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Kinetic Basicities of Aqueous Binary Mixtures: A Surprisingly Good Linear Correlation with the Gas Phase Basicity of the Organic Cosolvent
Author(s) -
Pines Ehud,
Fleming Graham R.
Publication year - 1993
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.199300022
Subject(s) - chemistry , protonation , solvation , proton , hydrogen bond , molecule , aqueous solution , phase (matter) , organic molecules , proton affinity , solvent , organic base , ion , inorganic chemistry , computational chemistry , organic chemistry , physics , quantum mechanics
A remarkably good correlation between the rate of proton transfer from excited protonated 1‐aminopyrene and the gas phase basicities of the organic component in water: organic solvent binary mixtures has been found. We suggest that use of anilinium acids minimizes the effect of anion solvation and Coulomb interactions and enables the influence of the organic cosolvent on the proton transfer to be clearly observed. The model proposed is one in which the proton is always transferred to a water molecule and a concerted proton transfer to a water molecule solvated by the organic cosolvent also occurs. The cosolvent influence is then on this latter species via hydrogen bond interactions. The correlation holds in pure water but not in pure organic solvents where, clearly, the proton must be transferred to the organic molecule.