Twenty-Fourth Symposium (International) on Combustion/The Combustion Institute, 1992/pp.

1-17

HOTI'EL PLENARY LECTURE

THE ROLE OF THEORY IN COMBUSTION SCIENCE

F. A. WILLIAMS
Center for Energy and Combustion Research
Department of Applied Mechanics and Engineering Sciences
University of California, San Diego
La Jolla, CA 92093-0310 USA

Prometheus has been identified as the mythological deliverer of combustion science to

mankind. 1 Sciences traditionally have been divided into two parts--experiment and theory..
A question therefore arises naturally: Was Prometheus more nearly an experimenter or a
theoretician? My purpose is to attempt to review for you the history of the contribution of
theory to the science of combustion. To do so I need to describe "'theory" and "science"
and to try to trace combustion from antiquity on into the future. A conclusion will be that
today most sciences; and notably that of combustion, must be divided into three rather than
the traditional two parts. But first, let's address that burning question raised above.

Mythology he knew and understood things that not even the

When I was a child, my parents brought my sis-
ter and me by railroad one day from our home in
rural New Jersey to New York City, where we mar-
veled at the skyscrapers and visited Rockefeller
Plaza. There, next to what is now the ice-skating
rink, stands a statue, coincidentally erected in the
month that I was born, showing Prometheus with
a baton of fire in his right hand, attractively exe-
cuted by Paul Manship. Although my parents in-
sisted that we study the statue, I learned only that
he was some sort of Greek god or hero--I was much
more impressed by the train ride, the gigantic
buildings and the spectacular show inside Radio City
Music Hall. What a strange quirk of fate it is that
he represents the oldest symbol of what was to be-
come my chosen profession.
And no mean profession (avocation in Japan) it
is, if we may judge from the qualities of Prome-
theus. His name translates as forethought, the op-
posite of that of his brother Epimetheus, after-
thought. They were sons of one of the Titans, who
were the first beings in the world that were not
purely destructive and the fathers of the gods, such
as Zeus, the ruler. In one account, the gods asked
the brothers to create animals and humans, and
Epimetheus quickly gave the best attributes he could
imagine to various animals, then ran out of ideas
for humanity and requested help from Prometheus,
who completed the creation, endowing us with an
9
upright, noble stature and presence of mmd.
9 2
Wisdom is the most prevalent characteristic of
Prometheus in mythology. Always a friend to man,
ruling gods could fathom. He exhibited amazing
determination and ability to withstand torture--even
though he had helped Zeus overthrow the Titans,
as punishment for bringing fire to mankind Zeus
chained him to a Caucasus mountaintop at the edge
of the world, where (Fig. 1) each day for thirteen
generations (or, in different accounts, 30 or 30,000
years) he endured the excruciating pain of an eagle
devouring his liver (which grew back each night),
rather than reveal to Zeus the name of the woman
with whom Zeus would sire a son who eventually
would overthrow him. The qualities of Prometheus
must surely be a great aid to anyone in our profes-
sion.
Experimenter or theoretician? Assuredly the lat-
ter. There is no indication that Prometheus ever
built something which he found that he didn't quite
like, then tried again and improved it, nor did he
even need to observe in order to understand the
world about him. On the contrary, he thought things
out completely ill advance, and when he took an
action the result conformed exactly to his theoret-
ical conception.
Mankind created the myths of Prometheus some-
time between 1000 and 700 B.('. This seems an ap-
propriate age in which to begin a narrative of the-
ory in any science, because it is the earliest time
to which written records of generalized concepts that
ultimately lead to establishment of a science can be
traced. The Mesopotamian writing, from the cradle
of civilization, which dates up to 2000 years earlier,
does not appear to exhibit such generalizations. To
satisfy their desire to understand the underlying ra-
2 HOTI'EL PLENARY LECTURE
/
rZ'..
FIG. 1. The punishment of Prometheus for giving
fire to mankind (T. Velasquez).
tionale for their existence, the early Greeks con-
nected theory with experiment by creating special
gods who guided the grand experiments of nature.
The Greek heritage of mythology surely must have
influenced Aristotle, around 350 B.C., in developing
his theory of matter. Aristotle's theory led to the
first science in which combustion played a promi-
nent part.
The First Half-Million Years of Combustion
Research
Felix Weinberg's entertaining description 1 of
mankind's use of fire for 500,000 years, culminating
in his ability to start fires, beginning about 30,000
years ago, demonstrates clearly that experiment held
sway in the field of combustion for more than 99%
of its history. The prehistoric Copper, Bronze and
Iron Ages also were eras of experiment, without ex-
ception. Experiment alone does not a science
make--otherwise cookbooks should be treated as
scientific documents. The classic Greek philosophy,
associated with Mesopotamian astrology and espe-
cially Egyptian craftsmanship, resulted, in about A.D.
100, in a true science, with both theoretical and
experimental components, the science of alchemy. 3
Alchemy
Although the principal objective of the alchemist
was to turn base metals into gold, many useful as-
pects of metallurgy were involved in alchemy. The
theory, going back to Aristotle, took the hot-cold
and moist-dry qualities and combined them into the
four elements, earth (cold, dry), water (cold, moist),
air (hot, moist) and fire (hot, dry). Not a science of
combustion you say, and I agree, even though
combustion formed one-quarter of its foundation.
Yet still a science, in that theory suggested exper-
iments and experiment contributed to refinement
of theory. Transmutation was built in from the start,
in that by varying the proportions of the qualities,
the four elements and everything in between could
be obtained. As the science evolved, it also tended
to deteriorate, for about 300 to 900 years, because
theory and experiment went separate ways, with
increasingly esoteric theoretical writings (for ex-
ample, relating gold to the essence of the soul) that
became totally divorced from experiment,
It remained for the Arabs, around A.D. 1000, in
Baghdad and C6rdoba, to reunite these two essen-
tials and to greatly advance the modern science of
alchemy. Books by the Spanish metallurgist Geber
(or Jabir), at the beginning of the Renaissance,
around 1310, set forth foundations of the modern
science, for example identifying mercury and sulfur
as providing the melting and burning (rusting)
properties of metals, respectively. Geber's treatises
established the experimentally based, hard-science
underpinning of alchemy for 300 years. 3 It re-
mained for Antoine Lanrent Lavoisier (France), Jo-
seph Priestley (England) and Karl Wilhelm Scheele
(Sweden), in the decade 1770-1780, to finally com-
plete the experiments that would replace alchemy
by a new and better science of chemistry.
Phlogiston
For nearly 100 years of the post-Renaissance pe-
riod (including most of the eighteenth century), be-
tween the decline of alchemy and the rise of mod-
ern chemistry, the theory of phlogiston reigned,
championed largely by the German scientist Georg
Ernst Stahl. Combustion was even more a part of
this theory than of alchemy. Fire (phlogiston) was
a fundamental substance, not just a combination of
two qualities, and during combustion a material lost
phlogiston. When its phlogiston was completely
gone, the material could no longer burn.
This was a semi-quantitative theory in that there
was some sort of a concept of conservation of phlo-
giston, and it enjoyed considerable success in ex-
plaining experimental observations. However, as
measurements of mass changes during combustion
were refined, the theory encountered increasing
 THE ROLE OF THEORY IN COMBUSTION SCIENCE
difficulty. Some materials (charcoal) lost weight and
others (iron) gained it in combustion. Although the
initial experiments that isolated elements such as
hydrogen and oxygen ("dephlogisticated air") were
interpreted, for example by Henry Cavendish and
by Joseph Priestley, in terms of the theory of phlo-
giston, the quantitative science of chemistry, with
its periodic table of elements (finally given by Men-
deleyev in 1869) eventually emerged (beginning
around 1800) as a much more useful and self-con-
sistent theory of matter. Alas, with more than 100
elements, combustion is not even one (small con-
solation that Promethium, radioactive rare earth,
atomic number 61, is one). Few if any other profes-
sions can, have suffered a decline and humiliation
so great as that experienced by ours in the first part
of the nineteenth century!
Emergence of the Science of Combustion
We did, however, begin to bounce back in the
latter half of that century. No longer a building block
for theories of matter, combustion could now be
studied just for itself.
It is relevant to distinguish between the science
and the technology of the subject. The march of
technology has never hesitated. It uses science
whenever possible but often, especially in combus-
tion, forges ahead by trial and error, or fortuitously
by application of scientific misconception, but with-
out scientific understanding, as it did during the
first half-million years. Steam engines were devel-
oped while phlogiston was dominant, and the in-
dustrial revolution, with its steamboats and loco-
motives, surged forward during the period of
disgrace of combustion in science, benefiting from
