10
EFFECT OF OXYGEN ON THERMAL
NITRIC OXIDE AT HIGH TEMPERATURES
F. K A U F M A N and L. J. D E C K E R
INTRODUCTION
An earlier investigation1 h a d shown that the
thermal decomposition of N O is a homogeneous,
bimolecular reaction above a b o u t 1,400 ~ K a n d
that its rate is unaffected by a d d e d N2 or He, or
by changes in the surface to volume ratio. T h a t
study h a d been carried out in a static system, with
very good reproducibility, a n d free from the
ambiguities of flow systems. I n the t e m p e r a t u r e
range 1,370 to 1,530 ~ K, the rate constant was
found to be 2.6 x 1012 e -6a'8 • O.6/RT c.c. mo1-1
sec-1. This value of the activation energy n o w
supersedes a considerable array of earlier ones
whose great range was due to questionable
experimental work or over-simplification of results
obtained u n d e r highly complicated conditions. I n
view of Vetter's results2 it was clear that a catalysis
by 0 2 was to be expected at still higher tempera-
tures a n d the beginnings of such an effect were
barely observed 1 at 1,473 ~ K. R e c e n t work by
Fenimore a n d Jones a on the decomposition of N O
in flames at 2,200 to 2,400 ~ K showed inhibition
by 02, but did not lead to a satisfactory
mechanism.
T h e decomposition of N O at flame t e m p e r a -
tures is of m u c h interest in propellant chemistry
and in flame studies4 where the mechanism of
certain f u e l - N O flames has precipitated some
controversy5. T h e r e is little d o u b t that the
oxygen effect is due to atom reactions of the type
2 Spectrophotometric analyses for unreacted N O
O + NO ~-O~ + N Ho~ = + 32.1 kcal
-2
3
N + NO ~-N2 + O Ho~ = - 75.05kcal
-3
T w o points must be stressed. (a) T h e AH of
these steps is now settled 6, i.e. D ~ [N2] = 225.1
kcal, Do~ [Oz] = 117-96 kcal, which means that
this ' c h a i n ' reaction scheme is not a chain at all,
but, as Fenimore and Jones have pointed out a, a
slow, e n d o t h e r m i c reaction of atomic oxygen
whose ultimate regeneration by reaction 3 is
immaterial since thermal equilibrium is likely to
exist between O and Oz. (b) T h e r e is i n d e p e n d e n t
information on the rates of these oxygen a n d
57
DECOMPOSITION OF
nitrogen atom reactions 7-9 which (:an be applied
directly.
This paper describes experiments in a static
system up to 1,690 ~ K with initial [O~]/[NO]
ratios from zero to 40. A very satisfactory account
of all experimental results can be given within a
simple mechanism a n d in agreement with the
available information on the rates of atom
reactions.
EXPERI MENTAL
T h e decompositions were carried out in cylindrical
porcelain reaction flasks (McDanel Refractory
Porcelain Company) fitted with an inlet tube and
a thermocouple well. Their volume was approxi-
mately 350 c.c. T h e furnace consisted of an
a l u n d u m tube (Norton) w o u n d with heavy
K a n t h a l wire, B. and S. 13, 6 turns p e r inch. T h e
winding extended 389 in. beyond the tapered end
of the reaction vessel on both ends to ensure
temperature uniformity. T h e furnace tube was
housed in a larger cylindrical enclosure m a d e of
sheet aluminium and transite, and filled with fine
alumina powder. T h e furnace resistance was
about 9 ohms. At a reactor t e m p e r a t u r e of
1,690 ~ K it dissipated 1,000 W. T e m p e r a t u r e
uniformity was very good, about _+ 1~ C over the
main volume. A capillary insert in the inlet tube
kept the cold volume to a m i n i m u m of 1 to 2 per
cent of total volume.
were carried out by conversion to NO~ with large
excess of 0 2 in a 10 cm absorption cell and
determination of the optical density at 3,200 and
4,000 h . In runs with little decomposition, 0 2
was converted to an NO2 - N2Oa equilibrium
mixture with large excess of N O and analysed at
several wavelengths between 3,450 and 3,600 .~.
Details of the method are presented in reference 1.
N O was prepared from cylinder gas (Matheson)
by slow passage through a large tube tilled with
ascarite and through a trap at dry-ice tempera-
ture, followed by condensing at - 195 ~ C. It was
distilled once, then repeatedly sublimed until
infra-red analysis showed no trace of higher
oxides o f nitrogen and an N 2 0 content of 0.01
per cent or less. Nitrogen (Matheson, pre-purified)
 M E C H A N I S M OF COMBUSTION REACTIONS

