v NBS

PUBLICATIONS

r A111D2 TBOmi

NAT'L INST OF STANDARDS & TECH R.I.C.

All 102730091

Westley, Francls/Compllatlon of chemical QC100 .11573 NO. 73 V2;1987 C.2 NBS-PUB-C NSRDS-NBS 73, Part 2

U.S. DEPARTMENT OF COMMERCE / National Bureau of Standards
BB he National Bureau of Standards 1 was established by an act of Congress on March 3, 1901. The Bureau’s overall M goal is to strengthen and advance the nation’s science and technology and facilitate their effective application for public benefit. To this end, the Bureau conducts research to assure international competidveness and leadership of U.S.

industry, science arid technology. NBS work involves development and transfer of measurements, standards and related science and technology, in support of continually improving U.S. productivity, product quality and reliability, innovation

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Provides the national system of physical and chemical measurement;

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Conducts research and provides measurements, data, standards, reference

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'Headquarters and Laboratories at Gaithersburg, MD, unless otherwise noted; mailing address

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2Some divisions within the center are located at Boulder, CO 80303.

^Located at Boulder, CO, with some elements at Gaithersburg, MD
Compilation of Chemical Kinetic

Data for Combustion Chemistry.

Part 2. Non-Aromatic C, H, O, N, and S

Containing Compounds. (1983)

Francis Westley, John T. Herron,

and R. J. Cvetanovid

Research Information Center

National Bureau of Standards

Gaithersburg, Maryland 20899

AiBst

DUoo

- u<is

no 13

V-t - y

14?7

Geochemical Kinetics Division

Center for Chemical Physics

National Bureau of Standards

Gaithersburg, MD 20899

U.S. DEPARTMENT OF COMMERCE, C. William Verity, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

Issued December 1987
Library of Congress Cataloging-in-Publication Data

(Revised for VoL 2)

Westley, Francis. Compilation of chemical kinetic data for combustion chemistry.

(NSRDS-NBS; 73, pt. 1- ) Includes bibliographies and index. Contents: Pt. 1. Non-aromatic C, H, O, N, and S containing compounds (1971-

1982)—pt. 2. Non-aromatic C, H, O, N, and S containing compounds (1983).

1. Combustion — Tables. 2. Chemical reaction. Rate of—

Tables. L Herron, John Thomas, 1931-

EL CvetanoviC, Ratimir J. HI. Center for Chemical Physics (U.S.). Chemical Kinetics Division. IV. Title. V. Series: NSRDS-NBS ; 73, pt 1, etc. QC100.U573 no. 73 pL 1, etc. 602M8s 87-20244

[QD516] [541.3’6T0212]

NSRDS-NBS 73, Part 2

Natl. Stand. Ret Data Ser., Natl. Bur. Stand. (U.S.), 73, Part 2, 142 pages (Dec. 1987) CODEN: NSRDAP

© 1987 by the Secretary of Commerce on Behalf of the United States Government

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1987

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

The National Standard Reference Data System was established in 1963 for the purpose of promoting the critical evaluation and dissemination of numerical data of the physical sciences. The

program is coordinated by the Office of Standard Reference Data of the National Bureau of Stan- dards but involves the efforts of many groups in universities, government laboratories, and private

industry. The primary aim of the program is to provide compilations of critically evaluated physical and chemical property data. These tables are published in the Journal of Physical and Chemical

Reference Data, in the NSRDS-NBS series of the National Bureau of Standards, and through other

appropriate channels.

The task of critical evaluation is carried out in various data centers, each with a well-defined

technical scope. A necessary preliminary step to the critical evaluation process is the retrieval from

the world scientific literature of all papers falling within the scope of the center, followed by the

extraction and organization of the numerical data contained in these papers. The present publication

presents such a compilation of data prepared by the NBS Chemical Kinetics Data Center. Further information on NSRDS and the publications which form the primary output of the

program may be obtained by writing to the Office of Standard Reference Data, National Bureau of

Standards, Gaithersburg, MD 20899.

David R. Lide, Jr., Director

Office of Standard Reference Data

III
Contents

1. Introduction 1

1.1. Overview 1

1.2. Scope 1

1.3. Guide to the Table 2

1.3.1. General 2

1.3.2. Arrangement of the Table 2

1.3.3. Order of Reactions 2

L3.4. Chemical Formulas and Nomenclature 2

1.4. Acknowledgments 2

1.5. References to the Introduction 2

2. Summary of Symbols and Units 2

3. Index of Reactions 4

4. Table of Chemical Kinetic Data for Combustion Chemistry 18

5. References to the Table 127

6. Conversion Factors for Rate Constants 133

7. Erratum to NSRDS-NBS 73, Part 1 134

IV
Compilation of Chemical Kinetic Data for Combustion Chemistry.

Part 2. Non-Aromatic C, H, Oy N, and S Containing Compounds.

(1983)

Francis Westley, John T. Herron, and R. J. CvetanovIC

Chemical Kinetics Division, Center for Chemical Physics, National Bureau of Standards, Gaithersburg, MD. 20899

Chemical kinetic data for reactions of importance in combustion chemistry are compiled. Experimental, theoretical, evaluated, or estimated rate constants are given for reactions of O, 03 , H, H2, OH, H02, H20, N, N3, NO, N02, N20, NH,

NH2, SH, HzS, SO, S02, and the aliphatic, alicyclic, and heterocyclic saturated and

unsaturated Q to Cu hydrocarbons, alcohols, aldehydes, ketones, thiols, ethers,

peroxides, amines, amides, and their free radicals. The data were taken from the

literature published in 1983. Data omitted from Part 1 of this series, covering the

period 1971 to 1982, are also included. The data are reported as rate constants or in terms of the parameters A , n , and B of the extended Arrhenius expression k — A(T /298)" x exp(— B IT), where B = E /R. Data are given for 434 reactions.

Key words: Arrhenius parameters; carbon; chemical kinetics; combustion; compilation; free radicals; gas

phase; hydrocarbons; hydrogen; nitrogen; oxygen; rate of reaction; sulfur.

1. Introduction

1.1.

OvarvSsw

This report provides a compilation of chemical ki- netic data for use by modelers, experimentalists, and theoreticians interested in developing a detailed understanding

of gas phase combustion processes involving fossil fuels. It

is part of a larger effort to develop a comprehensive eval- uated chemical kinetic data base, and is a necessary prelude to that effort. The present compilation covers the

literature published in 1983. It supplements the recently

issued compilation which covered the literature from 1971

to 19821

.

1.2.

Scop®

Data are given for the reactions of aliphatic, alicyclic,

and heterocyclic, saturated and unsaturated hydrocarbons

and their derivatives, and for the reactions with inorganic

species containing hydrogen, oxygen, nitrogen, and sulfur with themselves and with hydrocarbons and their derivatives. Not included are reactions involving aromatic

species, halogens, halogen derivatives, ions, and, with few

exceptions, excited states. The data have been abstracted from the literature published in 1983. Data omitted from Part 1 of this series covering the period 1971 to 1982, are also included.

Only publications containing numerical data have been

abstracted. The abstracted data are either rate constants at some given temperature or the parameters^, n, and B of

the extended Arrhenius expression k = A(T /298)" x

exp{—B IT). Additional data on temperature range, pressure, nature of the third body, and the type of data (i. e., experimental, theoretical, estimated, etc.) are also provided.

1.3.

Quid® to th® Tab!®

1.3.1. Genera!

The compilation is divided into two parts — a table of

rate constants and a bibliography, which contains the ref- erences to the cited literature. The following describes the

arrangement of the table with respect to contents and the

order in which reactions are listed.

1.3.2. Arrangement of the Table

The table is arranged in eight columns. These list the

chemical reaction, the data type, the temperature, the rate constant or the Arrhenius A factor, the n factor, the B

factor where B - E /R, a term indicating the appropriate

units for the rate constants, and an error factor. Other

necessary information such as the bibliographic citation, pressure and nature of bath gas, and notes on methodology or other factors is given in the same column as the

chemical reaction. A detailed description follows:

(1) Column 1 gives the chemical reaction. The names of

the reactants given are the Chemical Abstracts Standard

Names. Synonyms, enclosed in parentheses, are in some

cases also given. Product names are given only in those

cases in which the product is a bridged compound.

The bibliographic citation is given in the form of a Ref- erence Code, which consists of the last two digits of the

year of publication, followed by the first three letters

1
of the names of the first and second author (if present)

separated by a slash. An integer index is attached at the

end when it is necessary to differentiate between otherwise identical Codes.

This column may also include information on the experimental method, analytical procedures, nature of the third

body, pressure, identity of reference reaction in the case

of relative rate measurements, or other comments.

(2) Column 2 indicates the type of data. Data type codes

are described in Sec. 2.

(3) Column 3 gives the temperature or temperature

range.

(4) Column 4 lists the rate constant or the Arrhenius A

factor, or the ratio of the rate constants.

(5) Col umn 5 gives the factor n for the extended Arrhenius expression k — A(T /298)"exp(— B IT).

(6) Column 6 gives the parameter B for the extended

Arrhenius expression/: = A(r/298)"exp(— BIT), where

B is the Arrhenius activation energy divided by the gas

constant, i.e., B — E /RIn the case of relative rate measurements the quantity reported is the difference

B —B (ref), where# (ref) is the value of B for the reference

reaction.

(7) Column 7 indicates the units of the rate constant or

the Arrhenius A factor.

(8) Column 8 gives the error factor as reported in the

original work.

1.3.3. Order of Reactions

The reactions are listed following the order of arrangement given in Table 1 of “The NBS Tables of Thermodynamic Properties”.2 In the present compilation the

reactants contain any of the elements O, H, S, N, and C,

and the order used is: O system, H-O system, S-O-H sys- tem, N-O-H-S system, and C-O-H-S-N system. Examples

of the ordering of reactant species are given below:

(1) O system: O, O* 03

(2) H-O system: H, H* OH, H02, H20, H202

(3) S-O-H system: S, S2, SO, S02, S03, SH, H2S

(4) N-O-H-S system: N, N2, NOz, N03, N20, N203, NH, etc.

(5) C-O-H-S-N system: C, CO, CO* CH, CH2, CH3, CH4, etc.

Index of reactions given in Sec. 3 follows the same or- der of arrangement and can be used to find the page

where a particular reaction is located in the Table of

Chemical Kinetic Data for Combustion Chemistry. The

reaction of ethylene with oxygen atoms, for example, is located at its proper place in the “O ATOM Reactions” at the beginning of the Index, since O atom (the O system)

precedes ethylene (the C system).

1.3.4. Chemical Formulas and Nomenclature

Where possible, chemical formulas are written in semistructural form. The following conventions are used:

(1) For Ci through Q saturated hydrocarbons and their O, S, and N derivatives, semi-structural formulas are

used, e.g., (CH3)2CH2 CH2ONO. Beyond C5 the con- densed forms are used, e.g., CH3(CH2) 8CH2CN.

(2) Unsaturated compounds are written to show the position of the double or triple bond, e.g., ch2 =c=ch2

.

(3) The structures of all alicyclic and heterocyclic compounds are specified with figures in the text.

1.4. Acknowledgments

This work was supported by the Department of Energy, Division of Basic Energy Sciences and the Office of

Standard Reference Data of the National Bureau of Standards. The authors are especially indebted to Mrs.

Geraldine Zumwalt and Ms. Rhoda Levin for their atten- tion to many details in the keyboarding, editing and preparation of the manuscript.

1.5. References to the Introduction

! F. Westley, J. T. Herron, and R. J. CvetanoviC “Compilation of Chemical Kinetic Data for Combustion Chemistry. Part 1. Non-Aromatic C, H, O, N, and S Containing Compounds. (1971-1982)”, NSRDS-NBS 73, Part 1, U. S. Government Printing Office, Washington, D.C. 20402, (1987).

2D. D. Wagman, W. H. Evans, V. B. Parker, R. H. Schumm, I. Halow,

S. M. Bailey, K. L. Churney, and R. L. Nuttall, J. Phys. Chem. Ref. Data 11, Suppl. 2 (1982).

2. Summary of Symbols and Units

Data Type Codes:

EX (experimentally measured absolute value)

RL (experimentally measured relative value)

RN (RL normalized to absolute value)

TH (theoretical value)

DE (derived indirectly, e.g. using reverse rate and

equilibrium constant, or computer simulation of a complex mechanism)

2
CO (computed numerically)

ES (estimated, by analogy etc)

SE (selected in the literature as probable “best”

value)

Type of excitation: f (vibrationally excited)

* (electronically excited)

Decadic exponent notation: 1.2(11) (stands for 1.2 x 1011)

Temperature (T): in kelvins (K).

Arrhenius parameters are defined by

k =A(T /298)"exp(— 5 IT).

Unit Codes for k, k Ik (ref), A, A IA (ref):

1 (s"

1 ) 2 (cm3 mol"1 s"

1 ) 3 (cm6 mol"2 s"

1 ) 1/1, 2/2 etc. (dimensionless)

2/1 (cm3 mol"1 ), etc.

(T /298) and n [the exponent of (T /298)] are dimensionless.

Units for B, B—B (ref): kelvins (K). (Activation

energy E =RxB).

k (ref), A (ref) and B (ref) are the values for the “reference

reaction” in relative rate determinations.

k err. factor: Estimated overall Uncertainty Factor. It multiplies and divides k otA to indicate approximate error

limits. It does not imply that errors in k are necessarily

lognormally distributed.

3
3. Index of Reactions

0 ATOM Reactions:

0 + 0 3 18

0 + H2 18

0 + OH 18

0 + H02 18

0 + H2 02 19

0 + NO (+ M) 19

0 + NH 20

0 + NH2 20

0 + HNO 20

0 + CHO 20

0 + HCHO 20

O + CH3 0N02 21

O + CH=CH 21

O + CH2=CH2 21

0 + CH2=C=0 22

0 + CH3 CH2 0N0 2 22

O + CH3 C=CH 22

O + CH3 CH=C=0 23

O + CH^COCH 23

0 + CH2 =CHC^CH 23

0 + CH 3 CH2 C=CH 23

0 + CH3 CH2 CH=C=0 24

0 + (CH3 ) 2 C=C=0 24

0 + CH3 CH2 CH 2 CH2 OH 24

0 + CH3 CH2 CH(OH)CH3 25

0 + (CH3 ) 2 CHCH2 OH 25

0 + (CH3 ) 3 COH 25

0 3 Reactions:

03 + SO 25

03 + OCHCHO 26

0 3 + CH3 C(0)0N02 26

0 3 + CH 3 C(0)CH0 26

0 3 + cis-CH 3 CH=CHCH3 26

0 3 + cy - CH=CHCH=CH0 (Furan) 26

0 3 + cy - CH=CHCH=CHS (Thiophene) 26

O3 + cy-C5 Hg (Cyclopentene) 27

0 3 + cy-CH=CHCH=CHCH2 CH2 (1 , 3-Cyclohexadiene) 27

0 3 + cy-CH=CHCH2 CH=CHCH2 ( 1 , 4- Cyclohexadiene) 27

03 + cy-CH=CH(CH2 )4 (Cyclohexene) 27

4
V

O 3 + bicy-CyHg Bicyclo [ 2 . 2 . 1 ]hepta- 2 , 5 -diene

(2 , 5-Norbornadiene) .... 27

O3 + bicy-CyHpo Bicyclo [ 2 . 2 . 1 ]hept- 2 -ene (2-Norbornene) .... 28

O 3 + cy-CyHp2 (Cycloheptene) 28

O 3 + bicy-CgH^2 (Bicyclo [ 2 . 2 .

2

] oct- 2 -en) 28

H ATOM Reactions:

H + 0 2 (+ M) 28

H + H02 28

H + SH 29

H + HN3 29

H + CO (+ M) 29

H + CH2 29

H + CHO 30

H + HCHO 30

H + CH3 SH 30

H + CH3 NH2 30

H + C 2 0 30

H + CH2=CH2 (+ M) 31

H + CH 3 CH 3 31

H + cy-CH2 CH2 0 (Oxirane) 31

H + 0=C=C=C=0 32

H + C 3H3 (1-Propynyl, or 2-Propynyl, or 1 , 2-Propadienyl) 32

H + CH=CC=CH 32

H + CH 3 CH2 CH=CH2 32

D + CH 3 CH2 CH=CH2 32

H + cis-CH3 CH=CHCH3 33

D + cis-CH3 CH=CHCH3 33

H + trans-CH3 CH=CHCH3 33

D + trans-CH3 CH=CHCH3 33

H + (CH3 ) 2 C=CH2 (+ M) 33

D + (CH 3 ) 2 C=CH2 34

H + C 6H 5 CH2 34

H2 Reactions:

H2 + C 2 O 34

OH RADICAL Reactions:

OH + H02 34

OH + H2 02 34

OH + S0 2 (+ M) 35

OH + NO (+ M) 35

OH + N02 (+ M) 36

OH + CO 36

OH + CH4 36

OH + CHO 36

5
OH + HCHO 37

OH + CH 3 OH 37

OH + CH 3 OOH 37

OH + CS 2 38

OH + CH 3 SH 38

OH + CH 3 ONO . 38

OH + CH=CH 39

OH + CH2=CH2 39

OH + CH3 CH 3 39

OH + OCHCHO 39

SH + CH 3 CH2 SH 40

OH + (CH 3 ) 2

S 40

OH + 0=C=C=C=0 40

OH + CH2 =C=CH2 40

OH + CH 3 CH=CH2 40

OH + CH 3 CH2 CH 3 41

OH + CH 2 =CHCHO 41

OH + CH 3 C(0)CH0 42

OH + (CH 3 ) 2 CO 42

OH + CH 2 =CHCH=CH2

. 42

OH + trans - CH 3 CH=CHCH3 42

OH + CH 3 CH2 CH2 CH 3 43

OH + cy-CH=CHCH=CHO (Furan) 43

OH + CH 3 CH=CHCHO 43

OH + CH 2 =C(CH3 )CHO 43

OH + CH 3 C(0)CH=CH2 44

OH + cy-CH=CHCH=CHS (Thiophene) 44

OH + CH2 =C=CHCH2 CH 3 45

OH + cis - CH2=CHCH=CHCH3 45

OH + CH2 =CHCH2 CH=CH2 45

OH + CH2 =C=C(CH3 ) 2 45

OH + CH2=C(CH3 )CH=CH 2 46

OH + cy-CH=CHCH2 CH2 CH2 (Cyclopentene) 46

OH + trans -CH 3 CH=CHCH2 CH 3 46

OH + (CH3 ) 2 C=CHCH3 46

OH + cy-CH=CHCH=CHCH2 CH2 (1 , 3 -Cyclohexadiene) 47

OH + cy- CH=CHCH2 CH=CHCH2 (1 , 4-Cyclohexadiene) 47

OH + trans -CH 2 =CHCH-CHCH2 CH 3 47

OH + trans -CH2 =CHCH2 CH=CHCH3 48

OH + CH 2 =CHCH2 CH2 CH=CH2 4 8 OH + CH 3 =CHCHCH=CHCH3 48

OH + CH2=CHC(CH3 )=CHCH3 48

OH + CH 2 =CHC=CH(CH3 ) 2 49

OH + CH2 =C(CH3 )CH2 CH=CH2 49

OH + CH2 =C(CH3 )C(CH 3 )=CH2 49

OH + cy- (CH2 ) 4 CH=CH (Cyclohexene) 50

OH + (CH 3 ) 2 C=C(CH3 ) 2 50

OH + cy-CgH^ 2 (Cyclohexane) 50

OH + bicy-CyHs (2 , 5 -Norbornadiene) 51

6
V

OH + bicy-CyH^o (2-Norbornene) 51

OH + CH2 =C (CH 3 ) CH2 CH2 CH=CH2 51

OH + cy-CH=CH(CH2 )

5

(Cycloheptene) 52

OH + bicy-CyHp2 (Norbornane) 52

OH + 1 , 3 -C 6 H4 (CH 3) 2 (m-Xylene) 52

OH + bicy-CgH^ 2 (Bicyclo [ 2 . 2 . 2 ] oct- 2 - ene ) 53

OH + CH2 =C(CH3 )CH2 CH2 C(CH3 )=CH2 ( 1 , 5 -Hexadiene , 2,5-dimethyl-).. 53

OH + ( CH 3 ) 2 C=CHCH=C ( CH 3

)

2 (2 , 4 -Hexadiene , 2 , 5 - dimehyl - ) 53

OH + bicy-CgH^4 (Bicyclo [ 2 . 2 . 2 ] octane) 54

OH + bicy-CgH ]^4 (Pentalene, octahydro-) 54

OH + cis-bicy-CgH^g (lH-Indene, octahydro, cis-) 54

OH + trans-bicy-CgH^g (lH-Indene, octahydro, trans-) 55

OH + CgH5 CH=C(CH3) 2 (/3-Dimethylstyrene) 55

OH + exo- tricy-C^QH^g (4 , 7 -Methano- 1H- Indene , octahydro-,

( 3aa , 4/3 , 7/3 , 7aa) - ) 56

OH + tricy-C^o^l 6 (Adamantane) 56

OH + cis-bicy-C^o^l 8 (Naphthalene, decahydro-, cis-) 56

OH + trans -bicy- C^QH^g (Naphthalene, decahydro-, trans-) 57

H02 RADICAL Reactions:

H02 + H0 2 (+ M) 57

H02 + NO (+ M) 57

H 2 0 Reactions:

H2 0 + N2 0 5 . 58

H2 0 + CH 3 C( 0 ) 0N02 (Peroxide, acetyl nitro) 58

S0X- COMPOUND Reactions:

SO + 02 58

SO + SO (+ M) 58

S02 + N02 58

502 + CH 3 C( 0 ) 0N0 2 (Peroxide, acetyl nitro) 59

50 3 + N02 59

SHx -C0MP0UND Reactions:

SH + 0 2 59

SH + SH 59

SH + H2

S 59

SH + NO 60

SH + CH 2 =CH2 60

7
^x" COMPOUND Reactions:

N + OH 60

N + H02 60

N + N3 60

N + NH2 61

N + CN(v=n) 61

N + NCC 61

N3 + N 3 61

NxOy-COMPOUND Reactions:

NO + NH2 61

NO + CH 3 C(0)0N02 (Peroxide, acetyl nitro) 62

N02 + CH 3 C(0)0N02 (Peroxide, acetyl nito) 62

N02 + (CH 3 ) 2 NNH2 62

NQ2 + (CH 3 ) 3 CN0 62

N2 0 (+ M) 62

NxHy _ COMPOUND Reactions:

NH + NH2 63

NH(a1A) + HN3 63

NH(a1A) + CH2 =CH2 63

NH(a1 A) + CH 3 CH3 63

NH2 + 02 (+ M) 64

NH2 + N0 2 64

NH2 + NH2 (+ M) 64

C ATOM Reactions:

C + NCCN 64

C0X -C0MP0UND Reactions:

CO + 02 64

CO + N2 0 65

CO + CH 3 C(0)0N02 (Peroxide, acetyl nitro) 65

CH RADICAL Reactions:

CH(v=n) + 02 65

CH(v=n) + N2 65

CH + N2 (+ M) 66

8
CH + NO 66

CH(v=n) + CH3 OH 66

CH + CH=CH 66

CH + CH2=CH2 67

CH2 Reactions:

CH2 (a1A1 ) + 02 67

CH2 (a 1A1 ) + H2 67

CH2 (a 1A1 ) + N2 67

CH2 (a^-A^) + NO 67

CH2 (a 1A1 ) + CO 68

CH2 (a 1A1 ) + CH4 68

CH2 (X3 B 1 ) + CH^CH 68

CH2 (a 1A1 ) + CH2 =CH2 68

CH2 (a 1 A1 ) + CH3 CH3 69

CH2 (a1A1 ) + CH2 =C=0 (Ketene) 69

CH2 (a1A1 ) + CH 3 CH 2 CH 3 69

CH2 (a1 A1 ) + (CH 3 ) 2 C=CH2 69

CH 3 RADICAL Reactions:

CH3 + 02 (+ M) 70

CH 3 + H2S 71

CH3 + CH 3 (+ M) 71

CH3 + CH4 71

CH3 + HCHO (Formaldehyde) 72

CH 3 + CH 3 O (Methoxy) 72

CH 3 + CH 3 CH2 72

CH 3 + CH 30C( 0 ) (Methyl, methoxyoxo-) 72

CH 3 + (CH 3 ) 2

S (Dimethyl sulfide) 73

CH 3 + CH 3 N=NCH3 (Azomethane) 73

CH 3 + CH2 =C=CH2 (Allene) 73

CH3 + (CH 3 ) 2 CH (Isopropyl) 73

CH 3 + (CH 3 ) 2 CO (2-Propanone) 74

CH 3 + (CH 3 ) 3 C ( tert-Butyl) 74

CH 3 + (CH3 ) 3 CH (i-Butane) 74

CH4 Reactions:

CH4 (+ M) 74

CHx0y- COMPOUND Reactions:

CHO (+ M) 75

CHO + 02 (+ M) 75

CHO + CHO 75

HCHO (+ M) 75

HC(0)00H (Performic acid) 75

9
CH3 0 + CH 3 O 76

CH3 O + CH30C( 0 ) (Methyl, methoxyoxo-) 76

CH302 (+ M) 76

CH3 O 2 + CH 3 O2 76

CSx -COMPOUND Reactions:

CS + 0 2 77

CS + O3 77

CS + N02 (+ M) 77

CHxSy- COMPOUND Reactions:

CH 3 S + NO (+ M) 77

CN RADICAL Reactions:

CN(v=n) + 02 78

CN + H2 78

CN + HCN 78

CHxN

y

- COMPOUND Reactions:

HCN (+ M) 78

C 2HX

- COMPOUND Reactions:

CH2 =C : + CH4 78

CH2 =CH (+ M) 78

CH2 =CH + 0 2 79

CH2 =CH + CH4 79

CH2=CH2 (+ M) 79

CH2=CH2 + CH2 =CH2 79

CH2=CH2 + cy-C 5 H0 (Cyclopentene) 80

CH3 CH2 + N02 80

CH3 CH2 + CH2 =CH2 80

CH3 CH2 + CH 3 CH2 80

CH3 CH 3 (+ M) 81

C 2 Hx0y- COMPOUND Reactions:

CH=C=0 + CH=CH 81

CH2 =C=0 (+ M) 81

CH2 =C=0 + CH 3 COOH 81

10
V

CH2 =C=0 + CH 3 COSH 82

CH(0)CH2 + 02 (+ M) 82

CH(0)CH2 + NO (+ M) 82

CH30C( 0 ) + CH 30C( 0 ) (Methyl, methoxyoxo- ) 83

CH 3 CHO + CH 3 C(O)ON0 2 (Peroxide, acetyl nitro) 83

cy-CH2 CH2 0 (Oxirane) (+ M) 83

cy-CH2 CH2 0 + H 83

HC(0)0CH3 (Methyl formate) 84

CH3 C(0)00H (+ M) 84

CH 3 CH2 02 + CH 3 CH2 0 2 84

c 2Hx

sy- C0MP0UND Reactions:

CH 3 SCH 2 + CH4 84

C 2 HxOyS z

- COMPOUND Reactions:

CH 3 SC(0)SH (Thioacetic acid) 85

C 2NX- COMPOUND Reactions:

NCCN (+ M) 85

c 2 HxN

y

- COMPOUND Reactions:

CH2 CN + N02 (Methyl, cyano- + N02 ) 85

CH2 =CHNH2

t (Ethenamine) = cy-CH2 CH2 NHt (Aziridine) 86

CH 3 N=NCH3 (Azomethane; Diazene, dimethyl-) 86

C 2 Hx0

y

Nz

- COMPOUND Reactions:

CH 3 C( 0 ) 00N02 + (CH 3 ) 2 C=CH2 (Peroxide, acetyl nitro + Isobutene) 86

C 3 (Carbon trimer) Reactions:

C 3 + 02 87

C 3 + CH4 87

C 3 + CH=CH 87

C 3 + CH2 =CH2 87

C 3 + CH 3 C=CH 88

C 3 + CH 3 CH=CH2 88

C 3 + CH3 CH2 CH=CH2 88

C 3 + cis-CH3 CH=CHCH3 88

C 3 + (CH 3 ) 2 C=CH 2 89

C 3 + CH3 CH 2 CH2 CH 3 89

C 3 + (CH3 ) 2 C=CHCH3 89

C 3 + CH 3 CH2 CH2 C^CCH3 (2-Hexyne) 89

11
C 3 + (CH 3 ) 2 C=C(CH3 ) 2 90

C 3 Hx -COMPOUND Reactions:

CH2 =CHCH2 + NO (+ M) 90

CH2 =CHCH2 + CH2 =CHCH2 90

cy-C 3 Hg (Cyclopropane) 90

(CH3 ) 2 CH (i-Propyl) 91

(CH3 ) 2 CH + (CH 3 ) 2 CH 91

CH3 CH2 CH 3 (+ M) 92

C 3Hx0y-C0MP0UND Reactions:

CH2 =CHCH2 02 ( 2 - Propenyldioxy) 92

cy-CH2 CH2 CH2 0 (Oxetane) 92

cy-CH2 CH2 CD2 0 (Oxetane-2 , 2-d2 ) 93

cy-CH(CH3 )CH2 0 (Oxirane, methyl-) 93

CH 3 CH 2 C(0)00H (Propaneperoxoic acid) 93

(CH 3 ) 2 CH02 + CH3 CH=CH2 (Ethyldioxy, 1-methyl- + 1-Propene) 94

(CH 3 ) 2 CH0 2 + (CH 3 ) 2 C=CH2 94

(CH3 ) 2 CH02 + CH 3 CH2 C(CH3 )=CH2 94

(CH3 ) 2 CH0 2 + (CH 3 ) 2 CH=CHCH3 94

C 3 HxNy- COMPOUND Reactions:

CH3 CH2 CN (Propanenitrile) 95

C 3 Hx0

y

N2

- COMPOUND Reactions:

CH3 CH2N=C=0 (Ethyl isocyanate) 95

CH 3 CH2 CH2 00N02 (Propyl peroxynitrate) 95

C4HX -C0MP0UND Reactions:

cy-CH=CHCH2 CH2 (v=5,6) (Cyclobutane) 96

CH3 CH=CCH3 + H2 (1-Propenyl, 1 -methyl- + Hydrogen molecule) 96

cis -CH 3 CH=CHCH3 (+ M) 96

CH3 CH2 CHCH3 + H2 (Propyl, 1-methyl- + Hydrogen molecule) .... 96

CH 3 CH2 CHCH3 + cis-CH3 CH=CHCH3 97

(CH 3 ) 3 C + (CH3 ) 3 C (t- Butyl) 97

C4Hx0y- COMPOUND Reactions:

cy - C ( 0 ) CH=CHC (0)0 (Maleic anhydride) 97

cy-C(0)CH2 CH 2 C(0)0 (Succinic anhydride) 97

CH3 C(0)0CH=CH2 (Vinyl acetate) 97

12
V

cy-CH(CH3 )CH2 C( 0)0 (/3-Butyrolactone) 98

CH3 C( 0 ) 0C( 0 )CH3 (Acetic acid anhydride) 98

CH 3 CH2 OCH=CH2 (Ethene, ethoxy-) 98

CH3 C( 0 ) 0CH 2 CH 3 (Ethyl acetate) 98

CH30C( 0 ) 0CH2 CH3 (Carbonic acid ethyl methyl ester) 98

CH3 CH2 CH 2 C( 0 ) 00H (Butaneperoxoic acid) 98

(CH3 ) 2 CHC( 0 ) 00H (Propaneperoxoic acid, 2-methyl-) 99

( 0113)300 (+ M) (t-Butoxy) 99

(CH 3 ) 3 COOH(v=6 ) (t-Butyl hydroperoxide) 99

C 4Hx0

y

S z- COMPOUND Reactions:

CH3 C( 0 ) SC( 0 )CH 3 (Ethanethioic acid anhydrosulf ide ) 99

C 4Hx

N

y

- COMPOUND Reactions:

CH2 =CHCH2 NCt (1-Propene, 3-isocyano-) 100

C 4HxO

y

Nz -COMPOUND Reactions:

(CH3 ) 2 CHNCO (Isopropyl isocyanate) 100

CH3 C(0)NHC(0)CH3 (Acetamide, N-acetyl-) 100

C 5 Hx -C0MP0UND Reactions:

bicy-CgHg (Bicyclo [ . 2 . 1 . 0 ] pent- 2 -ene ) 101

cy-C 5Hg (Cyclopentene) 101

cy-C 5 Dg (Cyclopentene-dg) 101

(CH2 ) 2 >C<(CH2 )

2

(Spiropentane) 101

cy-CgHg (Cyclopentyl) 102

cy-C 5 H9 + N02 (Cyclopentyl + Nitrogen oxide (N02 )) 102

cy-C 5 H 3 o (Cyclopentane) 102

CH3 CH2 CH 2 CH2 CH 3 (n-Pentane) 103

(CH3 ) 4

C (+ M) (Neopentane) 103

C 5 Hx

0

y

- COMPOUND Reactions:

cy-CH2 CH2 CH=CHCH2 0 (2H-Pyran, 3,6-dihydro-) 103

(CH3 ) 2 CH0CH=CH2 (Ethyl isopropyl ether) 103

CH3 CH2 0C( 0 ) 0CH2 CH 3 (Carbonic acid diethyl ester) 103

CH3 CH2 0C( 0 ) 0CD 2 CD 3 (Carbonic acid ethyl ethyl-d5 ester) 104

CH30C( 0 ) 0CH(CH3) 2 (Carbonic acid methyl 1 -methylethyl ester) 104

C 5 HxO

y

Nz- COMPOUND Reactions:

CH 3 C( 0 ) 0CH(CH3 )CN (Propanenitrile , 2- (acetyloxy) - ) 104

(CH 3 ) 3 CNCO (t-Butyl isocyanate) 104

(CH3 ) 2NC( 0 ) 0CH 2 CH 3 (Carbamic acid, dimethyl-, ethyl ester) .. 104

13
C 6 Hx -COMPOUND Reactions:

trans - CH 2 =CHCH=CHCH=CH2 (1 , 3 , 5-Hexatriene , (E)-) 105

cy-CH2 CH 2 CH=CHCH=CH ( 1 , 3 - Cyclohexadiene) 105

cy-C(CH3 )=CHCH=CHCH2 ( 1 , 3 - Cyclopentadiene , 1-methyl-) 105

cy-CH=C(CH 3 )CH=CHCH2 (1 , 3-Cyclopentadiene , 2-methyl-) 105

bicy-CgHg (Bicyclo [ 2 . 2 . 0]hex-2-ene) 105

bicy-CgHg (Bicyclo [ 2 . 1 . 0 ] pent- 2 -ene , 1-methyl-) 106

bicy-CgHg (Bicyclo [ 2 . 1 . 0 ] pent- 2 -ene , 2-methyl-) 106

cy-CgH^Q (Cyclohexene) 106

(cy-CH2 CH2 CH2 CH)CH=CH2 (Cyclobutane, ethenyl-) 107

cy-CgH]_ 2 (+ M) (Cyclohexane) 107

n-CgH]^ (n-Hexane) 107

CgHx0y- COMPOUND Reactions:

cis-cy-0C(0)CH(CH3 )CH(CH3)C(0) ( 2 , 5 - Furandione

,

dihydro- 3 ,4-dimethyl- , cis-) 107

trans , cy-OC(O) CH(CH3) CH(CH3) C(0) ( 2 , 5 - Furandione

,

dihydro-3 ,4-dimethyl- , trans-) 108

cy-CH2 C(CH3 ) 2 CH2 C(0) (Cyclobutanone , 3,3-dimethyl-) 108

CH30(CHCH2 CH2 CH=CH0-cy) 2H-Pyran, 3 ,4-dihydro-2-methoxy- ) 108

CH3 CH 2 C(0)0C(0)CH2 CH 3 (Propanoic acid anhydride) 108

CH 3 C(0)0CH(CH3 )C(0)CH3 (2-Butanone , 3 - (acetyloxy- ) 108

CH 3 C(0)0CH(CH3 )C(0)0CH3 (Propanoic acid, 2- (acetyloxy) -

,

methyl ester) .... 109

CH 3 C(0)0CH2 CH2 C(0)0CH3 (Propanoic acid, 3 - (acetyloxy) -

,

methyl ester) .... 109

CH 3 C(0)0CH2 CH2 0C(0)CH 3 (1,2 - Ethanediol diacetate) 109

CH 3 CH2 CH2 CH2 OCH=CH2 (n-Butyl vinyl ether) 109

(CH 3 ) 3 COCH=CH2 (t-Butyl vinyl ether) 109

CH3 C(0)0C(CH3 ) 3

( t-Butyl acetate) 109

CH3 CH(0H)CH2 C(0)0CH2 CH3 (Butanoic acid, 3-hydroxy-,

ethyl ester) .... 110

(CH 3 ) 2 C(0H)CH2 C(0)0CH3 (Butanoic acid, 3 -hydroxy- 3 -methyl -

,

methyl ester) .... 110

CH 3 0C(0)0C(CH 3 ) 3 (Carbonic acid 1,1-dimethyl methyl ester) ... 110

CgHxSy- COMPOUND Reactions:

CH3 C(0)CH2 SCH2 CH=CH2 (Acetonyl allyl sulfide) 110

CgHxNy-COMPOUND Reactions:

(CH 3 ) 2 CHN=NCH(CH3 )

(Azoisopropane) 110

14
C 6 Hx

O

y

Nz- COMPOUND Reactions:

CH3 C( 0 ) 0C(CH3 ) 2 CN (Propanenitrile , 2- (acetyloxy) -2-methyl- ) . 110

(CH 3 ) 2 NC( 0 ) 0CH(CH3)2 (Carbamic acid, dimethyl-,

1

-

methylethyl ester) 110

C 7 Hx-C0MP0UND Reactions:

cy- CH=CHCH=CHCH=CHCH2 (1 , 3 , 5-Cycloheptatriene) Ill

(cy-CH2 CH2 CH2 CH) C(CH3 )=CH 2 (Cyclobutane, (1-methylethenyl) - )

