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CO NBS TECHNICAL NOTE 866

U.S. DEPARTMENT OF COMMERCE/ National Bureau of Standards
NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards' was established by an act of Congress March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation's science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts

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Sciences" Applied Radiation " — Quantum Electronics 1 — Electromagnetics 3 — Time

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THE OFFICE FOR INFORMATION PROGRAMS promotes optimum dissemination and

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8 Part of the Center for Radiation Research.

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» Part nf thp Center for RtiilHino Tprhnr.lr.ov
"* STAKTDABD3 LIBRARY 2 8 JUL

Chem.cal Kinetic and

Photochemical Data for

C 100

Modelling Atmospheric Chemistry 1515_

Edited by

Robert F. Hampson, Jr., and David Garvin

Physical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

This work was supported by

The Department of Transportation

Climatic Impact Assessment Program,

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

*< "*

U.S. DEPARTMENT OF COMMERCE, Rogers C. B. Morton, Secretary

NATIONAL BUREAU OF STANDARDS, Richard W. Roberts, Director

Issued June 1975
Library of Congress Catalog Card Number: 75-600025

National Bureau of Standards Technical Note 866

Nat. Bur. Stand. (U.S.), Tech. Note 866, 118 pages (June 1975) CODEN: NBTNAE

Supersedes NBSIR 74-430

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1975

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402

(Order by SD Catalog No. C 13.46:866). Price $1.85 (Add 25 percent additional for other than U.S. mailing)
FORWARD

The National Standard Reference Data System was established in

1963 for the purpose of promoting the critical evaluation and dissemination of numerical data of the physical sciences. The program

is coordinated by the Office of Standard Reference Data of the National

Bureau of Standards, but involves the efforts of many groups in universities, government laboratories, and private industry. The primary

aim of the program is to provide compilations of critically evaluated

numerical data. These tables are published in the Journal of Physical

and Chemical Reference Data , the NSRDS-NBS Publication Series of the

National Bureau of Standards, and through other appropriate channels.

The present report consists of tables of data assembled for use

in modelling the chemistry of the stratosphere. It represents contributions from the Chemical Kinetics Information Center, other NSRDS

data centers, and a number of individual experts. Support for the

preparation of those tables has been provided by the Department of

Transportation, under the Climatic Impact Assessment Program, and by

the Office of Standard Reference Data.

David R. Lide, Jr.

Chief, Office of Standard

Reference Data

111
TABLE OF CONTENTS

Abstract 1

1. Introduction 1

1.1 Content and History 1 1.2 Related Data Evaluations 3 1.3 Guide to the Tables 4

2. Chemical Reaction Matrix 9

3. Table. Data for chemical reactions and photochemistry

of neutral species 10

4. Supplemental Table. Rate constant for the reaction

HO + N0 2 (+ N 2

)

-» HN0

3 (+ N2

) as a function of

temperature and total gas concentration 72

5. Reference List and Notes 74

Appendices :

1. Chemical Thermodynamic Properties of Selected

Molecular Species 91

2. Addenda and Errata 105

3. Conversion Tables 110

IV
Chemical Kinetic and Photochemical Data

for Modelling Atmospheric Chemistry

R. F. Hampson, D. Garvin, Editors

A table of data for gas phase chemical reactions

and photochemistry of neutral species is presented.

Specifically, it gives preferred values for reaction

rate constants, photoabsorption cross sections, and

quantum yields of primary photochemical processes and

also cites recent experimental work. It is intended

to provide the basic physical chemical data needed as input data for calculations modelling atmospheric

chemistry. An auxiliary table of thermo chemical data for

the pertinent chemical species is given in the appendix.

Key words: Atmospheric chemistry; chemical kinetics; data

evaluation; gas phase; photoabsorption cross section; photochemistry;

quantum yield; rate constant.

1 . Introduction

1.1. Content and History

This technical note consists of a table of data on the kinetics

of chemical reactions and the photochemistry of neutral species. This

is supplemented by a table of thermochemical d ata for the species

involved. It is designed for use in modelling the chemistry of the

stratosphere

The table is 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. S. Domalski, E. E. Ferguson, D. Garvin,

R. F. Hampson, R. D. Hudson. L. J. Kieffer, H. I. Schiff, R. L. Taylor,

D. D. Wagman. and R. T. Watson in "The Natural Stratosphere of 1974",

E. Reiter, editor, Climatic Impact Assessment Program Monograph 1, U. S.

Department of Transportation. The present table will also appear in the

This work was supported by the Climatic Impact Assessment Program,

Office of the Secretary, Department of Transportation and by the Office

of Standard Reference Data, N.B.S.
final version of the monograph to be published in the Fall of 1975.

The table includes contributions of rate evaluations by other

scientists. These contributors represented in the present edition are

D. L. Baulch, D. D. Drysdale and D. G. Home, 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; W. H. Breckenridge, University of Utah,

and E. S. Domalski and D. D. Wagman of the NBS Physical Chemistry

Divi sion

Several preliminary versions of the main table in this Note have

been distributed. The history is explained below. The date of

preparation of each version is given in the upper left hand corner of

each page. The present version, dated November 22, 1974 supersedes

all earlier tables. Addenda and errata, which may be found as Appendix

2, update the main table to March 1975.

The first version of this 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. Another

revised and expanded version was distributed in NBSIR 74-430 in January.

1974.

The present table updates these. In particular, it incorporates

pertinent new data presented at the Symposium on Chemical Kinetics

Data for the Lower and Upper Atmosphere, Airlie House, Warrenton.

Virginia, September 1974.

The two NBS reports referred to above also contained separate

tables of rate data on vibrational energy transfer processes (R. Taylor),

high temperature air reactions (R. Taylor), and ion-molecule reactions

(E . E. Ferguson). The high temperature air reactions have been

incorporated in the present table. The other two have been published

independently as indicated below.

a. Vibrational energy transfer processes - R. Taylor,

"Energy Transfer Processes in the Stratosph re," Can. J.

Chem. 52, 1436 (1974).

b. Ion-molecule reactions - E. E. Ferguson. "Rate Constants

of Thermal Energy Binary Ion-Molecule Reactions of

Aeronomic Interest." in Atomic Data and Nuclear Data Tables

12, 159 (1973).
The present tables (and earlier versions) include recommended

values for reactions of O(-'-D) atoms. The evaluation of these data

is explained in the CIAP Monograph 1 and has been published separately

as R. J. Cvetanovic, "Excited State Chemistry in the Stratosphere,"

Can. J. Chem. _52, 1452 (1974).

1.2. Related Data Evalutions

This table relies heavily upon other modern data evaluation work.

Some pertinent sources are summarized here.

Contributors to this data survey were mentioned in section 1.1.

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 H 2 -0 ? system" D. L. Baulch, D. D. Drysdale, D. G.

Home and A. C. Lloyd, (Butterworths, London, 1972) and volume 1,

"Homogeneous gas phase reactions of the H2~N^-02 system" D. L. Baulch

D. D. Drysdale and D. G. Home, (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 (Advances in Environmental

Science and Technology, J. N. Pitts. Jr. and R. L. Metcalf, editors,

Wiley-Interscience, volume 4, 1974).

Kinetic data for reactions of the hydroperoxyl radical have been

evaluated in "Evaluated and Estimated Kinetic Data for Gas Phase Reactions

of the Hydroperoxyl Radical" A. C. Lloyd, Intern. J. Chem. Kinet. 6_. 169-228 (1974) .

Kinetic data for reactions of chlorine atoms and chlorine oxides

have been evaluated by R. T. Watson in "Chemical Kinetics Data Survey

VIII. Rate Constants of C10 x of Atmospheric Interest" NBSIR 74-516

(distributed by Chemical Kinetics Information Center, National Bureau

of Standard^, Washington. D. C. 20234.)
1.3. Guide to the Table

1.3.1. General

This table provides current (November 1974) information on reaction rate constants, quantum yields and absorption cross sections.

For many reactions, preferred values are given. The reactions included

in the table are summarized on a "reaction grid" described in section

1.3.4., Arrangement of the Table. 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 following remarks summarize the content of the table. It

lists 271 reactions and gives a preferred value of the rate constant

for 160 reactions, 136 based on recent reviews and 24 based on recent

(1972-1974) experimental work. New data entries (1972-1974) are given

for 121 reactions.

Several principles have been used in the selection and presentation

of data.

(a) Where a preferred value is given for a rate constant or photochemical quantity, it is so indicated by an asterisk

placed ahead of the reference column.

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

and tbere are no newer data, the evaluation is adopted and

usually, but not always, marked with an asterisk. The

original data covered by the evaluation are not listed

separately .

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

are listed and a preferred value is indicated (marked by

an asterisk)

.

(d) Where desirable, the available recent data sets are listed,

and a selection is made or a preferred value is synthesized

from them.

(e) The uncertainty in a preferred value given in the table is

the evaluator's estimate of that value's reliability. This

is a subjective judgment that, to a high degree of

probability, the true value of the quantity lies within the

bounds indicated.
Uncertainties are indicated in several ways:

A < k < B means k lies in the range between A and B.

k < B means B is an upper limit.

k ~ B means that Bis only a rough guide to the value of k.

k = A ± B means that a reasonably reliable estimate of the

likely error can be stated. This is an estimate by the

evaluator of the absolute accuracy of the preferred value.

It is a subjective judgment derived from intercomparison

of data sets, consideration of related reactions studied

with the same technique, estimates of how well the parameters

could have been controlled, and comparison with theory. It means that in the evaluators judgment, the true value will

lie within the indicated limits to a high level of confidence

(90 to 95 percent)

.

Sometimes it is more appropriate to give logiQk = C ± D,

"k uncertain to E percent" or "k uncertain to a factor of F",

all three of which are equivalent statements of multiplicative

limits . The statement that k has the value k^ and is uncertain

to a factor of F means k /F < k < kF.

The identity of the contributor who selected a particular preferred

value has been retained wherever possible. This is shown by initials

after the appropriate entry in the Reaction/Reference column. The

editors take responsibility for any unidentified selections and for

inadvertant ommission of identification of selectors.

1.3.2. Conventions Concerning Rate Constants

a. General Convention . Almost all of the reactions in the

table 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[AB

2 J/dt = k[A][B] 2

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] ) and 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.,

N0

2 + N0„ (+M) -> NO (+M)

M

HNO -» HO + N0„

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

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

2

l [NO3] and k[HN03

] respectively. The units

given for the k's. s _J- 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

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

atmosphere, 1962.

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 -t 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 table contains 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 = krKeq

" or k r = kf/Keq

These expressions, which are those used in the analyses, are based

on equating the two rates at equilibrium.

f r

k

f [A] = kr [B]

K = [B]/[A] = k

f /k

r

.

1.3.3. Convention Concerning Optical Absorption Coefficients

These are reported in the table as "absorption cross sections

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

I/I Q = exp(-cr[N]J&)

a = (l/([N]A))ln (I

o /I)

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

0" is the absorption cross section, cm^ molecule" , [N] is the

concentration of absorbers, molecules cm, and i 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)" 1 cm"

1

, base e, multiply by 2.69 x 10 19 .

1.3.4. Arrangement of the Tables

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 reactants means that data for the reaction are in the

table- Combination reactions, A + B + M-*AB+M are above the main

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

the diagonal

.
The first four columns in the reaction grid indicate whether the

table contains the following data for a particular species listed along

the left edge of the grid: 1. (ABS . J) , ultraviolet or visible

photoabsorption cross section; 2. (Q.Y.), quantum yields for primaryphotochemical processes; 3. (E.TR.), rate coefficients for processes

involving energy transfer from excited species; and 4. (DISS.) rate

data for its thermal dissociation.

b. Sequence of Reactions . The order in which reactions are listed follows the grid. All reactions of atoms, the first species,

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

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

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

left) on the grid, Bimolecuiar and combination reactions with the same reactants appear together in the table.

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:

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

numbers at the left side of the grid

(2) Arrange this set of numbers in ascending order, e.g. 1, 3 not 3, 1; 4, 10, 11 not 10, 11, 4.

(3) 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 reference 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.
2.m Chemical Reaction Matrix

K = Data in table, = 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

CO >• t cq » < Or i a o o o o o (^

cm m o O <N m

n ooo<N<-sir*xxx < oozzzzzzzzzzx;

o o o o o

: x x x u.o u cj x x

CJ U cm <N o o -* o 1 zz u ucm o cm en c> m ( O X x x x x : O O U U U U i

' U U U U O

1

2

3

5

6

78

91011

1213

1415

16

1718

19

20

2122

232425

26

2728

29

30

31

3233

3435

36

3738

39

» 40

41

42

43

4445

46

4748

49

50

51

52

53

54

5556

57

5859

60

61

0(1D)

0(1S)

0202(1A)EK - 02 (IS) 03

NO

N02

K

E K

K K K K K

K K K K

K K

K K K

K K

K K K

K K N03

N2N20

N205 NH

K K K K K K

K K K - K

NH2

NH3

HO

HO 2

K - K K K -

- - K K

K

K

K - - K K K

K K K

- K K K

H2H20

H202 HNO

HN02

K K - K K K K K

K K K

K K -

K

K -

HN03

SO

S02 S03 S20

K

K - K - K

HSH2S HS03

H2S04

CICIO

C102

C103

HC1 H0C1

K

K K

H0C10

N0C1 N02C1

C12

CO

CO 2 CH0

CH20

CH3 CH30

- K K - K - K K K K

CH302 CH30H

CH300H

CH3N02

CH3N03

K

CH4 C2H4 C2H6

C3H6

C3H8

K - K K K K

K JUS.

November 22, 1974 Bimolecular Reactions: A + B--C + D +

* and C120

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71
4. Rate constant for the reaction HO + N0

? (+ N ) -» HNO„ (+ N )

as a function of temperature and total gas concentration.

W. Tsang

National Bureau of Standards

May, 1974

Rate constants for this reaction are provided here in tabular

form covering the temperature range 190-350 K and the total

concentration range 10 - 3 x 10 molecule cm . They are

recommended for use in modelling of the atmosphere.

These numbers were obtained using the correlation developed

by W. Tsang, Int. J. Chem. Kinetics _5, 947, (1973), and also presented

in R. F. Hampson, editor, "Chemical Kinetics Data Survey. VI",

NBSIR 73-207 (Aug. 1973). The calculations have been made with the

same parameters as used for the graphs and tables presented earlier.

This correlation is rated as good to a factor of 2 in k on an

absolute scale throughout the range tabulated. It is, however, fitted

to the room temperature data and is presumably better in this region

than the rating stated above. Relative values throughout the table

may be good to 25% in k. Thus the second decimal place in log k

should be considered a guard digit. Linear interpolation should be

used

.

The correlation passes through the low pressure data of Anderson,

Margitan, and Kaufman, J. Chem. Phys. 60, 3310-3317 (1974) but has a

smaller pressure dependence than they found.

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i-i CJ 1 4-1 c CM

CO o CTi

i—l

a . 3 CM s cu i—l fj J= 1 o 4J II CW

IW

—

S-i o r*

CO

i—l 00 00 3 o o o r-l 1—1

cu

1—1 CU . o rC 00 £

4-1 • a)

Q) 4-1

4-1 CJ •s, CO fi

CU

Ug

rC 4-1 3

4-> rQ t—

3 o

S-l cn CJ o

14-1 •\ CO

i—l 4-1

— 1 •r4

rVS cn CM c

oo i •H o CU

I—l i—

S-l 3 0) c o hQ

1-1 cu

R

CO I—l 3

4-1 o C

rO

R o rC vO CJ O R cO H a a)

73
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Kinetics Data for the Lower and Upper Atmosphere, Airlie House, Warrenton

Virginia, September 1974. Proceedings to be published Intern. J. Chem. Kinet.

Huie, R. E., and Rerron, J. T., "The Rate Constant for the Reaction 3

+ N02 ->

2 + N03 Over the Temperature Range 259-362° K," Chem. Phys. Lett. 27.

. 411-414 (1974a)

Huie, R. E., Herron, J. T., and Davis, D. D., "Absolute Rate Constants for

the Reaction +

2 + m -> 3 + M Over the Temperature Range 20C-346°K

»"

J. Phys. Chem. 76, 2653-2658 (1972)

Husain, D., Kirsch, L. J., and Donovan, R. J., "A Kinetic Study of 0(23P,)

by Atomic Absorption Spectroscopy Following the Flash Photolysis of

Ozone," J. Photochem. I, 69-73 (1972)

Jacob, A., and Winkler, C. A., "Kinetics of the Reactions of Oxygen Atoms

and Nitrogen Atoms with Sulphur Trioxide," J. Chem. Soc. Faraday

Trans. I 63, 2077-2082 (1972)

James, F. C., Kerr, J. A., and Simons, J. P., "a Direct Measurement p,f

the Rate of Reaction of the Methyl Radical with Sulphur Dioxide, J. Chem.

Soc. Faraday Trans. I 69, 2124-2129 (1973)

Johnston, H. S., "Gas Phase Reaction Rate Theory," The Ronald Press Co.,

New York (1966), Chapter 1

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NBS-NSRDS-20 , 1968. (Supt. of Documents, U.S. Govt. Printing Office,

Washington, D.C. 20402)

Johnston, H. S., "Catalytic Reduction of Stratospheric Ozone by Nitrogen

Oxides, Adv. Environ. Sci. and Technology 4. 263-380 (1974), J. N. Pitts. Jr.,

and R. L. Metcalf, editors, Wiley-Inter science

Johnston, H. S., private communication (1973)

Johnston, H. S., Chang, S.-G., and Whitten, G., "Photolysis of Nitric Acid

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Johnston, H. S., and Graham, R., "Gas Phase Ultraviolet Absorption Spectrum

of Nitric Acid Vapor," J. Phys. Chem. 77, 62-63 (1973)

Johnston, K. S., Morris, ii. D., Jr., and Van den Bogaerde, J., "molecular

Modulation Kinetic Spectrometry. ClOO and C10

2 Kadicals in tne Photolysis of

Chlorine in Oxygen," J. Amer. Chem. Soc. 9J., 7712-7727 (1969)

Jones, I. T. N., and Bayes, K. D., "Photolysis of Nitrogen Dioxide, J. Chem.

Phys. 59. 4836-4344 (1973)

83
Jones, E. J., and Wulf, 0. R., Absorption Coefficient of Nitrogen Pentoxide

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Phys. £, 875-877 (1937) •

Kaufman, F. , Aeronomict< Reactions Involving Hydrogen. A Review of Recent

Laboratory Studies," Ann. Geophys. 2&, 106-114 (1964=)

Kerr, J. A., and Parsonage, M. J., "Evaluated Kinetic Data on G-as Phase

Addition Reactions: Reactions of Atoms and Radicals with Alkenes,

Alkynes and Aromatic Compounds," (Butterworths, 1972)

Klemm, R. B., Payne, W. A., and Stief, L. J., "Absolute Rate Parameters for the

Reaction of Atomic Hydrogen with HoO?," Presented at Symposium on Chemical

Kinetics Data for the Lower and Upper Atmosphere, Airlie House, Warrenton

Virginia, September 1974. Proceedings to be published Intern. J. Chem. Kinet.

Kondratiev, V. N.

fc "Kons^tanty Skorosti Gazofaznykh Reaktgij Spravochnik,

(Izdatelstvo Nauka , Moskva, lgTOj^also issued as Rate Constants of

Gas Phase Reactions, Reference Book," R. M. Fristrom, Ed., Translated

by L. J. Holtschlag C0M-72-1Q014, Office of Standard Reference Data, NBS

(1972) (Distributed by National Technical Information Service, Springfield, Va. 22151)

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Study of the Kinetics of the Reactions of D Atoms and Atoms with NH,

# " J. Chem. Phys. 5J, 4497-4501 (1969)

Kurylo, M. J., "Absolute Rate Constants for the Reaction H + + M ->

H0

2 + m Over the Temperature Range 203-404 K," J. Phys. Chem. 76, 3518-

3526 (1972)

Kurylo, M. J., "Kinetics of the Reactions 0H(v = 0) + NH

3 -> h2o + NH?

and OH(v = 0) + _> HOo + Oo at 298°K." Chem. Phys. Letts. 23, 467-

471 (1973) * ' d

Kurylo, M. J., Braun, W., Kaldor, A., Freund, S. M., and Wayne, R. P.,

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H H

2

s # " j. chem. Phys. 54, 943-^46 (1971)

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4»

Lloyd, A. C, "Evaluated and Estimated Kinetic Data for Gas Phase Reactions

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3P)

Atoms, Free Fro.ii Excited Molecules, and Their Reaction with 3

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Combust. 12th (Combustion Institute, Pittsburgh, 1969) 307-311

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85
Morris, S. D., Jr., and Niki, H., Reaction of Methyl Radicals with Atomic

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3570-3572 (1971)

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June 1974

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Payne, W. A., Stief, L. J., and Davis, D. D. , "a Kinetics Study of the Reaction

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" Chem Phys. Lett 29

31-34 (1974) d * ' * ~'

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86
Rawlins, W. T., and Gardiner, W. C, Jr., "Rate Constant of OH + OH = I^q + o from 1500 to 2000 K," J. Chem. Phys. 50, 4676-4631 (1974)

Ridley, B, A., Davenport, J. A., Stief, L. J., and Welge, K. H., "Absolute

Rate Constant for the Reaction H + H

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J. Chem. Kinet. 4, 255-263 (1972)

c 6

Schofield, K., "Evaluated Chemical Kinetic Rate Constants for Various Gas

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Simonaitis, R., and Heicklen, J., The Reactions of HOp w ith Carbon Monoxide

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1096-1102 (1973a)

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309-314 (1973c)

Simonaitis, R. , and Heicklen, J., "The Reaction of HO

? w ith NO and NO?

" J. Phys. Chem. 78, 653-657 (1974)

Simonaitis, R., and Heicklen, J., "Reactions of CH-o? with NO and NO-

"

J. Phys. Chem. 78, 2417-2421 (1974)

Slagle, I. R., Pruss, F. J., Jr., and Gutman, D., "Kinetics into the Steady

n State. I. Study of the Reaction of Oxygen Atoms with Methyl Radicals,"

Intern. J. Chem. ivinet. 6, 111-123 (1974)

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

Resonance Fluorescence. I. 0( 3P) + Q + m -> 0„ + M and 0( 3P) + NO + M ->

N0

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

Slanger, T. G., Wood, B. J., and 21ack, G., "investigation of the Rate Coefficient

for 0(3p) + NO

g -> o

2 + NO," Intern. J. Chem. Kinet. 5. 615-620 (1973)

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

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Resonance Absorption Part 2. Reactions of OH with Co, C h . and C H_

'

J. Chem. Soc e Faraday Trans. II 69, 1617-1627 (1973)

4 d

Smith, I, W. M a , and Zellner, R., "Rate Measurements of Reactions of OH

by Resonance Absorption, Part 3. Reactions of OH with H_ £u hydrogen

and Deuterium Halides," J. Chem. Soc. Faraday Trans. II 70, 1045-1056 (1974a)

Smith, I. W, M., and Zellner, R. , "Rate Measurements of Reactions of OH by

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at Symposium on Chemical Kinetics Data for the Lower and Upper Atmosphere,

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Sperling, H. P., and Toby, S., "The Photochemical Decomposition of Caseous

Formaldehyde/' Can. J. Chem. 51, 471-475 (1973)

Stedman, D. H.„ and Niki, H«^ 'Kinetics and Mechanism for the Photolysis of

Nitrogen Dioxide in Air, J. Phys. Chem. 77, 2604-2609 (1973)

Stedman, D« H., Wu, C. K. , and Niki, H«, "Kinetics of Cas-Phase Reactions

of Ozone with Some Olefins," J. Phys. Chem. 77, 2511-2514 (1973)

Stuhl, F, s "Absolute Rate Constant for the Reaction OH + NH„ _> nh2 + H20,"

J. Chem. Phys. 5g, 535-537 (1973a)

Stuhl* Fe , Rate Constant for the Reaction of OH with n-C h n g a Naturforsch.

Pt A 28, 1383-1384 (1973b) 4 1U*

Stuhl, F. , Determination of Rate Constants for the Reactions of OH with

Propylene and Ethylene by a Pulsed Photolysis-Resonance Fluorescence

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Stuhl, F„, "Determination of the Rate Constant for the Reaction OH + H

2

s by a Pulsed Photolysis - Resonance Fluorescence Method, Ber. Bunsenges.

Physik. Chem 9 78, 230-232 (1974)

Stuhl, F. , and Niki, H., "Detection of Oxygen ( 3P) Atoms in Pulsed Vacuum

UV Photolysis of NO and Its Application to Atom Reactions,' Chem.

Phys. Lett. 2. 197-200 (1970)

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

Reactions of 0( 3P) with NO, 2f CO, N2

, and COg Using a Pulsed Vacuum-uv

Photo lysis-Che mi luminescent Method," J. Chem. Phys. 55, 3943-3953 (1971)

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

of OH with R^ j^ t and' CO Using a Resonance-Fluorescent Detection Method,"

J. Chem. Phys. 52, 3671-3677 (1972)
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Kinetics Data Survey VII, Tables of Rate and Photochemical Data for

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Thrush, B. A,, Letter to D, Garvin (Sept. 1973) reevaluating work in his

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Intern. J. Chem. Kinet. 6, 417-428 (1974)

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89
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H0

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3

and HNO^/' Chem. Phys. Lett. ?6, 72-74 (1974)

90
APPENDIX 1.

Chemical Thermodynamic Properties of Selected Molecular Species

E. S. Domalski, D. Garvin, and D. D. Wagman

Two tables are provided showing chemical thermodynamic properties

of selected molecular species of interest in stratospheric chemistry. In

these tables there are sufficient data for the usual calculations of heats

of reaction and equilibria.

The first table lists enthalpy and Gibbs energy of formation, entropy and

heat capacity data. The information was extracted from "Selected Values

of Chemical Thermodynamic Properties" (D. D. Wagman, et. al., NBS

Technical Note 270-3, January 1968) except as indicated in the Notes.

The thermodynamic properties tabulated are:

1. enthalpy of formation at OK and 298. 15K,

2. Gibbs energy of formation at 298. 15K,

3. enthalpy increment between OK and 298. 15K,

4. entropy at 298. 15K,

5. heat capacity at constant pressure at 298. 15K.

The values given for the heats of formation are based on experimental

thermodynamic and spectroscopic measurements except where otherwise indicated;

o the values of S , C and H° -Hn for the gaseous species were calculated

p ZyO U

by standard statistical-mechanical equations, using corrections for vibrational anharmonicities, rotational stretching, and rotation-vibration interactions where these data were available.

91
The second table presents bond dissociation energies or bond

strengths. These usually are the enthalpies of simple bond scission

reactions. However, there are some cases in which there is a

substantial contribution from rearrangement of electronic structure

in the products (reducing the bond energy).

The values given here for some molecules will differ slightly

from values adopted by the CODATA Task Group on Key Values for

Thermodynamics (see CODATA Bulletin 10, published by the International

Council of Scientific Unions Committee on Data for Science and

Technology, December 1973). These differences will have no

significant effect on the enthalpies or free energies of reaction

calculated from the tables.

92
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m 0O W 00 st o St i-t st CM m O 00 en m © en ON

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m <t <* 5 O co 3 m CM i^. st tH OS vo r^ l-l CM tH 00 00 © •* m m CM en en m m en t-i CM tH CM

i-i t-i i I-H fe>

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Notes

1. Hampson, R. F. et al, J. Phys. Chem. Ref . Data 2, 267-312 (1973)

[Data sheet on + hv (u.v.) p. 303.

2. Contributions of the higher electronic states of molecular oxygen

to the enthalpy, entropy, and heat capacity at 298 K are

insignificant.

3. Stull, D. R. and Prophet, H. "JANAF Thermochemical Tables" 2nd.

ed. NSRDS-NBS 37 (1971).

4. Tsang, W. Estimated from kinetic data on the decomposition of

N H, . Chapter 12, NBS Report 10904, 1 July 1972.

5. NB." Report 10904, l ju ly 1972, pp. 239-307.

6. R. A. Fletcher and G. Pilcher, Trans. Faraday Soc. 66_, 794-799

(1970) provide more recent data for £Hf°, 298.15 K.

7. Data obtained from Benson and O'Neal ("Kinetic Data on Gas

Phase Unimolecular Reactions", NSRDS-NBS -21, Feb. 1970, page 55).

8. We estimated the AHf °[CH~0

9 (g) ] by assuming that: (a) the breaking

of the 0-0 bond in CH 0„ was equivalent to the 0-0 bond scission

(37 kcal mol"'~) in CH OOCH and (b) the breaking of the 0-H bond

in CH H was equivalent to the 0-H bond scission (104 kcal mol )

in CH OH.

° o o 9. Values for AHf , S , and Cp at 298.15 K were calculated using

the group additivity method described by Benson and O'Neal

("Kinetic Data on Gas Phase Unimolecular Reactions", NSRDS-NBS -

21, Feb. 1970, ppg. 40-42).

99
o -1

10. The value for AHf [CH

3

0N0(g)] = -16.5 kcal mol " was derived

from the combustion data of Geiseler and Thierfelder (Z. physik,

Chem., N.'T., 29, 248-257 (1961)), and the equilibrium data of

Leermakers and Ramsperger (J. Am. Chem. Soc. 54, 1837-1845

(1932)) for: CH

3 0H(g) +-N0C^(g) = CH

3

0N0(g) +HCX(g).

11. The value for £Hf° (CH

3

0N0

2 (g)) = -29.8 kcal mol"' was derived

from the work of Ray and Ogg (J. Phys. Chem. 63, 1522-1523

(1959)) on the enthalpy of reaction of N^ with CHgONO.

12. We have chosen S° [CH

3

ON(>

2 (g)] = 76.1 cal mol" K~ based upon

low temperature thermal data of Gray and Smith (J. Chem. Soc.

1953 2380-2385). Calculations from microwave studies by

Dixon and Wilson (J. Chem. Phys. 35, 191-198 (1961)) give S° =

-1 -1

72.15 cal mol K .

13. Davies, J. V., and Pritchard, H. 0., J. Chem. Thermodynamics

o 4, 23-29 (1972) provide more recent AHf data.

14. Data on AHf , S°, C

p obtained from S. W. Benson and H. E.

O'Neal ("Kinetic Data on Gas Phase Unimolecular Reactions",

NSRDS-NBS-21, Feb. 1970, page 567).

15. Rossini, F. D., Pitzer, K. S., Arnett, R. L., Braun, R. M.

and Pimentel, G. C, "Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and Related Compounds",

API Research Project 44, Carnegie Press, Pittsburgh, 1953.

100
16. £Rf° data from Pittam and Pilcher (J. Chem. Soc, Faraday

Trans. I, 68, 2224-2229 (1972).

17. AHf° data from R. L. Nut tall, A. H. Laufer and M. V. Kilday.,

J. Chem. Thermodynamics 3, 167-174 (1971).

18. Devore, J. A., and O'Neal, H. E., J. Phys. Chem. 73_, 2644-

2648 (1969).

19. Data on S° and C were obtained from Note (14), page 589;

data on ZXHf° came from Note (18).

20. Spectroscopic studies of N. Basco and R. D. Morse, J. Molec.

Spectros. 4_5, 35 (1973); R. A. Durie and D. A. Ramsay, Can.

J. Phys. 36, 35 (1958); P. A. G. O'Hare and A. C. Wahl, J.

Chem. Phys. 54, 3770 (1971); L. Andrews and J. I. Raymond,

J. Chem. Phys. 55, 3087 (1971); D. R. Johnson and F. X. Powell,

Bull. Am. Phys. Soc. 13, 594 (1968); A. Carrington, P. N. Dyer,

and D. H. Levy, J. Chem. Phys. 47 , 1756 (1967) were examined

and used to calculate the thermodynamic properties.

21. Arkell, A., and Schwager, I., J. Am. Chem. Soc. 89, 5999

(1967); Johnston, H., Morris, E. D., and Vanden Bogaerde, J.,

J. Am. Chem. Soc. 91, 7712 (1969), Clyne, M. A. A. and White,

I. F., Trans. Faraday Soc. 67, 2068 (1971).

22. Studies by D. J. Gardiner, J. Mol. Spectroscopy 38, 476 (1971)

and G. E. Herberich, R. H. Jackson, and D. J. Miller, J. Chem.

Soc. (A) 1966 , 336 were examined and the data used to calculate

the thecmodynamic properties.

101
23. The spectroscopic data of K. 0. Christe, C. J. Schack and

E. C. Curtis, Inorg. Chem. 10, 1589 (1971) were used.

24. Thermal Constants of Substances (Termichesky Konstanty

Veshchestv), Vol. IV, V. P. Glushko, Editor, Moscow (1970).

25. The combustion data of A. T. Hu and G. C. Sinke, J. Chem.

Thermodynamics 1_, 507-513 (1969) were used to derive ^Hf°

298.15 K values for CC1,, CHCl and CH

2

C1 in the liquid state

26. The vaporization data of D. L. Hildenbrand and R. A. McDonald,

J. Phys. Chem. 63_, 1521-1522 (1959) were used.

27. The combustion data of R. A. Fletcher and G. Pilcher, Trans.

Faraday Soc. 67, 3191-3201 (1971) were used to calculate

AHf° [CH

3

Cl(g)].

28. J. Chao, A. S. Rodgers, R. C. Wilhoit, and B. J. Zwolinski,

J. Phys. & Chem. Ref. Data 3, 141-162 (1974) provide a recent

evaluation of the thermodynamic properties of CH„CC1„

.

10^
o Bond Dissociation Energies, D at K •

Reaction kj/mol kcal/mol Note (1)

1L7.97±0.1

24.24±0.5 (2)

103.25±0.01

101.3±0.5

63.2±1

46±3

118.0±0.2

49.5±0o5

88.5±2.0

225o07±0o01

150.1 (2)

71.83 (2)

49±5 (2) N-0

2 - 20 493.59±0.4

o - o

2 + 101.4±2.1

H

2

-» 2H 432.00±0.04

HO - H + 423.8±2.1

HO - HO + 264.4±4 - H +

2 192+13

H

2 - HO + H 493.7±0.8

H

2 2 - 2H0 207.1±2.1

H

2 2 - H'+ H0

2 370o3±8 o 4

N - N + N 941.69±0.04

NO -* N + 627.9

N0„ - NO + 300.5

NO - N0

2 + 205±21

NO - N + NO 474o9±4 - N

2 + 161.3

HNO - H + NO 203 - NH + 475

trans-HN0

2 -

HO + NO 209.

