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UNITED STATES DEPARTMENT OF COMMERCE • Alexander B. Trowbridge, Secretary

NATIONAL BUREAU OF STANDARDS • A. V. Astin, Director

Tables of Bimolecular Gas Reactions

A. F. Trotman-Dickenson* and G. S. Milne*

*Prepared under contract at the Edward Davies Chemical Laboratory

Aberystwyth, Wales

NSRDS-NBS 9

National Standard Reference Data SeriesNational Bureau of Standards 9

(Category 6—Chemical Kinetics)

Issued October 27, 1967

For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C. 20402 - Price $2 (Buckram)
Library of Congress Catalog Card Number: 67-60026
Foreword

The National Standard Reference Data System is a government-wide effort to give to the

technical community of the United States optimum access to the quantitative data of physical

science, critically evaluated and compiled for convenience. This program was established in 1963

by the President’s Office of Science and Technology, acting upon the recommendation of the

Federal Council for Science and Technology. The National Bureau of Standards has been assigned

responsibility for administering the effort. The general objective of the System is to coordinate and

integrate existing data evaluation and compilation activities into a systematic, comprehensive

program, supplementing and expanding technical coverage when necessary, establishing and

maintaining standards for the output of the participating groups, and providing mechanisms for

the dissemination of the output as required.

The NSRDS is conducted as a decentralized operation of nation-wide scope with central coordination by NBS. It comprises a complex of data centers and other activities, carried on in government agencies, academic institutions, and nongovernmental laboratories. The independent operational status of existing critical data projects is maintained and encouraged. Data centers that are components of the NSRDS produce compilations of critically evaluated data, critical reviews of

the state of quantitative knowledge in specialized areas, and computations of useful functions

derived from standard reference data.

For operational purposes, NSRDS compilation activities are organized into seven categories

as listed below. The data publications of the NSRDS, which may consist of monographs, loose-leaf

sheets, computer tapes, or any other useful product, will be classified as belonging to one or another

of these categories. An additional “General” category of NSRDS publications will include reports on detailed classification schemes, lists of compilations considered to be Standard Reference

Data, status reports, and similar material. Thus, NSRDS publications will appear in the following

eight categories:

Category Title

12

3

4

5

6

7

8

General

Nuclear Properties

Atomic and Molecular Properties

Solid State Properties

Thermodynamic and Transport Properties

Chemical Kinetics

Colloid and Surface Properties

Mechanical Properties of Materials

Within the National Bureau of Standards publication program a new series has been established, called the National Standard Reference Data Series. The present report, which is in Category 6 of the above list, is Number 9 of the new series and is designated NSRDS-NBS 9.

A. V. Astin, Director.

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Contents

Page Foreword iii Preface 1 Notes on the tables 1 Tables

Atom reactions

Hydrogen atoms (H) 4

Fluorine atoms (F) 15

Chlorine atoms (Cl) 16

Bromine atoms (Br) 22

Iodine atoms (I) 25

Sulphur atoms (S) 27

Sodium atoms (Na) 28

Potassium atoms (K) 37

Radicals containing one carbon atom

Methyne (CH) 38

Methylene (CH2 ) 39

Methyl (CH3) 40

Difluoromethylene (CF2 ) 56

Trifluoromethyl (CF3) 57

Misc. halogenated methyls (CFH2 , CF2 C1, CC13) 62

Formyl (HCO) 64

Methoxy (CH.s O) 65

Methylthio (CH3 S) 67

Chloroformyl (C1CO) 68

Cyano (CN) 69

Radicals containing two carbon atoms

Ethynyl (C 2 H) 70

Ethyl (C 2 H5 ) 71

Perfluoroethyl (C 2 F5 ) 75

Misc. halogenated ethyls (C„H Cl, C„H Cl , C„H CL, C..HC1 , C„C1,, C„F.C1,

C2F,C12

, C2 F2 C1;j , C2 F4 Br, C2 H4 Br)

' ' 76

Carbonylcarbene (CCO) 78

Acetyl and trifluoroacetyl (CH.{ CO, CF3 CO) 79

Ethoxy (C2 H5 0) 80

Radicals containing three carbon atoms

Allyl (CH2 CHCH2

) 81

n-Propyl (CH3 CH2 CH2

) 82

iso-Propyl (CH^CHCH.j) 83

Perfluoropropyl (CF;j CF2 CF2

) 84

Misc. halogenated propyls (CC13 CH2 CH2

, ICH2 CH2 CH2

) 85

Isopropoxy ((CH;{ ) 2 CHO) 86

Radicals containing four carbon atoms

Butyls (CH3 CH2 CH2 CH2

, CH3CHCH2 CH3

, (CH3

)2CHCH2

, (CH3)3 C) 87

J-Butoxy ((CH3

)3 CO) 88

v
Miscellaneous carbon-containing radicals Page Peracid radicals (CH;{ CO.} , C2 H5 CO;J ) 89

Peroxy radicals ((CH:5 )

;} C02

, cyclo-C6 H9 02

, C6H5 C(CH.{ )2 02

) 90

Phenyl radicals (CeHsj 91

Tolyl (CH.{ C6H4

) 92

Inorganic radicals

Hydroxyl (OH) 93

Hydroperoxyl (H02

) 96

Imino (NH) 97

Amino (NH2

) 98

Difluoroamino (NF2

) 99

Nitrate (NO.{ ) 100

Thiyl(HS)... 101

Chloromonoxy (CIO) 102

Borine (BH.{ ) 103

Fluosulfates (F.

} SO, FSO;j ) 104

Radical — radical reactions

Radical disproportionation 105

Disproportionation/combination ratios 108

Molecule — molecule reactions

Reactions involving hydrogen and hydrogen halides 118

Reactions involving organic radicals 120

Reactions involving nitric oxide 122

Reactions involving nitrogen dioxide 124

Misc. bimolecular molecule — molecule reactions 126

Odds and ends

Termolecular reactions 127

Inversion (group transfer) reactions 128

vi
Tables of Bimolecular Gas Reactions

A. F. Trotman-Dickenson and G. S. Milne

This survey covers the kinetics of bimolecular and termolecular gas reactions that do not involve atoms or molecules in electronically excited states. Bimolecular reactions are here defined as reactions

in which two molecules are involved as reactants, that yield two or more molecules as products. Those

reactions in which two molecules combine to form one molecule are most usefully considered as the reverse of unimolecular reactions which will be dealt with in another survey. Reactions of oxygen and

nitrogen atoms have been omitted as they will also form the subject of another survey. The literature from 1954 to December 31, 1965 has been exhaustively searched and it is hoped that

for this period nothing has been omitted that should have been included. The survey of earlier work has been based on one of the writers’ books on “Gas Kinetics” which

covered the literature to 1954. Use of the book for over ten years has revealed few omissions and these have been included in these tables. Data for the period January to August 1966 has been included

where possible.

Key Words: Chemical kinetics, gas, bimolecular, reactions, tables, rate constants, activation energies, Arrhenius equation, data.

Preface

This survey covers the kinetics of bimolecular

and termolecular gas reactions that do not involve

atoms or molecules in electronically excited states. Bimolecular reactions are here defined as reactions

in which two molecules are involved as reactants,

that yield two or more molecules as products. Those

reactions in which two molecules combine to form

one molecule are most usefully considered as the reverse of unimolecular reactions which will be

dealt with in another survey. Reactions of oxygen

and nitrogen atoms have been omitted as they will

also form the subject of another survey.

The literature from 1954 to December 31, 1965

has been exhaustively searched and it is hoped that

for this period nothing has been omitted that should

have been included.

The survey of earlier work has been based on one

of the writers’ books on “Gas Kinetics” which

covered the literature to 1954. Use of the book for over ten years has revealed few omissions and these

have been included in these tables. Data for the

period Janaury to August 1966 has been included

where possible.

Originally it was hoped to make this survey a

critical study from which reliable data could be

distilled. As the work proceeded it became evident

that this was not a realistic goal. Only a small

fraction of the reactions has been the subject of

investigation by several workers. When several

studies have been made the results fall into two

classes. In the first class are those reactions that

have been repeatedly investigated. It is then usually

found that the discrepancies are greater than the

random errors and that some systematic differences

exist. It is not possible to decide which value is most

nearly correct. In the second class are those reactions that have been investigated under widely

different conditions. In these cases the best result

for one purpose may not be the best for another, so

that no useful choice can be made. We therefore

decided to make the tables as comprehensive as possible so that users can readily discover what

information is available.

It is likely that some reactions have been omitted

and that other errors have crept in. We shall be

grateful if readers will write to tell us of suggested

improvements. It is hoped to publish supplements

to these tables every two or three years.

Notes on the Tables

All the rate data is in the simple Arrhenius form

A

- = Ae~ ElRT. “A ” factors and rate constants are in cm. mole. sec. units throughout. Activation energies

are in kcal/mole and temperatures in degrees centigrade.

Where data has been represented by equations

of the type

k = BTne~ H!RT (n=l,|,:i),

B and H have been converted to the simple form

by means of the equations

A = e

nBTn and E — H + nRT,

where T is the absolute temperature at the midpoint of the experimental range.

1
Where the rate equation is reported as a more

complex function of temperature, it has been quoted

as such in the tables.

Most of the data is for simple radical/molecule

metathetical reactions of the type

R i + R2X = R iX + R2

where R i is an atom or radical attacking a molecule

R2X. X is the atom transfered in the reaction.

For each radical R i there is a separate table

(see contents). The first column of each table consists of a list of molecules R 2X with which R i reacts. Columns three to five contain the Arrhenius

values and the experimental temperature ranges.

Column six gives an indication of the nature of the

experimental method used to obtain the data.

The following abbreviations have been used in

describing the radical source: P photolysis.

F.P. flash photolysis

T thermal reaction

S.T. shock tube

D.F. diffusion flame

M.D.F. modified diffusion flame

M.L. mean life method

Dil. F. dilute flame

M.B. molecular beam

+ H Hg photosensitized addition of H atoms to olefines. — H Hg photosensitized removal of H atoms

from saturated compounds.

+ CH3 CH3 radical attack on the parent compound.

The other radical source abbreviations used, such

as H2 /discharge and H2/O2 flame, are self ex- planatory.

The table for each attacking species R 1 is split

into six sections defined by the atom X being

transferred. In the order used in the tables these

are: (i) hydrogen atom transfer

(ii) fluorine atom transfer

(iii) chlorine atom transfer

(iv) bromine atom transfer

(v) iodine atom transfer

(vi) oxygen atom transfer

Only in the case of methyl radicals are all six

categories used.

In the few cases not covered by this classification

e.g., transfer of an atom from the radical to the

molecule as in

H02 + C0 = C02 + 0H,

either the reaction is written in full, or the products

of the reaction are indicated in a footnote.

A seventh category of reactions not already

covered (e.g., group transfer and inversion reactions)

is included at the end of each table.

Simple ratios of rate constants (of the form ki/k2 ) are presented in separate tables, these proved much

more difficult to classify, and wherever necessary,

explanations of the construction of these tables are included at the head of the table.

Rate data is available in the literature as complex

functions of several rate constants: this data has

not been included, but references as to where it is available are given at the appropriate sections in

the tables.

Where data is considered to be doubtful this is indicated in a footnote. As far as possible, an

attempt has been made to include criticism of data

by cross reference. Thus, where several references

are given for one set of Arrhenius values, the first reference contains the values themselves; the other

references indicate the sources of supplementary

data and/or comment on the values shown.

Where a sufficient quantity of data has been

collected for any one reaction, recommended

Arrhenius values are given. They are compatible

in all cases with the values for the reverse reaction

(where these are known).

List of Tables

1.

Atom Reactions

1. Hydrogen atoms H..

2. Fluorine atoms F..

3. Chlorine atoms Cl.

4. Bromine atoms Br.

5. Iodine atoms I... 6. Sulphur atoms S..

7. Sodium atoms Na

8. Potassium atoms K..

2.

Radicals Containing One Carbon Atom

1. Methyne CH.

2. Methylene CH2 3. Methyl CH;1 4. Difluoromethylene CF2 .

Page4

15

16 22

25

27

28

37

38

39

40

56

2
List of Tables — Continued

2.

Radicals Containing One Carbon Atom — Continued

5. Trifluoromethyl CF3 6 . Misc. halogenated methyls CFH2

, CF2 C1, CClr

7. Formyl HCO

8. Methoxy CH.,0

9. Methylthio CR,S

10. Chloroformyl C1CO

11. Cyano CN

Page 5762

64

65

67

68

69

3.

Radicals Containing Two Carbon Atoms

1. Ethynyl

2. Ethyl

3. Perfluoroethyl

4. Misc. halogenated ethyls.

5. Carbonylcarbene

6 . Acetyl and trifluoroacetyl

7. Ethoxy

C2 H 70 C,H5 71 C2F5 75 C2 H4 C1, C2H:i Cl2

, C2 H2 Cl:i , c2 hci4

, c2 ci5

, c2 f4 ci, c2 f.

( ci2

. CCO 78 CH.jCO, CF.CO 79

( 7,11,0 80

4.

Radicals Containing Three Carbon Atoms

1

.

Allyl 2 ., n-propyl

3. iso-propyl

4. Perfluoropropyl

5. Misc. halogenated propyls 6. Isopropoxy

CH2 CHCH2 CH.CH.CH,

CHjCHCH.j

CF3 CF2 CF2 cci.) ch2 ch2

, ich2 ch2 ch2 (CH.t ) 2 CHO

8182

8384

8586

5.

Radicals Containing Four Carbon Atoms

1. Butyls CHCHXFECH.,, CFLCHCFLCH.., (CILLCHCIL, (CRLC... 87

2 . t-Butoxy (CH:| )

;I C0. 88

6.

Miscellaneous Carbon-Containing Radicals

1 . Peracid radicals CH.{ CO.t , C^-CO,

2. Peroxy radicals (CH:i )

:! C02

, cyclo-C( .H,

J 02

, C6H5 C(CH:) ) 2 02 3. Phenyl radicals Cfi H5 4. Tolyl CH:! CbH4

8990

9192

7. Inorganic Radicals

1. Hydroxyl

2. Hydroperoxyl...

3. Imino

4. Amino

5. Difluoroamino

6 . Nitrate

7. Thiyl 8. Chloromonoxy

9. Borine

10. Fluorosulfates

OH

HO.,

NR

NH2 nf2 NO.,

HS.

CIO

BH., F.,SO, FSO.,

8. Radical-Radical Reactions

1. Radical disproportionation

2. Disproportionation/combination ratios

9. Molecule-Molecule Reactions

1. Reactions involving hydrogen and hydrogen halides

2. Reactions involving organic radicals

3. Reactions involving nitric oxide

4. Reactions involving nitrogen dioxide

5. Miscellaneous bimolecular molecule-molecule reactions

93

96

9798

99

100

101 102

103

104

105

108

118

120

122 124

126

10. Odds and Ends

1 . Termolecular reactions

2. Inversion (group transfer) reactions

3

127 128
Reaction of Hydrogen Atoms

Index

(a) Hydrogen atom transfer Page Reaction with

1. Hydrogen , 5

2. Alkaries 5

3. Cyclo-alkanes 6

4. Aromatic hydrocarbons 6

5. Aldehydes and ketones 6

6. Metal alkyl 7

7. Halogenated alkanes 7

8. Hydrogen halides 8

9. Hydrides of oxygen and nitrogen 8

(b) Fluorine atom transfer.... 8

(c) Chlorine atom transfer 8

(d) Bromine atom transfer 9

(e) Iodine atom transfer 9

(f) Oxygen atom transfer 9

(g) Ratios of rate constants

1. Reactions of the type (1) H+RH=H2 +R (2) H+01=01H

where RH is any hydrogen containing compound and 01 is an

olefine 10

2. Reactions with hydrocarbons and hydrocarbon derivatives 11

3. Reactions of the type (1) H + HA = H-2 +A (2) H+A-2 = HA + A

where A is a halogen atom 12

4. Miscellaneous ratios 12

4
Metathetical Reactions of Hydrogen Atoms With Hydrogen

Reactions Notes E logio A Temperature range

Radical source Reference

(kcal mole -1

) (cm 3 mole~ 1 sec~ ‘) °C h + h2 (a) 6.68 13.78 1 (b) 7.5 ±1 13.7 10-730 2

(d) (c) 8.0 ±0.5 14.05 10-730 8

logio k = 15.45 — 3.49 > 10 3/T + 3.84 x 10 S/T2 27-171 H2/tungsten spiral 11

(e) (f) A- = 1.18 X \0' 5 T~ 1/2T sxp (-9.21 x 10 3/RT) 27-171 H2/tunsgten spiral 12

H + HD (a) 6.96 13.12 1

H + HD (a) 7.04 13.06 1

h + d2 (a) 7.48 13.32 1 7.30 ±0.1 12.64 ±0.05 95-195 H2 /tungsten spiral 13 d+h2 (a) 6.14 13.37 1

(0 A: = 3 . 63 X 10 15T~ ll2T 3xp (— 9.4 J X \03/RT) 1-195 D2 /tungsten spiral 12

D + HD (a) 6.40 12.99 1

D + HD (a) 6.48 12.93 1

D + D, (a) 6.09 13.49 1

Notes

(a) A self-consistent set of values derived from absolute rate calculations.

(b) Review of literature data (refs. 3 to 6). (c) Review of literature data (refs. 3 to 7). (d) For a critical summary of the (then) available experimental

data, see refs. 9 and 10.

(e) Recalculation of the data from ref. 11.

(f) T is the tunneling factor.

References

1.

Polanyi, J. Chem. Phys. 23, 1505 (1955).

2. Trotman-Dickenson, “Gas Kinetics,” p. 169 et seq. (Butter- worths, London, 1955).

3. Farkas and Farkas, Proc. Roy. Soc. 152A, 124 (1935).

4. Geib and Harteck, Z. Phys. Chem. Bodenstein Festband

849 (1931).

5. Melville and Robb, Proc. Roy. Soc. 196A, 445 (1949).

6. Van Meersche, Bull. Soc. Chim. Belg. 60, 99 (1951).

7. Boata, Careri, Cimino, Molinari, and Volpi, J. Chem. Phys.

24, 783 (1956).

8. Weston, J. Chem. Phys. 31, 892 (1959).

9. Shavitt, J. Chem. Phys. 31, 1359 (1959).

10. Rapp and Weston, J. Chem. Phys. 36, 2807 (1962).

11. Schulz and Le Roy, J. Chem. Phys. 42, 3869 (1965).

12. Ridley, Schulz, and Le Roy, J. Chem. Phys. 44, 3344 (1966).

13. Schulz and Le Roy, Can. J. Chem. 42, 2480 (1964).

Metathetical Reactions of Hydrogen Atoms

Reactants Notes E logio A Temperature range

Radical source Reference

( kcal mole ~ l ) (cm 3 mole~ l sec

-1

) °C

HYDROGEN ATOM TRANSFER

Alkanes

ch4 (a) 7.0 ±1.5

6.6

4.5 ±1.2

10.5 10.01 ±0.2

130-290

99-163

99-163

H., /tungsten filament H„/tungsten filament

12

3

5
Metathetical Reactions of Hydrogen Atoms — Continued

Reactants Notes E logic A Temperature rangeRadical source Reference

(kcal mole ~ l ) (cm 3 mole ~ 1 sec

-

1

) °C

(a) 9.0 12.5 130-420 4

(a) 8.0 12.6 477-547 5

11.5 14.3 950-1530 CH4 /0„ flame 6

15.1 14.53 400-480 H.,/0,, ignition l (b) 11.05 14.19 8

/ =2.9 X 10 10 610 H.,/0., ignition 9

7.4 ±1.1 11.8 212-530 H.,/discbarge 10

8.0 13.9 697-863 H.,0„ ignition 11 (w) (q) 13.5 450 D.,/discharge 12

(w) (c) 7.8 13.0 347-465 D.,CO photolysis 13

(r) 9.6 12.6

c2 h2 (d) 1.5 14

C2 H_| (e) 6.6 ± 1 13.26 500-625 H.,/0., ignition 15 C2 Hk 6.8 12.53 80-163 H.,/tungsten filament 16

12.0 13.17 410-550 H.,0., ignition 17

(e) 14 ±1 14.76 500-625 H.,/0., ignition 15

(q) 9.0 ±0.2 24 ±2 H., /discharge 18

12.2 14.52 410-550 H.,/0., ignition 7 (0 9.9 ±1.0 14.20 ±0.4 25-1230 19

9.7 ±2 14.1 720-1160 C.,H ( ./ H.,/0., flame 105

<g) /. =3.0X 109 630 20

(h) 9.0 13.5 50-250 C.,Hk/C.1 H(

. radiolysis 21

(0 9.71 ±0.58 14.12 ±0.25 31-1227 22

6.20 13.6 752-917 H,/0., ignition 11 (w) (i) 9.0 14.4 30-306 D,S/C.,Hk photolysis 23

C ,H (

. (e) 1.1 ± 1 12.45 500-625 H,/0., ignition 15

(w) (i) 5.0 13.7 - 25-205 D.,S + C H(

. photoly- 23

C.H. 8.5 13.43 410-550

SIS

H.,/0., ignition 17

(e) 8.3 ±1 13.56 500-625 H.,/0., ignition 15

8.8 13.80 410-550 H.,/0., ignition 7

(h> 7.4 13.7 57-217 C Hk radiolysis 24

8.2 14.12 95-170 H., /tungsten filament 25

(j) /. = 4.53 x 10 11 520 H.,/0

2 ignition 26

(f) 7.83 ±0.79 13.81 ±0.37 28-520 26

(w) (q) 8.0 Room temp. H„/discharge 27

(w) (i) 7.2 14.5 30-250 D„S + C ,H S photolysis 23

CH:1 CH;CHCH:1 (w) (i) 5.0 14.1 28-230 D.,S + C4 HS photolysis 23

re-C4 H10 <q) 8.9 Room temp. H.,/discharge 27

(j) /, =5.1 x 10" 520 H.,/0., ignition 28

(0 7.5 ±0.5 13.9 ±0.2 27-520 28

(b) 6.7 13.3 50-250 n — C,H |(1 radiolysis 21

(k) 7.1 13.82 70-170 H., /tungsten filament 29

(w) (q) 7.9 Room temp. H., /discharge 27

(w) (i) 7.1 14.5 30-250 d.,s + c4 h 10 23

photolysis

<q) 9.3 H.,/discharge 30

6.0 13.47 410-550 H.,/0., ignition 17

(e) 5.6 ±1 12.89 500-625 H.,/0., ignition 15

5.1 12.76 410-510 H.,/0., ignition 7

(111 5.1 13.1 50-250 /-C4 H |(| radiolysis 21

<J) /, =9.2 x 10 11 520 H„/02 ignition 28

6
Metalhetical Reactions of Hydrogen Atoms — Continued

Reactants Notes E logio A Temperature range

Radical source Reference

(kcal mole 1

) (cm 3 mole ~ 1 sec

~

*) °C

(0 6.8 ±0.5 14.0 ±0.2 27-520 28

(w) (i) 6.3 14.5 30-350 D2 S + C4 H]0 23

photolysis

,?-C- h]2 (q) 8.5 Room temp. H.,/discharge 27

(w) (q) 7.8 Room temp. D„/discharge 27

neo-C.H r> (q) 9.2 Room temp. H2/discharge 31

n' C6 HM (q) 9.1 Room temp. H../discharge 27

(0 5.9 25-305 32

(w) (q) 8.0 Room temp. D., /discharge 27

Cyclo Alkanes

cyclo-C.jH,. (q) 9.5 Room temp. H., /discharge 27

(w) (q) 9.3 Room temp. D2/discharge 27

cyclo-C4 HK (q) 8.2 Room temp. H2 /diseharge 27

(w) (q) 7.7 Room temp. D2 /discharge 27

cyclo-C6 Hio (q) 7.5 Room temp. H2 /discharge 27

(w) (q) 6.6 Room temp. D2 /discharge 27

cyclo-C6H12 (q) 8.0 Room temp. H2/discharge 27

(w) (q) 7.2 Room temp. D2/discharge 27

Aromatic hydrocarbons

C H (q) < 7 Room temp. H2 /discharge 27

^6 6 (w) (q) < 6 Room temp. D.,/discharge 27

Aldehydes and ketones

HCHO ( 1 ) 2.6 13.21 252-397 H2 CO/D2 photolysis 33

(f) 3.49 13.46 327-727 34

(f) 3.26 113.29 250-400 34

A- = (2.7 ±0.7) x 10 10 27 H„/discharge 35

A = 3-5 X 10 12 547 HCHO pyrolysis 36

(w) ( 1) 2.7 13.21 252-397 H..CO/D., photolysis 33 DCDO (1) 3.6 13.21 252-397 H.CO/D.CO 33

photolysis

w) (m) 3.0 13.3 308-341 D.,CO photolysis 13

(w) (1) 3.6 13.21 252-397 h2 co/d..co 33

photolysis

ch:! cho (q) =£6 25 H./discharge 37

CH3 COCH3 (q) 8.8 Room temp. H2/discharge 38

(w) (q) 8.0 Room temp. D„/discharge 38

Metal alkyl

CH,HgCH3 (q) =£ 6

25 H„/ discharge 106

Halogenated methane

CF.jH (a) 5.0 12.7 | 832-1011 1

1

../ 0., ignition 11

7
Metathetical Reactions of Hydrogen Atoms — Continued

Reactants Notes E logio A Temperature range

Radical source Reference

(kca! mole- 1 ) (cm 3 mole- 1 sec

-1

) °c

Hydrogen halides

H F (n) 35.0 13.00 3527-5027 HF shock wave 39

decomposition

H Cl 5.2 13.4 628-798 H,/HC1 thermal 40

reaction

(a) 4.5 41 H Br 2.2 13.79 832-1011 H2 /02 ignition 11 0.9 13.1 548-711 H.,/HBr thermal 42

reaction

(o) 3.7 14.04 700-1400 43

(r) 2.9 13.8

HI 0.7 ±0.25 13.70 ±0.07 394-527 H,/I2 thermal 44

reaction

1.17 ±0.35 13.8 ±0.2 394-465 H,/I2 thermal 107

reaction Hydrides of oxygen

and nitrogen

h2 o k = 6.6±0.9x 10 9 799 H2 /02/N2 0flame 45

(a) 20.4 13.96 37-642 108

(a) 21.6 14.84 687-807 H2 /02 ignition 46

(0 21.1 ±1.5 14.48 ±1.0 27-1727 47

D,0 <a) 25.5 15 1012-1227 109

A- = 5.0 X 109 799 H2/02 flame 48

A = 3.6 X 109 799 H2 /0„ flame 49

(p) (f) 21.8 13.93 799 H2/02 flame 45

h2 o2 (a) 18.8 16.39 687-807 H2 02 ignition 46

n2h4 2.0 11.54 25-150 H,/ discharge 50

FLUORINE ATOM TRANSFER

30 ±5 15.3 1030-1670 H2 /02 and C2 H2 /02 51 flames

CHLORINE ATOM TRANSFER

0.9 ±1.3 22-152 HC1/D2 and DC1/H., 52

photolysis

>2.1 25-75 H2/Cl2 /02 photolysis 53

>2.9 54 > 1.8 25-100 H„/Cl2/02 photolysis 55 > 1.6 0-85 H.,/Cl

2 /0, photolysis 56

<2.5 57

(s) ~ 5 2034 Molecular beam 58

8
Metathetical Reactions of Hydrogen Atoms — Continued

Reactants Notes E logio A Temperature range

Radical source Reference

{heal mole -1

) (cm 3 mole

1 sec

-1

) °C

BROMINE ATOM TRANSFER

Br2 3.7 14.97 700-1400 43 CF:i Br 17.45 15.64 832-1011 H.,/0., ignition 11

02 F4 Br2 14.5 16.0 855-1013 H,/02 ignition 11

IODINE ATOM TRANSFER

I

2 0.0 ±0.5 14.6 ±0.2 394-465 H2/I

2 thermal

reaction

107

OXYGEN ATOM TRANSFER

02 7 =5.0 X 109 485 H.,/0., ignition 60

A =6.7x 109 520 H2/02 ignition 60

A- = 2.7 X 109 520 H.,/02 ignition 61

A = 6.6 x 10* 520 H.,/0., ignition 62

15.1 13.75 H2 /02 ignition 63 k= 1.43 X 10 12 1380 H2 /02 ignition 64

20.0 ±2.0 14.9 1012-1227 H2 /0„ flame 109

A = 1.5 x 10 11 827 H.,/0„ flame 110

(t) 14.9 13.72 H.,/0., ignition 65

15.9 ±0.8 13.89 570-660 H2 /CO/0„ ignition 66

A- = 6.0 X 109 540 H.,/02 ignition 34

15.0 ±0.6 13.59 590-660 C.,HJCO/0., ignition 111

16.3 552-1089 H2 /02 ignition 67

17.4 ±0.7 14.82 ±0.2 1853-2772 H2 /0„ flame 68

(a) A = 1 .83 X 103 20 69

(a) A = 3.28 X 103 37 70

(0 17.8 ±1.0 15.08 ±0.8 27-327 70

(f) 16.9 ±1.0 14.86 ±0.8 1227-1427 70

18.9 ±0.9 620-1080 H.,/0., ignition 71

15.6 ±0.6 13.66 570-660 H2/C0/0„ ignition 72

(0 16.49 ±0.70 14.31 ±0.28 20-1377 73

17.0 13.69 999-1923 C2 H2 /02 oxidation 74

17.75 15.0 687-807 H.,/02 ignition 46

A = 1.6 x 10>° 642 H.,/0., flame 108

(0 16.50 14.34 20-1400 112

o. A =(2.4 ±0.3) x 10 12 Room temp. Diffusion flame 75

A =(1.6 ±0.3) X 10 12 Room temp. H2 discharge 76 HA (u) A =(1.9 — 3.0) x 10" 447 H2 0„ ignition 77

(u) A- = 1.1 x 10 2 500 H2 /0., slow reaction 78 n2 o 16.3 ±2.0 14.62 990-1510 H2 /N.,0/0„ flame 110

A- = 4.3 X 10'° 627 H.,/N.,0/0„ flame 108

A =2.9 X 10 n 1084 H2 /N„0/0„ flame 108

A = (4.3 ± 1.5) x 10 10 627 H2/N.,0/0„ flame 45

(f) 13 ±1.5 13.7 ±0.4 150-1487 45

9
Metathetical Reactions of Hydrogen Atoms — Continued

Reactants Notes E logio A Temperature range

Radical source Reference

{kcal mole -1

) (cm 3 mole -1 sec -1

) °C

no2 A = 3.2 > 10 13 221-261 H2/C12 N0, thermal 79

1 reaction

k = 2.9 X 1013 25 H2/ discharge 80

A = (2.9 ±0.3) X 1013 Room temp. H2

/ discharge 76

(v) A = 5.5 X 1013 360 H2 /02 ignition 81

CO., 33.3 15.48 944-1072 H2 /02 flame 113

(b) 29.7 14.89 1000-1500 8

A = 8.4 X 108

1

799 H.,/02 flame 49

Ratios of Rate Constants (Hydrogen Atoms)

(i) Reactions of t he type (1) H + RH = H2 + R where RH is any hydrogen containing compound.

(2). H + OL = OLH where OL is an olefine.

RH OL Notes A'l/A'2 E\—E% logio A i/A 2 Temperature rangeRadical source Reference

( kcal mole-1

) °C

ch4 c2 h4 2.6 x 10~ 6 120 CH4 -H 82

c2 h4 c2 h4 — 1.0 x 10 -3 24 n-C 4 H 10 -H 83

(i.e. = 0) C2 Hk c2 h 2.5 X 10”5 25 C.^Hj. radiol> sis 84

c,hh c,h6 4.5 x 10^ 2 24 n-C4 Hio -H 83

(4.10 ±0.37) X 10-2 25 C 4 H«

-H 85

c:i dh c,dh (6.3 ± 2.3) X 10~2 25 n-C4 H I0 -H 85

C,HS c2 h4 1.9 X 10“3 25 C:( Hh -H 86

1.5 x 10~3 24 c:i hk -h 87

C:( HS c,hb 5.2 x 10-4 25 C ,H n radioly sis 88

1,3-C4 Hk 1,3-C4H6 3.2 x 10“ 2 24 /i-C

4 H, 0 -H 83

1-C 4 Hs i-c4 h8 8.1 x 10“ 2 24 n-C 4 H 10 -H 83

i-C4H„ cc4 hh 2.0 x 10“ 2 24 ;i-C

4 H 10 -H 83

cisC4 Hs -2 cisC 4 H8 -2 6.6 X 10^ 2 24 n-C4 H, 0 -H 83

transC4 HH-2 transC4 Hs-2 11. 7x 10~ 2 24 n-C4 H I0 H 83

n-C4 Hio C:1 Hh 1.4 x 10-3 25 n-C4 H in -H 85

n-C4 H,0 CA 1.3 x 10 -3 25 n-C4 H 10 -H 85

/-C4 H10 c2 h4 8.6 X 10-3 25 (-c4 h 10 H | 86

8.1 X 10- 3 24 LC4 H i0 H 1 87

10
Ratios of Rate Constants Hydrogen Atoms) — Continued

RH OL Notes kilk-t Ei-Et log io A il

A

2 Temperature range

Radical source Reference

ikcal mole~ ') °C

cyclo-Cs H10 cyclo-C^H^ 5.7 x 10- 3 24 cyclo-C.H I0 -H 89

n-C,H 12 C2 H4 3.7 X lO-3 25 n- C.H]2 -H 86

2.2 X lO^3 24 u-C5 H]2 -H 87

«-C.H I2 c5 h10 (y) ^ 4.5 X lO"3 21 n-C.H 12 -H 114

*'-c

5h12 c2 h4 10.6 x lO’ 3 25 i-C,H |2 -H 86

(CH.,)

2 C: (CH.,)2 C: -2.5 x lO 2 24 TM-c4 HI0 -h 83

C(CH3

)2 C(CH.,)2 (i.e. = 0)

«-C6 HH c2 h4 3.7 x lO"3 25 «-c,h 14 -h 86

neo-Cfi H14 c2 h4 1.8 X lO" 3 25 neo-CH H I4 -H 86

(CH,)„CHCH, c2 h4 11.6 X lO-3 25 (CH3

) 2 CHCH.> CH, -H 86

ch2ch3 CH. -H

(CH.( )2 CHCH c2 h4 21.0 x lO- 3 25 (CH.,)

2 CHCH 86

(CH3)2 (CH:i )2 -H h2 s C2 H4 0.5 30 H2 S photolysis 90

ch;! sh c2 h4 0.54 ±0.12 0.59 50-220 CH.,SH photolysis 91

(ii) Miscellaneous reactions of hydrogen atoms with hydrocarbons and hydrocarbon derivatives.

Reaction Notes Ei E‘2 loglo-4 l/A ‘2 k\!k2 Temperature rangeRadical source Reference

(1) H + CCl.jD = CC1., + HD

(2) H + CC13 D = CC12 D + HC1

( kcal mole ')

1.1

°C

Room temp. H2

/ discharge 92

(1) H + CCl.,Br = CC1., + HBr

(2) H + CCl.jBr = CCl,Br + HC1 0.49 Room temp. H.,/ discharge 115

(1) H + CC1,F = CC1, + HF

(2) H + CC1,F = CC12 F + HC) 0.071 Room temp. H2

/ discharge 115

(1) H + CCl2 BrH = CCl2 Br+H2 (2) H + CCl2 BrH = CCIBrH + HC1

1.7 Room temp. H2

/ discharge 92

(1) H + CCl2 BrH = CC12 H + HBr

(2) H + CCl'BrH = CCIBrH + HC10.8 Room temp. H2

/ discharge 92

(1) H + C:t H# = C; ,H5 + H2 (2) H + C.( Hh = C.,H7 + H2 32 25 C.,HS radiolysis 88

(1) H + (CH3)3 CD = C4 H9 + HD

(2) H + (CH3

) 3CD = C4 Hh D + h2

1.2 25 t-G4 H9 D photolysis 93

247-168 0- 67—2

11
Ratios of Rate Constants (Hydrogen Atoms) — Continued

Reaction Notes e,-e2 logioA i/A-2 EIE> Temperature range

Radical source Reference

(heal mole-1

) °C

(1) D f(CH.! ),CD = C4H9 + D2 (2) D + (CH,),CD = C4 Hx D + HD

1.2 25 z’-C

4 H4 D photolysis 93

(1) H±z'-C5 H12 = c.hu + h2 (2) H + CjHj , = C5 H10 + H2 (z) 5.2 X 10-2 25 i-C,H12-H 94

(1) H + 1-C5 H10 = C5 Hh + H2 (2) H + n-C5 H12 = C5Hn + H2 8.8 21 n-C5 H)2 -H 88

(1) H + z-C.H =C.H +H

(2) H + C.Hj, = C.H 12 (z) 5.9 x 10-3 25 t-C-H 12-H 94

(1) H + n-Ce H14 = C6 Hrt + H2 (2) H + C6H1S = C6 H14

5.3 X 10-3

1.3 X 10“3 25

25

n-Cw H14 -H n-CBH,4 /l-CBH12 -H

94

94

(1) H + CH.jCHiCHCHO = CRi CH:CHCO + H2 (2) H + CH.CRCHCHO = CH,CH:CH2 + HCO

~0.5

210-350 (CH,)2 CO/

CH:! CH:CHCHO

photolysis

95

(iii) Reactions of the type ( 1 ) H + HX = H., + X

(2) H + X2 = HX + X where X is a halogen

(1) H + HC1 = H2 + C1 «0.05 25 H2 /C12 photolysis 96

(2) H + C12 = HC1 + C1 1.54 ±0.13 -0.84±0.1 0-62 HpCl., photolysis 97

(1) H + HBr=H2 + Br (aa) 0.12 327-1197 H.,/Br2 thermal 98

reaction

(2) H + Br2 = HBr + Br 0.1 162-310 H.,/Br„ photolysis 99

0.12 ±0.009 25-300 H.( /Br2 thermal 100

reaction 0.099 1027-1427 H„/Br2 thermal 101 ±0.007 reaction

(1) h + hi = h2 + i 0.070 ±0.02 394 H.,/1, thermal 44

reaction

(2) H + I

2 = HI + I 0.082 527 H2

/I., thermal 44

±0.012

0.06 700

reaction 102

(1) D + DI = D2 +

1

(2) D + I

2 = DI + I 0.073 527 D2/I

2 thermal 116

reaction

(iv) Miscellaneous Ratios

(1) h + d2 = hd + d

(2) h + hci|h2 + ci 14 ±4 22 HC1/D., photolysis 52

(1) d + hd = d2 + h

(2) D + DC1 = D2 + C1 65 22 H.,/DC1 photolysis 52

(1) D + HC1 = HD + C1 0.5 ±0.4 22 52

(2) D + HC1 = DC1 + H 5. ±4 152 D../HC1 photolysis 52

12
Ratios of Rate Constants (Hydrogen Atoms) — Continued

Reaction Notes Ex —E-> logn)Ai/A2 A-./A* Temperature range

Radical source Reference

( kcal mole 1 ) °C

(1) H + D., = HD + D

(2) H + HBr= H2 + Br 0.55 22 D2 /HBr photolysis 52

(1) h + no2 = no + oh

(2) H + C12 = HC1 + C1 -3.13 0.42 227-267 H2 /C12 /N0, thermal 79

reaction

(1) D + C.,H(

. = C2 H. + HD 1.2 X 10- 3 25 Dl photolysis 103

(2) D + DI = D., + I 8.7 x ICC3 100 DI photolysis 103

(1) h + h2 s = hs + h2 0.60 50]

(2-) h + o; = ho„ 0.137 93 [ H2 S photo-oxidation 104

0.171 100j

Notes

(a) Estimated from the reverse reaction.

(b) This value was used by the authors in the region 1000-

1500 °C, but its origin was not stated.

(c) Measured relative to D + D2 CO = D2 + DCO for which

k — 10 13 - 30 exp (—3000 RT).

(d) Private communication from Asaba.

(e) Taken from Tikhomirova and Voevodsky, “Chain oxidation

of Hydorcarbons in the Gas Phase" (Russ), Moscow, 1955.

(f) Critical survey of literature data.

(g) “A rough estimate.”

(h) Measured relative to H + C.jH,. = C:! H7 for which A = 10 13 - 5 exp (— 2600/RT).

(i) Measured relative to D + H., = HD + H for which A = 10 13- 4 exp (— 5000/RT).

(j) Measured relative to H + 0.2 = OH + O for which k= 5.1 X 109

at 520 °C.

(k) Measured relative to H + C.jH,, = C.( H7 + H2 for which

A = 10 1411 exp (— 8200/RT).

(l) Measured relative to D + H9 = HD + H for which A = 10 13 - 92 exp (— 6000/RT).

(m) Measured relative to D + H2 = HD + H for which A = 10 13 - 46 exp (— 5400/RT).

