Pernitric acid, decomposition

Den Hertog and Overhoff - observed that when pyridine in sulfuric acid is added to molten potassium sodium nitrate the 3-nitro derivative is formed at 300°C, whereas at 450°C 2-nitropyridme is the main product. The latter is probably a free-radical process. Schorigin and Toptschiew obtained 7-nitroquinoline by the action of nitrogen peroxide on quinoline at 100°C, possibly through the homolytic addition of NOa. Laville and Waters reported that during the decomposition of pernitrous acid in aqueous acetic acid, quinoline is nitrated in the 6- and 7-positions. They considered that the reaction proceeds as shown in Scheme 3. 

The 0-0 bond in peroxides and hydroperoxides is often rather weak. Pernitrous acid already decomposes readily at room temperature (see below), and the decomposition of peroxodisulfate at 70 °C is used in technical processes, but H202... 

Graham, R. A., Winer, A. M., Pitts, J. N., Jr., "Temperature Dependence of the Uni-molecular Decomposition of Pernitric Acid and Its Atmospheric Implications," Chem. Phys. Lett. (1978) in press. 

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