Combustion Chemistry

ACS
SYMPOSIUM
SERIES
The Chemistry of Combustion

Processes
Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.fw001
Thompson M. Sloane, EDITOR

General Motors Research Laboratories
Based on asymposiumsponsored by
the Division of Industrial
and Engineering Chemistry
at the 185th Meeting
of the American Chemical Society,
Seattle, Washington,
March 20-25, 1983
American Chemical Society, Washington, D.C. 1984

In The Chemistry of Combustion Processes; Sloane, T.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1983.
249
Library of Congress Cataloging in Publication Data

The chemistry of combustion processes.
( A C S symposium series, I S S N 0097 6156; 249)
Includes bibliographies and indexes.

1. CombustionCongresses.
I. Sloane, Thompson M., 1945. II. American
Chemical Society. Division of Industrial and
Engineering Chemistry. III. American Chemical
Society. Meeting (185th: 1983: Seattle, Wash.)
IV. Series.
QD516.C537
1984
I S B N 0 8412-0834 4
541.3'61
84-2816
Copyright 1984
American Chemical Society
A l l Rights Reserved. The appearance of the code at the bottom of the first page of each
chapter in this volume indicates the copyright owner's consent that reprographic copies of the
chapter may be made for personal or internal use or for the personal or internal use of specific
clients. This consent is given on the condition, however, that the copier pay the stated per
copy fee through the Copyright Clearance Center, Inc., 21 Congress Street, Salem, MA 01970,
for copying beyond that permitted by Sections 107 or 108 of the U . S . Copyright Law. This
consent does not extend to copying or transmission by any meansgraphic or electronicfor
any other purpose, such as for general distribution, for advertising or promotional purposes,
for creating a new collective work, for resale, or for information storage and retrieval systems.
The copying fee for each chapter is indicated in the code at the bottom of the first page of the
chapter.
The citation of trade names and/or names of manufacturers in this publication is not to be
construed as an endorsement or as approval by A C S of the commercial products or services
referenced herein; nor should the mere reference herein to any drawing, specification, chemical
process, or other data be regarded as a license or as a conveyance of any right or permission,
to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or
sell any patented invention or copyrighted work that may in any way be related thereto.
Registered names, trademarks, etc., used in this publication, even without specific indication
thereof, are not to be considered unprotected by law.
PRINTED IN THE UNITED STATES OF AMERICA

ACS Symposium Series

M. Joan Comstock, Series Editor
Advisory Board
U.S. Geological Survey
Geoffrey D. Parfitt
Carnegie Mellon University
Martin L. Gorbaty
Exxon Research and Engineering Co.
Theodore Provder
Glidden Coatings and Resins
Herbert D. Kaesz
University of CaliforniaLos Angeles
James C. Randall
Phillips Petroleum Company
Rudolph J. Marcus
Office of Naval Research
Charles N. Satterfield
Massachusetts Institute of Technology
Marvin Margoshes
Technicon Instruments Corporation
Dennis Schuetzle
Ford Motor Company
Research Laboratory
Robert Baker
Donald E. Moreland
USDA, Agricultural Research Service
W. H. Norton
J. T. Baker Chemical Company
Robert Ory
USDA, Southern Regional
Research Center
Davis L. Temple, Jr.

Mead Johnson
Charles S. Tuesday
General Motors Research Laboratory
C. Grant Willson
IBM Research Department

FOREWORD
The ACS SYMPOSIUM SERIES was founded in 1974 to provide
a medium for publishing symposia quickly in book form. The
format of the Series parallels that of the continuing ADVANCES
IN CHEMISTRY SERIES except that in order to save time the
papers are not typeset but are reproduced as they are sub
mitted by the authors in camera-ready form. Papers are re
viewed under the supervision of the Editors with the assistance
of the Series Advisory Board and are selected to maintain the
integrity of the symposia; however, verbatim reproductions of
previously published papers are not accepted. Both reviews
and reports of research are acceptable since symposia may
embrace both types of presentation.

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.pr001
PREFACE
IN RECENT YEARS, combustion science has undergone a dramatic transfor
mation as modern analytical tools have been applied to the study of
combustion systems. Techniques involving molecular beams and lasers,
which have been so successful at breaking new ground in the fields of
spectroscopy and chemical reaction kinetics and dynamics, are now yielding
information in increasingly microscopic detail about the physics and chemis
try of combustion processes. These new techniques, particularly laser tech
niques, have gone beyond the demonstration stage and have made significant
contributions to our knowledge.
This volume focuses on the understanding of chemical aspects of
combustion processes that has been achieved with these new experimental
methods and with the concurrent increase in theoretical work. The signifi
cance of these topics in current combustion science is due principally to their
role in the strongly linked areas of energy conservation, pollutant emissions,
and safety. For example, the subject of detonations is of primary importance
in the transportation safety of natural gas in both the liquid and gaseous
state. New methods of ignition may yield more efficient combustion pro
cesses in automobile engines. A better understanding of the chemistry of fuel
nitrogen conversion to nitric oxide will aid in reducing nitric oxide emissions
from coal-fired combustors and from combustors utilizing heavy fuels made
from coal and shale. A determination of the mechanism of soot formation
and destruction will help to make the highly efficient diesel engine more
environmentally acceptable in transportation vehicles and should also aid in
reducing soot emissions from combustors burning coal and heavy liquid
fuels.
I would like to thank the authors and speakers for their contributions
that made this symposium such a worthwhile endeavor. Thanks are also due
to the publishers for providing the means to record the proceedings of this
symposium.
T H O M P S O N M. S L O A N E
General Motors Research Laboratories

Warren, Michigan
December 1983
vu

1
Role of C Hydrocarbons in Aromatic Species
Formation in Aliphatic Flames
4
Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001
J. A. COLE , J. D. BITTNER , J. P. LONGWELL, and J. B. HOWARD

Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge,
MA 02139
The free-radical addition reaction expressed as
1,3-butadienyl + acetylene-->benzene + H-atom
is shown to account for benzene formation in the
preheat region of a low-pressure, near-sooting,
premixed 1,3-butadiene flame using an estimated
rate constant, Log k = 8.5 - 3.7/2.3 RT l/(mols),
and measured species concentration profiles. Using
similarly estimated rate constants with activation
energies of 1.8, 0.6, and 3.7 kcal/mol it i s shown
that 1,3-butadienyl addition to C4H2, C4H4, and
C3H4 also accounts for the formation of phenylacetylene and styrene but not toluene. Other reaction
mechanisms involving C-4 hydrocarbons also are con
sidered but are too slow in this flame. Concentra
tion and molar flux profiles obtained by molecular
beam sampling with on-line mass spectrometry are
presented for 31 species.
Aromatic hydrocarbons are known to be important in soot formation
in flames. The aromatic structure may abet molecular growth lead
ing to PAH and soot formation through i t s ability to stabilize
radicals formed from addition of aromatic radicals to unsaturated
aliphatics such as acetylenic species (1*2) Accordingly, both
aromatics and unsaturated aliphatics would be important for growth
processes. Both types of species are prevalent in the flame zone
where growth occurs. Aromatic structures with unsaturated side
chains also are observed there (1^2)
1
Current address: Energy and Environmental Research Corporation, 18 Mason, Irvine, CA

92714
Current address: Cabot Corporation, Concord Road, Billerica, MA 01821
2
0097-6156/84/0249-0003506.00/0
1984 American Chemical Society
CHEMISTRY OF COMBUSTION PROCESSES
I n a l i p h a t i c f l a m e s a r o m a t i c r i n g s must be f o r m e d f r o m n o n a r o m a t i c p r e c u r s o r s , b u t an a c c e p t e d mechanism f o r t h i s c r i t i c a l
s t e p has n o t a p p e a r e d i n t h e l i t e r a t u r e .
A t t e m p t s t o d e r i v e mech
anisms f o r benzene f o r m a t i o n i n flames have s u f f e r e d p r i m a r i l y
from the l a c k of p e r t i n e n t k i n e t i c o r thermodynamic d a t a .
Further
more, we h a v e f o u n d no l i t e r a t u r e w h e r e i n f o r m a t i o n r a t e s o f b e n
z e n e , o r o t h e r a r o m a t i c s , p r e d i c t e d f r o m a mechanism a r e compared
w i t h r a t e s measured i n a flame.
We w i l l n o t a t t e m p t t o r e v i e w h e r e t h e many mechanisms w h i c h
have been proposed t o account f o r a r o m a t i c f o r m a t i o n i n a l i p h a t i c
flames.
S u f f i c e i t to say t h a t these f a l l b a s i c a l l y i n t o t h r e e
c a t e g o r i e s : i o n i c mechanisms; c o n c e r t e d , p e r i c y c l i c mechanisms;
and f r e e r a d i c a l m e c h a n i s m s .
The r e a c t i o n k i n e t i c s o f d i f f e r e n t h y d r o c a r b o n i o n s i n f l a m e s
are not s u f f i c i e n t l y understood to permit t e s t i n g of proposed i o n molecule r e a c t i o n s l e a d i n g to aromatic formation. This area i s of
i n t e r e s t f o r f u r t h e r s t u d y , e s p e c i a l l y o f g r o w t h mechanisms f o r
l a r g e r a r o m a t i c s p e c i e s and s o o t . W i t h r e g a r d t o p e r i c y c l i c mech
a n i s m s s u c h as D i e l s - A l d e r r e a c t i o n s , o b s e r v a t i o n s made i n b u t a
d i e n e flames have l e d t o p r o p o s a l s t h a t b u t a d i e n e r e a c t i n g w i t h
o t h e r o l e f i n s m i g h t be r e s p o n s i b l e f o r a r o m a t i c f o r m a t i o n ( 4 - 6 ) .
Flame and p y r o l y s i s s t u d i e s , h o w e v e r , h a v e shown no e v i d e n c e o f
D i e l s - A l d e r r e a c t i o n s . As d e s c r i b e d b e l o w , we h a v e compared known
r e a c t i o n r a t e s w i t h measured f o r m a t i o n r a t e s i n b u t a d i e n e flames
and f o u n d D i e l s - A l d e r r e a c t i o n s t o be t o o s l o w t o be s i g n i f i c a n t
(7,8).
N e v e r t h e l e s s , a l i n k b e t w e e n f o u r - c a r b o n s p e c i e s and PAH f o r
m a t i o n w o u l d be c o n s i s t e n t w i t h t h e p r o m i n e n c e o f C-4 h y d r o c a r b o n s
i n f l a m e s where PAH o r s o o t a r e b e i n g f o r m e d . I n p a r t i c u l a r ,
l - b u t e n - 3 - y n e (C4H4; v i n y l a c e t y l e n e ) c o n c e n t r a t i o n p r o f i l e s m i m i c
t h o s e o f b e n z e n e and PAH i n many f u e l - r i c h f l a m e s ( 9 ) .
In t h i s work the net f o r m a t i o n r a t e s of benzene, t o l u e n e ,
p h e n y l a c e t y l e n e , and s t y r e n e , and c o n c e n t r a t i o n s o f p o s s i b l e p r e
c u r s o r s , w e r e d e t e r m i n e d as a f u n c t i o n o f d i s t a n c e f r o m t h e b u r n e r
i n t h e p r i m a r y r e a c t i o n zone o f a l o w - p r e s s u r e , n e a r - s o o t i n g 1,3butadiene-oxygen-4% argon flame.
These r a t e s a r e compared w i t h
e s t i m a t e d r a t e s f o r s e v e r a l r e a c t i o n mechanisms.
Experimental
The a p p a r a t u s i s a l o w - p r e s s u r e f l a t - f l a m e b u r n e r w i t h a m o l e c u l a r beam s a m p l i n g i n s t r u m e n t h a v i n g a q u a r t z p r o b e and an o n - l i n e q u a d r u p o l e m a s s - s p e c t r o m e t e r ( F i g u r e 1 ) . The d e s i g n f e a t u r e s and
measurement t e c h n i q u e s a r e t h e same as t h o s e d e s c r i b e d e l s e w h e r e
(1,10).
A n e a r - s o o t i n g l a m i n a r p r e m i x e d f l a t f l a m e was p r o d u c e d a t a
b u r n e r chamber p r e s s u r e o f 2.67 k P a (20 t o r r ) w i t h 52.1 n o r m a l
cm
s"
(0.1 MPa, 298 K) o f f e e d gas c o n s i s t i n g o f 29.5 m o l %
1 , 3 - b u t a d i e n e , 67.5 m o l % o x y g e n , and 3.0 m o l % a r g o n , c o r r e s p o n d i n g
t o a f u e l - e q u i v a l e n c e r a t i o , , o f 2.4 and a c o l d - g a s v e l o c i t y o f
3

1.
COLE ET AL.
C4 Hydrocarbons
in Aromatic Species Formation
0.5 ms
a t 298 . A t t h i s p r e s s u r e and c o l d - g a s v e l o c i t y t h e
s o o t i n g l i m i t was f o u n d a t 2.46.
A l l o f t h e g a s e s u s e d w e r e more t h a n 9 9 % p u r e and w e r e u s e d
as s u p p l i e d b y t h e m a n u f a c t u r e r s .
I n d i v i d u a l s p e c i e s w e r e i d e n t i f i e d b y mass and i o n i z a t i o n p o
tential.
T h e i r mole f r a c t i o n s were measured a t t h e c e n t e r l i n e o f
the f l a m e as a f u n c t i o n o f d i s t a n c e from t h e b u r n e r as d e s c r i b e d
elsewhere (1,10).
E s t i m a t e d p r o b a b l e e r r o r s f o r s p e c i e s m o l e f r a c t i o n a r e shown
i n Table I below.
The m o l e f r a c t i o n s o f t h e l a r g e s t h y d r o c a r b o n
T a b l e 1.
Estimated Probable Errors f o r Species Mole-Fraction

Measurements
Species
Major Species
H 0
2
^2^2
Hydroxyl
H-atom
Other r a d i c a l s
S p e c i e s l a r g e r t h a n Benzene
Estimated Probable Error

+ 3%
+ 8%
+12%
+17%
+19%
+50%
f a c t o r o f two
s p e c i e s were determined r e l a t i v e t o each o t h e r w i t h g r e a t e r a c c u

r a c y than t h e e r r o r s a s s o c i a t e d w i t h t h e i r a b s o l u t e mole f r a c t i o n s
would suggest.
The m o l e f r a c t i o n p r o f i l e s w e r e n u m e r i c a l l y smoothed and d i f
f e r e n t i a t e d i n order t o determine the s p e c i e s molar f l u x e s .
This
p r o c e s s was r e p e a t e d o n t h e f l u x p r o f i l e s i n o r d e r t o p r o v i d e n e t
m o l a r r a t e s o f f o r m a t i o n o r d e s t r u c t i o n f o r e a c h s p e c i e s . The
n u m e r i c a l t e c h n i q u e s have been d e s c r i b e d p r e v i o u s l y (1,2,7,10).
P r o b a b l e e r r o r s a s s o c i a t e d w i t h f l u x e s and r e a c t i o n r a t e s s o d e
termined cannot be s t a t e d e x p l i c i t l y because t h e p e r t u r b a t i o n o f
the s a m p l i n g p r o b e o n t h e o n e - d i m e n s i o n a l f l a m e a s s u m p t i o n h a s n o t
been a s s e s s e d q u a n t i t a t i v e l y .
N e v e r t h e l e s s , t h e o v e r a l l a c c u r a c y suggested by element b a l
a n c e s i s e n c o u r a g i n g . The c a l c u l a t e d t o t a l - c a r b o n mass f l u x a g r e e s
to w i t h i n 30% throughout t h e flame w i t h t h e v a l u e determined from
the measured f u e l f e e d r a t e .
The a g r e e m e n t i s t o w i t h i n 5% i n t h e
r e g i o n o f t h e flame c o n s i d e r e d i n t h i s work.
The g a s t e m p e r a t u r e p r o f i l e s u s e d f o r t h i s a n a l y s i s w e r e c a l
c u l a t e d from t h e assumption o f e q u i l i b r i u m i n t h e r e a c t i o n
1
H- + H 0 % H
2
+ OH
(1)
T h i s r e a c t i o n appears t o be e q u i l i b r a t e d beyond t h e p r i m a r y r e a c
t i o n zone ( r e g i o n o f t o t a l f u e l a n d / o r o x y g e n c o n s u m p t i o n ) i n t h i s

f l a m e and e l s e w h e r e ( 1 1 ) .
The t e m p e r a t u r e was
p a r i n g the e q u i l i b r i u m equation
X
_ H
X
c a l c u l a t e d by
com
H 0
9
X
2
0H
w i t h t h e known s t a n d a r d G i b b s e n e r g y charge, G, f o r R e a c t i o n (1)

as a f u n c t i o n o f t e m p e r a t u r e ( 1 2 ) .
In t h i s case the e q u i l i b r i u m
c o n s t a n t , K, i s r e l a t e d t o G
by
AG
= -RT
In
The r e s u l t i n g t e m p e r a t u r e p r o f i l e i s shown i n F i g u r e 2.
The temp
e r a t u r e i n t h e p r i m a r y r e a c t i o n zone was e s t i m a t e d by l i n e a r e x
t r a p o l a t i o n t o 300 a t t h e b u r n e r . P r o p a g a t i o n o f e r r o r c a l c u l a
t i o n s s u g g e s t s a maximum p r o b a b l e e r r o r o f +150
K.
Experimental
R e s u l t s and
Discussion
The m o l e - f r a c t i o n and m o l a r - f l u x p r o f i l e s o b t a i n e d f o r 31 s p e c i e s
a r e shown i n F i g u r e s 3-8.
I n s p e c t i o n of the f l u x p r o f i l e s i n
F i g u r e 3 r e v e a l s l i t t l e e v i d e n c e o f r e a c t i o n up t o a b o u t 5 mm f r o m
t h e b u r n e r . B u t a d i e n e i s consumed i n t h e r e g i o n 5-10 mm,
although
p r i m a r i l y b e y o n d 7 mm ( F i g u r e 3 ) . Oxygen c o n s u m p t i o n , h o w e v e r ,
does n o t become n o t i c a b l e u n t i l a b o u t 8.5 mm ( F i g u r e 4) and p r o
d u c t i o n o f CO, 0 0 , and H 0 o c c u r s l a t e r s t i l l ( F i g u r e s 3 and 5 ) .
N e v e r t h e l e s s some o x i d a t i o n o c c u r s p r i o r t o 8.5 mm as i s e v i d e n c e d
by t h e f l u x e s o f t h e o x y g e n a t e d s p e c i e s i n F i g u r e 4.
The s p e c i e s
C3H4O and C4H5O p r o b a b l y r e s u l t f r o m t r i p l e t ( g r o u n d s t a t e ) 0-atom
a t t a c k on b u t a d i e n e and aline ( 1 3 , 1 4 ) .
T h e r e f o r e 0-atom may p l a y
a r o l e i n b u t a d i e n e d e s t r u c t i o n . Such b e h a v i o r w o u l d be c o n s i s t e n t
w i t h the o b s e r v a t i o n t h a t the f r a c t i o n a l d e c o m p o s i t i o n r a t e ( s ~ l ) of
b u t a d i e n e a t t h e 1120 p o s i t i o n i n t h i s f l a m e , where 0 atoms a r e
a v a i l a b l e by d i f f u s i o n f r o m t h e o x i d a t i o n z o n e , i s s i g n i f i c a n t l y
l a r g e r t h a n t h a t m e a s u r e d i n t h e p r e s e n c e o f 0 a t 1120 i n an
approximately isothermal flow reactor (15).
H y d r o c a r b o n s p e c i e s w i t h one, two, o r t h r e e c a r b o n atoms a r e
r e p r e s e n t e d i n F i g u r e 6; t h o s e w i t h f o u r c a r b o n atoms i n F i g u r e 7.
The b e h a v i o r and p o s i t i o n o f t h e C4H4 m o l e f r a c t i o n p r o f i l e ( F i g
u r e 7) a r e s t r i k i n g l y s i m i l a r t o t h o s e o f a l l t h e a r o m a t i c s p e c i e s
shown i n F i g u r e 8.
I n c o n t r a s t , the p r o f i l e s of d i a c e t y l e n e
(C4H2, F i g u r e 7) and t h e p o l y a c e t y l e n e s ( C H and C H , F i g u r e 8)
are s i m i l a r to those of a c e t y l e n e ( F i g u r e 6 ) .
F i g u r e 8 shows t h a t b e n z e n e and t h e o t h e r s i n g l e - r i n g a r o m a t i c s whose f o r m a t i o n r a t e s a r e s t u d i e d h e r e a r e f o r m e d m a i n l y i n t h e
r e g i o n o f b u t a d i e n e c o n s u m p t i o n . T h e i r maximum n e t r a t e s o f f o r m
a t i o n o c c u r p r i o r t o 9.5 mm.
Since s i g n i f i c a n t 0
consumption
b e g i n s a t 8.5 mm and o x i d a t i o n i s e v i d e n t p r i o r t o t h a t , t h e q u e s
t i o n a r i s e s as t o w h e t h e r o x i d a t i v e c o n s u m p t i o n o f a r o m a t i c s c o n
t r i b u t e s s i g n i f i c a n t l y t o t h e i r net r e a c t i o n r a t e s i n the r e g i o n
of i n t e r e s t here
2

1.
COLE ET AL.
C4 Hydrocarbons
ELECTRON
MULTIPLIER
OUADRUPOLE MASS
FILTER
IONIZER
4 INCH
DIFFUSION
PUMP
LN -COOLED
WALLS
2
COLLIMATOR
TUNING FORK
CHOPPER
6 INCH
DIFFUSION
PUMP
CALIBRATION GAS
EFFUSIVE
SOURCE
-I SKIMMER
QUARTZ PROBE
BURNER
MECHANICAL
VACUUM PUMP
6 INCH
DIFFUSION
PUMP
PREMIXED GASES
F i g u r e 1. M o l e c u l a r beam mass s p e c t r o m e t e r f l a m e
apparatus.
10
LU
20
.:
30
sampling
40
HEIGHT ABOVE BURNER (mm)

Figure 2.
assuming
and u s e d
0= 2 ;
pressure
Temperature p r o f i l e i n n e a r - s o o t i n g . P o i n t s , c a l c u l a t e d
e q u i l i b r a t i o n o f H + EÔ zz OH + , a n d c u r v e , e s t i m a t e d
i n d a t a a n a l y s i s a n d mechanism p r e d i c t i o n s . C o n d i t i o n s :
C^Hg/0 /3.0#Ar f l a m e ; c o l d gas v e l o c i t y = 0.5 m/s ; a n d
= 2.67 kPa.
2

PROCESSES
CHEMISTRY OF COMBUSTION
F i g u r e 3. M o l e f r a c t i o n a n d f l u x p r o f i l e s o f m a j o r s p e c i e s i n
near-sooting.
C o n d i t i o n s same as i n F i g u r e 2.

COLE ET AL.
C4 Hydrocarbons
1.

PROCESSES
10
F i g u r e 5. M o l e f r a c t i o n a n d f l u x p r o f i l e s o f H, H^, OH, a n d EÔ

i n near-sooting.

I.
COLE ET AL.
C Hydrocarbons
4
10
12
14
16
11
II
DISTANCE FROM BURNER, mm
T I M E , ms
F i g u r e 6. Mole f r a c t i o n and f l u x p r o f i l e s o f one-, two-, and

three-carbon species i nnear-sooting.
C o n d i t i o n s same as i n F i g ure 2.

F i g u r e
M o l e f r a c t i o n and f l u x p r o f i l e s o f f o u r - c a r b o n
i n near-sooting.

species
1.
COLE ET AL.
C Hydrocarbons
4
13
DISTANCE FROM BURNER,mm
T I M E , ms
F i g u r e 8 . M o l e f r a c t i o n a n d f l u x p r o f i l e s o f s p e c i e s w i t h masses
b e t w e e n 7^ a n d 10U amu i n n e a r - s o o t i n g .
C o n d i t i o n s same a s i n
Figure 2.

14
Using the r a t e constant of T u l l y et a l . ( 1 6 ) , the temperature

p r o f i l e o f F i g u r e 2, and t h e m e a s u r e d b e n z e n e and h y d r o x y l m o l e
t i o n s , t h e p r e d i c t e d r a t e o f b e n z e n e d e s t r u c t i o n by OH i s i n s i g n i f
i c a n t compared t o t h e m e a s u r e d n e t b e n z e n e f o r m a t i o n r a t e u n t i l
a f t e r t h e l a t t e r p a s s e s t h r o u g h i t s maximum v a l u e a t 8.5 mm.
At
8.5 mm t h e p r e d i c t e d d e s t r u c t i o n o f b e n z e n e by h y d r o x y l i s one p e r
cent of the measured f o r m a t i o n r a t e , i n c r e a s i n g o n l y t o t e n p e r c e n t
a t 9.3.
A s i m i l a r e s t i m a t i o n was made f o r b e n z e n e d e s t r u c t i o n by
0-atom u s i n g t h e r a t e c o n s t a n t o f N i c o v i c h e t a l . (17) and r e a s o n
a b l e e s t i m a t i o n s f o r 0-atom m o l e f r a c t i o n s .
T h i s y i e l d e d v a l u e s of
two p e r c e n t and 17 p e r c e n t a t 8.5 mm and 9.3 mm r e s p e c t i v e l y .
The
l a c k of a d d i t i o n a l o x i d a t i o n r a t e c o n s t a n t s p r e c l u d e d s i m i l a r c a l
c u l a t i o n s f o r the other aromatic s p e c i e s .
Benzene F o r m a t i o n
Mechanisms
The f o r m a t i o n o f a r o m a t i c s by r e a c t i o n s i n v o l v i n g 1 , 3 - b u t a d i e n e was
considered.
S e v e r a l D i e l s - A l d e r r e a c t i o n s were c o n s i d e r e d , the
f a s t e s t o f w h i c h i s C^H
+ C H owing t o i t s l a r g e A r r h e n i u s f a c t o r
and t h e h i g h c o n c e n t r a t i o n o f a c e t y l e n e . However, t h e r a t e o f t h i s
r e a c t i o n i s l e s s t h a n 10~3 o f t h e m e a s u r e d r a t e o f b e n z e n e f o r m a
tion.
T h e r e f o r e D i e l s - A l d e r r e a c t i o n s do n o t a p p e a r t o be s i g n i f i
cant f o r aromatics f o r m a t i o n i n t h i s system.
F r e e r a d i c a l mechanisms i n v o l v i n g 1 , 3 - b u t a d i e n e a l s o h a v e b e e n
considered.
The r e a c t i o n s e q u e n c e
6
2 3-
4 6 *
( 2 )
6 V
* - 6V
C
c-C H - t
6
c-C H
6
(3)
c-C H
-v C H
6
+ H
+ H-
(4)
(5)
p r o v i d e s a thermodynamically f a v o r a b l e r o u t e t o benzene f o r m a t i o n
i n the 1,3-butadiene flame d i s c u s s e d here.
The r a t e l i m i t i n g s t e p
i n t h i s s e q u e n c e i s R e a c t i o n 5 w i t h a r a t e c o n s t a n t Log k^ =
12.-4/ ( s " ) , where = 2.3 RT k c a l / m o l ( 1 8 , 1 9 ) .
However, t h e
c o n c e n t r a t i o n o f Q i n t h i s f l a m e i s o n l y a few p e r c e n t o f t h a t
o f b e n z e n e ( 2 0 ) . T h i s l e a v e s R e a c t i o n 5 t o o s l o w by a f a c t o r o f
10 to 10 .
An a l t e r n a t i v e t o R e a c t i o n 5 i s t h e r e a c t i o n s e q u e n c e
1
c-C Hg + R- t
c - C H - + RH
c-C H - t
6
C H
6
4- H-
(6)
(7)
Reaction 6 i s r a t e l i m i t i n g here w i t h a t y p i c a l r a t e constant of

L o g k^ = 8.5-5.5/0 ( i l m o l " s " ) (21) f o r m e t a t h e s i s by h y d r o c a r b o n
radicals.
-abstraction by -atom m i g h t be f a s t e r , w i t h an A r r h e n 1

1.
COLE ET AL.
C4 Hydrocarbons
15
i u s f a c t o r c o n c e i v a b l y as l a r g e as l O ^ - . However, t h e p r e d i c t e d
r a t e o f b e n z e n e f o r m a t i o n w o u l d s t i l l be l e s s t h a n a few p e r c e n t o f
that which i s observed.
I n a d d i t i o n r e a c t i o n s e q u e n c e s i n v o l v i n g C/H^ as a b e n z e n e
p r e c u r s o r were c o n s i d e r e d . Because of the r e q u i r e d p r o t o n a t i o n of
t h e number 3 c a r b o n atom, h o w e v e r , a l l o f t h e s e mechanisms p r o v e d
t o be t o o s l o w ( 7 ) .
R a d i c a l a d d i t i o n of 1,3-butadienyl to acetylene provides a
r o u t e t o benzene f o r m a t i o n through the sequence
1,3-C H - + C H
4
C H - *
6
* C H 6
c-C H 6
(8)
(9)
(7)
The 1 , 3 - b u t a d i e n y l r a d i c a l i s p r i m a r i l y a b y - p r o d u c t o f b u t a d i e n e
p y r o l y s i s i n t h i s system but r e s u l t s from v i n y l a d d i t i o n t o ace
t y l e n e i n flames of other a l i p h a t i c f u e l s .
I n a r o m a t i c f l a m e s 1,3b u t a d i e n y l may be p r o d u c e d by o x i d a t i v e and p y r o l y t i c d e c o m p o s i t i o n
o f a r o m a t i c s p e c i e s , as s u g g e s t e d i n a s t u d y o f b e n z e n e f l a m e s ( 1 0 ) .
A l t h o u g h R e a c t i o n 8 has n o t been s t u d i e d e x p l i c i t l y , a r a t e
c o n s t a n t o f L o g k^Q - 8.5-3.7/ (-mol~ls~l) was i n f e r r e d f r o m
m e a s u r e d d a t a f o r s i m i l a r r e a c t i o n s 7).
Comparison of t h i s v a l u e
w i t h r a t e e s t i m a t e s f o r s i m i l a r r e a c t i o n s (22) s u g g e s t s t h a t t h i s
a c t u a l l y may be a r a t h e r c o n s e r v a t i v e f i g u r e .
Reaction 8 i s rate
l i m i t i n g i n t h i s sequence.
F i g u r e 9 shows t h e a g r e e m e n t b e t w e e n t h e p r e d i c t e d b e n z e n e
f o r m a t i o n r a t e u s i n g t h i s mechanism and t h e m e a s u r e d r a t e t h r o u g h o u t t h e r e g i o n o f n e t b e n z e n e p r o d u c t i o n . The m e a s u r e d r a t e i s 5
t o 10 t i m e s h i g h e r t h a n t h e p r e d i c t e d r a t e .
In view of the uncert a i n t i e s e n c o u n t e r e d a t e a c h s t e p i n t h e a n a l y s i s we f e e l t h a t t h i s
l e v e l of agreement, coupled w i t h the congruence of the f o r m a t i o n
r a t e p r o f i l e s , p r o v i d e s e v i d e n c e o f t h e v i a b i l i t y o f t h i s mechanism
i n the 1,3-butadiene flame.
Formation
of Other Aromatic
Species
Because o t h e r a c e t y l e n i c s p e c i e s were a l s o p r e s e n t i n the b u t a d i e n e

flame, r a t e c o n s t a n t s were e s t i m a t e d f o r the a d d i t i o n of t h r e e of
them, C3H4 ( p r o p y n e ) , C4H2 ( b u t a d i y n e ) , and C4H4 ( b u t e n - 3 - y n e ) t o
1 , 3 - b u t a d i e n y l ( 7 ) . These a d d i t i o n r e a c t i o n s w i t h subsequent c y c l i z a t i o n o f t h e a d d u c t , f o l l o w e d by -elimination ( a n a l o g o u s t o
R e a c t i o n s 8, 9, and 7) l e a d t o f o r m a t i o n o f t o l u e n e , p h e n y l a c e t y l e n e , and s t y r e n e , r e s p e c t i v e l y .
The r a t e c o n s t a n t s shown b e l o w ( T a b l e I I ) w e r e e x t r a p o l a t e d
f r o m r a t e d a t a u s i n g an E v a n s - P o l a n y i a p p r o a c h s i m i l a r t o t h a t d i s
c u s s e d r e c e n t l y by M c M i l l e n and G o l d e n ( 2 3 ) . The a s s u m p t i o n o f e q u a l
A r r h e n i u s parameters i s i n h e r e n t i n the e s t i m a t i o n technique.
Sub
s e q u e n t c y c l i z a t i o n and -elimination s t e p s a r e a f f e c t e d n e g l i g i b l y

16
Table I I .
Rate Constants
1,3-butadienyl
f o r A d d i t i o n of A c e t y l e n i c Species
a t 800
Equation
4 5*
->
3 4
4 2
4 4
4 5'
4 5'
Rate Constant,
<-
C H ?
->
k,
*mol
(10)
1 Q
8.5-3.7/0
(11)
10
8.5-1.8/
(12)
to
s"
8.5-0.6/0
by t h e p r e s e n c e o f s i d e c h a i n s on t h e a r o m a t i c r i n g ( 2 4 ) .
Conse
q u e n t l y , R e a c t i o n s 10-12 a r e r a t e l i m i t i n g f o r t h e i r r e s p e c t i v e
r e a c t i o n sequences.
F i g u r e s 10-12 show t h e m e a s u r e d r a t e s o f f o r m a t i o n o f t o l u e n e ,
p h e n y l a c e t y l e n e , and s t y r e n e compared w i t h t h e r a t e s p r e d i c t e d by
R e a c t i o n s 10-12. Of t h e s e t h r e e , o n l y t o l u e n e ( F i g u r e 10) shows a
s e r i o u s d i s a g r e e m e n t b e t w e e n p r e d i c t i o n and o b s e r v a t i o n . The e a r l y
d e c l i n e i n t h e t o l u e n e f o r m a t i o n r a t e (^7;5 mm) may be due t o r a p i d
b e n z y l r a d i c a l f o r m a t i o n . A c u r s o r y e x a m i n a t i o n o f t h e C7H7 and
CyHg f l u x p r o f i l e s i n F i g u r e 8 s u p p o r t s t h i s p o s s i b i l i t y .
Never
t h e l e s s , t h e m a g n i t u d e o f d i s c r e p a n c y b e t w e e n m e a s u r e d and p r e d i c t
ed r a t e s s u g g e s t s t h a t some o t h e r mechanism i s p r o b a b l y r e s p o n s i b l e
f o r t o l u e n e f o r m a t i o n i n t h i s system.
Role of V i n y l a c e t y l e n e
The b e h a v i o r o f C4H4 r e l a t i v e t o b e n z e n e and PAH has b e e n o b s e r v e d
i n o t h e r a l i p h a t i c f l a m e s , i n c l u d i n g t h o s e o f methane ( 2 5 , 2 6 ) ,
a c e t y l e n e ( 7 , 2 7 ) , and e t h y l e n e ( 2 7 ) , as w e l l as b e n z e n e f l a m e s ( 1 ,
1 0 ) . As an e x a m p l e , F i g u r e 13 shows d a t a f o r e t h y l e n e and a c e t y
l e n e f l a m e s e x t r a c t e d f r o m t h e w o r k s o f C r i t t e n d e n (28) and C r i t
t e n d e n and L o n g ( 2 7 ) . T h i s c o r r e l a t i o n may be e x p l a i n e d i f 1,3b u t a d i e n y l c a n be shown t o be t h e p r i m a r y p r e c u r s o r f o r f o r m a t i o n
o f C 4 H 4 , as w e l l as PAH.
T h a t C4H4 i s i n d e e d r e l a t e d t o C4H3 i s i n d i c a t e d by t h e p r e s
e n t d a t a as w e l l as d a t a f r o m two o t h e r f l a m e s s t u d i e d i n t h e same
e x p e r i m e n t a l s y s t e m a t t h e same b u r n e r v e l o c i t y and p r e s s u r e , name
l y , a s t o i c h i o m e t r i c 1 , 3 - b u t a d i e n e f l a m e (7) and a n e a r - s o o t i n g
b e n z e n e f l a m e ( 1 0 ) . I n a l l t h r e e c a s e s , t h e r a t i o o f t h e peak c o n
c e n t r a t i o n o f C4H5 t o t h a t o f C4H4 i s a b o u t 1:30 ( e . g . , F i g u r e 7 ) ,
and t h e C^H^ peak o c c u r s a b o u t 1 mm ( o r a b o u t 0.3 ms) b e f o r e t h a t
of C4H4.
T h i s b e h a v i o r i s i n d i c a t i v e o f an i n t e r m e d i a t e / p r o d u c t
r e l a t i o n s h i p b e t w e e n C^H^ and C 4 H 4 .
The k i n e t i c s o f t h e r e l a t i o n
s h i p seems t o v a r y l i t t l e among t h e s e d i f f e r e n t f l a m e s .
I n t h e p r e s e n t d a t a , t h e n e t f o r m a t i o n r a t e o f C4H4 p e a k s e x
a c t l y where t h e n e t r a t e o f C4H5 c o n s u m p t i o n i s maximum (9.3
mm),
and t h e f o r m e r i s a b o u t 1 0 - t i m e s t h e l a t t e r .
I t i s l i k e l y that
4 4 * f o r m e d by R e a c t i o n ( 1 3 ) . E q u i l i b r i u m f o r t h i s r e a c t i o n
C

1.
C4 Hydrocarbons
COLE ET A L .
=
0
I
2
MEASURED RATE
17
I=
10
HEIGHT ABOVE BURNER (mm)
F i g u r e 9.
Comparison o f measured n e t r a t e s o f benzene f o r m a t i o n
with predicted formation rates f o rnear-sooting.
C o n d i t i o n s same
as i n F i g u r e 2 .
0 -
//
<
ce
"
<
-j
MEASURED R A T E
"
k-[c H ][l-C H -f ;
10
HEIGHT A B O V E BURNER (mm)
F i g u r e 1 0 . Comparison o f measured n e t r a t e s o f t o l u e n e f o r m a t i o n
with predicted formation rates f o r near-sooting.

18
PROCESSES
F i g u r e 11.
Comparison o f measured n e t r a t e s o f p h e n y l a c e t y l e n e
formation with predicted formation rates f o r near-sooting.
Condi
t i o n s same a s i n F i g u r e 2 .
MEASURED RATE
k-[c H ][l-C H ]
<
ce
10
HEIGHT A B O V E BURNER (mm)
F i g u r e 12.
Comparison o f measured n e t r a t e s o f s t y r e n e f o r m a t i o n
with predicted formation rates f o r near-sooting.

1.
C4 Hydrocarbons
COLE ET AL.
10
12
14
19
16
HEIGHT A B O V E BURNER (cm)
Figure 13.
%ô
4 U'
mole f r a c t i o n p r o f i l e s i n ( t o p )
C H p / 0 / A r f l a m e a n d ( b o t t o m ) C H^/0 / A r f l a m e . D a t a f r o m
C r i t t e n d e n a n d L o n g ( 2 7 ) a n d C r i t t e n d e n ( 2 8 ) . The d a s h e d l i n e f o r
CgHg i n t h e l o w e r f i g u r e s u g g e s t s a d i s c r e p a n c y b e t w e e n t h e d a t a
p r e s e n t e d i n t h e two r e f e r e n c e s .
9
a n ( i

20
1,3-C H
4
C H
4
+ H-
(13)
favors
p r o d u c t i o n t h r o u g h o u t t h e r e g i o n o f PAH p r o d u c t i o n (<9
mm). F u r t h e r m o r e , u s i n g a n e s t i m a t e d r a t e c o n s t a n t ( 7 ) o f
Log k
= 13.8 - 41.7/ ( s " ) t h e p r e d i c t e d r a t e o f C4H4 p r o d u c t i o n
from 1 , 3 - b u t a d i e n y l exceeds t h e measured r a t e by a f a c t o r o f n e a r l y
200 a t 9.3 mm.
1
1 3
Conclusions
The o b s e r v e d r e l a t i o n s h i p b e t w e e n t h e p r o f i l e s o f C4H4 and a r o m a t
i c s i n hydrocarbon flames i s c o n s i s t e n t w i t h the hypothesis that
1,3-butadienyl i s t h e c r i t i c a l i n t e r m e d i a t e s p e c i e s f o r t h e forma
t i o n o f t h e s e compounds. The h y p o t h e s i s i s s u p p o r t e d b y c o n s i d e r
a b l e agreement between p r e d i c t e d r a t e s o f a d d i t i o n r e a c t i o n s o f
1 , 3 - b u t a d i e n y l r a d i c a l and m e a s u r e d n e t f o r m a t i o n r a t e s o f b e n z e n e ,
p h e n y l a c e t y l e n e , and s t y r e n e i n a 1 , 3 - b u t a d i e n e f l a m e .
However,
t h e need f o r b e t t e r r a t e d a t a i s c l e a r l y i n d i c a t e d .
The h y p o t h e s i s t h a t 1 , 3 - b u t a d i e n e may be r e s p o n s i b l e f o r b e n
zene p r o d u c t i o n i s i n c o n s i s t e n t w i t h t h e d a t a p r e s e n t e d h e r e .
However, t h i s c o n c l u s i o n i s b a s e d on t h e l o w m e a s u r e d m o l e f r a c
t i o n s o f t h e i n t e r m e d i a t e s p e c i e s c y c l o h e x a d i e n e (C^Hg) w h i c h may
be p e c u l i a r t o t h e s e e x p e r i m e n t a l c o n d i t i o n s . T h e r e f o r e , t h i s
c o n c l u s i o n does n o t r u l e o u t t h e p o s s i b l e s i g n i f i c a n c e o f 1,3butadiene i n other combustion systems.
Acknowledgments
We a r e g r a t e f u l t o E x x o n R e s e a r c h and E n g i n e e r i n g Company f o r f i
n a n c i a l s u p p o r t o f t h i s r e s e a r c h t h r o u g h t h e EXXON/MIT C o m b u s t i o n
R e s e a r c h P r o g r a m , and t o P h i l l i p R. W e s t m o r e l a n d f o r many v a l u a b l e
discussions.
Literature Cited
1. Bittner, J. D.; Howard, J. B., 18th Symp. (Intl.) on Combus
tion, The Combustion Institute, 1981, p. 1105.
2. Bittner, J. D.; Howard, J. B., in "Particulate Carbon-Forma
tion During Combustion"; Siegla, D. C.; Smith, G. W., Eds.;
Plenum: New York, 1981; pp. 109-137.
3. Homann, . H.; Wagner, H. Gg., 11th Symp. (Intl.) on Combus
4. Schalla, R. L.; McDonald, G. E., Ind. and Eng. Chem. 1953,
45, 1497-1500.
5. Thomas, ., Combustion and Flame 1962, 6, 46-62.
6. Glassman, I., "Phenamenological Models of Soot Processes in
Combustion" Rept. 1450, Dept. of Mech. and Aerospace Engineer
ing, Princeton Univ., 1979.
7. Cole, J. ., M. S. Thesis, Massachusetts Institute of Technol
ogy, Cambridge, Mass., 1982.

I. COLE ET AL.
C Hydrocarbons in Aromatic Species Formation

4
8. Cole, J. .; Bittner, J. D.; Longwell, J. P.; Howard, J. B.,

Combustion and Flame, in press.
9. Bittner, J. D.; Cole, J. .; Longwell, J. P.; Howard, J. B.,
to be published.
10. Bittner, J. D., Sc.D. Thesis, Massachusetts Institute of Tech
nology, Cambridge, Mass., 1981.
11. Bittner, J. D.; Howard, J. B., 19th Symp. (Intl.) on Combus
12. "JANAF Thermochemical Tables" NSRDS-NBS37, 1971, 2nd ed.
13. Atkinson, R.; Darnall, K. R.; Lloyd, A. C.; Winer, A. M.;
Pitts, J. N., Jr., Adv. Photochem. 1979, 11, 375-488.
14. vetanovic, R. J., Adv. Photochem. 1963, 6, 115-82.
15. Burke, E. J . ; Brezinsky, K.; Glassman, I., "Preliminary High
Temperature Studies of 1,3-Butadiene Oxidation" presented at
the Eastern States Section/The Combustion Institute Meeting,
Atlantic City, N.J., December 1982.
16. Tully, F. P.; Ravishankara, A. R.; Thompson, R. L.; Nicovich,
J. M.; Shah, R. C.; Kreutter, . M.; Wine, P. H., J. Phys.
Chem. 1981, 85, 2262-9.
17. Nicovich, J. M.; Gump, C. .; Ravishankara, A. R., J. Phys.
Chem. 1982, 86, 1684-94.
18. Ellis, R. J.; Frey, . M., J. Chem. Soc. 1966, A, 553-6.
19. Benson, S. W.; Shaw, R., Trans. Farad. Soc. 1967, 63, 985-92.
20. Cole, J. ., unpublished data.
21. James, D. G. L.; Suart, R. D., Trans. Farad. Soc. 1968, 64,
2735-51.
22. Benson, S. W.; Haugen, G. R., J. Phys. Chem. 1967, 71, 1735-46.
23. McMillen, D. F.; Golden, D. ., Ann. Rev. Phys. Chem. 1982, 33,
493-552.
24. Frey, . M.; Walsh, R., Chem. Rev. 1969, 69, 103-24.
25. D'Alessio, .; DiLorenzo, .; Sarofim, A. F.; Beretta, F.;
Masi, S.; Venitozzi, C., 15th Symp. (Intl.) on Combustion, The
Combustion Institute, 1975, p. 1427.
26. D'Alessio, .; DiLorenzo, .; Borghese, .; Beretta, F.; Masi,
S., 16th Symp. (Intl.) on Combustion, The Combustion Institute,
1976, p. 695.
27. Crittenden, B. D.; Long, R., Combustion and Flame 1973, 20,
359-68.
28. Crittenden, B. D., Ph.D. Thesis, University of Birmingham,
England, 1972.
RECEIVED November 30, 1983

21
2
Quantitative Chemical Mechanism for Heterogeneous
Growth of Soot Particles in Premixed Flames
STEPHEN J. HARRIS
Physical Chemistry Department, General Motors Research Laboratories, Warren, MI 48090
In this article we present the first quantitative chem

ical mechanism for the heterogeneous growth of soot
particles in premixed flames. We have found that the
increased surface growth rate in sootier (richer)
flames is due primarily to an increase in the surface
area available for growth; the concentration of the
gas phase growth species is similar from flame to
flame. Growth decreases as the soot ages in the
flame, but this is due to a decrease in the reac
tivity of the soot and not to a depletion of growth
species. Acetylene supplies nearly all of the mass
for soot growth, and our data suggest that soot
growth can be understood in terms of a first order
decomposition reaction of acetylene on the soot
surface.
Soot f o r m a t i o n i n p r e m i x e d f l a m e s may b e d i v i d e d i n t o p a r t i c l e
i n c e p t i o n ( " n u c l e a t i o n " ) and growth s t a g e s ( 1 ) . I n t h e n u c l e a t i o n s t a g e t i n y (1-2 nm) s o o t p a r t i c l e s a r e c r e a t e d , w h i l e d u r i n g
the g r o w t h s t a g e t h e s o o t p a r t i c l e s c o a l e s c e and a l s o a c c r e t e
h y d r o c a r b o n m o l e c u l e s ("growth s p e c i e s " ) f r o m t h e b u r n e d g a s e s .
These g r o w t h s p e c i e s r e a c t c h e m i c a l l y w i t h a n d become i n c o r p o r a t e d i n t o t h e s o o t p a r t i c l e s i n a h e t e r o g e n e o u s p r o c e s s known a s
s u r f a c e growth, and they account f o r n e a r l y a l l t h e f i n a l soot
mass. G r e a t e f f o r t s h a v e b e e n made t o w a r d s u n d e r s t a n d i n g s o o t
n u c l e a t i o n , and a number o f mechanisms h a v e b e e n p r o p o s e d ( 1 ) ;
however, no c o m p a r a b l e e f f o r t h a s b e e n made t o w a r d s u n d e r s t a n d i n g
s u r f a c e growth.
I n t h i s a r t i c l e we p r o p o s e t h e f i r s t q u a n t i t a t i v e
c h e m i c a l mechanism o f s o o t p a r t i c l e s u r f a c e g r o w t h i n p r e m i x e d
f l a m e s . A more d e t a i l e d a c c o u n t o f t h i s w o r k w i l l b e p u b l i s h e d
elsewhere ( 2 ) .
0097-6156/ 84/ 0249-0023506.00/ 0

24
Experimental
Premixed flames of
and a 79-21 m i x t u r e o f A r and 0^ were
s t a b i l i z e d on a w a t e r - c o o l e d p o r o u s p l u g b u r n e r w i t h a n i t r o g e n
shroud.
B e c a u s e t h e f l a m e s were n e a r l y 1 - d i m e n s i o n a l , m e a s u r e ments made as a f u n c t i o n o f h e i g h t above t h e b u r n e r c o u l d be c o n v e r t e d i n t o measurements made as a f u n c t i o n o f t i m e f r o m knowl e d g e o f t h e h o t gas v e l o c i t y .
S o o t was d e t e c t e d u s i n g s t a n d a r d
R a y l e i g h s c a t t e r i n g and e x t i n c t i o n t e c h n i q u e s (3,4) u s i n g an
a r g o n l a s e r , a l l o w i n g scôt number ^ d e n s i t y , mean p a r t i c l e d i a m e t e r ,
and volume f r a c t i o n (cm - s o o t / cm - f l a m e ) t o be d e t e r m i n e d . A l l
measurements w e r e made f a r downstream f r o m t h e s o o t n u c l e a t i o n
zone (The s m a l l e s t p a r t i c l e s d e t e c t e d had d i a m e t e r s o f a b o u t 8
nm.) i n a r e g i o n o f t h e f l a m e where r a d i c a l c o n c e n t r a t i o n s had
d r o p p e d t o t h e i r e q u i l i b r i u m v a l u e s (5) and where s o o t g r o w t h was
the main chemical process o c c u r r i n g . Temperatures, determined
f r o m t h e b r i g h t n e s s and e m i s s i v i t y o f t h e s o o t , v a r i e d m a i n l y
b e t w e e n 1650 and 1750 K.
Samples o f b u r n e d g a s e s were c o l l e c t e d
w i t h a w a t e r - c o o l e d q u a r t z m i c r o p r o b e and b a t c h a n a l y z e d f o r CO,
CO^, C^H^, and CH. w i t h IR and mass s p e c t r o m e t r y .
In the r e g i o n
o f t h e f l a m e e x a m i n e d , A r , CO, C0, H^, and HÔ made up a b o u t 97%
o f t h e gas p h a s e m a t e r i a l ; C o 2 ' CH^, and t r a c e amounts o f o t h e r
h y d r o c a r b o n s made up t h e r e s t .
S o o t and c o n d e n s a b l e
hydrocarbons
( " v o l a t i l e s " ) w e r e c o l l e c t e d on a w a t e r - c o o l e d p l a t e and s u b j e c t e d t o t h e r m o g r a v i m e t r i c , e l e m e n t a l , and B.E.T. s u r f a c e a r e a
analysis
(B.E.T. a n a l y s i s d e t e r m i n e s t h e s u r f a c e a r e a o f f i n e l y
d i s p e r s e d p a r t i c l e s by m e a s u r i n g t h e amount o f
a d s o r b e d on t h e
p a r t i c l e s a t 77 K.)
H
Results
Two d y n a m i c a l p r o c e s s e s o c c u r i n t h e b u r n e d gas r e g i o n o f p r e m i x e d
f l a m e s ( 4 ) . F i r s t , s m a l l s p h e r i c a l s o o t p a r t i c l e s c o l l i d e and
c o a l e s c e i n t o l a r g e s p h e r i c a l p a r t i c l e s , a process which reduces
t h e t o t a l amount o f s u r f a c e a r e a w i t h o u t c h a n g i n g t h e t o t a l mass.
The s e c o n d p r o c e s s i s s u r f a c e g r o w t h , w h i c h a c c o u n t s f o r an i n c r e a s e i n t h e t o t a l s o o t mass and adds s u r f a c e a r e a . The n e t
e f f e c t i s t h a t w h i l e t h e number d e n s i t y f a l l s ajnd t h e mean d i a m e t e r r i s e s , t h e t o t a l s o o t s u r f a c e a r e a p e r cm
o f f l a m e , meas u r e d o p t i c a l l y , changes v e r y l i t t l e as t h e s o o t a g e s .
These
e f f e c t s a r e d i s p l a y e d i n F i g u r e s 1 and 2. However, F i g u r e 2
shows t h a t t h e r e i s a s t e e p i n c r e a s e i n t h e s o o t s u r f a c e a r e a as
t h e f l a m e s become r i c h e r .
Curves i n the upper p a r t of F i g u r e 3
show s o o t volume f r a c t i o n s f o r f i v e f l a m e s w i t h d i f f e r e n t C/0
( c a r b o n / o x y g e n ) r a t i o s as a f u n c t i o n o f t i m e ( s o o t a g e ) . A l l o f
t h e i n c r e a s e i n mass i n e a c h f l a m e i s a t t r i b u t e d t o s u r f a c e
growth.
To o b t a i n s u r f a c e g r o w t h r a t e s we d i f f e r e n t i a t e t h e v o l u m e
f r a c t i o n c u r v e s , c o n v e r t i n g v o l u m e t o mass u s i n g a d e n s i t y o f 1.8
g/cm . A l t h o u g h a l l t h e c u r v e s a p p e a r t o h a v e s i m i l a r s l o p e s

2.
HARRIS
Heterogeneous Growth of Soot Particles
25
40
30
CO
10
1 l
20
CD
CO
V
10
k_
10
10
10
-L
20
Time (msec)
30
F i g u r e 1.
Mean d i a m e t e r a n d s o o t p a r t i c l e d e n s i t y as a f u n c t i o n
o f t i m e ( h e i g h t above t h e b u r n e r ) f o r a t y p i c a l f l a m e .
1.4
1.2
CO
1.0
\
0.8
0.6
5 0.4
(J)
0.2
-L
10
20
30
Time (ms)
2
3
Figure 2.
T o t a l s o o t s u r f a c e a r e a ( < d > N) p e r cm o f f l a m e .
The s y m b o l s r e f e r t o t h e s t o i c h i o m e t r y : , -C/0 = . 7 6 ;
, -0.82;
and , - 0 . 9 .
(Reproduced w i t h p e r m i s s i o n from R e f . 2 .
Copy
r i g h t 1 9 8 3 , Gordon a n d B r e a c h . )
m

PROCESSES
26
Figure 3.
T o p , s o o t volume f r a c t i o n s f o r f l a m e s w i t h t h e ^ i n d i c a t e d C/0 r a t i o s ; a n d b o t t o m , s u r f a c e g r o w t h r a t e s p e r cm o f s o o t
surface.
(Reproduced w i t h p e r m i s s i o n from Ref. 2.
C o p y r i g h t 193,
Gordon and B r e a c h . )

2.
HARRIS
27
when p l o t t e d o n s e m i - l o g p a p e r , t h e d e r i v a t i v e s a r e a c t u a l l y
q u i t e d i f f e r e n t a n d i n c r e a s e v e r y s u b s t a n t i a l l y w i t h t h e C/0
ratio.
However, o f more f u n d a m e n t a l i n t e r e s t t h a n t h e t o t a ] ,
g r o w t h r a t e ( g / s ) i s t h e s p e c i f i c s u r f a c e g r o w t h r a t e (g/cm - s ) ,
which takes i n t o account the greater s u r f a c e area a v a i l a b l e f o r
growth i n the r i c h e r ( s o o t i e r ) flames ( F i g u r e 2 ) . S p e c i f i c
s u r f a c e g r o w t h r a t e s , p l o t t e d i n t h e l o w e r h a l f o f F i g u r e 3, v a r y
r e l a t i v e l y w e a k l y w i t h C/0 r a t i o compared t o t h e t o t a l s u r f a c e
growth r a t e s .
Discussion
In o r d e r t o i n t e r p r e t t h e s u r f a c e growth r e s u l t s
we assume t h a t s u r f a c e g r o w t h i s d e s c r i b e d b y
dM/dt = S k . [
quantitatively,
g i
] i
(1)
where M i s t h e scjot mass c o n c e n t r a t i o n , S i s t h e t o t a l s o o t s u r

f a c e a r e a p e r cm o f f l a m e , [ g . ] i s t h e m o l e f r a c t i o n o f t h e i ' t h
g r o w t h s p e c i e s , k^ i s t h e r a t e c o n s t a n t f o r t h e s u r f a c e r e a c t i o n
w h i c h c o n v e r t s g. i n t o s o o t , a n d j . i s t h e r e a c t i o n o r d e r . The
f a c t t h a t t h e s p e c i f i c s u r f a c e g r o w t h r a t e s ( 1 / S ) dM/dt a r e s i m i
l a r i n flames w h i c h have v e r y d i f f e r e n t t o t a l growth r a t e s and
w h i c h p r o d u c e v e r y d i f f e r e n t amounts o f s o o t a l l o w s u s t o p l a c e
s e v e r a l s i g n i f i c a n t c o n s t r a i n t s on the growth process and on the
s u r f a c e growth s p e c i e s .
( i ) S u r f a c e g r o w t h i s much f a s t e r i n
r i c h e r f l a m e s p r i m a r i l y b e c a u s e t h e r e i s more s u r f a c e a r e a a v a i l
a b l e f o r growth; thus, growth s p e c i e s c o n c e n t r a t i o n s a r e s i m i l a r
i n the d i f f e r e n t flames.
( i i ) Growth r a t e s f a l l s t e e p l y as t h e
s o o t a g e s , b u t t h i s f a l l i s n o t due t o d e p l e t i o n o f t h e g r o w t h
species.
The r e a s o n i s t h a t i f t h e [ g . ] a r e r o u g h l y i n d e p e n d e n t
o f t h e s t o i c h i o m e t r y , a n d i f t h e y a r e igh enough t o s u p p l y a l l
o f t h e mass i n c r e a s e i n t h e r i c h e s t f l a m e , t h e n t h e r e must b e a n
e x c e s s o f them i n a l l t h e l e a n e r f l a m e s , where t h e i n c r e a s e i n
s o o t mass i s much l e s s .
S i n c e the s p e c i f i c growth r a t e i n t h e
r i c h e s t f l a m e i s a l m o s t t h e same a s i n t h e l e a n e r f l a m e s , t h e r e
i s a l s o no d e p l e t i o n o f g r o w t h s p e c i e s i n t h e r i c h e s t f l a m e ,
( i i i ) From t h e t o t a l amount o f s o o t mass p i c k e d up i n t h e r i c h e s t
f l a m e , we c a l c u l a t e t h a t e i t h e r t h e g r o w t h s p e c i e s m o l e f r a c t i o n s
t o t a l more t h a n 0.1/W, where W i s t h e (mean) m o l e c u l a r w e i g h t o f
t h e g r o w t h s p e c i e s , o r t h a t t h e y a r e i n r a p i d (compared t o r e a c t i o n w i t h soot) e q u i l i b r i u m w i t h a r e s e r v o i r o f other species
whose m o l e f r a c t i o n s t o t a l more t h a n 0.1/W. Among t h e h y d r o c a r bons i n t h e b u r n e d g a s e s , o n l y methane a n d a c e t y l e n e h a v e m o l e
fractions that high.
( i v ) The y o u n g e s t s o o t p a r t i c l e s t h a t we
d e t e c t h a v e d i a m e t e r s o f a b o u t 8 nm and m o l e c u l a r w e i g h t s w e l l
above 100,000 b u t c o n t a i n o n l y o f t h e o r d e r o f 10 n u c l e i ( 6 , 7 ) .
Thus t h e y a r e composed a l m o s t e n t i r e l y o f g r o w t h s p e c i e s .
Since
t h e r e i s no o b v i o u s way b y w h i c h t h e y o u n g g r o w i n g p a r t i c l e s c a n
l o s e p u r e c a r b o n , t h e C/H ( c a r b o n / h y d r o g e n ) r a t i o o f t h e g r o w t h

28
s p e c i e s c a n n o t be h i g h e r t h a n t h a t o f t h e young s o o t , a b o u t 2 t o
2 . 5 ( 3 ) . (As t h e s o o t ages i t s C/H r a t i o i n c r e a s e s t o a b o u t 8
(3).)
To i d e n t i f y t h e g r o w t h s p e c i e s , we c o n s i d e r w h i c h h y d r o c a r bons i n t h e p o s t f l a m e g a s e s s a t i s f y t h e above c o n s t r a i n t s .
The
v o l a t i l e m a t e r i a l may e a s i l y be e l i m i n a t e d . F o r e x a m p l e , i t s
c o n c e n t r a t i o n i s a b o u t 100 t i m e s h i g h e r i n b e n z e n e f l a m e s t h a n i n
flames of a l i p h a t i c f u e l s ( 8 ) , but the growth r a t e s are n e a r l y
i d e n t i c a l ( 9 ) . A l s o , t h e r e i s a l w a y s much l e s s v o l a t i l e m a t e r i a l
t h a n s o o t i n t h e f l a m e ( 3 ) , so t h e r e c a n n o t be enough o f i t ( c o n s t r a i n t s ( i i ) and ( i i i ) ) t o a c c o u n t f o r t h e l a r g e i n c r e a s e i n
s o o t mass w i t h age.
P o l y a c e t y l e n e s (C,H
to C H have been o b s e r v e d ) a r e e q u i l i b r a t e d w i t h a c e t y l e n e i n f l a m e s ( 1 0 ) . Bonne e t a l . (10) and
Homann and Wagner (8) a r g u e d t h a t t h e l a r g e s t o f t h e s e a r e r e s p o n s i b l e f o r most o f t h e s u r f a c e g r o w t h , b u t t h e i r a r g u m e n t s were
o n l y c o r r e l a t i o n s and w e r e t h e r e f o r e n o t c o n v i n c i n g .
In f a c t ,
t h e e v i d e n c e shows t h a t t h e y a r e n o t i m p o r t a n t .
For example,
except f o r d i a c e t y l e n e ( C ^ t ^ ) , a l l of the p o l y a c e t y l e n e s v i o l a t e
c o n s t r a i n t ( i v ) . Furthermore, i n order f o r the h i g h e r p o l y a c e t y l e n e s t o be as i m p o r t a n t as C^H^,
their
w o u l d h a v e t o be
s u b s t a n t i a l l y h i g h e r s i n c e t h e i r c o n c e n t r a t i o n s a r e so much l o w e r
(10).
However, T e s n e r has f o u n d (11) t h a t i n any homologous
s e r i e s o f h y d r o c a r b o n s an i n c r e a s e i n m o l e c u l a r w e i g h t l e a d s t o
o n l y a " t i n y " i n c r e a s e i n the s u r f a c e growth r a t e s .
Finally,
deep i n t h e p o s t f l a m e g a s e s f a r b e y o n d t h e n u c l e a t i o n z o n e ,
o x y g e n has b e e n consumed and C^H^ w i l l be f o r m e d f r o m C^H^
by
t h e p y r o l y s i s mechanism m o d e l l e d by Tanzawa and G a r d i n e r
12)
F o r t h e r i c h e r f l a m e s t h e m o d e l g i v e s a C^H^ f o r m a t i o n r a t e o n l y
20% o f t h e peak m e a s u r e d r a t e o f s o o t f o r m a t i o n .
This r e s u l t
means t h a t d i a c e t y l e n e c a n n o t be r e s p o n s i b l e f o r s u r f a c e g r o w t h ,
s i n c e t h e e q u i l i b r i u m r e a c t i o n s c o n n e c t i n g C2H2 and C^H
w o u l d be
too slow to prevent d i a c e t y l e n e from b e i n g d e p l e t e d , v i o l a t i n g
c o n s t r a i n t s ( i i ) and ( i i i ) .
Even i f t h e m o d e l w e r e n o t a c c u r a t e
enough t o e l i m i n a t e d i a c e t y l e n e on t h i s b a s i s a l o n e , i t a l s o
makes an i m p o r t a n t q u a l i t a t i v e p r e d i c t i o n . I f d i a c e t y l e n e i s
i m p o r t a n t l y i n v o l v e d i n soot growth, then d e s t r u c t i o n of d i a c e t y l e n e on t h e s o o t s u r f a c e w i l l s u b s t a n t i a l l y p e r t u r b t h e v a l u e o f
t h e e q u i l i b r i u m r e l a t i o n s h i p b e t w e e n a c e t y l e n e and d i a c e t y l e n e , R
= [ C , H ] [ H ] / [ C H ] . However, v a l u e s o f R measured i n h e a v i l y
s o o t i n g (10) and i n n o n s o o t i n g (13) f l a m e s were e s s e n t i a l l y
i d e n t i c a l , i m p l y i n g t h a t s u r f a c e growth i s i n f a c t a n e g l i g i b l e
sink for
C,H~.
O n l y C j L and CH
a r e p r e s e n t a t h i g h enough c o n c e n t r a t i o n
to s a t i s f y c o n s t r a i n t ( i i i ) .
However, g i v e n methane's c o n c e n t r a t i o n and t h e f a c t t h a t methane and a c e t y l e n e a r e n o t e q u i l i b r a t e d
i n t h e f l a m e s ( 1 3 ) , CH, c o u l d n o t p r o v i d e a m a j o r f r a c t i o n o f t h e
m a t e r i a l f o r soot growth w i t h o u t b e i n g s u b s t a n t i a l l y d e p l e t e d ,
v i o l a t i n g c o n s t r a i n t ( i i ) and c o n t r a d i c t i n g o u r c o n c e n t r a t i o n
m e a s u r e m e n t s . T h u s , methane i s n o t i m p o r t a n t f o r s u r f a c e g r o w t h .

2.
HARRIS
29
( S i m i l a r l y , v i n y l a c e t y l e n e c o u l d not be important s i n c e i t t o o
i s n o t e q u i l i b r a t e d w i t h a c e t y l e n e (13).) Therefore, whether o r
n o t ^2^2 ^
- ^ a c t u a l l y decomposes o n t h e s o o t s u r f a c e , c o n s e r
v a t i o n o f mass r e q u i r e s t h a t p r a c t i c a l l y a l l o f t h e s o o t mass i s
p r o v i d e d , d i r e c t l y o r i n d i r e c t l y , by the a c e t y l e n e i n the burned
gases.
I t remains t o determine whether s u r f a c e growth c a n be f u l l y
a c c o u n t e d f o r by d i r e c t d e c o m p o s i t i o n o f C^R^.
Bonne e t a l . ( 1 0 )
a r g u e d t h a t C^H^ c o u l d n o t be i m p o r t a n t s i n c e g r o w t h c e a s e d a t
l o n g t i m e s w h i l e t h e ^2^2
i
remained h i g h .
However,
g r o w t h may c e a s e e v e n m t h e p r e s e n c e o f t h e g r o w t h s p e c i e s i f
t h e s o o t becomes u n r e a c t i v e a s i t a g e s . The f a c t s t h a t a s i t
ages s o o t l o s e s i t s r a d i c a l c h a r a c t e r (10) a n d t h a t i t s c h e m i c a l
c o m p o s i t i o n becomes more g r a p h i t i c s u g g e s t t h a t i t s r e a c t i v i t y
does i n d e e d f a l l .
(Since t h e temperatures vary w i t h s t o i c h i o m e t r y
by a s much a s 100 K, t h e s u b s t a n t i a l f a l l i n t h e r a t e c o n s t a n t
w i t h t i m e i s n o t due p r i m a r i l y t o t h e d e c r e a s e i n t e m p e r a t u r e
w i t h h e i g h t above t h e b u r n e r , w h i c h i s a l s o a b o u t 100 K.) I f we
assume t h a t a c e t y l e n e i s t h e p r i n c i p a l g r o w t h s p e c i e s , t h e n a p l o t
of l n ( s p e c i f i c growth r a t e ) vs lnfC^H^] g i v e s a r e a c t i o n order o f
j=0.90.7 (2 s i g m a ) ; t h a t i s , t h e r e a c t i o n i s f i r s t o r d e r . The
a p p a r e n t f i r s t o r d e r r a t e c o n s t a n t k may t h e n be d e t e r m i n e d , a n d
i t i s p l o t t e d i n F i g u r e 4. The s p r e a d i n t h e d a t a w h i c h a p p e a r s
i n the lower p a r t o f F i g u r e 3 i s l a r g e l y e l i m i n a t e d .
I n d e p e n d e n t d a t a on s u r f a c e g r o w t h h a v e b e e n p r o v i d e d b y
A r e | e v a e a l . ( 1 4 ) . A t 1700 t h e y m e a s u r e d a r a t e c o n s t a n t o f
10
g/cm - s - a t m f o r s u r f a c e g r o w t h o n p u r e c a r b o n f r o m ^2^2*
w h i c h i s s i m i l a r t o t h e r a t e c o n s t a n t t h a t we c a l c u l a t e f o r o l d
( h i g h C/H r a t i o ) s o o t i n o u r f l a m e .
The agreement s u p p o r t s t h e
c o n c l u s i o n t h a t s u r f a c e growth i s c o n t r i b u t e d p r i m a r i l y by a c e t y
lene.
F i n a l l y , we n o t e t h a t s i n c e t h e s p e c i f i c g r o w t h r a t e s a r e
s i m i l a r i n f l a m e s w h i c h p r o d u c e v e r y d i f f e r e n t amounts o f s o o t ,
t h e p r o c e s s e s c o n t r o l l i n g t h e u l t i m a t e s o o t l o a d i n g must o c c u r
p r i o r t o the growth stage; t h a t i s , d u r i n g the n u c l e a t i o n stage.
Thus, even though s u r f a c e growth i s r e s p o n s i b l e f o r p r a c t i c a l l y
a l l o f t h e mass o f m a t u r e s o o t p a r t i c l e s , i t a p p e a r s t h a t r i c h e r
f l a m e s p r o d u c e more s o o t b e c a u s e t h e y h a v e a h i g h e r n u c l e a t i o n
r a t e and t h e r e f o r e more s u r f a c e a r e a f r o m t h e b e g i n n i n g o f t h e
growth stage.
t s e
Summary a n d C o n c l u s i o n s
(1) We h a v e f o u n d t h a t t h e i n c r e a s e d s u r f a c e g r o w t h i n r i c h e r
flames i s accounted f o r p r i m a r i l y by t h e i n c r e a s e d s u r f a c e area
a v a i l a b l e f o r growth i n t h e s e f l a m e s , and n o t by a h i g h e r con
c e n t r a t i o n o f growth s p e c i e s .
Thus, r i c h e r flames a r e s o o t i e r
because they have a h i g h e r n u c l e a t i o n r a t e .
(2) D e p l e t i o n o f g r o w t h s p e c i e s does n o t o c c u r i n o u r f l a m e s .
T h e r e f o r e , t h e f i n a l s i z e r e a c h e d b y t h e s o o t p a r t i c l e s , when s u r -

30
10 2 r -
1 0 -3
C / O = 0 76
.80
82
90
.94
_i
10'
10
20
Time (ms)
30
F i g u r e h. A p p a r e n t f i r s t - o r d e r r a t e c o n s t a n t f o r t h e r e a c t i o n
converting acetylene t o soot.
(Reproduced w i t h p e r m i s s i o n from
Ref. 2 .
C o p y r i g h t 1983, Gordon and Breach.)
f a c e growth has v i r t u a l l y ceased, i s n o t determined by d e p l e t i o n

b u t r a t h e r by a d e c r e a s e i n t h e r e a c t i v i t y o f t h e s o o t .
(3) We have shown t h a t t h e a c e t y l e n e i n t h e b u r n e d g a s e s i s
t h e s o u r c e f o r most o f t h e mass o f m a t u r e s o o t p a r t i c l e s .
Fur
t h e r m o r e , we h a v e f o u n d t h a t t h e m e a s u r e d g r o w t h r a t e s a r e c o n s i s
tent w i t h the assumption that a f i r s t order decomposition r e a c t i o n
o f a c e t y l e n e w i t h t h e s o o t s u r f a c e i s r e s p o n s i b l e f o r most o f t h e
s o o t g r o w t h , a l t h o u g h d i a c e t y l e n e may a l s o p l a y some r o l e .
Literature Cited
1.
2.
3.
4.
5.
6.
7.
Gaydon, A. G.; Wolfhard, H. G. "Flames" 1979, Chapman and

Hall, 4th edi., London.
Harris, S. J . ; Weiner, A. M. Combustion Science and Technol
ogy 1983, 31, 155. Ibid, 32, 267.
D'Alessio, .; DiLorenzo, .; Sarofim, A. F.; Beretta, F.;
Masi, S.; Venitozzi, C., 15th Symposium (International) on
Combustion, The Combustion Institute, 1975, 1427.
Haynes, .; Wagner, H. Gg. Energy and Combustion Science
1981, 7, 229.
Millikan, R. C. J. Phys. Chem. 1962, 66, 794.
Howard, J. B.; Wersborg, B. L.; Williams, C. G. in Faraday
Symposium No. 7, Fogs and Smokes, Faraday Division, Chemical
Society, Longon, 1973, 109.
Smith, G. W. Combustion and Flame 1982, 48, 265.

2.
8.
9.
10.
11.
12.
13.
14.
HARRIS
31
Homann, . H.; Wagner, H. Gg., 11th Symposium (International)

on Combustion, The Combustion Institute, 1967, 371.
Haynes, B. S.; Jander, H.; Wagner, H. Gg. Ber. Bunsenges.
Phys. Chem. 1980, 84, 585.
Bonne, U.; Homann, . H.; Wagner, H. Gg., 10th Symposium
(International) on Combustion, The Combustion Institute,
1965, 503.
Tesner, P. A. Comb. Expl. Shockwaves 1979, 15, 111.
Tanzawa, T.; Gardiner, W. C. J. Phys. Chem. 1980, 84, 236.
Bittner, J. P. Ph.D. Thesis, Massachusetts Institute of
Technology, Department of Chemical Engineering, 1980.
Arefeva, E. F.; Rafalkes, I. S.; Tesner, P. A. Khimiya
Tverdogo Topliva (Solid Fuel Chemistry) 1977, 11, 113.
RECEIVED October 26,
1983

3
Ion Concentrations in Premixed Acetylene-Oxygen
Flames near the Soot Threshold
D. G. KEIL, R. J. GILL, D. B. OLSON, and H. F. CALCOTE
AeroChem Research Laboratories, Inc., Princeton, J 08542

Total ion concentration profiles were measured through
the flame front of laminar, premixed, low pressure
acetylene-oxygen flames at equivalence ratios, , from
1.5 to 4.0. Peak total ion concentrations decrease
with increasing up to and beyond the soot threshold
( = 2.4). At close to the soot threshold, a second
peak appears in the ion profiles. This second peak
contains some of the same ions, e.g., C H +, as the
first peak which is ascribed to chemi-ionization. The
second peak reaches a minimum, at = 2.9, well on
the fuel rich side of the soot threshold, and then
rises again with increase in equivalence ratio. In a
sooting, = 3.0, flame the concentrations measured
are in reasonable agreement with measurements by
others using molecular beam sampling techniques. The
results refute the arguments against an ionic mecha
nism based on reported observations that the total
ion concentration increases at the soot threshold. The
measured ion concentrations are consistent with an
ionic mechanism of soot nucleation.
1 3
Ions a r e observed i n a l l premixed hydrocarbon flames.

I n near
s t o i c h i o m e t r i c flames, t h e major ions a r e s m a l l (molecular weight
< 100 amu); t h e y r e s u l t f r o m t h e p r i m a r y c h e m i - i o n i z a t i o n r e a c t i o n CH + 0 = C H 0 a n d s u b s e q u e n t i o n - m o l e c u l e r e a c t i o n s . R e c e n t
f l a m e i o n s a m p l i n g mass s p e c t r o m e t r i c s t u d i e s ( 1 ) o f p r e m i x e d
C H / 0 f l a m e s h a v e shown t h a t a s t h e f l a m e s a r e e n r i c h e d t o n e a r
o r b e y o n d s o o t t h r e s h o l d , t h e l i g h t e r mass i o n s ( < 300 amu) d e crease i n c o n c e n t r a t i o n r e l a t i v e t o t h e growth o f l a r g e r ions ( >
300 amu).
T h i s has been c i t e d as evidence t h a t r a p i d ion-molecule
r e a c t i o n s convert small hydrocarbon "precursor" ions (e.g., C H ,
C H , and C H ) t o l a r g e r and l a r g e r i o n s w h i c h e v e n t u a l l y b e come s o o t p a r t i c l e s ( 2 , 3 ) . The i n t e r m e d i a t e s i z e i o n s w i t h masses
b e t w e e n a b o u t 100-500 amu c o r r e s p o n d t o p o l y c y c l i c a r o m a t i c h y d r o +
0097-6156/84/0249-0033506.00/0
34
c a r b o n (PCAH) i o n s . The h i g h e r mass i o n s a r e l e s s w e l l i d e n t i

f i e d , b e i n g g e n e r a l l y g r o u p e d i n mass r a n g e s , b u t a r e assumed t o
i n v o l v e continued growth to soot p a r t i c l e s .
I n s t u d i e s of s o o t i n g
C 2 H 2 / O 2 f l a m e s , Homann (4) and Homann and S t r o e f e r (5) h a v e ob
t a i n e d l o w r e s o l u t i o n i o n mass d a t a t o a b o u t 1 0 amu, c o v e r i n g t h e
range from p u r e l y m o l e c u l a r i o n s to charged p a r t i c l e s observable
by e l e c t r o n m i c r o s c o p y ( e q u i v a l e n t t o s p h e r e s w i t h d i a m e t e r s o f
a b o u t 6 nm).
A l t h o u g h t h e y f o u n d t h e mean i o n mass i n c r e a s e d
throughout the flame, they d i d not a s s o c i a t e these i o n s w i t h the
l o w mass PCAH i o n s s i n c e t h e t o t a l i o n i z a t i o n i n c r e a s e d s h a r p l y a t
t h e h e i g h t i n t h e f l a m e f o r t h e o n s e t o f s o o t i n g . Due t o t h e
f a i r l y low i o n masses o b s e r v e d i n t h i s r e g i o n ( i . e . , h i g h i o n i z a
t i o n p o t e n t i a l s ) , t h e r m a l i o n i z a t i o n was a l s o r u l e d o u t .
Several
p o s s i b l e mechanisms f o r t h e p r o d u c t i o n o f s u c h l a r g e m o l e c u l a r
i o n s h a v e r e c e n t l y b e e n c o n s i d e r e d by C a l c o t e (6) who
concluded
t h a t c o n t i n u e d g r o w t h o f s m a l l e r c h e m i - i o n s by r e a c t i o n s w i t h
m a j o r f l a m e n e u t r a l s p e c i e s s u c h a s C H o r C4H2 i s t h e most l i k e
l y mechanism f o r t h e p r o d u c t i o n o f l a r g e m o l e c u l a r i o n s i n f l a m e s .
On t h e o t h e r h a n d , G o o d i n g s , T a n n e r , and Bohme (7_) and M i c h a u d ,
D e l f a u , and B a r a s s i n (8) f a v o r b u i l d u p o f l a r g e n e u t r a l s p e c i e s by
f r e e r a d i c a l r e a c t i o n s f o l l o w e d by an i o n - m o l e c u l e r e a c t i o n o f a
s m a l l i o n w i t h t h e n e u t r a l s p e c i e s t o p r o d u c e a l a r g e i o n . Homann
and S t r o e f e r f a v o r t h e r m a l i o n i z a t i o n o f t h e l a r g e n e u t r a l s p e c i e s
by e n e r g y a c c u m u l a t i o n as t h e s p e c i e s grows ( 5 ) .
D e l f a u e t a l . (9.) m e a s u r e d t h e t o t a l i o n c o n c e n t r a t i o n p r o
f i l e s i n a s e r i e s of low p r e s s u r e C2H2/O2/N2 premixed f l a m e s from
n o n s o o t i n g t o h e a v i l y s o o t i n g u s i n g L a n g m u i r p r o b e s and a m o l e c u
l a r beam F a r a d a y c a g e t e c h n i q u e .
On t h e f u e l l e a n s i d e o f t h e
s o o t t h r e s h o l d , t h e peak i o n c o n c e n t r a t i o n s d e c r e a s e d w i t h i n
c r e a s i n g e q u i v a l e n c e r a t i o w h e r e a s on t h e f u e l r i c h s i d e , t h e peak
ion concentrations increased with equivalence r a t i o .
Since the
minimum peak i o n c o n c e n t r a t i o n seemed t o o c c u r n e a r t h e c r i t i c a l
e q u i v a l e n c e r a t i o f o r s o o t f o r m a t i o n , D e l f a u e t a l . and t h e n
Haynes and Wagner (10) c o n c l u d e d t h a t t h e i o n s i n t h e s o o t i n g
f l a m e s a r e t h e r e s u l t o f s o o t f o r m a t i o n and n o t t h e c a u s e .
Close
e x a m i n a t i o n of the r e s u l t s of D e l f a u e t a l . ( 9 ) , however, d i s
c l o s e s t h a t t h e i o n c o n c e n t r a t i o n r e a c h e s a minimum v a l u e somewhat
r i c h e r than the c r i t i c a l equivalence r a t i o f o r soot f o r m a t i o n , ;
compare = 2.2 w i t h f o r minimum i o n c o n c e n t r a t i o n o f 2.3.
A d d i t i o n a l l y , t h e r e have been q u e s t i o n s about the v a l u e of the
t o t a l i o n c o n c e n t r a t i o n i n n e a r s o o t i n g and s o o t i n g f l a m e s , com
pared to the u l t i m a t e soot p a r t i c l e c o n c e n t r a t i o n s
(10-12).
These c o n f l i c t i n g i n t e r p r e t a t i o n s o f t h e i o n i z a t i o n b e h a v i o r
near soot t h r e s h o l d s b o t h w i t h v a r i a t i o n s of the e q u i v a l e n c e
r a t i o and t h e peak l o c a t i o n s i n t h e f l a m e and t h e q u e s t i o n s
a b o u t t h e t o t a l i o n c o n c e n t r a t i o n s p r o m p t e d us t o measure a b s o l u t e
i o n c o n c e n t r a t i o n p r o f i l e s i n t h e w e l l s t u d i e d 2.7 k P a (50 cm s~*
u n b u r n e d gas v e l o c i t y ) p r e m i x e d C H / 0 f l a m e i n an a t t e m p t t o
b e t t e r d e f i n e t h e t h r e s h o l d b e h a v i o r and t o d e t e r m i n e t h e a b s o l u t e
ion concentrations.

3.
KEILETAL.
Ion Concentrations in Acetylene-Oxygen
Flames
35
E x p e r i m e n t a l Apparatus and P r o c e d u r e s
Low P r e s s u r e Flame A p p a r a t u s . A l l e x p e r i m e n t s w e r e p e r f o r m e d o n
f l a t , p r e m i x e d l o w p r e s s u r e , 2.7 k P a (20 T o r r ) C H / 0 f l a m e s s t a
b i l i z e d o n a w a t e r c o o l e d b u r n e r . T h i s 8.6 cm d i a m b u r n e r was
c o n s t r u c t e d o f a p p r o x i m a t e l y 900, 0.12 cm i . d . s t a i n l e s s s t e e l
t u b e s m i c r o b r a z e d i n t o two s t a i n l e s s s t e e l p e r f o r a t e d p l a t e s t o
f o r m a w a t e r j a c k e t a r o u n d t h e t u b e s . Gases w e r e m e t e r e d u s i n g
calibrated c r i t i c a l flow o r i f i c e s .
The b u r n e r was i n s t a l l e d i n a
l o w p r e s s u r e v e s s e l pumped b y a 140 L s ^ (300 CFM) m e c h a n i c a l
vacuum pump. Unburned g a s v e l o c i t i e s (298 a n d 2.7 kPa) i n a l l
c a s e s were 50 cm s " .
E q u i v a l e n c e r a t i o s f r o m = 1.5 t o 4.0 were
s t u d i e d w i t h most e m p h a s i s on a s o o t i n g = 3.0 f l a m e .
Visible
s o o t e m i s s i o n became a p p a r e n t a t a s o o t t h r e s h o l d o f = 2.4 t o
2.5.
2
L a n g m u i r P r o b e . A w a t e r - c o o l e d e l e c t r o s t a t i c p r o b e was c o n s t r u c
t e d f r o m s e v e r a l t e l e s c o p i n g b r a s s t u b e s a r o u n d a 0.124 cm i . d .
s t a i n l e s s s t e e l t u b e c o n t a i n i n g a P t / 1 0 % Rh p r o b e w i r e i n s u l a t e d
by f i n e q u a r t z a n d T e f l o n s l e e v e s .
The p r o b e w i r e , u s u a l l y 0.025
cm d i a m , p r o t r u d e d 0.1 t o 1.0 cm f r o m t h e end o f t h e t u b e s e x p o s e d
to t h e flame gases. T h i s probe assembly i s r e f e r r e d t o a s t h e
" f i x e d p r o b e . " A s i m i l a r a s s e m b l y was a l s o u s e d i n w h i c h t h e P t /
Rh w i r e c o u l d be q u i c k l y e x t e n d e d i n t o t h e f l a m e f r o m a n e n c l o s i n g
h o u s i n g b y f i x e d amounts ( 0 t o 1 cm) o r w i t h d r a w n i n t o t h e c o o l e d
h o u s i n g b y e x t e r n a l l y m o v i n g a 0.127 cm d i a m P t / R h w i r e b u t t w e l d e d
to t h e f i n e probe w i r e .
A vacuum t i g h t s l i d i n g 0 - r i n g s e a l was
used around t h e l a r g e r w i r e .
T h i s " p u l s e d " probe apparatus m i n i
mized soot d e p o s i t i o n on t h e probe w i r e by i n s e r t i n g the w i r e i n
the f l a m e j u s t l o n g enough t o t a k e a measurement. T h i s p r o b e was
u s e d a t a d i s t a n c e o f 0.5 cm o r f a r t h e r f r o m t h e b u r n e r , where
s o o t d e p o s i t i o n o n t h e p r o b e was a p r o b l e m .
I n b o t h c o n f i g u r a t i o n s , t h e p r o b e was b i a s e d r e l a t i v e t o t h e
g r o u n d e d b u r n e r w i t h a v a r i a b l e d.c. power s u p p l y . P r o b e c u r r e n t s
w e r e m e a s u r e d w i t h a n e l e c t r i c a l l y f l o a t i n g K e i t h l e y M o d e l 602
electrometer.
P r o b e r e s i s t a n c e t o g r o u n d was t y p i c a l l y 1 0
ohms,
m e a s u r e d b e f o r e and a f t e r e a c h e x p e r i m e n t .
F u l l current-voltage p r o f i l e s i n low pressure C H / 0 flames
w i t h = 1.5 t o 3.5 were m e a s u r e d u s i n g t h e " f i x e d " p r o b e t o d e t e r
mine t h e probe c u r r e n t a t plasma p o t e n t i a l , Vp, by e x t r a p o l a t i o n .
The " p u l s e d " p r o b e was u s e d o n l y a t c o n s t a n t v o l t a g e s (-20 a n d
-40 V) i n o r d e r t o m i n i m i z e e x p o s u r e t i m e s ( = 1-2 s ) t o t h e f l a m e
and was u s e d m a i n l y u n d e r s o o t i n g c o n d i t i o n s , 2.4 ^ 4 . 0 .
1 3
Probe Theory.
E x p e r i m e n t a l probe c u r r e n t s a t t h e plasma p o t e n t i a l ,
where d i f f u s i v e t r a n s p o r t o f i o n s t o t h e p r o b e d o m i n a t e s c o n v e c t i v e t r a n s p o r t , were c o n v e r t e d t o i o n c o n c e n t r a t i o n s u s i n g t h e
e q u a t i o n d e r i v e d by C a l c o t e ( 1 3 ) :

36
1.5
In
(D
H e r e n_j_ i s t h e i o n c o n c e n t r a t i o n ( c m " ) o f i o n s w i t h mass m+ and

mean f r e e p a t h .
( I + ) i i s the c u r r e n t at plasma p o t e n t i a l c o l
l e c t e d by a c y l i n d r i c a l p r o b e w i r e o f r a d i u s r and l e n g t h .
The
s y m b o l s e, k, and r e p r e s e n t t h e e l e c t r o n c h a r g e , B o l t z m a n n ' s c o n
s t a n t , and t h e t e m p e r a t u r e (), r e s p e c t i v e l y . The p a r a m e t e r s X
and a r e d e f i n e d : X = + 2 and = ( X - 4 ( r + + ) )
.
P r o b e c u r r e n t s m e a s u r e d a t h i g h n e g a t i v e b i a s e s were c o n v e r t
ed t o i o n c o n c e n t r a t i o n s u s i n g t h e C l e m e n t s and Smy t h i c k s h e a t h
t h e o r y (14) f o r i o n c o l l e c t i o n i n a f l o w i n g p l a s m a u n d e r c o n d i
t i o n s where c o n v e c t i v e r a t h e r t h a n d i f f u s i v e t r a n s p o r t o f i o n s t o
the probe r e g i o n dominates:
+
2A
^ /
/ 2
(n
fln(I /2n e v
+
v V ) /
^ .
f
r i, )]
(2)
where i s t h e i o n m o b i l i t y , e i s t h e p e r m i t t i v i t y o f s p a c e , V f
i s t h e l o c a l f l o w v e l o c i t y , and I i s t h e p r o b e c u r r e n t c o l l e c t e d
a t n e g a t i v e V v o l t s r e l a t i v e t o plasma p o t e n t i a l .
S i n c e t h e assumed mode o f i o n t r a n s p o r t t o t h e p r o b e w i r e d i f
f e r s i n t h e d e r i v a t i o n o f E q u a t i o n s 1 and 2, t h e most a p p r o p r i a t e
t y p e o f measurement depends on t h e l o c a l f l a m e c o n d i t i o n s , t h e
d e g r e e o f i o n i z a t i o n , t h e mass d i s t r i b u t i o n o f i o n s , e t c .
Esti
mates o f t h i s i n f o r m a t i o n w e r e u s e d a l o n g w i t h c e r t a i n p r o b e
t h e o r y c r i t e r i a t o s e l e c t t h e most a c c u r a t e method f o r e a c h i n d i
v i d u a l measurement ( 1 5 ) .
The a p p l i c a t i o n o f E q u a t i o n s 1 and 2 r e q u i r e s i n f o r m a t i o n on
f l a m e t e m p e r a t u r e s , f l o w v e l o c i t i e s , and i o n m o b i l i t i e s / m e a n f r e e
p a t h s t h r o u g h o u t t h e f l a m e , as w e l l as t h e p r o b e w i r e d i m e n s i o n s .
T h i s i n f o r m a t i o n i s u s e d b o t h t o s e l e c t t h e t y p e o f measurement t o
make ( e . g . , p r o b e c u r r e n t s a t p l a s m a p o t e n t i a l o r a t l a r g e n e g a
t i v e p o t e n t i a l s ) and t o c a l c u l a t e t h e i o n c o n c e n t r a t i o n , n .
De
t a i l s o f p r o b e t h e o r y s e l e c t i o n as w e l l as t h e d e t e r m i n a t i o n o f
t h e n e c e s s a r y l o c a l f l a m e and i o n t r a n s p o r t p r o p e r t i e s a r e g i v e n
e l s e w h e r e . The a p p r o a c h , h o w e v e r , i s s u m m a r i z e d h e r e .
Flame t e m p e r a t u r e p r o f i l e s a g a i n s t d i s t a n c e f r o m t h e b u r n e r
a r e b a s e d on s o d i u m l i n e r e v e r s a l measurements o f Bonne and Wagner
(16) i n s i m i l a r 2.7 k P a , 50 cm s " C H / 0 f l a m e s .
I n flames not
m e a s u r e d by Bonne and Wagner, t h e p r o f i l e s were s c a l e d w i t h c a l c u
l a t e d a d i a b a t i c f l a m e t e m p e r a t u r e s . An u n c e r t a i n t y o f 100 i n
t h e t e m p e r a t u r e r e s u l t s i n a m i n o r ( < 10%) e r r o r i n t h e c a l c u l a t e d
ion concentrations.
Flow v e l o c i t i e s are determined from the l o c a l
t e m p e r a t u r e and e q u i l i b r i u m c o m p o s i t i o n (mole c h a n g e ) .
I o n t r a n s p o r t p r o p e r t i e s a r e e s t i m a t e d on t h e b a s i s o f t h e
i o n masses i n t h e f l a m e .
The method u s e d t o e s t i m a t e t h e s e num
b e r s i s n o t s t r a i g h t f o r w a r d s i n c e an e x t r e m e l y w i d e r a n g e o f i o n
+

3.
KEIL ET AL.
37
Flames
masses i s o b s e r v e d i n s o o t i n g f l a m e s .
We h a v e c o n s i d e r e d i o n
masses o b s e r v e d i n o u r f l a m e i o n mass s p e c t r o m e t r i c s t u d i e s o f l o w
mass i o n s ( < 300 amu) and i n t h e h e a v y f l a m e i o n (100 < mass < 1 0
amu) s t u d i e s by Homann and c o w o r k e r s C4,.5) u s i n g t h e i r v a r i a b l e
h i g h - p a s s i o n mass f i l t e r i n s o o t i n g f l a m e s ( = 2 . 8 - 3 . 2 5 ) .
Our mass s p e c t r o s c o p i c s t u d i e s h a v e shown t h a t i n n o n s o o t i n g
f l a m e s t h e d o m i n a n t i o n s a r e e i t h e r H 0 (19 amu) o r C H
(39
amu) w i t h C H
dominating i n the r i c h e r of the nonsooting
flames.
I n s o o t i n g f l a m e s ( ^ 2 . 4 ) C H
a l s o d o m i n a t e s w i t h i n a b o u t 1 cm
from the burner.
Beyond t h i s r e g i o n , t h e i o n masses r a p i d l y i n
c r e a s e so we must depend on t h e s t u d i e s o f Homann e t a l .
The r e c e n t i o n mass r e s u l t s o f Homann and S t r o e f e r (_5) were
s c a l e d t o Homann s more c o m p l e t e r e s u l t s (4) (heavy i o n mass d i s
t r i b u t i o n s d e t e r m i n e d a t more d i s t a n c e s f r o m t h e b u r n e r i n h i s =
2.9, 2.7 k P a f l a m e ) .
The r e s u l t a n t p r o f i l e o f m e d i a n i o n mass
v e r s u s d i s t a n c e f r o m t h e b u r n e r was s h i f t e d 0.2 cm c l o s e r t o t h e
b u r n e r (based o n Homann and S t r o e f e r ^ e x p e r i m e n t s on t h e e f f e c t
o f f l o w v e l o c i t y on i o n p r o f i l e s ) t o c o r r e c t f o r t h e s m a l l v e l o c i
t y d i f f e r e n c e b e t w e e n t h e i r u n b u r n e d gas v e l o c i t y ( = 4 3 cm s"" )
f o r w h i c h t h e y r e p o r t d a t a and o u r u n b u r n e d gas v e l o c i t y (50 cm
s"" ).
This s h i f t i s c o n s i s t e n t w i t h t h e i r observed s h i f t of the
peak i o n s i g n a l l o c a t i o n w i t h v e l o c i t y .
S i n c e Homann and S t r o e f e r
f o u n d l i t t l e d i f f e r e n c e i n t h e 2 cm mass d i s t r i b u t i o n b e t w e e n =
2.8 and = 3.5, t h e r e s u l t s s h o u l d a p p l y e q u a l l y t o a = 3.0
flame.
"Smooth" e x t r a p o l a t i o n s o f t h e i o n masses were made beyond
4 cm and t o mass 39 a t 0.9 cm.
T h i s p r o c e d u r e r e s u l t e d i n t h e m e d i a n i o n mass p r o f i l e shown
i n F i g u r e 1 a s a smooth c u r v e .
A l s o shown a r e t h r e e p o i n t s o f
m e d i a n c h a r g e d p a r t i c l e masses f r o m t h e e l e c t r o n - m i c r o s c o p e
study
o f Adams ( 1 7 ) . A p a r t i c l e d e n s i t y o f 1.5 g cm"" was u s e d t o c o n
v e r t Adams r e p o r t e d p a r t i c l e d i a m e t e r t o m a s s e s . T h e r e i s good
agreement w i t h i n a f a c t o r o f 2 b e t w e e n t h e c h a r g e d p a r t i c l e masses
and t h e m e d i a n i o n mass p r o f i l e .
The g r e a t e s t u n c e r t a i n t i e s i n
t h e m e d i a n i o n mass a r e s e e n t o o c c u r a t d i s t a n c e s b e t w e e n 1 and 2
cm f r o m t h e b u r n e r where t h e mass i n c r e a s e s by more t h a n two
orders of magnitude.
I n t h e r e d u c t i o n o f o u r L a n g m u i r p r o b e d a t a we assumed t h i s
i o n mass p r o f i l e i n a l l s o o t i n g f l a m e s w i t h ^ 2 . 7 5 .
I n the
s l i g h t l y s o o t i n g = 2.5 f l a m e , we u s e d t h e i n t e r m e d i a t e p r o f i l e
shown a s a d a s h e d l i n e i n F i g u r e 1, b a s e d o n a somewhat a r b i t r a r y
g e o m e t r i c mean b e t w e e n t h e i o n masses i n a n o n s o o t i n g = 2.0
f l a m e (m_j_ = 39 amu) and t h o s e i n a h e a v i l y s o o t i n g f l a m e .
The
u n c e r t a i n t i e s i n t r o d u c e d b y t h e s e a p p r o x i m a t i o n s w i l l be d i s c u s s e d
w i t h p r e s e n t a t i o n of the r e s u l t s of t h i s study.
Our mass s p e c t r o m e t r i c s t u d i e s h a v e shown t h a t m a j o r i o n s <:
500 amu a r e c o n s i s t e n t i n mass w i t h p o l y c y c l i c a r o m a t i c
hydrocar
bon (PCAH) i o n s . E x p e r i m e n t a l i o n m o b i l i t i e s o f a w i d e mass r a n g e
o f PCAH i o n s (18,19) were e x t r a p o l a t e d t o v e r y h i g h masses i n o r
d e r t o e s t i m a t e t h e m o b i l i t i e s o f t h e h e a v y m e d i a n mass i o n s ( F i g
ure 1 ) . This e x t r a p o l a t i o n p a r a l l e l s a Langevin-type equation,
s

38
10
3
. . .
<
5
Ui
- - - - - - :
/
/
%
1Q2
DISTANCE ABOVE BURNER, cm

F i g u r e 1.
E s t i m a t e d m e d i a n i o n masses b a s e d on Homann a n d c o
w o r k e r s h e a v y i o n masses ( s e e t e x t ) i n s o o t i n g f l a m e s .
Solid
l i n e used t o convert Langmuir probe c u r r e n t s t o i o n c o n c e n t r a t i o n s
i n f l a m e s w i t h 0 > 2 . 5 ; d a s h e d l i n e i s g e o m e t r i c mean o f s o l i d
l i n e a n d mass 39 a n d was u s e d i n 0 = 2 . 5 f l a m e , o, c h a r g e d p a r
t i c l e mass ( I T ) ; a n d d e n s i t y = 1.5 g cm~^.

