NBSIR 80-2118

Tables of Rate Constants for Gas

Phase Chemical Reactions of

Sulfur Compounds (1971-1979)

Francis Westley

Chemical Kinetics Division

Center for Thermodynamics and Molecular Science

National Measurement Laboratory

National Bureau of Standards

U.S. Department of Commerce

Washington. D.C. 20234

July 1980

Interim Report

Prepared for Morgantown Energy Technology Center

Department of Energy

Morgantown, West Virginia 26505

Fice of Standard Reference Data

itional Bureau of Standards

ashington, D.C. 20234

c, 2 Jl
1

m

*
NBSIR 80-2118

TABLES OF RATE CONSTANTS FOR GAS

PHASE CHEMICAL REACTIONS OF

SULFUR COMPOUNDS (1971-1979)

Francis Westley

rational bureau

07 STANDARDS

LIBRARY

wov 2 4 1980

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im

Chemical Kinetics Division

Center for Thermodynamics and Molecular Science

National Measurement Laboratory

National Bureau of Standards

U.S. Department of Commerce

Washington, D.C. 20234

July 1980

Interim Report

Prepared for Morgantown Energy Technology Center

Department of Energy

Morgantown, West Virginia 26505

and

Office of Standard Reference Data

National Bureau of Standards

Washington, D.C. 20234

U.S. DEPARTMENT OF COMMERCE, Philip M. Klutznick, Secretary

Luther H. Hodges, Jr., Deputy Secretary

Jordan J. Baruch, Assistant Secretary for Productivity, Technology, and Innovation

NATIONAL BUREAU OF STANDARDS. Ernest Ambler, Director
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Table of Contents

Abstract 1 Introduction 2 Guidelines for the User 4

Table of Arrhenius Parameters for Chemical Reactions of

Sulfur Compounds 12

Reactions of: S(Sulfur atom) 12

$2(Sulfur dimer) 20

S0(Sulfur monoxide) 21

S02(Sulfur dioxide 23

S0

3

(Sulfur trioxide) 28

S20(Sul fur oxide^O) ) 29

SH (Mercapto free radical) 29

H2S (Hydroqen sulfide 31

CS (Carbon monosulfide free radical) 32

CS2 (Carbon disulfide) 33

COS (Carbon oxide sulfide) 35

CH^S* ( Methyl thio free radical) 36

CH^SH (Methanethiol ) 36

cy-CF^CF^S (Thiirane) 37

CH^SCF^* (Methyl, (methyl thio)-, free radical) .... 38

CH^CF^SH (Ethanethiol ) 38

(CH-^S (Methane, thiobis-) 39

CH3SO2CH3 (Methane, sulfonylbis-) 39

cy-CF^CF^CF^S (Thietane) 40

cy-fCFIgJCHCF^S (Thiirane, methyl-) 40

( CH

3

) gCHSH (2-ProDanethiol ) 40

cy-CF^CF^CF^CF^S (Thiophene, tetrahydro-) 40

CHgCfSjSCF^CHg (Ethane(dithioic) acid ethyl ester) . . 40

CFIgCF^CF^CF^SH (Butanethiol ) 40

( CH3) 3CSFI (2-Propanethiol , 2-methyl-) 41

CF^CFICF^SOgCH^ (1-Propene, 3-methyl sul fonyl ) 41

CH^SC^OCF^CFIg (Carbonothioic acid 0-ethyl

S-methyl ester). 41
CH

3

0C(0)SCH

2 CH

3

(Carbonothioic acid S-ethyl

0-methyl ester) . 41

CH

3

0C(0)SCH(CH

3 )2 (Carbonothioic acid 0-methyl

S- (1 -methyl ethyl ) ester) 41

CH

3

SC(0)0CH(CH

3 )2 (Carbonothioic acid S-methyl

0- (1 -methyl ethyl ) ester) 41

CH

3

SC(0)0C(CH

3 )2 (Carbonothioic acid 0-(l ,1 -dimethyl

ethyl) S-methyl ester) 41

CH

3

0C(0)SC(CH

3

) 3

(Carbonothioic acid S-(l ,1 -dimethyl

ethyl) 0-methyl ester) 42

CH^SjSCE^C^C^C^ (Ethane(dithioic) acid butyl

ester) 42

CH

3 C(S)SCH(CH3

)CH

2

CH

3

(Ethane(dithioic) acid 1-methylpropyl ester) 42

CH

3 C(S)SC(CH

3

) 3

(Ethane(dithioic) acid 1,1-dimethyl

ethyl ester) 42

Bibl iography 43

Appendix: Conversion Tables 54
TABLES OF RATE CONSTANTS FOR GAS PHASE CHEMICAL

REACTIONS OF SULFUR COMPOUNDS (1971-1979)*

Francis Westley

National Bureau of Standards

Chemical Kinetics Division

Center for Thermodynamics and Molecular Science

Washington, DC 20234

A table of rate constants for gas phase chemical reactions of

sulfur compounds is presented. Specifically, it gives in tabular form

the values of the parameters for the modified Arrhenius equation k =

B _ AT exp(-E/RT). The table covers the reactions of sulfur containing

molecules and free radicals - S, S

2

, SO, S02» SO^, S

2

O, SH, H

2

S, CS,

CS

2

, COS, CH^S*, CH^SH, cy-^CHgS, CH-^SC^* and a number of thiols,

thioethers and thioesters - with other compounds. The table includes 16

unimolecular, 187 bimolecular, and 11 termolecular reactions totalling

214 distinct chemical reactions. There are 348 distinct entries, distributed

as follows: 26 for first order reactions, 294 for second order reactions

and 28 for third order reactions. The kinetic data were compiled from

109 experimental papers and 6 critical reviews published between 1970

and 1979.

Key words: Arrhenius parameters, chemical kinetics, combustion, decomposition,

free radicals, gas phase, hydrocarbons, hydrogen, nitrogen

oxygen, rate of reaction, sulfur.

This work was supported by the Department of Energy and by the Office

of Standard Reference Data of the National Bureau of Standards.
2

INTRODUCTION

This publication consists of a table of rate constants for reactions

of inorganic and organic sulfur compounds in the gas phase, as well as

of their reactions with other bodies. The table is a compilation of

rate constants given in 109 experimental papers and 6 critical reviews

published between 1970 and 1979. Its purpose is to provide the kineticist

and combustion modeler with a comprehensive and easy-to-use source on

kinetic data for chemical processes involving sulfur compounds. The

table gives 348 distinct reaction rate constants from the above mentioned

sources. A list of references including the 115 papers, arranged alphabetically

by author for each separate year, is appended at the end of the table.

