NAT'L INST. OF STAND & TECH NIST

ERENCE PUBLICATIONS

Chemical Kinetics Data Survey

Yll. Tables of Rate and Photochemical

Data for Modelling of the Stratosphere

(Revised)

David Garvin, R. F. Hampson, Editors

Physical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

January 1974

Supersedes NBSIR 73-203 (May 1973)

Prepared for natic impact Assessment Program

Q/L' artment of Transportation

100 hington, D. C. 20590

KJo. 1-3-430

NBSIR 73-430

CHEMICAL KINETICS DATA SURVEY

VII. TABLES OF RATE AND PHOTOCHEMICAL

DATA FOR MODELLING OF THE STRATOSPHERE

(REVISED)

David Garvin, R. F. Hampson, Editors

Physical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D. C. 20234

January 1974

Supersedes NBSIR 73-203 (May 1973)

Prepared for Climatic Impact Assessment Program,

Department of Transportation

Washington, D. C. 20590

U. S. DEPARTMEIMT OF COMMERCE. Frederick B. Dent. Secretary

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

Page

1. Introduction Z

2. Related Material 3

3. Needed Work 4

4. Tables from "The Natural Stratosphere" Climatic Impact

Assessment Program Monograph No. 1, E. Reiter, editor 4

4.1 Chemical Reactions and Photochemistry of

Neutral Species 4

Chemistry Panel

4.1.1 Introduction 4

4.1.2 Conventions Concerning Rate Constants 5

4.1.3 Convention Concerning Optical 7 Absorption Coefficients

4.1.4 Arrangement of the Table 7 4.1.5 Table 10

4.2 Vibrational Energy Transfer Processes 70

R. L. Taylor

4.2.1 Introduction 70

4.2.2 Table 71

4.3 High Temperature Air Reactions 80

R. L. Taylor

4.4 Ion-Molecule Reactions 82

E. E. Ferguson

4.4.1 Explanation of Tables 82

4.4.2 Table I - Binary Positive-Ion Reactions 85

4.4.3 Table II - Binary Negative-Ion Reactions 96

ii
chemical Kinetics Data Survey

VII. Tables of Rate and Photochemical Data for

Modelling of the Stratosphere (Revised)

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

ion-molecule reactions

Key words: 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
1. 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, P. J. Crutzen, R. J. Cvetanovic^ M. L.

Corrin, D. D. Davis, E. E. Ferguson, D Garvin, R. F. Hampson, R. D. Hudson, L.J. Kieffer, H. I. Schiff and R. L. Taylor, in "The Natural

Stratosphere" E. Reiter, editor. Climatic Impact Assessment Program

Monograph No. 1. The present tables are essentially those in the version of this monograph which will be distributed in the Summer of 197A.

The first version of the table of data on the chemical reactions

and photochemistry of neutral species was prepared by the Chemistry

Panel on the Natural Stratosphere in December, 1972 at the Fort

Lauderdale, Florida meeting and received limited distribution in the

first preliminary draft of CIAP Monograph No. 1. A revised and expanded

version was distributed in NBSIR 73-203 in May, 1973. This version

incorporates changes and additions suggested at the meeting of the

Chemistry Panel in Boulder, Colorado in October, 1973. From time to

time, interim versions of this table have been distributed on a limited

basis. Since October, 1973 the date of preparation has been given in

the upper left hand corner of each page. The version of CIAP Monograph

1, to be distributed in 1974 has tables dated 12/3/73. This version

distributed here dated January 4, 1974 supersedes all earlier versions.

It is virtually the same as that dated 12/3/73.

The tables include contributions of rate evaluations by other

scientists. These contributors represented in the present edition are

D. L. Baulch, D. D. Drysdale and D. G. Horne , University of Leeds;

J. Heicklen, Pennsylvania State University; A. C. Lloyd, University of

California, Riverside; T. G. Slanger, Stanford Research Institute;

J. Troe and K. Glanzer, Ecole Poly technique Federale de Lausanne;

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

The tables are in several parts:

(1) Chemical reactions and photochemistry of neutral

species (by the entire Chemistry Panel).

(2) Vibrational energy transfer processes (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.

2
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. Comments by readers have been helpful in improving

these tables, and we would like to express our appreciation for them.

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.

2. 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 of chemists at NBS have been published in

J. Phys. Chem. Ref. Data 2, 267 (1973). Earlier versions of these

evaluations had been distributed as NBS Report 10692 (January 1972) and

NBS Report 10828 (April 1972) . Additional evaluations have been published in NBSIR 73-207 (August 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 H2-O2 system" D. L. Baulch, D. D. Drysdale, D. G. Horne and A. C.

Lloyd, (Butterworths, London, 1972) and volume 2, "Homogeneous gas phase

reactions of the H2-N2-O2 system" D. L. Baulch, D. D. Drysdale and

D. G. Horne, (Butterworths, London, 1973). 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,

-ditors, Wiley-Interscience , volume 4, 197A)

3
3. 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 denoted as not evaluated in the chemical reaction matrix

immediately before Table I. These will be incorporated in the later

versions of the tables. We will also welcome comments and corrections

of any of the recommendations.

4. Tables from "The Natural S'tratosphere" Climatic Impact

Assessment Program Monograph No. 1, E. Reiter, editor

4.1 Chemical Reactions and Photochemistry of

Neutral Species (Chemical Panel)

4.1.1 Introduction

These tables provide current (January, 1974) information on reaction rate constants, quantum yields and absorption cross sections. For

many reactions, best estimates or recommended values are given. The

reactions included in the tables are summarized on a "reaction grid"

in section 4.1,4, Arrangement of the Tables. That grid also shows

processes for which data (or data evaluations) are needed.

Most of the more important stratospheric reactions are in the

tables, A number of the less important ones and some related systems

are included, often simply for comparison.

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. The original data covered by the evaluation

are not listed separately.

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

both are listed and a preferred value is indicated

(marked by an asterisk) ,

(c) Where desirable, the available recent data sets

are listed, and a selection is made or a preferred

value is synthesized from them.

4
These selections are necessarily tentative because there is 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 persons making new selections or syntheses are usually identified by initials. These are either authors of

the chapter or contributors identified below.

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

Leeds; J. Heicklen, Pennsylvania State University; A. C. Lloyd, University of California, Riverside; T. G. Slanger, Stanford Research Institute; J. Troe and K. Glanzer, Ecole Poly technique Federale de Lausanne;

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

Earlier versions of these tables have appeared in the first draft

of this Monograph (November 1972) and as NBSIR 73-203 (May 1973).

Probably there will be future versions. The latest one should be used.

Each is identified by a date on each page of the tables.

4.1.2 Conventions Concerning Rate Constants

A. General Convention . Almost all of the reactions in the tables are elementary processes. For them the rate expression is derivable from a statement of the reaction, e.g.

A + 2B - AB^

-d[A]/dt = -(1/2) d[B]/dt = d[AB2]/dt = k[A][B]^

Note that the stoichiometric coefficient for B, i.e. 2, appears in the

denominator before B's rate of change (which is equal to 2k[A][B]^) as well as a power on the right hand side.

Wherever there may be any doubt an explicit rate expression is

given,

B, 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". For many

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.,

NO2 + NO^ (-H^) - N20^ (+M)

M

HNO^ HO + NO^

5
The rate expressions to be used do not have the concentration of M in

them, e.g., Rate = k[N02] [NO3] and k[HN03] respectively The units

given for the k's, s"-*- for first order, and cm''"-^ molecule "'-s"-'- for second

order, are consistent with this convention.

cases is

altitude, temperature and number density regime used in

altitude/km temp . /K log[Mj1 /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

al titude

C. Forward and Reverse Reactions . In some cases there are no data on

a reaction of interest but there are data on the "reverse" reaction.

Occasionally, for

A - B (f)

B - A (r) an evaluation will use the data on the "reverse" reaction together with

an equilibrium constant to obtain the other rate constant. Obviously

this is an approximation but it often is a useful method of estimating

non-measured physical properties.

The tables contain notations to warn the reader when this procedure has been used, such as "based on reverse reaction," or when both

reactions _f and r are listed together "kf = ^r^q" °^ ^r ~ ^^f/^eqThese expressions, which are those used in the analyses, are based on equating the two rates at equilibrium:

K^^= [B1/[A1 = kj/k_^.

6
4.1.3 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(-a[N]je)

a = (i/([N]je))in aji)

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

O 9 1 a is the absorption cross section, cm'^ molecule"-"- , [N] is the concentration of absorbers, molecules cm"^, and 1 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 con- vert "cross sections" to absorption coefficients in (atm at 273 K) "'cm'-'-

,

base e, multiply by 2.69 x 10-'-".

4.1.4 Arrangement of the Table

A. Reaction Grid . The contents of the data table and the location

of a reaction in it are shown on the "reaction grid," that follows this

discussion.

This grid shows the molecules of interest for stratospheric chemistry along the top and left edges. The symbol "K" in the intersection

for two reac tants means that data for the reaction are in the table

Combination reactions, A-hB-fM~*AB-l-M are above the main diagonal.

Bimolecular reactions, typically A + B C + D, are below the diagonal.

B. Sequence of Reactions . The order in which reactions are listed

follows the grid. All reactions of 0 atoms, the first species, shown

in its row and column are listed first, then those of the second

species, O(-'-D) , with all species other than 0 atoms, and so on. Thus

a particular reaction is placed with the reactant highest (or to the

left) on the grid. Bimolecular and combination reactions appear together.

The algorithm used to assign reaction locations is to construct an ordered ascending sequence of number pairs (or triplets), one for each

reaction according to the following rules:

(a) Assign numbers to each reactant in an equation. Use

the numbers at the left side of the grid.

(b) Arrange this set of numbers in ascending order, e.g

1, 3 not 3, 1; 4, 10, 11 not 10, 11, 4

7
(c) Order the sets in ascending order, giving priority to

the lower number in the corresponding position of two

-sets being compared, e.g. 1,4; 1,7; 4,10,10; 4,10,11;

18, 24 etc. This completes the assignment of reaction

sequence.

If a reaction is not filed according to this scheme, a cross ref- erence appears at the proper spot. Exceptions are made principally to

put forward and reverse reactions together.

C. Status of the Data . The reaction grid also shows what data are available and what are needed, A "dash" (-) means that the reaction

may be ignored for stratospheric chemistry. An "0" means that data

are needed or existing data should be evaluated. Often this means the

reaction is important, but at times it means that data are required so that the importance of the reaction can be assessed. A blank intersection merely means that no decision can be made at present. Finally,

data are included in the table for some reactions that are unimportant.

They are presented for comparison.

8
ChernlcalReactlon Matrix

K = Data in tabli!, 0 = Data selection or new data needed,

- = Unimportant for stratospheric chemistry, E = Data elsewhere In the chapter, (Blank) = Role of process not assessed

Combination Reactions: A+B+M-AB+M

. • ss tn H (rt (O . . »-i -t <ym a o o o o o

w

ST tn o O

o o e; 2: i:

f-i o o o (M ^ <N z z; z 2 S

CN rsl O O O O

cnO (N P-l o

z o o o ^

X to c/l crt

o

c/) o t/i

C/l (NJ C/l Cvt ^

X X X X (_) CIO

C102 C103

HCl

HOCl

HOCIO NOCl N02C1 C12 CO

<N X o o o o O OOOOzz ^«o»oao^ (NOCN'^'^'^f^f^f'n'^-TXXXX'^ OXXXXXXXXXxr<<Nnm.T

1 0

2 0(ID)

3 0(1S)

t) 02

5 02(ia)

- - K -

- - K - K 0 E

- ^ K

K

- K K K - K - - - K. - -- K K

- K -

- 0

- - K - -

6 02 (IE)

7 03

8 H

9 NO

10 N02

K K E K

K 0 K

K K 0 K

K -

K K K K K K

K K K K

X - - -

K K K K - - - -

- - K K 0

K 0

-

-

- K K

- K K K

K 11 N03

12 N2

13 N20

14 N205

15 NH

K K 0 K

- - E K

E 0 - K K K 0 K

K

K K K K K

K

0

K K K - - - - (Sc - -

- - - - 0 - ....

-

- -

16 NH2

17 NH3

18 H

19 HO

20 H02

- K

0 0 E K

0 0 0 K

K - 0

K K K -K

K

K

0 K 0 - K

K - - K

K K K -

- K K K

- K

K -

\- K

K

K K K ifS -

- K k\

...

K

-

- - 21 H2

22 H20

23 H202

24 HNO

25 HN02

K

0 0 E K

K 0 - K

0 0 K

E 0 0 -

K K - K - K K K K - K K K - K

K

K - K - - K - K - K - - K - K - - K K

K - K K K

- K K - - K K K K - _

26 HN03

27 SO

28 S02

29 S03

30 S20

K K 0 K

0 0

0 0 0 - 0 0--

K -

- K K

- K K

K -

- 0 -

0 -

- 0 K K -

K K

0 - 0

-

-

- K

31 HS

32 H2S

33 HS03

34 H2S04

35 CI 0 0 0 K

- - 0

0 0 0

- -

- -

36 CIO

37 C102

38 C103

39 HCl

40 HOCl

0 0

0

0

K

K

0

-

0

0

0 K

K

41 HOCIO

42 NOCl

43 N02C1

44 C12

45 CO

0 0

- E

- K - K K - - -

-

- - K - - K K

46 C02

47 CHO

48 CH20

49 CH3

50 CH30

- - E -

K K

- K K - - K - K

KK - K

- K

K

- K K

- K K K

K 51 CH302

52 CH30H

53 CH300H

54 CH3N02

55 CH3N03

0 0 0 K 0 - 0 0 0 -

0 - K rC K

56 CH4

57 C2H4

58 C2H6

59 C3H6

60 C3H8

K K K - - K

K K K

- K

K

K

- - - K - K K

K K

K

K

- K

61 C4H10 K K January 4, 1974 Bimolecular Reactions: A + B- C + D+ ...

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REFERENCES

Ahunada, J. J., Michael, J. V., and Osborne, D, T,, Pressure

Dependence and Third Body Effects on The Rate Constants for

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Tsang, W. , "Comparison between Experimental and Calculated

Rate Constants for Dissociation and Combination Reactions

Involving Small Polyatomic Molecules, Intern. J. Chem.

Kinetics 5, 947-963 (1973)

Vardanyan, I. A., Dangyan, T. M,, and Sachyan, G. A,, "Rate

Constants for the Reaction HO^ + CO -> CO^ + OH," Dokl.

Phys. 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 HO^ with Carbon Monoxide," J. Phys. Chem. 76

3301-3302 (1972)

Walker, R. W, , "Activation Energies of the Reversible Reaction

between Hydrogen Atoms and Methane to give Hydrogen and

Methyl Radicals," J. Chem. Soc, Sect. A, 2391-2398 (1968)

Walker, R. W. , Cortiments on "Gas-Phase Oxidation of Butene-2:

The Role of Acetaldehyde in the Reaction," Ray, D. J. M.

,

Diaz, R. R., and Waddington, D. J., Symp. Combust 14th

(Combustion Institute, Pittsburgh, 1973) 265-266

VJashida, N, , and Bayes, K. D. , "The Rate of Reaction of Methyl

Radicals with Atomic Oxygen, Chem. Phys. Letts. 23., 373-

375 (1973)

V7ashida, ^J.

, Martinez, R. I., and Bayes, K. D., "The Oxidation

of Formyl Radicals," typescript, Univ. of California (Los

Angeles) (1973)

V/atson, R. T, , [A Review of the Kinetics of the Reactions of

the Chlorine-Oxygen System], University of California,

Berkeley, Manuscript Tables (1973)

Wayne, R. P. private communication (1973)

68
Westenberg, A. A, and deHaas , N., "steady-Sta te Intermediate

Concentrations and Rate Constants, Some HO Results," J.

