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 % CHCl₃/CCl₄, (CH₃)₂SO/CCl₄ (CH₃)₂SO/CHCl₃, and CHCl₃/<i>n</i>-C₆H₁₄, 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 % CHCl₃ or (CH₃)₂SO increases in each of the solvent mixtures studied.

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