a n d oxygen (Burdett O x y g e n Co., 99.5 per cent

02) were used w i t h o u t purification. i

T h e procedure of kinetic experiments was so

designed to cancel errors t h a t m a y h a v e been due
to variable addition of oxygen or nitrogen. N O
was a d m i t t e d to the reactor to the desired pressure
11 ~
E
0
,~1
E

?l-

(15 to 50 m m Hg) a n d m e a s u r e d to 0.1 m m Hg.

T h e reactor was isolated, the line p u m p e d out,
a n d 30 to 50 seconds later, a k n o w n N2 - 0 2
mixture ranging from pure N2 to p u r e 0 2 was
a d m i t t e d to the reactor in large excess to give a
total pressure of a b o u t 60 m m Hg. T h e reaction
was then allowed to proceed to a b o u t 40 to 70
per cent completion (usually 6 to 15 rain.) a n d
was stopped b y expansion into the absorption cell.
T h e expansion was done in a way to minimize the
accumulation of gas from the cold volume in the
cell as previously described 1. This procedure
eliminated all variability due to cold volume,
compression a n d mixing with a d d e d gases, a n d
other effects of large changes in total pressure. It
was justified by the experimental fact t h a t a d d e d
N2 had no effect on the rate over the entire
t e m p e r a t u r e range.
RESULTS
O n e h u n d r e d kinetic runs were carried out. O f
these, 47 were done in the first reaction flask which
failed at 1,580 ~ K. T h e r e m a i n i n g 53 were done
in the second flask from t ,575 to 1,690 ~ K. T h e last
25 runs were done using the above procedure at
1,575, 1,606, 1,637, 1,663, a n d 1,690 ~ K. At
1,690 ~ K the furnace failed.
T h e first 30 experiments were performed at
1,378 to 1,530 ~ K to overlap with the earlier
investigation. Several runs at 1,378 ~ K gave a
bimolecular kl = 190 + 10 c.c. tool -1 sec -1 a n d
at 1,476 ~ K, k, = 850 • 40 c.c. mo1-1 sec-'. T h e
earlier resuhs 1, kl = 2.6 x 1012e-63.slRT give 198
at 1,378 ~ K, a n d 910 at 1,476 ~ K. This represents
excellent a g r e e m e n t w h e n it is considered t h a t the
present results were obtained in a flask 1/5 the
size, of a different material (porcelain versus
quartz), a n d geometry (cylindrical versus spherical)
of t h a t used before. No oxygen effect was found
at 1,378 a n d 1,476 ~ K, b u t a small increase of kl
was observed at 1,530 ~ K giving a r a n g e of 2,000
to 2,700 c.c. tool -1 sec -1 for kl w h e n oxygen
addition was varied from zero to a n eightfold excess
over [NOlo. Some of these experiments also
showed a slight increase of kl w i t h increasing time
of reaction, indicating catalysis b y the oxygen
formed in the decomposition.
T h e results of the last 25 runs, at the highest
temperatures, a n d with variable amounts of
added 02, are shown in Figure 1. T h e fictitious
second-order rate constant, k, is here plotted
versus (pO2) 1/2 a n d its increasing dependence on
a d d e d oxygen is clearly shown. T h e r e is seen to
Io
0 iO 20 50 40
k x iO5, {mrn. ser
Figure l. Secondorder rate constants./'or NO decomposition
with added oxygen
be strong catalysis by small amounts of 02, b u t
w h e n the initial pO2/pN o is a b o u t 4, the effect is
near its m a x i m u m , a n d for m u c h higher ratios,
it decreases again. This is particularly pro-
nounced at the highest temperatures, where the
peak k is three times kl a n d where the decrease at
high p O 2 is clearly evident. These runs r a n g e d
from 40 to 70 per cent decomposition a n d e n o u g h
0 2 was formed t o r a i s e k well above kl even in
the absence of a d d e d 02. T h e decomposition
runs of pure N O are therefore entered in Figure 1
for the average value of pO~ present d u r i n g the
experiment. T h e values for p O 2 = 0 are extra-
polated from lower t e m p e r a t u r e s using kl -= 2-4
x 1012e -63'a/RT. Figure 1 is only a graphical
s u m m a r y of the results a n d is not further used in
the calculations.
CALCULATION AND DISCUSSION
W e use the following set of assumptions. Con-
current with the simple, bimolecular decom-
position of N O , there is reaction by steps 2, --2,
a n d 3. R e a c t i o n - 3 is negligibly slow in this
t e m p e r a t u r e range, i.e. the equilibrium con-
centration of N O is very small a n d n o N2 effect
was ever observed. Atomic oxygen is in t h e r m a l
equilibrium, with 02, a n d N is in steady state b y
steps 2, - 2 , a n d 3. This leads to the rate
expression
- d [NO] 2k2K [NO] [O2] 1/~"
dt - - kl [NO] 2 + k-2 [02] (1)
1-I- - - - -
k3 [NO]
where K = [O211/2][O]. I t is clearly of the correct
form to explain the d a t a if the ratio k2/ka is small.
For k-2/k3~_ 0.07, the d e n o m i n a t o r of the
second t e r m is a p p r o x i m a t e l y 1 as long as
[O2]][NO] < , ~ 1, i.e. small amounts of added 0 2
give rise to catalysis of m a g n i t u d e proportional to
[O211/2 . F u r t h e r increase of [02] will make the
second t e r m of the rate expression r e a c h a maxi-
m u m a n d then decrease again. For very large