3.
KEILETAL.
39
Flames
g i v i n g us confidence i n t h e procedure.
Corrections of the resul
t a n t i o n m o b i l i t i e s w e r e made f o r f l a m e t e m p e r a t u r e , p r e s s u r e , a n d
for composition using B l a n c s law.
1
R e s u l t s and D i s c u s s i o n
Ion c o n c e n t r a t i o n s w e r e d e r i v e d f r o m t h e e x p e r i m e n t a l p r o b e d a t a
b a s e d o n t h e mass d i s t r i b u t i o n s i n F i g u r e 1 i n s o o t i n g f l a m e s ( ^
2.5) e x c e p t i n r e g i o n s c l o s e t o t h e b u r n e r (0 t o 1 cm) where 39
amu ( C H + ) was u s e d f o r t h e mass o f t h e f l a m e i o n s .
I n the lean
e r f l a m e s ( < 2 . 4 ) , mass 39 was u s e d i n t h e c a l c u l a t i o n s w i t h t h e
e x c e p t i o n o f t h e = 1.5 f l a m e i n w h i c h o u r f l a m e i o n s a m p l i n g
mass s p e c t r a l s t u d i e s i n d i c a t e t h a t beyond a b o u t 1.2 cm, t h e d o m i
n a n t i o n i s H 0 (mass = 19 amu).
The r e s u l t a n t p r o f i l e s a r e
shown i n F i g u r e 2 where t h e d a s h e d l i n e s a r e b a s e d o n C a l c o t e ' s
t h e o r y and t h e s o l i d l i n e s a r e b a s e d o n t h e t h i c k s h e a t h t h e o r y o f
C l e m e n t s a n d Smy. The e r r o r b a r a t 5 cm o n t h e = 3.0 p r o f i l e i s
representative of ther e p r o d u c i b i l i t y of theabsolute concentra
t i o n s d e t e r m i n e d a t d i f f e r e n t t i m e s . The r e p o r t e d p r o f i l e s r e p r e
s e n t p o i n t b y p o i n t a v e r a g e s . The peak i o n c o n c e n t r a t i o n s i n t h e
s o o t i n g f l a m e s w e r e g e n e r a l l y more r e p r o d u c i b l e t h a n w e r e t h e c o n
c e n t r a t i o n s f a r t h e r away f r o m t h e b u r n e r . The t r a n s i t i o n s b e t w e e n
d a s h e d p r o f i l e s and s o l i d p r o f i l e s i n s o o t i n g f l a m e s w e r e s u b j e c t
to some s m o o t h i n g , b e i n g b a s e d on s e p a r a t e e x p e r i m e n t s , b u t t h e
o v e r l a p was w i t h i n t h e u n c e r t a i n t i e s .
The r e g i o n n e a r t h e b u r n e r
i n s o o t y f l a m e s gave t h e l e a s t r e l i a b l e m e a s u r e m e n t s , due i n p a r t
to l a r g e temperature g r a d i e n t s , r a p i d l y changing i o n masses, and
low i o n c o n c e n t r a t i o n s .
The n o n s o o t i n g f l a m e s ( = 1.5, 2.0) e x h i b i t a s i n g l e p e a k
w h i c h d e c r e a s e s i n m a g n i t u d e and s h i f t s downstream w i t h i n c r e a s i n g
.
A t = 2.5, n e a r t h e t h r e s h o l d f o r s o o t i n g , ( = 2 . 4 - 2 . 5 ) , a
s e c o n d peak c o n s i d e r a b l y f a r t h e r downstream b e g i n s t o a p p e a r . T h i s
s e c o n d peak o c c u r s a t a d i s t a n c e where t h e m e d i a n i o n mass i s
g r e a t l y i n c r e a s i n g ( F i g u r e 1 ) . The c a l c u l a t e d r e l a t i v e i o n c o n c e n
t r a t i o n s a t t h e f i r s t a n d s e c o n d peak i n t h i s p r o f i l e a r e d e p e n d
e n t o n t h e r e l a t i v e i o n masses assumed i n t h e peak r e g i o n s t h r o u g h
the i o n m o b i l i t i e s u s e d i n E q u a t i o n 2. F o r t h e h e a v y i o n s i n t h e
r e g i o n o f t h e s e c o n d p e a k , we h a v e f o u n d t h a t t h e c o n v e r s i o n f a c
t o r from probe c u r r e n t s t o i o n c o n c e n t r a t i o n s i s r o u g h l y p r o p o r
t i o n a l t o m^. " due t o t h e f a i r l y weak dependence o n . I n genre r a l , t h i s i s a s m a l l mass e f f e c t , b u t i t c a n be s i g n i f i c a n t i f
the mass i s c h a n g i n g r a p i d l y ; a n o r d e r o f m a g n i t u d e i n c r e a s e i n
mass l e a d s t o a 5 0 % g r e a t e r c a l c u l a t e d n_j_. I n r i c h e r , h e a v i l y
s o o t i n g f l a m e s ( = 3.0, 3.5) t h e s e c o n d p e a k becomes more a c c e n
t u a t e d w h i l e t h e f i r s t peak c o n t i n u e s t o d e c r e a s e w i t h i n c r e a s i n g
.
I n t h e s e f l a m e s , t h e i o n p r o b e c u r r e n t s show d i s t i n c t d o u b l e
peaks.
T h u s , a l t h o u g h t h e s e c o n d p e a k i n t h e = 2.5 f l a m e m i g h t
be c o n s i d e r e d a n a r t i f a c t o f t h e c o n v e r s i o n o f p r o b e c u r r e n t s t o
i o n c o n c e n t r a t i o n s , i t c l e a r l y i s n o t so i n t h e r i c h e r f l a m e s . The
m a g n i t u d e o f t h e s e c o n d peak d e c r e a s e s a s i n c r e a s e s f r o m 2.5 t o
3
18

40
10
I
1
I
3
'
4

Figure 2 . T o t a l i o n concentration p r o f i l e s from Langmuir probe.
Results i n s o l i d l i n e s based on currents measured with l a r g e nega
t i v e b i a s and Equation 2 (ik) ; dashed l i n e s based on currents at
plasma p o t e n t i a l and Equation 1 ( 1 3 ) . E r r o r bar at 5 cm f o r 0 =
3 . 0 flame represents r e p r o d u c i b i l i t y o f measurements at v a r i o u s
times.

3.
KEIL E l AL.
Flames
41
2.9.
F u r t h e r e n r i c h m e n t o f t h e f l a m e t o = 3.5 r e v e r s e s t h e
t r e n d w i t h a l a r g e i n c r e a s e i n t h e m a g n i t u d e o f t h e s e c o n d peak.
The i o n c o n c e n t r a t i o n s a t t h e p e a k s a r e p l o t t e d a s a f u n c t i o n
o f e q u i v a l e n c e r a t i o i n F i g u r e 3. I g n o r i n g f o r t h e moment a n y d i f
f e r e n t i a l b e t w e e n t h e f i r s t and s e c o n d maxima, i t i s s e e n t h a t
peak i o n c o n c e n t r a t i o n i n a s e r i e s o f f l a m e s o f i n c r e a s i n g f u e l
r i c h n e s s beyond = 1.5 d e c r e a s e s w e l l beyond ( ~ 0 . 5 e q u i v a l e n c e
u n i t s ) t h e c r i t i c a l t h r e s h o l d f o r soot f o r m a t i o n , , i n d i c a t e d by
t h e shaded a r e a . T h i s phenomenon i s more marked t h a n t h a t o b s e r v e d
by D e l f a u e t a l . (9) i n t h e i r C 2 H 2 / O 2 / N 2 f l a m e s w h e r e t h e l o w e s t
maximum o c c u r r e d a b o u t 0.1 e q u i v a l e n c e u n i t g r e a t e r t h a n . T h i s
o b s e r v a t i o n r e f u t e s any argument a g a i n s t t h e i o n i c s o o t f o r m a t i o n
mechanism b a s e d on a n i n c r e a s e i n peak i o n i z a t i o n a t t h e s o o t
threshold equivalence r a t i o .
0
As i n t h e i n v e s t i g a t i o n b y D e l f a u e t a l . , t h e f i r s t maximum
i n the present study i s a s s o c i a t e d w i t h i o n s d e r i v e d from normal
f l a m e c h e m i - i o n i z a t i o n p r o c e s s e s b e c a u s e , a s t h e f l a m e i s made
i n c r e a s i n g l y f u e l r i c h , t h e p o s i t i o n o f t h e maximum v a r i e s c o n t i n
u o u s l y and i t s magnitude d e c r e a s e s w i t h i n c r e a s i n g even i n t h e
s o o t i n g f l a m e s a s one w o u l d e x p e c t .
The s e c o n d maximum i s e x
p l a i n e d b y D e l f a u e t a l . ( 9 ) a s due t o " d i r e c t t h e r m a l i o n i z a t i o n
of l a r g e p o l y n u c l e a r a r o m a t i c m o l e c u l e s and carbon p a r t i c l e s l e s s
t h a n 2 nm d i a m e t e r o f l o w i o n i z a t i o n p o t e n t i a l s . "
This explana
t i o n h a s a l r e a d y b e e n q u e s t i o n e d b y Howard and P r a d o ( 2 0 ) . I n t h e
D e l f a u e t a l . paper and t h e r e f e r e n c e d d i s c u s s i o n , t h e second peak
i s i d e n t i f i e d w i t h t h e " i o n i z e d p a r t i c l e " peak ( a t h i r d p e a k )
w h i c h w i l l be d i s c u s s e d b e l o w .
Examination of Figure 5 i n t h e
paper o f D e l f a u e t a l . i n d i c a t e s t h a t t h e i r f i r s t and second peaks
c o r r e s p o n d t o o u r f i r s t and second peaks w h i c h b o t h o c c u r , a s w i l l
be shown, b e f o r e t h e peak i n " c h a r g e d p a r t i c l e s " a s i d e n t i f i e d b y
W e r s b o r g , Yeung, and Howard ( 2 1 ) .
Another d i f f i c u l t y w i t h t h eDelfau et a l . e x p l a n a t i o n i s that
t h e s e c o n d peak c o n t a i n s many o f t h e same s m a l l i o n s a s t h e f i r s t
p e a k ; s e e e . g . , F i g u r e 4. We have i d e n t i f i e d s e v e r a l i o n s i n t h e
s e c o n d peak i n c l u d i n g :
C i H , C i H n , C i H n , C i H n , and
i o n s c o n t a i n i n g 2 1 , 2 3 , 2 5 , 2 7 , and 29 c a r b o n atoms. T h e s e i o n s
a r e f a r t o o s m a l l t o be p r o d u c e d b y t h e r m a l i o n i z a t i o n a n d no
m e c h a n i s t i c path has been i d e n t i f i e d f o r t h e p r o d u c t i o n o f s m a l l
i o n s from l a r g e i o n s o r charged p a r t i c l e s ( 6 ) .
The l o c a t i o n s o f t h e two maxima a r e p l o t t e d a s a f u n c t i o n o f
t h e e q u i v a l e n c e r a t i o i n F i g u r e 5. I n t h e n o n s o o t i n g f l a m e s , t h e
( f i r s t ) maxima t e n d t o move away f r o m t h e b u r n e r w i t h i n c r e a s i n g
e q u i v a l e n c e r a t i o , w h i l e t h e s e c o n d maxima b e h a v e s i m i l a r l y i n t h e
sooting flames.
F i g u r e 6 shows a c o m p a r i s o n o f t h e t o t a l i o n c o n c e n t r a t i o n
p r o f i l e d e t e r m i n e d i n t h e p r e s e n t s t u d y o f t h e = 3.0 f l a m e w i t h
r e l e v a n t d a t a from o t h e r s t u d i e s . These i n c l u d e p r o f i l e s o f t o t a l
i o n s , c h a r g e d p a r t i c l e s , a n d n e u t r a l s p e c i e s . The p r o f i l e i n d i
c a t e d b y HS r e p r e s e n t s m o l e c u l a r beam F a r a d a y c a g e measurements b y
Homann a n d S t r o e f e r (.5). The p r o f i l e i s a c t u a l l y a n a v e r a g e o f
+

42
F i g u r e 3.
Maximum t o t a l i o n c o n c e n t r a t i o n s as a f u n c t i o n o f
equivalence r a t i o .
Same f l a m e s as F i g u r e 2 .
o , maxima c l o s e s t
t o b u r n e r ; a n d , s e c o n d maxima. S o o t t h r e s h o l d i s i n d i c a t e d
by s h a d i n g .
F i g u r e h.
C-^Hp
i o n p r o f i l e s u s i n g f l a m e s a m p l i n g mass s p e c t r o m e t e r t e c h n i q u e i n C2H2/O2 f l a m e ( 2 . 1 k P a , 50 cm s"~ u n b u r n e d
velocity).
C r i t i c a l threshold, 0 2.5.
C

3.
KEILETAL.
Flames
43
Figure 5.
L o c a t i o n s o f t h e t w o i o n c o n c e n t r a t i o n maxima i n F i g u r e
3.
Soot t h r e s h o l d i n d i c a t e d b y shading.
I
1 0
10
C H
>1000amu
11
ft
~
:
^ ^ X V l O N S (AeroChem)
10
fi
UJ
CO
%
/
1 0
/-NEUTRAL
SOOT
-
X/VCHARGED"
nC\
"
10
- IONS (HSP
//
\ll

F i g u r e 6.
Comparison o f present 0 = 3.0 Langmuir probe t o t a l i o n
concentration p r o f i l e with other r e s u l t s .
AeroChem, L a n g m u i r
p r o b e ; H S , m o l e c u l a r beam F a r a d a y cage (5_) ( s e e t e x t ) ; n e u t r a l s o o t
and c h a r g e d s o o t ('21); C H Q a n d > 1000 amu, n e u t r a l s p e c i e s ( 2 2 ) .
1 Q

44
t h e i r r e s u l t s f o r 6 = 2.8 and = 3.25 f l a m e s , w h i c h a r e s i m i l a r

i n s h a p e , t h e r i c h e r f l a m e e x h i b i t i n g somewhat h i g h e r i o n c o n c e n
trations.
The r e s u l t a n t p r o f i l e has a l s o been s h i f t e d 0.2
cm,
v i d e supra, towards the burner to c o r r e c t f o r the s m a l l v e l o c i t y
d i f f e r e n c e b e t w e e n t h e i r f l a m e and t h e o t h e r 50 cm s "
flames
r e p r e s e n t e d i n the f i g u r e .
T h e r e i s o v e r a l l good agreement b e
tween t h e i r t o t a l i o n c o n c e n t r a t i o n p r o f i l e and t h e L a n g m u i r p r o b e
result.
HS, h o w e v e r , d i d n o t o b s e r v e t h e f i r s t p e a k 1 cm f r o m t h e
b u r n e r , p r o b a b l y b e c a u s e t h e i r t e c h n i q u e was l e s s s e n s i t i v e t o t h e
l o w e r mass i o n s o b s e r v e d i n t h i s r e g i o n o f t h e f l a m e .
They may
n o t h a v e l o o k e d c l o s e r t o t h e b u r n e r b e c a u s e , as a l r e a d y d i s c u s s e d ,
t h i s i s a d i f f i c u l t r e g i o n i n w h i c h t o t a k e measurements ( s e e
Homann*s comments f o l l o w i n g R e f . 2 2 ) , and t h e y had no r e a s o n t o
e x p e c t a n o t h e r peak t h e r e .
F i g u r e 6 shows two n e u t r a l s p e c i e s p r o f i l e s f r o m t h e m o l e c u
l a r beam mass s p e c t r o m e t r i c s t u d y by B i t t n e r and Howard ( 2 2 ) .
The
polycyclics Ci H
and, a t a b o u t an o r d e r o f m a g n i t u d e l o w e r c o n c e n
t r a t i o n , C i ^ H e ( n o t shown) p e a k e a r l y i n t h e f l a m e a t a b o u t 0.5
and 0.7 cm, r e s p e c t i v e l y , w h i l e l a r g e n e u t r a l s > 1000 amu
(rela
t i v e c o n c e n t r a t i o n s c a l e ) peak i n the r e g i o n of the second i o n
maximum. Homann and Wagner (23) a l s o o b s e r v e d a p e a k o f l a r g e
n e u t r a l s p e c i e s they c a l l e d "soot p r e c u r s o r s " i n the r e g i o n where
t h e s e c o n d i o n maximum i s o b s e r v e d .
The g e n e r a l c o r r e s p o n d e n c e o f
two maxima i n b o t h t h e i o n c o n c e n t r a t i o n and t h e l a r g e n e u t r a l
species i n sooting flames r a i s e s s e v e r a l questions.
Are these
i o n s and n e u t r a l s a s s o c i a t e d w i t h e a c h o t h e r ?
I f so, are the i o n s
the source of the n e u t r a l s , or v i c e versa?
They c e r t a i n l y a p p e a r
t o h a v e a common g e n e s i s .
Does t h e a p p e a r a n c e o f t h e s e c o n d i o n
maximum h e r a l d s o o t f o r m a t i o n ?
These q u e s t i o n s r e m a i n u n a n s w e r e d
at t h i s time.
A l s o shown i n F i g u r e 6 a r e p r o f i l e s f o r l a r g e ( > 1 . 5 nm)
soot
and c h a r g e d p a r t i c l e s f r o m m o l e c u l a r beam e l e c t r o n m i c r o s c o p y
s t u d i e s o f Howard and c o w o r k e r s ( 2 1 ) . As shown a b o v e , t h e m a s s e s
a s s o c i a t e d w i t h the charged p a r t i c l e s agree w e l l w i t h the median
mass i o n p r o f i l e shown i n F i g u r e 1 b a s e d on Homann and S t r o e f e r s
work. The d i f f e r e n c e s b e t w e e n t h e HS and AeroChem p r o b e p r o f i l e s
and t h e c h a r g e d p a r t i c l e p r o f i l e may be e x p l a i n e d by a r g u i n g t h a t
t h e two t e c h n i q u e s u s e d t o p r o d u c e t h e HS and AeroChem p r o f i l e s do
not respond to heavy, charged soot p a r t i c l e s , w h i l e the e l e c t r o n
m i c r o s c o p e study used t o produce the charged soot p r o f i l e does not
d e t e c t s m a l l i o n s . However, t h e s e d i s c r i m i n a t i o n e f f e c t s must be
g r e a t e r t h a n m i g h t be e s t i m a t e d i f t h e t h r e e p r o f i l e s a r e l o c a t e d
c o n s i s t e n t l y w i t h respect to the burner.
A t 2 cm, Homann and
S t r o e f e r o b s e r v e d a m e d i a n i o n mass o f r o u g h l y 10** amu
correspond
i n g t o an " i o n " d i a m e t e r ( s p h e r e s w i t h d e n s i t y 1.5 g cm"" ) g r e a t e r
t h a n 2.5 nm, w i t h i n t h e r e p o r t e d s e n s i t i v i t y o f t h e e l e c t r o n m i c r o
s c o p e s t u d i e s ( > 1 . 5 nm) . I f t h e t h r e e measurement t e c h n i q u e s ,
L a n g m u i r p r o b e , F a r a d a y c a g e , and e l e c t r o n m i c r o s c o p e , m e a s u r e t h e
same s p e c i e s , why do t h e measurements d i f f e r by an o r d e r o f m a g n i
tude at t h i s d i s t a n c e ?
E v e n a l l o w i n g an e f f e c t i v e l o w e r dtecta-

3.
KEIL ET AL.
b i l i t y l i m i t o f 2.5 nm w i t h t h e e l e c t r o n m i c r o s c o p e measurement,
t h e mass d i s t r i b u t i o n f r o m t h e Homann and S t r o e f e r s t u d y a t 2 cm
( 5 0 % o f t h e i o n s > 2 . 5 nm) i n d i c a t e s t h a t t h e t o t a l i o n c o n c e n t r a
t i o n s f o r t h e t h r e e measurements s h o u l d b e i n much c l o s e r a g r e e
ment. The d i f f e r e n c e s a r e p r o b a b l y a t t r i b u t a b l e t o e x p e r i m e n t a l
e r r o r a n d t o t h e f a c t t h a t t h r e e somewhat d i f f e r e n t s y s t e m s w e r e
studied.
I f c o n s i s t e n c y i s e v o k e d a t 3.5 cm f r o m t h e b u r n e r b y a r b i
t r a r i l y s h i f t i n g t h e F a r a d a y c a g e ( 5 ) and L a n g m u i r p r o b e p r o f i l e s
i n F i g u r e 6 t o h i g h e r c o n c e n t r a t i o n s r e l a t i v e t o t h e Howard e t a l .
p a r t i c l e measurements ( 2 1 ) , so t h a t a l l t h r e e c u r v e s m a t c h a t t h i s
d i s t a n c e , t h e n t h e peak i o n c o n c e n t r a t i o n s i n t h e s h i f t e d p r o f i l e s
a r e 1.0 t o 1.4 1 0
cm"" , compared t o t h e peak n e u t r a l p l u s
c h a r g e d p a r t i c l e c o n c e n t r a t i o n o f 1.2 1 0
c m . The i o n c o n c e n
t r a t i o n i s s u f f i c i e n t l y l a r g e t o provide support f o r t h e hypothesis
of i o n i c p r e c u r s o r s f o r t h e soot c o n c e n t r a t i o n observed i n t h e
f l a m e b e c a u s e t h e peak i o n c o n c e n t r a t i o n i s c o m p a r a b l e t o t h e f i n a l
soot c o n c e n t r a t i o n .
I t s h o u l d be n o t e d , however, t h a t i o n s o o t
p r e c u r s o r q u e s t i o n s a r e u l t i m a t e l y more s t r o n g l y r e l a t e d t o f l u x e s
and r a t e s o f p r o d u c t i o n t h a n t o c o n c e n t r a t i o n s .
The c o r r e c t e d i o n and c h a r g e d p a r t i c l e p r o f i l e s i n F i g u r e 6,
c o u p l e d w i t h t h e i n f o r m a t i o n i n F i g u r e 1, c o u l d b e l o o k e d a t a s a
smooth p r o g r e s s i o n f r o m s m a l l i o n s t o l a r g e m o l e c u l a r i o n s t o l a r g e
c h a r g e d s o o t p a r t i c l e s w h i c h p r o d u c e n e u t r a l p a r t i c l e s on r e c o m b i n
a t i o n , c o n s i s t e n t w i t h a n i o n i c mechanism o f s o o t f o r m a t i o n .
I n summary, we h a v e measured t o t a l i o n c o n c e n t r a t i o n p r o f i l e s
i n a s e r i e s o f p r e m i x e d , l o w p r e s s u r e C H / 0 f l a m e s (2.7 k P a , 50
cm s " u n b u r n e d v e l o c i t y ) .
I n r i c h s o o t i n g flames, t h e i o n concen
t r a t i o n i s o b s e r v e d t o m a x i m i z e a t two d i s t a n c e s f r o m t h e b u r n e r .
The maximum c l o s e s t t o t h e b u r n e r i s a t t r i b u t e d t o n o r m a l c h e m i i o n i z a t i o n w h i l e t h e s e c o n d maximum h a s b e e n shown t o c o n t a i n many
l a r g e i o n s a s w e l l a s a number o f t h e s m a l l e r i o n s o b s e r v e d i n t h e
f i r s t maximum. W i t h i n c r e a s i n g f u e l r i c h n e s s f r o m n o n s o o t i n g t o
h e a v i l y s o o t i n g f l a m e s , t h e peak i o n c o n c e n t r a t i o n i n t h e f i r s t
maximum d e c r e a s e s m o n o t o n i c a l l y .
The i o n c o n c e n t r a t i o n a t t h e
s e c o n d maximum, w h i c h b e g i n s t o a p p e a r i n f l a m e s n e a r t h e c r i t i c a l
e q u i v a l e n c e r a t i o f o r s o o t f o r m a t i o n ( = 2.4 t o 2 . 5 ) , a l s o d e
c r e a s e s w i t h f u e l e n r i c h m e n t w e l l beyond . T h i s d i f f e r s from t h e
o b s e r v a t i o n s r e p o r t e d by D e l f a u e t a l . (9) f o r a s e r i e s o f i n
c r e a s i n g l y r i c h e r low pressure C H /0 /N flames i n which the i o n
c o n c e n t r a t i o n i n t h e s e c o n d maximum i s l o w e s t a t a n e q u i v a l e n c e
r a t i o j u s t t o t h e r i c h s i d e ( a b o u t 0.1 e q u i v a l e n c e u n i t s ) o f .
The s o u r c e o f t h e s e c o n d maximum ( i n i o n s and n e u t r a l s ) i s n o t
c l e a r b u t i t seems t o be r e l a t e d t o s o o t p r e c u r s o r s .
The peak i o n c o n c e n t r a t i o n i n t h e w e l l - s t u d i e d = 3.0 f l a m e
(2.7 k P a , 50 cm s " ) h a s b e e n e s t a b l i s h e d t o be a b o u t 5 1 0 cm"
by two v a s t l y d i f f e r e n t t e c h n i q u e s i n two l a b o r a t o r i e s . T h i s c o n
c e n t r a t i o n i s comparable t o t h e n e u t r a l and charged soot concen
t r a t i o n s determined by a t h i r d technique i n a t h i r d l a b o r a t o r y .
D i f f e r e n c e s i n s p a t i a l i o n and c h a r g e d p a r t i c l e c o n c e n t r a t i o n p r o 1 0
1 0
45
Flames
- 3

46
f i l e s c a n be a t l e a s t p a r t l y a t t r i b u t e d t o d i s c r i m i n a t i o n e f f e c t s
i n t h e v a r i o u s t e c h n i q u e s u s e d . The i o n c o n c e n t r a t i o n s a r e s u f f i
c i e n t l y h i g h t o p r o v i d e i o n i c p r e c u r s o r s f o r t h e soot produced
l a t e r i n t h i s flame.
We c o n c l u d e t h a t t h e i o n i c s o o t f o r m a t i o n
mechanism r e m a i n s v i a b l e .
Acknowledgment s
T h i s work was s u p p o r t e d b y t h e A i r F o r c e O f f i c e o f S c i e n t i f i c Re
s e a r c h (AFSC) u n d e r C o n t r a c t F49620-81-C-0030.
The U n i t e d S t a t e s
Government i s a u t h o r i z e d t o r e p r o d u c e and d i s t r i b u t e r e p r i n t s f o r
governmental purposes n o t w i t h s t a n d i n g any c o p y r i g h t n o t a t i o n h e r e
on.
Literature Cited
1. Olson, D.B.; Calcote, H.F., in "Eighteenth Symposium (Inter
national) on Combustion"; The Combustion Institute: Pitts
burgh, 1981; p. 453.
2. Olson, D.B.; Calcote, H.F., in "Particulate Carbon: Formation
During Combustion"; Siegla, D.C.; Smith, G.W., Eds.; Plenum:
New York, 1981; p. 177.
3. Calcote, H.F. Combust. Flame 1981, 42, 215.
4. Homann, K.H. Ber. Bunsenges. Phys. Chem. 1978, 83, 738.
5. Homann, K.H.; Stroefer, ., in "Soot in Combustion Systems
and Its Toxic Properties"; Lahaye, J.; Prado, G., Eds.;
Plenum: New York, 1983; p. 217.
6. Calcote, H.F., in "Soot in Combustion Systems and Its Toxic
Properties"; Lahaye, J.; Prado, G., Eds.; Plenum: New York,
1983; p. 197.
7. Goodings, J.M.; Tanner, S.C.; Bohme, D.K. Can. J. Chem. 1982,
60, 2766.
8. Michaud, P.; Delfau, J.L.; Barassin, ., in "Eighteenth Sym
posium (International) on Combustion"; The Combustion Insti
tute: Pittsburgh, 1981; p. 443.
9. Delfau, J.L.; Michaud, P.; Barassin, A. Combust. Sci. Techn.
1979, 20, 165.
10. Haynes, B.S.; Wagner, H.Gg. Progr. Energy Combust. Sci. 1981,
7, 229.
11. Olson, D.B.; Calcote, H.F., in "Eighteenth Symposium (Inter
national) on Combustion"; The Combustion Institute: Pitts
burgh, 1981; Comments by Wagner, H.Gg. and authors' reply,
p. 463.
12. Olson, D.B.; Calcote, H.F., in "Particulate Carbon: Formation
During Combustion"; Siegla, D.C.; Smith, G.W., Eds.; Plenum:
New York, 1981; Comments by Ulrich, G.D. and Lahaye, J., pp.
201, 203.
13. Calcote, H.F., in "Eighth Symposium (International) on Com
bustion"; Williams and Wilkins: Baltimore: 1962; p. 184.

3. KEIL ET AL.
Ion Concentrations in Acetylene-Oxygen Flames
14. Clements, R.M.; Smy, P.R. J. Appl. Phys. 1969, 40, 4553.
15. Keil, D.G.; Olson, D.B.; G i l l , R.J.; Calcote, H.F., in prepa
ration for Combust. Flame, 1983.
16. Bonne, U.; Wagner, H.Gg. Ber. Bunsenges. Phys. Chem. 1965,
69, 35.
17. Reported in: Prado, G.P.; Howard, J.B., in "EvaporationCombustion of Fuels"; Zung, J.T., Ed.; American Chemical
Society: Washington, DC, 1978; p. 153.
18. Griffin, G.W.; Dzidic, I.; Carroll, D.I.; Stillwell; R.N.,
Horning, E.C. Anal. Chem. 1973, 45, 1204.
19. Hagen, D.F. Anal. Chem. 1979, 51, 870.
20. Howard, J.B.; Prado, G.P., Comments and Delfau et al. re
plies, Combust. Sci. Techn. 1980, 22, 189.
21. Wersborg, B.L.; Howard, J.B.; Williams, G.C. in "Fourteenth
Symposium (international) on Combustion"; The Combustion In
stitute: Pittsburgh, 1973; p. 929.
22. Bittner, J.D.; Howard, J.B.; in "Particulate Carbon: Forma
tion During Combustion"; Siegla, D.C.; Smith, G.W., Eds.:
Plenum: New York, 1981; p. 109.
23. Homann, K.H.; Wagner, H.Gg., in "Eleventh Symposium (Interna
tional) on Combustion"; The Combustion Institute: Pittsburgh,
1967; p. 371.
RECEIVED December 21, 1983

47
4
Reactivities and Structures of Some Hydrocarbon
Ions and Their Relationship to Soot Formation
JOHN R. EYLER
Department of Chemistry, University of Florida, Gainesville, FL 32611
+
The reactions of three ions, C H3 , C H +, and C H +,

which have been sampled from fuel-rich and sooting
flames, have been studied with a variety of flame
neutrals using an ion cyclotron resonance (icr) mass
spectrometer.
Three different mass spectrometric
techniques have been used to differentiate isomeric
forms of the ions whose reaction rate coefficients
were measured. These include icr reactivity differ
ences, reactive collisions in a triple quadrupole mass
spectrometer, and collision-induced dissociaton reac
tions in a reversed-geometry, double-focusing mass
spectrometer. As a complement to experimental work,
theoretical calculations have been carried out to
predict the visible and ultraviolet absorption spectra
of several isomeric forms of C H3 and C H5 , as well
as the relative stability of a number of isomeric
forms of the latter ion. The structure determination
and the ion/molecule reactivity studies both provide
results consistent with and supportive of recently
proposed ionic mechanisms for soot nucleation.
3
The e x i s t e n c e o f i o n s i n f l a m e s has been known f o r many y e a r s ,

w i t h L a n g m u i r p r o b e s (1) and mass s p e c t r o m e t r i c s a m p l i n g (2) u s e d
i n a number o f t h e e a r l y i n v e s t i g a t i o n s .
H o w e v e r , i o n number
d e n s i t i e s were f o u n d t o be much h i g h e r t h a n c o u l d be e x p l a i n e d by
e q u i l i b r i u m thermal i o n i z a t i o n at the temperatures occuring i n
flames.
C a l c o t e (3) f i r s t s u g g e s t e d t h e c h e m i i o n i z a t i o n mechanism
CH* + 0 + HCO + e "
+
(1)
w h i c h i s now g e n e r a l l y a c c e p t e d as t h e most i m p o r t a n t i o n f o r m a t i o n mechanism i n many f l a m e s .

I n r e c e n t y e a r s a number o f g r o u p s
( 4 - 7 ) have used i m p r o v e d mass s p e c t r o m e t r i c s a m p l i n g t e c h n i q u e s t o
0097-6156/84/0249-0049506.00/0
50
o b t a i n d e t a i l e d p r o f i l e s o f i o n s i n b o t h f u e l - l e a n and - r i c h
f l a m e s , and t o e x p l a i n t h e i o n c h e m i s t r y i n v o l v e d i n t h e f o r m a t i o n
and l o s s o f t h e o b s e r v e d i o n s ( 8 ) . S i n c e most c o m b u s t i o n
pro
c e s s e s have been shown t o p r o c e e d v i a n e u t r a l and f r e e - r a d i c a l
r e a c t i o n s , the importance of i o n s i n combustion
( a s opposed t o
t h e i r e x i s t e n c e ) has n o t been e s t a b l i s h e d . One a r e a o f c o m b u s t i o n
c h e m i s t r y where i o n s and i o n / m o l e c u l e r e a c t i o n s may p l a y a c r i t i
c a l r o l e , and w h i c h has been e m p h a s i z e d i n o u r s t u d i e s t o d a t e , i s
t h a t of soot n u c l e a t i o n i n f u e l - r i c h flames.
A r e c e n t r e v i e w by C a l c o t e (9) d i s c u s s e s many o f t h e p r o p o s e d
mechanisms o f s o o t n u c l e a t i o n , b o t h n e u t r a l and i o n i c , and p r e s
e n t s t h e c a s e f o r an i o n / m o l e c u l e scheme, b e g i n n i n g w i t h CoH^
and
sequentially
a d d i n g p r i m a r i l y a c e t y l e n e and p o l y a c e t y l e n e
molecules
i n rapid
condensation
and c o n d e n s a t i o n - e l i m i n a t i o n
r e a c t i o n s which l e a d t o p o l y c y c l i c a r o m a t i c hydrocarbon i o n s of
m/z 500 - 1000 amu.
This p a r t i c u l a r ion/molecule soot n u c l e a t i o n
m o d e l has been e l u c i d a t e d f u r t h e r i n an a r t i c l e by C a l c o t e and
O l s o n ( 10) where a s e r i e s o f i o n / m o l e c u l e r e a c t i o n s were combined
w i t h a c e t y l e n e o x i d a t i o n r e a c t i o n s and a c o m p u t a t i o n a l
model
developed.
T h i s model gave i o n p r o f i l e s r e a s o n a b l y s i m i l a r t o
those a c t u a l l y observed
i n s o o t i n g f l a m e s , and a l s o p r e d i c t e d
c o n c e n t r a t i o n s o f i o n s s u f f i c i e n t l y h i g h t h a t t h e y m i g h t be c o n
s i d e r e d as s o o t n u c l e a t i o n s i t e s . A s p e c t s o f an i o n i c mechanism
f o r s o o t n u c l e a t i o n a r e d i s c u s s e d i n more d e t a i l i n a n o t h e r a r t i
c l e i n t h i s v o l u m e , so no more w i l l be s a i d a t t h i s p o i n t about
t h e g e n e r a l f e a t u r e s o f t h e scheme.
I t s h o u l d be n o t e d , h o w e v e r ,
t h a t o b j e c t i o n s t o i t have been r a i s e d r e c e n t l y ( 1 1 ) .
Our work i n t h i s a r e a has been prompted by a number o f weak
n e s s e s o f t h e i o n / m o l e c u l e s o o t n u c l e a t i o n scheme o f C a l c o t e and
O l s o n ( 10) ( n o t e d by t h e a u t h o r s i n t h e i r a r t i c l e ) .
V e r y few
e x p e r i m e n t a l s t u d i e s have been c a r r i e d out t o d e t e r m i n e t h e r a t e
c o e f f i c i e n t s f o r r e a c t i o n s of s m a l l hydrocarbon ions w i t h v a r i o u s
flame n e u t r a l s .
N o t i n g t h i s l a c k o f d a t a , C a l c o t e and O l s o n s e t
a l l r a t e c o e f f i c i e n t s i n t h e i r model t o t h e ( n o t u n r e a s o n a b l e )
v a l u e o f 2 10~
cm / s . As w i l l be s e e n l a t e r i n t h i s a r t i c l e ,
a l a r g e number o f i s o m e r i c s t r u c t u r e s a r e p o s s i b l e f o r e v e n s m a l l
h y d r o c a r b o n i o n s , and l i t t l e , i f a n y , r e l i a b l e t h e r m o c h e m i c a l d a t a
e x i s t s f o r any o f them.
C a l c o t e and O l s o n , i n t h e i r m o d e l , c h o s e
what seemed t o be t h e most r e a s o n a b l e s t r u c t u r e f o r many o f t h e
i o n s i n v o l v e d , and e s t i m a t e d h e a t s o f f o r m a t i o n i n t h e many c a s e s
where none c o u l d be found i n t h e l i t e r a t u r e .
In an a t t e m p t t o p r o v i d e more a c c u r a t e d a t a on i o n / m o l e c u l e
r e a c t i o n s , i o n s t r u c t u r e s , and i o n t h e r m o c h e m i s t r y w h i c h may be
r e l e v a n t t o s o o t f o r m a t i o n , we have i n i t i a t e d a p r o g r a m t o o b t a i n
such i n f o r m a t i o n i n c o n t r o l l e d l a b o r a t o r y s t u d i e s .
Ion/molecule
r e a c t i o n r a t e c o e f f i c i e n t s f o r t h e r e a c t i o n s o f m a j o r (and i n i
t i a l l y low m o l e c u l a r w e i g h t ) i o n i c s p e c i e s found i n f u e l - r i c h and
s o o t i n g f l a m e s w i t h a v a r i e t y o f f l a m e n e u t r a l s have been and a r e
c o n t i n u i n g t o be d e t e r m i n e d .
We have used s e v e r a l mass s p e c t r o
m e t r i c t e c h n i q u e s , i n c l u d i n g i o n c y c l o t r o n resonance
( i c r ) mass

4.
Hydrocarbon
EYLER
Ions and Soot
Formation
51
spectrometry,
triple
quadrupole
tandem mass s p e c t r o m e t r y , and
c o l l i s i o n - i n d u c e d d i s s o c i a t i o n i n a r e v e r s e d - g e o m e t r y ZAB-2F mass
s p e c t r o m e t e r t o probe t h e s t r u c t u r e s o f s m a l l hydrocarbon
ions.
And we have complemented o u r e x p e r i m e n t a l s t u d i e s w i t h t h e o r e t i c a l
c a l c u l a t i o n s o f t h e e n e r g i e s and s p e c t r a o f c e r t a i n i o n s whose
s t r u c t u r e s a r e n o t w e l l e s t a b l i s h e d . The r e m a i n d e r o f t h i s a r t i
c l e w i l l d i s c u s s o u r work on t h r e e i o n i c systems w h i c h a r e s e e n i n
e a r l y stages of t h e ion/molecule chemistry i n f u e l r i c h flames:
CU*
,C H
and C H .
+
Experimental
The m a j o r i t y o f t h e s t u d i e s t o be r e p o r t e d h e r e have been c a r r i e d
out u s i n g i o n c y c l o t r o n r e s o n a n c e mass s p e c t r o m e t r y .
This v a r i a
t i o n o f mass s p e c t r o m e t r y and i t s many a p p l i c a t i o n s have been
d i s c u s s e d i n d e t a i l i n s e v e r a l r e v i e w a r t i c l e s ( 1 2 - 1 4 ) and a t
l e a s t one book ( 1 5 ) . B r i e f l y , i t u s e s c o m b i n a t i o n s o f s t a t i c
e l e c t r i c and m a g n e t i c f i e l d s t o t r a p gaseous i o n s a t l o w p r e s s u r e s
for
t i m e p e r i o d s o f up t o s e v e r a l s e c o n d s i n d u r a t i o n .
During
t h e s e l o n g t r a p p i n g p e r i o d s , t h e i o n s c a n be s u b j e c t e d t o e l e c t r o
magnetic r a d i a t i o n , o f t e n from tunable l a s e r s , t o study
their
spectroscopic properties, or their r e a c t i v i t y with various neutral
compounds p r e s e n t i n t h e t r a p p i n g r e g i o n c a n be f o l l o w e d .
With
t h e p u l s e d i c r method ( 16) d e t e r m i n a t i o n o f i o n / m o l e c u l e r e a c t i o n
r a t e c o e f f i c i e n t s f o r q u a s i - t h e r m a l i o n s a t temperatures from c a .
300 t o s e v e r a l h u n d r e d h i g h e r c a n be made i n a s t r a i g h t f o r w a r d
manner ( 1 7 - 1 9 ) .
The s t r u c t u r e s o f i s o m e r i c i o n s c a n a l s o be
probed w i t h t h i s t e c h n i q u e s i n c e i o n s o f d i f f e r e n t s t r u c t u r e o f t e n
e x h i b i t d i f f e r e n t r e a c t i v i t i e s toward
selected neutrals.
This
a p p r o a c h was f i r s t employed by G r o s s and c o - w o r k e r s
( 20) i n a
s t u d y o f C^H, i s o m e r s , and h a s been u t i l i z e d more r e c e n t l y by
A u s l o o s and L i a s ( 2 1 - 2 2 ) f o r C H
and C ^ H ^ i o n s .
F o r one s t u d y i n v o l v i n g t h e d i f f e r e n t i a t o n o f C ^ H ^ i s o m e r s ,
a F i n n i g a n t r i p l e q u a d r u p o l e mass s p e c t r o m e t e r was e m p l o y e d .
This
t y p e o f mass s p e c t r o m e t r i c i n s t r u m e n t a t i o n h a s been d e s c r i b e d i n
s e v e r a l p u b l i c a t o n s ( 2 3 - 2 4 ) and h a s been a p p l i e d t o a number o f
p r o b l e m s ( 2 5 - 2 6 ) i n a n a l y t i c a l c h e m i s t r y . The f i r s t q u a d r u p o l e i s
used t o s e l e c t an i o n o f i n t e r e s t , t h e s e c o n d , i n a n r f - o n l y mode,
i s used as a t r a p i n w h i c h t h e i o n u n d e r g o e s ( i n o u r case r e a c
t i v e ) c o l l i s i o n s w i t h a s e l e c t e d n e u t r a l g a s , and t h e t h i r d q u a
d r u p o l e i s used t o a n a l y z e t h e r e s u l t s o f t h o s e c o l l i s i o n s .
Work
on C,H^ s t r u c t u r e d i f f e r e n t i a t i o n was c a r r i e d o u t on a VG A n a l y
tical
Instruments
ZAB-2F r e v e r s e - g e o m e t r y
d o u b l e - f o c u s i n g mass
spectrometer (27) a t the Naval Research Laboratory i n Washington,
DC.
U s i n g t h e MIKES-CID ( 2 8 ) a p p r o a c h , a p a r t i c u l a r m/z i o n i s
passed through t h e magnetic s e c t o r o f t h e s p e c t r o m e t e r and, w i t h
k i n e t i c e n e r g y u s u a l l y i n t h e 4-8 keV r a n g e , c o l l i d e s w i t h a g a s
i n t h e second f i e l d f r e e r e g i o n .
The p r o d u c t s o f t h i s c o l l i s i o n
a r e e n e r g y a n a l y z e d by an e l e c t r o s t a t i c a n a l y z e r , w i t h t h i s i n f o r
mation
then
related
t o t h e mass o f t h e c o l l i s i o n
products.
+

52
T h e o r e t i c a l s t u d i e s on i o n s t r u c t u r e s and s p e c t r a were c a r r i e d out

u s i n g i n i t i a l l y t h e Amdahl 450-V7 and more r e c e n t l y t h e IBM 3081D
computer of t h e N o r t h e a s t R e g i o n a l D a t a C e n t e r a t t h e U n i v e r s i t y
o f F l o r i d a , and a D i g i t a l Equipment C o r p . VAX 11/780 m i n i c o m p u t e r
i n the Quantum T h e o r y P r o j e c t a t UF.
Results
CoHo^.
3 3
m a j o r i o n sampled f r o m a w i d e range of f u e l T i c h a n d s o o t i n g f l a m e s , and has been t a k e n as t h e s t a r t i n g p o i n t
f o r t h e i o n i c s o o t f o r m a t i o n scheme p r o p o s e d by C a l c o t e and O l s o n
( a l t h o u g h t h e r e i s s t i l some u n c e r t a i n t y as t o i t s e x a c t f o r m a t i o n
mechanism i n c e r t a i n f l a m e s ) ( 1 0 ) .
Two i s o m e r i c s t r u c t u r e s a r e
important i n d i s c u s s i n g i t s r o l e i n flame systems.
The f i r s t i s
t h e c y c l o p r o p e n y l i u m i s o m e r , I , w h i c h has been most o f t e n formed
i s
t n e
H
C
and s t u d i e d i n mass s p e c t r o m e t r i c and t h e o r e t i c a l work t o d a t e .

T h i s i s g e n e r a l l y r e c o g n i z e d as the most s t a b l e C^H^
isomer, w i t h
a t h e o r e t i c a l l y c a l c u l a t e d h e a t of f o r m a t i o n of 253 k c a l / m o l
(29),
w h i c h i s i n q u i t e good agreement w i t h t h e 256 2 k c a l / m o l d e t e r mined ( 3 0 ) by e x p e r i m e n t .
C^H^"*" i o n s p o s s e s s i n g t h i s s t r u c t u r e
can be formed f o r s t u d y i n a mass s p e c t r o m e t e r by e l e c t r o n i m p a c t
on a number of p r e c u r s o r s , i n c l u d i n g aline (C^H^) and t h e v a r i o u s
p r o p a r g y l h a l i d e s (C^H^X).
A second and p o t e n t i a l l y more i m p o r tant C^H^
s t r u c t u r e i s t h a t of t h e l i n e a r p r o p a r g y l i u m i o n , I I .
+
C = = C
H
II

4.
EYLER
Hydrocarbon
Ions and Soot
53
Formation
The h e a t o f f o r m a t i o n o f t h i s i o n has been c a l c u l a t e d ( 2 9 ) t o be

31-34 k c a l / m o l h i g h e r t h a n t h a t o f t h e c y c l o p r o p e n y l i u m i o n , a g a i n
i n f a i r agreement w i t h t h e 25 k c a l / m o l d i f f e r e n c e f o u n d ( 3 0 )
experimentally.
F a r l e s s t h e o r e t i c a l and e x p e r i m e n t a l a t t e n t i o n
has been g i v e n t h i s f o r m o f t h e C^H^"" i o n , a l t h o u g h t h e r e was a t
l e a s t one s u g g e s t i o n ( 3 1 ) t h a t i t m i g h t be i m p o r t a n t i n f l a m e s .
Mass s p e c t r o m e t r i c s t u d y o f t h e p r o p a r g y l i u m
i s o m e r h a s become
more s t r a i g h t f o r w a r d w i t h t h e r e p o r t ( 3 2 ) by A u s l o o s and L i a s t h a t
s i g n i f i c a n t f r a c t i o n s o f t h e i s o m e r c a n be p r o d u c e d by c h a r g e
t r a n s f e r reactions of small ions ( A r , X e , C 0 , N e , etc.) w i t h
p r o p a r g y l c h l o r i d e and b r o m i d e .
Work i n o u r l a b o r a t o r i e s h a s
shown t h a t even h i g h e r p r o p o r t i o n s o f I I r e l a t i v e t o I c a n be
obtained
by e i t h e r e l e c t r o n i m p a c t on o r c h a r g e exchange w i t h
p r o p a r g y l i o d i d e ( s y n t h e s i z e d by a h a l i d e exchange r e a c t i o n w i t h
propargyl bromide).
O t h e r i s o m e r i c C^H^* s t r u c t u r e s have been
c a l c u l a t e d ( 2 9 ) t o be 1 eV o r h i g h e r i n e n e r g y t h a n I I , and have
not been s e r i o u s l y s t u d i e d o r d i s c u s s e d i n c o n n e c t i o n w i t h f l a m e
mechanisms.
1
Because of i t s s t a b i l i t y , t h e c y c l o p r o p e n y l i u m
i o n , I , has
been t h o u g h t t o be r e l a t i v e l y u n r e a c t i v e t o w a r d s i m p l e h y d r o c a r b o n
fuels.
T h i s has been c o n f i r m e d i n a s t u d y ( 3 3 ) by w o r k e r s f r o m
t h e N a t i o n a l B u r e a u o f S t a n d a r d s , who found t h a t I was u n r e a c t i v e
with
ethylene,
aline, and more i m p o r t a n t l y ,
a c e t y l e n e and
diacetylene.
T h i s i s o m e r i c f o r m o f t h e i o n d i d show moderate
r e a c t i v i t y t o w a r d some h y d r o c a r b o n s s u c h as i s o - C ^ H g , t r a n s - 2 p e n t a n e , and 1 , 3 - c y c l o - C ^ H g .
I o n s w i t h t h e s t r u c t u r e I I were
q u i t e r e a c t i v e w i t h many o r t h e 26 n e u t r a l s p e c i e s s t u d i e d . I n
p a r t i c u l a r , r e a c t i o n o f I I w i t h a c e t y l e n e p r o d u c e d C5H3 and C^Hc
i o n p o p u l a t i o n s w i t h r e a c t i v e and u n r e a c t i v e components.
The
r e a c t i v e i s o m e r s o f t h e s e i o n s combined w i t h a c e t y l e n e t o f o r m
CyH
i o n s , which probably possessed a s t a b l e , c y c l i c s t r u c t u r e .
I t t h u s a p p e a r s t h a t i f an i o n i c s o o t f o r m a t i o n mechanism s i m i l a r
t o t h a t p r o p o s e d by C a l c o t e
( 9 ) i s important
i n combustion
systems, the l i n e a r , propargylium
i o n , II,
i s the important
reactive precursor.
A s u g g e s t i o n h a s been made ( 3 4 ) t h a t C^H^"" d o e s n o t r e a c t
s e q u e n t i a l l y w i t h a c e t y l e n e t o form s m a l l p o l y c y c l i c i o n s , but
r a t h e r d i r e c t l y w i t h aromatic n e u t r a l s (benzene, t o l u e n e , methyln a p h t h a l e n e s , i n d e n e ) t o f o r m t h e i n i t i a l p o l y c y c l i c i o n s i n one
step.
W h i l e t h e s e n e u t r a l s have o n l y been seen as m i n o r compon e n t s i n f l a m e s , t h e i r r e a c t i o n s w i t h C ^ H ^ may n o n e t h e l e s s be
important
s i n c e t h e y would e l i m i n a t e 3-5 s e q u e n t i a l
acetylene
r e a c t i o n s , each w i t h i t s p o s s i b i l i t y f o r b r a n c h i n g i n t o u n r e a c t i v e
as w e l l as r e a c t i v e s p e c i e s . We have used ( 3 5 ) e l e c t r o n i m p a c t on
p r o p a r g y l i o d i d e t o p r o d u c e b o t h c y c l o p r o p e n y l i u m and p r o p a r g y l i u m
i o n s i n o u r i c r mass s p e c t r o m e t e r
and t h e n s t u d i e d t h e i r s u b s e quent
ion/molecule
reactions
with
small
aromatic
neutral
molecules.
The r e s u l t s f o r b o t h i o n i c s t r u c t u r e s a r e g i v e n i n
Table I , along w i t h the expected r a t e c o e f f i c i e n t c a l c u l a t e d
a s s u m i n g a n i o n - i n d u c e d d i p o l e model ( 3 6 ) .
One sees t h a t as w i t h
x

54
other hydrocarbon s p e c i e s , the propargylium i o n r e a c t s

quite
r a p i d l y w i t h a l l of the n e u t r a l s , w h i l e the c y c l o p r o p e n y l i u m form
r e a c t s slower or not at a l l .
These r e s u l t s i n d i c a t e t h a t d i r e c t
r e a c t i o n o f ^* w i t h c y c l i c n e u t r a l s may i n d e e d be an i m p o r t a n t
c h a n n e l i n an i o n i c s o o t f o r m a t i o n mechanism, s i n c e t h e r a t e
c o e f f i c i e n t s are quite high.
However, i m p o r t a n c e o f t h i s c h a n n e l
relative
t o s e q u e n t i a l a c e t y l e n e a d d i t i o n r e a c t i o n s cannot be
a s s e s s e d u n t i l more o f t h e r a t e c o e f f i c i e n t s , i o n i c s t r u c t u r e s ,
and h e a t s of f o r m a t i o n have been d e t e r m i n e d f o r t h e r e a c t i o n s i n
t h e l a t t e r scheme.
Table I .
R a t e C o e f f i c i e n t s f o r Some R e a c t i o n s o f C^H-j
+
+ Reactant Neutral
Reactant Neutral
Cyclic
C H
3
Acetylene
(C2H2)
- P r o d u c t s
Linear
Langevin
N.R.
12
11
Benzene
(C^H^)
N.R.
15
16
Toluene
(CyHg)
0.17
15-20
16
Naphthalene
(C
H )
0.17
7.0
13
N.R
5.7
2-Methylnaphthalene ( n i o ^
0.21
1.6
Indene
4.4
18-20
1 Q
1-Methylnaphthalene
(C^H^)
c
(CgHg)
A l l r a t e c o e f f i c i e n t s i n cm /s 10 .
N.R. = no r e a c t i o n o r r e a c t i o n l e s s t h a n c e l l
= not c a l c u l a t e d .
loss.
The r e a c t i v i t y o f t h e p r o p a r g y l i u m f g r m and t h e n o n r e a c t i v i t y o f t h e c y c l o p r o p e n y l i u m f o r m o f C^H^

toward a c e t y l e n e
l e d t o d e v e l o p m e n t o f a new mass s p e c t r o m e t r i c t e c h n i q u e f o r t h e
d i f f e r e n t i a t i o n of s t r u c t u r a l isomers. I n c o l l a b o r a t i o n (37) w i t h
D r s . Y o s t and F e t t e r o l f i n o u r d e p a r t m e n t we have used r e a c t i v e
c o l l i s i o n s o f low k i n e t i c e n e r g y i o n s i n t h e c e n t e r q u a d r u p o l e of
a t r i p l e q u a d r u p o l e mass s p e c t r o m e t e r t o d i f f e r e n t i a t e between t h e
two i s o m e r i c forms of C^H/**. C^H^
i o n s were formed by e l e c t r o n
i m p a c t on p r o p a r g y l c h l o r i d e , b r o m i d e , and i o d i d e , m a s s - s e l e c t e d
i n t h e f i r s t q u a d r u p o l e , t h e n p a s s e d i n t o t h e second q u a d r u p o l e
w i t h e n e r g i e s o f 2-20 eV where t h e y r e a c t e d w i t h a c e t y l e n e ^
Ions
r e s u l t i n g f r o m t h e s e r e a c t i o n s , as w e l l as u n r e a c t e d C^H^
ions,
w e r e t h e n m a s s - a n a l y z e d i n t h e t h i r d q u a d r u p o l e . The i n t e n s i t y o f
C
, formed by t h e r e a c t i o n o f t h e p r o p a r g y l i u m form o f C
+

4.
EYLER
Hydrocarbon
Ions and Soot
Formation
with acetylene,
increased s l i g h t l y r e l a t i v e to unreacted C3H3
when propargyl bromide instead of c h l o r i d e was used as precursor
of
; a marked increase was seen when propargyl iodide was
used.
These r e s u l t s are consistent with i c r ion r e a c t i v i t y data
that show e l e c t r o n impact upon propargyl iodide produces predomi
nantly the l i n e a r , propargylium C ^ H ^ i o n , while use of
the
bromide or c h l o r i d e produces almost e x c l u s i v e l y the c y c l o p r o p e n y l
ium i o n .
Since quadrupole mass spectrometers have been employed i n
some flame sampling s t u d i e s , our d i f f e r e n t i a t i o n of ion s t r u c t u r e s
with a t r i p l e quadrupole instrument suggests the p o s s i b i l i t y of
a c t u a l l y determining the s t r u c t u r e s of selected ions sampled mass
s p e c t r o m e t r i c a l l y from flames.
Such s t r u c t u r e determination could
serve to confirm, or f u r t h e r e l u c i d a t e , an i o n i c soot n u c l e a t i o n
pathway.
The number d e n s i t i e s determined for C^H^"*" ions i n s e v e r a l
experimentally studied flames are s u f f i c i e n t l y high that use of
l a s e r induced fluorescence
( l i f ) might be considered as a r e l a
t i v e l y n o n - i n t r u s i v e probe for mapping the i n t e n s i t y d i s t r i b u t i o n
of these ions i n the flame.
However, some knowledge of the ener
gies of the various excited states of the ions i s necessary before
a serious attempt at using l i f can be made.
The excited s t a t e
energetics depend, of course, on the s t r u c t u r e of the C ^ H ^ isomer
under c o n s i d e r a t i o n .
No experimental determination of the excited
states of e i t h e r form of the ion considered here has been c a r r i e d
out.
One rather complete t h e o r e t i c a l c a l c u l a t i o n has been p e r
formed (38) on the cyclopropenylium i o n , with the SCF LCAO-MO CI
r e s u l t s i n d i c a t i n g that the f i r s t excited s i n g l e t of the i o n l i e s
some 8.5 eV above the ground s t a t e .
The e x c i t a t i o n wavelength f o r
lif
studies on t h i s s t r u c t u r e would thus be ca. 146 nm, shorter
than that c u r r e n t l y a v a i l a b l e from commercial l a s e r s .
However^
one might expect that the l i n e a r , propargylium form of the C3H3
ion would possess l o w e r - l y i n g excited s t a t e s .
No c a l c u l a t i o n of
the excited state energetics of t h i s s t r u c t u r a l isomer has been
performed.
In c o l l a b o r a t i o n with D r s . Zerner and Edwards of the
U n i v e r s i t y of F l o r i d a Quantum Theory P r o j e c t , we are c u r r e n t l y
i n v e s t i g a t i n g t h i s problem. A spectroscopic INDO program (39) has
been used to obtain e x c i t a t i o n energies for the propargylium
structure,
and to confirm the e a r l i e r (38)
results
for
the
cyclopropenylium i o n .
Several low l y i n g excited s t a t e s , i n the
range 3-5 eV above the ground s t a t e , have been p r e d i c t e d , but a l l
are symmetry forbidden to f i r s t o r d e r , and the forbiddeness i s not
broken by v i b r o n i c c o u p l i n g .
A second, more d e t a i l e d set of
c a l c u l a t i o n s , i n c o l l a b o r a t i o n with Drs. Sabin and Oddershede,
using a p o l a r i z a t i o n propagator method (40) has produced r e s u l t s
somewhat
more promising than reported above.
A transition
r e q u i r i n g 5.36 ev energy (corresponding to a photon wavelength of
231 nm) with an o s c i l l a t o r strength of 0.14 has been p r e d i c t e d .
This t r a n s i t i o n might be excited
by l a s e r
r a d i a t i o n from a
frequency doubled dye l a s e r mixed with the fundamental output of a
Nd:YAG pump l a s e r .
Thus l i f d e t e c t i o n of l i n e a r , propargylium
+
55

56
C3H3 i o n s i n f l a m e s i s a p o s s i b i l i t y , a l t h o u g h i n t e r f e r e n c e s f r o m
other
(possibly
aromatic)
s p e c i e s e x c i t e d by l i g h t
i n this
w a v e l e n g t h r e g i o n would have t o be e l i m i n a t e d .
^ H ^ .
The C^H^" " i o n , a l t h o u g h n o t a m a j o r i o n i n a c e t y l e n e
Tlames, has been s e e n i n c e r t a i n o t h e r s t u d i e s ( 4 1 ) , i n c l u d i n g
t h o s e p r o b i n g benzene f l a m e s .
We a l s o o b s e r v e d t h i s i o n i n one o f
our e a r l y i n v e s t i g a t i o n s ( 4 2 ) o f s e q u e n t i a l i o n / m o l e c u l e r e a c t i o n s
i n a c e t y l e n e , where i t was p r o d u c e d by t h e r e a c t i o n o f C ^ H ^ i o n s
w i t h t h e p a r e n t n e u t r a l compound.
Similar to the i c r result
d i s c u s s e d above f o r C ^ H ^ , t h e C ^ H ^ i o n was p r o d u c e d as a m i x t u r e
o f isomers^, one r e a c t i v e toward a c e t y l e n e , and one u n r e a c t i v e . As
w i t h CUH^ , t h e two most l i k e l y i s o m e r i c s t r u c t u r e s a r e a c y c l i c
one I I I , t h e p h e n y l i u m i o n , and an a c y c l i c i o n IV.
+
H
III
IV
An ab i n i t i o ( 4 3 ) and a MINDO/3 ( 4 4 ) c a l c u l a t i o n have g i v e n somewhat d i f f e r i n g v a l u e s f o r t h e heat o f f o r m a t i o n o f t h e p h e n y l i u m

i o n ( 2 8 0 v s . 245 k c a l / m o l , a l t h o u g h see r e f . 44 f o r a d i s c u s s i o n
which resolves t h i s d i f f i c u l t y ) .
E x p e r i m e n t a l AH v a l u e s a r e i n
t h e r a n g e 266-270 k c a l / m o l ( 4 5 , 4 6 ) . S i m i l a r l y , t h e open c h a i n
i s o m e r IV has been c a l c u l a t e d t o have a heat o f f o r m a t i o n 17 and
16 k c a l / m o l h i g h e r t h a n t h e p h e n y l i u m by t h e ab i n i t i o and MINDO/3
calculations, respectively.
The MINDO/3 r e s u l t s g i v e s u b s t a n t i a l l y h i g h e r heats of f o r m a t i o n f o r o t h e r i s o m e r i c forms.
We used b o t h i c r r e a c t i v i t y s t u d i e s and c o l l i s i o n - i n d u c e d
d i s s o c i a t i o n ( c i d ) i n a ZAB-2F d o u b l e - f o c u s i n g ,
reversed-geometry
mass s p e c t r o m e t e r t o s t u d y t h e s t r u c t u r e s o f C ^ H c i s o m e r s ( 4 7 ) .
B o t h l i n e s o f i n v e s t i g a t i o n made u s e o f t h e e a r l i e r r e p o r t ( 4 8 )
t h a t C ^ H ^ i o n s p o s s e s s i n g t h e p h e n y l i u m s t r u c t u r e c o u l d be formed
by p r o t o n t r a n s f e r t o h a l o b e n z e n e s ,
f o l l o w e d by t h e l o s s o f H X .
I o n s s o formed i n t h e i c r mass s p e c t r o m e t e r were found t o be
unreactive
toward
acetylene,
indicating
that
i n sequential
i o n / m o l e c u l e r e a c t i o n s i n a c e t y l e n e , t h e p h e n y l i u m C^-Hc i s o m e r i s
f

4.
Hydrocarbon
EYLER
Ions and Soot
57
Formation
unreactive and the a c y c l i c isomer IV i s the r e a c t i v e species*

This conclusion was f u r t h e r borne out by an extensive s e r i e s of
cid experiments c a r r i e d out i n c o l l a b o r a t i o n with Dr. J . E . Campana
at the Naval Research Laboratory.
^6 5
*formed i n a
v a r i e t y of ways:
d i r e c t e l e c t r o n impact on a number of n e u t r a l
precursors;
proton-assisted
dehydrohalogenation reactions
like
those shown (48) to produce phenylium i o n s ; and s e q u e n t i a l ace
tylene ion/molecule r e a c t i o n s .
The l a t t e r two formation schemes
were c a r r i e d out i n the mass spectrometer's high-pressure chemical
i o n i z a t i o n source.
Mass selected C ^ H ^ ions were i n v e s t i g a t e d
using both charge s t r i p p i n g (49) reactions and fragmentation i n t o
C^H^
and C^Hg i o n s , where the t h e o r e t i c a l c a l c u l a t i o n s
(44)
predicted that the a c y c l i c isomer should produce r e l a t i v e l y more
of the l a t t e r i o n . Both classes of high energy processes v e r i f i e d
that
the r e a c t i v e
isomer produced by s e q u e n t i a l
ion/molecule
reactions
i n acetylene
has the a c y c l i c s t r u c t u r e IV and the
unreactive isomer possesses the phenylium s t r u c t u r e .
Thus s i m i l a r
behavior ( a c y c l i c r e a c t i v e , c y c l i c unreactive) has been found for
both C H
and C H
ions.
H
o n s
C^H^.
Reaction of the propargylium form of CoH~"*" with acetylene
"Has" been shown ( 33) to produce both C ^ H ^ ana C ^ H .
In flame
sampling experiments the l a t t e r ion i s u s u a l l y more abundant (34)
(although under c e r t a i n c o n d i t i o n s , the r e l a t i v e abundances of the
two product ions are reversed (50)).
Our work to date has concen
trated on C ^ H ^ because i t can be formed i n r e l a t i v e l y high abun
dance i n our i c r mass spectrometer from a number of n e u t r a l p r e
cursors.
There i s s u b s t a n t i a l confusion, however, as to the
r e l a t i v e s t a b i l i t y of the s e v e r a l p o s s i b l e isomeric s t r u c t u r e s of
this ion.
Most t h e o r e t i c a l studies (51) have concentrated on the
c y c l i c structure, V,
+
V
while some experimental work was i n t e r p r e t e d (52) i n terms of both
a c y c l i c and an a c y c l i c isomer.
However, a number of other s t r u c
tures , as seen i n Figure 1, can be e n v i s i o n e d , and a few of even
the more u n l i k e l y looking of these have been the subject of
t h e o r e t i c a l c a l c u l a t i o n s (53).
We have formed C H
ions from
four n e u t r a l precursors and studied t h e i r r e a c t i o n s with various
flame molecules.
In a d d i t i o n , because of the lack of a consistent
5

PROCESSES

4.
EYLER
Hydrocarbon
Ions and Soot
Formation
59
theoretical
treatment
of the energetics of the many p o s s i b l e
isomeric forms of C c H ^ , we have c a r r i e d out MINDO/3 c a l c u l a t i o n s
on many of them, and more d e t a i l e d ab i n i t i o c a l c u l a t i o n s on three
of them.
Two d i f f e r e n t primary i o n i z a t i o n schemes were employed to
form C ^ H ^ i o n s .
The f i r s t was conventional e l e c t r o n impact on
cyclopentadiene, d i c y c l o p e n t a d i e n e , l-penten-3-yne, and norbornadiene.
The second involved charge t r a n s f e r reactions i n the i c r
analyzer c e l l from CO to norbornadiene (54). Results (55) of
these r e a c t i v i t y studies are given i n Tables II - V.
As can be
seen, d i f f e r e n t n e u t r a l precursors produce isomers of d i f f e r i n g
r e a c t i v i t y , ranging from quite slow ( c a . 3 10
cc/s i n Table
IV) to very high ( c a . 5 1 0 ~
i n Table I V ) . Because of uncer
t a i n t y i n the i d e n t i t y of the various C c H ^ s t r u c t u r a l isomers, we
have l a b e l l e d them simply A-D i n the Tables. The r e a c t i o n c o e f f i
cients determined f o r isomer A are at the lower range of those
which can be conveniently measured by the i c r technique, and may
represent non-reactive ion loss from the i c r analyzer c e l l .
+
10
Table I I .
Rate C o e f f i c i e n t s for Some Reactions of C c H

Formed from Cyclopentadiene
C H
5
+
5
Ions
+ Reactant Neutral * Products

Ion Structure
Reactant Neutral
Acetylene
Aline
0.20
0.45
0.32
0.16
0.62
0.27
(C~H,)
Benzene
Toluene
Naphthalene
1-Methylnaphthalene
2- Methylnaphthalene
Indene
All
rate c o e f f i c i e n t s
0.54
0.56
0.22
0.18
0.21
0.39
i n cm /s
10

60
Table I I I .
Rate C o e f f i c i e n t s f o r Some Reactions of CjH^ Ions

Formed from Dicyclopentadiene
+ Reactant Neutral Products
Ion S t r u c t u r e
Reactant N e u t r a l
Acetylene
Ethylene
Propane
1,3-Butadiene
Aline
0.71
0.49
0.70
0.72
0.38
Benzene
Toluene
Naphthalene
1-Methylnaphthalene
2-Methylnaphthalene
Indene
0.93
1.10
0.31
0.33
0.39
0.46
All
rate c o e f f i c i e n t s
Table IV.
i n cm /s 10
Rate C o e f f i c i e n t s for Some Reactions of C H

from l-penten-3-yne
5
C H
5
+
5
Formed
+ Reactant Neutral + Products

Ion Structure
Reactant Neutral
Acetylene
Ethylene
Propane
Methane
1,3-Butadiene
Aline
0.070
0.050
0.070
0.030
0.16
0.020
0.40
2.9
1.10
0.60
2.5
2.3
Benzene
Toluene
Naphthalene
1-Methylnaphthalene
2-Methylnaphthalene
Indene
0.40
0.30
0.030
N.R.
0.023
0.090
3.4
4.0
1.0
0.70
3.0
8.0
A l l rate c o e f f i c i e n t s i n cm /s 10
N.R. = no r e a c t i o n or r e a c t i o n less than c e l l
loss.

4.
Hydrocarbon
EYLER
T a b l e V
Ions and Soot
61
Formation
R a t e C o e f f i c i e n t s f o r Some R e a c t i o n s o f C H
Formed f r o m N o r b o r n a d i e n e
5
C H
5
+
5
+
5
Ions
+ Reactant N e u t r a l + Products
Ion S t r u c t u r e
Reactant N e u t r a l
Acetylene
Ethylene
Propane
Methane
1,3-Butadiene
Aline
0.20
0.23
0.63
0.53
Benzene
Toluene
Naphthalene
1- M e t h y l n a p h t h a l e n e
2-M e t h y l n a p h t h a l e n e
Indene
0.51
4.4
0.27
0.20
2.4
8.6
All
2.7
2.2
3
10
r a t e c o e f f i c i e n t s i n cm /s 10 .
Isomers and C, whose r a t e c o e f f i c i e n t s d i f f e r by l e s s t h a n a

f a c t o r o f two i n most c a s e s , may a c t u a l l y be t h e same i s o m e r
formed w i t h d i f f e r i n g d e g r e e s o f i n t e r n a l e x c i t a t i o n .
However,
t h e s u b s t a n t i a l r e a c t i v i t y d i f f e r e n c e s between A and o r C, and
o r C and D, l e a d us t o t h e c o n c l u s i o n t h a t a t l e a s t t h r e e , and
p o s s i b l y f o u r , d i f f e r e n t i s o m e r i c s t r u c t u r e s a r e formed f r o m t h e s e
precursors.
To a i d i n i s o m e r i c i d e n t i f i c a t i o n i n t h e C^H^ r e a c t i o n s , we
u n d e r t o o k a s e r i e s o f MINDO/3 c a l c u l a t i o n s t o d e t e r m i n e t h e h e a t s
o f f o r m a t i o n o f t h e s t r u c t u r e s shown i n F i g u r e 1. The MINDO/3
method h a s been d e m o n s t r a t e d t o g i v e q u i t e r e a s o n a b l e r e s u l t s f o r
g e o m e t r i e s and h e a t s o f f o r m a t i o n o f b o t h n e u t r a l and p o s i t i v e l y
charged hydrocarbon s p e c i e s ( 5 6 ) .
We used a g r a d i e n t g e o m e t r y
o p t i m i z a t i o n r o u t i n e w i t h a m o d i f i e d MINDO/3 p r o g r a m on o u r campus
Amdahl 450-V7 c o m p u t e r .
The r e s u l t s ( 5 5 ) a r e shown i n T a b l e V I ,
where t h e l o w e s t e n e r g y i s o m e r i s p r e d i c t e d t o be t h e v i n y l c y c l o propenylium i o n , w i t h s e v e r a l a c y c l i c isomers next h i g h e s t i n
e n e r g y , and some o f t h e c y c l i c s p e c i e s h i g h e r s t i l l .
MINDO/3 i s
known t o have s e v e r a l d e f i c i e n c i e s , i n c l u d i n g u n d e r e s t i m a t i o n o f
s m a l l r i n g s t r a i n and p r e d i c t i o n o f t h e s t a b i l i t y o f t r i p l e bonds
ca. 5 k c a l / m o l t o o l o w . S i n c e t h e lowest heat o f f o r m a t i o n found
i n o u r c a l c u l a t i o n s was f o r a compound w i t h a three-membered r i n g ,
and s i n c e t h e a c y c l i c i s o m e r s c o n t a i n t r i p l e b o n d s , t h e MINDO/3
+

62
Table VI.
MINDO/3 R e s u l t s f o r 0 ,- I s o m e r s
Structure*
m
1,
k,
j,
i,
h
c,
f,
e,
d,
b,
a,
AH
g
Dc ,
triplet
cis-"linear"
trans-"linear"
"linear"
vinylcyclopropenylium
h
Figure 1 for structural
(kcal/mol)
288
270
268
266
257
256
255
253
252
247
242
238
pyramid
D^ ,
singlet
dimethyleneeyclopropenylium
methylenecyclobutenylium
*See t e x t and
details.
r e s u l t s are suspect.
We have t h u s c h o s e n t h r e e i s o m e r i c f o r m s , a ,
b and c f r o m F i g u r e 1 and c a r r i e d out ab i n i t i o c a l c u l a t i o n s u s i n g
a 4-31G
b a s i s s e t and a m o d i f i e d G a u s s i a n 80 ( 57) package on our
Quantum T h e o r y P r o j e c t VAX 11/780 computer.
These more d e t a i l e d
c a l c u l a t i o n s c o n f i r m t h e o r d e r of s t a b i l i t y f o r the t h r e e i s o m e r s
f o u n d u s i n g MINDO/3. We a r e c u r r e n t l y u s i n g a f o u r t h o r d e r manybody p e r t u r b a t i o n t h e o r y
package ( 5 8 ) w h i c h i n c l u d e s
single,
d o u b l e and q u a d r u p l e e x c i t a t i o n s t o see i f the r e l a t i v e s t a b i l i
ties
of
the
three
isomeric
forms
chosen
shift
further.
P r e l i m i n a r y r e s u l t s show t h a t i s o m e r s a and b have e s s e n t i a l l y t h e
same h e a t of f o r m a t i o n , w h i l e t h e ^ of c r e m a i n s c a . 15 k c a l / m o l
higher.
The r e l a t i v e s t a b i l i t y o r d e r p r e d i c t e d by our MINDO/3 c a l c u
l a t i o n s has
l e d to a t e n t a t i v e assignment of
isomers,
a l t h o u g h t h i s may have t o be m o d i f i e d when f i n a l r e s u l t s of the
more d e t a i l e d quantum m e c h a n i c a l c a l c u l a t i o n s d i s c u s s e d above a r e
available.
We
a s s i g n the v i n y l c y c l o p r o p e n y l i u m s t r u c t u r e
(a)
c a l c u l a t e d t o be l o w e s t i n e n e r g y , t o the u n r e a c t i v e i s o m e r A.
The m o d e r a t e l y r e a c t i v e i s o m e r s and C, w h i c h may be t h e same
i s o m e r w i t h d i f f e r e n t amounts of i n t e r n a l e n e r g y , we a s s i g n t o one
o r more of t h e a c y c l i c forms s i m i l a r t o b i n F i g u r e 1. The h i g h l y
r e a c t i v e i s o m e r , D, we a s s i g n the n e x t h i g h e r e n e r g y c y c l i c s t r u c
t u r e , c, f r o m F i g u r e
1.
R e a c t i v i t y d i f f e r e n c e s between the
s p e c i e s A and o r C, and o r C and D a r e so g r e a t t h a t we
b e l i e v e t h e y a r e t h e r e s u l t of the i o n s p o s s e s s i n g
different
i s o m e r i c s t r u c t u r e s , and not j u s t c o n t a i n i n g d i f f e r i n g amounts o f
i n t e r n a l energy. I f t h i s s t r u c t u r a l assignment proves c o r r e c t , i t
p r o v i d e s a d i f f e r e n t c a s e f r o m t h a t w h i c h h e l d f o r C^H^"" and
1

4.
EYLER
Hydrocarbon
Ions and Soot
63
Formation
C^Hc . Now the c y c l i c isomer i s less s t a b l e , and more r e a c t i v e ,

with the a c y c l i c less r e a c t i v e , and a d i f f e r e n t , mixed c y c l i c and
l i n e a r s t r u c t u r e (the v i n y l c y c l o p r o p e n y l i u m ion) i s the l e a s t
reactive species.
A synthesis of both experimental and t h e o r e t i c a l
results
generated by e a r l i e r workers and our group s t i l l seems i n s u f f i
cient to determine c o n c l u s i v e l y which isomeric s t r u c t u r e should be
assigned to the various r e a c t i v e species which have been observed
experimentally.
The technique of p h o t o d i s s o c i a t i o n of gaseous
ions trapped i n an i c r mass spectrometer has been used s u c c e s s
fully
for s t r u c t u r a l i d e n t i f i c a t i o n
i n a number of
previous
studies ( 59),
and we hope to apply i t to the present
case.
However, i t i s necessary to have some idea of the approximate
spectra of the various C ^ H ^ isomers which might be expected, i n
order to see i f they are s u f f i c i e n t l y d i f f e r e n t that s t r u c t u r a l
d i f f e r e n t i a t i o n might be accomplished.
A l s o , some idea of the
p o s i t i o n s of various absorption bands i s necessary i n order to
know which l i g h t sources (and most often which wavelengths of
tunable l a s e r s ) must be used for the p h o t o d i s s o c i a t i o n .
In
c o l l a b o r a t i o n with Drs. Zerner and Edwards of the UF Quantum
Theory P r o j e c t , we have t h e o r e t i c a l l y predicted the spectra of
four C5H5*" isomers, using the INDO s p e c t r a l p r e d i c t i o n program
(39).
Results are shown i n Figure 2 for four of the p o s s i b l e
isomeric s t r u c t u r e s given i n Figure 1.
One sees that at l e a s t one
i s predicted to have a moderately intense absorption band i n the
near u l t r a v i o l e t r e g i o n , which should be a c c e s s i b l e by e i t h e r
excimer-pumped or Nd:YAG-pumped dye l a s e r s (but unfortunately not
by our e x i s t i n g flashlamp-pumped dye l a s e r ) .
With an improved
laser
c a p a b i l i t y (or perhaps using m u l t i p l e photon i r
laserinduced d i s s o c i a t i o n (60) with our cw CO2 l a s e r ) , we should be
able to assign more completely the C^H^ isomeric s t r u c t u r e s .
Conclusion
Studies of the s t r u c t u r e and r e a c t i v i t i e s of the three ions d i s
cussed i n t h i s a r t i c l e have continued to bear out the p o s s i b i l i t y
of an i o n i c mechanism for soot formation.
The r e a c t i o n rate
c o e f f i c i e n t s are c e r t a i n l y rapid and i n general l a r g e r than those
used by Olson and Calcote (10) i n t h e i r model, at l e a s t for c e r
t a i n isomeric forms of the ions and at the temperatures of ca. 325
used i n our work.
However, u n t i l more s o p h i s t i c a t e d
flamesampling mass spectrometers are employed, the exact isomeric form
of the many ions seen i n flames cannot be known, and thus cannot
be r e l a t e d d i r e c t l y to our work. As i s to be expected, d e t a i l s of
the r e a c t i v i t y or n o n r e a c t i v i t y of various isomers vary as one
moves from one i o n i c species to another.
Thus i n some cases
(C^H^ ) a c y c l i c forms are less r e a c t i v e , while the c y c l i c isomers
react r a p i d l y , while i n others (C^H^" ", C^H/ ") the opposite i s the
case.
Those channels where the c y c l i c Ions are l e s s r e a c t i v e
suggest an opportunity f o r the formation of c y c l i c neutrals i n
1


10,000
en
u
<a
"Linear"
Ring
Photon Energy/cm'
+40 ,000
+
50,000
11
F i g u r e 2.
Theoretically predicted spectra of four 0
f r o m F i g u r e 1.
20,000
h, P l a n a r
430,000
Vinylcyclopropenylium
c, Bent Ring (26)
b,
a,
isomers
+
60 ,000
70
m
in
m
C/3
"0
00
00
4.
EYLER
Hydrocarbon
Ions and Soot
Formation
65
flames by ion recombination with electrons or hydride transfer

reactions.
Our findings on the r e a c t i v i t y of C3H3
ions with
aromatic n e u t r a l s suggest that this may be an important channel i n
the formation of larger c y c l i c i o n s , as postulated e a r l i e r (34).
While i s o l a t e d
laboratory experiments
involving
reactions
which may be important i n flames provide information under con
t r o l l e d c o n d i t i o n s , these conditions may be somewhat removed from
those which are found i n flames.
C l e a r l y our r e a c t i o n rate d e t e r
minations should be extended to higher temperatures, which may
cause the a s s o c i a t i o n reactions seen to have lower r a t e s , due to
d i s s o c i a t i o n of the ion/molecule r e a c t i o n complexes formed. A l s o ,
studies at higher pressures should be performed, where there i s
increased opportunity for c o l l i s i o n a l s t a b i l i z a t i o n of the c o l l i
sion complexes.
As data from work i n our l a b o r a t o r i e s and those
of others accumulate, they can be used to r e f i n e computational
models such as those already reported (10), i n order to more f u l l y
t e s t the proposed i o n i c soot formation mechanism.
Acknowledgments
Acknowledgment i s made to the Donors of The Petroleum
Fund, administered by the American Chemical S o c i e t y ,
p a r t i a l support of this r e s e a r c h .
Research
for
the
Literature Cited
1. Lawton, J.; Weinberg, F.J. "Electrical Aspects of Combus
tion"; Clarendon Press: Oxford, 1969.
2. Knewstubb, P.F.; Sugden, T.M. Nature 1958, 181, 1261.
3. Calcote, H.F. in "Eighth Symp. (Int'l.) on Combustion"; Wil
liams and Wilkins Co.: Baltimore, 1962; p. 184.
4. Hayhurst, A.N.; Kittelson, D.B. Combustion and Flame 1978,
31, 37.
5. Delfau, J.L.; Michaud, P.; Barassin, A. Combust. Sci. and
Tech. 1979, 20, 165.
6. Olson, D.B.; Calcote, H.F. in "Eighteenth Symp. (Int'l.) on
Combustion"; The Combustion Institute: Pittsburgh, 1981; p.
453.
7. Goodings, J.M.; Bohme, D.K.; Sugden, T.M. in "Sixteenth Symp.
(Int'l.) on Combustion"; The Combustion Institute, Pitts
burgh, 1977; p. 891.
8. Goodings, J.M.; Bohme, D.K.; Ng, C.-W. Combustion and Flame
1979, 36, 27.
9. Calcote, H.F. Combustion and Flame 1981, 42, 215.
10. Olson, D.B.; Calcote, H.F. in "Particulate Carbon Formation
during Combustion"; Siegla, D.C.; Smith, G.W., Eds.; Plenum:
New York, 1981; p. 177.
11. Goodings, J.M.; Tanner, S.D.; Bohme, D.K. Can. J. Chem. 1982,
60, 2766.

66
PROCESSES
12. Baldeschwieler, J.D.; Woodgate, S.S. Accts. Chem. Res. 1971,

4, 114.
13. Beauchamp, J.L. Ann. Rev. Phys. Chem. 1971, 22, 527.
14. Henis, J.M.S. in "Ion-Molecule Reactions, Vol. 2"; Franklin,
J.L., Ed.; Plenum: New York, 1972; p. 395.
15. Lehman, T.A.; Bursey, M.M. "Ion Cyclotron Resonance Spectrom
etry"; Wiley: New York, 1976.
16. McIver, R.T., Jr., Rev. Sci. Instrum. 1978, 49, 111.
17. Ausloos, P.; Eyler, J.R.; Lias, S.G. Chem. Phys. Lett. 1975,
30, 21.
18. Aue, D.H.; Bowers, M.T. in "Gas Phase Ion Chemistry, Vol. 2";
Bowers, M.T., Ed.; Academic: New York, 1979, p. 2.
19. Bartmess, J.E.; McIver, R.T., Jr., in "Gas Phase Ion Chem
istry, Vol. 2"; Bowers, M.T., Ed.; Academic: New York, 1979;
p. 88.
20. Gross, M.L.; Russell, D.H.; Aerni, R.J.; Bronczyk, S.A. J.
Am. Chem. Soc. 1977, 99, 3603.
21. Jackson, J.A.A.; Lias, S.G.; Ausloos, P. J. Am. Chem. Soc.
1977, 99, 7515.
22. Ausloos, P. J. Am. Chem. Soc. 1981, 103, 3931.
23. Yost, R.A.; Enke, C.G. Anal. Chem. 1979, 51, 1251A.
24. Slayback, J.R.B.; Story, M.S. Ind. Res. Dev., February 1981,
128.
25. Fetterolf, D.D.; Yost, R.A. Mass Spectrom. Rev. 1983, 2, 1.
26. Brotherton, H.D.; Yost, R.A. Anal. Chem. 1983, 55, 549.
27. Morgan, R.P.; Beynon, J.H.; Bateman, R.H.; Green, B.N. Int.
J. Mass. Spectrom. Ion Phys. 1978, 28, 171.
28. Cooks, R.G. in "Collision Spectroscopy"; Cooks, R.G., Ed.;
Plenum: New York, 1978.
29. Radom, L.; Hariharan, P.C.; Pople, J.A.; Schleyer, P.v.R. J.
Am. Chem. Soc. 1976, 98, 10.
30. Lossing, F.P. Can. J. Chem. 1972, 50, 3973.
31. Knewstubb, P.F.; Sugden, T.M. in "Seventh Symp. (Int'l) on
Combustion"; Butterworths: London, 1959, p. 247.
32. Ausloos, P.J.; Lias, S.G. J. Am. Chem. Soc. 1981, 103, 6505.
33. Smyth, K.C.; Lias, S.G.; Ausloos, P. Combust. Sci. and Tech.
1982, 28, 147.
34. Michaud, P.; Delfau, J.L.; Barrasin, A. in "Eighteenth Symp.
(Int'l) on Combustion"; The Combustion Institute: Pitts
burgh, 1981, p. 433.
35. Brill, F.W.; Baykut, M.G.; Eyler, J.R., manuscript in prepar
ation.
36. Giomousis, G.; Stevenson, D.P. J. Chem. Phys. 1958, 29, 294.
37. Fetterolf, D.D.; Yost, R.A.; Eyler, J.R. Org. Mass Spectrom.,
in press.
38. Takada, T.; Ohno, K. Bull Chem. Soc. Japan 1979, 52, 334.
39. Ridley, J.; Zerner, M. Theor. Chim. Acta 1973 32, 111.
40. Oddershede, J. in "Advances in Quantum Chemistry, Vol. II";
Lowdin, P.O., Ed.; Academic: New York, 1978; p. 275.

4.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
EYLER
Hydrocarbon Ions and Soot Formation
67
Vinckier, C.; Gardner, M.P.; Bayes, K.D. in "Sixteenth Symp.

