Chapter
1.3.3 The Chemical Industry
1.4 Catalysis as a Multidisciplinary Science
1.4.1 The Many Length Scales of a “Catalyst”
1.4.2 Time Scales in Catalysis
1.5 The Scope of this Book
1.6 Appendix: Catalysis in Journals
2.2 The Rate Equation and Power Rate Laws
2.3 Reactions and Thermodynamic Equilibrium
2.3.1 Example of Chemical Equilibrium: The Ammonia Synthesis
2.3.2 Chemical Equilibrium for a Nonideal Gas
2.4 The Temperature Dependence of the Rate
2.5 Integrated Rate Equations: Time Dependence of Concentrations in Reactions of Different Orders
2.6 Coupled Reactions in Flow Reactors: The Steady State Approximation
2.7 Coupled Reactions in Batch Reactors
2.8.1 The Mean-Field Approximation
2.9 Langmuir Adsorption Isotherms
2.9.1 Associative Adsorption
2.9.2 Dissociative Adsorption
2.9.3 Competitive Adsorption
2.10.1 Langmuir–Hinshelwood or Eley–Rideal Mechanisms
2.10.2 Langmuir–Hinshelwood Kinetics
2.10.3 The Complete Solution
2.10.4 The Steady State Approximation
2.10.5 The Quasi-Equilibrium Approximation
2.10.6 Steps with Similar Rates
2.10.7 Irreversible Step Approximation
2.10.8 The MARI Approximation
2.10.9 The Nearly Empty Surface
2.10.10 The Reaction Order
2.10.11 The Apparent Activation Energy
2.11 Entropy, Entropy Production, Auto Catalysis, and Oscillating Reactions
2.12 Kinetics of Enzyme-Catalyzed Reactions
3.2 The Boltzmann Distribution and the Partition Function
3.3 Partition Functions of Atoms and Molecules
3.3.1 The Boltzmann Distribution
3.3.2 Maxwell–Boltzmann Distribution of Velocities
3.3.3 Total Partition Function of a System
3.4 Molecules in Equilibrium
3.5.1 Reaction Probability
3.5.2 Fundamental Objection against Collision Theory
3.6 Activation of Reacting Molecules by Collisions: The Lindemann Theory
3.7 Transition State Theory
3.8 Transition State Theory of Surface Reactions
3.8.1 Adsorption of Atoms
3.8.2 Adsorption of Molecules
3.8.3 Reaction between Adsorbates
3.8.4 Desorption of Molecules
4 Catalyst Characterization
4.2 X-ray Diffraction (XRD)
4.3 X-ray Photoelectron Spectroscopy (XPS)
4.4 X-ray Absorption Spectroscopy (EXAFS and XANES)
4.4.1 Extended X-ray Absorption Fine Structure (EXAFS)
4.4.2 X-ray Absorption Near-Edge Spectroscopy (XANES)
4.6 Mössbauer Spectroscopy
4.7 Ion Spectroscopy: SIMS, LEIS, RBS
4.8 Temperature-Programmed Reduction, Oxidation, and Sulfidation
4.9 Infrared Spectroscopy
4.10 Surface Science Techniques
4.10.1 Low Electron Energy Diffraction (LEED)
4.10.2 Scanning Probe Microscopy
5.1 Requirements of a Successful Catalyst
5.2 The Structure of Metals, Oxides, and Sulfides and Their Surfaces
5.2.2 Surface Crystallography of Metals
5.2.3 Oxides and Sulfides
5.2.4 Surface Free Energy
5.3 Characteristics of Small Particles and Porous Material
5.3.1 The Wulff Construction
5.4.4 Shaping of Catalyst Supports
5.5 Preparation of Supported Catalysts
5.5.2 Impregnation, Adsorption, and Ion Exchange
5.5.3 Deposition Precipitation
5.6 Unsupported Catalysts
5.7.1 Structure of a Zeolite
5.7.2 Compensating Cations and Acidity
5.7.3 Applications of Zeolites
5.8.1 Ten Commandments for Testing Catalysts
5.8.2 Activity Measurements
6.2.1 The Van der Waals Interaction
6.2.2 Including the Repulsive Part
6.3.1 Bonding in Molecules
6.4.1 The Newns–Anderson Model
6.4.2 Summary of the Newns–Anderson Approximation in Qualitative Terms
6.4.3 Electrostatic Effects in Atomic Adsorbates on Jellium
6.5 Important Trends in Surface Reactivity
6.5.1 Trend in Atomic Chemisorption Energies
6.5.2 Trends in Molecular Chemisorption
6.5.3 Trends in Surface Reactivity
6.5.4 Universality in Heterogeneous Catalysis
6.5.6 Appendix: Density Functional Theory (DFT)
7 Kinetics of Reactions on Surfaces
7.1 Elementary Surface Reactions
7.1.1 Adsorption and Sticking
7.1.3 Lateral Interactions in Surface Reactions
7.1.4 Dissociation Reactions on Surfaces
7.1.5 Intermediates in Surface Reactions
7.1.6 Association Reactions
7.2 Kinetic Parameters from Fitting Langmuir–Hinshelwood Models
7.3 Microkinetic Modeling
7.3.1 Reaction Scheme and Rate Expressions
7.3.2 Activation Energy and Reaction Orders
7.3.3 Ammonia Synthesis Catalyst under Working Conditions
8 Catalysis in Practice: Synthesis Gas and Hydrogen
8.2 Synthesis Gas and Hydrogen
8.2.1 Steam Reforming: Basic Concepts of the Process
8.2.2 Mechanistic Detail of Steam Reforming
8.2.3 Challenges in the Steam Reforming Process
8.2.4 The SPARG Process: Selective Poisoning by Sulfur
8.2.5 Gold–Nickel Alloy Catalyst for Steam Reforming
8.2.6 Direct Uses of Methane
8.3 Reaction of Synthesis Gas
8.3.2 Fischer–Tropsch Process
8.4 Water–Gas Shift Reaction
8.5.1 History of Ammonia Synthesis
8.5.2 Ammonia Synthesis Plant
8.5.3 Operating the Reactor
8.5.4 Scientific Rationale for Improving Catalysts
8.6 Promoters and Inhibitors
8.7 The “Hydrogen Society”
8.7.1 The Need for Sustainable Energy
8.7.2 Sustainable Energy Sources
8.7.4 Hydrogen Fuel Cells
9 Oil Refining and Petrochemistry
9.2.1 Heteroatoms and Undesired Compounds
9.2.2 Hydrotreating Catalysts
9.2.3 Hydrodesulfurization Reaction Mechanisms
9.3.1 Fluidized Catalytic Cracking
9.3.2 Reforming and Bifunctional Catalysis
9.4 Petrochemistry: Reactions of Small Olefins
9.4.1 Ethylene Epoxidation
9.4.2 Partial Oxidation and Ammoxidation of Propylene
9.4.3 Polymerization Catalysis
10 Environmental Catalysis
10.2 Air Pollution by Automotive Exhaust
10.2.1 The Three-Way Catalyst
10.2.2 Catalytic Reactions in the Three-Way Catalyst: Mechanism and Kinetics
10.2.3 Concluding Remarks on Automotive Catalysts
10.3 Air Pollution by Large Stationary Sources
10.3.1 Selective Catalytic Reduction: The SCR Process
10.3.2 The SCR Process for Mobile Units
Concepts of Modern Catalysis and Kinetics
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