I AIAA-89-1740

A Review of Reaction Rates in High Temperature Air

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Chul Park
NASA Ames Research Center, Moffett Field, CA

AlAA 24th Thermophysics Conference

Buffalo, New York / June 12-14, 1989

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370 L’Enfant Promenade, S.W., Washington, D.C. 20024
 A REVIEW OF REACTION RATES IN HIGH TEMPERATURE AIR
Chul Park*
NASA Ames Research Center, Moffeu Field, CA
Abstract
The existing experimental data on the rate coefficients
for the chemical reactions in nonequilibrium high temper-
ature air are reviewed and collated, and a selected set of
such values is recommended for use in hypersonic flow cal-
cuilations. For the reactions of neutral species, the m-
ommended values are chosen from the experimental data
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that existed mostly prior to 1970, and are slightly differ-
ent from those used previously. For the reactions involving
ions, the recommended rate coefficients are newly chosen
from the experimental data obtained more recently. The
reacting environment is assumed to lack thermal equilib-
rium, and therate coefficients are expressedas a function of
the controlling temperahue, incorporating the recent multi-
temperature reaction concept.
Nomenclature
C = reaction rate constant in the forward (endotherm-
ic) rate coefficient, cm3mo~e-'sec-'
= forward (endothermic) reaction rate coefficient,
kr
t
cm3mole-' sec-'
= reverse (exothermic) reaction rate coefficient,
kr
cm3mole-' sec-' for two-body reactions and
cm6mole-zsec-' for three-body reactions
M = unidenIi6ed colliding third body
n = preexponential power on temperature in reaction
rate coefficient expression
T = translational-rotational temperature, K
= \AT;.K
= electron temperature, K
= vibrational-electronic temperature, K
Introduction
As man's exploration extends farther into space, there
is increasing need for accurate data on the aemthermody-
namic environments around the space vehicles during the31
atmospheric entry flights. An accurate description of such
environment also requires proper accounting of the thermo-
chemical nonequilibrium phenomena occuning in the flow-
field around such vehicles. The limited heat-shielding abil-
ity of the surface materials of such vehicles prescribes that
the density of the flight regime must be inversely propor-
tional to the cube of speed of the vehicle so that the surface
heat transfer rates remain below the allowed maximum val-
*Research Scientst: Associate Fellow, AIAA.
This paper is declared a work of the U.S.Government and
is not subject to copyright protection in the United States.
1
ues. The low density leads to the thermo-chemical nonequi-
librium conditions in which the thermodynamic and chem-
ical s t a m of the gas are controlled by the rate processes.
One major problem in calculating such phenomena is the
uncertainty in the magnitudes of the rate coefficients for the
thermochemicalprocesses. The rate coefficients are deter-
mined traditionally through experiments: theoretical deter-
mination has not yet been made for the air reactions to the
degree of reliability needed. The existing experimental data
on high tempemture air reaction rates contain a consider-
ableamountof scatter. For the hypersonic applications, one
needs to select a set of the most reliable rate coefficients.
The first effort to review and choose the most reliable
set of reaction rate coefficient values for high temperature
air was made by Viicenti and Kruger.' Their recommended
set of rate coefficientscovered all major neutral-species re-
actions and the NO+ associative ionization reaction. The
first review that included other ionic reactions was made
by Bomer? Kang and Dunn' selected a set independently
from Bomer. Subsequently, Baulch et al! reviewed the
reactions among the neutral species. Park and Menees'
adopted a still different set of rate coefficients by incorpo-
rating the values recommended by Baulch et al., the values
of Johnston for oxygenreactionsp and the data on nitric ox-
ide reactions and electron-impact ionization reactions that
became available at that time. The niuic oxide reactions
have been reviewed separately by Hanson and Salimian' in
1984. The Park and Menees' values are modified slightly
in the subsequent works of Park*-'' in order to be compat-
ible with the radiation data obtained in shock Nbes at the
post-shock temperalures in excess of 15,000 K.
Parkg-'O and Candler and his c ~ w o r k e r s ~ ~success-
-'~
fly reproduced numerically the experimentally-observed
aemthermodynamic and radiative properties of the flows in
shock tubes and around hypersonic objects using the modi-
fied Park and Menees' set of rate coefficients. An indepen-
dent study of Wong and Bussing" also found the same set
to be most reliable. However, such validation of the model
was done only for either the non-ionizing or the weakly ion-
izing regime wherein the vibrational excitation and dissoci-
ation are the only significant reactions. Therefore. the reac-
tion schemes and the rate values involving the ionic species
cannot be considered vali-. The ionic reactions would
be important in a hyperbolic Eanh entry flights such as that
expected for the Mars-mm vehicle.
Considerable amount of experimental data on ionic re-
actions,especially on associative ionization and charge ex-
change, have been obtained since the late 1960's which
have not been incorporated in any reaction package, includ-
ing that by Park and Menees. The primary object of the
 present work is to update and modifythe reaction rate Coef-
ficient set of Park and Menees by incorporating these data.
Secondarily, the present work incorporates the recent work
of ParkI6 in which the experimental data on dissociation
rates of 02 and Nz obtained prior to 1970 are interpreted
using a multi-temperature model. T h i i y , for the NO ex-
change reactions and the electron-impact ionization reac-
tions for which the recommended values in Park and Me-
nees’ package are retained, the present work provides the
reasons for the particular choices. Thmugh these, a new
complete set of reaction rate coefficients is derived for use
in computing the highly ionized environments amund the
hypersonic vehicles flying in air.
The validation CalcuIation by Park and Candler used a
multi-temperatllremodel in which the dissociation rate co-
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efficients are assumed to be a function of the geomenic au-
erage temperature between the translational-mtationationaland
the vibrational-electronic temperatureTo =a. constant,
where. E is the energy of the reaction and k is the Boltzmann
The vi-
and T. is the temperature controlling the reaction
brational temperature is calcualted in turn using an elab-
orate procedure. Park and Candler show that the model
is essential in reproducing the existing experimental data
numerically. However, the rate Coefficients used in these
calculations were those obtained by interpreting the exper-
imental data using the traditional one-temperature model
which assumes that the vibrational temperature is the same
as the translational temperatm.
The multi-temperature model accounts. among others,
for the fact that a large amcunt of vibrational energy is re-
moved during dissociationbecause the dissociation process
occurs mostly from the high vibrational states. As a result,
the higher the rate coefficient. the lower becomes the vibra-
tional temperature during the dissociation pnxess, which in
turn results in a smaller absolute rate of dissociation. For
this reason, the calculated aerothermodynamic properties
are relatively insensitive to the choice of the dissociation
rate coefficients in the multi-temperature model. Conse-
quently, the change made in the rate coefficient values for
the dissociation reactions will not alter the results of calcu-
lation by Park and Candler.
General Remarks
In the high temperature air environment arowda hyper-
sonic vehicle flying in air, the following I1 species must
be consid& Nz. @, NO, N, 0, N;, q,NO+, N+,O*.
and e-. The significant reactions occurring among these
species are listed in Table I. Most of the reactions appear-
ing in the Table have already been considered in the reviews
mentioned in Inmduction. The only diffmnce exists for
the electron-impact dissociation, reaction No. 16, and the
chargeexchange reactions, reactions 24 through 33 in the
Table.
The reaction scheme by Parklo contains the electron-
impact dissociation of NZ,@, and NO. None of these re
actions has ever been studied experimentally. Nevertheless,
for NZ,the pmess
Nz + e e N + N + e
is liely to be very fast, because the vibrational excitation
ofNz bythecollisions ofelectrons is v e r y f a ~ t ’ ~Forthis
.’~
reason, this reaction is retained in the present list, Table I.
The corresponding reactions for Oz and NO are expected .IJ
to be small because the electron-impact vibrational excita-
tion rate coefficients are. very small for these mo~ecules.”
Therefore, they are. omitted in the present list. The list of
charge-exchange reactions is chosen from the data base yet
untapped in the early reviews.
One can regard either the endothermic or the exothermic
reactions as the forward reactions. In the present work,the
endothermic reactions are taken always to be the forward
reactions. The forward reaction rate coefficient is written
in the form
kf = CT.”exp(-E/kT,) ,
rate. In the nonequilibrium environment encountered dur-
ing the hypersonic flight in the Eanh’s atmosphere, gen-
d y one must recognize three different temperatures9J0:
the translational-rotational temperature T,the vibrational-
electronic temperahue Tu, and the electron thermal temper-
ature T.. If the vibrational temperatures of different molec-
ular species are not equal, then a multiple vibrational fern-
peraIure can exist. If the coupling among the vibrational
modes of the molecular species is strong. then one has only
one Tu.Because of the strong coupling between the vibra-
tional mode of Nz and T, w T.. When this W
relation is invoked, there remains only two t e m p e r a m , T
and T, = T . As mentioned earlier, Park9*’’ considered the
.
geometricaverage temperatureT . to be the controllingtem-
perature for the dissociation reactions. Since the relative
velocity beween a heavy particle and an electron is nearly
equal to the the velocity of the electron, the reactions in-
volving electrons as a reactant are controlled mostly by the
e l e c m temperatureT . and T, which characterizies the vi-
brational distribution. Since Tvw T ., the rates of such re-
actions become a function almost entirely of T. alone (there
is a small influence of the mtational temperature T).
The purpose of the present review is to select from the
existing experimental data base the most reliable set of val-
ues for the reaction rate constant C and the pre-exponential
power n for use in this multi-temperature environment.
Many of the existing experimental data were obtained in
a one-temperature environment where all three tempera-
hues were equal. Since C and n are defined to be inde-
pendent of the temperatures, their values obtained in a one-
temperatureenvironment are.valid in the multi-temperature
environment.
The chemical reaction rates can be determined experi-
mentally either in a heating environment behind a shock
wave or a cooling environment in the expanding Bow such
as that in a hypersonic nozzle. The expeximents in a heat-
ing environment yield the forward rate coefficients, while‘--’
those in an cooling environment yield the reverse rate coef-
ficients. The rate coefficient for the revme reaction of any
 - Bble 1. Listofreactionsandtheirralecoefficientsforreactionsinair,intheunils~f~~mole-'sec~';Tisthetranslational-
rotational temperam, T, is the electron temperahue, and To is the geometrical average between T and the vibrational
temperahue T., T. = a.
No. Reaction Reaction Recommended Remark Park (Ref. IO)
Energy, Rate Expression,
-ole cm3mole-' sec-I