58
 EFFECT OF OXYGEN ON T H E R M A L DECOMPOSYFION OF NITRIC O X I D E
[02], it will be proportional to [08] 1/2 and there
will be inhibition by added oxygen. Since it was
not possible to measure the rate of decomposition
over small increments of N O , the rate expression
must be integrated. This presents difficulties
w h e n [02]o is small because the exact differential
equation is of the form
- dx Bx (C - x)l/2
dt = Ax2 + , (2)
I+D C-x
x
x = [NO]. T h e integration was therefore carried
out only for those runs where [Oz] could be
considered constant, i.e. the runs with 30 m m H g
or more initially added 08. I n most cases, 4 to
6 m m H g of 0 8 were formed during the run and
an error of 2 to 3 per cent at most was m a d e by
setting the oxygen concentration equal to the
a m o u n t a d d e d initially plus one-half the 0 8
formed in the decomposition. T h e simplified
equation now becomes
-dr - klx2 [ ,]
1 +
x-{-
where/~ = 2k2/kl . K[O211/2 and a = k-2/k3[021,
and it was integrated to give the relation
kl (tl - to) 1 1 fl [1
Xl Xo a "]- 3
+ --- log --
Initial calculations of experiments at constant
T with various [O2]o showed that in order to give
the desired dependence of a and fl on [O2], the
ratio k-2]ka would have to lie between 0.05 and
0.1. A value of 0.070 was chosen at 1,575 ~ K a n d
slowly increasing ratios of 0.072, 0.075, and 0-079
used at the higher temperatures. This choice is
discussed further below.
E a c h run was corrected for the short time (30
to 50 sec) after admission of N O but before
addition of the N2 - 02 mixture to the reaction
vessel. After all preliminary corrections, each
experiment supplied a set of (h - to), Xo, a n d Xl.
W i t h a known,/3 was determined by iteration. An
a p p r o x i m a t e /3 was guessed a n d used in equation
3 as (a + /3) and (x + a + fl) to solve for an
i m p r o v e d value of/3. This was repeated until no
further i m p r o v e m e n t was obtained.
F r o m the definition of/3 a n d kr
2k2 K
/3 ~ ~- [0211/2 - /,-~[0211/2
it is seen that k~ should be a constant at constant T.
W i t h increasing T there should be a rise in k~.
This is indeed observed. T a b l e 1 shows the d a t a
of two of the five temperatures, k~ is i n d e p e n d e n t
of [08] and rises with T.
T h e graph of log kf~ versus l I T is shown in
Figure 2. The highest t e m p e r a t u r e is represented
by a single point which lies too high. F r o m the
graph, k~ = 15 • e 35 • 1/RT (mol/c.c.)l/2.
-3'-~ le
-3.4
"~ -3.E
-3-7
"L
,\
-5,8
[
5"8 5"9 6"0 6.1 6-2 6.3 64
/ x I04
T
a
(3)
Figure 2. Temperature dependence of Kf~
I n the range T = 1,500 to 1,700 ~ K , the
equilibrium constant K = 5.015 x e - 5 9 ' 3 1 R T
(mol/c.c.)l/2, corrected for the new, slightly higher
D[O2]. Using kl = 2.4 • 1012e-63"8/RTc.c. mo1-1
I see -1, we evaluate ks = 3.6 x 1012e-39"5 • 1/RT.
Xo Xl T h e results that E2 = 39.5 _ 1 kcal is a most
.
xo)] (4)
reasonable one. T a k e n together with the endo-
thermic AH of 32.1 kcal of reaction 2, it implies
that reaction - 2 has an activation energy of
about 7.5 kcal. R e c e n t experiments with active
nitrogen by Kistiakowsky a n d Volpi s and in our
laboratory 9 have shown that reaction 3 is ex-
tremely fast and has no activation energy a n d that
reaction 2 is slow "at room temperature 8,
k-2 = 2 x 1012e 6.2/aT Extrapolating k2 to the
temperature range 1,500 to 1,700 ~ K and com-
bining with the experimental finding that k-2/k3
is about 0.07 makes k3 - 4 x 1018 c.c. mo1-1
sec -1, a normal value for a fast, bimolecular
reaction. The ratio, k-2/k3, therefore has an
activation energy of 6.2 kcal a n d rises slowly
between 1,575 and 1,690 ~ K as stated above.
The agreement of the direct experimental
E - 2 = 6.2 kcal with the value of 7.5 kcal in this
work is also quite good, since it actually represents
agreement between the calculated E2 = 38-2 kcal
and our experimental E2 = 39.5 _+ 1 kcal. T h e
pre-exponential factor of k2, 3.6 • 1018 c.e.
mo1-1 sec -1 is high. Using k _ 2 = 2 x 1012e-6"2/aT
and the known equilibrium constant, /s k2 =
4.2 x 1011e aS..~/RT. This discrepancy of a factor
of 9 is reduced to one of a factor of 5 w h e n the
activation energies are matched. Considering the
great extrapolation of k-2 from the range 400 to
500 ~ K in which it was measured, to 1,500 to
1,700 ~ K, this factor is not serious.
59
 M E C H A N I S M OF COMBUSTION REACTIONS

