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OVERALL REACTION RATES OF NO AND N~ FORMATION

FROM FUEL NITROGEN

G. G. DE SOETE
Laboratory of Aerothermics, lnstitut Fran~ais du P~trole, Rueil-1~[almaison, France

From measurements c~rrled out on fiat premixed hydrocarbon/oxygen argon (or helium)
flames, into which small amount~ of ammonia, or cyanogen are added, overall reaction rates
of formation of NO and N~ are determined. From similar measurements effected on nitrogen-
diluted ethylene/oxygen flames, an overall rate of prompt NO formation is obtained.
The discussion of these rate constants indicates that the relative importance of HCN mole-
cules as intermediates in the fuel NO mechanism increases according to the following sequence
of primary fuel nitrogen compounds: ammonia, cyanogen and molecular nitrogen; this last is
found to behave like a true fuel nit.rogen compound in the early flame stages.
Experimental values of the total yield of nitric oxide obtained from the added nitrogen com-
pounds have been determined; they are found to be in good agreement with yields calmllated
by nunLerical integration ef the empirical overall reaction rates of NO and N2 formation,
showing almost tim same dependence of the -NO yield on temperature, initial fuel nitrogen
concentration and oxygen concentration.

Introduction primary fuel nitrogen compound. Consequently

in the early flame stages, even the :N2 molecule
In the last years, it has been accepted as a good can behave like a fuel nitrogen compound.
assumption that the general schcme of the fuel Rcpmsentlng the primary nitrogen compound
NO mechanism includes (a) a total or partial by AZ and the intermediate nitrogen compounds
transformation of the primary fuel nitrogen by the symbol XN, the overall mechanism can be
compound into a series of secondary, intermediate presented as follows:
nitrogen compounds (HCN, CN, NH:, NH, N)
which (b) are subjected to a double competitive
reaction path, one consisting in their transforma- 4-OX
NO
tion into NO by the attack of an oxygen-con-
AZ ~ XN~ "
taining species OX, the other leading to N2 /

