thus an increase in A/cp at constant pD. provided that there is no appreciable modification in w. keeping Le = 1. However.. Since the fuel mass fraction is Y. there may be a change in the average reactant concentration in the reaction zone. Increasing pD with A/c. The Unimolecular Decomposition Flame with Lewis Number of Unity 161 of the other curves. the p. A quantitative estimate of the magnitude of the effects of relative diffusion of reactant and heat can be obtained on the basis of the structure of the convectivediffusive zone of Figure 5. Since w is proportional to the fuel concentration. x Y. If A/cp is increased with pDlz held constant. while causing less change in the composition curves. onestep chemistry. increases the burning velocity proportionally but leaves the extent of the T profile in physical space unchanged. u.o(l . the way in which the curves in Figure 5. . then Le # 1. proportional to cp/A. increasing A/cp should spread the T curve (and. if the Zel'dovich number p were not largethen no influence of A/cp on w would be anticipated. assumption 10 is violated. and the analysis in this section is invalid. the structure illustrated in Figure 5. w is proportional to the reactant concentration (in the reaction zone) to the nth . may be expected physically to spread the reaction region of elevated temperature over a larger range of reactant concentration. .4indicates that for reasonable values of p.4.Le 5. held constant decreases m (physically by diffusively reducing the reactant concentration in the reaction zone. thereby effectively increasing the average reactant concentration in the reaction zone and hence increasing w. However. consequently. and equation (2) implies that m (A/c.5. If there were a singlezone structure to the flamethat is. Increasing A/cp and pD. where the conditions z = Y = 1 have been imposed at the reaction zone (5 = 0).. for large p arises through the influence on the reactant concentration in the reaction zone... An increase in A/cp at fixed pD.. a) .. Since thermal effects alone were considered in deriving equation (l).5 will be modified can be inferred from reasoning like that in Section 5. The asymmetry in the effects of variations of A/c. thereby decreasing w) and consequently increases the spatial extent of the T curve (in proportion to and of the concentration curves [in proportion to (pD12)3/2J. the expansion of the convectivediffusive solution about 4 = 0 is Y. the spatial extent of the composition curves is narrowed. For a onereactant proces of reaction order n. In this zone 6 = 0. which indicates that in the reaction zone. the fuel concentration is proportional to Le.2. because of the increase in m at constant pD.. and pD. A symmetric behavior could be anticipated if the reaction extended throughout the entire thickness of the deflagration.
See B. [13]. For n < 1.1274 for n = 2.l. This modification is needed because. A. At higher orders. in the reaction zone is proportional to Le p.equation (l). to appear (1985).In 2) for n = 0. so that w is proportional to Le”fi”.~ (76) ) where r denotes the gamma function [T(n + 1) = j. * In equation (76) A is defined as in equation (45) but with the additional factors v ~ . as is evident from the functional form y”.71 + ~ ( f i .3440 for n = 1.970 for n = 3. and powers of p appear that depend on the reaction order./(. expansions of these quantities about their hotboundary values appear. the reactant concentration tional to ( p D cp//z). which depends on n. the extent of the concentration profiles is seen to be proporMore precisely. assumption 9 and many of its consequences no longer are valid for n # 1 [for example. and y = 2. . yneKydy = n!] and A = {p+l/[2r(n Here y. l ( Y l . approximations corresponding to assumption 11 are unnecessary because the reaction rate is relevant only near the burntgas state.4. for n > 1. To the lowest order. in which a balance between convection. onestep process of order n is [36]* .times the initial concentration). with the rate expression given by equation (18)./m. although M = 1 and N = 2. the reaction goes to completion (y = 0) at a finite value of y~ in the reaction zone. it is sufficient to evaluate the quantities in the definition of Afor example. Occurrence of these finer details of the reactionzone structure is comprehensible qualitatively on the basis of the relative rapidity with which the reaction rate decreases with decreasing reactant concentration at very low reactant concentrationsthis rapidity is low for small n and high for large n.6. There have been a number of analyses employing activationenergy asymptotics for tworeactant. Williams. Jm. onestep chemistry. without performing the asymptotic analysis. equation (76) provides a flamespeed formula in which every factor except the constant 2r(n + 1) could have been obtained by physical reasoning based on Figure 5. and diffusion develops at a very low concentration level (of order p(“+ ‘ ) i ( n .162 a Theory of Laminar Flames power. reviews also may be found elsewhere [lo]. CST. where 5 is of order unity.~ [ 4+n i)(n + 2)/2 . there is a thick downstream region.y = 1. has been evaluated by numerical integration for various values of n [36] and is shown in Figure 5. Rogg and F. reaction. For Le = 1 a twoterm expansion of the burningrate eigenvalue for a onereactant. y = 0. o p / W l ) ’ on ~ l the righthand side. equations (16) and (34) are revised]. + 1)1>{1+ 2 ~ . in equation (45)at the hot boundary. Most of these have been summarized by Mitani [40]. In the asymptotic analysis to lowest order. representative values are y = 2(1 .l/cp)Len. and therefore from. the extent of the temperature profile from equation (2) the burning velocity is is proportional to and from the Y solution in the convectiveproportional to diffusive zone.
WlY2.)"'& "2B1. on the reaction order n. are the corresponding Lewis numbers (Lei = A/pD. v.0/v2W2Yl."' Le. .. in which a = p(4 . n 2 . the formulations have been based not on equation (8) but instead on diffusion equations of the type dY.. 2 are the two reactants and n . (77) where D i is a diffusion coefficient for species i in the mixture. oo 72Y 7: 0'n2 2 Wnl+nZl n l + n z + l PoCp. Jv."' x J e E1~2RaTm. . + 1 (78) where G(nl. = 1.m 1 P Le.cp). with 4 = v.. Equation (77) is derived formally by assuming that an inert species i = N is present in great excess so that the other species effectively diffuse through this inert. . while Le. N . a) = ~omy"'(y + aY2eFYdy. .. Apparently results based on equation (77) can be surprisingly good [41] if the inert is taken to be an average product. . equation (76). If i = 1.3. then to the lowest order in p' the asymptotic analysis yields [40] ' 0 = [ 22.1)/Le2.1.l(v. and Le. i = 1. whose concentration profile is calculated a posteriori from I. if species 2 is ..5. and n2 identify the reaction orders with respect to these reactants. The Unimolecular Decomposition Flame with Lewis Number of Unity 163 0 I 2 3 4 5 J PI FIGURE 5. Equation (78) holds for4 > lthat is. Dependence of the term y in the formula for the burningrate eigenvalue./dx = ( m / p D i ) ( q .6.o being the equivalence ratio. With notable exceptions [41].ti).
a) = T(n. if it is found that 4 < 1. rich. then G(n. however. Equations (78) and (79) have the merit of exhibiting explicitly the influences of transport coefficients on flame speeds and of providing explanations for some initially counterintuitive results (for example. n2 1). For offstoichiometric conditions.2. The extra 1 in n1 n2 1 for p comes from the thinness of the reaction zone in comparison with the flame thickness. ormore preciselyif 4 . For onestep reactions the analyses that have been given here for flame structures and flame speeds have successfully removed many of the most restrictive assumptions that were introduced beginning in Section 5..2.1 is small compared with p'). 6. For stoichiometric conditions (4 = 1. such as influences of variable Lewis numbers. in particular. Formulas like equations (78) and (79) are useful for calculating the flame speed as a function of the equivalence ratio. and therefore the ratereduction factor (Le2/PY2does not appear in equation (79). and Tm peaks near 4 = 1. usually smoothly because of equilibrium dissociation of products.1 to be large compared with p'.a) = an2r(nl l). since El/RoTm is large. for example. that the high diffusion coefficient of H2 tends to reduce the burning velocity of a fuellean H202 flame). Assumptions 81 1 have been largely eliminated. but these formulas cannot be employed in the absence of appropriate chemicalkinetic information for overall rate parameters. If conditions are sufficiently far from stoichiometry for 4 . and equation (78) reduces to + + + (79) The principal features of these flamespeed results are readily comprehensible physically from the previous discussion.164 Theory of Laminar Flames present in excess of the stoichiometric requirement or if the mixture is stoichiometric. n 2 . n 2 . and lean mixtures (see. we have G(n. species 2 is not depleted appreciably. Usually the strongest variation occurs in the Arrhenius factor. with some minor questions remaining. then equation (78) may be employed merely by interchanging the definitions of species 1 and 2 throughout.. the powers of fi and of the Lewis numbers in equation (78). and n2generally differ in stoichiometric. It must. [42]). the overall rate parameterssuch as El.. be recognized that many of the quantities appearing in these equations vary with 4. Assumption 7 could be circumvented in an asymptotic analysis by use of the idea + + . The remaining powers for p (nl and n 2 ) and the Lewis numbers come from the rate expression w and reflect the fact that in the reaction zone the concentration of reactant i is of order Lei/p times its initial concentration because of the concentration reduction through the convectivediffusive zone. n. It is also quite significant that in onestep approximations. Consider.
i = 1. N..4. Equation (80) is the ratio of equation (7) to equation (13). the quantities w i . If assumptions 17 of Section 5. planar. and finally dividing by equation (13). The physical effects that have been considered here refer specifically to steady. For steady.t j .4. 5. compare equation (112)].1. If an ignition temperature is defined in such a way that wi = 0 for .which is given by equation (40). it is unclear that much further work directed toward removal of other underlying assumptions would be warranted prior to study of the importance of the onestep approximation. 1. The independent variable employed here is the normalized dimensionless temperature z.5.2 and 9.1. Investigations of multiplestep kinetics are addressed in the following section.4. . planar. then the flame equations may be taken as dtJd7 = (A/2/m2cP)(wJf). ]  (1  (82) is a linear function of z and tj. additional physical phenomena occur if these assumptions are relaxed (see Sections 8. the critical remaining approximation is that of a onestep reaction. a ) / . and the average molecular weight W = l / x l q / K . FLAMES WITH MULTIPLESTEP CHEMISTRY 5. The 2N dependent variables ciand X i appear in the 2N expressions given in equations (80) and (81) (with pressure constant. I: = X i W $ T . and equation (81) can be derived from equation (8) by first expressing in terms of X i . .2 and the isobaric approximation p = constant are retained.5). Discussion of the background and the nature of the problem 5. adiabatic deflagrations.and so on are known functions of z and Xi). adiabatic flames (assumptions 1 and 2).. K. Formulation Let us now consider flames in which more than one chemical reaction occurs. then using equation (19) to eliminate W/p. . and departures from assumptions 3 and 4 could be investigated readily.4. (80) and (81) where f 1 " j= 1 hy(cj .[namely.1. Flames with MultipleStep Chemistry 165 that the reaction occurs mainly near the hot boundary.
To). However.4. while = ti at T = 1 and chemical equilibrium exists (wi = 0) at T = 13 is expected to determine a (unique) solution to equations (80) and (81) only for a particular value of the mass burning rate m.1. reliable and general approaches to the accurate calculation of flame structures and flame speeds for arbitrary reaction kinetics do not yet appear to be available. for idealgas mixtures with Dufour effects neglected. thereby requiring a search in a multidimensional space to satisfy suitable conditions at the cold boundary [43]. Thus. planar.2 and 4. namely. The main limitation to the formulation given is assumption 7 to the effect that cp.3).merely at This assumption can be removed.166 Theory of Laminar Flames T below the ignition temperature and wi is given by equation (18) for T above the ignition temperature. adiabatic.hj. Although it is conceivable that nonmonotonic behavior of T could occurfor example.To). [45]. . notwithstanding the significant advances made in recent years (see Section 5. . with complicated chemistry. then a reasonable set of boundary conditions [for example. m)/cp(Tm . The normalized temperature z. This “multipleeigenvalue” aspect of the problem has led to questionable suggestions to the effect that flammability limits may be associated with the nonexistence of solutions to equations (80) and (8 l). where each h j is a known function of T and cp is arbitrary since it cancels from the equations. but these are difficult to begin because. These modifications should not introduce appreciable additional complexity if solutions are to be sought by numerical integration. the formulation then becomes quite general. with complicated chemistry the integration of equations (80) and (8 1) faces computational difficulties. f= ( h j t j . formal expansions about the hot boundary demonstrate the necessity of selecting values of more than one parameter for starting a numerical integration. and isobaric approximations. with T = IT . For example. tendencies for stepwise integrations in the direction of increasing T to diverge from the hotboundary point motivate integrations starting at the hot boundary. given by equation (40). associated not only with “stiffness” (Sections B. is a convenient independent variable only if it varies monotonically with distance through the flame. and numerical integrations of the ordinary differential equations have been completed successfully only by the introduction of special devices 11441. for flames in which endothermic reactions become dominant at the highest temperaturesno practical examples of adiabatic flames with temperature peaks or valleys are known.1) but also with complications from molecular transport and from eigenvalue aspects.To)/(Tm the expense of complicating the definition off in equation (82).i= c p = constant.2. [46] that seem better suited t o some flames than to others.5. = ei at z = 0 and all ti are specified at T = 0. subject only to the steady. It is also straightforward to include Soret diffusion by adding appropriate terms to equation (8 1).2. the use of T seems appropriate from the viewpoint of monotonicity.co ej.
as has been seen in the previous section. the objectives are to develop physical insight.3.4. are associated with chaincarrier distributions.reasonable accuracy even if predictions of chaincarrier distributions are poor.1.4. In the order of increasing difficulty.2. Three specific objectives of studies with real kinetics may be identified. planar. Objectives of Analyses There are two broad classes of theoretical analyses of steady. The methods employed in studies with model kinetics often are analytical in character. 5. Literature Investigations with model kinetics date from the early work of Zel'dovich and Semenov [47]. isobaric deflagrations with multiplestep reaction kinetics. thereby possibly obtaining better values for poorly known rate parameters of certain elementary steps. studies with model kinetics and studies with real kinetics. Flames with MultipleStep Chemistry 167 5. These predictions are of interest not only because of their relationships to fundamental transport and chemicalkinetic properties of chain carriers but also because observable properties of flames. Studies in the latter category endeavor to employ correct kinetic data for particular flames to the extent that these data are known. and concentration profiles of major species often can be obtained with. they depend on overall levels of chaincarrier concentrations but seldom are affected appreciably by distributions of radicals or atoms in the cooler portions of the flame. such as emission of chemiluminescent radiation. adiabatic. Concentration profiles of major species usually are controlled mainly by the burning velocity and transport coefficients.4.5. Thus the most challenging problem in laminarflame theory is to predict the distributions of chain carriers in flames. to predict the distributions of temperature and of major species (principally reactants and products). Burning velocities often are influenced primarily by conditions near the hot boundary. In particular. while those for studies with real kinetics usually are numerical. they are to predict the burning velocity. namely. temperature profiles. A number of different model mechanisms have been studied on the basis of analytical approximations designed to .1. Studies have shown that burning velocities. and to predict the distributions of species present in lower concentrations (principally chain carriers). As indicated in Appendix B. their objectives are to improve knowledge of chemical processes in specific flames and to achieve agreement with experimental results. Studies in the former category employ relatively simple rate expressions designed to retain some essentials of the full chemistry in various flames but not based on accepted rate parameters for any specific flame. the burning velocity per se seldom is a sharp discriminant of proper kinetic details. the chemistry of flames generally involves chain reactions. not to obtain predictions for real flames that can be compared with experimental results.
to search for the full range of possible behaviors. the mechanism A + B + 2C (at a negligible rate). then no matter how small 6 is. The tworeactant. [34]. then there usually is a single flame with two reaction zones separated by a transport zone. respectively. Mechanisms that have been studied include the sequential reaction A B C . Additional mechanisms that have received consideration are the straightchain model [lo] A + B + 2C + B. these quantities need not be defined precisely here). as 6 becomes sufficiently large the step B + C begins to occur in the reactivediffusivezone of the flame and to influence the flame speed (it may be anticipated that even if bz > 0.168 Theory of Laminar Flames provide estimates of flame speeds (for example.2). then at sufficiently small values of 6. the techniques of asymptotic analysis have been brought to bear on simple mechanisms. embedded within the convectivediffusive + + + + + + + + + + * Numerical methods rather than asymptotic analyses were employed in the first of these references. If a1 I processes with highly reactive reaction intermediaries). [62]. aC. if 6 is sufficiently small. . [48][51]). For there to be a positive net heat release. and also related processes with varying extents of chain branching. there is a thick convectivereactive zone for B + C. endothermic. C as a chain carrier and D as a product. here a. If p2 = 0 with positive. traveling faster than the second. in which A functions as a reactant. the process A + B cannot proceed without energy input from B C. a1 + a2 must be positive. [%I. C. but these two reaction zones merge at sufficiently large values of 6. and let 6 be a measure of the ratio of the rate of the second step to that of the first (since the discussion is purely qualitative. [57]. Let ak and Pk represent nondimensional heat releases and activation energies. then two separate flames may occur. and A C + D C (or 2C + D). A + B. in this case. in addition to this structure there appears zone. however. If 6 is larger. and 6 are stoichiometric coefficients. C + yB + 6D has been considered for sequential process A + PB conditions under which species B is present in excess [59]. downstream from the A B flame. A + C D + C. Related tworeactant mechanisms also have been investigated [60]. and generally both steps occur in the same thin reactivediffusive 0 and P2 is large. A C 2C. which models a branchedchain reaction with carrier C [lo]. More recently. and to calculate flame speeds and concentration and temperature profiles. [6 1). reactivediffusivezone for A + B. B as an inert. and B1 is large in all problems of interest. Most of the work has treated both p’s as being large and both a’s as being positive. for the first and second steps ( k = 1. A brief consideration of the mechanism A + B + C may serve to illustrate the range of possibilities that occur. When a1 I to be the possibility (for sufficiently small values of 6) of a thin. there may be a range of values of P2 and 6 for which B + C occurs in a downstream region having a 0 and Pz = 0 (a case that may model convectivereactive balance). the first. [52][56]* and the competing reaction A + B. P. . A . B C. y.
many different flame structures may be encountered.5. A + C. Although solving timedependent partial differential equations numerically usually is thought to be more complicated than solving ordinary differential equations. A + B. the solutions usually converge rapidly to a description of the steadystate flame. Experience has shown that by marching forward in time. the reverse is true for the laminarflame problem with complex chemical kinetics because of the eigenvalue character of the problem. The approaches to numerical integration fall into two broad categories. then the solutions will reveal the instability. The majority of the recent investigations [67][87] employ the latter technique. the last two references are general reviews that mention flamestructure studies by numerical methods. timedependent. . [63][87]*. [88]). onedimensional * Concerning the work employing numerical methods. partial differential equations that reduce to the equations for the steady flame when the transient terms vanish. With the availability of large computers. there are examples in which this has occurred (for example. and different percentages of reactant converted to B and C [%I . the ignition procedure may be presumed to select one of the multiplicity of solutions. when they can be obtained . Flames with MultipleStep Chemistry 169 zone that precedes the exothermic reactivediffusive zone of B + C. namely. Investigations with real kinetics have employed expansions about the hot boundary for the purpose of calculating burning velocities [33] and various numerical methods of integration to obtain burning velocities and profiles of temperature and of species concentrations [30]. Standard routines for the integration of systems of parabolic equations may be employed. the timedependent approach offers many advantages. with known boundary conditions upstream and downstream from the flame and with guessed initial profiles of temperature and concentrations. the integration of ordinary differential equations that describe the steady flame and the integration of onedimensional. Thus it is seen that even for the simple example of A + B + C. with different flame temperatures. However. many relevant papers coauthored by DixonLewis. selected to approximate those of the steadily propagating flame.4. there is even a range of parameters in which two stable steadystate solutions for the flame structure exist. [43][46]. the earliest studies [63][66] and a small fraction of the more recent work [43][46] involve the former. The timedependent approach tends to establish the steadily propagating flame in the same way that nature does. it should be emphasized that the extensive citation of literature given here is not complete and omits. in particular. For the competing reaction. if the flame is unstable to onedimensional disturbances. In principle. Foremost among these are the inherently greater accuracies of the solutions. different flame speeds. numerical integration of the ordinary differential equations also possesses advantages.
170 Theory of Laminar Flames programs achieve finer intervals in space than twodimensional programs. using a formulation like that in equations (80) and (81). thus the numerical solutions tend to move away from the correct integral curve whether the integration is performed in the direction of increasing or decreasing z. From this discussion it should be evident that further research on the numerical integration of the laminarflame equations seems warranted. Since these are too numerous to be discussed here. later studies adopted instead a variable related to 5. there may be merit in trying to integrate first from the cold boundary with an ignitiontemperature approximation. Burningvelocity calculations It has been seen from the viewpoint of asymptotic analysis that when a onestep approximation is applicable for the chemical kinetics. there are onedimensional methods involving collocation that are better classified as twodimensional methods. this can be a significant benefit if different reactions are of importance in different narrow zones of the flame. with complex chemistry. [44]. In all these investigations. the advantage would be thatirrespective of the complexity of the kineticsonly one parameter. a procedure that achieves simplification with onestep chemistry and often yields good approximations to the flame speed at early stages in the computation. A successful technique of this type would enable a pseudostationary value of the burning velocity to be identified and the corresponding temperature and concentration profiles to be calculated with good accuracy. the burning * In this respect. Many important conclusions concerning chemical kinetics in specific flames have been obtained in the references cited (for example. and criteria similar to those previously developed for identifying divergent solutions might be applicable for locating the correct integral curve. In addition. However. would be available for adjustment. these integrations generally exhibit saddlelike divergences as z is decreased as a consequence of the varying kinetics [44]. [63][85]) and in related work. In view of these difficulties. Criteria therefore must be developed for modifying parameters in a manner designed to overcome these divergences [44]. the burning rate. the reader is referred to the references. . Successful integrations of the ordinary differential equations have been obtained for relatively few flames. the ordinary differential equations can provide multiple steadystate solutions when they exist (a relatively difficult task for timedependent methods) and unstable solutions as well.4.1.* In principle. the integration was started first from the hot boundary. Thus both classes of the numerical approaches have attractive attributes. Only the earliest work [43].4. using a modern routine for “stiff’ equations. which could aid in the understanding of flame structures. 5. [63][66] employed z as the independent variable.
0 >  j = l .T . ~i = j and The problem in equation (83) is wellposed and solvable by matrix methods.. a. E ~ . This conclusion remains true for multiplestep kinetics if the sequence of reactions can be reduced to an effective onestep process through introduction of a suitable combination of steadystate and partialequilibrium approximations. . and the derivatives d X i / d z at z = 1 are readily computed from equation (83). = ti. If D i j may be assumed to have the same temperature dependence for each pair of species.4./W. KO= (Cj”= cj. . A progress variable t for the effective onestep process may be defined.5. . i = 1. with all eigenvalues being negative. w0/W [in which average molecular weight]. as described in Section B. h( T ) .5. the flux fractions t i remain equal to their ~ .o). .2. Flames with MultipleStep Chemistry 171 velocity is determined by matching the solution in a downstream reactivediffusive zone at the hot boundary to the inert solution in the upstream convectivediffusive zone. Then . ) / P D ~ ~ one . may derive a linear system with constant coefficients from equation (81): d ( X i . . when the generally weak dependence of 1 on cominitial values.O)/d€J= Xi = j= 1 c CiJ(Xj  N >  xj. N . and by defining Leij. then by writing D i j = D i j .Throughout the convectivediffusivezone. and an equation of the form dt/dz = Ao(z) may be derived from equation (SO).. These derivatives provide linear relationships between X i and z in the reaction zone that enable the rates wi there to be expressed explicitly in terms of z. . at 0 = 0. where A is inversely proportional to m2 and o(z) is known.Xi. .j + i 5 x ~ Leij. . . ~ . o Leij. where D i . N.2. equation (81) (or the generalization thereof that eliminates assumption 7) reduces to a system of linear ordinary differential equations for X i ( z ) that may be solved subject to the known final equilibrium values X i ..i = 1.o = 1. at z = 1. and position is neglected. which changes from 0 to 1 across the reaction zone.)i#j is the initial [Xi.J where X i . o g ( T )and 1=1 .(T. . and A0 are constants and the functions g and h are nondimensional.
In addition to giving the burning rate. These and other unique characteristics of individual flames may motivate future theoretical studies. threebody recombination processes may be sufficiently slow to occur in a downstream convectivereactive zone that does not influence the flame speed. This may occur under appropriate conditions for bromine molecules in hydrogenoxygen flames to which HBr has been added. paralleling that of Section 5. Particular species may be produced and consumed in relatively narrow upstream reaction zones in such a manner that they exert a minimal effect on the burning velocity and can be ignored at first and then calculated later in an analysis specifically addressing their reaction zone. and the upstream structure and propagation velocity may be calculated first by neglecting these processes . The function o(z) may be sufficiently complicated to necessitate a numerical evaluation of the integral for obtaining A.172 Theory of Laminar Flames provides the first approximation to the burningrate eigenvalue after a suitable expansion for o(z). The simplifications that have just been indicated to follow from the application of this approximation underscore the importance of having methods for ascertaining the validity of the approximation.2. There may be a single reaction zone with a reactivediffusive character at the hot boundary.2 is applied to nonisothermal systems involving molecular transport. This procedure fails if an insufficient number of justifiable steadystate and partialequilibrium approximations is available. For example.6. This situation appears to prevail for the ozone decomposition flame under many conditions. then the recombination region may be analyzed afterward. The discussion .3.5. Criteria for the applicability of the extended steadystate approximation have been developed by Giddings and Hirschfelder [64] and improved by Millan and Da Riva [89]. it is sometimes referred to as the extended steadystate approximation. Suitable knowledge of the kinetics may still enable asymptotic methods to be employed for calculating burning velocities and some structural aspects.4. but within which more than one independent reaction must be considered because of inapplicability of steadystate types of approximations. This situation often is encountered in real flames and is largely responsible for their individual structural features. this procedure may be extended to provide the concentration and temperature profiles from the solution to equation (83) and the integral of equation (13). 5. The extended steadystate approximation When the steadystate approximation of Section B. has been introduced. This necessitates development of special analyses for the structure of the reactivediffusive zone. even if the flame speed is not controlled by conditions in the hottest part of the flame.2. In the rest of this chapter we shall be concerned primarily with methods for testing the validity of the steadystate approximation for chain carriers.
then equation (81) reduces to dXrldz = (IR'T/cppWDr)[Xr . equation (81) may be simplified for species r. the net mass rate of production of any reaction intermediary r is negligibly small. Factors that may contribute to inapplicability of the steadystate approximation in flames [89]. relations such as equation (85) permit explicit representation of X . . The flame equations may then be solved explicitly to give all the mole fractions. Since the production terms w. A statement of the extended steadystate approximation is that throughout the flame. (85) The integral of equation (80) for i = r is then t r = 0 because the initial (as well as final) chaincarrier concentration is zero. The discussion and results are applicable qualitatively for a given chain carrier in flames containing any number of chain carriers. 6 1. and the flux fractions of all of these species are zero. [90] are (1) too short a residence time in the flame for the chaincarrier concentration to reach its steadystate value and (2) the diffusion of chain carriers away from regions of maximum chaincarrier concentration. and the problem is reduced to that of a onestep reaction. (86) where the diffusion coefficient for species Y in the multicomponent mixture (D. Since stoichiometry conditions relate the remaining ti. are functions of z and of the mole fractions X i . . (87) . It can be shown [9l] that when X . consideration will be restricted to systems in which only one intermediary exists.1). . .3. this will be denoted by the subscript r.5.(W/W)trl/f. 5. . Conservation equations for reaction intermediaries For the sake of simplicity. Since reaction intermediaries are present in low concentrations. equation (80) is dcrldz = (Wm2cp)(wr/f). in terms of z and the remaining Xi. Flames with MultipleStep Chemistry 173 here largely follows [89].) has been defined by N. in terms of z.4.4. Equation (86) may be taken as qualitatively true in flames even though the diffusion velocities of major species differ. and the other species will be denoted by the subscriptsjo = 1.only one independent expression remains in equation (80). For species r. if the diffusion velocities are the same for all species other than r. wr = 0. including the X .1 l/Dr j= 1 C (XjIDrj). Thus if equation (85) is valid for all chain carriers. N . the mole fractions of all these reaction intermediaries may be eliminated from the flame equations.
in which E .* 5. is of the form W./W) and then differentiating the resulting equation and substituting for dE. (90) R = Lb/m2cp (9 1) is a dimensionless function of T and the X j ' s excluding X.X.. and reaction for the chain carriers. convection. Then w. Since the steadystate approximation (w. = b(a .1 species other than r because X . (89) where a and b may depend on z and all X j except X. = L R 0 T / c p p W D . The result.. produces the primary influence of diffusion upon the radical concentration profile.  which may depend on the composition (excluding X ./dz from equation (87).). < 1) and T.4. Substituting equation (89) into equation (88) yields qx. does not appear. < 1 implies that the term corresponding t o j = Y will be small. = L/pD. These same three physical effects must appear irrespective of the formulation and would also arise in testing criteria for partial equilibria. ~ It is reasonable to define the Lewis number for the radical r as Le. = 0) implies that x. for j # r. This term. A useful form for equations (86) and (87) may then be obtained by multiplying equation (86) by (f/Le.)( W. A criterion for the applicability of the extended steadystate approximation For illustrative purposes let us assume that chain breaking occurs through a process that is of the first order with respect to species r.174 Theory of Laminar Flames The sum in the quantity f [equation (82)] appearing in the denominators of equations (86) and (87) now extends only over the N . is a study of which will yield a criterion for the applicability of the extended steadystate approximation.). since X . . which goes to zero as D.cp. The three terms in equation (88) represent diffusion.za (92) * It will be noted that the diffusion coefficient of the radical affects only the first term of the operator 9in equation (88). Hence f depends only on T and c .) = R(a in which  X.4.+ 0.
. 5. and [from equation (89)].4. one approach to solving equation (88) for small deviations from the steady state is to assume that X r = C Xr.. is a characteristic flame thickness [see equation (4)]. .4.n/K”. It follows that 6/v = t. according to the discussion in Section 5.. Exactly how large R must be is.. is a characteristic residence time in the flame. = b(aX. hence a criterion for the applicability of the steadystate approximation is that R be large.5. n=O m (96) where 0 is a constant representative of the magnitude of R. (93) Equation (93) will be satisfied if R is sufficiently large. we expect that accurate predictions of chaincarrier distributions will require a larger R than will accurate predictions of burning velocities. Substituri:ig equations (96) and (97) into equation (90) and collecting terms . = b(a . p / b = t.‘). 9 tch. and other forms for w..1. Methods of analysis for testing steadystate approximations Since the steadystate approximation applies if R is sufficiently large.. is a characteristic chemical time for the destruction of chain carriers. also lead essentially to equation (93). (94) where 6 = A/mc. (97) where b‘ I 1 and b‘ expresses the variation of R through the flame. The physical significance of the criterion in equation (93) may be seen by noting that equation (91) implies that 0 = (6/V)/(P/b). The value of 0 may be chosen in such a way that R 5 rn’.X. equation (90) shows that this approximation will be valid if I g ( X r >I/Q 4 Xr . The result given in equation (95) is easily shown to be independent of the special assumption introduced with regard to the order of the reaction causing removal of the chain carriers.4. [93] in an entirely different context and is referred to as Damkiihler’s first similarity group. Flames with MultipleStep Chemistry 175 from equation (89). such as w. Hence R = tres/tch. not determined by these approximate considerations.5. (95) and the steadystate approximation will be valid if t.X#?)and w. of course. The time ratio in equation (95) was first introduced by Damkohler [92].
If the intermediary under consideration is not a chain carrier but is merely produced and consumed through unimportant side reactions. For very small deviations from the steady state. n l)/b’. and b’(z) and 9 ( a ) are evaluated. . Special situations exist for which this procedure simplifies considerably. treating different zones differently. = 0 in the flame equations. Thus the flame equations are first solved with X .l(z)/a. The approach that has been described here is an example of a perturbation method for large Damkohler numbers and may be termed Damkzhlernumber asymptotics. an approach based on matched asymptotic expansions. causing As the hot boundary is approached ( 9 ( X . and in the solution procedure described above 9 and b’ need not be recomputed (through the flame equations) in each step because they remain unchanged. It is possible that the Damkohlernumber expansion will often be good in the hot reaction zone but poor elsewhere. )to approach zero [see equation (88)]. Since equation (90) then implies that X r . 2. X j ) + Xr. profile) can therefore be determined completely by setting X .o = a for the steadystate distribution and X r . Under these circumstances. it is often reasonable to omit the recomputation of 9 and b‘ in successive steps even for chain carriers.(z) is then computed from equation (99) and the flame equations are again solved with X .. equation (90) reduces to a linear nonhomogeneous differential equation with known variable coefficients. therefore. may be helpful. and the coefficients of the linear differential operator 9 ( X .. The structure of the flame (excluding the X . On the other hand. near the cold boundary b‘ is small and. . X. This process is continued until sufficient convergence is obtained. . z + l). the operator 9 is computed. napproaches zero at the hot boundary for n 2 1. b‘. while radical distributions away from the hot reaction zone have relatively little influence on the main characteristics of the flame. n = 1. X. . It has been developed on the basis of an expansion that does not distinguish among special zones within the flame. = a(z. the series given in equation (96) should converge rapidly as the adiabatic flame temperature is approached.176 Theory of Laminar Flames involving the same powers of gives Xr. a. = a(z. After this structure is determined. then the burning velocity and the composition profiles of all other species in the flame are virtually unaffected by the presence of this intermediary.). ) are known functions of z. n= 9 ( X r . Sharper definitions of values of consistent with the steadystate approximation (in the zone where it is applied) might thereby be developed. f goes to zero. the series tends to converge slowly upstream [see equation (99)]. (99) for small deviations from the steady state. . Therefore.
0. In this manner.6. analytical approaches have been less successful. the validity of simplifying approximations can vary strongly with the initial pressure. + + .(z)/Q with a(z. 0 + 2 0 . In addition. it appears that the steadystate approximation for oxygen atoms (with the mechanism 0. An alternative approach to the estimation of minimum acceptable values of is to introduce simplified functionsf(z). Better rateconstant data are needed to aid in the application of the methods discussed herein to specific flames. M + 0. + 0 + M. Numerical integrations have been applied successfully to the hydrogenoxygen flame. ) is reasonably accurate at sufficiently low initial concentrations of ozone (between 20% and 30% by volume. at least for the last two of these chain carriers [42]. The primary reason for the differences is uncertainty in values of reactionrate parameters.4. Key specific reactionrate constants sometimes are uncertain by an order of magnitude at representative flame temperatures.4. and W.(z). Observations on theories of flame structure It would be of interest to employ results like those in the preceding section to ascertain the applicability of the steadystate approximation in specific flames. and composition of the reactant mixture. This has been done by different investigators.5. Because of the complexity of the chemical kinetics. a(z). the former must be sufficiently small. For example./W that enable equation (88) to be solved analytically [89]. OH. the validity of the steadystate approximation for bromine atoms in this flame is less clear and is likely to be significantly dependent on initial conditions. often with conflicting conclusions. For the hydrogenbromine flame. Flames with MultipleStep Chemistry 177 On the basis of the approach defined here. Le. X j ) . Few flames have rate parameters known as accurately as those for the hydrogenoxygen flame. a a a a 5. For the ozone decomposition flame in an ozoneoxygen mixture initially at room temperature and atmospheric pressure.. 2 100 has been obtained as an approximate criterion [89]. Comparison of the with those for = c c then provides an solutions for finite values of indication of how small can be if the steady state is to be reasonable. b’(z). temperature. for example) but inaccurate at high ozone concentrations (above 30%). these conditions must be specified in stating whether the steadystate assumption is applicable. Therefore. This flame affords a good testing ground for theoretical methods of prediction. there appears to be a wide range of conditions under which the steadystate approximation for hydrogen atoms is excellent. and H leads to reasonable agreement between calculated and measured burning velocities. even though estimates indicate that the steady state is inapplicable.. minimum values of consistent with an acceptable steadystate approximation may be estimated by comparing X. there are conditions under which introduction of the steadystate approximation for the intermediaries 0.
asymptotic analysis may be restricted less to model kinetics and applied more to real kinetics. So many elementary steps are involved in soot production in flames that accurate calculations of soot concentrations are difficult whether numerical or analytical methods are employed. Activationenergy asymptotics currently comprise the most promising analytical approaches for studying the hydrogenoxygen flame and other flames. Measured burning velocities are readily correlated by expressions like equation (78).2. A single primary reactivediffusive zone with a rate that can be approximated as a onestep process may control the flame speed for typical hydrocarbonair flames. For the hydrogenoxygen system. Aside from the fact that successful analytical methods provide formulas for the burning velocity and for temperature and concentration profiles. fundamentally justified simplifications applicable for these more complex fuels is a continuing. in spite of the availability of numerical methods. In general. it appears that flamestructure simplifications appropriate to activationenergy asymptotics may vary appreciably with initial conditions. such as combinations of reaction steps to form different overall effective reactions in different parts of the flame. simplified overall kinetic expressions for soot processes appear to be needed. Often this a posteriori calculation can be simplified by use of activationenergy asymptotics. and their production rates may be calculated after the rest of the flame structure has been obtained. However. such as hydrocarbonair flames. the overall rates may be modified in such a way that fewer variations in flame structure occur as initial conditions are varied. This is especially true for the production of oxides of nitrogen by the Zel’dovich mechanism (Section B. recent numerical integrations for methaneair flames.178 Theory of Laminar Flames There is motivation to pursue analytical methods based on asymptotic analysis for the hydrogenoxygen flame. although the hydrogenoxygen chain is involved in the kinetics of hydrocarbon combustion. .5.5) because of the strong temperature dependence of the rate. they may be ignored at first. There are important chemical processes involving species present in low concentrations that exert little or no influence on the flame speed and on other aspects of the flame structure. for methanolair flames. and for other flames with full kinetics (to the extent known at present) show numerous species participating in many reactions [86]. worthwhile topic of research. asymptotic methods may reveal interesting intricacies of the flame structure. it may be anticipated that in the future. Notable among these are the production of oxides of nitrogen in fuelair combustion and the production of solid carbonaceous materials (soot) in fuelrich hydrocarbon combustion. It is possible that. The complexities of the hydrogenoxygen flame underscore uncertainties associated with more complex systems. To the extent that these trace species do not influence the flame propagation. there may be many different hydrogenoxygen flames. that may be hidden by purely numerical results. Identification of useful.
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When the air is preheated to a sufficiently high temperature and fuel (usually hydrogen) is added.1. then after traveling a distance on the order of ten tube diameters. We shall 182 . and a highspeed (about 3 x lo5 cm/s) nearly planar combustion wave often emerges and travels at a constant velocity through the remainder of the combustible mixture to the end of the tube. An unsteady transitional region develops. If the open tube containing the combustible gas mixture is sufficiently long. then the shock wave ignites the mixture.CHAPTER 6 Detonation Phenomena Let us reconsider the experiment described at the beginning of Section 5. the deflagration wave begins to accelerate markedly. plane) strong detonation. This highspeed wave is a detonation. these are strong detonations that propagate faster than the ChapmanJouguet velocity and that decay slowly toward the ChapmanJouguet condition. The rate of development of the detonation can be enhanced by closing the ends of the tube. and the ensuing combustion has been observed to transform the shock into a (steady. Standing detonations (stationary in the laboratory) may be produced by adjusting air flow conditions in a convergingdiverging nozzle so that a Machreflected normal shock sits downstream from the nozzle exit. which is invariably found to propagate at a speed correspondingly closely to the upper ChapmanJouguet point (Chapter 2).1. if the pressure ratio across the shock wave is very large. Detonations can also be initiated by passing a sufficiently strong shock wave through a combustible mixture in a shock tube.
6.1. Significant strides toward improved understanding of detonation structure began in the late 1950s with the gradual recognition of the prevalence of unsteady.4. von Neumann [6].2. initially we shall consider the onestep firstorder reaction R + P in a binary mixture with a Lewis number of unity and an effective Prandtl number o f t . that is. cp) and F. The two differential equations describing the wave structure in such a system were derived in Section 5. we shall begin by adopting assumptions 110 of Section 5. z = 0. Hypotheses leading to mathematical predictions of the speed of propagation of these waves were given by Chapman [3] and Jouguet [4]. Background material and references to the large body of literature on detonations that existed prior to 1960 may be found in books [S][13] and in reviews [14]. Detonations in media that are not purely gaseous will be discussed in Section 6. PLANAR DETONATION STRUCTURE 6. Since the material on detonations is too extensive to be developed fully here.1.2. 6.a) normalized dimensionless stagnation temperature [equation (512)]. nonplanar wave patterns. It will be recalled that cp is the ratio of the velocity [equation (526)].1. Detonations were first investigated scientifically by Berthelot and Vieille [l] and by Mallard and le Chatelier [2]. cp) are defined in equations (532) and (534).6. and Doring [7]. Planar Detonation Structure 183 consider the structures and propagation velocities of detonations produced by the methods described above. and t is the reaction progress variable [equation (517)]. Properties of the governing equations The solution to equations (535) and (536) is a line in the threedimensional (cp.3.1. the reader is directed to the literature cited above for further details. the wealth of information that has been obtained more recently is covered in reviews [16][22] and in newer books [23][28]. and reasonable postulates for the wave structure were presented by Zel’dovich [S]. nonplanar phenomena can properly be begun and is most easily illustrated by analyzing the simplest representative system. The status of the mathematical problem is summarized in Section 5. beginning at the singular point cp = 1.7. In the following section we shall discuss the structure of steady.2. [l5].2 and are given by equations (535) and (536). z is the local velocity to the upstream (x = . z. Factors influencing detonation propagation velocities are considered in Section 6. Important unsteady and nonplanar aspects of detonation phenomena are treated in Section 6. planar detonation wave must be understood before investigations of unsteady. in which FJz. Governing equations The structure of a steady.1. respectively. onedimensional. gaseous detonations.2.(z. t) space. . plane. Therefore.
The denominator for equation (535) and equation (536) vanishes when t = 7. the singularities will be located at the points or lines where both the numerator and the denominator vanish.1.1. z = 1. The numerator of equation (535) vanishes when and the numerator of equation (536) vanishes when .184 Detonation Phenomena T FIGURE 6. In this plane. and to sketch integral curves between the singularities using the slopes given by equations (535) and (536). and diffusion vanishes [see Section 5.2. Location of Singularities Since the numerator and the denominator on the righthand side of equation (535) or equation (536) are bounded in the region of interest. T .1. (1) which defines a slanting plane containing the cp axis in Figure 6.1. equation (519)]. 6. for example. it is necessary to locate the singularities of equations (535) and (536) in the region of interest. heat conduction precisely balances viscous dissipation. Physically acceptable solutions must lie entirely within a region shaped like the interior of a semiinfinite beam of unit square cross section. to determine the behavior of the solutions in the neighborhoods of these singularities. Schematic illustration of the (cp. as illustrated in Figure 6. t) region in which the solution for the t = 0 and ending at the singular point cp = cpm.2.1. t = 1. In order to deduce the general shape of the solution curve. structure of a combustion wave must lie.
along this line. which is the only condition with any degree of complexity]. are illustrated in Figure 6. since y generally lies within a very narrow range of values.2 for the curves labeled M . = 0. Since the only tdependent condition above is t = 7.2. z) plane defined by equation (6) is the Rayleigh line [along which equation (22) relates the properties at every point].. heat conduction. Hence the line in the (cp. (4).2. t) space on the (cp. S ) plane. and mainly on M. in which a’z is sketched as a function of cp for various values of M . From equation (534) it is clear that the solution to equation (3) in the region of interest is the plane 5 = 1. because in equation (6) the relationship between this product and cp depends only on y and M . z. the viscous force term in equation (55) is zero. = 5 and M . z. the generatrices of which are parallel to the E axis. Planar Detonation Structure 185 Since equations (2) and (3) are independent of E .2. we find that this parabola is given by or [solving equation (6) for cp] by where the notation implies that cp+(z) 2 cp(z). Equations (l). (4) In view of the discussion in Section 5.3.1. and ( 5 ) imply that the lines t = z = 1 and E = z = 0 may be taken to be the singular lines of importance for equation (536). z) plane. The product a‘z was chosen as the vertical coordinate in Figure 6. equation ( 2 ) ] is valid. their solutions will define cylindrical surfaces. we may also want to treat the plane as a solution to equation (3) in order to remedy the coldboundary difficulty. and diffusion vanish. viscous effects. applicable to all of these curves and easily deduced from equations (6) and (7). Solving for z. E ) space] given by equation (6) with the plane given by equation (1) is the singular line of equation (535). The intersection of the parabolic surface [in (cp. Equation (532) shows that equation (2) defines a parabola in the (cp. From equation (531) it can be seen by recalling the meaning of the variables that when equation (6) [that is.6. as given by the Rayleighline condition [that is. .it will be convenient to view the location of the singularities in a projection of the (cp. Pertinent facts. The construction of such a projection is aided by Figure 6.1. by equation (6).
d correspond to strong and weak detonations and weak and strong deflagrations. 1). (cp. c. equation (9) represents the coldboundary point. O)]. 4 = (q(1). for M . 2. 11. T. Schematic diagram illustrating the properties of various Rayleigh lines. The most important singular points are those common to both equations (535) and (536). < l).namely.186 Detonation Phenomena Detonations / \ M. By using equation (7) and the results of Section 2. it can be seen that equation (10) is the hotboundary point for a weak detonation or a strong deflagration and equation (11) is the hotboundary point about T = 0.2. 6 ) = ( L O . respectively. 4 = (cp+U). = . equation (8) identifies the coldboundary point [(cp. while for a deflagration (that is. (1 1) Equation (7) shows that for a detonation (that is. T .1.5). > l). Figure 2.Deflagrations FIGURE 6. b.2 (for example. (10) and (Cp. cp = ~ ~ (then 0 )yields the equidimensional equation . for M . End states at points a. 1.
however. t = 1) from ( T I 1. q) = 0 over a short range of T in order to remedy the coldboundary difficulty (see Section 53. cp = ~ ~ (then where a = 0 for cpLt(0) = 1 (the cold boundary) and a = 1 for cp. Equation (12) shows that the nature of the singularity depends quantitatively but not qualitatively on the value of cp.2.t) plane. and therefore cp+(l) = q(l).6. equation (234) [in which CI = a'y/(y . t = 0) [equations (8) and (9)]. all others bend away from the singularities. E I I) is which implies that T > t along this curve. these singularities are found to be saddle points in the (7. Hence equation (536) implies that t = 0 as T increases in the neighborhood of either of these points (that is. Expanding equation (535) 0 )yields the equidimensional equation about T = 0. t = 1) [equations (10) and (1 l)] can be deduced by expanding equation (536) about these points.(O) # 1 (the other singularity at T = 0). we must assume that F.2. For ChapmanJouguet waves. 6. causing equations (10) and (11) to coalesce into a single point. for any reasonable reaction order. t I 1). In the neighborhood of ( T = 0 . only one integral curve reaches (z = 1. In this manner.l)] implies that the quantity under the radical sign in equation (7) vanishes at T = 1.1. The qualitative properties of the singularity do depend on our choice of a firstorder reaction. The nature of the singularities (T = 1. For equations (8) and (9) we may assume (in view of the preceding discussion) that 6 = 0. T > t here). Let us next investigate the relationship between T and cp near the points defined by equations (8)(11). The slope of the curve that reaches ( T = 1. The general solution to equation (13) is . Planar Detonation Structure I87 for a strong detonation or a weak deflagration. Solutions in the neighborhoods of singular points Let us first consider the relationship between t and z near the points defined by equations (8)(11).(z.1. only one solution reaches the singularity from the permissible region and this solution has T > t near the singularity.2). t = 1) from the permissible region (T I 1 .
the precise properties of the solutions differ for various ranges of values of the parameters (that is.l)”(Mi .3. z) plane.l)”(Mi . 6. M. z) plane.depending on the type of wave. z = 01 is a saddle point and [cp = cp+(O) = 1. Figure 6. Analysis of the integral curves in the (cp. z) plane.1) > 0. z = 11 [equations (10) and (1 l)] have been considered in detail by Hirschfelder and Curtiss [29]. z) plane. for all realistic reactions.) and depend on the order of the reaction. but c = 0 when ( .1) > 0. These results enable us to use equation (535) and the previously deduced properties of the singularities in the (cp. The singularities [cp = cp+(l). z = 11 (the end state for strong detonations or weak deflagrations) always exhibits a nodal type of behavior in the (cp. z = 11 (the end state for weak detonations or strong deflagrations) always exhibits a saddle type of behavior in the (cp. z) plane for deflagrations and a nodal point in the (cp. z) plane in the neighborhoods of these points is somewhat more complicated than analysis for the other singularities . c = 0).3. pass through the singularity when (. Thus an infinite number of integral curves. we conclude that [cp = cp(O). it can be deduced from equation (13) or (14) that the singularity is a saddle point in the (z. > 1 for detonations and Mg < 1 for deflagrations.3 clearly illustrates the nodal type of behavior of solutions about cp+(O) and cp(l) and the saddle type of behavior of solutions about cp (O) and cp+( 1). the point [cp = cp+(l). The hot boundary is located at cp(l) or cp+(l).t) relationship along the solution curves is relatively simple.1.1) 5 0 [since cp must approach cp*(O) as z goes to zero]. z = 01 is a saddle point and [cp = cp+(O).2. and the point [cp = cp(l). when (. z = 11 and [cp = cp(l).l)”(Mi . in fact. z) plane for detonations. General properties of the integral curves The (t. cp) plane. as stated previously. this is the primary reason that the burning velocity is an eigenvalue for deflagrations.188 Detonation Phenomena where c is an arbitrary constant when ( .1) < 0 (that is. On the other hand.1)”(Mi . while wavestructure solutions exist with any propagation velocity (greater than or equal to the ChapmanJouguet wave speed) for detonations. The encircled signs are the signs of the slopes of the integral curves in regions bounded . equation (536) and the result that z > t in the neighborhoods of the hot and cold boundaries suggest that z > t throughout the range 0 < z < 1 and that t varies monotonically with z in this region. and such singularities are nodal points in the (cp. The cold boundary (cp = 1) is located at cp (O) for deflagrations and at cp+(O) for detonations. This projection is shown in Figure 6. z = 01 is a nodal point for detonations. z = 0) is a saddle point in the (cp. z = 01 is a nodal point for deflagrations. Thus the cold boundary (cp = 1. all integral curves (with t = 0) in the neighborhood of the singular point. Nevertheless. Since M . z) plane in order to construct the projection of the solution curves on the (cp. and that [cp = cp(O) = 1.
On the other hand. c) space. B. strong detonations exist for any propagation speed (above the upper ChapmanJouguet wave speed).3.3. z) behavior of the solution ensures that at most one integral curve from the coldboundary singularity reaches the hotboundary point in (cp. weak detonations can exist only for particular reactionrate functions at any given wave speed.. solutions to equations (535) and (536) for the structure of strong deflagrations do not exist.3 corresponds to a different value of some wave parameter (for example. that is. Similarly.6. each solution cutve shown in Figure 6. Since cp+(O) and cp(l) are both nodes. z) plane] and therefore do not satisfy the hotboundary conditions. no integral curves pass between cp(O) and cp+(l)in Figure 6.3. ) . that is. z = 11do so with E # 1 [and hence with infinite slope in the (cp. that is. Planar Detonation Structure 189 i Rayleigh line FIGURE 6. Thus. by z = 0.1. only one integral curve (the curve labeled f ) passes between cp+(O) and cp+(l)in Figure 6. and so on) the ( E . z = 1. It is interesting that consideration of the basic (elliptic versus hyperbolic) character of the external . that is. Schematic diagram of the projection of solution curves of (535) and (536) on the (cp. It should be emphasized that for given parameters ( M o . these signs depend only on the result that z > E for 0 < z < 1 and the assumption (adopted for clarity) that z < E for z > 1 and z < 0.E l . Hence. acceptable solutions passing between these two points will exist for a range of values of the wave parameters. z. an infinite number of integral curves connect these two points in Figure 6.(l). and the Rayleigh line. only one integral curve (the curve labeled b) passes between cp(O) and cp( 1). Finally. weak deflagrations propagate with a definite wave speed that depends on the reaction rate. the reactionrate frequency factor B .3. 7 ) plane. regardless of the reaction rate. all other integral curves from the cold boundary that pass through [cp = cp.
Since equations (533) and (534) imply that dt/d< > 0. Searches for strong deflagrations in combustion could focus on systems with both extraordinarily high burning velocities and endothermic attributes near the hot boundary. 6. Currently it is unclear whether fundamental reactionrate limitations will preclude the occurrence of strong deflagrations in combustion. z) plane of the integral curve on the Rayleigh line is infinite (unless E = z) and the slope in the region to the left of the Rayleigh line is positive (unless t 2 z) the integral curve cannot reach the Rayleigh line unless E becomes equal to z at some point in the region 0 < z < 1. We may therefore conclude that solutions to equations (535) and (536) cannot satisfy the boundary conditions for strong deflagrations.3. and so on. Remarks on deflagrations A more detailed demonstration that strong deflagrations do not exist can be given. For ordinary deflagration waves. Solutions for structures of strong deflagrations may be obtained if an endothermic process follows the exothermic reaction [3 13. all known deflagrations in the laboratory are weak deflagrations. a Lewis number of unity. while the 5: derivative of equation (519) shows that d 2 z / d t 2 = dc/d<. a Prandtl number of 2. t = 11 of a strong deflagration. we have shown only that strong deflagrations are impossible in binary systems with a firstorder reaction. Once t exceeds z.1. leads to roughly the opposite variation in the number of free parameters [30] . the results pertain to different questions and are not in conflict. M .3. the integral curve must cross the Rayleigh line at some point between z = 0 and z = 1 in order to reach the hotboundary point [cp = cp+(l). Since the above argument relies on the assumptions used to derive equations (535) and (536). Since the slope in the (cp. equation (536) shows that z continues to decrease as t (or 5 ) increases. with the wave treated as a discontinuity. with M o < 1. Since the result depends on the structure of the wave. it is impossible to invent a generally valid proof. Hence z will not approach the required hotboundary condition z = 1 at E = 1. However. z) plane which exceeds that of the Rayleigh line. Equation (14) shows that the initial . the result has been found to be true.2). and therefore z becomes less than E.190 Detonation Phenomena flow. t = 0) with z > E and with a slope in the (cp.z = 1. Hence. These solutions have been proposed for astrophysical problems of stellar and galactic winds involving ionizationrecombination fronts [32]. At t = z. is very small compared with unity and the Rayleigh line is very nearly a straight line with slope d(cr’z)/dcp = 1 in the range 0 I z I 1 (see Figure 6. it follows that z begins to decrease as 4 (or E ) increases. the solution curve leaves the cold boundary (cp = 1. as is illustrated at cp(O) in Figure 6. for all combustion systems that have been studied. equation (519) shows that dz/d< = 0. From equations (7) and (14) it is easily shown that. z = 0.
