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Journal of Spectroscopy
Volume 2016, Article ID 6978560, 12 pages
Review Article

Speciation in Solutions of Lithium Salts in Dimethyl Sulfoxide, Propylene Carbonate, and Dimethyl Carbonate from Raman Data: A Minireview

1Joint Department of Electrochemical Energy Systems, 38A Vernadsky Ave., Kyiv 03142, Ukraine
2Kh. I. Amirkhanov Institute of Physics and Analytical Center of Common Access, 94 M. Yaragsky St., Makhachkala 367003, Russia

Received 19 August 2016; Accepted 10 October 2016

Academic Editor: Christoph Krafft

Copyright © 2016 M. I. Gorobets et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


Our recent Raman studies of cation and anion solvation and ion pairing in solutions of lithium salts in dimethyl sulfoxide, propylene carbonate, and dimethyl carbonate are briefly overviewed. Special attention is paid to differences in our and existing data and concepts. As follows from our results, cation solvation numbers in solutions are low (~2) and disagree with previous measurements. This discrepancy is shown to arise from correct accounting for dimerization, hydrogen bonding, and conformation equilibria in the solvents disregarded in early studies. Another disputable question touches upon the absence of free ions in solutions of lithium salts in carbonate solvents and the statement that the charge transfer in carbonate solutions is caused by SSIPs. Direct proofs of the nature of charge carriers in the solvents studied have been obtained by means of analyses of vibrational dynamics. It has been found that collision times for free anions are short and evidence weak interactions between anions and solvent molecules. In SSIPs, collision times are an order of magnitude longer thus signifying strong interactions between anions and cations. In CIPs, collision times become shorter than in SSIPs reflecting the transformation of the structure of concentrated solutions to that of molten salts.