Вісники НТУ "ХПІ"

The type of short range solvation of Li⁺ , Na⁺ K⁺ , Rb⁺ , Cs⁺ , NH₄⁺ , Cl⁻ , Br⁻ , I⁻, ClO₄⁻ ions has been determined and analyzed in formamide (FA), Nmethylformamide (MFA), N-dimethylformamide (DMF) at 298.15 K. In order to determine the type of ion solvation we used familiar-variable quantitative parameter (d – ri), where d is the translational displacement length of ion, ri is its structural radius. It was found that the difference (d – ri) is equal to the coefficient of attraction friction (CAF) of ions normalized to the solvent viscosity and hydrodynamic coefficient. The sign of the CAF is determined by the sign of the algebraic sum of its ion-molecular and intermolecular components. In amide solutions the studied cations are cosmotropes (positively solvated ((d – ri) > 0), structure-making ions) and anions are chaotropes (negatively solvated ((d – ri) < 0 ), structurebreaking ions). In the amide series, regardless of the sign (d – ri), the near-solvation enhances, which can be explained by the weakening of the specific interaction between the solvent molecules. The decrease of d and respectively (d – ri) with increasing cation radius in a given solvent is the result of weakening of its coordinating force due to the decrease of charge density in the series Li⁺–Na⁺–K⁺–Rb⁺–Cs⁺ . The increase of d (and (d – ri), correspondingly) for the ions studied in the series FA-MFA-DMF can be explained by the weakening of intermolecular interactions in this series, which leads to the strengthening of solvation. It was found that for the halide ions in the series FA-MFA-DMF the regular growth of d parameter is explained by the weakening of the solvent structure. It was shown that Li⁺ ion with the lowest diffusion coefficient among cations and the highest d value forms kinetically stable complexes in amide solutions.

Вісники НТУ "ХПІ"

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