new sciences such as chemistry. Moreover, at least
by present-day standards, the contributions of com-
bustion science to the initial development of the
Diesel and Otto engines, towards the end of the
nineteenth century, ranged from pitifully small to
nonexistent. Especially with the latter, premixed
flames came into widespread use--Weinberg 1 has
emphasized that during most of history only diffu-
sion flames were known, although partially pre-
mixed diffusion flames, including transient heat
feedback from the condensed phase to the cool in-
coming air, date back appreciably, to times when
artisans skillfully blew air into their charcoal fur-
naces to achieve superadiabatic temperatures for
metallurgical processing. My topic is the science,
not the technology (however important it may be),
and so no more about applications.
What are the elements of the science of com-
bustion? How and when were they found? Diverse
answers have been given to these questions.
Many years ago a student brought to me a type-
set paragraph pertaining to the definition of com-
3
bustion science, which impressed me so greatly that
after 30 years I still have it displayed on the wall
of my office. I don't know who wrote it, and I would
be indebted to anyone who can tell me. A slightly
paraphrased version of the passage is the following:
"Although combustion is based on scientific prin-
ciples, no one is certain exactly what they may be.
To become knowledgeable about the burning of fuel,
one must personally observe experiments to reach
reasonable conclusions about the hows, whats, whys
and whens of combustion. But in doing so there is
always the extreme hazard of misinterpretation,
which may lead the observer to errors greater than
those already in the literature." Although there cer-
tainly is nonnegligible truth in this statement, I
subscribe to a less pessimistic view.
The science of combustion stands on four ped-
estals (which do not resemble the four elements of
alchemy). These four supporting structures are
thermodynamics, chemical kinetics, fluid mechanics
and transport processes, each a mature science in
itself. I claim that "to become knowledgeable about
the burning of fuel" one must not only observe ex-
periments but also first master these four sci-
ences-so great a task that it is remarkable so many
of us are here! Although the main principles of
thermodynamics and fluid mechanics, needed in
combustion, had developed over many centuries and
were available early in the nineteenth century, the
sciences of chemical kinetics and of molecular
transport processes, with their essential background
in the kinetic theory of gases, did not begin to
flourish until the middle of that century. Therefore,
the science of combustion, as we know it, cannot
have been born until the last half of the nineteenth
century. The experiments of Sir Humphry Davy
(1815), of Robert Bunsen (1866), of Claude Louis
Berthelot and Paul Marie Eugene Vieille (1881, 1882)
and of Ernest Mallard and Henry Louis le Chate-
lier (1881, 1883), and the theories of Vladimir Alek-
sandrovich Mikhel'son (1890), of David Leonhard
Chapman (1899) and of Emile Jouguet (1905) in fact
led to the emergence of the science of combustion
around the turn of the century. In tracing the role
of theory in the modern science of combustion, the
starting point should be with these forebears. How-
ever, before moving on to specifics, I would like to
offer some general comments about the nature of
our science itself and about what is good theory.
Characteristics of the Science of Combustion
Any definition that attempts to completely de-
scribe combustion science should encompass its re-
lationship to its four supporting sciences. An aspect
of many combustion processes is their abrupt changes
in space and/or time of various properties, nota-
bly temperature, and this aspect has often been
 HO'Iq'EL PLENARY LECTURE
suggested as a suitable basis for a definition. For
example, Frank-Kamenetskii, in his excellent ex-
position of the subject, 4 preferred to include self-
acceleration in the definition, calling combustion the
science of large heat release and of either chain
branching or large activation energy. However, not
all combustion processes are abrupt; homogeneous
thermal explosions are not abrupt in space, station-
ary laminar flames not in time, and combustion in
rocket plumes, for example, typically is abrupt nei-
ther in space nor in time. For these reasons, 1 pre-
fer to call combustion the science of exothermic
chemical reactions in flows with heat and mass
transfer, or more briefly, exothermic chemistry in
flows. So far as I can see, some form of exother-
micity, somewhere, is always essential to the sub-
ject, except, perhaps, for some endothermic
branched-chain processes,4 and with "chemistry" this
can draw together the thermodynamics and chem-
ical kinetics. The "flows" are designed to bring in
the fluid mechanics and transport processes, al-
though this clearly is imperfect in that solid-solid
deflagrations involve flow only in a generalized sense,
and strictly homogeneous explosions necessitate an
even greater extension of the usual meaning of the
term. The difficulty, of course, stems from trying
to express many aspects in few words. It is impor-
tant to find a definition that does not exclude any
of the attendees at the symposia!
I have often heard combustion described as a
"mature" science. It seems to me that this is in-
appropriate--and not only because of the imma-
turity of its practitioners. It certainly must be less
mature than the fonr sciences on which it is based.
Just because combustion itself has been around for
mankind's half-million years does not mean that its
science has existed that long or must have been de-
pleted by now. There are plenty of things yet to
be discovered in our field--we are not at the end
of the untraveled road.
A more appropriate descriptor of combustion
would be an applied science, or a derived science.
Its foundation is derived from other sciences, and
it is applied in the sense that the fundamental
equations that describe combustion processes are
believed to be known. The distinction here is be-
tween pure and applied sciences, since in pure sci-
ences, such as particle physics, the underlying
equations are not known. The task of the theore-
tician in a pure science is to find the equations,
while in an applied science it is to solve them.
The last description tends to make our job ap-
pear too mechanical. All we need to do is to solve
equations, but the physicist can invent them--our
field should be assigned to the dullards! Well, things
are just not all that black and white. We certainly
know that those equations aren't particularly easy
to solve. In fact, what brought me into this field
was a graduate combustion course, given by Martin
Summerfleld at Princeton in 1954, which two friends
and I took as undergraduates. He wrote down the
full equations describing chemically reacting flows,
from the article by von K~trm~in and Penner. ~ I
looked at those equations and said to myself: "Surely
there is enough there to occupy me for a lifetime."
That observation certainly appears to have been
valid.
Our job is not just to solve--it is also to inter-
pret and to understand. In doing so we can be as
inventive as the physicist. We can identify new ap-
proximations for solving the Schrodinger equation
to describe chemical-kinetic processes in combus-
tion. We can call on concepts of chaos to address
turbulent combustion processes. Our applied sci-
ence has as much variety as any pure science. Dull,
mechanical actions, in either theory or experiment,
are not what we need. The unexpected experimen-
tal observation and the conceptually new theoreti-
cal idea are the sources of our advancement.
Characteristics of Good Theory
Given the complexity of the conservation equa-
tions of combustion, it can be tempting to conclude
that only detailed numerical treatments c a n pro-
duce good theory. I maintain that this is absolutely
false. Expanding a little on ideas that others have
expressed before, I propose three maxims for com-
bustion theory: Theory needn't be right to be good,
theory needn't be mathematical to be right, and
theory needn't be incomprehensible to be mathe-
matical. Each of these three statements clearly re-
quires some discussion.
Theory Needn't be Right to be Good:
The main point behind this statement is that the
progress in theory that improves human under-
standing is achieved through simplifications that are
never exactly right. A classical example is the Burke-
Schumann theory of diffusion flames. 6 Oxygen as
negative fuel? Shades of phlogiston! Not only does
the chemical kinetics need to be infinitely fast and
proceed in just one step, but also the diffusion
coefficients of fuel and oxygen must be equal. What
nonsenseT Yet, this is a remarkably useful way to
describe diffusion flames and greatly improves our
understanding of them. Resulting accuracies in pre-
dicted flame shapes and flame heights typically are
better than 20%. I remember puzzling time and
again over the question of how this theory can be
so good. The various different ways to arrive at the
theory, such as postulating full chemical equilib-
rium or strongly temperature-dependent reaction
rates, shed different lights on its meaning. Fur-
thermore, studies of the ways in which this theory
 THE ROLE OF THEORY IN COMBUSTION SCIENCE
is not right have greatly improved our understand-
ing of diffusion flames.
Many excellent theoretical contributions in com-
bustion are not exactly right. Consider, for exam-
ple, activation-energy asymptotics, as applied by
Zel'dovich and Frank-Kamenetskii to laminar flame
propagation. 7 This captures essential physics, even
though real combustion chemistry is seldom ever
