Publication costs assisted by The Pillsbury CompanyThe b a n spectra of dissolved carbon dioxide at ca. 10 "C and 45 atm pressure are reported for the two solvents H20 and D20. Comparisons are made with spectra of the gas and liquid phases of C02. Results indicate that only one species, COz(aq), is detected in solution by the experimental technique employed, and that HZC03 and other carbonates have insufficient concentrations in pure water for us to observe them directly. Attention is given to the significant spectral changes in COz(aq) upon change in solvents, H20 to D20.

The infrared and Raman spectra for the polyhalide ions (ICl2−, ICl4−, BrCl2−, and Br3−) are presented. From these data, the X—Y stretching force constant fr, the interaction force constants frr between bond stretching coordinates at 180° to each other, and the interaction force constant frr′ for bond stretching coordinates at an angle of 90° (for ICl4−) have been calculated. The values of fr for the trihalide ions are roughly one-half the values for the free halogens, and the values of the interaction force constants frr are very large (approximately 35% the value of the stretching constant fr). These rather unusual force constants have been interpreted in terms of the description of the bonding in these ions using p orbitals, which was first suggested by Pimentel. In fact, these results offer rather strong support for the recent evidence from nuclear quadrupole coupling constant measurements of Cornwell and Yamasaki favoring this structure. Attention is drawn to the qualitative similarity between these force constants and those for the HF2− ion.

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An experimental procedure for obtaining the reflection spectrum in the infrared from solid benzene is described. The results are analyzed according to the method of Robinson and Price to give the index of refraction n and the absorption coefficient κ as a function of frequency. Integration of the latter gives the absolute intensity Γi of the ith fundamental, without requiring a knowledge of the path length. Since the path length is the most uncertain variable in the evaluation of absolute intensities from absorption measurements in condensed phases, the intensity results even from these relatively crude reflection measurements are probably as accurate as those from absorption studies. Comparisons are made with other studies on benzene, and the discrepancies are discussed.