(n) Rate constant estimated in computer calculations. E value assumed and A factor varied.

(o) Estimated from kinetic data.

(p) The value of E was assumed, and A calculated from the rate constant.

(q) A steric factor of 0.1 was assumed.

(r) Calculated from the recommended value for the reverse

reaction.

(s) Steric factor = 0.13.

(t) Used at flame temperatures.

(u) Measured relative to H + 02 = 0H + 0 for which A = 10 14 31 exp (— 16500/RT).

(v) Measured relative to H + 02 + H2 = H02 + H2 for which

Ar = 5.5 X 10‘° cm6 mole2 sec

-1

(w) Reactions with D atoms.

(x) Calculated from the recommended value for the reverse

reaction.

(y) C.H10 refers to the mixture of pentenes formed in the primary reaction.

(z) C5Hu

is a radical formed in the primary process, probably

either CH:i C(CH:j )CH2 CH:! or CH:1 CH(CH,)CHCH,.

(aa) The author shows that this value is compatible with his results in the temperature range shown.

References

1. Majury and Steacie, Disc. Faraday Soc. 14, 45 (1953).

2. Le Roy, Disc. Faraday Soc. 14, 120 (1953).

3. Berlie and Le Roy, Can. J. Chem. 32, 650 (1954).

4. Pritchard, Pyke, and Trotman-Dickenson, J. Am. Chem.

Soc. 77, 2629 (1955).

5. Benson and Jain, J. Chem. Phys. 31, 1008 (1959).

6. Fenimore and Jones, J. Phys. Chem. 65, 2200 (1961).

7. Gorban and Nalbandyan. Russ. J. Phys. Chem. 36, 946

(1962).

8. Intezarova, Kondratiev, and Mukhoyan. Kinetika i Kataliz

5, 585 (1964).

9. Azatyan, Nalbandyan, and Tsui, Kinetika i Kataliz 5, 201

(1964).

10. Jamieson and Brown, Can. J. Chem. 42, 1638 (1964).

11. Skinner and Ringrose, J. Chem. Phys. 43, 4129 (1965).

12. Steacie, Can. J. Res. 15B, 264 (1937).

13. Klein, McNesby, Scheer, and Schoen, J. Chem. Phys. 30,

58 (1959).

14. Chase and Weinberg, Proc. Roy. Soc. 275A, 411 (1963).

15. Voevodsky and Kondratiev, “Progress in Reaction Ki- netics,” p. 41 (Pergamon Press, 1961).

16. Berlie and Le Roy, Disc. Faraday Soc. 14, 50 (1953).

17. Gorban and Nalbandyan. Dokl. Akad. Nauk. S.S.S.R. 132, 1335 (1960).

18. Trost and Steacie, J. Chem. Phys. 16, 361 (1948).

19. Baldwin, 9th Int. Comb. Symp., p. 604 (Academic Press, N.Y., 1963).

20. Blackmore and Hinshelwood, Proc. Roy. Soc. 271 A, 34

(1963). 21. Yang, J. Phys. Chem. 67, 562 (1963).

22. Baldwin and Melvin, J. Chem. Soc. 1785 (1964).

23. Darwent and Roberts, Disc. Faraday Soc. 14, 55 (1953).

24. Yang, J. Am. Chem. Soc. 84, 3795 (1962).

25. Kazmi, Diefendorf, and Le Roy, Can. J. Chem. 41, 690

(1963).

26. Baldwin, Trans. Faraday Soc. 60, 527 (1964).

27. Sehiff and Steacie, Can. J. Chem. 29, 1 (1951).

28. Baldwin and Walker, Trans. Faraday Soc. 60, 1236 (1964).

29. Kazmi and Le Roy, Can. J. Chem. 42, 1145 (1964).

13
30. White. Winkler, and Kenalty, Can. J. Res. 20B, 255 (1942).

31. Trost and Steacie. J. Chem. Phys. 16, 361 (1948).

32. Norrish and Purnell. Proc. Roy. Soc. 243 A, 449 (1958).

33. McNesby, Scheer, and Klein, J. Chem. Phys. 32, 1814

(1960). 34. Baldwin and Cowe, Trans. Faraday Soc. 58, 1768 (1962). 35. Brennen, Gay, Glass, and Niki, J. Chem. Phys. 43, 2569

(1965).

36. Klein, Scheer, and Schoen, J. Am. Chem. Soc. 78, 50

(1956).

37. Trost. Darwent. and Steacie, J. Chem. Phys. 16,353(1948).

38. Harris and Steacie, J. Chem. Phys. 13, 554 (1945).

39. Jacobs, Giedt, and Cohen, J. Chem. Phys. 43, 3688 (1965). 40. Steiner and Rideal, Proc. Roy. Soc. 173A, 503 (1939). 41. Bigeleisen, Klein, Weston, and Wolfsberg, J. Chem. Phys.

30, 1340 (1959). 42. Steiner Proc. Roy. Soc. 173A, 531 (1939). 43. Cooley and Anderson, Ind. and Eng. Chem. 44, 1402 (1952). 44. Sullivan. J. Chem. Phys. 36, 1925 (1962). 45. Dixon-Lewis, Sutton, and Williams, J. Chem. Soc. 5724

(1965). 46. Skinner and Ringrose, J. Chem. Phys. 42, 2190 ( 1965).

47. Kaufman and Del Greco. 9th Int. Comb. Symp., p. 659

(Academic Press, N.Y., 1963).

48. Dixon-Lewis, Sutton, and Williams, Disc. Faraday Soc. 33, 205 (1962). 49. Dixon-Lewis, Sutton, and Williams. Trans. Faraday Soc. 61, 255 (1965).

50. Schiavello and Volpi, J. Chem. Phys. 37, 1510 (1962). 51. Fenimore and Jones, Comb, and Flame 8, 231 (1964).

52. DeVries and Klein, J. Chem. Phys. 41, 3428 (1964).

53. Hertel, Z. Phys. Chem. 15B, 325 (1931).

54. Padoa and Butirone, Accad. Lincei, 25, 215 (1916); and

Gazz. Chim. Ital. 47, 6 (1917).

55. Porter, Bardwell, and Lind. J. Am. Chem. Soc. 48, 2603

(1926).

56. Krauskopf and Rollefson, J. Am. Chem. Soc. 56, 327 (1934). 57. Trotman-Dickenson, “Gas Kinetics,’' p. 184 (Butterworths,

London, 1955).

58. Seidel, Martin, and Mietzner, Z. Phys. Chem. 47B, 348

(1965).

59. Campbell and Hirschfelder, Univ. of Wisconsin report

CF-2108 NORD 9938.

60. Semenoff, Acta. Physicochim. 20, 291 (1945).

61. Baldwin, Trans. Faraday Soc. 52, 1344 (1956).

62. Baldwin and Simmons, Trans. Faraday Soc. 53, 964 (1957). 63. Semenoff, Nalbandyan, and Karmilova, Zhur. Phys. Chem.

32, 1193 (1957). 64. Schott and Kinsey, J. Chem. Phys. 29, 1177 (1958).

65. Kondratiev, 7th Int. Comb. Symp., p. 41 (Butterworths,

London, 1959).

66. Azatyan, Voevodskii, and Nalbandyan, Kinetika i Kataliz 2, 340 (1961).

67. Fujimoto, Bull. Chem. Soc. Japan 36, 1233 (1963). 68. Lovachev, Comb, and Flame 7, 388 (1963).

69. Clyne, 9th Int. Comb. Symp., p. 211 (Academic Press, N.Y., 1963).

70. Kaufman and Del Greco, 9th Int. Comb. Symp., p. 659

(Academic Press, N.Y., 1963).

71. Miyama and Takeyama, J. Chem. Phys. 41, 2287 (1964).

72. Azatyan, Nalbandyan, and Tsui, Kinetika i Kataliz 5, 201

(1964).

73. Baldwin and Melvin. J. Chem. Soc. 1785 (1964).

74. Glass, Kistiakowsky, Michael, and Niki, J. Chem. Phys.

42, 608 (1965).

75. Garvin and McKinley, J. Chem. Phys. 24, 1256 (1956).

76. Phillips and Schiff, J. Chem. Phys. 37, 1233 (1962).

77. Forst and Giguere. J. Phys. Chem. 62, 340 (1958).

78. Baldwin and Mayor, Trans. Faraday Soc. 56, 103 (1960).

79. Rosser and Wise, J. Phys. Chem. 65, 532 (1961). 80. Schiff, Disc. Faraday Soc. 33, 285 (1962). 81. Ashmore and Tyler, Trans. Faraday Soc. 58, 1108 (1962).

82. Back and Van der Auwera, Can. J. Chem. 40, 2339 (1962). 83. Jennings and Cvetanovic, J. Chem. Phys. 35, 1233 (1961). 84. Yang and Gant, J. Phys. Chem. 65, 1861 (1961). 85. Takahasi and Cvetanovic, Can. J. Chem. 40, 1037 (1962). 86. Holroyd and Klein. J. Phys. Chem. 67, 2273 (1963).

87. Holroyd and Pierce, J. Phys. Chem. 68, 1392 (1964).

88. Back, J. Phys. Chem. 64, 124 (1960). 89. Stock and Gunning, Can. J. Chem. 38, 2295 (1960). 90. Arthur and Bell, J. Chem. Soc. 4866 (1962). 91. Inaba and Darwent, J. Phys. Chem. 64, 1431 (1960). 92. Clark and Tedder, Trans. Faraday Soc. 62, 405 (1966). 93. Okabe and Becker, J. Am. Chem. Soc. 84, 4004 (1962). 94. Kuntz, J. Phys. Chem. 69, 2291 (1965). 95. Pitts, Thompson, and Woolfolk, J. Am. Chem. Soc. 80,

66 (1958). 96. Bigeleisen, Klein, Weston, and Wolfsberg, J. Chem. Phys.

30, 1340 (1959). 97. Klein and Wolfsberg, J. Chem. Phys. 34, 1494 (1961). 98. Levy, J. Phys. Chem. 62, 570 (1958). 99. Bodenstein and Lutkemeyer, Z. Phys. Chem. 114, 208

(1924). 100. jBodenstein and Jung, Z. Phys. Chem. 121, 127 (1926). 101. Britton and Cole, J. Phys. Chem. 65, 1302 (1961). 102. Horie, Ishii, and Amano, J. Phys. Chem. 68, 1264 (1964). 103. Carter, Hamill, and Williams, J. Am. Chem. Soc. 77,

6457 (1955). 104. Darwent and Krasnansky, 7th Int. Comb. Symp., p. 3 (Butterworths, London. 1959).

105. Lenimore and Jones, 9th Int. Comb. Symp., p. 597

(Academic Press, N.Y., 1963).

106. Harris and Steacie. J. Chem. Phys. 13, 559 (1945). 107. Sullivan. J. Chem. Phys. 30, 1292 (1959). 108. Dixon-Lewis, Sutton, and Williams, 10th Int. Comb.

Symp., p. 495 (Comb. Inst. Pittsburgh, 1965). 109. Fenimore and Jones, J. Phys. Chem. 62, 693 (1958). 110. Fenimore and Jones, J. Phys. Chem. 63, 1154 (1959). 111. Azatyan, Nalbandyan. and Tsui, Dokl. Akad. Nauk.

S.S.S.R. 147, 361 (1962). 112. Westenberg and Fristrom, 10th Int. Comb. Symp.. p. 473

(Comb. Inst. Pittsburgh, 1965).

113. Fenimore and Jones'; J. Phys. Chem. 62, 1578 (1958). 114. Back, Trans. Faraday Soc. 54, 512 (1958). 115. Clark and Tedder, Trans. Faraday Soc. 62, 399 (1966). 116. Sullivan, J. Chem. Phys. 39, 3001 (1963).

Review

1. Thrush, "Progress in Reaction Kinetics," Vol. 3. p. 65 tPergamon Press, London, 1965).

14
Metathetical Reactions of Fluorine Atoms

Reactants Notes E logio A Temperature range

Radical source Refer- ence

HYDROGEN ATOM TRANSFER

Hydrogen (kcal mole *) (cm 3 mole 1 sec *) °C h2 (a) 1.71 ±0.22 14.07 25-150 ch4 /h2 /f2 p 1, 4

Alkanes

ch4 (a) 1.21 ±0.80 14.09 - 75-78 CH4/C2Hb/F2 t 2, 4

c2h6 0.28 13.78 -60-20 standard T 2, 4 ch:( ch2 ch.( (a) 0.00 ±0.25 13.52 - 60-20 C2He/C:i HK/F2 T 2, 4 CH:j CH2 CH:i (a) 0.00 ±0.25 13.10 -60-20 C2 HK/C,H8/F2 t 2, 4 CH:( CH2 CH2 CH:t (a) 0.00 ±0.70 13.46 -60-20 n -C4 H10/C:t H8 /F2 T 2, 3, 4 ch,ch2 ch2 ch, (a) 0.00 ±0.65 13.37 - 60-20 n-C4 H ]0/C:! H8/F2 T 2, 3, 4

(CH:i ):j CH (a) 0.00 ±0.70 13.65 - 60-20 n-C4 HJi-C4HJF2 T 2, 3, 4

(CH:! ) :i CH (a) 0.00 ±0.80 12.84 - 60-20 n-C4 HJi-C4 HJF2 T 2, 3, 4

(CH:! ) 4 C (a) 0.00 ±0.80 13.75 - 60-20 t-C4H10/(CH:! ) 4 C/F2 T 2, 4

Cyclo-Alkane

cyclo-C.jH,. (a) 0.00 ±0.10 13.46 cyclo-C.jH,./

C

:j H8/F2 T 2, 4

CHLORINE ATOM TRANSFER

CC14 A = 2 X 10 13 20 cci4/f2 t 5

OXYGEN ATOM TRANSFER

2.8 0-20 F2/0;! p

Notes

(a) These values are based on the assumed value k — 10 13 - 78 exp (— 280/RT) for the reaction F + C.,H6 = C2 H5 + HF.

References

1. Mercer and Pritchard, J. Phys. Chem. 63, 1468 (1959).

2. Fettis, Knox, and Trotman-Dickenson, J. Chem. Soc. 1064

(1960).

3. Anson, Fredricks, and Tedder, J. Chem. Soc. 918 (1959).

4. Fettis and Knox, “Progress in Reaction Kinetics," Vol. 2, p. 3 (Pergamon Press, N.Y., 1964).

5. Clark and Tedder, J. Phys. Chem. 68, 2018 (1964).

6.

Starico, Sicre, and Schumacher, Anales Assoc. Quim.

Argentina 50, 120 (1962). Reviews

1. Fettis and Knox, “Progress in Reaction Kinetics,” Vol. 2, p. 3 (Pergamon Press, N.Y., 1964).

2. Fettis, Knox, and Trotman-Dickenson, Can. J. Chem. 38,

1643 (1960).

15
Reaction of Chlorine Atoms

Index

(a) Hydrogen atom transfer Page Reaction with

1. Hydrogen 17

2. Alkanes 17

3. Cyclo-alkanes 17

4. Halogenated alkanes 18

5. Hydrogen halide 19

(b) Chlorine atom transfer

Reaction with

1. Halogenated alkanes 19

2. Halogens and pseudo-halogens 19

3. Carbonyls, etc 19

(c) Bromine atom transfer 20

(d) Oxygen atom transfer 20

(e) Miscellaneous reactions 20

16
Metathetical Reactions of Chlorine Atoms

Reactants Notes E log 10 A Tempera- Radical source Refer

ture range ences

HYDROGEN ATOM TRANSFER

(fecal mole ') (cm3 mole 1 sec ') °C

Hydrogen

h2

(a)

2=5.9

3= 5.8

6.1 ±1.0

k = (4.8 ±0.4) x

5.9 5.48 ±0.14

5.48

14.3 10 11

13.92 ±0.03

13.92

25-75 - 73-23

0-25

250

628-798

0-798

h2/ci2 h2/ci

2 Cl2 discharge

h2/ci2/no

h2/hci

p

p

T

T

12

3, 38

5, 64

7, 5

HD (b) 5.97 13.83 -33-77 h2/hd/ci2 P 8, 41 HT (b) 6.03 13.79 -38-72 h2 /ht/ci2 P 9

(b) 6.28 13.82 - 30-70 h2 /hd/ht/ci2 P 41

d2 (b) 6.60 13.78 0-32 h2 /co/ci2 P 10, 11, 7

(b) 6.70 13.84 30-178 h2/d2/ci2 P 12

(b) 6.61 13.76 - 30-70 hd/d2/ci2 P 41 DT (b) 6.90 13.73 - 30-70 dt/d2 /ci

2 P 41

Tx

2 (b) 7.17 13.73 - 30-70 t2/d2 /ci2 P 41

Alkanes

ch4 (b) 3.85 ±0.18 13.42 20-211 ch4/h2 /ci2 P 13, 16 cd4

(i) 5.76 13.73 31-188 ch4/cd4 /ci2 P 12

C2H6 (b) 1.04 ±0.08 13.96 -41-385 ch4/c2 h6/ci2 P 14, 15

(b) 1.00 14.08 76-290 CH4 /C2 H6/C12 P 16

^2^6 (i) 1.32 13.75 30-160 c2 h6/c2 d6/ci2 P 12

c:! h8 (b) 0.67 .14.28 25-211 c:! h(1 /c2h6/ci2 P 16

CH.,CH2 CH:( (b) 0.98 14.03 - 70-230 C2 Hfi /C:i H8 /Cl2 P 14, 15

CH.j CH2 CH.j (b) 0.66 13.87 - 70-230 C2 H6/C:i HK/Cl

2 P 14, 15 CH:1 CH2 CH2 CH:( (b) 0.77 13.93 - 70-200 C2 H6/n-C4H10/Cl

2 P 14, 17

CH.( CH2 CH2 CH:j (b) 0.25 13.95 — 70-200 C2 H>-C4 H10/C12 P 14, 17

(CH:i )

:i CH (b) 0.86 14.29 25-211 C2 H6/i-C 4 H I0 /Cl2 P 16

(CH.t ):,CH (b) 0.80 14.09 -80-100 C2 H6/i-C 4 H10/Cl2 P 14, 17

(CH:! )

:! CH (b) 0.02 13.24 -80-100 C2H6/i-C4 H10/Cl2 P 14, 17

(CH;i ) 4 C (b) 0.90 14.25 - 70-230 C.,H8/(CH.t )4 C/Cl2 P 14

(b) 0.70 14.09 25-211 C2 H6/(CH.,)4 C/C12 P 16

Cyclo-alkanes

cyclo-C.jH,. ,b) 4.12 13.73 20-260 C2 Hfi /cyclo- c:1 hs/ci2 P14

17
Metathetical Reactions of Chlorine Atoms — Continued

Reactants Notes E logio A Temperature range

Radical source Refer ences

( kcal mole _1

) (cm 3 mole~ l sec

-1

) °C

cyclo-C 4 HK (b) 0.80 14.43 -30-105 C.jHs /cyclo- 14 C4 HK /C12 p

cyclo-C.H 10 (b) 0.58 14.47 25-211 C.,HJcyc\o- 16 C,H 10 /C12 p

talogenated alkanes

CH,C1 (b) 3.36 13.76 25-211 ch4 /ch.( ci/ci2 p 16

(b) 3.3 ±0.1 13.5 ±0.7 0-300 CH^Cl/various 18 rh/ci2 p p

(c) 3.08 13.5 85-180 C2 C14 /CH:! C1/C12 p 19 CH2 C12 5.5 14.6 28

3.0 13.43 0-300 CH2 Cl2/various 18 RH/C12 p p

(c) 3.12 13.4 110-210 C2 C14 /CH2 C12 /C12 p 19

CHC1, 6.5 14.6 28

3.35 12.84 0-300 ch4 /chci ! /ci.) p 18. 27

(c) 3.33 13.2 140-210 C2 C14 /CHC1:i /C12 p 19. 20, 21

CDC1, (d) 4.06 ±0.2 12.69 -20-180 CHCl.yCDCl./Cl., p 22

(d) 4.79 13.30 109-203 CHcycDcyci, p 12

C.,H.C1 2 5 (b) 1.50 ±0.2 13.66 25-211 C2 H,./C2 H5 C1/C12 p 16 CH2 C1CH,C1 3.0 13.4 23

C2 H;i Cl.

j 3.5 13.5 23

CHC12 CHC12 3.3 13.8 23

c2hcl 5.4 13.9 28

3.3 12.8 110-210 C.,C1,/C.,HCUCL, p 19. 24

3.4 12.7 18 CH:j CH2 CH2 CH2F (e) 0.77 ±0.10 13.0 0-230 C4 HS) F/C12 p 25. 26, 29 ch:! ch2 ch2 ch2 f (e) 0.62 ±0.15 13.1 0-230 c4 h!( f/ci2 p 25. 26, 29 ch,ch2 ch2ch2 f (e) (0.37 ±0.10) (13.3) 0-230 C4 H,,P/C12 p 25, 26, 29 ch,ch2 ch2 ch2 f (e) 0.77 13.1 0-230 c4 h„f/ci2 p 25, 26, 29 ch:i ch2 ch2 ch2 ci (e) 0.77 ±0.20 13.4 35-146 c4 h,,ci/ci

2 p 26, 29 ch:1 ch2 ch2 ch2 ci (e) 0.30 ±0.40 13.3 35-146 C4 H,,C!/C12 p 26. 29 ch3 ch2 ch2 ch2 ci (e) 0.22 ±0.10 13.7 35-146 c4 h,,ci/ci

2 p 26, 29 ch,ch2 ch2 ch,ci (e) (0.77) (13.4) 35-146 C4 H,, Cl/Cl, p 26, 29

cf.1 ch2 ch2 ch2 ch:1 (e) 2.0 12.2 0-230 CF:; C4 H,,/C12 p 25

cf.,ch2 ch2 ch2 ch:! (e) 0.6 13.0 0-230 cf: .c

4 h,,/ci2 p 25

18
Metathetical Reactions of Chlorine Atoms — Continued

Reactants Notes E log io A Temperature range

Radical source References

(kcal mole~ l ) ( cm 3 mole -l sec

-1

) °C

CF,CH2 CH2 CH2 CH, (e) (0.3) (13.3) 0-230 CF;i C4 H,,/C12 P 25

cf,ch2 ch2 ch2 ch:( (e) 0.5 12.8 0-230 CF;i C4H„/C12 P 25

Hydrogen Halide

HC1 6.57 ±0.49 39-150 HCL/D2/C12 P 39

CHLORINE ATOM TRANSFER

Halogenated alkanes

CH:( C1 (f) (g) 25.0 14.0 23, 30

CH2 C12

(1) (g) 21.4 14.0 23, 30

CHCl.t (1) (g) 21.0 14.0 23, 30

CC14

(1) 18.9 14.3 23

(h) 20.0 14.0 28

C2 H5 C1 (0 21.5 14.3 23, 30 ch2 cich2 ci (f) 21.3 14.3 23, 30 chci2 ch2 ci (9 20.6 14.3 23, 30

chci2 chci2

(f) 20.4 14.3 23, 30

CHCl2 CCl.t (h) 19.0 14.5 28

(9 18.3 14.3 23, 30

(f) 17.9 ±1.0 13.8 ±0.5 31

C2 C16(f) 19.5 14.4 23

(h) 18.0 13.5 28

Halogens and pseudohalogens

BrCl (h) 1.1 ±0.4 12.3 20-60 32

IC1 4.5 11.7 30^60 IC1 P 33, 35

CNC1 34 14 1727-2527 C1CN S.T. 34

Carbonyls, etc.

COC1 0.83 14.6 25-55 C0/C12 P 36

C0C12 (h) 19.9 14.4 25-55 28

(a) 23.5 14.5 15-450 43

19
Metathetical Reactions of Bromine Atoms

Reactants Notes E logi oA Tempera- Radical source Referture range ences

HYDROGEN ATOM TRANSFER

Hydrogen ( kcal mole-1

) (cm3 mole 1 sec *) °C

h2 19.4 ±0.2 14.36 227-302 H2 /Br2 T 1, 2

18.6 ±0.6 13.93 277-327 H2 /Br2 T 3, 2

17.6 13.86 200-300 H2 /Br2 P 4

(a) 19.8 13.36 700-1400 6

A = (0.89 anc1 1.03) X 1011 1123 H2/Br2 T 7

A- = (0.91 anc1 0.79) X 10 n 1168 H2 /Br2 T 7

(b) 17.8 13.7 18

18.3 14.03 327-1197 H2 /Br2 T 8

19.2 ±1.8 14.25 1027-1427 H2 /Br2 T 2

(b) 19.7 ±0.4 14.43 ±0.14 227-1427 9

19.17 14.24 832-1011 H2 /02/CF:) Br ignition 32

19.7 14.43 HD (i) 20.3 14.37 168-350 HD/H2 /Br2 T,T 34

HT (i) 20.4 14.34 168-350 HT/H2 /Br2 T, P 34

D2 20.2 14.89 211-in H2 /Br2 T 3, 2

20.4 ±1.0 14.08 1027-1427 H2/Br2 T 2

(i) 21.0 14.31 168-350 H2/D2/Br T.P 34

(b) 21.4 ±0.4 14.29 277-1427 9

21.4 14.29

Alkanes

ch4 18.2 ±0.5 13.8 150-210 CH4 /Br2 P 10

(c) (d) 18.3 14.0 204-341 CH./CH^Cl/Br, T. P 11 17.3 13.15 150-300 22

18.2 13.8

c2 h6 13.6 ±0.5 35-90 C2 H6/Br2 P. 13

(d) 13.4 ±0.1 13.90 ±0.04 59-199 C2 H(i /CH.! Br/Br2 T 11, 14

(e) 12.3 13.29 25-121 CH.^UFJC^J 15 Br2 T

C:i HK (d) 10.15 ±0.14 13.71 ±0.07 13-145 C:i H8/C2 HK /Br2 T 11, 14

rc-C

4 H)0 (d) 10.23 ±0.23 13.22 ±0.14 -6-98 n-C4 H10/i-C4 H,o/ 11, 14, 20 Br2 T

i-C

4 H)0 (d) 7.51 ±0.20 13.30 ±0.11 34-148 i-C4 H10/C:i H8 /Br

2 T 11, 14, 20

(h) 11.7 17.6 40-95 i -C4 H10/Br2 P 16, 17

neo-C5 H12 (d) 14.29 ±0.13 14.24 ±0.06 57-200 neoC7H 1 „/C,,H(./Br., T 11

(h) 18.2 17.0 98-152 neo-C5 HI2 /Br2 P 19, 17

Aromatic hydrocarbon

C6 H5 CH:i (h) 7.6 13.5 82-132 C6 H5 CH:t /Br2 P 21, 25, 17

Halogenated alkanes

CH:S F (e) 14.8 12.86 150-300 CH4 /CH.( F/Br2 P 12 ch2 f2 (e) 15.3 12.52 150-300 CH4 /CH2 F2/Br2 P 12

22
Metathetical Reactions of Bromine Atoms — Continued

Reactants Notes E logi oA Temperature range

Radical source Refer- ences

(kcal mole-1

) ( cm3 mole-1 sec

-1

) °C

CHF, (e) 21.1 23.0

12.28

13.46

150-300

361-431

CHF.( /C2 F5 H/Br2 P

CF:i H/Br2 - T

1222

CH,C1 14.45 ±0.16 13.62 ±0.06 59-200 CH:) C1/C2 H6/Br2 T, P 11

CHC1, 9.3

10.

12.36 147-182 CHCl.j/Br, T

CHC1.( /Br2 P

23, 1724 CH:i Br 16.05 13.7 150-230 CH.,Br/Br2 P 10, 11, 14

CH.jCH^F (e) 10.3 12.38

\ 39-121 C2 Hfi /C2 H.F/Br2 p 15

CH:i CHF^ ( e ) 13.3 12.52 96-230 CH4/C2 H4 F2/Br2 P 15

ch:! cf. (e) 22.2 13.18 243-379 CF:) H/CH ( CF:i /Br2 P 15

cf:! ch2 f (e) 18.2 12.73 130-322 CH2 F2/CF.! CH.,F/ Br2 P

15

cf2 hcf2 h (e) 18.1 12.75 118-283 ch2 f2/cf.1 ch2 f/ Br2 P

15

cf:! cf2 h (e) 18.0 12.20 150-300 CH4 /C2 F,H/Br2 12

cf:! cf2 cf2 h 17.8 “12.08 146-286 CH4/C:i F7 H/Br2 T 15 CH;i CH2 CH2 CH2 F (f) 11.6 13.2 62-185 ch.,ch2 ch2 ch2 f/ Br2

“ p“

26 ch,ch2 ch2 ch2 f (0 11.5 13.1 62-185 CH:i CH2 CH2 CH2 F/ Br2 p

26

ch..ch2 ch2 ch2 f (0 (10.2) (13.6) 62-185 ch ! ch2 ch2 ch2 f/

Br., P

26 ch:( ch2 ch2 ch2f (0 13.0 13.0 62-185 CH.t CH2 CH2 CH2 F/ Br2

" P‘

26

CF,CH2 CH2 CH2 CH, (g) (0 11.0 13.2 0-230 CF:i CH2 CH2 CH2 CH:( / Br2 P

26 CF:t CH2 CH2 CH2 CH, (f) (10.2) (13.6) 0-230 cf.! ch2 ch2 ch2 ch.,/ Br2 p

26

CF,CH2 CH2 CH2CH:i (f) 13.0 13.1 0-230 CF.( CH2 CH CH2 CH.t / Br2

“ $

26

Alcohols

CHsOH

ch,ch2oh

6.3

2.6 ±2.0

11.65 76-135

70-150

CH:! OH/Br2 P

C2 H.OH/Br2 p

27

28

CHLORINE ATOM TRANSFER

Cl2 6.9 ±0.4 12.65 ±0.2 20-60 Br2 /Cl

2 P 29

BROMINE ATOM TRANSFER

Alkyl halides

CH;! Br 22.9 13.7 150-297 CH4/Br2 P, T 10, 17 CH2 Br2 14.0 10, 17

23
Metathetical Reactions of Bromine Atoms — Continued

Reactants Notes E logioA Temperature range

Radical source Refer- ences

{kcal mole-1

) (cm3 mole -1 sec

-1

) °C

CCl.jBr 10.3 13.91 146-183 CCl.t Br/Br„ T 30

Hydrogen halide

HBr (a) 43.8 14.4 700-1400 6

41.7 13.9 25-302 H2 /Br2 T 33, 17

Halogen

BrCl A: = (3.1 ±0.8) > 103 20 Br2 /Cl

2 P 29

OXYGEN ATOM TRANSFER

37 14.3 603-700 N2 0/Br2 T

MISCELLANEOUS REACTIONS

Br + Na., = NaBr + Na A:= 1.5 X 10 14 -300 Br2 /Na D.F. 35

Notes

(a) Estimated from a general review of kinetic data.

(b) Critical survey of literature data.

(c) These values are less reliable than those given for other compounds, by the same authors.

(d) All values are related to Br + CH ,Br = CH2 Br + HBr as standard, for which A = 1013 - 73 exp (— 16050/RT).

(e) Measured relative to CH4 + Br = CH3 + HBr for which

A = 101315 exp (— 17300/RT). This is a recalculation of data from

ref. 10. To compare these values with the others, E should be

increased by 1 kcal/mole and log A by 0.65 units. (0 The values at the 8 or y positions (bracketed) are assumed

the same as for the 2 position in n-butane (ref. 11). The other

values are calculated relative to this. These values must be con- sidered very approximate.

(g) Very small quantities of CF.U!HBrCH2 CH2 CH.j were

formed, but not in sufficient quantities for the Arrhenius factors

to be estimated.

(h) These values are believed to be in error (ref. 17)

(i) Measured relative to Br + H2 = H + HBr, for which k = 1014 - 43 exp (- 19,700/RT).

References (Bromine Atoms)

1. Bodenstein and Lind, Z. Phys. Chem. 57, 168 (1906).

2. Britton and Cole, J. Phys. Chem. 65, 1302 (1961).

3. Bach, Bonhoeffer, and Moelwyn-Hughes, Z. Phys. Chem.

27B, 71 (1935).

4. Bodenstein and Lutkemeyer, Z. Phys. Chem. 114, 208

(1924).

5. Steiner, Proc. Roy. Soc. 173A, 531 (1939).

6. Cooley and Anderson, Ind. and Eng. Chem. 44, 1402 (1952).

7. Britton and Davidson, J. Chem. Phys. 23, 2461 (1955).

8. Levy, J. Phys. Chem. 62 , 570 (1958).

9. Fettis and Knox, Progress in Reaction Kinetics, Vol. 2, p. 3 (Pergamon Press, 1964).

10. Kistiakowsky and Van Artsdaleiv, J. Chem. Phys. 12, 469

(1944).

11. Fettis, Knox, and Trotman-Diekenson, J. Chem. Soc. 4177

(1960).

12. Tarr, Coomber, and Whittle, Trans. Faraday Soc. 61,

1182 (1965).

13. Andersen and Van Artsdalen, J. Chem. Phys. 12, 479

(1944).

14. Fettis and Trotman-Diekenson, J. Am. Chem. Soc. 81,

5260 (1959).

15. Coomber and Whittle, Trans. Faraday Soc. 62, 1553 (1966).

16. Eckstein, Scheraga, and Van Artsdalen, J. Chem. Phys.

22, 28 (1954).

17. Benson and Buss, J. Chem. Phys. 28, 301 (1958).

18. Campbell and Fristom, Chem. Rev. 58, 173 (1958).

19. Hormats and Van Artsdalen, J. Chem. Phys. 19, 778

(1951).

20. Anson, Fredricks, and Tedder, J. Chem. Soc. 918 (1959).

21. Anderson, Scheraga, and Van Artsdalen, J. Chem. Phys.

21, 1258 (1953). 22. Corbett, Tarr, and Whittle, Trans. Faraday Soc. 59, 1609

(1963).

23. Sullivan and Davidson, J. Chem. Phys. 19, 143 (1951). 24. Braunworth and Schumacher, Kolloidzschr. 89, 184

(1939).

25. Swegler, Scheraga, and Van Artsdalen, J. Chem. Phys.

19, 135 (1951).

26. Galiba, Tedder, and Watson, J. Chem. Soc. 1321 (1964).

27. Buckley and Whittle, Trans. Faraday Soc. 58, 536 (1962).

28. Tarr and Whittle, Trans. Faraday Soc. 60, 2039 (1964).

29. Christie and Thrush, Trans. Faraday Soc. 55, 1139 (1959).

30. Davidson and Sullivan, J. Chem. Phys. 17, 176 (1949). 31. Kaufman, Gerri, and Pascale, J. Chem. Phys. 24, 32

(1956). 32. Skinner and Ringrose, J. Chem. Phys. 43, 4129 (1965). 33. Bodenstein and Jung, Z. Phys. Chem. 121, 127 (1926). 34. Timmons and Weston, J. Chem. Phys. 41, 1654 (1964). 35. Polanyi, “Atomic Reactions.” (Williams and Norgate,

London, 1932).

Review

1. Fettis and Knox, “Progress in Reaction Kinetics, Vol. 2, p. 3 (Pergamon Press, London, 1964).

24
Metathetical Reactions of Iodine Atoms

Reactants Notes E logioA Temperature rangeRadical source Refer- ences

HYDROGEN ATOM TRANSFER

Hydrogen ( kcal mole ') (cm3 mole 1 sec ') °C

h2 33.9 ±0.3 14.32 ±0.11 105-360 HA T i 33.5 ±0.2 14.20 ±0.07 394-527 HA T 2

A- = 4.6 X 10* 700 HI and HA T 3, 4

d2 34.5 ±0.3 14.06 ±0.10 394-527 DA T 5

Alkanes

ch4 (a) 33.5 14.70 260-316 6, 7 34.1 14.70 260-316 CHA T 7 35.0 ±1.1 14.95 275-345 CH4 /I

2 T 8 c2 h6 27.9 14.22 263-303 c2 h5 i/hi t 9

c,h8 25.5 ± 1 14.53 ±0.36 307-340 c:! h8/i

2 t 10 ch:! ch2 ch:! 25.0 14.22 307-340 C:! Hk/I2 T 10

*- C4H, 0 21.4 ±0.5 13.88 ±0.15 252-310 tcaa t 11

Alkenes

CH2 :CHCH;! 18.04 ±0.32 13.25 ±0.14 208-300 CH2 :CHCH A T 22

1-CH2 :CHCH2 CH.! 13.2 ±0.4 12.83 ±0.15 204-253 CH2 :CHCH2 CH.,/ 12 h T

Aromatic hydrocarbon

CBH5CH;i A =4.8 x 107 501 c2 h5i/c6 h5 ch3 t 13

Aldehyde

CH:i CHO 15.7 13.3 222-268 CH:i COI/HI T 14

Alcohol

(CH:! ) 2 CHOH 20.5 14.07 207-300 (CH:i )2 CHOH/I2 T 23

IODINE ATOM TRANSFER

Alkyl halides

ay 19.8 14.3 270-320 CH.t I/HI T 15, 16

20.5 (k— 1.60 x 103

) 280 CH ( I/HI T 17. 16

20.5 ± 0.5 14.4 ±0.2 260-316 CH.jI/HI T 6

19.2 13.71 CH.J/HI T 18

CF.,1 17.60 13.8 167-485 cf:! i/hi t 18 c2 h,i 16.7 13.62 250-300 c2 h.i/hi t 15, 16 3*18.2 (A = 6.8 X 103

) 260 c2 h5 i/hi t 17, 16

17.1 ±0.7 14.01 ±0.28 263-303 c2 h.i/hi t 9 n-C;i H7I 5= 18.5 (A = 12. ? X 103

) 290 «-C:i H7 I/HI T 17, 16

ich2 ch2 ch2 i 19.5 14.0 19

(CH.j):( CI 13.0 ±0.7 13.7 ±0.4 252-310 (CH.t ).

( CH/I2 t 11 25
Metathetical Reactions of Iodine Atoms — Continued

Reactants Notes E logio4 Tempera- Radical source Referture range ences

(kcal mole-1

) (cm3 mole-1 sec

-1

) °C

Acetyl halide

CH;i COI 14.6 13.9 222-268 CH,COI/Hl T 14

Hydrogen halide

HI 36.4 14.32 ±0.20 105-360 h2/i

2 t 1 36.5 394-527 h2 /i

2 t 2

OXYGEN ATOM TRANSFER

n2 o 38 14.45 603-700 n2 o/i2 t 20

MISCELLANEOUS REACTIONS

1 + Na, = Nal + Na k= 2.6X 10 13 -300 I

2/Na D.F. 21

Notes

(a) Calculated from the reverse reaction.

(b) Estimated from thermodynamic data.

References (Iodine Atoms)

1. Sullivan, J. Chem. Phys. 30, 1292 (1959).

2. Sullivan, J. Chem. Phys. 36, 1925 (1962).

3. Horie, Ishii, and Amano, J. Phys. Chem. 68, 1264 (1964).

4. Graven, J. Am. Chem. Soc. 78, 3297 (1956).

5. Sullivan, J. Chem. Phys. 39, 3001 (1963).

6. Flowers and Benson, J. Chem. Phys. 38, 882 (1963).

7. Golden, Walsh, and Benson. J. Am. Chem. Soc. 87, 4053

(1965).

8. Goy and Pritchard, J. Phys. Chem. 69, 3040 (1965).

9. Hartley and Benson, J. Chem. Phys. 39, 132 (1963).

10. Nangia and Benson, J. Am. Chem. Soc. 86, 2773 (1964).

11. Teranishi and Benson, J. Am. Chem. Soc. 85, 2887 (1963).

12. Benson. Bose, and Nangia, J. Am. Chem. Soc. 85, 1388

(1963).

13. Yang and Conway, J. Chem. Phys. 43, 1296 (1965).

14. O'Neal and Benson, J. Chem. Phys. 37, 540 (1962).

15. Sullivan, J. Phys. Chem. 65, 722 (1961).

16. Ogg, J. Am. Chem. Soc. 56, 526 (1934).

17. Benson and O’Neal, J. Chem. Phys. 34, 514 (1961).

18. Body, Downs, Gow, and Horrex, J. Phys. Chem. 67, 719

(1963).

19. Benson, J. Chem. Phys. 34, 521 (1961).

20. Kaufman, Gerri, and Pascale, J. Chem. Phys. 24, 32

(1956).

21. Polanyi, “Atomic Reactions” (Williams and Norgate,

London, 1932).

22. Golden, Rodgers, and Benson, J. Am. Chem. Soc. 88,

3196 (1966).