(Int'l.) on Combustion"; The Combustion Institute: Pitts
burgh, 1976, p. 881.
B r i l l , F.W.; Eyler, J.R. J. Phys. Chem. 1981, 85, 1091.
Dill, J.D.; Schleyer, P.v.R.; Brinkley, J.S.; Seeger, R.;
Pople, J.A.; Haselbach, E. J. Am. Chem. Soc. 1976, 98, 5428.
Tasaka, M.; Ogata, M.; Ichikawa, H. J. Am. Chem. Soc. 1981,
103, 1885.
McMahon, T.B. Ph.D. Thesis, California Institute of Technol
ogy, Pasadena, 1973.
Rosenstock, H.M.; Larkins, J.T.; Walker, J. A. Int. J. Mass.
Spectrom. Ion Phys. 1973, 11, 309.
Eyler, J.R.; Campana, J.E. Int. J. Mass. Spectrom. Ion
Phys., in press.
Speranza, M.; Sefcik, M.D.; Henis, J.M.S.; Gaspar, P.P. J.
Am. Chem. Soc. 1977, 99, 5583.
Ast, T. in "Advances in Mass Spectrometry, 8B"; Quayle, .,
Ed.; Heyden & Son, Ltd.: London, 1980; p. 555.
Olson, D.B., personal communication.
Borden, W.T.; Davidson, E.R. J. Am. Chem. Soc. 1979, 101,
3771.
Occolowitz, J.L.; White, G.L. Aust. J. Chem. 1968, 21, 997.
Stohrer, W.D.; Hoffman, R. J. Am. Chem. Soc. 1972, 94, 1661.
Buckley, T.J. Ph.D. Thesis, university of Florida, Gaines
ville, 1982 and Lias, S.G.; Ausloos, P.; Buckley, T.J., un
published results.
B r i l l , F.W. Ph.D. Thesis, University of Florida, Gaines
ville, 1983.
Bingham, R.C.; Dewar, M.J.S.; Lo, D.H. J. Am. Chem. Soc.
1975, 97, 1285.
Available from Quantum Chemistry Program Exchange, Department
of Chemistry, Indiana University.
Bartlett, R.J.; Purvis, G.D. Phys. Scr. 1980, 21, 255.
Dunbar, R.C. in "Gas Phase Ion Chemistry, Vol. 2"; Bowers,
M.T., Ed.; Academic: New York, 1979; Ch. 14.
Bomse, D.S.; Berman, D.W.; Beauchamp, J.L. J. Am. Chem. Soc.
1981, 103, 3967.
RECEIVED November 30,
1983

5
Nitrogen Chemistry in Flames
Observations and Detailed Kinetic Modeling
A N T H O N Y M . D E A N , M A U - S O N G C H O U , and D A V I D S T E R N
Corporate ResearchScience Laboratories, Exxon Research and Engineering Company,

Linden, NJ 07036
Spatially resolved concentration measurements of

NH, NH2, NH3, NO and OH in atmospheric pressure
ammonia flames are compared to predictions obtained
with a one-dimensional flame algorithm using a
detailed reaction mechanism. Several reactions
were observed to be equilibrated, and this informa
tion was used to obtain estimates of the oscillator
strength for NH2 as well as the heat of formation
of NH. Use of a conventional mechanism of ammonia
oxidation predicted concentration profiles in marked
disagreement with the observations. However, it was
possible to obtain much more satisfactory fits
to the data by including reactions between various
NHi (i = 1-2) species to form N-N bonds; these
adducts could then decompose to form ultimately N2.
These good fits were obtained with rate constants
estimated from unimolecular decomposition theory
and used with no adjustments.
Recent advances i n b o t h l a s e r d i a g n o s t i c i n s t r u m e n t a t i o n and
computer m o d e l i n g a l g o r i t h m s have p r o v i d e d k i n e t i c i s t s w i t h
e x c i t i n g new o p p o r t u n i t i e s f o r c h a r a c t e r i z a t i o n o f c o m p l e x chemi c a l s y s t e m s . I n t h i s p a p e r we d e s c r i b e o u r u s e o f t h e s e t o o l s
t o e l u c i d a t e t h e k i n e t i c s o f n i t r o g e n s p e c i e s i n f l a m e s . Our
e f f o r t s h a v e f o c u s e d upon ammonia o x i d a t i o n s i n c e i t c a n b e
shown t o p l a y a k e y r o l e i n t e r m s o f NO p r o d u c t i o n i n f u e l - b o u n d n i t r o g e n f l a m e s ( 1 ) a s w e l l a s NO r e d u c t i o n v i a NH3 a d d i t i o n t o
f l u e gas i n t h e T h e r m a l DeNO p r o c e s s ( 2 , 3 ) . A l t h o u g h t h e r e
h a v e b e e n a h o s t o f p r e v i o u s s t u d i e s o f ammonia o x i d a t i o n i n
b o t h s h o c k t u b e s (4) and f l a m e s ( 5 ) , c o n s i d e r a b l e a m b i g u i t y
r e m a i n s w i t h r e s p e c t t o t h e d e t a i l s o f t h e mechanism. We h a v e
a t t e m p t e d t o remove some o f t h e s e u n c e r t a i n t i e s b y m e a s u r i n g
a b s o l u t e c o n c e n t r a t i o n s o f b o t h s t a b l e s p e c i e s and r e a c t i v e
i n t e r m e d i a t e s t h r o u g h t h e f l a m e f r o n t r e g i o n and c o m p a r i n g t h e s e
c o n c e n t r a t i o n - d i s t a n c e p r o f i l e s t o those o b t a i n e d by n u m e r i c a l l y
x
0097-6156/84/0249-0071 $06.00/0
72
s o l v i n g t h e 1-D f l a m e e q u a t i o n s .
A d i s c u s s i o n o f t h e measurement
t e c h n i q u e s i s f o l l o w e d by t h e m e c h a n i s t i c a n a l y s i s .
P o r t i o n s of
t h i s m a t e r i a l h a v e b e e n c o v e r e d i n more d e t a i l i n o u r r e c e n t
papers (6-8).
Experimental
A r r a n g e m e n t and
Observations
F i g u r e 1 shows a s c h e m a t i c o f t h e a p p a r a t u s .
T h i s has been
d e s c r i b e d i n d e t a i l i n R e f s . 6 and 7; o n l y an o v e r v i e w i s p r e
sented here.
The 3.8 cm d i a m e t e r b u r n e r i s d e s i g n e d t o p r o d u c e a
f l a t h o r i z o n t a l f l a m e f r o n t s o t h a t one c a n map o u t t h e f l a m e
c h e m i s t r y by m e a s u r i n g s p e c i e s c o n c e n t r a t i o n s a t v a r i o u s v e r t i c a l
d i s t a n c e s above t h e b u r n e r s u r f a c e . T h i s g e o m e t r y a l l o w s one t h e
considerable s i m p l i f i c a t i o n of u t i l i z i n g a one-dimensional flame
code f o r t h e k i n e t i c a n a l y s i s .
The l a s e r beam i s f o c u s e d t o g i v e
a c o n s t a n t beam d i a m e t e r o f "w0.15 mm a c r o s s t h e f l a m e .
Again
t h i s s i m p l i f i e s the i n t e r p r e t a t i o n of the l i n e - o f - s i g h t absorption
measurements. F u r t h e r m o r e , t h i s s m a l l d i a m e t e r p e r m i t s good
s p a t i a l r e s o l u t i o n of the flame f r o n t region.
I n our atmospheric
p r e s s u r e f l a m e s , t h e f l a m e f r o n t was l e s s t h a n 1 mm t h i c k .
A v e r a g i n g techniques were used f o r c o l l e c t i o n o f b o t h a b s o r p t i o n
and f l u o r e s c e n c e d a t a , w i t h 100 l a s e r p u l s e s p e r d a t a p o i n t b e i n g
typical.
The l a r g e t e m p e r a t u r e g r a d i e n t s n e a r t h e b u r n e r s u r f a c e
c a u s e d some beam s t e e r i n g , b u t d i r e c t measurement showed t h i s
d e f l e c t i o n t o be n e g l i g i b l e , i . e . , l e s s t h a n 0.08 mm, a t d i s t a n c e s
l a r g e r t h a n 0.3 mm a b o v e t h e s u r f a c e .
The gas m i x t u r e s f e d t o t h e b u r n e r w e r e p r e p a r e d i n a s t a i n
l e s s s t e e l m a n i f o l d u s i n g e l e c t r o n i c f l o w c o n t r o l l e r s . A range
o f r i c h ammonia f l a m e s was s t u d i e d i n w h i c h t h e f u e l e q u i v a l e n c e
r a t i o r a n g e d f r o m 1.28 t o 1.81. F l a m e t e m p e r a t u r e s w e r e m e a s u r e d
w i t h P t / P t - 1 3 % R h t h e r m o c o u p l e s . The b e a d d i a m e t e r was o n l y 0.12
mm so t h a t t h e r a d i a t i o n c o r r e c t i o n was o n l y 80 K.
OH, NH, NH^, and NH3 w e r e measured i n a b s o r p t i o n w h i l e NO
was m e a s u r e d i n f l u o r e s c e n c e .
The a b s o r p t i o n measurements w e r e
reduced to c o n c e n t r a t i o n s v i a curve-of-growth techniques w h i l e
t h e NO measurements w e r e c a l i b r a t e d a g a i n s t a b s o r p t i o n i n a l e a n
ammonia f l a m e w h e r e t h e NO c o n c e n t r a t i o n was h i g h e r .
I t was
assumed t h a t t h e e x t e n t o f f l u o r e s c e n c e q u e n c h i n g was t h e same i n
t h e r i c h and l e a n f l a m e s ( 7 ) . S u f f i c i e n t s p e c t r o s c o p i c i n f o r m a
t i o n was a v a i l a b l e f o r a l l b u t NH2 t o a l l o w a b s o l u t e c o n c e n t r a t i o n
a s s i g n m e n t s . N H d a t a c o u l d o n l y be o b t a i n e d a s [NH^] f , w h e r e
f ^ was t h e unknown o s c i l l a t o r s t r e n g t h .
S i n c e t h e OH a b s o r p t i o n measurements w e r e made o n i n d i v i d u a l
r o t a t i o n a l l i n e s , i t was p o s s i b l e t o o b t a i n [ 0 H ] j . A s s u m i n g a
B o l t z m a n n d i s t r i b u t i o n f o r t h e r o t a t i o n a l e n e r g y l e v e l s , one c a n
o b t a i n the r o t a t i o n a l temperature from a p l o t of ln[0H]j versus
. An example o f s u c h d a t a i s shown i n F i g u r e 2.
#


YAG-PUMPED
DYE LASER/WEX
REF.
DETECTOR
SPECTROMETER
FLAT FLAME
P.M.T.
SAMPLE
DETECTOR
BOX-CAR
AVERAGER
RATIOMETER/
AVERAGER
F i g u r e 1. S c h e m a t i c d i a g r a m o f t h e e x p e r i m e n t a l a r r a n g e m e n t s f o r
l a s e r absorption and l a s e r - i n d u c e d f l u o r e s c e n c e .
(Reproduced
w i t h p e r m i s s i o n f r o m R e f . 7 C o p y r i g h t 193, J . Chem. P h y s . )
BEAM SPLITTER
74
-4.8 H
1.28
= .9 mm
T , = 2239 20
rn
-6.4 H
1
0
500
1 1
1000 1500 2000 2500 3000
3500
-1
ROTATIONAL ENERGY (cm )

F i g u r e 2 . Measurement o f OH r o t a t i o n a l t e m p e r a t u r e a t a h e i g h t
o f 0 . 9 mm above t h e b u r n e r f o r an ammonia f l a m e w i t h a n e q u i v a
l e n c e r a t i o o f 1 . 2 8 . (Reproduced w i t h p e r m i s s i o n from Ref. 6 .
C o p y r i g h t 1 9 8 2 , J . Chem. P h y s . )

5.
DEAN ET AL.
75
NH2 O s c i l l a t o r S t r e n g t h .
As mentioned e a r l i e r , l a c k o f a r e l i
a b l e o s c i l l a t o r s t r e n g t h f o r NH2 p r e v e n t e d a s s i g n m e n t o f a b s o l u t e
c o n c e n t r a t i o n s . However, we w e r e a b l e t o combine a b s o l u t e
measurements o f OH, NH, a n d NH3 w i t h r e l a t i v e measurements o f NH^
to demonstrate t h a t t h e r e a c t i o n s
NH
+ OH = N H
NH
+ OH = NH + H 0
+ H 0
(1)
(2)
were p a r t i a l l y e q u i l i b r a t e d .
T h i s f a c t allowed us t o c a l c u l a t e
a b s o l u t e NH2 c o n c e n t r a t i o n s a n d t h u s o b t a i n f ^ . The u s e o f two
r e a c t i o n s n o t o n l y allowed a c o n s i s t e n c y check, b u t a l s o served
t o p r o v i d e an e s t i m a t e f o r AH (NH).
The a p p r o a c h u s e d assumes t h a t H2O r a p i d l y assumes a n e q u i l i
brium c o n c e n t r a t i o n i n flames.
W i t h ^ 0 f i x e d i n t h i s way, one
can e x p l i c i t l y v e r i f y whether o r n o t R e a c t i o n s 1 and 2 a r e e q u i
l i b r a t e d by computing t h e r a t i o s :
f
[NH ].f /C[NH ].[OH])
(3)
[]/([ ]...[])
(4)
R e p r e s e n t a t i v e v a l u e s o f ( 3 ) a n d (4) a r e t a b u l a t e d i n T a b l e I .
Although t h e i n d i v i d u a l c o n c e n t r a t i o n s v a r y w i d e l y , each o f these
r a t i o s i s constant w i t h i n experimental e r r o r a t d i f f e r e n t heights
above t h e b u r n e r , i n d i c a t i n g t h a t e a c h o f t h e r e a c t i o n s i s e q u i
librated.
C a l c u l a t i o n o f K e q i s more u n c e r t a i n f o r R e a c t i o n 2
b e c a u s e o f t h e u n c e r t a i n h e a t o f f o r m a t i o n o f NH. G i v e n t h i s
u n c e r t a i n t y , one c a n v a r y AHf(NH) u n t i l f i o b t a i n e d f r o m
R e a c t i o n 2 a g r e e s w i t h t h a t o b t a i n e d f r o m R e a c t i o n 1. Such a n
a p p r o a c h y i e l d s f i = 5.05 1 0 w i t h A H f ( N H ) = 89 k c a l / m o l e .
T h i s v a l u e o f AHf ( N H ) i s c o n s i s t e n t w i t h t h e JANAF v a l u e o f
90+4 k c a l / m o l e ( 9 ) b u t h i g h e r t h a n t h e 84.22.3 k c a l / m o l e p r o p o s e d
by P i p e r ( 1 0 ) . S i n c e t h e r e a r e a d d i t i o n a l u n c e r t a i n t i e s i n
AHf(NH ) a n d t h e a b s o l u t e c o n c e n t r a t i o n o f NH3, NH, a n d OH, t h e s e
v a l u e s o f f ^ a n d AHf(NH) c a n n o t be t a k e n a s d e f i n i t i v e a s s i g n
m e n t s , b u t t h e y do r e p r e s e n t s i g n i f i c a n t i m p r o v e m e n t s o v e r e a r l i e r
work.
- 5
R o t a t i o n a l E x c i t a t i o n o f OH. One o f t h e most s u r p r i s i n g a s p e c t s

o f o u r d a t a was t h e o b s e r v a t i o n o f r o t a t i o n a l l y h o t OH i n t h e
f l a m e f r o n t o f = 1.28 a n d = 1.50 f l a m e s . R o t a t i o n a l
t e m p e r a t u r e s ^200 h i g h e r t h a n r a d i a t i o n c o r r e c t e d t h e r m o c o u p l e
measurements w e r e o b s e r v e d ; t h e s e w e r e n o t e x p e c t e d s i n c e r o t a
t i o n a l energy t r a n s f e r i s so f a s t a t atmospheric p r e s s u r e .
Such
e x c i t a t i o n was n o t o b s e r v e d b e y o n d t h e f l a m e f r o n t i n a n y o f o u r
ammonia f l a m e s a n d n o t e v e n w i t h i n t h e f l a m e f r o n t o f a methane


1.58
8.08
0.79
0.54
0.724
8.46
1935
1929
2.5
3.0
^Reference 6.
d i s t a n c e above burner s u r f a c e .
1.55
8.32
0.69
m
m
in
"0
73
c
m
H
00
in
H
1.50
8.20
1.11
0.90
0.91
1.37
0.986
+3
9.22
C m
12
10.0
/10
1938
[NH]
[NH,,]fJOH]
2;0
+3
1.52
C m
22
"
1.40
/10
1.40
^^2^ * ^ i
[OH][NH,1
2.56
12.0
17
e
[NHJ/10 cm~
1941
1.5
1.45
11
8.33
[NIL.]f /10 cm"

8.71
2.04
2.54
14
[NH]/10 cm"
5.28
= 4.79/2.81/1.00)
14.3
1938
14
1.0
Z/mm T/K [OH]/10 cm~
- 1.28 (NH /0 /N
Table I . P a r t i a l E q u i l i b r i u m i n Ammonia Flames
5.
DEAN ET AL.
11
flame.
I t a p p e a r e d t h a t t h e s o u r c e o f t h i s e x c i t e d OH was a n
e x o t h e r m i c r e a c t i o n w h i c h was u n i q u e t o t h e f l a m e f r o n t r e g i o n o f
t h e ammonia f l a m e .
A r a t e a n a l y s i s o f t h e mechanism w h i c h i s
d i s c u s s e d l a t e r i n d i c a t e s two r e a c t i o n s w h i c h s a t i s f y t h e s e
criteria:
NH
+ 0
NH + NO
NH + OH
= -14 k c a l / m o l e
= -96 k c a l / m o l e
+ OH
Both o f these r e a c t i o n r a t e s peak i n t h e flame f r o n t r e g i o n , and

b o t h h a v e t h e p o t e n t i a l t o p r o d u c e v i b r a t i o n a l l y e x c i t e d OH.
S i n c e v i b r a t i o n a l r e l a x a t i o n i s much s l o w e r t h a n r o t a t i o n a l
r e l a x a t i o n , a p p r e c i a b l e q u a n t i t i e s o f v i b r a t i o n a l l y e x c i t e d OH
c o u l d b e f o r m e d . The o b s e r v e d r o t a t i o n a l e x c i t a t i o n c o u l d r e s u l t
from cascading o f t h i s e x c i t a t i o n i n t o h i g h r o t a t i o n a l l e v e l s o f
the ground v i b r a t i o n a l l e v e l d u r i n g t h e r e l a x a t i o n p r o c e s s .
D e t a i l e d K i n e t i c Modeling.
Recent advances i n computation t e c h
n i q u e s ( 1 1 ) h a v e made i t much e a s i e r t o compute c o n c e n t r a t i o n d i s t a n c e p r o f i l e s f o r f l a m e s p e c i e s . The o n e - d i m e n s i o n a l i s o b a r i c
flame equations a r e solved v i a a steady s t a t e s o l u t i o n using
f i n i t e difference expressions.
A n added s i m p l i f i c a t i o n i s t h a t
the energy e q u a t i o n c a n be r e p l a c e d w i t h t h e measured t e m p e r a t u r e
profile.
I n t h e a d a p t i v e mesh a l g o r i t h m , t h e e q u a t i o n s a r e f i r s t
s o l v e d on a r e l a t i v e l y c o a r s e g r i d .
Then a d d i t i o n a l g r i d p o i n t s
c o u l d be i n c l u d e d i f n e c e s s a r y , and t h e p r e v i o u s s o l u t i o n i n t e r
p o l a t e d o n t o t h e new mesh w h e r e i t s e r v e d a s t h e i n i t i a l s o l u t i o n
estimate.
T h i s p r o c e s s was c o n t i n u e d u n t i l s e v e r a l t e r m i n a t i o n
c r i t e r i a were s a t i s f i e d .
The s t a r t i n g p o i n t i n d e v e l o p m e n t o f a n ammonia f l a m e mech
a n i s m was a mechanism p r e v i o u s l y u s e d t o m o d e l ammonia o x i d a t i o n
i n a f l o w t u b e n e a r 1300 ( 3 ) . A d d i t i o n a l r e a c t i o n s w e r e added
t h a t were thought t o be important a t t h e h i g h e r flame t e m p e r a t u r e s .
C a l c u l a t i o n s w i t h t h i s mechanism p r o d u c e d p r o f i l e s i n marked d i s
agreement w i t h o u r d a t a .
The p r e d i c t i o n s w e r e s l o w e r t h a n
o b s e r v e d ; d e c a y o f NH^ s p e c i e s was much t o o s l o w , a n d OH p e a k e d
t o o l a t e b y a b o u t 2.5 mm. To make m a t t e r s w o r s e , f a r t o o much NO
was f o r m e d . The NO p r o b l e m was e s p e c i a l l y t r o u b l e s o m e i n t h a t
attempts t o i n c r e a s e t h e r a t e o f N H i decay o n l y served t o produce
e v e n more NO, s i n c e NO was t h e p r i m a r y d e c a y c h a n n e l f o r t h e N H i
s p e c i e s . A p o s s i b l e r e s o l u t i o n o f t h i s dilemma i n v o l v e s r e a c t i o n s
o f t h e N H i s p e c i e s w i t h e a c h o t h e r t o f o r m N-N b o n d s .
These
c o m p l e x e s c o u l d t h e n s p l i t o f f atoms t o u l t i m a t e l y f o r m N2I n t h i s way one c o u l d a c h i e v e a n o v e r a l l f a s t e r d e c a y o f NH^
w i t h o u t p r o d u c i n g more NO. I n d e e d , c a l c u l a t i o n s u s i n g s u c h a
mechanism showed much b e t t e r a g r e e m e n t w i t h o u r d a t a .
Table I I
l i s t s t h e " c o n v e n t i o n a l " mechanism a s w e l l a s t h e a d d i t i o n a l
NHi + N H i r e a c t i o n s which d r a m a t i c a l l y improve t h e f i t . F i g u r e 3

78
T a b l e I I . M e c h a n i s m f o r R i c h Ammonia F l a m e s
k = AT
Reaction
exp(-E/RT)
(kcal/mole) Comments
UPDATED FLOW REACTOR MECHANISM

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
NH 3+M=NH 2+H+M
NH +H=NH2+H2
NH +0=NH2+OH
NH +OH=NH + H 0
NH +0=NH+OH
NH +0H=NH+H 0
NH2+H=NH+H2
NH +0 =HNO+OH
NH 2+N0=NNH+0H
NH +NO=N +H 0
NH +NO=N20+H2
NIT +HNO=NH +NO
NH +NNH=N +NH
NH+0 =HN0+0
NH+N0=N2+0H
NH4OH=N+H20
NH4OH=HN0+H
NH+H=N+H2
NH+0=N0+H
NH+0=N+0H
NH+N=N2+H
HN0+M=N0+H+M
HN0+0H=N0+H 0
HN0+H=N0+H2
HN0+0=N0+0H
HN0+N=N0+NH
HN0+N=H+N 0
NNH+M=N 2+H+M
NNH+0H=N +H20
NNH+N0=N 2+HNO
N+N0=N +0
N+0 =NO+0
N+OH=NO+H
N 0+M=N +0+M
N 0+H=NH+N0
N 0+H=N +OH
N CHO=N +0
N20+0=N0+N0
H +OH=H 0+H
H+0 =0H+0
0+H =0H+H
H+H0 =0H+0H
0+HO =O +OH
OH+H0 =H 0+0
3
4.80E+16
2.46E+13
1.50E+12
3.26E+12
2.00E+13
3.00E+10
1.00E+12
5.10E+13
6.10E+19
9.10E+19
5.00E+13
1.75E+14
1.00E+13
6.00E+12
1.20E+13
5.00E+11
5.00E+11
3.00E+13
6.30E+11
6.30E+11
6.30E+11
1.86E+16
3.60E+13
4.80E+12
5.00E+11
1.00E+11
5.00E+10
1.50E+15
3.00E+13
2.50E+12
1.60E+13
6.40E+09
6.30E+11
2.70E+14
3.80E+14
7.60E+13
1.00E+14
1.00E+14
2.20E+13
3.70E+17
1.80E+10
2.50E+14
4.80E+13
5.00E+13
0.
0.
0.
0.
0.
0.68
0.5
0.
-2.46
-2.46
0.
0.
0.
0.
0.
0.5
0.5
0.
0.5
0.5
0.5
0.
0.
0.
0.5
0.5
0.5
0.
0.
0.
0.
1.0
0.5
0.
0.
0.
0.
0.
0.
-1.0
1.0
0.
0.
0.
93929.
17071.
6040.
2120.
1000.
1290.
2000.
30000.
1866.
1866.
24800.
1000.
0.
3400.
0.
2000.
2000.
0.
0.
8000.
0.
48680.
0.
0.
0.
2000.
3000.
35000.
0.
0.
0.
6300.
0.
54100.
34500.
15100.
28020.
28020.
5150.
17500.
8900.
1900.
1000.
1000.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
Ref.
3
3
3
3
3
3
8
3
3
3
15
3
3
8
8
16
16
1
16
16
16
3
3
16
16
16
16
8
3
3
16
16
16
17
18
19
19
19
3
20
3
3
3
3
Continued
5.
Table I I .
79
DEAN ET A L .
M e c h a n i s m f o r R i c h Ammonia F l a m e s
Reaction
45.
46.
47.
OH+OH=0+H 0
H0 +NO=N02+OH
H+N0 =NO+OH
48.
49.
0+N0 =N04O2
H+0 +M=H0 +M
H 0/21./***
N02+M=N0+0+M
0+0+M=02+M
H+H+M=H2+M
H /2.5/
H 0/15./
H+0H+M=H 0+M
/2.57
H 0/15./
(Continued)
( k c a l / m o l e ) Comments
3
3
3
3
3
0.
0.
0.
0.
0.
1090.
-260.
1500.
600.
-995.
1.10E+16
1.38E+18
3.60E+16
0.
-1.0
-0.6
66000.
340.
0.
Ref. 3
Ref. 3
R e f . 21
8.80E+21
-2.0
0.
R e f . 21
50.
51.
52.
Ret.
Ref.
Ref.
Ref.
Ref.
6.30E+12
3.43E+12
3.50E+14
1.00E+13
1.50E+15
53.
INCLUSION OF NH + NH REACTIONS
16100.
0.
2000.
54.
55.
56.
NH +NH =N H +H
NH +NH =N H
N H +H=N H +H
1.00E+13
5.00E+12
1.00E+12
0.
0.
0.5
57.
H+OH=N +H 0
2 4
2 3 2
3.00E+10
0.68
1290.
58.
N H.+0=N H-+0H
2 4
2 3
2.00E+13
0.
1000
59.
60.
N H =N H +H
+H=N H +H
2 3
2 2 2
1.20E+13
1.00E+12
0.
0.5
61.
N H^+0H=N H +H 0
2 3
2 2 2
3.00E+10
0.68
1290.
62.
N H +0=N H +OH
2 3
2 2
2.00E+13
0.
1000.
63.
64.
N H =NNH+H
H+H=NNH+H
2 2
2
3.40E+12
1.00E+12
0.
0.5
58000.
2000.
Ref. 8
Ref. 8
Same a s
H+NH2
Same a s
OH+NH2
Same a s
0+NH2
Ref. 8
Same a s
H+NH2
Same a s
0H+NH2
Same a s
0+NH
Ref. 8
Same a s
H+NH
?
65000.
2000.
65.
N H +OH=NNH+H 0
3.00E+10
0.68
1290.
Same a s
0H+NH2
66.
N H -K)=NNH+OH
2.00E+13
0.
1000.
Same a s
0+NH
67.
68
NH+NH=NNH+H
NH+NH =N H +H
5.00E+13
5.00E+13
0.
0.
0.
0.
NOTE :
Rf. S
Ref. 8
R a t e c o n s t a n t u n i t s a r e m o l e , cm, s e c
,K.
*** i . e . , r a t e c o n s t a n t i n c r e a s e d b y a f a c t o r o f 21 f o r H 0 a s t h e
t h i r d body.
2

80
Distance Above Burner (mm)
Figure 3. Comparison o f ( l e f t ) observed and ( r i g h t ) c a l c u l a t e d

p r o f i l e s f o r an ammonia flame with an equivalence r a t i o o f 1.50.

DEAN ET AL.
5.
81
compares t h e s e p r e d i c t i o n s w i t h t h e expanded mechanism t o o u r

o b s e r v a t i o n s f o r t h e = 1.50 f l a m e .
Both c a l c u l a t i o n s and o b s e r v a t i o n s c o n t a i n p o t e n t i a l sources
o f e r r o r , a n d d e t a i l e d c o m p a r i s o n s s h o u l d b e made w i t h t h e s e i n
m i n d . The c o n c e n t r a t i o n measurements o f NH a n d OH a r e p r o b a b l y
a c c u r a t e t o 20%, e x c e p t t h a t OH i n t h e f l a m e f r o n t r e g i o n c o u l d
be l o w i f t h e r e w e r e a p p r e c i a b l e v i b r a t i o n a l e x c i t a t i o n .
NO
measurements w e r e c a l i b r a t e d v i a a b s o r p t i o n ( 7 ) a n d s h o u l d a l s o
be a c c u r a t e t o 20%. NH3 i s more u n c e r t a i n , 30%, s i n c e t h e r e i s
a l a r g e r u n c e r t a i n t y i n t h e e x t i n c t i o n c o e f f i c i e n t used (12).
N H i s p r o b a b l y o n l y a c c u r a t e t o w i t h i n a f a c t o r o f two b e c a u s e
of t h e u n c e r t a i n t i e s i n f j _ .
Uncertainty i s introduced into the
c a l c u l a t i o n s b y t h e u n c e r t a i n h e a t s o f f o r m a t i o n o f NH and NH2.
W i t h t h e s e u n c e r t a i n t i e s , major emphasis s h o u l d be p l a c e d upon
comparison o f t h e shapes o f t h e c o n c e n t r a t i o n p r o f i l e s .
Using these g u i d e l i n e s , t h ecomparisions i n F i g u r e 3 a r e
generally quite satisfactory.
N o t e t h a t NH i s p r o p e r l y d e s c r i b e d
i n terms o f b o t h p r o f i l e shape a s w e l l as a b s o l u t e c o n c e n t r a t i o n .
The c a l c u l a t e d NO p r o f i l e n e a r t h e b u r n e r i s t o o h i g h , b u t t h e
o v e r a l l d e c a y seems t o b e r e a s o n a b l y w e l l d e s c r i b e d .
This d i s
crepancy c l o s e t o t h e burner s u r f a c e c a n be r e s o l v e d by u s i n g a
l a r g e r r a t e constant f o rthe r e a c t i o n
NH + NO + N
+ OH
However, c o n s i d e r i n g t h e u n c e r t a i n t y i n a b s o l u t e c o n c e n t r a t i o n s ,
i t was f e l t t h a t t h i s was i n s u f f i c i e n t j u s t i f i c a t i o n f o r u s e o f
a higher value.
OH i s a l s o p r o p e r l y p r e d i c t e d , w i t h t h e e x c e p t i o n
o f t h e r e g i o n n e a r t h e p e a k , a n d t h i s d i s c r e p a n c y may w e l l b e a
m a n i f e s t a t i o n o f v i b r a t i o n a l l y e x c i t e d OH a s d e s c r i b e d e a r l i e r .
NH c a n be seen t o have t h e proper shape, and t h e a b s o l u t e
concentration p r e d i c t i o n s a r e probably acceptable considering t h e
large e r r o r bars here.
The p r e d i c t e d ammonia d e c a y r a t e a t
l a r g e r d i s t a n c e s a b o v e t h e b u r n e r i s somewhat s l o w e r t h a n
o b s e r v e d . However, e v e n i n t h i s c a s e w h e r e t h e f i t l e a v e s some
t h i n g t o b e d e s i r e d , i t i s v a s t l y i m p r o v e d o v e r what i t was f o r
t h e c a s e where t h e NH. + NH. r e a c t i o n s w e r e e x c l u d e d .
In general, theJits i l l u s t r a t e d i n Figure 3 a r e s i m i l a r t o
t h o s e o b s e r v e d a t t h e o t h e r two e q u i v a l e n c e r a t i o s ( 8 ) .
A
p a r t i c u l a r l y encouraging aspect of t h e c a l c u l a t i o n s a t a l l three
equivalence r a t i o s i s that they p r o p e r l y p r e d i c t t h e v a r i a t i o n
of b o t h peak h e i g h t and peak l o c a t i o n o f t h e r a d i c a l s p e c i e s
w i t h r e s p e c t t o changes i n t h e e q u i v a l e n c e r a t i o .
Thus, i t
a p p e a r s t h a t t h e mechanism g i v e n i n T a b l e I I p r o p e r l y a c c o u n t s
f o r most o f o u r e x t e n s i v e d a t a b a s e o n r i c h ammonia f l a m e s .
Although i t i s impossible t o prove that t h i s i s t h e c o r r e c t
mechanism, t h e p r o p e r p r e d i c t i o n o f s o many s p e c i e s o v e r a r a n g e
o f c o n d i t i o n s s t r o n g l y s u g g e s t s t h a t t h e scheme u s e d i s a r e a s o n
able approximation t o r e a l i t y .
I t i s e v i d e n t t h a t t h e NH-^ + NH^
r e a c t i o n s a r e t h e k e y i n g r e d i e n t t o o b t a i n i n g t h i s good f i t .
As
2

82
PROCESSES
mentioned e a r l i e r , omission o f these r e a c t i o n s l e d t o p r e d i c t i o n s

w h i c h b o r e no r e s e m b l a n c e t o o u r d a t a ( 8 ) .
Figure 4 o u t l i n e s the important r e a c t i o n s of the n i t r o g e n
s p e c i e s i n r i c h ammonia f l a m e s .
The most i m p o r t a n t r e a c t i o n s
p r o d u c i n g N a r e NNH d i s s o c i a t i o n a n d NH + NO. I n t u r n , most o f
t h e NNH i s p r o d u c e d f r o m N H2 d i s s o c i a t i o n w h i c h i s p r o d u c e d v i a
t h e r e a c t i o n NH + NH2. O t h e r N H i + N H i r e a c t i o n s a r e l e s s i m p o r
tant.
Thus, t h e N H i ^ i r e a c t i o n s a r e p r i m a r i l y r e s p o n s i b l e
f o r 2 p r o d u c t i o n ; i t i s now c l e a r why o m i s s i o n o f t h e s e c h a n n e l s
l e d t o s u c h marked changes i n t h e p r e d i c t e d p r o f i l e s .
One w o u l d
n o t e x p e c t s u c h c h a n g e s i n p r e d i c t e d p r o f i l e s i n l e a n ammonia
f l a m e s ; h e r e [NH^] w o u l d b e s u f f i c i e n t l y l o w t h a t t h e N H i + N H i
r e a c t i o n s could s a f e l y by omitted.
Figure 4 a l s o o u t l i n e s a p o s s i b l e reason f o r the continuing
c o n t r o v e r s y a s t o t h e i d e n t i t y o f t h e N H i s p e c i e s w h i c h was
r e s p o n s i b l e f o r t h e NH^ + NO r e a c t i o n when e x a m i n i n g NO p r o d u c t i o n
i n t h e c o m b u s t i o n o f n i t r o g e n doped f u e l s .
An a n a l y s i s o f t h e
reactions i n Figure 4 indicates that ther e l a t i v e concentration
of N H i s p e c i e s w i l l v a r y w i t h c o n d i t i o n s . I n t h i s work where
l a r g e q u a n t i t i e s o f NH a n d NH2 a r e p r e s e n t , N2 p r o d u c t i o n o c c u r s
via NHi NHi
d i s c u s s e d a b o v e . However, i n t h e more t y p i c a l
c a s e o f s m a l l amounts o f n i t r o g e n o u s d i l u e n t , t h e NH^ c o n c e n t r a
t i o n s should be t o o l o w f o r these r e a c t i o n s t o be s i g n i f i c a n t .
There t h e r e l a t i v e p o p u l a t i o n o f the N H i species w i l l be governed
by t h e c o m p e t i t i o n b e t w e e n t h e v a r i o u s NH^ + NO r e a c t i o n s a n d t h e
hydrogen a b s t r a c t i o n s :
2
X + NH. > HX + NH. ..
l - l
L a r g e r r a d i c a l c o n c e n t r a t i o n s (X) w o u l d f a v o r h i g h e r
concentra
t i o n s o f atoms; t h e n + NO w o u l d b e i m p o r t a n t .
Lower r a d i c a l
c o n c e n t r a t i o n s w o u l d t e n d t o i n c r e a s e t h e i m p o r t a n c e o f NH + NO.
F i n a l l y , much l o w e r t e m p e r a t u r e s , i . e . , 1200 f o r t h e T h e r m a l
DeNO p r o c e s s , w o u l d make NH^ + NO a k e y r e a c t i o n .
x
E s t i m a t i o n o f R a t e C o n s t a n t s f o r N ^ + NH^^ a n d N Q J D i s s o c i a t i o n .
The k e y s t o t h e s u c c e s s o f t h e mechanism a r e t h e NH^ + NH^
r e a c t i o n s as w e l l as t h e subsequent u n i m o l e c u l a r d i s s o c i a t i o n
o f t h e N^H^ s p e c i e s f o r m e d f r o m t h e s e r e a c t i o n s . A t y p i c a l
scheme i s t h e f o l l o w i n g :
H
NH + N H
f
1T
H
H^NNH
NNH
H N N H
r
kjM]
H^NNH
lk
NNH +

DEAN ET AL.
NH
NH
OH
HNO
NH
NH
NH
NKL
NH
2
NO
0
H NO
NH
NH
NH
NO
NH
NO
NH
NH, NH
NO
NH
I NO
i Ni 0
IH,0
M,H
NNH 1
M,NH
Figure k. Important r e a c t i o n s o f n i t r o g e n species i n r i c h

amnioni a f1ame s.

84
T h i s i s w r i t t e n i n t h e mechanism a s t h e f o l l o w i n g
NH + N H
N H
2
= N H
= NNH + H
sequence:
(68)
+ H
(63)
with
"68
*H
and
"63
One t h u s o b t a i n s t h e a p p a r e n t r a t e c o n s t a n t s IC53 a n d k 6 3 b y
e v a l u a t i o n o f t h e r a t e constants f o r t h e elementary steps ( k f ,
k , k g , and k ) a n d u s i n g t a b l e s o f t h e K a s s e l i n t e g r a l ( 1 3 ) t o
estimate t h e degree o f f a l l - o f f (I) from t h e l i m i t i n g h i g h p r e s
s u r e r a t e c o n s t a n t , k^. k c a n b e t a k e n t o b e t h e h i g h p r e s s u r e
recombination r a t e constant; k i s the c o l l i s i o n a l s t a b i l i z a t i o n
r a t e c o n s t a n t ; k and k a r e t h e u n i m o l e c u l a r r a t e c o n s t a n t s
c o r r e s p o n d i n g t o N-N a n d N-H bond f i s s i o n , r e s p e c t i v e l y , o f t h e
c o l l i s i o n complex. These decay r a t e c o n s t a n t s were e s t i m a t e d
f r o m t h e RRK e x p r e s s i o n .
r
S-l
w h e r e A i s t h e p r e e x p o n e n t i a l f a c t o r , -* i s t h e amount o f v i b r a
t i o n a l e n e r g y i n e x c e s s o f t h a t r e q u i r e d t o b r e a k t h e bond o f
interest,
i s t h e t o t a l energy o f t h e complex, and S i s t h e
e f f e c t i v e number o f o s c i l l a t o r s ( 1 4 ) . S i s computed v i a t h e
relation
C
Q
b
"
vib
R
F o r t h i s p a r t i c u l a r c a s e o f HNNR^, t h e N-H bond i s o n l y ^ 5 5 k c a l /

m o l e w h i l e N-N i s ^ 8 5 k c a l / m o l e .
Hence k n k and k >> k [ M ]
a t f l a m e t e m p e r a t u r e s a n d kg ^ k f = 5 1 0 ^ m^ m o l e " ! s " l , a
t y p i c a l recombination r a t e constant.
T h u s , t h i s pathway t o N-N
bond f o r m a t i o n i s v e r y r a p i d a n d t h i s r e a c t i o n p l a y s a k e y r o l e
in the kinetics.
r
Summary
By c o m b i n i n g l a s e r d i a g n o s t i c s w i t h i m p r o v e d c o m p u t e r
a l g o r i t h m s f o r m o d e l i n g l a b o r a t o r y f l a m e s , we h a v e b e e n a b l e t o

5.
DEAN ET AL.
85
develop an improved mechanism f o r ammonia o x i d a t i o n at high temp

eratures.
The combination of absorption and l a s e r induced f l u o r
escence have y i e l d e d absolute concentrations of important flame
species.
The s u b - m i l l i m e t e r s p a t i a l r e s o l u t i o n allowed us to
monitor species w i t h i n the flame f r o n t , and the sub-ppm s e n s i t i v
i t y allowed us to measure key r e a c t i v e i n t e r m e d i a t e s .
These
concentration p r o f i l e s provided us with the necessary data base
f o r development of a d e t a i l e d mechanism.
Since the a l g o r i t h m
used a c c u r a t e l y and e f f i c i e n t l y accounted f o r the e f f e c t of
d i f f u s i v e transport w i t h i n the flame, we had the luxury of doing
a r e l a t i v e l y simple, steady s t a t e experiment where we could
s i g n a l average to o b t a i n adequate s e n s i t i v i t y f o r r a d i c a l s .
Since
transport was p r o p e r l y handled, we could focus e x c l u s i v e l y upon
the k i n e t i c s .
In t h i s sense the modeling was s i m i l a r to modeling
a shock wave experiment, but here we had the opportunity to
monitor r e a c t i v e intermediates.
There are a host of h i g h temperature systems which should now
be amenable to t h i s combined d i a g n o s t i c / m o d e l i n g approach.
It
should g i v e k i n e t i c i s t s an e x t r a weapon w i t h which to approach
complex systems.
Literature Cited
1. Morley, C., Eighteenth Symposium (International) on Combustion,
Combustion Institute, Pittsburgh, PA (1981), p. 23, and
references therein.
2. Lyon, R. ., U.S. Patent No. 3,900,554 (1975).
3. Dean, A. M.; Hardy, J. E.; Lyon, R. K.; Nineteenth Symposium
(International) on Combustion, Combustion Institute,
Pittsburgh, PA (182), p. 97.
4. Fujii, N.; Miyama, H.; Koshi, M.; Asaba, T.; Eighteenth
Symposium (International) on Combustion, Combustion Institute,
Pittsburgh, PA (1981), p. 873, and references therein.
5. Fisher, C. J., Combust. Flame, 30, 143 (1977), and references
therein.
6. Chou, M.S.; Dean, A. M.; Stern, D.; J. Chem. Phys., 76,
5334 (1982).
7. Chou, M. S.; Dean, . M.; Stern, D.; J. Chem. Phys., 78,
5962 (1983).
8. Dean, A. M.; Chou, M. S.; Stern, D.; Int. J. Chem. Kinetics
(submitted).
9. Chase, M. W., Jr.; Curnutt, J. L.; Downey, J. R., Jr.;
McDonald, R. .; Syverud, A. N.; Valenzuela, . .; J. Phys.
Chem. Ref. Data, 11. 695 (1982).
10. Piper, L. G.; J. Chem. Phys., 70, 3417 (1979).
11. Smooke, M. D., "Solution of Burner Stabilized Pre-Mixed
Laminar Flames by Boundary Value Methods," Sandia National
Laboratories Report 81-8040 (1982).
12. Menon, P.G.; Michel, K. W.; J. Phys. Chem., 71, 3280 (1967).

86
13. Emanuel, G., "Table of the Kassel Integral," Aerospace Report

No. TR-0200(4240-20)-5 (1969).
14. Benson, S.W., Thermochemical Kinetics, 2nd Edition, Wiley,
New York (1976).
15. Roose, T. R., Ph.D. thesis, Stanford University (1981).
16. Westley, F., "Table of Recommended Rate Constants for
Chemical Reactions Occurring in Combustion," NSRDS-NSB 67
(1980).
17. Dean, A. M.; Steiner, D. C.; J. Chem. Phys., 66, 598 (1977).
18. Cattolica, R. J.; Dean, A. M.; Smooke, M. D.; "A HydrogenNitrous Oxide Flame Study," Sandia Report SAND 82-8776 (1982).
19. Baulch, D. L . ; Drysdale, D. D.; Home, D. G.; Evaluated
Kinetic Data for High Temperature Reactions, Vol. 2,
Butterworth, London (1973).
20. Cohen, N.; Westberg, K. R.; "Chemical Kinetic Data Sheets
for High Temperature Chemical Reactions," Aerospace Report
No. ATR-82(7888)-3.
21. Warnatz, J.; Eighteenth Symposium (International) on
Combustion, Combustion Institute, Pittsburgh, PA (1981),
p. 369.
RECEIVED November
10, 1983

6
Formation of NO and N from NH3 in Flames
2
R I C H A R D J . BLINT and C A M E R O N J . D A S C H
Physics Department, General Motors Research Laboratories, Warren, MI 48090
Ammonia oxidation at high temperatures is an interesting

kinetic system of significant technological importance
for NO formation and destruction. Recent work has
largely been devoted to the moderate temperature (1300K)
region in which NH can quantitatively destroy NO. This
report describes flame studies (1800-2800 K) of NH oxi
dation in which NH is a model compound for the conver
sion of fuel-bound nitrogen to NO and N . A detailed (42
reactions) reaction scheme has been constructed from
literature rate constants which predicts our measured
flame speeds, major species profiles, and NO levels in
ammonia-oxygen-diluent flames. These predictions
require that the radical pool size and the N /NO branch
ing can be correctly described. This mechanism has been
further tested against our measurements of NO emissions
from CH -air flames doped with NH andNO.WhileinNH3
flames NH is pivotal, the Fenimore-type "loading"
experiments indicate a more prominent role for atoms
and the Zeldovitch reactions in hydrocarbon flames. In
part, this is a result of the higher radical concentra
tions in hydrocarbon flames. Full reaction mechanisms
will be necessary to predict the relative conversion of
fuel bound nitrogen to NO and N .
3
The i n t e r a c t i v e k i n e t i c s of NH and NO at high temperatures have

r e c e i v e d a great d e a l of a t t e n t i o n i n recent y e a r s .
Much of t h i s
a t t e n t i o n o r i g i n a t e d from the work of Fenimore who i n v e s t i g a t e d
the conversion of f u e l bound n i t r o g e n to NO i n many flames.
He
found two important p r o p e r t i e s of the NO p r o d u c t i o n : 1) the y i e l d
of NO was independent of the f u e l - n i t r o g e n type and 2) the NO
tended to be s e l f l i m i t i n g such that a s a t u r a t i o n v a l u e of NO
could not be exceeded.
3
Fenimore (1)
formulated a schematic,
two step k i n e t i c
0097-6156/84/0249-0087S06.00/0
88
r e p r e s e n t a t i o n which d e s c r i b e d t h i s s a t u r a t i o n e f f e c t . The model

assumes that a l l the f u e l n i t r o g e n passes through a r e a c t i v e ,
amine intermediate N * . The f i r s t step i s a general o x i d a t i o n
r e a c t i o n which forms NO
k*
* + Ox
-> NO + products
and the second step destroys both NO and the NO precursor
k*
* + NO
+ N
+ products
The NO y i e l d , [ N O ] / [ f u e l - N ] , i s a f u n c t i o n o n l y of
[ N O ] s a t s k [ O x ] / k ; . T h i s formulation f o r the f u e l - n i t r o g e n conver
s i o n to NO has been f u r t h e r t e s t e d by Haynes et a l . ( 2 , 3 ) and by
Fenimore ( 4 , 5 ) .
The e s s e n t i a l feature of t h i s formulation i s the second r e d u c t i o n
step.
T h i s r e a c t i o n had p r e v i o u s l y been recognized as important
from the f a s t r a t e of decay of NO produced i n ammonia flames
(6,7).
T h i s r e a c t i o n process has been e x p l o i t e d i n the Exxon
DeNOx process for NO removal by the c o n t r o l l e d a d d i t i o n of NH to
combustion e f f l u e n t s .
3
The simple phenomenology and l a r g e economic importance f o r f u e l

n i t r o g e n conversion has encouraged many i n v e s t i g a t o r s to t r y to
i d e n t i f y the N* intermediate and i t s r e a c t i o n r a t e s k j and k ? .
Neither Kaskan and Hughes (8) or Fenimore (3,4) could c o n c l u s i v e l y
demonstrate e i t h e r N H , NH, or as being e x c l u s i v e l y p i v o t a l .
D i r e c t measurements of the NH + NO r e a c t i o n r a t e have shown i t to
be f a s t (9,10) and important, e s p e c i a l l y at lower temperatures
such as 1300K where the DeNOx process i s most e f f i c i e n t . T h i s
lower temperature regime i s w e l l understood as a r e s u l t of e x p e r i
ments and extensive k i n e t i c modeling (11,12).
2
Our approach to the f u e l n i t r o g e n conversion to NO problem has

been to examine the k i n e t i c s of NH as a model compound u s i n g
d e t a i l e d flame c a l c u l a t i o n s with modelable flame experiments.
T h i s work has emphasized the major flame p r o p e r t i e s i n c l u d i n g the
flame speed, temperature and major species s p a t i a l p r o f i l e s , and
the post-flame NO c o n c e n t r a t i o n . These measurements and c a l c u l a
t i o n s a r e performed on s t a t i o n a r y f r e e flames.
3
In t h i s paper we f i r s t summarize the a b i l i t y of the NH k i n e t i c

mechanism of Dasch and B l i n t (13) to d e s c r i b e the major p r o p e r t i e s
of ammonia-oxygen-diluent flames. T h i s mechanism i s constructed
s o l e l y from l i t e r a t u r e r a t e constants and i s s p e c i f i c a l l y v a l i d
o n l y f o r flames leaner than 0=1.2 Having v a l i d a t e d the ammonia
mechanism, we then i n v e s t i g a t e the y i e l d of NO from methane-air
flames which have been doped with NH and NO. The NH doped
3

6.
BUNT AND DASCH
Formation of NO and from

2
NH
89
methane flames are a t y p i c a l model system for f u e l - n i t r o g e n NO

production.
The k i n e t i c modeling(14) of t h i s complete n i t r o g e n
and hydrocarbon flame system and i t s success represents a major
advance i n the f u l l r e p r e s e n t a t i o n of the f u e l - n i t r o g e n problem.
This work r e l i e s on the CH mechanism of Warnatz(15) which has
been t e s t e d against many flame p r o p e r t i e s i n c l u d i n g d e t a i l e d temp
erature species p r o f i l e s ( 1 6 ) .
There are no C-N c o u p l i n g r e a c t i o n s
between the C H and NH mechanisms although these r e a c t i o n s are
known to be important for the p r o d u c t i o n of "prompt NO" i n r i c h
flames (0>1.2).
4
M i l l e r et a l . (17) have performed s i m i l a r c a l c u l a t i o n s f o r the

ammonia flame experiments of Fenimore and Jones (6) and Maclean
and Wagner (7). Dean and coworkers ( t h i s Symposium) have a l s o p e r
formed experiments and c a l c u l a t i o n s with an emphasis on r a d i c a l
intermediates.
These c a l c u l a t i o n s show that i n ammonia flames NH i s m a r g i n a l l y
more important than NH and N. Furthermore, the important oxidant
changes with s t o i c h i o m e t r y .
Mixed CH -NH -N0 flames show even a
wider v a r i a t i o n i n the r e l a t i v e r o l e of N H , NH, and N. In near
s t o i c h i o m e t r i c NO doped methane flames, of course, the Z e l d o v i t c h
mechanism i n v o l v i n g i s e x c l u s i v e l y important. S u r p r i s i n g l y ,
i s a l s o most important i n the NH doped C H flames. This i s a con
sequence of the l a r g e r r a d i c a l p o o l i n hydrocarbon flames than NH
flames.
Under both these extremes most of the doped n i t r o g e n
appears as NO. Under combined NH and NO doping the flames are
somewhat more s i m i l a r to ammonia flames i n which NH i s important
for the r e d u c t i o n of NO to N . These combined NH -N0 doping
experiments e x e r c i s e more r i g o r o u s l y the r e d u c t i v e p a r t s of the
mechanism than the Fenimore-type NH doping experiments.
2
It appears that the q u a n t i t a t i v e p r e d i c t i o n of Fenimore's simple

[NO]sat parameter w i l l r e q u i r e a l a r g e k i n e t i c mechanism. The
combined NH and NO doping experiments t e s t Fenimore*s two step
mechanism i n a new way, but i t i s found that the s i n g l e [NO]sat
parameter can s t i l l c o r r e l a t e the r e s u l t s ( 1 4 ) .
3
Experiments
The experimental methods are e x t e n s i v e l y d e s c r i b e d i n e a r l i e r
papers (13,14,16). Temperature and major species p r o f i l e s were
determined by spontaneous Raman spectroscopy i n f r e e flames s t a b i
l i z e d on a s l o t burner. Flame speeds were determined by p a r t i c l e
tracks on the same burner and by the Guoy method on c o n i c a l
flames.
T o t a l NOx measurements were performed i n the postflame
region of a f l a t , water cooled, Meker burner. On the f l a t burner
gas flows were adjusted to give a s l i g h t l y wrinkled flame c o r r e
sponding to f r e e flame c o n d i t i o n s .
Gas samples are extracted with
a water c o o l e d , quartz microprobe analyzed with a chemiluminescent

90
PROCESSES
analyzer.
Temperatures measured simultaneously with a c o r r e c t e d
thermocouple agree w e l l with c a l c u l a t e d a d i a b a t i c flame tempera
tures.
The temperatures were constant f o r at l e a s t 5 cm above the
burner. The NOx concentrations t y p i c a l l y v a r i e d l e s s than 10%
w i t h i n 1.0 cm of the flame f r o n t and then were constant f o r at
l e a s t 5 cm. The systematic u n c e r t a i n l y of the NOx measurements i s
10%.
Computational Method
The experimental observables f o r the f r e e flames i n t h i s study
were modeled using the GMR flame program(18). T h i s program solves
the unsteady s t a t e species and enthalpy conservation equations and
allows them to progress i n time u n t i l the steady flame s o l u t i o n i s
o b t a i n e d . Boundary c o n d i t i o n s f o r f r e e flames were used. Three
types of information are r e q u i r e d f o r these c a l c u l a t i o n s : 1) the
r e a c t i o n mechanism, 2) the t r a n s p o r t p r o p e r t i e s and 3) the thermo
dynamic p r o p e r t i e s of a l l the s p e c i e s .
The r e a c t i o n mechanism
(given i n Ref. 16) i s constructed from l i t e r a t u r e v a l u e s .
The 10
H-0 r e a c t i o n s are w e l l e s t a b l i s h e d .
The 32 a d d i t i o n a l amine and
NO r e a c t i o n s are l a r g e l y taken from Ref. 19, 9, and o t h e r s .
Although NHi-NHj hydrazine r e a c t i o n s were t e s t e d , they were not
important for these near s t o i c h i o m e t r i c flames and were not
r e t a i n e d i n the mechanism. Selected values are taken f o r r e a c
t i o n s which are r a d i c a l branching or termination r e a c t i o n s and
hence e s p e c i a l l y important. The 65 a d d i t i o n a l r e a c t i o n s of the
CH mechanism are from Warnatz(20). There are no C-N c o u p l i n g
r e a c t i o n s between the NH and C H mechanisms, although i t i s known
that these are important i n r i c h e r flames.
The d i f f u s i o n and con
d u c t i o n terms i n the flame program a r e c a l c u l a t e d from Stockmayer
p o t e n t i a l parameters i n the F i c k ' s Law l e v e l of approximation
(21).
The thermodynamics are taken from the JANAF c o m p i l a t i o n up
through the 1978 r e v i s i o n . The heat of formation f o r NH was taken
as 84.7 kcal/mole (22).
4
Pure NH Flames
3
To t e s t the r e a c t i o n mechanism pure ammonia-oxygen-diluent flames

were s t u d i e d under a wide range of s t o i c h i o m e t r i e s and d i l u t i o n s .
Peterson and Laurendeau(23) had p r e v i o u s l y studied NH doped H
flames which e l u c i d a t e much of the NHi o x i d a t i o n chemistry. The
present experiments probe the same r e a c t i o n s and a l s o r e a c t i o n s
between nitrogeneous s p e c i e s .
Flame speeds were f i r s t considered
i n order to e s t a b l i s h a subset of l i t e r a t u r e r e a c t i o n r a t e s which
would d e s c r i b e t h i s major flame f e a t u r e . Comparison of the other
flame features confirm that the flame speed i s a good t e s t bed for
the r e a c t i o n mechanism.
3
The d i f f i c u l t y and the value of e v a l u a t i n g a r e a c t i o n mechanism

based on flame speed over such a l a r g e range of d i l u t i o n s and

6.
91
Formation of NO and 2 from NH3
BLINT AND DASCH
equivalence r a t i o s i s that r e a c t i o n e f f e c t s at a p a r t i c u l a r temp

e r a t u r e range or flame c o n d i t i o n could be inadequate f o r those at
another.
These flame speed data occur over the a d i a b a t i c flame
temperature range of 2270 to 2900 K .
Flame Speeds.
O v e r a l l , the c a l c u l a t e d flame speeds agree w e l l
with experiment.
Flame speed c a l c u l a t i o n s as a f u n c t i o n of d i l
uent c o n c e n t r a t i o n with 0=0.8 (the peak of the s t o i c h i o m e t r i c
dependence) a r e shown i n F i g u r e 1. The c a l c u l a t e d flame speeds
are l e s s temperature dependent than experiment.
Considering the
s t o i c h i o m e t r i c dependence of the flame speeds, the c a l c u l a t i o n s of
flame speed a r e i n greater e r r o r away from the peak (0=0.8) and
exceed the experimental e r r o r a t both r i c h and lean l i m i t s .
Flame P r o f i l e s Major species and temperature p r o f i l e s p r o v i d e a
d e t a i l e d d e s c r i p t i o n of the s t r u c t u r e of these flames.
Three
flames a t i n i t i a l 0 to N r a t i o s of 0.58 were probed using l a s e r
Raman spectroscopy,
the equivalence r a t i o s were 0 . 7 , 1.0 and
1.29.
The c a l c u l a t e d and measured temperature p r o f i l e s f o r the
0=0.7 flame (given i n F i g u r e 2) shows good agreement. S i m i l a r
agreement i s found at 0=1.0 and 1.27. F i g u r e 2 a l s o gives the
oxidant decay p r o f i l e which i s another measure of the flame w i d t h .
Since the r a t i o of 0 to N i s being measured, d i f f e r e n c e s i n the
c a l c u l a t e d and the experimental species p r o f i l e s a r e due t o d i f
ference e i t h e r i n the decay r a t e of the oxygen or i n the growth
r a t e of the n i t r o g e n . For the flames measured, the 0 / N r a t i o
tends t o drop somewhat more q u i c k l y than the c a l c u l a t i o n s .
In the
leaner two flames the H t o N p r o f i l e reaches a maximum a t about
1800K, w e l l before the temperature maximum. The c a l c u l a t i o n s
reproduce the s p a t i a l d i s t r i b u t i o n and s t o i c h i o m e t r i c trends of
the H p r o f i l e but a r e a f a c t o r of 3-10 low i n magnitude. While
the c a l c u l a t e d flame speeds show d e v i a t i o n s as a f u n c t i o n of
equivalence r a t i o , the flame widths seem to be uniformly w e l l
described.
2
Nitrogen Oxide C o n c e n t r a t i o n s . The major o b j e c t i v e of t h i s work

i s the understanding and p r e d i c t i o n of the NO c o n c e n t r a t i o n s . The
equivalence r a t i o dependence of the NO i s given i n F i g u r e 3. The
experimental and c a l c u l a t e d values a r e a l s o compared with the
e q u i l i b r i u m NO concentrations f o r the corresponding a d i a b a t i c
flame.
As has been p r e v i o u s l y observed the NO decreases with
i n c r e a s i n g equivalence r a t i o , e x h i b i t i n g a s l i g h t maximum at 0 . 7 .
as has been p r e v i o u s l y observed.
As seen, the NO i s always
"super- e q u i l i b r i u m " and more so i n r i c h flames.
G e n e r a l l y the
measured and c a l c u l a t e d NO concentrations are the same except f o r
very r i c h flames. The c a l c u l a t i o n s a l s o reproduce the steep temp
e r a t u r e dependence of the NO c o n c e n t r a t i o n .
Not only does the NO
c o n c e n t r a t i o n i n c r e a s e with flame temperature, i t i s p r o g r e s s i v e l y
d r i v e n more " s u p e r - e q u i l i b r i u m " .

92
120 1
100
~ 80-
CD
60-
F i g u r e 1.
Experimental and c a l c u l a t e d
flame speeds v s . i n i t i a l mole
f r a c t i o n o f N i n ammonia-oxygenn i t r o g e n flames with 0= 0 . 8 .
2
40200 0.1 0.2 0.3 0.4 0.5

2 MOLE FRACTION
Figure 2. Experimental and c a l c u l a t e d s p a t i a l p r o f i l e s o f tempera

t u r e and 0 / N r a t i o f o r a = 0.7 ammonia-oxygen-nitrogen flame.
9

6.
BLINT AND DASCH
93
Formation of NO and 2 from NH3
Major Pathways and Reactions E f f e c t s .

As seen above the
experimental data (flame speeds, flame widths and NO concentra
t i o n s ) a r e w e l l d e s c r i b e d by the k i n e t i c mechanism. A schematic
of the whole k i n e t i c c h a i n f o r the combustion of the nitrogeneous
species i s shown i n F i g u r e 4.
The r e l a t i v e i n f l u e n c e of r e a c t i o n s
on a species are determined by a f l u x a n a l y s i s (13,15). T h i s i s a
flame averaged a n a l y s i s , but i t t y p i c a l l y gives r e s u l t s s i m i l a r to
a comparison of net r e a c t i o n rates i n the r e a c t i o n zone.
To f u r
ther t e s t the e f f e c t of the s p e c i f i c r e a c t i o n changes we r e c a l c u
l a t e s e l e c t e d flames.
One important c o n c l u s i o n from such analyses i s that most interme
d i a t e species are i n steady s t a t e or " k i n e t i c a l l y l i m i t e d " .
This
c o n d i t i o n a r i s e s from v e r y f a s t r a d i c a l r e a c t i o n s .
These lead to
t i g h t k i n e t i c c o u p l i n g and chemical r e d i s t r i b u t i o n among the
intermediates much more q u i c k l y than changes due to advection or
diffusion.
The consumption r e a c t i o n s f o r i n d i v i d u a l species w i l l
vary the concentration to match i t s p r o d u c t i o n r a t e .
In the
flames studied these r a t e s never d i f f e r by more than 20% f o r a l l
the r a d i c a l s (H, 0, OH, H 0 , HNO, N H , NH, N) comprising the "rad
i c a l p o o l " . The k i n e t i c a l l y l i m i t e d s t a t e allows some s i m p l i f y i n g
r e l a t i o n s between the intermediates to be expressed, and these
have been discussed by B l i n t and Dasch(13) f o r a number of the
nitrogenous i n t e r m e d i a t e s .
However, t h i s s t a t e a l s o implies that
the s i z e of the intermediate pool w i l l depend on the d i f f e r e n c e
between c h a i n branching and terminating r e a c t i o n s .
These r e a c
t i o n s can be q u i t e slow r e l a t i v e to the c h a i n propagating r e a c
t i o n s but have a l a r g e r i n f l u e n c e s i n c e they c o n t r o l the r a d i c a l
pool s i z e .
These r e a c t i o n s are separately considered f o l l o w i n g
the d e s c r i p t i o n of the primary pathways.
2
In these flames over 95% of the n i t r o g e n atoms are combusted to

N .
Since N i s predominantly formed by r e a c t i o n s of NO with NHi,
approximately h a l f the n i t r o g e n atoms are c y c l e d through NO while
the other h a l f are o x i d i z e d no f u r t h e r than N H i . Since the amine
r a d i c a l s c o n t r i b u t e to the N formation i n the rough r a t i o s of
3:1:1 f o r NH :NH:N, the primary pathway to N can be w r i t t e n by
the two sequences shown i n heavy l i n e .
These sequences account
for about two t h i r d s of the NO and N f o r m a t i o n . While t h i s i n d i
cates a p i v o t a l r o l e f o r N H , n e i t h e r NH nor r e a c t i o n s with NO
can be e l i m i n a t e d from the r e a c t i o n scheme.
2
One of the dominant r e a c t i o n s i s NH with NO branching to the two

sets of p r o d u c t s ,
2
NH
+ NO
N
N
+ + OH
+ H 0
2
(RD
(R2)
As d i s c u s s e d i n Ref. 16 the branching r a t i o of 70% R l and 30% R2

94
100 000
10 000
Figure 3. Experimental and c a l c u l a t e d

maximum NO concentrations as a funct i o n of equivalence r a t i o f o r
ammonia-oxygen-nitrogen flames
with f i x e d i n i t i a l mole f r a c t i o n
of N = 0.4.
1000
NH3
NH
HNO
Figure 4.
Schematic of the d e t a i l e d
k i n e t i c mechanism f o r ammonia
combustion.

6.
BLINT AND DASCH
Formation of NO and from

2
NH
95
was used. To t e s t the e f f e c t of changing the branching r a t i o the

flame speeds were r e c a l c u l a t e d u s i n g the branching r a t i o of 40/60
suggested by S i l v e r , e t . a l . ( 9 ) .
For flames with i n i t i a l N d i l u
t i o n s of 0.4 the flame speeds are slower and the dependence as a
f u n c t i o n of equivalence r a t i o i s m o d i f i e d . The maximum i n the
flame speed i s s h i f t e d r i c h e r than 0=0.8. The f l u x a n a l y s i s f o r
r e a c t i o n s R l and 2 shows a r e d u c t i o n of about 30% f o r the f l u x of
the p r o d u c t s . The flame width of the 0=0.5 N ( i n i t i a l ) = 0 . 4 flame
increases by almost a f a c t o r of three with the change i n the
branching r a t i o . C l e a r l y t h i s branching r a t i o has a l a r g e e f f e c t
on the flame p r o p e r t i e s of ammonia flames.
2
Another r e a c t i o n with a s i g n i f i c a n t e f f e c t on the flame p r o p e r t i e s

is
NH + 0
* HNO + 0
L i t t l e i s known about t h i s r e a c t i o n . We have used the v a l u e sug

gested by Peterson and Laurendeau(23). The s e n s i t i v i t y was t e s t e d
with the r a t e constant that Branch e t . a l .
(12) developed f o r the
lower temperatures of the "Thermal Denox" problem. Using t h i s
smaller r a t e constant (at flame temperatures) on two flames (0=0.5
N ( i n i t i a l ) = 0 . 4 and 0=0.8 N ( i n i t i a l ) = 0 . 1 ) we f i n d 15-20%
decreases i n the flame speed and 40-50% decreases i n the f l u x con
t r i b u t i o n from t h i s r e a c t i o n . O v e r a l l the e f f e c t of reducing the
NH + 0 r a t e i s to reduce the r a t e of p r o d u c t i o n of HNO i n each of
the flames; no s i g n i f i c a n t v a r i a t i o n of t h i s e f f e c t with e q u i v a
lence r a t i o was observed. Changing the products of the r e a c t i o n
to NO and OH as suggested by B i n k l e y and Melius(24) gives r e s u l t s
s i m i l a r to reducing the r a t e . With these products fewer r a d i c a l s
are generated; hence the flame speed i s reduced by more than 20%
and the flame widths thicken s l i g h t l y .
2
NO Y i e l d i n Pure and Doped CH Flames

4
Having v a l i d a t e d the mechanism on ammonia-oxygen flames, the y i e l d

of NO from n i t r o g e n doped C H - a i r flames was examined. Both NH
and NO doping were i n v e s t i g a t e d .
Only post-flame NO c o n c e n t r a
t i o n s were measured. These are compared with c a l c u l a t i o n s of the
f u l l k i n e t i c s and with a d i a b a t i c e q u i l i b r i u m c a l c u l a t i o n s . The
c a l c u l a t e d p r o f i l e s i n d i c a t e the complexity of the NO dynamics i n
these flames.
The temperature and major species p r o f i l e s i n the
undoped flames had been studied i n e a r l i e r work(16).
Three near
s t o i c h i o m e t r i c methane-air flames having i n i t i a l equivalence
r a t i o s ( 0 ) of 0.8, 1.0 and 1.2 are d i l u t e d with l e s s than 5 volume
percents of NH or NO. In t h i s s e c t i o n NO c o n c e n t r a t i o n
is
expressed both as a mole f r a c t i o n and as a f r a c t i o n of the t o t a l
nitrogen concentration:
4
NO fraction=[N0]/([N0]+2[N ]+[NH ]+[NH ]+[NH]+[N]+

2
[HN0]+2[N 0])

96
PROCESSES
T h i s approach removes any e f f e c t s due to changing numbers of molar

species w i t h i n the flame.
Pure Methane Flames.
In a pure methane flames the NO f r a c t i o n
undergoes a small jump passing through the flame f r o n t , then
increases l i n e a r l y with t i m e - d i s t a n c e .
This l i n e a r increase i s
due to low NO c o n c e n t r a t i o n a f t e r the flame f r o n t (approximately
30 ppm i n a s t o i c h i o m e t r i c flame) which i s f a r l e s s than the e q u i
l i b r i u m c o n c e n t r a t i o n of NO (3100 ppm). The reaction(R3) d r i v i n g
the formation of NO i s p a r t of the Z e l d o v i t c h mechanism:
0 + N NO +
+ 0
NO + 0
+ OH + NO +
(R3)
(R4)
(R5)
The reverse r e a c t i o n s are n e g l i g i b l e .

The Z e l d o v i t c h mechanism i s
r a t e l i m i t i n g i n these near s t o i c h i o m e t r i c flames having no added
n i t r o g e n s p e c i e s . There i s no s i g n i f i c a n t NH or p r o d u c t i o n .
NO doped Methane Flames. Most of the NO passes through the flame
unreacted, and the NO p r i m a r i l y a c t s as an i n e r t d i l u e n t .
Dilut
ing the flames with 1.5% NO causes the a d i a b a t i c flame tempera
tures to drop by about 100 and the c a l c u l a t e d flame speeds to
decrease by about 10%. The NC f r a c t i o n decreases by l e s s than 10%
through the flame f r o n t f o r these flames which were doped f a r
above the e q u i l i b r i u m NO concentrations (420-3700 ppm depending on
stoichiometry).
In the experiments there was no post flame decay
i n the NO concencentrations ( 5 % ) , while the c a l c u l a t i o n s do show
some decay (<2%/mm) which depends upon s t o i c h i o m e t r y .
The c a l c u
l a t e d post flame conversion r a t e of NO to N decreases as the
s u p e r - e q u i l i b r i u m r a d i c a l s ( e . g . ; 0 and OH) decay.
2
The very slow r e d u c t i o n of the NO through the flame i s a r e s u l t of

the back r e a c t i o n s of the extended Z e l d o v i t c h mechanism. atoms
are slowly produced from NO by r e a c t i o n s R4 and R5 but then r a p
i d l y react again with NO v i a R3. R3 i s the major r e a c t i o n produc
ing N with i t s f a s t e s t r a t e o c c u r i n g at the r a d i c a l maximum just
past the i n f l e c t i o n p o i n t i n the temperature p r o f i l e .
2
Two minor r e a c t i o n s do produce species which d i r e c t l y i n v o l v e the

f u l l ammonia r e a c t i o n mechanism. These produce NH and NH from
HNO. atom production from NH c o n t r i b u t e s o n l y of the order of
5% of the t o t a l atom p r o d u c t i o n . Even t h i s small c o n t r i b u t i o n
of the HN0-KNH ,NH)->N pathway i s r e s t r i c t e d to the high r a d i c a l
region of the flame f r o n t .
2
NH Doped Methane Flames. While the a d d i t i o n of NO to a methanea i r flame a c t s p r i m a r i l y as a d i l u e n t , the a d d i t i o n of NH r i c h e n s

the mixture l e a d i n g to competition f o r the a v a i l a b l e oxygen.
This
r i c h e n i n g e f f e c t a l s o reduces the e q u i l i b r i u m NO c o n c e n t r a t i o n of
these near s t o i c h i o m e t r i c flames (O.8<0<1.2).
3

6.
BLINT AND DASCH
Formation of NO and N from
97
NH
The measured post-combustion NO concentrations values are gener

a l l y s i m i l a r to the c a l c u l a t e d c o n c e n t r a t i o n s ( F i g u r e 5 ) . The meas
ured NO concentrations tend to be higher at the higher ammonia
dopings. While the NO concentrations i n c r e a s e with NH doping,
the f r a c t i o n of ammonia converted i n t o NO decreases with a c o r r e
sponding i n c r e a s e i n the N f r a c t i o n . T h i s i s the s a t u r a t i o n
behavior e x t e n s i v e l y studied by Fenimore ( l 4 ) and Haynes(2,3).
A f t e r the NO reaches a c r i t i c a l s t e a d y - s t a t e v a l u e , a d d i t i o n a l
f u e l - n i t r o g e n i s converted to N . This behavior i s a l s o seen i n
the c a l c u l a t e d NO p r o f i l e s .
3
I n t e r e s t i n g l y , the major source r e a c t i o n of N i n these ammonia

d i l u t e d methane-air flames i s again r e a c t i o n R3. The "H shuffle"
r e a c t i o n s form a f a s t pathway from NH to atoms.
The extended
Z e l d o v i t c h r e a c t i o n s R3, R4, and R5 then determine the NO and N
production.
T h i s behavior i s i n marked c o n t r a s t to the pure ammo
n i a flame pathways (Figure 4) where NH and NH were s i g n i f i c a n t N
soucrces, and HNO was the major precursor of NO.
2
T h i s d i f f e r e n c e i n behavior between NH and C H flames r e s u l t s

from an approximate doubling of the r a d i c a l c o n c e n t r a t i o n from a
0=1.0 ammonia flame to a 0=1.0 C H / a i r flame.
T h i s change p r o
motes the NH->N pathway over the NH-+HN0 pathway.
3
Combined NO and NH Doped Methane Flames. Adding both NO and NH

to methane-air flames provides the opportunity to enhance the
reducing e f f e c t of the NHi + NO r e a c t i o n s .
T y p i c a l l y the flames
are doped with NO concentrations f a r i n excess of the e q u i l i b r i u m
c o n c e n t r a t i o n s ; consequently we see NO concentrations which are
a p p r e c i a b l y reduced by the NH a d d i t i o n .
3
The c a l c u l a t e d NO concentrations f o r the low dopings o f NH^ show

good agreement with experiment. Table I i s a comparison or the
Table I . E x p e r i m e n t a l , c a l c u l a t e d and e q u i l i b r i u m NO concentrations

i n ppm f o r the methane-air flames d i l u t e d with 1.5% NO.
ADDED
HH,(%)
0.0
0.3
1.0
3.0
5.0
exp.
0 = 0.8
cal.
eq.
0 =: 1.0
exp.
cal.
0 = 1..2
cal.
exp.
eq.
13500 12000 3700
12200 12500 3100
14200 12800 3800

14200 11500 3600
14900 10200 2700
13500 13300 2400

13800 9300 914
12200 6400 250
**
**
**
**
**
**
eq.
12500 12700 420

11000 11700 350
8000 9600 232
7800 5000 70
**
**flame not c a l c u l a t e d

**
**
98
m e a s u r e d , c a l c u l a t e d and e q u i l i b r i u m NO c o n c e n t r a t i o n s f o r t h e
f l a m e s d i l u t e d by 1.5% NO and doped w i t h v a r y i n g amounts o f NH .
above e q u i l i b r i u m . D e v i a t i o n s seem t o o c c u r p r i m a r i l y a t h i g h
d o p i n g s o f ammonia. T y p i c a l l y t h e c a l c u l a t i o n s g i v e l o w v a l u e s .
The a g r e e m e n t i s somewhat w o r s e t h a n t h e t a b l e i n d i c a t e s s i n c e t h e
c a l c u l a t e d NO c o n c e n t r a t i o n s s l o w l y d e c r e a s e w i t h i n c r e a s i n g d i s tance post-flame w h i l e the experimental c o n c e n t r a t i o n s a r e constant .
3
F i g u r a 6 shows c a l c u l a t e d s p a t i a l p r o f i l e s o f NO f r a c t i o n and
t e m p e r a t u r e i n a 0=0.8 m e t h a n e - a i r f l a m e doped w i t h 5% NH
and
1.5% NO.
T h i s i s a t y p i c a l p l o t o f t h e NO f r a c t i o n f o r t h e comb i n e d l o a d i n g e x p e r i m e n t s . There i s an i n i t i a l p r e c i p i t o u s drop i n
the NO c o n c e n t r a t i o n e a r l y on i n t h e t e m p e r a t u r e p r o f i l e , f o l l o w e d
by a s l i g h t r i s e and t h e n t h e v e r y s l o w d r o p i n t h e NO c o n c e n t r a t i o n w i t h d i s t a n c e . The i n t e r m e d i a t e NO peak shown i n t h i s p a r t i c u l a r e x a m p l e i s f r e q u e n t l y f o u n d , a l t h o u g h some NO p r o f i l e s
show o n l y t h e i n i t i a l r a p i d d r o p and t h e v e r y s l o w s e c o n d a r y
reduction.
The i n i t i a l NO d e s t r u c t i o n f o u n d i n t h e s e h i g h NO
d i l u t i o n s ( 1 . 5 % ) i s due t o t h e NH +N0 p a t h w a y . I n c o n t r a s t t o t h e
NH d o p e d f l a m e s , t h e s e f l a m e s do h a v e NO e a r l y i n t h e t e m p e r a t u r e
r i s e where t h e NH o c c u r s . The r e d u c t i o n o f t h e NO a s shown i n
F i g u r e 6 o c c u r s i n a v e r y narrow temperature range. T h i s i n i t i a l
NO d e s t r u c t i o n i s a m a j o r p o r t i o n o f t h e NO d y n a m i c s o v e r t h e
e n t i r e flame. S p e c i f i c a l l y , R l i s found t o account f o r a t l e a s t
1/3 o f t h e NO c o n v e r t e d i n t o N as m e a s u r e d b y a f l u x a n a l y s i s o f
N .
The m i d f l a m e f e a t u r e s a r e due t o t h e e x t e n d e d Z e l d o v i t c h
r e a c t i o n s a n d show a c o m p l i c a t e d i n t e r p l a y o f t e m p e r a t u r e and NH
decay.
C o m p a r i n g t h e NH
and NO c o n c e n t r a t i o n s i n t h i s z o n e , t h e
NO r i s e i s c l e a r l y f r o m NH
which d i d not p a r t i c i p a t e i n the e a r l y
r e d u c t i o n o f NO.
These m i x e d NO and NH
e x p e r i m e n t s show t h a t t h e f u l l t e m p e r a t u r e
r a n g e a n d a l l t h e b r a n c h e s o f t h e r e a c t i o n mechanism a r e i m p o r t a n t
f o r d e s c r i b i n g t h e e v o l u t i o n o f f u e l - n i t r o g e n even i n n e a r s t o i chiometric flames.
3
Conclusions
P u r e ammonia f l a m e s a r e s t u d i e d e x p e r i m e n t a l l y and t h e o r e t i c a l l y
t o i s o l a t e t h e amine c h e m i s t r y . Ammonia and NO d o p e d m e t h a n e - a i r
flames a r e a l s o s t u d i e d as models f o r f l a m e s w i t h f u e l - b o u n d
n i t r o g e n a n d f l a m e s d i l u t e d w i t h NO f r o m EGR. We c o n c l u d e f r o m
these s t u d i e s :
1. P u r e ammonia f l a m e s f o l l o w major p a t h w a y s w h i c h a r e d i f f e r e n t
f r o m d o p e d h y d r o c a r b o n f l a m e s . NH
i s pivotal for determ i n i n g r e l a t i v e N a n d NO y i e l d s i n ammonia f l a m e s .
2

6. BUNT AND DASCH

2
10 L
1
2
3
4
% N H DOPING
0.00
0.10
0.20
0.30
DISTANCE IN LABORATORY F R A M E (cm)
NH
99
Figure 5. C a l c u l a t e d and measured

maximum NO concentrations f o r 0 =
0.8 methane-air flames as a f u n c t i o n
of t o t a l NH^ doping.
Figure 6. Temperature and NO f r a c t i o n s p a t i a l p r o f i l e s f o r 0 = 0.8

methane-air flame doped with 5%
(vol) NH and 1.5% NO.
3

100
2. NO alone doped i n t o methane flames i s only reduced by the slow

t h r e e - r e a c t i o n Z e l d o v i t c h mechanism. No a p p r e c i a b l e r e d u c t i o n
due to the ammonia r e a c t i o n mechanism i s found.
3. Contrary to pure ammonia combustion where the primary source of
N comes from r e a c t i o n s of NH with NO, ammonia doped i n t o
methane-air flames i s combusted to N v i a the + NO r e a c t i o n .
2
4. Mixtures of NO and NH i n methane-air flames e x h i b i t separate

regions of reducing NO to N and then o x i d i z i n g NH to NO.
The reducing r e g i o n i s due to the NH +N0 r e a c t i o n s , while the
o x i d i z i n g zone i s dominated by the Z e l d o v i t c h r e a c t i o n s .
The
r e l a t i v e importance of the two mechanisms i s dependent on the
shape of the temperature p r o f i l e of the flame.
It i s
concluded that the reducing e f f e c t of f u e l - n i t r o g e n on
hydrocarbon f u e l mixtures c o n t a i n i n g NO i s dependent on the
flame s t r u c t u r e .
3
Acknowledgments
We wish to thank R . E . Teets and J . H . Bechtel f o r h e l p f u l d i s c u s
s i o n s , L . Green and S. Howell f o r t e c h n i c a l a s s i s t a n c e , and A . D .
Gara f o r encouragement and support.
Literature Cited
1. Fenimore, C.P. Combust. Flame 1972, 19, 289.

2. Haynes, B.S.; Iverach, D.; Kirov, N.Y. Fifteenth Symposium
(International) on Combustion 1975, p. 1103.
3. Haynes, B.S. Combust. Flame 1977, 28, 81.
4. Fenimore, C.P. Combust. Flame 1976, 26, 249.
5. Fenimore, C.P. Seventeenth Symposium (Internation) on
Combustion 1979, p. 661.
6. Fenimore,C.P;Jones, G.W. J. Phys. Chem. 1961, 65, 298.
7. MacLean, D.I.; Wagner, H. Gg. Eleventh Symposium
(International) on Combustion 1967, p. 871.
8. Kaskan W.E.; Hughes, D.E. Combust. Flame 1973, 20, 381.
9. Silver, J.A.; Kolb, C.E. J. Phys. Chem. 1982, 86, 3240.
10. Roose, T.R.; Hanson, R.K.; Kruger, C.H. Eighteenth
Symposium(International) on Combustion 1981, p. 853.

6.
BLINT AND DASCH

2
NH
101
11. Lyon, R.K.; Dean, A.M.; and Hardy, J.E. Nineteenth

Symposium (Internation) on Combustion 1983.
12. Branch, M.C.; Kee, R.J; Miller, J.A. Combust. Sci.
Tech. 1982, 29,147.
13. Dasch, C.J.; Blint, R.B. "A Mechanistic and Experimental
Study of Ammonia Flames", General Motors Research Lab
oratories Report GMR-4232, and Eastern States Fall Meet
ing, The Combustion Institute, 1982, Paper ESS/CI 82-71.
14. Blint, R.B.; Dasch, C.J. "Experiments and Calculations of
NO Yield from NH and NO in CH Flames", General Motors
Research Research Report, 1983.
15. Warnatz, J. Ber. Bunsenges. Phys. Chem. 1979, 83,950.

16. Bechtel, J.H.; Blint, R.J.; Dasch, C.J.; Weinberger, D.A.
Combust. Flame 1981, 42, 197.
17. Miller, J.A.; Smooke, M.D.; Green, R.M.; Kee., R.J.
"Kinetic Modeling of the Oxidation of Ammonia in Flames",
Western States Section Fall Meeting, The Combustion
Institute, 1982, Paper WSS/CI 82-93.
18. Dasch, C.J.; Blint, R.B. "An Improved Spalding-Stephenson
Transformation for One Dimensional Flame Calculations",
accepted for publication in Combust. Sci. Tech.;
and Western States Section Fall Meeting, The Combustion
Institute, Paper WSS/CI 82-89, 1982.
19. Salimian, S.; Hanson, R.K. Combust. Sci. Technology
1980, 23, 225.
20. Warnatz, J. Eighteenth Symposium (International)
on Combustion 1981, p.853.
21. Hirschfelder, J.O.; Curtiss, C.F.; Bird, R.B. Molecular
Theory of Gases and Liquids John Wiley & Sons Inc., New York,
1954.
22. Piper, L.G. J. Chem. Phys. 1979, 70, 3417.
23. Peterson, R.C.; Laurendeau, N.M. Central States Section,
The Combustion Institue, 1982, Paper CSS/CI 82-15.
24. Binkley, J.S.; Melius, C.F. "Oxidation of the NH and NH2
Radicals", Western States Section Fall Meeting, The
Combustion Institute, 1982, Paper WSS/CI 82-96.
1983

7
Reactions of NH and N H with and O2
2
Theoretical Studies
C. F. MELIUS and J. S. BINKLEY

Sandia National Laboratories, Livermore, CA 94550
Calculations involving fourth-order Mller-Plesset

perturbation theory with bond a d d i t i v i t y corrections
were used to investigate the reactions of NH2 and
NH with O and O . New heats of formation were used
f o r NH (47 kcal-mole ) and NH (87 kcal-mole ). We
find that the NH O complex is barely stable. Thus, the
rate constant for NH + O should be very small with the
most probable products at high temperatures being NHO+O.
For NH+O, we find that the reaction forming HNO+O i s
spin forbidden on the lower lying singlet surface. Thus,
at room temperature the l i k e l y products are O+O and
H+NO, which are accessible on the singlet surface.
For NH+O and NH+O, we find that stable inter
mediate complexes can be formed with no activation
barrier. These can undergo direct dissociation by
losing a hydrogen or can undergo a 1,2-hydrogen shift
with further dissociation forming OH. The reaction path
way involving molecular complex formation should dominate
at room temperature while direct hydrogen abstraction by 0
atoms should dominate at high temperatures.
2
-1
-1
The r e a c t i o n s o f N H and NH w i t h 0 and 0 p l a y i m p o r t a n t r o l e s i n

t h e o x i d a t i o n o f ammonia and f u e l bound n i t r o g e n s a s w e l l a s i n
t h e r e d u c t i o n o f N0 's(l-12). However, t h e r a t e c o n s t a n t s f o r
these r e a c t i o n s d i f f e r d r a s t i c a l l y i n t h e various chemical
r e a c t i o n m o d e l s which have been d e v e l o p e d ( 1 - 6 ) . Even t h e
e x p e r i m e n t a l l y measured r a t e c o n s t a n t s show a wide v a r i a t i o n and
d i f f e r s i g n i f i c a n t l y from the corresponding i s o e l e c t r o n i c counter2
0097-6156/84/0249-0103506.00/0
104
PROCESSES
p a r t s i n v o l v i n g c a r b o n and oxygen ( 6 , 1 3 - 2 3 ) . F u r t h e r m o r e , i t i s
n o t even c l e a r what t h e p r o d u c t s o f t h e s e r e a c t i o n s s h o u l d b e .
To a i d t h e m o d e l e r s i n d e v e l o p i n g improved r e a c t i o n mechanisms as w e l l as t o a i d t h e e x p e r i m e n t a l i s t s i n t h e i r i n t e r p r e t a t i o n o f t h e d a t a , we have c a l c u l a t e d t h e e n e r g e t i c s o f m o l e c u l a r
i n t e r m e d i a t e s and p r o d u c t s a r i s i n g f r o m t h e s e r e a c t i o n s . O u r
a p p r o a c h was t o u s e t h e h i g h l y a c c u r a t e f o u r t h o r d e r M p l l e r P l e s s e t p e r t u r b a t i o n t h e o r y (24) with b o n d - a d d i t i v i t y c o r r e c t i o n s . (25)
In t h e n e x t s e c t i o n , we b r i e f l y p r e s e n t t h e t h e o r e t i c a l
a p p r o a c h . We t h e n p r e s e n t and d i s c u s s t h e r e s u l t s f o r t h e
r e a c t i o n s NH +o , NH+0 , NH +0, and NH+0.
2
Theoretical
Approach
The method i s d i v i d e d i n t o two d i s t i n c t s t e p s . The f i r s t s t e p

c o n s i s t s o f ab i n i t i o c o m p u t a t i o n o f t h e t o t a l e n e r g i e s o f t h e
d e s i r e d m o l e c u l e . T h i s i s accomplished by f i r s t d e t e r m i n i n g t h e
t h e o r e t i c a l e q u i l i b r i u m geometry o f t h e molecule u s i n g t h e
6-31G*(26j b a s i s and s p i n - r e s t r i c t e d H a r t r e e - F o c k ( 2 7 ) t h e o r y
f o r c l o s e d - s h e l l m o l e c u l e s and s p i n - u n r e s t r i c t e d H a r t r e e - F o c k
(28) t h e o r y f o r o p e n - s h e l l m o l e c u l e s . U s i n g t h e s e g e o m e t r i e s
two a d d i t i o n a l c a l c u l a t i o n s a r e p e r f o r m e d . Z e r o - p o i n t v i b r a t i o n a l
c o r r e c t i o n s a r e d e r i v e d u s i n g a n a l y t i c a l l y computed (29) s e c o n d d e r i v a t i v e s o f t h e energy with r e s p e c t t o the i n t e r n a l degrees o f
freedom.
In t h e second c a l c u l a t i o n e l e c t r o n c o r r e l a t i o n e f f e c t s
are d e t e r m i n e d u s i n g M f l l l e r - P l e s s e t p e r t u r b a t i o n t h e o r y c a r r i e d
o u t t o f o u r t h - o r d e r (24) u s i n g t h e 6-31G** ( 2 6 ) b a s i s
( d e n o t e d MP4/6-31G**). Combining t h e d a t a f r o m t h e s e two c a l culations leads to a v i b r a t i o n a l l y corrected, electron-correlated
t o t a l energy f o r a given molecule.
These t h e o r e t i c a l c a l c u l a t i o n s a r e s u b j e c t t o s y s t e m a t i c
e r r o r s a r i s i n g f r o m b a s i s s e t t r u n c a t i o n and n e g l e c t o f h i g h e r
p e r t u r b a t i o n o r d e r e l e c t r o n c o r r e l a t i o n e f f e c t s . T h e r e f o r e , we
have added a s e c o n d s t e p t o o u r p r o c e d u r e i n which we a t t e m p t t o
a c c o u n t f o r t h e s e d e f i c i e n c i e s by a d d i n g e m p i r i c a l l y d e r i v e d
B o n d - A d d i t i v i t y - C o r r e c t i o n (BAC) f a c t o r s t h a t a r e based on t h e
t y p e s o f bonds p r e s e n t i n t h e g i v e n m o l e c u l e . The c o r r e c t i o n
f a c t o r s f o r NH (9.4 k c a l - m o l e " ) and OH (10.7 k c a l - m o l e " ) bonds
are o b t a i n e d a s t h e d i f f e r e n c e between t h e t h e o r e t i c a l and
1

7.
MELIUS AND BINKLEY
Reactions of NH and NH with and 0

2
105
e x p e r i m e n t a l e n e r g i e s f o r c o m p l e t e d i s s o c i a t i o n o f NH3 and 2,
r e s p e c t i v e l y , a v e r a g e d o v e r t h e number o f Dnds i n t h e m o l e c u l e .
In a s i m i l a r f a s h i o n , c o r r e c t i o n f a c t o r s f o r t h e n i t r o g e n - o x y g e n
and o x y g e n - o x y g e n bond t y p e s a r e d e v e l o p e d f r o m a c o m p a r i s o n o f
the t h e o r e t i c a l r e s u l t s with v a r i o u s experimental values o f -0-
c o n t a i n i n g m o l e c u l a r s p e c i e s . In t h i s c a s e t h e bond a d d i t i v i t y
c o r r e c t i o n s depend b o t h on t h e bond d i s t a n c e a s w e l l a s t h e bond
t y p e . An a d d i t i o n a l c o r r e c t i o n f a c t o r f o r s p i n c o n t a m i n a t i o n i n
the s p i n - u n r e s t r i c t e d Hartree-Fock wavefunction i s i n c l u d e d .
U s i n g t h e t h e o r e t i c a l l y computed t o t a l e n e r g i e s , v a l u e s
were be o b t a i n e d f o r t h e a p p r o p r i a t e , N, 0 - c o n t a i n i n g s p e c i e s .
T h i s p r o c e d u r e t a c i t l y assumes t h e t r a n s f e r a b i l i t y o f t h e c o r
r e c t i v e f a c t o r s f r o m one m o l e c u l e t o a n o t h e r and i s s u b j e c t t o a n y
l i m i t a t i o n s imposed b y t h e o r i g i n a l e x p e r i m e n t a l v a l u e s . The f u l l
d e t a i l s and a c r i t i c a l a n l y s i s o f t h i s p r o c e d u r e w i l l be p u b l i s h e d
separately.
The c a l c u l a t e d h e a t s o f f o r m a t i o n f o r v a r i o u s s t a b l e and metas t a b l e i n t e r m e d i a t e s and p r o d u c t s f o r t h e r e a c t i o n s NH2+O2, +2,
NH +0, and + 0 a r e shown i n F i g u r e s 1-4. The h e a t s o f f o r m a t i o n
f o r t h e p o l y a t o m i c s a g r e e w i t h known e x p e r i m e n t a l h e a t s o f f o r
m a t i o n t o w i t h i n s e v e r a l k c a l - m o l e " . The e x c e p t i o n s a r e NH and
NH2 where t h e e x p e r i m e n t a l e s t i m a t e s v a r y w i d e l y . ( E x p e r i m e n t a l
v a l u e s f o r N H r a n g e f r o m 40-46 k c a l - m o l e " w h i l e e x p e r i m e n t a l
v a l u e s f o r NH r a n g e f r o m 81-90 k c a l - m o l e " ) . We t h e r e f o r e have
used o u r r e c e n t l y c a l c u l a t e d v a l u e s o f ^(2) = 47 k c a l - m o l e "
and ^ ( ) = 87 k c a l - m o l e " a s b e i n g t h e most r e l i a b l e ( 2 5 ) .
Included i n t h e f i g u r e s a r e schematic curves which connect
v a r i o u s i s o m e r s w i t h each o t h e r and w i t h r e a c t a n t s o r p r o d u c t s .
T r a n s i t i o n s t a t e p o t e n t i a l e n e r g y b a r r i e r s have n o t been c a l
c u l a t e d f o r t h e s e p r o c e s s e s . However, we have i n c l u d e d t h e s e
s c h e m a t i c c u r v e s ( w i t h an i n d i c a t i o n o f w h e t h e r t h e t r a n s i t i o n
s t a t e b a r r i e r s h o u l d be l a r g e , s m a l l , o r n o n e x i s t e n t ) i n o r d e r t o
h e l p t h e r e a d e r f o l l o w p o s s i b l e r e a c t i o n mechanisms.
2
NH?+Q?. S e v e r a l r e a c t i o n schemes have been p r o p o s e d f o r NH2+2

( v a l u e s f o r a l l r e a c t i o n s were computed i n t h i s s t u d y ) :
NH +0
*-0+ 0
proposed by Gesser ( 7 ) ,
2
= -83 k c a l - m o l e "

(1)
106
Figure 1. C a l c u l a t e d energies o f p o s s i b l e intermediates and

products f o r the r e a c t i o n o f NH^
2'
V e r t i c a l s c a l e represents
at OK.
Connecting curves s c h e m a t i c a l l y i n d i c a t e p o s s i b l e
r e a c t i o n pathways.
+
+ H0
120-
Figure 2.
Same as i n Figure 1 f o r NH + 0,

MELIUS AND BINKLEY

2
7.
F i g u r e h.
Same as i n F i g u r e 1 f o r NH + 0.

