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Acids and BasesSolvent Effects on Acid-Base Strength$
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Brian G. Cox

Print publication date: 2013

Print ISBN-13: 9780199670512

Published to Oxford Scholarship Online: May 2013

DOI: 10.1093/acprof:oso/9780199670512.001.0001

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Determination of Dissociation Constants

Determination of Dissociation Constants

(p.39) 4 Determination of Dissociation Constants
Acids and Bases

Brian G. Cox

Oxford University Press

The determination of dissociation constants in non-aqueous and mixed-aqueous solvents is described. pH-scales, upon which the dissociation constants are based, are defined and compared with the corresponding aqueous scales. Experimental measurements, mostly based on potentiometric titrations using a glass electrode or spectrophotometric measurements of acid-base equilibria, are detailed. Absolute pKa-values are typically anchored to suitable indicator acids, such as picric acid, whose dissociation constants can be conveniently determined by several independent methods. Solute–solute interactions, especially specific association reactions, such as ion-pair and homohydrogen-bond formation, invariably accompany, and often dominate, acid–base equilibria in non-aqueous media. In mixed-aqueous solvents, simultaneous electrode calibration and pKa-determination may be achieved in a single, simple potentiometric titration. The measurement of autoionization constants, which quantify the tendency of a solvent to self-ionize, is also described.

Keywords:   pH-scales, glass electrodes, acid–base indicators, activity coefficients, ion association, homohydrogen-bonds, solvent autoionization

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