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

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3.6 Oscillating reactions* 73 I Figure 3.9: Key steps of the Belousov-Zhabotinsky reaction. d) The Oregonator 33 TheOregonatormodelcanbeusedtodescribetheBelousov-Zhabotinsky reaction. I Schematic model and kinetic equations: A+Y 1 → X+R (1) X+Y 2 → 2R (2) A+X 3 → 2X+2Z (3) (3.210) B+Z 5 → 1 2 Y (5) 2X → 4 A +R (4) with A=BrO − 3 B=CH 2 (COOH) 2 + BrCH(COOH) 2 R=HOBr X=HBrO 2 Y=Br − Z=Ce 4+ . Using dimensionless time ( = 5 [B] ), we obtain 33 The name ‘Oregonator’ stems from the workplace of its inventor Noyes (University of Oregon).
3.6 Oscillating reactions* 74 [X] [Y] [Z] = 1 [A] [Y] − 2 [X] [Y] + 3 [A] [X] − 2 4 [X 2 ] 5 [B] − 1 [A] [Y] − 2 [X] [Y] + 1 = 2 5 [B] [Z] 5 [B] = 2 3 [A] [X] − 5 [B] [Z] 5 [B] (3.211) (3.212) (3.213) I Figure 3.10: Numerical integration of the Oregonator model (rate constants in lmol −1 s −1 : 1 =0005, 2 =10, 3 =10, 4 =10, 5 = 0004; initial concentrations in mol l −1 : [A] = 001, [B] = 10, [X] 0 =00, [Y] 0 =00, [Z] 0 =000025.)
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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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Page 63 and 64: 3.4 Generalized first-order kinetic
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Page 81 and 82: 3.6 Oscillating reactions* 66 3.6 O
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Page 91 and 92: 3.7 References 76 4. Experimental m
Page 93 and 94: 4.3 The discharge flow (DF) techniq
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Page 97 and 98: 4.4 Flash photolysis (FP) 82 4.4 Fl
Page 99 and 100: 4.4 Flash photolysis (FP) 84 I Figu
Page 101 and 102: 4.6 Stopped flow studies 86 4.6 Sto
Page 103 and 104: 4.8 Relaxation methods 88 4.8 Relax
Page 105 and 106: 4.9 Femtosecond spectroscopy 90 I F
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Page 109 and 110: 4.10 References 94 5. Collision the
Page 111 and 112: 5.1 Hardspherecollisiontheory 96
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Page 115 and 116: 5.1 Hard sphere collision theory 10
Page 117 and 118: 5.2 Kinetic gas theory 102 I The 1D
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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
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Page 131 and 132: 5.4 Advanced collision theory 116 W
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5.4 Advanced collision theory 124 I
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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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