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

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5.4 Advanced collision theory 133 I Table 5.3: Types of long-range intermolecular interactions. system () charge-charge (Coulomb) () = 1 2 2 4 0 charge-dipole ( ) = −→ · −→ = − cos 4 0 2 dipole-dipole ( 1 2 )= charge-quadrupole Θ ∝ −3 dipole-quadrupole Θ ∝ −4 charge-induced dipole ∝ −4 quadrupole-quadrupole ΘΘ ∝ −5 induced dipole-induced dipole ∝ −6 μ 1 · μ 2 − 3(μ 1 · r)(μ 2 · r) 2 4 0 3 I Table 5.4: Long-range intermolecular interactions ( =15 D, =3Å 3 , =1, =0;energies in kJ mol; forcomparison: =25kJ mol @ =298K). ³ ´ ³ ´ system =5Å =10Å ion-ion 278 139 ion-dipole 17.4 4.35 ion-induced dipole 3.34 0.21 dipole-dipole 2.17 0.27 b) Lennard-Jones (6-12) potential for nonpolar molecules A realistic intermolecular potential for non-polar molecules is the Lennard-Jones (6-12) potential ∙ ³LJ ´12 ³ LJ ´6¸ LJ () =4 LJ − (5.198) LJ is usually given in reduced form in units of K as ∗ LJ = LJ (5.199)
5.4 Advanced collision theory 134 I Figure 5.25: Schematic plot of the Lennard-Jones potential. I Estimation of LJ parameters: Values for LJ and LJ are typically derived from transport properties (e.g., viscosity), thermodynamic data (vdW parameters), or <strong>—</strong> if there is no better way <strong>—</strong> from empirical correlations (see, e.g., Svehla1963) with critical data, boiling temperatures, . . . I Table 5.5: Lennard-Jones for some gases (Mourits1977). LJ (pm) ( LJ ) (K) LJ (pm) ( LJ ) (K) He 2560 102 N 2 3738 820 Ne 2822 320 O 2 3480 1026 Ar 3465 1135 CH 4 3790 1421 Kr 3662 1780 CF 4 4486 1673 Xe 4050 2302 CCl 4 5611 4155 H 2 2930 370 CO 2 3943 2009 SF 6 5199 2120
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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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Page 109 and 110: 4.10 References 94 5. Collision the
Page 111 and 112: 5.1 Hardspherecollisiontheory 96
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Page 115 and 116: 5.1 Hard sphere collision theory 10
Page 117 and 118: 5.2 Kinetic gas theory 102 I The 1D
Page 119 and 120: 5.2 Kinetic gas theory 104 I Figure
Page 121 and 122: 5.2 Kinetic gas theory 106 5.2.2 Th
Page 123 and 124: 5.2 Kinetic gas theory 108 • Resu
Page 125 and 126: 5.3 Transport processes in gases 11
Page 131 and 132: 5.4 Advanced collision theory 116 W
Page 133 and 134: 5.4 Advanced collision theory 118 I
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Page 163 and 164: 7.1 Foundations of transition state
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Page 193 and 194: 8.2 Lindemann mechanism 178 8.2 Lin
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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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