Page 12 - Introduction to chemical reaction engineering and kinetics

xii Contents

3.2 Experimental Measurements: General Considerations 4 5
3.3 Experimental Methods to Follow the Extent of Reaction 46
3.3.1 Ex-situ and In-situ Measurement Techniques 46
3.3.2 Chemical Methods 46
3.3.3 Physical Methods 47
3.3.4 Other Measured Quantities 48
3.4 Experimental Strategies for Determining Rate Parameters 48
3.4.1 Concentration-Related Parameters: Order of Reaction 49
3.4.2 Experimental Aspects of Measurement of Arrhenius Parameters A and EA 57
3.5 Notes on Methodology for Parameter Estimation 57
3.6 Problems for Chapter 3 6 1

4 . DEVELOPMENT OF THE RATE LAW FOR A SIMPLE SYSTEM 64
4.1 The Rate Law 6 4
4.1.1 Form of Rate Law Used 64
4.1.2 Empirical versus Fundamental Rate Laws 65
4.1.3 Separability versus Nonseparability of Effects 66
4.2 Gas-Phase Reactions: Choice of Concentration Units 66
4.2.1 Use of Partial Pressure 66
4.2.2 Rate and Rate Constant in Terms of Partial Pressure 67
4.2.3 Arrhenius Parameters in Terms of Partial Pressure 68
4.3 Dependence of Rate on Concentration 6 9
4.3.1 First-Order Reactions 69
4.3.2 Second-Order Reactions 71
4.3.3 Third-Order Reactions 72
4.3.4 Other Orders of Reaction 75
4.35 Comparison of Orders of Reaction 75
4.3.6 Product Species in the Rate Law 78
4.4 Dependence of Rate on Temperature 7 9
4.4.1 Determination of Arrhenius Parameters 79
4.4.2 Arrhenius Parameters and Choice of Concentration Units for Gas-Phase
Reactions 80
4.5 Problems for Chapter 4 80

5 . COMPLEXSYSTEMS 87 -
5.1 Types and Examples of Complex Systems 8 7
51.1 Reversible (Opposing) Reactions 87
5.1.2 Reactions in Parallel 88
5.1.3 Reactions in Series 88
5.1.4 Combinations of Complexities 88
5.1.5 Compartmental or Box Representation of Reaction Network 89
5.2 Measures of Reaction Extent aud Selectivity 90
5.2.1 Reaction Stoichiometry and Its Significance 90
5.2.2 Fractional Conversion of a Reactant 91
5.2.3 Yield of a Product 91
5.2.4 Overall and Instantaneous Fractional Yield 92
5.2.5 Extent of Reaction 93
5.2.6 Stoichiometric Table for Complex System 93
5.3 Reversible Reactions 9 4
5.3.1 Net Rate and Forms of Rate Law 94
5.3.2 Thermodynamic Restrictions on Rate and on Rate Laws 95
5.3.3 Determination of Rate Constants 97
5.3.4 Optimal T for Exothermic Reversible Reaction 99
5.4 Parallel Reactions 100
5.5 Series Reactions 103