one-step, and it makes us realize that the burning
velocity itself is an imprecise quantity, in that its
value can be expressed only as an asymptotic ex-
pansion. Another example is provided by the re-
cent intense studies of reduced chemical-kinetic
mechanisms. We could go on and on with citations
of theories that are not "right," but close enough
to being right, and successful enough in providing
new viewpoints, to be very good theories. The best
theories are pretty nearly right for some things, and
a task of the theoretician is to point out what those
things are. However, even theories that are proven
quite wrong can be good in inspiring research that
improves understanding--an example is the excess-
enthalpy theory, which held that the total enthalpy
in a laminar flame must be positive for the flame
to propagate.
The general idea can even be carried to the ex-
treme of claiming that theories that are too nearly
right are not very good in that they do not con-
tribute to improve understanding. "That theory is
no good. Why, it's not even wrong!" As a recent
example, we have been interested in axisymmetric
flows in laterally burning cylindrical solid-propel-
lant rocket chambers, wondering whether the flat-
tening of the radial profiles of axial velocity towards
the downstream end is due to turbulence or com-
pressibility. More than one group of investigators
has successfully developed and run Navier-Stokes
codes for this problem, with both k-E modeling and
compressibility included; proudly exhibiting the
flattening but, professing their belief in k-E turbu-
lence and in its importance to the phenomenon, not
being willing to take out one or the other of the
effects to show unquestionably what causes it. The-
ory that is exactly right not only will contain too
much to comprehend but also ultimately may be-
come tautological--devoid of content--testing only
the practitioner's ability to run the computer. If you
want to make progress in theory, you've got to make
at least a little error (preferably knowingly).
Theory Needn't be Mathematical to be Right:
This and the following statement refer to math-
ematics, a word studiously avoided until now. The
discussion of mathematical theory will be restricted
here to its role in combustion, and "right" now
means pretty nearly right, but a little wrong, so as
not to be no good. Despite recent apparent de-
clines in mathematical abilities of undergraduates,
5
the young people in our field, by and large, have
better mathematical backgrounds than the older
generation. Many forefathers fear being driven to
despair by their inadequacy in adaptive gridding,
asymptotics, and so on, up the mathematical al-
phabet. The poor old combustion experimenter, in
his modest laboratory, may begin to feel out of touch
with modern reality. To see why, it is necessary
only to scan the volumes of the combustion sym-
posia for their mathematical content.
Of fourteen papers in the first symposium, only
that of Burke and Schumann was mathematical--it
involved partial differential equations, fairly ad-
vanced mathematics for the field in 1928 (perhaps
the trouble has been with us longer than we re-
alize). Back then combustion scientists generally
knew arithmetic, trigonometry, algebra and some
aspects of calculus and of ordinary differential equa-
tions. Most of the earlier advances in combustion
theory, such as the distinction between deflagra-
tions and detonations identified by Chapman and
Jouguet, had mainly required a thorough knowl-
edge of nonlinear algebraic equations. In the sec-
ond symposium (1937), five out of twenty-five pa-
pers involved ordinary or partial differential
equations, a whopping 20%, up from less than 10%
in the first. Representative is the second-sympo-
sium paper by Bernard Lewis and Gunther von
Elbe, which addressed deflagration theory, employ-
ing partial differential equations.
Partial differential equations certainly are central
to combustion science; after all, the conservation
equations, s as finally developed fully, largely through
the efforts of Joe Hirschfelder and his collabora-
tors, 9 and of Theodore von K~irm~inand friends, 1~
around the time of the third symposium (1949), are
expressed most conveniently in partial differential
form. Aspects of early advances in the field in-
volved other branches of mathematics, such as or-
dinary differential equations for Cyril Norman Hin-
shelwood's and Nicolai Nicolayevich Semenov's
seminal developments in chemical kinetics11'12 and
integral equations for Hoyt Hottel's extensive con-
tributions to radiative transfer, 13 but partial differ-
ential equations surely can be said to form the core.
They have become a must in the repertoire of the
combustion scientist.
Nowadays, more than one-third of the sympo-
sium papers make essential use of mathematics at
the level of differential equations or beyond. And
what a variety of mathematical topics we find! Mod-
eling does not appear in the ten-volume index of
the tenth symposium but has numerous entries in
the ten-volume index of the twentieth. Asymptotic
analysis has begun to creep in, and the twenty-sec-
ond even has an entire section on fractals. Is our
mathematics getting out of control? Are we headed
towards the divorce of theory and experiment ex-
perienced by alchemy?
 HOTTEL PLENARY LECTURE
Certainly not. As far back as the Renaissance we
learned that theory had to keep in touch with ex-
periment to maintain healthy science, and we are
not about to forget. Increase in mathematical con-
tent with increasing time is a characteristic of every
science. Modem chemistry was born from the d e -
sire to have something more quantitative than the
sciences that preceded it. The march from algebra,
through differential equations, to asymptotics, sto-
chastics and fractals is a natural progression of a
healthy science. But this doesn't mean that we all
need to become mathematicians. We do need to
read to find out something about these concepts,
but if we encounter a book based on the "theorem-
proof" format we can put it down and find another
that speaks a more human language. The essential
thing in the theory is the concept, which often can
be exhibited most clearly when stripped of its
equations. Excessively mathematical theories tend
not to be very revealing.
Moreover, it should not be concluded that in the
first symposium only the Burke-Schumann paper
involved theory. Most of the other papers also in-
volved good theory, but not mathematical theory.
It is true that, as time goes on, mathematical as-
pects of the theories that are right increase. How-
ever, those aspects needn't dominate--they merely
reflect the general progression of human thinking.
Advanced mathematics is not essential in correct
theory.
Theory Needn't be Incomprehensible to be
Mathematical:
This statement addresses the formidability of too
many mathematically couched papers. There can be
a tendency to believe that mathematical content is
directly proportional to the number of symbols or
the number of equations. On the contrary, an in-
verse proportionality usually is more nearly correct.
Mathematics is a language that should be written
so that it can be read, with the same type of phras-
ing and punctuation as any other language, and
obfuscating symbols in excessive number detract
from that objective. It is unnecessary to write down
every little algebraic step. Let's only introduce
symbols that we need and use significantly, and de-
fine them clearly. This usually requires rereading
and rewriting each of our papers a few times. Un-
less a mathematical paper is comprehensible, it
probably does not contain a good mathematical the-
ory. One example of a well-written mathematical
paper is Graham Dixon-Lewis's invited paper on
structures of laminar flames in the twenty-third
symposium; 14 many other examples could be cited
from symposium volumes.
Tripartite Science
A revolution in the science of combustion began
about twenty years ago. The last theory-oriented
plenary lecture, the excellent review given b
Howard Emmons at the thirteenth symposium, L5
marked the end of the era in which computation--
the numerical solution of differential equations--
could only be considered to be a tool of theory. He
showed a calculation by G. A. Ball of the shape of
a thin premixed flame traveling along a gravity-free
channel, obtained by a relaxation method and rep-
resenting a significant accomplishment of numerical
computation at the time that it was performed. Why
is the resulting convex shape what was calculated?
That is a question for theory to address. We know
what equations predicted that shape, but we don't
have a good understanding of why that is what they
predicted. Suddenly, theory needs not only to try
to explain experimental observations--it also needs
to explain computational results. With the four-
teenth symposium we begin to see more and more
numerical solutions of partial differential equations
with high accuracy, and these become dominant
methods for modeling of combustion processes. Ex-
plosive computer advances have now made the me-
chanics of the Ball computation nearly trivial and
have enabled us to include many more phenomena
in numerical integrations (although research on the
Ball problem continues, mainly concerning appro-
priate boundary conditions at the wall).
Today it can be said, without controversy, that
there are three significant parts to combustion sci-
ence-experiment, computation and theory. Mu-
tual comparisons of all three help to advance the
science. So many phenomena are included in typ-
ical computational results that agreement between
experiment and computation no longer explains ex-
perimental results. Theory is needed to provide un-
derstanding of the results. Nowadays, advances in
theory are achieved as much by comparison with
