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Liquid-Phase Reaction Rate Constants
Liquid-Phase Reaction Rate Constants
E. T. Deni soy Institute of Chemical Physics Moscow, USSR
Translated from Russian by R. K. Johnston
IFljPLENUM NEW YORK-WASHINGTON - LONDON
Library of Congress Cataloging in Publication Data
Denisov, Evgenil Timofeevich. Liquid-phase reaction rate constants.
Translation of Konstanty skorosti gomoliticheskikh zhidkofaznykh reaktsil. Includes bibliographies. 1. Chemical reaction, Rate of-Tables, etc. I. Title.
QD502.D4613 541'.39 73-79419 ISBN 978-1-4684-8302-4 ISBN 978-1-4684-8300-0 (eBook) DOl 10.1007/978-1-4684-8300-0
The original Russian text, published by Nauka Press in Moscow in 1971, has been corrected by the author for the present edition. This translation is published under an agreement with Mezhdunarodnaya Kniga, the Soviet book export agency.
KOHCT8HTW CKOPOCTH rOMonHTH~eCKHX MHAKO$83HMX pesK4HA • E ~T. LhlHKCOS
KONSTANTY SKOROSTI GOMOLITICHESKIKH ZHIDKOFAZNYKH REAKTSII E. T. Denisov
© 1974 IFI/Plenum Data Company Softcover reprint of the hardcover 1 st edition 1974 A Division of Plenum Publishing Corporation 227 West 17th Street, New York, N.Y. 10011
United Kingdom edition published by Plenum Press, London A Division of Plenum Publishing Co~pany, Ltd. 4a Lower John Street, London WIR 3PD, England
All rights reserved
No part of this publication may be reproduced in any form without written permission from the publisher
PREFACE
The past 25 years in chemical kinetics have seen major advances in studyiqg the mechanisms of complex chemical reactions, in particular free radical reactions. Many different methods have been developed for quantitative studies of elementary chemical reactions. Thousands of rate constants have been measured, for hundreds of diverse chemical reactions. It is becoming more and more difficult for the chemist to orient himself in the voluminous and rapidly growing literature of chemical reaction kinetics. This leads to major expenditures of time in searching out, collecting. and evaluating quantitative kinetic data; to unnecessary repetition (duplication) of research; and to a situation in which the rich material already accumulated in the field of chemical kinetics is very often not fully utilized in comparing, interpreting, and analyzing new experimental data. There is a pressing need for the creation of a series of handbooks on reaction rate constants. Such work was begun several years ago at the initiative of V. N. Kondrat'ev, and is now going forward under his direction at the Institute of Chemical Physics of the USSR Academy of Sciences.
This book is devoted to liquid-phase, homolytic reactions. Part One contains data on monomolecular reactions in which molecules decompose to form radicals, as well as data on bimolecular and trimolecular reactions that form free radicals. Also collected in Part One are data on the probability of radical escape into the bulk volume from a "cage" of solvent with various initiators, as well as values of the stoichiometric inhibition coefficients for various phenols and aromatic amines that are used as free radical acceptors. In Part Two, rate constants are collected for reactions of decomposition, substitution, and addition of radicals to molecules, as well as radical recombination and disproportionation reactions. Part Three contains data on ion--molecule reactions that are accompanied by radical formation, as well as reactions of
v
vi PREFACE
free radicals with metal ions and acid anions, reactions of ion-radicals and solvated electrons, and ionic oxidationreduction reactions with electron transfer. In this book, rate constant values are presented along with a statement of the conditions and a brief characterization of the method of measurement.
I wish to express deep gratitude to Academician V. N. Kondrat'ev for having inspired me to this not easy but useful task, and for having aided me with counsel. The last chapter of this book was written by V. N. Berdnikov. For assistance in collecting the reaction rate constants, I thank A. L. Buchachenko, R. L. Vardanyan, S. S. Ivanchev, N. F. Kazanskaya, G. M. Nazin, A. A. Shteinman, and V. Ya. Shlyapintokh. I also wish to express gratitute to Z. A. Denisova for painstaking work in preparing the manuscript for publication.
