HYDROGEN PEROXIDE AND ITS ANALOGUES: VI. INFRARED SPECTRA OF H₂O₂, D₂O₂, AND HDO₂

Abstract

The absorption spectrum of hydrogen peroxide was re-examined with a prism instrument in the region 1.5 to 25p. A pair of well-resolved perpe~iclicular bands arising from torsional oscillation of the OH groups \\?ere found centered about 460 and 575 cm.?. The overtone band a t 3 . 8 ,~ was shown to be a hybrid with prominent rotational str~rcture and some indicatio~is of doubling. Its assignnlent to the combination v?+vs implies a positive anharrnonicity. Four new overtone bands were observed in liquid hydrogen peroxide. The infrared spectrum of d c u t e r i~~l n peroxide was ~neasured for the first time in the solid and vapor states. Previous investigations of the ~nolecular spectrum of hydrogen peroxide (2, 6, 10, 30, 34) have served to confirm the structure now accepted for that molecule but, otherwise, they have left unanswered a number of important questions, such as the assignment of the weak band a t 3.SP and the frequency of the four symmetric modes, especially v r the torsional oscillation. In an eiiort to solve some of these problems the infrared spectrum of that compound was measured again under a wider range of conditions than covered heretofore. In addition, the completely cleuterated peroxide was prepared and its spectrum in the vapor state was recorded for the first time. RiIixtures of these two isotopic peroxides mere used to obtain valuable information on the hybricl molecule HDO?. Unlortunately, study of the latter was severely limited by interference from the parent molecules HzOz and D z 0 2 , always present in large proportions, in addition to traces of HzO, DzO, and HDO. Finally the spectra of the three peroxides dissolved in a non-polar solvent have helped elucidate the region of the 0-H and 0-D stretching fundamentals. While the subject remains far from exhausted the new results have made possible calculation of the force constants of the molecule (11) and an appreciable refinement in our knowledge of the structural parameters.

Infrared Spectra and Radiation Stability of H2O2 Ices Relevant to Europa

“…A weak near-IR feature at 4725 cm Ϫ1 can be seen in the upper trace of Fig. 1, which is reasonably close to the 4775 cm Ϫ1 value reported for room-temperature liquid H 2 O 2 (Bain and Giguère, 1955). Comparing the area of the narrow 2821 cm Ϫ1 band with that of the broad 4725 cm Ϫ1 band showed them to be in a ratio of about 6.5:1.…”

Hydrogen Peroxide on the Surface of Europa

“…Similar arguments rule out other simple hydrocarbons and ammonium-bearing minerals (18). A more like- ly candidate for the 3.50-|xm feature is H 2 0 2 , which produces 2v 2 , v 2 +v 6 , and 2v 6 combination-bending-mode absorption (19,20) at -3.5 |xm and has been predicted to occur on icy satellite surfaces (6). For comparison to the NIMS data, we measured (21) the diffuse reflectance of H 2 0 2 mixtures in water ice and found a band at 3.504 |xm (Fig.…”

Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H2O Complexes with Oxidants

“…[36] This proposal, however, was refuted when the skew structure of H 2 O 2 was established. In 1955, Bain and Giguerre [37] proposed the existence of new tautomeric forms of H 2 O 2 and undertook a special investigation in order to detect them on the basis of IR spectra of H 2 O 2 isotopomers, but failed. Later, the concept of the participation of oxywater as an intermediate of oxidative processes was frequently used in many studies.…”