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Thermal decomposition of nitrated tributyl phosphate

Conference ·
OSTI ID:210292
; ; ;  [1]
  1. Georgia Institute of Technology, Atlanta, GA (United States)

Tri-n-butyl phosphate (TBP), nitric acid and water mixtures are subject to thermal decomposition. The gaseous and liquid decomposition product yields are highly path dependent. Higher temperatures accelerate decomposition rates, but may result in lower extent of reaction than comparable low temperature cases. Actual extent of reaction, and gaseous by-products generation, are affected by the presence of Zr(IV), condensate reflux back into the reaction vessel, the water/HNO{sub 3} and the HNO{sub 3}/TBP molar ratios, and whether the decomposition occurs at isobaric or constant volume conditions. Higher gaseous production results from condensate reflux, lower H{sub 2}O/HNO{sub 3} ratios, and with excess HNO{sub 3} and water present as a second liquid phase. Principal gaseous products include N{sub 2}, CO, CO{sub 2}, NO and N{sub 2}O. Measurable concentrations of NO{sub 2} were not observed, although gas coloration indicative of NO{sub 2} were obsessed during the beginning of decomposition measurements. Principal liquid products are dibutyl phosphoric acid and butyl nitrate. Air sparging of TBP solutions (e.g., thru transfers using air lift pumps) may increase the hazards of TBP decomposition reactions by lowering the H{sub 2}O/HNO{sub 3} molar ratios. Runaway reactions were not observed under the conditions of this study. Possible reaction mechanisms and pathways are discussed.

OSTI ID:
210292
Report Number(s):
CONF-9509139--
Country of Publication:
United States
Language:
English

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