Ionic association and solvation in solutions of magnesium and nickel perchlorates in acetonitrile |
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| Authors: | O. N. Kalugin V. N. Agieienko N. A. Otroshko V. V. Moroz |
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| Affiliation: | (1) Karazin Kharkiv National University, Kharkiv, Ukraine |
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| Abstract: | The paper presents the conductometric data on solutions of Mg(ClO4)2 and Ni(ClO4)2 in acetonitrile over the temperature ranges 5–55°C for Mg(ClO4)2 and 25–75°C for Ni(ClO4)2. The extended Lee-Wheaton equation for unsymmetrical electrolytes was used to determine the limiting equivalent conductivities of the Mg2+, Ni2+, and ClO 4 ? ions and first-step ionic association constants with the formation of [KtClO4]+ ion pairs. Lower ionic association constants for Ni(ClO4)2 compared with Mg(ClO4)2 were a consequence of stronger non-Coulomb repulsion in the formation of [KtClO4]+ ion pairs because of the formation of a firmer solvation shell by the nickel compared with magnesium cation. The structure-dynamic parameter of ionic solvation was estimated. It was found that spatial-time correlations in the nearest environment of ions increased in the series ClO 4 ? > Mg2+ > Ni2+. |
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