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Ionic equilibrium in mixtures of protophobic and protophilic polar non‐hydrogen bond donor solvents: acids,salts, and indicators in acetone containing 5 mol% DMSO
Authors:Nikolay O Mchedlov‐Petrossyan  Dmitriy Yu Filatov  Sergey T Goga  Alexander V Lebed
Institution:Department of Physical Chemistry, V. N. Karazin Kharkov National University, 61077, Kharkov, Ukraine
Abstract:Properties of a protophobic polar non‐HBD solvent can be strongly modified by introduction of a small amount of a protophilic polar non‐HBD solvent. In this paper, acetone (AC) with 5 mol% additive of DMSO, a solvent with equation image , was considered as a media for acid–base reactions. Conductance was used for determination of dissociation constants of a set of salts, hydrogen chloride, and picric acid. The last‐named was also studied by UV‐vis spectroscopy. The introduction of 5 mol% of DMSO results in suppressing, to some extent, the homoconjugation processes in AC media as well as of proton hydration by (possible) traces of water. The dissociation of salicylic acid and 2,4‐dinitrophenol was examined utilizing quinhydrone electrodes in a cell with liquid junction. The pKa values of buffer acids and equation image values of buffer solutions were calculated by taking into account the incomplete dissociation of salts. The response of the glass electrode appeared to be satisfactory, which allowed the estimation of the pKa value of benzoic acid. The apparent ionization constants of 22 acid–base indicators in buffer mixtures and perchloric acid solutions were determined in (AC + 5 mol% DMSO) using the spectrophotometric procedure. Copyright © 2009 John Wiley & Sons, Ltd.
Keywords:acetone–  DMSO mixed solvent  acids  apparent ionization constant  conductance  dissociation constant  glass electrode  indicator dyes  quinhydrone electrode  salts  UV‐vis spectroscopy
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