107
108
NH +o
2
*-0+0
= -10 k c a l - m o l e "
PROCESSES
(2)
(3)
f i r s t p r o p o s e d b y H u s a i n and N o r r i s h ( 8 ) ,
NH +o
2
*- 00
= -5 k c a l - m o l e "
f i r s t p r o p o s e d b y J a y a n t y , e t a l . ( 1 3 ) and f a v o r e d by Hack, e t a l .
(14), and
NH +o
*-+0
= +45 k c a l - m o l e "
(4)
f i r s t p r o p o s e d b y Takeyama and Miyama ( ) .
As c a n be seen f r o m F i g u r e 1, NH 00 does n o t f o r m a v e r y
s t a b l e complex, h a v i n g a N H - 0 bond e n e r g y o f l e s s t h a n 6
k c a l - m o l e " . Our c a l c u l a t i o n s a r e c o n s i s t e n t w i t h t h e e s t i m a t e s
by P a g s b e r g , e t a l . ( 1 5 ) and Benson ( 1 6 ) and i m p l y t h a t t h e
i n t e r p r e t a t i o n o f t h e e x p e r i m e n t a l r a t e d a t a by Hack, e t a l . ( 1 4 )
s h o u l d be r e e x a m i n e d w i t h r e s p e c t t o f o r m i n g p r o d u c t s , s i n c e t h e
1,3-hydrogen s h i f t t o f o r m 00 s h o u l d have a s i g n i f i c a n t
b a r r i e r . T h u s , i t i s u n l i k e l y t h a t r e a c t i o n s ( 1 ) and ( 2 ) a s w e l l
as ( 4 ) v i a t h e 00 complex w i l l have l a r g e r a t e c o n s t a n t s . T h e
r e c e n t t h e o r e t i c a l c a l c u l a t i o n s o f Pouchan and C h a i l l e t ( 1 7 ) ,
u s i n g a l e s s s o p h i s t i c a t e d s u b s e t o f t h e method employed h e r e ,
f i n d NH 00 t o be unbound b y 13 k c a l - m o l e " . However, t h e i r c o n
c l u s i o n s a r e c o n s i s t e n t with ours i n tending t o r u l e out r e a c t i o n
(3).
Thus, w h i l e t h e r e a r e s e v e r a l e x o t h e r m i c p r o d u c t s f o r t h e
r e a c t i o n o f N H + 0 ( e . g . , 00+, 0+0, N 0 + H , and N0+H 0),
t h e r e a r e no s i m p l e r e a c t i o n pathways t o f o r m them.
Based on F i g u r e 1, we b e l i e v e t h e most p r o b a b l e r e a c t i o n t o
be
1
NH +0 *- 0+0
2
= +30 k c a l - m o l e "
(5)
as s u g g e s t e d b y Benson ( 1 6 ) , p a r t i c u l a r l y a t t h e h i g h e r tempera
t u r e s i n f l a m e c o n d i t i o n s . Such a mechanism i s c o n s i s t e n t w i t h
t h e o b s e r v a t i o n t h a t a t room t e m p e r a t u r e t h e measured r a t e c o n
stant f o r NH +0 i s n e g l i g i b l y small (<6xl0 cc mole" s e c "
determined by L e s c l a u x (18), <5xl0^ c c m o l e " s e c " determined
by P a g s b e r g ( 1 5 ) , < 9 x l 0 ^ c c m o l e " s e c " d e t e r m i n e d by C h e s k i s
et a l . ( 2 1 ) .
5

7.
MELIUS AND BINKLEY

2
109
( 1 9 ) ) . The l a c k o f a s t a b l e complex e x p l a i n s why t h e room tem

p e r a t u r e r a t e i s much s m a l l e r t h a n t h a t o f t h e i s o e l e c t r o n i c
r e a c t i o n o f CH +o t o f o r m t h e CH3OO complex (14)>
s t a b l e by 26 k c a l - m o l e " . The e n d o t h e r m i c i t y o f 30 k c a l - m o l e "
f o r r e a c t i o n ( 5 ) (no b a r r i e r s h o u l d e x i s t on t h e e x i t c h a n n e l ) i s
c o n s i s t e n t w i t h b o t h t h e t e m p e r a t u r e dependence o f 37.7 2.6
k c a l - m o l e " f i t t o i n d u c t i o n t i m e s o f v a r i o u s shock t u b e
e x p e r i m e n t s ( 1 0 ) and w i t h t h e need f o r a l a r g e a c t i v a t i o n e n e r g y
f o r t h e r e a c t i o n o f N H + 0 used i n v a r i o u s m o d e l s o f ammonia
o x i d a t i o n (1-3,5,6). The d i r e c t hydrogen a b s t r a c t i o n r e a c t i o n
(4) c a n a l s o o c c u r (on t h e q u a r t e t p o t e n t i a l e n e r g y s u r f a c e ) ,
and s h o u l d have a s l i g h t a c t i v a t i o n b a r r i e r i n a d d i t i o n t o b e i n g
endothermic.
w h i c h
i s
NH+0 . Two r e a c t i o n pathways have been p r o p o s e d f o r NH+0 .

One, s u g g e s t e d b y H u s a i n and N o r r i s h ( 8 ) , i n v o l v e s a r e a r r a n g e m e n t
c o l l i s i o n t o f o r m NO, i . e . ,
2
+0 *-0+0
= -56 k c a l m o l e "
T h i s r e a c t i o n pathway
s u p p o r t e d by Drummond
Duxbury and P r a t t (3)
m o d e l i n g . The second
displacement reaction
(6)
i s f a v o r e d by Takeyama and Miyama ( ) ,

( 1 2 ) and o t h e r s ((>), and used b y
and b y A z u h a t a , e t a l . ( 4 ) i n t h e i r
r e a c t i o n pathway i n v o l v e s t h e more d i r e c t
f o r m i n g HNO, i . e . ,
+0 *-0+0
= -1 k c a l m o l e "
(7)
W h i l e t h e r e h a s been some c o n c e r n t h a t r e a c t i o n ( 7 ) may be

e n d o t h e r m i c , o u r c a l c u l a t e d h e a t o f f o r m a t i o n f o r NH o f 87
k c a l - m o l e " implies that (7) i s e s s e n t i a l l y thermal n e u t r a l .
R e a c t i o n ( 7 ) i s f a v o r e d b y Z e t z s c h and Hansen ( 2 0 ) as b e i n g
s i m p l e r t h a n ( 6 ) and i s used by F u j i i , e t a l . (j5), M i l l e r ,
e t a l . (1), and L y o n , e t a l . (2) i n t h e i r m o d e l i n g e f f o r t s .
In e i t h e r c a s e , t h e a c t i v a t i o n b a r r i e r used by t h e m o d e l e r s i s
s m a l l ( 3 k c a l - m o l e " ) o r a b s e n t . The r a t e c o n s t a n t f o r NH+0?
p r o d u c t s a t room t e m p e r a t u r e i s s m a l l ( 5 . 1 x 1 0 ^ c c m o l e ^ s e c "
as measured by Z e t z s c h and Hansen ( 2 0 ) ; < 2 x l 0 c c m o l e " s e c "
as measured b y P a g s b e r g , e t a l . ( 1 5 ) ) , a l t h o u g h a r a t e c o n s t a n t o f
3 . 6 x 1 c c m o l e ^ s e c " was measured i n d i r e c t l y by M c C o n n e l l
1
1 0
1 1

110
PROCESSES
To a s s i s t i n d i s t i n g u i s h i n g between t h e p o s s i b l e r e a c t i o n
pathways and r a t e c o n s t a n t s , we p r e s e n t t h e c a l c u l a t e d e n e r g e t i c s
o f t h e NH+0 s y s t e m i n F i g u r e 2. The s y s t e m i s c o m p l i c a t e d i n
t h a t t h r e e p o t e n t i a l e n e r g y s u r f a c e s must be c o n s i d e r e d . We c a n
i m m e d i a t e l y r u l e o u t t h e q u i n t e t s u r f a c e s i n c e no l o w - l y i n g i n t e r
mediate s t a t e s o r f i n a l products e x i s t f o r t h i s surface. The
l o w e s t r e a c t i o n pathway e x i s t s f o r t h e s i n g l e t s u r f a c e , f o r which
t h e 0 0 i n t e r m e d i a t e ( s t a b i l i z e d b y t h e N-0 bond e n e r g y which i s
e s t i m a t e d t o be 22-29 k c a l - m o l e " ) c a n be f o r m e d w i t h o u t any s i g
n i f i c a n t b a r r i e r . The 0 0 s p e c i e s i s i s o e l e c t r o n i c w i t h o z o n e , a
b i r a d i c a l s i n g l e t s p e c i e s ( 2 8 - 3 0 ) . The 0 0 s p e c i e s c a n u n d e r g o
r i n g c l o s u r e f o l l o w e d b y s c i s s i o n o f t h e 0-0 bond t o f o r m t h e
s t a b l e n i t r o h y d r i d e i s o m e r . Our c a l c u l a t i o n s i n d i c a t e t h a t t h e
a c t i v a t i o n e n e r g y f o r t h i s r i n g c l o s i n g and r e o p e n i n g s h o u l d be
l e s s t h a n t h e 22-29 k c a l - m o l e " bond e n e r g y formed from t h e
i n c o m i n g NH+0 .
Having f o r m e d n i t r o h y d r i d e , t h e r e i s s u f f i c i e n t i n t e r n a l
e n e r g y t o b r e a k t h e N-H bond t o f o r m H+N0 , i . e . ,
2
NH+0
*-+0
= -28 k c a l m o l e "
(8)
o r t o u n d e r g o a 1,2-hydrogen s h i f t t o f o r m t h e more s t a b l e 0 0
which c a n decompose t o f o r m 0+0 ( r e a c t i o n ( 6 ) ) a s w e l l a s H+N0
( r e a c t i o n ( 8 ) ) . Under t h e a p p r o p r i a t e c o n d i t i o n s one c o u l d f o r m
t h e 0 0 complex r a t h e r than t h e more s t a b l e 0 0 . I t s h o u l d be
noted t h a t t h e d i r e c t d i s p l a c e m e n t r e a c t i o n f o r m i n g HN0+0( P)
( r e a c t i o n ( 7 ) ) c a n n o t o c c u r t h r o u g h t h e s t a b l e H N O O ^ A ) complex
but must o c c u r on t h e h i g h e r l y i n g t r i p l e t s u r f a c e . Removing t h e
0 atom f r o m ^ ' ) would p r o d u c e H N 0 ( A ) + 0 ( P ) a n a l o g o u s t o
t h e i s o e l e c t r o n i c r e a c t i o n 0 ( ) + 0 ( g ) - ^ 0 ( 2 g) + 0 ( P ) .
However, u n l i k e 0 + 0 , t h i s r e a c t i o n i s e n d o t h e r m i c b y 19
k c a l - m o l e " , which would e x p l a i n why t h e r a t e c o n s t a n t f o r NH+0
i s s m a l l e r than t h a t f o r t h e i s o e l e c t r o n i c 0+0 (29) exchange
reaction.
R e a c t i o n ( 7 ) w i l l o c c u r on t h e t r i p l e t s u r f a c e t h r o u g h t h e
metastable HN00( A') i n t e r m e d i a t e . T h i s i n t e r m e d i a t e i s
c a l c u l a t e d t o be o n l y s l i g h t l y e n d o t h e r m i c ( 4 k c a l - m o l e " ) .
T h e r e s h o u l d be a v e r y s m a l l a c t i v a t i o n b a r r i e r on t h e i n c o m i n g
r e a c t i o n path. Of greater s i g n i f i c a n c e i s the outgoing r e a c t i o n
2

7.
MELIUS AND BINKLEY
111
Reactions of H and NH with and 0

2
p a t h ( H N 0 0 ( A ' ) H N 0 + 0 ( P ) ) which must undergo a t w o - e l e c t r o n

a v o i d e d c u r v e c r o s s i n g v i a a b r e a k i n g o f p l a n a r symmetry, g i v i n g
r i s e t o an a d d i t i o n a l 5-15 k c a l - m o l e " e n e r g y b a r r i e r . Thus, t h e
a c t i v a t i o n e n e r g y f o r r e a c t i o n ( 7 ) s h o u l d be l a r g e r t h a n t h e
3 k c a l - m o l e " used by t h e m o d e l e r s .
T a k i n g both s u r f a c e s i n t o a c c o u n t , we c o n c l u d e t h a t t h e room
t e m p e r a t u r e p r o c e s s s h o u l d be dominated by r e a c t i o n s ( 6 ) and ( 8 )
on t h e s i n g l e t s u r f a c e w h i l e a t h i g h t e m p e r a t u r e s , r e a c t i o n ( 7 )
should dominate.
1
NHp+Q. Two s e t s o f p r o d u c t s have been p r o p o s e d (22,23) f o r t h e

r e a c t i o n o f N H w i t h a t o m i c oxygen:
2
+0 *-HN0+H
= -28 k c a l - m o l e "
(9)
NH +o * - 0 +
= -9 k c a l - m o l e "
(10)
and
2
T h e r e h a s been some q u e s t i o n as t o whether o r n o t r e a c t i o n

(10) i s e n d o t h e r m i c o r e x o t h e r m i c . Based on o u r c a l c u l a t e d h e a t s
o f f o r m a t i o n o f NH and NH , r e a c t i o n (10) s h o u l d be e x o t h e r m i c by
9 k c a l - m o l e " . The r a t e c o n s t a n t f o r NH +0 a t room t e m p e r a t u r e
i s 2.1 l O ^ c c m o l e " s e c " a s measured by G e h r i n g , e t a l . ( 2 2 ) .
T h i s i s s m a l l e r t h a n t h e measured r a t e c o n s t a n t s f o r t h e i s o e l e c
t r o n i c s p e c i e s C H and OH r e a c t i n g w i t h 0 atom.
Our t h e o r e t i c a l r e s u l t s (shown i n F i g u r e 3) i n d i c a t e t h a t
b o t h r e a c t i o n s ( 9 ) and (10) a r e p o s s i b l e . On t h e d o u b l e t s u r f a c e ,
NH +0 s h o u l d f o r m t h e H N0 i n t e r m e d i a t e w i t h o u t an a c t i v a t i o n
b a r r i e r . T h i s complex c a n r e a d i l y d i s s o c i a t e t o f o r m HNO+H
(Reaction ( 9 ) ) . The r a d i c a l i n t e r m e d i a t e i s s u f f i c i e n t l y e x o t h e r
mic t h a t i t c a n a l s o undergo a 1,2-hydrogen s h i f t t o f o r m HNOH
which c a n d i s s o c i a t e t o f o r m e i t h e r HNO+H o r NH+OH ( R e a c t i o n s ( 8 )
or ( 9 ) ) .
T h e r e s h o u l d a l s o be s u f f i c i e n t e n e r g y f o r H N0 t o d i s s o
c i a t e t o N0+H
2
2s
NH +0
2
*-0+
= -85 k c a l - m o l e "
(11)
However, t h e dominant r e a c t i o n i s e x p e c t e d t o be t h e d i r e c t d i s
placement r e a c t i o n (9) with s m a l l e r branching r a t i o s f o r r e a c t i o n s
(10) and even l e s s f o r ( 1 1 ) .

112
PROCESSES
On t h e q u a r t e t s u r f a c e , no i n t e r m e d i a t e complex e x i s t s t h a t
i s s t a b l e w i t h r e s p e c t t o NH +o . However, h y d r o g e n a b s t r a c t i o n
( r e a c t i o n (10)) can occur, having a small a c t i v a t i o n b a r r i e r .
On t h e o t h e r hand, t h e r e i s no pathway t o t h e e x o t h e r m i c p r o d u c t s
N ( S ) + H o.
T h u s , we c o n c l u d e t h a t a t room t e m p e r a t u r e , t h e r e a c t i o n
NH +o s h o u l d be d o m i n a t e d by r e a c t i o n ( 9 ) w i t h some s m a l l e r
b r a n c h i n g p r o b a b i l i t y f o r r e a c t i o n s (10) and ( 1 1 ) , a l l o c c u r r i n g
on t h e d o u b l e t s u r f a c e w i t h no a c t i v a t i o n e n e r g y . A t h i g h e r
t e m p e r a t u r e s , t h e h y d r o g e n a b s t r a c t i o n r e a c t i o n (10) s h o u l d
d o m i n a t e . We f i n d no r e a s o n t o e x p e c t t h e NH +o r e a c t i o n r a t e
a t room t e m p e r a t u r e t o be a p p r e c i a b l y s m a l l e r t h a n i t s i s o e l e c
t r o n i c c o u n t e r p a r t s , CH3+0 and OH+0.
2
NH+0. The r e a c t i o n NH+0 i s , i n many r e s p e c t s , a n a l o g o u s t o t h e

r e a c t i o n o f NH +o. Two s e t s o f r e a c t i o n p r o d u c t s have been used i n
c o m b u s t i o n m o d e l i n g , (1,3,5,) i . e . ,
2
NH+0
*-0+
= -74 k c a l - m o l e "
(12)
NH+0
*-0+
= -24 k c a l - m o l e "
(13)
and
F o r r e a c t i o n ( 1 2 ) an a c t i v a t i o n e n e r g y o f 5 k c a l - m o l e " i s
used w h i l e f o r r e a c t i o n (13) t h e a c t i v a t i o n e n e r g y used i s v e r y
small (0.1 k c a l - m o l e " ) .
I n F i g u r e 4, we p r e s e n t t h e r e s u l t s
f o r t h e i s o m e r i c c o m p l e x e s on t h e l o w e s t s i n g l e t ( A ) and
t r i p l e t ( A") s u r f a c e s . These r e s u l t s a r e c o n s i s t e n t with
o t h e r work on t h e HNO s y s t e m ( 3 4 , 3 5 ) .
The HNO r a d i c a l i n t e r m e d i a t e s c a n be formed from NH+0 w i t h o u t
an e n e r g y b a r r i e r . The f o r m a t i o n e n e r g y o f t h e c o m p l e x e s i s
s u f f i c i e n t t o e i t h e r d i s s o c i a t e t o H+NO ( r e a c t i o n ( 1 2 ) ) o r a l l o w
t h e 1,2-hydrogen s h i f t ancj d i s s o c i a t i o n t o OH+N ( r e a c t i o n ( 1 3 ) ) .
The A " s u r f a c e i s d i r e c t l y a n a l o g o u s t o t h e d o u b l e t s u r f a c e f o r
NH +o ( F i g u r e 3 ) . F o r t h e A s u r f a c e t h e d o m i n a n t p r o d u c t s h o u l d
be NO+H t h o u g h some N+OH c a n be f o r m e d . On t h e o t h e r hand, HNO
formed on t h e -' s u r f a c e c a n o n l y d i s s o c i a t e t o H+NO s i n c e
f o r m a t i o n o f OH+N i s s p i n f o r b i d d e n . A t h i g h e r t e m p e r a t u r e s , t h e
d i r e c t h y d r o g e n a b s t r a c t i o n r e a c t i o n c a n o c c u r , p a r t i c u l a r l y on
the q u i n t e t s u r f a c e , r e q u i r i n g a small a c t i v a t i o n energy.
T h u s , f o r NH+0 we c o n c l u d e t h a t t h e r e a c t i o n r a t e s h o u l d be
1

7.
MELIUS AND BINKLEY
Reactions of NH and NH
with and 0
113
f a s t , w i t h no a c t i v a t i o n e n e r g y f o r r e a c t i o n s (12) and (13) g o i n g

t h r o u g h t h e HNO i n t e r m e d i a t e and w i t h a s l i g h t a c t i v a t i o n e n e r g y
f o r t h e d i r e c t hydrogen a b s t r a c t i o n r e a c t i o n ( 1 3 ) .
Conclusions
The c a l c u l a t i o n a l a p p r o a c h used h e r e i n v o l v i n g f o u r t h - o r d e r
M j a l l e r - P l e s s e t p e r t u r b a t i o n t h e o r y w i t h bond a d d i t i v i t y
c o r r e c t i o n s (BAC-MP4), h a s been shown t o be a p o w e r f u l t o o l f o r
d e t e r m i n i n g h e a t s o f f o r m a t i o n o f m o l e c u l a r s p e c i e s and f o r
a n a l y z i n g p o s s i b l e r e a c t i o n p a t h w a y s . F o r N H and NH r e a c t i n g
w i t h 0 and 0 we have been a b l e t o d i s t i n g u i s h between l i k e l y and
u n l i k e l y r e a c t i o n p r o d u c t s b a s e d on t h e s t a b i l i t y o f v a r i o u s
r e a c t i o n i n t e r m e d i a t e s compared t o t h e r e a c t a n t s and p r o d u c t s .
The r e a c t i o n s s t u d i e d h e r e a r e t y p i c a l o f many systems i n
t h a t t h e y a r e complex, i n v o l v i n g m u l t i p l e p o t e n t i a l e n e r g y s u r
f a c e s w i t h c o m p e t i n g p a t h w a y s , even when t h e same p r o d u c t c h a n n e l
e x i s t s . T h u s , t h e o r e t i c a l r e s u l t s such a s t h e s e can be h e l p f u l
b o t h i n a n a l y z i n g e x p e r i m e n t a l r a t e c o n s t a n t s a s w e l l as i n com
p u t e r m o d e l i n g o f r e a c t i o n s y s t e m s . A d d i t i o n a l work i s needed t o
a d d r e s s t h e r e a c t i o n pathways f o r p r o d u c t s g o i n g t o o t h e r p r o
d u c t s , s i n c e o t h e r p a r t s o f t h e p o t e n t i a l e n e r g y s u r f a c e may be
i n v o l v e d . We a r e c u r r e n t l y i n t h e p r o c e s s o f d e v e l o p i n g an
a p p r o a c h f o r c a l c u l a t i n g t r a n s i t i o n s t a t e e n e r g y b a r r i e r s (which
were o n l y i n c l u d e d s c h e m a t i c a l l y i n t h i s p a p e r ) , which can be o f
comparable accuracy t o the r e s u l t s presented here.
Acknowledgments
The a u t h o r s would l i k e t o g i v e p a r t i c u l a r t h a n k s t o Dr. R. J .
B l i n t o f General Motors f o r encouraging our i n v e s t i g a t i o n o f
t h e s e N-H-0 r e a c t i o n s and p r o v i d i n g e n l i g h t e n i n g d i s c u s s i o n s
i n v o l v i n g t h e p o s s i b l e r e a c t i o n m e c h a n i s m s . T h e a u t h o r s would a l s o
l i k e t o thank D r s . J . A. M i l l e r , W. A. G o d d a r d , and M. J . F r i s c h
f o r h e l p f u l discussions i n v o l v i n g various aspects o f t h i s
r e s e a r c h . T h i s work was s u p p o r t e d by t h e U. S. Department o f
E n e r g y , B a s i c E n e r g y S c i e n c e , C h e m i c a l P h y s i c s Program.

114
PROCESSES
Literature Cited
1. J . A. Miller, Combustion and Flame , 1981, 43, 81.

2. R. K. Lyon, A. M. Dean, and J. E. Hardy, Nineteenth Symposium
(International) on Combustion, The Combustion Institute,
Pittsburgh, PA, 1982, 97.
3. J . Duxbury and . H. Pratt, 15th Symposium (Int.) Combust.
(Proc.) 15th, 1975, 843.
4. S. Azuhata, R. Kaji, H. Akimoto, and Y. Hishinuma, 18th Symp.
(Intl.) Combustion Proc. , 18th, 1981, 845.
5. C. J. Dasch and R. J. Blint, General Motors Research
Publication-4232(1982).
6. N. F u j i i , H. Miyama, M. Koshi, and T. Asaba, 18th Symp.
(Intl.) Combustion Proc., 18th, 873 (1981).
7. H. Gesser, J. Am. Chem. S o c , 1955, 77, 2626.
8. D. Husain and R. G. W. Norrish, Proc. R. Soc. London, 1963,
273A, 145.
9. T. Takeyama and H. Miyama, J. Chem. Phys., 1965, 42, 3737.
10. D. C. Bull, Combustion and Flame , 1968, 12, 603.
11. J . N. Bradley, R. N. Butlin, and D. Lewis, Trans. Faraday
Soc., 1968, 64, 71.
12. L . J. Drummond, Combustion Science and Technology, 1972,
5, 175.
13. R. K. Jayanty, R. Simonaitis, and J. Heicklen, J. Phys. Chem.,
1976, 80, 433.
14. W. Hack, 0. Horie, and H. Gg. Wagner, J. Phys. Chem., 1982,
86, 765.
15. P. B. Pagsberg, J. Eriksen, and H. C. Christensen, J. Phys.
Chem., 1979, 83, 582.
16. S. W. Benson, 18th Symp. (Intl.) Combustion P r o c , 18th,
1981, 882.
17. C. Pouchan and M. Chaillet, Chem. Phys. Lett., 1982, 90,
310.
18. R. Lesclaux and M. Demissy, Nouv. J. Chim., 1977, 1, 443.
19. S. G. Cheskis and O. M. Sarkisov, Chem. Phys. Lett., 1979,
62, 72.
20. C. Zetzsch and I. Hansen, Ber. Bunsenges Phys. Chem., 1978,
82, 830.
21. J . C. McConnell, J. Geophys. Res. 1973, 78, 7812.
22. M. Gehring, K. Hoyermann, H. Schacke, and J. Wolfrum, 14th
Symp. (Int.) Combust. Proc 14th, 1973, 99.

7.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
MELIUS A N D BINKLEY
Reactions of H and NH with and 0

2
115
E . A. Albers, K. Hoyermann, H. Gg. Wagner, and J. Wolfrum,

12th Symp. (Int.) Combust. Proc., 12th, 1969, 313.
R. Krishnan, M. J. F r i s c h , and J. A. Pople, J. Chem. Phys.
1980, 72, 4244; R. Krishnan and J. A. Pople, Int. J.
Quant. Chem., 1978, 14, 91.
J . S. Binkley and C. F . Melius, to be published.
P. E. Hariharan and J. A. Pople, Theor. Chim. Acta, 1973,
28, 213.
C. C. J. Roothaan, Rev. Mod. Phys., 1951, 23, 19.
J . A. Pople and R. K. Ne sbet, J. Chem. Phys., 1954, 22,
571.
J . A.Pople, R. Krishnan, H. B. Schlegel, and J. S. Binkley,
Int. J. Quant. Chem., 1979, 513, 225.
P. J. Hay, T. H. Dunning, and W. A. Goddard, J. Chem. Phys.,
1975, 62, 3912.
K. Yamaguchi, S. Yabushita, and T. Fueno, J. Chem. Phys.,
1979, 71, 2321.
A. J. Varandas and J. N. Murrell, Chem. Phys. L e t t . , 1982,
88, 1.
L . B. Harding and W. A. Goddard, J. Amer. Chem.Soc.,1978,
100, 7180.
P. J. Bruna, Chem. Phys., 1980, 49, 39; P. J. Bruna and
C. M. Marian, Chem. Phys. Lett, 1979, 67, 109.
O. Nomura and S. Iwata, Chem. Phys. Lett., 1979, 66, 523.
RECEIVED
December 21, 1983

8
Fast Flames and Detonations
J O H N H . S. LEE
McGill University, Mechanical Engineering Department, 817 Sherbrooke St. W., Montreal,
Quebec, H3A 2K6, Canada
This paper centers on the problem of turbulent flame

acceleration by obstacles and the prediction of the
dynamic detonation parameters of fuel-air mixtures.
Current state-of-the-art in the understanding of
these phenomena, as well as progress made in achiev
ing empirical and quantitative descriptions of these
combustion processes, are reviewed. The specific
topics discussed are i) the maximum attainable tur
bulent flame speed in an obstacle array, ii) compu
ter simulation of turbulent flame accelerations,
iii) correlation between the detonation cell size
and the dynamic parameters of fuel-air detonations,
and iv) the transition from deflagration to detona
tion. Future directions in the investigation of
these problems are also discussed.
The p r i m a r y c o n c e r n o f e n g i n e e r s i n v o l v e d i n t h e d e s i g n o f n u c l e a r
r e a c t o r s , c h e m i c a l p l a n t s , o f f - s h o r e p l a t f o r m s and t a n k e r s , i s t h e
o v e r p r e s s u r e - t i m e d e v e l o p m e n t when l a r g e v o l u m e s o f f u e l - a i r m i x t u r e s a r e a c c i d e n t a l l y f o r m e d a n d i g n i t e d . The p r o b l e m o f e s t i mating t h i s o v e r p r e s s u r e - t i m e development i s an e x t r e m e l y complex
one.
D e p e n d i n g o n t h e i n i t i a l and b o u n d a r y c o n d i t i o n s , t h e same
c o m b u s t i b l e m i x t u r e c a n y i e l d v o l u m e t r i c o r mass b u r n i n g r a t e
t h a t d i f f e r s by a few o r d e r s o f magnitudes. F o r example, t h e
burning v e l o c i t y o f laminar flames i n s t o i c h i o m e t r i c mixtures o f
t h e common h y d r o c a r b o n f u e l s w i t h a i r i s o f t h e o r d e r o f h a l f a
meter p e r second, c o r r e s p o n d i n g t o flame speeds ( i . e . , r e l a t i v e t o
the f i x e d o b s e r v e r ) o f about a few meters p e r second.
However,
u n d e r s u i t a b l e c o n d i t i o n s , t h e same m i x t u r e s c a n s u s t a i n f a s t t u r b u l e n t flames w i t h flame speeds o f t h e o r d e r o f hundreds o f meters
per second.
Quite o f t e n , these f a s t flames t r a n s i t spontaneously
t o d e t o n a t i o n s w h i c h p r o p a g a t e t o a t y p i c a l v e l o c i t y o f a b o u t 1800
m/sec i n t h e s e s t o i c h i o m e t r i c f u e l - a i r m i x t u r e s . The o v e r p r e s s u r e - t i m e d e v e l o p m e n t depends o n t h e mass b u r n i n g r a t e o r t h e
f l a m e s p e e d w h i c h , i n t u r n , depends s t r o n g l y o n t h e b o u n d a r y
conditions (mainly the confinement).
0097-6156/84/0249-0119509.00/0
120
I n c l o s e d v e s s e l s ( f u l l y c o n f i n e d ) , t h e e v e n t u a l peak p r e s s u r e o b t a i n e d depends p r i m a r i l y on t h e e n e r g e t i c s o f t h e m i x t u r e s .
The b u r n i n g r a t e c o n t r o l s t o some e x t e n t t h e amount o f h e a t (hence
the p r e s s u r e l o s s ) d u r i n g t h e combustion p r o c e s s i t s e l f and t h i s
w i l l r e s u l t i n a l o w e r v a l u e f o r t h e f i n a l p e a k o v e r p r e s s u r e . The
peak o v e r p r e s s u r e f o r c o n f i n e d e x p l o s i o n s c o r r e s p o n d s c l o s e l y t o
the t h e o r e t i c a l c o n s t a n t volume o r i s o c h o r i c e x p l o s i o n p r e s s u r e
f o r t h e p a r t i c u l a r m i x t u r e , w h i c h c a n be c a l c u l a t e d r e a d i l y f r o m
e q u i l i b r i u m t h e r m o d y n a m i c s when l o s s e s a r e i g n o r e d . The e s t i m a t i o n o f t h e r a t e o f o v e r p r e s s u r e r i s e , h o w e v e r , i s much more d i f f i c u l t s i n c e i t depends on t h e mass b u r n i n g r a t e o r f l a m e s p e e d .
For s l o w l a m i n a r f l a m e s , t h e r a t e o f p r e s s u r e r i s e i s slow and
v e n t i n g i s o f t e n q u i t e e f f e c t i v e i n l i m i t i n g t h e peak o v e r p r e s s u r e
t o any d e s i r e d l e v e l .
I n unconfined c o n d i t i o n s , the overpressure
r i s e a s s o c i a t e d w i t h slow d e f l a g r a t i o n s a r e u s u a l l y n e g l i g i b l y
small.
Under t h e a p p r o p r i a t e boundary c o n d i t i o n s and confinement,
slow d e f l a g r a t i o n s can a c c e l e r a t e r a p i d l y t o very f a s t t u r b u l e n t
deflagrations.
T u r b u l e n t f l a m e s depend s t r o n g l y on t h e b o u n d a r y
c o n d i t i o n s which determine the magnitude o f the displacement f l o w
v e l o c i t y and hence t h e t u r b u l e n c e l e v e l i n t h e unburned m i x t u r e .
T h u s , t u r b u l e n t f l a m e s p e e d s may r a n g e f r o m s l i g h t l y above l a m i n a r
flame speeds o f a few meters p e r second t o a few hundreds o f meters
p e r s e c o n d j u s t p r i o r t o t h e o n s e t o f d e t o n a t i o n . The r a t e o f
o v e r p r e s s u r e r i s e i s s t r o n g l y dependent on t h e flame speed. F o r
f a s t d e f l a g r a t i o n above a f e w t e n s o f m e t e r s p e r s e c o n d , v e n t i n g
becomes i n e f f e c t i v e .
Confinement a l s o p l a y s a d e c r e a s i n g l y minor
r o l e i n c o n t r o l l i n g t h e peak o v e r p r e s s u r e a c h i e v e d .
For violent
t u r b u l e n t flames w i t h s u p e r s o n i c speeds o f t h e o r d e r o f a few
hundreds o f meters p e r second, o v e r p r e s s u r e s o f t h e o r d e r o f a
few b a r s a r e o b t a i n e d e v e n i n u n c o n f i n e d g e o m e t r y .
Fast turbulent d e f l a g r a t i o n s often t r a n s i t spontaneously t o
detonations.
For f u l l y developed s e l f - s u s t a i n e d d e t o n a t i o n ,
b o u n d a r y c o n d i t i o n s and c o n f i n e m e n t p l a y m i n o r r o l e s .
The ChapmanJouguet v e l o c i t y and o v e r p r e s s u r e a r e based on t h e e n e r g e t i c s o f
t h e m i x t u r e a n d c a n be e v a l u a t e d f r o m e q u i l i b r i u m t h e r m o d y n a m i c
computations.
D u r i n g t h e o n s e t o f d e t o n a t i o n , t h e t r a n s i e n t peak
o v e r p r e s s u r e s d e v e l o p e d c a n be much h i g h e r t h a n t h e e q u i l i b r i u m
d e t o n a t i o n p r e s s u r e s . T r a n s i t i o n from d e f l a g r a t i o n t o d e t o n a t i o n
i s t o be a v o i d e d w h e n e v e r p o s s i b l e b e c a u s e o f t h i s e x t r e m e l y h i g h
pressure t r a n s i e n t a t the onset of detonation.
The p r e d i c t i o n o f t h e o v e r p r e s s u r e - t i m e h i s t o r y a s s o c i a t e d
w i t h t h e combustion o f an e x p l o s i v e m i x t u r e under s p e c i f i e d c o n d i t i o n s i s the c e n t r a l problem o f r e s e a r c h i n the l o s s p r e v e n t i o n
field.
I n t h e p a s t d e c a d e , s i g n i f i c a n t p r o g r e s s h a s b e e n made i n
t h e u n d e r s t a n d i n g o f t h e f u n d a m e n t a l mechanisms i n v o l v e d i n t h e
complex combustion p r o c e s s e s .
Prompted by t h e urgency i n r e s o l v i n g s a f e t y i s s u e s i n LNG t r a n s p o r t , o f f s h o r e o i l p r o d u c t i o n p l a t f o r m s , and n u c l e a r r e a c t o r s , e x t e n s i v e r e s e a r c h p r o g r a m s on g a s

8.
LEE
Fast Flames and
121
Detonations
e x p l o s i o n s i n v o l v i n g l a r g e s c a l e f i e l d e x p e r i m e n t s have b e e n c a r ried out i n various countries.

A number o f r e v i e w s h a v e a l r e a d y
b e e n w r i t t e n d e s c r i b i n g t h e i m p o r t a n t p r o g r e s s made i n t h i s f i e l d
(1-4).
The p r e s e n t p a p e r e m p h a s i z e s t h e more r e c e n t r e s u l t s , p a r t i c u l a r l y t h e a u t h o r ' s own w o r k , i n t h i s v e r y r a p i d l y a d v a n c i n g
field.
However, a c e r t a i n amount o f f u n d a m e n t a l i d e a s e x p o s e d i n
p r e v i o u s a r t i c l e s w i l l be r e p e a t e d t o make t h e p a p e r s e l f - c o n tained.
The e a r l i e r r e v i e w p a p e r s , p a r t i c u l a r l y R e f e r e n c e s 1 a n d
2, s h o u l d be r e f e r r e d t o f o r a c o m p l e t e d i s c u s s i o n o f t h e t u r b u l e n t f l a m e a c c e l e r a t i o n mechanisms.
T u r b u l e n t Flame A c c e l e r a t i o n
(General
Considerations)
I t h a s b e e n e s t a b l i s h e d t h a t b y f a r t h e most i m p o r t a n t mechanism
o f f l a m e a c c e l e r a t i o n i s t h a t due t o t u r b u l e n c e c r e a t e d b y o b s t a c l e s i n the p a t h o f the p r o p a g a t i n g f l a m e . As a r e s u l t o f t h e
l a r g e t e m p e r a t u r e change a c r o s s a f l a m e , t h e r e c o r r e s p o n d s a n i n c r e a s e i n t h e s p e c i f i c volume. This l e a d s t o a d i s p l a c e m e n t f l o w
i n the unburned m i x t u r e ahead o f the p r o p a g a t i n g flame w i t h a v e l o c i t y o f a b o u t t h e same o r d e r o f m a g n i t u d e a s t h e s p e e d o f t h e
propagating flame i t s e l f .
Large p h y s i c a l obstructions i n t h i s
displacement f l o w w i l l c r e a t e a v e l o c i t y g r a d i e n t f i e l d as w e l l as
shear l a y e r s . As t h e flame advances i n t o t h i s v e l o c i t y g r a d i e n t
f i e l d , t h e f l a m e s h e e t w i l l be " s t r e t c h e d " a n d " f o l d e d
resulting
i n an enlargement o f the b u r n i n g area and thus i n c r e a s i n g t h e
v o l u m e t r i c o r mass b u r n i n g r a t e . T u r b u l e n c e i n t h e s h e a r l a y e r s
i n t h e wake o f t h e o b s t r u c t i o n s a l s o e n h a n c e s t h e l o c a l b u r n i n g
v e l o c i t y o f t h e " f o l d e d " flame sheet because o f the higher t u r b u lent transport rates.
T h i s combined e f f e c t o f l a r g e s c a l e f l a m e
f o l d i n g and f i n e r s c a l e t u r b u l e n t enhancement o f t h e l o c a l b u r n i n g
v e l o c i t y c o n t r i b u t e s t o i n c r e a s e the v o l u m e t r i c b u r n i n g r a t e .
Hence, a h i g h e r e f f e c t i v e " g l o b a l " t u r b u l e n t f l a m e s p e e d i s o b tained.
H i g h e r flame speeds w i l l i n t u r n l e a d t o h i g h e r d i s p l a c e ment f l o w v e l o c i t i e s i n t h e u n b u r n e d m i x t u r e , w h i c h t h e n g i v e r i s e
t o more s e v e r e v e l o c i t y g r a d i e n t s a n d h i g h e r t u r b u l e n t i n t e n s i t y
i n t h e shear l a y e r s . This p o s i t i v e feedback loop c o n s t i t u t e s a
v e r y p o w e r f u l f l a m e a c c e l e r a t i o n mechanism. Flame s p e e d s o f t h e
order o f hundreds o f meters p e r second and even spontaneous t r a n s i t i o n s from d e f l a g r a t i o n t o d e t o n a t i o n have been o b s e r v e d i n
r a t h e r i n s e n s i t i v e f u e l - a i r mixtures under a p p r o p r i a t e
conditions.
P i o n e e r i n g s t u d i e s o f f l a m e a c c e l e r a t i o n i n a n o b s t a c l e a r r a y were
c a r r i e d o u t b y Chapman a n d W h e e l e r (6) u s i n g o r i f i c e p l a t e s i n a
r o u n d t u b e a n d b y S h c h e l k h i n (7), who u s e d a c o i l e d w i r e h e l i x i n s i d e t h e tube t o c r e a t e t h e t u r b u l e n c e .
I n the p a s t decade, e x t e n s i v e e x p e r i m e n t s on flame a c c e l e r a t i o n have been c a r r i e d o u t a t
G t f t t i n g e n a n d M c G i l l U n i v e r s i t y . The i n v e s t i g a t i o n s a t t h e I n s t i t u t f t t r P h y s i k a l i s c h e Chemie i n G B t t i n g e n h a v e b e e n r e v i e w e d b y
Wagner ( 8 ) , w h i l e t h e s t u d i e s c a r r i e d o u t a t t h e Shock Wave
P h y s i c s L a b o r a t o r y a t M c G i l l h a v e b e e n s u m m a r i z e d b y Moen ( 4 ) i n
1981.
L a r g e s c a l e e x p e r i m e n t s i n a 2.5 m d i a m e t e r b y 10 m l o n g
1 1

122
t u b e h a v e a l s o b e e n c a r r i e d o u t i n Norway and t h e s e s t u d i e s have

been r e v i e w e d b y H j e r t a g e r ( 9 ) . F a i r l y l a r g e s c a l e e x p e r i m e n t s on
f l a m e a c c e l e r a t i o n s have a l s o b e e n r e p o r t e d b y G e i g e r (10) o f t h e
B a t t e l l e I n s t i t u t e i n F r a n k f u r t and b y Zeeuwen ( 1 1 ) o f t h e TNO i n
Holland.
U r t i e w ( 1 2 ) and S t r e h l o w ( 1 3 ) h a v e a l s o b e e n c a r r y i n g
o u t some l a b o r a t o r y s c a l e s t u d i e s on o b s t a c l e i n d u c e d f l a m e a c
c e l e r a t i o n s a n d a m a j o r l a r g e s c a l e f a c i l i t y c a l l e d FLAME ( a r e c
t a n g u l a r r e i n f o r c e d c o n c r e t e c h a n n e l 1.8 m x 2.4 m 30 m), h a s
r e c e n t l y b e e n c o m p l e t e d a t S a n d i a N a t i o n a l L a b o r a t o r y i n New
Mexico f o r flame a c c e l e r a t i o n s t u d i e s i n ^ - a i r m i x t u r e s (14) i n
connection w i t h l i g h t water nuclear r e a c t o r s a f e t y research.
I t may be c o n c l u d e d t h a t a l l t h e s e s t u d i e s on t u r b u l e n t f l a m e
a c c e l e r a t i o n by r e p e a t e d o r p e r i o d i c o b s t a c l e s have thus f a r p r o
duced e s s e n t i a l l y t h e f o l l o w i n g r e s u l t s .
They d e m o n s t r a t e t h a t
f l a m e s , even i n r a t h e r i n s e n s i t i v e f u e l - a i r m i x t u r e s , c a n , under
appropriate conditions, accelerate very r a p i d l y to very high
speeds and develop v e r y h i g h o v e r p r e s s u r e s .
The a c c e l e r a t i o n r a t e ,
t h e f l a m e s p e e d a t t a i n e d and t h e a s s o c i a t e d o v e r p r e s s u r e s d e v e
l o p e d a r e a l l f u n c t i o n s o f t h e p a r t i c u l a r f u e l , t h e m i x t u r e compo
s i t i o n , d e t a i l s o f t h e o b s t a c l e c o n f i g u r a t i o n s and t h e confinement
and g e o m e t r y o f f l a m e i t s e l f .
On a q u a l i t a t i v e b a s i s , t h e f l a m e
a c c e l e r a t i o n mechanisms a r e f a i r l y w e l l u n d e r s t o o d . On a q u a n t i
t a t i v e b a s i s , " a - p r i o r i " p r e d i c t i o n s o f t h e t u r b u l e n t flame speed
and p r e s s u r e d e v e l o p m e n t w i t h g i v e n i n i t i a l a n d b o u n d a r y c o n d i
t i o n s a r e s t i l l i n t h e f a r d i s t a n t f u t u r e . The two f o r m i d a b l e
p r o b l e m s t h a t h a v e t o be overcome a r e i ) t h e p r e d i c t i o n s o f t h e
t r a n s i e n t t r a n s m i s s i b l e t u r b u l e n t f l o w s t r u c t u r e i n t h e unburned
m i x t u r e ahead o f t h e f l a m e , and i i ) t h e p r e d i c t i o n s o f t h e combus
t i o n p r o c e s s e s f o r any g i v e n t u r b u l e n t f l o w s t r u c t u r e .
Computer
m o d e l l i n g w i t h a p p r o p r i a t e e m p i r i c a l i n p u t f r o m e x p e r i m e n t s may
p l a y a n i m p o r t a n t r o l e i n p r o v i d i n g an a n a l y t i c a l t o o l f o r q u a n t i
t a t i v e p r e d i c t i o n s w i t h i n a l i m i t e d range o f experimental
condi
tions.
The k i n d o f u s e f u l e x p e r i m e n t a l i n f o r m a t i o n w o u l d be m a x i
mum s t e a d y s t a t e v a l u e s f o r t h e t u r b u l e n t f l a m e s p e e d s i n g i v e n
obstacle arrays.
The maximum t u r b u l e n t f l a m e s p e e d r e p r e s e n t s a
c r i t i c a l b a l a n c e between t h e p o s i t i v e (enhanced t u r b u l e n t
diffusiv i t i e s ) a n d n e g a t i v e ( q u e n c h i n g ) mechanisms o f t u r b u l e n t combus
tion.
I n f o r m a t i o n on t h e dependence o f t h i s maximum f l a m e s p e e d
on t h e t y p e o f f u e l a n d m i x t u r e c o m p o s i t i o n (hence t h e c h e m i c a l
k i n e t i c s ) and t h e o b s t a c l e c o n f i g u r a t i o n s ( t u r b u l e n t f l o w s t r u c
t u r e ) may be u s e d t o c o n s t r u c t t h e k i n d o f e m p i r i c a l r e l a t i o n s h i p s
needed f o r t h e s e computer models. Most o f t h e e x p e r i m e n t a l s t u
d i e s thus f a r , p a r t i c u l a r l y t h e l a r g e s c a l e e x p e r i m e n t s , have been
c a r r i e d o u t i n r a t h e r " s h o r t " a p p a r a t u s , where t h e l e n g t h o f t h e
f l a m e t r a v e l i s n o t l a r g e , a s compared t o i t s t r a n s v e r s e d i m e n s i o n
( i . e . , L/D r a t i o f o r t u b e ) .
Thus, o n l y t h e i n i t i a l t r a n s i e n t
phase o r t h e a c c e l e r a t i o n p r o c e s s i s o b s e r v e d .
I n t h e p a s t few
y e a r s , a n e x t e n s i v e e x p e r i m e n t a l p r o g r a m was i n i t i a t e d t o i n v e s t i
g a t e t h e dependence o f t h e maximum s t e a d y s t a t e t u r b u l e n t f l a m e
s p e e d o n f u e l s , c o m p o s i t i o n and o b s t a c l e c o n f i g u r a t i o n s .
This
p a p e r p r e s e n t s some o f t h e r e s u l t s o b t a i n e d t o d a t e .

8. L E E
Fast Flames and
(Recent R e s u l t s )
To o b t a i n t h e maximum s t e a d y s t a t e t u r b u l e n t f l a m e s p e e d r e q u i r e s
r e l a t i v e l y long flame t r a v e l .
Three s t e e l combustion tubes o f
a b o u t 12 m l o n g a n d r e s p e c t i v e d i a m e t e r s o f 5 cm, 15 cm, a n d 30 cm
are used.
E v e n f o r t h e l a r g e s t 30 cm t u b e , t h e f l a m e p r o p a g a t i o n
c a n be o b s e r v e d o v e r a d i s t a n c e o f a b o u t 40 t u b e d i a m e t e r s . The
tubes a r e c l o s e d a t b o t h ends, w i t h i g n i t i o n e f f e c t e d by a s p a r k
a t one e n d . F o r a b o u t 8 0 % o f t h e f l a m e t r a v e l , t h e b o u n d a r y c o n d i t i o n s a t t h e o t h e r e n d o f t h e t u b e do n o t p l a y a n y s i g n i f i c a n t
roles.
The f l a m e p r o p a g a t i o n i s e s s e n t i a l l y t h e same a s t h a t f o r
a t u b e w i t h a n open downstream e n d . P r e m i x e d m i x t u r e s o f v a r i o u s
f u e l s ( C H , H , C H^, CH^, C H ) w i t h a i r a r e f i l l e d i n t o t h e t u b e
through standard procedures. D i a g n o s t i c s c o n s i s t o f time o f a r r i v a l , i o n i z a t i o n gauges ( s p a c e d a b o u t 0.5 m a p a r t ) f o r f l a m e
s p e e d measurements a n d p i e z o e l e c t r i c t r a n s d u c e r s ( a t v a r y i n g l o c a t i o n s a l o n g t h e tube) f o r m o n i t o r i n g t h e p r e s s u r e development. I t
was d e c i d e d t o u s e one s t a n d a r d t y p e o f s i m p l e o b s t a c l e c o n f i g u r a t i o n ( i . e . , c i r c u l a r o r i f i c e plates of various blockage r a t i o s ,
BR = ( 1 - [ d / D ] ) , s o t h a t t h e f l o w s t r u c t u r e i s r e l a t i v e l y
s t r a i g h t f o r w a r d a n d s y m m e t r i c a l , t h u s p e r m i t t i n g a n a l y s i s t o be
c a r r i e d o u t . I n t h e 5 cm d i a m e t e r t u b e , a " S h c h e l k h i n s p i r a l "
made o u t o f a 6.3 mm d i a m e t e r c o p p e r t u b i n g w i t h a p i t c h o f 5 cm
i s a l s o used f o r comparison purposes.
I n g e n e r a l , t h e f l a m e upon i g n i t i o n w i l l a c c e l e r a t e r a p i d l y
and r e a c h s t e a d y s t a t e w i t h i n a f e w m e t e r s o f f l a m e t r a v e l f o r
most o f t h e o b s t a c l e c o n f i g u r a t i o n s s t u d i e d .
L i t t l e attention
thus f a r h a s been devoted t o t h e a n a l y s i s o f t h e r a t e o f a c c e l e r a tion.
The s t e a d y s t a t e f l a m e s p e e d i s d e t e r m i n e d b y a v e r a g i n g
o v e r t h e s p e e d s o b t a i n e d f r o m a number o f d i f f e r e n t i o n i z a t i o n
p r o b e s . Under c e r t a i n c o n d i t i o n s , t h e s t e a d y s t a t e flame speed
may show l a r g e f l u c t u a t i o n s .
To d e m o n s t r a t e t h e g e n e r a l f e a t u r e s ,
t h e r e s u l t s f o r H - a i r m i x t u r e s i n t h e 5 cm t u b e u s i n g a 3 m
l e n g t h o f S h c h e l k h i n s p i r a l (BR = 0.44) i s shown i n F i g u r e 1. I t
c a n be o b s e r v e d t h a t t h e f l a m e a c c e l e r a t e s t o a maximum s t e a d y
s t a t e v a l u e i n about 1 m f o r a wide range o f H
concentration.
T h i s maximum s t e a d y s t a t e t u r b u l e n t f l a m e s p e e d depends a l s o o n
t h e H c o n c e n t r a t i o n i t s e l f a n d r a n g e s f r o m a b o u t 100 m/sec (y 10%
H ) t o a b o u t 1800 m/sec ( 3 0 % ^ H ^ 4 5 % H ) . Upon e x i t i n g t h e 3 m
length o f the obstacle ( i . e . , the Shchelkhin s p i r a l ) i n t o t h e
"smooth" t u b e , t h e f l a m e i m m e d i a t e l y d e c e l e r a t e s .
F o r H ^ 15%,
t h e f l a m e d e c e l e r a t e s t o a new a n d much l o w e r s t e a d y s t a t e v a l u e
c o r r e s p o n d i n g t o t h e smooth w a l l b o u n d a r y c o n d i t i o n .
However, f o r
H ^ 15%, t h e flame r e a c c e l e r a t e s and t r a n s i t s t o d e t o n a t i o n a f t e r
a couple o f meters o f flame t r a v e l ( t h e t r a n s i t i o n d i s t a n c e depends o n t h e H c o n c e n t r a t i o n ) .
We s h a l l e l a b o r a t e more o n t h e
t r a n s i t i o n phenomenon i n a l a t e r s e c t i o n .
The maximum s t e a d y - s t a t e t u r b u l e n t f l a m e s p e e d s a s a f u n c t i o n
2
123
Detonations

F i g u r e 1. V a r i a t i o n o f f l a m e s p e e d w i t h d i s t a n c e f o r H - a i r
m i x t u r e s i n a 5-cm d i a m e t e r t u b e w i t h a 3-m l e n g t h o f S h c h e l k h i n
spiral obstacle.
p

8. LEE
Fast Flames and
Detonations
125
o f H c o n c e n t r a t i o n f o r t h e 5 cm a n d 15 cm d i a m e t e r t u b e s u s i n g
c i r c u l a r o r i f i c e o b s t a c l e s o f BR = 0.44 a n d 0.39 s p a c e d one t u b e
d i a m e t e r a p a r t a r e shown i n F i g u r e 2. The r e s u l t s i n d i c a t e t h a t
f o r t h e c a s e o f H - a i r m i x t u r e s , t h e dependence on t u b e d i a m e t e r
as w e l l a s b l o c k a g e r a t i o s i s n o t v e r y s t r o n g .
This suggests that
f o r t h i s v e r y s e n s i t i v e f u e l , t h e 5 cm s c a l e i s a l r e a d y s u f f i
c i e n t l y l a r g e when compared t o t h e c h e m i c a l l e n g t h s c a l e o f t h e
mixture f o r t h e combustion processes t o a s s e r t a s i g n i f i c a n t s c a l e
dependence on t h e t u b e d i a m e t e r .
S i m i l a r remarks a p p l y t o t h e
dependence o f t h e f l a m e s p e e d on t h e b l o c k a g e r a t i o .
For the
" r o u g h n e s s " s c a l e a s s o c i a t e d w i t h BR = 0.44 a n d 0.39 ( o r D - d - 1 . 6
cm a n d 0.63 cm f o r t h e 15 cm a n d 5 cm t u b e r e s p e c t i v e l y ) , t h e c h e
mical length scale f o r the s e n s i t i v e H - a i r mixture i s also s u f f i
c i e n t l y s m a l l f o r t h e f l a m e t o h a v e a s t r o n g d e p e n d e n c e on t h e
r a n g e o f t h e b l o c k a g e r a t i o o f 0.39 ' BR 0.44.
However, s t r o n g
e r dependence o n s c a l e w o u l d be a n t i c i p a t e d f o r t h e v e r y l e a n H a i r m i x t u r e s w h e r e t h e c h e m i c a l l e n g t h s c a l e w o u l d b e l a r g e r . The
dependence o f t h e f l a m e s p e e d on m i x t u r e c o m p o s i t i o n i s , h o w e v e r ,
much more p r o n o u n c e d . F o r H 1 3 % , f l a m e s p e e d s i n b o t h t u b e s
a r e o f t h e o r d e r o f a b o u t 100 m/sec. Then a v e r y s h a r p "jump"
o c c u r s a t H - 1 3 % when t h e f l a m e s p e e d i n c r e a s e s a b r u p t l y b y
three o r four f o l d .
T h i s a b r u p t i n c r e a s e may b e c r e d i t e d t o t h e
change i n t h e c h e m i c a l l e n g t h s c a l e . A s p o i n t e d o u t b y A t k i n s o n
(15) among o t h e r s , t h e r e a c t i o n + 0 -* OH + 0 i s i n c o m p e t i t i o n
w i t h t h e t h r e e body r e a c t i o n , H + 0 + M -> H 0 + M w i t h t h e l a t t e r
b e i n g more d o m i n a n t f o r t e m p e r a t u r e s b e l o w 1300K. A t a b o u t 1 3 %
H , t h e a d i a b a t i c f l a m e t e m p e r a t u r e i s o f t h e o r d e r o f 1300K.
T h u s , a c h a n g e o v e r t o t h e more r a p i d OH b r a n c h i n g r e a c t i o n may
t a k e p l a c e a t H - 1 3 % a n d g i v e r i s e t o a more r a p i d i n c r e a s e i n
t h e f l a m e s p e e d . The c h e m i c a l l e n g t h s c a l e i s a l s o s i g n i f i c a n t l y
r e d u c e d when t h e k i n e t i c mechanism changes t o r a p i d OH b r a n c h i n g .
2
A second r a p i d i n c r e a s e i n t h e flame speed occurs a t H

25%
f o r both tubes.
This corresponds t o a t r a n s i t i o n t o the detona
t i o n r e g i m e . The d e t o n a t i o n v e l o c i t y i n t h e o b s t a c l e f i e l d i s
t y p i c a l l y a b o u t 1500 m/sec a n d i s p r a c t i c a l l y i n d e p e n d e n t o f t h e
H
c o n c e n t r a t i o n up t o H - 45%.
For higher H
concentrations,
the d e t o n a t i o n v e l o c i t y a b r u p t l y drops back t o the v a l u e s f o r de
f l a g r a t i o n s p e e d s o f t h e o r d e r o f 800 m/sec. The s e v e r e p r e s s u r e
Cor momentum) l o s s e s due t o t h e p r e s e n c e o f t h e o b s t a c l e s a c c o u n t s
f o r t h e sub-Chapman-Jouguet d e t o n a t i o n v e l o c i t i e s o b s e r v e d . The
n o r m a l v e l o c i t i e s a r e a b o u t 2000 m/sec a s o b s e r v e d i n smooth t u b e s
f o r H c o n c e n t r a t i o n s i n t h e range ( i . e . , 25% ^ H 45%).
I n t h e r a n g e o f 1 3 % ^ H 25%, t h e f l a m e s p e e d showed a c o n
tinuous steady i n c r e a s e w i t h the H c o n c e n t r a t i o n .
This regime
i s p r o b a b l y dominated by the p r e s s u r e l o s s e s and gasdynamic "chok
ing" at the o r i f i c e .
A h i g h e r r a t e o f energy r e l e a s e ( i . e . , flame
power) a c c o u n t s f o r t h e s t e a d y c o n t i n u o u s i n c r e a s e o f t h e t u r b u
l e n t flame speed w i t h f u e l ( i . e . , H ) c o n c e n t r a t i o n .
Preliminary
e x p e r i m e n t s i n t h e 30 cm d i a m e t e r t u b e o b t a i n e d r e c e n t l y showed
similar qualitative results.
2

126
Figure 2 .
Comparison between the maximum t u r b u l e n t flame speed
f o r H^-air mixtures i n the 5-cm and 15-cm diameter tube w i t h
o r i f i c e plate obstacles.

8. L E E
Fast Flames and
Detonations
127
The peak o v e r p r e s s u r e a s s o c i a t e d w i t h t h e s e s t e a d y s t a t e f a s t
d e f l a g r a t i o n s i n H 2 ~ a i r m i x t u r e s a r e shown i n F i g u r e 3. S i m i l a r
t o t h e f l a m e s p e e d , t h e dependence o n t u b e d i a m e t e r a n d b l o c k a g e
r a t i o s a r e a l s o m i n i m a l . The same q u a l i t a t i v e t r e n d i s o b s e r v e d
f o r t h e dependence o f t h e p e a k o v e r p r e s s u r e on t h e m i x t u r e compo
sition.
The m a g n i t u d e o f t h e p e a k o v e r p r e s s u r e i s a l s o c o m p a t i b l e
w i t h t h e t h e o r e t i c a l e s t i m a t e based on t h e flame speeds g i v e n i n
F i g u r e 2. T h u s , t h e s e f a s t f l a m e s do c o r r e s p o n d t o v e r y h i g h mass
or v o l u m e t r i c b u r n i n g r a t e s a n d a r e n o t a s s o c i a t e d w i t h t h e k i n e
m a t i c s o f t h e m o t i o n o f t h e u n b u r n e d m i x t u r e s ahead o f t h e f l a m e .
In f a c t , f o r t h e s u p e r s o n i c flames ( i . e . , flame speeds g r e a t e r
t h a n t h e sound s p e e d i n t h e u n b u r n e d m i x t u r e s ) , t h e p r e s s u r e - t i m e
p r o f i l e s from t h e p i e z o e l e c t r i c t r a n s d u c e r s l o c a t e d a t v a r i o u s
p o s i t i o n s a l o n g t h e tube i n d i c a t e a s e r i e s o f " p r e s s u r e s p i k e s "
corresponding t o t h e a r r i v a l o f t h e r a t h e r extended t u r b u l e n t
b u r n i n g zone.
The s t r u c t u r e o f t h e s e f a s t t u r b u l e n t f l a m e s i s
s i m i l a r t o t h a t o b s e r v e d b y Oppenheim e t a l . ( 1 6 ) f o r t h e t u r b u
l e n t d e f l a g r a t i o n s j u s t p r i o r t o t h e o n s e t o f d e t o n a t i o n . To
v i s u a l i z e b e t t e r these f a s t d e f l a g r a t i o n s , t h e r e a d e r s s h o u l d con
s u l t t h e w o r k s o f Oppenheim a n d c o - w o r k e r s who t o o k e x t e n s i v e h i g h
speed s t r o b o s c o p i c l a s e r S c h l i e r e n photographs o f t h e s e f a s t t u r
b u l e n t flames w i t h e x c e p t i o n a l c l a r i t y and time r e s o l u t i o n .
F o r t h e o t h e r h y d r o c a r b o n f u e l s , t h e more s e n s i t i v e ones
( i . e . , C2H2 a n d C2H4) a s w e l l a s C3H3 a n d CH4 a r e s t u d i e d i n t h e
s m a l l e r 5 cm t u b e . The s t e a d y s t a t e f l a m e s p e e d s c o r r e s p o n d i n g t o
o r i f i c e p l a t e o b s t a c l e s o f BR = 0.44 f o r C2H2, C2H4 a n d C H g a r e
shown i n F i g u r e 4 a s f u n c t i o n s o f t h e m i x t u r e c o m p o s i t i o n ( i . e . ,
e q u i v a l e n c e r a t i o where s t o i c h i o m e t r i c c o m p o s i t i o n c o r r e s p o n d s
t o = 1 ) . F o r a c e t y l e n e w h i c h i s e v e n more s e n s i t i v e t o f u e l
t h a n h y d r o g e n , i t i s o b s e r v e d t h a t i g n i t i o n b y t h e weak s p a r k u s e d
became e r r a t i c when t h e C2H2 c o n c e n t r a t i o n i s l e s s t h a n a b o u t 3.5%.
However, when i g n i t i o n i s s u c c e s s f u l , t h e f l a m e a c c e l e r a t e s v e r y
r a p i d l y t o s t e a d y s t a t e v a l u e s o f a b o u t 800 m/sec. S i m i l a r t o H 2 a i r m i x t u r e s , abrupt t r a n s i t i o n t o t h e d e t o n a t i o n regime occurs a t
a r o u n d 5.5% C2H2 ( = 0 . 6 6 ) .
After that, the detonation velocity
shows a s l i g h t c o n t i n u o u s i n c r e a s e w i t h t h e C2H2 c o n c e n t r a t i o n .
F o r t h e l e s s s e n s i t i v e f u e l e t h y l e n e (C2H4), q u e n c h i n g i s o b s e r v e d
f o r C2H4 c o n c e n t r a t i o n l e s s t h a n a b o u t 4.5% ( - 0 . 6 7 ) .
By q u e n c h
i n g , i t means t h a t i g n i t i o n i s s u c c e s s f u l b u t f o l l o w i n g a r a p i d
a c c e l e r a t i o n , t h e f l a m e i s t h e n s u d d e n l y q u e n c h e d . The q u e n c h i n g
phenomenon i n v o l v e s t h e f l a m e f i r s t a c c e l e r a t i n g t o a s u f f i c i e n t l y
h i g h v e l o c i t y a f t e r t h e p a s s a g e t h r o u g h a number o f o r i f i c e p l a t e s ,
t h e n a s t h e f l a m e s p e e d r e a c h e s some c r i t i c a l v a l u e , t h e t u r b u l e n t
m i x i n g r a t e becomes s u f f i c i e n t l y f a s t t o c o o l t h e b u r n i n g zone a s
t h e f l a m e emerges f r o m t h e o r i f i c e .
E x t i n c t i o n t h e n r e s u l t s . The
q u e n c h i n g l i m i t depends o n t h e o r i f i c e d i a m e t e r f o r a g i v e n f u e l
and m i x t u r e c o m p o s i t i o n . The s t u d y o f t h i s q u e n c h i n g phenomenon
has a l r e a d y b e e n r e p o r t e d b y T h i b a u l t e t a l . (17) a n d t h e q u e n c h
ing c r i t e r i o n i s found t o be s i m i l a r t o t h a t f o r t h e flame s t a b i
l i z a t i o n b y b l u f f b o d i e s where t h e " b l o w - o f f " l i m i t r e q u i r e s a
3

128
15
5 cm
15 c m
B.R. = 0 . 4 4
TUBE
TUBE
B.R. =
0.39
1
1
A
10
le/
1/
.. 1
10
15
20
25
30
35
40
CONCENTRATION
F i g u r e 3. P e a k o v e r p r e s s u r e s
g a t i n g i n an o r i f i c e o b s t a c l e
I
45
f o rturbulent H^-air
array.
flames propa

8. L E E
Fast Flames and
129
Detonations
2000r
0.4
(Zb
0.6
0.8
1.0
EQUIVALENCE
1.2
1.4
1.6
1.8
RATIO
F i g u r e k.
Maximum t u r b u l e n t flame speeds f o r C^H - a i r , C^H^-air,
and C Hg-air mixtures i n a 5-cm diameter tube witn o r i f i c e obsta
cles .

130
c r i t i c a l b a l a n c e between the c h e m i c a l l e n g t h of the s c a l e r e a c t i n g

m i x t u r e and t h e f l u i d d y n a m i c m i x i n g l e n g t h s c a l e .
F o r H2 and
C2H2 w h e r e t h e q u e n c h i n g r e g i m e f o r t h e s i z e o f t h e o r i f i c e p l a t e s
u s e d was n o t o b s e r v e d , t h e c h e m i c a l l e n g t h s c a l e i s s u f f i c i e n t l y
s m a l l as compared t o t h e m i x i n g l e n g t h s c a l e .
I t i s expected that
h i g h e r blockage r a t i o s would l e a d to a s i m i l a r quenching regime
f o r t h e more s e n s i t i v e m i x t u r e s o f H2 and C2H2 i n a i r .
F o r p r o p a n e (C3H8), s i m i l a r r e s u l t s a r e o b t a i n e d .
Quenching
i s a g a i n o b s e r v e d f o r C3H3 l e s s t h a n a b o u t 3% on t h e l e a n s i d e and
g r e a t e r t h a n 4.5% on t h e r i c h s i d e .
Thus, o n l y w i t h i n a v e r y n a r
row band o f C3H3 c o n c e n t r a t i o n ( i . e . , 3% ^ C3H3
4.5%) when f l a m e
a c c e l e r a t i o n and s u b s e q u e n t p r o p a g a t i o n i s p o s s i b l e i n t h e 5 cm
t u b e w i t h t h e o r i f i c e p l a t e o b s t a c l e s u s e d f o r BR = 0.44.
For a
s m a l l e r b l o c k a g e r a t i o , t h e r a n g e o f C3H3 c o n c e n t r a t i o n where p r o
p a g a t i o n i s p o s s i b l e s h o u l d i n c r e a s e . F o r t h e same b l o c k a g e r a t i o
o f BR = 0.44, i n t h e 5 cm t u b e , s t e a d y p r o p a g a t i o n f o r m e t h a n e - a i r
m i x t u r e s c a n n o t be o b s e r v e d f o r a l l c o n c e n t r a t i o n s w i t h t h e f l a m mability limits.
Upon i g n i t i o n , t h e f l a m e w o u l d a c c e l e r a t e and
t h e n q u e n c h i t s e l f when i t s v e l o c i t y r e a c h e s some c r i t i c a l v a l u e .
Due t o t h e s e v e r e q u e n c h i n g e f f e c t s w i t h o r i f i c e p l a t e s o f
BR = 0.44 f o r t h e l e s s s e n s i t i v e C3H3 and CH4 i n t h e 5 cm t u b e ,
e x p e r i m e n t s w e r e c a r r i e d o u t u s i n g a " S h c h e l k h i n s p i r a l " as ob
stacles i n s t e a d of o r i f i c e p l a t e s .
The s p i r a l i s c o n t i n u o u s and
presents l e s s blockage to the displacement flow. I t i s d i f f i c u l t
t o d e f i n e an e q u i v a l e n t b l o c k a g e r a t i o f o r t h e s p i r a l o b s t a c l e and
t h e r e f o r e the p r o j e c t e d " b l o c k e d " a r e a to the f l o w i s used.
For a
w i r e d i a m e t e r o f 6.3 mm, t h e s p i r a l p r e s e n t s an e q u i v a l e n t b l o c k
age r a t i o o f 0.44 i n t h e 5 cm t u b e .
Using the Shchelkhin s p i r a l ,
r e s u l t s f o r CH4, C3H3 as w e l l as H2 a r e shown i n F i g u r e 5.
Flames
i n m e t h a n e - a i r m i x t u r e s a r e now n o t s e l f - q u e n c h e d and a r e i n gene
r a l l e s s t h a n 400 m/sec o v e r t h e e n t i r e r a n g e o f e q u i v a l e n c e r a t i o .
However, a t a b o u t t h e s t o i c h i o m e t r i c c o m p o s i t i o n o f - 1, w h e r e
i t i s most s e n s i t i v e , m e t h a n e - a i r
flames demonstrate a l a r g e
f l u c t u a t i o n i n w h i c h t h e f l a m e s p e e d may t a k e on v a l u e s b e t w e e n
400 m/sec and 800 m/sec. F o r C3H3, a more o r l e s s c o n t i n u o u s i n
c r e a s e t o d e t o n a t i o n speeds a r e observed i n the s p i r a l o b s t a c l e
field.
The d e t o n a t i o n r e g i m e p e r s i s t s f o r t h e r i c h C3H3 m i x t u r e s
u n t i l a sharp t r a n s i t i o n back to the d e f l a g r a t i o n regime occurs
^ 1.6.
Thus f o r a l e s s o b s t r u c t e d f l o w f i e l d , b o t h CH4 and C3H3
demonstrate the e x i s t e n c e of h i g h steady s t a t e t u r b u l e n t flame
speeds, a l t h o u g h the magnitude of the flame speed i s s l i g h t l y l e s s
t h a n t h e c o r r e s p o n d i n g v a l u e s f o r t h e more s e n s i t i v e f u e l s .
The
importance of the flame speed s c a l e i s apparent f o r l e s s s e n s i t i v e
mixtures with larger chemical length scales.
For H2~air mixtures,
r e s u l t s w i t h i n the s p i r a l o b s t a c l e are s i m i l a r to t h a t f o r the
o r i f i c e p l a t e o b s t a c l e s . With l e s s b l o c k a g e , hence p r e s s u r e
l o s s e s , t h e d e t o n a t i o n v e l o c i t i e s a r e now c l o s e t o t h e t h e o r e t i c a l
Chapman-Jouguet v a l u e s .
F o r t h e l e s s s e n s i t i v e m i x t u r e s , t h e s c a l i n g up t o l a r g e
d i m e n s i o n s ( i . e . , t u b e d i a m e t e r ) becomes i m p o r t a n t .
Figure 6

8. L E E
Fast Flames and
OBSTACLE
B.R.
=0.44
SPIRAL
131
Detonations
EQUIVALENCE
RATIO
Figure 5.
C o m p a r i s o n o f t h e maximum f l a m e s p e e d f o r CH^, C ^ H Q ,
and H i n a 5-cm t u b e w i t h a S h c h e l k h i n s p i r a l o b s t a c l e .

132
Figure 6 .
Maximum t u r b u l e n t flame speeds f o r CLHg-air and C ^ - a i r
i n the 15-cm diameter tube -with o r i f i c e o b s t a c l e s .

8. L E E
Fast Flames and
Detonations
133
shows t h e r e s u l t s f o r CH4 a n d C3H3 i n t h e 15 cm t u b e w i t h o r i f i c e

p l a t e o b s t a c l e s o f BR = 0.39.
F o r C3H3, s u d d e n t r a n s i t i o n t o h i g h
speed s u p e r s o n i c d e f l a g r a t i o n s o c c u r s a t e q u i v a l e n c e r a t i o s 0.75 a n d - 1.2. F o r 0.75 a n d ^ 1.2, t y p i c a l f l a m e s p e e d s
a r e o f t h e o r d e r o f 100 m/sec and b e l o w . Maximum f l a m e s p e e d o c
c u r s a t a r o u n d s t o i c h i o m e t r i c c o m p o s i t i o n o f - 1. However, e v e n
f o r t h e c a s e o f propane, t r a n s i t i o n s t o d e t o n a t i o n s a r e n o t o b s e r v
ed.
S i m i l a r r e s u l t s a r e o b t a i n e d f o r methane, b u t t h e range o f
composition i n which steady s t a t e p r o p a g a t i o n w i t h o u t quenching i s
s l i g h t l y narrower than propane. F o r example, t h e t r a n s i t i o n t o
t h e s u p e r s o n i c r e g i m e now o c c u r s a t 0.85 $j ^ 1.1 i n s t e a d o f
0.75
< 1.2 f o r p r o p a n e . Maximum f l a m e s p e e d s f o r CH4 a t - 1
i s a b o u t 750 m/sec, w h i c h i s s l i g h t l o w e r t h a n t h e c o r r e s p o n d i n g
v a l u e f o r p r o p a n e o f a b o u t 850 m/sec. I t s h o u l d b e n o t e d t h a t
t h e s e maximum f l a m e s p e e d s a r e c o m p a t i b l e t o t h o s e r e p o r t e d b y
Moen e t a l . (18) a n d H j e r t a g e r (19) i n a much l a r g e r s c a l e a p p a r a
t u s (2.5 m d i a m e t e r a n d 10 m l o n g ) . However, w i t h a n L/D r a t i o o f
4 i t i s d o u b t f u l t h a t t h e f l a m e s p e e d v a l u e s r e p o r t e d b y Moen a n d
H j e r t a g e r do r e p r e s e n t t h e f i n a l s t e a d y s t a t e v a l u e s . C u r r e n t e x
p e r i m e n t s i n t h e 30 cm t u b e w i l l e l u c i d a t e f u r t h e r on t h e i m p o r t
ant s c a l i n g problem.
(Computer S i m u l a t i o n )
T h e r e e x i s t numerous c o m p u t e r codes c a p a b l e o f s i m u l a t i n g m u l t i
d i m e n s i o n a l t i m e d e p e n d e n t t u r b u l e n t r e a c t i n g f l o w s . A number o f
a t t e m p t s h a v e a l r e a d y b e e n made t o a d a p t t h e s e c o m p u t e r c o d e s t o
model the problem o f t u r b u l e n t flame a c c e l e r a t i o n by r e p e a t e d ob
s t a c l e s (20-22). With the a p p r o p r i a t e i n p u t from experiments,
t h e y a l l managed t o r e p r o d u c e r e a s o n a b l y w e l l t h e t r e n d o f t h e e x
perimental results.
Due t o t h e e x p e n s e s i n v o l v e d i n c a r r y i n g o u t
l a r g e f u l l s c a l e e x p e r i m e n t s , computer m o d e l l i n g o r s i m u l a t i o n
w i l l p l a y an i m p o r t a n t r o l e i n p r o v i d i n g e s t i m a t e s o f p r e s s u r e de
velopments i n f u l l s c a l e s i t u a t i o n s under a v a r i e t y o f i n i t i a l and
b o u n d a r y c o n d i t i o n s , b a s e d on i n p u t f r o m a f e w s e l e c t e d s c a l e d
down e x p e r i m e n t s .
These c o m p u t e r c o d e s a r e i n g e n e r a l , s u f f i
c i e n t l y complex so t h a t t h e y a r e n o t a c c e s s i b l e t o t h o s e o u t s i d e
t h e g r o u p t h a t d e v e l o p e d them. A t a n y r a t e , a c q u i r i n g t h e e x p e r
t i s e r e q u i r e d t o u s e any one o f t h e s e c o d e s w o u l d t a k e a commit
ment o f one o r two m a n - y e a r s . D e p e n d i n g o n t h e a c c u r a c y d e s i r e d ,
the c o s t i n r u n n i n g t h e s e computer codes i s n o t t r i v i a l and i s
q u i t e o f t e n comparable t o t h e c o s t o f t h e a c t u a l performance o f
s c a l e d down e x p e r i m e n t s .
T h u s , e x c e p t f o r Government I n s t i t u t i o n s
and l a r g e R e s e a r c h C e n t e r s , i t i s n o t l i k e l y t o s e e a w i d e s p r e a d
use o f t h e s e c o m p l e x c o m p u t e r c o d e s .
I t i s o f i n t e r e s t t o r e v i e w some o f t h e r e s u l t s p r o d u c e d b y
one o f t h e s e c o m p u t e r c o d e s .
Due t o t h e h i g h r u n n i n g c o s t , t h e
V o r t e x Dynamics Code (22) w o u l d n o t l i k e l y b e a n a t t r a c t i v e c a n d i
date t o u s e i n s i m u l a t i n g a c t u a l complex s i t u a t i o n s .
The " k - "
t y p e code o f H j e r t a g e r (23) o r t h e CONCHAS-SPRAY code r e c e n t l y

134
a d a p t e d t o t h e f l a m e a c c e l e r a t i o n p r o b l e m by M a r x (24) w o u l d be
more a p p r o p r i a t e f o r s u c h p u r p o s e s .
However, t h e V o r t e x Dynamics
Code g i v e s an a c c u r a t e d e s c r i p t i o n o f t h e t u r b u l e n t f l o w s t r u c t u r e
and t h e b e h a v i o u r o f t h e f l a m e s u r f a c e as i t p r o p a g a t e s t h r o u g h
the v o r t i c i t y f i e l d .
T h u s , t h e V o r t e x Dynamics Code c a n be u s e d
t o s u p p l e m e n t t h e f u n d a m e n t a l s t u d i e s on f l a m e a c c e l e r a t i o n s by
p r o v i d i n g a r e a l i s t i c p i c t u r e of the development of the flame
s t r u c t u r e i n the complex t u r b u l e n t f i e l d .
I n o t h e r words, the
V o r t e x Dynamics Code p r o v i d e s a h i g h s p e e d s c h l i e r e n m o v i e o f t h e
complex t u r b u l e n t flame s t r u c t u r e t o f a c i l i t a t e t h e i n t e r p r e t a t i o n
of t h e a c t u a l p r e s s u r e - t i m e and f l a m e s p e e d d a t a f r o m e x p e r i m e n t s .
The a c t u a l t a k i n g o f h i g h s p e e d s c h l i e r e n m o v i e s i n f l a m e a c c e l e r a t i o n s i n a t m o s p h e r i c f u e l - a i r m i x t u r e s i s n o t f e a s i b l e due t o t h e
h i g h p r e s s u r e and l a r g e s c a l e s i n v o l v e d .
Then t h e V o r t e x Dynamics
Codes c a n be l o o k e d a t as more o f an e x p e r i m e n t a l d i a g n o s t i c t e c h n i q u e t h a n an a l g o r i t h m f o r e s t i m a t i n g t h e p r e s s u r e d e v e l o p m e n t o f
flame a c c e l e r a t i o n s i n complex s i t u a t i o n s .
F i g u r e 7 shows a s e l e c t e d s e q u e n c e o f a c o m p u t e r g e n e r a t e d
m o v i e u s i n g t h e V o r t e x D y n a m i c s Code o f a f l a m e p r o p a g a t i n g i n a
two d i m e n s i o n a l c h a n n e l w i t h b a f f l e p l a t e s as o b s t a c l e s s p a c e d one
c h a n n e l w i d t h a p a r t . As t h e f l a m e a d v a n c e s f r o m t h e c l o s e d end
( i g n i t i o n ) of the tube, the displacement f l o w through the o r i f i c e
c r e a t e s s h e a r l a y e r s as i n d i c a t e d by t h e r e g i o n s o f c o n c e n t r a t e d
vorticities.
On t h e o u t f l o w t h r o u g h t h e o r i f i c e , a v e l o c i t y g r a d i e n t i s g e n e r a t e d u p s t r e a m o f an o r i f i c e and t h e d i s t o r t i o n o f t h e
f l a m e as i t p r o p a g a t e s i n t o t h i s g r a d i e n t f i e l d i s c l e a r l y a p p a r e n t i n t h e f o u r t h f r a m e o f F i g u r e 7.
The v e r y r a p i d s t r e t c h i n g o f
t h e f l a m e as t h e f l a m e " t i p " i s b e i n g c o n v e c t e d by t h e j e t s
through the o r i f i c e i s i l l u s t r a t e d i n the l a s t frame.
I t should
be n o t e d t h a t i n t h i s s e q u e n c e o f c o m p u t a t i o n s , t h e f l a m e s h e e t i s
t r e a t e d as a t h i n s u r f a c e w i t h c o n s t a n t l o c a l b u r n i n g v e l o c i t y .
When a dependence o f t h e l o c a l b u r n i n g v e l o c i t y on t h e t u r b u l e n c e
f i e l d i s i n d u c e d i n t h e c o m p u t a t i o n s , a much more r a p i d b u r n i n g
w i l l occur i n the shear l a y e r s .
The c o m p u t e r g e n e r a t e d m o v i e
shown i n F i g u r e 7 c o r r e s p o n d s v e r y c l o s e l y t o t h e a c t u a l h i g h
speed s c h l i e r e n photographs o f flame a c c e l e r a t i o n through a b a f f l e
obstacle (25).
The V o r t e x D y n a m i c s Code has b e e n a p p l i e d r e c e n t l y t o t h e
s t u d y o f f l a m e a c c e l e r a t i o n i n a m u l t i p l e compartment chamber (26).
F i g u r e 8 shows a s e q u e n c e f r o m t h e c o m p u t e r g e n e r a t e d m o v i e u s i n g
t h e V o r t e x D y n a m i c s Code. A g a i n , t h e g e n e r a t i o n o f v o r t i c i t y i n
t h e s h e a r l a y e r s i n t h e wake o f t h e o b s t a c l e s i s c l e a r l y i l l u s trated.
The s t r e t c h i n g o f t h e f l a m e u n t i l b u r n i n g o c c u r s s i m u l t a n e o u s l y i n a l l t h e c o m p a r t m e n t s c a n a l s o be o b s e r v e d .
Of p a r t i c u l a r i n t e r e s t to note i s t h a t v o r t i c i t y generated i n upstream
s h e a r r e g i o n s i s c o n t i n u o u s l y c o n v e c t e d downstream by t h e f l o w .
T h u s , as t h e f l a m e a d v a n c e s , i t w i l l be p r o p a g a t i n g i n t o an i n c r e a s i n g l y more i n t e n s e v o r t i c i t y f i e l d , w h i c h i s due t o b o t h t h e
g e n e r a t i o n t h a t occurs l o c a l l y a t the shear l a y e r s , p l u s t h a t conv e c t e d from upstream shear r e g i o n s . T h i s l e a d s to v e r y i n t e n s e

LEE
Fast Flames and
Detonations
135
8.
Figure 7 Computer s i m u l a t i o n o f flame a c c e l e r a t i o n i n an a r r a y

o f o r i f i c e o b s t a c l e s using the Vortex Dynamics Code.

136
Tim e =
0.00
/
/
0.50
!
\
/
0.75
/
1
i ' W
1.00
1
F i g u r e 8. Computer s i m u l a t i o n u s i n g t h e V o r t e x Dynamics Code f o r
f l a m e a c c e l e r a t i o n i n m u l t i p l e compartment c h a m b e r s .

8. L E E
Fast Flames and
Detonations
137
t u r b u l e n c e and t h u s v e r y h i g h b u r n i n g r a t e s .
T h i s mechanism o f
l o c a l b u r n i n g r a t e enhancement due t o v o r t i c i t y swept down f r o m
upstream shear r e g i o n s i s v e r y important.
I t may r e s u l t i n a d e c r e a s i n g dependence o f t h e f l a m e a c c e l e r a t i o n r a t e o n t h e l o c a l
boundary c o n d i t i o n s . T h i s a l s o i m p l i e s t h a t v e r y h i g h b u r n i n g
r a t e s c a n o c c u r i n t h e g a s e s t h a t a r e v e n t e d f r o m one r e g i o n t o
a n o t h e r due t o t h e v o r t i c i t y c o n t a i n e d i n them. The above d i s cussions i l l u s t r a t e the k i n d o f combustion t o t h e fundamental
u n d e r s t a n d i n g o f flame a c c e l e r a t i o n t h a t computer s i m u l a t i o n c a n
p r o v i d e . To make a c t u a l t u r b u l e n c e measurements e x p e r i m e n t a l l y
f o r t h e s e a c c e l e r a t i n g f l a m e s and p e r f o r m t h e n e c e s s a r y d a t a r e d u c t i o n and a n a l y s i s t o a c h i e v e t h e same k i n d o f q u a n t i t a t i v e d e s c r i p t i o n o f t h e t u r b u l e n t f i e l d p r o v i d e d b y the V o r t e x Dynamics
Code w o u l d be a f o r m i d a b l e t a s k . T h u s , e v e n t h o u g h t h e s i m u l a t i o n
thus f a r has n e g l e c t e d i m p o r t a n t c o m p r e s s i b i l i t y e f f e c t s and b u r n i n g r a t e - t u r b u l e n c e c o u p l i n g , much c a n b e l e a r n e d a l r e a d y f r o m t h e
f l u i d dynamic p r o c e s s e s t h a t i t r e p r o d u c e s .
Detonations
A l t h o u g h n o t a common o c c u r e n c e f o r f u e l - a i r m i x t u r e s , p a r t i c u l a r l y u n d e r open u n c o n f i n e d c o n d i t i o n s , d e t o n a t i o n s c a n n o t b e i g nored i n r i s k a n a l y s i s .
The d i s t i n c t i v e c a p a b i l i t i e s o f d e t o n a t i o n waves n e c e s s i t a t e t h e n e e d t o a c q u i r e a c o m p l e t e u n d e r s t a n d i n g o f t h e phenomena s o t h a t t h e p r e c i s e c o n d i t i o n s i n w h i c h a d e t o n a t i o n wave c a n b e i n i t i a t e d and p r o p a g a t e d a r e known. I n t h i s
way, a r e a l i s t i c a s s e s s m e n t o f t h e d e t o n a t i o n h a z a r d s a s s o c i a t e d
w i t h a g i v e n i n s t a l l a t i o n c a n be o b t a i n e d .
I n g e n e r a l , d e t o n a t i o n waves i n s t o i c h i o m e t r i c m i x t u r e s o f
most o f t h e common h y d r o c a r b o n f u e l s w i t h a i r p r o p a g a t e a t a b o u t
1800 m/sec w i t h a n o v e r p r e s s u r e i n c r e a s e o f a b o u t 15 b a r s a c r o s s
t h e wave. I t i s a c u r i o u s f a c t o f n a t u r e t h a t t h e same e x p l o s i v e
m i x t u r e t h a t n o r m a l l y burns w i t h a l a m i n a r flame speed o f about a
few m e t e r s p e r s e c o n d c a n a l s o s u p p o r t t h e i n t e n s e c o m b u s t i o n a s s o c i a t e d w i t h t h e s e s u p e r s o n i c d e t o n a t i o n waves. The p r o c e s s e s
t h a t go o n i n s i d e t h e s t r u c t u r e o f d e t o n a t i o n f r o n t s a r e e x t r e m e l y
complex, i n v o l v i n g m u l t i - d i m e n s i o n a l shock i n t e r a c t i o n s i n an i n t e n s e t u r b u l e n t r e a c t i n g medium. However, i t i s a l s o a c u r i o u s
f a c t o f n a t u r e t h a t on t h e b a s i s o f t h e c a l c u l a t i o n s u s i n g t h e oned i m e n s i o n a l Chapman-Jouguet m o d e l w i t h e q u i l i b r i u m t h e r m o d y n a m i c s
w h i c h i g n o r e t h e complex s t r u c t u r e , the p r e d i c t e d d e t o n a t i o n p r o p e r t i e s ( i . e . , d e t o n a t i o n v e l o c i t y , o v e r p r e s s u r e , e t c . ) a r e found
to be q u i t e c l o s e t o t h a t observed e x p e r i m e n t a l l y , even near t h e
detonation l i m i t s .
On t h e o t h e r h a n d , t h e d y n a m i c d e t o n a t i o n
parameters (eg., d e t o n a b i l i t y l i m i t s , i n i t i a t i o n energy, c r i t i c a l
tube diameter, e t c . ) , cannot be o b t a i n e d from t h i s e q u i l i b r i u m
Chapman-Jouguet t h e o r y .
The c o m p l e x d y n a m i c p r o c e s s e s t h a t go o n
i n s i d e t h e s t r u c t u r e o f t h e d e t o n a t i o n wave ( i . e . , t h e p r o p a g a t i o n
mechanism) must now b e t a k e n i n t o c o n s i d e r a t i o n i f t h e s e d y n a m i c
d e t o n a t i o n p a r a m e t e r s a r e t o b e p r e d i c t e d . Thus f a r , no t h e o r y

138
PROCESSES
e x i s t s t h a t can g i v e even s e m i - q u a n t i t a t i v e e s t i m a t e s o f t h e s e
dynamic parameters.
Computer s i m u l a t i o n s u s i n g m u l t i - d i m e n s i o n a l
r e a c t i v e s h o c k c o d e s h a v e b e e n d e m o n s t r a t e d b y F u j i w a r a (27) and
Oran ( 2 8 ) . Both groups have reproduced two-dimensional
cellular
d e t o n a t i o n s f r o m t h e i r r e s p e c t i v e c o m p u t e r c o d e s . However, t h e
computation time r e q u i r e d i s extremely long f o r the r e q u i r e d time
and s p a t i a l r e s o l u t i o n s .
I t i s n o t l i k e l y t h a t e x t e n s i v e computer
s i m u l a t i o n s o f t h e d e t o n a t i o n phenomena w i l l be made. I t i s a l s o
n o t c l e a r a t p r e s e n t j u s t what u s e f u l i n f o r m a t i o n one c a n d e r i v e
from t h e s e computer s i m u l a t i o n s t o j u s t i f y t h e h i g h c o s t o f r u n
n i n g them f o r t h e d e t o n a t i o n p r o b l e m .
On t h e e x p e r i m e n t a l s i d e , s i g n i f i c a n t a d v a n c e s h a v e b e e n made
i n the e a r l y s i x t i e s i n the understanding of the fundamental pro
c e s s e s t h a t go on i n s i d e t h e d e t o n a t i o n f r o n t i t s e l f .
However,
t h i s b a s i c k n o w l e d g e a c q u i r e d was n o t e x p l o i t e d u n t i l t h e l a t e
s e v e n t i e s when t h e d e t o n a t i o n c e l l s i z e was r e c o g n i z e d as a u s e f u l
fundamental parameter t h a t represents t h e chemical l e n g t h s c a l e of
t h e d e t o n a t i o n p r o c e s s , a n d h e n c e c a n be c o r r e l a t e d t o a l l t h e
i m p o r t a n t dynamic parameters.
The measurement o f t h e c e l l s i z e
u s i n g c a r b o n s o o t d e p o s i t e d on a t h i n p o l i s h e d m e t a l f o i l i n s e r t e d
i n t o t h e d e t o n a t i o n tube has been w e l l e s t a b l i s h e d i n t h e e a r l y
sixties.
However, c e l l s i z e measurements i n f u e l - a i r m i x t u r e s
w e r e n o t r e v i v e d u n t i l t h e l a t e s e v e n t i e s b y B u l l (29) and
K n y s t a u t a s (30,31) when t h e u s e f u l n e s s o f c e l l s i z e d a t a became
apparent.
The f i r s t s t e p i n e s t a b l i s h i n g t h e c o r r e l a t i o n b e t w e e n
c e l l s i z e and t h e d y n a m i c p a r a m e t e r s was made b y Edwards ( 3 2 ) who
s u g g e s t e d t h a t t h e c o r r e l a t i o n b e t w e e n t h e c e l l s i z e "" and t h e
c r i t i c a l t u b e d i a m e t e r "d
( i . e . , d = 13 ) f i r s t o b s e r v e d by
M i t r o f a n o v and S o l o u k h i n (33) i n 1964 s h o u l d b e u n i v e r s a l .
The
g e n e r a l i t y o f t h e s i m p l e l a w d = 13 was c o n f i r m e d by t h e e x t e n
s i v e e x p e r i m e n t a l w o r k o f K n y s t a u t a s (30,31) who m e a s u r e d s i m u l t a
n e o u s l y t h e c e l l s i z e as w e l l a s t h e c e n t r a l t u b e d i a m e t e r f o r a
number o f f u e l s o v e r a r a n g e o f f u e l - a i r c o n c e n t r a t i o n s and i n i
t i a l pressures.
The d = 13 l a w l e d t h e a u t h o r t o d e v e l o p a s i m p l e m o d e l
w h e r e b y t h e c r i t i c a l e n e r g y f o r i n i t i a t i o n c a n be p r e d i c t e d when
t h e c e l l s i z e and t h e e q u i l i b r i u m Chapman-Jouguet d e t o n a t i o n
s t a t e s a r e known. T h i s s i m p l e s o - c a l l e d s u r f a c e e n e r g y m o d e l o f
Lee (34) gave p r e d i c t i o n s f o r t h e c r i t i c a l i n i t i a t i o n c h a r g e
weight f o r v a r i o u s hydrocarbon f u e l - a i r mixtures i n c l o s e accord
w i t h t h e e x p e r i m e n t a l d a t a o b t a i n e d by E l s w o r t h ( 3 9 ) .
The r e l a t i o n s h i p b e t w e e n d e t o n a b i l i t y l i m i t s and t h e c e l l
s i z e i s b a s e d on a s u g g e s t i o n made by Wagner (35) i n 1 9 6 0 , who
f i r s t s t a t e d t h a t t h e a p p e a r a n c e o f t h e s i n g l e h e a d e d s p i n wave
s t r u c t u r e should correspond t o the d e t o n a b i l i t y l i m i t i n the given
tube.
S i n c e t h e n , t h i s s u g g e s t i o n o f Wagner was d e m o n s t r a t e d t o
be t r u e b y Donato ( 3 6 ) , who showed e x p e r i m e n t a l l y t h a t f o r m i x t u r e
c o m p o s i t i o n s o u t s i d e t h e l i m i t when t h e s i n g l e h e a d s p i n s t r u c t u r e
f i r s t a p p e a r e d , a d e t o n a t i o n when d i s t u r b e d w i l l f a i l and w i l l n o t
r e - t r a n s i t b a c k t o t h e d e t o n a t i o n mode. R e c e n t w o r k by
11

8. L E E
Fast Flames and
139
Detonations
V a s i l i e v (37) a l s o c o n f i r m s t h i s c r i t e r i o n f o r d e t o n a t i o n l i m i t
b a s e d on t h e o n s e t o f t h e s i n g l e h e a d e d s p i n s t r u c t u r e .
Thus,
w i t h t h e c e l l s i z e a s a f u n c t i o n o f m i x t u r e c o m p o s i t i o n s known,
t h e d e t o n a b i l i t y l i m i t s i n t u b e s c a n r e a d i l y b e e s t a b l i s h e d . The
c r i t e r i o n i s that thel i m i t i n g mixture composition should give a
c e l l s i z e which i s o f t h e o r d e r o f t h e tube diameter i t s e l f .
L i m i t c r i t e r i a f o r o t h e r tube geometries and f o r u n c o n f i n e d c o n d i
t i o n s h a v e y e t t o b e e s t a b l i s h e d . However, t h e r e i s no d o u b t
t h a t t h e l i m i t c o n d i t i o n s s h o u l d be c o r r e l a t e d t o t h e fundamental
chemical l e n g t h s c a l e o f the mixture ( i . e . , c e l l s i z e ) .
A thorough r e v i e w o f t h e dynamic p a r a m e t e r s o f gaseous d e t o
n a t i o n waves a n d t h e i r c o r r e l a t i o n s w i t h t h e c e l l s i z e h a s b e e n
g i v e n b y t h e a u t h o r r e c e n t l y ( 3 8 ) . However, f o r t h e s a k e o f com
p l e t e n e s s , some o f t h e more i m p o r t a n t r e s u l t s m e n t i o n e d i n t h e
above d i s c u s s i o n s w i l l b e g i v e n . F i g u r e 9 shows t h e d e t o n a t i o n
c e l l s i z e f o r t h e common h y d r o c a r b o n f u e l s a s a f u n c t i o n o f e q u i
v a l e n c e r a t i o ( = 1 c o r r e s p o n d s t o s t o i c h i o m e t r i c c o m p o s i t i o n ) .
They a l l t a k e o n t h e s h a p e o f U - c u r v e s w i t h t h e minimum c e l l s i z e
o c c u r r i n g a t about the s t o i c h i o m e t r i c c o m p o s i t i o n .
Since t h e sen
s i t i v i t y o f the mixture i s i n v e r s e l y p r o p o r t i o n a l t o t h e c e l l s i z e ,
we s e e f r o m F i g u r e 9 t h a t a c e t y l e n e i s t h e most s e n s i t i v e f u e l
w i t h a minimum c e l l s i z e = 0.5 cm, w h i l e methane, w h i c h h a s a
minimum c e l l s i z e a b o u t two o r d e r s o f m a g n i t u d e l a r g e r ( = 33 cm)
i s t h e l e a s t s e n s i t i v e o f t h e common f u e l s .
The r e s t o f t h e
a l k a n e f a m i l y (C3H8, C2H6, C4H10) a l l h a v e a b o u t t h e same c e l l
s i z e and h e n c e s i m i l a r s e n s i t i v i t y .
The o r d e r o f s e n s i t i v i t y t o
d e t o n a t i o n f o r the v a r i o u s f u e l s as i n d i c a t e d by t h e i r r e s p e c t i v e
c e l l s i z e i n F i g u r e 9 a r e i n accord t o t h a t e s t a b l i s h e d by M a t s u i
and L e e (39) who d e v i s e d a d e t o n a t i o n h a z a r d number b a s e d o n t h e
c r i t i c a l i n i t i a t i o n e n e r g y w i t h t h e most s e n s i t i v e f u e l o f C2H2 a s
t h e r e f e r e n c e . The s o l i d c u r v e s i n F i g u r e 9 r e p r e s e n t t h e c o r r e l a
t i o n = A where
i s t h e i n d u c t i o n zone l e n g t h computed t h e o
r e t i c a l l y b a s e d on t h e d e t a i l e d c h e m i s t r y o f t h e m i x t u r e ( 4 0 ) .
The p r o p o r t i o n a t e l y c o n s t a n t A i s o b t a i n e d b y f i t t i n g a t = 1.
The g e n e r a l U-shaped b e h a v i o u r i s r e p r o d u c e d b u t t h e e r r o r c a n b e
quite s i g n i f i c a n t f o r o f f stoichiometricmixtures.
The c o r r e l a
t i o n t o d e t a i l e d c h e m i s t r y i n a s i m p l e = AZ r e l a t i o n s h i p i s n o t
of s u f f i c i e n t accuracy f o r p r e d i c t i o n purposes.
I n other words,
u s i n g one e x p e r i m e n t a l d a t a p o i n t t o d e t e r m i n e A a n d compute t h e
c e l l s i z e henceforth using d e t a i l e d chemistry i s not accurate
enough f o r p r a c t i c a l p u r p o s e s .
T h i s i s due t o t h e f a c t t h a t most
dynamic d e t o n a t i o n parameters a r e s e n s i t i v e f u n c t i o n s o f t h e c e l l
s i z e (eg., E ^ ) .
3
Based on t h e c e l l s i z e d a t a o b t a i n e d e x p e r i m e n t a l l y ( F i g u r e
9), t h e c r i t i c a l tube diameter " d
c a n be o b t a i n e d by s i m p l y mul
t i p l y i n g b y a f a c t o r o f 1 3 . F i g u r e 10 shows a c o m p a r i s o n b e t
ween t h e d = 13 c o r r e l a t i o n a n d t h e e x p e r i m e n t a l r e s u l t s f r o m
t h e d i r e c t measurements o f " d
i t s e l f from l a r g e s c a l e e x p e r i
m e n t s . The agreement i s q u i t e good i n v i e w o f t h e d i f f i c u l t i e s i n
c o n t r o l l i n g c l o s e l y t h e experimental parameters i n l a r g e s c a l e
f i e l d experiments.
, f
f f

PROCESSES
140

Fast Flames and
Detonations
141
8. L E E
0.
1.
2.
3.
EQUIVALENCE RATIO
F i g u r e 10. Comparison o f t h e c r i t i c a l tube diameter w i t h t h e

d = 13 c o r r e l a t i o n .