For ease of reference the sulfur-containing reactant in a bimolecular

or termolecular reaction is always placed first, so that a grouping of

the reactions according to the standard order of sulfur compounds is

obtained. However, 14 bimolecular reactions and one termolecular reaction

involve two sulfur-containing reactants. For that reason, these 15

reactions are listed twice, the second time with the order of the sulfurcontaining reactants reversed. (E.g.: COS + S -> CO + S£ is also listed

as: S + COS -* Sp + CO.) As a result, the total number of tabulated

entries is 363, although the real number of distinct entries is only

347. The arrangement of the tables and the standard order of chemical

compounds are described in detail below, in the "Guidelines for the

User".

The presentation of kinetic data is standardized and simplified as

much as possible. Rate constants are expressed in terms of the modified

D Arrhenius equation k = AT exp(-E/RT). In general uncertainties are

given only for the rate constant k itself and not for the individual
3

parameters in this equation. Sometimes an uncertainty is given for the

value E/R and has been included in the uncertainty stated for the value

of the rate constant. Rate constants are expressed in units of s \

o I -] c _ o i cm mol s , and cm mol s for reactions of first, second and third

order respectively. Conversion tables for other units are appended at

the end of this publication.

This publication is not the result of the effort of a single person,

but of the whole staff of the Chemical Kinetics Division. My thanks to

all of them. In particular, I wish to thank Dr. David Garvin, Deputy

Director of the Center for Thermodynamics and Molecular Science, and Dr.

Robert F. Hampson, Jr., Director of the Chemical Kinetics Information

Center, for their more than helpful suggestions and constant guidance;

Dr. Wing Tsang, Chief of the Chemical Kinetics Division, and Dr. John T.

Herron of the Chemical Kinetics Division, for their encouragement; Dr.

Bert R. Staples, Chief of the Electrolyte Data Center, for allowing us

to program the tables through a computer; Mrs. Betti joyce Molino and

Mrs. Carla G. Messina from the Office of Standard Reference Data for

applying the OMNIDATA and GPSDIC programs to the present tables; and

Mrs. Janice L. Jones and Mrs. Delores E. Dorman for typing a difficult

typescript with particular care.
4

GUIDELINES FOR THE USER

General

As pointed out above, the presentation of the kinetic data in this

publication is an attempt to simplify and standardize them. Units of

rate constants used in this table are the cubic centimeter, the mole and

the second. The choice of a standard form for uncertainty limits is

somewhat more complicated, but when a series of recommended rate constants

is to be presented in a tabular form, the uncertainty limits can not be

omitted, for an uncertainty assigned to the recommended value of a rate

constant is an estimate by the evaluator of the absolute accuracy of the

preferred value. It is to be emphasized that in the present tables the

concern is with the overall uncertainty of a reaction rate constant and

not with the expression of precision of a set of experimental measurements.

Most of the uncertainty limits included in this table are uniform within

the respective temDerature ranae indicated. However, for a limited

number of reactions, the data warrant or require variable limits. In

such cases, a note under the respective data indicates for which interval

of the temperature range there is a change in the uncertainty limits.

It is thouqht that the uncertainty limits expressed in the form of

lower and upper k factors - f and F, respectively - are the most suitable

for tabulation. Thus, if k Q

is the central value of a rate constant the

limits of reliability for the rate constant k Q are defined by the

relationship:

fk

Q < k < Fk

o (1)

i.e. multiplication of the central value k Qby f and F gives respectively

the lower and upper reliability limits of the rate constant. In this
5

standardized formulation of uncertainty limits, the value of f is less

than unity and the value of F is greater than unity.

However the k factors are not the only way to express the uncertainty

limits of a rate constant and different authors use different forms to

indicate the degree of reliability of a recommended rate constant. It

follows that certain mathematical relationships are needed to translate

the different forms of uncertainty limits into the standard form used in

this table (lower and upper k factors). The formulas used to transform

any form of uncertainty limits into the standard form were given and

discussed at length in the introduction of a previous publication and

will not be repeated here.

Arrangement of the table

This publication is in two parts:

Part I . The table arranged in nine columns gives the chemical

reaction, the order of reaction n, the "third body" collision partner M,

the rate constants ratio k/k

rg ^, the temperature range in kelvins, the

D parameters A, B and E/R for the modified Arrhenius equation k = AT exp(-

E/RT) and the uncertainty limits expressed as k factors f and F.

Part II . The bibliography of part I, including the full references

for the 109 experimental papers and 6 critical reviews from which the

present table was compiled. Following the bibliography, two conversion

tables for equivalent second and third order rate constant units are

appended.

The arrangement of the table in part I is as follows:

Column 1 the chemical reaction indicating both the reactants and

the products. In the same column, under each chemical reaction, the

* Wcstley, Francis, "Tables of Recommended Rate Constants for Chemical

Reactions Occurring in Combustion", NBSIR 79-1941 (1979) (1st ed.);

NSRDS'-NBS 67 (1930) (2nd ed.).
6

names of the reactants are given. The chemical nomenclature adopted is

the one used in the Chemical Substance Indexes of Chemical Abstracts.

Alternative names are not given. The chemical names of the products are

not given. The line with chemical names is indented with respect to the

line above it. Under the chemical names, the short reference to the.

reviewer's book or article is given.* It includes the last two digits of

the year of the publication followed by the first three letters of the

author's name. If two authors are given, a slash separates each author's

three letters. Again, the short reference line is indented with respect

to the line above it. e.g.:

78 MAR/HER indicates the experimental rate constant for the

reaction between dimethyl sulfide and ozone, published

by Martinez and Herron in 1978.

The last line of column 1, placed under the line including the

short reference, begins with the heading NOTE:. It is given only when

necessary and might include information about the dependence of k factors

on temperature range, or the reaction taken as reference when a value

for the ratio k/k^ is given in column 3, or other information pertinent

to the reaction indicated above. For a couple of reactions . taken from

Baulch, et al . (76 BAU/DRY) the relationship k-j = Kk_^ included in the

note indicates that the rate constant was calculated from the equilibrium

constant K and the rate constant k_-j of the reverse reaction. In such

cases, the author usually gives the rate constant of the reverse reaction

immediately after the data for the forward reaction. The arrangement of

the present table based on the standard order, does not allow the forward

rate constant of a reaction to be followed immediately by its reverse

rate constant. The reader will have to locate the rate constant of a

reverse in its proper place in the table.
7

Column 2 , with the heading n, indicates the order of the reaction

displayed in column 1. The value of n is 1, 2, or 3, which defines the

proper standard units for the reactions, as follows:

1 for first order reactions s

3 -1 -1

2 for second order reactions cm mol s

6 -2 "1

3 for third order reactions cm mol s

The reaction order is indicated for every reaction included in the table

and the digit indicating its value is aligned with the short reference.