E. T. Denisov
CONTENTS
Preface
List of Tables
Symbols
Abbreviations •
PART ONE - REACTIONS OF MOLECULES
CHAPTER I. MONOMOLECULAR REACTIONS
1. Methods for Measuring Rate Constants of Monomolecular Reactions •
2. Rate Constants for Decomposition of Peroxide Compounds • • •
3. Decomposition of Azo Compounds •
4. Decomposition at C - C, N - N, N - C, N - 0, and C-Metal Bonds •••
5. Decomposition of Iodobenzene Dichloride
6. Correlation Equations
7. Effect of Pressure and Solvent on Monomolecular Reactions
v
xiii
xxiii
xxv
1
3
8
10
10
11
11
13
CHAPTER II. BIMOLECULAR AND TRIMOLECULAR REACTIONS 87
1. Methods for Measuring Rate Constants of Bimolecular Reactions • •
vii
87
viii
2. Diels-Alder Reaction •••
3. Bimolecular Reactions with Peroxide Participation
4. Oxidation-Reduction Reactions with Participation of Cl02, 02, and C12 • • • • • •
5. Reactions with Rupture of Metal-Carbon Bond .•.•••
6. Trimolecular Reactions.
CHAPTER 111. THE CAGE EFFECT
1. Questions of Theory
2. Methods for Measuring Initiator Efficiency •
3. Initiator Efficiency •
LITERATURE CITED (Part One)
CONTENTS
89
89
91
92
92
109
109
111
114
135
PART TWO - REACTIONS OF FREE ATOMS AND RADICALS
CHAPTER IV. METHODS FOR MEASURING RATE CONSTANTS OF RADICAL REACTIONS
1. Measurement of Relative Rate Constants of Radical Reactions
2. Measurement of Absolute Rate Constants of Reactions of Atoms and Radica Is . . . . . . . · . . .
CHAPTER V. ISOMERIZATION AND DECOMPOSITION OF FREE RADICALS . . . . ·
1. Isomerization of Free Radicals
2. Decomposition of Free Radicals ·
157
157
164
173
173
174
CONTENTS
CHAPTER VI. RADICAL SUBSTITUTION REACTIONS
1. Reactions of Atoms •••••
2. Reactions of Radicals Having Free Valence on Oxygen • • • •
3. Reactions of Radicals Having Free Valence on Carbon ••••
4. Chain Transfer in Radical Polymerization
5. Reactions of Radicals Having Free Valence on Nitrogen
6. Correlation Equations for Radical Substitution Reactions • •
CHAPTER VII. ADDITION REACTIONS OF ATOMS AND RADICALS • • • •
1. Addition of Atoms and Radicals to Molecular Oxygen
2. Addition at C = C Bond •••
3. Addition to Aromatic Compounds •
4. Addition to Quinones, Carbonyl Compounds, Nitriles, and Nitro Compounds • • • •
CHAPTER VIII. RECOMBINATION AND DISPROPORTION-
ix
179
179
181
183
183
184
184
351
351
351
353
354
ATION OF FREE ATOMS AND RADICALS • 399
1. Recombination of Atoms
2. Disproportionation and Recombination of Alkyl and RO· Radicals
3. Reactions between Peroxy Radicals
4. Reactions of Radicals Having Free Valence on Nitrogen or Tin
399
399
401
402
x
5. Reactions between Free Radicals of Different Types
CHAPTER IX. EFFECT OF SOLVENT ON FREE RADICAL REACTIONS
1. Solvent Viscosity
2. Internal Pressure of Liquid
3. Nonspecific Solvation
4. Hydrogen Bond between Molecules
5. Radical Hydrogen Bond
6. Formation of 7f-Complexes ••
LITERATURE CITED (Part Two) •••
CHAPTER X.
