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NITRIC OXIDE FORMATION FROM N2 IN FLAMES"

THE IMPORTANCE OF "PROMPT" NO
A. N. HAYHURST* a n d 1. M. VINCE**
Dr'part OlC#tt e!! ('hcnlical I'Sil#ineerin~t and "Fuel Techmdo~l)'. Stlel#iehl I_'nil"ersit.v,
Mappin St.. Y,he[liehl S I 3JD. Emlland

I. I N T R O l i I ' ( ' T I O N in the combustion air, and nitrogenous fuel impurities

Two of the gaseous oxides of nitrogen, nitric oxide
( N O / a n d nitrogen dioxide (NO,I, collectively known
in a pollution context as NO,, are emitted from
combustion processes as trace species. These oxides
are normally present in the atmosphere in low con-
centrations, as a rcsuh maml? of forest fires or
lightning, and have a role in lhe fixation of nitrogen.
However. the high local concentrations of NO., gene-
rated in man-made flames have a variety of harmful
effects on the environment. The oxides of nitrogen
have proved to be the most intractable of gaseous
pollutants from combustion. This is partly explained
by the fact that they were the last to be recognized as
a nuisance and the obvious steps customarily taken to
reduce emissions of CO. unburnt hydrocarbons (HC)
and soot tended to maximize NO~. In addition, an
imperfect understanding of how NO, is formed has
been responsible. In particular, a given mathematical
model of NO~ formation has often proved useful in
some systems and yet has been most unsatisfactory in
several others. It is also fair to say that combustion
modifications designed to suppress NO., have, until
recently, fallen puzzlingly short.
Because the main way of producing NOx in flames
(the so-called Zel'dovich mechanism x) is relatively
slow, the interaction between turbulence and chemical
kinetics can be important. Nevertheless, this review
concentrates mainly on kinetic effects. This is partly
because most light has been shed on the subject by
observations made in simple non-turbulent systems,
especially burners producing flames in plug flow, and
partly because "'prompt" NO production, the central
subject of the reviews, involves chemical reactions
which are much faster than the Zel'dovich ones, so
that turbulence-kinetics interactions are relativeh'
unimportant.
2. FORMATIONOF NO~ 1N FLAMES
In general, there are two sources for the nitrogen in
NO., emitted from combustion systems: these are N_,
* Present address: Depamaaent of Chemical Engineering,
Cambridge L nixersity. Pembroke St.. Cambridge CB2 3RA.
England.
** Present address: Department of Chemical Engineering
and Chemical Technolog.\. Imperial College. London SW7.
England
{leaving aside any exotic nitrogenous rocket fuelsl.
Fuel-NO is per se outside the scope of this review,
although much of the material presented below in
Section 2.2 comes from experiments with fuel-N.
Except in the case of rich ~equivalence ratio, q$ > 2).
cool ( T < 2000Kt flames or those doped with nitro-
genous additives, the concentration of NO tdenoted by
[NO]t measured in combustion gases is always below
the equilibrium concentration at the hot-gas tempera-
ture, commonly by several orders of magnitude.
However, equilibrium for ambient atmospheric
temperatures is greatly exceeded and the flame [NO]
is said to be "'frozen" by a rapid quenching of the
combustion gases. Clearly, kinetics are of paramount
importance in characterizing NO~ formation and
destruction in flames, because the rate-determining
reactions are too slow for equilibrium considerations
to apply. As mentioned above, emission levels for
turbulent diffusion flames are also strongly influenced
by combustion aerodynamics.
2.1. T h e Zel'dovich Mechanism
Fixation of nitrogen requires the breaking of the
unusually strong bond holding together the N2
molecule--its dissociation energy is 941kJmo1-1.
Several flame radicals could, in principle, achieve this
at a reasonable rate. The "prompt" mechanism
described below in Section 2.2. relies on hydrocarbon
fragments. Zel'dovich I discovered the following chain
mechanism :
O+N,~NO+N (1)
N + 02 --* NO + O. (2)
Reaction (1) is now universally accepted as the rate-
determining step in the formation of virtually all
NO in the post-flame gases, i.e. in the region where
radical recombination is almost complete and tempera-
ture well defined.2 The rate constant for reaction (1)
is commonly quoted 3"4 as approximately
5 x 1013 exp ( - 37,890/T)ml mol- 1 s- i.
Owing largely to the difficulty in obtaining reliable
measurements of local [O], there is an uncertainty of
at least a factor of two in the pre-exponential term)
This is an important uncertainty, as there is con-
troversy regarding the relative contributions of other
mechanisms to NO formation: •
36 A.N.H..x3 HL ~ST and I. M. \'Ix('l
Kinetic inconsistencies in N2OH2 flames with
additives led to the suggestion by Fenimore and
Jones 6 that reaction (2) might be bypassed, especially
in rich flames, by the reaction
N + OH ---+NO + H.
The effect of including reaction {3) in kinetic calcu-
lations is most pronounced when [NO] is high and
the reverse reaction becomes important. The forward
step is indistinguishable, in terms of NO formation
rate, from reaction (2); in either case, two molecules
of NO are produced from each N2 molecule ruptured
in the rate-determining step. Minor roles have been
ascribed to N_,O~ and also to HNO. s The former
has been found to be quite important in cold, lean.
well-stirred flames. 9
From the foregoing, it appears that NO formation
should be highly dependent on temperature, linearly
dependent on oxygen atom concentration, and
independent of fuel type. Final levels of emission
should be roughly proportional, for isothermal flames,
to post-temperature residence times. Steps to minimize
NO~, emissions, based on these conclusions, have
succeeded up to a point {see Section 4 below), but
quantitative predictions of NO formation rates based
on the Zel'dovich mechanism have been generally
unsatisfactory.
2.1.1. Supra-equilibrium reulicals
The importance of allowing for supra-equilibrium
concentrations of radicals when measuring NO.<
formation rates in and near the primary reaction zone
appears to have been first pointed out by Thompson
et al. ~° Assuming rapid balancing-" of radical inter-
conversions, these workers and others ~ - l ~ were
able to account, within experimental accuracy, for the
observed rates of formation of NO in a wide variety
of flames. Here it should be mentioned that the
literature value for the rate constant of reaction 11)
is considered by some ~-" to be too low by a factor of
two. Other workers ~5.1o have measured [O] spectro-
scopically and validated the extended Zel'dovich
mechanism. Despite such concordance, however, NO
levels have consistently been found in excess of pre-
diction, whether m well-stirred, *~~ turbulent-
diffusion, ~~''~9 or laminar premixed Ilames. z°'-'
2.1.2. Temperature fluctuations
For turbulent diffusion flames, the interaction
between chemical kinetics and aerodynamics com-
plicates the picture. Temperature Iluctuations have
been invoked '2'23 as a cause for the excess NO,-. As
mentioned above, the rate-determining step of the
Zel'dovich mechanism is highly temperature-sensitive,
having a large activation energy of E~ = 314 kJ tool
Gouldin 22 evolved the criterion that for turbulent
fluctuations to be neglected :
{E,/R:I}e[IT'}'-/:I z] ~ I
where T is the time-mean temperature aud T' the
characteristic fluctuation amplitude. Jones :~" tbund
that allowing for temperature fluctuations would
increase the calctlhlted yield of NO, from a turbulent
system by typically an order of magnitude. Thompson
{3} et a/., 25 applying coherent structure theory, and bearing
in mind the high diffusion coefficients of H and He.
suggested that in the vicinity of the reaction zone [ 0 ]
was raised to approximately its equilibrium xah,e at
the peak temperature.
It must be emphasized that. on account of the
complexity of turbulent combustion, it has not yet
proved possible to test the temperature fluctuation
theories even semi-quantitatively. Semerjian and
Vranos e6 altered combustion chamber configurations
to damp their high amplitude temperature oscillations.
but found no corresponding change in NO., con-
centration, Sadakata and Beer 2; measured local NO
formation rates in a swirling turbulent diffusion flame
of methane in air. They made allowance for supra-
equilibrium [O] and, up to a point, for temperature
fluctuations ; turbulent diffusivity was determined from
He-tracer experiments. In the main reaction zone. NO
formation was much faster than predicted by the
Zel'dovich mechanism.
In conclusion, it should be stressed that Gouldin's
criterion -'2 {mentioned above) completely fails to allow
for the fact that. for the rate of reaction to be affected
by temperature oscillations, the time constant of the
chemical reaction concerned has to be significantly
less than the period of the oscillations.
2.1.3. The role o l N 0 2
NO has a mean half-life of several days in the
atmosphere before conversion to NO2, the directly'
harmful agent, which has generally been believed to
represent no more than 5°. of exhaust NO.,: on
quenching, NO is frozen at a high concentration with
respect both to NO, and N2. Fairly recently, however.
very high levels of NOe have been monitored of up to
80",, of NO.,. especially from gas turbines. -'s-3°
Cernansky and Sawyer 2~ haxe offered a plausible
scheme lbr anomalously high [NO,]. hmgeing oll the
temporary coexistence of high radical concentrations.
high [O2], and relatively cold conditions a set of
circt, mstances awlihlble in turbulent diffusion flames.
More problematical is the short-lived NO_, found in
high concentrations in tile flame and p#'dtame regions
by Merryman and Levy 3~in laminar premixed CHa. 'air
l]ames 10.1 I bar. 1600 2000 K). with or without added
fuel-N. Considering the axial NO and NO_, coll-
centration proliles reported, ~ highly tmequilibrated
with respect to each other far downstream of tile
flame zone, it is dilticult not to conclude that the
NO2 is hlrgely a sampling artehict.-- In fact, Wendt
and Ekmann 33 failed to repeat Merryman and Levy's
observations. Also, Fenimore, ~a on adding NO to lean
premixed llames of CO and.'or He in air. found
[NOz]/[NO] much greater than the equilibrium ratio
in the reaction zone. but the ratio fell to approximately
 I>rompt nitric oxide
equilibrium level in the post-lhunc gases, in filet, only
in the coolest flames 17 < 12(X) K) was there
appreciable fl'eezing of NO2. Duterque, ~s m adding
NO to a prcmixcd flame in quantities sullicient to
double concentrations measured without additive,
found N O , levels unafl'ccted. For the purpose of this
discnssion, il is in some ways of no consequence
whether or not these measured high [NO.,] are
spurious, because any reasonable scheme for the
formation of NO2 entails NO as a precursor, e.g. :
N O + 1-lO2 -> NO2 + OH
NO+O+ M--+NO2 + M
N O + 02 ---, NO2 + O.
The fact that each of these schemes is likely to have a
relaxation time larger than the residence time of NO
in a llame is a very' strong indication thal N O : plays
no part whatsoever in most flames. This has been
confirmed recently by Johnson et al., ~" who consider
N O , to be formed during sampling. At this stage
then, the origins of N O remain to be fully elucidated,
because as stated above, the Zel'dovich mechanism is
frequently inadequate to account for both the high N O
formation rates in the primary reaction zone, and for
the final N O emissions from hydrocarbon flames.
2.2. Prompt N O
In the preceding section it was stated that the
Zel'dovich mechanism often underpredicts N O forma-
tion rates, and that extensions of the basic system to
150
MIX = 1 05 x STOICHIOMETRIC FUEL
T= 2300 K
O O
mE 100 0 0 T TM 21#397
r~mo 50 =0 80
0~ i "[--2127
0 ~0 20
TIME MILLISECONDS
Fl(i. 1 Measured [NO] along lbur ethylene-air flames as a
functior~ of reaction time: i.e. the distance of the point of
sampling from the burner face divided b} the calculated
xelocit> of the burned gases. The mixture strength and
temperature of each flame are as quoted IReproduced with
permission from Fenimore-'".t
37
allow for supra-equilibrium [O], temperature fluctu-
ations, and various nitroxy compounds, have yielded
equivocal results. Fenimore, 2" obtaining axial [ N O ]
proliles Ibr prcmixcd lhit Ilamcs, extrapolated the
almost linear portions of these profiles in the burnt
gases back to the burner head. A rapid generation of
NO in the reaction zone was in certain cases indicated
by, positive intercepts, which he hibelled "'prompt"
NO. This is shown in Fig. 1. The variation of the
intercept with fuel type, temperature, pressure and
stoichiometry was in each case inconsistent with pre-
dictions based on the ZeFdovich scheme alone.
F'enimore 2° was led to postulate that prompt NO
arises from the attack by a hydrocarbon fragment
on molecular nitrogen. The likelihood of such a
pathway is examined below, on the basis of
Fenimore's:" and other workers" findings.
2.2.1. Effect <?[raryhlH comhustiml condilion.~
2.2.1.1. Fuel t),'pe. Fenimore 2° found no prompt NO
in H2 or moist CO flames, but did find it m ethylene,
methane and propane flames. This distinction has
been confirmed by many investigators, in premixed
flames,12.21 in a jet-st irred reactor,1 ~ and m turbulent
diffusion flames. 3~ NO formation, according to the
Zel'dovich mechanism, is independent of fuel type,
except in so far as temperature and [O] are affected.
Now, for the same temperature and stoichiometry,
hydrocarbon flames display lower concentrations than
hydrogen flames of all non-hydrocarbon radicals,
such as H, O H and O. because hydrocarbon fragments
inhibit chain branching.
2.2.1.2. Temperature. In contrast to the highly endo-
thermic reaction (1), Fenimore found prompt N O
levels to be only weakly temperature dependent. Many
workers 3s-'~° have confirmed this. The finding is not
inconsistent with a rate-determining step involving a
hydrocarbon radical and a nitrogen molecule, as
discussed below.
2.2.1.3. Pressure. The patterns of pressure depen-
dence for prompt N O levels found by Fenimore, 2°
and others "~m'~ are generally inconsistent with the
Zel'dovich mechanism. Fenimore 2° found that, for a
flame of 0 = 0 . S and P = 1-3bar, prompt [ N O ]
varied approximately as P~ 2 This seems to rule out 39
supra-equilibrium [O] as the main cause of fast early
formation of NO. as higher pressures promote radical
recombination at the expense of chain propagation.
2.2.1.4. Stoichiometry. Fuel-rich flames have been
found to give more prompt N O than lean or stoichio-
metric flames of the same temperatureJ ~'~s'2~ and
indeed Fenimore 2° found a peak at q5 = 1.4, as shown
in Fig. 2. This is perhaps the most compelling of
Fenimore's reasons for rejecting the Zel'dovich scheme
as the source of prompt NO, since [O] decreases by
orders of magnitude in going from moderately lean
to rich conditions. In contrast. CH and C~ both have
concentration maxima at (h = 2.5 in oxy-acetylene
flames) 2 Iverach et al., 2~ in repeating and extending
Fenimore's experiments, found that. in order for the
38 A.N. HA'¢Ht:rSTand I. M. \qxce

