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

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10.1 Kinetics of enzyme catalyzed reactions (homogeneous catalysis) 217 I Figure 10.2: Lineweaver-Burk plot. 10.1.2 Inhibition of enzymes: Extended reaction mechanism: E+S 1 À ES (10.29) −1 ES 2 → E+P (10.30) E+I 3 À EI (10.31) −3 The EI complex is catalytically inactive, since I blockstheactivesiteofE. Inhibition constant: = [EI] [E] [I] = 3 −3 (10.32) I Reaction rate (Fig. 10.2): y [ES] = ≈ 0 (10.33) 1 = 1 +(1+ [I]) × 1 (10.34) 2 [E] 0 2 [E] 0 [S] 0 y The slope of the plot of −1 vs. [S] −1 0 goes up (see Fig. 10.2). Exercise 10.1: Derive Eq. 10.34 with a reasonable assumption for the concentrations of I. ¤
10.2 Kinetics of heterogeneous reactions (surface reactions) 218 10.2 Kinetics of heterogeneous reactions (surface reactions) I Examples for heterogeneous reactions (gas-solid interface): Many reactions, which are very slow in the gas phase, take place as heterogeneous reactions in the presence of a heterogeneous catalyst: • catalytic hydrogenation • NH 3 synthesis (Haber-Bosch) • catalytic exhaust gas treatment (internal combustion engines) • catalytic DeNO processes • CO oxidation • oxidative coupling reactions of CH 4 (oxide catalysts) • atmospheric reactions (at gas-solid and gas-liquid interface) 10.2.1 Reaction steps in heterogeneous catalysis Heterogeneous reactions take place via a series of steps: • Diffusion in gas (or liquid) phase to catalyst surface. • Adsorption: — “physical” adsorption (“physisorption”), — “chemical” adsorption (“chemisorption”). • Diffusiononthesurface. • Chemical reaction on the surface. • Desorption. • Diffusion away from surface. 10.2.2 Physisorption and chemisorption We distinguish between “physical” adsorption (“physisorption”) and “chemical” adsorption (“chemisorption”) on a surface based upon the adsorption energies (surface binding energies). ⇒ Fig. 10.3. • Physisorption: — van-der-Waals type interaction, — typical bond energy: ∆ ≤−40 kJ mol −1 ,
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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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Page 277 and 278: Appendix B 262 Appendix A: Useful p
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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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