Kinetics of Chemical Reactions

This second, extended and updated edition presents the current state of kinetics of chemical reactions, combining basic knowledge with results recently obtained at the frontier of science.
Special attention is paid to the problem of the chemical reaction complexity with theoretical and methodological concepts illustrated throughout by numerous examples taken from heterogeneous catalysis combustion and enzyme processes.
Of great interest to graduate students in both chemistry and chemical engineering.

Auteur
Guy B. Marin is professor in Chemical Reaction Engineering at Ghent University (Belgium) and directs the Laboratory for Chemical Technology. The investigation of chemical kinetics constitutes the core of his research. He has co-authored more than 600 papers in high impact journals and is co-inventor in 3 patents. He is editor-in-chief of 'Advances in Chemical Engineering', co-editor of the 'Chemical Engineering Journal' and member of the editorial boards of 'Industrial & Engineering Chemistry Research', 'Current Opinion in Chemical Engineering' and the 'Canadian Journal of Chemical Engineering'. He is member of Scientific Advisory Boards in France, Denmark and the Netherlands. He is 'Master' of the 111 project of the Chinese Government for oversees collaborations in his field.

Professor G. Yablonsky is an Associate Research Professor of Chemistry at Parks College and the College of Arts and Sciences. Previously (1997-2007), he was a Research Associate Professor in the Department of Energy, Environmental and Chemical Engineering as Washington University in St. Louis. He is a world recognized expert in the area of chemical kinetics and chemical engineering, in catalytic technology particularly, which is one of main driving forces of sustainable development. He has authored two monographs and more than 200 peer-reviewed papers on these topics.

Denis Constales is associate professor of mathematical analysis at Ghent University. His work centres on the application of of integral transforms, special functions and computer algebra to problems ranging from hypercomplex analysis to applied mathematical modelling, with a strong emphasis on topics from chemical engineering and reaction kinetics. He has co-authored two monographs and more than 100 peer-reviewed papers on these subjects.

Contenu

Preface to First Edition xv

Preface to Second Edition xix

1 Introduction 1

1.1 Overview 1

1.2 Decoding Complexity in Chemical Kinetics 2

1.3 Three Types of Chemical Kinetics 2

1.3.1 Applied Kinetics 3

1.3.2 Detailed Kinetics 3

1.3.3 Mathematical Kinetics 3

1.4 Challenges and Goals. How to Kill Chemical Complexity 4

1.4.1 Gray-Box Approach 4

1.4.2 Analysis of Kinetic Fingerprints 5

1.4.3 Non-steady-state Kinetic Screening 6

1.5 What Our Book is Not About. Our Book among Other Books on Chemical Kinetics 6

1.6 The Logic in the Reasoning of This Book 7

1.7 How Chemical Kinetics and Mathematics are Interwoven in This Book 7

1.8 History of Chemical Kinetics 8

References 12

2 Chemical Reactions and Complexity 17

2.1 Introduction 17

2.2 Elementary Reactions and the Mass-Action Law 19

2.2.1 Homogeneous Reactions 19

2.2.2 Heterogeneous Reactions 21

2.2.3 Rate Expressions 22

2.3 The Reaction Rate and Net Rate of Production of a Component A Big Difference 23

2.4 Dimensions of the Kinetic Parameters and Their Orders of Magnitude 24

2.5 Conclusions 26

Nomenclature 26

References 28

3 Kinetic Experiments: Concepts and Realizations 29

3.1 Introduction 29

3.2 Experimental Requirements 29

3.3 Material Balances 30

3.4 Classification of Reactors for Kinetic Experiments 31

3.4.1 Steady-state and Non-steady-state Reactors 31

3.4.2 Transport in Reactors 31

3.4.3 Ideal Reactors 32

3.4.3.1 Batch Reactor 32

3.4.3.2 Continuous Stirred-tank Reactor 33

3.4.3.3 Plug-flow Reactor 34

3.4.4 Ideal Reactors with Solid Catalyst 34

3.4.4.1 Batch Reactor 34

3.4.4.2 Continuous Stirred-tank Reactor 35

3.4.4.3 Plug-flow Reactor 35

3.4.4.4 Pulse Reactor 35

3.4.5 Determination of the Net Rate of Production 36

3.5 Formal Analysis of Typical Ideal Reactors 36

3.5.1 Batch Reactor 36

3.5.1.1 Irreversible Reaction 36

3.5.1.2 Reversible Reaction 38

3.5.1.3 How to Distinguish Parallel Reactions from Consecutive Reactions 40

3.5.2 Steady-state Plug-flow Reactor 43

3.5.3 Non-steady-state Continuous Stirred-tank Reactor 43

3.5.3.1 Irreversible Reaction 43

3.5.3.2 Reversible Reaction 44

3.5.4 Thin-zone TAP Reactor 45

3.6 Kinetic-model-free Analysis 46

3.6.1 Steady State 46

3.6.2 Non-steady State 47

3.6.2.1 Continuous Stirred-tank Reactor 47

3.6.2.2 Plug-flow Reactor 48

3.7 Diagnostics of Kinetic Experiments in Heterogeneous Catalysis 49

3.7.1 Gradients at Reactor and Catalyst-pellet Scale 49

3.7.2 Experimental Diagnostics and Guidelines 49

3.7.2.1 Test for External Mass-transfer Effect 51

3.7.2.2 Test for Internal Mass-transport Effect 51

3.7.2.3 Guidelines 52

3.7.3 Theoretical Diagnostics 52

3.7.3.1 External Mass Transfer 53

3.7.3.2 External Heat Transfer 54

3.7.3.3 InternalMass Transport 56

3.7.3.4 Internal Heat Transport 59

3.7.3.5 Non-steady-state Operation 59

Nomenclature 59

References 62

4 Chemical Book-keeping: Linear Algebra in Chemical Kinetics 65

4.1 Basic Elements of Linear Algebra 65

4.2 Linear Algebra and Complexity of Chemical Reactions 67

4.2.1 Atomic Composition of Chemical Components: Molecules Consist of Atoms 68

4.2.1.1 Molecular Matrix 68

4.2.1.2 Linear Algebra and Laws of Mass Conservation 68

4.2.1.3 Key Components and Their Number 70

4.2.2 Stoichiometry of Chemical Reactions: Reactions Consist of Chemical Components 72

4.2.2.1 Stoichiometric Matrix 72 4.2.2.2 Difference and Simila...