Chemical Kinetics: Fundamentals and Recent Developments: Fundamentals and Recent Developments
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Table of contents
- Cover
- CHEMICAL KINETICS: Fundamentals and New Developmentsiii
- Copyright Pageiv
- Contentsix
- Prefacev
- Part 1: General Problems of Chemical Kinetics1
- Chapter 1. General ideas of chemical kinetics1
- 1.1. Subject of chemical kinetics1
- 1.2. History of the appearance of chemical kinetics3
- 1.3. Rate of chemical reaction5
- 1.4. Law of mass action8
- 1.5. Order and rate constant of the reaction8
- 1.6. Arrhenius law13
- Part 2: Elementary Gas Phase Reactions16
- Chapter 2. Theory of elementary reactions17
- 2.1. General statements and definitions17
- 2.2. Methods for calculation of rate constants of elementary reactions46
- Chapter 3. Methods for studying elementary reactions67
- 3.1. Instrumental methods for experiments67
- 3.2. Methods of detection of active species75
- 3.3. Methods for obtaining active species95
- Chapter 4. Experimental studies of gas-phase reactions98
- 4.1. Unimolecular reactions98
- 4.2. Bimolecular reactions110
- 4.3. Femtochemistry128
- Part 3: Chemical Reactions in Liquid Phase136
- Chapter 5. Diffusion-controlled reactions in solution136
- 5.1. Brief characterization of the liquid state of matter136
- 5.2. Reactions controlled by molecular diffusion139
- 5.3. Cage effect in liquid144
- 5.4. Cage effect in solid polymers152
- 5.5. Pulse methods for studying the kinetics of fast reactions157
- Chapter 6. Bimolecular reactions in solutions. Influence of medium160
- 6.1. Theory of encounters in liquid160
- 6.2. Theory of activated complex164
- 6.3. Comparison of bimolecular reactions in gas and liquid phases166
- 6.4. Reactions of polar particles169
- 6.5. Reactions of ions175
- 6.6. Correlation equations in chemical kinetics178
- Chapter 7. Radical reactions184
- 7.1. Decomposition of molecules to radicals184
- 7.2. Isomerization of free radicals191
- 7.3. Decomposition of free radicals196
- 7.4. Recombination and disproportionation of radicals196
- 7.5. Free radical addition201
- 7.6. Radical abstraction reactions217
- 7.7. Radical substitution reactions236
- 7.8. Reactions of biradicals236
- 7.9. Radical reactions in solid polymer238
- Chapter 8. Reactions of ions and radical ions250
- 8.1. Dissociation to ions and ion recombination250
- 8.2. Mechanisms of heterolytic reactions255
- 8.3. Reactions of carbocations and carbanions271
- 8.4. Ion redox reactions279
- 8.5. Redox reactions of ions with molecules286
- 8.6. Redox reactions of ions with atoms and radicals289
- 8.7. Reactions of radical anions294
- 8.8. Methods of studying fast ion reactions296
- Chapter 9. Reactions of molecules305
- 9.1. Isomerization and decomposition of molecules305
- 9.2. Bimolecular reactions with concerted rearrangement of bonds309
- 9.3. Molecular complexes311
- 9.4. Molecular halogenation of olefins315
- Part 4: Chain Reactions317
- Chapter 10. Chain non-branched reactions317
- 10.1. Steps of chain non-branched reaction and conditions of its accomplishment317
- 10.2. Competition of chain and molecular reactions322
- 10.3. Kinetic regularities of chain reaction325
- Chapter 11. Oxidation of organic compounds by molecular oxygen331
- 11.1. Elementary steps of chain oxidation331
- 11.2. Kinetics of initiated oxidation of organic compounds339
- 11.3. Kinetics of autoxidation of hydrocarbons in liquid phase342
- 11.4. Inhibition of oxidation reactions349
- Chapter 12. Chain branched reactions368
- 12.1. Theory of chain branched reaction368
- 12.2. Combustion of hydrogen373
- 12.3. Chain reactions with energy branching379
- 12.4. Chemical lasers based on chain reactions381
- Chapter 13. Methods for studying chain reactions386
- 13.1. Methods of identification of radicals and intermediate386
- 13.2. Method of free radical acceptors387
- 13.3. Methods of chain reaction initiation390
- 13.4. Photochemical methods for studying elementary steps393
- 13.5. Methods of studying liquid-phase oxidation of organic compounds396