. Ill

(cy-CgH;Q)CH3 (+ M) (Cyclohexane, methyl-) Ill

c 7 Hx°y" COMPOUND Reactions:

bicy-C 7 Hg0 (Bicyclo [ 3 . 2 . 0 ] hept- 2 -en- 6 -one) 112

cis-cy-CH(CH3 )CH 2 CH=CHCH(CH3 )0 (2H-Pyran, 3,6-dihydro2 , 6 -dimethyl- , cis-) .... 112

c is , trans - cy - OCH ( CH 3) CH ( CH=CH2) CH ( CH 3 ) Oxe tane

,

3 -ethenyl

2 , 4 -dimethyl - ) .... 112

cy-OCH(OCH2 CH 3 )CH2 CH 2 CH=CH (2H-Pyran, 2 -ethoxy- 3 , 4-dihydro- ) . 112

c is - cy - OCH ( OCH3

) CH2 CH ( CH3) CH=CH (2H-Pyran, 3,4-dihydro2-methoxy-4-methyl , cis-) .... 112

trans - cy - OCH (OCH 3

) CH 2 CH ( CH 3) CH=CH (2H-Pyran, 3,4-dihydro2-methoxy-4-methyl , trans-) .... 113

(CH3 ) 2 CHCH2 C( 0 ) 0CH2 CH 3 (Butanoic acid, 3-methyl-,

ethyl ester) .... 113

CH 3 C( 0 ) 0CH2 CH2 CH2 CH20CH3 (1-Butanol, 4-methoxy- , acetate) .... 113

CH3 CH(0H) CH(CH3

) C (0) OCH 2 CH 3 (Butanoic acid, 3-hydroxy2-

methyl- , ethyl ester) .... 113

(CH 3 ) 2 C( 0H)CH2 C( 0 ) 0CH2 CH 3 (Butanoic acid, 3-hydroxy3-

methyl-, ethyl ester) .... 113

C-7 Hx

0yNz

- COMPOUND Reactions:

CH 3 C( 0 ) 0CH(CH3 )CH 2 N(CH3)2 (2-Propanol, 1- (dimethylamino) -

,

acetate ester) .... 113

(CH 3 ) 2 NC( 0 ) 0C(CH3)

3

(Carbamic acid, dimethyl-,

1 , 1 - dimethylethyl ester) .... 113

CsHx -C0MP0UND Reactions:

cy - CH=CHCH=CHCH=CHCH=CH (1 , 3 , 5 , 7-Cyclooctatetraene) 114

[ cy - CH=CHCH=CHCH=CHCH=CH t = bicy-CgHgt] (+ M) 114

bicy-CgHg (1 , 5-Dihydropentalene) 115

[bicy-CgHgt (1 , 5 -Dihydropentalene)^ tricy-CgHgt] (+ M) 115

tricy-CgHg (Semibullvalene) 115

15
syn- tricy-CgHg (Tricyclo [4 . 2.0.02>5] oc ta-3,7 - diene ,

( la , 2a , 5a

,

6 a) - .... 115

anti- tr icy- CgHg (Tricyclo [4 . 2.0.o2.5] oc ta-3, 7 -diene

,

(la, 2 /3 , 5/3 , 6a)- 116

pentacy-CgHg (Cubane) 116

cy-CH=CHCH=CHCH2 CH=CHCH2 (1 , 3

,

6 -Cyclooctatriene) 116

cy - CH=CHCH=CHCH=CHCH ( CH3 ) (+ M) (1 , 3 , 5-Cycloheptatriene

,

7 -methyl- ) .... 116

bicy-CgHgD2 (Bicyclo [ 2 . 2 . 1 ] hept- 2 -ene , 5 -methylene -

2

- ) 116

bicy-CgHio (Bicyclo [ 3 . 2 . 0]hept-2-ene , 6 -methylene-) 117

bicy-CgHgD2 (Bicyclo [ 3 . 2 . 0 ] hept- 2 -ene , 6 -methylene -d2- ) 117

bicy-CgHgD2 (Bicyclo [ 3 . 2 . 0 ]hept-2 -ene-7 , 7 -d2 , 6 -methylene - ) .. 117

bicy-CgH^o (Bicyclo [ 3

2 . 0 ] hept- 6 -ene , 2 -methylene-) 117

bicy-CgH^Q (Bicyclo [ 4 . 2 . 0 ] octa-2 , 4-diene) 118

tricy-CgH^o (Tricyclo [4 . 1 . 0

0 ^ > 7 ]heptane , 3 -methylene - ) 118

cis - cy- CH ( CH 3) CH (CH3) C (=CH2) C (=CH 2 )

( Cyclobutane

,

1 , 2-dimethyl-3 ,4-bis(methylene) - , cis-) .... 118

trans - cy - CH ( CH3

) CH ( CH 3) C (=CH2) C (=CH2 )( Cyclobutane

1 , 2-dimethyl-3 ,4-bis(methylene) - , trans-) .... 118

syn- cy - CH ( CH3) C

( =CH2

) C (~CHCH 3

) CH2

( Cyclobutane

1-ethylidene- 3 -methyl - 2 -methylene , (Z)- .... 119

syn, syn-cy-C(=CHCH3 )C(=CHCH3 )CH2 CH2 (Cyclobutane

,

1 , 2 -diethylidene , (Z,Z)-) .... 119

syn, anti-cy-C(=CHCH3 )C(=CHCH3 )CH2 CH2 (Cyclobutane

,

1 , 2 -diethylidene , (E,Z)-) .... 119

(cy-CgH^^)CH2 CH3 (+ M) (Cyclohexane, ethyl-) 119

cy-(CH2 ) 4CH(CH3 )CH(CH3 ) (+ M) (Cyclohexane, 1,2-dimethyl-) ... 119

cy- (CH2 ) 3 CH(CH3

) CH2 CH(CH3 ) (+ M) (Cyclohexane, 1 , 3 -dimethyl- ) 120

cy- (CH2 ) 2 CH(CH3 ) (CH2 ) 2 CH(CH3 ) (Cyclohexane, 1,4-dimethyl-) ... 120

n-CgH^g (n-Octane) 120

CgHx0y-C0MPQUND Reactions:

bicy-CgH3 QO (Bicyclo [ 3 . 2 . 0 ]hept- 3 -en- 6 -one , 5-methyl-) 120

exo-bicy-CgH;Lo02 (Bicyclo [ 2 . 1 . 0 ] pent- 2 -ene - 5 -carboxylic acid,

5-methyl, methyl ester (la, 4a, 5a)-) .... 121

endo-bicy-CgH3 Q02 (Bicyclo [ 2 . 1 . 0 ] pent- 2 -ene - 5 -carboxylic acid,

5-methyl, methyl ester (la , 4a , 5/3) - ) .... 121

cy-C(CH3 ) 2 CH2 C(CH3 ) 2 C(0) (Cyclobutanone

,

2 , 2 ,4 , 4- tetramethyl- ) .... 122

(CH3 ) 2 CHC(0)0C(0)CH(CH3 ) 2 (Propanoic acid, 2-methyl-,

anhydride) .... 122

CH3 C(0)0CH2 CH 2 CH(CH3 )CH2 CH 3 (1 -Pentanol , 3-methyl-, acetate) . 122

CH 3 C(0)0CH2 CH2 CH2 CH(CH3 ) 2 (1-Pentanol , 4 -methyl - , acetate) ... 123

CH3 C(0)0CH(CH3 )C(CH 3 ) 3 (2-Butanol, 3,3-dimethyl-, acetate) .. 123

(CH 3 ) 3 CCH2 C(0)0CH2 CH 3 (Butanoic acid, 3,3-dimethyl-,

ethyl ester) .... 123

(CH3 ) 3 COOC(CH3 ) 3 (Peroxide, bis (1 , 1-dimethylethyl) - ) 123

16
CgHx

Sy- COMPOUND Reactions:

(CH3 ) 3 CSSC(CH3)

3

(Disulfide, bis ( 1 , 1 -dime thylethyl) - ) 123

C 9 -COMPOUND Reactions:

cy-CH=CHCH=CHCH=CHCH(CH2 CH 3 ) (+ M) (1 , 3 , 5-Cycloheptatriene

,

7 -ethyl-) 124

(cy-CgH^^)CH2 CH2 CH 3 (Cyclohexane, propyl-) 124

CH3 C( 0 ) 0CH 2 CH2 (CHCH2 CH 2 CH 2 CH2 -cy) (Cyclopentaneethanol acetate) 124

CH 3 C( 0 ) 0C(CH3 ) 2 C(CH3)3 (2-Butanol, 2 , 3 , 3- trimethyl- , acetate) 124

CH 3 C( 0 ) 0CH(CH2 CH 3 )C(CH 3)3 (3-Pentanol, 2,2-dimethyl-, acetate) 124

(CH3 ) 3 C0C( 0 ) 0C (CH 3)

3

(Carbonic acid bis (1 , 1- dime thylethyl)

ester) .... 125

C^o to C 14 -COMPOUND Reactions:

(cy-CH=CHCH=CHCH=CHCH)CH(CH3 ) 2 (+ M) 125

bicy-C^obig (Naphthalene, decahydro- ; Decalin) 125

(cy-C 6H 11 )CH2 CH2 CH2 CH 3 (Cyclohexane, butyl-) 125

CH3 C( 0 ) 0CH2 CH2 (CHCH2 CH2 CH2 CH 2 -cy) (Cyclohexaneethanol acetate) 125

CH 3 C (0)0CHCHCH 3 ) 2 C(CH3 )

3

( 3 - Pentanol , 2 , 2 , 4- trimethyl -

,

acetate) .... 126

CH 3 C( 0 ) 0C(CH3 ) (CH(CH3)2)2 (3-Pentanol, 2 , 3 ,4- trimethyl-

,

acetate) .... 126

(cy-CgH^^)CH2 (CH2 ) 4CH 3 (Cyclohexane, hexyl-) 126

n-C]^2N26 (n-Dodecane) 126

(cy-CgH^]^)CH2 (CH2 ) 6 CH 3 (Cyclohexane, octyl-) 126

17
4. Table of Chemical Kinetic Data for Combustion Chemistry

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

0 1 * o2 1 o2 Oxygen atom + Ozone

83 WIN/NIC EX 237-377 (3 . 37±1 . 26) ( 12) 0 1950±110 2 Reaction of 0 atoms with Ozone in

a flow system.

0 atoms generated by pulsed Laser Photolysis of 0^ at 532 nm. Time-resolved Resonance-fluorescence

P = (15-150) torr. [03 ]/[0] o = 1940-21700

0 + H

2

-» OH + H Oxygen atom + Hydrogen molecule

78 CAM/HAN EX 350-490 (3 . 1±0 . 5) ( 13 ) 0 4950±300 2 Reaction of 0 atom with H2 in a dischargeflow stirred reactor. 0 atoms generated by

reacting N with NO.

O + OH -* 02 + H Oxygen atom + Hydroxyl

83 BRU/SCH2 EX 298 Reaction of 0 atom with OH in a fast-flow

reactor. Laser-magnetic resonance. Resonance-fluorescence . Resonance-absorption

P = (1-5) torr. (He, or Ar)

83 TEM EX 296 Reaction of 0 atoms with OH by Far-IR Laser- Magnetic-Resonance Spectrometry.

( 1 . 87±0 . 30 ) ( 13

)

(4 . 0±1 . 2) ( 13 )

2

2

O + H02-* OH + 02 Oxygen atom + Hydroperoxo

79 TEM EX 298 (2 . 0±0 . 6 ) ( 13 ) 2 Reaction of 0 atoms with H02 in an iso- thermal flow-reactor. ESR-spectrometry

LMR-spectrometry . 0 atoms generated by dissociation of 0

2 in a microwave discharge. H02 generated by reacting F with H

202

. 83 BRU/SCH2 EX 298 (3 . 13±0 . 48) ( 13) 2 Reaction of 0 atom with H02 in a fast-flow

reactor. Laser-Magnetic Resonance. Reso- nance-fluorescence. Resonance-absorption

P = (1-5) torr. (He, or Ar)

18
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

83 KEY RL 299 1.7±0.2 2/2

Reaction of 0 atom with HO2 in a fast discharge-flow system. HO2 generated by reacting H with O2 in excess

.

H atom generated by a microwave discharge

of H

2 in He. Resonance-fluorescence

.

kref : 0 + OH - 02 + H. P(Total) = 2 torr.

83 RAV/WIN EX 298 ( 3 . 73±0 . 66) ( 13 ) 2 Reaction of 0 atoms with HO2 by Pulsed- Laser-Photolysis /Resonance- fluor esc enc e

.

0 atoms and HO2 generated by Photolysis of O

3 and H2O2 in N2

, at 248.5 nm. , by using

a KrF excimer laser. P(N2

) = (10-500) torr. [H0£] > [03 P]

.

[H20

2

] = (0.30-1.71)xl0 16 molec.cm-3

. k isindependent of N

2 pressure.

0 + H2O2

"+ OH + HO2

(a)

-* o

2 + e2o (b)

Oxygen atom + Hydrogen peroxide

83 WIN/NIC EX 298-386 ( 6 . 81+3 . 25 ) (11 ) 0 2000±160 2 Reaction of 0 atoms with H

2O2 in a flow- system equipped with a Pyrex reactor and

a Brass reactor. 0 atoms generated by pulsed Laser Photolysis

of O3 at 532 nm. Time-resolved Resonance-fluorescence

.

[0] Q = (0.4-57)xl0 13 molec.cm-3. P = (15-150) torr.

0 + NO (+ M) -* 0

2 + N (+ M) (a)

-* N02

(+ M) (b) Oxygen atom + Nitrogen oxide (NO)

83 SCH/KOH (kb

. M = He) EX 200-370 ( 8 . 27±0 . 58 ) ( 15) 0 -290±17 3

(kb

. M = He) EX 300 2.25(16) 3

(kb

. M = NO) EX 200-370 ( 1 . 36±0 . 05 ) ( 16

)

0 -355±11 3

(kb. M = NO) EX 300 4.57(16) 0 0 3

(kb

. M = n

2

) EX 200-370 ( 8 . 85±0 . 83 ) ( 15) 0 -380+25 3

(kb

. M = n

2

) EX 300 3.19(16) 3

(kb. M = ch4

) EX 200-370 ( 1 . 02±0 . 18 ) ( 16) 0 -414+40 3

(kb

. M = ch 4

) EX 300 4.17(16) 3

19
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Reaction of 0 atoms with NO in a reactive

chamber with a VUV-Laser emitting light

at about 160 nm. Small amounts of 0 atoms generated in the H2 ~Laser photolysis of NO. Chemiluminesxcence emission.

P(He , or N

2

, or CH^) = (10-55) torr. P(NO) = (0.04-1.11) torr.

O + NH -» NO + H (a) (main channel) - OH + N (b) Oxygen atom + Imidogen

83 TEM EX 296 ( 5 . 0±2 . 0 ) ( 13 ) 2 k a + kjj. Far-IR Magnetic-Resonance Spectrometry.

O + RH2 - OB + NH (a) - HNO + H (b)

Oxygen atom + Amidogen

83 TEM (k a

) (kb

) Reaction of 0 atoms with NH2 by Far-IR Laser-Magnetic-Resonance Spectrometry.

O + HNO -» OH + NO

Oxygen atom + Nitrosyl hydride

83 TEM EX 296 5.0(12) 2 Reaction of 0 atoms with HNO by Far-IR

Laser-Magnetic -Resonance Spectrometry.

0 + CHO -» OH + CO (a)

-* H + C02

(b)

Oxygen atom + Methyl, oxo- (Formyl)

78 CAM/HAN RL 425 (4 . 0±2 . 0 ) (-1) 2/2

k

a /kb- Estimated rate ratio. Reaction of 0 CHO in a discharge-flow stirred reactor. 0 atoms generated by reacting N with NO. CHO generated by reacting H with CO.

0 + HCHO -» OH + CHO

Oxygen atom + Formaldehyde

83 GUE/VAN

Reaction of 0 atoms with HCHO in premixed

flames. Molecular-beam sampling.

Mass-spectrometry. Unspecified T-range.

P = (22.5-40) torr.

EX -1400 4.0(13) 0 1807 2

• 20

EX 296 (7,,0±3..0X12)

EX 296 (4.,6±1..2X13)
Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

o + ch3ono2

-» oh + ch2ono2 Oxygen atom + Nitric acid methyl ester

77 SAL/THR EX 294-473 1.5(13) 0 2646±120 2 Reaction of 0 atoms with Methyl nitrate

in a fast-flow system. 0 atoms generated by dissociation of 0

2 (1% in Ar) through a microwave-discharge.

P(Total) = (0.75-15) torr.

O + CH=CH -* CO + CH2(a) 0 + CH^H -» H + CH=C=0 -* CH2=C=0 (b)

-* C=00 + H2

(c)

-* OH + CH^C (d)

Oxygen atom + Ethyne

83 HOM/WEL1

kjj + k(j. Reaction of 0 atoms with Ethyne in

a discharge-flow reactor. 0 atoms generated

by the reaction: N + NO -* N

2 + 0, or by decomposition of 0

2 in a microwave

discharge. Mass-spectrometry. Channel (b) occurs at lower temperatures, while channel

(d) occurs at high temperatures.

P(Total) = 2 torr.

83 H0M/WEL2

kjj. Reaction of 0 atoms with CH^CH, studied

in a flow-reactor, with or without added

H atoms

.

P(Total) = 2 Torr.

O + CH2==CH£ HCHO + CH2

(a) CHO + CH3 (b)

-¥ ch2=c=o + h

2

(c)

-* O

ZA (d)

-* H + CH2CHO (e) Oxygen atom + Ethene

83 FON/MAE < kb

+ k e- P(He) = 0 . 5 torr.

)

< kb

+ k

e

•

P(He

)

= 2 torr . )

< kb

+ k

e

'

P(He) = 5 torr . ) (kb

+ k

e

'

P(He) = 0.5 torr. )

< kb

+ k

e P(He) = 2 torr . )

< kb

+ k

e

•

P(He) = 5 torr .

)

< kb + k

e

’

P(He

)

= 0 . 5 torr . )

< k

b

+ k

e

P(He) = 2 torr . )

(kb

+ k e

•

P(He) = 5 torr . )

EX 295-1330 ( 1 . 6±0 . 5 ) ( 13 ) 0 1550 2

EX 1000 2(12) 2

EX 298 (4 . 10±0 . 48 ) ( 11

)

2 EX 298 ( 4 . 04±0 . 60 ) ( 11

)

2 EX 298 ( 3 . 79±0 . 18 ) ( 11

)

2 EX 552 ( 1 . 57±0 . 06) ( 12) 2 EX 552 ( 1 . 45±0 . 08 ) ( 12) 2 EX 552 ( 1 . 45±0 . 04 ) ( 12) 2 EX 736 (2 . 95±0 . 20 ) ( 12

)

2 EX 736 (2 . 77±0 . 22 ) ( 12

)

2 EX 736 (2. 77+0. 24) (12) 2

21
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Reaction in He diluent, by discharge-flow.

Molecular-beam sampling. Mass-spectrometry.

83 SRI/KAU EX 298 ( 4 . 76±0 . 60 ) ( 11 ) 0 0 2

k 0

. Channel (e) is major path. Discharge-flow

reactor. 0 atoms generated by dissociation of

C>2 in a microwave-discharge, in He diluent.

Resonance-fluorescence. P-independent k. [Ethene] = (0 . 5-6. 0 )xl0^ molec . cm 3

.

[0] o = (0.2-1.2)xl0 natom.cnf 3

. P(Total) = (0 . 42-6) torr.

83 TEM RL 296 0.44±0.15 0 0 2/2

^b^overall" Laser-Magnetic-Resonance

Spectrometry.

O + C02=C=O -» products

Oxygen atom + Ethenone (Ketene)

83 WAS/HAT EX 230-449 ( 1 . 76±0 . 47 ) ( 12) 0 679±78 2 Fast-flow. Pulse-Radiolysis. Resonanceabsorption. Photoionization Mass-spectrometry. 0 atoms generated by dissociation of CO2 in Ar. Measurements at 298 made by using

an 0 atoms source generated by dissociation

of either a 02/He mixture, or a NO/N2 /He

mixture in a microwave-discharge.

P(Ketene) = (18-62) mtorr. P(C02

) = (2.37-3.39) torr. P(Ar ) = (417-526) torr.

O + CH3CH2OHO2 * OB + CH3CHNO2

Oxygen atom + Nitric acid ethyl ester

77 SAL/THR EX 294-473 2.6(13) 0 2598±313 2 Low-pressure fast-flow system, with a Pyrex

reactor. 0 atoms generated by dissociation of

O2 (12 in Ar) through a microwave-discharge.

P(Total) = (0.75-15) torr.

O + CH3OCH -» CO + CH3CH (a) - H + [C3H3O] (b) Oxygen atom + 1-Propyne

83 HOM/WEL1 EX 295-1330 ( 1 . 5±0 . 4 ) (13) 0 1060 2

^overall- Discharge-flow. 0 atoms generated

by the reaction: N + NO * N2 or by decom- position of O2 in a microwave-discharge.

Mass-spectrometry. P(Total) = 2 torr.

22
4. Tabla of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n E, k,A k err. type A,A/A(ref) B-B(ref) units factor

O + CHgCH=C=0 -» products

Oxygen atom + 1-Propen-l-one (Methylketene

)

83 WAS/HAT EX 230-449 (2 . 89±0 . 79) ( 12) 0 249±82 2 Fast-flow reactor. Pulse-Radiolysis.

Resonance-absorption . Photoionization

Mass-spectrometry. 0 atoms generated

by dissociation of CO2 in Ar. Measurements at 298 K made by using an 0 atom source generated by dissociation

of either a 02 /He mixture, or a N0 /N2 /He

mixture in a microwave-discharge.

P(Methylketene) = (2. 0-8. 8) mtorr. P(C02

) = (2. 5-3. 9) torr. P(Ar) = (450-540) torr.

O + CH^CCsCH -» products

Oxygen atom + 1 , 3-Butadiyne

83 HOM/WEL1 EX 300-1000 (2, 8±0 .6) (13) 0 870 2 Discharge-flow reactor. 0 atoms generated

by the reaction:

N + NO - N

2 + 0, or by decomposition of O

2 in a microwavedischarge. Mass-spectrometry.

P(Total) = 2 torr.

0 + CH^XH=CH2 products

Oxygen atom + l-Buten-3-yne

83 HOM/WEL1 EX 295-500 (3 . 0±1 . 1 ) ( 13 ) 0 910 2 Discharge-flow reactor. 0 atoms generated

by the reaction:

N + NO - N

2 + 0, or by decomposition of O2 in a microwavedischarge. Mass-spectrometry.

P(Xotal) = 2 torr.

O + CH3CH2C=CH -* CO + CH3CH=CH2

(a)

-* any other products (b) Oxygen atom + 1-Butyne

83 H0M/WEL1 EX 290-1000 (2 . 3±0 . 7 ) ( 13 ) 0 870 2

^overall' Low-pressure discharge-flow reactor. 0 atoms generated by the reaction:

N + NO - N

2 + 0, or by decompositioq of 03 in a microwave-discharge. Mass-spectrometry. P(Total) = 2 torr.

23'
4 . Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

0 + CH3CH2CEMX) -* products

Oxygen atom + 1-Buten- 1-one (Ethylketene

)

83 WAS/HAT EX 230-449 ( 3 . 23±0 . 50 ) ( 12 ) 0 224±47 2 Fast-flow reactor. Pulse-Radiolysis.

Resonance-absorption . Photoionization

Mass-spectrometry. 0 atoms generated by

dissociation of CO2 in Ar. Measurements at 298 K made by using an 0 atoms source generated by dissociation

of either a 02 /He mixture, or a NO/N2 /He

mixture in a microwave-discharge.

P(Ethylketene) = (1. 8-7.2) mtorr. P(C02

) = (2. 5-3. 5) torr. P(Ar) = (450-550) torr.

O + (033)2000 -* products

Oxygen atom + 1-Propen-l-one, 2-methyl-

(Dimethylketene

)

83 WAS/HAT EX 230-449 ( 3 . 57±0 . 57 ) ( 12 ) 0 569±43 2 Fast-flow reactor. Pulse-Radiolysis.

Resonance-absorption . Photoionization

Mass-spectrometry. 0 atoms generated by

dissociation of C02 in Ar . For experiments

at 298 K the measurements were made by using

an 0 atoms source generated by dissociation

of either a 0

2 /He mixture, or a NO/N2 /He

mixture in a microwave-discharge.

P(Dimethylketene ) = (2. 3-8. 5) mtorr. P(C02

) = (2. 6-3. 5) torr. P(Ar ) = (450-540) torr.

O t CH3CH2CH2CH2

0H OH t CH3CH2CH2CHOH ( a ) - OH + [CAH8OH] (b) Oxygen atom + 1-Butanol

83 ROS 1

) (k

a

) EX 298-606 ( 1 . 35±0 . 39) ( 13 ) 0 1756+505 2 The 0 atom abstracts an H atom only from

a CH bond in position a to OH.

(k OVerall ) EX 298 ~ 606 2.99(13) 0 1780±190 2 1.17 The 0 atom abstracts an H atom from any CH bond

*) Flow-system. 0 atoms generated by reacting N with NO. N atoms generated by dissociation of

N

2 in a microwave-discharge.

Gas-chromatography.

24
Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A

type A,A/A(ref) B-B(ref) units

0 + CH3CH2CH(OH)CH3

-* OH + CH3CH2C(OH)CH3 (a) - OH + [C^HgOH] (b) Oxygen atom + 2-Butanol

83 ROS x

) (k a) The 0 atom abstracts an H atom only from

a CH bond in position a to OH. ^overall ^ The 0 atom abstracts an H atom from any CH bond.

* ) Flow-system. 0 atoms generated by reacting N with NO. N atoms generated by dissociation

N2 in a microwave-discharge.

Gas-chromatography

.

O + (CH3

) 2CHCH2OH - OH + (CH3) 2CHCHOH (a)

-» OH + [C4H8OH] (b) Oxygen atom + 1-Propanol, 2-methyl-

(k

a

) The 0 atom abstracts an H atom only from

the CH bond in position a to OH. ^overall^

The 0 atom abstracts an H atom from any CH bond.

1

) Flow-system. 0 atoms generated by reacting N with NO. N atoms generated by dissociation

of N

2 in a microwave-discharge.

Gas-chromatography

.

O + (CH3

) 3COH -* OH + [CAH8OH]

Oxygen atom + 2-Propanol, 2-methyl83 ROS

Flow-system. 0 atoms generated by reacting

N with NO. N atoms generated by dissociation of N

2 in a microwave-discharge Gas- chromatography. The 0 atom abstracts an H atom from any CH bond.

o

3 + so -» o2 + so2 Ozone + Sulfur monoxide

83 BLA/SHA

SO generated by ArF Laser-photodissociation

of S02 at 193 nm. P(S02

) = 30 mtorr

.

P(02

) < 0.4 torr.

EX 298-606 (3 . 06±0 . 49 ) ( 12 ) 0 1083±289 2

EX 298-606 4.47(12) 0 1190±190 2

EX 298-606 ( 1 . 39±0 . 18) ( 12) 0 1010±289 2

EX 298-606 3.66(12) 0 1100±150 2

EX 298-606 4.99(12) 0 2190±270 2

EX 230-420 2.89(12) 0 1170+120 2

k err. factor

1.17

1.14

1.22

1.33

25
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

O-j + OCHCHO -* products

Ozone + Ethanedial (Glyoxal, or Diformyl)

83 PLU/SAN

Reaction in a Teflon bag.

[OCHCHO] ~3.0xl0 15 molec.cm' 3

.

O3 + CHgC(0)0N02 -» products

Ozone + Peroxide, acetyl nitro

76 PAT/ATK2

Reaction in a Teflon-lined aluminum tank. Gas-chromatography. Mass-spectrometry.

IR-Absorption spectrometry.

[Peroxide] = (2. 9-9. 6) ppm.

[O3] = (13-660) ppm.

O3 + CH-jC(0 )CH0 -» products

Ozone + Propanal, 2-oxo- (Methylglyoxal)

83 PLU/SAN

Reaction in a Teflon bag.

[CH 3C(0)CH0] ] ~3.0xl0 15 molec.cm' 3

.

EX 298 <1.81(3)

EX 296 3.24(4)

EX 298 <3.61(3)

0

O3 + cis-CH3CH=cacu3

-» products

Ozone + 2-Butene, (Z)-

83 ATK/ASC4

Irradiation in a Teflon reaction bag.

Gas-chromatography

[Ozone] Q = (0. 12-1.2)xl0^3 molec.cm'3

°3 + <Qj -* products

Ozone + Furan

83 ATK/ASC2

Irradiation in a Teflon reaction bag.

Gas-chromatography

P(Total) = 735 torr.

[Ozone] Q = 2.38xl0'*’ 3 molec.cm 3

.

°3 + ^ 1)

-* products

Ozone + Thiophene

83 ATK/ASC2

Irradiation in a Teflon reaction bag.

Gas-chromatography. P(Total) = 735 torr. [Ozone] Q = B.SSxlO''-3 molec.cm' 3

.

EX 297 (8 . 31±0 . 96) ( 7 )

EX 298 ( 1 . 46±0 . 17 ) (6)

EX 298 <3.61(4)

0 2

2

2

2

2

2

26
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

03 + -» products

Ozone + Cyclopentene

83 ATK/ASC4

Irradiation in a Teflon bag.

Gas-chromatography

.

[Ozone] Q = (0 . 12- 1 . 2 )xl0^ 3 molec.cm

03 + -* products

02one + 1 , 3-Cyclohexadiene

83 ATK/ASC4

Irradiation in a Teflon bag. Gas - chromatography

.

[Ozone] Q

= (0 . 12-1 . 2)xl0* 3 molec.cm

03 + -* products

Ozone + 1 , 4-Cyclohexadiene

83 ATK/ASC4

Irradiation in a Teflon bag.

Gas-chromatography

.

[Ozone] Q

«=* (0. 12-1.2)xl0^3 molec.cm

» products

Ozone + Cyclohexene

83 ATK/ASC4

Irradiation in a Teflon bag.

Gas-chromatography

.

[Ozone] Q = (0. 12-1 . 2)xl0 13 molec.cm'

EX 297 ( 1 . 66±0 . 20 ) (8)

EX 297 ( 1 . 19+0 . 17 ) ( 9)

EX 297 ( 3 . 85±0 . 45) ( 7

)

EX 297 (6 . 26±0 . 84 ) (7

)

2

2

2

2

Ozone + Bicyclo [2 . 2 . l]hepta-2 , 5-diene

(2, 5-Norbornadiene)

83 ATK/ASC4 EX 297 (2 . 81±0 . 78) (9 ) 2 Irradiation in a Teflon bag.

Gas-chromatography

.

[Ozone

]

Q = (0.12-1.2)xl0 13 molec.cm" 3

.

27
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Ozone + Bicyclo [2 . 2 . l]hept-2-ene (2-Norbornene

)

83 ATK/ASC4 EX 297 ( 1 . 29±0 . 21 ) ( 9 ) 2 Irradiation in a Teflon bag. Gas-chromatography. [Ozone] Q = (0. 12 -

1 . 2 )xl 0 ^ molec.cm-3.

O3 + -» products

Ozone + Cycloheptene

83 ATK/ASC4 EX 297 ( 1 . 92±0 . 22) (8) 2 Irradiation in a Teflon bag. Gas-chromatography. [Ozone] Q = (0 . 12-1 . 2)xl0 :'- 3 molec.cm-3

.

Ozone + Bicyclo [2 . 2 . 2] oct-2-ene

83 ATK/ASC4 EX 297 (4 . 38±0 . 54 ) (7 ) 2 Irradiation in a Teflon bag. Gas-chromatography. [Ozone] Q = (0 . 12-1 . 2)xl0 13 molec.cm-3

.

H + 02

(+ M) - OH + 0 (+ M) (a)

-* H02

(+ H) (b) Hydrogen atom + Oxygen molecule

83 PRA/WOO EX 231-512 (2 . 85±1 . 27 ) ( 14 ) 0 -796±159 3 kb

. Fast-flow discharge. P = (2-10) torr. Mass-spectrometry . Gas-chromatography. M = Ar. [H] = (2 . 6-6 . 0 )xl0^ molec.cm-3

.

[02

] = (0-6.0)xl0 15 molec.cm-3

.

H + H02

-» H2 + 02

(a)

-+ OH + OH (b) - H

20 + 0 (c) Hydrogen atom + Hydroperoxo

83 PRA/WOO (kb

/k Q

) RL 231-464 2.75 0 320+120 2/2 2.45

(kb/k

a

) RL 298 2. 3+0.

2/2

<kb

/k

a

) RL 550 7 . 2±3 .

2/2

(k

a

) SE 231-464 1.02(12) 0 -200±170 2 3.39

(kb

) SE 231-464 2.82(13) 0 *T20±120 2 2.29 Fast-flow discharge. P = (2-10) torr. M = Ar

H02 generated by the reaction:

H + 0

2 + M -* H02 + M.

28
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

H + SH -» H

2 + S Hydrogen atom + Mercapto

81 TIE/WAM

Laser-induced Fluorescence in the (320-330) nm. region. SH generated by H2S photodissociation

in Ar through an ArF excimer Laser,

at 193 nm. P(H2

S] = (30-100) mtorr

.

P(Ar ) = (5-10) torr.

H + HN3 - NH2 + N2(a) - H

2 + N3 (b) Hydrogen atom + Hydrazoic acid

83 K0D1

kg/kfa. Photolysis of Hydrazoic acid

in Xe, at 313 nm. Rate constant ratio estimated on the basis of a proposed mechanism.

Gas-chromatography.

IR-spectrometry

.

P(Xe) = (0-600) torr. P(HN3

) = 50 torr.

EX 298 <1.02(13)

RL 303 1.15

2

2/2

H + CO (+ M) -* CHO (+ M)

Hydrogen atom + Carbon monoxide

78 CAM/ HAN (M = n2

> EX 425 (1.. 44±0 . 12 ) ( 14

)

(M = Ar) EX 425 (9.. 7±0 . 9) ( 13

)

Discharge-flow stirred reactor. H atoms generated by dissociation of H2

.

H + CH2-» H

2 + CH Hydrogen atom + Methylene

83 H0M/WEL2 ES 295 5.0(13)

ES 500 5.5(13)

ES 1000 6.0(13)

Estimations based on a suggested mechanism

for the reaction of Ethyne with 0 atoms, studied in a high-temperature flow-reactor,

with or without added H atoms.

P = 2 torr.

2

2

2

29
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

H + CHO -* H2 + CO (a)

-» ECHO (b) - 0 + CH2

(c) Hydrogen atom + Methyl, oxo78 CAM/HAN RL 425 2.1±0.3 2/2

k

a /k re f. Discharge-flow stirred reactor.

H atoms generated by dissociation of H

2

. CHO generated by reacting H with CO.

k ref : 0 + CHO -* products

H + HCHC -» H

2 + CHO (a)

-» CH2OH (b) Hydrogen atom + Formaldehyde

83 GUE/VAN EX -1400 2.0(14) 0 2607 2 k

g

. Premixed flames. Molecular-beam sampling.

Unspecified T-range. P = (22.5-40) torr

H + CH-jSH -* H

2

S + CH3 (a)

-» H

2 + CH3S (b) Hydrogen atom + Methanethiol (Methyl mercaptan)

83 AMA/YAM (k a

) DE 312-454 6.9(12) 0 841 2

(kb

) DE 312-454 2.9(13) 0 1311 2 Discharge-flow reactor. P = (2. 7-2. 9) torr.

H 1 CH3NH2 H2

t CH2NH2

( a

)

- H2

+ CH3NH (b) Hydrogen atom + Methanamine (Methylamine

)

73 BLU/WAG EX 473-683 ( 1 . 8±0 . 3 ) ( 13 ) 0 2667±151 2 k 0 + k^. Fast-flow reactor. H atoms generated,

by decomposition of H

2 in a microwave discharge. ESR- , and Mass-spectrometry.

[CH3 NH2

] q = 6 . OxlO 17 molec.cm' 3

. P = 5.4 torr.

H + C

20 -» CH + CO

Hydrogen atom + Carbon oxide (C2

0)

83 HOR/BAU EX 298 (2.23±0 . 60) (13) 2 Flow-reactor. M = Ar . C

20 generated in the C3O2 photolysis by KrF excimer Laser pulses

at 248 nm. and detected by Laser-induced

fluorescence. H atoms generated in a micro- wave discharge mixture. [C3 0

2

] = 0.4 mtorr.

[H] = (0.8-6. 5) mtorr. [H2

] = (1.5-70) mtorr. P(Total) =1.1 torr. (Ar)

30
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

83 SCH/MEU EX 298 ( 1 . 93+0 . 72) ( 13 ) 2 Flow-reactor. C^O generated by the photolysis

of 0=C=C=C=0 with a KrF excimer laser pulse

at 248 nm. H atoms generated by dissociation

of H

2 in Ar by a microwave-discharge. Laser- induced Fluorescence. [H] = (0. 8-8.0) mtorr

.

[CgC^] = 0.4 torr.

H + CH2=CH2(+ M) -* H2 + CH2=CH (+ M) (a) + CH3CH2

(+ M) (b) Hydrogen atom + Ethene

83 SRI/KAU (P(Total) = 0.42 torr.) EX 298 7.47(10) 2 (P(Total) = 6.0 torr.) EX 298 2.02(11) 2 k

Q + k^. Discharge-flow reactor. H atoms generated by dissociation of H2 in a microwave-discharge . Resonance-fluorescence

.

M = He. P(Total) = (0.42-6) torr. [Ethene] = ( 0 . 5-6 . 0 )xl0^ molec.cm

[H] q ~ 8xl0*°atom. cm'^

.

Other rate constants tabulated for various pressures within the given

P-range. The rate constant increases

with the pressure.

H + CHgCH-j + C03 + CH^ Hydrogen atom + Ethane

83 BAC ES 823 <4.4(1) 2

Thermolysis of Ethane.

P = 300 torr.

ES 983 <1.4(2) 2

H + ^ - [CH2CH2OH]f -* CH2=CH2 + OH (a)

•+ CH2=CH + H20 (b)

- h2 + A. < c > Hydrogen atom + Oxirane (Ethylene oxide)

83 LIF/BEN (k

a

) ES 830-1200 9.5(10) 0 2516 2

(kb

) ES 830-1200 5.0(9) 0 2516 2

(k

c

) ES 830-1200 2.0(13) 0 4177 2 Pyrolysis of Ethylene oxide diluted in Ar, behind reflected shock-waves, in a singlepulse shock-tube. Gas-chromatography.

P = (1.5-10) atm. Rate constants estimated

on the basis of a suggested mechanism.

31
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

H + 0=C=C=C=0 -» products

Hydrogen atom + 1 , 2-Propadiene-l , 3-dione

76 HAC/PIL

Isothermal discharge-flow. ESR-spectrometry

P = (2-4) torr.

