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

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10.2 <strong>Kinetics</strong> of heterogeneous reactions (surface reactions) 223 10.2.5 Types of heterogeneous reactions a) Dissociative Adsorption I Scheme: A 2 () + − | S − | S − 2 À −2 − A | S − A | S − (10.55) I Adsorption isotherm: • Adsorption rate: • Desorption rate: y with Θ = 2 2 (1 − Θ) 2 (10.56) −2 Θ 2 (10.57) ( 2 × ) 12 1+( 2 × ) 12 (10.58) = 2 −2 (10.59) I Figure 10.6: Potential energy curves for dissociative adsorption.
10.2 <strong>Kinetics</strong> of heterogeneous reactions (surface reactions) 224 b) Surface catalyzed unimolecular dissociation I Scheme: A() + − | S − 3 À −3 − A | S − 4 → Products (10.60) I Example: Decomposition of PH 3 on a W metal surface. I Decomposition rate and two limiting cases: [P] = 4 Θ = 4 × A 1+ A (10.61) (1) A ¿ 1: The reaction becomes first-order in A . [P] = 4 A (10.62) (2) A À 1: The reaction becomes zeroth order, i.e., independent of A ! [P] = 4 (10.63) c) Bimolecular reactions I Scheme: A() + − | S − À − − A | S − (10.64) − A | S − + − B() + B − | S − 5 → | S − − À − A − B − B | S − (10.65) | S − S − 6 → Products (10.66) I Reaction rate: Assuming that A and B compete for the same active sites, we have (1 − Θ − Θ )= − Θ (10.67) y [P] (1 − Θ − Θ )= − Θ (10.68) = 5 Θ Θ = 5 (1 + + ) 2 (10.69)
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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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Page 229 and 230: 9.2 Heat explosions 214 10. Catalys
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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
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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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