Chemistry of Organic Nitrates: Thermal Oxidative and Catalytic Chemistry of Organic Nitrates
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Abstract
Our previous research showed that the rates for unimolecular thermal fragmentation of the O−N bond of organic nitrates are the same in air as they are under a nitrogen atmosphere. This is contrary to what literature studies have reported. When the rate of reaction was followed by infrared (IR) spectroscopy, as in previous literature studies, the IR absorption of the unsaturated carbonyls generated during the reaction complicated the IR analysis and the rates deceptively appeared to slow in air. The current study shows that unsaturated carbonyls can also be formed under a nitrogen atmosphere when hydroperoxide is added. Hydroperoxides created naturally most likely give rise to the unsaturated carbonyl compounds when the reaction is carried out in air. Evidence suggests that the products of organic nitrate thermal chemistry accelerate the decomposition of the model hydroperoxide. The details of this chemistry are critical for controlling the oxidation of hydrocarbons. The reaction of organic nitrates with v...