Abstract

Three factors appear to affect <i>n</i>-alkane molecular vibrations in CHCl₃/CCl₄ solutions. These are: (1) Physical restriction of the νCH₃ and νCH₂ vibrations by solvent molecules. (2) Intermolecular hydrogen bonding between <i>n</i>-alkane protons and the free pair of electrons on Cl atoms of either CCl₄ or CDCl₃. The positively charged alkane protons arise during the dipole moment changes, δ<i>P</i>/δ<i>Q</i>, occurring during a full cycle of the νCH₃ and νCH₂ modes. (3) The physical restriction of solvent molecules, which is greater in the case of CDCl₃ than in the case of CCl₄ due to a high degree of CDCl₃ orientation about <i>n</i>-alkane molecules due to repulsion of the C-D of CDCl₃ by the <i>n</i>-alkane νCH₃ and νCH₂ protons, which allows stronger C-D:Cl bonds to be formed between solute and solvent.

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