Abstract

The νC=O frequency for ethylene carbonate is in Fermi resonance with the first overtone of the skeletal breathing mode, and the extent of Fermi interaction is affected by solvent/solvent interaction. The νC=O frequencies have been corrected for Fermi resonance, and the corrected νC=O frequencies have been correlated with the mole % CHCl<sub>3</sub>/CCl<sub>4</sub>, (CH<sub>3</sub>)<sub>2</sub>SO/CCl<sub>4</sub> (CH<sub>3</sub>)<sub>2</sub>SO/CHCl<sub>3</sub>, and CHCl<sub>3</sub>/<i>n</i>-C<sub>6</sub>H<sub>14</sub>, the solvent reaction field, and νC=O for acetone recorded in the same solvents. Solute/solvent interactions are discussed. The acceptor number of the solvent vs. the νC=O frequencies apparently correlates in a different manner for the solvents which form intermolecular hydrogen bonds with the solute. Steric factors are suggested as being one of the reasons that the AN values and νC=O frequencies do not give nonambiguous correlations. The νC=O mode for ethylene carbonate shifts continuously to lower frequency as the mole % CHCl<sub>3</sub> or (CH<sub>3</sub>)<sub>2</sub>SO increases in each of the solvent mixtures studied.

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