1^

NBSIR 73-206

Chemical Kinetics Data Survey

Y. Sixty-six Contributed Rate and

Piiotociiemical Data Evaluations on

Ninety-four Reactions

David Garvin, Editor

Physical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

May 1973

interim Report

Prepared for Climatic Impact Assessment Program, Department of Transportation,

Office of Standard Reference Data, N.B.S.,

and

Measures for Air Quality Program, N.B.S.
I

i
NBSIR 73-206

CHEMICAL KINETICS DATA SURVEY

V. SIXTY-SIX CONTRIBUTED RATE AND

PHOTOCHEMICAL DATA EVALUATIONS ON

NINETY-FOUR REACTIONS

David Garvin, Editor

Physical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

May 1973

Interim Report

Prepared for Climatic Impact Assessment Program, Department of Transportation,

Office of Standard Reference Data, N.B.S.,

and

Measures for Air Quality Program, N.B.S.

U. S. DEPARTMENT OF COMMERCE, Frederick B. Dent, Secretary

NATIONAL BUREAU OF STANDARDS, Richard W. Roberts, Director
ERRATA-NBSIR 73-206, second printing

page 13 Reaction Mechanism, 5th line: delete and NO

^ page 17 Table III:

Heading for columns E, F, G, H and I should read

Absolute rate constants, k/10 cm^ molecule ^

page 38 Table I: 1) The values given for e(T ^ 300 K) for \ = 230,

240, 250, 260, and 270 nm are in units of

5 2 10 cm /mol

2) The value of e(T = 1100 K) at X = 260 nm should

5 2 1.9 X 10 cm /mol

July 24, 1973
Table of Contents

I. Introduction 3

II. Related Reports 5

III . Needed Work 6

IV. Evaluations

A. Reactions of 0('''D) R. J. Cvetanovic 7

B. Reactions of 0(''"S) T. Slanger, K. H. Welge 22

C. Reactions of O^C'^'A) and of SO W. H. Breckenrldge 33

D. Photochemistry of J. Troe 34

E. H + H2O2

1) Comments on data sheet J. Troe 41

2) Reply to comments D. Drysdale 42

F. Photochemical and Rate Data J. Heicklen 43

for CH^ONO, CH^O, and 01^02

G. Reactions of the H2-N2-O2 system D. L. Baulch 49

D. D. Drysdale

D. G. Horne

i
Reactions of the ^2~^2~^2 ^^^^^^ which data sheets have

been contributed by D. L. Baulch, D. D. Drysdale and D. G. Home

N + N + M-»N2+M

N2+M-»N + N + M

N + NO -» N2 + 0

N2 + 0 N + NO

N + NO2 -» NO + NO

NO + NO -» N + NO2 '

N + 0 + M NO + M

NO + M -» N + 0 + M ,

N + O2 -» NO + 0

NO + 0 N + O2

N + 0^ NO + O2

N2 + O2 N2O + 0

N2O + 0 N2 + O2

NO + NO N2O + 0

N2O + 0 NO + NO

NO + NO2 + ^2 ~^ ^^2 ^^3

NO2 + NO^ NO + NO2 + O2

NO + NO^ -* NO2 + NO2

NO2 + NO2 -> NO + NO^

NO + 0 + M NO2 + M

NO2 + M NO + 0 + M

NO + O2 + M NO^ + M

NO + 0^ NO2 + O2

NO2 + O2 -» NO + 0^

ii
+ NO^ + M -» N20^ + M

N20^ + M -» + NO^ + M

+ 0 + M -> NO^ + M

NO^ + M + 0 + M

+ 0^ -* NO^ + O2

NO^ + O2 -+ NO2 + 0^

NO^ + NO^ -» NO2 + NO2 + O2

N + OH NO + H

N2 + HO -» N2O + H

N2O + H N2 + HO

H + NO + M HNO + M

HNO + M~^H + NO + M

H2 + NO HNO + H

H + HNO H2 + NO

NO + HO NO2 + H

NO2 + H NO + HO

H2O + NO -» HNO + OH

HO + HNO -» H2O + NO

HNO + HNO -* n^O + N2O

NH^+M-»NH2 + H + M

NH2 + H + M -» NH^ + M

NH^ + H -» NH2 + H2

NH2 + H2 NH^ + H

NH^ + 0 -> NH2 + HO

NH2 + HO NH^ + 0

NHg + HO NH2 + H2O

NH2 + H2O -» NH^ + HO

iii

1
L I
chemical Kinetics Data Suirvey

V. Sixty -Six Contributed Rate and Photochemical Data

Evaluations on Ninety-Four Reactions

Abstract

This report records the data evaluations contributed to the

Climatic Impact Assessment Program chemical kinetics survey during

the period Nov 1972 - April 1973 by various kineticists and photochemists. Data are included on reactions of 0('''D), 0(''"S), 02(^^),

CH^ONO, CH^O, CH^O^, ^2^2' ^^2' ^^2 H2-N2-O2 system.

Keywords: atmospheric chemistry, chemical kinetics, data evaluation,

gas phase reactions, optical absorption cross sections, photochemistry,

quantum yields, rate constants.

1

I. Introduction

This report is a collection of rate constant evaluations

contributed to the Climatic Impact Assessment Program survey of

rate and photochemical data. These evaluations, data sheets and

comments are background material explaining some of the evaluations

in the CIAP rate and photochemical data tables that are being issued

in a separate report (NBS Report 73-203).

The evaluations have been contributed by kineticists and data

analysts familiar with the available experimental data. The preferred

values given reflect the current state of the art and provide guidance

for modellers on rate constants and photochemical mechanisms.

All of the recommendations given here have been incorporated in

the CIAP tables.

We are indebted to the following persons for the contributions

to this survey that appear in this report:

R. J. Cvetanovic, Division of Chemistry, National Research Council

of Canada, Ottawa, Canada.

T. Slanger , Stanford Research Institute, Menlo Park, California.

K. H. Welge, Centre for Research in Experimental Space Science and

Chemistry Department, York University, Toronto, Canada.

W. H. Breckenridge , Department of Chemistry, The University of Utah,

Salt Lake City, Utah.

3
J. Troe , Department de Chlmle, Ecole Poly technique Federate de

Lausanne, Lausanne, Switzerland.

J. Helcklen, Department of Chemistry, The Pennsylvania State

University, University Park, Pennsylvania.

D. L. Baulch , D. D. Drysdale , D. G. Horne , Department of Physical

Chemistry, University of Leeds, Leeds, England.

4
II. Related Reports

1. Hampson, R. F. (editor) Survey of Photochemical and Rate Data

for Twenty-Eight Reactions of Interest in Atmospheric Chemistry.

To appear in J, Phys. Chem.. Ref. Data 2^ No. 2 (Summer 1973).

These are slightly revised versions of data sheets originally

distributed as NBS Reports 10692 and 10828.

2. Garvin^ D. (editor) Chemical Kinetics Data Survey IV. Preliminary

Tables of Chemical Data for Modelling of the Stratosphere, NBS

Report 73-203 (May 1973). This is a collection of tables from

the preliminary draft of a chapter on Stratospheric Chemistry

for "The Natural Stratosphere" E. Reiter, editor, Climatic Impact

Assessment Program Monograph 1. (1973).

3. Johnston, H. and Garvin, D., Working Papers for a Survey of Rate

Data for Chemical Reactions in the Stratosphere NBS Report 10931

(October 1972) . This describes the survey of rate data being

undertaken for CIAP.

4. Hampson, R. F. (editor) Chemical Kinetics Data Survey VI.

Photochemical and Rate Data for Twelve Gas Phase Reactions of

Interest for Stratospheric Chemistry, NBS Report 73-207 (May 1973).

These are newly prepared data sheets. They supplement reference

1, above, and the present report.

5
III. Needed Work

Although recommendations have been made for rate constants,

absorption coefficients and quantum yields of many of the reactions

thought to be important in the polluted s tratosphere^, much remains

to be done. We will welcome suggestions of the best values to be

used for any of the reactions listed as not evaluated in NBS Report

73-203 (immediately before Table I). These will be incorporated in

the tables. Detailed evaluations will be issued in companion reports

(such as this report).

We will also welcome comments and corrections of any of the

recommendations

.

6
G. Special Cases

G.l. REACTIONS 0? -'("''^2' -^-'^-''^ (R-J- Gvetanovic)

Relat iv e Rate Consta nts at 30 0 K

©('''D^) atoms have long radiative life time and are in general

extremely reactive chemically and susceptible to rapid collisional deexcitation . They are therefore difficult to observe

directly in laboratory experiments. As a consequence, with

relatively fevi exceptions, all the available kinetic information

in the literature is in the form of relative rate constants

obtained in competitive experiments . As a rule measurements of

several rates relative to a single reference reaction are

reported but a substantial variety of reference reactions has

been used in different investigations. While, fortunately,

it is the I'elative rates which are usually of primary interest

for stratospheric modeling, absolute values are necessary in

some cases. A satisfactory conventional evaluation of the

rate data for a single elementary reaction at a time is clearly

not possible. The present evaluation has therefore been

carried out with the main object of deriving first from the

experimental relative values in the literature a consistent

and reliable set of average relative rate constants. The set

is then placed on an absolute scale by adopting for one of the

reactions an absolute rate constant consistent with the

available experimental absolute values.

7
The experimental values of the relative rate constants

considered are listed in Table I. Some reactions not of

stratospheric interest are also included so that the relative

values can be reduced more readily to a common basis for

direct comparison and test of mutual consistency. To test

the mutual consistency of the data and obtain representative

average values three different procedures can be used: 1)

separate assessment of groups of sets with a common experimental

reference reaction (e.g. all the sets of rates measured

relative to 0^ or N2O, etc.), 2) reduction of all the sets

(in as much as possible) to a common basis by adopting an

arbitrary single reference reaction, and 3) computer evaluation

of the mean relative rates by a least squares method. The

latter two procedures have been adopted for the present

evaluation .The second procedure has the advantage of being

capable of revealing quickly any data which show gross

Inconsistencies and should be rejected. Thus, for example,

in relative rate measurements a constant systematic error may

sometimes affect appreciably the value for the reference

reaction itself but cancels out when the other relative rates

in the set are compared between themselves . Some examples

of this will be pointed out. An important Justification for

the adopted procedures is provided by the, on the whole,

remarkable mutual consistency of the data from very diverse

8
sources when treated in this manner.

Table II gives the recalculated relative rate constants

reduced to a cormnon basis by taking the reaction with

as the standard reference reaction. In a few cases the

sets did not contain the CO^ reaction itself or it was felt

that the CO^ value was less reliable. The underlined mean

values of other ratios of rate constants (e.g. ^neopentane/^C02

k k Xe/ CO^, etc.) have then been used to carry out an indirect

reduction to the common CO^ base. These underlined values

were not used in the computations of the averages. It is

evident that some sets listed in Table I have been omitted

from Table II. This has been done either because a meaningful

recalculation relative to CO^ could not be made or because the

reduced data were obviously in gross disagreement with the

other values. However, the omissions are relatively minor and

Table II contains essentially all of the comprehensive sets of

relative rate data in the literature. The values in

parentheses in Table II have not been used in the computation

of the averages because there appears to be some indication

that they may involve considerably more than the random errors.

(The value In parentheses for C^Hg in the Yamazaki , Cvetanovic

6^b set is no doubt an example of the type discussed above of

a substantial, perhaps interpretative, systematic error in a

reference reaction in a series of relative determinations).

9
The mean values of the relative rates in Table II and their

standard deviations are shown in the last two rows. The

standard deviations are relatively moderate in most cases

and the mean values represent a reasonably consistent set

of relative rate constants. Two blank columns have been left

in Tables I and II, for NH^ and H^O^, to show that rate

constants are not available for these two compounds and should

be determined. In the meantime it may be assumed that the

value for NH^ is probably between that for and CH^^ , and the

value for H^O^ is likely to be as large as that for H^O and

could be appreciably larger.

The mean values of the relative rate constants have

been also computed using a N.B.S. program (code name "Omnitcb")

for the linear least squares analysis . The computations have

been carried out by Dr. Robert P. Hampson at the National

Bureau of Standards. Omnitab computations for the sets of data

used in Table II, but omitting the values in parentheses for 0^

and C^Hg and all the values for Kr, Ar and SF^, give the mean

relative rate constants in Column B of Table III. With some

minor exceptions they are very similar to the mean values in

Column A, taken from Table II. The mean values in Column C of

Table III have been obtained for the same data as in B plus the

nine absolute values in the literature (listed in Columns D, E

and F of Table III). The mean relative values obtained are again

very similar, with the notable exception of the mean value for

10
ozone, which is reduced by about 30 percent. This difference

indicates a significant disparity between the relative and

the absolute rate measurements for ozone and shows the need

for additional determinations

.

Absclui:e Rate Constants az 300K

The available absolute rate constants of 0("^D2) reactions

are listed in Columns D-F of Table III. The earlier values

for 0^ of Noxon (1970) and for 0^ of Gilpin, Schiff and Welge

(1971) are consistent with the recent measurements of Heidner

and Husain (1973). The previous value for 0^ of Heidner, Husain

and Wiesenfeld (1972) is somewhat larger.

To make best Use of the available absolute rate

constants to set all the relative rate constants on an absolute

scale, the following three Omnitab computations have been

compared betv/een themselves and with the absolute values in

the literature. 1) The set of the relative Omnitab values from

Column B of Table III has been converted to absolute scale

by adopting the value ^CO^ = 2.1 x lO""''^ of Heidner and Husain

(1973) - the absolute values obtained are given in Column G of

Table III. 2) Omnitab computations of the absolute rate

constants for the data of Column B plus the nine absolute values

(in Columns D-F) are given in Column H of Table III. 3) Omnitab

computations as in the preceding case but without the 0^ value

of Heidner, Husain and Wiesenfeld (1972) gave almost uniformly

11
1 to 3 percent larger absolute values than in Column H of

Table III - the results of these computations are therefore

not shown separately in Table III. From a comparison of

these three computed sets of absolute values with the measured

absolute values a "recommended" set of absolute values was

derived and is listed, together with an estimate of the likely

uncertainties, in Column I of Table III. The estimated

uncertainties are relatively moderate in all cases except for

ozone, for which it may be as large as a factor of two. Further

determinations for ozone are evidently highly desirable.

Temperature Dependence

The temperature dependence of the rate constants of

the Oi'^D^) reactions is not known although it is likely to be

generally very small or negligible. This is supported by the

observed rapid occurrence of some of these reactions at

cryogenic temperatures. At the same time, Simonaitis and

::cloklen (1972) have recently reported a slight increase in

CO with temperature, as indicated in Table I. Evidently

further work is required. In the meantime it is probably best

to assume that the set of absolute values listed in Table III

holds also at the typical stratospheric temperatures.

Hot Atom Effect

Heicklen and his coworkers (Goldman, Greenberg,

Helcklen (1971), Greenberg and Heicklen (1972), Simonaitis,

Greenberg, Heicklen (1972)) have recently postulated

12
Involvement and a measurable kinetic contribution of "hot"

OC'^D^) atoms in some 0(''"D2) reactions. Unpublished subsequent

work to verify this postulate (Paraskevopoulos et al. 1972,

unpubl.) has shown at best" very minor effects, bordering on

the experimental error. Further work is needed. In the

meantime it would not seem Justifiable to recommend any

corrections in stratospheric modelling for potential "hot"

0("^D2) atom effects.

Reaction Mechanism

All the available evidence shows that at atmospheric

(and stratospheric) pressures there is no stable adduct

formation (i.e. only deexcitation of ©(''"D^) occurs) in the

0("''D2) reactions with such simple gases as , 0^, CO, CO^

and the same is probably also true for NO and NO^ . In

agreement with this Gaedtke et al . (H. Gaedtke , et al. (1972))

have found an extremely small third order rate constant for the

formation of N2O from and 0('^D2) in the presence of excess

N2 as the third body (k=3 x 10"^^ cm^ molecule"^ s~"^). In

1 ? the reaction of 0( D2 ) with O2 the products appear to be O(-^P),

02^'^'^^) and 62^ ( vibrationally excited ground electronic state

of O2). McCullough and McGrath ( 1973 ). believe that the

production of 02^ is quite extensive but Snelling (unpubl.)

finds that 0^{-^Z "*") is produced in at least 7555 of the O(-^Dt)

+ O2 reactive collisions and Gauthier and Snelling (unpubl.) fi]

that approximately 25 to 50? of it is formed in the first

vibrational level. The products of the reaction of 0(^02)

with 0^ appear to be 0^^ , 0^ and 0(^P). Davenport,

13
Schiff and Welge (1972) have shown that the ratio of

(0^ + 0^) to (0^ +0+0) reaction channels is approximately

unity. In the case of NO^, abstraction of an oxygen atom

no doubt occurs but the electronic (or vibrational) state

of the 0^ formed is uncertain. 0('^D2) attack on NpO proceeds

along two reaction paths: a) to form + 0^ and b) to form

2N0; the ratio k /k, is very close to one (P.M. Scott, et al.

a D

1971).

In the reactions of 0(^^02) with H^, H2O and paraffins little

or no (<ca 3%) deactivation to O(-^P) occurs. gives HO + H,

H^O gives 2H0 and in the case of paraffins there are tv;o

predominant reaction channels : insertion into the CH bonds to

form "hot" alcohols and abstraction of H to form HO and alkyl

radicals. The "hot" alcohols are collisionaly stabilized at

sufficiently high pressures, especially so in the case of

larger paraffin molecules. With CH^ and C^H^, on the other

hand, no collisional stabilization can be expected at the low

atmospheric and stratospheric pressure and the products are

HO and CH^ from CH^ and HO, C2H^, CH^ and CH2OH from ethane.

With some paraffins there is also a small amount of molecular

elimination i.e. direct formation of two stable molecules from

the initial adduct . In the case of CH^^ the products of the

molecular elimination are H2 and CH2O and its yield is 9% of

the total reaction (Lin and DeMore (1972)).
o

o o o O o

H

O o

O

1 o

O

O — —

ooo —

O

VX ——

"

-

rH rH cvrH

O' ?\

1 l-l C5v CM o

rH rH rH rH

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to C

"jo

CJ r-l O

vb CO

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cu -- —

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CV t—CV —

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cv —

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t- — -

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rH rH rH \o 0^ o rH

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15
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CM

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CVJ 6C OJ CM o

rH

t/N

cvj

LTN CO

rH

f-H LTN OJ

Ovl

CO K o

rH OCvl

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\0 LTv QO trH

on K

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rH O

rH o o

rH o

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rH

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rH

rH

rH

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rH orH

OJ

rH

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rH

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rH

rH

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rH

CVJ &

C^l

01-. fn OJ !n OJ on

C7\

CVJ on CM CvJ o|on o u~\ on o

CVJ 8

r-i rH

oJ

rH rH rH rH rH rH rH rH rH rH

rH

rH rH 1

o

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Ch

LTV H-=)- o\ -3- H

in

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CJv

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CVJ ^ o

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CvJ o

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C?N on t—

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t—

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(u §

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a:

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pL, D-. CO cn CJ
TABLE III. Sumniaiy of the mean relative rates and the

absolute rate constants of reactions of 0(''"D ) atoms at 298 K

Mean relative rates Absolute rate constants (lO cc.molec sec" )

b ) c ; c

)

Table II Ctanitab Ncr.on Gilpin Hsidner, Omnitab ReconiKeiided (1970) et al Husain ' Values

(1971) (1973)

A B C D E F G K I

°2 •35 .1(2 .In .6±.3 .70±.05 .88 .61 .75±.15

°3 3.79 U.21 2.82 2.5*1 3.5±.3''^

^. {-.2

8.8 k.? 5.0+2.5

CO .46 .1*2 .1*2 .73±.07 .87 .62 .75*. 15

COg 1 1 1 2.1±.2 2.10 l.W 1.8±.3

^2 . 30 • 30 .69-. 06 .64 1.1. .55±.15

NgO 1.31 1.23 1.21 2.57 1.19 2.2±.li

NO 1.07 1.16 l.llt 2.14!* 1.69 2.1+.1*

NO^ 1.56 1.55 1 r- 1 1.51* 3.26 2.28 2 . 8± . 5 NH^

«2 1. 86 1.63 1.61 3.1»3 2.39 2.9±.5

HgO 2.21 1.9't 1.91* 3.0±.3 1(.09 2.86 3. 5*.

6

H^O^

2.U2 2.26 2.22 l*.7l< 3.29 U.0±,7

2.72 2.71 2.67 5.68 3.91* l*.8+.9

C^Hg U.30 U.U7 1».1*2 9.38 6.53 8.0+1.5

7.0 6.91* 6.eu 1I1.6 10.1 12.3±2.3

Xe .89 .83 .78 I.7I4 1.16 1.1*±.3

a) Expressed relative to the CO^ rate taken OS unity.

b) Mean values from Table II.

c) Least squares computations of the mean relative and absolute rate constants ceirried out at the

National Bureau of Standards by Dr. Robert F. Hampson. Column B : Omnitab computations for the sets of data used In Table II (omitting all the values for Kr, Ar and SF^ and the values In parentheses

for Og and C^Hg) . Coluims C and H : Omnitab computations of the mean relative and absolute rate constants, respectively, using the same data as in B plus the nine absolute values in Colimns D, E and P. Column G : The relative data of Column B placed on an absolute scale by taking for CO^ the

value of 2.1 x 10~^°cc.molec~"'"sec~^.

d) Heldner, Husain and Wiesenfeld (1972).
References

Bledenkapp, D., and Bair, E. J., "Ozone Ultraviolet Photolysis.

I. The Effect of Molecular Oxygen," J. Chem. Phys. 52_, 6II9

(1970)

Biedenkapp, D., Hartshorn, L. G., and Bair, E. J., "The

O(-^D) + H^O Reaction," Chem. Phys. Ltrs. 5, 379 (1970)

Castellano, E., and Schumacher, H. J., "Die Klnetlk des

Photochemischen Ozonzerfalles Im Licht der Welleniange 313 niy ,

Zeitschrift fUr Physikalische Chemie Neue Folge 76_, 258 (1971)

Clark, 1. D., and Noxon, J. F., "Optical Emission from 0(''"D)

and 0^{h E^) in Ultraviolet Photolysis of 0^ and 0^ and CO^.

II. ," J. Chem. Phys. 57, 1033 (1972)

Davenport, j., Schiff, H. I., and Welge, K. H. , (Private

Communication)

DeMore, V/. B., "O('^D) Quenching Efficiency of 0„ Relative to

Other Gases," J. Chem. Phys. 52_, ^309 (1969 ) Donovan, R. J., Husain, D., and Kirsch, L. J., "Reactions of

Oxygen Atoms, Part II. Relative Rate Data for the Quenching

0(2 D^) using the OH Radical as a Spectroscopic Marker," Chem.

Phys. Ltrs. 6, ^88 (1970)

Ellenrieder, G., Castellano, E., and Schumacher, H. J., "Die

Kinetik und der Mechanismus des Photochemischen Ozonzerfalls

im Licht der Welleniange 2537 8," Zeitschrift fUr Physikalische

Chemie Neue Folge 76_, 2^0 (1971)

Fortin, C. J., Snelling, D. R., and Tardif, A., "The Ultraviolet

Flash Photolysis of Ozone and the Reaction of 0( D) with HpO,"

Canadian J. Chem. 50_, 27^7 (1972)

Gaedtke, H., Glanzer, K. , Hippler, H., Luther, K., and Troe, J.,

paper presented at the l^th Symposium on Combustion, 1972

Gauthier, M., and Snelling, D. R., "Mechanism of Singlet

Molecular Oxygen Formation from Photolysis of Ozone at 2537 a,"

J. Chem. Phys. 5^, ^317 (1971)

18
Gauthier, M., and Snelling, D. R., (Private Communication)

Gilpin, R., Schlff, H. 1., and Welge, K. H. , "Phot odissoclation

of 0^ in the Hartley Band. Reactions of 0(^D) and ^±th

0^ and O^," J. Chem. Phys. 55, 108? (1971)

Goldman, C. S., Greenberg, R. I., and Heicklen, J., "The

Reactions of O('^D) with Ozone and Nitrous Oxide," Intl. J.

Chem. Kinet. Ill, 501 (1971)

Greenberg, R. I., and Heicklen, J., "The Reaction of 0( D) with

CH|^," Intl. J. Chem. Kinet. IV, 4l7 (1972)

Heidner, R. F., and Husain, D., "Quenching of 0(2'^!)^) by

Atmospheric Gases," Nature, Phys. Sci. 241 , 10 (1973)

Heidner, R. P., Ill, Husain, D., and Wiesenfeld, J. R.,

"Kinetic Study of Electronically Excited Oxygen Atoms,

0{2^D^)f by Time-Resolved Atomic Absorption Spectroscopy in

the Vacuum Ultra-Violet (A = 115.2 nm, 0(3'^Dp° <- 2^0^))," Chem.

Phys. Ltrs. 1_6, 530 (1972)

Katakis, D., "Tracer Study of the Reactivity of O(-^D)," J. Chem.

Phys. 47., 541 (1966)

Langley, K. P., and McGrath, W. D., "The Ultra-Violet Photolysis

of Ozone in the Presence of Water Vapor," Planet. Space Sci. I9 , 413 (I97I)

Langley, K. P., and McGrath, W. D., "The Ultra-Violet Photolysis

of Ozone in the Presence of Molecular Oxygen," Planet. Space

Sci. 19, 416 (1971)

Lin, C. L., and DeMore, W. B., "Reactions of O^D with Methane

and Ethane," J. Phys. Chem. H, 863 (1973)

Lissi, E., and Heicklen, J., "The Photolysis of Ozone,"

J. Photochem. 1, 39 (1972)

Loewenstein, M., "Relative Quenching Rates of 0(''"D) by COp, Np,

and O^," J. Chem. Phys. 54, 2282 (1971)

McCullough, D. W. , and McGrath, W. D., "Electronic - Vibrational

Energy Transfer in the Reaction of O('^D) Atoms with Molecular

Oxygen," J. Photochem. 1, 241 (1973)

19
Mlchaud, P., Paraskevopoulos , G., and Cvetanovic, R. J.,

unpublished results.

Noxon, J. F., "Optical Emission from 0("^D) and O^Cb'^Z^) in

Ultraviolet Photolysis of 0 and 00^," J. Chem. Phys. 52_, I852

(1970)

Paraskevopoulos , G., et al. (Private communication, 1972).

Paraskevopoulos 5 G., and Cvetanovic, R. J., "Competitive Reactions

of the Excited Oxygen Atoms, 0(-'"D)," J. Am. Chem. Soc. £1, 7572

(1969)

Paraskevopoulos , G., and Cvetanovic, R. J., "Relative Rate of

Reaction of 0(-^D2) with H^O," Chem. Phys. Ltrs. 9., 603 (1971)

Paraskevopoulos, G., Preston, K. F., and Cvetanovic, R. J.,

"Relative Rate of Deactivation of 0( D^)'2 by Molecular Oxygen,"

J. Chem. Phys. 5^, 3907 (1971)

Paraskevopoulos, G., Symonds, V. B. , and Cvetanovic, R. J.,

"Relative Rate of Reaction of O(^Dp) with HpO," Canadian J.

Chem. _50, I838 (1972)

Preston, K. F., and Cvetanovic, R. J., "Collisional Deactivation

of Excited Oxygen Atoms in the Photolysis of NOp at 2288 8,"

J. Chem. Phys. 45., 2888 (I966)

Scott, P. M., and Cvetanovic, R. J., "Relative Rate for

Reactions of 0( D) Atoms Generated by Flash Photolysis of

Ozone," J. Chem. Phys. 5iL, 1440 (1971)

Scott, P. M., Preston, K. F., Andersen, R. J., and Quick, L. M.,

"The Reaction of the Electronically Excited Oxygen Atom

0(-^D2) with Nitrous Oxide," Can. J. Chem. _|49_, I808 (1971)

Simonaitis, R., Greenberg, R. I., and Heicklen, J., "The

Photolysis of N^O at 2139 S and 1849 S," Intern. J. Chem.

Kinetic 4, 497 (1972)

Simonaitis, R., and Heicklen, J., "The Reaction of OH with

NO^ and the Deactivat

Kinetic _4, 529 (1972)

NO^ and the Deactivation of O(-^D) by CO," Intern. J. Chem.

20
Simonaitis, R., and Heicklen, J., "The Reaction of 0( D) with

and the Reaction of OH with C^Hg," Intern. J. Chem. Kinetic

5, 231 (1973)

Slanger, T. G., and Black, G., "The COp Photolysis Problem,"

J. Chem. Phys. 51, I889 (1971)

Snelling, D. R., unpublished results.

Snelling, D. R., and Bair, E. J., "Nonadiabat ic Decomposition

of N^O in the Deactivation of O('^D) by N^," J. Chem. Phys. 47.,

228 (1967)

Yamazaki, H., "On the Deexcitation of the Singlet Excited

Oxygen Atoms," Canadian J. Chem. £8, 3269 (1970)

Yamazaki, H. , and Cvetanovi(5, R. J., "Isotopic Exchange of the

18 Excited Oxygen Atoms with CO , and Their Collisional Deactivation," J. Chem. Phys. 4_0, 582 (1964)

Yamazaki, H. , and CvetanoviC, R. J., "Collisional Deactivation

of the Excited Singlet Oxygen Atoms and Their Insertion into

the CH Bonds of Propane," J. Chem. Phys. hi, 3703 (1964)

Young, R. A., Black, G., and Slanger, T. G., "Reaction and

Deactivation of O(-^D)," J. Chem. Phys. 49, 4758 (I968)

21
Chemical Kinetics Data Survey

The reaction of 0('''S) with CO

^

(1) 0(''-S) + -* ?

Preferred value ; = 3.1 X 10"'''^exp(-2630/RT) cni'^niolecule^''"s'''"

Temperature range: 200 K < T < A50 K

Reliability: A = 3.1 + 0.5 x lo'"""^ cm"^molecule"''"s"'''

E = 2630 + 200 cal/mole

thus, log k + 0.15

Remarks ; The data of Atkinson and Welge (c) Is used essentially Intact, as It

Is the only temperature-variant experiment. Two other 300 K experimental points are considered (a,b) which serve to slightly modify and

set reliability limits on the expression.

References considered ; (a) E. C. Zipf, Can. J. Chem. 1863 (1969)

(b) S. V. Filseth, F. Stuhl and K. H. Welge, J. Chem. Phys. 52, 239 (1970)

(c) R. Atkinson and K. H. Welge, J. Chem. Phys, 57, 3689 (1972)

Evaluator;

Tom G, Slanger

Date: February 1973

22
Chemical Kinetics Data Survey

1

The reaction of 0( S) with 0

^

(1) 0(^S) + 0^ - ?

Preferred value

= 5,8 X 10 cm^molecule ^

T = 300 K; probably temperature Independent

Reliability: k + 1 x lo'^^ , thus log k + 0.07

Remarks ; There has been only a single measurement of k^.

References considered ; G. London, R. Gilpin, H. I. Schiff, and K. H. Welge, J, Chem. Phys.

54, 4512 (1971)

E valuator:

Tom G, Slanger

Date: February 1973

23
Chemical Kinetics Data Survey

The reaction of 0('*'S) with N^O

(1) 0(''"S) + N^O - ?

P re fe rre d val ue ; k^ = l,4x 10 cm'^molecule ^s

T = 300 k

Reliability: k + 0.3 x lo""*"^, thus log k + 0.1

Remarks

:

-13

Four measurements have been reported: 5.9 x 10 (ref, a),

1.6 X lo""*"""" (ref. b) , 1.5 x lo"''"''" (ref. c) , 1.1 x lo'"'""'" (ref. d)

.

The preferred value and the reliability are derived from the values

of ref. b,c,d giving equal weight to each of them. Ref. (a) has

been disregarded.

References considered ; (a) R. A. Young and G. Black, J. Chem. Phys. 44, 3741 (1966)

(b) R. A. Young, G. Black and T. G. Slanger, J. Chem. Phys. 49,

4769 (1968)

(c) F. Stuhl and K, H. Welge, Can. J. Chem. _47, 1870 (1969)

(d) S. V. Filseth, F. Stuhl, and K. H. Welge, J. Chem. Phys. 52. 239 (1970)

Evaluator;

Karl H. Welge

Date: February 1973

24
Chemical Kinetics Data Survey

The reaction of 0( S) with 0

^

(1) 0(^S) +02^?

Preferred value ;

= 4.3 X lO'^^ exp(-1700/RT) cm^molecule~''"s""'"

Temperature range: 200 K <T< 377K

-12 3 -1 -1

Reliability: A = 4.3 + 0.7 x 10 cm molecule s E = 1700 + 200 cal/mole

thus^ log k + 0.15

Remarks

Two temperature -variant data sets, those of Atkinson and Welge (e)

and of Slanger, Wood and Black (f) were combined. Four 300 K

measurements (a_,b,c,d) were also considered.

References considered:

(a) E. C, Zlpf, Bull. Am. Phys, Soc. 12, 225 (1967)

(b) R. A. Young, G. Black and T. G, Slanger, J. Chem. Phys, 50,

309 (1969)

(c) S. V. Fllseth and K. H. Welge, J. Chem. Phys. 51, 839 (1969)

(d) S. V. Fllseth, F. Stuhl, and K. H. Welge, J. Chem. Phys. 52,

239 (1970)

(e) R. Atkinson and K. H. Welge, J. Chem. Phys. 52^ 3689 (1972)

(f) T. G. Slanger, B. J. Wood and G. Black, Chem. Phys. Letters 17

401 (1972)

Evaluator;

Tom G. Slanger

Date: February 1973

25
Chemical Kinetics Data Survey

The reaction of 0('''S) with CH

^

(1) 0(''-S) + CH^ ?

Preferred value:

kj^ = 2 X 10 cm"^molecule

T = 300 K

Reliability: log k+ 0.4

Remarks

:

The preferred value is based on two works (ref. a,b). One work (a)

-14

yielded k(CH,) = 4.7 x 10 . The other (b) yielded a relative value

-4

k(CH,)/k(N^O) = 6 X 10 . Using for k(N^O) the preferred value

-II -15

1.4 X 10 yields k(CH^) = 8.4 x 10 . For a more accurate value

another measurement is indicated.

References considered;

(a) S. V. Filseth, F. Stuhl, and K. H. Welge, J. Chem. Phys. 52,

239 (1970)

(b) R. A. Young, G. Black, and T. G. Slanger, J, Chem. Phys. 50_,

309 (1968)

Evalua^tor;

Karl H. Welge

Date: February 1973

26
Chemical Kinetics Data Survey

The reaction of O('^S) with H^O

(1) 0(^S) + H^O - ?

Preferred value:

. ^ ,--10 3 1 . -1 -1

> 10 cm molecule s

T = 300 K

Reliability: log k + 1

Remarks

Two measurements have been reported: ~ 4 x 10 (ref. a) and

7 X 10 (ref, b) » Reliability limited mostly by concentration

measurement. Recent experience Indicates that the rate constant Is

more likely a few times 10 ,

References considered:

(a) F. Stuhl and K. H. Welge, Can. J, Chem. 47, 1870 (1969)

(b) S. V. Fllseth, F. Stuhl, and K. H, Welge, J, Chem. Phys. 52^,

239 (1970)

E valuator:

Karl H. Welge

Date: February 1973

27
Chemical Kinetics Data Survey

The reaction of O('^S) with NH

^

(1) 0(^S) + NH^ ?

Preferred value;

, _ . T_-10 3 , - -1 -1 . , k-. = 5 X 10 cm molecule s

T = 300 K

Reliability: k + 50 thus log k + 0.2

Remarks ; There exists only one measurement (ref, a). The reliability Is an educated guess. The accuracy of the measurements was limited by

NH^ concentration measurement.

References considered ; (a) S, V, Fllseth, F. Stuhl, and K. H. Welge, J. Chem. Phys. 52

239 (1970)

Evaluator ; Karl H. Welge

Date: February 1973

28
Chemical Kinetics Data Survey

The reaction of 0(^S) with 0(^P)

(1) 0(^S) + O(-^P) - ?

Preferred value

-12 3 -1 -1

kj^ = 7,5 X 10 cm molecule s

T = 300 K

Reliability: k+SOj^, log k + 0.2

Remarks

:

There has been only a single measurement of k, . Products are

1 -1

probably 2 0( D) ; for this reaction Ah(300) = -24.6 kJ mol

(-5.9 kcal mol"-'')

References considered;

W. Felder and R. A. Young^ J. Chem. Phys. 56, 6028 (1972)

Evaluator

:

Tom G. Slanger

Date: February 1973

29
Chemical Kinetics Data Survey

The reaction of 0(^S) with NO

(1) 0(^S) + NO ?

Preferred value ; -11 1/2 3 -1-1 k^=3.2xl0 T cm molecule s

Temperature range: 200 < T < 291 K

Reliability: k + 10 %^ log k + 0.05

Remarks : The preferred value is based on measurements (ref . a) at 200 K,

k(200 = (5.0 + 0.6) X lo""'"^, at 291 K, k(291) = (5.7 + 0.6) x lo"-*-^ -10

and (ref. b) at room temperature, k (room) = 5.5 x 10 . Two other

measurements (ref. c and d) at room temperature have been disregarded.

-10

Ref . (c) reported 8 x 10 . Ref . (d) reported k(NO)/k(N„0) = 60 yielding

-10 -11

k(NO) = 8.4 X 10 using for k(N20) the preferred value l.A x 10

Rejection of ref. (c) and (d) is somewhat arbitrary. The lower values

have been chosen because they include T-varlant measurement. Because

NO is important in auroral events, another investigation may be

appropriate to measure the degree of reliability. Averaging all values

yields an arithmetic mean of 6.5 x 10

References considered ; (a) R. Atkinson and K. H. Welge, J. Photochem. , in press (1973)

(b) G. Black, T, G. Slanger, G. A. St. John and R. A. Young, Can. J.

Chem. 47, 1872 (1969)

(c) S. V. Fllseth, F. Stuhl, and K, H, Welge, J. Chem. Phys. 52^,

239 (1970); ibid, erratum 57, 4064 (1972)

(d) R, A. Young, G. Black, and T, G. Slanger, J. Chem. Phys. 50,

309 (1969)

E valuator;

Karl H. Welge

Date; February 1973

30
Chemical Kinetics Data Survey

The reaction of O('^S) with NO

^

(1) 0(^S) + ?

Preferred value:

, _ ^ -_-10 3 . 1-1-1 = 5 X 10 cm molecule s

T = 300 K

Reliability: k ± 50 % , log k + 0.2

Remarks

There exists only one measurement (ref. a). The error limit is an educated guess. The accuracy was determined mainly by concentration measurement uncertainty.

References considered : (a) S. V. Filseth, F. Stuhl, and K. H. Welge, J. Chem. Phys. 52

239 (1970)

Evaluator

Karl H. Welge

Date: February 1973

31
Chemical Kinetics Data Survey

1

The reaction of 0( S) with

(1) oc-'-s) + N2 ?

Preferred value ; -17 3 -1 -1

< 5 X 10 cm molecule s

Temperature range: 200 K < T < 380 K

Remarks

Sfime upper limit measured In both papers considered (a,b).

References considered ; (a) F. Stuhl and K. H. Welge, Can. J. Chem. 1870 (1969)

(b) R. Atkinson and K, H. Welge, J. Chem. Phys. 57, 3689 (1972)

E valuator;

Tom G. Slanger

Date; February 1973

32
Rate constants for reactions of A) and of sulfur monoxide

Reaction

CO + O^C A) -> quenching

or reaction

CO + A) -+ CO2 + 0

SO + 02(^A) SO(^A) + O2

SO^ + 02(''"A) -* quenching

SO + O2 SO2 + 0

SO + SO -» SO2 + S

3 -1-1

k/cm molecule s

< 3 X 10

16

< 9 X 10

-27

(3.5 ± 0.36) X 10

< 2 X lO"-*-^

•13

< 8 X 10

T/K

300

300

300

300

300

.-13

3.0 X 10 exp (-2800/T) 400-2500

,-15 < 3 x 10

< 2 X 10

13

300

1000

Ref

References

1. W. H. Breckenridge and T. A. Miller, J. Chem. Phys . 56 , 465 (1972).

2. E. R. Fisher and M. McCarty, Jr., J. Chem. Phys . 45, 781 (1966).

3. Evaluations of K. Schofield, to be published in Journal of Physical and

Chemical Reference Data , Issue No. 1, Vol. 2_, 1973 .

Evaluator

W. H. Breckenridge

February, 1973

33
HO^ + hu

Chemical Kinetics Data Survey

1. Primary Photochemical Transitions

Reaction kJ/mol 0 kcal /mol X threshold (nm)

192 (1^5.9) 623 (1)

-»-H + 0^ (a"'"A ) 2 g

286 (68. U) hn (2)

-•H + O.(bV)

2 g

3U9 (83. U) 3U3 (3)

^OH + 0(^P) 262 (62.6) U56 ih)

-)-0H + 0(''"D) U53 . (108.0) 265 (5)

AHq calculated using values from ref. (a).

2 . Data

2a. Absorption Spectrum and Absorption Coefficient

Wavelenprth Ran^e Observation

195 ~ 2U5 nm Continuous abs . spectrum vith maximum

at 200 - 210 nm, obtained at 300 K

from photolysis of H^Og , photolysis of

HgOg in the presence of 0^ and photolysis of Clg in the presence of

H^O^ (b)

34
HO^ + hu

195 - 290 run Continuous abs . spectrum with

maximiam at I95 - 210 nm, obtained

at 1100 K from pyrolysis of H^O^

(c, d)

185 - 260 nm Continuous abs. spectrum with

maximiom at 200 - 210 nm, obtained

at 300 K from photolysis of water (e)

210 - 300 nm Continuous abs . spectrum with

maximum at 230 - 2U0 nm, obtained

at 300 K in aqueous solution from

puis? radiolysis (f

)

2b. Quantum yields

200 - 260 nm No direct measurements; estimate:

0^ " If derived from temperature

dependence and shape of absorption

spectrum in (d)

3. Preferred Values

a. Absorption coefficients

195 < ^ < 290 nm. Evaluation of ref. (d) Data for

T i 300 K and T = 1100 K given in Table I and Fig. 1.

Data of ref. (b) according to ref. (d) may be represented
HO^ + hu

in(^) = InC-^-^^) - a(o - o)' o u max max

with X = e(u_ )= 1.2-10 cm /mol, u = U8t80 cm

-8 2

and a ~ 1.9*10 cm .

"b. Quantum yields

200 < X < 250 nm: 0^i-W^) ~ 1

X < 200 nm : no recommendation

k. Remarks

a. Absorption coefficients

The evaluation of ref. (d) is used. The aequous solution data

shov a solvent shift of about + 30 nm compared to the gas phase.

The integrated absorptions (at the right of the maximum) for

the solution (f).the gas phase at 300 K (b) and the gas phase

at 1100 K (c) agree vithin about 10^. The gas phase 300 K data

of ref. (e) are about 30^ higher than those of ref. (b). The

gas phase 1100 K data (after accounting for the temperature

dependence) are about 10^ higher than those of ref. (b). The

causes of the discrepancies are problems in calculating the

HOg concentrations in the different systems. All authors state

an uncertainty of a factor of 2. The consistency, hovever, points

to an tincertainty of atmost 30^. Absorption spectra to lower

excited states as postulated in ref. (g) have not been detected.

36
H0„ + hu

"b. Quantum yields

The estimate of a total quantum yield of 1 is "based on the

completely continuous shape of the absorption at energies

highly in excess of the threshold energies for reactions

(l) - (U). The estimate of a predominsint photolysis path

to OH + 0 is "based on the temperature dependence of the

a"bsorption spectriun: The steep slope of the potential surface

of the excited state vertically ahove the ground state minimum

is predominantly in the direction of the normal vi"bration u^,

which corresponds to an 0 - 0 stretching. The steep slope of

the upper potential surface and the absence of any structure near the threshold of reaction (5)j points to reaction {h) as predominant channel instead of reaction (5)

37
HOg + hu

Table I

Values of absorption coefficient of HO , I85 - 290 nm

X(nm) e(T<300 K) , cm /mol Ref e(T=1100 K) , cm /mol Ref

185 1.0 • 10^ - e*

1.1 ' b 8 • 10^ d

200 1.2 ' b 8.5 d

210 1.2 . 8.5 • d

220 1.0 b 7.5 • d

230 6.7 • b 6.3 - d

2U0 3.6 ' b k.3 d

250 1.8 d 3.0 d

260 1 d h.9 • d

270 0.5 d 1.1 • d

The absorption coefficient is defined by the equ.

:

3 with 1 in cm and C in mol/cm

*) fitted to the data of ref. b using equal e-values at 210 nm

38
39
HO^ + hu

5. References

a) JANAF Thermochemical Tables, Dov Chem. Co. Middland (Mich.)

1965

b) T.T. Paukert and H.S. Johnston, J. Chem. Phys. 282U (19T2)

c) J. Troe, Ber. Biinsenges. Physik. Chem. Jl, 9^6 (1969);

H. Kijewski and J. Troe, Intern. J. Chem. Kinetics 3.s 223 (l9Tl)

d) H. Kijevski and J. Troe, Helv. Chim. Acta 205 (19T2)

e) C.J. Hochanadel et al, J. Chem. Phys . kh26 (1972)

f) G. Czapski and L.M. Dorfman, J. Phys. Chem. 68, II69 (196U)

g) A.D. Walsh, Adv. in Molec. Spectroscopy I, 159 (Pergamon,

London I962)

J. Troe

January 1973

AO
Comments on the reaction H + H^O^ -* H„ + HO

The preferred value for this reaction as shown in the CIAP Monograph

No. 1 Tables (preliminary) is that of Baulch, Drysdale, Horne and

Lloyd. J, Troe has commented on this selection in the light of his more recent experiments. These comments are given below together

with a reply by D. D. Drysdale.

Since the Leeds evaluation, we have measured rates and

profiles in the H2 - and CO - catalyzed pyrolysis of H2O2

(H. Kijewski and J. Troe, Int. J. Chem. Kin. 3, 223 (1971)).

Our data allow one to derive ~ (k^ + k^) x (0.09 ± 0.04),

where H + H2O2 - H2 + HO2 (k^^) H + HO2, - H2 + O2 (k^) and

H + HO2 -* 2 OH (k^) at 900 - 1100 K, in this limit independent

of k2. For the rate constant k2 of H + H2O2 "* OH + H2O, all

ratios k»/k^ which are smaller than 20 are compatible with

13 3 our results. Using k^ ~ 7 "10 cm /mol sec and k^/k^ ~ 5 (see Refs. in the article cited above), we obtain k^ (1000 K) ~

12 9+0 3 3

10 • - • cm /mol sec. With the lowest possible k„ + k, value

13 3

3 4

of about 2*10 cm /mol sec, we would obtain k^(1000 K) ~

12.3±0.3 3

10 * * cm /mol sec. The data preferred in the data sheet,

as adopted from the Leeds evaluation, would give at 1000 K

11.4 3

k- ~ 10 * cm /mol sec and are thus far outside of our range.

12 With the value of Albers et al. of k^ = 0.43 • (7±4) • 10

. 4200 , _ ^.,^12 , 4200. 3, ^ ij • exp(- rp ) - 3*10 exp(- ) cm /mol sec, one would obtain

11 6"^ 0 3 3

kj^(1000 K) ~ 10 • - • cm /mol sec, which is not much better.

A consistent picture could only be obtained with a larger acti13 vation energy of k^. A rate expression of e.g. k^^ = 5*10

exp(- ^^^^) cm"^/mol sec would agree with the data of Albers et al. Ki

reasonably well and meet our lowest possible value of k^(1000 K) ~

12.3 3

10 * cm /mol sec. We estimate the uncertainty worse than given

in the data sheet, perhaps a factor of 4. For k^ we have no recom14 3 mendation, except that k2(1000 K) < 10 cm /mol sec and that we also realize the inconsistency between the data of Albers et al.

and of Baldwin et al.

J, Troe

February, 1973

41
H + H^O^ + HO

^

Dr. Tree's recent results are in conflict with our evaluation

and other data in this temperature region. Both Troe's and

Baldwin's results were obtained from studies of complex kinetic

systems and it is difficult to resolve which of these is the

more reliable. We prefer for the moment to base our evaluation

on the extensive data of Albers et. al. with which Baldwin's

results also agree. However, in the light of Dr. Troe's results

we feel that our recommended expression should be used only in

the temperature range 300 - 500 K with error limits in log k

of ± 0.3

D. L. Baulch, D. D. Drysdale

May, 1973

14.0

_ 12.0

o

E

o

10.0

8.0

T/K

1000 500 300

o Baldwin et al (I)

X Albers et al (2)

O KijewsKi a Tree (3) • Baulch et al (4)

±, Lowest possible value of k|

from Kijewski a Troe (5)

Troe (5)

5^

1.0 2.0 3.0

io^t'/k"'

H + H2O2 -* + HO2 Rate constant as a function of temperature

(Baulch, Drysdale)

42
Photochemical and Rate Data for Methyl nitrite,

Methoxy and Methylperoxy

Julian Heicklen

PHOTOCHEMISTRY OF CH3ONO

The photolysis of CH3ONO has been studied extensively. The results

have been reviewed and extended by Wiebe and his coworkers . ^ ' ^ All

investigators agree that the principal primary process is

CH3ONO + hv ^ CH3O* + NO la

where the CH3O radical product can have considerable excess energy and

decompose to CH2O + H if not stabilized.

It was Napier and Norrish who first showed that photodecomposition

is not the sole reaction when radiation is absorbed. Part of the time

an isomer is formed which reverts back to CH3ONO.

CH3ONO + hv ^- Isomer CH3ONO lb

Other possible reactions of CH3ONO photolysis are

CR3ONO + hv CH2O + HNO Ic

H + CH2O + NO Id

Wiebe et al.^ determined the relative importance of reactions la-Id with

3660A incident radiation by studying the photolysis of GIsO^'^NO in the presence

of ^^NO and measuring the production of CHsO^^NO, ^"NaO, ^^NaO, and ^^NaO.

The N2O is produced from the reaction

2HN0 -> H2O + N2O "

. 2

Wiebe et al. found that no 2 9f^^o or 2 8>^^o was produced, from which they

concluded that reactions Ic and Id do not occur. From the quantum yields of

CHjO^^NO and ^o^^O, they deduced that reaction la proceeds with 76% efficiency.

With 3660A incident radiation, the efficiencies are for reaction la, 0.76 - 0.02,

for reaction lb, 0.24 ± 0.04, for reactions Ic and Id combined < 0.02. The

relative importance of these reactions with other incident wavelengths is

not known.

43
REACTIONS OF CH3O RADICALS

The reactions of CH3O radicals which might be important in the stratosphere

are those with O2, O3, NO, NO2 , and CO. Unfortunately, the measurements are

few and mostly at room temperature. No absolute measurements have been made

for any of these rate constants. However, some relative rate constants do

exist.

Consider the reactions

CH3O + 02-^ HO2 + CH2O 3

CH3O + NO CH3ONO 4a

CH3O + NO ^ CH2O + HNO 4b

CH3O + NO2 CH3ONO2 5a

CH3O + NO2 CH2O + HONO 5b

CH3O + CO -> products 6

Wlebe and Heicklen^ studied the photolysis of CH3ONO in the presence of

NO-CO mixtures and estimated k6/k^ 5 x 10" ** for temperatures between 25 and

150*C. Presumably, under stratospheric conditions, the ratio [NO]/ [CO] is

sufficiently large, so that reaction 6 is unimportant.

The relative importance of reactions 3, 4, and 5 were examined at room

temperature by Wiebe et al.^ by examining the photolysis of CH3ONO in the

presence of NO-O2 and NO-NO2 mixtures. From these studies they found that

ka/kit = 4.7 X 10~^ (± 20%) and kk/ks = 1.2 ± 0.1. Reaction 3 probably proceeds

with an activation energy of about 6 kcal/mole. Thus at stratospheric

temperatures ('Vj 200*K) , ks/ki^ should be even smaller. Two values of kj^a/ksa

have been reported at higher temperatures from pyrolysis studies. Phillips

and Shaw" reported k^a/^sa = 1.8 at 90°C, whereas Baker and Shaw^ found

-k^a/ksa = 2.7 at 130*'C. The value of kita/ksa from Wiebe et al.^ is 1.1 at

44
25** C. Thus the ratio k^a/^sa appears to be temperature dependent.

The value for the branching ratio kt,b/k^ is obtained from the N2O

quantum yield in the photolysis of CH3ONO, since all the N2O is produced from

reaction 2. Surprisingly, a consistent value of this ratio has been difficult

to obtain and values from 0 to 0.5 have been reported.^ The difficulty has

arisen because of the decomposition of the energetic CH3O* radical produced

in the photolysis. Recently three studies done at high pressures to stabilize

the CH3O radicals have all found the same value of 0.055 for the quantum yield

of N2O production. ^

» ^

» ^ Two of the studies^'® were done at 25'*C, but the

other extended the results to 150''C. When the quantum yield data for J^aO

are combined with the efficiency for reaction la, then k^b/kn = 0.145 ± 0.015

from 25-150°C.

The branching ratio ks^/ks is not firmly established. Only t-wo experimental

studies give information on this ratio. Baker and Shaw^ pyrolized (0130)2 st

130*0 in the presence of NO2 and obtained ksb/ks = 0.10 ± 0.01. Wiebe et al.,^

in their studies, found ksa/ks = 0.9 ± 0.1 at 25°C, which is consistent with

the Baker and Shaw finding and suggests that ksa/ksb has little if any

temperature dependence.

Tv70 estimates have been made for absolute rate coefficients of the above

reactions. Arden et al.^ estimated ki^ 'X^ 0.8 x 10 cm^/molecule sec.

Heicklen** deduced that ks = 0.27 x 10"^^ cmVmolecule sec at 25° C. The

ratio of these two numbers gives k3/ki4 3.4 x 10"^ in good agreement with

the measured value of 4.7 x 10

45
REACTIONS OF CH3O2 RA.DICALS

Even less is known about the reactions of CH3O2 radicals than about

those of aiaO radicals. The reactions of importance should be those with

O3, NO, NO2, and CO. Of these only the reactions with NO and NO2 have been

studied.^** The rate coefficients are not known, but some information is

available on the branching ratios. The possible reaction channels are

CH3O2 + NO -> CH3O2NO 7a

CH2O + HONO 7b

CH3O + NO2 7c

CH3O2 + NO2 CH3O2NO2 8a

CH2O + HONO2 8b

CH3O + NO3 8c

Spicer et al.^° examined the above reactions and found that when CH3O2 was

reacted with either NO or NO2 at 25°C, the major product was CH3ONO2.

They interpreted the CH3ONO2 production to represent that fraction of the

reaction that proceeded either via reaction 7a or reaction 8a. It was

deduced that reaction 7c occurred < 2% of the time since CH3ONO was not

produced in the CH3O2-NO system, as it surely would have, been if CH3O

were present. Reaction 8c was considered unlikely since it is endothermic

by 'V' 4.5 kcal/mole. Thus it was concluded that the efficiencies of reactions

7a, 7b, and 7c are 0.6 ± 0.1, 0.4 ± 0.1, and < 0.02. Likewise, the efficiencies

for reactions 8a, 8b, and 8c are 0.75 ± 0.05, 0.25 ± 0.1, and < 0.1.

46
Table I: Best estimates of rate coefficients.

uoeiricienc VaXue uni cs T, C Reference

0.76 ± 0.02 None 25 2

0.24 ± 0.04 None 25 2

(kic + kid)/ki^ < 0.02 None 25 2

ke/k^ 5 X

10"** None 25-150 1

ka/kv 4. 7x10" ^(±20%) None 25 2

k.» 'V/ 0.8 X

10"^^ cm^/sec — 9

k3^ 'v. 0.3 X 10"^^ cm^/sec 25 4

k.»/k5 1.2 ± 0.1 None 25 2

kt,a/k5a i.i None 25 2

kita/ksa 1.8 None 90 5

k.,a/k5a 2.7 None 130 6

ki,b/ki4 0.145 ± 0.015 None 25-150 1,2,8

ksb/ks 0.10 ± 0.01 None 130 6

ksa/ks 0.9 ± 0.1 None 25 2

k7a/k7 0.6 + 0.1 None 25 10

k7b/k7 0.4 ± 0.1 None 25 10

kyc/k? < 0.02 None 25 10

kea/ke 0.75 ± 0.05 None 25 10

kefe/ks 0.25 ± 0.1 None 25 10

kec/ks < 0.1 None 25 10

a) X = 3660A

b) k3 'V' 1.6 X 10"^^ exp. (-6500/RT) cmVsec (Ref. 9) . R = 1.987 cal/mole-°K.

47
References

1. H. A. Wiebe and J. Heicklen, J. Am. Chem. Soc. , 95 , 1 (1973).

2. H. A. Wiebe, A. Villa, T. M. Hellrnan, and J. Heicklen, J. Am. Chem.

Soc. , 95, 7 (1973).

3. I. M. Napier and R. G. W. Norrish, Proc. Roy. Soc , 299A , 317 (1967).

4. J. Heicklen, Adv. Chen. Series , No. 76, Vol. II, 23 (1968).

5. L. Phillips and R. Shaw, 10th Symposium (International) on Combustion,

Cambridge, England (1965) p. A53.

6. G. Baker and R. Shaw, J. Chen. Soc. , 1965 , 6965.

7. For a review of the early literature see J. Heicklen and N. Cohen,

Adv. PhotocheTTw , 5_» 157 (1968).

8. G. E. McGraw and H. S. Johnston, Intern. J. Chem. Kinetics , 1, 89 (1969)

9. E. A. Arden, L. Phillips, and R. Shaw, J. Chem. Soc , 196A , 5126.

10. C. W. Spicer, A. Villa, H. A. Wiebe, and J. Heicklen, J. Am. Chem. Soc. , 95, 13 (1973).

A8
Chemical Kinetics Data Survey

The combination of nitrogen atoms AH(300)

kJ mol ^ (kcal mol ^) I. N + N + N2 N2 + N2 -9A5.3 C-225.9)

Preferred value;

= 8.3 X 10" exp[+500/T] cm molecule' s"

where ^4P^ = 2k[N]^[Nj

d t z Temperature range: 100 < T < 600 K

Reliability: Uncertainty in log k + 0.2 (200-600 K: the uncertainty

is greater below 200 K)

Remarks;

The large scatter of the data at 300 K is due to a lack of appreciation

of the complex nature of the surface decay of N atoms in the experimental

systems studied. The expression is based on data obtained in the temperature range 100-600 K by (28,32,33,36-38,41 and 44): only in these

papers are the effects of both first and second order surface recombination considered. All other data are rejected.

Campbell and Thrush's relative efficiencies (N^: Ar; He = 1; 1: 1.4 at

298 K) (32) are probably the most reliable.

References considered;

1. E. Rabinovltch, Trans. Faraday Soc. 3^, 283 (1937)

2. J, Berkowltz, A. A, Chupka and G. B. Kistiakowsky , J. Chem. Phys.

25^, ^57 (1956)

3. W. Forst, H.G.V. Evans and C. A. Winkler, J. Phys. Chem. 61, 320 (1957)

4. M. Camac, J. Camm, S, Feldman, J. Keck and C, Petty, Inst. Aeron* Sci.,

Preprint No. 802 (1958)

5. P. Harteck, R. R. Reeves and G. Mannella, J. Chem. Phys. _29, 608 (1958)

6. T. Wentink, J. 0. Sullivan and K. L. Wray, J. Chem. Phys. 29_, 231 (1958)

7. R. A. Young and R. Sharpless, Bull. Amer . Phys. Soc. 3, 320 (1958)

8. R. A. Back, W. Button and C. A. Winkler, Can. J. Chem. 37_^ 2059 (1959)

9. J, C. Camm and J. C. Keck, Avco Everett Res. Lab., RR67 (1959)

10, J, T. Herron, J, L. Franklin, P. Bradt and V. H. Dlbeler, J. Chem.

Phys. 30. 879 (1959)

II. R. Kelly and C. A. Winkler, Can. J. Chem. 37_, 62 (1959)

12. M. H. Saxe and N. N. Llchtin, Am. Chem. Soc, Spring Meeting (1959)

13. C, A, Barth, Jet Propulsion Lab., JPL Research Summary 36.9 (1964)

p. 64

14. C. Mavroyannis and C. A. Winkler, Can. J. Chem. 37_, 1601 (1961)

49
References considered (cont'd);

15. R. A. Allen, J. C. Keck and J. C. Camm, Phys. Fluids 5, 284 (1962)

16. S, W. Benson and T. Fueno, J. Chem. Phys. 36^, 1597 (1962)

17. C. B. Kretschmer, Aerojet-General Corp., Report AN-671 (1962)

18. T. C. Marshall, Phys. Fluids 5, 743 (1962)

19. T, C. Marshall and R. A. Kawcyn, Phys. Fluids 5_, 1657 (1962)

20. L. I. Avramenko and V. M. Krasnen'kov, Izvest. Akad, Nauk SSSR, Ser.

Khlm. , I, 1196 (1963)

21. D. S. Burch, Oregon State Univ., unnumbered report (1963) AD 428 624

22. H. B. Dunford, J. Phys. Chem. 67, 258 (1963)

23. C. B. Kretschmer and H. L. Petersen, J. Chem. Phys. 39_, 1772 (1963)

24. G. R. Carruthers, Ph.D. Thesis, Univ. of Illinois (1964): Dissertation Abstr. 25, 6448 (1965)

25. R. A. Young, R. L. Sharpless and R. Strlngham, J. Chem. Phys. 41 , 1497 (1964)

26. I. M. Campbell and B. A. Thrush, Chem. Comm. 250 (1965)

27. I. M. Campbell and B. A. Thrush, Trans. Faraday Soc. 62, 3366 (1966)

28. K. M. Evenson and D. S. Burch, J. Chem. Phys. 45^, 2450 (1966)

29. S. Miyazaki and S. Takahashi, Mem. Def. Acad. Japan 6, 305 (1966)

30. S. Miyazaki and S. Takahashi, Mem. Def. Acad. Japan 6, 411 (1966)

31. S. Takahashi, Mem. Def. Acad. Japan _5, 305 (1966)

32. I. M. Campbell and B. A. Thrush, Proc, Roy. Soc. A296, 201 (1967)

33. M.A.A. Clyne and D. H. Stedman, J. Phys. Chem. 71, 3071 (1967)

34. R.E.W. Jansson and L. A. Middleton, Brit. J. Appl. Phys. 18, 1079

(1967)

35. J. P. Appleton, M. Steinberg and D, J. Liquornik, J. Chem. Phys. 48 , 599 (1968): 49, 2468 (1968)

36. I. M. Campbell and B. A. Thrush, Trans. Faraday Soc. 64, 1265 (1968)

37. I. M. Campbell and B. A. Thrush, Trans. Faraday Soc. 64, 1275 (1968)

38. R. M, Lambert, M, I. Christie, R. C. Golesworthy and J. W. Linnett,

Proc. Roy. Soc. A302, 167 (1968)

39. S. Miyazaki and S. Takahashi, Bull. Chem. Soc. Japan 41, 1456 (1968)

40. S. Miyazaki and S. Takahashi, Mem. Def. Acad. Japan 8, 791 (1968)

41. K, H. Becker, W. Groth and D. Kley, Z. Naturforsch. 24A , 1840 (1969)

42. H. H. Bromer and W. Zwirner, Z. Naturforsch. 24A, 118 (1969)

43. V. H. Shui, J. P. Appleton and J. C. Keck, J. Chem. Phys. 53, 2547

(1970)

44. W. Brennen and E. C. Shane, J. Phys. Chem. 75, 1552 (1971)

Evaluators:

D. L. Baulch, D. D. Drysdale and D. G. Horne

Date: March 1973

Additional information on this reaction may be found in "Evaluated Kinetic

Data for High Temperature Reactions. Volume 2. Homogeneous Gas Phase

Reactions of the H2-N2-O2 System" (Butterworths, 1973 in press) by

these authors.

50
Chemical Kinetics Data Survey

The dissociation of nitrogen

kJ mol

945.3

AH(300)

-1

(kcal mol ) (1) (225.9)

2

Preferred value;

Temperature range: 6000 < T < 15 000 K

Reliability: log k + 0.5

Definition: -d[N2]/dt= k^^CN^]

Remarks

;

The dissociation of ^2 been studied by shock tube, following the

reaction by Interferometry (1,2), by pressure changes at the end wall

1 +

(4) and by monitoring v.u.v. absorption at 117.6 nm (N2(X E )^,, ^ ^^q) (3).

We prefer the expression obtained in the latter work by Apple ton et al

(3): It is in good agreement with theoretical calculations by Shul et al

The results of (2 and 3) suggest that k(M = Ar)/k(M = N2)~ 0.4 at

6400 K, but no firm conclusion can be drawn about the relative efficiencies of N and except that k(M = N) > k(M = ^2). Hanson and

Baganoff (4) found k(M = N)/k(M = N2) to vary with temperature.

References considered:

1. B. Gary, Phys. Fluids 8, 26 (1965)

2. S. Byron, J. Chem. Phys. 44, 1378 (1966)

3. J. P. Appleton, M. Steinberg and D, J, Llquornlk, J. Chem. Phys.

48, 599 (1968) ; 49, 2468 (1968)

4. R. K. Hanson and D. Baganoff, AIAA J. 10, 211 (1972)

5. V. H, Shul, J, P. Appleton and J, C. Keck, J. Chem. Phys. 53 , 2547 (1970)

Eyaluators;

D, L, Baulch, D, D. Drysdale and D. G, Home

Date: March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions, Volume 2. Homogeneous

Gas Phase Reactions on the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

(5).

51
Chemical Kinetics Data Survey

The reaction of N v?lth NO

(1) N + NO N2 + 0

Preferred value:

-11 3 -1

k- = 2,7 X 10 cm molecule s

Temperature range: 300 K < T < 5000 K

Reliability: log k + 0.1 at 300 K increasing to log k + 0.3 in

range 2000-5000 K

Remarks

Expression based on room temperature data for k^ (primarily those of

(11) and (13)) and the data above 2000 K for (k^ = 1.3 x lo"'''^ 3 1 «-! exp{-38.0 x 1000/t} cm molecule s ; log K^^^^^^O) = 7.57,

log Kj^2(^000) = ^'^2, log K^2(^000) = ^'^^^ log K^2<^^^0^) ^ 2.62).

(1) N + NO N2 + 0

(2) N2 + 0 N + NO

References considered ;

1. C. P. Fenimore and G. W. Jones, J. Phys. Chem. 61, 654 (1957)

2. P. Harteck and S. Dondes, J. Chem. Phys. 27_, 546 (1957)

3. G. B. Kistiakowsky and G. G. Volpi, J. Chem. Phys. 28, 665 (1958)

4. F. Kaufman and L, J. Decker, 7th Combustion Symp., 57 (1959)

5. G. J. Verbeke and C. A. Winkler, J. Phys. Chem. 64, 319 (1960)

6. M.A.A. Clyne and B. A. Thrush, Proc. Roy. Soc. A261 , 259 (1961)

7. M.A.A. Clyne and B. A. Thrush, Nature 189, 56 (1961)

8. J. T. Herron, J. Chem. Phys. 35, 1138 (1961)

9. J. T. Herron, J. Res. Natl. Bur. Stands. 65A, 411 (1961)

10. C. B. Kretschmer, Aerojet-General Corp., AN-671 (1962)

11. L. F. Phillips and H. I. Schiff, J. Chem. Phys. 3^, 1509 (1962)

12. Y. Takezaki and S. Mori, Bull. Inst, Chem. Res. Kyoto, 45, 388 (1967)

13. C, Lin, D. A, Parkes, and F, Kaufman, J. Chem. Phys. 53, 3896 (1970)

Evaluator

;

D, L. Baulch, D. D. Drysdale, and D. G. Home

AH(300)

L"""- (k

-313.7 (-74.98)

kJ mol ^ (kcal mol ''')

Date: February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

52
Chemical Kinetics Data Survey

The reaction of with 0

kJ mol

313.7

AH(300)

-1

(kcal mol ) (1) N2 + 0 -* N + NO (74.98)

Preferred value : = 1.3 X lO"''"*^ exp[-38.0 x 10"^/t} cm^molecule''''"s'''"

Temperature range: 2000 K < T < 5000 K

Reliability: log k + 0.3

Remarks

The expression is based on the data of (1,2 and A) and is compatible

with the room temperature data for k - (2.7 x 10"^ cm-^ molecule "^s'^)

and a zero activation energy for reaction (-1). (log K(300) = -5A.0)

(1) + 0 N + NO

(-1) N + NO -* N^ + 0

The satisfactory [NO] profiles calculated in (3 and 5) using similar

expressions for k^ substantiate the above choice for k^.

References considered:

1. R. E. Duff and N. Davidson, J. Chem. Phys. 31, 1018 (1959)

2. K. L. Wray and J. D. Teare, J. Chem. Phys. 36_, 2582 (1962)

3. C. T. Bowman, Combustion Sci. Tech. 3, 37 (1971)

4. J. B. Livesey, A. L. Roberts and A. Williams, Combustion Sci, Tech.

4, 9 (1971)

5. H. K. Newhall and S. M. Shahed, 13th Combustion Symp. 381 (1971)

Evaluator:

D, L, Baulch, D, D, Drysdale and D, G. Horne

Date: February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press). by these authors.

53
Chemical Kinetics Data Survey

The reaction of N with NO^ to form NO

(1) N + NO^ - NO + NO

Preferred value : None, See remarks

k defined by -d[N02]/dt = 1/2 d[NO]/dt

r - Remarks

;

There are insufficient data to merit the recommendation of a rate

constant expression. The most reliable determination of the overall

rate constant is that of Phillips and Schiff (5) who estimated

-11 3 -1 -1

k = k^ + k^ + k^ + k^ = (1.8^ + 0,2^ x 10 cm molecule s at 300 K

(1) NO2 + N NO + NO

(2) .

, NO2 + N ^ N2O + 0

(3) NO2 + N -» N2 H- O2

(4) NO2 + N-^N2H-0 + 0

However their estimate that k^/k = 0.33 (300 K) is high relative to

the value of k^/k = 0.12 (--'298 K) obtained by Dmltrlev et al (6).

Furthermore it can be Inferred from the results of Clyne and Thrush (3)

that (k2 + 2k^)/k^ =4,7+1.2 (300-700 K) and this also Implies that

Phillips and Schiff 's value for k^/k may be too high. There is an obvious need for more data on reactions 1-4.

References considered;

1, P, Harteck and S, Dondes^ J. Chem. Phys. _27, 546 (1957)

2, G. J, Verbeke and C, A, Winkler, J, Phys, Chem. 64, 319 (1960)

3, M.A.A. Clyne and B. A. Thrush, Trans. Faraday Soc, _5I^ 69 (1961)

4, J. P. Doering and B. H, Mahan, J. Chem. Phys, 34^ 1617 (1961)

5, L, F, Phillips and H. I. Schiff, J. Chem. Phys. 42, 3171 (1965)

6, L. A. Dmltrlev, S, A, Kamenetskaya and S. Ya. Pshez he tskll,

Khlm, Vys, Energ, 1, 205 (1967), English translation p. 175

Evaluator ; D. L, Baulch, D, D. Drysdale and D. G, Home

AH(300)

( -325.2 (-77.72)

kJ mol "'' (kcal mol ^)

= k[N][N02]

Date: February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

54
Chemical Kinetics Data Survey

The reaction of NO with NO

to form N and NO^ (1) NO + NO -» N + NO

Preferred value ; None, See remarks

Remarks;

There are no experimental data for this reaction, Thermodynamically

this reaction Is unfavored and It will be exceeded by the parallel

reaction

(2) NO + NO - N2O + 0

at all temperatures.

Evaluator ; D. L. Baulch, D. D, Drysdale and D. G. Home

AH(300)

["'• (k(

325.2 (77.72)

kJ mol (kcal mol ^)

Date; February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

55
Chemical Kinetics Data Survey

The combination of N and 0

(1) N + 0 + M -» NO + M

Preferred value ; = 1.8 X IO'^^t"^'^ cm^molecule'^s"-"- (M = N^)

Temperature range: 200 K < T < 400 K

Reliability: log k + 0.2

Remarks

;

The expression Is that suggested by Campbell and Thrush (7). The

results from (A) and, to a lesser extent, (5) are in agreement with

this expression.

There are too few data to enable the recommendation of third body

efficiencies. However the efficiencies determined by Campbell and

Thrush (7,8 and 9) should be fairly reliable: they are listed in the

following table.

Relative Efficiencies of Third Bodies, Determined

by Campbell and Thrush

M 298K 196K Reference

^2 1 1

Ar 0.77 0.73 7 He 0.35 7 «2 2.2 8

H^O 6.7 9

CO^ 3.0 9

2.2 9

References considered :

1. P. Harteck, R. R. Reeves and G. Manella, private communication to

F. Kaufman, Prog. Reaction Kinetics I, 1 (1961)

2. C. Mavroyannls and C. A. Winkler, Can. J. Chem, 39_, 1601 (1961)

3. K. L. Wray, J, D. Teare, B. Kivel and P. Hammerllng, 8th Combustion

Symp. 328 (1962)

4. C. B. Kretschmer and H. L. Petersen, J. Chem. Phys. 39_, 1772 (1963)

5. C. A. Barth, Ann. Geophys. 20^ 182 (1964)

6. I. M. Campbell and B. A, Thrush, Trans. Faraday Soc. 62, 3366 (1966)

7. I. M. Campbell and B. A. Thrush, Proc. Roy. Soc. A296, 222 (1967)

8. I. M. Campbell and B. A. Thrush, Trans. Faraday Soc. 64, 1265 (1968)

AH(300)

l"-"- (k

-631.6 (-150.96)

kJ mol ' (kcal mol ^)

56
N+0+M-*NO+M

References (contd.)

9. I. M. Campbell and B. A. Thrush, Trans. Faraday Soc. 64, 1275 (1968)

10. S. Takahashl, Mem, Defense Acad. Japan 8^, 611 (1968)

11. V. H. Shul, J. P. Appleton and J. C. Keck, 13th Combustion Symp.,

21 (1971)

Evaluators;

D. L, Baulch, D. D, Drysdale and D, G. Horne

Date: February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

57
Chemical Kinetics Data Survey

The dissociation of NO

(1) NO + M

Preferred value;

None, See remarks

N + 0 + M

AH(300)

kJ mol ^ (kcal mol ^)

631.6 (150.96)

Remarks ; There are Insufficient data to enable a reliable recommendation to be

made. The rate constant expressions of Wray and Teare (3) are probably the best available and we suggest that they be used until further

data are available. They are (4200-6700 K) 6,6 X lo'S"^"^ exp[-75,5 x 10"^/t} cm^molecule'"'''s"''* (M =

Ar, 0^, N2)

(4000-6600 K) 1.3 x 10"^t"^'^ exp[-75,5 x 10^/t} cm^olecule'-'-s"'^ (M =

NO, N, O)

These expressions should be used with caution. They were derived on

the assumption that k (M = N^, = k(M = Ar) and k(M = N, 0) =

k(M = NO), Furthermore they were obtained from a data analysis In

which It was assumed that the blmolecular reaction of NO gave N2 and

©2 directly as products,

(2) NO + NO -» N2 + O2

whereas Camac and Felnberg (5) have subsequently demonstrated that the

alternative reaction

(3) NO + NO N2O + O

-

occurs to a significant extent.

References considered ;

1. E, Freedman and J. W, Dalber, J, Chem. Phys. 34, 1271 (1961)

2. W. G. Vincenti, Arnold Engineering Development Center, AEDC TN-61-65

(1961). AD 256 239

3. K, L, Wray and J, D. Teare, J. Chem. Phys, 36.^ 2582 (1962)

4. R, L, McKenzle, Natl. Aeron. Space Admin,, NASA TN D-3287 (1966)

5. M. Camac and R, M. Felnberg, 11th Combustion Symp. 137 (1967)

Evaluator ;

D. L. Baulch, D, D, Drysdale and D, G, Horne

Date; February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

58
Chemical Kinetics Data Survey

The reaction of N v?lth 0 ^ kJ mol

AH(300) -1-1

(kcal mol ) (1) N + O2 - NO + 0 -133.2 (-31.83)

Preferred value :

= 1.1 X lO""""^! exp{-3.l5 x 10^/t} cm^olecule'-'-s'*''-

Temperature range: 300 K < T < 3000 K

Reliability: log k+ 0.12 In the range 300-1500 K Increasing to

log k + 0.3 at 3000 K

Remarks:

The majority of the data for this reaction are in excellent agreement.

The selected expression is based primarily on the discharge -flow

results of (6,11,14 and 15). This expression is substantiated by the

data at higher temperatures of (5, 16 and 18) and is in excellent

agreement with the data for the reverse reaction. An Arrhenlus

expression cannot describe the data as adequately as the expression

chosen here.