numerical results of computational projects as by
comparison with experimental results obtained in
the laboratory, Computer laboratories provide the
new dimension, The three branches of the science
are now comparably important and are destined to
remain so.
Specific Contributions of Theory
Up until now, I have not really started to do what
was expected of me, and at this point there isn't
space to do it--you deserve a combustion theorist's
apology. I wanted to take a long view and to place
some prejudices before you. Having done so, I turn
to the specifics that you had anticipated. My Sa-
tanic verse is hereby concluded--on to more tech-
nical topics.
Even twenty years ago, Emmons 15 was able only
to present a selection of the many contributions of
theory to combustion science. Although I have eased
my task by dividing the field into three parts, so
 THE ROLE OF TtlEORY IN COMBUSTION SCIENCE
that I can exclude modeling and simulation based
on computation, I am still faced with too many con-
tributions to theory to review in one paper (even
had I started from the beginning with specifics). I
shall therefore content myself with a few examples,
asking forgiveness in advance from the many whom
I overlook--would that I could cite you all. At the
end of each topic, I shall try to indicate currently
outstanding research questions or future directions.
Reduced Chemistry
At least for problems in no more than one space
dimension, computers now enable full chemistry to
be handled routinely in combustion computations.
However, simplified chemistry is needed for higher
dimensions or for turbulence, as well as for im-
proved understanding in one dimension. While
sensitivity analysis and related techniques 16'17 en-
able many steps of lesser importance to be identi-
fied and discarded, more drastic reductions are
needed in advancing theory. These reductions come
systematically from steady-state and partial-equilib-
rium approximations, or from generalizations thereof.
Although such approximations have been known for
many years, ~ advances in asymptotic analysis now
place us in a much better position to identify these
approximations and test their accuracy.IS'l~ Impor-
tant reduced mechanisms have recently been de-
veloped for many combustmn . problems. 20 ' 21 ' 22
For hydrogen flames, systematic simplifications
that result in the one-step approximation 2Ha + 02
2H20 are of little use, except for correlating main
radical concentrations, H, OH and O (not HOz) in
the hottest part of diffusion flames at low strain, 23'24
but the two-step approximation
3H2 + O2 ~ 2H20 + 2H (1)
2H + M ~ H 2 + M, (2)
with rates determined, respectively, mainly by the
rates of the elementary steps
H+02~OH + O, (3)
H +Pc+ M~H()2+ M, (4)
has been found to be remarkably good for predict-
ing diffusion-flame extinction and profiles of tem-
perature, of concentrations of major species and of
concentrations of all intermediates except HOz and
H202. z~ The two-step description involves steady-
state approximations for O, OII, tlO2 and H20~ and
arrives at (1) by adding to (3) rapid shuffle steps to
cancel OIl and O algebraicaily;~" similarly, addition
of rapid HO2 and shuffle steps to (4) gives (2) whose
rate is that of the slowest step (4) in the sequence.
Such simple algebraic derivations are quick al-
though subject to pitfalls identifiable from asymp-
totic methods of greater rigor.
Fur methane flames, comparable accuracy de-
mands a four-step approximation, which through a
similar derivation can be written with
CH4 ~- 2H + H20 ~ CO + 4H2, (5)
CO + H20 ~- COz + ttz, (6)
added to (1) and (2), the rates of (5) and (6) being
determined, respectively, mainly by the rates of the
elementary steps
('tt4 + H ~ CIt3 + He, (7)
CO+ OH~CO2+ H. (8)
The fuel-consumption (5) and oxygen-consumption
(1) steps are different here, with the former re-
moving radicals and the latter producing them. Ex-
tensions to higher hydrocarbons and to alcohols are
in progress; some results for these more compli-
cated problems already are available, 21'25 and more
definitive resolutions may be expected in the near
fnture (for example, this week).
We may also anticipate extensive development of
reduced chemistry for pollutant production (NO, CO,
etc.) in combustion. Reduced mechanisms for pro-
pellant combustion, especially solid propellants, also
are progressing. For example, for the propellant-
related flames of methane with nitrogen dioxide, a
good four-step mechanism composed of (5), (6),
NO2 + H2 ~ NO + H20, (9)
2NO----> N2 + 02, (10)
has recently been identified, 26 the rates of the last
two being controlled, respectively, mainly by the
rates of
NO2 + H--~ NO + OH, (11)
NO+ H~N + OH. (12)
The rebirth of reduced chemistry, which occurred
about five years ago, will be fundamental to ad-
vances in theory for many years to come, supplant-
ing the use of model chemistry not tied to specific
reactants.
Premixed Laminar Flames
Restricting attention to steady, planar flames, we
note truly remarkable advances in theory since the
review of Emmons.15 The significance of the early
 HOTTEL PLENAI4.Y LECTURE
TJ
SLOPESMATCH
\ /
Y F u ~ y F ~ .~ t'~ Tb
i DIFFUSIVE ~ ~ ~t"~-- REACTIVE-
i L_. ZON
Tu ,i-"~-~'~_~/(o..v.,cn) ~' I ~)./(puVuCp,B)
0 0" x d
FIC. 2. Illustration of zone structure and match-
ing for premixed laminar flames according to AEA
(Y~. = fuel mass fraction, A = thermal conductivity,
p, = unburnt gas density, v= = burning velocity,
= Zerdovich number defined "after equation 13).
work of Zel'dovich and Frank-Kamenetskii7 for de-
scriptions based on the one-step, Arrhenius ap-
proximation was not fully appreciated then, al-
though the general character of the problem and of
the burning-velocity behavior was known. It was not
realized that their 1938 results7 represent the lead-
ing term in an asymptotic expansion for the burn-
ing velocity. Asymptotic analysis, especially matched
asymptotic expansions, now a mainstay of combus-
tion theory and the principal mathematics course
that graduate students in the field should be en-
couraged to take after partial differential equations,
was virtually unknown to our field at that time. The
formal expansion of Bush and Fendell,'27 as further
extended and elucidated in textbooks, zs'zg'3~ dem-
onstrated the asymptotic character of the result and
led to activation-energy asymptotics (AEA). Since
the value of the small parameter, /3-] of Fig. 2,
typically is on the order of 0. I, two-term (rather
than leading-term) expansions are desirable for pro-
ducing accuracy of theoretical predictions compa-
rable with experimental accuracy. 3~ The funda-
mental AEA tool of the combustion theoretician
revealed the laminar-flame structure ilhlstrated in
Fig. 2.
It is especially interesting to read Is from Em-
mon's plenary lecture of 1970 that "for essentially
all interesting fuels, the details of chemical kinetics
are so complex, if known at all, that flame speeds
are much easier to measure than to calculate." This
statement embodies in a nutshell how amazingly far
we have come in twenty years. Details of chemical
kinetics and elementary rates are known, for ex-
ample for methanol, well enough to enable planar,
adiabatic flame speeds to be calculated more ac-
curately than they can be measured, and moreover,
with today's computers and programs, these cal-
culations are routine--the opposite of the quoted
statement has come true. Although theory was in-
volved in developing the numerical methods, pres-
ent-day theory largely is directed towards under-
I ;. (),I(,~ VuCp)-- =I
1 I
I I H2 AND COOXIDATIONZONE T,
X/(~uC0 "1 I ~ i
i PRzEHEAT
rl~. T "'~:~--------FUEL-C~SUMPTION ZONE!
,
Fie,. 3. Illustration of the structure of the laminar
premixed methane-air flame according to RRA (same
notation as Fig. 2).
standing the computational (and experimental)
results. Asymptotic methods, applied to real chem-
istry, have clarified the structure of the ozone de-
composition flame. 32'aa'34 Understanding of the
structure of the methane flame has been obtained
by such methods, as'a6 as illustrated in Fig. 3. In
this more recent work, rate-ratio asymptotics (RRA)
replaces AEA, the principal small parameters, (5 and
~, representing the ratio of the rate constant for step
(3) to that for step (7) a n d (T/, - T ~ - T,),
respectively, where Th and Tu are the burnt and
unburnt gas temperatures, and T O is the tempera-
ture of the fuel-consumption zone, the temperature
at which the product of the rates of steps (4) and
(7) is effectively equal to the square of the rate of
step (3). In RRA the ratio of the rates of two im-
portant reactions in a critical zone, or the ratio of
the flow rate to the rate of an important reaction,
is treated as the small parameter in developing the
solution by matched asymptotic expansions. We are
in the midst of an explosion of theoretical expla-
nations of flame structures and burning velocities,
on the basis of underlying elementary chemical ki-
netics, by combinations of AEA and PtBA, for many
interesting fuels. Figure 4 illustrates buruing-veloc-
9 . 37
lty agreements obtained for methane flames.
Laminar Diffusion Flames
The same array of asymptotic tools that have been
applied to premixed flames has been brought to bear
on laminar diffusion flames9 AEA has done wonders
for our understanding of planar, laminar diffusion-
flame structure and extinction. 39 The S-shaped curve
of the peak temperature as a fimction of a Damkfhler
number that is inversely proportional to the exter-
nally imposed strain rate was already available more
than twenty years ago, 15 but the knowledge that four
different regimes (diffusion-flame, premixed-flame,
partial-burning and ignition regimes) occur along its
branches was not. One or another of these four re-
gimes of AEA reaction-zone structures has been en-
 THE ROLE OF THEORY IN COMBUSTION SCIENCE 9