Phys. Chem. 76, 1586-1593 (1972)

Westenberg, A, A,, and deHaas, N. , "Measurement of the Rate

Constant for H + H^CO -> H^ + HCO at 2y7-b5 2*^K," J. Phys.

Chem. 76, 2213-2214 (1972)

V/estenberg, A, A, and deHaas, N. , "Rates of CO + OH and + OH Over an Extended Temperature Range," J. Chem. Phys. 58 , 4061-4065 (1973a)

V7estenberg, A. A. and deHaas, N. , "Rate of the Reaction OH + OH -> H^O + O," J. Chem. Phys. 58, 4Cfc6-4C71 (1 973b)

Wilson, Wm. E, , Jr., "a Critical Review^^of the Cias-Pl^ase

Reaction Kinetics of the Hydroxy 1 Radical, J. Phys. Chem.

Ref. Data i, 535-573 (1972)

Wong, W. , and Davis, D. D. , "a Flash Photolysis-Resonance

Fluorescence Study of the Reaction of Atom.ic Hydrogen with

Molecular ox^^gen: H + O^ + M -> HO^ + M, (to be published

in Intern. J. Chem. Kinetics, 1973)

Wu, C. H., Morris, E. D. , Jr.,„and Niki , H., "The Reaction of

Nitrogen Dioxide with Ozone," J. Phys. Chem. 22. 2507-2511

(1 973)

V7yrsch, D. , Wendt, H. R. , and Hunziker, H. E., "Modulation

Kinetic Spectroscopy of Hg/H^/O^/CO Mixtures: Reactions of

HgH and ^^2*" Intern. Symp. on Free Radicals

( Eerchtesgaden-Konigs see , Sept. 4-7, 1973) Paper No, 36

69
4.2 Vibrational Energy Transfer Processes (R. L. Taylor)

4.2.1 Introduction

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. The table provided here was prepared

in December 1973.

70
1^

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References

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Black, G. , and Eckstrom, D. J. , "Excitation and Deexcitation of Vibration

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Buchwald, M. I. , McFarlane, R. and Bauer, S. H. , Laboratory of Plasma

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79
r; + 'o O CO CO CO CO f—

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1 ro vo

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H H 1 CO t—

1 X CO

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1 1 CM t-( 1 CM o

o o 1 o o 1 CM O a.

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o

o

o

V

EhVo

o

o

SI+

cs o

r

+o

+o

ooo

V

H

V

o

o

o

CM

s

+

CM z

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o

oo

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o

o

o

o

V

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oCM

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T+o

+

o

+

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80
References

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M. Camac and R. M. Feinberg

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S. C. Lin and J. D. Teare

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

81
4.4 Ion Molecule Reactions (E. E. Ferguson)

4.4.1 Explanation of Tables

The reactions are listed in the order: (1) atomic ions reacting

with neutrals, (2) molecular ions reacting with neutrals. The ions are listed according to atomic number except that obviously related reactions

may be grouped. No distinction is made between ion-atom interchange and

charge- transfer 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:

k : Rate constant in

Uncertainty: See Introduction

Method : Indicated by the

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.

SA Stationary Afterglow

This is a high pressure experiment in which reactant ions can

safely be assumed to be 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 - 600 K.

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 states. 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 low pressure

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

may have been produced in excited states which can be quite misleading.

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

cm sec (molecule implied)

for Discussion

following abbreviations

82
pressure mass spectrometer ion sources measure reaction cross sections

rather than reaction rate constants. Since most applications require

rate constants this introduces a small uncertainty. Essentially

Ja(E)E£dE must be approximated by a(E)Es, while in rate constant measur

ing experiments (FA, SA, DT) the experiment itself accomplishes the

integration. The low pressure MS experiments also involve a small elec

trie 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,

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 measure

as a function of ion kinetic energy in ICR but most reported values are essentially at thermal energy.

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, 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^/kb

It is often the case that the overall ion loss rate, k^ + k-^, is much

more precisely measured than is the branching ratio. There are 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

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.

83
Remarks: Given at the end of each Table

The data refer largely to thermal energy (thermalized room tempera

ture 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.

8^
4.4.2

Reaction

+ 0 - 0* + H

h'*' + Fe - Fe* + H

h"^ + - COH* + 0

He* + products

He* + - n"^ + N + He - Ng* + He

He* + O2 - O* + 0 + He - 0* + He

He* + CO - C* + 0 + He

He +NO-iN + 0 + He

He + HgO - products

He -t- COg - 0 + CO + He - CO* + 0 + He

Ho + CH(^ -• products

•I- He + *-2^6 products

C + Og - CO +0

+ COg - CO + CO

TABI£ I. Bltwry Po3ltlve-Ion Reuctlona

k(cEi^6eo"^) Uncertainty Method

3.8(-10) ± 50?t lM-9)

l-9(-9)

3.0(-9) < 1 (-13)

1.2(-9)

± 30^

± 305^

± 3C^

FA

B

FA

FA

FA

FA

Reference

Fehsenfeld 1972a

Rutherford 1972c

Fehsenfeld 1972a

Fehsenfeld 1971a

Fehsenfeld IjS^a

Farragher I97O

Reisarks

a

g

J\ - 1.5. y>

NOTE;

1.0(-9) + 0.3> -0.2 DT Helnerl I969 k /k. =1.2;

1.85(-9) ± 15/^ ICR La udens lager 1973

1.2(-9) ± 2C^ FA DunMn 1968a

1.5(-9) ± 30^6 MS Warneck 1967a k /k. = 1.1

FA Scbneltekopf I968 k /k, = 2.2. lA5(-9) ± 155^ SA Sayers 1964

1.0(-9) ± 30^6 FA Farragher 1970 \/\ = 1-6

8.5(-10) + 2.5j -2.0 DT Helmerl I969 k /k. = 14- c

1.5(-9) ± 25St ICR Laudenslager 1973

1.2(-9) ± 305& MS Warneck I967

1.10(-9) ± aA Bayers 196i+

l-7(-9) .± 3C^ FA Fehsenfeld 1966a

2.0(-9) ± 155t ICft Laudenslager 1973

1.6(-9) ± 30jt Moran I966

l-7(-9) ± 3C^ FA Fehsenfeld 1966a

2.1(-9) ± 3C^ MS Moran I966

2.0(-9) ± 155^ ICR Laudenslager 1973

5 6f-l0^ ± 0 s FA Hovard 1Q70

»*.5(-io) ± ZOf, FA Bolden 1972

1.2(-9) ± 3056 FA Fehsenfeld 1966a

l.6(-9) ± 15* ICR Laudenslager 1973

l.5(-9) i 1516 ICR Bowers 1972

2.3(-9) ± 15* ICR Bowers 1972

l.l(-9) i 3C^ FA Fehsenfeld 1966b

9.0(-10) ± 30^ ^G Frunklln I965

I..9C-9) ± 30^ FA FchncnfclJ 1966b

1.6(-9) ± 30^ D Schlldcrout 1970 a rate constant the notation

3.8 (-10) is used to indicate 3.8 x 10~10.

