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

More documents

Recommendations

Info

5.1 Hardspherecollisiontheory 99 Rule-of-thumb: Time between collisions: =03mbary =03mm (5.43) =1000mbar (5.44) 1 1 = 2 × (5.45) =15 × 10 −10 s (5.46) ≈ 01ns (5.47) ¤ 5.1.2 Allowance for a threshold energy for reaction I The threshold energy E 0 : The majority of reactions exhibit a threshold energy, below which the reaction does not occur (quantum mechanical tunneling is excluded here). The molecules must have a minimum energy min to overcome this reaction threshold energy 0 . For our structureless spherical molecules, we consider only translational energy : 36 0 : no reaction (5.48) 0 : reaction (5.49) I Boltzmann distribution: Fraction of molecules with translational energy 0 : µ ( 0 ) =exp − µ 0 =exp − 0 (5.50) I Resulting rate constant: or µ 12 max = 2 8 × × − 0 (5.51) µ 12 max = 2 8 × × − 0 (5.52) I Arrhenius activation energy: Applying the definition of the apparent (Arrhenius) activation energy ,wefind that = 2 ln = 0 + 1 (5.53) 2 As we see, is not constant but (slightly) -dependent: The slope of a plot of ln max vs. −1 increases as →∞(or −1 → 0). The Arrhenius preexponential factor would not be constant as well, it is also slightly -dependent. 36 We use and 0 to indicate the energies in molecular units, and and 0 for the respective values in molar units.
5.1 Hard sphere collision theory 100 5.1.3 Allowance for steric hindrance I The sterical factor p: In addition, even if 0 , not every collision will lead to a reaction, because real molecules are not structureless: A reaction requires a specific orientation of the molecules. This is taken into account by introducing a steric factor : µ 12 max = × 2 8 × × − 0 (5.54)
Page 1 and 2:
Physical Chemistry 3: — Chemical
Page 3 and 4:
iii 2.7 Temperature dependence of r
Page 5 and 6:
v 7.1.2 Formal kinetic model 149 7.
Page 7 and 8:
vii 12 Photochemical reactions 241
Page 9 and 10:
ix Preface This scriptum contains l
Page 11 and 12:
xi Disclaimer Use of this text is e
Page 13 and 14:
xiii I Figure 2: Organisational mat
Page 15 and 16:
xv I Figure 6: Recommended textbook
Page 17 and 18:
1.2 Time scales for chemical reacti
Page 19 and 20:
1.2 Time scales for chemical reacti
Page 21 and 22:
1.3 Historical events 6 I Empirical
Page 23 and 24:
1.4 References 8 2. Formal kinetics
Page 25 and 26:
2.1 Definitions and conventions 10
Page 27 and 28:
Page 29 and 30:
Page 31 and 32:
2.2 Kinetics of irreversible first-
Page 33 and 34:
2.2 Kinetics of irreversible first-
Page 35 and 36:
2.3 Kinetics of reversible first-or
Page 37 and 38:
2.3 Kinetics of reversible first-or
Page 39 and 40:
2.4 Kinetics of second-order reacti
Page 41 and 42:
2.4 Kinetics of second-order reacti
Page 43 and 44:
2.5 Kinetics of third-order reactio
Page 45 and 46:
2.6 Kinetics of simple composite re
Page 47 and 48:
Page 49 and 50:
Page 51 and 52:
2.7 Temperature dependence of rate
Page 53 and 54:
Page 55 and 56:
Page 57 and 58:
3.1 Determination of the order of a
Page 59 and 60:
3.2 Application of the steady-state
Page 61 and 62:
3.2 Application of the steady-state
Page 63 and 64: 3.4 Generalized first-order kinetic
Page 73 and 74: 3.5 Numerical integration 58 I Surv
Page 75 and 76: 3.5 Numerical integration 60 2 ord
Page 77 and 78: 3.5 Numerical integration 62 3.5.5
Page 79 and 80: 3.5 Numerical integration 64 , Func
Page 81 and 82: 3.6 Oscillating reactions* 66 3.6 O
Page 83 and 84: 3.6 Oscillating reactions* 68 • B
Page 85 and 86: 3.6 Oscillating reactions* 70 (5) S
Page 87 and 88: 3.6 Oscillating reactions* 72 I Fig
Page 89 and 90: 3.6 Oscillating reactions* 74 [X]
Page 91 and 92: 3.7 References 76 4. Experimental m
Page 93 and 94: 4.3 The discharge flow (DF) techniq
Page 95 and 96: 4.3 The discharge flow (DF) techniq
Page 97 and 98: 4.4 Flash photolysis (FP) 82 4.4 Fl
Page 99 and 100: 4.4 Flash photolysis (FP) 84 I Figu
Page 101 and 102: 4.6 Stopped flow studies 86 4.6 Sto
Page 103 and 104: 4.8 Relaxation methods 88 4.8 Relax
