Acids and Bases by Cox, Brian G. -- Read -- Imperial Library of Trantor

Index

Cover 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

2.4.1 The strength of the X–H bond 2.4.2 Charge dispersion on anions, A[sup(-0], or cations, BH[sup(+)] 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

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 Appendix 4.1 Dissociation of acetic acid in the presence of sodium chloride Appendix 4.2 Ion-pair formation and pK[sup(a)]-determination Appendix 4.3 Determination of homohydrogen-bond association constants, K[sup(AHA)] 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

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 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

Index

A B C D E F G H I K L M N P R S T V W Z

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