- 13.6. Methods for studying inhibitors of chain reactions400
- 13.7. Method for shifting limits of chain ignition404
- Part 5: Homogeneous Catlysis406
- Chapter 14. General kinetics regularities in homogeneous catalysis406
- 14.1. General principles of homogeneous and enzyme catalysis406
- 14.2. Simple catalytic reactions408
- 14.3. Methods of analysis of kinetic schemes410
- 14.4. Kinetic classification of catalytic reactions413
- 14.5. Kinetic equations of multistage catalytic reactions414
- 14.6. Inhibitors and activators in catalysis417
- 14.7. Kinetics of cooperative processes420
- 14.8. On the methods of studying the mechanism of catalytic reactions425
- Chapter 15. Acid-base catalysis430
- 15.1. Acids and bases430
- 15.2. Acid-base equilibrium432
- 15.3. Proton transfer rate constants436
- 15.4. Quantum-chemical theory of proton transfer439
- 15.5. Theory of acid-base catalysis441
- 15.6. Reactions catalyzed by acids and bases444
- Chapter 16. Redox catalysis452
- 16.1. Catalysis of hydrogen peroxide decomposition by iron ions453
- 16.2. Catalysis of hydrocarbon oxidation with dioxygen by transition metals455
- 16.3. Cobalt-bromide catalysis461
- 16.4. Catalytic epoxidation of olefins by hydroperoxides464
- 16.5. Oscillating oxidation reactions467
- Chapter 17. Catalysis by metal complexes472
- 17.1. Electron structure and catalytic properties of metal complexes472
- 17.2. Specific features of electronic structure of transition metal clusters474
- 17.3. Mechanisms of reactions in the coordination sphere of metal complexes477
- 17.4. Hydrogenation and activation of C-H bonds482
- 17.5. Carbonylation, carboxylation, hydrofomylation, and hydrochlorination485
- 17.6. Polymerization, oligomerization, and metathesis487
- 17.7. Oxidation490
- 17.8. Metal complex electrocatalysts492
- 17.9. Water oxidation493
- 17.10. Long-range electron transfer495
- 17.11. Concerted reactions, Synchronization factor497
- 17.12. The principle of optimum motionŽ in elementary acts of chemical and enzymatic processes499
- 17.13. Multi-electron mechanisms of redox reactions. Switching molecular devices500
- Chapter 18. Enzymes as catalysts502
- 18.1 .Basic conceptions and definitions502
- 18.2. Main statements of enzymatic catalysis theory503
- 18.3. Chemical Mechanisms of Enzyme Reactions505
- 18.4. Mechanisms of chosen enzyme reactions507
- 18.5. Protein intramolecular dynamics and catalytic activity of enzymes517
- 18.6. Energy and entropy parameters of enzymatic processes521
- 18.7. Enzyme catalysis today and chemistry of the 21th century522
- Bibliography525
- Index537
Comprehensive manual embracing essentially all the classical and modern areas of chemical kinetics. Provides details of modern applications in chemistry, technology and biochemistry.
Special sections of the book treat subjects not covered sufficiently in other manuals, including: modern methods of experimental determination of rate constants of reactions including laser pico- and femtochemistry, magnetochemistry, and ESR; and descriptions of advanced theories of elementary chemical processes.
- Comprehensive manual covering practically all areas of chemical kinetics, both classical and modern.
- Adequate coverage given to topics not covered sufficiently by other works.
- Covers fundamentals and recent developments in homogeneous catalysis and its modeling from a chemical kinetics perspective.
Special sections of the book treat subjects not covered sufficiently in other manuals, including: modern methods of experimental determination of rate constants of reactions including laser pico- and femtochemistry, magnetochemistry, and ESR; and descriptions of advanced theories of elementary chemical processes.
- Comprehensive manual covering practically all areas of chemical kinetics, both classical and modern.
- Adequate coverage given to topics not covered sufficiently by other works.
- Covers fundamentals and recent developments in homogeneous catalysis and its modeling from a chemical kinetics perspective.