References considered ;

1. K. Vetter, Z. Elektrochem. 53, 369 (1949)

2. C. P. Fenlmore and G. W. Jones, J, Physic. Chem. j61, 654 (1957)

3. P. Harteck and S. Dondes, J. Chem. Phys. _27, 546 (1957)

4. G. B. Kistiakowsky and G. G. Volpl, J. Chem. Phys. 22, 1411 (1957)

5. F. Kaufman and L, J. Decker, 7th Combustion Symp. 57 (1959)

6. M.A.A. Clyne and B. A. Thrush, Proc. Roy. Soc. A261, 259 (1961)

7. M.A.A. Clyne and B. A. Thrush, Nature 189 , 56 (1961)

8. C. Mavroyannis and C, A. Winkler, Chemical Reactions in the Lower

and Upper Atmosphere (Intersclence, N.Y. , 1961) p. 287

9. C. B. Kretschmer and H. L. Petersen, J. Chem. Phys. 39_, 1772 (1963)

10. A. S. Vlastaras and C. A. Winkler, Can. J. Chem. _45, 2837 (1967)

11. W. E. Wilson, J. Chem. Phys. 4^, 2017 (1967)

12. S. Mlyazaki and S, Takahaskl, Mem. Defense Acad. Japan 8^ 469 (1968)

13. K. H. Becker, W. Groth and D. Kley, Z. Naturforschung 24A, 1280 (1969)

14. I. D. Clark and R. P. Wayne, Proc. Roy. Soc, A316, 539 (1970)

15. A. A. Westenberg, J. M, Roscoe and N. DeHaas, Chem. Phys. Letts. 7_, 597 (1970)

16. C. T. Bowman, Combustion Scl. Tech. 3, 37 (1971)

17. J. B. Livesey, A. L. Roberts and A, Williams, Combustion Scl. Tech.

4^ 9 (1971)

18. H. K. Newhall and S. M. Shahed, 13th Combustion Symp. 381 (1971)

59
Evaluators;

D, L, Baulch, D. D. Drysdale and D. G. Horne

Date: February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

60
Chemical Kinetics Data Survey

The reaction of NO with 0

kJ mol

133.2

AH(300)

1

(kcal mol ) (1) NO + 0 -» N + 0 (31.83)

2 Preferred value : = 2,5 X lo'^^ T exp[-19.3 x 10^/t} cm\olecule"''"s"''"

Temperature range: 1000 K < T < 3000 K

Reliability: log k + 0.12 at 1000 K Increasing to log k + 0.3 at 3000 K

Remarks : The expression Is calculated from the reverse rate constant,

1.1 X

10** T exp[-3.15 x 10 /T] cm molecule s , and equilibrium

data, log K(IOOO) = -7.66, log K(1500) = -5.34, log K(2000) = -A. 17,

log K(3000) = -3.00. It Is In excellent agreement with the data of

(2 and 5) . K =

References considered:

1. F. Kaufman and J. R. Kelso, J. Chem. Phys. 23_, 1702 (1955)

2. F. Kaufman and L. J. Decker, 7th Combustion Symp. 57 (1959)

3. K.G.P. Sulzmann and C.B, Ludwlg, General Dynamics Corp. /Convalr

Division, Report ZPh-087 (1961), AD 269 383.

4. K. L. Wray and J. D. Teare, J. Chem. Phys. 36, 2582 (1962)

5. T. C. Clark, S. H. Garnett and G. B. Klstiakowsky , J. Chem. Phys.

51, 2885 (1969)

Evaluator : D. L. Baulch, D. D. Drysdale and D. G. Horne

Date: February 1973

Additional Information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions, Volume 2. Homogeneous

Gas Phase Reactions of the ^2'^2~^2 ^y^*^^"^" (Butterworths, 1973 in

press) by these authors.

61
Chemical Kinetics Data Survey

The reaction of nitrogen atom with ozone

kJ mol

-525.4

AH(300)

-1

(kcal mol ) (1) (-125.6)

Preferred value;

-13

k, = 5.7 X 10

^ cm molecule s

Temperature range: 298K

Reliability: Uncertainty in log k^:± 0.2 at 298K

Remarks ; Two determinations of have been made in discharge -flow systems.

Chen and Taylor (1) found as the only stable product and deduced

a value for k^ by assuming a detailed mechanism giving rise to N2O.

However, Phillips and Schlff (2) could not detect in the products

of the 0^ + N reaction. They determined k^^ by monitoring the removal

of 0^ by mass spectrometry and applying a second order derivation.

Their value of k^ at 298 K is recommended above.

References considered :

1. M. C, Chen and H. A. Taylor, J. Chem. Phys. 34, 1344 (1961)

2, L. F. Phillips and H. I. Schlff, J. Chem. Phys. 36, 1509 (1962)

Evaluators :

D. L. Baulch, D. D, Drysdale and D. G. Home

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterwor ths, 1973 in

press) by these authors.

62
Chemical Kinetics Data Survey

The reaction of N2 with O2 to

form N

^O and 0

(1) N2 + O2 - + 0

AH(300)

kJ mol (kcal mol ^ 331.3 (79.18)

Preferred value;

1.0 X lo""''^ exp[-55.2 x 10^/t] cm"^molecule'''"s"-'"

Temperature range: 1200 K < T < 2000 K

Reliability: log k + 0.4

Remarks

There are no experimental data for the rate of this reaction. The

above expression Is calculated from our recommendation for the rate

"*10 3 3

of the reverse reaction (k = 1.7 x 10 exp{-14.1 x 10 /t] cm

-1 -1

^^"^ molecule" s" , 1200-2000 K) and equilibrium constant data (log K(IOOO)

-17.98, log K(1500) = -12.10 and log K(2000) = -9.12).

References considered ; None

Evaluator:

D, L. Baulch, D. D. Drysdale and D. G. Horne

Date: February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

63
Chemical Kinetics Data Survey

The reactlcm of, N ^ O with 0 to form and 0 AH(300)

kJ mol

-331.3

-1

(kcal mol ) (1) + 0 - N2 + 0 (-79.18)

2

Preferred value; = 1.7 X lO""'"^ exp[-14.1 X 10"^/t} cm-^molecule~-''s"-'-

Temperature range: 1200 K < T < 2000 K

Reliability: log k + 0.4

Remarks

;

The data from (1,6,8,9,10 and 11) indicate that k^/k = 1.0 + 0.2 in

the range 1000-2800 K.

(1) + 0 - N2 + O2

'

( 2) N2O + 0 - NO + NO

The recommended rate constant expression is based on this ratio and our recommendation for k , i.e. the expression derived by Fenimore and Jones

(5), k2 = 1.7 X 10" exp[-14.1 x 10 /t] cm molecule" s" (1200-2000 K)

.

References considered : l.F. Kaufman, N, J. Gerri and R. E. Bowman, J. Chem. Phys. 25_, 106 (1956)

. 2. G. B. Kistiakowsky and G. G. Volpi, J. Chem. Phys. 27_, 1141 (1957)

3. J. T. Herron and H, I. Schiff, Can. J. Chem. 36, 1159 (1958)

4. J. N, Bradley and G. B. Kistiakowsky , J. Chem. Phys. 35, 256 (1961)

5. C, P. Fenimore and G. W. Jones, 8th Combustion Symp. 127 (1962)

6. W. Jost, K, W. Michel, J. Troe and H. Gg. Wagner, Z. Naturforschung

19a, 59 (1964)

7. E. S. Fishburne and R. Edse, J. Chem. Phys. 44, 515 (1966)

8. D. Gutman, R, L. Belford, A. J. Hay and R. Pancirov, J. Phys. Chem.

70, 1793 (1966)

9. A. A. Borisov, Kin. i Kat. 9, 482 (1968). English translation p. 399.

10. S. C. Barton and J. E. Dove, Can. J. Chem. _47, 521 (1969)

11. H. Henrici and S. H. Bauer, J. Chem. Phys. 50, 1333 (1969)

E valuator ;

D. L, Baulch, D. D. Drysdale and D. G. Home

Date; February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

64
Chemical Kinetics Data Survey

The reaction of NO with NO

to form N„OandO

AH(300)

kJ mol

150.7

-1

(kcal mol ) (1) NO + NO - N„0 + 0 (36.02)

Preferred value ; k = 2.2 X lO"''"^ exp[-32.1 x 10^/t} cm^molecule""''s""^

2

k defined by -d[NO]/dt = 2k[N0]

Temperature range: 1200 K < T < 2000 K

Reliability: log k + 0.3

Remarks

This is the expression derived by Kaufman and Kelso (6). Kaufman and

Kelso (6) and Freedman and Daiber (8) monitored the rate of NO removal

but assumed that the reaction gave N2 + O2 as products,

(2) NO + NO - N2 + O2

Yuan et al (7) also followed the removal of NO but did not specify the

reaction products. However Camac and Feinberg (10) have demonstrated

that the products of the bimolecular reaction of NO were N2O + 0.

(1) NO + NO -» N2O + 0

An Arrhenius expression plotted through the data from (5,6,7,8 and 10)

gives an anomalously high A-factor and predicts values of k ^ which

disagree with the direct data for k ^, We consider that the high temperature data (7,8 and 10) represent upper limits for k-^ because of the

occurrence of other NO-consuming reactions which were not adequately

allowed for in the data analyses. The expression of Kaufman and Kelso

(6) satisfactorily describes the data of (5 and 6) and also is in

agreement with the data of Fenimore and Jones (9) for k ^.

(-1) N2O + 0 = NO + NO

References considered :

1. S. Dushman, J. Am. Chem. Soc„ 43, 397 (1921)

2. J. Zeldovich, Acta Physicochim. URSS, _21, 577 (1946)

3. K. Vetter, Z. Elektrochem. 53, 369, 376 (1949)

4. H. Wise and M. F. Freeh, J. Chem. Phys. 20, 22 (1952)

5. H. Wise and M. F. Freeh, J. Chem. Phys. 20, 1724 (1952)

6. F. Kaufman and J. R. Kelso, J. Chem. Phys. 23^, 1702 (1955)

7. E. L. Yuan, J, I. Slaughter, W. E. Koerner and F. Daniels, J. Phys.

Chem. 63, 952 (1959)

8. E. Freedman and J, W. Daiber, J. Chem. Phys. 34, 1271 (1961)

9. C. P. Fenimore and G, W. Jones, 8th Combustion Symp. 127 (1962)

10, M. Camao and R. M. Feinberg, 11th Combustion Symp. 137 (1967)

65
NO + NO - N^O + 0

Evaluator :

D. L. Baulch^ D. D. Drysdale and D. G. Horne

Date: February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

66
Chemical Kinetics Data Survey

The raaction pf ]S[ r. Q with 0 to form NO AH(300)

-1

(1) N^O + O - NO + NO

kJ mol

-150.7

(kcal mol ) (-36.02)

Preferred value;

—10 3 3 —1 **1 kj^ = 1.7 X 10 exp{-14.1 x 10 /t] cm molecule s k^ defined by -d[N20]/dt = 1/2 d[N0]/dt = k^[N20][0]

Temperature range: 1200 K < T < 2000 K

Reliability: log k + 0.3

Remarks

The expression is that suggested by Fenimore and Jones (8). The

experimental data are scattered. The results from (6 and 12) refer

to the removal of N2O by reactions 1 and 2,

(1) N^O + 0 NO + NO

The available evidence (2,11,13,14,15 and 16) suggests that ^^,^^2 ~

I. 0+0.2 in the temperature range 1200-2000 K and so we have divided

the data from (6 and 12) by two. The flame study of Fenimore and Jones

(8) utilized a relatively direct technique for monitoring reaction 1

and their rate expression is in excellent agreement with our recommendation for reaction (-1) (1200-2000 K)

(-1) NO + NO N2O + 0

References considered:

1. F. C. Henriques, A.B.F. Duncan and W. A. Noyes, J. Chem. Phys. 6,

518 (1938)

2. F. Kaufman, N.J. Gerri and R. E. Bowman, J. Chem. Phys. _25, 106 (1956)

3. G. B. Kistiakowsky and G. G. Volpi, J. Chem. Phys. 27^ (1957)

4. C. P. Fenimore and G. W. Jones, J. Phys. Chem. 62^, 178 (1958)

5. J. T. Herron and H. I. Schiff, Can. J. Chem. 36l, 1159 (1958)

6. J. N. Bradley and G. B, Kistiakowsky, J. Chem. Phys. 35, 256 (1961)

7. F, Kaufman, Progress in Reaction Kinetics 1, 1 (1961)

8. C, P. Fenimore and G. W. Jones, 8th Combustion Symp. 127 (1962)

9. B. D. Fine, Natl. Aeron. Space Admin,, NASA TND-1528 (1962)

10. C. B, Kretschmer, Aerojet-General Corp., Report AN-671 (1962)

II, W. Jost, K. W. Michel, J. Troe and H. Gg. Wagner, Z. Naturforschung

19a, 59 (1964)

12. E. S. Fishburne and R. Edse, J. Chem. Phys. 44, 515 (1966)

(2)

2 N2O + 0 - N2 + 02

67
N^O + 0 -» NO + NO

References (contd) ; 13. D. Gutanan, R. L. Belford, A. J. Hay and R. Panclrov, J. Phys. Cham,

70, 1793 (1966)

14. A. A. Borisov, Kin. 1 Kat. 9, 482 (1968), English translation p. 399.

15. S. C. Barton and J, E. Dove, Can. J. Chem. 42, 521 (1969)

16. H. Henrici and S. H. Bauer, J. Chem. Phys. 50, 1333 (1969)

E valuator ; D. L, Baulch, D, D. Drysdale and D. G. Horne

Date: February 1973

Additional information on this .reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

68
Chemical Kinetics Data Survey

The reaction of nitric oxide^

nitrogen dioxide and oxygen

AH(300)

kJ mol

-19.2

-1

(kcal mol

(1) NO + + O2 + NO (-A.59)

(N0„ is the symmetric nitrate radical)

P re fe rre d val ue ; = 8 X 10" exp[-fAOO/T] cm molecule' s"

Temperature range: 300 < T < 500 K

Reliability; Uncertainty in log k^ : ±0.4 in temperature range quoted

The above expression is based entirely on the rate constant for the reverse reaction and equilibrium data. Above 500 the activation

energy steadily increases and becomes positive above ^ 800 K. The

value of k^ deduced from a study of the NO2 catalysed oxidation of

CINQ at 298 K by Ray and Ogg (1) is within a factor of two of the

above expression.

References considered;

1. J. D. Ray and R. A. Ogg, J. Chem. Phys. 26, 984 (1957)

Evaluators

D, L, Baulch, D. D, Drysdale and D. G. Horne

Date; April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

Remarks

69
Chemical Kinetics Data Survey

The reaction of nitrogen dioxide

with nitrogen trioxide AH(300)

kJ mol (kcal mol ^)

(1) + NO^ - NO + + O2 19.2 (4.59)

(NO^ is the symmetric nitrate radical)

Preferred value:

-13 3 -1 -1

k-j^ = 2.3 X 10 exp(-1600/T) cm molecule s

Temperature range: 300 < T < 850 K

Reliability: Uncertainty in log k^: ±0.4 in the temperature

range quoteid

Remarks

:

Reaction 1 is analogous to reaction 2 and is not a simple dissociation

of NO^ to NO and O2.

NO2 + NO^ -» NO + NO2 + O2 (1)

NO2 + NO2 -* NO + NO + O2 (2)

The existing data on k^^ were derived from analyses of the kinetics

of (a) the thermal decomposition of N20^ (1,2^5) and (b) the initial

stages of the bimolecular NO2 decomposition reaction (3,6). The

approximate value of k^ deduced by Berces and Forge teg (7) from a study of the photolysis of HNO^ vapor is not considered.

The first order rate constant for N20^ disappearance (k ) can be

related to the product of k^ and the equilibrium constant k^/k ^.

N20^ + M NO2 + NO^ + M (3,-3)

Expressions for k^^ have been calculated from data on k of Johnston

and Tao (2) and Daniels and Johnston (1). In a shock ?ube study of

N20^/Ar mixtures, Schott and Davidson (5) monitored NO^ and interpreted

the decay in terms of reactions 1,-3 and 4.

NO^ + NO^ NO2 + NO2 + O2 (4)

However, in view of some inconsistencies in their final results,

their value should not be considered reliable.

70
+ NO^ - NO + NO2 + O2

Remarks (cont'd);

Ashmore and co-workers (3,6) investigated the early stages of

the decomposition of NO2 in which NO^ contributes to the kinetics.

First, they obtained an order of magnitude estimate for k^/k^.

NO + NO^ - NO2 + NO2 (5,-5)

but subsequently derived an expression for k /k k which, combined

-13

with thermodynamic data from (4 and 5) yielded k^^ = 2.0 x 10

exp[-160G/T] cm molecule s

We suggest that the data derived from Ashmore and Burnett (6) and

Johnston and Tao (2) are the most reliable and base the recommended

expression on them.

References considered:

1. F. Daniels and E. H. Johnston, J. Am. Chem. Soc. 43, 53 (1921)

2. H. S. Johnston and Y.-S. Tao, J. Am. Chem. Soc. 7^, 2949 (1951)

3. P. G. Ashmore and B. P. Levitt, Research (Correspondence) 9_, S25 (1956)

4. J. D. Ray and R. A. Ogg, J. Chem. Phys. 26, 984 (1957)

5. G. Schott and N. Davidson, J. Am. Chem. Soc. 80, 1841 (1958)

6. P. G. Ashmore and M. G. Burnett, Trans, Faraday Soc. _58, 253

(1962)

7. T. Berces and S. Forge teg. Trans, Fajaday Soc. _66, 640 (1970)

8. H. S, Johnston, J. Am. Chem. Soc. 73, 4542 (1951)

Evaluators

;

D. L. Baulch, D. D, Drysdale, D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

71
Chemical Kinetics Data Survey

The reaction of nitric oxide with

nitrogen trioxide AH(300)

kJ mol (kcal mol '') (1) NO + NO^ + -95.2 (-22.75)

(NO^ is the symmetric nitrate radical)

Preferred value : ^ -11 3 -1 -1 ~ 2 X 10 cm molecule s

- d[NO]/dt = <l/2)d[N02]/dt = k^[N0][N02]

Temperature: 300 K

Reliability: Uncertainty in log k^: ±0.7

Remarks

Values of k^ have been obtained only from analyses of complex systems.

Johnston (1) and Hisatsune et al (3) examined the kinetics of the

^2^5^^^ system and estimated k^k^/k

^ NO + NO^ NO^ + NO2 (1)

N^O^ + M NO2 + NO^ + M (2,-2)

Using equilibrium data on reaction 1, the results of Hisatsune et al

(3) lead to 1.8 x lO"-*--^ cm-^molecule~ls~l, close to Johnston's lower

limit (k > 1.6 x lO'H cm^molecule "^s"!) .

Ford et al (5) analysed the photolysis of NO2/O2 mixtures and interpreted the results in tems of a mechanism comprising six reactions.

They deduced k^k 2/^2 their value depended on values of

k^ and k^ (2) which are probably unreliable. The value of k^ calculated from their result (6.5 x lO"-'-^ cm^molecule'^s"!) is about a factor of two less than Hisatsune 's result (3).

NO2 + O3 NO^ + O2 (3)

NO + 0^ NO2 + O2 (4)

The remaining data are very scattered. Ashmore and Burnett (6)

examined the kinetics of the early stages of NO2 decomposition in

which reaction-1 contributes to the initial removal of NO2. The

expression deduced for k ^ (473-707 K) gives k, about a factor of ten

less than the room temperature values described above. The reason

for this is not clear. Husain and Norrish (7) studied the flash

photolysis of NO2/N2 mixtures, monitoring NO^ by kinetic spectroscopy,

and deduced a value of the ratio k^/k^.

