ESR Study of NO3 and NO2 Produced on uv Irradiation of HNO3 Solutions at 77°K

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Abstract
The paramagnetic species produced on uv photolysis of nitric acid at 77°K were studied using electron spin resonance. The primary photochemical process HNO3→OH+NO2 is followed by OH+HNO3→H2O+NO3. Three species are observed. One species is a triplet and is characteristic of the NO2 spectrum. The second is a singlet in H14NO3 (g=2.018) and a nonfully resolved doublet in H15NO3. On the basis of its blue color, absorption spectrum, photodecomposition on irradiation in its wave bands, competitive elimination on addition of OH radical scavengers, and hyperfine structure it is identified as the NO3 radical. The third species (g=2.0075), is produced as a product of the photodecomposition of NO3, and is tentatively assigned to NO.

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