1 Q+@-+O+O+Q 118.1 2x I d ' T,-'~sexp(-59,5001r,) 9 . 6 8 ~ld2T,-z exp(-59,500flo)

2 02+NO-+OeOcN0 118.1
3 Q+Nz-+O+O+N2 118.1
4 @+O-+o+ocO 118.1
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exp(-59,500/T,,) Estim 9 . 6 8 ~ld2T,-Zexp(-59,500flo)
2 ~ 1 d ' T exp(-59,500/r.)
'~ 9 . 6 8 ~ld2T,-2exp(-59,500fle)
1d2c1.5exp(-59.500&) 2 . 9 0 ~I ~ ~ 2 e x p ( - 5 9 , 5 0 0 f 1 0 )

5 Q+N-+OeOcN 118.1 ld2c1.sexp(-59,500/r.) Estim 2 . 9 0 ~l ~ ~ z e ~ p ( - 5 9 , 5 0 0 f I ' J

6 NO+Q-+N+O+NO 162.5 5~10~~exp(-75,5OC/r.)

7 NO+NO-+N+O+NO 162.5 I.lx 10'7exp(-75.500&)
8 NO+Nz -iN+O+N2 162.5 5x 101sexp(-75,500/r.)
9 NOCO+N+O+O 162.5 l.lx 1017exp(-75,500/r,)
10 NO+N-+N+O+N 162.5 l.lx 1017exp(-75,500/To)

It N2+&-+N+N+02 225.1 7 x Id'T;'" e ~ p ( - 1 1 3 . 2 0 0 ~ ~E)stim 3 . 7 0 ~Id'?;;'.6exp(-113,200/T,J

12 NZ+NO-+N+N+NO 225.1 7 x 1d1c1.6 exp(-113,200/r.) Estim 4 . 9 8 ~ld'?;;1.6exp(-113.200/Ta)
13 Nz+Nz-iN+N+Nz 225.1 7 ~ 1 d ' T ' .exp(-113,2CO/Tn)
~ 3 . 7 0 ~Id'~1.6exp(-113,ZOC&)
14 Nz+O-+N+N+O 225.1 3x ld2q1.6exp(-113,2COflo) Estim 4.98~Id'1;;'~~exp(-113,Z00fl~)
r1.6
- 15
16
Nz+N-tN+N+N
Nz+e-+N+N+e
225.1
225.1
3x 1d2c1 .6
exp(-113,2CWDn)
9x I P T ; ' " e~p(--113,2CW~~)Estim
1.60x Id2 exp(-~13,200fr0)
8.30~1~T;'~~exp(-113,200fl.)

17 Nz+O-tNO+N 75.19 10'7T' exp(-3837O/T)

6.4~ 6.4 x IO' T1
exp(-38,370m
18 NOCO-tQ+N 31.83 8.4~
1O1*exp(-19,45Om 8Ax 10'2exp(-19,450/D

19 N+O-iNO++e 63.65 5 . 3 1012exp(-32,000m

~ 1.53x IO9 exp(-32,ooOm
20 N+N-+Nt+e 134.2 2x 10'3exp(-67,500/r) 1 . 7 9 ~109'l?,n exp(-67,500m
21 OFO-tO;+e 160.3 I.lx lOI3 exp(-80,600/r) 3 . 8 5 ~109'P.49exp(-80,600/r?

