Kinetics of Homogeneous Multistep Reactions

Friedrich G. Helfferich (Author)

9780444826060, Elsevier Science

Hardback, published 25 January 2001

426 pages
22.9 x 15.1 x 2.7 cm, 0.93 kg

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.

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.

Subject Areas: Chemical engineering [TDCB], Industrial chemistry [TDC], Physical chemistry [PNR], Analytical chemistry [PNF], Chemistry [PN]