PART THREE - IONIC HOMOLYTIC REACTIONS
OXIDATION-REDUCTION REACTIONS OF IONS WITH MOLECULES
1. Oxidation of Organic Compounds by Variable-Valence Metal Ions
2. Reaction of Variable-Valence Metal Ions with Oxygen, Peroxides, and Quinone s • • • • • . • .
CHAPTER XI. REACTIONS OF ATOMS AND RADICALS WITH IONS •• • • • •
1. Reactions of Hydrogen Atom •
2. Reactions of Free Radicals ••
CONTENTS
402
427
427
427
428
430
431
432
443
479
479
485
531
531
531
CONTENTS
CHAPTER XII. REACTIONS OF ION-RADICALS AND SOLVATED ELECTRONS •
1. Reactions of Ion-Radicals
2. Solvated Electron
xi
561
561
561
CHAPTER XIII. IONIC OXIDATION-REDUCTION REACTIONS 607
1. Methods for Measuring Reaction Rates for Electron Transfer from Ion to Ion • • • • • •
2. Electron Exchange Reactions
3. Oxidation-Reduction Reactions between Ions •
LITERATURE CITED (Part Three)
607
608
608
735
LIST OF TABLES
CHAPTER I. MONOMOLECULAR REACTIONS
1
2
3
3A
4
5
6
7
8
9
10
11
Rate Constants for Benzoyl Peroxide Decomposition • • • • • •
Decomposition of Benzoyl Peroxide in Various Solvents
Decomposition of Symmetrically Substituted Benzoyl Peroxides
Decomposition of Unsymmetrically Substituted Benzoyl Peroxides and Phthaloyl Peroxide ••
Decomposition of Acetyl Peroxide in Various Solvents • • •
Decomposition of Symmetrical Diacyl Peroxides, RCOOOCOR
Decomposition of Unsymmetrical Diacyl Peroxides, RlCOOOCOR2 ••••
Decomposition of Peroxides, ROOR
Decomposition of Unsymmetrical Peroxides, RlOOR2
Decomposition of Peroxides, (CH3)3COOCOR •
Decomposition of Dibasic Peroxides
Decomposition of Hydroperoxides in Aromatic Solvents •••••
xiii
17
18
19
21
23
24
32
35
38
40
50
56
xiv LIST. OF TABLES
12
13
14
15
16
17
18
19
20
21
22
23
24
Decomposition of Azobisisobutyronitrile
Decomposition of R- N = N - R
Decomposition of Rl - N = N - R2
Decomposition at C - C Bond
Decomposition at N - N Bond
Decomposition of Compounds with Rupture of N - C or C -0 Bond •
Decomposition of Nitrogen Pent oxide
Decomposition of Nitro Compounds
Decomposition at C-Metal Bonds .••
Decomposition of XC6~IC12 • • • • • •••
Constants in Correlation Equations log k = log ko + pa • • • •
Compensation Effect for Monomolecular Decomposition Reactions
Volume Change ~V# in Decomposition of Molecules • • • • •
25 Range of Variation of k for Decomposition of Initiators in Various Solvents ••••
CHAPTER II. BIMOLECUIAR AND TRIMOLECUIAR REACTIONS
26 Dimerization of Unsaturated Compounds •••
27 Volume Change in Diels-Alder Reaction
28 Reactions of Amines with Peroxides • •
29 Reaction ROOR + R'R~Free Radicals
30 Reactions of Rydroperoxides 2 ROOR-.-!S.. Complex-4Free Radicals • .--:-:-
57
60
66
70
72
74
77
78
80
81
82
83
84
85
93
94
95
99
100
LIST OF TABLES
31
32
33
34
Reactions with Participati~ of Peroxide, ROOH + M ~ Complex-4 Free Radicals "
Reaction of Electron Transfer, ~N: + Cl02 ~ ~W + Cl02
Reactions of Molecules with Oxygen " •
Reaction C2H5Li + RX~C2H5 + LiX + R"
35 Trimolecular Reactions of Radical Formation
CHAPTER III" THE CAGE EFFECT
36
37
38
Stoichiometric Inhibition Coefficients
Probability of Radical Escape into Bulk Volume (e) in Decomposition of Azobisisobutyronitrile
Probability of Radical Escape into Bulk Volume in Decomposition of Various Initiators
CHAPTER IV" METHODS FOR MEASURING RATE CONSTANTS OF RADICAL REACTIONS
No Tables
CHAPTER V" ISOMERIZATION AND DECOMPOSITION OF FREE RADICALS
39
40
41
42
Relative Rate Constants of Isomerization XC6R4C(CH3)2CH2~(CH3)2CCH2C6R4X
Relative Rate Constants for Decomposition of RORlR2CO" Radicals
Relative Rate of Splitting of Various Alkyl Groups from RlR2R3CO· Radicals • • • • • • • • • • • •
xv
103
105
106
107
108
115
121
128
175
176
176
177
xvi LIST OF TABLES
CHAPTER VI" RADICAL SUBSTITUTION REACTIONS
43
44
45
46
47
48
Hydrogen-Atom Reactions in Aqueous Solution at Room Temperature (230 ) """""""
Hydrogen-Atom Reactions of the Type RH + H"--7 H2 + R" in Hydrocarbon Solution at 230
Reactivity of Various Groups in Reactions with H"
Abstraction of Halogen Atom by Hydrogen (H" + RX~HX + R") in n-Hexane Solution at 230
Partial Reaction Rate Constants for Abstraction of H from C-H Bonds of Hydrocarbons by Chlorine Atoms "