(z. no reaction occurs along this curve. € =z (16) throughout the detonation wave. = u/u. approximately. while deflagrations propagate at low subsonic velocities.3. 6. Equations (16) and (524) show that.1. is sufficiently small. the upstream portion of the detonation structure will lie very near the line T = 0 connecting the points cp+(O) and cp(O) in Figure 6. the temperature must become relatively large in the detonation wave before T begins to change appreciably from its value (T = 0) at the cold boundary. In terms of dimensional variables. Equations (16) and (533) lead to d W = FAT. Planar Detonation Structure 191 slope of the integral curve at the cold boundary approaches this same value as M .3. An estimate of the order of magnitude of the lefthand side of equation (519) then shows that dz/d< 4 1 (since the change in T through the wave is AT = l).. is much smaller for detonations. cp). that is. cp) 5 41 (15) in a detonation wave.cp).6. This result has a number of important implications concerning detonation structure. approximately. this condition implies that T/T. typically F. cp) 5 10 in a deflagration wave and F.1. Since the change in t through the detonation wave is A€ = 1.(T.3.1) of an isobaric wave. t = Y in the wave. and the detonation structure will be represented by a curve similar to the one labeled c in Figure 6. Hence. Approximate solution for the structure of a detonation Since detonations propagate at supersonic velocities. defined in equation (534). and the structure of the upstream part of the wave is obtained by integrating . Since the (cp. Since 6 = T = 0 along curve a. the solution itself must have d(cc'z)/dcp = 1 everywhere when M . diffusion is negligible. equations (15) and (533) imply that a representative dimensionless distance scale A< is large compared with unity for detonations (it is of the order of unity for deflagrations). which is equivalent to the assumption (introduced in Section 5. equations (531) and (17) determine the approximate structure of the detonation.3.4. and therefore equation (519) implies that. the mass flow rate m is much larger for detonations than for deflagrations. the dimensionless reactionrate function F. In view of equations (534) and (15). T ) projection of the solution curve lies between the Rayleigh line and the straight line through the cold boundary with this initial slope. Consequently. + 0.(z. (17) which serves to eliminate t from the problem. The solution curve c is closely approximated by curve a followed by curve b in Figure 6.
Since equation (527) shows that the temperature T depends on both cp and z and equation (7) shows that cp(z) is a fairly complicated function. and the structure of the downstream part of the wave is obtained by integrating equation (17) with cp = cp(z).z)} = constant. Hence. (20) where t2is a constant and the dimensionless specific reactionrate constant at 5 = cc is F E lim {t'.F (C52). Since the characteristic distance over which properties change appreciably is A5 % 1. Since curve c lies close to curve a followed by curve b. The relationship between cp and z along curve b is therefore given approximately by F. we concluded that these two curves afford a good approximation to the structure of most planar detonations. cp) = 0.5.4 (the labels a through fidentify corresponding curves in Figures 6.3 represents the most reasonable structure. equation (20) is the solution to equation (17) throughout the downstream portion of the wave. the integral in equation (19) must generally be evaluated numerically. cp(z)]/(1 r+ 1 . For the highly unrealistic case in which the activation energy is zero (El = 0) and the pressure and temperature dependences of A and B1are such that the factor in brackets in equation (534) is a constant. The relationship between pressure and volume along this curve is illustrated in Figure 6. cc) is * = 1 . Discussion of detonation structure We have inferred that for planar detonations. the solution to which is cp = cp(z).. equation (19) shows that the asymptotic 5 dependence of z (as 5 .192 Detonation Phenomena equation (531) with z = 0 between cp+(O) and cp(O). . The integration can be performed analytically. namely. where cp(z) is given by equation (7). curve b lies very close to the Rayleigh line.[z. the result is where t1is an arbitrary constant.3 and 6.(z. along curve b (the downstream part of the wave) the term dq/d< may be neglected in equation (531). Since .1. However. 6.4). curve c in Figure 6.
von Neumann [6]. The ab (shockdeflagration) structure of detonations was first proposed by Zel’dovich [ S ] .  l/p no heat release occurs along curve a.6. Planar Detonation Structure 193 Shock Hugoniot (Hugoniot curve for zero heat release) Hugoniot curve von Neurnann spike Final state for strong detonation a Rayleigh line P I Initial state’ ( j I I I \\ 1/PO FIGURE 6. the shock wave heats the reactants to a temperature at which they can react at a rate that is high enough for the ensuing deflagration to propagate as fast as the shock. It is likely to apply to sufficiently strong detonations (overdrivenwaves. Hence a good approximation to the usual detonation structure is a shock wave followed by a deflagration.4).2).2.6 and 6. Curve b represents the structure of a deflagration with upstream conditions given by the point q ( 0 ) (which is called the von Neumann spike in Figure 6. for the most commonChapmanJouguet wavesmore recent studies. which require special consideration (see Section 6. This is quite reasonable on physical grounds.see Sections 6. The structure of a highspeed “deflagration” of this type necessarily differs greatly from the deflagration structure discussed in Chapter 5.1. [33]) and of good experimental measurements performed mainly in the 1950s (for example. However. it was widely believed that the ZND structure was representative of most real detonations.3. . see review in [38]). This structure excludes weak detonations. this curve represents the structure of a normal shock wave in the reactant gas.4. and Doring [7] and may be referred to as the ZND wave structure. Schematic illustration of detonation structure in a pressurevolume plane. [34][37]. On the basis of numerical calculations of steady.2.3). planar detonation structure (for example.
6. [38]).1. where a. the intermolecular collision rate) before an appreciable amount of heat release could occur in the shock wave. these detonations generally possess a complex threedimensional substructure involving transverse waves that produce a steady. is of the same order of magnitude as molecular velocities. Therefore. further deductions on the basis of the ZND structure deserve to be pursued here. as given by equation (18).a0 M . The result that Ax is of the order of a few mean free paths in the shock wave casts doubt upon the validity of our continuum equations for the upstream portion of a detonation. The dimensionless distance over which cp changes appreciably in the shock wave. the chemical reaction rate would have to approach the maximum conceivable reaction rate (that is. [22][25].    6.3 and 6. the shock waves that occur in detonations are strong enough to be treated as discontinuities for nearly all purposes. for example. established that this structure usually is unstable and that. It appears probable that such highly reactive mixtures usually would explode in a more or less homogeneous manner instead of supporting a propagating detonation wave. is A< yMg/ ( M : . The structure of ZND detonations The approximate solution given in equation (18) for the structure of the upstream part of the detonation wave was first derived by Becker [41] . is the initial velocity of sound. This increase should not substantially modify our other conclusions regarding the wave structure. There is a fundamental reason that large departures from the ZND structure (such as curve e in Figures 6. equation (E27) combined with equation (E34)] indicates that Ax is of the order of a few molecular mean free paths.194 Detonation Phenomena to be discussed in Sections 6. . [16][18]. Thus. in fact. planar wave only on the average (for reviews see.1). In general. No kinetictheory analyses of detonation structure have been reported.3.4) are not to be expected for steady. molecules suffer only two or three collisions in passing through shocks of the strengths ordinarily encountered in detonations. A< y for detonations with a reasonable amount of heat release. Hence. [39]) yield wave thicknesses that are nearly twice as large as those obtained from continuum theory and that are in better agreement with the few available experimental results [40]. this implies that the width of the shock wave in physical dimensions is Ax 4yp/3m = 4yp/3p. Since a.5 and 6. Knowledge of the ZND structure nevertheless is essential to the understanding of the threedimensional structure (to be discussed in Section 6. that is. Kinetictheory analyses of strong shock waves in nonreactive gases (for example. the kinetic theory expression for the viscosity p [for example. In view of equations (511) and (518) and the fact that K z 0. since chemical reactions can proceed only through molecular collisions.2.3). planar waves. but such analyses would be expected to show a similar increase in the width of the upstream (shock) portion of the detonation wave.
5. Since no reaction occurs in the shock wave. The spatial dependence of the flow variables for a shock wave in a gas is illustrated by the upstream (lefthand) portion of the curves in Figure 6. and diffusion) are negligible. which can be shown to violate the second law of thermodynamics in ideal gases with constant specific heats. thereby making it essentially an initialvalue problem . it does not depend on assumptions 9 and 10 of Section 52). On the other hand. heat conduction. The absence of significant molecular transport removes the eigenvalue character of the deflagration problem. There is no solution for the structure of a wave in which cp increases from cp(O) to cp+(O) as t increases.6.co to + 00. The difference i s primarily a consequence of the much larger mass flow rate (or convection velocity) in detonations. This deflagration wave is therefore radically different from those discussed in Chapter 5.the chemical reaction rate influences the length of the reaction zone but not directly the speed of the wave. Equation (18) shows that as 5 increases from . Planar Detonation Structure 195 for shock waves in nonreactive gases.1. and the chemical reaction rate is not high enough to produce these large gradients.5. The solution given in equation (19) for the downstream part of the detonation wave represents a highspeed deflagration in which the kinetic energy is appreciable but the transport processes (viscosity. (that is. The spatial dependence of the flow FIGURE 6. simple analytical solutions for the shockwave structure cannot be obtained from the continuum equations unless the effective Prandtl number is 1 (assumption 8) [42]. cp decreases monotonically from cp+(O) to cp(O). equation (18) is valid for arbitrary reaction mechanisms and diffusion coefficients. this would represent a finiteamplitude expansion wave. Representative variation of flow properties in a detonation wave. very large gradients would be necessary to generate transport fluxes comparable in magnitude to the convective fluxes. . [43].
. the shock wave extends from 5 = . Clearly. N (21) X i= mole fraction of species i. Since transport effects are neglected in equation (19). isothermal.196 Detonation Phenomena variables in the deflagration is illustrated in the downstream (righthand) part of Figure 6. . . Because of the high velocity. the problem of computing the structure of the downstream portion of the detonation wave for any reaction mechanism merely involves a forward integration of a set of equations of the form dXi/dx (x = distance. and in using equations (18) and (19) without modification.2.cp(O)]/(p_(O) = 6. a small ambiguity arises in connecting the solutions given in equations (18) and (19).2. In view of the range of validity of equations (18) and (19) discussed above. In fact. the continuity. Equation (21) is comparable in complexity to the equations governing the time dependence of the concentrations of chemical species in a homogeneous.5 shows a small decrease in temperature as the hot boundary is approached. momentum.* However. X. and pressure to Xi. equation (19) can also be made to apply to a system involving any onestep reaction . .5. it occurs for ChapmanJouguet waves because. of course. ZND detonations involving chain reactions can be analyzed more easily than the deflagrations with chain reactions discussed in Section 5. since transport by suitably modifying the definition of F c ( ~cp). . where 6 is a number that is small compared with unity. the shock wave must be cut off at an arbitrary point and tacked onto the beginning of the deflagration in order to obtain a singlevalued solution for the detonation structure.(X. i = 1. .). . Mathematically.00 to 5 = + co. N = number of chemical species). the temperature decreases (and the Mach number. The cutoff point may be defined as the point at which [cp .5 are modified imperceptibly when 6 is varied from lo’ * The restriction to onestep reactions may be removed by replacing equation (19) by equation (21). For typical detonations the width of the shock wave is so small in comparison with the width of the reaction zone that curves similar to those shown in Figure 6.. effects are negligible. the equation does not depend on assumptions 8 and 10 of Section 5. = J. as heat is added. while (for Arrhenius rate functions) the deflagration extends from a finite value of 5 to 5 = + 00. temperature. This effect is not present for most strong detonations . Hence the two waves overlap. energy.5. density. . Figure 6. these two equations describe the structure of a ZND detonation involving any onestep reaction and satisfying assumptions 18 of Section 5. provided that the rate constants and heats of reaction are known for all elementary reaction steps. reacting system (see Appendix B). the pressure is not constant in the deflagration region of Figure 6. and state equations reduce to algebraic expressions relating velocity...4. increases) along the Rayleigh line when the Mach number is between 1/& and 1.
Analysis of the reaction region of a steady. the shock wave may be treated as a discontinuity. Propagation Velocities for Detonations Traveling in Tubes I97 to Wood [44] recognized that ambiguities of this kind are characteristic of problems of the boundarylayer type. Therefore. Morecomplex approximations to the chemical kinetics generally have required numerical integrations [33]. Activationenergy asymptotics with the chemistry approximated as a onestep process have been introduced on the basis of physical reasoning [13] and through formalisms of matched asymptotic expansions [47]. A related expansion was developed independently [45].3 and 6. The work in [47] involves a double limit that also describes slight merging of the shock with the reaction zone. [48]* to identify an induction zone followed by a shorter heatrelease zone and to obtain asymptotic expressions for the length of the induction zone.1.6. . planar waves but also to unsteady. Here we shall first consider detonations produced by * See also H.2. “An Analytic. it affords one helpful simplification in the complicated analyses of transverse wave structures. For purposes of further analyses of detonation structure. thereby providing an analytical approximation to curve c in Figures 6. Cheng. Both the viscous interaction between the shock and the reaction region and the molecular transport within the reaction region are small perturbations that do not appear to exert qualitatively significant influences on the wave structure.4.2. he has obtained a natural connection between the shock and deflagration solutions. Basic considerations for plane waves We have seen that considerations of detonation structure do not restrict the detonation propagation velocity (at least for strong and ChapmanJouguet waves).2. the “support” provided by the chemical reactions is of a nonplanar compressible gasdynamic character with negligible molecular transport. wave speeds must depend on the experimental configuration and can be discussed only within the framework of a class of experiments. 6. PROPAGATION VELOCITIES FOR DETONATIONS TRAVELING IN TUBES 6. ZND detonation is facilitated by the introduction of simplifications in the chemical kinetics. Asymptotic Theory of Shock Supported Arrhenius Reactions and Ignition Delay in Gas. This conclusion appears to apply not only to steady. An asymptotic analysis with the reaction rate assumed to be zero below an ignition temperature and constant above it has been reported [46]. K. It also alters the interpretation of a detonation as a deflagrationsupported shock. [49]. by means of a boundarylayer expansion near the shock and an expansion in powers of l/A( near the Rayleigh line.” unpublished (1970) for an early version of the study in [48]. threedimensional structures. planar.
6. there is a net increase in the gas velocity in the direction of propagation of the wave (in the laboratory frame) between the end of the tube and the detonation. They find that the time rate of increase of the pressure immediately behind the detonation wave is negative for strong detonations.5) weak detonations Closed end of tube (moving with velocity . [34]). the gas velocity behind the detonation is directed toward the wave (in the laboratory coordinate system) and is subsonic with respect to the wave (see Chapter 2). Steady.6). = l). Many experimental studies have been concerned with systems of this kind. For a strong detonation propagating into a quiescent gas mixture. This same qualitative argument cannot be used to rule out weak detonations. Detonation wave (stationary) c . Since the Mach number behind a strong detonation is subsonic (relative to the detonation wave).c FIGURE 6.198 Detonation Phenomena igniting a combustible mixture with a spark at the closed end of a tube. When the ChapmanJouguet condition is reached ( M . Brinkley and Kirkwood [SO] have formalized the dynamic argument by analyzing a model in which the detonation is of infinitesimal thickness and the pressure behind the wave initially decreases monotonically (with finite slope) toward the closed end of the tube. detonations in such systems are found to travel at the ChapmanJouguet wave speed after an unsteady period of development. Hence (compare Figure 2. positive for weak detonations. and zero for ChapmanJouguet waves. this rarefaction wave will overtake the detonation and therefore weaken it. Such a velocity increase requires that a rarefaction wave follows the detonation. Empirically. When transformed to a coordinate system moving with the detonation velocity. Since the gas velocity is necessarily zero at the closed end of the tube.oo) 1 t ' t . all velocities in the + x direction. The presence of the rarefaction wave is well substantiated experimentally (for example. strong detonations are easily ruled out by dynamic considerations. decreasing the detonation velocity until the Mach number behind the wave becomes sonic. this velocity change becomes an increase from a subsonic speed immediately behind the detonation to a supersonic speed at the closed end of the tube (see Figure 6. Schematic illustration of the velocity profile behind a detonation wave propagating in a tube. . the rarefaction wave can no longer affect the detonation.
2. the rate of condensation increases as the temperature decreases. this success does not produce simple formulas for predicting the onset of condensation. [Sl]. for example. This hypothesis may be supported by the fact that unlike chemical reaction rates. This idea of treating the condensationwave problem as an eigenvalue problem reminiscent of the deflagration problem has not yet been exploited with the objective of obtaining simplified descriptions of condensation waves.3 leads to the idea that a condensation wave can exist in a supersonic nozzle flow only at a definite location that depends on the wave structure. Proposals that weak detonations also represent various processes occurring in geological transformations have been presented [52].2. Propagation Velocities for Detonations Traveling in Tubes 199 (as well as strong detonations) approach the ChapmanJouguet condition as time increases for the BrinkleyKirkwood model.2. Good agreement with the experimental measurements on the location and width of the condensation wave is obtained. Numerical integrations of sets of ordinary differential equations are performed to describe homogeneous nucleation and droplet growth in supersonic flows with negligible molecular transport in the streamwise direction. Consideration of Figure 6. 6. Weak detonations are believed to represent the “condensation shocks” observed in supersonic wind tunnels [12]. Supercooled water vapor in a supersonic stream has been observed to condense rapidly through a narrow wave.3.3. 6.2. The approach is discussed in [54] and [55].2. Theoretical analyses of condensation waves for steady supersonic flows in nozzles are based primarily on the early work of Oswatitsch C. it appears reasonable to assume that condensation shocks are weak detonations.1.6. However. Effects of tube walls As experiments on detonation waves in tubes were refined. A ZND structure is not possible for weak detonations. The amount of liquid formed is so small that the equations for purely gaseous waves are expected to apply approximately. Simplified approaches to the analysis of condensation waves can provide useful results and improved understanding of the wave structure. and chemical reaction rates generally are not high enough to produce a direct transition to the end state. One such approach has been reported recently [56]. for example). Further comments on weak detonations A very convincing argument against the existence of weak detonations utilizes the results on detonation structure presented in Section 6.531. it soon became apparent that these waves do not propagate precisely at the . Since a normal shock wave would raise the temperature above the saturation point (thus ruling out the ZND structure. and the flow is observed to be supersonic downstream from the condensation wave.
the velocity in the boundary layer exceeds the velocity in the reaction zone. For example. (46) through (49)] for the reaction zone (excluding the boundary layer). then the ideal gas equation of state implies that the density in the boundary layer exceeds the density in the reaction zone. For example. and therefore as the boundary layer grows. Conditions relating properties across oblique shock waves readily show that this divergence implies that the shock front must be slightly convex toward the unburned gas. who accounted for the influence of the boundary layer behind the shock front in a ChapmanJouguet wave with the ZND structure. this effect has been observed but. Hence. detonation velocities have been observed to decrease approximately linearly with the reciprocal of the initial pressure in a tube of fixed diameter. the mass flux pv in the boundary layer exceeds the mass flux in the reaction zone. [57]). . The calculation of detonation velocities from the quasionedimensional flow equations is considerably more difficult than the calculations discussed in Chapter 2. The first satisfactory explanation of these effects was presented by Fay [58]. if it is assumed (quite reasonably) that the pressure is independent of the coordinate y (normal to the direction of propagation of the wave) and that the wall of the tube is maintained approximately at room temperature.7. Fay’s model is illustrated in Figure 6. influences the detonation velocity to a negligible extent. Also.7. On the other hand. Furthermore. Geometric considerations clearly imply that in this frame. in itself.200 Detonation Phenomena ChapmanJouguet speed. Schematic diagram of a detonation near a tube wall [SS]. the streamlines in the reaction zone must diverge (at a rate determined by the rate of increase of the displacement thickness of the boundary layer). detonation velocities decrease approximately linearly with the reciprocal of the tube diameter at fixed initial conditions. standard experimental practice is to plot the detonation velocity as a function of the reciprocal of the tube diameter and to extrapolate to zero to obtain the “true” experimental wave speed (for example. where a coordinate system that is stationary with respect to the detonation wave has again been adopted. since the equations of Chapter 2 must now be replaced by quasionedimensional flow equations with a small rate of increase of area [that is. the fact that the flow diverges throughout the reaction zone does affect the detonation velocity. the wave speed now depends on the Shock front ’1 Reaction zone+ ‘&(Mell TBoundary layer Tube wall FIGURE 6.
This result exhibits the observed inverse dependence on diameter.1). By estimating the reaction rate from schlieren studies of detonations and by utilizing an empirical formula for the rate of growth of a supersonic turbulent boundary layer. A phenomenon similar to that occurring at the throat of a convergingdivergingnozzle can therefore occur.2. = 1. then we may question whether the result that v.4. where 6* is the boundarylayer displacement thickness at the plane where M = 1. which is empirically [34] approximately inversely proportional to the pressure) is in rough agreement with the observed pressure dependence. On the basis of approximate calculations of the detonation velocity for representative systems containing stoichiometric hydrogenoxygen mixtures [58].3.1 6*/d. is consistent with the endwall condition. the fractional decrease in the detonation speed (below its classical value) is found to be Avo/vo = 2. and d is the diameter of the tube. obtained in Section 2.3). addition of heat increases M and an increase in area decreases M). the fact that the characteristics propagate at the frozen sound speed implies [59] that the upstream end of the rarefaction wave that follows the detonation (Section . The ChapmanJouguet condition must therefore be applied at the finite value of x at which the rate of growth of the boundary layer is appropriately related to the reaction rate.co. Propagation Velocities for Detonations Traveling in Tubes 20 1 profiles of the static and dynamic pressures in the reaction zone.2. and (since 6* should be approximately proportional to the width of the reaction zone.6. Events occurring downstream from this ( M = 1) plane cannot affect the detonation because in the downstream region the velocity with respect to the wave is supersonic both inside and outside of the boundary layer. the flow can experience a smooth transition through M = 1. Ambiguities associated with frozen and equilibrium sound speeds If a detonation is viewed as a plane ChapmanJouguet wave traveling steadily in a tube in a direction away from its closed end. at a point where the rate of increase of area is in the proper proportion to the rate of increase of stagnation enthalpy. the propagation velocity is influenced by the wave structure. 6. that is. from M < 1 to M > 1. Fay solved this last problem by noting that the effects of area increase and of heat addition counteract each other in quasionedimensional flow (in the subsonic regime. the condition cannot be applied at x = co because the boundary layer would eventually occupy the entire cross section of the tube at some finite value of x. Another problem lies in determining where to apply the downstream ChapmanJouguet condition M . From the standpoint of the method of characteristics for reacting gas mixtures (Section 4.3. Fay obtained numerical values of Avo/vo which varied from 1 % to 4 % and which were in good agreement with experimental results (see Table 6. = ue.
from the requirement that the pressure and velocity gradients must remain finite where rarefaction joins the detonation). 53% CzHz + 47% air 1552 2820 6. This result suggests that contrary to the conclusion reached in Section 2.3 6. (22) where the notation is that introduced in Chapter 1. m/sec 2830 3660 3823 1522 0 2 00 calculated 1. = af.4 + + + 5He 3. it appears that the detonation will propagate steadily if its downstream (chemical equilibrium) condition is applied at v..2.(i + j ) = 0. From Figure 6. p. Although it is clear that there are hotboundary complexities associated with the behaviors of planar detonations having . uo AVO  x 102.3. a point situated slightly onto the weakdetonation branch of the equilibrium Hugoniot.e.6 1.202 Detonation Phenomena TABLE 6.4 1. and (491)] N j= 1 1 wj(dh/a ?:>. it is found that the condition which must be applied at this point is [compare equations (454).1.8 before reaching state C .7 1. 2H2 + + 13He 4. the end states for detonations propagating in closed tubes correspond to the frozen ChapmanJouguet condition indicated by point C in Figure 6.2 2. 2H2 + + 13A 1. Composition AVO . 16% HZ + 84% 2.8 it may be seen that this conclusion poses difficulties in connection with the wave structure. (455).0 observed 1. [61].1) can smoothly join the downstream end of the detonation wave only at a point where the flow velocity relative to the detonation wave is the frozen sound speed af .5 4. 2H2 2. Comparison of calculated and observed fractional velocity deficit at 1atm pressure in 1cm radius tubes [SS] DO. m .3. From the characteristic analysis (specifically. The gas mixture in a ZND wave would meet the equilibrium Hugoniot at point D in Figure 6. where the Mach number based on the frozen sound speed is unity.0 2. 2H2 0 2 0 2 0 2 0 2 5.3 1. i.x 102.6 1.8 [59]. and a transition from D to C is difficult to visualize.2 3.I. Y. Since equation (22) will be satisfied if w j = 0 for all j . which is the statement of chemical equilibrium for the system. Possibilities that have been considered for resolving these difficulties include the investigation of “pathological” [59] systems in which equation (22) (which merely states that the enthalpy change is zero when a small amount of reaction occurs at constant pressure and density) is satisfied with some w j # 0 and the analysis of systems with endothermic reactions near the hot boundary (to aid in a DC transition) [60].
The prevalence of the threedimensional phenomenon. . these effects are small (typically less than 1 % in the detonation velocity) and masked in the laboratory by multidimensional structures of ChapmanJouguet waves.2.5. for nearlimit or singlespin detonationsaverage sustained detonation velocities below the theoretical values by amounts up to about 20 % are observed. Propagation Velocities for Detonations Traveling in Tubes 203 P ilibrium Hugoniot) Equilibrium ChapmanJouguet point Frozen ChapmanJouguet point negative of the square he detonation velocity) FIGURE 6. Schematic illustration of the difference between frozen and equilibrium ChapmanJouguet detonations. Effects of threedimensional structures Observations of threedimensional structures for ChapmanJouquet detonations propagating in closed tubes range from spinning detonations (Section 6.3) slightly in excess of the theoretical onedimensional ChapmanJouguet speed calculated on the basis of chemical equilibrium downstream. necessitates its consideration in the development of accurate theories for propagation velocities. To substantiate this speculation remains a challenging theoretical problem.8. af. It seems likely that when the characteristic dimensions of the nonplanar disturbances are small compared with the tube diameter.2. # ue. Appropriate analyses that couple the threedimensional behavior to the wave field behind the detonation are difficult to develop with accuracies sufficient to distinguish between equilibrium and frozen sound speeds. largely through the onset of a reduced average extent of combustion.3. arising from instability of the planar wave and discussed in Section 6.3. the threedimensional effects will result in average propagation velocities (after removal of the wall effects discussed in Section 6.6. When the characteristic transverse dimensions are largerfor example.1) in weak mixtures to “turbulent” detonations [62] in strong mixtures.2. 6.
Peculiar detonations that appeared to propagate along helical paths in tubes with round cross sections . the pressurized reservoir serves to maintain the downstream gas pressure above that of the ChapmanJouguet state until the reflected wave from the end of the reservoir overtakes the detonation.2. they propagate at the velocity of the shock wave initially established in the shock tube.2 we have been considering detonations in closed tubes filled with combustibles and ignited weakly at one end. If the amount of heat released in the reaction is high enough to generate pressure waves locally that can interact significantly with the leading shock.3. If the overall reaction is exothermic at all.204 Detonation Phenomena 6. Gasdynamic (inviscid) interactions with boundaries tend to weaken the strong detonation rapidly to a ChapmanJouguet wave. then the potential for development of instability arises. Shock tubes have become standard tools for studying chemical kinetics at high temperatures [65]. 6. for example. It is possible instead to initiate the detonation by exploding a strong charge (of a solid explosive. This weakening is enhanced if the end of the tube at which the charge is exploded is open to a lowpressure reservoir. The evident stability of these waves clearly demonstrates that sufficiently strong planar detonations are stable . If the shock wave (or “blast” wave) from the explosive is stronger than the shock that precedes the reaction zone in the ZND structure of the ChapmanJouguet wave. but provision of a sufficiently highpressure reservoir at the initiation end retards the decay.3. This is the principle of operation of a shock tube. Often the reactant material is introduced in small amounts so that the reaction occurs nearly isothermally. With a sufficiently large reservoir at sufficiently high pressure. as discussed in the following section. Spinning detonations and stability considerations It is curious that the basis for the discovery of transverse structures in detonations existed more than 50 years ago. The transverse structures that are observed at or near ChapmanJouguet conditions are consequences of this type of instability. thenin principlethe shock followed by the reaction region together comprise a strong detonation wave. Shock tubes have often been used to investigate strong (and ChapmanJouguet) detonations in a controlled fashion (see. TRANSVERSE STRUCTURES FOR DETONATIONS 6.1. then a strong detonation is established . Shock waves in suitably designed tubes are very planar and decay extremely slowly through viscous interactions. for example) in the tube. this is termed an overdriven wave.6. [12] and [62][64]). it is merely necessary to burst a diaphragm between the reservoir and the combustible to establish a strong detonation . Chemical reactions behind a shock wave produced in a shock tube Up until now in Section 6.
The experimental prevalence of multiheaded spin has prompted categorical statements to the effect that all selfsustaining detonations exhibit significant threedimensional structure [25]. and other characteristics of spinning detonations [75][76].3. clarifications of these structures could have been obtained much earlier (through use of the available experimental techniques to study mixtures progressively removed from limits of detonability).urn. These “spinning detonations” leave a helical inscription on a smokecovered foil that has been placed on the inside wall of the tube.Therefore. In this frame of reference. [67]. In this respect.6.urn). jectories of the strongest waves. The acoustic aspect of the theory suggests that transverse modes other than the spinning (travelingwave) mode may occur.3. In particular.The resulting predictions are in reasonable agreement with experiment. Had it been realized that spin is merely a particular manifestation of the currently wellknown transverse structures. then an acoustic theory may be applied to predict the spin frequency. the leading planar shock moves at the velocity uo .4). the slope of the helical path on the tube wall.the sound speed of the burnt gas. the general properties of the writings have been described theoretically [73][76]. For 30 years after their discovery. The number of transverse nodes in the tube is observed to increase with an increase in the tube diameter or with an increasing departure from the limit of detonability. with the tacit understanding that the transverse waves often do not involve rotation. The writings on the walls mark the tratechniques [23][25]. and they may also be studied by many types of photographic [68][72]. the resulting smokedfoil patterns on walls may be very regular or highly irregular. detonations in mixtures far removed from the limit of detonability may be described roughly as multipleheaded spinning detonations. For a planar ChapmanJouguet wave in an infinitely long tube and in a frame of reference in which the burnt gas is at rest. Transverse Structures for Detonations 205 were observed [66]. If it is accepted that a spinning mode of propagation exists. the slope of the helical path will be proportional to arn/(vo. This conclusion is difficult to substantiate in general because of the complexity of the needed .purely spinning modes are forbidden. Depending on the experimental conditions. Experiments show that morecomplex modes exist. spinning detonations were thought to be unusual phenomena associated only with gas mixtures near the limits of detonability (Section 6. if the markings on the wall occur where the tangential wave crest intersects the leading shock (thereby providing local maxima of pressure and temperature). but their identification is more difficult. the circumferential velocity of a traveling tangential acoustic wave at the wall is a known constant times urn. in tubes with noncircular cross sections. The belief that no ChapmanJouguet detonations are planar rests on the conclusion that all such planar waves are unstable to certain nonplanar disturbances.
. and [92]). To obtain a rough physical understanding of the mechanism of the instability.~ Y ( Y. 1. where 61. The analytical work introduces linearizations about this steadystate solution and employs various different approximations for the rates of chemical reactions.. these may not represent the most unstable mode and therefore may not be observed experimentally. The general idea that emerges is that if the overall rate of heat release increases sufficiently rapidly with increasing temperature or extent of reaction. If v is the gas velocity with respect to the shock at the Neumann condition. the ZND structure usually is unstable even to planar disturbances. The failure to find ChapmanJouguet detonations without transverse structures reflects the inability to encounter real chemical systems with reactionrate properties suitable for stability. Since the instability depends on the wave structure. assume that properties remain constant at their Neumannspike values for an induction distance l. ~ Y / ( Y+ I). From normalshock relations for an ideal gas with constant specific heats in the strongshock limit. thereby giving rise to pulsating detonations . then 1. usually in a onedimensional approximation (for example. may be expressed approximately in terms of the explosion time t. The amplification rate varies with the transverse wavelength and may achieve a maximum at a particular wavelength but apparently does not vanish at either large or small wavelengths.206 Detonation Phenomena stability analysis. after which all of the heat of combustion is released instantaneously. More recent numerical studies have dealt with the nonlinear timedependent equations. The results indicate that few. the Neumannstate conditions are expressible by v/vo = p o / p = (Y . inviscid conservation equations having the ZND steadystate solution. [28]. For example.( n .. [87]. attention may be focused first on a planar detonation subjected to a onedimensional. timedependent perturbation. real combustible gas mixtures admit stable planar ChapmanJouguet waves. P = p o M . a sufficient number of stability studies have now been performed [77][92] to provide a good qualitative understanding of the instability question. if the rate of heat release decreases monotonically with an increasing extent of reaction behind the shock. 6v E 6T 6T 6P a.1).v T P +r=ufiy . In particular. and T = TOM. if any. If uo is perturbed by an amount 6 v o .MY + I). As the simplest structure model. . = vt..MY + 1)’. given by equation (B57) as 1.. planar ChapmanJouguet detonations are stable for suitable rate functions. then 1. It should be understood that since the stability predictions involve reactionrate properties.6v 6t. However. a model for the steady detonation structure is needed to proceed with a stability analysis. is perturbed by an amount 61. The stability investigations address the timedependent. then the mechanism for the instability is absent. then a mechanism exists for amplification of disturbances. however.
is is the Mach number at the Neumann state. (529). thereby strengthening it and increasing uo further.2 ~( 2(n  I)]. which involves convection in the downstream direction followed by propagation of an acoustic wave in the upstream direction. consideration should be given to jump conditions for interactions at the shock and Jm + . A characteristic period for this instability mechanism. it is found that the specific criterion on E/RoT given above is quite conservative in that detonations are stable for a range of values of E/RoT large enough to satisfy the inequality. in terms of the specific heat c p and the heat release q per unit mass of the mixture. the quantity Bo in equation (B57) having been made proportional to p"Ta' [see equation (B51)]. This locally causes an increase in p and T that is convected downstream at velocity u. Even for the simplified model adopted./6uo > 0.1) > i. the strength of the compression that is generated may be insufficient to strengthen the leading shock appreciably. and the steady detonation would be anticipated to be stable to planar disturbances. The discussion given here has been qualitative and does not constitute a correct stability analysis. (23) from which it may be seen that 61. 3 .l)/y. where M % The condition for occurrence of the onedimensional instability mechanism is thus seen to be that E/RoT be sufficiently large. somewhat like a piston motion. Transverse Structures for Detonations 207 in which n is the overall order of the reaction (the pressure exponent) and ci measures the temperature exponent of the preexponential factor.1) > f. In general. by use of equations (231) and (232). For a sufficiently strong ChapmanJouguet wave. < 0) of the heatrelease front when the perturbation arrives at 1.6 . Use of the strongshock relations then gives 61. the temperature at the Neumann state is T = (q/cp)4y(y . Thus instability also requires that E/RoTm or Ecp/Roqbe sufficiently large for ChapmanJouguet waves. The consequent decrease in the ignition time then causes an upstream displacement (61.l)/(y 1).This local increase of heat release generates a compression wave. generation of an expansion wave instead of a compression would be expected by 6vo > 0. From comparison with more complex results. if E/(RoT)+ ci + ( n .u with respect to the leading shock (where a is the sound speed at the Neumann state) and overtakes the shock. which propagates upstream at velocity a . Assume that an external perturbation of the leading shock introduces 6vo > 0./le = ( 6 ~ 0 / ~ 0 ) [1 2E/(R0T). otherwise. It appears physically that for overdriven waves there will be a further requirement that the heat release be sufficiently large. it may be shown by use of equations (234). in terms of the final temperature it is T = Tm2(y. if E/RoT is so small that equation (23) gives 61. and (530) that./6uo < 0 if E/(RoT)+ ci + ( n .
208
Detonation Phenomena
reaction fronts, to allowance for outgoing waves beyond these boundaries, and to inclusion of acoustic waves propagating in both directions in between ; equation (43) may be taken as an integral condition for defining l,, with the integral performed in a Lagrangian frame. A proper analysis of the simplified model would be too lengthy to be included here. Moreover, it is better to take into account distributed heat release, as is done in current analyses (for example, [92]). Even the linear stability analyses then become quite complicated. Simplifications in the stability investigations and greater generality in presentation of results might be achieved by formal application of asymptotic analysis for large values of E/RoT with the distributed reaction. Although some consideration has been given to large values of this parameter, the full power of activationenergy asymptotics has not yet been brought to bear on the problem. Accurate analyses for real systems include such factors as multistep chemistry and variable heat capacities and become very complicated. Thus far our stability discussion has been restricted to onedimensional instabilities. Mathematical formulations of multidimensional instability problems are readily written [78][85], [SS], and although the resulting mathematical problems are not appreciably more complicated than those for onedimensional perturbations, it remains difficult to draw general conclusions from analyses. A stability approach in terms of ray trajectories for transverse acoustic waves helps to clarify physically the character of the multidimensional instability [25], [93]. The types of processes discussed abovegeneration of acoustic waves by heat release in hot, highpressure regions and their subsequent propagation (now nonplanar) and interaction with the leading shockare involved in the instability mechanism. Simplified physical models may be developed [23] based on ideas of nonplanar wave propagation. In one such model [77] a disturbance with a transverse wavelength of order 1, is considered within the context of the simplified structure discussed above, and a criterion for instability is proposed on the basis of isentropic propagation of the wirve generated at the reaction front. Although simplified models may aid in physical understanding, their results [including that obtained from equation (23)] are inaccurate and only suggestive. There is need for development of a better understanding of the instability mechanism.
6.3.2. Theories of transverse structures
Instability analyses do not provide good indications of fully developed transverse structures of detonations because these structures correspond to highly nonlinear phenomena. A great deal of nonlinear evolution would occur between onset of instability and attainment of a mature multidimensional detonation structure. Intersections of oblique shocks are known to constitute a central element in transverse structures of detonations [69], [72]. Obliqueshock relations are therefore relevant to the nonplanar structure.
6.3. Transverse Structures for Detonations
209
In a frame of reference fixed with respect to an oblique shock, let $ be the angle between the approach velocity and the shock plane and 6 be the deflection angle of the flow upon passage through the shock, as illustrated in Figure 6.9 for the wave labeled incident shock. For an ideal gas with constant specific heats, it is then readily shown [94] that in the adopted frame,
M: =
2 ( y  1)Mf 2yMf sin2 I )  (y  1)
+
+
2
+ (y  1)MI sin2$ ’
2M: cos2$
(24)
pz2yM: P1
sin’ $  (y  1)
Y + l
and
where the subscripts 1 and 2 identify conditions upstream and downstream from the shock, respectively. If two intersecting shocks are considered with different angles $ in the same uniform approach flow, then it is found to be impossible for both 6 and p 2 , given by equations (25) and (26), to be the same for both shocks; that is, steady doubleshock interactions do not exist. However, it may be shown [95] that steady tripleshock intersections do exist, as illustrated in Figure 6.9. These tripleshock interactions lie at the core of understanding of multidimensional detonation structures.
Approach
velocity
FIGURE 6.9. Schematic diagram of reactive tripleshock interaction.
\
Incident shock
210
Detonation Phenomena
The wave labeled incident shock in Figure 6.9 leads the other waves and differsfrom them in that in a frame fixed with respect to the wave pattern, the component of the approach velocity tangential to the shock is directed toward the point of intersection. It is in this respect that the leading shock is “incident,” or incoming, and the others are outgoing. The incident shock must be sufficiently oblique to have M , > 1. The transmitted, or Machstem, shock that it intersects is more nearly normal, hence stronger, and it generally has a subsonic downstream Mach number ( M , < 1). To satisfy continuity of the pressure and flow direction across the illustrated slipstream, the indicated reflected shock is needed. This reflected shock is the weakest of the three. The triple point is the point at which the three shocks meet. The pattern in Figure 6.9 is conveniently viewed as a limiting case of a problem in which a shock in one medium is incident on another medium [95], the limit being that in which the two media become identical. The two media are separated along a streamline through the triple point and the slipstream, and the Machstem shock is the shock transmitted into the second medium, the analogy with ray optics then being evident. The steady wave pattern described here is well known in nonreactive ) for the incident shock, the gasdynamics. For given values of M I and I configuration is determined more or less uniquely (see [95], for example, for a discussion of uniqueness). In selfsustaining detonations the incident shock may not be sufficiently strong to initiate chemical heat release in the time available, but the strong Machstem shock usually is. In Figure 6.9 a heatrelease front therefore is shown behind the Machstem shock. The streamwise distance from the Machstem shock to the heatrelease front is the induction distance. For the conditions represented by Figure 6.9, the induction distance behind the incident or reflected shock has been taken to be too long for a reaction front to be shown in the figure. The heat release, of course, will modify the flow field and change the conditions from those calculated for nonreactive wave interactions. A relatively simple manner in which tripleshock intersections may combine to produce transverse structures for detonations is illustrated in Figure 6.10. This figure represents wall traces left by a detonation with a twodimensional structure having conditions that are uniform in the direction normal to the figure. The markings on the smoked wall are produced by triple points like the one illustrated in Figure 6.9.* The triple points are observed to propagate along curved paths and to collide periodically. The shockwave pattern is indicated in Figure 6.10 at one point along one of the markings. At this point the incident and reflected shocks extend above the
* This has been demonstrated experimentally beyond doubt by A. K. Oppenheim and coworkers, who employed highspeed photographic techniques to photograph simultaneously in real time the wave pattern and the wall markings as they develop during detonation propagation.
6.3. Transverse Structures for Detonations
21 1
Direction of propagation of detonation
FIGURE 6.10. Sketch of a regular pattern of smokedfoil inscriptions on the wall of a detonation tube with a rectangular cross section.
trajectory of the triple point in the figure, and the Machstem shock and slipstream extend below. The figure indicates that the incident shock is slightly curved and extends to another symmetrically located triple point on an adjacent wall trace. All the shocks in the detonation in fact are curved and are intensified mainly where the triple points collide; they then tend to decay therafter. For the pattern in Figure 6.10, the incident and Machstem shocks both are strong enough to generate heat release at some distance behind them, but the rate of this heat release is considerably less than that occurring at the triplepoint collisions. The markings in Figure 6.10 may be viewed as corresponding to a standing transverse mode in a tube. A readily measurable characteristic of the detonation illustrated in Figure 6.10 is the transverse spacing s shown, often called the cell size, since detonations with transverse structures have been called cellular detonations. Calculation of s is a primary objective of theories of transverse structures. The spacing is regular in Figure 6.10; considerably more complex patterns with both regular and irregular spacings have been observed and explained at least partially on the basis of various types of triplepoint trajectories. Transverse spacings in selfsustaining ChapmanJouguet detonations are observed to decrease with an increasing pressure or with an increasing amount of heat release of the combustible mixture. For spinning detonations the transverse spacings are of the same order of magnitude as the tube diameter. Theories for calculating s are based on simplifications that adopt ray acoustics for analyzing the propagation of trapped transverse waves [25], [93], [96][98] or on attempts to integrate numerically the full twodimensional, timedependent equations of gasdynamics with shock discontinuities and with finite rates of heat release [27], [49], [99], [loo]. Even the former approach usually employs numerical integrations for calculating ray trajectories [97], and in spite of these complexities, the best theoretically predicted values of s differ from the observed values by amounts on the order of a factor of two. In principle, numerical integration of the full equations describes the process correctly, but although these calculations have
212
Detonation Phenomena
produced interesting wave dynamics similar to those observed, the computations are timeconsuming, even with the largest electronic computers [loo]. Moreover, idealizations and simplifications providing analytical results usually lie at the heart of theories that develop impoved understanding. Thus far, analytical theories for transverse structures of detonations have been developed only on the basis of the acoustic approximation for transverse rays [98]. The spacing s varies with the initial pressure, temperature, and chemical composition in the same way that the induction length 1, varies. Thus the ratio s/l, may be taken as constant in a first approximation. The value of s is appreciably larger than 1,; perhaps s/l, % 10 or 30 [1011.Thus s/vo may be on the order of the period of the longitudinal disturbance, identified in the preceding subsection. The fundamental reasons for this are not entirely clear. 6.3.3. Standing detonations Experimentally, the standing detonations, defined at the beginning of this chapter, do not exhibit the transverse structures discussed above [102][106]. For these strong waves the experimental environment is steady and threedimensional (usually axially symmetric). The velocity is subsonic behind the normal shock existing in the flow before the detonation is formed, and the rarefaction discussed in Section 6.2.1 is not present. Therefore, the fact that these are strong detonations is entirely consistent with the boundary conditions. The length of the reaction zone downstream from the normal shock typically is comparable with the characteristic longitudinal length of the wave pattern downstream from the nozzle exit. Therefore, it is currently unclear whether transversewave patterns would develop if the reaction zone were very short in comparison with the external wavepattern dimension. Based on the stability considerations of Section 6.3.1, it might be anticipated that a transverse structure would occur if the wave conditions were near enough to the ChapmanJouguet conditions but that the ZND structure would be observed for sufficiently strongly overdriven waves. These standing detonations, or variants thereof, have been suggested for use in ramjet combustion chambers for supersonic propulsion at high Mach numbers [1071[ 1lo]. 6.3.4. Detonability limits and quenching thickness A number of practically important phenomena associated with detonations pose fundamentally more difficult theoretical problems than those addressed above. These include the initiation of detonations, transmission of a detonation from confined to unconfined spaces, quenching of a detonation, and limits of detonability. Discussion of these phenomena may conveniently be introduced by considering quenching of detonations first.
6.3. Transverse Structures for Detonations
213
It is found experimentally that selfsupported propagation of a detonation through a combustible mixture contained in a tube with rigid walls cannot occur if the tube diameter is less than a critical value, a quenching diameter for the detonation. Similarly, selfsupported propagation does not occur through a combustible mixture contained between two rigid, parallel, infinite plates if the distance between the plates is less than the critical quenching distance for the detonation. Replacement of one of the two plates by an infinite, quiescent, inert gas again results in failure of the detonation if the thickness of the combustible layer is less than the critical quenching thickness for the detonation, the value of which appreciably exceeds the detonation quenching distance of the same mixture [llll[113], For an infinite, planar slab of combustible bounded on both faces by an inert gas, the critical slab thickness for selfsustained detonation is approximately twice the quenching thickness. Bases have been laid for the development of a degree of theoretical understanding of these phenomena of quenching of detonations [ l l l ] , [114][121]. Although the development of a description of detonation quenching necessitates consideration of detonation structure, an approximate physical understanding of the phenomenon may be obtained without addressing the complexities of cellular structures of detonations. The quenching typically occurs near conditions of spin, for example, with at most a small number of cells present, so that the wave that is quenched may be approximated as being planar and noncellular ; experimentally, cellular structures often are not observed during quenching [111][113]. Therefore, we may consider a model like that illustrated in Figure 6.7, with a reaction zone of length 1 following a normal shock. As discussed in Section 6.2.3, for a detonation traveling in a tube the boundarylayer growth has the effect of an area expansion on the quasionedimensional reaction zone and therefore tends to reduce the Mach number, while the heat release tends to increase the Mach number. It seems logical that for the detonation to exist the latter effect must exceed the former at the Neumann state; otherwise behind the leading shock the subsonic Mach number will begin to decrease further, with an associated temperature and reactionrate decrease, and the system will not be likely to be able to recover to reach the ChapmanJouguet state. Thus a quenching criterion is that the areaexpansion effect exceeds the heatrelease effect at the Neumann state. If A is the effective crosssectional area of the quasionedimensional flow and T ois the stagnation temperature, then for an ideal gas with constant specific heats [1223 in variablearea, isentropic flow,
214
Detonation Phenomena
while in constantarea flow with heat addition,
dM M
2yM2
(29)
According to the specified criterion, the detonation exists only if at the Neumann state, d T o / T odivided by the coefficient of dM/M on the lefthand side of equation (29) exceeds dA/A divided by the coefficient of dM/M on the lefthand side of equation (28). For sufficiently strong leading shocks, the value of M at the Neumann state is such that this criterion to reduce approximately to
dTo/To > 2 dA/A.
(30)
An equality may be used in equation (30) to define approximately a general condition for detonation quenching. If for orderofmagnitude purposes, dTo/dx is approximated as Toll,then this equality becomes dAJdx % A/(21), in which 1 may be estimated from experimental results (for example, [123]~1251). In applying the general criterion of equation (30) to detonations confined by walls, available approximations [58], [117] may be employed for relating dA/dx to the growth rate of the displacement thickness 6* of the boundary layer; roughly,
dA/dx
[pW(vo  ~ ) / ( p v ) ] ( 4 A / d6*/dx H)
= (pw/p){8A/CH(y 1>1> dd*ldx,
where pw is the density of the gas at the wall and H is the hydraulic diameter (four times the ratio of the area to the perimeter of the duct, which is the diameter for a circular tube and twice the height for a channel). In using this formula, d6*/dx may be approximated as 6*/1, where 6* is the boundarylayer thickness at the Chapmanjouguet plane; the condition for quenching then becomes very roughly
6*
( y

1)H/8.
(31)
Orderofmagnitude estimates of quenching diameters and of quenching distances may be obtained from equation (31) if boundarylayer theory is the Reynolds employed to estimate 6*namely, 6* FZ l/&where number is Re = pl(vo  v)/p, in which p is the coefficient of viscosity at the Neumann state (typically Re 2 lo5). To apply equation (30) to the estimation of a quenching thickness for a combustible layer adjacent to an inert gas, we must consider the shock pattern in the inert. An approximate model for this shock pattern is illustrated in Figure 6.11. Although not perfectly consistent with the triplepoint discussion related to Figure 6.9, in a first approximation it may be assumed that the detonation generates an oblique shock with deflection
6.3. Transverse Structures for Detonations
215
FIGURE 6.11. Schematic diagram of model for detonation adjacent to a compressible medium [121].
angle 6 in the inert gas and that this deflection angle also occurs at the boundary of the combustible and thereby imposes a divergence in the crosssectional area of the reacting flow. The geometry in Figure 6.1 1 shows that in terms of the thickness h of the detonable layer, dA/dx = (A/h)tan 6. Equation (25) may be used for 6, with the shock angle t,h obtained in terms of the pressure ratio and the upstream Mach number ( M , ) from equation (26). To achieve an approximate lateral pressure balance, the pressure ratio p2/p1 may be taken to be the pressure ratio p + across the undisturbed detonation given by equation (231) for a ChapmanJouguet wave. With MI = v,,/d, where d is the speed of sound in the inert gas, the cited formulas suffice to determine t,h and 6. If ii % a, then a1 ebraic manipulations show 1 1 4 and tan that for sufficiently strong waves, sin t j % l / 2; that is, t,h rz 7 6 rz l/y. Thus the approximate condition for quenching, obtained from the orderofmagnitude version of equation (30), is
J
1
%
(y/2)h.
(32)
Since 6*/1 is small, comparison of equations (31) and (32) shows that the hydraulic diameter for quenching under confinement is smaller than the quenching thickness for the combustible bounded by the compressible medium. The reason for the difference clearly is that the relief provided by the compressible boundary allows d In A/dx behind the leading shock to be larger than it can be for a detonation under confinement. There are procedures for making more accurate estimates of quenching conditions than those outlined here. For example, differences between properties of the inert gas and of the combustible may be taken into account [l 11). It is interesting that very weak walls can often effectively provide
216
Detonation Phenomena
complete confinement [112] because at the short time scales relevant to passage of the reaction zone, the inertia rather than the strength of the wall is relevant. A wall with mass m per unit area subjected to a pressure p moves a distance (p/rn)t2/2 in time t, and confinement will be provided if this is small compared with 1 during the passage time l/uo. Thus (p/m)(l/2ui) 4 1 leads to confinement, a condition that is roughly m po 1, since the pressure behind the shock is p = p o ui for a strong detonation, where p o is the initial density of the combustible. Since solid materials typically have densities times the length on the order of 103p0, the wall thickness need only be of the reaction zone to provide confinement in representative experiments. From these results it may be inferred that properties of bounding gaseous media may significantly influence quenching thicknesses. Quenching of detonations is relevant to the subject of detonability limits. It is known experimentally that combustible gas mixtures diluted sufficiently with inerts, or fueloxidant mixtures that are too rich or too lean, cannot be made to support a selfsustained detonation; these mixtures are said to lie outside the detonability limits. In practice, detonability limits are narrower than the flammability limits to be discussed in Chapter 8, in that there are mixtures capable of supporting deflagrations but not detonations, although theoretically this need not always be true because the phenomena differ. Explanations of detonability limits were sought first solely on the basis of chemicalkinetic mechanisms and rates [126], [127] but later it was realized that quenchingthickness phenomena provide better bases for pursuing explanations [Ill], [116], [117], [120], [128]. According to these later views, detonability limits may be equated to quenching limits for detonations and therefore depend on the size and configuration of the system. Even with these newer explanations of detonability limits, there tend to be mixtures for which these limits are insensitive to dimensions of the system at sufficiently large dimensions. If the induction time t , or the reactionzone length 1 increases greatly with a small amount of dilution for chemicalkinetic reasons, then in equation (31) or (32) the variation of 6* or 1 with dilution will be so great that no matter how large the value of the dimension H or h is within practical bounds, the quenching condition will be achieved approximately at a fixed limit composition, calculable from the equation by use of a representative value for H or h. This type of behavior enables simplified criteria for the nonexistence of selfsustained detonations to be specifiedfor example, that the temperature at the Neumann state of the ChapmanJouguet wave lie below a critical value. If chemicalkinetic mechanisms are such that there exists a critical dilution above which 1 increases strongly with increasing dilution and below which 1 is much less sensitive to dilution, then this critical dilution may represent a detonability limit determined by the chemistry and effectively independent of the configuration. In this sense, chemical kinetics sometimes may control detonability limits, with quenching details playing a very minor role. The relative
+
6.3. Transverse Structures for Detonations
217
importance of the chemical kinetics and of the system configuration to detonability limits for specific combustible mixtures currently is a topic of uncertainty. 6.3.5. The transition from deflagration to detonation Ways to initiate detonations in detonable mixtures may be subdivided into direct initiation and indirect initiation. In direct initiation a sufficient amount of energy is deposited rapidly in the mixture, which results in the immediate emergence of a detonation after an initial period of adjustment, without the intervening establishment of a deflagration. In indirect initiation the ignition source is weaker and produces a deflagration, which subsequently undergoes a transition to detonation. Criteria for direct initiation involve the energy of the igniter, while the process of indirect initiation is independent of the ignition mechanism. Since direct initiation fundamentally is a simpler process, it deserves some comment prior to a discussion of the transition from deflagration to detonation. On the basis of the ZND detonation structure, a simple criterion can be stated for direct initiation. It seems evident that the energy deposited in the combustible medium must be sufficient to maintain a shock at least as strong as the leading shock of a ChapmanJouguet wave for a time period at least as long as the chemical induction time (or perhaps the overall chemical reaction time) at the Neumann state if the detonation structure is to be established directly by the initiator. This idea was developed by Zel'dovich in the 1940s [129][131] and in essence underlies morerecent theories for direct initiation [22], [132][140]. Use may be made of the similarity solutions for strong blast waves [141][143] to show that the energy (for spherical waves, k = 3), the energy per unit length (for cylindrical waves, k = 2), or the energy per unit area (for planar waves, k = 1) that must be deposited instantaneously in order to initiate a detonation directly is approximately
uk
= Ckrk(Y)POUO
k+2 k te,
(33)
where C , = 1, C2 = 27~,C3 = 471, and the function r k ( Y ) , dependent on both k and the ratio of specific heats, typically is roughly of order unity [22]. Numerical integrations of the timedependent conservation equations [144][146] tend to provide a little additional support for equation (33). Recent work [139], [140] has focused on clarifying influences of the time history of energy deposition on the initiation conditions; in addition to a minimum critical energy, clearly there must exist a minimum critical power as well because an initiator with a power level that is too low cannot establish a shock wave as strong as the leading shock of the ChapmanJouguet wave. Indirect initiation involves a transition from deflagration to detonation. This process has been studied extensively for waves propagating in tubes, and many reviews are available [141[28]. The detonation develops
218
Detonation Phenomena
through a complicated sequence of unsteady, nononedimensional events. The earliest studies of detonation development consisted of experimental measurements of detonation induction distances (the distance required for the steady detonation to form in the tube) [147][154]. Observations that the induction distance depends on the gas composition [148], [149] indicate that the chemical reaction rates are of importance, and observations that the induction distance depends on the tube diameter [l50] suggest that wallinteraction effects are of importance. Wall roughness, turbulenceproducing grids, and vents in the tube also affect the induction distance. Refined experimental techniques have given detailed pictures of the mechanism of transition from deflagration to detonation [16][24], [155][158]. The process is known to involve acceleration of the deflagration by the expanding hot gases behind the wave, generation of Mach waves by the flame, coalescence of the Mach waves to form shock waves, development of turbulence ahead of and within the deflagration caused by the increased flow velocities, and a complicated wave interaction in the multiwave, turbulent system to produce the final ChapmanJouguet detonation. Oppenheim [158][161] and others [162], [163] have developed simplified onedimensional, laminar, multiwave models of the transition process that are capable of correlating many of the experimental observations. The simplest picture [159], [160], [163], involving only two wave discontinuities (a shock wave and a flame), predicts that both waves must propagate at velocities greater than the ChapmanJouguet speed before they can coalesce to form the ChapmanJouguet detonation. From a much more detailed graphical analysis [161], it was found to be possible to obtain a wave pattern that was in excellent agreement with the experimental results of [l55]. More recent studies employ moresophisticated computational techniques [164]. The fundamental problems posed by the transition process remain formidable. It is difficult to explain the high turbulent flame speeds needed for coalescence of a deflagration with a shock; localized initiations of explosions by focused pressure waves and a more nearly direct development of a detonation from these energy sources are likely to play an important role that causes deflagrationshock coalescence to be unnecessary. Studies of wave interactions in reacting media [165][168] therefore are relevant to the transition process, while onedimensional timedependent analyses of fast deflagrations propagating at velocities approaching sonic would not appear to be very relevant. The importance of the buildup of pressure waves in promoting transition to detonation indicates that confining a combustible mixture by walls aids in the development of a detonation. Detonations are more difficult to initiate in unconfined combustibles [169]. If a transition from deflagration to detonation is to occur in the open, then unusually large flame accelerations are needed, and these are more difficult to achieve without confinement. Numerical integrations of the conservation equations demonstrate that
6.4. Detonations in Solids, Liquids, and Sprays
219
transition to detonation is rare in the open [170]. There are similarity solutions for flamesupported pressure fields in the absence of confinement [171][177], and these solutions tend to be stable in that they resist coalescence of the flame with the pressure waves to produce a detonation [173], [1773. Therefore, provision of even partial confinement can significantly enhance the tendency for transition to occur. To obtain improved quantification of the dependence of transition on the degree of confinement is a topic of current research [178]. Since the initiation of a detonation is achieved more readily under confinement, there is interest in establishing the conditions that are necessary for a ChapmanJouguet detonation traveling in a tube to be transmitted into an unconfined combustible at an open end of the tube [179][188]. It is found experimentally that the critical tube diameter needed is much greater than the quenching diameter for the detonation; the value is approximately 13 times the cell size sthat is, roughly on the order of 2001, (see Section 6.3.2). A degree of theoretical understanding of this observation has been developed [183]. To ascertain influences on detonation behavior of the extent of confinement in various configurations remains a topic of active research.
