A 11 ID 2 1 M t> 3 5 7

All 1021 46357

Weslley, Francis/Tables of rate constant QC100 .U573 V72;1982 C.2 NBS-PUB-C 1982 NSRDS-NBS 72

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Tables of Rate Constants

for Gas Phase Chemical Reactions

of Sulfur Compounds (1971-1980)

Francis Westley

Chemical Kinetics Division

Center for Chemical Physics

National Bureau of Standards

Washington, DC 20234

Prepared for

Morgantown Energy Technology Center Department of Energy

Morgantown, W V 26505

Office of Standard Reference Data

National Bureau of Standards Washington, DC 20234

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

and

Issued May 1982
Library of Congress Cataloging in Publication Data

Westley, Francis Tables of rate constants for gas phase chemical reactions of sulfur compounds (1971-1980)

(NSRDS-NBS ; 72) “Issued May 1982.”

1. Chemical reaction, Rate of—Tables. 2. Sulphur compounds

Tables. I. Morgantown Energy Technology Center. II. United

States. National Bureau of Standards. Office of Standard Reference

Data. Ill Title. IV. Series. QC100.U573 no. 72 [QD502] 602M8s 82-2094

[546’. 7232] AACR2

NSRDS-NBS 72

Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 72, 42 pages (May 1982) CODEN: NSRDAP

© 1982 by the Secretary of Commerce on Behalf of the United States Government

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1982
Foreword

The National Standard Reference Data System provides access to the quantitative data of physical science, critically evaluated and compiled for convenience and readily accessible through a

variety of distribution channels. The System was established in 1963 by action of the President’s

Office of Science and Technology and the Federal Council for Science and Technology, and

responsibility to administer it was assigned to the National Bureau of Standards.

NSRDS receives advice and planning assistance from a Review Committee of the National

Research Council of the National Academy of Sciences-National Academy of Engineering. A number of Advisory Panels, each concerned with a single technical area, meet regularly to examine

major portions of the program, assign relative priorities, and identify specific key problems in need of further attention. For selected specific topics, the Advisory Panels sponsor subpanels

which make detailed studies of users’ needs, the present state of knowledge, and existing data re- sources as a basis for recommending one or more data compilation activities. This assembly of advisory services contributes greatly to the guidance of NSRDS activities. The System now includes a complex of data centers and other activities in academic insti- tutions and other laboratories. Components of the NSRDS produce compilations of critically evaluated data, reviews of the state of quantitative knowledge in specialized areas, and computations of useful functions derived from standard reference data. The centers and projects also establish criteria for evaluation and compilation of data and recommend improvements in ex- perimental techniques. They are normally associated with research in the relevant field. The technical scope of NSRDS is indicated by the categories of projects active or being

planned: nuclear properties, atomic and molecular properties, solid state properties, thermodynamic and transport properties, chemical kinetics, and colloid and surface properties. Reliable data on the properties of matter and materials are a major foundation of scientific and technical progress. Such important activities as basic scientific research, industrial quality control, development of new materials for building and other technologies, measuring and correcting

environmental pollution depend on quality reference data. In NSRDS, the Bureau’s responsibility

to support American science, industry, and commerce is vitally fulfilled.

Ernest Ambler, Director
Contents

Foreword iii

1. Introduction 1 2. Guidelines for the User 2 Table of Arrhenius Parameters for Chemical Reactions of Sulfur Compounds 5 Reactions of: S (Sulfur atom) 5

S_, (Sulfur dimer) 11 SO (Sulfur monoxide) 12 S02 (Sulfur dioxide) 13 SO , (Sulfur trioxide) 18 SoO (Sulfur oxide) , 18 SH (Mercapto free radical) 18 H,S (Hydrogen sulfide) 20

CS (Carbon monosulfide free radical) 21 CS, (Carbon disulfide) 22

COS (Carbon oxide sulfide) 23

CH ,S- (Methylthio free radical) 25

CH,SH (Methanethiol) 25

cy-CH XH2 S (Thiirane) 25

CH ,SCH,- (Methyl, (methylthio)-, free radical) 26

CH ,CH ,SH (Ethanethiol) 26

(CH ,) 2S (Methane, thiobis-) 27

CH ,SSCH , (Disulfide, dimethyl-) 27

CH jSOXH, (Methane, sulfonylbis-) 27

cy-CH CHXH2 S (Thietane) 28

cy-(CH JCHCHjS (Thiirane, methyl-) 28

CH,CHXH2 SH ( 1 -Propanethiol) 28

(CH ,)XHSH (2-Propanethiol) 28

cy-CH XH_XHXH2 S (Thiophene, tetrahydro-) 28

CH ,C(S)SCHXH , (Ethane(dithioic) acid ethyl ester) 28

CHXHXHXH.SH (1-Butanethiol) , 28

(CH ,),CSH (2-Propanethiol, 2-methyl-) 28

CH2 = CHCH2 S02 CH , (1-Propene, 3-methylsulfonyl) 29

CH ,SC(0)0CH ,CH , (Carbonothioic acid O-ethyl S-methyl ester) 29

CH ,0C(0)SCH2 CH . (Carbonothioic acid S-ethyl O-methyl ester) 29

CH ,CH 2 CH XHXH,SH (1-Pentanethiol) 29

CH ,0C(0)SCH(CH ,) 2 (Carbonothioic acid O-methyl S-(l-methylethyl) ester) 29

CH ,SC(0)0CH(CH ,) 2 (Carbonothioic acid S-methyl O-(l-methylethyl) ester) 29

CH ,(SC(0)0C(CH ,) 2 (Carbonothioic acid 0-(l, 1-dimethyl ethyl) S-methyl ester) 29

CH ,0C(0)SC(CH ,), (Carbonothioic acid S-(l, 1-dimethyl ethyl) O-methyl ester) 29

CH ,C(S)SCH XHXH XH , (Ethane(dithioic) acid butyl ester) 29

CH ,C(S)SCH(CH ,)CH 2 CH , (Ethane(dithioic) acid 1-methyl-propyl ester) 29

CH X(S)SC(CH ,) , (Ethane(dithioic) acid, 1,1-dimethyl ethyl ester) 30

(CH,),CSC(CH ,), (Propane, 2,2'-thiobis[2-methyl]-) 30

(CH ,),CSSC(CH ,), (Disulfide. his[l,l-dimethylethyl]-) 30

3. Bibliography 31 Appendix: Conversion Tables 36

IV
Tables of Rate Constants for Gas Phase Chemical

Reactions of Sulfur Compounds (1971-1980)

Francis Westley

Chemical Kinetics Division. Center for Chemical Physics, National Bureau of Standards, II ashington, DC 20234

A table of rate constants tor 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 = AT 'exp(-E/RT ). The table covers the reactions of sulfur containing molecules and free

radicals, S, S,, SO, S02 , SO,, S_,0, SH, H,S, CS, CS2

, COS, CH .S-, CH,SH, cy-CH2 CH2 S, CH,SCH

and a number of thiols, thioethers, and thioesters, with other compounds. The table includes 19

unimolecular, 208 bimolecular, and 13 termolecular reactions totaling 240 distinct chemical

reactions. There are 441 rate constants associated with these reactions, distributed as follows: 30 for

first order reactions. 377 for second order reactions, and 34 for third order reactions. The kinetic data were compiled from 145 experimental papers anc 1980.

Key words: Arrhenius parameters; chemical kinetics; combustioi hydrogen; nitrogen; oxygen; rate of reaction; sulfur.

1. 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 substrates. The table is a compilation of rate constants given in 145

experimental papers and 8 critical reviews published between

1971 and 1980. Its purpose is to provide the kineticist and

combustion modeler with a comprehensive and easy-to-use source of kinetic data for chemical processes involving sulfur compounds. The table gives 441 distinct reaction rate constants from the above mentioned sources. A list of

references including the 153 papers, arranged alphabetically

by author for each separate year, is appended at the end of the table. The table includes a limited number of reactions involving

excited states like S*('D) and SO?; however, no attempt was made to cover all the papers from the literature dealing with such excited species. The reader interested in the reaction

kinetics of electronically excited species is encouraged to consult Keith Schofield’s excellent review: “Critically

Evaluated Rate Constants for Gaseous Reactions of Several

Electronically Excited Species,” J. Phys. Chem. Ref. Data 8,

723 (1979). 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, 18

8 critical reviews published between 1971 and

i; decomposition; free radicals; gas phase; hydrocarbons;

bimolecular reactions and 1 termolecular reaction involve 2

sulfur-containing reactants. For that reason, these 19

reactions are listed twice, the second time with the order of

the sulfur-containing reactants reversed, e.g., COS + S —

CO + S2 is also listed as S + COS —*• S2 + CO. As a

result, the total number of tabulated entries is 460, although

the real number of distinct entries is only 441. The

arrangement of the tables and the standard order of chemical

compounds are described in detail in the next section “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 Arrhenius equation k =

AT '‘expi-E/RT ). In general, uncertainties are given only

for the rate constant k itself and not for the individual 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 ', cm’mol 's ', and

crn’moUX 1 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 go to all of them. In particular, I wish to thank Dr. Robert F. Hampson, Jr., Director of the Chemical

Kinetics Data Center, for his more than helpful suggestions

and constant guidance; Dr. John T. Herron, Chief of the

1
Chemical Kinetics Division, and Dr. Wing Tsang, of the Chemical Kinetics Division, for their encouragement; Dr. Bert R. Staples, Manager of the Electrolyte Data Center, for assistance in computer formatting; Mrs. Bettijoyce Molino

and Mrs. Carla G. Messina from the Office of Standard

Reference Data for applying the OMNIDATA and GPSDIC

programs to photocompose the present tables; Mrs. Janice L. Jones for typing the original text with particular care; and

Mrs. Miriam Oland from the Technical Information and

Publications Division for retyping the text for photocomposition.

2. 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. Dnits for rate constants used in this table are the cubic

centimeter, the mole, and the second. The uncertainties given

in this table are derived from the error limits specified by

the author of the original paper or critical review. These

have been converted to a standard format, as described

below. 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 temperature range 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. Uncertainty limits expressed in the forpi of lower and

upper k factors, f and F, respectively, are used in this tabulation. Thus, if kt] is the central value of a rate constant

the limits of reliability for the rate constant ku are defined by

the relationship:

Ai < k < Fk„ (1)

i.e., multiplication of the central value kn by f and F gives,

respectively, the lower and upper reliability limits of the rate constant. In this standardized formulation of uncertainty

limits, the value ofy 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

1 and will not be

repeated here.

1 Westley, Franois, “Tables of Recommended Rate Constants for Chemical

Reactions Occurring in Combustion,” NBSIR 79-1941 (1979) (1st ed.); NSRDS-NBS 67 (1980) (2d ed.).

Arrangement of the Table

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/krvf, the temperature

range in kelvins, the parameters A, B, and E/R for the modified Arrhenius equation k = AT "expi-E/RT ), and the uncertainty limits expressed as k factors f and F. The bibliography includes the full references for the 145

experimental papers and 8 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 is as follows: Column 1, the chemical reaction indicating both the

reactants and the products. In the same column, under each

chemical reaction, the 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 the

first three letters of each author’s name. 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.

Recommended values for rate constants or ratios are indicated in parentheses after the short reference, e.g., 76

BAU/DRY (Recommended k)\ 72 KER/PAR (Recommended

ratio). The last line of column 1, placed under the line including

the short reference, 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!

rrf 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 ] = A7r_, included in the note indicates

that the rate constant was calculated from the equilibrium

constant K and the rate constant k_ ] 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. Column 2, with the heading n, indicates the order of the

reaction displayed in column 1. The value of n is J, 2, or 3, which defines the proper standard units for the reactions, as

follows:

-i scm ’mob's

1 cm'moP's

1

9

1 for the first order reactions 2 for the second order reactions 3 for third order reactions
The reaction order is indicated for every reaction included in the table and the digit indicating its value is alined 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 0, N>, N2 0, S02, SO ,, C02

. For the reaction SO, + OH + M —* H0S02 + M, the third body, a mixture of N, and 02

, 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 alined with the short reference and the reaction order. Column 4, with the heading k/kM, 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 alined with the short reference given

in column 1 and with the reaction order given in column 2. 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 alined with the short references given in column 1, as well as with the reaction order given in column 2. Column 6, with the heading^, gives the value of A for the equation k = AT '‘exp(-E/RT ). A is expressed as a number

less than 10 followed by the exponent in parentheses, e.g., 3.5 (+14) should be read as 3.5 X 10 4 1 '. 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 alined 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 k — AT "expi-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 alined with the short reference and reaction order information.

Column 8, with the heading E/R, indicates the value of E/R for the equation k = AT "exp(-E/RT). Since E is the

activation energy in cal mol 1 and R the gas constant with a value ol 1.987 cal mol 1 K ', it follows that the units of E/R

are kelvins. I he values given in column 5 for E/R may vary lrom 0 to over 100,000 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 alined with the

short reference and reaction order information. Column 9, with the heading “£ factors” and two

subheadings, ‘

’ and 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): fk0 < k < Fk()

. 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 alined 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 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 Contents, which give only

the first reactants of the chemical reactions included in this work, are in the standard order (S, S>, SO, SO_,, SO ( , S2 0,

SH. H2 S, CS, CS2

, COS, CH.S-, cy-CH_,CH 2 S, etc.) and are each part of the S-O-H-C system. The first reactant always

includes an S atom, and may include any of the O, H, or C

atoms. The second, or the third reactants may include any of

the O, H, S, N, or C atoms, and this sequence arranged

according to the standard order defines the O-H-S-N-C

system.

