Acids and bases : solvent effects on acid-base strength / Brian G. Cox.

Format:

Book

Author/Creator:

Cox, Brian G.

Language:

English

Subjects (All):

Acid-base chemistry.

Acids.

Physical Description:

1 online resource (339 p.)

Place of Publication:

Oxford : Oxford University Press, 2013.

Summary:

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. Thisbook seeks to enhance our understanding of acids and bases by reviewing and analysing their behaviour in non-aqueous

Contents:

Cover; Title Page; Copyright Page; Contents; 1 Introduction; 1.1 Why are non-aqueous solvents important?; 1.1.1 Range of accessible pH-values; 1.1.2 Reactivity of acids and bases; 1.1.3 Ionizable compounds and high-performance liquid chromatography (HPLC); 1.2 Classification of solvents and their properties; 1.2.1 Electron donor-acceptor properties of solvents; References; 2 Acid-Base Equilibria: Quantitative Treatment; 2.1 Definitions; 2.2 pH and acid-base ratios; 2.3 pH-dependence of species distribution; 2.4 Acid strengths and molecular structure: dissociation constants in water

3.3.3 Solvation in mixed solvents3.4 Solvation of non-electrolytes; 3.5 Solvation energies and solvent properties; 3.6 Solvation and acid strength; 3.7 Summary; Appendix 3.1 Composition of mixed solvents; References; 4 Determination of Dissociation Constants; 4.1 pH-scales; 4.1.1 pH in aqueous media; 4.1.2 pH in non-aqueous media; 4.2 Influence of solution concentration: activity coefficients; 4.3 Ion association; 4.4 Homohydrogen-bond formation; 4.5 Experimental methods for the determination of dissociation constants; 4.5.1 Potentiometric titration using a glass electrode

4.5.2 Acid-base indicators4.6 Autoionization constants of solvents; Appendix 4.1 Dissociation of acetic acid in the presence of sodium chloride; Appendix 4.2 Ion-pair formation and pKa-determination; Appendix 4.3 Determination of homohydrogen-bond association constants, KAHA; References; 5 Protic Solvents; 5.1 Autoionization constants; 5.2 Methanol; 5.2.1 Neutral acids: carboxylic acids, phenols; 5.2.2 Cationic acids: protonated anilines, amines, N-heterocycles; 5.2.3 Summary; 5.3 Higher alcohols; 5.4 Alcohol-water mixtures; 5.5 Salt formation in alcohols and aqueous-alcohol mixtures

5.6 Formamide, acetamide, N-methylpropionamide5.7 Formic acid; References; 6 High-Basicity Polar Aprotic Solvents; 6.1 Dimethylsulphoxide; 6.1.1 Neutral acids: carboxylic acids, phenols and thiophenols, water and methanol, anilines and amides, carbon acids; 6.1.2 Cationic acids (neutral bases); 6.1.3 Amino acids; 6.2 N-methylpyrrolidin-2-one, N, N-dimethylformamide, N, N-dimethylacetamide; 6.2.1 Neutral acids; 6.2.2 Cationic acids (neutral bases); 6.3 Liquid ammonia; 6.4 Summary; 6.5 Estimation of dissociation constants in basic aprotic solvents; References

7 Low-Basicity and Low-Polarity Aprotic Solvents

Notes:

Includes index.

ISBN:

0-19-164934-1

1-283-94385-9

0-19-164933-3