Physical Chemistry 3: — Chemical Kinetics — - Christian-Albrechts ...

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vi 8.7 References 202 9 Explosions 203 9.1 Chain reactions and chain explosions 203 9.1.1 Chain reactions without branching 203 9.1.2 Chain reactions with branching 204 9.2 Heat explosions 207 9.2.1 Semenov theory for “stirred reactors” ( =const) 207 9.2.2 Frank—Kamenetskii theory for “unstirred reactors” 211 9.2.3 Explosion limits 212 9.2.4 Growth curves and catastrophy theory 212 10 Catalysis 214 10.1 Kinetics of enzyme catalyzed reactions (homogeneous catalysis) 214 10.1.1 The Michaelis-Menten mechanism 215 10.1.2 Inhibition of enzymes: 217 10.2 Kinetics of heterogeneous reactions (surface reactions) 218 10.2.1 Reaction steps in heterogeneous catalysis 218 10.2.2 Physisorption and chemisorption 218 10.2.3 The Langmuir adsorption isotherm 219 10.2.4 Surface Diffusion 222 10.2.5 Types of heterogeneous reactions 223 11 Reactions in solution 227 11.1 Qualitative model of liquid phase reactions 227 11.2 Diffusion-controlled reactions 230 11.2.1 Experimental observations 230 11.2.2 Derivation of 230 11.3 Activation controlled reactions 234 11.4 Electron transfer reactions (Marcus theory) 235 11.5 Reactions of ions in solutions 238 11.5.1 Effect of the ionic strength of the solution 238 11.5.2 Kinetic salt effect 238 11.6 References 240
vii 12 Photochemical reactions 241 12.1 Basic radiative processes in a two-level system; Einstein coefficients 241 12.2 Fluorescence quenching (Stern-Volmer equation) 242 12.3 The radiative lifetime 0 and the fluorescence quantum yield Φ 243 12.4 Radiationless processes in photoexcited molecules 244 12.4.1 The Born-Oppenheimer approximation and its breakdown 244 12.4.2 Avoided crossings of two potential curves of a diatomic molecule 248 12.4.3 Quantum mechanical treatment of a coupled 2×2 system 250 12.4.4 Radiationless processes in polyatomic molecules: Conical intersections 252 13 Atmospheric chemistry* 256 14 Combustion chemistry* 257 15 Astrochemistry* 258 16 Energy transfer processes* 259 17 Reaction dynamics* 260 18 Electrochemical kinetics* 261 A Useful physicochemical constants 262 B The Marquardt-Levenberg non-linear least-squares fitting algorithm 263 C Solution of inhomogeneous differential equations 267 C.1 General method 267 C.2 Application to two consecutive first-order reactions 268 C.3 Application to parallel and consecutive first-order reactions 270 D Matrix methods 273 D.1 Definition 273 D.2 Special matrices and matrix operations 274 D.3 Determinants 277 D.4 Coordinate transformations 278 D.5 Systems of linear equations 280 D.6 Eigenvalue equations 282
Page 1 and 2: Physical Chemistry 3: — Chemical
Page 3 and 4: iii 2.7 Temperature dependence of r
Page 5: v 7.1.2 Formal kinetic model 149 7.
