Molecular Beam Mass Spectrometric Sampling of Methane Flame

UNIVERSITY OF CALIFORNIA
Los Angeles
A FIBFIS Sampling Study of
Formation of Nitric-Oxide in a Premixed
Fuel-Rich Methane-Air Flame
A thesis submitted in partial satisfaction
of the requirement for the degree
Raster of Science in Engineering
by
Ivan A. Gargurevich
1980
The thesis of Ivan A. Gargurevich is approved.
U, D. Van Vorst
Ouen I, Smith
Eldon L. Knuth, Committee Chair
University of California, Los Angeles
1980
To Horn and Dad,
Lucia,
Cynthia,
Irene,
Sergio,
and Carmen,
TABLE OF CONTENTS
PAGE
LIST«OF FIGURES . . . . Vi
LIST OF TABLES ... viii

ix
LIST OF SYMBOLS . .
xii
ACKNOWLEDGMENTS
ABSTRACT OF THE THESIS xiii

CHAPTER 1. INTRODUCTION . ,.",'," i
CHAPTER 2. PREVIOUS STUDIES OF NO FORMATION IN
HYDROCARBON FLAMES . . .. 10
2.1 The Formation of NO in Fuel-Lean Flames . j_g
2.2 Prompt NO Formation ........... 15
2.3 Formation of NO in Fuel-Rich Flames ... 22

2.4 Mechanisms of Methane Oxidation ..... 30
2.4.1 Methane Oxidation in Fuel-Lean
Flames .............. 30
2.4.2 Methane Oxidation in Fuel-Rich
Flames .............. 34
CHAPTER 3. EXPERIMENTAL APPARATUS 44
3.1 An Introduction to Sampling Techniques
in Combustion Studies .......... 44
3.2 Possible Composition Distortions in MBMS

Sampling of Flames ........... 53
3.2.1 Free-3et Expansion ........ 54
1
PAGE
3.2.2 Chemical Relaxation in Supersonic
Expansion ............. 59
3.2.3 Species Condensation ....... 63

3.2.4 Pressure Diffusion ........ 65
3.2.5 Relaxation Phenomena ....... 69
3.2.6 Skimmer Interference . . . . . 0 . 71
3.2.7 Mach-Number-Focusing „ . 72
3.2.8 Background Scattering ....... 76
3.2.9 Flame Perturbations by Sampling
Cones 77
3.3 The U.C.L.A. MBMS Sampling System .... 83
CHAPTER 4. EXPERIMENTAL PROCEDURE AND DATA RE-
DUCTION ......... 87
4.1 Composition Measurements ......... 87
4.2 Temperature Measurements ......... 91
4.3 Calibration Procedures .......... 93
CHAPTER 5. EXPERIMENTAL RESULTS ... 96
5.1 Temperature Measurements in the Flame . . 97

5.2 Stable Species Profiles . . 110
5.3 Formation of Nitric-Oxide in the Flame . . 112
5.4 C2H2, C2H6 Profiles . .. . 124

5.5 CH. and H2CO Species in the Flame .... 130
CHAPTER 6. CONCLUSIONS .... 136
REFERENCES . . . . . . 140
LIST OF FIGURES
FIGURE PAGE
1. node of coal formation . 3
2. The dependence of CH20, C2H4, C2H2, and H2
peak concentrations on flame equivalence
ratio ................... 40
3. The dependence of peak C2H,, C2H2, and H2
on peak JCH-, } for a range of flames $ =

0.56 to 1.25 \ 41
4. The U.C.L.A. MB[*]S sampling system ..... 50
5. Temperature ratio as function of dimension-
less flou time for free jet gas flows from
orifice 52
6. Free-jet shock structure .......... 55
7. Schematic diagram of model considered in
Mach-number-focusing 74
8. Intensity vs. electron energy for Argon . . 89

9. Temperature profile measured using TDF tech-
nique ..... ......... 93

10. Temperature profile measured using TOF tech-
niques 100
11. Normalized Oxygen profile (tip dia. = 2.0

104
mm, d^ = 0.24 mm)
12. Normalized Oxygen profile (tip dia. = 0.5 mm,
d^. = 0.30 mm) ........ . . ..... 105

FIGURE PAGE
.
13. C02 normalized profile (tip dia. = 2.0 mm,
d# = 0.24 ram) ................ IDS

14. Normalized C02 profile (tip dia. = 0.5 mm,
d^. = 0.30 mm) . . . . . .107
15. 02, CI-L, and C02 mole-fraction profiles for
CH^-Air flame ................ ill
16. NO concentration profile .......... 114
17. NI-U concentration profile .......... 115
18. HCN concentration profile .......... lie
19. Normalized m/e = 30 profile 117
20. Normalized m/e = 17 profile ......... 119
21. Normalized m/e = 43 profile ......... 123

22. C2H2 concentration profile ......... 126
23. Normalized m/e = 27 profile . .... . . . . 127

25. C-atom concentration profile ........ 131
26. CM concentration profile .......... 132
27. CH2 concentration profile 133
LIST OF TABLES
TABLE PAGE
1. Methane oxidation in fuel-lean mixtures ... 35

2. Methane oxidation in fuel-rich mixtures ... 36
\M 1
-
LIST OF SYMBOLS
a speed of sound
C. calibration constant appearing in Eq. (56)
£•
d effective source-orifice diameter
d.£ cone orifice diameter
d, skimmer entrance diameter
D binary diffusion coefficient
E C3 electron energy in ev
#
E activation energy
f mole fraction of heavier species
h total enthalpy
I. ion signal intensity of species i
ID electron emission in mamp
k. foruard reaction rate coefficient for the ith
reaction
k__ • reverse reaction rate coefficient for the ith
reaction
K equilibrium constant
Kn Knudsen's number
'"Id skimmer entrance - detector distance
m mean molecular ueight
m. molecular ueight of species i
m/e mass to charge ratio
n number density
n, number density at detector
n, number density at skimraer entrance
p pressure
j mass density
Re Reynolds number
S speed ratio
i
Sj_ speed ratio perpendicular to jet axis
Sc Schmidt number
T temperature
Tj^ static temperature perpendicular to jet axis
T,, static temperature parallel to jet axis
t time
u most probable velocity of molecules
v diffusion velocity
X nach disk location
Y r-lach disk diameter

YDD diameter of the barrel shock
thermal diffusivity
u~~t enrichment factor as defined in Eq. (49)
n calibration factor appearing in Eq. (56)
0 (Fuel/Air) actual/(Fuel/Air) stoich., equiva-
lence ratio
0 heat capacity ratio, C /c
'Vu in,p relaxation time at constant h,p
CT relaxation time at constant T.p
I »P
L AB mean time between collisions of A and B mole-
cules
\ mean free path
cr hard sphere collision cross section
Subscripts
eq denotes equilibrium values

0 denotes stagnation conditions
1 denotes conditions at skimmer entrance
frozen process
ACKNOULEDGPIENTS
I uould like to express ray gratitude to Dr.

Eldon Knuth for his continued guidance and encourage-
ment during the time this uork was performed.
Also, I uant to thank all members of the Mole-
cular Beam Lab. for their cooperation, and especially
to Dr. 0. Smith, Fir. Uayne E. Rodgers, and Ph.D. stu-
dent S. Yoon for sharing their knowledge and useful
information.
This study uas supported by NSF under Grant
No. ENG-7709190.
XII
ABSTRACT OF THE THESIS
A MBWS Sampling Study of
Formation of Nitric-Oxide in a Premixed
Fuel-Rich Methane-Air Flame
by
Ivan A. Gargurevich
Plaster of Science in Engineering

University of California, Los Angeles, 1980
Professor Eldon L. Knuth, Chair
The formation of NO in a fuel-rich, premixed
methane-air flame at one atmosphere uas studied using
molecular-beam-mass-spectrometric (MBMS) sampling tech-
niques.
A flat flame of equivalence ratio 1.37 uas
sampled uith particular attention given to NO, HCN, HNCO,

and MB., species. The onset of formation of HCN uas
found to occur prior to the formation of NO, approxi-
mately at the same time as the formation of NH,, and very

near the primary reaction zone of the flame. Decay of
HCN leads to NH- formation, and, to a lesser extent, to

iJ
NO formation. HNCO is observed at very lou concentrations
in the post-flame gases, and acts as an intermediate in
HCN decay. The peak mole fractions of HCN and NH^

about 67 and 44 ppm., respectively,and Nitric-
Oxide reaches a mole fraction of 56 ppm. after all of the
HCN, and NH^ have decayed. The Zeldovich mechanism,
taking into account radical overshoot, accounts, at
most, for 10 ppm. of the NO formed in the flame; the
rest is the result of HCN decay.
The same flame uas sampled for C, CH } CH,-,,

and CI-U« The peak mole fractions of C, CH, and CH-
were found to be about 206, 481, and 908 ppm., respec-
tively, uith an uncertainty of a factor of approximately

2. Because of their greater concentrations, CH and CH~
are the most likely to lead to HCN formation. The con-
tribution to the CH., profile from CH, could not be to-
tally eliminated, even at electron energies as lou as
13.3ev. No effort uas made to estimate its mole frac-
tion in the flame. The CH-, profile peaks uithin the pri-
mary reaction zone.
The flame uas also sampled for H-CO. Its
formation is observed to occur before the formation
of CHr, and upstream from the reaction zone of the flame.

J
The rate of formation CH-, does not reach significant

levels until most of the formaldehyde has decayed.
A relatively large concentration of acetylene
(2100 ppm.) uas found; its formation and decay occurred
mostly uithin the primary reaction zone. Ethane, in
much smaller concentrations, uas also observed in the
same region. The tuo-carbon species provide additional
xiv
paths for the decay of CH- and must be included in the
kinetic modeling of fuel-rich hydrocarbon flames,
Visible attachment of the flame to the quartz
cone uas observed for the flame of equivalence ratio
1.37. Temperature measurements, made using time-of-
flight (TOF) techniques, shoued that the effect of

attachment is to decrease the measured temperature gra-
dient within the reaction zone. A cone of smaller
tip diameter minimizes this effect. Relative inten-

sity profiles shoued also smaller measured gradients
uithin the primary reaction zone for a cone of relative-
ly large tip diameter. Attachment of the flame to the

cone persisted approximately until the end of the pri-
mary reaction zone.
xv
CHAPTER 1
INTRODUCTION
In the last decade, in order to satisfy an

ever-increasing demand for energy, and as a result of
continuing decline in the domestic production of crude
oil, the United States has been forced to import crude
oil and refined products in increasing amounts. It is
83
forecast that, in 1980, thirty percent of our total
energy uill come from the Middle East Nations. Fur-

thermore, since 1972, the fraction of the energy used
for producing the U.S. GiMP uhich has been based on
imported oil has doubled, increasing from a level of
about 13£o of the U.S. GNP in 1972 to about 26% of
the U.S. GNP in 1978. Since the end of 1978 the OPEC
cartel has raised the price of its exported crude by
61j£, and it is estimated that by 1985 it uill reach
nA
340 per barrel .
In 1985 the U.S. could be import-
83
ing as much as 15 million barrels per day and, with
an estimated price of $40 per barrel, the cost for
1985 would be $220 billion. By comparison, the value
of oil imports into the U.S.A. in 1972 uas $4.5 billion,

The finite limits of U.S.A. oil and natural
84
gas reserves are fairly well established ; both could
be exhausted in ten years if they uere worked to their
fullest capacity. However, the estimated resources
of coal amount to approximately 90,000 x 10 Btu.
(or about 430 billion tons) which at the present con-
sumption rates would last for about 666 years.
In the near future, the U.S.A. will have to
find or exploit alternative sources of energy if it

is to play an important role in the world community.
In Duly 1979, President Carter announced his Energy
Plan. The main objectives of the Plan were to dimin-
ish oil imports, to accelerate the conservation of oil
fuel, and to spend $88 billion over ten years to pro-
mote synthetic-fuel production from coal and shale
rock. According to Carter's Energy Plan for about the
next ten years, oil imports would be kept at the 1977
level of 8.2 million barrels per day; 2,5 million bbl./
day would be gained by synthetic fuel production and 2
million bbl./day through conservation and conversion
measures. Carter's Plan would require coal production
to double by 1985 (in 1979 coal production was 625

million tons per year) °r, in the seven-year period
1979-1986, 107 million tons of new capacity would have
to be added every year.

ORIGINAL PLANT MATERIAL CCA' ?/AC c RA.'
(VISUAL MiCHOSCCPY)
FESINGUS MATERIAL
CUT1CL£S,S?OH£S
RESETS
WOOC, CGnX
j
CiRSCNIZATION
V,iCF.CN!TE
RANK F EAT— L i G N 1 TH U S —• 3 i ~J M ! N G U S —"A r-JTH= AC ~

KIGH M=D.
C5A
%C 60 ra 80 S3
%0 25 15 3
Ci!-CR:riC I2CCO 1200 o I4OCO ISOOa S55GC
VALUE
Fig, 1. Mods of coal formation . ( Source : Ref. 85 .)

It is clear then that combustion of coal and
products derived from coal and shale rock will be play-
ing an important role in the U.S. energy picture for years
to come. (Nuclear energy supplies about 3% of the
total energy produced in the U.S. today. Its devel-
opment, however, has encountered much opposition and it
is unlikely that construction of new nuclear plants
uill be started in the 1980's). Coal originates pri-
marily from plants. Fig. 1 shows the steps in coal

formation. Through a series of evolutionary changes,
the primary products of the original decomposed plant
matter becomes transformed sequentially into peat,

lignite, subbituminous coal, bituminous coal, and fi-
nally to anthracite. Uith these transformations the
carbon content increases and the oxygen content decreases.

n j-
Studies ' indicate that there is some correlation be-
tween coal rank and its aromaticity, 40-50^5 aromatic
carbon content for subbituminous coal and 90% aromatic

carbon content for anthracite. These studies showed
no correlation between H/C mole ratio and percent aro-

matic carbon. Oxygen occurs predominantly as pherolic
or etheric groups in coal. Sulfur found in coal has
a similar functional chemistry to Oxygen. Sulfur con-
tent in coal varies from 2 to 3 percent. Nitrogen
occurs predominantly as pyridine or pyrrolic type rings,
and coal contains typically from 1 to 2 percent nitrogen

by ueight. Coal structure is consistent with highly
I-5
substituted aromatics uhich are not highly condensed.
I
Coal undergoes primary decomposition in the tempera-
ture range 400 - 450 C.
The realization of limited and non-reneuable
energy resources and the increasing role of combustion
in the years ahead uill require extensive research

in the areas of energy conservation and combustion
problems. As a result of President Carter's Energy
Plan, there uill be a shift to direct coal burning
by the Utilities Companies and Industry. The health,
safety and environmental threats posed by mining and
burning of coal are severe. Increased coal burning
uill result in larger emissions of sulfur dioxide,
carbon dioxide, and nitric oxide into the atmosphere.
The accumulation of carbon dioxide might result in

the so called "Greenhouse" effect predicted by many
scientists. The large amounts of ash that uill result
from coal burning uill have to be disposed of in an

environmentally safe manner. The production of syn-
thetic fuel uill also cause environmental problems.
Furthermore, the production of synthetic fuel might

require huge amounts of uater for hydrogen production.
The strain on existing uater supplies might be consider-
able and one can foresee legal battles for uater rights
betueen the coal-producing states.

