Liquid-PhaseReaction Rate ConstantsE.T. DenisovInstituteof Chemical PhysicsMoscow,UssRTranslated fromRussianbyR.K.JohnstonIFI/PLENUMNEWYORK-WASHINGTON-LONDON
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
PREFACEThe past 25 years in chemical kinetics have seen majoradvancesin studying the mechanismsof complex chemical re-actions, in particular free radicalreactions.Many differ-ent methods have been developed for quantitative studies ofelementary chemical reactions.Thousands of rate constantshave been measured, for hundreds of diverse chemical reac.tions. It is becoming more and more difficult for the chemistto orient himself in the voluminous and rapidly growing liter-ature of chemical reaction kinetics.This leads to majorexpenditures of time in searchingout,collecting, and eval-uating quantitative kinetic data;to unnecessary repetition(duplication)of research; andsituation in which thetoarich material already accumulatedin the field of chemicalkinetics is very often not fully utilized in comparing,interpreting, and analyzingnewexperimental data. There isa pressing need for the creationof a series of handbooks onreaction rate constants.Suchworkwasbegunseveralyearsago at the initiative of V. N. Kondrat'ev, and is now goingforward under his direction atthe Institute of ChemicalPhysics of the USSR Academy of Sciences.This book is devoted to liquid-phase, homolytic reactions.Part One contains data on monomolecular reactions in whichmolecules decompose to formradicals, as wellas data on bi-molecular and trimolecular reactions that form free radicals.Also collected in PartOnedataareon theprobability ofradical escape into the bulkvolumefrom a"cage" of solventas wellwith various initiatorsasvaluesof the stoichio-metric inhibition coefficientsforvariousphenols and aromaticamines that are used asfreeradicalacceptors.In Part Two,rate constants are collectedforreactions of decomposition,substitution, and additionofradicalsto molecules,as wellas radical recombinationand disproportionation reactions.Part Three contains dataon ion--molecule reactions that areaccompanied by radical formation, as well as reactions of
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
viPREFACEfree radicals with metal ions and acid anions, reactions ofion-radicals and solvated electrons, and ionic oxidation-reduction reactions with electron transfer.In this book,rate constant values are presented along with a statementof the conditions and a brief characterization of the methodof measurement.I wish to express deep gratitude to AcademicianV.N.Kondrat'ev for having inspired me to this not easy butuseful task, and for having aided me with counsel.The lastchapter of this book was written by V. N. Berdnikov.Forassistance in collecting the reaction rateconstants,Ithank 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 manuscriptforpublication.E.T. Denisov
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
CONTENTSPrefacevxiiiList of TablesxxiiiSymbols.AbbreviationsxxVPART ONE-REACTIONS OF MOLECULES1CHAPTER I.MONOMOLECULAR REACTIONS1.Methods for Measuring Rate Constants3of Monomolecular Reactions2.Rate Constants for Decomposition of8PeroxideCompounds103.Decomposition of Azo Compounds4.Decomposition atC-C,N-N,N-C,10N-O,and C-Metal Bonds11Decompositionof Iodobenzene Dichloride5.116.Correlation Equations7.Effect of Pressure and Solvent on13Monomolecular Reactions87CHAPTER II.BIMOLECULAR AND TRIMOLECULAR REACTIONSl.Methods forMeasuringRateConstants87of Bimolecular Reactionsvi
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
viliCONTENTS892.Diels-Alder Reaction3.Bimolecular Reactions with Peroxide89Participation4.Oxidation-Reduction Reactions withParticipation of c102,02,91and C125.Reactions with Rupture of Metal-Carbon92Bond926.Trimolecular Reactions109CHAPTER III.THE CAGE EFFECT109l.Questions of Theory2.Methods for Measuring Initiator111Efficiency1143.Initiator Efficiency135LITERATURE CITED(PartOne)PART TWO -REACTIONSOF FREE ATOMS AND RADICALSCHAPTER IV.METHODSFOR MEASURING RATE CONSTANTS157OF RADICAL REACTIONSl. Measurement of Relative Rate Constants157of Radical Reactions2. Measurement of Absolute Rate Constantsof Reactions of Atoms and164RadicalsISOMERIZATIONAND DECOMPOSITION OFCHAPTER V.173FREE RADICALS173l.Isomerization of Free Radicals1742. Decomposition of Free Radicals
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