formation by the attack of a nitrogen-containing
substance, mainly NO itself. L2'~
Substantial support of this hypothesis has been
folmd in the experimental data on the dependence
of NO yields on fuel nitrogen and oxygen con-
tents of the gases and also in the particular shape
of the concentration profiles of some of these
intermediates (e.g., IICN 4) in the flame front.
The distinction between a special fuel NO
mechanism and the so called thermal mechanism
must be based on the possibility of some of these
intermediates being formed (their formation re-
quiring the presence of some unstable species, the
existence of which is practically restricted to the
early flame stages) and also, to a lesser extent, on
t]m bond energy of the nitrogen atom in the
1093
N~
+NO
One may distinguish between successive and
parallel intermediates; cventtmlly there may also
exist one or more indispensable intermediates,
through thc formation of which the overall trans-
formation of the primary fuel nitrogen compound
must necessarily pass. The primary nitrogen
compound may also be transformed to some
extent directly into NO and N2, and in this case
it must be considered as a parallel intermediate.
If XN~ is one of the successive intermediates,
the succession of which constitutes the ith parallel
branch of the overall reaction path, one can ex-
press the formation rate Vn of XN/and the rates
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1094 COMBUSTION SYSTEMS
of its transformation into NO (V~i) or into N,,
(V~i) as follows:
V~,.= k ~ X a z " X r m ~ (1)
~ = b~Xx.~ ~ X e , ~" (2)
V3~= k~Xx~ ~ X ~ o ~' (3)
XAz, X~a, etc., indicate the mole fraction of tim
primary fuel nitrogen compound, respectively of
the fuel, etc.; the reaction order f with t~espect to
the fuel is fmzaal]y introduced in order to account
for the fact that some fuel derived substances
(like C~ or CH) play a role in the formation of the
intermediate.
The overall formation rate of NO and N~ from
fuel nitrogen may bc expressed either by the sum
EW_% respectively ZWu, or as a function of the
primary Iucl nitrogen comI)ound :
Va = kaXaz~Xo~ b (overall formation rate of NO)
(4)
I%=kBXAzr 't (overall formation r#ce of N~)
(5)
Comparison of empirical values of Ira and Vn
with experimentally determined expressions of
I,~ and Va~, m~y be helpful in discussing the
relative importance of parallel intermediate nitro-
gen compounds in the formation of NO and Ne
from fnel nitrogen.
Taking into account both the fuel NO mecha-
nism and the thermal mechanism, the overall
variation of NO as a function of time is given by:
dXxo/dt= VA-- "V~-t- "Vc-- I'~ (6)
where Vc and VD are, respectively, the mean
reaction rates of formation and decomposition of
NO by some thermal mechanism, c.g., the
Zeldovich mechanism. Similarly, the overall
variation of N2 as a flmction of time is glvcn by:
dXN~/dt = -- VA-~ Vn-- Ve-~- VD (7)
If there is no molecular nitrogen in the flammable
mixture, the term Vc in Eqs. (6) and (7) may be
neglected.
In what follows, the determination of rate
constants for ~ , VB, Vn', V2;, and V~i is described
from experimental data obtained with fiat pre-
mixed flames. B a ~ d on these rate constants the
relative importance of the particular inter-
mediates HCN and N is discussed for different
kinds of fuel nitrogen compounds.
Experimental
1. Method
Flat premixcd ethylene/oxygen flames, diluted
with either argon, helium or nitrogen, are stabi-
lized on a water cooled burner of sintered bronze.
In the case of argon or helium diluted flames,
small ammmts of nitrogen compounds (C~N2,
NIL or NO) are added. Samples are withdrawn
at the symmetry axis of the flame as a function of
the distance z from the burner, by a water cooled,
stainless steel probe, and ~re analyzed for 0~,
hydrocarbons, II2, CO and C02 by gas chroma-
tography and for NO and NO2 by a chemi-
luminescent analyzer. Cyanogen and hydrocyanic
acid in the flame gases are determined by ohcmlcal
methods after successive absorption in a slightly
acid AgN03 solution and a NaOH solution. A de-
tailed description of the experimental method has
been given in previous publications.2'5
Temperature profiles are determined as a
function of x by the sodium line reversal method.
Variations of the flame temperature of th.c order
of 400~ with no significant change in the pro-
files of the main combustion products, could be
achieved by changing the degree of m:liabaticity
of the flame by vaxying the totalflow ra~ethrough
the burner. Flame temperatures were varied
between 1800 ~ and 2400~ equivalence ratios
were varied from 0.6 to 1.5.
2. Determination of Rate Constants
Using the concentration profiles, especially
those of NO, IICN, and C~N~, corrected for
diffusion effects, and the temperature profiles,
the overall reaction rates are determined as
indicated below.
A. Addition qf cyanog~t tn ethylene/azy~en/
argon Jh~mes. T~)ica[ profiles of NO, HCN, C~N2
and temperature are shown in Fig. 1 for a near
stoichiometric mixture at two different tempera-
ture distributions.
In order to find the relative importance of HCN
as an intermediate, the overMl reaction of NO
and N2 formation may be split into two parallel
paths, the first passing through HCN formation
as an intermediate, the second--lf it exists--
eventually going through the formation of other
unknown intermediate nitrogen compounds XN.
Consequently, two series of rate expressions for
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REACTION RATES OF NO AND N2 1095

'~176 2100-

Fro. 1. Profiles of nitric oxide, hydrocyanic acid, cyanogen and temperature iD the wet combustion
products. Elarmnable mixture: 7.5% ethyleneA 21.2% oxygen+71.3% argon+265 ppm C~q~. Burner
flow rate: 198 cm3 sec-~ (continuous lines) asLd441 cm* see-~ (dashed lines).