A number of second and third order reactions includes a second and, respectively, third body M. For these reactions,

M will always be placed after all other reactions, e.g.,

SO,, + M — SO, + O + M.

or SO + O + M —> SO, + M.

J Wagman, D. [).. Kvans. W. H.. Parker. V, B.. Halou. I.. Bailey. S. M.. and Schumm, R. H.. “Selected V allies of Chemical Thermodynamic Properties,” NBS Tech. Note 270-3. pp. 5. 10. 22 (1968).

3
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., SO, -f- HO, — products.

Display of Chemical Reactions and Formulae

In order to define the reaction products, the reactants are

written using semi-struc.tural formulas. All saturated normal

hydrocarbons are written so as to show separately each methyl and methylene group in the chain: CH t , CH ,CH „ CH^CH.CHj. Unsaturated hydrocarbons are written to show

the position of double or triple bonds. The unpaired electron 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 ^XHMethyl, hydroxy-, free radical -CH.OH

Methylthio free radical CH,SIf the unpaired electron of an alkyl radical belongs to a carbon in the middle of the chain, it is indicated inside parentheses following the carbon atom, e.g..

Propyl, 1-methyl-, free radical

(sec-butyl) CH ,CH2 CH(-)CH

If the oxygen atom of an oxy radical is attached to the terminal carnon atom, the radical is written in the usual manner: CH,0. 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 parentheses following the C atom: (CH ,)X(0-)CH ,CH The

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

as for the oxy free radicals: CH^O.,-, CH ( S. Atoms like (), H, S, N, C, and simple radicals like OH,

H0_„ SH, NH, CH, CH2 , CH„ CS, CN are written without a

dot.

Acknowledgment

This work was supported by the Department of Energy

and by the Office of Standard Reference Data of the National Bureau of Standards.

.4
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compound:

Chemical reactions

S + CL — SO + 0

Sulfur atom +- Oxygen molecule 71 FAI/VAN

72 DAV/KLE1

72 DON/LIT

75 CLY/TOW

79 CLY/WH1

80 BAU/COX (Recommended k). k factors apply at 298K only.

S + 0:l — SO + 0,

Sulfur atom -/- Ozone 75 CLY/TOW

80 BAU/COX (Recommended k).

S + H2 — SH + H

Sulfur atom -f- Hydrogen molecule 76 BAU/DRY (Recommended k).

k, = Kk ,. 75 BEN/GOL

Semi-empirical evaluation.

S*(

1 D) + H_> —» products

Sulfur atom + Hydrogen molecule 72 LIT/DAL

krpf: S*('D) + CH, =CH2 -> products.

S + OH — SO + H

Sulfur atom -/- Hydroxylfree radical 75 BEN/GOL

Semi-empirical evaluation. 79 JOU/LEB

S + OH — SH + 0

Sulfur atom + Hydroxyl free radical 75 BEN/GOL

Semi-empirical evaluation.

S + S+ M—>S., + M

Sulfur atom 79 NIC/AMO

S + S, — S2 + s

Sulfur atom + Sulfur dimer 75 BEN/GOL

Semi-empirical evaluation.

S + SO — S2 + O

Sulfur atom -+- Sulfur monoxide 75 BEN/GOL

Semi-empirical evaluation.

S + SO — SO + S

Sulfur atom -/- Sulfur monoxide 75 BEN/GOL

Semi-empirical evaluation.

S + SH — S2 + H

Sulfur atom -/- Mercapto free radical

73

SCH

75 BEN/GOL

Semi-emprical evaluation. 79 NIC/AMO

Upper limit k.

n M k/k„, 77 K A B E/R

(in k)

k factors

f F

2 298 1.7 ( + 12) 0.9 1.1 2 252-423 1 .3 ( + 1 2

)

0 0±50 0.8 1.2 2 295 1 ,0( + 12

)

- - 0.8 1.2 2 298 9.0 ( + 11) - - 0.8 1.2 2 296-410 1.0( + 12) 0 - 1 53 ± 1 08 0.7 1.4 2 230-400 1.2 ( + 12) 0 0 ± 1 00 0.7 1.4

2 298 7.2 ( + 12) 0.7 1.3. 2 298 7.2 ( + 12) 0.5 2.0

2 298 1 -3 ( -1) - - 0.5 1.5

2 2.5 ( + 12

)

0.5 13640

2 0.22 300 - - -

2 6.3 ( + 11) 0.5 0

2 298 4.0 ( + 13

)

- - 0.8 1.2

2 1.3 ( + 12

)

0.5 12700

3 295 4.3 ( +18

)

- - 0.8 1.2

2 6.3 (+11) 0.5 0

2 6.3 (+11) 0.5 1 1500

2 6.3 ( + 11) 0.5 0

2 295 2.4 ( + 13

)

2 6.3 ( + 11) 0.5 0

2 295 <3.0( + 12

)

- -

5
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions n M k/kr„ f 77 K A B E/R

(in K)

k factors

f F

S + SH — SH + S

Sulfur atom -/- Mercaplo free radical 75 BEN/GOL

Semi-empirical evaluation.

2 6.3 (+11) 0.5 4000

S + N 2 -* NS + N

Sulfur atom -f- Nitrogen molecule 75 BEN/GOL

Semi-empirical evaluation.

2 4.0( + 12) 0.5 55200

S*('D) + N, —* products

Sulfur atom -j- Nitrogen molecule 72/LIT/DAL

k r „,: S*('D) + CH, = CH, + products

2 0.062 300 - - -

S + NO — SO + N

Sulfur atom -j- Nitrogen oxide(NO) 75 BEN/GOL

Semi-empirical evaluation.

2 4.0( + ll) 0.5 17260

S + NO^ NS + 0

Sulfur atom Nitrogen oxide(NO) 75 BEN/GOL

Semi-empirical evaluation.

2 1.0 ( + 12

0.5 17365

S*('D) + NO — products

Sulfur atom -/- Nitrogen oxide(NO) 72 LIT/DAL

k rrl: S*('D) + CH. = CH, —» products

2 0.68 - - -

S + NO + M — SNO + M

Sulfur atom Nitrogen oxide(NO) 78 VAN/OBI

Limiting high-pressure k. 78 VAN OBI

ko (low pressure).

2

3

CO,

CO,

298

298

9.3 ( +12

1.9 ( +17

- - 0.8 1.2

S + NO, — SO + NO

Sulfur atom -/- Nitrogen oxidefNOJ 75 CLY/TOW

79 CLY/WHY

2

2

298 296-410

3.7 ( + 13)

3.0 ( + 13

0 -84 ±60

0.8

0.8

1.2

1.2

S*('D) + N,0 — NS + NO

Sulfur atom -f- Nitrogen oxide(N2 0) 72 LIT/DAL

k rrl: S*('D) + CH2 = CH2 —> products (Approximate ratio).

2 0.1 300 - - -

S + NH — SH + N

Sulfur atom -j- Imidogen free radical 75 BEN/GOL

Semi-empirical evaluation.

2 6.3 ( + 11) 0.5 4000

S*('D) + CO —* products

Sulfur atom + Carbon monoxide 72 LIT/DAL

k rHl : S*('D) + CH., = CH, —> products

2 0.19 300 - - -

S*('l>) + C0> —* products

Sulfur atom -/- Carbon dioxide 72 LIT/DAL

k r ,. r: S*('D) + CH ,=CH , —> products

2 0.24 300 - - -

6
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

S*('D) + CH, —* CH ,SH

Sulfur atom -f- Methane 72 LIT/DAL

k n. f: S*('D) + CH., = CH2 —

products 80 ADD/DON

s + cs — cs + s

Sulfur atom + Carbon monosulfide free radical 75 BEN/GOL

Semi-empirical evaluation.

s + cs — s, + c

Sulfur atom -f- Carbon monosulfide free radical 75 BEN/GOL

Semi-empirical evaluation.

S + CS + M — CS2 + M

Sulfur atom -j~ Carbon monosulfide free radical 76 BAU/DRY (Recommended k).

k, = Kk_,.

S + CS, — So + CS

Sulfur atom + Carbon disulfide 76 BAU/DRY (Recommended k).

S + COS —< S, + CO

Sulfur atom -f- Carbon oxide sulfide 72 JAK/AHM

Evaluation. 74 KLE/DAV

76 BAU/DRY (Recommended k).

S*('D) + COS —<• S2 + CO

Sulfur atom -f- Carbon oxide sulfide 72 LIT/DAL

krt, r: S*('D) + CH2 =CH2 —> products 79 ADD/BYR

79 SHE/SAF

k r,f: S*('D) + COS — S(

! P) + COS

(Optimization). 80 ADD/DON

S + CN -» CS + N

Sulfur atom -j~ Cyanogen free radical 75 BEN/GOL

Semi-empirical evaluation.

s + c2 — cs + c

Sulfur atom -j~ Carbon dimer 75 BEN/GOL

Semi-empirical evaluation.

S + CH=CH —* cy-CH =CHS

Sulfur atom -f- Ethyne 71 STR/OC

k/k„,f

: 6.2exp( -1007/T ).

k„.r: S + CH2 = CH , cy-CH2 CH2 S

Conventional photolysis method. 72 KER/PAR (Recommended k).

S + CH=CH —products

Sulfur atom -j- Ethyne 78 VAN/SAF

n M k/kr,. f 77 K A B E/R

(in K)

k factors

f F

2 0.076 300

2 295 l.K + 14) - - 0.7 1.3

2 6.3 ( + 11) 0.5 0

2 1.6(+12) 0.5 40463

3 1800-3700 8.7 (+13) 0 -4370 0.5 1.5

2 298 3.9 ( + 11) - - 0.5 1.5

2 298 l-K+10). - -

2 233-245 9.2 ( + 11) 0 1825±60 0.9 1.1 2 230-2600 1.7 ( + 12) 0 2050 ±230 0.3 3.0

2 1.5 300 - - - 0.7 1.3

2 290 7.2 ( +13

)

_ _ 0.8 1.3 2 2.4 298 -

2 295 1 .8 ( + 14) - - 0.7 1.3

2 6.3 ( + 11) 0.5 0

2 6.3 ( + 11) 0.5 0

2 298-450 - - -

2 298 1.7 ( + 11) - -

2 298-484 3.4 ( + 13

)

0 1510±200 0.4 1.6

7
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemieal reactions

S + CD=CD —* products

Sulfur atom -R Ethyne-d., 78 VAN/SAF

S*('D) + ch,=ch2 ->ch2 =chsh

Sulfur atom Ethene 79 SHE/SAF

Optimization.

S + CH_, = CH , cy-CH 2 CH2 S

Sulfur atom -f- Ethene

71

CON/VAN

Flash photolysis method. 71 STR/OC

krpr

: S + CH, = CH. -> cy-CHoCHjS

Conventional photolysis method. 72 DAV/KLE2

72 KER/PAR (Recommended k).

S*('D) + CH2 =CH2 —» cy-CH2 CH2S*

Sulfur atom -R Ethene 79 SHE/SAF

Optimization.

S + CD, = CH , — cy-CD2 CH2 S

Sulfur atom -f- Ethene- 1,1 -d2 71 STR/OC

k r „ r: S + CH2 =CH, — cy-CH2 CH2 S

Conventional photolysis method.

S + cis-CHD =CHD —* cy-CHDCHDS

Sulfur atom -/- cis-Ethene-l,2-d., 71 STR/OC

kr „ r: S + CH., =CII, -> cy-CH 2 CH2 S

Conventional photolysis method.

S + CD2 = CD2 -h- cy-CD2 CD2 S

Sulfur atom -f- Ethene-d4 71 STR/OC

k r„ r: S + CH2 = CH2 -» cy-CH 2 CH2 S

Conventional photolysis method.

S*('D) + CH ,CH , —* products

Sulfur atom -/- Ethane 72 LIT/DAL

k ref: S*(' D) + CH2 = CH 2 —> products

S + cy-CH2 CH2 S S2 + CH2 = CH 2 Sulfur atom -f- Thiirane 71 STR/OC

k/kr,,: 8.3exp(+906/T)

k rrf: S + CH. = CH . cy-CH,CH2 S

Conventional photolysis method.

73

KLE/DAV1

S + CH ,C=CH -» cy-(CH ,)C=CHS

Sulfur atom -j- 1-Propyne 71 STR/OC

k/kr ,. f: 6.2exp( -453/T)

k r „ f: S + CH , = CH. — cy-CH2 CH,S

Conventional photolysis method. 72 KER/PAR (Recommended k).

S + CH ,C=CH —* products

Sulfur atom -/- Propyne 78 VAN/SAF

n M k/kr „ f 77 K A B E/R

(in K)

k factors

f F

2 298 2.3( + l 1

- - 0.8 1.2

2 298 4.2 ( + 13) - -

2 298 9.0( + 1 1

- - 0.9 1.1

2 1.0 298-450 - - -

2 218-442 4.3 ( + 12

0 795 ±40 0.9 1.1 2 298 8.1 (+11) ‘ ‘

2 298 3.8 ( +13

- -

2 1.07 298-450 - -

2 1.04 298-450 - - -

2 1.14 298-450 - - -

2 0.17 300 - - -

2 298-450 - - -

2 298-355 2.7 (+13) 0 0 0.9 1.1

2 298-450 - - -

2 298 1-1 ( + 12) - -

2 298-449 2.0 ( + 130 453+100 0.4 1.6

8
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

S + CH: ,CH = CH, — cy-(CH,)CHCH S

Sulfur atom -/- Propene 71 CON/VAN

Flash photolysis method. 71 STR/O'C

k/kr„ r: 1.0exp(+574/T)

k„f: S + CH_, = CH, — cy-CHoCHoS

Conventional photolysis method. 72 KER/PAR (Recommended k). 72 KER/PAR (Recommended ratio). k rr[: S + CH2 = CH, — cy-CH2 CH2 S 73 KLE/DAV2

S*(‘D) + CH ,CH = CH , — cy-(CH,)CHCH2 S

Sulfur atom -f- Propene 72 KER/PAR (Recommended ratio). k rpf: S*('D) + CH, = CH2 -> cy-CH2CH2 S

S + cy-(CH ,)CHCH2 S —* S2 + CH ! CH = CH2 Sulfur atom + Thiirane.methyl- 71 STR/OC

k/kref: 8.4exp( + 1057/T)

k ref: S + CH2 =CH2 — cy-CH2 CH2 S

Conventional photolysis method.

S + CH:l CH2 C=CH ->• products

Sulfur atom -f- 1-Butyne 78 VAN/SAF

S + CH t C=CCH , —» cy-(CH ,)C = C(CH ,)S Sulfur atom -f- 2-Butyne 71 STR/O'C

k/krpf: 2.7exp( +654/T)

kre(: S + CH2 =CH2 — cy-CH2 CH2S

Conventional photolysis method. 72 KER/PAR (Recommended k).

S + CH.,C=CCH j — products

Sulfur atom + 2-Bulyne 78 VAN/SAF

S + CH_, = CHCH = CH2 —> cy-(CH 2 = CH)CHCH2 S

Sulfur atom -f- 1, 3-Butadiene 71 STR/O'C

k/kr(f: 2.4exp( + 1027/T)

kref: S + CH2 = CH2 cy-CH2 CH2S

Conventional photolysis method. 72 KER/PAR (Recomended k).

S + CH-,CH2 CH=CH2 —*• cy-(CH,CH2 )CHCH2 S

Sulfur atom + 1-Butene 71 CON/VAN

Flash photolysis method. 71 STR/O'C

k/kre(: 0.75exp( +866/T)

krpf: S + CH2 =CH2 -> cy-CH2 CH_,S Conventional photolysis method. 72 KER/PAR

72 KER/PAR (Recommended ratio). krr)

: S + CH2 = CH2 — cy-CH 2 CH2 S 73 KLE/DAV2

n M k/k„.r 77 K A B ElR

(in K)

k factors

f F

2 298 6.0( + 12) 0.8 1.2

2 298-450 - - -

2 298 5.8 (+12)

2 6.9 298 - - -

2 214-500 3.6 ( + 12

)

0 190 ±45 0.2 5.2

2 1.7 300 - - -

2 298-450 - - -

2 298 3.3 ( +12

)

- - 0.9 1.1

2 298-450 - - -

2 298 1 .9 ( + 13

)

- -

2 298 1 .6 ( +13) - - 0.9 1.1

2 298-450 - - -

2 298 6.0( + 13) - -

2 298 9.0 ( +12

)

- - 0.9 1.1

2 298-450 - - -

2 298 9.3 ( + 12

)

2 10.0 298 - -

2 216-475 4.5 (+12

)

0 180 ±45 0.1 4.0

9
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

S + cis-CH ,CH =CHCH , — cy-(CH ,)CHCH(CH ( )S Sulfur atom cis-2-Butene 71 STR/O'C

k/kr ,, r: 0.53exp( + 1050/T)

kri. f: S + CHj = CH , -» cy-CHXH2 S

Conventional photolysis method. 72 KER/PAR (Recommended k). 72 KER/PAR (Recommended ratio). k r,„: S + CH , = CH 2 - cy-CH.CHoS

S + cis-CH jCH = CHCH , —» products

Sulfur atom -f- cis-2-Butene

73

DAV/KLE

S + trans-CH ,CH=CHCH , — cy-(CH t )CHCH(CH,)S

Sulfur atom -f- trans-2-Butene 71 CON/VAN

Flash photolysis method. 71 STR/O'C

k/krH : 0.65exp( + 1010/T

k ref: S + CH_, = CH, -> cy-CHXH,S

Conventional photolysis method. 72 KER/PAR (Recommended k). 72 KER PAR (Recommended ratio). k ref: S + CH2 =CH, — cy-CHXH,S

S + (CH ,)X=CHo - cy-(CH ,) 2CCH2S

Sulfur atom 1-Propene, 2-methyl- 71 CON/VAN

Flash photolysis method. 71 STR/O'C

k/kr ,. f

: 0.97exp(+1190/T)

krf(: S + CH, = CH2 cy-CHXH,S

Conventional photolysis method. 72 KER/PAR (Recommended k). 72 KER/PAR (Recommended ratio). krrf: S + CH , = CH2 ^ cy-CHXH,S

S*('D) + (CH ,) 2 C=CH_, — cy-(CH ;) 2 CCH 2 S

Sulfur atom -j- I-Propene, 2-methyl- 72 KER/PAR (Recommended ratio). kref: S*('U) + CH2 = CH2 — cy-CHXH,S

S + CH jCH2 C=CCH t — products

Sulfur atom -f- 2-Pentyne

78 VAN/SAF

S + CH 1 CHXHXH = CH2 cy-(CH,CH2 CH2)CHCH2 S

Sulfur atom + 1-Pentene 72 KER/PAR (Recommended k).

S + CH ,CH2 C(CH j) = CH 2 — cy-(CH t CH2 )C(CH: ,)CH2 S

Sulfur atom -p 1-Butene, 2-methyl- 71 STR/O'C

k/k r ,,: 0.78exp( + 1424/T)

krrl

: S + CH. = CH. cy-CH 2 CH_,S Conventional photolysis method. 72 KER/PAR (Recommended k).

n M k/k r ,. ( 77 K A B E/R

(in K)

k factors

f F

2 298-450 - - -

2 298 1 ,4( + 13

2 16.0 298

2 219-500 2.8( +120 -1 16±45 0.9 1.1

2 298 1.2(+13) - - 0.8 1.2

2 298-450 - - -

2 298 1.4( + 13)

2 20.0 298

2 298 3.6 ( + 13) _ _ 0.9 1.1

2 298-450 - - -

2 298 4.0 ( + 13)

2 50.0 298

2 3.5 300 - - -

2 298 1 .8 ( +13

- - 0.8 1.2

2 298 8.1 (+12) - --

2 298-450 - - -

2 298 7.4 ( +13

—

10
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

S + CH,CH = C(CH,), — cy-(CH,)CH[C(CH,)o]S

Sulfur atom + 2-Butene, 2-methyl- 71 STR/O'C

k /

rt. r

: 0.51exp( + 1515/T)

k„r

: S + CH, = CH_, cy-CHXH.S

Conventional photolysis method. 72 KER/PAR (Recommended k). 72 KER/PAR (Recommended ratio).

k„.f

: S + CH_, = CH_, — cy-CH 2 CH,S

S + (CH ,) 2 C = C(CH ,) 2 —* cy-[(CH: ,) 2]CC[(CH ,) 2 ]S Sulfur atom -f- 2-Butene, 2, 3-dimethyl— 71 CON/VAN

Lower limit k. Flash photolysis method. 71 STR/O'C

k/k„f: 0.50exp( + 1 690/T)

kref: S + CH2 = CH, -> cy-CH2 CH2 S

Conventional photolysis method. 72 KER/PAR (Recommended k).

S + (CH ,) 2 C = C(CH ,) 2 —products

Sulfur atom -f~ 2-Butene, 2,3-dimethyl- 73 DAV/KLE

S2 + 0 —>• S + SO

Sulfur dimer Oxygen atom 73 SCH

Approximate k. Given with caution. 75 BEN/GOL

Semi-empirical evaluation.

S2 + H —< S + SH

Sulfur dimer -f- Hydrogen atom 75 BEN/GOL

Semi-empirical evaluation.

s2 + s — s + s2 Sulfur dimer + Sulfur atom 75 BEN/GOL

Semi-empirical evaluation.

S2 + S2 + M — S4 + M

Sulfur dimer 72 LAN/OLD

73 LAN/OLD

Given with caution. 79 NIC/AMO

S2 + N — S + NS

Sulfur dimer -f- Nitrogen atom 75 BEN/GOL

Semi-empirical evaluation.

s2 + c — S + CS

Sulfur dimer -f- Carbon atom 75 BEN/GOL

Semi-empirical evaluation.

S2 + M^S + S + M

Sulfur dimer 80 HIG/SAI

n M k/k„. 77K A B FJR

(in k)

k fa

f

ctorsF

2 298-450 - - -

2 298 6.5 ( + 13) 2 56.0 298

2 298 >6.2 ( + 13) - - 0.9 i.i

2 298-450 - - -

2 298 8.5 ( +13

)

- -

2 252-500 2.8 ( +12

)

0 -650 ± 115 0.6 1.4

2 1050 4.2(+12) - -

2 6.3( + l 1

)

0.5 0

2 7.9( + 12) 0.5 8355

2 6.3 ( + 11) 0.5 0

3 CO* 293 9.1 ( + 17) 0.1 10. 3 co2 293 CO On + CO - -

3 295 CO + CO - - 0.9 1.1

2 6.3 (+11) 0.5 4000

2 6.3 ( + 11) 0.5 0

2 Ar 4500-6000 4.8 ( + 13) 0 38750

11
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

SO + 0 — 0 + SO

Sulfur monoxide ~h Oxygen atom 75 BEN/GOL

Semi-empirical evaluation.

SO + 0 — S + 0,

Sulfur monoxide -f- Oxygen atom 75 BEN/GOL

Semi-empirical evaluation.

SO + 0 + M — SO, + M

Sulfur monoxide -f- Oxygen atom 71 MIY/TAK1

76 BAU/DRY (Recommended k).

SO + 0, — SO., + 0

Sulfur monoxide -h Oxygen molecule 72 BRE/MIL

Upper limit k. 80 BAU/COX (Recommended k). k factors apply at 298k only.

SO + 0;i — SO, + 0,

Sulfur monoxide -/- Ozone 80 BAU/COX (Recommended k). k factors apply at 298K only. 80 ROB/SMI

SO + 0,(v= n) SO,* + 0,

Sulfur monoxide Ozone 74 KAL/BRA

k ref: SO + 0, — SO,* + 0,

SO + H — 0 + SH

Sulfur monoxide -h Hydrogen atom 75 BEN/GOL

Semi-empirical evaluation.

SO + H — S + OH

Sulfur monoxide ~h Hydrogen atom 75 BEN/GOL

Semi-empirical evaluation.

SO + OH — SO, + H

Sulfur monoxide -/- Hydroxyl free radical 73 SCI! (Recommended k). 79 JOU/LEB

SO + S — 0 + S, Sulfur monoxide + Sulfur atom 75 BEN/GOL

Semi-empirical evaluation.

SO + S —< S + SO

Sulfur monoxide -h Sulfur atom 75 BEN/GOL

Semi-empirical evaluation.

n M k/k r

,. f 77 K A B E/R

(in K)

k factors

f F

2 6.3( + ] 1

0.5 0

2 2.0( + 1 1

0.5 2770

3 Ar 298 7.3( + 16) 0.9 1.1 3 298 6.7 (+13) ~ _ 0.7 1.3

2 297 <5.0 ( +7) - -

2 300-1000 3.6 (+11) 0 3300±500 0.3 3.2

2 220-300 1 .5 ( + 12

0 1 100±400 0.5 2.0

2 296 5.2 ( + 10

- - 0.8 1.2

2 2.4 300 - - - 0.8 1.3

2 6.3 ( + 110.5 19930

2 4.0 (+12) 0.5 11200

2 298 3.3 (+13) 0.5 2.0 2 298 5.1 (+13) 0.8 1.2

2 6.3 (+11) 0.5 11500

2 6.3 (+11) 0.5 0

12
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

SO + SO — SO, + S

Sulfur monoxide 72 BRE/MIL

Upper limit k. 73 SCH

Upper limit k. 73 SCH

Upper limit k. 75 CHU/CAL

SO + SO + M — (SO)., + M

Sulfur monoxide 80 HER/HUI

2-8 torr.

SO + SO., -> SO, + SO,

Sulfur monoxide -f- Sulfur trioxide 75 CHU/CAL

SO + (SO), — SO, + S,0

Sulfur monoxide + Sulfur monoxide dimer 80 HER/HUT

2-8 torr.

SO + N — 0 + NS

Sulfur monoxide + Nitrogen atom 75 BEN/GOL

Semi-empirical evaluation.

SO + N — S + NO

Sulfur monoxide -f- Nitrogen atom 75 BEN/GOL

Semi-empirical evaluation.

SO + NO, ->• S02 + NO

Sulfur monoxide -f- Nitrogen oxidefNOf 71 CUP/GLA

kref: 0 + NO, — 0, + NO

71 MIY/TAK2

80 BAU/COX (Recommended k). 80 CLY/MAC

SO + c — o + cs

Sulfur monoxide + Carbon atom 75 BEN/GOL

Semi-empirical evaluation.

SO + C — S + CO

Sulfur monoxide + Carbon atom 75 BEN/GOL

Semi-empirical evaluation.

SO + M —• S + 0 + M

Sulfur monoxide 78 AST/GLA

Rate constant expressed as k[Ar],

SO, + 0-4|0 + 0,

Sulfur dioxide + Oxygen atom 76 BAU/DRY (Recommended k).

k, = Kk_,. 80 GRI/REE

80 SLA/GRI

n M k/kn. r 77 K A B E/R

(in K)

k factors

f F

2 297 <3.0 (+10)

2 300 < 1 .8 ( +9) - -

2 1000 < 1 .2 ( + 1 1 ) - -

2 298 5.0 ( +8) - - 0.2 1.8

3 298 1.6( +17

)

- -

2 298 1.2 ( +9) - - 0.4 1.6

2 298 2 . 0

( + 10) - -

2 1.6( +12

)

0.5 8254

2 6.3 (+11) 0.5 4000

2 1.6 300 _ _ _

2 298 1.2 ( +16

)

_ _ 0.9 1.1 2 298 8.4 ( + 12

)

- - 0.5 2.0 2 295 8.2 ( +12

)

“ 0.9 1.1

2 6.3 ( + 1 1 ) 0.5 0

2 6.3 (+11) 0.5 0

2 Ar 5700-7200 1.6( +14) 0 55330+3610 0.3 4.0

2 440-2100 1.3 ( + 14) -0.5 9980 0.3 1.7

2 2630-3570 4.0 ( + 12

)

0 9210 0.9 1.1 2 3500 3.8 ( + 11) - - 0.9 1.1

13
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions n M k/kr „r 77 K A B E/R

(in K)

k factors

f F

SO, + 0 + M — S0: , + M

Sulfur dioxide -j~ Oxygen atom 73 SCH

M = Ar, 0,, N,, He.

k factors are larger at other temperatures. 74 ATK/P1T3

75 WES/DEH2

75 WES DEH2

M,.rl: He(l.O) 75 WES DEH2

Mrff: SO,(9.5) 75 WES DEH2

M„ff: N 2 (2.4) 78 ATK/PIT4

78 ATK/PIT4

78 ATK PIT4

79 MER/LEV

80 BAU/COX (Recommended k). k factors apply at 298K only. 80 BAU/COX (Recommended k). k factors apply at 298K only.

3

3

33

3

3

33

3

3

3

3

N,0

He

He

SO,

N,

Ar

N,SO,

N,

Ar

250-1000

299-392

248-415

297

297

297

299-400

300

299

1685 200-400

200-2500

3.6 ( + 1 4

3.3 ( + 16)

3.9( + 16)

3.0 ( + 1 4

2.9 ( + 1 5

7.2 ( + 1 4

1.1 ( + 16)

5.0( + 14)

3.4 ( + 15)

7.4( + 14)

1.5( +16)

5.4 ( +28

0

0

0

0

0

-3.75

-500

1 000 ±200

1400 ±50

1010± 1 50

1000±200

2650 ±200

0.5

0.8

0.9

0.7

0.9

0.8

0.7

0.5

0.5

2.0

1.2

1.1

1.3

1.1

1.2 1.3

2.

2.0

S02 + 02 *('A

f )^S0;, + 0

Sulfur dioxide ± Oxygen molecule 76 DEM 2 298 1 .3 ( +8)

S02 * + 0, —* products

Sulfur dioxide + Oxygen molecule 78 PAR/HEI

k„f: S02 * 'SO,, or SO,

(S02 * is a singlet formed on absorption).

2 0.05 298 - - -

'S02 ± 02 — products

Sulfur dioxide -f- Oxygen molecule 78 PAR/HEI

kref: 'SO, ± S02 —> products

(

1 S02 is a fluorescent singlet).

2 0.29 298 - - -

S02 *('B i ) + 0, — products

Sulfur dioxide -/- Oxygen molecule 78 PAR/HEI

krpf: SO-j’f'B,) + S02 —* products

2 0.36 298 - - -

SO, + 0;, -V SO;, + 0,

Sulfur dioxide + Ozone 74 DAV/PRU

Upper limit k.

2 300 <6.0 ( +1) - -

S02 ± H ± M — HS02 + M

Sulfur dioxide + Hydrogen atom 76 BAU/DRY (Recommended k). 3 1660-2120 5.1 ( + 15) 0.5 1.5

S02 ± OH —* products

Sulfur dioxide + Hydroxylfree radical 80 COX/DER 2 297 4.0 ( + 1 1 ) 0.8 1.2

SO, + 0H(v = 9) —*• HSO,

Sulfur dioxide -f~ Hydroxylfree radical 72 WOR/COL

Lower limit k. Unreported T assumed to be 298K.

2 298 > 1 .4 ( + 1 0

- - 0.8 1.2

14
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

SCC + OH + M — HOSO, + M

Sulfur dioxide -f- Hydroxy!free radical 74 COX2

Evaluation. Rate constant expressed as k[M]

with M = N, + 0) at 1 atm. 75 CAS/DAV

Limiting high-pressure k (760 torr).

75

CAS/DAV

k„ (low pressure: <20 torr).

75

GOR/MUL1

In an atmosphere of water vapor. 75 HAR/WAY

75 HAR/WAY

76 ATK/PER3

At 760 torr.

76

ATK/PER3

Limiting high-pressure k. 76 ATK/PER3

k„ (low-pressure k). 77 CAS/TAN

Limiting high-pressure k (760 torr).

77

CAS/TAN

k„ (low-pressure k).

77

CAS/TAN

k„ (low-pressure). On the basis of ku (297) and Ea experimental values. 77 CAS/TAN

k„ (low-pressure k). Alternative T-dependent expression. 79 DAV/RAV

Total pressure 1 atm. (extrapolated value). 80 BAU/COX (Recommended k). k„ (low-pressure k). k factors apply at 298K only. 80 BAU/COX (Recommended k). Limiting high-pressure k. k factors apply at 298K only. 80 HAR/ATK

Total pressure 650 torr. 80 HAR/ATK

Total pressure 650 torr. 80 HAR/ATK

Total pressure 650 torr.

SO, + HO, — SO, + OH

Sulfur dioxide + Hydroperoxylfree radical 73 PAY/STI

Evaluation. 74 LLO

Evaluation. Ratio data versus k rel for reaction HO, + HO, — H2 0, + 0, 79 BUR/CLI

Upper limit k.

SO, + HO, —* products

Sulfur dioxide + Hydroperoxylfree radical 79 GRA/WIN

Upper limit k.

SO, + HO, + M —* HO,SO, + M

Sulfur dioxide + Hydroperoxyl free radical 79 BUR/CLI

Upper limit k.

n M k/k„, 77 K A B E/K

(in K)

k factors

f F

2 294 3.6 ( + 11

)

- - 0.9 1.1

2 N, 298 3.6( + ll) - -

3 N, 298 5.8 ( + 16) - -

2 H.O 435 1.1 ( + 12

)

- - 0.9 1.1

3 Ar 298 1.6 (+17) _ _ 0.7 1.3 3 N, 298 2.6 (+17) - - 0.9 1.1 2 Ar 298 4.0 ( + 1

1

)

- - 0.9 1.1

2 Ar 298 5.0 ( + 1 1

)

- -

3 Ar 298 5.9 ( +16) - - 0.8 1.2

2 N, 297 3.6 ( + 1 1

)

- -

3 N

,

297 5.8 ( + 16

)

- -

3 n2 253-297 5.0 ( +14) 0 -1410

3 n2 253-297 2.5 ( +29

)

-5.1 0

2 n2 298 5.4 (+11) - - 0.8 1.3

3 n2 200-400 1.7 (+24) -2.9 0 0.5 2.0

2 200-400 1.2 ( + 12

)

0 0 0.4 2.5

2 Ar 298-424 7.0( +9) 0 -1193+150 0.7 1.5

2 sf6 298-424 7.6 ( + 10

)

0 -753 ±150 0.7 1.

2 N, 298-424 + o

C4 0 -956

2 300 5.2 ( +8) _ _ 0.8 1.2

2 300 5.2 ( +8) - - 0.9 1.2

298 <1.2 ( +7) - -

2 300 <6.0 ( +5) - -

3 He 298 < 1.5 ( +14

)

- -

15
Fable of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions n M k/kr „ f 77 k A 11 E/R

(in K)

k factors

f F

SO, + SO,*('B,) — SO*('A..,‘Z-) + SO,

Sulfur dioxide 75 CHU/CAL 2 298 2.2 ( + 12) 0.8 1.2

SO, + SO,*('B,) — SO + SO,

Sulfur dioxide 78 MAR/REI

In an atmosphere of water vapor. (Approximate k).

2 298 2.0 ( +14) - -

SO, + SO,*('B,) —>• S0*('2 ) + SO,

Sulfur dioxide 75 CHU/CAL 2 298 4.2 ( + 10) 0.9 1.1

SO, + NO, SO, + NO

Sulfur dioxide -f- Nitrogen oxidefNO.J 71 ARM/CUL

77 FRE/PAL

Extended validity of k reported in 71 ARM/CUL (above), up to 2000K.

2

2

703-1 193 430-1850

6.3 (+12)

6.3 ( + 12)

0

0

13950 16000

SO, + NO,* —

products

Sulfur dioxide -R Nitrogen oxidelNOJ 78 IWA/PRE

At 50 torr.

2 298 8.2( + 10

- -

SO, + NO, SO, + NO,

Sulfur dioxide -R Nitrogen oxidefNO J 75 DAU/CAL

Upper limit k.

2 300 <4.2 ( +3) - -

SO, + N,Or> — SO, + N,0,

Sulfur dioxide R Nitrogen oxide(N.,OrJ 75 DAU/CAL

Upper limit k.

2 300 <2.5 ( +1) - -

'SO,* + CO — SO + CO,

Sulfur dioxide -f- Carbon monoxide 73 CEH/HEI

k rrf: 'SO,* + SO, —* products. k/krrf = 5.0x10 '(at 2537 A") 73 CEH HEI

k/kn. r = 1.5x10-'(at 3130 A")

2

2

300

300

- - -

SO,* + CO — SO + CO,

Sulfur dioxide -R Carbon monoxide 73 CEH/HEI

k r(, r

: S02 * — products k/krel

- = 2.2xlO r> (3130 to 3261 A") (SO,* is a vibrationally excited singlet).

2 300 - - -

SO,** + CO^SO + CO,

Sulfur dioxide + Carbon monoxide 73 CEH/HEI

k r„: SO,** — SO,

k rrf = 1.8x10-’ (2537 to 3261 A”) (SO,** is a chemically active triplet).

2 300 - - - 0.7 1.4

SO, + CO + M —>• products

Sulfur dioxide + Carbon monoxide 71 BAU/JEF

At 27-170 torr pressure.

2 Ar 1770-2453 2.7 ( + 12) 0 24300 ±600 0.8 1.3

16
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds -— Continued

Chemical reactions n M k/kr„f 77 k A B E/B

(in k)

k factors

f F

S02 + CH, + M — CH ,S0, + M

Sulfur dioxide -f- Methylfree radical 73 JAM/KER

Limiting high-pressure k.

2 298 1 8( + 1 1 ) - - 0.9 1.1

S02 + CH ,0, — CH,02 S02 Sulfur dioxide -f- Methyldioxyfree radical 79 SAN/SIM

79 SIM/HEI

kr,r: NO + CH,02 — N02 + CH ,0

2

2 3.0025

298 296

4.9 ( +9) - - 0.9

0.8

1.1 1.2

S02 + CH,02 —

products

Sulfur dioxide + Methyldioxyfree radical 79 KAN/MCQ

Best k estimate, based on apparent

rate constant (ka|M , 2k).

2 296 3.2 ( +9) - - 0.8 1.2

SO, + CH=CH —* products

Sulfur dioxide + Ethyne 71 FIF/MOR

Given with caution.

2 1550-2150 3.2 ( + 10) 0.5 20535

S02 ** + CH, = C=CH, —» products

Sulfur dioxide -f 1,2-Propadiene 78 PAR/HE1

kr>

. f

: S02 ** + CH2 = C = CH2 —

CO + other products (S02 ** is a non-emitting triplet).

2 4.0 298 - - -

S02 *(’B,) + cis-CH,CH =CHCH, —

[cis-CH ,CH = CHCH ,.S02 ]* Sulfur dioxide -f- cis-2-Butene 74 DEM/CAL 2 294 1.3 ( + 14) 0.9 1.1

S02 *(

:, B,) + trans-CH ,CH = CHCH , —

[trans-CH ,CH = CHCH ,.S02 ]* Sulfur dioxide + trans-2-Butene 74 DEM/CAL 2 294 1 .2 ( + 14) 0.9 1.1

S02 *('B|) + (CHJjCH —* products

Sulfur dioxide + Propane, 2-methyl78 SU /CAL

Evaluation.

2 298 8.4 ( + 12) - -

SOo’l'B,) + (CH,),CH —* products

Sulfur dioxide + Propane, 2-methyl- 78 SU /CAL

Evaluation.

2 298 8.7 (+11) - -

S02 *(*B,) + cis-CH ( CH,CH = CHCH , —

[S02 .CH 1 CH2 CH = CHCH 1 ]'1'

Sulfur dioxide + cis-2-Pentene 76 WAM 2 295 6.3 ( + 13

)

0.8 1.2

S02 *('B,) + trans-CH,CH2 CH = CHCH ,

[S02 .CH,CH 2 CH=CHCH,]*

Sulfur dioxide + trans-2-Pentene 76 WAM 2 295 1 .0 ( + 14) - - 0.7 1.3

17
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

SO, + M—-SO + O + M

Sulfur dioxide 75 KIE

78 AST/GLA

Rate constant expressed as k[ A r). 78 JUS/RIM

79 GRI/REE

80 SAI/YOK

80 TYA/BAB

80 TYA BAB

SO, + 0 — SO, + 0,

Sulfur trioxide -f- Oxygen atom

71

MER/LEV

k determined in H,S flame. 71 MER/LEV

k determined in COS flame. 72 JAC/WIN

73 SCH

Given with caution. 79 MER/LEV

SO, + 0 + M — SO, + 0, + M

Sulfur trioxide Oxygen atom 75 WES/DEH1

75 WES DEH

Meff: He(l.O) 75 WES I)EH 1 Mprf: S0,(<10.0). Upper limit ratio. 75 WES DEH l MdT: N2 (1.4)

SO, + H,0 ->• H,S04 Sulfur trioxide + Water 75 CAS/DAV

SO, + SO — SO, + SO,

Sulfur trioxide + Sulfur monoxide 75 CHU/CAL

SO, + N — SO, + NO

Sulfur trioxide + Nitrogen atom

72

JAC/WIN

75 WES/DEI1

Upper limit k.

SO, + M SO, + 0 + M

Sulfur trioxide 78 AST/GLA

Rate constant expressed as k[Ar]. 79 AST/GLA

S,0 + 0 — so + so

Sulfur oxide(S2 0) + Oxygen atom

74

STE/ALV

Evaluation.

SH + 0 — S + OH

Mercapto free radical -f~ Oxygen atom

73

SCH

Theoretical estimate.

75

BEN/GOL

Semi-empirical evaluation.

n M k/k r ,. f 77 K A B E/R

(in K)

k factors

f F

2 Kr 2900-5200 1.7( + 16) 0 56370 ±2000 0.6 1.6 2 Ar 3700-6500 4.01 + 14) 0 53890 ±2 170 0.5 2.0

2 Ar 2500-3400 2.91 + 16) 0 58590 ±2270 0.5 2.2 2 Ar 2800-3880 8.01 + 15) 0 54355 0.7 1.3 2 Ar 4300-6200 3.51 + 14) 0 52805

2 Ar 4000-6000 3.31+15) 0 54150

2 S02 4000-6000 5.0( + 14) 0 33520

2 1100-1400 6.51+14) 0 5435

2 900-1600 2.81 + 14) 0 6040

2 300-500 1-5 ( +8) 0 500

2 1480-1550 2.81 + 14) 0 6040

2 1685 1.51+11) - -

3 He 298-507 5.01+16) 0 -785 0.9 1.1 3 He 298 7.31 + 17) - - 0.9 1.1

3 SO, 298 <7. 3( + 18) - -

3 N2 298 1.01 + 18) - - 0.9 1.1

2 298 5.5( + l 1

- - 0.8 1.2

2 298 1.2 ( +9) - - 0.4 1.6

2 300 3.0( +8)

2 298 <6.0 ( +6)

2 Ar 1700-2500 3.21 + 15) 0 3 1880 ±1320 0.6 1.6

2 Ar 1700-2500 3.21 + 15) 0 3 1900 ±300 0.6 1.6

2 298 9.01+11) - - 0.9 1.1

2 298-2500 2.31 + 11) 0.67 956

2 6.31 + 11) 0.5 4000

18
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

SH + 0 —> SO + H

Mercapto free radical ~h Oxygen atom 75 BEN/GOL

Semi-empirical evaluation. 75 CUP/GLA

SH + H — S + hC

Mercapto free radical + Hydrogen atom 72 LAN/OLD

73 BRA/TRU

75 CUP/GLA

76 BAU/DRYT (Recommended k). 79 NIC/AMO

SH + H —>• H + SH

Mercapto free radical + Hydrogen atom 75 BEN/GOL

Semi-empirical evaluation.

SH + S -* H + S2 Mercapto free radical -j- Sulfur atom 73 SCH

75 BEN/GOL

Semi-empirical evaluation 79 NIC/AMO

Upper limit k.

SH + S —> S + SH

Mercapto free radical + Sulfur atom 75 BEN/GOL

Semi-empirical evaluation.

SH + SH — H, + S, Mercapto free radical 73 SCH

Estimated upper limit k.

SH + SH — H2 S + S

Mercapto free radical 72 LAN/OLD

Upper limit k. 73 BRA/TRU

76 BAU/DRY (Recommended k). 79 NIC/AMO

SH + N — H + NS

Mercapto free radical -j- Nitrogen atom 75 BEN/GOL

Semi-empirical evaluation.

SH + N — S + NH

Mercapto free radical -j- Nitrogen atom 75 BEN/GOL

Semi-empirical evaluation.

SH -f- NO —> products Mercapto free radical -j- Nitrogen oxide(NO) 73 BRA/TRU

SH + C— H + CS

Mercapto free radical A~ Carbon atom 75 BEN/GOL

Semi-empirical evaluation.

n M k/k„. 77 K A H E/R

(in K)

k fa

f

"torsF

2 6.3 ( + 11) 0.5 0

2 295 9.6( + 13

)

- - 0.7 1.3

2 293 <6.0 ( + 12)

2 298 2.5 ( + 1.3) - -

2 298 1 -5 ( + 1 3

)

- - 0.7 1.3 2 298 1.5 (+13) - - 0.5 1.5 2 295 1.3( + 13) 0.8 1.2

2 6.3 ( + 11) 0.5 0

2 295 2.4( + 13

)

2 6.3 ( + 11) 0.5 0

2 295 <3.0( + 12

)

- -

2 6.3 ( + 11) 0.5 4000

2 295 <3.0 ( + 10) - -

2 293 < 1 .8 ( + 1 3

)

_ _

2 298 7.8 ( + 12

)

_ _

2 295 7.8 ( + 12

)

- - 0.5 1.5 2 295 1.9( + 13) — — 0.9 1.1

2 6.3 ( + 11) 0.5 403

2 6.3 ( + 11) 0.5 9060

2 298 6.3 ( + 11) - -

2 6.3 (+11) 0.5 0

19
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions n M k/kr„, 77 K A n El R

(in k)

k factors

f F

SH + C — S + CH

Mercapto free radical -f- Carbon atom 75 BEN/GOL 2 4.0 ( + 1 1 ) 0.5 6090

Semi-empirical evaluation.

H,S + 0 — SH + OH

Hydrogen sulfide -f- Oxygen atom 73 SCH 2 200-350 3.8( + l 1 ) 0 920 ±45 0.5 2.0 76 WHY/TIM 2 263-495 4.4( + 12) 0 1660 +50 0.9 1.1 78 WHY/TIM 2 263-495 4.4( + 12

0 1660 ±50 0.8 1.2 80 BAU/COX (Recommended k). 2 250-500 4.3 ( + 12) 0 1660±150 0.8 1.3 k factors apply at 298K only.

D_,S + 0 — SD + OD

Hydrogen sulfide(D2S') -f- Oxygen atom 76 WHY/TIM 2 298-450 6.3( + 12) 0 2145±155 0.5 1.5

H2 S ± 0 — products Hydrogen sulfide + Oxygen atom 78 SLA/BAL 2 281-497 1-5 ( +13

0 1920±45 0.8 1.2 k based on editor's least square fit of 6

given experimental points. 79 SIN/IRW 2 297-502 1.6( +13

0 2171 ±202 0.5 1.5

H2 S + 0, — SO, + H,0

Hydrogen sulfide -/- Ozone 75 BEC/INO 2 298 < 1.2 ( +4) - - Upper limit k. Unreported T assumed to be 298K. 75 GLA/TOB1 2 293-343 4.9 (

10 ) 0 3420

Estimated k. 75 GLA/TOB2 2 298-343 1 .6 (

12 ) 0 2620 ±600 0.2 6.3 75 BAU/DRY (Recommended k). 2 298 4.0 ( +2) - - 0.1 10.0

H,S + H — SH + H,

Hydrogen sulfide -f- Hydrogen atom 71 KUR/PET 2 190-464 CO + CM 0 860 ±30 0.9 1.1 72 ROM/SCH 2 298 2.3( + l 1

) - - 0.8 1.3 73 BRA/TRU 2 298 5.0( + l 1 ) - - 76 BAU/DRY (Recommended k). 2 190-470 7.8 (

12 ) 0 860 ±50 0.5 1.5 79 NIC/AMO 2 295 5.0 ( + 11) - - 0.9 1.1 80 HUS/SLA 2 300 5.2 ( + 11) - - 0.9 1.1

D2 S + D — SD + D2 Hydrogen sulfide(D,S) -f- Deuterium atom 80 HUS/SLA 2 300 4.8 (

1 1

- - 0.9 1.1

H 2 S + OH — SH + H,0

Hydrogen sulfide -j- Hydroxyl free radical 73 WES/OEH3 2 298-885 1.4( + 13 ) 0 443 74 STU 2 298 1.9 ( +12 ) - - 0.8 1.2 76 BAU/DRY (Recommended k). 2 298-900 6.3( +12 ) 0 200± 150 0.7 1.3 k factors changing to: f = 0.5 and F = 1.5 at 900K. 76 PER/ATK1 2 297-427 3.1 ( + 12) 0 0 0.9 1.1 80 BAU/COX (Recommended k). 2 250-400 6.6( + 12 ) 0 225±225 0.8 1.3 k factors apply at 298K only.

H,S + OH —» products (overall) Hydrogen sulfide -/- Hydroxyl free radical 72 NIK/MORI 2 300 5.2 (

12 ) - - Approximate k. 80 COX/SHE 2 297 3.0( + 12) - 0.9 1.1

20
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

H.,S + 0H(v =9) — products Hydrogen sulfide + Hydroxy! free radical 72 WOR/COL

Lower limit k. Unreported T assumed to be 298K.

H,S + CH , — SH + CH

,

Hydrogen sulfide -f- Methyl free radical

76

KER/PAR

Tentative k value.

H2S + M — SH + H + M

Hydrogen sulfide 76 HIG/SAI

77 BOW/DOD

CS + 0 — S + CO

Carbon monosulfide free radical + Oxygen atom

71

HAN/SMI

Evaluation. 73 SCH

Approximate k. 73 SCH

Approximate k. 75 BEN/GOL

Semi-empirical evaluation. 77 LIL/RIC

78 KOL

Unreported T assumed to be 300K. 80 BAU/COX (Recommended k). k factors apply at 298K only.

CS + 0 — S T- CO(v = n) Carbon monosulfide free radical + Oxygen atom

72

HAN/RID

krt. f

: CS + 0 —>• S + C0(v= 13) Ratio increasing from 0.1 to 0.9 between

v =7 and v=12, then decreasing to 0.3 from

v = 14 to v= 15. Unreported T assumed to be 298K. 75 SLA/GRA1

76 BID/BRE

CS + 0 —>• SO + c

Carbon monosulfide free radical -f Oxygen atom 75 BEN/GOL

Semi-empirical evaluation.

CS + 02 — SO + CO

Carbon monosulfide free radical +

Oxygen molecule

73

SCH

Estimated upper limit k.

CS + 0, — COS + 0

Carbon monosulfide free radical +

Oxygen molecule 73 SCH

Estimated upper limit k.

CS + H — S + CH

Carbon monosulfide free radical + Hydrogen atom 75 BEN/GOL

Semi-empirical evaluation.

n M k/kr,.f 77 K A B E/R

(in K)

k factors

f F

2 298 >1.5 ( + 11) - - 0.6 1.4

2 300-600 2.0 ( + 11

)

0 2065 ±150 0.4 2.5

2 Ar 2380-3000 1.3 ( +16) 0 46300

2 Ar 2700-3800 2.0( + 13

)

0 37300±960 0.7 1.5

2 298 8.4 ( + 12) - -

2 298 8.4( + 12

)

- - 0.5 2.0

2 900 9.0 ( + 13

)

- - 0.5 2.0

2 6.3 (+11) 0.5 0

2 150-300 1.6(+14) 0 760 ±140 0.8 1.2 2 300 1.3 ( + 13) - - 0.8 1.2

2 150-300 1.6( + 14) 0 760 ±250 0.8 1.3

2 0.1 298 - - -

2 305 1.2 ( + 13) 0.9 1.1 2 300 1 .4 ( + 13

)

" 0.8 1.2

2 1.6( +12

)

0.5 28940

2 298 <1.8( +6) - -

2 298 < 1 .8 ( +6) - -

2 1 .3 ( + 13

)

0.5 50930

21
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions

CS + II — Sll + C

Carbon monosulfide free radical + Hydrogen atom

75

BEN/GOL

Semi-empirical evaluation.

CS ± S — S ± CS

Carbon monosulfide free radical -/- Sulfur atom 75 BEN/GOL

Semi-empirical evaluation.

CS + S — C + S, Carbon monosulfide free radical ± Sulfur atom 75 BEN/GOL

Semi—empirical evaluation.

CS + S + M — CS, + M

Carbon monosulfide free radical -f- Sulfur atom 76 BAU/DRY (Recommended k).

k, = Kk_,

CS + N —* S + CN

Carbon monosulfide free radical ~h Nitrogen atom 75 BEN/GOL

Semi-empirical evaluation.

CS + N — C + NS

Carbon monosulfide free radical -f- Nitrogen atom 75 BEN/GOL

Semi-empirical evaluation.

CS + c -> s + c. Carbon monosulfide free radical -/- Carbon atom 75 BEN/GOL

Semi-empirical evaluation.

CS + C — C + CS

Carbon monosulfide free radical -f- Carbon atom 75 BEN/GOL

Semi-empirical evaluation.