22 o+e-+O++e+e 314.1 3 . 9 ~1d3T;3.78exp(-158,MOFe) Estim 3.9~1d~T;~~~~exp(-158,500~~)

23 N+e-tN++e+e 335.1 2 . 5 ld3T;3.*2
~ exp(-168,600/1;) 2.5 x Id3T;3.82
e~p(-168,600~~)

24 NO++O+N++ 153.4
25 Oi+N-+N++& 56.74
26 NOCO'-+N'a 30.48
27 O;+Nz -iNi+Oz 80.95
28 O~+O-+O++o2 35.75
29 NO'+N-+O*+Nz 25.37
30 NO++-Oi+NO 64.81
31 NO++O-+O;+N %.64
32 O'+Nz-+N;+O 45.20
33 NO'+N-+N;+O 70.57

3
 reaction is uniquely related to the forward rates through the
equilibrium constant & (detailed balance relationship) in
the form
k = kr/&
if the distribution of the internal states of the reactant
species is independent of time and is uniquely determined
by the thermodynamic state. Such a condition can exist
only if the internal states of the reactant species are pop-
ulated according to the so-called quasi-steady-state distri-
bution. The quasi-steady-state distribution is one in which
the rates of inward and outward collisional transitions for
any state are both independently much larger than the rate
of temporal change of the population of that state. only
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It is traditional to assume that the atomic recombination
rate is a function of the translational temperature, T,alone.
This is based on the intuitive argument that the reactants
do not possess the vibrational mode in this case. However, '4
the vibrational temperalure does affect the reverne rate in-
directly because the highly vibrationally-excitedmolecules
tend to dissociate easily, that is, a "backstreaming" transi-
tions occur. In any cooling environment, the observed re-
combination rate is a dif€ere.nce between the sum of all re-
combining transitions and the sum of all dissociating tran-
sitions. Therefore, the dissociation of these highly-excited
molecules caused by high vibrational temperature affects
the effectiverecombination rate. Furlherresmh is needed
to determine the atomic recombination rates in general.

under this condition, the temporal change term can be set Table 2. List of experiments for determination of rates of
to zero, so that the populations of the internal states be
come a function of the thermodynamic state independently
dissociation of Q and NZ .
of time. The quasi-steady-state condition is usually satis- Author(s) Measured Instrument Methodof M
fied for the electron-impact ionization and ionic reccmbm- quantity -ation rate ccef-
tion processes, because these processes are dictated by the ficient det-
collisions of electrons which are usually very fast For chis ermination
reason. the ionization rates can reliably be deduced from the
recombination rates determined in an expanding flow,and &.+M--r O+O+M
vice versa However, for mast other reactions,the quasi-
steady-state condition does not exist behind a shock wave, Mathews total time-frozen overilu 0 2
and therefore. thedissociation ratescannotbe deducdfrom density Mach-Zehnder profile
the measurements made in an cmling flow, or vise versa. Byron total Saeak overall a.0
The techniques for calculating the equilibrium constant in- density Mach-Zehnder profile
troduced in the detailed balance relationship are well estab- V
lished even for the very high temperature environment en- SchexnayderQ density1550 A initial O2
countered in the aerospace applications (see., e.g. Ref. 19), and Evans absorption slope
and therefore will not be discussed here. Genedov 02 density2245 A initial 02.N~
Lesov absorption slope
metal total X-ray overall q.0
density absorption profile
Camac and 02 density1470 A initial Q.0
Vaughn absorption slope
N?.+M-r N + N + M
cary total time-frozen overall N2,N
density Mach-Zehnder profile
Byron total Sneak overall N2.N
density Mach-Zehnder profile
Appleton N2 density1176 A initial N2.N

. et al absorption
Hansonand end-wall pressure
slope
overall N2.N
Baganoff pressure gage profile

Similarly, between the associative ionization such as

N+O -+NO*+e
Figure. 1. Rate wfficient for thermal dissociation of 9by and its reverse reaction (dissociative recombination) such'
the collisions of Q determined experimentally using one as
temperature model.and the two recommended curvefiu. N+O t N O + + e ,
 the principle of detailed balance must be applied with a
caveat. A majority of the electrons approaching the ion p s -
sesesanangularmomentumwithrespecttotheiontoolarge
Y
for a stable molecular complex to form. Consequently, the
resulting complex disintegrates back to the ion + electron
state rather than fall into the potential splitting into two
atoms. The rate of transition from the complex into the
splitting potential depends partly on the vibrational disai-
bution of the molecular ion. Thus. the dissociative recorn-
bination rate is mostly a function of T. and T,. The rate of
associative ionization, on the other hand, is mostly a func-
tion of the translational temperature. However, because of
the "backsueaming" transitions mentioned above, the two
rates can be affectedweakly by the temperatures controlling
their respective reverse rates. Such considerations must be
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& molecules. In air, the most important third body M is
either 9.0,or Nz . The techniques used in the exper-
iments are summarized in Table 2. Since Oz dissociates
sipikantly at tempemms above about 2.000 K, the low-
temperature limit of these experimental data is about 2,000
K. The high-temperature limit is set by the experimental
limitation: when the temperature becomes high, the rates
become too large to be resolved accurately, unless the Row
density is reduced. One can not reduce the flow density be-
low a certain limit. because the sensitivity of measurement
becomes poor. This limitation sets the high-temperature
limit of the measurement of this process at about 7000 K.
In all these measurements, a short incubation time was
observed immediately behind the shock wave before the on-
wtofdissoc&ion. ms was ataibuted by all investigators

extended to all other types of reactions. to the vibrational excitation process. They have assumed

I T
o2 + 02-o+ 0 + o2
1 02*N2-oro*N2 1. o2 + 0 - 0 *ot 0

h
OPEN: 1.1 OPEN: 1-T
SOLIO: 2.T S O L I D 2.1

0 0 MATHEWS
0 W BYRON
o +
SCHEXNAYDER
AN0 EVANS
A A GENERALOV
AND LOSEV
v T RINK.181

t
0 OCAMAC
AND VAUQHN
1021~,-l.5,-595Wlr~' 0 0 GENERALOV 0 *BYRON
AND LOSEV- 0 aRlNKn.I

1s 2.0 26
I
3.0
Ilb) , ,
1s
,
2.0
, ,
2s
I
IC) ,
1.6
, ,
2.0
, ,
2s
104rr, to4rr.. K-1 104rr. 1o4rr.. K-' io'lr, 104rr.. ~ - 1

Figure 2. The rate coefficienu for thermaldissociationof & by the collisions of & ,0,and Nz determined experimentally
using the onetemperature model, and the those determined using two-temperature model.