23. Walsh and Benson, J. Am. Chem. Soc. 88, 3480 (1966).

Review

1. Fettis and Knox, “Progress in Reaction Kinetics,” Vol. 2, p. 3 (Pergamon Press, London, 1964).

26
Ratios of Rate Constants (Sulphur Atoms)

Reactions Notes £,-£

2

Xog^AijA-i A1/A2 Tempera- Radical Source Referture Range ences

(kcal mole~ x ) °C

(1) S( 1 D) + COS = CO 4- S2 (2) S('D) + CH4 = CH:) SH 17.8 25 COS P 1

(1) S('D) + COS = CO + S2 (a) 2.2 25 COS P 2

(2) S( 1 D) + C2 H,. = C2 H5 SH 2.04 25 COS P 1

(1) S('D) + COS = CO + S2 (2) S(‘D) + C.,HS = C:j H7 SH 1.9 25 COS P 2

(1) S( 1 D) + COS = CO + S2 (2) Sf^J + t-C^j^C^HySH 2.04 25 COS P 1

Notes References

(a) Ratio decreases with pressure. 1. Knight, Strauss, and Gunning, J. Am. Chem. Soc. 85, 2349

(b) Data also given (ref. 2) on S atom insertion into cyclo- (1963).

C.jH,., cyclo-C 4 HK

, and cyclo-C-H |(|

. 2. Knight, Strauss, Malm, and Gunning, J. Am. Chem. Soc. 86,4243(1964).

27

247-168 0- 67—3
Reactions of Sodium Atoms

Index

(a) Fluorine Atom Transfer Page Reactions with

1. Halogenated alkanes 29

2. Halogenated alkenes 29

3 . Halogenated acids and acid halides 29

4. Halogenated aromatic derivatives 29

5 . Polyfluorides 29

(b) Chlorine Atom Transfer

Reactions with

1. Halogenated alkanes 29

2. Halogenated alkenes 31

3 . Halogenated aromatic derivatives 31

4. Cyanides 32

5 . Halogenated acids, acid chlorides, esters, etc 32

6. Polyhalides 32

7 . Oxychlorides 33

8. Halogens and pseudo-halogens 33

9 . Hydrogen halide 33

(c) Bromine Atom Transfer

Reactions with

1 . Halogenated alkanes 33

2. Halogenated alkenes 34

3 . Halogenated aromatic derivatives 34

4. Acid bromides 35

5 . Halogens and pseudo-halogens 35

6. Hydrogen halides 35

(d) Iodine Atom Transfer

Reactions with

1. Halogenated alkanes 35

2. Halogenated alkenes 35

3 . Halogenated aromatic derivatives 35

4. Halogens 35

5 . Hydrogen halides 35

(e) Cyanide Group Transfer 35

28
Metathetical Reactions of Sodium Atoms

Reactants Notes (>£ log 10 k Tempera- Radical source References

ture range

FLUORINE ATOM TRANSFER

Halogenated alkanes {kcal mole ') {cm 3 mole 1 sec ') °C

cf.2 (b) (e) 6.5 log (Ay ) 1/2 313 D.F. 4

(e) 5.0 log (Ay ) 1/2 310 D.F. 5

cfh2 (b) (c) 6.1 log (Ay.) 1/2 313 D.F. 4

cf2 h (b) (d) 6.2 log (A>) 1/z 313 D.F. 4

CF, (b) 13.83 313 D.F. 4

13.97 310 D.F. 5

CFH.j >25 <8.7 240 D.F. 1, 6 ~ 18.5 7.3 247 2, 3 ch2 f2 14.0 8.8 247 2, 3 chf:! 14.0 8.8 247 2, 3

CF, 12.6 9.4 247 2, 3

cyclo-CK F12 7.1 11.7 247 2, 3

cyclo-CHFn CF:i 6.7 12.0 247 2, 3

Alkenes

c2f. 8.8 11.0 247 2, 3

Acids and acid halides

CF.jCOOH 4.0 13.0 247 2, 3

CF:i COF 7.6 11.5 247 2, 3

Halogenated aromaties

c„h5f < 8.7 247 19

Miscellaneous

SFk 3.3 13.3 247 2, 3

CHLORINE ATOM TRANSFER

Halogenated alkanes

CH:i Cl 7.5 10.7 240 D.F. 1, 6

10.9 270 7 11.8 325 M.D.F. 8

(f) 9.8 11.1 313 D.F. 9

8.2 D.F. 10

11.8 220 M.L. 11

29
Metathetical Reactions of Sodium Atoms — Continued

Reactants Notes < a> E log io A Temperature range

Radical source References

( kcal mole ') (cm 3 mole~ 1 sec~ *) °C

CH2 C1„ 11.75 275 D.F. 1, 6

12.4 270 7

11.8 250 D.F. 12

CHC1, 12.7 275 D.F. 1. 6

13.5 270 7 13.0 250 D.F. 12

CC14 13.3 275 D.F. 1, 6

14.5 270 7

14.0 250 D.F. 12

(g) (0 8.4 12.17 310 M.D.F. 13 14.35 247 D.F. 14 CH2 FC1 (g) (0 10.1 10.97 313 D.F. 9

chf2 ci 10.0 247 3

(g) (0 10.0 11.0 313 D.F. 9

CF..CI

1 10.7 247 3

9.2 1L3 313 D.F. 9

(0 7.4 275-315 D.F. 15

(g) (f) 10.2 10.9 310 M.D.F. 13 CF2 C12 (g) (0 9.0 to 9.5 11.5 to 11.7 310 M.D.F. 13

CFC1, (g) (0 8.7 to 9.2 11.8 to 11.9 310 M.D.F. 13

C2 H,C1 10.9 275 D.F. 6. 1 10.2 260-380 D.F. 16, 17

7.8 292-391 D.F. 10 CH,C1CH2 C1 11.8 275 D.F. 6

(a) 7.0 12.0 285 D.F. 18 ch:! chci2 11.9 275 D.F. 6

CH.,CC1, 13.6 247 D.F. 14 CH:1 CH2 CH.,C1 (a) 9.1 11.1 275 D.F. 6

(a) 9.0 11.0 261 D.F. 18

10.7 267 D.F. 19 CH:1 CHC1CH:{ 11.2 275 D.F. 6 CH2 C1CH2 CH2C1 11.7 275 D.F. 6 CH:i CHClCH,Cl 12.0 275 D.F. 6

CH:i CH2 CHC12 12.2 275 D.F. 6

(CH:i ) 2 CCl2 12.4 275 D.F. 6

12.6 247 D.F. 14 CH:1 CH2 CH2 CH2 C1 11.2 275 D.F. 6

CH.t CH2 CHClCH;j 11.4 275 D.F. 6

30
Metathetical Reactions of Sodium Atoms — Continued

Reactants Notes WE log 10 / Temperature rangeRadical source References

(kcal mole ~'

)

( cm 3 mole~ 1 sec~ ‘) °C

<CH,)2 CHCH2 C1 11.2 275 D.F. 6

(CH;J ).,CC1 11.5 275 D.F. 6

11.4 247 D.F. 14

ch,ch2 ch2 ch2 ch2 ci

11.4 275 D.F. 6

(CH.,)

2 CHCH2 CH2 C1 11.4 275 D.F. 6

(CH,)2 CC1CH2 CH;! 11.9 275 D.F. 6

Alkenes

CH2 :CHC1 10.7 275 D.F. 6

trans-CHClXHCl 11.3 275 D.F. 6

cis-CHCl:CHCl 11.4 275 D.F. 6 CH2 :CHCH2 C1 12.3 275 D.F. 6

12.5 260 D.F. 18 CH2 :CC1CH, 11.0 275 D.F. 6 CJHXHXHCl b 5 13.0 275 D.F. 18

C6H5 CH:CHCH2 C1 13.9 275 D.F. 18

Aromatic chlorides

and their derivatives

C6H5 C1 9.4 247 D.F. 19

11.2 244 M.L. 25

11.8 270 D.F. 1

Cs H,CH2 C1 14.7 275 D.F. 6

13.7 284 D.F. 18 CHXHXHXl b 5 2 2 13.4 285 D.F. 18

o-FC,.H4 C1 10.3 247 D.F. 19

m-FC6H4 Cl 9.8 247 D.F. 19

p-fc6 h4 ci 9.1 247 D.F. 19

oX1C6H4 C1 11.2 247 D.F. 19

o CH.! 00CCk H4 C1 13.4 247 D.F. 19

2Xl-pyridine 12.7 247 D.F. 19

3Xl-pyridine 10.0 247 D.F. 19

Cyanides

CNCH2 C1 13.9 285 D.F. 18

31
Metathetical Reactions of Sodium Atoms — Continued

Reactants Notes WE log io k Temperature rangeRadical source References

( kcal mole _1

) (cm 3 mole

1 sec~ ’) °C

CNCH2 CH2 C1 11.8 285 D.F. 18

Acids, acid chlorides.

esters, etc. CH2 C1C00H 13.3 247 3

CH,C0C1 12.7 275 D.F. 6, 1 13.4 247 D.F. 3, 2 0 D.F. 10 CTFC0C1 o 5 14.7 240 D.F. 1 cicooc2 h5 11.6 247 D.F. 3, 2 ch2 cicooc2 h5 13.2 247 D.F. 3, 2

cich2 ch2 oh 11.7 285 D.F. 18 CH:i COCH2 Cl 13.7 275 D.F. 6

14.0 247 D.F. 2

ch.,och2 ci 11.3 247 3, 2

Polyhalides

Bci;i 11.7 270 D.F. 7

SiCl 4 11.6 270 D.F. 7

11.8 247 D.F. 14

CH.jSiCl.j 9.8 247 D.F. 14

(CH.,)

2SiCl2 9.3 247 D.F. 14

(CH.,).,SiCl 9.4 247 D.F. 14

PC1:I 14.2 270 D.F. 7

TiCl4 14.0 270 D.F. 7

GeCl4 14.7 270 D.F. 7

AsCl., 14.2 270 D.F. 7

SnCl4 14.5 270 D.F. 7

SC12 14.8 270 D.F. 7

S2 C12 14.2 270 D.F. 7

Oxychlorides

C0C12 13.9 270 D.F. 7

Cr02 Cl2 14.1 270 D.F. 7

P0C1, 14.4 270 D.F. 7

32
Metathetical Reactions of Sodium Atoms — Continued

Reactants Notes (*»£ log 10 k Temperature range

Radical source References

[kcal mole '

)

( cm 3 mole~ l sec~ ') °C

Halogens and pseudohalogens

Cl2 14.6 Dil. F. 20

CNC1 14.0 285 D.F. 18

13.9 250 D.F. 1

Hydrogen halide

HC1 12.4 327 Dil. F. 21, 20

BROMINE ATOM TRANSFER

lalogenated alkanes

CH,Br 13.3 240 D.F. 1, 6

12.8 270 7

12.6 255 D.F. 12

12.2 200 M.L. 11 12.8 242 M.L. 11

(h) 3.4 10 CH2 Br2 13.6 255 D.F. 12

13.5 255 M.L. 12

CHBr.j 14.6 255 D.F. 12

13.9 255 M.L. 12

CFBr:i 14.3 255 D.F. 12

CF,Br (a) 2.3 285 D.F. 15 CHFBr2 13.7 255 M.L. 12 CH2 ClBr 13.3 255 D.F. 12

13.3 255 M.L. 12

CHClBr, 14.3 255 D.F. 12

13.7 255 M.L. 12

CHCl2 Br 14.0 255 D.F. 12

13.6 255 M.L. 12

CCl,Br 14.5 255 D.F. 12

14.0 255 M.L. 12

C2H5Br 12.8 240 D.F. 1 12.4 247 D.F. 19

12.7 263 D.F. 18

33
Metathetical Reactions of Sodium Atoms — Continued

Reactants Notes Ca > E logm 1‘ Temperature rangeRadical source References

( kcal mole “') (cm 3 mole~ 1 sec 1 ) °C

CH2 BrCH2 Br 13.3 247 3

cyclo-C.( H5 Br 12.0 247 D.F. 22

cyclo-C4 H7 Br 12.6 247 D.F. 22

cyclo-C5 H9Br 13.1 247 D.F. 22

ch,ch2 ch2 ch2 12.8 247 D.F. 22 CH2 Br

cyclo-C6Hn Br 12.7 23

12.7 247 D.F. 22

Alkenes

CH2 :CHBr 12.4 269 D.F. 18

11.2 247 D.F. 22

CK H.CH:CHBr 13.1 270 D.F. 18

CB H5 CH:CHCH2 Br 14.6 285 D.F. 18

Aromatic bromides

and their derivatives

C«H5 Br 12.3 255 M.L. 24

11.4 247 D.F. 19

13.2 244 M.L. 25

13.4 260 D.F. 1 12.1 247 D.F. 14

o-ClCLH.Br o 4 12.6 247 D.F. 19

m-ClC^H^Br 11.9 247 D.F. 19

p-ClC6H4 Br 11.6 247 D.F. 19

o-BrCH H4 Br 13.4 247 D.F. 19

o-CNCfi H4 Br 13.3 247 D.F. 19

m-CNCH H4 Br 12.6 247 D.F. 19

p-CNCfi H4 Br 12.8 247 D.F. 19

o-HOCB H4 Br 12.2 247 D.F. 19

m-HOC6H4 Br 11.8 247 D.F. 19

o-CH.( C6 H4 Br 11.5 247 D.F. 19

m-CH..CK H ,Br 11.2 247 D.F. 19

34
Metaihetical Reactions of Sodium Atoms — Continued

Reactants Notes (a

> E log 10 / Temperature range

Radical source References

( kcal mole 1

) ( cm 3 mole 1 sec *) °C

p-CH,C(i H | Br 11.3 247 D.F. 19

o-CH.jOC^H^Br 11.9 247 D.F. 19

p-CH.) OC(; H4 Br 11.6 247 D.F. 19

o-CH 00C H Br .» n -4 13.8 247 D.F. 19

m-CH.OOC .H Br 3 o -4 12.6 247 D.F. 19

p-CH:! OOCK H4 Br 12.6 247 D.F. 19

a-Bromonaphthalene12.7 247 3

/3-Bromonaphthalene

12.1 247 3

2:Br-pyridine 13.3 247 D.F. 19

3:Br-pyridine 11.9 247 D.F. 19

CK H.CH.,CH.,Br o 5 2 2 13.6 280 D.F. 18

Acid bromide

CH:| COBr 13.9 300 D.F. 1

Halogens and pseudohalogens

CNBr 14.1 273 D.F. 18

Hydrogen halide

HBr 13.8 327 Dil. F. 21. 20

IODINE ATOM TRANSFER

Halogenated alkanes

ch4 i 14.7 240 D.F. 6

14.5 240 M.L. 11 13.7 250 M.L. 12

13.6 255 D.F. 12

13.6 277 D.F. 23

0 D.F. 10

CF.,I 14.0 247 3

1.7 285-295 D.F. 15

C2 H,I 14.0 240-270 D.F. 1 14.3 276 D.F. 18 ch,ch2 ch2

i 13.4 240 D.F. 1 35
Metathetical Reactions of Sodium Atoms — Continued

Reactants Notes <a)£ log io k Temperature range

Radical source References

(kcal mole 1

) (cm 3 mole~ 1 sec~ ') °C

Alkenes

CH2 :CHI 13.4 263 D.F. 18

Aromatic iodides -

ck ht 14.7 240 D.F. 1 14.3 244 M.L. 25

Halogens

h 14.8 Dil. F. 20

Hydrogen halide

HI 14.7 327 Dil. F. 20, 21

CYANIDE GROUP TRANSFER

CH,CN <6.6 247 3 CH.CH,CN bo 2 9.8 247 3 CH2(CN)COOC2 H5 11.6 247 3

Notes

(a) The activation energies E are calculated from the formula

k — 10 14 - 7 exp (-E/RT).

(b) These values are lower limits.

(c) ke is the rate contant for the combination reaction 2CFHo = c2 f2 h4 .

(d) kc is the rate constant for the combination reaction 2CF2 H = C;>F4 H2 .

(e) kf is the rate constant for the combination reaction 2CF2 = C2 F4 .

(f) Calculated assuming a steric factor of unity.

(g) These values refer to the rate constants for the primary

process.

(h) Estimated from a critical survey of literature data.

References

1. Von Hartel and Polanyi, Z. Phys. Chem. 11B, 97 (1930).

2. Warhurst, Quart. Rev. Chem. Soc. 5 , 44 (1951).

3. Trotman-Dickenson, “Gas Kinetics,” p. 219 (Butterworths,

London, 1955).

4. Reed and Rabinovitch, J. Phys. Chem. 61, 598 (1957).

5. Kaufman and Reed, J. Phys. Chem. 67, 896 (1963).

6. Hartel, Meer, and Polanyi, Z. Phys. Chem. 19B, 139(1933).

7. Heller and Polanyi, Trans. Faraday Soc. 32, 633 (1936).

8. Reed and Rabinovitch, J. Chem. Phys. 27, 988 (1957).

9. Reed and Rabinovitch, J. Phys. Chem. 61, 598 (1957).

10. Kerr, Lissi, and Trotman-Dickenson, J. Chem. Soc. 1673

(1964).

11. Frommer and Polanyi, Trans. Faraday Soc. 30, 519 (1934).

12. Haresnape, Stevels, and Warhurst, Trans. Faraday Soc. 36, 465 (1940).

13. Kaufman and Reed, J. Phys. Chem. 67, 896 (1963).

14. Gowenlock and Thomas, J. Chem. Soc. 5068 (1965).

15. Hodgins and Haines, Can. J. Chem. 30, 473 (1952).

16. Cvetanovic and Le Roy, J. Chem. Phys. 20, 1016 (1952).

17. Cvetanovic and Le Roy, Can. J. Chem. 29, 597 (1951).

18. Evans and Walker, Trans. Faraday Soc. 40, 384 (1944).

19. Riding, Scanlon, and Warhurst, Trans. Faraday Soc. 52,

1354 (1956).

20. Polanyi, “Atomic Reactions” (Williams and Norgate,

London, 1932).

21. Schay, Z. Phys. Chem. 11B, 291 (1930). 22. Friswell, Gowenlock, and Thomas, J. Chem. Soc. 6323

(1965). 23. Whittle (Ph. D. Thesis, Manchester, 1951).

24. Warhurst, Trans. Faraday Soc. 35, 674 (1939). 25. Fairbrother and Warhurst. Trans. Faraday Soc. 31 , 987

(1935).

Reviews

1. Polanyi, “Atomic Reactions” (Williams and Norgate, London, 1932).

2. Bawn, Ann. Rep. Chem. Soc. 39, 36 (1942).

3. Warhurst, Quart. Rev. Chem. Soc. 5 , 44 (1951).

36
Melathetical Reactions of Potassium Atoms

Reactants Notes E log io k Tempera- Radical source Reference

ture range

CHLORINE ATOM TRANSFER

(.kcal mole) 1 HC1

Cl2 (b)

(cm3 mole 1 sec *) 14.0 °C

327 Dil F. 1, 2

BROMINE ATOM TRANSFER

HBr 14.6 327 Dil F. 1. 2

(a) 3.4 M.B. 3

Br2 (b)

IODINE ATOM TRANSFER

HI 15.3 327 Dil F. 1, 2

CH,I (a) <0.3 M.B. 5

Notes

(a) These quantities cannot be identified with normal Arrhenius factors.

(b) See reference 4. Ratios of Rate Constants (Potassium Atoms)

The table refers to ratios of rate constants for reactions of the following types:

K+R,X = KX + R1 (1) K + R2X = KX + R2 (2)

where X is any halogen atom.

RiX RoX Notes Ei — E'2 A2 /Ai k-zl ki Temperature range Radical source Reference

CH,C1 C2 H5 C1

(kcal mole~ x ) 0.4 ± 0.09 0.83 ±0.10

°C

217-333 D.F. 6 CH:! C1 CH.( COCl 360 285 D.F. 6

C2 H5 C1 (CH.,)

2 CHC1 — 0.13 ± 0.14 2.18 ±0.25 238-325 D.F. 7

c2 h5 ci (CH3

);) CC1 2.27 ±0.55 0.78 ±0.4 229-275 D.F. 7

CH,Br c2 h5 ci 4.4 0.52 230-316 D.F. 6 CH:j Br CH;i COCl 1.4 3.5 229-318 D.F. 6

CH.j1 C2 H5 C1 38 285 D.F. 6 CH:i I CH.jCOCI 0 7.0 238-322 D.F. 6

37
References 4. Krocsak and Schay, Z. Phys. Chem. 19B, 344 (1932).

5. Herschbach, Kwei, and Norris, J. Chem. Phys. 34, 1842

1. Schay, Z. Phys. Chem. 11B, 291 (1930). (1961).

2. Polanyi, “Atomic Reactions,” p. 46 (Williams and Norgate. 6. Kerr, Lissi, and Trotman-Dickenson, J. Chem. Soc. 1673 London, 1932). (1964).

3. Taylor and Datz, J. Chem. Phys. 23, 1711 (1955). 7. Emovon and Lissi, J. Chem. Soc. 3509 (1964).

Metathetical Reactions of Methyne Radicals

Reaction Notes E logio/1 Temperature range

Radical source Reference

CH + NH f = HCN

+ h2 + h

( kcal mole~ l

) A->6x 10 10 (cm 3 mole~ i sec

-1

) °C

no indication C2 H.,/NH:! flames 1

Reference

(1) Safrany, Reeves, and Harteck, J. Am. Chem. Soc. 86, 3160 (1964).

38
Ratios of Rate Constants (Methylene Radicals)

Reactions Notes £i-£2 l0g 1()^l/^2 A'l/A'2 Tempera- Radical source Referture range ence

( kcal mole_1

) °C

(1) ch2 + ch2 co = c2 h4 + co (a) 2.3 6-9 i

(2) CH2 + CO = CH2 CO (b) 1.25 4-16 CH2 CO/ 13 CO p i

(1) CH2 + CH2 CO = C.,H4 + CO

(2) CH2 + C2H4 = C:! H6 4.8 28-81 ch2 co/o2 p 2

(1) CH2 + CH2 CO = C2 H4 + CO

(2) CH2 + C2 H2 = C;j H4 (c) 0.9 ±0.1 no indication ch2 co/c2 h2 F.P. 3

(1) CH2 + CH2 CO = C2 H4 + CO

(2) CH2 + H2 = CH, + H -0.8 -40-99 ch2 co/h2 P 4, 5, 7

(1) CH2 + CH2 CO = C2 H4 + CO

(2) CH2 + CD4 = CH2 D2 + CD2 -0.9 0.15 27-298 ch2 co/cd4 P 6, 7

Notes

(a) and (b) represent two methods of estimating Ai/A^: the dis- crepancy lies outside the experimental error.

(c) k represents the sum of the rate constants for the reactions CH2 + C2 H2 = HC:CCH.j and CH2 + C2 H2 = H2 C:C:CH,.

References

1.

Wilson and Kistiakowsky, J. Am. Chem. Soc. 80, 2934

(1958).

2. Holroyd and Noyes, J. Am. Chem. Soc. 78, 4831 (1956).

3. Terao, Sakai, and Shida, J. Am. Chem. Soc. 85, 3919 (1963).

4. Gesser and Steacie, Can. J. Chem. 34, 113 (1956).

5. Chanmugam and Burton, Can. J. Chem. 34, 1021 (1956).

6. Chanmugam and Burton, J. Am. Chem. Soc. 78, 509 (1956).

7. Bell and Kistiakowsky, J. Am. Chem. Soc. 84, 3417 (1962).

Review

1. Frey, “Progress in Reaction Kinetics,” Vol. 2, p. 133 (Pergamon Press, London, 1964).

39
Methyl Radical Reactions

Index

(a) Hydrogen atom transfer

Reaction with Page

1. Hydrogen

2. Alkanes

3. Cyclo-alkanes

4. Alkenes

5. Alkynes

6. Aromatic hydrocarbons

7. Halogenated aromatics

8. Alcohols

9. Thiols

10. Amines

11. Imines

12. Amides, azines, etc..

13. Aldehydes

14. Ketones

15. Esters

16. Acids and acid anhydrides

17. Ethers and epoxides

18. Peroxides

19. Nitriles

20. Metal alkyls

21. Halogenated alkanes

22. Hydrides of nitrogen, oxygen, and sulphur

23. Hydrogen halides

(b) Fluorine atom transfer

(c) Chlorine atom transfer

(d) Bromine atom transfer

(e) Iodine atQm transfer

(f) Oxygen atom transfer

(g) Group transfer reactions

(h) Ratios of rate constants

1. Reactions with halogens and hydrogen halides

2. Miscellaneous reactions

41

41

43

43

43

44

44

45

45

45

46

46

47

48

48

49

49

49

49

49

50

50

50

50

51

51

51

51

51

52

53

40
Metathetical Reactions of Methyl Radicals

Reactants Notes E lo g uA Tempera-

"

Radical source Referture range ences

HYDROGEN ATOM TRANSFER

Hydrogen ( kcal mole *) (cm3 mole 1 sec ') °C

h2 (d) 10.0 ±0.5 11.5 130-290 CH.jCOCHj P 1, 2, 3

9.9 ±0.5 11.7 25-250 HglCH.^ T 4, 3

13 ±2 13.4 50-250 Cd(CH.,)2 P 5

(a) 13.2 ±1.0 12.5 136-318 CH,COCH s P 6

10.2 ±0.5 11.52 99-207 ch2 co p 7

(b) 12.85 12.75 8

A = 4.1 X 108 507 CH,OCH, T 9

10.2 12.50 697-863 H2 /02 ignition 10

( y) 10.2 ±0.2 11.7 130-290 CD.COCD., P 1, 2

( y) 11.1 12.0 150-300 CD,COCD, P 3

10.0 11.5 HD 10.0 11.1 140-296 CH,COCH, P 3

( y) 10.7 11.4 137-298 CD:i COCD:! P 3 HD 11.5 11.5 135-296 CH.jCOCH, P 3

( y) 10.7 11.2 137-299 CD.jCOCD., P 3

d2 (d) 11.8 ±0.1 11.8 130-290 CH t COCH, P 1, 2, 3

(c) 15.3 ±1.0 14.8 258-451 CH.CHO P 6

(a) 14.3 ±0.6 12.5 150-458 CHTCOCH, P 6

12.7 ±0.3 12.3 27-253 HgfCH.^ P 12

A = 2.0 X 108 507 CH ( OCH, T 9

12.1 ±0.6 11.79 151-299 ch,coch 5 p 13

11.9 11.4 140-425 CHTCOCH, P 14

( y) 10.9 ±0.3 11.4 130-290 CD,COCD, P 1, 2 Alkanes

CH4 14.9 12.00 200-350 CH,COCH, P 16. 17

( y) A = 1.7 x 10s 182 CD.jCOCD.j P 18, 19

( y) 14.3 11.5 350-525 CD,COCD, P. T 20

( y) A = 3.6 X 10® 320 CD.jCOCD., P 21

( y) 14.1 11.8 200-350 17

CH;j D (y) (e) 12.8 10.42 27-327 22

CD.,H (e) 13.8 11.21 27-327 22 cd4 12.93 ±0.65 11.26 153-428 CH,COCH, P 23, 17

(v) 18.4 12.95 200-350 CD,COCD:i P 17

c2 h6 12.0 10.6 770-890 C2 H6 t 24

A = 1.4 X 108 630 C2 Hk t 25

( y) (f) 9.9 ±1.1 500-560 CD.jCDO T 29, 51

(y) 10.4 ±0.4 11.3 116-294 CD ( COCD, P 19, 26

( y) 11.8 12.21 162-341 CD.jCOCDj P 21

( y ) 12.1 12.3 260-490 CD ( COCD t P 27

( y) 11.5 ±0.2 11.9 246-524 CD.jCOCD., P. T 28

CH,CD:I ( y) 12.2 12.0 260-490 CD.jCOCDj P 27, 39

CH,CD, ( y) 14.1 12.1 260-490 CD.jCOCDj P 27, 39

41
Metathetical Reactions of Methyl Radicals — Continued

Reactants Notes E l°g

104 Temperature range

Radical source Refer- ences

(kcal mole-1

) (cm3 mole-1 sec

-1

) °C

c2 d6 14.8 ±0.3 12.3 328-507 CH.COCH., P. T 28

(y) 13.6 12.3 260-490 CD.COCD., p 27 C,HX (g) k = 3.3 X 109 580 C,Hh t 29

10.3 11.91 300-460 CD,COCD, p 30 CH:i CD2 CH:

, (y) 11.6 12.08 300-450 CD,COCD:i P 31, 39 CH:j CD2 CH.t (y) 11.6 11.85 300-450 CD.COCD., P 31, 39

n-C4 H,(, 8.3 ±0.2 11.0 122-198 CH.COCH., P 19, 26

8.2 ±0.5 11.3 130-220 Hg(CH.)2 P 32

(h) 9.5 ±0.5 11.5 Hg(CH.)2 P 32

8.6 ±0.3 11.2 92-223 Hg(CH.)2 p 33

(h) A = 1.3 X 107 182 Hg(CH.( )2 P 34

9.1 ±0.3 11.4 79-162 <CH.( ) 2 N2 p 35

9.6 11.92 250-449 CD.jCOCD^ p 36

(y) (f) 10.3 ±0.2 500-560 CD.CDO T 29 ch:1 cd2 cd2 ch ! (y) 11.7 12.09 356-450 CD.jCOCD., P 36

ch.,cd2 cd2 ch, (y) 11.7 12.12 356-450 CD:j COCD:1 P 36

iso-C4HJ0 7.6 ±0.2 11.0 76-194 CHjCOCH, P 19. 26

7.4 ±0.3 10.8 93-220 HglCH.j^ P 33

6.6 ± 0.3 10.3 25-169 (CH.( )2 N2 p 35

7.7 10.3 111-146 d.t.b'.p. t 37

(y) A = 2.05 x 107 198 CD^COCD., P 38

(y) (f) 9.0 ±0.6 500-560 CD:i CDO T 29

(CH:i )

:i CH (y) 8.2 11.47 300-460 CD.jCOCD, P 30 (CH:i ) a CD (y) 11.7 12.26 300-460 CD.COCa, P 30, 39

(CH:j ):! CD (y) 9.8 11.57 300-460 CD:1 COCD t P 30, 39

n-C-H 8.1 ±0.2 11.0 89-178 CH..COCH, p 19. 26

A = 1 .Ox 109 540 n-C.H,., T 40

9.9 ±2.7 540-580 «-C.H l2 t 29

iso-C 5H12 A = C .9 X 109 540 iso-C.H,., T 40

neo-C-H,., 10.0 ±0.3 11.3 138-292 CH.COCH, P 19, 26

10.4 ±0.3 11.3 131-251 HgiCH

P

33

A = 0.2 X 109 540 neo-C-H,., T 40

(y) (0 10.8 ±0.2 500-560 CDXDO T 29

8.1 ±0.2 11.1 92-184 CH.COCH, P 19. 26

(CH:; )2CHCH(CH,)., 6.9 ±0.2 10.8 T O

CM CH.COCH. P 19. 26

6.8 ±0.2 10.7 28-220 Hg(CH..)„ P 33

(y) (0 7.3 ±0.8 500-560 CDXDO T 29

(y) 7.8 ±0.4 11.3 166-293 CD.COCD, P 26

(C2 H,)XH 6.8 ±0.3 10.5 76-238 Hg(CH.,)2 P 41

«-Cs H lx A = .6 x 109 500 /)Xx H ls T 40

42
Metaihetical Reactions of Methyl Radicals — Continued

Reactants Notes E log,

04 Temperature range. Radical source Refer- ences

(kcal mole-1

) (cm3 mole~ l sec

-1

) °C

(CH,),CCH2

/. =0 .7 X 109 500 (CH ).,CCH, 40

CH(CH,)2 CH('cH„)2 T

fCH,)2 CHCH(CH.) /. = 1

.

9 X 109 500 (CH.).,CHCH(CH.,) 40 CH(CH,)2 CH(CH T

(y) 7.9 ±0.4 11.3 141-332 Cl) COCD

.

P 26 iCH :; ),CC(CH,), (y) 9.5 ±0.4 11.3 162-322 Cl) COCD. P 26

Cyclo-alkanes

cyclo-C,Hfi 10.2 ±1.0 11.1 100-250 Hg(CH.s )2 P 42

(y) 10.3 ±0.4 11.0 139-292 CD.COCD, P 43

(y) 12.9 12.18 248-404 CD,COCD, P 44

cyclo-C4H8 (y) 9.3 ± 0.4 11.4 154-307 CD,COCD, P 43

10.1 12.18 262-402 CD,COCD, P 45

cyclo-C5H10 (i) k = 5. 7X 10 7 303 Hg(CH,)2 T 46

(y) 8.3 ±0.2 11.4 66-296 CD,COCD, P 43

(y) 9.1 12.24 250-402 CD,COCD, P 44

(y) 9.0 12.10 160-500 CD:i COCD, P 47

cyclo-C,.H 12 8.3 ±0.2 11.3 65-189 CH,COCH, P 43

8.3 ±0.3 11.2 81-220 Hg(CH,)2 P 33

(y) 9.5 12.47 254-481 CD.jCOCD, P 48

cyclo-C 7 H 14 (y) 8.9 12.49 48

Alkenes

ch|ch2 (y) 10.0 ±0.4 11.3 188-340 CDgCOCD, P 49

(y) (0 7.3 ±1.0 500-560 CD,CDO T 29

CH,CH:CH2 8.2 11.04 107-168 D.T.B.P 50

(y) 7.7 ±0.4 10.8 163-304 CD,COCD, P 49

(y) (f) 8.0 ±0.3 500-560 CD,CDO T 29, 51

CH,CH:CHCH, (y) 7.7 ±0.4 11.1 188-342 CD,COCD, P 49 CH2 :CHCH2 CH, (y) 7.6 ± 0.4 11.2 189-340 CD,COCD, P 49

(CH,)2 C:CH2 (y) 7.3 ±0.4 10.9 168-304 CD,COCD, P 49

ch,ch2 ch2 (y) 7.6 ±0.4 11.2 188-346 CD,COCD, P 49 CH:CH2

(CH,)2 CHCH:CH2 (y) 7.4 ±0.4 11.3 189-346 CD,COCD, P 49

(CH,)2 C:C(CH,)2 (y) 7.8 ±0.4 11.6 188-341 CD,COCD, P 49

Alkynes

HCiCH (y) 14.0 200-500 CD.COCD, P 52

DC:CD 18.4 200-500 CH,COCH, P 52

247-168 0-67—4

43
Metathetical Reactions of Methyl Radicals — Continued

Reactants Notes E Temperature range

Radical source Refer- ences

(kcal mole" 1

) (cm3 mole~ 1 sec

-1

) °C

CH:j C:'CCH, (y) 8.6 ±0.4 11.6 213-346 CD.jCOCD., P 43 CH'CCH2 CH:j (y) 9.1 ±0.4 11.9 183-347 CD.jCOCDj P 43

Aromatic hydrocarbons

CeHB II 8 x 10 6 209 D.T.B.P. T 53

(y) 9.2 ±0.4 10.4 183-327 CD.jCOCD, P 43

C6 H5 CH:i (h) 7 ± 2 10.0 103-249 Hg(CH.j)2 P 54

11.0 ±2 130-230 D.T.B.P. P 55

7.3 ±0.3 11.2 149-250 Hg(CH.,)2 P 33

O') 13.03 ±0.27 12.92 ±0.08 346-701 56. 57, 58

(z) 7.4 ±0.3 10.47 100-253 CH^COCH., P 59

9.2 ±0.3 11.4 159-270 D.T.B.P. T 53

A = (4.0 .± 0.8) x 105 60 CH,N.,CH., P 60

(y) 8.3 ±0.3 11.0 120-334 CD:i COCD:i P 43 c6h5cd. A- =(2.3 ±0.4) X 104 60 CH.( N2 CH.( P 60

10.2 10.7 100-300 72 c6h5 cd3 k = ( 2.6-fc0.2) x 104 60 CH,NXH„ P 60

11.3 11.8 102-284 CH.jCOCH., P 72

c6 d5 ch:! II 00 fc0.8) x 105 60 CH.,N.,CH., P 60

9.6 11.6 106-284 CH.( COCH:i P 72 C6D5 CH;j A = (1.0 t0.2) x 104 60 ch.,n2 ch., P 60

A = 5.1 x 104 182 CH,COCH:l P 72

C6 D5 CD:j A = (3.7

-t0.2) x 104 60 CH:i N2 CH.t P 60

Cfi H5 C2 H5 (z) 7.0 ±0.3 10.82 85-183 CH.jCOCH., P 59

C6H5 CH(CH.,)2 (z) 6.4 ±0.5 10.76 123-249 CH:i COCH:1 P 59

o-CK H4(CH:j ) 2 (z) 7.8 ±0.3 11.13 101-205 CH:1 COCH:i P 61

m-C6H4 (CH:j ) 2 (z) 8.5 ±0.3 11.45 100-197 CH.,COCH;1 P 61

p-Cfi H4 (CH:i )2 (z) 7.4 ±0.2 10.82 99-197 CH ( COCH.t P 61

(k) k = 3. 1 X 107 484 P-C6 H4 <CH.(

) 2 T 62

C6 H4 (CH.,)

2 (k) (1) k = 6

C75 On X o 700 C6 H4 (CH.,)

2 T 63

Halogenated aro- matics

o-CH:i C6 H4 F (z) 6.0 ±0.4 9.76 330-460 CH.COCH, P 64

m-CH.,C6 H4 F (z) 7.1 ±0.2 10.32 330-460 CHjCOCH., P 64

p-CH.( C6H4F (z) 5.7 ±0.4 9.60 330-460 CH:( COCH t P 64

44
Metathetical Reactions of Methyl Radicals — Continued

Reactants Notes E Temperature range

Radical source Refer- ences

(kcal mole~ l ) {cm3 mole~ l sec

1

) °C

Alcohols

CH.s OH 8.2 ±0.2 10.7 103-219 CH,COCH, P 43

8.2 ±0.5 10.6 100-250 Hg(CH,)2 P 42

8.7 ±0.2 10.76 ± 0.07 133-199 CH,COCH, P 65

(y) 8.4 ±0.1 10.68 ±0.05 125-250 CD,COCD, P 73

CH.jOH (m) 10.4 11.38 133-199 CH.jCOCH, P 65

(y) (m) 8.1 10.38 125-250 CD.jCOCD, P 73 CD,OH 6.4 ±0.7 9.25 ±0.3 133-199 CH,COCH, P 65

(y) 9.0 ±0.1 10.46 ±0.03 125-245 CD.jCOCD, P 73 CD,OH 11.7 ± 0.6 11.25 ±0.28 133-199 CH.jCOCH, P 65

(y) 9.3 ±0.1 10.18 ±0.06 125-245 CD,COCD, P 73 C2 Hg OH (y) 8.7 ±0.4 11.5 189-341 CD.jCOCD, P 43

(CH:! ) 2 CH(OH) (y) 7.3 ±0.4 11.0 214-347 CD.jCOCD, P 43

Thiols

CH:i SH A = 1 CO X © 30 CH.jCOCH, P 66

CD:i SH 4.1 ±0.2 11.03 ±0.15 130-200 CH.jCOCH, P 74

CD.jSH 8.3 ±0.1 10.88 ±0.05 130-200 CH.jCOCH, P 74

c2 h5 sh k = 3 5X 107 30 CH.jCOCH, P 66

(CH;i ) 2 CHSH k = 4 1 X 107 30 CH,COCH, P 66

(CHs),CSH A = 5 9X 107 30 CH.jCOCH, P 66

Amines (primary)

CH,NH2 7.6 10.9 125-157 D.T.B.P. T 67

7.2 ±0.2 10.59 ±0.12 CH.,N„CH, P 68

(y) 8.4 ± 0.4 11.3 183-340 CD.jCOCD, P 43 ch:1 nh2 (m) 8.7 ±0.7 10.99 ±0.37 120-175 ch,n2 ch. P 69, 68 ch,nh2 (m) 5.7 ±0.40 9.55 ±0.22 120-175 ch,n2 ch. P 69, 68

ch,nd2 9.00 ±0.20 11.15 ±0.12 120-175 ch,n2 ch. P 69, 68

ch,nd2 7.00 ±0.30 9.61 ±0.16 120-175 ch,n2 ch. P 69. 68

cd,nh2 6.00 ±0.50 9.77 ±0.28 120-175 ch,n2 ch. P 69, 68 CD:i NH2 10.10 ±0.30 10.86 ±0.16 120-175 ch,n2 ch. P 69, 68

C2 H,NH2 7.1 11.2 125-157 D.T.B.P. T 67

7.3 ±0.3 10.89 ±0.18 110-180 ch,n2ch. P 75 ch,ch2 nh2 k = 6 3X 105 150 CH,N,CH, P 75

45
Metathetical Reactions of Methyl Radicals — Continued

Reactants Notes E l°g,

04 Temperature range

Radical source Refer- ences

(kcal mole-1

) (cm3 mole~ l sec' 1) °C

CH:i CH2 NH2 8.1 11.2 110-180 CH:i N2 CH:! p 75 ch,ch2 nh2 6.5 9.9 110-180 CH:j N2 CH:1 p 75 ch,ch2 nd. 7.6 ± 0.4 10.04 ±0.21 110-180 ch.,n2 ch3 p 75 cd:! ch2 nd2 k= 1. 3x 105 150 CH:i N2 CH3 p 75

Amines (secondary)

(CH.,)

2 NH 7.2 11.7 125-157 D.T.B.P. p 67

7.00 ±0.30 11.20 ±0.13 120-180 CH:i N2 CH:i p 70

(y) 7.2 ±0.4 11.3 184-341 CD COCD.t p 43

(CH.,)

2 NH 6.40 ± 0.30 10.81 ±0.21 120-175 CII..N2 CH;t p 70 (CH3

)2 ND 8.70 ±0.60 11.46 ±0.28 120-175 ch3n2ch3 p 70

(CH:! ) 2 ND 7.80 ±0.40 10.65 ±0.22 120-175 ch:1 n2 ch:! p 70

(C2 H.)2 NH 7.2 11.8 125-157 D.T.B.P. T 67

(n) 5.7 ±1.0 10.7 123-260 CH.( COCH:i P 71

((CH:i ) 2 CH)2 NH 7.8 12.0 125-157 D.T.B.P. T 67

Amines (tertiary)

(CH;j );i N 8.0 11.4 132-269 CH.s COCH.. P 71

8.9 ±0.1 11.9 ±0.1 123-232 CH.jCOCH., P 76

(y) 8.8 ±0.4 11.8 193-302 CD:i COCD:i P 43

(C2 H5

) 3N (n) 5.3 ±1.0 10.4 123-260 CH.COCH, P 71

Imines

(CH2

) 2 NH 4.8 ±0.3 10.7 125-157 D.T.B.P. T 77

(o) 5.28 10.76 100-216 CH,COCH ( P 78

4.77 ±0.44 10.29 ±0.23 110-175 CH.jN.CH., P 79. 80

(y) 5.4 10.94 120-260 CD.COCD, P 78

(CH2

) 2 NH (m) 10.10 ±2.80 11.44 ±1.48 110-175 CH.,N2 CH:j P 79. 80

(CH2

) 2 NH 4.57 ±0.10 10.17 ±0.05 110-175 CH3 N2 CH:1 P 79. 80

(CH2

)2 ND 6.34 ±0.21 10.17 ±0.13 110-175 CH ,N2 CH.t P 79. 80

(CH2

) 2 NC(CH:i ).