FLAME T = 2300 K stoichiometric flames, i.e. in most practical systems.

/
Yet Fenimore 2° found measurable prompt NO at
/ oh=0.8, as have Malte e t al. TM at 05= 0.7. and
o50 R
/
/ 2 lOO K Bachmaier et al. 4 at 05 = 0.6. Fenimore estimated -'°
E
o.
/
z/4 that prompt NO can constitute ~30°o of the total
NO emission from a gas turbine under normal
t,-.
&. operating conditions. This point is further discussed
w
below.
One conclusion from the mutually supporting
observations outlined in the previous section would
seem at first glance to be irresistible ; there is indeed a
0 I 1 I 1 pathway, distinct from the Zel'dovich reactions, for
12 16
NO formation in flames, whose rate-determining, or
at least initiating, step is the attack of a hydrocarbon
2 -- fragment on a nitrogen molecule in the flame front,
...i
and it remains merely to find all the intermediates
o and quantify the kinetics. The "'prompt" concept has,
O however, remained controversial, partly because the
'z'l -- O - © primary reaction zone is the most problematical flame
region, both chemically (temperature undefined, supra-
iv-
equilibrium concentrations of radicals, short-lived
species, etc.) and from the sampling point of view. But
an avoidable stumbling block has been the procedure
0.8 12 16 of extrapolating axial [NO] profiles from the near-
MIXTURE STRENGTH
linear region in the burnt gases to the burner head.
Fro. 2. Upper plot: [ N O ] formed in or very near the and ascribing the intercept wholly to prompt NO. It is
primary reaction zone of ethylene flames, for various mixture clear from the foregoing that this procedure usually
strengths, qS. Lower plot: the same data with [ N O ]
expressed as a fraction of its equilibrium concentration in overestimates prompt NO, since reaction (1) is faster
the final burnt gases. (Reproduced with permission from in the flame zone. So how much of the intercept
Fenimore. -~o) is truly "'prompt", i.e. independent of reaction (1)?
Sarofim and Pohl, 1"*from work on premixed methane
Zel'dovich mechanism to account for N O generated in
flames, concluded that, except possibly for very rich
the reaction zone the O - a t o m concentration in some
flames, supra-equilibrium O-atom concentrations
rich hydrocarbon flames w o u l d be required to exceed
could account for all of the intercept-NO; these
its equilibrium value by a factor of several thousand,
workers also hypothesized that Fenimore's H2/CO
corresponding to two orders of magnitude above the
flames were subject to greater heat losses than his
concentrations actually encountered. In addition, the
hydrocarbon flames, thus depressing [O3 and the rate
supra-equilibrium zone would have to extend for more
of reaction (1). Recently, however, several workers
than 1 ms into the burnt gases. Both these require-
have actually measured local temperatures and [O]
ments are clearly unfulfilled according to Millikan.".3
(and [OH] too, by Malte e t a / . ~s) directly, and found
However, substantial hydrocarbon concentrations are
the Zel'dovich mechanism inadequate. For instance.
found in just those regions where the Zel'dovich
Blauwens et al. ~'~ calculated from results in hot. lean
mechanism proves inadequate. As a crude check on
ethylene flames that Zel'dovich-NO production in the
the validity of the above, lverach et al. "-~ also calcu-
flame front was negligibly slow. Bowman and Seery "~s
lated the ratio of [N]rcqt,ircd:[N]cquilibri...... assuming N
found no evidence in shock-tube studies for prompt
to be an obligatory intermediate in NO formation by
NO ; however, as Iverach et al. 21 pointed out, the high
any pathway, and thus, if anything, overestimating the
temperatures in these studies have a masking effect
ratio. Significantly. ratios greater than seven were not
(see below). Bowman et al, have since found evidence 17
encountered: the most common value was around
for prompt NO in a jet-stirred reactor. Gay et al., "~5
unity. As a final comment, one strong piece of evidence
using molecular beam spectroscopy, found that net NO
(discussed belowj in favour of the prompt route is the
production does not commence until the post-flame
detection of HCN and CN near the reaction zone of
gases; this conclusion was arrived at in spite of their
hydrocarbon flames. These species are likely inter-
recording a peak in the flame zone corresponding to
mediates in the production of prompt NO.
a molecular weight of 30, which they ascribed 'largely
to H2CO, and in small part to C~~O, an interpretation
2.2.2. 7he cml/rocer.sy o r e r the e . \ i s t e m ' e ~![prompt NO
that brought criticism from Bowman and Seery. "~3
The general impression one gleans from the If the "'prompt" hypothesis is accepted, it remains to
literature is tha.t prompt NO need be invoked, if at isolate the components of intercept-NO. Its measure-
all, only in rich llames, while the Zel'dovich mcnt provides only an upper limit for the prompt NO
mechanism, after a certain anloun[ o f adjusting, concentration, even in rich. relatively cool ttames,
adeqtlalcly predicts It~rmation rales in lean and where tile inlercept is at least readily measurable,

