Solvation spectra. Part 39.—Infra-red and Raman studies of aqueous and non-aqueous solutions containing perchlorates

Abstract

The O—H stretching frequency for methanol in the system methanol + dichloromethane + tetra-alkylammonium perchlorate is almost equal to that for a band which appears when perchlorate salts are dissolved only in methanol. The band is therefore assigned to methanol molecules hydrogen-bonded to perchlorate anions. A band which appears in the spectrum of HOD in H₂O when perchlorates are added is, by analogy, similarly assigned. Other arguments against a previous theory that, for aqueous solutions, this band is due to free OD groups, are advanced. The influence of the cation upon the band for solvent molecules not associated with perchlorate ions is discussed.