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Acid dissociation constants of protonated substituted pyridine N-oxides and cationic homoconjugation constants of these acids with conjugate N-oxides have been determined by potentiometric titration in mixed polar non-aqueous solvents (acetonitrile - acetone and acetonitrile - dimethyl sulfoxide) with increasing (from 0 to 1) mole fraction of acetonitrile. In acetonitrile - dimethyl sulfoxide mixtures, the acid dissociation constants (expressed as pKa) and cationic homoconjugation constants (expressed as log KBHB+) vary non-linearly with increasing mole fraction of acetonitrile. In systems with the least basic N-oxides, local minima of pKa have been observed. In acetonitrile-acetone mixtures, both the pKa and the cationic homoconjugation constant values changed irregularly in the acid-base systems studied and the character of those variations could not be unambiguously determined.
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Tom
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1341--1350
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- Department of General Chemistry, University of Gdańsk, Sobieskiego 18, 80-952, Gdańsk, Poland
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bwmeta1.element.baztech-article-BUJ1-0019-0042