6.4. DETONATIONS IN SOLIDS, LIQUIDS, AND SPRAYS
Our attention thus far has been focused on detonations in gaseous combustibles. There are many liquid and solid materials that are capable of experiencing exothermic decomposition in a detonative mode. These include many solid propellants as well as explosives such as trinitrotoluene (TNT). Detonative processes in liqud and solid combustibles are fundamentally like detonative processes in gases in many ways; the foregoing material is relevant. However, there are special complications that arise from the phase changes and especially from the extremely high pressures produced. The pressures achieved are so high (on the order of los atm) that an appropriate equation of state for the system is uncertain, and therefore ChapmanJouguet detonation velocities cannot be calculated by the methods of Chapter 2. In fact, measurement of detonation velocities becomes an important way to obtain information about the equation of state through use of ChapmanJouguet and Hugoniot relations. In addition, fundamentals of reactionrate theory become hazy at these high pressures. Thus it is unclear whether the instability mechanism of gaseous detonations (Section 6.3.1) is generally operative for solid explosives ; experimentally, the reaction zones of high explosives are usually found to be very thin, and local departures from planar waves often seem to be dominated by granular structures of the material. Over larger distances the wave front tends to be curved and appears to propagate in the charge as if it were unconfined because the pressures
220
Detonation Phenomena
achieved not only exceed the yield strengths of wall materials but also typically are large enough in acting on the wall inertia to produce a significant displacement over a reactionzone length. There are critical charge diameters below which detonation cannot occur, much like quenching diameters for detonations in gases, but usually corresponding to unconfined conditions (except for some liquid and dilute explosives). These often are called failure diameters because the detonation fails to propagate in charges of smaller diameters. In solid or liquid explosives, reactive molecules are continually interacting, and limitations on detonation structures associated with molecular mean free paths no longer apply. It becomes entirely possible for significant release of chemical energy to occur within the structure of the leading shock. This fact motivates new approaches to studies of detonation structure on the basis of molecular dynamics [189], [190]. Although the fundamental complexities that are encountered make the problem difficult, further pursuit of these lines of investigation seems desirable. Questions of practical importance concern failure diameters and conditions necessary for initiation of detonation. Theoretical descriptions of failure conditions in terms of chemical induction times have been developed [1911[196] for solid and liquid explosives through reasoning that bears a relationship to that of Section 6.3.4 for gases. Susceptibility to initiation is usually measured by impact tests in standard configurations that effectively expose the material to one or more shock waves and result in sensitivity classifications for the material. With this type of initiation, the process of transition from shock to detonation is relevant. Initiation also may occur as a consequence of a deflagration propagating through the material, and the process of transition from deflagration to detonation then is of interest. Although there have been many investigations of these various transition processes for propellants as well as for high explosives (see, for example, [1971[208]), numerous unknown aspects remain; representative questions concern the homogeneous and heterogeneous rate processes that may occur. Background information concerning detonations in solid and liquid explosives is available in a number of books [ll], [209][215]. Additional information may be found not only in the proceedings of the combustion symposia and of the international colloquia on gasdynamics of explosions and reactive systems but also in the proceedings of the international symposia on detonation, published by the U S . Office of Naval Research. These last symposia have been held periodically, approximately once every 5 years. Sprays of liquid fuels in gaseous oxidizers can also support detonations. Reasonably extensive theoretical [216][223] and experimental [219], [224][230] studies of detonations in sprays have been reported in the literature, and reviews are available [231][234]. Since the liquid fuels must vaporize and mix with the oxidizer before combustion can occur, it is
If the fuel has a sufficiently high vapor pressure. of aluminum powder [235] or coal dust [236]) and have been involved in dust explosions in grain elevators. R. Burkhardt. FTS1226IA (GDAM AYT45). FTS1227IA (GDAM AYT46). Lewis and G. 542 (1940). Fiz. Jouguet. Flames and Explosions of Gases.R. 9. Vieille. see also “Theory of Combustion and Detonation of Gases. Acad. 2. Physik 43. 347 (1905). adjacent to oxidizing gases [237][242] . 0. (1961). Acad. 0 . NACA Tech. New York: Interscience (l948). Otherwise. 549 (1942). It may be said in general that for any system capable of experiencing combustion or exothermic chemical reactions. 3. 421 (1943). and reaction zones therefore are much longer than the reaction zones of gaseous detonations.D. Memo. No. 18 (1881). Dayton (1949). 4. for example. Wright Patterson Air Force Base. 47. 2nd ed. Among other configurations in which detonations have been observed and studied are thin films of liquid fuels on surfaces . 1st ed. WrightPatterson Air Force Base. 90 (1899). Doin. No. Friedrichs. J. Mallard and H. L. Chapman. Rend. 579627. Mag. Zhur. Phil. Sci. W. B. “Theory of Detonation Waves. 6.” Tech. Berthelot and P.. some degree of theoretical understanding of these detonations has been developed [243][247]. W. B. Incomplete combustion and losses to boundaries then tend to occur. 204234.” Tech. the heterogeneous reactions can occur rapidly enough to support nearly ChapmanJouguet waves in systems of dimensions encountered in practice.” Prog. Sci. (1951). Paris (1917). Rept. Doring.. Courant and K . 8. English translation. Detonations also may occur in solidgas mixtures (for example. Doring and G. Compt. and the detonation velocity correspondingly is less than the theoretical maximum ChapmanJouguet value. Y. Supersonic Flow and Shock Waves. No. the possibility of detonation deserves consideration at least for safety reasons. 5. then the detonation may propagate through the gas approximately independently of the liquid droplets. Rept. le Chatelier. No. 238 (April 1942) O. breakup and vaporization of fuel droplets is a dominant aspect of the propagation mechanism. Rept. 7. M. Combustion. L. MathPmatique 6. Zel’dovich. Nevertheless. Paris 93. E. 511554. E. Compt. von Elbe. 10. J . Ann. 145 (1881). The mechanisms of propagation of these detonations are not well understood. Teor. “Contribution to the Theory of Detonation. When the solid fuel particles are sufficiently fine. Rend. Eksp. Academic Press. Paris93.References 221 generally more difficult to initiate detonations in sprays than in gas mixtures. . Mkchanique des Explosifs. if not for scientific reasons.S. von Neumann. 1261 (1950). Dayton (1949). New York. No. Rept. the existence of detonations in nonvolatile sprays under suitable conditions is now a wellestablished fact.. D. REFERENCES 1.
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Solid propellants conveniently are subdivided into two categories. a typical example is a polybutadiene acrylicacid copolymer as the fuel with crystals of ammonium perchlorate as oxidizer. but in practice it is a mixture of constituents. because a detonation would be damaging.CHAPTER 7 Combustion of Solid Propellants Solid propellants are solid materials that are capable of experiencing exothermic reactions without the addition of any other reactants. They are employed mainly as propellants for rocket vehicles and as propelling charges for projectiles in guns. In heterogeneous propellants the solid is heterogeneous. in principle. The most common homogeneous propellants are doublebase propellants. solidpropellant formulations must be sufficiently metastable to resist transition to detonation. There are heterogeneous propellants in which one or both of the constituents could serve as 229 . There are many different composite propellants. thus forming a composite material that is termed a composite propellant. sensitive explosives generally are not employed as solid propellants. In homogeneous propellants the solid is homogeneous. usually consisting of a continuous fuel matrix or binder containing oxidizer particles. the solid may consist of a single constituent such as nitrocellulose. the fuel and oxidizer being intimately mixed at the molecular level. so named because they are composed mostly of two exothermic compounds (usually nitrocellulose and nitroglycerin). homogeneous and heterogeneous propellants. It is intended that the propellants will deflagrate. Therefore. but singlebase and triplebase propellants also have been used.
In addition to being of fundamental interest. These materials may deflagrate in a process in which a single exothermic reaction front propagates through the solid. mixtures of molybdenum with boron) [9]. gaseous products of combustion are needed in propulsion applications . Readers may consult this literature for more detailed information. In addition. Therefore. and the surface is observed to regress normal to itself at a definite rate. and so on. in which oxidizer crystals are added to the homogeneous propellant. Although processes of this type are of fundamental interest and also of applied interest in materials processing. Thus both doublebase and composite propellants may be metalized. they burn from the surface inward. various other heterogeneous additives often are used. where various elements of their combustion mechanisms will be reviewed. Most books on rocket propulsion devote at least one chapter to solid propellants [1][5]. propellant composition. there are compositemodified doublebase propellants. Heterogeneous propellants will be considered briefly in Section 7. metal particles (such as aluminum) are added and these burn in the gaseous reaction products of the propellant constituents and enhance performance. different approaches to the analyses of their combustion processes will be indicated.7. DESCRIPTION OF STEADY DEFLAGRATION OF A HOMOGENEOUS SOLID The simplest examples of deflagrating solids are those in which all reactants and products are in the solid state (for example. An objective of theories of solidpropellant deflagration is to ascertain the dependence of this linear regression rate or burning rate on the ambient pressure. 7. No less than three books [6][S] have been concerned solely with solidpropellant topics.1. This subject is used here more as a means for introducing various fundamental concepts than as an accurate derivation of burning rates of real solid propellants. the last [S] being a 700page text on the subject. The present chapter is concerned with theories of deflagration of solid propellants. and even the compositepropellant constituent ammonium perchlorate can deflagrate alone at sufficiently high ambient pressures). There are a number of useful background references on solid propellants and their combustion. the burning rate is of importance to the design of systems such as rocket motors that employ solid propellants.230 Combustion of Solid Propellants a homogeneous propellant (for example. temperature. Gasification steps more commonly tend to be endothermic. most of the attention will be devoted to homogeneous propellants . the simplest example of a solid propellant would be a solid that gasifies in an exothermic rate process at a planar solidgas interface. When solid propellants deflagrate. A simple model mechanism for propellant deflagration involves an endothermic .
). containing both fuel and oxidizing species in the same molecule) [12]. A model of this type can be useful for limited purposes. the burning rate appears * There have been some recent clarifications of combustion mechanisms of propellants containing these materials [see N. followed by an exothermic gasphase reaction.5trinitrohexahydro1. For example. moreover. However. and the combustion of doublebase propellants then usually involves reactions occurring in the condensed phase. The problem becomes especially difficult if it is necessary to account for twophase flow that occurs in foam or fizz zones. by further study it was found that this solid melts and then vaporizes during burning instead of subliming directly. one member of a class of materials. (1981). 187194. A twophase region has been called a dispersed phase.* Unless the liquid layer on the surface of the solid is very thin. Instead.N . and in the gas phase. chemical formula (N0. analysis of the deflagration of homogeneous solid propellants is a challenging field of research. Nitrocellulose burns with a subsurface reaction zone in which the solid softens appreciably. Kubota. The foam zone may be observed. if the neglected aspects influence the phenomenon of interest to a sufficiently small extent. . 7777851. in the dispersed phase. CH. a gasphase region in which condensed particles that leave the surface of the homogeneous solid experience exothermic gasification. gas producing reaction. Although analyses of the reacting dispersed phase have been developed [13][ 151. A number of liquid monopropellantsfor instance. in the burning of doublebase propellants with sufficiently high contents of nitroglycerin. and then. Description of Steady Deflagration of a Homogeneous Solid 23 1 sublimation of the solid at an interface. At low nitroglycerin fractions. including materials currently subjected to continuing investigation for use in propellants.' these theories will not be addressed in detail here. the foam zone typically is less prominent than a fizz reaction zone. after a dark zone. followed by a fizz zone. a simplified model will be considered in which there is a sharp planar boundary between condensed and gaseous phases. ethyl nitrateburn by a mechanism that differs from this only in that vaporization replaces the sublimation step [lo].7. such as RDX (1. . for most doublebase formulations. and a foam reaction zone may exist. Because of these complex combustion mechanisms. At one time ammonium perchlorate was thought to deflagrate by the simple model mechanism just defined. (1982). for example.3.3. 18th Symp. A number of energetic crystals behave in this same general way. by a luminous gasphase flame.5triazine. significant exothermic reactions were inferred to occur in the liquid phase [ll]. Burning rates may be controlled primarily by chemicalreaction processes occurring in one phase. called nitramines. such as for calculating burning rates. bubbles may develop within it in the course of the exothermic. 19th Symp.1.
Given the fundamental physical and chemical parameters describing each of these processes. “Deflagration Mechanisms of DoubleBase Propellants at Moderate and High Pressures. * See also F.232 Combustion of Solid Propellants . A number of different burningvelocity formulas may therefore be obtained. Williams. one would like to be able to predict the linear regression rate of the solid (that is. x is the coordinate normal to the surface. A.Condensed phase ? J G a s e p .We are interested in computing the mass burning rate m (g/cm2 . it is convenient here to assume that the solid and the gas are infinite in extent and to adopt a coordinate system in which the flow is steady. As in most steady. depending on which processes are dominant. the velocity at which the interface between the gaseous and condensed phases moves relative to the stationary solid). We shall first discuss interface processes and then consider spatially distributed processes in different phases.1. At a higher temperature.” unpublished (1976). plane. .* Thus simplified models may be relevant to the burning of real propellants. Since the processes described above occur in series. A simplified model that may provide a reasonable representation of the steadystate.1 Model of a burning solid.h a s e Condensedphase reaction zone * Gaseousphase reaction Gaseous products Nonreacting solid 0 X FIGURE 7.1. s) at which the solid must move in the +x direction so that the interface will remain at x = 0. the condensed phase gasifies either in a simple (endothermic) sublimation process or in a more complex (endothermic or exothermic) chemical reaction. to depend mainly on reactions occurring in the condensed phase [16][18]. in Figure 7. The gases evolved react exothermically in the gas phase to produce the final (gaseous) reaction products. the interface is located at x = 0. the slowest processes may be expected to govern the overall burning rate. Heat conducted into the solid from the reaction region raises its temperature to a point at which a phase transition or some other (endothermic or exothermic) chemical (equilibrium or rate) process begins to occur. planar flow problems. the solid extends to x = . and the gas extends to x = + co. onedimensional burning of a homogeneous solid is illustrated schematically in Figure 7.GO. Thus.
Proceeding as in Section B. Hence. the mass burning rate becomes m = W.Y. E is the activation energy for the sublimation process. (2) where W. for illustrative purposes.y l(kOT. Related analyses of more realistic systems may be found in [19] and [20]. unimolecular process : %(s) %(g). we then find that + m = W. for example./T. and 4 + is the same kind of partition function for the activated complex without the degree of freedom corresponding to translational motion in the direction of the reaction coordinate. respectively. (1) where ‘9Xl is the chemical symbol for the subliming species. and s and g denote solid and gas phases.2. Hence./h)(q# /ql)eE’RoTl. (4) where ko is Boltzmann’s constant. y + is related to the actual number of moles of species 1 per unit area. m = ~IYlw. and T denotes the average time for an activated complex to sublime. is the molecular weight of species 1 (the species of which the solid is composed). we shall study the simplest case of a onecomponent condensed phase that sublimes in a onestep. is the interface temperature (at x = 0). can be expressed as a ratio of partition functions per unit surface area through reasoning similar to that leading to equation (A24) for K./T).. Ro is the universal gas constant. then the number of moles per unit area per second leaving the surface is Y + / T . 7.2. APPLICATIONS OF TRANSITIONSTATE THEORY Let us consider the case in which the burning rate is determined by the rate at which molecules from the condensed phase enter the gas. Applications of TransitionState Theory 233 7. where K: is the equilibrium constant for surface concentrations for the process in which the complex is formed. Since the same number of partition functions appear in the numerator and in the denominator of equation (4) . h is Planck’s constant. We shall focus our attention on the process occurring at the interface x = 0. If y+ denotes the number of moles of activated complexes (for the sublimation process) per unit surface area. through the equilibrium condition y + / y l = K:. From the viewpoint of the transitionstate theory. Solid propellants generally contain a number of different chemical species.7.3.4. Transitionstate theory (Appendix B) provides information concerning the rate of this gasification process. (3) The equilibrium constant K . yl. However. q 1 is the partition function per unit surface area for species 1 (with the groundstate energy factor removed). each of which may gasify by processes of varying complexity.
234
Combustion of Solid Propellants
(because of the assumption of a unimolecular process), the “per unit surface area” parts of q+ and q1 cancel and therefore can be neglected. The surface concentration y1 appearing in equation (4) is easily related to the density and molecular weight of the solid. Geometrically, $ I 2 is seen to be the number of moles per unit volume in the solid. Hence,
where p, is the specific gravity of the solid. In view of equation (5), equation (4) becomes
Equation (6) is the required massburningrate formula, which (under our present assumptions) determines m in terms of the interface temperature T and the properties of both the solid and the activated complex. In order to use equation ( 6 ) ,we must measure, estimate, or compute the value of T, for the burning solid. The surface temperature usually depends on the amount and rate of heat release in the gas (and perhaps in the solid) as well as on the heat transfer rates in the gas and in the solid. Therefore, equation (6) should be supplemented by an analysis of the thermal processes occurring in the system. An example of such an analysis will be considered in Section 7.5. In the remaining part of this section we shall discuss a more basic difficulty encountered in attempting to use equation (6). The structures of the solid and of the activated complex affect m through the parameters E and q2/q1 in equation (6). Generally, so many different possibilities exist for the structure of the complex that these parameters cannot be calculated from purely theoretical considerations. Semiempirical procedures must therefore be used to determine the burning rate from equation ( 6 ) even when is known. In order to amplify these assertions, let us consider the ratio q + / q l . The partition function for species 1 on the surface of the solid differs considerably from that for species 1 in the gas. The translational degrees of freedom of the gas molecule generally become vibrational degrees of freedom in the solid, and some (or all) of the rotational modes in the gas may also become vibrational modes (librations) for the solid. Furthermore, the activated complex on the surface of the solid may differ in more than one way from nonactivated surface molecules ; for example, rotational motion may be less inhibited for the complex (leading to fewer librations and a greater number of fully excited rotational modes), or vibrational modes corresponding to translational motion of the center of mass may assume different frequencies in the complex. A very simple case is that in which q+ differs from q1 principally in having one less vibrational factor, as indicated in Section B.3.6 for the unimolecular gaseous reaction; that is,
7.3. Approach to Interfacial Equilibrium
235
where q, denotes this vibrational factor. However, equation (7) represents only one of many possibilities. In view of these uncertainties, the actual structure of the complex is usually best determined by using all available data concerning the structure of the sdid (to find q l ) in conjunction with measured gasification rates, in order to obtain q + through equation (6). These rate measurements may be performed for the burning solid, in which case equation (6) merely provides a formula for correlating data, or for a gasification process in which the gaseous combustion is supressed (for example, sublimation at pressures below the limit of flammability). With the latter strategy, equation (6) is first used in order to obtain q + from experiments that do not involve combustion, and afterward equation (6) also determines m for the burning solid. Actually, a measurement of m gives q+ C E I R T T , not q t alone [see equation (6)]; since E is generally also unknown, the measurements must be performed at different interface temperatures in order to determine E (from the primary dependence of m) and q + separately. The program outlined above has not been attempted for conventional solid propellants, primarily because propellant compositions are so complex that a simple formula of the type given in equation (6) is not expected to be valid. However, a number of propellant ingredients have been studied extensively from our present viewpoint. Experiments on the rate of sublimation of a solid in a vacuum [21][26] [for which equation (6) is least questionable, since gasphase processes cannot affect the measured sublimation rates] and experiments in which the solid is pressed against a heated plate at atmospheric pressure [27][31] have been performed. Hypotheses concerning the mechanism of the sublimation process and the structure of the complex have been invented in order to correlate the measured m values The heatedplate, or linearpyrolysis, experiments [26][28], [30][33]. demand special consideration of gasphase processes in their analysis [S], [30],[33][38] as a penalty that must be paid for their abilities to approach the higher surface temperatures achieved in solidpropellant deflagration. Alternative methods for reaching high temperatures, such as laser heating, also need gasphase analyses for their full interpretation [39], [40]. The presence of the gaseous phase can cause a departure from equation ( 6 ) as a consequence of the possibility of attainment of interphase equilibrium. 7.3 APPROACH TO INTERFACIAL EQUILIBRIUM
At the surface of a burning solid, the reverse process
may be fast enough to alter appreciably the formula for the burning rate given in equation (6). Equation (8) represents the process in which the gaseous species evolved from the solid returns to the surface. This process may be described from the viewpoint of molecular gas kinetics, which is presented
236
Combustion of Solid Propellants
in Section B.4.3. By reasoning analogous to that leading to equation (B80), we find that the mass per unit area per second returning to the solid is WIPla,where 8, [which is given by equation (B78) when the vapor is an ideal gas] is the number of moles of species 1 (in the gas) per unit area per second striking the surface, and a is a (dimensionless) surface accommodation coefficient or evaporation coefficient for molecules of species 1. Thus, equation (6) should be replaced by the expression
= ~ 1 1 213 3
1
P, ( k 7;/h)(q#/ql)eE'RoT1  W l P l E .
o
(9)
The factor P, introduces into equation (9) an explicit dependence of m on the concentration c l , i of species 1 in the gas adjacent to the interface [see equation (B78)]. Except for this difference, equation (9) contains the same kinds of parameters as does equation (6), since the coefficient a can be analyzed from the viewpoint of transitionstate theory. Although a may depend in general on and the pressure and composition of the gas at the interface, a reasonable hypothesis, which enables us to express a in terms of kinetic parameters already introduced and thermodynamic properties of species 1, is that a is independent of the pressure and composition of the gas [ a = a(TJ3. Under this condition, at constant the last term in equation (9) is proportional to the concentration c l,i and the first term on the righthand side of equation (9) is independent of cl, i.Therefore, by increasing the concentration (or partial pressure) of species 1 in the gas, the surface equilibrium condition for species 1m = 0can be reached. If pl,,(TJ denotes the equilibrium partial pressure of species 1 at temperature T , then when m = 0, equation (9) reduces to
W,[pl, e( TJ/Ro T J J a = W :'3p:i3(k0 TJh)(q# / q l)e E'RoTl,
where use has been made of equation (B78) and of the idealgas equation for species 1 (cl = pl/RoT).This relation shows that a(7J is given by
a
=
[ p , , e( 331 ' J ~ ( p , / W 1 ) 2 ~ 3 ( k 0 ~ / h /)q l() eq  E,' R O T 1
(10)
under our present assumptions. In view of equation (B78) and the idealgas law, equation (10) implies that equation (9) can be written in the alternative form
= w1/3 2 / 3
1
P, ( k T/h)(q,/q,)e
0
E/RoT,
C1  ~ 1 , i / ~ l , e ( T i > l ,
(11)
where pl, is the partial pressure of species 1 in the gas at x = 0. The new parameter p1,,(TJ, appearing in equations (10) and ( l l ) , is the equilibrium vapor pressure, which is given by equation (A23) and is where L is the heat of sublimation. approximately proportional to eKLIRoTZ, If pl,e(ZJ cannot be calculated from known thermodynamic properties or measured by conventional techniques, its value may sometimes be deduced by measuring m with the solid pressed against a heated plate [34]. After pl,,(TJ has been obtained, to compute the burning rate of the solid from
7.3. Approach to Interfacial Equilibrium
237
equation (1 1) entails considering gasphase reactions in order to determine p l , i . Equation (11) is, therefore, somewhat more difficult to use than is equation (6). If pl,i/pl,e(TJ < 1, then equation (11) merely provides a small correction to equation (6). However, p l , i / p l ,,(Ti) may approach unity for some burning solids. In such cases, the gasification process, equation (l), no longer governs the overall burning rate ; some other process becomes rate controlling. In extreme cases it is sometimes reasonable and convenient to replace equation (1 1) by the simpler requirement of surface equilibrium, namely,
P1,i
= Pi,e(Th
(12)
in computing the mass burning rate from an analysis of another process, such as finiterate chemistry in the condensed or gaseous phase. If surface equilibrium prevails, then it is relatively straightforward to generalize the interface condition to chemical processes that are more complex than equations (1) and (8). This of interest, since propellant materials often experience processes of this type; for example, NH, C10, undergoes dissociative sublimation into NH, and HC10, [33]. For a general process v;YJlj in the gas, in which the condensed material is transformed to the surface equilibrium condition (for an ideal gas mixture and a solid whose thermodynamic properties are independent of pressure) is
j= 1
n
N
pyli = KJT)~
(13)
where K,(T) is an equilibrium constant for partial pressures [compare equation (A26)]. When equation (13) is applied with p j = p X , , it is important to realize that the mole fractions X j in the gas are not deducible directly from the composition of the solid. There are relationships for interface flux conservation of species, obtainable from equation (158), but these involve diffusion velocities in addition to the concentrations. A nearby source or sink for a species in the gasfor example, a reaction sheetcan influence the relative concentration of that species at the interface through differential diffusion. It is desirable to be able to ascertain in advance whether equation (6) or equation (12) is the better approximation. A few general observations can be made concerning this question. Polymeric materials generally gasify in irreversible rate processes, effectively exhibiting an infinite value of P ~ , ~ ( they T ) ; may be considered to exist in metastable states because molecules entering the interface from the gas do not combine to add to the polymer chain in the solid. On the other hand, for most simple subliming or is I much larger than the values of m typically vaporizing materials, W , ~ , C encountered in solid deflagration, and it may then be seen from equation (9) that surface equilibrium is a good approximation. The smaller CI is, the
238
Combustion of Solid Propellants
less likely it will be that equation (12) can be used. An increasing extent of molecular rearrangement upon gasification is associated with a decreasing likelihood of achieving interfacial equilibrium. For a simple dissociative sublimation such as that of NH,C10,, surface conditions may or may not correspond to equilibrium (they usually do for NH,CIO, [33], but not necessarily for the dissociative vaporization of B, 0, [41]). For processes that are more complex than these, finite surface rates usually are encountered. In doublebase propellants, the situation is more complicated in that the nitrocellulose component cannot achieve equilibrium, while equilibrium vaporization of nitroglycerin may occur. This complexity enables interfacial equilibrium to be unimportant for some processes (for example, steady deflagration [40]) but possibly of significance for others (for example, radiant ignition [42]). Use of the more general interface condition given by equation (ll),instead of equation (6) or equation (12), has not been made in studies of deflagration of solids but could be warranted if a is in an appropriate intermediate range.
7.4. DEFLAGRATION CONTROLLED BY CONDENSEDPHASE REACTION RATES
If there is exothermicity in the condensedphase reaction zone illustrated in Figure 7.1, then the burning rate may be controlled by reactions that occur in this zone. Deflagration analyses paralleling those discussed in Chapter 5 may be developed for condensedphase combustion. For illustrative purposes, let us assume that the condensedphase reaction is the onestep process
WdS)
+
%(s),
(14)
which may be considered to precede equation (1). An Arrhenius reaction of zero order will be treated here for simplicity. The most important physical difference between condensedphase and gasphase reactions is that diffusion of species is much slower in the condensed phase; here we shall neglect molecular diffusion entirely to expose this difference most strongly. A formulation like that of Chapter 5, with the assumption of low Mach number 0,approximately a constant) introduced at the ouset, results in
dYJdx
=
wl/m
(15)
and
ildT/dx = m(h0 Yo
+ h,Y,) + constant,
(16)
in place of equations (57)and (59). With the heat released per unit mass of
7.4. Deflagration Controlled by CondensedPhase Reaction Rates
239
reactant consumed in the condensed phase defined as q, (16) may be written as
=
h:

hy, equation
where the subscript 0 identifies conditions at x = a (at which point dT/dx = 0) and where c p is the specific heat at constant pressure for species 0 and 1, assumed equal. In equation (15) for a zeroorder reaction, we write
w1 = p ~ l ~ a i e  E ~ / R o T
(18)
[compare equation (516)], in which all quantities now of course refer to the condensed phase. Boundary conditions for equations (15) and (17) are that Y,= Yl,,andT=T0atx=  m a n d t h a t Y , = l a n d T = q a t x = O . The problem that has been defined here possesses the coldboundary difficulty discussed in Section 5.3.2 and can be approached by the same variety of methods presented in Section 5.3. The asymptotic approach of Section 5.3.6 has been seen to be most attractive and will be adopted here. Thus we shall treat the Zel'dovich number
as a large parameter. Although a relationship between Y, and T like equation (524) cannot be derived because the Lewis number differs from unity, the variable Yl can be eliminated by differentiating equation (17) and using equation (15). From the solution to the resulting equation for T, the value of m is then found from the integral of equation (15), namely,
= w 1 dx/(l  yl,o), in which the asymptotic expansion of this divergent integral is intended. There is an upstream convectivedifuusive zone in which only convection and heat conduction occur. In the variable 5 defined in equation (518), the solution in this zone is Y, = Y,, and
J,
0
where a matching condition has been anticipated in putting q equal to the upper limit of the integral on the lefthand side. This solution allows for a variable heat capacity, and subsurface phase changes (for example, melting) are readily included by introducing delta functions in c p . In the reactivediffusive zone the stretched variables q =  b5 and
240
Combustion of Solid Propellants
may be introduced to produce in lowest order the problem d2yldq2 = AeCY7 (23) with y = 0 at q = 0 and dy/dq + 1 as q 4 c c (through matching), where
which is assumed to be of order unity. The first integral of equation (23), subject to the matching condition, gives (25) provided that 2A I1. In the innerzone variables that have been introduced, the first approximation to equation (20) is
d y l d n = (1  2Ae')''2,
&=A
where
[
m
eYdq,
(26)
Use of equation (25) in equation (26) produces, after algebra,
A = B (1  +a).
In dimensional terms, this result is
ROpLBl T;i +221eE1/R0T~
(28)
m = ( El(1

Y,,)[ " c p d T
To
%(I 1  Y1,J 2
The subscripts i here on p and A indicate that they are to be evaluated in the condensed phase at T = ?I. The derivation of equation (29) has not employed conservation conditions at the interface with the gas; hence the value of .T; remains undetermined. Therefore, additional physical information must be introduced to calculate rn. The simplest condition to apply at the interface is adiabaticity, dT/dx = 0, which serves to isolate the solid from the gas and shows from equation (17) that l;; c,dT = qs(l  Y l , o ) therefore , giving 7;. In this case equation (29) reduces to a formula for rn derived originally by Zel'dovich [43]. It is interesting to compare the resulting expression with equation (575) for a gaseous flame with a Lewis number of unity. In the first approximation the two formulas differ only by an additional factor of j'/' on the righthand side of equation (575). This difference is readily understandable on the basis of the physical reasoning given in Section 5.3.7. Diffusion of the reactant is responsible for a factor p'/' in equation (575) through the consequent reduction in the reactant concentration (hence in the reaction rate)
1
I.
(29)
7.4. Deflagration Controlled by CondensedPhase Reaction Rates
24 1
in the reaction zone. This diffusion is not present in the condensedphase deflagration, and the corresponding factor is therefore absent. The reactant concentration in the condensedphase reaction zone is of the same order of magnitude as it is in the cold propellant. This fact could have been used to scale equation (15), thereby producing, with equation (23), a pair of simultaneous differential equations for describing the reactionzone structure 1401. The solutions obtained with the adiabatic boundary condition are unstable to onedimensional disturbances (see Section 9.2). The derivation of equation (29) is invalid if q,(l  Y1,J > c p dT, since equation (17) then implies that dT/dx < 0 at x = 0, so that contrary to assumption, the peak temperature of the condensed phase no longer occurs at its surface. In a sense, the adiabatic condition represents a limiting condition at which the condensedphase deflagration breaks away from the surface and ceases to be influenced by interface or gasphase processes. From the viewpoint of the condensedphase analysis, it is necessary that q,(1  Yl, o) I j$o c, dT. When the inequality prevails in this relationship, heat is fed into the condensed phase at its surface. With To, q,, and other condensedphase properties fixed, this energy input increases m because the consequent increase in IT; exerts a larger influence on the Arrhenius factor in the numerator of equation (29) than on the integral in the denominator. Strictly speaking, whenever the inequality holds, the burning rate is not controlled entirely by condensedphase processes because interface or gasphase processes then influence m by modifying IT;. The simplest approach to the use of equation (29) in these nonadiabatic cases is to assign Ti a constant value, a “gasification temperature” that is presumed to be known, but this approach fails to address the question of the physics that determine the value of q. If we consider Ti fixed and q, decreasing, then we find that the derivation of equation (29) remains valid as q, vanishes or becomes negative. The requirements of the analysis are that 7; > To and that there be a distributed condensedphase Arrhenius reaction with large. The reaction may be exothermic, energetically neutral, or endothermic ; in the latter case, A and B are negative. Under these conditions, the condensedphase reaction naturally does not control the deflagration rate, but equation (29) provides a relationship between m and 7; that is necessary for compatibility with the condensedphase processes. Many polymeric binders of composite propellants experience endothermic gasification of this type. In fact, the basis of the analysis given here was first developed for endothermic linear pyrolysis of polymeric materials [44], [45]. A number of modifications and generalizations of the analysis presented here can be explored [14], [40], [45]. A reaction order of zero has been selected here for simplicity of development. By working with two simultaneous differential equations in the reaction zone, the formulation is easily extended to an arbitrary reaction order n. For 0 < n < 1, a modified version
242
Combustion of Solid Propellants
of equation (29) is readily derived [45]. With the most natural assumption of unimolecular decomposition, we have n = 1, but for n 2 1, a difficulty is encountered in that equations (15) and (16) allow Y, to approach unity only as x + + co ;just as in the gaseous flame (see Section 5.3.7), an infinite time is needed for complete conversion of reactant to product at these larger values of n. To place the interface at a finite location with n 2 1, a value of Y, less than unity must be selected at the interface [45]. The selection may be made arbitrarily on the grounds of insensitivity of predictions to the value chosen within a reasonable range, or an additional physical phenomenon such as equilibrium vaporization, equilibrium solubility, or onset of dispersion may be introduced formally to fix the surface value of Y, [14]. Indeed, these physical phenomena may be relevant even for 0 5 n < 1, and equation (29) may be modified accordingly by taking Y, < 1 at the surface in carrying out the analysis. These refinements have been introduced mainly in conjunction with an assumption of surface adiabaticity [141. In addition, adiabatic analyses are available for arbitrary n 2 0 for situations in which the condensed phase extends to x = + co [14]. Effects of nonadiabaticity associated with radiant flux incident on the surface of the solid have been analyzed by methods similar to that given here [40]. So long as the finiterate chemistry occurs in a single reactivediffusive zone extending to the surface of the condensed phase, the analysis need not be restricted to a onestep reaction. Known mechanisms of homogeneous polymer degradation may be taken into accountfor example, [45]. The results continue to be expressible in formulas that resemble equation (29) but that usually are somewhat more complicated. There are numerous possibilities for using equation (29) in conjunction with interface or gasphase conditions to determine both m and 7;. For example, the condensed product of equation (14) conceivably might experience the rate process of equation (1) as soon as Y, = 1, so that equations (6) and (29) become two independent expressions for m and T . Alternatively and somewhat less unlikely, surface equilibrium may occur so that equation (12) determines in equation (29); in this case, a gasphase analysis is generally needed to find p , , i. It appears that in most real homogeneous propellants, the products of the exothermic condensedphase reactions are mainly gaseous, so that considerations of dispersion or possibly of gasphase reactions are most relevant for determining T in equation (29), and equations (6), (ll), or (12) are not directly useful. The general similarity between equations (6) and (29) may be noted. Both exhibit an Arrhenius dependence of m on T , and measurements of the variation of m with T , therefore do not distinguish between the two equations, even though the processes represented fundamentally are quite different, one being an interface reaction and the other in reality a distributed condensedphase reaction. The activation energy E for the surface reaction is seen to correspond to E,/2, half of the activationenergy for the
7.5. Deflagration Controlled by GasPhase Reaction Rates
243
bulk reaction, because of the squareroot dependence of the deflagration rate on the homogeneous reaction rate. This squareroot relationship clearly applies in endothermic linear pyrolysis as well. Thus in steady deflagration or linear pyrolysis, for many purposes the distributed condensedphase reaction may be approximated as a surface reaction having half of the true activation energy, thereby achieving simplifications in the analysis. Fundamentally, equation (6) is seldom every correct for polymers, but since equation (29) often is, equation (6) may be employed, with suitably adjusted values of E and of the preexponential factor. If the solid were inert and the interface gasification process were exothermic, releasing the energy qi per unit mass of solid gasified, and if the system were adiabatic with negligible energy input from the gas, then lF:,cpdT = q i would determine IT;., after which equation (6) would give m. This result, which constitutes the simplest complete model for solidpropellant deflagration, can be made to correspond to the adiabatic version of equation (29) by putting E , / 2 = E and q i = q,(l  Y1,J and equating the factors preceding the exponential. Gasphase reaction rates may modify these results if heat conduction from the gas to the interface occurs.
7.5. DEFLAGRATION CONTROLLED BY GASPHASE REACTION RATES
If we overlook the processes occurring in the region x I0 in Figure 7.1, then the illustrated burning mechanism of the solid closely resembles that of a premixed gaseous laminar flame. To proceed with an analysis, let us assume for illustrative purposes that the gaseous reaction is the onestep unimolecular process %(i4 1IJz2(g), (30)
+
where the subscript 2 identifies the reaction product, and also adopt (in the gaseous region) the other basic simplifying assumptions employed in Section 5.3 (namely, lowspeed flow and assumptions 111 of Chapter 5). Then the results of Section 5.3 can be applied to a deflagrating solid in which premixed gasphase reactions influence the burning rate. The purely gaseous deflagration extends from x =  co to x = + 00, with cold boundary conditions applied at x =  co ; but the gaseous region of the burning solid extends only from x = 0 to x = + co,with cold boundary conditions applied at x = 0. This is the primary difference between a gaseous laminar flame and our present model of a burning solid. Any governing equations that can be derived for the gaseous flame without making reference to the cold boundary conditions will apply equally well to the burning solid in the region x > 0. If the normalized mass flux fraction of products is defined as t 1  (tZ.m  t2)/A~2, (31)
244
Combustion of Solid Propellants
where t2 is the flux fraction of species 2, the subscript co identifies conditions at x = co,and At2 is the total change in t2 in the gas, the normalized mass fraction of products is defined as
+
Y
1  (Y2,, 
Y2)/At2,
and the dimensionless temperature is defined as
7 1 c,(T  T,)/q, (33) where c p is the (constant) specific heat at constant pressure for the gas and q is the total heat released in the gas per unit mass of the gas mixture, then, through a development similar to that given in Chapter 5, the reader may show that equations (524) and (542) can be derived without using the coldboundary conditions. Thus the relations
+
Y=T
(34)
and
dt/dT
= h / ( Z  t),
(35)
where the dimensionless reactionrate function w(z) and the (constant) dimensionless massburning rate A are given by equations (543) and (549, respectively, remain valid in the gaseous region for the burning solid. Actually, in order to remove all reference to conditions at x = a in the purely gaseous problem, the quantity a' appearing in equation (543) must be defined as
a' = q/(c,T,  d,
(36)
which is equivalent to equation (529) for the gaseous flame. The boundary conditions for equation (35) at x = co for the burning solid are the same as those for the gaseous flame; namely, t = 1 and z = 1 [see equations (31) and (33)]. However, as we have already stated, the coldboundary conditions differ in the two problems. For the burning solid, the definition of At2 implies that
+
At2 = t 2 , ,

t2,i,
where the subscript i identifies conditions in the gas at the interface (x = 0). Hence, equation (31) shows that t = 0 at x = 0. Equation (33) implies that T = ziat x = 0, where (37) Therefore, the coldboundary condition (at x = 0) for equation (35) in the burning solid is t = 0 and T = zi. It will be noted that these boundary conditions ( E = 0 at T = zi and t = 1 at T = 1) are formally identical with the boundary conditions introduced in Secti,on 5.3.2 in order to remedy the coldboundary difficulty for the
Ti
1 k
C,(T
 T,)/q.
7.5. Deflagration Controlled by GasPhase Reaction Rates
245
gaseous flame. In Chapter 5 the quantity zi was a dimensionless ignition temperature for which a pseudostationary value was chosen ; for the present problem, on the other hand, ziis a welldefined dimensionless measure of the interface temperature. Thus the coldboundary difficulty does not arise in the present problem; the presence of the condensed phase has removed it by cutting off the reaction at the interface. A consequence of the equivalence of the two problems is that any of the procedures discussed in Section 5.3 for determining the laminar flamespeed eigenvalue A of equation (545) can be applied without modification for finding A as a function of zi,a’, and [defined in equation (544)] in the present problem. In using these procedures, one should recognize that w(z) is given by equation (543) only for z > z i ;w = 0 for z < zi. Results of the asymptotic analysis of Section 5.3.6 have been used in a number of investigations of solidpropellant deflagration [43], [46][49]. From the discussion associated with equation (575) (where now a = q/c,T, and b ,’ = E,q/Roc,T2), it is seen that A is then found to be independent of when the gasphase properties and the zithat is, m is independent of overall energetics (T,) are fixed. In this respect, the gasphase reaction controls m completely; other processes serve only to establish values for other quantities, such as q ,when the asymptotic analysis that has been given is applicable. With adiabatic combustion, departure from a complete control of m by the gasphase reaction can occur only if the derivation of equation (575) becomes invalid. There are two ways in which this can happen; essentially, the value of m calculated on the basis of gasphase control may become either too low or too high to be consistent with all aspects of the problem. If the gasphase reaction is the only rate processfor example, if the condensed phase is inert and maintains interfacial equilibriumthen m may become arbitrarily small without encountering an inconsistency. However, if a finiterate process occurs at the interface or in the condensed phase, then a difficulty arises if the value of m calculated with gasphase control is decreased below a critical value. To see this, consider equation (6) or equation (29). As the value of rn obtained from the gasphase analysis decreases (for example, as a consequence of a decreased reaction rate in the gas), the interface temperature q, calculated from equation (6) or equation (29), also decreases. According to equation (37), this decreases zi.Eventually, corresponds to at a sufficiently low value of m, the calculated value of zi = 0. As this condition is approached, the gasphase solution approaches one in which d T/dx = 0 at x = 0, and the reaction zone moves to an infinite distance from the interface. The interface thus becomes adiabatic, and the gasphase processes are separated from the interface and condensedphase processes. At this limiting condition, the gasphase deflagration becomes irrelevant to the solidpropellant deflagration. Either equation (6) or (29) can now
246
Combustion of Solid Propellants
be used to calculate the burning rate in conjunction with a condition of surface adiabaticity. If L denotes the net chemical enthalpy per unit mass needed for gasification of the condensed phase, then an energy balance for the condensed phase shows that this adiabaticity condition can be written as c,dT
JT,
=

L,
which serves to determine IT; without reference to the gaseous phase. In principle, equation (38) can be applied irrespective of the sign of L and irrespective of whether the value of obtained from it is greater than or less than To. For example, for the model that led to equation (29), if species 1 undergoes endothermic sublimation or vaporization after Yl = 1 with a heat of vaporization per unit mass of L,, then L = L,  q,(l  Y1,J. For solid propellants, it is usual that L < 0 and > To when equation (38) applies.* An abrupt change from gasphase control of m to interface or condensedphase control occurs when surface adiabaticity is reached. In this sense, even if the conductive energy feedback from the gas is a small but positive fraction of the total amount of heat release that occurs prior to complete gasification, the gasphase reaction controls the burning rate. If the gasphase reaction rate is reduced further, below a value corresponding to surface adiabaticity, then there no longer exists a gasphase solution with an m that is consistent with condensedphase and interface conditions. A “breakaway” phenomenon occurs in which the burning rate is controlled by condensedphase or interface processes, and the gasphase deflagration propagates more slowly than the solidpropellant deflagration. Under these conditions, after the gasphase deflagration has moved away, the gasphase chemistry occurs in a convectivereaction process with negligible molecular transport, anchored by the condensedphase deflagration and analyzable by methods discussed in Section B.2.5, for example. Analyses have been given of this gasphase reaction zone, which no longer influences the burning rate [14], [SO], [Sl]; expressions for the distance from the interface to the region of major gasphase reaction have been obtained by application of explosion theory. The second way in which the derivation of equation (575) can fail is for the thickness of the reactivediffusive zone in the gas to become comparable in size with the thickness of the convectivediffusive zone. This occurs if (T,  7;)/T, becomes of order p’, which would be favored by low overall
* This entire discussion has been subject to the restriction that L is not sufficiently large and positive to require, 7; in equation (38) to be less than absolute zero. If the condensed phase is sufficiently endothermic to violate this restriction, then equation (38) cannot be satisfied, surface adiabaticity cannot be approached, 5, cannot approach zero, and solidpropellant deflagration with gasification cannot occur in the absence of some energy input from the gas phase. In this case the gasphase reaction must always control the burning rate (at least when the burning involves complete gasification); if the surface equilibrium defined by equation (12) applies, then unusual shapes of curves of the burning rate as a function ofpressure are obtained [8], [49].
we find from an overall energy balance that T.. need not be large for a mathematically welldefined deflagration problem to exist. then there is a single gasphase zone in which reaction. For brevity. (39) * Strands are long cylinders with burning inhibited on all faces except one of those normal to the axis. C491.5. and the interface with the condensed phase forms a boundary of the reactivediffusive zone at a finite location in the stretched variable.T. If b is not large. which is readily developed. Nonadiabatic deflagration of solid propellants is of practical interest in many contexts.3. Effects of energy losses may differ for different mechanisms of burning and for different types and locations of losses. C541. Deflagration Controlled by GasPhase Reaction Rates 247 activation energies for the gasphase reaction. [53]. discussions of other systems may be found in the literature [S]. heat losses may be responsible for limits of deflagration. and convection all are important. . The reaction zone in the gas then requires a modified analysis. but m becomes bounded in the limit of an infinite gasphase reaction rate.3 and 5. = T. whereupon the convectivediffusive zone in the gas disappears. To illustrate a few of the phenomena that may occur.)/T. In laboratory experiments on linear burning of strands of solid propellants. . Analysis shows that when equation (575) fails for these reasons. Thus far our discussion pertains to conditions of overall adiabaticity. increasing m (by increasing the gasphase reaction rate) eventually causes (T. but with equation ( 6 ) or equation (29) applicable.4 may be used to analyze the gasphase deflagration in these cases. to become of order b'. the gasphase reaction continues to control the burning rate. then the gasphase reaction zone continues to involve a diffusivereactive balance in the first approximation.3. then under the assumption that this radiation is not absorbed elsewhere in the system.qR/(mCp). Since the presence of the condensed phase has removed the coldboundary difficulty. Enhancement or control of burning rates may be considered by external application of radiant energy fluxes [40]. If q R denotes the radiantenergy flux from the surface.7. let us consider radiantenergy loss from the interface between the condensed and gaseous phases. If fi is large. This same effect occurs with surface equilibrium [equation (12)] if increasing the pressure p is the means for increasing the gasphase reaction rate (but not if p is held constant and the reaction rate is increased instead by increasing the preexponential constant in the rate expression). a process that often is significant in laboratory experiments with strand burners. such applications of these methods have been made [52]. diffusion.* In rocket motors these losses tend to be reduced by energy input from hot surroundings. 0 . and a corresponding modification to equation (575) occurs. attention will be restricted to systems that are controlled by gasphase reaction rates and for which equation ( 6 ) applies. The methods of Sections 5.
where Tm. which corresponds to a system in which the value of . in equation (38) is negative (that is. heat losses affect the burning rate only through their influence on T. In the pressure range where two solutions for m exist.248 Combustion of Solid Propellants FIGURE 7. Therefore. Equation (39) can be derived formally from the general interface energy conservation condition given in equation (161) and the energyconservation equation for the gas and the solid [for example. C. under adiabatic conditions (qR = 0) for the same initial temperature To. a solution no longer exists for m when the pressure p is less than a critical limiting value. and there are two solutions if p exceeds this value. the equation cannot be satisfied) and the overall order (the pressure exponent) of the distributed gasphase reaction is two. T. It may thus be seen in general that whenever equation (575) applies. B. . qR depends on the surface temperature (typically q R is proportional to T f ) . the derivation of which is somewhat complicated algebraically* even on the basis of equation (575). This result. (59)]. The absence of a solution at low pressures is an example of a prediction of a deflagration limit caused by heat loss (see Chapter 8). and D are positive constants.a is the value of T. in both cases it is found that if qR > 0. In equation (39). the increase in qR is obtained by an increase in C. Schematic illustration of the pressure dependence of the mass burning rate when the gasification process is an unopposed rate process. Nevertheless. it is usually assumed that the lower burning rate represents an unstable solution and that the upper is correct physically (compare Sections * The equation to be investigated may be shown to be roughly of the form where A. when q R # 0. . is illustrated schematically in Figure 7. now depends on both Ti and m through equation (39).the situation is somewhat more complicated if the gasphase reaction zone extends to the surface of the condensed phase.2.T.2. in equation (575) for m.
differing according to the equilibrium versus finiterate character of the gasification step in the dispersed phase.1. The consequent occurrence of twophase flow adds substantial complication to the deflagration mechanism. Polyvinylnitrate is a material that appears to burn in a process controlled by dispersedphase combustion. Some further discussion of the function m(p) will be given in the following section. solid rods. given the model of Section 7.7. [SS]. and good agreement between theoretical predictions and experimental observations has been obtained [56]. 7. Dispersion Phenomena and Other Influences 249 3. strictly speaking.3).6.1. then the theoretical problem is more complicated because accurate conditions for the onset or termination of dispersion become necessary in developing analyses with reasonable accuracy. geometric configuration of the dispersion (gaseous bubbles. and other attributes.2. let us introduce the dispersed phase mentioned in Section 7. An example of a propellant in which conditions for onset of dispersion are relevant to the burning mechanism is nitrocellulose. Dispersion might begin as a consequence of attainment of an equilibriumlike condition for transition to dispersion or in a rate process for subsurface generation of gases. since then the problem may be analyzed by asymptotic methods on the basis of purely dispersedphase control. at the interface in Figure 7. are not represented by the model illustrated in Figure 7. DISPERSION PHENOMENA AND OTHER INFLUENCES Let us now consider combustion mechanisms that. Results are available for a few models that have dispersedphase control [13][15].1. and so on).1 at 100 atm [ls].4 and 8. for which it has been observed that the ratio of the energy feedback (energy transferred from the dispersed phase to the condensed phase) to the energy released in the condensed phase varies from about 0.4 for condensedphase processes. The new difficulties encountered are fundamental because the physics of these processes are not well understood. For example. When dispersedphase processes contribute in any essential way to the burning rate. the location of the heat release in the dispersed phase (for example. in the condensed or gaseous component or at their boundaries). liquid spheres. If processes occurring in other zones are important as well.4.3 at 5 atm to about 0. Specifically. species 1 of equation (14) might be presumed to initiate dispersion upon attainment of an equilibrium relationship of the form .6. the problem is simplest if the other phases may be treated as nonreactive and the reaction rate in the dispersed phase is strongly temperaturesensitive. There are numerous possible models of this type.
and n are three positive constants that serve to characterize m and its pressure and temperature sensitivities. At the high pressures encountered in the use of gun propellants ( p on the order of 1000 atm). Theoretical analyses often may provide agreement with experiment m = . for specifying the energy feedbackis needed. Thus a wide variety of complications may arise. and rc./dp). = p(d~. and Yl. and f ( p ) is an increasing function of p. the value of m depends only on the two parameters To and p . then rates of nucleation might be relevant. Measurements of m. Various empirical relationships for m have been developed in thc past. A good theory of propellant deflagration.. small amounts of energy feedback can be significant because of the strong dependences of the exponential factors on q. This function would be proportional to the partial pressure of species 1 in the gas if an equilibrium condition for absorption of this species applies. c. is called an explosion temperature and n is a pressure exponent of the burning rate. and n. B. Temperature and pressure sensitivity coefficients are defined as rcT = (d In m/dTo). and the problem of developing a correct analysis is challenging. In equation (41). representing an energy of nucleation and with B. T. T . T.” If the transition to dispersion is a rate process. These include (a (41) cp”/(T. The identity (dn/dTo). should agree with experiment concerning the values of m. is a heat of solution. which must be less than unity if the propellant is to burn in a stable manner in a rocket chamber.250 Combustion of Solid Propellants where L.. When a given propellant formulation burns in the absence of externally applied perturbations. A third conditionfor example. and n = In m/a In P ) . Equation (40) and results of a condensedphase analysis provide two relationships among three unknowns. is a solubility constant. Although the situation would be simplest if an adiabatic condition (zero temperature gradient) were achieved at the onset of dispersion. Thus a nonnegligible coupling between the reaction zones often remains. and a formula like equation (40) again may be derived. all are of use in helping to ascertain deflagration mechanisms. Much research remains to be done in analyzing the deflagration of most of the homogeneous propellants for which dispersedphase processes are important. rc. applicable for a range of values of To and p .~is a consequence of the definitions. Use of an equation like equation (40) as a downstream boundary condition for analysis of the condensedphase reaction does not eliminate the necessity of analyzing the dispersedphase processes. .To) as well as relationships involving other functional dependences on p [8]. or it might be proportional to the total hydrostatic pressure if the phase transition is influenced by mechanical properties of a solid having a limiting “strength.i. becoming proportional to m2. m. ~ .n. but with L. it is quite possible that the fundamental rate constants for the condensedphase reactions become pressure dependent. respectively.
