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BK

Second edition

Amsterdam : Elsevier, [2021]

xii, 681 stran : ilustrace ; 26 cm

ISBN 978-0-444-64039-0 (brožováno)

Obsahuje bibliografii a rejstřík

002000515

Preface xi // CHAPTER 1 Introduction l // 1.1 Introduction 1 // 1.2 Initial difficulties in the development of chemical kinetics in the twentieth century 2 // 1.3 Chemical kinetics: the current view 5 // References 15 // CHAPTER 2 Reaction rate laws 17 // 2.1 Reaction rates 17 // 2.2 Factors that influence the velocities of reactions 19 // References 35 // CHAPTER 3 Experimental methods 37 // 3.1 Application of conventional techniques to // study reactions 38 // 3.2 Application of special techniques for fast reactions 54 // References 90 // CHAPTER 4 Reaction order and rate constants 93 // 4.1 Rates of elementary reactions 93 // 4.2 Rates of complex reactions 100 // 4.3 Methods for solving kinetic equations 109 // 4.4 Simplification of kinetic schemes 128 // 4.5 Global and target analysis of kinetic data 135 // References 138 // CHAPTER 5 Collisions and molecular dynamics 139 // 5.1 Simple collision theory 141 // 5.2 Improved collision theory 146 // 5.3 Collision cross section 150 // 5.4 Calculation of classical trajectories 157 // 5.5 PES crossings 163 // 5.6 Molecular dynamics 167 // References 172 // CHAPTER 6 Reactivity in thermalised systems 173 // 6.1 Transition-state theory 173 // 6.2 Semi-classical treatments 186 // V // 6.3 Intersecting-state model 198 // References 221 // CHAPTER 7 Relationships between structure and reactivity 225 // 7.1 Quadratic free-energy relationships 225 // 7.2 Linear free-energy relationships 229 // 7.3 Other kinds of relationships between structure and reactivity 237 // References 244 // CHAPTER 8 Unimolecular reactions 247 // 8.1 Lindemann—Christiansen mechanism 247 // 8.2 Hinshelwooď s treatment 250 // 8.3 Rice—Ramsperger—Kassel—Marcus treatment 253 // 8.4 Local random matrix theory 256 // 8.5 Energy barriers in the isomerisation of cyclopropane 258 // References 261 // CHAPTER 9 Elementary reactions in solution 263 //

9.1 Solvent effects on reaction rates 263 // 9.2 Effect of diffusion 265 // 9.3 Diffusion constants 269 // 9.4 Spin-statistical factors in diffusion-controlled reactions 275 // 9.5 Reaction control 277 // References 293 // CHAPTER 10 Reactions on surfaces 295 // 10.1 Adsorption 295 // 10.2 Adsorption isotherms 300 // 10.3 Kinetics on surfaces 303 // 10.4 Transition-state theory for reactions on surfaces 308 // 10.5 Model systems 312 // References 315 // CHAPTER 11 Substitution reactions 317 // 11.1 Mechanisms of substitution reactions 317 // 11.2 Sn2 and SN1 reactions 318 // 11.3 Langford—Gray classification 320 // 11.4 Symmetrical methyl group transfers in the gas-phase 324 // 11.5 State correlation diagrams of Pross and Shaik 327 // 11.6 Intersecting-state model 329 // 11.7 Cross-reactions in methyl group transfers in the gas phase 334 // 11.8 Solvent effects in methyl group transfers 336 // References 341 // CHAPTER 12 Chain reactions 343 // 12.1 Hydrogen—bromine reaction 343 // 12.2 Reaction between molecular hydrogen and chlorine 346 // 12.3 Reaction between molecular hydrogen and iodine 347 // 12.4 Calculation of energy barriers for elementary steps in hydrogen—halogen reactions 348 // 12.5 Comparison of the mechanisms of the hydrogen—halogen reactions 351 // 12.6 Pyrolysis of hydrocarbons 353 // 12.7 Explosive reactions 358 // 12.8 Polymerisation reactions 366 // References 368 // CHAPTER 13 Acid-base catalysis and // proton-transfer reactions 369 // 13.1 General catalytic mechanisms 369 // 13.2 General and specific acid—base catalysis 374 // 13.3 Mechanistic interpretation of the pH dependence // of the rates 377 // 13.4 Catalytic activity and acid—base strength 386 // 13.5 Salt effects 389 // 13.6 Acidity functions 390 // 13.7 Hydrated proton mobility in water 392 // 13.8 Proton-transfer rates in solution 398 //

13.9 Proton-transfer model system 406 // References 407 // CHAPTER 14 Enzymatic catalysis 409 // 14.1 Terminology 409 // 14.2 Factors that accelerate enzymatic action 412 // 14.3 Michaelis—Menten equation 418 // 14.4 Mechanisms with two enzyme—substrate complexes 423 // 14.5 Inhibition of enzymes 424 // 14.6 Effects of pH 429 // 14.7 Temperature effects 431 // 14.8 Isomerisation of dihydroxyacetone phosphate to glyceraldehyde 3-phosphate catalysed by triose-phosphate isomerase 433 // 14.9 Hydroperoxidation of linoleic acid catalysed by soybean lipoxygenase-1 435 // 14.10 Enzymes in drug design 437 // References 438 // CHAPTER 15 Pharmacokinetics 441 // 15.1 Origins and current use of pharmacokinetics 441 // 15.2 Drug administration and absorption 443 // 15.3 Drug distribution 445 // 15.4 Drug metabolism and excretion 447 // 15.5 Pharmacokinetics models 449 // References 461 // CHAPTER 16 Transitions between electronic states 463 // 16.1 Mechanisms of energy transfer 463 // 16.2 The “Golden Rule” of quantum mechanics 470 // 16.3 Radiative and radiationless rates 474 // 16.4 Franck—Condon factors 480 // 16.5 Radiationless transition within a molecule 488 // 16.6 Triplet energy (or electron) transfer between molecules 492 // 16.7 Electronic coupling 504 // 16.8 Triplet energy transfer rates 512 // References 519 // CHAPTER 17 Electron-transfer reactions 523 // 17.1 Rate laws for outer-sphere electron exchanges 523 // 17.2 Theories of electron-transfer reactions 525 // 17.3 ISM and electron-transfer reactions 540 // 17.4 Non-adiabatic self-exchanges of transition-metal complexes 548 // 17.5 Electron self-exchanges of organic molecules 550 // 17.6 Inverted regions 552 // — I ).l—fclectron transler at electrodes 562 // References 575 // CHAPTER 18 Oscillatory reactions 579 // 18.1 Non-linear systems 579 // 18.2 Chaos 587 // 18.3 Oscillatory reactions 592 ///

18.4 The Coimbrator 596 // References 601 // Contents // Appendix 1: General data 603 // Appendix 2: Statistical thermodynamics 605 // Appendix 3: Parameters employed in ISM calculations 613 // Appendix 4: Semi-classical interacting state model 617 // Appendix 5: The Lippincott—Schroeder potential 623 // Appendix 6: Quantum-mechanical radiationless transition theory 629 // Appendix 7: Problems 643 // Index 673