(

113. 5±1

38.58 (2)

NO - NO + NO 35.1±0.8 8.4±0.2 N-0

N o0. - NO„ + N0 o 53.2 12.7 (2)N-N

2 4 2. I N„0 C - N0 o + NO. 89.5 21.4 (2) N-0

2 5 2 j

48,6 (2)

113.5

49.07 (2) N-0

HNO - HO + NO 200 47.8 (2) N-0

NH - H + N 356±8 85±2

NH - H + HN 360 86 (2,3)

103
Bond Dissociation Energies, D at K

o

Reaction kJ/mo 1 kcal/mol Note (1)

NH -» NH. + H 453 108 (2,3)

CO -» C + 1071.94 + 0.4 256.2 ± 0.,1

CO -» CO + 525.9 + 0.,4 125.7 ± 0,,1

CHO -» CH + 859 205 (2)

-» CO +H 119.7 28.6

CH -» CHO + H 314 75

CH -» CH

3 + 378 90.4 (2,3)

-» H + H C = 88.2 21.1 (2,3)

CH3°2 ~* ^S + 173. 41.5 (2,3)

HCH3+ C*2 53.6 12.8 (2,3)

CH

3

-» CH

2 + H 469.9 + 0.,4 112.3 ± 0,,1

CH. - CH„ + H

4 3 425.1 + 8,.4 101.6 ± 2.,0

CH OOH -> CH + HO 184. 44.0 (2,3)

-» CH

3 + H02 295. 70.6 (2,3)

CH ONO -» CH

3 + N02 248 59.2 (2,3)

CH

3 N02

-* CH

3 + N02 254 60.6 (2,3)

CH

3 ON02

-» CHO + N0

2 174 41.6 (2,3)

-» CH + N0

3 341 81.6 (2,3)

SO -» S + 517.1 + 8 123.6 + 2

so

2

-> SO + 547.3 + 8 130.8 ± 2,,0

S0„ -» S0 o + 342.7 + 4 81.9 i L

Notes

1. Unless another source is indicated , the values are those recommended by

Darwent, B. deB., "Bond Dissociation Energies in Simple Molecules," Natl.

Stand. Ref. Data Series - Natl. Bur. Standards 31 (January 1970).

2. Calculated from heats of formation in the accompanying table "Chemical

Thermodynamic Properties of Selected Molecular Species". Sources of data

are indicated in notes to that table.

3. Calculated for 298 K, values at OK not being available.

104
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112
Announcement of New Publications on

Chemical Kinetics Data

Director, Chemical Kinetics Information Center

Chemistry Building A158

National Bureau of Standards

Washington, DC 20234

Dear Sir:

Please add my name to the announcement list for new publications on chemical kinetics and photochemical data

from the Chemical Kinetics Information Center.

Name

Institution

Address

City State Zip code

(NBS TN 866)

113
U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

1. I'l'HI.K A 1 ION OH Kl POR 1 NO. NBS TN-866

2. dov't Accession

No.

4. II I !.!: ANI1 SUBTITLE

Chemical Kinetic and Photochemical Data for

Modelling Atmospheric Chemistry

3. Recipient's Accession N<

5. Publ icat ion Date June 1975

6. Performing Organization ( o<

7. author(S)

R. F. Hampson, Jr. , and David Garvin; Editors

8. Performing Organ. Report No.

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NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

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3165409

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Department of Transportation

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( Covered Final

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15. SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number : 75-600025

16. ABSTRACT (A 200-word or less (actual summary ol most significant information. If document includes a significant

bibliography or literature survey, mention it here.)

A table of data for gas phase chemical reactions and photochemistry of

neutral species is presented. Specifically, it gives preferred values for

reaction rate constants, photoabsorption cross sections, and quantum yields

of primary photochemical processes and also cites recent experimental work.

It is intended to provide the basic physical chemical data needed as input

data for calculations modelling atmospheric chemistry. An auxiliary table

of thermochemical data for the pertinent chemical species is given in the

append ix.

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;

gas phase; photoabsorption cross section; photochemistry; quantum yield;

rate constant

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The following current-awareness and literature-survey tonographies are issued periodically by the Bureau: (Oogenic Data Center Current Awareness Service A literature survey issued biweekly. Annual subscription: Domestic, $20.00; foreign, $25.00. Liquefied Natural Gas. A literature survey issued quarterly. Annual subscription: $20.00. Superconducting Devices and Materials. A literature

survey issued quarterly. Annual subscription: $20.00. Send subscription orders and remittances for the pre- ceding bibliographic services to National Technical Information Service, Springfield, Va. 22161.

Electromagnetic Metrology Current Awareness Service

Issued monthly. Annual subscription: $100.00 (Special rates for multi-subscriptions). Send subscription order and remittance to Electromagnetics Division, National Bureau of Standards, Boulder, Colo. 80302.
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