Chemical Kinetic and Photochemical Data for Modelling Atmospheric

T ° F ^ <**

1. • z CO NBS TECHNICAL NOTE 866 \ * 'VaT of

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

established by an act of Congress March 3, 1901. The National Bureau of Standards' was advance the Nation's science and technology The Bureau's overall goal is to strengthen and for public benefit. To this end, the Bureau conducts and facilitate their effective application Nation's physical measurement system, scientific research and provides: (1) a basis for the (2) technical basis for equity in trade, and technological services for industry and government, (3) a public safety. The Bureau consists of the Institute for and (4) technical services to promote Research, the Institute for Applied Technology, Basic Standards, the Institute for Materials Technology, and the Office for Information Programs. the Institute for Computer Sciences and THE INSTITUTE FOR BASIC STANDARDS provides the central basis within the United physical measurement; coordinates that system States of a complete and consistent system of with measurement systems of other nations; and furnishes essential services leading to accurate and uniform physical measurements throughout the Nation's scientific community, industry, and commerce. The Institute consists of a Center for Radiation Research, an Office of Meas- urement Services and the following divisions: Applied Mathematics — Electricity — Mechanics — Heat — Optical Physics — Nuclear 1 3 Sciences" Applied Radiation " — Quantum Electronics — Electromagnetics — Time and Frequency " — Laboratory Astrophysics " — Cryogenics ".

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1 Headquarters and Laboratories at Gaithersburg, Maryland, unless otherwise noted; mailing address Washington, D.C. 20234. 8 Part of the Center for Radiation Research. > Located at Boulder, Colorado 80302. » Part nf thp Center for RtiilHino Tprhnr.lr.ov "* STAKTDABD3 LIBRARY

2 8 JUL Chem.cal Kinetic and

Photochemical Data for C 100 1515_ Modelling Atmospheric Chemistry

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 uni- versities, 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 (+ N ) -» HN0 (+ N ) as a function of 2 2 3 2 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 the -0 reactions of H 2 ? 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

2 -d[A]/dt = -(1/2) d[B]/dt = d[AB 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 + N0„ (+M) -> NO (+M) 2

M HNO -» HO + N0„

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

them, e.g., Rate = k[N0 [NO3] and k[HN0 ] respectively. The units 2 l 3 _J given for the k's. s - for first order, and cm" molecule s for second order, are consistent with this convention.

The altitude, temperature and number density regime used in these cases is

-3

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

15 220 18.60 20 217 18.27 25 222 17.93 30 227 17.58 35 235 17.26 40 250 16.92 45 260 16.60

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 k rKeq 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 [A] = k [B] f r

K = [B]/[A] = k /k . f 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 = exp(-cr[N]J&) Q

a = (l/([N]A))ln (I /I) o where I and I are the intensities of incident and transmitted light, 0" is the absorption molecule" [N] is the cross section, cm^ , 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 1 1 19 273 K)" cm" , base e, multiply by 2.69 x 10 .

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 inter- section 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 primary- photochemical 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 inter- section 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 else- where in the chapter, (Blank) = Role of process not assessed

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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.~~~~~~

~~~~~~72 1\ 1 I1 '', 1 1 11 —1 i '> i I~~~~~~

~~~~~~e o o • u vO M-l i—l~~~~~~

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~~~~~~I 1 4-1 1 1 1 i i i i Tl~~~~~~

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1 CT> i—i 4-> t— cu CD — in vO 00 o O o CM rQ 4J S-i cn 3 o vO CM CM CM CM CM cn cn cn cn on S-l cn CJ cO cfl o i—i i—i r-l i—l i—l i—l i—i i—i i—i i-H i—i o S-i . S3 i i 14-1 CO rC i 1 1 i i •\ CO i—l 4-1 c o — o G T3 1 •r4 iH rVS cn 4J -o CM c vO i—i i O cu CM vO 00 00 CM oo •H I—l CM CO U o CT> O cn in m vO o CU I—l i— S-l 01 cc! ctf i—i vO CM cn cn cn cn cn cn cn on cn 3 0) 3 i— r-l r-l i—i i—i i—i i—i i—i r—i i—i i—i c o hQ i 1-1 rO 1 1 i i cu R nj CO I—l 3 4-1 4-1 o C rO R cu o rC rC o o o o o o o o o o vO CJ ON H on r-l cn m o r-i on m O R cO CM CM CM CM CM cn m on on H a a)

~~~~~~73 5. Reference List~~~~~~

~~~~~~Ahumada, J, J. f Michael, J. V., and Osborne, D. T., "Pressure Dependence and Third Body Effects on The Rate Constants for H + H +"n0, and H + CO," J. Chen. Phys. 57, 3736-3745 (1972)~~~~~~

~~~~Albers, E. A,, Hoyermann, K., Warner, H. Gg., and Wolf rum J., "study of the Reaction of~~ ~~Ammonia with Oxygen Atoms," Symp. Combust, 12th (Combustion Institute, Pittsburgh, 1969) 313-321~~~~

Albers, E. A., Hoyermann, K. 9 Wagner, H. Gg«, and Wolfrum J., "Absolute Measurements of Rate Coefficients for the Reactions of H ana Atoms with 0," Symp. Combust. 13th (Combustion Institute, ^02 and H2 Pittsburgh, 1970) 81-88

Allen, E. R. , and Moortgat, G. K., "Kinetic Studies of the Termolecular Reactions of Hydrogen Atoms with Nitric Oxide and with Molecular Oxygen," Third Intern. Symp. Gas Kinetics, Brussels (1973), Abstract Dl

~~~~~~Anderson, J. G., and Kaufman, F., "Kinetics of the Reaction 0H(v = 0) + 0„ -> H0 + o ," Chem. Phys. Lett. 19.. 483-486 (1973) 2 2~~~~~~

~~~~~~Anderson, J. G., Margitan, J. J., and Kaufman, F., "Gas Phase Recombination of OH with NO and N0 " 3310-3317 2f j. Chem. Phys. £0, (1974)~~~~~~

~~~~~~Arin, L. M., and Warneck, P., "Reaction of Ozone with Carbon Monoxide," J. Phys. Chem. 76, 1514-1515 (1972)~~~~~~

~~~~~~Arnoldi, D., and Wolfrum, J., "The Reaction of Vibrationally Excited HC1 with t Oxygen and Hydrogen Atoms," Chem. Phys. Lett. 24, 2.34-2.38 <( 1974)~~~~~~

~~~~~~Atkinson, R., and Cvetanovic, R. J., "Determination of the Ra^es of Hydrogen Atom Reaction with NO by a Modulation Technique, Can. J. Chem. 51, 370-372 (1973)~~~~~~

~~~~~~Atkinson, R., and Pitts, J. N., Jr., "Temperature Dependence of the Reaction~~~~~~

~~~~~~Rate Constants for 0( 3P) Atoms with ^ = 2^» c3% a™1 N°( M ^0), Determined by a Modulation Technique," Chem. Phys. Lett. 27, 467-470 (1974)~~~~~~

Balakhnin, V. P., Egorov, V. I., and Intezarova, E. I., "Kinetics Investigation of the Elemental Reactions of Oxygen Atoms in the Gas Phase by EPR. II. The Reaction + HC1 = OH + CI,' Kinetics and Catalysis 12, 258 (1971); tr. of: Kinetika i Kataliz 12, 299 (1971)

~~~~~~R., W., Atoms Baldwin, R. Gethin, M A., and Walker, R. "Reaction of Hydrogen with Nitrous Oxide," J. Chem. Soc. Faraday Trans. I 69, 352-358 (1973)~~~~~~

~~~~Baldwin, R. R., Fuller, A. R. , Long thorn, D., ana Walker, R. W., "Addition of Formaldehyde to Slowly Reacting Hydrogen + Oxygen Mixtures, J. Chem. Soc. Faraday Trans. I 63, 1362-1367 (1972)~~~~

~~~~~~74 , W., S. J., CarDoti Baldwin, R. R. Walker, R. and Webster, w The Monoxide- Sensitized Decomposition of Hydrogen Peroxide," Combust, Flame 15 . 167-172 (1970)~~~~~~

~~~~~~Ball, M, J,, and Larkin, G. S., "Determination of the Rates of Atomic Re- actions by the Discharge-Flow Method," Nature Phys. Sci. 245> 63-64: (1973)~~~~~~

Basco, N., James, D. G. L., and James, F. C, "A Quantitative Study of Alkyl Radical Reactions by Kinetic Spectroscopy. II. Combination of the Methyl Radical with the Oxygen Molecule," Intern. J. Chem. Kinet. 4, 129-149 (1972)

Basco, N., James, D. G. L., and Suart, R. D. , "a Quantitative Study of Alkyl Radical Reactions by Kinetic Spectroscopy. Part I. Mutual Combination of Methyl Radicals and Combination of Methyl Radicals with Nitric Oxide," Intern. J. Chem. Kinet. 2, 215-234 (1970)

~~~~~~Bass, A. M., and Laufer, A. H. , "The Methyl Radical Combination Rate Constant as Determined by Kinetic Spectroscopy, Intern. J. Chem. Kinet. 5, 1053- 1065 (1973)~~~~~~

Batt, L., McCulloch, R. D., and Milne, R. T., "Thermochemical and Kinetic Studies - of Alkyl Nitrites (RONO) m D(RO-NO), The Reactions between RO and NO, and the Decomposition of RO, 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.

