CONTENTSix179CHAPTERVI.RADICAL SUBSTITUTION REACTIONS1791.Reactions of Atoms2.Reactions of Radicals Having Free181Valence on Oxygen3.Reactions of Radicals Having Free183Valence on Carbon4.183Chain Transfer in Radical Polymerization5.Reactions of Radicals Having Free184Valence on Nitrogen6.Correlation Equations for Radical184Substitution ReactionsADDITION REACTIONS OFATOMS ANDCHAPTER VII.351RADICALS1.Addition of Atoms and Radicals to351Molecular Oxygen3512.Addition at C=C Bond3533. Addition to Aromatic Compounds4.Addition to Quinones,CarbonylCompounds, Nitriles, and354Nitro CompoundsCHAPTER VIII.RECOMBINATIONANDDISPROPORTION-399ATIONOF FREE ATOMS AND RADICALS399l.Recombination ofAtoms2.Disproportionation and Recombination399of Alkyl and Ro*Radicals4013.Reactions between Peroxy Radicals4.Reactions of Radicals Having Free402Valence on Nitrogen or Tin
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 DISPROPORTIONix 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
xCONTENTS5.Reactions between Free Radicals of402Different TypesCHAPTERIX.EFFECT OF SOLVENT ON FREERADICAL427REACTIONS1.427Solvent Viscosity2.427Internal Pressure of Liquid3.428Nonspecific Solvation4304.Hydrogen Bond between Molecules4315.Radical Hydrogen Bond4326.Formation of T-Complexes443(Part Two)LITERATURE CITEDPART THREE-IONIC HOMOLYTIC REACTIONSCHAPTER X.OXIDATION-REDUCTION REACTIONS OF479IONSWITHMOLECULES1.Oxidation of Organic Compounds by479Variable-Valence Metal Ions2.Reaction of Variable-Valence MetalIons with Oxygen, Peroxides,485and QuinonesCHAPTERXI.REACTIONSOFATOMSANDRADICALS531WITH IONS.5311.Reactions of Hydrogen Atom2.531Reactions of Free Radicals
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
CONTENTSxiCHAPTER XII.REACTIONS OF ION-RADICALSAND561SOLVATED ELECTRONS1.561Reactions of Ion-Radicals2.Solvated Electron561607CHAPTER XIII.IONIC OXIDATION-REDUCTION REACTIONS.1.Methods for Measuring Reaction Ratesfor Electron Transfer from607Ion to Ion2.608Electron Exchange Reactions3.Oxidation-Reduction Reactionsbetween608Ions735LITERATURE CITED(Part Three)
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
LISTOFTABLESCHAPTER I.MONOMOLECULAR REACTIONS1Rate Constants for Benzoyl Peroxide17Decomposition2Decomposition of Benzoyl Peroxide18in Various Solvents3Decomposition of Symmetrically19Substituted Benzoyl Peroxides3ADecomposition of UnsymmetricallySubstituted Benzoyl Peroxides21and Phthaloyl Peroxide4Decomposition of Acetyl Peroxide in23Various Solvents5Decomposition of Symmetrical Diacyl24Peroxides,RCOoocOR6Decomposition of Unsymmetrical Diacyl32Peroxides,RicooocOR2357Decomposition of Peroxides,RooR.8Decomposition of Unsymmetrical38Peroxides,Ri00R2409DecompositionofPeroxides,(CH3)3COoCOR.5010Decomposition of Dibasic Peroxides11Decomposition of Hydroperoxides in56Aromatic Solventsxili
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
xivLIST.OF TABLES5712Decomposition of Azobisisobutyronitrile1360DecompositionofR-N=N-R1466Decomposition of Ri-N=N-R27015Decomposition at C-C Bond7216Decomposition at N-N Bond17Decomposition of Compounds with74Ruptureof N-C orC-oBond1877Decomposition of Nitrogen Pentoxide1978Decomposition of Nitro Compounds2080Decomposition at C-Metal Bonds.8121Decomposition of xC6HIcl222Constants in Correlation Equations82logk=logko+po23Compensation Effect for Monomolecular83Decomposition Reactions24Volume Change Av+ in Decomposition84ofMolecules25Range of Variation of k forDecomposition of Initiators85in Various SolventsCHAPTER II.BIMOLECULAR ANDTRIMOLECULAR REACTIONS9326Dimerization of Unsaturated Compounds.9427Volume Change in Diels-Alder Reaction9528Reactions of Amines with Peroxides9929Reaction ROOH+R'H->Free RadicalsK30Reactions of Hydroperoxides 2 RooH100Complex_k,Free Radicals
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