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

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4.9 Femtosecond spectroscopy 93 4.10 References Busch 1999 K. W. Busch, M. A. Busch, Cavity-Ringdown Spectroscopy, ACSSymposium Series, Vol 720, American <strong>Chemical</strong> Society, Washington, 1999. Brown 2000 S.S.Brown,A.R.Ravishankara,H.Stark,J.Phys.Chem.A104, 7044 (2000). Friebolin 1999 H.Friebolin, Ein- und zweidimensionale NMR-Spektroskopie, Wiley- VCH, Weinheim, 1999. Guo 2003 Y. Guo, M. Fikri, G. Friedrichs, F. Temps, An Extended Simultaneous <strong>Kinetics</strong> and Ringdown Model: Determination of the Rate Constant for the Reaction SiH 2 +O 2 .Phys.Chem.Chem.Phys.5, 4622 (2003). OKeefe 1988 A.O’Keefe,D.A.G.Deacon,Rev.Sci.Instrum.59, 2544 (1988).
4.10 References 94 5. Collision theory So far, we have considered more or less complex chemical reactions following more or less complicated rate laws, but we have only considered the rate coefficients appearing in the rate laws as empirical quantities, which had to be determined experimentally. We shall now ask the question, whether we can rationalize and predict those rate coefficients using theoretical models. Towards these ends, we have to look at the reactions at a microscopic, molecular level. In particular, we have to • consider the relation between the microscopic (individual molecule) properties and the macroscopic (thermally averaged) rate quantities (rate constants, product branching ratios) • develop models for the microscopic (molecular level) progress of individual elementary reactions, including the different molecular degrees of freedom (quantum states). • develop sufficiently simplified models averaging over the molecular degrees of freedom which still allow us to make practically useful, relevant, and sufficiently accurate predictions. We shall do so in the next four chapters. I Collision theory: To begin with, this chapter considers bimolecular reactions in the gas phase. These obviously require a collision between two molecules as condition for a reaction to take place. • We start with the hard sphere collision model of structureless particles as the simplest model for bimolecular reactions. Although this model has two major flaws, it leads to the right result because of a compensation of errors. • We then consider results of kinetic gas theory, which allow us to properly take into account the molecular speed distributions. • We apply the hard sphere collision model to understand transport processes in the gas phase (diffusion, heat conductivity, viscosity). • We then proceed with a correct derivation of advanced collision theory models starting from differential cross sections (which can be measured in crossed molecular beam experiments). Advanced collision theory is the method of choice for fast gas phase reactions which can be studied in detail by molecular beam experiments and handled by quantum theory.
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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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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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