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

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6.3 Trajectory Calculations 145 I Figure 6.8: The reaction H + Cl 2 isareactionwithanearlyTS.Thereactionisknown to yield HCl with an inverted vibrational state distribution (⇒ HCl-Laser). I Figure 6.9: Bimolecular reaction with a late TS.
6.3 Trajectory Calculations 146 7. Transition state theory 7.1 Foundations of transition state theory The concept of transition state theory (TST) or activated complex theory (ACT) goes back to H. Eyring and M. Polanyi (1935). TST is a statistical theory; it does not give information on the exact dynamics of a reaction. It does, however, give (statistical) information on product state distributions. There are two forms of TST: • Macrocanonical TST ⇒ ( ) for a macrocanonical ensemble of molecules with aconstant (an ensemble of molecules with energy states populated according to the Boltzmann distribution - each state being equally likely.) • Microcanonical TST (TST) ⇒ () for a microcanonical ensemble of molecules with specific energy. We will consider only the first version. The detailed application of TST also depends on whether or not the reaction has a distinctive potential energy barrier (⇒ conventional TST or variational TST). I Figure 7.1: Transition State Theory (TST): Fundamental equations and applications.
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Physical Chemistry 3: — Chemical
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iii 2.7 Temperature dependence of r
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v 7.1.2 Formal kinetic model 149 7.
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vii 12 Photochemical reactions 241
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ix Preface This scriptum contains l
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xi Disclaimer Use of this text is e
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xiii I Figure 2: Organisational mat
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xv I Figure 6: Recommended textbook
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1.2 Time scales for chemical reacti
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1.2 Time scales for chemical reacti
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1.3 Historical events 6 I Empirical
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1.4 References 8 2. Formal kinetics
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2.1 Definitions and conventions 10
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2.2 Kinetics of irreversible first-
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2.2 Kinetics of irreversible first-
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2.3 Kinetics of reversible first-or
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2.3 Kinetics of reversible first-or
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2.4 Kinetics of second-order reacti
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2.4 Kinetics of second-order reacti
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2.5 Kinetics of third-order reactio
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2.6 Kinetics of simple composite re
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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
Page 109 and 110: 4.10 References 94 5. Collision the
Page 111 and 112: 5.1 Hardspherecollisiontheory 96
Page 113 and 114: 5.1 Hardspherecollisiontheory 98 I
Page 115 and 116: 5.1 Hard sphere collision theory 10
Page 117 and 118: 5.2 Kinetic gas theory 102 I The 1D
Page 119 and 120: 5.2 Kinetic gas theory 104 I Figure
Page 121 and 122: 5.2 Kinetic gas theory 106 5.2.2 Th
Page 123 and 124: 5.2 Kinetic gas theory 108 • Resu
Page 125 and 126: 5.3 Transport processes in gases 11
Page 131 and 132: 5.4 Advanced collision theory 116 W
Page 133 and 134: 5.4 Advanced collision theory 118 I
Page 135 and 136: 5.4 Advanced collision theory 120 5
Page 141 and 142: 5.4 Advanced collision theory 126 a
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Page 155 and 156: 6.2 Polyatomic molecules 140 I Figu
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Page 163 and 164: 7.1 Foundations of transition state
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Page 191 and 192: 8.1 Experimental observations 176 (
Page 193 and 194: 8.2 Lindemann mechanism 178 8.2 Lin
Page 195 and 196: 8.2 Lindemann mechanism 180 I Half-
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8.4 The specific unimolecular react
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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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