that the vibrational excitation process ends before disso-

Reactions of Neutral Species
Thermal Dissociation of (h
The rate coefficients for the thermal dissociation of 9.
&+M -O+O+M,
where the colliding third-body species M is an air species,
were measured in References 20 to 24. (There are sev-
eral additional experiments in which M is argon. These
data are irrelevant for the present purposes, and therefore
are not included.) These measurements were made behiid
the primary shock in a shock tube. The rate coefficients
were deduced from the rates of change of global flow den-
sity or from the rates of change of the number density of
ciation starts, so that, during the dissociation process, the
vibrational temperature was equal to the translational tem-
perature. That is, a one-temperature model was used. In
Figure 1, these experimentaldata are compared in an Arrhe-
Nus plot As seen in the figure, the deduced rate-coefficient
values differ by an order of magnitude between the largest
and the smallestobtained values over the tested temperature
range. The largest deviation is seen for the data of Schex-
nayder and Evans?'
In 1968,Johnston6 reviewed, assessed the reliability of,
andrecommendedabestestimateoftheratecoefficientdata
for the reactions involving oxygen. His review covered the
recombination raw measured at room temperature, as well
as the high temperafure dissociation data. He put particular

5
 emphasis on reconciling the high-temperature and the low-
temperature data. In 1969, Bermes made a similar review
for thereactions of interest in atmospheric entry flights. His
review covered only the high-temperature data obtained in
the shock lube. In Figure 1, the two expressions re.€om-
mended by the reviewers are compared with the experimen-
tal data for the case of M = 0,. As seen in.the figure, there
is only a small difference between the two recommended
expressions.
In 1988, Park reinteqreted the experimental data us-
ing atwo-temperaturemode1.'6The two-temperaminter-
pretation enabled Park to numerically recreatethe observed
quantities more closely than by the one-temperature inter-
pretation. Moreover, all existing data for the same reaction
could be reproduced using a single set of the C and n val-
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A question arises about the maximum temperature to
which these recommended rate coefficients can be used. In
flight, the translationaltemperature can reach over 50,000
K immediately behind the normal shock wave. Exmp- w
olating the one-temperature rate coefficients (which have
been determined for the range of up to about 7.000 K) to
such t e m p e r a m is not justified. However, in the multi-
temperam model, the average temperature To does not ex-
ceedabout 10.000Kbefore02 isalmosttotallydissociated.
Hence, the two-temperture expression can be considered to
be useful even when the hanslational temperature exceeds
50.000 K.The rate coefficient values chosen he= chould
be considered veriIied, beucuse they are virtually the same
as those used by Park99'0 and in their calcu-
lations.

ues. The rate expressions deduced by the two-temperature

model in that study are I3 -
W,*O-NO*N
(02+02 -,0+0+0,)
aQxLm
kf = 2 x 1021T;1.5exp(-59,500/T.) , 6 x 10"T"up(--)
18403
T

(9+Nz - + O + O + N z )

kr = 2 x 102'T;1~5exp(-59,500/T.),

(02 +O-+O+O+O)

kf = 1 x 10"T;'.sexp(-59,500/T.).

These expressions are compared in with the original one-

temperature data in Fig. 2. The figure shows that the scatter
among the existing data becomes small when they are inm-
preted by the two-temperature model using the present set
of expresions. They are recommended in W l e 1 for this
reason.
For the cases where M = NO or N, no data are available.
7-
Following the practices of Borne$, theratecoefficientsare
estimated for these reactions to be the same as for that for
Ch and 0.respectively, as
6-
(0, + N O - + O + O + N O )

kf = 2 x 102'T;1~5exp(-59,500/T,),
(a+ N + O + O + N )
u
5~ I 2 3 4 5
lull

kr = 1 x IO 22 T,-15 exp(-59,500/T.) Figure 3. The rate coefticient for the reaction N2 +0+
NO+N.
In Table 1,the rate coefficient expressions mommended
here are compared with those of Park." The main differ- Exchange Reactions Involvinn Nitric Oxide
ence between the two is on the pexponential power n
At 2.500 K, the two sets yield approximately the Same rate
The rates of the two exchange reactions involving NO,
values.
Nz+O+NO+N,
There are no independent measurements of the rate coef-
ficients for the reverse reactions for this process, that is. the
NO+O - 1 9 + N ,
threebody atomic recombination reactions.Therefore, one
must deduce them from the forward rate coefficients using canbemeasured bystudyingthereactionsinashock-heat&
the detailed balance relationship discussed in General Re- gas mixture containing NO, N q ,or N2 0. Since NO emits'. '
marks, even though, as stated therein. the accuracy of such infrared radiation at about 5.3 pn, the rate measurement
a process is doubtful. is made by observing the changes in the emission at this
 wavelength. Otherwise, the extent of absorption of the CO
laser radiation at 4.5 p by the test gas is used as the measure
./ of the NO concentration. The existing experimental data
are contained in References 24 through 36.
Figure 3 shows the existing data on these reactionsin the
temperature range above 2,000 K. As seen here, the data
have been taken at temperatures below 4,000" K. All data
have been interpreted assuming that the vibrational states
are in equilibrium with the mslational temperature, that
is, using the one-temperature model. Withii the measured
temperature range, all data agree fairly closely, that is, to
within a factor of 3. According to Monat et al.,7P4 the mea-
sured data can be represented approximately by
(Nz+O-tNO+N)
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not have a large negative n, because such would imply a
negative barrier. Considering that the n value for 9 dis-
sociation,which has areaction energy of 118 kcal/mole, is
-1.5, it would seem appropriate to assume n for the ex-
change reaction, with a reaction energy of 75 ECaVmole,
to be about -1. Taking n to be -1, and demanding that
the experimental data at 4,000 K are reproduced,the most
appropriate expression of the rate coefficient for the high
temperature range becomes
(Nz +O-+NO+N)
kf = 6 . 4 x 10'7T-1exp(-38,370/T), .
This recommended expression is shown in Fig. 3 for com-
parison,and is Listed in Table 1as the recommended value.

kf = 1.84 x 1014exp(-38,370/T). 12
Since the reaction energy for the exchange reaction is rela-
tively small (smaller than those for the dissociation reac-
tions of 9, Nz, or NO), the reaction rate coefficient is
IE
likely to depend mostly on the thermal energy of the col-
lisions and the steric factor than on the vibrational tempera-
ture of the reactant molecules. The numerical experimenta-
tion in which the radiation data is reproducd0 shows that
the existing radiation data cannot be reproduced unless T
is considered to be the only c o n t d i i g temperature for this
reaction.

