XxLIST OF TABLES97Manifestation of Molecular HydrogenBonds in Reactions of Radical436Substitution.98439Reactions of Hydrogen-Bonded RO2.CHAPTER X.OXIDATION-REDUCTION REACTIONS OF IONSWITH MOLECULES99488Oxidation byPentavalent Vanadium Ions100493Oxidation by Trivalent Manganese Ions101497Oxidation by Trivalent Iron Ions102500Oxidation by Trivalent Cobalt Ions103Oxidation by Cerium Ions in Aqueous508Solutions104Oxidation of Variable-Valence Metal518IonsbyOxygen105Reactions of Ions with Hydrogen522Peroxide in Aqueous Solutions106Reactions of Metal Ions and Complexes524withPeroxidesOxidation of Fe2+ Ions by Quinones107529REACTIONS OF ATOMS AND RADICALS WITHCHAPTER XI.IONS107aReactions of Hydrogen Atoms withIons atRoom Temperature (20-250)533108540Reactions of Radicals with IonsCHAPTER XII.REACTIONS OF ION-RADICALS ANDSOLVATED ELECTRONS109563Reactions of Ion-Radicals with Molecules :571110Reactionsbetween Ion-Radicals
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
LISTOFTABLESxxi111Reactions of Solvated Electrons withMolecules and RadicalsinAqueousSolutionsatRoom573Temperature112RateConstants for Reactions of agwith IonsinAqueousSolutions595(20-250)at Room TemperatureCHAPTER XIII.IONIC OXIDATION-REDUCTION REACTIONS113609Rate Constants for Electron Exchange114Oxidation-Reduction Reactionsbetween624Ions
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
SYMBOLSReaction rate constant, expressed in sec-l forkfirst-order reaction, liter/mole.sec forsecond-order reaction, and liter2/mole2.secfor third-order reactionKEquilibriumconstantEActivation energy,kcal/moletoTemperature in degrees CelsiusToTemperature in degrees Kelvine=4.575T/1000APreexponential factor, with dimensionality corresponding to that of k for the reactionWyRate of chain reactionkpChain propagation rate constant in chain reactionktRate constant for reaction between two radicalsWiandkiRespectively, rate and rate constant for reactionof radical formation from molecules.If radi-cals R- are formed at a rate Wi and are de-stroyed only by reaction with each other (rateconstant kt),then in the stationary regimeWi=2kt[R-j2eProbability of escape of radicals into the bulkvolume from a "cage" of solvent; if k is therate constant for decomposition of initiatorinto two radicals,then ki =2 ekCConcentration,mole/iiterxxili
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 = 2kt [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
SYMBOLSxxivInHInhibitor or acceptor of free radicalsHenumberofInhibition coefficient,equalto theradicals successively reacted with one mole-cule of inhibitor andconversion productsfrom the inhibitor molecule
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
ABBREVIATIONSThe following abbreviations, which denote methods for measur-ing rate constants, are not listed in the original Russiantext but have been compiled here for convenience.Abbrevia-tions used here (in the English translation) are listedind column; abbreviations used in the originalthe left-handlisted in the right-handRussian text are transliterated andcolumn for reference.Catal.Ionic catalytic reactionsKatalizCINHTsINGInhibited chain reactionCLKhLChemiluminescenceCSMRIVConsumption of starting materialDPSPDegree of polymerizationEPEPEmulsion polymerizationEPREPRElectron paramagnetic resonanceFMFMFlash methodICANRAInitial consumption of(radical)acceptorPOIIMIntermittent illumination methodIIPVIPIntroduction of initiatorfragments into polymerIMIMIsotope methodJMJMJet methodKEPFKOKPKinetics of end productformationKICRKTsIRKinetics of initiatedchainreactionKin. Racem.Kin.Kinetics of racemizationRas.KNPKNP[not identified]KRACKRARKinetics of radicalacceptorconsumptionKRRKRR[not identified]MCRMKRMethod of competingreactionsNKNK[not identified]NKRNKRNonstationary kineticssofradicalchain reactionXXV
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