4.
142
B a s e d on t h e e x p e r i m e n t a l l y o b t a i n e d c e l l s i z e d a t a , t h e s u r f a c e e n e r g y m o d e l c a n be u s e d t o p r e d i c t t h e i n i t i a l i n i t i a t i o n
e n e r g i e s . The r e s u l t s a r e shown i n F i g u r e 11 as s o l i d l i n e s .
E x p e r i m e n t a l d a t a a r e t h o s e o b t a i n e d by E l s w o r t h ( 4 0 ) . I n g e n e r a l ,
q u i t e good agreement i s o b t a i n e d . More r e c e n t l a r g e e x p e r i m e n t s
p e r f o r m e d by B e n e d i c k (41) i n d i c a t e d t h a t E l s w o r t h s e n e r g y d a t a
i s too low n e a r the l i m i t s .
T h i s i s due t o t h e l i m i t e d s i z e o f
E l s w o r t h s apparatus which i s i n s u f f i c i e n t to observe the e v e n t u a l
f a i l u r e o f t h e d e t o n a t i o n wave when t h e i n i t i a t i o n c h a r g e u s e d i s
large.
The new r e s u l t s o f B e n e d i c k f o r t h e w e a k e r n e a r l i m i t m i x t u r e s are found to agree b e t t e r w i t h the s u r f a c e energy theory.
T h u s , we see t h a t as f a r as p r e d i c t i o n s o f t h e d y n a m i c d e t o n a t i o n s t a t e s , t h e r e e x i s t e m p i r i c a l r e l a t i o n s h i p s and s i m p l e a n a l y t i c a l t h e o r i e s t h a t c a n p r o d u c e q u i t e a d e q u a t e r e s u l t s once t h e
c e l l s i z e f o r t h e m i x t u r e i s known. However, t h e d e t e r m i n a t i o n o f
the c e l l s i z e , although a r e l a t i v e l y simple experimental procedure,
is quite irregular.
The u s e o f v e r y l o n g f o i l s so t h a t t h e p r o p a g a t i o n can be o b s e r v e d o v e r a l o n g e r d i s t a n c e , i m p r o v e t h e a b i l i t y
to i d e n t i f y the dominant c e l l s i z e .
However, t h e smoked c o a t i n g
o f l a r g e and l o n g m e t a l f o i l s and i n s e r t i n g them i n t o t h e d e t o n a t i o n tube poses e x p e r i m e n t a l d i f f i c u l t i e s i n p r a c t i c e .
For a
g i v e n m i x t u r e , t h e a c c u m u l a t i o n o f a l a r g e number o f r e c o r d s a l s o
h e l p s i n o b t a i n i n g a more a c c u r a t e and unambiguous v a l u e f o r t h e
cell size.
A t p r e s e n t t h e r e a p p e a r s t o be no b e t t e r means t o
d e t e r m i n e t h i s i m p o r t a n t b a s i c l e n g t h s c a l e and t h e r e i s no d o u b t
t h a t e f f o r t s must be d i r e c t e d t o w a r d t h e e s t a b l i s h m e n t o f b e t t e r
e x p e r i m e n t a l t e c h n i q u e s f o r c e l l s i z e measurements.
1
T r a n s i t i o n from D e f l a g r a t i o n to
Detonation
Unconfined f u e l - a i r detonations are extremely d i f f i c u l t to i n i t i a t e and r e q u i r e i n g e n e r a l v e r y p o w e r f u l i g n i t i o n s o u r c e s s u c h

as a s o l i d e x p l o s i v e c h a r g e o f t h e o r d e r o f a b o u t 100 grams. T h u s ,
i t i s u n d e r s t a n d a b l e t h a t f u e l - a i r d e t o n a t i o n s a r e c o n s i d e r e d as
n o n - c r e d i b l e e v e n t s i n an a c c i d e n t a l s c e n a r i o when t h e a b s e n c e o f
v e r y p o w e r f u l i g n i t i o n s o u r c e s e q u i v a l e n t t o , s a y , 100 grams o f
h i g h e x p l o s i v e s , c a n be d e m o n s t r a t e d . However, d e t o n a t i o n s can
a l s o be f o r m e d f r o m d e f l a g r a t i o n waves when t h e l a t t e r managed t o
a c c e l e r a t e to a s u f f i c i e n t l y h i g h flame speed. Thus, the p o s s i b i l i t y o f a t r a n s i t i o n f r o m d e f l a g r a t i o n t o d e t o n a t i o n (D.D.T.
h e n c e f o r t h ) becomes t h e c e n t r a l p r o b l e m and d e t e r m i n e s i f
d e t o n a t i o n h a z a r d s c a n be i g n o r e d o r n o t i n a g i v e n s i t u a t i o n . I n
g e n e r a l , the flame speeds a t the onset of d e t o n a t i o n are found to
be o f t h e o r d e r o f a b o u t 800 m/sec e x p e r i m e n t a l l y . T h u s , t h e
p o s s i b i l i t y o f a DDT h i n g e s on t h e q u e s t i o n o f f l a m e a c c e l e r a t i o n s .
I f p o w e r f u l f l a m e a c c e l e r a t i o n mechanisms s u c h as t u r b u l e n c e gener a t e d by r e p e a t e d o b s t a c l e s and t h e r i g h t k i n d o f b o u n d a r y c o n d i t i o n s ( c o n f i n e m e n t ) a r e p r e s e n t , t h e n DDT i s a d e f i n i t e p o s s i b i lity.
In long confined channels w i t h a d i s t r i b u t i o n of l a r g e

Fast Flames and
Detonations
143
8. L E E
EQUIVALENCE
RATIO
Figure 1 1 . Comparison o f t h e o r e t i c a l p r e d i c t i o n s o f c r i t i c a l
i n i t i a t i o n energy with E l s w o r t h s experimental data.
1

144
PROCESSES
o b s t a c l e s i n t h e f l o w , few w o u l d d e b a t e t h e p o s s i b i l i t y o f a DDT.
However, i n a p a r t i a l l y o r t o t a l l y u n c o n f i n e d e n v i r o n m e n t o r i n
the absence o f a s u f f i c i e n t l y l o n g flame t r a v e l f o r t h e a c c e l e r a t i o n t o t h e r e q u i r e d f l a m e s p e e d t o t a k e p l a c e , DDT i s t h e n c o n s i d e r e d t o be a h i g h l y i m p r o b a b l e e v e n t .
This conclusion i s mainly
b a s e d on t h e l a c k o f a v i a b l e mechanism whereby t h e n e c e s s a r y c o n d i t i o n s f o r t h e o n s e t o f d e t o n a t i o n t o o c c u r c a n be p r o d u c e d w i t h out flame a c c e l e r a t i o n s .
I n 1 9 7 8 , K n y s t a u t a s e t a l . (42) r e p o r t e d
t h a t d i r e c t i n i t i a t i o n o f a s p h e r i c a l d e t o n a t i o n c a n be a c h i e v e d
when a s u f f i c i e n t l y i n t e n s e t u r b u l e n t j e t o f h o t c o m b u s t i o n p r o d u c t s ( o f t h e same m i x t u r e ) i s i n j e c t e d i n t o t h e u n c o n f i n e d c l o u d
o f e x p l o s i v e m i x t u r e . By d i r e c t i n i t i a t i o n , i t i s meant t h a t t h e
d e t o n a t i o n i s formed " i n s t a n t a n e o u s l y " i n t h e immediate v i c i n i t y
o f t h e i g n i t i o n s o u r c e ( i . e . , t h e t u r b u l e n t j e t ) w i t h o u t any p r e d e t o n a t i o n flame t r a v e l o r run-up d i s t a n c e . I n o t h e r words, i t i s
no l o n g e r n e c e s s a r y t o r e l y on f l a m e a c c e l e r a t i o n mechanisms t o
b r i n g a b o u t t h e DDT. As l o n g a s c e r t a i n r e q u i r e d c o n d i t i o n s c a n
be g e n e r a t e d l o c a l l y , w h i c h i n t h i s c a s e i s t h e r a p i d t u r b u l e n t
m i x i n g b e t w e e n h o t p r o d u c t g a s e s and t h e u n b u r n e d m i x t u r e , t h e n
onset o f d e t o n a t i o n r e s u l t s .
T h i s important experiment of
K n y s t a u t a s p r o d u c e d t h e much s o u g h t a f t e r mechanism f o r DDT t o
o c c u r i n an u n c o n f i n e d c l o u d . The p o s s i b i l i t y o f a s m a l l l o c a l
c o n f i n e d e x p l o s i o n which subsequently r u p t u r e d i t s containment
and r e s u l t e d i n a v e n t i n g o f t h e h o t p r o d u c t g a s e s t o t h e o u t s i d e
m i x t u r e i s c e r t a i n l y a v e r y common a c c i d e n t s c e n a r i o i n i n d u s t r i a l
environments.
However, t h e e x p e r i m e n t s o f K n y s t a u t a s were c a r r i e d
o u t i n s e n s i t i v e o x y g e n e n r i c h e d f u e l - a i r m i x t u r e s and o n l y f o r
t h e c a s e o f t h e most s e n s i t i v e f u e l o f s t o i c h i o m e t r i c C2H2~air
when t h e t u r b u l e n t j e t i n d u c e d DDT was he a b l e t o o b s e r v e DDT. I t
i s obvious that t h e s c a l e o f t u r b u l e n t mixing r e g i o n r e q u i r e d f o r
t h e l e s s s e n s i t i v e f u e l s w o u l d be much l a r g e r t h a n t h e maximum
s i z e o f a 20 cm d i a m e t e r j e t t h a t was u s e d by K n y s t a u t a s .
No
l a r g e s c a l e s t u d i e s were f o l l o w e d u p , and s i n c e t h e n o n l y f u n d a m e n t a l s t u d i e s w e r e c o n t i n u e d t o l e a r n more a b o u t t h e dependence
o f t h e c h e m i s t r y on t h e m i x i n g r a t e , t u r b u l e n c e s c a l e and j e t
diameter.
There a r e t h r e e recent r e p o r t s o f l a r g e s c a l e experiments
where DDT was o b s e r v e d .
I n a flame propagation experiment i n a
p a r t i a l l y c o n f i n e d r e c t a n g u l a r c h a n n e l , DDT was o b s e r v e d i n ^ - a i r
m i x t u r e (^40% H2) b y P f f H r t n e r ( 4 3 ) . The l o c a l t u r b u l e n t m i x i n g
r e g i o n was c a u s e d b y a s m a l l v e n t i l a t i o n f a n w h i c h was l e f t o n
d u r i n g the flame propagation.
Thus, as t h e flame f r o n t a r r i v e s a t
t h e f a n , t h e r a p i d m i x i n g c a u s e d by t h e f a n b e t w e e n t h e h o t g a s e s
i n t h e f l a m e z o n e and t h e u n b u r n e d m i x t u r e i s s u f f i c i e n t t o r e s u l t
i n t h e o n s e t o f d e t o n a t i o n . A l t h o u g h 4 0 % H2 i n a i r * i s a f a i r l y
s e n s i t i v e mixture, P f f B r t n e r ' s observation nevertheless confirmed
t h e mechanism o f m i x i n g i n d u c e d DDT i n an u n c o n f i n e d c l o u d .
R e c e n t l y , G e i g e r (44) o f t h e B a t t e l l e I n s t i t u t e i n F r a n k f u r t
a l s o r e p o r t e d t h e o b s e r v a t i o n o f a DDT i n u n c o n f i n e d s t o i c h i o m e t r i c H2~air m i x t u r e s .
I n G e i g e r s experiment, a r e c t a n g u l a r box
f

8. LEE
Fast Flames and
Detonations
0.50 m 0.50 m 1 m, c l o s e d a t t h e i g n i t i o n e n d a n d c o n n e c t e d
through a s m a l l o r i f i c e a t t h e o t h e r end t o a l a r g e volume o f t h e
same e x p l o s i v e m i x t u r e c o n t a i n e d i n a l m x l m x 3 m
p l a s t i c bag,
was u s e d .
The t u r b u l e n t j e t d i s c h a r g e d f r o m t h e o r i f i c e p r o v i d e s
a p o w e r f u l i g n i t i o n s o u r c e . However, i n t h i s e x p e r i m e n t DDT was
not observed i n the j e t m i x i n g r e g i o n .
The p o w e r f u l j e t i g n i t i o n ,
however, l e d t o t h e development o f a v e r y f a s t d e f l a g r a t i o n .
DDT
was t h e n l a t e r o b s e r v e d when t h e f l a m e h a d p r o p a g a t e d some d i s t
ance down t h e bag.
A g a i n , the m i x t u r e used i s a l s o a f a i r l y sen
s i t i v e one.
Moen (45) a l s o r e p o r t e d t h e o b s e r v a t i o n o f DDT i n a n u n c o n
f i n e d v o l u m e o f a much l e s s s e n s i t i v e o f f - s t o i c h i o m e t r i c m i x t u r e
o f C 2 H 2 - a i r (y5% C^l^ '
i n t e n t i o n o f M o e n s e x p e r i m e n t was
n o t t o i n v e s t i g a t e t h e DDT phenomenon. However, a m i s f i r e o f t h e
i n i t i a t i n g charge r e s u l t e d i n flame p r o p a g a t i o n ( i n s t e a d o f a
detonation) i n t h e tube, which subsequently discharged i n t o a
l a r g e v o l u m e o f t h e same m i x t u r e c o n t a i n e d i n a l a r g e p l a s t i c b a g
a t t h e e n d o f t h e t u b e . The t u b e i s "U).63 m d i a m e t e r a n d 3 m l o n g
and t h e p l a s t i c b a g i s 2 m d i a m e t e r a n d 3.5 m l o n g .
From h i g h
s p e e d m o v i e r e c o r d s , Moen was a b l e t o e s t i m a t e t h e v e l o c i t y o f t h e
h o t g a s e s d i s c h a r g i n g f r o m t h e t u b e , a n d f o u n d i t t o b e a b o u t 550
m/sec. A s i n t h e c a s e o f G e i g e r s e x p e r i m e n t , DDT a g a i n d i d n o t
occur a t t h e immediate v i c i n i t y o f t h e tube e x i t .
The j e t was o b
s e r v e d t o i m p i n g e on a v e r t i c a l w a l l a t t h e end o f t h e p l a s t i c bag,
c r e a t i n g a r e c i r c u l a t i o n zone ( v o r t e x ) a t t h e base ( i . e . , between
t h e w a l l a n d t h e g r o u n d ) . The o n s e t o f d e t o n a t i o n was o b s e r v e d t o
o c c u r i n t h i s r e c i r c u l a t i o n v o r t e x a n d once f o r m e d , t h e d e t o n a t i o n
p r o p a g a t e d t h r o u g h o u t t h e e n t i r e v o l u m e o f m i x t u r e a t a b o u t 1700
m/sec, c o r r e s p o n d i n g q u i t e c l o s e l y t o t h e a n t i c i p a t e d ChapmanJouguet v a l u e .
There a r e t h r e e r e c e n t l a r g e s c a l e experiments t h a t r e p o r t e d
t h e o c c u r e n c e o f DDT i n u n c o n f i n e d m i x t u r e s . They a l l s u p p o r t t h e
t u r b u l e n t j e t m i x i n g mechanism a d v a n c e d b y K n y s t a u t a s e t a l . The
flame a c c e l e r a t i o n e x p e r i m e n t s r e p o r t e d e a r l i e r i n S e c t i o n 3 have
helped considerably t o e l u c i d a t e the necessary c o n d i t i o n s r e q u i r e d
f o r t h e o n s e t o f DDT. I n t h e c o n f i n e d t u b e e x p e r i m e n t s i t was
found t h a t onset o f d e t o n a t i o n r e q u i r e s flame speeds o f t h e o r d e r
o f a b o u t 800 m/sec. T h i s g i v e s t h e minimum t u r b u l e n t i n t e n s i t y
r e q u i r e d f o r t h e m i x i n g . The minimum s i z e o f t h e m i x i n g r e g i o n
( t u b e d i a m e t e r ) i t s e l f , was a l s o f o u n d t o b e o f t h e o r d e r o f t h e
cell size.
T r a n s l a t e d t o t h e unconfined environment, i t appears
t h a t DDT w o u l d o c c u r i f a s u f f i c i e n t l y i n t e n s e t u r b u l e n t m i x i n g
region o f a s i z e o f the order o f t h e dimension o f t h ec e l l s i z e
of the m i x t u r e c o u l d be formed.
Once t h i s i n i t i a t i o n k e r n e l i s
produced, then onset o f d e t o n a t i o n r e s u l t s and t h e d e t o n a t i o n w i l l
s u b s e q u e n t l y p r o p a g a t e throughout t h e a v a i l a b l e unburned volume.
Much i n v e s t i g a t i o n , p a r t i c u l a r l y l a r g e s c a l e e x p e r i m e n t s , a r e
n e e d e d t o c l a r i f y and d e f i n e more p r e c i s e l y t h e r e q u i r e d c o n d i
t i o n s p o s t u l a t e f o r DDT. However, i t a p p e a r s t h a t t h i s i m p o r t a n t
q u e s t i o n c a n b e answered s a t i s f a c t o r i l y i n t h e n e a r f u t u r e .
T
145

146
Conclusions
T u r b u l e n t f l a m e a c c e l e r a t i o n by an o b s t a c l e a r r a y s h o u l d r e m a i n as
the c e n t r a l problem i n e x p l o s i o n r e s e a r c h , b o t h i n terms of d i r e c t
a p p l i c a b i l i t y o f i t s r e s u l t s t o p r a c t i c a l s i t u a t i o n s , and t h e
w e a l t h o f f u n d a m e n t a l k n o w l e d g e t h a t c a n be d e d u c e d f r o m i t s s t u d y .
I t c a n be s a i d t h a t t h e q u a l i t a t i v e u n d e r s t a n d i n g o f t h e mechan i s m s i n v o l v e d i s now f a i r l y c o m p l e t e .
However, l i t t l e p r o g r e s s
has b e e n made t o d a t e i n t e r m s o f a c h i e v i n g a q u a n t i t a t i v e d e s c r i p t i o n o f t h e phenomenon. E v e n e m p i r i c a l r e l a t i o n s h i p s o f a
s u f f i c i e n t g e n e r a l i t y g i v i n g the flame a c c e l e r a t i o n r a t e or the
maximum f l a m e s p e e d a t t a i n a b l e as a f u n c t i o n o f m i x t u r e c o m b u s t i o n
and o b s t a c l e c o n f i g u r a t i o n s h a v e y e t t o be f o r m u l a t e d . E v e n
t h o u g h numerous e x p e r i m e n t s h a v e b e e n p e r f o r m e d i n t h e p a s t y e a r s ,
r a n g i n g f r o m s m a l l l a b o r a t o r y s a c l e f l a m e t u b e s o f a few c e n t i m e t e r s i n d i a m e t e r t o v e r y l a r g e t u b e s o f 2.5 m d i a m e t e r , and
f l a m e g e o m e t r i e s v a r y i n g f r o m p l a n a r t o c y l i n d r i c a l i n open f i e l d s
where t h e c l o u d c o v e r s an a r e a o f 600 m , q u a n t i t a t i v e i n f o r m a t i o n
r e g a r d i n g t h e dependence o f t h e o b s e r v e d c o m b u s t i o n p r o c e s s e s on
t h e f l u i d d y n a m i c s f i e l d s p e c i f i c o f t h e g e o m e t r y and o b s t a c l e
u s e d , h a v e n o t b e e n o b t a i n e d . M o s t o f t h e s t u d i e s w e r e made on
the i n i t i a l t r a n s i e n t development of the flame.
I t i s this addit i o n a l d e g r e e o f c o m p l e x i t y t o an a l r e a d y e x t r e m e l y i n v o l v e d p r o b lem o f n o n - l i n e a r c o u p l i n g b e t w e e n f l u i d d y n a m i c s and c h e m i s t r y
t h a t prevents the r e s u l t s from b e i n g analyzed p r o p e r l y .
The
a u t h o r b e l i e v e s t h a t s p e c i a l a t t e n t i o n s h o u l d be d e v o t e d i n s t e a d
t o t h e s t u d y o f t h e s t e a d y s t a t e r e g i m e where a c r i t i c a l b a l a n c e
b e t w e e n t h e p o s i t i v e and n e g a t i v e a s p e c t s o f t u r b u l e n c e on combust i o n o c c u r s . I t i s t h e a c c u m u l a t i o n o f e x p e r i m e n t a l d a t a on t h i s
s t e a d y s t a t e r e g i m e f o r t h e dependence o f t h e f l a m e s p e e d on m i x t u r e c o m p o s i t i o n , o b s t a c l e c o n f i g u r a t i o n s and t u b e d i a m e t e r t h a t
w i l l e v e n t u a l l y permit the f o r m u l a t i o n of e m p i r i c a l c o r r e l a t i o n s
leading to quantitative understanding.
I n the steady s t a t e regime,
e x p e r i m e n t a l measurements o f t h e v e r y c o m p l i c a t e d t u r b u l e n t f l o w
s t r u c t u r e a s s o c i a t e d w i t h the o b s t a c l e f i e l d are at l e a s t " i n t e r prtable". T h i s may t h e n l e a d t o more f u n d a m e n t a l c o r r e l a t i o n s
i n v o l v i n g t h e use o f f l u i d m e c h a n i c s p a r a m e t e r s r a t h e r t h a n geom e t r i c a l parameters c h a r a c t e r i s t i c of the o b s t a c l e c o n f i g u r a t i o n .
T h u s , c o r r e l a t i o n s o f a more u n i v e r s a l n a t u r e emerge. I n r e v i e w ing the e x i s t i n g f a c i l i t i e s of the v a r i o u s e x i s t i n g r e s e a r c h
g r o u p s , t h e r e a p p e a r s t o be a l a c k i n i n t e r m e d i a t e s c a l e f l a m e
t u b e s o f t h e o r d e r o f a m e t e r i n d i a m e t e r and p e r h a p s and L/D
r a t i o o f t h e o r d e r o f 100.
I t appears t h a t , except f o r m i x t u r e
compositions w e l l o f f - s t o i c h i o m e t r y , the chemical l e n g t h s c a l e s of
most f u e l s w o u l d n o t l i k e l y e x c e e d t h e v a l u e where a s t r o n g dep e n d e n c e on t u b e d i a m e t e r s o f a b o u t 1 m w o u l d s t i l l be p r e s e n t .
T h u s , v a l u a b l e d a t a can be a c q u i r e d r e a d i l y i n s u c h i n t e r m e d i a t e
s c a l e f a c i l i t i e s . A l t h o u g h i t may l a c k t h e " i m p r e s s i v e n e s s " o f a
h a l f o r f u l l s c a l e t e s t o f an a c t u a l g e o m e t r y , t h e w e a l t h o f
s c i e n t i f i c i n f o r m a t i o n o b t a i n e d from these s i m p l e tube experiments
2

8. LEE
Fast Flames and Detonations
147
i s w e l l worth thee f f o r t .
L i t t l e i s known a b o u t t h e s t r u c t u r e o f
these steady s t a t e f a s t flames a t p r e s e n t , even on a q u a l i t a t i v e
basis.
T h i s s h o u l d o c c u p y some p r i o r i t y i n a r e s e a r c h p r o g r a m
s i n c e c o r r e c t i n t e r p r e t a t i o n o f any e x p e r i m e n t a l r e s u l t s r e s t
h e a v i l y o n h a v i n g a c l e a r p i c t u r e o f what t h e f l a m e l o o k s l i k e .
Computer s i m u l a t i o n u s i n g v a r i o u s c o d e s s h o u l d c o n t i n u e t o
p l a y an important r o l e .
However, t h e o b j e c t i v e s must c l e a r l y b e
defined.
There i s a b i g d i f f e r e n c e between t h e computer s i m u l a t i o n o f a c e r t a i n experiment and t h e computer p r e d i c t i o n o f t h e
outcome o f e x p e r i m e n t s a s y e t t o b e p e r f o r m e d . M o s t o f t h e e x i s t ing codes a r e o f t h e former n a t u r e and t h e i r u s e f u l n e s s r e s t s on
t h e i r e v e n t u a l d e v e l o p m e n t t o become a p r e d i c t i v e c o m p u t e r c o d e .
The d e t o n a t i o n phenomenon i s i n a much b e t t e r p o s i t i o n . Emp i r i c a l correlations of s u f f i c i e n t unidersality already exist.
Together w i t h simple a n a l y t i c a l t h e o r i e s , p r a c t i c a l i n f o r m a t i o n on
t h e d y n a m i c d e t o n a t i o n p a r a m e t e r s c a n now be p r e d i c t e d w i t h a c ceptable accuracy.
However, a l l t h e s e c o r r e l a t i o n s a n d t h e o r i e s
s t i l l hinge on t h e c e l l s i z e b e i n g t h e fundamental i n p u t parameter.
Experimental d e t e r m i n a t i o n o f t h e c e l l s i z e i s n o t an easy t a s k .
Smoked p a t t e r n s a r e i n g e n e r a l h i g h l y i r r e g u l a r , r e q u i r i n g a n
"experienced eye" o r a w e a l t h o f data t o permit meaningful s t a t i s t i c a l averaging.
T h e r e i s l i t t l e d o u b t t h a t much e f f o r t i s now
required to f a c i l i t a t e the determination of thec e l l size. A t
p r e s e n t , t h e q u e s t i o n o f c e l l r e g u l a r i t y a n d i t s dependence o n
i n i t i a l and boundary c o n d i t i o n s (eg., i g n i t i o n s o u r c e , tube l e n g t h
and g e o m e t r y , e t c . ) i s n o t c l e a r .
Fundamental r e s e a r c h i s needed
to s u p p o r t t h i s quest f o r the development o f a t e c h n i q u e f o r
unambiguous c e l l m e a s u r e m e n t s .
The p r o b l e m o f DDT h a s now emerged t o b e much l e s s d i f f i c u l t
t h a n i t was once t h o u g h t t o b e .
I n e s s e n c e , t h e DDT p r o b l e m r e duces t o t h e i ) d e t e r m i n a t i o n o f t h e c o n d i t i o n s n e c e s s a r y f o r t h e
o n s e t o f d e t o n a t i o n , and i i ) t h e f l u i d m e c h a n i c s o f t u r b u l e n t
m i x i n g o f a r e a c t i v e medium t o a c h i e v e t h i s s e t o f c r i t i c a l c o n d i t i o n s f o r the onset o f d e t o n a t i o n . Both problems can be i n v e s t i g a t e d more o r l e s s i n a d e c o u p l e d f a s h i o n . The d e t e r m i n a t i o n o f
the c o n d i t i o n s necessary f o r the onset o f d e t o n a t i o n i s essent i a l l y a s t a b i l i t y p r o b l e m w h e r e one l o o k s a t t h e g r o w t h o f s h o c k
waves i n medium a t t h e v e r g e o f a u t o e x p l o s i o n . The s e c o n d p r o b lem o f m i x i n g i s a more c o m p l e x one.
There e x i s t s l i t t l e data on
intense transient j e t mixing.
C l e a r l y fundamental s t u d i e s a r e
needed t o a c q u i r e a p r e d i c t i o n o f the m i x i n g r a t e f o r g i v e n i n i t i a l
conditions.
Due t o l a c k o f s y s t e m a t i c l a r g e s c a l e DDT e x p e r i m e n t s a t
p r e s e n t , i t i s j u d g e d i m p o r t a n t t o c a r r y some o f t h e s e l a r g e s c a l e
experiments t o determine t h e c r i t i c a l dimensions o f the mixing r e gions necessary f o r the v a r i o u s f u e l - a i r m i x t u r e s .
Gas e x p l o s i o n s w i l l c o n t i n u e t o b e a n a c t i v e r e s e a r c h a r e a i n
the f o r e s e e a b l e f u t u r e as l o n g as energy p r o d u c t i o n and t r a n s p o r t
p l a y a dominant r o l e i n t h e economics o f a c o u n t r y .
However,
s c i e n t i f i c p r o g r e s s can o n l y be advanced r a p i d l y i f s u f f i c i e n t
American Chemlcaf
Society Library
1155 16th St. N. W.
Washington,
D. C. Society:
20038Washington, DC, 1983.
ACS Symposium Series;
American Chemical
148
c o m m u n i c a t i o n and c o l l a b o r a t i o n b e t w e e n v a r i o u s r e s e a r c h i n s t i t u t i o n s i n t h e d i f f e r e n t c o u n t r i e s can be e f f e c t e d .
Unfortunately,
s e l f i n t e r e s t s o f sponsoring agencies often put severe r e s t r i c t i o n s o n t h e open d i s s e m i n a t i o n o f i n f o r m a t i o n and d i s c o u r a g e s
communication and c o l l a b o r a t i o n o f t h e s c i e n t i s t s i n v o l v e d . I t
a p p e a r s t h a t t h i s i s p e r h a p s t h e most i m p o r t a n t i s s u e t h a t h a s t o
be i m m e d i a t e l y r e s o l v e d .
Acknowledgment
T h i s p a p e r was w r i t t e n a l m o s t h a l f a y e a r s i n c e t h e t a l k was
given.
Thus, t h e t e x t resembles t h e t a l k o n l y i n t h e o v e r a l l objective.
C o n s i d e r a b l e amounts o f new m a t e r i a l h a v e b e e n added and
I w i s h t o t h a n k D r . C a l v i n Chan f o r p r o v i d i n g me w i t h t h e new r e s u l t s on f a s t t u r b u l e n t f l a m e s i n t h e t h i r d s e c t i o n o f t h i s p a p e r .
Literature Cited
1. Lee, J.H., Moen, I. Prog. Energy Combust. Sci. 1980, 6,
359-389.
2. Lee, J.H., Guirao, C.M. Plant Operations Progress 1982, Vol. 2,
No. 2, pp. 84-89.
3. Lee, J.H. Plant Operations Progress 1983, Vol. 2, No. 2,
pp. 84-89.
4. Moen, I. "The Influence of Turbulence on Flame Propagation in
Obstacle Environments" in "Fuel-Air Explosions"; Lee, J.H.,
Guirao, C.M., Eds.; University of Waterlook Press, 1982.
5. Lee, J.H. Fire Safety Journal 1983, Vol. 5, pp. 251-263.
6. Chapman, W.R., Wheeler, R.N.V. Journal Chem. Soc. 1926, 2139.
7. Shchelkhin, I.I. J. Exp. Theo. Phys. (USSR) 1940, 10, 823.
8. Wagner, H. "Some Experiments about Flame Acceleration", in
"Fuel-Air Explosions", Lee, J.H., Guirao, C.M., Eds.; Univer
sity of Waterloo Press, 1982.
9. Hjertager, B.H. "Numerical Simulation of Turbulent Flame and
Reisure Development in Gas Explosions", in "Fuel-Air Explo
sions", Lee, J.H., Guirao, C.M., Eds.; University of Waterloo
Press, 1982.
10. Geiger, W. "Quantification of Hazards from Vapour Cloud Explo
sions Research within the German Safety Program", in "Fuel-Air
Explosions", Lee, J.H., Guirao, C.M., Eds.; University of
Waterloo Press, 1982.
11. Zeeuwen, J.P., Van Wingerden Kees "On the Scaling of Vapour
Cloud Explosion Experiments", paper presented at the 9th
ICODGERS, Poitiers, France, 1983.
12. Urtiew, P.A. "Recent Flame Propagation Experiments at LLNL
within the Liquified Gaseous Fuels Spill Safety Program", in
"Fuel-Air Explosions", Lee, J.H., Guirao, C.M., Eds.; Univer
13. Strehlow, R.A., University of Illinois, Champagne-Urbana,
Private Communication (1983).

8. LEE
Fast Flames and
Detonations
149
14. Berman, ., Sandia National Laboratory, New Mexico, Private

Communication (1983).
15. Atkinson, R., Bull, D.C., Shuff, P.J. Combustion and Flame
1980, 39, 297.
16. Meyer, J.W., Urtiew, P.., Oppenheim, A.K. Combustion and
Flame 1970, 14, 13.
17. Thibault, P., Liu, Y.K., Chan, C., Lee, J.H., Knystautas, R.,
Guirao, C.M., Hjertager, B.H., Fuhre, K. Proc. 19th Symp.
(Int.) on Combustion 1982, pp. 599-606.
18. Moen, I.O., Lee, J.H.S., Hjertager, B.H., Fuhre, K., Eckhoff,
R.K. Combustion and Flame 1982, 47, 31-52.
19. Hjertager, B.H., Combus. Sci. and Techn. 1982, 27, 159-170.
20. Haselman, L.C. "TDC - A Computer Code for Calculating Chemi
cally Reacting Hydrodynamic Flows in Two Dimensions",
Lawrence Livermore National Laboratory, UCRL-52931, May 1980.
21. Hjertager, B.H. "Numerical Simulation of Turbulent Flame and
Pressure Development in Gas Explosions", in "Fuel-Air
Explosions", Lee, J.H., Guirao, C.M., Eds.; University of
Waterloo Press, 1982.
22. Ashurst, W.T. and Barr, P.K. "Discolte Vortex Simulation of
Flame Acceleration due to Obstacle Generated Flow", Sandia
National Laboratory (Livermore) Report, SAND 82-8724 (1982).
23. Hjertager, B.H. Comb. Sc. Techn. 1982, 27, 159-170.
24. Marx, ., Sandia National Laboratory (Livermore), Private
Communication (1983).
25. Wolanski, P. "Gas and Dust Explosion Research in Poland", in
"Fuel-Air Explosion", Lee, J.H., Guirao, C.M., Eds.; Univer
26. Lee, J.H., Knystautas, R., Chan, C., Barr, P.K., Grcar, J.F.,
Ashurst, W.T. "Turbulent Flame Acceleration: Mechanisms and
Computer Modeling", International Meeting on High-Water Reac
tor Severe Accident Evaluation, Cambridge, Mass., Aug. 28 Sept. 1 (1983), also appeared as Sandia Report SAND 83-8655.
27. Taki, S., Fujiwara, T. Proc. 18th Symp. (Int.) on Comb. 1981,
pp. 1671-1681.
28. Oran, E., Boris, J.P., Young, T., Flanigan, ., Burks, T.,
Picone, M. Proc. 18th Symp. (Int.) on Comb. 1983, pp. 16411649.
29. Bull, D.C., Elsworth, J.E., Shuff, P.J., Metcalfe, E. Comb.
Flame 1982, 45, 7-22.
30. Knystautas, R., Guirao, C.M., Lee, J.H.S., Sulmistras, A.
"Measurements of Cell Size in Hydrocarbon-Air Mixtures and
Predictions of Critical Tube Diameter Initiation Energy and
Detonability Limits", 9th Int. Colloq. on Dynamics of
Explosions and Reactive Systems (1983).
31. Knystautas, R., Lee, J.H., Guirao, C.M. Comb. Flame 1982,
48, 63-83.
32. Edwards, D.H., Thomas, G.O., Nettleton, M.A. J. Fluid
Mechanics 1979, 95:1, 79-96.

150
33. Mitrofanov, V.V., Soloukhin, R.I., Soviet Phys.-Dokl. 1964,

9, 1055.
34. Lee, J.H., Knystautas, R., Guirao, C.M. "The Link Between
Cell Size, Critical Tube Diameter Initiation Energy and
Detonability Limits", in "Fuel-Air Explosions", Lee, J.H.
Guirao, C.M., Eds.; University of Waterloo Press, 1982.
35. Dove, S.E., Wagner, Hg. Proc. 8th Symp. (Int.) on Comb. 1960,
589-600.
36. Donato, M. "The Influence of Confinement on the Propagation
of Near Limit Detonation Waves", Ph.D. Thesis, McGill
University, Montreal, 1982.
37. Vasiliev, A.A. Fiz. Goreniya Vzryva 1982, 18, 2, 132-136.
38. Lee, J.H.S. Ann. Rev. Fluid Mech. 1984, 16, 311-336.
39. Matsui, ., Lee, J.H. Proc. 17th Symp. (Int.) on Comb. 1978,
1269-1289.
40. Elsworth, J.E., Shell Research Limited, Thornton Research
Center, U.K., Private Communication.
41. Benedick, W., Sandia National Laboratory, New Mexico, Private
Communications (1983).
42. Knystautas, R., Lee, J.H., Moen, I., Wagner, Hg., Proc. 17th
Symp. (Int.) on Comb. 1978, 1235-1245.
43. Pffrtner, I.C.T., Karlsruhe, West Germany, Private
Communications.
44. Geiger, W., Battelle Institute, Frankfurt, W. Germany,
Private Communications.
45. Moen, I., Defense Research Establishment Suffield, Alberta,
Canada, Private Communications.
RECEIVED January 16, 1984

9
Chemical Kinetic-Fluid Dynamic Interactions
in Detonations
ELAINE ORAN
Laboratory for Computational Physics, Naval Research Laboratory, Washington, DC 20375
We summarize a number of simulations aimed at

deciphering some of the basic effects which arise
from the interaction of chemical kinetics and fluid
dynamics in the ignition and propagation of detona
tions in gas phase materials. The studies presented
have used one- and two-dimensional numerical models
which couple a description of the fluid dynamics to
descriptions of the detailed chemical kinetics and
physical diffusion processes. We briefly describe,
in order of complexity, a) chemical-acoustic
coupling, b) hot spot formation, ignition and the
shock-to-detonation transition, c) kinetic factors
in detonation cell sizes, and d) flame acceleration
and the transition to turbulence.
I n t h i s p a p e r we d e s c r i b e some o f t h e b a s i c e f f e c t s w h i c h a r i s e
s p e c i f i c a l l y from t h e c o u p l i n g between c h e m i c a l k i n e t i c s and f l u i d
dynamics i n combustion systems. Although t h e p a r t i c u l a r emphasis
h e r e i s on t h e i g n i t i o n a n d p r o p a g a t i o n o f d e t o n a t i o n s , many o f
the more f u n d a m e n t a l i n t e r a c t i o n s d e s c r i b e d a r e g e n e r a l l y a p p l i cable t o flames.
The s e l e c t i o n o f t o p i c s i s b y no means meant t o
be c o m p r e h e n s i v e ; r a t h e r , i t r e p r e s e n t s a p o t p o u r r i o f i d e a s w h i c h
complement e a c h o t h e r a n d t h o s e p r e s e n t e d i n t h e o t h e r p a p e r s i n
t h i s s e s s i o n o f t h e Symposium. A l t h o u g h we m a i n l y u s e c a l c u l a t i o n s p e r f o r m e d a t NRL t o e x t r a c t a n d i l l u s t r a t e t h e d e t a i l s o f
the i n t e r a c t i o n s , we have drawn l i b e r a l l y on t h e r e s u l t s o f e x p e r iments and a n a l y t i c t h e o r y .
Chemical-Acoustic
Coupling
Studies o f c h e m i c a l - a c o u s t i c c o u p l i n g a r e concerned w i t h t h e
i n t e r a c t i o n s between sound waves a n d t h e p r o c e s s e s i n v o l v e d i n
This chapter not subject to U.S. copyright.
Published 1984, American Chemical Society
152
chemical r e a c t i o n s , which c o u l d i n v o l v e e i t h e r the g e n e r a t i o n of

new s p e c i e s o r e n e r g y r e l e a s e o r a b s o r p t i o n (1)
There a r e
e s s e n t i a l l y two a p p r o a c h e s t o d i s c u s s i n g c h e m i c a l - a c o u s t i c i n t e r actions.
The f i r s t i s t o c o n s i d e r the e f f e c t s of e n e r g y r e l e a s e
o r o t h e r n o n e q u i l i b r i u m p r o p e r t i e s o f t h e m i x t u r e on the sound
waves t h e m s e l v e s .
The e a r l i e s t work i n t h i s a r e a was done by L o r d
R a y l e i g h i n the n i n e t e e n t h c e n t u r y .
F i g u r e 1 shows a summary o f
L o r d R a y l e i g h s r e s u l t s on the e f f e c t s of e n e r g y r e l e a s e on t h e
p h a s e and a m p l i t u d e o f sound waves We see t h a t e x a c t l y how t h e
f r e q u e n c y and a m p l i t u d e o f the sound wave a r e a l t e r e d depend on
where i n t h e c y c l e o f t h e sound wave t h e e n e r g y i s r e l e a s e d .
S i n c e t h i s e a r l y work, s i g n i f i c a n t t h e o r e t i c a l r e s u l t s have been
o b t a i n e d w h i c h d e s c r i b e how sound waves a t t e n u a t e as t h e y t r a v e l
through m i x t u r e s s l i g h t l y p e r t u r b e d from c h e m i c a l e q u i l i b r i u m ( 2 4).
We know t h a t sound waves c a n be a m p l i f i e d as t h e y p r o p a g a t e
t h r o u g h n o n e q u i l i b r i u m m i x t u r e s (5,6) and t h a t a shock forms
b e f o r e a t h e r m a l e x p l o s i o n when a sound wave p r o p a g a t e s t h r o u g h an
e x p l o s i v e m i x t u r e ( 7 , 8 ) . F i n a l l y , we have l e a r n e d t h a t sound
waves p r o p a g a t i n g t h r o u g h e x o t h e r m i c m i x t u r e s c a n be a m p l i f i e d and
new modes can be e x c i t e d ( 9 , 1 0 ) .
I n p a r t i c u l a r , sound waves a r e
a m p l i f i e d d u r i n g the process of c h e m i c a l energy r e l e a s e i t s e l f ,
and t h i s e f f e c t has a t e n d e n c y t o d i e o u t once the s y s t e m has
r e a c h e d a new e q u i l i b r i u m
The o t h e r a p p r o a c h t o t h i s p r o b l e m i s t o l o o k a t how t h e
p r e s e n c e o f t h e sound wave changes t h e c h e m i c a l r e a c t i o n p r o c e s s .
F i r s t , we know t h a t f l u c t u a t i o n s i n the t e m p e r a t u r e and p r e s s u r e
can a l t e r c h e m i c a l r e a c t i o n t i m e s .
G i l b e r t e t a l . (11) have shown
how s i n g l e - s t e p u n i m o l e c u l a r d i s s o c i a t i o n o r c o n v e r s i o n can
p r o d u c e a p r e d i c t a b l e a m p l i t u d e and d i s p e r s i o n change i n a sound
wave. From t h i s t h e y p r o p o s e d u s i n g a c o u s t i c changes t o h e l p
f o l l o w and d i a g n o s e c h e m i c a l r e a c t i o n s . Toong and c o w o r k e r s
(9,10) have shown t h a t sound waves enhance e n e r g y r e l e a s e r a t e s i n
exothermic systems.
A l l o f the a n a l y s i s d e s c r i b e d i n the l a s t two p a r a g r a p h s has
b e e n done on s y s t e m s w i t h a t most an i d e a l i z e d , o n e - s t e p A r r h e n i u s
k i n e t i c s model, and most o f the a n a l y s i s has b e e n done i n a
l i n e a r approximation.
R e c e n t work by Oran and B o r i s (12) has u s e d
n u m e r i c a l s i m u l a t i o n s t o show t h a t sound waves can n o t o n l y a f f e c t
t h e e n e r g y r e l e a s e t i m e as Toong has shown, b u t c a n a l s o d r a s t i c a l l y r e d u c e t h e the p e r i o d b e f o r e t h e r e i s any e n e r g y r e l e a s e ,
w h i c h we d e f i n e as t h e c h e m i c a l i n d u c t i o n t i m e .
These s i m u l a t i o n s
c o u p l e d a d e t a i l e d c h e m i c a l r e a c t i o n mechanism f o r h y d r o g e n - o x y g e n
c o m b u s t i o n t o a s o l u t i o n o f t h e c o n s e r v a t i o n e q u a t i o n s f o r mass,
momentum and e n e r g y . The s h o r t e n e d i n d u c t i o n t i m e i s a p r o p e r t y
o f t h e n o n l i n e a r c o u p l i n g b e t w e e n t h e i n t e r m e d i a t e species c o n c e n t r a t i o n s and the changes i n d e n s i t y and t e m p e r a t u r e w h i c h
r e s u l t f o r m t h e p r e s e n c e o f t h e sound w a v e s . F o r t h i s e f f e c t t o
o c c u r , i t i s n e c e s s a r y t o have a number o f s p e c i e s and a number o f

ORAN
Interactions in
Detonations
Phase of heat supply

Effect
relative to
Effect on
n
phase of pressure amplitude frequency
0
In phase
Increase
None
Opposite phase
Decrease
None
Quarter-period
before
None
Increase
Quarter-period
after
F i g u r e 1. R a y l e i g h ^ c r i t e r i o n f o r t h e e f f e c t s
on t h e a m p l i t u d e a n d p h a s e o f a s o u n d w a v e .
o f heat r e l e a s

154
reaction
r a t e s c o u p l i n g them: i t i s n o t a r e s u l t t h a t w o u l d come
f r o m an a n a l y s i s w h i c h was b a s e d on a o n e - s t e p A r r h e n i u s r e a c t i o n
rate
F i g u r e 2 shows two c a l c u l a t i o n s w h i c h have been done w i t h
t h e d e t a i l e d model d e s c r i b e d a b o v e .
The s i m u l a t i o n s a r e f o r
hydrogen-oxygen m i x t u r e s d i l u t e d w i t h argon. For both cases the
p e r i o d o f t h e imposed sound wave was c h o s e n s o t h a t t h e r e a r e
a b o u t t h r e e p e r i o d s w i t h i n a c h e m i c a l i n d u c t i o n t i m e . The a m p l i t u d e o f t h e imposed sound wave was t h e same i n b o t h cases
Each
f i g u r e shows t h e t e m p e r a t u r e v e r s u s t i m e p r o f i l e s a t t h r e e l o c a t i o n s i n t h e m i x t u r e . I n the upper f i g u r e , t h e r e i s about a f i f t e e n m i c r o s e c o n d d i f f e r e n c e i n the i n d u c t i o n t i m e g e n e r a t e d by t h e
p r e s e n c e o f t h e sound wave. I h e r e i s a 150 m i c r o s e c o n d d i f f e r e n c e
i n t h e b o t t o m f i g u r e , b u t t h i s c a s e i s even more i n t e r e s t i n g i f we
n o t e t h a t t h e s t a t i c i n d u c t i o n t i m e f o r t h i s m i x t u r e i s a b o u t 1500
microseconds.
Thus t h e r e has been a t o t a l d e c r e a s e i n t h e i n d u c t i o n t i m e o f a b o u t a f a c t o r o f t e n . F i g u r e 3 shows a s t a t i c
q u a n t i f i c a t i o n o f t h e i n d u c t i o n t i m e t h r o u g h a s e n s i t i v i t y parame t e r d e f i n e d on t h e t o p o f t h e f i g u r e .
Large v a l u e s of the cont o u r s i n d i c a t e t h a t the m i x t u r e s ' i n d u c t i o n t i m e w i l l change s u b s t a n t i a l l y due t o t h e p r e s e n c e o f sound w a v e s . The v a l u e o f t h i s
p a r a m e t e r f o r t h e upper m i x t u r e i n F i g u r e 2 i s a b o u t 10, and f o r
the l o w e r m i x t u r e a b o u t 35.
The r e s u l t o f t h i s work i s t h a t t h e p r e s e n c e o f sound waves
c a n change c h e m i c a l i n d u c t i o n t i m e s and e n e r g y r e l e a s e t i m e s .
F u r t h e r m o r e , e n e r g y r e l e a s e can a m p l i f y e x i s t i n g sound waves and
g e n e r a t e new ones I h e o v e r a l l c o n c l u s i o n i s t h a t t i m e s c a l e
a n a l y s e s may have t o be m o d i f i e d t o a c c o u n t f o r the p r e s e n c e o f
these coupling e f f e c t s .
Hot S p o t s , R e a c t i v e C e n t e r s , and t h e S h o c k - t o - D e t o n a t i o n
Transition
L o c a l f l u c t u a t i o n s i n t e m p e r a t u r e , d e n s i t y and p r e s s u r e a r e a l w a y s
p r e s e n t , even i n homogeneous, p r e m i x e d s y s t e m s .
I n s y s t e m s whose
s e n s i t i v i t y t o p e r t u r b a t i o n s i s h i g h , t h e s e f l u c t u a t i o n s c a n have
s u r p r i s i n g c o n s e q u e n c e s and a l t e r t h e b e h a v i o r f r o m c o n v e n t i o n a l
e x p e c t a t i o n s . We saw t h i s above when we i n v e s t i g a t e d t h e s e n s i t i v i t y o f t h e h y d r o g e n - o x y g e n m i x t u r e t o t h e p r e s e n c e o f sound
w a v e s . I t has a l s o been shown t h a t t h e same systems a r e j u s t a s
s e n s i t i v e t o e n t r o p y p e r t u r b a t i o n s ( 1 2 ) . Below we d e s c r i b e a
s y s t e m i n w h i c h the combined e f f e c t s o f sound wave and e n t r o p y
p e r t u r b a t i o n s cause n o n - i d e a l b e h a v i o r b e h i n d i n c i d e n t s h o c k s .
The s t u d y i s b a s e d on the r e c e n t shock tube s t u d i e s by Edwards
e t a l . (13) w h i c h have shown i g n i t i o n s t a r t i n g f r o m one o f a
s e r i e s of hot s p o t s behind the shock.

ORAN
interactions in Detonations
9.
Tim* (*)
F i g u r e 2. C a l c u l a t e d t e m p e r a t u r e v s . t i m e a t t h r e e l o c a t i o n s
r e a c t i v e m i x t u r e s t h a t a r e p e r t u r b e d b y a s o u n d wave.

156
F i g u r e 3. C o n t o u r s o f t h e s e n s i t i v i t y p a r a m e t e r d e f i n e d a t t h e
t o p o f t h e f i g u r e as a f u n c t i o n o f t e m p e r a t u r e , T, a n d t h e i n d u c
t i o n parameter, .

9.
ORAN
157
Interactions in Detonations
I n o r d e r t o e x p l o r e p o s s i b l e mechanisms and u n d e r s t a n d t h e
i m p l i c a t i o n s f o r s e n s i t i v e s y s t e m s , we have p e r f o r m e d a s e r i e s o f
n u m e r i c a l s i m u l a t i o n s u s i n g t h e model d e s c r i b e d i n t h e l a s t s e c t i o n o f t h i s paper ( 1 4 ) . S p e c i f i c a l l y , the c a l c u l a t i o n s s i m u l a t e d
an i n c i d e n t shock d r i v e n by a h i g h p r e s s u r e h e l i u m d r i v e r i n t o a
low p r e s s u r e r e g i o n c o n t a i n i n g a c o m b u s t i b l e m i x t u r e o f h y d r o g e n
i n a i r . F i g u r e 4 shows t h e r e s u l t s f r o m one s u c h c a l c u l a t i o n
w h i c h shows a r a t h e r s u r p r i s i n g e f f e c t :
i g n i t i o n does n o t o c c u r
a t t h e contact d i s c o n t i n u i t y , which i s t h e r e g i o n which i s heated
f o r t h e l o n g e s t t i m e . A c a r e f u l l o o k a t t h e s e c a l c u l a t i o n s shows
t h a t some s m a l l amount o f e n e r g y r e l e a s e h a s o r i g i n a l l y o c c u r e d a t
the c o n t a c t d i s c o n t i n u i t y , and t h i s h a s g e n e r a t e d p r e s s u r e p u l s e s
w h i c h have t r a v e l e d f o r w a r d a n d a c c e l e r a t e d t h e s h o c k f r o n t .
This
p r o c e s s h a s c r e a t e d a r e g i o n b e h i n d t h e shock f r o n t w h i c h i s a t a
h i g h e r temperature and p r e s s u r e than t h a t o f t h e o r i g i n a l shock
front.
Since the mixture i s i n a s e n s i t i v e r e g i o n o f the temperat u r e - p r e s s u r e p l a n e , t h e i n d u c t i o n t i m e b e h i n d t h e s h o c k now h a s
been somewhat r e d u c e d . T h i s p r o c e s s r e p e a t s i t s e l f u n t i l one o f
t h e r e a c t i o n c e n t e r s i g n i t e s a n d forms a r e a c t i o n wave. S i n c e t h e
c a l c u l a t i o n i s o n e - d i m e n s i o n a l and C a r t e s i a n , t h e r e a r e r e a l l y two
r e a c t i o n waves g e n e r a t e d :
one m o v i n g f o r w a r d i n t h e d i r e c t i o n o f
the i n c i d e n t s h o c k , and a n o t h e r moving b a c k w a r d s t o w a r d t h e c o n t a c t d i s c o n t i n u i t y . T h i s i s shown i n F i g u r e 5. The f o r w a r d
moving wave c a n t r a n s i t i o n t o a d e t o n a t i o n even b e f o r e i t r e a c h e s
t h e i n c i d e n t s h o c k wave. When i t r e a c h e s t h e s h o c k wave, t h e r e i s
an a b r u p t i n c r e a s e i n shock v e l o c i t y .
The b a c k w a r d moving wave
t r a v e l s more s l o w l y and when i t r e a c h e s t h e c o n t a c t d i s c o n t i n u i t y ,
i t sends a p r e s s u r e p u l s e i n t o t h e d r i v e r g a s .
F i g u r e 6 shows t h e
t i m e h i s t o r y o f t h e d e v e l o p m e n t o f t h e r e a c t i o n c e n t e r s and t h e
p r o c e s s o f i g n i t i o n and t r a n s i t i o n t o d e t o n a t i o n .
Thus we have s e e n a n o t h e r c a s e where t h e i n t e r a c t i o n o f sound
waves a n d e n t r o p y p e r t u r b a t i o n s w i t h c h e m i c a l r e a c t i o n s h a s
a l t e r e d t h e t i m e s c a l e s and even t h e l o c a t i o n o f t h e p h y s i c a l p r o c e s s e s . T h i s i s a much more c o m p l i c a t e d a n d l e s s i d e a l i z e d example
t h a n t h e sound wave s t u d y d e s c r i b e d i n t h e p r e v i o u s s e c t i o n . The
sound wave c a l c u l a t i o n s , however, d i d i s o l a t e t h e i n t e r a c t i o n s a n d
l o o k e d a t what was r e q u i r e d t o q u a n t i f y t h e e f f e c t .
Here we have
not o n l y seen t h e d i r e c t e f f e c t o f v a r i a t i o n s i n t h e i n d u c t i o n
t i m e s due t o t h e p r e s e n c e o f p e r t u r b a t i o n s , b u t a l s o t h e i n d i r e c t
e f f e c t o f an a l t e r a t i o n o f t h e background p h y s i c a l c o n d i t i o n s ,
i . e . , t h e Mach number o f t h e s h o c k , due t o p r e s s u r e p u l s e s g e n e r a t e d by energy r e l e a s e .
K i n e t i c Factors and Detonation
Cell
Sizes
I t h a s been known f o r some t i m e t h a t a smooth, p l a n a r p r o p a g a t i n g

d e t o n a t i o n i s u n s t a b l e . T h i s means t h a t s m a l l p e r t u r b a t i o n s c a n
t r i g g e r t h e i n s t a b i l i t y and t h e s y s t e m may change t o a more s t a b l e
s t r u c t u r e . F o r e x a m p l e , E r p e n b e c k (15) d e v e l o p e d a c r i t e r i o n f o r

158
'
1200
'
'
"
time - 57033
time-13493
1000
b_LL
289 73
800
L
57993
1200
1000
-J
328 43
800
589
1200
1000
800
386 63
599 33
1200
1000
L
50
60
70
POSITION (cm)
80
800,
80
90
100
110
POSITION (cm)
F i g u r e k.
The u p p e r p o r t i o n s o f c a l c u l a t e d p r o f i l e s o f t e m p e r a
t u r e as a f u n c t i o n o f p o s i t i o n from a s i m u l a t i o n o f a shock p r o p a
g a t i n g i n a r e a c t i v e hydrogen-oxygen m i x t u r e t h a t has a r e l a t i v e l y
h i g h s e n s i t i v i t y a s d e t e r m i n e d f r o m F i g u r e 3.


(cm)
C a l c u l a t e d t e m p e r a t u r e and p r e s s u r e p r o f i l e s
t i m e s t h a n i n F i g u r e h.
POSITION
at
later
160
POSITION (cm)
F i g u r e 6.
L o c a t i o n as a f u n c t i o n o f t i m e o f t h e s h o c k f r o n t , c o n t a c t s u r f a c e r e a c t i o n c e n t e r s , r e a c t i o n waves, and d e t o n a t i o n f r o n t
f o r t h e c a l c u l a t i o n shown i n F i g u r e s k a n d 5 .

9.
ORAN
Interactions in
Detonations
161
when an overdriven detonation f r o n t was s t a b l e , given an a c t i v a t i o n energy and a s i n g l e - s t e p Arrhenius r e a c t i o n r a t e . Such a

s t a b i l i t y a n a l y s i s gives a "go, no-go" answer, but i t does not
give information about the e v o l u t i o n of the i n s t a b i l i t y .
This
aspect was treated by F i c k e t t and Wood (16), who performed numeric a l simulations of Erpenbeck's model problem. They d i d indeed
f i n d that the f r o n t o s c i l l a t e s due to the coupling of the f l u i d
dynamics and energy r e l e a s e .
We a l s o know now that detonations do not propagate as smooth
f r o n t s . Their e q u i l i b r i u m s t r u c t u r e i s composed of a set of
i n t e r a c t i n g , i n t e r s e c t i n g shock waves, which we c a l l the i n c i d e n t
shock, the Mach stem, and transverse waves. Further, we know that
the i n t e r s e c t i o n of the i n c i d e n t shock and Mach stem i s a t r i p l e
p o i n t whose p o s i t i o n i n time describes the rhombic shape we c a l l a
"detonation c e l l . "
The i n c i d e n t shock i s not steady, but i s cont i n u o u s l y decaying; and the transverse wave, a r e f l e c t e d shock
i n t e r s e c t i n g the Mach stem and the i n c i d e n t shock, s h u t t l e s back
and f o r t h across the detonation f r o n t . A detonation c e l l i s
r e i n i t i a t e d when c o l l i s i o n s occur between transverse waves moving
i n opposite d i r e c t i o n s . Behind the shock f r o n t s , there i s a react i o n zone which varies i n distance from the f r o n t depending on the
length of time i t has been since c e l l r e i n i t i a t i o n . The v e l o c i t y
of the leading shock v a r i e s from above the Chapman-Jouguet value
to below i t and takes a sudden jump when the c e l l s t r u c t u r e i s
r e i n i t i a t e d by transverse wave c o l l i s i o n s . Detonation c e l l s have
been measured by coating the i n s i d e of a detonation tube with soot
and l e t t i n g the t r i p l e p o i n t trace out the p a t t e r n .
In general
the p a t t e r n i s q u i t e i r r e g u l a r , but a c h a r a c t e r i s t i c c e l l s i z e can
be determined f o r a p a r t i c u l a r m a t e r i a l at a given temperature and
pressure.
E x c e l l e n t summaries of what i s known about the c e l l
s t r u c t u r e have been given by Strehlow (17) and by F i c k e t t and
Davis (18).
Thus we see that the f a c t o r s that determine the detonation
c e l l s i z e are complicated i n t e r a c t i o n s of f l u i d dynamics and
chemical k i n e t i c s . The f l u i d dynamics here involves a number of
i n t e r a c t i n g shock waves, pressure waves, sound waves, and p e r t u r bations due to energy r e l e a s e . The chemical r e a c t i o n s are occurr i n g i n an environment which i s always subjected to f l u c t u a t i o n s
and pressure p e r t u r b a t i o n s .
Thus we have gone up i n l e v e l of
complexity i n the flow p r o p e r t i e s . However, t h i s problem encompasses a l l of the issues we discussed i n the previous s e c t i o n .
Numerical simulations of the s t r u c t u r e of multidimensional
detonations have been c a r r i e d out by Taki and Fujiwara (19) and by
Oran et a l . (20). Because of the expense involved i n these simul a t i o n s , both groups used a phenomenological model meant to
describe the b a s i c features of energy release, and coupled t h i s to
a s o l u t i o n of the conservation equations f o r the f l u i d dynamics.

162
B e l o w we summarize some o f t h e r e s u l t s o b t a i n e d b y Oran e t a l .

( 2 0 ) , w h i c h used c h e m i c a l models t h a t had t h e a b i l i t y t o r e p r e s e n t
t h e change i n c h e m i s t r y due t o p r e s s u r e a n d t e m p e r a t u r e p e r t u r b a t i o n s i n the c h e m i c a l l y s e n s i t i v e regime.
As m e n t i o n e d above, t h e c e l l s i z e o f a d e t o n a t i o n depends on
the p a r t i c u l a r m i x t u r e and i t s p r e s s u r e and t e m p e r a t u r e .
Thus t h e
number o f d e t o n a t i o n c e l l s t h a t w i l l be formed by a s e l f - p r o p a g a t i n g d e t o n a t i o n i n a t u b e depends on t h e h e i g h t o f t h e t u b e . I n
p r a c t i c e , however, i f t h e tube i s n o t h i g h enough, t h e d e t o n a t i o n
w i l l e x t i n g u i s h due t o l o s s e s t o t h e w a l l s . F o r t h e c a l c u l a t i o n s ,
however, we do n o t have t o i n c l u d e w a l l l o s s e s , and we assume f o r
now t h a t we a r e d i s c u s s i n g t w o - d i m e n s i o n a l C a r t e s i a n g e o m e t r y .
The e x p e r i m e n t a l e q u i v a l e n t w o u l d be a v e r y t h i n t u b e . I f t h e
t u b e h e i g h t i s l e s s t h a n one c e l l h e i g h t , a p e r t u r b e d h a l f - c e l l
s t r u c t u r e w i l l e v o l v e . I f t h e tube h e i g h t i s one c e l l h e i g h t , a
f u l l c e l l w i l l d e v e l o p , e t c . N o t e t h a t b e c a u s e o f t h e symmetry o f
the c e l l s , i t s h o u l d be p o s s i b l e t o o b t a i n many o f t h e two-dimens i o n a l f e a t u r e s by s i m u l a t i n g a h a l f o f a c e l l .
F i g u r e 7 shows t h e r e s u l t s o f s i m u l a t i o n s o f a d e t o n a t i o n
p r o p a g a t i n g down a tube f i l l e d w i t h a m i x t u r e o f h y d r o g e n , o x y g e n
and a r g o n .
The t u b e h e i g h t i s s l i g h t l y g r e a t e r t h a n h a l f o f a
d e t o n a t i o n c e l l h e i g h t . Itie s i m u l a t i o n was done f o r a m a r g i n a l
detonation:
t h a t i s , a d e t o n a t i o n which i s c l o s e t o the v a l u e s o f
p r e s s u r e , t e m p e r a t u r e , and s t o i c h i o m e t r y f o r w h i c h i t w i l l d i e
out.
F i g u r e 7 c o n t o u r s a q u a n t i t y we c a l l t h e i n d u c t i o n parame t e r , w h i c h i s a measure o f t h e amount o f m a t e r i a l r e a c t e d .
S u p e r i m p o s e d on t h e s e c o n t o u r s i s t h e shock f r o n t as d e t e r m i n e d b y
t h e jump o f t e m p e r a t u r e a n d p r e s s u r e . Thus t h e m a t e r i a l t o t h e
r i g h t i s t o t a l l y u n s h o c k e d and u n r e a c t e d . The m a t e r i a l t o t h e
l e f t o f the temperature contour i s i n v a r i o u s stages of r e a c t i o n
completion.
The i n t e r e s t i n g f e a t u r e w h i c h i s n o t i c e a b l e b o t h i n t h e s e
s i m u l a t i o n s and i n t h e e x p e r i m e n t s b y Edwards (20) i s t h e f o r m a t i o n o f t h e p o c k e t s o f u n b u r n e d gas w h i c h o c c u r s when t h e t r a n s v e r s e wave c o l l i d e s w i t h t h e w a l l .
B e c a u s e o f t h e symmetry o f a
c e l l , t h i s i s e q u i v a l e n t t o t h e c o l l i s i o n o f two t r a n s v e r s e w a v e s .
F i g u r e 8 shows c o n t o u r s f r o m a s i m u l a t i o n i n a much s h o r t e r t u b e .
The a d v a n t a g e o f t h i s i s t h a t t h e h a l f c e l l s t r u c t u r e i s f o r c e d
and t h e c a l c u l a t i o n i s much more r e s o l v e d . Here i t i s much e a s i e r
to s e e t h e p o c k e t s b e i n g f o r m e d .
I t i s particularly interesting
t o n o t e t h a t t h e p o c k e t s have a t e m p e r a t u r e a n d p r e s s u r e t h a t a r e
i n an e x t r e m e l y s e n s i t i v e r e g i m e i n t h e t e m p e r a t u r e - p r e s s u r e
p l a n e , a s d e t e r m i n e d f r o m c a l c u l a t i o n s s u c h as t h o s e i n F i g u r e 3.
Thus many o f t h e i r b u r n i n g p r o p e r t i e s and t h e i r e n e r g y r e l e a s e
p r o p e r t i e s w i l l be d e t e r m i n e d n o t b y t h e i r i n i t i a l p r e s s u r e and
t e m p e r a t u r e , b u t by t h e m y r i a d o f p r e s s u r e and e n t r o p y

9. ORAN
163
p e r t u r b a t i o n s w h i c h t h e y f e e l due t o t h e e x t r e m e l y d y n a m i c
environment i n which they e x i s t .
There a r e a l s o a number o f i m p l i c a t i o n s o f t h e s e u n r e a c t e d
gas p o c k e t s . The f i r s t i s t h a t we now have a way o f c r e a t i n g a n
inhomogeneous m a t e r i a l o u t o f a homogeneous m a t e r i a l .
The p o c k e t s
o f m a t e r i a l a r e a t d i f f e r e n t p r e s s u r e s a n d t e m p e r a t u r e s , a n d have
a d i f f e r e n t c o m p o s i t i o n than t h e c o m p l e t e l y burned m a t e r i a l around
them. S e c o n d , s u c h p o c k e t s c o u l d p r o v i d e t h e p e r t u r b a t i o n n e c e s s a r y t o i n i t i a t e a n i n s t a b i l i t y and t h u s p r o v i d e t h e i n i t i a l i m p e t u s t o a mechanism t h a t w o u l d a l l o w t h e m a t e r i a l t o f o r m a new
number o f d e t o n a t i o n c e l l s c h a r a c t e r i s t i c o f t h e chamber s i z e . I n
an open e n v i r o n m e n t where t h e r e a r e no w a l l s , t h e p o c k e t s c o u l d
p r o v i d e t h e p e r t u r b a t i o n n e c e s s a r y t o a l l o w new c e l l s t o g e n e r a t e
and t h e number o f c e l l s t o i n c r e a s e . And f i n a l l y , t h e p o c k e t s
c o u l d p r o v i d e a mechanism f o r t h e e x t i n c t i o n o f d e t o n a t i o n s . A
s c e n a r i o c o u l d e v o l v e i n w h i c h more a n d more e n e r g y r e l e a s e i s
d e l a y e d b e c a u s e t h e p o c k e t s become b i g g e r and b i g g e r .
Flame A c c e l e r a t i o n a n d T r a n s i t i o n t o T u r b u l e n c e
Here we a r e i n t e r e s t e d i n mechanisms o f t h e t r a n s i t i o n p r o c e s s .
Some o f t h e b a s i c q u e s t i o n s we must a d d r e s s a r e f l u i d d y n a m i c s
questions:
how do l a m i n a r f l o w s t r a n s i t i o n t o t u r b u l e n t f l o w s a n d
what a r e t h e mechanisms o f v o r t i c i t y g e n e r a t i o n . Then we a s k how
the presence o f c h e m i c a l r e a c t i o n s and energy r e l e a s e a l t e r these
s i t u a t i o n s o r g e n e r a t e a d d i t i o n a l mechanisms t h r o u g h c o u p l i n g
interactions.
T h i s i n v o l v e s q u e s t i o n s such as how do f l a m e s
s t r e t c h and i n c r e a s e t h e i r s u r f a c e a r e a , and t h e r e b y i n c r e a s e t h e
b u r n r a t e and f l a m e v e l o c i t y .
The t r a n s i t i o n p r o c e s s i s o f t e n i n i t i a t e d by one o f a number
of i n s t a b i l i t i e s such as a R a y l e i g h - T a y l o r i n s t a b i l i t y , i n which a
heavy f l u i d i s a c c e l e r a t e d through a l i g h t f l u i d , o r a K e l v i n He l m h o l z i n s t a b i l i t y w h i c h i s t h e c l a s s i c s h e a r f l o w i n s t a b i l i t y .
F i g u r e 9 shows a t w o - d i m e n s i o n a l s i m u l a t i o n o f a R a y l e i g h - T a y l o r
i n s t a b i l i t y w h i c h was done w i t h a L a g r a n g i a n n u m e r i c a l method i n
w h i c h t h e u s u a l q u a d r i l a t e r a l c o m p u t a t i o n a l g r i d i s r e p l a c e d by a
g r i d o f t r i a n g l e s ( 2 1 ) . Such a n i n s t a b i l i t y a t a p r o p a g a t i n g
i n t e r f a c e p r o v i d e s a mechanism f o r f l a m e s t r e t c h i n g and t h u s f l a m e
acceleration.
F i g u r e 10 shows a t w o - d i m e n s i o n a l FCT E u l e r i a n
s i m u l a t i o n of a Kelvin-Helmholz i n s t a b i l i t y generated a t the
i n t e r f a c e between two c o f l o w i n g g a s e s o f d i f f e r e n t v e l o c i t i e s
(22).
The c o h e r e n t s t r u c t u r e s w h i c h f o r m t h r o u g h t h i s i n t e r a c t i o n
are i m p o r t a n t f o r m i x i n g and t h e t r a n s i t i o n t o t u r b u l e n c e i n gas
jets.
There i s a l s o a n o t h e r method o f g e n e r a t i n g v o r t i c i t y and t h u s
a way o f t r a n s i t i o n t o t u r b u l e n c e w h i c h i s n o t b a s e d on a f l u i d
i n s t a b i l i t y , b u t s i m p l y on t h e s t r a i g h t f o r w a r d g e n e r a t i o n o f

164
CYCLE =3.0lxl0
TIME=740M0'
2.5
0.75
0.38
r.t
>-
0.0
00
2.5
5.0
XICM)
CYCLE = l.20xl0
TIME=2.99xKT
\ )
>
>-
0.0
X (CM)
F i g u r e 7a. Contours o f t h e i n d u c t i o n parameter f o r c a l c u l a t i o n s

of a d e t o n a t i o n p r o p a g a t i n g i n a m i x t u r e o f hydrogen, oxygen, and
argon. High v a l u e s o f t h e i n d u c t i o n parameter i n d i c a t e t h a t t h e
m a t e r i a l i s a b o u t t o r e l e a s e e n e r g y . The p o s i t i o n o f t h e s h o c k
f r o n t i s marked b y t h e heavy dark s o l i d l i n e .

9.
ORAN
165
CYCLE = 9.01x10
r
TIME =2.24x10"
2.5r
F i g u r e 7b. C o n t o u r s o f t h e i n d u c t i o n p a r a m e t e r f o r c a l c u l a t i o n s
of a d e t o n a t i o n p r o p a g a t i n g i n a m i x t u r e o f hydrogen, oxygen, and
argon. High v a l u e s o f t h e i n d u c t i o n parameter i n d i c a t e t h a t t h e
m a t e r i a l i s a b o u t t o r e l e a s e e n e r g y . The p o s i t i o n o f t h e s h o c k
f r o n t i s marked b y t h e heavy d a r k s o l i d l i n e .

166
INDUCTION PARAMETER CONTOURS

TIME = l.37xl0"
CYCLE = 9.01x10*
0.5
f\
\\\
1
I',
|;
0.0
.9
i
W
!
X(CM)
1.01
0.76
0.51
0.26
0.01
3.6
X (CM)
F i g u r e 8a.
Same a s F i g u r e s 7 a a n d 7b e x c e p t f o r a s m a l l e r t u b e .

9.
167
ORAN
TEMPERATURE CONTOURS
CYCLE = 9.0IXI0
rc: /I
0.5
TIME = I.37xl0~
K
4500
3500
2500
H/
1500
500
i 1
i! 1
1.9
X (CM)
CYCLE=I.IOxl0
3.6
5
TIME= I.73xl0"
X (CM)
Figure 8b.
Same a s F i g u r e s Ta a n d 7b e x c e p t f o r a s m a l l e r t u b e .

168
F i g u r e 9Calculation o f Rayleigh-Taylor i n s t a b i l i t y using the

L a g r a n g i a n t e c h n i q u e w i t h a u t o m a t i c zone r e s t r u c t u r i n g .
A heavy
f l u i d f a l l s t h r o u g h a l i g h t f l u i d , a n d t h e r e i s a f r e e s u r f a c e on
the t o p .

9.
ORAN
169
Figure 10. One frame from the c a l c u l a t i o n o f the e v o l u t i o n o f a

Kelvin-Helmholtz i n s t a b i l i t y a t the surface o f a round j e t o f a i r
i n t o an a i r background.
C y l i n d r i c a l symmetry was used and the a x i s
of symmetry is- the l e f t - h a n d boundary.
Theînflow speed i s about
10 cm/s, and the outer co-flow i s about 10 cm/s.

170
v o r t i c i t y by t h e i n t e r a c t i o n o f p r e s s u r e waves w i t h d e n s i t y g r a d i e n t s o r o b s t a c l e s . These a r e two q u i t e d i f f e r e n t mechanisms.

The
i n t e r a c t i o n w i t h d e n s i t y g r a d i e n t s has r e c e n t l y been d i s c u s s e d by
P i c o n e e t a l . (23) who l o o k a t v o r t i c i t y g e n e r a t i o n t h r o u g h the
i n t e r a c t i o n o f weak s h o c k s and d e n s i t y g r a d i e n t s t y p i c a l o f an
expanding flame.
Through the i n t e r a c t i o n o f t h e p r e s s u r e wave
w i t h t h e f l a m e , t h e s c a l e o f the i n h o m o g e n e i t y i s h a l v e d .
Then as
a n o t h e r p r e s s u r e wave i n t e r a c t s w i t h t h i s n e w l y c r e a t e d inhomogen e i t y , the s c a l e i s a g a i n h a l v e d .
F i g u r e 11 shows r e s u l t s o f
P i c o n e s w h i c h were done t o s i m u l a t e s h o c k tube e x p e r i m e n t s by
M a r k s t e i n (24) . As t h e p l a n a r s h o c k p a s s e s t h r o u g h t h e s p h e r i c a l
d e n s i t y p e r t u r b a t i o n , v o r t i c i t y i s g e n e r a t e d and the s c a l e of the
inhomogeneity i s halved.
As t h e r e f l e c t e d s h o c k p a s s e s t h r o u g h
the d e n s i t y g r a d i e n t a g a i n , the s c a l e i s h a l v e d a g a i n .
M a r k s t e i n ' s e x p e r i m e n t s were done w i t h a f l a m e i g n i t e d i n a s h o c k
tube.
P i c o n e ' s c a l c u l a t i o n s were done f o r a d e n s i t y d i s c o n t i n u i t y
m o d e l e d on t h a t e x p e c t e d f o r a f l a m e .
Conclusions
and
Summary
I n the e x a m p l e s g i v e n above we have t r i e d t o d e s c r i b e some o f t h e

phenomena w h i c h a r i s e as a r e s u l t o f c h e m i c a l k i n e t i c - f l u i d
dynamic c o u p l i n g . F i r s t , we d e s c r i b e d s t u d i e s o f the i s o l a t e d
e f f e c t s o f c h e m i c a l - a c o u s t i c c o u p l i n g , e m p h a s i z i n g t h e e f f e c t s on
the c h e m i c a l k i n e t i c s .
The major c o n c l u s i o n i s t h a t sound waves
and e n t r o p y p e r t u r b a t i o n s c a n a l t e r c h e m i c a l t i m e s c a l e s , and t h a t
t h i s e f f e c t can be q u a n t i f i e d . We t h e n d e s c r i b e d a s y s t e m i n
w h i c h sound waves and e n t r o p y p e r t u r b a t i o n s b e h i n d a s h o c k wave
c a u s e d e a r l y i g n i t i o n a t u n p r e d i c t a b l e l o c a t i o n s and a t r e d u c e d
i g n i t i o n times.
A s e r i e s o f r e a c t i o n c e n t e r s f o r m e d and one o f
t h e s e c l o s e t o the shock f r o n t e v e n t u a l l y i g n i t e d .
The l a s t two s e c t i o n s d e a l t w i t h s y s t e m s i n w h i c h the f l o w
was t w o - d i m e n s i o n a l and t h u s s u b s t a n t i a l l y more c o m p l i c a t e d .
F i r s t we d e s c r i b e d some o f the p r o p e r t i e s o c c u r r i n g i n p r o p a g a t i n g
d e t o n a t i o n s , f o r w h i c h t h e s t r u c t u r e i s h i g h l y d e p e n d e n t on t h e
c h e m i c a l k i n e t i c - f l u i d dynamic i n t e r a c t i o n s . F i n a l l y , i n the l a s t
s e c t i o n we d i s c u s s e d some p r o c e s s e s and mechanisms i n v o l v e d i n t h e
t r a n s i t i o n to turbulence, which i s important f o r flames.
As we p r o c e e d e d i n t o the v a r i o u s s e c t i o n s i n t h i s p a p e r , we
d e s c r i b e d a s e r i e s o f p r o g r e s s i v e l y more c o m p l e x i n t e r a c t i o n s .
Each new t o p i c c o n t a i n e d most of the c o m p l i c a t i o n s p r e s e n t i n t h e
p r e v i o u s l y d i s c u s s e d t o p i c s . The b a s i c i n g r e d i e n t s i n t h e s t u d i e s
p r e s e n t e d a r e r e a s o n a b l e r e p r e s e n t a t i o n s of b o t h the f l o w f i e l d
and t h e c h e m i c a l k i n e t i c s .
The c o m p l e x i t y a r o s e b e c a u s e we c o n s i d e r e d m u l t i d i m e n s i o n a l e f f e c t s and expanded the range o f s c a l e s
considered.
In g e n e r a l , the c u r r e n t l e v e l o f u n d e r s t a n d i n g of the
d e t a i l s of the i n t e r a c t i o n s between the c h e m i s t r y and f l o w i s l e s s
a c c u r a t e as t h e f l o w and t h e c h e m i c a l r e a c t i o n s become more and

9. OR AN
171
DENSITY CONTOURS
30.0,
0.0
0.19 ms
(cm)
0.72 ms
0.38
0.49
0.60
1.11
1.40
1.88
10.0
Figure 1 1 .
Density contours f o r the s i m u l a t i o n o f a weak shock
passing through a d e n s i t y g r a d i e n t . Time i s marked on top o f each
frame. The i n c i d e n t shock i s passing through the gradient a t 0 . 1 9
ms, and by 1.11 ms the r e f l e c t e d shock has passed through.

172
more complex. However, as we have t r i e d to show, we are j u s t now

at the stage where we can begin to include t h i s e f f e c t a c c u r a t e l y
i n simulations
Acknowledgments
The author would l i k e to thank Drs. Jay B o r i s , John Gardner,
Michael Picone, Marty F r i t t s , Ted Young, and K. Kailasanath f o r
t h e i r h e l p . This work has been sponsored by the Naval Research
Laboratory through the O f f i c e of Naval Research.
Literature Cited
1. Oran, E.S.; Gardner, J.H., "A Review of Research in ChemicalAcoustic Coupling," NRL Memo. Report 5121, Naval Research
Laboratory, 1983.
2. Einstein, ., Sitzber. Deut. Akad. Wiss. Berlin, Kl.-Math.naturn., 1920, 380.
3. Chu, B.T., Proc. of Heat Transfer and Fluid Mechanics
Institute, 1958, p. 80.
4. Clarke, J.F.; McChesney, M., "The Dynamics of Real Gases";
Buttersworth: Washington, D.C., 1964, p. 182.
5. Clarke, J.F., Comb. Sci. Tech. 1973, 7, 241.
6. Srinivasen J.; Vincenti W.G., Phys. Fluids 1975, 18, 1670.
7. Clarke, J.F., Prog. Astro. Aero. 1981, 76, 383.
8. Blythe, P.., J. Fluid Mech. 1969, 37, 31.
9. Toong, T.Y., Combust. Flame 1972, 18, 207.
10. Abouseif, G.E.; Toong, T.Y.; Converti, J., Seventeenth
Symposium (International) on Combustion, 1979, p.1341.
11. Gilbert, R.; Ortoleva, P.; Ross, J., J. Chem. Phys. 1973, 58,
3625.
12. Oran, E.S.; Boris, J . , Combust. Flame 1982, 48, 149.
13. Edwards, D.H.; Thomas, G.O.; Williams, T.L., Combust. Flame
1981, 43, 187.
14. Kailasanath, K.; Oran, E.S., Combust. Sci. Tech. 1983, to
appear
15. Erpenbeck, J.J., Phys. Fluids 1965, 8, 1192.
16. Fickett, W.; Wood, W.W., Phys. Fluids 1966, 9, 903.
17. Strehlow, R.A., "Fundamentals of Combustion", Krieger: New
York, 1979; Chapt. 9.
18. Fickett, W., and Davis, W.C., "Detonation", University of
California Press: Berkeley, 1979.
19. Taki. S.; Fujiwara, T., Eighteenth Symposium (International)
on Combustion, 1981, p. 1671.
20. Oran, E.S.; Young, T.R.; Boris, J.P.; Picone, J.M.; Edwards,
D.H., Nineteenth Symposium (International) on Combustion,
1982, p. 573.
21. Fritts, M.J.; Boris, J.P., J. Comp. Phys. 1979, 31, 173.

9.
ORAN
173
22. Boris, J.P.; Fritts, M.J.; Oran, E.S., "Numerical Simulations

of Shear Flows in the Splitter Plate and Round Jet", Naval
Research Laboratory Memo Report, to appear 1983.
23. Picone, J.M.; Oran, E.S.; Boris, J.P.; Young, T.R., Proc. 9th
ICODERS, To appear 1984.
24. Markstein, G.H., "Nonsteady Flame Propagation," Pergamon:
Oxford, 1964.
RECEIVED October 28, 1983

10
Chemical Kinetic Factors in Gaseous Detonations
CHARLES K. WESTBROOK
University of California, Lawrence Livermore National Laboratory, Livermore, CA 94550
Computer modeling techniques have been applied to

the study of hydrogen and hydrocarbon oxidation in
gaseous detonation waves. Characteristic reaction
times and lengths are computed which correlate well
with observed detonation parameters, including
c r i t i c a l tube diameters for transition to spherical
detonation, detonation cell sizes, c r i t i c a l i n i t i a
tion energies, and lean and rich limits for detona
tion in a linear tube. Inhibition or extinction of
a detonation is shown to occur from increases in
the ignition delay time, and increased detonability
or kinetic sensitization results from decreased
ignition delay times.
Detonation waves a r e an important c l a s s o f combustion phenomena,
due both t o the p o t e n t i a l s a f e t y hazards which they represent
and t o t h e i n s i g h t s i n t o fundamental combustion processes which
they provide. Gaseous detonations have been examined f o r many
years, i n both experimental and t h e o r e t i c a l s t u d i e s . More r e c e n t l y , computer modeling s t u d i e s o f detonation waves have begun
t o appear. The chemical k i n e t i c s submodels have been considered
t o be the weakest p a r t o f e x i s t i n g detonation models. However,
recent development o f comprehensive k i n e t i c r e a c t i o n mechanisms
f o r the o x i d a t i o n o f many p r a c t i c a l f u e l s ( 1 , 2 ) has changed t h i s
situation significantly.
The present paper r e p o r t s progress t h a t has been made on
chemical k i n e t i c s i n detonations and how w e l l k i n e t i c p r e d i c t i o n s c o r r e l a t e w i t h a v a i l a b l e experimental data.
The success
o f t h i s approach i n reproducing experimental data i l l u s t r a t e s
the c e n t r a l r o l e o f k i n e t i c s i n detonations, and i t suggests
s t r o n g l y t h a t t h i s technique provides a r e l i a b l e b a s i s f o r pred i c t i n g detonation p r o p e r t i e s f o r c o n d i t i o n s which have not y e t
been explored e x p e r i m e n t a l l y .
For example, very few e x p e r i mental data a r e a v a i l a b l e f o r detonation p r o p e r t i e s a t i n i t i a l
0097-6156/ 84/ 0249-0175$06.00/ 0
176
p r e s s u r e s above 1 atm, a t i n i t i a l t e m p e r a t u r e s d i f f e r e n t f r o m
n o r m a l room t e m p e r a t u r e , o r f o r m i x t u r e s i n w h i c h t h e o x i d i z e r
i s a i r r a t h e r than oxygen. A l l t h e s e can b e o f extreme p r a c t i c a l i n t e r e s t t o t h e i n d u s t r i a l community i n h e l p i n g t o u n d e r stand the hazards
sociated w i t h e x p l o s i v e m i x t u r e s and t o know
how a c c i d e n t a l d i s a s t e r s c a n b e p r e v e n t e d . A s a f u r t h e r e x t e n s i o n o f t h i s type o f approach, t h i s type o f modeling can suggest
k i n e t i c means o f m o d i f y i n g t h e d e t o n a t i o n p a r a m e t e r s o f a g i v e n
f u e l - o x i d i z e r mixture, e i t h e r enhancing o r i n h i b i t i n g detonab i l i t y through the use o f a p p r o p r i a t e c h e m i c a l a d d i t i v e s .
Chemical K i n e t i c s
At t h e p r e s e n t t i m e , t h e f u e l s w h i c h c a n b e d e s c r i b e d b y t h i s
m o d e l i n g a p p r o a c h i n c l u d e h y d r o g e n , c a r b o n monoxide, methane,
methanol, ethane, e t h y l e n e , a c e t y l e n e , propane, and p r o p y l e n e .
The r e a c t i o n mechanism u s e d t o d e s c r i b e t h e o x i d a t i o n o f t h e s e
f u e l s h a s been d e v e l o p e d a n d v a l i d a t e d i n a s e r i e s o f p a p e r s
(3-7). T h e e l e m e n t a r y r e a c t i o n s and t h e i r r a t e e x p r e s s i o n s a r e
summarized i n R e f e r e n c e (_7) a n d a r e n o t r e p r o d u c e d h e r e d u e t o
s p a c e l i m i t a t i o n s . R e v e r s e r e a c t i o n r a t e s a r e computed f r o m t h e
f o r w a r d r a t e s and t h e a p p r o p r i a t e thermodynamic d a t a (J3). T h i s
mechanism h a s been shown t o d e s c r i b e t h e o x i d a t i o n o f methane
(3,A), m e t h a n o l (_5), e t h y l e n e (6), and p r o p a n e and p r o p y l e n e (7)
o v e r w i d e r a n g e s o f e x p e r i m e n t a l c o n d i t i o n s . I t h a s a l s o been
u s e d t o d e s c r i b e t h e s h o c k t u b e o x i d a t i o n o f e t h a n e (4,9), a n d
a c e t y l e n e (10).
The p a r a m e t e r r e g i m e s i n a d e t o n a t i o n a r e s i m i l a r t o t h o s e
i n s h o c k t u b e s , s o t h e most i m p o r t a n t t e s t o f t h i s t y p e o f mecha n i s m i s i t s a b i l i t y t o r e p r o d u c e s h o c k t u b e i g n i t i o n d a t a . One
example o f t h i s v a l i d a t i o n p r o c e s s compared computed i g n i t i o n
d e l a y t i m e s 7) w i t h e x p e r i m e n t a l r e s u l t s o f B u r c a t e t a l .
(11).
I n t h e e x p e r i m e n t s , m i x t u r e s o f p r o p a n e , oxygen, a n d
a r g o n were s t u d i e d i n r e f l e c t e d s h o c k waves a t i n i t i a l t e m p e r a t u r e s f r o m 1250 t o 1700 K, p r e s s u r e s from 2 t o 15 a t m o s p h e r e s ,
and e q u i v a l e n c e r a t i o s f r o m 0.5 t o 2.0. From t h e e x p e r i m e n t a l
r e s u l t s , i t was f o u n d t h a t t h e i g n i t i o n d e l a y t i m e c o u l d b e
approximated i n terms o f the i n i t i a l temperature T a n d r e a c
t a n t c o n c e n t r a t i o n s ( i n moles/cm^) b y
0
= 4.4 " * exp(21240/T )

1
[C H ]0.57[o ]-1.22
3
In e a c h c o m p u t a t i o n was d e f i n e d a s t h e t i m e c o r r e s p o n d i n g t o
t h e maximum r a t e o f r e a c t i o n between CO a n d 0 atoms.
Other
r e a l i s t i c d e f i n i t i o n s o f , s u c h a s t h e t i m e o f maximum r a t e
of p r e s s u r e o r temperature r i s e , gave n e a r l y i d e n t i c a l r e s u l t s .
From t h e computed i g n i t i o n d e l a y t i m e s a n d i n i t i a l r e a c t a n t
c o n c e n t r a t i o n s , model v a l u e s o f t h e c o r r e l a t i o n f u n c t i o n 3
1
= [023
2 2
[C3H ]-0.57
8
u s
(mole/cm3)0.65

10.
WESTBROOK
Kinetic Factors in Gaseous Detonations
177
were c a l c u l a t e d , and t h e r e s u l t s a r e summarized i n Figure 1.