In 1974, transportation accounted for 54/5
n £!
of the total liquid fuel consumption ' in the U.S.
It is most likely that transportation uill depend pri-
marily on liquid fuels in the near future. Most of
the liquid fuel being consumed today in America is
lou in aromatics content and has a high H/C content
(the average H/C ratio being 1.9). Houever, unless
extensive hydrocracking and hydrogenation are conducted,
the properties of synthetic fuels are different from
those of the fuels being used today in transportation.
Synthetic fuels are high in aromatics content and have
a H/C ratio of about 1.2-1.5. Transformation of syn-
thetic fuels from coal into more "gasoline-like" fuel
Rfi
results in an energy loss of about 2Qfa of the heat
of combustion of the syncrude being processed. The
elimination of restrictions on H/C ratio and boiling
range in fuel manufacture uould result in a consider-
able reduction in the cost of the fuel. As a result
of its properties, synthetic fuel combustion uould re-
sult in the emission of large amounts of soot by the
internal combustion engine . Thus, extensive research
is needed to eliminate the need for high levels of hy-
drogenation and boiling range conversion in the manu-
facture of fuels from coal. Furthermore, more research
is needed in the chemistry of soot formation and burn-
out.
It is evident that, in the future, ue uill
have to burn prime fuels more efficiently with less pollu-
tion and ue shall also have to burn much material that
is not nou considered suitable fuel at all. As Uein-

oY
berg points out, progression in combustion systems
is in the direction of more controllability. The pro-
gression has been from diffusion flames (the reaction
zone is aluays near stoichiometric, corresponding to

the maximum possible flame temperature and hence the
largest NO emission) to premixed flames, uhich allows
one to vary flame temperature, burning velocity, ig-
nition temperature, and stability criteria by controlling
the fuel/air ratio to the uell-stirred reactor. Uein-
berg proposes that the next step should be breaking auay
from this dependence on initial fuel/air ratio and con-
trol the reaction rates in the flame independently.
To take this desirable step on combustion systems, ue
must control the reaction rate independently by making

the temperature in the reaction zone a separate para-
meter, using variable heat recirculation, injection

of free radicals, radiation, etc.
This study is concerned with the kinetics of
formation of nitric oxide in an atmospheric, fuel-rich,
premixed, methane-air flat flame, and it is part of a

series of studies that are being conducted in U.C.L.A.
with regards to nitric oxide formation from fuel-ni-

trogen in flames. To give the reader an idea of the
magnitude of this NO formation, in the study of methane-
air flat flames by R. Gay at U.C.L.A., a concentration
of 140 ppm. uas reported in the post-flame gases of a
mixture of equivalence ratio 1.1. In this same flame,
the primary reaction zone uas characterized by the
rapid formation and decay of formaldehyde uith a max-
imum concentration of 540 ppm., and NO formation uas
restricted to the post-flame region. The primary reac-
tion zone uas located uithin the first 5mm. from the
burner surface. In the study of NO formation in a fuel-

rich flame, the coupling betueen the NO-formation reac-
tions and the combustion reactions must be considered.
This requires a knouledge of the combustion mechanism,

and for methane combustion, although extensively studied,
there are questions regarding the rate-determining
step, the f^CO-decay mechanism, the fate of CH~ species,
and the role of t^ hydrocarbons. Nitric oxide above
that predicted by the Zeldovich mechanism is said to

form via the formation and decay of HCN. The forma-
tion mechanism for this species has been studied but
very little is knoun about its decay mode. Experiments
indicate that NHj_ species and OCN-species might play

an important role in the decay of HCN.
It is the aim of this study to ansuer or
clarify some of the questions regarding the kinetics

of NO formation in fuel-rich, premixed methane-air flames.
It is hoped that this uill be of some value in the study
of NO formation in flames containing fuel-nitrogen.
The study of flames uill be conducted using
a molecular-beam-mass-spectrometer (MBNS) sampling

system. This system has been shoun to meet all the
requirements for sampling of high temperature systems
uith excellent balance. The use of MBFIS sampling sys-

tems could undoubtedly play an important role in com-
bustion research in the near future. MBPIS sampling
techniques allou one to follou stable and radical spe-
cies uith minimum distortion. This is valuable help
in the study of (a) oxidation mechanisms and (b) rate
coefficients of elementary reactions. As mentioned
above, MBNS sampling techniques are being used at U.C.L.A.
to study the fate of nitrogen-bearing species and,
more recently, sulfur-containing species in flames.
These studies uill no doubt help determine more effi-
cient and more clean uays to burn fuels such as coal
or liquid fuels derived from it.

CHAPTER 2
PREVIOUS STUDIES OF NO FORMATION
IN HYDROCARBON FLAMES
2.1 The Formation of NO in Fuel-Lean Flames
It is generally accepted that the formation

of nitric oxide in the post-flame gases of lean or
near-stoichiometric hydrocarbon-air flames is modeled
by reactions originally proposed by Zeldovich .
0 + N2 # NO •»• N (1)
N + 02 £ NO + 0 (2)
From experimental data, Zeldovich and co-uorkers con-
cluded that the rate of MO formation in fuel-lean or
near-stoichiometric hydrocarbon flames uas much slouer
than the combustion rate, and that the NO-formation
rate could be calculated assuming equilibration of

2
the combustion reactions. Lavoie, Heyuood and Keck
have indicated that the reaction
N -f OH £ NO + H (3)
also can contribute to NO production, especially in
near-stoichiometric and fuel-rich mixtures, and it is
nou generally included in kinetic studies of NO forma-
tion.
3
Uestenberg studied the kinetics of NO forma-
10
tion in lean, premixed hydrocarbon flames. Using re-
actions (1), (2), and (3), he derived equation (4)

for the rate of NO formation
= 2k1(D)(N2) 1"(ND)2/K(02)(N2) (4)

dt
k2(02)+k3(OH)
where K is the equilibrium constant for the overall

reaction Nj + Oj v1 2ND. In the derivation of equation
(4), it is assumed that (i) the reactions occur under
constant-volume conditions, (ii) d(N)/dt is close to
zero; and (iii) Reaction (5) is equilibrated in the
post-flame gases.
0 + OH ^ H + 02 (5)
The fact that condition (iii) is quickly attained in
the secondary zone of flames has been amply demon-

n Tn
strated ' . Calculation of the NO formation rate
by Equation (4) requires values of the local tempera-
ture and concentrations of 02, N 2 , 0, and OH. Houever,

as first suggested by Zeldovich, Uestenberg took final
equilibrium values of the temperature, and of the N 2 ,
0~, OH, and 0 concentrations.
Using the equilibrium approximation of IM2,
0?, OH, and 0 concentrations, Bowman obtained the
following NO formation rate (using data from Ref. 4)
11
16
d(NO) 6x10 T ~"2expf^69,090/T
r "l x ( 0 0J)
dt eq k eq/ 2 'eq eq
moles (6)
cm sec
Elevated temperatures and high 02 concentrations in

the post-combustion gases result in relatively high
NO-formation rates. Experimental studies of NO for-

mation in the post-combustion zone of laboratory flames
support this simplified mechanism.
Neuhall and Shaded studied the formation
of nitric oxide in the immediate vicinity of a flame
front propagating through a high-pressure combustion
vessel in order to investigate the formation of nitric
oxide under conditions similar to those occurring in

internal combustion engines. Spectroscopic techniques
uere used to determine NO concentrations. Experimental

data uere obtained for hydrogen-air mixtures at pres-
sures of 240, 325, and 340 psia, and 0.7, 0.9 and 1.0
equivalence ratios respectively. Temperatures ranged
from 2000°K to 2500°K. They found that under these

conditions NO is formed primarily in the post-flame
gases, and that the rate of NO formation can be pre-

dicted by the Zeldovich mechanism, uith oxygen- and
nitrogen- atom concentrations set equal to their chem-
ical-equilibrium values.
*>
Livesey et al s t u d i e d the f o r m a t i o n of NO
12
in atmospheric-pressure, premixed, oxy-propane flames.
They used many small diameter stainless steel tubes as
flameholders. An outer shield of argon uas used to
H§r -
prevent outside nitrogen from reaching the combusted
gases. Gas samples uere taken through a uater-cooled
probe and analyzed for N0Xv by the Saltzman method.
Temperatures in the burned gas region uere determined
spectroscopically from the temperatures of rotationally
excited OH. Temperatures uere in the vicinity of 2800°K.
They shoued that reactions (1) and (2) are sufficient
to explain the rate of formation of NO in the post-
flame gases.
The effects of combustion -modifications on
the formation of nitric oxide in CH^/air flames uere
studied by England . A 250,000 Btu/hr ring-type burner
uas used. Nitric oxide in the flue gas uas measured
uith a long-path infrared analyzer at concentrations
from 2 to 500 ppm. Gas samples uere uithdraun by a
uater-cooled quartz probe. He found that nitric oxide
emissions could be reduced by 9Q?0 from peak levels by
burning very fuel-rich flames, and that by reducing
the air preheat from 650°F to 50°F, peak nitric-oxide
levels dropped 67%. The louer NO levels at louer air
temperatures uere due to louer flame temperatures.
England also obtained data for NO concentrations uhen
up to 32/o of the combustion gases uere recirculated.
Nitric oxide in a flame burning uith a combustion air
temperature of 650°F uas reduced by B2% from the peak
levels by 32^ recirculation. Nitric-oxide production
uas lowered uith product-gas recirculation because
of a reduction in the methane-air flame temperature.
These results could have been predicted from Equation
(6); louer flame temperature, Teq

Dn , results in a smaller
rate of formation of nitric oxide. Reduction in the
oxygen level has a similar effect on the rate of NO
formation.
14
2.2 "Prompt" NO Formation
That the formation of NO in the primary re-
action zone might involve a mechanism other than the

g
Zeldovich mechanism uas first indicated by Fenimore
in the Thirteenth Symposium (international) on Combus-

tion. He measured the formation of NO in premixed
atmospheric flames of ethylene, methane, and propane
uith N2 " ^2 mixtures. Post-flame gases were uithdraun

by a quartz microprobe and collected in an evacuated
flask. NO and N02 concentrations uere determined by

chemical analysis. Temperatures uere measured by the
Sodium-line reversal method 20 and uere constant over
the region investigated. Fenimore found that the kin-
etics of NO formation in the post-flame region is de-
scribed by the Zeldovich mechanism, Houever, extra-
polation of the measured NO formation curves back to

zero time gave positive intercepts, indicating, as Feni-
more suggested, a transient formation of NO in the
primary reaction zone, the growth rate of uhich uas

too fast to be explained by the Zeldovich mechanism.
He labeled this intercept NO as "prompt" NO. Since
positive intercepts uere not found in hydrogen or CO
flames, Fenimore suggested reactions such as
CH + N2 ^ HCN + N (7)
C2 + N 2 ^ 2CN (8)
15
to explain the "prompt" NO.
Controversy aroused regarding "prompt" NO,
and numerous investigators have made experimental stud-
ies to prove or disprove "prompt" NO formation.
Bowman 12
" investigated the formation of NO
in shock-induced combustion of H2/02/N2
Concentration time-histories of NO, OH, and H?0 uere
measured during reaction using spectroscopic techniques,,
NO formation rates uere found to exceed the rates pre-
dicted by the post-flame zone mechanism. It uas shoun
that the observed rates uere consistent uith reactions
(1) through (3), if 0 and OH concentrations uere cor-
rectly determined. In the region of rapid NO formation,
observed radical concentrations uere in excess of cal-
culated equilibrium values. Hence, the rapid NO forma-
tion rates uere found to be the consequence of non-equil-
ibrium combustion chemistry.
Further evidence for non-equilibrium chemistry
in the reaction zone of flame uas gathered by Bouman
and Seery 21 . They studied shock-induced combustion
of CH/L - 0? - N 2 mixtures dilutad in argon. Concen-
tration histories of NO, OH, and C02 uere measured
using spectroscopic techniques. Initial temperature
uas in the range 2600 - 3200^, and the initial pres-
sure uas 3.5+ 0.5 atm. They found NO-formation rates
to be consistent uith reactions (1), (2), and (3).
16
Furthermore, discrepancies between observed NO forma-
tion rates and those using an "equilibrium" model for
NO formation uere explainable in terms of "radical
overshoots" in the reaction zone. They did not find
evidence to suggest that other reactions uere of im-
portance in the NO-formation mechanism.
Sarafim and Pohl studied NO formation in

one atmosphere premixed methane-air flat flames of
equivalence ratios from 0.89 to 1.15, Gases uere burned

on a water-cooled porous-disk, flat-flame burner.
Gas samples uere withdrawn through a water-cooled stain-
less-steel probe. NO concentrations were determined

by a modified Saltzman method; other species were mea-
sured using a gas chromatograph. They found that the
peak rates of NO formation in the flame zone were one
to two orders of magnitude greater than the values
in the post-flame zone, and to be consistent with the
modified Zeldovich mechanism (Reactions (1) - (3)),
when free-radical concentrations (of 0, OH, and H)
were correctly estimated.

The "Radical Overshoot Theory" requires a
detailed consideration of the kinetics of the fuel
combustion, or the use of other suitable approximate
methods to compute the non-equilibrium concentrations
of 0, OH, and H near the primary reaction zone in order
to determine NO formation rates. Detailed combustion
17
mechanisms are known for only a feu fuels — H?, CO,
and CFL (methane oxidation will be discussed in a la-
ter section), and a simplified approach involving the

"partial equilibrium" of Reactions (9) - (11) is used
in most cases.
H + 02 £ OH + 0 (9)
0 + H2 ^ OH + H (10)
H2 + OH £ H20 + H (11)
In the "partial equilibrium" approach, the radical
reactions (9) - (11) are considered to be equilibrated

in the flame. This is not to say that the radical
concentrations are equal to their equilibrium values,

rather the ratio of the products to reactants concen-
trations for each of the reactions (9) - (11) is equal
to the reaction equilibrium constant. The concentra-
tions of 0 and OH then can be related to the concen-

trations of stable species uhich are readily measured.
11
Sarofim and Pohl obtained good agreement betueen
observed and calculated "partial equilibrium" NO forma-
tion rates in lean and slightly rich hydrocarbon flames,
Pesters and Flahnen 27 conducted sampling of lean and
.
stoichiometric CH,/02 flames and observed "partial
equilibrium" of Reactions (9) - (11).
Recently, Gay et al 13
' studied one-atmosphere
premixed methane-air flat flames using a molecular-

beam-mass-spectrometer (MBPIS) sampling system. A ua-
18
ter-cooled, copper porous-plug burner urns used. The
gas temperature immediately dounstream from the primary
reaction zone uas measured using the molecular-beam-

time-of-flight technique. For equivalence ratios of
0.8, 1.0, 1.1, tuo distinct regions uere found: a
primary reaction zone uhere formation and consumption
of H~CO takes place, and a secondary reaction zone
uhere NO is formed. Their studies shou that contrary
to the "prompt NO" involved by other investigators,
the formation of NO (if any) in the primary reaction
zone is negligible for flames of equivalence ratio
<I.1. They concluded that the modified Zeldovich mechan-
ism explains NO formation rates in the secondary re-

action zone if radical concentrations and temperature
during combustion are properly evaluated.
Iverach, Basdin, and Kirov studied the
validity of the Zeldovich mechanism in fuel-lean and
fuel-rich hydrocarbon flames in order to end the con-

troversy surrounding "prompt" NO. Propane, ethylene,
acetylene, 6Qfa Ho/40/o ChL, and mixtures of hydrogen

and carbon monoxide uere burned uith air on a uater-
cooled, Neker-type burner. Samples uere taken through
a uater-cooled aluminum tube. NO, CO, C^ concentra-
tions uere determined uith infrared analyzers, 0^ uith

a paramagnetic analyzer, and hydrocarbons uith a flame-
ionization detector. Temperatures uere determined by
19
the sodium-line reversal method and theoretical pro-
cedures. Their experiments showed the following:
(1) for nonhydrocarbon flames, the extended Zeldovich
mechanism is applicable for all fuel-air equivalence
rates, (2) for hydrocarbon flames, the mechanism is
applicable, for both in-flame and post-flame regions,
for #£l,15, and for post-flame region for 0<1.5, pro-
vided that the B^-atom concentration is determined cor-
rectly, and (3) for all regions of fuel-rich hydrocar-
bon flames ($>1.5), and for regions in the vicinity
of the primary reaction zone of moderately rich flames
($>1.15), the mechanism is not tenable because it re-
quires improbably high &-atoms concentrations. They
concluded that reactions such as (7), (8), and possi-
bly (12)
C + N£9 £ CN + N (12)
might be responsible for the large rate of NO forma-
tion in fuel-rich flames and the primary reaction zone
of moderately rich flames (j8>1.15).

28
Ay and Sichel carried out a numerical analy-
sis of the combustion of methane in nitrogen-oxygen
mixtures in order to clarify the relationship between

prompt NO and overshoots in radical concentrations.
Diffusion and heat conduction, which are important
in laminar flames, were neglected in their analysis;
nevertheless, their results show the link between rad-
20
ical overshoot, flame temperature, and the NO forma-
tion rate. Their analysis agrees with the experiments
of Iverach et al , namely, "prompt" NO in near-stoichi-
ometric and lean flames, which is related to the high
rates of NO formation in the recombination and post-
flame zones, can be explained by the Zeldovich mechan-
ism provided the appropriate free radical concentrations
are used; for rich mixtures the NO concentrations com-
puted using the detailed kinetics were far belou experi-
mentally observed values, and the Zeldovich mechanism
fails to explain NO production in rich mixtures.

2.3 Formation of MO in Fuel-Rich Flames
As indicated first by Fenimore and later

supported by the experiments of Iverach et al , "prompt"
NO formed in fuel-rich hydrocarbon flames cannot be

explained by super-equilibrium concentrations of the
radicals 0, OH, and H since the concentrations required
to explain the observed NO-formation rates uould be
significantly larger than "partial equilibrium" values.