+
13

17 c\ po+o--h+tj
raxLm
n, .n -I* * I* + m

-L
-
"€
i IO-
% 7
0 a5 1.0K
IP I
S 2.0
9-
Figure 5. The rate coefficientfor dissociationof N2 by the
E collisions of Nz and N.
El B- 0 WRAYmdTEARE
$
LL
V KAUFMAN md DECKER
0 KAUFMANmdKEIJO -,iP 4 shows the existing data for the reaction NO

't A H,4NSONud
+ 0 -+ N + 9. As seen in the figure, the existing data
agree among themselves fairly well. Hanson et al?7rec-
ommended the expression
6
0 I 2 3 4 5 6 7
WIT kf = 2.36 x 109Texp(-19,45O/T)
Figure 4. The rate coefficient for the reaction NO + 0 +
02 +N. for the temperature range b m 300 to 2000 K. Hanson and
Salimian7 recommended the expression
The last expression has a temperature-independent pre-
exponential factor, n = 0. It leads to unrealistically large kf = 3.81 x 1O9Texp(-2O,820/T)
rate coefficient values for very high temperatures (T above
about 20,000K). This problem can be remedied if a nega- for the temperature range from 1500 to 5000 K. These ex-
tive n value is given. The existing data do not extend pressions have a n-value of +I, and leads to unrealistically
-- sufficiently high temperatures to enable determination of
the pre-exponential power nin the high temperatm range.
large rate values at very high temperatures. For the same
reason as for the Nz + 0 reaction above, it would be ap-
The magnitude of n should be dependend partly on the re- propriate to assign a smaller n value here also. Since the
action energy: a reaction with a small reaction energy can reaction energy is only half that of the Nz + 0 reaction, an

7
 n value of approximately zero would be more appropriate
for thii reaction. By fitting the experimental data with n =
0, and requiring that the resulting expression fit the data at
3000 K, one obtains
(No+o-+or+N)
kr = 8.4 x 1012exp(-19,450/T)
for use in the temperature range above about 3000 K.This
expressionisshowninFig. 4,andrecommendedinTable 1.
Since the forward rates of these two exchange reactions are
conh.olled by T, the reverse rates should also be considered
a function only of T. The rate coefficient values for these
two reactions are identical to those in the original set by
parklo used in h i validation calculations. Therefore the
Downloaded by IOWA STATE UNIVERSITY on September 25, 2014 | http://arc.aiaa.org | DOI: 10.2514/6.1989-1740
rate coefficient values chosen here should be regarded as
verified.
Figure 6. The rate coefficients for thermal dissociation of
Nz by the collisions of Nz and N determined experimen-
tally using the one-temperture model, and those detennind
using two-temperature model.
Thermal Dissociation of N,
Molecular nitrogen in air dissociates mostly through the
exchange reactions mentioned above. To a minor extent, it
dissociates through the impacts of heavy particles
Nz+M -+N+N+M.
The main colliding particles in this case are NZ,N, and 0.
Nihogen molecules absorb strongly at about 110nm, and so
its density can be measured using absorption specnoscopy
at this wavelength. The rate coefficient for the nitrogen
dissociation reaction can be determined from the rates of
change of bulk gas density or of Nz density or the rate of
disappearanceof NZ . identical to that used by Park'' (seeTable 1). The revene
The rate coefficient for this reaction was measured in
References 38 to 41. The techniques used in the measure-
ment are summarized in Table 2. The existing data for the
case where M = Nz. shown in Figure 5, cover a tempera- W
hue range of up to about 15,000" K. These data have been
interpreted differently baween B o m r and Baulch et al.
ParkI6 reinterpre.ted the experimental data using the
two-temperature model, and deduced the best-fit parame-
ters. The rate parameters so chosen am
(N2 +Nz - i N + N + N z )
kf = 7 x 1021T;1.6e~p(-113,200/T8),
(Nz + N - t N + N + N )
kr = 3 x 10"T;'"exp(-113,200/Ta) .
These values are recommended in Table 1, and compared
with the values used by F'ar"'. As seen here, the two sets
are only slightly 3fferent. considering that the flow prop-
erties are relative.y insensitive to the rate coefficient val-
ues for lhis reaction. The present expressions are compared
with the original data in Figure 6.For the rest of the M's the
rate values are estimatedas indicated in the Table. The rate
coefficient values chosen here should be regarded as ver-
ified, because they are virmally identical to those used by
Park9-loand Candler11-14 in their validation calculations.
Also, in Reference 42, the flow field mound a cylinder is
calculated using the present set of rate coefficients. The re-
sults are compared with the experimental data. Excellent 'i/
agreement is seen betvreen ths data and the calculations.
Since there is no independent measurement of the
reverse-rate coefficients, one must resort to the detailed bal-
ance relationship in order to deduce them from the forward-
rate coefficients, even though the procedure is not reliable.
Electron-ImDact Dissociation of N,
In References 9 and 10, Park pointed out that the exist-
ing radiation data taken in shock tubes can be reproduced
numerically only by assuming that the rate coefficient for
the electron-impact dissociation of Nz
Nz +e -+N+N+e
is several hundred times faster than those by the collisions
of neutral m s . The rates of this reaction is controlled by
the electron temperature in both forward and reverse direc-
tions, because the relative velocity of encounter is almost
equal to the elecnon thermal velocity. However the exact
value of the rate coefficient could not be determined from
the numerical experimentation. By assuming that this rate
coefficient is 300 times m e r than that for N2 + 0 --, N+
N + 0.one obtains
(N2 + e + N + N + e)
rC, = 9 x 10~T~'"exp(-113,200/T.),
I
I
which is recommended in W l e 1. 'Ihi expression is nearly
 rate coefficientcan be deduced from the forwardrate coeffi-
cient through the use of the equilibrium constant evaluated
at T.. For the molecules 9, and NO, the corresponding
v
process can be ignored, as mentioned in Introduction. The
rate coefficient chosen here is compatible with the existing
experimental data, and therefore can be considered as veri-
fied,though not rigorously.
Thermal Dissociation of Nitric Oxide
As mentioned. Nnic oxide NO emits radiation at 5.3 p.
and so its concentration can be determined without much
difficulty. The rate coefficient for the reaction
NO+M - + N + O + M
Downloaded by IOWA STATE UNIVERSITY on September 25, 2014 | http://arc.aiaa.org | DOI: 10.2514/6.1989-1740
for the same purpose. Koshi et al. measured the intensi-
ties of emission at 4.87 and 5.22 pm. From these, vibra-
tional temperature and NO density were determined simul-
taneously. The three sets of data are compared in Fig. 7
for the case M = NO. Bormer recommended the C and n
values of Wray and Teare. Baulch et alp and Hanson and
Salimian' considered none of these data to be reliable and,
therefore, made no recommendation. Considering the fact
that the three sets of data agree to within an order of mag-
nitude, and especially that the data by Wray and Teare and
by Koshi et al. agree to within a factor of 3, it would seem
prudent to assert that this rate coefficient can be considered
known. The data by Koshi et al. should be considered most
accurate because the Vibrationaltemperature variation is ac-
counted for. Thus the recommended rate expression is that

by Koshi et al. with T replaced by T.:

should be measurable in principle by studying the rate of
disappearance of NO behind a shock wave. However, this
procedure is quite difficult because of the competing ex-
change reactions. The N and 0 atoms produced by the reac-
tion react with NO through the NO exchange reaction pm-
cesses described above. It is especially difficult to separate
the effectiveness of the various colliding partners M present
in such an experiment.
&I NO,
= 0,or N)
kr = 1.1 x 101'exp(-75,500/T.).
Koshi et al. considered the rate coefficientsfor M = Nz
and 9 to be 1/22 of those for NO, 0, and N. In Table 1.
these values are shown as the recommended values. The
reverse-rate coefficients for the process must be deduced
from the forward-rate coefficients, even though the proce-