! 6.6 9.6 125-157 D.T.B.P. T 67 CHXH:NC(CH:; ). 7.8 11.1 125-157 D.T.B.P. T 67

Amides, azines, etc. hconh2 6.6 10.5 170-247 CH.jCOCH., P 81

HCONHCH., 7.6 10.9 161-287 CH..COCH., P 81

HCON(CH.t ) 2 8.3 11.4 120-298 ch:! coch:i P 81

46
Metathetical Reactions of Methyl Radicals — Continued

Reactants Notes E iog.c/* Temperature range Radical source Refer- ences

( kcal mole-1

) {cm3 mole-1 sec

-1

) °C

ch:( conh2 (q) 9.2 ±0.3 10.8 144-224 ch:! conh2 P 82

CH:! CON(CH,)2 8.3 ±0.2 11.3 ± 0.1 106-232 CH:i COCH:! P 76

(CH,)2 NCON(CH:i ) 2 7.3 ±0.2 11.0 ±0.1 108-235 CH,COCH:i P 76 ch:( onh2 4.53 ±0.25 10.70 ± 0.15 70-190 ch2 n,ch:! P 83 ch:) ond2 5.88 ±0.22 10.55 ±0.12 70-190 ch:! n2 ch:( P 83

(CH:j ) 2 N.NH2 5.80 ±0.20 11.34 ±0.12 110-180 CH,N2 CH:i P 68

(CH:i ) 2 N.NH2 (r) 8.5 11.6 110-180 CH:! N2 CH:i P 68

CH:i CH:NN:CHCH, 6.1 10.5 125-157 D.T.B.P. T 67 CH:! N2 CH;i 7.6 ±0.3 11.1 60-182 ch,n2 ch, P 84

7.3 10.49 25-150 CH.i N.,CH.! P 85

6.86 ±0.18 10.37 - 47-50 CH.,N0 CH„ P 86

8.4 ±0.3 11.40 80-180 CH.,N„CH., P 87

(s) 7.83 ±0.08 10.97 ±0.04 70-190 CH,N.,CH, P 83

8.7 11.47 50-180 CH.jN.CH., P 89 CH:! N:N(0)CH;j 6 ± 2 27-121 CH;j N:N(0)CH:! P 90

Aldehydes

HCHO A- = 4 7 X 10 7 120 CH..C0CH../0,. P 91

6.2 ±0.3 11.06 80-180 CH.,N„CH., P 87

6.6 11.25 111-146 D.T.B.P. T 37 DCDO 7.9 ±0.3 11.15 80-180 ch,n2 ch:( P 87

CH.jCHO 7.9 ±0.3 12.15 124-156 D.T.B.P. T 92

6.8 11.5 91-165 CH.,N„CH, P 93

8.5 12.4 133-291 CH,CHO P 94

8.7 109-345 CH,CHO P 95

7.6 ±0.2 11.9 ±0.1 119-175 D.T.B.P. T 96

6.8 11.50 25-250 CH,N.,CH, P 97

(y) (f) 6.5 ±0.3 500-560 CDjCDO T 29

ch:! cdo 7.9 11.8 27-158 ch.,n|ch:! P 93

c2 h.cho 7.5 11.9 122-156 D.T.B.P. T 99, 92

CH2 :CHCH2 CHO 10.9 13.3 119-175 D.T.B.P. T 96

n-C.,H_CHO 7.3 ±0.3 1 1.8 ± 0.2 119-175 D.T.B.P. T 96

ra-C,F7 CHO 5.55 ±0.20 11.20 27-306 CH:i COCH,/ 98 C:i F.CHO P

iso-C H.CHO 8.7 ±0.3 12.6 ±0.2 119-175 D.T.B.P. T 96

n-C,H,,CHO 8.0 ±0.3 12.1 ±0.2 119-175 D.T.B.P. T 96

iso-C, H.CHO 8.4 ±0.3 12.3 ±0.2 119-175 D.T.B.P. T 96

47
Metathetical Reactions of Methyl Radicals — Continued

Reactants Notes E Temperature range

Radical source Refer- ences

(kcal mole-1

) (cm3 mole-1 sec

-1

) °C

sec-C4 H(i CHO 10.4 ±0.3 13.1 ±0.3 119-175 D.T.B.P. T 96

t-C4 H;i CHO 10.2 ±0.3 13.0 ±0.3 119-175 D.T.B.P. T 96

Ketones

CH.jCOCH.j (t) 9.7 ±0.1 11.6 121-300 CH.jCOCH.j P 100

(h) 9.6 ±0.4 11.5 100-250 CH.jCOCH.j P 101

9.7 ±0.2 11.8 125-220 CH.jCOCH., and 102 Hg(CH:i )2 P

9.8 11.59 271-439 CH.jCOCH., P 103

9.5 ±1.5 11.5 127-175 D.T.B.P. t 104

9.5 ±0.3 11.8 130-155 D.T.B.P. T - 105

9.8 ±0.4 11.60 27-412 CH.jCOCH., P 13

9.56 11.43 132-292 CH.s COCH:j P 2, 15 CD:j COCD,H (y) (u) 9.95 ±0.15 10.74 120-250 CD.jCOCD.j p 73

(y) (u) 9.48 9.87 125-200 CD:( COCD.s p 74 cd:! cocd:! (y) 10.3 ±0.2 11.6 138-292 CDjCOCD., P 100

(y) 10.6 ±0.3 11.8 130-290 CD^COCD., p 1 (y) 11.6 ±0.3 11.8 135-290 CD.COCD., P 3

(y) 11.6 12.07 150-250 CD.jCOCD.j p 30

(y) 11.44 ±0.05 11.66 ±0.03 120-250 CD.jCOCD, p 73

(y) 11.29 ±0.03 11.57 ±0.01 125-200 CD^COCD.j P 74

(y) 10.9 ±1.0 11.5 130-200 CD:! COCD:j P 110

CF.jCOCH.j 8.9 12.0 25-113 CF;) COCH:t P 109 CH,COC2H5 7.4 10.6 79-190 CH;! COC2H5 p 166 c2 h5 coc2 h5 8.0 ±0.2 11.8 130-155 D.T.B.P. T 105

7.0 ±0.1 11.2 26-134 CH.jNgCH.j P 85

(y) k = 2. 9X 10 7 141 CD.COCD, p 111

cyclo-C.jHgCOCH.j 9.6 ±1 60-170 cyclo-C.jH.COCH., P 112 C6H5 COCH:! ,7.4 10.7 273-407 C„H_COCH.. 6 5 .1 P 113 CH:j COCOCH, 7.1 ±0.2 28-200 CH jCOCOCH., P 114

8.5 11.3 140-198 CH.N.CH., P 116

7.7 28-200 CH;i COCOCH:i P 115

Esters

HCOOCH., 9.0 10.9 77-230 CH.COCH, P 117

9.8 11.3 117 HCOOC2 H5 8.2 10.5 77-230 CH:i COCH:1 p 117 hcooch2 ch2 ch:! 7.3 10.1 74-178 CH.jCOCH., p 118 HCOOCH(CH:s ) 2 8.9 10.9 94-181 CH.jCOCH., P 118 hcooch2 ch2 8.2 10.6 75-186 CH.t COCH:! P 119 ch2 ch:!

48
Metathetical Reactions of Methyl Radicals — Continued

Reactants Notes E lo SwA

(kcal mole ') (cm3 mole 1

Temperature range

Radical source Refer- ences

sec *) °C

CH:! COOCH:i

CH.jCOOCD.,

CH,C00CD:1 C2 H5 COOC2 H,

ch;! ocooch:!

Acids and acid

anhydrides

CH,COOD

(CH:i C0)2 0

10 ±0.5

10 ± 0.5 10 ±0.5

14 ±1

8.2

8.9 ±0.7

10.2

9.6

11.2

11.4

11.4

11.8

11.3

10.29 ±0.34

11.1

11.3

63-216

151-340

145-350

151-274

72-344

122-253

CH.jCOOCH.,

CH,COCH,

CR( COOCD:i

CH.jCOCH.,

C2 H5 COOC2 H.

CH.jCOCH.j

P

P

P

P

P

P

120

121 122

121

123

106

105-285 CH.jCOOD P

107-196 (CH:i C0)2 0 P

124

125

Ethers and epoxides

CH.jOCH.,

(C2 H5

)2 0

f(CH..)2 CH]2 0

"CK

ch2 -ch2 Peroxides

CH,OOCH,

((CH:j )CHO)2

((CH:! )XO)2

Nitriles

CH.S CN

C2 H.CN

Metal alkyls

Hg(CH.,)

2

Cd(CH,)2

(y) (0

9.5 ±0.2

8.4 ±1.5

10 ± 2

10.8 ± 1.0

11.5

11.0

11.8

9.75 ±0.5 12.14

(y) 7.3 ±0.4 11.1

9.6 ±2 11.0

10.0

11.7 ±0.3

14.5 ±2.5

12.56

A =4.7 x 10 5

/. = 5.3 x 106

12.4

(y) 10.0 ±0.5

(y) 8.5 ±0.5

11.5

11.5

(h) 10.8 9.0 ±0.5

10.8 ±0.3

i0.2 ± 1.0 ^

(y) 10.0 ± 1.0

11.7 11.3

11.7 10.97

/. =4.8x 10 7 11.22

14 ±2 12.8

108-198 CHjCOCH., P

100-250 Hg(CH,)2 P

199-292 CH..OCH, -H

500-560 CD.CDO T

145-179 D.T.B.P. T

179-339 CD.jCOCD.,

43

42

12629

127

43

100-200 Hg(CH ) 42

124-185

26

77

130-155

103-145

CH,OOCH,

((CH.,)

2 CHO)2 ((CH,)2 CHO)2

D.T.B.P.

D.T.B.P.

P

P

T

T

128

129

129

10537

100-290

133-297

CD.,COCD„

CD,COCD:j

130

130

25-250

25-250

28-251

160-238

407

125-202

HglCH.j),

Hg(CH,)2 Hg(CH,)2 CH,COCH,

Hg(CH.,)2 CD^COCD,

131 13133

110

132 110

200-275 Cd(CH:i ) 2 P 5

49
Metathetical Reactions of Methyl Radicals — Continued

Reactants Notes E Temperature range

Radical source Refer- ences

(kcal mole-1

) (cm3 mole_1 sec^ 1

) °C

Halogenated alkanes

CFH, (v) 8.7 ±0.3 11.6 125-211 CH,COCH, P 133, 135

(y) 11.8 11.2 193-331 CDjCOCD., P 134

CF2 H2 (V) 6.2 ±0.3 10.5 129-192 CH,COCH, P 133, 135

(y) 10.4 11.0 122-301 CD,COCD, P 134 CFH (y) 9.8 9.8 142-293 CD.COCD, P 136, 137

10.4 10.0 144-309 cd;! cocd, P 138

G2F.H (y) 9.7 10.8 135-318 CD,COCD:i P 138

c,f7 h (y> 9.3 10.6 129-323 CD.COCD, P 138 CH;iCl (v) 9.4 ±0.3 11.8 127-207 CH.jCOCH, P 133, 135 CH2C12 (v) 7.2 ±0.3 11.3 129-211 CH,COCH, P 133, 135

CHCl.j (v) 5.8 ±0.3 10.8 132-203 CH,COCH, P 133, 135

6.8 30 CH;t COCH;! P 139

CH.Br (v) 10.1 ±0.3 12.5 121-208 CH:i COCH, P 133, 135

CH,Br2 (v) 8.7 ±0.3 12.2 126-177 CH.COCH, P 133, 135

Hydrides of nitrogen.

oxygen, and sulphur

NH, 9.8 ±0.9 1 1.00 ±0.42 110-180 CH,N„CH., P 88. 68

10.0 ±0.2 10.9 ±0.1 144-308 CH.t COCH, P 76

(y) 10.0 ±0.4 10.8 180-339 cd:! cocd. P 43

ND, 10.9 ±0.9 11.00 ±0.42 110-180 ch,n2 ch:1 P 88, 68

n2 h7 5.00 ±0.1 1 1 .00 ± 0.05 110-180 ch,n2 ch:) P 88. 68

h2 o (b) 24.7 13.57 8 h2 s 2.6 11.4 50-140 CH,COCH, P 140

(w) 3.6 12.1 200-360 CH:i CHO P 141

Hydrogen halides

HC1 2.3 ±1 11.6 28-150 CH.jCOCH., P 142

(e) 4.51 12.1 143, 144

HI (x) 2.30 12.50 260-316 CH..I/HI T 145

FLUORINE ATOM TRANSFER

14.1 13.3 157-168 D.T.B.P.. T

50
Metalhetical Reactions of Methyl Radicals — Continued

Reactants Notes E logiuY Temperature range

Radical source Refer- ences

(kcal mole ') (cm3 mole~ l sec' 1

) °C

CHLORINE ATOM TRANSFER

CC14 12.9 ±0.7 13.4 90-145 D.T.B.P. T 146, 147 cc1

3 cn 10.4 ±1.0 12.9 90-145 D.T.B.P. T 147

C2 C16 10.1 ±0.9 11.8 90-145 D.T.B.P. T 146. 147

CsH5 CC13 7.6 ±0.8 10.3 90-145 D.T.B.P. T 147 CC13 COCC13 9.7 ±0.8 12.6 90-145 D.T.B.P. T 146, 147

BROMINE ATOM TRANSFER

CF.,Br 12.5 ±1.0 13.3 90-145 D.T.B.P. T 147

CF2 Br2 6.4 ±1.0 11.0 90-145 D.T.B.P. T 147

CClgBr 7.1 ±0.9 13.2 90-145 D.T.B.P. T 147

CCl2 Br2 7.6 ±1.1 13.8 90-145 D.T.B.P. T 147

CBr4 7.9 ±1.1 14.2 90-145 D.T.B.P. T 147

IODINE ATOM TRANSFER

1

A = 2x 10 12 —

2

x 10 13 20 CH.,I/02 p 148

A = 2.0 X 10 16 50 CH,I P 149

(aa) 1.50 13.0 260-316 CH.jI/HI T 145

A =1.1 X 10 13 60 CH.jI F.P. 165

7.5 ±1.0 13.8 90-145 D.T.B.P. T 147

OXYGEN ATOM TRANSFER

o2 (bb) k = 5. 3 x 108 498 ch:) coch,/o2 t 150 no2 5.7 12.75 1150-1590 CH^NO., ignition 151

GROUP-TRANSFER REACTIONS

14CH.. + CH..COCH3 (ee) A =T5.2 X 106 350 CH.jCOCH., P 16 = ,

'4CH3COCH, + CH.,

CH., + CF.jCOCF., 5.7 ±1.5 9.3 163-245 ch,n2 ch, P. T 171 = CH.jCOCF., + CF.t 6.2 ± 1.0 11.4 85-210 CF.COCF., P 172

7.0 ±1.0 11.7 48-240 CH.jCOCH.,/ 173 CF.jCOCF., P

51
Metathetical Reactions of Methyl Radicals — Continued

Reactants Notes E logio A Temperature range

Radical source Reference

(kcal mole 1

) (cm 3 mole

1 sec" ') °C

CH, + C2 F5 COC2 F5 7 ± 1 184-240 (C2 F5

) 2 CO p 174 = CH.,COC2F5 + C2F5

CD.( + CH,HgCH, k = 8. (?X 105 180 CD.,COCD: , P 175, 176 = CD:1 HgCH.t + CH:j

CH. + CD.SH^H.SH 7.6 10.73 130-200 CH.,COCH;j P 74 + CD,

CH.t + CF.jCOCH., 14 150-350 CF..COCH., P 109 = C2H6 + CF:t CO

CH„ + CH„C0C0CH„ 5.6 10.7 100-200 ch3 cococh:! p 114 = CH.( COCH, + CH..C0

6.6 100-200 ch:) cococh: , p 115

CH.( + CH,CH:CHCHO 7.45 ±1.30 11.8 ±0.4 120-250 CH;) COCH:i P 177 ^H.CHtCHCH., + CH0

CH., + CH.,HgCH.t 1.0 7 175-220 CH.jHgCH, P 131, 178 = C2 Hs + (Hg + CH,t )

Ratios of Rate Constants (Methyl Radicals)

(i) Reactions with halogens and hydrogen halides.

Reaction Notes £>-£2 logio A 1 /A 2 k,/k2 Temperature range

Radical source Reference

( kcal mole -1

) °C

(1) CH., + HBr = CH ) + Br

(2) CH., + Br2 = CH.,Br + Br 2.0 -0.7 37-210 CH,/Br/HBr P 167, 168

(1) ch., + hi = ch4 + i 0.15 280 CH.,I/HI T 152, 154

(2) CH., + I

2 = CH.! I + I 0.13 ±0.03 270-310 CH,I/HI T 153, 154

1.3 ±0.5 -0.38 126-295 CH,COCH, P 155

0.8 ±1.0 -0.50 ±0.40 260-316 CH.,I/HI T 145

0.75 -0.64 83-192 CH.,I/HI P 164

(1) CH, + HBr — CH4 + Br

(2) CH, + I

2 = CH,I + I 0.8 ±0.3 60 CH,I/HBr/I2 P 163

1.37 ±0.26 -0.30 ±0.13 80-164 CH.COCH, P 156

0.95 -0.88 83-192 CH,I/HBr P 164

(1) CH.i + HBr = CH ) + Br

(2) CH., + HI = CH4 + I (cc) 1.1 ±0.4 0.15 25 CH3I/HBr P 157

52
Ratios of Rate Constants (Methyl Radicals) — Continued

(i) Reactions with halogens and hydrogen halides. — Continued

Reaction Notes Ei-E2 logiod i!A‘i kilk2 Temperature range

Radical source Reference

(1) ch., + ch.,i = ch4 + ch2 i

(2) CH3 + HI = CH4 + I

(kcal mole~ ') 0.03 °C

270-310 CH:i I/HI T 153, 154

(1) CH., + HC1 = CH4 + C1

(2) CH, + I

2 = CH.,I + I (dd) 2.4 -1.46 98-160 CH.,I/HC1 P 164

(1) CH., +

1

2 = CH.,I +

1

(2) CH, + NO = CH: ,NO 6 25 ch.,i/no p 158

(1) CH, + CH =CH4 + CH,

(2) CH., + I

2 = CH.,I + I 6.5 ±2 -3.8 30-252 ch:! i/ch4 /i2 p 161

(ii) Miscellaneous reactions.

Reaction Notes E\ E2 log io A 1 M2 Al/A-2 Temperature range

Radical source Reference

(1) CH.i + CH,CD, = CH.! D

+ ch.s cd2 (2) ch., + ch,cd, = ch4 +ch2 cd3

( kcal mole~ 1

)

0.6 ±0.04 -0.32

°C

328-424 ch,n2ch3 T 159, 27

(1) ch3 + ch3 cd2 ch3 = ch3 d + ch3 cdch-

(2) CH + CH CD CH = CH4 + ch2 cd2 ch,

-1.7 -0.66 312-421 ch: ,n2 ch:1 T 159, 27

(1) CH., + (CH3)3 CD = CH3 D + (CH.jl.jC

(2) CH.! + (CH.! ).

1 CD = CH4 + CH2(CH: ,)2 CD

-2.3 -0.51 305-359 ch.,n2 ch: , T 159, 27

(1) CD.j + CD2 COCD2 CH2 CH.i = CD4 + [C5 D4 Hs OJ

(2) CD4 + CD.! COCD2 CH2 CH.i = CD3 H + [C5 D5H4 0]

0.7 35-144 cd.,cocd2 ch2 ch,' P. T

36

(1) CH.i + CH.! OCH2 CH.! = CH4 + [C.

s h70]'

(2) CH., + CH^OCH., = CH4 + ch2 och3

4 to 12 525 CH.,OCH., T 160

(1) CH., + HCHO = CH4 + HCO

(2) CH, + CH.,OCH., = CH4 + ch2 och; ,

3 507 CH,OCH., T 9

(1) ch., + o2 = hcho + oh

(2) CH., + 02 + M= CH:l 02 + M

1.0 x 10- 8 kilk2 [M] = 0.49

25

162 ch.,i/o2 p

ch3 n2 ch.,/o2 P

170

162

53
Notes

(a) When corrected, these activation energies are 10.5 and 12.2 kcal respectively (see ref. 11).

(b) This value was used (without a source being quoted), in the range 1000-1500 °C.

(c) Use of the more recent activation energy for CH3+CH3CHO

gives E = 12.0 kcal (see ref. 11). (d) For a re-analysis of these results see reference 15.

(e) Calculated from the reverse reaction.

(f) Assuming an activation energy of 9.2 kcal/mole for the

reaction CD3 + CDg CDO = CD4 + CD3 CO.

(g) Assuming A:=10 12 - 3 exp (— 13,600/RT) for the reaction ch3 +c2 d8 =ch;! d + c2 d5

. (h) The quantities were not calculated in this manner by the

original authors.

(i) Assuming A'=10 u - 7 exja (— 10,800/RT) for the reaction CH3 + CH3 HgCH3 = CH4 + CH3HgCH2

.

(j) Pyrolysis of a series of methyl metal derivatives.

(k) Assuming A = 10 118 exp (— 12.000/RT) for die reaction ch.,+d2 =ch,d+d.

(l) No distinction made between o, m, and p xylenes.

(m) Calculated assuming a zero secondary isotope effect.

(n) These are not the values quoted by the authors, but cor- rected (see ref. 67) for arithmetical errors.

(o) No significant quantities of CH3 D were formed, when

acetone was photolyzed in presence of (CD2

) 2 NH.

(p) These values are doubtful.

(q) No significant quantities of CH.( D formed during the photolysis of CH.s COND2

. (r) Calculated assuming the parameters for abstraction from

the — NH2 group, are as for those in hydrazine.

(s) See also references 69, 70, 75, 79, 80, and 88.

(t) Several other studies are in excellent agreement with those

listed. See references 1, 23, 59, 65. 74, 106, 107, and 108.

(u) “A” factor doubtful.

(v) The results for CC14

, CH.,C19 , and CH:! C1 are invalid: the others are to be regarded with some suspicion (see ret. 135). (w) Assuming A = 10 11

9

exp (— 7600/RT) for the reaction CH3 + CH:1 CHO = CH4 + CH CO.

(x) The authors consider the activation energy to be ~ 1 kcal

too high.

(y) The attacking radical is CD3

. (z) The variations reported within these series may be spurious

as variations in E are compensated by variations in A.

(aa) The authors consider the activation energy to be ~ 1 kcal

too high.

(bb) The products of this reaction are HCHO and OH.

(cc) Activation energy difference calculated assuming identical A factors.

(dd) “Hot” methyl radicals may have played an important part

in this system.

(ee) Assuming A=10116 exp (— 9800/RT) for the reaction ch3 + ch3 coch3 = ch4 + CH2 COCH3

.

References (Methyl Radical Reactions)

1. Majury and Steacie, Disc. Faraday Soc. 14, 45 (1953).

2. Majury and Steacie, Can. J. Chem. 30, 800 (1952).

3. Whittle and Steacie, J. Chem. Phys. 21, 993 (1953).

4. Phibbs and Darwent, Trans. Faraday Soc. 45, 541 (1949).

5. Anderson and Taylor. J. Phys. Chem. 56, 498 (1952).

6. Davison and Burton, J. Am. Chem. Soc. 74, 2307 (1952).

7. Gesser and Steacie, Can. J. Chem. 34, 113 (1956). y 8. Intezarova, Kondratiev, and Mukhoyan. Kinetika i Kataliz,

5, 585 (1964).

9. Benson and Jain, J. Chem. Phys. 31, 1008 (1959).

10. Skinner and Ringrose, J. Chem. Phys. 43, 4129 (1965).

11. Wijnen and Steacie, Disc. Faraday Soc. 14, 118 (1953).

12. Rebbert and Steacie, Can. J. Chem. 32, 113 (1954).

13. Chanmugam and Burton, J. Am. Chem. Soc. 78, 509 (1956).

14. McNesby, Gordon, and Smith, J. Am. Chem. Soc. 78, 1287

(1956).

15. Pritchard and Pritchard, Can. J. Chem. 41, 3042 (1963).

16. Dainton, Ivin, and Wilkinson, Trans. Faraday Soc. 55,

929 (1959).

17. Creak, Dainton, and Ivin, Trans. Faraday Soc. 58, 326

(1962).

18. Trotman-Dickenson, “Gas Kinetics,” p. 199 (Butterworths,

1955).

19. Trotman-Dickenson and Steacie, J. Phys. Chem. 55, 908

(1951).

20. McNesby and Gordon, J. Am. Chem. Soc. 76, 4196 (1954).

21. Wijnen, J. Chem. Phys. 23, 1357 (1955). 22. Dainton, Ivin, and Wilkinson. Trans. Faraday Soc. 53,

1204 (1957).

23. Dainton and McElcheran, Trans. Faraday Soc. 51, 657

(1955).

24. Brodskii, Kalinenko, and Lavrovskii, J. Chem. Soc. 4443

(1960).

25. Blackmore and Hinshelwood, Proc. Roy. Soc. 271A, 34

(1963).

26. Trotman-Dickenson, Birchard, and Steacie, J. Chem.

Phys. 19, 163 (1951).

27. McNesby, J. Phys. Chem. 64, 1671 (1960).

28. McNesby and Gordon, J. Am. Chem. Soc. 77, 4719 (1955).

29. Rice and Varnerin, J. Am. Chem. Soc. 77, 221 (1955).

30. Jackson, McNesby, and Darwent, J. Chem. Phys. 37,

1610 (1962).

31. Jackson and McNesby, J. Am. Chem. Soc. 83, 4891 (1961).

32. Gomer, J. Am. Chem. Soc. 72, 201 (1950).

33. Rebbert and Steacie, J. Chem. Phys. 21, 1723 (1953).

34. Smith and Taylor, J. Chem. Phys. 7, 390 (1939). 35. Jones and Steacie, Can. J. Chem. 31, 505 (1953). 36. McNesby and Gordon, J. Am. Chem. Soc. 78, 3570 (1956). 37. Blake and Kutschke, Can. J. Chem. 37, 1462 (1959).

38. Blake, Henderson, and Kutschke, Can. J. Chem. 39, 1920

(1961).

39. Rice and Vanderslice, J. Am. Chem. Soc. 80, 291 (1958). 40. Blackmore and Hinshelwood. Proc. Roy. Soc. 268A, 36

(1962). 41. Rebbert and Steacie, Can. J. Chem. 32, 40 (1954). 42. Phibbs and Darwent, Can. J. Res. 28B, 395 (1950). 43. Trotman-Dickenson and Steacie, J. Chem. Phys. 19, 329

(1951). 44. McNesby and Gordon, J. Am. Chem. Soc. 79, 825 (1957). 45. Gordon, Smith, and Drew, J. Chem. Phys. 36, 824 (1962). 46. Russell and Bernstein, J. Chem. Phys. 30,607 (1959). 47. Gordon, Can. J. Chem. 43, 570 (1965). 48. Gordon and Smith, J. Phys. Chem. 66, 521 (1962). 49. Trotman-Dickenson and Steacie, J. Chem. Phys. 19,

169 (1951).

50. Miyoshi and Brinton. J. Chem. Phys. 36, 3019 (1962).

51. Rice and Varnerin, J. Am. Chem. Soc. 76, 2629 (1954). 52. Drew and Gordon. J. Chem. Phys. 31, 1417 (1959). 53. Mulcahy, Williams, and W’ilmhurst, Austral. J. Chem.

17, 1329 (1964).

54. Taylor and Smith. J. Chem. Phys. 8, 543 (1940).

55. Szwarc and Roberts, Trans. Faraday Soc. 46, 625 (1950).

56. Price and Trotman-Dickenson, J. Chem. Soc. 4205 (1958).

57. Price and Trotman-Dickenson, Trans. Faraday Soc. 53,

939 (1957).

58. Price and Trotman-Dickenson. Trans. Faraday Soc. 53,

1208 (1957).

59. Burkley and Rebbert, J. Phys. Chem. 67, 168 (1963).

60. Cher, J. Phys. Chem. 68, 1316 (1964).

61. Sanders and Rebbert, J. Phys. Chem. 67, 170 (1963).

62. Burr and Strong. J. Chem. Phys. 43, 1432 (1965). 63. Burr and Strong, J. Am. Chem. Soc. 86, 5065 (1964).

64. Wunderlich and Rebbert. J. Phys. Chem. 67, 1382 (1963).

65. Harrison and Shannon. Can. J. Chem. 41, 2455 (1963).

66. Kerr and Trotman-Dickenson, J. Chem. Soc. 3322 (1957).

54
67. Brinton, Can. J. Chem. 38, 1339 (1960).

68. Gray and Thynne, 10th Int. Comb. Symp., p. 435, Comb.

Inst., Pittsburgh (1965).

69. Gray and Thynne, Trans. Faraday Soc. 59, 2275 (1963).

70. Gray, Jones, and Thynne, Trans. Faraday Soc. 61, 474

(1965).

71. Kozak and Gesser, J. Chem. Soc. 448 (1960).

72. Cher, Hollingsworth, and Sicilio, J. Phys. Chem. 70, 877

(1966). * 73. Shaw and Thynne, Trans. Faraday Soc. 62, 104 (1966).

74. Greig and Thynne, Trans. Faraday Soc. 62, 379 (1966).

75. Gray and Jones, Trans. Faraday Soc. 62, 112 (1966).

76. Edwards, Kerr, Lloyd, and Trotman-Diekenson, J. Chem.

Soc. 621 (1966).

77. Brinton and Volman. J. Chem. Phys. 20, 25 (1952).

78. Klemm, Can. J. Chem. 43, 2633 (1965).

79. Gray and Jones, Trans. Faraday Soc. 61, 2161 (1965).

80. Gray and Jones, Can. J. Chem. 43, 3485 (1965).

81. Cafferata, Kerr, and Trotman-Diekenson. J. Chem. Soc. 1386 (1965).

82. Spall and Steacie, Proc. Roy. Soc. 239A, 1 (1957).

83. Thynne, Trans. Faraday Soc. 60, 2207 (1964).

84. Jones and Steacie, J. Chem. Phys. 21, 1018 (1953).

85. Ausloos and Steacie, Can. J. Chem. 32,593 (1954).

86. Toby, J. Am. Chem. Soc. 82, 3822 (1960).

87. Toby and Kutschke, Can. J. Chem. 37, 672 (1959). 88. Gray and Thynne, Trans. Faraday Soc. 60, 1047 (1964).

89. Toby and Nimoy, J. Phys. Chem. 70, 867 (1966).

90. Gowenlock, Can. J. Chem. 42, 1936 (1964).

91. Hoare, Trans. Faraday Soc. 49, 1292 (1953). 92. Brinton and Volman. J. Chem. Phys. 20, 1053 (1952).

93. Ausloos and Steacie, Can. J. Chem. 33, 31 (1955). 94. Dodd, Can. J. Chem. 33, 699 (1955). 95. Calvert, Pitts, and Thompson, J. Am. Chem. Soc. 78,

4239 (1956). 96. Birrell and Trotman-Diekenson, J. Chem. Soc. 2059 (1960). 97. Kerr and Calvert. J. Phys. Chem. 69, 1022 (1965). 98. Pritchard, Hsia, and Miller, J. Am. Chem. Soc. 85, 1568

(1963).

99. Volman and Brinton. J. Chem. Phys. 22, 929 (1954). 100. Trotman-Diekenson and Steacie, J. Chem. Phys. 18,

1097 (1950).

101. Saunders and Taylor, J. Chem. Phys. 9, 616 (1941). 102. Gomer and Kistiakowsky, J. Chem. Phys. 19, 85 (1951). 103. Mandelcorn and Steacie, Can. J. Chem. 32, 331 (1954). 104. Jacquiss, Roberts, and Szwarc, J. Am. Chem. Soc. 74,

6005 (1952). 105. Pritchard, Pritchard, and Trotman-Diekenson, J. Chem.

Soc. 1425 (1954). 106. Thynne and Gray, Trans. Faraday Soc. 58, 2403 (1962). 107. March and Polanyi, Proc. Roy. Soc. 273A, 360 (1963).

108. Brinton, J. Am. Chem. Soc. 83, 1541 (1961). 109. Sieger and Calvert, J. Am. Chem. Soc. 76, 5197 (1954). 110. Oswin, Rebbert, and Steacie, Can. J. Chem. 33, 472

(1955). 111. Wijnen. J. Chem. Phys. 22, 1631 (1954). 112. Pitts and Norman, J. Am. Chem. Soc. 76, 4815 (1954). 113. Duncan and Trotman-Diekenson, J. Chem. Soc. 4672

(1962). 114. Blacet and Bell, Disc. Faraday Soc. 14, 70 (1953).

115. Bell and Blacet, J. Am. Chem. Soc. 76, 5332 (1954).

116. Ausloos and Steacie, Can. J. Chem. 33,39 (1955). 117. Thynne, Trans. Faraday Soc. 58, 676 (1962). 118. Thynne, Trans. Faraday Soc. 58, 1394 (1962).

119. Thynne, Trans. Faraday Soc. 58, 1533 (1962). 120. Wijnen, J. Chem. Phys. 27, 710 (1957). 121. Wijnen, Can. J. Chem. 36, 176 (1958). 122. Wijnen, J. Chem. Phys. 28, 939 (1958). 123. Wijnen, J. Am. Chem. Soc. 80, 2394 (1958). 124. Ausloos and Steacie, Can. J. Chem. 33, 1530 (1955). 125. Ausloos, Can. J. Chem. 34, 1709 (1956).

126. Marcus, Darwent, and Steacie, J. Chem. Phys. 16, 987

(1948). 127. Long and Skirrow, Trans. Faraday Soc. 58, 1403 (1962). 128. Thynne and Gray, Trans. Faraday Soc. 59, 1149 (1963). 129. McMillan, J. Am. Chem. Soc. 83, 3018 (1961). 130. Wijnen, J. Chem. Phys. 22, 1074 (1954). 131. Gomer and Noyes, J. Am. Chem. Soc. 71, 3390 (1949). 132. Kallend and Purnell, Trans. Faraday Soc. 60, 103 (1964). 133. Raal and Steacie, J. Chem. Phys. 20, 578 (1952). 134. Pritchard, Bryant, and Thommarson, J. Phys. Chem.

69, 664 (1965). 135. Ridge and Steacie, Can. J. Chem. 33, 396 (1955). 136. Pritchard, Pritchard, Schiff, and Trotman-Diekenson,

Trans. Faraday Soc. 52, 849 (1956). 137. Pritchard, Pritchard, Schiff, and Trotman-Diekenson,

Chem. and Ind. 896 (1955). 138. Pritchard and Thommarson, J. Phys. Chem. 68, 568

(1964). 139. Cvetanovic, Raal, and Steacie, Can. J. Chem. 31, 171

(1953).

140. Imai and Toyama, Bull. Chem. Soc. Japan 33, 652 (1960). 141. Imai and Toyama, Bull. Chem. Soc. Japan. 33, 1120

(1960).

142. Cvetanovic and Steacie, Can. J. Chem. 31, 158 (1953). 143. Pritchard, Pyke, and Trotman-Diekenson, J. Am. Chem.

Soc. 77, 2629 (1955). 144. Pritchard, Pyke, and Trotman-Diekenson, J. Am. Chem.

Soc. 76, 1201 (1954).

145. Flowers and Benson, J. Chem. Phys. 38, 882 (1963). 146. Tomkinson, Galvin, and Pritchard, J. Phys. Chem. 68,

541 (1964). 147. Tomkinson and Pritchard, J. Phys. Chem. 70, 1579

(1966). 148. Christie, Proc. Roy. Soc. 244A, 411 (1958). 149. Souffle, Williams, and Hamill, J. Am. Chem. Soc. 78,

917 (1956). 150. Barnard and Honeyman, Proc. Roy. Soc. 279A, 244

(1964).

151. Hiraoka and Hardwick, J. Chem. Phys. 39, 2361 (1963). 152. Benson and O’Neal, J. Chem. Phys. 34, 514 (1961). 153. Sullivan, J. Phys. Chem. 65, 722 (1961).

154. Ogg, J. Am. Chem. Soc. 56, 526 (1934). 155. O’Neal and Benson. J. Chem. Phys. 36, 2196 (1962). 156. Fettis and Trotman-Diekenson, J. Chem. Soc. 3037 (1961). 157. Farren, Gilbert. Linnett and Read, Trans. Faraday Soc. 60, 740 (1964).

158. Christie and Frost, Trans. Faraday Soc. 61, 468 (1965). 159. Rice and Vanderslice. J. Am. Chem. Soc. 80, 291 (1958).

160. Anderson and Benson, J. Chem. Phys. 36, 2320 (1962). 161. Willard and Harris, J. Am. Chem. Soc. 76, 4678 (1954). 162. Wenger and Kutschke, Can. J. Chem. 37, 1546 (1959). 163. Anderson and Kistiakowsky, J. Chem. Phys. 11, 6 (1943). 164. Williams and Ogg, J. Chem. Phys. 15, 696 (1947). 165. Davidson and Carrington, J. Am. Chem. Soc. 74, 6277

(1952).

166. Ausloos and Steacie, Can. J. Chem. 33, 1062 (1955). 167. Kistiakowsky and Van Artsdalen, J. Chem. Phys. 12,

469 (1944). 168. Benson and Buss, J. Chem. Phys. 28, 301 (1958). 169. Batt and Cruickshank, J. Phys. Chem. 70, 723 (1966). 170. Heicklen and Johnston, J. Am. Chem. Soc. 84, 4030

(1962). 171. Pritchard and Steacie, Can. J. Chem. 35, 1216 (1957). 172. Alcock and Whittle, Trans. Faraday Soc. 61, 244 (1965). 173. Giles and Whittle, Trans. Faraday Soc. 61, 1425 (1965). 174. Price and Kutschke, Can. J. Chem. 38, 2128 (1960). 175. Rebbert and Ausloos, J. Am. Chem. Soc. 86, 2068 (1964). 176. Rebbert and Ausloos, J. Am. Chem. Soc. 85, 3086 (1963). 177. Allen and Pitts, J. Phys. Chem. 70, 169 (1966). 178. Trotman-Diekenson, “Gas Kinetics,” p. 237 et seq. (Butterworths, London, 1955).