owing to the sharp decline in NO formation in tile
post-flame region: in hot, lean llames, timeerror in the
intercept can easily exceed 100",,.
One approach towards increased accuracy has been
to study low-pressure premixed flames, thus spatially
stretching timereaction zone. at'¢a'a~ This has led to tile
elucidation of the kinetics of various reactions
supposedly revolved in prompt NO formationff8"5°
In addition, Hayhurst and co-workers 4°'st's2 have
succeeded in experimentally separating in an un-
ambiguous way "prompt" from supra-equilibrium
Zel'dovich NO in a variety of premixed H2 flames,
containing small amounts of hydrocarbons. The
response of prompt NO to variations in temperature
and stoichiometry was very' much as expected from
Fenimore's work. 2°
Though some of the evidence is indirect and
circumstantial, it seems lllal the simplest way' to
account for the facts dependence of intercept-NO
on fuel type. temperature, pressure and stoichiomelry
is to accept the reality of prompt NO. In the following
subsections, possible pathways for NO formation in
line with this hypothesis will be examined in detail.
It is worth noting at this stage that models'.8"53"s'~
based on these pathways generally give excellent agree-
ment with experiment, in contrast with the several
M hoc assumptions required if prompt NO is not
accepted. ~a..,6
2.2.3. T h e i b r m a t i o ~ oJHCN
Supposing the attack of a hydrocarbon fragment
on N 2 is indeed the first step on the road to prompt
NO, it is natural to 10ok for simple cyano species
(CN. HCN. C=Nzl as intermediates. Bachmaier et al.'*
used two methods of measuring [HCN] in a series of
premixed flames of varying stoichiometry and tempera-
ture in the range 1900-2250K: both methods yielded
similar values and some results are shown in Fig. 3.
TIME, MILLISECONDS
5 10 15
I I
25 ~-- I 1
o + OH ~ C H + H2OJ. although CH2 was formed
1 mainly from CH3 in methane flames, but in ethylene
z'lO
0 10 20 30 40 50
HEIGHT, mm
Flc;. 3. HCN profiles along tirol-rich propane-air flames of
different equi~alence ratios. O IReproduced with permission
from Bachmaier er ol.a)
Prompt nitric oxide 3u
In the lean tlames, no HCN was detected. In flames
with 4)= 1.1 1.35, HCN appeared in tile reaction
zone, and rapidly disappeared in the region of fast
early NO formation, hi the richest flames ~4~> 1.5L
however, HCN was detectable, its concentration having
attained a steady level, even after 15ms; moreover.
[HCN] increased with ¢k, outstripping [NO] m the
richest flames. In a similar system, cyano species
(mainly HCN) were found in above-equilibrium con-
centrations by Haynes eta/., 53 w h o corroborated tile
above findings, adding the observation that. for any
series of flames, maximum intercept [NO] was
associated with the highest initial rate of [HCN] decay.
Morley s'L recorded another piece of important
evidence, namely the near-independence of [HCN].
corrected for N= and hydrocarbon concentrations
(expressed as [CH~] in the burnt gases), on temperature
and fuel type. This is a requirement which must be
met by any pool of precursors of prompt NO. Again,
HCN was found in hydrocarbon flames, but not in
CO/H2 flames, by Takagi et al. 3v A very strong
reason for invoking the cyano pool of HCN and CN,
with concentrations coupled by, a rapid balance of
HCN + H = CN + H> is its role as a near-obligatory
intermediate in the conversion of fuel-N to NO. as
discussed below.
The mechanism of HCN formation from N= is still
open to debate, for three main reasons: there are so
many short-lived hydrocarbon radicals which might
conceivably attack N> the kinetics of these reactions
are incompletely known, and the extent of equilibration
within the radical pool in the flame zone is, unlike the
case in hydrogen flames, obscure and variable. This
last point is well illustrated by the findings of Peeters
and Vinckier,5° who measured radical concentrations
with a quadrupole mass filter in low-pressure flames of
methane (or ethylene)/Oz/Ar. The results were in
accord with the assumption that CH and CH2 were
equilibrated with each other, but CH3 was only
partially equilibrated with respect to these. CH was
found not to be formed directly from CH~ (through
20
the seemingly plausible steps CH3 + O ~ C H 2
ones it came from CiH,, + O--* CH= + CH=O, The
destruction pathways for CH and CH= depended
strongly on stoichiometry, in line with CH + H
C + H= and CH + O2 ---,products being important.
It might be noted that Bulewicz et al. '*z found [CH]
and [Ca] linked via [OH], although they did reject
direct interconversion between the two.
A certain amount of reductio ad absurdum has been
attempted, despite the difficulties. Hayhurst and
McLean sx eliminated on energetic grounds all oxy-
genated fragments except CH30 as possibilities for
attacking N=, and noted that the transition state for
CH30 ~ N2 ---,HNCO + NH2 lacked plausibility.
CHyO is, in any event, one of the less abundant
radicals present. The reactions
C2+N2-'*CN+CN AH½'gs= 34kJmol 1 (41
40 A.N. HAYHURSTand I. M. VL',CE

C2H + N2 "0" HCN + CN AH.~98= 93 kJ m o l - x

(5)
C + N2 --*CN + N AH~98 = 193kJmol - t (6)
are generally regarded as making insignificant con-
tributions : reaction (6) is presumably too endothermic,
while reactions (4) and (5) are four-centred reactions.
This latter objection does not seem sufficient grounds
to disqualify reactions (4) and (5) outright, as they are
not desperately endothermic (although, of course, e~
activation energies can exceed heats of reaction), and
C2 and CzH are present in appreciable concentrations
in a typical reaction zone (and beyond, in very rich
flames55). Besides, the credentials of the two remaining
candidates, 0 0.25 0.50 0.75 1.0
Volume '70 CH~ in unburnt gases
CH + N2 ---*HCN + N AH~98 = 13kJmol -~ (7) Flcl. 5. Dependence of the yield of prompt NO. adjustel
for any change in [N2], on the amount of methane added
CHz + Nz --* H C N + NH AH~g8 = 126 kJ m o l - t
to a flame ([Hz]/[O2]/[N2] = 3.0/1.0/5.7: temperature =
(8) 1900 K). (Reproduced with permission from Hayhurst and
Vince.'~°I
are not unexceptionable: reaction (7) is spin-forbidden,
while reaction (8), like reactions (4) and (5), is sterically
hindered. Nevertheless, Blauwens et al., ~'3 using mass
molecule of the hydrocarbon additive. They argued
spectrometry to measure axial concentration profiles
that this must rule out a primary attack on N2 by
of C, CH, CHz, CzH and NO in the reaction zone
any species containing two or more carbon atoms,
of premixed low-pressure hydrocarbon flames, ruled
which in their view left CH and CHz as the only
out on simple kinetic grounds all but reactions (7)
plausible candidates for reaction with N2. Because
and (8). Hayhurst and Vince '~° burned premixed
of their stability, HCN (or CN) is inevitably one of
H2/O2/N2 flames and measured the yield of prompt
the products of this primary reaction, as seen in
N O directly from the increment in [ N O ] caused by
reactions (4)-(8).
trace additions of hydrocarbons (CH4, C2H4, C3H,0
To discriminate between CH and CHz, accepting
to the burner supplies. This is shown in Fig. 4, where
for the moment that the list has been legitimately
the final differences between curve 1, for no carbon
whittled down to these two, is difficult in the extreme,
present, and curves 2-5, with increasing quantities of
since there are too many variables for the number of
hydrocarbon additive, are amounts of prompt NO.
boundary conditions that can be experimentally
These were found to be proportional to IN2], the
imposed. There seems no way to distinguish between
quantity of hydrocarbon added (as demonstrated in
the products of reactions (7) and (8), owing to the
Fig. 5), and also to the number of carbon atoms in a
balanced reaction
NH + O H = N+H20
.sz,---.--5 operating. Morley, 5"* opting for reaction (7j, and
413
assuming equilibrium concentrations for oxygen atoms,
obtained a value for k7 of 2.4 x 10-1"~mlmol-ls -1
at ~2400 K, which is of the same order of magnitude
~. 3~ ~ 4 as that obtained from room temperature flash
eg photolysis. 56 Such a small temperature coefficient and
the low collision frequency implied by Morley's data

