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

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2.7 Temperature dependence of rate coefficients 35
2.7.1 Arrhenius equation 35
2.7.2 Deviations from Arrhenius behavior 37
2.7.3 Examples for non-Arrhenius behavior 38
2.8 References 40
3 Kinetics of complex reaction systems 41
3.1 Determination of the order of a reaction 41
3.2 Application of the steady-state assumption 43
3.2.1 The reaction H 2 + Br 2 → 2 HBr 43
3.2.2 Further examples 45
3.3 Microscopic reversibility and detailed balancing 47
3.4 Generalized first-order kinetics* 48
3.4.1 Matrix method* 48
3.4.2 Laplace transforms* 53
3.5 Numerical integration 57
3.5.1 Taylor series expansions 58
3.5.2 Euler method 58
3.5.3 Runge-Kutta methods 59
3.5.4 Implicit methods (Gear): 61
3.5.5 Extrapolation methods (Bulirsch-Stoer) 62
3.5.6 Example: Consecutive first-order reactions 62
3.6 Oscillating reactions* 66
3.6.1 Autocatalysis 66
3.6.2 Chemical oscillations 67
3.7 References 75
4 Experimental methods 76
4.1 End product analysis 76
4.2 Modulation techniques 77
4.3 The discharge flow (DF) technique 78
4.4 Flash photolysis (FP) 82
4.5 Shock tube studies of high temperature kinetics 85
4.6 Stopped flow studies 86