55
Difluoromethylene Radicals

Reaction Notes E logi oA Temperature range

Radical source Reference

CF2 + 02 = CO + 2F + 0

( kcal mole-1

) 14.98 (cm3 mole-1 sec

-1

) 12.30 > °C

1307-2117 c2f4/o2 s.t. r 1

References

1. Modica and La Graff, J. Chem. Phys. 43 , 3383 (1965).

56
Trifluoromethyl Radicals

Reactants Notes E \ogi0A Tempera- Radical source Reference

ture range

HYDROGEN ATOM TRANSFER

4

Hydrogen (kcal mole J

) (mole-1

cc. sec

-1

) °C

h2 9.5 ±0.7 11.86 59-158 CF.COCF, 1 8.8 11.60 219-346 CF.jN.CF.j 2

(a) 25.1 11.89 832-1011 3 HD 10.5 ±1.5 11.78 102-174 cf.cocf, 1 HD 10.2 ±1.5 11.35 102-174 cf:! cocf:! 1 d2 10.2 ±0.7 11.45 86-196 CF.COCF., 1 9.7 11.44 220-346 CF.rN2 CF:j 2

Alkanes

ch4 10.3 ±0.5 11.70 122-251 CF.jCOCF; 4

10.6 11.73 170-310 CF.jCHO 5

9.5 ±2 11.2 30-350 CF.jCOCF., 6

11.0 ±0.1 11.98 84-261 CF.jCOCF.j 7 11.3 ±0.5 11.96 ±0.22 153-295 CF.COCF., 8

11.0 11.98 CHD:i 10.5 ±0.3 11.04 55-354 cf:! cocf:! 9

CHD;, 12.75 ±0.3 11.33 55-354 cf:( cocf:! 9

CD, 12.1 ±2.1 11.18 106-287 cf:! cocf:( 7

c2 hk 7.5 ±0.5 11.68 81-216 CF.jCOCF., 4

7.5 11.63 220-350 CF:! N2 CF;i 2

c:! h8 6.2 11.67 200-310 CF.j N2 CF.j 2

6.5 ±0.5 11.75 27-119 CF:i COCF:! 10

«-C4 H,o 5.1 ±0.3 11.15 29-93 CF.jCOCF'., 10

5.5 ±1.0 10.9 30-350 CF.jCOCF., 6

5.3 11.46 200-310 CF:j N2 CF:j 2

iso-C4 HI0 4.7 ±0.3 11.15 28-84 CF.jCOCF., 10

4.7 11.17 170-240 CF.jCHO 5

(CH,).,CD 7.4 ±1.0 12.48 62-208 CF.COCF., 7

neo-C5 H]2 7.6 11.76 250-320 CF:( N2 CF.t 2

CH.t C(CH.t )2CH2 CH, 1.7 10.22 250-300 cf:! n2 cf:! 2

Cyclo-Alkanes

cyclo-C.H 10 4.7 11.54 210-300 cf:! n2 cf;! 2

cyclo-Cg H ]2 5.0 ±0.2 11.44 19-91 CFjCOCF., 11

57
Trifluoromethyl Radicals — Continued

Reactants Notes E lognv4 Temperature range

Radical source Reference

(kcal mole~ l ) (mole -1

cc. sec

-1

) °C

Aromatic hydrocarbons

CA 6.3 ±0.20 11.35 23-86 CF.( COCF, 11

(b) 7.7 11.44 cf,n2 cf. 2 cs h5ch:! (b) 6.0 11.33 CF.l N2 CF.i 2 5.91 ±0.30 11.59 ±0.20 27-110 CF,CbCF., 12

5.37 ±0.26 11.10 25-81 CF,COCF:1 11 c6h5 cd, 5.8 ±0.4 10.13 22-72 CF:i COCF:l 13

°-C6H4(CH;j )2 5.55 ±0.54 11.68 37-68 CF.COCF, 11

Halogenated Aromatics

Ch H5 C1 5.5 ±0.3 10.56 20-118 CF,COCF:i 14 CH.Br b 5 5.9 ±0.5 11.53 23-95 CF:i COCF:i 14

cb h5 i 4.5 ±0.1 10.86 75-150 CF,COCF, 14

C,.H_CH,C1 bo 2 8.0 ±0.3 12.46 67-151 CF:i COCF, 14

C6H5 CC13 8.8 ±0.6 12.55 104-171 CF.COCF, 14

CfiFjCH., 6.38 10.75 CF.COCF, 15

Aldehydes

CH.CHO 4.2 10.84 170-250 CF.CHO 5 CF.pHO 8.4 11.73 150-400 CF.CHO 5

Ketones

CH.COCH, 8.0 11.51 250-320 CF,N„CF, 2 6.9 ± 0.

1

10.77 29-169 CF.COCF, 16

8.27 ±0.17 11. 52 ±0.08 85-240 CF:t COCF:i 17, 16 CF:j COCH:i 6.6 11.3 25-350 CF.tCOCH.i 18

C.H-.COCF:, 7.2 ±0.5 9.7 158-304 C6H5COCF, 19

lalogenated Methanes

CH.jCl 10.6 ±0.2 12.11 ±0.08 144-400 CF:t COCF:i 8

CHXL 7.6 ±0.1 11. 19 ±0.08 85-204 CFtCOCF.i 20 CHCFi 6.6 ±0.1 11. 04 ±0.06 94-296 CF.COCF, 20

5.3 ±0.1 10. 16 ± 0.07 35-338 CF|N>CF-i 21 6.3 ±0.6 1 1 .98 118-251 CF:! COCF, 7

58
Trifluoromethyl Radicals — Continued

Reactants Notes E logi oA Temperature range

Radical source Reference

( kcal moie~ l ) ( mole ~ 1 cc. sec

~

') °C

CDC1* 9.0 ± 0.4 11.78 65-264 CF: iCOCE;) 7 CH.jBr (d) 10.9 ±0.3 12.19 ± 0. 14 150-260 CF.tCOCF.i 8

(e) 9.9 ±0.1 11. 63 ±0.06 150-260 CF.iCOCF;) 8 CH:i l 7.5 ±0.3 10.63 ± 0. 16 55-210 cf:i cocf| 8

Hydrogen halides

and hydrogen

sulphide

HC1 5.1 ±0.5 11.05 20-205 CF,COCF, 26

HBr 2.9 ±0.5 11.78 CF,COCF, 26

k = 3.

00 X o 26 CF;i COCF;i 22 h2 s 3.88 ±0.26 11.65 ±0.16 63-100 CE.s COCF, 27

CHLORINE ATOM TRANSFER (i)

Cl2 3.6 ±0.5 12.89 126-235 cf:) cocf;! 26

CH.S C1 3= 17 CF:) COCF:j 20 CH2 C12 11.8 ± 0.7 11.49 ±0.1 306-449 CF.i COCF.i 20

CHC1, (f) 12.0 ±0.2 12.08 ±0.1 95-296 CF^COCF., 20

11.0 ±0.4 11.33 ±0.2 35-338 CF.! N2 CF.i 21

CCL, 9.3 ±0.4 11.79 ±0.2 122-288 CF.jN.CF., 21

10.4 ±0.1 12.57 ±0.04 96-240 CF:i CbCF;! 20

c6h5 ci ± 13 20-118 CF.COCF., 14

c6h5 ch2 ci ± 13 67-151 cf:! cocf:! 14

c6h5 cci3 9.7 ±0.5 12.49 104-171 CF.jCOCFj 14

BROMINE ATOM TRANSFER

Br2 0.7 ±0.5 12.36 178-327 CF;) COCF.t 26 CH:i Br (d) 8.4 ±0.1 10.83 ±0.06 150-260 CF.jCOCE., 8

(e) 8.1 ±0.2 10.41 ±0.10 150-260 CF;i COCF:j 8

C,.H,Br (g) 1.7 ± 1.1 7.91 23-95 CF.jCOCF., 14

Cfi F Br o o (g) 0.3 ±0.6 7.38 39-107 cf;! cocf.( 14

HBr (a) 84.2 10.71 832-1011 23

247-168 0-67 —5

59
Trifluoromethyl Radicals — Continued

Reactants Notes E log io A Temperature range

Radical source Reference

( kcal mole -1

) (mole -1

cc. sec

-1

) °C

IODINE ATOM TRANSFER

I

2 0.0 ±0.5 12.42 CF:i COCF.j 26

CH,I 3.3 ±0.15 9.59 ±0.08 55-210 CF3 COCF3 8

c6 h5

i 3.1 ±0.6 10.33 75-150 CF,COCF:j 14

OXYGEN ATOM TRANSFER

n2 o (h) 24.0 13.15 316-375 CF3COCF3 24

Ratios of Rate Constants (Trifluoromethyl Radicals)

Reaction Notes Ei~E2 log 10 A \/A 2 Temperature range

Radical source Reference

(kcal mole - 1 ) °C

(1) CF., + Br2 -0.52 ±1.88 0.93 ± 0.60 361-431 CF.,H thermal 22 = CF.,Br + Br bromination

(2) CF., + HBr — 2.17 ±0.16 0.58 ±0.08 55-334 CF.,COCF., 25 = CF.,H + Br

(1) CF., + I

2 = CF.,I + I

(2) CF., + HBr -2.98 ±0.12 0.64 ±0.06 85-230 CF.,COCF., 25 = CF3H + Br

(1) CF., + CHD., = CF.,H + CD,,

(2) CF3 + CHD3 -2.2 -0.29 55-354 CF3COCF3 9 = CF3D + CHD2

(1) cf., + ch2 d2 = CF,H + CHD2 (2) CF., + CH2 D2 In ki//c2 == In 1.400 + 0.42 X IO6 //

12 727-1067 CF3N2 CF3 28 = cf.,d + ch2 d

Notes

(a) CF Br inhibition of H2 /02 shock tube ignition.

(b) Values less reliable than others quoted by the same

authors.

(c) Results combined with data from reference 16.

(d) At low (25mm Hg) CH Br pressures.

(e) At high (180mm Hg) CH.,Br pressures.

(f) This result is preferred to that obtained with CF3N2 CFr

(g) “A” factor unreasonable.

(h) Result described as “semi-quantitative.”

(i) For data involving fluorine atom transfer, see reference 29.

References

1. Ayscough and Polanyi, Trans. Faraday Soc. 52, 960 (1956).

2. Pritchard, Pritchard, Schiff, and Trotman-Dickenson,

Trans. Faraday Soc. 52, 849 (1956).

3. Skinner and Ringrose, J. Chem. Phys. 43, 4129 (1965).

4. Ayscough, Polanyi, and Steacie, Can. J. Chem. 33, 743

(1955).

5. Dodd and Smith, J. Chem. Soc. 1465 (1957).

6. Pritchard, Pritchard, and Trotman-Dickenson, Chem. and

Ind. 564 (1955).

7. Carmichael and Johnston, J. Chem. Phys. 41, 1975 (1964).

60
8. Alcock and Whittle, Trans. Faraday Soc. 61, 244 (1965).

9. Sharp and Johnston, J. Chem. Phys. 37, 1541 (1962).

10. Ayscough and Steacie, Can. J. Chem. 34. 103 (1956).

11. Charles and Whittle, Trans. Faraday Soc. 52, 849 (1956).

12. Holmes and Kutschke, Trans. Faraday Soc. 58, 333

(1962).

13. Charles, Pearson, and Whittle, Trans. Faraday Soc. 57,

1356 (1961).

14. Giles and Whittle, Trans. Faraday Soc. 62, 128 (1966).

15. Charles, Pearson, and Whittle, Trans. Faraday Soc. 59,

1156 (1963).

16. Pritchard and Dacey, Can. J. Chem. 38, 182 (1960).

17. Giles and Whittle, Trans. Faraday Soc. 61, 1425 (1965).

18. Sieger and Calvert, J. Am. Chem. Soc. 76, 5197 (1954).

19. Smith and Calvert, J. Am. Chem. Soc. 78, 2345 (1956).

20. Alcock and Whittle, Trans. Faraday Soc. 62, 134 (1966).

21. Alcock and Whittle, Trans. Faraday Soc. 62, 664 (1966).

22. Corbett, Tarr and Whittle, Trans. Faraday Soc. 59, 1609

(1963).

23. Skinner and Ringrose, J. Chem. Phys. 43, 4129 (1965).

24. Bell and Kutschke, Can. J. Chem. 42, 2713 (1964). 25. Tucker and Whittle, Trans. Faraday Soc. 61, 866 (1965).

26. Amphlett and Whittle, Trans. Faraday Soc. 62, 1662

(1966).

27. Arthur and Bell, Can. J. Chem. 44, 1445 (1966). 28. Johnston and Tschuikow-Roux, J. Chem. Phys. 36, 463

(1962). 29. Stewart and Cady, J. Am. Chem. Soc. 77, 6110 (1955).

61
Metathetical Reactions of Halogenated Methyl Radicals

Reactants Notes E logi oA Tempera- Radical source Reference

ture range

(i) Reactions of CFH2 Radicals

Hydrogen atom (kcal mole 6 (cm3 mole 1 sec *) °C

transfer

cfh2 cocfh2 (a) 8.0 ±0.1 10.71 100-300 cfh2 cocfh2 p 1

(ii) Reactions of CF2 C1 Radicals

Hydrogen atom

transfer

cyclo-C5 H10

Chlorine atom

transfer

CF2 C1C0CF2 C1

(b)

(b)

(b)

5.3 ±0.4

4 ± 1 ~ 3

50-227

20-180

20-184

CF2 C1C0CF2 C1 p

cf2 cicocf2 ci p

cf2 cicocf2 ci p

2

34

II

(I (iii) Reactions of CC13 Radicals

]l Hydrogen atom

transfer

h2 (c) 11.3 ±0.5 14.86 248-302 CCl:j Br P 5 ch3ch2 ch2 ch. (d) 11.2 10.1 146-257 CCl3 Br P 6, 7

CH.j CH2 CH2 CH.! (d) 7 5 9.9 146-257 CCl.,Br P 6, 7

HBr (d) A: = 2.76 X 1011 190 CCl.jBr P 6

Chlorine atom

transfer

Cl2 (d) 5.3 12.86 70-155 CHCyCl, P 8, 9

CCl.jBr 18.6 ± 1 225-294 CCl.jBr P 10

17.4 ±1 248-302 CCl:! Br p 5

CC13C0CC13 7 ± 1 107-252 CCl3COCCl:t P 11

-m

62
Ratios of Rate Constants (Trichloromethyl Radicals)

Reactants Notes Ei — E2 logioAi/A? Temperature range

Radical source Reference

(1) CCl;i ±n-C4 H10 =sec-C4 Hg +CCl.j H

(kcal TOo/e-1

) °C

(2) CCl.t + n-C4 H10 = P-C4H9 + CC1:| H

(1) cci.,-Uc4 h,0 =(CH.! ).

! C + CC1.! H

-3.08 ±0.46 0.43 ±0.25 197-294 CCl;i Br p 7

(2) CCl., + n-C4 H10 =sec-C4H9 +CCl.,H

-2.40 0.30 132-189 CCl.jBr p 7

Notes

(a) Calculated assuming A:=1014 cm3 mole-1 sec

-1 for the combination of CFH2 radicals.

(b) Calculated assuming k = 10 14 cm3 mole -1 sec

-1 for the combination of CF2 CI radicals.

(c) Calculated assuming &=1010- 7 cm3 mole -1 sec

-1 for the combination of CCT.s radicals.

(d) Calculated assuming A:=1011 - 80 cm3 mole -1 sec

-1 for the combination of CCI3 radicals.

References

1. Pritchard, Venugopalan, and Graham, J. Phys. Chem. 68,

1786 (1964).

2. Majer, Phillips, and Robb, Trans. Faraday Soc. 61, 122

(1965).

3. Bowles, Majer, and Robb, Trans. Faraday Soc. 58. 1541

(1962).

4. Bowles, Majer, and Robb, Trans. Faraday Soc. 58, 2394

(1962).

5. Hautecloque, Compt. Rend. 25 7, 131 (1963).

6. Tedder and Watson, Trans. Faraday Soc. 62, 1215 (1966).

7. McGrath and Tedder, Bull. Soc. Chim. Beiges 71 , 772

(1962).

8. Chiltz, Martens, and Mahieu, Nature 180, 1068 (1957).

9. Chiltz, Mahieu, and Martens, Bull. Soc. Chim. Beiges 67,

33 (1958).

10. Hautecloque, Compt. Rend. 256, 2601 (1963).

11. Hautecloque, Compt. Rend. 254, 3671 (1960).

Review

1. Chiltz, Goldfinger, Huybrechts, Martens, and Verbecke,

Chem. Rev. 63, 355 (1963).

63
Relative Rate Constants (Formyl Radicals)

Reactants Notes Ei Ei logio A i/A 2 kilk2 Temperature range

Radical source Refer- ences

(1) hco + no„ = hno2 + co

(2) hco + no2 = hco2 + no

( kcal mole-1

)

0.65 0.5

°C

100-220 ch2 o/no2 t 1, 2

(1) HCO(+ M) = CO + H(+ M)

(2) HC0 + 02 = C0 + H02 2.7X 10-9 cm -3 mole

36 CH:! COCH:i /02 P 3

References

1. Shaw, J. Chem. Soc. 1517 (1964).

2. Pollard and Wyatt, Trans. Faraday Soc. 45, 760 (1949).

3. Pearson, J. Phys. Chem. 67, 1686 (1963).

64
Metathelical Reactions of Methoxy Radicals

Reactants Notes E log 10 A Tempera- Radical source Referture range ences

HYDROGEN ATOM TRANSFER

Alkanes (kcal mole *) (cm3 mole 1 sec *) °C

ch4 (a) 11.0 11.8 125-250 15

c2 h6 (b) 7.1 11.5 200-400 CH3 OOCH3 T 1, 2, 3

c,h8 (b) 5.2 11.3 200-400 CH3 OOCH3 T 1, 2, 3

n-C4 H]0 (c) (b) 2.9 10.5 200-400 CH3 OOCH3 T 1, 2, 3

iso-C4 H]0 (b) 4.1 11.0 190-260 CH3 OOCH3 T 1, 2, 3

(CH.( )4 C (b) 7.3 11.8 200-300 CH3 OOCH3 T 1 , 2

Cyclo-Alkanes

cyclo-C:j H6 (b) 9.7 12.2 200-400 CH3 OOCH3 T 1 , 2

EstersHCOOCH, 8.2 12.2 124-185 CH:j OOCH:) T 4, 5 CH3COOCH3 ~ 4.5 63-216 CH3 COOCH3 P 6 , 14 CH3COOCD3 (d) ~ 5 30-201 CH3 COOCD3 P 7, 14

Ratios of Rate Constants (Methoxy Radicals)

Reactants Notes E1 E2 logio A 1/A2 Temperature rangeRadical source References

(1) CH3O + CH3OH = CH30H + CH2 0H

(2) CH3O + HCHO

= CH30H + HC0

(1) CH3O + HCHO

= CH30H + HC0

(2) 2CH3O = CH3OH + HCHO (f)

(kcal mole -1

)

3.0 — 4.3

Ai/A 2

1/2 = 10 3 68 exp (— 3000/RT)

°C

155-180

50-135

CH3OOCH3 P

D.T.B.P. T. P

8 , 12

9

(1) CH30 + 02 = CH2 0

+ ho2

( 2) 2 CH..O = CH OH

+ ch2 o (f) kjk^ = 0.59 room temp. ch3i/o2 p 10

(1) CH3 + CH2 (OCH.( )2 = CH30H + [C3H7 02]

( 2 ) CH.,b = H + CO + H2 A 1 /A2 = 1.14 x 105 cm3 mole -

1

459 CH2 (OCHa

)2 T 11

65
Notes

(a) Calculated from the back reaction.

(b) The A factors were deduced by a semi-empirical method

by Berces and Trotman-Dickenson (ref. 1). The original work

contained an arithmetical mistake that resulted in an over- estimate of log A of 0.3 units.

(c) This value seems likely to be incorrect.

(d) The reactant radical in this case is CD.s O.

(e) For further data on methoxy radicals see reference 13.

(f) Units are cm3/2 mole - 1/2 sec -1/2

.

References

1. Berces and Trotman-Dickenson, J. Chem. Soc. 348 (1961).

2. Shaw and Trotman-Dickenson, J. Chem. Soc. 3210 (1960).

3. Shaw and Trotman-Dickenson, Proc. Chem. Soc. 61 (1959).

4. Thynne and Gray, Trans. Faraday Soc. 59, 1149 (1963).

5. Thynne and Gray, Proc. Chem. Soc. 295 (1962).

6. Wijnen, J. Chem. Phys. 27, 710 (1957).

7. Wijnen, J. Chem. Phys. 28, 939 (1958).

8. Takezaki and Takeuchi, J. Chem. Phys. 22, 1527 (1954).

9. Hoare and Wellington, 8th. Int. Comb. Symp., p. 472

(Williams and Wilkins, 1962).

10. Heicklen and Johnston, J. Am. Chem. Soc. 84, 4030

(1962).

11. Molera, Fernandez-Biarge, Centeno, and Arevalo, J. Chem.

Soc. 2311 (1963).

12. Takezaki, Miyazaki, and Nakahara, J. Chem. Phys. 25 , 536 (1956).

13. Dever and Calvert, J. Am. Chem. Soc. 84, 1362 (1962).

14. Wijnen, J. Chem. Phys. 28, 271 (1958).

15. Shaw and Thynne, Trans. Faraday Soc. 62 , 104 (1966).

Reviews

1. Gray and Williams, Chem. Rev. 59, 239 (1959).

66
Metathetical Reactions of Methylthio Radicals

Reactants Note E logio A Temperature range

Radical source Refer- ences

HYDROGEN ATOM TRANSFER

CH4 (a)

{kcal mole ') 18.2 (cm3 mole 1 sec *) 12.1 °C

130-200 1 CH;j CH0 6.8

4.8

11.9

12.0 189-396 CH.s CHO/CH.! SH

400-440 CH.jCHO/CHjSH

Notes

(a) Calculated from the reverse reactions.

References

1. Greig and Thynne, Trans. Faraday Soc. 62, 379 (1966).

2. Birrell, Smith, Trotman-Dickenson, and Wilkie, J. Chem.

Soc. 2807 (1957).

3. Imai and Toyama, Bull. Chem. Soc. Japan 33, 1408 (1960).

67
Reactions of Chloroformyl Radicals

Reactions Notes E log io A Temperature range

Radical source References

(kcal mole-1

) (cm3 mole~ l sec _I

) °C

COCl + Cl2 = COCl2 2.96 12.4 25-55 CO/Cl2 P 1 + C1 COCl + NOCl = Cl2 + CO + NO

(a) 3.1 10.8 15-450 5

(or COCl2 + NO) 1.14 13.68 25-55 C0/C12/N0C1 p 2 C0C1 + 02 = C02 + CIO

3.3 10.9 20-200 Cl2 /02/C0 P 3, 4

Notes

(a) Review of literature data.

References

1. Burns and Dainton, Trans. Faraday Soc. 48, 39 (1952).

2. Burns and Dainton, Trans. Faraday Soc. 48, 52 (1952).

’ 3. Rollefson, J. Am. Chem. Soc. 55, 148 (1933).

4. Trotman-Dickenson, “Gas Kinetics,” p. 259 et seq. (Butter-

/

! worths, 1955).

5. Bodenstein, Brenschede, and Schumacher, Z. Phys. Chem.

40B, 121 (1938).

68
Metathetical Reactions of Cyano Radicals

Reactions Notes E logio A Temperature range

Radical source; References

(kcal mole -1

) (cm 3 mole - 1 sec

-1

) °c

h2 + cn=hcn + h ~ 7 D.F. 1

cicn + cn=c2 n2 + ci 6.0 13.05 1727-2527 C1CN S.T, 2

C2N2 + CN = products 2.1 10.86 28-174 c2 n2 f.p. 3 o2 +cn=nco + o A = 4.(>X 10 12 room temp. c2 n2/o2 f.p. 5

A = 5.5 X 10 12

j room temp. c2 n2/o2 F.p. 3

Ratios of Rate Constants

Reactions Notes Ei-E2 logio A 1 IA 2 kjkt Temperature range;

Radical source References

(1) ch4 + cn = ch,

+ HCN

(2) C2 H6 + CN = C2 H5 + HCN

(kcal mole -1

)

3.7 ±0.2 1.31

°C

30-150 ICN P 4

(1)

C2 H6 + CN = C2 H5 + HCN

(2) C3Hg + CN = n-C3H7 + HCN -0.1 ±0.2 0.00 30-150 ICN P 4

(1) c2 h6 + cn = c2 h5 + HCN

(2) C3H8 + CN = i-C3H7 + HCN -0.1 ±0.3 0.04 30-150 ICN P 4

(1) C3 H8 + CN = n-C3 H7 + HCN

(2) C3 H8 + CN = t-C 3H7 + HCN -0.1 ±0.3 0.08 30-150 ICN P 4

References

1. Hartel and Polanyi, Z. Phys. Chem. Bll, 97 (1930).

2. Schofield, Tsang, and Bauer, J. Chem. Phys. 42, 2132

(1965).

3. Paul and Dalby, J. Chem. Phys. 37, 592 (1962).

4. Goy, Shaw, and Pritchard, J. Phys. Chem. 69, 1504 (1965).

5. Basco, Proc. Roy. Soc. 283A, 302 (1965).

69
Ratios of Rate Constants (Ethynyl Radicals)

(i) Reactions of the type (1) C2 H + RH = C2 H2 + R

(2) C2 H + BrC2 H = C4H2 + Br.

RH Notes k il k 2 Temperature

Radical source References

Alkanes °C

ch4 0.020 27 BrC2 H P 1

c2h6 0.40 27 BrC2 H P 1

n-C4 Hi0 1.05 27 BrC2 H P 1

iso-C 4 H10 1.25 27 BrC2 H P 1

(CH3

)4C 1.1 27 BrC2 H P 1

(CH3

) 3 C.C(CH3)3 1.2 27 BrC2 H P 1

Cyclo-alkanes

cyclo-C3 H6 0.21 27 BrC2 H P 1

cyclo-C 4 H8 1.35 27 BrC2 H P 1

spiro-C 5 H8 0.64 27 BrC2 H P 1

cyclo-C 5 H10 2.1 27 BrC2 H P 1

cyclo-C6 H12 3.2 27 BrC2 H P 1

cyclo-C6 D12 2.3 27 BrC2H P 1

Halogenated alkanes

C2H3 C1 0.14 27 BrC2 H P 1

(ii) Reactions of the type (1) C2 H+ RH = C2 H2 + R

(2) C2 H + CH2 :CHCH2 CH3 =c2 h2 +c4 h7

RH Notes A‘l/A'2 Tempera- Radical source Reference

ture

Alkenes °C

CH2 :CHCH3 0.63 27 BrC2 H P 2

cis-CH3 CH:CHCH3 1.04 27 BrC2 H P 2

trans-CH3 CH:CHCH3 1.06 27 BrC2 H P 2 CH2 :C(CH3

) 2 0.90 27 BrC2 H P 2 CH2 :CHCH2 CH2 CH3 1.7 27 BrC2 H P 2 CH2 :CHCH(CH3

)2 1.22 27 BrC2 H P 2

References

1. Tarr, Strausz, and Gunning, Trans. Faraday Soc. 61 , 1946 2. Tarr. Strausz, and Gunning, Trans. Faraday Soc. 62 , 1221

(1965). (1966).

70
Metathetical Reactions of Ethyl Radicals

Reactants Notes

_i

E logio'4 Temperature range

Radical source Reference

HYDROGEN ATOM TRANSFER

Hydrogen ( kcal mole -1

) (cm 3 mole~ 1 sec -1

) °C

h2 (a) 11.5 ± 1 1 4.05 12.19 752-917 H2/02 ignition S.T. 2

(b) 11.3 ±0.5 11.51 83-322 (C 2 D,)

2 CO p 3

15.9 12.8

d2 13.3 ±0.5 12.0 54-287 (C 2H5

) 2 CO p 1

Alkanes

n-C4 H10 15.2 11.77 420-530 n-C4Hio T 4

(b) 10.4 11.03 106-325 (C2 D5

) 2 CO p 5

J

- C4 H10 (b) 8.9 10.62 87-319 (C2d5

)2co p 5

neo-C5 H12 (b) 12.6 11.25 86-324 p 5

cyclo-C6 H12 (b) 10.4 ±0.5 11.42 ±0.2 99-293 (C2 D5

) 2 CO p 3

« C6 H14 (b) 10.1 ±0.5 11.14 ±0.2 87-252 p 3

n-C7 H16 10.6 ±0.4 11.69 ±0.2 124-200 (C2 H5

) 2 CO p 6

Alkenes

l,5-CflH 10 6.3 ±0.4 10.1 ±0.2 71-175 (C2 h5

) 2 co p 7

1-C 7 Hh 8.3 ±0.5 11.19 ± 0.3 85-200 (C 2 Hs

) 2 CO p 6

i-c8 h16 8.3 ±0.2 11.19 ±0.3 85-180 (C2H5

) 2 CO p 6

7.5 ±0.5 10.6 ±0.3 66-152 (C2 H5

) 2 CO p 9

trans 4-C8H16 8.7 ±1.0 11.5 ±0.6 85-165 (C2 H5

) 2 CO p 6

(CH;i ) 2 C:CHCH:

C(ch3

)2 7.6 ±0.4 11.1 ±0.2 53-147 (C2 H5

) 2 CO p 9

Cyclo alkenes

cyclohexadiene,-l,3- 5.4 ±0.5 10.6 ±0.3 25-160 (C 2 H5

) 2 CO p 9, 8

cyclohexadiene,-l,4- 5.8 ±0.1 11.3 ±0.1 50-140 (C 2 Hs

) 2 CO p 10

cyclohexene 8.2 ±0.5 11.5 ±0.3 23-250 (C2 H5

)2 CO p 6

7.5 ±0.4 10.2 ±0.2 40-210 (C2 H5

)2 CO p 10

cycloheptatriene 6.5 ±0.5 10.9 ±0.3 50-130 (C2 H5

) 2 CO p 10

cyclooctatetraene 8.6 ±1.2 11.6 ±0.7 50-130 (C2 Hs

) 2 CO p 10

cyclooctadiene,-l,5. 6.8 ±0.7 10.9 ±0.4 60-130 (C 2 H5

) 2 CO p 10

71
Metathelical Reactions of Ethyl Radicals — Continued

Reactants Notes E logio A Temperature range

Radical source Reference

(kcal mole-1

) (cm 3 mole ~ 1 sec~ *) °C

Alkynes

j-C 7 Hi2 7.6 ±0.2 10.9 ±0.1 23-180 (C2H5

) 2 CO p 6

Aldehydes

C2 H5 CHO 7.6 ±1.0 11.5 134-156 D.T.B.P. T 11 5.9 10.8 91-315 C2 H5 CHO p 12

6.3 100-175 c2 h5cho p 12, 13

Ketones

CH3COC2 H5 8.0 ±0.1 11.0 79-234 ch3 coc2 h5 p 16

(C2 H5

) 2 CO 7.4 10.9 25-225 (C2 H5

) 2CO p 14, 21

7.6 11.0 41-158 (C2 h5

)2n2 p 15

7.8 ±0.2 11.1 ±0.1 50-215 (C2 Hs

) 2CO p 6

8.9 11.7 75-170 (C2 h5

) 2co P 17 (CH3 CD2

) 2 CO (c) 11.7 11.4 24-365 (CH3 CD2

) 2 CO p 18

(CH3 CD2

) 2CO (c) 8.7 11.6 24-365 (CH3 CD2

) 2 CO p 18, 19

9.2 ±0.4 11.1 ±0.1 24-365 (CH3 CD2

) 2 CO p 19

(C2 Ds

) 2 CO (b) 9.6 ±0.4 11.3 160-314 (C2 D5

) 2 CO p 19 9 0 ±0.5 10.95 50-324 (C2 D5

)2 CO p 5

C2 F5COC2 Hs 6.8 10.85 100-250 c2 f5 coc2 h5 p 37

c3f7 coc2 h5 7.2 10.9 80-362 c3 f7 coc2 h5 p 20

EstersHCOOC2 H5 7.8 10.6 77-230 ch3coch3 p 17

c2 h5cooc2 h5 9.8 11.5 108-344 c2 h5cooc2 h5 p 22

C2 H5 COOCH2 CH:

ch2 5.8 ±1.4 9.7 ±0.8 79-160 (C2 H5

) 2 CO P 23

Azo-compounds

(C 2 H5

) 2 N2 7.5 10.9 74-178 (C2 h5

) 2 n2 p 24

8.0 ±0.2 11.4 27-175 (C2 H5

) 2 N2 p 25

Metal alkyl

(C2 H5

) 2 Hg 6.2 10.3 75-200 (C2 H5

) 2 Hg P 26

Hydrogen halide

HI

4

1.1 11.92 263-303 hi/c2h5

i t 27

72
Metathetical Reactions of Ethyl Radicals — Continued

Reactants Notes E logio^f Temperature range

Radical source Reference

(kcal mole* 1 ) (cm3 mole -1 sec

-1

) °C

* CHLORINE ATOM TRANSFER

Cl2 1.0 13.1 28

IODINE ATOM TRANSFER

(d) 0.2 12.50 263-303 hi/c2h5

i t 27

OXYGEN ATOM TRANSFER

r;

2 o (e) 31.0 17.8 553-588 c2 h6/n2 o T 29

Ratios of Rate Constants (Ethyl Radicals)

Reaction Notes E\—Ei logiod 1 /A 2 kilk2 Temperature range

Radical source Reference

(1) C2 H5 + HBr = C2 H6 + Br

(2) C2 H5 +Br2 =C2 H5 Br+Br

(kcal mole~ 1 )

0 -0.22

°C

30-90 C2 H6/Br2 /HBr P 30, 36

(1) c2h5 +hi=c2 h6 + i

(2) C2H5 +

1

2 = C2 H5

I +

1

0.90 -0.58

0.15 0.13 ±0.03

260

250-280

263-303

c2 h5i/hi t

c2 h5 i/hi t

c2 h5 i/hi t

33, 32

31, 32

27

(1) C2H5 + HBr = C2 H6 + Br

(2) C2H5 + I

2 =C2 H5

I + I 2.29 ±0.08 0.23 ± 0.04 55-115 ch3coc2h5 p 34

(1)

C2 H5 + I

2 = C2 H5I + I

(2) C2 H5 + 02 = C2 H502 13 25 c2 h5i/o2 p 35

(1) c2 h5 + i

2 = c2h5

i + i

(2) C2 H5 + NO = C2 H5 NO 7 25 c2 h5 i/no p 35

Notes

(a) Estimated from the reaction D2 + C2 H5

, assuming the

difference in activation energies to be equal to the difference

of the zero-point energies.

(b) The attacking radical is C„D5

. (c) The attacking radical is CH3 CD2

. (d) Calculated, assuming the activation energy of 0.2 kcal/mole.

(e) This A factor seems improbably high.

References

1. Wijnen and Steacie, J. Chem. Phys. 20, 205 (1952).

2. Skinner and Ringrose, J. Chem. Phys. 43 , 4129 (1965).

3. Boddy and Steacie, Can. J. Chem. 39, 13 (1961).

4. Purnell and Quinn, Proc. Roy. Soc. 270A, 267 (1962).

5. Boddy and Steacie, Can. J. Chem. 38, 1576 (1960).

6. James and Steacie, Proc. Roy. Soc. 244A, 289 (1958).

7. James and Troughton, Trans. Faraday Soc. 62, 145 (1966).

73
8. Brown and James, Proc. Chem. Soc. 81 (1962).

9. Brown and James, Can. J. Chem. 43, 1102 (1965).

10. Brown and James, Can. J. Chem. 43, 660 (1965).

11. Volman and Brinton, J. Chem. Phys. 22, 929 (1954).

12. Kerr and Trotman-Dickenson. J. Chem. Soc. 1611 (1960).

13. Blacet and Pitts, J. Am. Chem. Soc. 74, 3382 (1952).

14. Kutschke, Wijnen, and Steacie, J. Am. Chem. Soc. 74,

714 (1952).

15. Ausloos and Steacie, Can. J. Chem. 32, 593 (1954).

16. Ausloos and Steacie, Can. J. Chem. 33, 1062 (1955).

17. Thynne, Trans. Faraday Soc. 58, 676 (1962).

18. Wijnen and Steacie, Can. J. Chem. 29, 1092 (1951).

19. James and Steacie, Proc. Roy. Soc. 245A, 470 (1958). 20. Pritchard and Thommarson, J. Phys. Chem. 69, 1001

(1965).

21. Brinton and Steacie, Can. J. Chem. 33, 1840 (1955). 22. Wijnen, J. Am. Chem. Soc. 80, 2394 (1958). 23. James and Troughton, Trans. Faraday Soc. 62, 120 (1966).

24. Ausloos and Steacie, Bull. Soc. Chim. Beiges. 63, 87

(1954). 25. Cerfontain and Kutschke, Can. J. Chem. 36, 344 (1958). 26. Ivin and Steacie, Proc. Roy. Soc. 208A, 25 (1951). 27. Hartley and Benson, J. Chem. Phys. 39, 132 (1963). 28. Goldfinger, Huvbrechts, Martens, Meyers, and Olbrechts,

Trans. Faraday Soc. 61, 1933 (1965). 29. Kenright and Trenwith, J. Chem. Soc. 2079 (1959). 30. Anderson and Van Artsdalen, J. Chem. Phys. 12, 479

(1944).

31. Sullivan, J. Phys. Chem. 65, 722 (1961). 32. Ogg, J. Am. Chem. Soc. 56, 526 (1934). 33. Benson and O’Neal, J. Chem. Phys. 34, 514 (1961).

34. Fettis and Trotman-Dickenson, J. Chem. Soc. 3037 (1961). 35. Christie and Frost, Trans. Faraday Soc. 61, 468 (1965). 36. Benson and Buss, J. Chem. Phys. 28, 301 (1958). 37. Thommarson and Pritchard. J. Phys. Chem. 70, 2307

(1966).
Perfluoroethyl Radicals

Reactants Notes E log io A Tempera- Radical source Reference

ture range

HYDROGEN ATOM TRANSFER

(kcal mole _ *) ( mole 1 cc sec

~

') °C

h2 11.9 12.72 137-237 '(C 2F5

) 2 CO 1

(a) 12.4 ±0.2 13.20 146-313 c2 f5 cho 2

d2 (a) 12.6 ±0.2 12.45 135-339 c2f5 cho 2

14.1 ±0.3 13.08 154-259 < c2f5

) 2 n2 3 ch4 10.6 11.62 150-272 (C2 F5

) 2 CO 1

c2h6 8.7 ±0.2 12.18 84-226 (C2 f5

) 2 n2 3

cyclo-C6 H12 6.0 ±0.2 12.18 28-132 (C2f5

)2 n2 3

CF3 CHO 9.7 ±0.2 12.40 138-220 (C2F5

) 2 N2 3

c2 f5 cho 4.5 ±0.2 10.49 27-307 c2f5 cho 4

4.9 ±0.2 10.74 135-339 c2f5cho 2 ch3 coch3 8.4 ±0.2 11.71 82-220 (C 2 F5

) 2 N2 3

c2f5 coc2 h5 5.6 ±0.2 11.34 50-250 C2F5 COC2 H5 5

Notes References

(a) These results are less reliable than those obtained from

perfluoro ketone systems.

1. Price and Kutschke, Can. J. Chem. 38, 2128 (1960).

2. Pritchard and Foote, J. Phys. Chem. 68, 1016 (1964).

3. Pritchard, Dacey, Kent, and Simonds, Can. J. Chem. 44,

171 (1966).

4. Pritchard, Miller, and Foote, Can. J. Chem. 40, 1830(1962).

5. Thommarson and Pritchard, J. Phys. Chem. 70, 2307 (1966).

247-168 0-67—6

75
V

e:

t

t

f

Metathetical Reactions of Halogenated Ethyl Radicals

Reactions Notes E logio/1 Temperature range

Radical source Reference

CHjjCHjjCI + C^ = CH2 C1CH2 C1 + C1

(kcal mole -1

) 0

(cm 3 mole -1 sec

-1

) °C

CH2 :CH2 /C12 P 1, 2

c2 h3 ci2 +ci2 = CH2 C1CHC12 + C1

(c) 0.92 ±0.05 11.75 ±0.2 25-55 CH2 :CHC1/C12 P 1, 2, 3

CHC^CHCl + Cl, = CHC12CHC12 + C1

2.74 ±0.6 11.7 ±0.3 30-65 cis-CHCBCHCl/C^ P 4, 3

c2 hci4 +ci2 = CHC12 CC13 + C1

(b) 5.1 ±0.2 11.5 ±0.2 80-140 CHC1:CC12 /C12 P 5, 3, 12

C2 C15 + C12 = C2 C16 + C1 (a) 5.5 11.3 87-247 CCl2 :CCyCl2 P 6, 7

CF2 CF2 C1 + C12 = CF2 C1CF2 C1 + C1(d) 0.8 30-60 CF2 :CF2 /C12 P 13

C2 F3 C12 + C12 = C2F3 C13 + C1

(e) 2.3 30-60 CF2 :CFC1/C12 P 13

CFC^CFCl + CL, = CFC12 CFC12 + C1(f) 5.35 ±0.3 30-70 CFClrCFCl/Clj P 14

C2F4 Br+ HBr= C2 F4 Br2 + H

51.2 13.07 855-1013 H2/02/C2F4 Br2 S.T.

i15

Ratios of Rate Constants (Halogenated Ethyl Radicals)

Reactions Notes Ei Ei loglO cl l/sl 2 kjki Temperature range

Radical source References

(kcal mole -1

) °C

(1) C2 H4 Br= C2 H4 + Br

(2) C2 H4 Br + HBr = C2 H5 Br + Br 14 ±2 25-54 C2 H4/HBr 16, 18 y radiation

(1) C2 H4 Br = C2 H4 +Br

(2) C2 H4 Br + Br2 = C2H4 Br2 + Br 6.1 60-80 C2 H4 /Br2 P 17

76
Notes

(a) Data on this reaction can also be found in references 8 to 11.