85
Table I Continued

Renotlon k(cm'^oec ^) Uncertainty Method Refci-ence

+ HgO - con* + H 2.0( -9) ± 30/' FA Boldcn 1972

+ Na -• Na"*^ + N very small B Rutherford 19T2a

-f + N + Mg - Mg + N 1.2(-9) B Rutherford 1971

N + TIa - Ca + N l.l(-9) B Rutherford 19T2b „+ „ ^ + N + Fe - Fe + N :,.5(-9) B Rutherford 1972c

+ 4- N + - NH + H 7 ( -10) ± 30^6 FA Fehsenfeld 1967a

N* + CO - CO* + N 5 (-10) ± 3<yf> FA Fehsenfeld 1967b

N* + NO - NO* + N 8 (-10) ± 30?^ FA Goldan I966

N* + Og - O^* + N - NO +0

7 (-10) ± 3<^ FA Farragher I97O

5 (-10) ± 30^^ DT Johnsen I97O

6 (-10) ± 30^^ FA Dunktn I968

6.l(-10) ± 30?& MS

FA

Warneck 1967b

Goldan I966

7 ( -10) MS AquUanti I966

N + HgO - HgO + N 2.6(-9) ± 0.1; FA Howard 1970

2.6(-9) ± 30^ FA Bolden 1972

N* + COg - COg* + N 1.3(-9) ± 30* FA Fehsenfeld 1967b 0*'+ H - H* + 0

0* + Na -• Na* + 0

6.8(-l0)

smalJ.

± 50* 1 and Keq

B

'Fehsenfeld 1972a

Rutherford 1972b

0* + Mg - Mg* + 0 small B Rutherford I97I

0 + Ca - Ca +0 7.6(-10) B Rutherford 1972b

0 + Fe - Fe +0 2.9(-9) B Rutherford 1972c

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

0* + Ng - NO* + N 1.3(-12) ± 15* FA Schmeltekopf 1958

1.2(-12) ± 10* FA

FA

Dunkln I968

Ferguson I969

+ 2- + 0 (T)) + Ng Ng +0 ~1 (-9) B Rutherford 1971

0* + NO - NO* + 0 < 1 (-12) FA Dunkln 1971a

0* + Og - Og* + 0 2,0(-ll) ± 15* FA Dunkln I968

2.0( -11) +0.4,-0.3 SA

SA

FA

Copsey 1966

Smith 1968

Ferguson I969 2.0(-U) ± 0.5 MS Warneck 1967b

0* .+ COg - Og* + CO 1.2(-9) ± 30* FA Fehoenfeld 1966c

1.0(-9) ± 30f' MS PnulDon 1966

86
Tabic 1 Continued

Reaction . k( 3 -In cm sec ; Uncertainty Method Reference

0* + HgO - H^O"^ + 0 2.3 '-9) ± 0.25 FA Howiird 1970

2.K '-9) ± 30X FA Boldcn 1972 - N^Q* + 0 2.2 -10) ± 1.3 MS Ryan 1972

- - NO"^ + NO 2.3 -10) ± 1.1+ MS Ryon 1972

k

a

= 6.3 -10) ± 3011, FA Dunkin 1971a - NO^"*" + 0 1.6( -9) ± 305^ FA Dunkln 1971a

Na* + -. NaO"^ + O2 < 1 ( -11) FA Ferguson I968

Mg* + 0^ - MgO'*' + Og 2.3( -10) ± 50^ FA Ferguson I968

S'*' + NO - NO"^ + S 1*.2( -10) ± 20^6 FA Fehsenfeld 1973a

s"^ + O2 - SO* + 0 1.6( -11) ± 205& FA Fehsenfeld 1973a

s"^ + CO^ -• products < 1 ( -12) FA Fehsenfeld 1973a

Ar"^ + - ArH* + H 6.8( -10) ± 20^t ICR Bowers 1969a

7.0( -10) ± 30^ FA Adams 1970 Ar^ + - Ng"^ + Ar 6.6( -11) ? MS Warneck 1967c

5 ( -11) ± 755^ ICB Laudenslager 1973

Ar* + CO - CO* + At 1.2( -10) ± 3C^ MS Warneck 1967c

9-0( -11) ± 30jl> FA Fehsenfeld 1966d

5 ( -11) ± 90^ ICR Laudenslager 1973 At* + NO - NO* + Ax 3.9( -10) ± 30?^ MS Warneck 1967c

2.5( -10) ± 30^ ICR Laudenslager 1973

Ar"*" + Og - Og* + At -10) ± 30^6 Warneck 1967c

5.0( -11) ± 3056 FA Adams 1970

7 ( -11) ± 50?^ ICR Laudenslager 1973

5.0( -3J.) ± 25St SA Smith 1970

Ar"^ + HgO - HgO* + Ar - ArH* + OH

-9) ± 0.1 FA Howard 1Q70

1.6( -9) ± 30^ FA Bolden 1972

Ar"*" + CO2 - CO* + At 7.0( -10) ± 3036 MS Warneck 1967c

7.6( -10) ± 3(^ FA Fehsenfeld 1966d

l*.6( -10) ± 15^ ICR Laudenslager 1973

Ar"^ + CHj^ - CRj* + H + Ar 6.5( -10) ± 3096 MS Jones 1971

-* CHg* + Hg + Ar IM -10) ± 30^^ IB Jones 1971 *\ = 9.0( -10) ± 303t FA Bolden I97O

-• products 1.3( -9) ± 159^ ICR Bowers 1972

-* products -9) ± 155t ICR Bowers 1972

K* + 0^ - KO* + Og

1

< 1 ( -11)

87

FA Ferguson I968
Tuble I ContinvciJ

RcMCtlOli k(cm-^oec ^) Unccrt iliity MeLhoJ Rererence Rciti;irk3

Cu"*" + 0^ - CuO""' + 1.6(-10) ± 50,( FA Fcrf^ution I'jGQ

Fe"*" + 0^ - VcO^ + 0._, 1.5(-10) * "jOjL FA Ferguson I96O

2.0( -9) i 10/, M3 Reuben I962

1.85(-9) MS Warneck 196Td

1.95(-9) ± 20^;; ICR Bowers 1969b

+ - N^H"" + H 1.95(-9) ± 20f, ICR Bowers 1969a

+ Ar - AtH"^ i H 1.2(-9) ± 2Ci, ICR Bowers 1969a

N2"^ + N - N"^ + <1 (-11) FA Ferguson I965

Ng"^ + 0 - NO'*^ + N l.l+(-10) X2 FA Fehsenfeld I97O

- O"^ + Ng <1 (-11) FA Fbrguson I965 t

N^"^ + H2 - Nj,Il'* + H l.Y(-9) ± 30^ FA Fchsenfeld 1967a l.M-9) ± 20^ ICR Bowers I969

"2' * °2 - ^2' ^ "2 6.6(-ll) ± 30^ FA Farragher 1970

6 (-11) DT Johnsen 1970 h

5 (-11) ± 30;^ FA Ferguson I969

6.5(-ll) ± 1 MS Aquilanti I966 - NO* + NO <3 (-1^) KS V/arneck 1967b

Ng"^ + CO - CO"^ + N^ 7 (-11) ± 305& FA Fehsenfeld 196Tb

Ng"^ + NO - NO'^ + Ng 3.3(-10) ± 30^fc FA Fehsenfeld I97O

l;.8(-10) ± 30% MS Warneck 1967b

N2"*" + - H^O* + 2.2(-9) ± 0.3 FA Howard 1970 - NgH"^ + OH 2.0(-9) ± .305fc FA Bolden 1972

Ng"^- + COg - CO2* + 9 (-10) ± 30^^ FA Fehsenfeld 1967b

+ Na - Na"^ + N^ 5.8(-10) ± 5c?;t FA Farragher I969

1.9(-9) E Rutherford 1972a g

N^"^ + Mg - Mg"^ + N^ T.2(-10) B Rutherford 1971a g

Ng"^ + Ca - Ca* + N^ 1.8(-9) B Rutherford 1972b_ g

Ng* + Fe - Fe"^ + i*.3(-10) B Rutherford 1972c g 0^ + N - no"*' + 0 1.8(-10) X2 FA Goldan I966

O^"'' + - no"*" + NO <1 (-15) FA Ferguson 19^5 0

O^'*' + NO - no''' + ©2 6.3(-10) ± 3C^ FA Fehsenfeld 1970

7.7(-10) ± SOjt MS Warneck 1967e

7.2(-10) ± 1.5 DT Johnsen I97O

^2"^ + HOg - NO2''" + ©2 6.6(-10) ± 30^ FA Fehsenfeld 1973b

O2'* + NH^ - NK^"" + O2 2.M-9) ± 30J FA Fehsenfeld 1973c

Og* + Na - Uu* + O2 6.7(-10) ± 50% FA Farragher I969 l.M-9) B Rutherford 1972u g

/
Tuble I Continued

Reaction Uncertulnty Method Reference Remurl'