NO formation (V:a and ~%) and for N2 formation experimental condition

(V~ and ~z) have to be considered, the rates V=
XHcN+ Xc~N~+ XxN<<X~o
and V= accounting for all NO and N: formation
which does not go through HCN as an inter- nitric oxide may be considered as ~he only im-
mediate. Reaction rates V~ and Vn are therefore portant co-reactant for the rates Val and ~e.
to be considered as overall reaction rates of for- The change as a function of time of the mole
mation of NO and N2 from hydrocyanic acid. fractions of NO, HCN, and C2N2 due to chemical
The reaction rate of HCN formation from reaction, is given by:
Cyanogen will be indicated by V1. Accordingly,
the overall reaction rates of NO and N~ formation dXc~/dt = -- V1-- V22-- V32
from cyanogen are ~,espectively given by: = U~dXcN/dx--Dc.Nd2XcN/daY (10)
dXrfc~/dt= VI-- V21-- V~
Va = V=+ V= (s)
= UTdXHcN/dx--D~cNaCXHcN/dx~ (11)
VB = I751-~ - ~/~2 (9)
dX~,.o/dt = V21+ V~_-- Val-- ~ 2 - - VD
As all rate constants are determined at the = U~dXNo/dx--DNod2XNo/d% (12)
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1096 COMBUSTION SYSTEMS

TABLE I
Experimental determination of reaction rates V~, V~, V~, V~,, V~, Va, and V~ for the case of addition of
cyanogen to ethylene/oxygen/argon flames

Experimental
conditions Equations used Reaction rates (see-') Eq. No.

All mixtures From Eqs. (11) and (12):

(fuel lean or
rich)
t>t*** 2V~=--d(X~cN+X~o)/dt-VD ~V~l=3"lO~X~csX~oexp(-6OOOO/RT) (13i
and:
XncN<<X~o 2V2, = - d ( X n o ~ - X N o ) / d t + V D -*V~l~lO'~ ~ exp (--67 O00/RT) (14)
Lean mixtures From Eqs. (11) and (14):
t=t**<t*** V,/k,~Xo~ ~= (Xacs)*** ~V~= 1.3.10aXes exp(--2000 to (15)
5000/RT)
(supposing first order with respect to Xc~)
Rich mixtures From Eq. (11) into which Eqs. (13)
t <t*** and (14) have been substituted -*V, = 2.5.10~Xc~ exp ( - 0 to 5000/RT) (15bis)
Lean mixtures From Eqs. (10) and (15) :
t<t*** --~V~= 1.5.10"Xc~Xo~ ~ e x p ( - 3 3 O00/RT) (16)
Rich mixtures From Eqs. (10), (15), and (16):
t<t*** --~V,~=3.9.10~XosXso e x p ( - 2 6 O00/RT) (17)
All mixtures Sum of Eqs. (10), (11), and (12) :
all t values 2V.r = - d (XcN + X a c s - Xso)/dr ..-~VA=I.6-10~X~Xo~ exp(-4OOOO/RT) (18)
+V.
Subtraction of Eq. (12) from the
sum of Eqs. (10) and (11):
2V8 = - d (XoN +X~cN +X~o)/dt ~VB=5.5.10~XcsXso e x p ( - 3 2 O00/RT) (19)
- V/)

In Eq. (10), Xc~ stands for twice the value of
Xc~N~; UT is the gas velocity at temperature T
and D is the molecular diffusivity of the species
under consideration at the same temperature.
The values of Vn were calculated according to an
empirical expression of the thermal NO de-
composition rate 5 determined previously.
Selecting appropriate experimental conditions,
the rate constants of V1, Vsl, V22, V~I, V,~, V~ and
IzB can he determined, as shown in Table I. It
should be kept in mind that
(a) Under fuel lean conditions, reaction rates
Vs~ and Va2 may be neglected in a good approxi-
mation in the above expressions; this follows from
the fact that for fuel lean mixtures the total NO
yield is close to unity (see further);
(b) the time derivative of the HCN concen-
tration is zero at t=t** (see Fig. 1);
(c) at t_>t*** (see Fig. 1) the value of Xc~
becomes zero; consequently reaction rates V1,
V~ and V~ may be neglected.
The different parameters entering in the rato
expressions (temperature coefficient, partial
orders and pre-exponential constant) are deter-
mined successively from sets of experlment~l
points for which the parameter to be determined
was the only unknown variable, the other param-
eters either being kept constant or taken into
account according to their previous determina-
tion.
The precision of the temperature coefficients
in Table I is -4-3 to 5 kcal/mole; the partial
reaction order b with respect to molecular oxygen,
which appears in expressions (14), (16), and (18),
is found to be itself a function of the oxygen con,
centration, as shown in Fig. 2.
B. Addition of ammonia to methane/oxygen/'
helium flanges. Empirical expressions of VA and
VB are c h a i n e d from NO profiles, using an inte-
gration method, as described in an earlier publi-
cation.~ The overall rate expression obtained in
t h a t way for NO formation depends on the choice
of the order with respect t~* Ch; assuming the
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REACTION RATF~"; OF NO AND N, 1097