Page 105 and 106: 4.9 Femtosecond spectroscopy 90 I F
Page 107 and 108: 4.9 Femtosecond spectroscopy 92 I F
Page 109 and 110: 4.10 References 94 5. Collision the
Page 111 and 112: 5.1 Hardspherecollisiontheory 96
Page 113: 5.1 Hardspherecollisiontheory 98 I
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
Page 135 and 136: 5.4 Advanced collision theory 120 5
Page 141 and 142: 5.4 Advanced collision theory 126 a
Page 145 and 146: 5.4 Advanced collision theory 130 (
Page 151 and 152: 5.4 Advanced collision theory 136
Page 153 and 154: 5.4 Advanced collision theory 138 6
Page 155 and 156: 6.2 Polyatomic molecules 140 I Figu
Page 157 and 158: 6.2 Polyatomic molecules 142 I Mode
Page 159 and 160: 6.3 Trajectory Calculations 144 •
Page 161 and 162: 6.3 Trajectory Calculations 146 7.
Page 163 and 164: 7.1 Foundations of transition state
Page 165 and 166:
7.1 Foundations of transition state
Page 167 and 168:
7.1 Foundations of transition state
Page 169 and 170:
7.2 Applications of transition stat
Page 171 and 172:
Page 173 and 174:
Page 175 and 176:
7.3 Thermodynamic interpretation of
Page 177 and 178:
Page 179 and 180:
Page 181 and 182:
Page 183 and 184:
Page 185 and 186:
7.4 Transition state spectroscopy 1
Page 187 and 188:
Page 189 and 190:
Page 191 and 192:
8.1 Experimental observations 176 (
Page 193 and 194:
8.2 Lindemann mechanism 178 8.2 Lin
Page 195 and 196:
8.2 Lindemann mechanism 180 I Half-
Page 197 and 198:
8.3 Generalized Lindemann-Hinshelwo
Page 199 and 200:
Page 201 and 202:
Page 203 and 204:
Page 205 and 206:
Page 207 and 208:
8.4 The specific unimolecular react
Page 209 and 210:
Page 211 and 212:
Page 213 and 214:
Page 215 and 216:
8.5 Collisional energy transfer* 20
Page 217 and 218:
8.6 Recombination reactions 202 8.7
Page 219 and 220:
9.1 Chain reactions and chain explo
Page 221 and 222:
9.1 Chain reactions and chain explo
Page 223 and 224:
9.2 Heat explosions 208 • positiv
Page 225 and 226:
9.2 Heat explosions 210 (3) We can
Page 227 and 228:
9.2 Heat explosions 212 9.2.3 Explo
Page 229 and 230:
9.2 Heat explosions 214 10. Catalys
Page 231 and 232:
10.1 Kinetics of enzyme catalyzed r
Page 233 and 234:
10.2 Kinetics of heterogeneous reac
Page 235 and 236:
Page 237 and 238:
Page 239 and 240:
Page 241 and 242:
Page 243 and 244:
11.1 Qualitative model of liquid ph
Page 245 and 246:
11.2 Diffusion-controlled reactions
Page 247 and 248:
11.2 Diffusion-controlled reactions
Page 249 and 250:
11.3 Activation controlled reaction
Page 251 and 252:
11.4 Electron transfer reactions (M
Page 253 and 254:
11.5 Reactions of ions in solutions
Page 255 and 256:
11.5 Reactions of ions in solutions
Page 257 and 258:
12.2 Fluorescence quenching (Stern-
Page 259 and 260:
12.4 Radiationless processes in pho
Page 261 and 262:
Page 263 and 264:
Page 265 and 266:
Page 267 and 268:
Page 269 and 270:
Page 271 and 272:
Page 273 and 274:
14 Combustion chemistry* 258 15. As
Page 275 and 276:
16 Energy transfer processes* 260 1
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
Page 291 and 292:
Appendix D 276 I Multiplication by
Page 293 and 294:
Appendix D 278 D.4 Coordinate trans
Page 295 and 296:
Appendix D 280 D.5 Systems of linea
Page 297 and 298:
Appendix D 282 D.6 Eigenvalue equat
Page 299 and 300:
Appendix E 284 Secular equation: de
Page 301 and 302:
Appendix E 286 Appendix E: Laplace
Page 303 and 304:
Appendix F 288 Appendix F: The Gamm
Page 305 and 306:
Appendix G 290 Appendix G: Ergebnis
Page 307 and 308:
Appendix G 292 I Anschauliche Bedeu
Page 309 and 310:
Appendix G 294 Ergebnis: = 1 X
Page 311 and 312:
Appendix G 296 (2) Grenzfall für
Page 313 and 314:
Appendix G 298 G.4 Mikrokanonische
Page 315 and 316:
Appendix G 300 G.5 Statistische Int
Page 317 and 318:
Appendix G 302 y = (G.7
Page 319 and 320:
Appendix G 304 G.8 Zustandssumme f
Page 321 and 322:
Appendix G 306 G.9 Zustandssumme f
show all

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

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?