Kinetics of Homogeneous Multistep Reactions


  • Friedrich Helfferich, Professor Emeritus, Pennsylvania State University, Philadelphia, USA

This book addresses primarily 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.
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Book information

  • Published: January 2001
  • Imprint: ELSEVIER
  • ISBN: 978-0-444-82606-0


This book not only provides practical engineers a handy tool to analyze industrial reactions in the field, but also leads students to handle complicated problems in the classrooms. I used part of the contents in Helfferich's book to teach a graduate-level course on chemical reaction engineering. Everyone was amazed by the powerfulness of the mathematic tools to eluicidate complicated chemical reaction networks.
Dr. Jia-Ming Chern, Prof. of Chemical Engineering, Tatung Technical University., February 2001

I applied the tools provided from this book to three different areas: Enzyme reactions, homogenous catalytic reactions and polymeric reactions. The results of such applications are extremely useful for the development of kinetic models. The combination of the theoretical approach in terms of practical mathematics and the experimental consideration from this book is unique and excellent. This book is needed for process engineers in the chemical industry and also provides the industrial approach for kinetic studies that are very useful information for the teaching of reaction kinetics.
Daniel S. Hsieh Ph.D, MC Research & Innovation Centre Inc., February 2001
This book is one of the very few kinetic books, if not the only one, extensively covering the real-world reactions, which are typically much more complicated than the ideal reactions discussed in textbooks. The book provides very useful tools for reducing a complicated reaction network so that it can be modeled with a manageable number of not only equations (computational load) but also parameters (experimental load). The tools have been successfully applied to a few industrial chemical processes, some of which are discussed in the book as examples. Although this book is intended to be a reference for industrial practitioners it should also be an excellent reference for graduate students working in the field of reaction kinetics/engineering.
Dr. Alan Hwang, Exxon-Mobil Research and Engineering, February 2001
This book provides a unique perspective on chemical kinetics. Written by a man who spent most of his career in the chemical process industry, the book never veers very far from practical matters. The treatment of the mathematics of mutlistep reactions is original and cannot be found in any other textbook. I have found these methods to be useful in my research, and they have become an integral part of the kinetics, catalysis, and reaction engineering classes I teach. The book would make a very nice accompaniment to an advanced undergraduate or graduate-level kinetics course.
Phillip E. Savage, University of Michigan, February 2001
I have thoroughly enjoyed reading this book, which should become a MUST for every aspiring kineticist. Never have I seen in one place the number of rate equations for such a variety of reaction networks and cycles. The author even gives real chemical examples that fit most of the schemes. What impressed me most is that all are based on more-or-less fundamental principles. For example, in almost every chapter after it was introduced in Chapter 4, specific illustrations of the Bodenstein approximation are given. In addition, there are dozens of good examples from the author's experience at Shell and others' that will be useful to all of us in education.
J. W. Hightower, Rice University, February 2001

Table of Contents

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.