~~~~~~Baulch, D. L. , and Drysdale, D. D., "An Evaluation of the Rate Data for the Reaction CO + OH -> C0 " Combust. Flame £3. 215-225 (1974) 2 + h,~~~~~~

Baulch, D. L., Drysdale, D. D., Home, D. G., and Lloyd, A. C, "Evaluated Kinetic Data for High Temperature Reactions, Vol. 1: Homogeneous Gas Phase Reactions of the ^-(^ System," (Butterworths, London, 1972)

~~~~~~Baulch, D. L., Drysdale, D. D. # and Rome, D. G., [unpublished data sheets prepared for this survey] University of Leeds, 1973~~~~~~

Baulch, D. L», Drysdale, D. D., and Home, D. G., "Rate Constants for Re- actions of the \-\-O2 System," in Chemical Kinetics Data Survey V. Sixty-six Contributed Rate and Photochemical Data Evaluations on Ninety-four Reactions, NBSIR 73-206, D. Garvin, Ed., National Bureau of Standards, Washington, D. C. (1973) pages 49-115

~~~~~~Bayes, K. D., letter to RFH, March 11, 1974~~~~~~

~~~~~~Becker, K. H., Groth, W., and Schurath, U., "Reactions of 1A c? ( ) w ith Ozone," Chem. Phys. Letts. 14, 489-492 (1972) g~~~~~~

~~~~~~75 Becker, K. H., Groth, W., and Thran, D., "Mechanism of the Air Afterglow NO + -> N0 " 2 + hv> S ymp. combust. 14th (Combustion Institute, Pitts- burgh, 1973) 353-363~~~~~~

Becker, K. H., Inocencio, M., and Schurath, U., "The Reaction of Ozone with Hydrogen Sulfide and its Organic Derivatives," Presented at Symposium on Chemical Kinetics Data for tne Lower and Upper Atmosphere, Airlie House, Warrenton Virginia, September 1974. Proceedings to be published Intern. J. Chera. Kinet.

~~~~~~Becker, K. H., Schurath, U., and Seitz, H., "Ozone-Olefin Reactions in the Gas Phase. 1. Rate Constants and Activation Energies," Intern. J, Chem. Kinet. 5, 725-739 (1974)~~~~~~

~~~~~~Bedford, G., Mand Thomas, J. H., "Reaction between Ammonia-and Nitrogen Dioxide, J. Chera. Soc. Faraday Trans. I £3, 2163-2170 (1972)~~~~~~

~~~~~~Beraand, P. P., Clyne, M. A. A., and Watson, R. T., "Atomic Resonance Fluorescence and Mass Spectrometry for Measurements of the Rate~~~~~~

~~~~~~Constants for Elementary Reactions: 0(3p \ + + jjo? -> NO ? and NO + _> Chem. Soc. Faraday Trans. II 70. 564-576 (1974) 3 N 2 + Op," J.~~~~~~

~~~~~~"Benson, S. W. H. E. , Gas A and O'Neal, "Kinetic Data on Phase Unimolecular Reactions, NBS-NSRDS-21 (1970). (Supt. Doc, U.S. Govt. Printing Office, Washington, D.C. 20402)~~~~~~

~~~~~~Bevan, P. L., and Johnson, G. R. A., "Kinetics of Ozone Formation in the Pulse Radiolysis of Oxygen Gas," J. Chem. Soc. Faraday Trans. I 69, 216-227 (1973)~~~~~~

~~~~~~Biaurae, F. , "Nitric Acid Vapour Absorption Cross-Section Spectrum ana Its Photodissociation in the Stratosphere," J. Photochera. 2, 139-149 (1973)~~~~~~

Bishop, W. P., and Dorfraan, L. M., "Pulse Radiolysis Studies. XVI. Kinetics of the Reaction of Gaseous Hydrogen Atoms with Molecular Oxygen by Fast Lyman-a Absorption Spectrophotometry," J. Chem. Phys. 52, 3210-3216 (1970)

Bradley, J. N., Hack, W., Hoyerraann, K., and Wagner, H. Gg., "Kinetics of the Reaction of Hydroxyl Radicals with Ethylene and with C, fydro carbons,' J. Chem. Soc. Faraday Trans. I 69, 1889-1898 (1973)

~~~~~~Breckenridge, W. H., and Miller, T. A., "Kinetic Study by EPR of the Production~~~~~~

~~~~~~and Decay of SO(!a) in the Reaction of (!a w j.th SO(^~)," J. Chem. ? g ) phys. 56, 465-474 (1972)~~~~~~

~~~~~~Brown, R. D. H., and Smith, I. W. M., "Absolute Rate Constants for the Reactions~~~~~~

~~~~~~of 0(^P) Atoms with HCl and HBr," Intern. J. Chem. Kinet., in press (1974)~~~~~~

76 Brown, R. D. H., Glass, G. P., and Smith, I. W, M., "Relaxation of HCl(v = l) and*DCl(v = l) by CI and Atoms," Abstract of paper given at 4th Conference on Chemical and Molecular Lasers, St. Louis Missouri, October 1974. Proceedings of meeting to be published IEEE J. Quantum Electronics.

~~~~~~Calvert, J. &., Kerr, J. A,, Demerjian, K. L., and McQuigg, R. D., "PhQ to lysis of Formaldehyde as a Hydrogen Atom Source in the Low jr Atmosphere, Science ±7jj, 751-752 (1972)~~~~~~

~~~~~~Campbell, I. M., and Gray, C. N., "Rate Constants for 0( 3P) Recombination~~~~~~

~~~~~~and Association with N( 4S)," Chem. Phys. Letts. 18, 607-609 (1973)~~~~~~

Castleman, A. V,, Jr., Davis, R. E., Munkelwitz, H. R. , Tang, I. N., and Wood, W. P., "Kinetics of Association Reactions Pertaining to ^sOa Aerosol Formation, 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.

~~~~~~Chapman, C. J., and Wayne, R. P., "The Reaction of Atomic Oxygen and Hydrogen with Nitric Acid," Intern. J. Chem. Kinet. £, 617-630 (1974)~~~~~~

~~~~~~Chung, K., Calvert, J. G., and Bottenheim, J. W., "The Photochemistry of Sulfur~~~~~~

~~~~~~Dioxide Excited within its First Allowed Band (3130 A) and the 'Forbidden' Band (3700-4000 A)," Intern. J. Chem. Kinet., in press (1974)~~~~~~

~~~~~~Clark, I. D., Jones, I. T. N. , and Wayne, R. P., "The Kinetics of the Reaction~~~~~~

~~~~~~between Og(*A- ) and Ozone," Proc. Roy. Soc. London A 317, 407-416 (1970)~~~~~~

~~~~~~Clyne, M. A. A,, Private communication (1974)~~~~~~

~~~~~~M. A., J. Clyne, A. w and Coxon, A., "Kinetics Studies of Oxyhalogen Radical Systems," Proc. Roy. Soc, (London) A 303, 207-231 (.1968)~~~~~~

~~~~~~Clyne, M. A. A., and Cruse, H. W., "studies of Ground-State 2P 3/2 Halogen~~~~~~

~~~~~~Atoms Using Atomic Resonance Absorption," Trans. Faraday Soc. 67 . 2869-2885 (1971)~~~~~~

Clyne, M. A. A., and Cruse, H. W., "Atomic Resonance Fluorescence Spectrometry for Rate Constants of Rapid Bimolecular Reactions. Part 1. Reactions + N0 J. Chem. Soc. Faraday Trans. II 1281- 2# ci + C1N0, Br + C1N0," 6£, 1299 (1972)

~~~~~~Clyne, M. A. A., and Down, S., "Kinetic Behaviour gf OH X2n ana A2^ using Molecular Resonance Fluorescence Spectrometry, J. Chem. Soc. Faraday Trans. II 2Q, 253-266 (1974)~~~~~~

Clyne, M. A. A., and Walker, R. F., "Absolute Rate Constants for Elementary Reactions in the Chlorination of CH CD CH CHgC^, 0HC1 CDC1 4# 4# 3Cl, 3 , 3 and CBrClg^ j. Chem. Soc. Faraday Trans. I £9, 1547-1567 (1973)

~~~~~~77 Collins, R. J,, Husain, D., and Donovan, R. J., Kinetic and Spectroscopic~~~~~~

~~~~~~Studies of lA^ Absorption Spectroscopy in the 2 ( a ^y Time-Resolved Vacuum Ultra-violet," J. Chem. Soc. Faraday Trans. II 69, 145-157 (1973)~~~~~~

~~~~~~Coltharp, R. N., Worley, S. D., and Potter, A. E., "Reaction Rate of Vibra- tionally Excited Hydroxy 1 with Ozone," Appl. Optics ±0, 1786-1789 (1971)~~~~~~

~~~~~~Cox, R. A., "The Photolysis of Nitrous Acid in the Presence of Carbon Monoxide and Sulphur Dioxide, J. Photochem., in press (1974a)~~~~~~

Cox, R. A., "The Photolysis of Gaseous Nitrous Acid - A Technique for Obtaining Kinetic Data on Atmospheric Photo-Oxidation Reactions," Presented at Symposium on Chemical Kinetics Data for the Lower and Upper Atmosphere, Airlie House, Warrenton Virginia, September 1974b. Proceedings to be published Intern. J. Chem. Kinet.

