Reactive chemical pathway of tributyl phosphate with nitric acid

• Published in: Process safety and environmental protection Vol. 116; pp. 677 - 684
• Main Authors: Smitha, V.S., Kumar, J. Samuel Vara, Surianarayanan, M., Seshadri, H., Lakshman, N.V.
• Format: Journal Article
• Language: English
• Published: Rugby Elsevier B.V 01-05-2018; Elsevier Science Ltd
• Subjects: Accelerating rate calorimeter; Butanol; Chemical compounds; Degradation products; Diluents; Dilution; Exothermic reactions; High temperature; