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Hydrogen bonding in hydrogen peroxide and water. A Raman study of the liquid state
Author(s) -
Giguère Paul A.,
Chen Hung
Publication year - 1984
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1250150313
Subject(s) - supercooling , raman spectroscopy , hydrogen peroxide , hydrogen bond , chemistry , molecule , anhydrous , hydrogen , liquid water , crystallography , spectral line , analytical chemistry (journal) , organic chemistry , thermodynamics , physics , astronomy , optics
The Raman spectra of pure, anhydrous H 2 O 2 and its deuteriated analogues, D 2 O 2 and HDO 2 , were examined in the liquid state up to 40 °C and supercooled down to −75 °C. The OH ( OD ) stretching bands show a broad, single‐peaked contour, and a strongly temperature‐dependent asymmetry‐ Decomposition by analog computer reveals two overlapping bands, about 100 cm −1 apart, with different temperature behavior. In contrast with water, there is no indication in the hydrogen peroxide spectra of ‘free,’ i.e. non‐hydrogen‐bonded, OH groups, in keeping with the flexible geometry of the molecule and its electronic configuration. Based on these spectra, and by analogy with water, a two‐state model is proposed featuring a continuum of hydrogen‐bonded H 2 O 2 molecules, with elose‐packed OH groups in two kinds of environments. The hydrogen bonds are slightly weaker (12–15%) than those in water. Hydrogen peroxide is the best analog for studying the structure of water.