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. Solvent properties are reviewed, along with the
magnitude of the interaction energies of solvent molecules with
(especially) ions; the ability of solvents to participate in hydrogen
bonding and to accept or donate electron pairs is seen to be crucial.
Experimental methods for determining dissociation constants are
described in detail. In the remaining chapters, dissociation constants
of a wide range of acids in three distinct classes of solvents are
discussed: protic solvents, such as alcohols, which are strong
hydrogen-bond donors; basic, polar aprotic solvents, such as
dimethylformamide; and low-basicity and low polarity solvents, such as
acetonitrile and tetrahydrofuran. Dissociation constants of individual
acids vary over more than 20 orders of magnitude among the solvents,
and there is a strong differentiation between the response of neutral
and charged acids to solvent change. Ion-pairing and hydrogen-bonding
equilibria, such as between phenol and phenoxide ions, play an
increasingly important role as the solvent polarity decreases, and
their influence on acid-base equilibria and salt formation is
described.
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Solvent Effects on Acid-Base Strength
Produktdetaljer
ISBN
9780191649349
Publisert
2020
Utgiver
Vendor
OUP Oxford
Språk
Product language
Engelsk
Format
Product format
Digital bok
Forfatter