The s o l i d l i n e represents t h e o v e r a l l experimental c o r r e l a t i o n
f u n c t i o n o f Burcat e t a l . , while t h e i n d i v i d u a l symbols r e p r e
sent computed values o f 3 . The s p e c i f i c c o n d i t i o n s f o r each
Mixture i d e n t i f i e d i n Figure 1 can be found i n Reference (11).
The general agreement between computed and experimental data i s
very good, i n d i c a t i n g t h a t t h e r e a c t i o n mechanism i s p r o p e r l y
reproducing t h e shock tube i g n i t i o n behavior f o r t h i s f u e l .
S i m i l a r d e t a i l e d comparisons have been c a r r i e d out i n previous
modeling s t u d i e s with b a s i c a l l y t h e same r e a c t i o n mechanism f o r
ethylene ( 6 ) , methane and ethane (A), and methanol ( 5 ) . The
H2 o x i d a t i o n submechanism has been e x t e n s i v e l y v a l i d a t e d , with
nearly a l l o f the elementary r e a c t i o n r a t e s being w e l l known.
In the past, detonation models have used g l o b a l r a t e expres
s i o n s t o compute chemical i n d u c t i o n times f o r f u e l - o x i d i z e r mix
t u r e s , but such expressions a r e o f t e n not s a t i s f a c t o r y , even
when they have been based on shock tube data.
Most shock tube
experiments a r e c a r r i e d out with high d i l u t i o n by Ar, He, o r
N2, so that f u e l and oxygen concentrations a r e u s u a l l y q u i t e
low.
However, o v e r a l l r e a c t i o n order and a c t i v a t i o n energy i n
g l o b a l i n d u c t i o n time c o r r e l a t i o n s o f t e n change with the amount
o f d i l u t i o n . G l o b a l r a t e parameters can a l s o change with equiv
alence r a t i o , pressure and temperature. As a r e s u l t , i n d u c t i o n
times computed from g l o b a l expressions can be s e r i o u s l y i n e r r o r
when a p p l i e d t o u n d i l u t e d f u e l - o x i d i z e r mixtures, making a de
t a i l e d k i n e t i c mechanism an e s s e n t i a l part o f the present deto
n a t i o n model.
The k i n e t i c submechanism f o r the i n h i b i t i o n s t u d i e s was a l s o
developed by a s e q u e n t i a l process, beginning w i t h HBr (12) and
the other halogen a c i d s HC1 and HI, followed by r e a c t i o n s i n
v o l v i n g methyl, v i n y l , and e t h y l h a l i d e s (13) and CF3Br (14).
The
i n h i b i t i o n mechanism and r e a c t i o n r a t e s a r e given i n
Reference (13).
Detonation Model
The model used here i s t h e Zeldovich-von Neumann-Doring (ZND)
model i n which, l o c a l l y , a detonation c o n s i s t s o f a shock wave
t r a v e l i n g a t t h e Chapman-Jouguet (CJ) v e l o c i t y , followed by a
r e a c t i o n zone. The shock wave compresses and heats t h e f u e l o x i d i z e r mixture which then begins t o r e a c t .
I n most mixtures
the f u e l o x i d a t i o n c o n s i s t s o f a r e l a t i v e l y long i n d u c t i o n
p e r i o d during which t h e temperature and pressure remain n e a r l y
constant, followed by a r a p i d r e l e a s e o f chemical energy and
temperature i n c r e a s e .
F o r each f u e l - o x i d i z e r mixture, a c a l c u
l a t i o n i s f i r s t made o f t h e relevant CJ c o n d i t i o n s .
From t h e
detonation v e l o c i t y D Q J , t h e c o n d i t i o n s i n t h e von Neumann
spike,
including
t h e temperature
, pressure
P i , and
p a r t i c l e v e l o c i t y u i o f the post-shock unreacted gases can be
computed and then used as i n i t i a l c o n d i t i o n s f o r t h e chemical

178
F i g u r e 1.
C o r r e l a t i o n f u n c t i o n s f o r shock tube i g n i t i o n o f propane. S o l i d l i n e i s o v e r a l l c o r r e l a t i o n from Burcat et a l . ( i l ) ;
symbols are computed values.

10.
WESTBROOK
179
k i n e t i c s m o d e l . The s h o c k v e l o c i t y v a r i e s w i t h i n a s i n g l e d e t o n a t i o n c e l l from an i n i t i a l v a l u e o f a b o u t 1.6 D j t o a m i n i mum o f a b o u t 0.6 D Q J , so t h e C J c o n d i t i o n s u s e d h e r e r e p r e s e n t

a v e r a g e v a l u e s , and computed i n d u c t i o n t i m e s w i l l a l s o b e
averages.
The r e a c t i v e m i x t u r e i s assumed t o r e m a i n a t a c o n s t a n t
volume o v e r i t s r e a c t i o n t i m e , and t h e i n d u c t i o n t i m e i s d e f i n e d
i n terms o f i t s temperature h i s t o r y .
Most o f t h e
mixtures
underwent a l a r g e t e m p e r a t u r e i n c r e a s e o f more t h a n 1000 K, and
t h e i n d u c t i o n t i m e i s d e f i n e d as t h e t i m e o f maximum r a t e o f
temperature increase.
I n most c a s e s , t h i s c o i n c i d e s a p p r o x i m a t e l y w i t h t h e t i m e a t w h i c h t h e t e m p e r a t u r e has c o m p l e t e d
about h a l f o f i t s t o t a l i n c r e a s e . T h i s i s not, s t r i c t l y speaking, a t r u e i n d u c t i o n p e r i o d , o f t e n d e f i n e d as the time r e q u i r e d
f o r a s m a l l ( i . e . 1-5%) t e m p e r a t u r e o r p r e s s u r e i n c r e a s e , b u t i t
r e p r e s e n t s a t i m e s c a l e f o r t h e r e l e a s e o f a s i g n i f i c a n t amount
o f energy. In a d d i t i o n to the i n d u c t i o n time , i t i s u s e f u l
t o d e f i n e the i n d u c t i o n length T ( D C J - U I ) , which r e p r e
sents a c h a r a c t e r i s t i c length s c a l e i n the post-shock unreacted
gas m i x t u r e .
As a r e s u l t o f t h e s e s i m p l i f i c a t i o n s , t h e computed i n d u c t i o n
t i m e s and l e n g t h s d e f i n e c h a r a c t e r i s t i c t i m e and l e n g t h s c a l e s
r a t h e r t h a n t h e p r e c i s e h i s t o r y o f a gas e l e m e n t t h r o u g h t h e
d e t o n a t i o n f r o n t . The e v o l u t i o n o f t h e r e a c t e d gas s u b s e q u e n t
t o the i n d u c t i o n p e r i o d considered here i s dominated by the
f l u i d mechanics o f the p o s t - i n d u c t i o n expansion o f the r e a c t i o n
products.
T h i s e x p a n s i o n r e d u c e s t h e p r e s s u r e and d e n s i t y o f
t h e s e p r o d u c t s and a l t e r s t h e k i n e t i c e q u i l i b r i u m , l e a d i n g
eventually to the C J s t a t e . Since v i r t u a l l y a l l of the react a n t s h a v e been consumed b y t h i s t i m e , t h e k i n e t i c s o f t h i s
f i n a l e x p a n s i o n p h a s e a r e c o n t r o l l e d by r e l a t i v e l y s l o w r a d i c a l
recombination processes.
The p r e s e n t model d o e s n o t a t t e m p t t o
f o l l o w t h a t e n t i r e r e l a x a t i o n p h a s e , c o n c e n t r a t i n g o n t h e de
t a i l s o f t h e i n d u c t i o n k i n e t i c s i n t h e von Neumann s p i k e .
T h i s model o f t h e d e t o n a t i o n n e g l e c t s some p o t e n t i a l l y s i g
n i f i c a n t e f f e c t s a r i s i n g from h y d r o d y n a m i c - k i n e t i c
interac
tions.
Variations o f density,
temperature,
and particle
v e l o c i t y i n the post-shock unreacted mixture are not c o n s i d
ered.
M u l t i p l e s h o c k wave r e f l e c t i o n s , r a r e f a c t i o n s , i n t e r a c
t i o n s w i t h c o n f i n i n g w a l l s , c e l l u l a r s t r u c t u r e , and r e l a t e d
e f f e c t s a r e a l s o n o t t r e a t e d d i r e c t l y by t h e p r e s e n t s i m p l i f i e d
m o d e l . A r e a l l y c o m p r e h e n s i v e d e t o n a t i o n s i m u l a t i o n model w i l l
h a v e t o i n c l u d e s u c h i n t e r a c t i o n s and a t l e a s t two and p r o b a b l y
even t h r e e space dimensions, but such a treatment i s beyond the
scope o f the present formulation.
I n c a s e s where s u c h i n t e r a c
t i o n s a r e i m p o r t a n t , t h i s a p p r o a c h may n o t be a d e q u a t e .
Results
Many C J and i n d u c t i o n d e l a y t i m e c a l c u l a t i o n s h a v e been c a r r i e d

180
out, examining t h e e f f e c t s o f v a r i a t i o n s i n many p h y s i c a l and

chemical parameters.
F o r fuel-02 and f u e l - a i r mixtures, t h e
equivalence r a t i o can be v a r i e d over the complete range from
pure o x i d i z e r t o pure f u e l .
For s t o i c h i o m e t r i c fuel-02 mix
t u r e s t h e amount o f d i l u t i o n by N2 can be v a r i e d between =
0 ( i s t h e i n i t i a l r a t i o o f N2 t o O2, so = 0 c o r r e
sponds t o a fuel-02 mixture) and = 3.76 ( i . e . f u e l - a i r ) .
Other d i l u e n t s such as CO2, H2O, and Ar have been used. The
i n i t i a l pressure has been v a r i e d between 0.01 and 10.0 atmo
spheres, and the i n i t i a l temperature between 200 and 500 i n
s t o i c h i o m e t r i c f u e l - C ^ and f u e l - a i r .
F i n a l l y , s m a l l amounts
o f s e l e c t e d halogenated s p e c i e s have been i n c l u d e d i n f u e l - a i r
mixtures i n i t i a l l y a t atmospheric temperature and pressure.
As an example, computed values o f t h e i n d u c t i o n l e n g t h
are summarized i n F i g u r e 2, showing the e f f e c t s o f v a r i a t i o n s i n
the f u e l - o x i d i z e r equivalence r a t i o .
The dashed curves
represent f u e l - a i r and t h e s o l i d curves fuel-02 mixtures.
R e s u l t s f o r propane (not shown) a r e very s i m i l a r t o those f o r
ethane.
A l l o f these r e s u l t s assume t h a t t h e i n i t i a l pressure
i s atmospheric and the i n i t i a l temperature i s 300 K. There i s a
s i g n i f i c a n t d i f f e r e n c e between the hydrocarbon r e s u l t s and those
f o r hydrogen. F o r each hydrocarbon, values o f f o r fuel-02
are lower than those f o r f u e l - a i r by a f a c t o r o f about 100, and
the minimum value o f f a l l s on t h e r i c h s i d e o f s t o i c h i o
m e t r i c . However, f o r H2-O2 mixtures, values o f a r e only
a f a c t o r o f 10 lower than those f o r H2-air (15), and the m i n i
mum value o f occurs on t h e lean s i d e o f s t o i c h i o m e t r i c . I n
d u c t i o n lengths have been computed f o r a wide v a r i e t y o f other
i n i t i a l c o n d i t i o n s as w e l l , and the remaining s e c t i o n s o f t h i s
paper w i l l show how these i n d u c t i o n lengths can be r e l a t e d t o
s p e c i f i c detonation p r o p e r t i e s .
Detonation l i m i t s .
The most important r e s u l t o f t h e k i n e t i c
modeling work has been the observation t h a t the i n d u c t i o n l e n g t h
i s approximately p r o p o r t i o n a l t o t h e c h a r a c t e r i s t i c detona
t i o n c e l l width a. For s t o i c h i o m e t r i c f u e l - a i r and fuel-oxygen
mixtures i n i t i a l l y a t atmospheric temperature and pressure, t h e
r a t i o a/ i s approximately 20 and 35 r e s p e c t i v e l y , based on
observed c e l l s i z e s from experimental s t u d i e s (16-18).
Similar
agreement i s obtained between computed i n d u c t i o n lengths and
experimental c e l l s i z e data a t i n i t i a l pressures t h a t a r e d i f
ferent from atmospheric (19,20). C o r r e l a t i o n s with c e l l s i z e
data o f Manzhalei e t aTT ll9)
f o r CH4-O2, C2H2-O2, and
H2-O2 mixtures a r e shown i n F i g u r e 3. Here i n i t i a l p r e s
sures are v a r i e d between 0.01 and 10 atmospheres, and the agree
ment w i t h computed r e s u l t s i s good when a/ = 29, c o n s i s t e n t
with t h e p r o p o r t i o n a l i t y obtained above a t atmospheric pres
sure. The computed r e s u l t s reproduce even the s l i g h t curvature
i n t h e H2-O2 measurements.
This p r o p o r t i o n a l i t y can then be
used t o p r e d i c t the l e a n and r i c h l i m i t s o f detonation i n l i n e a r

F i g u r e 2. Computed i n d u c t i o n lengths f o r f u e l - o x i d i z e r mixtures.

Dashed curves are f o r f u e l - a i r mixtures ; s o l i d curves f o r f u e l - O ^
mixtures.

182

10.
Kinetic Factors in Gaseous
WESTBROOK
Detonations
183
tubes, i f i t i s assumed t h a t single-head s p i n n i n g detonation

occurs a t t h e l i m i t s w i t h a t r a n s v e r s e wave spacing t h a t i s
twice t h e tube diameter.
This has been done (15,21-24), u s i n g
experimental data from a v a r i e t y o f sources (25-29). Using t h e
computed i n d u c t i o n l e n g t h , the experimental tube diameter can be
used t o p r e d i c t t h e l i m i t compositions.
Alternatively, the
l i m i t composition can be given and t h e model w i l l p r e d i c t t h e
tube diameter r e q u i r e d .
C r i t i c a l tube diameter.
I t has been found (30-32) t h a t , f o r a
planar detonation i n a l i n e a r tube o f c i r c u l a r c r o s s s e c t i o n t o
i n i t i a t e an unconfined s p h e r i c a l d e t o n a t i o n , t h e tube must have
a diameter d l a r g e enough t o accomodate a t l e a s t 13 t r a n s
verse waves. Since the k i n e t i c i n d u c t i o n l e n g t h i s p r o p o r t i o n a l
to t h e t r a n s v e r s e wave spacing, i t should a l s o be p r o p o r t i o n a l
t o t h i s c r i t i c a l tube diameter d . I n F i g u r e 4 we r e l a t e
these q u a n t i t i e s , together with experimental data (33-35). I n
these
experiments,
stoichiometric
fuel-C^
mixtures
were
d i l u t e d by s u c c e s s i v e l y l a r g e r amounts o f , u n t i l t h e r a t i o
3 o f N2/O2 i n t h e unreacted mixture was equal t o 3.76, t h e
value o f 3 i n normal a i r . I n F i g u r e 4 t h e experimental data
are represented by symbols, w i t h i n d i c a t i n g C2H^-oxidizer
mixtures s t u d i e d by Z e l d o v i c h e t a l . ( 3 5 ) , p l u s i n d i c a t i n g
C2H4-oxidizer mixtures s t u d i e d by Moen e t a l . ( 3 4 ) , and a l l
other symbols showing data o f Matsui and Lee (33 Both con
v e n t i o n a l s t o i c h i o m e t r i c mixtures and "CO s t o i c h i o m e t r i c " mix
t u r e s are shown. The best agreement between computed and meas
ured r e s u l t s i s obtained when d = 380 . Combined with t h e
c e l l s i z e p r o p o r t i o n a l i t y from F i g u r e 2 o f a = 29 , these
computations p r e d i c t
= 13.1 a
(1)
which i s i n e x c e l l e n t agreement w i t h t h e o b s e r v a t i o n s t h a t 13
c e l l diameters a r e r e q u i r e d f o r t h e c r i t i c a l tube diameter.
Because t h e o v e r a l l agreement between computed p r e d i c t i o n s o f
d and experimental values shown i n F i g u r e 4 i s good f o r a l l
o f t h e f u e l s considered (as w e l l as f o r propane and hydrogen,
not shown), t h e model can be used t o p r e d i c t values f o r f u e l o x i d i z e r mixtures which have not been s t u d i e d e x p e r i m e n t a l l y .
I t i s a l s o important t o note t h a t H2-O2 responds much d i f
f e r e n t l y t o d i l u t i o n by ? than do t h e hydrocarbon mixtures.
Although
H2-O2 has a value o f s i m i l a r
t o that o f
C2H5-O2, t h e computed v a r i a t i o n
o f with d i l u t i o n f o r
H2 i s much l e s s than f o r t h e hydrocarbons, so t h a t f o r
H2-air i s very s i m i l a r t o t h a t o f s t o i c h i o m e t r i c C2H2-air.
C r i t i c a l tube diameters have a l s o been measured f o r s t o i
c h i o m e t r i c f u e l - o x i d i z e r mixtures a t pressures d i f f e r e n t from
atmospheric (33,36-38).
Comparisons between experimental values
for d
and computed values o f a t d i f f e r e n t
initial
c

184
T3
Air 4
Figure k.
V a r i a t i o n of computed i n d u c t i o n l e n g t h and c r i t i c a l tube
diameter with degree of n i t r o g e n d i l u t i o n f o r s t o i c h i o m e t r i c f u e l o x i d i z e r mixtures.
The symbols are described i n the t e x t .

10.
WESTBROOK
185
pressures are shown i n Figure 5. Again the general agreement i s

good when d = 380 . Several other p o i n t s a r e worth not
ing.
F i r s t , f o r a l l o f the hydrocarbon-02 mixtures,
c
= k i -a
(2)
i s c o n s i s t e n t w i t h experimental observations (33). However, f o r

H2-O2 there i s a d e f i n i t e curvature i n the computed r e s u l t s
when they a r e p l o t t e d l o g a r i t h m i c a l l y as i n F i g u r e 5, although
over the pressure range s t u d i e d e x p e r i m e n t a l l y t h e apparently
l i n e a r r e s u l t s are reproduced w e l l by the k i n e t i c model. A l l o f
the f u e l - a i r computed r e s u l t s show curvature i n F i g u r e 5. Of
p a r t i c u l a r i n t e r e s t i s t h e computed curve f o r H2-air which i s
m u l t i p l e - v a l u e d f o r some values o f d o r . S i m i l a r t o ex
p l o s i o n l i m i t curves f o r H2-O2 (28), t h i s behavior i s due t o
changes with pressure i n the dominant elementary r e a c t i o n chains
which occur i n H2 o x i d a t i o n , p a r t i c u l a r l y the competition be
tween the r e a c t i o n s
c
+ 0
+ 0
2
2
= 0 + OH
+ = H0 + M
2
No experimental data could be found t o compare w i t h t h i s pre

d i c t e d behavior o f H2~air mixtures a t d i f f e r e n t i n i t i a l p r e s
s u r e s ; i t would be i n t e r e s t i n g t o see i f the same value o f d
would be found a t s e v e r a l d i f f e r e n t i n i t i a l pressures, as t h e
k i n e t i c model p r e d i c t s . F u r t h e r , because o f t h e curvature and
m u l t i p l e - v a l u e d behavior shown f o r some mixtures i n F i g u r e 5,
Equation 2 should not be used f o r e x t r a p o l a t i n g r e s u l t s t o p r e s
sures o u t s i d e the range a c t u a l l y s t u d i e d e x p e r i m e n t a l l y .
The model has a l s o been used t o p r e d i c t t h e v a r i a t i o n o f
i n d u c t i o n length with i n i t i a l gas temperature
T
(35). At
constant i n i t i a l pressure, the i n d u c t i o n length and c r i t i c a l
tube diameter were found t o i n c r e a s e s l o w l y with T . The
v a r i a t i o n i n i n i t i a l d e n s i t y w i t h T i s t h e r e f o r e more impor
t a n t than the s l i g h t increase i n elementary r e a c t i o n r a t e s w i t h
T.
These r e s u l t s suggest t h a t t h e d e t o n a b i l i t y o f c o l d gas
mixtures, such as those which can r e s u l t from s p i l l s o f l i q u e
f i e d n a t u r a l gas (LNG) o r other c r y o g e n i c a l l y s t o r e d f u e l s , w i l l
be s l i g h t l y g r e a t e r than t h e same mixtures a t normal ambient
temperatures.
c
C r i t i c a l energy o f d i r e c t i n i t i a t i o n .
The k i n e t i c s model has
been used t o p r e d i c t the amount o f energy necessary t o i n i t i a t e
unconfined detonations, using t h e r e l a t i o n o f Z e l d o v i c h e t a l .
(35)
E
AJ
where j = 1, 2, o r 3 f o r p l a n a r , c y l i n d r i c a l ,
(3)
or spherical

186
configurations,
r e s p e c t i v e l y . Comparisons
between computed
v a l u e s o f A J a n d c r i t i c a l h i g h e x p l o s i v e i n i t i a t o r masses
(39-46) show good a g r e e m e n t ( 1 5 , 2 1 - 2 4 ) .
F o r example, i n F i g u r e
6 t h e c r i t i c a l mass o f T e t r y l h i g h e x p l o s i v e r e q u i r e d t o i n i t i
a t e unconfined s p h e r i c a l d e t o n a t i o n i n C2H-air
(43) i s
p l o t t e d a s a f u n c t i o n o f e q u i v a l e n c e r a t i o . A l s o shown i s
t h e computed c u r v e f o r f o r t h e same m i x t u r e s ( 2 1 ) . T h e
shape o f the c u r v e a n d the v a l u e o f c o r r e s p o n d i n g t o t h e
minimum v a l u e o f E (and maximum d e t o n a b i l i t y ) a r e b o t h r e p r o
duced very w e l l by the numerical k i n e t i c model. S i m i l a r agree
ment was f o u n d w i t h t h e o t h e r f u e l - a i r m i x t u r e s f o r which d a t a
were a v a i l a b l e .
F o r i n i t i a t i o n o f s p h e r i c a l d e t o n a t i o n b y means o f a l i n e a r
t u b e , Lee e t a l . (33,47) and U r t i e w and T a r v e r (48) r e l a t e d t h e
c r i t i c a l i n i t i a t i o n e n e r g y t o t h e work which must b e done t o
produce a s u f f i c i e n t l y s t r o n g source i n the unconfined gas. The
resulting expression
3
g i v e s the c r i t i c a l energy i n terms o f the c r i t i c a l tube diameter

d and t h e p r e s s u r e P, p a r t i c l e v e l o c i t y u , and s h o c k v e l o c i t y
D o f t h e C J s t a t e . T h i s c a n be combined w i t h t h e r e l a t i o n
between d and , g i v i n g
c
o T
( )
Computed v a l u e s o f E , b a s e d o n t h e k i n e t i c model ( w i t h ko =
0.1964) a g r e e w e l l (23,24) w i t h v a l u e s d e r i v e d from e x p e r i m e n t a l
measurements i n f u e l - 0 2 m i x t u r e s ( 3 3 , 4 9 ) .
F o r a l l o f t h e s e c o r r e l a t i o n s , p e r h a p s t h e most s i g n i f i c a n t
c o n c l u s i o n i s t h a t t h e computed c u r v e s a g r e e s i m u l t a n e o u s l y w i t h
the e x p e r i m e n t a l r e s u l t s f o r a l l o f t h e f u e l s examined. The
r a t i o s between t h e e x p e r i m e n t a l a n d p r e d i c t e d v a l u e s o f E a r e
e s s e n t i a l l y t h e same i n e a c h c a s e . T h i s means t h a t s i m i l a r p r e
d i c t i o n s c a n b e made f o r o t h e r f u e l s f o r which e x p e r i m e n t a l d a t a
a r e l a c k i n g b u t f o r which a r e l i a b l e k i n e t i c mechanism e x i s t s .
c
I n h i b i t i o n o f d e t o n a t i o n . Chemical a d d i t i v e s can have a l a r g e

e f f e c t on experimentally observed i g n i t i o n delay times.
Small
amounts o f NO2, N2O, H2, o r h i g h e r a l k a n e s c a n s i g n i f i
c a n t l y r e d u c e t h e i n d u c t i o n t i m e i n CH4-O2 a n d C f y - a i r
mixtures
(4,9,42,46,50-55).
Conversely, halogenated
species
h a v e b e e n shown (56,57) t o i n c r e a s e t h e i n d u c t i o n t i m e i n
fuel-02 mixtures.
S i n c e t h e i n d u c t i o n time i s a c r i t i c a l
factof
i n determining
the detonability o f fuel-oxidizer
m i x t u r e s , h a l o g e n a t e d compounds a n d o t h e r s p e c i e s may h a v e a n
important r o l e i n reducing the d e t o n a b i l i t y hazards o f p r a c t i c a l
fuels.

10.
WESTBROOK
187
Detonations
d - (meters)
c
0.1
0.001
100
Induction length (meters)

Figure 5 .
V a r i a t i o n o f computed i n d u c t i o n l e n g t h and experimental
l y measured c r i t i c a l tube diameter with i n i t i a l pressure.
Solid
curves are computed r e s u l t s f o r fuel-O^ mixtures ; dashed curves
f o r f u e l - a i r mixtures ; and dotted l i n e s with symbols represent
experimental data from Matsui and Lee ( 3 3 ) .
"
10"
DO
Deto- /
nation /
c
03
c
10"
DOO#
No detonation
10
C H Air
2
Bull et al (1979)
Detonation
No detonation
I
1
10"
Equivalence ratio
Figure 6 .
Cube o f computed i n d u c t i o n l e n g t h i n ethane-air mixtures,
with data from B u l l et a l . ( U 3 ) .

188
Using
t h e present
model,
t h e k i n e t i c response o f
h y d r o c a r b o n - a i r m i x t u r e s t o t h e a d d i t i o n o f v a r y i n g amounts o f
halogenated s p e c i e s h a s been examined (13).
These i n h i b i t o r s
i n c l u d e t h e h a l o g e n a c i d s HC1, HBr a n d H I , a s w e l l a s m e t h y l ,
v i n y l , a n d e t h y l c h l o r i d e s , b r o m i d e s , a n d i o d i d e s . T h e common
f l a m e r e t a r d a n t CF3Br was a l s o u s e d . A s a n example o f t h e s e
r e s u l t s , computed v a l u e s o f t h e i n d u c t i o n l e n g t h a r e shown
i n F i g u r e 7 f o r C2H4-air.
From t h i s f i g u r e i t i s c l e a r
that, r e l a t i v e t o the case without i n h i b i t o r s , a l l o f the a d d i
t i v e s increased the i n d u c t i o n length. This i n c r e a s e i s s m a l l e s t
when C I atoms a r e a d d e d , r e g a r d l e s s o f w h e t h e r t h e a d d i t i v e i s
HC1,
CH3CI, C2H3CI, o r C2H5CI, a n d o n l y
the results
w i t h 1% HC1 a r e shown i n F i g u r e 7. T h e i o d i d e s were most e f
f e c t i v e a s i n h i b i t o r s , a n d t h e b r o m i d e s were n e a r l y a s e f f e c t i v e
as t h e i o d i d e s . T h e compound CF3Br was s l i g h t l y more e f f e c
t i v e a s a n i n h i b i t o r t h a n CH3Br, s i n c e t h e F atoms remove
a d d i t i o n a l H atoms from t h e r e a c t i n g m i x t u r e s , p r o d u c i n g t h e
r e l a t i v e l y i n e r t s p e c i e s HF. A l l o f t h e i n h i b i t o r s a c t a s
c a t a l y s t s f o r t h e r e c o m b i n a t i o n o f H atoms, l o w e r i n g t h e s i z e o f
the r a d i c a l pool and reducing t h e r a t e o f chain branching by
means o f t h e r e a c t i o n
H + 0
= 0 + OH
The r i c h l i m i t f o r d e t o n a t i o n i n a 7 0 mm t u b e , m e a s u r e d b y
B o r i s o v a n d Loban ( 2 7 ) , i s <)>R = 2.5. A t t h i s p o i n t =
1.04 1 C T m. B a s e d o n t h e e a r l i e r d i s c u s s i o n , t h e same
v a l u e o f w i l l c o r r e s p o n d t o t h e r i c h l i m i t i n t h e same t u b e
f o r o t h e r m i x t u r e s a s w e l l . A s i n h i b i t o r s a r e added t o t h e
r e a c t i v e f u e l - a i r mixture, t h e value o f equivalence r a t i o c o r
r e s p o n d i n g t o = 1.04 m i s g r a d u a l l y r e d u c e d . F o r
1% HI t h i s g i v e s a r i c h l i m i t o f 4>R - 2.0, s h o w i n g a s u b
s t a n t i a l narrowing o f the detonation l i m i t s . Because the curves
i n F i g u r e 7 a r e v e r y s t e e p o n t h e f u e l - l e a n s i d e , most o f t h e
reduction i n detonation l i m i t s occurs a t t h e r i c h l i m i t rather
than a t t h e l e a n l i m i t . The i n c r e a s e i n i n d u c t i o n l e n g t h with
i n h i b i t o r s a l s o r e s u l t s i n an increase i n t h e c r i t i c a l energy
f o r i n i t i a t i o n o f d e t o n a t i o n , w h i c h c a n b e s e e n e a s i l y from
E q u a t i o n 5.
2
- 2
Conclusion
D e t o n a t i o n s a r e e x t r e m e l y complex phenomena a n d i n v o l v e many
competing p h y s i c a l and chemical processes. Complete t h e o r e t i c a l
models o f the i n i t i a t i o n , s t a b i l i t y , and s t r u c t u r e o f d e t o n a t i o n
waves r e q u i r e a n a c c u r a t e d e s c r i p t i o n o f t h e c h e m i c a l k i n e t i c s
o f t h e i n d u c t i o n p h a s e . T h e p r i m a r y g o a l o f t h e p r e s e n t work i s
t o d e m o n s t r a t e t h a t k i n e t i c mechanisms a r e now a v a i l a b l e w h i c h
are able t o p r e d i c t the i n d u c t i o n delay period f o r a v a r i e t y o f
practical fuels.

Figure 7
Computed i n d u c t i o n lengths f o r e t h y l e n e - a i r mixtures
showing the e f f e c t s o f a d d i t i o n of s e l e c t e d i n h i b i t o r s .
Also
shown i s the p r e d i c t e d r i c h l i m i t f o r the propagation o f detonation
i n a l i n e a r tube, based on the data without i n h i b i t o r s present o f
Borisov and Loban ( 2 7 ) .

190
I t was o b s e r v e d t h a t computed i n d u c t i o n d e l a y t i m e s a n d
induction lengths c o r r e l a t e well with observed experimental det
o n a t i o n phenomena, i n d e p e n d e n t o f f u e l t y p e , o x i d i z e r t y p e ,
nitrogen d i l u t i o n , i n i t i a l pressure, i n i t i a l temperature, and
equivalence ratio.
T h i s g e n e r a l agreement emphasizes t h e
central role that chemical k i n e t i c s plays i n t h e detonation
p r o c e s s , d e t e r m i n i n g t h e c h a r a c t e r i s t i c l e n g t h and time s c a l e s .
Eventually, complete coupled multidimensional f l u i d mechanics
and k i n e t i c s m o d e l s w i l l a p p e a r , b u t t h e p r e s e n t s i m p l i f i e d
approach s t i l l provides a great deal o f u s e f u l information.
Acknowledgments
Many v a l u a b l e d i s c u s s i o n s w i t h D r . P. A. U r t i e w , P r o f e s s o r F . L .
D r y e r , a n d P r o f e s s o r J . H. L e e a r e g r a t e f u l l y a c k n o w l e d g e d .
T h i s work was p e r f o r m e d u n d e r t h e a u s p i c e s o f t h e U. S. D e p a r t
ment o f E n e r g y b y t h e L a w r e n c e L i v e r m o r e N a t i o n a l L a b o r a t o r y
u n d e r c o n t r a c t No. W-7405-ENG-48.
J.
Literature Cited
1. Westbrook, C. ., and Dryer, F. L., Eighteenth Symposium
(International) on Combustion, p. 749, The Combustion
Institute, 1981.
2. Westbrook, C. ., and Dryer, F. L., "Chemical Kinetics
Modeling of Hydrocarbon Combustion", Prog. Energy and Comb.
Sci., to appear, 1983.
3. Westbrook, C. K., Creighton, J., Lund, C., and Dryer, F. L.,
Phys. Chem. 81, 2542 (1977).
4. Westbrook, C. ., Comb. Sci. Tech. 20, 5 (1979).
5. Westbrook, C. K., and Dryer, F. L., Comb. Sci. Tech. 20, 125
(1979).
6. Westbrook, C. K., Dryer, F. L., and Schug, K. P., Nineteenth
Symposium (International) on Combustion, p. 153, The
Combustion Institute, Pittsburgh, 1983.
7. Westbrook, C. K., and Pitz, W. J., "A Comprehensive Chemical
Kinetic Reaction Mechanism for the Oxidation and Pyrolysis
of Propane and Propene, submitted for publication, 1983.
8. JANAF Thermochemical Tables, U. S. National Bureau of
Standards NSRDS-NBS 37 and Supplements. D. R. Stull and H.
Prophet, eds., 1971.
9. Westbrook, C. K., and Haselman, L. C., Prog, i n Astr. and
Aero. 75, 193 (1981).
10. Jachimowski, C. J., Comb. Flame 29, 55 (1977).
11. Burcat, ., Lifshitz, ., Scheller, K., and Skinner, G. .,
Thirteenth Symposium (International) on Combustion, p. 745,
The Combustion Institute, Pittsburgh, 1971.
12. Westbrook, C. K., Comb. Sci. and Tech. 23, 191 (1980).
13. Westbrook, C. K., Nineteenth Symposium (International) on
Combustion, p. 127, The Combustion Institute, Pittsburgh,
1983.
10.
14.
15.
16.
E.,
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
WESTBROOK
Detonations
191
Westbrook, C. ., "Numerical Modeling of Flame Inhibition by

CF Br", Comb. Sci. and Technol., in press (1983).
Westbrook, C. ., Comb. Sci. and Tech. 29, 65 (1982).
Bull, D. C., Elsworth, J . E., Schuff, P. J., and Metcalfe,
Comb. Flame 45, 7 (1982).
Strehlow R. A. and Engel, D. C., AIAA J. 7, 492 (1969).
Strehlow, R. A. and Rubins,P.M.,AIAAJ.7, 1335 (1969).
Manzhalei, V. I., Mitrofanov, V. V., and Subbotin, V. .,
Fiz. Goren. Vzr., 10, 102 (1974).
Vassiliev, . ., Fiz. Goren. Vzr. 18, 132 (1982).
Westbrook, C. K., Comb. Flame 46, 191 (1982).
Westbrook, C. ., and Urtiew, P.., Fiz. Goren. Vzr., in
press, 1983.
Westbrook, C. K., Pitz, W. J., and Urtiew, P. ., "Chemical
Kinetics of Propane Oxidation in Gaseous Detonations",
submitted for publication, 1983.
Westbrook, C. K., and Urtiew, P. ., Nineteenth Symposium
(International) on Combustion, p. 615, The Combustion
Institute, Pittsburgh, 1983.
Pawell, D., Vasatko, M., and Wagner, H. Gg., "The Influence
of Initial Temperature on the Limits of Detonability", AFOSR
69-1095TR AD-692900, 1967.
Kogarko, S. M., Soviet Physics-Tech. Phys. 3 (28), 1904
(1958).
Borisov, . ., and Loban, S. ., Fiz. Goren. Vzr. 13, 729
(1977).
Lewis, B. and von Elbe, G., Combustion, Flames and
Explosions of Gases, Academic Press, New York, 1961.
Michels, H. J., Munday, G., and Ubbelohde, A. R., Proc. Roy.
Soc. London A 319, 461 (1970).
Mitrofanov, V. V., and Soloukhin, R. I., Sov. Phys. Dokl. 9,
1055 (1964).
Edwards, D. H., Thomas, G. O., and Nettleton, . ., J.
Fluid Mech. 95, 79 (1979).
Lee, J. H., Knystautas, R., and Guirao, C. M., Proceedings
of the International Specialist Meeting on Fuel-Air
Explosion, Montreal, Canada, p. 157, University of Waterloo
Press, 1982.
Matsui, H., and Lee, J. H., Seventeenth Symposium (Inter
national) on Combustion, p. 1269, The Combustion Institute,
Pittsburgh, 1979.
Moen, I. O., Donato, M., Knystautas, R., and Lee, J. H.,
Eighteenth Symposium (International) on Combustion,p.1615,
The Combustion Institute, Pittsburgh, 1981.
Zeldovich, Ya. B., Kogarko, S. M., and Semenov,.N.,Sov,
Phys. Tech. Phys. 1, 1689 (1956).
Vassiliev, . ., and Grigoriev, V. V., Fiz. Goren. Vzr. 16,
177 (1980).
Vassiliev, . ., Fiz. Goren. Vzyrva 18, 98 (1982).
Knystautas, R., Lee,J.H.,and Guirao, C. M., Comb. Flame
48, 63 (1982).
3

192
39.
40.
41.
42.
43.
44.
45.
Atkinson, R., Bull, D. C., and Shuff, P. J., Comb. Flame 39,
287 (1980).
Bull, D. C., Trans. I. Chem. Eng. 57, 219 (1979).
Bull, D. C., Elsworth, J. E., and Hooper, G., Acta Astr. 5,
997 (1978).
Bull, D. C., Elsworth, J. E., and Hooper, G., Comb. Flame
34, 327 (1979).
Bull, D. C., Elsworth, J. E., and Hooper, G., Comb. Flame
35, 27 (1979).
Carlson, G. ., Comb. Flame 21, 383 (1973).
Nicholls, J. ., Sichel, M., Gabrijel, Z., Oza, R. D. and
Vander Molen, R., Seventeenth Symposium (International) on
Combustion, p. 1223, The Combustion Institute, Pittsburgh,
1979.
46. Vander Molen, R., and Nicholls, J. ., Comb. Sci. Tech. 21,
75 (1979).
47. Lee, J. H. and Matsui, H., Comb. Flame 28, 61 (1977).
48. Urtiew, P. ., and Tarver, C. M., Prog. Astr. Aero. 75, 370
(1981).
49. Vassiliev, . ., Nikolaev, Yu. ., and Ulianitski, V. Yu.,
Fiz. Goren. Vzyrva 15, 94 (1979).
50. Burcat, ., Comb. Flame 28, 319 (1977).
51. Slack, M. W., and Grillo, A. R., Comb. Flame 40, 155 (1981).
52. Dorko, . ., Bass, D. M., Crossley, R. W., and Scheller,
K.,
Comb. Flame 24, 173 (1975).
53. Dabora, . ., Comb. Flame 24, 181 (1975).
54. Crossley, R. W., Dorko, . ., Scheller, K., and Skinner, G.
B.,
Comb. Flame 19, 373 (1972).
55. Eubank, C. S., Rabinowitz, M. J., Gardiner, W. C., Jr., and
Zellner, R. E., Eighteenth Symposium (International) on Com
bustion, p. 1767, The Combustion Institute, Pittsburgh, 1981.
56. Skinner, G. B., and Ringrose, G. H., J. Chem. Phys. 43, 4129
(1965).
57. Skinner, G. B., Halogenated Fire Suppressants, ACS Symposium
Series 16, R. G. Gann (ed.). American Chemical Society, 295
(1975).
RECEIVED October 28, 1983

11
Review of Plasma Jet Ignition
R.M.CLEMENTS
Department of Physics, University of Victoria, Victoria,B.C.,V8W 2Y2, Canada
During the last decade or so there has been consider

able interest in lean-burn, spark ignited, internal
combustion engines. Motivating reasons behind this
are the reduction of pollutants and increased fuel
economy. However such lean mixtures are difficult
to ignite and have longer burn times by comparison
to stoichiometric mixtures. One way of alleviating
these problems is with plasma jet ignition. The
mechanical construction of typical igniters as well
as associated electrical circuitry required to power
igniters are discussed. The igniter produces a puff
of gas which is the ignition kernel. How this puff
behaves is examined when it is either in the
presence or absence of a combustible mixture. This
is done in the light of the relative roles of fluid
mechanical turbulence and chemical effects. Finally,
the practical aspects of using these igniters in
internal combustion engines as well as associated
problems are discussed.
Lean burn, spark i g n i t e d , i n t e r n a l combustion ( i c ) engines
e s p e c i a l l y a s used i n motor v e h i c l e s have r e c e i v e d c o n s i d e r a b l e
a t t e n t i o n d u r i n g t h e p a s t f e w y e a r s . The r e a s o n s f o r t h i s a r e
w e l l known: by c o m p a r i s o n w i t h s t o i c h i o m e t r i c o r r i c h m i x t u r e s ,
l e a n m i x t u r e s p r o d u c e a l o w e r p o l l u t a n t l e v e l and i m p r o v e d f u e l
economy. T h e r e a r e p r o b l e m s a s s o c i a t e d w i t h l e a n b u r n ,
s p e c i f i c a l l y t h e m i x t u r e i s s l o w b u r n i n g and h a r d t o i g n i t e .
T h e r e a r e numerous p r o p o s a l s f o r t h e a l l e v i a t i o n o f t h e s e
problems, i n c l u d i n g charge s t r a t i f i c a t i o n , h i g h l e v e l s o f
t u r b u l e n c e o r s w i r l i n d u c e d by s p e c i a l v a l v e o r p i s t o n d e s i g n , a s
w e l l as improved e l e c t r i c a l i g n i t i o n systems.
These a r e r e v i e w e d
by D a l e and Oppenheim ( 1 ) One s u c h f o r m o f enhanced i g n i t i o n
s y s t e m i s p l a s m a j e t i g n i t i o n ( P J I ) and t h i s i s t h e s u b j e c t o f
t h e p r e s e n t r e v i e w . B e c a u s e a c o m p a n i o n p a p e r i n t h i s symposium
0097-6156/84/0249-0193506.00/0
194
s e r i e s ( S l o a n e and R a t c l i f f e ( 2 ) ) c o n c e n t r a t e s on the c h e m i s t r y o f
i g n i t i o n the p r e s e n t paper w i l l emphasize the r o l e of f l u i d
m e c h a n i c s w i t h t h e c h e m i c a l r o l e somewhat s u b o r d i n a t e d .
Finally
b e c a u s e o f t h e l a r g e number o f r e s e a r c h p a p e r s i n t h e a r e a o f P J I
t h e p r e s e n t r e v i e w w i l l be aimed t o w a r d g e n e r a l c o n c e p t s and no
a t t e m p t w i l l be made t o r e v i e w e v e r y p a p e r p u b l i s h e d i n t h i s
field.
B a s i c P J I System
F i g u r e 1 shows t h e s i m p l e s t t y p e o f p l a s m a j e t i g n i t e r o f t h e
d e s i g n u s e d by Topham e t a l ( 3 ) and A s i k e t a l ( 4 ) . W h i l e t h e r e
i s a wide v a r i a t i o n i n the d i f f e r e n t d e s i g n s , the d e s i g n i n d i c a t e d
in Figure 1 i s t y p i c a l .
However t h e r e a r e two i n t e r e s t i n g d e s i g n
variations.
The f i r s t e n t a i l s p l a c i n g a n o z z l e a t t h e j e t o r i f i c e
( s e e f o r example Oppenheim e t a l ( 5 ) ) . The s e c o n d i s t h e
i n c o r p o r a t i o n o f a gas i n l e t i n t o t h e s m a l l b l i n d chamber o f t h e
i g n i t e r , as p r o p o s e d by W e i n b e r g e t a l ( 6 ) . The l a t t e r means t h a t
t h e chamber o f t h e p l a s m a i g n i t e r need n o t c o n t a i n t h e same gas
m i x t u r e as t h a t o u t s i d e t h e p l a s m a j e t c a v i t y .
A l t h o u g h somewhat d i f f e r e n t i n d e s i g n d e t a i l s , a l l o f t h e s e
i g n i t e r s work i n t h e same manner. An a r c s t r i k e s between t h e
c e n t e r e l e c t r o d e and t h e end p l a t e .
T h i s a r c h e a t s t h e gas i n t h e
c a v i t y and t h e o v e r p r e s s u r e e x p e l l s a t h i n j e t o f h i g h l y l u m i n o u s
p l a s m a . I t s h o u l d be n o t e d t h a t t h e r e i s e s s e n t i a l l y no
i n t e r a c t i o n between t h e c u r r e n t i n t h e a r c and i t s own s e l f produced magnetic f i e l d .
T h i s was n o t t h e s i t u a t i o n i n t h e
i g n i t e r s i n v e s t i g a t e d by B r a d l e y and C r i t c h l e y (_7) o r H a r r i s o n and
Weinberg
(8).
A l t h o u g h t h e c i r c u i t s t o power t h e i g n i t e r u s e d by t h e
different investigators
3-5) d i f f e r i n d e t a i l t h e y a r e
basically similar.
The c i r c u i t c o n s i s t s e s s e n t i a l l y o f two
s t a g e s . The f i r s t s t a g e p r o d u c e s a h i g h v o l t a g e (10s o f kV) l o w
e n e r g y (100 mJ t y p i c a l l y ) p u l s e w h i c h c a u s e s t h e i n i t i a l breakdown
o f t h e gap i n t h e p l a s m a i g n i t e r .
A l o w v o l t a g e ( s a y < 1 kV)
m a i n t a i n s the e l e c t r i c a l d i s c h a r g e d i s s i p a t i n g e n e r g i e s i n the
o r d e r o f a few j o u l e s w i t h maximum c u r r e n t s b e t w e e n 100A and
1000A. T y p i c a l l y the t i m e t o c u r r e n t maximum i s i n t h e o r d e r o f a
few 10s o f .
S t r e a k p h o t o g r a p h s (_3, _5) have shown t h a t t h e
l u m i n o u s p l a s m a j e t i s a few c e n t i m e t e r s l o n g and a f t e r c u r r e n t
maximum t h e j e t q u i c k l y becomes n o n - l u m i n o u s . The v e l o c i t y o f t h e
f r o n t o f t h i s l u m i n o u s j e t r a n g e s f r o m a b o u t h a l f t h e speed o f
sound t o s l i g h t l y o v e r t h e s p e e d o f sound f o r t h e s e c o n d i t i o n s .
These s t r e a k s o f t e n a l s o show c o n s i d e r a b l e s t r u c t u r e b e h i n d t h e
luminous f r o n t .
Some o f t h i s s t r u c t u r e c a n be i n t e r p r e t e d as
gaseous m a t e r i a l e j e c t e d from the i g n i t e r a t v e l o c i t i e s
c o n s i d e r a b l y h i g h e r than t h a t of the luminous f r o n t .

II.
CLEMENTS
195
Figure 1.
A cross s e c t i o n o f a t y p i c a l simple plasma j e t i g n i t e r .
(Reproduced w i t h permission from Ref. 3 . Copyright 1 9 7 5 , The
Combustion I n s t i t u t e . )

196
The

Gaseous P u f f P r o d u c e d by P J I and
Ignition
For t y p i c a l combustion r e a c t i o n s i n d u c t i o n times are i n the

o r d e r o f m i l l i s e c o n d s . However f o r many o f t h e e x p e r i m e n t s
d i s c u s s e d a b o v e , t h e l u m i n o u s j e t p r o d u c e d by t h e i g n i t e r d i e s
away i n t i m e s an o r d e r of m a g n i t u d e s h o r t e r t h a n t h i s q u a n t i t y .
I n order to i n v e s t i g a t e t h i s , time r e s o l v e d S c h l i e r e n photography
i s e m p l o y e d . T h i s was f i r s t done by Oppenheim e t a l (5) and
s u b s e q u e n t l y by o t h e r w o r k e r s .
F i g u r e 2 (A) shows p h o t o g r a p h s o f
the t e l e v i s i o n s c r e e n of a time r e s o l v e d S c h l i e r e n system f o r a
plasma j e t i g n i t e r i n t o a i r at four atmospheres p r e s s u r e .
The
p u f f o f w a r m i s h gas w h i c h e x i s t s l o n g a f t e r a l l p l a s m a j e t
l u m i n e s c e n c e has d i s a p p e a r e d
i s n o t e w o r t h y and a p p e a r s v e r y much
l i k e an a t m o s p h e r i c t h e r m a l o r a t u r b u l e n t p u f f as d e s c r i b e d by
R i c h a r d s ( 9 ) . I n f a c t i t i s m a t h e m a t i c a l l y s i m i l a r to the
t u r b u l e n t p u f f d e s c r i b e d by R i c h a r d s and t h e r e l a t i o n s h i p s w h i c h
he d e r i v e s f o r h i s l a r g e s c a l e t u r b u l e n t p u f f s a p p l y t o t h e p u f f
g e n e r a t e d by t h e p l a s m a j e t . Thus e v e n t h o u g h t h e t i m e and l e n g t h
s c a l e b e t w e e n t h e two t y p e s o f p u f f s may d i f f e r up t o o r d e r s o f
m a g n i t u d e t h e same m a t h e m a t i c a l a n a l y s i s d e s c r i b e s b o t h ( 1 0 ) .
C l e a r l y , as d i s c u s s e d i n some d e t a i l by O r r i n e t a l ( 1 1 ) ,
f l u i d m e c h a n i c a l e f f e c t s a r e not t h e w h o l e s t o r y when one i s u s i n g
t h e p l a s m a j e t as a s o u r c e o f i g n i t i o n .
F i g u r e 2 ( B ) show a s e r i e s
o f p h o t o g r a p h s o f i g n i t i o n by a p l a s m a j e t and f o r c o m p a r i s o n
( F i g u r e 2 ( C ) ) by a c o n v e n t i o n a l s p a r k i n a c o m b u s t i o n bomb
c o n t a i n i n g a methane-air m i x t u r e at f o u r atmospheres p r e s s u r e .
F o r t h e s e p i c t u r e s t h e n o r m a l i z e d a i r - f u e l r a t i o = 1.3 and f o r
a l l c a s e s the c o m b u s t i o n chamber d i m e n s i o n s a r e 3 cm x 4 cm x
9 cm.
The s t r i k i n g s i m i l a r i t y o f t h e p l a s m a j e t w i t h and w i t h o u t
combustion i s v e r y e v i d e n t from the photographs. T h i s would tend
to imply that at l e a s t f o r t h i s mixture s t r e n g t h turbulence i s
g o v e r n i n g t h e c o m b u s t i o n p r o c e s s , o r a t l e a s t the e a r l y s t a g e s
t h e r e o f . A l s o the d r a m a t i c d i f f e r e n c e between a c o n v e n t i o n a l
s p a r k i g n i t i o n and t h e p l a s m a j e t i g n i t i o n i s c l e a r l y shown and i t
i s e v i d e n t t h a t the combustion f o r spark i g n i t i o n i s c o n s i d e r a b l y
slower than t h a t f o r the plasma j e t . T h i s i s a g a i n c o n s i s t e n t
w i t h t h e h i g h l e v e l s o f t u r b u l e n c e g e n e r a t e d by t h e p l a s m a j e t and
t h e i r a f f e c t on the c o m b u s t i o n p r o c e s s .
B e c a u s e t h e S c h l i e r e n p h o t o g r a p h s shown i n F i g u r e 2 ( B ) and
(C) a r e a t b e s t q u a s i - q u a n t i t a t i v e t h e more q u a n t i t a t i v e
measurement o f p r e s s u r e i n s i d e t h e c o m b u s t i o n chamber v e r s u s t i m e
has b e e n made.
F i g u r e 3 shows s u c h a g r a p h f o r t h e same
c o n d i t i o n s as shown i n F i g u r e 2 ( B ) and ( C ) . The d i f f e r e n c e
between c o n v e n t i o n a l s p a r k i g n i t i o n and P J I a r e v e r y e v i d e n t .
To
f a c i l i t a t e c o m p a r i s o n s b e t w e e n t h e two s y s t e m s f o r d i f f e r e n t
v a l u e s of a i r - f u e l r a t i o the f o l l o w i n g parameters are d e f i n e d .
D e l a y t i m e i s t a k e n as t h e t i m e f r o m t h e s t a r t o f t h e e l e c t r i c a l
p u l s e t o t h e i g n i t e r t o t h e t i m e when the p r e s s u r e r e a c h e s 10% o f
i t s maximum v a l u e and b u r n r a t e i s t a k e n as t h e mean s l o p e between
10% maximum p r e s s u r e and 90% maximum p r e s s u r e .
Figure 4 gives


F i g u r e 2.
T i m e - r e s o l v e d S c h l i e r e n p h o t o g r a p h s o f a c o n s t a n t volume c o m b u s t i o n
chamber a t k atm. p r e s s u r e .
The v e r t i c a l d i m e n s i o n o f e a c h frame i s 0.3 cm.
A, p l a s m a j e t i g n i t e r i n t o a i r ; B, p l a s m a j e t i g n i t i o n o f a m e t h a n e - a i r m i x
t u r e w i t h = 1.3; and C, c o n v e n t i o n a l s p a r k i g n i t i o n o f a m e t h a n e - a i r m i x
t u r e w i t h = 1.3.
Numbers a r e t i m e i n ms.
198
20
CONVENTIONAL SPARK
90%
<
Q_ 10
DELAY
TIME
PLASMA JET
Ii
50
100
150
200
250
t(ms)
Figure 3. A pressure (p) time ( t ) h i s t o r y o f combustion i n a
constant volume chamber f o r a methane-air mixture w i t h = 1.3.
(Reproduced with permission from Ref. 20. Copyright 1983, Com
b u s t i o n Science and Technology.)
CONVENTIONAL SPARK
10
PLASMA
07
0.8
0.9
1.0
JET
1.1
1.2
1.3
Figure k. Induction delay v s . f o r a methane-air mixture i n a

constant volume chamber.
(Reproduced w i t h permission from Ref.
20. Copyright 1983, Combustion Science and Technology.)
11.
CLEMENTS
199
d e l a y t i m e v e r s u s w h i l e F i g u r e 5 g i v e s t h e b u r n r a t e v e r s u s .
The d i f f e r e n c e b e t w e e n t h e c o n v e n t i o n a l s p a r k and P J I a r e v e r y
evident.
A l l the preceding data a r e not f o r u l t r a lean mixtures ( i . e .
m i x t u r e s n e a r o r beyond t h e n o r m a l l e a n l i m i t o f f l a m a b i l i t y ) .
A l s o t h e gas i n s i d e t h e chamber o f t h e p l a s m a j e t i g n i t e r i s t h e
same a s t h e m i x t u r e i n t h e m a i n c o m b u s t i o n chamber. T h i s d a t a i s
c o m p a t i b l e w i t h t h e premise t h a t t h e plasma j e t causes a h i g h
d e g r e e o f t u r b u l e n c e w h i c h i n c r e a s e s t h e f l a m e f r o n t a r e a and t h i s
a c c o u n t s f o r t h e r e d u c t i o n i n d e l a y t i m e and i n c r e a s e i n b u r n
rate.
I n an i n i t i a l b r i e f r e p o r t by W e i n b e r g e t a l ( 6 ) and i t s
s u b s e q u e n t e x p a n s i o n by O r r i n e t a l ( 1 1 ) t h e e f f e c t o f d i f f e r e n t
g a s e s and l i q u i d s i n t h e p l a s m a j e t c a v i t y was i n v e s t i g a t e d .
They
w o r k e d a t b o t h c o n s t a n t volume ( 6 ) and c o n s t a n t p r e s s u r e ( 1 1 ) . An
i g n i t e r o f t h e b a s i c d e s i g n w h i c h i s a t t r i b u t e d t o them i n t h e
p r e c e d i n g s e c t i o n was u s e d t o i g n i t e l e a n ( i n t h e o r d e r o f 2 )
m e t h a n e - a i r m i x t u r e s . The i g n i t e r c a v i t y was f i l l e d w i t h d i f f e r
e n t g a s e s ( f o r example h y d r o g e n , methane, a r g o n , e t c . ) and d i f f e r
e n t l i q u i d s ( f o r example a l c o h o l s , a l d e h y d e s , b e n z e n e , w a t e r e t c ) .
The s i z e o f t h e c o m b u s t i n g r e g i o n was measured u s i n g S c h l i e r e n
t e c h n i q u e s and t h e c o n c e n t r a t i o n o f numerous i n t e r e s t i n g s p e c i e s ,
f o r example H, OH, 0, e t c . were a l s o m e a s u r e d . I t i s c l e a r t h a t
t h e h i g h e n e r g i e s d e v e l o p e d i n a p l a s m a j e t w i l l g e n e r a t e numerous
r a d i c a l s which a r e o f i n t e r e s t i n t h e i g n i t i o n o f t h e combustion
reaction.
T h e i r g o a l was t o f i n d o u t w h i c h were most i m p o r t a n t
and a l s o t o s e p a r a t e t h e f l u i d m e c h a n i c a l e f f e c t s w h i c h have b e e n
d i s c u s s e d p r e v i o u s l y i n t h e present paper, from c h e m i c a l e f f e c t s .
B r i e f l y s t a t e d , t h e c o n c l u s i o n s were t h a t f o r t h e s e v e r y l e a n
m i x t u r e s a t o m i c h y d r o g e n i s o f u t m o s t i m p o r t a n c e and t h a t r o u g h l y
s p e a k i n g ( a t l e a s t up t o a g i v e n minimum h y d r o g e n c o n c e n t r a t i o n i n
t h e s p e c i e s c o n t a i n e d i n t h e p l a s m a j e t c a v i t y ) t h e more h y d r o g e n
the s p e c i e s c o n t a i n e d t h e b e t t e r t h e i g n i t i o n p r o p e r t i e s were.
F o r t h e s e v e r y l e a n m i x t u r e s t h e y f o u n d t h a t a r g o n was 'an e x c e p
t i o n a l l y poor i g n i t i o n s o u r c e .
Inasmuch a s Zhang e t a l ( 1 2 )
f o u n d t h a t f o r m i x t u r e s n e a r s t o i c h i o m e t r i c a r g o n was a v e r y good
s o u r c e o f i g n i t i o n , one c a n s u r m i s e , b a s e d on a l l t h e d a t a
presented here, t h a t f o r m i x t u r e s near s t o i c h i o m e t r i c f l u i d
m e c h a n i c a l e f f e c t s d o m i n a t e and c h e m i c a l e f f e c t s a r e s u b o r d i n a t e d
p r o b a b l y b e c a u s e t h e r e a r e t h e needed c o n c e n t r a t i o n o f r a d i c a l s
p r e s e n t no m a t t e r what one u s e s a s a g a s i n t h e p l a s m a j e t c a v i t y .
However f o r e x t r e m e l y l e a n ( 6 , 11) m i x t u r e s t h e c h e m i c a l e f f e c t s
p r e d o m i n a t e and i n f a c t a h i g h d e g r e e o f t u r b u l e n c e may w e l l be
counterproductive to effective i g n i t i o n .
As a f i n a l comment: i t
i s n o t i n c o n c e i v a b l e t h a t o t h e r r a d i c a l s p e c i e s , as y e t n o t
i n v e s t i g a t e d , c o u l d p l a y a major r o l e i n t h e i g n i t i o n p r o c e s s .
1
P J I i n Engines
T h e r e have been a number o f i n v e s t i g a t i o n s
(4^, 13-16) on t h e

200
e f f e c t s o f P J I on t h e p e r f o r m a n c e o f t h e i n t e r n a l c o m b u s t i o n
e n g i n e . The i n v e s t i g a t i o n s have c o n s i d e r e d n o t o n l y t h e u s u a l
l i q u i d f u e l g a s o l i n e , but a l s o t h e gaseous f u e l s methane and
propane.
Most o f t h e i n v e s t i g a t i o n s , b u t n o t a l l 0 4 ) , have been
done on s i n g l e c y l i n d e r l a b o r a t o r y t e s t e n g i n e s t h e most p o p u l a r
b e i n g a CFR e n g i n e . R e s u l t s f r o m t h e s e i n v e s t i g a t i o n s a r e
e s s e n t i a l l y m u t u a l l y c o n s i s t e n t and t h u s r a t h e r t h a n d i s c u s s e a c h
of t h e e x p e r i m e n t s i n d i v i d u a l l y a t y p i c a l one w i l l be d i s c u s s e d i n
a little detail.
A l s o o f t h e f u e l s d i s c u s s e d methane i s t h e
s i m p l e s t and shows t h e s t r o n g e s t e f f e c t s when u s i n g P J I . H e n c e ,
f o r s i m p l i c i t y t h e e x p e r i m e n t by P i t t and C l e m e n t s ( 1 5 ) w i l l be
discussed.
The e n g i n e u s e d i n t h i s e x p e r i m e n t ( 1 5 ) was a s i n g l e c y l i n d e r
L-head t e s t e n g i n e c o n n e c t e d t o an e l e c t r i c dynamometer.
The
s t a n d a r d c o m p a r i s o n i g n i t i o n s y s t e m was a c a p a c i t i v e d i s c h a r g e
s y s t e m ( C D I ) s t o r i n g a b o u t 30 raJ and t h e P J I s y s t e m s t o r i n g 1.2 J .
A l o w c o m p r e s s i o n r a t i o o f 4:1 was u s e d i n o r d e r t o a v o i d any
p r o b l e m s o f e l e c t r i c a l m i s f i r e w i t h t h e p l a s m a j e t . The e n g i n e
d i s p l a c e m e n t was a b o u t 500 cm and a l l t e s t s were t a k e n a t 2000
rpm and a c o n s t a n t methane f l o w o f 0.43 1/s.
The e n g i n e c y l i n d e r
p r e s s u r e h i s t o r i e s were measured by a p i e z o - e l e c t r i c p r e s s u r e
t r a n s d u c e r . A summary o f t h e r e s u l t s i s as f o l l o w s .
Typically
the CDI s y s t e m r e q u i r e d 20 more t i m i n g advance t h a n d i d t h e P J I
s y s t e m f o r o p t i m a l p e r f o r m a n c e o f b o t h s y s t e m s . However when
c o n d i t i o n s were n o t o p t i m i z e d t h e P J I s y s t e m showed c o n s i d e r a b l y
l e s s c y c l e - t o - c y c l e v a r i a t i o n of the p r e s s u r e h i s t o r y .
Also PJI
e x t e n d e d t h e l e a n m i s f i r e l i m i t f r o m = 1.2 t o s l i g h t l y beyond
=1.3.
For t h e c o n d i t i o n s d i s c u s s e d i n t h e p r e c e d i n g p a r a g r a p h , even
f o r o p t i m a l c o n d i t i o n s , t h e r e was some c y c l e - t o - c y c l e v a r i a t i o n i n
the p r e s s u r e h i s t o r y .
Thus t o o b t a i n m e a n i n g f u l r e s u l t s t h e
a v e r a g e o f a l a r g e number ( s a y 100 o r more) o f p r e s s u r e t r a c e s
must be t a k e n . A g r e a t d e a l o f t h i s v a r i a t i o n i s b e c a u s e t h e a i r f u e l r a t i o v a r i e s from c y c l e to c y c l e .
T h i s r e s u l t s from the f a c t
t h a t t h e b u r n and s c a v e n g i n g a c t i o n o f t h e p r e v i o u s c y c l e a f f e c t s
the a i r - f u e l r a t i o f o r t h e c y c l e i n q u e s t i o n .
In order to
a l l e v i a t e t h i s p r o b l e m t h e e n g i n e was m o t o r e d a t t h e d e s i r e d speed
(2000 rpm) and t h e a i r - f u e l r a t i o s t a b i l i z e d a t t h e d e s i r e d v a l u e .
The i g n i t i o n was f i r e d o n l y once and t h e c y l i n d e r p r e s s u r e h i s t o r y
r e c o r d e d . F i g u r e 6 i s o b t a i n e d from the average of t e n such
" s h o t s " and as u s u a l g i v e s l o g pV^ a s a f u n c t i o n o f c r a n k a n g l e .
H e r e i s c y l i n d e r p r e s s u r e , V i s c y l i n d e r volume and i s t h e
r a t i o o f s p e c i f i c h e a t s . One s e e s f r o m t h i s f i g u r e t h a t t h e r e i s
e s s e n t i a l l y no d i f f e r e n c e b e t w e e n t h e two c u r v e s e x c e p t t h a t an
a d d i t i o n a l 20 o f advance i s r e q u i r e d f o r t h e CDI s y s t e m . I n t h i s
f i g u r e o p t i m a l t i m i n g i s c h o s e n f o r b o t h i g n i t i o n s y s t e m s and t h e
mixture i s stoichiometric.
However, f o r l e a n m i x t u r e s ( s a y >
1.2) t h e r e i s a d i f f e r e n c e b e t w e e n t h e s t a n d a r d i g n i t i o n s y s t e m
and t h e P J I s y s t e m d u r i n g t h e c o m b u s t i o n p h a s e ; t h e P J I s y s t e m
causing a f a s t e r burn.
3

11.
CLEMENTS
201
1500
01
0.5
1.0
1.5
I
2.0
Figure 5. Burn rate (/) vs. f o r a methane-air mixture i n

a constant volume chamber.
(Reproduced w i t h permission from Ref.
20. Copyright 193, Combustion Science and Technology.)
Figure 6. Log pV^ vs. t i m i n g angle f o r combustion o f a methanea i r mixture ( = 1.0) i n a s i n g l e - c y l i n d e r t e s t engine. (Repro
duced w i t h permission from Ref. 15. Copyright 193, Combustion
Science and Technology.)

202
I n a manner s i m i l a r t o t h a t done f o r c o n s t a n t volume

c o m b u s t i o n t h e i g n i t i o n d e l a y t i m e i s d e f i n e d as b e i n g t h e t i m e
b e t w e e n when t h e i g n i t i o n s y s t e m f i r e s and when l o g pV^ r e a c h e s
10% o f i t s maximum v a l u e , and a l s o t h e b u r n t i m e i s t h e t i m e
between 10% and 90% on t h e l o g pV^ d i a g r a m .
T a b l e I shows t h e s e
t i m e s f o r b o t h i g n i t i o n s y s t e m s and f o r two a i r - f u e l r a t i o s as a
f u n c t i o n o f t i m i n g . A g a i n one s e e s an a p p r e c i a b l e d e c r e a s e i n t h e
T a b l e I . I g n i t i o n D e l a y and C o m b u s t i o n Times f o r l o g pV"Y a n a l y s i s

( R e p r o d u c e d w i t h p e r m i s s i o n f r o m R e f . 15. C o p y r i g h t 1983,
" C o m b u s t i o n S c i e n c e and T e c h n o l o g y " . )
PJI
Spark
Time
(BTDC)
20
30
40
50
40
50
60
70
80
Air-Fuel
Ratio
1.0
1.0
1.0
1.0
1.2
1.2
1.2
1.2
1.2
Ignition
Delay
(ms)
1.3
1.4
1.4
1.8
2.0
2.3
2.4
2.3
CDI
Combustion
Time
(ms)
1.9
2.1
2.1
2.0
2.1
2.2
2.3
2.3
Ignition
Delay
(ms)
2.6
2.5
2.8
3.2
3.0
3.3
3.6
4.0
4.4
Combustion
Time
(ms)
2.0
2.0
2.0
2.1
2.5
2.8
2.8
2.6
2.0
i g n i t i o n d e l a y w i t h P J I b u t m i n i m a l change i n t h e c o m b u s t i o n t i m e
f o r t h e two v a l u e s o f shown.
T h u s , i n a more q u a n t i t a t i v e manner, one s e e s t h e same
r e s u l t s as were d i s c u s s e d f o r t h e s i t u a t i o n o f t h e e n g i n e r u n n i n g
i n a c o n t i n u o u s mode.
Problems
with PJI
T h e r e a r e b a s i c a l l y two p r o b l e m s a s s o c i a t e d w i t h P J I and t h e s e a r e
inter-related.
For e s s e n t i a l l y a l l the experiments reviewed i n
t h e p r e s e n t paper e n e r g i e s i n t h e o r d e r o f 1 J a r e d i s s i p a t e d e a c h
time the i g n i t i o n system f i r e s .
Thus i n a t y p i c a l m u l t i - c y l i n d e r
e n g i n e e l e c t r i c a l power i n t h e o r d e r o f 100 W i s r e q u i r e d f o r , s a y
a u t o m o t i v e a p p l i c a t i o n s ; t h i s i s a n o n - n e g l i g i b l e amount o f power.
S e c o n d l y , because o f the l a r g e c u r r e n t s which f l o w i n the plasma
j e t i g n i t e r t h e r e i s a g r e a t d e a l of e l e c t r o d e e r o s i o n . That t h i s
i s so I s no s u r p r i s e i n t h a t i t has l o n g been known ( 1 7 ) t h a t f o r
e v e r y coulomb o f c h a r g e p a s s e d between two e l e c t r o d e s a c e r t a i n

11. CLEM ENTS
203
amount o f e l e c t r o d e m a t e r i a l i s e r o d e d . These two p r o b l e m s have

been c o n s i d e r e d by Smy e t a l . ( 1 8 ) and t h e y c o n c l u d e t h a t i g n i t e r
l i f e t i m e s i n t h e o r d e r o f 10 o r so h o u r s a r e t o be e x p e c t e d .
O b v i o u s l y t h e s i m p l e s t s o l u t i o n t o t h e above two p r o b l e m s i s
t o r e d u c e t h e amount o f e n e r g y d i s s i p a t e d i n t h e i g n i t e r .
Thus
a t p r e s e n t t h e r e a r e i n v e s t i g a t i o n s aimed a t d e t e r m i n i n g t h e
minimum amount o f e n e r g y w h i c h needs t o be d e l i v e r e d t o t h e
i g n i t e r i n o r d e r t o g e n e r a t e a p r o p e r l y f o r m e d i g n i t i n g p u f f and
a l s o t h e t e m p o r a l manner i n w h i c h t h i s e n e r g y s h o u l d be
d e p o s i t e d . Oppenheim ( 1 9 ) h a s u s e d a s m a l l w a t c h j e w e l a s t h e
o r i f i c e i n t h e p l a s m a j e t and t h u s r e d u c e d t h e e r o s i o n o f t h e end
p l a t e o f t h e plasma j e t . T h i s concept c o u p l e d w i t h e l e c t r o d e
m a t e r i a l s w h i c h a r e d i f f i c u l t t o e r o d e may w e l l m i t i g a t e t h e
l i f e t i m e problem as r e l a t e d t o t h e plasma j e t . F i n a l l y , i t
appears p o s s i b l e t o m e c h a n i c a l l y generate a puff which i s i n the
f l u i d m e c h a n i c a l s e n s e s i m i l a r t o t h a t g e n e r a t e d by a p l a s m a j e t .
P i t t e t a l ( 2 0 ) have used a f a s t a c t i n g m e c h a n i c a l v a l v e t o
g e n e r a t e t h e h i g h l y t u r b u l e n t p u f f . T h i s p u f f t h e n p a s s e s between
two l o w e n e r g y c o n v e n t i o n a l s p a r k e l e c t r o d e s . The r e s u l t i s v e r y
s i m i l a r t o P J I and s u c h a s y s t e m r e q u i r e s v e r y l i t t l e e l e c t r i c a l
energy.
Conclusions
F o r P J I i g n i t i o n o f non t u r b u l e n t m i x t u r e s i t a p p e a r s t h a t f o r
v a l u e s o f 1 f l u i d m e c h a n i c a l e f f e c t s dominate t h e development
of t h e i g n i t i o n s t a g e w h i l e f o r v a l u e s o f n e a r o r beyond t h e
conventionally defined lean flammability l i m i t i t i s chemical
e f f e c t s which dominate. F o r h i g h l y t u r b u l e n t m i x t u r e s , i . e .
i n t e r n a l c o m b u s t i o n e n g i n e s , when t h e m i x t u r e s t r e n g t h i s n e a r
s t o i c h i o m e t r i c and f o r o p t i m a l t i m i n g o f e a c h i g n i t i o n s y s t e m
t h e r e a p p e a r s t o be m i n i m a l d i f f e r e n c e between them. However f o r
l e a n mixtures P J I extends t h e l e a n l i m i t a p p r e c i a b l y . F o r a l l
s i t u a t i o n s P J I i s much l e s s s e n s i t i v e t o t i m i n g t h a n i s t h e
c o n v e n t i o n a l i g n i t i o n s y s t e m . T h i s may w e l l be u s e f u l i n d u a l
f u e l v e h i c l e s , f o r example g a s o l i n e and methane f u e l e d v e h i c l e s .
I n t h i s c i r c u m s t a n c e i t i s n o r m a l l y n e c e s s a r y t o advance t h e
i g n i t i o n some 20 when c h a n g i n g f r o m g a s o l i n e t o methane a s a
fuel.
W i t h P J I a n o p t i m a l t i m i n g c o u l d be c h o s e n w h i c h w o u l d
c a u s e good c o m b u s t i o n f o r e i t h e r f u e l and t h e t i m i n g advance l e f t
unchanged.
F i n a l l y from a p r a c t i c a l p o i n t o f view t h e problems
r e l a t e d t o h i g h e n e r g y c o n s u m p t i o n and h i g h e l e c t r o d e wear must be
overcome b e f o r e P J I c a n become a c o m m e r c i a l l y v i a b l e i g n i t i o n
source.
Acknowledgments
T h i s work was s u p p o r t e d by N a t i o n a l S c i e n c e s and E n g i n e e r i n g
R e s e a r c h C o u n c i l o f Canada a s w e l l as t h e B r i t i s h C o l u m b i a S c i e n c e
Council.

204
Literature Cited
1. Dale, J.D.; Oppenheim, A.K. SAE paper No. 810146, 1981.
2. Sloane, R.M.; Ratcliffe, J.W. "Experimental and
Computational Studies of the Chemistry of Ignition
Process", this symposium.
3. Topham, D.R.; Smy, P.R.; Clements, R.M. Combust. Flame,
1975, 25, 87.
4. Asik, J.R.;, Piatkowski, P.; Foucher, M.J.; Rado,W.G.SAE
paper No. 770355, 1977.
5. Oppenheim, A.K.; Teichman, K.; Horn, K; Stewart,H.E.SAE
paper No. 780637, 1978.
6. Weinberg, F.J.; Horn, K.; Oppenheim, A.K.; Teichman, K.
Nature 1978, 272, 341.
7. Bradley, D.; Critchley, I.L. Combust. Flame 1974, 22, 143.
8. Harrison, A.J.; Weinberg, F.J. Combust. Flame 1974, 22, 263.
9. Richards, J.M. J. Fluid Mech. 1965, 21, 97.
10. Topham, D.R.; Zhang, J.X.; Clements, R.M.; Smy, P.R. J. Phys.
D:
Appl. Phys. 1982, 15, L65.
11. Orrin, J.E.; Vince, I.M.; Weinberg, F.J. in "Eighteenth
Symposium (International) on Combustion", The Combustion
Institute: Pittsburgh, 1981, p. 1755.
12. Zhang, J.X.; Clements, R.M.; Smy, P.R. Combust. Flame 1983,
50, 99.
13. Dale, J.D.; Smy, P.R.; Clements, R.M. Combust. Flame 1978,
31, 173.
14. Tozzo, L.; Dabora, E.K. "Nineteenth Symposium (International)
on Combustion", The Combustion Institute: Pittsburgh, 1982,
p. 1467.
15. Pitt, P.L.; Clements, R.M. Combustion Sci. and Tech. 1983,
30, 327.
16. Edwards, C.F.; Dale, J.D.; Oppenheim, A.K. SAE paper No.
830479, 1983.
17. Cobine, J.D. "Gaseous Conductors", Dover Publications, 1958;
p.
301.
18. Smy, P.R.; Clements, R.M.; Dale, J.D.; Simeoni, D.;
Topham, D.R. J. Phys. D: Appl. Phys. 1983, 16, 783.
19. Oppenheim, A.K., personal communication.
20. Pitt, P.L.; Ridley, J.D.; Clements, R.M. Combustion Sci. and
Tech.,
accepted for publication.
RECEIVED October
26, 1983

12
Chemistry of Spark Ignition
An Experimental and Computational Study

THOMPSONM.SLOANE and JOHNW.RATCLIFFE
Physical Chemistry Department, General Motors Research Laboratories, Warren,MI48090
The chemistry of ignition has been investigated by
time-resolved molecular beam mass spectrometry and
schlieren photography. A simultaneous characteri
zation of the physical and chemical properties of
flame ignition has yielded the first detailed chemi
cal information about the process. Time-of-flight
detection has allowed a correspondence to be made
between the oxygen signal detected as a function
of time after the spark and the oxygen concentra
tion at the sampling cone tip. Flame propagation
appears to begin about 0.2 cm from the spark elec
trodes rather than between the electrodes as has
been conventionally assumed. A one-dimensional
combustion model shows that heat loss to the elec
trodes can cause the flame to begin at a distance
from the electrodes rather than in the electrode
We h a v e p r e v i o u s l y d e m o n s t r a t e d ( 1 ) o u r a b i l i t y t o make t i m e r e s o l v e d mass s p e c t r o m e t e r s a m p l i n g measurements o f a f l a m e
p r o p a g a t i n g t h r o u g h a c o m b u s t i o n bomb. Our i n t e r e s t i n m a k i n g
t h e s e k i n d s o f measurements i s t o s t u d y t h e c h e m i s t r y o f i g n i t i o n b y v a r i o u s i g n i t i o n methods a n d t o d e t e r m i n e t h e v a l u e o f
t h e s e d i f f e r e n t methods f o r c o m b u s t i o n m o d i f i c a t i o n .
This report
p r e s e n t s our f i r s t r e s u l t s on t h e chemistry o f spark i g n i t i o n .
T h e r e a r e a t l e a s t two r e a s o n s why a d e t a i l e d s t u d y o f
s p a r k i g n i t i o n i s w o r t h w h i l e . F i r s t , v e r y l i t t l e i s known a b o u t
the chemistry o f spark i g n i t i o n .
The i d e n t i t y a n d q u a n t i t y o f
r a d i c a l s p r o d u c e d i n d i f f e r e n t m i x t u r e s compared t o t h e amount
of energy d e p o s i t e d a s heat c o u l d be a n i m p o r t a n t f a c t o r i n t h e
i g n i t a b i l i t y o f t h e s e m i x t u r e s . A n i m p r o v e d method o f i g n i t i o n
c o u l d decrease the hydrocarbon emissions from a d i r e c t - i n j e c t i o n
0097-6156/84/0249-0205506.00/0
206
s t r a t i f i e d c h a r g e e n g i n e and c o u l d a l s o remedy p r o b l e m s due t o

wet o r f o u l e d s p a r k p l u g s i n homogeneous s p a r k i g n i t e d e n g i n e s .
Second, knowledge o f the c h e m i s t r y o f s p a r k i g n i t i o n s e r v e s as a
b a s e l i n e of comparison w i t h o t h e r t y p e s o f i g n i t i o n such as
p l a s m a j e t and p h o t o c h e m i c a l i g n i t i o n .
The d i f f e r e n c e s o b s e r v e d
among t h e s e d i f f e r e n t t y p e s o f i g n i t i o n i s r e l a t e d t o t h e d i f f e r e n c e s i n t h e c h e m i s t r y and f l u i d m e c h a n i c s a s s o c i a t e d w i t h
them. The p r e s e n t s t u d y t h e r e f o r e f o r m s a n i m p o r t a n t s t e p i n
o u r i n v e s t i g a t i o n i n t o t h e mechanism o f c o m b u s t i o n i n i t i a t i o n
w i t h the i n t e n t to modify the combustion process i n a f a v o r a b l e
way t h r o u g h t h e i g n i t i o n p r o c e s s .
T h e r e i s v e r y l i t t l e known a b o u t t h e c h e m i s t r y o f i g n i t i o n
by e l e c t r i c s p a r k , o r by any o t h e r means f o r t h a t m a t t e r .
A
number o f p h y s i c a l c h a r a c t e r i z a t i o n s h a v e g i v e n r i s e t o a g e n e r a l l y a c c e p t e d o v e r a l l p i c t u r e o f how i g n i t i o n p r o c e e d s .
One s u c h
d e s c r i p t i o n o f what i s known a b o u t s p a r k i g n i t i o n i s g i v e n i n
L e w i s and v o n E l b e ( 2 ) . W i t h i n t h e s m a l l v o l u m e o f h e a t e d gas
p r o d u c e d by t h e s p a r k t h e r e i s u n d o u b t e d l y some i o n i z a t i o n and
d i s s o c i a t i o n i n a d d i t i o n t o t h e r m a l h e a t i n g . I t i s n o t known
what d i s t r i b u t i o n o f e n e r g y i n t h e s e d i f f e r e n t f o r m s p r o v i d e s an
optimum m i x f o r i g n i t i o n .
I t i s a p p a r e n t , t h o u g h , t h a t a minimum
amount o f e n e r g y i s n e c e s s a r y t o p r o d u c e a f l a m e k e r n e l o f a
certain c r i t i c a l size.
I f t h i s c r i t i c a l s i z e i s not a t t a i n e d ,
the flame does not propagate.
The r e s u l t s o b t a i n e d h e r e g i v e a q u a l i t a t i v e p i c t u r e o f t h e
e v o l u t i o n o f c h e m i c a l components f o r a n e l e c t r i c s p a r k i n t h r e e
m i x t u r e s , two o f w h i c h i g n i t e and one o f w h i c h d o e s n o t i g n i t e .
We w i l l show t h e t i m e and s p a t i a l e v o l u t i o n o f t h e c o n c e n t r a t i o n
o f a n i m p o r t a n t r a d i c a l a s w e l l a s r e a c t a n t s . We a l s o show
simultaneous f l a s h S c h l i e r e n p i c t u r e s of the i g n i t i o n to charact e r i z e t h e p h y s i c a l a s p e c t s o f t h e i g n i t i o n p r o c e s s and o f t h e
s a m p l i n g method. Our f i r s t r e s u l t s o f t i m e - o f - f l i g h t d e t e c t i o n
w h i c h y i e l d g r e a t l y enhanced t i m e r e s o l u t i o n w i l l be p r e s e n t e d
f o r o x y g e n . A c o m p a r i s o n o f t h e s e e x p e r i m e n t s w i t h t h e unchopped
s i g n a l enhances t h e v a l u e of the d a t a p r e s e n t e d .
Experimental
The a p p a r a t u s u s e d i n t h e m o l e c u l a r beam s a m p l i n g e x p e r i m e n t s has
b e e n p r e v i o u s l y d e s c r i b e d i n d e t a i l (j.) . A s c h e m a t i c d i a g r a m i s
shown i n F i g u r e 1. A q u a r t z cone h a v i n g a n i n c l u d e d a n g l e o f 60
a t t h e t i p mounted on t h e w a l l o f t h e c o m b u s t i o n bomb s a m p l e s t h e
r e g i o n o f i n t e r e s t by s e r v i n g a s t h e n o z z l e o f a m o l e c u l a r beam
sampling system.
A m u l t i c h a n n e l a n a l y z e r r e c o r d s mass s p e c t r o m e t e r s i g n a l s as a f u n c t i o n o f t i m e a f t e r t h e s p a r k . The s p a r k i s
2 y s i n d u r a t i o n and i s p r o d u c e d by a c i r c u i t w h i c h i s s u p p l i e d
w i t h 200 mJ o f e l e c t r i c a l e n e r g y .
The l o c a t i o n o f t h e 0.1 cm
s p a r k gap c a n be changed so t h a t d i f f e r e n t r e g i o n s o f t h e d e v e l o p i n g f l a m e c a n be s a m p l e d . F i l l i n g and e m p t y i n g o f t h e bomb,

12.
SLOANE AND RATCLIFFE
207
TIME-RESOLVED M O L E C U L A R B E A M M A S S S P E C T R O M E T R Y
OF TRANSIENT COMBUSTION P H E N O M E N A
Gas Manifold
X-Y Recorder
Minicomputer |
Pulse Counting
II
Electronics
Multichannel Analyzer
Collimators
Ignition
Source
Vacuum _
Chamber
Exhaust
Quadrupole
Mass Spectrometer
Quartz Sampling Cone
Combustion Bomb
Figure 1. Schematic diagram o f the apparatus. (Reproduced w i t h

permission from Rf. 1. Copyright 1983, Combust. S c i . Technol.)

208
s p a r k t i m i n g , and d a t a c o l l e c t i o n a r e p e r f o r m e d u n d e r t h e c o n
t r o l o f a m i c r o c o m p u t e r so t h a t s i g n a l c a n be o b t a i n e d f r o m
repetitive ignitions.
The bomb was f i l l e d t o a n i n i t i a l p r e s
s u r e o f 32 k P a w i t h m i x t u r e s o f C H ^ - 0 ~ A r h a v i n g d i f f e r e n t
stoichiometries.
The r a t i o o f o x y g e n t o a r g o n was i d e n t i c a l t o
t h e 02^2
r a t i o i n a i r f o r a l l b u t one e x p e r i m e n t .
I n order to i n c r e a s e the time r e s o l u t i o n i n these e x p e r i
m e n t s , a t i m e - o f - f l i g h t c h o p p e r was p l a c e d 6.9 cm downstream f r o m
t h e cone t i p , b e t w e e n t h e bomb and t h e skimmer. The c h o p p e r
b l a d e has f o u r e q u a l l y s p a c e d s l o t s and i s d r i v e n by a 400 Hz
s y n c h r o n o u s m o t o r . The r e s u l t i n g s h u t t e r f u n c t i o n g i v e s an open
t i m e o f 50 y s f o l l o w e d by a c l o s e d t i m e o f 575 y s .
Taking i n t o
a c c o u n t t h e f l i g h t t i m e d i s t r i b u t i o n f r o m t h e s a m p l i n g cone t i p
t o t h e c h o p p e r , s i g n a l s c a n t h e n be o b t a i n e d w i t h a t i m e r e s o l u
t i o n o f a b o u t 100 y s a t 625 y s i n t e r v a l s f o r a g i v e n t i m e r e l a
t i o n s h i p b e t w e e n t h e c h o p p e r p o s i t i o n and t h e s p a r k .
This type
o f measurement has b e e n made f o r a r g o n and o x y g e n i n a s t o i c h i o
m e t r i c m i x t u r e w i t h t h e t i p o f t h e cone l o c a t e d 0.5 cm and
0.2
cm f r o m t h e s p a r k e l e c t r o d e s .
We c o n s i d e r e d i t l i k e l y t h a t p l a c i n g t h e c h o p p e r b e t w e e n t h e
n o z z l e and t h e skimmer m i g h t i n t e r f e r e w i t h t h e s u p e r s o n i c e x p a n
s i o n d o w n s t r e a m o f t h e n o z z l e . We w e r e p l e a s a n t l y s u r p r i s e d t o
f i n d t h a t t h i s was n o t t h e c a s e b e c a u s e we o b t a i n e d v e l o c i t y
d i s t r i b u t i o n s w i t h t h e c h o p p e r l o c a t e d b e t w e e n t h e n o z z l e and t h e
skimmer w h i c h w e r e i d e n t i c a l t o t h e d i s t r i b u t i o n s o b t a i n e d when
t h e c h o p p e r was l o c a t e d i n t h e more c o n v e n t i o n a l p o s i t i o n down
s t r e a m o f t h e skimmer. T h i s i s u n d o u b t e d l y due t o t h e noni d e a l i t y o f t h e f l o w t h r o u g h t h e cone w h i c h w i l l be d e s c r i b e d
later.
S c h l i e r e n p h o t o g r a p h s o f t h e s p a r k k e r n e l and t h e d e v e l o p i n g
flame were o b t a i n e d u s i n g a c o n v e n t i o n a l arrangement. A f l a s h lamp-pumped dye l a s e r was u s e d t o f u r n i s h a 1 y s l i g h t p u l s e
( 6 0 0 nm) t o i l l u m i n a t e t h e i n t e r i o r o f t h e c o m b u s t i o n bomb.
By d e l a y i n g t h e l a s e r p u l s e f o r a v a r i a b l e t i m e a f t e r t h e s p a r k ,
t h e p r o g r e s s o f t h e i g n i t i o n k e r n e l and t h e f l a m e c o u l d be
f o l l o w e d at v e r y short delay times f o r s e q u e n t i a l i g n i t i o n s .
A
s e r i e s o f p i c t u r e s w h i c h shows t h e f l a m e a p p r o a c h i n g and t h e n
p a s s i n g t h e c o n e t i p i s shown i n F i g u r e 2.
T h e r e i s no n o t i c e
a b l e d i s t o r t i o n o f the f l a m e as i t approaches the t i p because the
f l a m e shape i n the absence o f the probe i s v i r t u a l l y i d e n t i c a l to
t h e f l a m e shape w i t h t h e p r o b e p r e s e n t .
This i s consistent with
t h e f i n d i n g o f Y o o n and K n u t h (3) t h a t a t c o m p a r a b l e p r e s s u r e i n
a s t e a d y - s t a t e f l a m e s a m p l i n g e x p e r i m e n t t h e c o n e has no a p p r e
c i a b l e e f f e c t on t h e f l a m e .
The l e n g t h o f t h e o r i f i c e i s s h o r t
enough (~0.015 cm o r t w i c e t h e d i a m e t e r ) t h a t t h e r e s h o u l d be
l i t t l e r a d i c a l recombination i n the o r i f i c e ( 3 ) .
The v e l o c i t y d i s t r i b u t i o n o f a r g o n sampled w i t h t h e q u a r t z
c o n e a t 32 k P a and 300 K, t h e i n i t i a l p r e s s u r e and t e m p e r a t u r e ,
c o r r e s p o n d s t o a t e r m i n a l Mach number o f a b o u t 2.8 i n t h e m o l e c
u l a r beam, w h i c h i s somewhat s m a l l e r t h a n t h e e x p e c t e d Mach

209
12. SLOANE AND RATCLIFFE
Figure 2. S c h l i e r e n photographs o f a s t o i c h i o m e t r i c flame p a s s i n g

the sampling cone.

210
number o f 16.6.
T h i s i s v e r y l i k e l y due t o t h e p r e s e n c e o f a
boundary l a y e r a l o n g the i n s i d e w a l l s o f the s a m p l i n g cone which
p r e v e n t s much o f t h e c o o l i n g w h i c h a c c o m p a n i e s t h e i s e n t r o p i c
e x p a n s i o n o f t h e sampled g a s .
When t h e cone i s r e p l a c e d by a
s i m p l e f r e e j e t s o u r c e h a v i n g t h e same o r i f i c e s i z e , t h e Mach
number c h a r a c t e r i z i n g t h e v e l o c i t y d i s t r i b u t i o n o b t a i n e d i s a b o u t
15.
F u t u r e e x p e r i m e n t s w i l l be p e r f o r m e d w i t h c o n e s h a v i n g a
l a r g e r i n c l u d e d a n g l e t o attempt t o minimize t h i s problem.
A c c o r d i n g t o t h e w o r k o f Y o o n and K n u t h , we s h o u l d be a b l e t o u s e
a s a m p l i n g c o n e w i t h a n a n g l e o f 110 w i t h o u t u n d u l y d i s t u r b i n g
t h e f l a m e . P r e l i m i n a r y e x p e r i m e n t s w i t h s u c h a cone y i e l d
v e l o c i t y d i s t r i b u t i o n s w h i c h a r e n e a r l y i d e n t i c a l t o t h a t obt a i n e d w i t h t h e f r e e j e t s o u r c e . T h i s has c o n f i r m e d o u r s u s p i c i o n t h a t t h e s m a l l e r a n g l e cone u s e d i n t h e s e e x p e r i m e n t s
c a u s e s a t h e r m a l i z a t i o n o f t h e beam i n a t h i c k b o u n d a r y l a y e r
w h i c h f i l l s t h e r e g i o n o f t h e cone j u s t downstream o f t h e o r i f i c e .
T h i s b o u n d a r y l a y e r may be p r e s e n t w i t h t h e 110 c o n e , b u t i t
a p p a r e n t l y does not i n t e r f e r e w i t h the c o r e of t h e j e t because of
t h e l a r g e r a n g l e . We e x p e c t t o a c h i e v e h i g h e r beam i n t e n s i t i e s ,
n a r r o w e r v e l o c i t y d i s t r i b u t i o n s , and l e s s v e l o c i t y s l i p , i . e . ,
l e s s d i f f e r e n c e i n t h e v e l o c i t y o f d i f f e r e n t components, w i t h
t h i s c o n e . P e r h a p s t h e most i m p o r t a n t a d v a n t a g e t o be g a i n e d i s
a narrow v e l o c i t y d i s t r i b u t i o n because t h i s has a d i r e c t e f f e c t
on t h e t i m e r e s o l u t i o n i n t h e s e e x p e r i m e n t s .
I n v i e w o f t h e f a c t t h a t t h e s a m p l i n g c o n d i t i o n s a r e somewhat l e s s t h a n i d e a l , t i m e - d e p e n d e n t s i g n a l s o b t a i n e d f o r r a d i c a l s must be v i e w e d w i t h some c a u t i o n . The t i m e dependence o f
t h e m a j o r c o m p o n e n t s , h o w e v e r , s h o u l d be u n a f f e c t e d by t h e l o w
Mach number f l o w t h r o u g h t h e s a m p l i n g c o n e . S u b s e q u e n t e x p e r i m e n t s w i t h t h e 110 cone s h o u l d p r o v i d e much more d e f i n i t i v e i n f o r m a t i o n on r a d i c a l r e l a t i v e m o l e f r a c t i o n s , t e m p e r a t u r e , and
p e r h a p s a l s o a b s o l u t e m o l e f r a c t i o n s o f a number o f components.
Results
S c h l i e r e n Photography of the I g n i t i o n K e r n e l . S c h l i e r e n photog r a p h s t a k e n a t v e r y s h o r t t i m e s a f t e r t h e s p a r k (3-44 y s ) show
t h a t a l t h o u g h t h e cone does c a u s e a d i s t u r b a n c e o f t h e s h o c k wave
p r o d u c e d by t h e s p a r k when i t i s l o c a t e d 0.2-0.5 cm f r o m t h e
e l e c t r o d e s , t h e r e i s v e r y l i t t l e v i s i b l e e f f e c t on the d e v e l o p ment o f t h e s p a r k k e r n e l .
The p h o t o g r a p h s show t h a t i n a s t o i c h i o m e t r i c m i x t u r e a s p h e r i c a l r e g i o n o f h o t gas a b o u t 1 cm i n
d i a m e t e r i s f o r m e d v e r y r a p i d l y ( i n a b o u t 15 y s ) . T h i s r e g i o n
t h e n expands s l o w l y i n a t o r o i d a l shape and b e g i n s t o p r o p a g a t e
a s shown i n F i g u r e 3.
The p r e s e n c e o f t h e cone had no n o t i c e a b l e
e f f e c t on how f a s t t h e f l a m e d e v e l o p e d .
The q u a l i t a t i v e b e h a v i o r
o f t h e d e v e l o p i n g f l a m e f o l l o w e d v e r y c l o s e l y t h a t w h i c h was
o b s e r v e d by L i t c h f i e l d (4-) under s i m i l a r c o n d i t i o n s .
M a s s S p e c t r o m e t r i c S a m p l i n g o f R e a c t a n t s . The p r i n c i p a l
o f t h e s a m p l i n g cone w e r e 0.0, 0.2, and 0.5 cm away f r o m

locations
the
211
12.
F i g u r e 3 . I g n i t i o n k e r n e l and d e v e l o p i n g flame i n t h e presence

a n d a b s e n c e o f t h e cone a t t h r e e d i f f e r e n t t i m e s a f t e r t h e s p a r k .
The cone i s a b s e n t i n a , b , a n d c , a n d i s p r e s e n t i n d , e , a n d f .
The p i c t u r e s were t a k e n a t t h e f o l l o w i n g t i m e s a f t e r t h e s p a r k :
a a n d d , 18 ; b a n d e , 6h ; a n d c a n d f , 900 s .