-23 I o _o o

-.~
~ O ~0 0
-2Z5 +z 1
__.\o
-22 ~
o.
~

\
.21.5 ,-,) o \'\.~.. ~n"
:o, O_
e- In -X, ,n. _~
n.'
O

I I I I I l
l~o.2. Reaction rate Vu: dependence on oxygen concentration, determined according to Eq~. (11) and (12).
Ethylene/oxygen/argon flame~J doped with cyanogen ; t > t***.

mine value b a.~ determined in the case of eyano-
p n addition, the following expreasion is obtained :
Va = 4-10*X.~-~,Xo# exp(-- 32 O00/R T) (see -~)
(2O)
The following overall reaction rate of N.~ fnrma-
w is obtained:
Ira= 1.8. lO~X.x~,X.~o
)<exp(--27 I~)O/RT) (~e -1) (21)
C. Prampl .NO forrrmlion in ethylene/oxygen~
~,ragen flames. NO profiles obtained in fuel rich
9 ixtures show typical discontinuities (Fig. 3).
The sudden change in the slope of th~,e profiles
dase behind the flame front, together with the
daape of the IICN profiles, suggests that in the
Jarty flame stages molecular nitrogen behaves like
lfuel nitrogen compound, according to an overall
~action scheme quite analogous to the one pre-
viously described: NO and Na are partly formed
with tlCN as an intermediate, at reaetion rates
V.2~, respectively ~'~1. There may of course exist
parallel paths nf prompt NO formation, passing
through other intermediates XN, which are
acenunted for by the unknown rates I".~ (NO
formation) and Van (N., formation).
Accolxiing to Eqs. (4)-(6), one then has:
T~ = V:I+ V=
(overall prompt NO formation rate) (22)
VB= V,t+ Vu
(overall prompt N~ fornmtiou rate) (23)
(dX.~o/'dt) (prompt) = IrA- VB= dXxo/dt
-- Vc@T~ (24)
Even for fuel-rich flames, the oxygen concen-
tration in these early flame stages ks still reN
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1098 COMBUSTION SYSTEMS

TABLE II
NO yields from NtII added to methane/oxygen/helium flames, and from C~N~ or NO added to
ethylene/oxygen/argon flames; influence of equivalence ratio, temperature and fuel nitrogen content

Temperature NO yield (R)

