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

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11.4 Electron transfer reactions (Marcus theory) 237 I Conclusion: Equation 11.55 predicts the ET rate constant to increase with increasing exoergicity (−∆ ª ) of the reaction. However, once −∆ ª , the rate constant is predicted to decrease again (see Figs. 11.6D and 11.7). The prediction of this unexpected inverted Marcus regime before any experimental data were available is the hallmark of Marcus theory. I Figure 11.6: I Figure 11.7:
11.5 Reactions of ions in solutions 238 11.5 Reactions of ions in solutions Reactions of ionic species in liquids are one exception to the rule that reactions in the liquid phase usually have similar rates as in the gas phase (the other exception being electron transfer reactions). The reason is that the charged species are very sensitive to their environment, in particular solvation. Changes of the charge distribution are accompanied by correspondingly large solvation shell rearrangements. 11.5.1 Effect of the ionic strength of the solution The main effect arises from the stabilization of shielding every ion in solution by the oppositely charged ”ionic atmosphere” or “ion cloud” (⇒ Debye-Hückel theory, Appendix ??). I Equilibrium constant for hAB ‡ i : ‡ = ‡ = ‡ £ ‡ ¤ [][] (11.56) I Activity coefficient from Debye-Hückel theory: log = − 2 12 (11.57) with (for water at =298K, according to Debye-Hückel theory) =0509 l 12 mol −12 (11.58) I Ionic strength: = 1 X 2 (11.59) 2 11.5.2 Kinetic salt effect I TST rate constant: [ ] = £ ‡ ‡¤ = ‡ ‡ [][] (11.60) ‡ Defining 0 as the rate constant for the ideal solution, where all =1, this becomes = 0 ‡ (11.61)
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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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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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8.3 Generalized Lindemann-Hinshelwo
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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
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Page 299 and 300: Appendix E 284 Secular equation: de
Page 301 and 302: 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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