72
NO + NO^ -* NO2 + NO2

Remarks (cont'd) :

NO2 + 0 + M -» NO^ + M (5)

The value of k^ assumed in this work may be a factor of five too

high and consequently k^ may be considerably less than their value

-10 3 -1 -1

(1.4 X 10 cm molecule s . Finally, Morrison et al (9) interpreted the thermal oxidation of NO in terms of a complex mechanism

involving the species NO^, ^2^3^ ^^2^4 ^2^5 ^'^'^ deduced a value for

the ratio k, k,/k , at 300 K.

i b -b

NO + O2 - NO^ (6,-6)

In view of the complexity of this system no reliance can be placed

on the value of k^ obtained by combining this ratio with equilibrium

data on reaction h, assuming NO^ to be the symmetric nitrate radical.

We suggest that the consensus value k^^ ~ 2 x 10 '''''' cm"^molecule '''s

'' be used at 300 K, but recommend wide error limits.

References considered :

1, H. S. Johnston, J. Am. Chem. Soc. T3, 4542 (1951)

2, H. W, Ford, G. J. Doyle and N. Endow, J. Chem. Phys. 26, 1336

(1957)

3, I, C, Hisatsune, B. Crawford and R. A. Ogg, J, Am. Chem, Soc,

79, 4648 (1957)

4, G. Schott and N. Davidson, J, Am. Chem. Soc, 80, 1841 (1958)

5, H, W, Ford, G. J, Doyle and N. Endow, J. Chem. Phys. 32, 1256

(1960)

6, P, G, Ashmore and M. G. Burnett, Trans. Faraday Soc. _58, 253

(1962)

7, D. Husain and R.G.W. Norrish, Proc. Roy. Soc. A273 , 165 (1963)

8, M. Nicolet, J. Geophys, Res, 70, 679 (1965)

9, M, E. Morrison, R. G. Rinker and W. H. Corcoran, I. and E.G.

Fundamentals 5, 175 (1966)

Evaluators

D. L. Baulch, D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

73
Chemical Kinetics Data Survey

The disproportionation of nitrogen dioxide AH(300)

kJ mol (kcal mol ^)

(1) + NO + NO^ 95.2 (22. 75)

(NO^ is the symmetric nitrate radical)

Preferred value:

cNone

Remarks

;

There are few data specifically concerning reaction 1., Art approxi-

-18 3 -1 -1

mate value of 2.2 x 10 cm molecule s (707 K) was obtaipecj by

Ashmore and Levitt (1) in a study of the early stages of NO2 decomposition. In similar work Ashmore and Burnett (A) and Graham (.5) obtained expressions for k^^ in close agreement with each other and

with (1). However, the available data on the reverse reaction can- not be reconciled with these expressions, and although we suggest an approximate value for k ^ at 300 K, it is not possible with the

existing data, to recommend an expression for k^^.

NO2 + NO2 ^ NO + NO^ (1,-1)

References considered :

1. P. G. Ashmore and B. P, Levitt, Research (Correspondence) ^,

S25 (1956)

2. I. C. Hisatsune, B, Crawford and R. A. Ogg, J. Am. Chem, Soc.

79, 4648 (1957)

3. G. Schott and N. Davidson, J. Am. Chem. Soc. 80, 1841 (1958)

4. P. G. Ashmore and M. G. Burnett, Trans. Faraday Soc. 5^, 253

(1962)

5. E. W, Graham, Ph.D. Thesis, University of California, Berkeley

(1963)

6. N. Davidson and G. L. Schott, J. Chem. Phys. T]_, 317 (1957)

Evaluators :

D. L, Baulch, D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Voluem 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

74
Chemical Kinetics Data Survey

The combination lof NO and 0

kJ mol

-306.-^

Ah(300)

-1

(kcal mol ) (1) NO + 0 + M N0„ + M (-73.23)

Preferred value

:

k. = 3.0 X 10

-33

exp[-H).94 X 10 /t} cm molecule" s~ (M 1

Temperature range: 200 K < T < 500 K

Reliability: log k + 0.08

Remarks;

The selected expression is based primarily on the data of Clyne and

Thrush (9), Kaufman and Kelso (13) and Hartley and Thrush (15) and

also the data of Klein and Herron (11) after taking into account the

relative third body efficiencies of N2 and The following table

lists the relative third body efficiencies that we recommend for use at ~300 K. M = 0„22N^ Ar He C0„22224^6 N_0 H^O D„0 CH, CF, SF,

1 1.4 1.0 0.7^ 2.1 2.1 6.1 5.0 2.2 2.2 2.6

These efficiencies are derived primarily frcm the data in (13); the

data in (5,6,7,9 and 15) were also considered. There is no information available on the variation of efficiencies with temperature.

References considered :

1, F. Kaufman, N. J. Gerri and R. E. Bowman, J. Chem. Phys. 25 , 106 (1956)

2. H. W. Ford and N. Endow, J. Chem. Phys. Z7, 1156 (1957)

3. G. B. Kistiakowsky and G. G. Volpi, J. Chem. Phys. 27^ ll'^l (1957)

4. P. Harteck, R. R. Reeves and G. Mannella, J. Chem. Phys. 2_9,

1333 (1958)

5. F. Kaufman, Proc. Roy. Soc. A247 , 123 (1958)

6. F. Kaufman, J. Chem. Phys. 2^, 352 (1958)

7. E. A. Ogryzlo and H. I. Schiff, Can. J. Chem. 37.^ 1690 (1959)

8. D. Garvin, P. P. Gwyn and J. W. Moskowitz, Can. J. Chem. 38.^ 1795

(1960)

9. M.A.A. Clyne and B. A. Thrush, Proc. Roy. Soc. A269, 404 (1962)

10. H. W. Ford and S. Jaffe, J. Chem. Phys. 38, 2935 (1963)

11. F. S. Klein and J. T. Herron, J. Chem. Phys. 41, 1285 (1964)

12. A. A. Westenberg and M. deHaas, J. Chem. Phys. 40, 3087 (1964)

13. F. Kaufman and J, R. Kelso, Symp. Chemiluminescence, Durham, N.C.,

(1965)

14. E. A. Schuck, E. R. Stephens and R. R. Schrock, J. Air Pollution

Control Assocn. 16, 695 (1966)

75
NO + 0 + M - NO^ + M

References (contd.)

15. D. B. Hartley and B. A. Thrush, Proc. Roy. Soc. A297 , 520 (1967)

16. S. Miyazaki and S. Takahashl, Mem. Def. Acad. Jap. 8, 777 (1968)

17. S. Takahashi, Mem. Def. Acad. Jap. 8, 611 (1968)

18. H. H, Bromer and W. Zwirner, Z. Naturforschung 24a , 118 (1969)

19. J. Troe, Bar. Bunsenges. Phys. Cheip. 13, 906 (1969)

20. T. G. Slanger and G, Black, J. Chem. Phys. 5^, 3717 (1970)

21. R. Atkinson and R. J. Cvetanovic, J. Chem. Phys. 55, 659 (1971)

22. F. Stuhl and H. Nikl, J. Chem. Phys. 55, 3943 (1971)

23. R. Atkinson and R. J. Cvetanovic, J. Chem. Phys. _56, 432 (1972)

Evaluator

D. L, Baulch, D. D. Drysdale and D. G. Horne

Date: February 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

76
Chemical Kinetics Data Survey

The dissociation of NO ^ to NO and 0 AH(300)

-I -1

kJ mol (kcal mol ) (1) NO^ + M - NO + 0 + M 306.4 (73.23)

Preferred value :

= 1.8 X lO"^ exp[-33 x 10"^/t} cm\olecule""'"s"''' (M = Ar)

Temperature range: 1400 K < T < 2400 K

Reliability: log k + 0.1

Remarks

This is the expression derived by Troe (9). Apart from the preliminary results presented in (1), the various experimental determinations

of this rate constant are in remarkable agreement (2,4^6,7,9 and 10).

The only information on the relative efficiencies of different collision

partners is the estimate by Flshburne and Edse (8) that k(M = O2) =

k(M = Ar), 1600-2000 K, but this is not borne out by their ov?n experimental results and is therefore not recommended.

References considered :

1. M. Steinberg and T. F. Lyon, 131st Natl. Meeting Am. Chem. Soc.

51R (1957)

2. R. E. Huffman and N. Davidson, J. Am. Chem. Soc. 81, 2311 (1959)

3. B. P. Levitt, Trans. Faraday Soc. 58, 1789 (1962)

4. H. Hlraoka and R. Hardwick, J. Chem. Phys. 2361 (1963)

5. B. P. Levitt, Trans. Faraday Soc. _59, 59 (1963)

6. E, S, Flshburne, D. M. Bergbauer and R. Edse, Aerospace Res, Labs.,

ARL 65-169 (1965)

7. E, S, Flshburne, D. M. Bergbauer and R. Edse, J. Chem, Phys. 43,

1847 (1965)

8. E. S. Flshburne and R. Edse, J. Chem. Phys. 44, 515 (1966)

9. J. Troe, Ber. Bunsenges. Physlk. Chem. Ti, 144 (1969)

10. E. Zimet, J. Chem. Phys. 53, 515 (1970)

Evaluators

D. L. Baulch, D, D. Drysdale and D. G. Horne

Date: February 1973

Additional Information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterwor ths, 1973 in

press) by these authors.

77
Chemical Kinetics Data Survey

The combination of nitric oxide and

molecular oxygen AH(300)

kJ mol ^ (kcal mol ^)

(1) NO + O2 + M -» NO^ + M -19.2 (-4.59)

(NO^ is the symmetric nitrate radical)

P re fe rre d value

;

None

Remarks ; This reaction has been invoked occasionally in the literature but

there appears to be no direct evidence for it: only circumstantial

evidence exists for the alternative process giving rise to the

unsymmetrlc ONOO radical (2). Bahn (1) has confused reaction 1

with reaction 1, implying that NO2 acts only as a collision partner

NO + O2 + M - NO^ + M (1)

NO + NO2 + O2 - NO2 + NO^ (2)

but it is likely that the mechanism is more complex than a simple

three body collision: it is possibly similar to the nitric oxide

oxidation reaction 3 (2).

NO + NO + O2 -* NO2 + NO2 (3)

References considered ;

1. G, S. Bahn, "Reaction Rate Compilation for the H-O-N System,"

(Gordon and Breach, New York, 1968) p. 65

2. D, L. Baulch, D, D. Drysdale and D. G. Home, Evaluated Kinetic

Data for High Temperature Reactions, Vol. II, (Butterworths,

London, 1973) p. 285

Evaluators ; D, L, Baulch, D, D, Drysdale and D, G. Horne

Date: April 1973

Additional information on this reaction may be found in reference

(2) .

78
Chemical Kinetics Data Survey

The oxidation of nitric oxide by ozone

(1) NO + 0^ - NO2 + 0^

Preferred value;

-12 3 -J. = 1.5 X 10 exp(-1330/T) cm molecule s Temperature range: 200 K < T < 350 K

Reliability: Uncertainty in log : ± 0.2 in temperature

range quoted

Remarks

;

Reaction 1 has been studied principally in flow systems^ following

reaction by u.v. absorption photometry (3^5), mass spectrometry (A^

10) and by monitoring the emission from the excited product NO2 (6^7).

NO + 0^ - NO2 H- 0^ (1)

A stopped-flow technique (1) and a static photolysis system (NO2 in air)

(2) have also been used. The determinations by Thrush and his co- workers (6,7) appear to be the most reliable: the above expression is

based principally on their work. Apart from the work of Ford (2) and

Borok (3), which are unreliable on experimental grounds_, the remaining

data lie within a factor of 1.6 of our recommendation.

AH(300)

199.9 (-47.78)

-1 -1

kJ mol (kcal mol )

The chemilumine scent reaction has been studied in detail by Clyne

et al (6) and Clough and Thrush (7) at low pressures (~ 2 mm Hg)

.

Clyne et al (6) showed that the emission intensity was described by

the relationship

I [N0][0 ]/[M]

O J where I is dependent on the nature of M (7). They determined I =

20.7 exp[-2100/T] s'^ for M = N2,02 in the spectral range 600-875 ran. Assuming a linear increase in intensity to 1100 nm^ the pre-exponential

factor becomes 1,2 x lO^s"^ for the wider spectral range 600-1100 nm,

Clough and Thrush (7) resolved the overall rate constant k^ into two

components k- and k- , where ^ la lb

NO + 0^ NO2 + O2 (la)

NO + 0^ NO2 + ©2 (lb)

The temperature dependence of k. was assumed identical to that of

I (6).

79
NO + 0^ NO2 + O2

Remarks (cont'd) ; Fontijn et al (9) have shown how the chemilumine scent reaction may

be used to monitor NO (or 0„) in polluted air. They used Clyne's

expression for I^(M = N2^02) in the range 600-875 nm_, but quote the

pre-exponential factor as 12 instead of 20,7 (6),

References considered ; ^

1. H. S. Johnston and H. J. Crosby, J. Chem. Phys. 19, 799 (1951);

22, 689 (1954)

2. H. W. Ford, G. J, Doyle and N. Endow, J. Chem. Phys. 2_6, 1337 (1957)

3. M. T. Borok, Russ, J. Phys. Chem. 3^, 1123 (1961)

4. L. F. Phillips and H. I. Schif f, J. Chem. Phys. 36, 1509 (1962) ; 37., 924 (1962)

5. J. E. Marte, E. Tschuikow-Roux and H. W. Ford, J. Chem. Phys, 39_,

3277 (1963)

6. M.A.A. Clyne, B, A, Thrush and R. P. Wayne, Trans, Faraday Soc.

60, 359 (1964)

7. P. N. Clough and B, A, Thrush, Trans. Faraday Soc, _63, 915 (1967)

8. K. Schofield, Planet. Space Sci, 1_5, 643 (1967)

9. A. Fontijn, A, J, Sabadell and R, J, Ronco, Anal, Chem, 575

(1970)

10. H. D, Sharma, R. E. Jervis and K. Y, Wong, J, Phys. Chem, 74,

923 (1970)

Evaluators ; D, L, Baulch, D, D. Dirysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

80
Chemical Kinetics Data Survey

The reaction of nitrogen dioxide with oxygen AH(300)

kJ mol

199.9

-1

(kcal mol ) (1) (A7.78)

3

Preferred value : = 2.8 X lO""''^ exp[ -25, 400/T] cm molecule s

Temperature range: 200 < T < 350 K

Reliability: Uncertainty in log k^^ : ±0,2 in temperature

range quoted

Remarks

:

There are no data available on the rate of this reaction. The above

expression is based on the rate constant for the reverse reaction and

equilibrium data: it cannot be recommended for use at the high temperatures at which the reaction may be significant.

References considered :

Evaluators

:

D. L. Baulch, D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions, Volume 2, Homogeneous

Gas Phase Reactions of the H -N -0 System" (Futterworths^ 1973 in

press) by these authors.

81
Chemical Kinetics Data Survey

The association of nitrogen dioxide AH(300)

and nitrogen trioxide , , -1 , -1^ ° kJ mol (kcal mol ) (1) + NO^ + M - N^O^ + M -92.9 (-22.2)

(NO^ is the symmetric nitrate radical)

Preferred value ; k° = 2.8 X 10" cm molecule" s" (M=N20^ + NO) at 300 K

=° -12 3 -1 -1

kj^ = 3.8 X 10 cm molecule s

Temperature: 300 K

Reliability: Uncertainty in log k°: ±0.3

Uncertainty in log k^: ±0.4

Remarks

There are no data available on the rate of this reaction. The

values of k° and k^ suggested above have been calculated from

data on the reverse reaction (references 1 and 2 respectively)

and the equilibrium constant.

References considered:

1. H. S. Johnston and R. L. Perrine, J. Am. Chem. Soc. _73, 4782

(1951)

2. R. L. Mills and H. S. Johnston, J. Am. Chem. Soc. 73, 938

(1951)

Evaluators :

D, L. Baulch, D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

82
Chemical Kinetics Data Survey

The dissociation of nitrogen pentoxide AH(300)

-1

kJ mol (kcal mol

(1) N20^ + M NO^ + NO^ + M 92.9 (22.2)

(NO^ is the symmetric nitrate radical)

Preferred value : k° = 2.2 X lo" exp(-9700/T) cm molecule' s' , (M=i^205 + NO)

Temperature range: 300 < T < 340 K

k^ = 5.7 X 10^^ exp(-10 600/T) s""*- Temperature range: 273 < T < 300 K

Reliability: Uncertainty in log k°: ±0,3 in temperature range

quoted

CO Uncertainty in log k^^ : ±0.4 in temperature range

quoted

Remarks

The decomposition of ^20^ proceeds with the dissociation reaction 1

N20^ + M NO2 + NO^ + M (1)

which is in its second order region at pressures below 0.1 mm Hg

(3). Data on the second order rate constant k° were derived by

-3

three methods: (a) kinetic analysis (8) of low pressure (< 2 x 10

mm Hg) data on N20^ decomposition (1), (b) kinetic analysis of the

decomposition of ^2©^ in the presence of NO (2,3,5^6) and (c)

extrapolation of shock tube data on the apparent second order rate

constant to zero pressure (7). The value derived by me thod(c) cannot

be considered reliable as the extrapolation was based on only two

experimental points. The remaining data are in satisfactory agreement: in view of the observation (2) that Mills and Johnston's

results (3) may be high on account of heterogeneous effects, we prefer

Johnston and Perrine's data (2) and recommend their expression for k°.

Mills and Johnston (3) provide the only reliable data on the limiting

high pressure first order rate constant k'^, obtained by extrapolating

the apparent first order rate constant to infinite pressure. Amell

and Daniels (4) and Hisatsune et al (6) quote first order rate constants, but these were obtained in the fall-off region and cannot be

given any weight in this evaluation. We recommend the expression

derived by Mills and Johnston (3),

83
N20^ + M -* + NO^ + M

References considered:

1, E. F. Linhorst and J. H, Hodges, J. Am, Chem. Soc, 56_, 836

(1934)

2, H. S. Johnston and R. L. Perrine, J. Am, Chem, Soc, 73, 4782

(1951)

3, R. L, Mills and H. S, Johnston, J. Am. Chem. Soc, 73, 938

(1951)

4, A, R. Amell and F. Daniels, J, Am, Chem. Soc. 7%, 6209 (1952)

5, H. S. Johnston, J. Am. Chem. Soc. 7^, 1567 (1953)

6, I, C. Hisatsune, B. Crawford and R, A, Ogg, J, Am, Chem. Soc,

79, 4648 (1957)

7, G, L. Schott and N, Davidson, J, Am. Chem. Soc. 80, 1841 (1958)

8, R, A, Ogg, J, Chem, Phys, 18, 572 (1950)

Evaluators:

D, L, Baulch, D, D, Drysdale and D, G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions, Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butte rworths, 1973 in

press) by these authors.

84
Chemical Kinetics Data Survey

The combination of NO ^ and 0 atoms AH(300)

-1

kJ mol (kcal mol

(1) + 0 + M NO^ + M -211.2 (-50.5)

(NO^ is the symmetric nitrate radical)

Preferred value:

(M=N2)

-11 3 -1 -1 = 1.8 X 10 cm molecule s

1 o £. r, 1 n"32 6 -2-1

kj^ = D.J X 10 cm molecule s

Temperature; 295 K

00 o Reliability: Uncertainty in log k^ and log k^ : ±0.4 at 295 K

Remarks

:

The 0-atom addition and abstraction reactions 1 and 2 become competitive only at pressures of the order of one atmosphere.