H i C^Hg CH (a)

-* CHgC^CH (b) Hydrogen atom + 1-Propynyl, or 2 Propynyl,

or 1 , 2-Propadienyl

83 H0M/WEL2 (k

fl + kb

)

(k

a + kb

)

<*a + kb

) Estimations based on a suggested mechanism

for the reaction of Ethyne with 0 atoms in

a high-temperature flow-reactor, with or without added H atoms. P = 2 torr.

H + CH^CCaCH -* products

Hydrogen atom + 1 , 3-Butadyine

83 H0M/WEL2

Estimations based on a suggested mechanism

for the reaction of Ethyne with 0 atoms in in a high-temperature flow-reactor, with or without added H atoms. P = 2 torr.

H + CH3CH2CH=CH2

-* CH3CH2CB2CH2

(b)

Hydrogen atom + 1-Butene

83 KYO/WAT

kb

. Pulse-Radiolysis. Resonance-Absorption.

H atoms generated by pulse-irradiation of H

2 with high-energy electrons. P(H2

) = 600 torr. P(l-Butene) = (0.01-0.1) torr.

D + CH3CH2CH=€H2-* CH3CB2CHDCH2

(a)

-* CH3CH2CHCH2D (b)

Deuterium atom + 1-Butene

83 KYO/WAT

kQ. Pulse-Radiolysis. Resonance-absorption.

D atoms generated by pulse-irradiation of D

2 with high-energy electrons. P(D2

) = 600 torr. P(l-Butene) = (0.01-0.1) torr.

EX 296-481 ( 1 . 7±0 . 6 ) ( 13 ) 0 1480±180 2

ES 295 2.7(13) 2 ES 500 4.3(13) 2 ES 1000 6.3(13) 2

ES 295 1.3(12) 2 ES 500 3.5(12) 2 ES 1000 7.5(12) 2

EX 200-500 ( 1 . 49±0 . 26 ) ( 13 ) 0 751±47 2

EX 200-500 ( 1 . 46±0 . 43 ) ( 13 ) 0 826±85 2
4. Table of Chemical Kinetic Data for CombuEtion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

H + cis-CH-jCH=CHCHg -» H2 + CH3CH=CHCH2

(a)

-* H

z + CH3CHCH=CH2

(b)

-» CH3CH2CHCH3 (c) Hydrogen atom + 2-Butene, (Z)-

83 KYO/WAT EX 200-500 ( 1 . 61±0 . 23 ) ( 13 ) 0 965±42 2 k

c

. Pulse -Radiolysis . Resonance-Absorption.

H atoms generated by pulse-irradiation of H

2 with high-energy electrons. P(l-Butene) = (0.01-0.1) torr. P(H2

) = 600 torr.

D t c i s -CH3CH=CHCH3-* CH3CHDCHCH3 Deuterium atom + 2-Butene, (Z)-

83 KYO/WAT EX 200-500 ( 1 . 36±0 . 11 ) ( 13 ) 0 1048±24 2 Pulse-Radiolysis. Resonance-Absorption. D atoms generated by pulse-irradiation of D

2 with high-energy electrons. P(D 2

) = 600 torr. P(l-Butene) = (0.01-0.1) torr.

H + trans-CH3CH=CHCH3-» H2 + CH3CH=CHCH2

(a)

-* H2 t CH3CHCH=CH2

(b)

-* CH3CH2CHCH3 (c) Hydrogen atom + 2-Butene, (E)-

83 KYO/WAT EX 200-500 (2 . 39±0 . 16 ) ( 13 ) 0 1055±19 2 k c

. Pulse-Radiolysis. Resonance-Absorption.

H atoms generated by pulse-irradiation of H

2 with high-energy electrons. P(H2

) = 600 torr. P(l-Butene) = (0.01-0.1) torr.

D + trans-CH3CH=CHCH3

-» CH3CHDCHCH3 Deuterium atom + 2-Butene, (E)-

83 KYO/WAT EX 200-500 ( 1 . 40±0 . 14 ) ( 13 ) 0 1025±27 2 Pulse-Radiolysis . Resonance-Absorption.

D atoms generated by pulse-irradiation of D

2 with high-energy electrons. P(D2

) = 600 torr.

P( 1-Butene) = (0.01-0.1) torr.

H + (CH3

) 2C=CH2

(+ M) - (CH3

) 3C (+ M) (a) Hydrogen atom + 1-Propene, 2-methyl- (Isobutene)

83 KYO/WAT EX 200-500 ( 1 . 25±0 . 10 ) ( 13 ) 0 433±25 2 k

Q

. Pulse-Radiolysis Resonance-Absorption.

H atoms generated by pulse-irradiation of u

2 with high-energy electrons. P(H2

) = 600 torr. P(l-Butene) = (0.01-0.1) torr.

33
4, Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K

type

k ,k/k (ref )

A, A/A(ref

)

n B

B-B(ref)

k,A k err. units factor

D + (CH3

) 2C=CH2

-* (CH3

) 2CDCH2

(a)

-* cch3

) 2CCH2D (b) Deuterium atom + 1-Propene, 2-methyl- (Isobutene)

83 KYO/WAT EX 200-500 ( 9 . 28±0 . 11 ) ( 12 ) 0 442±41 2 k^. Pulse-Radiolysis. Resonance-Absorption.

D atoms generated by pulse-irradiation of D

2 with high-energy electrons. P(l-Butene) = (0.01-0.1) torr

P(D2

) = 600 torr.

Hydrogen atom + Methyl, phenyl- (Benzyl) * Benzene, methyl- (Toluene)

75 LUU/GLA ES 298 ( 5 . 95±4 . 05 ) ( 13 ) 2 Benzyl generated by Flash-photolysis of ~0.06

torr. 1,3,5-Cycloheptatriene, in Ar or N

2

.

H2 + C20 -» products

Hydrogen momecule + Carbon oxide (C20)

83 HOR/BAU EX 298 ( 4 . 22±1 . 81 ) ( 11 ) 2 Flow-reactor. M = Ar. C20 generated in the

C

302 photolysis by KrF excimer Laser pulses

at 248 nm. and detected by laser- induced

Fluorescence. P(Total) = 1.6 torr. (Ar).

[H2

] = (1.5-70) mtorr. [0] =2.1 mtorr

[C3O2) = 7 mtorr.

OH + HQ2-* H20 + 02 Hydroxyl + Hydroperoxo

83 SCH EX 298 ( 4 . 46±0 . 12 ) ( 13 ) 2 Reaction of OH with H02 in a fast-flow

reactor. Laser-magnetic resonance. Resonancefluorescence. Resonance-absorption.

P = (1-5) torr. (He, or Ar)

83 TEM EX 296 (4.0±1.2(13) 2 Reaction of OH with H02 by Far-Infrared

Laser-Magnetic-Resonance Spectrometry

OH + H

202 + H02 + H2Q

Hydroxyl + Hydrogen peroxide

83 LAM/MOL EX 241-413 (6 . 47+1 . 84 ) (10) 2.5 -838±86 2

EX 294 ( 1 . 08+0 . 18 ) ( 12

)

2
Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

The preexponential factor expressed as: (T/298)^'^. Reaction in a Pyrex cell. Resonance-fluorescence. OH generated by

Flash-photolysis of H

2O2 , or HONO2

. P(H0N02

) = (5-10) torr. P(He) = 760 torr

.

P(H20

2

) = (0.7-1. 2) torr.

83 TEM EX 296 (1.0±0.2(12) 2 Reaction by Far-IR Laser-Magnetic-Resonance

Spectrometry

.

OH + S02

(+ M) - HS03 (+ M)

Hydroxyl + Sulfur dioxide

83 PAR/SIN (M = N2

. P = 55 torr. ) EX 297 ( 1 . 4±0 . 4 ) ( 11) 2

(M = N

2

• P 760 torr.) EX 297 ( 5 . 7±0 . 8) ( 11) 2

(M = SFg. P = 100 torr.

)

EX 297 (3 . 0±0 . A ) ( 11) 2 (Limiting low-pressure k.)

Extrapolation of experimental

data to low P's.

ES 297 5.7(16) 3

(Limiting high-pressure k.) ES 297 (7 . 4±0 . A ) ( 11) 2 Fit of experimental data to Lindeman mechanism.

Reaction of OH with S02 in excess N

2 by

Flash-photolysis /Resonance- absorption.

OH generated by Flash-Photolysis of N

20/H2

mixtures, or by Photolysis of H

2

0. P(N2

) = (55-760) torr. P(H2

) = 50 torr.

(OH] = ( 1 . 81-3 . ODxlO^ molec.cm"^.

[S02

] ~2.1xl0^ molec.cm ^

.

Pressure-dependent reaction. Other k’s at different pressures in the (55-760) torr. range are given. The pressure dependence

is given by the expression:

k = (7.4xlO U )/(l+237/P)

where P is in torr. and k is in cm^mol’^s

-

*.

OH + NO (+ M) - HONO (+ M)

Hydroxyl + Nitrogen oxide (NO)

83 BUR/WAL EX 295 (3 . 99±0 . 36) ( 17 ) 3 M = N

2

. M-efficiencies relative to N

2 are: 1.00(N2 ), 0 . 55(He) , 0.67(Ar).

Discharge-flow system. OH generated by reacting H with N02

. Resonance- fluorescence

.

P(Total) = (1-5) torr.

35
4 . Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + N02

(+ M) -* H02 + NO (+ M) (a)

-» H0N02

(+ M) (b) Hydroxyl + Nitrogen oxide (N02

) 83 BUR/WAL EX 295 ( 9 . 79±0 . 73 ) ( 17 ) 3 M = N2

. M-efficiencies relative to N2 are: 1.00(N2

), 0 . 59 ( Ar ) , 0.59(He), O.96(02

), 1.67(C02

). Discharge-flow system. OH generated by reacting H with N02

. Resonance-fluorescence

P(Total) = (1-5) torr.

OH + CO - H + C02(a)

-+ any other products (b)

Hydroxyl + Carbon monoxide

83 RAV/THO <k

a

> EX 250-350 ( 1 . 33±0 . 55) ( 11

)

0 145±100 2

(k

a

) EX 298 ( 8 . 67±0 . 72 ) ( 10

)

2 Resonance-fluorescence . Flash-photolysis

OH generated by pulse-radiolysis of H

2

0, at 165 nm. [OH] = (l-lO)xlO^ molec.cm-3

.

[CO] = (0. l-6.0)xl0 15 molec.cm-3

. Experimental rate constants at various

temperatures within the (251-1040) K range

are tabulated, giving a strongly curved Arrhenius plot. A non-linear least-squares

fit gives the expression:

k = 6 . 02xl0 23 exp( -30 . 03±1 . 22x10 -3

T

)

cm3mol

- ^s -3

. OH + CH^ -» H20 + CHg

Hydroxyl + Methane

83 BAU/CRA RN 403-696 2.87(11) 2.13 1233 2/2

(Alternate eqn. ) RN 403-696 1.65(11) 2.4 1060 2/2

The preexponential factors expresed as: (T/298) n

. Reaction in a conventional

"mercury free” vacuum line. OH generated

by photolysis of H

20 at 184.9 nm. Gas-chromatography. [CO] = (5.7-75) torr.

[H20] = (12.3-28.1) torr. P(Total) < 97.5 torr.

k ref : OH + CO -> H + C02

OH + CHO -* H20 + CO

Hydroxyl + Methyl, oxo83 TEM EX 296 ( 1 . 1±0 . 3 ) ( 14 ) 2 Far-IR Laser-Magnetic-Resonance Spectrometry.

36
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + HCHO -* H20 + CHO (a) - H

20 + CHOf (b) - HCOOH + H (c) Hydroxyl + Formaldehyde

83 GUE/VAN EX -1400 4.1(13) 0 710 2 k

0

. Premixed flames. Molecular-beam sampling.

Mass-spectrometry

.

Unspecified T-range.

P = (22.5-40) torr.

83 TEM EX 296 ( 5 . Oil . 0 ) ( 12) 2 k a

. Far-IR Laser-Magnetic-Resonance

Spectrometry.

OH + CH3OH -» 020 + CH20H (a)

-* H20 + CH3O (b) Hydroxyl + Methanol

83 HAG/LOR (k

a + kb

) EX 295-420 ( 7 . 23±1 . 81 ) ( 12) 0 810±50 2

< k

a

/< k a + kb>> RL 298 ( 1 . 1±0 . 3 )

( -1

)

2/2

< k a'< k a + kb» RL 393 (2 . 2±0 . 7 )

( - 1

)

2/2

Laser-photolysis/Resonance- fluorescence

.

OH generated by Laser-photolysis

of H0N02 at 248 nm. P(H0N02

) <75 mtorr

.

[OH] = 4.0x10^ molec.cm

- ^.

83 TUA/CAR1 RL 300 0.314±0.024 2/2 k a + kjj. Teflon rectangular vessel. FTIR-Spectrometry

.

OH generated by reacting O

3 with NH2=NH2

.

^ref' + (CH3

) 20 -* products.

P = 735 torr.

OH + CH3OOH -» H

20 + CH2OOH (a) - H

20 + CH302

(b) Hydroxyl + Hydroperoxide, methyl83 NIK/MAK (k a

/kb

) RL 298 0.77±0.15 2/2

(k

a + kb

) RN 298 6.02(12) 2 FTIR-technique . OH generated by photolysis

of CH3 0N0, or CH 3 CH20N0. kg + kb derived from the ratios

< k

a + k

b

)/krefl and (k

a + kb

)/kref2 where k ref 1

: OH + CH2=CH2

, and

k ref2

' OH + CH3CHO.

37
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(re£) B-B(ref) units factor

OH + CS2

-» SH + COS (a)

-* SOH + CS (b)

-* any other products (c) Hydroxyl + Carbon disulfide

83 BAR/BEC EX 293 ( 1 . 63±0 . 36) ( 12) 2

v overall. FTIR-Spectroscopy using photolytic

and nonphotolytic competitive techniques.

The effective k is dependent on T,P, and 0

2 concentrations.

P(Total) = 760 torr.

OH + CHgSH -* products

Hydroxyl + Methanethiol (Methyl mercaptan)

83 LEE/TAN EX 296 ( 1 . 54±0 . 27 ) ( 13 ) 2 Discharge-flow. OH generated by the reaction:

H + N02

-* OH + NO.

H atoms generated by decomposition of H

2 in He, by a microwave-discharge.

Resonance- fluorescence

[OH] = 7xl0 10 molec.cm' 3

. [CH^SH] = ( 1 . 3-9 . 7 )xl0 ^ 3 molec.cm-3

. 83 MAC/POU EX 293 ( 1 . 26±0 . 60 ) ( 12) 2 Discharge-flow. EPR-spectrometry

OH + CH-jONO -» products

Hydroxyl + Nitrous acid methyl ester

83 TUA/CAR1 1

) RL 300 0 . 038±0 . 007 2/2

k ref : 0H + CH

3 (CH2 ),CH

3 - products

83 TUA/CAR1 1

) RN 300 ( 1 . 33±0 .24(11) 2 Put on absolute basis by using the literature

value of the rate constant for the reaction: OH + CHgCCH^^CHg -* products.

83 TUA/CAR1 1

) RL 300 0 . 04 1±0 . 009 2/2

k re f

; OH + (CH3

) 20 -+ products.

83 TUA/CAR1 1

) RN 300 (8.43±2. 40(10) 2 Put on absolute basis by using the literature

value of the rate constant for the reaction: OH + (CH 3

) 20 -» products.

83 TUA/CAR1 *) SE 300 1.08(11) 2 Average of the two normalized rate constants given above

1

) Teflon vessel. FTIR-Spectrometry . OH generated by reacting O3 with NH2=NH2

. P = 735 torr.

38
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + CH^CH -* H + CH2=C=0 (a) - h

2 + ce=c=o (b) CO + CH3 (c)

-» H + CH^COE (d)

-» [HO.CH^CH]* (e) Hydroxyl + Ethyne

83 TEM EX 296 (9 . 4±2 . 0) ( 10) 2

^overall - R0ac tion of OH with CH=CH by FarIR Laser-Magnetic-Resonance Spectrometry.

OH + CH2=CH2-» CH2CH2OH -» products (a)

-* H20 + CH2+CH (b) Hydroxyl + Ethene

83 TUL EX 291-591 ( 1 . 05±0 . 32) ( 12) 0 -462±108 2 k

a

. Reaction in a flow-reactor, in He diluent. OH generated by the 193 nm. photolysis of N20 to O(^D) and N2 and subsequent

reaction of 0(^D) with H

2

0. Tunable dye Laser Fluorescence. P(He) = (50-600) torr.

OH + CH3CH3 -• H20 + CH3CH2 Hydroxyl + Ethane

83 BAU/CRA X

) RN 300-2000 1.11(12) 1.9 570 2/2 OH generated by the photolysis of H

20 at 184.9 nm. Gas - chromatography

.

P(Total) < 97.5 torr. [CO] = (5.7-75) torr.

[H2

0] = (12.3-28.1) torr.

k ref : OH + CO - H + C02 83 TUL/RAV x

) EX 297-800 3.41(12) 1.05 911 2 Flash-photolysis . Resonance-fluorescence

.

OH generated by Flash-photolysis of H20. *) The preexponential factors expressed as: (T/298

)

n

.

OH + OCHCHO -» products

Hydroxyl + Ethanedial (Glyoxal, or Diformyl)

83 PLU/SAN RN 298 (6 . 93±0 . 24 ) ( 12) 2 Reaction of OH with Glyoxal by a competitive

technique, in an environmental chamber. OH generated by photolysis of a CH3 ONO/Air

mixture.

k re £: OH + -* products.

39
4. Table of Chemical Kinetic Data for Combustion Chemistry - Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + CH3CH2SH -* products

Hydroxyl + Ethanethiol (Ethyl mercaptan)

83 LEE/TAN

Discharge-flow. OH generated by the reaction:

H +,N02 - OH + NO. H atoms generated by decomposition of H

2 in a microwave-discharge.

Resonance-fluorescence

[OH] = 7xl0^ 3 molec . cm 3

. [CH3SH] = ( 1 . 3-9 . 7 )xl0 12 molec. cm

-3

. 83 MAC/POU

Discharge- flow. EPR-spectrometry

OH + (CHg) 2

S -* products

Hydroxyl + Methane, thiobis- (Dimethyl sulfide)

83 MAC/POU

Discharge-flow. EPR-Spectrometry.

EX 296

EX 293

EX 373 EX 573

( 2 , 21±0 . 11 )

(

13 )

( 1 . 63±0 . 12 ) ( 13

)

(. 54+0 . 36 )

(

12 )

( A . 70±0 . 60 ) ( 12

)

2

2

2

2

OH + 0=C=C=OO -» C02 + CH=<X3 (a)

-» any other products (b) Hydroxyl + 1 , 2-Propadiene-l , 3-dione

76 HAC/PIL • EX 296-481 ( 5 . 0±2 . 0 ) ( 12) 0 1560±130 2

^overall ' Discharge-flow.

ESR-Spectrometry

P = (2-4) torr.

OH + CH2=C=CH2 - products

Hydroxyl + 1,2-Propadiene (Aliens)

83 OHT RN 297 ( 6 . 20±0 . 66) ( 12 ) 2 Reaction in 0

2

/N2 gas, in a quartz reaction

cell. OH generated by H

202 photolysis.

P(H202

) = 1 torr. P(02

) = 10 torr - P(Total) ~ 760 torr. (mostly N

2

). P(Allene) ~ 1 mtorr.

k determined relative to the reaction:

OH + CH2=CHCH=CH2

-* products

OH + CE^CE=CB2 products

Hydroxyl + 1-Propene

83 ATK/ASC2 X

) RL 298 4.74±0.17 2/2

k re ^: OH + CH3 (CH2 )^CH3 -* products.

83 ATK/ASC2 1

) RN 298 ( 1 . 63±0 . 07) ( 13 ) 2 Placed on an absolute basis by using the k for the reaction of OH with Hexane.

40
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

1

) Irradiation in a Teflon bag. OH generated

by Photolysis of CHgONO in Air. Gas-chromatography. P(Total) = 735 torr. [Methyl nitrite] = 2.38x10^ molec.cm ^

.

83 OHT RN 297 ( 1 . 76±0 . 06) ( 13 ) 2 Reaction of OH with 1-Propene in O

2 /N2 gas, in a quartz reaction cell. OH generated by

photolysis of H2O2. P(H202) = 1 torr. P(02

) = torr. P(Total) ~ 760 torr. (mostly N

2

).

P( 1-Propene) ~ 1 mtorr. k determined relative

to the reaction: OH + CH2=CHCH=CH2-* products.

83 SMI EX 255-A58 9.58(10) 0 -1A70±130 2 1.18 EX 298 ( 1 . 14±0 . 18 ) ( 13

)

2 Discharge-flow. Resonance-fluorescence. OH generated by the reaction: H + NO2

-* OH + NO2 [1-Propene] = (0 . 07-8 . 51)xl0^ molec.cm .

OB + CH3CH2CB3

-» H

20 + (CB3

) 2CB (a) - H20 + CH3CH2CB2

(b) Hydroxyl + Propane

83 BAU/CRA 1

) ( k

a +kb

) RN 300-2000 1.03(11) 3. A 590 2/2

"Mercury free” vacuum system. OH generated

by Photolysis of H

20 at 18A.9 run. Gas-chromatography. [CO] = (5.7-75) torr.

k ref : OH + CO -» H + C02

. P(Total) < 97 . 5 tor .

[H2

0] = (12.3-28.1) torr.

83 TUL/RAV 1

) (k

a + k

fa

) EX 297-800 2.79(12) 1.A0 A28 2 Flash-photolysis . Resonance-fluorescence

.

OH generated by Flash-photolysis of H

2

0.

1

) The preexponential factors expressed as: (T/298) n

.

OH + CH2=CHCHO -» H20 + CH2=CHCO (a)

-* any other products (b) Hydroxyl + 2-Propenal (Acrolein) (Acrylaldehyde

)

83 ATK/ASC3 ( koverall /k ref > RL 299 0.727±0.050 2/2

kref: OH + CH3 CH=CH2 * products.

(koverall ) RN 299 ( 1. 10±0 . 08) (13) 2 Irradiation of Acrolein/Methyl nitrite/Air

mixtures in a Teflon reaction bag. OH generated by photolysis of CH3ONO in Air. Gas-chromatography. P = 735 torr. [Methyl nitrite] Q = 2.38x10'^ molec.cm

- ^.
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

^overall pl- ac8c* on an absolute basis by

using the k for OH + 1-Propene.

OH + CH3C(0)CH0 -* products

Hydroxyl + Propanal, 2-oxo- (Methylglyoxal)

83 PLU/SAN

Competitive technique, in an environmental

chamber. OH generated by photolysis of a CH3 ONO/Air mixture. The rate constant put

on an absolute basis by using k for the reaction:

OH * 0 products

[Methylglyoxal] ~2.4xl0^ molec.cm 3

. [CH3ONO] ~(3-20)xl0 13 molec.cm' 3

.

RN 298 ( 1 . 04±0 . 08) ( 13

)

OH + (CH3

) 2CO -» H20 + CH2C(0)CH3

(a)

-» any other products (b)

Hydroxyl + 2-Propanone (Acetone)

83 CHI/BIG <k overall ) RN 298 (3 . 98±0 . 54 ) (11)

Reaction in a 20 1. Pyrex chamber. OH generated by HONO vapors in synthetic air. Gas-chromatography . IR-spectrometry

k determined relative to the reaction: OH + CH-^CH^^CHj -» products.

OH + CH2=CHCH=CH2

-* products

Hydroxyl + 1,3-Butadiene

83 OHT RN 297 ( 1 . 62±0 . 13 ) ( 13

)

Reaction in 02 /N2 S as. in a quartz cell. OH generated by photolysis of H

202

P(H20

2

) = 1 torr. P(02

) = 10 torr

P(Total) ~ 760 torr. (mostly N2).

P( 1 , 3-Butadiene ) ~ 1 mtorr

OH + trans-CH3CH=CHCHg -* products

Hydroxyl + 2-Butene, (E)-

83 OHT RN 297 (3 . 67±0 . 19) ( 13

)

Reaction in 0

2 /N2 gas, in a quartz cell. OH generated by photolysis of H

202

. P(H202) = 1 torr. P(02

) = 10 torr. P(Total) ~ 760 torr. (mostly N2).

P(trans-2-Butene) ~ 1 mtorr. k determined

2

2

2

2

relative to the reaction: OH + cis-CH2=CHCH=CHCH3 - products.

42
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

oh i cii^ci^cn cn

3

+ + ch^ch^ch^ch^

^ a ^

-+ H2® CH3CH2CHCH3 (b) Hydroxyl + Butane

83 TUA/CAR1 (k

g + kb

) RL 300 0.347±0.005 2/2

Reaction in a Teflon vessel. FTIR-Spectrometry

.

OH generated by reacting O3 with NH2=NH2

.

P(Total) = 735 torr

.

k re f

: OH + + products.

OH + jJ

-* products

Hydroxyl + Furan

83 ATK/ASC2 *) RL 298 7.04+0.50 2/2

k re £: OH + CH3(CH2)^CH3 + products.

83 ATK/ASC2 *) RN 298 (2 . 4 1±0 . 18 ) ( 13 ) 2 Placed on an absolute basis by using the

k for the reaction of OH with Hexane.

* ) Irradiation of C^ONO/Furan/Air mixtures in a Teflon reaction bag. OH generated by Photolysis

of CH3ONO in Air. Gas-chromatography.

P(Total) = 735 torr. [Methyl nitrite] = 2.38xl0* 4 molec . cm

OH + CH3CH=CHCHO products

Hydroxyl + 2-Butenal (Crotonaldehyde

)

83 ATK/ASC3 *) RL 299 1.39±0.16 2/2

k re f

: OH + CH3CH=CH2 + products.

83 ATK/ASC3 *) RN 299 (2 . 19±0 . 24 ) ( 13 ) 2 Placed on an absolute basis by using the

k for the reaction of OH with CH3CH=CH2

.

1

) Irradiation of Crotonaldehyde/CHjONO/Air

mixtures in a Teflon bag. OH generated by

photolysis of CH3ONO in Air. Gas-chromatography

.

P(Total) = 735 torr. [Methyl nitrite] Q = 2.38x10*3 molec. cm

-

"*. OH + CH2=C ( CH3 ) CHO -* products

Hydroxyl + 2-Propenal, 2-methyl- (Methacrolein)

83 ATK/ASC3 1

) RL 299 1.13±0.09 2/2

k re £: OH + CH3CH=CH2 -+ products.

83 ATK/ASC3 1

) RN 299 ( 1 . 72±0 . 14 ) ( 13 ) 2 Placed on an absolute basis by using the

k for OH + CH 3CH=CH2

.

43
4 . Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

* ) Irradiation of Methacrolein/CH-jONO/Air

mixtures in a Teflon bag. OH generated

by photolysis of CHgONO in Air. Gas-chromatography.

P(Total) = 735 torr. [Methyl nitrite] Q = 2.38x10^ molec.cm

-

'1

.

OH + CH-jC( 0)CH=CH2 -» products

Hydroxyl + 3-Buten-2-one (Methyl vinyl ketone)

83 ATK/ASC3 X

) RL 299 0.747±0.055 2/2

k re f

: OH + CH3CH=CH2 * products.

83 ATK/ASC3 X

) RN 299 (1. 13±0 . 08) ( 13) 2 Placed on an absolute basis by using the

k for OH + CH3 CH=CH2

.

* ) Irradiation of Methyl vinyl ketone/CH^ONO/Air

mixtures in a Teflon bag. OH generated

by photolysis of CHgONO in air. Gas-chromatography.

P(Total) = 735 torr. [Methyl nitrite] Q = 2.38x10^ molec.cm ^ .

OH + -* products

Hydroxyl + Thiophene

83 ATK/ASC2 1

) RL 298 1.68±0.06 2/2

k re f

: OH + CH3 (CH2)^CH3-* products.

83 ATK/ASC2 X

) RN 298 (5 . 77±0 . 23 ) < 12) 2 Placed on an absolute basis by using the

k for OH + Hexane.

1

) Irradiation of Methyl nitrite/Thiophene/Air

mixtures in a Teflon bag. OH generated

by photolysis of CH3ONO in Air. Gas-chromatography.

P(Total) 735 torr. [Methyl nitrite] = 2.38x10'''*' molec.cm

- ^.

83 MAC/JOU EX 293-473 (7 . 83±4 . 82) ( 10 ) 0 -1750±200 2 Discharge-flow reactor. OH generated by the reaction: H + NO -* OH + N. OH atoms gene- rated by dissociation of H2 traces in He by

a microwave-discharge. EPR- spectrometry

[OH] q = (0 . 5-1 . 9)xl0 11 atoms . cm ^

[Thiophene] Q = (0 . 23-4 . 87 )xl0'*'^ molec.cm-1

. P = (0.47-0.60) torr.

44
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + CH2=C=CHCH2CH3

-» products

Hydroxyl + 1,2-Pentadiene

83 OHT Reaction in 0

2 /N2 gas, in a quartz cell. OH generated by photolysis of H

202

. P(H20

2

) = 1 torr. P(02

) torr. P(Total) ~. 760 torr. (mostly N2

).

P( 1 , 2-Pentadiene ) ~ 1 mtorr.

k determined relative to the reaction:

OH + CH2=CHCH=CH2

-*• products .

RN 297 (2 . 19±0 . 08 ) ( 13 ) 2

OH + cis-CH2=CHCH=CHCH3

-* products

Hydroxyl + 1 , 3-Pentadiene , (Z)-

83 OHT Reaction in 02 /N2 gas, in a quartz cell. OH generated by photolysis of H20

2

_ P(H20

2

) = 1 torr. P(02

) torr. P(Total) ~ 760 torr. (mostly N

2

). P( cis-1 , 3-Pentadiene ) ~ 1 mtorr.

k determined relative to the reaction: OH + CH2=CHCH=CH2 - products.

RN 297 (6 . 20±0 . 18 ) ( 13 ) 2

OH + CH2=CHCH2CH=CH2

-* products

Hydroxyl + 1, 4-Pentadiene

83 OHT Reaction in 0

2 /N2 gas, in a quartz cell. OH generated by photolysis of H20

2

. P(H20

2

) = 1 torr. P(02

) = 10 torr. P(Total) ~ 760 torr. (mostly N

2

). P( 1 , 4-Pentadiene) ~ 1 mtorr.

k determined relative to the reaction: OH + CH 3 CH=CH2

-* products.

RN 297 ( 3 . 05±0 . 08 ) ( 13 ) 2

OH + CH2=C=C(CH3

) 2

-* products

Hydroxyl + 1,2-Butadiene, 3-methyl83 OHT Reaction in 0

2 /N2 gas, in a quartz cell. OH generated by photolysis of H

202

. P(3-Methyl-1 , 2-Butadiene ) ~ 1 mtorr. P(Total) ~ 760 torr. (mostly N

2

). P(02

) = 10 torr. P(H20

2

) 1 torr. k determined relative to the reaction: OH + CH2=CHCH=CH2 - products.

RN 297 ( 3 . 49±0 . 11 ) ( 13 ) 2

45
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + CH2=C(CHg )CH=CB2“* products

Hydroxyl + 1,3-Butadiene, 2-methyl83 OHT Reaction in O2/N2 gas, in a quartz cell. OH generated by photolysis of H2O2. P(H202) = 1 torr. P(02> = ^ torr. P(2-Methyl-1, 3-Butadiene) ~ 1 mtorr. P(Total) ~ 760 torr. (mostly N2).

k determined relative to the reaction: OH + CH2=CHCH=CH2

-* products.

OH + o -* products

Hydroxyl + Cyclopentene

83 ATK/ASC5 1

) k ref : OH + CH2=C(CH

3 )CH=CH2 - products.

83 ATK/ASC5 1

) Placed on an absolute basis by using the

k for OH + 2-Methyl- 1,3-Butadiene (Isoprene).

* ) Irradiation of Cyclopentene/CH^ONO/Air

mixtures in a Teflon bag.

Gas-chromatography. P(Total) = 735 torr. (Methyl nitrite] Q

= 2.38x10^ molec.cm”^

00 + traas-CH^CTbCBCE^CH-j -* products

Hydroxyl + 2-Pentene, (E)-

83 OHT RN 297 ( A . 13±0 . 13 ) ( 13 ) 2 Reaction in O2/N2 gas, in a quartz cell. OH generated by photolysis of H2O2. PCH202) = 1 torr. P(02> torr. P(Total) ~ 760 torr. (mostly N2).

P(trans-2-Pentene) ~1 mtorr.

k determined relative to the reaction: OH + CH2=CHCH=CH2 -* products.

OH + ( CHg ) 2C=CHCH3

-* products

Hydroxyl + 2-Butene, 2-methyl83 OHT RN 297 ( 5 . 25±0 . 16 ) ( 13 ) 2 Reaction in O2/N2 gas, in a quartz cell. OH generated by photolysis of H2O2. P(H202) = 1 torr. P(02) = torr. P(Total) - 760 torr. (mostly N2).

P(2-Methyl-2-Butene) ~1 mtorr.

RN 297 (6 . 08±0 . 18 ) ( 13

)

RL 298 0 . 666±0 . 024 2/2

RN 298 (3 . 85±0 . 14 ) ( 13

)

k determined relative to the reaction: OH + CH2=CHCH=CH2 - products.

46
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + -» products

Hydroxyl + 1 , 3-Cyclohexadiene

83 ATK/ASC5 1

) k ref : OH + CH2=C(CH3 )CH=CH2 83 ATK/ASC5 1

)

products

.

Placed on an absolute basis by using the

k for OH + 2-Methyl-l , 3-Butadiene (Isoprene).

*) Irradiation of 1,3-Cyclohexadiene/CH3 ONO/Air

mixtures in a Teflon bag.

Gas-chromatography. P(Total) = 735 torr. [Methyl nitrite] D = 2.38xl0* 3 molec.cnT 3

.

OH + -* products

RL 298

RN 298

Hydroxyl + 1 , 4-Cyclohexadiene

83 ATK/ASC5 1

) RL 298

k ref : OH + CH2=C(CH

3 )CH=CH2

-* products.

83 ATK/ASC5 1

) RN 298 Placed on an absolute basis by using the k for OH + 2-Methyl-l, 3-Butadiene (Isoprene).

1

) Irradiation of 1 , 4-Cyclohexadiene/CH-jONO/Air

mixtures in a Teflon bag.

Gas-chromatography. P(Total) = 735 torr. [Methyl nitrite] Q = 2.38xl0~ 3 molec.cm-3

. 83 OHT RN 297 Reaction in 0

2

/N2 gas, in a quartz cell. P(H202

) = 1 torr. P(02

) = 10 torr. OH generated by photolysis of H

202

. P(l,4-Cyclohexadiene) ~ 1 mtorr. P(Total) -760 torr. (mostly N

2

). k determined relative to the reaction: OH + CH2=CHCH2CH2CH=CH2 - products.

1.62+0.05

( 9 . 40±0 . 33 ) ( 13

)

0 . 988±0 .040

( 5 . 70±0 . 23 ) ( 13

)

( 5 . 94±0 . 19 ) ( 13

)

OH + tr ans -CH2=CHCH=CHCH2CH3

-+ products

Hydroxyl + 1 , 3-Hexadiene , (E)-

83 OHT RN 297 (6 . 92+0 . 18) ( 13

)

Reaction in 0

2 /N2 gas, in a quartz cell. OH generated by photolysis of H

202

. P(H202

) = 1 torr. P(02

) = 1° torr - P(trans-1 , 3-Hexadiene ) - 1 mtorr. P(Total) - 760 torr. (mostly N

2

). k determined relative to the reaction: OH + CH2=CHCH=CH2 + products

.

2/2

2

2/2

2

2

2

47
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + trans-CH2=€HCH2CH=CHCHg -* products

Hydroxyl + 1 , 4-Hexadiene , (E)-

83 OHT X

) RN 297 ( 5 . 19±0 . 24 ) ( 13 ) 2 k determined relative to the reaction: OH + CH3 CH=CH2 - products.

83 OHT 1

) RN 297 ( 5 . 57±0 . 33 ) ( 13 ) 2 k determined relative to the reaction: OH + CH2=CHCH=CH2

-* products

^) Reaction in 0

2 /N2 gas, in a quartz cell. OH generated by photolysis of H

202

. P(H202

) = 1 torr. P(02) = 10 torr. P(trans-1 , 4-Hexadiene ) ~ 1 mtorr. P(Total) ~ 760 torr. (mostly N

2

).

OH + CH2=CHCH2CH2CH=CH2

-* products

Hydroxyl + 1 , 5-Hexadiene

83 OHT *) RN 297 (3 . 52±0 . 20 ) ( 13 ) 2 k determined relative to the reaction: OH + CH3CH=CH2

-» products

83 OHT 1

) RN 297 (3 . 82±0 . 08) ( 13 ) 2 k determined relative to the reaction:

OH + CH2=CHCH=CH2

-* products.

*) Reaction in 02 /N2 gas, in a quartz cell. OH generated by photolysis of H202 P(H20

2

) = 1 torr. P(02

) = 10 torr. P(Total) ~ 760 torr. (mostly N

2

)

P( 1 , 5-Hexadiene) ~ 1 mtorr.

OH + CH3CH=CHCH=CHCH3

-* products

Hydroxyl + 2 , 4-Hexadiene (mixture of cis.cis- and trans , trans- forms

)

83 OHT RN 297 (8 . 31±0 . 30 ) ( 13 ) 2 Reaction in 0

2

/N2 gas, in a quartz cell. OH generated by photolysis of H

202

. P(H202

) = 1 torr. P(02) = 10 torr. P(Total) ~ 760 torr. (mostly N2

). P(2, 4-Hexadiene) ~ 1 mtorr.

k determined relative to the reaction: OH + CH2=CHCH=CH2

-* products

OH + CH2=CHC (CHg )=CHCH3 products

Hydroxyl + 1,3-Pentadiene, 3 -methyl83 OHT RN 297 ( 8 . 37±0 . 48) ( 13

)

2
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Reaction in O2/N2 gas, in a quartz cell. OH generated by photolysis of H2O2. P(3-Methyl-1,3-Pentadiene) ~ 1 mtorr. P(Total) ~760 torr. (mostly N2).

P(H202) = 1 torr. P(02

) = 10 torr.

k determined relative to the reaction: OH + cis-CH2=CHCH=CHCH2 -* products.

OH + CH2=CHC=CH(CH3 )2 -* products

Hydroxyl + 1 , 3-Pentadiene , 4-methyl83 OHT RN 297 (8 . 07*0 . 24 ) ( 13 ) 2 Reaction in O2/N2 gas, in a quartz cell. OH generated by photolysis of H2O2

.