CS, + 0 — CO + S, Carbon disulfide Oxygen atom 79 HSU/SHA

CS, + O —>• CS + so

Carbon disulfide ± Oxygen atom 71 TAK

75 WEI/TIM

76 BAU/DRY (Recommended k).

CS2 + 0 —*• COS + S

Carbon disulfide -j- Oxygen atom 73 SCH

Approximate k. 74 SLA/GIL

k n.

j : CS, + 0 —

products 76 BAU/DRY (Recommended k). 77 GRA/GUT

k ri .,: CS, + 0 —* products

within the given T range, the k/kr,, f ratio decreases from 0.098 +0.004 at 249K to 0 081 ±0.007 at 500K.

n M k/kr „ f 77 K A B El R

(in K)

k factors

f F

2 2.0 ( + 13) 0.5 48870

2 6.3 ( + 11) 0.5 0

2 1.6 ( +120.5 40463

3 1800-3700 8.7 ( + 13) 0 -4370 0.5 1.5

2 1.3 ( + 12

0.5 1160

2 4.0 (+12) 0.5 37200

2 5.0( + l 1

0.5 20435

2 6.3 (+11) 0.5 0

2 298 3.5 ( + 10) - - 0.9 1.1

2 298 1 .4 ( + 1 2

0.9 1.1 2 218-293 1.7 ( + 13) 0 645 ±35 0.9 1.1 2 200-1000 2.2 ( + 13

0 700 0.7 1.3

2 1100 1.2 ( +12

- -

2 0.093 302 - - -

2 302 2.2 (+11) _ _ 0.5 1.5 2 0.098 249-500

22
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions n M k/k„.f 77 K A ll E/E k factors

(in K) f F

CS, + 0 — COS ± S —continued 77 GRA GUT 2 249-500 1-7 ( + 11) - - 0.9 1.2 Within the given T range, k increases from 1.7x10" at 249K to 5.5xl0"cm , mol' l s"

1

at 500K.

CS, -f- 0 — products Carbon disulfide + Oxygen atom 74 SLA/GIL 2 302 2.4( + 1 2

)

- - 74 GRA/GUT 2 249-500 1.7( + 12) - - 0.9 1.1 Non-linear Arrhenius behavior. Within the given T range, k increases from 1.7x10'"

at 249K to 6.7x1

0

1 “cm 'mol' 's'

1 at 500K. 80 BAU/COX (Recommended k). 2 200-500 3.5 ( + 13) 0 700± 100 0.6 1.6

k factors apply at 298K only.

CS, ± OH — products Carbon disulfide -j- Hydroxyl free radical 78 ATK/PER 1 2 300 <4.2 ( + 10) - - Upper limit k. 78 ATK PERI 2 425 <6.0 (+10) - - Upper limit k. 78 KUR2 2 296 1-1 ( +11

)

- - 0.8 1.2 80 BAU/COX (Recommended k). 2 298 < 1 .2 ( + 1 1

)

- - 5.0 Upper limit k. 80 COX/SHE 2 297 2.6 (+11

)

- - 0.7 1.3 80 IYE/ROW 2 298 <1 -8 ( +9) - - Upper limit k. 80 WIN/SHA 2 251 <6.0 ( +9) - - Upper limit k. 80 WIN SHA 2 297 <9.0 ( +8) - - Upper limit k. 80 WIN SHA 2 363 <9.6 ( +8) Upper limit k.

CS2 + S — CS + s2 Carbon disulfide -f- Sulfur atom 76 BAU/DRY (Recommended k). 2 298 3.9 ( + 11) - - 0.5 1.5

CS, + M — CS + s + M

Carbon disulfide 76 BAU/DRY (Recommended k). 2 Ar 1800-3700 2.6 ( + 1 5

)

0 38960 ±9000 0.5 1.5 80 SAI/TOR 2 Ar 2000-2900 2.5 ( + 1 4

)

0 37240

CS, ± M —> products Carbon disulfide 74 TRA 2 6.8 ( + 14) 0 36000 ±700

k measured in shock tube. Unspecified high T range.

cos + 0 — SO + CO

Carbon oxide sulfide -/- Oxygen atom 71 KRE 2 300-523 9.8 ( +12

)

0 2265

71 KRE/SIM 2 300-523 9.8 (

12 ) 0 2265 72 BRE/MIL 2 297 7.2 ( +9) - - 0.8 1.2 74 KLE/STI 2 263-502 9.9 ( + 12) 0 2167 ±28 0.9 1.1 75 WEI/TIM 2 239-404 1 .2 ( +13 ) 0 2150±35 0.8 1.2 76 MAN/BRA (Recommended k). 2 296 8.4 ( +9) - - 0.9 1.1 k factors changing to: f = 0.3 and F = 3.0 above 300K. 78 YOS/SAI 2 298 7.1 ( +9) - - 0.9 1.1 80 BAU/COX (Recommended k). 2 220-600 1 .6 (

13 ) 0 2250± 150 0.6 1.6

k factors apply at 298K only. 80 ROB/SMI 2 296 1.0( +10) - - 0.9 l.l
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continue

Chemical reactions

COS + 0*('D) -* SO + CO

Carbon oxide sulfide + Oxygen atom

75

GAU/SNE

k : 0, + 0*('D) -> 02 *('2

| , +

) + 0

75 GAU SNE

Evaluation.

COS ± H — CO + SH

Carbon oxide sulfide -/- Hydrogen atom 72 ROM/SCH

75 TSU/YOK

76 BAU/DRY (Recommended k). 76 LEE

77 LEE/STI

COS + OH — products Carbon oxide sulfide -/- Hydroxyl free radical

78

ATK/PER1

Upper limit k. 78 ATK PERI

Upper limit k. 78 KUR2

80 BAU/COX (Recommended k). Upper limit k. 80 COX/SHE

Upper limit k.

COS + 0H(v =9) —> products Carbon oxide sulfide -f- Hydroxyl free radical 72 WOR/COL

Unreported T assumed to be 298K.

COS + S —> CO + S2 Carbon oxide sulfide -/- Sulfur atom 72 JAK/AHM

Evaluation. 74 KLE/DAV

76 BAU/DRY (Recommended k).

COS + S*('D) — CO + S2 Carbon oxide sulfide -j- Sulfur atom 72 LIT/DAL

k ri. f: CH2 = CH2 + S*('D) —>• products 78 SHE/SAF

k rrf: COS + S*('D) -> COS + S(

! P) Optimization. 79 ADD/BYR

80 ADD/DON

COS + CD, — CO + CD,S

Carbon oxide sulfide -h Methyl—d\ free radical 72 JAK/AHM

Evaluation.

COS + CN — SCN + CO

Carbon oxide sulfide -/- Cyanogen free radical 79 ADD/LEI

Lower limit k.

COS ± M —*• products Carbon oxide sulfide 74 TRA

k measured in shock tube. Unspecified, high T range.

n M k/k r „, 77 K A H eik

(in K

k factor 1'

f 1

2 4.1 300

2 300 1.8( + 14) - -

2 298 1 .3 ( + 10) 0.8 1.3 2 300-525 9. 1 ( + 1 2 ) 0 1965 ±185 0.9 1.1 2 298 1.3 (+10) - - 0.8 1.3 2 298-478 9.8 ( + 1.3

0 2775 + 40 0.9 1.1 2 261-500 5.5 ( + 12) 0 1940 ±55 0.8 1.2

2 299 <4.2 ( +9) - _

2 430 <1.2 ( + 10) - -

2 296 3.4 ( + 10) _ 2 298 <3.6( +10) - - 5.0

2 297 <2.4( + 10

- -

2 298 1.5 ( +10

- - 0.4 1.6

2 298 1.1 ( +10) _ _

2 233-245 9.2 ( + 11) 0 1825+60 0.9 1.1 2 230-2600 1.7 ( + 12) 0 2050 ±230 0.3 3.0

2 1.5 300 - - -

2 2.4 298 - - -

2 290 7.2 ( +13

0.8 1.3 2 295 1.8( + 14) " 0.7 1.3

2 354-490 3.8 ( + 11) 0 57 1 0 ± 175 0.6 1.8

2 295 > 1.8( + 13) - -

2 8.3 ( + 14

0 31 700 ±650

24
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions n M k/k„.r 77 K A B E/R

(in K)

k factors

f F

CH,S + CH=CH - CH ,SCH=CH

Methylthio free radical + Ethyne 72 KER/PAR (Recommended k). 2 298-333 7.9 ( +7)

CH,S + CH. = CH_, — CH.SCHXH,

Methylthio free radical + Ethene 72 KER/PAR (Recommended k). 2 298 4.8 ( +8) _ _

CH,S + cy-CH _,CH,S — CH,S, + CH, = CH,

Methylthio free radical + Thiirane 72 JAK/AHM

Approximate k.

2 304-478 3.2( + ll) 0 4430

CH ,S + CH,CH=CHCH, —* CH,CH(SCH,)CH( )CH,

Methylthio free radical + 2—Butene 72 KER/PAR

cis-trans equilibrium-weighted k.

2 298-333 1.6( +9) - -

CH ,SH — CH , + SH

Methanethiol 70 BEN/O'N

Critical evaluation.

1 1005-1102 3.2 ( + 15) 0 38550

CH,SH + 0 —* products

Methanethiol + Oxygen atom 76 SLA/GRA

78 KIR/VET

78 SLA/BAL

Non-linear Arrhenius behavior. Within the given T range, k increasing from l.lxlO 1 "

at 254K to 2.6x 10'~cm 'moC's

-1 at 495K.

22

2

300

300-661 254-495

l.K + 12)

8.5 ( + 12) l.K + 12)

0 -625 ±36 0.9 1.1

CH,SH + OH —* products Methaneth iol -j~ Hydroxyl free radical 80 COX/SHE 2 297 5.4 ( + 13

)

0.9 1.1

CH,SH + CH, -> CHoSH + CH , Methanethiol + Methyl free radical 76 KER/PAR (Recommended k). 2 303 1.2 ( +8) 0.5 2.0

CD,SH 4- CH, CD,S + CH,

Methane—d^-thiol -h Methylfree radical 76 KER/PAR (Recommended k). 2 400-500 1.1 (+1 1

)

0 2065 ±500 0.5 2.0

CD,SH + CH , CD,SH + CH: ,D Methane-d \-thiol -f- Methylfree radical 76 KER/PAR (Recommended k). 76 KER/PAR (Recommended k).

2

2

400-500

400-500

7.6 ( + 1 0

)

l.l(+ll)

0

0

4200 ±250

2065±500

0.5

0.5

2.0

2.0

CD ,SH + CH , -* CD.SH + CH ,D Methane-dA-thiol d~ Methyl free radical 76 KER/PAR (Recommended k). 2 400-500 7.6( + 10

)

0 4200±250 0.5 2.0

cy-CHXHoS* CH , = CHSH

Thiirane 79 SHE/SAF 1 298 5.0 ( + 1 0

)

cy-CH, CH,S + 0 — CH, = CH2 + SO

Thiirane + Oxygen atom 76 LEE/TIM 2 268-424 8.1 ( + 12) 0 18±20 0.9 1.1
Fable of Arrhenius parameters for gas phase chemical reactions of sulfur compounds Continued

Chemical reactions

cy-CH ,CH ,S + 0 , —* CH, = CH , + other products

Thiirane Ozone 80 MAR/HER

8 torr. pressure.

cy-CH,CHoS + H — CH, = CH, + SH

Thiirane -T Hydrogen atom 75 YOK/AHM

cy-CH 2 SCH2 + 11^ cy-CH.SCH + H

Thiirane -f- Hydrogen atom 76 LEE

cy-CHXH.S + S — CH2 = CH, + S, Thiirane -T Sulfur atom 71 STR/O'C

k/krH : 8.3exp(+906/T)

k rel: CH 2 = CH2 + S — cy-CH 2 CH2 S

Conventional photolysis method. 73 KLE/DAV1

cy-CH,CH_,S + CH , —* CH2 = CH2 + CH,S

Thiirane + Methyl free radical 72 JAK/AHM

cy-CH2 CH2S + CD, —» CH2 =CH2 + CD.,

S’

Thiirane -f- Methyl-d, free radical 72 JAK/AHM

Evaluation.

cy-CH2 CH2 S + CD, —> cy-CH 2 CH( )S + CD,H

Thiirane -T Methyl-d t free radical 72 JAK/AHM

Evaluation. 76 KER/PAR (Recommended k).

cy-CH2 CH2 S + CH,S — CH2 = CH2 + CH,S2 Thiirane ~h Methyllhio free radical 72 JAK/AHM

Approximate k.

CH ,SCH, + CH, — (CH,)2 S + CH

Methyl, (methyllhio)-, free radical ~T Methane 76 ART/LEE

Evaluation based on k_, and thermodynamic

data.

CH ,CH 2 SH — CH2 =CH2 + H2 S

Ethanethiol 70 BEN/O'N

Critical evaluation.

CH,CH2 SH -s- CH,CH2 + SH

Ethanethiol 70 BEN/O'N

Critical evaluation.

CH ,CH ,SH + 0 — products

Ethanethiol + Oxygen atom 76 SLA/GRA

78 KIR/VET

78 SLA/BLA

Non-linear Arrhenius behavior. Within the given T range, k increasing from 1 .9x 1

1 “

at 257K to 3.2xlO l_ cm'moL's

-1 at 495K.

n M k/kr „, 77 K A R E/R

(in K)

k factors

f F

2 296 <1.0( +4) - -

2 300-425 5.7(+13) 0 978 ±88 0.9 l.l

2 298 7. 1 ( +11) - - 0.8 1.2

2 298-450 - - -

2 298-355 2.7 ( + 13) 0 0 0.9 1.1

2 304-478 7.1 ( +10) 0 3370±400 0.3 3.3

2 303-477 5.9 ( + 100 3270 ±500 0.2 4.4

2 303-477 2.2 ( + 11) 0 4800 ±500 0.3 4.0

2 300-500 2.2 ( + 11) 0 4800 ±500 0.5 2.0

2 304-478 3.2 ( + 11) 0 4430

2 393-518 6.3 ( + 11) 0 7662

1 785-938 1 .0 ( + 13

0 25900

1 785-938 6.3 ( + 15) 0 36336

2 300 1.7 ( + 12)

2 304-425.8 ( + 12

0 -391 ±18 0.9 1.1 2 257-495 1.9 ( + 12)

26
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds Continued

Chemical reactions

CH ,CH ,SH + CH ., -* products

Ethanelhiol -h Methyl free radical 76 KER/PAR

Tentative k.

