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Kinetics of Homogeneous Multistep Reactions : Volume 38 - Friedrich Helfferich

Kinetics of Homogeneous Multistep Reactions

Volume 38

Hardcover

Published: 8th February 2001
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This text primarily addresses the chemist and engineer in industrial research and process development, where competitive pressures put a premium on scale-up by large factors to cut development time. To be safe, such scale-up should be based on "fundamental" kinetics, that is, mathematics that reflect the elementary steps of which the reactions consist. The book forges fundamental kinetics into a practical tool by presenting new effective methods for elucidation of mechanisms and reduction of mathematical complexity without unacceptable sacrifice in accuracy. For elucidation of pathways and networks, the book provides a host of new rules relating typical network configurations to observable kinetic behavior. Any configuration producing behavior contrary to observation cannot be correct, so incorrect networks can be rejected by whole classes instead of one by one. For modeling, the book provides general equations and algorithms applicable to networks of arbitrary size and configuration. Equations for specific networks can be recovered from these by simple substitutions. The procedures are illustrated with examples of industrial reactions, including olefin hydroformylation and alcohol ethoxylation in detergent manufacture, hydrocyanation and paraffin oxidation in du Pont's Nylon process, and free-radical polymerization of styrene among many others. Many of the rate equations derived have not been published previously. Although the book is restricted to homogeneous reactions, it should be of use also for heterogeneous catalysis as the principles apply equally to reactions on catalyst surfaces. While not covering reactor design, the book points out how facets of complex kinetics impact reactor choice or present pitfalls to beware of.

Preface
Introduction
References
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
Summary
References
Fundamentals
Statistical basis: molecularities and reaction orders
Nonideality
Temperature dependence
Compilation of rate equations of multistep reactions
Consistency criteria
Summary
References
Determination of rates, orders, and rate coefficients
Research reactors
Analytical support
Reaction orders and apparent rate coefficients
Numerical work-up, error recognition, and reliability
Summary
References
Tools for reduction of complexity
Rate-controlling steps
Quasi-equilibrium steps
Quasi-stationary states: the Bodenstein approximation
Relative abundance in catalysis and polymerization and long-chain approximation
Summary
References
Elementary step combinations
Reversible reactions
Parallel steps
Coupled parallel steps
Sequential steps
Competing steps
Reactions with fast pre-dissociation
General solution for first-order networks
Summary
References
Practical mathematics of multistep reactions
Simple and non-simple pathways and networks
Pseudo-first order rate coefficients
Simple pathways
Simple networks
Non-simple pathways and networks
Summary
References
Network elucidation
Order and rank
"One plus" rate equations
Relationships between network properties and kinetic behavior
Other criteria and guidelines
Auxiliary techniques
Summary
References
Homogeneous catalysis
Single-species catalysis
Complex catalysis
Classical models of enzyme kinetics
General formula for single catalytic cycles: Christiansen mathematics
Reduction of complexity
Relationships between pathway properties and kinetic behavior
Cycles with external reactions
Multiple cycles
Competing reactions (cycles with common members)
Dual- and multiple-form catalysts (connected cycles)
Reactions with multiple products (cycles with common pathway segments)
Self-accelerating reactions (autocatalysis)
Analogies to heterogeneous catalysis
Summary
References
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 free radicals
Inhibition and induction periods
Summary
References
Polymerization
Types of polymerization reactions
Step-growth polymerization
Free-radical polymerization
Ionic polymerization
Coordination polymerization
Chain-growth copolymerization
Summary
References
Mathematical Modeling
Strategies of process development
Effective mathematical modeling
"Shortsightedness" of elementary reaction steps
Model validation
Summary
References
Unusual thermal and mass-transfer effects
Anomalous temperature dependence
Uncommon heat-transfer problems
Uncommon mass-transfer problems
Summary
References
Glossary of symbols
Author Index
Subject Index
Table of Contents provided by Publisher. All Rights Reserved.

ISBN: 9780444826060
ISBN-10: 0444826068
Series: Comprehensive Chemical Kinetics
Audience: Professional
Format: Hardcover
Language: English
Number Of Pages: 426
Published: 8th February 2001
Publisher: Elsevier Science & Technology
Country of Publication: GB
Dimensions (cm): 22.9 x 15.2  x 1.91
Weight (kg): 0.93
Edition Number: 2