P(4-Methyl-1, 3-Pentadiene) ~ 1 mtorr. P(02

) = 10 torr. P(H202) = 1 torr. P(Total) ~760 torr. (mostly N2).

k determined relative to the reaction: OH + cis-CH2=CHCH=CHCH3

-> products.

OH + CH2=C(CH3 )CH2CH=CH2 products

Hydroxyl + 1 , 4-Pentadiene , 2-methyl83 OHT RN 297 (4 . 81±0 . 49) ( 13) 2 Reaction in O2/N2 gas, in a quartz cell. OH generated by photolysis of H

202. P(2-Methyl-1 , 4-Pentadiene) ~ 1 mtorr. P(02

) = 10 torr. P(H202

) = 1 torr. P(Total) ~760 torr. (mostly N

3

). k determined relative to the reaction: OH + cis-CH2=CHCH=CHCH3

-* products.

OH + CH2=€(CH3 )C(CH3 )=€H2 -* products

Hydroxyl + 1,3-Butadiene, 2 , 3-dimethyl83 OHT RN 297 (4 . 81±0 . 49) ( 13) 2 Reaction in 0

2 /N2 gas, in aquartz cell. OH generated by photolysis of H

302. P(2, 3-Dimethyl-l, 3-butadiene) ~ 1 mtorr. P(02

) = 10 torr. P(H202) = 1 torr. P(Total) ~760 torr. (mostly N

3

). k determined relative to the reaction:

OH + CH2=CHCH=CH2 - products.

49
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + products

Hydroxyl + Cyclohexene

83 ATK/ASC5 X

) RL 298 (6 . 7±0 . 17 )

( -1 ) 2/2

k ref : 0H + CH2=C(CH

3 )CH=CH2 - products.

83 ATK/ASC5 X

) RN 298 (3 . 87+0 . 10) ( 13 ) 2 Placed on an absolute basis by using the

k for OH + 2-Methyl-l , 3-Butadiene (Isoprene).

1

) Irradiation of Cyclohexene/CH3 ONO/Air

mixtures in a Teflon bag.

Gas-chromatography. P(Total) = 735 torr. [Methyl nitrite] Q = 2.38xlO X:X molec.crrT^.

83 OHT RN 297 (3 . 86±0 . 15) ( 13 ) 2 Reaction in 02 /N2 gas, in a quartz cell. OH generated by photolysis of H20

2

_ P(H202

) = 1 torr. P(02

) = torr • P(Total) ~760 torr. (mostly N

2

). P(Cyclohexene) ~ 1 mtorr.

k determined relative to the reaction: OH + CH2=CHCH2CH2CH=CH2 - products

OH + (CH3

) 2C=C(CH3

) 2

•+ products

Hydroxyl + 2-Butene, 2, 3-dimethyl83 ATK/ASC5 X

) RL 298 1.14±0.04 2/2

k ref : OH + CH2=C(CH3 )CH=CH2

-+ products.

83 ATK/ASC5 X

) RN 298 ( 6 . 57±0 . 24 ) ( 13 ) 2 Placed on an absolute basis by using the

k for OH + 2-Methyl-l , 3-Butadiene (Isoprene).

X

) Irradiation of 2 , 3-Dimethyl-2-Butene/CH3ONO/

Air mixtures in a Teflon bag.

Gas-chromatography. P(Total) = 735 torr. [Methyl nitrite] Q = 2.38xlO X ^ molec.cm

- ®.

OH + -» products

Hydroxyl + Cyclohexane

83 ATK/ASC3 X

) RL 299 0.270±0.016 2/2

k ref : ^H + CH3 CH=CH2

-+ products.

83 ATK/ASC3 X

) RN 299 (4 . 10+0 . 25) ( 12) 2 Placed on an absolute basis by using the

k for OH + CH3 CH=CH2

.

50
4. Table of Chemical Kinetic Data for Combustion Chemistry - - Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

* ) Irradiation of Cyclohexane /CHgONO/Air mixtures in a Teflon bag. OH generated by

photolysis of CHgONO in Air. Gas-chromatography. P = 735 torr. [Methyl nitrite] Q = 2.38x10^ molec.cm ^

.

Hydroxyl + Bicyclo [2 . 2 . 1 ]hepta-2 , 5-diene

(2, 5-Norbornadiene

)

83 ATK/ASC5 1

) Rl 298 1 . 19±0 . 10 2/2

k ref : OH + CH2=C(CH3 )CH=CH2-» products.

83 ATK/ASC5 X

) RN 298 ( 6 . 87±0 . 60 ) ( 13 ) 2 Placed on an absolute basis by using the

k for OH + 2-Methyl-l , 3-Butadiene (Isoprene).

X

) Irradiation of 2 , 5-Norbornadiene/CHgONO/Air

mixtures in a Teflon bag.

Gas-chromatography. P(Total) = 735 torr. [Methyl nitrite] = 2.38xlO X ^ molec.cm ^

.

Hydroxyl + Bicyclo [2 . 2 . l]hept-2-ene (2-Norbornene)

83 ATK/ASC5 1

) RL 298 0 . 488±0 . 040 2/2

kref : OH + CH2=C(CH3 )CH=CH2 - products.

83 ATK/ASC5 1

) RN 298 (2 . 81±0 . 23 ) ( 13

)

2 Placed on an absolute basis by using the

k for OH + 2-Methyl-l , 3-Butadiene (Isoprene).

1

) Irradiation of 2-Norbornene/CHgONO/Air mixtures in a Teflon cylindrical bag.

Gas-chromatography. P(Total) = 735 torr. [Methyl nitrite] Q = 2.38xlO X ^ molec.cm

- ^.

OH + CH2=C(CHg )CH2CH2CH=CH2

-» products

Hydroxyl + 1 , 5-Hexadiene , 2-methyl83 OHT RN 297 ( 5 . 75±0 . 26 ) ( 13 ) 2 Reaction in 0

2 /N2 gas, in a quartz cylindrical cell. OH generated by photolysis of H20

2

. P(2-Methyl-1 , 5-Hexadiene ) ~ 1 mtorr.

P(H20

2

) = 1 torr. P(02

) = 10 torr. P(Total) ~760 torr. (mostly N

2

). k determined relative to the reaction:

OH + CH2=CHCH2CH2CH=CH2 - products.

51
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err, type A,A/A(ref) B-B(ref) units factor

OH + -» products

Hydroxyl + Cycloheptene

83 ATK/ASC5 X

) RL 298 0.737±0.023

k ref : OH + CH2=C(CH3 )CH=CH2 - products.

83 ATK/ASC5 X

) RN 298 ( A . 26±0 . 13 ) ( 13

)

Placed on an absolute basis by using the

k for OH + 2-Methy1-1, 3 -Butadiene (Isoprene).

1

) Irradiation of Cycloheptene/CHjONO/Air

mixtures in a Teflon bag.

Gas-chromatography

[Methyl nitrite] Q = 2.38x10^ molec . cm P(Total) = 735 torr.

2/2

2

OH + -* products

Hydroxyl + Bicyclo [2 . 2 . 1] heptane (Norbornane)

83 ATK/ASC1 1

)

krefOH + -* products

RL 299

83 ATK/ASC1 1

) RN 299 Placed on an absolute basis by using the

k for OH + Cyclohexane.

1

) Irradiation of Norbornane/CHjONO/Air mixtures

in a Teflon bag. H generated by photolysis of

CH-jONO/Air mixtures at 290 nm. and 735 torr. Gas-chromatography

CHj

Hydroxyl + Benzene, 1,3-dimethyl- (m-Xylene)

83 ATK/ASC1 1

)

k ref : OH +

83 ATK/ASC1 1

)

-* products.

RL 299

RN 299

0 . 731±0 . 018

( 3 . 33±0 . 09 ) ( 12

)

2 . 85±0 . 18

( 1 . 30±0 . 08 ) ( 13

)

2/2

2

2/2

2 Placed on an absolute basis by using the

k for OH + Cyclohexane.

52
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

1

) Irradiation of m~Xylene/CH3ONO/Air mixtures

in a Teflon bag. OH generated by photolysis of

CH 3 ONO/Air mixtures at 290 nm. and 235 torr

.

Gas-chromatography

.

OH + -» products

Hydroxyl + Bicyclo [ 2 . 2 . 2] oct-2-ene

83 ATK/ASC5 X

) RL 298 0.404±0.019

k ref : OH + CH2=C(CH3 )CH=CH2 - products.

83 ATK/ASC5 1

) RN 298 (2.34+0.11X13)

Placed on an absolute basis by using the

k for OH + 2-Methy 1-1 , 3-Butadiene (Isoprene).

*) Irradiation of Bicyclo [2 . 2 . 2] oct-2-ene/

CHgONO/Air mixtures in a Teflon bag.

Gas-chroir.atography

.

P(Total) = 735 torr. [Methyl nitrite] Q = 2.38x10^ molec.cm

2/2

2

OH + CH2=C ( CHg ) CH2CH2

C ( CH3

) =CH2

-* products

Hydroxyl + 1 , 5-Hexadiene, 2 , 5-dimethyl83 OHT RN 297 (7 . 23±0 . 11) ( 13 ) 2 Reaction in 02 /N2 gas, in a quartz cell. OH generated by photolysis of H

202

.

P( 2 , 5-Dimethyl-l , 5-Hexadiene ) ~ 1 mtorr. P(Total) ~760 torr. (mostly N

2

). P(H202

) = 1 torr. P(02

) = 10 torr.

k determined relative to the reaction: OH + CH2=CHCH2CH2CH=CH2 - products.

OH + ( CH^ ) 2C=CHCH=C ( CH3

) 2

-» products

Hydroxyl + 2 , 4-Hexadiene , 2 , 5-dimethyl83 OHT RN 297 (1.26+0.06X14) 2 Reaction in 0

2 /N2 gas, in a quartz cell. OH generated by photolysis of H

202

. P(2, 5-Dimethyl-2, 4-Hexadiene) ~ 1 mtorr.

P(H202

) = 1 torr. P(02

) = 10 torr. P(Total) ~760 torr. (mostly N

2

). k determined relative to the reaction: OH + CH2=C(CH3 )CH2CH2CH=CH2 + products.

53
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

OH + -» products

Hydroxyl + Bicyclo [2 . 2 . 2] octane

83 ATK/ASC1 1

)

k ref : OH + -* products.

83 ATK/ASC1 1

) Placed on an absolute basis by using the

k for OH + Cyclohexane.

1

) Irradiation of Bicyclo [2 . 2 . 2] octane/CHjONO/

Air mixtures in a Teflon bag. OH generated

by photolysis of CHgONO/Air mixtures at 290 nm. and 735 torr. Gas-chromatography

RL 299

RN 299

1 . 96±0 . 13

( 8 . 91±0 . 60 ) ( 12)

2/2

2

OH + -» products

Hydroxyl + Pentalene, octahydro-

(Bicyclo[3.3.0] octane

)

83 ATK/ASC1 1

)

k ref : °H + products.

83 ATK/ASC1 1

) Placed on an absolute basis by using the

k for OH + Cyclohexane.

1

) Irradiation of Bicyclo [ 3 . 3 . 0 ] octane/CH^ONO/

Air mixtures in a Teflon bag. OH generated

by photolysis of CH^ONO/Air mixtures at 290 nm. and 735 torr. Gas-chromatography

RL 299

RN 299

1 . 47±0 . 07

( 6 . 69±0 . 36 ) ( 12

)

OH + Pr°ducts

Hydroxyl + lH-Indene, octahydro-, cis- (cis-Bicyclo[4. 3 . 0] nonane)

83 ATK/ASK1 1

)

‘ref • OH +

RL 299 2 . 29±0 . 16

2/2

2

2/2

products
4. Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(re£) B-B(ref) units factor

83 ATK/ASC1 *) RN 299 ( 1 . 04+0 . 08) ( 13 ) 2 Placed on an absolute basis by using the

k for OH + Cyclohexane.

1

) Irradiation of cis-Bicyclo [ 4 . 3 . Olnonane/

CHgONO/Air mixtures in a Teflon bag. OH generated by photolysis of CHgONO/Air

mixtures at 290 nm. and 735 torr. Gas -chromatography.

OH + -» products

Hydroxyl + lH-Indene, octahydro-, trans- (trans-Bicyclo [ 4 . 3 . 0]nonane)

83 ATK/ASC1 1

)

k ref : OH + -+ products.

83 ATK/ASC1 1

) Placed on an absolute basis by using the

k for OH + Cyclohexane.

1

) Irradiation of trans-Bicyclo [4 . 3 . 0 Jnonane/

CHgONO/Air mixtures in a Teflon bag. OH generated by photolysis of CHgONO/Air

mixtures at 290 nm. and 735 torr. Gas -chromatography

.

RL 299

RN 299

2.35+0.17

( 1 . 07±0 . 08) ( 13

)

OH + products

2/2

2

Hydroxyl + Benzene, (2-methyl- ) -propenyl-

(/3-Dimethylstyrene)

83 CHI/BIG RN 298 ( 1 . 99±0 . 30 ) ( 13) 2 Photooxidation of /3-Dimethylstyrene

in a Polymethylmetacrylate

smog-chamber

.

OH generated by HONO vapors in synthetic air. Gas-chromatography

.

k determined relative to the reaction: OH + ( CHg ) gCCHgCH ( CHg

)

2 + products.

55
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Hydroxyl + A , 7-Methano-lH-Indene, octahydro-,

(3aa,4/?,7/3,7aa:)- (Tricyclo[5.2. 1 . 0^ ®] decane

)

(exo-Tetrahydrodicyclopentadiene

)

83 ATK/ASC1 X

) RL 299 1.51±0.05 2/2

k

re f

: OH + -* products.

83 ATK/ASC1 X

) RN 299 (6 . 87±0 . 24 ) ( 12) 2 Placed on an absolute basis by using the

k for OH + Cyclohexane.

1

) Irradiation of exo-Tetrahydrodicyclopentadiene/CHjONO/Air mixtures in a Teflon bag. OH generated by photolysis of CHgONO/Air

mixtures at 290 nm. and 735 torr. Gas-chromatography

OH + -» products

Hydroxyl + Tricyclo [3 . 3 . 1 . 1^ ’ ^] decane (Adamantane)

83 ATK/ASC1 1

) RL 299

k ref • OH + -* products.

83 ATK/ASC1 1

) Placed on an absolute basis by using the

k for OH + Cyclohexane.

* ) Irradiation of Adamantane/CHgONO/Air

mixtures in a Teflon bag. OH generated by photolysis of CHgONO/Air

mixtures at 290 nm. and 735 torr. Gas -chromatography

RN 299

3 . 07±0 . 27

( 1 . 39±0 . 13 ) ( 13

)

2/2

2

OH + products

Hydroxyl + Naphthalene, decahydro-, cis- (cis-Decalin) ( cis-Bicyclo [4 .4 .0] decane)

83 ATK/ASC1 X

) RL 299 2.65±0.18 2/2

56
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

‘ref : OH + -* products.

83 ATK/ASC1 1

) Placed on an absolute basis by using

the k for OH + Cyclohexane.

* ) Irradiation of cis-Decalin/CH^ONO/Air

mixtures in a Teflon bag. OH generated by photolysis of CHjONO/Air

mixtures at 290 ran. and 735 torr. Gas-chromatography

.

OH + -» products

RN 299 ( 1 . 21±0 . 08 ) ( 13

)

Hydroxyl + Naphthalene, decahydro-, trans- (trans-Bicyclo [4.4.0] decane ) (trans-Decalin)

83 ATK/ASK1 1

) RL 299

‘ref OH + -* products.

83 ATK/ASC1 1

) Placed on an absolute basis by using

the k for OH + Cyclohexane.

1

) Irradiation of trans-Decalin/CHjONO/Air

mixtures in a Teflon bag. OH generated by photolysis of CHgONO/Air

mixtures at 290 nm. and 735 torr. Gas-chromatography

.

RN 299

2 . 72±0 . 16

( 1 . 24±0 . 07 ) ( 13

)

H02 + HO

z

(+ M) -* H

202 + 02

(+ M)

Hydroperoxo

79 TSU/NAK EX 298 (2 . 8±0 . 3 ) ( 12) Disproportionation of H02 in a quartz flow- reactor. H02 generated by reacting H with 0

2

. H atoms generated by Hg-photosensitized

decomposition of H2

. P = 760 torr.

H02 + NO (+ M) -» 0

2 + HNO (+ M) (a) - OH + N02

(+ H) (b) - H0N02

(+ M) (c) Hydroperoxo + Nitrogen oxide (NO) 78 HAC/KAU EX 296 ( 3 . 5±1 . 0 ) ( 12)

2

2/2

2

2

2 k^. Discharge-flow. LMR-Spectrometry

.

P = 5.25 torr.

57
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(rer), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

79 TEM EX 298 (4 . 4±1 . 0 ) ( 12)

kjj. Flow-system. ESR-Spectrometry . LMR- spectrometry . H02 generated by the reaction:

H + 02 + M -* H02 + M.

h

2o + n2o5 - hono2 + hono2 Water + Nitrogen oxide (N20^)

83 TUA/ATK EX 298 ( 7 . 83±1 . 20 ) (2

)

Reaction in Teflon environmental chambers. This value should be considered an upper

limit to the homogeneous k.

2

2

H20 + CHgC(0)0N02-» products

Water + Peroxide, acetyl nitro

76 PAT/ATK2 EX 296 ( 1 . 34±0 . 20 ) ( 1 ) 2 Reaction in a Teflon-lined aluminum tank. Gas-chromatography . Mass-spectrometry

IR-Absorption spectrometry.

[Peroxide] = (7. 6-8. 3) ppm.

[H2

0] = (5900-12000) ppm.

SO + 02 - S02 + o

Sulfur monoxide + Oxygen molecule

83 BLA/SHA EX 230-420 1.45(11) 0 2370±250 2 2.0 SO generated by ArF Laser-photodissociation

of S02 at 193 nm. P(S02

) = 30 mtorr.

P(02

) < 550 torr.

83 GOE/SCH EX 262-363 6.02(10) 0 2180±117 2 1.46 Static conditions. P(Total) = (1-200) mtorr.

SO + SO (+ M) -» S02 + S (+ M)

Sulfur monoxide

83 MAR/HER EX 298 =2.10(9) 2 4.0 Discharge-flow reactor. SO generated by

the reaction: 0 + CS2-* SO + CS. 0 atoms generated by passing a dilute N

20/Ar

mixture through a microwave-discharge.

SQ2 + fJ02 SOg + NO

Sulfur dioxide + Nitrogen oxide (N02

) 83 PEN/CAN EX 298 ( 1 . 4±0 . 1 ) (-2) 2 Static reactor. Second derivative UV-spectrometry. [ S02 ] = ( 8 . 07-8 . 73 )xl0-*-® molec.cm-3

. [N02

] = (0 . 78-4 . 40 )xl0 ^ molec.cm 3

58
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k ,k/k ( ref)

,

A, A/A(ref

)

n B, k,A k err. type B-B(ref) units factor

SC>2 + CH3C(0)0N02 -» products

Sulfur dioxide + Peroxide, acetyl nitro

76 PAT/ATK2 EX 296 < 8.10 2 Reaction in a Teflon-lined aluminum tank. Gas-chromatography . Mass-spectrometry

.

IR-Absorption spectrometry.

[502

] = ( 1260-3540 ) ppm. [Peroxide] = 0.042 ppm.

S03 + N0

2

"* products

Sulfur trioxide + Nitrogen oxide (N02

) 83 PEN/CAN EX 298 (8.8±0.8)(4) 2 Static reactor. Second derivative UV- spectrometry technique.

[503

] = ( 5 . 72-0 . 64 )xl0 16 molec.cm' 3

. [N02

] = 2 . 53xl0 16 molec.cm' 3

.

SB + O2 -* products

Mercapto + Oxygen molecule

81 TIE/WAM EX 298 <1.93(9) 2 Laser-induced fluorescence technique in the (320-330) nm. region. SH generated by H

2

S photodissociation in Ar through an ArF

excimer Laser, at 193 nm. Upper-limit k. P(H2

S] = (30-100) mtorr. P(Ar) = (5-10) torr. SH + SH -» H

2

S + S

Laser-induced fluorescence technique in the (320-330) nm. region. SH generated by H

2

S photodissociation in Ar through an ArF

excimer Laser, at 193 nm. Upper-limit k. P(H2S) = (30-100) mtorr.

P(Ar) = (5-10) torr.

SH + H2S -* products

Mercapto + Hydrogen sulfide

81 TIE/WAM EX 298 <1.02(13) 2 Laser-induced fluorescence technique in the

(320-330) nm. region. SH generated by H2S photodissociation in Ar through an ArF

excimer Laser, at 193 nm. P(H2S) = (30-100) mtorr. P(Ar ) = (5-10) torr.

Mercapto

81 TIE/WAM EX 298 <1.02(13) 2

59
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

SH + NO -* products

Mercapto + Nitrogen oxide (NO) -* products

81 TIE/WAM EX 298 3.37(11) 2 Laser-induced fluorescence technique in the (320-330) nm. region. SH generated by H2S photodissociation in Ar through an ArF excimer Laser, at 193 nm. P(H2S) = (30-100) mtorr

[NO] = (0.5-40) torr. P(Ar ) = (5-10) torr.

SH + CH2=CH2-» products

Mercapto + Ethene

81 TIE/WAM EX 298 <1.39(9) 2 Laser-induced fluorescence technique in the

.(320-330) nm. region. SH generated by H2

S photodissociation in Ar through an ArF excimer Laser, at 193 nm. Upper-limit k. P(H2S) = (30-100) mtorr. P(Ar ) = (5-10) torr.

H + OH -* NO + H Nitrogen atom + Hydroxyl

83 BRU/SCH2 EX 298 (2 . 53±0 . 48 ) ( 13 ) 2 Fast-flow reactor. Laser-magnetic Resonance. Resonance-fluorescence

Resonance-absorption

P = (1-5) torr. (He, or Ar)

N + HC>2 -* products

Nitrogen atom + Hydroperoxo

83 BRU/SCH2 EX 298 ( 1 . 33±0 . 30 ) ( 13 ) 2 Fast-flow reactor. Laser-magnetic resonance. Resonance- fluorescence

Resonance-absorption

P = (1-5) torr. (He, or Ar)

N + N

3 - N2

(B3H

6

) + N

2

(X 12

g+

) Nitrogen atom + Azide

83 YAM/FUE EX 298 (9 . 64±6 . 63 ) ( 12) 2 Discharge-flow reactor. N atoms generated by

dissociation of N

2 in a microwave-discharge,

through a N

2 /Ar mixture. N3 generated by

the reaction: Cl + HN3 -* HC1 + N3

60
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

N + NH2 - NH + NH (a)

-* N

2 + H (b) Nitrogen atom + Amidogen

83 WHY/PHI3 (k

a + kb

) EX 296 ( 7 . 29±0 . 84 ) ( 13

)

Fast-flow system. NH2 generated by

photolysis of NH3 at 193 nm. N atoms generated by microwave discharge.

Laser-induced Fluorescence.

[NH3

] ~ 3.0xl0 U molec.cnf 3

.

N + CN(v=n) -* N

2 + C Nitrogen atom + Cyanogen

83 WHY/PHI2 EX 300 (6 . 02±0 . 78) ( 13

)

Fast-flow reactor. CN generated by the ArF Flash-photolysis of NCCN at 193 nm.

N atom generated by microwave-discharge.

Laser induced Fluorescence.

N + NCC - CN + CN Nitrogen atom + Methylidyne, cyano83 WHY /PHI 2 (n = 0,1) ES 300 6.02(13)

Fast-flow reactor. N atom generated by

microwave-discharge

.

NCC generated by reaction of C atom with NCCN.

C atom generated by reacting CN with N atom. Laser induced fluorescence.

*3 + N3 - N2

(B3n

g

) + N2X

1Z

g+

) + N2

(X1X

g+

) Azide

83 YAM/FUE EX 298 8.43(11)

Discharge-flow reactor. N3 generated by the reaction:

Cl + HN

3 - HC1 + N3

NO + NH2

-» [NH2NO] -» N2 + H2

Of Nitrogen oxide (NO) + Amidogen

83 WHY/ PHI 3 EX 297 ( 1 . 09±0 . 07 ) ( 13

)

Fast-flow system. NH2 generated by the NH3 photolysis

at 193 nm. Laser-induced Fluorescence.

[NH

3

J ~ 3.0xl0 3 ^ molec.cm-3.

2

2

2

2

2

61
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

NO + CH3C(0)0N02 * products

Nitrogen oxide (NO) + Peroxide, acetyl nitro

76 PAT/ATK2 EX 296 (2 . 83±0 . 83 )

( -4 ) 1 Reaction in a Teflon-lined aluminum tank. Gas -chromatography . Mass -spectrometry.

IR-Absorption spectrometry.

[Peroxide] = (A. 1-17. 6) ppm.

[NO] = (26-211) ppm.

NO2 + CH3C(0)0N02

-* products

Nitrogen oxide (N0£) + Peroxide, acetyl nitro

76 PAT/ATK2 EX 296 ( 1 . 05±0 . 49 ) (3 ) 2 Reaction in a Teflon-lined aluminum tank. Gas-chromatography . Mass-spectrometry

IR-Absorption spectrometry.

[Peroxide] = (3. 0-9. 3) ppm.

[N02

] = (26-52) ppm.

N02 + (CH3

) 2NNH2

-* BONO + (CH3

) 2NNH Nitrogen oxide (N02

) + Hydrazine, 1 , 1-dimethyl-

-* Nitrous acid + Hydrazyl, 2, 2-dimethyl83 TUA/CAR2 EX 300 ( 1 . 39±0 . 12) (7

)

Postulated first step in the overall reaction: 2N02 + (CH3

) 2NNH2 - 2H0N0 + 0.5[CH

3

) 2NN=NN(CH

3

) 2] Reaction in a Teflon vessel. FTIR-Spectrometry . P = 735 torr.

[N02

] = (0-4 . 66)xl0^ molec.cm

- ^.

[1, 1-Dimethylhydrazine] = ( 1 . 21-4 . 35)xl0 1 ^

molec.cm ^

N02 + (CH3

) 3CNO + - NO + (CH3

) 3CN02 Nitrogen oxide (NO) + Propane, 2-methyl-2-nitroso83 JOH/MEC EX 291-318 6.76(8)

Static reactor. Mass-spectrometry.

P = (1-3) torr.

N

20 (+ M) -* N

2 + 0 (+ M) (a)

-* any other products (b) Nitrogen oxide (N20)

(k overall) EX 1600-2000 2.43(12) 0 18470 1 Thermolysis of N20 in a shock-tube. Time-of- flight Mass- spectrometry.

2

0 23905±755 2 2.1

62
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n E, k,A k err. type A,A/A(ref) B-B(ref) units factor

NH + NH2

-* NH2NH (a)

-* any other products (b) Imidogen + Amidogen

83 TEM (k overall) EX 296 (8 . 0±3 . 0 ) ( 13 ) 2 Far-IR Laser-Magnetic-Resonance Spectrometry.

NH(a1A) + HN3

-* RH2 + N3 (a) - N

2 + NH=NB* (b) Imidogen + Hydrazoic acid

83 KOD1 <k

a

> RL 303 0.746 2/2

83 K0D1 (kb

) RL 303 1.23 2/2

Photolysis of HN 3 in Xe , at 313 nm. Gas-chromatogr aphy . IR-Spectrometry

.

Rate constant ratios estimated on the basis of a proposed mechanism.

k ref : NH(a 1A) + HN 3-» 2H + 2N2 P(Xe) = (0-600) torr. P(HN3

) = 50 torr.

1 H NHCa^A) + CH2=CH2

-* [CH2=€HNH2 =

^jt ]

Imidogen + Etliene

-* [Ethenamine (Vinylamine) = Aziridine]

83 KOD3 RL 303 1.64 2/2

Photolysis of HN 3 vapor in presence of Ethene, at 313 nm. Rate constant ratio estimated on the basis of a proposed mechanism.

Gas-chromatography. IR-Spectrometry.

k ref : NHCa^A) + HN3

-* products

P(Ethene) = (0-188) torr. P(HN3

) = (0-105) torr.

NH/a^A) + CB3CH3

-» CH3CB2NH2

*

Imidogen + Ethane

83 KOD2 RL 303 3.34(-l) 2/2

Photolysis of HN3 vapor in presence of

Ethane, at 313 nm. Gas-chromatography. IR-Spectrometry

.

Rate constant ratio estimated on the basis of a proposed mechenism.

P(Ethane) = (0-450) torr. P(HN 3

) = 50 torr.

k ref" NH(a^A) + HN 3

-* products.

63
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

NH2 + C>2 (+ M) -* products

Amidogen + Oxygen molecule

83 HAC/KUR EX 295 (A. 8+1.0)

(

8 ) 2 Discharge-flow reactor. M = He. NH2 generated by reacting F atoms with NHg . P(Total) = 3 torr.

NH2 + NO2 ^2® + H2O (major channel)

Amidogen + Nitrogen oxide (NO2

) 83 WHY /PHI 3 EX 297 ( 1 . 27±0 . 11) ( 13 ) 2 Fast-flow system. NH2 generated by the photolysis of NH3 at 193 nm. Laser-induced Fluorescence.

[NH3

] ~ 3.0xl0 14 molec.cm-3

.

NH2 + NH2 ( + M) + NH + NH3 (+ M ) (a) + NH2NH2

(+ M ) (b)

-+ any other products (b) Amidogen

83 TEM (ka/koverall 5 111 296 <2.0(-3) 2/2

Far-IR-Laser-Magnetic-Resonance Spectroscopy

C + NCCN + CN + NCC Ethanedinitrile (Cyanogen, or Oxalonitrile

)

+ Carbon atom

83 WHY/PHI2 ES 300 -1.81(13) 2 Fast-flow reactor. C atom generated by

reacting CN with N atom. CN generated

by ArF Laser Flash-Photolysis of NCCN

at 193 nm. N atom generated by microwavedischarge. Laser induced Fluorescence.

CO + o2-* co2 + o

Carbon monoxide + Oxygen molecule

71 GAR/MCF

* Incident shock-waves waves in H2 /02 /C0/Ar

mixtures. Data-fit to induction time by

computer simulation.

83 THI/ROT

Reaction behind reflected shock-waves. Atomic -Resonance absorption Spectrophotometry. P(Total) = 1350 torr.

[02

] = ( 0 . 02-4 . 92 JxlO '*' 2 molec.cm-3

. [CO] = (0 . 12-2. 46)xl0 17 molec.cm-3

.

DE 1400-2500 3.1(11) 0 19124 2

EX 1700-3500 5.06(13) 0 31800 2

64
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CO + n2o -» co2 + n2 Carbon monoxide + Nitrogen oxide (N 20)

83 LOI/CAR EX 1060-1220 5.01(13 0 22144±1510 2 Reaction in a static cell, k determined by applying the thermal theory of explosion to the measurements

of the critical ignition pressure.

CO + CHgC(0)0N02

-» products

Carbon monoxide + Peroxide, acetyl nitro

76 PAT/ATK2 EX 296 <8.10(1)

Reaction in a Teflon-lined aluminum tank. Gas-chromatography . Mass-spectrometry

.

IR-Absorption spectrometry.

[Peroxide] = 11 ppm.

[CO] = 232 ppm.

CH(v=n) + 0

2

-* CO + OB* Methylidyne + Oxygen molecule

83 DUN/GUI (v = 0) (v = 1) Reaction in a cylindrical stainless cell,

by using a crossed-beam C02 Laser pump

and a tunable dye Laser. CH generated by IR multiphoton

dissociation of CHgOH.

Laser-induced fluorescence. P(Methanol) = 30 mtorr.

83 LIC/BER

Reaction in Ar buffer, by chemiluminescence

monitoring

.

P(Ar) = 20 torr.

EX 298 ( 1 . 26±0 . 12 ) ( 12

)

EX 298 (2 . 59±0 . 24 ) ( 12

)

EX 298 ( 4 . 82±1 . 81 ) ( 13

)

2

2

2

2

CH(v=n) + N

2 - HCN + N Methylidyne + Nitrogen molecule

83 DUN/GUI (v = 0) EX 298 ( 4 . 28±0 . 36 ) ( 10 ) 2

(v = 1) EX 298 ( 1 . 81±0 . 30 ) ( 12) 2 Reaction in a cylindrical stainless-steel

cell, by using a crossed-beam C02 Laser pump and a tunable dye Laser. CH generated by IR multiphoton

dissociation of CH^OH. Laser-induced Fluorescence. P(Methanol) = 12 mtorr.

65
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH + N

2

(+ M) -* HCN2(+ M)

Methylidyne + Nitrogen molecule

297 (1.20±0. 60X13)

297 ( 1 . 02±0 . 18 ) ( 17

)

297-675 (1.02±0. 18X10)

This weighted linear least-squares fit fails to adequately describe the data

at the lowest and highest temperatures

studied and is valid only over a limited

T-range (probably 297-450 K. ) At higher

temperatures, the activation complex de- composes to give other products, probably

HCN + N, which dominate above 1000 K. *) Reaction in Ar diluent. Laser-photolysis.

Laser-induced fluorescence. CH generated

by multiphoton dissociation of CHBr-j

P(Total) = (25-787) torr.

83 BER/LIN A

) CO Limiting high-pressure k. (RRKM calculation).

83 BER/LIN 1

) ES Extrapolated limiting low-pressure k.

83 BER/LIN X

) EX

CH + NO -* CO + NH* Methylidyne + Nitrogen oxide (NO)

83 LIC/BER EX 298 ( 1 . 51±3 . 01) ( 14

)

Reaction in Ar buffer by chemilumninescence

monitoring. P(Ar) = 20 torr.

2

3

-981±65 2

2

CH(v=n) + CH-jOH -» products

Methylidyne + Methanol

83 DUN/GUI (v = 0) ES 298 (6 . 38±0 . 36) ( 13 ) 2 (v = 1) ES 298 ( 2 . 02±0 . 15 ) ( 14 ) 2 Reaction in a cylindrical stainless steel

cell, by using a crossed-beam C02 Laser pump and a tunable dye laser. CH gene- rated by IR multiple photon dissociation

of CH3OH. Laser-induced Fluorescence.

CH + CH'^CH -* ,/\ * products

Methylidyne + Etnyne

83 BER/FLE EX 171-657 (2 . 10±0 . 25) ( 14 ) 0 -61±36 2 Reaction in a Laser-photolysis/Laser-induced

Fluorescence apparatus. CH generated by

multiphoton dissociation of CHBr^

at 266 nm. P(Total) = 100 torr.

66
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH + CH2=CH2

-» A -* CH2CH=CH2

(a)

-» any other products (b) Methylidyne + Ethene

83 BER/FLE (k

a

) EX 160-652 ( 1 . 3A±0 . 16) ( 1A ) 0 -173±35 2 Laser-photolysis/Laser-induced Fluorescence

.

CH generated by multiphoton dissociation

of CHBrg at 266 nm. P(Total) = 100 torr.

CH2 (a*Aj) + 02-* products

Methylene + Oxygen molecule

83 LAN/PET EX 295 ( A . A6±0 . 30 ) ( 13 ) 2 Cw Laser resonance-absorption technique. CH2

(a :*'A^) generated by the photolysis of Ketene at 308 nm. , with a XCl-excimer.

P(Ketene) = (0. 1-0.2) torr. P(He) = (A-6) torr.

Cfl^Ai) + H

2

-* products

Methylene + Hydrogen molecule

83 LAN/PET EX 295 (6 . 32±0 , 30 ) ( 13 ) 2 Cw Laser Resonance-Absorption technique. CH2 (a^A

1

) generated by the photolysis of Ketene at 308 nm. with a XCl-excimer.

P(Ketene) = (0. 1-0.2) torr. P(He) = (A-6) torr.

CH2 (a^A^) + H2

-» products

Methylene + Nitrogen molecule

83 LAN/PET EX 295 (6 . 63±0 . 60 ) ( 12) 2 Cw Laser Resonance-absorption technique. CH2

(a 1A 1

) generated by the photolysis of Ketene at 308 run., with a XCl-excimer.

P(Ketene) = (0. 1-0.2) torr. P(He) = (A-6) torr.

CH2(a^Aj) + NO -» products

Methylene + Nitrogen oxide (NO)

83 LAN/PET EX 295 (9. 6A±0 . 90 ) ( 13 ) 2 Cw Laser Resonance-absorption technique. CH2

(a 1A^) generated by the photolysis of Ketene at 308 nm. , with a XCl-excimer.

P(Ketene) = (0.1-0. 2) torr. P(He) = (A-6) torr.

67
4 . Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH2 (a*A^) + CO -» products

Methylene + Carbon monoxide

83 LAN/PET EX 295 ( 2 . 95±0 . 24 ) ( 13 ) 2 CW Laser Resonance-absorption technique.

CH^a^A^) generated by the photolysis of Ketene at 308 nm. , with a XCl-excimer.

P(Ketene) = (0. 1-0.2) torr. P(He ) - (4-6) torr.

CH^a^A^) + CH^ -* products

Methylene + Methane

83 LAN/PET EX 295 ( 4 . 22±0 . 24 ) ( 13 ) 2 Cw Laser Resonance-absorption technique.

CH^a^A^) generated by the photolysis of Ketene at 308 nm. , with a XCl-excimer.

PCKetene) = (0. 1-0.2) torr. P(Be ) = (4-6) torr.

CH2(X3B1

) + CB=CH - CH2=C=CH2

(a)

-» CBgOCH (b)

-* CgH2 + H

2

(c)

-* C3H3 + H (d)

Methylene + Ethyne

83 HOM/WEL2 (k

c

)

(k

Q

)

(k

c

)

(k d

) (kd

)

<kd

> Estimations based on a suggested mechanism.

High-temperature flow-reactor, with or

ES 295 8.5(10) 2 ES 500 2.0(11) 2 ES 1000 5.0(11) 2 ES 295 1.8(12) 2 ES 500 2.7(12) 2 ES 1000 3.6(12) 2

without added H atoms.

P = 2 torr.

CH2(a*A^) + CH2=CH2

-» products

Methylene + Ethene

83 LAN/PET EX 295 (9 . 03±0 . 36) ( 13) 2 Cw Laser Resonance-absorption technique. CH2 (a^A^) generated by the photolysis of Ketene at 308 nm. , with a XCl-excimer.

P(Ketene) = (0. 1-0.2) torr. P(He) = (4-6) torr.

68
4 . Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH2

(a-*Aj) + CHgCHg -» products

Methylene + Ethane

83 LAN/PET EX 295 ( 1 . 14±0 . 12) ( 14 ) 2 Cw Laser Resonance-absorption technique.

’CH2(a^\A^) generated by photolysis of Ketene at 308 ran. , with a XCl-excimer.