Cupitt, L. T., and Glass, G. P., "Reactions of SH with Atomic Oxygen and Hydrogen,' Presented at Symposium on Chemical Kinetics Data for the Lower and Upper Atmos- phere, Airlie House, Warrenton Virginia, September 1974. Proceedings to be published Intern. J. Chem. Kinet.

~~~~~~Daubendiek, R. L., and Calvert, J. G., "a Study of the N Ocr-SQj-O-* c c ° Reaction System, Environ. Lett., in press (1974) °~~~~~~

Davis, D. D., "Absolute Rate Constants for Elementary Reactions of Atmospheric Importance: Results from the University of Maryland's Gas Kinetics Laboratory,, Report #1, Chemistry Department, University of Maryland, July 1974

2 Davis, D. D., Braun, W., and Bass, A. M., "Reactions of C1 P . . Absolute Rate Constants for Reaction with H^ 0%, C2 Ife, CH2 C12 , C2CI4, and C~C J Chem Ki net. 101-114 (1970) 6H 12." In* ern » » » £,

Davis, D. D., Fischer, S., and Schiff, R. , "Flash Photolysis-Resonance Fluorescence Kinetics Study: Temperature Dependence of the Reactions OH + CO -> C0 + H and OH + CH -> + CH " J. Chem. Phys. 2213- 2 4 1^0 3# 6J, 2219 (1974)

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

~~~~~~the Reaction 0( 3P) + NO _> + the Temperature Range 230-339K," NO 2 Over J. Chem. Phys. 58, 530-535 (1973)~~~~~~

~~~~~~Davis, D. D., Payne, ¥•', and Stief, L., "The Hydroperoxyl Radical jj^n~~~~~~

~~~~~~Atmospheric Chemical Dynamics: Reaction with Carbon Monoxide, Science 179 . 280-282 (1973)~~~~~~

Davis, D. D., Prusazcyk, J., Dwyer, M., and Kim, P., "A Stop-Flow Time of Flight Mass Spectrometry Kinetics Study. Reaction of Ozone with Nitrogen Dioxide and Sulfur Dioxide, J. Phys. Chem. 78, 1775-1779 (1974) Davis, D. D», Wong, W., and Lephardt, J., "A Laser Flash Photolysis-Resonance Fluorescence Kinetic Study: Reaction of 0( 3P) with 0„ " Phys. °* chem. Lett, 22, 273-278 (1973)

~~~~Davis, D. D., Wong, W., and Schiff, R., "A Dye Laser Flash Photolysis Kinetics Study of the Reaction of Ground-State Atomic Oxygen with Hydrogen Peroxide," J. Phys. Chem. 78, 463-464 (1974)~~~~

Demerjian, K. L., Kerr, J. A., and Calvert, J. G., "The Mechanism of Photo- chemical Smog Formation," Adv. Environ. Sci. and Technology 4, 1-262 (1974) J. N. Pitts, Jr., and R. L. Metcalf, editors, Wiley-Interscience

~~~~~~DeMore, W. B., "Rate Constants for the Reactions of Hydroxy! and Hydro- peroxyl with Ozone," Science i§&. 735-737 (1973)~~~~~~

~~~~~~DeMore, W, B# , "Arrhenius Constants for the Reactions of Ozone with Ethylene and Acetylene," Intern. J. Chem. Kinet. 1, 209-220 (1969)~~~~~~

DeMore, W. B. , Rate Constant Ratio for the Reactions of OH with 0~ arid CO, 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.

~~~~~~DeMore, W. B., and Tschuikow-Roux, E., 'Temperature Dependence of the Reactions of OH and H0 " J. Phys. Chem. 78, 1447-1461 (1974) 2 w ith~~~~~~

~~~~~~Dillemuth, F. J., Skidmgre, D. R., and Schubert, C. C, "The Reaction of Ozone with Methane, J. Phys. Chem. 64, 1496-1499 (i960)~~~~~~

~~~~Donovan, R. J., Husain, D., and Kirsch, L. J., Reactions of Atomic Oxygen. Part 1: The Rate of the Reaction + -> 0~ ? + m + M (M = He, Ar and Kr)," Trans. Faraday Soc. §6, 2551-2559 (1970)~~~~

~~~~~~Fettis, G. C, and Knox, J. H., Rate Constants of Halogen Atom Reactions, G. Porter, Ed., Progress in Reaction Kinet. (Pergamon Press) 2, 1-38 (1964)~~~~~~

~~~~~~Findlay, F. D., and Snelling, D. R., "Temperature Dependence of the Rate~~~~~~

~~~~~~Constant for the Reaction (*A -, 0," ) + ° -> 20? + J. Chem. Phys. ~"54, 2750-2755 (1971) g~~~~~~

~~~~~~1 " Findlay, F. D., and Snelling, D. R., "Colli sional Deactivation of 0„( A ) * g * J. Chem. Phys. 55., 545-551 (1971a)~~~~~~

~~~~~~Fisher, E. R., and McCarty, M., Jr., "study of thejteaction of Electronically Excited Oxygen Molecules with Carbon Monoxide," J. Chem. Phys. 45, 781- 784 (1966)~~~~~~

~~~~~~" Foner, S. N., and Hudson, R. L. , "Mass Spectrometry of the H0 dp Free Radical J. Chem. Phys. 36, 2681-2688 (1962)~~~~~~

~~~~~~79 ,~~~~~~

~~~~~~Francis, P. D., The Production of Ox/ gen Atoms in a Microwave Discharge and th* Recombination Kinetics in a Gas Flow System, Brit. J. Appi. Phys. 2, < 717-1730 (169)~~~~~~

~~~~Gaedtke, H. , Glanzer, X., Hippler, H., Luther, K., and Troe, J., "Addition Reactions of Oxygen Atoms at High Pressures," Symp. Combust. 14th (Combustion Institute, Pittsburgh, 1973) 295-303~~~~

Gardiner, W. C., Jr., Mallard, W. &., McFarland, M., Morinaga, L., Owen, J. h. Rawlins, W. T., Takeyama, T., and Walker, B. F., "Elementary Reaction Rates from Post-Induction-Period Profiles in Shock- Initiated Combustion, Symp. Combust. 14th (Combustion Institute, Pittsburgh, 1973) 61-72

~~~~~~Gardiner, W. C, Jr., Mallard, W. G., and Owen, J. H., "Rate Constant of OH + H _ h + H to 1600 K," J. Chem. Phys. 6£, 2290-2296 2 2 from 1350 (1974)~~~~~~

Gauthier, M., and Snelling, D. R. , "Production et DSsexcitation de Q^D), 1 + ) dans la Photolyse de l'Ozone A 253.7 nm," Centre (^ ) et ? ( I, de Recherches Pour la Defense Valcartier, Quebec, Canada, DREV R-704/74 (February, 1974)

Gehring, M., Hoyerraann, K, f Schacke, H., and Wolfrum, J., "Direct Studies of Some Elementary Steps for the Formation and Destruction of Nitric Oxide in the H-N-0 System," Symo. Combust. 14th (Combustion Institute, Pittsburgh, 1973 99-105

Ghormley, J. A,, Ellsworth, R. L., and Hochanadel, C. J., Reaction of Excited Oxygen Atoms with Nitrous Oxide. Rate Constants for Reaction of Ozone with Nitric Oxide and with Nitrogen Dioxide," J. Phys. Chem. 77, 1341- 1345 (1973). Erratum: 78, 2698 (1974)

~~~~~~Glanzer, K., and Troe, J., [unpublished data sheets prepared for this survey] Ecole Poly technique Federals de Lausanne (1973)~~~~~~

~~Glavas, S., and Toby, S., The Reaction between Ozone and Hydrogen Sulfide, typescript, School of Chemistry, Rutgers University, New Brunswick, N.J., and private communication from S. Toby (1974)~~

~~~~~~Gordon, R. J., and Lin, M. C, "The Reaction of Nitric Oxide with Vibrationaily Excited Ozone," Chem. Phys. Lett. 22, 262-268 (1973)~~~~~~

Gordon, S., and Mulac, W. A., "Reaction of the OHU2*) Radical Produced by the Pulse Radiolysis of Water Vapor, 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.

Gordon, S., Mulac, W., and ^fetngia, P., "Pulse Radiolysis of Ammonia Gas. II. 2 Rate of Disappearance of the NFi B- p (x ) Radical," J. Phys. Chem. 75, 2087- 2093 (1971) 80 Gorse, H. A., and Volman, D. H«, "Photochemistry of the Gaseous Hydrogen Peroxide-Carbon Monoxide Systems Rate Constants for Hydroxyl Radical Reactions with Hydrogen Peroxide and Isobutane by Competitive Kinetics, J. Photochem. 1, 1-10 (1972)

Gorse, R. A., and Volman, D. H* v "Photochemistry of the Gaseous Hydrogen Peroxide-Carbon Monoxide System II: Rate Constants for Hydroxy 1 Radical Reactions with Hydrocarbons and for Hydrogen Atom Reactions with Hydrogen Peroxide, J. Photochem* 3, 115-122 (1974)

~~~~~~Graham, R. A., and Johnston, H. S., "Kinetics of the Gas-Phase Reaction between Ozone and Nitrogen Dioxide," J. Chem. Phys. 60, 4628-4629 (1974)~~~~~~

~~~~~~Gray, D., Lissi, E. , and Heicklen, J., "The Reaction of Hydrogen Peroxide with Nitrogen Dioxide and Nitric Oxide," J. Phys. Chem. 76, 1919-1924 (1972)~~~~~~

~~~~~~Greiner, N. R., Hydroxyl Radical Kinetics by Kinetic Spectroscopy. V Reactions with H and CO in the Range 300-500 °K," J. Chem. Phys-. 51, 5049-5051 (1969)~~~~~~

~~~~~~Greiner, N. R., Hydroxyl Radical Kinetics by Kinetic Spectroscopy. VI. Reactions with Alkanes in the Range 300-500°K," J. Chem. Phys. 03, 1070-1076 (1970)~~~~~~

~~~~~~Greiner, N. R., "Hydroxyl Radical Kinetics by Kinetic Spectroscopy. VII. 'ihe • Reaction with Ethylene in the Range 300-500°K," J. Chem. Phys. 03., 1284- 1285 (1970a)~~~~~~

~~~~~~Hack, W., Hoyerraann, K., and Wagner, H. Gg, , Reaktionen des hydroxy 1- radikals mit Ammoniak und Hydrazin in der gas phase," Ber. Bunsenges. Physik. Chen. 78, 386-391 (1974)~~~~~~

Hampson, R. F., (editor), 'Survey of Photochemical and Rate Data for Twenty- Ei^ht Reactions of Interest in Atmospheric Chemistry," J. Phys. Chem. Ref. Data 2, No. 2 pgs. 267-312 (1973). These are revised versions of data sheets originally distributed as NBS Reports 10692 and 10828.

~~~~~~Hams on, R. F. , (editor), "Chemical Kinetics Data Survey VI. Photochemical and Rate Data for Twelve Gas Phase Reactions of Interest for Atmospheric Chemistry," NBSIR 73-207 (1973a)~~~~~~

