NBSIR 203

Chemical Kinetics Data Survey

IV. Preliminary Tables of Chemical

Data for Modelling of the

Stratosphere

David Gatvin, 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

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NBSIR 73-203

CHEMICAL KINETICS DATA SURVEY

IV. PRELIMINARY TABLES OF CHEMICAL

DATA FOR MODELLING OF THE

STRATOSPHERE

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

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

NATIONAL BUREAU OF STANDARDS, Richard W. Roberts. Director
i
Table of Contents

I . Introduction 3

II. Related Material 6

III. Needed Work 7

IV. Tables

1) Chemical reactions and photochemistry of neutral species. 8

2) Energy transfer reactions. 64

3) High temperature air reactions. 70

4) Ion-molecule reactions. 72

Second Printing - July 1973

i

Chemical Kinetics Data Survey

IV. Preliminary Tables of

Chemical Data for

Modelling of the Stratosphere

Abstract

Chemical kinetic and photochemical data for gas phase reactions

pertinent to the chemistry of the stratosphere are presented in

four tables. These tables give recommended values and also cite

recent experimental work. They give data in the following subject

areas: chemical reactions and photochemistry of neutral species,

energy transfer reactions, high temperature air reactions, and ionmolecule reactions.

Keywords: atmospheric chemistry, chemical kinetics, data evaluation,

energy transfer, gas phase, high temperature air chemistry, ion-molecule

reactions, optical absorption cross sections, photochemistry, quantum

yield, rate constants.

1
0
I , Introduction

This report consists of a set of tables of rate constants and

photochemical data. These are preliminary tables designed for use

in modelling of the stratosphere. They are being distributed now

for interim use and for criticism by kineticists.

The tables are an extract from the chapter "Chemistry of the

Stratosphere" by H. S. Johnston, R. J. Cvetanovic, D. D. Davis,

E. E. Ferguson, D. Garvin, R. D. Hudson, H. I. Schiff and R. Taylor,

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

Assessment Program Monograph No. 1. The first draft was prepared

in November 1972.

The tables as distributed here have been revised to include

new data and also to include contributions of rate evaluations by

other scientists. These contributers represented in the present

edition are D. L. Baulch, D. D. Drysdale and D. G. Home (University

of Leeds), J. Heicklen (Pennsylvania State University), W. H.

Breckenridge (University of Utah), T. G. Slanger (Stanford Research

Institute) and K. H. Welge (York University).

3
The tables are in several parts:

(1) Chemical reactions and photochemistry of neutral species

(by the entire group).

(2) Energy transfer reactions (R. Taylor).

(3) High temperature air reactions (R. Taylor).

(4) Ion-molecule reactions (E. E. Ferguson).

Bibliographies are included. These are also taken from the

chapter. Occasionally the tables include comments that refer the

reader to the text. This auxilliary information has not been included

in this report.

It is the goal of the authors of these tables to provide

recommended values for as many chemical processes pertinent to

the stratosphere as possible. Where practical the basis of the

recommendation has been made evident by citing recent experimental

work

.

But this is a preliminary selection. There may be pertinent work

that has been omitted, incorrect citations of numbers, inadequate

interpretation and even faulty recommendations. The reader will

provide a valuable service by pointing these out to us and by

suggesting better recommendations.

4
Correspondence about these tables should be sent either to

David Garvin, B-152 Chemistry Building, National Bureau of Standards

Washington, D. C. 20234 or to H. S. Johnston, Department of Chemistry,

University of California, Berkeley, California 94720.

5
II. Related Material

These tables rely heavily upon other modern data evaluation

work. Some pertinent sources are summarized here.

Contributors to this data survey were mentioned in the

introduction. Their evaluations are given in more detail in

NBS Report 73-206 (May 1973).

Evaluations by a team at NBS have been distributed in NBS

Report 10692 (January 1972) and NBS Report 10828 (April 1972).

These will appear, in slightly revised form, in J. Phys

.

Chem. Ref. Data 2 No. 2 (Summer 1973).

Evaluations by a group at the University of Leeds under the

direction of D. L. Baulch have been published in "Evaluated Kinetic

Data for High Temperature Reactions, volume 1, Homogeneous gas

phase reactions of the ^2~^2 system" D. L. Baulch, D. D. Drysdale,

D. G. Home and A. C. Lloyd, (Butterworths, London, 1972). Earlier

evaluations by the same group have appeared in five reports from the

Department of Physical Chemistry, University of Leeds, entitled

"High Temperature Reaction Rate Data".

Data on reactions occurring in photochemical smog have been

evaluated in "The Mechanism of Photochemical Smog Formation" by

K. L. Demerjian, J. A. Kerr and J. G. Calvert (to appear in Advances

in Environmental Science and Technology, J. N. Pitts, Jr. and R. L.

Metcalf, editors, Wi ley-Interscience, volume 4, 1974).

6
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 stratosphere, 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 this report

(immediately before Table I). These will be incorporated in the

tables. Detailed evaluations will be issued in companion reports

(such as NBS Report 73-206). We will also welcome comments and

corrections of any of the recommendations.

7
I. Tables of Rate and Photochemical Data

Introduc tion

These tables provide current (May. 1973) best estimates for

reaction rate constants, quantum yields and absorption cross sections.

The reactions reviewed and other reactions for which selected data

are needed are listed in a table of contents at the beginning of the

table itself. Some of the reactions reviewed are not classed as

important. Data are given for them for purpose of comparison. Other

sections of the chapter also include data. See "High temperature

air chemistry" for nitrogen oxide formation reactions in that regime,

"Energy transfer kinetics for the stratosphere" and "Ionic reactions".

Evaluations of data and remarks on specific chemical problems are

gathered into section G "Special cases of important reaction systems".

The data have been selected by members of the Chemistry Panel

and by other kineticists who have volunteered to review reactions of

interest to them. Several principles have been used in the selection

and presentation of data.

(a) Where there is a recent published evaluation of the

data and there are no newer data, the evaluation is

adopted

(b) Where there is an evaluation but there are new data,

both are listed and a preferred value is indicated

(marked by an asterisk)

8
(c) Where desirable, the available recent data sets are

listed, and a selection is made or a preferred

value is synthesized from them.

The persons making new selections or syntheses are usually

identified by initials.

These selections are necessarily tentative because there it much

current research on these atmospheric reactions. Indeed, we have

often been influenced in making our selections by preliminary

results that have been made available to us. As new data are published they will be incorporated in the tables.

The Panel expresses its appreciation to scientists who have

provided reports on their current work and who have suggested

improvements. We are particularly indebted to those who have contributed evaluations of data: D. D. Baulch, D. D. Drysdale and

D. G. Home, University of Leeds; J. Heicklen, Pennsylvania State

University; T. G. Slanger, Stanford Research Institute and K. H.

Welge, York University and W. H. Breckenridge, University of Utah

Conventions Concerning Rate Constants

for Some Dissociation and Combination Reactions

Some reactions of these types are not of integral kinetic order over

the stratospheric pressure and temperature range. That is, although

they require an energy transfer agent, "M, " they are in the "pressure

fall-off region".

9
For such reactions we tabulate rate constants that include the effect

of the energy transfer agent and give rates for various altitudes.

The reactions are written to deemphasize "M, " e.g.,

or N0

2 + N03 (+M) -» N

2

0

5 (+M)

HN0

3

3 HO + N0

2

The rate expressions to be used do not have the concentration of

M in them, e.g., Rate = k[N0

2

] [NO^] and k[HN0

3

] . The units given

-1 -3 -1

for the k's, s for first order, and cm molecule s for second

order, are consistent with this convention.

The altitude, temperature and number density regime used in these

cases is

-3 altitude/km temp . /K log[M] /molecule cm

15 220 18.60

20 217 18.27

25 222 17.93

30 227 17.58

35 235 17.26

40 250 16.92

45 260 16.60

Except for the temperature at 15 km this table follows the U. S.

standard atmosphere, 1962. In tables to be prepared in the future

we intend to allow for observed temperature and number density

variations at each altitude.

10
4

Convention concerning optical absorption coefficients

These are reported in the tables as "absorption cross sections per

molecule, base e". They are defined by the equations

I/I = exp(-cr[N]£)

a = (l/([N]i))ln (I o /l)

where I and I are the intensities of incident and transmitted light,

2 -1

(7 is the absorption cross section, cm molecule , [N] is the

_3 concentration of absorbers, molecules cm , and * is the path length,

cm. Other definitions and units are frequently used. The terms

"absorption coefficient" and "extinction coefficient" are common.

It is always necessary to know what concentration units, path length

units and type of logarithim (base e or base 10) are used in the

definition.

To convert "cross sections" to absorption coefficients in

(atm at 273 K) cm , base e, multiply by 2.69 x 10

11
5

Arrangement of the Table

1. Reactions are listed only once. They are in groups in this order:

(a) Reactions among oxygen species: 0, 0 , C^C A), O^i^^)

and 0^ and reactions of 0 with all species.

(b) Reactions of hydrogen/oxygen species: H, H

2

, HO, HCL,

H^O, H^O^ among themselves and with group a, above.

(c) Reactions of nitrogen/hydrogen/oxygen species: N,

NO, N02< N0

3

, N

2 0, N

2 0

5

, NH, NH , NH^ , HNO, HNO^,

HNO^ among themselves and with molecules in earlier groups.

(d) Reactions of sulfur compounds: SO, S0

2 , S0^, H2 S0^

among themselves and with molecules in earlier groups.

(e) Reactions of carbon compounds, CO, CH^, CH^, CHO, CH 0,

CH 0, CH^O,^, ^2^4' ^2^6' ^3^6'

2. A reaction is placed in the last group to which any reactant

belongs, e.g. NO + 0^ = N0

2 + 0

2 in group c

.

3. Within a group, reactions are filed with the reactant later

in the list for the group N0

2 + NO^ -» N2

0,_ under N0^ .

4. All reactions of a substance with those before it in the filing order

appear together. The sequence is reaction with the earliest substance

in the sequence first, e.g . NO + 0, then NO + 0

2

, . . . . NO + N.

(The order of substances in a group is atom, compounds of only

the primary element, then those with 0, those with H, those with H and

0 etc. That is, combinations with the element in each earlier group in

orde r .)

"Note: the placement of all reactions of 0( 1d) and ( ls

^ in § rouP 1 is an exception to the general rules.
Contents of the Table and Other Reactions of Interest

a. Reactions among Oxygen Species

Reactions reviewed

0 -]- 0 + M -> o

2 + M

0

2

+ 0 + M Q

3

4- M

0(~D) + 0

2 , 03

, CO, C0

2 , N2

,

N

2

C, NO, N0

2 , H2, H

2 0, CH

4

,

C

2 H6 , NH3 , H

2

0

?

0(

XS) + o, o

2 , o

3

, co

2

,

N

2

, N

2 0, NH

3

, NO, N0

2 , H

2

0, CH

4

0

2

( 1A) + M -> 0

2 + M

0

2

(

1T) + M -4 0

2 + M

0„ + hv -> 0 + 0

2

0

3 + 0 -» o2 + o2

Reactions not reviewed for which selections are needed

0

2 + hv •* 0 + 0

09 ( 1A) + 0, -*

13
b. Reactions of

Reactions reviewed

H + 0

2 + M -» H02 + M

H + 0

3

-* HO + 0

2

HO + HO -* H + H0

2

H

2 + 0

2 *

H

2 0 + 0

H0 + M-»H + 0+ M

HO + 0 -» H + 0

2

HO + 0

3

-> H0

2 + 0

2

HO + H -» H

2 + 0

HO + H + M -» H

2 0 + M

H °2 + °3 ~* H0 + 20

2

H0

2 + H0

2 H

2 02 + 0

2

H0

2 + M-+H + 0

2 +M

-» HO + 0 + M

H0

2 + H -» H

2 + 0

2

-* H

2 0 + 0 ^

-> HO + HO

H0

2 + HO -» H

2 0 + 0

2

rogen/oxygen species

H

2 02 + hv -> HO + HO

H

2°2 + ° (3p) "* H0

2 + H°

* H2° + °2

H

2 02 + H -» H2

+ H0

2

-» H

2

0 + HO #

H

2

0

2 + HO -» H

2 0 + H02

Reactions not reviewed for which

selections are needed

H + 0 + M HO +' M

HO + hv -» H + 0

HO" + M -> HO + M

H0

2 + hv -»

H0

2 + 0 HO + 02

H

2 0 + hv -» H + HO

* Selection needed.

14
c. Reactions of nitrogen/hydrogen/oxygen species

Reactions reviewed

N + 0 + M^NO + M

N

2 + 0 -» NO + N

N + 0

2

-> NO + 0

N + 0

3

-» NO + 0

2 N + HO + NO + H

NO + 0 -» 0

2 + N

NO +' 0 + M -* N0

2 + M

N0

2 + NO + 0

2

-> N0

2 + N0

3

H + N0

2

-> HO + NO

HO + N0

2 (+M) HN0

3

(+M)

H

2 0 + NO + N0

2

-» 2HN0

2 N0

3 + hv -» NO + 0

2 *

N0

3 + M -» N0

2 + 0 + M

NO + 0

2 + M -» N0

3

+ M *

0

2 + NO + NO -» N0

2 + N0

2 NO + 0

3

-» N0

2 + 02 NO + H + M -» HNO + M

NO + H

2 HNO + H

NO + H0

2

-> N0

2 + HO

NO + H

2 0 -» HNO + HO

NO + H

2 02

-* HO + HN0

2 N + NO -» N

2 + 0

NO + NO -» N

2 0 + 0

N0

2 + M-+N + 0 + M

N0

2

4- 0 + M + N0

3 + M

N0

2 + N -* Products

N0

2 + 0 * NO + 0

2 N0

2

+ °2 ~* N° + °3

N0

2 + °3 "* N0

3 + °2

N0

2 + N0

2

-» NO + N0

3 *

N0

3

+ °2 ~* N0

2 + °3

N0

3

+ N0

3

-> N0

2 + N0

2

+ 0

2 N0

3 + NO -» N0

2 + N0

2 NO„ + NO -> NO- + NO + 0 o 3 2 2 2 N0

3 + N0

2 (+M) -» N

2 0

5

(-5-M)

N

2 0 + 0 -> NO + NO - N

2 + 0

2 N

2 0

5 + hv 4 0 + ... *

N

2 0

5 (+M) "» N0

2 + N0

3 N2°5 + H 2° ~* 2HN0

3

0 + NH

3 HO + NH

2 HNO + M-*H + NO + M

0

2 + HNO -> NO + H0

2 H + HNO -» H

2 + NO

HO + HNO 4 H

2 0 + NO

HNO + HNO -> H

2 0 + N

2 0

HN0

2 + hv -» HO + NO *

•^Selections needed

15
HN0

2 + H -* products *

HO + HN0

2

-> H

2 0 + N0

2 HN0

3 + hV -» HO + N02

0 + HN0

3

-> HO + N0

3 H + HN0

3

-> products

HO + HN0

3

-» H

? 0 + N0

3

Reactions not reviewed for which

selections are needed

NO + hv -* N + 0

NO + HO (+M) -* HN0

2 + M

NO + H0

2 (+M) + HN0

3 + M

N0

2 + hy) -> NO + 0

N0

2 + H0

2 (+M) ~* H0

2N02 N0

2 + H0

2

-> HO + N0

3 N0

3 + hv -> NO + 02 N

2 0 + hv -> N

2 + O^D)

0 + N

2 0

5

-> . . .

N2°5 + H0 "*

0 + NH ->

0

2 + NH 4

0 + NH

2

0

2 + NH2 4

HO + NH

3

-» H

2 0 + NH

2 HNO + hv -» H + NO

16
d. Reactions of sulfur /nitrogen/hydrogen/oxygen species

Reactions reviewed

o

3

+ SO -» o

2 + so

2 H

2

S0^ (aerosols) + hv -*

0 + S0

2 + M -* S0

3

+ M 0( D) + H

2 S04 (aerosols)

H0

2

+ S0

2

-» S0

3

+ HO N

2 05

+ H

2

S04

Reactions not reviewed for which NH^ + K

2

S °4 ^ +M^

~' NH

4HS °4

selections are needed

SO + hv -> S + 0

o

2

+ SO -> so

2 + 0

S0

2

+ hv -» SO + 0

0 + so,

°3 + S °2 +

HO + S0

2 (+M) -» H0S0

2

S0

3

+ hv "* S0

2

+ 0

o + so

3

-»

HO + S0

3

(+M) <* H

2 SC

4

H

2

0 + SO -> H

2

SO^

°3 + S 2°

•Selection needed

17
e. Reactions of carbon species

Reactions reviewed

o

3 + co -> co

2 + o

2

CO + HO + C0

2 + H

CO + H0

2

-» C0

2 + HO

CH

3 + 0

2

-» CH

2 0 + HO

0

2 + CH3 + M -* CH

3 02 + M

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0

3 + CH^ products

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2

0

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2

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2

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CH

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0

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0

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0

2

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2

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2

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3

0

2 N0

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0

2

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3

C

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3 6 3 3 6 3

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Reactions not reviewed for which

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-» 0„ + NO," typescript, Stanford

Research Institute, January 30, 1973

3 Slanger, To G. and Black, G., "Reaction Rate Measurements of 0( P)

3

Atoms by Resonance Fluorescence. I. 0( P) + + M -* 0- + M and

0(

3 P) + NO + M - N0

2 + M," Jc Chem; Phys. 53, 3717-3721 (1970)

Slanger, T„ G. and Welge, K. H., "Rate Constants for Reactions of 0( S), 1

Data sheets prepared for this survey, Januar}' 1973

Stedman, D. H c and Niki, H., "Kinetics and Mechanism for the Photolysis

of NO2 in Air," typescript (to be published)

Stuhl, F., "Absolute Rate Constant for the Reaction OH + NH_ - NH„ +

3 2

H

2 0," typescript (1973)

61
Stuhl, Fo and Niki, H 0 , "Detection of Oxygen ( P) Atoms in Pulsed Vacuum

UV Photolysis of NO and Its Application to 0 Atom Reactions/' Chem„

Phys„ Letters ]_, 197-200 (1970)

Stuhl, F. and Niki, H., Measurements of Rate Constants for Termolecular

3 Reactions of 0( P) with NO, Oj, CO, N

2

, and C0

2 Using a Pulsed

Vacuum-uv Photolysis-Chemilumine scent Method," Jo Chem. Phys„ 55 ,

3943-3953 (1971)

Stuhl, F. and Niki, H. , "Pulsed Vacuum-uv Photochemical Study of Reactions of OH with H

2 , 02

, and CO Using a Resonance -Fluorescent

Detection Method," J 0 Chem 0 Phys 0 57, 3671-3677 (1972)

Tsang, W., "Comparison between Experimental and Calculated Rate Constants

for Dissociation and Combination Reactions Involving Small Polyatomic

Molecules," typescript, Natl. Bur. Std 0 (November 1972)

Vardanyan, I„ A., Dangyan, T. M<> , and Sachyan, G. A., "Rate Constants

for the Reaction H0

2 + CO - C0

2 + OH," Dokl. Phys 0 Chem. 205, 632-634

(1972); tr. of Dokl. Akad» Nauk SSSR 205, 619-621 (1972)

Volman, D. H» and Gorse, R. A., "Rate Constant for the Reaction of H0

2 with Carbon Monoxide," J. Phys. Chem. 76, 3301-3302 (1972)

Walker, Ra W„, "Activation Energies of the Reversible Reaction between

Hydrogen Atoms and Methane to give Hydrogen and Methyl Radicals,"

Jo Chem0 Soc, Secto A, 2391-2398 (1968)

62
Westenberg, Ae A« and deHaas, N„, "Steady-State Intermediate Concentrations and Rate Constants. Some HC^ Results/' J. Phys. Cheirio 76 ,

1586-1593 (1972)

Wilson, Wm0 E„, JrOJ "A Critical Review of the Gas-Phase Reaction

Kinetics of the Hydroxyl Radical," J. Phys c Chem. Ref. Data 1, 535-

573 (1972)

Wong, Wo and Davis, Do D. , "Kinetic Study of the Absolute Rate Constant

of H + 0„ + M, " typescript, University of Maryland (1972)

63
Chemical Kinetics Data Survey

Rates of Energy Transfer Processes

The rate constants are all listed for the exothermic reaction path.

