to 171.67.34.69. Redistribution subject to AIP license or copyright; see http://jcp.aip.org/about/rights_and_permissions 768 HUNTER, DAVENPORT, AND SETTEponents. Although Pinkerton and Bauer have already shown that molecules of high reaction rate greatly alter the absorption when added to molecules of low reaction rate, our results in the relaxation region show that the result is a mutual one.
A.Raman spectra excited by 4880-A argon-ion-Iaser radiation and recorded photoelectrically have been obtained from a series of ternary aqueous solutions by back scattering and by 90° scattering using Cary and Jarrell-Ash double monochromators, respectively. The OD stretching region of HDO (and D 2 0), 2300-2800 cm-I, and the OH stretching region of H 20 plus HDO, ~2800-3800 cm-I, were examined for the following solutes: ((C.H,).NCI, and (15) Xe. (See Addendum for other solutes.) In addition, Raman spectra were obtained from HDO in H20 at pressures from 1 to 3790 bar at 25°C, and from a 5.0M solution of NaCIO. in HDO and H 20 at pressures of 690 and 3450 bar at 25°C. Several pronounced intensity maxima were observed in the OD and OH stretching regions for salts of extremely strong acids, (1)-(4), and some qualitative correlations with the strengths of the corresponding acids were found for (1)-(10). Solutes (1)-(11) were also found to act as structure breakers in water, but (12) was found to enhance structure, and some hydrogen bonding was found for (13). Further, no significant spectral effects were noted for (15) when the Xe concentration of the molten clathrate hydrate was 0.8M at 70°C and 1720 bar. For (14), however, an intense low-frequency OD stretching component was observed near 2483 cm-I • The (C 4 H,).N+ cation is the first found to produce pronounced effects in the OD and OH stretching regions, and the 2483 cm-I OD stretching component appears to arise from a marked structure-making effect. The effect of pressure on the OD stretching contour of HDO in H 20 was observed to be small. Only a slight decrease in the frequency of the nonhydrogen-bonded component centered near 2660 cm-I was uncovered to pressures of 3790 bar, and no significant pressure effect was observed for the NaCIO. solution to 3450 bar. The highpressure spectra indicate that pressure is not very effective in breaking the hydrogen bonds in water, and the filling of holes as the result of a redistribution of angles and distances in the hydrogen-bonded network is suggested as a more important effect.