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 126.96.36.199 Line Broadening of X-Ray Diffraction (XRD) Peaks 188.8.131.52 Extended X-Ray Absorption Fine Structure (EXAFS) 3.3.3 Magnetic Measurements 3.3.4 Chemisorption Methods 184.108.40.206 H2 Chemisorption 220.127.116.11 CO Chemisorption 18.104.22.168 02 Chemisorption 22.214.171.124 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 (Damkohler Number) 126.96.36.199 Isothermal Conditions 188.8.131.52 Nonisothermal Conditions 4.2.2 Intraphase (Internal) Gradients (Thiele Modulus) 184.108.40.206 Isothermal Conditions 220.127.116.11 Nonisothermal Conditions 18.104.22.168 Determining an Intraphase (Internal) Effectiveness Factor from a Thiele Modulus 4.2.3 Intraphase Gradients (Weisz-Prater Criterion) 22.214.171.124 Gas-Phase or Vapor-Phase Reactions 126.96.36.199 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 Approaches5.3.4 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-Phase Species 7.4 Reaction Models with no RDS 7.4.1 A Series of Irreversible Steps - General Approach 7.4.2 Redox Reactions: The Mars-van Krevelen Rate Law 7.5 Data Analysis with an Integral Reactor 7.6 Occurrence of a Very High Reaction Order References Problems 8: Modeling Reactions on Nonuniform (Nonideal) Surfaces 8.1 Initial Models of a Nonuniform Surface 8.2 Correlations in Kinetics 8.3 Formalism of a Temkin Surface 8.4 Consequences of Temkin's Model 8.4.1 Adsorption Isotherms 8.4.2 Kinetic and Catalytic Behavior References Problems 9: Kinetics of Enzyme-Catalyzed Reactions 9.1 Single-Substrate Reactions 9.2 Dual-Substrate Reactions References Problems Subject Index.
(source: Nielsen Book Data)
This advanced textbook teaches readers to design kinetic experiments involving heterogeneous catalysts, to characterize these catalysts, to acquire rate data, to find heat and mass transfer limitations in these data, to select reaction models, to derive rate expressions based on these models, and to assess the consistency of these rate equations. Special emphasis is placed on assessing mass transfer effects. Discussion of adsorption isotherms and reaction models explains the limitations of these models and their application. Ideal and nonideal surfaces are considered, as well as enzyme catalysis. Exercises and worked examples abound. The book will be used in courses in kinetics or catalysis and also as a supplement in advanced chemical engineering courses on kinetics and reactor design. It will be used in the disciplines of Chemical Engineering, Materials Science, Fuels Science, and Chemistry. This should be a tremendously useful reference book as industrial scientists design runs with heterogeneous catalysts, interpret their experimental data, and model the kinetics to describe their results. (source: Nielsen Book Data)