The forementioned investigators proposed that reactions
such as (7), (8), and (12) played an important role

in the NO formation process
CH + N HCN + N ( 7)
+ N 2CN ( 8)
C + N 2 £ CN 4- N (12)
uith subsequent reactions of N-atoms-via Reaction (3)
to form nitric oxide. The production of NO in these

flames then requires a detailed combustion mechanism
for the fuel in consideration. (This is also true
of some leaner flames, see Section 2.2). Methane com-

bustion mechanisms are considered in the next section,
and as the reader uill find out, there still are un-
certainties regarding the rate determining step and

the rate coefficients of reactions involved in the
mechanisms. The rapid NO formation rate near the re-
action zone of rich flames requires that reactions
22
such as (7) - (12) be very fast. The experimental
data of Bachmaier et al 29 support this proposal.
Hayhurst and McLean studied a fuel-rich

flame of unburnt composition H2/02/N2: 3/1/4.75 and
a flame of the same composition except that 1% of the
hydrogen uas replaced by acetylene. The flame uas
burnt at atmospheric pressure on a uater-cooled burner

made from stainless-steel hypodermic tubes. The burnt
gas temperature reached 2000°K. Gas samples uere taken
through a uater-cooled probe (made of quartz) into a

chemiluminescent NO analyzer. They found that the
amount of NO in the acetylene seeded flame uas over
that formed in the Hz

0/00/N0 flame via the modified
z /.
Zeldovich mechanism. Based on thermochemical data
alone, they proposed reactions
CH + N2 £ HCN + N ( 7)
CH2 + N 2 ^ HCN + NH (13)
folloued by
N + OH ^ NO + H (3)
NH + OH £ N + H20 (14)
to explain the "prompt" NO formation. Furthermore,
they suggested that HCN is coupled to CN by equilibra-
tion of
HCN + H £ CN + H2 (15)
uith NO resulting from one of the tuo exothermic reac-
tions
23
CN + 02 £ CO -f NO (16)
CN + OH ^ CO + NH (17)
Reaction (17) is followed by (14) and then by reaction
(3).
22
Haynes et al detected the presence of cyano
species in fuel-rich hydrocarbon flames. Uarious pre-
mixed hydrocarbon-air and nonhydrocarbon-air flames
(including a CH, - H2 air flame with equivalence ratio
of 1.42) uith and without the addition of small amounts

of pyridine were burnt on a water-cooled Fleker-type
burner. Samples were withdrawn from the post-flame

gases via water-cooled probes (silica or Alumina), ana-
lyzed continuously for CO and C02 (NDIR analyzers),

-.- -
02 (paramagnetic), and NO (chemiluminescent). The con-
centrations of cyano species and NH. species in the

post-flame gases were determined chemically, and H-
atoms concentrations by the Li/LiOH absorption tech-

f~y *~f O /i
nique ' . Temperatures uere determined uith Na-line
reversal measurements. They found NO, HCN, and NH.
concentrations in excess of equilibrium values. (The

measured values of NH. concentration are viewed with
caution, however, since they were highly susceptible
to sampling conditions). The observed NO formation
rates were larger than predicted by the Zeldovich mechan-
ism with 0-atom concentrations inferred from measured
H-atoms concentrations using a partial-equilibrium ap-
24
proximation for the system H - OH - 0 - H2 - H20. The
formation of cyano-species uas found to be related
to the decay of hydrocarbons and in very rich flames
occurs well into the post-flame gases. Furthermore,
it uas concluded that HCN decays via CN and the rate-
determining reaction
CN + C02 £ OCN + CO (18)
Morley also studied fuel-rich flames, in-
cluding CH, - 02 ~ MO flames with equivalence ratios
from 1.20 to 1.95. A method involving direct sampling
of natural flame ions into a mass spectrometer uas
used to calculate the concentrations of HCN, NH 3 , and
NO. He found that the HCN concentration is proportional
to the N2 concentration independent of the fuel type,
that the HCN concentration increases uith increasing
equivalence ratio, and that HCN-decay leads to both
INUand NO, the relative proportions depending on the
equivalence ratio. Morley suggests the reaction se-
quence,
CH + N2 <* HCN + N (7)
HCN + H ** CN + H2 (15)
HCN + OH £ CN -i- H20 (19)
uhere (15) and (19) are balanced, to explain the forma-
tion of HCN and CN in the flame. The subsequent de-
cay of HCN is consistent uith the reaction
CN + OH £ NCO + H (20)
25
being the rate-limiting step, and it leaves the nitro-
gen from HCI\1 as N H - . Nitric oxide and nitrogen are
produced by reactions involving the NH. species and

Reaction (3)
N + OH ,-• NO + H ( 3)
17
("ligauchi et al modeled the combustion of
CH^ - Qj " No f-'-ames using a 40-reaction mechanism.

They studied flat flames burning on a cooled stainless-
steel porous plate at 0.1 atm. pressure. They used a
quartz probe to sample the flame. NO uas detected
X
using chemiluminescence; H, OH, and 0 using ESR; CN-
species using chemical means, and stable species using
gas chromatography. For equivalence ratios from 0.88
to 1.42, they concluded that the Zeldovich mechanism
is inadequate to predict "prompt" NO formation, and
that HCN is formed prior to NO. They favored Reaction
(13) over Reaction (?) on thermochemical grounds and
pointed out the violation of the spin-correlation rule
by Reaction (7). Other species like C, C2 did not con-
tribute significantly to "prompt" NO formation because

of their low concentrations in the flame. They sug-
gested that
H2CO + M CO + H2 H- M (21)
is the rate determining step in methane oxidation.

95
Pecters, Blauuens, and Smets measured
the concentrations of NO, 0, and fuel fragment radi-
26
icals such as CH, CH2, C2, by means of molecular-beam
sampling and mass spectrometric detection in a number
of hydrocarbon/02/N2 flames. The fuel uas ethylene,
ethane, or methane. They found that even in hot, fuel-
lean flames, the Zeldovich mechanism cannot account
for the rapid NO formation in the flame front. They
derived an expression for the NO generation rate in the
flame front of all flames investigated in terms of the
CH2 or CH radical concentrations. They concluded that
both of the processes
CH + N 2 * HCN + N (7)
CH2 + N 2 £ HCM + NH (13)
in each case followed by rapid oxidation of the prod-
ucts, may be the principal source of NO in the flame
front, and that other hydrocarbon fragments, C, C2,
C 2 H do net contribute to "prompt" NO formation because
of their lou concentrations in the flame front.
The actual mechanism of decay of hydrogen
cyanide in hydrocarbon-air mixtures is uncertain.
The studies by Haynes and Morley previously mentioned
are in contradiction in regards to uhich reaction is
the rate-determining step in the decay. In order to
elucidate the HCN-decay mechanism uhich concludes uith
2 fi
the formation of NO, Haynes recently conducted a
study of premixed hydrocarbon flames burning on a ua-
ter-cooled neker-type burner seeded uith fuel-nitro-
27
'
gen in the form of pyridine, ammonia, or nitric oxide
in amounts up to 2000 ppm. of nitrogen species in the
post-flame gases, A water-cooled silica probe uas
used to sample the gases. NO uas determined continu-

ously by a nondispersive infrared analyser (l\IDIR).
Cyano species and total amine species uere determined
using chemical means. H-atom concentration in the
hot gases uas determined by the Li/LiOH absorption method,
Post-flame temperatures were determined by the Sodium-
line reversal method. Based on the experimental re-
sults, Haynes proposed two parallel rate-controlling
steps: one which is first order in OH, possibly reac-
tion (22)
HCN + OH *• HOCN + H (22)
the other which is second order in OH:
HCN + OH * CN + H20 (23)

CN + OH *• OCN + H (24)
The relative contributions of (22) and (24) vary with
temperature, uith Reaction (24) dominating at high
temperatures. The OCN- species decay very rapidly
to form NH.-species
1
+H
HOCN (cyanic)^HIMCO (isocyanic)^ NH2 -f CO (25)
OCN + H % NH + CO (26)
As Haynes points out, measurements of OCN and NH.

species are required to confirm the proposed mech-
anism.
23
("lorley considers the fate of the NH. spe-
cies. He indicates that the nitrogen hydrides can
be interconuerted by reactions of the type,
NHXV + H ± NHX , + H^-9, x=l,2,3
V —X (27)
which may or may not be balanced, and the oxidation
and the formation of N^ taking place by
N + OH £ NO + H ( 3)
'2 + NO ^ N2 + H20
NHo (28)
NH + NO * N 0 + OH (29)
N + NO ^ N 2 + 0 (3U)
Furthermore, at relatively lou temperatures, the above
reactions might lead to a build-up of amine species.
Experimental measurements are needed.
29
2.4 Mechanisms of Methane Oxidation
In order to predict the formation of nitric oxide
in fuel-rich flames and some lean flames of hydrocarbons
(see Sections 2.2, 2.3), the concentration histories of the
free radicals are necessary. The kinetics of methane oxygen
systems have been studied extensively over the years.
Nevertheless, many uncertainties remain, both with respect
to the oxidation mechanism and the rates of the elementary
reactions which form part of the mechanism. Furthermore,
in the richer methane flames, C^-hydrocarbon decay and
formation has to be accounted for, and the mechanism grous
in complexity.
2.4.1 Methane Oxidation in Fuel-Lean Flames
Studies include shock-tube experiments by Cooke

3D 31 32
and Williams , Bouman , Heffington et al , Brabbs and
Brokau , molecular-beam-mass-spectrometer sampling of

27
flames by Peeters and Mat-men , numerical analysis and flou
34
reactor experiments of Uestbrook et al , the kinetic sur-
35 9697
vey of Engleman , and recent uork by other authors .
In Table 1 (p. 35), the 23 reaction mechanism for

31
the shock-initiated CH,-oxidation proposed by Bouman " is
reproduced. This mechanism has been used extensively by
other investigators. Bowman's analysis shows that, in the
temperature range 1900 - 2400°K, this mechanism correctly
3D
predicts the time of occurring and magnitude of the radical
(0, OH, H) concentration overshoots, and also predicts a
departure from a "partial equilibrium" state during the
initial stages of the radical concentration overshoots.
Boni and Penner ^ ficonducted a sensitivity ana-
lysis of the mechanism proposed by Bowman at 2QOO°K. Their
analysis showed that Reactions (Rl), (R7), (R16) and (R25)
are the most important reactions for all of the species
CH4 + n £ CH3 + H + N (Rl)
H + 02 £ 0 + OH (R7)
CH3 + 02 £ H 2 CO + OH (R16)
H2CO + PI £ HCO + H + M (R25)
In addition Reaction (R15) is important for the major free
radical species, i.e., OH, 0, and CH20. The 0-atom profile
is dominated by Reactions (Rl), (R7), (R16), (R25), (R15)
(as cited by Bowman) plus Reactions (R24) and (R3)
CH3 + 0 £ H2CO + H (R15)
HCO + fl £ CO + H + N (R24)
CH4 + H £ CH3 + H2 (R3)
98
The mechanism of Reaction (R16) has recently been studied ,
and the oxidation of methyl radicals was shown to occur
through the steps
CH^\J + 0 * CH<-90 + H
CH3 + 02 ^ CH30 + 0
CH3 + 0 £ CH20 + H2
31
The methoxy radicals produced react by means of
CH3D + M £ CH20 + H + M
CH30 + 02 £ CH20 + H02
The reaction of CM, uith 02 and the thermal decomposition
of CI-UO are the most important pathways of methyl radical
oxidation,
Peeters and Mai-men 27 measured the concentration
of all species, stable as uell as unstable, throughout the
reaction zone of lou-pressure lean methane-oxygen flames.
The results of their analysis shou that (i) CH, reacts 15%
uith OH, 15% uith 0, and 10% uith H; (ii) CH,
O
is destroyed
by 0 atoms; (iii) CH90 disappears 4Q?o by thermal decompo-
*
sition, 40% by reaction uith OH, and 20% by 0 attack; (iv)
CHO reacts mostly uith 02; (u) H02 is destroyed 45% by OH,
40% by 0, and 15% by H, Their studies shou that the rate
limiting step is the decomposition of formaldehyde
CH20 + N = CO + H2 + 1*1 (31)
They argued that Reaction (31) explains quantitatively the
function of Hz
9 in the flame, and the activation energy of
Reaction (31) is in good agreement uith the overall "acti-

vation energy" of lean-CH^/02 flames (about 40 kcal/mole).
On this basis, they rejected reactions such as
CH20 + 0 £ CO + H + HO (32)
CHO + N ^ C O + H + N (R24)
Furthermore, they pointed out that Reaction (R25) of Bouman

may uell be the rate-determining step in shock studies,
and Reaction (31) cannot contribute significantly to the

removal of CH20 in shock tubes since the major part of the
CH20 is consumed by H atoms in a chain mechanism initiated
by Reaction (R25). Their results also shou that C02 is
formed mostly via Reaction (R9)
CO + OH £ C02 + H (R9)
The important reactions in Peeters mechanism are
CH4 H- OH £ CH3 + H20
CH4 + 0 £ CH3 + OH
CH3 + 0 £ CH20 + H
CH20 + N $ CO + H2 + M
CH20 + OH(0) £ CHO + H20(OH)

CHO + 02 £ CO + H02
H02 + OH(0) * 02 + H20(OH)
H02 + H ^ 20H
H + 02 ^ OH + 0
0 + H2 ^ OH + H
OH + H2 £ H20 + H
OH + OH £ H20 + 0
CO + OH £ C02 + H
•7 C
(For extensive kinetic data see England ). Further
support for Reaction (31) as the rate-determining step
in flames can be found in the investigations of Migauchi
et al . They studied premixed CH4/02/N2 flames at 0.1
33
atm. and equivalence ratios between 0.88 and 1.42. They
found the rate-controlling reaction of methane oxidation
to be Reaction (31) uith a rate constant k31=2.1x!015 exp
(-17,620/T) mol"1cm3sec"1.
2.4.2 Methane Oxidation in Fuel-Rich Flames
In the combustion of fuel-rich hydrocarbon
flames,the -concentrations of hydrocarbon fragments are high

enough that their recombination reactions become important
and hydrocarbons higher than the original fuel are found as

intermediates.
In CH^-oxidation, the chemistry of C2-hydrocar-
bons becomes important in the fuel-rich mixtures. Gardiner
and Olson 37 have conducted a series of shock tube experi-
ments and numerical analysis of fuel-rich CH,/02/Ar mix-
tures. The reactions of CH 2 » C^H,, and CoH- were found to
play an important role in their shock tube experiments.
The result of their experiments can be modeled by a sixty-
three-reaction mechanism which is reproduced in Table 2
(18000<T<2700°K). They omitted species CH and C2 on the

basis that their concentrations and reaction rates are too
small to affect the overall course of reaction. The spe-
cies ChUO and d-U02 were omitted on similar bases. Their

sensitivity analysis showed primary sensitivity to the py-
rolysis reactions (1) and (30), and to the oxidation reac-
tions (7) and (48). Additional sensitivity is present for

TABLE 1,
Methane oxidation in fuel lean mixtures
Reaction Rate constant, kf*
CH,-i-H+M 2X1017 exp(- 44 500/77)

2. 6X10" exp(- 6290/2T)
3. CH4+H-»CH,+H, 2.24X10*7'' ex p ( - 4 400/7")
4. CH,+O— CH,+OH 2.1X10" exp( -4 560/r)
5. H,+OH—H+H,O 2.9X10" exp( -5530/T)
6. O+Hj—H+OH 3.2X10'< exp( -7540/r)
7. H+Oj—O+OH 2.2X10" exp( -8 450/r)
8. O H + O H —O+H.O 5.5X10" exp( -3520/r)
9. CO+OH— CO,+H 4.0X10U exp( -4030/T)
flO. CO+O4-M— CO.+M 5.9X10"exp( -2060/D
11. H+OH+Ar— H,O+kr
12. H+OH+H,O-»HzO-}-H,O
f!3. Oi+Ar-Ô+O+Ar 7.9X1011 exp(-52770/r)
tH. H,+Ar—H+H+Ar 2.2X10" exp(-4S300/r)
15. CH.+O-^HjCO+H 1X10"
16. CH.+O)— H,CO+OH 2X10"
f!7. CH.+OH— HjCX^+H, 4X10"
18. H,CO+O— HCO+OH 5X1011 exp(-2300/r)
19. H,CO+OH— HCO-1-Hrf) 5.4X10" exp(-3 170/r)
20. H-CO+H— HCO+H, 1.35X10" exp(-l 890/7")
21. HCO+O— CO+OH 1X10"
22. HCO+OH— CO+H^) 1X10"
23. HCO+H—CO+H, 2X10"
24. HCO+M— CO+H+M 5XlOue.xP(-9570/r)
25. H,CO+M-» HCO+H +M 4X10 U exp(-lS500/r)
26. H+HO,-*OH+OH 2.5X10"exp(-950/r)
27. H+O.+M—HO.+M 1.5X10" exp(500/r)
|2S. C,H,— CH4+CH, 8X10" exp(-4 500/r)
f29. C-H.+O— C^H^+OH 4X10"exp(-32SO/r)
t30. HCO+O,— CO+HO, 4.2X10"exp(-7200/7')
Units: cm, cal, °K, mole, sec. t Re.iction not included in final mecnanism.
35
TABLE 2.
Methane oxidation in fuel rich mixtures
Rate Constant0
Reaction IogIOX n 0
(1) CH 4 + M = CH3 + H + M 17.67 0 46,900

(2) CH 4 + H = CH3 H- H 2 14.86 0 7,600
(3) CH4 + O = CH3 + OH 7.07 2.1 3,840
(4) CH4 + OH = CH3 + H 2 O b 3.54 3.1 1,010
(5) CH4 + CH 2 = CH3 + CH3C 13.00 0 0
(6) CH3 + M = CH 2 + H + M c ' d 16.67 0 46,900
(7) CH3 + O 2 = CH 2 O + OH 11.84 0 4,530
(8) CH3 + H = CH 2 + H 2 c ' e 14.86 0 7,600
(9) CH3 + O = CH 2 O + H 13.83 0 0
(10) CH 3 + OH = CH 2 O + H 2 12.87 0 0
(11) CH 3 + C H 2 = C 2 H 4 + H 13.30 0 0
(12) CH 2 + C H 2 = C 2 H 2 + H 2 13.50 0 0
(13) CH 2 + O 2 = CH 2 O + 0 14.00 0 1,860
(14) CH 2 0 + M = CHO + H + M 16.70 0 36,235
(15) CH 2 0 + H = CHO + H 2 13.30 0 1,660
(16) CH 2 O + 0 = CHO + OH 13.70 0 2,300
(17) CH 2 O + OH = CHO + H 2 O 15.70 0 6,540
(18) C H O + M = H +CO + M 14.47 0 7,400
(19) CHO + O 2 = HO 2 -i-CO 12.53 0 0
(20) CHO + H = CO + H 2 13.30 0 0
(21) CHO + O = CO + OH 13.48 0 0
(22) CHO + OH = C O + H 2 O 13.48 0 0
(23) C 2 H 6 + M = CH 3 -t-CH 3 + M / ' 111.29 -25.3 80.020
(24) C2H6 + H = C2H5 + H2 14.12 0 4,715
(25) C 2 H S + O = C 2 H 5 + OH 13.26 0 3,070
(26) CoH 6 + OH = C 2 H 5 + H20g 13.80 0 1,810
(27) C 2 H 6 * CH3 = C 2 H 5 -H CH4h 14.74 0 10,820
(28) C 2 H 5 + M = C 2 H 4 + H + M1 14.67 0 13,390
(29) C 2 H 5 + O 2 = C 2 H 4 + HO 2 12.18 0 2,445
(30) C 2 H 5 + H = CH3 + CH 3 13.57 0 0
(31) C 2 H 5 + H = C2H4 + H2 12.27 0 0
(32) C2H4 + M = C2H2 + H2 + M 17.32 0 39,810
(33) C2H4 + M = C2H3 + H + M 17.41 0 48.600
(34) C 2 H 4 + H = C2H3 + H 2 14.84 0 7,300
(35) C2H4 + 0 = C H 3 i - C H O 13.35 0 1.360
(36) C 2 H 4 + OH = CH3 + CH2O 13.00 0 0
(37) C 2 H 3 + M = C2H2 * H + M 14.90 0 15,850
(38) C->H 3 + H = C 2 H 2 + H2C 13.00 0 0
(39) C2H2 + M = C 2 H - H H + M 16.62 0 53,850
(40) C 2 H 2 + H = CoH + H2;' 0.89 3.2 250
(41) C 2 H 2 + O = CH 2 + CO 13-72 0 1,860
36
-
Rate Constant0
Reaction Iog10>l n 6
(42) C 2 H 2 + OH = CH3 + CO 12.08 0 250

