Kinetics of Homogeneous Multistep Reactions
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Kinetics of Homogeneous Multistep Reactions

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Friedrich G. Helfferich
953 g
254x178x24 mm
38, Comprehensive Chemical Kinetic

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.
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.