~ 3 support his choice of reaction (7); i.e. low A H " , but

z 20
spin-forbidden, as mentioned above. However,
• 2 Miyauchi et al.. "~8 probing the reaction zone of rich,
I low pressure methane fhtmes, and subjecting their
10 results to numerical analysis involving 27 reactions
for methane oxidation, and nine for NO Ibrmation,
found an almost quantitative agreement between
I 1 1 predictions and results, although the sole HCN-
5 10 15 forming mechanism included was reaction (8). Finally,
Axial distance from reaction zone (ram) Blauwens el ,I.. "~'*examining [CH] and [CH2] profiles
FI(;. 4. Measured concentrations of NO along the axis of a in low-pressure flames of various hydrocarbons, found
flame [[CH2]/[O2]/[N2] = 3.0/I.0/3.3; temperature=
it impossible to distinguish between reactions (7) and
2350 KI with various amounts of acetylene added : curve 1.
()['~i; 2, 0.987,i; 3. 3.02",, ; 4, 4.43,, ; 5, 6.(18",i. t Reproduced ~8), as [NO] was proportional to both radical con-
with permission from Hayhurst and Vince.4°l ccntrations. Their calculated upper-limit rate constants,
 Prompt nitric o x i d e 41

k . = g × I011 e x p ( - 5 5 6 0 / T ) , Reactions (9a) and (9b) are usually presumed

and
k~ = 2.8 x 10 I - ' e x p ( - l l . 4 O O / T ) m l m o l e - l s
were ahnost equally good at representing tile results.
Clearly. any blend of reactions 17) and (8) would do
no less well, but Benson ~v has argued for a pre-
dominance of reaction (7)over reaction (8).
In all of the above, it has been assumed that the
immediate products of the hydrocarbon--nitrogen
reaction include a cyano radical or molecule, which
is probably HCN, but interconversions are possible,
as discussed in the next section. Eberius et al. "u
found that H C N added to low-pressure flames first
disappeared and then reappeared: they took this
finding as evidence that a distinct nitrogenous inter-
mediate occurs before H C N formation in undoped
tlames. Their reasoning is. however, open to question,
because in the doped flames H C N is subjected to
pyrolysis prior to the reaction zone. There are. of
course, se\eral roundabout routes to HCN, some su
involxing N O itself, e.g.
C H ) + NO ---,CH,~NO --+ C H e N O H ---, H C N + H20.
Even so. it is difficult to conceive of mechanisms
whereby a small hydrocarbon fragment might split a
nitrogen molecule without eventually producing H C N
or CN. The importance of these two species is also
brought out by the fact that all the N O produced in
combustion systems from fuel-N compounds is via
one or other of them as intermediates. 54 Consequently,
after the initial formation of H C N and CN, the
chemistry of the formation of prompt and fuel-NO is
identical.
2.2.4. T h e destruction o / ' H C N
The xarious fates of N a n d / o r N H generated in
reactions 171 and (8) are discussed in the section
below. It is sufficient to note here that H C N and
CN are clearly not obligatory intermediates in the
formation of all prompt NO, since, for example, N,
produced in reaction (71. can yield an equivalent
amount 5~ of N O via reaction (2), the much less
energetic Zel'dovich step. Nevertheless, there are
competing pathways for reaction of NHi species, and
NO destruction is favoured in tile flame zone, so it is
not surprising that H C N has been estimated to
interx ene in the production of ~ 90°0 of prompt NO. 3~
Cvano species do not seem to form N O directly
under flame conditions, although the minor reaction
CN * O , ~ NO + CO has been documented 59 after
roona-temperature flash photolysis. Dechaux and
De Soete "° found tile initial rate of H C N disappearance
to be noticeabl) higher than the initial rate of N O
formation in H C N - d o p e d methane/oxygen/argon
flame,,, suggesting the presence of an intermediate
betu een .HCN and NO. Sexeral workers have suggested
parallel or series roles for the NH~ species, as discussed
in the ,ection belou.
balanced ~ in tile flame :
HCN + H~---'~- CN + Hz
1 ,tl 41 (ga)
II' II,
HCN + OH~--""-"~'CN + HzO (9b)
so that there is an element of indistinguishability about
H C N and CN. Plausible routes for HCN decay may
therefore involve HCN a n d / o r C N : C_,N2 formation
involves termolecular collisions, so is doubtless too
slow to be considered in this context. Haynes et al. s3"~v
found - d ( l n [ H C N ] ) , d t proportional to [ O H ] and
[H], implying either a direct attack on H C N (not via
reactions (9a) and (9b)) by O H or H. or else decay
through C N
Fenimore ~2 opted for attack on HCN m
HCN + H : O --, H N C O ~- H2 (10)
H N C O + H 2 0 ~ NH~ + ( ' 0 2 (11)
having found - d ( l n [ H C N ] I / d t proportional to
[ H 2 0 ] 2 / [ H z ] in a variety of flames doped with
pyridine or NH3. Fenimore's reasoning is not
altogether convincing. Owing to the balanced reaction
OH-rH.,=H + H 2 0 in the flame zone, we have
[ O H ] proportional to
[H203[HI [H23.
or
[H 20]/[H2] 1 2)( [ H I ' [HI ~.qt,
or
([H20]/[H_,] 1.2}.
to a first approximation, for a given region of the
flame, within which the degree of supra-equilibrium
does not vary very much. In other words, [ O H ] z
varies linearly with [HzO]Z/[H2], and little remains to
distinguish Fenimore's mechanism 62 from Morley's 54
with a rate determined by reaction (12);
H C N + O H --, CN + H 2 0 (gb)
C N 4- O H --, O C N + H
OCN+Hi -* CO+NH~ (12)
nothing, that is, except for a factor of [ H 2 0 ] arising
from H 2 0 being on the right-hand side of the balanced
reaction (9b). This ~as not varied much by either
worker, although Fenimore's data 62 lend some support
to his pathway above. In this context, Morley's
comment s4 is pertinent; the H C N disappearance rate
seemed to vary with the first power of [H], but,
because supra-equilibrium radical concentrations lead
to a temperature lower than adiabatic, and hence to a
lower [ H C N ] decay rate, the dependence may well be
of higher order.
On energetic grounds, decay of the cyano pool is
more likely 51 through C N than HCN, even though
the latter is usually more abundant by an order of
magnitude. Thus, even H C N + O ~ O C N + H, with a
rate coefficient 63 of
5.2 x 101-' exp ( - 4 0 9 0 T)ml tool- i s-
42 A.N. HAYHURSTand 1. M. Vlxce
is too slow 5"~ to account for the observed extremely
rapid rates of HCN disappearance. In contrast, the
step
CN + 02 --. OCN + O (13)
has little or no activation energy6. and is favoured by
Mulvihill and Phillips,65 even for a fuel-rich flame.
Their argument is perhaps the most compelling, relying
as it does on few assumptions, and not baulked by
inaccuracies in kinetic data or measurements of trace
concentrations. A premixed hydrogen flame (4) = 2.25,
T = 1500K) was doped with up to 1% C2Nz, and
the products monitored with a quadrupole mass
spectrometer. [CO] was calculated after calibration
in the absence of cyanogen. Approximately equal
amounts of HCN and CO/CO2 mixture were found,
indicating that the main primary reaction 66
H + C2N2 -~ HCN + CN
is followed almost exclusively by reaction (13), rather
than reactions (9); i.e. that CN disappears virtually
before equilibration of the cyano pool has begun.
It seems from the above that temperature is possibly
the main factor in deciding which oxidant will attack
CN; in Mulvihill and Phillips' work, 65 at 1500K it is
02, in Morley's,5. at 2500 K it is OH, while Haynes
et al., 53 working in an intermediate region (~ 1800-
2400 K), found COz the most likely candidate;
CN + CO2 -~ OCN + CO. (14)
However, this reaction was discounted later by
Haynes. 67 The progression (13), (14), (12) is probably
in ascending order of activation energies, but the
effect of temperature on [OH] must not be over-
looked. Finally, Haynes 67 has proposed an alternative
scheme for fuel-rich flames, wherein reaction (12)
prevails above 2300 K, but a parallel step, first-order
in [OH], possibly
HCN + OH ---,HOCN + H,
or some kinetically-equivalent process, is more
important at lower temperatures I1950-2300K).
Recently, Fenimore68 has concluded that the rate of
disappearance of HCN is first order in both HCN
and OH. which adds weight to the idea of OH
attacking HCN or CN.
Haynes 67 and Morley 54 agree on kinetic grounds
that OCN and HOCN must be rapidly removed, i.e.
that the. rate-determining step in the oxidation of
HCN is the formation of cyanate, and not a breaking
of the C - N bond a conclusion in line with the
temperature effect noted above. Possible sequences s4.~'v
are:
OCN + H z = H N C O + H
HNCO+ H~NH2 +CO
or
+11
HOCN-~HNCO _,NH2 +CO
OF
OCN + H ~ N H +CO
leading to species of the type NH~. Overall then. it is
clear that the last word still remains to be said on
the disappearance of HCN.
2.2.5. The role o(NHi species i, the post:/tame ,qases
The NH~ species ti = 0-3) interact in diverse ways
with a flame's NO metabolism. Their fate in the flame
zone, where they usually react quantitatively, also
belongs to a discussion of fuel-NO, as well as of
prompt NO. In the post-flame gases they may react
with hydrocarbon fragments 69'7° to form HCN, e.g.
R + N--,HCN + . . .
CH + NH3 --* HCN + H2 + H
or with an oxidant to form NO in the obligatory
final step in the generation of prompt NO, or with NO
itself, yielding N,. Temperature, stoichiometry, nature
of the fuel, and identity and concentration of the
nitrogenous species all have a bearing on the relative
importance of these roles. Thus, pieces of evidence
obtained by different workers, which at first glance
seem conflicting, may well turn out to be
complementary.
In the absence of hydrocarbons, i.e. in all but the
richest hydrocarbon flames, the post-flame decay of the
NH~ species is quantitatively accounted for by the
production of NO and N,,. This fact is translatable
into the following widely accepted 53.54.62 scheme:
NI + Ox ~ NO + ... (15)
NI' + NO --* N2 + '" ", (16)
where Ox is an oxygen-containing species and NI and
Nl' are nitrogenous intermediates, which by default
consist of one or more of the NHi species. It is
sometimes assumed, TM possibly on insufficient grounds
(but cf. Haynes 72) that NI and NI' are identical. This
need not be so, as the NH~ species are interconvertible
by the (equivalent) reactions
NH~ + IOjH = NH~_ t + H2(O)
whose rates are comparable with those of the ammonia-
depletion pathways, 7~ although indeed a steady state
may not always be achieved (see below). From reactions
115) and (16), we have
d[NO]/dt = k,5[N/] [O.\-] - kz6[Nl'] [NO]. (i)
In rich flames seeded with nitrogenous compounds,
and in very rich, relatively cool, unseeded flames, a
peak for [NO] occurs near the reaction zone, because
[ O H ] ( - [ O x ] , presumably, in these flames) decays
and [NO] builds up. Here d[NO]/dt = 0, and
[NO] ...... = k~5[Nl] [Ox]/I,,6[Nl']. (ii)
Using axial concentration profiles of stable species
and radicals in premixed Ilat flames, eqs (i) and (ii)
have been stretched and strained to imply identities
for N/, N/' and 0 \ , as well as values for k~5 and
k~6, in given systems. Table I summarizes the flame
conditions, assumptions, relevant results and con-
clusions of several investigators.
 lAmi I Summary ofrecenlatlemptstoclarifytheroleoftheNH~speciesinpr°mpt NOfl~rmation