Equivalence Diluent (XAz)0 at t*
AZ ratio % X10 ~ ~ measured calculated

NH8 0,78 72.3He 1274 2140 0.98 0,95

1.00 71.0He 1230 2150 0,94 0,91
1,14 7 0 , 3 He 1160 2355 0,63 0.65
1.31 6 9 . 4 He 1275 2300 0.32 0.37
1.31 6 9 . 4 He 1275 2040 0.26 0.32
1.44 68.8 He 1190 2347 0.28 --
1.44 68.8 l i e 1190 1874 0.27 0.27
C~N, 0,70 67,6 Ar 260 2420 0.91 0.93
0.70 67.6 Ar 260 2370 0.85 0.89
0,70 67.6 Ar 260 2215 0,83 0,80
0.70 67.6Ar 1040 2215 0.76 0.73
0,77 69.2 Ar 265 2420 0,83 0.91
0.85 71.0At 265 2440 0.02 0.90
0.85 71.0 Ar 265 2355 0,89 0.87
0.85 71.0 Ar 265 2160 0.82 0.79
1.00 71.6 Ar 250 2460 0.96 0.92
1.08 71.2 Ar 265 2490 0.78 0.76
1,08 71.2 Ar 265 2370 0.74 0.70
1.08 71.2 Ar 265 2200 0.57 0.65
1.20 70.6 Ar 265 2475 0.51 0.55
1.20 70.6 Ar 1230 2430 0.49 0.52
1.31 70.1Ar 260 2465 0.40 0.43
1.43 69.4 Ar 260 2430 0.31 0.32
1,58 68.7 Ar 265 2400 0.29 0.27
1,58 68.7Ar 265 2350 0.25 0.22
1.58 68.7 Ar 265 2155 0.25 0,19
1.58 68,7Ar 1200 2395 0.25 9.24
1.58 68.7Ar 2070 2405 0.19 0.20
NO 0.70 67.6 Ar 220 2315 0.68 --
0.70 67.6Ar 220 2130 0.90 --
0.70 67.6 Ar 970 2315 0.98 --
0.70 67.6 Ar 970 2130 0.92 --
0.70 67.6 Ar 1965 2130 0.90 --
0.77 69.2 Ar 225 2385 0.98 --
0.85 71.0 Ar 225 2395 0.93 --
1.00 71.6At 230 2450 0.90 --
1.07 71.2Ar 230 2485 0.77 --
1.07 71,2At 230 2170 0.72 --
1.20 70.6At 230 2450 0.53 --
1.31 70.1Ar 220 2430 0.44 --
1.43 6 9 , 4 Ar 215 2460 0.36 --
1.58 68.7 Ar 290 2410 0.25 --
1.58 68.7 Ar 290 2170 0.23 --
1,58 68.7Ax 1140 2170 0.23 --
1.58 68.7 Ar 1995 2170 0.20 --
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REACTION RATES OF NO AND N, 1099

r/\ ! / ,ooo-

.J~" time---,.. '-~'-~--o

~" 1, 2, (msec) p
Fzo. 3. Profiles of NO~, hydrocyanic acid and temperature in the wet combustion products. ~lanunable
mixture: 10.3% ethyleneS-23.9% oxygen-b65.8% nitrogen. Burner flow rates: 264 cm~ sec-1 (continuous
lines) ; 131 cm~sec-~ (dashed lines) ; 73 cm~ sec-~ (dashed-dotted lines).

a~ively high; for this reason the value of
(dXso/dt)(prompt) will be approximately equal
to V~ and can therefore be determined from the
NO profiles according to Eq. (24). TILe best
fitting values of V~ are again obtalned when
accepting a partial order with respect to 02 equal
to b; on the other hand Vx is found to be of the
first order with respect to the nitrogen and to the
fuel concentration:
Va~(dX~o/dl) (prompt) = 1.2" 107Xo,bXs~YRH
Xexp(--60000/RT) (sec-~) (25)
The precision of the temperature eoeffident is of
the order of =t=5 kcal/mole.
The overall r~te of formation of t t C N from N~,
indicated by the symbol V4, may be determined
from the H C N profiles, according to the equation:
This was done for a nitrogen mole fraction of
0.62; under that condition 1;4 was given by:
V4=8.4.10tsXR~~ exp(--30 O00/RT) (sec-l)
(~7)
The pre-exponential constant includes the nitro-
gen mole fraction; the precision of the tempera-
ture coefficient is =1=5kcal/mole.
3. Nitric Oxi& Yields from Furl Nitrogen
The NO yield, R, is defined as the ratio of the
nmximum amount of fuel NO (reached at time
t*, see Fig. I) to the amount one would have if all
the initial fuel nitrogen (XAz)0 were converted
into NO:

dXHcN/dt= V4-- V21--F31 (26) R = (XNo),/(XAz)o (28)

