Reactivity of tributyl phosphate degradation products with nitric acid: Relevance to the Tomsk-7 accident
- Westinghouse Hanford Company, Richland, WA (United States)
The reaction of a degraded tributyl phosphate (TBP) solvent with nitric acid is thought to have caused the chemical explosion at the Tomsk-7 reprocessing plant at Tomsk, Russia in 1993. The estimated temperature of the organic layer was not high eneough to cause significant reaction of nitric acid with TBP or hydrocarbon diluent compounds. A more reactive organic compound was likely present in the organic layer that reacted with sufficient heat generation to raise the temperature to the point where an autocatalytic oxidation of the organic solvent was initiated. Two of the most likely reactive compounds that are present in degraded TBP solvents are n-butanol and n-butyl nitrate. The reactions of these compounds with nitric acid are the subject of this study. The objective of laboratory-scale tests was to identify chemical reactions that occur when n-butanol and n-butyl nitrate contact heated nitric acid solutions. Reaction products were identified and quantitified, the temperatures at which these reactions occur and heats of reaction were measured, and reaction variables (temperature, nitric acid concentration, organic concentration, and reaction time) were evaluated. Data showed that n-butyl nitrate is less reactive than n-butanol. An essentially complete oxidation reaction of n-butanol at 110-120 C produced four major reaction products. Mass spectrometry identified the major inorganic oxidation products for both n-butanol and n-butyl nitrate as nitric oxide and carbon dioxide. Calculated heats of reaction for n-butanol and n-butyl nitrate to form propionic acid, a major reaction product, are -1860 cal/g n-butanol and -953 cal/g n-butyl nitrate. These heats of reaction are significant and could have raised the temperature of the organic layer in the Tomsk-7 tank to the point where autocatalytic oxidation of other organic compounds present resulted in an explosion.
- OSTI ID:
- 210286
- Report Number(s):
- CONF-9509139--
- Country of Publication:
- United States
- Language:
- English
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