Column 3 , with the heading M, defines the inert reaction partner

("third body") when the chemical reaction displayed in column 1 includes

the letter M. Most of the third bodies displayed in column 3 include no

more than three characters (e.g.: Ar, He, H

2

O, ^ ^0, SC^, SO^, CC^).

For the reaction SO

2 + OH + M -* HOSO

2 + M the third body, a mixture of

N

2 and Og, is indicated in the note, in column 1. No indication is

given if M is undefined in the paper. When displayed, the third body is

aligned with the short reference and the reaction order.

Column 4 , with the heading k/k gives the ratio of the rate

constant of the reaction indicated in column 1 and the rate constant of

a reference reaction. In most cases this ratio is a dimensionless

number. However, when the order of the reaction indicated in column 1

is different from the order of the reference reaction, the ratio of the

rate constants is no longer dimensionless and the expression for the

ratio of rate constants is not given in column 3 (for lack of space),

but in the note, at the end of column 1. The reference reaction is

always indicated in the notes. The dimensionless rate ratios given in

column 3 are aligned with the short reference given in column 1 and with

the reaction order given in column 2.
8

Column 5 , with the heading T/K, gives the temperature range of

validity for the corresponding rate parameters. For some reactions only

one temperature is given, meaning that the reaction was studied only at

one temperature. If no temperature is indicated, it means that the

kinetic parameters of the corresponding reaction are valid throughout.

The data estimated by Benson and Golden in their report "Estimating the

Kinetics of Combustion" (75 BEN/GOL) are in this category. The temperatures

are aligned with the short references given in column 1, as well as with

the reaction order given in column 2.

Column 6 , with the heading A, gives the value of A for the equation

D k = AT exp(-E/RT). A is expressed as a number less than 10 followed by

the exponent in parenthesis, e.g., 3.5 (+ 14) should be read as 3.5 x + 1

10 . The coefficient of the A factor has no more than one digit after

the decimal point. The units of the A factor are the same as for the

rate constant. For those cases when the recommended value is only for

one temperature , the entry under this column is in fact the value of

the rate constant k at this temperature. The data for the A factor are

aligned with the short reference and reaction order information. If a

dash appears in this column, it means that no A factor value was reported

by the evaluator for the corresponding reaction. In such a case a rate

ratio is given in column 4.

Column 7 , with the heading B, gives the value of B for the equation

B _

k = AT exp(-E/RT). The value of B usually lies between 0 and 4, negative

or positive. No more than one digit is given after the decimal dot. A

dash in this column means that no B value was reported by the evaluator.

The data for B are aligned with the short reference and reaction order

information.
9

Column 8 , with the heading E/R, indicates the value of E/R for the

D equation k = AT exp(-E/RT). Since E is the activation energy in cal

mol"^ and R the gas constant with a value of 1.987 cal mol K

*

, it

follows that the units of E/R are kelvins. The values given in column 5

for E/R may vary from 0 to over 100000 kelvins. The E/R values may be

positive or negative. Some of the E/R values included in the table are

followed by an uncertainty with plus or minus signs. As pointed out in

the introduction, these uncertainties may be ignored, as they are included

in the lower and upper k factors indicated in the right column of the

table. A dash in this column means that no E/R value was reported by

the evaluator. The values for the E/R factor are aligned with the

short reference and reaction order information.

Column 9 , with the heading "k factors" and two subheadings, "f" and

"F", indicates the two uncertainty k factors, the lower factor f in the

left subcolumn and the upper factor F in the right subcolumn. To find

the uncertainty limits of a reaction, its rate constant is to be multiplied

by the two factors, as shown in (1): fk

Q

< k < Fk

Q

. The values of both

factors are always positive. If no uncertainty limits are indicated by

the evaluator, both subcolumns of the column 6 are left blank. The k

factors are aligned with the short reference and reaction order information.

Ordering of chemical reactions .

The general rule for ordering the chemical reactions listed in

column 1 of the table is the standard order of arrangement as described

in NBS Technical Note 270-3 . A detailed discussion of this rule was

presented in the introduction to the publication noted in the preceding

footnote (NBSIR 79-1941/1979, or NSRDS-NBS 67/1980) - and will

* Wagman, D.D. , Evans, W.H., Parker, V.B., Halow, I., Bailey, S.M. , and

Schumm, R.H., "Selected Values of Chemical Thermodynamic Properties,"

NBS Tech. Note 270-3 pgs. 5, 16, 22 (1968).
10

not be repeated here. It suffices to say that this rule is applied to

the first reactants of the reactions listed in this table, as well as to

the reactants following the first, and that the first reactant of a

reaction takes precedence over the following ones. The compounds listed

in the Table of Contents, which give only the first reactants of the

chemical reactions included in this work, are in the standard order (S,

S

2

, SO, S0

2

, S0

3

, S

2 0, SH, H

2

S, CS, CS

2

, COS, CH

3

S-, cy-CH

2

CH

2 S, etc.)

and are each part of the S_-0-H-C system. (The first reactant always

includes an S atom, and may include any of the 0, H, or C atoms). The

second, or the third reactants may include any of the 0, H, S, N, or C

atoms, and this sequence - arranged according to the standard order -

defines the 0-H-S-N-C system.

A number of second and third order reactions includes a second

and - respectively - third body M. For this type reactions, M will always be

placed after all other reactants , (e.g. : S0

3 + M -* S0

2 + 0 + M, or SO

+ 0 + M - S0

2 + M).

Most of the chemical reactions included in the table are balanced.

There are a number of reactions with unspecified products. In such a

case, the word "products" appears after the arrow (e.g.: S0

2 + H0

2

->

products)

.

Display of Chemical Reactions and Formulae

In order to define the reaction products, the reactants are written

using semi -structural formulas. All saturated normal hydrocarbons are

written so as to show separately each methyl and methylene group in the

chain: CH^, CH

3

CH

3

, CH

3

CH

2

CH

3

. Unsaturated hydrocarbons are written so

as to show the position of double or triple bonds. The unpaired electron
n

of an alkyl radical is always indicated, with the exception of Methyl

free radical, e.g.:

Methyl free radical CH^ (no dot)

Ethyl, 1 -methyl-, free radical (Isopropyl) (CH^CH*

Methyl, hydroxy-, free radical

Methyl thio free radical

•ch

2

oh

ch

3 sIf the unpaired electron of an alkyl radical belongs to a carbon in

the middle of the chain, it is indicated inside a parenthesis following

the carbon atom, e.g.:

Propyl, 1 -methyl-, free radical (sec-Butyl) CH

2

CH

2

CH( • )CH

2 If the oxyaen atom of an oxy radical is attached to the terminal

carbon atom, the radical is written in the usual manner: CH^O. If the

oxygen atom of the oxy radical is attached to a C atom in the middle of

the chain, then the oxygen atom, together with the unpaired electron,

are inside a parenthesis following the C atom: (CH

2

) 2 C(0‘ K^CH^.

The rules for writing peroxo, and other free radicals are the same as

for the oxy free radicals: CH^*, CH^S.

Atoms, like 0, H, S, N, C, and simple radicals like OH, HO^ , SH,

NH, CH, CH

2

, CH^, CS, CN are written without dot.
12

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43

Bibl iography

1970

70 BEN/O'N Benson, S. W., and O'Neal, H. E., "Kinetic Data on Gas Phase

Unimolecular Reactions," NSRDS-NBS 21 (1970). (Supt.

Doc., U. S. Govt. Printing Office, Washington, D.C.

20402).

1971

71 ARM/CUL Armitage, J. W. , and Cull is, C. F., "Studies of the Reaction

between Nitrogen Dioxide and Sulfur Dioxide," Combust,

and Flame 16, 125 (1971 ).

71 BAU/JEF Bauer, S. H., Jeffers, P., Lifshitz, A., and Yadava, B. P.,

"Reaction between CO and SO

2

at Elevated Temperatures:

A Shock-Tube Investigation," Symp. Combust. 13 (Combustion

Institute Pittsburgh, Pa., (1971) 417.

71 CON/VAN Connor, J. Van Roodselaar, A., R. W., and Strausz, 0. P.,

"The Addition of Group Via Atoms to Tetramethyl thylene.

An Addition Reaction with a Negative Activation Energy,"

J. Am. Chem. Soc. , 93, 560 (1971 ).

71 FIF/MOR Fifer, R., Moreau, R. , and Bauer, S. H., "The Reactions

between S0£ and C

2

H

2

(and ^H^) at Elevated Temperature.

A Single-Pulse Shock Tube Investigation," Int. J. Chem.

Kinet. 3, 249 (1971 ).

71 HAN/SMI Hancock, G., and Smith, I. W. M., "Infra-red Chemiluminescence

from Vibrational ly Excited CO. Part 1. The Reaction of

Atomic Oxygen with Carbon Disulphide," Trans, of Faraday

71 KRE

Soc, 67, 2568 (1971).

Krezenski, D. C., "Competitive Reaction of 0( P) with Ozone

and Carbonyl Sulfide," Diss. Abstr. Int. B 32_, 2633 (1971 ) 71 KRE/ SIM Krezenski, D. C., Simonaitis, R. , and Heicklen, J., "The

3 Reactions of 0( P) with Ozone and Carbonyl Sulfide," Int.

J. Chem. Kinet. 3, 467 (1971).

71 KUR/PET Kurylo, M. J., Peterson, N. C., and Braun, W., "Absolute Rate

of the Reaction H + H

2

S," J. Chem. Phys. 54, 943 (1971).
44

71 MER/LEV

71 MIY/TAK1

71 MIY/TAK2

71 STR/O'C

71 TAK

72 DAV/KLE1

72 DAV/KLE2

72 DON/LIT

72 HAN/RID

72 JAC/WIN

Merryman, E. L. , and Levy, A., "Sulfur Trioxide Flame ChemistryH

2

S and COS Flames," Sym. Combust. 1^, (Combustion

Institute Pittsburgh, Pa., 1971) 427.

Miyazaki, S. , and Takahashi, S., "On the Reaction of Oxygen

Atom with Carbon Disulphide, Part 2. Memoirs of the Defense

Acad. (Japan) Vj_» 307 (1971 ).

Miyazaki, S., and Takahashi, S., "On the Reaction of Oxygen Atom

with Carbon Disulphide. Part 3. Memoirs of the Defense

Acad. (Japan) Tl_, 329 (1971 ).

Strausz, 0. P. , O'Callaghan, W. B., Lown, E. M. , and Gunning, H. E.,

"Reactions of Sulfur Atoms. XII. Arrhenius Parameters

for the Addition to Olefins and Acetylenes," J. Am.

Chem. Soc. 93, 559 (1971 ).

Takahashi, S., "On the Reaction of Oxygen Atom with Carbon-Disulphide.

Part 1," Memoirs of the Defense Acad. (Japan) 1J_, 191 (1971).

1972

Davis, D. D. , Klemm, R. B. , and Pilling, M. , "A Flash Photolysis-Resonance Fluorescence Kinetics Study of Ground-State

Sulfur Atoms: I. Absolute Rate Parameters for Reaction

of S(

3

P) with 0

2

( 3 !)," Int. J. Chem. Kinet. 4, 367 (1972).

Davis, D. D. , Klemm, R. B., Braun, W., and Pilling, M.

"A Flash Photolysis-Resonance Fluorescence Kinetics Study

of Ground-State Sulfur Atoms. II. Rate Parameters for

Reaction of S(

3

P) with C^," Int. J. Chem. Kinet. 4,

383 (1972).

Donovan, R. J., and Little, D. J., "The Rate of the Reaction

S(

3 P

j

) + 0

2

," Chem. Phys. Lett. 13., 488 (1972).

Hancock, G., Ridley, B. A., and Smith, I. W. M. , "Infra-red

Chemiluminescence from Vibrationally Excited CO. Part 2.

Product Distribution from the Reaction 0 + CS ^ CO + S,"

Chem. Soc., Faraday Trans. II 68, 2117 (1972).

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

of Oxygen Atoms and Nitrogen Atoms with Sulfur Trioxide,"

J. Chem. Soc., Faraday Trans. I 68_, 2077 (1972).
45

72 JAK/AHM Jakubowski, E. , Ahmed, M. G., Lown, E. M. , Sandhu, H. S.,

Gosavi, R. K. , and Strausz, 0. P., "Sulfur Atom Abstraction

from Epi sulfides and Carbonyl Sulfide by Methyl Radicals,"

J. Am. Chem. Soc. 94, 4094 (1972).

72 KER/PAR Kerr, J. A., and Parsonage, M. J., "Evaluated Kinetic Data on Gas Phase Addition Reactions: Reactions of Atoms and Radicals

with Alkenes, Alkynes and Aromatic Compounds," (Butterworths,

London, 1972).

72 LAN/OLD Langford, R. B., and Oldershaw, G. A., "Flash Photolysis of

72 LIT/DAL

H

2

S," J. Chem. Soc., Faraday Trans. I 68, 1550 (1972).

Little, D. J. , Dalgleish, A., and Donovan, R. J., "Relative

Rate Data for the Reactions of S^Dg) using the NS Radical

as Spectroscopic Marker," Faraday Dis. Chem. Soc. 53_, 211

(1972).

72 NIK/MORI Niki, H. , Morris, E. D. Jr., and Breitenbach, L. P., "Reaction

of OH with H

2

S," Am. Chem. Soc. 164th Meeting (Abstracts of

Papers) 164, PHYS-116 (1972).

72 ROM/SCH Rommel, H., and Schiff, H. I., "The Reactions of H Atoms with

72 WOR/COL

H

2

S and COS," Int. J. Chem. Kinetics 4, 547 (1972).

Worley, S. D. , Coltharp, R. N. , and Potter, A. E. Jr., "Rates

of Interaction of Vibrationally Excited Hydroxyl (v = 9)

with Diatomic and Small Polyatomic Molecules," J. Phys. Chem. 76, 151 1 (1972).

1973

73 BRA/TRU Bradley, J. N., Trueman, S. P. , Whytock, D. A., and Zaleski,

T. A., "Electron Spin Resonance Study of the Reaction of

Hydrogen Atoms with Hydrogen Sulphide," J. Chem. Soc.,

Faraday Trans. I 69, 416 (1973).

73 CEH/HEI Cehelnik, E. , Heicklen, J. , Braslavsky, S., Stockburger, L.,

and Mathias, E., "Photolysis of SO^ in the Presence of

Foreign Gases IV. Wavelength and Temperature Effects with

CO," J. Photochem. 2., 31 (1 973).
46

73 DAV/KLE

73 JAM/KER

73 KLE/DAV1

73 KLE/DAV2

73 LAN/OLD

73 PAY/STI

73 WES/DEH3

74 ATK/PIT3

74 CAD/WIC

74 C0X2

Davis, D. D. , and Klemm, R. B., "A Flash Photolysis-Resonance

Fluorescence Kinetics Study of the Reactions of GroundState Sulfur Atoms. V. Rate Parameters for the Reaction

3

of S( P) with cis-2-Butene and Tetramethyl ethylene, " Int.

J. Chem. Kinet. 5^, 841 (1973).

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

of the Rate of Reaction of the Methyl Radical with Sulphur

Dioxide," J. Chem. Soc. , Faraday Trans. I 69, 2124 (1973).

Klemm, R. B., and Davis, D. D., "A Flash Photolysis Resonance

Fluorescence Kinetics Study of Ground-State Sulfur Atoms.

3

III. Rate Parameters for Reaction of S( P) with Ethylene

Episulfide," Int. J. Chem. Kinet. 5_, 149 (1973).

Klemm, R. B., and Davis, D. D. , "A Flash Photolysis-Resonance

Fluorescence Kinetics Study of Ground-State Sulfur Atoms.

3

IV. Rate Parameters for Reaction of S( P) with Propene and

1-Butene," Int. J. Chem. Kinet. 5_, 375 (1973).

Langford, R. B., and Oldershaw, G. A., "Mechanism of Sulfur

Formation in the Flash Photolysis of Carbonyl Sulphide,"

J. Chem. Soc., Faraday Trans. I 69_, 1389 (1973).

Payne, W. A., Stief, L. J., and Davis, D. D. , "A Kinetics

Study of the Reaction of HC^ and SC^ and NO," J. Am. Chem.

Soc. 95 7614 (1973).

Westenberg, A. A., and DeHaas, N. , "Rate of the Reaction

OH + H

2

S -> SH + H

2

O over an extended Temperature Range,"

J. Chem. Phys. 59, 6685 (1973).

1974

Atkinson, R. , and Pitts, J. N. Jr., "Rate Constants for the

3 Reaction of 0( P) Atoms with 502^^0) over the Temperature

Range 299-392 K," Chem. Phys. Lett. 29, 28 (1974).

Cadle, R. D. , Wickman, H. H., Hall, C. B., and Eberle, K. M.,

"The Reaction of Atomic Oxygen with Formaldehyde , Crotonaldehyde, and Dimethyl Sulfide," Chemosphere 3_, 115

(1974).

Cox, R. A., "The Photolysis of Nitrous Acid in the Presence

of Carbon Monoxide and Sulphur Dioxide," J. Photochem.

3, 291 (1 974).
47

74 DAV/PRU Davis, D. D. , Prusazcyk, J., Dwyer, M. , and Kim, P., "A

Stop-Flow Time-of-Fl ight Mass Spectrometry Kinetics

Study. Reaction of Ozone with Nitrogen Dioxide and Sulfur

Dioxide," J. Phys. Chem. 78_, 1775 (1974). -

74 DEM/CAL Demerjian, K. L. , Calvert, J. G. , and Thorsell, D. L., "A

3

Kinetic Study of the Chemistry of the SO

2

( B-j ) Reactions

with cis-and trans-2-Butene, " Int. J. Chem. Kinet. 6_, 829 (1974).

74 KAL/BRA Kaldor, A., Braun, W., and Kurylo, M. J., "Infrared Laser

Enhanced Reactions: O

3 + SO," J. Chem. Phys. 61_. 2396

(1974).

74 KLE/DAV Klemm, R. B., and Davis, D. D. , "A Flash Photolysis-Resonance

Fluorescence Kinetics Study of the Reaction S(

3

P) + OCS,"

J. Phys. Chem. 78, 1137 (1974).

74 KLE/STI Klemm, R. B. , and Stief, L. J., "Absolute Rate Parameters for

the Reaction of Ground State Atomic Oxygen with Carbonyl

Sulfide," J. Chem. Phys. 61_, 4900 (1974).

74 LLO Lloyd, A. C., "Evaluated and Estimated Kinetic Data for Gas

Phase Reactions of the Hydroperoxyl Radical," Int. J. Chem. Kinet. 6 , 169-228 (1974).

74 SLA/GIL Slagle, I. R. , Gilbert, J. R. , and Gutman, D. , "Kinetics of

the Reaction between Oxygen Atoms and Carbon Disulfide,"

J. Chem. Phys. 61_, 704 (1974).

74 STE/ALV Stedman, D. H., Alvord, H., and Baker-Blocker, A., "Chemiluminescent

Reactions of Di sulfur Monoxide," J. Phys. Chem. 78_, 1248 (1974)

74 STU Stuhl , F., "Determination of the Rate Constant for the Reaction

OH + H

2 S by a Pulsed Photolysis-Resonance Fluorescence

Method," Ber. Bunsenges. Phys. Chem. 78_, 230 (1974).

74 TRA Trafton, W. E. Jr., "High Temperature Gas Phase Kinetic

Studies of Carbonyl Sulfide, Nitrous Oxide, and Carbon

Disulfide in a Shock Tube with Boundary Layer Corrections,"

Diss. Abstr. Int. B 34, 5935 (1974).

1975

75 BLC/ING Becker, K. H., Inocencio, M. A., and Schurath, U. , "The Reaction

of Ozone with Hydrogen Sulfide and its Organic Derivatives,"

Int. J. Chem. Kinet. 7 (Symp. 1), 205 (1975).
48

75 BEN/GOL

75 CAS/DAV

75 CHU/CAL

75 CLY/TOW

75 CUP/GLA

75 DAU/CAL

75 GAU/SNE

75 GLA/TOB1

75 GLA/T0B2

75 GOR/MUL1

75 HAR/WAY

75 SLA/GRA1

Benson, S. W., Golden, D. M. , Lawrence, R. W., Shaw, R. , and

Wool folk, R. W. , "Estimating the Kinetics of Combustion

Including Reactions Involving Oxides of Nitrogen and

Sulfur," Environmental Protection Agency Report No.

EPA-600/2-75-01 9, August 1975.

Castleman, A. W. Jr., Davis, R. E., Munkelwitz, H. R.

Tang, I. N., and Wood, W. P., "Kinetics of Association

Reactions Pertaining to f^SO^ Aerosol formation," Int.

J. Chem. Kinet. 7 (Symp. 1), 629 (1975).

Chung, K. , Calvert, J. G. , and Bottenhelm, J. W., "The Photochemistry of Sulfur Dioxide Excited within its First

Allowed Band (3130 A) and the "Forbidden" Band (3700-

4000 A)," Int. J. Chem. Kinet. 7, 161 (1975).

Clyne, M. A. A., and Townsend, L. W., "Rate Constant Measurements

for Rapid Reactions of Ground State Sulphur 3p

4 (^Pj) Atoms,"

Int. J. Chem. Kinet. 7_ (Symp. 1 ), 73 (1975).

Cupitt, L. T. , and Glass, G. P., "Reactions of SH with Atomic

Oxygen and Hydrogen," Int. J. Chem. Kinet. _1 (Symp. 1),

39 (1975).

Daubendiek, R. L., and Calvert, J. G., "A Study of the N

2

O

5

-SO

2

-O

2 Reaction System," Environmental Lett. 8 , 103 (1975).

Gauthier, M. J. E. , and Snelling, D. R. , "La Photolyse de

L'ozone a 253.7 nm: Desacti vation de 0( D) et de 02 ^T) par

Les Gaz de L' atmosphere," J. Photochem. 4, 27 (1975).

Glavas, S., and Toby, S., "The Reaction between Ozone and

Hydrogen Sulfide: Kinetics and Effect of Added Gases," Am.

Chem. Soc. ACS Symp. Ser. 1_7, 122 (1975).

Glavas, S., and Toby, S., "Reaction between Ozone and Hydrogen

Sulfide," J. Phys. Chem. 79, 779 (1975).

2

Gordon, S., and Mulac, W. A., "Reaction of the 0H(X IT) Radical Produced by the Pulse Radiolysis of Water Vapor,"

Int. J. Chem. Kinet. (Symp. 1), 289 (1975).

Harris, G. W., and Wayne, R. P., "Reaction of Hydroxyl Radicals

with NO, NO

2

and S 02 S " J. Chem. Soc., Faraday Trans. I

71_, 610 (1975).

Slagle, I. R., Graham, R. E. , Gilbert, J. R. , and Gutman, D.

"Direct Atoms with Carbon Monosulphide," Chem. Phys. Lett.

32, 184 (1 975).
49

l

75 TSU/YOK

75 WEI/TIM

75 WES/DEH1

75 WES/DEH2

75 YOK/AHM

76 ART/LEE

76 ATK/PER3

76 BAU/DRY

76 BID/BRE

76 DUM

76 HIG/SAI

76 KER/PAR

Tsunashima, Yokota, T. , Saferik, I., Gunning, H. E., Strausz, 0. P.,

"Abstraction of Sulfur Atoms from Carbonyl Sulfide by

Atomic Hydrogen," J. Phys. Chem. 79, 775 (1975).

Wei, C-N. , and Timmons, R. B., "ESR Study of the Kinetics of the

Reactions of 0(^P) Atoms with CS

2 and OCS," J. 'Chem. Phys.

62, 3240 (1975).

Westenberg, A. A., and DeHaas, N. , "Rate of the 0 + SO^ Reaction,"

J. Chem. Phys. 62, 725 (1975).

Westenberg, A. A., and DeHaas, N., "Rate of the Reaction 0 + SO

2 + M > SO

3 + M," J. Chem. Phys. 63, 5411 (1975).

Yokota, T. , Ahmed, M. G. , Safarik, I., Strausz, 0. P., and

Gunning, H. E. , "Reaction of Hydrogen Atoms with Thiirane,"

J. Phys. Chem. 79, 1758 (1975).

1976

Arthur, N. L. , and Lee, M-S., "Reactions of Methyl Radicals,

I. Hydrogen Abstraction from Dimethyl Sulphide," Aust. J. of Chem. 29, 1483 (1976).

Atkinson, R. , Perry, R. A., and Pitts, J. N. Jr., "Rate Constants

for the Reactions of the OH Radical with ^(M-Ar and Ng) and

S0

2

(M-Ar)," J. Chem. Phys. 65, 306 (1976).

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

Kinetic Data for High Temperature Reactions, Vol . 2: Homogeneous Gas Phase Reactions of the O

2 -O.3 System, the CO-O

2 -H

2 System, and Sulphur-Containing Species," (Butterworths

,

London, 1976).

Bida, G. T. , Breckenridge, W. H. , and Kolin, W. S., "A Kinetic

Study of the very Fast Reaction: 0(^P) + CS -* CO + S(^P),"

H. Chem. Phys. 64, 3296 (1976).

Dumas, J. L. , "Etude de la Reactivite Chimique de 1'oxygene

singulet produit en Phase Gazeuse. I. Etudes en Phase

Homogene," Bull. Soc. Chim. France, 658 (1976).

