Acids and bases :

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 a...

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Bibliographic Details
Main Author: Cox, Brian G.
Format: Printed Book
Published: Oxford : Oxford University Press, 2013.
Subjects:
Acids.
Bases (Chemistry)
Solvents.
Table of 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.

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