Partial Rate Constants for Bromination (Br" + RH~BrH + R") " " " " "
49 Relative Rate Constants for
50
51
52
53
54
Bromination of Compounds XC6H4R
Reactions of H Abstraction by Hydroxyl in Aqueous Solutions at 230
Partial Rate Constants for Reaction of Hydroxyl Radicals ~Tith C-H Bond in Aqueous Solution at 230 and pH 9 • " " " " • • " "
Rate Constants for Reaction (CH3)3CO" + RH-7(CH3)3COH + R"
Partial Rate Constants for Reactions (CH3)3CO" + HC~ ~(CH3)3COH + "C~ (400 ) ••••••••••••
Abstraction of H by Cumyloxy Radicals
185
187
189
190
191
195
198
200
215
216
233
233
LIST OF TABLES
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
Rate Constants for Reaction ROZ + RH ~ ROOH + R· in RH Medium • • •••••
Reactivities of Various Peroxy Radicals • • • • •
Peroxy-Radical Reactions of the Type ROO· + R' H --:;,. ROOH + R' •
Reactions of Peroxy Radicals with Inhibitors (Phenols, Amines)
Rate Constants for Reactions of H Abstraction by Phenoxyl Radicals
Reaction of Hydrogen Exchange between Phenoxyl Radical and Phenol
Reactions of H Abstraction from Hydrocarbons (RH) by Nitroxy Radicals • • • • • • . • • • •
Abstraction of H by Methyl Radicals
Partial Rate Constants for Reactions X-H + CH3--:;" CH4 + X· (65 0 )
Abstraction of Halogen Atoms by Methyl Radica Is, R-X + CH3 ~ CH3X + R·
Abstraction of Hand Cl Atoms by C13C· Radicals . . • . . . . . . . . •
Abstraction of H Atoms by F3C· Radicals
Relative Rate Constants for Reactions of Phenyl Radical in CC14 at 600
Competition of Two Substitution Reactions ••••••••
Relative Rate Constants for Reactions of P-XC6H4 Radicals in CC14 at 60° .•........•..•
xvii
235
240
241
249
273
279
281
283
293
294
295
302
302
307
308
xviii LIST OF TABLES
70
71
72
73
74
75
76
Reactions of H Abstraction by Various Alkyl Radicals • • •
Abstraction of Halogen Atoms by Various Radicals
Chain Transfer in Bulk Polymerization of Styrene • • • • • • • • • • •
Chain Transfer in Bulk Polymerization of Methyl Methacrylate •••••
Chain Transfer in Bulk Polymerization of Vinyl Acetate • • • • • • • •
Chain Transfer in Bulk Polymerization of Various Monomers
Rate Constants for Reactions of Diphenylpicrylhydrazyl with RH •••
77 Correlation Ratios for Radical Substitution Reactions •
CHAPTER VII. ADDITION REACTIONS OF ATOMS AND RADICALS
78
79
80
81
82
83
84
Addition of Atoms and Radicals to Oxygen •
Reaction Rate Constants for Addition of Atoms at C = C Bond •••
Addition of Radicals at C = C Bond •
Addition of ROi at C = C Bond in Medium of Corresponding Olefin
Relative Rate Constants for Addition Reactions of Phenyl Radical •
Chain Propagation Rate Constants in Radical Polymerization •••
Copolymerization Rate Constants
309
312
315
328
332
334
338
344
355
356
357
363
365
365
368
LIST OF TABLES
85 Copolymerization Parameters q and £
for Calculating Copolymerization Constants •••••••••• •
86 Addition of Atoms and Free Radicals to Aromatic Compounds •
87 Addition of Free Atoms and Radicals to
88
Quinones, Carbonyl Compounds, Acids, and CO •••••••
Addition of Radicals to Nitriles, Nitro Compounds, and Schiff Bases
CHAPTER VIII. RECOMBINATION AND DISPROPORTIONATION OF FREE ATOMS AND RAD ICALS
89 Rate Constants for Recombination of Atoms in Solution ••••
90 Ratio between Disproportionation and
91
92
93
94
95
Recombination of Radicals with Free Valence on Carbon • • • •
Total Rate Constants for Self-Reactions of Alkyl Radicals ••••••
Rate Constants for Self-Reactions of HO· and RO· Radicals • • • • •
Rate Constants for Self-Reactions of Peroxy Radicals •••••
Recombination of Radicals Having Free Valence on N or Sn • • • • • •
Rate Constants for Reactions of Different Types of Radicals with Each Other • • • •
CHAPTER IX. EFFECT OF SOLVENT ON FREE RADICAL REACTIONS
96 Diffusion Coefficients of Atomic Iodine at 250 ••••••
xix
375
380
389
394
403
404
405
411
413
424
425
435
xx LIST OF TABLES
97
98
Manifestation of Molecular Hydrogen Bonds in Reactions of Radical Substitution • • • • •
Reactions of Hydrogen-Bonded ROZ •
CHAPTER X. OXIDATION-REDUCTION REACTIONS OF IONS WITH MOLECULES
99
100
101
102
103
104
105
106
107
Oxidation by Pentavalent Vanadium Ions • •
