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- Raman study of cation and anion solvation is performed.
- Solvation numbers of cations are close to two and do not vary with concentration.
- Solvation numbers of anions are close to four in concentrated solutions.
- Solvation phenomena do not determine the properties of salt systems.
Raman study of cation and anion solvation in dimethyl sulfoxide, propylene carbonate and dimethyl carbonate solutions of six lithium salts has been performed in the concentration range from 0.05 to 0.25 molar fraction of a salt. The dependences of the amount of the solvent particles involved in dimerization, hydrogen bonding, and solvation have been determined, and the mean solvation numbers have been found. It is concluded that in all solutions studied, notwithstanding the differences in the physical properties of the solvent and in the structure of the anion, both the lithium cation and the anion solvation equilibria are quantitatively similar. In all cases, solvation numbers of cations are close to two and do not vary with the growth of concentration. In particular, in molten LiXÂ·4S solvates, LiS4+ entities expected from the phase diagrams do not exist. It has been found that for the solvent molecules in dimers and in solvation spheres, non-coincidences between vibrational frequencies of isotropic and anisotropic lines, ÎÎ½NCEÂ =Â Î½anisoÂ âÂ Î½iso are of opposite signs signifying that the mutual orientation of molecules is different. In all systems studied, solvation numbers of anions decrease if the salt content is growing and are close to four in concentrated solutions. These striking similarities in the structure and concentration of solvated entities clearly signify that solvation phenomena have no decisive importance in determining the properties of salt systems.
Journal: Journal of Molecular Liquids - Volume 205, May 2015, Pages 98-109