50 I I I I I 2100 i i

ASYMPTOTIC

40 1900

50
r Tf(K) tTO0

> 20 .,/,.,%
I/ /
.-,
9 \\\\
1500
/~' NUMI~RICAL e '
to /If INTEGRATION / .
EXPERIMENTAL
MEASUREMENT
tS00 I
I I I I o 015 1,0 t .5
4 0.6 0.8 i.O ~-.2 t .4 i.6 ts (s)
EQUIVALENCE RATIO
FIG. 6. Dependence of the maximum tempera-
FIG. 4. The burning velocity of methane-air flames ture on the effective inverse strain rate for meth-
at 1 atm. and an initial temperature of 300 K, ac- ane-air diffusion flames, according to asymptotic
cording to asymptotic analysis with reduced chem- analysis with a three-step mechanism (curve), nu-
istry, 37 numerical integration with full chemistry, '7 merical integration with a four-step mechanism (tri-
and experiment. 38 angles), and experiment (squares), from Seshadri and
Peters. 4~

countered time and again in widely diverse prob-

lems in combustion theory. Basically, given a fuel
and oxidizer, there are four different ways in which
they can burn, three thin-sheet and one not: They
can both be used up in a thin reaction zone, one
can be used up there but not the other, neither
may be used up, or the reaction may be distributed
over a thick region. In many situations, the result-
ing asymptotic descriptions have done more than
improve our understanding of the phenomena--they
have also given reasonably accurate formulas for ig-
nition and extinction conditions. 4~
Methods of RRA have been successful for diffu-
sion flames as well. The methane-air diffusion-flame
structure according to RRA, in the coordinate of
mixture fraction Z, is illustrated in Fig. 5, which
shows the separate fuel-consumption and oxygen-
~OXYGEN-CONSUMPTION ZONE
, I"_, THICKNESS
0(()
~FUEL-CONSUMPTIONZONE
T Tcr THICKNESS0(8)
0 Zc
Z
FIG. 5. Illustration of the structure of the meth-
ane-air diffusion flame according to RRA.
consumption zones. The extinction portion of the S-
curve is shown in Fig. 6. Research is in progress
to obtain the ignition portion by these techniques
(which is of interest for application to diesel com-
bustion, for example) and to extend these methods
to other fuels. We may anticipate advances in de-
scriptions of structures of many real diffusion flames
by asymptotic methods.
Autoignition, Detonation and Explosion
Asymptotic methods are also becoming corre-
spondingly useful for analysis of time-dependent
autoignition with real chemical kinetics, not only
for hydrogen 42 but also for hydrocarbons;4z they
clearly define different stages in the ignition pro-
cess. Although empiricism still is involved for hy-
drocarbons, further advancement towards funda-
mental descriptions may be expected in the future.
i Progress towards understanding the ZND
(Zerdovich, yon Neumann, D6ring) detonation
structure 44'45'46 and its implications for both trans-
verse and longitudinal exothermic gas-dynamic in-
stabilities in detonations was in full swing twenty
years ago. Consequently we currently have a rea-
sonable knowledge of the omnipresence of cellular
detonationsY However, newer mathematical meth-
ods, based on AEA, bifurcation analysis and mul-
To tiple-scale expansions useful for improved numeri-
10 cal integrations, are leading to further
improvements. 4s'49 We need to apply such meth-
ods to address the important questions of detona-
tion transmission from one region to another and of
detonation failure in narrow tubes or in eonfigura-
10 HOTTEL PLENARY LECTURE
tions bounded by inerts, for which we currently have
qualitative understanding and empirical correla-
tions. 5~
Development of explosions from autoignition
processes, in some cases leading eventually to det-
onation, exhibits complicated dynamics providing
challenges in advancement of understanding, not
only with respect to the complex gas-dynamic as-
pects but also in determining where transport and
chemical-kinetic effects occur, scales of different re-
gions and influences of different chemistry. Theory
in this area continues to progress, 4s'51'52'53again with
extensive help from asymptotic analysis.
Ignition Theory
Mainly in the decade of the 1970s, AEA was ap-
plied extensively to time-dependent ignition prob-
lems, 54'55'56 providing one of the main arenas in
which the power of that technique was demon-
strated. Solutions to many ignition problems are now
available, 3~ illustrating juxtapositions of different
spatial zones and temporal stages in ignition pro-
cesses. Recent worko~'Ss is applying asymptotic
methods to address influences of more complicated
chemical kinetics on ignition times and on ignition
distances in boundary-layer flows. Further research
also is needed concerning effects of geometry, such
as sharp corners, 59 on ignition.
Deflagration of Solids and Liquids
Although Lewis and Prandtl numbers generally
are of order unity for gases, they both tend to be
large for condensed phases. This and variations of
transport coefficients can affect reaction-zone struc-
tures, 6~ in one limit yielding difffusion-free defla-
gration. Instabilities and bifurcations, leading to
oscillatory propagation with supera-diabatic temper-
atures, approaching chaos, and to spinning defla-
grations, then occur. 61 Understanding of these and
related phenomena has been developed by theo-
retical analyses. 62-e5
Condensed-phase chemical kinetics generally be-
come important in propellant deflagration, and in-
teractions between chemistry, transport and flow can
be complex. Moreover, different propellants typi-
cally behave differently. ~ Theoretical analyses for
specific propellants provide insights on deflagration
mechanisms.
For example, for nitramines melting forms a liq-
uid layer in which decomposition occurs, but there
is also vaporization and further exothermicity in both
a primary and a secondary gas-phase flame zone.
Only the chemistry of the condensed phase and
primary zone affects the deflagration rate appreci-
ably. Analyses applying AEA to one-step approxi-
mations for the chemistry in each of these zones
and treating the liquid-gas interface as planar can
produce excellent agreement with measured defla-
gration rates and their pressure and temperature
sensitivities. 6s Although this ignores bubbling ob-
served in the liquid layer, study of this two-phase
flow69 reveals that, despite the necessity of intro-
ducing a sublayer of nonequilibrium vaporization and
the intrusion of a number of physical phenomena,
notably Marangoni convection, in influencing the
two-phase behavior, the deflagration rates pre-
dicted by the planar-interface model are modified
only slightly. Outstanding challenges to theoreti-
clans include development of reduced chemistry to
explain the two-stage gas-phase combustion and to
identify the source of the values of the energetic
and rate constants that are successful in the one-
step approximations.
Flame Spread
Theory has contributed to understanding of pro-
cesses of flame spreading through condensed fuels
in recent years. Emmons discussed this subject
twenty years ago, 15 but further advances have been
made. 7~ In particular, for spread along solid fuels
there are improved kernel decompositions, 72-7s ex-
tending the original analysis of John de Ris.76 In-
troducing an Oseen approximation for countercur-
rent gas flow over the surface of a thermally thick
or thermally thin solid fuel, de Ris76 derived a set
of linear partial differential equations with constant
coefficients having different boundary conditions in
the two semi-infinite domains at the fuel surface
ahead of and behind the point of flame attachment.
That set is equivalent to a set of integral equations
that is suited for solution through Fourier trans-
forms by the Wiener-Hopf technique of kernal
splitting in complex-variable theory. Although he