The form of the rate constants listed in the following table have

been fitted to experimental data where available and either use a

theoretical temperature dependence for extrapolation, or the general

trend of the data itself has been used to suggest the temperature

dependence

.

R. L. Taylor

May 1973

64
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67
REFERENCES

1. Bitterman, S. and R. L. Taylor, Survey of Vibrational Relaxation Data

for Atmospheric Molecular Constituents, Avco Everett Research Laboratory Note 789, 1969

2. Borrell, P. and B. E. Millward, J. Chem. Phys. 50; 1911 (1969)

3. Breshears, W. D. and P. F. Bird, J. Chem. Phys. 48, 4768 (1968)

4. Buchwald, M. I. and S. H. Bauer, J. Phys. Chem. 76, 3108 (1972)

5. Center, R. E. , submitted for publication 1972

6. Keifer, J. H. and R. W. Lutz, Eleventh Symposium (International) on Combustion, p. 67 (1967)

7. Kovacs, M. A. and M. A. Mack, Appl. Phys. Lett. 20, 487 (1972)

8. Margottin-Maclou, M. , L. Doyenette, and L. Henry, Appl. Opt. 10 , 1768 (1971)

9. McNeal, R. J., M. E. Whitson, Jr., and G. R. Cook, Chem. Phys. Lett.

16, 507 (1972)

10. Millikan, R. C. and D. R. White, J. Chem. Phys. 39, 3209 (1963)

11. Moore, C. B., R. E. Wood, B. L. Hu, and J. T. Yardley, J. Chem. Phys.

46, 4222 (1967)

12. Moore, C. B. (Submitted for publication 1971).

13. Rosser, W. A., Jr., A. D. Wood, and E. T. Gerry, J. Chem. Phys. 50,

4996 (1969)

14. Rosser, W. A., Jr. and E. T. Gerry, J. Chem. Phys. 51, 2286 (1969)

15. Rosser, W. A., Jr., R. D. Sharma, and E. T. Gerry, J. Chem. Phys. 54 , 1196 (1971)

16. Rosser, W. A. and E. T. Gerry, J. Chem. Phys. 5_4, 4131 (1971)

17. Sato, Y., S. Tsuchiya, and K. Kuatani, J. Chem. Phys. 50, 1911 (1969)

18. Sato, Y. and S. Tsuchiya, J. Phys. Soc. Japan 13, 1120 (1972)

19. Seery, D. J., J. Chem. Phys. 56; 631, 4714 (1972)

20o Simpson, C. J. S. M. and T. R. D. Chandler, Proc. Roy. Soc. A3JL7,

269 (1970)

68
21. Stephenson, J. C. and C. B. Moore, J. Chem. Phys. 56, 1295 (1972)

22. Taylor, R. L. and S. A. Bitterman, Rev. Mod. Phys. 41, 26 (1969)

23. vonRosenberg, C. W., K. N. C. Bray, and N. H. Pratt, Thirteenth Symposium

(International) on Combustion, p. 89 (1971)

24. vonRosenberg, C. W., K. N. C. Bray, and N. H. Pratt, J. Chem. Phys. 5_3,

3230 (1972)

25. Worley, S. D. , R. N. Coltharp, and A. E. Potter, J. Chem. Phys. 55_,

26 (1971)

26. Worley, S. D. , R. N. Coltharp, and A. E. Potter, Jr., J. Phys. Chem.

76, 1511 (1972)

69
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r^-\ 01 CO n) CO X—

/—

/-—

CO c^ - . ro OV ft. u 0) CM a1 CM d) CM CM VO vO CM VO vO p vO H vO vO vO VD ^-^ *—

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CM II o m 1 u VO vO o cd II II .id II 55 II r-l OA II 53 H a: CM X

c o" cT X. o

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CM

CO

00

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O

o

o

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H

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o

o

oCM

o

o

o

VH

V

o

oo

CM

+

CM O

ta

+o

+o

S

+

CM

53ta

++

o

o

o

VH

V

o

oo

CM

a

+o

53ta

+o

+

53

O

O

V

•HVOO

o

CM

o

+

CM

o

S3+

S3

O

vOm

COa

x

0)

r-l

I

X

CM

CM

II

O

OO

V

H

V

o

o

o

CM

o

+o

S3

CM o

+

s

o

o

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o-X

<u CM

tn

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References

D. L. Baulch, D. D . Drysdale, D. G. Home, and A. C. Lloyd, High

Temperature Reaction Rate Data, Report No. 4, Dept. of Physical

Chemistry, The University, Leeds (1969).

M. Camac and R. M. Feinberg

Eleventh Symposium (International) on Combustion, p. 137 (1967).

S. C. Lin and J. D. Teare

Phys. Fluids 6, 355 (1963).

K. L. Wray, "Chemical Kinetics of High Temperature Air" Progress in

Astronautics and Rocketry Vol. 7, p. 181, 1962.

71
REACTION -RATE TABLES

I. Binary Positive -Ion Reactions

II. Binary Negative -Ion Reactions

EXPLANATION OF TABLES

The reactions are listed in the order: (l) atomic ions reacting with

neutrals, (2) molecular ions reacting with neutrals. The itns , are listed

according to atomic number except that obviously related reactions may be

grouped. No distinction is made between ion-atom interchange and chargetransfer reactions, i.e. those in which heavy particles are transferred as

contrasted to electrons . The rate constant is defined as the coefficient

( k in the expression - d[A ]/dt =k[A ][b] where [A ] and [b] are the ion

and neutral concentrations in the reaction A

+

+ B -* products.

The entries in the Tables are:

o -1 -1

k * Rate constant in cm sec (molecule implied)

Uncertainty See Introduction for Discussion

Method

FA Flowing Afterglow

This is a relatively high pressure experiment with many reactant ion

collisions prior to reaction so that the reactants are almost always known

to be in their ground states. This method has the greatest chemical versatility of all of the methods and so has produced a large fraction of the

available data. FA data have been obtained in the temperature range 80 -

600°K.

72
SA Stationary Afterglow

This is a high pressure experiment in which reactant ions can safely

be assumed to he in their ground states in most cases. The ionizing discharge may however produce excited or dissociated neutral reactants.

Photoionization sources have alleviated this problem but have been very

limited in their chemical versatility. Some SA experiments have covered

a range of gas temperatures from about 180 - 60C°PL

DT Drift Tube

This technique has only recently been applied to ion-molecule reactions

with good results. The reactants are expected to be in their ground s"=tes„

The method has the advantage of yielding reaction rate constants for ion

translational energy going from thermal up into the several electron volt

range. The data on energy dependences thus tends to augment thermal

energy data in many cases

MS Mass Spectrometer Ion Source

Most MS data in the literature have been obtained at lew press ;._ e

(thin target conditions) and this raises the possibility that the ions

may have been produced in excited states which can be quite misles.il„i^\

Some MS experiments } particularly those of Kebarle have worked at relatively high pressure and have thereby avoided this problem.. Low pressu 3

mass spectrometer ion sources measure reaction cross sections rather than

reaction rate constants. Since most applications require rate ccli£ ~:5_iits 1 this introduces a small uncertainty. Essentially Ja(E)E 2dE must be

73
approximated by o(e) E

2

, while in rate constant measuring experiments

(FA, SA, DT) the experiment itself accomplishes the integration. The

low pressure MS experiments also involve a small electric field in the

ion sampling so that the cross sections are measured somewhat above

thermal energy.

B Beam

Beam data are always obtained at energies in excess of thermal. The

extrapolations to low energy introduces some uncertainty into the low

energy cross sections. This is more serious for ion-atom interchange

reactions than for charge -transfer reactions in most cases. The beam

technique has been a very versatile technique in the kinds of neutral

reactants which can be studied, as for example metal atoms, and thus very

important in aeronomy. Beam experiments of course provide ion kinetic

energy dependences of the cross sections from fairly high ion kinetic

energies to energies substantially in excess of thermal.

i ICR Ion Cyclotron Resonance

The ICR technique has now been utilized for quantitative reaction

rate constant measurements for several years and is proving to be a very

valuable addition to the ion chemists armory. Since the ICR technique

involves low pressure experiments the possibility of excited state reactant

ions exists. Rate constants can in principle be measured as a function of

ion kinetic energy in ICR but most reported values are' essentially at thermal

energy.

74
D Discharge

A gaseous discharge is a somewhat unwieldy and complicated device for

determining individual reaction rate constants and very few such applications

have been carried out

In a few cases, binary ion -neutral reactions give more than one set of

products j usually two. In such cases two reaction channels may be given

and denoted by a and b for purposes of differentiating the separate rate

constants k

&

and k^ or to define a branching ratio, k /k^* It is often

the case that the overall ion loss rate, k

&

+ k , is much more precisely

measured than is the branching ratio. There aie cases where the reaction

products are undetermined and simply listed as "products". There are

also cases where no reaction was detected to give any products and this is

also indicated by "products" in order to exclude all possibilities.

References Given at the end of each Table.

The references are given by the first author of the paper and the f

year. All the papers of a given first author and year are further sequenced

by a small letter a, b, c, . . . etc. following the year.

Remarks Given at the end of each Table

.

The data refer largely to thermal energy (thermalized room temperature

measurements) but in some cases energy or temperature dependencies are available and this is so indicated in the column headed "Remarks".

In many cases reactions have been measured by more than one method and/or

in more than one laboratory. Measurements which have been improved or which

are otherwise considered to be obsolete or in error have not been tabulated.

75
TABLE I. Blnury Positive-Ion Reuctions

Reaction 3 -1\ k(cm see ) Uncertainty Method Reference Remarks

H

+

+ 0 - 0

+

+ H 3-8(-10) ± 5056 FA Fehsenfeld 1972a a H* + Fe - Fe

+

+ H 7.^(-9) B Rutherford 1972c 6

H

+

+ NO -• N0++ H l-9(-9) ± 30^ FA Fehsenfeld 1972a

H

+ + CO

g - COH

+

+ 0 3-0(-9) ± 3056 FA Fehsenfeld 1971a

Ob He* + Hg - products < 1 (-13) FA Fehsenfeld l°6{a .

He+

+ Ng * N

+

+ N + He , - N

2

+ He |

1.2(-9) ± 3056 FA Farragher 1970 k

a/k

b = 1.5, b

1.0(-9) + 0.3,-0.2 DT Heimerl 1969 V*b - 1.2; c

1.85(-9) * 15* ICR Iaudenslager 1973

1.2(-9) ± 20jt FA Dunkin 1968a d

• l-5(-9) ± 30S6 MS Warneck 1967a = 1.1

FA Schmeltekopf 1968 K/\ = 2.2, f lA5(-9) ± 15* SA Sayer6 1964 „ + -+ He + 0

£ - 0 + 0 + He + - Og + He l.o(-9) ± 30^ FA Farragher 1970 \/\ = 1.6

8.5(-10) + 2.5*,-2.0 DT Heimerl 1969 = k, c

1.5(-9) ± 25* ICR Lauden8lager 1973

1.2(-9) ± 3056 MS Warneck 1967

1.10(-9) ± 15* SA Sayers 196V

He

+ + CO - C+

+ 0 + He l-7(-9) ± 30* FA Fehsenfeld 1966a

2.0(-9) ± 15* ICS Iaudenslager 1973

1.6(-9) ± 30* MS Moran I966

He+

+ NO -i N

+

+ 0 + He 1.7(-9) ± 30* FA Fehsenfeld 1966a

2-K-9) ± 30* MS Moran I966

2.0(-9) ± 15* ICR Iaudenslager 1973

He+

+ HgO - products 5-6(-l0) ± 0.5 FA . Howard 1970

4.5(-10) ± 30* FA Bolden 1972

He* + COg - 0

+ + CO + He

. - C0

+ + 0 + He 1.2(-9) ± 30* FA Fehsenfeld 1966a

Ho + CH^ -* products

He+

+ CgHg — products

C

+ + Og - CO* + 0

C + COg - CO + CO

; 1.6(-9) ± 15* ICR Iaudenslager I973

1-5 (-9) ±15* ICR Bowers 1972

2.3(-9) ± 15* ICR Bowers 1972

l.l(-9) ± 30* FA Fehsenfeld 1966b

9-0(-10) ±30* MS Franklin I965

1.9C-9) ± 30* FA Fehsenfeld 1966b

1.6(-9) ±30* D Schlldcrout 1970

76
Table I Continued

Reaction k(cra oec ) Uncertainty Method Reference Rcmaj

C

+ + H„0 - COH+ + H

2 2.0(-9) ± 30/- FA Boldcn 1972

N

+ + Nq - Na+

+ N very small B Rutherford 1972a g

N

+

+ Mg -• Mg

+

+ N 1.2(-9) B Rutherford 1971 g

N

+

+ Va - Ca

+ + N l.l(-9) B Rutherford 1972b g N

+

+ Fe - Fe + N 1.5(-9) B Rutherford 1972c g

N

+

+ H0 NH

+

+ H

2

7 ( -10) ± 30/. FA Fehsenfeld 1967a

H* + CO -» C0

+ + N 5 (-10) ± 30$ FA Fehsenfeld 1967b

N

+

+ NO - N0

+ + N 8 (-10) ± 303& FA Goldan I966

K

+

+ 0o - 0o+

+ N - N0

+ + 0 7 (-10) ± 30/ FA Farragher 1970

; 5 (-10) ± 3036 DT Johnsen 1970 h

6 (-10) ± 3054 FA Dunkin 1968 d

6.l(-io) ± 305^ MS

FA

Warneck 1967b

Goldan 1966 k/k = 2 - K*K>

7 (-10) MS Aquilanti I966 k/k, = 1. a d N

+ + Ho0 - H_0+

+ N

2 2 2.6(-9) ± OA FA Howard 1970

2.6(-9) ± 30^ FA Bolden 1972

N

+

+ C0„ - C0o++ N

2 2 l-3(-9) ± 3036 FA Fehsenfeld 1967b

0

+" + H - H

+

+ 0

0

+

+ Na - Na

+

+ 0

6.8(-10)

small

± 50$ 1 and

Xea

;B

'Fehsenfeld 1972a

Rutherford 1972b

a

g

0

+

+ Mg - Mg" + 0 small 3 Rutherford 1971 g

0 + Ca -» Ca +0 7.6(40) B Rutherford 1972b • g

0

+

+ Fe -» Fe+* 0 2.9C-9) B Rutherford 1972c g

0

+

+ K0 - 0H

+

+ H 2.0(-9) ± 30$ FA Fehsenfeld 1967a

0

+

+ N_ - N0

T

+ N

2 1.3(-12) ± 15^ FA Schmeltekopf 1968 i

1.2(-12) ± 1056 FA

FA

Dunkin 1968

Ferguson 1969 .J O*^) + N_ - N

* + 0 2 2 ~1 (-9) B '

. Rutherford 1971 g 0

+

+ NO -• N0

+

+ 0 < 1 (-12) £*A Dunkin 1971a

0

+

+ 0„ -1 o«

T

+ 0

2 2 2.0( -11) ± 15$ FA Dunkin 1968

2.0( -11) +0.4,-0.3 SA

SA

FA

Copsey 1966

Smith I968

Ferguson I969

k

J,k

2.0(-ll) ± 0.5 MS Warneck 1967b

+ + o .+ co

2 - o

2 + CO 1.2(-9) ± 3096 FA Fehaenfeld 1966c

± 30/. MS Paulson I966

77
Reaction .

Tabic I Continued

kCcm^sec" 1

) Uncertainty Method Reference

0

+

+ HgO - H

20

+ + 0 2.3 '-9)J I ± 0.25 FA Howard 1970

2.1+ '-9) ±x jv/' ^Ci FA Bolden 1972

0

+

+ N 0 _ Ng0

+

+ 0 2.2 -10 ) +X 1X . J^ MS Ryan 1972

~* N0

+

+ NO 2 3 -10 ) ± l.h MS Ryan 1972

y

a + k

b

= 6 ^ -10) x jv-^/j FA Dunkin 1971a

0

+ + NC>2 -• N0

2

+

+ 0 1.6 -9) ±x ^Oi J v/u FA Dunkln 1971a

Na

+ + 0^ -• Na0+

+ 0

2 < 1 -11) FA Ferguson I968

Me

+

i n$ + 0 _ MgO

+ + 0

2 2.3 -10) ±x SOip FA Ferguson 1968

S+

+ NO - N0

+

+ S lt-.2( -10) x 205& FA Fehsenfeld 1973a

S+

+ 0

2 _ so

+

+ 0 1.6( -11) -xx; ± 2050 FA Fehsenfeld 1973a

+

Skj + CO

2

—t products < 1 -12) FA Fehsenfeld 1973a

Ar

+ + — ArH+ + H 6.8( -10) ± 2056 ICR Bowers 1969a

-10) FA Adams 1970

Ar

+ + _, jjg* + Ar 6.6( -11) MS Warneck 1967c

s i\ -li)xxy +x 7S<£ 1 ICR Laudenslager 1973

Ar

+ + CO co + Ar 1.21 -10) -fc ^0<£ MS , Warneck 1967c

q 0( -11)XX ^ x j*-7> FA Fehsenfeld 1966d

c= i ? \ -11) -xx; x ICR laudenslager 1973

Ar

+ + NO N0

+

+ Ar 3-9( -10) ± 30£ • MS Warneck 1967c

in\ x 3U?> Laudenslager 1973

+ At + 0^ —* Cl

^"

-4- At» .10) x rirfL MS Warneck 1967c

-xx

;

xx ji-'p ICvL FA -Adams 1970

*7 i x Laudenslager 1973

J v\ -n

)

-XX ^ x d^-fi SA Smith 1970

A n+ KT +• h n

2

. liilg^ ~+ At*

—* nXn ^ VJfl l.M -9) x 0.1 FA Howard 1970

l.6( -q) x FA Bolden 1972

ATa j-+ cn

2 ro 4. Ax -xu; irO xx ^rrf, JU?) Warneck 1967c

-xuj irA xX ^ntl Jl^b TTA Fehsenfeld 1966d

-io

;

x 1 Crf lL-n Laudenslager 1973 Ar

+ + CH^ - CH^ + H + Ar 6.5( -10) ± 3<>% MS Jones 1971 - CH2

+ + H

2

+ Ar i.M -10) ± 305& is Jones 1971

+ k

b

= 9.0( -10) ± 30£ FA Bolden 1970

-• products l-3( -9) ± 15^ ICR Bowers 1972 Ar

+

C2

H

6 — products 1.1( -9) ± 15^ ICR Bowers 1972 K

+

+ 0,

3 - K0

+

+ 0

2 < 1 ( -11) FA Ferguson I968

Remarko

78
Tuble I Continued

Reliction k( cin^sec"^) Uncertainty Method Reference

Cu

+

+ 0, - Cq0

+

+ 0„

j d 1.6(-10) * 50* FA Ferguson 196O

Fe

+ + 0, - Fe0+

+ 0_

5 d 1.5(-10) ± 5056 FA FerguGon 1968

Hp

+

+ II - H,

+

+ H 2.0( -9) ± 10]!, MS Reuben I962

i.85(-9) MS Warneck 1967d

l-95(-9) * 205S ICR Bowers 1969b

H

2

+

+ N

2 - N2H

+

+ H 1-95C-9) ± 20# ICR Bowers 1969a

H

2

+

+" Ar - ArH

+

+ H i.2(-9) ± 20/. ICR Bowers 1969a

N

2

+

+ N - N

+ + N

2 <i (-11) FA Ferguson I965

Ng

+

+ 0 - N0

+

+ N l.U(-lO) X2 FA Feheenfeld I97O - 0

+ + N

2 <1 (-11) FA Ferguson I965 N

2+

+ H

2 - N2H

+

+ H l-7(-9) ± 305t FA Fehsenfeld 1967a l.M-9) ± 20f> ICR Bowers 1969 N* + 0„ - 0* + N- £ C C. C. 6.6(-U) ± 3036 FA Farragher 1970

6 (-11) DT Johnsen 1970

5 (-11) ± 30* FA Ferguson 1969 6.5(-H) ± 1 MS Aqullanti I966 - H0+

+ NO <3 (-1M MS Warneck 1967b

Ng

+ + CO - C0

+

+ N

2

" 7 (-11) ± 30* FA Fehsenfeld 1967b

Ng

+

+ NO - N0

+

+ N

2 3.3(-10) ± 3056 FA Fehsenfeld 1970

4.8(-10) ± 3036 MS Warneck 1967b

N

2

+

+ H

20 - H

20

+ + N

2

1 2.2(-9) ± 0.3 FA Howard 1970 - N

2

H

+

+ OH | 2.0(-9) ±.3056 FA Bolden 1972 N

2

+

- + C02 - C0

2+

+ N

2

9 (-10) ± 30* FA Fehsenfeld 1967b

N0

+ + Na - Na

+

+ N0 5.8(-10) ± 5036 FA Farragher 1969

1.9(-9) B Rutherford 1972a N* + Mg - Mg

+

+ N_

C. tL 7.2(-10) B Rutherford 1971a

N_

+

+ Ca - Ca

+

+ N0 c. tL 1.8(-9) B Rutherford 1972b N* + Fe - Fe

+ + N0 d d

»*.3(-10) B Rutherford 1972c

0o+

+ N -« N0

+

+ 0

d 1.8(-10) X2 FA C-oldan I966

0

2

+

+ N

2 - N0

+

+ NO < 1 (-15) FA Ferguson 1965

0g

+

+ NO - N0++ Og 6.3(-10) ± 3OJ5 FA Fehsenfeld 1970

7.7(-10) ± 30^ MS warneck 19o7e

7.2(-10) ± 1.5 DT Johnsen 1970

Og+

+ NOg - NOg

+ + Og 6.6(-10) ± 30g6 FA Fehsenfeld 1973b

Og

+

+ NH

3 - NH

3

+

+ Og 2.M-9) ± 30* FA Feheenfeld 1973c Og* + Na - Nu

+

+ Og 6.7(-10) ± 5036 FA Farragher I969 l.M-9) B Rutherford 1972u

79
Tuble I Continued

Reaction k(cra^sec"''') Uncertainty Method Reference

, j, . . 0„ (a n ) + Na - Nq + 0„ 2 u 2 2.0 (-9) B Rutherford 1972a

0g

+

+ Na - NaO

+

+ 0 1.2 (-10) B Rol 1968

< 7 (-11) FA Fnrragher I969

0

2

+

+ Mg - Mg

+

+ 0

2 1.2 (-9) B Rutherford 1971a

+ h + °2 ^ a J

+ ^ "* ^ + °2 > 3 (-9) B Rutherford 1971a

0

2

+

+ Ca - Ca

+

-f 0

2 1.8 (-9) B Rutherford 1972b

+ U + 0„ (a II ) + Ca - Ca + 0„ 2

4 u 2 3-5 :-9) B Rutherford 1972b

0

2

+

+ Fe -• Fe

+ + 0

2 1.1 :-9) B Rutherford 1972c

N0

+

+ Na - Na++ NO 7-7 :-u) ± 50* FA Farragher 1969

N0

+

+ Mg - Mg

+ + NO 8.1 :-io) B Rutherford 1971a

N0

+

+ Ca -* Ca

+

+ NO k.o (-9) B Rutherford 1972b

N0

+

+ Fe - Fe

+ + NO 9.2 -10) B Rutherford 1972c

N0

+ + 0

3 - N0

2+

+ 0

2 < 1 -ik) FA Fehsenfeld 1973b

C0

+ + 0 - 0+

+ CO l.M -10) ± 50* FA Fehsenfeld 1972a

CO

+ + W — products < 2 ( -n) FA Fehsenfeld 1972a

C0

+

+ NO - N0

+

+ CO 3-31 -10) ± 30* FA Fehsenfeld 1972a

C0

+

+ - COH

+

+ H 2.0( -9) ± 30* FA Fehsenfeld 1967a

co

+

+ o

2 - o2

+

+ CO 2.0( -10) ± 30* FA Fehsenfeld 1966b

co

+

+ co

2 - co

2+

+ CO l.X( -9) ± 30* FA Fehsenfeld 1966b

CO

+

+ HgO - products 2.2( -9) ± 30* FA Bolden 1972

SiO

+

+ 0 - Si++ 0

2

-10) FA Fehsenfeld 1969a

SiO

+ + N - Si+

+ NO ~ 2 ( -10) FA Fehsenfeld 1969a - NO

+

+ Si - 1 ( -10) FA Fehsenfeld 1969a

MgO

+

+ 0 - Mg

+ + 0

2 ~ 1 ( -10) FA Ferguson I968

SO

+ + CO - s

+

+ co2 < 1 ( -12) FA Fehsenfeld 1973a

H

3+

+ N

2 - MgH

+ + H

2

l-5( -9) ± 30* FA Burt 1970

1.0( -9) •± 30* MS Aquilanti I965

Hj+

+ CO -* COH

+

+ H

2 lA( -9) ± 30* FA Burt 1970

+ NO - NOH

+

+ H

2 iM -9) ± 30* FA Burt 1970

H

3

+

+ C0

2 - C02H

+

+ H

2 1.9( -9) ± 3o£ FA Burt 1970

Hj* + N02 — N0

+ + OH + Hg 7 ( -10) ± 30* FA Burt 1970 H

3+

+ N

20 - N20H

+

+ H

2 1.8( -9) ± 30* FA Burt 1970 H

3

+

+ CH^ - CH

5

+

+ ^ 1.6( -9) ± 30* FA Burt 1970

7-5( -10) ± 30* MS Aquilanti 1966a

H

3

+

+ C2

H

4 - C^5* + H2 1.9( -9) ± 30* FA Burt 1970 - C

2H

3

+

+ 2H2

1.2( -10) ± 30* FA Burt 1970

80
Reaction

+

• e; c C2

H

3

+ 1! 2

+

ir ri c H3°

+

+ H

2 +

H

3 + NH,* +

N„H

+ + co

? C02

H

+ + N

2 N

2H

+ + N

20 No

01I+

+ N

2 N

2

H

+

+ cn

k CH

5

+ + N

2 HgH

+

+ H

20 H

30

+

+ N

g H

20

+

+ H

g

0 H

30

+

+ OH

H

20 + lie Na + H

20

H

20 + Ca

H

20

CO,

Fe

h H - HCO' + 0 - H + CO„

co

2 + 0 0

2

+ GO - 0 + CO,

C02

+ N CO/ + H

2 co

2+

+ fro

co2+

+ o

2 N02

+ + NO

-> products

CO

gH + H - NO + CO„

°2 + C0

2 - NO + NO, - SO

+

+ CO,

so

2 + 0£ H

30

+

+ Ca

N, +

+ 0o

O

h

+ + H

20

3 -N2

+ H

2

0

32

+

-N2

+ 0

2

5 >0H + H2

0 r- H

30 'HgO + OH

o

2

+ so

2 Ca

+

+ H

2

0 + H

0

2

+ + 2N

2

'

°2

+

+ °

3 °2

+ -"2° + °2

0

2

-H20 + N

2

Table 3 Continued

kfcjn^r.oc" 1

) Uncertainty Method

3.0

3-6

9-2

7,9

8.9

5

1.7

1.8

1.6

1.9

h.o

1.5

2.6

< 1

L.k

1.2

5-0

2.9

3-0

2.8

1+

3

1.5

1-3

2.2

k

> 5

l.U

> 1 ~ 3-2

Reference Rein: irk

;-io) ± 30^ FA Burt 1970

:-9) FA Burt 1970

:-9) FA Burt 1970

:-io) ± 30,' FA Burt 1970

-10) ± 30,o. FA Hurt 1970

-10) ± 30^o FA Burt 1970

-10) FA Burt 1970

I -y ) ± FA "Rnl At=-rt 1 Q7P

-9) ± 307; MS Good 1970

-9) ± avf, MS Gupta 1967

-9) B Rutherford 1972a

-9) B Rutherford 1972b

-9) B Rutherford 1972c

-10) * 5o£ FA Fehsenfeld 1971a

-10) x 2 FA Fehsenfeld 1970

-11) FA Fehsenfeld 1970

-9) ± 30=4 FA Fehsenfeld 1967a

-10) ± 3056 FA Fehsenfeld 1970

-11) ± 30^ FA Fehsenfeld 1970

-10) ± 305& FA Fehsenfeld 1969'b

-10) ± 2C# FA Fehsenfeld 1973a

-10) ± 20^ FA Fehsenfeld 1973a

-9) B Rutherford 1972b

-10) ± 30^ FA Dunkln 1971b

-10) . ± 2 FA Fehsenfeld i972b

-9) ± 0.5 FA Howard 1972

-9) ± 50^ MS Good 1970

-9) ± 50^ FA Fehsenfeld 1971b

-9) ± 2 FA Howard 1972

-11) FA Adams 197b

-9) ± 0.5 FA Howard 1972

-9) MS Good 1970

-9) FA Fehsenfeld 1971b

80°K

81
Table I Continued

Re cction k(cm sec ) Uncertainty Mo thod Reference

0

2

+

-IIo0 + H^O - H

3 0

+, OH + Og 1.0 ' o) 4 O.h PA Howard 1972

9 -10) ± 30% ms Good l

k 170

1.9 -9) FA Fchscnl'cld 1971b - K^0

+

+ OH + 0

£

2 -10) ± -1 FA Howard 1972

3 ( -10) ± 1 MS Good 1970

fi 3 1 -10) FA Fehsenfeld 1971b

NO

+ -CO„

c + Ho0 - N0

+

-H o0 + C0

2 - 1 ( -9) FA Dunkln 1971b

N0

+ (H„0)„ + H

20 - H

30

+ (H2

0) 2

+ HW0

2 7 ( -11) ± 2 FA Howard 1972

8 ( -11) ± 50$ FA Fehsenfeld 1971c

7 1 -11) ± 30$ SA Puckett 1971a

NO

+

-NO + H

2

0 * NO -H 0 + NO lAi -9) ± 0.3 SA Puckett 1971a

NO

+

-NO + IfH^ - KO

+

-NH

3

+ NO 1.3( -9) ± 0.2 SA Puckett 1971a

N0

+

-K2

0 + NO - NO

+ -NO + KgO 9 ( -Ik) ± 2 SA Puckett 1971a

NO

+ .H„0 + NH

3 - mk

+

+ hko

2 1.0( -9) ± 30$ FA

' Fehsenfeld 1971d

N02

+

-H20 NH

3 - NH^

+

+ HNO 1.1( -9) ± 30$ FA Fehsenfeld 1973c

NO

+

'KH

3 + NH - NH^

+ + ONNHg 9.K -10) ± 30$ SA Puckett 1971b

NH

3

+ + NH

3 - NH^

+

+ KHg 1.9< -9) ± 0.2 ICR Huntress 1971a

1.5( -9) ± 30$ MS Melton I966

l-7( -9) ± 30$ FA Fehsenfeld 1973c

+ - NHj^+ * HgO 2.1( -9) ± ^cfi FA Fehsenfeld 1973c I^O^O) + KH

3 — products 2.6( -9) ± 30$ FA Fehsenfeld 1973c

H

30+

(H2

0) 2 + KH

3 — products 1.6( -9) ± 30$ . FA Fehsenfeld 1973c'

H

30

+

(H20)

3 + KH3 — products 2.1( -9) ± 30$ FA Fehsenfeld 1973c

HH^

+

(H2

0) + NH

3 - NH

U

+ (NH

3

) + H

20 JL.2( -9) ± 30$ FA Fehsenfeld 1973c

NH

lf+

(H2

0) 2

+ nk. - NH

u

+

(lffl3 )(H2

0) + H

2

0

a 9 (-10) ± 30$ FA Fehsenfeld 1973c

82
FOOTNOTES

Agrees veil with extrapolated beam measurements

Farragher gives k

&

= 6. 5 (-10) ± 1.3, K = ;+.2(-10) ±0.9

Heimerl gives k as a function of ion kinetic energy to ~ 0.1 eV

Rate constant found to be independent of temperature, 300-600°K

Rate constant proportional to T"

1 in thermal range

Rate constant independent of Ng vibrational temperature from 300-600°K but ratio ^ /k^ increases vith

Extrapolated from beam energies. This leads to additional uncertainty in k, probably reliable to within

factor of 2.

Johnsen gives k as function of ion kinetic energy to ~ 1 eV

Schmeltekopf gives k as function of Ng vibrational temperature from 300-6000°K •

Rate constant given for temperature range 80-600 K

Gives rate constant proportional to T

2 in thermal range.

Ryan gives k&

+ k^ = ^.3 (-10) ± 0.6. Dunkin 1971 erroneously neglects channel b

Probably endothermic

Measurements on this reaction have given rate constants ranging from k(-12) to 6.6(-ll), depending on

experimental conditions. This is almost surely due to the near resonance involved and the difficulties are elaborated in Adams 1970b where a pressure dependent k is observed. This is also discussed by Adams, Dean, and Smith, Int. J. Mass Spectrometry and Ion Phys . 10, 63, 1972.

It has also been shown (FA) that k < lO

-1

^ cm^ sec"

1 at 600°K

More details of this experiment, including the rate constant cited are given by Rol and Entemann in a

General Dynamics/Qonvair Report GDC-DBE69-002 of January 1969

Rate constant is not given but cross section data down to 10 eV shows clearly that rate constant is quite

large

Reaction is endothermic

83
REFERENCES TABLE I

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V. Aquilanti, A. Galli, A. Giardini Guidoni, and G. G. Volpi, J. Chem. Phys. 4_3 1969 (1965)

V. Aquilanti and G. G. Volpi, J. Chem. Phys. 44, 2307 (1966a)

V. Aquilanti and G. G. Volpi, Ricerca Sci. 36 259 (1966b)

R. C. Bolden and, R. S. Hem'svorth, M. J. Shaw, and N. D. Twiddy, J. Phys. B 3, 45 (1970)

R.'C. Bolden and N. D. Twiddy, Faraday Disc. 5_3_, 192 (1972)

M. T. Bowers and D. D. Elleman, J. Chem. Phys. 5JL, 46o6 (1969a)

M. T. Bowers, D. D. Elleman, and J. King, Jr., J. Chem. Phys. 50, 4787 (1969b)

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J. A. Burt,' J. L. Dunn, M. J. McEwan, M. M. Sutton, A. E. Roche, and H. I. Schiff, J. Chem. Phys. 52, 6062

(1970)

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A. L. Farragher, J. A. Peden, and W. L. Fite, J. Chem. Phys. 50, 287 (1969)

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F. C. Fehsenfeld, A. L. Schmeltekopf, P. D. Goldan, H. I. Schiff, and E. E. Ferguson, J.

(1966a)

F

.

c. Fehsenfeld, A. L. Schmeltekopf, and E E. Ferguson, J. Chem Phys. 45, 23 (1966b)

F. c. Fehsenfeld, E. E. Ferguson, and A. L. Schmeltekopf, J. Chem Phys

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44, 3022 (1966c)

F. c. Fehsenfeld, E. E. Ferguson, and A. L. Schmeltekopf, J. Chem Phys. 45, 404 (I966d)

F. c. Fehsenfeld, A. L. Schmeltekopf, and E E. Ferguson, J. Chem. Phys. 46, 2802 (1967a)

F. c. Fehsenfeld, L. Schmeltekopf, and E E. Ferguson, J

.

Chem. Phys. 46, 2019 (1967b)

F. C. Fehsenfeld, Can. J. Chem. hjj 1808 (1969a)

F. C. Fehsenfeld, E. E. Ferguson, and M. Hosesman, Chem. Phys. Letters 4, 73 (1969b)

F. C. Fehsenfeld, D. B. Dunkin, and E. E. Ferguson, Planet. Space Sci 18, 1267 (1970)

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F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys. 5_4, 439 (l971d)

F. C. Fehoenfeld and E. E. Ferguson, J. Chem. Phys. 56, 3066 ( 1972a)

F. C. Fehsenfeld and E. E . Ferguson, Radio Sci. 7, 113 ( 1972b)

F. C. Fehsenfeld and E. F; . Ferguson, J. Geophys. Res. 78, II69 (1973a)

F. C. Fehsenfeld, E.- E. Ferguson, and C. J. Howard, J. Geophys. Res. 78, 327 (1973b)

F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys.' (1973c) in press

. 84
E. E. Ferguson, F. C. Fehsenfeld, P. D. Goldan, A. L. Schmeltekopf , and H. I. Schiff, Planet. Space Sci. 13,

823 (1965)

E. E. Ferguson and F. C. Fehsenfeld, J. Geophys. Res. 73, 6215 (1968)

E. E. Ferguson, D. K. Bohme, F. C. Fehsenfeld, and D. P.. Dunkin, J. Chem. Phys . 5_0, 5039 (1969)

J. L. Franklin and M. S. 3. Munson, Tenth Combustion Symposium, p. 561, Combustion Institute, Pittsburgh, Pa.

(I96p)

P. D. Goldan, A. L. Schmeltekopf , F. C. Fehsenfeld, H. I. Schiff, and E. E. Ferguson, J. Chera. Fnys . hk, 1+095

(1966)

A. Good, D. A.Durden, and P, Kebarle, J. Chen. Phys. 5_2, 212, 222 (1970)

S. K. Gupta, E. G. Jones, A. G. Harrison, and J. J. Myher, Can. J. Chem. 1+5, 3107 (1967)

J. Heimerl, R. Johnsen, and M. A. Biondi, J. Chem. Phys. 51, 501+1 (1969)

C. J. Howard, H. V/. Bundle, and F. Kaufman, J. Chera. Phys. 5_3, 371+5 (1970)

C. J. Howard, K. V/. Runale, and F. Kaufman, J. Chem. Phys. 55, 1+772 (1971)

C. J. Howard, V. M. Bierbaujn, H. V.

7

. Rundle, and F. Kaufman, J. Chem. Phys. 5_J_, 3I+9I (1972)

V. T. Huntress, M, Mosesman, and D. D. Elleman, J. Chem. Phys, jk, 81+3 (1971)

R. Johnsen, H. L. Brown, and M. A. Biondi, J. Chen. Phys. 52, 508-0 (1970)

E. G. Jones and A. 0. Harrison, Int. J. Mass Spectro. Ion Fhys . G_, 77 (1971)

J. B. Laudenschlager and M. T. Bowers, Chem, Phys. Letters (1973) in press

E. W, McDaniel, V. Cermak, A. Dalgarno, E. E, Ferguson, and L. Friedman, Ion -Molecule Reacticns, Wiley, New

York 1970

T. F. Moran and L. Friedman, J. Chem. Phys. If 5, 3337 (i960)

C. E. Melton, J. Chem. Phys. 1+5. 5515 (1966)

J. F. Paulson, R, L. Mosher, and F. Dale, J. Chem. Phys. kh, 3025 (1966)

L. J. Puckett and M. W. Teague, J. Chem. Phys. 5j+, 2561+ ( 1971a)

L. J. Puckett and M. W, Teague, J. Chem. Phys. 5k, 1+860 ( 1971b)

B. G. Reuben and L. Friedman, J. Chem. Phys . 37, 1636 (1962)

P. K. Rol and E. A. Entenann, J. Chem. Phys. U9, 11+30 (1968)

J. A. Rutherford, R. F. Mathis, B. R. Turner, and D. A. Vrccra, J. Chem. Phys. 55_, 3785 (1971a)

J. A. Rutherford and D. A. Vroom, J. Chem. Phys. 5_5_, 5622 (1971b)

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J. A. Rutherford, R. F. Mathis, R. Turner, and D. A, Vroom, J. Chem. Fhys. 5_7, 3087 (1972b)

Jo A. Rutherford and D. A. Vroom, J. Chem. Phys. 5_7, 3091 (1972c)

K. R. Ryan, J. Chem. Phys. 57, 271 (1972)

J. Sayers and D. Smj.th, Disc. Faraday Soc. 37, 167 (l9cl+)

S. M. Schildcrout, J. G. Collins, and J. L. Franklin, J. Chem. Phys. 5_2, 57o7 (1970)

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D. Smith and R. A. Fouracre, Planet. Space Sci. 16, 21+3 (1968)

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85
P. Warneck, J. Chem. Phys . k]_, U279 (1967a)

P. Warneck, J. Geophys. Res. J2, 1651 (1967b)

P. Warneck, J. Chem. Phys . ^6, 513 (1967c)

P. Warneck, J. Chem. Phys. U6, 502 (l967d)

P. Warneck, Planet. Space Sci. 15, 13U9 (l967e)

86
TABLE II. Binary HcgMtlvc-Ion Rouctlonu

Refiction k(cm sec" ) Uncertainty Mothod RuiVronce

H* + H - Hg + e 1.3'('-9) ± 50i FA Schneltckopf 1967

1.8(-9) X2 FA Fehsenfeld 1973a

H" + CO - HCO + e ~5 (-U) FA Dunkin, 197C

H" + NO - UNO + e l*.6(-lp) ±. 30,t FA Dunkin, 1970

H" + 0_ - HO. + e 2 2 1.2(-9) ± 0.2. FA Dunkin, 1970 - 0" + OH < 1 (-11) FA Dunkin, 1970 - 0

" + H

2 < 1 (-11) FA Dunkin, 1970 - OH" + 0 < 1 (-11) FA Dunkin, 1970

H~ + No0 - OH" + N„ 2 2 l.K-9) ± 0.3 FA Dunk_in, 1970

H" + NO„ - NO ~ + H

2 2

2.9(-9) ± 3C?i FA Ferguson, I969

H" + H„0 - OH" + }U 2 7? 3-8(-9) ± 30s MS Melton, 1971

C" + Hg products < 1 (-13) . FA Fehsenfeld 1970

C" + CO - CgO + e 4.1(-10) ± 30£ FA Fehsenfeld, 1970

c" + o

2 - 0" + CO U.o(-io) ± 30^ FA- Fehsenfeld, 1970

C" + No0 - CO + N„ + e 2 2 9.0(-10) ± 30£ FA Fehsenfeld, 197C

C" + CO_ - 2C0 + e 2 k.l(-ll) ± 3C# FA Fehsenfeld, 1970

0* + 0 - 0„ + e 2 1.9 (-1Q) X2 FA Fehsenfeld, I967

0" + N - NO + e 2.2(-10) X2 FA Fehsenfeld, I967

0" + Hg — HgO + e 7.0(-10) ± 0.5 DT Parkes, 1972a

6.o(-io) ± 30^ FA Ferguson, 1969

7.2(-10) ± 1 DT Moruzzi, I960 - OH" + H 3.3(-H) ± 0.5 DT Parkes, 1972a

0" + CO - CO„ + e 2

6. 5 (-10) ± 1 DT Moruzzi, 1968

0" + NO - N0„ + e 2

7-3(-10)

2.2(-I0)

± 30^

± 0.7 ± 0.5

FADT

DT

Ferguson, I969

Parkes, 1972a Moruzzi, 1963

l.6(-io) ± 30^ FA Ferguson, 1969

0" + N„ - N„0 + e 2 2 < 5 (-13) DT Moruzzi, I968

< 1 (-12) FA Fehsenfeld, I966 OJ 1

^ ) - 0, + e

2' b' 3. ~ 3 (-10) FA Fehsenfeld, 1969a

0" + H~0 - OH" + OH l.U(-9) ± 3C# MS Melton, 1971

0" + NgO - NO" + NO 2.2(-10) ± O.lt FA Marx, 1973

2.5( -10) ± 0.5 ICR Marx, 1973

•1.95 (-10) ± 0.06 DT rarkes 1973 0" + NOg - N02

' +0 1.2(-9) ± 30* FA Ferguson, I969

o* + o

3 - o

3

" + 0 5-3(-10) X2 FA Fergus on, I969

0* + CH^ - OH" + CRj l.l(-lO) i 0.1 DT Parkes, 1972a

l.o(-io) ± 20^ FA Bohmc, I969

87
Table II continued

Reaction k(cin^ecc"1

) Uncertainty Method

0" + CH, CgH^O + e 1^.05 (-10) ± 0.5 DT

CgH

?

" + HgO 1.9 (-10) ± 0.3 DT

o" + cju CgHgO + e 1.3 (-9) ± 0.09 DT

CgH" + OH 8.0 (-10) ± o.s DT

CgOH + H 8 [-11) X 1 DT

0" + CH,- 2 6 OH" + CgH,. 7.0 (-10) x 20$ FA 0" + C Hn

• 38 OH" + C^H^ 9.3 !-10) x 20$ FA

0~ + n - C. H_ OH" + c. h 1.2 :-9) x 2056 FA

F* + H HF + e 1.6 '-9) X2 FA

O " tig H S + p < 1 -15)

s" + Og SOg + e 3.0 •-11) FA n " ^ i. +> ha HPT + e» 9.01 -10)

1.01 -9) X2 FA

0H~ + H H n 4- 1.01 -9) VOAC TTA

1.8( -9) AcYO VA

OH* + 0 HOg + e 2.0( -10) ± so4 FA

0H~ + N HMO + e < 1 ( -11) FA

OH" + NOg NOg" + OH 1.9( -9) FA

HS~ + H KgS + e 1.3( -9) X2 FA

CN~ + H HCH + e 8.0( -10) X2 FA

no" + Og 0g~ +*N0 5.0( -10) ± ^oi FA

NO" + KgO HO ~

A,v + N

g

ng 2.8( -Ik) X 0.2 DT

KO" + NOg NOg" + NO jM -10) ±— ^Oi DT

Vg n Jit UUUL m l-5( -9) X2 FA O

" + N NO11 + ec i*.o( -10) . j<a

Vg T V

°3 e 3-3( -10) x FA

0

~ U + H

2 H2

TT7" 1 1 P t" ^ < 1 ( -12) FA

°2 +

°2l V

on^fj^ j-+ ae ~ 2 ( -10) • VA A ~ J. W A

2 2 A ~ J. W

°3 + N

2 < 1 ( -12) Ul

°2 + N02 MA ~ 4- A 8.0( -10) fn

o

2

" + o

3 °3~ + °2 3.0( -10) ± 30$ FA o

2

" so

2 SOg- * o2

l*.8( -10) * 30* FA

NOg" + H OH" + NO 3-0( -10) X2 FA

k.0{ -10) XT FA

II0g" 0 products < 1 ( -11) FA

NOg* + N producto < 1 ( -11) FA

Reference Remarks

Parkes, 1972a

Parkes, 1972a

Parkes, 1972a

Parkes, 1972a

Parkes,. 1972a

Bohme, I969

Bohme, I969

Bohme, 1969

Fehsenfeld, 1973a

Fehsenfeld, 1969b

Fehsenfeld, 1969b

Ferguson, I969

Fehsenfeld, 1973a

Ferguson, 1969

Fehsenfeld, 1973a

Fehsenfeld, 1966

Fehsenfeld, 1966

Ferguson, 1969

Fehsenfeld, 1973a

Fehsenfeld, 1973a

McFarland, 1972 e

Parkes, 1973

McFarland, 1972

Fehsenfeld, 1973a

Fehsenfeld, 1967

Fehsenfeld, 1967

Fehsenfeld, unpublished

Fehsenfeld, 1969a

Parkes, 1923

Ferguson, I969

Fehsenfeld, I967

Fehsenfeld, 1973b

Fehsenfeld, 1972

Fehsenfeld, 1973a

Fehsenfeld, unpublished

Fehsenfeld, unpublished

88
Tublc II continued

Reaction k(cnA- cc"^) Uncertainty Method Reference Rcmu

N0

2

" + N02 - NO^* + NO ~ 1* (-12) FA Fehncnfcld, 1969c

N02

" + °3 "* + °

2 1.0 (-11) ± 50^6 FA Fehsenfeld, I968

O^" + H - OH" + 0

2 8.4 (-10) X2 FA Fehsenfeld, 1973a

0^" + Ng -• products < 1 (-15) FA Fchsenfcld, unpublis hed

0^" + NO — products 1.0 (-11) ± 50$ FA Fehsenfeld, 1967 f

0^" + co2 - co^" + o

2 4.0 (-10) i 30^ FA . Fehsenfeld, I967

5-5 (-10) ± 0.5 DT Parkes, 1972b

0^" + N02

-* products 2.8 ;-io) ± 30?; FA Dunkln, 1972

. o^" + so2 - so^" + o

2 1.7 '-9) ± 30-/. FA Fehsenfeld, 1973*>

co^" + o - o

2

~ + co

2 8.0 -11) ± 50£ FA Fehsenfeld, 1967

CO^" + NO - N02

" + C02 9.0 -12) X2 FA Fehsenfeld, I967

1.8| -11) ± 30^6 FA Fehsenfeld, 1973b

CO^' + N02 - products 2 ( -10) X2 FA Fehsenfeld, 1973b

co^" + so2 - so ~ + co

2

2.3( -10) ± 3056 FA Fehsenfeld, 1973b

NO^ + N — products < 1 I -11) FA Fehsenfeld, 1969c

NO^" + 0 - products < 1 I -11) FA Feh6enfeld, 1969c

0^" + o - o

3

~ + o

2 - 0" + 20

2

)

-10) ± 50* FA Fehsenfeld, 1969c k

a

0^" + CO - co^" + o

2 < 2 ( -11) - FA Adams, 1970

0^" + NO N0

3

_* + 0

2 -10J ± 30^ FA Adams, 1970 h

d TM 4- prt —• nn * 4- rT h 2 h 2

-10) ± JO?' £A AnnTTlS , J.y (U

0^" + HgO - Og'-HgO + 0

2 l-5(

l.k{

-9)

-9)

MS

DT

Payzant, 1972

Pack, 1971

CO^" + 0 - CO^" + 0

£ - V + C°2

! x. s <

J

-10) ± 50* FA Fehsenfeld, 1969c k

a >kb

CO^ + NO -• NO^ + C0

2 4.8( -ii) ± 30^ FA Fehsenfeld, 1969c h

°2~" II2

0 + N0 N03~ + H2° 3.1( -10) ± 3°£ FA Adams, 1970

Og'-HgO + C0

2 - CO^" + HgO 5.8( -10) ± 3056 FA Adams, 1970

0

2

"'H20 + "* products 3 ( -10) ± 30* FA Fehsenfeld, 1973b

0g"(H2

0)2

+ °

3 - products 3-"+( -10) ± 3»£ FA Fehsenfeld, 1973b

NO^ + NO — uo

2

+ rio2 l-5( -11) X2 FA Adams, 1970. h

N0

3

" + NO - N02" + N02 ~ 3 ( -15) DT Parkes, 1972c 1

0

2

"-H20 + 0

2 - 0^" + H^O 2.5( -15) ± 1 DT Parke s, 1971 i

0

3 "(H

20) + C0

2 - products 3 ( -10) X2 FA Fehsenfeld, 1973b

0

3"(H

2

0) 2

+ C0

2 - producto 2 ( -10) X2 FA Fehsenfeld, 1973b

89
TubJc II continued

Reactions k(cm^ccc"^) Uncertainty Method Reference Rcmarko

C0

3 "(H

2

0) + i;o products 1.8(-ll) X2 FA Fehsenfeld, 1973b

C0

3 "(H

20) + H02

products 1.5 (-10) X2 FA Fehsenfeld, 1973b

N02

*(II 20) + so

2 N0

2 "(S0

2

) + H

20 1.5(-9) ± 30^ FA Fehaonfeld, 1973b SO^ + N0

2 KOg* + S02

+ 0

2 2.5(-10) X2 FA Fehsenfeld, 1973b

N0

3

" + S0

3 i (-10) X2 FA Fehsenfeld, 1973b

so

3

" + H

2C HgSO^ + e < 1 (-12) FA Fehsenfeld, 1973b

90
FOOTNOTES

a) There is a theoretical value for k by J. C. Browne and A. Dalgarno, J. Phys. B. (Atomic and Molec. Phys.

2, 885, I969). The value at thermal energy is 2.0(-9) and the energy dependence is also given.

b) k independent of ion energy, 0-5 eV.

c) F. Kaufman, J. Chem. Phys. h6, 2kk9, 1967 points out that a detailed balancing argument can be used to

-13 3 -1 calculate k < 10 cm sec from dissociative electron attachment data for NgO.

d) Because this reaction has often been measured with energetic 0 ions for which the rate constant is lower

than for thermal ions, there has been a spread in published rate con?t£.nts. This effect leads to a

pressure dependence for k when the 0 is produced from N^O as has usually been the case. This

problem is resolved in Marx 1973 and all earlier measurements are rationalized.

e) The electron affinity of NO is so low (~ 0.02i+ eV kT) that collisional detachment is rapid in almost

all gases. Such data for a number of gases are given in McFarland 1972.

f) Products reported to be NO^ + 0 in reference. This is uncertain, it is more likely that products are

N02

" + 0

2

.

g) Products uncertain, either NO,-, or NO^ or both.

h) There are two forms of NO^ , suggested as being the stable nitrate ion O-N-0 and the higher energy peroxide ion O-N-0-0 (which is denoted NO^ ). q

i) Reaction is endothermic

j ) Probably endothermic

91
REFERENCES, TABIE II

N. G. Adams, D. K. Bohme, D. B. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, J. Chern. Fhys. 52, 3133 (1970)

D. K. Bohme and F. C. Fehsenfeld, Can. J. Chem. Vf, 2717 (1969)

D. B. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, J. Chem. Fhys. 53, 987 (1970).

D. B. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, Chem. Phys . Letters 15_, 257 (1972)

F. C. Fehsenfeld, E. E. Ferguson, and A. L. Schmeltekopf , J. Chem. Phys. ^5_, l8kh (1966)

F. C. Fehsenfeld, A. L. Schr.eltekopf , H. I. Schiff, and E. E. Ferguson, Planet. Space Sci. 15, 373 (1967)

F." C. Fehsenfeld and E. E. Ferguson, Planet. Space Sci. 16, 701 (1968)

F. C. Fehsenfeld, D. L. Albritton, J. A. Burt, and II. I. Schiff, Can. J. Chem. kj_, 1793 (1969a)

F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys. 51, 3512 (1969b)

F. C. Fehsenfeld, E. E. Ferguson, and D. K. Bohme, Planet. Space Sci. 17, 1759 (1969c)

F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys.- 53, 26l^ (1970)

F. C. Fehsenfeld and E. E. Ferguson, Planet. Space Sci. 20, 295 (1972)

F. C. Fehsenfeld, C. J. Howard, and E. E. Ferguson, J. Chem. Phys., Vol. 58 (1973a) in press

F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys. Vol. 59 (1973b) in press

E. E. Ferguson, F. C. Fehsenfeld, and A. L. Schmeltekopf, Adv. in Chem. Series 80, 83 (1969)

R. Marx, G. Mauclaire, F. C. Fehsenfeld, D. B. Dunkin, and E. E. Ferguson, J. Chem. Pnys. Vol. 58 (1973) in

press

M. McFarland, D. B. Dunkin, F. C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, J. Chem. Phys. 56, 2358

(1972)

C. E. Melton and G. A. Neece, J. Am. Chem. Soc. 93., 6757 (1971)

.

J. L. Moruzzi, J. W. Ekin, and A. V. Phelps, J. Chem. Phys. k8, 3070 (1968)

J. L. Pack and A. V. Phelps, Bull. Am. Phys. Soc. 16, 21k (1971)

D. A. Parkes, Trans. Faraday Soc. 67, 711 (1971)

D. A. Parkes, J. Chem. Soc. Faraday Trans. I. 68, 6l3 ( 1972a)

D. A. Parkes, J. Chem. Soc. Faraday Trans. I. 68, 627 ( 1972b)

D. A. Parkes and T. M. Sugden, J. Chem. Soc. Faraday Trans. II, 68, 600. ( 1972c)

D. A. Parkes, J. Chem. Soc- Faraday Trans., I. 68, 2103 (1973)

J. D. Payzant and P. Kebarle, J. Chem. Phys. 56, 3^82 (1972)

A. L. Schmeltekopf, F. C. Fehsenfeld, and E. E. Ferguson, Astrophys . J., lk8, L155 (1967)

92
FORM NBS-1 14A (1-71) U.S. DEPT. of COMM. 1. PUBLICATION OR REPORT NO. 2. Gov't Accession

BIBLIOGRAPHIC DATA NBSIR 73-203

N°"

3. Recipient's Accession No.

4. TITLE AND SUBTITLE

CHEMICAL KINETICS DATA SURVEY

IV. rreiimmary latsies oi Lnemical Data tor Modelling

of the Stratosphere

5. Publication Date

6. Performing Organization Code

7. AUTHOR(S) „ , , „ Dr. David Garvin8. Performing Organization

NBSIR 73-203

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

Washington, DC 20590

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.) Chemical kinetic and photochemical data for gas phase reactions pertinent to

the chemistry of the stratosphere are presented in four tables. These tables

give recommended values and also cite recent experimental work. They give data

in the following subject areas: chemical reactions and photochemistry of neutral

species, energy transfer reactions, high temperature air reactions, and ion-molecule

reactions.,

17. key WORDS (Alphabetical order, separated by semicolons) Atmospheric chemistry; Chemical kinetics;

Data evaluation; Energy transfer; Gas phase; High temperature air chemistry; Ion-molecule

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