(CH ,)_,S + 0 CH ,S(0) + CH,

Methane, thiobis-, + Oxygen atom 76 LEE/TIM

76 SLA/GRA

78 SLA/BAL

Possible non-linear Arrhenius behavior. Within the given T range, k decreasing from 3.8x10'

1 at 252K to 2.2x10' cm 'mol" V at 493K. 80 LEE/TAN 1

(CH,),S ± 0 — products Methane, thiobis-, + Oxygen atom 74 CAD/WIC

(CH ,),S + 0, —» products Methane, thiobis-, + Ozone

78

MAR/HER

Upper limit k.

(CH ;l ),S + H — CH: ,SH + CH,

Methane, thiobis-, ~t~ Hydrogen atom 79 YOK/STR

80 YOK/STR

Indirect measurement.

(CHJ,S ± H —>• CH ,SCH, + H2 Methane, thiobis-, + Hydrogen atom 76 LEE

(CH ,) 2S + OH —* products Methane, thiobis-, ± Hydroxylfree radical 78 ATK/PER1

78 ATK PERI

78 KUR1 (Recommended k). 80 COX/SHE

(CH ,) 2 S + CH , — CH ,SCH 2 + CH , Methane, thiobis-, -f Methyl free radical 76 ART/LEE

CH ,SSCH , + 0 — products

Disulfide, dimethyl-, -f- Oxygen atom 80 LEE/TAN2

CH.SSCH, + H — CH ,S + CH,SH

Disulfide, dimethyl-, -f- Hydrogen atom 80 EKW/JOI)

CH ,SSCH , + OH —> products

Disulfide, dimethyl-, + Hydroxyl free radical 80 COX/SHE

CH SO.CH ^ CH,S02 + CH: , Methane, sulfonylbis- 70 BEN/O N

Critical evaluation.

n M k/k ri , 77 K A B E/K

(in K)

k factors

f F

2 303 3.5 ( +7) - - 0.5 2.0

2 268-424 8.6 ( + 1 2

)

0 -366 ± 16 0.9 1.1 2 300 3.8 ( + 1 3

)

- -

2 252-493 3.8 ( + 13

)

2 272-472 7.7 ( + 12) 0 -404 ±30 0.9 1.1

2 300 3.3 ( + 11) - -

2 296 <5.0 ( +5) - -

2 300-472 1.7 ( + 13

)

0 1320 ±44 0.8 1.2 2 300-472 1.7 (+13) 0 1319±44 0.8 1.2

2 300 9.0 ( + 10) - - 0.7 1.3

2 300 5.9 ( + 12) 0.9 1.1 2 299-430 3.3 ( + 12

)

0 — 1 79 ± 150

2 273-426 3.7 ( + 12

)

0 134± 135 0.6 1.4 2 297 5.5 ( + 1 2

)

” " 0.8 1.2

2 393-518 4.2 ( + 11) 0 4613±82 0.8 1.2

2 270-329 1.3 ( + 14

)

0 0 0.9 l.l

2

. 298-428 5.7 ( + 12) 0 -50 ±50 0.8 1.2

2 297 1 .3 ( + 14

)

- - 0.6 1.4

1 783-913 2.0 ( + 14) 0 30500

27
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions n M k/kr „ f 77 K A B E/fi

(in K)

k factors

f F

cy-CH .CH .CH .S + CH, -* cy-CH XH( )CH2 S + CH,

Thietane + Methyl free radical 76 KER/PAR

Tentative k.

2 300-450 3.2 ( + 11) 0 4630 +750

ey-(CH.,)CHCH,S + S — CH,CH =CH2 + S, Thiirane, methyl-, -f Sulfur atom 71 STR/O'C

k/k,,.,: 8.4exp( + 1057/T)

k r,„: CH , = CHo + S cy-CHXH,S

Conventional photolysis method.

2 298-450 - - -

cy-(CH JCHCHoS + CH , — CH,CH = CH2 + CH,S

Thiirane. methyl-, ~T Methyl free radical 72 JAK/AHM

Evaluation.

2 339-435 2.H + 11) 0 3750±830 0.1 8.3

cy-(CH ,)CHCH ,S + CH , —» cy-[(CH 2 )CHCH_,]S + CH,

Thiirane, methyl-, -f- Methylfree radical 72 JAK/AHM 2 339-435 1.0( + l 1 ) 0 4160±440 0.3 3.0

CH ,CH2 CH,SH + 0 — products 1-Propanethiol + Oxygen atom 78 KIR/VET 2 303-421 8.3 ( + 12) 0 -494 ±22 0.9 1.1

(CH,)XHSH + CH, —products 2-Propanethiol -T Methylfree radical 76 KER/PAR

Tentative k.

2 303 4.1 ( +7) - -

cy-CH .CH_.CH_.CHoS + H CHXHXHXR.SH

Thiophene, tetrahydro-, ~t~ Hydrogen atom 78 HOR/NIS

At 5 torr.

2 295-576 8.5 ( +120 1010

CH,C(S)SCH2CH; , — CH4 + CSo + CH, = CHo

Ethane(dithioic) acid ethyl ester 78 ALA/BIG

78 ALA BIG

k based on reported AH* and AS*.

i

i

629 651-716

1 -8 ( -3)

9.2 ( + 12) 0 22730

CH ,CHXHXHoSH + 0 — products 1-Butanethiol + Oxygen atom 78 KIR/VET 2 306-419 5.8 ( + 12) 0 -321 ± 19 0.9 1.1

CH ,CH .CH .CH.SH + H — CH ,CHXHXH, + H.S

1 -Butanelhiol ~T Hydrogen atom 78 HOR/NIS

At 5 torr.

2 295-576 1.6( + 12) 0 1120

CH: ,CHXHXH,SH + H — CH,,CHXHXH2 S + H 2 l-Butanelhiol + Hydrogen atom 78 HOR/NIS

At 5 torr.

2 • 295-576 1.3( + 13)

n

0 1600

(CH ,) ,CSH ^ (CH,)X = CH2 + H.S

‘2-Propanethiol, 2-methyl70 BEN/O'N

Critical evaluation.

1 950-1230 2.5 ( + 13

0 27830

(CH ,),CSH +CH , —* (CH ,) ,CS + CHX(CH ,) 2 SH + CH,

2-Propanethiol, 2-methyl-, -T Methyl free radical 76 KER/PAR

Tentative k.

2 303 5.9 ( +7) - -

28
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions n M k/k„tf 77 K A B E/P

(in k)

k factors

f E

CH2 =CHCH_,S02CH i —» CH2 =CHCH2 + CH,SO,

1-Propene, 3—methylsulfonyl— 70 BEN/O'N

Critical evaluation.

1 573-633 5.0 (+12) 0 28030

CH: ,SC(0)0CHXH , — CH,SH + CO, + CH, = CH,

Carbonolhioic acid 0-ethyl S-methyl ester 79 ALA/BIG

79 ALA BIG

k based on reported AH1 and AS1

.

1

1

629 490-5501 -0 ( -4)

1.8 ( + 12) 0 23500

CH ,0C(0)SCH2 CH , —*• CH ,0H + COS + CH2 = CH,

Carbonolhioic acid S—ethyl 0—methyl ester 79 ALA/BIG

79 ALA BIG

k based on reported AH* and AS*.

1

1

629 490-550

7.8< -7)

1.2 ( + 13

)

0 27800

CH,CH2 CH2 CH2 CH2SH + 0 — products

1-Penlanethiol -f Oxygen atom 78 KIR/VET 2 302-409 6.2(+12) 0 -328± 19 0.9 1.1

CH,0C(0)SCH(CH,)2 ^CH,0H + C0S + CH,CH = CH,

Carbonolhioic acid 0-methyl S-(l-methylethyl)

ester79 ALA/BIG

79 ALA BIG

k based on reported AH1 and AS*.

1

1

629 440-480

4.6 ( -5)

8.4( + 12) 0 25000

CH ,SC(0)0CH(CH t )2 —*• CH ,SH + C02 + CH,CH =CH2 Carbonolhioic acid S-methyl 0-(1 -methylethyl)

ester79 ALA/BIG

79 ALA BIG

k based on reported AH* and AS*.

(Evacuated sealed tube method).

1

1

629 547-584

9.4 ( -3)

6.7 ( + 11) 0 20060

CH ,SC(0)0C(CH CH,SHH + C02 + CH, = C(CH,)2 Carbonolhioic acid 0-(1, 1-dimethylethyl) S-methyl ester 79 ALA/BIG

79 ALA BIG

k based on reported AH* and AS*.

(Inhibited sealed tube method).

I

1

629 479-502

4.2 ( -1)

5.4 ( + 10) 0 16080

CH ,0C(0)SC(CH ,), —> CH ,0H + COS + CH2 = C(CH i )2 Carbonolhioic acid S-(l, 1-dimethylethyl) 0-methyl ester 79 ALA/BIG

79 ALA BIG

k based on reported AH* and AS*.

1

1

629 370-420

1-2 ( -3)

1 .4 ( + 1 2

)

0 21800

CH ,C(S)SCH2 CH2 CH2 CH, —

CH, + CS2 + CH2 = CHCH2 CH,

Ethane(dithioic) acid butyl ester 78 ALA/BIG

78 ALA BIG

k based on reported AH* and AS*.

1

1 629 651-716

3.3 ( -3)

1.2 ( +13

)

0 22500

CH ,C(S)SCH(CH :t )CH,CH , —

CH, + CS2 + CH2 =CHCH2 CH, + cis-, and trans-CH ,CH = CHCH , Ethane(dithioic) acid 1-methylpropyl ester 78 ALA/BIG

78 ALA BIG

1

1

629 584-639

7.4 ( -2)

6.7 ( + 12) 0 20210

k based on reported AH 1 and AS1

.

29
Table of Arrhenius parameters for gas phase chemical reactions of sulfur compounds — Continued

Chemical reactions n M k/k r „ r T/K A B E/R

(in K)

k factors

f F

CII,C(S)SC«:H ,), — CH , + CS, + (CH,)_,C=CH.

Ethane(dithioic) acid 1, 1 -dimelhylelhyl ester 78 ALA/BIG

78 ALA BIG

k based on reported AH* and AS1

i

i 629

448-502

3.1 ( -1)

1.1 ( + 13) 0 19600

(CH ,).|CSC(CH ,) i — (CH,);! = CH2 + H,S + (CH,):1 SH + (CH ,) :| SH

Propane, 2,2'-thiobis[2-meth vl- 80 MAR/BAR i 633-686 1.3 (+15) 0 2 7545 ±962 0.5 2.0

(CH ,),CSSC(CH ,).,— (CH,)2C=CH2 + other products

Disulfide, bis( 1. 1-dimethylelhyl)- 76 M AR/BAR

In a stirred-flow system. 76 MAR BAR

In a static system.

i

i

603-673

519-573

4.0 ( + 14)

4.0(+13)

0

0

221 30 ±480

21290±240

0.4

0.6

2.5

1.6

30
70 BEN/O’

71 ARM/Cl I.

71 HAL /.I I I

71 CON/VAN

71 Cl 1701,

71 FAI/VAN

71 FIF/MOR

71 HAN/SMI

71 FRF

71 KRE/SIM

71 Kl'R/PET

71 MER/LEV

71 MIY/TAK1

71 MIV/TAK2

71 STR/O’C

71 TAk

72 BRE/MIL

3. Bibliography

1970

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, DC

20402).

1971

Armitage, J. W., and Cullis, C. F., “Studies of the Reaction Between Nitrogen Dioxide and Sulfur Dioxide,” Combust. Flame 16. 125(1971).

Bauer, S. IF, Jeffers, P., Lifshitz, A., and Yadava, B. P.. “Reaction Between CO and SO, at Elevated Temperatures: A Shock-Tube Investigation,” Symp. (Int.) Combust.. (Proe.) 13. 1970 (Pub!. 1971)417.

Connor, J., Van Roodselaar, A., Fair, R. W., and Strausz, 0.

P., "The Addition of Group Via Atoms to Tetramethylthylene. An Addition Reaction with a Negative Activation Energy,” J. Am. Chem. Soc. 93, 560 (1971).

Cupitt, L. T.. and Glass, G. P., “Calculation of Absolute

Concentrations of SH and SO from the E. S. R. Spectra,” Trans. Faraday Soc. 67. 1 (1971).

Fair, R. W., Van Roodselaar, A., and Strausz, O. P., “The

Reaction of S( 'P) Atoms with Molecular Oxygen,” Can.

J. Chem. 49, 1659 (1971).

F’ifer, R., Moreau, R.. and Bauer, S. H., “The Reactions Between SCF and C^H^ (and C2 H ,) at Elevated Temperature. A Single-Pulse Shock Tube Investigation,”

Int. J. Chem. Kinet. 3, 249 (1971). Hancock, G., and Smith, I. W. M., “Infra-red Chemiluminescence from Vibrationally Excited CO. Part

1. The Reaction of Atomic Oxygen with Carbon

Disulphide,” Trans. Faraday Soc. 67. 2586) (1971). Krezenski, D. C., “Competitive Reaction of 0( 'P) with Ozone

and Carbonyl Sulfide,” Diss. Abstr. Int. B 32. 2633

(1971). Krezenski, I). C., Simonaitis, R., and Heicklen, J.. “The

Reactions of O('P) with Ozone and Carbonyl Sulfide,”

Int. J. Chem. Kinet. 3, 467 (1971). Kurylo, M. J., Peterson, N. C., and Braun, W., “Absolute

Rate of the Reaction H -p H,S,” J. Chem. Phys. 54. 943 (1971). Merryman, E. L., and Levy. A., “Sulfur Trioxide Flame

Chemistry—H.S and COS F’lames,” Symp. (Int.) Combust., (Proc.) 13. 1970 (Publ. 1971) 427.