- No* +' Oj 2.0 [-9) B Rutherford 1972a g 0* + Na - NuO* + 0 1.2 [-10) B Rol 1968 P

< 7 '-11) FA Fnrrogher I969 0^ + Mg - Mg* + ©2 1.2 -9) B Rutherford 1971Q g - Mg* + Og > 3 ( -9) B Rutherford 1971a i.s

0^ + Ca - Ca* + Og 1.8 -9) B Rutherford 1972b g 0*{&^^^ + Ca - Ca* + Og 3.5( -9) B Rutherford 1972b g 0^ + Fe - Fe* + Og 1.1( -9) B Rutherford 1972c g

NO"^ + Na - Na* + NO 7.7( -11) ± 50!^ FA Farragher I969

NO* + Mg - Mg* + NO 8.1( -10) B Rutherford 1971a g

NO* + Ca - Ca* + NO h.0\:-9) B Rutherford 1972b g

NO* + It - Fe* + NO 9.2( -10) B Rutherford 1972c g

NO* + 0^ - NOg* + Og < 1 ( -ih) FA Fehsenfeld 1973b

CO* + 0 - 0* + CO xM -10) ± 50^6 FA Fehsenfeld 1972a

CO* + N -• products < 2 ( -11) FA Fehsenfeld 1972a

CO* + NO - NO* + CO 3.3( -10) ± 3C^ FA Ftehsenfeld 1972fl

CO* + - COH* + H 2.0( -9) ± 30?^ FA Fehsenfeld 1967a

CO* + Og - O2* + CO 2.0( -10) ± 30f> FA Fehsenfeld 1966b

CO* + CO^ - COg* + CO 1.1( -9) ± 3C^ FA Fehsenfeld 1966b

CO* + HgO -• products 2.2( -9) ± 3(^ FA Bolden 1972

SiO* + 0 - Si* + O2 ~2 ( -10) FA Fehsenfeld 1969a

SIO* + N - SI* + NO ~ 2 ( -10) FA Fehsenfeld 1969a - NO* + Si - 1 ( -10) FA Fehsenfeld 1969a

MgO* + 0 - Mg* + O2 ~ 1 ( -10) FA Ferguson 1968

SO* + CO - S* + COg < 1 ( -12) FA Fehsenfeld 1973a <*N2 - NgH* + H2 1.5( -9) ± 30* FA Burt 1970

1.0( -9) •± 303t MS Aquilanti I965

Rj* + CO - COH* + iM -9) ± 30^6 FA Burt 1970

Kj* + NO - NOH* + iM-9) ± 30?^ FA Burt 1970

K3* * CO2 - CO2H* + Hg 1.9( -9) ± 30f, FA Burt 1970

H^* + NO2 - NO* OH + Hg 7 ( -10) ± 30* FA Burt 1970

"3* * ''2° - NgOH* + 1.8( -9) ± 3C^ FA Burt 1970

H3* + CHi^ - CHj* + Hg 1.6( -9) ± 305^ FA Burt 1970

7.5( -10) ± 3036 MS Aquilanti 19660 - C2H5* * H2 1.9( -9) ± 3056 FA Burt 1970 - C2H3**2H2 1.2( -10) ± 30^ FA Burt 1970

89
Reaction

Tuble 1 Continued

k(cm sec ) Uncertainty Method Reference Reimirko

JL* + C„H„ 3 2 2 2 3 2 l-9( -10) ± 30f, FA Burt 1970

H,* + H„0

3 2 H^O* + H„

3 2 ~ 3.0( -9) FA Burt 1970

H,* + NIL ~ 3.6( -9) FA Burt 1970

n„h"^ + co_ CO h"" + N„

2 2 9.2( -10) ± 30/. FA Burt 1970

KJi*' + N„0

2 2

N^OH"^ + N„

2 2 7.9( -10) ± 30?;, FA Eurt 1970

N„H* + CH, CH^"^ + N,, 5 2 8.9( -10) ± 30fo FA Burt 1970

NJI"^ + H„0 ? 2H^O"^ + N_

3 2 ~ 5 ( -10) FA Burt 1970

H„0"^ + H„0

2 2

H^O"^ + OH

3 l-7( -9) ± 30^ FA Bolden 1972

1.8( -9) ± 3o;t MS Good 1970

1.6( -9) ± 20^ MS Gupta 1967

H^O"^ + Na

2

Na"^ + H„02l-9( -9) B Rutherford 1972a g

HgO"*" + Ca - Ca"^ + H2O 1*.0( -9) B Rutherford 1972b g

HgO* + Fe Fe"^ + HgO 1.5( -9) B Rutherford 1972c g

CO^^ + H HCO"^ + 0

h"^ + CO2

6 ( -10) ± 50^^ FA Pehsenfeld 1971a

CO2 + 0 ©2 + CO

2.6 - 0 + CO,-10) X 2 FA Pahsenfeld I97O

CO/ +• N products < 1 ( -11) FA Fehsenfeld I97O co/ + «2 CO^H* + H iM -9) ± 3(^ FA Fehsenfeld 1967a

COg"^ + f(0 no"*' + CO2 1.2( -10) ± 30^ FA Fehsenfeld I97O co/ + O2 + CO2 5.0( -11) ± 30^ FA Fehsenfeld 1970

NO no"*" + NO2 2.9( -10) ± 30^ FA Fehsenfeld 19c'S'b so/ + CO so" + CO2 3.0( -10) ± 20^ FA Fehsenfeld 1973a so/ + O2 + SO2 2.8( -10) ± 20^ FA Fehsenfeld 1973a

KjO*' + Ca Ca" + «2° + H kM -9) B Rutherford 1972b

°2 °2* + 2N2 ^ ( -10) ± 30^^ FA Dunkln 1971b 0/ + 0 + °3 3 ( -10) . ± 2 FA Fehsenfeld l972b 0/ + HgO O2* E^O + °2 1.5( -9) ± 0.5 FA Howard 1972

1.3( -9) ± 503^ he Good 1970

2.2( -9) ± 30^ FA Ftehsenfeld 1971b

•Ng + H^O H2O + "2 ^ ( -9) ± 2 FA Howard 1972

°2 + ^^2 > 5 ( -11) FA Adorns 197b

•OH + H^O H^O^-HgO -t OH l.k{ -9) ± 0.5 FA Howard 1972

> 1 ( -9) MS Good 1970

3.2( -9) FA Fehsenfeld 1971b

80°K

90
Table I Continued

Re ictlon k(cm^6ec ^) Uncertainty Mjthod Reference

+ 1.0( 9) 0.1* f'A Howurd 1972

9 ( -10) ± 50f> MS Good 1970

1.9( -9) ± FA FehGcnrcld 1971b - H^O* + OH + 2 ( -10) •1 FA Howard 1972

3 ( -10) ± 1 MS Good 1970

« 3 ( -10) FA Fehcenfeld 19711)

+ - NO^-HgO + COg ~ 1 ( -9) FA Dunkln 1971b

N0'^(H20)^ + - H^0"'(H20)2 + HMO2 7 ( -11) ± 2 FA Howard 1972

8 ( -11) ± 5056 FA Feheenfeld 1971c

7 ( -11) ± SA Puckett 1971a

+ - NO'^-H^O + NO l.M -9) ± 0.3 SA Puckett 1971a

+ NH^ - NO^-NH^ + NO l-3( -9) ± 0.2 SA Puckett 1971a

) + NO - NO'^'NO + HgO 9 ( -11.) ± 2 SA Puckett 1971a

NO^-HpO + HH^ - NH,^"^ + HWOg 1.0( -9) ,303^ FA Fehsenfeld 1971d

+ HH^ - NH, + HNOh 3 l.l( -9) ± FA Fehsenfeld 1973c

+ NH^ - NHj^"^ + ONNHg 9.1( -10) ± 30^ SA Puckett 1971b

+ NH^ - NHjj^"^ + NUg 1.9( -9) ± 0.2 ICR Huntress 1971a

1.5( -9) 3(^ MS Melton 1966

l-7( -9) ± 30^ FA Fehsenfeld 1973c

+ NH^ - NH,^* J- HgO 2.1( -9) ± 305^ FA Fehsenfeld 1973c

+ KH^ — products 2.6( -9) ± 305t FA Fehsenfeld 1973c

+ NEj - products 1.6( -9) ± 30f, FA Fehsenfeld 1973c'

+ NH^ -• products 2.1( -9) FA Fehsenfeld 1973c

NH.*(H_0) + NH^ - NHi^'^CNH^) + HgO x.2( -9) ± 3Cff, FA Fehsenfeld 1973c

NH,^*(H20)2 + NH^ + HgO

^9 ( -10) ± 305^ FA Fehsenfeld 1973c

91
FOOTNOTES

Agrees well with extrapolated beam measurements

Farragher gives = 6.5(-10) ± 1.3, = i4-.2(-10) ± O.9

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

Rate constajit found to be independent of temperature, 3OO-6OO K

Rate constant proportional to T in thermal range

Rate constant independent of vibrational temperature from 300-600°K but ratio k^/k^ increases v/ith T^

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 vibrational temperature from 3OO-60OO K

Rate constant given for temperature range 8O-6OO K

_X Gives rate constant proportional to T ^ in thermal range.

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

Probably endothermic

Measurements on this reaction have given rate constants ranging from U( -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.

-15 3 -1 It has also been shown (FA) that k < 10 cm sec at 6OO K

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

General Dynamics/Convair Report GDC-DBE69-002 of January I969

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

large

Reaction is endothermic

The energy dependence of this reaction is given in McFarland, et al, J. Chem. Phys. 60, Jan. 1, 197^.

(The full reference is M. McFarland, D. L. Albritton, F. C. Fehsenfeld, E. E Ferguson and

A. L. Schmeltekopf, and all known data is summarized in figures In this paper).

Current measurements in progress suggest that this rate constant

may be slightly larger than 10

92
REFERENCES TABLE I

N. G. Adams, D. K. Bohme, D. B. Dunkin, and F. C. Fehsenfeld, J. Chern. Phys . I95I (l970a)

N. G. Adams, D. K. Bohme, D. B. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, J. Chem. Phys. 3133 (l970b)

V. Aquilanti, A. Galli, A. Giardini Guidoni, and G. G. Volpi, J. Oiem. Phys. I969 (I965)

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

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

R. C. Bolden and, R. S. Hemsworth, M. J. Shaw, and N. D. OViddy, J. Phys. B 3, 1^5 (1970)

R.'C. Bolden and N. D. Tv;iddy, Faraday Disc. I92 (l9T2)

M. T. Bov/ers and D. D. Elleman, J. Chem. Phys. §1., 4606 (1969a)

yi. T. Bov/ers, D. D. Elleman, and J. King, Jr., J. Chem. Phys. 50, h^8^ (1969b)

M. T. Bowers and D. D. Elleman, Chem. Phys. 16, 1*86 (I972)

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)

M. J. Copscy, D. Smith, and j. Sayers, Planet. Space Sci. llt^ 10k7 (I966)

D. B. Dunkin, F. C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, J. Chem. Phys. h^j 13^5 (1968)

D. B. Dunkin, M. McParland, F. C. Fehsenfeld, and E. E. Ferguson, J. Geophys. Res. 76, 3820 (l971a)

D. B. Dunkin, F. C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, J. Chem. Phys. 5I+, 3817 (l971b)

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

A. L. Farragher, Trans. Faraday Soc. 66, Ikll (I970)

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

(1966a)

P. C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, J. Chem. Phys. k5_, 23 (1966b)

F. C. Fehsenfeld, E. E. Ferguson, and A. L. Schmeltekopf, J. Chem. Phys. khj 3022 (1966c)

F. C. Fehsenfeld, E. E. Ferguson, and A. L. Schmeltekopf, J. Chem. Phys. hOk (l966d)

F. C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, J. Chem. Phys. h6, 2802 (1967a)

F. C. Fehsenfeld, A. L. Schmeltekopf, and E. E. Ferguson, J. Chem. Phys. h6j 2019 (1967b)

F. 0. Fehsenfeld, Can. J. Chem. kj, I808 (1969a)

F. C. Fehsenfeld, E. E. Ferguson, and M. Mosesman, Chem. Hiys. Letters k_, 73 (1969b)

F. C. Fehsenfeld, D. B. Dunkin, and E. E. Ferguson, Planet. Space Sci 18, 1267 (l970)

F. C. Fehsenfeld and E. E. Ferguson, J. Geophys. Res. 76, 814-53 (l971a)

F. C. Fehsenfeld, M. Mosesman, and E. E. Ferguson, J. Chem. Phys.

^ 2115 (l971b)

F. C. Fehsenfeld, M. Mosesman, and E. E. Ferguson, J. Chem. Phys. §5^ 2120 (l971c)

F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys, '^ih, I+39 (l971d)

F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys. 56, 3066 (l972a)

F. C. Fehsenfeld and E. E. Ferguson, Radio Sci. 7, II3 (l972b) »

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

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

F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys; (l973c) in press 93
E. E. Ferguson, F. C. Fehsenfeld, P. D. uoldan, A. L. Schj^eltekopf , and H. I. Schiff, Planet. Space Sci. 1^,

823 (1965)

E. E. Ferguson and F. C. Fehsenfeld, J. Geophys. Res. 73, 6215 (I968)

E. E. Ferguson, D. K. Bohme, F. C. Fehsenfeld, and D. E. DunVan, J. Cham. Phys . §0^ 5039 (I969)

J. L. Franklin and M. S. B. Munson, Ttenth Combustion EympoEium, p. 56I, Combustion Institute, Pittsburgh, Pa.

(1965)

P. D. Goldan, A. L. Schnieltekopf, F. C. Fehsenfeld, H. I. Schiff, and E. E. Ferguson, J. Chem. Phys. kh, i)-095

(1966)

A. Good, D. A.Durden, and P. Kebarle, J. Chem. Phys.

^

212, 222 (1970)

S. K. Gupta, E. G. Jones, A. G. Harrison, and J. J. Myher, Can. J. Chem. 3IO7 (I967)

J. Heimerl, R. Johnsen, and M. A. Biondi, J. Chem. Phys. 504l (I969)

C. J. Howard, H. W. Rundle, and F. Kaufman, J. Chem. Phys. 37I+5 (I970)

C. J. How.ird, H. W. Rundle, and F. Kaufman, J. Chem. Phys. 55, h^^2 (I971)

C. J. Howard, V. M. Bierbaujn, H. W. Rundle, and F. Kaufman, J. Chem. Phys. 57, 314-91 (1972)

W. T. Huntress, M. Mosesman, and D. D. Elleinan, J. Chem. Phys.

^ 81+3 (l97l)

R. Johnsen, H. L. BroTM, and M. A. Biondi, J. Chem. Phys. 52, 508O (197O)

E. G. Jones and A . Harrison, Int. J. Mass Spectro. Ion Phys. 6j 77 (l97l)

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

E. W. McDaniel, V. Cemak, A. Dalgarno, E. E. Ferguson, and L. Friedman, Ion -Mole cule React-i ons

,

Wiley, New

York 1970

T. F. Moran and L. Friedjuan, J. Chem. Phys. h5_, 3837 (1966)

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

J. F. Paulson, R. L. Mosher, and F. Dale, J. Chem. Phys. Uh^ 3025 (I966)

L. J. Puckett and M. W. Teague, J. Chem. Phys.

^ 256I+ (1971a)