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1100 COMBUSTION SYSTEMS
In all our experiments in which either ammonia,
or amines, or cyanogen, or even NO itself is
added to hydrocarbon/oxygen flames as the only
nitrogen source, the same observations were
made: (a) The NO yield is particularly sensitive
to the oxygen content, and therefore to the
equivalence ratio; some experimental results are
given in Table II. For lean to stoichiometric
mixtures R is close to unity, whereas it decreases
progressively to much smaller values in fuel rich
mixtures. (b) A rather small effect of temperature
and initial fuel nitrogen concentration on R has
been observed; increase of temperature results in
an increase of the NO yield according to a tem-
perature coefficient between 3 and 10 kcal/mole,
depending on the equivalence ratio.
In the case of prompt NO formation, it is more
useful to consider the absolute value of total
prompt NO, indicated b y (XNo)., rather than
the relative yield. Experimental values are given
in Fig. 4 as a function of equivalence ratio and
temperature. The typical evolution of (Xso). as
a function of equivalence ratio, characterized by
a maximum, follows from the competition of two
factors, viz., the amount of H C N and the con-
centration of 02, which vary inversely when the
equivalence ratio is changed.
Discussion
Two main points will be discussed: (a) the
validity of the empirical expressions derived for
the overall formation rates of NO and N2 from
fuel nitrogen compounds will be checked by com-
paring experimental values of the NO yield R
with values calculated by numerical integration
of these overall reaction rates; (b) the relative
importance of H C N and atomic nitrogen as inter-
mediates of fuel NO formation will be discussed.
1. Comparison Between Experimental and
Calculated Values of the NO Yield R
The vahte of (XNo)* can be calculated by
numerical integration of Eq. (6), into which the
empirical expressions for Va, VB, and VD have
been substituted; integration is up to the time t*
for which Eq. (6) becomes equal to zero. The mole
fraction of the fuel nitrogen compound AZ is
estimated by the expression:
Xxz = (XAz)o--ft(va+ VB)dt (29)
The values of the oxygen concentrations that
enter into VA were taken from experimental pro-
files. The results agree very well with the experi-
mental values, and especially account for the
observed effect of oxygen concentration and for
the rather small effect of temperature (see Table
II).
2. Relative Importance of H C N as an Inter-
mediate
An overall chemical reaction path going
through a number of consecutive steps is expected
to present a temperature dependence character-
ized by an overall temperature coefficient which
is at least equal to the highest activation energy of
the successive elementary steps. Consequently,
comparison of Em (given b y Eq. 14) with the
values of the temperature coefficients of Vx
[given b y Eqs. (18), (20), and (25)7, as well as
comparison of E~I (given b y Eq. 13) with the
values ~of the temperature coefficients of Vs
[-given by Eqs. (19) and (21)'], suggests t h a t the
relative importance of H C N as an intermediate in
NO formation, respectively N2 formation, de-
creases according to the following sequence of
initial nitrogen compounds: N~ (by the prompt
NO mechanism), cyanogen, ammonia. From the
same comparisons, it follows t h a t in none of these
cases can the hydrocyanic acid be considered as
an indispensable intermediate. Accordingly, a
progressively growing importance of some other
parallel intermediate nitrogen compounds must
be postulated (such as N H or NH2, as suggested
recently by others 8.6).
H C N seems to play a more important role in
the mechanism of prompt NO formation. This
can be shown b y comparing the experimental
values of total prompt nitric oxide (Xxo)., with
values calculated by numerical integration of the
following expression, in which all NO formation
is through H C N as an intermediate:
(dXNo/dt) (prompt) = XHCN(/~IXo, ~ - k~aXxo)
(30)
The results, shown in Fig. 4, indicate that almost
90% of prompt NO is formed by way of HCN.
3. Relative Importance of Atomic Nilrogen as an
Intermediate in the Fuel NO Mechanism
In this section we would llke to examine the
extent to which overall reaction rates derived
above are consistent with the hypothesis accord-
ing to which N atoms would play the role of final
and indispensable intermediates in the formation
of NO and N2 from fuel nitrogen. The objective
is not to prove this hypothesis, but only to see in
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REACTION RATES OF NO AND N, 1101