Page 9 and 10: ix Preface This scriptum contains l
Page 11 and 12: xi Disclaimer Use of this text is e
Page 13 and 14: xiii I Figure 2: Organisational mat
Page 15 and 16: xv I Figure 6: Recommended textbook
Page 17 and 18: 1.2 Time scales for chemical reacti
Page 19 and 20: 1.2 Time scales for chemical reacti
Page 21 and 22: 1.3 Historical events 6 I Empirical
Page 23 and 24: 1.4 References 8 2. Formal kinetics
Page 25 and 26: 2.1 Definitions and conventions 10
Page 31 and 32: 2.2 Kinetics of irreversible first-
Page 33 and 34: 2.2 Kinetics of irreversible first-
Page 35 and 36: 2.3 Kinetics of reversible first-or
Page 37 and 38: 2.3 Kinetics of reversible first-or
Page 39 and 40: 2.4 Kinetics of second-order reacti
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Page 51 and 52: 2.7 Temperature dependence of rate
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3.1 Determination of the order of a
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3.2 Application of the steady-state
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3.2 Application of the steady-state
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3.4 Generalized first-order kinetic
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3.5 Numerical integration 58 I Surv
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3.5 Numerical integration 60 2 ord
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3.5 Numerical integration 62 3.5.5
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3.5 Numerical integration 64 , Func
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3.6 Oscillating reactions* 66 3.6 O
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3.6 Oscillating reactions* 68 • B
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3.6 Oscillating reactions* 70 (5) S
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3.6 Oscillating reactions* 72 I Fig
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3.6 Oscillating reactions* 74 [X]
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3.7 References 76 4. Experimental m
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4.3 The discharge flow (DF) techniq
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4.3 The discharge flow (DF) techniq
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4.4 Flash photolysis (FP) 82 4.4 Fl
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4.4 Flash photolysis (FP) 84 I Figu
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4.6 Stopped flow studies 86 4.6 Sto
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4.8 Relaxation methods 88 4.8 Relax
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4.9 Femtosecond spectroscopy 90 I F
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4.9 Femtosecond spectroscopy 92 I F
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4.10 References 94 5. Collision the
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5.1 Hardspherecollisiontheory 96
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5.1 Hardspherecollisiontheory 98 I
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5.1 Hard sphere collision theory 10
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5.2 Kinetic gas theory 102 I The 1D
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5.2 Kinetic gas theory 104 I Figure
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5.2 Kinetic gas theory 106 5.2.2 Th
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5.2 Kinetic gas theory 108 • Resu
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5.3 Transport processes in gases 11
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5.4 Advanced collision theory 116 W
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5.4 Advanced collision theory 118 I
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5.4 Advanced collision theory 120 5
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5.4 Advanced collision theory 126 a
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5.4 Advanced collision theory 130 (
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5.4 Advanced collision theory 136
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5.4 Advanced collision theory 138 6
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6.2 Polyatomic molecules 140 I Figu
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6.2 Polyatomic molecules 142 I Mode
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6.3 Trajectory Calculations 144 •
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6.3 Trajectory Calculations 146 7.
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7.1 Foundations of transition state
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7.2 Applications of transition stat
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7.3 Thermodynamic interpretation of
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7.4 Transition state spectroscopy 1
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8.1 Experimental observations 176 (
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8.2 Lindemann mechanism 178 8.2 Lin
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8.2 Lindemann mechanism 180 I Half-
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8.3 Generalized Lindemann-Hinshelwo
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8.4 The specific unimolecular react
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8.5 Collisional energy transfer* 20
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8.6 Recombination reactions 202 8.7
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9.1 Chain reactions and chain explo
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9.1 Chain reactions and chain explo
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9.2 Heat explosions 208 • positiv
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9.2 Heat explosions 210 (3) We can
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9.2 Heat explosions 212 9.2.3 Explo
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9.2 Heat explosions 214 10. Catalys
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10.1 Kinetics of enzyme catalyzed r
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10.2 Kinetics of heterogeneous reac
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11.1 Qualitative model of liquid ph
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11.2 Diffusion-controlled reactions
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11.2 Diffusion-controlled reactions
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11.3 Activation controlled reaction
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11.4 Electron transfer reactions (M
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11.5 Reactions of ions in solutions
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11.5 Reactions of ions in solutions
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12.2 Fluorescence quenching (Stern-
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12.4 Radiationless processes in pho
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14 Combustion chemistry* 258 15. As
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16 Energy transfer processes* 260 1
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Appendix B 262 Appendix A: Useful p
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Appendix B 264 The Marquardt-Levenb
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Appendix C 266 • Convolution of t
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Appendix C 268 C.2 Application to t
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Appendix C 270 C.3 Application to p
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Appendix D 272 Final solutions for
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Appendix D 274 D.2 Special matrices
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Appendix D 276 I Multiplication by
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Appendix D 278 D.4 Coordinate trans
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Appendix D 280 D.5 Systems of linea
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Appendix D 282 D.6 Eigenvalue equat
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Appendix E 284 Secular equation: de
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Appendix E 286 Appendix E: Laplace
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Appendix F 288 Appendix F: The Gamm
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Appendix G 290 Appendix G: Ergebnis
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Appendix G 292 I Anschauliche Bedeu
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Appendix G 294 Ergebnis: = 1 X
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Appendix G 296 (2) Grenzfall für
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Appendix G 298 G.4 Mikrokanonische
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Appendix G 300 G.5 Statistische Int
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Appendix G 302 y = (G.7
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Appendix G 304 G.8 Zustandssumme f
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Appendix G 306 G.9 Zustandssumme f
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Physical Chemistry 3: — Chemical Kinetics — - Christian-Albrechts ...

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