split the kernel exactly for his thermally thick fuel,
de Ris76 accomplished this only approximately for
thermally thin fuels. Delichatsios 75 was able to split
the kernel exactly for the thermally thin fuel and
thereby removed a discrepancy of about a factor of
two between theoretical and experimental spread
rates. Wichman74 replaced the Oseen approxima-
tion by a linear velocity gradient and succeeded in
solving the resulting system having variable coeffi-
cients, again by the Weiner-Hopf technique, thereby
obtaining improved correlations of measured rates
of creeping spread along thermally thick fuels. 72
Integral equations arise in an essential way in
describing concurrent or upward flame spread. Al-
though approximate solutions have been obtained
that afford reasonable agreement with experimental
spread rates, 77'78 more research is needed, espe-
cially concerning behaviors of spread along charring
fuels. Further theoretical studies also could be
 THE ROLE OF THEORY IN COMBUSTION SCIENCE
helpful on spread over surfaces of liquid fuels, on
influences of gravity in flame spread, on spread
through porous fuel beds and on spread through
fuel particle clouds, including effects of radiant en-
ergy transfer. Although there have been significant
recent advances in these areas, appreciable addi-
tional progress may be anticipated in the near fu-
ture.
Flame Instabilities
Premixed laminar flames are especially rich in in-
stability phenomena, our theoretical understanding
of which has progressed continually, beginning more
than a half-century ago. The Darrieus-Landau hy-
drodynamic instability 79 of the planar flame, always
present when the density of the fresh mixture ex-
ceeds that of the burnt gas, necessitates stabilizing
effects from diffusive-thermal phenomena at short
wavelengths and from body-force (buoyancy) or ap-
paratus-boundary phenomena at long wavelengths
for the planar flame to exist. Despite excellent ear-
lier work, s~ the final comprehension that enables
this statement to be made definitively stems mainly
from the research of Paul Clavin and his
collaborators 79 in the 1975-85 decade. Those stud-
ies succeeded in assimilating earlier theory and in
developing new theory to arrive at the general con-
clusion stated above, which self-consistently ex-
plains observed flame instabilities.
Diffusive-thermal phenomena and body-force
phenomena can be destabilizing (as for fuel-lean hy-
drogen flames and upward-propagating flames, re-
spectively), in which cases, instead of planar flames,
cellular or curved flames are observed. When hy-
drodynamic instability and a body-force effect
through a stabilizing gravitational acceleration g are
both included, then a dispersion relation for a
wavenumber k and a growth rate proportional to
e~ is found to be
(13)
where Vu and vb are the velocity with respect to
the wave in the unburnt and burnt gas, respec-
tively, (the burning velocity), and r is the ratio of
the burnt-gas density to the unburnt-gas density.
Since ~" < 1, (13) shows that o" > 0 when g < 0,
which is gravitational instability. Diffusive-thermal
instability is richer and is exhibited most clearly by
putting ~" = 1 to eliminate the other two instabil-
ities. The result, derived by Joulin and Clavin, sl is
a more complicated dispersion relation, 3~ the im-
11
~(L-1)~)LSATIN o-P
TR
ULASVAETLN
IN
IG
G,
~I \,.k
4(1+~3)
ITRAVELN
ff
IG
21/2 ~ [ / " ' " ,=k
6 m (7
18/5--
i i , ,
t'.2 ~ ~ k
~n (tlF2)
I
FIG. 7. Regions of diffusive-thermal instability in
a Lewis-number, heat-loss plane, with dispersion
relations illustrated by insets. 8'
plications of which are illustrated in Fig. 7, where
L is the Lewis number of the deficient reactant (the
ratio of the thermal diffusivity to its molecular dif-
fusion coefficient), /3 = E(Tb - T , ) / ( R T ~ ) i s the
Zel'dovich number, and the horizontal scale (with
/x the ratio of the burning velocity of a nonadiabatic
planar flame to that of the adiabatic planar flame)
is a measure of the rate of heat loss. Although the
theoretical analysis employed AEA, recent studies
by RRA indicate that, with proper interpretation,
the AEA results apply well to real flames.
Diffusive-thermal instabilities have been ana-
lyzed with variable-density effects, s2's3's4 with in-
fluences of an upstream flame-holder, sS-s9 and with
influences of stretch, 9~ for example. The theory has
amassed an extensive body of information in recent
years. 2s'29,3~ The diverse character of flame in-
stabilities has, in fact, attracted wide attention be-
yond the combustion communityb in the general
physics of nonlinear phenomena. 2 Besides poly-
hedral, cellular structures, spinning structures and
oscillations with period doubling, approach to chaos
is observed in certain flames, as described, for ex-
ample, by the Kuramoto-Sivashinsky equation. 91'92
Since flame chaos is simpler than the chaos of Na-
vier-Stokes turbulence in that it can occur (from high
activation energy and unequal diffusion) even in just
one space dimension, for example, study of flame
instabilities provides a useful approach to the de-
velopment of understanding of nonlinear phenom-
ena. Much more research remains to be performed
on the nonlinear theory of flame instabilities.
Flames in Nonuniform Flows
A closely related topic concerns the structure and
dynamics of premixed flames in nonuniform flows.
12 HOTTEL PLENARY LECTURE
Strain along a flame sheet modifies the flame struc-
ture, making it thinner. Karlovitz93'94 called this
"flame stretch," and its effect can be measured by
a nondimensional parameter K, often called the
Karlovitz number. For weak stretch and curvature
of a nearly planar flame, the influence of both of
these perturbations arise through a single parame-
ter, the nondimensional flame stretch,
1 f
K = -- } I)u(V " n)
Vu (14)
- ~n" (Vu) + (Vv) r 9n ,
where 1 is the undisturbed flame thickness, n is a
unit vector normal to the flame sheet, pointing to-
wards the fresh mixture, and (Vv) is the d vadic gra-
dient of the local velocity field, with (Vv) its trans-
pose, the sum being twice the strain-rate tensor.
The first term in (14) defines the stretch due to
curvature. Weak stretch corresponds to small K,
moderate stretch to K of order unity and strong
stretch to K large; strain and curvature exert quan-
titatively different influences for moderate or strong
stretch.
AEA analyses have been completed for weak,
moderate and strong stretch of planar flames in
counterflows, including influences of variable den-
sity, of Lewis numbers different from unity, of non-
adiabaticity arising from product-gas temperatures
T~ being different from the adiabatic flame tem-
perature T,~f, of different strain rates in different or-
thogonal directions, and of swirl having vorticity
normal to the plane of the flame. 95-99 Represen-
tative results for influences of nonadiabaticity with
Lewis numbers L of unity are shown in Fig. 8,
which demonstrates abrupt extinction for suffi-
ciently subadiabatic conditions. For adiabatic flames,
AEA shows abrupt extinction to be achievable only
with difficulty and only for L > 1; at large tr grad-
ual extinction occurs for all H and L. The first the-
oretical analysis of this type of problem was given
by Klimov,100 who did not use formal AEA expan-
sions but obtained leading-order effects. For suffi-
ciently weak stretch, there are indications from RRA
that AEA results can be made to apply with real
chemistry, but this will not always extend to larger
stretch, 1~ and more research is needed on this
question. For weak stretch, the burning velocity can
be approximated as
V = vue -b', (15)
where Vu refers to the unstrained flame, and bl is