212
s p a r k e l e c t r o d e s . The methane s i g n a l a s a f u n c t i o n o f t i m e a f t e r
t h e s p a r k i s shown i n F i g u r e 4 f o r t h e c o n e p l a c e d a t t h e e l e c
trodes.
R e s u l t s f o r two e q u i v a l e n c e r a t i o s a r e shown; t h e
=1.0
m i x t u r e i g n i t e s and t h e =0.35 m i x t u r e d o e s n o t .
I n the s t o i
c h i o m e t r i c c a s e t h e methane s i g n a l d i s a p p e a r s r a t h e r s l o w l y .
As
a c o m p a r i s o n t h e r e s u l t s i n F i g u r e 5a show a much e a r l i e r methane
disappearance.
I n t h i s F i g u r e t h e cone i s l o c a t e d 0.2 cm f r o m
t h e s p a r k gap.
T h i s means t h a t t h e methane i s d i s a p p e a r i n g
0.2
cm f r o m t h e gap b e f o r e i t d i s a p p e a r s a t t h e s p a r k gap i t s e l f .
W i t h t h e cone l o c a t e d 0.5 cm away f r o m t h e gap, t h e methane
d i s a p p e a r a n c e b e g i n s a t v e r y n e a r l y t h e same t i m e as i t d o e s a t
0.2 cm a r d d e c r e a s e s somewhat more s l o w l y as shown i n F i g u r e 6.
W h i l e t h e r e a p p e a r s t o be a b a r e l y n o t i c e a b l e amount o f i n c r e a s e
i n t h e methane s i g n a l a f t e r 0.5 ms i n F i g u r e 5 a , t h e methane
d e c r e a s e s m o n o t o n i c a l l y t o t h e p o s t - c o m b u s t i o n v a l u e a t 0.5
cm.
T h i s i n c r e a s e i s p r o b a b l y due t o u n b u r n e d methane d i f f u s i n g i n t o
t h e 0.2 cm r e g i o n , a l t h o u g h i t i s c l e a r t h a t t h e amount i s v e r y
s m a l l i n t h i s case.
To s e e how t h i s b e h a v i o r c h a n g e s w i t h d i l u t i o n , t h e methane
s i g n a l f o r =1.0 and a n o x y g e n - a r g o n r a t i o o f 0.32 was m e a s u r e d .
The r e s u l t s a r e shown i n F i g u r e 5b.
Methane d i s a p p e a r a n c e b e g i n s
a t a b o u t t h e same t i m e as f o r 0 / = 0.376, b u t much more u n
b u r n e d methane i s d i f f u s i n g i n t o t h i s r e g i o n . A r e s u l t v e r y
s i m i l a r t o F i g u r e 5b i s o b t a i n e d f o r 0 / A r = 0.376, =0.5 w i t h
t h e c o n e l o c a t e d 0.2 and 0.3 cm away f r o m t h e s p a r k gap.
F i g u r e 7 shows t h e o x y g e n s i g n a l a s a f u n c t i o n o f t i m e w i t h
and w i t h o u t t i m e - o f - f l i g h t c h o p p i n g f o r a s t o i c h i o m e t r i c m i x t u r e
and t h e c o n e t i p l o c a t e d 0.5 cm f r o m t h e c h o p p e r .
The c h o p p e d
s i g n a l has b e e n a p p r o x i m a t e l y c o r r e c t e d f o r t h e f l i g h t t i m e t o
the chopper u s i n g the measured a r r i v a l time d i s t r i b u t i o n .
The
v e l o c i t y d i s t r i b u t i o n ( n o t shown) does n o t c h a n g e much w i t h t i m e ,
i n d i c a t i n g t h a t t h e a p p a r e n t s t a g n a t i o n t e m p e r a t u r e o f t h e sam
p l e d gas c h a n g e s l i t t l e .
T h i s m u s t be due t o t h e t h e r m a l i z a t i o n
o f t h e gas as i t p a s s e s t h r o u g h t h e cone w h i c h i s a l s o r e s p o n s i
b l e f o r l o w Mach number f l o w o f a r o o m - t e m p e r a t u r e g a s .
Sub
s e q u e n t e x p e r i m e n t s w i t h a 110 c o n e y i e l d v e l o c i t y d i s t r i b u t i o n s
w h i c h a r e c h a r a c t e r i s t i c of the temperature of the sampled gas.
T h e r m a l i z a t i o n o f t h e s a m p l e d gas j u s t d o w n s t r e a m o f t h e s a m p l i n g
o r i f i c e i s an e x p l a n a t i o n w h i c h r e c o n c i l e s these p o s s i b l y con
f l i c t i n g observations:
the low apparent s t a g n a t i o n temperature
o f t h e b u r n e d g a s and t h e a b s e n c e o f v i s i b l e f l a m e d i s t o r t i o n
due t o t h e p r e s e n c e o f t h e c o n e ( s e e F i g u r e 2 ) . F i g u r e 8 g i v e s
the 0
s i g n a l o b t a i n e d w i t h t h e s a m p l i n g c o n e t i p l o c a t e d 0.2
cm
from the e l e c t r o d e s . I n b o t h p o s i t i o n s , the chopped s i g n a l i n
c r e a s e s a b r u p t l y a t t h e t i m e o f t h e s p a r k , and t h e n d e c a y s
r a p i d l y w i t h i n 50-100 y s o f t h e s p a r k .
We b e l i e v e t h a t t h e
a b r u p t i n c r e a s e i n s i g n a l i s due t o t h e p a s s a g e o f t h e s h o c k
wave, a l t h o u g h t h i s i n c r e a s e i s r e f l e c t e d i n t h e u n c h o p p e d
s i g n a l o n l y a t 0.2 cm.
We c a n o n l y s p e c u l a t e t h a t p e r h a p s t h i s
h a p p e n s b e c a u s e t h e s h o c k i s i n t e n s e enough a t 0.2 cm t o be
2

12.
S LOAN AND RATCLIFFE
METHANE O c m
213
\^
'" '..
= i.o
<
'"..."
CD
CO
= .35
_J
.5
1.0
1.5
2.0
2.5
3.0
TIME (ms)
3.5
4.0
4.5
5.0
Figure U. Methane s i g n a l as a f u n c t i o n o f time f o r two d i f f e r e n t

equivalence r a t i o s . The sampling cone i s l o c a t e d at the e l e c t r o d e s .

214
0.2
cm
(a) 02/Ar = .376
<
CO
(b)0 /Ar=32
2
1.5
1.0
TIME
2.0
(ms)
Figure 5 Methane s i g n a l f o r 0 = 1.0 and two d i f f e r e n t O^/Ar r a t i o s .

The cone i s 0.2 cm from the e l e c t r o d e s ,
a, 0 /Ar = 0.376; and b,
0 /Ar = 0.32.
p
Figure 6 . Methane s i g n a l f o r 0 = 1 . 0 , 0^/Ar = 0 . 3 7 6 .

0 . 5 cm from the e l e c t r o d e s .
The cone i s

12.
Chemistry of Spark
Ignition
215
0.5 cm
SPARK
0.5
1.0
1.5
TIME (ms)
2.0
Figure 7 Oxygen s i g n a l f o r 0 = 1.0, 0 /Ar = 0.376, with the cone

l o c a t e d 0.5 cm from the e l e c t r o d e s . Both unchopped and chopped
s i g n a l i s shown. The time o f the spark i s i n d i c a t e d with an arrow.
Open c i r c l e s , chopped; and dots, unchopped.
Figure 8. Oxygen s i g n a l f o r 0 = 1.0, 0^/Ar = 0.376, with the cone

l o c a t e d 0.2 cm from the e l e c t r o d e s . Chopped and unchopped s i g n a l s
are shown. Open c i r c l e s , chopped; and dots, unchopped.

216
n o t i c e a b l e i n t h e unchopped s i g n a l b u t has d e c a y e d i n s t r e n g t h
a t 0.5 cm so t h a t t h e r e s u l t i n g i n c r e a s e i s l o s t i n t h e a v e r a g
ing over a l a r g e range of t r a n s i t times.
Mass S p e c t r o m e t r i c S a m p l i n g o f R a d i c a l s . M e t h y l r a d i c a l s and
h y d r o g e n atoms w e r e o b s e r v e d i n t h e s p a r k r e g i o n .
The h y d r o g e n
atom s i g n a l w i t h t h e cone a t 0 and 0.2 cm f o r t h e s t o i c h i o m e t r i c
m i x t u r e i s shown i n F i g u r e 9.
The H atom s i g n a l was
undetectable
a t 0.5 cm f o r t h i s m i x t u r e .
F i g u r e 10 shows t h e H atom r e s u l t s
f o r =0.35. The s i g n a l s a p p e a r t o be s t r o n g e r t h a n f o r e i t h e r
=1.0 o r 0.5, p a r t i c u l a r l y a t 0.5 cm w h e r e t h e r e i s a s m a l l b u t
d i s c e r n i b l e s i g n a l . This i s consistent with i g n i t i o n c a l c u l a
t i o n s we h a v e p e r f o r m e d u s i n g o x y g e n atom d i s s o c i a t i o n as t h e
i g n i t i o n method. I n m i x t u r e s t h a t i g n i t e , t h e i n i t i a l l y h i g h
o x y g e n atom c o n c e n t r a t i o n r e l a x e s r a p i d l y t o a v a l u e c h a r a c t e r
i s t i c o f t h e f l a m e . O t h e r r a d i c a l s i n t h e H-O-OH s y s t e m i n
crease to t h e i r c h a r a c t e r i s t i c steady-state flame values.
In
m i x t u r e s w h i c h do n o t i g n i t e , t h e 0 atom c o n c e n t r a t i o n r e l a x e s
more s l o w l y . An a n a l o g o u s s i t u a t i o n o c c u r s i f e i t h e r o r OH
are i n i t i a l l y i n excess s i n c e r e a c t i o n s i n v o l v i n g the
^-O^
s y s t e m a r e v e r y f a s t a t c o m b u s t i o n t e m p e r a t u r e s , d r i v i n g H, 0,
and OH t o w a r d t h e i r e q u i l i b r i u m v a l u e s f o r t h e #2~2 y
t h a t t e m p e r a t u r e . We know t h a t l a r g e amounts o f H, 0, and
CH^
a r e p r o d u c e d i n t h e s p a r k b e c a u s e CH^ and a r e o b s e r v e d d i r e c t l y
and 0 c a n be o b s e r v e d i n t h e a b s e n c e o f methane. I n m i x t u r e s
t h a t i g n i t e , the c o n c e n t r a t i o n s of t h e s e r a d i c a l s should d e c r e a s e
more r a p i d l y t h a n i n a n o n - i g n i t i n g m i x t u r e due t o t h e more r a p i d
r e a c t i o n s of the ^ - 0 2
system which i n v o l v e these r a d i c a l s i n the
d e v e l o p i n g f l a m e and due t o more r a p i d r e a c t i o n s w i t h t h e f u e l .
As m e n t i o n e d p r e v i o u s l y , any i n t e r p r e t a t i o n o f t h e s e atom
measurements must be l o o k e d upon w i t h a r a t h e r s k e p t i c a l eye due
t o t h e n o n - i d e a l s a m p l i n g c o n d i t i o n s u n d e r w h i c h t h e y w e r e ob
t a i n e d . The e f f e c t o f beam t h e r m a l i z a t i o n i n a l t e r i n g r a d i c a l
c o n c e n t r a t i o n s may be d i f f e r e n t f o r d i f f e r e n t p o s i t i o n s o f t h e
c o n e r e l a t i v e t o t h e s p a r k . More d e f i n i t i v e r a d i c a l measurements
w i l l be o b t a i n e d w i t h a more s u i t a b l e c o n e . T h i s w o r k i s c u r
r e n t l y i n progress.
s
a t
Discussion
S i n c e the v e l o c i t y d i s t r i b u t i o n of the sampled oxygen appears t o
be a p p r o x i m a t e l y i n d e p e n d e n t o f t h e t i m e a t w h i c h i t was s a m p l e d ,
we c a n s a f e l y assume t h a t t h i s i s a l s o t h e c a s e f o r methane.
If
we assume t h a t t h e a r r i v a l t i m e d i s t r i b u t i o n f o r methane i s a p p r o x
i m a t e l y t h e same as t h a t f o r o x y g e n e x c e p t f o r t h e d i f f e r e n c e i n
t h e m a s s e s , t h e t i m e s c a l e s o f t h e methane measurement shown i n

12.
217
0 cm
0.2 cm
io
TIME (ms)
1.5
2.0
Figure 9 Hydrogen atom s i g n a l f o r

0 = 1.0 at two cone l o c a t i o n s .
5

0 cm
<
0.2 cm
u r e 1 0 . H y d r o g e n atom s i g n a l f o r
0.35 a t t h r e e cone l o c a t i o n s .
.5
1.0
TIME (ms)

1.5
12.
F i g u r e s 5a and 6 s h o u l d be r o u g h l y comparable.
T h i s means t h a t
t h e methane b e g i n s t o d i s a p p e a r a t 0.5 cm f r o m t h e cone a b o u t
60 y s a f t e r i t b e g i n s t o d i s a p p e a r 0.2 cm f r o m t h e c o n e .
This
d i f f e r e n c e i s l e s s than o u r time r e s o l u t i o n , and the r e s u l t
a g r e e s w e l l w i t h t h e o x y g e n m e a s u r e m e n t s . A l t h o u g h we have n o t
y e t m e a s u r e d t h e v e l o c i t y d i s t r i b u t i o n o f a n y components w i t h
t h e c o n e l o c a t e d a t t h e e l e c t r o d e s , t h e r e c a n be no a m b i g u i t y
a b o u t t h e o b s e r v a t i o n t h a t methane d i s a p p e a r a n c e b e g i n s a t 0.2
cm a n d 0.5 cm b e f o r e i t b e g i n s a t t h e e l e c t r o d e s .
The o n l y way
t o c o n c l u d e f r o m t h e d a t a t h a t methane d i s a p p e a r a n c e b e g i n s a t
t h e e l e c t r o d e s a t t h e same t i m e a s o r s o o n e r t h a n i t b e g i n s t o
d i s a p p e a r a t 0.5 cm i s t o assume t h a t t h e v e l o c i t y d i s t r i b u t i o n
o f t h e sampled methane a t 0 cm i s c h a r a c t e r i s t i c o f a much l o w e r
a p p a r e n t s t a g n a t i o n t e m p e r a t u r e t h a n t h e methane sampled a t 0.5
cm.
S i n c e t h e a p p a r e n t s t a g n a t i o n t e m p e r a t u r e o f t h e methane
d e t e c t e d a t 0.5 cm i s n e a r room t e m p e r a t u r e , t h i s a s s u m p t i o n
c a n n o t be v a l i d .
T h e r e f o r e , u n b u r n e d methane must r e m a i n i n t h e
s p a r k gap a f t e r t h e f l a m e b e g i n s t o d e v e l o p . T h i s f l a m e d e v e l o p
ment p r o b a b l y b e g i n s a t a d i s t a n c e o f a b o u t 0.2 cm f r o m t h e
e l e c t r o d e s i n t h e s t o i c h i o m e t r i c m i x t u r e . The methane p r o f i l e s
o b t a i n e d i n a more d i l u t e s t o i c h i o m e t r i c m i x t u r e (shown i n
F i g u r e 5b) a n d i n a m i x t u r e w h e r e 2/Ar=0.376 a n d =0.5 ( n o t
shown) s u g g e s t t h a t f o r t h e s e m i x t u r e s f l a m e p r o p a g a t i o n b e g i n s
a t a somewhat g r e a t e r d i s t a n c e f r o m t h e s p a r k e l e c t r o d e s .
L e w i s and v o n E l b e ( 2 ) a n d o t h e r s , i n t h e i r d e s c r i p t i o n o f
s p a r k i g n i t i o n , assume t h a t t h e f u e l i s b u r n e d i n s i d e t h e s p a r k
kernel.
A p p a r e n t l y t h i s i s n o t t h e case i n t h e experiment
r e p o r t e d here. R e s u l t s c o n s i s t e n t w i t h the presence o f unburned
f u e l i n t h e s p a r k k e r n e l h a v e b e e n r e p o r t e d by M a l y a n d V o g e l
( 5 ) . They f o u n d t h a t f o r a 60 n s b r e a k d o w n , t h e c e n t e r o f t h e
s p a r k k e r n e l c o o l e d o f f v e r y r a p i d l y a f t e r the breakdown.
They
s u g g e s t e d t h a t t h e s h o c k wave g e n e r a t e d b y s u c h a f a s t s p a r k
causes a r a p i d expansion o f t h e gas i n t h e e l e c t r o d e r e g i o n .
T h i s e x p a n s i o n w o u l d have l i t t l e e f f e c t o n t h e u n b u r n e d m i x t u r e
n e a r t h e e l e c t r o d e s due t o t h e i r v i s c o u s e f f e c t , s o t h e m i x t u r e
i n t h i s b o u n d a r y l a y e r w o u l d be s u c k e d i n t o t h e r a r e f i e d r e g i o n
near t h e e l e c t r o d e s l e f t b e h i n d by t h e r a p i d l y expanding gas.
Our s p a r k i s u n d o u b t e d l y r a p i d enough (2 y s d u r a t i o n ) t o p r o d u c e
t h i s same e f f e c t b e c a u s e we c a n o b s e r v e a s h o c k wave d u e t o t h e
spark i n our s c h l i e r e n photographs.
I n a d d i t i o n , t h e cone c a n
c a u s e a b o u n d a r y l a y e r t o be formed w h i c h a d d s t o t h e amount o f
unburned m i x t u r e which c a n f l o w i n t o t h e e l e c t r o d e r e g i o n .
Experiments i n v o l v i n g e l e c t r o d e l e s s i g n i t i o n , such as by a l a s e r
s p a r k , w o u l d be u s e f u l i n v e r i f y i n g w h e t h e r t h i s phenomenon
occurs.
I t i s n o t n e c e s s a r y , however, t o c o n s i d e r t h e f o r m a t i o n o f
v i s c o u s b o u n d a r y l a y e r n e a r t h e e l e c t r o d e s a n d s a m p l i n g cone i n
o r d e r t o a t l e a s t q u a l i t a t i v e l y e x p l a i n t h e o x y g e n a n d methane
results.
We h a v e p e r f o r m e d o n e - d i m e n s i o n a l c a l c u l a t i o n s w i t h a
c o d e u s e d b y u s i n p r e v i o u s w o r k (6,7) t o s i m u l a t e t h e i g n i t i o n

220
p r o c e s s . We b e g i n t h e c a l c u l a t i o n a t t h e t i m e t h e s p a r k k e r n e l
i s f u l l y f o r m e d , and assume a t e m p e r a t u r e d i s t r i b u t i o n c e n t e r e d
i n a 4 cm w i d e c o n t a i n e r a s shown i n F i g u r e 1 1 . The p o s i t i o n o f
maximum t e m p e r a t u r e g r a d i e n t i s l o c a t e d 0.5 cm o n e i t h e r s i d e o f
the center of the c o n t a i n e r i n accord w i t h the o u t l i n e of the
spark k e r n e l i n the s c h l i e r e n photographs.
Oxygen and methane
a r e d i s s o c i a t e d i n amounts s u c h t h a t 0.4% o f t h e t h e r m a l e n e r g y
d e p o s i t e d i n e a c h g r i d r e g i o n goes i n t o d i s s o c i a t i o n o f o x y g e n
and 0.4% i n t o methane d i s s o c i a t i o n a t t = 0 . A h e a t l o s s due t o
t h e p r e s e n c e o f t h e s p a r k e l e c t r o d e s i s i n t r o d u c e d by i n s e r t i n g
a n e x t r a t e r m i n t h e e n e r g y e q u a t i o n a s was done p r e v i o u s l y (6)
to simulate a cooled crevice.
We assume t h a t t h e e l e c t r o d e gap
i s 0.08 cm a c r o s s and t h e e l e c t r o d e f a c e s a r e 0.08 cm w i d e .
The
e l e c t r o d e s a r e l o c a t e d a t t h e c e n t e r o f t h e c o n t a i n e r and a r e
e q u i d i s t a n t from the a x i s .
The t e m p e r a t u r e o f t h e e l e c t r o d e s
i s the f o l l o w i n g :
T (x)
e
=0.1
T ( x ) + 270
where T ( x ) i s t h e temperature of the gas a t a p o i n t x. T h i s

e x p r e s s i o n a l l o w s t h e e l e c t r o d e s t o i n c r e a s e i n temperature as
t h e g a s n e a r t h e e l e c t r o d e s g e t s warmer, b u t a t a much s l o w e r
r a t e than the gas.
The r e s u l t i n g t i m e e v o l u t i o n o f t h e 0^ and CH^ c o n c e n t r a t i o n s
a t t h r e e l o c a t i o n s i n t h e c o n t a i n e r i s shown i n F i g u r e 12. The
methane and o x y g e n d i s a p p e a r more r a p i d l y a t 0.2 cm t h a n a t
e i t h e r 0.0 o r 0.5 cm.
I f no h e a t l o s s i s i n c l u d e d i n t h e c a l c u
l a t i o n s , o r i f the f r a c t i o n of heat energy g o i n g i n t o d i s s o c i a
t i o n o f 0 and CH^ i s 0.1 r a t h e r t h a n 0.004, methane and o x y g e n
disappearance i s very r a p i d a t the center.
We make no c l a i m t o h a v e m o d e l e d a c c u r a t e l y t h e i g n i t i o n
p r o c e s s b e g i n n i n g w i t h t h e formed s p a r k k e r n e l , a l t h o u g h t h a t
a p p e a r s t o be p o s s i b l e and w i l l be i n v e s t i g a t e d f u r t h e r .
We
p e r f o r m e d t h e s e c a l c u l a t i o n s t o show t h a t a t l e a s t one phenom
enon, w h i c h we know must be p r e s e n t i n o u r e x p e r i m e n t s , c a n
q u a l i t a t i v e l y a c c o u n t f o r t h e e x p e r i m e n t a l r e s u l t s we h a v e o b
t a i n e d . V i s c o u s b o u n d a r y l a y e r s may a l s o c o n t r i b u t e t o t h e
r e l a t i v e l y s l o w b u r n i n g o f methane a t x=0.0. We p l a n e x p e r i m e n t s
w i t h e l e c t r o d e l e s s i g n i t i o n , such as l a s e r s p a r k s , t o f u r t h e r
understand t h i s aspect of the i g n i t i o n process.
2
Conclusions
The e x p e r i m e n t s r e p o r t e d h e r e show t h e c h e m i c a l e f f e c t o f h e a t
l o s s to the spark e l e c t r o d e s i n the i g n i t i o n process. For r a p i d
s p a r k s o f t h e t y p e u s e d h e r e , f l a m e d e v e l o p m e n t b e g i n s a b o u t 0.2
cm away f r o m t h e e l e c t r o d e s r a t h e r t h a n a t t h e e l e c t r o d e s o r a t
t h e edge o f t h e s p a r k k e r n e l .
T h i s new c h e m i c a l i n f o r m a t i o n
p r o v i d e s a d e s c r i p t i o n o f the s p a r k i g n i t i o n p r o c e s s w h i c h has

12.
221
4.0
Figure 11.
culation.
I n i t i a l temperature d i s t r i b u t i o n f o r the i g n i t i o n c a l
= 2.0 cm
= 2.5 cm
50 100 150 200 250

TIME (ms)
Figure 12. Oxygen and methane

as a f u n c t i o n o f time f o r the
i g n i t i o n c a l c u l a t i o n at three
locations.

222
n e v e r b e e n o b t a i n e d b e f o r e . As t h e r e s u l t s o b t a i n e d a r e p r e l i m
i n a r y i n n a t u r e , h o w e v e r , a more d e t a i l e d i n v e s t i g a t i o n o f s p a r k
i g n i t i o n w i t h improved sampling c o n d i t i o n s i s c u r r e n t l y i n p r o
gress .
Literature Cited
1.
2.
3.
4.
5.
6.
7.
Sloane, T. M.; Ratcliffe, J. W. Combust. Sci. Technol. 1983,

33, 65.
Lewis, .; von Elbe, G. Combustion, Flames and Explosions of
Gases; Academic Press Inc., 1961.
Yoon, S.; Knuth, E. L. Progr. Astronaut. Aeronaut. 1981,
74, 867.
Litchfield, E. L. Combust. Flame 1961, 5, 235.
Maly, R.; Vogel, M. Seventeenth Symposium (International) on
Combustion; The Combustion Institute: Pittsburgh, 1979,
p. 821.
Sloane, T. M.; Schoene, A. Y. Combust. Flame 1983, 49, 109.
Sloane, T. M. Combust. Sci. Technol. 1983, 34, 317.
RECEIVED December 21, 1983

13
Elementary Combustion Reactions
Laser Photolysis-Laser-Induced Fluorescence Kinetic Studies
FRANK P. TULLY
Sandia National Laboratories, Livermore, CA 94550
A new, laser-based, chemical kinetics technique
has been demonstrated in studies of the reactions
of the hydroxyl radical with ethane and ethylene.
A widely-tunable, quasi-cw, ultraviolet laser
source for exciting transient-species fluorescence
in chemical kinetics experiments has been built
and is described. The reaction between OH and
C H is shown to proceed through both OH addition
and -atom abstraction routes.
2
Combustion processes are d r i v e n by e n e r g y - r e l e a s i n g chemical r e

actions.
D e t a i l e d knowledge o f t h e c h e m i c a l k i n e t i c s o f these
i n d i v i d u a l r e a c t i v e steps i s r e q u i r e d input t o combustion models.
F o r more t h a n a d e c a d e , e l e m e n t a r y g a s - p h a s e r e a c t i o n k i n e t i c s
has b e e n s u c c e s s f u l l y s t u d i e d w i t h t h e f l a s h p h o t o l y s i s / r e s o n a n c e
f l u o r e s c e n c e technique ( 1 - 8 ) . T y p i c a l l y , f o l l o w i n g broadband
p h o t o l y s i s o f a m o l e c u l a r p r e c u r s o r , r e a c t a n t d e c a y s h a v e been
measured u n d e r p s e u d o - f i r s t - o r d e r k i n e t i c c o n d i t i o n s w i t h cw
r e s o n a n c e lamp e x c i t a t i o n o f f r e e r a d i c a l f l u o r e s c e n c e .
Increased
u t i l i z a t i o n o f l a s e r probes i n k i n e t i c s t u d i e s i s e x e m p l i f i e d by
the recent p u l s e d - l a s e r p h o t o l y s i s / p u l s e d - l a s e r - i n d u c e d f l u o r e s
c e n c e e x p e r i m e n t s o f M c D o n a l d , L i n and c o w o r k e r s ( 9 - 1 3 ) .
I n t h e p r e s e n t w o r k , a new k i n e t i c s c o n f i g u r a t i o n u t i l i z i n g
a p u l s e d l a s e r f o r p h o t o l y s i s and a quasi-cw, u l t r a v i o l e t l a s e r
f o r f l u o r e s c e n c e e x c i t a t i o n has been d e v e l o p e d . T h i s t e c h n i q u e
c o m b i n e s t h e b e s t f e a t u r e s o f t h e two k i n e t i c methods m e n t i o n e d
above. L a s e r p h o t o l y s i s g e n e r a l l y p e r m i t s g r e a t e r r e a c t a n t f o r
m a t i o n s p e c i f i c i t y t h a n does f l a s h l a m p p h o t o l y s i s .
Laser-induced
fluorescence d e t e c t i o n outperforms resonance f l u o r e s c e n c e detec
t i o n because o f i t s i n c r e a s e d f l u o r e s c e n c e e x c i t a t i o n f l u x , de
c r e a s e d s c a t t e r e d l i g h t s i g n a l , and w a v e l e n g t h t u n a b i l i t y .
Cw
fluorescence e x c i t a t i o n i s d e s i r a b l e over pulsed f l u o r e s c e n c e
e x c i t a t i o n due t o i t s f r e e d o m f r o m p u l s e - t o - p u l s e n o r m a l i z a t i o n
c o n s t r a i n t s and, most i m p o r t a n t l y , b e c a u s e o f i t s e f f i c i e n t d u t y
c y c l e and t h e c o n s e q u e n t i n c r e a s e d d e n s i t y o f p o i n t s o b t a i n a b l e
0097-6156/84/0249-0225S06.00/0
226
i n measured m o l e c u l a r c o n c e n t r a t i o n v e r s u s t i m e p r o f i l e s .
This
high data point density f a c i l i t a t e s accurate slope determinations,
r e a d i l y r e v e a l s even s u b t l e d e v i a t i o n s from p s e u d o - f i r s t o r d e r ex
p o n e n t i a l d e c a y s , and o f f e r s i n f o r m a t i o n on s e c o n d a r y r e a c t i o n s
by c a r e f u l l y mapping s u c h d e v i a t i o n s i n d u c e d b y c o n t r o l l e d p e r t u r
bations of the i n i t i a l reactant conditions.
Many m o l e c u l a r i n t e r m e d i a t e s o f i m p o r t a n c e t o c o m b u s t i o n and
atmospheric c h e m i s t r y have p r i m a r y e l e c t r o n i c t r a n s i t i o n s i n t h e
n e a r u l t r a v i o l e t r e g i o n o f t h e e l e c t r o m a g n e t i c s p e c t r u m . We have
t h e r e f o r e constructed a w i d e l y - t u n a b l e , quasi-cw, u l t r a v i o l e t
l a s e r s o u r c e f o r e x c i t i n g t r a n s i e n t - s p e c i e s f l u o r e s c e n c e i n chem
i c a l k i n e t i c s experiments.
A s s u m m a r i z e d i n F i g u r e 1, a model o c k e d A r l a s e r o p e r a t i n g a t 514.5 nm s y n c h r o n o u s l y pumps an
e x t e n d e d - c a v i t y dye l a s e r , p r o d u c i n g , w i t h v a r i o u s dyes, t u n a b l e
r a d i a t i o n f r o m 540 nm t o 900 nm. The dye l a s e r f u n d a m e n t a l o u t
put c o n s i s t s o f a t r a i n o f p u l s e s o f 3-6 n J e n e r g y and 8-10 ps
d u r a t i o n a t a r e p e t i t i o n r a t e o f 246 MHz. T h i s o u t p u t i s
f r e q u e n c y d o u b l e d u s i n g t e m p e r a t u r e - and a n g l e - t u n e d s e c o n d h a r
monic g e n e r a t i o n c r y s t a l s .
The u l t r a v i o l e t l a s e r r a d i a t i o n p r o
duced i n t h i s p r o c e s s i s then used t o e x c i t e f l u o r e s c e n c e i n t h e
reactive r a d i c a l s of i n t e r e s t .
Three f e a t u r e s of t h i s l a s e r source merit f u r t h e r d i s c u s s i o n .
F i r s t , i n a t y p i c a l k i n e t i c e x p e r i m e n t , t h e 1/e c h e m i c a l l i f e t i m e
o f t h e p h o t o l y t i c a l l y p r o d u c e d r a d i c a l s v a r i e s between 0.2 and
25 ms, a r e p r e s e n t a t i v e mean b e i n g t i / = 2 ms. F o r s t a t i s t i c a l
r e a s o n s , one d e s i r e s t o c o l l e c t a minimum o f 20 c o n c e n t r a t i o n
v e r s u s t i m e d a t a p o i n t s p e r 1/e c o n c e n t r a t i o n d e c a y p e r i o d . F o r
multichannel s c a l i n g d e t e c t i o n , these t y p i c a l k i n e t i c c o n d i t i o n s
i m p l y a maximum d w e l l p e r i o d p e r c h a n n e l o f 100 y s . The u l t r a
v i o l e t l a s e r s o u r c e d e s c r i b e d above e m i t s 2.5 10** p u l s e s p e r
100 y s i n t e r v a l ; t h u s , r e l a t i v e t o c h e m i c a l d e c a y s , t h i s r a p i d l y
p u l s e d s o u r c e i s v i e w e d b y t h e e x p e r i m e n t a s a cw e x c i t a t i o n
probe.
S e c o n d , g i v e n t h a t a p u l s e d initition/cw d e t e c t i o n
k i n e t i c s c o n f i g u r a t i o n i s d e s i r e d , one may a s k why a cw l a s e r
s o u r c e i s n o t u s e d . The r a t i o n a l e h e r e i s t h a t t h e v i s i b l e - t o u l t r a v i o l e t c o n v e r s i o n e f f i c i e n c y i s much h i g h e r when t h e q u a s i cw s o u r c e r a t h e r t h a n a cw s o u r c e i s u s e d . F r e q u e n c y d o u b l i n g
e f f i c i e n c y v a r i e s i n p r o p o r t i o n t o t h e f u n d a m e n t a l peak power
d e n s i t y present i n t h e second harmonic g e n e r a t i o n c r y s t a l ,
(P /Po))ot . T a b l e I l i s t s t y p i c a l p u l s e r e p e t i t i o n r a t e s ,
f u n d a m e n t a l peak power d e n s i t i e s and f r e q u e n c y d o u b l i n g e f f i
c i e n c i e s obtainable with various v i s i b l e l a s e r sources.
For the
cw and q u a s i - c w dye l a s e r s o u r c e s , peak power d e n s i t i e s a r e e s
t i m a t e d a s s u m i n g t h a t 1.0 w a t t o f v i s i b l e r a d i a t i o n i s f o c u s e d
t o a 50 ym s p o t w i t h i n t h e f r e q u e n c y d o u b l i n g c r y s t a l .
Because
t h e beam e n e r g y i s b u n c h e d i n t o s h o r t d u r a t i o n p u l s e p a c k e t s
w i t h t h e q u a s i - c w s o u r c e , t h e o b t a i n a b l e f o c u s e d peak power d e n
s i t y and t h e r e s u l t a n t s e c o n d h a r m o n i c g e n e r a t i o n e f f i c i e n c y a r e
much l a r g e r w i t h t h i s s o u r c e t h a n w i t h a cw dye l a s e r s o u r c e .
From 1.0 w a t t o f dye l a s e r r a d i a t i o n a t 616 nm, f o r e x a m p l e , we
2a)

13.
TULLY
Elementary Combustion
500
Reactions: Kinetic Studies
600
227
700
800
Ar"*" PUMP
DYE LASER
TT:
ADP
A T :
I-
ADA
RDA
UREA, LFM, TARTARIC ACID
LilOo
CH 0
CH0
II
CS SO
So
CN
OH
250
CH0
H
5
I
300
SH
NH
350
L
400
FLUORESCENCE EXCITATION WAVELENGTH (nm)
F i g u r e 1. L a s e r - i n d u c e d f l u o r e s c e n c e d e t e c t i o n o f U V - a b s o r b i n g
free radicals.
The v e r t i c a l l i n e s d e n o t e t h e -wavelengths t h a t
a r e most u s e f u l i n f l u o r e s c e n c e e x c i t a t i o n .

228
Table
I.
Second H a r m o n i c G e n e r a t i o n
Pulse
Repetition
R a t e (Hz)
Peak Power Dens i t y (MW/cm )
Nd/YAG-pumped
dye l a s e r
30
50,
unfocused
10-25
cw dye l a s e r
cw
0.05,
focused
0.1
q u a s i - c w dye
laser
f r o m V i s i b l e Dye L a s e r s
2.46 1 0
20,
focused
Second H a r m o n i c Gene r a t i o n E f f i c i e n c y (%)
o b t a i n a v e r a g e u l t r a v i o l e t l a s e r powers o f 80 mW and 1 mW upon

f r e q u e n c y d o u b l i n g t h e q u a s i - c w and cw f u n d a m e n t a l beams, r e s p e c
tively.
The h i g h u l t r a v i o l e t f l u x s o o b t a i n e d w i t h t h e q u a s i - c w
l a s e r s o u r c e w i l l p e r m i t e f f i c i e n t s t u d y o f many p r e v i o u s l y u n observable chemical processes.
Finall"
the uncertainty p r i n c i
p l e d i c t a t e s t h a t s h o r t d u r a t i o n l a s e r a l s e s have wide s p e c t r a l
b a n d w i d t h s . We measure FWHM l a s e r l i n e w i d t h s o f ~ 50 GHz f o r t h e
f u n d a m e n t a l beam. T h i s w i d t h i s much l a r g e r t h a n a t y p i c a l
Doppler-broadened a b s o r p t i o n l i n e i n a d i a t o m i c molecule, and, as
d e s c r i b e d b e l o w f o r OH d e t e c t i o n , a b s o r p t i o n l i n e c o i n c i d e n c e s
must be l o c a t e d and e x p l o i t e d t o o p t i m i z e t h e l a s e r - i n d u c e d f l u o
rescence d e t e c t i o n e f f i c i e n c y of diatomic r a d i c a l s w i t h t h i s
quasi-cw, u l t r a v i o l e t source.
This constraint l a r g e l y disappears
when m o n i t o r i n g p o l y a t o m i c r a d i c a l s , a s t h e s e p a r a t i o n s b e t w e e n
t h e i r r o - v i b r o n i c t r a n s i t i o n l i n e s a r e comparable t o Doppler
l i n e w i d t h s , thereby making a l l o f t h e source u l t r a v i o l e t r a d i a
t i o n a b s o r b a b l e by t h e r a d i c a l .
These c o n s i d e r a t i o n s a r e d i s
c u s s e d i n d e t a i l b y Inoue e t a l ( 1 4 ) i n t h e i r c o m p a r i s o n o f t h e
laser-induced fluorescence spectroscopies of the molecular
homologs OH and C H 0 .
The a p p l i c a t i o n o f t h e q u a s i - c w , u l t r a v i o l e t l a s e r s o u r c e t o
k i n e t i c s t u d i e s was d e m o n s t r a t e d i n t h e l a s e r p h o t o l y s i s / l a s e r i n d u c e d f l u o r e s c e n c e e x p e r i m e n t s shown s c h e m a t i c a l l y i n F i g u r e 2.
C h e m i c a l r e a c t i o n s were i n i t i a t e d by 193-nm p h o t o l y s i s o f N 0 i n
N 0 / H 0 / h y d r o c a r b o n / h e l i u m gas m i x t u r e s .
The 0(*D) atoms formed
by p h o t o d i s s o c i a t i o n r a p i d l y c o n v e r t e d t o OH t h r o u g h r e a c t i o n
w i t h H 0 , and t i m e - r e s o l v e d OH c o n c e n t r a t i o n s were measured a s
f u n c t i o n s o f h y d r o c a r b o n number d e n s i t y b y l a s e r - i n d u c e d f l u o
rescence.
H y d r o x y l r a d i c a l f l u o r e s c e n c e was e x c i t e d b y pumping
t h e n e a r l y c o i n c i d e n t P j l , 0^3, and Q ^
( 0 , 0 ) band > *
t r a n s i t i o n s a t 308.16 nm, ( 1 5 ) and r a d i a t i o n e m a n a t i n g f r o m t h e
r e a c t i o n volume i n a downward d i r e c t i o n was skimmed by b l a c k a n o d i z e d c o l l i m a t o r s , f o c u s e d by q u a r t z l e n s e s , s e l e c t e d by a
b a n d p a s s f i l t e r (308.3 nm p e a k , 8 nm FWHM), and d e t e c t e d b y an
RCA 8850 p h o t o m u l t i p l i e r o p e r a t i n g i n t h e p h o t o n - c o u n t i n g mode.
P


PDP 11/23
MINI
COMPUTER
Figure 2. Schematic diagram o f the l a s e r p h o t o l y s i s / l a s e r - i n d u c e d fluorescence

chemical k i n e t i c s apparatus. (Reproduced w i t h permission from Ref. 20. Copyr i g h t 1 9 8 3 , North-Holland.)
ANALYZER
MULTICHANNEL
230
CHEMISTRY OF
COMBUSTION
PROCESSES
The p h o t o m u l t i p l i e r o u t p u t p u l s e s were a m p l i f i e d , d i s c r i m i n a t e d ,
and f e d i n t o a m u l t i c h a n n e l s c a l e r , and OH f l u o r e s c e n c e d e c a y s
w e r e s i g n a l a v e r a g e d o v e r 25-250 e x c i m e r l a s e r s h o t s .
The f i r s t k i n e t i c s e x p e r i m e n t s p e r f o r m e d w i t h t h i s a p p a r a t u s
d e a l t w i t h t h e a b s t r a c t i o n o f h y d r o g e n atoms by OH f r o m methane
and e t h a n e , OH + RH
H 0 + R.
R e l i a b l e rate c o e f f i c i e n t data
f o r t h e s e r e a c t i o n s had p r e v i o u s l y been o b t a i n e d i n f l a s h
p h o t o l y s i s / r e s o n a n c e f l u o r e s c e n c e s t u d i e s , (7,16) and agreement
w i t h t h e s e p u b l i s h e d d a t a s e r v e d a s a r e q u i r e d c h e c k on t h e p e r
f o r m a n c e o f t h e new k i n e t i c s c o n f i g u r a t i o n . The r e s u l t s f o r t h e
r e a c t i o n between OH and C H a r e shown i n F i g u r e 3.
The r a t e
c o e f f i c i e n t s measured i n t h e p r e s e n t w o r k a l l f a l l a b o u t 5% b e l o w
t h o s e o f R e f . 16; s u c h agreement i s w e l l w i t h i n t h e e s t i m a t e d 10%
a c c u r a c y l i m i t s o f t h e two s t u d i e s . I n b o t h s e t s o f e x p e r i m e n t s ,
t h e OH e x c i t a t i o n and f l u o r e s c e n c e w a v e l e n g t h s were r e s o n a n t , and
o p t i m i z i n g the [0H]-time p r o f i l e s r e q u i r e d maximizing the d e t e c
t e d f l u o r e s c e n c e s i g n a l (S) w h i l e m i n i m i z i n g t h e d e t e c t e d s c a t
t e r e d l i g h t background ( B ) . For s i m i l a r v a l u e s of [0H] _Q, the
r a t i o S/B i n t h e p r e s e n t work e x c e e d e d t h a t o f R e f . 16 b y more
t h a n an o r d e r o f m a g n i t u d e . Two f a c t o r s c o n t r i b u t e d t o t h i s
marked improvement i n S/B.
F i r s t , the absorbable photon f l u x
generated w i t h the quasi-cw, u l t r a v i o l e t l a s e r source exceeded
t h a t f r o m an OH r e s o n a n c e lamp by a f a c t o r o f 2-3.
S e c o n d , and
most s i g n i f i c a n t , t h e d e t e c t e d s c a t t e r e d l i g h t s i g n a l f r o m t h i s
c o l l i m a t e d l a s e r s o u r c e was 10-25 t i m e s l e s s t h a n t h a t t y p i c a l l y
o b t a i n e d w i t h a v o l u m e - s o u r c e , OH r e s o n a n c e lamp 08).
Further
i m p r o v e m e n t s i n S/B a r e e x p e c t e d i n f u t u r e e x p e r i m e n t s i n w h i c h
OH f l u o r e s c e n c e w i l l be e x c i t e d by s i n g l e - f r e q u e n c y u l t r a v i o l e t
l a s e r r a d i a t i o n o b t a i n e d by i n t r a c a v i t y f r e q u e n c y - d o u b l i n g an
a c t i v e l y s t a b i l i z e d cw r i n g dye l a s e r .
E n c o u r a g e d by t h e s e r e s u l t s , we began t o s t u d y h y d r o x y l
r a d i c a l r e a c t i o n s f o r which only l i m i t e d k i n e t i c i n f o r m a t i o n i s
available.
A d e t a i l e d i n v e s t i g a t i o n of the r e a c t i o n
2
(1)
i s i n progress.
A t p r e s e n t , k i n e t i c measurements have b e e n made
at 600 T o r r h e l i u m t h r o u g h o u t t h e t e m p e r a t u r e r a n g e 291-796 K,
and a t 291 o v e r t h e p r e s s u r e r a n g e 50-600 T o r r h e l i u m .
Abso
l u t e r e a c t i o n r a t e c o e f f i c i e n t s k j were d e t e r m i n e d , o r , i n some
c a s e s , a p p r o x i m a t e d , as d e s c r i b e d b e l o w .
We c a r r i e d out a l l e x p e r i m e n t s u n d e r p s e u d o - f i r s t - o r d e r
k i n e t i c c o n d i t i o n s w i t h [0H][t^H^ ] . E x c l u d i n g s e c o n d a r y r e
a c t i o n s t h a t s i g n i f i c a n t l y d e p l e t e o r r e f o r m OH, [OH] v a r i e d
exponentially w i t h time:
[0H]
[ 0 H ] exp
q
-(kJCjHj
+ k )t = [0H]
d
exp(-k't)
w h e r e k' i s t h e m e a s u r e d p s e u d o - f i r s t - o r d e r d e c a y r a t e , k j i s
t h e b i m o l e c u l a r r a t e c o e f f i c i e n t f o r R e a c t i o n ( 1 ) , [0 ^] i s
2

13.
Elementary Combustion Reactions: Kinetic Studies
TULLY
231
- ^
12
> i o - H
10
-13
1.5
1
2
1
1
2.5
3
1000/T(K)
3.5
F i g u r e 3. A r r h e n i u s p l o t o f r a t e c o e f f i c i e n t d a t a f o r t h e r e a c t i o n
OH + CpHg - H 0 + CgH . , R e f . l 6 , f l a s h p h o t o l y s i s / r e s o
nance r l u o r e s c e n c e ; , t h i s work, l a s e r p h o t o l y s i s / l a s e r - i n d u c e d
fluorescence.
E r r o r s p e c i f i c a t i o n s a r e +2 p r e c i s i o n l i m i t s i n
both cases.
2

232
t h e ( c o n s t a n t ) e t h y l e n e c o n c e n t r a t i o n , and
i s the f i r s t - o r d e r
r a t e c o n s t a n t f o r OH r e m o v a l i n t h e a b s e n c e o f [C^H^] due t o d i f
f u s i o n f r o m t h e r e a c t i o n volume and t o r e a c t i o n w i t h b a c k g r o u n d
i m p u r i t i e s . We o b s e r v e d e x p o n e n t i a l [OH] d e c a y s , s u c h as t h a t
shown as l n [OH] v e r s u s t i m e i n F i g u r e 4 a , f o r a l l e x p e r i m e n t s
a t = 291 and 361.5 K.
However, as we v a r i e d f r o m 438 t o 666
K, n o n - e x p o n e n t i a l f e a t u r e s i n t h e [OH] p r o f i l e s became i n c r e a s
i n g l y apparent.
A t y p i c a l [OH] p r o f i l e o b t a i n e d a t 591 i s
p l o t t e d f o r c o m p a r i s o n i n F i g u r e 4b.
F o r e x p o n e n t i a l [OH] p r o
f i l e s , - k was e q u a t e d t o t h e c a l c u l a t e d l e a s t - s q u a r e s s l o p e of
t h e d e c a y t a k e n o v e r a t l e a s t a f a c t o r o f t e n v a r i a t i o n i n [OH].
When a n a l y z i n g n o n e x p o n e n t i a l [OH] p r o f i l e s , we e s t i m a t e d - k
from the steep i n i t i a l s l o p e of the decay. I n e i t h e r case, the
k
v a l u e s o b t a i n e d a t a g i v e n t e m p e r a t u r e and p r e s s u r e were
p l o t t e d , as shown i n F i g u r e 5, as a f u n c t i o n o f t h e c o r r e s p o n d i n g
ethylene concentration. Bimolecular rate c o e f f i c i e n t s kj(T,P)
were then determined from the s l o p e of the l e a s t - s q u a r e s s t r a i g h t
l i n e t h r o u g h t h e ( [ C H j , k ' ) d a t a p o i n t s . The h i g h - p r e s s u r e l i m i t e d r a t e c o e f f i c i e n t s k ( T ) m e a s u r e d i n t h i s w o r k and i n
p r e v i o u s s t u d i e s a r e p l o t t e d , a l o n g w i t h v a r i o u s summary a n a l y t i c
r e p r e s e n t a t i o n s , i n F i g u r e 6.
A t 291 K, k j was f o u n d t o be p r e s s u r e - d e p e n d e n t ,
and i t
r e a c h e d a h i g h - p r e s s u r e - l i m i t e d v a l u e o f (8.470.24) 1 0 ~
cm
molecule"
s " above 400 T o r r h e l i u m .
T h i s v a l u e f o r k j ( 2 9 1 K)
i s i n e x c e l l e n t agreement w i t h t h e r e s u l t s o f p r e v i o u s s t u d i e s
(17-19).
From 291-438 K, t h e r e a c t i o n mechanism i s d o m i n a t e d by
e l e c t r o p h i l i c a d d i t i o n o f OH t o t h e e t h y l e n e d o u b l e b o n d , and
t h e t e m p e r a t u r e dependence o v e r t h i s r a n g e o f t h e h i g h - p r e s s u r e l i m i t e d r a t e c o e f f i c i e n t may be r e p r e s e n t e d by t h e e x p r e s s i o n
k j ( T ) = (1.740.53) ""
exp (918214)/RT cm m o l e c u l e "
s" ,
w h e r e q u o t e d e r r o r s r e p r e s e n t 2 v a l u e s and
= ^^
(20,21).
Our o b s e r v a t i o n o f n o n e x p o n e n t i a l [OH] p r o f i l e s i n t h e
t e m p e r a t u r e r a n g e 438-666 can o n l y be i n t e r p r e t e d i n t e r m s o f
a c h e m i c a l p r o c e s s w h i c h r e f o r m s OH d u r i n g t h e 1-20 ms d u r a t i o n
of the experiment.
This process i s the decomposition back t o
r e a c t a n t s o f t h e t h e r m a l i z e d a d d u c t H 0 C H . I n d e e d , a t 591 K,
we o b s e r v e d t h a t a t v e r y l o n g t i m e s t h e [OH] d e c a y s a g a i n became
e x p o n e n t i a l w i t h a slope of - k
(see F i g u r e 4b). T h i s s i t u a t i o n
r e s u l t s o n l y when t h e OH + C H + M ^
0 0 ^ + M r e a c t i o n has
e s t a b l i s h e d dynamic e q u i l i b r i u m , w i t h the t h e r m a l i z e d adduct
s e r v i n g , i n e f f e c t , as a t e m p o r a r y s i n k f o r OH.
The r a t e c o
e f f i c i e n t d a t a d e r i v e d f r o m n o n e x p o n e n t i a l [OH] p r o f i l e s must
t h u s be c o n s i d e r e d a p p r o x i m a t e , and t h e y a r e i n c l u d e d i n F i g u r e
6 o n l y t o show t h e d e c r e a s i n g t r e n d i n " n e t " r e a c t i v i t y b e t w e e n
OH and C H w i t h i n c r e a s i n g t e m p e r a t u r e .
These r e s u l t s and t h e i r
i n t e r p r e t a t i o n are e n t i r e l y analogous to those obtained i n s t u d
i e s o f h y d r o x y l r a d i c a l a d d i t i o n t o a r o m a t i c h y d r o c a r b o n s (22-25).
We have a l s o made v e r y p r e l i m i n a r y k i n e t i c measurements on
R e a c t i o n (1) a t = 704 and 796 K.
The [OH] p r o f i l e s c o l l e c t e d
a t t h e s e t e m p e r a t u r e s show a l o w e r d e g r e e o f n o n e x p o n e n t i a l
f
1 2
12
lt
1+
lf

TULLY
13.
I
0
1
10
1
20
233
1 1 1
30
TIME (milliseconds)
40
50
F i g u r e k.
T y p i c a l [OH] c o n c e n t r a t i o n p r o f i l e s o b t a i n e d i n k i n e t i c
measurements o f t h e r e a c t i o n OH + C^H^ products; a , = 2 9 1 K ,
= 6 t o r r h e l i u m , a n d [CpH. ] = 3.W 1 0
m o l e c u l e cm" ; b ,
= 5 9 1 K , = 600 t o r r h e l i u m , a n d [ C ^ ] = 2 . 7 8 10
molecule
cm" .
(Reproduced w i t h p e r m i s s i o n from Ref. 2 0 . C o p y r i g h t
1983, North-Holland.)
3
1 3
lk

234
1000
F i g u r e 5 M e a s u r e d d e c a y r a t e k' a s a f u n c t i o n o f e t h y l e n e c o n
c e n t r a t i o n f o r e x p e r i m e n t s a t = 291K a n d = 100 t o r r h e l i u m .
T h r e e d i f f e r e n t C2H^/He s o u r c e g a s m i x t u r e s were s a m p l e d . The
e s t i m a t e d a c c u r a c y o f t h e [C^Hi] measurements i s 5%.
(Reproduced
w i t h p e r m i s s i o n from Ref. 20. C o p y r i g h t 1983, North-Holland.)

13.
TULLY
Elementary Combustion
Reactions: Kinetic Studies
235
\ \
\ .
\
\
10
to
to
10
0.5
1.5
\
\
\
\
.
1
2.5
3.5
1000 / ()
Figure 6.
Arrhenius p l o t f o r the r e a c t i o n OH + C^H^ products:
O, t h i s work, exponential [OH] decays ; X, t h i s work, nonexponential
[OH] decays; , Ref. I T ; , Ref. 2 1 ;
, Ref. 2 0 ;
,
Ref. 2 6 ;
*
' , Ref. 2 7 ; and
-, Ref. 2 8 .

236
behavior than those measured i n the range 515-666 K. However,

k* values at f i x e d ethylene concentrations v a r i e d somewhat when
p h o t o l y s i s pulse energies were changed; we have not yet i d e n t i
f i e d the source of t h i s e f f e c t . Nevertheless, s e m i - q u a n t i t a t i v e
estimates of k (704-796 K) may be d e r i v e d from these measure
ments, and the r e a c t i o n r a t e c o e f f i c i e n t appears to grow with
i n c r e a s i n g temperature over t h i s range. We b e l i e v e t h i s increase
in k j ( T ) to be caused by the onset of the hydrogen a b s t r a c t i o n
channel f o r Reaction (1), OH + C H
H 0 + C H .
Twoparameter expressions f o r t h i s a b s t r a c t i o n channel r a t e c o e f f i
c i e n t have p r e v i o u s l y been derived from complex, high-temperature
k i n e t i c s t u d i e s i n three reviews (26-28). As seen i n Figure 6,
our p r e l i m i n a r y measurements y i e l d poor agreement with these
recommendations. Further d i r e c t , " s i n g l e - r e a c t i o n
s t u d i e s of
t h i s a b s t r a c t i o n process w i l l be needed to c l a r i f y these d i s
crepancies.
In summary, we have demonstrated that p h o t o l y s i s / f l u o r e s
cence chemical k i n e t i c s techniques must e x p l o i t ongoing advances
i n l a s e r technology. A h i g h l y - s e n s i t i v e , quasi-cw, u l t r a v i o l e t
l a s e r source was constructed and used i n d e f i n i t i v e chemical
k i n e t i c s experiments.
OH-ethylene r e a c t i o n s have been charac
t e r i z e d i n terms of OH a d d i t i o n and hydrogen atom a b s t r a c t i o n
channels, and questions have been r a i s e d concerning both the
importance of the a d d i t i o n process and the accuracy of p r e s e n t l y
recommended k i n e t i c parameters f o r the a b s t r a c t i o n process at
combustion temperatures.
2
I+
11
Acknowledgment s
T h i s research was supported by the O f f i c e of Basic Energy
Sciences, U. S. Department of Energy. The author g r a t e f u l l y
acknowledges h e l p f u l d i s c u s s i o n s with J . . M. Goldsmith,
J . S. B i n k l e y , M. L. Koszykowski, C. F. Melius and R. E. Palmer.
He a l s o wishes to thank R. D. Gay, S. C. Gray, A. R. Van Hook
and G. D. Cosgrove f o r t h e i r c o n t r i b u t i o n s to t h i s work.
Literature Cited
1. Braun, W.; Lenzi, M. Discussions Faraday Soc. 1967, 44, 252.
2. Kurylo, M. J.; Peterson, N. C; Braun, W. J. Chem. Phys.
1970, 53, 2776.
3. Davis, D. D.; Huie, R. E.; Herron, J. T.; Kurylo, M. J.;
Braun, W. J. Chem. Phys. 1972, 56, 4868.
4. Stuhl, F.; Niki, H. J. Chem. Phys. 1972, 57, 3671.
5. Davis, D. D.; Fischer, S.; Schiff, R. J. Chem. Phys. 1974,
59, 628.
6. Atkinson, R.; Hansen, D. .; Pitts, J. N., Jr. J. Chem.
Phys. 1975, 62, 3284.
7. Tully, F. P.; Ravishankara, A. R. J. Phys. Chem. 1980, 84,
3126.

13. TULLY
237
8. Ravishankara, A. R.; Nicovich, J. M.; Thompson, R. L.;

Tully, F. P. J. Phys. Chem. 1981, 85, 2498.
9. McDonald, J. R.; Miller, R. G.; Baronavski, A. P. Chem.
Phys. 1980, 30, 133.
10. Lin, M. C.; McDonald, J. R. in "Reactive Intermediates in
the Gas Phase"; Setser, D. W., Ed.; Academic: New York,
1979; p. 233.
11. Sanders, N.; Butler, J. E.; Pasternack, L. R.; McDonald,
J. R. Chem. Phys. 1980, 48, 203.
12. Butler, J. E.; Fleming, J. W.; Goss, L. P.; Lin, M. C.
Chem. Phys. 1981, 56, 355.
13. Nelson, H. H.; McDonald, J. R. J. Phys. Chem. 1982, 86,
1242.
14. Inoue, G.; Akimoto, H.; Okuda, M. J. Chem. Phys. 1980,
72, 1769.
15. Dieke, G. H.; Crosswhite, H. M. J. Quantum Spectry. Rad.
Transfer 1962, 2, 97.
16. Tully, F. P.; Ravishankara, A. R.; Carr, K. Intern. J.
Chem. Kinet. 1983, 15, 1111.
17. Atkinson, R.; Perry, R. .; Pitts, J. N., Jr. J. Chem.
Phys. 1977, 66, 1197.
18. Lloyd, A. C.; Darnall, K. R.; Winer, A. M.; Pitts, J. N.,
Jr. J. Phys. Chem. 1976, 80, 789.
19. Cox, R. A. Intern. J. Chem. Kinetics Symp. 1975, 1, 379.
20. Tully, F. P. Chem. Phys. Lett. 1983, 96, 148.
21. Gordon, S.; Mulac, W. A. Intern J. Chem. Kinetics Symp.
1975, 1, 289.
22. Perry, R. .; Atkinson, R.; Pitts, J. ., Jr. J. Phys.
Chem. 1977, 81, 296.
23. Perry, R. .; Atkinson, R.; Pitts, J. N., Jr. J. Phys.
Chem. 1977, 81, 1607.
24. Tully, F. P.; Ravishankara, A. R.; Thompson, R. L.;
Nicovich, J. M.; Shah, R. C.; Kreutter, . M.; Wine, P. H.
J. Phys. Chem. 1981, 85, 2262.
25. Nicovich, J. M.; Thompson, R. L.; Ravishankara, A. R.
J. Phys. Chem. 1981, 85, 2913.
26. Warnatz, J. in "Chemistry of Combustion Reactions";
Gardiner, W. C., Jr., Ed.; Springer-Verlag: New York, 1983;
Chap. 5.
27. Westley, F. "Table of Recommended Rate Constants for
Chemical Reactions Occurring in Combustion"; NBSIR 79-1941,
November 1979.
28. Westbrook, C. K.; Dryer, F. L. "Chemical Kinetics Modeling
of Hydrocarbon Combustion"; Lawrence Livermore National
Laboratory Report No. UCRL-88651; February, 1983.
RECEIVED November 30, 1983

14
Reaction Rate of OH and C H near 1100 Kelvin
2
Laser Pyrolysis-Laser Fluorescence Measurement
PAUL W.
FAIRCHILD ,
G R E G O R Y P. S M I T H , and D A V I D R. C R O S L E Y
SRI International, Menlo Park, C A 94025
A laser pyrolysis/laser fluorescence apparatus has

been used to measure the rate constant for the
reaction of hydroxyl radicals with acetylene at
temperatures near 1100K. A pulsed CO laser rapidly
heats a mixture of SF , N , and H O , pyrolyzing the
peroxide to form OH. The radicals are detected by
laser-induced fluorescence, produced by a dye laser
fired at a variable time delay following the infrared
laser. Addition of C H causes a decrease in the OH
signal with time, permitting a measurement of the rate
constant. At 1100 50K a value of 3 x 10 cm sec
was obtained, with no significant pressure dependence
over the range 10-100 torr. A Troe-type calculation
has been carried out for the pressure-dependent
addition channel known to occur for this reaction at
lower temperature, and shows a temperature dependence
of the fall-off such that the rate channel should be
slow at 1100K. Thus our results and these previous
experiments are consistent, and a direct reaction
channel important above 1000K is indicated.
This
combined temperature/pressure dependence must be
included in combustion models incorporating detailed
chemical kinetics.
2
-13
-1
As e x e m p l i f i e d by s e v e r a l p a p e r s w i t h i n t h i s symposium, computer
models o f combustion p r o c e s s e s w h i c h i n c o r p o r a t e e x t e n s i v e and
d e t a i l e d c h e m i c a l k i n e t i c s a r e now f e a s i b l e .
Such c a l c u l a t i o n s
are
capable
of t r e a t i n g
systems
varying
widely
i n time
Current address: T R W , Space and Technology Group, Redondo Beach, CA 90278
0097-6156/ 84/ 0249-0239506.00/ 0


240
s c a l e - s t a b l e f l a m e s t h r o u g h d e t o n a t i o n s - and o v e r a l a r g e range
of t e m p e r a t u r e and p r e s s u r e . The i n p u t t o t h e s e models c o n s i s t s
o f m e c h a n i s t i c and r a t e c o n s t a n t d a t a f o r t h e r e a c t i o n s i n v o l v e d ;
f o r a t l e a s t some of t h e k e y r e a c t i o n s t h e s e r a t e c o n s t a n t s must
be w e l l d e t e r m i n e d f r o m i n d e p e n d e n t e x p e r i m e n t s .
Particularly
i m p o r t a n t i s k n o w l e d g e of t h e r a t e c o n s t a n t s a t i n t e r m e d i a t e and
high
temperatures
and,
i n cases
where
three-body
addition
mechanisms can c o n t r i b u t e , a t v a r y i n g p r e s s u r e s a t each t e m p e r a
ture.
S i m p l e e x t r a p o l a t i o n of room t e m p e r a t u r e v a l u e s i s o f t e n
i n a d e q u a t e f o r t h e s e p u r p o s e s , w h i l e measurements d i r e c t l y a t h i g h
t e m p e r a t u r e s , as i n f l a m e s t h e m s e l v e s , a r e o f t e n c o m p l i c a t e d by
t h e o c c u r r e n c e of o t h e r r e a c t i o n s as w e l l .
We have d e v e l o p e d a new t e c h n i q u e of l a s e r p y r o l y s i s / l a s e r
f l u o r e s c e n c e , o r LP/LF (1_), d e s i g n e d t o f u r n i s h d i r e c t measurement
of r a t e c o n s t a n t s of r e a c t i o n s i n v o l v i n g f r e e r a d i c a l s at e l e v a t e d
temperatures (800-1400K).
A p u l s e d CO2 l a s e r i s u s e d t o h e a t a
sample c o n t a i n i n g a p r e c u r s o r t h a t p y r o l y z e s t o f o r m r a d i c a l s .
These r a d i c a l s a r e t h e n d e t e c t e d u s i n g l a s e r - i n d u c e d f l u o r e s c e n c e
(LIF).
The measurement o f t h e r a d i c a l r e m o v a l r a t e s i n t h e
p r e s e n c e of added r e a c t a n t t h e n y i e l d s t h e r a t e c o n s t a n t f o r t h e
s e l e c t e d c o n d i t i o n s o f t e m p e r a t u r e (T) and p r e s s u r e ( P ) .
In t h e p r e s e n t s t u d y we have a p p l i e d the LP/LF method t o t h e
measurement o f t h e r a t e c o n s t a n t f o r t h e OH + C2H2 r e a c t i o n , a t
~ 1100K and between 10 and 100 t o r r .
T h i s r e a c t i o n may be o f
c r u c i a l i m p o r t a n c e i n t h e mechanism o f s o o t f o r m a t i o n , a t o p i c
a l s o t r e a t e d i n s e v e r a l p a p e r s w i t h i n t h i s symposium.
Previous
d i r e c t measurements have been p e r f o r m e d i n t h e range = 230 t o
420K, where a d i s t i n c t p r e s s u r e dependence i n d i c a t e d t h e dominance
of
an a d d i t i o n
mechanism.
We
find
little
o r no
pressure
dependence a t t h e e l e v a t e d
temperature
and
an o v e r a l l
rate
c o n s t a n t b e l o w t h e room t e m p e r a t u r e v a l u e .
A t h e o r e t i c a l d e s c r i p t i o n of t h e a d d i t i o n r e a c t i o n , based on
T r o e ' s f o r m u l a t i o n (_2) of u n i m o l e c u l a r r e a c t i o n r a t e t h e o r y , has
been c o n s t r u c t e d t o a d d r e s s t h e q u e s t i o n of t h e c o n s i s t e n c y of o u r
r e s u l t s and
the e a r l i e r
low t e m p e r a t u r e measurements.
These
c a l c u l a t i o n s show a d r a m a t i c combined t e m p e r a t u r e and p r e s s u r e
dependence o f t h i s r a t e c o n s t a n t w h i c h must be i n c l u d e d when t h i s
r e a c t i o n i s i n c o r p o r a t e d i n t o models of combustion c h e m i s t r y .
These
results
illustrate
the
need
to
combine
individual
experimental data w i t h a t h e o r e t i c a l overview i n order to o b t a i n a
d e s c r i p t i o n v a l i d o v e r t h e range of and l i k e l y e n c o u n t e r e d i n
combustion systems.
Laser P y r o l y s i s / L a s e r Fluorescence
The LP/LF t e c h n i q u e u t i l i z e s
s o u r c e and a p u l s e d dye l a s e r ,
CO2 l a s e r , as t h e probe l a s e r
e x p e r i m e n t a l s e t - u p i s shown
t a i n i n g an i n f r a r e d a b s o r b e r
p u l s e d CO2 l a s e r as t h e h e a t i n g
delayed i n time w i t h r e s p e c t to the
f o r d e t e c t i o n of the r a d i c a l s .
The
i n F i g u r e 1.
A gas m i x t u r e c o n
( S F , ) , a b a t h gas (), a r a d i c a l

14.
FAIRCHILD ET AL.
Reaction Rate of OH and C H

2
near 1100 Kelvin
p r e c u r s o r ( l U O / R ^ C ^ ) , and a r e a c t a n t (C2H2) f l o w s t h r o u g h t h e c e l l
and i s i r r a d i a t e d by t h e CC>2 l a s e r .
The S F ^ a b s o r b s t h e CC^ l a s e r
radiation
and c o l l i s i o n a l l y
transfers
this
energy
to the
s u r r o u n d i n g g a s . The t e m p e r a t u r e o f t h e h e a t e d m i x t u r e i s c h o s e n
by t h e C0 l a s e r f l u e n c e and t h e SF^ p r e s s u r e u s e d .
Once h e a t e d ,
thermal
decomposition
of
the peroxide
produces
hydroxyl
radicals.
The f r e q u e n c y d o u b l e d dye l a s e r i s t u n e d t o a n a b s o r p
t i o n l i n e o f t h e OH ( t y p i c a l l y t h e
l i n e f o r t h e (0,0) band o f
the
^ -^\
transition),
producing
fluorescence which i s
d e t e c t e d t h r o u g h a s m a l l monochromator and a v e r a g e d w i t h a g a t e d
boxcar i n t e g r a t o r .
V a r i a t i o n o f t h e d e l a y between t h e l a s e r s
p e r m i t s t h e r e l a t i v e OH d e n s i t y t o be mapped as a s f u n c t i o n o f
time f o l l o w i n g t h e i n i t i a l h e a t i n g p u l s e .
By t u n i n g t h e dye l a s e r
through a s e r i e s of r o t a t i o n a l a b s o r p t i o n l i n e s , the p o p u l a t i o n
d i s t r i b u t i o n among g r o u n d s t a t e r o t a t i o n a l l e v e l s and hence t h e
t e m p e r a t u r e c a n be d e t e r m i n e d a t e a c h d e l a y t i m e .
The dye l a s e r beam i s 2 mm i n d i a m e t e r and t h e f l u o r e s c e n c e
i s f o c u s s e d o n t o a 2 mm s l i t o r i e n t e d p e r p e n d i c u l a r t o t h e beam.
T h i s p r o v i d e s p o i n t - t y p e p r o b i n g o f t h e h e a t e d g a s , and p e r m i t s us
to s e l e c t a p a r t i c u l a r s p a t i a l r e g i o n f o r p e r f o r m i n g t h e k i n e t i c s
experiments.
F o l l o w i n g t h e i n i t i a l h e a t i n g p u l s e , a s e r i e s o f gas d y n a m i c
proceses take place, a l t e r i n g
the environment
i n the heated
r e g i o n , w h i c h i s c y l i n d r i c a l w i t h a 1 cm d i a m e t e r .
A shock wave
proceeds
outward
from the heated r e g i o n w h i l e a r a r e f a c t i o n
( e x p a n s i o n ) wave p r o p a g a t e s i n w a r d .
Upon r e a c h i n g t h e c e n t e r o f
the
h e a t e d c y l i n d e r , t h i s e x p a n s i o n wave r e f l e c t s and p r o c e e d s
o u t w a r d ; t h e n e t r e s u l t i s a t w o - s t a g e c o o l i n g and a n e x p a n s i o n o f
the
h e a t e d g a s . T h i s c o o l i n g p r o c e s s t a k e s p l a c e i n ~ 30 ,
t h a t i s , t h e t r a n s i t t i m e f o r t h e e x p a n s i o n wave a c r o s s t h e h e a t e d
r e g i o n a t t h e speed o f sound a t t h e e l e v a t e d t e m p e r a t u r e .
The
typical
cooling
o f 200-300K e f f e c t i v e l y
quenches
the high
a c t i v a t i o n energy r a d i c a l p r o d u c t i o n r e a c t i o n .
A f t e r this time,
t h e r e c o n t i n u e t o be m i n o r r e f l e c t e d and r e f r a c t e d waves n e a r t h e
center of the c e l l ,
b u t t h e d e n s i t y and t e m p e r a t u r e
remain
c o n s t a n t t o w i t h i n about 5% o v e r t h e 100 sec
time p e r i o d i n which
the
r e a c t i o n r a t e s a r e measured.
Further cooling occurs slowly
(< /) by t h e r m a l c o n d u c t i v i t y a c r o s s t h e i n t e r f a c e between
the
initially
h e a t e d and u n h e a t e d r e g i o n s , b u t does n o t a f f e c t
r e s u l t s on t h e t i m e s c a l e o f t h e p r e s e n t e x p e r i m e n t s .
Although
we
directly
measure
the temperature
i n each
e x p e r i m e n t , we must r e l y on a computer c a l c u l a t i o n ( 3 ) o f t h e
temperature-density
relationship
produced
by t h e g a s d y n a m i c
processes.
In order t o v e r i f y
that
t h e code i s p r o p e r l y
describing
the s i t u a t i o n ,
we
have
performed
a series of
measurements o f t h e OH d e n s i t y and t e m p e r a t u r e a s a f u n c t i o n o f
t i m e (_1_,_4) In F i g u r e 2 i s shown t h e e v o l u t i o n o f f o l l o w i n g t h e
CO2 l a s e r p u l s e f o r two d i f f e r e n t g a s m i x t u r e s , p u r e S F ^ a n d
SF^ +
In t h e l a t t e r c a s e , w h i c h h a s a h i g h e r h e a t c a p a c i t y
ratio,
a larger
cooling
i s observed.
These
measurements,
2
241

242
F i g u r e 1.
S c h e m a t i c d i a g r a m o f t h e e x p e r i m e n t . The t i m e d e l a y
A t i s a c t u a l l y c o n t r o l l e d b y an e x t e r n a l c i r c u i t t h a t f i r e s t h e
CO^ a n d YAG l a s e r s e q u e n t i a l l y .
The f l u o r e s c e n c e i s f o c u s e d o n t o
t h e s l i t o f a monochromator, d e t e c t e d by a p h o t o m u l t i p l i e r t u b e ,
and a v e r a g e d -with a g a t e d b o x c a r i n t e g r a t o r .
(Reproduced w i t h
p e r m i s s i o n f r o m Rf. 1.
C o p y r i g h t 1 9 8 2 , The C o m b u s t i o n I n s t i t u t e . )
Figure 2.
M e a s u r e d t e m p e r a t u r e as a f u n c t i o n o f t i m e , a t c e l l
center.
C i r c l e s , 100 t o r r SFg o n l y ,
-+
lÔOK. Note t h e
l o w v a l u e o f y p r o d u c e s l e s s c o o l i n g b y t h e e x p a n s i o n wave. S q u a r e s ,
100 t o r r S F g , 30 t o r r N , T. ...
= 1300K.
(Reproduced w i t h
p e r m i s s i o n f r o m Rf. 1.
C o p y r i g h t 1 9 8 2 , The C o m b u s t i o n I n s t i t u t e . )
T
i n
i a l

14.
FAIRCHILD ET AL.

2
near 1100 Kelvin
243
p e r f o r m e d a t t h e c e n t e r o f t h e c e l l where t h e i n f l u e n c e o f t h e g a s
dynamics
and p o t e n t i a l
fluctuations
are greatest,
are i n
qualititative
agreement
with
t h e code
calculations.
In
p a r t i c u l a r , the overcooling of the mixture
a t a b o u t 20
sec
appears i n both t h e computation and t h e experiment.
In Figure 3
i s shown t h e s i g n a l l e v e l a s a f u n c t i o n o f d e l a y t i m e a t t h e
center of the c e l l .
A n a r r o w g a t e i s u s e d on t h e b o x c a r s o t h a t
t h e s i g n a l i s p r o p o r t i o n a l t o t h e OH d e n s i t y and i s u n a f f e c t e d by
q u e n c h i n g c o l l i s i o n s (_4).
The r i s e i n t h e f l u o r e s c e n c e r e f l e c t s
t h e p r o d u c t i o n o f OH f r o m t h e p y r o l y s i s o f t h e ^ 0 2 * The s h o r t
i n d u c t i o n t i m e and l i n e a r r i s e o f t h e OH s i g n a l i n d i c a t e s t h a t t h e
decomposition
i s t i m e - i n d e p e n d e n t and t h a t t h e energy t r a n s f e r
f r o m t h e SF^ i s f a s t .
T h i s h a s been v e r i f i e d i n s u b s e q u e n t
e x p e r i m e n t s i n w h i c h t h e r o t a t i o n a l t e m p e r a t u r e o f t h e OH measured
by
1-1 and 0-0 e x c i t a t i o n a r e f o u n d t o be t h e same, w i t h i n
experimental error.
The s o l i d l i n e i n F i g . 3 shows t h e d e n s i t y
p r o f i l e p r e d i c t e d by t h e code a t t h e c e n t e r o f t h e c e l l .
The
d e c l i n e a n d f i n a l v a l u e , a t t i m e s > 50 , f o l l o w w e l l .
The
disagreement
between
computation
and experiment
f o r the
o s c i l l a t i o n n e a r 30 vsec i s c a u s e d a t l e a s t p a r t i a l l y b e c a u s e t h e
l a s e r beam a v e r a g e s o v e r t h e c e n t r a l 2 0 % o f t h e c e l l , w h i l e t h e
code p r e d i c t i o n s a r e f o r t h e e x a c t c e n t e r , where s u c h o s c i l l a t i o n s
a r e most s e v e r e .
H a l f w a y between t h e c e l l c e n t e r a n d t h e edge o f t h e h e a t e d
r e g i o n , t h e code p r e d i c t s o n l y m i n o r o s c i l l a t i o n s a n d f l u c t u a t i o n s
i n t h e d e n s i t y , and v e r y l i t t l e i n i t i a l o v e r c o o l i n g . T h i s i s t h e
r e g i o n c h o s e n f o r t h e k i n e t i c s measurements.
Confidence i n our
ability
to correctly
predict the density i n this
region i s
o b t a i n e d f r o m t h e p r e v i o u s measurements ( 1 ) o f t h e OH+CH^ r a t e
c o n s t a n t between 800 a n d 1400K, w h i c h show, w i t h i n t h e s c a t t e r o f
i n d i v i d u a l p o i n t s o f 3 0 % , v e r y good agreement w i t h t h e v a l u e s
e x p e c t e d f r o m a n e x t r a p o l a t i o n o f r e s u l t s up t o 1050K f r o m o t h e r
investigators.
The r a t e c o n s t a n t s a r e t h e n d e t e r m i n e d by m e a s u r i n g t h e time
dependence o f t h e OH d e n s i t y , f i r s t i n t h e a b s e n c e and t h e n i n t h e
p r e s e n c e o f a known amount o f added r e a c t a n t .
The measurements
begin
a t 30-40 d e l a y ,
after
the expansion
waves have
settled.
From t h e l o g a r i t h m o f t h e r a t i o v e r s u s t i m e , t h e r a t e i s
o b t a i n e d ; the slope of these r a t e s vs the r e a c t a n t pressure then
furnishes the rate constant f o r the given c o n d i t i o n s .
Reactant
c o n c e n t r a t i o n s a r e c h o s e n l a r g e enough t o e f f e c t an o b s e r v a b l e
d e c a y d u r i n g t h e 100 measurement t i m e i n t e r v a l , and a r e a l s o
l a r g e enough compared t o OH t o e n s u r e t h a t p s e u d o - f i r s t - o r d e r
kinetics i s valid.
One
f e a t u r e o f t h e L P / L F method i s t h e r a p i d h e a t i n g ,
compared t o c o n v e n t i o n a l h e a t e d f l o w s .
This permits reactions t o
be measured u n d e r c o n d i t i o n s when one o r a n o t h e r o f t h e r e a c t i o n s
m i g h t p y r o l y z e d u r i n g t h e much l o n g e r r e s i d e n c e t i m e s needed f o r
thermalization i n a flow c e l l .
On t h e o t h e r h a n d , t h e t e m p e r a t u r e
(measured f o r e a c h r u n by t h e r o t a t i o n a l e x c i t a t i o n s c a n s ) i s n o t

244
TIME ()
Figure 3 .
Narrow gate experiment measuring the d e n s i t y o f OH as a
f u n c t i o n of time a f t e r the C 0 heating p u l s e , at the center o f the
pyrolysis c e l l .
P o i n t s , experimental r e s u l t s ; s o l i d l i n e , p r e d i c
t i o n s from computer c a l c u l a t i o n ; and dashed l i n e , p y r o l y s i s r a t e o f
HÔ^ at the i n i t i a l temperature.
(Reproduced with permission from
Ref. k.
Copyright 1 9 8 3 , J o u r n a l o f Chemical P h y s i c s . )
2

14.
FAIRCHILD ET AL.

2
near 1100 Kelvin
245
known as a c c u r a t e l y as i n f l o w t u b e s ; t h e p r e c i s i o n i s 50K h e r e .
T h i s does n o t c o n s t i t u t e a s i g n i f i c a n t s o u r c e o f e r r o r i n t h e
p r e s e n t e x p e r i m e n t s , where t h e t e m p e r a t u r e
dependence o f t h e
r e a c t i o n r a t e i s g e n t l e , b u t may f o r o t h e r c a s e s .
Also, the
s u b s e q u e n t t h e r m a l c o n d u c t i v i t y c o o l i n g l i m i t s t h e range o f t i m e
o v e r w h i c h measurements c a n be made.
Experimental
results
D a t a f o r t h e decay o f t h e OH d e n s i t y f o r s e v e r a l p r e s s u r e s o f C9H2
a t a p a r t i c u l a r a n d a r e shown i n F i g . 4, a s w e l l as t h e p l o t
from which t h e r a t e constant f o r these c o n d i t i o n s i s determined.
The s c a t t e r e x h i b i t e d i s i n a c c o r d w i t h o u r e s t i m a t e s o f 10-20%
run-to-run error.
A s e r i e s o f s u c h measurements was made f o r b a t h
gas p r e s s u r e s r a n g i n g f r o m 10 t o 100 t o r r .
T y p i c a l bath gas
m i x t u r e s c o n t a i n e d e q u a l amounts o f N a n d SF^. The r e s u l t s a r e
g i v e n i n F i g . 5. As s e e n i n t h e f i g u r e , t h e r e a r e two s e t s a t
= 1070 50K a n d 1180 40K f o r w h i c h
the results are
indistinguishable within the error bars.
The dashed l i n e i s a
least-squares
f i t to the rate
c o n s t a n t s as a f u n c t i o n o f
pressure.
The f i t t e d
s l o p e i s c o n s i s t e n t w i t h no p r e s s u r e
v a r i a t i o n , given the spread i n t h e r e s u l t s .
We c o n c l u d e t h a t a t
t h i s t e m p e r a t u r e , ~ 100K, t h e OH + ^2^2
^
*- i n d e p e n d e n t o f
pressure
and proceeds
through
a
direct
channel
such
as
abstraction.
W i t h i n 2 e r r o r b a r s , a t l e a s t 6 5 % o f t h e r e a c t i o n
p r o c e e d s by t h i s c h a n n e l a t 100 t o r r .
Assuming o n l y a p r e s s u r e
i n d e p e n d e n t mechanism, t h e s e r e s u l t s g i v e k =(2.6 0.3) 1 0 "
cm s~"* a t 1140K a v e r a g e t e m p e r a t u r e .
P r e l i m i n a r y r u n s c a r r i e d o u t a t ~ 900K i n d i c a t e t h a t a t t h i s
cooler
temperature
t h e r e does e x i s t
a significant
pressured e p e n d e n t component ( 5 ) . The e r r o r b a r s shown i n F i g . 5 a r e
a v e r a g e d e v i a t i o n s f r o m t h e mean o f t h e 3-5 measurements made a t
e a c h and u s i n g v a r i o u s ^2
P
pressures.
Error
e s t i m a t e s d e r i v e d from d a t a s c a t t e r , l a s e r f l u c t u a t i o n s (monitored
a t l e s s t h a n 5%) and f l o w r e a d i n g a c c u r a c y , and u n c e r t a i n t i e s i n
the
density
resulting
from
both
error
i n t h e temperature
measurements and c o n f i d e n c e i n t h e code c a l c u l a t i o n s g i v e s i m i l a r
v a l u e s . E r r o r e s t i m a t e s a r e d i s c u s s e d i n more d e t a i l i n R e f s . O ,
_4, a n d 5 ) . The s c a t t e r o f t h e OH+CH^ r e s u l t s f r o m e x p e c t e d v a l u e s
agreed w e l l w i t h t h e e r r o r bars e s t i m a t e d s e p a r a t e l y i n t h i s
way.
The u n c e r t a i n t y o f ~ 50K i n e a c h t e m p e r a t u r e i s d i r e c t l y
o b t a i n e d from t h e s c a t t e r i n t h e Boltzmann p l o t s used t o o b t a i n
from the r o t a t i o n a l p o p u l a t i o n s .
2
Discussion
The r e a c t i o n o f OH w i t h C2H2 a p p e a r s t o have two p r i m a r y r e a c t i o n
p a t h w a y s . Measurements made i n t h e 230-430K t e m p e r a t u r e range (j6,
_7_, 8) show an unambiguous p r e s s u r e d e p e n d e n c e .
Thus a t t h e s e
cooler temperatures
t h e r e a c t i o n i s dominated
by a n a d d i t i o n
channel

246
1
13
k = 3.8 10" cm sec"
20
60
80
100
t ^sec)
Figure ha.
Ratio o f OH L I F s i g n a l with added C H t o that with no
added CpH^ as a f u n c t i o n o f delay time a f t e r the C 0 l a s e r p u l s e .
= 11TDK and = 32 t o r r .
C i r c l e s , 1.02 t o r r C H ; t r i a n g l e s ,
1.85 t o r r C H ; squares, 2.27 t o r r C H ; and diamonds, 2.53 t o r r
2
^2^2 *

FAIRCHILD ET AL.
Reaction Rate of OH and
C2H2
near 1100 Kelvin
14.
American Chemical
Society Library
1155 16th St. N. W.
D. C.
2003S
ACS Symposium Series;Washington,
American Chemical
Society:
Washington, DC, 1983.
247
248
OH + C H DEPENDENCE
20
40
60
(torr) S F
80
N
100
Figure 5. Measured value o f the OH + C^Hp r a t e constant as a func

t i o n o f t o t a l pressure o f SFg + N .
C i r c l e s , l l 8 0 + UOK; and t r i
angles, 1070
50K. Dashed l i n e i s a l e a s t - s q u a r e s f i t t o the
rate constants.
2

14.
FAIRCHILD ET AL.
near 1100 Kelvin
249
i
+ M j
C H 0H + M
(1)
1
1
*
i n w h i c h t h e i n i t i a l l y e n e r g e t i c a d d u c t C H O H i s s t a b i l i z e d by
c o l l i s i o n w i t h some o t h e r m o l e c u l e .
At higher temperatures the
reaction
likely
proceeds
by a
direct
mechanism,
probably
abstraction
OH + C H
C H + H 0
(2)
OH + C H
2
a l t h o u g h p r e v i o u s h i g h t e m p e r a t u r e measurements (9,
10) were made
o n l y i n a f l a m e , e a c h a t a s i n g l e p r e s s u r e , and must be s t r i c t l y
c o n s i d e r e d i n f e r e n t i a l r e g a r d i n g t h e r e a c t i o n c h a n n e l and r a t e .
The p r e s e n t e x p e r i m e n t a l r e s u l t s show c l e a r l y , h o w e v e r , t h a t a
d i r e c t , pressure-independent
channel
i s t h e m a i n one i n t h e
n e i g h b o r h o o d o f HOOK.
Our r e s u l t s
taken
together w i t h these lower
temperature
measurements (6_, 7j 8) r a i s e q u e s t i o n s w h i c h we have a t t e m p t e d t o
answer u s i n g u n i m o l e c u l a r and b i m o l e c u l a r r e a c t i o n r a t e t h e o r y .
The f i r s t i s , s i m p l y , a r e t h e r e s u l t s a t l o w and h i g h t e m p e r a t u r e
consistent?
F u r t h e r , what
i s the expected
behavior
i n the
i n t e r m e d i a t e r e g i o n and u n d e r what c o n d i t i o n s does t h e d i r e c t o r
a d d i t i o n channel dominate?
We have c a l c u l a t e d t h e a d d i t i o n c h a n n e l r a t e c o n s t a n t u s i n g
the
RRKM a p p r o a c h t o u n i m o l e c u l a r
r e a c t i o n r a t e t h e o r y , as
f o r m u l a t e d by T r o e (_2) t o match RRKM r e s u l t s w i t h a s i m p l e r
computational approach.
The p r e s s u r e dependence o f t h e a d d i t i o n
r e a c t i o n ( 1 ) c a n be s i m p l y d e c r i b e d by a L i n d e m a n n - H i n s h e l w o o d
mechanism,
written
most
conveniently
i n the d i r e c t i o n
of
decomposition of the s t a b l e adduct :
k
3
C H OH + M +
2
C H OH*
2
The
*
indicates a
decomposition.
Then
k
the rate constant
the
+ M
+ OH
having
(3)
(4)
sufficient
energy
for
" (1 + k / k _ [ M ] )
4
+ k./k [M])
0
_ 1
(5)
f o r t h e a d d i t i o n r e a c t i o n i s g i v e n by
ki
where
- l " k_ [M] + k
3
C H
molecule
and
C H OH
= K k_
1
are equilibrium constants.
(6)
Eqn. ( 5 ) p r o v i d e s

an
250
inadequate
d e s c r i p t i o n o f t h e k i n e t i c s o f r e a c t i o n ( 1 ) . The
reason
i s that
the r a t e
constants
k_^
and k^,
viewed
m i c r o s c o p i c a l l y , depend on t h e e n e r g y o f t h e h o t a d d u c t C2H2OH ,
and t h i s must be a c c o u n t e d f o r i n a p r o p e r d e s c r i p t i o n .
Here l i e s
a l s o t h e p h y s i c a l reason f o r the temperature
dependence o f t h e
p r e s s u r e f a l l - o f f r e g i o n o f t h e r a t e c o n s t a n t , t h a t i s , where t h e
r e a c t i o n i s between s e c o n d and t h i r d o r d e r o v e r a l l .
At higher
t e m p e r a t u r e , t h e C2H2OH w i l l span a l a r g e r r a n g e o f e n e r g y a n d
have a h i g h e r a v e r a g e e n e r g y .
Thus r e a c t i o n ( 4 ) w i l l be f a s t e r
w h i l e r e a c t i o n ( 3 ) w i l l r e q u i r e more c o l l i s i o n s t o s t a b i l i z e t h e
more e n e r g e t i c a d d u c t .
The c o r r e c t a p p r o a c h i s t h e s u b j e c t o f RRKM t h e o r y ; we u s e
t h e c o m p u t a t i o n a l l y s i m p l e r p r o c e d u r e as g i v e n by T r o e ( 2 ) .
He
writes
k_^
in
the
form
of
a
correction
to
the
Lindemann-Hinshelwood e x p r e s s i o n
log k
e l
- l o g [ k / ( l + k [M])]
(7)
+ logF /[1- {logik^/k^M])} ]

T
The
factor F
i s a m o d i f i c a t i o n of reduced
Kassel integrals
d e s i g n e d t o r e p l i c a t e f u l l RRKM r e s u l t s and i s c a l c u l a b l e f r o m
known o r e s t i m a t e d t h e r m o c h e m i c a l / s t r u c t u r a l p r o p e r t i e s o f t h e
adduct.
k
i s obtained from t r a n s i t i o n s t a t e theory, u s i n g the
p a r t i t i o n f u n c t i o n o f t h e a c t i v a t e d c o m p l e x and , t h e b a r r i e r
to recombination.
These a r e d e t e r m i n e d
f r o m t h e s i z e and t h e
t e m p e r a t u r e dependence o f t h e e x p e r i m e n t a l h i g h p r e s s u r e l i m i t i n g
rate constants.
k
i s g i v e n by a n e x p r e s s i o n i n v o l v i n g a
Lennard-Jones c o l l i s i o n r a t e c o n s t a n t , an i n t e g r a l i n v o l v i n g t h e
d e n s i t y of s t a t e s f o r the adduct,
approximated
h e r e by t h e
p r o c e d u r e g i v e n i n ( 2 ) , and a p a r a m e t e r w h i c h r e p r e s e n t s t h e
e f f i c i e n c y o f energy t r a n s f e r i n an average c o l l i s i o n between
C H O H and M.
The d e t a i l s o f t h e c o m p u t a t i o n a l p r o c e d u r e s a r e g i v e n i n ( 2 ) ,
and
t h e c h o i c e o f t h e p a r a m e t e r s u s e d i s d i s c u s s e d i n (5)
B r i e f l y , t h e a d d u c t s t r u c t u r e i s e s t i m a t e d w i t h good c o n f i d e n c e by
a n a l o g y t o s i m i l a r m o l e c u l e s , and
i s determined
t o be 1.2
k c a l / m o l e , by t h e b e s t f i t t o t h e t e m p e r a t u r e dependence o f k a s
d e t e r m i n e d by M i c h a e l e t a l . ( 7 ) o v e r t h e r a n g e 227-413K.
The
remaining parameters which a r e then a d j u s t e d t o produce the best
f i t a r e t h e f r e q u e n c i e s o f t h e CCO d e f o r m a t i o n and OH t o r s i o n mode
of t h e adduct i n t h e t r a n s i t i o n s t a t e , t h e thermodynamic s t a b i l i t y
o f t h e a d d u c t , and t h e v a l u e o f .
The v a l u e s u s e d f o r t h e s e
p a r a m e t e r s must be c o n s t r a i n e d t o be p h y s i c a l l y r e a s o n a b l e .
The
f i n a l v a l u e s , 205 cm" f o r e a c h o f t h e two v i b r a t i o n s , an a d d u c t
s t a b l e by 34 k c a l / m o l e , and a n a v e r a g e e n e r g y t r a n s f e r r e d p e r
c o l l i s i o n o f 0.36 k c a l / m o l e , f u l f i l l t h i s c r i t e r i o n .
The r e s u l t s o f t h e f i t s a r e compared i n F i g . 6 w i t h t h e
p r e s s u r e dependence o f k. f o r t h e f i v e t e m p e r a t u r e s i n v e s t i g a t e d
T

14.
FAIRCHILD ET AL.
100
C2H2
near 1100 Kelvin
251
200
P, torr
F i g u r e 6 . R a t e c o n s t a n t d a t a o f Rf. 7 ( c i r c l e s ) a n d R e f . 6 ( t r i a n g l e s ) f o r t h e OH + ^ r e a c t i o n a t 2 2 8 K , 2 5 T K , a n d 2 9 8 K . The
s o l i d l i n e i s a f i t t o t h e d a t a o f Rf. 7 a n d t h e d a s h e d l i n e i s a
f i t t o t h e d a t a o f R e f . 6 . See t e x t f o r d i s c u s s i o n o f t h e f i t t i n g
p r o c e d u r e . Marked on each p l o t i s t h e c a l c u l a t e d v a l u e o f k ^ ,

252
by M i c h a e l e t a l . ( 7 ) . We c o n s i d e r t h e computed c u r v e s t o be a n
e x c e l l e n t r e p r e s e n t a t i o n of the data over t h i s broad range.
Also
i n c l u d e d on F i g s . 6 a n d 7 a r e t h e r e s u l t s o f P e r r y and W i l l i a m s o n
( 8 ) f o r two t e m p e r a t u r e s .
T h e i r d a t a a r e n o t f i t as w e l l , due
l a r g e l y t o t h e p o i n t s i n e a c h c a s e a t t h e two h i g h e s t p r e s s u r e s
w h i c h do n o t c o n f o r m t o t h e g r a d u a l a p p r o a c h t o k p r e d i c t e d by
e x p r e s s i o n s ( 5 ) and ( 7 ) .
The s i n g l e p o i n t o f P a s t r a n a and C a r r
( 1 1 ) a t room t e m p e r a t u r e a n d 1 t o r r i s w i t h i n e x p e r i m e n t a l e r r o r
o f t h e v a l u e p r e d i c t e d by t h e f i t .
W i t h t h i s c o n f i d e n c e i n o u r t h e o r e t i c a l model o f t h e p r e s s u r e
dependence o f t h e a d d i t i o n c h a n n e l ( 1 ) f o r t h e OH + C2H2 r e a c t i o n
up
t o 420K,
we
may
extend
the calculations
to higher
temperature.
The r e s u l t s a r e shown i n F i g . 8 f o r a p r e s s u r e o f
100 t o r r , t h e h i g h e s t a t t a i n e d i n t h e LP/LF e x p e r i m e n t s , and a
p r e s s u r e o f 760 t o r r , c o r r e s p o n d i n g t o a n a t m o s p h e r i c
pressure
flame.
From F i g . 8 i t c a n be s e e n t h a t t h e a d d i t i o n c h a n n e l may be
expected t o c o n t r i b u t e only a minor p a r t of the o v e r a l l r e a c t i o n
r a t e f o r t h e c o n d i t i o n s o f o u r e x p e r i m e n t s p e r f o r m e d a t HOOK.
Some p r e s s u r e dependence a t 900K, as s e e n i n t h e p r e l i m i n a r y r u n s
at t h i s
lower
temperature
( 5 ) , i s a l s o i n accord w i t h the
calculation.
Thus t h e p r e s e n t r e s u l t s and t h o s e measured a t l o w e r
t e m p e r a t u r e s (_6^, _7_, 8) a r e c o n s i s t e n t . The p r e d i c t i o n s f o r t h e
i n t e r m e d i a t e temperature
r e g i o n may be u s e d as a g u i d e t o t h e
m o d e l l e r i n c l u d i n g t h i s r e a c t i o n i n a d e t a i l e d treatment of flame
chemistry.
We e m p h a s i z e , however, t h a t t h e c a l c u l a t i o n i s n o t a
substitute
f o r accurate
experimental
determination.
The
p a r a m e t e r s on w h i c h i t r e l i e s , w h i l e r e a s o n a b l e , a r e based more on
t h e h i g h p r e s s u r e end o f t h e l o w - t e m p e r a t u r e
d a t a whereas t h e
c r u c i a l r e g i o n f o r 1 atm and b e l o w i s much f u r t h e r i n t o t h e
f a l l - o f f at higher temperatures.
That i s , k (1 atm) depends on k
a t l o w t e m p e r a t u r e and k a t h i g h t e m p e r a t u r e .
(We a l s o n o t e t h e
the c a l c u l a t i o n s
shown i n F i g . 8 c o r r e s p o n d
t o 100 t o r r N2
p r e s s u r e , w h i l e t h e e x p e r i m e n t a l gas m i x t u r e i n c l u d e s s i g n i f i c a n t
amounts o f a more e f f i c i e n t c o l l i d e r , S F ^ .
Thus t h i s
rough
prediction
corresponds
to
lower
experimental
pressure,
a p p r o x i m a t e l y 50 t o r r ) .
A l s o i n c l u d e d on F i g . 8 i s t h e r a t e c o n s t a n t d e t e r m i n a t i o n
f o r r e a c t i o n ( 2 ) i n a f l a m e by F e n i m o r e and J o n e s ( 9 ) . The l i n e
drawn i n t h i s r e g i o n f o r t h e t e m p e r a t u r e dependence o f t h e d i r e c t
r e a c t i o n ( 2 ) corresponds t o an A r r h e n i u s form.
I t has a f r e q u e n c y
f a c t o r 2 1 0 " cnr* s e c " a n d a c t i v a t i o n e n e r g y o f 9 k c a l / m o l e ,
e s t i m a t e d r e s p e c t i v e l y by t h e OH + CH^ A - f a c t o r and an e s t i m a t e o f
f o r r e a c t i o n ( 2 ) c o u p l e d w i t h a 2 k c a l / m o l e b a r r i e r .
While
this
forms a r e a s o n a b l e
d e s c r i p t i o n o f t h e two e x p e r i m e n t a l
r e s u l t s , i t w o u l d be d e s i r a b l e t o measure p o i n t s i n t e r m e d i a t e i n
temperature.
F i n a l l y , there a r e s e v e r a l questions not addressed i n the
present d i s c u s s i o n .
One i s t h e z e r o - p r e s s u r e i n t e r c e p t a t l o w
t e m p e r a t u r e i n f e r r e d by M i c h a e l e t a l . ( 7 ) and a t t r i b u t e d t o a
1 1

C2H2
near 1100 Kelvin
FAIRCHILD ETAL.
F i g u r e 7.
Same a s F i g u r e 6 f o r 362K a n d 1+20K.