'I
dure is not reliable. The present set of coefficient expres-
\
\ -
No +NO N + O +NO sions is quite different from that used by Park." However,
\ this point is immateriak the accuracy of the rate coeffi-
- II \
\
\ -
cients for this process is immaterial in the calculation of
the flow field around a hypersonic object, because most NO
molecules are removed through the exchange reactions de-
scribed earlier, rather than through the thermal dissociation
process.
Reactions Involving Ionized Species
Dissociative Recombination and Associative Ionization
The rate coefficients for the exothermic dissociative re-
combination reactions
N+0 t NO+ + e ,
N+N tNzf+e,
O + 0 -0; + e ,
have been measured by several different techniques. The
--- rates of these reactions are dictated by the electron thermal
5
0 I
KOSHle<d

2
, \ ,
3 4
temperature T, and the vibrational and electronic tempera-
tures of the molecular ions. If. further, the vibrational and
ld/t electronic temperatures of the ions can be assumed to be
Figure 7. The rate coefficient for thermaI dissociation of qual to T., then the rate coefficients become a function
NO by the collisions of NO. only of T,. Because of the strong coupling between the
vibrational mode of Nz and electron thermal mode, the as-
Nevertheless, the rate copefficienthas been measured by sumption T. M T, is probably well justified in air. Dunn and
Freedman and Daibe~?~ Wray and Teare,% and Koshi et Lordi4547 and Eschenroeder et al." studied the rates of
Freedman and Daiber determined the rates of change change of electmn density in an expanding flow produced
- of the concentration of NO by measuring the rates with by a shock tunnel using Langmuir probes and microwave
which the absorption intensity of the radiation at 2,465 A detectors, and the expressed the rate coefficients as a func-
changed. Wray and Teare used the wavelength of 1,270 A tion of Te. Dunn and Lon3 measured electron temperature

9
 simultaneously with the electron densities. The prcssure
.- in the reflected-shock region in these experiments was be-
tween 10 and 50 am.The temperature was such as to pro-
duce a weak dissociation. The observed changes in electron
density in the expanding nozzle were amibuted to the dis-
sociative recombination reactions.
Downloaded by IOWA STATE UNIVERSITY on September 25, 2014 | http://arc.aiaa.org | DOI: 10.2514/6.1989-1740
mzcna(-nmt*l
Figure 8. The rate coefficientfor dissociative recombina-
tionNO+ + e + N + O .
Although the experiments are saaightforward, the va-
lidity of the interpretation has not yet been satisfactorily
demonsuated for this particular technique. The expand-
ing flow in a nozzle tends to be in equilibrium in the up-
slream =@on where the density is high, and fmzen in the
downstream region where density is low. The method thus
measures the rate coefficient prevailing at around the f?eez-
ing point For the N; + e and 0;+ e reactions, the pres-
ence of N+ and 0 ' cannot be ruled out because the charge
exchange reactions N; + N + NZ + N+ and 0;+ 0
9 + Of require only a small energy and therefore. could
be fast (The charge exchange reactions converting NO+
ions to other ions usually take a substantial energy.) The
atomic ions tend to recombine mostly through the radiative
recombination processes at such low electron densities.
Eschenroeder et alp9 attempted to deduce the rate coef-
ficient for NO+ recombination from the observed rate of
decay of electron density in the wake of a sphere flying
through a ballistic range. The rate coefficient deduced from
this experiment was 25 times larger than that &mined from
the expanding nozzle experiment This casts doubt on the
validity of the both methods.
Nitric oxide ion NO+ can be produced in a flame also.
From the r a m of change of electron density in the flow of
bumed gas, one can deduce the NO++ e rate?' In a flame,
the diffusion phenomenon is significant, and tends to affect
the net rate of change of electron density.
More precisely conmlled experiments were conducted
using electrical discharges. For this purpose the molecu-
lar test gas, NO, Nz, or a, is mixed in abath of anoble
gas such as neon. An eleceical current is passed through
the mixture at a pressure of a few Torr over a time period
t y p i d y of a few hundred microseconds. This time is suf-
ficiently long to ionize the molecules to form the molecular
ions to be studied, but insufficient to establish a total equi-
librium. The rate coefficient is deduced from the rate of 4
decay of electrons or rate of formation of atoms. Electron
density can be determined either with a Langmuir probe,
microwave detector, or simple conductivity detector. The
rate.of formationof atoms is determined using a mass spec-
trometer. Such measurements can be &ne either in a static
chamber, a flowing tube, or in a shock tube. In the shock-
tube experiment, theelectrical discharge is made shortly be-
fore the anival of the primary shock.
I@' : Q Id P 4 6 rd
--nmT.I
Figure 9. The rate coefficient for dissociative recombina- W
tionN; + e + N + N.
Results of such experiments are given in References 51
to 61. In Figure 8, these experimental data are compared.
As seen in the figure, all existing data agree fairly well
except those obtained by Burdea and Hayhurst?o using a
flame and those obtained by Dunn and Lordi4' in an ex-
panding nozzle. If the data by Dunn and Lardi are inter-
preted to be valid only at the freezing point, which was
about 2500 K for this case, then they agree with the rest
also. The best mean seems to be
(N + 0 + NO' + e)
k, = 9 x 10'8T;o." .
In Figure 9, a similar comparison is made for the N; +
e In the nozzle expansion experiment by
DUMand h r d i , freezing occurred at about 4,000 K. Their
value at this temperamagrees approximately with the rest.
The best mean for this reaction seems to be
(N+NcN;+e)
k, = 2.7 x 10'8T;o.s .
In Figure IO, a similar comparison is made for the 0;
+e For this reaction, all existing
data agree fairly weU except the nozzle data of Dunn and\-'
Lordi?' Thefi'eezingpointinDunnandLardi's experiment
was about 2,500 K. The discrepancy between the nozzle
 flow data and the rest could be amibuted to the 0;+ 0 + (N + 0 -+ NO' +e)
O2 + O+ charge-exchange process. Ignoring these data,the
32,000
best fit seems to be kf = 5.28 x 1012 exp(--
Y ( O + O t O $ +e) T ),
(N+N-+N;+e)
kr = 1.5 x 101sT:0.5 .
67,500
kf = 2.04 x 1013exp(--
The rate coefficients for the reverse reactions to the T ),
above three dissociative recombination processes, that is,
the associative ionization rates, are calculated from the (O+O-+O; +e)
above three expressions assuming that the forward and re- kr = 1.12 x 1013exp(-- 80,600
verse rates are related by the equilibrium constants evalu- T )
ated at the elecmn temperam T. of 3000 and 6OOO K.
The resulting expressions are assumed to be a function of These expressions are recommended in 'hble 1. The re-
the heavy-particle translational temperature T.The result- verse rate coefficients k, should be deduced from the last
Downloaded by IOWA STATE UNIVERSITY on September 25, 2014 | http://arc.aiaa.org | DOI: 10.2514/6.1989-1740

ing ratecoefficient expressions are: set of expressions through the use of the relationship

kr = k f ( T J / L ( T c ) .
Validity of the choice of this set of rate coefficient values
has not yet been verified by a systematic comparison with
the experimental data.