For homogeneous propellants. for * This is especially true if at least one of the propellant constituents can experience exothermic deflagration in the absence of the other. the factor ( T . Most of the currently used heterogeneous propellants are of this type. These effects may be produced in conventional doublebase propellants by suitable addition of burningrate catalysts (typically certain metalorganic salts) to the propellant formulation. values for which can be selected within reason to obtain good agreement with measurements. There are theories that predict positive values of k different from unity [40]. In recent years an appreciable amount of research has been devoted to the development of comprehensive models that take into account all effects that are known to be potentially relevant. COMBUSTION OF HETEROGENEOUS PROPELLANTS In principle.To)in the denominator may often be raised to a positive power k different from unity without introducing disagreement with measurements. many other phenomenafor example.* Moreover. Model propellants can be considered in which neither constituent can burn without the other. 7. To include all the potentially significant phenomena in a theoretical analysis becomes a formidable task that can be pursued only through the introduction of drastic idealizations for each of the phenomena considered. These theories perform important functions beyond the correlation of existing data. gasphase combustion appears to be of greater importance for heterogeneous propellants than for most homogeneous propellants. It has been shown experimentally that these catalysts usually operate by modifying the interaction between the condensedphase and dispersedphase reaction zones [57]. since measurements can be made only over a limited range of To less than T. Combustion of Heterogeneous Propellants 25 1 concerning c and n without predicting the temperature sensitivity correctly [40]. . [ S S ] . Thus dispersion phenomena are of importance to the deflagration of homogeneous propellants in a number of ways. the occurrence of diffusion flames between fuel and oxidizer constituentsbecome relevant to the combustion process. There are plateau propellants that exhibit an intermediate range of pressure over which m is practically independent of p and mesa propellants for which m(p) achieves a maximum at a particular value ofp then a minimum at a higher value.7. all the theoretical complexities that we have discussed for homogeneous propellants also may arise in attempts to analyze the deflagration of heterogeneous propellants. For these propellants gasphase or liquidphase heat release subsequent to mixing or heterogeneous heat release at points of contact between the two constituents must play an essential role in the deflagration mechanism. such analyses must be deemed incorrect in a fundamental sense.7. In general.7. The results are expressions for burning rates that contain several adjustable parameters.. .
they enable estimates to be made of burning rates of heterogeneous propellant formulations that differ somewhat from those that have been subjected to measurement. and we shall discuss in a little more detail a few of the simplified models that address only certain specific phenomena. In fact. who included a gasphase decomposition flame of ammonium perchlorate. a gasphase diffusion flame was added as well. The principal trend of research on comprehensive models is toward additional complexity rather than toward independent evaluation of the appropriateness of the values of parameters employed. The intent is to develop codes that reproduce burning rates of propellants of practical interest rather than to clarify fundamentals of the chemical kinetics and of the physical processes that occur during deflagration. without addressing questions of dependences on other parameters. fuel pyrolysis. better understanding of these aspects can be obtained (including unforeseen restrictions on complete models). The origins of comprehensive models are usually traced to the work of Hermance [59]. the more recent publications seldom ever even bother to list the values of the parameters that were employed. then we shall make a few comments on the burning of black powder. The criteria for successful models mainly have been taken to be agreement between theoretical and experimental dependences of burning rates on pressure for a variety of propellants involving different binders. This is especially true for rate parameters such as overall activation energies. Later. different oxidizer particle size distributions. The models contain various energy balances and different prescriptions for averaging over sizes and locations of oxidizer particles in the fuel matrix. [63]). Although values of parameters in models have been selected successfully to produce good agreement with measured burning rates. A topic of recent interest has been to account for effects of bimodal size distributions (for example. However. and improved predictions of dependences of burning on certain parameters can be developed. The train of development may be followed in a sequence of publications [60][63]. and a heterogeneous reaction between fuel and oxidizer at their interface.252 Combustion of Solid Propellants example. and so on. we shall consider composite propellants. the relationships between the values so obtained and independently determined values for the fundamental processes that they are intended to describe by and large remain uncertain. primarily with ammonium perchlorate as oxidizer. Here we shall merely cite some literature and reviews of comprehensive models. By focusing attention on limited aspects of the combustion mechanisms. First. The analytical formulations generally are expressed in terms of sets of simultaneous nonlinear algebraic equations that are solved by exercising routines for electronic computers. they tend not to lead to detailed understanding of specific aspects of the combustion processes. and they thereby indicate propellant modifications that may be tried for tailoring combustion characteristics in manners desired in applications. .
and geometric properties that include the particle size and statistical parameters of the particle configuration [65].). By calculating an average time for propagation of burning along optimum paths. constant rates of normal surface regression. in addition. (which depends upon p ) . [66]. Thus. the average burning rate of the propellant can be expressed in terms of the regression rate of the oxidizer spheres. in terms of the mass burning rate of the oxidizer. presumed known. [64]) have been proposed for averaging over these variables to obtain average burning rates from burning rates of individual particles. The simplified model that gives equation (42) helps to explain potential influences of oxidizer particle size and particle loading on propellant burning rates. in which the fuel and oxidizer components were assigned different surface temperatures that served to provide them with equal regression rates. it is necessary that the average surface temperatures differ. constant radius with known. If a pressure dependence of m is to be obtained in a simplified analysis. to characterize the fuel binder as a barrier having a burnthrough time that is a known. This relationship has been taken to be an energy balance relating the energy feedback from a gasphase flame to the energy needed for gasification of the propellant. eters A and E in expressions like m = to achieve the same average values of m / p for each constituent. Various methods (for example.7. is proportional to the average burnthrough time of the binder. The earliest simplified models of composite propellant combustion were models in which pyrolysis laws like equation (6) were applied separately constituents [8]./(A i Bm. . One approach is to characterize the oxidizer particles as monopropellant spheres of a specified. By equating the two regression rates. This observation led to the twotemperature concept. increasing function of the shortest distance between the surfaces of burning and adjacent nonburning spheres and to characterize the configuration of the oxidizer spheres as being nearly a tightly packed hexagonal lattice with a probability density function assigned to a parameter that defines a small departure from symmetry [65]. The model is beneficial in demonstrating how the packing configuration can influence even the pressure dependence of the average burning rate of the composite propellant.. a representative result for the mass burning rate of the propellant is [65] (42) where A and B depend on geometric parameters of the oxidizer distribution within the propellant and on the densities of the constituents and B. [28]. Since the paramto the fuel (F) and oxidizer (0) differ for fuel and oxidizer. a relationship between the two temperatures is obtained.7 Combustion of Heterogeneous Propellants 253 A formidable problem encountered in modeling composite propellant deflagration concerns the statistics of oxidizer particle sizes and locations. and one additional relationship is then needed to determine completely the two temperatures and the regression rate of the propellant. m. then = m m. as needed for steady burning. the average burnthrough time of the binder.
1 for the BurkeSchumann problem. but for purposes of clarifying processes occurring locally. Choices must be made in imposition of an energy balancefor example. [S]. However. the gasphase equations . Another class of simplified models focuses on diffusion flames between gases generated from fuel and oxidizer constituents. This model has been augmented in various approximate ways to include premixed gasphase flames as well [4]. thereby greatly improving agreement with meassured pressure dependences of burning rates of propellants but also preventing detailed analyses of gasphase flow fields from being accomplished with reasonable effort. The former view might be better €or sufficiently finely mixed propellant constituents and the latter for coarser formulations. or it may be considered that the mixing is relatively slow and unimportant and that the oxidizer gases support a decomposition flame that is responsible for the energy feedback. The concept was first discussed in the literature in [28]. [67][69]. The approximations in the gasphase portion of the analysis are essentially the same as those discussed in Section 3. A sandwich propellant is a heterogeneous propellant composed of a series of parallel slabs of fuel and oxidizer. Summerfield [67] first discussed a model in which the rate of diffusion of gaseous fuel and oxidizer to a conical flame sheet above a fuel pocket controlled the overall burning rate of the propellant (see also [28]). Burning occurs on a face that is perpendicular to the planes of the slabs. investigators have often studied a small number of slabsfor example. alternately placed side by side and bonded together. the latter was employed in the original developments [28]. [71]) or close over the fuel or oxidizer components (under nonstoichiometric conditions. Many experimental studies have been made of the combustion of sandwich propellants (see [70] and references quoted therein). An analysis of an infinite array of uniform fuel slabs alternating with uniform oxidizer slabs has been completed in a flamesheet approximation for diffusion flames that either extend from the lines of contact between solid fuel and oxidizer to infinity (under conditions of overall stoichiometry. It may be imagined that mixing of fuel and oxidizer gases is rapid and that the gasphase flame is a premixed flame in the resulting gas mixture. in defining precisely what heats whatand there are consequent uncertainties and inaccuracies in the twotemperature models. [72]).254 Combustion of Solid Propellants the gasphase flame must be premixed. A heterogeneous propellant is approximated by an infinite number of slabs. only one slab of oxidizer and one of fuel or one of fuel between two of oxidizer. The advantage of the sandwich geometry is the simplification in analysis produced by the absence of variations in one of the directions. the general conclusion that different constituents are likely to have different average surface temperatures is an important aspect that has found application in most of the newer modeling efforts. [66]. [28]. To enable investigations of influences of diffusion flames to be pursued most simply. a sandwich model of propellant combustion has been conceived and subjected to a number of studies.
charcoal. the gaseous fuel being treated as inert [74]. theoretical analyses have been performed for a semiinfinite. These heterogeneities result in local unsteadiness of the burning. Although these percentages correspond to stoichiometry for the overall reaction 2KN0. in qualitative agreement with observed decreases in burning rates of heterogeneous propellants with increasing oxidizer particle sizes. thermal conductivity. The analysis predicts a decrease in burning rate with increasing slab thickness.5). then intrinsic oscillations of the propellant combustion may develop [77]. there are many aspects in which the model did not attempt to achieve agreement with experiments performed with sandwich propellants. such as in details of the shape of the burning surface. heat of gasification. Through nonlinear effects the heterogeneities themselves can modify the average burning rate [76]. heat capacity. These oscillatory burning phenomena are discussed further in Chapter 9. and rate parameters may be considered [77]. These analyses have provided some new understanding but have not taken into account potential influences of finiterate chemistry in the gasphase diffusion flamesinfluences that have been suggested [75] to affect burning rates of heterogeneous propellants and that may be treated with help of the asymptotic methods discussed in Section 3. Pyrolysis laws like equation (6) were applied to each propellant constituent. In this model the propellant is burnt on a face parallel to the planes of the slabs.1.7. 3c02. heat of combustion. and sulfur in weight percentages of about 75. However. there is a similarity to the analysis of oscillatory burning of homogeneous propellants (see Section 9. It is a mixture of saltpeter.7 Combustion of Heterogeneous Propellants 255 are solved in a halfspace with surface conditions describing interface species and energy conservation. and 10. 15. The model has no bearing on the occurrence of diffusion flames but instead is a vehicle for studying influences of heterogeneities within the solid on the combustion behavior. while the pyrolysis parameters of the other constituent determined the difference in heights of the fuel and oxidizer surfaces in an approximation in which these surfaces were planar. Black powder is a heterogeneous propellant of unusually complex structure in that three different solid phases are involved.4. [77]. endothermically pyrolyzing fuel slab adjacent to a semiinfinite. Another type of sandwich propellant is the “sideways sandwich” suggested independently in [76] and [77]. endothermically pyrolyzing oxidizer slab [73] and for this same configuration with the oxidizer supporting a gasphase decomposition flame and with the diffusion flame neglected. Heterogeneities in the solid’s density. In efforts to predict surface shapes better. and if mechanisms exist for communication of the unsteadiness to distant portions of the burning surface. and the constituent most difficult to pyrolyze thereby determined the burning rate. timedependent conservation equations describe the burning . 3C S + K2S N. Onedimensional. (43) + + + + .
The normal regression rate of black powder as a function of pressure at 25°C ~831. 0.256 Combustion of Solid Propellants the observed products of combustion are not entirely those of equation (43) but instead include a variety of species such as NO. and the pellets often are glazed with graphite before use. . and very high [SS] pressures. normal regression rates of surfaces of pellets or of tightly pressed powdershave been measured at reduced [S4]. In addition. results are shown in Figure 7. for example. with p representing the density of the bulk propellant. Burning ratesthat is.1 ' I I I I I I 1 0 I00 I000 1 0 . I Blackwood & Bowden o Belyaev & Maznev 0 1 0 Glazkova & Tereshkin Belyaev et al. Noble [78] and Vieille [79]. where the regression rate is Y E m / p .. Detailed experimental studies have been performed by use of more modern techniques [80][83]. 0 0 0 p atm FIGURE 7. rates of spread of flames among arrays of pellets loo I 0. and K. spreading flames rapidly and in a reasonably reproducible manner through a somewhat loosely packed configuration of pellets. with particle sizes between 1 and 100 p.SO. elevated [SS]. Each of the three reactants in equation (43) is present in a separate phase in particulate form. The combustion of black powder has been subjected to scientific scrutiny since antiquity.. contributed to knowledge of its burning characteristics.3.3. for transmitting combustion from the initiator to the main propelling charge in gun propellants) because it provides a margin of safety by being relatively difficult to ignite while maintaining reliability since once ignited. The particles are mixed and pressed into cakes that are ground into pellets having mean diameters typically between 300 p and 3000 p. This ancient art produces a propellant that even today is better suited than any other for certain specialized applications (for example. it burns vigorously even at reduced pressures. NO.
the four drawings illustrate the motions of salt particles at four successive time steps for a situation in which there is multiplication by a factor of three in each step. Melting of S (and possible of KNO. C J is the surfacetovolume ratio (the total pellet surface area per unit chamber volume). Although the theory of the process has not been developed. replaced by u [83]. mainly oxygen. Flame spread among pellets of black powder appears to involve emission of fine droplets of hot salts containing K.4. produced from the decomposition of KNO. and 6 is the void fraction (the ratio of the volume not occupied by the pellets to the total chamber volume). pg is the density of the product gas. A theoretical model has been developed for the rate of normal regression of a burning surface of black powder [87][89]. m is the normal mass burning rate of the propellant.. Combustion of Heterogeneous Propellants 257 have been measured [SO] and found to be much larger than normal regression rates. it appears that this model does not reasonably provide agreement with observed burning rates [91]. Further theoretical and experimental studies of the flamespread processes could help to clarify the extent to which formulas like equation (44) may be applicable. Despite contentions to the contrary [90]. SO. where they rapidly induce local ignitions [83]. There are theories for burning of gaspermeable propellants [92][95]. these produce spread rates on the order of 60 cm/s. with multiplication of the number of particles at each stop through a local surface ignition leading to renewed particle emissions [83]. from a burning liquid layer on the surface of a pellet and impingement of these particles on the surfaces of adjacent pellets. the resulting spread velocity appears to resemble that of equation (44) in some respects.) leading to mixing and exothermic reaction in a melt layer is known to be significant in ignition of black powder [80]. Two candidate mechanisms for theoretical description of the flame spread are the motion of hot gases through the gaspermeable propellant and a random walk of hot K. particles through the propellant matrix. particle velocities on the order of 5000 cm/s have been observed. which may be simplified and applied to flame spread in black powder to provide as an estimate of the spread velocity [S3] I/ = b / P g ) ( d 4 (44) where 1 is a representative length of the propellant charge. The model involves a controlling twophase (dispersedphase) reaction zone in which carbon particles burn in a gaseous oxidant. where u is the velocity of the hot salt particle and 6 is the average distance between surfaces of adjacent blackpowder pellets. .7. No theories have been pursued yet for calculating the regression rate of black powder on the basis of control by condensedphase reactions.7. The randomwalk model is illustrated schematically in Figure 7. At atmospheric pressure. and rates of heat release in a melt layer also may control the rate of normal regression [83]. SO. with m / p .
5.4. More accurate experimental evidence indicates that contrary to equation (45). which was taken to be independent of M [ZS]. The first proposed empirical burningrate formulas were of the form m = mo + k M .8.258 Combustion of Solid Propellants 0 0 FIGURE 7. (45) where m is the local mass burning rate. M is the local average mass flux of gas parallel to the surface (averaged over a cross section of the chambersee Figure 7. Along the downstream surface of the propellant in these motors. below which M has . the average value of the component of velocity parallel to the surface of the solid has been assumed to be zero. EROSIVE BURNING In all the models for the deflagration of solids discussed above. 7. a “threshold” value of M exists. This phenomenon is termed erosive burning. In particular. The twodimensional nature of the process initially forced semiempiricism upon theoretical descriptions of erosive burning. and k is an erosion constant.m is not exactly a linear function of M . However. The consequent increased convective heat transfer to the downstream portion of the charge increases the burning rate in the downstream region. mo is the mass burning rate in the absence of erosion [as given by one of the above models]. (c) (4 Schematic model of random walk with multiplication [83]. the gas velocity parallel to the burning surface can attain high subsonic values.5). practical designs for solid propellant rocket motors usually employ laterally burning charges such as that illustrated in Figure 7.
and turbulent boundary layers are anticipated. and k . Reynolds numbers based on M and on R or z in Figure 7. motor. The idea that turbulent convective heat transfer from the hot combustion products outside the boundary layer provides an additive contribution to the heat flux reaching the propellant surface and.and a number of different flow regimes may therefore be anticipated.k 2 m / M . therefore. which in turn increases the rate of heat transfer to the propellant and hence the burning rate [99]. to the burning rate underlies equation (46) [96] .8. Most of the theoretical . which becomes significant in upstream regions where m is of the same order as M . can be chosen in such a way that the function m(M) agrees with results of reasonably accurate experiments [28]. are independent of mO. to a regime having Reynolds numbers appropriate for laminar boundary layers (see Chapter 12). Schematic diagram of a laterally burning charge in a solid propellant rocket little or no effect on m [28]. to conditions of small crossflow in which boundarylayer ideas are inapplicable. (46) where z is the axial distance from the upstream point at which M = 0 and the (undetermined) constants k . Erosive Burning 259 FIGURE 7.5. ranging from negligible crossflow near z = 0. The prediction that the last term in equation (46) does not depend on m0 is in agreement with experiment [97]. Equations (45) and (46) are only two of many formulas that have been used to describe erosive burning [8]. Most of the formulas that have been suggested are based on physical concepts of influences of crossflow on propellant burning. Among these concepts is the idea that high external velocities produce a turbulent boundary layer (see Chapter 12) on the propellant surface and thereby effectively increase the thermal diffusivity of the gas.M .7. and the values of the constants k . and k . [98]. to a regime in which the Reynolds numbers are well above critical values for transition to turbulence. A burningrate formula that tends to reproduce this threshold phenomenon is [96] m = mo + k l ( M 4 / 5 / ~ ’ / 5 ) e . the exponential factor in this equation is intended to account for reduction in this convective heat transfer through the “blowing” effect of mass transfer from the propellant surface. and z.5 (0 Iz I 1) typically vary from 0 to lo8.
the theoretical problems remain difficult. frictionless. the superscript 0 identifies core conditions at z = 0 (where M = 0). the external flow may be approximated as a steady.parabolic partial differential equations of turbulent reacting flow were integrated numerically across the entire chamber without breaking the flow into a core region and a boundary layer. adiabatic flow of an ideal gas with constant specific heats. no work of this kind appears to have been undertaken. [1001[lo41 by refining or modifying the physical descriptions of boundarylayer flows with finiterate chemistry. with the ratio of the crossflow velocity to the normal velocity treated as a small parameter. in which M* = yp0/[2(y2 . In addition. which are below the threshold for erosion and within which “negative erosion” often is observed (a small decrease in m with increasing M over a range of values of M ) [8].5) in obtaining conditions outside the boundary layer. in a constantarea channel with gas injection normal to the flow direction. In one study [1101. erosive burning of solid propellants presents one of the more challenging problems because simplifications achievable for nonpremixed combustion (Chapter .l)c. these investigations usually provide graphical results rather than burningrate formulas. respectively. numerical integrations of the boundarylayer equations with finiterate chemistry included have been performed for laminar and turbulent flows with erosiveburning applications in mind [lOS][ 1091. represents the value of M at chocking conditions (a Mach number of unity). Equation (47) is used along with the mass balance M = J : (P/A)mdz (where the perimeter P and crosssectional area A are given by 271R and nR2. There have been many newer studies in which attempts have been made to improve burningrate formulas for erosive burning [8]. Although the most recent studies of erosive burning [102][110] have helped greatly to improve our understanding of the process. Fundamental theories of negative erosion might be pursued through perturbation analyses of the deflagration theories discussed in previous sections.(M/M*)2]1’2. a procedure that may be useful in accounting for rotationality in the core [1113. In boundarylayer studies.260 Combustion of Solid Propellants investigations emphasize the latter regimes rather than the conditions of small crossflow. This flow may be shown to be described by algebraic equations [8] such as where y is the ratio of specific heats. for the circular cylindrical grain of Figure 7. and $ = [l . Even in laminar boundarylayer flows. The main difficulties in analyses then arise in attempting to describe the boundarylayer flows.
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Methods for achieving ignition include exposure of the combustible to a sufficiently hot surface. Ignition is the process whereby a material capable of reacting exothermically is brought to a state of rapid combustion. Therefore. extinction. Although ignition. to hot inert gases. to a small pilot flame. to a radiant energy source. to an electrically heated wire. motors. to an explosive charge. they share many common elements. the presentation to be given here will be less precise. Description of these phenomena by theories as rigorous as those presented in Chapters 26 is a formidable task that can be completed only by treating each problem individually. it is instructive to treat them from a relatively common viewpoint. General principles are difficult to extract from detailed analyses of specific problems. and guns. It has long been of practical interest from numerous viewpoints. These methods have been listed here roughly 265 . Therefore. and Flammability Limits A number of classical combustion phenomena are fundamentally more complex than the processes that have been considered thus far. in an effort to expose general ideas. ranging from the desire to prevent unwanted explosions in transportation and storage of combustibles to the need to initiate controlled combustion in furnaces. These phenomena are related in one way or another to processes of ignition or extinctionprocesses that generally are multidimensional and timedependent. Extinction. and flammability limits appear to be highly diverse phenomena. Analyses will be restricted to the simplest illustrative models.CHAPTER 8 Ignition. or to an electrical spark discharge.
Adoption of the energybased viewpoint may be motivated by the fact that energetic aspects practically always are relevant to the phenomena to be studied. including passing the flame through tubes of small diameter (a design principle of flame arrestors). reactant removal. by explosives in large productionwell fires). This fact enables common theories to be developed on the basis of energy considerations. adding sufficiently large quantities of a material (such as water or a chemical fire extinguishant) that slows combustion. quenching. Extinction (quenching) of deflagrations or of diffusion flames may be achieved in various ways. detonation can be initiated directly (see Section 6. General strategies for extinguishment may be listed as cooling. extensive tabulations of limits of flammability have been prepared [l]. such as radical diffusion or surface reactions. There tends to be an inverse relationship between the temperature or strength of the ignition source and the time of exposure required for ignition. [2]. extinction. They are of practical interest especially in connection with safety considerations because mixtures outside the limits of flammability can be handled without concern about ignition. Flammability limits are limits of composition or pressure beyond which a fueloxidizer mixture cannot be made to burn. which serve to correlate a number of different observed characteristics of ignition. Extinction phenomena are of interest in problems of safety and of fire suppression as well as in various aspects of control of combustion processes in industry and propulsion. In so doing. and flammability limits.266 Ignition. but weaker sources require longer exposures. and chemical inhibition. or physically removing the flame from the reactant mixture by inducing high gas velocities (blowing the flame away. For this reason. There are many situations in which analyses of these phenomena reasonably may employ onestep.5). Since processes of flame extinction usually occur relatively rapidly if at all. Rates of chemical reactions always have a bearing on ignition. for example. and flammability limits. Arrhenius approximations to the rates. flame removal. and Flammability Limits in the order of increasing temperatures of the ignition sources. We shall focus our attention here on results explained by energyconservation requirements and heat losses. removing an essential reactant from the system (an approach especially suitable for diffusion flames). we exclude the consideration of special effects associated with finer details of chemical kinetics. practical methods may be placed in one or more of these four categories. Extinction. In extreme cases of strong sources. Meanings of these tabulations and their relationships to ignition and extinction phenomena will be considered here in Section 8.3. strong sources ignite quickly. Seldom ever can energy conservation be neglected in addressing . as accomplished. more emphasis has been placed on ascertaining critical conditions for extinction than on extinction times.2. attention here is restricted to situations in which ignition results in a deflagration or a diffusion flame.
after their removal. “The Flammability Limits of Gases.Br) are added to fuelair flames. the more complicated the analyses tend to become. and Flammability Limits 267 topics in combustion. A. In wellplanned studies of influences of specific aspects of chemicalkinetic mechanisms. We begin in Section 8.5.2 will be seen to be relevant to premixedflame extinction. Canada: University of Waterloo Press. M. but rather involve questions of which of the two is of greater importance. Vapors and Dusts: Theory and Experiment. S.1 and 8. N. The considerations in Sections 8. to quenching distances (see Section 8.3. Babkin. V.* * Morerecent reviews of flammability limits are given by L.6) afford a useful vehicle for analyzing ignition and extinction phenomena. For example.4. replacing it with the less active Br atom. Waterloo. A . the chemical fire suppressant CF.. Lee and C.l). Although lists may be prepared of examples like these that illustrate the significance of specific chemicalkinetic mechanisms. C & F 2 0 . . activationenergy asymptotics were applied to the problem of diffusionflame extinction.4.4. N. V’yun. activationenergy asymptotics (Section 5. It will be seen in Section 8. V.2. + Br removes the very active H atom. There are many situations in which chemicalkinetic details have been established as significant. Guirao eds. and in Sections 3.3 and that discuss the relevant experiments in greater detail. S . .2 and 8. H . under appropriate conditions ignition of a fuelair mixture by laser radiation is appreciably enhanced if the frequency of the light is suitable for dissociation of 0. V. J.4. Current uncertainties lie not at the level of asking whether energetic aspects or changes in chemicalkinetic mechanisms govern the phenomena. Krivulin. mechanisms of reaction of oxygen atoms are important in this ignition process. 259 (1973) and by M . Arrhenius approximation to the chemistry. In Section B.” in FuelAir Explosions.1 with some rough physical ideas and observations that serve to define terms and to relate various ignition and extinction phenomena.3 that the greater the degree of heterogeneity of the system. the remaining influences may be attributed to particular aspects of chemical kinetics.2 are restricted to homogeneous mixtures of premixed combustibles. 1982. the energetic effects are taken into account . and to flammability limits. V.2) for analyzing premixedflame propagation with homogeneously distributed heat losses and next (Section 8. Baratov. Hertzberg. Lovachev. the problem of homogeneous thermal explosions. Bunev. 348.3) in discussing a variety of ignition problems. corresponding ideas were introduced in studying the simplest problem related to ignition theory. thereby reducing the overall rate of heat release.Ignition. and A . The analysis to be given in Section 8.3 and 3. Extinction. A. we shall not discuss them further. then extinction is promoted at least partially because the step H + HBr + H. With the onestep. Here the method will be used first (Section 8. If brominecontaining species (for example. References [3][5] are earlier books that present the material from viewpoints different from that of Sections 8.
6 is the (adiabatic) laminar flame thickness. [ 6 ] ) by numerical integration for slabs of various thickness. since the plane. discrepancies exceeding a factor of 2 or 3 will not be surprising. cp is the average specific heat at constant pressure. Analysis (for example. is the adiabatic flame temperature. other effects). It can also be shown to be roughly equivalent to a number of other reasonable physical statementsfor example. MINIMUM IGNITION ENERGIES AND QUENCHING DISTANCES When a combustible mixture is ignited by heating a plane slab of the gas. Flames will not propagate through very narrow channels because of heat losses to the walls (and. timedependent conservation equations describe the process. po is the initial density of the mixture. a propagating laminar flame develops. A formula expressing the rule is where His the minimum ignition energy. T. shows (for instance. The rule also clearly represents an oversimplified approximation . This ignition criterion is immanently reasonable.. These results and those of various related experimental and theoretical studies (such as [4][8]) can be summarized by the following approximate rule. and Tois the initial temperature of the mixture. is the (adiabatic) laminar burning velocity. When use is made of equation (54) for 6. ignition by means of a hot slab of gas represents one of the simplest conceivable ignition problems. the temperature decays to the ambient temperature by heat conduction without producing ignition. onedimensional. that the rate of liberation of heat by chemical reactions inside the slab must approximately balance the rate of heat loss from the slab by thermal conduction. Extinction. The minimum value of A has often been related to the results of flamequenching experiments. Arrhenius kinetics) that for slabs thinner than a critical thickness.268 Ignition. equation (1) reduces to the statement that the minimum ignition energy per unit area is where . 1is the average thermal conductivity of the gas and u. A minimum ignition energy may be obtained explicitly from equation (2) by identifying a minimum crosssectional area A for the slab.1. and Flammability Limits 8. Ignition will occur only if enough energy is added to the gas to heat a slab about as thick as a steadily propagating adiabatic laminar Jame to the adiabaticpame temperature. while for thicker slabs. it is found that the amount of energy (per unit surface area of the slab) added to the gas must exceed a definite minimum value for ignition to occur. Theoretically. with onestep. initially raised to the adiabatic flame temperature. A is the crosssectional area of the slab. possibly. Although experiments have been performed in a number of different configurations .
and therefore that the rule expressed by equation (1) will be valid. If the ignition source selectively enhances particular steps in . the minimum ignition energy is found to be equation ( H = d2A(T. 2 2 3 In view of equation (54). The results that have been given here for the minimum ignition energy are subject to various chemicalkinetic restrictions related to the nature of the ignition source. ~ (8) Equation (6) correctly predicts the approximate temperature and pressure dependences of the minimum ignition energy. (4) where a(approximate1y 40) is a multiplicative factor that is not strongly dependent on the properties of the system. provided that the slab area A is greater than the area of a square with sides of length equal to the quenching distance (that is. 6. [16]. alternative forms of equation (6) are H =a ’ (6) (7) 6A2(Tm . the results of these heat loss studies agree with other heat loss theories [16].pou~ and H = ~ ~ 6 ~ p . and d evidently is that of a propagating deflagration. When this condition is used in 2 ) . a popular procedure is to confine the combustible mixture between parallel flat plates and to define the quenching distance d as the minimum plate separation for which flame propagation can be achieved. d is determined by the factors discussed in Section 8.To)/c. It is reasonable to assume that multidimensional effects will be small. c . .To)/c. and the thickness 6 of the (adiabatic) flame is given by equation (54). [9][15]. Equations (54) and (4) yield d = aA/. [17] in predicting that [see equation (30)] d = ah.po 00 3 (5) whence equation (3) becomes H = a2A3(Tm.2.1. For systems in which heat losses control the quenching process.To)/u0.8. [5]. The same chemical mechanism therefore must be involved in H if correlations like those of equations (3) or (6)(8) are to be obiained. Equation (3) will determine the minimum ignition energy in terms of fundamental properties of the system only if an expression for the quenching distance d can be found.(T To)./c. [17] and with experiment [4].pouo. When the heat loss is assumed to occur through thermal conduction. A 2 d’). Minimum Ignition Energies and Quenching Distances 269 [4]. The chemistry involved in uo. (3) The approximate correlation between quenching distance and minimum ignition energy expressed by equation (3) is (roughly) substantiated experimentally [4].
For example. personal communication. pilot flames are ideally suited to the approach (because they provide temperatures and compositions in the range assumed). [22]. [28]. it is known that there is a critical electrode spacing giving a minimum value of H [4]. [23]. [25]. Simple formulas to account for increases in the ignition energy by convective gas flow past the electrodes [ZO]. then the basis of the correlations becomes questionable. although the initial temperatures produce ions and radicals and are much higher than the adiabatic flame temperature. [18][29]. Among the ignition procedures identified in the previous section (see also [l8] for a classification). [28]. and hotgas techniques often produce temperatures below the adiabatic flame temperature by amounts sufficient to raise doubts concerning the use of equations (6)(8). Most of the experiments on which the correlations are based are sparkignition experiments. electricalwire. From the viewpoint of chemical kinetics. but when the spark gap exceeds the quenching distance. Sparks add measurable energy rapidly enough for their effects to be characterized in terms of an H . but experimentally it is difficult to introduce a pilot flame rapidly enough into a combustible mixture to avoid nonhomogeneities and associated heat losses that have not been taken into account here. spherical or cylindrical ignition kernels are more realistic. when the spacing is less than the quenching distance. thereby increasing the energy requirement as the spacing is increased. There is an optimum * H. . Emmons. radiationsource. Approximate analyses of spherical and cylindrical ignition sources [191[21] produce expressions that differ from equation (6) at most by a roughly constant multiplicative factor that can be absorbed into a’. this does not seem to exert a significant influence on the chemical kinetics of flame development. [25]. and Flammability Limits 3 the kinetic mechanism. if it involves surface reactions. or if it produces temperatures much higher or much lower than the adiabatic flame temperature. [lS]. the spark may heat a cylindrical region of length equal to the electrode spacing. the required energy for ignition may exceed the minimum ignition energy appreciably because of heatconduction losses to the electrodes. although the actual shape of the region of elevated temperature may be quite complex (for example.270 Ignition. [24]. toroidal regions of hot gas influenced by buoyancy have been observed*). the hotsurface. [23][27]. A considerable amount of attention has been devoted to studies of processes of spark ignition [4]. [28] also have been devised. Extinction. W. [22]. This last effect can be included approximately in equation (7) by replacing a 6 there by the actual electrode spacing [20]. and many facts have been uncovered concerning the mechanism. [24]. Another factor influencing the minimum ignition energy for spark ignition is the spark duration [20]. and by the presence of liquid fuel droplets [27]. [26]. The slab geometry that has been considered here is not representative of most sparkignition arrangements. by turbulence [20].
Thus the minimum value of the minimum sparkignition energy. Methods of analysis The earliest studies of heatloss effects in premixed flames were based on analytical approximations to the solution of the equation for energy conservation [35][39]. critical conditions for ignition are characterized better by an ignition temperature [IS] (the source temperature needed to produce ignition) than by an ignition energy because losses through heat conduction and through igniterinduced fluid flow are substantial. In the introduction to this chapter. [9]. it is of interest to develop the theory of flame propagation with heat losses.[43] and. typically on the order of 1 mJ for stoichiometric gaseous hydrocarbonair mixtures at atmospheric pressure.3. An expression for a will be derived in Section 8. and ignition analyses will be considered in Section 8. Premixed Flames with Heat Losses 27 1 duration for minimum energy. Two such approximations that have been sufficiently popular to be presented in books are those of Spalding (see [40]) and of von Karmhn (see [S]). The material that has been presented in this section is of an approximate. To avoid the complexities of multidimensional analyses.2. more recently. [35]. This fact was recognized in early work [4]. As the heating time is increased.2. generated by the spark. steadyflow model. activationenergy asymptotics [44] . [36]. that propagate away quickly without contributing to ignition [31]. this last loss increases as the spark duration decreases because of a consequent increase in shock strength. we indicated that although changes in chemical kinetics may influence limit phenomena. heat losses to the surroundings of the flame practically always are important. typically on the order of 50 ps. the energy that must be supplied by the ignition source increases because of energy lost from the ignition region by conduction and radiation prior to ignition [30].8. electrically heated wires.2. physical nature and leaves open questions. but a significant amount of energy is also lost in shock waves. Later work involved numerical integrations [I411. For example.2. or pilot flames. In rare instances for spark or glow discharges of very long duration. is attained at particular values of the electrode spacing and of the spark duration.1. hot gases. 8. PREMIXED FLAMES WITH HEAT LOSSES To address topics of flame quenching and of flammability limits more thoroughly. why is the value of a so large? These questions may be addressed by detailed analyses that begin with the conservation equations in differential form. [32][34] and was used in predicting limit conditions [17]. 8.[46]. and especially for heated surfaces. . Analyses of this type are developed in the following sections. the consequences of heat losses will be explored here within the framework of a onedimensional.
(10) (1 1) where the burningvelocity ratio is I* = m/m. it will be found that no solution for the burning velocity exists.7 for others.cpx/A and obtain the equation d 2 z / d t 2 .A.6.6 for this rate function and in Section 5.L d z / d t = . We shall focus our attention on the steadystate temperature distribution. w is the chemical reaction rate (mass of fuel converted per unit volume per second). A is a constant mean thermal conductivity. heat production. Extinction. the nondimensional temperature z has been defined in terms of the initial temperature To of the combustible mixture.To)/(qoYF0). and Flammability Limits Current computational capabilities enable twodimensional formulation to be solved numerically [47]. Thus. it expresses a balance among heat conduction.3. nonadiabatic flame. qo is the heat released in the chemical reaction per unit mass of fuel converted. thus indicating the presence of flammability limits. m is the constant mass flow rate per unit area in the + x direction.. the approach may be described as a thermal theory of flame propagation. + K. activationenergy asymptotics have been applied to the adiabatic version of equation (9) for a particular rate function w . and L is the heat loss per unit volume per second by radiation or conduction to the walls. and heat loss in an element of thickness dx. In Section 5. c p is a constant average specific heat at constant pressure. we introduce the nondimensional streamwise coordinate 5 = m.3. Equation (9) follows from equation (143) and the onedimensional form of equation (140) (with A = constant and c p = constant) provided that the phenomenological heatloss term L is inserted.w A d 2 T / d x 2 .(T . Here we first address a model problem from the viewpoint of asymptotics. the nondimensional reaction rate Awl( Y F o m ~ chas p ) been written as the product of a burningrate eigenvalue . and the initial mass fraction Y. The first objective of the following analysis will be to compute the burning velocity for a simplified model of a plane. Under certain conditions involving nonvanishing heat losses. two burning velocities will be obtained.272 Ignition./. thermalenthalpy convection. if multiplied by dx. x is the coordinate normal to the flame. the burning rate is known on the basis of these results and to employ the known adiabatic mass burning rate ma for the purpose of nondimensionalization. Since equation (9) is the only differential equation that will be used in the initial discussion.3. one of which presumably corresponds to an unstable flame. in analogy with equation (518).. of fuel as z = c. which is assumed to be determined by the equation (9) where the flame is at rest in the adopted coordinate system. Under other conditions. burningrate formulas are given in Section 5. onedimensional. Here it is convenient to presume that for L = 0.mep dTfdx = wqo + L.
and in the first approximation the solution < < .8. for example. is the adiabatic flame temperature. where one constant has been selected to satisfy T = 0 at = . Use of equations (10) and (1 1) in this expression gives cf P = Jwlf . times a suitable power of b held fixed [see. In this case. Downstream from the reaction zone only T constant would be consistent with a convectivediffusivebalance.co and the other to place z = T .). a contraction of the coordinate is suggested by equation (lo). then flamestructure solutions do not exist is of with the present formulation. ~ ( z ) .(dT/dO.TO)/(ROTzf)? Tf P(1 . The heatloss distribution. upstream from the4reaction zone in equation (10) there is a convectivediffusive balance with negligible loss in the first approximation. (12) The expansion parameter is the Zel'dovich number (13) = To + qoYFo/c. and for large fl we expect that there will be a narrow reaction zone centered about the position of maximum T . with IC of order b'.2. co is considered with A. at ~ = 0. where f identifies conditions just downstream from the reaction zone.. an arbitrary selection of the origin of the coordinate system. such that ( = </p is treated as being of order unity. Premixed Flames with Heat Losses 273 A. The limit p . It is found that if ~ ( z )is of order unity or larger over a range of of order unity. at first let us assume that ~ ( z ) order P' everywhere. = f?fm w dx from the fuelconservation equation. and the nondimensional heatloss rate is K(T) = kL/(qoYFO mzC. the expression above equation (575)]. Under the assumption that all the fuel is consumed in the reaction zone. and E represents the overall activation energy. Ro is the where universal gas constant. and the approximate solution < z = zfe": (15) is obtained. of the adiabatic problem [defined by equation (545) for the adiabatic problem. Outside this reaction zone. The heatloss term is analogous to that appearing in equation (B52) and is assumed to be nonnegative and to vanish at the initial temperature (T = 0). the function W ( T ) depends exponentially on P. As exemplified by equation (566).is a critical factor in the structure of the nonadiabatic flame.T f ) = IpmK d< . for example] with a nondimensional function o(T). (14) as a nondimensional representation of the influences of heat losses on the decrease in flame temperature. we may readily derive the expression my. therefore. the reactionrate term in equation (10) will be exponentially small.
To. A matching of this solution to equation (1 5 ) can be written as The form of the reactionrate function is germane to equation (18). we obtain from equation (10) (dy/dq)2 = (2Aa/P) SI.z ) / z J . To achieve agreement with the nonadiabatic version of the theory whose adiabatic reactionrate function is given by equation (566). and Flammability Limits Convective. the nonadiabatic form for a thermal theory possesses a greater degree of arbitrariness than does that for a complete theory with onestep. (17) in the first approximation where a matching condition implied by equation (16). (19) . The effect of diffusion is a perturbation of first order in the convectiveloss zone. which is expected to exhibit a reactivediffusive balance in the first approximation. It thus becomes clear that in the first approximation. which therefore may be called a convectiveloss zone. If.1.1. we may put o = (zf ..u entails investigating the structure of the reaction zone. dy/dy + 0 as y + 0 to leading order. is obtained.z)exp{p(l .z)]}. 0 dy. has been applied.z)/[1 . L is proportional to T .a(l . Schematic representation of the temperature distribution through a flame with heat losses.214 Ignition. The calculation of . then equation (16) explicitly gives z = T f e . Extinction. for example. The threezone structure of the nonadiabatic flame is shown schematically in Figure 8.C U ( p B ) .ReactiveI diffusive diffusive I zone zone I Convectiveloss zone FIGURE 8.an exponential decay of temperature over a length scale having 5 or order B. a convectiveloss balance exists in equation (10) in the large downstream region. Arrhenius kinetics. with y~ = b< being the relevant nondimensional space coordinate of order unity. Just as equation (571) was derived but with y = P(zJ . so that from equation (12) K can be written as (c/P)z with c being a constant or order unity.
for 1 < l/e there are two values of p for each 1. then with L approximated as being linear in T. since equation (14) implies that 1 .2. giving an upper and a lower burning velocity. These are the results that were identified at the beginning of this section. it may be shown that equation (20) always follows from equation (18) to the present order of approximation. where CI = (Kf. we find from equations (12) and (14) by use of equations (15) and (16) that Tf = Zf  2A. (20) Through investigation of complete theories with various other onestep Arrhenius rate functions (for example. plotted in the form of as a function of I.4  I 0 0 . which enables 1 to be calculated explicitly as a function of p. tworeactant systems with reaction orders different from unity). (23) .4 1 FIGURE 8.UP*. The burningvelocity ratio as a function of the heatloss parameter for nonadiabatic flames. Equation (14) may be used in equation (20) to provide an expression for p in terms of a heatloss parameter. (22) The solution to equation (22) for 1 is 1 = p 2 ln(l/p2).L(Tf)/(m"cf). = P2/2) p 2 = eD(l7f).8.2. = ic(zf)/p. whence by use of equation (15) in the integral in equation (14) it may be shown that with the definition which represents a loss parameter of order unity. at 1 = l/eand that there are no solutions for 1 > l/e. Premixed Flames with Heat Losses 215 0. 1 0.zf is of order P'. The result. It is seen that dl/dp = 0 at p = l/& that is. Tf = To + zfqoYFo/cp.2. equation (20) may be written as p 2 = . is shown in Figure 8. From equation (16) it may be seen that (dzldt).2 0.T o ) / K f and . is introduced. If the dimensional flame temperature.3 0. to the lowest order equation (18) then gives (with A.
Spalding took w = (1 .4 [replace cpz . put w constant over a finite range of 5 for which zi < z < 1 and zero otherwise. in defining p . The development that has been presented here is not the most general asymptotic analysis. In these theories.9). with its greater complexity. it also reveals the structural aspects summarized in Figure 8. and Flammability Limits where L(T. Pursuit of this more general analysis for problems retaining the full speciesconservation equations for onestep. is not needed in applications having representative accuracies of 10 %. The asymptotic analysis possesses the advantage that the resulting formulas. it may equally well be written as which shows directly that the reduction in the burning rate is due entirely to the influence of the reduced flame temperature on the Arrhenius factor in the reactionrate expression.) is the loss function L evaluated at T = T. such as equations (24) and (25).1. may be applied more directly with more readily available rate parameters (for example.q in equation (396)]. A generalization of greater fundamental significance would be to formulate the problem employing m instead of m. in equation (23). this permits orderunity departures of T . The doublevalued solution arises through the influence of m on T. E ) .4. the reactionzone equations then differ from those typified by equation (570) and resemble those of the premixedflame regime discussed in Section 3. and the extinction condition is found from equations (12) and (21) to be where equation (13) has been employed in the last equality... The results thereby obtained are quite similar to those derived here. The rate functions considered in early analyses that did not employ asymptotics may be contrasted with equation (19). then the resulting extinction conditions reduce to those derived herein.z)”zm with m and n constants. while von Karma. large values of p may be approximated qualitatively by a large value of m or by zi near unity (for example.q2 by cp . by use of equation (518) it is readily possible to account for a variable thermal conductivity 1.the result is that A is to be evaluated at 7 ’ ’in the formulas that have been given. & from unity and exponentially small ratios m/m. . zi = 0. It appears that generally fi is large enough that the more general analysis. and extinction occurs before the rate of heat loss becomes large enough to impose an appreciable enthalpy gradient within the thin reaction zone. in forming the nondimensional coordinate 5 and T. instead of T. To the order to which equation (20) has been derived. Arrhenius processes reveals that solutions may be obtained when IC is of order unity over a range of 4 of order unity. where ziis a nondimensional ignition temperature.276 Ignition. For example. Extinction. there being a nonnegligible enthalpy gradient within the reaction zone.. If fi is sufficiently large.
2 may be expected to apply.. We shall postpone any further discussion of these stability questions until the following chapter. Flame stability is the subject of the following chapter. In view of the established difficulty in obtaining stable flames on the lower branch. [48]. Premixed Flames with Heat Losses 217 8. there are diffusivethermal instabilities that are influenced by heat loss and that have led to various statements concerning the dependence of the stability in Figure 8. The foundations of the analysis producing Figure 8. with 1 = l/e providing a correct extinction criterion (within about 10 % accuracy since corrections of order 1 / j may be anticipated).2. If the reactant concentration is . Experimentally. It seems sufficient here to reemphasize that if special types of flame instabilities are not observed in an experiment. from equation (22). at least for sufficiently small values of I. it should be emphasized here that the complete stability question is complex. The stability is likely to be influenced by the experimental configuration and by parameters not appearing in equation (22).3. then the upper branch of Figure 8.. a small portion of the lower branch in the vicinity of the maximum value of 1 apparently has been stabilized [36]. having trnfc.p) of order unity (where t denotes time and p o the initial density)..2.2. However. At least for a onereactant mixture with a Lewis number of unity. [49]. in which the operator controls both the massflow rate and the rate of heat loss from a plane flame located above a cooled porous plate. For Lewis numbers different from unity. also suggest stability only for the upper branch [46]. although by means of experiments with a flatflame burner.2 fail on the lower branch when p becomes sufficiently small. Whether both solutions may be observed experimentally depends on the stability of the steady state. this refinement does not appear to warrant development. Analyses in which the flame is allowed to evolve only on a long time scale.2 on the Lewis number [46]. Use of the more general asymptotic approach identified in the preceding subsection can provide results that extend more accurately to smaller values of p. The existence of two flame speeds Figure 8. 8. Static stability arguments have suggested that the upper branch is stable and the lower unstable [36].. the upper branch appears stable. and it is the upper branch that generally is ascribed physical meaning and along which the flame possesses its usual structure. Concentration limits of flammability The dependence of the calculated flame speed on the initial reactant concentrations arises primarily through the influence of the concentrations on the adiabatic flame temperature T. clearly shows the existence of steadystate solutions for two different flame speeds if 0 < 1 < l/e.2./(Lp. it seems quite likely that the entire upper branch is stable and that the practical extinction condition therefore can be identified with I = lje.2.8.
and a critical value of e P E i R o T m may f therefore be identified for extinctions from equation (24). where 4 denotes the equivalence ratio for a fueloxidizer mixture (see Section 5. [2] may be attributed to a larger value of L ( T f )for downward propagation. Extinction. achieves Rich and lean limits are seen to occur in Figure 8.7 xf exp (EIR0Taf) f I 0 I 0. Relevant parameters are exhibited explicitly in equation (24).3.7).3. The evaluation of L(7”) will be considered in Section 8.3 where eE’RoTaf with its critical value for extinction. The comparatively weak variation of I $ causes a strong variation of eEiRoTaf. the remaining factors may be considered constant in any given series of experiments.3.3. .5 1 . In a first approximation.2. exhibiting extinction condition for defining flammability limits. It has already been indicated in Section 5. This enables flammability limits to be tabulated without extensive reference to the experimental configuration [2]. That limits usually are somewhat wider for flames propagating upward in tubes than for flames propagating downward [l]. differences in values of parameters such as L( 7 ’ ’ )between different experiments produce relatively small changes in the limiting values of 4.5 2 4 FIGURE 8. Illustration of the dependence of the adiabatic flame temperature and of the Arrhenius factor on the equivalence ratio. where questions will be addressed relating to the physics of losses and also to the accuracy with which equation (24) follows from equation (21). then the quantity in equation (24) that varies most strongly is rnz. and Flammability Limits varied with the pressure and the initial temperature held fixed.278 Ignition. 0 1.5. An accurate application of equation (24) to the calculation of flammability limits entails accounting for variations other than that of eCEiRoTaf. The situation is illustrated schematically in Figure 8. especially in the wings near the limits. Therefore. mainly because of its proportionality to eE’RoTaf.
The behavior. 8..8. equation (9) may be derived with L = 4uT4/1.2. (26) where o is the StefanBoltzmann constant and 1. Since n > 1 for practically all flames. the righthand side of equation (24) decreases more rapidly than the lefthand side as p decreases. in a sense.2. In this case. From the definitions of B. without heat loss. and of the absorptivity K . It will be seen in the following section that L ( T f ) pm. where m FZ 0 for conductive or convective losses and 0 i m I 1 for radiative losses. values that are appropriate in the vicinity of each limit separately should be employed. and below a critical pressure flame propagation does not occur for any value of 4 . m. then a limiting pressure is reached.In terms of the overall order n (the pressure exponent) of the overall reaction rate. The flammable range of 4 usually narrows as the pressure is decreased. and the limiting equality may therefore be expected to be surpassed at a sufficiently low pressure. a critical value of 4) at which the exothermic chemistry is shut off completely. An even more likely candidate for producing flammability limits that are independent of the apparatus over a very wide range of conditions is a solely radiative heat loss from an optically thin gas. given in . the value of the rate of heat loss is irrelevant to the flammability limit over practical ranges of conditions. Although it is highly unlikely that this occurs. in calculating flammability limits. In cases of this kind (some of which may be envisaged from chemicalkinetic considerations but none of which have been established indisputably to occur for real combustible mixtures). corresponds to a heatloss theory with a very large value of E. the presence of heat loss is essential.5. Premixed Flames with Heat Losses 219 that parameters such as i l and E vary with 4.4. flammability limits may effectively be controlled by chemical kinetics if there is a value or a narrow range of 4 at which the overall rate of heat release decreases abruptly. These observations are consistent with equation (24). is the Planck mean absorption length. below which flame propagation cannot be achieved.   8. p". since then a very small heat loss may produce the same limit as a large loss.2. by use of equation (E50) in suitable versions of equations (115) and (128). by one or two orders of magnitude. Pressure limits of flammability It is often observed experimentally that if the relative concentrations of the reactants and the initial temperature of the mixture are kept fixed but the pressure p is decreased. however. Estimates of heat loss Flammability limits can be truly independent of the experimental apparatus only if there is a critical point (for example. in which the main pressuredependent quantities are mi and L(Tf).
1 molecules. and predicted limits from radiant loss are apparatusindependent. radiation at the ambient temperature is entirely negligible. an exception to this rule may be the ozone decomposition flame. varies strongly with position x in the flame because of the changes in the concentrations and degrees of excitation of the emitters. we note that convergence of the integral in equation (21) requires ~(z) to approach zero as z approaches zero. Joulin has completed the necessary analysis in recent work not yet published. For this reason. We may note that if Azi is small (for example. which might not occur until sizes on the order of meters are reached. is likely to radiate much more strongly than either the intermediate oxygen atom or the product oxygen molecule. in this case. to be used in calculating extinction.T:. and a better approach is to allow I . the pressure dependence is weaker.* * G.5. / 1 . then equation (21) becomes approximately 1 = B I C ( ~ ) A Z ~ where / ~ . It might be expected that chemiluminescent emissions will often be strong but restricted to the main reaction zone. of order lip). not dependent on the experimental environment. until the gas begins to become optically thick. then ic(zi) may be large (for instance. it may be seen from equation (E50) that I . ozone. In addition. the generality of equation (21). in which the reactant. which admits a wide class of variations of L. Extinction. ~ ( qis ) obtained through equation (12) from an average value L in the region of emission. when reabsorption is not negligible.2). Therefore. Typically. and although the corresponding diffusionflame problem has been investigated [SO].5. First. a number of relevant general observations can be made. the asymptotic analysis requires modification in that a radiant loss term belongs in equation (17). Although the needed details of flamestructure information usually are unavailable for real flames. In flames radiant losses often are negligible until a value of z is reached at which radiatively active intermediate or product species are present. is proportional to pressure at constant temperature and relative composition (see Section E. 1/1. These results were employed in the preceding subsection. with the last term viewed as representing absorption of radiation emitted by the surroundings. dimensions of the experimental apparatus do not influence any of the terms in equation (9). . is particularly helpful for use with radiant loss. is a local property of the gas mixture. which. goes to zero in the fresh mixture. is proportional to the number density of emitting In equation (26). If the radiation is dominated by chemiluminescence from an intermediate that exists only over a short range AT about the value z = zi. and Flammability Limits Section E.280 Ignition. in equation (26) to vary in such a way that 1/1. in turn. extinction conditions for premixed flames are unavailable. For radiant loss often this has been achieved by putting L proportional to T 4 . of order unity rather than of order 1/P) while still enabling equation (21) with 1 = l/e.2. An accurate application of equation (21) with 1 = l/e to calculate extinction with radiant loss can be made only if K ( Z ) is known accurately.
wherein it was found that the upstream and downstream contributions were equal (their sum giving the factor of 2 in the equation). appreciable changes in the loss rate usually produce relatively small changes in the limits. the associated energy losses may be negligible in comparison with radiation from major stable products (such as from H. surface [SO]. but if any of them are.3 in discussing Figure 8. in typical experiments these losses are larger than radiant losses. only ~ ( 7 occurs losses anywhere in the upstream convectivediffusive zone will influence 1. [that is. . is 1. Near rich limits of hydrocarbon flames. for spherical particles of radius r. with number density ns. depend on the experimental configuration [l].1 .for example.. as represented by equation (24). Therefore. and that in this case equation (24) may therefore be used with the factor of 2 replaced by 1.2. If the concentration profiles of the products in the flame are similar to those of the normalized temperature and if the rate of radiant emission from the products is proportional to T4. then the rich limits of sooting hydrocarbon flames almost certainly can be attributed to radiant loss from soot. soot is sometimes produced in the flame.)4/(nr.2 or possibly unity. It appears that for radiant losses from reaction products ~ ( 7 is ~ )often appreciably more important than the integral in equation (21). only the loss rate at its beginning can contribute to the reactionzone behavior and to extinction ~ ) in the first term in equation (21)].2t. These emissivity t. convective losses are good candidates for explaining tabulated limits. However. in contrast.( a p 1. The carbonaceous particlesor any other solid particleseasily can be the most powerful radiators of energy from the flame. then we find from equations (12) and (26) that K is proportional to z(z + a .1)5 .1)4 + [(zf + a' . which suggests that radiation emitted downstream from the reaction zone is about five times as important as that emitted upstream in contributing to extinction. and we have indicated in Section 8.3 that near the limits. and surface temperature T. Since precise values of flammability limits usually do.8. Since the downstream zone is convective in character.2.n. = (T/T. they often have been excluded as mechanisms that may be responsible for fundamental limits of flammability. whence 1 in equation (21) becomes proportional to zf(zf + tll . Currently it is uncertain whether any of the tabulated flammability limits are due mainly to radiant loss (since convective and diffusive phenomena will be seen below to represent more attractive alternatives). Premixed Flames with Heat Losses 28 1 Estimates often indicate that although chemiluminescence may provide flames with their distinctive colors. an approximate formula for 1.l)". Conductive or convective losses of energy from the flame necessarily depend on the geometry of the apparatus. The function ~ ( z )is difficult to compute for soot radiation for use in equation (21) because it depends on the histories of number densities and of size distributions of the particles produced . This may be contrasted to the situation in which L is linear in z.O and C 0 2 in hydrocarbon flames). in fact.1)5]/5.) parameters depend on the chemical kinetics of soot productiona complicated subject.