~~~~~~Hanst, P. L., Stephens, E. R., Scott, W. E., and Doerr, R. C, "Atmospheric t| Ozone-Olefin Reactions," (The Franklin Institute, Philadelphia, Pa. 1958)~~~~~~

~~~~~~Harker, A., and Johnston, H. S., "Photolysis of Nitrogen Dioxide to Produce Transient 0, N0 N ," Phys. Chem. 77. 1153-1156 (1973) 3 and 2 5 J.~~~~~~

~~~~~~Heicklen, J., "Gas-Phase Reactions of Alkylperoxy and Alkoxy Radicals," Adv. Chem. Ser. (Amer. Chem. Soc, Washington) 76, 23-39 (1968)~~~~~~

81 Heicklen, J.» Photochemical and Hate Data for Methyl Hi trite, Kethcxv and Methylperoxy,' Chenical Kinetics Data Survey V. Sixty-six Contribu*ed Rate and Photochemical Data Evaluations on Ninety-four Reactions, NBSIR 73-206, D. Garvin, Ed., National Bureau of Standards, Washington, D.C. (1973) pages 43-48

~~~~~~Herron, J. T., and Kuie, R. E«, Rate Constants for the Reactions of Ozone ti with Ethene and Propene, from 235.0 to 362.0 K," J. Phys. Chem. 78, 2085- 2088 (1974)~~~~~~

~~~~~~Herron, J. T., and Huie, R. E., "Rate Constants for the Reactions of Atomic~~~~~~

~~~~~~Oxygen (03P) with Organic Compounds in the Gas Phase, J. Phys. Chem. Ref. Data 2, 467-518 (1973)~~~~~~

~~~~~~Herron, J. T., and Huie, R. E., "Rates of Reaction of Atomic Oxygen. II. Some C £ t0 c8 Alkanes," J. Phys. Chem. 73, 3327-3337 (1969)~~~~~~

Hikida, T., Eyre, J. A., and Dorfman, L. M., "Pulse Radiolysis Studies. XX. Kinetics of Some Addition Reactions of Gaseous Hydrogen Atoms by Fast Lyman-a Absorption Spectrophotometry," J. Chem. Phys. 54, 3422-3428 (1971)

~~~~~~Hippler, H., and Troe, J., Hochdruckbereich der Rekombination + ? _> °3," Ber. Bunsenges. Physik. Chem. 75, 27-32 (1971)~~~~~~

Hippler, H., Schippert, C, and Troe, J., "Photolysis of NQ ? q^^ Collisional Energy Transfer in the Re act ions O + NO -> N0 _> ," 2 a^ y + no2 N03 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.

~~~~~~Hochanadel, C. J., Ghormley, J. A., and Ogren, P. J., "Absorption Spectrum and Reaction Kinetics of KO c? Kadical in the Gas Phase," J. Chem. Phys. ~"~56, 4426-4432 (1972)~~~~~~

~~~~~~Hollinden, G. A., Kurylo, M. J., and Timmons, R. B., Electron Spin Resonance M Study of the Kinetics of the Reaction of 0( 3P) Atoms with R-s j f # phys. Chem. 74, 988-991 (1970)~~~~~~

~~~~~~Holmes, H. H., and Daniels, F., "The Photolysis of Nitrogen Oxides: \o*. N ," 630-637 ? 4 and N02 J. Amer. Chem. Soc. 56, (1934)~~~~~~

~~~~~~Howard, C. J., and Evens on, K. M., "Laser Magnetic Resonance Study of the Gas Phase Reactions of OH with CO, NO, and N0 " ? j # chem. Phys. ""61, 1943-1952 (1974)~~~~~~

~~~~~~Huestis, D. L., Black, G., Edelstein, S. a., and Sharpless, R. L., "Fluorescence and Quenching of lA (^ ) and Liquid Oxygen." J. Chem. Phys. 2 g [02( g)]2 in £0, 4471-4474 (1974)~~~~~~

82 Huie, R. E. ( and Herron, J. T., Temperature Dependence of the Rate Constants for Reactions of Ozone with Some Olefins," 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.

~~~~~~Huie, R. E., and Rerron, J. T., "The Rate Constant for the Reaction 3 + N02 -> Temperature Range 259-362° K," Chem. Phys. Lett. 27. 2 + N0 3 Over the~~~~~~

~~~~~~. 411-414 (1974a)~~~~~~

~~~~~~Huie, R. E., Herron, J. T., and Davis, D. D., "Absolute Rate Constants for the Reaction + K »" 2 + m -> 3 + M Over the Temperature Range 20C-346° 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~~~~~~

~~~~~~Johnston, H. S., "Gas Phase Reaction Kinetics of Neutral Oxygen Species,"~~~~~~

~~~~~~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 Vapor," J. Phys. them. 78, 1-7 (1974)~~~~~~

~~~~~~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 in tne Photolysis of 2 Kadicals~~~~~~

~~~~~~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 in the Ultraviolet and the Visible Absorption Spectrum of N0„ " J. Chem. Phys. £, 875-877 (1937) •~~~~~~

~~~~~~Kaufman, F. , Aeronomic Reactions Involving Hydrogen. A Review of Recent t< 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. Gazofaznykh Reaktgij Spravochnik, fc "Kons^tanty Skorosti (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, Spring- field, Va. 22151)

~~~~~~Kurylo, M. J., Hollinden, G. A., LeFevre, H. F. , and Timmons, R. B., "ESR " Study of the Kinetics of the Reactions Atoms with NH, of D Atoms and # J. Chem. Phys. 5J, 4497-4501 (1969)~~~~~~

~~~~~~Kurylo, M. J., "Absolute Rate Constants for the Reaction H + + M -> H0 m Over the Temperature Range 203-404 K," J. Phys. Chem. 76, 3518- 2 + 3526 (1972)~~~~~~

~~~~~~Kurylo, M. J., "Kinetics of the Reactions 0H(v = 0) + NH -> 3 h2o + NH? and OH(v = 0) + _> 298°K." Chem. Phys. Letts. 23, 467- * HOo + Ood at 471 (1973) '~~~~~~

~~Kurylo, M. J., Braun, W., Kaldor, A., Freund, S. M., and Wayne, R. P., "infra-red Laser Enhanced Reactions: Chemistry of Vibrationally Excited 1*)." J. Photochem. 3, 71-8'? (1974) 3 with NO and O^~~

~~~~~~Kurylo, M. J., Peterson, N. C., and Braun, W., "Absolute Rate of the Reaction " H H s j. chem. Phys. 54, 943-^46 (1971) 2 #~~~~~~

~~~~~~Laufer, A. H., and Bass, A. M., "Rate Constants of the Combination of Methyl Radicals with Nitric Oxide and Oxygen," typescript. National Bureau of Standards, Washington, D. C. (1974)~~~~~~

Lin, C. L.^ and DeMore, W. B., "o^D) Production in Ozone Photolysis Near 31 00 A, J. Photochem. 2, 161-164 (1973) Lloyd, A. C, "Evaluated and Estimated Kinetic Data for Gas Phase Reactions of the Hydroperoxyl Radical," Intern. J. Chem. Kinet. 6, 169-228 (1974) Supersedes NBS Report 1044?

3 Lundell, 0. R., Ketcheson, R. D., and Schiff, H. I., "The Production of 0( P) Atoms, Free Fro.ii ," Excited Molecules, and Their Reaction with 3 Symp. Combust. 12th (Combustion Institute, Pittsburgh, 1969) 307-311

~~~~~~Mack, G. P. R., and Thrush, B. A., "Reaction of Oxygen Atoms with Carbonyl~~~~~~

~~~~~~Compounds. Part 1. Formaldehyde," J. Chem. Soc. Faraday Trans. I 69 . , 209-215 (1973)~~~~~~

~~~~~~Margitan, J. J., Kaufman, F., and Anderson, J. G., "The Reaction of OH with CH 4» Geophys. Res. Lett. 1, 80-31 (1974)~~~~~~

~~~~~~McCrumb, J. L. , and Kaufman, F., "Kinetics of the + 0,, Reaction," J. Chem. Phys. 57, 1270-1275 (1972)~~~~~~

~~~~~~MCKenzie, A., Mulcahy, M. F. R., and Steven, J. R., "Kinetics of Decay of Hydroxy 1 Radicals at Low Pressure," J. Chem. Phys. 59, 3244-3254 (1973)~~~~~~

~~~~~~McQuigg, R. D., and Calvert, J. G., "The Photodecomposition of CiLo, CD?0, CKDO and CH at Xenon Flash Lamp Intensities," J. Amer. ? o-ci)pO Mixtures Chem. Soc. 91, 1590-1599 (1969)~~~~~~

~~~~~~Meaburn, G. M., Perner, D., LeCalve, Ji, and Bourene, M., "A Pals ed-Kadio lysis Study of Atomic Oxygen Reactions in the Gas Phase," J. Phys. Chem. 72, 3920-3925 (1968)~~~~~~

Meagher, J. F. , and Heicklen, J., The Photolysis of Hydrogen Peroxide in the Presence of Carbon Monoxide, Dept. of Chemistry and Center for Air Environment Studies, The Pennsylvania State University, University Park Pennsylvania, CAES Publication No. 370-74 May, 1974

~~~~Milks, D. , and Matula, R. A., "A Single-Pulse Shock-Tube Study of the Reaction between Nitrous Oxide and Carbon Monoxide, Symp. Combust. 14th (Combustion Institute, Pittsburgh, 1973) 33-96~~~~

~~Moortgat, G. K., and Allen, E. m R., "The Room Temperature Reactions of Hydrogen- Atoms in Molecular Oxygen," National Center for Atmospheric Research, Boulder (1973). Abstract of unpublished work.~~

~~~~Morley, C, and Smith, I. W. M., 'Rate Measurements of Reactions of OJi by Resonance Absorption. Part I. Reactions of OH with WJ NO,' ? and J. Chem. Soc. Faraday Trans. It 68, 1016-1030 (1972)~~~~

~~~~~~Morris, E. D., Jr., and Niki, H., "Mass Spectrometric Study of the Reaction of Hydroxyl Radical with Formaldehyde," J. Chem. Phys. 55, 1991-1992 (1971)~~~~~~