Id 2 4 Q lo'
.uo.o*IoIIuIIyuL'

Figure 10. The rate coefficient f a dissociative recombina-

tionO;+e+O+O.

( N + O - + N O ++e)
T 32,000
k = 5.28 x IO"(-
6,000
)exH-- T 1,
( N + N - + N ; +e)
T 67,500
kf = 2.04 x loL3(- )'.5ex~--
6,000 T ) 0 I 2 3 4
1un
(O+O-tO;+e) Figure 11. The rate coefficients for associative dissociation
reactions N + 0 + NO' + e, N + N -+ Nt + e, and 0 +
0 -+ 0;+ e deduced from the dissociative recombination
rate coefficients.
These deduced rate coefficients are shown by solid lines
Elecmn-Immct Ionization of Atomic S m i e s
in Fig. 11. All these rate coefficients have a positive pre-
exponential power tl for the temperatwe range shown. At It is quite difficult to determine the rate coefficients of
high temperatures,it is unlikely that nwould remain posi- electron-impact ionization of N and 0 atoms directly be-
tive. For this reason,the rate coefficients are. exmpolated hind a shock wave, because of the compounding of other
c-
from 6,000 K to higher tempertures assuming n = 0. The ionization mechanisms. However, in the ionization or ionic
results are shown in Fig. 11 with dashed lines. Their ex- recombination of atoms through the impacts of elecmns,
pressions are the electronic states are very nearly in quasi-steady-state

11
 For this reason, the forward rate coeffi- tion becomes (0+ e -+ O++ e + e)
cient can be deduced from the reverse reaction rate coeffi-
cient.
Park67@ measured the ionic recombination rate of
atomic nitrogen
N+ e + N + + e + e
by observing the rate of decrease of electron density in an
expanding nozzle. The ionization rate can be deduced from
the recombination rate by utilizing the equilibrium constant
for this reaction, in the form
( N + e - + N ++ e + e )
kf = 2.5 x 1033T;3~82ex~-168,200/T.).
The recombination rates of atomic oxygen
Downloaded by IOWA STATE UNIVERSITY on September 25, 2014 | http://arc.aiaa.org | DOI: 10.2514/6.1989-1740
kf = 3.9 x 1033T~3.78e~p(-158,500/Te)
W
These expressions are recommended in Table 1. The re-
verseratecoefficients shouldbededucedfrom thekf values
through the use of the equilibrium constant evaluated at T..
The present values are identical to those used by Park."
It should be noted that these expressions are valid only in
the collisiondominant situation, that is, when the electron
density is suf6cient for the radiation effect to be negligible
in the quasi-steady-state distribution of the internal states.
Such a situation exists at elecwn densities more than about
.
cm" Validity of the choice of these rate coefficient

O+etO++e+e, values has not yet been verified by an independent experi-

have never been measured. However, one canestimate the ment.
recombination rate firom those of similar atoms. Dunn"
measured the rate of recombination of the carbon atom
C, and plotted and compared his results along with those- c
of other atoms. The results are reproduced in Figure 12.
The data include those of argon, cesium, mereu~y'C'*~~, Chargeexchangereactions have been studied in the past
h e l i ~ m , ~and
.'~ as wen as those of carbon and mostly in order to understand and characterize the ionic re-
nitrogen. As seen in the figure, the recombination rate coef- actions occuning in the upper atmosphere. In the upper at-
ficients are fairly similar. If one assumes the recombination mosphere, ionic species are formed mostly by the absorp-
rate of O+ to be the same as that of N*, and assumes the tion of sunlight or the bombardment by electrons. The en-
forward rates to be related to the reverse rates through the suing reactions are all exothermic. In the laboratory, the
equilibrium constant, the expression for the O+recombina- chemical species to be studied are produced by either irra-
diation or electrical discharge, in much the same manner as
inthearmosphere,andtheequilibrationprocessin theprod- V
uct gas is Species densities are determined
using a spectral photometer or mass-spectrometer. There
are. four variations to the technique. In the flowing after-
glow experiment, a steady flow of reacting gas mixture is
produced by an electrical discharge, and the species den-
sities are determined with a spectral photometer (see, e.g.,
k
" 25-
Ref. 77). In the photo-ionization-mass spectrometer tech-
nique, the lequired species are produced by the pulsed irra-
$
E diation of ultraviolet radiation, and the species densities are
E
". determined using a mass-spectrometer!' In the drift-tube
A2
technique, the ions are pulled by an electrical potential, and
24- the drift velocity of the ions are measured (see, e.g., Ref.
e 103). In the crossed-beam technique, the beams of neutral
2 and ion species are produced by separate beam generators,
E
and are crossed. The radiation emiaed in the mixing re-
8 gion is measured to deduce the rate of the reactions in the
5 23-
E regi0n.9~In many of such experiments, the reactant ions
were monoenergetic. These experimental data sources are
8
E summarily listed in Table 3.
22 -
Table 3. List of experimental data source for the rate coeffi-
cients for charge exchange reactions. The rate coefficients
are in the units of cm3sec-' ,
21' ' \ ,
6 Id 2 4 6 lo' 2
ELCC~RON irrrpoum.~~..
K Author(s) Year Method Valueat300K'
Figure 12. The rate coefficients for onic recombination of
wmmon atomic ions. N++&-+NO++O

12
 -+O;+N Johnsen et al 1970 drift-tube 3-l'
-NW+ Lmdinger et al 1974 drift-tube 4.3-l'
Fite et al 1963 afterglow 5-l' KobayashiXaneko 1974 4.6-l'
u
Goldan et al 1966 afterglow 1-9 Lmdinger et al 1975 drift-tube 4.4-I'
Aquilanti,Volpi 1966 afterglow 7-l'
0;+N+NO++O
Stebbing et al 1966 e-beam smallat highT Goldan et al 1966 afterglow 1.8-l'
Wameck 1967 photo-ioniz1.6-1° (NO++O) Fehsenfeld
1977 drift-tube 1.2-l'
4.5-10 (o:+N)
.. I

Dunkin et al 1968 afterglow 66'' N;I+O-iO++Nz

Johnsen et al 1970 drift-tube 5-1° NcFarland et al -
1974 afterglow I-"
Nevnaber et al 1971 cross-beam 5-1° N;I+O-+NO++N
Ru;herford,Vmm 1971 cross-beam Fehsenfeld et al 1969 aftarglow 1.4-j0
McFarland et al 1973 drift-tube 5-10 McFarland et al 1974 afterdow 1.3-l'
Lindinger et al 1974 drift-tube 4.4-10
OKeefe et al 1986 cyclotron branching ratios
Downloaded by IOWA STATE UNIVERSITY on September 25, 2014 | http://arc.aiaa.org | DOI: 10.2514/6.1989-1740