Higashihara, R. , Saito, Ko. , and Yamamura, H. , "S

2 Formation

during the Pyrolysis of H^S in Shock Waves," Bull. Chem.

Soc. Japan 40, 965 (1976).

Kerr, J. A., and Parsonage, M. J., "Evaluated Kinetic Data on Gas Phase Hydrogen Transfer Reactions of Methyl Radicals,"

(Butterworths, London 1976).
76 LEE

76 LEE/TIM

76 PER/ATK1

76 SLA/GRA

76 WAM

76 WHY/TIM

•50

Lee, J. H., "Gas Phase Kjinetic Study of some Simple Atom-Molecule

Reactions using fast flow and Flash Photolysis-Resonance

Fluorescence Techniques," Diss. Abstracts Int. 36., 6192 (1976).

Lee, J. H., Timmons, R. B., and Stief, L. J., "Absolute “Rate

Parameters for the Reaction of Ground State Atomic

Oxygen with Dimethyl Sulfide and Epi sulfide," J. Chem.

Phys. 64, 300 (1976).

Perry, R. A., Atkinson, R. , and Pitts, J. N. Jr., "Rate

Constants for the Reaction OH + H

2

S - H

2

O + SH and

OH + NH

3

H

2

O + NH

2

over the Temperature Range 297-427°K,"

J. Chem. Phys. 64, 3237 (1976).

Slagle, I. R. , Graham, R. E. , and Gutman, D. , "Direct Identification

of Reactive Routes and Measurement of Rate Constants in the

Reactions of Oxygen Atoms with Methanethiol , Ethanethiol,

and Methyl sul fide," Int. J. Chem. Kinet. 8, 451 (1976).

Wampler, F. B. , "Photochemistry of the S02> 2-Pentene System

at 3660 A," Int. J. Chem. Kinet. 8, 935 (1976).

Whytock, D. A., Timmons, R. B., Lee, J. H., Michael, J. V.,

Payne, W. A., and Stief, L. J., "Absolute Rate of the Reaction

3 of 0( P) with Hydrogen Sulfide over the Temperature Range

263 to 495 K," J. Chem. Phys. 65, 2052 (1976).

1977

77 BOW/DOD

77 CAS/TAN

77 FRE/PAL

77 GRA/GUT

77 LEE/STI

Bowman, C. T., and Dodge, L. G. , "Kinetics of the Thermal

Decomposition of Hydrogen Sulfide behind Shock Waves," Symp.

Combust. 1_6, (Combustion Institute Pittsburgh, Pa., 1977) 971.

Castleman, A. W. Jr., and Tang, I. N., "Kinetics of the Association

Reaction of SO

2

with the Hydroxyl Radical," J. Photochem.

6, 349 (1977).

Freund, H. , and Palmer, H. B., "Shock-Tube Studies of the Reactions

of NO

2 with N02> S02> and CO," Int. J. Chem. Kinet. <9, 887 (1977).

Graham, R. E. , and Gutman, D. , "Temperature Dependence of Rate

Constants and Branching Ratios for the Reaction of Oxygen

Atoms with Carbon Disulfide," J. Phys. Chem. 81_, 207 (1977).

Lee, J. H., Stief, L. J., and Tinsnons, R. B., "Absolute Rate

Parameters for the Reaction of Atomic Hydrogen with Carbonyl

Sulfide and Ethylene Episulfide," J. Chem. Phys. 67, 1705

(1 977).
78 ALA/BIG

51

1978

i 78 ATK/PER1

78 ATK/PIT4

78 HOR/NIS

78 IWA/PRE

78 KOL

78 KUR1

78 KUR2

78 MAR/HER

78 MAR/REI

Al-Awadi, N. , Bigley, D. B., and Gabbott, R. E. , "The Gasphase Pyrolysis of Dithioacetates: a Remarkable Constancy

of Substituent Effects," J. Chem. Soc. Perkin Trans. II,

1223 (1978).

Atkinson, R. , Perry, R. A., and Pitts, J. N. Jr., "Rate Constants

for the Reaction of OH radicals with COS, CS

2 and CH-^SCH^

Over the Temperature Range 299-430 K," Chem. Phys. Lett.

54, 14 (1978).

Atkinson, R. , and Pitts, J. N. Jr., "Kinetics of the Reaction

3

0( P) + SO

2 + M -> SO^ + M over the Temperature Range

of 299°-440°K," Int. J. Chem. Kinet. 10, 1081 (1978).

Horie, 0., Nishino, J. , and Amano, A., "The Reaction of Hydrogen

Atoms with 1-Butanethiol and Thiolane The Role of Chemically

Activated 1-Butanethiol ," Int. J. Chem. Kinet. 10.,

1043 (1978).

Iwamoto, K. , Presser, N. , and Ross, J., "Kinetics of Aerosol

Formation in Irradiated Gaseous NO

2 -SO2 Mixtures," J. Chem.

Phys. 68, 663 (1978).

Kollin, W. S., "Gas Phase Reactions of Carbon Monosulfide Studied

by the Fast Flow Technique," Diss. Abst. Int. B 39 , 771

(1978).

Kurylo, M. J. , "Flash Photolysis Resonance Fluorescence Investigation of the Reaction of OH Radicals with Dimethyl

Sulfide," Chem. Phys. Lett. 58, 233 (1978).

Kurylo, M. J. , “Flash Photolysis Resonance Fluorescence Investigation of the Reactions of OH Radicals with OCS and

CS

2

," Chem. Phys. Lett. 58, 238 (1978).

Martinez, R. I., and Herron, J. T. , "Stopped-Flow Study of

the Gas-Phase Reaction of Ozone with Organic Sulfide:

Dimethyl Sulfide," Int. J. Chem. Kinet. 10., 433 (1978).

Marvin, D. C. , and Reiss, H. , "Cloud Chamber Study of the Gas

Phase Photooxidation of Sulfur Dioxide," J. Chem. Phys.

69, 1897 (1 978).
52

78 PAR/HEI

78 SLA/BAL

78 SU/CAL

78 VAN/OBI

78 VAN/SAF

78 WHY/TIM

79 ADD/LEI

79 ALA/BIG

79 AST/GLA

79 BUR/CLI

Partymiller, K. , and Heicklen, J., "The Photolysis of Sulfur

Dioxide in the Presence of Foreign Gases XII: Photolysis

of SC>2 at 313.0 nm In the Presence of Both Allene and

Oxygen," J. Photochem. 8, 167 (1978).