Experm3cntal conditions Stated a s s u m p t i o n s Results Conclusions Authors

[NO],,, increased by added !-t20 or (-'02. NI'= NH2;Ox=OH; Fenimore 62

tt('andothcrfllels;7= 1525 2 1 4 0 K ; [ O H ] = [OHIo. in
burnt gases ; N14; lowered by inerts. NI probably = NH2. though
q~ 1.2 1.93; NIt3 or pyridine added
balanced [NO],, = 7 × 10 ~[O1-t] 2 e x p ( - 5 7 . 0 0 0 ; T ) (151 may not be single-step
al 1300 8700 ppm. Results of olhers
CO-l-dOlled mol ml '
NI N / ' consisls of N ~ NH Kuskan and I l n g h e s ' "
NII3/Oz Ilames: "1 = 2010 K ; q~ - 0.84; N 2 0 . H N O and N2Hi Nlli balanced; | O i l ] < | O H I o , ;
have no impact ; [NO] > [NO]~, and o r Nt12; [ O t t ] depressed
N i l ~, NH, NO, ()H concentrations
certain reaction rates. by very fast reactions:
measnred NIl, ~- OH ~ N H i ~ + H_,O
by analogy
NI = NI' = rain. 6 0 " . N. with | t a y n e s "2
('21-12 or ('211,, fuel; 7 = 1950 2350K ; NHi balanced ; With enough fuel-N.
HC fragments absent [NO],,*,/EOH] ...... = 1.2 + 0.2; [ N I ] varies possible contribution from
~/~ 1.5 or 1.7; NIl3. pyridine or N O
from post-flame gases ; with [ O H ] 3. (Results don't hold for hottest N H / N i l 2 . In hot llames.
added up to 2000 ppm. Radical cones.
H C N not formed in pfg and richest flames.) N O + H ---,N + O H becomes ...#
from measured [H]
important: in very rich flames.
HC fragments in pfg
|no]*=2 3 × [OH]~q O\- = O t t ; h , ~ . k l 6 = 2 3 |Tenimor e-5 =.
( ' , l t , , l l a m e s ; T = 1860 2 2 5 0 K , NI = N I ' ;
~k = 0.9 2.0; four N - c o m p o u n d s added [ O H ] = [OH]¢q, even F.
near flame front o
NI is composite: O x is Haynes el al. 53
Various t i c and other fuels; NI and NI' With sufficient fuel-N, LNO] ---,[ N O ] ....
indistinguishable, i.e. characteristic of flame. [NO],,, varies with probably O H ; k ~ k , 6 is of
T = 1830 2 4 5 0 K ; q S = 1.4 2 . 4 ; u p t o
[NO],. = k,~/kt6[O.x] fuel, T, the order of one in HC flames
5000 ppm pyridine added. Radical cones
from measured [H]
HC flames; three N - c o m p o u n d s added; NHI largely equilibrated Several overall rates and activation energiesNH~ pool disappears mainly De Soete 3s
T = 1800 2 4 0 0 K ; q ~ = 0 . 6 1.5 internally through N
None 2-step disappearance of N O ; Ist with 1 : I {161 probably consists of two D u x b u D and Pratt s
Shock-tube studies ; N H 3 / N O mixtures
very dilute i n A r ; l - = 1450 3250K; disappearance of NH3, 2nd with an induclion tast reactions involving
O t t and NH monitored period = that in t t 2 / N O system NH + NO and N i t , + N O
[ C O ] decay 1st order k,s/kl~ > 0.5; rain. value ifO.\ = O2 NI :~ N; NI probabl,, - NH Seery and Zabielski-'
('O/NII3/O2/Ar flames; T = 1400K;
4, = 0.23 in [ O 2 ] ; NI = N I '
Very fuel-rich combinations of None Estimates of rates of 115) and 116) N / ' - N I t , -115) is possibly Fenimore ~'~
either N H : + I t 2 0 or
N 20 /O2 /N2 /H 2/CH,, with measurements
NIt3 + O t l
of NO. NH~. HCN. CH,~ concs
Note: Flames premixed and laminar, except where stated. Values for k~5 and k,~, have not been included, being in all cases lenlativc. [NO],, refers to steady Icxcl of
[ N O ] far into burned gases: [NO],* = transient peak near llame zone. at lime t,,,. Subscript "eq" denotes the xalue of a quanlit~ for equilibrium in the burned gases.
44 A.N. HAYHL:RSTand [. M. V]NCE
A glance at the table should show the near-
impossibility of generalizing meaningfully about the
post-flame role of the NH~ species; an exhaustive
evaluation is in any case beyond the scope of this
work, although for our purposes weight should be
attached to Refs 8, 53 and 72. A few truisms may be
attempted, however:
(1) Reaction (16) is the only one which effectively
depletes the pool of nitrogenous pollutants.
(2) Altering the balance between reactions (15) and
(16) may be the simplest way of controlling prompt
NO (and perhaps also fuel-NO) without compromising
measures against thermal NO.
(3) The overall rate constants k~5 and k~6 are of
the same order of magnitude over a wide range of
flame conditions.
(4) Internal equilibration of the NH~ systems is rapid
by flame-chemistry standards (see Kaskan and Hughes'
conclusions in Table 1, and also note the transient
effect on [OH] in propane flames with N-additive,
noted by Puechberty and CottereauV¢). In hot flames,
however, where [OH] is very high and the Zel'dovich
mechanism becomes important, depletion of N atoms
can be too fast for equilibration,v-"
(5) Each of reactions (I 5) and (16) may involve more
than one of the NH~: thus, full equilibration may not
be crucial. The NH; system may itself act in parallel
with the HCN-NH~ pathway, as shown semi-
quantitatively by De Soete, 3s since in generating a
molecule of HC N an N atom is released, by reaction 17).
2.2.6. Prompt NO in very rich .flames
For each CH-N_, reaction, up to two molecules of
NO are presumed to be formed: one via HCN, the
other in the ZeFdovich fast reactions (2) and/or (3).
The relaxation time for the latter under conditions
in the flame is not more than a few tens of micro-
seconds, but prompt NO formation is sometimes
incomplete after a period of several milliseconds, as
Hayhurst and McLean s~ have noted. As described
above, HCN and NH3 have been detected far into
the post-llame region of hydrocarbon flames, in con-
centrations above those for focal equilibrium and
PYROLYSIS OR pRE-HEATING l
ZONE
RH * H~ ~ ~ CHi * "'"
CH i * N2 ~
I"IG. 6. , ~ u n l n l a r y o f t h e m e c h a n i s m
from left to right. The fuel is a hydrocarbon R t l
abov.e the measured [NO]. Figure 6 then. is the
most plausible scenario for prompt NO tbrmation in
a moderately rich flame of say 4' = 1.5. Sho~n there
are pyrolysis reactions giving CH or CH= upstream of
the reaction zone. with subsequent steps leading to NO.
From data obtained by' Hayhurst and Vince, s= it is
clear that the prompt mechanism in ~erv rich flames
is not completely as portrayed above. The x measured *°
the yield of prompt NO generated b~ controlled
amounts of a hydrocarbon added to a variet~ of
premixed flames of H_,, O z and Nz. as alreadx described
in Fig. 4. In very rich flames t~h > 2.5) the x found:
(1) Concentrations of prompt NO exceeding those
for equilibrium by up to a factor of 20.
(2) When the amount of added hydrocarbon ex-
ceeded 18~ by volume, the total measured concentration
of NO rose in the region of the reaction zone to a
maximum, followed by a sharp drop. Although NO
was accordingly disappearing from the burned gases,
it was possible to estimate the total prompt NO
produced, by extrapolation back to the reaction zone.
(3) The quantity of prompt NO produced in a flame
was not only proportional to [N_,], but also to the
amount of hydrocarbon added, provided this latter
was less than 1%, as noted above in Fig. 5. Larger
concentrations restflted in a maximum, and subsequent
decline in prompt NO levels, as shown in Fig. 7. In
spite of these diminished prompt NO yields, e.g. for
hydrocarbon additions of about 3",,, [NO] in fact
remained above its equilibrium value.
(4) As seen in Fig. 7. the maximum prompt [NO]
declined with increasing 4),
(5) It was noted above that the yield of prompt NO
was found "*° to be linear in the number of carbon
atoms in a molecule of the hydrocarbon. Although
this still held in these very fuel-rich flames, the lines
no longer passed through the origin and the slope
became smaller as 4~ was increased. These trends are
shown in Fig. 8, for both low and high C'.
If these rich-flame anomalies amounted merely to a
slowed increase of prompt [NO] with increasing 0
and C-content, one could try to rationalize them in
terms of Fig. 6. In this case, because o1 a dearth of
I
REACTION ZONE BURNEO GASES
I
I
I
HCN * NHi_ 1
I NHi_I , H ~ NHI-z* H 2
I N * O H I O 2 "-~" NO * HIO
I (H)CN * OH - - " " NCO ~ NHi • CO
I
NHi, OH~NO, ...
I
=" INCREASING RESIOENCE TIME
for producing prompt NO in a p r e m i x e d Ilanl¢ ~itll gas I l o w i l l g
 Prompt nitric oxide
10 ~=25
,z, a
_m
•,~ 6 --
,z,
g
o I
0 1 2 3
°/o C2H 2 IN BURNT GASES
FIG. 7. Prompt nitric oxide concentrations (all normalized
on IN2] = 70'!o by volume) as a function of the amount of
C:H2 added to three very rich flames of H2 + O2 + N2,
all at 1900K. The equivalence ratios of the parent Ha
flames are as shown.
oxidant radicals, H C N a n d / o r NH3 would survive in
appreciable concentrations, and normalized
[n]~.o~,,,~ = [ N O ] + [ H C N ] + [nI-13]
should still vary linearly with the concentration of
hydrocarbon additive. That it is far from doing so, is
obvious from (2) and 13J above, since destruction of
NO, or an intermediate in N O formation, is taking
