INVESTIGATION OF SOLVATION IN LITHIUM PERCHLORATE -PROPYLENE CARBONATE-DIMETHYL CARBONATE SYSTEM BY RAMAN SPECTROSCOPY

Abstract

The difference of solvent properties can significantly affect the solvation phenomena in individual and, especially, in mixed solutions. In particular, it can be assumed that in mixed solvents, i.e. in systems with intermediate dielectric permittivity (mixtures of linear and cyclic carbonic acid esters), cations will bind molecules of linear esters more strongly and bind molecules of cyclic esters more weakly than it takes place in individual solvents. In the present work the Raman spectra of lithium perchlorate solvents in propylene carbonate (PC), dimethyl carbonate (DMC) and their mixture in a wide range of salt concentrations are studied. It is shown that the solvation effects of the cation are clearly traced in the region of symmetric ring vibrations (~690-730 cm-1) of propylene carbonate and in the region of deformation vibrations of CCA (~520 cm-1) of dimethyl carbonate. These effects are also evident in the mixed solvent. The so-called method of differential spectroscopy was used to judge the structural changes of mixed-solvent systems. It consisted in constructing spectra of lithium salt solutions in mixed solvents, additive sum of spectra of lithium salt solutions in PC and DMC, as well as their difference (differential spectra). The analysis of differential spectra allows us to conclude that in systems with mixed solvent there is a weakening of interaction of propylene carbonate molecules with ions, and there is a preferential solvation of cations and anions by dimethyl carbonate molecules. Also, unlike propylene carbonate, dimethyl carbonate solvates perchlorate ions, which follows from the line contour changes in the region of CH3-group vibrations (2970 cm-1) solvation of anions is also observed in the mixed solvent. For citation: Rabadanov K.Sh., Gafurov M.M., Akhmedov M.A., Rabadanova D.I., Magomedova A.G. Investigation of solvation in lithium perchlorate -propylene carbonate-dimethyl carbonate system by raman spectroscopy. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2024. V. 67. N 5. P. 36-42. DOI: 10.6060/ivkkt.20246705.6967.