Slagle, I. R. , Balocchi, F. , and Gutman, D. , "Study of the

Reactions of Oxygen Atoms with Hydrogen Sulfide, Methanethiol

Ethanethiol, and Methyl Sulfide," J. Phys. Chem. 82,

1333 (1978).

Su, F. , and Calvert, J. G. , "The Mechanism of the Photochemical

Reactions of SO

2

with Isobutane Excited," Int. J. Chem.

Kinet. 10, 557 (1978).

Van Roodselaar, A., Obi, K. , and Strausz, 0. P., "The Reaction

3

of S( P) Atoms with Nitric Oxide," Int. J. Chem. Kinet.

10 , 31 ( 1978 ).

Van Roodselaar, A., Safarik, I., Strausz, 0. P., and Gunning,

H. E., "The Reactions of Sulfur Atoms. 15. Absolute

3

Rate Parameters for the s ( P

2 1 0^ + ^lkyne Reactions,"

J. Am. Chem. Soc. 100 , 4068 (1978).

Whytock, D. A., and Timmons, R. B. , "Absolute Rate of the

Reaction of 0(^P) with Hydrogen Sulphide," Nat. Bur.

Stand. Sp. Pub. 526, 339 (1978).

1979

Addison, M. C. , Leitch, A. J., Fotakis, C. , and Donovan, R. J.,

"Reactions of CN(X^Z

+

) with 0CS and Formation of SCN,"

J. Photochem. 10, 273 (1979).

Al-Awadi, N. , and Bigley, D. B., "Carbonate Pyrolysis. Part 5.

The Gas-phase Pyrolysis of Some Unsymmetrical Monothioicarbonates

and a Rationalisation of the Rates of Some Related Reactions,"

J. Chem. Soc. Perkin Trans. II, 497 , (1979).

Astholz, D. C. , Glanzer, K. , and Troe, J., "The Spin-forbidden

Dissociation-Recombination Reaction SO^ + SO

2 + 0,"

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Wilkinson, J. P. T. , "Atmospheric Reactions of the HO

2

Radical Studied by Laser Magnetic Resonance Spectroscopy,"

Proceedings Royal Soc. (London) A 368 , 463 (1979).
53

*

79 CLY/WHI

79 DAV/RAV

79 GRA/WIN

79 GRI/REE

79 JOU/LEB

79 KAN/MCQ

79 MER/LEV

79 SNA/SIM

79 SIM/HEI

79 SIN/IRW

79 YOK/STR

Clyne, M. A., and Whitefield, P. D. , "Atomic Resonance Fluorescence

for Rate Constants of Rapid Bimolecular Reactions," J. Chem.

Soc. , Faraday Trans. II 75, 1327 (1979).

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2

Oxidation

via the Hydroxyl Radical: Atmospheric Fate of HS0

X

Radicals,"

Geophys. Res. Lett. 6., 113 (1979).

Graham, R. A., Winer, A. M. , Atkinson, R. , and Pitts, J. N. Jr.,

"Rate Constants for the Reaction of HO

2 with HO2

, S0

2

» CO, N

2

O, trans-2-Butene, and 2,3-Dimethyl -2-butene at

300 K," J. Phys. Chem. 83, 1563 (1979).

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of Sulfur Dioxide Thermal Decomposition Rate in Shock

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of Some Elementary Reactions of Sulfur Compounds Including

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,

"Kinetic Flash Spectroscopic Study of the CH^-CH^

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921 (1979).

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," Int. J. Chem. Kinet. JJ_, 907 (1979).

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with Dimethyl Sulfide," J. Phys. Chem. 83_, 3196 (1979).
APPENDIX.:

CONVERSION

TABLES

EQUIVALENT

SECOND

ORDER

RATE

CONSTANTS

r
EQUIVALENT

THIRD

ORDER

RATE

CONSTANTS

55

*

»

r

See

note

to

Table

for

Second

Order

Rate

Constants
N8S-114A (REv. »-7«)

U.S. OEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO.

NBSIR 80-2118

aim

—

4. TITLE AND SUBTITLE

Tables of Rate Constants for Gas Phase Chemical Reactions

of Sulfur Compounds (1971-1979)

5. Publication Date July 1980

... 7. AUTHOR! S) Francis Westley

8. Performing Organ. Report No.

9. PERFORMING ORGANIZATION NAME AND ADDRESS

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, DC 20234

Unit No.

11. Contract/Grant No.

12. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, city, State, ZIP)

Morgantown Energy Technology Center, Department of Energy,

Morgantown, West Virginia 26505 and

Office of Standard Reference Data, National Bureau of Standards, Washington, D.C. 20234

13. Type of Report & Period Covered

Interim

. #-.****>, JL^iL — - imm

:

:

15. SUPPLEMENTARY NOTES

|

j Document describes a computer program; SF-185, FIPS Software Summary, is attached.

16. ABSTRACT (A 200-word or leaa tactual summary of moat alghificant information. If document includes a significant bibliography or

literature surrey, mention it here.) A table of rate constants for gas phase chemical reactions of sulfur compounds

is presented. Specifically, it gives in tabular form the values of the parameters

for the modified Arrhenius equation k = Arexp(-E/RT) . The table covers the

reactions of sulfur containing molecules and free radicals - S, S

2

, SO, S02

, S0

3

, S

2 0, SH, H2 S, CS, CS2

, COS, CH

3

S‘, CH3 SH, cy-CH

2

CH

2

S, OUSCH^- and a Humber

ofJ thiols, thioethers and^thioesters - witn other compounds.

J The^table includes

16 unimolecular, 187 bimolecular, and 11 termolecular reactions totalling 214

distinct chemical reactions. There are 348 distinct entries, distributed as follows: 26 for first order reactions, 294 for second order reactions and 28

for third order reactions. The kinetic data were compiled from 109 experimental

papers and 6 critical reviews published between 1970 and 1979.

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

operated py semicolons)

rrhemus parameters, chemical kinetics, combustion, decomposition, free radicals,

gas phase, hydrocarbons, hydrogen, nitrogen oxygen, rate of reaction, sulfur.

18. AVAILABILITY jX~t Unlimited

For Official Distribution. Do Not Release to NTIS

Order From Sup. of Doc., U.S. Government Printing Office, Washington, DC

20402, SD Stock No. SN003-003-

Order From National Technical Information Service (NTIS), Springfield, V A 22161

19. SECURITY CLASS 21. NO. OF

(THIS REPORT) PRINTED PAGES

UNCLASSIFIED 59

20. SECURITY CLASS 22. Price (THIS PAGE)

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