place in flames with more than ~ 1.500 by volume of
hydrocarbon added. Since the observations are such
that the bulk of this destruction must have occurred
within or close to the reaction zone, CH~ as well as
NH~ may be responsible. Possible reactions, with
reasonably low activation energies, include:
CH + N O --+ H C O + N
CH + NO---, H C N + O
N + H C N ---, N2 + CH
H C N + N O --+ N2 + H C O
NH + N O ~ N2 + OH
NH2 + N O --+ N , + H_,O
N + NO~N2 +O
NH~ + CH ~ H C N + H~
NH~ + NH~ ~ N_~ + H/H2.
It is not sinapl3 because kinetic data for some of these
reactions are lacking or uncertain that the choice is
bewildering: the main reason for diffidence is that
there is so little information available on the behaviour
of hydrocarbons in flames as rich as these--under-
standably, since if they were fuelled solely by hydro-
carbon, the sooting limit would long since have been
pas.,,ed.
45
~} = I 5, 1900 R
~tj
~ go
J ~
(3
Z 5, 1900 K i
3 O, }900 K
1 55, 2 350 R
2.
~ 5
E
Q.
I
I[
t
2
C ATOMS PER HYDROCARBON MOLECULE
FIG. 8. The measured variation of the yield of prompt NO
(after correction for any changes in [N2] and [hydro-
carbon]l with the number of carbon atoms in one molecule
of the hydrocarbon, added to a series of flames with
equivalence ratios, (p, and temperatures, as shown.
Myerson 76 has actually succeeded in destroying the
major portion of exhaust-NO (up to 90°0) in a flowing
system of simulated combustion effluents by injecting
a mixture of hydrocarbon and oxygen in carefully
controlled amounts. The most critical parameter was
the hydrocarbon : 0 2 ratio. If q~ of the oxidant stream
was a little over 2.0, [ N O ] was minimized without
appreciable H C N appearing. The hydrocarbon : initial
N O ratio was also important, for, as this ratio was
increased beyond an optimum around unity, H C N
replaced N O in the exhaust. Myerson suggested 76
(17)
(and no one has disagreed) that the 02 provides
reducing radicals such as CH, which then directly
reduce N O through steps such as reaction (17),
followed by reactions (18)-(20). The global reaction is
of the form
(18)
6 N O + 4CH ~ 4 C O + 2 H 2 0 + 3N>
(191
Again, Yamagishi et al. ~7 were able to plot a monotonic
(20)
decline in total combined nitrogen
( [ N O ] + [ H C N ] + [NH3]I
from 50 ppm at ~b = 1.4, to 8 ppm at (a = 2.0: [ H C N ]
had peaked at 4~ = 1.7. The evidence in this paragraph
shows the possibility of eliminating N O without
engendering H C N etc., and the way CH~ may bring
this about.
Iverach et a l } ' have outlined a situation wherein
[ N O ] may briefly exceed [NO]m,x as defined in eq. (ii),
viz. in or near the reaction zone of rich, relatively cool
46 A.N.H.~,YHt_Rsr and 1. M. Vzx(E
hydrocarbon flames, where [NH/] is very large and
[Ox] ( - [ O H ] ) is supra-equilibrium. In the post-flame
gases, however, [NO] drops back to [NO] .... this
decline being perpetrated solely through the NH~
pool. It seems improbable, however, that the observa-
tions catalogued above, especially (3), can be
interpreted without recourse to other reductants in
addition to the NH~ system. For one thing, HCN in
concentrations above that of NO has been shown ~
to survive far into the post-flame region of premixed
hydrocarbon flames of ~b = 1.5. The requisite high
[NH~] and supra-equilibrium [OH] are thus already
present at this equivalence ratio. Yet here, at 4' = 1.5
(and even 2.0), none of this axial decline, etc., was
observed by Hayhurst and Vince. ~2 Secondly, [NO]
is supposed to fall to [NO] .... in the post-flame
gases, a value that, under isothermal conditions, should
vary linearly with [OH], but be independent of any
other variable, if we assume that NI and NI' are
either equivalent or balanced (see above). Now, our
observations 5z resist such a description, because the
drop in [NO] is found to be very sudden--virtually
over within the reaction zone itself--and is a large
one. These are facts inconsistent with any reasonable
axial [OH] profile in similar H2 or C2H2 flames, s5
Again, although [OH]~q falls by 14'.~'o, and
[OH]/[OH]¢q is also presumably lowered, in going
f r o m 2'~ o t o 3,! 0 C 2 H 2 substitution in a hydrogefl flame
of q~ = 2.5, the corresponding fall in prompt [NO] is
over 8031, as shown in Fig. 7.
In addition to Iverach et al.'s scheme, '~ which
probably accounts for our observations of the post-
flame-front decay of [NO], it is necessary to postulate
another sink for NO in the flame. The most likely
candidate is Myerson's,76 involving reactions {17) and
(20), i.e. :
NO
CH + N O + H C O + N ,N2 + O
although similar contributions from CHz and CHs
cannot be ruled out. It appears, then, that while CH
disappears very early within the reaction zone in lean
and moderately rich flames before appreciable NO
formation through HCN {or cognate N) has taken
place, in extremely rich flames CH manages to survive
long enough to attack NO. The reactionts) of CH~
with NO must be a good deal faster than the activation
energy of 84 kJ tool ~ suggested by Myerson v6 would
allow, even accepting a value for the pre-exponential
factor of an order of magnitt, de higher than that
estimated for reactions {71 or {81 by Blauwens et al. ~
Experiments with fuel-N have lent independent
support s-' to the argument that CH~ + NO --,products
must be very fast at 1900 K.
No doubt CHi NHi reactions also abound, yielding
HCN, and thus not merely retarding, but derailing
prompt NO production, since NH~ is here acting as
yet another competitor against molecular nitrogen for
available CHi. Again, the probability of two NH~
radicals colliding to form N2 is enhanced when OH
is scarce. Halstead et al. TM found a surprisingly high
rate coellicient for CN + NO--, CO + N,, equal to
5 x l 0 1 ~ m l m o l - ~ s -~ at 2000K. Whether HCN
might thus react with NO in extremely' rich flames is
uncertain, but Haynes 6" found no evidence for such a
reaction at 4) = 1.66. De Soete. 38 from measurements
of overall reaction rates in a hydrocarbon flame with a
nitrogenous additive, suggests a rate constant for
HCN + NO ---,N., + HCO
of 3 x 101-' exp ( - 30.000 Tlml mol -* s 1.
3. THE POLLUTION SIGNIFICANCE OF PROMPT NO
One important finding of Hayhurst and Vince*°-~-'
is that the amount of prompt NO produced in a
premixed flame per N_, molecule and per C atom m
the burner supplies is virtually independent of flame
temperature (at least in the interval 1900-2350K.
and probably up to 2500K as well) and also of
stoichiometry, for q5 around 1.25-2.0. In lean flames.
however, prompt NO levels fall abruptly when q5
decreases below unity. In contrast, thermal NO
formation is highly dependent on temperature
(activation energy = 316 kJ mol- ~) and on residence
time at high 7", and dwindles in fuel-rich flames.
Also, it is not supposed to respond directly to vari-
ations in fuel type. Finally, fuel-NO production has
an effective activation energy which seems to be about
an order of magnitude below 3s that of thermal NO,
while the yield Y {ratio of NO finally emitted to fuel-N
fed to flame) is governed primarily by stoichiometry
and fuel-N content. In lean flames containing ,~ I °o N,
Y is frequently 1 0 0 " , . Fuel type can be relevant, with
some stable nitrogenous compounds requiring the
presence of a hydrocarbon for conversion to take
place, but for most fuel-N, including amines and CN
species, this does not strictly apply.
From the foregoing, it is obvious that prompt NO
will contribute most m cooler hydrocarbon flames of
so-called "'clean" fuels, and less in flames that are very
hot. very lean, contain substantial fuel-N, or are
partially fuelled by H2..CO. Much has been made in
the past of the fact that prompt [NO] peaks at fuel-
rich equivalence ratios, but the standpoint that it can
therefore be ignored in most practical applications is
challenged by three facts:
(I) Lean flames do produce some prompt NO.
Fenimore,-'° and others, 3"''~'~''~s have observed this.
Moreover, his intercept-NO increased markedly with
pressure, particularly in lean flames, so that at 3bar
prompt [NO] was about the same at q5 = 0.8 and
q5 = 1.4. Also, Hayhurst and Vince5-" found at 1900K
that the yield of prompt NO per hydrocarbon molecule
in the burner supplies wits near its peak value at
q5 = 0.88. Furthermore, there was a strong tendency
for this peak to shift towards the fuel-lean with
"decreasing temperature.
(2) Premixed flames, the vehicle for most research
to date on prompt NO, are seldom encountered outside
laboratories. Overall stoichiometry is irrelevant in the
rcaction zone of dilrusion Ilames, with or without
turbulence. As is well known, this zone is regularly
 Prompt nitric oxide 47