In all these devices. the chargeexchange reactions occur

N;+-iO;+Nz in the exothermic direction, as they do in the atmosphere.
Fehsenfeld e! al 1965 afterglow 1-10 Therefore, all existing experimental rate-coefficient data on
Goldan et al 1966 afterglow 1-10 charge-exchangereactions are for the exothermic reactions.
Stebbing et al 1966 e-beam small at high T In the flow around a hypersonic vehicle, the ionic species
Warneck 1967 photo-ioniz l.1-lo are formed mostly behind a shock wave through endother-
Dunkin et al 1968 afterglow 4.7-11 mic processes. Therefore, for use in the hypersonic flow,
Ferguson elal I969 afterglow 5-11 the endothermic reaction rates must be deduced from the
Johnsen et al 1970 drift-tube 6-" exothermic rate. data by means of the equilibrium relation-
McFarland et al 1973 drift-tube 5-11 ship.
Lindinger et al 1974 drift-tube 5-11 Typical experimental data are shown for the exothermic
pmcess 3+ @ -i 0;+ Nz in Fig. 13. In the figure, the
0++01-+0~+0 abscissa is the energy of the monoenergetic reactant ions.
- Batey et al 1965 afterglow
Copsey et al 1966 anerglow
1.6-"
2-11
In this case, three different technique yield approximately
the same results: Neynayber et alp2 used a crossed-beam
Stebbing et al 1966 e-beam smallathighT technique; Dunkin et al?* used a flowing afterglow tech-
Warneck 1967 photo ioniz 2-" nique: and Johnsen et and McFarland et al.'5 used
Hohme et al 1967 drift-tube 2-11 a drift-tube technique. The relatively close agreement be-
NakshbandiPasted 1967 afterglow 1.7-" tween the different sets of data is typical of almost all other
Dunkin et al 1968 afterglow 2-11 charge-exchange reactions.
Ferguson et al 1969 aftgerglow 2-11 The figureshows that the rate coefficient falls to a mini-
McFarland et al 1973 drift-tub$ 2-11 mum point as the collision energy increases and then again
Johnsen et al 1973 drift-tube 2-11 increases to a maximum. Though not shown in the figure,
Lindinger et al 1973 drift-tube 2-11 Refereme78givesthedatafrom1Oto 100eVshowingthat
O++Nz -iNO++N the rate coefficient falls steadily beyond 10 eV. The initial
Batey et al 1965 afterglow 2.8-" and the second fall occur because the duration of the colli-
Giese 1966 cross-beam 2-l1 at20000K sions is shorter at higher colliision energies. The fact that it
Copsey et al 1966 afterglow 2.4-12 rises in between is an anomaly. The anomalous rise is be-
Stebbing et al 1966 e-beam small at high T lieved to be due to the fact that a reactant, most likely O2in
Wameck 1967 photo-ioniz 4.6-'2 this case. is elecmnically excited because of the bombard-
Bohme et al 1967 drift-tube 7-12 ment of elecmns or ions. The excited @ tends to produce
Nakshbandipasted 1967 afterglow 3.7-12 either vibrationally or electronically excited 0; or Nz .
Schmeltekopf et al 1968 1.4-12 In deducing therate coefficientfor thereverse (endother-
mic) process 0;+ N2 -+ N; + @ for use in the hyper-
Dunkin et al 1968 afterglow 1.2-12
Ferguson et al 1969 afterglow 1-12 sonic flow through the use of the equilibrium constant, one
Rutherford,Vroom 1971 cross-beam must remember that the reactants 0;and Nz are mostly
JohnsenBiondi 1973 drifr-tube 12-12 in the electronic and vibrational ground states. Therefore,
McFarland et al 1973 12-12
the anomalous rise in the exothermic rate must be excluded
Lmdinger et al 1974 drift-tube 12-12
from the endothermic rate calculation. One can represent
the exothermic ratecoefficient data of the type shown in
L'
0; +NO+NO+ +O, Fig. 13 in the region of initial fall by an equation of the
Warneck 1967 photoioniz 7-1° f m
Fehsenfeld et al 1970 afterglow 6.3-1° E = c(E/300)¶ ,

13
 where E is the energy of the monoenergetic monoenergetic
ions expressed in degrees K. The constant c and the expo-
nent q can be determined fromthe experimental data The
experimental data show that the exponent q is either a small

--
negative number (typically -0.3) or zero. Denoting f(w) NO' r0
2 0; + N O
to be the Maxwellian velocity distribution function for the 0; -N N' +OI
velocity w, the rate coefficient for the exothermic process
excluding the anomalous excitation can be written as
m
2 c T 3
k,=4rL ~ f ( w ) w z d w =4- ( - )300
4r(q+z),
Downloaded by IOWA STATE UNIVERSITY on September 25, 2014 | http://arc.aiaa.org | DOI: 10.2514/6.1989-1740

NO' t N
No +O'
-- 0'
N'
+
+

7
0 I 2 3 4 b
1
Gn.

I
I2L
0.1 I 10
rnLLlSION mP(GY.rv
Figure 13. The rate coefficients for the exothermic charge
exchange reaction N; + 9-t 0;+ Nz.
where r (x) denotes the Gamma function of argwnent x.
By dividing this k, value by the equilibrium constant, one
obtains the rate coefficient for the endothermic process. In
both forward and reverse directions, the rate coefficient for
thesepmcessesmustberegardedtobedictatedbytheheavy
particle temperame T,because the effect of excitation is
removed from the consideration.
The rate Coefficients for endothermic charge-exchange
reactions are determined through the above procedure by
using the experimental data contained in References 14 to
103. For the cases in which the exothermic rate coefficient
is known only at mom temperature, the exponent q is as-
sumed to be zero. The endothermicrate coefficients are ob-
tained by applying the above procedure at 5,000 and 10,oOO
K. Theresultingendothermicratecoefficientsareexpressed
in the standard form involving the pre-exponential constant
C and the temperature exponent n These parameters are
given in Table 1. The rate coefficients are plotted in Fig.
14. The validity of the choice of this set of charge-exchange
rate coefficient values has not yet been tested.
Figure 14. The rate coefficients for endothermic charge ex-
change reactionsdeduced fromthe exothermic reaction rate
coefficients.
Conclusions
The existing experimental data on the rate coefficients
forthe reactions in nonequilibrium high temperature airare
reviwed. and a set of values is recommended as being most
reliable. The recommended values are chosen: for the ther-
mal dissociation of 02 and Nz,from the two-temperature
interpretation of old data by Park for the NO exchange re-
actions,fromtheexperimental&taobtainedbyHansonand
his asscciatcs;for the ionization of atomic species, the noz-
zle flow data by Park: and for the associative ionization and
chargeexchange reactions, from the collection of the ex-
perimental data obtained since the late 1960's using shock
tubes or other flowing devices. For the neuaal reactions,
the newly chosen set differs only slightly from that used
previously by Park and Candler in their validation of the
chemistry model. The associative ionization and charge-
exchange rates differ considerably, and are untested.
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Technique for Ion Mobility and Ion-Molecule Reaction
Rate Constant Measurements. 1. Appar;l~sand Mobility

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