282 Ignition. Conductive losses from the fingers to the cool gas are responsible for the lean flammability limit. the lean limits do not depend on the size of the apparatus.5. for hydrogenrich mixtures that do not experience the instability. On the other hand. of lean methaneair flames that can propagate downward in a tube 2 cm in diameter but are extinguished in a tube 5 cm in diametermay be explained on a similar basis [Sl]. The rate of heat loss per unit volume is then obtained through division by the volume of the element dxnD2/4: . conductive or convective losses never can be consistent exactly with the planeflame assumption that has been employed in our development. Unlike the radiant loss from an optically thin flame. Loss analyses must consider nononedimensional heat transfer and should also take flame shapes into account if high accuracy is to be achieved. For example. The conductive heat loss per unit volume from a plane flame in a circular tube of diameter D can be estimated by the following simple reasoning. the limits are observed to depend on the tube diameter [5 11.5.2.) estimated from an approximate analysis. and they show that diffusivethermal effects (Section 9.2) that leads to fingers of flames separated by a nonreactive. cool gas from which hydrogen has been removed by diffusion [Sl]. The observations thus are consistent with theoretical predictions [52]. The accuracy of the extinction prediction then depends mainly on the accuracy of the heatloss estimate. Consider an Eulerian element of gas of length dx in the tube whose walls are maintained at the temperature To.3) can influence extinction phenomena. [53] that take into account both the instability and the conductive loss. This is difficult to accomplish by methods other than numerical integration of partial differential equations. a mean temperature gradient ( T .)/(D/2). as is normally expected for conductive losses. in hydrogenoxygennitrogen mixtures. vertical tubes experience a cellular instability (see Section 9. hydrogenlean flames propagating downward in open. and the wall area nD dx. extinction formulas that in principle can be used with an accuracy as great as that of equation (21) for radiant loss are unavailable for convective or conductive loss. Unusual observationsfor example.T'. Since the dimensions over which this conduction occurs are independent of the tube diameter. The energy per second conducted to the walls from this element is the product of the thermal conductivity A. Therefore. Rough heatloss estimates are readily obtained from overall balances. The most convenient approach in accounting for convective or conductive losses appears to be to employ equation (24) with L(T. The sizes of the fingers are determined by the instability and are independent of the tube diameter. [52]. Extinction. and Flammability Limits Special sets of circumstances may conspire to produce limits independent of apparatus dimensions even if convective or conductive losses are important.
Premixed Flames with Heat Losses 283 This linear dependence of L upon T is consistent with the derivation of equation (24). we obtain equation (4) from equation (30). Quenching phenomena can thus be attributed to conductive heat losses. as well as on the tube geometry and the type of flow. By substituting equation (28) into equation (24) and solving the resulting expression for D . The dependence L ( T f ) 1/D2 implies that the lefthand side of equation (24) increases as the tube diameter D decreases. for example. at the burning velocity upstream and at the burntgas velocity downstream. Rates of heat transfer to the walls in these various configurations may be estimated by use of heattransfer coefficients.2. which is empirically approximately the same as (perhaps 25 or 50 greater than) the quenching distance d defined in Section 8. with a = J2eph. (28) Typically. Putting fi z 10 . we find   D = J2epbcP/(Am. An approximate formula for the quenching distanced can be obtained from equations (24) and (28). which are obtained from heattransfer correlations that depend on suitably defined Reynolds numbers (or perhaps Grashof numbers) [54]. indicate that b z 15 for circular tubes. (29) Equation (54) implies that equation (29) can be written as D = J2epb6. Neglecting the small difference between the quenching diameter and the quenching distance. In contrast.8. gas velocities in the direction of flame propagation may be influenced strongly by buoyancy and tend to be positive (upward) both before and after the flame passes. the gas velocity relative to the walls is directed from the cold to the hot side of the flame.4) and that L(Tf) l / D z . Equation (28) thus shows that L(Tf)is independent of pressure (as stated in Section 8. Influences of gas motion have been neglected in equation (27). and results quoted in [17] and [36].1. Since none of the other physical parameters in equation (24) depend on D. This minimum tube diameter is called the quenching diameter. for example. in a forced flow that maintains the flame stationary in the laboratory frame. variations in b are relatively weak. the velocity of the gas relative to the walls is approximately zero ahead of the flame and approximately the difference between burntgas and unburntgas velocities behind . These influences may depend strongly on the configuration of the apparatus in which the flame propagates.). for flames propagating upward.2. (30) where 6 is the thickness of the adiabatic laminar flame. It is thereby found that L(T’) = (bA/D2)(T’  To). an extinction condition is reached when the tube diameter D becomes sufficiently small. The results may be described by replacing the factor 8 in equation (27) by a factor b that depends on a suitably defined Reynolds number. For flames propagating downward in open tubes.
then analyses often can be performed on the basis of steadystate conservation . Here we merely identify a few illustrations.2. W. Thus we see that a is large as a consequenLe of two effects: First. 8. There is recent literature in which activationenergy asymptotics have been applied to the steadystate equations for various autoignition problems [55]. Quart.5.284 Ignition.2. introduce one example. Above a critical value of a parameter measuring the magnitude of the reaction rate. Dold. The situation has been discussed in Section B. In addition to specifications of critical conditions for ignition to occur. Mech. to appear. Timedependent conservation equations must be considered if the history of an ignition process is to be studied. If interest is focused on ascertaining critical ignition conditions. second. typically it is found that multiple steadystate solutions exist and that the one with the smallest value of the maximum temperature represents a stable. An example is the autoignition of a equations (for example.4 and an introduction from the viewpoint of asymptotics is available [46].5. and Flammability Limits and b z 15 in this formula gives a z 30. achieved in the preceding section through activationenergy asymptotics. and give reference to reviews for entrance to the literature. Reviews of problems of this type are available (see the literature cited in Section B.3. . this slowreaction solution no longer exists. Problems of ignition by means of an externally applied stimulus have also been introduced from the viewpoint of activationenergy asymptotics [46] . Math. which is not very different from the value a z 40 quoted in Section 8. [56]. there are a number of results concerning ignition times that provide the history of the ignition process. slow reaction. 4 ) .* an introduction to these is available [46].1. the large nondimensional activation energy makes the flame highly sensitive to small rates of heat loss and capable of being extinguished by extraction of a small fraction of the heat released . the convective enhancement of heat loss combined with the geometrically favorable factor for conductive loss cause the loss rate to be about an order of magnitude greater than might be guessed in the absence of a loss model. Section 3 combustible within a container whose walls are maintained at a fixed temperature. Extinction.4). * For an improved analysis see J. and ignition occurs. 4 . (1985). has been matched and in some ways surpassed for ignition phenomena. J. ACTIVATIONENERGY ASYMPTOTICS IN IGNITION THEORY The understanding of extinction phenomena. Appl. There are autoignition problems for which progress is being made in describing ignition histories by asymptotic methods [57][59].
The timedependent equation for conservation of energy for the material. which may be contrasted to the balance appearing in equation (9). Equation (31) may be derived formally from equations (111). is soluble in principle for T ( x . ActivationEnergy Asymptotics in Ignition Theory 285 an extensive review of research in this area that preceded activationenergy asymptotics is available [60]. analogous to equation (9). heat conduction and chemical heat release. after mixing of fuel vapors with an oxidizing gas [72][74]and the ignition of a reactive material exposed at time zero to Newtonian heating [75] to an elevated surface temperature [76]. Let a reactive material occupy the region x > 0. Specific problems that have been addressed by asymptotics include the ignition of a reactive material that occupies a halfspace and whose planar surface is subjected to a constant energy flux beginning at time zero [62]. is pc.8. to achieve the greatest simplicity we adopt a thermal theory. and to avoid complications assume that the material remains at rest and has a constant density p. [71]. the ignition of a solid by a radiant energy flux for situations in which the only exothermic reaction occurs in the gas phasefor example. . (31) where the remaining symbols and assumptions are the same as those of equation (9). t). initially at temperature To. (121a) and (122) by introducing a list of explicit assumptions. the ignition of a solid by processes involving exothermic heterogeneous reactions at its surface [69]. We shall briefly address the first of these problems as a vehicle for introducing the techniques. although in various applications that have been cited the full set of conservation equations has been considered.3. Let the material. [66]. (115). [70]. although coordinate transformations readily enable this assumption to be removed. we shall neglect effects of reactant depletion on the reaction rate and write = p~eE/RoT (32) in equation (31). and a review of applications of asymptotic methods to these problems has been published [61]. [63]. but we shall not do that here. The problem that has been stated here is wellposed in a mathematical sense and. [68]. aT/at  1 a2T/aX2 = wqo. where 1is the constant thermal conductivity of the material. To achieve the simplest thermal theory. ignition of the same material by a radiant energy flux with indepth absorption of radiation [ H I . Equation (31) expresses a balance of energy accumulation. the endothermic gasification of a solid by a constant energy flux [67]. Just as in the previous section. this same problem with heat loss at the surface to an inert material [65]. Consideration of the history (to calculate quantities like ignition times) necessitates retention of time derivatives in the conservation equations. therefore. be exposed to a constant heat flux q = 1 aT/ax at x = 0 for all time t > 0. where A is a constant having the dimensions of a reciprocal time.
Ignition processes often are characterized by a gradual increase of temperature that is followed by a rapid increase over a very short time period. This behavior is exhibited in the present problem if a nondimensional measure of the activation energy E is large. = I + 2&ez’’(4e) z erfc[z/(2&1 =~ ( z01. and where erfc denotes the complementary error function. the time at which the rapid temperature increase occurs. Extinction. a more precise definition oft.) for the inert solution given by equation (33).286 Ignition. t. Let t. Illustration of the solution to the problem of ignition by a constant heat ux. as is true in the applications.4.T. The inert problem. (33) where the nondimensional time and space variables appropriate to the inert problem are e = 4zt/(P~c. (35) respectively.. for example. Then t = RoT:/(ETo. . the properties of which are well known [77].4 for early t. The solution given by equation (33) is illustrated schematically by the curves in Figure 8. denote an ignition time. the material experiences only inert heat conduction because the heatrelease term is exponentially small in the large parameter that measures E. during most of the time that t < t. and Flammability Limits Reactivediffusive zone Transientdiffusive I \\x t Increasing T O . and that can be written as TIT./&) (36) . Let denote T(0. 0 X 8. arises in the course of the development. has a known solution that can be derived by Laplace transforms. with w = 0. In the present problem.) and (34) z = qx/(ATo). 0 F G IRE F 0 X 0.
a quantity of order unity. = To(1 + 2Jec/.) (38) given by equation (33). . for example. and thereafterbecause of the Arrhenius factorthe chemistry will become dominant and cause a rapid temperature increase.. is D. G (q0pLToA/q2)epE'RoTc = I/ .. In view of equations (32) and (33)..4 or to 1/p for the p of equation (13) or of Section 5. (37) whereD.8. simply to select 6 = RoTo/Eand to assume that 8. as calculated from the inert solution. as obtained from equation (34). ActivationEnergy Asymptotics in Ignition Theory 287 is an appropriate small parameter of expansion.To)] is best. The factor T.3. = 1. the additional restrictions then appear in the course of the analysis. A first approximation to the ignition time may be obtained by equating the heatrelease term in equation (31) to either of the other two terms. because equation (33) shows that this factor then approaches 2/n. which may be solved explicitly to give In the rough approximation D.6. from equation (37). use is made of equation (34) and of the solution T. the result is a transcendental equation for t. the temperature . The motivation for writing equation (37) is that the chemistry will remain insignificant everywhere until the maximum temperature. To obtain an ignition time t./(T..6. the ratio of a reaction rate to a heatconduction rate. and T/T0are of order unity. is the value of 0 at t = t. identified with ignition. analogous to the t of Section B. A more primitive approximation. A similar factor has appeared in /3. is a Damkohler number.2./E.. evaluated at x = 0. > To.3.5.. for ignition by a constant surface temperature T.3. becomes large enough for the rate of heat release to equal the inert rate of increase of thermal enthalpy. The only reason for not putting n/2 as a factor in equation (36) as well is to achieve some simplification in the final formulas. Here 0.&) is irrelevant for large values of 8. if less elegant. the inclusion of the additional factor TJ( To&) in the small parameter serves to assure that ignition occurs prior to homogeneous thermal explosion if t is to be small. It is sufficient. that at x = 0. = 1 [in place of the final equality in equation (37)]. obtainable by similar reasoning simply from a nondimensionalization of equation (31). Analogous factors appear in optimum selections of t for other ignition problems. this gives D. The smallness of t is attributable primarily to the necessary smallness of RoT. this cannot be seen until the analysis is completed.the definition t = RoTi/[E(T. as discussed in Section 5.
AlthoughD. According to equation (40). the definition * = C(T/To). Extinction. = 1 is easy to use.. and Flammability Limits plays the role of an ignition temperature.. let s = (6 . with X of order unity in an inner zone and Z of order unity in an outer zone [or.. . To proceed with an improved theory.)/(€~6.~ + .) (0 .. equation (37) gives an ignition temperature that decreases slowly as the ignition time increases. in an intermediate zone. we may investigate the process of transition to ignition by stretching the time variable about t = t. Since it is convenient to work with the difference between the true temperature and that given by the inert solution. . 6) = F(0. since equation (33) shows that T differs appreciably from To when z/. 6)1/(4%) (42) is introduced. = (43) 0. which in turn is appreciably less accurate than the result of a more thorough asymptotic analysis. F(z. In equation (43) and also in the equation in the (2.. it is less accurate than equation (37).O .. ) / 7 + . the ignition temperature depends on the externally applied heat flux but is independent of the heating time .h& is of order unity].s) coordinates. Use of this expansion to achieve a linearization within the exponential enables the combination of equations (31) and (32) to be written in the variables s and X as + a$/as with a$/aX selection =  (a2*/ax2y6= ( I / & ) & + ~ . where F is defined by equation (33). z about z = 0 and 6 = O. more precisely. namely. . Substitution into the differential equation then eventually reveals that space stretching also is needed if space derivatives are to appear at the lowest order in 6 . To consider a small perturbation about the inert solution with a nontrivial expansion of the Arrhenius factor.6.F(z. Solutions may be sought as power series in and a &. Here the (44) 0 as the heatflux boundary condition at X c =1n(DII&&) has been introduced as a first approximation in equation (41) to achieve an appropriate scaling.288 Ignition. is to be treated as being of order unity. the expansion of equation (33) r1 6 . To accomplish this.co (and also as Z + 30). To construct an expansion for small E in the stretched variables. . matching to the inert solution requires that t. 6.) + c. It is found that the variables X = z/(E&) and Z = z/& both occur. in that the reaction is negligible when the temperature is below this value and dominant when above. (41) where c is a constant translation to be selected so that an event best identifiable with ignition occurs at a value of s of order unity. .b + 0 as s + . is needed.
equation (41) shows that c = 0. occurs in a narrow zone at the surface that may be described as a reactivediffusive zone because the time derivative is seen to be of higher order in t there.8. where the chemical heat release causes an accelerating increase in temperature. a thin reactivediffusive zone at the surface. A numerical integration of equation (45) has shown that +(O. s) = co occurs at s = 0. There is an initial stage of inert heat conduction. and equation (44) therefore yields DII= 0.65/&. the equation cannot be meaningful everywhere.431. = $ ( a .4. Equation (45) describes a transient heatconduction problem having a surface heat flux that increases exponentially with the surface temperature. Since we originally defined 8 = 8. ] (45) Investigation of the properties of equation (45) provides the improved formula for the ignition time. The depth of the heated layer and the elevation of surface temperature increase in proporduring the inert stage under the influence of the surface heat flux. The infinity of $ may be described as a thermal runaway that develops in the stretched temperature variable. It is a consequence of the linearization within the exponential produced by the expansion in e and has + 4 .3. Of course. the divergence at a finite t is not contained in the original problem defined by equations (31) and (32). with t given by equation (36). Equation (46) differs from equation (37) by the factor 0.431. but these departures from the inert solution are small. The exponential nonlinearity in the boundary condition in equation (45) is known to cause $(O. Carrying the asymptotic expansion to higher order would produce 1 Lo(&) as a correction factor for equation (46). The view of the ignition process that arises from this analysis is illustrated in Figure 8. followed by a shorter stage of transition to an ignited state. a$pz = e*+' +(z.65/& (46) as an improved equation defining the ignition time. s) to approach infinity at a finite value of s. ActivationEnergy Asymptotics in Ignition Theory 289 twoterm expansion of the inner solution may be developed and matched with the leading order of the intermediate solution to produce the problem a$las = a2$/az2. This incremental heat flux is caused by the chemical reaction that. at ignition.at Z = 0. of order t. according to equation (43). tion to There are two additional zones during the transition stage. It seems natural to identify this runaway as a unique ignition event and to equate the time at which it appears to the ignition time. at larger values of s. s) = 0. and a broader transientdiffusive zone where the additional heat flux caused by the heat release is felt. The surface temperature as a function of time exhibits an inflection and then a runaway during the transition stage.
temperatures much higher than any of practical interest.4. In fact. Other definitions more closely tied to experiment include the time at which a selected. The shortest exposure time that results in satisfaction of an ignition criterion within a reasonable time after shutofffor example. ordinary differential equations in space or time. nogo definition. . the acceleration begins to diminish only when surface temperatures on the order of E/Ro are reached. Thus a great variety of mathematical problems is encountered in asymptotic analyses of ignition. which is characteristic of these problems. there always exists a degree of arbitrariness in defining an ignition time. It may involve partial differential equations as in equation (49. the time at which a specified rate of increase of temperature occurs. sufficiently high temperature is achieved at a specified position in the reacting system. as a consequence of the onset of reactant depletion. now in a material which. The nonlinear driving term of chemical heat release. Extinction.290 Ignition. soon satisfying an ignition criterion according to one of the other definitions given above. and a go.5. the time at which luminous radiant output from the system is first observed. Fundamentally. In reality. These subsequent stages can also be described by activationenergy asymptotics [63]. The nature of the mathematical problem encountered in the transition stage varies with the type of ignition problem considered. Ignition problems typically exhibit a distinguished stage of transition to ignition for small c. near t. the time at which radiation in a selected wavelength band associated with reaction intermediates or products is detected. or integral equations that cannot be reduced to differential equations [76]. nogo definition has been employed for our example problem in an analysis by methods in which the original partial differential equation. and the subsequent history of the system is observed. initially is approximately at the adiabatic flame temperature. the true surface temperature increases at a rapidly accelerating rate over time scales small compared with those having s of order unity. With this last definition. For the problem as formulated. in effect. and this stage must be analyzed to obtain expressions giving ignition times accurately. At very long times the process returns to one of inert heat conduction under the influence of the surface flux. may occur in a differential equation or in a boundary condition [such as equation (45)] and may act over different time and space scales.2. and Flammability Limits been encountered in a simpler context associated with thermal explosions in Section B. the ignition stimulus is applied for a fixed period of time and then removed instantaneously. This go. Often the maximum temperature decreases after the ignition source is turned off and then begins to increase rapidly a short time later. within a period of one exposure timeis then taken to represent the ignition time. the acceleration lessens at much lower temperatures. a flame develops and propagates into the material. on the order of an adiabatic flame temperature. The definition based on thermal runaway that has been introduced here is a mathematical definition embedded within activationenergy asymptotics. Subsequently.
15. U. Explosions. Bureau of Mines. Trans. New York: Academic Press. (1957). Explosion and Combustion Processes in Gases. U S . L.Mech. SOC. E. Washington. S. D R. W. Jr. 8998. Jost. E. Belles.S. This agreement implies that for the problem considered. G. D.. 14. An independence of this type often arises in ignition problems because c is relatively small in ignition. U S . 5. L. 11. Zabetakis. E. Berlad. Potter. 1. Chem. Jr. 1960. 2736. Potter. Government Printing Office. Eng. Putnam and R. Williams. 30. or the system may be close to a condition of transition from one ignition mechanism to another. 16891698. 298 (1959). (1953). 126138. Progress in Combustion Science and Technology. “Flammability Characteristics of Combustible Gases and Vapors. von Elbe. Washington. M. and the resulting ignition time was found to correlate well with equation (46). Jr. 3rd Symp. 58. Am.References 29 1 obtained from equations (31) and (32). However. New York: McGrawHill. Although methods of the type illustrated here may be employed in analyzing these more complex processes. 1264 (1956). Lefebvre. 1951. B. Penner and F.C. SOC. Jones. Spalding. Government Printing Office. New York: Pergamon Press. Ballal and A. 6th Symp. (1977). Lewis and G. U S . 16. F. more than one chemical process may be involved. D. REFERENCES 1. J. P h p . 1st ed. Berlad. Penner. A. and A. Phys. No. A. Cullen... Roy. 5th Symp. Chem. Spakowski. P. 264 (1953). Rosen. the ignition time is practically independent of the definition employed. 1946. A. Aircraft Engineering 25. G. (1965). Simon. 7. 9. F. A. This occurs both experimentally and theoretically and is attributable to the process being more complex than that analyzed here.. E. 728735. (1949). Potter. A. The low temperatures often associated with ignition events can in comparison with lo’ for typical flame and extinction cause c % processes . D. Berlad and A. 4th Symp. thus activationenergy asymptotics tend to be more accurate for ignition. vol. L. Jensen. 273 (1959). there are many ignition problems for which the value of the ignition time depends strongly on the definition adopted. “Limits of Flammability of Gases and Vapors. 352 (1958). 544 (1957). 12. 145181. A.” Bulletin 627. E. 43 (1953). 8. R. and A. 6. B. Coward and G. A. (1955). NACA Rept. 3. (1952). the theoretical problems become challenging. A. 1023 (1954). H. Combustion. H. 10.C. was integrated numerically [78]. D. S. B.” Bulletin 503. 31. 1959. E. Flames and Explosions of Gases. 2. J. Flammability and Ignition. London 245A. 16th Symp. S. . Proc. Jet Propulsion 27. for example. 4. 13. W. M. Detonations. 75. New York: Pergamon Press. Bureau of Mines. Mullins and S.
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68. W. CST 18. Jr. CST 10. B. 43 (1977). 77. (1981). 18071813. T. Kapila. 60. Liiian and F. Acta Astronautica 5. Kindelan and A. (1979). 19. J. Niioka and F. A. Kapila. A. Williams. 41. M. 495 (1981). Mexico (198 l). Kindelan and F. Williams. Liiian and A. A. 1 (1975). A. 1199 (1978). International Journal o f Engineering Science. B. 66. Liiian. 69. C & F 29. A. Williams. Bradley. 61. 73.. CST 6. 259 (1983). 62. A. 17th Symp. 89 (1971). Williams. Williams. 11631171. M. A. Math. 75. 76. A. 261 (1981). A. A. Bush and F. 223 (1972). A. 224227. A. A. 29 (1981). C & F 18. Merzhanov and A. 21 (1980). Kassoy. Averson. A. 91 (1971).References 293 58. A. 65. Kindelan and F. 74. Oaxaca. 67. Williams. H. K. Handbook of Mathematical Functions. M. CST 16. R. C & F 27. Poland and D. Niioka and F. 955 (1975). . 587 (1979). Niioka. A. 78. 36. 71. 445 (1975). 59. 40. 321 (1976). Williams. T. Acta Astranautica 2. G. 18th Svmp. Williams. Appl. Liiian and F. CST 3. A. 47 (1977). 70. 64. Kindelan and F. C & F 16. C & F 50. 207 (1978). T. New York: Dover Publications. Williams. Appl. Stegun. Crespo. CST 2. Niioka. Math. A. 11 (1970). 85 (1972). 39. 63. “Asymptotic Methods in Ignition Theory. M. F. A. Liiian and F. Acta Astronautica 2. 72. SZAMJ. Abramowitz and I. E. Williams. W.” Memoria del VII Congreso de la Academia Nacional de Ingenieria. M. T. SZAM J. K. H. 1965. Williams. Bush and F.
CHAPTER 9 Combustion Instabilities Instabilities arise in combustion processes in many different ways. which are specifically associated with the occurrence of combustion within a chamber. and system instabilities may be associated with feedsystem interactions or exhaustsystem interactions. a thorough classification is difficult to present because so many different phenomena may be involved. shock instabilities. and have been assigned different specific names in different contexts. Chamber instabilities may be caused by acoustic instabilities. In one approach [l]. or fluiddynamic instabilities within chambers. Within each of the three major categories are several subcategories selected according to the nature of the physical processes that participate in the instability. Three major categories are identified : intrinsic instabilities. which involve an interaction of processes occurring within a combustion chamber with processes operative in at least one other part of the system. a classification is based on the components of a system (such as a motor or an industrial boiler) that participate in the instability in an essential fashion. Here we shall try to mention. which may develop irrespective of whether the combustion occurs within a combustion chamber. most of the known instabilities that have been observed and studied. for example. for example. chamber instabilities. Thus intrinsic instabilities may involve chemicalkinetic instabilities. and system instabilities. diffusivethermal instabilities. or hydrodynamic instabilities. at least in passing. more detailed presentation will be reserved for a few of the types that have been investigated more 294 .
Next. which builds on the material presented in Section 7.4. Intrinsic instabilities of detonations were considered in Section 6.4. unexpected irregular histories of the chamber pressure as a function of time occasionally were observed in place of the smooth history for which the motor was designed [2]. Among the areas not covered here is that of intrinsic instabilities associated with chemicalkinetic mechanisms. To be specific we may consider cylindrical chambers of the type illustrated . [ S ] . acoustic instability of solidpropellant rockets.1. We begin by considering a particular chamber instability for which a substantial literature exists. Certain aspects of intrinsic instabilities of diffusion flames were mentioned briefly in Section 3. The final section addresses intrinsic instabilities of premixed flames.1 and will not be revisited. Acoustic Instabilities in SolidPropellant Rocket Motors 295 thoroughly.1. but reviews are available [11.4.5. for example.4. The arrangement of sections does not directly follow the categorization just given. a fundamental topic of central relevance to both laminar and turbulent flame propagation. Section 9. Certain chamber instabilities that are not related to acoustic instabilities (such as Coanda effectsoscillatory attachment of flows to different walls) will not be discussed here. In extreme cases the “secondary peaks” of pressure became large enough to cause structural failure of the motor. another subject that has received extensive analysis. Instabilities that result from soundwave amplification are called acoustic instabilities. will be addressed. diffusion flames appear to exhibit fewer intrinsic instabilities than premixed flames. ACOUSTIC INSTABILITIES IN SOLIDPROPELLANT ROCKET MOTORS 9. an intrinsic instability of solid fuels. System instabilities in other combustion devices are discussed in Section 9.5. Acoustic waves in chambers possess various modes of oscillation.3.3. these subjects are touched briefly in Section B.2.3 concerns chamber instabilities and system instabilities of liquidpropellant rocket engines. ~71). as exhibited in coolflame phenomena.1. [6]. The irregularities often were accompanied by regular pressure oscillations having frequencies comparable with the natural vibrational frequencies of sound waves in the rocket chamber [3] and can be caused by amplification of acoustic waves [4]. as indicated at the end of Section 9. 9. Oscillation modes At an early stage in the development of solidpropellant rocket motors.9. although under appropriate experimental conditions their effects can be observed.2. Extensive reviews of acoustic instabilities in solidpropellant rockets have been published (for example.1.
If p' is known. The equations for conservation of mass. We assume that this condition applies and write the sound speed as a = Jdp/dp. Equations (445) and (446) can be written as aplat + v . To develop acoustic equations for the product gas in the chamber. it remains constant. From equation (449) we see that if the flow is either chemically frozen or in chemical equilibrium.296 Combustion Instabilities in Figure 7.a2V2p' = 0. (3) where the derivative is evaluated at constant entropy and at either frozen or equilibrium conditions (compare Section 4. (6) which follows from equation (2).(pv) = o (1) and aviat + (vp)/p = o (2) if v * Vv is neglected in equation (446) on the assumptions that the mean velocity is negligibly small and that velocity fluctuations are small. quiescent state and neglect body forces and all transport fluxes. (7) .5. respectively. with burning assumed to occur only at the inner surface of the propellant charge and to go to completion in a distance small compared with all characteristic chamber dimensions. (446) and (447). 1 %M v = VV. Then for acoustic perturbations. but by making suitable use of equation (449) we need not retain equation (447). $ (. a velocity potential cp may be introduced such that * i w ~ b ~ C L . we first consider small departures from a uniform.enough for terms quadratic in them to be negligible. a(V v)/& may be eliminated with the aid of the linearization and use may be made of equation (4) to obtain a2p'/at2 . then the entropy does not vary with time along a particle path. P I =  (ima d a t . (5)  which is the wave equation of acoustics. momentum. d p = a2dp. Alternatively.which implies that with p = p(l + p') and p = p(l + p') (where jj and p are constant and where p' and p' are small compared with unity). P ' = YP'.4) in the uniform state. and energy are then equations (449. (4) where y = a2p/jj.which may be shown to reduce to the ratio of specific heats for an ideal gas with constant heat capacities.3. then the velocity field may be obtained from the time integral of the equation aqat =  (p/p)vp'. By taking the time derivative of equation (1) and the divergence of equation (2). and if the entropy is uniform at some time.
each of which is given by the product of(a Bessel function of the radial coordinate g(a trigonometric function of the axial coordinate zka trigonometric function of the azimuthal angle andka trigonometric function of time) The precise form of the oscillatory solution depends. [ S ] ) . subject to these conditions. k = m = 0. is the Bessel function of the first kind of order m. for example.1. .Ykrnn)]. . From equation (9) we see that the lowest (nonzero) frequency corresponds to the fundamental axial mode ( n = 1. Oscillations with only one frequency are monochromatic waves.. . are determined by [bkmn (9) Terms with m = k = 0 ( n # 0) describe longitudinal modes.2. that the normal component of velocity must be zero [and therefore = 0. and they have velocity nodes at nz/l = 0. at the upstream ( z = 0) and downstream ( z = 1) ends of the chamber.. and the (circular) frequencies w k . = a. The method of separation of variables. according to equation (S).. The general oscillatory solution to equation (9. cp also satisfies the wave equation. The derivation of equation (5) may be shown to require that I v/a I be small. as wk.9. on the boundary conditions which must be applied at the ends of the chamber and at the surface of the propellant. tangential modes in cylindrical chambers). those with rn = n = 0 ( k # 0) correspond to radial modes.(a)/da = 0. a m k IS the kth root of the equation dJ. this is called degeneracy and admits an infinite variety of monochromatic wave forms (for example. Bkmn and Ykmn are constant phase angles. namely. 2.O k m n r . longitudinal modes have pressure nodes at nzll = 3../‘ arnkl/~12(nn/02. and those with k = n = 0 (m # 0) represent tangential modes. is [ S ] p‘ = k=O m=O n = O 1 1 Jm(amkr/R)cos(nnz/j) cos(mcp + O k r n n t . 5 have been observed [ 3 ] . . (S) where k. grnk = 0. Frequencies corresponding to tangential modes with rn = 1. Thus each normal mode of oscillation [each term in equation (S)] defines a monochromatic wave. . w = aarno/R)when 1/R is sufficiently small. bkmn and ckmn are amplitude constants. Acoustic Instabilities in SolidBfopellant Rocket Motors consistent with equation (6). Properties of the solution to equation ( 5 ) are well understood (see.. of course. . There are special shapes of chambers for which more than one mode may have the same frequency.. for example. Thus. w = an/l) when 1/R is sufficiently large and to a tangential mode (k = n = 0. shows that solutions representing oscillatory wave propagation in a cylindrical chamber are conveniently expressed as a sum of terms. The simplest boundary conditions are for rigid walls. . m and n are integers. 1. Most of the normal modes describe standing waves. waves having nodal points for the velocity (points where the velocity is always zero) and for the amplitude of the pressure oscillations. . . + .P k m n ) + Ckrnn cos(rncp. . see equation (6)] at the propellant surface (Y = R ) and that (Vp’)norma. . 3. J .
we then obtainfrom a Taylor expansion through second order + . . In some cases.p / p . quiescent state can modify the modes of oscillation. and Ykmn.t /loon).peon). . as may be verified by use of equation (6). .. Multiplying this quantity by the density and using equation (1lo). . The component of velocity in the direction of propagation of a traveling wave is in phase with the pressure amplitude. For these modes. Conservation of acoustic energy To see how damping and amplification affect amplitudes of acoustic vibrations. With the definition p = j(1 p’) and with j j and h representing the values in the uniform state.Ckmn.t . and for velocity at nz/l = +. Between the nodal and antinodal positions. where u = (vl. the boundary conditions influence the solutions [for example. in that if one is proportional to cos(o. Identification of the energy in an acoustic field followed by development of a balance equation for the acoustic energy is a useful approach to the estimation of magnitudes of amplitudes.298 Combustion Instabilities may be found by use of equation (6).. Departures from the assumption of smallamplitude oscillations about a uniform. the pressure and velocity oscillations are out of phase by an amount n/2. The sum of the internal energy and kinetic energy per unit mass at any position and time in a gas is u + v2/2. we see that pressure nodes and velocity antinodes coincide. . if there were an open isobaric boundary. From this example. let us first define the acoustic energy. the amplitude remains constant along cp = f cok.ot/m).1. then p’ = 0 would be appropriate there. Nothing in what has been presented so far provides a basis for calculating the constants bkmn..2. we may treat the thermodynamic quantities p and h as unique functions of p in an expansion through second order about the uniform state. Nevertheless. Since entropy changes are of higher order.2.1.. Frequencies and spatial dependences of amplitudes are less strongly influenced by flow nonuniformities that are the magnitudes of the amplitudes of the various modes. . If m # 0 and either bkmO = 0 or ckmO = 0. as do velocity nodes and pressure antinodes. where h is the enthalpy per unit mass. the results that have been given form good first approximations for use in approaches to the analysis of acoustic instabilities. 9. evidence favoring traveling tangential waves in rocket motors has been obtained [3]. This enables questions of the occurrence of acoustic instability to be addressed by considering mechanisms of damping and amplification of acoustic waves. /?kmn. the other is proportional to sin(o. then the transverse mode describes a traveling wave that propagates in the f q direction with angular frequency okmO (that is. antinodes (points at which the amplitudes achieve maxima) occur for pressure at nz/l = 0. Transverse modes (those having n = 0) represent standing waves if bkmO= & ckmO.3. which may be written as u = h .. Also. and equation (8) would be changed]. we obtain an expression for the energy per unit volume.
spatial variations of mean thermodynamic properties. to second order with p = p(l p’).pv Vp’. although expressions for p’ and v valid to first order may be employed in the equation to evaluate e. By employing these results in the preceding expression.9. The substitution of equation (6) here then gives ae/at = pp‘ ap‘/dt . A conservation equation for emay be developed from equations (l). + (10) with y defined after equation (4). we find that the portion of the energy per unit volume associated with the acoustic field may be written as + + jp‘h/a2 + (Ljp’)’[hdzp/dp2]/2 + ( p ~ ’ ) ~ / ( 2 p+ a~ pv2/2. The local.V * v. instantaneous energy per unit volume in the acoustic field is therefore defined as e = ~ p ’ ~ / ( 2 y ) pv2/2. (1 1) which is the simplest form of the desired conservation equation. where use has been made of equation (3).p . The derivation of equation (11) has neglected the mean flow of gas in the chamber.jp‘ + p v 2 / 2 for the energy per unit volume. Here ph . (4). and it is not counted as an energy density of the sound field. we see that  &/at + pv . Differentiating this result with use of equation ( 3 ) gives d2(ph)/dp2 = l / ( p a 2 ) hd2p/dp2. A similar derivation of equation (10) may be found in [ 9 ] .p represents the energy of the uniform state.1. instantaneous flux of acoustic energy. ) + pp’h + (pp’)2/(2pa2) + pv2/2.(P’v)= 0. in which ap’/at = yap‘/at may be employed by use of equation (4). (6). to second order. Since. we see from equation ( 3 ) that a shorter expression for the above energy is + If this expression were integrated over a volume containing a fixed mass. Equation (1 1) shows that pp’v may be interpreted as the local. Since the linearized form of equation (1) is ap‘/at = . Acoustic Instabilities in SolidPropellant Rocket Motors 299 + pp’d(ph)/dp + ( j ~ [’ d)2 (~ p h ) / d p 2 ] / 2.av/at. The partial derivative of equation (10) with respect to time is aept = ( ~ j / y p’ap’/at ) + pv . then the integral of the first term here would vanish because the volume integral of pp’ is zero. and the rest of the expression is therefore to be associated with the energy of the acoustic field. the first term thus is associated with energy changes that are due to mass changes. and (101. d(ph)/dp = 1 h/a2 in the expression for the energy of the acoustic field. we have pp’ = pp‘ d p / d p (Ljp’)’(d2p/dp2)/2. and . the energy e is a quantity of second order. Equation (10) shows that since p‘ and v are firstorder quantities. Since d h = d p / p under the present conditions according to the definition of h and to equation (449) and the equation preceding it.
boundary conditions may be applied at a nozzle entrance plane having a low Mach number [4]. and the averaging procedure is useful only for high Q.300 Combustion Instabilities homogeneous dissipative effects such as the viscous terms in the equation for momentum conservation.t  fi) is zero for o1# o2. Although the Mach number is not small in a choked nozzle. usually on the basis of expansions for small values of the Mach number of the mean flow. in which V is to be obtained from steadyflow analyses with acoustics neglected and expressions for @ may be derived by considering specific mechanisms of dissipation. If there is degeneracy for a particular o. A conservation equation for ( e ) may be obtained from the time average of equation (12) if the time over which ( e ) varies appreciably is long compared with the averaging time. [17].(p’v) + V .(eT) + @ = 0. and double sums may be needed for ( e ) and (p’v). then a further decomposition of p’ into a sum over degenerate modes can be made. Especially challenging is the task of including flow nonhomogeneities that are expected to lead to refraction of sound waves and to be of significance in real rocket chambers. both ( e ) and (p’v) also may be written as a sum over monochromatic waves because the average of cos(o.t .o. A timeaverage value of e may be defined by integrating over a suitable time period. To avoid a lengthy development of equations. then the integration may be performed over one period of oscillation. The Q of an acoustic cavity is essentially the ratio of the time over which (e) varies to the longest oscillation period. The modified conservation equation then becomes ae/dt + pV . Let angular brackets identify the time average. a situation that usually is . A number of studies have been directed toward investigating the interaction between the sound and the flow [lo][16]. that is. phenomenological manner by adding to equation (11) the divergence of the rate of convection of acoustic energy by the local mean velocity V and the local instantaneous rate of dissipation of acoustic energy per unit volume @. If the acoustic field is monochromatic. If it is a superposition of monochromatic waves. then the integration is extended over a time long compared with the longest oscillation period. all cross terms average to zero. but wave interference may prevent ( e ) from being expressed as a single sum over degenerate modes. To take these effects into account by starting with the full set of conservation equations is a complicated problem that has been addressed partially in the literature from various viewpoints. With p’ represented as a superposition of monochromatic waves. the average acoustic energy is ( e ) . with use made of special analyses [18][21] of acoustic waves in the nozzle flow for ascertaining the appropriate boundary conditions. we may include effects of mean flow and of homogeneous dissipation in an ad hoc. the simple additivity of ( e ) is lost.
(16) where go is the value of 2 at t = 0. p(p'v) n d d   s.e2"'. The acoustic admittance A clearer interpretation of the boundary work may be obtained by neglecting convection and homogeneous dissipation and by focusing attention on a monochromatic wave field of frequency w. e V * n d d S . the average of equation (12) is d(e)/dr + pV*((p'v)) + V.((e>V) + (0)= 0. pp'vndd  S . For . The first term on the righthand side of equation (14) is the rate at which the boundaries do work on the acoustic field. Space averages of e also may be defined by integrating over a fixed volume V of the chamber.1. they almost invariably refer to time averages of the type indicated here.9.3. Equation (14) shows that the homogeneous dissipation. QdY. With the restriction to high Q. and define an amplification rate a by sv a= [. Depending on the sign of a. Acoustic Instabilities in SolidPropellant Rocket Motors 301 encountered in practice. if a remains constant. the net convection of acoustic energy across the boundary. Let the volume average of (e) be 2 = (e) d V / l v . the balance like equation (14) for 2 gives 2 = c. (15) Then. The volume average also may be applied to equation (13) to obtain an equation like equation (14) for (e). the convection term vanishes if the acoustic energy convected into the chamber is convected out at the same rate. (14) where n is the unit outwardpointing normal vector at the boundary and the area integrals are carried over the entire boundary.1. A boundary at which a rigidwall condition (5 * n = 0) or an isobaric condition (p' = 0) is exactly applicable clearly has (p'v) * n = 0 and therefore no boundary work. (e) 5 n d d 9 J'. d edV =  S . The problem of evaluating acoustic instability then reduces to the problem of calculating a. the acoustic energy in the chamber either increases or decreases exponentially with time. we shall be concerned mainly with the first and the third. Acoustic instability therefore may be considered to occur when ct > 0. 9.S . Use of the divergence theorem in equation (12) shows that dt f. (13) When balance equations for acoustic energy are used. and the boundary work all influence the average e in the chamber. (@) dV]l(Ziv). Of the three contributions to a that appear in equation (15).
an increase in pressure is associated with a positive outward velocity in the former case and with a negative outward velocity (a positive inward velocity) in the latter. where v n and p’ are given by equation (19). = Vei(wtY) (19) with the understanding that the real parts of these expressions represent the physical variables.y). The admittance and its reciprocal. . The average rate of work done per unit area on the acoustic field at the boundary point then is   (17) p(p’v) . On the average. It can be shown.y is the phase difference between pressure and outwardnormal velocity oscillations. are their constant phase angles. respectively.4 2 < 6 < 4 2 and positive. for example. corresponding to energy removal from the vibrations at the boundary. that a traveling wave incident on the boundary is reflected with a diminished amplitude if Re(9Y) > 0 and with an increased amplitude if Re{Y} < 0. play many roles in analyses of monochromatic wave fields [22]. We see from equations (19) and (20) that  the real part of which has the same sign as cos 6. With this notation. which is defined as the ratio of the complex outward velocity perturbation to the complex pressure perturbation. where Re{ } denotes the real part.302 Combustion Instabilities monochromatic waves.p) cos(ot  y) dt(w/2n) = . Suppose that at the boundary point of interest ‘ cos(ot . (18) where 6 = p . and p and y. Equation (17) may be written as = prei(wtP). This is negative.p).PP’V Jozz’w cos(ot . the normal specijic acoustic impedance. where the constant P‘ and V are the positive amplitudes of p’ and v n. the boundary work depends on the phase difference between p’ and v * n. boundary conditions near velocity nodes are expressed most easily in terms of the complex acoustic admittance 9/ of the boundary. The average rate of energy input per unit area to the acoustic field is found from equations (18) and (21) to be expressible as P (p’v) * n =  [(pP’)z/2]Re{CiY}. Complex representations of acoustic waves are convenient for many purposes. . if .n = .(PP’V cos 6)/2. if rc < 6 < n/2 or 4 2 < 6 I rc. corresponding to energy addition into the vibrations at the boundary. p’ = P v*n = V cos(ot .
and y = 0 may be introduced as a first approximation at these boundaries in analyzing the wave field. thereby facilitating amplificationrate estimates. This enables us to obtain a simplified expression for P for monochromatic waves. a=  (yu/2) L IPI2 Re{y} dd/ lPI2dK v (29) where the definition in equation (23) has been introduced. thus. From equation (20) we see that y = 0 at a rigidwall boundary and y = 00 at an isobaric boundary. (25) and the relationship for V. (27) where equation (26) and the definition of y following equation (4) have been employed. the amplitude measure appearing in equation (28) is the same as that in equation (22). (28) where ] P I 2represents the square of the magnitude of the complex pressure amplitude. Since I P I = P' at the boundary according to equations (19) and (24). it may be shown that the 2 defined above equation (15) is expressible as 2 = PJvIPI2dV/(2yV) = p L IV*VldV/(2V). The identity V (PVP) = VP VP . Equations (22) and (28) may be used in equation (15) to show that for conditions under which V = 0 and = 0. then iwv =    (j/P)VP (26)  J v (pP2/y)d V + Jv (PV V) d V = 0. where the complex amplitudes P and V are functions of position. both large and small values of the magnitude I y 1 may be expected to be found at various positions within a chamber. then substitution into equations (5) and (6) yields the Helmholtz equation for P. If the complex representations p' = Re{Pe'"'}.obtained by use of equation (25) implies that if either P = 0 or V n = 0 at all boundaries.1. By use of equation (24) and the result given in equation (27) in the definition of e that appears in equation (lo). Acoustic Instabilities in SolidPropellant Rocket Motors 303 An appropriate nondimensional measure of the admittance is Y = +v/4 (23) in which p/u is the characteristic impedance of the internal gaseous medium. . lyl < 1. v = Re{Ve'"'} (24) are introduced. V2P + (w'/u')P = 0.9. At solid boundaries like the propellant surface in rocket applications.P2w2/u2.
a dependence consistent with equation (16). Therefore. if lyl were of order unity. Studies of boundary effects on acoustic instability in rockets therefore involve expansions for ( y ( < 1. The approximate constancy of CI as oscillations grow or decrease in magnitude arises from the cancellation that results from the presence of I PI2 in both the numerator and the denominator of equation (29). which are small when [ y1 is small. We shall not discuss these modifications. Since the derivation of equations (15) and (16) implicitly required I c1I 6 w. Therefore. 9. In equation (28) it may be considered that 2 varies with time only because the pressure amplitude I PI is proportional to eat at every point in the chamber.1. the main task in analyzing influences of boundary work on amplification or damping of acoustic energy may be viewed as that of finding the real part of the acoustic admittance at the boundary. In addition to the growth or decay associated with Re{y). then the boundary would be well matched with the acoustic cavity. (30) where Re{y} is obtained from a suitable average of the nondimensional admittance over the boundary area. If amplitudes of oscillation become sufficiently large.1. Relative importance In the linear range. Im{y}. we see from equation (30) that IReol6 1 is needed for the approach adopted to be valid.4 Damping mechanisms 9.1. there are? modifications to the natural frequencies of vibration associated with the imaginary part. and . the fact that energy densities averaged over a cycle are additive may be considered to justify application of the present results separately to each frequency for acoustic fields composed of a superposition of monochromatic waves. and all the acoustic energy could be transmitted through the boundary in a time on the order of an oscillation period. equation (29) shows that CI M o Re{y}. results for the CI of equation (15) may be obtained separately for the various mechanisms of damping or amplification. Natural vibrational frequencies of sound in the chamber [see equation (9).304 Combustion Instabilities The contribution of the boundary work or of radiation of acoustic energy through the boundary to the rate of amplification of the acoustic field within the chamber can be estimated more readily from equation (29) than from equation (15).4. for example] are on the order of w z u d / K since V / dis a characteristic chamber dimension. Although attention here has been focused on monochromatic waves. and departures from the exponential dependence on t develop. then nonlinearities begin to become important.
for example.2. Chemical relaxation processes in the gas may produce small contributions to damping.1. p . then special damping devices (related. Damping mechanisms provide negative contributions to a. Losses through the choked end nozzle often are most important for acoustic modes that have longitudinal components. Many additional damping mechanisms may be envisioned under various circumstances [7] . and there is a useful summary in [12]. and ij to vary with the streamwise distance z through the nozzle. but homogeneous gasphase dissipation through viscosity and heat conduction generally is entirely negligible except at high frequencies. and these particles can provide appreciable damping. if problems of acoustic instability are encountered. The propagation of longitudinal acoustic waves in choked nozzles has been analyzed on the basis of the onedimensional. 9. Solid propellants often have fine condensed particles in their combustion products. Acoustic Instabilities in SolidPropellant Rocket Motors 305 the values of a for each may be added to assess the stability. and viscoelastic damping within an internally burning propellant grain then may become significant. There are many mechanisms of acoustic damping in chambers. p = p(l + p')] for the streamwise velocity u as wellthat is. Here we shall briefly consider theories for each of these effects. steadyflow nozzle analysis [20]. beginning first with processes of boundary damping. especially for modes having radial components. where it may be responsible for the general absence of very high modes. The chamber walls and the propellant itself can participate in the oscillations. A somewhat more thorough presentation is given in [7].9.3 for definitions of these damping devices . u = V(1 + u')and by allowing the mean quantities p.4. to the acoustic liners [23][26] or baffles [27] that have been used for sound attenuation in liquidpropellant rocket motors and in other equipment) may be employed. in a manner presumed known from a quasionedimensional. timedependent forms of equations (445) and (446) by introducing linearizations of the previously indicated type (for example.* We shall not address these topics further. The perturbation equations ap'lat + ij(ap'/az + au'/az) = o auyat + aul/az = pi (31) 2u7 d q d z ~ / ( p i j )a ] and  ppz (32) * See Section 9. Viscous and (to a lesser extent) heattransfer processes at the walls can provide nonnegligible contributions to damping for chambers with relatively large wall areas.1. Nozzle damping.
In terms of the hypergeometric function F . the constant multiplying of the singular terms may be set equal to zero.x ) d 2 P / d x 2. Handbook of Mathernaticul Functions. it may be shown that when 1 7 is linear in z . Abramowitz and I.x). and the differential equation x(l .2[1 + ik/(y + l ) ] x d P / d x . The nozzle throat is a singularity of this system because 3 = u there. If 6 is a linear function of z. threedimensional nozzle calculations have also been performed [29].z m t . where M = fi/u is the local Mach number. where (36) k = N z .306 Combustion Instabilities are obtained. c. Methods of numerical integration are available not only for these quasionedimensional equations but also for twodimensional equations that allow for modes having components that are not longitudinal [28] . 1965 . With the subscript t identifying throat conditions.l)(dF/dz)P = 0. and the condition that waves not be transmitted upstream from the supersonic section of the nozzle translates into the requirement that the solution in the subsonic part remains regular at the throat. the arbitrary constant in the regular part of the expansion of the solution may be assigned any convenient value. A. New York: Dover.* where c = 1 + * The notation here is the same as that of M.1)M2]. in which equations (4) and (24) (with v replaced by u') may be employed to derive the pair of firstorder ordinary differential equations yodV/dz and yV dVidz + fidP/dz + i o P = 0 (33) (34) + (u2/V)dP/dz + y(2du/dz + iw)V .El). in which the subscript 1 identifies conditions at the nozzle entrance. . b .[ik(l + ik/2)/(y + 1)]P = 0 may be derived. that would apply if the nozzlechamber interface were to occur at that point. then x = (U/Ut)2 = (y + 1)M2/[2 + (y . defined in equation (23). then equations (33) and (34) may be reduced to the hypergeometric equation [20]. with Y = (fi/U)(V/P) (35) evaluated at each point to obtain the local nondimensional admittance.(y . Stegun. 1 . the solution to this differential equation that remains regular at x = 1 is F(u. and a numerical integration may then be performed in the direction of decreasing z . Subtracting equation (33) from equation (34) yields an expression for V that can be substituted into equation (33) to provide a secondorder differential equation for P. Equations (33) and (34) may be expanded about the throat.
(y . which generally is small. expansions for large and small values of k may be obtained more generally from equations (33) and (34). that are of greatest practical interest may be obtained from the expansion of F for small value of x [ZO]. On the other hand. This solution 1 + ik)P .3. The last of these results is of greatest practical interest because [as seen from equation (36) for small MI] k is the frequency made nondimensional by the ratio of the length of the subsonic portion of the nozzle to the sound speed at the throat and is therefore roughly on the order of the ratio of the subsonic nozzle length to the chamber length. [31]. as a function of the nondimensional frequency k for various values of the nozzleentrance Mach number M . that Re{y. from equation (35). and nozzle losses become large.1. a b = 2[1 ik/(y l)] and ab = ik(1 can be used along with the expression I/ = [ ( y  + + + + ik/2)/(y + 1).1 for y = 1.X)dP/dx]/[(2 + ik)y] to calculate y.2 for longitudinal modes in a nozzle having a velocity linear with distance [20]. invalidating the approach of Section 9.} is small. Also.1.9. Acoustic Instabilities in SolidPropellant Rocket Motors 307 0 2 k 4 FIGURE 9. The result is shown in Figure 9. and that Re{y.} > 0. It is found from the solution for V linear in z that Re{y. The real part of the nondimensional nozzle admittance yy. It is seen from this result that for small M I .Re{y.( y + 1)(1 .1./M. without the restriction to a linear variation of V with z.} begins to become of order unity. for long nozzles or for values of M I approaching unity. Re{y. There exists a degree of experimental verification of the predictions [30].1. as assumed in Section 9. Transverse modes are predicted to be much less strongly influenced by the end nozzle than are modes with longitudinal components . Expansions of y. for the small values of M . with y = 1.} approaches M.3 and changing the wave form within the chamber substantially.2.} approaches l/y as k approaches infinity.1)/(2y) as k approaches zero.
Neglecting locally the effects of density changes and the spatial variations of acoustic amplitudes. with the coordinate system locally aligned in the direction of velocity oscillation. the oscillatory boundary layer at the wall is much thinner than the meanflow boundary layer [37]./T. from equation (38). the gas temperature in the chamber. so that the pressuregradient term will be cancelled by a noninertial effective bodyforce term in momentum conservation.1. where equation (24) has been employed for the acoustic field in the chamber. Wall damping Damping by wall friction may be addressed on the basis of the theory of oscillatory boundary layers [35]. we write the combination of equations (12) and (15) for the velocity u parallel to the wall as P w W d t = a(Pw W a Y ) / d Y . [36]./T.308 Combustion Instabilities [21] and might even be amplified slightly by the nozzle interaction. Here the subscript w indicates that the density p and viscosity p are to be evaluated in the gas at the wall. 9. and the tangential acoustic velocities just outside times those outside the meanflow the oscillatory boundary layer are (TWIT.3. (37) where a noninertial coordinate system has been employed in which the wall oscillates and the gas just outside the oscillatory boundary layer is at rest.4.is the wall temperature and T. and y is the coordinate normal to the wall. the rate of energy loss by a pistonlike mechanism is roughly pal P I 2 d 2 / l 2 . for a small subsonic vent of area d radiating energy from a chamber mode having its acoustic velocity perpendicular to the vent axis. The solution to equation (37) is readily found to be (38) v = (T. whence u = (Tw/TJ Re{Ve'"'} at y = 0 and u = 0 at y = co are boundary conditions. where 1 is the wavelength of the mode and the amplitude 1 PI is evaluated at the vent location. the timeaverage rate of energy dissipation per unit wall area can then be shown to be ' + This outline of a theory for wall dissipation shows first.)Re(Vexp[icot .) of velocity oscillation parallel to the surface.) boundary layer.(1 i)Jwyl). that the thickness of the oscillatory boundary layer is on the order of . where T . Under conditions in real motors. There is a body of literature on acoustic radiation from subsonic orifices [101[12]. [32][34]. Dissipation in the oscillatory boundary layer may be analyzed by considering a flat element of the surface exposed to the complex amplitude V (T'.