(b) The reactant radical is probably CHCLCClf.

(c) The reactant radical is probably CH2C1CHC12. (d) Calculated assuming zero activation energy for the combination of CF2 CF2 C1 radicals.

(e) Calculated assuming zero activation energy for the combination of C2F3CI2 radicals.

(f) Calculated assuming zero activation energy for the combination of CFC12 CFC1 radicals.

References

1. Dainton, Lomax, and Weston, Trans. Faraday Soc. 58, 308

(1962).

2. Ayscough, Cocker, Dainton, and Hirst, Trans. Faraday Soc. 58, 318 (1962).

3. Ayscough, Cocker, Dainton, Hirst, Lomax, and Weston,

Proc. Chem. Soc. 244 (1961).

4. Ayscough, Cocker, Dainton, and Hirst, Trans. Faraday Soc. 58, 295 (1962).

5. Dainton, Lomax, and Weston, Trans. Faraday Soc. 53, 460

(1957).

6. Dusoleil, Goldfinger, Maheiu-Van der Auwera, Martens, and

Van der Auwera, Trans. Faraday Soc. 57, 2197 (1961).

7. Adam, Goldfinger, and Gosselain, Bull. Soc. Chim. Beiges

65,549(1956).

8. Adam and Goldfinger, Bull. Soc. Chim. Beiges 65, 561

(1956).

9. Adam, Dusoleil, and Goldfinger, Bull. Soc. Chim. Beiges

65,942(1956).

10. Ackerman, Chiltz, Goldfinger, and Martens, Bull. Soc. Chim. Beiges 66, 325 (1957).

11. Chiltz, Maheiu, and Martens, Bull. Soc. Chim. Beiges 67,

33 (1958).

12. Chiltz, Dusoleil, Goldfinger, Huybrechts, Mahieu, Martens,

and Van der Auwera, Bull. Soc. Chim. Beiges 68, 5 (1959).

13. Castellano, Bergamin, and Schumacher, Z. Phys. Chem.

27, 112 (1961).

14. Vallana, Castellano, and Schumacher, Z. Phys. Chem. 46,

294 (1965).

15. Skinner and Ringrose, J. Chem. Phys. 43, 4129 (1965).

16. Armstrong and Spinks, Can. J. Chem. 37, 1210 (1959).

17. Schmitz, Schumacher, and Jager, Z. Phys. Chem. 5 IB,

281 (1942).

18. Oldershaw and Cvetanovic, J. Chem. Phys. 41, 3639

(1964).

Review

1. Chiltz, Goldfinger, Huybrechts, Martens, and Verbecke,

Chem. Rev. 63, 355 (1963).

77
Ratios of Rate Constants (Carbonylcarbene Radicals)

Ratios of the form (1) CCO + C.,02 = Polymer + nCO

(2) CCO + Cn H2n = Cn+1 H2n + CO

Where Cn H2n is an olefine, and Cn+ iH2n is the diene and/or alkyne formed by addition of a carbon atom

Olefine Notes Ai/A-2 Temperature

Radical source Reference

c2 h4 (a) 1.4 0 C3 02 p 1 (a) 1.26 0 C3 02 p 2

(b) 2.79 0 C3 02 p 2

CH.s CH:CH2 (a) 3.93 0 C3°2 p 2

(b) 9.72 0 c3 o2 p 2 CH2 :CHCH2 CH3 (a) 13.14 0 c3 o2 p 2

(b) 38.91 0 Cg02 p 2 CH2 :C(CH.s

) 2 (a) 14.04 0 C3 02 p 2

cis-CH3 CH:CHCH3 (a) 8.03 0 C3 02 p 2

trans-CH3CH:CHCH3 (a) 14.33 0 c3 o2 p 2

(CH3

) 2 C:CHCH3 (a) 34.38 0 C3 02 p 2

(CH3

)2 C:C(CH3) 2 (a) 67.20 0 C3 02 p 2

Notes References

(a) Photolysis at 2537 A.

(b) Photolysis at > 3100 A.

1. Bayes, J. Am. Chem. Soc. 84, 4077 (1962).

2. Baker, Kerr, and Trotman-Dickenson, J. Chem. Soc. 975A

(1966).
Metathetical Reactions of Acetyl Radicals

Reactants Notes E logioA Temperature range

Radical source Reference

i

2 + ch,co = CH:1 COI +

1

( kcal mole~') 0

( cm3 mole~ l sec

-1

) 12.6 °C

222-268 CH..COI/HI T 1

Ratios of Rate Constants (Acetyl and Trifluoroacetyl Radicals)

Reaction Notes E\ — £2 logio/1 1/4 2 kith Temperature rangeRadical source Reference

(1) CH,CO = CH, + CO

(2) CH,CO + HBr = CH.,CHO + Br

(kcal mole-1

) ~ 13

°C

100-300 CH.jCOCH., P 2

(1) CH,CO = CH, + CO

(2) CH3 CO + 02 = CH3 0 + C02 ~ 9 -4.68

(mole cm-3

) ch3 coch3/o2 P 3

(1) ch,co + hi = ch3 cho + i

(2) ch3 co + i

2 = ch3 coi + i 1.5 -0.47 222-268 ch3coi/hi t 1

(1) CF.,CO=CF.j + CO

(2) CF3 CO + Br2 = CF.,COBr + Br

(a) 6.0 -4.7 19-251 CF3COCF3/Br2 P 4

Notes

(a) Values very doubtful.

References

1. O'Neal and Benson, J. Chem. Phys. 37, 540 (1962).

2. Ridge and Steacie, Can. J. Chem. 33, 383 (1955).

3. Cerfontain and Kutschke, J. Am. Chem. Soc. 84, 4017

(1962).

4. Tucker and Whittle, Trans. Faraday Soc. 61 , 484 (1965).

79
Ratios of Rate Constants (Ethoxy Radicals)

NOTE: For further data on ethoxy radicals see reference 4. 3. Wijnen, J. Am. Chem. Soc. 82, 3034 (1960).

4. Heicklen and Johnston, J. Am. Chem. Soc. 84, 4394 (1962). References

1. Jolley, J. Am. Chem. Soc. 79, 1537 (1957).

2. Cerfontain and Kutschke, J. Am. Chem. Soc. 84, 4017

( 1952).

Review

1. Gray and Williams, Chem. Rev. 59, 239 (1959).
Metathetical Reactions of Allyl Radicals

Reactants Notes E logioA Temperature range

Radical source Reference

HYDROGEN ATOM TRANSFER

(kcal mole-1

) cyclo-C 5H10 31.8 ±3.6

C6H5CH3 CH2 :CHCH2 CH(CH3

) 2

(a) 14 to 17

12

(cm3 mole-1 sec

-1

) °C

450-514

459-592

450-530

CD3COCD3 CH2 :CHCH2 Br CH2 :CHCH2 CH

(CHa

T

1

2

3

Note

(a) Calculated assuming a steric factor in the range 10_1

to 10-2

.

References

1. Gordon, Smith, and McNesby, J. Am. Chem. Soc. 81,

5059 (1959).

2. Szwarc, Ghosh, and Sehon, J. Chem. Phys. 18, 1142 (1950).

3. Taniewski, J. Chem. Soc. 7436 (1965).

81
Metathetical Reactions of n-Propyl Radicals (a)

Reactants Notes E logioT Tempera- Radical source Reference

ture range

HYDROGEN ATOM TRANSFER

n-C3 H7 CHO

(kcal mole-1

) 6.7

(cm3 mole-1 sec

-1

) 11.0 °C

98-361 n-C3 H7 CHO P 1

n-C3H7 CHO 10.8 11.0 191-300 ti-C

3 H7 CHO P 1

(n-C3 H7

) 2 CO 6.5 10.4 55-161 (n-C3H7

)2 CO P 2 HCOOCH2 CH2 CH3 7.6 10.9 74-178 CH3COCH3 P 3

(n-C

3 H7

) 2N2 7.9 11.3 25-291 (n-C 3 H7

) 2 N2 P 4

Ratios of Rate Constants (n-Propyl Radicals)

Reactions Notes A‘l/^2 Temperature range

Radical source

Refer- ence

(1) n-C3H7 + HI = C3 Hh +

1

°C

(2)rc-C

3 H7 + L = c3 h7 i + i

(1) n-C3 H +

1

= c3 h7

i + i

0.11 290 n-C3 H7 I/HI t 5, 6

(2) n-C3 H7 + NO

= C3 H7NO

(1) n-C3 H7 +I2 = C3 H7 I + I

11 25 n-C3 H7 I/NO P 7

(2) n-C3 H7 + 02 = c,h702

22 25 n-C3 H7 I/02 P 7

Note References

(a) The rate constants are based on log k (cm3 mole-1 sec

-1

) 1. Kerr and Trotman-Dickenson, Trans. Faraday Soc. 55 , = 1013 4 for the combination of rc-propyl radicals. 921 (1959).

2. Masson, J. Am. Chem. Soc. 74, 4731 (1952).

3. Thynne, Trans. Faraday Soc. 58, 1394 (1962).

4. Kerr and Calvert, J. Am. Chem. Soc. 83, 3391 (1961).

5. Benson and 0‘Neal, J. Chem. Phys. 34, 514 (1961).

6. Ogg, J. Am. Chem. Soc. 56, 526 (1934).

7. Christie and Frost, Trans. Faraday Soc. 61 , 468 (1965).

82
Metathical Reactions of Isopropyl Radicals (a)

Reactants Notes E logioA Tempera- Radical source Reference

ture range

HYDROGEN ATOM TRANSFER

Hydrogen (kcal mole-1

) (cm3 mole-I sec

-1

) °C

h2 12.5 260-320 CH3CH:CH2 + H 1

Alkenes

cyclohexadiene-1 ,4 6.5 11.4 75-136 (t-C3H7

)2CO P 2

cyclohexadiene-1,3 7.1 ±0.7 11.5 ± 0.4 42-133 (i-C3H7

)2CO P 3

Aldehydes and

Ketones

i-C3H7 CHO 9.5 10.7 283-377 r-C

3 H7CHO P 4

j-C

3 H7 CHO 6.3 10.8 117-354 i-C

3H7 CHO P 4

(i-C

3 H7

)2 CO 8.5 ±0.1 11.1 100-400 (t'-C

3 H7

) 2 CO P 5

[(CH3

) 2 CD]2 CO (b) 9.3 ±0.3 10.6 200-400 [(CH3

) 2CD]2 CO P: 6

[(CHs

)2CD]2CO (b) 11.7 ± 1.1 11.3 300-400 [(CH3) 2CD]2 CO P 6

Ester

HCOOCH(CH3

) 2 6.6 9.9 94—181 ch3coch3 P 7

Azo-compound

(i-C

3 H7 )2 N2 6.5 ±0.5 9.9 30-120 (i'-C 3H7

) 9 N9 P 8

6.7 ±0.4 10.0 35-127 (t'-C

3 H7

)2 N2 P 9

Ratios of Rate Constants (Isopropyl Radicals)

Reactions Notes Ex-Ei. \ogioAx/A 2 kx/k2 Temperature range

Radical source Reference

(kcal mole-1

) °C

(1) i-C.

s H7 +

1

2 = C3 H? I + I

(2) i-C3 H7 + NO = C3 H7 NO 22 25 i-C.,H

7 I/NO P 10

(1) i-C 3 H7 +

1

2 = C3 H7 I + I

(2) (-C3 H7 + 02 = C3 H7 02 ~ 3 25 i-C3 H7I/02 P 10

(1) i-C.

s H7 + i-C

3 H7 I (c) 520(3130A) 35 i-C3 H7 I P 11 = c3 h6 +c3h8 +i

(2) i'-C

3 H7 +

1

2 = t-C3 H7 I + I (c) 170(2300A) 35 ;-c3 h7

i p 11

(1) C3 H7 + 02 = C3 Hh + H02 (2) C3 H7 + 02 = C3 H7 02 (d) 19.0 6.6 345-472 c3 hs/o2 t 12

83
Notes References

(a) The rate constants are based on log k (cm3 mole-1 sec

-1

) = 1012 9 for the combination of isopropyl radicals.

(b) The attacking radical is (CH3 )2CD.

(c) The difference in values is due to a hot radical effect. The

value at 3130 A approximates to the correct value for thermally

equilibrated isopropyl radicals.

(d) Summary of a large body of literature data. The propyl

radical is probably a mixture of n and isopropyl.

1. Hoey and Le Roy, Can. J. Chem. 33, 580 (1955).

2. James and Suart, J. Am. Chem. Soc. 86, 5424 (1964).

3. James and Suart. J. Phvs. Chem. 69, 2362 (1965).

4. Kerr and Trotman-Dickenson, Trans. Faraday Soc. 55,

921 (1959).

5. Heller and Gordon, J. Phys. Chem. 60, 1315 (1956).

6. Heller and Gordon, J. Phys. Chem. 62, 709 (1958).

7. Thynne, Trans. Faraday Soc. 58, 1394 (1962).

8. Durham and Steacie, Can. J. Chem. 31, 377 (1953).

9. Riem and Kutschke, Can. J. Chem. 38, 2332 (1960).

10. Christie and Frost, Trans. Faraday Soc. 61, 468 (1965).

11. McMillan and Noyes, J. Am. Chem. Soc. 80, 2108 (1958).

12. Sattersfield and Reid, J. Phys. Chem. 59, 283 (1955).

Perfluoropropyl Radicals

Reactants Notes E logny4 Tempera- Radical source Reference

ture range

HYDROGEN ATOM TRANSFER

(kcal mole-1

) (mole -1 cm3 sec

-1

) °C

h2 12.3 ±0.4 12.64 125-243 (n-C

3 F7

)2 CO 1

(a) 12.1+0.2 12.86 157-319 C3F7 CHO 2

d2 13.8 ±0.5 12.78 (n-C

3F7

)2 CO 1 (b) 12.9 ±0.8 12.69 85-182 (n-C3F7

)2CO 3

(a) 14.0 ±0.1 12.98 165-297 C3F7CHO 2 ch4 9.5 ±0.5 10.99 70-166 (n-C3 F7

)2CO 3

c2h6 (c) 9.2 ±0.5 12.24 87-1% (n-C3F7

)2CO 3

cyclo-C6 HI2 5.2 ±0.1 11.08 25-290 (n-C3 F7

)2CO 4

C3F7CHO (c) 4.0 ±0.3 10.27 28-315 C3F7 CHO 5

5.5 ±0.2 10.98 165-297 c3f7 cho 2

CH3COCH3 7.2 ±0.4 11.83 27-306 c3 f7 cho 6

C3F7COC2H5 8.4 ±0.3 11.77 80-362 c3 f7 coc2 h5 7

Notes

(a) These results are less reliable than those obtained from

perfluoro ketone systems.

(b) Assuming A= 101099 exp (— 9500/RT) for the reaction n - CaFz + CH4 = C3F7H + CH3. (c) For both these compounds it seems likely that errors have

been made in the determination of the activation energies,

although the rate constants were probably of the correct

magnitude.

References

1. Miller and Steacie, J. Am. Chem. Soc. 80, 6486 (1958).

2. Pritchard and Foote, J. Phys. Chem. 68, 1016 (1964).

3. Giacometti and Steacie, Can. J. Chem. 36, 1493 (1958).

4. Pritchard and Miller, J. Phys. Chem. 63, 2074 (1959).

5. Pritchard,. Miller, and Foote, Can. J. Chem. 40, 1830

(1962).

6. Pritchard, Hsia, and Miller, J. Am. Chem. Soc. 85, 1568

(1963).

7. Pritchard and Thommarson, J. Phys. Chem. 69, 1001 (1965).
Metathelical Reactions of Halogenated Propyl Radicals

Reactions Notes E logioA Temperature range

Radical source Reference

CC13CH2 CH2 + CCl.,Br = CCl3 CH2 CH2 Br + CC13

3.4

(kcal mole-1

) (cm.3 mole-1 sec

-1

) 8 °c

103-193 C2 H4 /CCl3 Br P 1

ich2ch2ch2 + i

2 = ich2 ch2 ch2 i+i

(a) 0.5 12.5 cyclo-C3 H6/I

2

' T 2

Note References

(a) Estimated from the equilibrium constant and collision theory.

1. Tedder and Walton, Trans. Faraday Soc. 60, 1769 (1964).

2. Benson, J. Chem. Phys. 34, 521 (1961).

85
Ratios of Rate Constants (Isopropoxy Radicals)

Reaction Notes Ei E2 \og10AJA2 kjk2 Temperature range

Radical source Reference

(1) i-C,H7 0 = CH ( CH0 + CH3 (2) ;-c 3 h7 o + (CH3

)2 choocc2 h5 = i-C

3 H7 OH + R

(kcal mole~l ) < 6

°C

28 C2 H5COOCH(CH3

)2 p

1

(1) i-C

3 H7 0=CH3CH0 + CH3 (2) i-C3 H7 0 + N0' = CH3 COCH3 +HNO

16 175-200 (CH3

)2 CHONO t 2

(1) i-C

3 H7 0 + CH3 CHO

= i-C 3 H7 OH + CH3 CO

(2) t-C..H7 0 + (i-C,H O)2 = t-C 3 H7 OH + R

27 ±4 26 (t-C

3 H7 0)2 P 3

References Review

Wijnen, J. Am. Chem. Soc. 82, 1847 (1960). 1. Gray and Williams, Chem. Rev. 59, 239 (1959). Ferguson and Phillips, J. Chem. Soc. 4416 (1965). McMillan, J. Am. Chem. Soc. 83, 3018 (1961). /

1 . 2 . 3.

86
Metathetical Reactions of Butyl Radicals

Reactants Notes E logioA Temperature rangeRadical source Reference

HYDROGEN ATOM TRANSFER

(i) n-butyl radicals (a) ( kcal mole-1

) (cm3 mole~ 1 sec

-1

) °C

n-C4 H9CHO 5.4 10.9 61-229 n-C4 H9CHO p 1 hcooch2 ch2 ch2 ch3

5.3 10.2 75-186 CH3 COCH3 p 2

(ii) sec-butyl

radicals

(a)

ch3ch2 ch

(CH3 )CHO

4.9 10.7 25-349 ch3ch2 ch

(CH3 )CHO p

3

(iii) iso-butyl

radicals

(a)

i-C4 H9 CHO 12.7 ±0.2 12.62 ±0.05 178-279 i-C 4H9CHO p 4

i-C 4H9CHO 6.5 ±0.1 11.71 ±0.07 117-230 i-C 4 H9CHO p 4

(t-C4H9

)2CO

(c)

7.6 6.8 ±0.211.4 11.06 ±0.09

78-194 (i-C

4 H9

) 2 CO p 54

(iv) t-butyl radicals (b)

(CH..)

3 CCHO 10.0 11.2 240-386 (CH3

)3CCHO p 6

(CH3

) 3 CCHO (d) 4.3 9.8 60-386 (CH3

) 3 CCHO p 6

Ratios of Rate Constants (t-Butyl Radical)

Reaction Notes Ei — Ei log10A,/A 2 ki/k2 Temperature rangeRadical source Reference

(kcal mole~l ) °C

(1) t-C

4 H9 + HBr=C4 H10 + Br

(2) t-C

4 H9 + Br2 = C4 H9Br + Br 8.0 5.11 40-85 (CH3

) 3 CH/Br2 T •7, 8, 9

(1) t-C

4 H9 + HI = C4 H10 + I 0.226 526 ] (2) t-C

4 H9 + I

2 =C4 H9

I + I 0.234 552

[ (CH3

)3 CH/I2 t 8

0.251 583 J

Notes

(a) The rate constants are based on log k (cm3 mole-1 sec

-1

) = 1014 for the combination of n-, sec-, and iso-butyl radicals.

(b) The rate constants are based on log k (cm3 mole-1 sec

-1

) = 1012 5 for the combination of t-butyl radicals.

(c) Recalculation of data from reference 5. (d) This value of the activation energy is probably low.

References

1. Kerr and Trotman-Dickenson, J. Chem. Soc. 1602 (1960).

2. Thynne, Trans. Faraday Soc. 58, 1533 (1962).

3. Gruver and Calvert, J. Am. Chem. Soc. 78, 5208 (1956).

4. Metcalfe and Trotman-Dickenson, J. Chem. Soc. 5072

(1960).

5. Kraus and Calvert, J. Am. Chem. Soc. 79, 5921 (1957).

6. Birrell and Trotman-Dickenson, J. Chem. Soc. 4218 (1960).

7. Eckstein, Scheraga, and Van Artsdalen, J. Phys. Chem.

22 , 28 (1954).

8. Teranishi and Benson, J. Am. Chem. Soc. 85, 2887 (1963).

9. Benson and Buss, J. Chem. Phys. 28, 301 (1958). 87
Melathetical Reactions of t-Butoxy Radicals

Reactants Notes E logi oA Temperature range

Radical source Reference

HYDROGEN ATOM TRANSFER

(CH3

) 3CH

(kcal mo/e-1

) 4.0

(cm3 mole-1 sec

-1

) 10.8 °C

25-79 D.T.B.P. P 4

Ratios of Rate Constants (t-Butoxy Radicals)

V

V

c

uh

r

Reaction Notes E\ E-2. logl(>/f 1 M2 Ai/A:2 Temperature range

Radical source Reference

(1) (CH3) 3CO + CH2 0 = (CH3

) 3 COH + HCO

(2) (CH3) 3CO

= ch3 + ch3 coch3

(kcal mole-1

)

(3.8 ±0.8)

X 105 cm3 mole-1

°C

135 D.T.B.P. T 1

(1) (CH3

) 3 CO + ((CH3

) 3 CO)2 = (CH3

) 3COH + R

(2) (CH3) 3 CO

= ch3 +ch3 coch3 -3 25-79 D.T.B.P. P 2

(1) (CH3

)3 CO + (CH2

) 2NH

= (CH3

) 3COH + R

(2) (CH3

)3 CO

= ch3 +ch3 coch3 — 12 ±2 129-154 D.T.B.P. P 3

References Review

1. Hoare and Wellington, 8th Int. Comb. Symp., p. 472 1. Gray and Williams, Chem. Rev. 59, 239 (1959). (Williams and Wilkins 1962).

2. McMillan and Wijnen, Can. J. Chem. 36, 1227 (1958).

3. Brinton and Volman, J. Chem. Phys. 20, 25 (1952).

4. McMillan, J. Am. Chem. Soc. 82, 2422 (1960).

88
Metathetical Reactions of Peracid Radicals

Reactants Notes E logi oA Temperature rangeRadical source Reference

HYDROGEN ATOM TRANSFER

(i) Peracetic Radicals (heal mole ') (cm3 mole 1 sec *) °C

CH,CHO h — (8.05 ± 2.40) X 106 20 CH.,CH0/02 P 1

(ii) Perpropionic

Radicals

c2 h.cho £ = (4.35 ±0.91) x 107 22 C2H5 CHO/02

Ratio of Rate Constants (Peracid Radicals)

Reaction Notes Ei — E-i lognv4 ilA2 hilki Temperature range

Radical source Reference

(i) Peracetic Radicals (kcal mole-1

) °C

(1) CH.! CO.s + CH3 CHO

=ch,co,h+ch..co

(2) 2CH.,CO;j = (CH.,C0)2 02 + 02

Ei — \Ei = 7.2± 1.0

20-30 ch.,cho/o2 p 2

(ii) Perpropionic Radicals

(1) c2 h5 co.( + c2 h5 cho

= c2 h5 co3 h+c2 h5 co

(2) 2C2H5CO.t = (C,Hs C0)2 02 + 02

Ei — ^£2 = 6.75 ±0.5

20-47 c2 h.cho/o2 p 3

References

1. McDowell and Sharpies, Can. J. Chem. 36, 268 (1958).

2. McDowell and Sharpies, Can. J. Chem. 36, 251 (1958).

3. McDowell and Sharpies, Can. J. Chem. 36, 258 (1958).

89
\V

c:

SB I

t* 1

/'

Metathetical Reactions of Peroxy Radicals

Reactants Notes E logioA Tempera- Radical source Reference

ture range

HYDROGEN ATOM TRANSFER

(i) Isobutyl peroxy

radicals

(kcal mole ') ( cm3 mole 1 sec

x

) °C

(CH:! )

:! CH (a) (b) 16.0 4 X 10"2Z 327-427 (CH.! ).i CH/02 -H 1

(ii) Cyclohexenyl per- oxy radicals

cyclohexene (a) (b) 7.0 6 X 10" 7Z 152-352 c6 h!0/o2 -h 1

(iii) Isopropyl ben- zene peroxy

radicals

C6H5CH(CH,)2 (a) (b) 7.0 2 X 10-6Z 252-357 C6 H5 CH(CH;j ) 2 -h 1

Notes Reference

(a) The peroxy radical is the radical formed by oxygen addi- 1. Burgess and Robb, Trans. Faraday Soc. 54, 1015 (1958). tion to any hydrocarbon radical produced in the primary act.

(b) “Z” is the collision number.

90
Metalhetical Reactions of Phenyl Radicals

Reactants Notes E logioA

(a) Temperature range

Radical source Reference

HYDROGEN ATOM TRANSFER

(kcal mole ') (cm3 mole 1 sec *) °C

h2 6.5 10.97 180-350 (C6H5

) 2 Hg P 1 CH4 7.5 11.19 180-350 (C,;H-)

2 Hg P 1 11.1 11.9 277-407 CH;j COC6H5 p 2

cyclo-C.jH,. 8.5 11.4 310-407 ch:! coc,.h5 p 2

*-c4 h10 6.7 11.8 277-407 CH COCk H. P .1 6 5 2

CH..C0C..H, •> 6 D 6.2 11.6 277-407 CH:! COC6 H5 p 2

CF,H 5.2 10.17 180-350 (CB H5

) 2 Hg P 1

GROUP TRANSFER REACTION

C6H5 + CK H5 COCH;i 6.2 9.6 277-407 ch.,coc6h5 p 2 = C6H5C6H5 + CH3CO

Note References

(a) These values are based on log k (cm3 for the combination of phenyl radicals. mole 10 ' 1. Fielding and Pritchard, J. Phys. Chem. 66, 821 (1962).

2. Duncan and Trotman-Dickenson, J. Chem. Soc. 4672 (1962).

247-168 0- 67—7

91
Ratios of Rate Constants (Tolyl Radicals)

Reactions Notes Ei-Ei \0gi<y4i/A2 kllk2 Temperature range

Radical source Reference

(1) CH.jCgH^CgH^CH.,^ = ch,c6h5 + ch,c6h4 ch2 (2) CH.,C6 H4 + D2 = CH,C6 H4 D + D

(a)

( kcal mole-1

)

10.7

°C

700 (CH.,)

2 C6 H4 /D2 t 1

(1) p-CH.! C6 H4 + C6 H4 (CH.,)

2 =ch,c6h5 + ch'.

) c6 h4 ch2 (2) p-CH.( Cfi H4 + D2 = CH C H D + D 3 6 4

(b) 24.6 484 p-(CH:j ) 2 C6H4 /D2 T 2

Notes

(a) No distinction was made between the o, m, and p xylenes.

(b) There appears to be a misprint in the original paper. The

numbering of the reactions has been reversed.

References

1. Burr and Strong, J. Am. Chem. Soc. 86, 5065 (1964).

2. Burr and Strong, J. Chem. Phys. 43, 1432 (1965).

92
Hydroxyl Radicals

Reactants Notes E logIOA Temperature range

Radical source Reference

HYDROGEN ATOM TRANSFER

Hydrogen (kcal mole ') (cm3 mole 1 sec *) °C

h2 11.0 14.52 105-216 H2 0/ discharge 1 A = 2.0 X 10 10 520 H2/02 ignition 2

(a) 10.0 14.1 3

10.0 14.40 H2 02 flames 4

A: = 4.3 X 109 37 N02 /H reaction 5

(b) 5.9 ±1.0 13.80 ±0.7 27-1700 6

* k = ( 3.5± 1.3) x 109 27 H2

/ discharge 7

(b) (c) 5.0(5.3) ±0.6 13.13(13.33) 27-799 8

(b) (c) 5. 3(5.5) ± 0.6 13.33(13.49) 27-799 9 A= 1.1 X 1012 642 H2 /02 flame 10 A = (3.9 ±0.2) X 109 27 N02/H reaction 11

(b) 5.2 13.36 27-1677 11 6.4 14.17 687-807 H2 /02 ignition 12

Alkanes

ch4 8.3 14.38 H2 0/ discharge 13

9.0 14.54 1027-1527 CH4 /02 flame 14

A = 2 X 1013 1377-1567 CH4/02 flame 15

6.5 14.15 930-1530 CH4/02 flame 16

(d) 7.9 14.36 17

c2 h2 A = 2 >< 1012 1400-1700 C2 H2 /02 flame 18

7.3 14.44 50-237 H2 0/ discharge 19

c2 h4 A= 1 >< 1013 977-1127 C2 H4/02 flame 20

6.4 14-60 77-178 H2 0/ discharge 19

c2h6 5.5 14.11 65-228 H2 0/ discharge 19 A = 2.5 X 1013 1147-1337 C2 H6/H2 /02 flame 34

(e) A = 2.1 X 1013 520 H2/02 ignition 21

A = 5X 1012 1027-1227 C2 H6/02 flame 20

C,H8 (e) A = 4.3 X 1013

I 520 H2/02 ignition 21

n-C4 H10 k = 5.8 x 1013 520 H2 /02 ignition 21

^•c4 h10 A = 3.2 <n _x O 520 H2 /02 ignition 21

Aldehydes

HCHO 0.9 14.11 73-216 H2 0/ discharge 22

(b) 13.0 15.7 73-1339 20 CH:i CHO 4.0 13.53 53-209 H2 0/ discharge 22

Acid

HNO., A= 1.0 X 1011 27 HNO., flash pho- 23

tolysis

Halogenated Alkane

CH.( Br A = 1.5 X bn 1527-1727 CH4 /0„ flame 24

93
Hydroxyl Radicals — Continued

Reactants Notes E logio^ Temperature range

Radical source Reference

(kcal mole 1

) (cm3 mole-1 sec

-1

) °C

OXYGEN ATOM TRANSFER

(g) 7.0 13.08 70-203 H2 0/ discharge 1 (a) 5.7 12.46 3

A = 9x 10 11 1677 CH4 /02 flame 15

(d) 5.7 12.46 17

(b) 7.7 12.85 127-1727 20

4.0 12 1107-1447 flame study. 25

(b) 6.2 ±0.6 12.6 ±0.3 107-1677 8

(b) (c) 0.5(0. 8) ± 0.6 11.5(11.7) ±0.3 200-800 8

A = (1.15± 0.5) X 10 11 27 N02 /H reaction 11

(b) 0.6 11.49 27-1677 11

MISCELLANEOUS REACTIONS

oh + f2 = hf+f + o 18.0 15.3 F.,/H

2 0 flames 26

18.0 13.85 497-557 F2 /H2 0 ignition 26

Hydroxyl Radicals (Rate Constant Ratios)

Reaction Notes e,-e2 iogioAJA-z ki/kz Temperature range

Radical source Reference

(kcal mole-1

) °C

(1) C,H + OH = C..H + H O

(2) H2 + 0H = H + H20

(0 12 540 H2 /02 ignigion 27

(1) c2 h8 ±oh = c.j h7 + h2 o

(2) H2 + 0H = H + H2 0 (1) 27 520 H2 /02 ignition 27

(1) n-C4 H10 + OH = C4 H4 + H2 0

(2) H2 + 0H = H + H2 0 (f) 36 520 H2 /02 ignition 27

(1) j-C ,H + OH = C.LL + HO

(2) H2 + 0H = H + H2 0 (f) 20 520 H2 /02 ignition 27

(1) hcho + oh = hco + h2 o

(2) H2 + 0H = H + H2 0 (0 42 540 H.,/0., ignition 27

(1) (C 2 H,)4 Si + OH

= (C2 H5

).

i Si.C2H4 + H.,0

(2) H2 + 0H = H + H2 0 (0 74 520 H.,/0., ignition 27

(1) h2 o2 + oh = ho2 ±h2 o 4.8 to 5.7 447 H.,/02 ignition 28

(2) H2 + 0H = H2 0 + H 7.1 500 H2 /02 ignition 29

5.5 440 H.,/02 ignition 30

4.3 ±0.3 440 H.,/02 pyrolysis 27

4.7 500 H., combustion 27

94
Hydroxyl Radicals (Rale Constant Ratios) — Continued

Reaction Notes . £,-£2 \og10A 1 IA 2 A1 /A2 Temperature range

Radical source Reference

( kcal moIe~ l ) °C

(1) h2 + oh = h + h2 o

(2) CO + OH = C02 + H 4.0 ±0.3 1.49 ±0.7 200-350 H2 0 photolysis 31

5.0 520 H2 /02 ignition 27

3.3 CO/H2 combustion 27

(b) 5.16 1.98 500-1002 27

(b) 4.6 ±0.3 1.87 27-1002 11

(1) d2 + oh = d + hdo

(2) C0 + 0H = C02 + H 6.4 ±0.3 2.20 ±0.09 200-300 H2 0 photolysis 31

(1) ch4 + oh = ch3 + h2 o

(2) CO + OH = C02 + H 7.3 2.28 400-650 H2 02 pyrolysis 32

(1) hcho + oh = hco + h2 o 33 525 H2 02 pyrolysis 32

(2) CH4 + 0H = CH3 + H2 0 27 600 H2 02 pyrolysis 32

22 650 H2 02 pyrolysis 32

33 500 CH. combustion 4 33

Notes

(a) Used at flame temperatures.

(b) Critical survey of literature data.

(c) AHf (OH) = 9.33 (10.0) kcal/mole.

(d) This value was used by the authors in the region 1000°-

1500° but its origin was not stated.

(e) Measured relative to OH + H2 = H2 0 + H, for which

k= 1.6 X 109 at 520 °C.

(f) Calculated on the assumption that oxygen atom reactions could be neglected.

(g) The products of this reaction are C02 + H.

References

1. Avramenko and Lorentso, Zhur. Fiz. Khim. 24, 207 (1950).

2. Baldwin, Trans. Faraday Soc. 52, 1344 (1956).

3. Kondratiev, 7th. Int. Comb. Symp., p. 41 (Butterworths,

London, 1959).

4. Fenimore and Jones, J. Phys. Chem. 65, 993 (1961).

5. Del Greco and Kaufman, Disc. Faraday Soc. 33, 128 (1962).

6. Kaufman and Del Greco, 9th. Int. Comb. Symp., p. 659

(Academic Press, N.Y., 1963).

7. Wise, Ablow, Sancier, and Wood, Project Squid, Semi

Annual Report, p. 59 (April, 1964).

8. Dixon-Lewis, Sutton, and Williams, Trans. Faraday Soc. 61 , 255 (1965).

9. Dixon-Lewis, Sutton, and Williams, J. Chem. Soc. 5724

(1965).

10. Dixon-Lewis, Sutton and Williams, 10th. Int. Comb. Symp.

Comb. Inst., p. 495 (Pittsburgh, 1965).

11. Dixon-Lewis, Wilson, and Westenberg, J. Chem. Phys.

44, 2877 (1966).

12. Skinner and Ringrose, J. Chem. Phys. 42 , 2190 (1965).

13. Avramenko and Kolesnikova, “Advances in photochemistry,” p. 25 (Interscience Publishers, N.Y., 1964).

14. Fenimore and Jones, J. Phys. Chem. 65 , 2200 (1961).

15. Westenberg and Fristom, J. Phys. Chem. 65 , 591 (1961).

16. Fristrom, 9th. Int. Comb. Symp., p. 560 (Academic Press

N.Y., 1963).

17. Intezarova, Kondratiev, and Mukhoyan, Kinetika i Kataliz 5, 585 (1964).

18. Fenimore and Jones, J. Chem. Phys. 41 , 1887 (1964).

19. Avramenko and Lorentso, Dokl. Akad. Nauk. S.S.S.R. 67, 867 (1949).

20. Westenberg and Fristrom, 10th. Int. Comb. Symp. Comb.

Inst., p. 473 (Pittsburgh, 1965).

21. Baldwin and Walker, Trans. Faraday Soc. 60, 1236 (1964).

22. Avramenko and Lorentso, Dokl. Akad. Nauk. S.S.S.R. 69, 205 (1949).

23. Husain and Norrish, Proc. Roy. Soc. 2 73A, 165 (1963).

24. Wilson, 10th. Int. Comb. Symp. Comb. Inst., p. 47 (Pitts- burgh, 1965).

25. lost, Schecker, and Wagner, Z. Phys. Chem. 45 , 56

(1965).

26. Nosova, Lovachev, and Vedeneev, Comb, and Flame 8,

163 (1964). 27. Baldwin, Jackson, Walker, and Webster, 10th. Int. Comb.

Symp. Comb. Inst., p. 473 (Pittsburgh, 1965).

28. Forst and Giguere, J. Phys. Chem. 62 , 340 (1958).

29. Baldwin and Mayor, Trans. Faraday Soc. 56, 103 (1960).

30. Baldwin and Doran, Trans. Faraday Soc. 57, 1578 (1961).

31. Ung and Back, Can. J. Chem. 42 , 753 (1964).

32. Hoare, Nature 194, 283 (1962). 33. Blundell, Cook, Hoare, and Milne, 10th. Int. Comb. Symp.

Comb. Inst., p. 445 (Pittsburgh, 1965).

34. Fenimore and Jones, 9th. Int. Comb. Symp., p. 560 (Academic Press, N.Y., 1963).

95
Metathetical Reactions of Hydroperoxyl Radicals

Reactants Notes E logioA Tempera- Radical source Reference

ture range

HYDROGEN ATOM TRANSFER

(kcal mole *) (cm3 mole 1 sec *) °C

24.0 11.08 H2 /02 ignition 1, 2 k= l. LX 107 500 H2 /02 ignition 3

14.8 ±2.2 617-1007 H2 /02 ignition 4

k=l.ljx 106 500 7

34.6 16.51 687-807 9

(a) 8.0 8.1 600-615 H2 /02 ignition 1, 8

(b) 30.0 13.26 600-615 H2 /02 ignition 2

Ratios of Rate Constants (Hydroperoxyl Radicals)

Reactions Notes £i-£2 log 10 A 1 IA 2 kjk. Temperature rangeRadical source Reference

(1) co + ho2 = co2 + oh

(2) H2 +H02 = H + H202

( kcal mole-1

)

9.5 ±2

°C

500 H2 /C0/02 ignition 5

(1) HCHO + HO,

=hco+h2 o2 (2) C0 + H02 = C02 + 0H 340 525 ch4 /o2 t 6

Notes

(a) These values must be rejected on thermochemical grounds.

(b) Is a recalculation of data from (a).

References

1.

Voevodsky, 7th. Int. Comb. Symp., p. 34 (Butterworths,

London, 1959).

2. Kondratiev, Dokl. Akad. Nauk. S.S.S.R. 137, 120 (1961).

3. Baldwin and Mayor, Trans. Faraday Soc. 56, 103 (1960).

4. Miyama and Takeyama, J. Chem. Phys. 41 , 2287 (1964).

5. Baldwin, Jackson, Walker, and Webster, 10th Int. Comb.

Symp. Comb. Inst., p. 423 (Pittsburgh, 1965).

6. Blundell, Cook, Hoare, and Milne, 10th. Int. Comb. Symp.

Comb. Inst., p. 445 (Pittsburgh, 1965).

7. Dixon-Lewis and Williams, Nature 196, 1309 (1962).

8. Poltorak and Voevodsky, Zhur. Fiz. Khim. 24, 299 (1950).

9. Skinner and Ringrose, J. Chem. Phys. 42, 2190 (1965).

96
Metathetical Reactions of Imino Radicals

Reactants Notes E logioA Temperature range

Radical source Reference

HYDROGEN ATOM TRANSFER

HNCO (a) 3.6

,

(kcal mole-1

)

.

(cm3 mole-1 sec

-1

)

" • <

°C

-31-200

-

HNCO P 1

Note

(a) The products of this reaction are NH2 and NCO.