~~~~~~85 Morris, S. D., Jr., and Niki, H., Reaction of Methyl Radicals with Atomic Oxygen," Intern. J. Chen. Kinet. 5, 47-53 (1972)~~~~~~

~~~~~~Morris, E. D., Jr., and Niki, H. , "Reaction of Dinitrogen Pentoxide with Water," J. Phys. Chera. 77, 1929-1932 (1973)~~~~~~

Morris, E. D., Jr., Stedman, D. K., and Niki, H,, Mass Spectrometric Study of the Reactions of the Hydroxy 1 Radical with Ethylene, Propylene, and Acetalaehyde in a Discharge-Flow System, " J. Amer. Chem. Soc. 93, 3570-3572 (1971)

~~~~~~Mulcaliy, M, P. R., and Williams,^. J., "Kinetics of Combination of Oxygen Atoms with Oxygen Molecules," Trans. Faraday Soc. 54, 59-70 (1968)~~~~~~

~~~~~~Nicholas, J. E., and Norrish, R. ft. W., "Some Reactions in the Chlorine and~~~~~~

~~~~~~Oxygen System Studied by Flash Photolysis," Proc. Roy. Soc. (London) A 507 . 391-397 (1968)~~~~~~

Overend, R,, Paraskevopoulos, G., and Cvet-movic, R. J., "Hydroxyl Radical Rate Measurement for Simple Species by Flash Photolysis kinetic Spectros- copy," Eleventh Informal Conference on Photochemistry, Vanderbilt Univ.* June 1974

~~~~~~Parkes, I*. A., Paul, D. M., Qulnn, C. P., and Robson, R. C, "i'he Ultraviolet Absorption by Alkylperoxy Radicals and Their Mutual Reactions," Chem. Phys. Lett. 22, 425-4P9 (1973)~~~~~~

~~~~~~Pastrana, A., and Carr, R.„W., Jr., "Rate of the Reaction of fydroxyl Radical with Acetylene," Intern. J. Chem. Kinet. 6, 587-595 (1974)~~~~~~

Pate, C. T,, Finlayson, B. J., and Pitts, J. M., Jr., "a Long Path Infrared Spectroscopic Study of the Reaction of Methylperoxy Free Radicals with Nitric Oxide," J. Am. Chera. Soc. 96, 6554-6558 (1974)

~~~~~~Payne, W. A., Stief, L. J., and Davis, D. D. , "a Kinetics Study of the Reaction of H0 Amer. Chem. Soc. 95, 7514-7619 (1975) ? with S0P and NO," J.~~~~~~

~~~~~~Peeters, J., and Mahnen, G., "Reaction Mechanisms and Rate Constants of Elementary Steos in Methane-Oxygen Flames," Symp. Combust. 14th (Combustion Institute, Pittsburgh, 1973) 133-141~~~~~~

~~~~~~Pitts, J. N., Jr., Sandoval, H. L., and Atkinson, R., "Relative Rate Constants for~~~~~~

the Reaction of OpD) Atoms with Fluorocarbons and N q " d9 Chem Phys. Lett ~'29 31-34 (1974) * ' *

~~~~~~Prays, V. -I., Jr., Slagle, I. K. , and Gutman, D., "Determination of Branching Ratios for the Reaction of Oxygen Atoms with Ethylene,' J. Phys. Chem. 78. 663-665 (1974)~~~~~~

~~~~~~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 Chem. Phys. 57, 520-523 (1972) 2 C0," J.~~~~~~

~~~~~~Sauer, M. C, Jr., "a Puis e-Radioly sis Study of the Dependence of the Reaction of Atomic Oxygen with Oxygen on the Nature of the Third Body," J. Phys. Chem. 71, 3311-3313 (1967)~~~~~~

~~~~~~Schofield, K.\ "The Rate of Destruction of (*A ) by Atomic Hydrogen," Intern. c 6 J. Chem. Kinet. 4, 255-263 (1972)~~~~~~

~~~~~~Schofield, K., "Evaluated Chemical Kinetic Rate Constants for Various Gas Phase Reactions," J. Phys. Chem. ::ef. Data 2, 25-84 (1973)~~~~~~

~~~~~~Simonaitis, R., and Heicklen, J., The Reactions of HOp w ith Carbon Monoxide and Nitric Oxide and the Reaction of 0(*D) with Water," J. Phys. Chem. 77, 1096-1102 (1973a)~~~~~~

~~~~~~" Simonaitis, R., and Heicklen, J., "The Reaction of H0„ w i'th 0, J. Phys. Chem. 77, 1932-1935 (1973b)~~~~~~

~~~~~~Simonaitis, R. , and Heicklen, J., "The Mechanism of the H_Q-catalyzed Chain~~~~~~

~~~~~~Photodecom-oosition of and the Reaction of HO with " J. Photochem. 2, 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)~~~~~~

~~~~I. R., Pruss, F. J., Jr., and Gutman, D., the Steady Slagle, "Kinetics into 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 3 3 Resonance Fluorescence. I. 0( P) + Q + m -> 0„ + M and 0( P) + NO + M ->~~~~~~

~~~~~~N0 + M," J. Chem. Phys. 53., 3717-3721 (1970) 2~~~~~~

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

~~~~~~for 0(3p) + NO -> o + NO," Intern. J. Chem. Kinet. 5. 615-620 (1973) g 2~~~~~~

Slanger, T. G., and Welge, K. H., "Rate Constants for Reactions of 0( 1 S)," in Chemical Kinetics Data Survey V. Sixty-six Contributed Rate and Photo- chemical Data Evaluations on Ninety-four Reactions, NBSIR 73-206, D. Garvin, Ed., National Bureau of Standards, Washington, D.C., (1973) pages 22-32 i

Smith, I. W c M. t and Zellner, R. , Rate Measurements of Reactions of OH b^ ' Resonance Absorption Part 2. Reactions of OH with Co, C h . and C H_ 4 d J. Chem. Soc e Faraday Trans. II 69, 1617-1627 (1973)

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 Resonance Absorption. Part 4. - Reactions of OH with NH, and HNO-*," 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.

~~~~~~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, "Absolute Rate Constant for the Reaction OH + NH„ 0," s _> nh2 + H2 J. Chem. Phys. 5g, 535-537 (1973a)~~~~~~

~~~~~~Stuhl* Fe , Rate Constant for the Reaction of OH with n-C Naturforsch. 4h1Un * g a Pt A 28, 1383-1384 (1973b)~~~~~~

Stuhl, F. , Determination of Rate Constants for the Reactions of OH with Propylene and Ethylene by a Pulsed Photolysis-Resonance Fluorescence Method," Ber 9 Bunsenges. Physik. Chem. 2Z, 674-677 (1973c).

~~~~~~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)~~~~~~

~~~~~~3 Stuhl, F. , and Niki, H., "Detection of Oxygen ( P) 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, Vacuum-uv 2f CO, N2 , and COg Using a Pulsed 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^ Detection Method," j^ t and' CO Using a Resonance-Fluorescent J. Chem. Phys. 52, 3671-3677 (1972) Takacs, G. A., and Glass, G. P., Reactions of Hydroxy! Radicals with Some Hydrogen Halides," J. Phys. Chem. 77, 194S-1951 (1973)

Taylor, R. L., "High Temperature Air Reactions," in NBSIR 74-430 Chemical Kinetics Data Survey VII, Tables of Rate and Photochemical Data for Modelling of the Stratosphere (Revised), D. Garvin and R. F. Hampson, Eds,, National Bureau of Standards, Washington, D.C., January 1974

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

~~~~~~Toby, F. S,, and Toby, S., "Reaction between Ozone and Allene in the Gas Phase," Intern. J. Chem. Kinet. 6, 417-428 (1974)~~~~~~

,3-Bu Toby, F. S. 4 and Toby, S., "The Reaction of Ozone with 1 tadi ene and with Allene, 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.

~~~~~~Trainor, D. W., and von Rosenberg, C. W., Jr "Flash Photolysis Study of the Gas #Jl Phase Recombination of Hydroxyl Radicals, J. Chem. Phys. 61, 1010-1015 (1974)~~~~~~

~~Tsang, W., "Comparison between Experimental and Calculated Rate Constants for Dissociation and Combination Reactions Involving Small Polyatomic Molecules," Intern. J. Chem. Kinet. 5, 947-963 (1973)~~

1 Vardanyan, I. A., Dangyan, T. M., and Sachyan, G. A., Rate Constants for the Reaction H0 CO -> C0 + OH," Dokl. Phys. Chem. 2JD5. 632-634 (1972); 2 + 2 tr. of Dokl. Akad. Nauk SSSR 205, 619-621 (1972) van den Bergh, H. E., and Callear, A. B. , "Spectroscopic Measurement of the Rate of the Gas-Phase Combination of Methyl Radicals with Nitric Oxide and Oxygen at 295 K," Trans. Faraday Soc. 67. 2017-2024 (1971)

Volman, D. H., and Gorse, R. A., "Rate Constant for the Reaction of H0~ with Carbon Monoxide," J. Phys. Chem. 76, 3301-3302 (1972) von Rosenberg, C. W., Jr., and Trainor, D. W., "Vibrational Excitation of Ozone Formed by Recombination, J. Chem. Phys. 61, 2442-2456 (1974)

~~~~~~Walker, R. W., Ph.D., thesis, Univ. of London, Queen Mary College, 1973~~~~~~

~~~~~~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, 2391-2393 (1968)~~~~~~

~~~~~~Walker, R. W., Comments on "Gas-Phase Oxidation of Butene-2: The Role of~~~~~~

~~~~~~Acetaldehyde in the Reaction," by Ray, D. J. M., Diaz, R. R. , and Wassington, D. J., Symp. Combust. 14th (Combustion Institute, Pittsburgh, 1973) 265-266~~~~~~