Acoustic Instabilities in SolidPropellant Rocket Motors 309 which practically always is less than 1 mm. for example. since a / o is the wavelength that determines the velocity gradient associated with the sound field.1. Since the constant C usually is less than unity. in the lower modes the ratio dimension. shows that the ratio of the rate of dissipation of acoustic energy by the oscillatory temperature boundary layer to that by the oscillatory velocity boundary layer is approximately C(a/y)’(IPl’/I VI’). &. of homogeneous damping to wall damping is on the order of the square root of the ratio of a mean free path to a chamber dimension. 9. 9.l)/y rather than to I Vl. as is V / d .1.1. which clearly is a small number under all conditions of interest. If the wall temperature remains constant. equations (E27) and (E34)].4. Usually the solid does not participate appreciably. where C = (y . From this estimate and equation (39) we see that the ratio of the homogeneous rate of viscous dissipation to the rate of viscous dissipation at the walls is roughly J[p/(pu)](w/u) ( w / a ) ( V / d ) .5. a/w is of the order of a characteristic chamber Therefore. The dissipative energy flux is seen from equation (39) to increase with the frequency in In the same way that acoustic velocity oscillations proproportion to duce an oscillatory velocity boundary layer. To see what those special conditions are we may first consider undamped oscillations in a onedimensional.4.4. 1 and c p are the thermal conductivity and the specific heat at constant pressure for the gas. for viscosity. The proportionality of this indicates that high modes can be relatively strongly damped ratio to 03/’ by homogeneous viscous dissipation. The amplitude of acoustic temperature oscillations is proportional to IPI(y . wall dissipation by velocity oscillations usually is greater than that by temperature oscillations. then an analysis of the temperature oscillations. analogous to that indicated above for the velocity oscillations. Homogeneous damping The homogeneous rate of dissipation of acoustic energy per unit volume by viscosity in the gas is of the order of pl VI’/(a/w)’.l ) ( T J f w ) d K in w which . so long as the solid temperature does not exactly follow the temperature oscillations of the gas (which is usual because of the greater thermal capacity of the solid). but under special conditions it does. Here p / ( p a ) is on the order of a molecular mean free path [see. while for lower modes.9. twomedium system having . d . acoustic temperature oscillations give rise to an oscillatory temperature boundary layer at the wall. Solid vibrations Homogeneous dissipation within a viscoelastic solid propellant can produce significant damping if the propellant participates in the oscillations. Similar estimates can be made (with similar conclusions) for homogeneous dissipation by heat conduction between temperature peaks and valleys of the sound waves.
solutions to equation (40) for R = 10 and S = 3are shown by the solid lines in Figure 9. R is on the order of lo3 and S is on the order of unity.2 are frequencies for gas modes that correspond to vibrations of the gas only (with zerodisplacement conditions applied at the propellant surface) and frequencies of solid modes for solid vibrations with freeboundary conditions applied to the solid at both of its surfaces./a be the ratio of the sound speed of the solid to that of the gas.310 Combustion Instabilities gas in the region 0 < z <f l and propellant in the region f l < z < 1. .a. Typically. f FIGURE 9.2. Letting R = (p. z =f l . and we enforce zerodisplacement conditions (dp’ldz = 0) at z = 0 and at z = 1 as well as equaldisplacement and equalpressure conditions for solid and gas at their interface.4 0.2 0. where 1 is the length of the cavity and f is the fraction of its volume occupied by gas [38].)/(pa) be the ratio of impedance of the solid to that of the gas and S = a. where A = cos (“:f)/ cos ~ [‘““h.2. where the relatively small value of R was selected to enable the relationships among the curves to be seen more easily. with the a for the solid representing its dilational sound speed. we may readily derive the equation for the natural vibrational frequencies. Although the wave equation for the solid involves two sound speeds [7]. Wl  2aa First solid mode 0 0 1 1 1 0. for simplicity we may apply equation (5) separately to each medium.8 I.6 0. twomedium system [38]. Natural vibrational frequencies as functions of the fractionf occupied by gas for a onedimensional. t ’ ] is the ratio of the pressure amplitude of the oscillation in the solid to that in the gas. Also shown in Figure 9.
With R large. where n is an integer. A number of analyses of influences of solid vibrations [38][41] contribute to the understanding of their unique attributes. partly because of viscoelastic damping but mainly because their freeboundary (constantpressure) interface condition removes the major source of amplification (see Section 9. For values off such that oscillation frequencies nearly coincide for a gas mode and a solid modenamely. equation (40) shows that if A is of order unity. we see through equation (10) that for solid modes the acoustic energy per unit volume. if it is not true that o l f nnu.f ) z (m + $)fSmore careful investigation of equations (40) and (41) is needed. we should focus our attention on gas modes. and we see that the oscillations of the solid are likely to be negligible. Therefore. Resonance between gas and solid oscillations occurs at mode crossings.3. then equation (40) requires A to be large. Since the gas fraction f in a rocket chamber increases with time during burning.1. is much larger in the gas than in the solid (that per unit volume is comparable). e/p. At resonance. n(1 . Relaxation damping Homogeneous dissipation by chemical or molecular relaxation processes in the gas may be addressed on the basis of a formulation like that given in Section 4. the resonance may be responsible for an intermittent disappearance of instability. e. As f is varied continuously. while [for example. appreciable acoustic energy from the gas is transmitted into the solid and may be dissipated there viscoelastically.f ) z (m + $) naS with m an integer. but the frequency eigenvalues never cross.4.1. while for gas modes the acoustic energy per unit mass. This condition defines gas modes. is comparable). Solid modes are not observed in acoustic instability of solidpropellant rockets. from equation (6)] the velocity amplitudes are much larger in the gas.4. 9.6. with roughly equal velocity amplitudes in the two media but a much larger pressure amplitude in the solid.5). then o l f z nna.9. is much larger in the solid than in the gas (that per unit mass. sharp transitions between gas modes and solid modes occur when R is large. while between crossings the large impedance difference of the two media effectively isolates one from the other. this may be true even if viscoelastic damping is negligible because the transfer of acoustic energy into the solid reduces that in the gas. which [from equation (41)] is seen to imply that ol(1 .2 in the vicinity of the modecrossing points (intersections of dotted lines) occurs. From these results. Wave equations arise in which a relaxation time z . except at the modecrossing conditions of resonance. Acoustic Instabilities in SolidPropellant Rocket Motors 31 1 For large values of R . and it is found that A is of an intermediate order of magnitude and that the frequency behavior seen in Figure 9. This condition defines solid modes having a freeboundary condition at the gas interface. e/p. for which we then see [from equation (41)] that the pressure amplitudes are of the same order of magnitude in the gas and solid.1.
Thus the dissipation rate is greatest when the reciprocal of the relaxation time equals the frequency of the acoustic oscillations and is negligible for long or short relaxation times (that is.o/uf  l)(wz)/[l + (oz)”. modes. compare Section 4. Most vibrational relaxations are too rapid to contribute significantly to CI.1.312 Combustion Instabilities and both equilibrium and frozen sound speeds appear .3. we obtain zs3 + bsz + zw2s + o2= 0.Here the frequency w is real by definition and b . Instead of looking for solutions precisely harmonic in time. Jlul(pw) is the previously identified thickness of an oscillatory boundary layer on a flat surface. A number of different regimes may occur [7].(w/2)(u. k . Because of this we may set s = io + B and assume that 18) < 101. and 1 is the wavelength of the acoustic field. by substituting 2) = Re{ Veikx+st} where V.1. 9. as needed to satisfy boundary conditions for normal into equation (4113). [43]. respectively. is a = .1 is small but positive.lO’w.7. particle damping can be of greater significance. The result here shows that the dimensionless decay rate. The theory of sound attenuation by spherical inert particles in the gas is well developed [44][49]. For example. In the notation of that section.4.2. we may seek solutions harmonic in space. at o z = 1. The solution to the resulting equation for B is B = . values of afo/aeofor the few that are not typically produce CI z .4). for frozen or equilibrium behavior. where b = u:o/u:o and o2= a f o k 2 .4.4. k being a wave number. (42) More thorough derivations of formulas equivalent to equation (42) may be found in the literature [42]. which is not a large damping effect. and s are constants. generalized to threedimensional flow by representing the velocities .4.3. Gasparticle flow with Stokes drag was considered in Section 4. to the order of approximation to which this result applies. Here rs is the particle radius. vanishes as wz approaches zero or infinity and attains a maximum value of ( U ~ ~ / U ~ 1)/4 .and most chemical times are either too short or too long. .6. which exhibits both wave damping and a small decrease in frequency. but that of greatest practical interest has rs @ Jam 1.a / o . with the Stokes drag law applicable. Particle damping As indicated in Section 9.1.~)(oz ib)/[b2 + + (oz)’]. as was done in Section 4. evaluating sz and s3 by expansion to first order in I B/w 1. a onedimensional version was written in equation (4113).(~0/2)(b. The contribution to the previously defined amplification constant CI = Re{B}.4.
Under frozen conditions.2. The dissipation rate 0 of equation (12) is the dot product of the negative of this force with gas velocity v. .6.ioz)/[l + (oz)'].e'"'}.c = 2r. The mass of particles per unit volume appears in equation (43) and can be expressed in terms of the gas density p.VJ. If equation (24) is employed for the gas velocity v. which occur for large particles [large z in equation (44)]. then by use of the equation of motion for a particle.. $nr:p. (49.a/z. by the formula &nrs3Ps) = P&l . while under equilibrium conditions (for small particles giving small z) the particles move with the gas.ldt = 6nr.dv. the negative of the rate of doing work on the gas by the particles. is introduced for the particle velocity. from equation (19.1. the consequent contribution to the amplification rate is r JY where the response time . Thus equilibrium and frozen sound speeds can be defined for particlegas mixtures in a manner entirely analogous to that for chemical relaxation. we can show that which reduces to equation (42) with aeo = &fO (49) if Z and z are uniform throughout the chamber.p (v. The optimum particle radius for maximum damping. that is. is found from equation (44) to be which ds). = Re{V. (45) Evaluation of the average in equation (43) necessitates investigation of the oscillatory velocity fields. .9. and (47) into equation (43). .2. as becomes clear from an alternative analysis [47].vs). Z . corresponding to o z = 1. introduced in Section 4. v.2Ps/(9Ph (44) identified in Section 4.p(v. the particles remain stationary. and a similar representation. Acoustic Instabilities in SolidPropellant Rocket Motors 313 as vectors.6nr. it may be seen from equation (440) that the force per unit volume exerted on the gas by the particles is n. = V(1 . per unit volume. and the mass of gas per unit mass of the system. Thus. has been introduced. (47) By substitution of equations (28).6. (46) [which is readily inferred from equation (440) for example] it is found that v.
G(r. many different approaches to the analysis of various types of damping mechanisms were indicated. and f is defined added. In Section 9. cl = . For a discussion of these effects and for a more detailed presentation of the velocitylag analysis. showing dimensionless damping coefficient as a function of dimensionless particle radius [SO].lo' o.) dr.3. there can be temperaturelag effects on particle damping associated with heat transfer to the particles. replaced by f : r:G(rs) dr.3. being the number of particles per unit volume in the radius range dr./f.. The variety of formulations exposed may help to show alternative paths to damping calculations.(a/m)3p. then a = .4. which may achieve a value on the order of . since values of 1 . with G(r.. In addition to the velocitylag effect analyzed here.(W/2)(PS/P.]. The experiments shown here involved a distribution of particle sizes.1 07 1 1 0 FIGURE 9.3 are not uncommon for certain metalized propellants.) dr." r.>drs./[2nps as z in equation (44) with r. . with an additional term representing the heattransfer contribution r:G(r. Comparison of theory and experiment concerning particle attenuation. see [7].) 1 0 m m r : ( ~ M 1 + (mz>'l>G(r.71 0 0 02 0. (50) in which z is given by equation (44). about r. The value of a at this maxtypically lies in the range of imum is w(l . as may be seen from Figure 9.2)/(42). and equation (50) was used for the theoretical curve in the figure. Predictions of particle damping have been found to agree well with measurement [ S O ] .1.) dr. The linearity implies that if there is a particle size distribution.314 Combustion Instabilities cm to cm. 0.2 as large as 0. in the figure.
multiplying the second equation by p‘/y and averaging over a cycle. 9. the first of these sources generally is the most important. we obtain which in fact turns out to be correct for heat addition to an inviscid. However.2.T).5. that amplification results if.5. much research has been done on this fluidmechanical topic in the field of aeroacoustics. Rayleigh recognized. heat addition occurs in phase with the pressure increases during the oscillation. Temkin for this reference. then equation (10) is e = j$i2/(2y) and equation (454) is Dp/Dt = a2Q/(c. and conversion of meanflow energy into acoustic energy through aerodynamic noisegeneration processes of various types.1. B. constantproperty. Of course. where Q denotes the rate of heat release per unit volume. Higgins in 1777. The second would be more relevant to liquidpropellant rockets. since molecular transport processes are involved in an essential way for example (as was seen for the steadystate combustion in Chapter 7). although it may become significant under special circumstances. as implied by equation (51). The third usually is negligible. for example. the amplification at a burning propellant surface is considerably more complex than the phenomena described by equation (5 l). by use of the first equation. finiterate chemistry in exothermic reactions that occur homogeneously throughout the chamber. the pistonlike mechanism implied by equation (51) when the heat release is localized and the result is expressed in terms of an acoustic admittance [as in equation (29)] is tied closely to the amplification by propellant combustion. quiescent state. Amplification criteria The mechanism of sound amplification by heat release was understood by Rayleigh [Sl]. described beautifully by Tyndall [53]* and dating back at least to an observation made by Dr. and reviews are available (for example. this is the Rayleigh criterion for sound generation by periodic addition and abstraction of heat [52]. Amplification mechanisms 9. Acoustic Instabilities in SolidPropellant Rocket Motors 315 9. In solidpropellant rockets.9.1.1. ideal gas experiencing smallamplitude acoustic oscillations about a uniform. [25]). Our attention here will be focused on the first mechanism.1.1.5. on the average. Qualitatively. if we erroneously neglect any velocity changes just to get a quick result. . It explains qualitatively many observations of singing and vibrating flames (and vibrations in tubes containing heated elements as well). Relative importance Among the mechanisms that may lead to amplification of acoustic oscillations are combustion at the burning surface. * I am indebted to S.
which is roughly (fiw/u)(p. which ranged from . is small (since the interface is nearly an isobaric pressure node) and is therefore more appropriate than the nondimensional admittance y (its reciprocal) for use in equation (22). but at x = . in comparison with chamber dimensions. the ratio of the rate of doing work on the field per unit area at the pressurenode condition of the solid mode to that at the velocitynode condition of the gas mode is on the order of Gpou(u. where the dimensions and velocities are small enough that the timevarying pressure is independent of x to a good approximation [54]. Putting m=E ( 1 m') and assuming that lm'l G 1. v n is the negative of the oscillating part of the gas velocity in the + x direction at x = + m.m and at x = +so for use in calculating acoustic amplification. In this frame. but the latter is negligible because of the density ratio. The pressure oscillations of the acoustic field are imposed on the combustion zone.2.1.). Although it is the velocity that appears most directly in the admittance that is responsible for the amplification. the value of which seldom is as large as Therefore. analysis of the combustion zone usually is performed more conveniently in terms of the mass flux m. for a given energy of the acoustic field. and from the solutions the admittance defined in equation (20) (with v now representing the difference of the velocity from its mean value) is evaluated at x = ./p. typically a few millimeters or less. we may express y of equation (23) as  + +  + where p is the ratio of the complex amplitude of m' to the complex amplitude of p'. appears.m. it is appropriate to approximate the combustion zone as an interface and to employ admittances to describe its influence on the sound field. we employed a coordinate x. Therefore. an apparent body force per unit volume of order povappears in the equation for momentum conservation.* Since n is the unit normal pointing outward from the chamber in equation (20). and since this ratio is small. .p. on the order of heatconduction lengths for deflagrations.)/(pu. the rate of amplification for solid modes is much smaller than that for gas modes. the nondimensional acoustic impedance. The difference of these two values arises in the acoustic analysis [39].V2/2times the real part of the impedance.00 deep in the solid to + m far into the gas. seen by the solid at its interface.4. effectively. r is the ratio of the complex amplitude of p' to the complex amplitude * For the solid modes discussed in Section 9.316 Combustion Instabilities In analyzing solidpropellant combustion in Chapter 7. v n is on the order of the ratio of the gas density to the solid density times that at x = m.r: and that at x = + x. solid modes are not excited. it is sufficient to evaluate CiY at x = m for use in amplification expressions such as equation (29). The difference of the impedance at x = .). However. the distances over which changes occurred were small. The combustionzone analysis may be performed in a noninertial frame that moves with the acoustic velocity. from the viewpoint of acoustic instability.5 and identified in Figure 9. Thus the righthand side of equation (22) is best expressed as . normal to the propellant surface./p. The combustionzone structure must be analyzed subject to these pressure oscillations. In terms of the thickness 6 of the combustion zone.
r may be evaluated in equation (52) from the quasisteady combustionzone analysis. the velocity amplitude has been eliminated by use of the expansion m/p = (E/p) (1 + m‘ . a complication has been identified on the basis of studies of the combustionzone structure [55]./o. . although this is somewhat of a misnomer. the periodically generated nonisentropic component is transported with fixed form at the mean gas velocity. However. the effect is predicted to be greatest in large chambers. the density and temperature oscillations are found to be related to the pressure oscillations by conditions that are not isentropic. this dissipation is much more rapid than the corresponding dissipation for acoustic waves because the wavelength. since equation (449) is not the wave equation.p’ + . Since the combustion has been completed.* Thus the combustion response may create a region large in comparison with the thickness of the steadystate combustion zone. z lo2cm/s and o z 103/s)are found to lie between 1 cm and 10 cm. small changes in p that may occur between this location and the downstream edge of the reaction zone usually are not addressed in analyses. . within which the wave field is modified by nonisentropic effects. ~ * Since the ratio of the decay length to the chamber dimension theoretically increases in proportion to the chamber dimension. as implied by equation (449). p’ = p’ and r = 1. is shorter (typically lo’ cm to 1 cm). often it is most convenient to evaluate p just after quasisteady combustion. Although this value assuredly is correct formally. which in extreme cases may reach a significant fraction of the chamber dimension.9. and when this is multiplied by as ( ~ . it is expected that l / y I Re{r} I 1. and r = l / y holds there. and therefore influences of uncertainties in the value of r are not large. . in the hope that use of the value so obtained may account approximately for dissipation in the nonisentropic zone. In the isothermal limit. It is strictly proper to employ equation (52) in an acoustic boundary condition for amplification calculations only outside the nonisentropic zone. We shall employ r = l / y and view dissipation in the nonisentropic zone to be counted as an additional damping contribution. By balancing the rate of heat conduction per unit area with the rate of change of thermal enthalpy per unit area in a halfwave. and all quantities are to be evaluated in the gas at x = +a. [56]. of order v. .1. Acoustic Instabilities in SolidPropellant Rocket Motors 317 of p‘. These “waves” decay through nonquasisteady heat conduction between their temperature peaks and valleys. / odivided v.). representative values (with v. Models based on the hypothesis of a quasisteady gasphase flame predict a nonisentropic relationship between p and p in the gas at the downstream edge of the gasphase reaction zone. Equation (4) implies that r = l / y in equation (52). When this is done. The consequent spatial and temporal oscillations of entropy have been termed entropy waves. for example. say v. a decay time may be estimated )~ by a thermal diffusivity. to obtain a characteristic decay length.
This observation enables the order of magnitude of the growth or decay rate to be estimated directly from equation (30). assumed here to be a known constant. The principal value of timelag concepts lies in the wide range of problems to which they can be applied with relative ease. or the burningrate response. Among the improvements to equation (54) is the introduction [17].5. A given element of reactant material requires a certain amount of time to burn. then in m(t) = EL1 + m’(t)] and p ( t ) = p[1 p’(t)].1.zJ. at which time m instantaneously assumes its steadystate value.3. timedependent conservation equations are linearized about any one of the steadystate solutions of Chapter 7 and p is calculated from a perturbation analysis. which requires that n > l/y and that wz be in an appropriate range for amplification to occur. we have m’(t) = np’(t . then the regression rate will take a certain amount of time to reach its new steady level. If n is the pressure sensitivity [appearing. at all x. whence amplification is predicted at low frequencies. [57][60].iwrl . [17]. for example. then it is found p=ne . . [59] of a sensitive part of zI that varies with pressure and gives results more versatile than equation (54). The many different possibilities for steadystate structures of the combustion zone indicated in Chapter 7 imply that many different analyses can be relevant to the calculation of p. The interval zl is the time lag. equation (52) indicates that y is of the same order of magnitude as the Mach number of mean flow of the burnt gas. Their principal deficiency lies in the difficulty of relating zl to the fundamental processes occurring. so that + (54) Thus the criterion in equation (53) becomes n cos(wzl) > l/y. As the simplest idealization of these observations. o < (l/zl) cos. we see that a necessary condition for amplification by the propellant combustion is The ratio p often is termed the response function. in equation (741)]. If the onedimensional. typically wzl is small. appropriate to the new pressure. Here we shall outline only two and comment on other approaches. for example. A critique and more thorough review of the timelag ideas has been published [7]. 9. and combustionzone analyses typically provide magnitudes of order unity for it.‘[l/(ny)]. More accurate computations necessitate calculating Re{pL). assume that a pressure change applied at time t has no effect on m until time t + z l .318 Combustion Instabilities By use of equation (52) in equation (29). and if a small pressure pulse is applied to a steadily burning propellant. Therefore. Timelag theories Many early analyses of timedependent solidpropellant combustion employed the concept of a combustion time lag [4].
denote the preexponential factor and the overall activation energy for the surface process.MROT. but it varies with t in this coordinate system.1. This latter characteristic time is PsMcpsm2). Representative values of z. specific heat. Under the assumption of . By mass conservation.1. Timelag approaches are useful for a first look at instability problems (including liquidpropellant rocket instability).)l.E.co and T = at x = 0. Combustion response Although many different processes may be involved in solidpropellant combustion. and thermal conductivity of the solid assumed constant. m = 4 expr . the equation for energy conservation in the solid becomes 7s = (56) The coordinate system is selected so that the solidgas interface. and E . who considered timedependent burning within the context of an approximation of constant temperature at the solidgas interface. The combustion mechanism addressed involves inert heat conduction in the solid. at x = . is maintained at x = 0. Boundary conditions for equation (56) are T = To.9. Thus it is attractive to assume that all processes remain quasisteady except the solidphase heat conduction. [62].5.a2T/ax2.the initial temperature of the propellant. given by equation (76) but also interpretable in terms of a distributed solidphase reaction in a thin zone (as indicated at the end of Section 7. surface gasification by an Arrhenius process and a gasphase deflagration having a high nondimensional activation energy. is written here in the form = p ... where conditions are identified by the subscript i. The interface Arrhenius law. in which use is made of the deflagration analysis of Section 7. lie in the range s to lop4s. and a more complete model has been explored. 9. and yet the results of many of the more recently published theories bear a close resemblance to its results. Acoustic Instabilities in SolidPropellant Rocket Motors 319 to be difficult to express the results in terms of distributions of time lags. estimates suggest that characteristic times for all of them may be short compared with the characteristic time for heat conduction in the solid. ~ . aTlax 1 . It is of interest to present an analysis of the last of these models because it is relatively simple. With the density. (55) where the subscripts identifies properties of the solid.4). Oscillatory burning has been analyzed under this assumption [63]. This idea dates back to the work of Zel'dovich [6 13. (57) where the constants B. . but more detailed analyses of the flow processes are better when they can be performed.4.5 [64]. which is comparable with typical values of l/o. m is independent of x everywhere.aTlat + mc.
and T.c. + (c. Equations (56)(59) provide a wellposed problem for addressing influences of harmonic pressure oscillations.(dT/d~)i= m[L.. P in equation (24).JL.AT + dAT/d( + pPdT/dt = d2AT/dt2.5 and equation (5. c.(T. Analysis of the quasisteady gasphase flame by activationenergy asymptotics [65] shows that also m = Cp”exp[ E1/(2RoT. is the (constant) specific heat at constant pressure for the gas. (dAT/d()i = s ( A T ) ~ pP + (S  l)pP(T . L. [65]) may be shown to be expressible as L. and t = xi%.TO)/(io~. represented as the sum of the particular solution and a solution to the homogeneous equation.320 Combustion Instabilities quasisteady. (60) By putting T = T + Re{ATei”‘} and linearizing equation (56) about T (under the assumption that I AT I 4 T).co.(T .)(T . adiabatic. (58) where L. and the solution to the homogeneous equation is a constant times es5. + c. . (58). the interface energy conservation condition readily (for example../(RoT?) = nP + (AT). The steadystate solution to equation (56) is easily seen to be T = To + (T . The perturbations of equations (57). gasphase combustion. (62) the positive sign of the square root having been selected to satisfy AT = 0 at 5 = . q is the (constant) energy per unit mass released in the gasphase reaction. . = L.To)exp(xEc.).(T.we may readily derive the perturbation equation ioz.To)+ E.75)]. (59) where C and n are positive constants ( n being half of the pressure exponent for the homogeneous gasphase reaction) and where El is the overall activation energy for the gasphase combustion [see Section 7. is defined in equation (55)./A. (63) may be derived.where s = (1 + J1+4ioz.  731.From the general solution.q + c. An overall energy balance may be applied to steadystate conditions (identified by an overbar) to give q = c.). (61) where z.. is the energy per unit mass required for gasification. A particular solution to equation (61) is (ioz. is the flame temperature (which varies with time).)].. and (59) give = (AT)iE.E1/(2RoT’.T). the pressure appears here only in equation (59).)’pLP(T . the relationship between the heatflux perturbation and the temperature perturbation at the interface.)/2.that is.T). and thermodynamics require L. .To)e5.) (64) . to vary with if cps # c.
large.2. An idea of the predictions concerning amplification may be obtained from expansions for small and large values of wz. variation have been employed with equation (58) in obtaining the last expression. [12].( B + 1). values between ( B + 1) . Typically. increases for 07. large and a behavior for small wz. Acoustic Instabilities in SolidPropellant Rocket Motors 321 and (dAT/dOi = ~ P ( ’ i i To) . = 0.B)s + A]. (65) where the overall adiabaticity and the L.T3. From equations (62) and (66) we find that Re{p} = n{l for wz.>E. with n.A’]/B2 + Re{p} = nB/& + .9. These results  + + . which occurs for A 2 6 in this case. in the vicinity of wz.(~p/~ps)(AT)m + (AT)i.. large values of A and of A / B lead to larger peak responses through the greater sensitivity provided by the high activation energies. Re{p} exhibits one broad maximum. showing a decreasing response with increasing wz.1. (66) where A = (T ./(ROT. (68) Equations (62) and (66) provide p as a function of wz. have appeared in the literature (for example. Use of equations (62)(65) to remove iwz. [66][74]). . and B appearing as the relevant steadystate combustion parameters. The enhancement is caused by the transient buildup of energy in the solidphase heatconduction zone and is typical of predictions of morecomplicated theories. where the envelope curves represent the maximum achieved for any value of A and the envelope asymptote is related to the intrinsic instability.CPT2. the height of which depends on the values of A and B and exceeds n for a range of values of A and B. for calculating the response function from models that do not rely on time lags. ( ~ i A T / d t(AT)i ) ~ .J ( B + 1)’ . A . from the system then yields / l = nBs/[s’  (1 + A .Z) (67) and B = 2E.4. for wz.)’[(B + 1)(2A 1) . [76]. A few representative theoretical response curves are shown in Figure 9. Some of the models admit a certain amount of nonquasisteady + (wz.. reviews are available [7]. The present model also exhibits an intrinsic instability if A or A / B is too large. small and demonstrate the quasisteady response for wz.( B + 1) (for A > 3 )and ( B 1) J ( B + 1)’ . [75]. . In general./(E1CP. if A is small or large but an increasing response for intermediate values of A . z z 1. amplification that decreases in proportion to 1 / 6 as wz. and ( A T ) . as will be discussed in Section 9. Many analyses of the general type outlined here.T.
Although experimental measurements of the response function are difficult to perform (except by inference from measured growth rates of pressure oscillations in chambers).322 Combustion Instabilities Envelope asymptote FIGURE 9. for which it was seen in Chapter 7 that the combustion mechanisms may be complex. Thus even if the model that has been analyzed here is inaccurate in detail. which allow them to exhibit transient energy accumulation. particularly with respect to condensedphase and dispersedphase processes. . Nevertheless. T i . results for any model that maintains quasisteady gasphase processes can be expressed in terms of the results that have been derived here. A . and B in terms of sensitivities of rn top. * It can be shown that by reinterpreting the parameters n. and T . behavior in the gas phase. most of the mechanisms described in Chapter 7 have not been investigated in the context of oscillatory response. A . Representative burningrate response curves obtained from equation (66). The equations allowing fully nonquasisteady combustion in the gas phase are complicated [54] and have not been explored completely. even on the basis of quasisteady gasphase approximations. This belief is based on the observations that gasphase combustion is usually at least of small importance for transmitting energy in propellant burning. with A = 28.4.* In fact. it seems likely to retain the qualitatively essential physics for describing response to pressure oscillations. it seems likely that the main elements of the response function for homogeneous propellants are reasonably represented by the analyses that have been performed. . showing a nondimensional measure of the amplification rate as a function of the nondimensional frequency for various values of the nondimensional activation energy for gasification. These models all pertain to homogeneous propellants. A useful philosophy is to attempt to develop general descriptions that are independent of specific details of combustion models [76]. the few results that have been reported for homogeneous propellants tend to agree qualitatively with predictions [77][80]. while condensedphase (or possibly dispersedphase) processes have longer response times. which can be important at high frequencies.
Acoustic Instabilities in SolidPropellant Rocket Motors 323 9.7. in which instabilities are strongest in specific. then lowfrequency. if the uncovering time is long. B > 0). There are reviews of the early studies [7] and of more recent work [82]. [82]. To employ a result like equation (66) directly is questionable. Relatively few theories have been addressed specifically to the acoustic response of heterogeneous propellants [82]. then an average is perceived by the acoustic field. Uncovering times often can be comparable with acoustic periods. nonacoustic oscillations may be superposed (at least locally) on the acoustic oscillations. described in Section 7. frequency ranges. narrow. Applications of timelag concepts to account for various aspects of heterogeneity have been made [60]. wher CI and p are constants [85]. [83]. the latter measuring the magnitude of a heterogeneity of the propellant and being independent of the acoustic amplitude.1. an additional term arises in equation (14) that is proportional to the product of the pressure amplitude and the heterogeneity amplitude. and the sideways sandwich model. the current situation is much less satisfactory. Response curves like Figure 9.5. although attempts have been made to evaluate parameters like A and B of equations (67) and (68) from complicated combustion models for use in responsefunction calculations [8 11. to amplitude thresholds that must be exceeded for growth to occur ( a > 0.7. a simplified modelincluding transient variations in stoichiometryhas been developed [84].4 may be found to possess more than one .9. Heterogeneity effects For heterogeneous propellants. The solutions to equation (69) differ from equation (16) and show that the heterogeneity interactions can lead to linear rather than exponential growths of acoustic amplitudes with time at low amplitudes (a > 0.1. B < 0) and to limiting amplitudes that are approached at long times (a < 0. The complexity of the combustion process was discussed in Section 7. When the propellant surface responds coherently. have been observed experimentally for composite propellants [86] and may be attributable to the heterogeneity of the solid. p > 0).5. A peculiar aspect of the response of heterogeneous propellants is associated with the periodic uncovering of different propellant constituents during normal regression [85]. If the uncovering time is short compared with an acoustic period. An equation of the form d&/dt =a &  +p (69) therefore is obtained. Description of the interaction necessitates augmentation of responsefunction concepts and entails considering a synchronization time needed for the establishment of a coherent phase of the heterogeneity over the propellant surface by action of the acoustic oscillations [85]. thereby leading to the possibility of significant interaction between heterogeneity and acoustics. has been explored for calculating the acoustic response [85]. Preferredfrequency phenomena.
8 where it was indicated that the burning rate m depends on the gas velocity parallel to the propellant surface. An analysis has been published [94] of a related problem. However. changes in the mean burning rate of the propellant in the presence of an acoustic field. Erosive burning was addressed in Section 7. arose early. Here we shall discuss only three topics involving nonlinearity: the response of the combustion zone to transverse velocity oscillations (conventionally termed velocity coupling). usually associated with high amplitudes of the acoustic field. which is more difficult because of the essential role played by finiterate chemistry. indicated in Section 7. [87][93]. Thus a mode transverse to the driving mode is generated. Even for these relatively simple problems. Some aspects of the results qualitatively resemble those anticipated from nonlinear effects. and they require special consideration. [123. The combustionzone analyses needed for calculating the response would be complicated because of the complexity of erosive burning. and the idea of introducing a velocitycoupled response function. then it may be expected to produce smallamplitude oscillations of m that locally may be related to the amplitude of the acoustic velocity oscillation through an admittancelike expression similar to equation (52). 9.1. . If the acoustic velocity in the gas adjacent to the burning surface is small compared with the local mean erosion velocity. can introduce many interesting effects into acoustic instability [76].324 Combustion Instabilities maximum. Of course. The process of transfer of normal oscillations to tangential oscillations must be studied to ascertain the efficiency with which the response can produce amplification. In addition to the meanflow erosion. and instabilities that involve the propagation of steepfronted waves (identified in the introduction as shock instabilities). and the new mode is not likely to be a normal mode of the chamber. It has long been recognized that acoustic erosion can affect the instability [7]. that of combustion of a solid fuel with a gaseous oxidizer in a laminar boundary layer. Nonlinear effects Nonlinear phenomena. on par with the pressurecoupled response function p. Although there are special conditions under which this makes sense. the influences of velocity coupling usually are nonlinear. little work has been done on the corresponding solidpropellant problem. The oscillations of rn can excite acoustic oscillations if there are pressure oscillations at the point in question to enable work to be performed on the acoustic field.6. a corresponding response to pressure oscillations also is to be anticipated.8. even at low acoustic amplitudes. there is acoustic erosion from most of the modes in a chamber experiencing acoustic instability. a difficulty in applying results of the analyses to the calculation of growth rates of acoustic fields arises from the fact that the velocity oscillations associated with oscillations of m are normal to the velocity oscillations of the driving field.
. this causes m‘ to be a function of lcos cot1 = {[l + co~(2wt>]/2}”~. Acoustic Instabilities in SolidPropellant Rocket Motors 325 All other types of velocity response are nonlinear in one way or another. With u proportional to cos cot. as well as harmonics. More generally. is the value of E at p’ = 0 (so that E ‘ # 0 at finite amplitude). It provides a mechanism for reaching limiting amplitudes that is an alternative to nonlinearities in the bulk of the chamber. are found. the erosive response extracts energy from the fundamental and feeds it into harmonics. It is easy to write formulas for this change if the response is assumed to be entirely quasisteady. shows that the fluctuating response m‘ is a function of I u 1. the Fourier expansion of which exhibits contributions from frequencies 204 401. Thus the response generates harmonics but does not affect oscillations at the driving frequency. eventually establishing a steady condition in which the amplitudes of the fundamental and of all harmonics are independent of time.p)]} (71) . It is theoretically possible that. For example. The amplitudes of the harmonics in m‘ increase as I u I increases. For example.(l p = p(1 + p’). ./7). This type of process has been described for heaterexcited acoustics oscillations in tubes [95]. 6w.9. which is of importance in producing “secondary peaks” of the mean pressure. for example. with a nonzero mean erosive velocity and a component of the acoustic velocity parallel to it. if the erosive velocity is u = uo(l + u’) and u’ is sinusoidal in time (so that its maximum is 2. contributions at frequency co. in boundary damping or in the pressurecoupled response. then with m = E.1. Another aspect of nonlinearity is a change in the mean burning rate.1) d0/2n that m‘ = 0 for 2 0 < 1 and ‘ E‘ = ( k M 0 / i i i 0 ) ( 2 / n ) { ~ ~1 . erosive effects (in the absence of an erosion threshold or of negative erosion) produce an increase in the mean burning rate with increasing velocity amplitude. then through adoption of equation (745) with M = M. By contrast. then equation (745) or equation (746). but none from frequency w.(1 + u’). we find through expansion to second order (by use of the average p’ = 0) that + which exhibits a decrease in the mean burning rate with increasing pressure amplitude for 0 < y1 < 1. even though the acoustic field itself remains entirely in a range of linearity. where v is the acoustic velocity tangent to the surface. as the intensity of the acoustic field increases. if there is no mean erosion and if frequencies are low enough for the propellant to respond to the acoustic erosion in an entirely quasisteady fashion. This same effect would be found in the presence of mean erosion if the acoustic velocity were normal to the mean erosive velocity. . if equation (741) is taken to apply m’) and under conditions of oscillatory pressure. it may be shown by evaluating jgn (I 1 + 2 u p sin 81 . For example.cOs1[1/(2. where E.
discontinuities are permitted across the normal shock. [loo]. The departures remain small if nonlinearities develop in damping processes at sufficiently low acoustic amplitudes and serve to limit the amplitudes to low levels. In the theoretical analysis of shock instability. The approach is based on methods that have been applied to related problems in nonreacting flows [103][ los]. since this corresponds to a zero threshold) and is given by For a few propellants. At a fixed value of the dimensional amplitude. However.326 Combustion Instabilities for 2 0 > 1. shock waves that are not too strong are presumed to propagate axially back and forth in a cylindrical chamber. Boundary conditions at the propellant surface ( z = 0) and at the . [102]. when the maximum acoustic erosive velocity equals the mean erosive velocity. a threshold for onset of an acousticerosive contribution to E occurs at the beginning of rectification. experimental evidence exists showing that a decrease in E'is produced by pressure oscillations and an increase by erosive velocity oscillations [90]. but the shock remains isentropic to this order of approximation. the increases in E that are of greatest practical concern for producing increases in jj in choked chambers in all probability are usually associated with effects of acoustic erosion. the largest E' in equation (71) occurs at uo = 0 (as expected. The onedimensional. there are motors that are linearly stable but nonlinearly unstable to finiteamplitude. As acoustic amplitudes increase. Since nonlinear effects are addressed. in qualitative agreement with the predictions of equations (70) and (71). In addition. In this case. shocklike disturbances. the same results are not expected to apply at frequencies. the wave forms begin to depart from those of the normal modes. [102]. E' decreases from the value given in equation (70). high enough that departure from quasisteady response occurs. the expansion is carried to second order in a small parameter t that measures the shock strength. 2 u 0 0 . timedependent conservation equations for an inviscid ideal gas with constant heat capacities are expanded about a uniform state having constant pressure j and constant velocity V in the axial ( z ) direction. Particular examples involve axial modes in cylindrical motors with internally burning tubular grains [99]. bouncing off a planar combustion zone at one end and a short choked nozzle at the other [lo ll. that is. A few analyses of nonquasisteady changes in the mean burning rate have been completed for various models of pressurecoupled response [76] and suggest that as the frequency increases. Theoretical methods for analyzing nonlinear growth and limiting amplitudes in this lowamplitude regime have been investigated [96][98]. There are systems in which the amplitudes become large and the acoustic waves begin to exhibit a steepfronted character like shock waves. A theoretical approach has been developed for analyzing these shock instabilities [lo ll. where the inverse cosine lies between 0 and 4 2 . Therefore.
. Acoustic Instabilities in SolidPropellant Rocket Motors 321 nozzle entrance ( z = I ) may be expressed in terms of real admittances.Calculation of these admittances entails analysis of the combustion zone and of the nozzle flow subject to shocklike perturbations. constancy of the Mach number at the nozzle entrance has been employed [loll. Few of the needed admittance analyses have been completed.9. The limiting amplitude. only Y c l ) appears for small values of M . For axial modes in tubular grains. it is found that the pressure increase across the shock is Ap = tpM[4y2/(y + I)]. It appears that. Solutions cyclic in time are sought. the steep fronts may develop from sinusoidal waves or may be established directly by an imposed pressure pulse. The solutions obtained describe the longtime behavior of slightly nonlinear waves. Thus in the first approximation the shock strength depends on the boundary admittances [see equations (73) and (74)]. . In rocketchamber experiments.Y y ) .5. For example. and a timelag approach to the description of the combustion zone has been adopted [102]. [I1021. (73) here t > 0. as is usual in perturbation procedures of this type. given by equation (74).3. may be thought of as being set by a balance between the net work input at the boundaries and a kind of dissipation in the shock. (74) Representative pressure and velocity fields are illustrated in Figure 9. For example characteristics may be introduced as independent variables and space and time may be treated as dependent variables. Yo and I . the admittances could be functions of the pressure history over a cycle at the boundary. ' . in general.. It is known that nonlinearity causes waves to steepen with time. (72) The small parameter of expansion for the shock strength is € = (j/V)(. the driving mechanism must involve a continuous nononedimensional energy input from the response of the propellant combustion to the passage of the shock over its surface and probably exhibits a significant erosive component. respectively. for small Mach numbers M of mean flow in the chamber. . and.1 = YLyp  + Yb?](P  p). eventually approaching shocks.1. + . where the sawtooth shapes of the waves may be seen. The analysis makes use of characteristics (Section 4. so that more mechanical energy is fed into the wave pattern at the combustion zone than is extracted at the nozzle.3) and may be performed in different ways [loll..Y y ) .. it is necessary to carry the analysis to second order if the complete solution at first order is required. thereby introducing additional complications into the formulation. but both Ycl)and Y c zoccur ) at larger [7]. [102]. The results relate the pressure and velocity fields and the shock strength to the admittances. [1011.by expansion to second order : T (0  6)0.
328 Combustion Instabilities P P  V V D t t f  Wave d i r e c p Wave direction t fixed I p fixed ! ~ f .5. Nonlinear perturbation methods. added to the righthand side. as will be indicated in the following section. The statement of energy conservation in the solid may be taken to be equation (56) with a heatrelease term. mentioned at the beginning of Section 7. 0 Z 1  I 0 c Wave direction f  1 Wave direction Z t I fixed .2. methods of numerical integration are needed in describing largeamplitude behaviors accurately. Accurate use of numerical methods for acoustic instability is difficult to achieve because so many physical processes with poorly known parameters usually are involved. If t of equation (73) is not small. a temperatureexplicit . There are intrinsic instabilities in burning solids that involve fewer processes and that are therefore better suited to investigation by numerical approaches. Although w q properly depends on the reactant concentration. say w q . somewhat analogous to the method just described. INHERENT OSCILLATIONS OF BURNING SOLIDS As an especially simple example of an intrinsic instability. also can be applied to these intrinsic instabilities. In general. then cyclic solutions cannot be obtained by the perturbation approach that has been outlined here. I 0 2 1 FIGURE 9. adiabatic. let us first consider the planar. Theoretically calculated nonsinusoidal wave shapes of pressure and velocity fields for shock instability [loll. 9.4. gasless combustion of a solid.1 and discussed in the middle of Section 7.
equations (75) and (76) give.15). * On a thermalexplosion time scale. Inherent Oscillations of Burning Solids 329 formulation may be achieved by adopting an expression like equation (718).a2T/dx2= . t ) and m(t). It is attractive to seek solutions by use of activationenergy asymptotics. whichthrough matchingcorrespond to conditions just on the negative side of x = 0 for the outer solution in the unstretched x variable.4. Then. Here x = 0 has been selected as the position at which the reactant has been consumed completely.[(aT/ax). then by stretching the coordinate about x = 0 and excluding variations on a very short time scale.2. Multiplying the differential equation by dT/ax and integrating over the same range yields [(aT/~x).identifies conditions “at minus infinity”in the stretched variable. then this can be shown to restrict the formulation to conditions such that changes with time are not too rapid.1. the formulation in employing equation (720) excludes a transient behavior within the reaction zone. in the first approximation. Use of these equations along with T = To = constant at x = m.9. if timedependent versions of equations (715) and (716) describe the original problem. with wq = qswl for x < 0 in the notation of Section 7.=oI2. and wy = 0 for x > 0. so long as attention is restricted to times small compared with the time for homogeneous thermal explosion of the reactant at temperature To. = constant at x = c c is in . (76) in which the asymptotic expansion of the integral may be evaluated relatively conveniently for temperatureexplicit rates.=~ is + of higher order in the nondimensional activation energy (the Zel’dovich number). By use of equation (720). It is consistent within the formal context of the asymptotics to restrict attention to problems in which (aT/a~). with use of equation (718). 0 wl(aT/ax) dx.=o+I2 = (2qs/&) J.* As can be inferred from the timedependent generalization of equation (7.qswl to the first approximation in the reaction zone. The burning rate m is expressed in terms of w1 by equation (720). the integral of this equation across the reaction zone is seen to be expressible as where the subscript x = 0. dT/dx = 0 at x = +a and a suitable initial profile for T(x) provides a wellposed problem for calculating T(x. If there is a narrow reaction zone in the vicinity of x = 0. imposition of T consistent with the differential equation. the augmented version of equation (56) becomes .
. A stability analysis of the steady state of equations (56)(59) may be developed in a straightforward manner [64].Y1. (79) (78) may be written as ( A .+ = 0 provide first approximations to the results obtained by a more formal derivation of jump conditions across the thin reaction zone. otherwise./c. . where a is the growth rate and o the frequency. To the lowest order in the Zel'dovich number. the formulation of Section 9.( A + B)l(a + io)zs.we may put n = 0 in equation (59) and B = c.=. = E1/(2R0). to achieve surface adiabaticity within the context of a linear expansion about equation (60). The resulting form of equation (58) corresponds to a surface that is adiabatic on the side x = O + and at which a constant energy per unit mass is released.B)' . o = 0 and a ~=.B)' + 1 I 2(A + B). it may then readily be seen that timedependent solutions in the absence of external pressure perturbations may occur if s2 .. = { 2 R 0 ~ . The problem for x < 0 becomes identical to that described by equations (56)(58). which has been assumed to be large in the course of the activationenergy asymptotics. / ( A B)' + 1 2(A + B)]. B.. From the derivation leading to equation (66). from which it is seen that for o # 0. Thus for describing small perturbations about the steady state in gasless combustion. and the sole remaining parameter is A [defined in equation (67)].330 Combustion Instabilities the last equality of which may also be inferred from equation (729).B)2 . (78) where now Equation 2(a + iw)z3. to enforce a constant surface heat release per unit mass.) = constant. +~ [ ( A .(T.( A .2 = [ ( A .l/2. Studies of the stability of the steady state therefore may be pursued as a special case of the stability analysis of the problem defined by equations (56)(59). = $ [ ( A .q c. Here ?I: denotes the value of T at x = 0. obtaining ( A T ) . the square of which yields AB + J1 + 4(a + iw)z. in equation (65). with the replacements E . / [ E ~Y1.] (}' l' and L .B)2 (A + B) .5. Specifically. Jv. . = A + B + s = [I + (az . Equation (77) and (dT/dx). T remains constant for x > 0. B ~ T ~ ' f 2 ~ .B ) J1 + 4 ( a + io)z."' ~. we must then put cp = c. Equation (56) applies on each side of the reaction zone in this threezone problem.1. A relatively simple technique is to look for solutions of the form T = T + Re{ATe(afi")t}.B ) . we have az.) = qs(l .    .7. Intrinsic instability to planar disturbances occurs if solutions having a > 0 exist.(1 + +A  B)s + A = 0.( A + B)] and co = This solution applies when ( A .4 may be employed with n = 0 and B = 1. = (AT)i from equation (64). in equation (68).o2+ 2iao)z.
Thus Figure 9. A stability diagram in the parameter space is shown in Figure 9.4. for example. it may be noted from equations (67) and (68) that A and A / B represent nondimensional activation energies for the interface and gasphase processes.6. that is.6. Diagram of regions of intrinsic instability of the steadystate combustion given by equation (60). Figure 9. we let B = 1 and find that intrinsic instability OO L . it may be shown that Figure 9. the coldboundary difficulty is not present in this model. if A > 1. the combustion is intrinsically unstable unless ( A .B)’ < A + B. In applying these results to the model of Section 9. If A < 1 or if A / B < 1.6 therefore shows that intrinsic instability occurs (even in the absence of pressure perturbations) when the nondimensional activation energies are sufficiently large. equal to zero . and the resulting stability boundary will not be expected to differ greatly from that shown in Figure 9. respectively. we may conclude that in a strict interpretation of the range of validity of the analysis. .6 even for relatively small values of A / B .5. Since equation (59) relies on an asymptotic expansion for large values of A / B . but. instability is to be anticipated whenever A > 1.6 is expected to provide at least a qualitatively reasonable approximation to the stability boundary for all values of A and A/B.9 2 Inherent Oscillations of Burning Solids 331 which is positive (implying instability) throughout its region of validity. To apply the results to the gasless combustion problem introduced at the beginning of this section. A stability boundary in the AB plane may be defined by setting the first expression for M. with suitable redefinitions of A and B.6 remains exactly correct. I . In fact. a generalization of equation (59) may be developed for finite values of A / B (still within the context of a quasisteady gas phase). then there is a critical value of A / B above which instability occurs.1. then according to the criterion obtained. I I I I I I I 2 4 6 8 1 0 AIB FIGURE 9. the combustion is intrinsically stable.
(1 .)]. apparently we should conclude that the steadystate solution to the adiabatic version of the problem of Section 7.. The hot flame may propagate until it consumes all the heated reactant. as a consequence of the fact that v1/v2is small for large Zel’dovich numbers. The transient heatconduction time required for this heating is roughly t . . we see that s’? v1 where C = C exp[ E. then its velocity will be roughly v2 = C exp[ .To)dx just ahead of the reaction sheet. EE As/(pscps) denotes the thermal diffusivity of the solid.. x2 = a.Yl. and the hot flame again may be initiated at its reaction front. [l09]. [l lo].. where v1 is the steadystate flame speed. ~ ) ’ ] ) ~ x’ constant. pscps(T ./v.the adiabatic flame temperature.O)/C. flame propagation in the solid is associated with an excess enthalpy per unit area given by a.332 Combustion Instabilities is predicted to occur if A > 3.o)/~ps. this gasless combustion problem possesses the coldboundary difficulty. Since 3 may not be a sufficiently large number.)/[p.)].(~Y . After the heating is completed.Elq. Approximate conditions for the existence of this hot flame are reasonably well satisfied because its thickness.o)/cps. therefore. From the second equality in equation (77). lasts for a time of about e2 = x1/v2. it is halted. The mechanism of the instability that has been described here suggests that intrinsic instability of gasless combustion evolves to an inherently pulsating mode of propagation rather than to a sustained explosion or . If a flame now begins to propagate adiabatically in the heated reactant. where T2 + = TI + 4 S U  YI. If a. and stability analyses for various models are available [76]. this occurs over a distance on the order of x1 and. As formulated. and the results are therefore restricted to large values of A . an adiabatic flame may again be established. and thereafter practically no propagation of the reaction front can occur until a new layer having thickness of order x1 is heated.When the hot flame encounters cold reactant.4 is intrinsically unstable../v2. = To q. a value considerably greater than the adiabatic flame temperature of the unheated reactant.. = x:/cis. = {2RoBlT~1+2A. is much less than the thickness x1 of the heated layer in which it propagates. the thickness of the heated layer of reactant is on the order of x 1 = a. then for the steadystate solution. The possibility of the occurrence of instabilities such as this in burning solids was known to Zel’dovich [61]. Under the present conditions of negligible diffusion..El/(2RUT. = To + 2qdl  yl. ~  and where 7./(2R07. This excess provides a local reservoir of heated reactant in which a flame may propagate at an increased velocity. The mechanism of the instability encountered here can be understood physically.
below which the reaction effectively ceases. which is less than the velocity u1 of the steady flame. If the reaction is of the Arrhenius form for temperatures above the switchon temperature.2. + t2) = 4 1 + (t2/tl)I. flame temperatures in excess of the steadystate adiabatic flame temperature occur. a value at which a splitting into more than one possible solution occurs (for example. For a problem of this kind. The ratio of the duration of a pulse to the time between pulses is roughly which is small when the Zel'dovich number is large. additional. then A is a suitable parameter for measuring the temperature sensitivity of the rate. there might be a critical temperature exceeding To. a tendency for this to occur has been found in numerical integrations [lo91 which show. It can be imagined that for sufficiently large Zel'dovich numbers. The coldboundary difficulty then disappears. with each series separated by quiet periods. an irregular series of pulses.9. perhaps corresponding to a phase transition. Inherent Oscillations of Burning Solids 333 extinction. [l 111. This conclusion has been substantiated theoretically by more detailed analyses [1091. The critical value would represent a bifurcation point. they may nevertheless yield stability limits that are roughly correct. and pulsating propagation has been observed experimentally for solids [ 112][114]. morerapid flames might develop and follow the first hot flame. The average velocity of propagation is XI/@. Numerical integrations [lo91 seem to indicate that for . while the deflagration is inherently oscillatory at larger values. such that the steadystate. These results verify that during the rapid portions of pulsating propagation. and a wellposed deflagration problem can then be defined without introducing asymptotic concepts. We have seen that there are interpretive difficulties associated with the use of activationenergy asymptotics for calculating limits of intrinsic instability in gasless combustion. for example. a steady solution and an oscillatory solution) and at which the character of the solution to the problem may change. Estimates of characteristics of pulsating propagation may be obtained from the model that has been described for the mechanism. it is to be expected that there will be a critical value of a parameter that measures the temperature sensitivity of the heatrelease rate. at the larger values of the activation energy. onedimensional combustion is stable for values of the parameter below the critical value. Real condensedphase processes might not be strictly Arrhenius. These results are in qualitative agreement with predictions of accurate theories. Although stability analyses based on activationenergy asymptotics may not provide accurate values of A at the bifurcation point.
then a nonlinear perturbation analysis can be developed for describing analytically the nature of the pulsating mode [Ill]. certain metalized composite propellants have been observed to burn in the laboratory with idehtifiable ranges of frequencies of oscillation [I IS]. the pulsating instability may be eliminated through stabilizing influences provided by energy input from the gasphase flame. Even if the solid propellant burns by a mechanism predominantly involving condensedphase reactions of large nondimensional activation energy. The results exhibit the same general behavior that was found from the numerical integrations [1091 for conditions near bifurcation. Heterogeneous solid propellants possess additional mechanisms with potentials for producing oscillatory burning. A 2 6 typically may be a better criterion for intrinsic planar instability than the criterion A > 3. sustained coherent oscillations of the combustion will occur. and under these conditions pulsating deflagration of a homogeneous solid propellant is anticipated.5. If attention is restricted to the vicinity of the bifurcation point. a mechanism like that just described may be relevant. It was indicated in Section 9.=. In effect. in this case. the difference between A and its bifurcation value is treated as a small parameter.+ = 0. the gasphase flame may be absent. is closer to the value inferred from the numerical integrations than is that obtained from the more formally correct asymptotic analysis.24. obtained above from the asymptotic analysis. relatively small rates of heat feedback to the surface through processes that are not too strongly dependent on temperature may produce stability of the steady deflagration. the resulting bifurcation value of A . The methods of analysis possess a qualitative similarity to those of the shockinstability analysis discussed at the end of the previous section./t. in the presence of a mechanism for synchronizing the phases of the oscillations over the surface of the propellant. particularly in the limit in which the pulse duration is short compared with the time between pulses. Although the theoretical explanations that have been proposed for chuffing [I 151[ 1 171 appeal to concepts of homogeneous thermal explosions and usually introduce more than one chemical step. it has often been called chgfing. The departure of the oscillation frequency from its value at bifurcation is expressed in the same type of series. For example. say t. so that inert heat conduction occurs for x > 0 as well. At sufficiently low pressures.and oscillatory solutions for temperature profiles are calculated as perturbations about the steady solution in the form of a power series in . give A > 2 as the criterion for instability [ill].1. approximately 4.334 Combustion Instabilities gasless combustion. the mechanism may involve chemical interactions between the metal and the oxidizer.5 that heterogeneities introduce at least local periodicities and that. This phenomenon has been observed at low pressures in strandburner and rocketmotor tests of certain propellants. Stability analyses in which equations (75) and (76) are employed with a &function heatrelease rate but without (i?T/dx). A review is +fi . For solid propellants..