Reference

1. Mui and Back, Can. J. Chem. 41 , 826 (1963).

97
Metathetical Reactions of Amino Radicals

Reactants Notes E logi oA Tempera- Radical source Referture range ences

(kcal mole-1

) (cm3 mole-1 sec

-1

) °C

nh2 + n2 h4 A = 7.9 X 1010 25 i =nh:) +n2h,

17 13.5 830-1130 n2 h4 s.t. 4

nh2 + o2 = nh + ho2 42.5 ±1.2 1277-2027 nh3 /o2 s.t. 2

Metathetieal Reactions of Amino Radicals

Ratios of Rate Constants

Reactants Notes £i-£2 logio/4i//f 2 a,/a2 Temperature range

Radical source Reference

(1) NH2 + (CH3 ) 2 N-NH2 = NH3 + (CH3

)2N-NH

(2) NH2 +(CH 3

) 2 N-NH2 = NH3 + (CH3 )(CH2 )N"NH2

(kcal mole-1

)

6.6 X 10-3

°C

250 (CH3

)2 N.NH2 t 3

References

1. Diesen, J. Chem. Phys. 39, 2121 (1963).

2. Takeyama and Miyama, J. Chem. Phys. 42, 3737 (1965).

3. Cordes, J. Phys. Chem. 65 , 1473 (1961).

4. Michel and Wagner, 10th Int. Comb. Symp. Comb. Inst.,

p. 353 (Pittsburgh, 1965).

98
Melathetical Reactions of Difluoroamino Radicals

Reactions Notes E logltvd Tempera- Radical source Reference

ture range

HYDROGEN ATOM TRANSFER

Alkanes ( kcal mole-1

) (cm3 mole-1 sec

-1

) °C

n-C4 H10 22.20 ±0.08 11.83 ±0.04 180-282 N2 F4/n-C 4 H10 T 1

cc4 h,0 18.49 ±0.10 10.49 ±0.04 155-282 n2f4//-c

4h10 t 1

cyclo-C5H10 .19.9l!± 0.11 10.93 ±0.05 180-282 N2F4/cyclo-C5H10 T 1

neo-C5 H12 26.68 ±0.07 13.22 ±0.03 180-282 N2F4/neo-C5 H12 T 1

Ketone

CH3COCH, 19.56 ±0.11 10.71 ±0.05 170-280 n2f4 /ch3 coch3 t 2

FLUORINE ATOM TRANSFER

f2 o 22.5 ±0.7 14.01 120-170 n2f4/f2 0 t 3

References 2. Grzechowiak, Kerr, and Trotman-Dickenson, J. Chem.

Soc. 5080 (1965).

1. Grzechowiak, Kerr, and Trotman-Dickenson, Chem. 3. Rubinstein, Sicre, and Schumacher, Z. Phys. Chem. 43 , 64

Comm. 109 (1965). (1964).

99
Metathetical Reactions of Nitrate Radicals

Reactions Notes E log io A Temperature range

Radical source Reference

( kcal mole* 1 ) (cm3 mole* 1 sec* 1

) °C

N03 + NO = 2N02 4 = 6x 1012 27 1 1.4 ±2.5 13.8 n2 05 s.t. 2

k = 2.7X 10 12 27 no2/o3 P 3

1.7 12.62 200-550 no2 t 4

Ar= 1 ><1014 25 no2 f.p. 5 no3 +no2 =no2 +no+o2 3.9 ±1.0 11.22 27-547 n2 o5 s.t. 1, 2

3.2 ±1.0 11.07 ±0.47 200-550 no2 t 4

no3 +noci=no2 +no2ci (a) £ = 7.0 x 10 7 40 noci/o3/n2 o5 t 6

£ = 2.3 X 107

1

40 2

Ratios of Rate Constants

Reactions Notes Ei E2 log io A i/A 2 kilk2 Temperature range

Radical source Reference

(kcal mole* 1

) °C

(1) N03 + NO = 2N02 (2) N03 + N0=N02 + no+o2 60 434 no2 t 7

(b) 1.4 2.2 20-30 no/n2 o5 t 8, 9

(c) 2.3 3.2 20-30 no/n2 o5 t 8, 9

Notes

(a) The A factor was assumed, only the rate constant was

determined.

(b) At 400 mm total pressure.

(c) At 57 mm total pressure.

References

1.

Davidson and Schott, J. Chem. Phys. 27, 317 (1957).

2. Schott and Davidson, J. Am. Chem. Soc. 80, 1841 (1958).

3. Ford, Doyle, and Endow, J. Chem. Phys. 32, 1256 (1960).

4. Ashmore and Burnett, Trans. Faraday Soc. 58, 253 (1962).

5. Husain and Norrish, Proc. Roy. Soc. 2 73A, 165 (1963).

6. Johnston and Leighton, J. Am. Chem. Soc. 75, 3612 (1953).

7. Ashmore and Levitt, Research 9, S25 (1956).

8. Hisatsune, Crawford, and Ogg, J. Am. Chem. Soc. 79,

4648 (1957).

9. Hisatsune, McHale, Nightingale, Rotenberg, and Crawford,

J. Chem. Phys. 23, 2467 (1955).

100
Metathetical Reactions of Thiyl Radicals

Reactant Note E log 10 A Temperature range

Radical source References

HYDROGEN ATOM TRANSFER

CH3 OCH3 (a)

(kcal mole _I

) 6.8

(cm3 mole-1 sec

-1

) 11 °C

360-440 ch3 och3/h2s t 1 , 2

Notes References

(a) For further data on systems containing HS radicals, see 1 . Imai and Toyama, Bull. Chem. Soc. Japan 34, 328 (1961). reference 3. 2. Anderson and Benson, J. Chem. Phys. 39, 1677 (1963).

3. Imai, Yoshida, and Toyama, Bull. Chem. Soc. Japan 35,

752 (1962).

101
Reactions of Chloromonoxy Radicals

Reactions Notes E logio A Temperature range

Radical source Reference

( kcal mole" 1

) (cm3 mole" 1 sec" 1 ) °C

CIO + C12 0 = C102 + Clj k == 108 C12 0 F.P. 1

CIO + CLO = 0+ 0, + C12 II yy 3X 10 7 C12 0 F.P. 1

C10 + N03 C1=N02 + Cl2 + 02 ~ 17 90-130 N03 C1 T 2

Ratios of Rate Constants (Chloromonoxy Radicals)

Reactions Notes E\ E2 logio 1 /A 2 ki/k2 Temperature rangeRadical source Reference

(1) C10 + C3H8 = H0C1

+ ch3 chch3 (2) C10 + C3 H8 =H0C1

+ ch3ch2 ch2

( kcal mole" 1

)

7.2 ±0.5

°C

100 C3 H8 /C12 0 T 3

References

1. Edgecombe, Norrish, and Thrush, Proc. Roy. Soc. 243A,

24 (1957).

2. Cafferata, Sicre, and Schumacher, Z. Phys. Chem. 29,

188 (1961).

3. Phillips and Shaw, Proc. Chem. Soc. 294 (1962).

102
Reactions of Borine Radicals

Reactants Notes E logio A Temperature range

Radical source Reference

(kcal mole~ l ) (cm 3 mole~ l sec~ l ) °C BH:j + B2 Hs = B:) H7 + H2 11.5 11.06 1, 9

BH., + B2 Db = BH.,BD

,

+ BD., 6.0 14.2 24-44 B! H./B,D„ t 4, 5, 6, 3

7.8 13.45 1

BH,+ BH,CO = B2 Hb + CO 7.0 11.4 0-30 bh3 co t 7, 4, 3

bh, + h2 o = bh2 oh

+ h2 6 11.28 51 b2 h6 /h2 o T 8, 9 bh,+hd = bh2 d + h2 7 11.6 9

Ratios of Rate Constants Involving Borine Radicals

Reaction Notes Ei Ei logio A i!

A

2 ki/k. Temperature range

Radical source Reference

(kcal mole~ x

) °C

(1) BH., + B2 Db = BD.,BH., + BD.,

(2) BH3 + D2 = BH2 D + HD 0.25 55 b2 hb/d2 t 2, 3

(1) bh.1 + o2 = bh2 oh + o

(2) BH, + CL + M = HBO,

+h2 + m 2.0 150-200 b2 h6/o2 t 1

References

1. Roth and Bauer, 5th Int. Comb. Symp., p. 710 (Reinhold,

N.Y., 1955).

2. Marcus, J. Chem. Phys. 23 , 1107 (1955).

3. Garabedian and Benson, J. Am. Chem. Soc. 86, 176 (1964).

4. Bauer, Shepp, and McCoy, J. Am. Chem. Soc. 75, 1003

(1953).

5. Trotman-Dickenson, “Gas Kinetics,” p. 237 et seq. (Butter

worths, London, 1955).

6. Maybury and Koski, J. Chem. Phys. 21, 742 (1953).

7. Burg, J. Am. Chem. Soc. 74, 3482 (1952).

8. Weiss and Shapiro, J. Am. Chem. Soc. 75, 1221 (1953).

9. Bauer, J. Am. Chem. Soc. 78, 5775 (1956).

103
Metathetical Reactions of F3SO and FSOs Radicals

Reactions Notes E logi0 4 Temperature range

Radical source Reference

f3 so+f2 =f4 so+f

(kcal mole -1

) 10.0 + 2

(cm 3 mole~ 1 sec

0 °C

5-20 f2/f2 so p 1

fso3 +f2 =f2 so3 +f 14.7 ±1.0 8.68 230-250 f2 /f2 s2 o6 t 2

References

1. Castellano and Schumacher, Z. Phys. Chem. N.F. 40, 51 2. Castellano and Schumacher, Z. Phys. Chem. N.F. 44, 57

(1964). (1965).

104
Radical Disproportionation Reactions

The reactions are classified in the same order as the tables of radical reactions. Thus the first set of reactions are those involving atoms,

followed by reactions of radicals containing one carbon atom, etc.

Reactions Notes E log io A log io A- Temperature range

Radical source Refer- ence

(kcal mole -

*)

.

(cm 3 mole ~ 1 (cm3 mole -1

sec

- *) sec

-1

) °C h + oh = h2 + o 5.8 ±1.5 12.76 ±1.0 25-2000 4

7.4 12.74 687-807 h2 /o2 s.t. 12

H + H02 = 20H 14.86 25 H2/02 - H 5

13.84 500 6 h + hno=h2 +no >9.78 20 H2 /discharge 1 > 10.48 -47 H2/discharge 2 12.78 ±0.25 1300-1700 H2 /02/N2 flame 3 H + C2F4 Br=C2F4 + HBr 11.5 16.3 855-1013 H2/02/C2F4 Br2 S.T. 7

C1 + C2 HC14 = C2HC13 + C12 13.85 224 CHCl:CCyCl2 P 25, 24

C1 + C2 C15 = C2 C14 + C12 1.2 15.6 24

Cl + COCl = CO + Cl2 0.8 14.6 25-55 CO/C^ P 33, 24

(a) 2.4 13.70 15-450 34

C1 + C13 = 2C12 V/ CM CO 20 Cl2 /discharge 19, 20

i + noi = no + i

2 12.60 60 no/i2 f.p. 30

2CN = C2 + N2 96 3177-4527 c2 n2 s.t. 14, 15

2C2 H3C12 = C2H3 C1 + C2H3 C13 0.3 12.9 25-55 CH2 :CHC1/C12 p 29

2CHC12 CHC1 = CHC1:CHC1

+chci2 chci2 0.5 ±0.5 13.47 ±0.3 30-65 cis-CHChCHCl/Cl, P 31

2C2 C15 = C2 C14 + C2 C16 0.08 11.66 87-247 C2 C14/C12 P 32

2CH3C03 = (CH3C0)2 02 13.95 20 ch3 cho/o2 p 27 + °2

2C,Hc C0, = (Co H,C0),0, 13.43 22 ch3 ch2 cho/o2 p 28 + °2 20H = H2 + 02 48.6 12.85 687-807 h2/o2 s.t. 12 20H = H2 0 + 0 12.18 37-107 H2/discharge 10

(b) 12.08 27 H2/discharge 11

1.0 ±0.5 12.88 ±0.3 25-2000 4

3.8 14.87 687-807 h2/o2 s.t. 12

(b) 12.19 27 N02 /H reaction 13 oh+hno = h2 o + no

(or H2 +N02

) 13.95 1300-1700 H2 /02/N0 flame 3 2H02 = H2 02 + 02 12.25 room temp. 6

13.81 25 H2 /02 - H 5 2NH2 = NH.s + NH 13.40 1627-2127 nh2 nh2 s.t. 8

11.66 nh3 F.p. 9

2N2H3 = 2NH3 + N2 ^ 12.48 150 H2 /discharge 18

105
Radical Disproportionation Reactions — Continued

The reactions are classified in the same order as the tables of radical reactions. Thus the first set of reactions are those involving atoms,

followed by reactions of radicals containing one carbon atom, etc.

Reactions Notes E logi 0 4 logio A Temperature range

Radical source Reference

( kcal mole -1

)

(cm 3 mole -

1

sec

-1

)

(cm 3 mole -1 see

- *) °C

2HNO = H2 0 + N2 0 > 7.48 ~ 8.9

27

190 NO/H reaction (CH3

) 2CHNO t

16

17 2N03 = 2N02 + 02 7.7 ±1.0 12.42 280-830 n2 05 s.t. 26

2C10 = Cl2 + 02 10.38

10.93 20

ci

20 F.P. 0,0 F.P.

21

22, 23

Ratios of Rate Constants (Radical Disproportion Reactions)

Reactions Notes Rate constants ratios Temperature rangeRadical source Reference

(1) H + H02 = 20H

(2) 2H02 = H2 02 + 02

cm3

, mole. sec. units

A

2 /A2 = 5.1 X 10»

°C

500 H2 /0„ ignition 35, 36

(1) 2HS = H2 + S2

( 2 ) 2HS = H2 S + S Ai/A2 = 0.15 room temp. h2 s p 37

(1) 2HNO = H2 0 + N2 0

(2) 2HNO = 2NO + H2 Ai/A 2 = 8 25 c2 h5 oh/no h 38

( 1 ) c2 h5 + c5 h9 o=c2 h+c2 hxooc2 h

(2) C2 H5 + C5 H9 02 = C2 H6 + C5 H8 02 A,/A2 =0.1 29 c2 h5 cooc2 h5 p 39

(1) 2C2 H5 0 = C2 H.0H + CH.! CH0

( 2 ) C2 H5 0 = CH3 + CH2 0

Ai/A 3 = 1.2 x 10 10

A,/A2 = (3±l)x 10 12

15230 c2 h5 cooc2 h. p c2 h5cooc2h5 p

40

40

(1 ) 2(CH.s).J CO = (CH3

) 3 COH + (CH3

) 2'CCH2 0

(2) (CH3

) 3 CO = CH.3 COCH3 + CH3

' Aj/A* =£ 3.0 x 10 8 25 ((CH3

)3 CO) 2 p 41

Notes

(a) Review of literature data.

5. Burgess and

(1958). 6 . Dixon-Fewis

Robb, Chem. Soc. Special Publ. No. 9 167

and Williams, Nature 196, 1309 (1962).

(b) Value based on E.S.R. measurements of the radical concentration.

References

1 . Clyne and Thrush, Trans. Faraday Soc. 57, 1305 (1961).

2. Clyne and Thrush, Disc. Faraday Soc. 33, 139 (1962).

3. Bulewicz and Sugden, Proc. Roy. Soc. 277A, 143 (1964).

4. Kaufman and Del Greco, 9th Int. Comb. Symp., p. 659

(Academic Press, N.Y., 1963).

7. Skinner and Ringrose, J. Chem. Phys. 43, 4129 (1965). 8 . Diesen, J. Chem. Phys. 39, 2121 (1963).

9. Salzman and Bair, J. Chem. Phys. 41, 3654 (1964).

10. Del Greco and Kaufman, Disc. Faraday Soc. 33, 128 (1962).

11 . Westenberg and De Haas, J. Chem. Phys. 43, 1550 (1965).

12. Skinner and Ringrose, J. Chem. Phys. 42, 2190 (1965).

13. Dixon-Fewis, Wilson, and Westenberg, J. Chem. Phys.

44, 2877 (1966).

14. Fairbairn. Proc. Roy. Soc. 267A, 88 (1962).

15. Paterson and Greene, J. Chem. Phys. 36, 1146 (1962).

16. Clyne, 10th Int. Comb. Symp., p. 311 (Comb. Inst., Pitts- burgh. 1965).

106
17. Ferguson and Phillips, J. Chem. Soc. 4416 (1965).

18. Schiavello and Volpi, J. Chem. Phys. 37, 1510 (1962).

19. Hutton and Wright, Trans. Faraday Soc. 61, 78 (1965).

20. Hutton, Nature 203, 835 (1964).

21. Edgecombe, Norrish, and Thrush, Proc. Roy. Soc. 243A,

24 (1957).

22. Lipscomb, Norrish, and Porter. Nature 174, 785 (1954).

23. Porter and Wright, Disc. Faraday Soc. 14, 23 (1953).

24. Goldfinger, Jeunehomme, and Martens, J. Chem. Phys.

29, 456 (1958).

25. Huybrechts, Meyers, and Verbecke, Trans. Faraday Soc. 58, 1128 (1962).

26. Schott and Davidson, J. Am. Chem. Soc. 80, 1841 (1958).

27. McDowell and Sharpies, Can. J. Chem. 36, 268 (1958).

28. McDowell and Sharpies, Can. J. Chem. 36, 1227 (1958).

29. Dainton, Lomax, and Weston, Trans. Faraday Soc. 58,

308 (1962).

30. Ayscough, Cocker, Dainton, and Hirst, Trans. Faraday

Soc. 58, 295 (1962). 31. Dusoleil, Goldfinger, Mahieu-van der Auwera, Martens,

and van der Auwera, Trans. Faraday Soc. 57, 2197 (1961).

32. Burns and Dainton, Trans. Faraday Soc. 48 , 39 (1952).

33. Bodenstein, Brenschede, and Schumacher, Z. Phys. Chem.

40B, 121 (1938).

34. Baldwin and Mayor, Trans. Faraday Soc. 56, 103 (1960).

35. Baldwin and Mayor, Trans. Faraday Soc. 56, 80 (1960).

36. Darwent and Roberts, Proc. Roy. Soc. 216A, 344 (1953).

37. Knight and Gunning, Can. J. Chem. 39, 2466 (1961).

38. Wijnen, J. Am. Chem. Soc. 82, 3034 (1960).

39. Wijnen, J. Am. Chem. Soc. 80, 2394 (1958). 40. McMillan and Wijnen, Can. J. Chem. 36, 1227 (1958).

247-168 0- 67—8

107
Disproportionation/Combination Ratios

Index

(a) Hydrogen Atom Transfer Page Reactions of

1. Hydrogen atoms, H 109

2. Methyl, CH3 109

3. Methoxy, CH3 0 110

4. Halogenated methyl, CC13 and CF2 H 110

5. Vinyl, CH2 CH Ill

6. Ethyl, C2 H5 Ill

7. Ethoxy, C2 H5 0 112

8. Hydroxy ethyl, CH3 CH(OH) 112

9. Halogenated ethyls, C2F5

, C2 H4 C1 112

10. Allyl, CH2 CHCH2 113

11. n-Propyl, CH3 CH2 CH2 113

12. iso-Propyl, CH3 CHCH3 113

13. Propoxy, CH3 CH2 CO 114

14. n-Perfluoropropyl, CF3 CF2 CF2 114

15. Butyls, CH3 CH2CH2 CH2

, CH3 CHCH2 CH3

, (CH3

)2CHCH2 , CH3

) 3 C 114

16. Monochlorobutyl, C4 H8 C1 115

17. Pentyl, n-C5 Hn , cyclo-C5H9 115

18. Hexyl, cyclo-C6Hn , C6 H13 115

19. Amino, NH2 115

20. Nitric oxide, NO 115

21. Iodine atom, 1 115

(b) Chlorine Atom Transfer

1. Halogenated methyl, CF2 C1 115

2. Halogenated ethyl, C2 H4 C1, C2 F2 C13 116

3. Monochlorobutyl, C4 Hg Cl 116

(c) Oxygen Atom Transfer

1. Methyl, CH3 116

108
Disproportionation/Combination Ratios

The following convention is used throughout this table, e.g. for ethyl and n-propyl radicals, the possible reactions are:

C2 H5 + n-C3 H7 = C5 HI2 (1) C2 H5 + n-C3 H7 = C2 H6 + C3 H6 (2) C2 Hs + n-C3 H7 = C2 H4 + C3 Hs (3)

k2 lki is listed as C2 H5/n-C 3 H7 and k3 /ki as n-C3 H7 /C2 H5

.

The table is constructed with reference to the radical receiving the transferred atom. In the above example, A2 /Ai is in the section on ethyl radicals and A3/Aj, with the n-propyl radicals. The radicals are further classified according to the number of carbon atoms they

contain. Thus the table starts with H atom reactions, followed by C, reactions (methyl radicals and halogen and oxygen containing derivatives of methyl radicals,) then by C2 reactions, etc.

Reactants Notes Adis/Acomb. Tempera- Radical source Reference

ture range

HYDROGEN ATOM TRANSFER

Hydrogen atom °C

h/c2 h5 0.05 ±0.03 26-203 (C 2 H5

) 2 CO + H2 -h 1

d/c2 h5 (a) 0.21 ±0.07 26-203 (C2H5)2CO + D2 -h 1

d/ch3 cd2 0.06 ±0.03 26-203 (CH3 CD2

) 2 CO+D2 -h 1

D/i-C3H7 0.2 85 2

H/Cs Hn

0.099 25 iso-C

5 H12 -H 3

h/c6 h13 0.12 25 n-C„H6 14 -H 4

Methyl

CH3/CH2 :CH 2.3 175 CH2 :CHCHO and 5 HCOOCH:CH2 + ch3 ch3/c2 h5 0.04 ±0.02 78-130 ch3 coc2 h5 p 6

0.055 77-230 hcooc2 h5 + CH:) 7 0.039 ±0.007 110-166 (CH4 ),C0 + (C9 H.),C0 8 p

0.039 ch3/ch3 cd2 0.06 ±0.01 90 (CH3

) 2 CO 9 + (CH3CD2

) 2 CO p

cd3/c2 h5 <0.08 27 (CD3) 2 CO + (C2 H5)2 CO

p

10

CH3/n-C3H7 0.095 ±0.01 74-178 HCOOCH2 CH2 CH3 11

0.025 ± 0.004 139-173

+ CH., n-C3 H7 CHO +CH:, 12

0.041 ±0.01 118-144 (CH3

) 2 CO

+ (n-C

3 H7

) 2 N2 P

8

(b) 0.14 13

109
Disproportionation/Combination Ratios — Continued

Reactants Notes Ardis/^comb. Temperature rangeRadical source Refers ence

°C

cd3 /ch3 ch2 cd2 0.05 25-28 cd3 cocd2 ch2 ch3 p 14 CH3/i-C

3H7 0.216 ±0.032 80-150 (CH3

)2 CO 15 + CH3 COCH(CH.s

) 2 P

0.195 94-181 HCOOCH(CH3

) 2 +ch3 11 0.21 cd3/ch3 cdch3 0.17 ±0.03 53-116 CD3 COCD(CH3

) 2 p 16 CH3 /n-C4 H9 0.15 70-195 hcooc4 h9 +ch3 13, 103 CH3 /sec-C 4 H9 0.30 - 103—1-25 cw-CH3CH:CHCH3 17 + H

0.07 107-168 CH3 CH:CH2 +CH:! 18 CH3 /f-C

4 H9 (c) 0.85 ±0.1 20-60 ((CH3

) 3 CO)2 p 19

0.88 25-79 ((CH3

) 3 CO)2 p 20

0.699 ±0.037 80-188 ((CH3

)3C)2CO p 15

(d) 0.806 21

0.80 CH3/n-C5Hn

0.1 63 CH3 COC5 Hu p 22 CD3 /cyclo-C5 H9 0.31 132-218 <cd3

)2 co p 23

ch3/cdo 2.5 80-180 (CH3

)2n2 p 24 ch3/ch3 o 1.25 29 ch3 cooch3 p 25

(a) 1.51 ±0.2 124-185 ch3 ooch3 t 26

ch3 /cd3 o 1.4 ±0.1 30-201 ch3 coocd3 p 27 cd3/cd3o 1.8 30-201 ch3 coocd3 p 27 ch3/ch3 co 0.06 29 ch3 cooch3 p 25

0.05 30 ch3 coocd3 p 104

=£ 0.095 55 ch3 co.coch3 -h 28

cd3/cd3 co 0.014 to 0.055 25 cd3 cocd2 ch2 ch3 P 14 ch3/ch3coch2 0.25 ±0.25 184-285 ch3coch3 p 29

CH3/(CH3)2CHO 3.4 26 ((CH3

)2 CHO), p 30

VIethoxy

ch3 o/ch3 o ^ 60 25 (CH3

) 2 n2 +o2 p 31

9.3 ±0.6 room temp. ch3 i+o2 p 32

ialogenated Methyls

CC13 /C2 H5 0.24 ± 0.04 25 (C2 H5

)2 C0 + CC14 p 33

0.22 ±0.03 0-58 c2 h4 +cci4 p 34

cci3/c2 h4 ci 0.11 ±0.02 26 c2 h4 +cci4 p 105

0.14 ±0.03 0-58 C2 H4 + cci4 p 34

cci3 /c2 h4 coc2 h5 0.9 ±0.1 25 (C2 H5

) 2 C0 + CC14 p 33

110
Disproportionation/Combination Ratios — Continued

Reactants Notes Adis/Acomb. Temperature range

Radical source Reference

°C

cf2 h/cf2 h 0.19 75-119 cf2 cih -h 35

Vinyl

CH2 :CH/CH2 :CH 1.1 175 CH2 :CHCHO and 5 HCOOCH:CH2 + ch3 (e) 0.5 272-301 5 0.02 50 (CH2 :CH)2 Hg P 36 CH2 :CH/C2 H5 0.03 161-175 (C 2 H5

) 2 CO p 37

Ethyl

C2 H./CH2 :CH 0.12 161-175 (C2 H5

) 2 CO p 37

c2 h5/c2 h5 0.36 75 (C2 H5

)2Hg P 38

0.46 200 (C2 H5 ),Hg P 38

0.11 25 (C2 H5

) 2 CO p 39

0.085 101 (C2 H5

) 2CO p 39

0.17 25 C2 H4 + H 40

0.22-0.61 42 c2 h4 +h 41

0.47 200 c2 h4 +h 41

0.10 25 c2 h5 cho p 42

0.13 350 (C 2 H5

) 2 Hg ~ T 43

0.13 122 C2 H5 CHO +CH.s 44

0.15 156 c2 h5cho +ch s 44

0.13 ±0.02 26-74 (c2 h5

)2 n2 p 45

0.12 100-200 (C 2 h5

) 2 co p 46

0.15 ±0.01 25 c2h4 +H 47

0.136 ±0.02 50-215 (C 2 h5

) 2 co p 48

0.12 ±0.01 27-118 (C 2 h5

) 2 n2 p 49

0.15 50-315 c2 h5cho P 50

0.14 77-230 hcooc2h5 +ch:) 7

[0.16 -651

(f) 0.13 ° (C.HJ.N, p 51, 52 |o.n 9 40J 0.130 ±0.007 115-150 (C2 H5

) 2 CO p 8

0.11 ±0.01 22 (C2 h5

)2 n2 f.p. 53

0.123 ±0.008 25-200 (C2 H5

)2 CO p 54

0.134 ±0.003 79-141 (C 2 H5

) 2 CO p 55

0.11 room temp. CH2 :CH2 +H 56

0.137 71-175 (C2 H5

) 2 CO p 106

0.135 ch:! cd2 /ch:) cd2 (g) 0.1 24-180 (CH.,CD2

) 2 CO p 57

c2 d5 /c2 d5 0.098 5 ± 0.008 50-197 (C2 D5

)2 CO p 58 c2 h5/ch2chch2 0.05 134-175 (C2 H5

) 2 CO p 106

C2 H5 /n-C.

( H7 0.14 117 (C2 H5

) 2 CO 59 + HCOOnC.H. P

0.081 ±0.01 61-129 (C2 H5) 2 CO 8 + (n-C

3 H7

)2N2 p

0.06 ±0.04 -78-+24 C:! Hh -h 60

0.08

111
Disproportionation/Combination Ratios — Continued

Reactants Notes Adis/Acomb. Temperature Range

Radical Source Refer- ence

°C

C2 H5/i-C

:i H7 0.2 room temp. CH2 :CH, 107 + CH3 CH:CH, +H

0.21 ±0.02 25 c3 h8 -h 61

0.43 ± 0.03 34-144 hcoooc3 h7 59 + (C2 Hs

) 2 CO p

0.43 48-112 c2 h5 cho 62 + t-CjHXHO P

0.43

C2 H5 /sec-C4 H9 0.23 ±0.01 25 -H 61

C2H5/i-C

4 Hg 0.02 ± 0.02 0 i- C.H 10 -H 60

C2 H5 /f-C

4 H9 0.3 room temp. CH2 :CH2 107 + (CH3

) 2 C:CH2 +H

0.53 73-80 (C2 H5

) 2 CO 62 + ((CH3

) 3 C)2 CO p

0.54 ±0.01 25 i-C

4Hio — H 61

0.54

C2 H5/cyclo-C

5 H9 0.27 ±0.05 25 cyclo-C5 H10 - H 61

C2 H5/n-C

5Hn

0.08 ± 0.04 0 n-C5 H12 -H 60

C2 H5/sec-C 5 Hn(h) 0.25 ±0.01 25 n-C5 H12 -H 61

C2 H5/t-C

5H11 0.60 ±0.01 25 (CH3

) 2 CHCH2 CH3 -h 61

C2 H_/cyclo-C6 H7 (i) 0.38 ± 0.03 50-120 (C 2 H5

) 2 CO p 64

C2Hs/(CH3

)3CCHCH3 0.20 ±0.02 25 (CH3

)3CCH2CH3 - H 61

C2 H5 /sec-hexyl (j

)

0.27 ±0.01 25 n-C6 H14 -H 61 C2 H5/(CH3

)2 CC3H7 0.74 ±0.03 25 (CH3

) 3 CHCH2 CH2 CH3 -h 61

C2 H5/(CH3

) 2 CCH(CH3) 2 0.72 ±0.01 25 (CH3)2 CHCH(CH:s ) 2 - H 61

C2 H5/CH3 C(C2 H5

) 2 0.8 25 CH3 CH(C2 H5

) 2 -h 61

c2h5/ch3 ch2 o 1.3 ±0.2 15-29 c2 h5cooc2 h5 p 65

thoxy

ch3 ch2 o/c2 h5 2.3 ±0.3 29 c2 h5cooc2 h5 p 65

ch3 ch2 o/ch3ch2 o 12 ±2 25 c2 h5 i+o2 p 66

[ydroxy ethyl

CH3 CH(OH)/CH3 CH(OH) (k) 0.3 25 C2 H5OH - H 67

ialogenated ethyl

c2f5 /c2 h5 0.56 21-240 c2f5 coc2 h5 p 112

C2 H4 C1/C2 H5 0.22 0-58 c2 h4 +cci4 p 34

112
Disproportionation/Combination Ratios — Continued

Reactants Notes /rdis/^comb. Temperature Range

Radical Source Reference

°C

C2 H4 C1/C2 H4 C1 «0.05 0-58 c2 h4 +cci4 P 34

*2 0.1 26 c2 h4 + cci4 p 105

(1) 0.36 23 c2 h4 +coci2 p 68

(m) 24 23 c2 h4 + coci2 p 68 c2 h4 ci/c4 h8ci (n) 0.40 23 c2 h4 + coci2 p 68

Allyl

ch2 chch2/c2 h5 0.13 134-175 (C2 H5

) 2 CO p 106

n-Propyl

n-C3 H7/C2 H5 0.058 ±0.01 61-129 (C 2 h5

) 2 co 8 + ( n-C3 H7

)2 N2 P

n-C3 H7/n-C

3H7 0.21 113 (n-C

3 H7

) 2 CO P 69

0.1 25 n-C3 H7CHO P 75

0.3 30-108 (n-C

3 H7

) 2 Hg P 63

0.125 ±0.01 100-150 (n-C3 H7

) 2 CO p 108

0.16 25-191 n-C3 H7CHO P 70

0.157 25-130 (n-C 3 H7

) 2 N2 P 71 0.14 74-178 hcooch2 ch2 ch3 11 + ch3 0.141 ±0.015 18-150 (n-C 3 H7

) 2 N2 P 8

0.14

c2 h5 cd2/c2 h5 cd2 0.15 25-28 ch3 ch2 cd2 cocd„ p 14

Iso-Propyl

iso-C

3 H7 /C2 H5 0.19 48-112 c2 h5 cho 62 + i-C

3 H7CHO p

0.2 room temp. CH2 :CH2 107 + CH3 CH:CH„ +H

0.07 34-144 (C2h5

) 2 C0 p 59

0.19

iso-C.

5 H7 /iso-C3 H7 1.5 30 CH3 CH:CH2 + H 72

2. 200 CH3 CH:CH2 +H 72

1. 270 (j-C

3 H7

) 2 Hg T 73

0.53 30 (i-C3 H7

)2N2 P 74

0.5 25 tc3 h7 ch6 p 75

0.77 25 CH3 CH:CH2 +H 76

0.48 320 CH.CHiCH, +H 76

0.6 200 (i-C.,H

7

) 2 CO P 77

0.65 20-261 j-C 3 H7 CHO p 109

0.5 ±0.05 room temp. CH.,CH:CH, + H 56

0.54 61-127 ((CH.s ) 2 CH)2 N2 p 78

0.65 94-181 HCOOt-C3 H7 +C.H, 11 0.58 ±0.04 75-136 ((CH.,)

2 CH)2 CO p 79

0.65 (CH3

)2 CD/(CH3

)2CD 0.63 ± 0.04 25-125 ((CH3

)2 CD)2 CO p 80

0.67 53-116 (CH3

) 2 CDCOCD3 p 16

iso-C

3 H?/sec-C4 H9 0.4 room temp. CH3 CH:CH2 107 + CH.i CH:CHCH.j + H

113
Disproportionation/Combination Ratios — Continued

Reactants Notes Adis/Acomb. Temperature Range

Radical Source Refer- ence

°C

iso-C..H 7/f-C.H 6 7' 4 Q9 0.5 room temp. CH3 CH:CH2 107 + (CH3

) 2 C:CH2 +H

0.70 72-82 (f-C

4 H9

) 2 CO 62 + (i-C

3 H7

)2CO p

iso-C.

s H7/cyclo-C6 H7

(i) 0.52 ±0.09 75-136 (£-C3H7)2CO P 79

Propoxy

c2 h5co/c2 h5 0.4 ±0.1 24 (C 2 Hs

) 2 CO fp 81

n-Perfluoropropyl

n-C3 F7/C2 H5 0.40 87-196 (n-C3 F7

) 2 CO P 82

(o) 0.021 exp (2.2/RT) 80-256 n-C3 F7 COC2 H5 P 83

Butyls

n'C4 H9/ra-C

4H9 5. 140 (n-C

4 H9

) 2 Hg P 84

0.94 ±0.05 70-195 HCOOn-C H +CH, 13

0.95 ±0.05 75-186 HCOOn-C4 H9 +CH, 103

(P) 10° 6 exp (-1.3/RT) 61-229 n-C4 H9 CHO P 15

0.95

sec-C4 H9/i-C

3 H7 (D 0.4 room temp. CH3 CH:CH2 107 + CH.j CH:CHCH.s + H

sec-C4 H9 /sec-C4 H9 (q) 1.64 25 CH.CH.CHlCH.^CHO 85

P

2.27 100 (CKfcH,CH(CHj),CO 86

P

1.5 room temp. CH.,CH:CHCH.( +H 110

0.95 - 103-+25 cisCH.jCHiCHCH,, 17 + H

=£ 1.2 107-168 CH3 CH:CH2 +CH.( 87

1.5 24 CH.CH.CITCH., +H 84

3.5 220 CH3CH2 CH:CH2 + H 84

0.63 ±0.08 - 78-+25 trans-CH.jCHrCHCH.j 88 + H

sec-C4 H9 /?-C 4 H9 (r) 0.23 room temp. CH3 CH:CHCH3 107 + (CH3

)2C:CH2 +H

iso-C

4 H9 /iso-C 4 H9 0.42 78-109 ((CH.,),CHCH,),CO P 86

0.17 26-124 (CH3

)2 CHCH2 CHO P 89

0.17

t-C

4 H9/C2 H5 (r) 1.7 room temp. CH2 :CH2 107 + (CH3

)2 C:CH2 +H

0.31 73-80 (£-C4 H9

)2 CO 62 + (C2 H5

)2 CO p

t-C

4 H9 /iso-C.,H 7 (r) 1.2 room temp. CH3CH:CH2 107 + (CH3

)2C:CH2 +H

0.67 72-82 (£-C

4 H9

)2CO 62

+ (i-C,H7

)2CO P

114
Disproportionation/Combination Ratios — Continued

Reactants Notes Adis/Acomb. Temperature Range

Radical Source Reference

°C

t-C 4 H9/sec-C4 H9 (r) 2.0 room temp. CHjCHtCHCH., 107 + (CH3

) 2 C:CH, +H

f-C

4 H9/t-C,H9 4.5 23 (CH.,)

2 C:CH2 +H 84

6.5 300 (CH3

) 2 C:CH2 +H 84

4.59 117-322 (t-C

4 H9

)2 CO P 86

7.4 20-60 (±C4 H90)2 p 90

4.38 27-230 r-C

4 H9 CHO P 91

3.19 50-80 R-C4 Hg

) 2 CO and 62

r-C

4 H9 CHO P

2.2 ±0.3

3.2 room temp. (CH3

)2C:CH2 +H 107

Monochlorobutyl

C4 Hx C1/C2 H4 C1 0.07 23 CH2 :CH2 + C0C12 P 68

Pentyls

n-C5Hn/ n-C 5 Hn

0.2 63 n- c5 hu coch3 p 22

c5 hu/c5 hu2.45 25 iso-C

5H12 — H 3 3=0.66 21 «-c5 h12 -h 92

cyclo-C5 H9/cyclo-C 5H9 0.19 29 cyclo-C5 H10 — H 93

1.0 24 cyclo-C5 H)0 — H 94

1.0 26-250 cyclo-C

5H10 - H 95

1.0

Hexyls

cyclo-C( .H n/cyclo-C( .H ]l 0.46 29 cyclo-Cfi H]2 — H 111

cyclo-CgHj 4 / cyclo-CgH, j (s) 0.42 29 93

c6h13/c64 0.97 ±0.08 25 «c8 h14 -H 4 Amino

nh2 /nh2 0.18 no indication nh3 f.p. 97

Nitric Oxide

NO/CH.,0 (t) 0.5 174 96 no/ch:! ch2 o 0.28 95-135 (C2 h5 0)2 p 96

NO/(CH3

)2CHO (u) 10.15 26 30

to. 175 79 (£-C

3 H7 0)2 p 30

Iodine atom

i/c 2 h5 0.33 ±0.03 28 (C 2 h5

) 2 co+c2 h5

i P 98

CHLORINE ATOM TRANSFER

Halogenated Methyl

CF2 C1/CF2 C1 «0.5 75-119 CF2 C1H - H 99

115
Disproportionation/Combination Ratios — Continued

Reactants Notes Adis/Acomb. Temperature Range

Radical Source Reference

Halogenated Ethyl

°C

C2H4 C1/C2 H4 C1

(m)

=£0.1

5.8 2623 c2 h4 + cci4 p c2 h4 + COCl2 P

10568 c2 f2 ci3 /c2 f2 ci. =£0.13 30-70 CF2 :CC12 + C12 P 100 C2 H4 C1/C4 Hs C1 (n) (v) 0.5 23 c2 h4 +coci2 p 68

Monochlorobutyl

C4 Hk C1/C2 H4 C1 (n) (w) 4.0 23 c2 h4 +coci2 p 68

OXYGEN ATOM TRANSFER

Methyl

ch3/no2 2.0 55-90 ch.,cho+no2 101

(X) (y) 2.4 25 ch..no2 p 102

(x) (y) 1.8 105 ch3 no2 p 102

Notes

(a) Authors consider this value to be too high.

(b) Unpublished work by Thynne.

(c) Author believes the radicals to be vibrationally exited.

(d) A recalculation of data from Kerr and Trotman-Dickenson,

J. Chem. Soc. 1609 (1960).

(e) Calculated from data of Le Roy and Tickner, J. Chem.

Phys. 19, 1247 (1951).

(f) The temperature dependence gives either Edis-Ecomb = — 0.3 kcal/mole or Adis/Acomb = T~ 0 - 7

.