NO^ + 0 + M - NO^ + M (1)

+ 0 -» NO + O2 (2)

Early work on the photolysis of in the presence of nitrogen at

1 atm assumed that reaction 1 occurred but did not investigate its

pressure dependence (1^2). Troe (A) studied the photolysis of

at 366 nm in N2 at pressures up to 200 atm and determined the ratio

k^/k2. He found reaction 1 to be in its third order region below

8 atm and in its fall off region at 10 atm. He obtained k?/k„ =

-20 3 -\ ca L I 1.1 X 10 cm molecule and k-/k„ = 3. The values of k" and

00 1 '- kj^ recommended above were calculated using k2 from (5). Smith (3)

also found a pressure effect in the relative rates of the reactions

of 0 with NO2 and CS2 which he attributed to reaction 1: values of k^

at 298 and 410 K indicated a pronounced negative temperature coefficient. However, in view of the complexity of the system studied, we

do not place any weight on Smith's results.

References considered :

1. H. W. Ford and N. Endow, J, Chem. Phys. 27, 1156, 1277 (1957)

2. E. A. Schuck, E. R. Stephens and R. R. Schrock, J. Air Poll.

Control Assocn. U, 695 (1966)

3. I.W.M. Smith, Trans. Faraday Soc. 64, 378 (1968)

4. J. Troe, Ber. Bunsenges. Physik. Chem. 73_, 906 (1969)

5. D. L. Baulch, D. D. Drysdale and D. G. Horne, Evaluated Kinetic

Data for High Temperature Reactions, Vol. II (Butte rworths,

1973), p. 271

85
NO^ + 0 + M NO^ + M

Evaluators :

D. L. Baulch, D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in reference (5).

r86
Chemical Kinetics Data Survey

The dissociation of nitrogen trioxide Ah(300)

kJ mol ^ (kcal mol ^)

(1) NO^ + M - + 0 + M 211.2 (50.5)

(NO^ is the symmetric nitrate radical)

Preferred value :

kj^ i« 8 X 10 cm molecule s M=N2

Temperature: 295 K

Remarks : There are no reliable data on the rate of reaction 1.

NO^ + M - + 0 + M (1)

The above value is calculated from the recommended value for the reverse rate constant and equilibrium data. Schott and Davidson (1)

estimated k^ (M=Ar) = 4.2 x 10 '^'^ cm"^molecule ''"s ^ at 1216 K from

results on the rate of disappearance of NO^ from shocked N20^/Ar

mixtures: little reliance can be placed on this figure as reaction

1 made only a minor contribution to the overall removal of NO^.

References considered ;

1. G. L. Schott and N. Davidson, J. Am. Chem. Soc. 80, 1841 (1958)

Evaluators

D. L. Baulch, D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

87
Chemical Kinetics Data Survey

The oxidation of nitrogen dioxide by ozone

(1) + O3 -* NO^ + O2

(NO^ is the symmetric nitrate radical)

P re fe rre d val ue ;

t= 9.8 X lo""*"^ exp(-3500/T) cm\olecule'''"s"''"

Temperature range: 286 < T < 302 K

Reliability: Uncertainty in log k^^: ± 0.3 in temperature range

quoted

Remarks : Direct determinations of k^^ have been made by stopped-flov; (1) and

stirred-flow (2) methods, monitoring reaction by absorption photometry.

The results, which differed by a factor of two, cannot easily be reconciled. However, in view of the apparent precision of Johnston and

Yost's data (1) we recommend that their expression for k^ (shown above)

be used, although with wide error limits, A recent paper by Scott

et al (3) describes an indirect determination of k^^ obtained in a study of the flash photolysis of NO2/O0 mixtures. In view of the

complexity of the system studied, we place no weight on their value

which lies a factor of 5 below the data of Johnston and Yost.

References considered :

1. H. S. Johnston and D. M. Yost, J. Chem. Phys. 17, 386 (1949)

2. H. W, Ford, G. J. Doyle and N. Endow, J. Chem. Phys. 26, 1336

(1957)

3. P. M, Scott, K. F. Preston, R, J, Andersen and L. M. Quick, Can.

J. Chem, 1808 (1971)

4. M, Nlcolet, J. Geophys. Res. TOj. 679 (1965)

Evaluators

;

D, L, Baulch, D, D, Drysdale and D, G. Horne

kJ mol

-104.6

-1

AH(300)

(kcal mol ^)

(-25.0)

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions, Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

88
Chemical Kinetics Data Survey

The reaction of nitrogen

trioxide with oxygen AH(300)

-1 -1

kJ mol (kcal mol ) (1) NO^ + 0^ - NO^ + 0^ 104.6 (25.0)

(NO^ is the symmetric nitrate radical)

Preferred value:

3 , , -1 -1

k^ = 7 X 10 cm molecule s

Temperature: 300 K

Reliability: Uncertainty in log k^^: ±0.3 at 300 K

Remarks

NO^ + 0^ + O3 (1)

There are no data on the rate of this reaction. The recommended

3 A 3 1 L expression for k ^ predicts k^ ~ 7 x 10 cm molecule s at

" -1

300 K and an activation energy of ~ 32 kcal mol . Clearly this

reaction will be unimportant at ambient temperatures.

References considered:

Evaluators

D. L. Baulch^ D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

89
Chemical Kinetics Data Survey

The decomposition of nitrogen trioxide

kJ mol

AH(300)

(kcal mol ^)

(-18.16)

(NO^ is the symmetric nitrate radical)

Preferred value; = 5 K lO" exp(-3000/T) cm molecule" s -d[N03]/dt = 2k^[m^]^

Temperature range: 293 < T < 309 K

Reliability: Uncertainty in log k^^: ±0.5 in temperature

range quoted

Remarks

;

Schott and Davidson (2) estimated k^^ from data of Schumacher and

Sprenger (1) on the decomposition of 0^ in the presence of 1^20^ at

293 and 309 K. Their expression is used by Johnston et al (3) and

is recommended above, but only 1*1 the narrow temperature range quoted.

The error at higher temperatures could be large, Schott and Davidson

also estimated k^^ = 3.8 x lO"-'-^ cm^molecule-^s-l at 820 K by monitoring the decay of NO^ in shocked N20^/N02/Ar mixtures. However, little

reliance can be placed on this figure.

References considered ;

1. H. J. Schumacher and G. Sprenger, Z. Physik. Chem. B2, 267 (1929)

2. G. Schott and N. Davidson, J. Am. Chem. Soc. 80, 1841 (1958)

3. H, S, Johnston, J. Lewis and L. Zafonte, Project Clean Air,

Task Force 7, Preliminary report, 1970

Evaluators;

D. L, Baulch, D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

90
Chemical Kinetics Data Survey

The reaction of nitrogen atom with hydroxy

AH(300)

kJ mol (kcal mol '') (1) N + OH NO + H -203.8 (-48.7)

Preferred value ; -11 3 -1 -1 - 5.3 X 10 cm molecule s Temperature range: 300 K

Reliability: Uncertainty in log k^ : ± 0.3 at 300 K

Remarks

The two available data on reaction 1 were obtained in discharge flow

-11 3 -1 -1

systems. Garvin and Broida (1) estimated k^ > 10 cm molecule s at 300 K from observations of the effect of H atoms on the 0^ + N

reaction. Campbell and Thrush (2) studied the reaction of mixtures

of N and 0 atoms with and deduced k^/k^ = 1.4 ± 0.1 from analyses

-11

of the atom decay rates. Taking k^ from (3) , we obtain k- = 5.3 x 10

cm

3-1-1

molecule s , which is recommended above. No information is

available on the temperature dependence^ although it is likely to

be small.

0 + OH - 0^ + H (2)

References considered ;

1. D. Garvin and H. P. Broida^ 9th Combustion Symp. 678 (1963)

2. I. M. Campbell and B. A. Thrush, Trans, Faraday Soc. 64, 1265

(1968)

3. D. L. Baulch^ D. D. Drysdale, D. G. Home and A. C. Lloyd,

Evaluated Kinetic Data for High Temperature Reactions. Vol, I (Butterworths, 1972) p. 37

Evaluators ;

D. L. Baulch, D. D, Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions, Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

91
Chemical Kinetics Data Survey

The reaction of hydroxyl with

nitrogen molecules

(1) ^2 + HO -» + H

AH(300)

kJ mol (kcal mol ^)

261.0 (62.38)

Preferred value ; = 2.5 X 10"*''^exp[-39 100/T] cm"^molecule""''s'''"

Temperature range: 700 < T < 2500 K

Reliability: Uncertainty In log k: +0.2 In the temperature range

quoted

Remarks

;

No experimental data are available on the rate of reaction 1, The

preferred expression was obtained by combining k

^ (q.v.) with

equilibrium data.

(-1) N2O + H N2 + HO

Clearly reaction 1 will become significant only at very high temperatures (T > 3000 K) at which the error in k^ calculated from the above

expression is unknown and may be large.

References considered:

None

Evaluators;

D. L, Baulch, D, D, Drysdale and D. G. Home

Date: March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

92
Chemical Kinetics Data Survey

The reaction of hydrogen atoms

with nitrous oxide AH(300)

-1

(1) + H N2 + HO

kJ mol

-261.0

(kcal mol ) (-62.38)

Preferred value;

Temperature range: 700 < T < 2500 K

Reliability: Uncertainty In log k: +0.2 In temperature range quoted.

Recent results by Baldwin et al (6) and Albers (reported In (7)) have

established that the activation energy Is higher than previously

supposed (3,8), If the early data of Fenlmore and Jones, obtained In

flame studies, are recalculated using a revised calibration of the

H-atom concentration, then, with the exception of two order of magnitude determinations at 400 K (2,4), the above expression adequately

describes all the data. These data arise from a variety of sources

viz, shock tube (5), flame (1,3), and discharge-flow systems (7) and

a study of the reactions of added to slowly reacting H2/O

mixtures (6),

^

References considered:

1. C. P. Fenlmore and G. W. Jones, J. Phys. Chem. 63, 1154 (1959)

2, M. Schlavello and G. G. Volpl, J. Chem. Phys. JT., 1510 (1962)

3, G. Dlxon-Lewls, M, M. Sutton and A. Williams, 10th Combustion Symp.

495 (1965); J. Chem. Soc. 5724 (1965)

4. G.R.Ao Johnson and M. Slmlc, J, Phys. Chem. Tl, 1118 (1967)

5. H. Henrlcl and S. H. Bauer, J. Chem, Phys. 50, 1333 (1969)

6, R, R, Baldwin, A. Gethln and R. W. Walker, JCS Faraday I, 69, 352 (1973)

?• M, Gehrlng, K. Hoyermann, H, Schacke and J. Wolfrum,. 14th Combustion Symp. (1972)

8. K. Schofield, Planet, Space Scl. 15, 643 (1967)

E valuators

:

D. L. Baulch, D. D. Drysdale and D. G. Horne

Date: March 1973

Additional Information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

Remarks

;

93
Chemical Kinetics Data Survey

The combination of hydrogen atom

with nitric oxide

(1) H + NO + M - HNO + M

P re fe rre d val ue ; = 1.5 X lO""^^ exp(+ 300/T) cm^molecule'^s"''", (M =

r Temperature range: 230 < T < 700 K

Reliability: Uncertainty in log k^^: ± 0.2 in temperature range quoted

Remarks ; There is good agreement between the five Independent determinations

of k^

NO + H + M - HNO + M (1)

The recommended expression is that derived by Kaufman (4) from the

discharge -flow data of Clyne and Thrush (1,2). Subsequent work has

supported the latter data at 300 K; in particular, Hiklda's value of

(7), obtained in a pulse radiolysis study, is in excellent agreement. The values obtained by Slmonaltis (3) and Hartley and Thrush

(5) are within a factor of four of the above expression: we do not

place any weight on Callear and Wood's approximate value obtained by

flash photolysis (6), Limited data on the relative efficiencies are given by Hartley and Thrush (5).

References considered : 1. M.A.A. Clyne and B. A. Thrush, Trans. Faraday Soc. 57_, 1305 (1961)

2. M.A.A. Clyne and B. A. Thrush, Disc. Faraday Soc. 33.^ 139 (1962)

3. R. Slmonaltis, J. Phys. Chem. 6_7, 2227 (1963)

4. F. Kaufman, Ann, Geophys. 2£, 106 (1964)

5. D. B. Hartley and B. A. Thrush. Proc. Roy. Soc. A297 , 520 (1967)

6. A. B. Callear and P. Wood. Trans. Faraday Soc. 67, 3399 (1971)

7. T. Hikida, J. A. Eyre and L. M. Dorfman, J. Chem. Phys. 54, 3422

(1971)

Evaluators ;

D. L. Baulch, D, D. Drysdale and D. G. Horne

AH(300)

-208.7 (-49.9)

kj mol ^ (kcal mol ^)

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

94
Chemical Kinetics Data Survey

The dissociation of HNO AH(300)

kJ mol

208.7

-1

(kcal mol ) (1) HNO + M-NO + H+ M (49.9)

Preferred value: = 5 X lO" exp[ -24,500/T] cm molecule" s M=H

2

Temperature range: 230 < T < 700 K

Reliability: Uncertainty in log k^ : ±0.2 in temperature

range quoted

Remarks

:

There are no experimental data on the rate of reaction 1.

The above expression is based on the recommended expression for the reverse rate constant and equilibrium data. The uncertainty in log k

at temperatures above 700 K cannot be estimated.

References considered:

Evaluators

:

D. L. Baulch^ D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths , 1973 in

press) by these authors.

HNO + M-»NO + H+ M (1)

95
Chemical Kinetics Data Survey

The reaction of hydrogen with nitric oxide AH(300)

kJ mol

227.3

-1

(kcal mol ) (1) + NO - HNO + H (54.3)

Preferred value; cm molecule s

Temperature

Reliability:

2000 K

Uncertainty in log k : ±0.2 at 2000 K

Remarks

;

There are no experimental data on reaction 1

NO + H2 -» HNO + H (1)

The above value is based on the recommended value of k (1) and

equilibrium data. The temperature dependence of k^^ is not known.

References considered :

1. C. J. Halstead and D. R. Jenkins, Chem. Phys. Letts. 2, 281

Evaluators :

D. L. Baulch, D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Buttervorths, 1973 in

press) by these authors.

(1968)

96
Chemical Kinetics Data Survey

The reaction of hydroaen atom with HNO AH(300)

kJ mol ^ (kcal mol ''')

(1) H + HNO + NO -227.3 (-54.3)

Preferred value:

-12 3 -1 -1 = 8o0 X 10 cm molecule s at 2000 K

lO""""^ ^ ^1 ^ lO""*"^ cm"^molecule"''"s"''' at 300 K

Reliability: Uncertainty in log k^ : ±0.2 at 2000 K

Remarks

:

Studies of the NO-catalysed recombination of H atoms in flames have

given values of k., in the region of 2000 K, We recommend k^ =

8 X 10

-12 cm3-1-1

molecule s obtained by Halstead and Jenkins from

Ey/Oy flames (5). Smith (6) has recently reported a value of

-12 3 -1 -1

4 X 10 cm molecule s from C„H„/0^/N^ flames: the reason for

this discrepancy is not obvious.

HNO + H - H2 + NO 1

At low temperatures, reaction 1 is fast and difficult to measure.

Clyne and Thrush (1) estimated a lower limit of 5 x lO"-"-^ cm

molecule'-'-s"-'- from a discharge-flow study of the H + NO reaction.

Kohout and Lampe (4)^ studying the mercury photosensitised reaction

between H2 and NO^ monitoring HNO and the product N^O by mass spectrometry, obtained an order of magnitude estimate of k^ which we cautiously recommend above. However, it must be noted that Callear

and Carr (7) have criticized Kohout and Lampe ' s experimental arrangement.

References considered:

1. M.AoA. Clyne and B. A, Thrush, Disc, Faraday Soc. 3^, 139 (1962)

2. E. M. Bulewicz and T. M. Sugden, Proc. Roy. Soc. A277 , 143 (1964)

3. R. M, Lambert, Chem, Comm. 850 (1966)

4. F. C. Kohout and F. W, Lampe, J. Chem. Phys. 46, 4075 (1967)

5. C, J, Halstead and Do R., Jenkins, Chem. Phys. Letts. 2, 281 (1968)

6. M. Y. Smith, Combustion and Flame 18, 293 (1972)

7. A. B. Callear and R. W. Carr, private communication (1972)

97
H + HNO -* + NO

Evaluators

;

D. L. Baulch, D. D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

98
Chemical Kinetics Data Survey

The reaction of hydroxyl with nitric

oxide to form nitrogen dioxide and

hydrogen atoms

(1) NO + HO NO2 + H

Preferred value ; = 2.8 X 10"''"^exp[-15 100/T] cm^molecule'-'^s"-'-

Temperature range: 298 < T < 633 K

Reliability: Uncertainty In log k: + 0.2 at 298 K increasing to ±0.3

at 633 K

Remarks

;

No experimental data are available on the rate of reaction 1

1. NO + OH - NO2 + H

-1. NO2 + H -» NO + OH

The preferred expression was obtained by combining k = 5.8 x 10

''"^

exp(-740/T) with equilibrium data. Clearly reaction 1 will become

significant only at high temperatures (T > 1500 K) at which the error

in k^ calculated from the above expression is unknown and may be large.

References considered:

None

Evaluators:

D. L. Baulch, D, D. Drysdale and D. G. Horne

AH(300)

-1 -1

kJ mol (kcal mol ) 121.3 (28.99)

Date: March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

99
Chemical Kinetics Data Survey

The reaction of hydrogen atoms with

nitrogen dioxide to form nitric

oxide and hydroxyl

(1) + H NO + HO

AH(300)

kJ mol (kcal mol ^)

-121.3 (-28.99)

Preferred value: = 5.8 X lo"'''^ exp[-740/T] cm\olecule~"'"s""'"

Temperature range: 298 < T < 633 K

Reliability: Uncertainty in log k: ±0.2 in

temperature range quoted

Remarks

'

'

The most reliable value of k, is that of Phillips and Schiff (3)

who examined reaction 1 in a discharge flow system, using mass

spectrometry.

NO2 + H -» NO + OH (1)

Rosser and Wise (1) obtained k^/k^ from a study of the H2/CI2/NO2

reaction:

GI2 + H - HCl + CI (2)

-10 3 -1 -1

taking k2 from (4) we obtain k^ = 1.5 x 10 cm molecule s at

500K. Ashmore and (2) examine the behaviour of NO2 in slowly

reacting H /O mixtures and deduced a value of k /k- : combining

-10 3 -1 -1

this with k„ from (5) we obtain k. = 1.8 x 10 cm molecule s at 633 K. O2 + H + H2 - HO2 + H2 (3)

The recommended expression is based on the latter value and

-11 3 -1 -1

k^ = 5 X 10 cm molecule s at 300 K (3) : the value

calculated from Rosser and Wise's data (1) lies within 12% of

this expression at 500 K.

100
NO^ + H NO + HO

References considered;

1. W. A. Rosser and Wise, J. Chem. Phys. 65, 532 (1961); 65^ 2277

(1961)

2. P. G. Ashmore and B. J. Tyler, Trans. Faraday Soc. 58^ 1108 (1962)

3. L. F. Phillips and H. I Schiff, J. Chem. Phys. 37_, 1233 (1962)

4. V. N. Kondratiev, Rate Constants of Gas Phase Reactions, (Science

Publishing House, Moscow (1970)

5. D. L. Baulch, D. D. Drysdale, D. G. Home and A. C. Lloyd, Evaluated Kinetic Data for High Temperature Reactions, Vol. 1 (Butterworths, London, 1972) p. 377

Evaluators

:

D, L. Baulch, D, D. Drysdale and D. G. Horne

Date: March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

101
Chemical Kinetics Data Survey

The reaction of water with nitric oxide

(1) + NO -» HNO + OH

Preferred value : = 3 X 10 "'"^ cin"^molecule '''s ^

Temperature: 2000 K

Reliability: Uncertainty in log : ±0.2 at 2000 K

Remarks

There are no experimental data on reaction 1.