~~~~~~89 Washlda, N., and Bayes, K. D., The Rate of Reaction of Methyl Radicals with Atomic Oxygen," Chem. Phys. Letts. 23, 373-375 (1973)~~~~~~

~~~~~~Washida, N. , Martinez, R. I., and Bayes, K, D., "The Oxidation of Formyl Radicals," typescript, Univ. of California (Los Angeles) (1973)~~~~~~

~~~~~~Watson, R. T., "Chemical Kinetics Data Survey VIII. Rate Constants of CIO~~~~~~

~~~~~~of Atmospheric Interest," NBSIR 74-515 (1974) (distributed by Chemical Kinetics Information Center, National Bureau of Standards, Washington, D.C.~~~~~~

~~~~~~. 20234)~~~~~~

~~~~~~Wayne, R. P., private communication (1974)~~~~~~

~~~~~~Westenberg, A. A., and deHaas, N., "steady-State Intermediate Concentrations and Rate Constants* Some HO,, Results," J. Phys. Chem. 75, 1586-1593 (1972a)~~~~~~

~~~~~~Westenberg, A. A., and deHaas, N., Measurement of the Rate Constant for H + H -> H + HCO at 29?-652°K," J. Phys. Chem. 76, 221-3-2214 (1972b) 2 co 2~~~~~~

~~~~~~Westenberg, A„ A., and deHaas, N. , "Rates of Co + OH and H + oh Over an ? Extended Temperature Range," J. Chera. Phys. 58, 4061-4065 (1973a)~~~~~~

~~~~~~" Westenberg, A. A., and deHaas, N., "Rate of the Reaction OH OH -> H q + Q f J. Chem. Phys, 58, 4066-4071 (1973b)~~~~~~

~~~~~~Wilson, Wnu E., Jr., "a Critical Review of the Gas-Phase Reaction Kinetics of the Hydroxy 1 Radical," J. Phys. Chem. Ref. Data 1, 535-573 (1972)~~~~~~

Wong, E. L., and Belles, F. £., "Rate Measurements for the Reaction of Hydrogen Chloride and Deuterium Chloride with Atomic Oxygen," Lewis Research Center, NASA, Cleveland, Ohio, NASA Tech. Note, NASA TN-D-6495 (1971)? Chem. Abstr. 76:18326q (1972)

~~~~~~Wong, W., and Davis, D. D., A Flash Photolysis-Resonance Fluorescence Study of the Reaction of Atomic Hydrogen with Molecular Oxygen: H + 0„ + m ->~~~~~~

~~~~~~H0 J. Chem. Kinet. 401-416 (1974) 2 + M," Intern. 6,~~~~~~

~~~~~~Wu, C e H„, Morris, E. D., Jr., and Niki, H., "The Reaction of Nitrogen Dioxide with Ozone," J. Phys. Chem. 77, 2507-2511 (1973)~~~~~~

Wyrsch, D., Wendt, H. R., and Hunziker, H. £., "Modulation Kinetic Spectroscopy of H0 ," Hg/H^/Og/co Mixtures; Reactions of HgH and 2 XI. Intern. Symp. on Free Radicals (Berchtesgaden-Konigssee, Sept. 4-7, 1973) Paper No. 36; see also, Ber« Bunsenges. Physik. Chem. 78, 204 (1974)

~~~~~~Zahniser, M. S., Kaufman, F., and Anderson, J. G., "Kinetics of the Reaction of OH with HC1," Chem. Phys. Lett. 27, 507-510 (1974)~~~~~~

~~~~~~Zellner, R., and Smith, I. W. M., "Rate Constants for the Reactions of OH with NH d HNO^/' Phys. Lett. ?6, 72-74 (1974) 3 an Chem. 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 inter- actions 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 I 1 V*1~~~~~~

~~~~~~ON r-. vO r~ OS cn m oo tH cn ,_, en i-l r»« vo 00~~~~~~

T3 i^ en i-i 00 O CM r^ 1^ p n) vo O 00 OS o OS 00 s CM - CT\ ocm if) •— 8 • i-. 33 00 a C^ IM n) as i-l •d- cn u 00 00 00 en •* 00 cn vo © 00 M-l en o m r-l vo CM 00 vO CM r^ a\ en 4-» O • • o • • o • O • • • • CO 3 m os 00 00 - (4 en m vO OS u m 00 st rH OS i-l OS 00 r^ r^ cn t-l o> ft. .-1 1^ 8 JH J* m r~- s m in o cn m OS m os © VO tH o 51 • In "J OS VO CM 1^ st CM os m r^ CM CM t-l r^ r^ OS CM w m c3 in CM en en m m en i-l CM tH t-l C h r-l i i i-l W a

~~~~~~rt OS r^ tH O > in m m tH tH i-i r^- i-i CM 1^ en 00 «d-~~~~~~

~~~~~~in aj~~~~~~

~~~~~~H rt 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 W~~~~~~

§ c ri a>> X to eg v-^ i-l J3 V U 01 u X 3 •\ CO o CO 0) o W l-l I-H •H tH ai 13 l-l CD o i-l 4J T3 X 3 TJ !-) ^-1 o o CJ o t-i X CD C 4-1 O B 9) l-l O CD •H u o i-l I-H CD H tH o (- 6 >s eo 43 4J 4-1 1-1 1-1 •H •O fr •-s y- fr <] W N t^ >^ ^ £1 S 4-1 •H 1-1 c G G 2 Q oo O i-l i-l e J= fl 43 CM 1-1 (3 c »* I-H h v-^ v*-* CM c CM en © c >.• v-^ o O o CM CM CM en CM 33 O CM CM CM o O © CM CM c o o O O O O o 33 3= s 33 P3 3B B Z B z B5 55 53 M

~~~~~~93 I~~~~~~

~~~~~~CM 00 O CO u Q~~~~~~

~~~~~~in r-- cm o o> CM o m o r- 3 O O co m oo co m C ro vO~~~~~~

~~~~~~o 00 r~ CO CM m vt i-l r~ r-l CO T vO r^ oo oo o in i-l m o\ CO CM M O CO CO CO \o vO oo o m o m~~~~~~

~~~~~~nj a. CTi i-l 00 o CO 00 o> CO CM CO o\ r-- 2 3 ? i-l 00 CO~~~~~~

~~~~~~C a! i£> vO sj- oo >• co ON Oi c W a o~~~~~~

~~~~~~o \0 O~~~~~~

~~~~~~vo \o cm in vf oo CM CM CM m m «3- o c3 J- CO CO CO CM CO CM CM CM CM .-H VD O \D VO VD S .5? o O O O O O O rH O I- Hi o > oo in vo r^ CO CM CM co 00 CO 00 ct\ a> oo co hi~~~~~~

~~~~~~J3 ,Q 60 00 60 •rH 60&060606060b06060~~~~~~

~~~~~~a «/5~~~~~~

~~~~~~c nl a>-~~~~~~

~~~~~~C W 3 rr 01 y X) X U 0) O •u CO V4 D 4J CD •H 3 a /-N •fl O CO 4-1~~~~~~

~~~~~~94 CM i-l~~~~~~

~~~~~~o in m~~~~~~

~~~~~~00 CM ^D 00~~~~~~

~~~~~~t-H «£> °° CT\ 00 VO~~~~~~

~~~~~~! SP 00 CO 0> CO ^ "^~~~~~~

~~~~~~CO CI CO~~~~~~

~~~~~~CO CT\ CO~~~~~~

~~~~~~co m co~~~~~~

Ol o> CO «-*

~~~~~~o^ vo cr>~~~~~~

~~~~~~o> N o in in m c*v m co oo ^d o o CM CO CO CO cS a~~~~~~

~~~~~~oOoOcJJcJJbOtxOOOOOOOOObOW) 00~~~~~~

~~~~~~2 2 CO CO CO CO c J. cj o u~~~~~~

~~~~~~95 * i 1 1i t 1 ii1 1 1 I I 1 1 i 1 1 1~~~~~~

~~~~~~o u-i CM CO o i-l 00 r~ I-. ON~~~~~~

~~~~~~4) XI r-- "^ vO ui vO ITl u-i o i— CM CM vO 00 o '- vO oo 00 u-i , CO in vO ^1- ITl m u-i VO VD O~~~~~~

•pp ITl rv] ON ON ON o *'' CM ITl vO r-~ CM in vO CO r^- l-H i— ON r^ 00 1 on CM u-i CO r— ^ CM u-i -* tNI u-i CO u-i oo CM UO VO CM oo o 00 X 1—1 CM CM CM CM CO CO -tf - etM in >r4 PS — o CO a 0- Cvl CM o 00 vO O i-l r^ i-i 1—1 00 vO 00 o on ON vO CO CM VO 00 4j O CM O vO O oo O O 53 (4 rH !— u-i 00 o vO CM r-- u-l in CO * CO o CO V 1 1—4 1 u-i CM CM u-l i-l CO i i-H i 1 CO CM _ 1 1 XI E <4 ^ > ni CM 1^- 00 a o ON O-i oo CM CO r-^ CM r~ r^ u-l J< I-l r-- 3 oo O o O -* 00 O O d- o s^

~~~~~~00 rt li*t CO r~ CM CO vw «~~~~~~

~~~~~~rt vO vO 00 CM CM r-~ i-l vO vO oo oo VO vO * CO CM i— > oo H £ .2? o O o o o o 4) Ih 0) -* 00 in r-l r^ vO oo ON o CM -d- oo oo CM CO c >~~~~~~

~~~~~~xi 01 XI 00 00 OO 00 00 00 00 00 00 00 00 00 oo (4 60 00 6 w W X) C «!~~~~~~

~~~~~~>- > a (4 Q .c c w c H w V 'J C .& (4 t-l 4-» u 6 (0 u >> XI w 4) w 3 a)~~~~~~

XI •i-i 0) c i-i X X <0 > 4J -r-l u i— i-l >N t4 3 o a) In 14 V4 o X> in 4-> 0) o 2 1 4) u n] o 4) x: a x; o •H 1— o 4J 4J 4J u u c X CO i-l o J3 2 O l-H X, o u (4 a) 41 4J p. a. o C o o o O PS O -C u I-l o CM XI CM u g g g g o o

~~~~~~96 1 i i I< t i —~~~~~~

