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

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11.1 Qualitative model of liquid phase reactions 229 I Two limiting cases: (1) Diffusion control: À − y = (11.7) This case is observed when =0and the diffusion coefficient is small. We shall find below that =4 (11.8) (2) Reaction (or activation) control: ¿ − y = − = {} (11.9) In this case, the reaction is said to be activation controlled because usually it has a sizable . can be described by TST: = ∆+ −∆+ (11.10)
11.2 Diffusion-controlled reactions 230 11.2 Diffusion-controlled reactions 11.2.1 Experimental observations The transition to diffusion control can be observed in the gas phase by studying the kinetics in highly compressed gases (up to =1000bar) or, even better, in supercritical media. At ≈ 1000 bar, the gas density reaches the density of the liquid phase. I Smoluchowsky-Kramers limit: At high densities, the rate constant becomes ∝ ∝ 1 (11.11) I Figure 11.2: Diffusion control of a unimolecular reaction: At very high pressures, the fragments recombine before they become separated by diffusion y the reaction becomes diffusion controlled. 11.2.2 Derivation of k In order to derive a theoretical expression for , we consider the distribution of the molecules around a molecule inthecenterofasphereasshowninFig.11.3.
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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
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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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Page 229 and 230: 9.2 Heat explosions 214 10. Catalys
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Page 273 and 274: 14 Combustion chemistry* 258 15. As
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Page 277 and 278: Appendix B 262 Appendix A: Useful p
Page 279 and 280: Appendix B 264 The Marquardt-Levenb
Page 281 and 282: Appendix C 266 • Convolution of t
Page 283 and 284: Appendix C 268 C.2 Application to t
Page 285 and 286: Appendix C 270 C.3 Application to p
Page 287 and 288: Appendix D 272 Final solutions for
Page 289 and 290: Appendix D 274 D.2 Special matrices
Page 291 and 292: Appendix D 276 I Multiplication by
Page 293 and 294: 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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