Ionic Interactions in Aqueous Solution: A Raman Spectral Study

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Abstract
The vibrational and the electronic spectra of the nitrate ion change with concentration in aqueous solutions of metallic nitrates M (NO3) n , and the changes vary with the cation M n+ present in the solution. The position, size, shape, and polarization of the ν1 Raman band of the nitrate ion and the position of the nearultraviolet absorption band of that ion have been measured as functions of concentration in solutions of the nitrates of Li, Na, K, NH4, Mg, Ca, Zn, and Al. Three correlations emerge from these data. (1) The changes in the peak frequency and in the half‐width of the Raman band are inversely related, and both appear to depend on the degree of hydration of the cation. (2) The changes in the specific intensity of the Raman band are paralleled by shifts in the ultraviolet absorption band and are resonance Raman effects. (3) In solutions of ammonium nitrate the spectral changes are very small, apparently because of the similarity between the ammonium ion and the water molecule.

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