Keywords:
Chemical kinetics.
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Electronic books.
Description / Table of Contents:
This book addresses primarily the engineer in industrial process development, the research chemist in academia and industry, and the graduate student intending to become a reaction engineer. In industry, competitive pressures put a premium on scale-up by large factors to cut development time. To be safe, such development should be based on "fundamental" kinetics that reflect the elementary steps of which the reaction consists. The book forges fundamental kinetics into a practical tool by presenting new, effective methods for elucidation of mechanisms and reduction of complexity without unacceptable sacrifice in accuracy: fewer equations (lesser computational load), fewer coefficients (fewer experiment to determine them). For network elucidation, new rules relating network configurations to observable kinetic behaviour allow incorrect networks to be ruled out by whole classes instead of one by one. For modelling, general equations and algorithms are given from which equations for specific networks can be recovered by simple substitutions. The procedures are illustrated with examples of industrial reactions including, among others, paraffin oxidation, ethoxylation, hydroformylation, hydrocyanation, shape-selective catalysis, ethane pyrolysis, styrene polymerization, and ethene oligomerization. Many of the rate equations have not been published before. The expanded edition of the 2001 title, Kinetics of Homogeneous Multistep Reactions includes new chapters on heterogeneous catalysis and periodic and chaotic re-actions; new sections on adsorption, statistical methods, and lumping; and other new detail. * Contains new chapters on heterogeneous catalysis, oscillations and chaos * Includes new sections on statistical methods, lumping adsorption and software and databases * Provides a better understanding of complex reaction mechanisms.
Type of Medium:
Online Resource
Pages:
1 online resource (508 pages)
Edition:
2nd ed.
ISBN:
9780080473185
Series Statement:
Issn Series ; v.Volume 40
URL:
https://ebookcentral.proquest.com/lib/geomar/detail.action?docID=288819
DDC:
541.394
Language:
English
Note:
Cover -- Preface -- Preface to Second Edition -- Contents -- Introduction -- References -- 1. Concepts, Definitions, Conventions, and Notation -- Classification of Reactions -- Steps, Pathways, Networks, and Cycles -- Rates -- Rate Equations and Activation Energies -- Orders, Molecularities, and Ranks -- Conversion, Yield, and Selectivity -- Phase-Equilibrium and Transport Properties -- Summary -- References -- 2. Fundamentals -- Statistical Basis: Molecularities and Reaction Orders -- Nonideality -- Temperature Dependence -- Compilation of Rate Equations of Multistep Reactions -- Consistency Criteria -- Thermodynamic Consistency -- Microscopic Reversibility -- Adsorption Equilibria and Rates -- Summary -- References -- General References -- Specific References -- 3. Experiments and Their Evaluation -- Research Reactors -- Batch Reactors -- Continuous Stirred-Tank Reactors -- Tubular Reactors -- Differential Reactors -- Techniques for Fast Reactions -- Analytical Support -- Reaction Orders and Apparent Rate Coefficients -- Irreversible Reactions with Single Reactant -- Irreversible Reactions with Two or More Reactants -- Reversible Reactions -- Gas-Phase Reactions at Constant Pressure -- Numerical Work-Up, Error Recognition, and Reliability -- Overview of Statistical Methods * -- Summary -- References -- General References -- Specific References -- 4. Tools for Reduction of Complexity -- Stoichiometric Constraints -- Rate-Controlling Steps -- Pathways of Irreversible Steps -- Pathways with Reversible Steps -- Quasi-Equilibrium Steps -- Quasi-Stationary States: the Bodenstein Approximation* -- Summary -- References -- 5. Elementary Combinations of Reaction Steps -- Reversible Reactions -- First Order-First Order Reactions -- First Order-Second Order Reactions -- Second Order-Second Order and Higher-Order Reactions -- Parallel Steps.
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Parallel First-Order Steps -- Parallel Second-Order Steps -- Parallel Steps of Different Orders -- Coupled Parallel Steps -- Sequential Steps -- Sequential First-Order Steps -- Sequential Steps of other Orders -- Competing Steps -- Reactions with Fast Pre-Dissociation -- General Solution for First-Order Networks -- Summary -- References -- General References -- Specific References -- 6. Practical Mathematics of Multistep Reactions -- Simple and Non-Simple Pathways and Networks -- Pseudo-First Order Rate Coefficients -- General Formula for Simple Pathways -- Simple Networks -- Network Reduction -- Rate Equations -- Yield-Ratio Equations [8] -- Non-Simple Pathways and Networks -- Summary -- References -- 7. Network Elucidation -- Order and Rank -- Reaction Orders -- Ranks and Delplot * -- One-Plus" Rate Equations -- Types of One-Plus Rate Equations -- Establishment of One-Plus Rate Equations from Experimental Data -- Relationships between Network Properties and Kinetic Behavior -- Simple Pathways [7,9] -- Simple Networks -- Non-Simple Pathways and Networks -- Other Criteria and Guidelines -- Auxiliary Techniques -- Summary -- References -- 8. Homogeneous Catalysis -- Single-Species Catalysis -- Complex Catalysis -- Acid-Base Catalysis -- Catalysis by Metal Complexes -- Classical Models of Enzyme Kinetics -- Michaelis-Menten Kinetics -- Briggs-Haldane Kinetics -- Reversible Cycles -- Common Features and Plots -- General Formula for Single Catalytic Cycles: Christiansen Mathematics -- Reduction of Complexity -- Relative Abundance of Catalyst-Containing Species * -- Rate-Controlling Steps -- Quasi-Equilibrium Steps -- Irreversible Steps -- Combinations of Approximations -- Relationships between Network Properties and Kinetic Behavior -- Cycles with External Reactions -- Ligand-Deficient Catalysts -- Inhibition, Activation, Decay, and Poisoning.