Miyazaki, S., and Takahashi, S., “On the Reaction of Oxygen Atom with Carbon Disulphide, Part 2,” Mem. Def. Acad.

Math. Phys. Chem. Eng. Yokosuka, Jpn. 11 . 307

(1971). Miyazaki, S., and Takahashi, S., “On the Reaction of Oxygen Atom with Carbon Disulphide. Part 3,” Mem. Def. Acad. Math. Phys. Chem. Eng. Yokosuka, Jpn. 11, 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,” Mem. Def. Acad. Math.

Phys. Chem. Eng. Yokosuka, Jpn. 11, 191 (1971).

1972

Breckenridge, W. IF, and Miller, T. A., “Kinetic Study by EPR of the Production and Decay of SO('A) in the Reaction of 0J ('A ) with SO( AT.” J- Chem. Phys. 56. 465 (1972).

72 DAV/KI-Fl Davis, D. 1)., 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('P) with 0-,('2),” Int. .1. Chem. Kinet. 4, 367 (1972). 72 l)AV/kFE2 Davis, I). I)., Klemm. IF IF, Braun, W., and Pilling, M., “A

Flash Photolysis-Resonance Fluorescence Kinetics Study

of Ground-State Sulfur Atoms. 11. Rate Parameters for Reaction of S("P) with (FH,,” Int. J. Chem. Kinet. 4, 383 (1972). 72 DON / FIT Donovan, R. J., and Little, D. J., “The Rate of the Reaction

S('P

;) + 0,,” Chem. Phys. Lett. 13.488(1972).

72 HAN/RII) 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 4- S,” .1. Chem. Soc. Faraday Frans. II 68. 2117

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1973

73 BRA/TRI Bradley, J. N., Trueman, S. P., Whytock, I). A., and Zaleski.

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31
73 KLE/DAV2 ] 975

73 LAN/OLD

73 PAV/STI

73 SCH

73 VES/DEH3

74 ATK/PIT3

74 CAD/WIC

74 C0X2

74 DAV/PRl

74 DEM/CAL

74 KAL/BRA

74 KLE/DAV

74 KLE/STI

74 LEO

74 SLA/GIL

74 STE/ALV

74 STU

74 TRA

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1974

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75 I1EC/ 1 NO

75 BEN/GOI.

75 CAS/I)AV

75 CHI /CAL

75 GEY /TOW

75 Cl P/C1.A

75 DA 17 CAL

75 GAl/SNE

75 GLA/TOBl

75 GLA/T0B2

75 OOR/MILl

75 HAR/WAY

75 k IE

75 SLA/ORA 1

75 TSU/YOK

75 WEI/TIM

75 W ES/DEH

75 WES/DEH2

75 YOK/AHM

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76 ART/LEE Arthur, N. L., and Lee, M-S., “Reactions of Methyl Radicals,

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76 ATK/PER3

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76 DIM

76 HIG/SAI

76 K KR /PAR

76 LKE

76 LEK/TIM

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76 MAR/BAR

76 PER/ATK1

76 SLA/GRA

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1977

77 BOil/DOD Bowman, C. T., and Dodge, L. G., “Kinetics of the Thermal

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78 A LA /BIG

78 AST/GLA

78 ATK/PER1

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78 HOR/MS

78 HVA/PRE

78 JLS/RIM

78 KIR/VET

78 K0L

78 kill I

78 kLR2

78 MAR/HER

78 MAR/REI

78 IOR/HEI

78 SLA/BAI.

78 SI /CAL

78 VAN/OBI

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79 GRI /REE

79 HSl/SHA

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80 BAU/COX

80 CITY /MAC

80 COX /SHE

80 EKW/JOI)

80 GRI /REE

80 HAR/ATk

80 HER/HI I

80 HIG/SAI

80 HIS/SLA

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Phys. Lett. 69. 378 (1980). Herron, J. T., and Huie, R. E., “Rate Constants at 298 K for the Reactions SO + SO + M —>• (SO), + M and SO + (SO), —y SO, + S.,0,” Chem. Phys. Lett. 76. 322 (1980). Higashihara, J’., Saito, K., and Murakami, L, “The

Dissociation Rate of S, Produced from COS Pyrolysis,”

Bull. Chem. Soc. Jpn. 53. 15 (1980). Husain, D., and Slater, N. K. H., “Kinetic Study of the Reactions of Hydrogen and Deuterium Atoms with Hydrogen Bromide and Deuterium Bromide by TimeResolved Resonance Fluorescence,” J. Chem. Soc.

F'araday Trans. 2 76, 276 (1980).

Iyer, R. W., and Rowland, F. S., “A Significant Upper Limit

for the Rate of Formation and OCS from the Reaction of OH with CS,,” Geophys. Res. Lett. 7 , 797 (1980).

Lee, J. H., Tang, I. N., and Klemm, R. B., “Absolute Rate

Constant for the Reaction of O( 'P) with CH ,SCH , from 272 to 472 K,” J. Chem. Phys. 72. 1793 (1980).

Lee, J. H., and Tang, I. N., “Absolute Rate Constant for the Reaction of 0("P) with CH ,SSCH . from 270 to 329 K,”

J. Chem. Phys. 72, 5718 (1980). Martin, G., and Barroeta, N., “Gas Phase Thermolysis of

Sulfur Compounds. II. Ditertiary Butyl Sulfide,” Int. J. Chem. Kinet. 12 , 699 (1980). Martinez, R. I.. and Herron, .1. I'.. “Stopped-Flow Study of

the Gas-Phase Reactions of Ozone with Organic Sulfides: Thiirane,” Chem. Phys. Lett. 72. 74 (1980).

34
80 ROB/SMI

80 SAI/TOR

80 SAI/VOK

80 SLA/GRI

80 TV A/ BAB

80 WIN/SHA

80 YOK/STR

Robertshaw, J. H., and Smith, I W. M., “Rate Data for O + OCS - SO + CO and SO + 0, ->• SO, +

0, by a New Time Resolved Technique,” Int. ,). Chem.

Kinet. 12, 729 (1980).

Saito, K., Toriyama, Y„ Yokubo, T., Higashihara, R., and Murakami, I., "A Measurement of the Thermal

Decomposition of CS, Behind Reflected Shock Waves,”

Bull. Chem. Soc. Jpn. 53, 1437 (1980).

Saito, K., Yokubo, I ., and Murakami, 1., “On the Thermal

Decomposition of SO, Diluted in Ar Behind Reflected Shock Waves,”.). Chem. Rhys. 73. 3017 (1980).

Slack. M., and Grillo, A., “Rate Coefficient Measurements

for SOj + O = SO + 0„" J. Chem. Phys. 73, 967

(1980). Tyaga Raju. M., Babu, S. V., and Subba Rao, V.. “Dissociation Rate Measurements in SO, + Ar

Mixtures Behind Incident Shock Waves,” Chem. Phys. T8. 41 1 (1980). Wine, P. H., Shah, R. C., and Ravishankara, A. R., "Rate of Reaction of OH with CS.,” .1. Phys. Chem. 84, 2499

(1980). Yokota, T.. and Strausz, O. P., “Reaction of Hydrogen Atoms

with Dimethyl Sulfide,” .1. Phys. Chem. 83, 3196

(1980).
Appendix: Conversion Tables

Equivalent second order rate constants

B A cm3 mol -1 s

-1 dm3 mol -1 s

-1 m3 mol -1 s

-1 cm3 molecule -1 s

-1 (mm Hg) -1

s

_I atm -1

s

_l ppm -1 min -1 m2 kN -1 s

-1

1 cm3 mol -1 s

-1 = 1 10 3 10 6 1.66X 10 -24 1.604 x 10 -5 7

-1 1.219 x 10 -2 7

-1 2.453 X 10 -9 1.203 x 10 -4 7

-1

1 dm3 mol -1 s

-1 = 103

1 10 -3 1.66X 10 -21 1.604 x 10 -2 7

-1 12.19 7 1 2.453 X 10 -8 1.203 X 10 -l 7

-1

1 m3 mol -1 s

-1 = 106 103

1 1.66x 10 -18 16.04 7

-1 1.219 x 10“ 7

-1 2.453 X 10 -3 120.3 7

-1

1 cm3 molecule -1 s

-1 = 6.023 X 1023 6.023 X 1020 6.023 X 10 17

1 9.658 x 10 18 7

-1 7.34X 1021 7

-1 •

1.478 x 10 15 7.244 x 10 19 7

-1

1 (mm Hg) -1 s

-1 = 6.236 x 10" 7

62.36 7 6.236 X 10 -2 7

1.035 x 10 -19 7

1 760 4.56X 10 -2 7.500

1 atm -1 s

-1 82.06 7 8.206 x 10 -2 7

8.206 x 10 -5 7

1.362 X 10 -22 7

1.316 X 10 -3

1 6x 10 -5 9.869 X 10 -3

1 ppm -1 min -1 -

at 298 K, 1 atm

total pressure

4.077 x 10 8 4.077 x 105 407.7 6.76x 10 -16 21.93 1.667 X 104

1 164.5

1 m2 kN -1 s

-1 = 8314 7 8.314 7 OO X£

—^o

1.38x 10 -2° 7

0.1333 101.325 6.079 X 10 -3

1

To convert a rate constant from one set of units A to a new set B find the conversion factor for the row A under column B and multiply the

old value by it, e.g. to convert cm3 molecule -1 s

-1 to m3 mol -1

s -

' multiply by 6.023 X 10 17

. Table adapted from High Temperature Reaction Rate Data No. 5, The University, Leeds (1970).

Equivalent third order rate constants

B cm 6 mol -2

s

-1 dm6 mol -2

s -1 m6 mol -2s -1 cm6 molecule -2s

-1 (mni Hg) -2

s - ’ atm -2s

_1 ppm -2 min -1 m4 kN 2 s

1

1 cm 8 mol -2

s

-1 = 1 10 -6 10 -12 2.76 x 10 -48 2.57 x 10 -,0 7

-2 1.48x 10-4 7-2 1.003 X 10 -19 1.447 x 10 -8 7

-2

1 dm6 mol -2

s -1 - 106

1 10 -6 2.76 X 10 -42 2.57x 10 -4 7

-2 148 7

-2 1.003 x 10 -13 1.447 X 10-2 7

-2

1 m6 mol -2s

-1 = 1012 106 1 2.76X 10 -36 257 7

-

1.48 X 10 8 7

-2 1.003 x 10 -7 1.447 X 104 7

-2

1 cm 6 molecule -2

s

-1 = 3.628 X 1047 3.628 X 1041 3.628 X 1035

1 9.328 X 1037 7

-2 5.388 x 1043 7-2 3.64x 1028 5.248 x 1039 7

-2

1 (mm Hg) -2

s -1 = 3.89x 10 9 7

2 3.89x 10 3 72 3.89x 10 -3 72

1.07 x 10 38 7

2

1 5.776 x 105 3.46X 10 -5 56.25

1 atm" 2 s -1 = 6.733 X 103 72 6.733 x 10 -3 P

6.733 x 10 -9 7

2

1.86x 10 -44 T2

1.73X 10 61 6X 10 -11 9.74x 10 -5

1 ppm 2 min -1 = at 298 K,

1 atm total pressure

9.97X 10 18 9.97x 10 12 9.97x 106 2.75x 10 -29 2.89x 104 1.667 x 10 10

1 1.623 x 106

1 m 1 kN -2

s -, = 6.91x 10 7 7

2

69.1 72 6.91x 10 -5 7

2 1.904 X 10 -40 P

0.0178 1.027 X 104 6.16X 10 -7

1

See note to table for second order rate constants.

36
U.S. DEPT. OF COMM. 1. PUBLICATION OR 2. Performing Organ. Report No. 3. Publication Date BIBLIOGRAPHIC DATA

SHEET (See instructions)

REPORT NO. NSRDS-NBS 72 May 1982

4. TITLE AND SUBTITLE

Tables of Rate Constants for Gas Phase Chemical Reactions of Sulfur Compounds

(1971-1980)

5 . author(S) Francis Westley

6. PERFORMING ORGANIZATION (If joint or other than N BS, see in struction s) 7. Contract/Grant No.

national bureau of standards

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

8 . Type of Report & Period Covered

N/A

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State, ZIP)

Morgantown Energy Technology Center and Office of Standard Reference Data

Department of Energy National Bureau of Standards

Morgantown, WV 26505 Washington, DC 20234

10.

SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number: 82-2094

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

11.

ABSTRACT (A 200-word or less factual summary of most significant information. I f document includes a significant

bibliography or literature survey, 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 = ATexp(-E/RT) . The table covers the reactions of sulfur containing

molecules and free radicals, S, S

?

, SO, SCL, S0^, S^O, SH, HoS, CS,

CS ?

, COS, CFLS-, CbLSH, cy-CH

? CH? S7 CH.SCH^* and a number of thiols,

thToethers ,and thioesters , with other compounds. The table includes 19

unimol ecul ar , 208 bimol ecul ar, and 1 3 termol ecul ar reactions totaling

240 distinct chemical reactions. There are 441 rate constants associated

with these reactions, distributed as follows: 30 for first order reactions,

377 for second order reactions, and 34 for third order reactions. The

kinetic data were compiled from 145 experimental papers and 8 critical

reviews published between 1971 and 1980.

12.

KEY WORDS (Six to twelve entries; alphabet! cal order; capitalize only proper names; and separate key words by semicolon s) Arrhenius parameters; chemical kinetics; combustion; decomposition; free radicals;

gas phase; hydrocarbons ; hydrogen; ni trogen; oxygen ; rate of reaction; sulfur

13.

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