L. J. Puckett and M. W. Teague, J. Chem. Phys. 5!+, 1+660 (197113)

B. G. Reuben and L. Friedman, J. Chem. Phys. ^l, 1^36 (1962)

P. K. Rol and E. A. Entenann, J. Chem. Phys. h^j lk30 (I968)

J. A. Rutherford, R. F. Mathls, B. R. Turner, and D. A. Vrcom, J. Chem. Phys.

^ 3765 (l971a)

J. A. Rutherford and D. A. Vroom, J. Chem. Hiys . 2L> 5622 (l971t)

J. A. Rutherford, R. F. Mathis, 3. R. Turner, and D. A. Vroon, J. Chem. Phys.

^ I+65U (l9T2a)

J. A. Rutherford, R. F. Mathis, E. R. Turner, and D. A. Vroom, J. Chem. Phys. 3087 (1972b)

J. A. Rutherford and D. A. Vroom, J. Chem. Phys.

^ 309I (1972c)

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

J. Sayers and D. Smith, Disc. Faraday Soc. 37^ 167 (l96h)

S. M, Schildcrout, J. G. Collins, and J. L. Franklin, J. Chem. Phys.

^ 5767 (l970)

A. L. Schmeltekopf , E. E. Ferguson, and F. C. Fehsenfeld, J. Chem. Phys. 1+8, 2966 (I968)

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

D. Smith, C. V. Coo'iall, N. G. Adams, and A. G. Dean, J. Fnys. B 3I+ (1970)

94
P, Warneck, J. Chem. Pliys . hj_, U279 (l96Ta)

P. Warneck, J. Geophys. Res. J2, 1651 (196Tb)

P. Warneck, J. Chem. Phys . h6_, 513 (19670)

P. Warneck, J. Chem. Phys. h6, 502 (l967d)

P. Warneck, Planet. Space Sci. 15_, 13^1-9 ( 19676

)

95
4.4.3 TABLE II. Blnnry Ncg!itlvc-Ion Rcuctlona

Reaction k(cm^oec ^) Uncertainty Mothod R-i Teronce

H" + H - + e 1.3(-9) ± 50'^ FA Schneltckopf 1967

1.8(-9) X2 FA Fehsenfeld 1973a

H' + CO - HCO + e -5 (-11) FA Dunkin, 197c

H' + NO - JfflO + e U.6(-lo) ±_ 30,t FA Dunkin, 1970

H' + ©2 - HO2 + e 1.2(-9) ± O.Z FA Dunklji, 1970 - 0" + OH < 1 (-11) FA Dunkin, 1970 - + H < 1 (-11) FA Dunkin, 1970 - OH' + 0 < 1 (-11) FA Dunkin, 1970

H" + NgO - OH' + N2 l.l(-9) ±0.3 FA Duni.tn, 1970

H' + NOg - KO2" + H 2.9(-9) ± 3C^ FA Ferguson, I969

H' + HgO - OH" + Hg 3.8(-9) ± 3o;i MS Mslton, 1971

C" + Kg products < 1 (-13) FA Fehsenfeld I97O

C' + CO - C^O + e 4.1(-10) ± 30^ FA Fehsenfeld, 1970

C" + Og - 0" + CO ll.O(-lO) ± 3oi> FA Fehsenfeld, I97O

C* + HgO - CO + Ifg + e 9.0(-10) ± 30^ FA Fehsenfeld, I97C

C" + COg - 200 + e '+.7(-li) ± 3C^ FA Fehsenfeld, 1970

0" + 0 - Og + e 1.9(-10) X2 FA Fehsenfeld, I967

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

0" + Hg - HgO + e T.o(-io) ± 0.5 DT Parkes, 1972a

6.o(-io) ± 30^ FA Ferguson, 19^9

7.2(-10) ± 1 DT Moruzzl, I96O - oh' + H 3.3(-U.) ± 0.5 DT Parkes, 1972a

0" + CO - COg + e 6.5(-l0) ± 1 DT Moruzzl, 1968

0' + NO - NOg + e

k.h[-l0)

i.'^i -loS 2.2(-10)

± 30^ ±07

± 0.5

FADT

DT

Ferguson, I969

X ox roc ^ , 7 i ^0 Moruzzl, 1968

1.6(-10) ± 305^ FA Ferguson, 19^9

O" + Ng -« NgO + e < 5 (-13) DT Moruzzl, 1968 < 1 (-12) FA Fehsenfeld, 196£ ~ 3 (-10) FA Fehsenfeld, 1969a