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Multiple Cycles* -- Competing Reactions (Cycles with Common Member) -- Dual- and Multiple-Form Catalysts (Connected Cycles) -- Reactions with Multiple Products (Cycles with Common Pathway Segments) -- Self-Accelerating Reactions (Autocatalysis) -- Product-Promoted Reactions -- Reactant-Inhibited Reactions -- Summary -- References -- General References -- Specific References -- 9. Heterogeneous Catalysis -- Adsorption and Reaction: Langmuir-Hinshelwood Kinetics -- Rate-Controlling Steps: the Hougen-Watson Formula -- Relative Abundance of Catalyst-Surface Species -- Simplification of Rate Equations -- Self-Acceleration -- Model Discrimination -- Criteria for Coefficients -- Concentration Dependence of Initial Rates -- Testing of Predictions -- Mass and Heat Transfer -- Mass Transfer to and from Catalyst Particle -- Mass Transfer and Reaction within Catalyst Particle (Thiele-Damkohler Theory [16,17]) -- Nonisothermal Catalyst Particles [26,27] -- Forced Convection within Catalyst Particle -- Heterogenized" Catalysis -- Shape Selectivity [47-50] -- Catalyst Deactivation [59-64] -- Summary -- References -- General References -- Specific References -- 10. Chain Reactions -- General Properties -- Initiation -- Reactions with Two Chain Carriers: the Hydrogen-Bromide Reaction -- Identification of Relevant Steps -- Transmission of Reactivity: Indirect Initiation, Chain Transfer -- Reactions with More than Two Radicals -- Rice-Herzfeld Mechanisms: Thermal Cracking -- Hydrocarbon Oxidation -- Reactions with Chain Branching: the Hydrogen-Oxygen Reaction -- Inhibition and Induction Periods -- Summary -- References -- General References -- Specific References -- 11. Polymerization -- Types of Polymerization Reactions -- Step-Growth Polymerization -- Functionality -- Mechanism and Rate -- Degree of Polymerization and Molecular Weight -- Radical Polymerization.
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Mechanism and Rate * -- Photochemical Initiation -- Chain Length -- Degree of Polymerization and Molecular Weight -- Ionic Polymerization -- Anionic Polymerization -- Cationic Polymerization -- Coordination Polymerization -- Mechanism -- Molecular-Weight Distribution and Degree of Polymerization -- Polymerization Rate -- Chain-Growth Copolymerization -- Polymer Composition: Reactivity Ratios and Copolymer Equation -- Polymerization Rate -- Summary -- References -- General References -- Specific References -- 12. Mathematical Modeling -- Strategies of Process Development -- Effective Fundamental Modeling -- Complete Fundamental Modeling with Bodenstein Approximation -- Streamlining for Large Networks -- Determination of Coefficients -- Shortsightedness" of Elementary Reaction Steps -- Lumping and Continuous Mixtures -- Model Validation -- Summary -- References -- 13. Unusual Thermal and Mass-Transfer Effects -- Anomalous Temperature Dependence -- Negative Apparent Activation Energy: Lower Rate at Higher Temperature -- Change in Rate Control with Change in Temperature -- Rate Maxima and Minima -- Activation Energies of Phenomenological Coefficients -- Uncommon Heat-Transfer Problems -- Uncommon Mass-Transfer Problems -- Mass Transfer and Reaction Rate -- Mass transfer and Selectivity -- Summary -- References -- 14. Instability, Periodic Reactions, and Chaos -- Instability -- Runaway and Multiple Steady States -- Periodic Reactions -- Complex Oscillations and Chaos -- Summary -- References -- General References -- Specific References -- 15. Software and Data Bases -- Software for Numerical Simulation -- Software for Statistics -- Data Bases -- Glossary of Symbols -- Author Index -- Subject Index -- List of Reproduced Illustrations.
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