a Markstein length, which can be calculated from
the flame structure. 79'83 From these results, for weak
stretch, a general equation for flame dynamics can
z.5 / '
z.o~
h ~ SOPERADIABATIC
t5 ~ /r0f-r~
~ H.13~r--~--)
k~
ADIABATIC 0
I.o SUBADIABATIC ,.,~'.I--~" - -
/ [.~ EXTINCTION
05
~ #i\u~176
TRAN,T,O.
~_____.~._~.~..J........
I I
~ lot 1/K t to
FIG. 8. The ratio /.t of the rate of heat release
per unit area of a strained premixed flame to that
of an unstrained flame as a function of the inverse
nondimensional strain rate for various nonadiabat-
icity parameters H (/3 = Zel'dovich number).
be derived. 3~176176176 Because of the restriction
to weak stretch, a linear expansion of the exponen-
tial in (15) is equally accurate and often most con-
venient, but in calculations such as simulations that
occasionally produce bK > 1, (15) has the virtue of
maintaining positive burning velocities.
Vortices are flow nonuniformities related to tur-
bulence, and progress has been made in describing
laminar-flame interactions with vortices. Flat flames
can be spun into sufficiently strong unstretched
vortex cores, resulting in a core of burnt gas with
a flame propagating outward from it. lo~ Stretch of
the vortex can arrest the outward propagation, giv-
ing cylindrical flames wrapped around vortices that
are good candidates for elements in turbulent com-
bustion. Also, since the radial pressure field of a
vortex depends on the gas density, if part of the
vortex core is fresh mixture and another part burnt
gas, the products will be driven along the core by
the pressure gradient at velocities that can greatly
exceed the laminar burning velocity.]~ Diffusion
flames also can be wrapped into unstretched vortex
cores, although this requires very strong vortices
seldom encountered in turbulent combustionJ ~
There has been an appreciable amount of recent
theoretical analysis of flame-vortex interactions, but
more remains to be done in the future, for example
concerning effects of vortex stretching and of real
chemistry.
Turbulent Combustion
Theories for turbulent combustion differ for pre-
mixed and nonpremixed systems and for reaction-
 THE ROLE OF THEORY IN COMBUSTION SCIENCE
401 LAMrN'~R 1 TURBLJt.E/TT
\ ~
oV It /I N--~--,4oU ~
"~
EXITVEI.0CI'P(mls)
f
FIG. 9. Dependence of the height of a turbulent-
jet diffusion flame on jet velocity.
sheet and distributed-reaction limits. 3~ Figure 9,
based on a diagram first presented by Hottel and
Hawthorne in the third symposium, 1~ illustrates a
variety of phenomena and problems that have been
studied theoretically for turbulent diffusion flames.
Although this is a continuing topic of theoretical in-
vestigation, discussion is restricted here to pre-
mixed turbulent flames.
In the reaction-sheet regime, a smooth function
G can be introduced, such that G < 0 in fresh mix-
ture, G > 0 in burnt gas, and G = 0 at the flame.
An evolution equation for the flame in the turbu-
lent flow can then be written as8~176176
gG
-- + v - V G = v IVGI,
8t
in which (14) and (15) may be used for the laminar
burning velocity V. Theoretical study of (16) is
playing a significant role in attempts to understand
premixed turbulent-flame propagation. Since there
are no requirements on G beyond those just stated,
it may be given different physical interpretations;
even its units are arbitrary. In one interpretation,
its root-mean-square fluctuation gives the turbulent
flame thickness, u l
For sufficiently weak turbulence, perturbation
methods have been employed to obtain burning
velocities and changes in turbulence across the
flame, n~dl3 On the basis of these results, it has
been widely accepted that for small values of the
ratio of the root-mean-square turbulent fluctuation
velocity u' to vu, the turbulent burning velocity dif-
fers from Vu by an amount proportional to (u'/Vu) 2.
However, there has been a recent challenge to this
result, n4 in effect based on the observation that the
Fourier decompositions do not achieve statistical
stationarity; this study, based on (16), deduces by
balancing flame-area growth through turbulent dif-
fusion with its consumption by transverse laminar-
flame propagation that the proportionality instead is
to (u'/vu) 4/3. This observation makes the inventive
renormalization methods, which have been ap-
plied to (16) to give intriguing results for turbulent
burning velocities at high turbulence intensi-
13
ties, nS"n6'n7 even more controversial than they were
initially.
- ~ Equation (16) applies at all scales in the reaction-
sheet regime and for large values of (u'/v,) in this
regime predicts multiple flamelets, enclosing pock-
ets of unburnt gas (but none of burnt gas). The
wrinkled flame surface in this multiple-sheet sub-
8o
regime may be described as a fractal, ns having a
fractal dimension of 21, but only for sizes between
the integral scale of turbulence (the large-eddy di-
mension) and the Gibson scale, n9 the eddy size at
which vu equals the eddy turnover velocity. If
Reynolds number is increased at fixed Damk6hler
number until the laminar-flame thickness is com-
parable to the Kolmogorov scale, then the Gibson
scale becomes equal to the Kolmogorov scale, and
flamelets begin to quench in the smallest eddies (the
Klimov criterion), giving rise to a broken-flamelet
regime. At higher Reynolds numbers in the bro-
ken-flamelet regime, (16) can apply only in eddies
having sizes between the integral scale and the Pe-
ters scale, n9 the eddy size below which the strain
rate is too high for laminar flamelets to exist in the
eddies. The recent identification of these important
length scales in premixed turbulent combustion, as
well as of others I2~ that are closely related and that
include considerations of hydrodynamic instability,
helps to mark the rapid development that the sub-
(16) ject has experienced in reeent years.
Not all recent developments in theories of pre-
mixed turbulent combustion are based on (16). For
example, the Bray-Libby-Moss approach, which
bears some relationship to (16) in presuming that
primarily only reactants and products are present,
employs different equations;121 a more detailed
presentation of these and other approaches soon will
be published. 122 Intense research currently is in
progress, for example related to (16), and impor-
tant, new theoretical results will soon be seen from
various groups. Today is a very exciting time in the
theory of turbulent combustion.
Concluding Comments
These last few sections clearly have been rushed
and compressed nearly to the point of incoherence.
A more leisurely monograph on the subject, of less
than 200 pages, is just now becoming available. 123
The last chapter of that monograph is entitled "The
Future" and offers more extensive speculations on
what may lie ahead than can be found in the brief
comments made in the preceding sections. Not only
have I been unable to give thorough citations here--
I have even had to exclude some entire topics
(droplets, sprays, combustion chambers, etc.). At
least you cannot help but leave with the sensation
that theory has been, is and will be a significant
14 HOTFEL PLENARY LECTURE
part of combustion science. A better presentation
would have been made by Prometheus.
Acknowledgment
I wish to thank Ed Law for the invitation that
gave me the opportunity to prepare this manuscript
and also for securing comments on my first draft
from a large n u m b e r of reviewers. My sincere grat-
itude goes to the dozen or so reviewers, most of
whose identities are unknown to me, who returned
reports for my consideration. The most critical and
least kind reports were the most useful and led to
many revisions, although I am fully aware that many
still will remain dissatisfied with this final product.
