XVLISTOFTABLES31Reactions with Participatiqn ofPeroxide,ROOH +M103Complex.kFree Radicals32Reaction of Electron Transfer,105>N:+ C102→>N+ + C10210633Reactions of Molecules with Oxygen34107Reaction C2HsLi + RX→>C2H5+LiX+R35Trimolecular Reactions of Radical108FormationCHAPTER III.THE CAGE EFFECT36115Stoichiometric Inhibition Coefficients37Probability of Radical Escape intoBulk Volume (e) in Decompo-121sition of Azobisisobutyronitrile38Probability of Radical Escape intoBulk Volume in Decomposition128of Various InitiatorsCHAPTER IV.METHODSFOR MEASURING RATECONSTANTS OF RADICAL REACTIONSNo TablesCHAPTER V.ISOMERIZATIONANDDECOMPOSITIONOFFREERADICALS39Relative Rate Constants of Isomerization175XC6H4C(CH3)2CH2—>(CH3)2CCH2C6H4X40176Ratio of Constants ka/ka for (cH3)3co:41Relative Rate Constants for176Decomposition of RoRiR2Co-Radicals42Relative Rate of Splitting of VariousAlkylGroupsfrom RiR2R3co177Radicals
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
xviLIST OFTABLESCHAPTER VI.RADICAL SUBSTITUTION REACTIONS43Hydrogen-Atom Reactions in AqueousSolution at Room Temperature185(230)44Hydrogen-Atom Reactions of the TypeRH + H'->H2 + R: in187Hydrocarbon Solution at 23045Reactivity of Various Groups in189Reactions with H'46Abstraction of Halogen Atom byHydrogen (H'+ RX->HX+R')190in n-Hexane Solutionat 23047Partial Reaction Rate Constants forAbstractionofH from C-HBonds of Hydrocarbons by191Chlorine Atoms48Partial Rate Constants for Bromination195(Br·+ RH->BrH + R')49Relative Rate Constants for198BrominationofCompounds XCHzR50Reactions of HAbstraction by Hydroxyl200in Aqueous Solutions at 23051Partial Rate Constants for Reactionof Hydroxyl Radicals with C-HBond in Aqueous Solution at215230andpH952Rate Constants for Reaction216(CH3)3CO·+RH->(CH3)3COH +R53Partial Rate Constants for Reactions(CH3)3CO- + HC<→>(CH3)3COH + C<233(400)23354Abstraction of H by CumyloxyRadicals
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
LISTOFTABLESxvii55Rate Constants for ReactionRO2 + RH→>ROOH + R: in235RH Medium56Reactivities of Various Peroxy240Radicals57Peroxy-Radical Reactions of the241Type ROO·+R'H>ROOH+R'58Reactions of Peroxy Radicals with249Inhibitors (Phenols, Amines)59Rate Constants for Reactions of H273Abstraction by Phenoxyl Radicals60Reaction of Hydrogen Exchange between279Phenoxyl Radical and Phenol61Reactions of HAbstraction fromHydrocarbons (RH)byNitroxy281Radicals62283Abstraction of H by Methyl Radicals63Partial Rate Constants for Reactions293X-H + CH3>CH4 + X(650)64Abstraction of Halogen Atoms by Methyl294Radicals, R-x + CH:>CH3X + R:65Abstraction of H and cl Atoms by Clgc'295Radicals.66302Abstraction of HAtoms by F3cRadicals67Relative Rate Constants for Reactions302of PhenylRadical in ccl4at 60068Competition of Two Substitution307Reactions69Relative Rate Constants for Reactionsof p-XC6H4Radicals in Cc14 at600308
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· (650 ) 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
xiliLISTOFTABLES70Reactions of H Abstraction by Various309Alkyl Radicals71Abstraction ofHalogenAtomsby312Various Radicals72Chain Transfer in Bulk Polymerization315of Styrene.73Chain Transfer in Bulk Polymerization328of Methyl Methacrylate74Chain Transfer in Bulk Polymerization332ofvinylAcetate75Chain Transfer in Bulk Polymerization334of Various Monomers76Rate Constants for Reactions of338Diphenylpicrylhydrazyl with RH .77Correlation Ratios for Radical344Substitution Reactions :CHAPTER VII.ADDITION REACTIONS OF ATOMS AND RADICALS78355AdditionofAtomsandRadicalstoOxygen79Reaction Rate Constants for Addition356of Atoms at C= C Bond.80357Addition of Radicals at CCBond..81Addition of RO2at C =C Bond in363Medium of Corresponding Olefin82Relative Rate Constants forAddition Reactions of365Phenyl Radical.83Chain Propagation Rate Constants in365Radical Polymerization.84368Copolymerization Rate Constants
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
LISTOFTABLESxix85Copolymerization Parameters q and for Calculating Copolymerization375Constants86AdditionofAtoms andFreeRadicalsto380Aromatic Compounds87Addition of Free Atoms and Radicals toQuinones, Carbonyl Compounds,389Acids,and co88Addition of Radicals to Nitriles,394Nitro Compounds, and Schiff BasesCHAPTER VIII.RECOMBINATIONANDDISPROPORTIONATIONOF FREEATOMSAND RADICALS89RateConstants for Recombination of403Atomsin Solution90Ratio between Disproportionation andRecombination of Radicals with404FreeValenceonCarbon.91Total Rate Constants for Self-Reactions405of Alkyl Radicals92Rate Constants for Self-Reactions of411Ho'and Ro'Radicals93Rate Constants for Self-Reactions of413Peroxy Radicals94Recombination of Radicals Having424Free Valence on N or Sn95Rate Constants for Reactions ofDifferent Types of Radicals425with Each OtherCHAPTER IX.EFFECTOF SOLVENT ONFREERADICALREACTIONS96Diffusion Coefficients of Atomic435Iodine at 250
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 25 0 •••••• xix 375 380 389 394 403 404 405 411 413 424 425 435