(43) C2H2 + C 2 H 2 = C4H3 + ff 13.00 0 22,650
(44) C 2 H 2 + C2H = C 4 H 2 + H 13.60 0 0
(45) C 4 H 3 + M = C 4 H 2 - | -H + M/ 15.93 0 30,200
(46) C 4 H 2 + M = C 4 H + H + U> 17.54 0 40,260
(47) H 2 + O2 = OH + OH 13.23 0 24,210
(48) H + O 2 = OH + O 17.08 -0.91 8,370
(49) O + H 2 = OH + H - 14.34 0 6,895
(50) OH + H 2 = H 2 O + H 13.72 0 3.270
(51) OH + OH = H 2 O + O 13.74 0 3,520
(52) H + O 2 + M = HO 2 + M 15.40 0 0
/C'i'V T
\,j j ) ti r>_ O
kj U
n -i-T \i — TJ f~}
jvi — rio^-* 4- \t
•*" 23.88 -2.6 0
(54) H2 + M = H + H + M 12.35 0.5 46,600
(55) O2 + M = O + O + M .11.27 0.5 48,165
(56) CO + Oo = CO2 + O 11.08 0 17,615
(57) CO + OH = CO2 + H k 12.60 0 4,025
(58) CO + O + M = CO2 + M 13.45 0 -2,285
(59) H 2 + HO 2 = H 2 O + OH 11.86 0 9,410
(60) H + H0 2 = OH + OH 14.40 0 960
(61) H + H0 2 = H 2 + O 2 13.40 0 350
(62) OH + H0 2 = H 2 O + O 2 13.70 0 500
(63) O + H0 2 = OH + O 2 13.70 0 500
0
Rate constants in the form A X 7" exp (-6/7"), in cm, mol, s, and K units. The reverse reaction rate constants were
computed using J A N A F thermochemica! data where possible and locally computed thermochemical data otherwise.
b
The T3 factor may extrapolate the rate constant loo high at higher temperatures, but is used here because this
expression goes through the high-temperature data.
c
Estimate. No sensitivity to the rate of this reaction was observed.
Êstimated to be equal to frj/10.
e
Estimated to be equal to Jr 2 .
^ This reaction is in the pressure-dependent falloff region of a unimolecular decomposition. This rate expression is
from Olson et al. [9] for experiments over the range 1330 < T < 2500 K and 0.10 <P < 0.50 a tm. Care must be taken
that this rate-constant expression be used only for the pressure and temperature conditions for which it is valid.
* This is a low-temperature value that agrees with the few high-temperature data.
h
Strongly curved Arrhenius behavior is observed for this reaction.
1
This rate-constant expression was obtained by RRK calculations of the falloff from the experimental high-pressure
limit expjession of Glanzer and Troe [ 4 7 J .
^ Preliminary results.
k
See Baulch and Drysdale [621 for a review of the literature on this reaction.
37
the CH2 reactions (ll) and (13), and reactions (14) and (2).
Literature values for rate constants uere used for Reac-
tions (1), (2), (13), (14), (30) and (48). The authors
cautioned that the H2CO-decay mechanism is uncertain and
insufficient experimental data is available. The numeri-
cal values for the rate constants of Reactions (7) and (11)
uere found by numerical analysis. They believe their re-
sults to give k? to uithin +5Q% and k, , uithin a factor of

2.
38
Harvey and Maccoll studied the formation of C?
hydrocarbons uithin methane-oxygen flames of equivalence
ratios 0.56 to 1.25 at 20 torr. Their experiments shoued
that for their experimental conditions the reaction
CH3 + CH3 + N £ C2Hg + 1*1

is uell into the fall-off region resulting in a lou re-
action rate (the maximum mole fraction of ethane in the
stoichiometric flame uas 5 x 10 ). Their results enabled
them to propose the following ethylene forming reactions
CH3 + CH2 £ C2H4 + H

The ChU and CI-U concentrations in these flames are in
equilibrium via
-x pit
H v* L»MO n/p
Figure 2 shows the dependence of CH20, C2H4, C2H2 and

H2 peak concentrations on flame equivalence ratio.
33
Figure 3 shows the dependence of C 2 H < , C2H2, and hU
on peak fCH for a range of flame equivalence ratios.
They also pointed out that at higher pressures the rate
of the combination of methyl radicals (CH, -f- CH,, + PI

O O
£ C 2 Hg + M) to ethane uill become competitive uith the
other sources of C2 hydrocarbons, and acetylene is formed
in the flame via
+ CHo x~ CoHo 4- HO
39
0-4
0-3
o
o
0-2
O
5
0-1
0-5 0-6 O-7 O-8 09 1-0 11 1-2 1-3

EQUIVALENCE RATIO
Fig. 2. The dependence of CH2O ,C2 H 2 , and H2

peak concentrations on flame equivalence ratio .
40
(PEAK CH3 MOLE FRACTION) 2 i 10s
Fig. 3. The dependence of peak C_H 4 C H and HS on peak

2 2 2 2 '
( CHS ) for a range of flames £ Z 0.56 to 1.25 .
41
Shock-tube studies of the early stages of
pyrolysis and oxidation of methane were conducted by

39
Tabayashi and Bauer . Temperatures ranged from 1950
to 2770°k, total densities (2.37 - 8.91) x ID"6 mol

— *Z
cm , and CH^/CU ratios 3.3 and 6.7. From their pyroly-

sis experiments in CH^/Ar mixtures, they concluded that
methane decomposes mainly via
CH + Pi £ CH, + H + n
C
2H5 + ^ * C2H4 *H * N
C2H3 + Fl £ C2H2 + H + M
methylene is produced mostly by the reaction
CH2 -r H2 £ CH3 + H
and consumed via reactions with CI-L and species gener-

ated during ChL-pyrolysis. Their oxidation studies
show that oxygen reacts only with the fragments of meth-
ane pyrolysis, and under the methane rich condition
oxidation starts predominantly via the reaction
CH3 + 02 £ H2CD + OH
rather than
H + 02 £ OH + 0
and the resulting OH radicals react rapidly with meth-
ane uhich is present in large excess,
CH4 + OH £ CH3 + H20

thereby generating more methyl radicals, uhich reinforce
the pyrolysis chain. Their calculated species profiles

best fit the observed profiles if the reaction rate
constant for the methyl radical-oxygen reaction is given
a value of 2.7 x ID12 x exp (-12,000/RT) cm3moi""1s~1.

Regarding the fate of formaldehyde, they found that
thermal decomposition of formaldehyde uas in agreement
with their experimental results and computer simulations
CH20 + M = CO + H2 + PI
Houever, an alternative mechanism consisting of the
following reactions
CH 2 0 + M £ CHO + H + 1*1
CHO + M ^ C O + H + IV1
CHO + 0 2 £ CO + H 2 0
CHO -f H £ CO + H2
CH20 + H £ H2 + HCO
could not be excluded.
The role of CH2 in CH^-oxidation uas found
to be ambiguous. This study also shous that oxidation
of CO to CO- occurs mainly via the reaction
CO + OH £ C02 -f H
CHAPTER 3
EXPERIMENTAL APPARATUS
3.1 An Introduction to Sampling Techniques in Combus-

tion Studies
40
As Knuth has suggested, specifications for
the ideal instrumentation for flames studies might in-
clude the following broad requirements: (a) monitor
all chemical species, including intermediate and free-
radical species, (b) function in temperature, pressure
and composition ranges typical of flames, (c) resolve
spatial measurements small in comparison uith the flame
thickness, and (d) monitor uithout disturbing the (non-
equilibrium) thermodynamic state of the system.
Shock tubes have been shoun to be suitable
for studies of high temperature processes, and excellent
revieus and books are available that describe their ap-
plicability in chemistry and physics. The shock-tube
method of studying high-temperature processes possesses
at least four major advantages over other methods41
~:
(1) The equilibrium temperature in the after-shock

region can be calculated accurately and re-
liably from the measured shock speed and
conservation of mass, energy, and momentum
considerations,
(2) The "slug" of gas behind the primary shock
is very uniform in pressure and temperature.
Uall effects are negligible because of the
short time scale.
(3) Practically any gas mixture can be heated
to any selected temperature by using the ap-
propriate shock strength.
(4) The heat release by the shock impact is ini-
tially in the form of kinetic energy, i.e.,
translational energy of the molecules.
The major disadvantage is the short observa-
tion time, which for the after-shock region, is usually
betueen 1QD and 400^sec, Thus, optical spectroscopy
is by far the most useful method of following the pro-
duction and/or consumption of individual species behind
shock waves. Typically, three or four species are mon-
itored. If only one optical path is available, then
a oiven set of conditions must be repeated for each of
the species monitored.
Ono of the principal problems with spectro-
scopic studies is that of determining absolute concen-
trations, since absorption coefficients are known only
for atoms, most diatomic molecules, and a few simple
poly-atomic species. In the absence of this knowledge
it is necessary to calibrate the system. This is dif-
45
ficult because radical concentrations of knoun values
are hard to obtain, the production of the radical it-
self might be an experimental challenge, and it is neces-
sary to calibrate over the temperature range to be stud-
ied since the temperature dependence of absorption coef-
ficients of complex molecules is unknown. One also
has to find absorption lines in the available spectral
regions uhich are not obscured by other species. Hence

the use of shock tubes in conjunction with optical spec-
troscopy satisfies requirement (d) most closely, require-
ment (a) least closely.

In an alternative technique, gas samples are
withdrawn from the flame using a sampling probs. Probe
sampling is a straightforward process; the sample is

withdrawn, quenched, and analyzed. The chief advantage
of this technique is that a wide variety of analytical
instruments can be used to follow the fates of species
within the flame. The main disadvantage is that compo-
sition changes due to additional chemical reactions
during transport from the flame to the analytical in-
strument^) are inevitable. Probes also have perturb-
ing effects on the flame that have to be considered:
aerodynamic, thermal, and catalytic effects. Some of
these have been eliminated by the use of very fine mi-

9n
croprobes made of quartz. The relative effects of
several different probe designs on flames have been studied
by England , Malta , and Allen . The use of sampling
probes meets requirement (a) relatively closely and re-

quirement (d) relatively poorly.
Sampling of ions from flames is another tech-

nique used by investigators to study the processes oc-
curring in the combustion mixture. In a typical appa-
ratus, the gas is sampled through a small hole at the
tip of a cone and expanded into a vacuum chamber at
10 to 10 torr. The system is designed to obtain
critical flow through the nozzle. The ions are formed
into a beam by an electrostatic lens and focused through

a small hole, typically 2mm. in diameter, into a second
chamber at 10 torr. which holds a quadrupole mass spec-
trometer and electron multiplier. Both positive and
negative ions can be detected by reversing the polari-
ties of various voltages. Ideally the expansion of the
gas into the vacuum should be fast enough to quench any
chemical reactions so that the expanded gas has approx-
imately the same composition as that in the flame.
This is usually the case for neutral molecules, but

because ion-molecules reactions are typically 1-2 orders
of magnitude faster than those betueen neutral molecules
considerable distortion of ion signal can occur .

This is particularly important for negative ions because
of the possibility of fast associative reactions. Fur-
thermore, the boundary layer that exists on the sampling
47
cone uill have an additional effect on the flame gas
composition before it expands through the nozzle .
This and the effects previously described can be min-
imized by proper design of the sampling system, giving
this technique an advantage over some other flame-sampl-
ing techniques, probe sampling for example. The chief
disadvantage of ion sampling is that it can be used
only for species uhose concentrations are known func-
tions of measurable ion concentrations. Hence this
technique satisfies requirement (d) most closely and
requirement (a) least closely.
The molecular-beam-mass-spectrometer (MBFIS)
sampling system satisfies the abovementioned requirements
uith better balance. The U.C.L.A. MBfIS sampling system
has been employed in the study of reactive mixtures since
1969, and numerous studies have been conducted in this
laboratory to eliminate or minimize all those effects
uhich might either distort the gas composition during
sampling or make the interpretation of measurements
a confusing task. A discussion of these perturbing

effects is left for the next section, and only a descrip-
tion of the system uill be made here.
The FIBMS sampling system consists typically
(see Figure 4) of a sampling cone (uhich might be en-
closed in a chamber for lou-pressure studies), source
chamber, skimmer, collimating orifice, detector chamber,

and quadrupole mass spectrometer detector. Inclusion
of an effusive source and a uheel-chopper in the collima-
tion chamber allows calibration of gas mixtures and
phase-sensitive detection. The source gas (at pressures
of up to several atmospheres and temperatures of several
thousand degrees Kelvin) expands through the sampling
orifice into the source chamber (uhere background pres-
sure is typically 10—3 to 10-1 torr.) and the core of
the resulting jet is skimmed and transferred into the
collimation chamber (uith background pressure from 10"~
to 10 ' torr.). The molecular beam is chopped in the
collimation chamber for phase-sensitive detection, and
the collimating orifice admits these molecules flying
along the system centerline into the detector chamber.
The mass-spectrometer detector generates a signal pro-
portional to the species density in the beam at the de-
tector.
As uas mentioned in the discussion of ion
sampling from flames, the intention here is to lower
suddenly the temperature and pressure of the reaction
mixture, so that further chemical changes are prevented
and the composition of the expanded gas approximates,
that of the flame.
49
FABRITEK WAVE
COMPUTER GENERATOR
TOP SIGNAL
EAI 2 5 0 QUAD. BEAM EFFUSIVE MOVABLE
MASS SPECTROMETER CHOPPER SOURCE SKIMMER
\ WATER-COOLED
HEAT SHIELD
ION
SIGNAL
DETECTOR EXCITOR
V A C U U M PUMP V A C U U M PUMP V A C U U M PUMP
LOCK-IN LSI-1 1
COMPUTER BURNER POSITION SIGNAL
AMP.
Fig. 4. The UCLA MBMS sampling system.

Thus, applicability of MBMS sampling techniques
to the study of chemical reactions in flames results
largely from the rapidity with uhich the gas tempera-
ture and pressure decrease during the expansion through
the orifice in the sampling cone. A plot of the tem-
perature ratio T/To versus dimensionless time, taken
from reference 40, is shoun in Figure 5. T is the gas

temperature, a is sound speed, t is flou time (zero
at the throat), x is axial distance (zero at the throat),

d is throat diameter, and subscript o refers to source
(stagnation) conditions. Furthermore, a point that
should be stressed is that, uhile in the sampling of ions
one is actually measuring average properties of the
gas that flous through the sampling orifice, in MBMS
sampling only that small fraction of the sampled gas
that flous in the vicinity of the orifice centerline
reaches the quadrupole mass spectrometer detector.
This results, as uill be explained in more detail in the
next section, in the detection of molecular-beams that
are much more representative of the flame gas.
51
Fig. 5 Temperature ratio as function of dimensSonless flow time
for free-jet gas flows from orifice.
52
3.2 Possible Composition Distortions in_ flBNS. Sampling
of Flames.
In an idealized model4 of molecular-beam
sampling, the sampled gas undergoes an isentropic free-
jet expansion through the source orifice and the speci-
fic-heat-ratio, ^Tf remains a constant throughout this
expansion. Flou remains a continuum upstream from the

skimmer entrance and becomes free-molecular downstream
from this surface. There is assumed to be no background
scattering of the free jet and the molecular beam.

