Infrared spectrum of HDO in aqueous solutions of perchlorates and tetrafluoroborates

Abstract

The OH and OD stretching bands of HDO in aqueous solutions containing the ions ClO4− and BF4− are split into two components. The high-frequency component, A, does not shift with temperature. It is interpreted as due to OH groups involved in weak [Formula: see text] or [Formula: see text] hydrogen bonds. This interpretation is in line with the corresponding OH frequencies of other systems containing ClO4− ions, such as methanolic solutions and crystalline hydrates. Solvent-separated ion pairs may account for the observed cation effect on band A. The low-frequency component, B, varies with temperature almost exactly like the corresponding band of pure water. It is interpreted to be due to those OH groups which are not associated with the anion. Components A and B are not resolved in solutions of most electrolytes because the distribution of strengths of interactions of OH groups with most anions overlaps that of [Formula: see text] interactions between water molecules.