T h e above analysis thus yields a consistent a rate proportional to [NO] [O2]t/2 for low [02],
interpretation of all runs with m u c h a d d e d b e c o m i n g i n d e p e n d e n t of [02] a n d inhibited by
oxygen a n d provides rate constants which agree 0 2 at high [02]. T h e second t e r m of equation 1
with other work. is at its m a x i m u m w h e n
Because of its dependence on [O211/2 for low [O2], [021 1 + ,,/2
the second t e r m in the differential rate expression 1
should become appreciable w h e n only very little
[NO] 3 (k_2/k3)
O3 is added. A t 1,663 ~ K, the fictitious second W i t h k-2/k3 = 0.07 to 0"08, [O2]/[NO] = 11.5 to
order rate constant w h e n no 0 2 is a d d e d was 10. Since [O2]/[NO] increases as each r u n
found to be 1-54 x 104 c.c. mol I see-1 for 55 per progresses a n d N O is decomposed, the m a x i m u m
cent decomposition, whereas kl, the extrapolated overall rate constant should be observed for
bimolecular rate constant in the absence of any somewhat lower initial [O2]/[NO] ratios. This is
0 2 effect is only 0.94. It a p p e a r e d t h a t the small indeed the case, the m a x i m a i n Figure 1 occur at
a m o u n t of oxygen formed d u r i n g the decom- initial ratios of 6 to 8. A t flame temperatures of
position raised the overall rate c o n s t a n t 60 per a b o u t 2,500 ~ K a n d 3,000 ~ K, this m a x i m u m
cent. This was verified in the following m a n n e r . instantaneous rate should be found at ratios of
T h e time interval of this experiment, No. 177, 5.5 a n d 4.5, respectively, a n d the m a x i m u m
was 8 minutes. I t was subdivided into 8 one- overall rates nearer initial ratios of 3.
m i n u t e intervals a n d the a m o u n t of N O decom- T h e results of this work c a n also be easily
posed was calculated for each m i n u t e using the extended to provide information on the rate of
rate constants o b t a i n e d with large 0 2 addition. formation of N O from N2 a n d 0 2 at high tem-
A n average value for [NO] a n d [02] was used peratures.
for each m i n u t e interval. It was found t h a t the TABLE 1
contribution of the second t e r m in the differential Calculated values of k~ = 2k2K/k 1
rate expression grew so quickly t h a t d u r i n g the I
eighth m i n u t e it was equal to t h a t of the first term. Run T poNO p002 [k I • 10e k~
T h e calculated a m o u n t of N O decomposed in the I
oK mm mm [ r a m / s e e -1 minX/2
entire run, 7.86 m m Hg, agreed perfectly with the
experimental value, 7.84 + 0.15 m m Hg. T h e 160 9 TI 33.85 188
