Low temperature infrared spectroscopic studies of the solvation of perchlorate ions

✍ Scribed by Imants M. Strauss; Martyn C.R. Symons

• Publisher: Elsevier Science
• Year: 1976
• Tongue: English
• Weight: 188 KB
• Volume: 39
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(76)80306-5

✦ Synopsis

Methanolic solutions containiig perchlorate ions dispIay a resolved, high-frequency O-H stretching band which shifts to lower frequencies on cooling, bat frozen aqueous glasses reveal two such bands, one in the (OH)free re$on (3570 cm-') and one at lower frequencies (ca. 3400 cm-').

The O-H stretching region of the vibrational spectrum of waier and hydroxylic solvents is generally a broad series of overlapping ban& that are hardly modified by the addition of electrolytes or nonelectrolytes. The band is narrowed and simplified because of decoupling when dilute solutions of HOD in Hz0 (O-D oscillator) or in D20 (O-H oscillator) are used but, still, in general, remains rather uninformative. However, solutions of perchlorates and related salts exhibit a resolved feature on the high frequency side of the main band and, therefore, such solutions have attracted considerable attention. Some workers have favoured an cxplanation proposed by Walrafen [ 1 ] , that this high-frequen-