Solvent Effects in Chemistry Second Edition by Erwin Buncel and Robert A. Stairs.
1 Physicochemical Foundations
2 Unreactive Solvents
3 Reactive Solvents
4 Chemometrics: Solvent Effects and Statistics
5 Theories of Solvent Effects
6 Dipolar Aprotic Solvents
7 Examples of Other Solvent Classes
8 New Solvents and Green Chemistry
9 Concluding Observations
Preface to the Second Edition:
The present work is in effect the second edition of Buncel, Stairs, and Wilson’s (2003) The Role of the Solvent in Chemical Reactions. In the years since the appearance of the first edition, the repertoire of solvents and their uses has changed considerably. Notable additions to the list of useful solvents include room‐temperature ionic liquids, fluorous solvents, and solvents with properties “switchable” between different degrees of hydrophilicity or polarity. The use of substances at temperatures and pressures near or above their critical points as solvents of variable properties has increased. Theoretical advances toward understanding the role of the solvent in reactions continue. There is currently much activity in the field of kinetic solvent isotope effects. A search using this phrase in 2002 yielded 118 references to work on their use in elucidating a large variety of reaction mechanisms, nearly half in the preceding decade, ranging from the SN2 process (Fang et al., 1998) to electron transfer in DNA duplexes (Shafirovich et al., 2001). Nineteen countries were represented: see, for example, Blagoeva et al. (2001), Koo et al. (2001), Oh et al. (2002), Wood et al. (2002). A similar search in 2013 yielded over 25,000 “hits.”
The present edition follows the pattern of the first in that the introductory chapters review the basic thermodynamics and kinetics needed for describing and understanding solvent effects as phenomena. The next chapters have been revised mainly to improve the presentation. The most changed chapters are near the end, and attempt to describe recent advances.
Some of the chapters are followed by problems, some repeated or only slightly changed from the first edition, and a few new ones. Answers to most are provided. We are grateful to two anonymous colleagues who reviewed the first edition when this one was first proposed, and who pointed out a number of errors and infelicities. One gently scolded us for using the term “transition state” when the physical entity, the activated complex, was meant. He or she is right, of course, but correcting it in a number of places required awkward circumlocutions, which we have shamelessly avoided (see also Atkins and de Paula, 2010, p. 844.). We hope that most of the remaining corrections have been made. We add further thanks to Christian Reichardt for steering us in new directions, and we also thank Nicholas Mosey for a contribution to the text and helpful discussions, and Chris Maxwell for Figure 5.11. We add David Poole, Keith Oldham, J. A. Arnot, and Jan Myland to the list of persons mentioned in the preface to the first edition who have helped in different ways. Finally, we thank the editorial staff at Wiley, in particular Anita Lekhwani and Cecilia Tsai, for patiently guiding us through the maze of modern publishing and Saravanan Purushothaman for careful copy-editing that saved us from many errors. Any errors that remain are, of course, our own.
EB, Kingston, Ontario
RAS, Peterborough, Ontario
April 15, 2015
Preface to the First Edition:
The role of the solvent in chemical reactions is one of immediate and daily concern to the practicing chemist. Whether in the laboratory or in industry, most reactions are carried out in the liquid phase. In the majority of these, one or two reacting components, or reagents, with or without a catalyst, are dissolved in a suitable medium and the reaction is allowed to take place. The exceptions, some of which are of great industrial importance, are those reactions taking place entirely in the gas phase or at gas–solid interfaces, or entirely in solid phases. Reactions in the absence of solvent are rare, though they include such important examples as bulk polymerization of styrene or methyl methacrylate. Of course, one could argue that the reactants are their own solvent.
Given the importance of solvent, the need for an in‐depth understanding of a number of cognate aspects seems obvious. In the past, many texts of inorganic and organic chemistry did not bother to mention that a given reaction takes place in a particular solvent or they mentioned the solvent only in a perfunctory way. Explicit discussion of the effect of changing the solvent was rare, but this is changing. Recent texts, for example, Carey (1996), Clayden et al. (2001), Solomons and Fryhle (2000), Streitwieser et al. (1992), devote at least a few pages to solvent effects. Morrison and Boyd (1992) and Huheey et al. (1993) each devote a whole chapter to the topic.
It is the aim of this monograph to amplify these brief treatments, and so to bring the role of the solvent to the fore at an early stage of the student’s career. Chapter 1 begins with a general introduction to solvents and their uses. While it is assumed that the student has taken courses in the essentials of thermodynamics and kinetics, we make no apology for continuing with a brief review of essential aspects of these concepts. The approach throughout is semiquantitative, neither quite elementary nor fully advanced. We have not avoided necessary mathematics, but have made no attempt at rigor, preferring to outline the development of unfamiliar formulas only in sufficient detail to avoid mystification.
The physical properties of solvents are first brought to the fore in Chapter 2, entitled “The Solvent as Medium,” which highlights, for example, Hildebrand’s solubility parameter, and the Born and Kirkwood–Onsager electrostatic theories. An introduction to empirical parameters is also included. Chapter 3, “The Solvent as Participant,” deals chiefly with the ideas of acidity and basicity and the different forms in which they may be expressed. Given the complexities surrounding the subject, the student is introduced in Chapter 4 to empirical correlations of solvent properties. In the absence of complete understanding of solvent behavior, one comes to appreciate the attempts that have been made by statistical analysis (chemometrics) to rationalize the subject. A more theoretical approach is made in Chapter 5, but even though this is entitled “Theoretical Calculations,” there is in fact no rigorous theory presented. Nevertheless, the interested student may be sufficiently motivated to follow up on this topic. Chapters 6 and 7 deal with some specific examples of solvents: dipolar‐aprotic solvents like dimethylformamide and dimethyl sulfoxide and more common acidic/basic solvents, as well as chiral solvents and the currently highlighted room‐temperature ionic liquids. The monograph ends with an appendix, containing general tables. These include a table of physical properties of assorted solvents, with some notes on safe handling and disposal of wastes, lists of derived and empirical parameters, and a limited list of values.
A few problems have been provided for some of the chapters. We were fortunate in being able to consult a number of colleagues and students, including (in alphabetical order) Peter F. Barrett, Natalie M. Cann, Doreen Churchill, Robin A. Cox, Robin Ellis, Errol G. Lewars, Lakshmi Murthy, Igor Svishchev, and Matthew Thompson, who have variously commented on early drafts of the text, helped us find suitable examples and references, helped with computer problems, and corrected some of our worst errors. They all have our thanks.
Lastly, in expressing our acknowledgments we wish to give credit and our thanks to Professor Christian Reichardt, who has written the definitive text in this area with the title Solvents and Solvent Effects in Organic Chemistry (2nd Edn., 1988, 534 p.). It has been an inspiration to us to read this text and on many occasions we have been guided by its authoritative and comprehensive treatment. It is our hope that having read our much shorter and more elementary monograph, the student will go to Reichardt’s text for deeper insight.
EB, Kingston, Ontario
RAS, Peterborough, Ontario
HW, Montreal, Quebec
⏩Edition: 2nd Edition
⏩Authors: Erwin Buncel and Robert A. Stairs
⏩Puplication Date: August 3, 2015
⏩Size: 6.01 MB
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