Oxidation by Trivalent Manganese Ions
Oxidation by Trivalent Iron Ions •
Oxidation by Trivalent Cobalt Ions
Oxidation by Cerium Ions in Aqueous Solutions ••••••• • • •
Oxidation of Variable-Valence Metal Ions by Oxygen • • • • • •
Reactions of Ions with Hydrogen Peroxide in Aqueous Solutions
Reactions of Metal Ions and Complexes with Peroxides • • • • • • • • •
Oxidation of Fe2+ Ions by Quinones •
CHAPTER XI. REACTIONS OF ATOMS AND RADICALS WITH IONS
107a Reactions of Hydrogen Atoms with Ions at Room Temperature (20-250 )
108 Reactions of Radicals with Ions
CHAPTER XII. REACTIONS OF ION-RADICALS AND SOLVATED ELECTRONS
109 Reactions of Ion-Radicals with Molecules •
110 Reactions between Ion-Radicals
436
439
488
493
497
500
508
518
522
524
529
533
540
563
571
LIST OF TABLES
111 Reactions of Solvated Electrons with
112
Molecules and Radicals in Aqueous Solutions at Room Temperature •••••
Rate Constants for Reactions of eaq with Ions in Aqueous Solutions at Room Temperature (20-250 )
CHAPTER XIII. IONIC OXIDATION-REDUCTION REACTIONS
113 Rate Constants for Electron Exchange •
114 Oxidation-Reduction Reactions between Ions . . . . . . . . . . . . . .
xxi
573
595
609
624
k
K
E
A
e
C
SYMBOLS
Reaction rate constant, expressed in sec- l for first-order reaction, liter/mole.sec for second-order reaction, and liter2 /mole 2 .sec for third-order reaction
Equilibrium constant
Activation energy, kcal/mole
Temperature in degrees Celsius
Temperature in degrees Kelvin e = 4.575 T/lOOO
Preexponential factor, with dimensionality corresponding to that of k for the reaction
Rate of chain reaction
Chain propagation rate constant in chain reaction
Rate constant for reaction between two radicals
Respectively, rate and rate constant for reaction of radical formation from molecules. If radicals Ro are formed at a rate Wi and are destroyed only by reaction with each other (rate constant k t ), then in the stationary regime Wi = 2k t [R 0] 2
Probability of escape of radicals into the bulk volume from a "cage" of solvent; if k is the rate constant for decomposition of initiator into two radicals, then ki = 2 ek
Concentration, mole/liter
xxiii
xxiv
InR
f
SYMBOLS
Inhibitor or acceptor of free radicals
Inhibition coefficient, equal to the number of radicals successively reacted with one molecule of inhibitor and conversion products from the inhibitor molecule
ABBREVIATIONS
The following abbreviations, which denote methods for measuring rate constants, are not listed in the original Russian text but have been compiled here for convenience. Abbreviations used here (in the English translation) are listed in the left-hand column; abbreviations used in the original Russian text are transliterated and listed in the right-hand column for reference.
Catal. CINH CL CSM DP EP EPR FM lCA
IIM IIP
1M JM KEPF
KICR
Kin. Racem. KNP KRAC
KRR MCR NK NKR
Ionic catalytic reactions Inhibited chain reaction Chemiluminescence Consumption of starting material Degree of polymerization Emulsion polymerization Electron paramagnetic resonance Flash method Initial consumption of (radical)
acceptor Intermittent illumination method Introduction of initiator
fragments into polymer Isotope method Jet method Kinetics of end product
formation Kinetics of initiated chain
reaction Kinetics of racemization [not identified]
Kinetics of radical acceptor consumption
[not identified] Method of competing reactions [not identified]
Nonstationary kinetics of radical chain reaction
xxv
Kataliz TsING KhL RIV SP EP EPR FM NRA
PO VIP
1M JM KOKP
KTsIR
Kin. Ras. KNP KRAR
KRR MKR NK NKR
xxvi
NMR NR Pol. POL PR PSD RICR RRC
RUCR SUNR TIM TJ TsINR
Nuclear magnetic resonance [not identified] Polarographic method [not identified] Pulse radio lysis Photochemical space discontinuity Rate of initiated chain reaction Products of radical recombination
in cage Rate of unbranched chain reaction [not identified] Tritium isotope method Temperature jump [not identified]
ABBREVIATIONS
YaMR NR Pol. POL IP FPP STsIR PR
STsNR SUNR ITM TS TsINR
Note: For a listing of abbreviations for names of ligands in metal complexes, see Chapter X, p. 482.