TABLE2. Prompt NO predicted in the exhaust of various overall-stoichiometric

flames burned in air

Prompt NO concentration
Fuel ppm as kg NOz/tonne ft,el as kg NO2/10 5 MJ

CH4 47 1.5 2.7

C2H¢, 55 1.6 3.1
C3H8 59 1.7 3.3
U.K. motor spirit 65-74 1.7 1.8 4.0 4.2
[C/H = 0.47-0.641
CzH4 67 1.8 2.9
CzH2 85 1.9 3.5
C6H6 85 1.9 4.6
CH 3OH 53 0.68 3.4

slightly fuel-rich. In a turbulent diffusion flame,
modelling is always precarious, so it is often a moot
point as to how much observed NO:, the Zel'dovich
mechanism explains. Nevertheless, clear-cut results are
not impossible to obtain: e.g. Vince 19 probed a
turbulent diffusion propane-air flame of overall
~b = 0.84, finding up to 12ppm NO, although the time-
averaged temperature (measured with a thermocouple)
was around 1250 K. A practical flame can, indeed, be
viewed as a slightly rich reaction zone promoting
prompt N O formation, surrounded by a fuel-lean
region, which protects the N O from destruction by
NH~; cf. the behaviour of fuel-NO yield with varying
stoichiometry.
(3) It is misleading to compare emissions for different
stoichiometries in ppm, as is often done in the case of
NOx, though for no other major pollutant nowadays.
The basis should surely be kg N O x / t o n n e of fuel
burned. Due simply to air dilution, all hydrocarbons
must yield an exhaust 70-80% more concentrated
in N O when burned at ~b = 1.4 rather than ~b = 0.7,
for the same N O output/weight of fuel.
Hayhurst and Vince 52 were able to develop a rule
of thumb to predict the amount of prompt N O
produced in a premixed flame. The rute gives the
concentration of prompt N O per unit concentration
of N2 and per unit concentration of carbon atoms
(added as hydrocarbon) in the burnt gases, as roughly
110 mol m l - 1 / ( m o l m1-1 N2) • (mol m1-1 C-atomst
when reduced to s.t.p, l l a t m . and 0°C). This corres-
ponds to prompt N O levels of about 5ppm for a
flame whose burnt gases contain 70"0 by volume of
N2 and 1',,, of carbon atoms originally present as
hydrocarbon. It is now a matter of straightforward
arithmetic to construct Table 2 for atmospheric-
pressure flames burned at an overall q~ = 1.0. The
final column in Table 2 was derived using calorific
values from Rose and Cooper. ~9 Also, this column
contains data for methanol. It is more than doubtful
that methanol would behave as a hydrocarbon in
producing prompt NO, since the C atom is already
linked to an oxygen one. Even so, it appears that
fairly high emissions of prompt N O are possible.
Neglecting any possible temperature dependence of
prompt N O formation and that it strictly holds for
premixed flames only, Table 2 can be further developed,
in making estimates of the prompt contribution as a
percentage of the total NO., emission measured from
various practical sources. The average emission data
in Table 3 are as quoted by Perkins. s° In constructing
Table 3, the natural gas in the first three rows was
assumed to be pure methane. The contribution from
prompt N O in gas engines and turbines of course
depends on the gas composition, so that the final
figures should be lowered if the fuel contains H2 or
CO. No allowance was made for the effects of pressure
on the entries for the last three rows: pressure effects
have been investigated by Fenimore. 2° Data for
residual fuel oil, coal and waste disposal are available.
However, it seems naive on the basis of the present
study to try to predict prompt N O levels in any but
homogeneous flames. It may fairly be conjectured,
nevertheless, that, since these last-named substances