P(Ketene) = (0. 1-0.2) torr.

(He) = (4-6) torr.

CH2( a^Aj ) 1 CH2=C=0 —* CH2

=CH2 1 CO

Methylene + Ethenone (Ketene)

83 LAN/PET EX 295 ( 1 . 63±0 . 12) ( 14 ) 2 Cw Laser Resonance-absorption technique.

CH^a^A^) generated by the photolysis of Ketene at 308 run., with a XCl-excimer.

P(Ketene) = (0. 1-0.2) torr. P(He) = (4-6) torr.

CH2

(a^Aj) + CH-jCH2CHg -» products

Methylene + Propane

83 LAN/PET EX 295 ( 1. 45±0 . 12) (14 ) 2 Cw Laser Resonance-absorption technique.

CH2(a'*'A^) generated by the photolysis of Ketene at 308 ran. , with a XCl-excimer.

P(Ketene) = (0. 1-0.2) torr. P(He) = (4-6) torr.

CH2 (a^A^) + (CH2

) 2C=CH2

-* products

Methylene + 1-Propene, 2-methyl- (Isobutene)

83 LAN/PET EX 295 ( 1 . 45±0 . 12) ( 14 ) 2 Reaction of CH2 (a^A^) with Isobutene by using a Cw Laser Resonance-absorption technique. CH2 (a^A^) generated by the photolysis of Ketene at 308 ran. , with a HCl-excimer.

P(Ketene) = (0. 1-0.2) torr. P(He) = (4-6) torr.

69
^

Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH3 + 02

(+ M) HCHO + 0 + H (+ M) (a)

-* CH30 + 0 (+ M) (b) - CO + OH + B

2

(+ M) (c) - HCHO + OH (+ M) (d)

-* CH302 (+ M) (e) Methyl + Oxygen molecule

83 HSU/SHA X

) (kb) DE 1150-1560 1.0(14) Rate constant determined by fitting the concen- tration time profiles data to a computer kinetic

modeling mechanism. RRKM calculation.

83 HSU/SHA X

) (kb) RE 1150-1560 4.42(19)

Three-parameter curve-fitting of three sets of rate constant expressions from literature. The preexponential factor expressed as: (T/298)

-

^

1

) Reaction of CH3 with 0

2 in incident shockwaves. CH3 generated by decomposition of CH3N=NCH3 in excess 02

. Concentration time

profile measured by using CO-Laser ResonanceAbsorption.

[CH3 N=NCH3

] = 0.021% and 0.04% in 02

. 83 SEL/BAY (k 0

. M = Ar)

P(Total) = 0.639 torr.

Pmax (02> = °' 2426 torr -

(k

e

. M = Ar)

EX

EX P(Total) = 5.921 torr.

Pmax (02

) = 0-0730 torr.

(k 0

. M = N

2

) P(Total) = 0.931 torr.

*W°2

> = °- 3552 torr -

(k

e

. M = N

2

) P(Total) = 5.420 torr.

pmax (02> - °- 0 TM3 torr -

(k

e

. M = He)

EX

EX

EX P(Total) = 1.078 torr.

Pmax (02

) = °- 3 «! torr •

(k

e

. M = He) EX P(Total) = 6.747 torr.

Pmax (02

) = 0.1234 torr. Photoionization Mass-spectrometry. CH3 gene- rated by Flash-photolysis of Methyl nitrite

at 193 nm. P(Total) = (0. 5-6.0) torr. Other rate constants given at various pressures within the indicated P-range. The rate constant increases with the pressure.

298

298

298

298

298

298

( 4 . 82±0 . 36 ) ( 9

)

( 3 . 68± 0 . 40 ) ( 10 )

( 6 . 81±0 . 36) (9

)

( 3 , 50±0 . 17 ) ( 10 )

( 5 . 54±0 . 48 ) ( 9)

(2 . 40±0 . 17 ) ( 10

)

0 15500±1100 2

-5.94 21300 2

2

2

2

2

2

2

70
4 . Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CHg + H2S “* CH^ + SH Methyl + Hydrogen sulfide

83 ARI/ART2 EX 334-432 1 . 0 ( 11 ) 0 1054±10 2 1.02 SE 334-432 1.38(11) 0 1105±30 2 1.23 Best value by combining the present

rate expression with the data found

in the literature.

Photolysis of Azomethane/H2S mixtures in a cylindrical silica reaction vessel. Gas-chromatography. P(Azomethane ) = 70 torr. P(H2S) =0.5 torr.

CH3 + CH3 (+ M) - CH3CH2 + H (+ M) (a)

-» CH2=CH2 + H

2

(+ M) (b) - CH3CH3 (+ M) (c) Methyl

81 SKI/ROG (k

c

. Limiting high-pressure k.)

Calculated on the basis of k = k_jK.

83 ART/ANA (k

c

) Molecular modulation spectrometry. CH3 generated by photolysis of Azomethane

at 350 nm. Rate constant extracted from the data by computer-non-linear parameter

estimation and numerical

integration procedures.

83 HAS/RIE (k

c

) Flash-photolysis of Dimethyl oxalate. Gas-chromatography, k calculated by using a computer integration interaction program.

83 MAC/PIL (k

c

. M = Ar)

Limiting high-pressure k.

(k

c

. M = Ar)

Limiting low-pressure k. Flash-photolysis. Absorption spectroscopy.

CH3 produced by laser-photolysis of Azomethane

at 193 nm. P = (5-500) torr.

DE 298

DE 308

DE 298

EX 296-577

EX 296-577

2.75(13)

1.90(13)

2.70(13)

( 1 . 67±0 . 11 ) ( 13

)

(2 . 18±1 . 20 ) ( 19)

2

2

2

0 -154±2 2

0 -1680±300 3

CH3 + CH^ -» CH3CH3 + H (a)

-* CH3CH2 + H2

(b) Methyl + Methane

83 BAC ES 802 <6.3(1) 2 k

0

. Thermolysis of CH^

.

P -1000 torr. Upper-limit k.

71
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH3 + HCHO -» CH4 + CHO

Methyl + Formaldehyde

83 ANA2

CHg generated by photolysis of Acetone.

17 -3 [Acetone] = 1.0x10 molec.cm . [Formaldehyde] = 3.6X10 1 ® molec.cm-3

. Total cone. = 5.4x10^® molec.cm 3

. Gas-chromatography

EX 500-603 ( 8 . 43±0 . 60 ) ( 11) 0 3500±48 2

CHg + CBgO -+ CH^ + HCHO (a) CBgOCHg (b) Methyl + Methoxy

83 HAS/RIE (k a

) Flash-photolysis of Dimethyl oxalate. Gas-chromatography

k calculated by using a computer

integration interaction program.

DE 298 1.68(13) 2

CHg 1 CO-j CD2^ CH^CH^CH^

Methyl + Ethyl

83 ART/ANA

Molecular modulation spectrometry.

CHg and CH 3 CH2 generated by photolysis

of Azomethane and Azoethane at 350 nm. k extracted from the data by computerbased non-linear parameter estimation

and numerical integration procedures.

DE 308 2.72(13) 2

83 KAN/PURI

CHg and CHgCH2 recombination. The radicals

generated by the pyrolysis of Propane in a static reactor, in presence of Ethene. Determined from the reverse reaction and thermochemical data. P(Ethene) = ( 1 . 5-6 . 0 )torr

P(Propane) = 200 torr.

DE 773-793 8.91(12) 0 -856 2

CHg + CHgOC(O) -* C03C(O)OCB3 Methyl + Methyl, methoxyoxo83 HAS/RIE

Flash-photolysis of Dimethyl oxalate. Gas-chromatography

k calculated by using a computer

integration interaction program.

DE 298 1.64(13) 2

72
Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH-j 1 (CHg ) 2S “* CH^ 1 CH3SCH2 Methyl + Methane, thiobis- (Dimethyl sulfide)

76 ART/LEE EX 393-488 4.17(11) 0 4613±82 2 1.20 Photolysis of (CH 3

) 2 S in a silica

reaction vessel.

Gas-chrortiatography

.

CDj + CH3H--NCH3 -» CH^ + COgN^NCf^

Methyl + Diazene, dimethyl- (Azoraethane)

83 ARI/ART1 EX 334-463 1.07(11) 0 3960±22 2 1.05 Photolysis of Azomethane in a silica

reaction vessel. Gas-chromatography

.

P = (18-73) torr.

CH3 + CH2=C=CH2 -» CH2C(CH3 )C=CH2

(a) * CH3CH2C=CH2 (b) Methyl + 1 , 2-Propadiene (Allene)

83 SCH/CLA x

) <kb

/kref ) RL 573-595 6 . 76 ( -1

)

0 -508±24 2/2

k ref : ch 3 + ch 3 n=nch3 - ch4 + CH2N=NCH3 83 SCH/CLA x

) (kb) RN 573-595 5.75(10) 0 3440±120 2 1.58 Put on an absolute basis using the k of the reference reaction.

1

) Addition of CH3 to CH2=C=CH2 in a static system.

CHg generated by decomposition of Azomethane

.

Gas-chromatography

.

Allene/Azomethane mixture = 1.5.

P

Q (Azomethane ) = 29 torr.

CH3 + (CH3

) 2CH -» CH4 + CH3CH=CH2

(a) - (CH3

) 3CH (b) Methyl + Ethyl, 1-methyl- (Isopropyl)

83 ART/ANA DE 308 2.20(13) 2 Molecular modulation spectrometry. CH3 and (CH3

) 2CH generated by photolysis

of Azomethane and Azoisopropane at 350 nm.

k extracted from the data by computerbased non-linear parameter estimation

and numerical Integration procedures.

73
4. Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data

type

T/K k ,k/k(ref )

A, A/A(ref

)

n B, B-B(ref

)

k , A

units

k err. factor

CH3 + (CH3

) 2CO -» CH4 + CH2C(0)CH3 (a) (CH3

) 3CO (b) * CH3CH2CH(CH3 )0 (c) Methyl + 2-Propanone

76 ART/LEE (k

fl ) Photolysis in a silica reaction nvessel. Gas-chromatography

EX 393-488 4.07(11) 0 4869±55 2 1.12

83 ARI/ART1 (k

fl ) Photolysis in a silica reaction vessel. Gas-chromatography. P = (20-66) torr.

EX 398-522 3.47(11) 0 4811±26 2 1.05

CH-g "1 (CHgJgC (CHg )^C

Methyl + Ethyl, 1,1-dimethyl- (tert-Butyl)

83 ART/ANA DE 308 1.25(13) 2 Molecular modulation spectrometry.

CHg and (0113)30 generated by photolysis

of Azomethane and Azo-t-butane at 350 nm.

k extracted from the data by computerbased non-linear parameter estimation

and numerical integration procedures.

CHg 1 (CU3

) 3CH CH^ "1 (CU3 ) gCHCHg (a) - CH4 + (CH3

) 3C (b)

Methyl + Propane, 2-methyl- (i-Butane)

83 ANA1 (k a + kb

) EX 478-560 ( 3 . 73±0 . 66 ) ( 11 ) 0 4402±84 2 Molecular modulation spectrometry.

CH3 generated by photolysis of Acetone.

17 -o [Acetone] = 1.1x10 molec . cm . 17 — Q [Isopropane] = 6.9x10 molec. cm . Total cone. = 2.8x10®® molec. cm

- ®. Gas-chromatography

83 MAR/SHA (k a

) ES 504-640 1.58(13) 0 6616 2 Pyrolysis of Isobutane sensitized by

Azomethane in a static reactor. Gas-chromatography. P = (40-300) torr

CH4 (+ M) -* CH3 + B (+ M) (a)

-* any other products (b) Methane

83 KLO/DRO (koverall ) EX 1600-2500 1.0(15) 0 50520 1 Shock-tube. Pyrolysis of CH4 in Ar, behind reflected shock-waves

[CH

4

] = 1-9% in Ar.

P = (0.6-1.0)xl0 6 Pa.

74
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A

type A,A/A(ref) B-B(ref) units

CHO (+ H) CO + B (+ M)

Methyl, oxo-, (Formyl)

(M = Ar) EX -1400 1.0(15) 0 7700 2 Decomposition of CHO in premixed flames. Molecular-beam sampling. Mass-spectrometry.

Unspecified T-range.

P = (22.5-40) torr.

CHO + 02

(+ M) - CO + HOz(+ M) (a)

-* CO

z + OH (+ M) (b)

-* HCOg (+ M) (c) Methyl, oxo- , (Formyl) + Oxygen molecule

83 GUE/VAN (k

fl ) Reaction of CHO with 0

2 in premixed flames Molecular-beam sampling. Mass-spectrometry

Unspecified T-range.

P = (22.5-40) torr.

83 TEM (k

a

) Reaction of CHO with 0

2 by Far-IR Laser- Magnetic-Resonance Spectrometry.

CHO + CHO -* CO + CO + H2

(a)

-* HCHO + CO (b) - OHCCHO (c) Methyl, oxo- (Formyl)

83 TEM (k 0 + kb

) EX 296 (2 . 5±0 . 8) ( 13 ) 2 Far-IR Laser-Magnetic-Resonance

Spectrometry.

HCHO (+ M) - H + CHO (+ M) (a)

-» H

2 + CO (+ M) (b) Formaldehyde

83 GUE/VAN (kb

. M = Ar) EX -1400 7.85(13) 0 12380 2 Premixed flames. Molecular-beam sampling.

Mass-spectrometry. Unspecified T-range.

P = (22.5-40) torr.

HC(0)OOH -» H

20 + C02 Methaneperoxoic acid (Performic acid)

83 LEV/PRI EX 403-513 2.14(11) 0 14266±1624 1 Thermolysis of Peracetic acid diluted in He or Ar, in a flow-type Teflon reactor.

[Peracid] = 0.03-l.lvol% (in He, or Ar).

P = 760 torr.

EX -1400 8.8(12) 2

EX 296 ( 3 . 2±0 . 7 ) ( 12 ) 2

k err. factor

29.5

75
4 . Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CHgO + CH30 -» HCBO + CHgOH (a)

-* CHgOOCHg (b) Methoxy

83 HAS/RIE (k

a

) DE 298 1.82(13) 2 Flash-photolysis of Dimethyl oxalate. Gas-chromatography,

k calculated by using a computer

integration interaction program.

CH30 + CH30C(0) -» HC(0)OCB3 + HCBO (a)

-» CH3OC(0)OCB3 (b) Methoxy + Methyl, methoxyoxo83 HAS/RIE <k a

) DE 298 8.80(12) 2

< kb> DE 298 8.80(12) 2 Flash-photolysis of Dimethyl oxalate. Gas-chromatography,

k calculated by using a computer

integration interaction program.

CH30

2

(+ M) - CB3 + 02

(+ M)

Methyldioxy

83 ANA/BLA (M = N

2

) RL 550 <2.86(-ll) 1/2

Molecular Modulation Spectrometry.

CH 3 0

2 generated by photolysis

of Acetone.

k ref : CH 3 + 02 (+ M) -* CH302 (+ M) .

CB302 + CB30

2

-» HCBO + CH3OH + 02

(a)

-» CH30 + CH30 + 02

(b)

-» CB3OOCH3 + 02

(c) Methyldioxy

83 ANA/BLA (kb

/k

a

) RL 550 2.3 2/2

(k

a

) ES 550 4.46(11) 2

(kb

) ES 550 1.03(11) 2 Molecular Modulation Spectrometry. CH3O2 generated by photolysis of Acetone

kb

/k Q ratio based on extrapolation

of data at lower temperature.

Data-fit

76
Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n 3, k,A k err. type A,A/A(ref) B-B(ref) units factor

CS + 02

-» COS + 0 (a) - CO + SO (b) Carbon monosulfide + Oxygen molecule

(k a

) EX 290-500 1.58(8) 0 1862±453 2

(k a

) EX 293 (2 . 7±1 . 0 ) (5) 2 Fast flow-reactor. CS generated by

dissociation of CS2 in an electric

discharge. ESR-, and Mass-spectrometry.

[Ar] = ( 1 . 0-5 . 0 )xl0 8 molec.cm 3.

[02

3 = (0.5-3.2)xl0 8 molec.cm” 8

.

[CS] = (0.3-1.5)xl0 8 molec.cm' 3

.

P = (0.39=8-1. 58)torr.

83 BLA/JUS (k

a + kb

. M = He) EX 298 ( 1 . 75±0 . 24 ) (5) 2 Laser-induced Fluorescence.

CS generated by Photodissociation

of CS2 at 193 nm.

[02

] = (99.6-99.99)% in He. P(CS2

) ~5mtorr

.

CS + o3

-* cos + o2 Carbon monosulfide + Ozone

83 BLA/JUS (M = He) EX 298 ( 1 . 81±0 . 24 ) (8 ) 2 Laser-induced Fluorescence.

CS generated by Photodissociation

of CS2 at 193 nm. P(CS2

) ~ 5 mtorr. P(He ) = (50-300) torr.

CS + NOz

(+ M) -* COS + NO (+ M) %* Carbon monosulfide + Nitrogen oxide (N02

) 83 BLA/JUS (M = He) EX 298 (4 . 58±0 . 66) (7 ) 2 Laser-induced Fluorescence.

CS generated by Photodissociation

of CS2 at 193 nm. P(He) = 24 torr. P(CS2

) ~5 mtorr. CH3S + NO (+ M) -* CH3SNO (+ M)

Methyl, mercapto- + Nitrogen oxide (NO)

83 HAT/AKI RL 303 2.0(3) 3/3

Photooxidation of CH

3 SH, CHgSCHg,

or CH

3 SSCH

3 with OH in air,

in a quartz vessel. FTIR-Spectroscopy . Gas-chromatography

.

OH generated by photolysis of CHgONO,

or CH

3 CH2ONO. Estimated ratio.

k ref : ch 3 s + Oz

(+ M) -* CH3 S02 (+ M)

.

77
Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CN(v=n) +02"* products

Cyanogen + Oxygen molecule

83 WHY/ PHI(n = 0) EX 300 (8.,13±1.. 20 ) ( 12)

(n = 1) EX 300 (7.. 53±1, 93 ) ( 12) Fast-flow reactor. CN generated by Flash-photolysis

of NCCN at 193 ran. Dye-laser induced Fluorescence.

CN + H

2

-» HCN + H Cyanogen + Hydrogen molecule

83 SZE/HAN1 ES 2700-3500 7.5(13) 2 1.36 Reaction in Ar, behind incident shock-waves. CN generated by NCCN dissociation.

P = ( 230-420 ) torr. Best data-fit.

CN + HCN - NCCN + H Cyanogen + Hydrocyanic acid

83 SZE/HAN2 ES 2720-3070 1.0(13) 2 2.0 Reaction in Ar, behind incident shock-waves.

CN generated by NCCN disociation.

P = (323-518) torr. T-independent k.

HCN (+ M) -» H + CN (+ M)

Hydrogen cyanide

77 TAB/FUE EX 2600-3600 ( 1 . 26±0 . 28 ) ( 16) 0 50171±700 2 Thermolysis in Ar, behind incident

shock-waves . Absorption-spectroscopy.

[HCN] = (0.2-1. 0) X in Ar.

CH2=C ' i CH^ CH2=CH 1 CH-j Ethenylidene (Vinylidene) + Methane

83 LAU/YUN DE 298 =3.01(7) 2 Calculated using the BSBL (Bond strengthBond length) method of Berces and Dombi

CB2=CH (+ M) -» CH=CH + e (+ M)

Ethenyl

83 KIE/KAP DE 2300-3200 7.59(11) 0 2516 2 Pyrolysis of 3Z Ethene in Kr behind incident

shock-waves

Data fit to a proposed mechanism.

78
4 . Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH2=CH + C>2 -* CH=CH + HO2 Ethenyl (Vinyl) + Oxygen molecule

83 TEM EX 296 ( 1 . 5±0 . 7 ) ( 12 ) 2 Reaction by Far-Infrared

Laser -Magnetic -Resonance Spectrometry

.

CH2CH + CH^ -» CH2=CH2 + CH3 Ethenyl (Vinyl) + Methane

83 LAU/YUN DE 298 =1.20(5) 2 Calculated using the BSBL (Bond Strength- Bond length) method of Berces and Dombi

.

CH2=CH2 < + M) - C0Z=CB + H (+ M) (a)

-» CffsCH + H

2

(+ M) (b) Ethene

83 KIE/KAP (k

a

) DE 2300-3200 ( 1 . 4±0 . 3 ) ( 15) 0 41180 2

(kb

) DE 2300-3200 ( 1 . 5±0 . 3 ) ( 15) 0 27900 2 Pyrolysis of 3% Ethene in Kr behind

incident shock-waves. Data fit to a proposed mechanism.

CH2=CH2 + CH2=CH2-* CH2=CH + CH3CH2

(a)

-

Ethene

83 AYR/BAC (k 0

) RN 748-819 1.86(14) 0 32310±1007 2 4.0 Pyrolysis in a static system,

with (CH 3

) a and CH3 CH

3 as additives.

Gas-chromatography

.

P(Ethene) = (100-300) torr

.

83 MAC/PAC (k

a

) DE 896 2.3(-l) 2 Pyrolysis in a flow-system.

Gas-chromatography

.

P = (23-78) torr. Estimation based on the relationships:

CH

3 CH2 + CH

3 CH2 - CH2-CH2 + CH3 CH

3 (d) and - CH3 CH2CH2CH3 (r)

79
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH2=CH2

+ o -* CH3CH3 +

-* CH3CH2 +

-* CH3CH2 +

Ethene + Cyclopentene

-* Ethane + 1 , 3-Cyclopentadiene (a)

-* Ethyl + 2-Cyclopenten-l-yl (b)

-* Ethyl + 3-Cyclopenten-l-yl (c) 80 BEN (kb

+ k

c

) DE 650-770 2.0(13) 0 22295 2 Estimation based on a proposed mechanism.

CH3CH2 + N02 - products

Ethyl + Nitrogen oxide (N02

) 83 PAR/GUT EX 298 (2 . 71±0 . 06) ( 13 ) 2 Reaction in a fast-flow system. CH3 CH2 generated by the reaction: CH3 CH 3 + Cl - CH3 CH2 + HC1 Cl atoms generated by dissociation of Cl2 in a microwave-discharge.

[Ethane] = ~(5-50)xl0^ 3 molec.cm-3

. [Cl] Q = (0.5-1.5)xl0 11 atom.cm

-3

. P(Total) = (0. 7-2.0) torr. (N02

)

ch3ch2 t ch2=ch2

-* ch3ch3 + ch2=ch

Ethyl + Ethene

83 MAC/PAC DE 896 8,0(7) 2 Pyrolysis in a flow-system.

Gas-chromatography.

P = (23-78) torr. Estimation based on the relationships:

CH

3 CH2 + CH 3CH2

-* CH2

->CH2 + CH

3 CH 3 (d) and

-* CH 3 CH2CH2CH3 (r)

CH3CH2 + CH3CH2

-* CH2=CH2 + CH3CH3 (a)

Ethyl

-» CH3CH2CH2CH3 (b)

83 ART/ANA (kb

) DE 308 8.77(12) 2 Molecular modulation spectrometry. CH3 CH2 generated by photolysis of Azoethane at 350 nm. k extracted from the data by computerbased non-linear parameter estimation

and numerical integration procedures.

80
*. Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A

type A,A/A(ref) B-B(ref) units

CH3CH3 (+ M) -» CH3 + CH3 (+ M) (a)

-* CH2=CH2 + H2

(+ M) (b) Ethane

81 SKI/ROG (k.

a

. 1% Ethane in Ar. P = 3 atm. EX 1045-1172 3.98(15)

(k a

. 3% Ethane in Ar . P = 3 atm.) EX 1007-1241 1.00(15)

(k 0

. 1% Ethane in Ar . P = 9 atm.) EX 1000-1105 5.01(15)

(k a

. 3% Ethane in Ar. P * 9 atm.) EX 1034-1126 3.16(16)

(k0

. Limiting high-pressure k.) ES 1000-1300 1.58(17)

Thermolysis behind reflected shock-waves,

in a single pulse shock-tube. Gas-chromatography

.

The limiting high-pressure expression is based on a RRKM extrapolation.

83 KAN/PUR2 (k

g

) EX 841-913 3.31(16)

(k

a

) SE 841-913 4.27(16)

Pyrolysis in a static reactor,

with or without No. (1-20) torr.

CH=C=0 + CH^CH -» CO + C3H3 (a)

-* any other products (b) Ethenyl, 2-oxo- + Ethyne

83 HOM/WEL2 (k a

) DE 295

(k

a

) ES 500

(k

a

) ES 1000 Estimations based on a suggested mechanism

for the reaction of Ethyne with 0 atoms, studied in a flow-reactor, with or without

added H atoms

.

P(Total) = 2 torr.

1 . 0 ( 10 )

1 . 0 ( 10 )

1 . 0 ( 10 )

CH2=00 (+ M) - CH2 + CO (+ M)

Ethenone (Ketene)

71 WAG/ZAB (Low-pressure region k.) EX 1300-2000 3.6(15)

(Limiting high-pressure k.) EX 1650 3.0(14)

Thermolysis of (0.01-0.5)% Ketene in Ar, behind reflected shock waves. Mass-spectrometry. M = Ar. [Ketene] = (0 . 03-1 . 2)xl0^ molec.cm ^

.

CH2

=C=€> + CH3COOH - CH3C(0)0C(0)CH3 Ethenone (Ketene) + Acetic acid

71 BLA/DAV2 EX 379-488 6.46(8)

Reaction in a static system.

0 42728±1862 1

0 41319±956 1

0 42124±1963 1

0 44338±2315 1

0 45798 1

0 44238±886 1

0 44489±362 1

22

2

0 29844±1007 2

0 35732 1

0 5564±29 2

k err

.

factor

6.31 2.51

6.31

7.94

2.75

1.51

1.12

81
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

ch2=c=o + CH3C0SH - cH3c(0 )sc(0 )ce3 Ethenone (Ketene) + Ethanethioic acid

74 BLA/SPE EX 401-501 2.69(+8) 0 4559±108 Reaction in a static system.

Reactioq, Reference Code, Notes Data

type

T/K k ,k/k (ref )

A , A/A( ref

)

B, k,A k err. B-B(ref) units factor

H(0)CH2

+ 02(+ M) - CH(0)CH202(+ M)

thyl, 2-oxo- (Vinoxy) + Oxygen molecule

83 GUT/NEL (M = N

2

. P(Total) = 1.5 torr . ) EX 295 ( 6 . 87±0 . 24 ) ( 10

)

2

(M = N2. P(Total) = 100 torr . ) EX 476 ( 9 . 94±0 . 84 ) ( 10

)

2 (M = SFg . P(Total) = 10 torr .

)

EX 292 ( 1 . 13±0 . 04 ) ( 11

)

2 (M = SF k . P(Total) = 90 torr .

)

EX 473 ( 1 . 33±0 . 05) ( 11

)

2

1.78

Reaction in N

2

, or SFg buffer gas. CH(0)CH2 generated by reacting Cl

atoms with Ethylene oxide. Cl atoms generated by the IR multiphoton

dissociation of CgHgCl.

Other rate constants at various

temperatures and pressures for M = N

2 and M = SFg, are also given.

CH(0)CH2 + NO (+ M) - CH(0)CH2N0 (+ M)

Ethyl, 2-oxo- (Vinoxy) + Nitrogen oxide (NO)

83 GUT/NEL (M = N

2

. P(Total) = 2.5 torr.) EX

(M =* N

2

. P(Total) = 300 torr.) EX

(M - SFg. P(Total) = 10 torr.) EX

(M = SFg. P(Total) = 40 torr.) EX (Limiting low-pressure k.) EX Data fit to Troe’s semiempirical expression, by using a non-linear

least-squares procedure.

(Limiting high-pressure k.) EX Data fit to Troe’s semiempirical expression, by using a non-linear

least-squares procedure.

Reaction of Vinoxy with NO in N

2

, or SFg

buffer gas. Vinoxy generated by reacting Cl atoms with

Ethylene oxide. Cl atoms produced by the

IR multiphoton dissociation of CgHgCl.

The limiting low-pressure and high-pressure

expressions were obtained by data-fit to Troe’s semiempirical relationship.

Other rate constants at various pressures,

for M = N

2 , are also given.

295 ( 1 . 63±0 . 05) ( 11

)

2 295 ( 1 . 13±0 . 04 ) ( 13

)

2 295 ( 4 . 18±0 . 15) ( 12

)

2 295 ( 8 . 03±0 . 35 ) ( 12

)

2 295 ( 2 . 37±0 . 31 ) ( 19

)

3

295 ( 1 . 51±0 . 18) ( 13

)

2

82
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH30C(0) + CH30C(0) -» CH30C(0)C(0)0CH3 Methyl, methoxyoxo83 HAS/RIE DE 298 1.73(13) 2 Dimethyl oxalate Flash-photolysis.

Gas-chromatography, k calculated using a computer integration interaction program.

CH3CHO + CH3C(0)0N02 -* products

Acetaldehyde + Peroxide, acetyl nitro

76 PAT/ATK2 EX 296 ( 4 . 45±0 . 81 ) ( 3 ) 2 Reaction in a Teflon-lined aluminum tank. Gas-chromatography . Mass-spectrometry

.

IR- absorption spectrometry.

[Peroxide] = (3. 9-5.1) ppm.

[CH3 CHO] = (83-312) ppm.

(+ M) -» CHgCHOf (+ M) -» CH3CBO (+ M) (a) - CH3 + CHO (+ M) (b) - CH4 + CO (+ M) (c) Oxirane -* Acetaldehyde

83 LIF/BEN (k

a

. Limiting high-pressure k. ) ES 830-1200 -7.26(13) 0 28787 1

(kb

. Limiting high-pressure k. ) ES 830-1200 -3.63(13) 0 28787 1

(k

c

. Limiting high-pressure k. ) ES 830-1200 -1.21(13) 0 28787 1 Pyrolysis behind reflected shock-waves, in a single-pulse shock-tube. Gas-chromatography.

P = (1.5-10) atm. M = Ar. Estimations based

on a suggested mechanism which was fit to the experimentally determined productdistributions of the pyrolysis products.

/°\ + H - CH2CH2OHf -» CH2=CH2 + OH (a)

-* CH2=CH + H20 (b) Oxirane (Ethylene oxide) + Hydrogen atom

83 LIF/BEN (k

a

) ES 830-1200 9.5(10) 0 2516 2

(kb

) ES 830-1200 5.0(9) 0 2516 2 Pyrolysis of Ethylene oxide diluted in Ar, behind reflected shock-waves, in a singlepulse shock-tube. Gas-chromatography.

P = (1.5-10) atm. Estimations based on a suggested mechanism

which was fit to the experimentally

determined product- distributions of the pyrolysis products.

83
Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

HC(0)0CH3

-* CH3OH + CO (a)

-» hcho + co (b) + 2H2 + 2CO (c) Fomic acid methyl ester (Methyl formate)

83 DAV EX 1180-1500 2.09(10) 0 25466±2617 1 6.17 Pyrolysis behind reflected shock-waves,

in a single-pulse shock-tube.

CH3C(0)00H (+ M) -» CH3 + C02 + OH (+ M)

Ethaneperoxoic acid (Peracetic acid)

75 LEV/PRI EX 403-488 4.04(13) 0 16960+277 1 1.70 EX 403-513 1.15(13) 0 16383±1913 1 38.0 Thermolysis of Peracetic acid diluted

'in He, Ar, or N

2 , in a flow-type

Teflon reactor.

[Peracid] = (0 . 03-1 . l)vol% (in He, or Ar). P= 760 torr.

CH3CH20

2 + ch3CH202

-» CH3CH20 + ch3ch2o + °2 (a)

-* ch3cho + ch3ch2oh + °2 (b)

—* CH3CH2OOCH2CH3 t 02

(c) Ethyldioxy

83 ANA/WAD (k a /kb

) RL 302 1 . 75±0 . 05 2/2

<Vkb> RL 333 2 . 12±0 . 10 2/2

(k

a /kb

) RL 373 2 . 45±0 . 15 2/2

(k a

) ES 302-373 3.49(10) 316±167 2 1.65

(kb

) ES 302-373 1.94(11) 683+24 2 1.08 Molecular Modulation Spectrometry.

CH3 CH202 generated by photolysis of trans-Azoethane in presence of O2 and N2

. Gas-chromatography . Mass-spectrometry

[trans-Azoethane] =4.8 torr.

[N2

] = (410-550) torr.

[

2

] = (5-150) torr.

ch3sch2 t CH^ + (CH3

) 2S 1 ch3 Methyl, (methylthio ) - + Methane

76 ART/LEE DE 393-488 6.31(11) 0 7662 2 Calculated by using the k of the reverse reaction and thermochemical data.
V Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH3C(0)SH -» CH2=C=0 + H

2

S (a) - CHa + COS (b) Ethanethioic acid (Thioacetic acid)

83 TAY1 (k a + kb

) EX 529-655 3.16(12) 0 20978 1 Thermolysis of CH 3C(0)SH in a stainless-steel reactor. NMR-Spectroscopy

.

Thioacetic acid is either separately

prepared, or produced by decomposition

of Diacetyl sulfide.

Channels (a) and (b) are the most

likely paths.

NCCN (+ M) -* CN + CN (+ M)

Ethanedinitrile (Cyanogen) (Oxalonitrile

)

71 SLA/FIS EX 2700-4000 ( 4 . 58±0 . 40 ) ( 14

)

71 SLA/FIS SE 1750-4000 X

) Thermolysis of 0.05-1% Cyanogen in Ar, behind incident shock waves.

[Ar] = (1.20-3.22)xlo 18 molec.cm-3

. P

Q = (5-40) mm.Hg. M = Ar.

1

) A combination of the above

rate constant with the data

of Tsang et al. is best fitted

by the expression:

k = 3.71xl0 6 T°' 5 (64771/T) 8 exp(-64771/T)

O _ 1 _ 1 cm mol s .

34726±856

1 ^

2

2

CH2CN + N02

-* products

Methyl, cyano- + Nitrogen oxide (N02

) 83 PAR/GUT EX 298 ( 1 . 16±0 . 05) ( 13) 2 Reaction of CH2CN with N02 in excess,

in a fast-flow system. CH2CN generated by the reaction:

CHjCN + Cl - CH2CN + HC1

Cl atoms generated by dissociation of Cl2 in a microwave-discharge.

[CH

3 CN] = ~( 5-50 )xl0 13 molec.cm-3

.

[Cl] 0 = ( 0 . 5-1 . 5 )xl0 33 atom. cm 3

. P(Total) = (0. 7-2.0) torr. (N02

)

85
Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

[CH2=CHNH2

-- ^ ] -» CH2=CH + NH2

(a)

-» CH3CN + H

2

(b)

- [CH2=CHNH = ^ ] + B (c)

-* CB3 + CH2CN (d) [Ethenamine = Aziridine]

83 KOD3 (k a /kd

) RL 303 7 . 34 (

1 ) 1/1

(kb/kd

) RL 303 H

CM 1 O

t—i 1/1

(k

c /kd

) RL 303 5 . 64 ( -1

)

1/1

Photolysis of HN3 vapor in presence of Ethene,

at 313 nm. Gas - chromatography . IR-spectrometry

The reactant, [Ethenamine - Aziridine] formed

by the reaction NHia^A) + CH2=CH2

. P(Ethene) = (0-188) torr. P(HN3

) = (0-105) torr. Rate constant ratios estimated on the basis of the above proposed mechanism.

ch3h=nch3 ch3 1 ch3 1 n2

(q)

-* cb3ch3 + n

2

(b) Diazene, dimethyl- (Azomethane)

83 MAR/SHA <k

a

) EX 577-640 4.37(13) 0 22950±674 i 3.31

(k

fi

. Previous and present data) SE 504-657 6.31(13) 0 23143±457 1 2.18 Thermolysis in a static system

with four Pyrex glass reactors. Gas-chromatography.

P = (4-300) torr.

83 SCH/CLA EX 573-595 7.08(15) 0 25897+1263 1 8.71 Thermolysis in a static system.

Gas-chromatography

P(Azomethane) = 29 torr.

CH3C(0)0N02 + (CH3

) 2C=CH2

-» products

Peroxide, acetyl nitro + 1-Propene, 2-methyl-

( Isobutene

)

76 PAT/ATK2 EX 296 <4.05(2) 2 Reaction in a Teflon-lined aluminum tank.

IR-Absorption spectrometry.

Gas -chromatography

Mass -spectrometry.

[Peroxide] = 5.8 ppm.

[CH3CHO] = 51 ppm.

86
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

C

3 + °2 c

2 (d3n > v=1) + CO + 0 (or C02

) (a)

-* any other products (b) Carbon trimer + Oxygen molecule

83 NEL/HEL EX 520 <1.20(8) 2

''overall - ^ MUltiphoton -Photolysis/Laserinduced Fluorescence detection apparatus.

C 3 generated by multiphoton UV-photolysis

of CjHg at 249 run. , by using a KrF

excimer Laser. Unreactive at 607 K and above. P(02

) = 90 torr.

C3 + CH^ -» products

Carbon trimer + Methane

83 NEL/HEL EX 600 <3.01(8) 2 Multiphoton UV-Photolysis /Laser -induced

Fluorescence detection apparatus.

C3 generated by multiphoton UV-Photolysis

of CgHg at 249 nm. , by using a KrF

excimer Laser. Unreactive at 607 K and above. P(CHA

) = 90 torr.

C

3 + CH-CH < products

Carbon trimer + Ethyne

83 NEL/HEL EX 296-610 ( 5 . 47*1 . 61 ) ( 12 ) 0 4065*161 2 Multiphoton UV-Photolysis /Laser-induced

Fluorescence detection apparatus.

C

3 generated by multiphoton UV-Photolysis

of CgHg at 249 nm. , bu using a KrF

excimer Laser.

P( CH-CH) = (0-30) torr.

C3 + CH2=CH2 < products

Carbon trimer + Ethene

83 NEL/HEL EX 296-610 ( 1 . 02*0 . 31 ) ( 12 ) 0 3277*168 2 Multiphoton UV-Photolysis /Laser- induced

Fluorescence detection apparatus.

C3 generated by multiphoton UV-Photolysis

of C

3 Hg at 249 nm. , by using a KrF

excimer Laser. P(CH2=CH2

) = (0-50) torr.

87
4. Table of Chemical Kinetic Data for Combustion Chemistry - - Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Cg + CHgC-CH < products

Carbon trimer + 1-Propyne

83 NEL/HEL EX 296-610 (2 . 97+0 . 28 ) ( 11 ) 0 121-5-35 2 Multiphoton UV-Photolysis /Laser- induced

Fluorescence detection apparatus.

