Acids and bases are ubiquitous in chemistry. Our understanding of them, however, is dominated by their behaviour in water. Transfer to non-aqueous solvents leads to profound changes in acid-base strengths and to the rates and equilibria of many processes: for example, synthetic reactions involving acids, bases and nucleophiles; isolation of pharmaceutical actives through salt formation; formation of zwitter- ions in amino acids; and chromatographic separation of substrates. This book seeks to enhance our understanding of acids and bases by reviewing and analysing their behaviour in non-aqueous solvents. The behaviour is related where possible to that in water, but correlations and contrasts between solvents are also presented. Fundamental background material is provided in the initial chapters: quantitative aspects of acid-base equilibria, including definitions and relationships between solution pH and species distribution; the influence of molecular structure on acid strengths; and acidity in aqueous solution. Solvent properties are reviewed, along with the magnitude of the interaction energies of solvent molecules with (especially) ions; the ability of solvents to participate in hydrogen bonding and to accept or donate electron pairs is seen to be crucial. Experimental methods for determining dissociation constants are described in detail. In the remaining chapters, dissociation constants of a wide range of acids in three distinct classes of solvents are discussed: protic solvents, such as alcohols, which are strong hydrogen-bond donors; basic, polar aprotic solvents, such as dimethylformamide; and low-basicity and low polarity solvents, such as acetonitrile and tetrahydrofuran. Dissociation constants of individual acids vary over more than 20 orders of magnitude among the solvents, and there is a strong differentiation between the response of neutral and charged acids to solvent change. Ion-pairing and hydrogen-bonding equilibria, such as between phenol and phenoxide ions, play an increasingly important role as the solvent polarity decreases, and their influence on acid-base equilibria and salt formation is described.
Les mer
This book seeks to enhance our understanding of acids and bases by reviewing and analysing their behaviour in non-aqueous solvents. The behaviour is related where possible to that in water, but correlations and contrasts between solvents are also presented.
Les mer
1. Introduction ; 2. Acid-base equilibria: quantitative treatment ; 3. Solvation and acid-base strength ; 4. Determination of dissociation constants ; 5. Protic solvents ; 6. High-basicity, aprotic solvents ; 7. Low-basicity and low-polarity aprotic solvents ; 8. Acid-base equilibria and salt formation ; 9. Appendices: Dissociation constants in methanol and aprotic solvents ; Index
Les mer
Acidbase equilibria are intimately coupled to many of the processes involved in synthetic and analytical chemistry, including reaction rates and selectivity, solubility and partition equilibria, catalytic cycles and chromatographic retention times. These equilibria are extraordinarily sensitive to the nature of the solvent, with some equilibrium constants changing by as much as 1010 on transfer from water to aprotic solvents. This book, by a practitioner with a lifetimes experience in the area, dissects a complex subject and provides a clear discussion of the several interacting factors that determine ionisation behaviour. It will be an invaluable resource to scientists involved with chemistry in non-aqueous solvents.
Les mer
The first extensive, systematic coverage of acids and bases in non-aqueous solvents Presentation and analysis of dissociation constants in different classes of non-aqueous media Widespread correlations between dissociation constants and acid and solvent type Quantitative aspects of acid-base chemistry Practical details on the measurement of dissociation constants
Les mer
Dr Brian G. Cox was educated at the University of Melbourne, followed by academic research or teaching posts at the Australian National University, the University of Stirling, Cornell University, and the Max-Planck Institut für biophys. Chemie, Göttingen. He subsequently held industrial positions of Corporate Research Associate with ICI and Syngenta, and Associate Principal Scientist and Consultant with AstraZeneca. In addition, he has held Visiting Professorships at the Universities of Surrey, St Andrews, Bologna, and Chieti, and University College, Dublin, and most recently acted as Senior Advisor in Chemistry at the Institute of Chemical and Engineering Science in Singapore.
Les mer
The first extensive, systematic coverage of acids and bases in non-aqueous solvents Presentation and analysis of dissociation constants in different classes of non-aqueous media Widespread correlations between dissociation constants and acid and solvent type Quantitative aspects of acid-base chemistry Practical details on the measurement of dissociation constants
Les mer

Produktdetaljer

ISBN
9780199670512
Publisert
2013
Utgiver
Vendor
Oxford University Press
Vekt
528 gr
Høyde
247 mm
Bredde
200 mm
Dybde
14 mm
Aldersnivå
UP, 05
Språk
Product language
Engelsk
Format
Product format
Innbundet
Antall sider
156

Forfatter

Biographical note

Dr Brian G. Cox was educated at the University of Melbourne, followed by academic research or teaching posts at the Australian National University, the University of Stirling, Cornell University, and the Max-Planck Institut für biophys. Chemie, Göttingen. He subsequently held industrial positions of Corporate Research Associate with ICI and Syngenta, and Associate Principal Scientist and Consultant with AstraZeneca. In addition, he has held Visiting Professorships at the Universities of Surrey, St Andrews, Bologna, and Chieti, and University College, Dublin, and most recently acted as Senior Advisor in Chemistry at the Institute of Chemical and Engineering Science in Singapore.