Thanks also go to the NSF, NASA, DOE and I ) O D
funding agencies that have supported my research
and to students, whose questioning and enthusiasm
help greatly in sharpening ideas.
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61. MERZttANOV, A. G. ANt) BOROVINSKAYA, I. P.:
Combust. Sei. Tcch. 10, 195 (1975).
62. MA'IXOWSKY,B. J. AND SIVASItINSKY,G. I.: SIAM
J. Appl. Math. 35, 465 (1978).
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432 (1981).
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(1985).
65. MARGOLIS, S. B. AND WILLIAMS, E. A.: Corn-
bust. Flame 79, 199 (1,990).
66. WILLIAMS, F. A., BARRI~RE, M. AND HUANG, N.
C.: Fundamental Aspects of Solid Propellant
Rockets, AGARDograph 116, Teehnivision
Services, 1969.
67. Kuo, K. K. AND SUMMERFIELD, M., Eds.:
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Fundamentals of Solid-Propellant Combus-
tion, Prog. Astron. Aeron. 90, AIAA, 1984.
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Symposium (International) on Combustion, p.
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B.: Combust. Flame 80, 329 (1990).
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ternational) on Combustion, p. 1281, The
Combustion Institute, 1977.
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8, 317 (1982).
72. WICIIMAN, I. S., WILLIAMS, F. A. AND GLASS-
MAN, I.: Nineteenth Symposium (Interna-
tional) on Combustion, p. 835, The Combus-
tion Institute, 1982.
73. WICtlMAN, I. S. AND WILLIAMS, F. A.: Com-
bust. Sci. Teeh. 32, 91; 33, 207 (1983).
74. WICHMAN, I. S.: Combust. Flame, 50, 287
(1983).
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A.: Proceedings, The First International Sym-
posium on Fire Safety Science, p. 75, Hemi-
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AND QUIXTIEBE, J.: Transactions ASME, J. lteat
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M6chanique Thdorique et Appliqu6e 2, 245
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Soc. London 372A, 367 (1979).
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Eds. : Combustion and Nonlinear Phenomena,
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Combust. Sci. Tech. 34, 257 (1983).
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Sci. Tech. 54, 237 (1987).
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LIAMS, F. A.: Phys. Fluids A2, 1213 (1990).
99. KIM, J. S., LIBBu P. A. AND WILLIAMS, F. A.:
Phys. Fluids A, to appear, 1992.
100. KIAMOV,A. M.: Zhur. Prikl. Mekh. Tekhn. Fiz.
No. 3, 49 (1963).
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104. MATALON, M.: Combust. Sci. Tech. 31,
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105. PETERS, N. AND WILLIAMS, F. A.: Twenty-Sec-
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tion, p. 495, The Combustion Institute, 1989.
106. CHOMIAK, J.: Combustion, A Study in Theory,
Fact and Application, Gordon and Breach,
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107. ASHURST, W. T. AND WILLIAMS, F. A.: Twenty-
COMMENTS
Horst-Henning Gortheer, DLR Stuttgart, Ger-
many. The nearly perfect agreement between ex-
perimental burning velocities with the simulated
ones (full chemistry) as shown in Fig. 4 might sug-
gest that the kinetic data for the reactions in ques-
tion are essentially known. Actually, the used rate
coefficients rest quite often upon estimates a n d / o r
extrapolations due to the lack of direct measure-
ments. This applies in particular to radical-radical
reactions or to other reactions leaving more than
one exit channel. The CH4/air flame is a good ex-
ample: here, for stoichiometric conditions, a burn-
ing velocity of only 0.36 m / s e c is calculated' if for
Third Symposium (International) on Combus-
tion, p. 543, The Combustion Institute, 1991.
108. HOa'rEL, H. C. AND HAWTHORNE, W. R.: Third
Symposium (International) on Combustion, p.
254, Williams and Wilkins, 1949.
109. WILLIAMS, F. A. : Turbulent Combustion, The
Mathematics of Combustion (J. D. Buckmas-
ter, Ed.), p. 97, Vol. 2 of Frontiers in Applied
Mathematics, SIAM, 1985.
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LIAMS, F. A.: Phys. Rev. A 37, 2728 (1988).
111. PETERS, N.: unpublished, 1991.
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116, 251 (1982).
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J. Fluid Mech. 228, 487 (1991).
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Lett. 68, 934 (1992).
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(1988).
116. SIVASHINSKY, G. I.: Combust. Sci. Tech. 62,
77 (1988).
117. YAKHOT, V.: Combust. Sci. Tech. 62, 127
(1988).
118. KERSTEIN, A. R.: Combust. Sci. Tech. 60, 441
(1988).
119. PETERS, N.: Twenty-First Symposium (Inter-
national) on Combustion, p. 1231, The Com-
bustion Institute, 1988.
120. KUZNETSOV, V. R. AND SABEL'NIKOV, V. A.:
Turbulence and Combustion, Hemisphere,
1990.
121. LIBBY,P. A. AND WILLIAMS, F. A., Eds.: Tur-
bulent Reacting Flows, Springer-Verlag, 1980.
122. LIBBY, P. A. AND WILLIAMS, F. A., Eds.: Tur-
bulent Reacting Flows, Academic Press, to
appear, 1992.
123. LI~qhN, A. AND WILLIAMS, F. A.: Fundamental
Aspects of Combustion, Oxford University
Press, to appear, 1993.
the reaction CH3 + O H rate coefficients are used
according to a theoretical model of Dean and
Westmoreland z and as much as 0.48 m / s e c (other-
wise the same model) if data according to a theo-
retical model of Pilling and coworkers 3 are used for
this same reaction. Obviously, the experimental re-
sults of Fig. 4 are right in between.
Another example as mentioned by Prof. Williams
in his oral presentation is the kinetic model for
CH3OH oxidation: calculated burning velocities are
highly dependent on (among others) the rate coef-
ficients for the thermal decomposition of CH2OH
and HCO radicals, respectively. The former reac-
 TIlE ROLE OF TttEORY IN COMBUSTION SCIENCE
tion has never been directly measured, whereas
measurements for the latter cover only the tem-
perature regime below 1000K, 4 so that a substantial
extrapolation is required.
A third example, which is of general interest for
the modeling of hydrocarbon flames, the continuing
uncertainty with regard to C2H3 reactions is ad-
dressed: For CztI3 + Oz, direct measurements exist
again only at temperatures below 100OK, whereas
from theoretical considerations a pronounced fall-off
behavior has been derived. 5 For the reaction C2H~
+ OH no direct measurements exist at all. 6
REFERENCES
LOSER, tl., STOTHAHt), N. D., IIUMPFER, R. AND
GROTHEER, II. H.: Direct measurements of CH3
+ OH. J. Phys. Chem., in press (1992). See also:
OSER, H., STOTIIARD, N. D., IIuMPFER, R., GRO-
TIIEEn, H. H. AND JUST, TU.: This Symposium,
Paper No. 70.
17
2. DEAN, A. M. ANI) WESTMORELAND, P. |~t.: Int. J.
Chem. Kin. 19, 207 (1987).
3. GSEEN, N. J., PEREI~, A. R., PILLING, M. J.
AND ROBESTSON, S. H.: Twenty-Third Sympo-
sium (International) on Combustion poster.
4. TIMONEN, R. S., I~TAJCZAK, E., GURMAN, D. AND
WAGNES, A. F.: J. Phys. (;hem. 91, 5325 (1987).
5. WESTMORELA.'~D, P. a.: this Symposium, Poster
No. 55.
6. WAI~Naa'Z, J.: this Symposium, Paper No. 2.
Author's Reply. Your comment is worthwhile.
Many unknowns remain in elementary rate param-
eters, and continuing research is needed to reduce
the uncertainties. For the methanol and methane
examples that you cite the uncertainties are much
less than for higher hydrocarbons, which 1 believe
need much more study of elementars' rates. The
agreement in Fig. 4 is based on best estimates of
elementary kinetic data and could not have been
achieved twenty years ago. Great progress has been
made in determining elementary rate parameters,
but there is certainly much more to be done.