Cg generated by multiphoton UV-Photolysis

of CgHg at 249 nm. , by using a KrF

excimer Laser.

P( 1-Propyne) = (0-1) torr.

Cg + CHgCH=CH2 i products

Carbon trimer + 1-Propene

83 NEL/HEL EX 296-610 ( 6 . 26+0 . 36 ) ( 10 ) 0 159+21 2 Multiphoton UV-Photolysis /Laser- induced

Fluorescence detection apparatus.

Cg generated by multiphoton UV-Photolysis

of CgHg at 249 nm. , by using a KrF

excimer Laser. P(l-Propene) = (0-6.25) torr.

Cg + CHgCT^CH^CHg S products

Carbon trimer + 1-Butene

83 NEL/HEL EX 296-610 ( 7 . 35+0 . 30 ) ( 10 ) 0 139+17 2 Multiphoton UV-Photolysis/Laser-induced

Fluorescence detection apparatus.

Cg generated by multiphoton UV-Photolysis

of CgHg at 249 nm. , by using a KrF excimer Laser. P(l-Butene) = (0-7) torr.

Cg + cis-CHgCH=CHCHg < products

Carbon trimer + 2-Butene, (Z)-

83 NEL/HEL EX 296-610 ( 1 . 26+0 . 06 ) ( 11 ) 0 -201+19 2 Multiphoton UV-Photolysis/Laser-induced

Fluorescence detection apparatus.

Cg generated by multiphoton UV-Photolysis

of CgHg at 249 nm., bu using a KrF excimer Laser. P(cis-2-Butene) = (0-1) torr.

88
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Cg + (CHg^C^f^ S products

Carbon trimer + 1-Propene, 2-methyl- (Isobutene)

83 NEL/HEL EX 296-610 (2 . 53*0 . 10 ) ( 11) 0 -759-5-15 2

' Multiphoton UV-Photolysis/Laser-induced

Fluorescence detection apparatus.

Cg generated by multiphoton UV-Photolysis

of CgHg at 249 nm. , by using a KrF excimer Laser. P(Isobutene) = (0-0.08) torr.

Cg + CHgCl^CI^CHg < products

Carbon trimer + Butane

83 NEL/HEL EX 607 <1.20(8) 2 Multiphoton UV-Photolysis/Laser-induced

Fluorescence detection apparatus.

Cg generated by multiphoton UV-Photolysis

of CgHg at 249 nm. , bu using a KrF

excimer Laser. P(Butane) = 90 torr. Unreactive above 607 K.

Cg + (CHg) 2C=CHCHg -* products

Carbon trimer + 2-Butene, 2-methyl83 NEL/HEL EX 296-610 (3 . 35+0 . 27 ) ( 11 ) 0 -1014±34 2 Multiphoton UV-Photolysis/Laser-induced

Fluorescence detection apparatus.

Cg generated by multiphoton UV-Photolysis

of CgHg at 249 nm. , by using a KrF

excimer Laser. P(2-Methyl-2-Butene) = (0-0.1) torr.

Cg + CHgCH2CH2C=CCHg -* products

Carbon trimer + 2-Hexyne

83 NEL/HEL EX 296-610 (6 . 50±0 . 05) ( 11) 0 -695±24 2 Multiphoton UV-Photolysis/Laser-induced

Fluorescence detection apparatus.

Cg generated by multiophoton UV-Photolysis

of CgHg at 249 nm. , by using a KrF

excimer Laser. P(2-Hexyne) = (0-0.07) torr.

89
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Cg + (CHg^OCCCBg^ + products

Carbon trimer + 2-Butene, 2, 3-dimethyl83 NEL/HEL

•Multiphoton UV-Photolysis /Laser-induced

Fluorescence detection apparatus.

Cg generated by multiphoton UV- Photolysis

of CgHg at 249 nm. , by using a KrF

excimer Laser.

P(2 , 3 -Dimethy 1-2-Butene ) = (0-0.08) torr

ch2=chch2 + no c+ m) -* ch2=chch2no (+ M)

2-Propenyl (Allyl) + Nitrogen oxide (NO) 82 TUL/MAC

Reaction in an Laser-Flash-Photolysis system.

Allyl generated by Flash-photolysis of

1 , 5-Hexadiene . [NO] = (50-100) torr. P(Total) = (50-500) torr. Limiting high-pressure k. The frequency factor: A = (2.11±0.36)xl0(12)cm3 .mol

_1

.s -1

, given above, is equivalent to: A = ( 3 . 35±0 . 10 )xl0 ^cm3

. molec . .s ^

However, the authors give a value of: A = ( 3 . 35±0 . 10 )xl0 ^cm3

. molec. ^ .

which is probably a misprint.

CH2=CHCH2 + CB2=CHCB2-* CH2=CHCH2CH2CH=C0CH2 2-Propenyl (Allyl)

82 TUL/MAC

Recombination of Allyl in a Laser-FlashPhotolysis system. Allyl generated by

Flash-photolysis of 1, 5-Hexadiene.

P(l, 5-Hexadiene) = 182 mtorr. P(Ar ) = 53 torr.

A (+ M) -» CHgCB=CH2

(+ M)

Cyclopropane

78 LEW/GIE (Limiting high-pressure k.

)

(k ref is k<o.) (limiting high-pressure k.)

(Limiting high-pressure k.)

(Second choice)

EX 296-610 ( 1 . 26±0 . 11 ) ( 12 ) 0 -917±33 2

EX 295-404 (2 . 11±0 . 36 ) ( 12 ) 0 -403+12 2

EX 293-571 ( 1 . 02±0 . 02) ( 13 ) 0 -132+12 2

RL 1038-1208 0 . 5±0 .

1

SE 1038-1208 1.58(15) 0 32713 1 ES 1038-1208 2.82(15) 0 32964 1

90
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Isomerization in Ar, or He diluent,

in a single-pulse shock-tube,

behind reflected shock-waves. Comparative-rate method with

Cyclohexane decomposition taken

as internal standard reaction.

Gas -chromatography.

P = (533-5097) torr.

80 FUR/PAC EX 897 1.72(-1) 1 Isomerization in a flow-reactor

with quartz tubes. Gas-chromatography

.

P = 50 torr.

82 LEW/BOS EX 983-1333 2.24(11) 0 12823 1 Thermal isomerization in Ar, in presence

of BCI3

, behind reflected shock-waves,

in a single-pulse shock-tube. Gas-chromatography

.

[Cyclopropane] = 1% in Ar. [BC13

] = 1% in Ar. P = (2 . 5-3 ) atm.

(CH3

) 2CH -» H + CH3CH=CH2

(a) CH3 1 CH2=CH2

(b) Ethyl, 1-methyl- (Isopropyl)

75 SZI/MAR3 RN 538-666 1.0(14) 0 18319±1057 1 6.31 Static-, or flow-system. (CH 3

) 2CH generated

by the pyrolysis of Azoisopropane.

Mass-spectrometry

.

Determined relative to the reaction:

(CH 3

) 2CH + (CH3

) 2CH -* (CH3) 2CHCH(CH3

) 2

(CH3

) 2CH + (CH3

) 2CB -* (CH3

) 2CHCH(CH3) 2

(a)

-» (CH3

) 2CHCH(CH3) 2

(b) Ethyl, 1-methyl- (Isopropyl)

83 ART/ANA (k

fl

) ES 308 5.96(12) 2 Molecular modulation spectrometry. (CH

3

) 2CH generated by photolysis of Azoisopropane

at 350 nm. k extracted from the data by

computer-based non-linear parameter

estimation and numerical integration

procedures

.

91
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH3CH2CH3 (+ M) + CH3CH2

(+ M) (a) - any other products ( + M) (b) Propane

83 ALA/KIE (k

a

) EX 1400-1800 ( 7 . 74±1 . 55) ( 11

)

0 28030

(k

a

. Limiting high-pressure k) TH 1400-1700 1.48(17) 0 43500 (RRKM extrapolation.)

(k

a

) EX 1800-2300 (2 . 68±0 . 54 ) (17

)

0 28280 Pyrolysis in incident shock-waves. Laser-schlieren technique.

P

Q = (3-25) torr. M = Kr. (2-4)% Propane in Kr

83 KAN/PURI (k

a

) EX 773-793 5.13(16) 0 41973±981 1 3.47 Pyrolysis in a static reactor,

in presence of Ethene. P(Propane) = 200 torr.

P( Ethene) = (1. 5-6.0) Tor.

CH2=CHCH202 ** CHZ

=CHCH2 i 02 2-Propenyldioxy

82 MOR/PIL EX 413-427 ( 1 . 6±0

8 ) ( 10 ) 0 6411±192 1 Laser Flash-photolysis system

with a Xenon lamp.

2-Propenyldioxy generated by the addition of 0

2 to Allyl, in turn generated by the Flash-photolysis

of 1 , 5-Hexadiene

Gas- chromatography.

[02

] = (0.49-1.38)xl0 17molec.cm' 3

. [Allyl] = 3xl0 13particles cm

-3

. P(Total) = 50 torr.

-» CEz

CE20CBz-» CH2=CH2 +HCHO (a)

CH^CIJzCli2P * CH2=CH2 t HCHO (b) Oxetane

83 ZAL/HUN (k

a + kb- Limiting high-pressure k) ES 668-758 2.63(15) 0 31214±457 1 2.04

< k

a> DE 673-758 1.3(15) 0 31515 1

< kb> DE 673-758 9.2(14) 0 31755 1 Thermolysis in a static vacuum system.

Gas-chromatography

P = (0.075-52.5) torr. Data fit to RRKM theory.

92
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

D

-» CH2CH20CD2

-» CH2=CH2 +DCDO (a)

-+ CH2CH2CD20 -» CH2=CH2 + DC®0 ( b >

-+ CH2CD20CH2

-* CH2=CD2 + HCHO (c)

-* CD2CH2CH20 + CH2=CD2 + HCHO (d) Oxetane-2 , 2-d2 83 ZAL/HUN (koverall . Limiting high-pressure k) ES 668-758 3.47(15) 0 31611+457 2

(k

a

) DE -723 1.3(15) 0 31996 1

(kb

) DE -723 9.2(14) 0 31755 1

<k

c

) DE -723 1.3(15) 0 31515 1

Thermolysis

(kd

) in a stativacuum system.

DE -723 9.2(14) 0 32236 1

Gas-chromatography

.

P = (0.075-52.5) torr. Data-fit to RRKM theory.

1.45

O

^^CHj

+ CH3CH2CHO (a)

-» (CH3

) 2CO (b) + ch2=chch2oh ( c

)

-* CH2=CHOCH3 (d) Oxirane

,

, methyl-, -+ Propanal (a) + Propanone (b) + 2-Propen-l-ol (c)

-+ Ethene, methoxy- (d) 77 FLO (k a

) EX 654-717 2.45(14) 0 29434±289 1 1.51

(kb

) EX 654-717 1.51(14) 0 30131±289 1 1.51

(kb

ffl. RRKM data-fit) ES 656-717 1.70(14) 0 30552 1

(k

c

) EX 656-717 7.94(12) 0 28760±241 1 1.41

(k d

) EX 656-717 3.24(13) 0 29578+373 1 1.70 Thermal isomerization in a static vacuumsystem, with packed and unpacked vessels.

in presence or absence of NO.

Gas--chromatography.

P = (5-326) torr.

CH3CH2C(0)OOH -» ch3ch2 + co2 + OH

Propaneperoxoic acid (Perpropionic acid)

83 LEV/PRI EX 403-513 1.35(13) 0 16671±1708 1 30.2 Thermolysis in He or Ar, in a flow-type

Teflon reactor.

[Peracid] = 0.03-1. lvol% (in He, or Ar).

P= 760 torr.

93
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A

type A,A/A(ref) B-B(ref) units

(CB3

) 2CB02 + CH3CH=CH2

-* (CH3

) 2CHO + /°\

Ethyldioxy, 1-methyl- (Isopropylperoxo) + 1-Propene

83 SWA/WAD EX 303-408 8.31(11) 0 8143+301 2 Reaction in a Pyrex vessel.

(CH3

) 2CH02 generated by photooxidation

of trans-2 , 2’ -Azopropane

P(l-Propene) = (200-400) torr. P(02

) = (300-500) torr. P(Total) = 750 torr.

(CH3

) 2CH02 + CCH3

) 2C=CH2 + (CB3

) 2CH0 + /®\ sC H. ^CH,

J

Ethyldioxy, 1-methyl- (Isopropylperoxo)

+ 1-Propene, 2-methyl- (Isobutene)

83 SWA/WAD EX 303-408 3.89(11) 0 7542+265 2 Reaction in a Pyrex vessel.

(CH3

) 2CH2 generated by photooxidation

of trans-2 , 2' -Azopropane

P(Isobutene) = (50-200) torr. P(Total) = (700-750) torr. P(02

) = 450 torr.

(ch3 > 2cho2 + ch3ch2c(ch3 )=ch2

Ethyldioxy, 1-methyl-, (Isopropylperoxo)

+ 1-Butene, 2-methyl83 SWA/WAD EX 303-408 3.89(11) 0 7542+265 2 Reaction in a Pyrex vessel. Isopropylperoxo generated

by photooxidation of trans-2, 2’ -Azopropane

P( Isobutene) = 80 torr. P(02

) = (300-400) torr. P(Total) = 500 torr.

(CH3

) 2CH02 + (CH3

) 2CH=CHCB3 - (CH3

) 2CHO + H,C A^CH,

H,C'

Ethyldioxy, 1-methyl-, (Isopropylperoxo)

+ 2-Butene, 2-methyl83 SWA/WAD EX 303-408 3.89(11) 0 7542±265 2

k err

factor

2.29

1.55

1.55

1.55
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Reaction in a Pyrex reaction vessel. Isopropylperoxo generated by photooxidation

of trans-2 , 2' -Azopropane

.

P( Isobutene) = 40 torr. P(Total) = 500 torr.

P(C>2) = 400 torr.

CH3CH2CN - CH3 + CH2CN (a) - CH2=CH2 + HCN (b)

-* C02=CeCN + H

2

(c) Propanenitrile

83 TRE (k

a

) EX 789-850 3.16(15) 0 39607±478 1 2.0 Pyrolysis in a static reactor.

P = (10-100) torr.

CH3CH2N=€=0 -* CH2CH2 + HN=C=0 (a)

-> CH4 + HCN + CO (b) Ethane, isocyanato- (Ethyl Isocyanate)

83 BLA/IJA (k a

. Unimolecular elimination) EX 701-803 1.58(12) 0 28183±453 1 1.6

(k

a

. Unimolecular elimination EX 723 2 . 25( -5

)

1

(kb

. Chain decomposition) EX 701-803 2.51(12) 0 26673±7 55 1 2.5

(kb. Chain decomposition) EX 723 9 . 33 ( -5

)

1 Thermolysis in carbon-coated, packed

and unpacked reaction vessels.

(Chains are quenched by inhibitors.)

P = (29-204) torr.

CH3CH2CH2OON02

-* CH3CH2CH20

2 + N02 Peroxynitric acid propyl ester

79 EDN/SPE DE 280-298 5.0(14) 0 9965 1 Decomposition in a flow reactor,

in air and in presence of NO. IR-spectrometry

.

P = 700 torr.

E

g measured directly.

The preexponential factor determined from

E a and the rate constant ratio of the reactions

:

ch

3 ch2ch2o

2 + no -* ch3 ch2ch2o + no2 and ch3ch2ch2o2 + no2 - ch 3 ch2ch2no2

95
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

(v=5, 6) -» CH2=CHCH=CH2

Cyclobutene

83 JAS/FRI (A = 13346 cm' 1

) EX 298 (3 . 5±0 . 8 ) (7

)

1

(A = 16602 cm' 1

) EX 298 (8.2±1. 1) (8) 1 Photoisomerization in a dye Laser. Tiotoacoustic spectrometry,

s- chromatography

t-spectrometry

P = (0. 1-60) torr. The rate constant, measured as a function

of energy and overtone transition,

is increasing with A.

CHjCH^CHj 1 H2"* cis CH^CH=CHCH2 1 0

1-

Propenyl, 1-methyl-, + Hydrogen molecule

83 COL/RIC ES 773-794 1.26(13) 0 12179 2 Thermal reaction in a static system, k determined from the experimental data

on the basis of a suggested mechanism.

cis-CH3CH=CHCH3 (+ M) -* CH3CH=CHCH2 + H (+ M) (a) - CH2=CHCH=CH2 + H

2

(+ M) (b)

-* CH2=CHCH2 + CH3 (+ M) (c) * trans-CH3CH=CHCH3 (+ M) (d)

2-

Butene, (Z)-

71 SPR/AKI (k d

)

(k d

) Isomerization a glass reaction cell. Gas-chromatography. M = N02

. P(cis-2-Butene ) = (1-30) torr. P(N02

) = (0. 1-3.0) torr.

ch3ch2chch3 + h

2

-* ch3cb2ch2ch3 + e

Propyl, 1-methyl-, + Hydrogen molecule

83 COL/RIC 1

) k ref : CH3CH2CHCH3

-» CH 3 + CH3 CH=CH2 Estimated ratio.

83 COL/RIC 1

) 1

) Thermal reaction in a static system

RL 773-794 7.8(2) 2/1

ES 773-794 3.98(13) 0 8907 2

EX 298-338 1.26(11) 0 6090±151 2 1.58 EX 298 ( 1 . 48±0 . 03 ) (2 ) 2

96
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH3CH2CHCH3 + cis-CH3CH=€HCH3

-* CH3CH2CH2CB3 + CH3CH=CCH3 Propyl, 1-methyl-, + 2-Butene, (Z)-

83 COL/RIC 1

) k re f

'• CH3CH2CHCH3 - CH3 + CH3 CH=CH2 Estimated ratio.

83 COL/RIC 1

)

1

) Thermal reaction in a static system.

(CH3

) 3C + (CH3) 3C -* (CH3) 2CH=CH2

+ (CH3

) 3CH (a)

-* (CH3

) 3CC(CH3) 3 (b) Ethyl, 1,1-dimethyl- (t-Butyl)

83 ART/ANA (k

fa

) ES 308 4.31(12) 2 Molecular modulation spectrometry.

(CH

3

) 3C generated by photolysis of Azo-t-butare at 350 nm. k extracted from the data by computerbased non-linear parameter estimation

and numerical integratiopn procedures.

RL 773-794 2.5(3) 2/1

ES 773-794 2.51(11) 0 4026 2

-» CO + CH^CH + C02

2 , 5-Furandione (Maleic anhydride)

81 BAC/PAR

Thermolysis in a static system.

Gas-chromatography

.

P = (0.7-20) torr.

EX 645-760 2.14(14)

-* CO + other products (a)

-* C02 + other products (b) 2 , 5-Furandione , dihydro- (Succinic anhydride)

83 YAM/BAC (k

fl ) EX 625-775 3.98(11)

(k

fa

) EX 625-775 3.16(5)

Thermolysis in packed, or unpacked vessels.

P = (4-20) torr.

CB3C(0)0CH=CH2 - (CB3

) 2CO + CO (a)

-» CH3CHO + CH2=C=0 (b) Acetic acid ethenyl ester (Vinyl acetate)

83 TAY3 (k a + k

fa

) EX 636-722 2.69(10)

(k

fa

) EX 600 2 . 12( -6

)

Thermolysis in a static system.

0 30649±503 1 2.0

0 26673 1

0 17111 1

0 21940 1

1

97
A. Table of Chemical Kinetic Data for Combustion Chemistry Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

H,Cn -» CH3CH=CH2 + C02

2-0xetanone, A-methyl- (/?-Butyrolactone)

83 FRE/WAT

Thermolysis in a static system.

P = (0.1-10) torr.

EX A82-523 2.A5QA) 0 19655±120 1 1.26

CH3C(0)0C(0)CH3-» CH3COOH + ch2=c=o

Acetic acid anhydride

71 BLA/SPE EX A70-6A3 1.86(11) 0 16202±226 1 1.55 Thermolysis in a static system.

ch3ch2och=ch2 ch2

=ch2 1 CB3CHO

Ethene, ethoxy- (Ethyl vinyl ether)

82 MCE/TA EX 617-677 6.65(11) 0 22363 1 EX 600 A . 32(-5) 1 Thermolysis in a stainless-steel reactor.

CH3C(0)0CH2CH3 - CHgCCOH + CH2=CH2 Acetic acid ethyl ester

83 LOU/TIN EX 679-737 2.51(12) 0 2A056±252 1 2.0 EX 673 7.5K-A) 1 Liquid phase thermolysis of Ethyl Acetate

diluetd in Toluene or m-Xylene,

in a microprocessor.

Gas-chromatography

CH30C(0)0CH2CH3 ch3oh 1 co2 + CH2=-_ C;i Carbonic acid ethyl methyl ester

83 TAY2 EX 626-682 1.59(12) 0 225A7 1 EX 600 7.61(-5) 1 Thermolysis in a stainless-steel reactor.

CH3CH2CH2C(0)00H -» ch3ch2ch2 + co2 + OE

Butaneperoxoic acid (Perbutyric acid)

83 LEV/PRI EX A03-513 9.55(12) 0 16527±20A5 1 55.0 Thermolysis in He or Ar, in a flow-type

Teflon reactor.

P = 760 torr. [Peracid] = (0.03-1.1) vol% (in He, or Ar).

98
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

(CH3

) 2CHC(0)00B -* (CH3) 2CH + C02 + OH

Propaneperoxoic acid, 2-methyl- (Perisobutyric acid)

83 LEV/PRI EX 403-513 1.41(13) 0 16467±1888 1 42.7,

Thermolysis in He or Ar, in a flow-type

Teflon reactor.

P = 760 torr. [Peracid] = (0.03-1.1) volZ (in He, or Ar).

(CH3

) 3CO (+ M) -* (CH3

) 2CO + CH3 (+ M)

Ethoxy, 1,1-dimethyl- (t-Butoxy)

82 BAT /ROB EX 402-443 3.98(14) 0 8002±604 1 3.98 (RRKM calculation.) ES 402-443 7.94(14) 0 8354 1 Thermolysis in a static system.

(CH3

) 3 CO generated by the decom- position of di-t-Butyl peroxide

diluted in NO. Gas-chromatography

.

Limiting high-pressure k. [t-BuO] = [NO] = ( 0 . 72-1 . 20 )xl0 16 molec.cm' 3

.

(CH3

) 3COOH(v=6) -* (CH3

) 3CO + OH

Hydroperoxide, 1,1-dimethyl ethyl-

(t-Butyl hydroperoxide)

82 RIZ/CRI EX 298 (4. 0+0.4) (6) 1 Unimolecular decomposition of t-Butyl

hydroperoxide excited to v = 6 (above

the barrier for dissociation), with a YAG pumped dye- laser. Time-resolved Laser-induced fluorescence.

P = (20-300) mtorr

.

Unreported T assumed to be 298 K.

CH3C(0)SC(0)CH3

-* CH3C(0)SH + CH2=C=0

Ethanethioic acid anhydrosulfide (Acetic thioanhydride , or Diacetyl sulfide)

74 BLA/SPE EX 459-526 1.05(11) 0 15757±770 1 4.68 Decomposition in a static system.

83 TAY1 EX 569-600 6.92(11) 0 19125 1 Thermolysis in a stainless-steel reactor. NMR-Spectroscopy

.

99
4. Table of Chemical Kinetic Data for Combustion Chemistry --Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(re£) B-B(ref) units factor

CE^CHCHgNCf 01i ~ ijCB2C

1-Propene, 3-isocyano-, (Allyl isocyanide)

-* 3-Butenenitryle (Allyl cyanide)

79 RED/BER2 (A = 746.4 nm.

)

EX 300 -6.0(5) 1 1.5

(A » 532.2 nm.

)

EX 300 4.6(8) 1 1.2 Photoisomerization with an intracavity

Vibrationally excited Allyl isocianide formed from Allyl isocianide by a cw dye Laser. Photoacustic spectrometry.

Gas-chromatography

P = (0-10) torr. k increases when A decreases, (k values

at intermediate wavelenghths are given

in a table .

)

( CH^ ) 2CHNCO —* CH3CH=CH2 + HN=C=0 (a)

-* CE4 + CH3CN + CO (b) Propane, 2-isocyanato- (Isopropyl isocyanate)

72 BAR/MIR (k

fl ) EX 686-771 5.13(12) 0 27831 2 UnimolecuLar elimination.

Thermolysis in a static reactor

Gas-chromatography

Mass-spa rtrometry

P = (70-433) torr.

83 BLA/IJA (k a

) EX 701-803 1.58(12) 0 26220±251 1 1.6

(k a

) EX 723 3 . 53 ( -4

)

1

(kb

> EX 701-803 2.51(10) 0 20533±2014 1 1.1

(kb

) EX 723 1 . 73 ( -3

)

1 Thermolysis in carbon-coated,

packed and unpacked reaction

vessels

(Chains are quenched by inhibitors .

)

P = (29-204) torr.

CH3C(0)NHC(0)CH3 - CH3C(0)NH2 + ch2=c=o

Acetamide, N-acetyl83 TAY1 EX 547-601 2.63(12) 0 19033 1 EX 600 4 . 37 ( -2

)

1 Thermolysis in a stainless-steel

reactor

NMR-Spectroscopy

100
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor ^ - o

Bicyclo [2 . 1 . 0]pent-2-ene -* 1 , 3-Cyclopentadiene

72 BAL/AND EX 323 ( 1 . 39±0 . 02 )

( -A ) 1 Thermal isomerization in an aluminum column. Gas -chromatography

.

+ H

2

Cyclopentene

73 KNE

Thermolysis in a Pyrex reaction vessel. Gas-chromatography . Mass-spectrometry

.

UV-Spectrometry . P = (4-34) torr.

Cyclopentene-dg

73 KNE Thermolysis in a Pyrex reaction vessel. Gas-chromatography . Mass-spectrometry

.

UV-Spectrometry. P = (4-34) torr.

txi CH2=CH2 1 C02^=CH2 ( a

)

(b)

Spiropentane -* Ethene + 1,2-Propadiene (a)

-* Cyclobutane, methylene- (b) 72 FLO/GIB (k a

) (k^. Isomerization)

Thermolysis in a static system, with or without CF 2CIF2

CI. Gas-chromatography. RRKM fit to the data, on the basis of

a proposed mechanism.

P(Spiropentane) = (0.9-335) torr. P(CF2C1CF2C1) = (0-721) torr.

73 KNE (k a

)

EX 753-803 (6 . 3±0 . 1 ) ( 12) 0 29089 1

EX 753-803 (9 . 9±0 . 2) ( 12) 0 30347 1

DE 663 7.94(13) 0 27932 1 EX 663 1.58(15) 0 27932 1

EX 753-803 ( 9 . 9±0 . 2) ( 12) 0 30347 1 Thermolysis in a Pyrex reaction vessel. Gas-chromatography. Mass-spectrometry.

UV-Spectrometry. P = (4-34) torr.

101
4. Table of Chemical Kinetic Data for Combustion Chemistry --Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

-* ch2=chch2ch2ch2

Cyclopentyl -* 4-Pentenyl

7 4 CAR/TAR2 DE 298 1.0(14)

Decyclization of Cyclopentyl in a Pyrex

reaction vessel. Cyclopentyl generated by reacting Cyclopentene with H atom, wich was itself

generated by the Hg-photosensitized

decomposition of H

2

. k calculated by

fitting the data to a model mechanism.

P = (0-11.1) torr.

0 17413±302 1 2.51

+ N02

-* products

Cyclopentyl + Nitrogen oxide (N02

) 83 PAR/GUT

Reaction in a fast-flow system.

Cyclopentyl generated by the reaction:

Cl atoms generated by dissociation of Cl2 in a microwave-discharge.

[Cyclohexane] = ~(5-50)xl0*3 molec.cm

[C1] Q = (0.5-1.5)xl0 U atom. cm

-3

. P(Total) = (0. 7-2.0) torr. (N02

)

EX 298 (2 . 23±0 . 06 ) ( 13

)

2

CH^CI^CE^CH^E^ (&)

- CH2=€H2 + A (b)

Cyclopentane

79 KAL/SHV (koverall > Pyrolysis of Cyclopentane-Pentane mixtures

in a flow-reactor. Gas-chromatography

[Cyclopentane] = (3.5-26.4) Z [Pentane) = (4.9-44.9) X. P ~ 1 torr.

kre f

; CH3CH3 -* products.

RL 978-1143 5. 3+1.

0 0 1/1

102
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH3CH2CH2CH3CH2-» products

Pentane

79 KAL/SHV RL 978*1143 1 . 3±0 . 1 0 0 1/1

Pyrolysis of Pentane-Cyclopentane mixtures

in a flow-reactor. Gas-chromatography.

[Cyclopentane] = (3.5-26.4)%

[Pentane] = (4.9-44.9)%

P ~ 1 torr.

^ref : o -* products

(CH3

) AC (+ M) -» (CH3

) 3C + CH3 (+ M)

Propane, 2,2-dimethyl- (Neopentane)

83 BER/SKI (M = Ar) EX 1140-1300 1.7(17) 0 42677 1 2.0 Pyrolysis behind reflected shock-waves. Resonance-absorption Spectroscopy.

Gas-chromatography.

[Neopentane] = ( 1 . 19-4 . 76 )xl0^ molec.cm

-* cb2=cbcb=cb2 + hcho

2H-Pyran, 3,6-dihydro79 FRE/LOD EX 602-647 2.86(14) 0 25254*221 1 1.42 Thermolysis in Pyrex, packed or unpacked

reaction vessels. Gas-chromatography

.

(CU3 ) 2

CflOCU--Cn2 CH3CH=CH2 t ch3cbo

Propane, 2-(ethenyloxy)- (Ethyl isopropyl ether)

82 MCE/TAY EX 617-677 3.37(12) 0 21960 1 EX 600 4 . 32(-4 ) 1 Thermolysis in a stainless-steel reactor.

CB3CH20C(0)0CH2CB3

-* CH2=CH2 + C02 + CB3CH2OH

Carbonic acid diethyl ester (Diethyl carbonate)

83 FAR/BEC EX 540-620 (1 . 94±1 . 33 ) (13 ) 0 23524*375 1 Thermolysis in sealed Pyrex tubes. Gas-chromatography. Arrhenius expression

calculated from the reported experimental

data.

103
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH3CH20C(0)0CD2CD3

-» CH2=CH2 + C02 + CD3CD2OB (a)

-» CD2=CD2 + C02 + CH3CB2OD (b) Carbonic acid ethyl ethyl-d^ ester

(Diethyl carbonate- 1,1, 2, 2-dj)

83 FAR/BEC (k 0 + k

fa

) (Calculated from the reported

experimental data.

)

(k

a /kb

) <w

Thermolysis in sealed Pyrex tubes. Gas -chromatography

EX 540-620 ( 1 . 59±1 . 03 ) ( 13

)

RL 540-620 (0.80±0.18)

RL 300 5.42

0 23572±369 1

0 574±131 1/1

1/1

CB30C(0)0CB(CB3

) 2

-» CB3OB + C02 + CB3CB2=CH2

Carbonic acid methyl 1-methylethyl ester (Isopropyl methyl carbonate)

83 TAY2 EX 595-661 1.09(13) 0 21668 1 EX 600 2 . 23 (-3

)

1 Thermolysis in a stainless-steel reactor.

CB3C(0)0CB(CH3 )CN CH3COOH + CB2=CHCH Propanenitrile , 2- ( acetyloxy )-

83 BER/CHU EX 583-683 7.59(12) 0 24454±313 1 1.95 Thermolysis in a static system.

P = (39-313) torr.

(CH3

) 3CNCO -* (CB3

) 2OCB2 + HM=C=0

Propane, 2-isocyanato-2-methyl- (-t-Butyl isocyanate)

72 BAR/MIR EX 683-693 3.89(13) 0 26371 2 Thermolysis in a static system.

Gas-chromatography

Mass-spectrometry

P = (70-433) torr.

83 BLA/IJA EX 701-803 2.51(13) 0 25969±151 1 1.26 EX 723 5 . 74 ( -3

)

1 Thermolysis in carbon-coated, packed and unpacked reaction vessels.

P = (29-204) torr.

(CB3

) 2NC(0)OCB2CH3

-* (CB3

) 2NB + co2 + cb2=cb2 Carbamic acid, dimethyl- ethyl ester

72 DAL/ZIO EX 643-703 1.26(12) 0 22315±201 1 Thermolysis in a static system.

Unreported, assumed T-range

104
4. Table of Chemical Kinetic Data for Combustion Chemistry Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

trans-CH2=CHCH=CHCH=CH2 cis-CH2=CHCH=CBCH=CE2

1, 3 , 5-Hexatriene , ( E

) — , + 1 , 3 , 5-Hexatriene , (Z)-

74 ORC/THR EX 588-640 (4 . 5±1 . 5) (12) 0 21808±241 1 (Limiting high-pressure k.) EX 640 7.08(-3) 1 Thermal isomerization

in a static system.

P = (1-20) mtorr.

+ Ho

1 , 3-Cyclohexadiene

74 ORC/THR

Thermolysis in a static system.

P = (1-20) mTorr.

EX 719-824 (4 . 7±2 . 2 ) ( 13 ) 0 31033±481 1

1 , 3-Cyclopentadiene , 1-methyl-

-* 1 , 3-Cyclopentadiene, 2-methyl

72 BAL/AND EX 323 8.2(-6) 1 Thermal isomerization

in an aluminum column. Gas -chromatography

.

1, 3-Cyclopentadiene, 2-methyl-

-* 1, 3-Cyclopentadiene, 1-methyl72 BAL/AND EX 323 5.8(-6) 1 Thermal isomerization

in an aluminum column. Gas-chromatography

.

Bicyclo[2.2. 0]hex-2-ene -* 1 , 3-Cyclohexadiene

76 GOL/LEI EX 376-425 (7 . 4±0 . 8) (13 ) 0 16583±45 1 Thermal rearangement

.

P = (240-420) torr.

105
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

- <>

- O <b>

''CH J Bicyclo[2. 1 . 0]pent-2-ene , 1-methyl- * 1,3-Cyclopentene, 1-methyl

-» 1,3-Cyclopentene, 2-methyl

72 BAL/AND <k

a

)

(k

fa

) Thermal isomerization in an aluminum column Gas-chromatography

Bicyclo[2. 1 . 0]pent-2-ene, 2-methyl- * 1, 3-Cyclopentadiene, 1-methyl (a)

-* 1 , 3-Cyclopentadiene, 2-methyl (b) 72 BAL/AND (k 0

) EX 323

(kb

) EX 323 Thermal isomerization in an aluminum column. Gas-chromatography

- (a)

- (b) EX 323 EX 323

1 . 94 (-4 ) 1.2(-4)

3.6(-5)

4 . 64 ( -5)

(+ M) - CH2=CHCH=€H2 + CH2=CH2

(+ M)

Cyclohexene

78 LEW/GIE (Limiting high-pressure k.)

(Limiting high-pressure k.)

Decomposition in a single-pulse shock-tube,

behind reflected shock-waves. Calibration experiments.

Gas-chromatography. M = Ar, or He. P = (533-5097) torr.

81 SKI/ROG (P = 3 atm. ) (P = 9 atm. ) Thermolysis behind reflected shock-waves,

in a single pulse shock-tube. M = Ar ( with added CH^ )

Calibration experiments.

Gas-chromatography

[Cyclohexene] = 0.9 % in Ar. [Methane] = 0.9 1 in Ar.

SE 1038-1208 1.41(15)

ES 1038-1208 2.00(15)

EX 1000-1241 1.00(16) EX 1000-1341 2,51(15)

1

1

1

1

0 33488 1

0 33689 1

0 33518±1007 1 3.16

0 33719±1359 1 3.16

106
Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

-o

Cyclobutane, ethenyl- -* Ethene + 1,3-Butadiene (a)

-+ Cyclohexene (b) 78 FRE/POT (k a

) EX 569-639 7.41(14) 0 25529191 1 1.16

<kb

) EX 569-639 7.14(13) 0 244801183 1 1.35

+ k

b> EX 569-639 5.25(14) 0 25059179 1 1.14 Thermolysis in a static system.

Gas-chromatography. P = (1-13.5) torr.

(+ M )

-* CH2=CHCB2

CH2CH2CH3 (+ M) (a)

-» any other products (b) Cyclohexane

81 SAT/KAL ^overall* EX 993-1103 8.91(18)

Pyrolysis in a tubular quartz reactor. M = Ar. P(Ar ) = 760 torr.

P( Cyclohexane) = 80 torr.

83 ZYC/BAC (koveraii) EX 1023-1123 7.8(16)

Thermolysis in a flow-reactor. Gas-chromatography. P = 760 torr.

CH3 (CH2 )^CH3

-* products

Hexane

83 EBE/EDE EX 650-840 8.32(13)

Thermolysis in a static reactor. Gas-chromatography

.

83 ZYC/BAC EX 953-1033 5.4(11)

Thermolysis flow-reactor. Gas-chromatography. P = 760 torr.

0 4474U1761 1 5.01

0 41378+481 1

0 31310 1

0 26463±241 1

0=c±y=0

H,C CHj

•+ CO + other products

-* C02 + other products

2 , 5-Furandione , dihydro-3 , 4-dimethyl-

,

(Succinic anhydride, 2,3-dimethyl-,

(a)

(b) ciscis

)

83 YAM/BAC (k

a

) <kb

) Thermolysis in packed, or unpacked vessels.

P = (4-13) torr.

EX 625-775 2.51(10)

EX 625-775 =1.58(8)

0 23956 1

0 21137 1

107
4. Tabl® of Chemical Kinetic Data for Combustion Chemistry --Continued

Reaction, Reference Code, Notes Data T/K k ,k/k(ref )

n B, k , A

type A, A/A(ref

)

B-B(ref) units

HjC ^

0= ^l - 0-7=0

CH3

-* CO + other products (a)

-» CO2 + other products (b)

2, 5-Furandione, dihydro-3 , 4-dimethyl- , trans-

(Succinic anhydride, 2,3-dimethyl-, trans-)

83 YAM/BAC (k

a

)

(kb

; Thermolysis in packed, or unpacked vessels.

P = (4-13) torr.

EX 625-775 3.54(9) EX 625-775 -1.58(8)

*0 H3c-|—I "* CH2

==C(CH3

) 2

+ CH2=C=0

ch3 Cyclobutanone, 3 , 3-dimethyl77 FRE/SMI EX 534-586 3.74(14)

Thermolysis in a static system, with packed

or unpacked vessels. Gas-chromatography.