254
Figure 8.
L o g k v s . l / T p l o t f o r t h e OH + C H r e a c t i o n .
Triangles,
100 t o r r v a l u e s o f R e f . 7 ; s q u a r e s , v a l u e s a t t h e h i g h e s t p r e s s u r e s
o f R e f . 7; d i a m o n d , f l a m e measurement o f R e f . 9 ; i n v e r t e d t r i a n g l e ,
f l a m e measurement o f R e f . 1 0 ; c i r c l e , t h e a v e r a g e o f o u r t w e l v e
experimental points.
k^ " l i n e i s a t r a n s i t i o n s t a t e t h e o r y h i g h p r e s s u r e a d d i t i o n r a t e c o n s t a n t t h a t f i t s t h e d a t a o f R e f . 7.
The
100 t o r r a n d 760 t o r r l i n e s a r e c o m p u t a t i o n a l f i t s t o t h e d a t a o f
R e f . 7 a t t h e s e t o t a l p r e s s u r e s . The a b s t r a c t i o n k. l i n e i s drawn
w i t h an A f a c t o r o f 2 1 0 "
cm s e c " and o f 9 K c a l / m o l .
p
1 1

14.
FAIRCHILD ET AL.

2
near 1100 Kelvin
255
r a p i d d i r e c t rearrangement of the adduct to form ketene and

-atom.
Our f i t i n d i c a t e s the data of R f . 7) i s c o n s i s t e n t with
a standard a d d i t i o n process, Reactions (1,3 and 4 ) , but do not
demand the t o t a l absence of ketene formation.
The rate constant
at 1 t o r r (11) suggests t h i s does not occur to an appreciable
degree, while molecular beam measurements (12) show ketene to be a
direct
product
at
low
pressure
although
in
undetermined
quantity.
Second, questions
of thermal decomposition of
the
s t a b i l i z e d adduct at high temperatures reduce f u r t h e r the net
c o n t r i b u t i o n of the a d d i t i o n channel.
L i f e t i m e s under 30 sec
are
p r e d i c t e d by the model for temperatures above 1000K at 100 t o r r .
F i n a l l y the reverse of the d i r e c t r e a c t i o n (2)
could
affect
measurements i n the presence of water vapor.
These issues are
discussed i n Ref. ( 5 ) .
Conclusions
The
LP/LF apparatus, developed
f o r the study of bimolecular
r a d i c a l reactions
at elevated
temperature, has been used f o r
measurements of the OH + C H2 r e a c t i o n .
At HOOK, t h i s r e a c t i o n
i s independent of pressure, i n d i c a t i n g the primary channel i s a
direct
route r a t h e r than a d d i t i o n to
form an adduct.
A
Troe-based
calculation
has
been performed f o r
the
addition
mechanism, known to dominate at low temperature from the pressure
dependence of p r e v i o u s l y measured rate constants between 230 and
430K.
The r e s u l t s of the c a l c u l a t i o n show a dramatic change i n the
f a l l - o f f as temperature i n c r e a s e s , and that the a d d i t i o n channel
i s expected to be very slow at HOOK and 100 t o r r .
For use i n
computer models
of
combustion systems i n c o r p o r a t i n g d e t a i l e d
chemical
kinetics,
it
is
important
that
this
combined
pressure-temperature dependence be taken i n t o account.
This i s
a l l the more e s s e n t i a l when a range of and may be encountered
during a given combustion process.
These
results
illustrate
the
desirability
of
combining
experimental r e s u l t s
with a t h e o r e t i c a l overview i n chemical
kinetics
investigations.
While
the
computations
for
the
intermediate , region are not a q u a n t i t a t i v e s u b s t i t u t e f o r
f u r t h e r experiments,
they can provide a u s e f u l guide for the
i n c l u s i o n of t h i s r e a c t i o n i n combustion chemical networks.
2
Acknowledgments
We thank David M. Golden for u s e f u l d i s c u s s i o n s and the suggestion
that we undertake the c a l c u l a t i o n of the a d d i t i o n channel.
This
research was supported by the Department of Energy, D i v i s i o n of
Basic Energy Sciences, under Contract No. DE-AC03-81ER10906.

256
Literature Cited
1. P. W. Fairchild, G. P. Smith, and D. R. Crosley, Nineteenth
Symposium (International) on Combustion, The Combustion
Institute, Pittsburgh, 1982, p. 107.
2. J. Troe, J. Phys. Chem. 83, 114 (1979); J. Chem. Phys. 66,
4758 (1977).
3. L. Seaman, "SRI PUFF 8 Computer Program for One-Dimensional
Stress Wave Propagation," Final Report, SRI Project 6802,
Menlo Park, 1978.
4. P. W. Fairchild, G. P. Smith and D. R. Crosley, J. Chem.
Phys., 79, 1795 (1983).
5. G. P. Smith, P. W. Fairchild and D. R. Crosley, J. Chem.
Phys., to be published.
6. R. A. Perry, R. Atkinson and J. N. Pitts, Jr., J. Chem.
Phys., 67, 5577 (1977).
7. J. V. Michael, D. F. Nava, R. P. Borkowski, W. A. Payne and
L. J. Stief, J. Chem. Phys. 73, 6108 (1980).
8. R. A. Perry and D. Williamson, Chem. Phys. Lett. 93, 331
(1982).
9. C. P. Fenimore and G. W. Jones, J. Chem. Phys. 41, 1887
(1964).
10. W. G. Browne, R. G. Porter, J. D. Verlin, and A. H. Clark,
Twelfth Symposium (International) on Combustion, The
Combustion Institute, Pittsburgh, 1969, p. 1035.
11. A. Pastrana and R. W. Carr, Jr., Int. J. Chem. Kin. 6, 587
(1974).
12. J. R. Kanofsky, D. Lucas, F. Pruss and D. Gutman, J. Phys.
Chem. 78, 311 (1974).
1983

15
3
Measurement of the C ( ) and C (X )

Disappearance Rates with O from 298 to 1300 Kelvin
2
STEVEN L. BAUGHCUM and RICHARDC.OLDENBORG
Chemistry Division, Los Alamos National Laboratory, Los Alamos, M 87545
The disappearance rates of C (a , v=0, 1, and

2) and C (X , v=0) in the presence of O have
2
been measured over the 298-1300 temperature

range. The C is produced by multiple-photon
dissociation of CF3CCCF3 at 193 nm and probed by
laser-induced fluorescence. The disappearance
rate of C (a , v=0) as a function of tempera
ture can be extremely well represented by the
Arrhenius expression k(T) = A exp (-E/RT), with
A = 1.49 0.03 x 10- cm molecule s and
= 0.98 0.02 kcal/mole. The quality of the fit
over such a large temperature range provides a
test of previously proposed models of the C2
+ O system, which do not predict simple Arrhen
ius behavior. Our results are consistent with a
model in which C and C are interconverted by
O via a long range interaction and reaction
occurs upon still closer approach, so that the
identity of the initial state is lost before
reaction occurs. Experiments with C (X ) + O
are consistent with this model.
2
11
-1
-1
Although radical-molecule r e a c t i o n s p l a y an important r o l e i n

combustion, s t a t e - s e l e c t e d measurements o f the r e a c t i o n rate
constants a t high temperature have been made f o r only a few
reactions.
Data on the temperature dependence o f r a d i c a l molecule r e a c t i o n rate constants are v i t a l f o r assessing the
importance of various r e a c t i o n s i n combustion and s i m i l a r high
temperature processes
and provide
important i n s i g h t i n t o the
d e t a i l s of the p o t e n t i a l energy surfaces i n v o l v e d .
Radicals
which are e l e c t r o n i c a l l y or v i b r a t i o n a l l y e x c i t e d may react with
d i f f e r e n t rates and produce d i f f e r e n t products compared to the
0097-6156/ 84/0249-0257506.00/ 0
258
ground s t a t e r a d i c a l .
T h u s , i t i s i m p o r t a n t t o do s t a t e s e l e c
t i v e m e a s u r e m e n t s , where p o s s i b l e .
D e t a i l e d r e a c t i o n mechanisms and k i n e t i c s a r e b e s t s t u d i e d
i n an e n v i r o n m e n t i n w h i c h s p e c i f i c r e a c t i o n s o r s e q u e n c e s o f
r e a c t i o n s c a n be i s o l a t e d .
I n o r d e r t o c o n d u c t s u c h s t u d i e s , we
have c o n s t r u c t e d a c e l l i n w h i c h t h e t e m p e r a t u r e c a n be c o n t i n u
o u s l y v a r i e d o v e r t h e 298-1300 t e m p e r a t u r e r a n g e . R a d i c a l s a r e
p r o d u c e d by p h o t o l y s i s o f s u i t a b l e p r e c u r s o r s w i t h a p u l s e d r a r e
g a s - h a l i d e e x c i m e r l a s e r and t h e r a d i c a l p o p u l a t i o n s p r o b e d by
laser-induced fluorescence (LIF).
LIF i s a powerful tool f o r
s t u d y i n g k i n e t i c p r o c e s s e s , s i n c e i t i s b o t h v e r y s e n s i t i v e and
s t a t e s e l e c t i v e , a l l o w i n g the study of r a d i c a l - m o l e c u l e reactions
u n d e r pseudo f i r s t o r d e r c o n d i t i o n s .
Furthermore, since s p a t i a l
l y i t i s a p o i n t d i a g n o s t i c , h i g h t e m p e r a t u r e s t u d i e s c a n be done
i n a r e l a t i v e l y s m a l l v o l u m e , w h i c h m i n i m i z e s some o f t h e e x p e r i
mental d i f f i c u l t i e s a s s o c i a t e d w i t h the h i g h temperatures, par
t i c u l a r l y thermal gradients.
A v a r i e t y o f i m p o r t a n t r a d i c a l s can
be p r o b e d by L I F , i n c l u d i n g OH, HS, CH, C , C and C H 0 .
Our i n i t i a l e x p e r i m e n t s have c e n t e r e d on t h e C
radical,
w h i c h i s known t o e x i s t i n h i g h c o n c e n t r a t i o n s i n f l a m e and o t h e r
combustion environments.
The p r e s e n c e o f a l o w - l y i n g e x c i t e d
electronic state
( a ^ ) w i t h i n 610 cm"
o f the ground
state
2
(X !*)
(1)
requires
that
kinetic
s t u d i e s be
done on b o t h
states
s i n c e b o t h w i l l be s i g n i f i c a n t l y p o p u l a t e d a t t h e t e m p e r a t u r e s o f
interest.
The k i n e t i c s o f C
w i t h a v a r i e t y o f r e a c t a n t s have
b e e n i n v e s t i g a t e d a t room t e m p e r a t u r e (2-7) and o v e r t h e 300600 t e m p e r a t u r e range ( 8 - 1 0 ) . We c h o s e t o s t u d y t h e C
+ 0
r e a c t i o n as a t e s t o f o u r a p p a r a t u s and t o f u r t h e r e v a l u a t e t h e
model p r o p o s e d by M a n g i r and c o w o r k e r s (6) w h i c h p r e d i c t e d nonArrhenius behavior of the disappearance rate c o n s t a n t s .
2
Experimental
The h i g h t e m p e r a t u r e c e l l ( F i g u r e 1) i s b a s e d on a d e s i g n by
F e l d e r and c o w o r k e r s (1_1).. A c e n t r a l h i g h - p u r i t y a l u m i n a t u b e i s
h e a t e d r e s i s t i v e l y i n two zones by P t / 4 0 % Rh r e s i s t a n c e w i r e .
T h e r m a l i n s u l a t i o n i s p r o v i d e d by an a l u m i n a h e a t s h i e l d s u r
r o u n d e d by z i r c o n i a f i b e r i n s u l a t i o n , w i t h t h e w h o l e a s s e m b l y
e n c l o s e d i n a w a t e r - c o o l e d b r a s s vacuum chamber. The t e m p e r a t u r e
i s measured b y t h e r m o c o u p l e s i n s e r t e d t h r o u g h 0 - r i n g s e a l s t o
p r o b e v a r i o u s r e g i o n s o f t h e oven.
The t h e r m o c o u p l e o u t p u t s a r e
sent to a M i c r i c o n microprocessor which a u t o m a t i c a l l y regulates
the h e a t e r c u r r e n t .
The r e a c t a n t and b u f f e r g a s e s a r e i n t r o d u c e d
a t t h e b o t t o m o f t h e c e l l and a r e h e a t e d as t h e y f l o w s l o w l y
(~0.15 sm) t h r o u g h t h e c e n t e r t u b e . A s m a l l amount o f t h e r a d i
cal p r e c u r s o r i n a helium mixture i s introduced v i a a waterc o o l e d v a r i a b l e l e n g t h i n l e t s y s t e m w i t h i n a few cm o f t h e o p t i
c a l p o r t s t o m i n i m i z e p y r o l y s i s and p r e - r e a c t i o n p r o b l e m s .
The
p r e s s u r e i s measured
with
a
c a p a c i t a n c e manometer
and
gas

15.
BAUGHCUM AND OLDENBORG
C (a Il )
2
and C (X X ) Disappearance Rates

2
259
flows with c a l i b r a t e d Tylan mass flow meters. The gas flow i s

s u f f i c i e n t l y f a s t to assure a f r e s h gas mix f o r each l a s e r shot.
At the pressures (20 t o r r ) and flow c o n d i t i o n s used, the thermal
gradients i n the region probed were l e s s than 1%.
The p h o t o l y s i s l a s e r i s a Lambda Physik EMG-102 rare gash a l i d e excimer l a s e r operating at 193 nm.
The r a d i c a l popula
t i o n s are probed using e i t h e r Quanta-Ray Nd:YAG laser-pumped dye
l a s e r s with n o n - l i n e a r mixing c r y s t a l s where appropriate or a
Molectron n i t r o g e n - l a s e r pumped dye l a s e r .
The excimer l a s e r
beam i s focused to a 3 x 3 mm beam and the probe l a s e r s are
combined using s u i t a b l e d i c h r o i c mirrors to probe the center of
t h i s spot.
The fluorescence i s imaged with a lens through a
s u i t a b l e d i e l e c t r i c f i l t e r onto the element of an RCA 31034A
p h o t o m u l t i p l i e r tube. The s i g n a l i s a m p l i f i e d and processed with
a PAR Model 162 boxcar averager.
The output of the boxcar i s
then sent to a computer f o r s o p h i s t i c a t e d data a n a l y s i s .
To
measure the chemical l i f e t i m e of the r a d i c a l , the time delay
between the excimer l a s e r and the probe l a s e r i s scanned while
monitoring the t o t a l fluorescence i n the wavelength region of the
band of i n t e r e s t .
For s p e c t r a l scans, the time delay i s f i x e d
and the dye l a s e r i s scanned over the region of i n t e r e s t .
The C
r a d i c a l i s produced by multiple-photon d i s s o c i a t i o n
of CF3CCCF3 at 193 nm.
Approximately 20 t o r r of helium i s used
to t r a n s l a t i o n a l l y and r o t a t i o n a l l y e q u i l i b r a t e the C with the
bath gas.
The d i s s o c i a t i o n produces both *C and C
and a s i g
n i f i c a n t amount of the C
i s v i b r a t i o n a l l y e x c i t e d . Our exper
iments i n d i c a t e that at these pressures helium i s not e f f e c t i v e
at v i b r a t i o n a l l y quenching the C , although the r a p i d r o t a t i o n a l
t h e r m a l i z a t i o n i s c l e a r l y evident.
For measurements of the
r e a c t i o n rates of C , 1-2 mtorr of C F 3 C C C F 3 i s used with 20 t o r r
of 99.99% helium and 0-0.8 t o r r of 99.99% 0 .
The C ( a i l , v=0) i s probed by e x c i t a t i o n of the Swan bands
2
<- a n
(d n
) on
the
(0,0) band at 516 nm
and
the fluorescence
from the (0,1) band monitored at 564 nm (I).

Excited vibrations
are probed e i t h e r by e x c i t a t i o n of the (v,v) band while moni
t o r i n g the (v,v+l) band or by e x c i t a t i o n of the ( v - l , v ) band with
observation
initially
x
(A n
of
the
monitored
<r **) on
(v-l,v-l)
by
either
band
excitation
the
(4,0)
fluorescence.
of
band
the
Phillips
at 691
nm
C (X !^)
2
band
or the
was
system
(3,0)
band at 771 nm while monitoring e i t h e r the (4,1) fluorescence at

791 nm or the (3,1) fluorescence at 899 nm.
Unfortunately, since
t h i s t r a n s i t i o n i s r e l a t i v e l y weak with a r a d i a t i v e l i f e t i m e of
11 Ms (12) and i n the red, monitoring the *C i s very d i f f i c u l t
particularly
at high temperatures
where blackbody
radiation
provides a s i g n i f i c a n t source of noise i n the experiments when
monitoring red f l u o r e s c e n c e .
LIF probes i n which the f l u o r
escence i n the blue or u l t r a v i o l e t i s monitored are much more
2

260
useful
f o r high temperature
1
bands
(D !
<- X !
experiments.
(1) would be
ideal
For
C ,
the M u l l i k e n
but the spectra a r i s i n g
from d i f f e r e n t v i b r a t i o n a l s t a t e s overlap badly.

these d i f f i c u l t i e s , we have used double resonance
1
probe
for C ( X I p .
The
(3,0)
band
of the A ^
<- X !*
transi
t i o n i s e x c i t e d at 771 nm.
F i f t y nanoseconds l a t e r , a second
l a s e r e x c i t e s the (2,3) band of the C
<- A !!
t r a n s i t i o n at
'
g
u
404 nm and fluorescence i s monitored from the (2,1) band at
359 nm.
Since
the
radiative
lifetime
of the C s t a t e i s
32 ns (13) the process i s very e f f i c i e n t and a much higher
s i g n a l - t o - n o i s e r a t i o i s obtained than with simple LIF on the
P h i l l i p s band. Further d e t a i l s of t h i s d i a g n o s t i c w i l l be pre
sented elsewhere (14).
1
To surmount
LIF as the
Results
3
The time behavior of the C ( a F I ) p o p u l a t i o n under t y p i c a l condi

t i o n s i s i l l u s t r a t e d i n F i g u r e 2. The very f a s t r i s e occurs when
the excimer l a s e r f i r e s and the C
i s produced. There i s some
e a r l y complicated time behavior followed by a much longer s i n g l e
exponential decay. The a n a l y s i s of the long time behavior i s the
goal of t h i s paper.
The more complicated a n a l y s i s of the e a r l y
time behavior, which depends on the r e a c t i o n r a t e , c o l l i s i o n a l
intersystem c r o s s i n g r a t e , v i b r a t i o n a l energy t r a n s f e r r a t e s , and
the r e l a t i v e 0 / 0
quantum y i e l d s from the d i s s o c i a t i o n , w i l l
be presented i n a l a t e r paper (140.
A Stern-Volmer p l o t of the disappearance rate of C ( a F I ,
2
v=0) as a f u n c t i o n of oxygen pressure at 886 i s shown i n

F i g u r e 3. The slope of t h i s p l o t i s the r e a c t i o n rate constant of
C ( a n , v=0) with 0
at 886 K.
The q u a l i t y of the f i t gives a
3
good i n d i c a t i o n of the p r e c i s i o n of the measurements.

s i m i l a r q u a l i t y were obtained f o r the other temperatures
P l o t s of
studied.
A l o g a r i t h m i c p l o t of the measured rate constants vs ^ f o r

the f i r s t
l e v e l s of the a n
s t a t e i s shown i n
u
F i g u r e 4.
The s t r a i g h t l i n e through the v=0 p o i n t s i s a f i t to
the Arrhenius equation, k(T) = A exp (-E/RT) with A = 1.49 0.03
x 10"
cm m o l e c u l e " s " and = 0.98 0.02 kcal/mole.
As can
be seen, the v=0 s t a t e i s very w e l l represented by the Arrhenius
expression.
The e x c i t e d v i b r a t i o n s do not e x h i b i t Arrhenius
behavior and the curves drawn through those p o i n t s are simply f o r
v i s u a l i z a t i o n of the data.
At room temperature,
the e x c i t e d
v i b r a t i o n a l l e v e l s disappear r a p i d l y upon c o l l i s i o n s with oxygen.
At higher temperatures, the rates f o r the v=0, v=l, and
v=2
s t a t e s seem to converge.
The d e t a i l e d a n a l y s i s of the temporal
11
three v i b r a t i o n a l

15.
Figure 1.
C ( Uj
2
and C (X X )
2
Disappearance Rates
Diagram o f the high-temperature
261
cell.
TIME (/is)
Figure 2 .
T y p i c a l time behavior o f d a ) w i t h 0^ pressure =
0 . 5 6 8 t o r r , helium pressure = 2 0 . 0 8 l t o r r , temperature = 886 K.

262
Figure
Log p l o t o f t h e measured disappearance r a t e
f o r C ( a , = 0, 1, a n d 2) w i t h 0 v s . l / T .
2

constants
15.
C (sl UJ
2
and
C (X X )
2
Disappearance Raies 263
b e h a v i o r o f t h e v=0 s t a t e s u p p o r t s t h e i d e a t h a t a t room t e m p e r a
t u r e v i b r a t i o n a l r e l a x a t i o n o f t h e e x c i t e d s t a t e s dominates t h e
k i n e t i c s w h i l e a t higher temperatures t h e e x c i t e d v i b r a t i o n a l
s t a t e s r e a c t w i t h v i b r a t i o n a l r e l a x a t i o n p l a y i n g a more m i n o r
role.
The
d a t a f o r t h e C ( X I ^ , v=0) s t a t e a r e p r e s e n t e d i n
1
F i g u r e 5. The s t r a i g h t
line
superimposed
on t h e p l o t
corresponds
of the Arrhenius f i t of the a n

(v=0) d a t a . The
u
measured p o i n t s f a l l s l i g h t l y b e l o w t h e s t r a i g h t l i n e r e p r e
senting the a state data.
The r e a s o n f o r t h i s w i l l be d i s c u s s e d
later.
to the r e s u l t s
Discussion
In t h e C
+ 0
system,
three b a s i c processes can occur:
1
C
+ 0
+ 0
Products
(1)
P r o d u c t s
(2)
k
e
3
C
1
r ~ * ^
ê
C
+
2
The
d i f f e r e n t i a l e q u a t i o n s f o r t h e s e p r o c e s s e s c a n be s o l v e d
a n a l y t i c a l l y and t h e r e s u l t s have b e e n p r e s e n t e d b y M a n g i r and
c o - w o r k e r s ( 6 ) . They s t u d i e d t h i s s y s t e m a t room t e m p e r a t u r e and
showed t h a t t h e i n t e r s y s t e m c r o s s i n g r a t e c o n s t a n t , k^ = 2.7 x
- 1 1
_ 1
- 1
10
c m m o l e c u l e s , was much f a s t e r t h a n t h e o b s e r v e d r e a c
t i o n rate constant.
I n t h a t c a s e , t h e e q u a t i o n s c a n be s i m p l i
fied t o give
k- + K k
( 4 )
obs =
where k ^
Q
both
i s t h e e x p e r i m e n t a l l y observed
3
and C
= i ^ e
disappearance
and i s t h e e q u i l i b r i u m c o n s t a n t ,
= -f
g
e x p (-
l
/RT)
J

rate for
264
0.5
1.0
1.5
2.0
1/T 1 0 0 0
2.5
3.0
3.5
(K" )
Figure
Log p l o t o f the disappearance r a t e constant f o r
C ( , = 0) with 0 v s . l / T . The s t r a i g h t l y i e i s the r e s u l t
or t h e a n a l y s i s o f the Arrhenius f i t o f the C (a
, = 0) data.
g

15.
C (a U )
2
and C (\'V )
Disappearance Rates 265
i s t h e e n e r g y s e p a r a t i o n b e t w e e n t h e s i n g l e t and t r i p l e t
s t a t e s , 610 c m " , and g
and g j a r e t h e d e g e n e r a c i e s o f t h e
t r i p l e t and s i n g l e t s t a t e s , r e s p e c t i v e l y .
Over t h e t e m p e r a t u r e
r a n g e o f o u r s t u d y , 298-1300 K, t h e e q u i l i b r i u m c o n s t a n t v a r i e s
f r o m 0.32 t o 3.06. T h u s , t h e t e m p e r a t u r e dependence o f t h e
o b s e r v e d d i s a p p e a r a n c e r a t e c o n s t a n t i s e x p e c t e d t o be n o n Arrhenius unless k
= k , w h i c h as a f i r s t a p p r o x i m a t i o n seems
unlikely.
P r e v i o u s e x p e r i m e n t s (10) i n t h e 300-600 r a n g e c o u l d
n o t d e t e r m i n e i f t h e d a t a were A r r h e n i u s i n b e h a v i o r o r n o t . Our
d a t a c l e a r l y shows t h a t t h e o b s e r v e d d i s a p p e a r a n c e r a t e c o n s t a n t
can be f i t e x t r e m e l y w e l l t o t h e f o r m
1 3
k(T)
= A e x p (-E/RT)
(5)
r e s u l t implies that k = k .
I n t e r s y s t e m c r o s s i n g b e t w e e n C and C b y c o l l i s i o n s w i t h
oxygen i s s p i n
allowed
and a p p a r e n t l y
efficient
since the
singlet-triplet
separation
i s o n l y 610 cm" .
Normally, the
c h e m i s t r y o f t h e s i n g l e t a n d t r i p l e t s t a t e s w o u l d be e x p e c t e d t o
be v e r y d i f f e r e n t and t h e a p p a r e n t r e s u l t t h a t k j = k i s t h e r e
fore
somewhat
surprising.
However,
i f the s i n g l e t - t r i p l e t
c r o s s i n g o c c u r s a t l o n g i n t e r a c t i o n d i s t a n c e s between t h e C and
0
and i f r e a c t i o n t h e n o c c u r s upon c l o s e r a p p r o a c h , t h e i d e n t i t y
of t h e i n i t i a l C
s t a t e w o u l d be l o s t .
Under t h e s e c i r c u m
s t a n c e s , t h e e x p e r i m e n t w o u l d y i e l d kx = k , s i n c e t h e s i n g l e t
and
triplet
i n t e r a c t i o n s w o u l d be i n d i s t i n g u i s h a b l e f r o m t h e
kinetic analysis.
An a n a l y s i s o f t h e i n i t i a l p r o d u c t s o f t h e
r e a c t i o n w o u l d be u s e f u l , b u t t h a t i s beyond t h e s c o p e o f o u r
experiments.
A number o f v e r y e x o t h e r m i c r e a c t i o n
channels
e x i s t (4), but i d e n t i f i c a t i o n o f the i n i t i a l products o f the r e
action i s very d i f f i c u l t .
The o b s e r v e d A r r h e n i u s b e h a v i o r may
i n d i c a t e t h a t t h e m a j o r p r o d u c t c h a n n e l s do n o t change a s t h e
temperature i s r a i s e d .
The o b s e r v a t i o n t h a t v i b r a t i o n a l e x c i
t a t i o n o f t h e C does n o t s t r o n g l y a f f e c t t h e r e a c t i o n r a t e may
indicate that the C
bond i s n o t b r o k e n d u r i n g t h e r e a c t i o n ,
i m p l y i n g C 0 as a p r o d u c t , b u t w i t h s u c h a l o w b a r r i e r t h e e x i t
c h a n n e l o f t h e p o t e n t i a l s u r f a c e may be more i m p o r t a n t i n d e t e r
mining the reaction product.
Our a n a l y s i s ( 1 4 ) o f t h e t e m p o r a l b e h a v i o r o f t h e C a n d
C
s i g n a l s a t room t e m p e r a t u r e and a t 900 i n d i c a t e s t h a t t h e
i n t e r s y s t e m c r o s s i n g r a t e s l o w s down a t h i g h e r t e m p e r a t u r e .
This
d e t a i l e d modeling i n d i c a t e s that a t higher temperatures t h e C
disappearance r a t e i s a f f e c t e d by t h e i n t e r s y s t e m r a t e b u t t h e
C
decay i s a s i n g l e e x p o n e n t i a l c o r r e s p o n d i n g t o t h e r e a c t i o n
rate.
T h i s e x p l a i n s why t h e C r a t e c o n s t a n t s show more s c a t t e r
and l i e b e l o w t h e l i n e p r e d i c t e d b y t h e C r e s u l t . The d e t a i l s
o f t h i s a r e c o m p l i c a t e d a n d w i l l be p r e s e n t e d l a t e r ( 1 4 ) .
This

266
Conclusions
We have d e m o n s t r a t e d
t h a t o u r a p p a r a t u s c a n be u s e d t o
o b t a i n p r e c i s e k i n e t i c d a t a o v e r t h e 300-1300 t e m p e r a t u r e
range.
These r e s u l t s w i t h C
+ 0
suggest t h a t the s i n g l e t t r i p l e t i n t e r s y s t e m c r o s s i n g o c c u r s a t l o n g range i n t e r a c t i o n s
w i t h o x y g e n and t h a t r e a c t i o n must o c c u r s u b s e q u e n t l y upon c l o s e r
approach.
These r e s u l t s c l e a r l y d e m o n s t r a t e t h a t k i n e t i c d a t a
o v e r a w i d e t e m p e r a t u r e r a n g e c a n sometimes p r o v i d e a d d i t i o n a l
insight into the p o t e n t i a l surfaces of the reaction.
Future
experiments are planned t o i n v e s t i g a t e the r e a c t i o n k i n e t i c s of
other r a d i c a l s .
2
Acknowledgments
T h i s work was done u n d e r
ment o f E n e r g y .
t h e a u s p i c e s o f t h e U. S. D e p a r t
Literature Cited
1. K. P. Huber and G. Herzberg, Molecular Spectra and Molecular
Structure IV. Constants of Diatomic Molecules; Van Nostrand
Reinhold: New York, 1979.
2. H. Reisler, M. Mangir, and C. Wittig,
Chem. Phys. 1979,
71, 2109.
3. V. M. Donnelly and L. Pasternack, Chem. Phys. 1979, 39, 427.
4. L. Pasternack and J. R. McDonald, Chem. Phys. 1979, 43, 173.
5. H. Reisler, M. Mangir, and C. Wittig, Chem. Phys. 1980, 47,
49.
6. M. S. Mangir, H. Reisler, and C. Wittig, J. Chem. Phys.
1980, 73, 829.
7. H. Reisler, M. S. Mangir, and C. Wittig,
J.
Chem. Phys.
1980, 73, 2280.
8. L. Pasternack, A. P. Baronavski, and J. R. McDonald, J.
Chem. Phys. 1980, 73, 3508.
9. L. Pasternack, W. M. Pitts, and J. R. McDonald, Chem. Phys.
1981, 57, 19.
10. W. M. Pitts, L. Pasternack, and J. R. McDonald, Chem. Phys.
1982, 68, 417.
11. W. Felder, A. Fontijn, . N. Volltrauer, and D. R. Voorhees,
Rev. Sci. Instrum. 1980, 51, 195.
12. P. Erman, D. L. Lambert, M. Larsson, and B. Mannfors, Astrophys. J. 1982, 253, 983.
13. L. Curtis, B. Engman and P. Erman, Physica Scripta 1976, 13,
270.
14. S. L. Baughcum and R. C. Oldenborg, to be published.
RECEIVED October 28,
1983

16
Reaction of Carbon Monoxide with Oxygen Atoms
from the Thermal Decomposition of Ozone
Effect of Added Gases
S I D N E Y T O B Y , S H A I L E S H S H E T H , and F R I N A S. T O B Y
Rutgers, The State University of New Jersey, Department of Chemistry, New Brunswick,
NJ 08903
The r e a c t i o n between carbon monoxide and oxygen atoms

produced by the thermal decomposition of ozone was
s t u d i e d i n the range 8 0 - 1 6 0 C .
The chemiluminescence
from CO2(1B2) was used to f o l l o w the course of the
reaction.
The e f f e c t of added carbon d i o x i d e ,
tetrafluoromethane and oxygen on the k i n e t i c s and
chemiluminescence was i n v e s t i g a t e d .
I t i s concluded
that there are simultaneous bimolecular and t h i r d body
channels f o r the r e a c t i o n of CO with 0-atoms to produce
e l e c t r o n i c a l l y e x c i t e d CO2.
The r e a c t i o n of oxygen atoms with carbon monoxide i s an important

r e a c t i o n i n many combustion systems. Although there i s an exten
s i v e l i t e r a t u r e on t h i s r e a c t i o n (1) there i s disagreement and
u n c e r t a i n t y on the m o l e c u l a r i t y of the r e a c t i o n , on the k i n e t i c
parameters and on the mechanism of the chemiluminescence.
We have
i n v e s t i g a t e d t h i s r e a c t i o n using 0-atoms from the thermal decompo
s i t i o n of ozone.
T h i s has advantages compared to systems where
0-atoms are produced by a discharge through molecular oxygen. We
have shown that t h i s i s a f e a s i b l e system to study the r e a c t i o n
0 + CO
p r o v i d i n g that trace i m p u r i t i e s are c a r e f u l l y removed
from the CO ( 2 ) .
We a l s o described how k i n e t i c data could be ob
t a i n e d from the chemiluminescence.
The present work extends t h i s
approach and i n v e s t i g a t e s the e f f e c t of added gases on the emitted
i n t e n s i t y so as to provide more information on the m o l e c u l a r i t y of
the r e a c t i o n .
Experimental
Section
The experimental system has been described p r e v i o u s l y (2, 3 ) . A

c y l i n d r i c a l quartz r e a c t i o n v e s s e l of volume 0.525L was s i t u a t e d
i n a thermostatted oven and the ozone concentration was measured
by absorption at 254nm.
Other gas concentrations were measured by
0097-6156/84/0249-0267$06.00/0
268
d i a p h r a g m gauges and a MKS B a r a t r o n c a p a c i t a n c e manometer. Chemi

l u m i n e s c e n c e was measured by s h u t t e r i n g t h e m o n i t o r i n g beam and
m e a s u r i n g t h e u n f i l t e r e d e m i s s i o n w i t h a 1P28 p h o t o m u l t i p l i e r .
Ozone was made by p a s s i n g o x y g e n ( M a t h e s o n U l t r a p u r e g r a d e )
t h r o u g h a n o z o n i z e r and p e r f o r m i n g s e v e r a l f r e e z e - t h a w c y c l e s s o
t h a t t h e O2 c o u l d be pumped away. C a r b o n monoxide was u s e d b o t h
f r o m M a t h e s o n R e s e a r c h G r a d e P y r e x b u l b s and f r o m c o m m e r c i a l c y
l i n d e r s a f t e r b e i n g d i s t i l l e d a t -196. I n b o t h c a s e s m e t a l c a r b o n y l s a r e p r e s e n t as i m p u r i t i e s and were removed by t h e method
d e s c r o b e d by Stedraan jet al ( 4 ) u s i n g a n i o d i n e / c h a r c o a l s p i r a l .
C a r b o n d i o x i d e and t e t r a f l u o r o m e t h a n e were d i s t i l l e d f r o m t h e
commercial m a t e r i a l s .
Computer s i m u l a t i o n o f t h e k i n e t i c mechanism was c a r r i e d o u t
u s i n g t h e p r o g r a m o f Brown ( 5 ) on a D i g i t a l E q u i p m e n t C o r p . VAX
780 c o m p u t e r .
Results
As n o t e d p r e v i o u s l y ( 2 ) r u n s c a r r i e d o u t i n t h e a b s e n c e o f a mod
e r a t o r g a s t e n d e d t o be e r r a t i c , p r o b a b l y b e c a u s e o f a v i b r a
t i o n a l l y excited chain propagator.
E x p e r i m e n t s were t h e r e f o r e
c a r r i e d o u t i n t h e p r e s e n c e o f added CO2, 0 2 o r CF4.
Ozone d e c a y p l o t s w e r e pseudo f i r s t o r d e r w i t h c o r r e l a t i o n
c o e f f i c i e n t s >0.99 and t y p i c a l e x a m p l e s a r e shown i n F i g u r e 1.
The pseudo f i r s t o r d e r c o n s t a n t s were d i v i d e d by t h e t o t a l c o n c e n
t r a t i o n u s i n g e f f i c i e n c i e s g i v e n by Hampson ( 6 ) and t h e r e s u l t i n g
second o r d e r c o n s t a n t s a r e g i v e n as k i n T a b l e I w i t h t h e e x p e r i
mental c o n d i t i o n s . A l s o given i n Table I are the r e l a t i v e emitted
i n t e n s i t i e s measured by t h e u n f i l t e r e d p h o t o m u l t i p l i e r .
I t was
d i f f i c u l t t o measure i n t e n s i t y a t t h e b e g i n n i n g o f t h e e x p e r i m e n t s
and t h e p a r a m e t e r /2> t h e i n t e n s i t y when [O3] = [ 0 3 ] Q / 2 , i s u s e d .
a
Discussion
When s u f f i c i e n t l y p u r i f i e d CO i s r e a c t e d w i t h O3 t h e r a t e l a w
r e d u c e s t o t h e s i m p l e f i r s t o r d e r dependence e x p e c t e d f r o m t h e
sequence.
0. + M
3
0
+ 0
+ 0 + M
2
20
U n d e r t h e c o n d i t i o n s o f o u r e x p e r i m e n t s k 2 [ 0 3 ] k _ i [2] f o r
v i r t u a l l y t h e e n t i r e r u n and a s s u m i n g a s t e a d y s t a t e i n [0] y i e l d s
- d [ 0 3 ] / d t = 2 k i [ 0 3 ] [ M ] and t h i s pseudo f i r s t - o r d e r dependence i s
s e e n i n F i g u r e 1. The l i t e r a t u r e v a l u e s ( 6 ) f o r 2 k j (M=C02 o r

16.
TOBY ET AL.
Reaction of Carbon Monoxide
with Oxygen Atoms
269
Table I.
C h e m i l u m i n e s c e n t I n t e n s i t i e s and R a t e C o n s t a n t s f r o m t h e
R e a c t i o n o f 0-atoms w i t h CO i n t h e P r e s e n c e o f Added
Gases
p(o >
P(C0)
p(co )
P(X)
1 /2 *
, "â
r
80C
0.25
0.25
0.25
8.08
7.35
7.40
0.8
5.0
23.0
0.75
0.5
0.7
1.43
0.73
0.29
2.2
1.9
5.1
3.5
3.05
3.24
6.34
4.85
6.1
7.4
6.9
6.2
7.3
5.25
5.65
6.3
6.0
6.05
5.6
4.8
5.9
15.0
15.9
29.2
25.5
6.29
30.2
52.2
54.3
46.9
39.7
36.6
17.0
4.10
1.8
1.65
9.6
4.1
7.65
4.0
23.5
14.2
3.42
3.70
2.88
3.44
2.60
3.22
2.44
14.7
10.4
7.47
8.51
8.07
10.2
22.6
13.7
8.68
11.5
5.29
7.34
4.83
6.70
4.25
115C
0.25
0.25
0.25
0.25
5.76
5.26
5.74
5.68
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.0
1.0
1.0
1.0
150C
8.50
8.48
4.00
4.0
21.7
1.51
0.76
0.76
0.19
1.56
1.38
4.24
21.3
160C
0.20
0.20
0.25
0.40
0.20
0.25
0.25
0.25
0.41
0.32
0.46
0.42
0.22
0.24
0.24
0.64
0.64
1.06
1.06
1.06
1.00
3.90
2.77
0.72
0.87
0.59
0.73
0.65
0.86
0.54
( a ) A t 150 X = CF^
2.5
2.5
23.0
5.0
16.0
5.0
10.0
10.0
3.65
4.41
3.00
3.72
2.96
4.40
2.75
5.34b
2.51
8.20
5.34
8.50
2.60
9.50
( b ) A t 160 0
1.29
1.58
1.30

270
e q u i v a l e n t ) a t 80, 115, 150 and 160 a r e 0.017, 0.32, 3.7 and

6.8
M*"ls"l r e s p e c t i v e l y . These v a l u e s are approached at the h i g h e r
v a l u e s o f added gas and t h i s i s w e l l i l l u s t r a t e d i n F i g u r e 2 where
the observed second o r d e r c o n s t a n t s are p l o t t e d a g a i n s t the p r e s s u r e o f added CF4 f r o m t h e d a t a i n T a b l e I . C l e a r l y t h e t h e r m a l
d e c o m p o s i t i o n o f ozone i s a p p r o a c h e d a t s u f f i c i e n t l y h i g h p r e s s u r e s
of d e a c t i v a t i n g gas.
P r e v i o u s s i m u l a t i o n work ( 2 ) showed t h a t t h e k i n e t i c s o f t h e
r e a c t i o n o f O3 w i t h i m p u r e CO c o u l d be d e s c r i b e d u s i n g an i n i t i a t i o n s t e p O3 + HX
where HX i s a h y d r o g e n - c o n t a i n i n g i m p u r i t y .
An
e q u a l l y good and more r e a l i s t i c s i m u l a t i o n was o b t a i n e d by p o s t u l a t i n g a n i c k e l c a r b o n y l i m p u r i t y as t h e i n i t i a t o r and u s i n g t h e
mechanism g i v e n by Stedman and B r a n c h ( 4 ^ f o r t h e r e a c t i o n o f O3
w i t h n i c k e l c a r b o n y l . Of p a r t i c u l a r c o n c e r n t o t h e p r e s e n t work
i s t h e f a c t t h a t t h e r e a c t i o n o f O3 w i t h c a r b o n y l s i s c h e m i l u m i n e s c e n t f r o m e x c i t e d m e t a l o x i d e s and t h i s e m i s s i o n c o u l d i n t e r f e r e
f r o m t h a t a r i s i n g f r o m 0 + CO
hv.
We sometimes f o u n d an e r r a t i c
e m i s s i o n a t t h e b e g i n n i n g o f t h e e x p e r i m e n t s w h i c h t h e n became
r e p r o d u c i b l e as t h e r u n p r o c e e d e d . Any e m i s s i o n f r o m
0 + Ni(C0)4
hv w o u l d f o l l o w t h e r a t e l a w 1 = k [O3]
[Ni(C0)4]
and w o u l d be e x p e c t e d t o d e c a y r a p i d l y b e c a u s e o f t h e s m a l l i n i t i a l
c o n c e n t r a t i o n o f c a r b o n y l ( < l p p b ( 4 ) ) . On t h e o t h e r h a n d , e m i s s i o n
f r o m 0 + CO + hv shows a r e l a t i v e l y s m a l l t i m e dependence when
t h e 0-atoms a r e formed f r o m O3 02) and t h u s u s e o f t h e
l\/2
p a r a m e t e r s h o u l d e l i m i n a t e any i n t e r f e r e n c e f r o m c a r b o n y l e m i s s i o n .
3
The
Mechanism
We p o s t u l a t e s t e p s 1, - 1 , 2 and t h e f o l l o w i n g s e q u e n c e w h i c h
d i f f e r s f r o m t h a t p r e v i o u s l y p r o p o s e d ( 2 ) by t h e a d d i t i o n o f
s t e p 8:
0 +
CO
0 + CO +
C0 ( B )
2
CO^^)
C0 ( B ) +
C0*( B )
C0 ( B ) +
* 3
C0 ( B )
C0
C0
hv
( B )
2

16.
TOBY ET AL.
with Oxygen Atoms
271
E*1
-1.15
-1.28
-1.25.
on
-1.30.
-1.35
-1.48
-1.45.
Ei-3
8.58
8.88
1.
1.5
2.80
time, s
F i g u r e 1.
T y p i c a l ozone d e c a y p l o t s a t 6 . P ( C 0 ) = 1 . 0 6 t o r r ,
P ( 0 ) = 0 . 2 5 t o r r , P ( C 0 ) = 2 . 5 ( c i r c l e s ) , 100 ( t r i a n g l e s ) , a n d
23 f s q u a r e s ) .
2
F i g u r e 2 . E f f e c t o f a d d e d CF^ o n m e a s u r e d ozone d e c a y c o n s t a n t a t
150.
The d a s h e d l i n e i s t h e l i t e r a t u r e v a l u e o f 2 ^ .

272
T a k i n g s t e a d y s t a t e s i n i n t e r m e d i a t e c o n c e n t r a t i o n s ( w h i c h was
v e r i f i e d by c o m p u t e r s i m u l a t i o n ) and s i n c e n e a r l y a l l t h e 0-atoms
d i s a p p e a r v i a s t e p 2 we o b t a i n f o r t h e e m i s s i o n i n t e n s i t y :
I
k
k
k [ C 0 ] [M] <k
( k
k^ + k
[M] ( k ^ + k
[M]))
(1)
E q u a t i o n ( 1 ) p r e d i c t s t h a t I [CO] a t c o n s t a n t [M] as p r e v i o u s l y
f o u n d ( 2 ) . We now assume t h a t k y [ M ] kfr and t h a t k5[M] k4
to obtain:
I
[CO]
(
6
k k
2
E q u a t i o n ( 2 ) i s t e s t e d i n F i g u r e 3 and shows t h e e x p e c t e d l i n e a r i t y
o f 1/[CO] i n [M] w i t h s l o p e s and i n t e r c e p t s w h i c h i n c r e a s e w i t h
temperature.
F i g u r e 3 contains the data i n Table I (except f o r the
r u n s w i t h added CF4) and d a t a f r o m p r e v i o u s work ( 2 ) . The s l o p e s
and i n t e r c e p t s f r o m F i g u r e 3 a r e l i s t e d i n T a b l e I I a n d F i g u r e 4.
Table I I .
S l o p e s and I n t e r c e p t s f r o m F i g u r e 3.
Temp C
Slope
2
nA K " x l 0 ~
Correlation
coefft.
Intercept
1
nA M ^ x K T *
80
0.20
115
1.6
132
0.46
1.5
0.943
150
1.2
4.2
0.952
160
2.4
4.7
0.988
U t i l i z i n g E q u a t i o n ( 2 ) an A r r h e n i u s p l o t o f these d a t a g i v e s
ln(k k k k "
k y ' V n A M~ ) = 42.7 -20.2/RT and l n
1

TOBY ET AL.
16.
.00
0.50
with Oxygen Atoms
273
1.00
, E3
F i g u r e 3 . P l o t o f I , /(CO) v s . (.) l 6 0 , t r i a n g l e s , 0 added.
Data from R e f . 2 a r e a t l 6 0 ( s q u a r e s ) , 150 (diamonds), 1 3 2
( s q u a r e s ) , 115
( u n f i l l e d t r i a n g l e s ) , a n d 80 ( u n f i l l e d c i r c l e s ) .
Q

274
F i g u r e h.
Arrhenius
p l o t o f s l o p e s and i n t e r c e p t s
f r o m F i g u r e 3.

16.
Reaction of Carbon Monoxide with Oxygen Atoms
TOBY ET AL.
1
275
( k k 3 k k 2 " k " / n A VT ) - 24.6-11.8/RT where R i s i n k c a l m o l e "

"*
We c a n n o t o b t a i n a b s o l u t e v a l u e s o f w h i c h i s dependent o n
the geometry o f o u r system, b u t combining the A r r h e n i u s l i n e s g i v e s
w i t h e s t i m a t e d e r r o r s l n (ksk ' /lf )
= 18.1 2.2 - ( 8 . 4 + l . D / R T .
C o m b i n i n g t h i s w i t h t h e v a l u e o f k3 o b t a i n e d p r e v i o u s l y ( 2 ) g i v e s
l n ( k / M ~ S " ) = 33.7 2.2 - ( 1 1 . 6 + l . D / R T .
Termolecular
r e a c t i o n s i n v o l v i n g 0-atoms have n e g a t i v e t e m p e r a t u r e c o e f f i c i e n t s
e x c e p t f o r t h e r e a c t i o n s w i t h N , SO2, and CO w h i c h have p o s i t i v e
a c t i v a t i o n e n e r g i e s . We may compare r e a c t i o n 8 w i t h t h e i s o e l e c
t r o n i c r e a c t i o n 0 + N + M N 0 + M f o r which the reported
a c t i v a t i o n e n e r g y i s 10.4 k c a l m o l e
(60.
1
- 1
A p o t e n t i a l energy diagram f o r t h e lower e x c i t e d s t a t e s o f

C 0 h a s been g i v e n by P r a v i l o v and S m i r n o v a ( 7 ) who have summarized
t h e r e c e n t l i t e r a t u r e on t h e r e a c t i o n o f 0-atoms w i t h CO. They
h a v e p o i n t e d o u t t h e c o m p l i c a t i o n s r e s u l t i n g f r o m i m p u r i t i e s and
h e t e r o g e n e o u s e f f e c t s on t h i s s y s t e m .
We c o n c l u d e t h a t t h e t h e r m a l d e c o m p o s i t i o n o f O3 i s a u s e f u l
s o u r c e o f 0-atoms p r o v i d i n g t h a t O3 d o e s n o t r e a c t a p p r e c i a b l y w i t h
t h e s u b s t r a t e . I n t h e c a s e o f t h e r e a c t i o n w i t h CO t r a c e s o f
c a r b o n y l i m p u r i t y c o m p l i c a t e t h e k i n e t i c s and c h e m i l u m i n e s c e n c e ,
e s p e c i a l l y a t t h e l o w e r t e m p e r a t u r e s . T h e s e c o m p l e x i t i e s c a n be
overcome and o u r r e s u l t s i n d i c a t e t h a t t h e r e a r e s i m u l t a n e o u s
b i m o l e c u l a r and t h i r d body c h a n n e l s f o r t h e r e a c t i o n o f 0-atoms
w i t h CO. T h i s may a c c o u n t f o r t h e d i s c o r d a n t l i t e r a t u r e f o r t h i s
reaction.
Acknowledgment
We t h a n k t h e R e s e a r c h C o u n c i l o f R u t g e r s U n i v e r s i t y f o r s u p p o r t
o f t h i s work.
Literature Cited
1. Dixon-Lewis, G.; Williams, D.J. in "Comprehensive Chemical
Kinetics" Vol. 17. Bamford, C.M.; Tipper, C.F., Eds.;
Elsevier: The Netherlands, 1977.
2. Toby, S.; Sheth, S.; Toby, F.S. Int. J. Chem. Kinetics 1983,
15, 0000.
3. Toby, S.; Ullrich, E. Int. J. Chem. Kinetics 1980, 12, 535.
4. Stedman, D.H.; Tammaro, D.A.; Branch, D.K.; Pearson, R.
Analyt. Chem. 1979, 51, 2340.
5. Brown, R.L. "A Computer Program for Solving Systems of
Chemical Rate Equations", NBSIR 76-1055, Natl. Bur. of
Standards, Washington, D.C., 1978.

276
6. Hampson, R.F. "Chemical Kinetic and Photochemical Data Sheets

for Atmospheric Reactions", FAS-EE-80-17, Natl. Bur. of
Standards, Washington, D.C. 1980.
7. Pravilov, A.M.; Smirnova, L.G. Kinetika i Kataliz 1981, 22,
832.
1983

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ix001
Author Index
Baughcum, Steven L., 257
Binkley, J . S., 103
B i t t n e r , J . D., 3
B l i n t , Richard J . , 87
Calcote, H. F., 33
Chou, Mau-Song, 71
Clements, R. ., 193
Cole, J . ., 3
Crosley, David R., 239
Dasch, Cameron J . , 87
Dean, Anthony ., 71
Eyler, John R., 49
F a i r c h i l d , Paul W., 239
G i l l , R. J . , 33
H a r r i s , Stephen J . , 23
Howard, J . ., 3
K e i l , D. G., 33
Lee, John H. S., 119
Longwell, J . P., 3
Melius, C. F., 103
Oldenborg, Richard C , 257
Olson, D. ., 33
Oran, E l a i n e , 151
R a t c l i f f e , John W., 205
Sheth, Shailesh, 267
Sloane, Thompson ., 205
Smith, Gregory P., 239
Stern, David, 71
Toby, Frina S., 267
Toby, Sidney, 267
T u l l y , Frank P., 225
Westbrook, Charles ., 175
Subject Index
A
Absorber, IR, s u l f u r
hexafluoride, 240-41
Absorption, l a s e r , nitrogen chemistry
i n ammonia flames, 72,73f
Abstraction route f o r hydrogen
atom, 230-36
Acceleration of flames
See alsoFlame speed
and turbulence, 121-33,163-70
Acetylene, k i n e t i c s
decay rate as function of
pressure, 245,246f
detonations, 176-90
reaction with hydroxyl, 239-55
reactions with C3H3 and C5H5
cations, 54t,59t,60t , 6 l t
Acetylene-air flames
d e f l a g r a t i o n to detonation, 142-46
speeds, 127-33
Acetylene-oxygen flame near soot
threshold
ion concentrations, 33-46
neutral species, formation, 44-46
polynuclear aromatics,
formation, 41-46
Acetylenic species, a d d i t i o n to
1,3-butadienyl, rate
constants, 15-l6t
Acoustic-chemical coupling, 151-54
A c t i v a t i o n energy, 112-13
A c t i v a t i o n energy, r e a c t i o n of NH and
oxygen, 109
Addition channel rate
constant, 249-54
Additives, i n h i b i t i o n o f
detonation, 186-90
A i r j e t surface, I69f
A l i p h a t i c flames, formation o f
aromatic species, 3-16
Aline, rate c o e f f i c i e n t s f o r
cyclopentadienyl cation
reactions, 59t,60t,6lt
Ammonia combustion, k i n e t i c
mechanism, 93,94f
Ammonia-doped methane flames, 96-98
Ammonia flame
hydroxide r o t a t i o n a l e x c i t a t i o n and
temperature, 72,74f,75-77
ion d i s s o c i a t i o n , 82-84
ion e q u i l i b r i u m , 76t
ion formation, 71-85
ion p r o f i l e s , 77,80f
o s c i l l a t o r strength of NH2, thermodynamic parameters, 75
Ammonia o x i d a t i o n , 103-13
k i n e t i c s , 77-85
k i n e t i c s of nitrogen oxide and
nitrogen gas formation, 87-100
concentrations as function of
equivalence r a t i o , 93,94f
mechanism, 90,93-95
Amplitude of sound wave and heat
release, 153f
Aromatic species formation i n
a l i p h a t i c flames, 3-16
a l i p h a t i c flames, r o l e of v i n y l
acetylene, 16-20
Arrhenius p l o t
rate c o e f f i c i e n t data, 230,231f
279

Author Index
Baughcum, Steven L., 257
Binkley, J . S., 103
B i t t n e r , J . D., 3
B l i n t , Richard J . , 87
Calcote, H. F., 33
Chou, Mau-Song, 71
Clements, R. ., 193
Cole, J . ., 3
Crosley, David R., 239
Dasch, Cameron J . , 87
Dean, Anthony ., 71
Eyler, John R., 49
F a i r c h i l d , Paul W., 239
G i l l , R. J . , 33
H a r r i s , Stephen J . , 23
Howard, J . ., 3
K e i l , D. G., 33
Lee, John H. S., 119
Longwell, J . P., 3
Melius, C. F., 103
Oldenborg, Richard C , 257
Olson, D. ., 33
Oran, E l a i n e , 151
R a t c l i f f e , John W., 205
Sheth, Shailesh, 267
Sloane, Thompson ., 205
Smith, Gregory P., 239
Stern, David, 71
Toby, Frina S., 267
Toby, Sidney, 267
T u l l y , Frank P., 225
Westbrook, Charles ., 175
Subject Index
A
Absorber, IR, s u l f u r
hexafluoride, 240-41
Absorption, l a s e r , nitrogen chemistry
Abstraction route f o r hydrogen
atom, 230-36
Acceleration of flames
See alsoFlame speed
and turbulence, 121-33,163-70
Acetylene, k i n e t i c s
decay rate as function of
pressure, 245,246f
detonations, 176-90
reaction with hydroxyl, 239-55
reactions with C3H3 and C5H5
cations, 54t,59t,60t , 6 l t
Acetylene-air flames
speeds, 127-33
Acetylene-oxygen flame near soot
threshold
ion concentrations, 33-46
neutral species, formation, 44-46
polynuclear aromatics,
formation, 41-46
Acetylenic species, a d d i t i o n to
1,3-butadienyl, rate
constants, 15-l6t
Acoustic-chemical coupling, 151-54
A c t i v a t i o n energy, 112-13
A c t i v a t i o n energy, r e a c t i o n of NH and
oxygen, 109
Addition channel rate
constant, 249-54
Additives, i n h i b i t i o n o f
detonation, 186-90
A i r j e t surface, I69f
A l i p h a t i c flames, formation o f
aromatic species, 3-16
Aline, rate c o e f f i c i e n t s f o r
cyclopentadienyl cation
reactions, 59t,60t,6lt
Ammonia combustion, k i n e t i c
mechanism, 93,94f
Ammonia-doped methane flames, 96-98
Ammonia flame
hydroxide r o t a t i o n a l e x c i t a t i o n and
temperature, 72,74f,75-77
ion d i s s o c i a t i o n , 82-84
ion formation, 71-85
ion p r o f i l e s , 77,80f
o s c i l l a t o r strength of NH2, thermodynamic parameters, 75
Ammonia o x i d a t i o n , 103-13
k i n e t i c s , 77-85
k i n e t i c s of nitrogen oxide and
nitrogen gas formation, 87-100
concentrations as function of
equivalence r a t i o , 93,94f
mechanism, 90,93-95
Amplitude of sound wave and heat
release, 153f
a l i p h a t i c flames, 3-16
a l i p h a t i c flames, r o l e of v i n y l
acetylene, 16-20
Arrhenius p l o t
rate c o e f f i c i e n t data, 230,231f
279

280
Arrhenius p l o t C o n t i n u e d
r e a c t i o n of carbon monoxide with
oxygen atoms, 272-75
reaction of hydroxyl and
acetylene, 252-54
reaction of hydroxyl and
ethylene, 232,235f
Atomic oxygen, 111-13
B a f f l e p l a t e flame obstacles, 134

Benzene
cation structures and r e a c t i v i t y i n
benzene flame, 56-57
formation i n near-sooting
1,3-butadiene flame, 14-15,17f
rate c o e f f i c i e n t s for reactions with
cyclopropenyl and cyclopentadienyl
cations, 54t,59t,60t,61t
Bimolecular rate c o e f f i c i e n t , 230
Bond a d d i t i v i t y c o r r e c t i o n s , 103-13
Bond energy, NH -0 , 105-8
Burn rate
methane-air mixture i n a constant
volume chamber, 199-201
b a f f l e p l a t e flame obstacles, 134-35
1,3-Butadiene, rate c o e f f i c i e n t s f o r
reactions with cyclopentadienyl
c a t i o n s , 59t,60t,6lt
1,3-Butadiene-oxygen-argon flame, near
sooting temperature p r o f i l e , 5-7
1,3-Butadienyl i n near-sooting flames,
a d d i t i o n of a c e t y l e n i c
species, 15-l6t
2
C
Carbon C r a d i c a l
disappearance rates with
oxygen, 257-66
formation by multiple-photon
d i s s o c i a t i o n , 259
Carbon dioxide e f f e c t i n carbon
monoxide r e a c t i o n with oxygen
atoms, 268,269t
Carbon dioxide l a s e r , 240-41
Carbon monoxide
k i n e t i c s of gaseous
detonations, 176-90
r e a c t i o n with oxygen atoms, 267-75
Carbon/oxygen r a t i o s and soot growth
mechanism, 23-31
Cations, isomers and structures
C 3 H 3 , 52-58
C 5 H 5 , 57-63
C 6 H 5 , 56-58
rate c o e f f i c i e n t s of reactions with
neutral species, 54t,59t,60t,6lt
2
C e l l design for high temperature

p y r o l y s i s , 258,261f
C e l l size and
detonation, 139-40,154,155t,180-83
Chemical-acoustic coupling, 151-54
Chemiluminescence of carbon dioxide
and carbon monoxide r e a c t i o n with
Collision-induced ion d i s s o c i a t i o n i n
double-focusing mass
spectrometer, 49-65
Combustion
ammonia, k i n e t i c s , 93,94f
methane-air f u e l mixture i n a con
stant volume chamber, 196-201
p r e d i c t i o n , 133-37
Convective ion transport, concentra
t i o n equation, 36
Cyclopentadiene c a t i o n formation, 59t
Cyclopropenylium isomer, s t r u c t u r e and
r e a c t i v i t y , 52-56
Decay rate
and acetylene pressure, 245,246f
and ethylene concentration, 232,234f
of ozone, 268,271f
pseudo f i r s t - o r d e r , 230
Decomposition
of ozone, thermal, 267-75
of ions i n ammonia flames,
unimolecular theory, 82-85
Deflagration to detonation, 142-46
Density of soot p a r t i c l e s i n ethyleneoxygen-argon flame, 24,25f
Density-temperature r e l a t i o n s h i p , 241
Detection
of laser-induced
fluorescence, 226,227f,229f
t i m e - o f - f l i g h t , molecular
beam, 206-8
Detonation
and c e l l
s i z e , 139-40,154,155t,180-83
and d e f l a g r a t i o n , 142-46
and flame a c c e l e r a t i o n , 119
of hydrocarbon fuels and equivalence
r a t i o , 139-40
k i n e t i c f a c t o r s , 154,155t,175-90
i n i t i a t i o n and propagation, 157-72
l i m i t s and induction length, 180-90
models, 177-80
and shock, 163,170,171
s p h e r i c a l , 186
Diameter of tube
detonation c e l l s i z e , 139-40
and k i n e t i c s of gaseous
detonations, 183-89

INDEX
281
Dicyclopentadiene, formation of
cyclopentadienyl c a t i o n s , 60t
D i f f e r e n t i a l overlapSee INDO or
MINDO
D i f f u s i o n processes i n i g n i t i o n and
propagation of detonations, 151-72
D i f f u s i v e transport of ions and con
centration equation, 35-36
Dimethylenecyclopropenylium
isomer, 57,58f,62,64f
Disappearance rates of C2 with oxygen,
e q u i l i b r i u m constants, 263-66
D i s s o c i a t i o n of ions
i n ammonia flame, rate
constants, 82-84
CF3CCCF3, multiple-photon, 257-66
C3K3, 52-58
C5H5,
57-63
C6H5,
56-58
H2NO, 111-12
Distance vs. flame speed i n hydrogena i r flames, 123-26

Doped methane flames
ammonia, 9 6 - 9 8
nitrogen oxide, 96,97-98
Double-focusing, reversed-geometry,
mass spectrometer, 49-65
Dye l a s e r , v i s i b l e , second harmonic
generation, 228t
Dynamics, f l u i d , i g n i t i o n and propaga
t i o n of detonations, 151-72
E l e c t r i c spark i g n i t i o n f o r d i f f e r e n t
f u e l mixtures, 206-21
E l e c t r i c a l c i r c u i t r y , plasma j e t
i g n i t i o n , 196-99
Electrodes, spark, and flame
propagation, 216-21
Electron c o r r e l a t i o n e f f e c t s and
fourth-order Moller-Plesset
perturba- t i o n theory, 104-5
Electron microscopy, molecular beam,
for i o n concentration
p r o f i l e s , 43-44
E l e c t r o s t a t i c probe, Langmuir, 35-46
Energy
a c t i v a t i o n , 112-13
bond, NH -0 , 105-8
i n i t i a t i o n of detonation and c e l l
s i z e , 139-46
i n i t i a t i o n of detonation, 185-86
t o t a l , using Hartree-Fock
theory, 104-5
Energy l e v e l s S e e INDO or MINDO
Engines
and plasma j e t i g n i t e r s , 199-203
s i n g l e - c y l i n d e r , 199-201
Equilibrium, i o n , i n ammonia
flames, 76t
2
Equilibrium constant f o r disappearance

rates of Co r a d i c a l s , 263
Equivalence r a t i o
ammonia flame
1.28, hydroxide r o t a t i o n a l
temperature, 72,74f
1.50, i o n p r o f i l e s , 77,80f
and f u e l detonation, 139-40
and f u e l detonation k i n e t i c s , 178-90
and nitrogen oxide
concentration, 93,94f
and reactant and r a d i c a l
formation, 212-21
near soot threshold, t o t a l ion
concentration, 33-46
Ethane
detonation, k i n e t i c s , 176-90
r e a c t i o n with hydroxyl
r a d i c a l , 230-36
Ethane-air f u e l mixtures, 185-88
Ethylene
and aromatic species
formation, 16-20
detonation, k i n e t i c s , 176-90
r e a c t i o n with hydroxyl
r a d i c a l , 230-36
cations, rate
coefficients, 59t,60t,6lt
Ethylene f u e l mixtures
a i r , 188-89
a i r , flame speeds, 127-33
helium, 232,234f
oxygen-argon, mechanism f o r growth
of soot p a r t i c l e s , 23-31
Excitation
of Swan bands, to get C , 259
r o t a t i o n a l , hydroxide ion i n ammonia
flame, 75-77
2
F
Faraday cage, molecular beam, 41,43-44
F i r s t - o r d e r rate constant, acetylene
to soot, 28-30
Flame a c c e l e r a t i o n
See a l s o Flame speed
propagation and spark
electrodes,
216-21
simulation, 133-37
turbulence and detonation
parameters, 119,121-33,163-70
Flame obstacles
b a f f l e p l a t e , 134
o r i f i c e p l a t e , 123-33,135f
Shchelkhin s p i r a l , 123-33
Flame sampling apparatus, 4-5,7f
Flame sampling mass spectrometer
technique f o r i o n p r o f i l e s , 4l,42f
Flame speed
acetylene-air flame, 127-33

282
Flame speedContinued
ammonia-oxygen f u e l , 91
d e f l a g r a t i o n to detonation, 142
vs. distance f o r hydrogen-air
flames, 123-26
Flames
acetylene-air
speed, 127-33
acetylene-oxygen, i o n concentrations
near soot threshold, 33-46
ammonia
ion d i s s o c i a t i o n k i n e t i c s , 82-84
ion formation k i n e t i c s , 71-85
nitrogen oxide and nitrogen gas
formation, 90,93-95
and oxygen
flame speeds, 91
p r o f i l e s , 91
r o t a t i o n a l e x c i t a t i o n of hydroxide
ion, 75-77
benzene, C6H5 cation s t r u c t u r e s and
r e a c t i v i t y , 56-57
1,3-butadiene-oxygen-argon, near
soot threshold, temperature
p r o f i l e , 5-7
ethylene-oxygen-argon, mechanism f o r
soot p a r t i c l e growth, 23-31
hydrogen-air
flame speed vs. distance, 123-26
methane-air, nitrogen oxide
concentrations, 95-98
nonsooting, i o n concentration, 39,41
Flow structure o f f u e l ,
turbulent, 133-37,122-23
F l u i d dynamics, i g n i t i o n and propagat i o n of detonations, 151-72
Fluorescence d e t e c t i o n , l a s e r induced, 55
i n ethane-air, 185-88
i n e t h y l e n e - a i r , 188-89
with laser p h o t o l y s i s , 225-36
with laser p y r o l y s i s , 239-55
with multiple photon d i s s o c i a t i o n of
C F 3 C C C F 3 , 257-66
F o i l , smoked, and detonation c e l l

s i z e , 139-40
Formation
hydroxide, 111-13
of nitrogen oxide and nitrogen gas
ammonia o x i d a t i o n , k i n e t i c s ,
87-100
heats, 103-13
Free r a d i c a l s ,
UV-absorbing, 226,227f,229f
F u e l - a i r mixtures
detonation parameters, 119,137-48
F u e l - a i r mixturesContinued
ethane-air, 185-88
ethylene-air, 188-89
methane-air, 196-201
Fuel mixtures
detonation, equivalence
r a t i o , 139-40
for e l e c t r i c spark i g n i t i o n , 206-21
ethylene-helium, 232,234f
flame speed and o r i f i c e
obstacles, 119-33
flow s t r u c t u r e , 133-37
flow s t r u c t u r e , t r a n s m i s s i b l e , i n
unburned f u e l , 122-23
hydrogen-oxygen, 154-59
Fuel o x i d a t i o n
hydrogen and hydrocarbon, 185-90
induction lengths of mixtures, 181f
k i n e t i c s , 176-78
G
Gas temperature p r o f i l e
c a l c u l a t i o n , 5-6
Gas mixtures, ethylene/HC, 232,234f
Gases, e f f e c t on ozone decay constant,
methane and oxygen, 268-71
Gaseous detonations, k i n e t i c
f a c t o r s , 175-90
Geometries of C 5 H 5 isomers, 62
Growth of soot p a r t i c l e s i n premixed
flames, q u a n t i t a t i v e
mechanism, 23-31
H
Hartree-Fock theory, t o t a l energy
computations, 104-5
Heat, s p e c i f i c , of single c y l i n d e r
test engine, 200
Heat r e l e a s e , e f f e c t on amplitude and
phase of sound wave, 153f
Heats o f formation, 103-13
Helium-ethylene gas mixtures, 232,234f
High-temperature c e l l f o r p y r o l y s i s ,
design, 258,26lf
Hot spots, 154
Hydrocarbon formation, mole f r a c t i o n
and f l u x p r o f i l e s i n near sooting
1,3-butadiene flame, 6,8-13
Hydrocarbon f u e l s
detonation, equivalence
r a t i o , 139-40
flame speed and o r i f i c e
obstacles,
119-33
o x i d a t i o n , 185-90
Hydrocarbon f u e l - a i r mixture,
detonations, 137-48

INDEX
283
Hydrocarbon ions i n soot formation,

r e a c t i v i t i e s and s t r u c t u r e s , 49-65
Hydrogen atom a b s t r a c t i o n
route, 230-36
Hydrogen atom s i g n a l , e l e c t r i c spark
i g n i t i o n , 212,215f,220-21
Hydrogen gas
detonation k i n e t i c s , 176-90
o x i d a t i o n , 185-90
mole f r a c t i o n and f l u x p r o f i l e s i n
near sooting 1,3-butadiene
flame, 6,8-13
Hydrogen-air flames
speed, 127-33
speed vs. distance, 123-26
Hydrogen-oxygen f u e l , shock
propagation, 154-58
Hydrogen-oxygen-argon model
flame a c c e l e r a t i o n and
turbulence, 163-70
k i n e t i c factors and detonation c e l l
s i z e s , 154,155t
sound wave perturbations, 154,155t
Hydroxide i o n
formation, 111-13
i n ammonia flames, 71-85
r o t a t i o n a l e x c i t a t i o n , 75-77
r o t a t i o n a l temperature, 72,74f
in 1,3-butadiene flame, mole
f r a c t i o n and flux
p r o f i l e s , 6,8-13
reactions
with acetylene, 241-54
with ethane and ethylene, 230-36
I
Ignition
e l e c t r i c spark f o r d i f f e r e n t f u e l
mixtures, 206-21
and perturbation waves, 241
plasma j e t
i g n i t e r s , 196-99
s p e c i f i c heat r a t i o , 200
shock to detonation
t r a n s i t i o n , 154-57
shock tube, of propane, 176-78
Indene, rate c o e f f i c i e n t s f o r reac
tions with cyclopropenyl and
cyclopentadienyl
c a t i o n s , 54t,59t,60t,61t
INDO (intermediate neglect of d i f
f e r e n t i a l overlap), cyclopropenyl
and cyclopentadienyl
cations, 55-56,61-63
Induction delay f o r methane-air mix
ture i n a constant volume
chamber, 196,198f
Induction length and detonation
l i m i t s , 180-90
I n h i b i t o r s of detonation, 186-90
I n i t i a t i o n and propagation i n
detonations, 157-72
I n i t i a t i o n energy and detonation c e l l
s i z e , 139-46
Intensity d i s t r i b u t i o n of ions i n
flame, 55
Intermediate neglect of d i f f e r e n t i a l
overlapSee INDO
Ion c y c l o t r o n resonance mass
spectrometry, reactions of
hydrocarbon ions, 51-63
Ion probe, Langmuir, 35-46
Ionic mechanism of soot
nucleation, 33,45-46
Ions
i n acetylene-oxygen flames near soot
threshold, 33-46
i n ammonia flames
d i s s o c i a t i o n , rate
constants, 82-84
e q u i l i b r i u m , 76t
formation i n ammonia flame,
k i n e t i c modeling, 77-82
d i f f u s i v e transport, 35-36
hydrocarbon, structure and reac
t i v i t y i n soot formation, 35
cyclopropenylium, 52-56
intensity distribution i n
flame, 55
phenylium, 56-57
propargylium, 52-56
masses and transport
p r o p e r t i e s , 36-38
IR absorber, 240-41
Isomers of hydrocarbon cations
C3H3,
52-58
C H , 57-63
C H , 56-58
5
J
Jet of a i r , surface, I69f
Jet i g n i t i o n , plasma, 193-203
Kelvin-Helmholtz i n s t a b i l i t y , surface
of a round j e t of a i r , I69f
Kinetics
of acetylene to soot, apparent
f i r s t - o r d e r rate constant, 28-30
of ammonia combustion, 87-100
of aromatic species formation i n
near-sooting 1,3-butadiene-oxygenargon flame, 14-20
of carbon monoxide r e a c t i o n with
of carbon r a d i c a l C2 disappearance
rates with oxygen, 257-66
and detonation c e l l s i z e s , 154,155t

284
KineticsContinued
of f u e l o x i d a t i o n , iYb-
of gaseous detonations, 175-90
of hydrocarbon i o n , 49-65
of hydroxyl r e a c t i o n
with acetylene, 239-55
with ethylene, 232,232f
of i g n i t i o n and propagation of
detonations, 151-72
of ion d i s s o c i a t i o n i n ammonia
flames, 82-84
of ion formation i n ammonia
flame, 77-82
by l a s e r photolysis/laser-induced
fluorescence, 225-36
L
Lagrangian technique with automatic
zone r e s t r u c t u r i n g , I68f
Langmuir probe, ion concentrations i n
acetylene-oxygen flame near soot
threshold, 36-46
Laser absorption i n ammonia
flames, 72,73f
Laser fluorescence
C r a d i c a l reactions with
oxygen, 260-66
nitrogen chemistry i n ammonia
flames, 72,73f
Laser p h o t o l y s i s , 259
Laser p h o t o l y s i s / l a s e r fluorescence of
hydroxyl r e a c t i o n s , 225-36
Laser p y r o l y s i s / l a s e r fluorescence of
hydroxyl r e a c t i o n with
acetylene, 239-55
Lasers, v i s i b l e dye, second harmonic
generation, 228t
2
M
Mass spectrometer, 4-5,7f
Mass spectrometry
reversed-geometry doublefocusing, 49-65
t r i p l e quadrupole, 49-65
flame sampling f o r ion
p r o f i l e s , 4l,42f
ion c y c l o t r o n resonance, 51-63
time-resolved molecular
beam, 206-8,210-16
Masses of ions and transport
p r o p e r t i e s , 36-38
Methane
and e l e c t r i c spark
i g n i t i o n , 212-14,220-21
detonation k i n e t i c s 176-90
and ozone decay constant, 268-71
c a t i o n s , rate
c o e f f i c i e n t s , 59t.60t.6lt
Methane-air f u e l
combustion i n a constant volume
chamber, 199-201
flame speeds, 127-33
Methanol detonations, k i n e t i c s , 176-90
Methyl r a d i c a l s , e l e c t r i c spark
i g n i t i o n , 216-18
Methylenecyclobutenylium
isomer, 57,58f,62,64f
Methylnaphthalene, rate c o e f f i c i e n t s
for reactions with cyclopropenyl
and cyclopentadienyl
cations, 54t,59t,60t,61t
MIKES-CID i n reverse-geometry doublefocusing mass spectrometer, 51
MINDO (modified intermediate neglect
of d i f f e r e n t i a l overlap),
cyclopropenyl and cyclopentadienyl
cations, 55-56,61-63
Molecular beam, 4-5,7f
Molecular beam e l e c t r o n microscopy,
ion concentration p r o f i l e s , 43-44
Molecular beam Faraday cage, 41,43-44
Molecular beam mass spectrometry,
time-resolved, 206-8,210-16
Moller-Plesset perturbation theory,
fourth-order, 103-13
Multiple-photon d i s s o c i a t i o n of
CF3CCCF3,
257-66
Naphthalene, rate c o e f f i c i e n t s f o r
reactions with cyclopropenyl and
cyclopentadienyl
c a t i o n s , 54t,59t,60t,61t
Neutral species
formation i n acetylene-oxygen flame
reactions of cyclopropenyl and
cyclopentadienyl c a t i o n s , rate
coefficients, 54t,59t,60t,6lt
Nitrogen chemistry i n ammonia
flame, 71-85
Nitrogen oxide concentration
i n ammonia-oxygen flames, 91
as function of equivalence
r a t i o , 93,94f
i n methane-air flames, 9 5 - 9 8
Nonsooting flames, ion
concentration, 39,41
Norbornadiene, formation of cyclopen
tadienyl c a t i o n s , 61t
Nucleation of soot, i o n i c
mechanism, 33,45-46
0
Obstacles, flame
b a f f l e p l a t e , 134
o r i f i c e plate, 123-33,135f

INDEX
285
Obstacles, flameContinued
Shchelkhin s p i r a l , 1 2 3 - 3 3
O r b i t a l o v e r l a p S e e INDO or MINDO
O r i f i c e p l a t e obstacles and flame
speed f o r hydrogen-air
mixtures,
123-33
O s c i l l a t o r strength NH i n ammonia
flame, thermodynamic
parameters, 75
Overpressures f o r hydrogen-air flames,
flame speed f o r hydrogen-air
mixtures, 125,127-28
Oxidation of f u e l
ammonia, 77-85,103-13
ammonia, k i n e t i c s o f nitrogen oxide
and nitrogen gas
formation, 87-100
hydrogen and hydrocarbon, 185-90
modeling and k i n e t i c s , 176-78
Oxygen, atomic, 111-13
r e a c t i o n with carbon monoxide with
added gases, 268,269t
Oxygen gas
i n 1,3-butadiene flame mole f r a c t i o n
and f l u x p r o f i l e s , 6,8-13
and C disappearance, 260,262f
e q u i l i b r i u m constants, 263-66
pressure e f f e c t
i n e l e c t r i c spark
i g n i t i o n , 212,215f,220-21
and ozone decomposition, 268,269t
reaction
with NH, 109-12
with NH , 105-9
Oxygenated hydrocarbons, mole f r a c t i o n
and f l u x p r o f i l e s i n near sooting
1,3-butadiene flame, 6,8-13
Ozone decomposition, thermal, 267-75
Plate obstacles, o r i f i c e , flame speed

for hydrogen-air mixtures, 1 2 3 - 3 3
Polynuclear aromatic molecules, forma
t i o n i n acetylene-oxygen flame
Pressure e f f e c t s
of acetylene on decay rate i n
hydroxy1-acetylene
r e a c t i o n , 245,246f
of oxygen on disappearance rate of
C r a d i c a l , 260,262f
on detonation parameters of f u e l o x i d i z e r mixtures, 180-90
Pressure p r o f i l e s i n shock to detona
t i o n t r a n s i t i o n , 154-59
Probe, Langmuir, ion concentrations i n
acetylene-oxygen flame near soot
threshold, 36-46
Propagation and i n i t i a t i o n i n
detonations, 157-72
Propane
detonation k i n e t i c s , 176-90
c a t i o n s , rate
c o e f f i c i e n t s , 59t,60t,6lt
shock tube i g n i t i o n , 176-78
Propane-air flame speeds, 127-33
Propargylium i o n , structure and
r e a c t i v i t y , 52-^56
Propylene, k i n e t i c s of gaseous
detonations, 176-90
Pulsed dye l a s e r , 240-41
Pyramid structure of C5H5
isomers, 57,58f,62,64f
Pyrolysis
design f o r high temperature
c e l l , 258,26lf
with fluorescence detection of
hydroxyl r e a c t i o n with
acetylene, 241-54
2
R
1-Penten-3-yne, formation of cyclopen
t a d i e n y l c a t i o n s , 60t
Perturbations,
i g n i t i o n wave, 241
sound wave, 154,155t
theory with bond a d d i t i v i t y
c o r r e c t i o n s , 103-13
Phase e f f e c t from heat release, sound
wave, 153f
Phenylacetylene, i n near-sooting
1,3-butadiene-oxygen-argon
flame, 15-16,I8f
Phenylium i o n , structure and
reactivity, 56-57
Planar structure of C5H5
Plasma j e t i g n i t e r s
a p p l i c a t i o n i n engines, 199-203
i g n i t i o n process, 1 9 6 - 9 9
Radicals
hydroxyl, reactions with ethane and
ethylene, 230-36
f r e e , UV-absorbing, 226,227f,229f
hydroxy, 239-55
mass spectrometric sampling, 216-18
Rayleigh-Taylor i n s t a b i l i t y , I68f
Reactive centers, 154
R e a c t i v i t i e s of hydrocarbon ions i n
soot formation, 49-65
Reversed-geometry, double-focusing
mass spectrometer, c o l l i s i o n induced d i s s o c i a t i o n r e a c t i o n of
ions, 49-65
Rotational e x c i t a t i o n , hydroxide i o n
i n ammonia flame, 75-77
Rotational temperature,
hydroxide, 72,74f

286
S
Schlieren photography
of spark i g n i t i o n , 208-11
time-resolved, 196,197f
Shchelkhin s p i r a l obstacle and flame
mixtures, 123-33
Shock and detonation, I63,170,171f
i n hydrogen-oxygen f u e l , 154-58
i n propane, 176-78
S i n g l e - c y l i n d e r t e s t engine, 199-201
S i n g l e t s t r u c t u r e of C5H5
Soot p a r t i c l e s
i n acetylene-oxygen flames near
threshold, 33-46
i n ethylene-oxygen-argon
flame,
diameter, density, and surface
area, 24,25f
formation
and hydrocarbon i o n r e a c t i v i t i e s
and s t r u c t u r e s , 49-65
mechanism, 23-31,33,45-46
volume f r a c t i o n s , ethylene-oxygenargon flame, 24,26f
Sound waves and chemical
processes, 151-54
Spark electrodes and flame
propagation, 216-21
Spark i g n i t i o n chemistry, 205-21
S p e c i f i c heat r a t i o f o r s i n g l e
c y l i n d e r t e s t engine, 200
Speed o f flame, 121-37
d e f l a g r a t i o n to detonation, 142
vs. distance f o r hydrogen-air
flames, 123-26
Spherical detonation, 186
S p i r a l obstacle, Shchelkhin, and flame
mixtures, 123-33
Stern-Volmer p l o t of the disappearance
rate of C2, 260,262f
Stoichiometry, carbon to oxygen, and
mechanism f o r soot growth, 23-31
Styrene formation i n near-sooting
1,3-butadiene-oxygen-argon
flame, 15-16,I8f
Sulfur hexafluoride as IR
absorber, 240-41
Surface area of soot i n ethyleneoxygen-argon flame, 24,25f
Surface growth of soot, equation, 27
Swan bands, e x c i t a t i o n , f o r C , 259
TemperatureContinued
and r a t e constant data f o r r e a c t i o n
of hydroxyl and
acetylene, 241-53
r o t a t i o n a l , f o r hydroxide, 72,74f
Tetrafluoromethane e f f e c t , 268,269t
Time-of-flight d e t e c t i o n , 206-8
Time-resolved molecular beam mass
spectrometry, 206-8,210-16
Time-resolved Schlieren
photographs, 196,197f
Toluene
formation i n near-sooting 1,3-butadieneoxygen-argon flame, 15-16,17f
rate c o e f f i c i e n t s f o r reactions with
cyclopropenyl and cyclopen
tadienyl
cations, 54t,59t,60t,6lt
Transmissible turbulent flow
s t r u c t u r e , 122-23
Transport of ions
convective, concentration
equation, 36
d i f f u s i v e , i o n concentration
equation, 35-36
T r i p l e quadrupole mass spectrometer,
c o l l i s i o n of hydrocarbon
ions, 49-65
T r i p l e t s t r u c t u r e o f C5H5
Tube diameter
and d e f l a g r a t i o n to
detonation, 145-46
and detonation c e l l s i z e , 139-40
and k i n e t i c s o f gaseous
detonations, 183-89
Turbulence and flame
a c c e l e r a t i o n , 121-37,163-70
Turbulent flow s t r u c t u r e ,
transmissible, 122-23
Two-dimensional flame, b a f f l e p l a t e
flame obstacles, 134-35
U
Unimolecular decomposition theory,
ions i n ammonia flames, 82-85
Unimolecular r e a c t i o n r a t e theory,
Troe, 249-54
UV-absorbing free
r a d i c a l s , 226,227f,229f
UV l a s e r source, laser-induced
fluorescence s t u d i e s , 230-36
Temperature
and density r e l a t i o n s h i p s , 241
V e l o c i t y , burning, and b a f f l e p l a t e
flame obstacles, 134-35
Vinylacetylene, r o l e i n aromatic
species formation, 16-20

287
INDEX
W
Water, mole f r a c t i o n and f l u x p r o f i l e s
i n near-sooting 1,3-butadiene
flame, 6,8-13
Zeldovich-von Neumann-Doring
model, 177
Vinylcyclopropenylium isomer,
structures, 57,58f,62,64 f
V i s i b l e dye l a s e r s , second harmonie
generation, 228t
Volume, constant, combustion
chamber, 196-201
Volume fractions of soot i n ethyleneoxygen-argon flame, 24,26f
Vortex Dynamics Code, flame
acceleration, 133-37
Production by Paula Brard

indexing by Florence Edwards
Jacket design by Anne G. Bigler
Elements typeset by Hot Type Ltd., Washington, D.C.
Printed and bound by Maple Press Co., York, Pa.


Combustion Chemistry

Transféré par

Informations du document

Titre original

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Combustion Chemistry

Transféré par

Droits d'auteur :

Formats disponibles

ACS

The Chemistry of Combustion

Thompson M. Sloane, EDITOR

American Chemical Society, Washington, D.C. 1984

Library of Congress Cataloging in Publication Data

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.fw001

Includes bibliographies and indexes.

In The Chemistry of Combustion Processes; Sloane, T.;

ACS Symposium Series

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.fw001

Davis L. Temple, Jr.

In The Chemistry of Combustion Processes; Sloane, T.;

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.fw001

In The Chemistry of Combustion Processes; Sloane, T.;

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.pr001

General Motors Research Laboratories

In The Chemistry of Combustion Processes; Sloane, T.;

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

J. A. COLE , J. D. BITTNER , J. P. LONGWELL, and J. B. HOWARD

Current address: Energy and Environmental Research Corporation, 18 Mason, Irvine, CA

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

CHEMISTRY OF COMBUSTION PROCESSES

In The Chemistry of Combustion Processes; Sloane, T.;

in Aromatic Species Formation

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

Estimated Probable Errors f o r Species Mole-Fraction

Estimated Probable Error

s p e c i e s were determined r e l a t i v e t o each o t h e r w i t h g r e a t e r a c c u

In The Chemistry of Combustion Processes; Sloane, T.;

CHEMISTRY OF COMBUSTION PROCESSES

w i t h t h e known s t a n d a r d G i b b s e n e r g y charge, G, f o r R e a c t i o n (1)

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

In The Chemistry of Combustion Processes; Sloane, T.;

in Aromatic Species Formation

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

HEIGHT ABOVE BURNER (mm)

In The Chemistry of Combustion Processes; Sloane, T.;

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

In The Chemistry of Combustion Processes; Sloane, T.;

in Aromatic Species Formation

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

In The Chemistry of Combustion Processes; Sloane, T.;

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

F i g u r e 5. M o l e f r a c t i o n a n d f l u x p r o f i l e s o f H, H^, OH, a n d E^O

In The Chemistry of Combustion Processes; Sloane, T.;

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

in Aromatic Species Formation

DISTANCE FROM BURNER, mm

F i g u r e 6. Mole f r a c t i o n and f l u x p r o f i l e s o f one-, two-, and

In The Chemistry of Combustion Processes; Sloane, T.;

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

In The Chemistry of Combustion Processes; Sloane, T.;

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

in Aromatic Species Formation

DISTANCE FROM BURNER,mm

In The Chemistry of Combustion Processes; Sloane, T.;

CHEMISTRY OF COMBUSTION PROCESSES

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001

Using the r a t e constant of T u l l y et a l . ( 1 6 ) , the temperature

Reaction 6 i s r a t e l i m i t i n g here w i t h a t y p i c a l r a t e constant of

In The Chemistry of Combustion Processes; Sloane, T.;

in Aromatic Species Formation

Publication Date: April 16, 1983 | doi: 10.1021/bk-1983-0249.ch001