Kinetics of Catalytic Reactions

Foreword Preface List of Symbols 1. Regular Symbols 2. Greek Symbols 3. Subscripts 1: Introduction 2: Definitions and Concepts 2.1 Stoichiometric Coefficients 2.2 Extent of Reaction 2.3 Rate of Reaction 2.4 Turnover Frequency or Specific Activity 2.5 Selectivity 2.6 Structure-Sensitive and Structure4nsensitive Reactions 2.7 Elementary Step and Rate Determining Step (RDS) 2.8 Reaction Pathway or Catalytic Cycle 2.9 Most Abundant Reaction Intermediate (MARI) 2.10 Chain Reactions 2.11 Reaction Rates in Reactors 2.12 Metal Dispersion (Fraction Exposed) 2.13 Meta1Support Interactions (MSI) References 3: Catalyst Characterization 3.1 Total (BET) Surface Area 3.2 Pore Volume and Pore Size Distribution 3.2.1 Hg Porosimetry Method 3.2.2 N2 Desorption Method 3.2.3 Overall Pore Size Distribution 3.3 Metal Surface Area, Crystallite Size, and Dispersion 3.3.1 Transmission Electron Microscopy (TEM) 3.3.2 X-Ray Techniques 3.3.2.1 Line Broadening of X-Ray Diffraction (XRD) Peaks 3.3.2.2 Extended X-Ray Absorption Fine Structure (EXAFS) 3.3.3 Magnetic Measurements 3.3.4 Chemisorption Methods 3.3.4.1 H2 Chemisorption 3.3.4.2 CO Chemisorption 3.3.4.3 02 Chemisorption 3.3.4.4 H2-02 Titration Techniques 3 3.5 Relationships Between Metal Dispersion, Surface Area, and Crystallite Size References Problems 4: Acquisition and Evaluation of Reaction Rate Data 4.1 Types of Reactors 4.1.1 Batch Reactor 4.1.2 Semi-Batch Reactor 4.1.3 Plug-Flow Reactor (PFR) 4.1.4 Continuous Flow Stirred-Tank Reactor (CSTR) 4.2 Heat and Mass Transfer Effects 4.2.1 Interphase (External) Gradients (Damkhler Number) 4.2.1.1 Isothermal Conditions 4.2.1.2 Nonisothermal Conditions 4.2.2 Intraphase (Internal) Gradients (Thiele Modulus) 4.2.1.1 Isothermal Conditions 4.2.2.2Nonisothermal Conditions 4.2.2.3 Determining an Intraphase (Internal) Effectiveness Factor from a Thiele Modulus 4.2.3 Intraphase Gradients (Weisz-Prater Criterion) 4.2.3.1 Gas-Phase or Vapor-Phase Reactions 4.2.3.2 Liquid-Phase Reactions 4.2.4 Other Criteria to Verify the Absence of Mass and Heat Transfer Limitations (The Madon-Boudart Method) 4.2.5 Summary of Tests for Mass and Heat Transfer Effects References Problems 5: Adsorption and Desorption Processes 5.1 Adsorption Rate 5.2 Desorption Rate 5.3 Adsorption Equilibrium on Uniform (Ideal) Surfaces-Langmuir Isotherms 5.3.1 Single-Site (Nondissociative) Adsorption 5.3.2 Dual-Site (Dissociative) Adsorption 5.3.3 Derivation of the Langmuir Isotherm by Other Approaches 5.3.4 Competitive Adsorption 5.4 Adsorption Equilibrium on Nonuniform (Nonideal) Surfaces 5.4.1 The Freundlich Isotherm 5.4.2 The Temkin Isotherm 5.5 Activated Adsorption References Problems 6: Kinetic Data Analysis and Evaluation of Model Parameters for Uniform (Ideal) Surfaces 6.1 Transition-State Theory (TST) or Absolute Rate Theory 6.2 The Steady-State Approximation (SSA) 6.3 Heats of Adsorption and Activation Barriers on Metal Surfaces: BOC-MP/UBI-QEP Method 6.3.1 Basic BOC-MP/UBI-QEP Assumptions 6.3.2 Heats of Atomic Chemisorption 6.3.3 Heats of Molecular Chemisorption 6.3.4 Activation Barriers for Dissociation and Recombination on Metal Surfaces 6.4 Use of a Rate Determining Step (RDS) and/or a Most Abundant Reaction Intermediate (MARl) 6.5 Evaluation of Parameter Consistency in Rate Expressions for Ideal Surfaces References Problems 7: Modeling Reactions on Uniform (Ideal) Surfaces 7.1 Reaction Models with a RDS Unimolecular Surface Reactions 7.2 Reaction Models with a RDS Bimolecular Surface Reactions 7.3 Reaction Models with a RDS Reactions between an Adsorbed Species and a Gas