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

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

Author/Creator:
Cox, Brian G.
Edition:
1st ed.
Publication:
Oxford : Oxford University Press, 2013.
Format/Description:
Book
xii, 143 p. : ill. ; 25 cm.
Subjects:
Acids.
Bases (Chemistry)
Solvents.
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.
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.
Notes:
Includes bibliographical references and index.
Local notes:
Acquired for the Penn Libraries with assistance from the George R. Fink Memorial Fund.
Contributor:
George R. Fink Memorial Fund.
ISBN:
9780199670512 (hbk)
019967051X (hbk)
9780199670529 (pbk)
0199670528 (pbk)
Publisher no.:
99953841215
Web link:
The George R. Fink Memorial Fund Home Page
The George R. Fink Memorial Fund Home Page  Bookplate