+fi * F... Inherent Oscillations of Burning Solids 335 available that includes discussion of influences of preferredfrequency combustion in heterogeneous propellants [1191. Manson.5. Since k. Spinning propagation of deflagrations in cylindrical samples of certain homogeneous solid combustibles has been observed experimentally [114]. fi .. The results show that the minimum value of A along this limit curve occurs at k. the smallest cylinder radius for the occurrence of this spinning propagation is roughly a z 3. This that result suggests that there may be materials for which 4 < A < 2 are incapable of experiencing pulsating combustion under any conditions but that can exhibit spinning combustion if the diameter of the cylinder is sufficiently large.2. Oppenheim and R.6 for large values of A but gives A = 1/2( < 1) at large values of A / B .6 is changed to I/$.3. r = a. A model for spinning propagation has been proposed [120]. I. The inherent oscillations that have been addressed here in fact correspond to a limiting case of the diffusivethermal intrinsic instabilities of flames. New York: American Institute of Aeronautics and Astronautics. “Stability of SolidPropellant Combustion to NonPlanar Perturbations” in Dvnarnlcs of Flumes and Reactioe Systems. Axial propagation in a cylinder of radius a is considered. admitting nonplanar perturbations in the model of [l 111described previously. Soloukhin. At large values of the Lewis number the character of the diffusivethermal instability is that which has been described here. timedependent phenomena.1). ( q ) / d q = 0 for the Bessel function of order n.5 that additional types of instability behavior may occur if diffusion of chemical species is not negligible. K.. although the physical mechanisms involved of course are very different.84. Higuera and A. The stability limit ( a = 0) may then be obtained in the form of a curve of k. uo is the flame speed of the unperturbed wave and qmn is the mth root of the equation d J . k.* Since the smallest nonzero value of qmn is q 1 z 1. J . eds. N. with an adiabaticity condition applied at the wall. vol. 95 of Progress in Astronautics und Aeronuutics. 1984. the stability boundary in Figure 9. as a function of A . There is a geometrical analogy here to spinning detonations (Section 6. = 1/2 and has A = 4. represents a nondimensional wave number of the disturbance in the transverse direction. Lifian.9. which will be introduced in Section 9. the equation analogous to equation (78) becomes a dispersion relation. the permissible number of spin cells increases as the diameter increases. In general. When trans= + verse disturbances are admitted. R. if A z 4. and a linear stability analysis has been worked out [121]. The ideas of oscillatory burning that have been considered thus far in the present section have been restricted to onedimensional.7 uoz. A. giving the complex frequency as a function of the wave number. an additional nondimensional parameter appearsnamely. J. which approaches the boundary shown in Figure 9. An algebraic expression of the type of equation (78) is obtained. which is below the value 2 + J5 that was obtained for the planar instability.. 248258. have shown that a similar phenomenon occurs for the model that led to equation (78). Bowen. It will be found in Section 9. = q m n u o ~ s where /a.
1. by locally enhancing rates of heat transfer. Here we shall merely give a brief discussion first of screaming. The main difference between the two types of motors lies in the character of the amplification mechanisms. Because of their fewer natural damping mechanisms. OSCILLATORY BURNING IN LIQUIDPROPELLANT ROCKET MOTORS Liquidpropellant rocket motors are no less susceptible to oscillatory burning than are solidpropellant motors. Equation (5 1) is useful for calculating contributions of homogeneous processes to amplification. then of chugging. and the latter involve perforated sheets on the chamber walls. A thorough presentation of the subject of combustion instability in liquidpropellant rockets has been published in a volume of more than 600 pages [122]. Conditions might occur under which mixing is rapid and combustion slower so that homogeneous gasphase chemical rate processes provide some amplification. most of the materials in Section 9. it can rapidly burn holes in propellant injectors or chamber walls. although various other descriptive terms also have been applied. Therefore.4.ough viscoelastic damping and solidparticle damping usually are absent for liquid propellants. for example. Analysis of acoustic amplification by combustion processes in liquidpropellant rockets is more diffcult than that for solidpropellant motors . Diffusion flames also may be established elsewhere than around droplets. at least to some extent. The former are solid surfaces extending into the flow to interfere with establishment of lowfrequency acoustic modes and to enhance attenuation. between fuel and oxidizer streams. Combustion is distributed more or less homogeneously throughout the chamber of a liquidpropellant motor and generally involves droplet combustion. and finally of instabilities at intermediate frequencies.1.1 is relevantespecially the discussions of oscillation modes and of damping mechanisms. Acoustic instabilities in liquidpropellant rocket motors share many features in common with those of solidpropellant motors. The former type has been called screaming and the latter chugging. Rarely has a development program for a liquidpropellant rocket been completed without encountering a problem of combustion instability. liquidpropellant motors more often need instability “fixes” like the baffles and liners mentioned at the end of Section 9. alth. and responses of these diffusion flames to acoustic oscillations may contribute to amplification. designed according to the principles of the Helmholtz resonator (described in the following section) to increase acoustic damping by dissipation in the oscillatory flow through the orifices. The two major types of combustion instabilities for liquidpropellant motors are acoustic instabilities (with frequencies greater than roughly lo3 cycles per second) and instabilities of lower frequencies that typically involve interactions between chamber processes and flow in the propellant feed lines.3. Screaming often is the more severe of the two in that.336 Combustion Instabilities 9.
[125]. Consequently. general inferences about aspects of scaling [122].3.6 and 4. and in various processes occurring in the combustion chamber. [ 1221. for example. Therefore.9. These frequencies are generally sufficiently low compared with the natural acoustic vibrational frequencies of the chamber that the pressure can be considered to be spatially uniform throughout the chamber. However. [124][127]. Equilibrium and frozen sound speeds with respect to droplet behavior may be identified (compare Sections 9. possesses the greatest potential relevance to acoustic instability in liquidpropellant rockets [1293. as a model for combustion in the wake region of a vaporizing droplet. Chugging is a system instability having frequencies less than roughly lo2 cycles per second and involving oscillations in the propellant feed lines and injection systems as well as in the combustion chamber. also have been applied [122]. A few analyses have been pursued concerning timedependent vaporization and diffusionflame combustion in which linearizations about known quasisteady solutions were developed with the objective of ultimately being able to calculate amplitude and phase relationships for use in an amplification expression like equation (51) [94]. Numerical integrations of nonlinear differential equations. Crocco [20] * Amplification expressions in general are not as simple as equation (51) for twophase flows in rocket motors [128].* The three specific diffusionflame problems analyzed were the stagnationpoint boundary layer on a vaporizing fuel [126].3 have been applied more often for liquidpropellant motors.1. the laminar boundary layer on a flat plate of vaporizing fuel 1941.2. These equations may involve a number of time lags. Timelag hypotheses have become relatively sophisticated for acoustic instabilities in liquidpropellant rockets [20]. which correspond to delays in the feed system. Further research on problems like these could improve our fundamental understanding of amplification mechanisms for combustion instabilities in liquidpropellant motors.4. [123]. the oscillations depend in a lessdetailed manner on the nature of the processes occurring in the chamber.6). with chemical kinetics and diffusion processes treated in overall quasisteady approximations. [127].5. and a masssource term may arise in equation (51) in the development of a conservation equation for the acoustic energy in the gas. the quantity @ must include amplification effects that arise from both energy sources and mass sources.1. interpreted. because of the complexity of the problem. and the laminar jet diffusion flame [124]. . the application to instability calculations has not been carried beyond the point of drawing rough. From the viewpoint of equation (14). in the injection system. Acoustic theories may be derived from the conservation equations of Chapter I1 for the purpose of analyzing acoustic amplification in spray combustion. and ordinary linear differential equations with time lags are well suited for describing the instability. Oscillatory Burning in LiquidPropellant Rocket Motors 331 because the direct use of admittances through approximations of planar burning surfaces seldom can be justified. timelag approximations of the type discussed in Section 9. [122]. Numerical estimates suggest that the last of these three problems.
* G. whose generation may be enhanced by pressure waves in suitable geometrical configurations. A number of reviews are available [20].3. The mixtureratio variations are convected through the chamber and. which often has been applied to instabilities of this type in motors. Toong. It is easy to imagine that a sustained oscillation in a longitudinal mode may be established in this manner. the frequency will be less than an acoustic frequency of the chamber. [122]. A closely related mechanism also can be involved in rumble instabilities in ramjet combustors. do not decay before reaching the nozzle.338 Combustion Instabilities has made a considerable amount of theoretical and experimental progress in deducing properties of the time lags of the conversion processes in the combustion chamber. Abouseif. in turn. higher than chugging but lower than screaming [122]. [129].2. so that a change in the pressure at the injector produces a change in the injected fueloxidizer mixture ratio. fails to distinguish mechanisms involving mixtureratio variations from those that do not. from which it may be seen that onedimensional instabilities of the planar detonation structure involve qualitatively the same type of process.1. without variations in the mixture ratio. delineating regions of selfexcited instabilities in the entire rocket system. discussed in Section 9. result in variations in the temperature of the burnt gas which. Theoretical analyses of lowfrequency oscillations involve determining the response of one section of the rocket system to vibrations in another section. then a sustained oscillation can develop. if the combustion is quasisteady and the consequent nonisentropic variations in burntgas temperature with pressure. [128].* A more detailed discussion of a phenomenon of this type was given in Section 6. There are mechanisms for oscillations at intermediate frequencies. Thus vorticity may play a role in intermediatefrequency oscillations under appropriate conditions. E. and the term is therefore insufficiently descriptive. . and T.1. A. Tsien [ 1301 has given clear illustrations of these analyses. may modify the nozzle flow. and developing feedback servomechanism techniques for stabilizing the system. 83 (1984). A similar mechanism can readily be envisioned for an endburning solidpropellant motor. Keklak. [1311[ 1341. For example. producing pressure perturbations that propagate back upstream acoustically to influence the pressure at the injector face. upon combustion. J. Convectiveacoustic instabilities of this general kind also could involve the convection of vortices with axes transverse to the flow direction or of swirls having longitudinal axes. and since half of the process is acoustic and the other half convective (which is slower). the injection rates of fuel and oxidizer may differ in their sensitivities to chamber pressure.5. C S T 3 6 . in propellant motors. Y. The term entropy waue.
SYSTEM INSTABILITIES IN COMBUSTION EQUIPMENT Chugging in liquidpropellant rockets is only one of many examples of system instabilities in combustion devices [135]. where j is the average gas density in the tube and u is the average outward velocity of gas in the tube. System Instabilities in Combustion Equipment 339 9. Here we shall not address problems involving acoustic wave propagation.j) = ( p d ) du/dt. a source of excitation. such as a suitably . and it may or may not be necessary to consider acoustic wave propagation in one or more of these components in theoretical analyses [138][142]. with frequency WH =a / J W . we shall restrict our attention to bulk modes. (8 1) The derivation of equation (81) is invalid unless the resulting Helmholtz frequency wHis small compared with the lowest natural frequency of acoustic waves in the chamber. a force balance on the gas in the tube is d(p . then a representative acoustic frequency is all.p). Assume that the atmospheric pressure remains constant at the outer end of the tube at a value p. dthat is open to the atmosphere.4. As may be seen from the contribution of Putnam to [137]. since otherwise an acoustic field with a nonuniform p would have to be considered. [136]. Since frictional damping always is present but has been neglected in the derivation of equation (80). and then substituting the result into the first expression. Applying equation ( 3 ) to the gas in the chamber. differentiating./(a/l) is the square root of the ratio of the volume of the tube to that of the chamber. and consider slowly varying processes for which the pressure p at the inner end of the tube is equal to the spatially uniform pressure within the chamber. a considerable amount of research has been performed on mechanisms of these instabilities. Interactions of processes occurring in intakes and exhausts with those occurring in the combustion chamber typically are involved. Conservation of mass for the gas of density p in the chamber is V d p / d t = p d v . we have d p / d t = (dp/dt)/a2. in which spatial variations of the pressure in the combustion chamber are negligible.9. Consider a gasfilled chamber of volume into which is inserted a tube of length 1 and of crosssectional area . we find that the pressure history is described by ( l V / d ) d 2 p / d t 2 = a2(p . (80) Equation (80) possesses solutions that are oscillatory in time. which is small for small tubes in large chambersthe configuration envisaged in the Helmholtz model. a related restriction limits the length 1 of the exit tube. By substituting this relation into the one preceding it. With friction neglected.4. The simplest example of an oscillation in a bulk mode is the classical Helmholtz resonator. If 1 is comparable with a characteristic length of the chamber. and the ratio cu.
growth of oscillations would need an excitation source even if there were no damping. the stability limitis defined by putting a = 0 in equation (85). is a suitable nondimensional frequency. Equation (81). Since in rocket designs the fractional rate of increase of L* is small compared with the rate of development of the instability. which is directly useful in design of the acoustic liners defined in the previous section.E) . 1 + (a + iW)/W. this ratio often is denoted by L*. dp/dt = (jj//m)(m. A mass balance for the gas inside a rocket chamber with a choked nozzle is Km = pCD + d(pL*)/dt. and its ratio to a characteristic exhaust velocity provides an estimate of the residence time of a fluid element in the gas phase inside the chamber. K is the ratio of the burning area to the throat area. Instability occurs when a > 0 in the solution to equation (85). An example of bulk modes in solidpropellant rockets is afforded by the lowfrequency. (85) where A and B are given by equations (67) and (68) and s by equation (79) [compare equation (66)]. and by employing equation (3).4 is considered.1. it is reasonable to neglect spatial variations of the pressure within the chamber. and therefore the neutral stability condition provides a relationship among the dimensionless .p). it is seen that 07. (82) where m is mass burning rate per unit area for the propellant. In view of equation (79).(p . we find that co.(1 + A . = (83) where a characteristic frequency for the instability is WL a2CD/L* (84) Since equation (84) shows that oL decreases as L* increases. instability [7]. or L*. The response of the burning rate to pressure variations is needed for use in equation (83). which are produced by propagation of acoustic waves. A characteristic length of importance in rocket design is the ratio of the gas volume in the chamber to the throat area of the nozzle. and C Dis a discharge coefficient for the nozzle.340 Combustion Instabilities phased rate of heat release by combustion in the chamber [see equation (51)]. if L* is sufficiently large. = nBs/[s2 . If the mechanism of Section 9. also often provides a reasonable approximation for frequencies of bulk modes in combustion devices even when the mean velocity of flow out of the chamber exceeds the oscillation velocity. must be available if sustained oscillations are to occur in the Helmholtz mode. then either by use of Laplace transforms or (more simply) by seeking soluit is readily found from equation (83) that tions proportional to e(a+iW)'. by subtracting the steadystate mass balance from equation (82). defined as the ratio of the mass flow rate through the nozzle to the product of the throat area with the chamber pressure.5.B)s + A]. The condition for neutral stabilitythat is.
5. B) (86) as an equation for the stability limit.1. dp/dt becomes sufficiently small compared with p . It is found that L* instability occurs when oLz. then it is observed that the nearly sinusoidal lowfrequency instability progressively evolves into a nonlinear phenomenon having the character of chuffing. The two characteristic times involved in the mechanism are the gasphase residence time in the chamber and the condensedphase. a propellant that does not exhibit the nonsinusoidal oscillations while burning in the open may experience them in a suitable chamber.5. A .. this critical valuethat is. Formulation through asymptotic methods We now restrict our attention to premixed gaseous combustibles and address the question of the intrinsic stability of their deflagrative processes. HYDRODYNAMIC AND DIFFUSIVE INSTABILITIES IN PREMIXED FLAMES 9. there is a critical value of wLz. Hydrodynamic and Diffusive Instabilities in Premixed Flames 341 parameters n. [143][147]. we may therefore write (aZC. discussed in Section 9.m2) = f(n7 A. The . the term chuflng as used in practice may apply to different fundamental phenomena. heatconduction time in the burning solid propellant. and B). Since iii is proportional to according to equation (59). The topic is a large one that has undergone extensive advancement in recent years./(c.5. There have been many studies of L* instability that support various inferences of the analysis outlined above [I 171. we see from equation (86) that for a given propellant L*p2" assumes a critical value at the stability limit. In view of equation (55).. and wLz.. where the function f is to be obtained is above from equation (85).l. If L*jj2"is progressively decreased below the critical value for instability. B. Theoretical investigations also have addressed questions of influences of spatial gasphase temperature variations [1481 and of solidphase heterogeneity [1491 on the instability. Here we shall only be able to touch on some of the highlights.2. a relatively short gasphase residence time.9. This prediction is in accord with experimental observations on L* instability [1431.lL*)p. Therefore. In other words. Thus it may be expected that for a given propellant (that is. for given values of n.p in equation (83)which corresponds to a chamber with a low capacity. and the instability appears when this product is less than its critical vaIue. The mechanism involved in this chuffing process need not necessarily be the same as that of the corresponding intrinsic instability since an essential role may be played by the fact that the ratio of the chamber residence time to the solid heatconduction time is small. 9. A .for the occurrence of instability. when 0 .
1. The constant a. transport and chemicalkinetic properties of the system [155][157]. a sawtoothtype history of the reactionzone location is a typical result 111641. Asymptotic analyses have demonstrated this to be true [160]. McIntosh and J. [159]. where x(t . B. We shall see that a richer variety * Additional studies with findings of unconditional stability are those of J. 161 (1984). I. [l50][153]. fundamentally.Some of the results indicated unconditional stability in adiabatic propagation for the classes of flames investigated [154]. C & F 3 . Prikl. The results of Section 9. a nonlinear ordinary differential equation with a time delay+ may be derived by asymptotic methods for describing fully nonlinear pulsations [1681. [161]. (1953). M. Zel'dovich and G. the limits of which depend on the thermodynamic. while others identified regions of instability. Clarke. CST 38. who addressed nonplanar disturbances as well. a direct correspondence between stability and flammability limits is not to be expected. and the analysis of Section 9. Here we shall be concerned with the stability of planar deflagrations to nononedimensional perturbations.1) signifies the function x ( t ) evaluated at b .342 Combustion Instabilities reader must consult reviews for more thorough presentations [137]. [lSS]. oscillatory propagation might occur if the thermal diffusivity is sufficiently greater than the diffusivity of the limiting reactant (the stoichiometrically deficient one whose concentration vanishes at equilibrium). 182189. + . Attempts to correlate flammability limits with stability limits have been unsuccessful.* At the time that these investigations were performed. B. [168].1. Zel'dovich. and of G. The equation is of a type that has been encountered in other contexts and may be written in nondimensional variables as adx/dt = e?(''' . limits of flammability under perfectly adiabatic conditions are not anticipated to exist . Most of the early analyses of the stability of planar deflagrations treated only onedimensional perturbations [1541[ 1591. where 5 represents the nondimensional distance of equation (518) between the flame holder and the steadystate reactionsheet position and b is the Zel'dovich number appearing in equation (566). 61 (1959). and numerical integrations with real kinetics have encountered the same phenomenon under certain conditions [ 1621. F. I. A. The delay is the time for a temperature perturbation to travel from the reaction sheet to the flame holder and back.2 suggest that even for gaseous reactants. 21. Barenblatt and Y . the oscillations tend to be sinusoidal if a is near 2in and sawtooth at small values of a. is er/(bl). C. 856 (1957) and Y . for example. Upstream heat loss to the flame holder of a flatflame burner can broaden the range of conditions over which the oscillations occur . Mat. analyses of pulsations of these " burnerstabilized" flames have been performed by both numerical and asymptotic methods [1631[ 1691. Barenblatt. In particular.2 suggests that an instability is likely to evolve to an oscillatory propagation rather than to extinction. For more recent. The steadystate solution x = 0 is unstable if a < 2 h . Richardson. 4 t h Symp. continuing work on this problem see. Although an oscillatory mode might turn out to be more susceptible to extinction by heat loss. an objective was to equate stability limits with flammability limits of the combustible mixture. of order unity. Mekh.
/Am and Pr. y . z. t ) = F ( y . E pouo/p. [ = ZU. . However. z. we shall not discuss influences of reaction mechanisms on stability. the chemical reaction is confined to a thin sheet in the flow. V . Hydrodynamic and Diffusive Instabilities in Premixed Flames 343 of behaviors is encountered. When analyses are pursued in outerscale variables. t)v. and the thermal diffusivity evaluated at the adiabatic flame temperature. v. I = L. with the unburnt gas extending to x = . and p 2 = (fp + K ) / ( $ ~ K . . t ) if the x coordinate is not parallel to the sheet in its local orientation. For the undisturbed flow.c13 and the burnt gas to x = + m. respectively. For all purposes except the analysis of the sheet structure. G(x. Prandtl numbers based on the first and a modified second coefficient of viscosity.. = ( i p .. An appropriate nondimensional  puu. and z = t v 2 / a m . it may readily be imagined that in the presence of a nonplanar disturbance. tworeactant process of large nondimensional activation energy. reaction intermediaries may diffuse laterally from one part of the flame to another and thereby affect the response of the flame to the disturbance./ci.f. Employ the steady.5. it is convenient to work in a coordinate system that moves with the sheet. the nondimensional functions p . can be written as aR/az a ( ~ u ) / a t v. = p/p.9. and V F has no longitudinal component since by definition F is not a function of x.cp. laminar flame speed.)cP./ct. At large values of the Zel’dovich number. equation (1l). The coordinate transformation also enables a nondimensional version of the equation for momentum conservation to be written from equations (12) and (15). To allow for defined as Pr. Attention will be restricted to a onestep. Since research on this topic has not yet progressed to a point at which clear general conclusions can be drawn. Departures from onestep kinetics can produce significant influences on flame stability even if the normal flame speed can be described well by a onestep approximation. t ) = Owhich in terms of the Cartesian coordinates (x. is a twodimensional gradient having dimensionless components (d/dq. with uo given by equation (578). ) may be introduced. For example. one review article is available that summarizes current knowledge on the g&e& fH3. the sheet may be treated as a surfacefor example. z ) may be written locally as x = F(y.v V F ) . Under the assumption that the reaction sheet is smooth and nowhere parallel to the x axis. variable viscosities. C . (RVJ = 0./(p. measured in the burnt gas. and the longitudinal mass flux relative to the reaction sheet is + +  (88) in which v1 is the x component of the velocity vector v. For this purpose. may be rc./CI. adiabatic.. = p(vl aF/at .f. (87) where R = pip. z. J./a.cp.  + + . for defining nondimensional space and time variables as 5 = xu. let the x coordinate be normal to the planar flame.. = p. where f ( y . vI is a transverse velocity vector composed of the velocity components in the y and z directions made nondimensional through division by v. a/a[). through a transformation of variables.. y~ = yv./A..
p2 = 1. we shall adopt these assumptions..344 Combustion Instabilities measure of the pressure is P = (p . Most of the analyses that have been performed treat p and K as constant. and GI are quantities that are proportional to derivatives of pl. so that Pr. The equation for conservation of energy will be written under the assumptions that the Mach number is small and that the work done by body forces is negligible. and it is often assumed that K = 0. we shall neglect the Dufour effect (and later the Soret effect). where pmis the downstream pressure of the steady. GI. (x) and transverse components of which will be written as Flland Fl.= 0 and GL = 0. we obtain x : = p ah aP + pv*Vh = + V*(AVT) at at N  V. the moregeneral forms exhibited here are of interest for discussing influences of variable transport properties and for pursuing further investigations. = SPr. so that . and a nondimensional body force per unit mass may be expressed as F = ~fiam/v the ~ longitudinal .ul = 1.pm)/(pm u i ) . respectively. In addition. and where the Laplacian operator in the transformed coordinate system is and GI. adiabatic deflagration. in which h = hi y i . so that by use of equation (16) in equation (372). Eventually. . both of which are accurate approximations for the deflagration problems considered. The longitudinal and transverse components of momentum conservation then become.
In addition. Therefore. to circumvent complexities associated with the multicomponent diffusion equation. .VY. .. Analysis has shown that there are conditions under which the Soret effect may even change the character of the instability [170].m).5.cp.1. m). we can take advantage of the appreciable simplification afforded by neglect of crosstransport effects. in demonstrating the results of interest here. Hydrodynamic and Diffusive Instabilities in Premixed Flames 345 It is not obvious that the crosstransport effects are unimportant in deflagration stability because it will be found that changes of diffusion coefficients or Lewis numbers by amounts on the order of 10 % can be significant. H i = hi/(cp. which appear through the H i with hi given by equation (1ll). in which it will be convenient to let the reference temperature T o be T. we shall neglect bodyforce and pressuregradient diffusion (likely good approximations) and shall employ the diffusion equation that would apply if the species i = N were present in great excess. its only influence appears to be a relatively small. With the nondimensionalizations i 2.. namely. but for usual flames. Tm).1 where the Lewis numbers are Lei = Am/(p. The somewhat lengthy form of equation (93) is a consequence of including variable transport coefficients as well as variable heat capacities. XV. equation (92) then becomes 9 N. in the transformed coordinates. . and L = nm(V * q R ) / [ ( P m 0. . = 4 ' 2 . (E25)]. = D.The term ap/at has disappeared because it is of the order of the square of the Mach number if changes in P are assumed to be of order unity. m)'TmI. c p .9. hi = PDi/(pm Di. including mixtures containing hydrogen (for which the effect might be anticipated to be greatest). quantitative modification to stability boundaries [153]. i = 1. . and Soret effects typically may reach 10% of those of the ordinary diffusion processes.mDi. where Di is the binary diffusion coefficient for the species pair i and N [compare equation 3 = T/Tm. N .
. 1). For nearstoichiometric conditions. . and with R related to these quantities through the equation of state. v i = Fv. but we shall not discuss it here and shall assume that attention is restricted to conditions v. 1 ) for reaction products and vi = 0 for nonreactive species.. the species i = 2 may become the limiting reactant at various times and positions along the flame sheet. i = 1) . Appropriate integrations of the differential equations across the reaction sheet serve to eliminate the rate term w from the system. tworeactant chemistry to be considered. 2 identify the reactants and consider i = 1 to be the limiting or deficient reactant.. but a revised asymptotic analysis of the steady. P . we let i = 1. 1 ) = (p.~) prodyct is equal to . J(W1v. thereby providing a set of reactionfree equations with reactionsheet jump conditions for analyzing the dynamics of the flame. where a dimensionless reactionrate function is + With the preceding assumptions and in the transformed coordinates. an interesting phenomenon may occur in the perturbation about the steady. (x/w) xr= (x. . l/(Wlv. vl. and (95) are suitable conservation equations for describing the evolutions of u. [ V1u. v. implies that the ratio W ~ / ( W ~for V~ any . If specific heats vary. An analysis of this effect has been developed [171]. (95) x.. The reactionzone equations " I> at . A l # 1 or di # 1. (90). RO = JF).v. adiabatic flame would give the correct formula..). .modified as suggested by equation (B16).. 1).W.. v 2 = .W ~ / ( W ~ V= . Equations (87). (93)..f)> where v1 = . consistent with equation (578). equation (1 4.1. For the onestep. lYJll ucts.~ w2 )/ (W. (89). planar solution. t'i/cIm)w/(Wlv.346 Combustion Instabilities The equations for conservation of chemical species contain the reactionrate terms that will be nonnegligible only in a narrow region about 5: = 0. )N  1. and diffusion flames emanating from the stoichiometric points on the flame sheet may then be present in the downstream region. lYJlz + produnder which it does not occur. . then equation (578) is not quite right. 0. equation (14) then becomes 6i =A X Lei +V~W + (Vld. For the reaction v.  (V.. instead of i = 1.
o is the initial mass fraction of the deficient reactant and the h: are the standard enthalpies of formation that appear in equation (11 1) and that are to be evaluated at the reference temperature T. It does imply that (since v 1 = l)(ax/d()[Lel/ (Leivi)] aY. (96) where the nondimensional heat released per unit mass of mixture has been defined as Q = Y l . P = EiQ/(RoL). in the formulation that has been given here. oLel) be continuous. +  + + xY=.in which Yl.. The conditions obtained from equations (89). and this result may be used in the jump condition obtained from energy conservation to show that + do/at  ril i= 1 vi(Hi.l These results require further that u. f ) av. When equation (95) is integrated across the sheet by use of equation (91) it is found that the discontinuity in a x / d ( is XI"=./a( is continuous [as may be derived directly from equation (95) by dividing by vi and adding to the equation for Y. m . Al. 9. . simply by integrating the equations across the reaction sheet.)au/d( and (V. + Pr. vL. ~ ( h 7vihp)/(cp. The first of the conditions quoted from equations (89) and (90) expresses a pressure discontinuity that balances the discontinuity in the viscous stress tensor. and (93) in effect involve only the longitudinal components of the stress tensor and of the heatflux vector. treating fl< as being of order unity) and then expanding the resulting equations in the small parameter fl. m> is continuous.9.5. and hi are continuous.HN.The relevant Zel'dovich number is < '. and from equa( H i .)(dx/d()/Lei is continuous. which (since vi = 0 by mass conservation in the chemical reaction) may be expressed in terms of the nondimensional heat release that (dY. R .(Pr. However. S)[au/d< (V.Tm). to eliminate w prior to integration]. from suitable combinations of equations (89) and (90) that P ./a<] &. f but this result is not sufficient because the integral is not readily expressed in terms of other variables. (90).' x (1 + IVIf12)1 Leivi wd(.IfN. a more thorough asymptotic analysis of 1 (ay1/8i">/~el + ./a()Q/ appears in equation (96) as the requirement that a9/d( ( Yl. and the second states that the streamwise gradients of the components of velocity tangent to the sheet are continuous. and be continuous in the first approximation and rely on the assumptions that p l .. p 2 .../a< are continuous. In this way it is found from equation (87) that Ru is continuous. all the jump conditions except those of equation (95) are obtained relatively easily. Hydrodynamic and Diffusive Instabilities in Premixed Flames 341 to be integrated may be developed formally by stretching the coordinate about ( = 0 by a factor fl (that is. Since the transverse coordinates and the time variable are not stretched. tion (93) that a9/a.
1 is of order P' downstream. where the function G is defined below equation (578).The differential equation describing the reactionzone structure in the first approximation. and Y2.the matching condition '.6. a)Y. the expressions + + (97) 6 = 6. n2. [175] systems.2. . in the formulation the order of magnitude of 11 .::n21 Lei' L ~ .. n2. at the leading order in p. so that for the reactionzone analysis. it contains all the essential information associated with the reactionzone structure.2. instantaneous values just downstream from the reaction sheet. so that in the scaled variables appropriate to the reaction zone. Y2. For most problems (for example. thereby enabling the equation to be integrated to provide. gradients of the total enthalpy and of the mixture ratio of the reactants are negligible in the first approximation within the reaction sheet. Therefore.f may be treated as being of order p.f .f constants representing the local.348 Combustion Instabilities the reactionzone structure is needed for deriving a jump condition for a y. /at. obtained from equations (94) and (95) (for i = 1) through appropriate scalings and stretching.V ~ ) "(98) ~' (I Le 1 + l V L f l 2 1 = in which equation (578) has been employed as a definition of G(nl.' Y'2 ex~C(B/Q1(1 . [173] and tworeactant [174]. Evaluation of these constants is aided by the further result that Yl = 0 (and hence aYl/a( = 0) downstream from the reaction zone. Because of the strong dependence of the reaction rate on temperature.o. and 8.oLel) to the lowest order. since 6 .1/61] ~ 2G(n1. to achieve the greatest flexibility in the analysis. Y 2 = Y2. The corresponding onereactant problem is readily . at least in the first approximations.= . with 6. The continuity conditions derived previously enable other gradients to be obtained from this result.. The necessary application of activationenergy asymptotics parallels that given in Sections 9.YivzLez/Lei may be employed. we have (a6/d[).6. Introduction of equation (97) into equation (98) renders the righthand side a function of Yl. both 6 YIQ/(Yl. 5.1 cannot be greater than P. is 1 a2y1 p + n z + 1 Y.YiQ/(Yi. also. for stability analyses).(dYl/at)c=o.oLei).oLel) and Y.1 and has been developed for both onereactant [172]. For example.Q/(Yl. Equation (99) relates the concentration gradient of the limiting reactant just upstream from the reaction sheet to the temperature and the concentration of the reactant in excess at the reaction sheet. Y2Le1/(v2Le2)are constant. a). Z ( .3.
These results aid in simplifying analyses of flame dynamics and contribute to the understanding of factors influencing flame motions (see Section 10.5. (93).f becomes of order unity. Stability analyses are conveniently pursued by perturbing these equations about their steady. These geometric aspects of global flame dynamics have not been investigated. Restrictions on the formulation pertain to wavelengths and frequencies of the disturbances.. Disturbances with wavelengths on the order of the flame thickness (5 of order unity) are permitted here. It may be noted that if a becomes large so that Y2./(v2Le2YI. (89). Results of this type have been developed within the approximation that the extent of thermal expansion across the flame is small [l5l]. hydrodynamic effects and diffusivethermal effects.2. then ~Y. These restrictions are satisfied well in a vast majority of problems. Cellular flamesflames that spontaneously take on a nonplanar shapeoften have structures affected most strongly by diffusivethermal .3). With equation (99) and the jump conditions that have now been obtained. If wavelengths are large compared with the entire flame thickness and frequencies are small compared with the transit time through the flame.5. 5 = 0. A significant contribution to the complexity of the equations that have been given here is the fact that the coordinate system adopted is noninertial and nonorthogonal. planar solutions.. Cellular flames There are three basic distinct types of phenomena that may be responsible for intrinsic instabilities of premixed flames with onestep chemistry: bodyforce effects. Hydrodynamic and Diffusive Instabilities in Premixed Flames 349 recoverable by putting n2 = 0 [so that the functions G in equation (99) cancel] and then letting v2 + 0. For example. 9. the wavelength must be large compared with the thickness of the reaction sheet and the frequency low compared with the transit time through the sheet.3. which implies that a mixture with a sufficient excess of species 2 behaves like a onereactant mixture.1 becomes small. but it could help in describing largescale flame motions and in allowing for situations in which the reaction sheet becomes parallel to the x axis at various points. and (95) with w = 0 comprise a reactionfree description of the flame dynamics. then a further integration across the flame can be performed to derive a single partial differential equation for f ( y . equations (87). These complications are offset by the simplification achieved by placing the reaction sheet at a fixed location.9. (90). It may be possible to obtain an orthogonal system of coordinates by generating the coordinates on the basis of the instantaneous flame shape.a) .. and it is found from the definition of G that the ratio of G's in equation (99) approaches unity. [176] and also for more general situations [177][180]. z. This would not be likely to introduce any appreciable simplification into the local analysis of the flame structure and dynamics. t).
34 (lower right).350 Combustion Instabilities FIGURE 9.Br in molar percentage of about 0.2 (photographs taken by B. it is desirable to discuss all three types of instabilities here. Therefore. propagating downward in an open tube 5 cm in diameter. Therefore. 1. for example.2. 2. However.8 and a molar ratio of hydrogen to oxygen of 1.7 are largely controlled by a particular diffusivethermal process. We shall first address bodyforce effects. Cellular premixed hydrogenoxygen flames. with respect to the burnt mixture. bodyforce and hydrodynamic phenomena also play interesting roles. the cellular flames shown in Figure 9. If the entire flame is viewed as a discontinuity moving at velocity v o with respect to the fresh gas and v. flames propagating upward may be expected to experience an instability that mathematically is a consequence of the term F in equations (89) and (90). 372. 9. and 2.01 (lower left)./g and a characteristic * See pages 371. then through dimensional reasoning. in a sense. phenomena. the ordering. visibility provided by addition of CF. and 458462 of [45]. Bodyforce instabilities It is well known* that a lessdense fluid beneath a moredense fluid is buoyantly unstable [181]. then hydrodynamic effects. is from largescale to smallscale phenomena. .03 (upper left).5. and finally diffusivethermal effects. a characteristic transverse length of the instability in the presence of a gravitational acceleration g may be guessed to be of order uou.7.1. Bregeon). with a mole fraction of nitrogen of 0.57 (upper right).
9. it has been observed that for initially quiescent mixtures ignited at the closed base of a vertical tube open at the top in the laboratory.2). By the preceding reasoning. an elongated flame having a roughly parabolic shape with its nose pointing upward rapidly develops. the streamlines of which diverge in approaching the flame. and achieves an approximately constant rise velocity of the nose (if the mixture is sufficiently weak to avoid the buildup of pressure that initiates transition toward detonation). In earth gravity (g z lo3cm/s2).. Since the nose of the flame is curved and finds itself propagating into a nonuniform flow. the wavelength . the flame motion in these upwardpropagation experiments is affected primarily by buoyancy. the effective nondimensional body force per unit volume becomes R(F. 3 m obtained . . Buoyant instabilities have been observed for flames propagating in larger vented enclosures [1841[186]. this last estimate suggests that the severity of the instability increases as the flame speed decreases. For weak combustible mixtures of different fuels in tubes of various diameters D. Acceleration of a flame sheet produces effects of the same type as those of body forces. A bodyforce instability is therefore associated with flame acceleration. so long as uo < v b . Consistent with the preceding estimates. Thus a flame acceleration in the direction of its motion (a positive rate of increase of . typical wavelengths are estimated to be on the order of a few centimeters and growth times in tens of milliseconds. Nevertheless. . As might be expected physically. Thus. h o / g . sealed at the top and open to the atmosphere at the bottom. and similar phenomena would be expected for premixed flames under appropriate conditions. theoretically [I1831 for the velocity at which an air column rises into a vertical tube filled with water. This may be seen from equation (89) by bringing Rd2f / d z 2 to the righthand side of the equation.5. the flame shape is quite similar to the shape of the air column. but in the flame experiments stabilization effects for nonplanar disturbances are provided by interactions with the burner and by the divergence of the streamlines. Experimentally. an effective body force appears as a consequence of flame acceleration. Hydrodynamic and Diffusive Instabilities in Premixed Flames 351 growth time of order .the measured rise velocities have been shown [182] to agree well with the value ub z 0 . instabilities have been seen in this configuration for diffusion flames on sufficiently large burners (greater than about 10cm diameter) [1871. This configuration is similar to that in which the buoyantly convective Rayleigh instability involving formation of Benard cells often has been studied for nonreactive fluids. The same mechanism is operative for steady flames of flatflame burners with the fuel flow directed downward. propagates upward. the singlelobe shape that is usually observed suggests that the wavelength of the buoyant instability is comparable with or larger than typical tube diameters.3.df/dz) is equivalent to a body force directed from the fresh mixture to the burnt gas.d2f/dz2). In a noninertial coordinate system that moves with the flame (or in which the flame moves at a constant velocity). the flame structure at the nose will differ from that of a normal flame (see Section 10.
we do not discuss influences of electric fields. A pattern of buoyant convection then begins to be established. [l89]. Therefore.2. Indeed. Because ofconditions in France during the second world war. For decelerating flames. Darrieus never was published. the bodyforce effects are stabilizing. Hydrodynamic instabilities A startling discovery in flame theory was made independently by Darrieus+ and Landau [190]. but he presented a paper entitled “Propagation d’un front de flamme” at two conferences in France.352 Combustion Instabilities and growth time of the instability may be estimated as v. the buoyancy terms in the conservation equations are comparatively small. to be discussed later. buoyancy may stabilize a deflagration without appreciably modifying the flame structure. This cooling increases the density of the burnt gas near the walls. or burnerstabilized flames with the flow upward. a relatively slow flame propagating downward in an initially quiescent. it appears to be necessary to include buoyancy in analyses of stability boundaries. There are special situations in which buoyancy can be responsible for instabilities in configurations that might appear to be buoyantly stable. La Technique Moderne (1938) and Congrts de Mkchanique Appliquee. Thus body forces may produce a variety of observable effects on premixedflame propagation./la2F/at21 and d 2 F / d t 2 ( These . in comparison with that of the combustion products in the center of the chamber. a stability analysis that neglects body forces and that treats the entire flame simply as a discontinuity in density that * Body forces relevant to flame structure may be electrical forces acting on ionized species for flames in strong electric fields. the ease with which stable laminar deflagrations are observed in the laboratory may be attributable largely to the stabilizing influence of buoyancy. Paris (1945). ’ .5. This has been done with the effect of flame curvature on the burning velocity included in a phenomenological way [137]. with the flame near the wall moving well ahead of the flame in the central part of the chamber. as well as on the basis of the conservation equations of the previous section [178]. Phenomena of this general type have been observed experimentally [lSS]. with good justification.v. a net rate of buoyant rise of downwardburning combustible gas in the center of a large chamber or in the open is a common phenomenon. Normal buoyancy effects are relatively farfield phenomena in that within the thickness of the thin flame (including the preheat zone as well as the reaction zone). flames propagating downward.* Nevertheless i buoyancy is responsible for observed flame stabilitg then it must have a significant influence on conditions for the occurrence of cellular flames. dux// H 9. For example. and buoyancy forces may then promote downward motion of the gases near the wall. weak combustible mixture contained in a chamber open at the top experiences conductive cooling of the burnt gas at the walls of the chamber. analyses of flame str c ure generally neglect buoyancy.2. the work of G. quantities decrease as the acceleration increases. Because of other mechanisms of instability. Therefore.
P I ) .v. with time derivatives and transverse gradients neglected within the flame. = 0. equation (87) shows that Ru is constant throughout the flame.1]/(1 + Ro). and integration of equation (90) yields Ru(v. This result.1/R. (89) and (90). The first step is to obtain jump conditions across the flame by integrating the equations with respect to 5 through the entire flame. the linearization gives aqag + v. f . R(au/az + a2f/az2 + u au/ag) = . nevertheless is both correct and readily comprehensible (see below) and certainly requires consideration in connection with cellularflame phenomena [1371. are q and [).jag) .= l/& (which is the ratio of densities of burnt and unburnt gas). P (with R = 1 for 5 > 0 and R = R. f = v. = R(av. u. u + = 1 and u. planar solution. for 5 < 0. equation (100) gives o > 0 and hence implies instability. > u. where the components of x. respectively). Since the flame speed is considered to be unmodified by the instability. f ( P + .af/az as 5 + fco]. .P . = constant for 5 < 0). if Re{a} > 0.aP/ag. vI+ + u + V . proportional to Re{eik'X1}. A quadratic equation for o is of C k g obtained. the planar deflagration is unconditionally unstable. where CJ is the nondimensional growth rate. in view of equation (88).) = P .u ..5. and .+ u . the integral of equation (89) gives Ru(u+ .) = V.. = 0. (100) Since R .Clear expositions of the character of this hydrodynamic instability of flame fronts may be found in [9] and [153J. the parts of the perturbations that vanish at infinity are then found to be proportional to ekt for 5 < 0 and to a linear combination and e"< for 5 > 0. The hydrodynamic instability can be derived directly from equations (87). The second step is to linearize the differential equations for the constantdensity flows on each side of the flame about the steady. and v. which is given by u = U (a constant defined to be unity for 5 > 0 and l/Ro for 4 < 0). Hydrodynamic and Diffusive Instabilities in Premixed Flames 353 propagates normal to itself at a constant speed u. > 1.9. The third step is to seek solutions to these linear equations with constant coefficients for perturbations that are sinusoidal in the transverse direction (for example. with respect to the more dense gas demonstrates that since thermal expansion across the flame causes p. (where the subscripts + and .jaz + u av. that u approach U . A dispersion relation may be sought by letting the time dependence of the perturbations be proportional to ear. largely contradictory to common experience in the laboratory. which satisfy the jump conditions at 5 = 0 and vanish as 5 + f co [thus requiring. < po (that is. the acceptable solution to which is CJ = k[Jl + ( R i .).l)/RO .identify conditions just downstream and upstream from the flame.v.V . P = 0 for 5 > 0 and 1 . where k = Ikl. whichwhen combined with the preceding relationshipproduces the condition of continuity of the velocity components tangent to the flame.+ v.
) at small values of (urn . is positive when urn > vo. Since the flame speed is the only dimensional parameter that appears in this stability problem. and approaches unity as v.vo)/v. we see that continuity of the tangential component of velocity across a tilted flame element required the streamlines to be deflected toward the local normal to the sheet in passage through the flame.* Since a flamesheet perturbation with an upstream flame displace * Compressibility and acoustics are absent from the equations of the previous section. . as indicated. they play negligible roles in the problems addressed because the Mach numbers involved are very small. it is clear on dimensional grounds that the growth rate must be proportional to the product of the wave number and flame speed.4  &TO/(v.8./vo + 00. + v. equation (100) states that the growth rate of the disturbance is proportional to the product of the transverse wave number with the geometricmean flame speed the factor of proportionality. Referring to Figure 9. the area increase causes a velocity decrease. This causes a stream tube of initial area A (which must be the same far upstream and far downstream. which vanishes if v. approaches (v. In dimensional variables.). That the constant of proportionality is positive may be traced to the fact that the flameshape perturbations are convected with the fluid. (J&+ urn00 . may be written as 6. since the perturbations vanish there) to be larger at the flame than far away if the sheet is convex toward the unburnt gas. In incompressible flow.. Schematic illustration of the mechanism of hydrodynamic instability.354 Combustion Instabilities FIGURE 9. as illustrated. .8.uo)/ (221. which depends only on the density ratio. = uo.
the resolution must lie in geometric or nonlinear hydrodynamic aspects of flame propagation and in effects of buoyancy. a tendency toward further displacement downstream. dF/& equals the perturbation of u.9. For stationary. From equation (100) we see that the growth rate is inversely proportional to the wavelength 1 of the disturbance. If a laboratory flame is contained within an apparatus whose walls exclude disturbances of wavelength greater than l. for any reasonable value of I. A formula that contributes to this explanation is equation (88)../u.. 271(a. stable flames can be observed in apparatuses with characteristic dimension D too large (for example. thereby causing the growth rate to achieve a maximum value at a particular wavelength appreciably greater than the flame thickness and to decrease thereafter with decreasing wavelength. but it may be anticipated that they often introduce stabilizing influences. Even for wavelengths on the order of 10 to 100 times the deflagration thickness. which shows that since the perturbation of u vanishes at the flame. 1 > I. The range of wavelengths for instability now becomes finite.)/k = 1. then the hydrodynamic instability is . D/6 2 100 [153]) to enforce a condition 1 < 1. planar flames in a vertically upward flow. therefore. The instability is of a purely diverging. It can be shown [137]. 1. to the bodyforce wavelength. it encounters a decreased fluid velocity and therefore (propagating at its normal speed) will tend to move even farther upstream. I = I. Gravity thus introduces stability for disturbances of large wavelengths. Hydrodynamic and Diffusive Instabilities in Premixed Flames 355 ment (F < 0) geometrically must have a curvature convex toward the unburnt gas. nonoscillatory character (a is real)./g E I h . For these flames. diffusive and thermal effects within the flame may cause the flame speed to depend appreciably on the flame shape and on the local flow field [137].. there are difficulties with this popular resolution of the contradiction between theory and experiment concerning hydrodynamic instability. if / h < I. As the wavelength decreases and approaches the thickness 6 of the deflagration.. 2nuO u. Unfortunately. Discussion of these diffusivethermal phenomena is postponed to the following subsection.5. small wrinkles grow more rapidly than large wrinkles. buoyancy must be a significant contributor to stability. < 1 < 1. it is no longer permissible to treat the flame as a discontinuity. then the hydrodynamic instability will not be observed. a downstream flame displacement results in streamtube contraction and. possibly becoming negative at a critical wavelength.. then equation (100) becomes in which the new term is the ratio of a dimensional wavelength characteristic of the transverse disturbance... [178] that if the hydrodynamic stability problem is addressed as before [190] but with the bodyforce terms in equations (89) and (90) retained in the differential equations. Conversely.
since flow separation occurs at the wall as the flame discontinuity passes. it has been inferred [1521. The velocityjump conditions across the flame sheet readily show that all curved flames that are not everywhere normal to the incoming flow produce vorticity . leaving a stagnant layer adjacent to the wall downstream from the flame sheet [1923. It is likely that this last condition applies to experiments in which large planar flames are stabilized in a uniform flow [153]. flames propagating downward in tubes and channels tend to become convex toward the unburnt gas. to the development of turbulence in shear flows). From numerical experiments with equations describing the selfevolution of flame surfaces in the limit of small values of the density change across the flame. Since 1. curved flames in channels or tubes in the absence of buoyancy may represent a stable configuration achieved by the longtime. For an expanding spherical flame in an initially quiescent medium the increase of the area of the flame sheet with time is known to delay the onset of hydrodynamic instability [196]. but the rotationality per se does not appear to be a significant aspect of stability. nonlinear evolution of hydrodynamic instability. it was presumed that the instability evolves to a chaotic state characteristic of turbulence. The flow streamlines then assume the pattern illustrated in the upper part of Figure 9. for propagation in channels this same effect is present because of the curvature of the flame. an additional factor of significance that may be dominant. However.356 Combustion Instabilities eliminated entirely. the time available for growth of the instability is limited by the intersection of the ray with the wall. [198][200] that the hydrodynamic instability evolves .modified by allowing the area A far downstream to be less than that far upstream. In the absence of disturbances like acoustic perturbations (which can flatten flames under appropriate circumstances [191]). except for the ray propagating along the centerline of the channel. for example. is proportional to u o u m . [197] .8. Thus selfturbulization of premixed flames was attributed to hydrodynamic instability (analogous. as suggested above. Even for nonhorizontal flames such as bunsenburner flames. the effect often can be substantial because typical values of 1. the stabilizing influence of buoyancy may not be negligible. downwardpropagating flames in tubes or channels with quiescent or irrotational flow upstream therefore have rotational flow downstream. and moreover. In the early investigations of hydrodynamic instability [9]. for flame propagation in channels in the absence of gravity is a rayoptics aspect of the development of hydrodynamic instability [193][195]. This viewpoint must be revised if the instability evolves to stable nonplanar structures. Buoyancy again may help greatly to stabilize the downwardpropagating flame against hydrodynamic instability. in a sense. for horizontal flame sheets in earth gravity are on the order of centimeters. Thus steadily propagating. for a given value of g the stabilization effect increases as the flame speed decreases. In most configurations flameinduced flow nonuniformities complicate matters. [190].
a complete analysis entails studying the influences of the perturbations on the internal structure of the flamefor example. Of course. on the average. The effects were first addressed theoretically in a semiphenomenological manner [204] by allowing the flame speed to depend on the radius of curvature of the flame sheet (the reciprocal of the mean curvature. [202]. Hydrodynamic and Diffusive Instabilities in Premixed Flames 351 to flames with steady. a Fourier decomposition will introduce a correction term proportional to k 2 in a formula like equation (100) for 0. . The changes in flame structure are associated with variations of the effective diffusivity of the limiting reactant [201]. Stability analyses like those discussed earlier can then be pursued for any value of 2. Significant diffusive influences in cellular flames were established in early work [137].9.and the new term will be most important for large values of k (small wavelengths). diffusive phenomena may play a role beyond their obvious relevance to the cusp structure at the ridges of the sheet. 9. is a constant intended to describe influences of flamestructure modifications on the flame speed. the first reported observations of these effects appear to be those for tent flames with periodic ridges on bunsentype burners. Diffusivethermal instabilities The principal features of the flame shown in Figure 9. However. Although it would seem that the hydrodynamic instability should be the dominant phenomenon in these large flames. mixture is written as a constant times 1 + 2/9.2. Thus evidence is growing against the idea that in the absence of other physical phenomena. they develop pebbled surface structures (with average sizes on the order of 10 cm) that appear to be chaotic in some respects and. the formulation may be viewed as one that retains only the first term in an expansion for small flame curvatures.7 cannot be understood on the basis of the instabilities discussed thus far because the flame speed and the density change vary little from one photograph to another. but the flame structure clearly varies greatly. 2. with the objective of calculating 2 from the fundamental chemical and transport properties of the system.5. It is observed experimentally that as large (up to 10m radius) spherical flame sheets expand. corrugated shapes that have sharp ridges pointed toward the burnt gas (while the diffusivethermal instability evolves to a somewhat similar but unsteady shape that exhibits a chaotic behavior). the socalled polyhedral flames [203]. here denoted by 9and taken to be positive for convexity toward the burnt gas and negative for convexity toward the fresh mixture). propagate at about twice the normal burning velocity [152]. the question certainly is not completely resolved. In particular since 1/94? = . The flame speed with respect to the unburnt where the Markstein length.3.V 2 F for small deflections of the flame sheet. the hydrodynamic instability of deflagrations leads to turbulence. without further inquiry into the flamestructure phenomena that determine 2.5.
where the arrows indicate directions of net fluxes of heat and species. and we now have a reasonably good general understanding of the influence on flame stability of the diffusive and thermal processes that occur within the flame.1)/(2Q)]. [205][225]. = 0 at [ = 0.* The instability mechanisms can be explained by reference to Figure 9.358 Combustion Instabilities Strongly diffusing diffusing reactant Normallv diffusing reactant Heat / \ U L Heat Fresh  U.o(l . 1944.9 Schematic illustration of the mechanism of diffusivethermal instability. The essential physical ideas apparently were first known to Zel’dovich. Nauk SSSR. A key element in the explanation is the fact that for large values of the Zel’dovich number.5.1 but may be motivated from it by employing Ru dY. if this equation is integrated with Ru constant and with the boundary conditions that Y. that is./d< = d’Y. the burning velocity depends mainly on the local flame temperature.eRut)] shows that Ru is proportional to exp[B(tlr . = Yl. This intuitively clear result is not entirely obvious from the formulation of Section 9. X Burnt FIGURE 9. Extensive research on the theory of these flamestructure modifications has been pursued [170][180]. then application of equation (99) to the solution [which is Y. Moscow: Akad. the burning velocity increases with increasing < * They were expressed in his early book./a[’ as a rough approximation to equation (95) in the preheat (convectivediffusive) zone for i = 1. = Yl. Theory of Combustion and Gas Detonation.o at = c o and Y. .9.