The beam composition at the detector is the same as
the source-gas composition.
In the design of a flBHS sampling system, var-

ious departures from the above model must be considered.
As the combustion mixture flous from the source to the
detector, the following are encountered: sampling-probe-

induced distortions of the gas composition, chemical
reactions during the expansion of the gas into the vac-
uum, species condensation, pressure diffusion, freez-

ing of vibrational, rotational or translational degrees
of freedom (in this order), skimmer interference, Flach-
number focusing, and scattering by background gases

(in any one of the lou-pressure chambers). Except for
probe-induced distortions, all of the above considera-
tions are treated in the paper by Knuth , and the dis-
53
cussion is based mostly on this reference and uork by
other authors with the U.C.L.A. MBMS sampling system.
3.2.1 Free Get Expansion.
Before proceeding into the discussion of com-
position distortions in MBMS sampling, the reader might
benefit from a brief introduction to the problem of
unconfined expansion from a sonic orifice into a lou-pres-

sure chamber.
As Sherman indicated, the problem of trans-
onic flou through an orifice or axisymmetric nozzle re-

mains unsolved. Houever, the supersonic region of the
flou is very little influenced by the transonic region,
and the method of characteristics can be applied in
the inertia-dominated region of high-Flach-number isen-
tropic flou.
The free-jet shock uave structure is shoun
in Figure 6. As pointed out above, the method of char-
acteristics is applied to the region inside the barrel
shock. Ouen and Thornhill were the first to carry

out the computations for gases uith T = 7/5 assuming
slightly supersonic flou at the orifice (M = 1 leads
to a singularity). Sherman and Anderson report

calculations for other values ofj. The main feature
of these calculations is that about one nozzle diameter

from the orifice the streamlines appear to radiate from
a "source" at x . Furthermore, the density decreases
along each streamline in proportion to the inverse square
distance from this "source." The isentropic core of the
flou appears to pass from the nozzle exit through a bar-
rel, the sides of uhich are the shock uaves generated
by the coalescence of compression uaves originated at

the jet boundary as the reflections of the initial ex-
pansion fan. The Mach disk is formed by the intersec-
tion of the lateral shock uaves.
55
SONIC MACH
ORIFICE DISK
BARREL
SHOCK
Fig. 6. Free-jet shock structure.
56
The variation of the mach number, M, along
the jet axis with distance x has been carried out by
Sherman and Ashkenas ' for'"/" = 5/3, 7/5, and by An-

derson49 for If = 1.30, 1.20, 1.10, and 1.05. They used
the best fitting formula
f TlP —1 ~'°
i«M»™»» I ^
d* xl
where A, and x are constants which can be obtained

o
from the above references. For other values ofT, one
may use the following equation suggested by Knuth ,
(34)
Note that Equation (33) has a singularity at x = x ,

and therefore it is only applicable if x >1.
d* '
It is important to point out effects that are
not considered in the ab'ove analysis of free-jet expan-

sion. (1) Boundary-layer growth on the converging nozzle.
The effect of this boundary layer will be to change
the effective orifice size (see Ref. 51 for a compre-
hensive analysis) and distort the flow pattern near the
orifice. In equations (33) and (34) an effective ori-
fice diameter then must be used.
(2) Freezing of vibrational, rotational, and transla-
tional degrees of freedom (always in this order). Freez-
ing of degrees of freedom will cause T to change in the
57
expansion and not be constant as assumed In Thornhill's
analysis. Freezing of translational degrees of free-
dom causes the flou to transit from continuum to free-

molecular. Equations (33) and (34) for the centerline
Flach number do not hold in the free-molecular flou re-
gion. It should be noted, houever, that the density
keeps decreasing as the inverse square of the distance
as a consequence of the source-point nature of the flou.
(3) To the author's knowledge the determination of
jet boundaries for gas mixtures uith diffusive separa-
tions (e.g., ba rodif fusion) has not been solved theo-
retically.
Sherman 46 determined the location of the Mach
disk empirically,
p = stagnation pressure
p = ambient pressure
This is independent of v and holds for 15 ^ P0/0 ^17,000.
52
Bier and Schmidt determined, from photographic studies
of jets, empirical relations for the nach-disk diameter
y
7 and the maximum diameter of the barrel shock y Q
m a
3
for 10 ± p / <. 10 .
v ^ 0.598
£n = 0.252 fp I (36)
d*
53
0.591
- - 0 316
d
*
Sometimes, values for the Mach number near

the sonic orifice (upstream of the effective "source"
at x ) and upstream of the orifice are needed. As in-
dicated above, Equation (33) is restricted to x/d*^l.

Values for M in these tuo regions have been determined
experimentally by Sherman and Ashkenas for o = 7/5,
and Anderson ' f or 1) = 5/3. Sharma arrived at ex-
pressions for T/T in terms of x/d* in these tuo regions

from theoretical considerations. His calculated Plach
numbers are larger than experimentally determined ones.
3.2.2 Chemical Relaxation in Supersonic Expansion
Successful nBHS sampling requires that all
chemical reactions occurring in the sampled gas mixture
are quenched, i.e., that they "freeze," as early as
possible in the free jet expansion through the sampling
orifice. If the chemical reaction is frozen upstream
of the sonic orifice, then the sampled gas is most repre-

sentative of the undisturbed gas composition. However,
if the reaction proceeds at large rates it uill be able
to follow changes in temperature and pressure up to
the nozzle throat, and in some cases several throat
diameters downstream.
59
Hayhurst studied the occurrence of chemical
reactions in the supersonic expansion of a gas into

a vacuum. His investigation focused on the hydration
of HjO4"
H30++ H20 + M # HgQ* + PI (38)

in an atmospheric premixed H2/02 flame uith nitrogen
added as a diluent. Reaction (38) is fast enough to
be equilibrated in the flame. For this purpose it is
necessary to calculate the variation of temperature,
pressure, and density of the gas in the free jet expan-
sion. Hayhurst arrived at a complete description of
the isentropic flou field by the method of character-
istics. (The free-jet problem has been treated by other

authors ' ). Note that in the high temperature and
pressure regions of the expansion, reaction (38) can
be assumed to be equilibrated at all times. Hayhurst
concluded, "The calculations described above shou that

there is continuum flou in the expansion of the gas through
-.7
the sampling nozzle for about 5 x 10 sec, after uhich
the flou is molecular. Consequently, if the relaxa-

tion time of any chemical reaction is much greater
_7
than 5 x 10 sec at atmospheric pressure, the reaction
X
uill not proceed during the expansion. If such condi-

tion holds for all possible chemical reactions, com-
position uill not be affected by sampling. This repre-

sents the case of ideal sampling. Houever, a reaction
60
_
uith a relaxation time less than 5 x 10 sec uill be
at equilibrium in the flame, where the time available

_3
is about 10 s, and uill be able to follow any changes
of temperature, etc., up to the nozzle throat. The
relaxation time of a reaction similar to (38) uill
increase once inside the nozzle, because of the fall

in gas pressure and temperature, so that a point even-
tually be reached at uhich equilibrium can no longer
be maintained and the composition uill become "frozen."
Consequently, the composition observed uill not neces-
sarily be that of the original sanple, but uill corres-
pond to conditions at some point in the sampling nozzle."
Ions from flames have also been sampled by f'lorley 45 .
His results are in agreement uith those of Hayhurst.
In vieu of the importance of chemical relax-
ation in systems at high temperature and pressure,
Knuth studied the chemical relaxation process in
flou systems. He identified the proper relaxation
time as being^ . , the relaxation time at constant
enthalpy and pressure, rather thariTy p , relaxation
time at constant temperature and pressure. (Relaxa-

tion time is defined as the time required for the de-
\
viation from equilibrium to reduce to 1/e its initial
value if the existing thermodynamic constraints uere
maintained.) Knuth combined Bray's sudden-freezing
model uith Phinney's 57 relaxation-time-freezing point
61
criterion, i.e.,
§tYh>p -C (39)
uhere D/Dt is the hydrodynamic derivative and C is

a constant, to arrive at a chemical relaxation equa-
tion, with C given a value of 0.5. Equation (54) of
40
Knuth provides a criterion for the early freezing
of a reaction. This equation is characterized by tuo

parameters; namely, the kinetic parameter defined as
the ratio of the chemical activation energy to the
random thermal energy, and the scaling parameter defined
as the ratio of the floui time to the collision time.
58
Young used a last-activated-collision model
to determine a criterion for the freezing of a chemi-
cal reaction. In this model, a given chemical reac-
tion freezes approximately at the location uhere the
sample molecule encountered its last activated collision,
Young studied chemical freezing of bimolecular reac-
tions involving an activation energy. The number of
activated collisions of a molecule uas computed along

the free-jet centerline. The results of this calcula-
tion indicate that chemical freezing in the free jet
is characterized by the kinetic and scaling parameters
as defined by Knuth. Furthermore, the analysis reveals
that complete chemical freezing in the free-jet is
obtained if the ratio of the logarithmic scaling factor
62
divided by the kinetic parameter is less than 0.5.
0 ~ / E* (40)
•V" = scaling parameter = d*/a YAR
o
E* = kinetic parameter = E*/kT
— . Q
Too — mean time between collisions of A and B molecules

AD
E* = activation energy
d* =, diam. of sonic orifice

( ) denotes stagnation conditions
These results can be used as a design criterion to
develop a sampling system uhich avoids composition
distortion by chemical reaction in the expansion.
3.2.3 Species Condensation
Species condensation in supersonic molecular

59
beams uas first observed by Bier et al in 1956.
Condensation uould make the interpretation of measure-
ments very complicated, but fortunately, as Knuth con-
cludes in his revieu, the probability of condensations

in FIBFIS sampling of high temperature systems is very
small .
The classical theory of homogenous conden-
sation postulates that a critical size nucleus is spon-
taneously formed uhich has the properties of the bulk
phase. Such theory cannot be applied to the rapid ex-
63
pansion occurring in a free jet for it leads to crit-
ical sizes that are of the same order of magnitude as
the molecular diameters . Instead a kinetic theory
approach ' has been used to predict condensation

in the free jet, and the rate limiting step is the form-
ation of dimers by termolecular collisions, not only
for monoatomic gases, but also for polyatomic gases.
Once the dimer is formed, tuo body reactions can produce
trimers and larger clusters which lead to the formation

cf a condensate.
Knuth shows that the ratio of the flou time
d*/a to the mean time,'f" , between consecutive three
body collisions is the relevant dimensionless scaling
parameter in dimer formation. The smaller the flou time,

relative to the mean time between termolecular collis-
ions, the smaller is the dimer production. This hy-
pothesis is supported by experiments conducted by several

{• I /- o
authors ' . They found that the excess dimer mole
fraction (relative to the equilibrium mole fraction
in the source) is approximately a linear function of

p d*. Note that the scalina parameter d*/y a is re-
~o o o
r\
lated to P by equation (56) of Reference 40. Further-
more, these experiments show that for d*/Ôa0 ^50

dimer formation is insignificant (see Table I of Ref.
40 for example), and that this rate decreases as TQ

.63, 64, 65
increases
64
-
3.2.4 Pressure Diffusion
For theoretical treatment of separation ef-

fects in free jets and shocks, the reader is referred
Fi R fi 7
to the continuum analysis by Sherman ' , Mikomi and
Takashima , and the kinetic theory approach to a shock-
uave structure in binary mixtures by Oberai . Our aim
here is to present the reader with the main results
of the above experiments and theory.
In his treatment of the free-jet of a binary
gas mixture, Sherman combines the continuum flou
conservation equations (Navier-Stokes), uith the bi-
nary diffusion equation (41) based on the Chapman-Enskog
theory of diffusion,
fv A f D A B Tf(l-f) fmA"mB V Inp

1 m
-7 (41)
Uhere the subscript A refers to the heavier species;

f is the mole fraction of the heavier species, m is
the mean molecular mass given by
m = fm ft + (l-f)m Q
D Q R and(A-are the binary diffusion coefficient and

H cj
thermal diffusivity, respectively; V. is the diffusion

velocity of the heavier species. Examination of Equa-
tion (41) leads to the following conclusions: (1)
In the free-jet expansion and in a shock transition,
65
the temperature and pressure gradients are in the same
direction. Thermal diffusion opposes barodiffusion
under these circumstances. Houever, an order-of-mag-
nitude analysis of Equation (41), as applied to the free-
jet or the shock uave, shou that barodiffusion is the
dominant separation mechanism. (2) In the free-jet

expansion, the temperature and pressure gradients exist
in the radial direction outuard from the centerline.
The higher pressures and temperatures occur on the

axis and decrease radially outuard as the Mach number
increases. Thus, barodiffusion in the free-jet uill
cause an enrichment of the heavy molecules along the
jet centerline (in barodiffusion the heavy molecules
diffuse to higher-pressure regions).
Sherman obtained an expression for f, the
mole fraction of the heavy species, along the center-
line of the jet, by expanding all variables in terms
of inverse pouers of the Reynolds number based on stag-
nation conditions and orifice diameter, d*, and solv-
ing for the first-order perturbation term in the mole
fraction, f, by integrating the equations (the zeroth

order approximation leads to isentropic flous, and
homogenous mixtures). This expression can be found
in Ref. 66. The theoretical results of Sherman have

70
been validated by the experimental results of Rothe ,
66
71 72
Sebacker , and Campargue . These results show that
the heavier species are enriched along the jet center-
line as predicted from the diffusion equation and that
most of the separation occurs over a distance of three
throat diameters from the sonic orifice. Furthermore,
negligible separation in the free jet was found for
Knuth
40 considers Sherman's results and shous
that for
C = o(i) (42)
Sc m -1
mass separation due to barodiffusion near the source
2
orifice is negligible for Re £ 10 . This criterion
is conservative for x/d* > 3 due to ordinary diffusion
(Sherman neglected ordinary diffusion in his theoreti-
cal treatment. Ordinary diffusion, houever, may have
to be considered for x/d* ^> 3). In Equation (42),
C is a constant, and subscript o refers to stagnation
conditions.
Extensive experimental studies of the shock
structure in binary gas mixtures (see Ref. 40 for an
extensive literature review) shou the validity of the
theoretical treatment of Sherman and Oberai The
following features should be noted: (1) Ouing to the
fact that barodiffusion accelerates the heavier mole-
cules through the shock, and the light species in the
67
opposite direction, the shock and the jet boundary are
enriched with the light gas molecules. (2) The over-
all shock thickness, in terms of upstream properties,
is larger than for a pure gas under similar conditions.

40
Knuth argues, "Effects of pressure diffusion in the
barrel shock are important in sampling studies if the
relative enrichment of light species extends to the
jet centerline." He continues, "The important role
of the pressure gradient through the barrel shock sug-
gests that a suitable criterion for no reversed separa-
tion effects at the jet centerline might be provided
by the criterion for a diffuse shock structure. As shoun

70
by Rothe , the shock thic
thickness, o , is related to the
flou parameters as follows
. VH.0 J3*
S ^
A diffuse shock is realized ifJ /X_5 is sufficiently
large. Furthermore, for
P
I/Re o /^ P«
i
s
reversed separation will be insignificant along the
jet centerline. (Separation effects due to the shock
structure have been called "reversed separation" and
"background invasion.")
68
3,2.5 Relaxation Phenomena
Considerations of relaxation effects in the

free-jet expansion are most relevant in FIBMS sampling
of combustion systems. This uill be more apparent af-
ter the discussion of Mach number focusing and the time-
of-flight temperature measurements.
Consider the free-jet flou of a gas with vi-
brational, rotational, and translational degrees of free-
dom active at source conditions. Recall from the Kinetic
Theory of gases that to achieve relaxation, i.e.,equil-
ibrium, of all degrees of freedom the number of colli-
sions required is the largest for vibration and the least
for translation. One can characterize the relaxation
process by a characteristic time *• (the time for the de-
viation from equilibrium to be reduced to 1/e its ini-
tial value if existing thermodynamic constraints are
maintained). Furthermore, one can define a relaxation
time for each of the degrees of freedom. Kinetic Theory
also shous that as the temperature and pressure of the
system decrease the relaxation time increases, since
collisions necessary for energy transfer between the
degrees of freedom become less frequent.
Thus, if a significant change in temperature
or pressure is realized in a very short time, as it is
in the case of a HEMS free-jet expansion (see Fig. 5),
69
and as uas shown above, the relaxation of specified degrees
of freedom will lag considerably from the change in the

thermodynamic constraints. Uhen this occurs, the degree
of freedom is said to be "frozen," and the proper criterion
for freezing is that I for the degree of freedom be much
larger than the flow time through a given state. Since vi-
bration requires the largest number of collisions for re-
laxation, it freezes first, and it is folloued by freezing
of rotational and translational degrees of freedom.
As uas discussed in Section 3.2.2, Knuth devel-
oped a freezing point criterion, namely
uhere c is a constant of order unity. As Knuth points out,

this criterion is valid for all relaxation processes oc-
curring in flou systems. For each relaxation process, the
terms "partial-equilibrium flou," and "partial-frozen flou"
are used to identify flou upstream and dounstreara, respec-
tively, from the freezing surface of the relaxation pro-
cess. Prediction of the location of each of the freez-
ing surfaces requires criterion (39), and the tempera-
ture dependence of the collision number for the degree
of freedom of interest. Furthermore, the variation
of the centerline Mach number uith distance along
the jet axis must be knoun. Expressions to predict
the Wach number can be found in Section 3.2.1. The
70
prediction of freezing-point locations is beyond the
scope of this discussion, and the reader is referred
to the uorks by Knuth et a!50» 73

