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Abstract: Clegg–Pitzer–Brimblecombe ion-interaction semi-empirical approach was rarely exploited for modeling electrolyte, particularly, in mixed solvent systems. Indeed, a review of the literature shows that the use of an exact and complete form of this model (PSC) was only limited to the works of two research groups for the investigation of electrolyte in mixed solvent systems. In this work, we have used both Pitzer and PSC ion-interaction theoretical approaches for modeling the non-ideal behavior of HCl in the ternary HCl+methanol+water electrolyte system. The modeling purposes were achieved based on the experimental determination of the mean molal activity coefficients for HCl in this ternary system by using the potentiometric data of a galvanic cell containing a pH glass membrane and Ag/AgCl electrodes. The measurements were performed over the electrolyte molality ranging from 0.01 up to 5.75mol/kg in mixed methanol (x%)+water (100− x%) solvent, with solvent mass fraction percents: x%=10, 20, 30, 40 and 50%, at 298.15±0.05K. [Copyright &y& Elsevier]

Abstract: A LFE (Linear Free Energy) analysis of kinetic data for different organic reactions in various organic aqueous solutions was carried out. The rate constants of these reactions were compared with those for the solvolysis of tert-butyl chloride in the same solvents in terms of the LFE Relationships, and linear plots were observed in a wide range of the co-solvent content. This similarity points to a common nature of the solvent effect in these reactions in variety of water–organic mixtures, regardless of largely different reaction mechanisms. We explain these results by the prevalence of hydrophobic stabilization of the initial state of these reactions in water-rich solvent mixtures. Recently the same conclusion was also made on the basis of investigations into sonication effects in kinetics of organic reactions. A considerable contribution of hydrophobic effects to the Y scale by Grunwald and Winstein was deduced. [Copyright &y& Elsevier]