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Louis P. Hammett Mitchill Professor Emeritus of Chemistry, Columbia University My interest in linear free energy relationships began when, just out of graduate school, I read in 1924 the article by Bmnsted and Pedersen which for the first time reported the existence of such a relationship. That interest continues to be an active one and, to judge merely by the extensive biblio graphies contained in the present volume, it is widely shared. To my mind a particularly happy aspect of the existence of linear free energy relationships has been the proof it supplies that one need not suppose that the behavior of nature is hopelessly complicated merely because one cannot find a theoretical reason for supposing it to be otherwise. The effect of a substituent in an organic molecule on rate or equilibrium of reaction involves a fourfold difference between relatively large quantities, a situation which always makes for difficult theory. Yet systematic organic chemistry could hardly have existed were it not true that like changes in structure lead to like changes in reactivity. Linear free energy relationships constitute the quantitative specialisation of this fundamental principle, and they stand indeed more in the office of teacher to theory than in that of learner from it.
Introducing the application of free energy correlations to elucidating the mechanisms of organic and bio-organic reactions, this book provides a new and illuminating way of approaching a potentially complex topic. The idea of how free energy correlations derive from polar substituent change is introduced, and common pitfalls encountered in the application of free energy relationships are described, along with the use of these anomalies in mechanistic studies. The concept of effective charge is described in detail, with examples of its application. Throughout, worked answers are provided for the problems posed. Databases of parameters, an extensive bibliography and comprehensive lists of further reading are also included. The text provides an invaluable source of information to senior undergraduates, postgraduates and to industrial researchers with an interest in mechanistic studies. It is the first such book in more than thirty years.
This book, Correlation Analysis in Chemistry: Recent Advances, is a sequel to our Advances in Linear Free Energy Relationships. t The change in the title is designed to reflect more accurately the nature of the field and the contents of the volume. The term LFER is still widely used, but it is often applied rather loosely to correlation equations that are not LFER in the restricted sense of a relationship involving logarithms of rate or equili brium constants on each side of the equation. The term "correlation analysis" seems to us more appropriate for the whole subject. The use of this term has compelled us also to introduce "chemistry" into the title; we have preferred not to prefix this with "organic" on the grounds that several areas of interest are not "organic chemistry" as usually understood, al though, of course, traditional applications of the basic relationships asso ciated with the names of Hammett and of Taft continue to be of interest. In the first volume we sought through our authors to provide a series of general articles covering the various aspects of the field as they seemed to us. Since the book was the first international research monograph in its field, each chapter, while giving prominence to recent developments, did not neglect earlier work, so that each article presented a comprehensive account of its own area.
Chemical Kinetics and Process Dynamics in Aquatic Systems is devoted to chemical reactions and biogeochemical processes in aquatic systems. The book provides a thorough analysis of the principles, mathematics, and analytical tools used in chemical, microbial, and reactor kinetics. It also presents a comprehensive, up-to-date description of the kinetics of important chemical processes in aquatic environments. Aquatic photochemistry and correlation methods (e.g., LFERs and QSARs) to predict process rates are covered. Numerous examples are included, and each chapter has a detailed bibliography and problems sets. The book will be an excellent text/reference for professionals and students in such fields as aquatic chemistry, limnology, aqueous geochemistry, microbial ecology, marine science, environmental and water resources engineering, and geochemistry.
Introducing the application of free energy correlations to elucidating the mechanisms of organic and bio-organic reactions, this book provides a new and illuminating way of approaching a potentially complex topic. The idea of how free energy correlations derive from polar substituent change is introduced, and common pitfalls encountered in the application of free energy relationships are described, along with the use of these anomalies in mechanistic studies. The concept of effective charge is described in detail, with examples of its application. Throughout, worked answers are provided for the problems posed. Databases of parameters, an extensive bibliography and comprehensive lists of further reading are also included. The text provides an invaluable source of information to senior undergraduates, postgraduates and to industrial researchers with an interest in mechanistic studies. It is the first such book in more than thirty years.
The Sixth Edition of a classic in organic chemistry continues its tradition of excellence Now in its sixth edition, March's Advanced Organic Chemistry remains the gold standard in organic chemistry. Throughout its six editions, students and chemists from around the world have relied on it as an essential resource for planning and executing synthetic reactions. The Sixth Edition brings the text completely current with the most recent organic reactions. In addition, the references have been updated to enable readers to find the latest primary and review literature with ease. New features include: More than 25,000 references to the literature to facilitate further research Revised mechanisms, where required, that explain concepts in clear modern terms Revisions and updates to each chapter to bring them all fully up to date with the latest reactions and discoveries A revised Appendix B to facilitate correlating chapter sections with synthetic transformations
Since its original appearance in 1977, Advanced Organic Chemistry has found wide use as a text providing broad coverage of the structure, reactivity and synthesis of organic compounds. The Fourth Edition provides updated material but continues the essential elements of the previous edition. The material in Part A is organized on the basis of fundamental structural topics such as structure, stereochemistry, conformation and aromaticity and basic mechanistic types, including nucleophilic substitution, addition reactions, carbonyl chemistry, aromatic substitution and free radical reactions. The material in Part B is organized on the basis of reaction type with emphasis on reactions of importance in laboratory synthesis. As in the earlier editions, the text contains extensive references to both the primary and review literature and provides examples of data and reactions that illustrate and document the generalizations. While the text assumes completion of an introductory course in organic chemistry, it reviews the fundamental concepts for each topic that is discussed. The Fourth Edition updates certain topics that have advanced rapidly in the decade since the Third Edition was published, including computational chemistry, structural manifestations of aromaticity, enantioselective reactions and lanthanide catalysis. The two parts stand alone, although there is considerable cross-referencing. Part A emphasizes quantitative and qualitative description of structural effects on reactivity and mechanism. Part B emphasizes the most general and useful synthetic reactions. The focus is on the core of organic chemistry, but the information provided forms the foundation for future study and research in medicinal and pharmaceutical chemistry, biological chemistry and physical properties of organic compounds. The New Revised 5th Edition will be available shortly. For details, click on the link in the right-hand column.
Of Part A.- 1. Chemical Bonding and Molecular Structure.- 1.1. Valence-Bond Approach to Chemical Bonding.- 1.2. Bond Energies, Lengths, and Dipoles.- 1.3. Molecular Orbital Theory.- 1.4. Hückel Molecular Orbital Theory.- General References.- Problems.- 2. Stereochemical Principles.- 2.1. Enantiomeric Relationships.- 2.2. Diastereomeric Relationships.- 2.3. Dynamic Stereochemistry.- 2.4. Prochiral Relationships.- General References.- Problems.- 3. Conformational and Other Steric Effects.- 3.1. Steric Strain and Molecular Mechanics.- 3.2. Conformations of Acyclic Molecules.- 3.3. Conformations o.