» 74
and Sharma54.
3.2.6 Skimmer Interference
Most of the literature pertinent to the free-

jet interference by the skimmer has been reviewed by
4D
Knuth . Criteria uhich facilitate the design of sys-
tems uith minimum skimmer interference can be found
in this reference. As Knuth points out, consequences
of this interference are (1) decrease of beam inten-
sity, (2) widening of the velocity distribution, and (3)
distortion of the beam composition, listed in order
of decreasing sensitivity to skimmer interference.
The aim here is to skim the isentropic core
of the free-jet uith minimum interference by the fol-
lowing considerations: (1) The length of the skimmer
must be such as to minimize stand-off shock (.due to

free-jet-interactions with the chamber wall) interfer-
ence.
(2) The shock structure must be attached to the skimmer
tip in order to effectively sample the isentropic core
of the jet. This puts a restriction on the external
cone angle one can use depending on the Mach number.
(3) The beam can be attenuated effectively by colli-
sions with molecules reflected off the inner surface
71
of the skimmer. This effect is minimized if the in-
ternal angle is sufficiently large.
(4) The effects of orifice size uere studied by Fisher

75
and Knuth . For a conical skimmer, the skimmer-in-
duced decrease in measured Plach number is less than
I
3^ if KnQ^ (= X ol/d,), uhere the mean-free-path A -,
is based on molecular density at the skimmer and on
collision cross section at source temperature, is great-

er than about 0.3-0.4. The first three considerations
lead to Equations (60) - (62) of Knuth.
3.2.7 Mach-Number-Focusing
Composition distortion due to Mech-number-
focusing is an unavoidable consequence of the differ-

ent velocity distributions of the heavier and lighter
species in the free-jet. The lighter species have a
greater tendency to fly auay from the centerline than
the heavier species. The end result is an enrichment

of the beam uith the heavier molecules.
Studies of P l a c h - n u m b e r - f o c u s i n g have b e e n
7£
made by Stern and Waterman for the case of parallel
continuum flou at the skimmer, Sharma for mixtures
73
of C02, Knuth et al for mixtures of monoatomic gases,
and Yoon and Knuth for mixtures of diatomic gases.
In examining the effects of Plach-number-fo-
cusing the follouing flou model is considered as de-
72
picted in Fig. (?):
(1) For a given species, transition from continuum
to free-molecule flou may or may not occur upstream
from the skimmer entrance.
(2) If transition occurs, then it takes place at a
surface uhich is spherical uith origin at the source

orifice.
(3) The molecular velocity distribution at the skimmer

entrance is, in general, a steady tuo temperature Plax-
uellian distribution superimposed on a spherically
symmetric radial hydrodynamic velocity.
Before free-molecule flou is realized in the
free-jet expansion, the translational temperatures
Ti and Ttl are equal. But, as the expansion proceeds,
the flou deviates from isentropic flou due to a large
decrease in the collision rate. T,t becomes frozen
earlier than Tj_ . Further dounstream, the variation
of T_L uith distance suitches from nearly isentropic
to a collisionless type dependence uhere Tj_ decreases
(due to geometrical cooling) uith a slope of -2. In

Rach-number-focusing studies, the relevant temperature
is Tj_
Knuth has shoun that the ratio of molecular
number density at the detector, n ,, to the molecular
number density at the skimmer entrance, n,, for a given
species can be expressed by

SOURCE
{The angles amax and £max are defined respectively by the line of sight from
the detector to the skimmer lip and by a radial line from the source to the
skimmer lip.)
Fig. 7. Schematic diagram of model considered in
Mach-number focusing .
74
(45)
n
Where the geometrical parameters are defined in Fig.
(7), and S^,, the speed ratio for the given species
at the skimmer entrance, is given by
=u (46)
2kT
m
i.e., the ratio of the hydrodynamic velocity to the
most probable random speed perpendicular to U, at the
skimmer entrance.
Writing Eg. (45) for a minor species A and
the major species B and taking the ratio of these tuo

expressions, one arrives at the enrichment factor 0(.,
) (47)
The enrichment factor depends on both system geometry
and the speed ratios. The effect of the speed ratios

on ®C , is knoun as Mach-number-focusing. For the spe-
2 ,.2
cial case that Sj, <^max -^ ôr ^ anc' B » ^-^' C47) 'De~
comes —, 2
(48)
i.e., independent of system geometry.

Three cases are generally considered: (1)
75
Continuum-flou up to the skimmer. (2) Transition
to free-molecule flou upstream from the skimmer. (3)
Transition of free molecule flou for only one of tuo
species in a binary mixture. The analysis through which
^ ± is obtained for each of the above three cases can
be very complicated. The reader uill find comprehen-
sive treatment of Mach-number-focusing effects in free-
jets in the references given at the beginning of this
section.
3.2.8 Background Scattering
Scattering of beam molecules by background
molecules may occur in all of the FIBMS sampling system
chambers. In practice, only scattering in the source
chamber might result in significant beam attenuation.
If the beam has intensity I in the absence of back-

77
ground scattering, Anderson and Fenn showed that
the effect of scattering can be expressed by
I = Io exp (-o- nx) (49)
Uhere I is the observed intensity, n is the number
density of scattering molecules,xis the distance over
uhich scattering occurs, and cr is the effective scat-
tering cross section.
Note that in a gas mixture, scattering might
result in distortion of the relative densities of the
76
several beam species. Knuth has developed criteria
to minimize this effect and the beam attenuation in the
source and collimating chambers.
3.2.9 Flame Perturbations By Sampling Cones
Feu studies have been made regarding the ef-

fect of sampling cones on flames. Furthermore, as
uill be shown, some of the theoretical studies that
have been made are not totally relevant to FIBMS sampling

systems.
78
Biorde et al investigated the effects of
probes on CFL/O^/Ar flames at 0.04 atm. They compared
the relative effects of a quartz-microprobe uith the
effects of quartz sampling cones of various angles and
orifice sizes. Comparisons uere made uith respect to
(1) visual perturbation of the flame, (2) stable species
concentration profiles, (3) temperature profiles, and
(4) sensitivity to radicals. Species profiles uere
obtained by MEMS sampling techniques. The measured

temperatures in the absence of a probe uere compared
uith temperatures measured tuo probe-orifice diameters

upstream of the sampling cone by means of a thermocou-
ple. Biordi et al.argue that this is the relevant
temperature. Their experiment led them to the follou-
ing observations:
•77
(1) As the cone angle increases, the reaction zone
appears to shift dounstreara and becomes narrower, and
the concentration gradients steepen. As they concluded,
"These effects may be rationalized in a qualitative
fashion as due to the cooling ahead of the probe and
'attachment' of the flame to the probe." The cooling
would only result in the translation of the concentra-
tion profile (the probe is actually sampling flame

gases corresponding to a point upstream of its actual
physical location). Attachment causes non-uniform
motion of the flame, and the relative changes in the con-
centration profiles are a result of it. As Biordi
indicates, attachment is disastrous if one requires
the information obtainable from the slopes of the spe-
cies profiles,
(2) The perturbed and unperturbed temperature profiles
differed by about 200°K in the low-temperature region
and by about 100°K in the high-temperature region.
Houever, for the cone for which visible attachment
occurred, the effect on the temperature uas so great

that it would be impossible to relate the temperature
with the composition profiles to the accuracy required
to calculate rates in the primary reaction zone.
(3) It uas possible to detect radical species, e.g.,
0 , OH, H, with all the cones investigated. The mi-
croprobe resulted in a 9Q% loss via wall and internal
78
collisions before a beam uas produced.
They found that a quartz sampling cone uith

40 total angle and thin leading edge minimized all
of the abouementioned distortions for their experimental
conditions, and that radical concentrations uere more
in agreement uith those obtained by other means. Higher
pressures would allou the use of larger cone angles

and thicker leading edges.
79 8D
Hayhurst et al ' studied distortions caused
by a sampling cone (1 to 2 mm. in length) projecting
from a flat plate into 1 atm. H2 - 0- - N« flames.

Ions formed in the flame uere formed into a beam by the
use of electrodes and focused through a small hole
into a detection system. The flow field model consisted
of a hemispherical point sink adjacent to a flat plate.
Their flou-field studies shou that in order to mini-
mize aerodynamic disturbances of the flame and boundary-
layer effects the use of long sampling cones of rela-
tively small external angles uith large orifice sizes
is required. These external effects include heat trans-

fer, catalytic reactions, and composition distortions
due to chemical reaction in the boundary layer. Hou-
ever, as pointed out, efforts to reduce boundary layer
effects are in conflict uith efforts to minimize com-
position distortions during the gas expansion through

the sonic orifice uhich require large internal cone
79
angles and small orifices . This is because the resi-
dence time of the gases before molecular flou is at-
tained is prolonged by making the cone more pointed
or by enlarging the orifice. (See section 3.2.2 on

chemical relaxation).
81
Smith " analyzed the problem of a long sampl-
ing cone in lou-pressure ChL/02 flames. Smith's model

consisted of a sink located at the tip of an infinitely
long cone with arbitrary cone angle. The main result

of his analysis is that the stagnation streamline moves
towards the cone tip as either the cone angle or the
sink strength is decreased. (The stagnation stream-
line separates that portion of the field that enters
the cone orifice from that uhich does not enter it.)
Smith's results shou that a compromise must be made be-
tween disturbances of the sample before and after it
passes through the sampling orifice. This is in agree-
ment uith Hayhurst's results discussed above, namely,

that during the expansion chemical freezing occurs
earlier if large cone angles and small orifices are
used. However, consideration of distortions on the

flame before expansion require the opposite.
The studies by Hayhurst et al,and Smith can
be used to predict the extent of cooling of the sampled
gas and of composition distortion due to the presence
80
of the cone when one is measuring the average properties
of the gas that flows through the sampling orifice.
This is the case for the sampling of ions that are

focused into an ion beam. Thus, for example, Smith
shous that if the fraction of sampled gas that has a
smaller residence time in the thermal boundary layer
than a given relaxation time for some chemical reac-
tion is large, then one can expect little composition
distortion due to cooling in the boundary layer before

sampling. (The thickness of the thermal boundary layer
is approximately equal to that of the momentum boundary
79
layer since Pr/^1), The average temperature drop
in the sampled gas due to boundary-layer cooling can
also be estimated from their results.
In MBRS sampling of flames, the free-jet
is skimmed along its centerline by the skimmer. Thus,
only a very small fraction of the gas that flous through
the sampling orifice ever reaches the detector. This

82
fraction can be uritten as follous
skimmer-orifice flou
= f(T)
sampling-orifice flou
Where d, = diameter of skimmer orifice, x, = distance
from sampling orifice to skimmer orifice, and f(7~)
is a function of specific-heat ratio. The ratio o^/x.

™T «~2
has values that range, from 10 " to 10 , and f(7")
81
has typically values of 1 or less. Thus the fraction
(50) is indeed small, and one may question the validity
of using the analysis by Hayhurst or Smith to predict
distortions in MBF1S sampling systems when measuring
neutral-species concentrations. That the use of aver-
age values is not justified for DBMS sampling of neutral

species is shoun by considering the influence of the
gas flowing along the sampling cone surface on the
gas flowing near the orifice centerline. The extent
of the forementioned influence can be estimated from
the ratio of tp, a characteristic time for flow through
the region in the vicinity of the sampling orifice
d*, to t_., the characteristic time for diffusion from

82
the uall to the centerline. Knuth ' has shoun that
the value of tp/tp is of the order 10—2 . This supports
the above argument. (The lack of information on probe-
induced distortion in MBHS sampling of 1 atm. premixed
flames has motivated a study uhich uas being carried
out at the U.C.L.A. molecular beam lab. at the time this
paper uas being uritten.)
82
3.3 The U.C.L.A. 1*181*13 Sampling System
The MBMS sampling system uhich uas used to
sample the premixed atmospheric methane-air flat flames
described here is depicted in Fig. 4. The background

—3 -1
pressure is of the order of 10 to 10 torr. in the
source chamber, 10~ to 10~' torr. in the collimating
—R —7
chamber, and 10 ' to 10 in the detector chamber. The
flame gas undergoes free-jet expansion through the
sonic nozzle, and only molecules flying along the cen-
ter-line of the system reach the detector.
The design of the U.C.L.A. MBMS sampling sys-
tem used here uas achieved by the considerations dis-
cussed in Section 3.2. The quartz sampling cone uas
selected on the basis of experiments, concurrent with
this study, carried out at the U.C.L.A. Molecular-Beam

Laboratory. It included a cone of total angle of 110°,
height of 50 mm., flat tip of 1.5 mm. of diameter,

orifice diameter of 0.27 mm., and a channel length
of 0.3 mm. More uill be said regarding sampline cones
in Chapter 5. The source chamber is pumped by a 16-

inch-diameter Stokes diffusion pump. The skimmer-to-
nozzle distance can be varied so as to maximize the
signal intensity at the detector. The brass skimmer
(orifice diameter 0.041 in.) transfers the core of
the free jet into the collimating chamber uhich is

pumped by means of a 10-inch diameter CUC diffusion pump.
The skimmer uas designed to minimize its interference
uith the beam. The skimmer internal half angle is 16°;

its external half-angle is 20°. The collimating ori-
fice (6 mm, diameter) can be closed by a valve. The
detector chamber is pumped by a 6-inch-diameter NRC-UHS
oil-diffusion pump. The baffle between the detector
chamber and its oil diffusion pump is refrigerated us-

ing Freon-12 to reduce background interference. The
mass spectrometer ionizer is placed uithin a liquid-
nitrogen cooled copper shroud uhich is itself attached
by means of a "cold finger" to a four-liter deuar (en-
closed by a vacuum uall) containing the liquid-nitro-
gen. The shroud reduces the background pressure in
the immediate vicinity of the mass spectrometer ionizer
by approximately a factor of five. The ionizer is
kept clean by constant heating uith a small coiled-tan-
talum-uire heater. The above features have alloued
detection of species in very lou concentrations. Con-
tamination of the detector-chamber walls can be reduced

by baking the walls externally.
The flat-flame burner has been designed and
its operation characterized by S, Saremi. Briefly,

it consists of a 2,30 inch disk (test section) of porous
brass, a burner housing, and a uater-cooling copper

line. Uniform mixing of fuel and air is achieved by
passing the mixture through a 15-foot teflon tubing
connected to the burner.
An EAI Quad. 250 mass spectrometer is used
for mass separation of the ions produced at the ionizer.
Its output is amplified by an electron multiplier oper-

ating ab -3kv. The signal is further amplified by an
100 mega-ohms, 15pf. pre-amplifier and fed into a lock-
in amplifier. The beam chopper in front of the colli-

mating orifice permits signal modulation. The fore-
mentioned lock-in amplifier is synchronized with the
beam chopper by means of a photodiode triggering system.
The lock-in amplifier allous time-averaging the modu-
lated signal from the pre-amplifier for periods up to
125 sec. The signal is finally fed into a channel
of an analog-to-digital converter connected to a LSI-11
computer uhich stores the data.
An effusive source consisting of a ceramic

tube uith an 0.040-in.-diameter orifice near its bot-
tom can be placed on or off the system centerline.

The effusive beam is used to calibrate the system and/or
to study fragmentation patterns of molecules as a func-
tion of temperature. The ceramic tube is heated by

means of a tantalum uire. A chromel-alumel thermocouple
is used to measure the temperature of the gas in the source
and a thermocouple gage to measure the pressure.
85
The source-gas temperature is measured by
the time-of-flight technique (TDF). For this purpose,
a TOP experimental set-up is placed along the system
centerline in the collimating chamber. This set-up
consists of an aluminum rod 25.6 cm. long uith a Bendix
magnetic strip electron multiplier detector at one end
and an electron-compact excitor at the other end.

The aim is to produce metastable species (mostly M^)
in the molecular beam by electron bombardment. The
ions in the beam are diverted by means of a small mag-
net attached to the aluminum rod before the detector.

Thus, the signal generated at the detector is produced
by the metastables alone. The electrons from the fila-
ment are collected by an anode connected to a uave gen-
erator uhich generates square uaves of uidth 1-5/Xsec.
at 1 msec, time intervals. The signal from the detector
is amplified by a pre-amplifier (100 mega-ohms,
15pf.) and then fed into a Fabritek signal-averaging

computer (model 1602) uhich includes a signal digitizer
and a sueep control unit. The output from the uave

generator is used to trigger the averaging procedure
of the Fabritck computer. The computer stores in mem-
ory the signal intensity as a function of time at

preset time intervals (4^Wsec.) and averages it. The
output can be displayed on an oscilloscope or recorded
on graph paper by a plotter.
86
CHAPTER 4
EXPERIMENTAL PROCEDURE AND DATA REDUCTION
4,1 Composition Measurements
Partial automation and recent addition of

a LSI-11 computer have simplified the collection of
experimental data and data-reduction. A servo-mechanism is

used to move the burner surface closer to or further
from the tip of the sampling cone. The burner can
be moved faster or slower as required by the experi-
ment. A voltage signal indicating the burner position
is sent to one channel of an analog-to-digital converter
of the computer. A total of 100 data points can be
taken in the axial direction of the burner in a span

of 0.6 cm. and stored in the LSI-11 computer. As men-
tioned in Section 3.3, the output from the electron
multiplier is amplified by a pre-amplifier and then

fed into a lock-in-amplifier for phase-sensitive analy-
sis. The net ion signal from the lock-in amplifier

is finally fed into a second channel of the analog-
to-digital converter of the LSI-11 computer and stored
in the computer memory. Computer programs were devel-
oped for this purpose.