P

Q = (0. 5-8.0) torr. a

OCHj

—* CHgOCH=CH2 "t CH2=CHCHO

2H-Pyran, 3 , 4-dihydro-2-methoxy-

-* Ethene, methoxy-, + 2-Propenal

72 FRE/HOP EX 569-626 2.63(14)

Thermolysis in a Pyrex vessel with vacuum

system. Gas-chromatography.

P = (1-9) torr.

ce3CH2c ( 0 ) esc ( 0 ) ce2ce3-» ch3cb2cooh + ch3ch=c=o

Propanoic acid anhydride

76 BLA/CRA EX 493-567 2.40(11)

Thermolysis in a static system,

with packed or unpacked vesels.

CB3C(0)QCH(CH3 )C(0)CH3 - CHgCOOH + CB2=CHC(0)CB3 2-Butanone, 3-(acetyloxy)-

83 HER/CHU EX 583-683 2.51(13)

Thermolysis in a static system.

P = (39-313) torr.

83 LOU/TIN EX 711-793 1.58(12)

EX 673 2.51(-3)

Liquid phase Thermolysis in Toluene or m-Xylene, in a microreactor.

Gas - chromatogr aphy

0 21798 1

0 21137 1

0 23186±101 1

0 24430±54 1

0 16888±391 1

0 24394±123 1

0 22899±252 1

1

108

k err. factor

1.20

1.10

2.09

1.58

2.0
A. Table of Chemical Kinetic Data for Combustion Chemistry — Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH3C(0)0CH(CH3 )C(0)0Ce3

-* CH3COOH + CB2=CHC(0)0CH3 Propanoic acid, 2- ( acetyloxy ) - , methyl ester

83 HER/CHU EX 583-683 2.82(13)

Thermolysis in a static system.

P = (39-313) torr.

83 LOU/TIN EX 725-790 2.00(13)

EX 673 6 . 30 ( -A

)

Liquid phase thermolysis in Toluene or m-Xylene, in a microreactor.

Gas-chromatography.

0 25200±60 1 1.12

0 25516±252 1 2.0

1

CH3C (0 )OCB2CH2C (0 )OCH3

-+ CHgCOOB + CB2=CBC(0)0CB3 Propanoic acid, 3- (acetyloxy)- , methyl ester

81 TAY EX 632-683 1.00(11) 0 19240 1

CB3C(0)0CB2CB20C(0)CB3-» CB3C(0)OCB=CB2 + CB3COOB

1,2-Ethanediol diacetate (1,2-Diacetoxyethane)

83 TAY

3

EX 683 2 . 4 (-4

)

1 EX 691 3 . 6

( -4 ) 1 Thermolysis in a static system with a stainless-steel reactor.

CB3CB2CB2CB20CB=CB2

-» cb3cb2cb=cb2 + cb3cbo

Butane, l-(ethenyloxy)- (n-Butyl vinyl ether)

82 MCE /TAY EX 650-681 1.92(11) 0 21367 1 EX 600 6 . 57 ( -5

)

1 Thermolysis in a stainless-steel reactor.

( cb3

) 3cocb=cb2

-* (cb3

) 2c=cb2 i cb3cbo

Propane, 2- (ethenyloxy) -2-methyl- (t-Butyl vinyl ether)

82 MCE /TAY EX 595-651 1.48(12) 0 19733 1 EX 600 7 . 68( -3

)

1 Thermolysis in a stainless-steel reactor.

CB3C(0)0C(CH3

) 3

-» CE3COOB + CB2=C(CB3

) 2 Acetic acid 1 , 1-dimethylethyl ester (t-Butyl acetate)

83 LOU/VER EX 582-627 1.91(14) 0 21050 1 Pyrolysis in a microreactor, or in a Pyrex

glass macroreactor. Gas-chromatography

.

109
A . Table of Chemical Kinetic Data for Combustion Chemistry --Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

CH-jCH ( OH ) CH2C ( 0 ) OCE^CH;} "+ CH^CHO 1 CLI -^C ( 0 ) OCH^,CH

Butanoic acid, 3-hydroxy-, ethyl ester

71 YAT/RAM

Thermolysis in capilary glass tubes. Gas-chromatography

(CH3

) 2C{0H)CH2C(0)0CH3

-» (CH3

) 2CO + CH3C(0)0CH3 Butanoic acid, 3-hydroxy-3-methyl- , methyl ester

71 YAT/RAM

Thermolysis in capilary glass tubes. Gas-chromatography

CH30C(0)0C(CH3

) 3

-» ch3oh + C02 + (CH3

) 2C=CH2 Carbonic acid 1,1-dimethyl methyl ester

83 TAY2

Thermolysis in a stainless-steel reactor.

CH3C(0)CH2SCH2CH=CH2

-* CH3C(0)CHS + ch3ch=ch2 2-Propanone, l-(2-propenylthio)-

(Acetonyl allyl sulfide)

-* Propanethyal, 2-oxo- + 1-Propene

83 MAR/ROP

Pyrolysis in a stirred-flow-reactor

Mass-spectrometry. P = (3-13) torr.

(CH3

) 2CHN=NCH(CH3

) 2 - (CH3

) 2CH + (CH3

) 2CH + N

? Diazene, bis ( 1-methylethyl)- (Azoisopropane)

75 SZ1/MAR2

Thermolysis in a static system.

Gas-chromatography

CH3C(0)0C(CN)(CH3

) 2

-* CH3COOH + CH2=C(CN)CH3 Propanenitrile, 2- ( acetyloxy )-2-methyl83 LOU/TIN

Liquid phase thermolysis in Toluene or m-Xylene, in a microreactor.

Gas -chromatography

(CH3

) 2NC(0)0CH(CH3

) 2 - (CH3

) 2NH + C02 + CH3CH=CH2 Carbamic acid, dimethyl-, 1-methylethyl ester

72 DAL/ZIO

Thermolysis in a static system. Assumed T-range.

EX 583-613 9.54(10) 0 19980 1

EX 563-593 2.19(11) 0 19678 1

EX 546-598 8.65(12) 0 18772 1 EX 600 2 . 22( -1

)

1

EX 586-625 8.91(9) 0 15036±361 1 1.95

EX 494-546 2.51(15) 0 22446+252 1 1.58

EX 640-713 7.94(11) 0 20232±252 1 2.0 EX 673 6 . 30 ( -2

)

1

EX 643-703 1.10(13) 0 21797±201 1

110
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor o1, 3 , 5-Cycloheptatriene -* Benzene, methyl- (Toluene)

76 GAY/GIL EX 990-1250 3.98(13) 0 25741±1203 1 2.0 Thermal isomerization behind shock-waves,

f 1 , 3 , 5-Cycloheptatriene] = (0.01-0.1) X in Ar.

PQ = 98-190 torr. P = (300-600) torr.

76 GAY/GIL EX 800-1130 3.98(13) 0 26186±253 1 1.26 Thermal isomerization by VLPP-Technique

.

Mass-spectrometry. P ~2 mtorr.

79 AST/TRO (M = Ar) EX 900-1300 2.69(13) 0 25079±722 1 1.58

(M = Ar. Limiting high-pressure k) ES 600-1400 1.25(14) 0 26523 1 (Extrapolation)

Isomerization behind incident and reflected

13 -3 shock-waves. [Ar] = 4.46x10 molec . cm .

CHj

(+ M) (+ M)

r

C=CH,

XCH, CH2=CH2

+ CH2=CHC(CH3 )=CB2

(a) CHj

(b)

Cyclobutane, ( 1-methylethenyl)-

-* Ethene + 1,3-Butadiene, 2-methyl- (a)

-* Cyclohexene, 1-methyl- (b) 78 FRE/POT <ka

> EX 574-624 1.66(15) 0 26345±213 1 1.42

(kb

) EX 574-624 5.77(13) 0 24636±278 1 1.58

(k

a + kb> EX 574-624 9.08(14) 0 25699±152 1 1.29 Thermolysis in a static system, with packed or unpacked Pyrex vessels. Gas-chromatography.

P = (1-13.5) torr.

(+ M) -* products

Cyclohexane, methyl81 SAT/KAL EX 988-1073 9.12(17) 0 40765±1711 1 5.01 Pyrolysis in a quartz reactor. M = Ar. P(Methylcyclohexane ) = 80 torr. P(Ar) = 760 torr.

83 ZYC/BAC EX 993-1083 1.2(16) 0 38130±722 1 Thermolysis in a flow-reactor. Gas-chromatography

.

P = 760 torr.

Ill
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k ,k/k ( ref)

n B, k , A

type A, A/A(ref

)

B-B(ref) units

i Cl1^ C^O

Bicyclo[3 . 2. 0 lhept-2-en-6-one

•* 1 , 3-Cyclopentadiene + Ethenone (Ketene)

72 EGG/C0C2 EX 471-534

H3 C

Pyrolysis in a static reactor, in Propene

diluent. Gas-chromatography.

P(substrate) = (148-223) torr. P(Propene) = (132-500) torr.

P

D = (15-485) torr

-* trans-CH3CH=CHCH=CH2 + CB3CHO

1.45(13)

2H-Pyran, 3 , 6-dihydro-2 , 6-dimethyl- , cis- * 1,3-Pentadiene, (E)- + Acetaldehyde

79 FRE/POT EX 573-624 8.13(13)

Thermolysis in a static system.

Gas-chromatography. P = (3-7) torr.

CH=CH2 ^'H3 H 3C

(major pathway)

Oxetane, 3-ethenyl-2 , 4 -dimethyl- , (2a, 30, 4a)

-* Acetaldehyde + 1,3-Pentadiene

80 CAR/MAI

Thermolysis static system.

P = (3.5-30) torr.

-» CH3CH20CH=CH2 + ch2=chcho

EX 599-657 2.63(13)

2H-Pyran, 2-ethoxy-3 , 4 -dihydro77 BAI/FRE EX 561-628 2.92(14)

Thermolysis in a static system. Gas -chromatography. P = (1-13) torr.

H

ch3och=ch2 1 ch3ch=chcho

2H-Pyran, 3 , 4-dihydro-2-methoxy-4-methyl- , cis

75 COL/FRE EX 560-618 9.08(13)

Thermolysis in a static system.

P = (4-12) torr.

0 18888±126 1

0 23612±144 1

0 24093±902 1

0 24308±75 1

0 23576±84 1

112

k err. factor

1.29

1.26

3.98

1.14

1.15
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k ,k/k (ref)

,

n B, k , A

type A,A/A(ref

)

B-B(ref) units

- cb3ocb=cb2 + cb3ch=chcbo

2H-Pyran, 3 , 4-dihydro-2~methoxy-4-methyl- , trans75 COL/FRE EX 560-618 1.76(14) 0 24233±144 1 Thermolysis in a static system.

P = (4-12) torr.

(GB3

) 2CBCB2C(0)0CB2CB3 + (CB3

) 2CHCH2COOB + CB2=CB2 Butanoic acid, 3-methyl-, ethyl ester

83 CHU/MAR EX 633-693 5.01(12) 0 24538±529 1 Pyrolysis in a static system.

P = (71-286) torr.

cb3c(0)ocb2cb2cb2cb2ocb3

—* cb3oob i cb2=cbcb2cb2ocb3

1-

Butanol, 4-methoxy-, acetate

78 CHU/ROT EX 643-693 2.34(13) 0 25200±349 1 Pyrolysis in a static system.

.

P = (67-216) torr.

CB3CB ( OB ) CB ( CB3

) C ( 0 ) OCB2CB3

-* CBgCBO + CB3CB2C(0)OCH2CH3 Butanoic acid, 3 -hydroxy- 2-methyl- , ethyl ester

71 YAT/RAM EX 573-603 1.78(11) 0 19628 1 Thermolysis in capilary glass tubes. Gas-chromatography

.

iCB3

5 2C ^ 0E>CH2C(0)0CH2CH3

H> CCB3

) 2CO

Butanoic acid, 3-hydroxy-3-methyl- , ethyl ester

71 YAT/RAM EX 563-693 1.58(11) 0 19376 1 Thermolysis in capilary glass tubes. Gas-chromatography

.

CB3C(0)0CB(CB3 )CB2N(CB3

) 2

-* CE,COOH + CH2=CBCB2N(CH3

) 2

2-

Propanol, 1- (dimethylamino )- , acetate ester

83 HER/CHU EX 583-683 4.57(12) 0 22361+301 1 Thermolysis in a static system.

P = (39-313) torr.

(CB3

) 2NC(0)0C(CB3

) 3

-+ (CB3

) 2NB + C02 + CB2=C(CB3

) 2 Carbamic acid, dimethyl-, 1 , 1-dimethylethyl ester

72 DAL/ZIO EX 643-703 7.41(12) 0 18993±201 1 Thermolysis in a static system. Assumed T-range.

k err

.

factor

1.28

1.29

1.70

1.16

113
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

(+ M) CO (+ M) (a)

+ CHhCH (+ M) (b)

1 , 3 , 5, 7-Cyclooctatetraene -* Peentalene, 1,5-dihydro- (a) Benzene + Ethyne

79 DUD/GLA1 <k A + kh>

Pyrolysis behind reflected shock-waves.

UV-, and IR-Absorption Spectrometry. M =

[Ar] = (0.06-1.2)xl020 molec.cm" 3

.

Ar.

83 MAR/PFO + kK ) 'a Ab

Thermolysis in a static system.

P = 0.3 torr.

(b)EX 1000-1400

EX 1000-1400

EX 1000-1400

EX 646-666

1.58(13)

3.98(12)

6.31(13)

6.31(14)

24177±601

23095

26944

27932±755

1.58

3.16

=\ t t (+ M)]

isomerization products (+ M) (a)

+ CH^CH (+ M) (b)

[1,3,5,7-Cyclooctatetraene - Bicyclo[4 . 2. 0]octa2,4,7-triene] -* isomerization products (a)

-* Benzene + Ethyne (b) 79 DUD/GLA2 (k

fl + kfa

)

A = 311.8 nm. <E> = 94.168 kcal.mol." 1

M * 1,3,5,7-Cyclooctatetraene.

(k

fl + kb

)

A = 247.4 nm. <E> = 118.045 kcal.mol. M = 1,3,5,7-Cyclooctatetraene.

(k 0 + kb

. M = He)

A = 282 nm. <E> = 103.872 kcal.mol" 1

.

(k a + kb

. M = He)

A = 245 nm. <E> = 119.168 kcal.mol" 1

. Isomerization and decomposition of Cyclooctatetraene by both, steady-state

Photolysis ’ iser Flash-photolysis.

EX 298

EX 298

EX 298

EX 298

1 . 1 ( 6 )

2.7(7)

4.5(6)

3.0(7)
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

1 , 5-Dihydropentalene -* Benzene, ethenyl- (Styrene)

79 DUD/GLA1 EX 1200-1600 1.26(13) 0 29109±962 1 2.0 Pyrolysis behind incident or reflected

shock-waves

.

M = Ar. UV-, and IR-Absorption spectrometry.

[Ar] = (0 . 06-0 . 12)xl0^ molec.cm 3

.

(main primary product)

1 , 5-Dihydropentalene -* Cyclopropa[cd]pentalene

,

2a , 2b , 4a , 4b-tetrahydro- (Semibullvalene

)

79 DUD/GLA2 EX 298 1.5(7) 1 <E> = 118.714 kcal.mol.'* at 246 nm. M = 1 , 5-Dihydropentalene

.

Isomerization by steady-state photolysis.

Cyclopropa [cd] pentalene , 2a , 2b , 4a, 4b-tetrahydro-

( Semibullvalene) -» 1 , 5-Dihydropentalene

79 DUD/GLA1 EX 740-900 6.31(14) 0 20689+1203 1 2.51 Pyrolysis behind incident or reflected

shock-waves

.

M = Ar

.

UV-, and IR-Absorption Spectrometry.

[Ar] = (1.2-3. 0 )xl0 19 molec.cm' 3

.

Tricyclo[4.2.0.0^’^]octa-3,7-diene, ( la, 2a, 5a , 6a)

(syn form) -* 1 , 3 , 5 , 7-Cyclooctatetraene

74 CAS /DEW EX X

) 2.29(13) 0 14494±171 1 2.19

EX 370 2 . 75(-4

)

1

* ) Temperature range not given.

75 FRE/MAR EX 363-394 1.66(14) 0 15345±81 1 1.23 Gas-chromatography

.

115
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A

type A,A/A(ref) B-B(ref) units

Tricyclo [4.2.0.0 2, ^]octa-3, 7 -diene , ( la

20

5/3, 6a)-

(anti form) -* 1 , 3 , 5, 7-Cyclooctatetraene

74 CAS /DEW EX *> 1.51(14) 0 16306±453 1 EX 370 1 . 40 ( -5) 1

J

) Temperature range not given.

75 FRE/MAR EX 385-419 1.02(14) 0 16402±86 1 Gas-chromatography

Pentacyclot A . 2 . 0 .

2 • ^0^ • 8 0^ > 7

] octane (Cubane) + 1 , 3 , 5 , 7-Cyclooctatetraene -* Benzene + Ethyne

83 MAR/PFO EX 507-521 7.94(14) 0 21943±352 1 Thermolysis of Cubans in static system.

P = 0.3 torr.

1 , 3 , 6-Cyclooctatriene -* 1 , 3 , 5-Cyclooctatriene

83 GRE/ORC

Static system. Gas-chromatography.

(+ M) -* products

EX 390-490 8.51(10) 0 1394 1±84 1

1,3, 5-Cycloheptatriene , 7-methyl79 AST/TRO EX 900-1400 1.79(13) 0 24478±601 1 (Limiting high-pressure k) ES 600-1400 9.77(13) 0 26030 1

( Extrapolation .

)

Isomerization behind incident and reflected shock-waves. M = Ar.

[Ar] = 4.81xl0 17 -1.20xl0 20 molec . cm'

D

Bicyclo[2.2. l)hept-2-ene , 5-methylene-d2“

-* Bicyclo[2.2. l]hept-2-ene-5,5-d2, 6-methylene72 HAS EX 530-561 3.16(13) 0 23100±151 1 Static reactor.

P = 1 torr.

k err. factor

3.63

1.23

2.0

1.20

1.58

1.26

116
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A

type A,A/A(re£) B-B(ref) units

Bicyclo[3 . 2 . 0]hept-2-ene, 6-methylene-

-* BicycloE .2.2. l]hept-2~ene, 5-methylene72 HAS EX 459-491 5.01(13) 0 19930±50 1 Static reactor.

P = 1 torr.

D Bicyclo [3 . 2 . 0 ]hept-2-ene , 6-methylene-d2_

-* Bicyclo[3.2.0]hept-2-ene-7,7-d2, 6-methylene73 HAS EX 468-499 2.51(13) 0 20584±201 1 Static reactor. NMR-spectrometry

.

P = 1 torr.

Bicyclo [3 . 2 . 0 ]hept-2-ene-7 , 7-d2> 6-methylene-

-* Bicyclo[2.2. l]hept-2-ene-5, 5-d2> 6-methylene- (a)

-* Bicyclo[2.2. l]hept-2-ene, 5-methylene-d2_ (b)

(k

g + kb

) EX 468-499 6.31(13)

Static reactor. NMR-spectrometry.

P = 1 torr.

Bicyclo [3 . 2 . 0 ]hept~6-ene, 2-methylene-

-» 1, 3-Cycloheptadiene, 5-methylene- (a)

-* 1, 3-Cycloheptadiene, 6-methylene- (b) 80 HAS/LOO (k

a + kfa

) EX 436-481 4.07(13)

Static reactor.

P = (0.075-5.25) torr. k is P-independent within this range.

0 20081±50 1

0 19024±81 1

k err. factor

1.58

1.58

1.26

1.20

117
4. Table of Chemical Kinetic Data for Combustion Chemistry ""Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

Bicyclo [ 4 . 2 . 0 ] octa-2 , 4-diene -» 1 , 3 , 5-Cyclooctatriene

83 GRE/ORC EX 330-475 2.40(12) 0 12858±180 1 1.70 Static reactor. Gas-chromatography.

nCH2 Tricyclo[4 .1.0.0^’ 7

] heptane, 3-methylene-

-* Bicyclo [3 . 2 . 0]hept-6-ene , 2-methylene- (a)

-* 1,3-Cycloheptadiene, 5-methylene- (b)

-* 1,3-Cycloheptadiene, 6-methylene- (c)

-* Cyclohexene, 3, 6-bis (methylene)- (d) 80 HAS/LOO (koverall ) EX Static reactor. P = (0.075-3.75) torr.

k is P-independent within this range.

396-446 3.02(12) 0 16376+221 1 1.70

HiC CH'

H,C CH,

products

Cyclobutane, 1 , 2-dimethyl-3-4-bis (methylene )- , cis-

-* products

72 GAJ/SHI EX 511 EX 528 Pyrolysis in a static reactor. P <10 torr.

pt. H]C >—

CHl . . IX X -+ products

CH,

Cyclobutane, 1 , 2-dimethyl-3 , 4-bis (methylene )- , trans-

-* products

72 GAJ/SHI EX 511 EX 528

2 . 9 ( -5 )

( 1 . 20±0 . 05 )

(

4 )

4 . 2 (5 )

( 1 . 50±0 . 05 )

( -4

)

1

1

1

1 Pyrolysis in a static reactor. P <10 torr.

118
4. Table of Chemical Kinetic Data for Combustion Chemistry Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

/CHj

*H

^CHj

CH,

products

Cyclobutane, l-ethylidene-3-methyl-2-methylene- , (Z)-

-* products

72 GAJ/SHI EX 528 Pyrolysis in a static reactor. P <10 torr.

(1. 10±0 . 05) (-3)

hjC CH,

h27:ch

products

Cyclobutane, 1,2-diethylidene, (Z,Z)- -* products

72 GAJ/SHI

Pyrolysis in a static reactor. P <10 torr.

EX 528 ( 5 . 6±0 . 1 )

( -4

)

HjC-. C

sHl HCV XH Z7 products

1

1

Cyclobutane, 1,2-diethylidene, (E,Z)- + products

72 GAJ/SHI

Pyrolysis in a static reactor. P <10 torr.

ch2 ch3

(+ M) products

EX 528 (3 . 9±0 . 1 )

(

4 ) 1

Cyclohexane, ethyl81 SAT/KAL EX 993-1093 7.08(19) 0 44741±1711 1 5.25 Pyrolysis in a quartz reactor. M = Ar. P(Ethylcyclohexane) = 80 torr. P(Ar) = 760 torr.

83 ZYC/BAC EX 953-1083 9.6(13) 0 31996±241 1 Thermolysis in a flow-reactor. Gas-chromatography.

P = 760 torr.

(+ M) -* products

Cyclohexane, 1, 2-dimethyl81 SAT/KAL EX 953-1073 5.50(12) 0 27730±2365 1 7.94 Pyrolysis in a quartz reactor. M = Ar.

P( 1 , 2-Dimethylcyclohexane ) = 80 torr. P(Ar ) = 760 torr.

119
A. Table of Chemical Kinetic Data for Con£>ustion Chemistry --Continued

Reaction, Reference Code, Notes Data T/K k ,k/k ( ref)n B, k , A

type A,A/A(ref

)

B-B(ref) units

(+ M) -*• products

Cyclohexane, 1 , 3-dimethyl81 SAT/KAL

Pyrolysis in a quartz reactor. M = Ar.

P( 1 , 3-Dimethylcyclohexane ) = 80 torr. P(Ar ) = 760 torr.

(+ M) -» products

CH,

Cyclohexane, 1 , 4-dimethyl81 SAT/KAL

Pyrolysis in a quartz reactor. M = Ar. P(l,4-Dimethylcyclohexane) = 80 torr. P(Ar ) = 760 torr.

EX 993-1098 6.92(12)

EX 963-1103 7.08(15)

CHgfCHgJgCHg (+ M) -* products

Octane

83 DOO/MAC EX 1100-1400 7.41(11)

(Theoretical fit) DE 1100-1400 4.57(11)

(Based on a proposed mechanism.)

Pyrolysis in a single-pulse shock-tube,

behind reflected shock-waves. Gas-chromatography. M = Ar, or H2

CH, - CH2=CHCH2CH=CHC(CH3 )=C(0)

-» products (b) Bicyclo [3.2. 0 ]hept-3-en-6-one , 5 -me thy 1-

-* Bicyclo [ 2 . 2 . l]hept-5-en-2-one , 5-methyl- (a)

-* 1 , 3 , 6-Heptatrien-l-one , 2-methyl- (b) 73 COC/EGG2 (k

fl + k

b

) EX 489-565 3.16(14)

Pyrolysis in a static system. Gas-chromatography.

P = (2.7-20) torr. The product of the channel

(b), 2-Methyl-l , 3 , 6-hexatrien-l-one , undergoes

rapid secondary reactions, to give two major

products

3-Methyl-bicyclo [3.2. 0]hept-3-en-6-one and 5-Methyl-l , 3-Cyclohexadiene-l-carboxaldehyde

as well as two minor products:

3 -Me thy 1-benzaldehyde and Toluene.

120

0 28183±2365 1

0 35682*1409 1

0 27064±1202 1

0 26463 1

0 22108±337 1

k err

factor

5.01

3.98

2.69

1.91
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

h5co(6)c-~t-ch h3Cxc(o}°ch3 O

c(o)oCHj

HjC'^'

C(0J0CH, H3C-v/^

Bicyclo [2 . 1 . 0 ] pent -2- ene-5- carboxylic acid

,

5-methyl-, methyl ester (la, 4a, 5a)- (exo form)

-* 2, 4-Cyclopentadiene-l-carboxylic acid,

1-methyl-, methyl ester

- 1, 3-Cyclopentadiene-l-carboxylic acid,

2-methyl-, methyl ester

= 1, 4-Cyclopentadiene-l-carboxylic acid,

5-methyl-, methyl ester

83 KLA/ADA (P = 0.4 torr.) EX 322

(P = 19.4 torr. ) EX 322 Gas-phase Thermolysis in a Pyrex vessel, k increases

with the pressure.

P = (0.4-20) torr.

EX 304-343 Liquid-phase Thermolysis,

0.5 Vol.% in Hexane.

( 1 , 77 ±0 . 07 )

(

4 )

(2 . 31±0 . 03 )

(

-4 )

1.22(14)

1

1

0 13191±96 1

HjC-^r-cfojOCHj HjCy-C(o)OCHj 3o c(o)oCH, H3 C-^

H3 C

c(o)oCH3

Bicyclo[2. 1 . 0] pent-2-ene-5-carboxylic acid,

5-methyl-, methyl ester ( la, 4a , 5/3 )- (endo form)

-* 2 , 4-Cyclopentadiene-l-carboxylic acid,

1-

methyl-, methyl ester

= 1 , 3-Cyclopentadiene-l-carboxylic acid,

2-

methyl-, methyl ester - 1 , 4-Cvclopentadiene-l-carboxylic acid,

5-methyl-, methyl ester

83 KLA/ADA (P=0.4 torr.) EX 322 ( 1 . 45±0 . 07) (-4 ) . 1

121
A. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K

type

k,k/k(ref )

A, A/A(ref

)

n B, B-B(ref)

k,A k err. units factor

83 KLA/ADA (P = 18.3 torr) EX 322 ( 1 . 98±0 . 01) ( -4 ) 1 Gas-phase Thermolysis in a Pyrex vessel, k increases

with the pressure.

P = (0.4-20) torr. EX 304-343 5.07(13) 0 12974±55 1 Liquid-phase Thermolysis,

0.5 Vol.% in Hexane.

-* (CH3

) 2C”CH2 + (CH3) 2C=C=0 (a) (major pathway

)

-* + CO (b) (minor pathway)

»1 Liij

Cyclobutanone, 2,2,4, 4-tetramethyl-

-* 1-Propane, 2-methyl-

+ 1-Propenone, 2-methyl- (a)

-* Cyclopropane, 1 , 1, 2, 2-tetramethyl-

+ Carbon monoxide (b)

(k

a

> EX 637-700 7.23(14) 0 28156±47 1 1.10

(kb

) EX 637-700 7.36(14) 0 29988+47 1 1.10

<k

a + V EX 637-700 8.91(14) 0 28269±47 1 1.07 Thermolysis in a static system.

IR- , and NMR-Spectrometry

Gas-chromatography

P

Q = (6-8) torr. Rate constants are P-independent

within this range.

(CH3

) 2CHC(0)0C(0)CH(CH3

) 2 - (CH3 )CHCOOH + (CH3

) 2C=€=0

Propanoic acid, 2-methyl-, anhydride

76 BLA/CRA EX 519-556 6.45(11) 0 18223±366 1 1.95 Thermolysis in a static system with

packed and unpacked vessels.

CH3C ( 0 ) OCH2CH2CH ( ch3 )CH2CH3 CH3COOH + CH2=CHCB(CH3 )CH2CH3 1-Pentanol, 3-methyl-, acetate

81 MAR/CHU EX 633-693 4.17(13) 0 25488±144 1 1.23 Pyrolysis in a static system.

P = (34-377) torr.

122
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A

type A,A/A(ref) B-B(ref) units

CH3C(0)0CH2CH2CH2CH(CB3

) 2 + CHgCOOH + CH2=CHCH2CH(CH3) 2

1-

Pentanol, 4-methyl-, acetate

81 MAR/CHU EX 633-693 6.61(12) 0 24430±72 1 Pyrolysis in a static system.

P = ( 34-377 ) torr.

CH3C(0)OCH(CH3C(CH3

) 3 - CH-jCOOH + CH2=€HC(CH3) 3 + other minor products

2-

Butanol, 3,3-dimethyl-, acetate

72 CHU/MAR EX 578-653 3.16(12) 0 22174±302 1 Pyrolysis in a static system.

P = (25-300) torr. The rate constant is P-independent

within the given range.

(CH3

) 3CCH2C(0)0CH2CH3

-» (CH3

) 3CCE2COOH + ch2=ch2 Butanoic acid, 3,3-dimethyl-, ethyl ester

83 CHU/MAR EX 633-693 1.10(13) 0 24911±120 1 Pyrolysis in a static system.

P = (71-286) torr.

(CH3

) 3CCX)C(CH3) 3

•+ (CH3

) 3CO + (CH3

) 3CO (a) - (CH3

) 2CO + (CH3

) 2CO + CH3 + CH3 (b) Peroxide, bis(l, 1-dimethylethyl)-

(tert-Butyl peroxide)

82 BAT/ROB k a

) EX 402-443 3.16(15) 0 18621+503 1 Thermolysis in a static system,

in presence of NO. Gas-chromatography

.

[tert-Butyl peroxide] = (0 . 72-1 . 20)xl0 33

_ O molec.cm . [NO] = (0.72-1.20)xl0 16 molec.cm' 3

.

(CH3

) 3CSSC (CH3

) 3

-» (CH3

) 2C=CH2 + HSSH + other products

Disulfide, bis(l, 1-dimethylethyl)-

76 MAR/BAR EX 603-673 3.98(14)

Thermolysis in a stirred-flow system.

76 MAR/BAR EX 519-573 3.98(13)

Thermolysis in a static system.

0 22132±481 1

0 21290±241 1

k err

.

factor

1.12

1.66

1.20

3.39

2.51

1.58

123
Table o£ Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A

type A,A/A(ref) B-B(ref) units

CH2 CHj ^ prot*ucts

1,3, 5-Cycloheptatriene, 7-ethyl79 AST/TRO EX 940-1350 1.38(13)

(Limiting high-pressure k, model A^) ES 900-1400 9.12(13)

(Extrapolated)

(Limiting high-pressure k, model A2

) ES 900-1400 3.89(13)

(Extrapolated)

Unimolecular isomerization behind incident

and reflected shock waves. M = Ar.

[Ar] = 1.81xl0 19 molec.cm 9

.

CHXHjCH,

6

-» products

Cyclohexane, propyl83 ZYC/BAC

Thermolysis in a flow-reactor. Gas-chromatography. P = 760 torr.

ch,c(o)och2ch2 6

-» CH-jCOOH + CH=CH2 6

EX 933-1073

Cyclopentaneethanol acetate - Acetic acid + Cyclopentane, ethenyl81 MAR/CHU EX 633-693 Pyrolysis in a static system.

P - (34-377) torr.

8 . 8 ( 12 )

1.58(13)

CH3C(0)0C(Ce3

) 2C(CH3 )3 - CH3COOH + CH2=C(CH3 )C(CH3

) 3

2-

Butanol, 2,3,3-trimethyl acetate

(1,1,2, 2-Tetramethylpropyl acetate

)

83 LOU/VER EX 538-582 1.66(14)

Pyrolysis in a microreactor, or in a Pyrex macroreactor . Gas-chromatography

CH3C (O)OCH (ch2ch3 )C cch3

) 3

-• CH3COOH + cis~CH3CH=CHC(CH3

) 3 (a)

-* CHgCOOH + trans-CH3CH=CHC(CH3

) 3 (b)

3-

Pentanol, 2,2-dimethyl-, acetate

72 CHU/MAR (k

a + kb

) EX 578-653 1.15(13)

Thermolysis in a static system.

P = (25-300) torr. k is P-independent

within the given range.

0 24141±601 1

0 25741 1

0 24947 1

0 28989±241 1

0 24947±385 1

0 19847 1

0 22572±393 1

k err

factor

1.58

1.82

1.23

124
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref), n B, k,A k err. type A,A/A(ref) B-B(ref) units factor

(CH3) 3C0C(0)0C(CH3 )3 -* (CH3

) 3COH + COz + (CH3

) 2C=€B2 Carbonic acid bis ( 1 , 1-dimethylethyl) ester

83 TAY2 EX 546-595 8.51(12)

EX 600 2 . 68( -1

)

Thermolysis in a stainless-steel reactor.

hc(ch3) 2 6 (+ M) -* products

1,3,5-Cycloheptatriene, 7- ( 1-methylethyl)

79 AST/TRO EX 960-1340 8.51(12)

(Limiting high-pressure k, model A->i

) ES 900-1400 2.19(14)

(Extrapolated)

(Limiting high-pressure k, model A2

) ES 900-1400 2.29(13)

(RExtr apolated

)

Unimolecular isomerization behind incident

and reflected shock waves in Ar.

[Ar] = 1.81x10^® molec.cm

- ^.

-» products

Naphthalene, decahydro-, (Decalin) (Unspecified form)

79 POP/PET EX 900-975 Thermolysis of Decalin/Dodecane mixtures in presence of H

20 vapor, in a static reactor. Mass-spectrometry. Gas-chromatography.

P( Hydrocarbons) “ 0.75 torr. CHjGHjCHjCHj

0

Cyclohexane, butyl83 ZYC/BAC

products

Thermolysis in a flow-reactor. Gas-chromatography

.

P “ 760 torr.

EX 923-1023

4.966(11)

7.4(12)

CHjCfbJOCHjCH

-» CH3COOH +

CH=CHa

Cyclohexaneethanol acetate

-* Acetic acid + Cyclohexane, ethenyl81 MAR/CHU EX 633-693 2.0(13)

Pyrolysis in a static system.

P “ (34-377) torr.

0 18653 1

1

0 23648±962 1 2.24

0 26402 1

0 24394 1

0 26162 1

0 28628±722 1

0 25031±409 1 1.91

125
4. Table of Chemical Kinetic Data for Combustion Chemistry -- Continued

Reaction, Reference Code, Notes Data T/K k,k/k(ref),

type A,A/A(ref)

CH3C

(

0 )OCBCH ( CB3

)

2c ( CH3 )

-» CBjCOOB + (CB3

) 2C=CBC(CB3) 3 + CB2=€(CB3 )CBC(CB3) 3 (+ other minor products)

3-Pentanol, 2 , 2 , 4-trimethyl- , acetate

72 CHU/MAR EX 578-653 Thermolysis in a static system.

P = (25-300) torr.

k is P-independent within the given range.

1.31(13)

CB3C(0 ) 0C(CB3 )[CB(CB3

) 2] 2 - CB3CQOB + (CH3

) 2C=C(CB3 )CB(CB3

) 2 3-Pentanol, 2 , 3 , 4-trimethyl acetate

( 1-Isopropyl-l , 2-dimethylpropyl acetate

)

83 LOU/VER EX 525-590 7.94(13)

Pyrolysis in a microreactor, or in

a Pyrex glass macroreactor. Gas-chromatography

CH2 (CH2)

4CH3 6 -» products

n B, k,A k err. B-B(ref) units factor

0 23452±116 1 1.20

0 19366 1

Cyclohexane, hexyl83 ZYC/BAC EX 923-1053 5.7(12)

Thermolysis in a flow-reactor. Gas-chromatography

P = 760 torr.

CB3 (CB2 ) ^qCB3

-» products

Dodecane

79 POP/PET

Thermolysis of Dodecane-Decalin mixtures in presence of H20 vapor, in a reactor with a 75 cm vessel. Mass-spectrometry . Gas-chromatography

P( Hydrocarbons) = 0.75 torr.

ch2 (ch2)

6ch3 6 -* products

EX 900-975 3.715(10)

0 28147±361 1

0 23167 1

Cyclohexane, octyl83 ZYC/BAC EX 923-1003 1.7(12) 0 26703±962 1 Thermolysis in a flow-reactor. Gas-chromatography. P = 760 torr.

126
5. References to the Table

71 BLA/DAV2

71 BLA/SPE

71 GAR/MCF

71 SLA/FIS

71 SPR/AKI

71 WAG/ZAB

71 YAT/RAM

72 BAL/AND

72 BAR/MIR

72 CHU/MAR

72 DAL/ZIO

72 EGG/COC

72 FLO/GIB

72 FRE/HOP

72 GAJ/SHI

72 HAS

73 BLU/WAG

73 COC/EGG2

Blake, P. G., and Davies, H. H., “Reaction of Keten. Part I. Kinetics of the Gas-phase Reaction

with Acetic Acid,” J. Chem. Soc. B, 1727 (1971). Blake, P. G., and Speis, A., “Kinetics of Thermal

Decomposition of Acetic Anhydride in Flow and

Static Systems,” J. Chem. Soc. B, 1877 (1971). Gardiner, W. C., McFarland, M., Morinaga, K., Takeyama, T., and Walker, B. F., “Initiation Rate

for Shock-Heated Hydrogen-Oxygen-Carbon

Monoxide-Argon Mixtures as Determined by OH

Induction Time Measurements,” J. Phys. Chem. 75, 1504 (1971). Slack, M. W., Fishbume, E. S., and Johnson, A. R., “Kinetics and Thermodynamics of the CN

Molecule. H. The Dissociation of CJ42,” J. Chem.

