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Acids and bases : solvent effects on acid-base strength
- Author
- Cox, Brian G.
- Title
- Acids and bases : solvent effects on acid-base strength / Brian G. Cox.
- Format
- Book
- Edition
- 1st ed.
- Published
- Oxford : Oxford University Press, 2013.
- Description
- xii, 143 p. : ill. ; 25 cm.
- Notes
- Includes bibliographical references and index.
- Contents
-
- Machine generated contents note: 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
- 2.4.1. The strength of the X-H bond
- 2.4.2. Charge dispersion on anions, A-, or cations, BH+
- 2.4.3. The nature of X in R-X-H
- 2.5. Carbon acids
- 2.6. Acid-base equilibria
- Appendix 2.1 Species distribution in acid-base systems
- References
- 3. Solvation and Acid-Base Strength
- 3.1. Solvation and acid dissociation constants: free energies of transfer
- Contents note continued: 3.1.1. Solvent-transfer activity coefficients
- 3.2. Determination of free energies of transfer
- 3.2.1. Non-electrolytes
- 3.2.2. Electrolytes
- 3.3. Free energies of ion solvation
- 3.3.1. Hydration of ions
- 3.3.2. Solvation in pure solvents
- 3.3.3. Solvation in mixed solvents
- 3.4. 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 indicators
- 4.6. Autoionization constants of solvents
- Contents note continued: 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-methylpropionamide
- 5.7. 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
- Contents note continued: 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
- 7.1. Acetonitrile
- 7.1.1. Neutral acids: carboxylic acids and phenols, carbon acids
- 7.1.2. Cationic acids (neutral bases)
- 7.2. Propylene carbonate, sulpholane, acetone, methyl iso-butyl ketone, nitrobenzene
- 7.3. Tetrahydrofuran
- References
- 8. Acid-Base Equilibria and Salt Formation
- 8.1. Charge-neutral equilibria
- 8.2. Charge-forming equilibria
- 8.2.1. Alcohols and mixed-aqueous solvents
- 8.2.2. Polar aprotic solvents
- 8.2.3. Non-polar aprotic solvents
- References
- 9. Appendices: Dissociation Constants in Methanol and Aprotic Solvents
- 9.1. Methanol
- 9.1.1. Carboxylic acids and phenols
- 9.1.2. Protonated nitrogen bases
- 9.2. Dimethylsulphoxide
- 9.2.1. Carboxylic acids, alcohols, phenols
- Contents note continued: 9.2.2. Inorganic acids and miscellaneous
- 9.2.3. Anilines, anilides, amides (N-H-ionization)
- 9.2.4. Carbon acids: ketones, esters, nitroalkanes
- 9.2.5. Carbon acids: nitriles, sulphones
- 9.2.6. Carbon acids: fluorenes
- 9.2.7. Cationic acids: anilinium, ammonium, pyridinium ions
- 9.3. N, N-Dimethylformamide
- 9.3.1. Neutral acids
- 9.3.2. Cationic acids
- 9.4. Acetonitrile
- 9.4.1. Neutral acids
- 9.4.2. Inorganic acids and miscellaneous
- 9.4.3. Cationic acids: ammonium, anilinium, pyridinium ions
- 9.4.4. Phosphazene bases
- 9.5. Tetrahydrofuran
- 9.5.1. Neutral acids
- 9.5.2. Cationic acids.
- 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. 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.
- Subject headings
- Acids. Bases (Chemistry) Solvents.
- ISBN
- 9780199670512 (hbk) 019967051X (hbk) 9780199670529 (pbk) 0199670528 (pbk)