-40-

I -30

~-20
I---
ft.
0
n.'
0. -10
..I

1 1.2 1.4 1.6

EQUIVALENCE RATIO :
Fto. 4. Total prompt NO, as a function of equivalence ratio and temperature. Ethylene/oxygen/nitrogen
flames (62% nitrogen). Continuous lines: experimental values. Dashed lines: values calculated on the
assumption that ttCN is an indispensable intermediate.

how far--if it is accepted--it might be congruous mediates, a takes one of the two following forms:
with the experimental data.
If X N represents an indispensable inter- a = kwroJke
mediate, and if one reduces the fuel NO mecha-
nism to the two leading reaction paths a = kAXo?/k~

I
XN+OX----*NO+..- where k~ and k6 are the rate constants of the
elementary reactions:
II
XN+NO ----~ Nr~-. 9 9 5
N+(h --~ NO+O
then the NO yield can be expressed b y the follow- %
6
ing equation, formerly derived in an equivalent N+NO ~ N~+O
form b y Fenimore~:
According to Eq. (31) the temperature depend-
R = -- 1-- [2a/(XAz)03" ln[1-- (XNo)./a"l (31) enco of R is governed by a coefficient equal to
EI--EII, and the hypothesis that N is an in-
where ~ stands for kiXox/kii. Depending on dispensable intermediate requires that E,4-- EB =
whether N atoms or the initial nitrogen com- Es--E6. This requirement is roughly consistent
pounds AZ are considered as indispensable inter- with the experimental values of EA and Es
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1102 COMBUSTION SYSTEMS
derived both in the ease of ammonia addition and
the case of cyanogen addition.
On the other hand, two discrepancies should be
noted that either tend to argue against the hy-
pothesis, or indicate that Eq. (31) does not
adequately describe the dependence of R on Xo2
and (XAz)0,viz. : (1) the fact that b is not equal to
unity and (2) the fact that Eq. (31) predicts a
much more important dependence of R on the
initial fuel nitrogen concentration, than was found
experimentally in the present work.
Acknowledgments
The work presented in this paper was supported
by the French Ministry of Enviromnental Protec-
tion.
COMMENTS
T. Asaba, University of Tokyo, Japan. In for-
mation of nitric oxide from fuel nitrogen, direct
oxidation of intermediates containing nitrogen
seems to be a more plausible route than routes
tbrough formation of atomic nitrogen, since
atomic nitrogen is highly reactive and needs much
energy to be produced. Is formation of atomic
nitrogen necessary?
Authors' Reply. At the present time, the relative
importance of N-atoms as intermediates in the
NO and N2 formation from fuel nitrogen seems
REFERENCES
1. F~NIMORE, C. P.: Combust. Flaum 19, 289
(1972).
2. D~ So~B, G. G.: Rev. Inst. Fr. P6t. Z8, 95
(1973); InEM: Combu~kion Institute European
Symposium, p. 439, Academic Press, 1973.
3. SLATER, S. M.: Nitric Oxide Formation in the
Com~yustianof Nitrogen-wontainingHydrocarbons.
Thesis Digest, Mass. Inst. of Teelm. (1973).
4. BACHMAIER~F., EBERIUS~K. H., ANDJUST, TH.:
Combust. Sci. Tcchnol. 7, 77 (1973).
5. D~ SO~TE, G. G.: Revue de l'Institut Franfais
du Pdtrole 27, 913 (1972).
6. DUXBURY, J. AND P~tATT, N. H.: Combustion
Iwstilute European Symposium, p. 433, Academic
Press, 1973.
difficult to determine. The fact that the overall
dependence of NO yield on temperature is
experimentally found to be governed by a tem-
perature coefficient E A - - E B ~ 3 to 10 kcal/mole
would at least be consistent with the hypothesis
of N-atoms being final indispensable inter-
mediates.
The production of N-atoms in the flame front
over the fuel-NO mechanism (by reactions like
CH-~-N~--~HCN-~-N) needs much less energy
than the formation of N-atoms from N2~-O
reaction.