TABLE 3. Emission factors for nitrogen oxides : the role of prompt NO

° o estimated due
Source Average emission factor (as NO:) to prompt NO

Natural gas :
household and
commercial 116 lb/million ft 3 gas burned 57
industry 214 Ib/million ft 3 gas burned 31
utility 390 lb/million ft 3 gas burned 17
Gas engines 770- 7300 lb/million ft 3 gas burned 2- 21
Gas turbines 200 lb/million ft 3 gas burned 30
Gasoline-powered
motor vehicle 113 lb 1000 gal. fuel 10
Diesel engine 222 lb: 1000gal. fuel 5
48 A.X. HAYHURSTand I. M. Xlx(E
are as a rule strongly contaminated with combined
nitrogen, the prompt mechanism is likely to be over-
shadowed. If, say Y = 50 o for a fuel containing 1 ",, N
by weight, then fuel-NO will account for 16.5 kg/tonne.
and prompt NO is certainly going to be <5'~o. In
this context, there is a piece of circumstantial evidence 8
that, in a fluidized-bed combustor, NO levels were
found to be unaltered when nitrogen in the com-
bustion air was replaced by argon.
A striking feature of Table 3 is the entry under gas
turbines. Through a quite different experimental and
calculation procedure, a similar estimate for a relative
contribution of prompt NO was obtained by
Fenimore. 2° Equally encouraging is the fact that, in
eight of the eleven hydrocarbon flames tested by
Bachmaier et al.ff intercept [NO] at q~ = 1.0 increased
with increasing C/H of the fuel@ust as in Table 2.
For the most part, absolute values recorded here are
within the error limits of Bachmaier et al. 4 All of this
agreement provides confirmation of the above rule of
thumb. Although its approximate nature should not
be forgotten, it does seem likely from Table 3 that
prompt NO constitutes a large minority of the total
NO in a variety of practical flames, and should be
borne in mind when designing modifications for
abatement.
4. PRACTICAL MEANS OF C O N T R O l . L I N G N O .
No serious attempt will be made here to provide
an exhaustive literature survey, but the most promising
approaches to the problem will be mentioned briefly,
in order that their relevance to and effects on prompt
NO can be estimated. In general, NOx emissions have
been combated by preventing their formation, by
destroying them in the post-flame gases or afterburners,
as well as by catalytic removal from the exhaust.
Owing to the insolubility of NO and the slowness of its
conversion to the more soluble NO,, gas washing has
not been a subject for research, although NO, emissions
are reduced s° by about 20",, in the course of SO_,
removal. Removal of nitrogenous material from the
fuel is, as a rule, financially prohibitive, except in the
case of natural gases containing commercially recover-
able quantities of ammonia.
To date, combustion modifications for NOx control
have almost always been designed with thermal NO in
mind. The rate-determining step
O + N2--*NO+ N
can be retarded by reducing one of three quantities:
peak temperature, residence time at or near peak
temperature, and O-atom concentralion. It is beyond
the scope of this section to comment on the fact that
the above sounds like a recipe for maximizing hydro-
carbon and CO emissions, but the encouraging con-
clusions ofTuttle et al. x2 are worthy of note.
L o w excess-air combustion, first applied in oil-fired
power station boilers as a means of combating SO3
corrosion and emissions, is capable of cutting the
output of NO~ by O-atom starvation, provided thai
heat transfer is maintained adequate to prexent
increased flame temperatures. Reduction~ of up to 30~'o
are possible m some boilersY 3 Brox~n et al, s~ con-
sidered low excess-air combustion more effective in
reducing fuel-NO, especialb at high fuel-N levels.
than thermal NO. Prompt NO formation is likeb to
be promoted by any shift to the fuel rich. but ~ill m~t
peak as long as any excess air is present.
Two-sta~le combustion, in which sub-stoichiometric
air is injected at the burner, and heat is removed
before the remainder of the combustion air is admitted.
is capable of somewhat larger reductions. The first
stage commonly entails -95",, of stoichiometric air.
but Turner and Siegmund ~' ha~e reported emissions
reduced to about half when lirst-stage air was 70",
(15"0 excess air overall). The stratified-charge internal
combustion engine is being de~eloped primarily
because of the incentive to suppress NO~. The expected
reductions have not been realized, at least not without
incurring heavy penalties in elficiency. "~ Opponents
of charge stratification point out that if fuel-rich and
fuel-lean regions exist side by side, a third (albeit less
extensive) region must also exist, i.e. stoichiometric.
and this must be the chief source of NO in these
systems. However, Tabaczynski and Klomp 8° have
shown analytically that. even with a stoichiometric
region containing 20". of the fuel, significant NO
reductions should be possible, especially in the low-to-
medium load range. Turner and Siegmund s5 have
found fuel-NO to be diminished as much as thermal
NO by staging. Nevertheless. prompt NO is likely to
be increased by up to an order of magnitude, accord-
ing to the arguments set out abo,,e in Section 2.2. For
although the choice
+NO/N2 + ...
NH/
/
+O~~x NO+...
will, with increasing 4~, be steered away from the
oxidative pathway (thus decreasing Y, the yield of
fuel-NO), this is overshadowed in the case of prompt
NO by the absolute reqtdremcnt for appreciable levels
of hydrocarbon radicals if NH; are to accumulate in
the first place. The effect of staging on HCN and NH 3
emissions should not be overlooked. Yamagishi et al. 77
(I)
found both NO., and total nitrogenot,s emissions to
decrease steadily with increasing (/5 in the primary
stage, but HCN levels peaked at q5 = 1.7. Similarly,
Martin and Dederick '~v obtained a minimum }" when
the primary Ilame was at (/5 = 1.2, but concluded
thai most of their fueI-N (NH ~1 was passing through
t h e Ilame tlnreacted.
Cooled e.vhaust-~laS recircuhttion (E(IR) reduces peak
Ilame temperature and oxygen partial pressure in the
initial part of the Ilame. as well as casting flame-
generated NO, in the role of fueI-N, which, if Y < 1,
leads to a "'geometric" decline m NO, emission. Not
 Prompt nitric oxide 49

surprisingly, therefore, thcre is synergism between Thc potential savings in development cost and time
flue-gas recirculation and two-stage or low excess-air arc enormous, A broad experimental programme to
combustion, making NO., reductions of 90,,, feasible assess the feasibility of such an approach in aircraft
with present technology.~ Curiously, EGR has been gas turbines was undertaken by Shaw, 89 who tested
found s~ not to affect fuel-NO, even at recirculation approximately 70 fuel additives in Jet A fuel, falling
ratios high enough to eliminate thermal NO; tile into six categories:
effects on prompt NO are thus probably also minimal.
(I) Soluble organo-metallics which become hetero-
Water il!iection has been estimated s~ to afford the
geneous catalysts.
least reduction (~ 10%1 for the highest cost/tonne (2) Oxygen atom scavengers or recombination
NO., of conventional combustion modifications in a
catalysts.
1000 MW boiler, although the technique shows promise
131 Additives to reduce peak temperatures.
in spark-ignition engines. Shaw ~9 found some multi-
(4) Additives to delay ignition.
component H,O emulsions reduced NO~ from gas
(5! Additives (e.g. dissolved polymers) to change
turbines, while others merely increased the NOz,/NO.,
spray fluid dynamics.
ratio. Although the usefulness of water injection in
16) Additives to decompose NO or to inhibit the
NO, abatement in a given appliance is thus hard to
NO producing chain reactions, e.g. aniline (!1.
predict, it seems certain that its effects on the prompt
!7~ Synergism among the above categories was
mechanism are negligible, since water addition acts also briefly investigated.
merely be reducing the temperature in the NO
formation zone. '~° Similarly, reducinfl air preheat or Category (It allowed up to 30", reduction at an
combustion imensitv, admittedly effective against addition rate of 2.5 % by volume : other additives, some
thermal NO, cannot be expected to influence prompt not containing metals, reduced NO, by up to 15°o.
NO much. Synergism was found between antimony triphenyl and
The cooled porous disc burner is another purely carbon tetrachloride, a combination known to be
thermal device. 9~ shown to reduce thermal NOx by a effective in reducing the flammability of plastics. In a
factor of ten without affecting prompt NO. related study, devoted solely to category (1), Altwicker
Through rery./uel-leuJ1 (down to q) = 0.451 premixed, and Shen ~7 found Mn compounds to be the most
recircutatory combustion, Schefer and Sawyer 3° have effective of all. with 10o by volume reducing stack
achieved low NO~ emissions without compromising NOx by 20°°. No doubt compounds in category (1)
combustion efficiency : a drawback of their approach is do not discriminate among prompt, fuel-, and thermal
the high proportion of NO_, in the NO,, of around NO, since their target is the NO molecule itself.
50-10Wo, depending on the temperature. Even leaner This applies also to many heterogeneous catalysts in
flames, at flow velocities so high that normal flame the exhaust system, such as Cr=O3 (Refs 98 and 99), or
stabilization would have been impossible, have been SnOz/Cr203 and AI203/Cr203 (Ref. I00), or even
described by Hilliard and Weinberg;9= the flames quartz (Ref. 101). Such catalysts are at present mostly
were anchored to the wake of a small plasma jet, expensive, not very efficient and soon poisoned.
whose energy requirement was 4°0 of the chemical However, one notable exception, now commonly used
throughput. Considerable reduction of NO emission in the U.S.A., are the Pt/Rh catalysts, ~°= enriched to
was demonstrated with a car battery operated plasma up to around 2000 of Rh. Apparently, small amounts
jet tested in the exhaust system of a saloon car. It is of these catalysts can reduce [NO] by 93°,0, and
obvious from the above discussion that very lean unburnt hydrocarbons by 96°0. In addition, they are
flames must generate nearly zero prompt NO. relatively cheap, in that only small amounts are
There is an exceptional abundance of data concern- required and last for long periods. ~°2 As to the other
ing tile effects of raryi~Lq burner parameters on NO.~ categories, (2) and (3! probably leave prompt NO un-
emissions, although a search of the literature has failed changed, but {4)-(6) are worth investigating further,
to turn up any study on prompt NO in this regard. particularly as they do not cause metal pollution,
Heap et al.. ~~ for example, reported a four-fold although Shaw s9 found NO~ to increase with the
variation in NO from natural gas and PF flames addition of any nitrogenous compounds.
~hen xarying several factors, such as the method of Gas-phase decomposition of NO in the combustion
fuel injection, swirl and velocity of the combustion products was first described by Lyon a03. Muzio et al. ~o,~
air. type and angle of the burner quarl, the amount of achieved 80°0 reduction by the addition of NH3 (1 : 1
primary air. and type and position of the fuel injector. for initial NOt in the presence of 2°'0 excess air.
Comparable findings emerged from the work of Sakai Temperature was crucial ; below 1150 K the destruction
et al. ~'~ on the internal combustion engine, Bartok of NO was too slow, while above 1250K the NH3
et ,l. s~ on utility boilers, and Jones 95 on jet aircraft. reacted preferentially with oxygen. Attempts by these
kefebxre ~ offers a comprehensive review of advanced workers to u~e hydrocarbons in place of NH3 failed,
cornbustor concepts. At present, the likely effect of unless the addition rate was such as to render the
most alterations of burner parameters on prompt NO mixture fuel-rich. In contrast, Myerson ~6 has furnished
can only be guessed at. detailed instructions for reducing NO by the addition
The possibility of mod!tSin~l the luel to reduce NO., of hydrocarbon plus oxygen (!t to the post-flame gases,
emis,,~on~ ha> not attracted the attention it deserves. at 1200-1700K. Up to 90°o of the total nitrogenous
50 A.N. HAYHURST and I. M. VJxcrE
emissions were removable from car exhaust products,
with only a small fuel penalty of no more than 7°0.
Fluidized combustion of coal generates virtually no
thermal NO~,, despite long residence times, since
temperatures are far too low. Thus emission levels
may meet existing standards by a considerable margin.
That the residual source of NO:, is fuel-N, rather than
from the p r o m p t mechanism, is proved s~ by tests which
showed no change in [NOx] when N2 in the com-
bustion air was replaced by argon. Calcium sulphate
catalyses ~°5 the reduction of N O by CO, as does
increased pressure in some cases.t°6
Acknowledgement--I.M.V. thanks Sheffield University for
the award ofa Styring Scholarship.
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