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Informationen zum Autor Robert A. Stairs, Ph.D, FCIC, is Professor Emeritus in the Department of Chemistry at Trent University at Peterborough, Ontario, having joined at its opening in 1964, after teaching at Cornell and at Queen's University in Kingston. During his 25 years at Trent, he served as chair of the Department twice. Since retiring, Prof. Stairs keeps up a close relationship with Trent, returning regularly for seminars and special events, and maintaining a modest research program. Erwin Buncel, PhD, FRCS, is Professor Emeritus in the Physical Organic Chemistry department at Queen's University. He received his Ph.D. in Organic Chemistry in 1957 and his D.Sc. in Physical Organic Chemistry in 1970, both at the Unversity of London. He has won several awards and honors, including the R.U. Lemieux Award in Organic Chemistry - Canadian Society for Chemistry in 1999 and he was a Fellow, World Innovation Foundation (2001). He has recently been elected a fellow of the Royal Society of Canada. Klappentext This book introduces the concepts, theory and experimental knowledge concerning solvent effects on the rate and equilibrium of chemical reactions of all kinds. It begins with basic thermodynamics and kinetics, building on this foundation to demonstrate how a more detailed understanding of these effects may be used to aid in determination of reaction mechanisms, and to aid in planning syntheses. Consideration is given to theoretical calculations (quantum chemistry, molecular dynamics, etc.), to statistical methods (chemometrics), and to modern day concerns such as "green" chemistry, where utilization and disposal of chemical waste or by-products in an environmentally safe way is as important as achieving the desired end products by all chemists nowadays. The treatment progresses from elementary to advanced material in straightforward fashion. The more advanced topics are not developed in an overly rigorous way so that upper-level undergraduates, graduates, and newcomers to the field can grasp the concepts easily. Zusammenfassung This book introduces the concepts, theory and experimental knowledge concerning solvent effects on the rate and equilibrium of chemical reactions of all kinds. Inhaltsverzeichnis Preface to the Second Edition viii Preface to the First Edition x 1 Physicochemical Foundations 1 1.1 Generalities 1 1.2 Classification of Solvents 4 1.3 Solvents in the Workplace and the Environment 6 1.4 Some Essential Thermodynamics and Kinetics: Tendency and Rate 7 1.5 Equilibrium Considerations 7 1.6 Thermodynamic Transfer Functions 9 1.7 Kinetic Considerations: Collision Theory 10 1.8 Transition?-State Theory 11 1.9 Reactions in Solution 16 1.10 Diffusion?-Controlled Reactions 16 1.11 Reaction in Solution and the Transition? State Theory 18 Problems 21 2 Unreactive Solvents 23 2.1 Intermolecular Potentials 23 2.2 Activity and Equilibrium in Nonelectrolyte Solutions 24 2.3 Kinetic Solvent Effects 28 2.4 Solvent Polarity 30 2.5 Electrostatic Forces 30 2.6 Electrolytes in Solution 33 2.7 Solvation 36 2.8 Single Ion Solvation 39 2.9 Ionic Association 42 2.10 Solvent Mixtures 47 2.11 Salt Effects 53 Problems 55 3 Reactive Solvents 57 3.1 Specific Solute/Solvent Interactions 57 3.2 Hydrogen Bonding 58 3.3 Acids and Bases in Solvents 59 3.4 Brønsted-Lowry Acids and Bases 60 3.5 Acidity Functions 62 3.6 Acids and Bases in Kinetics 65 3.7 Lewis Acids and Bases 76 3.8 Hard and Soft Acids and Bases (HSAB) 77 3.9 Scales of Hardness or Softness 78 3.10 Acids and Bases in Reactive Aprotic Solvents 82 3.11 Extremes of Acidity and Basicity 83 3.12 O xidation and Reduction 83 3.13 Aci...