~~~~~~CT\ en \D 00 00 O 00 VO in o> en 14D CT\ o a\ 00 VO p» r-l CJ T-( *o 00 o CM 00 o E CM~~~~~~

~~~~~~oi -d \D 00 .—~~~~~~

10 °pP in r\i ^o o *J3 m cn vO en CN CM CM CM CM CM CM OCM lD en cn en en —i o 00 w ed o W cvj fl) r~ en o en m CM \o 00 H 14-4 r^ 1— r~ r^ en a\ CM ai ^J (-3 O CM o> 00 a) <5 in o in in in cn en i 1 W CD CM o CM CM CM CM i a i o X T3 E C ^~ (X rt "5 > CM o CM in o o> a u vO \D •2 • M en O en o en ctn r-~ o> CM 2 • ;-. CM vo V43 CM < r^ CM CN en o CM 1 1 i— c CM en CM i i i z 1 !* Q c O O 2 CO CM o-\ CM i— CM K n tf r-^ o 00 CM o in CM C o ^-j CM CM e^ W § £> oo CM ^ CN CM f—' i— CM ^o <£> CM o CM 1 1

~~~~~~H 1 1 Ui 1 -5~~~~~~

~~~~~~< rt ,_, 00 CM O -* m ^ vO CO £> CM O > "3 X o O-i 00 \D m en o> o> c^ o> cn 00 2 o -tf o 1- •* w C en ^O CM o CO~~~~~~

XI QJ X 00 60 00 00 00 oo 00 60 60 60 60 o Ri 60 60 00 w 6 W w c ed > > a cd Q -C c W g w 4) CJ u a, c U c CJ CO 01 W ni S* c c o CO ed CJ en en CJ CJ X •a C 4J X W J3 01 CJ 4-J B u CJ erj 'A 3 3 T) CJ o CJ u u T3 i-i to C • H e u B o CJ o CJ ed •H VJ o o o XI ^-l CD -o CJ •H a CJ X o Vj 3 ^4 x c •o •r4 -a O •H -o 3 o X 3 o o (j •H ed Vj efl •H X •H o c O 3 M-l 3 <0 L X 6 u o U CJ o U m -4 u ed o CO T-l CJ C H o O 6 ecj U-J 13 4-J "3 •H JJ 3 X D. ^t •H o o CJ CJ IS T3 4J X. o o J= S 4J ^. 1-1 u 4J Vj CJ o o c CJ 4-J o o a E CJ CJ O •H C o c *H a c a >, eu M •H u X ^ o 2 1 H •H CJ X U) C o >J C o (J -D k Vj ^J 00 o O & •H r- O o H •H 14 o ^ 4J -C t-H 2 O O o U ^ X 13 n ed u a u H o o X Vj CJ 4-1 CJ 3 •H •H 2 X X! >, c o eej CM CJ (J u >, X C X a U en f=K c X. o 33 PS B s CJ CJ CJ

~~~~~~97 i — t t t 1~~~~~~

~~~~~~en NO en o~~~~~~

~~~~~~TJ ~"~- on r^ en en CN on ON ^3 m nO en in on _ O NO . OCN m ON CN 3 i-H i-H l-H CN • nl a u ON en NO I^- NO i-4 o 3 X m oo NO -* ON 00 o >H ON CN~~~~~~

~~~~en en cn n) r-t l-H i-H -* CN 00 en 00 NO O en oo o bJi 3 £ P^ r-. 00 en o oo m «3f Ih £ .2? -* o> en o cn i-H 0) Ih ID m cn o ON ON oo no cn cn C l-H £ m 3 NO i-H <—1 •— w i-H l-H~~~~

~~~~~~.fl o Xi a 00 oo 00 00 00 do oo oo •a c n) > Q.~~~~~~

Ri x c c 0) W u i-H c .2* CD l-H CO tt Ih T3 CO o •H u t4 01 y iH <0 CO u •o c N "-1 01 T3 o l-H x >n c •v •i-l •l-l >N 4-> X CO ^V c u •O >N X 0) 4J X CO o X 4-1 o u 4-> e C i-H oi 4J a Ih O 01 o c id x c e 01 6 O U o <4H o 01 o 6 -H O u o 3 i-H MH O Ih X l-H o u v. 1— >N O Ih O o x: i-H ft £ >N X U O l-H ea o X i-4 f* 43 4J O 3 X U tH u X 2 •u 01 l-H O 4-1 Ih t4 CJ h 01 e X ItH IH OJ 4J u g o •H u 4J en 4-1 l-H 2 CN u 4-1 cn i-H 1 ^N i-H i-H en 4-1 ^ l-H o i-H X 4J 4) o u i-H en ^H o o «, 1 en CN O en i-H o EC cn i-H 01 c 3 Ph c_> CN CN fB V s g B O u o O l-H H

~~~~~~98 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 ] by assuming that: (a) the breaking 9 (g)~~~~~~

~~~~~~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 0N0(g)] = -16.5 kcal mol " was derived 3~~~~~~

~~~~~~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 0H(g) +-N0C^(g) = CH 0N0(g) +HCX(g). 3 3~~~~~~

~~~~~~derived The value for £Hf° (CH 0N0 (g)) = -29.8 kcal mol"' was 11. 3 2~~~~~~

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

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

~~~~~~based upon have chosen S° [CH ON(> (g)] = 76.1 cal mol" K~ 12. We 3 2 Chem. Soc. low temperature thermal data of Gray and Smith (J.~~~~~~

~~~~~~studies by 1953 2380-2385). Calculations from microwave~~~~~~

~~~~~~give S° = Dixon and Wilson (J. Chem. Phys. 35, 191-198 (1961)) -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 obtained from S. W. Benson and H. E. , p~~~~~~

~~~~~~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 Thermo-~~~~~~

~~~~~~dynamic 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 C1 in the liquid state 2~~~~~~

~~~~~~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 Cl(g)]. 3~~~~~~

~~~~~~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)~~~~~~

~~~~~~- 20 493.59±0.4 1L7.97±0.1 2~~~~~~

~~~~~~o - o + 101.4±2.1 24.24±0.5 (2) 2~~~~~~

~~~~~~H -» 2H 432.00±0.04 103.25±0.01 2 HO - H + 423.8±2.1 101.3±0.5~~~~~~

~~~~~~HO - HO + 264.4±4 63.2±1~~~~~~

~~~~~~- H + 192+13 46±3 2 H - HO + H 493.7±0.8 118.0±0.2 2 H - 2H0 207.1±2.1 49.5±0o5 2 2~~~~~~

~~~~~~H - H'+ H0 370o3±8 o 4 88.5±2.0 2 2 2~~~~~~

~~~~~~N - N + N 941.69±0.04 225o07±0o01~~~~~~

~~~~~~NO -* N + 627.9 150.1 (2)~~~~~~

~~~~~~N0„ - NO + 300.5 71.83 (2)~~~~~~

~~~~~~NO - N0 + 205±21 49±5 (2) N-0 2~~~~~~

~~~~~~NO - N + NO 474o9±4 113. 5±1~~~~~~

~~~~~~- N + 38.58 (2) 2 161.3 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~~~~~~

~~~~~~HNO - H + NO 203 48,6 (2)~~~~~~

~~~~~~- NH + 475 113.5~~~~~~

~~~~~~trans-HN0 - 2 HO + NO 209. 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 + 378 90.4 (2,3) 3~~~~~~

~~~~~~-» H + H C = 88.2 21.1 (2,3)~~~~~~

~~~~~~+ 41.5 CH 3°2 ~* ^S 173. (2,3)~~~~~~

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

~~~~~~CH -» CH + H 469.9 + 0.,4 112.3 ± 0,,1 3 2~~~~~~

~~~~~~CH. - CH„ + H 425.1 + 8,.4 101.6 ± 2.,0 4 3~~~~~~

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

~~~~~~-» CH + H0 295. 70.6 (2,3) 3 2~~~~~~

~~~~~~CH ONO -» CH + N0 248 59.2 (2,3) 3 2~~~~~~

~~~~~~CH N0 -* CH + N0 254 60.6 (2,3) 3 2 3 2~~~~~~

~~~~~~CH ON0 -» CHO + N0 174 41.6 (2,3) 3 2 2~~~~~~

~~~~~~-» CH + N0 341 81.6 (2,3) 3~~~~~~

~~~~~~SO -» S + 517.1 + 8 123.6 + 2 so -> SO + 547.3 + 8 130.8 ± 2,,0 2 + 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 8 »~~~~~~

~~~~~~1* .3 * - S.3~~~~~~

~~~~~~& -~~~~~~

ft 3 c « 5 1 o O a a a i •H O IO J? 3 N 1 ** 5 8 < • 1 0. <3 3K X o & 6- o iH .H •H «H M M H M pj 3 a s a Ok CM S 3 '_ 5 ' ! t • • • • <7l O W O O •-4 o o «H O M i tH ri iH iH M +1 +1 H H tO I EH «" M N* W M (M 0> •< e- o o • • • • • en 10 eg p- rvj CO 2 £

~~~~~~S* M~~~~~~

~~~~~~£ s.~~~~~~

~~~~~~i ! 5 o A « e a aj 5~~~~~~

~~~~~~O 3 siO — J- ft c\j o S Bf I: I x r 3 ».~~~~~~

*» ow e B 5 * to i 1 8 • • O) i i r> Oi 0-1

~~~~~~108 i~~~~~~

~~~~~~01 rH J? & & & & & & & j? 5 * -*saassBaBB~-: •** *-* *-< ~-4 ~4 -H -: 1 I~~~~~~

~~~~~~s v~~~~~~

~~~~~~-* a IS ~-» CM~~~~~~

~~~~~~u £ a 5 ^ H f-4 S iO CD — m • • 0) >H •9 0) lO t> o CD o s CM «H (- •H -o o 5~~~~~~

