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

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x or QtiPlot) may be needed for data evaluation and presentation. 9 As practically all original scientific literature is published in English (British and American; in fact many chemists at some time in their professional lifes have to master the subtle differences between both), this scriptum is written in English to introduce students to the predominating language of science at an early stage. Students should also note that the working language of some of the research groups (including that of the author) in the <strong>Chemistry</strong> Department at CAU is English. Finally, I would like to encourage all students to ask questions when they appear, whether during the lecture or in the exercise classes! Kiel, June 22, 2013, F. Temps 9 Excel also allows you to plot simple functions and data, but is not sufficient for serious scientific applications.
xi Disclaimer Use of this text is entirely at the reader’s risk. Some sections are incomplete, some equations still have to be checked, some figures need to be redrawn, references are still missing, etc. No warranties in any form whatever are given by the author.
Page 1 and 2: Physical Chemistry 3: — Chemical
Page 3 and 4: iii 2.7 Temperature dependence of r
Page 5 and 6: v 7.1.2 Formal kinetic model 149 7.
Page 7 and 8: vii 12 Photochemical reactions 241
Page 9: ix Preface This scriptum contains l
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
Page 41 and 42: 2.4 Kinetics of second-order reacti
Page 43 and 44: 2.5 Kinetics of third-order reactio
Page 45 and 46: 2.6 Kinetics of simple composite re
Page 51 and 52: 2.7 Temperature dependence of rate
Page 57 and 58: 3.1 Determination of the order of a
Page 59 and 60: 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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