kinetic scheme is thus also able to explain the 161 1571.9 52.9 ] 597-4} 32.51 1.90
experimental results with little or no a d d e d 156 1573.4 25-7 I 33.6 I 33.23 1.81
153 1573-4 26-2 / 98"41 33.23 2.02
oxygen. It is in good a g r e e m e n t with Vetter's 155 1573.9 25.8 [ 100"7 i 33.47 1.94
experimental findings 2. A n earlier re-interpretation 154 1574.0 25-9 702-9 I 33-52 2-16
of some of his high t e m p e r a t u r e resultsl h a d given 152 1572.5 25.4 708.2 32.80 2.05
k2 = 8.3 x 1012e-4~ This was slightly in
error because K = 8.5 x e-6O'5/RT was used k~ average at 1,575 ~ K--1.997
instead of 5.0 x e 59.3/~T. T h e corrected 170 1640.1 ~ - - 99.4 73-35 3"29
k2 = 14 x 10122-41"7/RT is in satisfactory agree- 171 1638.2 25-6 I 618-8 71.74 3-06
m e n t with our present k2 = 3.6 x 10122-39"5/RT. 175 1637.5 15-0 I 33.0 71.14 3-13
W e c a n n o t explain F e n i m o r e a n d J o n e s ' results, 174 1637-6 16"2 101.6 71.23 3-09
176 1640.4 15.2 ] 628.2 73.60 3.14
b u t believe t h a t the application of the O a n d N
a t o m scheme to flames with excess H a does not k~ average at 1.637 ~ K--3-10
seem justified, as it neglects entirely any direct
reaction with H2. T h e i r results w i t h excess O3 REFERENCES
suggest t h a t the presence of H 2 0 a n d O H m a y be
1 KAUFMAN, F. a n d KELSO, J. R. J. chem. Phys.
partly responsible for their h i g h rate of decom-
23 (1955) 1702
position a n d its inverse square root d e p e n d e n c e V~TTER, K. Z. Elektrochem. 53 (1949) 369, 376
on 0 3. a FENIMORE, C. P. a n d JoNEs, G. W. J. phys.
T h e b e h a v i o u r of N O at still higher tempera- Chem. 61 (1957) 654
tures, in flames a n d explosions, can now be 4 ADAMS, G. K., PARKER, W. G. a n d WOLFHARD,
predicted with greater confidence. I n the absence H. G. Disc. Faraday Soc. 14 (1953) 97
of H2, CO, or other reactants whose high tem- 5 ROZLOVSKII, A. I. Zh. fiz. Khim. 30 (1956) 9 t 2 ,
perature reaction with N O has not yet been 1444
cleared up, the second t e r m in rate expression 1 6 BRIX, P. a n d HERZBERC, G. Canad. J. Phys. 32
(1954) 110
will overshadow the first with increasing tempera- 7 K A L I F M A N , F. J. chem. Phys. 28 (1958) 352
ture. Because of the low activation energy of s KISTIAKOWSKY, G. B. a n d VOLta, G. G. J. chem.
reaction - 2 , the ratio k-2/k3 will rise only very Phys. 27 (1957) 1141
slowly, a n d so the decomposition of N O will 9 KAUFMAN, F. a n d KELSO, J. R. J. chem. Phys.
retain some of the characteristics observed here; 27 (1957) 1209

60