~~~~~~^ £ bT~~~~~~

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~~~~~~ir ^> <-. t.~~~~~~

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§1o » i*. 4) 05 *

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~~~~~~5 5 9 ,2~~~~~~

~~~~~~107 1~~~~~~

» -^ to a.2 *

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~~~~~~: i~~~~~~

~~~~~~s s rt ~~SapL. w w t o 01 + e * ~ o u c S £ I i fe 1~~~~~~~~

~~~~~~•-< • £ g o & F £ fi B~~~~~~

108 rcot I'.- .5 o CM & S 4* 1=1 *-> a) s R CO * a 33 co U4 t/1 + 9 fa «I +J» o • « *» •cj O «J 33 *» » Si as a (S 9 t3 V u S §

~~~~~~8 * (E a) J= *> CM t CO p. s a CO "A CO O CO JS o 3 3 a o O w *-- en «c; • o *» CD • (X, a! P. S3~~~~~~

it) U *H s-a CO 1-4 CO JCJ o o O s O U cm «*

E eg + CO «) *% O PS CM » rH II CO BEJ £ *» 01 a s. » II t-t !* *4 *-^ *> •"2 I o e »« CO 13 CM tp • T-t Sen do CM p3 *j • p* <] «M «H a) co i o3 «.a) ".* S3 o «* "51 >J i • u ft a Sua • X CO co e +* eo o ** S & 3 3* ri *

~~~~~~109 ' » » '' '' ' ' ' i' > '» • 'i' »1~~~~~~

~~~~~~I-1 1 rt t— rt I-1 rt rt at 1~~~~~~

~~~~~~3 total 01 O 3 ex n > ro rt 3 LO 3 3 ppm 3 LO 3 LO Lo 1 a o 3 3 i 298K, "I rt o rt o o rt CO 00. rt h-i h-~~~~~~

~~~~~~CO min • 1 (D rt 1 1 1 rt O CO I-1 rt 1— 1 pressure rt c 1 CO CO "I II. CO rt h-» 1 1 1 II atm. = 1 CD I- rt~~~~~~

~~~~~~rt 1 II 1 I- II II II CO~~~~~~

~~~~~~1 rt~~~~~~

~~~~~~o 3 00 00 OS OS h- 1— rt CO LO X lO X • X • O o I-1 o ro o OS LO 6 rt ~J o F-1 LO l—1 to rt O ^1 OS O OS O Lo i H 00 CO rt H 1-3 LO CO 1 J—~~~~~~

~~~~~~00 00 OS Os rt rt 3 x • X • ro X O (-* O LO LO o CO o LO 1 3 I-1 rt O LO rt ro LO o O --4 O Os OS O LO rt Ln 1 ro 1 rt ro rt o rt rt CO~~~~~~

~~~~~~1 rt~~~~~~

~~~~~~3 00 oo Os OS I-" rt LO X o X • X • x • I-1 O o 3 LO to ro o l o rt rt I-* o I-1 LO I-1 ro LO OS rt I> O J>- O OS O OS O LO 1 1 1 1 1 I- LO Ln to CO i-3 H rt 1 rt~~~~~~

n 3 c LO CD CO as h-i h-1 t-1 i-i 3 1 (D re X X X X X • X o h- rr LO LO O rt OS Os OS rt1 1 1 pd CO H- 00 rt as rt OS rt LO h-> OS rt Os I- OS CD o o O ro O Ln O O o O (U 1 1 1 1 l c o K) I-1 IO H^ (-* to ro rt O as IO SO 00 H-1 4^ CD K- o 3 H H rt 1 O rt 3 CO CO LO rt 3 3* rt o CD < i O o O CO (— so 1— c CO 3 rt X X • OS X X 1 < rt LO Os OS Os 3 CD lo so t-* rt ID rt - M Ln O o rt O H LO O OS O 00 .£> O J> O .O re rt 3 CO 1 rt oo C rt LO 00 rt ro Ln j— O rt i rt rt i 1 i— HI rt 3 1 i— O rt CO T3 Hi 1 Co h-1 oo v; O CD

rt rt rt h-i 01 o X • Os X • X ro X rt as H~* O LO ro ro 1 I- OS rt £~ h-i h-1 >-• i— 1 LO O ~sl O O so so O so h-1 ro ro .E- 1 CO Ln l-1 rt rt ro 1-3 I rt rt CD j-1 X l i rt i— h-i M O O Os OS ro ro lo -o l> X X X X • X • X •o O t-1 X Ln J> .o 3 (- ~-j I-4 Os l-" -o I-1 Ln rt Ln rt Ln O SO h- O O 00 O LO O LO O L0 rt 1 O l h- 1 1 3 LO ho Ln LO OS SO Ln 3 1 l-»

~~~~~~h- SO »— 1— 3 OS X X ro X • X • N) - 00 Ln ISO o ro ro I-1 OS O rt O >- O |W Ln O SO O O J^ LO O LO O LO 1 1 I- t 1 I-* LO SO rt rt X~ CO H i rt rt 1 l rt i h- h-i rt~~~~~~

~~~~~~110 < i 1~~~~~~

~~~~~~CM CM CM~~~~~~

~~~~~~i i-H c OS en i-H r-4 i-H 1^- 00 m e 1 CM i O 1 CM on o n o CO o o o i-H o s0 1 O r-H O i-l O r-H~~~~~~

~~~~~~CM CM~~~~~~

~~~~~~1 CM i-i H 1 H~~~~~~

~~~~~~i CM~~~~~~

~~~~~~1 CM CM CM H 1 O H H i-H~~~~~~

~~~~~~r-4~~~~~~

~~~~~~1 CO CM CMH CMH CMH cu CO CM sO 00~~~~~~

~~~~~~r-H CM CM CM co H H H CM m CO a\ in CO 1 i SO i r-H CM oo o o CO O o o O i-H S0 CM i-l 0\ r-H CO i-H r- i-H 1-H r-H s 1 1 so CO Os OS o o t-1 . X X . X X X e 1-1 i-4 CO CO sO o\ sO~~~~~~

~~~~~~CM 10 CM H CM 1-1 H CO CM CM 1 -cr CO 1 i— H r-H CO o o CO O o O s0 CM i-H ON t—1 CO r-H l~- r-H i-4 B 1 SO SO 00 ON vO o r-4 O X X X . X OS 6 i-4 i-H CO CO sO OS SO T3~~~~~~

~~~~~~1-1 1 CM CM CM CO 1^- H H CO H CM~~~~~~

~~~~~~1-1~~~~~~

~~~~~~10 II~~~~~~

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~~~~~~111 i1 1 1 1 1 i( 1 1 \ 1 ( 1 11 1 I 1 '~~~~~~

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~~~~~~r— X X X X X X~~~~~~

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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 1~~~~~~

~~~~~~U.S. DEPT. OF COMM. 1. I'l'HI.K A 1 ION OH Kl POR 1 NO. 2. dov't Accession 3. Recipient's Accession N< BIBLIOGRAPHIC DATA No. SHEET NBS TN-866~~~~~~

~~~~~~4. II I !.!: ANI1 SUBTITLE 5. Publ icat ion Date~~~~~~

~~~~~~Chemical Kinetic and Photochemical Data for June 1975 Modelling Atmospheric Chemistry 6. Performing Organization ( o<~~~~~~

~~~~~~7. author(S) 8. Performing Organ. Report No.~~~~~~

R. F. Hampson, Jr. , and David Garvin; Editors 9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. Project /Task/Work Unit Ni NATIONAL BUREAU OF STANDARDS DEPARTMENT OF COMMERCE 11. Contract/Grant No. WASHINGTON, D.C. 20234 3165409

12. Sponsoring Organization Name and ( omplete Address (Street, City, State, ZIP) 13. Type of Report & Peril ( Covered Final Department of Transportation 14. Sponsoring Agency ( ode Washington, D.C. 20590

~~~~~~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

~~~~~~19. 21. NO. OF PAGES 18. AVAILABILITY [X Unlimited SECURITY CLASS (THIS REPORT) 118 For Official Distribution. Do Not Release to NT1S UNCLASSIFIED~~~~~~

~~~~~~i 20. ( 22. Price (X ^rdcr From Sup. of Doc,:., U.S.u..>. Government Printingrmtinu y\Office SECURITY LASS Washington, D.C. 2010 2, sn < at. No. ( i ^:46:866 (THIS PAGE)~~~~~~

~~~~~~Order From National Technical Information Service (NILS)~~~~~~

~~~~~~Springfield, Virginia 2 2 I "S UN( LASSIFIED U5COMM-DC 29042-P74 NBS TECHNICAL PUBLICATIONS~~~~~~

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National Standard Reference Data Series—Provides Order NBS publications (except NBSIR's and Biblio- quantitative data on the physical and chemical proper- graphic Subscription Services) from: Superintendent of ties of materials, compiled from the world's literature Documents, Government Printing Office, Washington, and critically evaluated. Developed under a world-wide D.C. 20402. BIBLIOGRAPHIC SUBSCRIPTION SERVICES The following current-awareness and literature-survey survey issued quarterly. Annual subscription: $20.00. tonographies are issued periodically by the Bureau: Send subscription orders and remittances for the pre- (Oogenic Data Center Current Awareness Service ceding bibliographic services to National Technical A literature Information Service, Springfield, Va. 22161. survey issued biweekly. Annual subscription: Domestic, $20.00; foreign, $25.00. Electromagnetic Metrology Current Awareness Service Liquefied Natural Issued monthly. Annual subscription: Gas. A literature survey issued quar- $100.00 (Spe- terly. Annual subscription: $20.00. cial rates for multi-subscriptions). Send subscription order and remittance to Electromagnetics Division, Superconducting Devices and Materials. A literature National Bureau of Standards, Boulder, Colo. 80302. U.S. DEPARTMENT OF COMMERCE National Bureau of Standards Washington. DC. 20234 POSTAGE AND FEES PAID U.S. DEPARTMENT OF COMMERCE OFFICIAL BUSINESS COM-215 SPECIAL FOURTH-CLASS RATE Penalty for Private Use. $300 BOOK

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