Infrared Spectra of Ices II, III, and V in the Range 4000 to 350 cm—1

Journal Article · Wed Jan 01 00:00:00 EST 1964 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.1725374· OSTI ID:4068384

Bertie, J. E.; Whalley, E.

The infrared spectra of Ices II, III, and V between 4000 and 350 cm^-1 were obtained. The ices were made at appropriate pressure and temperatures, cooled under pressure to liquid-nitrogen temperature, and removed from the pressure vessel. Mulls were made near liquid-nitrogen temperature using isopentane or perfluoropropane as mulling agents, and the spectra of the mulls at approximates 100 deg K were recorded. The spectra of ices made from H₂O, D₂O, 5% H₂O in D₂O, 5% D₂O in H₂O, and, for Ices II and III, 1% D₂O in H₂O were obtained. In general features, the spectra of pure H₂O and D₂O Ices II, III, and V are similar to those of Ice I. For most bands there is a shift of frequency from that in Ice I towards the vapor frequencies, but the shift is small compared with the shift between Ice I and the vapor. Ices II, III, and V are therefore essentially fully hydrogen bonded and are probably four coordinated. This agrees with a proposed structure for Ice III. In Ices II and III the bands due to the O-- H and the O--D stretching vibrations of HDO in dilute solution in D₂O and H₂O, respectively, show a good deal of fine structure, and are quite narrow, the half- width of the O--D bands being about 5 cm^-1. These are by far the sharpest O- H (or O-- D) stretching vibrations of hydrogenbonded O-- H-----O groups so far observed. Clearly, breadth is not inherent in the O-- H stretching bands of O-- H------O. There is also a good deal of fine structure in the bands due to rotational vibrations of water molecules in Ices II and III, and much of this fine structure broadens and weakens when a small amount of H₂O is added to D₂O, and of D₂O to H₂O The only simple explanation of this, and of the fine structure of the O-- H stretching bands, is that the hydrogen atoms in Ices II and III are ordered. No corresponding fine structure occurs in Ice V, and the hydrogen atoms are probably disordered, as in Ice I.

• Research Organization: National Research Council, Ottawa
• Sponsoring Organization: USDOE
• NSA Number: NSA-18-016022
• OSTI ID: 4068384
• Journal Information: Journal of Chemical Physics, Vol. 40, Issue 6; Other Information: Orig. Receipt Date: 31-DEC-64; ISSN 0021-9606
• Publisher: American Institute of Physics (AIP)
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION
ATOMS
CONFIGURATION
COOLING
CRYSTALS
DIAGRAMS
ENERGY LEVELS
FREQUENCY
HEAVY WATER
HYDROGEN
ICE
INFRARED RADIATION
ISOMERS
ISOTOPE EFFECTS
LATTICES
LOW TEMPERATURE
MEASURED VALUES
MIXING
MOLECULES
NUMERICALS
ORGANIC FLUORINE COMPOUNDS
OSCILLATIONS
PENTANE
PHASE DIAGRAMS
PHOTOMETRY
PREPARATION
PRESSURE
PROPANE
QUANTITY RATIO
ROTATION
SAMPLING
SPECTRA
SPECTRAL SHIFT
SPECTROSCOPY
TABLES
USES
VAPORS
VESSELS
WATER