The present detection system can resolve
87
species uhich differ by 1 amu. Species which differ
by less than 1 amu. e.g., CN (m/e = 26.0177) and C2H2
(m/e - 26.0378), cannot be resolved; their mass-spec-
trometric signals uill be detected at the same m/e
ratio, i.e., at m/e = 26 for the species in the above
example.
The signal intensity at a given mass-to-charge
ratio might be due to contributions of ions from stable
species, radical species, and fragments from a parent
molecule (fragmentation being a temperature dependent
process). Contributions from isotopes of rnajor species,

1 -Z TO
e.g., C H A , CO , also must be considered. The separa-
tion of these contributions to the signal intensity

at a given m/e ratio is facilitated in some instances
by the formation and decay of the different contribut-
ing species in different spatial regions of the flame,
and in some instances by differences in the electron
energy for the ionization processes (ionization, frag-
mentation) for different species. An extensive com-

pilation of ionization potentials (IP) and appearance
potentials (AP) of ions can be found in Ref. 88.

The electron energy scale uas calibrated
using the spectroscopically determined ionization po-
tential of Ar, 15.76 ev. For this purpose, several
ionization efficiency curves of Argon uere obtained.

One of these curves is reproduced in Fig. 8. The tail
4
6.0
•—»
09
5.0
*^
C
(5
i_
!5 4.0 —
0 •
M 3.0 -
^0
^N
^-» •
2.0 -
1.0 •
)) | - 1 • « 1 1 1 J
15 16 17 18 19 20
electron energy (ev) (uncorrected)
Fig. 8 . Intensity vs electron energy for Argon .
89
of the curve is due to the finite uidth of the elec-
tron energy distribution (about 1.5 - 2.0 ev). No ef-
fort uas made to reduce the uidth of this distribution.
A correction factor for the energy scale uas obtained
by comparing the electron energy at which the Argon
signal first appears uith the literature value of 15.76
ev.
The experiments uer e carried out at an elec-
tron energy uhich minimizes, in some cases, fragmenta-
tion of the molecule and contribution of other species.
This uas accomplished solely on the basis of appear-
ance and ionization potentials. Because of the uidth
of the electron energy distribution, the signal of
species that differ in IP or AP by less than 2 ev could
not be totally resolved (unless the species occurred
in different regions uithin the flame).
90
4.2 Temperature Measurements
The temperature of the flame gases uas de-

termined experimentally by TOF techniques. The exper-
imental set-up uas described in Section 3,3. In this
section, the analytical procedure used to determine
the temperature uill be described. The time-of-flight
for the metastable species uas determined from the
Fabritek computer output. To facilitate data reduc-
tion, the time of rise of the electronics uas deter-
mined and the time scale uas calibrated by means of
room temperature measurements.
The energy equation for adiabatic gas expan-
sion may be uritten
ho + U^
2 = hjL + u^2 ^^
uhere the enthalpy includes rotational, vibrational,
and translational contributions. For nitrogen, the
characteristic vibrational temperature is 3340 K so

that relatively little energy is stored in the vibra-
tional degrees of freedom at flame temperatures. Fur-

thermore, freezing of the vibrational modes is expected
to occur very early in the expansion. Thus, the en-
ergy equation reduces to
+ h
> < > =(
91
so that, uith freezing of rotational and translations!
degrees of freedom,
( c rot,o + c
tr,o + R)T
o = c
rot,oo Trot,eo
+ (C,tr,oo +R)!,.tr,<»3 -t-NU12 (53)
2
where the subscript <^> refers to frozen conditions,
Substituting for the values of the specific heats,

2
+ 3R + R\J = R T + 5 RT. + MU (54)
x
f) ' O rot, oo ft tr.0o 1 '
2
or the flame temperature TO

2
Ton = •=•
2 Trot,©o
r + is
5 T.tr,cx3 + FID, x(55)
1 '
7R
The most probable velocity of the molecules, U-,, is

determined from the TOF experiments. The terminal
rotational and translational temperatures, T

rot, oo
and T.
trjcxo respectively, uere estimated using the "sud-
den freeze" model described in Chapter 3. This proce-
dure is described in more detail in Refs. 74 and 82.
(Note that if no freezing of rotational and transla-
tional degrees of freedom occurs, then the energy equa-

2
tion reduces to T = P1U-, /7R).
o •*•
TOF temperatures measurements have the advan-
tage over other temperature measurements, e.g., ther-
mocouple measurements, that one is measuring the tem-
perature of gas at the same location and under the same
conditions as during the sampling experiment.
92
^•3 C.alibrat 1 on Procedures
The mass spectral signal intensity observed

for a particular ion, i, may be written
NXj^ (56)
Where n is a constant that relates the number den-
IP
sity of the parent neutral species in the ion source
to the number density in the flame, C. a constant that

includes gain factors and geometrical factors pertin-
ent to the ion source, 0*. the ionization cross section,
T. the transmission efficiency of ion i through the
mass filter, 'TP- number of secondary electrons ejected
at the conversion dynodes of the multiplier, N the
number density at the gas source (the flame in this

case), and X. the mole fraction of the species i.
In a methane-air flame, the mole fraction
of Argon remains approximately constant throughout

the different flame regions since it is an unreactive
species. Thus, the Argon signal uas used to normal-
ize all other species intensity signals, i.e.,
(57)
'Ar
uith X A knoun to good approximation, and C. ^ C Ar =
constant.
Calibration of the MBF1S sampling system en-
93
tailed experimental determination of the first tuo ratios
on the right-hand side of Egn. (57). For simplicity
i / Ar
the ratio n /n will be called (n )i, and the ra-
cS VJS i S
tio qT i Y i /0^ r T Ar >^ r uill be called ( n E F F ) i . Then,
(58)
Ar
The factor (ng)i includes effects such as pressure
diffusion in the free jet expansion, Mach-number-fo-
cusing, and skimmer interference. The factor (n^ppji

u
includes effects due only to the detection system.
Calibration of the ["IBMS sampling system for
a given species i can be done in two different manners.

In the first, a source gss of known composition sim-
ilar to the composition of the flame is sampled with
the F1BF1S system. This allows determination of the
product (n )i(r]r-pp)i since all other variables in Eq.
(58) are known. In the other method, an effusive source
is used to determine the detection system factor (hr-rr)i>
and then (n )i can be obtained from the product (h )i
(nrrrji or from a plot of (n )i vs. molecular weight.

rr
(The reader is referred to the discussion in Chapter 3,
where (n-)i is shown to depend largely on the molecular
weight of the species).

Stable species in the flame were calibrated
by the first method above, i.e., mixtures of known
94
composition uere put through the MBMS system and the
product (1)1 ( n r - ) i was determined. The effusive
source allowed the determination of (nrrr)i for the
species i; thus (n )i, and a plot of (n s )i vs. mole-

\P v/
cular weight could be obtained. The mole fraction
of stable species i in the flame was computed from
1 1
rÎ^^
Ar i M_miI-Lm"JJI A,n _
where X n , and I./I. are also knoun.

H IT iL M 37
For radicals, the mole fraction uas determined as fol-

lows: First, the beam factor (n s )i uas determined from a
I
plot of (n )i vsi m.. Then, (nrpp\i was estimated from
the literature values for the total ionization cross-
sections of Argon and the species i, and from the sen-
sitivity of the detector T. T"j/T"nr Tfcr » which uas es-

timated from the experiments conducted uith the stable
species as a function of molecular ueight. (TJote that

s a
lso a function of the molecular structure.
Ar
This introduces some uncertainty in this calibration
procedure). The radical mole fraction is then given
by, f
• *i
yi-^x
X
Ar (60)
The uncertainty in this procedure is approximately a
factor of 2.
95
CHAPTER 5
EXPERIMENTAL RESULTS
The measurements were made using a room-tem-
perature, one-atmosphere, premixed flat methane-air
flame of equivalence ratio 1.37. The flou rates uere
I
kept at 5.12 SCFH for methane and 35.6 SCFH for air.
Air was used as the shroud gas in order to minimize

the effect of buoyancy in the post-flame gases. The
flou rate of this shroud gas was set to minimize the
deformation of the edge of the flat flame.
The MBMS sampling system uas calibrated di-

rectly for the stable species CH^, 02, CQ-2, NH 3 , HCN
and NO. For other species, eg, radical species, the
calibration procedure described in Section 4.3 uas
used.
As mentioned before, the species profiles
uere taken uith the burner moving auay from the sampl-
ing cone. The electron energies uere selected to min-
imize fragmentation of the parent molecules, and to
resolve the various contributions at a given m/e ratio.
96
5.1 Temperature Measurements in the Flame
A temperature profile for the flame with

conditions as described above uas measured using the
TOF techniques. Fig. 9 shows this profile when a probe
of total angle 80°, orifice diameter 0.24 mm., channel
length 1.1 mm., and tip diameter of 2.0 mm. is used.
The post-reaction zone temperature corresponds approx-
imately to the adiabatic flame temperature.
97
2000
: :•
1500
2
o
a
o
H
1000
(b 11.37
3-0.24MM
*~
TIPDIA.I2.0MM
500
j_ _L
1 2 3 4 5
Distance (mm)
Fig. 9 . Temperature profile measured using

TOF technique .
98
During experiments, visible attachment of
the flame to the quartz sampling cone uas observed.
The attachment persisted up to a distance of about
0.35 cm. from the burner surface (for the above cone)
at which point the flame could be seen to detach itself

from the cone tip. Furthermore, when the cone uas in
its closest position to the burner surface (0.013 cm.),

the flame surrounding the cone uithin a radius depend-
ent on cone geometry showed discoloration.
Temperature profiles for cones of different

geometrical parameters (total angle, tip diameter, ori-
fice diameter, and channel length) can give useful
information regarding the effects of the forementioned
parameters on the flame. Fig. 10 depicts the tempera-
ture profile obtained uith a quartz cone of the same
total angle as the corresponding to Fig. 9 but uith a
tip diameter of 0.5 mm., an orifice diameter of 0.30
mm., and a channel length of 1.4 mm.
The following observations can be made from
Figs. 9 and 10. The uidth of the primary reaction zone

(defined as the region between the steepest temperature
gradient and the post-flame temperature) for the mea-

surements made with the cone of the larger tip diameter
is approximately 0.5 mm. larger than that observed
from the measurements made with the smaller tip dia-

meter. Furthermore, the slope of the temperature pro-
99
2000
9
e
1500
I
*-
CO
I 1000
e
$-1.37
o
TIPDIAZ0.5MM
0
500
1 2 3 4 5
Distance (mm)
Fig. 10. Temperature profile measured using

TOF technique .
100
file for measurements made uith the cone of smaller
tip diameter is greater. Note, houever, that the post-
reaction-zone temperature is approximately the same for
both cones.
101
Observations of the cones during the temper-
ature measurements shoued that for the cone uith the
smaller tip diameter the surface area of the cone that
uould glou red uas limited to the very tip of the cone
in contrast to the cone uith the larger tip diameter

for uhich a larger surface area uas observed to glou
red. Furthermore, uith the cone in the closest posi-
tion to the burner, the forementioned discoloration
of the flame uas least for the cone uith smaller tip
diameter. (The diameter of this region uas approxi-
mately 0.5-1.0 cm. for the larger tip.) Also, the
detachment of the flame from the cone surface occurred
approximately 0.5 mm. earlier for the smaller tip dia-
meter than for the larger tip diameter as the burner
moved auay from the cone tip.
Further insight into probe-induced distortions
of the flame is provided by the intensity profiles of

C02 and 02 measured uith the tuo different quartz cones.
These are shoun in Figs. 11-14. The effect of the larger
tip diameter is to reduce the measured rate of decay

of 02 and rate of formation of C02 uithin the reaction
zone of the flame. (The intensity profiles of C02 and
02 as uell as all other species intensity profiles,
are normalized by the Ar signal to eliminate the ef-
fects of temperature variation uithin the flame. For
this flame, the Argon mole fraction is approximately
102
8134 ppm.)
In conclusion, for a flame uith conditions
as described here, a cone uith a smaller tip diameter
uill reduce the extent of flame attachment to the quartz
cone. Attachment of the flame to the sampling cone
results in a decrease in the measured slopes of the
concentration profiles and temperature gradient uith—
in the primary reaction zone.
103
j
3D — O.oOmamp
o
Tio
^ 20
CM
co
tl
o
.0
2 3 4 5 6
Distance (mm)
Fig. 11. Normalized Oxygen profile ( tip dia-2.0 mm
dx=0.24 mm).
104
3.0
| zO.30 mamp
II
O
X
•5 2.0
OJ
CO
II
O
.0
i 2 3 4
Distance (mm)
Fig. 12. Normafized Oxygen profile (tip diazO.5 mm,

d ~ 0.30 mm ) .
105
I.!
(ja.37
»e —0.30mamp
\8 I.O
II
0
0.5
2 3 4
Distance (mm)
Fig. 13. CO2 Normalized profile ( tip diaz 2.0mm,

djp 0.24mm ) .
106
.5
Ee 120.50 ev
—0.30mamp
- 1.0
tl
o
II
O
! 0.!
2 3 4
Distance (mm)
Fig. 14. Normalized CC^profile (tip diaz0.5mm

)
n?
The effect of channel length and cone angle
have been studied by Yoon and Knuth 82
' in a study sub-
sequent to the preliminary experiments conducted in
this paper. As a result of their uork, the cone of to-

tal angle 110 , cone tip diameter 1,5 mm,, orifice dia-
meter 0,27 mm,, and channel length p.3 mm, was selected
as that which minimizes probe-induced distortions of

the three cones described here. (The shorter channel
length uas observed by Yoon and Knuth to minimize chem-
ical relaxation effects),
Yoon and Knuth found also that the properties

of the sampled gas for a stoichiometric flame are those
of the gas about five orifice diameters upstream from

the probe tip. Thus, temperature and concentration
profiles shown here and in the chapters to follow should
be shifted upstream by a distance about five tiroes the
orifice diameter of the probe.
Note that the use of a FIBMS sampling system
to obtain concentration profiles and flame temperatures
makes the data so obtained more self-consistent than

concentration profiles and temperatures obtained by
two different experimental techniques, e.g., WBFIS sam-
pling system for sampling of the flame, and a thermo-

couple to measure temperatures. Thus, temperature
and concentration profiles obtained by FIBFIS sampling
108
techniques makes data evaluation an easier task,
109
5.2 Stable Species Profiles
Fig. 15 depicts the mole fraction profiles

a
for the stable species CI-L, CU* nd CCU* Methane and
Oxygen are totally consumed before the end of the reac-
tion zone. The post flame mole fraction of carbon di-
oxide is near its equilibrium value of 5% (see Ref.
19).
110
TTT
Mole fraction
o p p
o
*
§
oo
£
ro o
o 3 1 i
Z (2
1
en
om o
a «y H Sr t / O
3 O ? V I*m M
* ^ o
r\i- of-*"
< 1« .-• *. • • M
ro
3
a •
*
•
•
•
•
•
p
O <
* .•
b
O •
o>
0
erOJh *
3 £ •
•
•
* •
•
•
a>
^t
-t
o
1 ««
2 o •©-
M
o
3
1 , 1 1
: 0.40mamp
; 1.37
•o^ m. *
en-
i
p "*•.. o
(0
o
0
®
i
I . I , ! i
•
o p p O O
0 O O b b
-^ Cn
Mole fraction
5.3 Formation of Nitric-Oxide in the Flame
The concentration profiles for NO, NH3, HCN

are shoun in Fig. 16, 17, and 18, respectively. The
NO (l.P. 9.25 ev)profile uas taken at an electron energy
of 13.56 ev; at this lou energy lev/el, contributions
of N15N15 and C12018 are effectively eliminated. In
the flame region uhere NO is observed to form, one
could expect a significant contribution from C2Hg.
Fig. 19 shous the relative intensity profile for m/e=30
at 13.56 ev. The first peak is attributed to HoCO,
and the second peak to C2Hg. The C2Hg in the flame
is all consumed at a distance of 0.45 cm. from the burner
surface, thus making no contribution to the NO peak.
(The first peak approximately 0.10 cm. is due to an
ethane impurity, 0.12% in the methane and in this ex-
perimental uork). Further support for the H2CO assign-
ment to the first peak can be found in Fig. 6 of Ref.
13.
The HCN (l.P. 13.73 ev) profile uas obtained
at an electron energy of 14.76 ev. In the region 0.35-
0.45 cm. from the zero burner position, the relative
contributions of HCN and C2H3 (uhich might include
contributions from other C2-hydrocarbons) could not
be resolved. Houever, by extrapolation of the portion
of the HCN profile to uhere there is no hydrocarbon
112
contribution, the onset of HCN formation can be seen
to occur at approximately 0.35 cm. from the burner
surface.
113
Concentration (ppm)
en O en
O O O
3 1 , . . . , - - . , . ,
*P
P Ps —
II I 1 I'
O -I -*•
z 4, 0 b
0 O Oi "^
o 3 J
0
2 o * * • 3
Z « en " • * -Q
2.
3
«
3
/
t •
!• •
£1 °
3' ,-s
*
* •
3 3 en ^ *
•
* *
»
3 ~
*
*
*
* —_ •
* •
CO ^m • *
*
Concentration (ppm)
cn O
0 0
Z! 1 1 1
*> J
M
<*-•
3"
/^-"
*i 44*
CO
O
o
o 0 ,, u
.•
3 S ^
c_n
=r
5 ^$
•
. •*
•
r4- O
5" fl»
•
•So f^
•
.
|HK
^
gr
^-JT1"0"
o> II ii M
_» —A
P CO CO
-Nl
?
3 °>
(D
w <
•o
Concentration (ppm)
cn O
•n O O
CO
•
I
0
/
OJr-
o
o
3 D
O
cn 0) 5T
r* ST
s 3
O
O
5*
3
T>
O^
o O
11 1 1
CO
-xl o O)
3 (D
0)
•o
C
2H6 (j) Z1-37
0.5
E^H 13.56ev
C5 !e z 0.
O 0.4 H 2 CO
II 0.3
O
s
O
CO
02 NO
11
O
* 0.
2 3 4
Distance (mm)
Fig. 19. Normalized m/er30 profile.
117
The concentration profile for NH-,
O
(I.P. 10.19ev)
uas obtained at an electron energy of 13.16 ev. In the
region uhere NHU forms, contributions from H90 frag-

mentation and OH radical species are possible, Hou-
ever, at 13.16 ev, fragmentation of H20 to OH (A.P.
18.3 ev) would be negligible even at flame temperatures.
89
The uork of Milne and Greene supports this assumption.
The hydroxyl radical (I.P. 13.17) might possibly con-
tribute to the peak at this electron energy. The rela-

tive intensity profile for m/e - 17 for the entire
region 0.0 - 0.6 cm. is shown in Fig. 20. Since OH
contribution is limited to the region 0.20-0.40 cm.

from the burner surface, the peak at about 0.55 cm.
is solely due to NH^j.
The concentration profiles for NO, NHg, and HCN have
not been corrected for fragmentation of the parent
molecules. Fragmentation of [10 is not likely to occur
until an electron energy of 20 ev is reached. There-

fore, at 13.56 ev, NO fragmentation uould be negligible
at flame temperatures. The A.P. of CN from fragmenta-
tion of HCN (I.P. 13.73 ev) is quoted to be 19.36 ev90.