2). then Tfdecreases at the bulge. = 1. however.= 1 perturbations. therefore. this reasoning is restricted to disturbances with transverse wavelengths that are large compared with the flame thickness. weakly diffusing reactants). In neglecting nonplanar influences within the preheat zone. wherever Y. the temperature remains constant and equal to the adiabatic flame temperature.5. as indicated at the beginning of Section 9. and with all perturbation lengths large compared with the flame thickness * It must. produce a critical wavelength 1. the equation for evolution of the reaction sheet with . fundamentally simpler physical mechanism that is purely thermal in character and that tends to provide a stabilizing influence for Le. However. sociated with the increase in Tf.* However. strongly diffusing reactant). so that the propagation speed is reduced there (see Section 8. Hi remains constant and from equation (95) that Yi + vi Y.9 the temperature is therefore constant everywhere on the reaction sheet and to the right thereof for this adiabatic system with equal diffusivities. Hydrodynamic and Diffusive Instabilities in Premixed Flames 359 flame temperature in the expected Arrhenius fashion. < 1. > 1. In the lower part of the figure. . heat is lost to the side from the bulge in the upper part of the figure. In the absence of hydrodynamic effects and any other I . In this last situation. thereby giving rise to the diffusivethermal instability. When Lei = 1 and hi = . This reasoning suggests that the diffusive and thermal effects within the flame tend to stabilize the hydrodynamic instability (that is. > 0 such that the flame is stable to disturbances with transverse wavelengths 1 < 1. it can be shown rigorously from equation (93) with L = 0 that If=. be increased. Conversely. while increasing the rate of heat conduction from the At the bulge. > l. if the thermal diffusivity is greater (Le. = l). then these increases are balanced in such a way that Tf is unchanged. which thus is seen to occur for Le. there is an additional. < 1. be less than the critical value for pulsating instability.5. remains constant.9. the heating rate is greater than that for the plane flame. and the reactant flux and conductive flux will both. the local gradients will be steepened sheet tends to reduce Tf. then Tf increases (as a consequence of the preferential diffusion of the reactant with respect to heat).) only if Le. These effects cause the wrinkled reaction sheet to tend to become planar and therefore constitute a stabilizing influence. From this. Increasing the rate of diffusion of the limiting reactant to the sheet increases the rate of heat release there and hence tends to increase the flame temperature T’. the local increase in flame speed. ascauses the bulge to tend to become larger. In Figure 9. in comparison with those of the normal flame. It is evident that a bulge in the reaction sheet extending toward the unburnt gas serves as a local sink for reactants and a local source for heat. and the local propagation speed therefore tends to be increased. = 0.1. If the thermal diffusivity equals the diffusivity of the limiting reactant (Le. if it is less (Le. where the hot gas tends to surround the cold combustible.Il for all species i.
the diffusive and thermal phenomena discussed here evidently do not always produce stabilizing influences for nonplanar disturbances... > Le. therefore. nonplanar cellular shapes. The consequences of the instability in unstable situations are understood only partially. and planar flames will not be observable in mixtures that satisfy this criterion. approached as z + co. For Le. < Le. # Le. upstream bulges can tend to be suppressed and downstream bulges can tend to be amplified by the mixtureratio variations. The stable solution to this equation.. f ) . is the planeflame solution a f / a z = 1.. For Le. At stoichiometric conditions for a mixture that has its maximum normal burning velocity at stoichiometry. which may therefore exert a largely . Contrary to the suggestion made in Section 9. there is nothing to stabilize the hydrodynamic instability at small wavelengths. > Le. such that diffusivethermal instability occurs for Le. In tworeactant systems with Le. The more strongly diffusing reactant can reach the sink at the upstreampointing bulge more readily than its weakly diffusing partner.360 Combustion Instabilities can be shown to be 1 + af/az = V . nonplanar diffusivethermal phenomena will be enhanced as the instability develops. a twodimensional.2.5. the wrinkles induce local mixtureratio variations. is not too close to unity. there is an additional purely diffusive effect..7 (perhaps moving somewhat chaotically). that can be understood even more readily than either of the two effects indicated above. the steepening gradients associated with development of the hydrodynamic instability accentuate magnitudes of nonplanar diffusivethermal effects. Even for Le.2. then the mixtureratio variations aggravate instability.. timedependent heatconduction equation for f + z in this case. When they do not. mainly in their (thermal) effect on the flame speed through T in nearstoichiometric mixtures their influences are comparable in magnitude to those of the diffusivethermal interactions. Therefore. If the limiting component is relatively strongly diffusing. hydrodynamic instability may prevent the plane flame from occurring unless walls or buoyancy provide sufficiently strong stabilizing influences. . and planar flames in a uniform flow then cannot exist. Since the Lewisnumber effects described in the previous paragraph involve changes in Tf that make themselves felt through the Arrhenius factor. the mixtureratio variation of a weakly diffusing limiting reactant is a stabilizing effect. often termed preferential diffusion of reactants. say Le. and it may be reasoned [201] the flame will evolve to relatively stable. Upstream bulges are relatively enriched in the strongly diffusing reactant and downstream bulges are consequently enriched in the weakly diffusing reactant. ( V . Our reasoning suggests that there is a critical value of the Lewis number of the limiting component. These variations make themselves felt on the dynamics of the reaction sheet f . like those seen at the top of Figure 9. < Le. they may be expected to be large compared with the smoothing effect discussed here if /? is large and if Le.
is just slightly below unity. Since the density ratio R. then Le. In fact. Although the curvature at the nose regions of large cells may be thought to be too small for diffusivethermal phenomena to be relevant there.1)/4]. + cx.ln R. the reaction sheet can be considered to be moved to a less accessible position. = 1 1 ~ P (2R. within the flame.9 (which is obtained at P = 20 for R . + 1. Thus it seems safe to conclude that Le. For estimating when diffusivethermal instabilities may occur./h R. even if the original source of the instability is hydrodynamic.7). it is important to know the value of the critical Lewis number. equals (48/n2) In 2 = 3. therefore. certainly does not exceed 0. the shapes of the cellular flames that develop may be dominated largely by diffusivethermal effects. which lead to cellularflame structures affected mainly by diffusivethermal phenomena. Although our reasoning suggested that Le. the diffusivethermal variations in T.5. = 1) to demonstrate the large influence of gas expansion. Therefore. as has been shown in a further investigation of variableproperty effects [223]. are in fact first initiated by the hydrodynamic instability. That the latter influences are also stabilizing may be understood by realizing that the decrease in density with increasing temperature increases transverse distances through transverse convection and therefore reduces transverse gradients of temperature and of concentrations locally in the vicinity of the reaction sheet. for most real combustible mixtures and. as R. a value that may be compared with the limit 0. with a partially insulating. the influence probably is somewhat greater than would be implied by equation (102) because the decrease in diffusivity with decreasing temperature helps to make the reaction sheet less accessible to reactants. . > Le. .9. that the observed instabilities.. for small reactionsheet curvatures and large Zel'dovich numbers. of the gas expansion associated with the heat release.37 at Ro = 2 and diverges as 4R. has shown [1771 that if the transport properties are constant ( p . Theoretical analysis of a onereactant. thereby are reduced (in effect. (102) in which the factor multiplying 1/P approaches 2[1 + 3(R. with the estimate 10 5 P 5 20. Le. typically has a value of about 5. for R . adiabatic system with constant specific heats. the associated divergence of the streamlines as they approach the sheet provides a strain configuration known [221] to be strongly stabilizing to ripples for diffusivethermal processes. and the smoothing effect associated with constancy of Tf is relatively enhanced. = p z = A1 = di = l). Hydrodynamic and Diffusive Instabilities in Premixed Flames 361 controlling influence on the final cellular shape (a shape somewhat like that seen at the bottom right of Figure 9.) x'ln(l + x) dx. we ignored the finite thickness of the reaction sheet (an effect of relative order 1/P) and did not specifically address influences. the corresponding value of Le. lowdensity layer of fluid placed in front of it).5.
shear viscosity introduces a very small stabilizing effect if the coefficient of viscosity increases as the fluid passes through the flame. this ordering is dictated by the fact that exp[P(Bf . and equations (93) and (95) are simplified somewhat.11 of order 1/p. In this approach it is usual to set v = 0. and in real gas mixtures this ordering usually is reasonable numerically. differs from unity by an amount of order unity. showing that gasexpansion effects increase Y appreis greater ciably. constantproperty analyses. thereby excluding the gasexpansion effects discussed above. we see that the difference between Le. 9’ than predicted by constantdensity. Through activationenergy asymptotics. does not appear in the dispersion relation and that. with this approximation it becomes feasible to admit disturbances with wavelengths less than the thickness of the preheat zone (but still large compared with the thickness of the reactivediffusive zone). Changes in the flame temperature of an order no larger than 1/p times the adiabatic flame temperature are required if the response of the reaction sheet is not to become exponentially large. [219]. With few exceptions [1771[ 1801. [223][225]. within the context of an expansion for long wavelengths of disturbances. through equation (93). There are nonplanar disturbances that. [ 1983[200]. theoretical analyses of wrinkled flames based on activationenergy asymptotics usually treat departures of Lei from unity as being of order 1/p [170]. through Pr. the viscosityinduced modifications in the convectivediffusive zone being cancelled by those in the reactivediffusive zone. The influence of viscosity within the flame on the hydrodynamic instability has been a subject of uncertainty since the early studies of instabilities [ 1371. If the coefficient of viscosity is constant.362 Combustion Instabilities By viewing the coefficient of 1/p in equation (102) as a quantity of order unity (even though it may be somewhat large numerically). [171]. the approach greatly simplifies the analysis and thereby enables qualitative diffusivethermal features shared by real flames to be studied without being obscured by the complexity of variations in density and in other properties. recent analyses of diffusivethermal phenomena in wrinkled flames have employed approximations [208] of nearly constant density and constant transport coefficients. The known diffusivethermal instabilities all appear for [Lei .1)/Q] appears in equation (99). [217][225]. [179]. For the investigation of diffusivethermal effects. [223] also provide expressions for the length Y (introduced at the beginning of the present subsection).. The asymptotic analyses [178]. Therefore. [173]. equations (87)(90) are no longer needed. induce relative diffusion of the reactant and heat to an extent sufficient to produce fractional changes of order unity in the flame temperature if Le. In particular. the viscosity modifies the gas expansion only slightly. Although results obtained with these approximations are quantitatively inaccurate. and unity formally is of order 1/p. [175][180]. while variableproperty effects decrease it somewhat. then there is no effect [178]. it has now been shown [223] that Pr. Physically. It .
For tworeactant flames [175]. in which the real part of the radical is to be taken to be positive. n.) applied.. with Le. with dispersion relations illustrated by insets. aG(n. Hydrodynamic and Diffusive Instabilities in Premixed Flames 363 is possible to include effects of heat losses by retaining L in equation (93).k ) = 1 + J1 + 4(a + k 2 ) . L proportional to 8 . Dispersion relations have been developed through activationenergy asymptotics for onereactant flames. the ratio of the burning velocity of the planar flame with heat loss to that under adiabatic conditions.10..9. The implications of equation (103) are illustrated in Figure 9.. Here the heat loss has been assumed to be linear in the temperature increment [Newtonian.5.10. we have [from equation (822)]. defined in equation (821). in which G and u are defined below equation (578). is defined by equation (81 1) so that in terms of the loss parameter I . ln(l/p) = 1/(2p2).O0 in equation (93) or IC proportional to z in equation (8lo)]. replaced by the effective Lewis number Le. . equation (103) may be (Le. Regions of diffusivethermal instability in a Lewisnumber. u)/an. where various stability boundaries are shown by solid lines in a plane of + k k k FIGURE 9. . The nonadiabatic result is [ 1731 where r(a. and p. heatloss plane. both adiabatic [2 131 and nonadiabatic [I731 ( L # 0). as well as for adiabatic tworeactant flames [175].Le.
10. agrees with that given by equation (102) for R.2. this region includes Le.1 and discussed in Section 9. giving . the dispersion relation exhibits a maximum growth rate at a preferred wavelength and damping at sufficiently small wavelengths (that is. One is the planar pulsating instability. producing a critical wavelength 1. . which are sketches of the dispersion relation. the former value. such as Newtonian loss. this stabilization at short wavelengths.364 Combustion Instabilities the measure P(Le. consistent with our earlier reasoning. could not be obtained in our earlier reasoning. The critical value Le.1) < 21/2 under adiabatic conditions ( p = 1) to 0 < P(Le. = 1.10. As the heat loss increases. this occurs at the largest values of the Lewis number.10.10 for sufficiently large values of the Lewis number. the solution to equation (103) for (r as a function of k . k is positive and CJ is complex.2//3 under adiabatic conditions to unity at the flammability limit.1) of the departure from unity of the effective Lewis number of the limiting reactant as a function of the nondimensional measure l/pz = ln(l/p2) of the rate of heat loss. the region of diffusivethermal stability is seen in Figure 9. = 1. Although these results depend quantitatively on the approximations. it is not yet clear whether observed traveling waves correspond to the traveling diffusivethermal instabilities illustrated in Figure 9. In the dispersion relations sketched in Figure 9. The steadystate solutions at values of p below l/& [that is. corresponding to the lower branch of the burningvelocity curve in Figure 8. at values of k above that at which CT passes through zero). of course. For traveling waves.5. the dashed curves represent Re{@}for conditions under which CT is complex. The stable and unstable behaviors are illustrated by the insets in Figure 9.21 are found to be unstable for all values of Le. Three additional types of diffusivethermal instability appear in Figure.10. There is a narrow range of parameters in which > 0) only in the traveling modes and another instability is experienced (Re{@} range in which instability is experienced in both traveling and pulsating modes (that is. .. [226][229] that in many circumstances oscillations are capable of being transmitted directly along the flame surface. In the range of cellular instability. they are likely to remain qualitatively correct under more general conditions.10 to narrow from 2 < P(Lel . the range of k over which Re{@}> 0 extends to k = 0). which was based on the restriction that the wavelength be large compared with the flame thickness. below which the cellular instability occurs is seen to increase from 1 . It has been found experimentally [153].1) < 18/5 at the flammability limit ( p = 1/&). of Le. Because of the constantdensity approximation that underlies equation (103). indicated at the beginning of Section 9. ln(l/p2) > 1 in Figure 9. The character of these travelingwave instabilities has been investigated theoretically [220]. The other two are instabilities that involve waves traveling along the reaction sheet. . > 0 for stability even in the range of diffusivethermal instability. 9.f proportional to exp[z Re{o}]Re{ei[k'xl+r'm~u~l }.
Internal Ballistics of SolidFuel Rockets. [230]. N. 2. R. * A step in this direction has been taken by T. patterns have been found [232] (at sufficiently large dilutions of the stream of hydrogen coming from the cylinder) in which the combustion occurs in periodically positioned stripes wrapped around the cylinder. . The cell sizes can be correlated on the basis of the wavelength for the maximum rate of amplification of the cellular instability. but near the limit these values decrease into an accessible range. The mechanism of this instability must be preferential diffusion of hydrogen. and the cellular and travelingwave instabilities may be expected to be observable more readily. A similar mechanism could apply to earlier observations of instability in coflowing hydrogenair diffusion flames [233]. Diffusivethermal instabilities rarely occur for diffusion flames. in the forward stagnation region of a porous cylinder. there are special effects that can widen somewhat the range of propagation of cellular flames [222]. through nitrogen and combustion products. the travelingwave instabilities appear to occur at values of Le. There must be inaccuracies in the correlation because of the constantdensity approximation and because of the evidently nonlinear character of the structures in Figure 9. Barrere and F. greater than those of real gas mixtures. (1969). over most of the range of heat loss. 893906. F. A. produced by the increase in the effective Lewis number identified earlier. 235 (1984). Research on nearlimit behavior is continuing. 4th Symp. 169181. with the consequence that there is insufficient hydrogen to support combustion in between.10 that the stable range of parameters is narrowed near the flammability limit. Sprenger.10 [202]. seen at the bottom of Figure 9. 1950.* The diffusivethermal instabilities that have been considered here pertain entirely to premixed flames.References 365 It is seen in Figure 9. The increase in size with increasing hydrogenoxygen ratio is associated with the increase in this wavelength. with no observable reaction between the stripes. to the combustion zones. Near the flammability limit. CST36. M . leaving a mixture between the cells that is too lean to burn. Williams.7. 3. Wimpress. R. REFERENCES 1. In a diffusion flame between air and hydrogennitrogen mixtures. New York: McGrawHill. Nonlinear analyses of flame shapes of cellular flames are needed. [231]. In particular. Mitani. Neither data on the stripe size and spacing nor theoretical analyses of the instability have yet been published. The cells seen in Figure 9. Smith and D. 12th Symp. (1953). but they can be observed under certain circumstances. P.7 arise largely through preferential diffusion of hydrogen to the bright zones.
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313 . Damkohler’s work was soon extended by Shchelkin [3] and others.CHAPTER 10 Theory of Turbulent Flames Although Mallard and le Chatelier [11 recognized that turbulence affected burning velocities. Accounts of a number of these early turbulentflame studies have appeared in textbooks [4][6]. it is now entirely appropriate to discuss theories of turbulent combustion here. In fact. the subject is so broad that we shall be able to cover only a portion of it and must refer to recent reviews [13][40] for more extensive presentations. a few of these approaches are sufficiently firmly based to enable analyses to be pursued with high confidence in limiting cases. In particular. and reviews of much of the early work on this subject as well are available [4]. In the first edition of this book the comment was made that. This statement is no longer true. Therefore. and a number of new approaches to the subject are available for both premixed and nonpremixed systems. scientific investigations of turbulent flames began in 1940 with Damkohler’s classical theoretical and experimental study [2] of premixed flames. Moreover. However. [6]. in a sense. In recent years remarkable progress has been made in the theory of turbulent flames. [27] is a 250page book devoted to the subject. [12]. the topic of premixed turbulent flames did not belong in a book on combustion theory because the theoretical basis of the subject was practically undeveloped. Theoretical analyses of turbulent diffusion flames began in the same decade [7][ll]. the theoretical understanding of premixed turbulent flames contributed by subsequent works prior to 1965 was not much greater than that originally developed by Damkohler.
i = 1. either theoretically or experimentally. characterized by fluctuations of velocities and state variables in space and time. the solution is strongly sensitive throughout most of the flow field to the initial and boundary conditions. such as the homogeneous thermal explosion of turbulent hydrogenoxygen mixtures. The Boltzmann equation must be supplemented by an equation for the twoparticle distribution in the absence of molecular chaos. combined with a proper set of initial and boundary conditions. to treat turbulence as a random process.1. There are particular problems in turbulent combustion. The NavierStokes equations. . Without molecular chaos. .7). for example. Therefore./dt. The following presentation is based entirely on this continuum view. . at sufficiently large values of a representative Reynolds number Re (see Section 3. t ) .3 74 Theory of Turbulent Flames The most fundamental question in turbulent combustion concerns the applicability of a continuum description. NavierStokes turbulence. that is. However. v. in which these kinetictheory effects have been found to be significant. However. it cannot be claimed that theories of turbulent combustion should necessarily be developed from the NavierStokes equations. equation (D2) is not closed because a twoparticle distribution function. while at the same time another molecule is in another volume element. and in reality the conditions cannot be specified accurately enough to obtain the deterministic solution. appears in an integral expression for df. occurs when the inertial forces are sufficiently large in comparison with the viscous forcesthat is. . . It is conventional to assume that the full NavierStokes equations (that is. N . the NavierStokes equations augmented by chemicalkinetic laws) govern turbulent combustion. are deterministic in that they are believed to possess a unique solution. representing the joint probability that a molecule is in one volume element of phase space. in reducing explosion times appreciably [43][45]. a more fundamental level of description may be needed to address certain phenomena. Turbulence develops from fluidmechanical instabilities of flows [53] when Re is large enough to prevent viscous damping from suppressing fluctuations. Certain studies in kinetic theory in which this has been accomplished [41]. a NavierStokes description appears to suffice for most phenomena. There are a number of excellent background books on NavierStokes turbulence in nonreactive fluids [46][52]. at high Re. especially the chemical reactionrate expression. Molecular chaos is a key hypothesis underlying the derivation in that it enables the collision contribution dfi/dt in equation (D2) to be expressed in terms of integrals involving only the oneparticle velocity distribution function fi(x. the most convincing derivation of this result for gases is based on kinetic theory (Appendixes D and E). It then becomes reasonable to introduce statistical methods and to seek only probabilistic aspects of the solutions. [42] through introduction of a weakened chaos hypothesis have revealed longrange correlations that persist on macroscopic time scales and thereby modify the full NavierStokes equations.
Conceptually.10.1. t ) that appears as the argument of we choose not to do so notationally for the sake of simplicity. In turbulence. and thus it is convenient to treat them separately. Studies of strange attractors are just beginning and have not yet found specific applications in turbulent combustion. t ) about a particular function u(x. t ) ] . temperature.1.1. . any stochastic variable. such as a component of velocity.defined by stating that the probability of finding the function in a small range 6u(x. turbulence possesses a “strange attractor” that draws its statistics away from input statistics and toward statistics that are characteristic of the flow system [54]. or the concentration of a chemical species. therefore. a stochastic function. which we might call u. A number of textbooks provide introductions to stochastic processes (for example.t). the best approaches to analyses of these two limits remain distinct today. we shall discuss theoretical descriptions of turbulent diffusion flames (Section 10. we may consider the initial and boundary conditions to be given only in a probabilistic sense. is a function of the continuous variables of space x and time t and is. the solution in most of the flow would be pseudorandom in that it would pass tests for randomness. In this sense. P[u(x. [ S S ] ) . this input information is modified so greatly by the many fluid instabilities that the statistical aspects of the turbulence are found to be virtually independent of those of initial and boundary fluctuations.1.2) and of turbulent premixed flames (Section 10. A complete statistical description of a stochastic function would be provided by a probabilitydensity functional. t ) is P[u(x. Probabilitydensity functionals With turbulent combustion viewed as a random (or stochastic) process. Although there are situations in which turbulence can tend to wash out the distinction between premixed and nonpremixed systems. It seems clear that even if a totally deterministic problem were specified. small changes in boundary or initial conditions lead to large and irregular changes in the solution away from the boundaries.< . mathematical bases are available for addressing the subject. PROBABILISTIC DESCRIPTIONS 10.of turbulent combustion in the following section. Symbols like v always will refer to arguments of probabilities unless there is an indication to the contrary. Although the statistical properties of the flow might be expected to depend on those assigned to the initial and boundary conditions. t)]du(x. The solution to the deterministic problem is said to exhibit chaos in that. Probabilistic Descriptions 315 Basics of the probabilistic description of turbulence will be presented in the following section.3). After presenting some background information on theories . 10.* * Although it is essential conceptually to make a distinction between a stochastic function and a particular function v ( x . for example.
. . &(x. it can be shown [56] from the NavierStokes equations that if v represents the velocity vector. then the variable whose value may be represented by v becomes a random variable instead of a random function. and JYrn P(v) d o = 1. . t ) ] if v is interpreted as a vector in N + 4 dimensions whose components represent values of velocity. they are of little help because useful methods of solution are navailable. t)] satisfies a functional differential equation that is linear and that in principle contains all the statistical information concerning the velocity field. t ) = 1. we must seek a description at a lessdetailed level than that of the probabilitydensity functional. since any simplification must delete some potentially relevant information contained in the probabilitydensity functional. for P[v(x. so that an ensemble of solutions is obtained. there are more unknowns than equations.376 Theory of Turbulent Flames Here. Although this fact and the ability to write the functional differential equation symbolically are comforting. Seeking lessdetailed levels of description invariably leads to formulations for which. { effectively involves a continuously infinite number of realvariable integrations extending over the entire function space. t)]dv(x. If. there is a functional differential equation. density. for example. where P(v) dv is the probability that the random variable lies in the range dv about the value v. from which the statistical properties can be calculated in accordance with a frequency interpretation of the stochastic process. This difficulty is the infamous “closure” problem of turbulence. and all chemical compositions in an Ncomponent mixture [27]. as described by O’Brien in [27]. then S[v(x. One line of research is to attempt to solve the timedependent NavierStokes equations for the reacting flow numerically. temperature. depending on the approach adopted. J Y[o(x. . By definition P(v) 2 0. fixed values of x and t . [57] and [SS]) by working with simplified equations such as the Euler equations. . the current capabilities of electronic computers in general are much too limited to enable this approach to be pursued. The probabilitydensity function for v may be denoted by P(o). For incompressible NavierStokes turbulence. and its statistics are described by a probabilitydensity function. attention is restricted entirely to particular. t ) is a volume element in the function space. and from the fundamental definition of measure or probability. To make progress in analyzing turbulent reacting flows. An avenue that has received exploration is the development of equations for evolution of probabilitydensity functions. for example. which exhibits itself in many different forms. another is formally to perform suitable integrations in * Depending on the problem. where { . For reacting flows. in one sense or another. this would be done either once for a sufficiently long period of time or many times. . One approach to obtaining an equation of evolution for P(v) is to introduce the ensemble average of a finegrained density. which has the same properties.* although some interesting results have been obtained in this way for relatively simple problems (for example.
[31]. for example in the vicinity of equation (38). notably in those for turbulent diffusion flames (Section 10. modeling is needed for the chemical source terms as well (in contrast to methods based on equations for evolution of probabilitydensity functions) because of their nonlinearity. real phenomenon for certain turbulent reacting flows [59][63]. the transportflux and gradient vectors have opposite directions. or gradient. these methods are illsuited for many turbulent combustion problems. react there. diffusion. [40]. the sign of the diffusivity changes somewhere. the convective terms in equations for energy and species conservation produce averages of the product of a velocity component with temperature or a species concentration. the chemistry interacts with the transport modeling through processes in which fluid elements are transported by turbulence to a location. There are classes of turbulent combustion problems for which moment methods are reasonably well justified [40]. [27]. Since the computational difficulties in use of moment methods tend to be less severe than those for many other techniques (for example. in countergradient diffusion. We shall develop those aspects later. the signs of the turbulent diffusivities must change within the flow if a momentmethod formulation is adopted. Related problems can arise in the modeling needed for methods based on evolution of probabilitydensity functions. they currently are being applied to turbulent combustion in relatively complex geometrical configurations [22].378 Theory of Turbulent Flames forms of these are called Reynolds stresses and typically are assumed to be proportional to gradients of average velocities. techniques involving evolution equations for probabilitydensity functions). * In normal. we shall not present them here. they have the same direction. When both gradient and countergradient diffusion occur in different regions of the flow. with constants of proportionality called turbulent viscosities or turbulent diffusivities.* Countergradient diffusion now is a wellestablished.+ Because of these difficulties with moment methods for reacting flows. and these may correspondingly be modeled as proportional to the gradient of the average temperature or of the average species concentration. now for energy or for chemical species. depending on the units. the chemistry can introduce severe difficulties in moment methods for reacting flows [17]. [28]. problems that stem from the chemistry remain in modeling the Reynolds transport [28]. This sketchy description will become defined better later. . as they are needed. As a consequence of this. [32]. Many of the aspects of moment methods play important roles in other approaches. with the coefficients again being turbulent diffusivities. Reynolds transport. [25]. [32]. Since it cannot be handled well by moment methods. Even if the difficulties in the chemical source terms are overcome. A number of reviews are available [22]. and then are transported back. Similarly. A consequence of this interaction is the occurrence of countergradient diffusion. in a rough physical sense.2). In use of moment methods in reacting flows.
During steady operation. and a flame can be a source for generation of further departures from isotropy. Probabilistic Descriptions 319 Nevertheless. and simplifications in statistical descriptions arise because of the stationarity. the most fundamental average is an ensemble average. In these flows. in that the statistical properties are invariant under translations in these directions. Turbulent combustion in a wellstirred reactor may be approximated as if it possessed homogeneity. which is considered to be different from turbulence. downstream from a uniform grid in a suitably designed combustion tunnel.10. The stochastic process is imagined to be reproduced many times. The statistics of streamwise and transverse velocity fluctuations must be the same in isotropic turbulence. Ensemble averages are relatively well adapted to application in reciprocatingengine combustion. Homogeneous turbulence [47] is turbulence whose statistical properties are independent of the selection of the origin of x. . the collection of reproductions is the ensemble. and there are a number of different ways to define averages.1. Homogeneity must not be confused with isotropy. Although there are different definitions of stationarity. where each cycle may be viewed as a separate member of the ensemble. In statistical methods. called homogeneous. definitions of averages per se require further discussion here because they arise in one way or another in all approaches. in which ensemble averages may be viewed instead as space averages. for example. there are corresponding simplifications in its statistical description. For example. ergodic theorems establish the equivalence of ensemble and time averages under suitable conditions of statistical stationarity of the stochastic process.* There are conditions under which ensemble averages may be replaced by space or time averages that may be obtained more simply. a turbulent flame positioned normal to the average flow. isotropy occurs only approximately even without combustion. we may consider a process to be stationary in a strict sense if all of its statistical properties are independent of the selection of the origin of time. and ensemble averages are equivalent to averages over either of the coordinates with respect to which the process is homogeneous. The experimental evaluation of some averages that depend on coordinate directions can be simplified somewhat by use of isotropy if it applies. averages may be viewed as time averages. There are turbulent flows in which homogeneity applies only in particular coordinate directions. is nearly homogeneous in the two transverse directions parallel to the grid. and the ensemble average is the sum of the values at the x and t of interest in each member of the ensemble. for example. which refers to invariance of statistical properties under rotation of the coordinate system. divided by the total number of members of the ensemble. * There are difficulties here associated with cycletocycle variation [64]. the turbulent flow through a continuous combustor such as a gas turbine or a ramjet appears to be stationary on physical grounds. There are other flows.
Favre defines the massweighted average of a variable v as i. The desirability of working with Favre averages is a topic of current controversy. Therefore. time. an appreciably greater compactness is obtained in the inertial terms . as v" = v . Then the average v" is not zero. A simplification can be achieved in variabledensity flow by selecting the product pv as a fundamental variable to be employed instead of v. The ensemble average of equation (11) (with overbars signifying averages) then is appt +v( p+ ~ pIvI) = 0. while others provide C. (1) where the local. = (p)/p and denotes the departure of v from i. or ensemble averages are employed. instantaneous fluctuations are p' = p . In this notation. a product of fluctuations does not arise in the average of the continuity equation.. Probabilitydensity functions appropriate for use in connection . The average of a product of fluctuations appears in equation (1). It is unclear whether the successful constantdensity modeling of Reynolds stresses is extendable more readily to pv" or to pv"v". and we may therefore choose to work with the averages p and V. the ri dyadic @ .pTT is found to be pv"v" = p(v"v"). the divergence term is then simply V * (pV). The simplification of equation (1) represented by equation (2) is relatively unimpressive. which have p' = 0 and 7 = 0 by definition. b u t 3 = 0 by definition. notable economies generally are achieved through introduction of these massweighted averages. but in many uses of averaged equations. A formulation in which this modification was effected has been developed by Favre [65]. In thorough studies there is unlikely to be a fundamental reason for making a choice because the identity pv" = pV + (@)demonstrates that one average is recoverable from the other once p and p'v' are obtained.380 Theory of Turbulent Flames Irrespective of whether space. questions arise as to what variables are to be selected for use (for example.V. equation (1) becomes appt + v ( p ~= ) 0. The economies associated with the introduction of Favre averaging therefore appear to constitute the determining factor in favor of its adoption. The simplifications that arise in convective and inertial terms are offset somewhat by complications produced in molecular transport terms. The controversy cannot be resolved on the basis of ease of measurement because some instruments provide v" most directly.i. as they must be for completeness. With p and pv as variables. but in the average of the equation for momentum conservation. for which averages are to be calculated) in analyses of turbulent combustion.p and v' = v . which involves four terms if the more conventional average is employed. Considering equation (11) we may guess that p and v are reasonable variables. modeling is introduced for effects of molecular transport irrespective of the averaging selected.
s.1. From P(v). The third and fourth central moments may be written as sc3 = J m (U m  ij)3P(~ dv ) (6) and KO4 = J. (5) m where the last equality follows directly from the definitions by expanding (v Either the variance or its positive root. and conventionally is denoted by UI2 = 0 2 == J m (U  I$~P(u) dv = v2  ij2. s is a measure of asymmetry of P(v). 0. as indicated at the end of the following section. u ' .1.0.10.3. is the second moment about zero.the standard deviation. . The variance is the second moment about the mean. However. 10. P(v) cannot be reconstructed completely even from a knowledge of the values of all of its moments because this is possible in principle only if P(v) obeys . Properties of probabilitydensity functions The basic definition of a probabilitydensity function is given in Section 10. measures the width of the distribution of P(v). with larger values of K corresponding to a shape more like a sharp.for example. with positive s implying a more gradual tailing off toward positive values of o than toward negative values. also termed the second central moment. Knowledge of the values of 6.1. the average of the random variable is readily calculated as This is also the first moment of P(u) about zero because the nth moment about zero is defined as Jm The meansquare value. and K would provide a significant amount of information about P(v).1. average) value. W (7) where s and K are called the skewness and kurtosis (or flatness factor). and K is a measure of how kinky P(v) is. here 0 represents the rootmeansquart: intensity of the fluctuations about the mean (that is. rectangular mesa than like a gently curved hill.ij)4P(v) dv. Probabilistic Descriptions 381 with massweighted averages have been defined by Bilger (see [27]). in general. respectively.(.
in equilibrium diffusion flames. where dg = Idg/dvI d v .2). then neither g nor Q(g) can be obtained even in principle from P(v) because it lacks information concerning the relative frequencies with which each of the different possible values of g occurs in the ensemble . a probabilitydensity function for a new random variable with its value represented by g . Equation (9) may be understood best by first considering functions g(v) that are monotonic. a probabilitydensity function for it cannot be generated from one for temperature (which fails to distinguish rich from lean mixtures). If g remains constant over a finite range of vfor example. is which may be evaluated directly by integration. . stating that all members of the ensemble for which the original random variable lies in the range d v about v also have the new random variable lying in the range dg about g . then g may be evaluated in terms of the moments of P(v). n) are the values of v for which g(v) takes on the value of g. it becomes clear that in the vicinity of g = g o . Considerations like those indicated here enable Q(g) to be generated for any singlevalued function g(v). If g(v) is multiplevalued.382 Theory of Turbulent Flames various continuity and convergence requirements that many probabilitydensity functions of practical interest do not satisfy. say g(v). n = l). but through consideration of the fraction of members of the ensemble for which g = g o . . the mixture fraction usually is a doublevalued function of temperature (see Section 3. The average of any singlevalued function of v. so that there is only one value of v for any given g (that is.then equation (9) simply produces infinity at g = g o . g = go for v1 < v < v. . Given g(v) and P(v).4. . equation (9) extends this result to nonmonotonic functions by adding the contributions from the members of the ensemble having the original random variable in the range dg/ I dg/dv I about each vi for which g(vi) = g. delta functions often arise in probabilitydensity functions for temperature and species concentrations. may be constructed according to the formula where vi ( i = 1. If g(v) possesses a powerseries expansion that converges wherever P(v) # 0. say Q(g). there is a deltafunction contribution to Q given by in turbulent combustion. . and the equation becomes Q(g)ldgl = P(v)Idvl. and therefore in the absence of additional information.
for example. dv. . may be values of two different components of velocity or of one velocity component and temperature. dv. In practice it is seldom convenient to consider n > 3. t 2 ) . . 0.) because from the underlying definitions. . the second) takes on a specified value or lies in a specified range. and v. then the adjectives onepoint. v. while if t . here v1 and v.. ... cross..1. . Twopoint probabilitydensity functions play important roles in describing stochastic processes whose underlying conservation equations involve derivatives with respect to x.. = t . twotime joint probabilitydensity function of one stochastic function. If v1 and v. v... about v. d v . Even for x1 = x2 and t . onetime) are of interest in turbulent combustion .10. # t. t... but t . then a relevant joint probabilitydensity function (for two random variables) may be denoted by P(u. Thus P(v. [ymP(vl. . onetime would be used. The definition requirements P(v. Here P(v. Probabilistic Descriptions 383 Knowledge of P(v) for one random variable at fixed x and t offers very limited information concerning a stochastic process because no aspects of relationships obeyed by the random variable at adjacent values of x and t are contained therein. about v.. is a value of the same stochastic function at a different position and time (x. To increase the amount of statistical information. v. . . but only those in which one random variable (for instance.) may be introduced. v. having been generated on a margin (the v l axis) from the projection of a joint function. relate to the same stochastic function. v. In equation (11) P(vl) would be called a marginal probabilitydensity function. .) dv. restricting attention to these members is establishing a .. v. v. as needed in evaluating Reynolds stresses and Reynolds transports.. = t. for example. v.. . .) 2 0 and . twotime would be applied to P(v. but x1 # x. joint probabilitydensity functions (now onepoint. .). then the further qualifier auto often is used.). and the second in the range dv. and allowing n to approach infinity suitably in principle could result in a complete statistical description of a stochastic process. if different. . the terminology twopoint. If v1 is a value of a stochastic function at a particular position and time (x. v.) d v . v. .viewed as the fraction of members of the ensemble in which both of the random variables are in their respective ranges.). It is always possible to recover P(vl) from P(v. m: [ = 1 (10) always apply... joint probabilitydensity functions may be introduced. If x1 = x.) is a twopoint.. In a similar manner. . . Often it is desirable to consider not all members of the ensemble. is defined as the probability that the first random variable lies in the range dv. where P(v. joint probabilitydensity functions may be defined for any number of random variables..
I)P. an intermittency function may be defined as a stochastic function having a value Z(x.)that is. Statistical independence is a strong property that is difficult to justify.). I u2)P(u2)= P(u2 I ul)P(u. P(u. 02) = P(U1 U . the value of the temperature at a point in a turbulent flame may be expected to be related statistically to the value of the fuel concentration there. is Bayes's theorem. then the notation P(u. conditioning on the requirement that fuel be present is another example of conditioning that sometimes can be useful. jets and wakes) that are partly turbulent and partly nonturbulent (in that the flow is partly irrotational).. For example.in which all four P's are different functions. Conditioning often is needed in turbulent combustion. the conditioned probabilitydensity function is the same as the marginal probabilitydensity function. ) P ( U 2 ) . Conditioned averages and conditioned moments can be defined in a straightforward manner since conditioned probabilitydensity functions obey all the properties of unconditioned probabilitydensity functions. In turbulent diffusion flames.lu2) is independent of u2 for all u. often there is interest in flows (for example. 1 u 2 ) is used for the conditioned probabilitydensity function. and the conditioning may be that rotational fluid be present. and the resulting probabilitydensity functions are called conditioned probabilityclensity functions.384 Theory of Turbulent Flames condition on the probability. A random variable with a value denoted by u1 is said to be statistically independent from a random variable with a value denoted by u2 if P(u.(u). if the conditioning does not affect the probabilitydensity function. If the conditioning is that the second random variable have the value u 2 . Thus P(ul I u 2 ) du. For example. 1 u 2 ) = P(u. (13) where Po(u) is the probabilitydensity function in the irrotational fluid and Pl(u) is that for the rotational fluid. the meaning of which should be clear in spite of the somewhat imprecise notation. and the value of the . t ) = 0 in irrotational flow and Z(x. From equation (12) it then follows that P(Ul. The meanings of the various probabilities show that P(U. It is conventional to place a vertical bar inside the parentheses in the notation for P and to write the conditioning restriction after the bar. and conditioning on I = 1 may be desirable for a number of purposes. t ) = 1 in rotational flow. is the probability that the first random variable lies in the range du.U2) = P ( U l ) P ( U 2 ) (14) for statistically independent random variables. about u1 while the second takes on the value u 2 .that is.(u) + IP. These flows are said to exhibit intermittency of the turbulence . We may decompose a probabilitydensity function as P(u) = (1 . I (12) A result of the definitions. In this case P(u.
then the random variables are said to be uncorrelated. for the ij and u" defined above equation (2). where the for i = 1. Fourier decompositions In analyses of turbulent combustion. . = j. j. v. In working with . . it is helpful for various purposes to view the processes in frequency or wavenumber spaces instead of in time or physical space.10.1. P(u) possesses the necessary nonnegative and normalization properties of probabilitydensity functions. If R . A much weaker property. JOm PP(P. defined in equation (5). 10..4. is vanishing of the covariance. 0) d p / P . Transforms with respect to different variables arise. (15) A nondimensional measure of the covariance is the correlation coefficient.)(v.) dv. = 0. the second cross central moment. Thus. It is especially useful in connection with the Favreaveraged formulation of the conservation equations.fiZ)P(V. ( U. Fourier transforms provide the desired decompositions. Use of equations (3) and (14) in equation (15) readily shows that R . .fi. implied by statistical independence but not implying it..1. v). A massweighted (or Favre) probabilitydensity function for the second random variable may then be defined as p"(4 = By definition. sometimes called the cross correlation. do. = 0 if the two random variables are statistically independent. 2 represent meansquare fluctuations (variances). (17) the first of which is similar to equation (3) and the second of which is like equation (5). R. The joint probabilitydensity function for the density of the gas and another random variable may be denoted by P(p. since corresponding averages are obtained from S(u) by the usual rules for averaging. a m .. Probabilistic Descriptions 385 velocity at a point will be related to the value of the velocity at a nearby point.
t. the formalism of FourierStieltjes transforms may be introduced to allow for anticipated nonanalytic behavior [47]. x.(x2. The quantities transformed may be the velocity components or state variables themselves or various averages of them. with cp(co) = j?..t. Transforms with respect to spatial coordinates or time are encountered more often. s_. . which assumes that R is defined for all real values of x and t (for example. thereby effecting simplifications in the analysis. In equation (20). For statistically stationary turbulence. R(x.) .eireik. e i o r f ( z ) which would be applied four times for the spacetime transforms.. eiwrcp(o) do/271. x 2 . t . t . we may define a fourdimensional Fourier transform as w.. f. namely.x .)may be treated similarly. for dz. corresponding quantities are the autocorrelation.. Here we shall consider only transforms of certain averages. s_. Correlations are readily recovered from their transforms by the inversion formula.x m m m m R b . or else this refinement can be bypassed by accepting illbehaved transforms (having delta functions in them). XI.)Y.) dx dz. the transform variable o is the frequency. by putting R = 0 for values outside the bounds of the flow of interest). .. Equations (20) and (22) in their full forms are seldom useful. x2.w . .. x.) and R(xl. t. (22) Cross correlations such as between temperature T and a mass fraction Y.. correlations. t . with v‘ = T‘ (the temperature fluctuation) and the transform W. T’(x.I. The spacetime velocity correlation tensor is defined as Its components could be evaluated from equation (1 5 ) if suitable probabilitydensity functions were known. .t. t. x.ireik. example. Particularly for velocity and state variables.. and the transform variable k is the wavenumber vector. t l > = I. The former is especially useful for coordinates in which the stochastic process is homogeneous.x m m m m R(x.namely. With x = x2 . and z = t . t . we may transform these functions with respect to velocity components to obtain “characteristic functions” from which the probabilitydensity functions can be recovered [55].) dx dz. w . J.386 Theory of Turbulent Flames probabilitydensity functions for velocities. The main advantage of introducing transforms in these situations is that differentiation becomes multiplication by the transform variable. For a scalar field such as the temperature T. t l ) = J.I.. . we havef(z) = j?. (20) where dx is a volume element in x space.I. t. and the latter if the process is statistically stationary.
(25) where the energy spectrurn. denoted here by Q(k.t. Similarly..x. t1)/(271)3] dk.. t l ) = J0%.xl). as an integral over wavenumber space. Spectral decompositions in frequency .. t. are transthese functions for x forms (or spectra) of time correlations at a particular position and can be especially useful. ) and called spectra of space correlations. . only through the difference z = t . and their transforms with respect to z alone depend only on o and the two positions. the space correlation obtained from equation (19) by setting t . x1. t . t. ) v’(xl 2  1 + x. = t depends only on r = I x2 .). for homogeneous turbulence.t.x.x 1I at fixed values of x 1 and t. . 4(x.e(k. t ... play central roles. For isotropic turbulence. (23) which is independent of x . = t.. Half of the trace of Q(k. tl). is (k/27c)’ times the traceof Q ( k .. ) dk.)since.)3 ~ I. for which the threedimensional transforms with t . its inverse transform is  1 v‘(xl. Q ( k . t .t . x.  d2(x1. t . if there is homogeneity in some coordinate directions. then transforms with respect to those coordinates may be useful. x. and t . t. is related to the average turbulent kinetic energy per unit masssay q(x. eik’XE(k. . then the integrand in equation (25) or in equation (26) may be viewed as the contribution (per unit range of wave number) to the turbulent kinetic energy or to the fluctuation intensity from eddies of size l/k. = x . t. and its spatial transform therefore depends only on k E Jkl. t .I.) and @(w. Probabilistic Descriptions 387 depend on t . . Ideas about the dynamics of turbulence have been developed by reference to fully homogeneous turbulence. ) = SU: [ 4 z k 2 @ ( k . x. ) at time t . from equation (19).. that is. t l ) = ~omeikrR(xl.)47cr2 dr. A spectral decomposition for intensities of fluctuations of scalar fields may be obtained from equation (21) in a similar manner. for example.. . namely. ) and @(k.)/(27~)~ in equation (23).10.). to be denoted here by E(k.) and becomes 47ck2E(k.J. w m a . denoted by @(a.. t l ) dk.t . t. x 2 . t l ) = (2. (24) in this case. putting x = 0 in equation (23) gives q(x. equation (23) shows that the average kinetic energy per unit mass can be expressed as an integral over a scalar wave number. (26) If l/k is interpreted as a turbulent eddy dimension.1.
The contribution from each scale can be obtained experimentally by measuring e(k).t .initially our discussion will mainly concern the dynamics at smaller scales. 10. then v‘(xl. .Ix2 . Here we shall write e(k). moreover. we may consider our remarks to apply to an average over directions.x 1 in the direction of 1. . t . The general physical concepts of turbulent motion. suppressing the dependence on x1 and t. The measurement task can be simplified appreciably in this experiment if it can be assumed that the turbulence is convected with negligible change past the fixed measurement tl)= station at the constant average velocity V. Scales of turbulence The dependence of e(k. Equation (25) suggests that a continuum of scales of turbulence contributes to q.388 Theory of Turbulent Flames for turbulent kinetic energy and for intensities of scalar fluctuations may be introduced in an analogous way for statistically stationary turbulence. thereby derived.1. In view of equations (19) and (24). v’(x2.t 2 ) for x2 = x 1 + V ( t 2 .. Taylor hypotheses are much more questionable for many turbulent flames because of rapid changes of fluctuations with position. Measurements of e(k) show that it vanishes at small and large values of k and reaches a maximum at an intermediate value. Although the approximation of isotropy is not exactly correct even for the simplest nonreacting turbulent flows in the laboratory and. the simplifications afforded by speaking in terms of a scalar k offset the greater precision associated with retaining k as a vector.tl).5. ) v ’ ( x . The classical experiment concerns the flow in a constantarea wind tunnel downstream from turbulenceproducing grids.. is reasonably good in many nonreacting flows for finding e(k) at all but the largest scales. The maximum usually occurs where l / k is on the order of the integral scale of the turbulence. tl)v’(xl. produced by the influence of combustion on the turbulence through the effects of heat release. have been verified reasonably well. which has been called a Taylor hypothesis. If this is acceptable. this involves measuring velocity fluctuations simultaneously at two different locations for the full range of distances between these locations. may be poorer for many turbulent reacting flows. An approximation of this type. This is an ambitious task that has been completed successfully for a number of turbulent flows. Integral scales (also called correlation lengths) may be defined explicitly in terms of correlation coefficients. xl. Consider any one component .xll/lVl). t l ) =v‘(x. Isotropy tends to be achieved more closely at small scales than at larger scales . and e(k) can be obtained from a measurement of the time history of the velocity fluctuation at a single point. For nonisotropic turbulence. so that with x2 .t l ) on k affords a convenient focus for discussing many properties of turbulent flows as well as various scales of turbulence. and we shall occasionally appeal implicitly to results for homogeneous turbulence because the ideas have been developed most thoroughly in that case. v’(xl.
= t . let r = Ix. exhibit a correlation. Since e(k) peaks near k = 111. and let u . if we were to consider equation (21) with x. Probabilistic Descriptions 389 of equation (19) for t . Under more general circumstances.and allow v . .. The eddies with sizes in this range have been called the energycontaining eddies. varying from x... depends on the direction of the unit vector.. and t. For other purposes integral time scales also are introduced. in equation (15) to represent the selected components of v(x. there are only two different values of I. For values of k below those corresponding to the energycontaining eddies.1.1. In general. e(k) falls rapidly toward zero with decreasing k . is sufficiently large. R . toward x. respectively. = P&l/ji. and v . = x.10. there may be significant additional structure in the function e(k) if the turbulence Reynolds number. The definition of R .. . is like that of Re of Section 3. in terms of the c. respectively.7. the question of selection of a component of a tensor then does not arise. From its definition we see that the integral scale 1 physically measures the distance over which the fluctuations occur in a relatively fixed phasethat is. fi R . (29) .. x . . ..t . of equation (16) and with T = t . one for diagonal elements of R and the other for offdiagonal elements. but with u and a there replaced by and 1. . in equation (15) refer to the variables at times t . ) and v(x. a unique integral scale 1 at (x. to a boundary of the fluid (indicated by a3 in the integral) in such a way that the unit vector from x. respectively [where the q is that of equation (25)]. ) .. the integral scale becomes in which the integration is performed with the point x. t . # x. the size of the apparatus imposes an upper limit on the maximum eddy size achievable (the minimum k having e # 0). . Thus the integral scale and the rootmeansquare velocity fluctuation are employed in defining the turbulence Reynolds number. isotropic turbulence at fixed t . then the integral time scale or correlation time would be rm with the c. For values of k above 111. l. for equation (19). t . and v . If a Taylor hypothesis applies. for example. maintains a fixed direction.. Integral scales may be defined for scalar fluctuations in a similar manner by considering equation (21) instead of equation (19). the largest concentration of turbulent kinetic energy occurs at scales in the vicinity of 1. fixed and with x.t . Then. on x 1 and t . of equation (16). . For homogeneous. ) may be defined as an average over the diagonal elements only and over all directions.xll. then a relationship between integral space and time scales can be developed. and on the component of equation (19) selected..
During the cascade. 1. thereby causing spectral mixing. over which only the inertial terms in the equation for momentum conservation are significant. When R . From equation (29) and the definitions. which is a cascade of energy from small to large wave numbers. Therefore. only quantity with the dimensions of e(k) obtainable from c and k is a dimensionless constant times c 2 / 3 k . measurement and physical reasoning agree in ascribing a distinctive shape to e(k). is considered to occur through interactions between components of different wave numbers. the peak of e(k) is followed with increasing k by a tailing off that is roughly symmetrical with the rise. 1. For R. namely. 6 1. e(k) decreases with increasing k in proportion to k . The inertial subrange ends when k becomes large enough for viscosity to be important. it is associated more closely with regimes and dynamics of turbulent motion than is Re. (30) which shows explicitly that I.' I 3 .5 such as equation (31) are not introduced herein. (defined below. . a condition often encountered in practice. in the inertial subrange. % 1. produced by the nonlinearity of the inertial terms. The dependence of e(k) on k in this inertial subrange or Kolmogorov subrange was deduced by Kolmogorov through dimensional analysis. The characteristic length at which this occurs. 1. where turbulence is dissipated by viscosity). Turbulence dies rapidly if R . v = . the viscous * Often the intensity in R. only k and the average rate of spectral transfer of energy can affect e(k). The viscous terms are the most highly differentiated terms in the equation for momentum conservation and therefore are largest relative to other terms at the smallest scales (largest k's).is defined in terms of just one component of velocity so that appears instead. Both scale (1) and intensity* (4%) of turbulence must be known to characterize it properly. there is an intermediate range of k between 111 (where turbulence is generated from meanflow instabilities) and 1/1. < 1 when R. we see that + + 1. $ 1. > 1. . For R. is based on properties of the turbulence. = (v3/c)"". Related constant factors that also occur in other definitions with isotropy iv/z. 1. the contribution at any given wave number then involves an integral over all other wave numbers. This deduction agrees with experimental observations for R.5 / 3 . is obtained through dimensional analysis as the length that may be constructed from c and a representative kinematic viscosity. A spectral transfer of energy. the Kolmogoroa length. The interaction becomes evident if the convolution theorem is applied to the Fourier transform of the inertial terms in the equation for momentum conservation in homogeneous turbulence [47] .ii/p.390 Theory of Turbulent Flames Since R. The average rate of spectral transfer must be the same as the average rate of dissipation of turbulent kinetic energy and dimensionally may be estimated as c = ( 2 ~ ) ~ " / 1 The . = l/Rf'". For k + l / l k .
we find through use of equation (29) that 1. Nonlinearities of the chemical production . 1 and I.1. A third. Nothing special occurs in the energy spectrum at k = l/l. % 1. production of turbulent kinetic energy. this represents an exponential decrease of e(k) with increasing k 2 .. at any given time f. By equating this quantity to E . the Taylor scale. and Reynolds numbers based on 1. represents a cutoff length below which no turbulent eddies exist. Probabilistic Descriptions 391 terms are much larger than the inertial terms in the equation for momentum conservation. Passive scalars (those that do not influence the velocity field) in the absence of chemical reactions can experience spectral transfers as a consequence of the convective terms in their conservation equations. The average rate of scalar dissipation. or 1. % 1. I. multiplications and averaging in the equation for momentum conservation an (unclosed) equation for dq/dt is derived.. We have now seen that for R. Here D is a representative coefficient of diffusion for the scalar field.10. < 1. is of a magnitude intermediate between that of I and I. The cascade concepts may be applied to intensities of scalar fields as well as to the turbulent kinetic energy. < 1. is the Taylor length. in a first approximation for R. If through suitable substitutions. where I. whence it is straightforward to demonstrate for homogeneous. and the equation becomes linear. constantdensity turbulence that e(k) becomes proportional to e2vk2t [47]. = I/&. There have been studies of influences of chemical reactions on the spectra of passive scalars [161. instead of 1 may be introduced if desired (and often are). then this equation is found to contain terms that may be interpreted as convection by the mean flow. The dissipation term is v times the meansquare value of the magnitude of the vorticity vector (V x v) and can be written as a nondimensional constant times v(2q)/L?. there are at least two special length scales. a much more rapid dropoff than the powerlaw behavior in the inertial subrange. Experiments confirm that the cascade is terminated abruptly by viscous dissipation approximately at k = Illk. $ 1. Dimensional analysis again provides the power of k in the inertialconvective subrange. Comparison of equations (30) and (31) shows that for R . Therefore.. plays a role analogous to that of E in the analyses.  (32) for the variable in equation (26). Time scales related to the various lengths may be defined through division by various velocities. that is. and dissipation of turbulent kinetic energy. j = 2D(VV') (VV'). I. it may be assumed that I . and an inertialconvective subrange can exist in which the integrand of equation (26) exhibits a powerlaw dependence on k analogous to that of e(k) [66]. arises in estimates of the magnitude of the average rate of viscous dissipation. turbulent diffusion.
theories that we also shall forego discussing for the sake of brevity. This research emphasizes coherent structures that occur in turbulent flows [67]. The focus is placed on frequencyhalving processes instead of the frequencydoubling effects operative in the cascade. Relationships are being identified to the onset of turbulence and to the development of spottiness of turbulence at large Reynolds numbers through vortexstretching mechanisms that tend to concentrate fine structures in localized regions of space. nevertheless appeal to concepts of coherent structures [68]. as in liquids or ionized gases. if shear layers are to grow in width (as.2). or mixture fractions. then a number of additional interesting aspects of cascade phenomena arise. Fluids 11. TURBULENT DIFFUSION FLAMES 10. We shall not have space here to present these approaches and must refer instead to reviews [18].2. 2305 (1968). [40].1.2. . These methods share some aspects in common with “age” theories of stirred reactors [19]. then there are hazards associated with attempts to apply the usual cascade concepts to it. Various time scales also are associated with the * If Prandtl or Schmidt numbers differ appreciably from unity. the increase in width of a turbulent shear layer with increasing distance downstream may be associated largely with vortexpairing processes that create larger structures from smaller structures. A conserved scalar is one that possesses no chemical source term (see Section 3. the formulation in the following section focuses on conserved scalars. These effects are complementary (not contradictory) to the cascade dynamics because they occur mostly at scales on the order of 1 or larger. for example. 10. Objectives of Analyses We saw in the last section that disparate length scales and time scales exist for turbulent flows. although not deductively based on the NavierStokes equations. a process that must occur.4. Phys. they do). [27]. and additional turbulence scales with distinguished attributes may be defined. We do not discuss these topics but instead refer the reader to C. it may be inferred that if a scalar is not conserved. of course. There are approaches to analyses of turbulent combustion that. * Most of the modern research on turbulence dynamics is addressing aspects that differ from those of the cascade concepts. For example. They may be responsible for an increase in 1 with increasing time as the turbulence evolves. The volume in which [29] appears is concerned with this subject. Gibson. we shall consider a promising approach to the theoretical analysis of turbulent diffusion flames. Much of the early research on turbulent flows [48] acknowledges scaleincrease phenomena. [69]. H. Partly for this reason.392 Theory of Turbulent Flames terms can modify cascade aspects of the spectra. a countercascade phenomenon that meshes well with the ideas of [54]. Instead.
and multiphase flow [75]. We shall see that good methods are available for analyzing problems of this type. those in which the various inlet streams. Methods for analyzing turbulent diffusion flames with fast chemistry have been developed recently [ls].2). There are many reasons for interest in turbulent diffusion flames. that is. will be discussed in this section. It seems clear