H2O + NO HNO + OH (1)

The above value is based on the recommended value of k (1) and

equilibrium data. The temperature dependence of k^ is not known.

References considered:

1. C. J. Halstead and D. R. Jenkins, Chem. Phys. Letts. 2^ 281

(1968)

Evaluators :

D. L, Baulch, D, D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found :n "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

AH(300)

kJ mol

290.6

-1

(kcal mol ) (69.46)

102
Chemical Kinetics Data Survey

The reaction of hydroxy! with HNO AH(300)

kJ mol ''' (kcal mol ''') (1) OH + HNO - + NO -290.6 (-69. A6)

Preferred value :

, _ , T_-ll 3 T 1-1-1

kj^ — 6 X 10 cm molecule s Temperature: 2000 K

Reliability: Uncertainty in log k^^ : ±0.2 at 2000 K

Remarks

:

Studies of the NO-catalysed recombination of atoms and radicals in

flames have given data on k^ in the region of 2000 K. We recommend

-11 3 -I -1

kj^ = 6 X 10 cm molecule s obtained by Halstead and Jenkins

from H-/0„ flames (2) but point out that Smith (3) has recently

-11 3 -1 -1

determined k^ = 1.8 x 10 cm molecule s at 2117 K in ^^^S^^Z^^l

flames. The reason for this discrepancy is not clear.

References considered ;

1. E. M. Bulewicz and T, M. Sugden, Proc, Roy. Soc. A277 , 143

(1964)

2. C, J. Halstead and D, R, Jenkins, Chem. Phys. Letts. 2, 281

(1968)

3. M. Y. Smith, Combustion and Flame 18, 293 (1972)

Evaluators : D. L, Baulch, D. D, Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

103
Chemical Kinetics Data Survey

The disproportionation of HNO AH(300)

kJ mol (kcal mol ''') (1) HNO + HNO H2O + N2O -358.9 (-85.8)

Preferred value:

-15 3 -1-1

k, = 4 X 10 cm molecule s 1 Temperature: 300 K

Reliability: Uncertainty in log k^: ±0,3 at 300 K

Remarks

Kohout and Lampe (2) provided the first conclusive evidence for

this reaction in a mass spectrometric study of the mercury -photosensitised H2/NO reaction

HNO + HNO H2O + N2O (1)

16 3 11 Their value for k^ = 6.7 x 10 cm molecule s was obtained by

comparing the decays of HNO and N2O following a period of photolysis,

Callear and Carr (3) obtained k^ = 4 x lO"-'-^ cm^molecule'^s'l by

studying the flash photolysis and mercury-sensitised flash photolysis

of H^/NO mixtures, monitoring HNO by kinetic spectroscopy. They

attribute this discrepancy to a systematic error in Kohout and Lampe '

s

work, arising from non-homogenous production of HNO in their photolysis

cell. We recommend that Callear and Carr's value be used at 300 K,

References considered :

1. M.A.A, Clyne, 10th Combustion Symp, 311 (1965)

2. F, C. Kohout and F. W. Lampe, J, Chem. Phys. 4_6, 4075 (1967)

3. A. B. Callear and R. W. Carr, private communication

Evaluators

D. L, Baulch, D, D. Drysdale and D. G. Horne

Date: April 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions, Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

104
Chemical Kinetics Data Survey

The dissociation of annnonla AH(300)

kJ mol (kcal mol ^)

(1) NH^ + Ar -» + H + Ar ^52. 3 (10$. 1)

Preferred value ; = 1.5 X 10 exp[-42 AOO/T] cm molecule s Unlmolecular reaction In Its second order region below 4 atm (3-6).

Temperature range: 2000 < T < 3000 K

Reliability: Uncertainty in log k: +0.3 in temperature range quoted

Remarks:

The decomposition of NH^ has been studied in the temperature range

2000-3300 K by shock tube techniques. The results are scattered,

particularly below 2500 K where Induction periods (4,5;, 6) and fractional orders (1) have been reported. Clearly, the mechanism is

complex (2), Henrici (4) monitored the removal of NH^ during the

induction period and deduced values of k(NH2 + Ar) from experiments

with very dilute NH^/Ar mixtures. At low temperatures (2000-2500 K)

and concentrations (0*03% NH„) his results lie significantly lower

than the other data (1,3,5,6): an Arrhenlus expression based on these

results is consistent with the data at 3000 K obtained at higher NH^

concentrations (3,4). However, until this work is confirmed, we cannot recommend Henrici *s expression for k(NH2 + Ar) and Instead suggest

the expression given above which is a compromise between the low con- centration data (4) and the data of Michel and Wagner (3). More work

is required to resolve the kinetics of ammonia decomposition between

2000 and 2500 K.

Of the remaining work, Jacobs (1) found a fractional order for NH^

removal, reflecting a complex mechanism, and his data cannot be used

directly to define k(NHo + Ar) , Takeyama and Mlyama's results (5) lie

somewhat higher than all the others, which may be due to the presence

of impurities in their reagent gases, Bradley's data (6) are very

scattered, perhaps as a consequence of the very high NH^ concentrations

used: he quotes an expression for k(NH2 + Ar) but gives no details of its

calculation.

References considered ; 1. T. A, Jacobs, J, Phys. Chem. 67_, 665 (1963)

2. H. E, Avery and J. N. Bradley, Trans. Faraday Soc. 60, 857 (1964)

3. K, W. Michel and H. Gg. Wagner, 10th Combustion Symp. 353 (1965)

4. H. Henrici, Ph.D. Thesis, Gottlngen (1966)

105
NH^ + Ar - NH^ + H + Ar

References considered (cont'd) ;

5. T. Takeyama and H. Miyama, Bull. Chem. Soc. Japan 39., 2352 (1966)

6. J. N. Bradley, R. N. Butlin and D. Lewls_, Trans. Faraday Soc. 63,

2962 (1967)

7. M, C. Branch and R, F, Sawyer, Dept. Mech. Eng., Thermal Systems

Division, Unlverlsty of California, Berkeley, Report TS-71-1 (1971)

8. K. Schofield, General Motors Corp., Delco Electronic Division,

Report TR-71-57 (1971)

E valuators;

D, L. Baulch, D. D. Drysdale and D. G. Horne

Date; March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Voluem 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterowrths, 1973 in

press) by these authors.

106
Chemical Kinetics Data Survey

The combination of amino with hydrogen

atOTis to form ammonia

(1) + H + Ar -» NH^ + Ar

Preferred value; = 1.2 X 10"'^\xp[112 00/T] cm^molecule'^s""^

Temperature range: 2000 < T < 3000 K

Reliability: Uncertainty In log k: +0.3 In temperature range quoted

Remarks;

The above expression Is based entirely on the rate constant of the reverse reaction and equilibrium data. Gordon et al (1) reported a value

of k(NH2 + H + M) at 300 K but this cannot be considered reliable as they

assumed that the competing reaction + ~* ^2^4 second

order region below 1 atm pressure. This is probably incorrect.

References considered ;

1. S. Gordon, W. Mulac and P. Nangla, J. Phys. Chem. 15, 2087 (1971)

Evaluators;

D. L, Baulch, D. D, Drysdale and D. G. Home

Date: March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

AH(300)

kJ mol ^ (kcal mol ^)

-452.3 (-108.1)

107
Chemical Kinetics Data Survey

The reaction of ammonia with hydrogen atoms

kJ mol

16.2

AH(300)

-1

(kcal mol ) (3.87) 2

Preferred value ; "'Ifi 3 —1 —1 < 10 cm molecule s at 800 K

Reliability: Approximate upper limit only

Remarks

;

The metathetlcal reaction 1 has been Invoked a number of times In a variety of systems (2,4,7,8,9) and k^^ deduced from kinetic analyses of

complex mechanisms (2,7,9).

1, -

_ NH^ + H NH^ + H2

However, discharge-flow studies have revealed that the true rate con- stant may be as much as two orders of magnitude less than the values

obtained In the other studies. Thus Albers et al (5) and Kurylo et al

(6) could detect no net consumption of hydrogen atoms when ammonia

was added to a stream of H-atoms In a discharge -flow system (800 and

750 K respectively). In subsequent experiments, Kurylo et al (6)

observed a substitution reaction to take place when D-atoms were reacted with NH^.

2. NH^ + D NH^D + H

More work on this system would be merited.

References considered ;

1. M. Schlavello and G. G, Volpi, J. Chem. Phys, 37, 1510 (1962)

2. K. T, Aganesyan and A, B. Nalbandyan, Dokl. Akad. Nauk SSSR 160 , 162 (1965)

3, R. Tunder, S. Mayer, E, Cook and L. Schleler, Aerospace Corp.

Report TR-100 (9210-02) -1 (1966)

4, F, T, Jones and T. J, Sworskl, Trans, Faraday Soc, 63^, 2411, 2426

5. E, A, Albers, K. Hoyermann, H. Gg. Wagner and J. Wolfrum, 12th

Combustion Symp. 313 (1969)

6. M. J. Kurylo, G. A. Holllnden, H. F. LeFevre and R. B. Tlmmons,

J, Chem. Phys, 51, 4497 (1969)

7. C. Willis, A. W. Boyd and 0. A. Miller, Can. J. Chem. 47, 3007

(1969)

8. J. A. Eyre and D. Smithies, Trans. Faraday Soc. 66, 2199 (1970)

9. A, W. Boyd, C. Willis and 0. A. Miller, Can. J. Chem. 49, 2283 (1971)

10. M. C, Branch and R, F. Sawyer, University of California, Berkeley,

Dept. Mech. Eng., Thermal Systems Div. , Report TS-71-1 (1971)

(1967)

108
Chemical Kinetics Data Survey

The reaction of amino with hydrogen molecules AH(300)

kJ mol ^ (kcal mol

1. + H2 - NH^ + H -16.2 (-3.87)

Preferred value; < 10 cm"^ molecule "'"s"''" at 800 K

Reliability: Approximate upper limit only

Remarks

There are no data available on this reaction. The above upper limit

is based on an estimate of the upper limit of the rate constant

(-1) NH^ + H -» + H2

**1 6 3 *•! 1 for the reverse reaction, k^^ < 10 cm molecule s at 800 K, and

equilibrium data.

References considered ;

1, E, A, Albers, K, Hoyermann, H, Gg. Wagner and J. Wolfrum, 12th

Combustion Symp. 313 (1969)

E valuators;

D. L. Baulch, D, D, Drysdale and D, G. Horne

Date: March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Buttecworths, 1973 in

press) by these authors.

110
NH^ + H - + H2

Evaluators;

D, L, Baulch, D, D. Drysdale and D, G. Home

Date: March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the ^2~^2~'^2 ^y^*-®TM" (ButterworthS;, 1973 in

press) by these authors.

109
Chemical Kinetics Data Survey

The reaction of ammonia with oxygen

atoms to form amino and hydroxyl AH(300)

-1

1.

kJ mol

23.8

(kcal mol ) (5.7)

Preferred value;

kj^ = 2.5 X 10 exp[-3020/T] cm molecule s

Temperature range: 300 < T < 1000 K

Reliability: Uncertainty In log k: + 0,2 In temperature range quoted.

The reaction between ammonia and oxygen atoms has been studied mainly In

discharge -flow systems (2,3,5,7^8): the stolchlome try was considered In

each case (except 2) and assumed to remain constant over the temperature

range studied. Despite a surprising variation In the stolchlome tries

observed (m = A[0]/ANH2 - 8(3), 4.4(5) and 2.9(7)), the agreement of the

data frOTi (3,5,7 and 8) Is good although only the results of Albers et al

(7) for a linear relationship on an Arrhenlus plot (300-1000 K) . The

curvature In (3 and 8) may be due to the presence of 0„ In the system:

molecular oxygen was absent from (5 and 7) but a curved Arrhenlus plot

was also obtained In (5). Helcklen and Cohen (9) have pointed out some Inconsistencies In the kinetic treatment used by Wong and Potter (3,5)

and accordingly we favor the work of Albers et al (7) and recommend

above the rate constant which Is based on their data.

Of the remaining determinations we reject Avramenko's data (2) as there

appears to have been some Impurity In their system. Fenlmore and Jones'

crude estimate (1) was based on NO yields In a NH2/H2/O2 flame at 1600 K

and cannot be considered reliable. Finally, although the expression

derived by Aganesyan and Nalbandyan(4) from a study of the Inhibition

of the CO/O2 lower explosion limit Is In reasonable agreement with the

other data, it is not possible to give It much weight in this evaluation.

References considered:

1. C, P. Fenlmore and G. W. Jones, J. Phys. Chem. 65, 298 (1961)

2. L. I. Avramenko, R, V. Kolesnlkova and N. L. Kuznetsova, Izvest.

Akad. Nauk, SSSR, Otd, Khlm, Nauk, 6^ 983 (1962)

3. E. L, Wong and A. E, Potter, J. Chem. Phys. 39_, 2211 (1963)

4. K, T, Aganesyan and A. B. Nalbandyan, Dokl. Akad. Nauk SSSR, 160

162 (1965). English translation, p. 18.

Remarks:

111
NH^ + 0 -* + HO

References considered (cont'd)

5. E. L, Wong and A. E. Potter, J. Chem. Phys. 43, 3371 (1965)

6. R. Tunder, S, Mayer, E, Cook and L, Schleler, Aerospace Corp. Report,

TR-100 (9210-02_}_-l (1966)

7. E. A, Albers, K, Hoyermann, H. Gg. Wagner and J. Wolfrum, 12th

Combustion Symp. 313 (1969)

8. M. J, Kurylo, G. A. Holllnden, H, F, LeFevre and R. B. Timmons, J,

Chem. Phys. 51, 4497 (1969)

9. J. Helcklen and N, Cohen, Comprehensive Chemical Kinetics, Vol. 6,

editors C. H, Bamford and C.F.H. Tipper (Elsevier, Amsterdam, 1972)

p. 1.

E valuators;

D. L, Baulch, D, D. Drysdale and D. G. Horne

Date: March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

112
Chemical Kinetics Data Survey

The reaction of amino with hydroxyl

to form ammonia and oxygen atoms AH(300)

-1

1 + HO NH^ + 0

kJ mol

-23.8

(kcal mol ) (-5.7)

Preferred value;cm molecule s

Temperature range: 300<T< 1000 K

Reliability: Uncertainty in log k: +0.2 in temperature range quoted

Remarks ; There are no data available on this reaction: the above expression

is based on the rate constant for the reverse reaction (1).

(-1) NH^ + 0 + HO

k_^ = 2,5 X 10'"'"^exp(-3020/T) cm\olecule""'"s°''' and

equilibrium data

The alternative reaction NH2 + HO -* H2O + NH may be favored.

References considered ;

1. E. A, Albers, K, Hoyermann^ H. Gg. Wagner and J, Wolfrum, 12th

Combustion Symp. 313 (1969)

E valuators ; D. L. Baulch, D. D, Drysdale and D. G. Horne

Date: March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butte rworths, 1973 in

press) by these authors.

113
Chemical Kinetic a Data Survey

The reaction of ammonia v/lth hydroxyl

to form amino and water

1. NH^ + HO -* +

Preferred value ; No recommendation. See remarks

Remarks

;

The few estimates of the rate constant of this reaction are badly

scattered and cannot be usefully evaluated. A room temperature value

of 3 X 10"^^ cm^molecule'ls"*! by Wolfrum (5) seems high and at variance

with recent results of Worley et al (6) which suggest that the reaction

may proceed by an exchange, generating H atoms analogous to the NH^ + D

reaction (4),

2 . NH^ + OH - NH2OH + H

Further data on this reaction are required.

References considered;

1. C. P. Fenlmore and G. W. Jones, J. Phys. Chem. 65, 298 (1961)

2. R, Tunder, S, Mayer, E. Cook and L. Schleler, Aerospace Corp. TR-100

(9210-02)-! (1966)

3. E, A. Albers, K, Hoyermann, H. Gg. Wagner and J. Wolfrum, 12th Combustion Symp. 313 (1969)

4. M. J, Kurylo, G. A. Holllnden, H. F, LeFevre and R. B. Tlmmons,

J. Chem. Phys. 51, 4497 (1969)

5. K. Hoyermann, W. Hack and J. Wolfrum (private communication, 1972)

6. S, D. Worley, R. N« Coltharp and A. E, Potter, Jr., J. Phys, Chem,

76, 1511 (1972)

E valuators;

D. L. Baulch, D, D, Drysdale and D. G, Home

Date: March 1973

Additional Information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2, Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

AH (300)

kJ mol ^ (kcal mol ^)

-47. 1 (-11.26)

114
Chemical Kinetics Data Survey

The reaction of amino with water

kJ mol

A7.1

Ah(300)

-1

(kcal mol ) (11.26)

Preferred value : No recommendation. See remarks

Remarks;

There are no data available on this reaction and there are insufficient

reliable data on its reverse for any estimate of the rate constant.

References considered ; None

Evaluators:

D. L, Baulch, D, D. Drysdale and D. G. Horne

Date; March 1973

Additional information on this reaction may be found in "Evaluated

Kinetic Data for High Temperature Reactions. Volume 2. Homogeneous

Gas Phase Reactions of the H2-N2-O2 System" (Butterworths, 1973 in

press) by these authors.

115
FORM NBS-IMA («-71) U.S. DEPT. OF COMM. 1. PUBLICATION OR REPORT NO. 2. Gov't Accession

BIBLIOGRAPUC DATA ^^^^^ ^ No.

3. Recipient's Accession No.

|

4. TITLE AND SUBTITLE

CHEMICAL KINETICS DATA SURVEY

V. Bxxty— bix uoncriDucea Kate ana rno tocnemical Data

Evaluations on Ninety-Four Reactions

5. Publication Date

6. Performing Organization Code

7. AUTHOR(S)

Dr. David Garvin

8. Performing Organization

NBSIR 73-206

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

10. Project/Task/Work Unit No. 3160409

11. Contract/Grant No.

12. Sponsoring Organization Name and Address

Climatic Impact Assessment Program

Department of Transportation

Washineton D C 2n'iQn

and National Bureau of Standards

13. Type of Report & Period Covered

Interim

14. Sponsoring Agency Code

15. SUPPLEMENTARY NOTES

16. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here.) This report records the data evaluations contributed to the Climatic Impact

Assessment Program chemical kinetics survey during the period Nov. 1972 - April

1973 by various kineticists and photochemists. Data are included on reactions

of 0(^D), 0(^S), 02(^A), CH^ONO, CH^O, CH^O^, ^^0^, HO^, SO, SO2 and the

H--N_-0- system.

17. KEY WORDS (Alphabetical order, separated by semicolons) Atmospheric chemistry; Chemical kinetics;

Data evaluation; Gas phase reactions; Optical Absorption cross sections;

Photochemistry; Quantum yields; Rate constants

18. AVAILABILITY STATEMENT 19. SECURITY CLASS

(THIS REPORT)

21. NO. OF PAGES

rXI UNLIMITED.

UNCL ASSIFIED

115

1 1 FOR OFFICIAL DISTRIBUTION. DO NOT RELEASE

TO NTIS.

20. SECURITY CLASS

(THIS PAGE)

UNCLASSIFIED

22. Price

USCOMM-DC 66244.P71