Phys. 54, 1652 (1971). Sprung, J. L., Akimoto, FL, and Pitts, J. N., Jr., “Nitrogen Dioxide Catalyzed Cis-Trans Isomerization of cis-2-Butene,” J. Amer. Chem. Soc. 93, 4358

(1971). Wagner, H. Gg., and Zabel, F., “Zum thermischen

Zerfall von Keten in der Gasphase,” Ber. Bunsenges. Phys. Chem. 71, 114 (1971). Yates, B. L., Ramirez, A., and Velasquez, O., “The

Thermal Decomposition of fl-Hydroxy Esters,” J. Org. Chem. 36, 3579 (1971). Baldwin, J. E., and Andrews, G. D., “The Thermal

Gas-Phase Partitioning of 1-Methyl- and 2-Methyibicyclo[2.1.0]pent-2-ene,” J. Am. Chem. Soc. 94, 1775 (1972). Barroeta, N., and Miralles, A., “Thermal Reactions

of Alkyl Isocyanates. I.,” J. Org. Chem. 37, 2255

(1972). Chuchani, G., Martin, G., Barroeta, N., and Maccoll, A., “Pyrolyses of Some Highly Branched Sec- ondary Acetates,” J. Chem. Soc., Perkin Trans. 2, 2239 (1972). Daly, N. J., and Ziolkowski, F., “Thermolyses of NN-Dimethylcarbamates and the Implications for Thermal ^-Elimination Reaction Mechanisms,” J. Chem. Soc., Chem. Commun. 911 (1972). Egger, K. W., and Cocks, A. T., “Kinetics of the Four-centre Elimination of Keten from Bicyclo[3.2.0]hept-2-en-6-one in the Gas Phase,” J. Chem. Soc., Perkin Trans. 2, 211 (1972). Flowers, M. C., and Gibbons, A. R., “Application

of the RRKM Theory of Unimolecular Reactions to the Thermal Reactions of Spiropentane,” J. Chem.

Soc., Perkin Trans. 2, 548 (1972). Frey, H. M., Hopkins, R. G., and Isaacs, N. S., “The

Thermal Unimolecular Decomposition of 2- Methoxy-3,4-dihydro-2H-pyran,” J. Chem. Soc., Perkin 2, 2082 (1972). Gajewski, J. J., and Shih, C. N., “Hydrocarbon

Thermal Degenerate Rearrangements. V. Stereo- chemistry of the 1,2-Dimethylenecyclobutane Self- Interconversion and Its Relation to the Allene

Dimerization and the Rearrangements of Other C6H8 Isomers,” J. Am. Chem. Soc. 94, 1675 (1972). Hasselmann, D., “Degenerierte Thermische Umlagerung von 5-Methylen-Bicyclo[2,2,l]Hepten-

(2),” Tetrahedron Letters No. 33, 3465 (1972). Blumenberg, B., and Wagner, H. Gg., “Die Reaktion von Methylamin mit Wasserstoffatomen,” Ber. Bunsenges. Phys. Chem. 77, 253 (1973). Cocks, A. T., and Egger, K. W., “The Gas-phase Thermal Reactions of l-Methylbicyclo[3.2.0]hept-2- en-7-one,” J. Chem. Soc. Perkin Trans. 2, 835

(1973).

73 FRE/HOP

73 HAS

73 KNE

73 ORC/THR

74 BLA/SPE

74 CAR/TAR2

74 CAS/DEW

74 ORC/THR

75 COL/FRE

75 FRE/MAR

75 LEV/PRI

75 LUU/GLA

75 RIC

75 SZI/MAR2

75 SZI/MAR3

76 ART/ LEE

76 BLA/CRA

76 GAY/GIL

Frey, H. M., and Hopf, H., “The Thermal Uni- molecular Decomposition of 2,2,4,4-Tetramethylcyclobutanone,” J. Chem. Soc. Perkin Trans 2, 2016

(1973). Hasselmann, D., “Entartete Umlagerung eines Bicyclischen Methylen-cyclobutans: 6-Methylen-Bicyclo[3.2.0]Hepten-(2) Mechanismus Seiner Isomerisierung zu 5-Methylen-Bicyclo[2.2.1]-Hepten-(2),” Tetrahedron Lett. 3739 (1973). Knecht, D. A., “Thermal Decomposition of Cyclopentene and Cyclopentene-dg in the Gas Phase,”

J. Amer. Chem. Soc. 95, 7933 (1973). Orchard, S. W., and Thrush, B. A., “Unimolecular

Isomerisation of Hexa-1, trans-3,5-triene and Symmetry-forbidden Pyrolysis of Cyclohexa-1,3-diene,”

J. Chem. Soc., Chem. Commun. 16 (1973). Blake, P. G., and Speis, A., “Reactions of Keten.

Part IV. Kinetics and Thermodynamics of the Gasphase Reaction: Thioacetic Acid + Keten -* Acetic Thioanhydride,” J. Chem. Soc. Perkin

Trans. 2, 1879 (1974). Carter, W. P. L., and Tardy, D. C., “Ring Opening

of Chemically Activated Cyclopentyl and Methylcyclobutyl Radicals,” J. Phys. Chem. 78, 1573

(1974). Case, R. S., Dewar, M. J. S., Kirschner, St., Petit, R., and Slegeir, W., “Possible Intervention of

Triplet States in Thermal Reactions of Hydrocarbons. A Study of the Rearrangements of Cyclobutadiene Dimers and Analogous Compounds,” J. Amer. Chem. Soc. 96, 7581 (1974). Orchard, S. W., and Thrush, B. A., “Photochemical

Studies of Unimolecular Processes. VI. The Uni- molecular Reactions of C^Ha Isomers and the Inter- pretation of their Photolyses,” Proc. R. Soc. Lond. A 337, 257 (1974); Supersedes 73 ORC/THR.

Collins, J. F., Frey, H. M., and Isaacs, N. S., “The

Thermal Decomposition of cis- and trans-2- Methoxy-4-methyl-3,4-dihydro-2H-pyran,” J. Chem. Soc. Perkin Trans. 2, 1 (1975). Frey, H. M., Martin, H.-D., and Hekman, M., “Thermolysis of syn- and anti-Dimers of Cyclobutadiene,’ J. Chem. Soc., Chem. Commun. 204 (1975). Levush, S. S., Prisyazhnyuk, Z. P., Shevchuk, U.

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76 GOL/LEI

76 HAC/PIL

76 MAR/BAR

76 PAT/ATK2

77 BAI/FRE

77 FLO

77 FRE/SMI

77 RED/BER

77 SAL/THR

77 TAB/FUE

78 CAM/HAN

78 CHU/RQT

78 FRE/POT

78 HAC/KAU

78 HIP/LUT

78 LEW/GIE

79 AST/TRO

79 DUD/GLA1

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79 DUD/GLA2

79 EDN/SPE

79 FRE/LOD

79 FRE/POT

79 KAL/SHV

79 POP/PET

79 RED/BER1

79 RED/BER2

79 TEM

79 TSU/NAK

80 BEN

80 CAN/CRI

80 CAR/MAI

80 FUR/PAC

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81 BAC/PAR

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128
81 CAN/CRI2

81 MAR/CHU

81 SAT/KAL

81 SKI/ROG

81 TAY

81 TIE/WAM

82 BAT/ROB

82 LEW/BOS

82 MCE/TAY

82 MOR/PIL

82 RIZ/CRI

82 TUL/MAC

83 ALA/KIE

83 AMA/YAM

83 ANA1

83 ANA2

83 ANA/BLA

83 ANA/WAD

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83 ARI/ART2

83 ART/ANA

83 ATK/ASC1

83 ATK/ASC2

83 ATK/ASC3

83 ATK/ASC4

83 ATK/ASC5

83 AYR/BAC

83 BAC

83 BAR/BEC

83 BAU/CRA

83 BER

83 BER/FLE

83 BER/LIN

83 BER/SKI

83 BLA/UA

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83 BLA/JUS

83 BLA/SHA

83 BRU/SCH1

83 BRU/SCH2

83 BUR/WAL

83 CHI/BIG

83 CHU/MAR

83 CQL/RIC

83 DAV

83 DOO/MAC

83 DUN/GUI

83 EBE/EDE

83 FAR/BEC

83 FON/MAE

83 FRE/WAT

83GON

83 GOE/SCH

83 GRE/ORC

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83 GUE/VAN

83 GUT/NEL

83 HAC/KUR

83 HAG/LOR

83 HAS/RIE

83 HAT/AKI

83 HER/CHU

83 HXP/LUT

83 HOM/WEL1

83 HOM/WEL2

83 HOR/BAU

83 HSU/SHA

83 JAS/FRI

83 JOH/MEC

83 KAN/PURI

83 KAN/PUR2

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130
83 KEY

83 KIE/KAP

83 KLA/ADA

83 KLO/DRO

83 KOD1

83 KOD2

83 KOD3

83 KYO/WAT

83 LAM/MOL

83 LAN/PET

83 LAU/YUN

83 LEE/TAN

83 LEV/PRI

83 LIC/BER

83 LIF/BEN

83 LOI/CAR

83 LOU/TIN

83 LOU/VER

Keyser, L. F., “Relative Rate Constants for the Reactions of Atomic Oxygen with HO? and OH Radicals,” J. Phys. Chem. 87, 837 (1983). Kiefer, J. H., Kapsalis, S. A., Al-Alami, M. Z., and Budach, K. A., “The Very High Temperature Pyrolysis of Ethylene and the Subsequent Reactions of Product Acetylene,” Combust. Flame 51, 79 (1983). Klamer, F.-G., and Adamsky, F., “Synthese und Umlagerung substituierter Bicyclo[2.1.0]pent-2-ene. Eine Thermische “walk” Umlagerung,” Chem. Ber.

116, 299 (1983). Klotz, H.-D., Drost, H., und Schulz, G., “Zum Einfluss der Stosswellenreflexion auf die Hochtemperaturpyrolyse von Kohlenwasserstoffen im

Stosswellenrohr,” Exper. Techn. Phys. 31, 125

(1983) (Ger). Kodama, S., “Reactions of NH Radicals. I. Photolysis of HN3 Vapor at 313 nm,” Bull. Chem. Soc. Jpn.

56, 2348 (1983). Kodama, S., “Reactions of NH Radicals. II. Photolysis of HN3 in the Presence of C2H6 at 313 nm,”

Bull. Chem. Soc. Jpn. 56, 2355 (1983). Kodama, S., “Reactions of NH Radicals. HI. Photolysis of HN3 in the Presence of C2H4 at 313 nm,”

Bull. Chem. Soc. Jpn. 56, 2363 (1983). Kyogoku, T., Watanabe, T., Tsunashima, S., and

Sato, S., “Arrhenius Parameters for the Reactions of Hydrogen and Deuterium Atoms with Four Butenes,” Bull. Chem. Soc. Jpn. 56, 19 (1983). Lamb, J. J., Molina, L. T., Smith, C. A., and

Molina, M. J., “Rate Constant of the OH + H2O2 -* HO? + H?0 Reaction,” J. Phys. Chem. 87, 4467 (1983). Langford, A. O., Petek, H., and Moore, C. B., “Collisional Removal of CH?(, Ai): Absolute Rate Constants for Atomic and Molecular Collisionai Partners at 298 K,” J. Chem. Phys. 78, 6650 (1983). Laufer, A. H., and Yung, Y. L., “Equivalence of Vinylidene and C?H?: Calculated Rate Constant for Vinylidene Abstraction from CH4,” J. Phys. Chem.

87, 181 (1983). Lee, J. H., and Tang, I. N., “Absolute Rate Constants for the Hydroxyl Radical Reactions with CH3SH and C2H5SH at Room Temperatures,” J. Chem. Phys. 78, 6646 (1983). Levush, S. S., Prisyazhnyuk, Z. P., and Kovalskaya, A. M., “Kinetics of the Thermal Gas Phase Decomposition of C1 -C4 Organic Peracids,” Kinet Catal.

24, 1098 (1983); tr. of KineL Katal. 24, 1294 (1983). Lichtin, D. A., Berman, M. R., and Lin, M. C., “Kinetic Studies of Initiated Reactions of CH and CN

Radicals,” Bull. Soc. Chim. Belg. 92, 656 (1983).

Lifshitz, A., and Ben-Hamou, H., “Thermal Reactions of Cyclic Ethers at High Temperatures. 1. Pyrolysis of Ethylene Oxide Behind Reflected Shocks,” J. Phys. Chem. 87, 1782 (1983). Loirat, H., Caralp, F., and Destriau, M., “Rate Constant and Activation Energy of the Exchange Reaction CO + N?0 — CO? + N? in the Temperature

Range 1060-1220 K. Application of the Thermal Explosion Theory to a System with Two Parallel Reactions,” J. Phys. Chem. 87, 2455 (1983). Louw, R., Tinkelenberg, A., and Werner, E. S. E., “Thermolytic Reactions of Esters. Part XHI. The

Effect of Electron Attracting a-substituents in Alkyl Acetates,” Reel. Trav. Chim. Pays-Bas 102, 519 (1983). Louw, R., Vermeeren, H. P. W., and Vogelzang,

M., “Thermolytic Reactions of Esters. Part 12. Steric versus Polar Effects on Pyrolytic p-Elimination of Acetic Acid fron (Tertiary) Alkyl Acetates,”

J. Chem. Soc. Perkin Trans. II, 1875 (1983).

83 MAC/JOU

83 MAC/PAC

83 MAC/PIL

83 MAC/POU

83 MAR/HER

83 MAR/PFO

83 MAR/ROP

83 MAR/SHA

83 NEL/HEL

83 NIK/MAK

83 QHT

83 PAR/GUT

83 PAR/SIN

83 PEN/CAN

83 PLU/SAN

83 PRA/WOO

83 RAV/THO

83 RAV/WIN

83 ROS

MacLeod, H., Jourdain, J. L., and Le Bras, G., “Absolute Rate Constant for the Reaction of OH with Thiophene between 293 and 473 K,” Chem. Phys.

Lett. 98, 381 (1983). MacKenzie, A. L., Pacey, P. D., and Wimalasena, J. H., “Induction Periods in the Formation of Ethane

fromn the Pyrolysis of Ethylene,” Can. J. Chem. 61, 2033 (1983). MacPherson, M. T., Pilling, M. J., and Smith, M. J. C., “The Pressure and Temperature Dependence of

the Rate Constant for Methyl Radical Recombination over the Temperature Range 296-577 K,”

Chem. Phys. Lett. 94, 430 (1983). MacLeod, H., Poulet, G., and Le Bras, G., “Etude

Cinetique des Reactions du Radical OH Avec

CH3SCH3, CH3SH et C?H5SH,” J. Chim. Phys.

Phys.-Chim. Biol. 80, 287 (1983). Martinez, R. I., and Herron, J. T., “Methyl Thiirane: Kinetic Gas-Phase Titration of Sulfur Atoms

in SrOy Systems,” Int. J. Chem. Kinet. 15, 1127

(1983). Martin, H.-D., PfOhler, P., Urbanek, T., and Walsh,

R., “Thermolyse von Ansaran, Ansaren und

Cuban,” Chem. Ber. 16, 1415 (1983). Martin, G., and Ropero, M., “Gas Phase Thermolysis of Acetonyl Allyl Sulfide,” React. Kinet. Catal.

Lett. 22, 171 (1983). Marshall, R. M., and Shahkar, G., “The Molecular Component in the Thermal Decomposition of Azomethane,” J. Chem. Soc. Faraday Trans. I 79, 1891 (1983). Nelson, H. FL, Helvajian, H., Pasternack, L., and McDonald, J. R., “Temperature Dependence of Cj(X1 2g +

) Reactions with Alkenes and Alkynes, 295-610 K,” Chem. Phys. 73, 431 (1983).

Niki, H., Maker, P. D., Savage, C. M., and Breiten- bach, L. P., “A Fourier Transform Infrared Study

of the Kinetics and Mechanism for the Reaction HO + CH3 OOH,” J. Phys. Chem. 87, 2190 (1983). Ohta, T., “Rate Constants for the Reactions of Diolefins with OH Radicals in the Gas Phase. Estimate

of the Rate Constants from Those for Monoolefins,”

J. Phys. Chem. 87, 1209 (1983). Park, J.-Y., and Gutman, D., “Reactions of Ethyl,

Cyclopentyl, and Cyanomethyl Radicals with Ni- trogen Dioxide,” J. Phys. Chem. 87, 1844 (1983). Paraskevopoulos, G., Singleton, D. L., and Irwin, R. S., “Rates of OH Radical Reactions. The Reaction OH + SO2 + N?t,” Chem. Phys. Lett. 100, 83

(1983). Penzhom, R.-D., and Canosa, C. E., “Second

Derivative UV Spectroscopy Study of the Thermal

and Photochemical Reaction of NO? with SO? and

SO?,” Ber. Bunsenges. Phys. Chem. 87, 648 (1983). Plum, C. N., Sanhueza, E., Atkinson, R., Carter, W.

P. L., and Pitts, J. N., Jr., “OH Radical Rate Constants and Photolysis Rates of a-Dicarbonyls,” Environ. Sci. Technol. 17, 479 (1983).

Pratt, G. L., and Wood, S. W., “Stoichiometry and

Rate of Reaction of Hydrogen Atoms with Oxygen,” J. Chem. Soc., Faraday Trans. I 79, 2597

(1983). Ravishankara, A. R., and Thompson, R. L., “Kinetic Study of the Reaction of OH with CO from

250 to 1040 K,” Chem. Phys. Lett. 99, 377 (1983). Ravishankara, A. R., Wine, P. H., and Nicovich, J. M., “Pulsed Laser Photolysis Study of the Reaction between 0(3P) and HO2,” J. Chem. Phys. 78, 6629

(1983). Roscoe, J. M., “The Reactions of 0(3P) with the Butanols,” Can. J. Chem. 62, 2716 (1983).

131
83 SCH

83 SCH/CLA

83 SCH/KOH

83 SCH/MEU

83 SEL/BAY

83 SMI

83 SRI/KAU

83 SWA/WAD

83 SZE/HAN1

83 SZE/HAN2

83 TAY1

83 TAY2

83 TAY3

83 TEM

Schwab, J. J., “Spectroscopy and Reaction Kinetics of Halogen-, Hydrogen-, and Oxygen-Containing Free Radicals,” Diss. Abstr. Int. 44, 1344-B (1983). Scherzer, K., Claus, P., and Dabbagh, M., “Kinetis- che Untersuchungen der Reaktionen von Methylradikalen mit Allen,” J. Prakt. Chem. 325, 680

(1983). Schieferstein, M., Kohse-HOinghaus, K., and Stuhl,

F., “Temperature Dependence of the Rate Constants of the Reaction O + NO + M -* NOj + M

(M = He, NO, Nfe CH4),” Ber. Bunsenges. Phys.

Chem. 87, 361 (1983). Schmidt, V. H., Meuser, R., Horie, O., Bauer, W.,

and Becker, K. H, “The Reaction of C20 Radicals with H Atoms,” Bull. Soc. Chim. Belg. 92, 655

(1983). Selzer, E. A., and Bayes, K. D., “Pressure Dependence of the Rate of Reaction of Methyl Radicals with O2,” J. Phys. Chem. 87, 392 (1983). Smith, R. H, “Rate Constant for the Gaseous Reaction between Hydroxyl and Propene,” J. Phys.

Chem. 87, 1596 (1983). Sridharan, U. C., and Kaufman, F., “Primary Products of the O + C2H4 Reaction,” Chem. Phys. Lett

102, 45 (1983). Sway, M. I., and Waddington, D. J., “Reactions of Oxygenated Radicals in the Gas Phase. Part 12. The

Reactions of Isopropylperoxyl Radicals and Alkenes,” J. Chem. Soc. Perkin Trans. II, 139 (1983). Szekely, A. Hanson, R. K., and Bowman, C. T., “High-Temperature Determination of the Rate Coefficient for the Reaction H2 + CN -* H + HCN,”

Int J. Chem. Kinet. 15, 915 (1983). Szekely, A., Hanson, R. K., and Bowman, C. T., “Shock-Tube Determination of the Rate Coefficient

for the Reaction CN + HCN — C2N2 + H,” Int J. Chem. Kinet 15, 1237 (1983). Taylor, R., “The Mechanism of Thermal Elimination. Part 14. Pyrolysis of Diacetamide, 2-Acetoxypyridine, Diacetyl Sulphide, and Thioacetic Acid: Possible Involvement of Enol Forms in Gasphase Eliminations,” J. Chem. Soc. Perkin Trans. II, 89 (1983). Taylor, R., “The Mechanism of Thermal Eliminations. Part 15. Abnormal Rate Spread in Pyrolysis of Alkyl Methyl Carbonates and S-Alkyl O-Methyl

Carbonates due to Enhanced Nucleophilicity of the Carbonyl Group,” J. Chem. Soc. Perkin Trans, n,

291 (1983). Taylor, R., “The Mechanism of Thermal Elimination. Part 17. Rate Data for Pyrolysis of Vinyl Acetate and 1,2-Diacetoxyethane,” J. Chem. Soc. Perkin Trans, n, 1157 (1983). Temps, F., “Study of Radical-Radical Reactions us- ing a FER-LMR Spectrometer,” Ber. -Max-PlanckInsL Stroemungsforsch., 140 pp. (1983) (Ger); Chem. Abstr. 100:127433g (1984).

83 THI/ROT

83 TRE

83 TUA/ATK

83 TUA/CAR1

83 TUA/CAR2

83 TUL

83 TUL/RAV

83 WAS/HAT

83 WHY/PHI!

83 WHY/PHX2

83 WHY/PHB

83 WIN/NIC

83 YAM/BAC

83 YAM/FUE

83 ZAL/HUN

83 ZYC/BAC

Thielen, K., and Roth, P., “Stosswellenunter- suchungen zum Start der Reaktion CO + 02 ,” Ber. Bunsenges. Phys. Chem. 87, 920 (1983). Trenwith, A. B., “Pyrolysis of Propionitrile and the Resonance Stabilisation Energy of the Cyanomethyl

Radical,” J. Chem. Soc. Far. Trans. I 79, 2755

(1983). Tuazon, E. C., Atkinson, R., Plum, C. N., Winer, A.

M., and Pitts, J. N., Jr., “The Reaction of Gas Phase N2Os with Water Vapor,” Geophys. Res. Lett. 10, 953 (1983). Tuazon, E. C., Carter, W. P. L., Atkinson, R., and

Pitts, J. N., Jr., “The Gas-Phase Reaction of Hydrazine and Ozone: A Nonphotolytic Source of OH

Radicals for Measurement of Relative OH Radical Rate Constants,” Int. J. Chem. Kinet. 15, 619 (1983). Tuazon, E. C., Carter, W. P. L., Brown, R. V., Winer, A. M., and Pitts, J. N., Jr., “Gas-Phase Reaction of 1,1-Dimethylhydrazine with Nitrogen Dioxide,” J. Phys. Chem. 87, 1600 (1983). Tully, F. P., “Laser Photolysis/ Laser-Induced

Fluorescence Study of the Reaction of Hydroxyl

Radical with Ethylene,” Chem. Phys. Lett. 96, 148

(1983). Tully, F. P., Ravishankara, A. R., and Carr, K., “Kinetic Study of the Reactions of the Hydroxyl

Radical with Ethane and Propane,” Int. J. Chem.

Kinet. 15, 1111 (1983). Washida, N., Hatakeyama, S., Takagi, H., Kyogoku,

T., and Sato, S., “Reaction of Ketenes with Atomic

Oxygen,” J. Chem. Phys. 78, 4533 (1983). Whyte, A. R., and Phillips, L. F., “Rate of Reaction

of CN(v = 0,l) with N Atoms,” Bull. Soc. Chim.

Belg. 92, 635 (1983); superseded by 83 WHY/PHI2.

Whyte, A. R., and Phillips, L. F., “Rate of Reaction

of N with CN(v = 0,lX” Chem. Phys. Lett. 98, 590 (1983). Whyte, A. R., and Phillips, L. F., “Rates of Reaction of NH2 with N, NO and N02,” Chem. Phys. Lett 102, 451 (1983). Wine, P. H., Nicovich, J. M., Thompson, R. J., and

Ravishankara, A. R., “Kinetics of 0(3Pj) Reactions with H2Q2 and O3,” J. Phys. Chem. 87, 3948 (1983). Yamamoto, S., and Back, R. A., “The Thermal and Photochemical Decompositions of Succinic Anhydride and 2,3-Dimethyl Succinic Anhydride in the Gas Phase,” Can. J. Chem. 61, 2790 (1983). Yamasaki, K., Fueno, T., and Kajimoto, O., “Studies on the Reaction N + N3 -» N2(B3 ng) + N2(X1Xg +

),” Chem. Phys. Lett. 94, 425 (1983).

Zalotai, L., Hunyadi-Zolthn, Zs., B6rces, T., and

MZLrta, F., “Kinetics of Gas Phase Decomposition of Oxetan and Oxetan-2,2-d2,” Int. J. Chem. Kinet. 15, 505 (1983). Zychlinski, W., Bach, G., Glauch, B., and Zirnmer- mann, G., “Kinetische Untersuchungen zur Pyrolyse von Mono-n-alkyl-cyclohexanen,” J. f. prakt. Chemie 315, 66 (1983).

132
6. Conversion Factors for Rate Constants

Equivalent second order rate constants

B A cm3 mol ' s

-1 dm3 mol -

' s

- ' m3 mol -1 s

- ' cm3 molecule -1 s

-1 (mm Hg) -1

s" 1 atm -1

s

_l ppm -1 min -1 m2 kN -

' s

-1

1 cm3 mol -1 s

-1 = 1 10 3 10 6 1.66X 10 ~ 24 1.604 x 10 -5 T ' 1.219 x io -2 p*

2.453 X 10 -9 1.203 X 10 -4 r->

1 dm3 mol -1 s

-1 = 103

1 10 3 1.66X 10 -2 ‘ 1.604 x 10 -2 p'12.19 P' 2.453 X 10 -o 1.203 x 10 - 'p>

1 m3 mol -

' s

' = 10“ 103

1 1.66X 10 - ' 8 16.04 P' 1.219 x 10“ p'

2.453 x 10 -3 120.3 7’ - '

1 cm3 molecule -1 s

-1 = 6.023 x 1023 6.023 x 1020 6.023 X 10' 7

1 9.658 x 10' 8 P*7.34x 102 ' T ' 1.478 x IO' 5 7.244 x 10' 9 p1

1 (mm Hg) -1 s

-1 = 6.236 x 10* T

62.36 T 6.236 x 10 -2 T1.035 X lO 'T

1 760 4.56x 10 -2 7.500

1 atm -1 s

- ' 82.06 T 8.206 x 10 -2 T

8.206 x 10 5 r1.362 x 10 -22 T1.316 x 10 -3

1 6 x 10 -5 9.869 x 10 -3

1 ppm -1 min -1 -

at 298 K, 1 atm

total pressure

4.077 X 10“4.077 x 105 407.7 6.76x 10 - ' 6 21.93 1.667 x 104

1 164.5

1 m2 kN -1 s

- ' = 8314 T 8.314 r 8.314 x io -3 r

1.38x io -2°r0.1333 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 -

' s

-1 to m3 mol -1 s-1 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 -2

s

- ' cm 8 molecule -2

s

- ' (mm Hg)" 2

9

- * atm 2

9

- 1 ppm 2 min -1 m4 kN -2

s

- '

1 cm 8 mol -2s -1 = 1 10 -9 IO - 12 2.76 X 10 -48 2.57 x 10

- '°P 2

1.48x 10 -4 P2

1.003 x 10

- ' 9

1.447 X 10-8 P2

1 dm 6 mol -2

s -1 = 108

1 10 -8 2.76 x 10 -42 2.57x 10 -4 P2 148 P2 1.003 X 10

- ' 3

1.447 x 10-2 P2

1 m6 mol -2

s

- ' = 10' 2 108

1 2.76X 10 -36 257 P2 1.48 x 10 8 P2 1.003 x 10 -7 1.447 x 104 P2

1 cm 6 molecule -2s - ' = 3.628 x 1047 3.628 x 104 ' 3.628 x 1035

1 9.328 x 1037 r

-2 5.388 x 1043 T

2 3.64x 1028 5.248 x 1039 P2

1 (mm Hg) -2

s -1 = 3.89x 10 9 P

3.89x 10 3 P

3.89x 10 -3 P1.07 x 10-38 P 1 5.776 x 105 3.46x 10 -5 56.25

1 atm 2 s

- ' = 6.733 x 10 3 P

6.733 x 10 -3 P

6.733 x 10 -9 P

1.86x 10 -44 P

1.73x IO -8

1 6X 10" 9.74x 10 -5

1 ppm -2 min -1 = at 298 K,

1 atm total pressure

9.97x 10' 8 9.97x 10' 2 9.97x 108 2.75x 10 -29 2.89x 104 1.667 x 10'°

1 1.623 x 10«

1 m 1 kN -2s

-

1

= 6.91x 10 7 P

69.1 P 6.91X 10 -5 P

1.904 x 10 -40 P

0.0178 1.027 x 10 4 6.16x 10 -7

1

See note to table for second order rate constants.

133
7. ERRATUM

to NSRDS-NBS 73, Part 1 Compilation of Chemical Kinetic Data for Combustion Chemistry.

Part 1. Non-Aromatic C, H, 0, N, and S Containing Compounds. (1971-1982)

Page No. Line No.

55 12 (from top) For entry 80 TOB/ULL, the reference reaction is:

k ref : 0 + CO -> C02. 94 10 (from top) Instead of: 0 + Cf^CHCF^CI^Ct^ products

it should be: 0 + cy-Cf^CHCf^CE^CI^ products

112 7 (from bottom) The first product of the reaction 0 + 1-Pentanethiol

is not OOH, but OH. 188 8 (from top) For entry 71 COW/KEI the data type is not RL, but RN. 192 18 (from top) Step (a) of the reaction is not H + (CH3 )2CHCHCH=CH2

but (CH 3

) 2CHCH=CH2

. 201 16 (from top) For the second entry 73 DAY/THO, the reference reaction is: k ref : OH + CO - H + C02

- 201 5 (from bottom) For entry 76 BRA/CAP the units are not 2, but 2/2. 203 12 (from top) Reaction OH + HD -* HDO + H is valid only for the last two entries under this heading, namely:

72 DIX with k = ( 9 . 6±0 . 5 ) ( 11 ) , and 73 DAY/THO with the same k. For the first two entries, 72 DIX with k/k re £ = 2.8±0.42, and

72 DIX, with k/k re £ = 2 . 4exp( 155/T ) , the reaction is: OH + H

2 - H20 + H. 242 1 (from bottom) The reference reaction is not OH + CH.JCH2CH2CH2 "* products, but

OH + CH2CH2CH2CH3 -* products.

252 14 (from bottom) For the first entry 74 GOR/VOL, the reference reaction is: k ref : OH + CO - H + C02

- 269 26 (from top) For entry 82 ATK/ASC2, the reference reaction is not OH + CH3 (CH2 )CH 3

, but OH + CH3 (CH2

) 4CH 3

. 269 19 (from top) For first entry 74 GOR/VOL, the reference reaction is: k ref : OH + CO - H + C02

. 276 20 (from top) The formula for 2 , 6-dimethyl-4-heptanone , incorrectly written, should be: (CH3

) 2CH2CHC(0)CHCH2 (CH 3

) 2

. 278 3 (from top) For the second entry 77 HAM/LII, the products of

the reference reaction are not H

202 + 02

, but D2O2 + 0

2

. 280 1 (from bottom) After this line, just before the page number,

the definition of footnote 2 should be indicated:

o

) k^. (All the entries marked with footnote 2 refer to step (b) of reaction HO2 + N (+ M) ).

134
Page No. Line No.

287

287

287

287

289

386

394

399

407

410

412

415

432

468

497

550

4 (from top)

5 (from bottom)

3 (from bottom)

2 (from bottom)

6 (from top)

9 (from bottom)

1 (from bottom)

8 (from top)

1 (from top)

3 (from bottom)

19 (from top)

14 (from top)

9 (from bottom)

1 (from top)

11 (from top)

7 (from bottom)

For entry 71 BAL/LAN, the reference reaction

is not CH3 CH3 + HCHO -* products, but H02 + HCHO -» H

202 + CHO. For first entry 71 BAL/LAN, the value of the rate ratio

is not 7.8(-2), but 8.8(-2), For the same entry, the reference reaction

is not HCHO + CH3CH2CH3-* products,

but H02 + HCHO - H

202 + CHO. For the second entry 71 BAL/LAN, the rate constant

is not k = 7.86(7), but k = 7.57(7). For entry 71 BAL/LAN, the reference reaction

is not HCHO + (CH3

) 3CH -* products, but H02 + HCHO - H

202 + CHO. The product of step (a) is not CH3CH2CH(CH3 )C(CH3

) 23 but CH 3CH2CH(CH

3 )C(CH3

) 2

. The first reactant of the reference reaction

is not CH3

, but CH30. The second product of the reaction CH3 0 + (CH3

) 3CH,

is not (CH3 )C, but (CH 3

) 3 C. The second product of the reaction CH3 0

2 + (CH3

) 2CH02 should be written (CH3

) 2CO. In the reaction of Mercaptomethyl + Thiirane, the reactants are not CH3 S + #172, but CH 3 + cy-CH2CH2

S. The first product of the reaction CN + C02 is not CNO, but NCO (Cyanato free radical).

The systematic name of NH2CO is not Amidogen, formyl-, but Methyl, aminooxo- (or Carbamyl).

The products of the reference reaction

are not CH3CH3CH3CH2CO, but CH3 CH3 + CH 3CH2CO. The product of step (a) is not CH2CH=CH3

, but CH3 CH=CH2

. The reactants of the reference reaction

are not (CH3

) 3 + H2 , but (CH3

) 3 C + H

2

. The first product of the reaction is the free radical

CH3C=CCH( • )CH3

.

135
NBS-114A (REV. 2-80) U.S. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instructions

)

1. PUBLICATION OR

REPORT NO.

NBS/NSRDS-73/2

2. Performing Organ. Report No. 3. Publication Date December 1987

4. TITLE AND SUBTITLE

Compilation of Chemical Kinetic Data for Combustion Chemistry. Part 2.

Non-Aromatic C, H, 0, N, and S Containing Compounds. (1983)

5. AUTHOR(S)

Francis Westley, John T. Herron, and R. J. Cvetanovid

6. PERFORMING ORGANIZATION (If joint or other than NBS. see instructions)

NATIONAL BUREAU OF STANDARDS

U.S. DEPARTMENT OF COMMERCE

GAITHERSBURG, MD 20899

7. Contract/Grant No.

8 . Type of Report & Period Covered

1983

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

Same as item 6.

10. SUPPLEMENTARY NOTES

Library of Congress Catalog Card Number: 87-20244

| | 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. If document includes a significant

bibliography or literature survey, mention it here)

Chemical kinetic data for reactions of importance in combustion chemistry are compiled. Experimental, theoretical, evaluated, or estimated rate constants are given for reactions of O, 03 , H, H2, OH, H02, H20, N, N3, NO, N02, N20, NH,

NH2, SH, H^, SO, S02, and the aliphatic, alicyclic, and heterocyclic saturated and

unsaturated Q to Ci5 hydrocarbons, alcohols, aldehydes, ketones, thiols, ethers,

peroxides, amines, amides, and their free radicals. The data were taken from the

literature published in 1983. Data omitted from Part 1 of this series, covering the

period 1971 to 1982, are also included. The data are reported as rate constants or in terms of the parameters A, n, and B of the extended Arrhenius expression k = A(T /298)" x exp(— B IT), where B = E /R. Data are given for 434 reactions.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolon s)

Arrhenius parameters; carbon; chemical kinetics; combustion; compilation; free radicals; gas phase;

hydrocarbons; hydrogen; nitrogen; oxygen; rate of reaction; sulfur.

13. AVAILABILITY

[xj Unlimited

| | For Official Distribution. Do Not Release to NTIS

[x~l Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.

20402.

Q3] Order prom National Technical Information Service (NTIS), Springfield, VA. 22161

14. NO. OF

PRINTED PAGES

142

15. Price

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TABLES

Third Edition

A Major Supplement from JOURNAL OF PHYSICAL AND CHEMICAL

REFERENCE DATA

Presenting Reliable Data Utilized by Chemists, Chemical Engineers, and Materials

Scientists from Around the World for Over 25 Years

JUST

PUBLISHED!

HERMOCHEMICAL

JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA is verv pleased

to publish the Third Edition of the JANAF THERMOCHEMICAL TABLES.

Since the first version appeared 25 years ago, the JANAF THERMOCHEMICAL

TABLES have been among the most widely used data tables in science and engineering.

You’ll find: • Reliable tables of thermodynamic properties of substances of wide interest • A highly professional approach with critical evaluations of the world’s thermochemical and spectroscopic literature • A concise and easy-to-use format

This Third Edition presents an extensive set of tables including thermodynamic properties of more than 1800 substances, expressed in SI units. The notation has been made consistent with

current international recommendations.

There is no other reference source of thermodynamic data that satisfies the needs of such a broad

base of users.

Order your 2-volume set of the JANAF THERMOCHEMICAL TABLES today! You’ll get over 1890 pages of valuable information that is crucial to your res earch—in two hardback volumes. SUBSCRIPTION INF ORMATION

The JANAF THERMOCHEMICAL TABLES, THIRD EDITION is a two- volume supplement of Journal of Physical and Chemical Reference Data.

1896 pages, 2 volumes, hardcover ISBN 0-88318-473-7 Supplement Number 1 to Volume 14, 1985

U.S. & Canada $ 130.00

All Other Countries $ 156.00

(Postage included.

)

All orders for supplements must be prepaid

Foreign payment must be made in U.S. currency by iniernational money order, UNESCO coupons, U.S. bank draft, or order through your subscription agency. For rates in Japan, contact Maru/en Co., Ltd. Please allow four to six weeks for your copy to be mailed.

For more information, write American Chemical Society, Marketing Communications Department, 1155 Sixteenth

Street, NW, Washington, DC 20036.

In a hurry? Call TOLL FREE 800- 424-6747 and charge your order!

Published bv the American Chemical Society and the Amencan Institute of Physics lor the National Bureau of Standards

. Government Printing Office: 1987 0-201-490 (60198)

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special publications appropriate to this grouping such as wall charts, pocket cards, and bibliographies.

Applied Mathematics Series—Mathematical tables, manuals, and studies of special interest to physicists,

engineers, chemists, biologists, mathematicians, computer programmers, and others engaged in scientific and

technical work.

National Standard Reference Data Series—Provides quantitative data on the physical and chemical properties

of materials, compiled from the world’s literature and critically evaluated. Developed under a worldwide pro- gram coordinated by NBS under the authority of the National Standard Data Act (Public Law 90-396).

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Order the above NBS publications from: Superintendent of Documents, Government Printing Office,

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information in the Federal Government regarding standards issued by NBS pursuant to the Federal Property

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