Thus, HCN fragmentation at 14,76 ev is likely to be neg-
ligible even at flame temperatures. The absolute par-
tial ionization cross sections for Ammonia by electron
impact, from the threshold energy up to 180 ev, have
91
been determined by Mark et al . At 19 ev, this partial
118
CO 0.4 OH
o <0 Z1.37
T™"
*
x *
O
E e - 13 - 16e v
II
0.3 je Z0.40mamp
o
p 02 NH3
Tic •
•
4
v^ *
E
0.1 — •
F • ' i. •!• • i i i
I 2 3. 4 6
Distance(mm)
Fig. 20. Normalized m/ez17 profile.
119
ionization cross section for fragmentation of NH X to
O
I\IH2 is about 21% of the total ionization cross section

of NH. At and belou 19 ev, only ionization of MH,
occurs. Thus, IMHU - fragmentation in the flame is
not likely to be important if the electron energy is
kept lou, and at 13.16 ev is believed to be negligible,
120
The relative intensity signal for m/e=43
is shoun in Fig. 21, The electron energy uas 20.5 ev.
The signal in the region 0-0.20 cm. can be attributed
to propane fragmentation, present as an impurity in the
methane gas. The peak at approximately 0.25 cm. is
most likely C^H--,. The last peak at 0.55 cm. from the
burner surface is attributed to HMCO (I,P. 11.60 ev).
The assignment is based upon the fact that HCM is also

seen to form and decay at this distance from the burner
surface, and HCN decay is likely to lead to the forma-
tion of HNCO. Measurements made at 11.7 ev further
support the assignment of the second peak to C-7H

O i7
.
Houever, the peak attributed to HNCO uas not aluays
reproduced. Direct calibration of HNCO uas not carried

out, but its peak mole fraction has been estimated from
Fig. 21 to be approximately 5 ppm.
The results of the experiments conducted
in this study support the mechanism by uhich the onset
of HCN formation preceeds the formation of "prompt
NO," and HCN decay results in the formation of the "prompt

NO" near the reaction zone. Furthermore, PJH-, is observed
as the intermediate product of HCN decay. The rapid
build-up of Ammonia in the post-reaction zone, houever,
seems to indicate that the formation of NO and N 2 from
NH- species does not take place quickly compared uith
the rate of HCN disappearance at a flame temperature
121
of 2000°k and ^ = 1.37. HNCO seems to play no import-
ant role in the decay of HCN since its concentration
in the flame is so lou.
122
(J) m.37
Ee- 20,5ev
CO .0 I e H 0.30 mamp
o
T-
X
|
C
3H7
TiO 0.5
HNCO
_• L
2 3 4
Distance (mm)
Fig. 21, Normalized m/e=43 profile.
123
5.4 C2H2, C2Hg Profiles
The concentration profile for acetylene in
the flame is presented in Fig. 22. The profile uas
obtained at an electron energy of 17.7ev. Since the
system uas not calibrated directly for C2H2, the cross

section data of Tate and Smith 95 uere used to obtain
the mole fraction. This profile uas measured uith the
quartz cone of 80 total angle and 2.0 mm. tip dia-
meter. The peak concentration of C2H2 in the flame
is approximately 2100 ppm. This concentration level

38
is in agreement uith the results of Harvey and Maccoll
There is not sufficient data in the literature regard-
ing the fragmentation of C2H2 and C 2 H- to calculate
the importance of each at flame temperatures. Houever,
as mentioned above, the peak concentration of C-Ho
obtained here is in agreement uith the measurements
of Harvey and flaccoll.

Fig. 23 shous the relative intensity profile
for m/e = 27 at 20.50ev. The HCI\I contribution in
the post-reaction zone can be seen. This profile uas

also obtained uith the cone of 80° total angle, and
2.0 mm. diameter (cf. Section 5.1). Uith the burner
positioned at the point uhere the maximum signal inten-
sity uas observed, an intensity vs. electron energy
124
-
profile uas measured. The signal uas observed to van-
ish at approximately 14.5 ev. Thus, C2H3 (l.P. 9.45ev)
concentrations in the flame are likely to be negligible
relative to those for C2H., and the signal presented
in Fig. 23 is mostly due to the fragmentation of C2H.
species.
125
Concentration (ppm)
— __ rx>
Cn O Cn O
O O O O
o .0 o o
•n 1 1 1 1
iQ*
•
to
10
•
O —
10
ôm"e"
X
10 II 41 II
CTi
o 0 -* ^
*. %»
• w -Nj
. W
rj
H
3 0 |\J ~ *-. o -^
g o
O
fl>
(ft
l-f ....
•
» «
«J -^
ao sS~GJ
3- ' . .
• .
•
* •
T»
3 3 ' .
so a-
~ -^^
' • .
^» •
*
O* [S. —. » *
...-•'
•
.«
•
.*
</l
•
.'
"""•
C
• 2HS
0.03
(j)Z 1.37
E e Z 20.50ev
[e ~0,30mamp
8 0.02
E
HCN
OJ
n
o
O.Ol-
2 3 4
Distance(mm)
Fig. 23. Normalized m/ez27 profile .
127
Figures 19 and 24 shou the relative inten-
sity profiles for m/e = 30 at 13.56 and 12.10 ev. re-
spectively. As was mentioned in Section 5.2, the second
peak is assigned to C9£•H,-
o.
Fragmentation and cross-
section data for C2Hg at lou electron energies are
not available in the literature. Thus, an upper-bound
on the concentration of C0£.H,-b was estimated from the
cross section data of Ref.92 and the fragmentation data
of Berry and Osberghaus 93 . The maximum concentration
of tfle was estimated to be 200 ppm. The uncertainty
uas estimated to be a factor of 2.
128
r 1.37
r I2.10ev
IT O.SOrnamp
1.0
03
O
T-
X
H2CO
O
4
0.5
C
2H6 NO
»• 4 ••
•
I .
2 3 4
Distance(mm)
Fig. 24. Normalized rn/ezSO profile .
129
5.5 C»i and H2CO Species in the Flame
The system uas not calibrated directly for
the species C, CH, CH 2 « The cross sections uere es-
timated by additive methods from the data of Rapp and

94
Kieffer . The uncertainty in these mole fractions
is estimated to be a factor of 2. The electron energy
uas kept low (about 2-3 ev. above the I.P. of the spe-
cies) to avoid fragmentation of the molecule by elec-

tron impact. The concentration profiles for C, CH,
CH2 are shoun in Figs. 25 - 27. Fragmentation of ChL
to C, CH, and ChU uas observed to occur prior to the

formation of each of these species. Thus, the peaks
identified as C, CH, and CH2 have no methane contribu-
tion. As mentioned earlier, the cross section for
ionization of each of the CH- species uas estimated
by additive methods. It is believed that the cross
sections estimated here are likely to be larger than

the actual cross sections; hence, this estimate uill
lead to lower mole fractions of the species in the
flame.
130
Concentration (ppm)
Cn O cn O
O '-O O O
•n
•P
10
01
•
IO
O
s±
O
•g 11 H II
O -i
o
Î•*•S
I %
TO
cn
Concentration (ppm)
__ rv> GJ -PS en
0 0 O O 0
O O, O O 0
•n
MAI
i 1i ' ii • ii i ti i ii
0) i- jn -e-
"""" ' ii • i
o
3C O -i -*
O V J^ •
K) O O b NI
3
S
3 0
ru ~~ ft) <D
3 <
•o
§. W
I" «
_• •
TJ —»
21
o 3
3 • ,
~3 3 , •
<§* "^
9
* •
« 0 .*
Cn
Concentration (ppm)
o
O o o O O O o o o o
o o o o o o o o o o
•n
G5'
i r ~r
•
ro
•-4 -o-
o
X
it H
00
P w o
OJ O ><J1
O o
W] O)
3 3 rt>
O o <
3
U
a
Q)
ts
t±
O
3
TJ
cn
3.0
(t) = 1-37
E Z 13.30ev
rt
o le — O.SOmamp
2.0
o
5
~
to
II
o
CH
\
.0
2 3
Distance (mm)
Fig. 28. Normalized rn/en15 profile.
134
The relative intensity profiles for H?CO
and CH|7 are shoun in Figs, 24 and 28 respectively.
These profiles uere taken uith the 80° total angle
cone of 2.0 mm. tip diameter. No effort uas made to
estimate the absolute concentrations of these species.
From Fig. 28, it can be observed that the CH, contribu-
tion cannot be totally eliminated even at lou electron
energies. (This profile uas obtained at 13.3 ev.)
From Fig. 24 the H2CO formation is seen to occur prior
to ChU formation. This profile uas obtained at an elec-
tron energy of 12.10 ev. The disturbance by the probe
in this region of the flame for the cone used in this
measurement is likely to be large (see. Ref.82), so
that the uncertainty in the mole fraction that one uould
estimate also uould be large.
135
CHAPTER 6
CONCLUSIONS
The experiments show conclusively that,near
the primary reaction zone of fuel-rich flames, NO forma-
tion occurs by a mechanism other than the Zeldovich
mechanism. The amount of NO formed via the Zeldovich
mechanism, taking into account radical overshoot near

2R
the reaction zone, uas predicted by Ay and Sichel in
their computer analysis. From their Fig. 4, the NO
formed by the foreraentioned mechanism is approximately
10 ppm. The experimental NO concentration in the flame
after all HCN and NH3 in the flame have decayed uas
determined in the study conducted here, to be approx-
imately 56 ppm. Furthermore, the rate of NO forma-
tion uas observed to be largest near the reaction zone
of the flame, prior to the decay of HCN, leveling off

after all the HCN and NH 3 have been consumed. Ammonia
uas observed in the post-reaction zone of the 0 = 1.37,

CH./Air flame as a consequence of HCN decay. The
rapid build-up of NH3 (peak mole fraction of 44 ppm.)

suggests that the decay of NH. species, interconverted
by reactions of the type,
NH X + H £ NH X-1 + H2 (27)
136
x = 1, 2, 3
via reactions
N + OH £ NO + H (3)
NH2 + NO £ N2 + H20 (28)
NH + NO £ N2 + OH (29)
N + NO £ N2 + 0 (30)
does not occur rapidly at flame temperatures.
The onset of formation of HCN occurs prior
to that of NO and approximately at the same time as
NH- formation. Houever, the decay of HCN is too slou
for it to be consumed completely before the onset
of NO formation. The flame uas sampled for HNCO.
Its peak mole fraction uas estimated to be approxi-
o fi
mately 5 ppm. This indicates, as suggested by Haynes ,
that HNCO decays by extremely rapid reactions, and
that the initial weakening of the C-N bond in HCN
to form the OCN - species is the rate limiting step
in HCN oxidation.
Concentration profiles uere obtained for
the species C, CH, CH~. The maximum mole fractions
of C, CH, and CH2 are approximately 206, 481, and
908 ppm., respectively. The most likely reactions
leading to the formation of HCN are
C + N2 £ CN + N (12)
CH + N2 £ HCN + N ( 7)
CH3 + N 2 £ HCN + NH (13)
137
The rate constants of Reactions (7) and (13)
oc
were calculated by Peeters et al. from experimental
data at 1820°K. Their values are given by
k? = 8 x ID11 exp (-11,000 /RT)
k13 = 2.8 x 1012 exp (-22,500 /RT)
in units of mole -1 cm3 sec-1 , uith a probable error
of a factor of 2. It is likely that the formation of
HCN can be explained by Reactions (7) and (13), uith
Reaction (13) dominating because of the larger concen-
tration of ChU in the flame. Reaction (12) uould also
contribute, but to a lesser extent.
C^-hydrocarbons uere observed to form and
decay mostly uithin the primary reaction zone of the
mo
flame. The peak £^2 ê fraction uas estimated to
be 2100 ppm., uncertain by a factor of 2. The C2-hy-
drocarbons provide additional paths for the consump-
tion of the methyl radical uhich contribute to keep-
ing the ratio of CO molecules to hUO molecules formed
from CH* oxidation equal to 0.5. Thus, this study
further indicates that C2 chemistry has to be consi-
dered in the kinetic modeling of methane oxidation
in fuel-rich flames.
The experimental data obtained from the flame
gives insight into the mechanism of CH,-oxidation in
fuel-rich flames. The formation of the methyl radical
138
does not reach significant rates until most of the for-
maldehyde in the flame has been consumed, (The hUCO-
forming reaction(s) keep the CHU concentration level
very low). Furthermore, the HUCO profile attains a
maximum before the primary reaction zone of the flame
is reached. The lou 0-atora concentrations in the re-
gion uhere FUCO rapidly forms suggests that the reac-
tion of CH3 uith oxygen is the main path for H~CO forma-
tion.
Visible attachment of the flame to quartz
cones of total angles 80°, and 110° uas observed in
the course of these experiments, for a flame of equiva-
lence ratio 0 = 1.37. The attachment to the cone per-
sisted throughout the primary reaction zone of the flame
and resulted in a decrease of both temperature and
concentration gradients uithin the primary reaction
zone. Quartz sampling cones of small tip diameters
reduce the attachment effects.
139
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UNIVERSITY OF CALIFORNIA

A FIBFIS Sampling Study of

Formation of Nitric-Oxide in a Premixed

Fuel-Rich Methane-Air Flame

A thesis submitted in partial satisfaction

of the requirement for the degree

Raster of Science in Engineering

Eldon L. Knuth, Committee Chair

University of California, Los Angeles

LIST OF TABLES ... viii

ABSTRACT OF THE THESIS xiii

2.3 Formation of NO in Fuel-Rich Flames ... 22

3.2 Possible Composition Distortions in MBMS

3.2.2 Chemical Relaxation in Supersonic

3.2.3 Species Condensation ....... 63

3.2.5 Relaxation Phenomena ....... 69

3.2.6 Skimmer Interference . . . . . 0 . 71

3.2.9 Flame Perturbations by Sampling

CHAPTER 4. EXPERIMENTAL PROCEDURE AND DATA RE-

4.2 Temperature Measurements ......... 91

4.3 Calibration Procedures .......... 93

CHAPTER 5. EXPERIMENTAL RESULTS ... 96

5.1 Temperature Measurements in the Flame . . 97

5.4 C2H2, C2H6 Profiles . .. . 124

CHAPTER 6. CONCLUSIONS .... 136

1. node of coal formation . 3

2. The dependence of CH20, C2H4, C2H2, and H2

peak concentrations on flame equivalence

on peak JCH-, } for a range of flames $ =

4. The U.C.L.A. MB[*]S sampling system ..... 50

5. Temperature ratio as function of dimension-

less flou time for free jet gas flows from

6. Free-jet shock structure .......... 55

7. Schematic diagram of model considered in

8. Intensity vs. electron energy for Argon . . 89

nique ..... ......... 93

11. Normalized Oxygen profile (tip dia. = 2.0

12. Normalized Oxygen profile (tip dia. = 0.5 mm,

d^. = 0.30 mm) ........ . . ..... 105

d# = 0.24 ram) ................ IDS

21. Normalized m/e = 43 profile ......... 123

24. Normalized m/e = 30 profile 129

1. Methane oxidation in fuel-lean mixtures ... 35

Y r-lach disk diameter

eq denotes equilibrium values

I uould like to express ray gratitude to Dr.

to Dr. 0. Smith, Fir. Uayne E. Rodgers, and Ph.D. stu-

dent S. Yoon for sharing their knowledge and useful

A MBWS Sampling Study of

Formation of Nitric-Oxide in a Premixed

Fuel-Rich Methane-Air Flame

Plaster of Science in Engineering

Professor Eldon L. Knuth, Chair

The formation of NO in a fuel-rich, premixed

methane-air flame at one atmosphere uas studied using

molecular-beam-mass-spectrometric (MBMS) sampling tech-

A flat flame of equivalence ratio 1.37 uas

sampled uith particular attention given to NO, HCN, HNCO,

found to occur prior to the formation of NO, approxi-

mately at the same time as the formation of NH,, and very

HCN leads to NH- formation, and, to a lesser extent, to

NO formation. HNCO is observed at very lou concentrations

in the post-flame gases, and acts as an intermediate in

HCN decay. The peak mole fractions of HCN and NH^