0" + HgO - OH" + OH lA(-9) MS Melton, 1971

0* + NgO - NO" + NO 2.2(-10) ± o.k FA Marx, 1973

2.5(-10) ± 0.5 ICR Marx, 1973

•1.95 (-10) ± 0.06 DT Parkes 1973

O' + NOg - NOg" + 0 1.2(-9) ± 30* FA Fterguoon, I969

0" + 0^ - 0^* + 0 5.3(-io) X2 FA Fergus ai, 1969

0' + CHj^ - OH" CRj l.l(-lO) ± 0.1 DT Pnrkes, 1972n

l.o(-io) i 20f, FA Bohme, I969

96
Table II continued

Reaction k(ciii cec" ) Uncertainty Method Reference Remarka

O' + C„H, C„H| 0 + e U.05(-10) ± 0.5 DT Parke s, 1972a

Cgllg" + H2O 1-9 (-3.0) ± 0.3 DT Pnrkcs, 1972a

O" + CJ{_

2t 2 CgH^O + e 1.3 (-9) ± 0.09 DT Parkeo, 1972q

C„H" + OH 2 8.0 (-10) ± 0.5 DT Parke s, 1972a

CoOH + H

2

8 (-11) ± 1 DT Parkes,. 1972a

0" + C^Hr 2 6 oh" + C^H^ 7.0 Mo) ± 2C^ FA Bohrae , I969

• 3 8

oh" + C,H„

3 T

9.3 -10) ± 20^ FA BoViBie , 1969

oh" + C| h„ 1.2 .-9) ± 205^ KA Bohrae, I969

F* + H HF + c 1.6 '-9) X2 FA Fehcenfeld, 1973a

S" + H„2

HgS + e < 1 ( -15) FA Fehsenfeld, 1969b

S' + 0_2 S0_ + e 2

3.0( -li) ± 303^ FA Fehsenfeld, 1969b

Cl" + H HCl + e 9.0( -10) X2 FA Ferguson, 19^9

1.0( -9) X2 FA Fehsenfeld, 1973a

oh" + H HgO + e 1.0( -9) X2 FA Ferguson, I969

1.8( -9) X2 FA Fehsenfeld, 1973a

oh" + 0 HOg + e 2.0( -10) ± 50^ FA Fehsenfeld, I966

oh" + N HMO + e < 1 ( -11) FA Fehsenfeld, I966

oh" + NOg KOg" + OH 1.9( -9) ± 30^ FA Ferguson, 19^9

ES" + H l-3( -9) X2 FA Fehsenfeld, 1973a

CH" + H HCN + e 8.0( -10) X2 FA Fehsenfeld, 1973a

no" + ©2 Og" +'N0 5.0( -10) ± 3C^i FA McJkrland, I972

no" + NgO NOg" + Ng 2.8( -11.) ± 0.2 DT Parkes , 107'-l

no" + NOg NOg* + KO IM -10) ± 305^ DT McForland, 1972

b»" + H

2

products 1.5( -9) X2 FA Fehsenfeld, 1973a

Og' + N NOg + e U.0( -10) ± 505^ FA Fehsenfeld, I967

Oo" + 0

2

0- + e 3 3.3( -10) ± 5C^ FA Fehsenfeld, I967

0„" + H„ 2 2 products < 1 ( -12) FA Fehsenfeld, unpublished

0„" + 0„(^A ) 20^ + e 2 ~ 2 ( -10) FA Fehsenfeld, 1969a

0„" + N„0 2 2 0," + No

3 2 < 1 ( -12) DT Parkes, 19^3

Og* + NOg N0„* + 0„ 2 2 8.0( -10) ± 3C^ FA Ferguson, 19^9 0„" + 0

2 3 0_" + 0„

3 2 3.0( -10) ± 305^ FA Fehsenfeld, I967

0„' + S0_ 2 2 so^" + 0_

2 2

l».8( -10) ± 30^ FA Fehsenfeld, 1973b

NOg* H oh" + NO 3.0( -10) X2 FA Fehsenfeld, I972

l».0( -10) X2 FA I>2hsenfeld, 1973a

KOg' + 0 products < 1 ( -11) FA Fehsenfeld, unpublished

KOg* + N producto < 1 ( -11) FA Fehsenfeld, unpublished

97
Table II cont'nued

Reaction k(an^i-oc ^) Uiiccr til liity Method Reference

NO * + NO NO^" + NO ~ U f-1?^ PA

NOg" + 0^ NO * + 0 1.0 ± 505!) FA Feh^jCnfeld^ 1968

" + H CiU~ + n 8.U X2 FA P^V> Cf»n fol 1973Q

0

" + N "* products < 1 FA Pehsenfeld ^ unpublished

" + NO 1.0 '-111 ± 50^ FA Fehsenfeld, 1967 f

0^" + COg COj" + ©2 U.O '-10) FA Fchsenfeld, 1967

5.5 '-10) ± 0.5 DT Parke s, 1972b

0

" + NO "* products 2.8 -10^ ± 30^^ FA Dunkin, 1972

0

" + SO -• SO " + 0 ^"3 2

1 7 -9) ± 30;^ FA Fehs en fe Id

,

—^ I

CO^" + 0 - Og" + co^ 8.0( -n) ± 50^ FA Fehsenfeld j 1^67

COj" + NO _ NOg" + CO2 9.O1 -12) X2 FA Fehsenfeld ^ 1967

1.8( -11) ± 30jt FA Fehsenfeld, 1973t)

CO " + NO

^ 2 products 2 1 -10) X2 FA Fehsenfeld, 1973b

CO^" + SOg — SO^" + CO2 2 ^1 -10) ± 3C^ FA Fehsenfeld, 1973b

NO^" + N -• products < 1 ( -11) FA plehsenfeld, 1969c wn " + n < 1 1 -11) FA Fehsenfeld, 1969c

0. " + 0 0

* + 0

^3 "2

-* 0" + 20^ /

-10) ± FA Fehsenfeld, 1969c k

a

Oj^* + CO — CO " + 0 ^^3 ^2 < 2 1 -11) FA Adams, 1970

Oj^" + NO •- NO^ + Og 2. Si -10) ± 3C^ FA Adans, 1970 h

0

~ + CO CO " +

0" -10^ ± 303^ FA Adams, 1970

0^- + HgO - Og'-HgO + ©2 1.5( -9) MS Payzant, 1972

1.1*( -9) DT Pack, 1971

CO]^" + 0 "* co^" + Og

0

" + CO "3 2

-10) ± 50^ FA Fehsenfeld, 1969c k

a

CO, ' + NO _ DO^ + COg 4.8( -11) ± 305& FA Fehsenfeld, 1969c h

0 ~*H 0 + NO -. »jo ~ + H 0 -10) ± ZO^ft FA Adams, 1970 0 "-H 0 + CO

2 2 _ COj^" + HgO 5.8( -10) ± 3C^ FA Adams, I970

0 "-H 0 + 0 "2 V "3

~* Tiy LJX "-AJ 1Li.'— 1 r* tCOc J 1 -10) ± 30^ FA Fehsenfeld, 1973b

ft "^Tr + n

2 * 2 2 3 -10) -1X1

± 30^ FA Fehsenfeld, 1973b

.« NOj NO -* NO * + ^10 1.5( -11) X2 FA Adams, 1970 h

VO ' + NO -* NO * + NO

2 ~ f -15) DT Parkea, 1972c 1

0„''U„0 + 0^ - 0, " + lUO 2.5( -15) ± 1 DT Parkas, 1971 1

©^'(HgO) + CO2 — products 3 ( -10) X2 FA Fehsenfeld, 1973b

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

98
Tublc II continued

Renctlona k(cm^cec"^) Uncertainty Method Refcr'-ncc Rcmarko

CO '(it o) + i;o prcxiucts 1.8(-ll) X2 FA FcliGcnrdd f 1973b

CO o) + NO^ products 1.5(-10) X2 FA rthscnfcld

,

1973b

NO "(II 0^ + so^ 1.5(-9) ± 30/p FA 1973b

SO, " + NOg KOg' + SOg + ©2 2.5(-10) X2 FA Fehscnfold

,

1973b

NO^" + SO^ 1 (-10) X2 FA Fehsenfeld, 1973b

SO^" + HgSO^ + e <1 (-11?) FA Fehsenfeld, 1973b

99
FOOTNOTES

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

2, 885, 1969)- The value at thermal energy is 2.0(-9) and the energy dependence is also given,

k independent of ion energy, 0-5 eV.

F. Kaufman, J. Chem. Phys. k6 , 2hh9, 19^7 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.

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

than for thermal ions, there has been a spread in published rate conetants. Ttiis effect leads to a

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

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

The electron affinity of NO is so low (~ 0.021+ eV =s kT) that collisional detachment is rapid in almost

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

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

NOg" + Og.

Products uncertain, either NOg or NO^ or both.

There axe two forms of NO^ , suggested as being the stable nitrate ion 0-N-O and the higher energy per-

- / I oxide ion 0-N-O-O (which is denoted NO^ ). q Reaction is endothermic

Probably endothermic

100
REFERENCES, TABIE II

N. G. Adams, D. K. Bohme, D. B. Dmikin, F. C. Fehsenfeld, and E. E. Ferguson, J. Chem. Phys.

^ 3133 (1970)

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

D. B. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, J. Chem. Phys. 5^, 98? (I970).

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. k3j iQh-k (1966)

F. C. Fehsenfeld, A. L. Schxeltekopf , H. I. Schiff, and E. E. Ferguson, Planet. Space Sci. 15^ 373 (I967)

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

F. C. Fehsenfeld, D. L. Albritton, J. A. Burt, and H. I. Schiff, Can. J. Chem. 47, 1'7'93 (l969a)

F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys. 5I, 3512 (1969b)

F. C. Fehsenfeld, E. E. Ferguson, and D. K. Bohme, Planet. Space Sci. 17, I759 (1969c)

F. C. Fehsenfeld and E. E. Ferguson, J. Chem. Phys. 53^ 26lf)- (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., 58, 58^1 (1973a)

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 • uson, J. Chem. Phys. 58, 3267 (1973)

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. £3, 6757 (l97l).

J. L. Moruzzi, J. W. Ekin, and A. V. Phelps, J. Chem. Phys. kS, 307O (1968)

J. L. Pack and A. V. Phelps, Bull. Am. Phys. Soc. I6, 2li+ (I971)

D. A. Parkes, Trans. Faraday Soc. 67, 711 (l97l)

D. A. Parkes, J. Chem. Soc. Fareiday Trans. I. 68, 613 (l972a)

D. A. Parkes, J. Chem. Soc. Faraday Trans. I. 68, 627 (l972b)

D. A. Parkes and T. M. Sugden, J. Chem. Soc. Faraday Trans. II, 68, 6OO (1972c)

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

J. D. Payzant and P. Kebarle, J. Chem. Phys. 56, 3^2. (1972)

A. L. Schmeltekopf, F. C. Fehsenfeld, and E. E. Ferguson, Astrophys. J., 1^, LI55 (1967)

101
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Photochemical Data for Modelling of the Stratosphere

(Revised)

5. l-'ubl ic ai ion Date January 1974

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bibliography or literature survey, mention it here.) Chemical kinetic and photochemical data for gas phase reactions pertinent

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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.

V

17. KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper name; separated by semicolons) 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

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