(g) The ethylene formed was more than 90 percent C2 H2 D2

.

(h) Sec-pentyl is a mixture of the radicals CH3 CH2 CHCH2 CH3 and CH3 CHCH2 CHiCH3

.

(i) Cyc/o-C6H7 is the cyclohexadienyl-1,4 radical.

(j) Sec-hexyl is a mixture of the radicals CH3 CH-C4 H9 and c2 h5 chc3 h7

. (k) This value is probably low.

(l) Combination product is 1.4—

C

4 H8 C12

. (m) Combination product is 1.3-C4 HK C12

. (n) Combination product is 1.6—

C

B H12 C12

. (o) Alternatively Adis/Acomb = 0.33 with a large scatter.

(p) Temperature coefficient very doubtful.

(q) In the range 25-243 °C, the results fit the expression

Adis/Acomb = 0.715 exp (500/RT).

(r) Very doubtful.

(s) Cyclo-C6Hn

is the methylcyclopentanyl radical.

(t) Unpublished work by h’hillips.

(u) The ratio could be 0.16 within the experimental error of both results.

(v) Products of the disproportionation reaction are C4 H8 and

1,2-C2 H4 C12. (w) Products of the disproportionation reaction are C2 H4 and

1,4-C

4 H8 C12

. (x) The “disproportionation reaction” is the sum of the rate constants for two reactions viz. (i) CH3 + N02 = CH3ONO, and

(ii) CH.S + N02 = CH3 0 + NO.

(y) Combination product is CH3 N02

.

References

(1) Heller and Gordon, J. Chem. Phys. 36, 2648 (1962).

(2) Heller and Gordon, J. Phys. Chem. 64, 390 (1960).

(3) Kuntz, J. Phys. Chem. 69, 2291 (1965).

(4) Kuntz, J. Phys. Chem. 69, 4396 (1965).

(5) Weir, J. Chem. Soc. 6870 (1965).

(6) Ausloos and Steacie, Can. J. Chem. 33, 1062 (1955).

(7) Thynne, Trans. Faraday Soc. 58, 676 (1962).

(8) Grotewold and Kerr, J. Chem. Soc. 4337 (1963).

(9) Heller, J. Chem. Phys. 28, 1255 (1958).

(10) Wijnen, J. Chem. Phys. 22, 1631 (1954).

(11) Thynne, Trans. Faraday Soc. 58, 1394 (1962).

(12) Grotewold and Kerr, J. Chem. Soc. 4342 (1963).

(13) Thynne, Proc. Chem. Soc. 18 (1961).

(14) Ausloos and Murad, J. Am. Chem. Soc. 80, 5929 (1958).

(15) Kerr and Trotman-Dickenson, J. Chem. Soc. 1609 (1960).

(16) Heller, J. Chem. Phys. 35, 1711 (1961).

(17) Rabinovitch and Diesen, J. Chem. Phys. 30, 735 (1959).

(18) Miyoshi and Brinton, J. Chem. Phys. 36, 3019 (1962).

(19) Frey, Proc. Chem. Soc. 385 (1959).

(20) McMillan, J. Am. Chem. Soc. 82, 2422 (1960).

(21) Blake, Henderson, and Kutschke, Can. J. Chem. 39,

1920 (1961).

(22) Wijnen, J. Am. Chem. Soc. 83, 3752 (1961).

(23) Gordon, Can. J. Chem. 43, 570 (1965).

(24) Toby and Kutschke, Can. J. Chem. 37, 672 (1959).

(25) Wijnen, J. Chem. Phys. 27, 710 (1957).

(26) Thynne and Gray, Trans. Faraday Soc. 59, 1149 (1963).

(27) Wijnen, J. Chem. Phys. 28, 939 (1958).

(28) Harrison and Lossing, Can. J. Chem. 37, 1478 (1959).

(29) Darwent, Allard, Hartman, and Lange, J. Phys. Chem.

64, 1847 (1960).

(30) McMillan, J. Am. Chem. Soc. 83, 3018 (1961).

(31) Dever and Calvert. J. Am. Chem. Soc. 84^ 1362 (1962).

(32) Heicklen and Johnston, J. Am. Chem. Soc. 84, 4030

(1962).

(33) Gregory and Wijnen, J. Chem. Phys. 38, 2925 (1963).

(34) Rocquitte and Wijnen, J. Am. Chem. Soc. 85 , 2053

(1963).

(35) Bellas, Strausz, and Gunning, Can. J. Chem. 43, 1022

(1965).

(36) Sherwood and Gunning, J. Phys. Chem. 69, 2323 (1965). 116
(37) James and Troughton, Trans. Faraday Soc. 62, 145

(1966).

(38) Ivin and Steacie, Proc. Roy. Soc. 208A, 25 (1951).

(39) Kutschke, Wijnen, and Steacie, J. Am. Chem. Soc. 74,

714 (1952).

(40) Moore and Taylor, J. Chem. Phys. 8, 504 (1940).

(41) Le Roy and Khan, J. Chem. Phys. 15, 816 (1947).

(42) Blacet and Pitts, J. Am. Chem. Soc. 74, 3382 (1952).

(43) Gowenlock, Polanyi, and Warhurst, Proc. Roy. Soc. 218A, 269 (1953).

(44) Volman and Brinton, J. Chem. Phys. 22, 929 (1954).

(45) Ausloos and Steacie, Bull. Soc. Chim. Beiges. 63, 87

(1954).

(46) Brinton and Steacie, Can. J. Chem. 33, 1840 (1955).

(47) Smith, Beatty, Pindar, and Le Roy, Can. J. Chem. 33,

821 (1955).

(48) James and Steacie, Proc. Roy. Soc. 244A, 289 (1958).

(49) Cerfontain and Kutschke, Can. J. Chem. 36, 344 (1958).

(50) Kerr and Trotman-Dickenson, J. Chem. Soc. 1611 (1960).

(51) Dixon, Stefani, and Szwarc. J. Am. Chem. Soc. 85, 2551

(1963).

(52) Matsuoka, Dixon, Stefani, and Szwarc, Proc. Chem. Soc. 304 (1962).

(53) Dingledy and Calvert, J. Am. Chem. Soc. 85, 856 (1963).

(54) Brown and James, Can. J. Chem. 43, 660 (1965).

(55) James and Troughton, Trans. Faraday Soc. 62, 120

(1966).

(56) Boddy and Robb, Proc. Roy. Soc. 249A, 518 (1959).

(57) Wijnen and Steacie, Can. J. Chem. 29, 1092 (1951).

(58) Boddy and Steacie, Can. J. Chem. 38, 1576 (1960).

(59) Thynne, Proc. Chem. Soc. 68 (1961).

(60) Holroyd and Pierce, J. Phys. Chem. 68, 1392 (1964).

(61) Holroyd and Klein, J. Phys. Chem. 67, 2273 (1963).

(62) Dominguez, Kerr, and Trotman-Dickenson, J. Chem.

Soc. 3357 (1962).

(63) Caule and Steacie, Can. J. Chem. 29, 103 (1951).

(64) Brown and James, Can. J. Chem. 43, 660 (1965).

(65) Wijnen, J. Am. Chem. Soc. 82, 3034 (1960).

(66) Heicklen and Johnston, J. Am. Chem. Soc. 84, 4030

(1962).

(67) Knight and Gunning, Can. J. Chem. 39, 2466 (1961).

(68) Heicklen, J. Am. Chem. Soc. 87, 445 (1965).

(69) Masson, J. Am. Chem. Soc. 74, 4731 (1952).

(70) Kerr and Trotman-Dickenson, Trans. Faraday Soc. 55,

572 (1959).

(71) Kerr and Calvert, J. Am. Chem. See. 83, 3391 (1961).

(72) Moore, J. Chem. Phys. 16, 916 (1948).

(73) Chilton and Gowenlock, Trans. Faraday Soc. 49, 1451

(1953).

(74) Durham and Steacie, Can. J. Chem. 31, 377 (1953).

(75) Blacet and Calvert, J. Am. Chem. Soc. 73, 661 (1951).

(76) Hoev and Le Rov, Can. J. Chem. 33, 580 (1955).

(77) Heller and Gordon, J. Phys. Chem. 60, 1315 (1956).

(78) Riem and Kutschke, Can. J. Chem. 38, 2332 (1960).

(79) James and Suart, J. Am. Chem. Soc. 86, 5424 (1964).

(80) Heller and Gordon, J. Phys. Chem. 62, 709 (1958).

(81) Fischer and Mains, J. Phys. Chem. 68, 188 (1964).

(82) Giacometti and Steacie, Can. J. Chem. 36, 1493 (1958).

(83) Pritchard and Thommarson, J. Phys. Chem. 69, 1001

(1965).

(84) Moore and Wall, J. Chem. Phys. 17, 1325 (1949).

(85) Gruver and Calvert, J. Am. Chem. Soc. 78, 5208 (1956).

(86) Kraus and Calvert, J. Am. Chem. Soc. 79, 5921 (1957).

(87) Miyoshi and Brinton, J. Chem. Phys. 36, 3019 (1962).

(88) Kubin, Rabinovitch, and Harrington, J. Chem. Phys. 37,

937 (1962).

(89) Metcalfe and Trotman-Dickenson, J. Chem. Soc. 5072

(1960).

(90) Frey, Proc. Chem. Soc. 385 (1959).

(91) Birrell and Trotman-Dickenson, J. Chem. Soc. 4218 f (1960).

(92) Back, Trans. Faraday Soc. 54, 512 (1958).

(93) Beck, Kniebes, and Gunning, J. Chem. Phys. 22, 678

(1954).

(94) Stock and Gunning, Can. J. Chem. 38, 2295 (1960).

(95) Gunning and Stock, Can. J. Chem. 42, 357 (1964).

(96) Arden, Phillips, and Shaw, J. Chem. Soc. 5126 (1964).

(97) Salzman and Bair, J. Chem. Phys. 41, 3654 (1964).

(98) Guercione and Wijnen, J. Chem. Phys. 38, 1 (1963).

(99) Bellas, Strausz, and Gunning, Can. J. Chem. 43, 1022

(1965). (100) Vallana, Castellano, and Schumacher, Z. Phys. Chem.

46, 294 (1965). (101) Phillips and Shaw, 10th Int. Comb. Symp., p. 423,

Combustion Institute, Pittsburgh (1965). (102) Rebbert and Slagg, Bull. Soc. Chim. Beiges 71, 709

(1962). (103) Thynne, Trans. Faraday Soc. 58, 1533 (1962). (104) Wijnen, J. Chem. Phys. 28, 271 (1958). (105) Roquitte and Wijnen, J. Chem. Phys. 38, 4 (1963). (106) James and Troughton, Trans. Faraday Soc. 62, 145

(1966). (107) Boddy and Robb, Proc. Roy. Soc. 249A, 547 (1959). (108) Whiteway and Masson, J. Chem. Phys. 25, 233 (1956). (109) Kerr and Trotman-Dickenson, Trans. Faraday Soc. 55,

921 (1959). (110) Boddy and Robb, Proc. Roy. Soc. 249A, 532 (1959). (111) Beck, Kniebes, and Gunning, J. Chem. Phys. 22, 672

(1954). (112) Thommarson and Pritchard, J. Phys. Chem. 70, 2307

(1966).

117
Molecule-Molecule Reactions (Hydrogen and Hydrogen Halides)

Reactions Notes E logioA Temperature range

Radical source Reference

(kcal mole-1

) (cm3 mole-1 sec

-1

) °C

H2 + 02 = 20H 45.0 (k = 84.0) 485 H2 /02 ignition 1 67.0 14.4 687-807 h2 /o2 s.t. 2 H2 + I

2 = 2HI (a) 39.0 14.1 10-235 HI T • 3 41.0 15.09 598-774 h2 /i

2 t 9. 10

k = 6.60 ±0.09 394 h2 /i

2 T 11 41.24 ±0.25 14.35 ±0.07 105-360 h2/i

2 T 12

D2 + I 2 = 2DI (b) (c) 41.47 ±0.20 14. 14 ±0.07 360-465 ivi, T 13

Hp + HI = H2 ° + HI 44 ±3 13.7 420-480 h2/i

2 /hi t 14

3= 47 420-480 h2/i

2/hi t 17 h2 + no2 = no + h2 o 18 9.3 384-434 H2 /02/N02 t 15

hci + no2 =hno2 23.4 11.6 100-420 hci/no2 t 23 + C1 HBr + N02 = HN02 13.0 11.0 180-310 HBr/NO, T 23 + Br HBr+C2 F4 = C2 F4 Br 54.6 16.96 858-1013 H2/02 /C2 F4 Br2 S.T. 22 + H

2HI = H2 + I

2 (d) (a) 44.0 13.9 10-235 HI T 3

49.2 15.56 597-774 HI 1 9, 10 44.20 ± 0.25 13.54 ±0.07 105-360 h2 /i

2 t 12

hi + ch:) i = ch4 + i

2 (e) 33.4 14.3 270-320 ch;! i/hi t 19

DI + CH.,I = CH3 D +

1

2 k = 1.54 250 CH3I/HI/DI T 20

hi+c2h5i=c2 h6 +i2 (e) 29.8 13.7 250-300 c2 h5 i/hi t 19

HI + n-C .H I = C..H (e) 19.2 14.1 260-300 n-C^Hyl/HI T 19 + I

2

Ratios of Rate Constants

Reactions Notes logio 4 1M2 ki/k-z Temperature range

Radical source Reference

(1) HBr + CH2 N2 = CH.i Br + N2 (2) HC1 + CH2 N2 = CH.',C1 + N2

( kcal mole -1

)

-1.5 -0.091

°C - 78-27 CH2 N2/HBr/HCl T 21

(1) HI + CH2N2 = CH.,1 + N2 (2) HBr + CH2 N2 = CH:! Br+N2 4 ± 2 27 CH2 N2 /HI/HBr T 21

(1) HI + CH2 N2 = CH i I + N2 (2) HC1 + CH2 N2 = CH:j Cl + N2 50 ±15 27 ch2 n2 /hi/hci T 21

118
Notes

(a) These values summarise a considerable body of early data

(references 4 to 8). (b) For data on the reaction HD + l2 =HI+DI, see reference 16.

(c) For a summary of early data see reference 3. (d) For data on the reaction 2DI=D„+I, see references 13 and 18.

(e) The A factor values originally reported (reference 19) are

too large by a factor of ten (reference 20). References

1. Semenov, Acta Physicochimica U.S.S.R. 20, 291 (1945).

2. Skinner and Ringrose, J. Chem. Phys. 42 , 2190 (1965).

3. Trotman-Dickenson, “Gas Kinetics,” p. 255 et seq. (Butter- worths, London, 1955).

4. Bodenstein, Z. Phys. Chem. 13, 56 (1894).

5. Bodenstein, Z. Phys. Chem. 22, 1 (1897).

6. Bodenstein, Z. Phys. Chem. 29, 295 (1899).

7. Kassel, Proc. Nat. Acad. Sci. Wash. 16, 358 (1930).

8. Kistiakowsky, J. Am. Chem. Soc. 50, 2315 (1928).

9. Graven, J. Am. Chem. Soc. 78, 3297 (1956).

10. Horie, Ishii, and Amano, J. Phys. Chem. 68, 1264 (1964).

11. Sullivan, J. Chem. Phys. 36, 1925 (1962).

12. Sullivan, J. Chem. Phys. 30, 1292 (1959).

13. Sullivan, J. Chem. Phys. 39, 3001 (1963).

14. Steiner, Trans. Faraday Soc. 36, 1111 (1940).

15. Crist and Wertz, J. Chem. Phys. 7, 719 (1939).

16. Magee, J. Am. Chem. Soc. 79, 5375 (1957).

17. Sullivan, J. Chem. Phys. 30, 1577 (1959).

18. Taylor and Crist, J. Am. Chem. Soc. 63, 1377 (1941).

19. Ogg, J. Am. Chem. Soc. 56, 526 (1934).

20. Newton, J. Chem. Phys. 18, 797 (1950).

21. Hassler and Setser, J. Am. Chem. Soc. 87, 3793 (1965).

22. Skinner and Ringrose, J. Chem. Phys. 43, 4129 (1965).

23. Rosser and Wise, J. Phys. Chem. 64, 602 (1960).

119
Molecule-Molecule Reactions (Hydrocarbons and Hydrocarbon Derivatives)

Reactions Notes E log 10 A Temperature range

Radical source Reference

Alkanes

CH4 + 03 = products

(kcal mole -1

) 15.35 13.90

(cm3 mole -1 sec

-1

) 11.21 11.15

°C

35-64

35-64

ch4 /o3/o2 ch4 /o3 tT 1

1

C2 Hk + C2 H4 = 2C2 H5 68.9 17.6 752-917 h2/o2 /c2 h4 S.T. 2

Alkenes and

aromatics

CH2 :CHCH:CH2 + C2 N2 = H2 + 2- cyano pyridine

31.6 12.20 325-450 c2n2 /c4h6 T 3

CH2 :CHCH:CH2 + CF3 CN = H2 + 2- trifluoromethyl

pyridine

21.5 9.32 350-520 CFgCN/C^H,. T 4

CH2 :CHCH:CH2 + cf:! cf2 cn=h2 + 2 -pentafluoroethyl pyridine

25.0 10.42 340-460 c2f5 cn/c4 h6 T 5

CH2 :CHCH:CH2 +cf3 cf2 cf2 cn = H2 + 2-perfluoropropyl pyridine

25.8 10.51 340^460 c3f7 cn/c4 h6 T 5

2C6 H6 = C 12 Hio + H2 40 14.0 900-1210 c6 h6 t 6

Alkynes

2C2 H2 = products (b) 50.2 16.57 352-472 c2 h2 t 7

2C2 H2 = C4 H2 + H2 (b) ~ 30 c2 h2 s.t. 8

2C2 H2 = C4 H2 + H2 (b) 36.4 ± 3 12.89 1127-2227 c2 h2 s.t. 9

2C2 H2 = C2 H2 * + C2H2 (b) 50 14.04 1227-2227 c2 h2 s.t. 10

2C2 H2 = C4 H3 + H (b)

(a)

38.8 ±7.5

41.6 ±0.6

13.47 ±0.78

13.77 ±0.11

1630-1922

347-2177 c2 h2 s.t. 1111

Hydrocarbon

derivatives

ch.( cho+o2 = ho2 +ch.( co29 ±2 320-380 ch3 cho/o2 T 12

CH.,1 + 1* — I = CH:i I* + 1 2

(c) 9.0 6.40 60-140 ch,i/i2 T 13

CH3 OCH3 + NO

= HNO

+ CH2 OCH3

43.4 14.0 500-600 CH30CH3/NO T 14

120
Notes

(a) Critical review of literature data.

(b) These values are included in the review estimate (a), the products of the reaction being considered to be C4 H3 + H.

(c) These values may be low because of complicating hetero- geneous reactions.

References

1. Dillemuth, Skidmore, and Schubert, J. Phys. Chem. 64,

1496 (1960).

2. Skinner and Ringrose, J. Chem. Phys. 43 , 4129 (1965).

3. Hawkins and Janz, J. Am. Chem. Soc. 74, 1790 (1952).

4. Jarvie and Janz, J. Phys. Chem. 60, 1430 (1956).

5. Monahan and Janz, J. Phys. Chem. 69, 1070 (1965).

6. Hou and Palmer, J. Phys. Chem. 69, 863 (1965).

7. Silcocks, Proc. Roy. Soc. 242 A, 411 (1957).

8. Greene, Taylor, and Patterson, J. Phys. Chem. 62, 238

(1958).

9. Aten and Greene, Comb and Flame 5 , 55 (1961).

10. Palmer and Dormish, J. Phys. Chem. 68, 1553 (1964).

11. Gay, Kistiakowsky, Michael, and Niki, J. Chem. Phys. 43,

1720 (1965).

12. Sokolova, Markevich, and Nalbandyan, Russ. J. Phys.

Chem. (Eng. Trans.) 35 , 415 (1961).

13. Schmied and Fink, J. Chem. Phys. 27, 1034 (1957).

14. McKenney, Wojciechowski, and Laidler, Can. J. Chem.

41, 1993 (1963).

121
Molecule-Molecule Reactions Involving Nitric Oxide

Reaction Notes E logio^ Temperature rangeRadical source Reference

(kcal mole -1

) (cm 3 mole -1 sec

-1

) °C

NO + CH3 OCH3 = HNO 43.4 14.0 500-600 CH3OCH3/NO t 1 + CH2 OCH:i NO + CCljCHO = HNO 37.1 13.5 356-421 cci3 cho/no t 20, 21 + CC13 C0

no + f2 =onf+f 1.5 ±1.0 11.78 — 78—1-27 no2 /f2 d.f. 2 NO + XeF4 = ONF 7 to 9 27-77 XeF4 /NO T 3 + XeF3 NO + XeF., = ONF 10 to 12 27-77 XeF4/NO j 3 + XeF

NO + Cl2 = NOCl + Cl *=(2.7:± 1.0) x 102 158 1 A = (8.3± 3.0) x 102 178 NOC1 T 4

*=(10.0±4.0)X 102 198

(b) 20.3 12.6 25-55 18 no + no2 ci=no2 6.9 11.92 1-71 N02 C1/N0 t 19 + NOC1

no+o3 =no2 +o2 2.5 ±0.3 11.90 -75—43 NO/O, T 5

A = 3 X 10 10 29 NO/03 T 6

(a) 2.55 ±0.22 12.08 -28-+ 78 no/o3 7 A= 7.(ix 10 9 60 no/o3 t 8 A= 1.5 X 10 10 25 N0.,/02 discharge 9

A = (1.26 ±0.30) X 10 10 25 0,,/N2 discharge 10

2.46 ±0.15 11.76 — 57—1-49 n'o/o3 t 11 no + no = n2 + o2 63.8 12.42 1062-1257 NO T 12. 13

63.1 13.49 1400-1800 NO T- 14

57.0 12.91 2730-4030 NO S.T. 15 no + n.,o = n2 + no. 50.0 14.3 1227-1927 NO/N2 0 S.T. 16

50.0 14.4 700-760 17 CH3 CH2 015 N0 + 14N0 21.4 ±0.5 11.48 130-150 CH.1 CH„015 N0/ 22 = CH3 CH2 014 N0

+ 15 NO

14 NO T

CF3 CH.,015 N0 + 14 N0 23.7 ±0.5 12.78 130-150 CF3 CH2 015 N0/ 22 = CF3 CH2 014 N0

4- 15NO

14NO T

122
[Notes

(a) Reaction carried out using supersonic nozzle technique.

(b) Estimated from the reverse reaction.

References

1. McKenney, Wojciechowski, and Laidler, Can. J. Chem. 41,

1993 (1963).

2. Rapp and Johnston, J. Chem. Phys. 33, 695 (1960).

3. Johnston and Woolfolk, J. Chem. Phys. 41, 269 (1964).

4. Ashmore and Spencer, Trans. Faraday Soc. 55, 1868 (1959).

5. Johnston and Crosby, J. Chem. Phys. 22, 689 (1954).

6. Ford, Doyle, and Endow, J. Chem. Phys. 26, 1337 (1957).

7. Marte, Tschuikow-Roux, and Ford, J. Chem. Phys. 39,

3227 (1963).

8. Borok, Zhur. Fiz. Khim. 35, 2275 (1961).

9. Phillips and Schiff, J. Chem. Phys. 37, 924 (1962).

10. Phillips and Schiff, J. Chem. Phys. 36, 1509 (1962).

11. Clyne, Thrush, and Wayne, Trans. Faraday Soc. 60, 359

(1964).

12. Kaufman and Kelso, J. Chem. Phys. 23, 1702 (1955).

13. Kaufman and Decker, 7th Int. Comb. Symp., p. 57 (Butter- worths, London, 1959).

14. Yuan, Slaughter, Koerner, and Daniels, J. Phys. Chem.

63, 952 (1959).

15. Freedman and Daiber, J. Chem. Phys. 34, 1271 (1961).

16. Fishburne and Edse, J. Chem. Phys. 41, 1297 (1964). ^ 17. Kaufman and Kelso, J. Chem. Phys. 23, 602 (1955).

18. Ashmore and Chanmugam, Trans. Faraday Soc. 49, 270

(1953).

19. Freiling, Johnston, and Ogg, J. Chem. Phys. 20, 327 (1952).

20. Verhoek, Trans. Faraday Soc. 31, 1521 (1935).

21. Trotman-Dickenson, “Gas Kinetics,” p. 212 (Butterworths,

London, 1955).

22. Kuhn and Gunthard, Helv. Chim. Acta. 43, 607 (1960).

247-168 0-67—9

123
Nitrogen Dioxide (Molecule-Molecule Reactions)

Reactions Notes E log 10 4 Temperature range

Radical source Reference

(kcal mole-1

) (cm 3 mole -1 sec

-1

) °C

no2 +h2 =no+h2 o 18. 9.3 384-434 h2 /o2 /no2 T 19 no2 +hcho = hno2 15.1 10.1 118-160 hcho/no2 t 20

+ HCO

NO., + CHOCHO 19.8 11.9 160-210 chocho/no2 t 21 = hno2 +cocho

no9 +ch3 cho=hno2 16.0 12.9 118-143 ch3 cho/no2 t 22 + CH.s CO

no2 +nh3 = hno2 27.5 12.7 327-527 nh3/no2 t 1 + nh2 no, + hci=hno2 + ci 23.4 11.6 100-420 hci/no2 t 2 N02 + HBr = HN02 + Br 13.0 11.0 180-310 HBr/N02 T 2 no2 + f2 =no2 f+f 10.5 12.2 28-70 no2 /f2 t 7 no2 +f2 o=no2f+fo 14.48 11.11 60-80 f2 o/no2 t 18 no2 + ci2 o=no2 ci 11.6 10.64 20-60 no2/ci2 o t 3 + 0C1

N02 + C102 =N03 + 0C1 11.5 10.68 3

no2 + noci=no 10.0 10.28 -20-+8 noci/cio2 t 4 + N02 C1 no2 + co=co2 +no 31.6 13.08 267-454 co/no2 t 5

27.8 11.68 225-290 co/no2 t 6

N02 ± 03 = N03 + 02 7.0 12.77 13-29 o3 /no2 T 8 k= 1.96 X 10 7 room temp. o3/no2 t 9

2N02 = N0 + N03 k = 2.6X 104 434 no2 t 10 23.90 ±0.60 11.89 ±0.25 200-430 no2 t 11

(a) 23. 12

2N02 = 2N0 + 02 (b) 27.10 12.69 320-380 no2 t 13, 11 26.90 12.60 357-747 no2 t 14, 11 26.90 ±0.10 12.60 ±0.04 200-550 no2 T 11, 10

2N02 = products (c) 25.6 11.8 319-383 15

(c) 25.0 ±5.0 13.40 1127-2027 no2 s.t. 16

(c) 25.7 12.95 1227-1827 no2 s.t. 17

124
Notes

(a) Estimated from the reverse reaction.

(b) These values were recalculated from the original data

(reference 11).

(c) These values represent the sums of the contributions from

2N02 = 2NO + 02 and 2N02 = NO + N03.

References

1. Rosser and Wise, J. Chem. Phys. 25, 1078 (1956).

2. Rosser and Wise, J. Phys. Chem. 64, 602 (1960).

3. Martin, Meise, and Engelmann, Z. Phys. Chem. 24, 285

(1960).

4. Martin and Kohnlein, Z. Phys. Chem. 17, 375 (1958).

5. Johnston, Bonner, and Wilson, J. Chem. Phys. 26, 1002

(1957).

6. Brown and Crist, J. Chem. Phys. 9, 840 (1941).

7. Perrine and Johnston, J. Chem. Phys. 21, 2202 (1953)

8. Johnston and Yost, J. Chem. Phys. 17, 386 (1949).

9. Ford, Doyle, and Endow, J. Chem. Phys. 26, 1336 (1957).

10. Ashmore and Levitt, Research 9, s25 (1956).

11. Ashmore and Burnett, Trans. Faraday Soc. 58, 253 (1962).

12. Schott and Davidson, J. Am. Chem. Soc. 80, 1841 (1958).

13. Bodenstein and Ramstetter, Z. Phys. Chem. 100, 106

(1922).

14. Rosser and Wise, J. Chem. Phys. 24, 493 (1956).

15. Kassel, “The Kinetics of Homogeneous Gas Reactions,”

p. 156 (Chemical Catalog Co., N.Y., 1932).

16. Huffman and Davidson, J. Am. Chem. Soc. 81, 2311 (1959).

17. Fishburne, Bergbauer, and Edse, J. Chem. Phys. 43, 1847

(1965).

18. De Staricco, Sicre, and Schumacher, Z. Phys. Chem. 39,

337 (1963).

19. Crist and Wertz, J. Chem. Phys. 7, 719 (1939).

20. Pollard and Wyatt, Trans. Faraday Soc. 45, 760 (1949).

21. Thomas, Trans. Faraday Soc. 49, 630 (1953).

22. McDowell and Thomas, Trans. Faraday Soc. 46, 1030

(1950).

125
Molecule-Molecule Reactions (Inorganic Molecules)

Reactions Notes E log io A Temperature range

Radical source Reference

( kcal mole * 1

) (cm3 mole~ 1 sec

-1

) °C

f2 +co=fco+f 13.5 ±1.2 11.67 15-45 f2 /co/o2 t 1, 2

f2 +cio2 =fcio2 +f 8.5 ±0.4 10.6 -46—26 f2/cio2 t 3

8.0 ±0.5 10.11 -46—26 f2/cio2 t 4

C12 + 03 = C10 + C102 26.0 ± 1 35-60 cyo3 t 5

2C1CN = Cl2 + C2 N2 60. 13. 1727-2527 C1CN S.T. 6

2NOC1 = Cl2 + 2NO 23.4 12.5 150-250 7

23.6 ±0.7 12.7 ±0.3 150-411 NOC1 T 8

2NOI = I

2 + 2NO k =£ 4 x 10 10 60 no/i2 f.p. 15

203 = 302 18.8 12.65 70-100 03 T 9 CO + 02 = C02 + 0 51.0 ±7.0 12.54 ±0.22 2127-2727 CO/02 S.T. 10 co + b2 h6 =bh3 (a) 17.65 11.32 0-60 11 + bh3 co

bf3 +bci =bf2 ci j x 10 3 23 BF3/BC.l

3 t 12 + bfci2 ph3 +b2 h6 11.4 9.5 -24-0 ph3 /b2 h6 t 14, 13, 11 = PH3 BH3 (g) +BH3

Notes

(a) Critical review of literature data.

References

1. Heras, Arvia, Aymonino, and Schumacher, Anales Asoc. Quim. Argentina 50, 120 (1962).

2. Heras, Arvia, Aymonino, and Schumacher, Z. Phys. Chem.

N.F. 28, 250 (1961).

3. Aymonino, Sicre, and Schumacher, J. Chem. Phys. 22.

756 (1954).

4. Aymonino, Sicre, and Schumacher, Anales Asoc. Quim.

Argentina 43, 26 (1955).

5. Schumacher, Z. Phys. Chem. 13 , 353 (1957).

6. Schofield, Tsang, and Bauer, J. Chem. Phys. 42, 2132

(1965).

7. Ashmore and Spencer, Trans. Faraday Soc. 55, 1868

(1959).

8. Ashmore and Spencer, Trans. Faraday Soc. 58, 1801

(1962).

9. Pshezhetskii, Morozov, Kamenetskaya, Sirystskaya, and

Bribova, Zhur. Fiz. Khim. 33 , 2306 (1959).

10. Sulzmann, Myers, and Bartle, J. Phys. Chem. 42 , 3969

(1965).

11. Garabedian and Benson, J. Am. Chem. Soc. 86, 176

(1964).

12. Nightingale and Crawford, J. Chem. Phys. 22, 1468

(1954).

13. Bauer, J. Am. Chem. Soc. 78, 5775 (1956).

14. Brumberger and Marcus, J. Chem. Phys. 24, 741 (1956).

15. Porter, Szabo, and Townsend, Proc. Roy. Soc. 270A,

493 (1962).

126
Termolecular Reactions

Reactions Notes E logi oA Temperature range

Radical source Reference

(kcal mole_1

) (cm 6 mole~ 2 sec~ 1 ) °C

2N0 + 02 = 2N02 (a) A = (7.45± 0.22) X 109 25 no/o2 T 1 A = 6.0 X 109 25 no/o2 T 2 k— 7.10 X 109 25 no/o2 T 3 2NO + Cl2 = 2NOC1 (b) 4.2 10.4 8, 9

6.0 11.4 100-250 NO/CL, T 10 2NO + Br2 = 2NOBr 1.6 10.6 -8-15 NO/Br2 T 11, 8 2NO + H2 = products (c) 47 18.7 700-825 no/h2 T 12, 8 no + no2 + o2

10 O -ic 11 8x 107 25 NOC1/NOJO, T 13 = N02 + NO,

(d) A = 3.0x 107 15 -0.96 7.32 200-430 no2 t 14 2N02 + 02 = 2NO, (e) 25 (A = 7x 10- 12

) 27 15 h + o2 + h2 = h2 o k=2 X 1011 830-1630 h2 /02 S.T. 16 + OH

CF,NO + 2NO k = 5.(

in X O 24 CF,I/NO P 17 = CF,+ N2 +'NO,

CH,NO + 2NO (0 -1.8 6.41 25-70 CH,I/NO P 18 = CH, + N2 + NO,

C2 H5 NO + 2NO (0 -2.9 6.28 25-70 c2h5 i/no P 18 = c2 h5 +n2 +no.

ch,ch2 ch2 no (f) -7 3.7 25-45 c,h7 i/no P 18 + 2NO = CH,CH2 CH2 + N2 + NO,

(CH,)2 CHNO + 2NO (f) -4 5.3 25-45 (CH lchi/no p 18 = (CH,)2 CH + N2 + NO,

(CH,),CNO + 2NO (f) -7.5 25-70 (CH ) CI/NO P 18 = (CH,),C + N2 + NO,

Notes

(a) Further data on this reaction can be found in references 4 to 7. (b) Critical survey of literature data. The Arrhenius plot is curved, and the values given are valid only at low temperatures.

(c) It is unlikely that the nitric oxide-hydrogen reaction is a simple termolecular process.

(d) Temperature independent. Estimated from the reverse

reaction.

(e) Estimated from the reverse reaction.

(f) These values are for an overall reaction which could be

RNO + NO ^ R(NO)2 ; R(NO)2 + NO = R + N2 + N03 .

References

1. Brown and Crist, J. Chem. Phys. 9, 840 (1941).

2. Smith, J. Am. Chem. Soc. 65, 74 (1943).

3. Johnston and Slentz, J. Am. Chem. Soc. 73, 2948 (1951).

4. Bodenstein and Lindner, Z. Phys. Chem. 100, 87 (1922).

5. Bodenstein and Wachenheim, Z. Electrochem. 24, 183

(1918).

6. Matthes, Miss Dissertation Berlin, 1933, quoted by Schumacher “Chemische Gasreaktion,” p. 314 (Steinhopff, Dresden,

1938).

7. Briner, Pfeiffer, and Malet, J. Chim. Phys. 21, 25 (1924).

8. Trotman-Dickenson, “Gas Kinetics,” p. 265 (Butterworths,

London, 1955).

9. Welinsky and Taylor, J. Chem. Phys. 6, 466 (1938).

10. Ashmore and Spencer, Trans. Faraday Soc. 55, 1868

(1959).

11. Krauss, Z. Phys. Chem. 175A, 295 (1936).

12. Hinshelwood and Mitchell, J. Chem. Soc. 378 (1936).

13. Ray and Ogg, J. Chem. Phys. 29, 984 (1957).

14. Ashmore and Burnett, Trans. Faraday Soc. 58, 253 (1962).

15. Schott and Davidson, J. Am. Chem. Soc. 80, 1841 (1958).

16. Belles and Lauver, J. Chem. Phys. 40, 415 (1964).

17. Heicklen, J. Phys. Chem. 70, 112 (1966).

18. Christie, Foot, and Voisey, Trans. Faraday Soc. 61, 674

(1965).

127
Inversion (Group Transfer) Reactions

Reactions Notes E logio^ Temperature rangeRadical source Reference

(kcal mole-1

) (cm3 mole-1 sec

-1

) °C

14 CH, + CH,COCH3 (a) k = 5Jlx 10® 350 ch3 coch3 p 1 = 14 CH3 COCH3 + CH3 ch3 +cf3 cocf3 5.7 ±1.5 9.3 163-245 CH3N2CH3 P and T 2 =ch3cocf3 +cf3 6.2 ±1.0 11.4 85-210 cf3 cocf3 p 3

7.0 ±1.0 11.7 48-240 ch3 coch3

/ 4 cf3 cocf3 p

ch3 +c2f5 coc2f5 7 ± 1 18T-240 (C2 F5

) 2 CO P 5 = ch3 coc2f5 +c2f5 CD, + CH,j HgCH.i k = 8S,

ir? X o 180 cd3 cocd3 p 6. 7 = CD3 HgCH3 + CH3

CH.! + CD.i SH = CH.! SH 7.6 10.73 130-200 ch3 coch3 p 8 +cd3 ch3 +cf3 coch3 14. 150-350 cf3 coch3 p 9 =c2 h6 +cf3 co

ch3 + ch3 cococh3 = CH3 COCH3 + ch3 co5.6 10.7 100-200 ch3 cococh3 p 10

6.6 100-200 ch3 cococh3 p 11 CH3 + CH3 CH:CHCHO 7.45 ±1.30 11.8 ±0.4 120-250 ch3 coch3 p 12 = CH CH:CHCH

+ CHO

CH3 +CH3HgCH3 1.0 7 175-220 (CH3

) 2 Hg P 13, 14 = C2 H6 + (Hg + CH3

)

c6h5 +c6h5 coch3 (b) 6.2 9.6 277-407 cb h5 coch3 p 15 = C6 H5 Ce H5 + CH3 CO

CF.s CH2 015 N0 + I4 N0 23.7 ±0.5 12.78 130-150 CF3 CH2 015 N0/i4 N0 16 = CF.s CH2 014 N0

+ 15 N0

T

CH3 CH2 015 N0 + 14N0 21.4 ± + 0.5 11.48 130-150 CH CH.,0 1SN0/14 N0 16 = CH3 CH2 014N0

+ 15N0

T

bh3 +b2d6 =bh3bd3 6.0 14.2 24-44 b2h6/b2 d6 t 17, 14. 21, + bd3 22

7.8 13.45 18 bh3 +bh3 co=b2 h6 7.0 11.4 0-30 bh3 co t 19, 17, 22 + C0

ph3 + b2h6 =bh3ph3 11.4 ±2 9.5 -24-0 20, 22 + bh3

128
JNotes

(a) Assuming A=10n - 6 exp (— 9800/RT) for the reactior CH, + CH3 COCH3 = CH4 + CH2 COCH.r

(b) refers to the phenyl radical.

References

1. Dainton, Ivin, and Wilkinson, Trans. Faraday Soc. 55.

929 (1959).

2. Pritchard and Steacie, Can. J. Chem. 35, 1216 (1957).

3. Alcock and Whittle, Trans. Faraday Soc. 61, 244 (1965).

4. Giles and Whittle, Trans. Faraday Soc. 61, 1425 (1965).

5. Price and Kutschke, Can. J. Chem. 38, 2128 (1960).

6. Rebbert and Ausloos, J. Am. Chem. Soc. 86, 2068 (1964).

7. Rebbert and Ausloos, J. Am. Chem. Soc. 85, 3086 (1963).

8. Greig and Thynne, Trans. Faraday Soc. 62, 379 (1966).

9. Sieger and Calvert, J. Am. Chem. Soc. 76, 5197 (1954).

10. Blacet and Bell, Disc. Faraday Soc. 14, 70 (1953).

11. Bell and Blacet, J. Am. Chem. Soc. 76, 5332 (1954).

12. Allen and Pitts, J. Phys. Chem. 70, 1691 (1966).

13. Corner and Noyes, J. Am. Chem. Soc. 71, 3390 (1949).

14. Trotman-Dickenson, “Gas Kinetics,” p. 237 et seq. (Butterworths, London, 1955).

15. Duncan and Trotman-Dickenson, J. Chem. Soc. 4672

(1962).

16. Kuhn and Gunthard, Helv. Chim. Acta. 43, 607 (1960).

17. Bauer, Shepp, and McCoy, J. Am. Chem. Soc. 75, 1003

(1953).

18. Roth and Bauer, 5th Int. Comb. Symp., p. 710

(Reinhold, New York, 1955).

19. Burg, J. Am. Chem. Soc. 74, 3482 (1952).

20. Brumberger and Marcus, J. Chem. Phys. 24, 741 (1956).

21. Maybury and Koski, J. Chem. Phys. 21, 742 (1953).

22. Garabedian and Benson, J. Am. Chem. Soc. 86, 176 (1964)

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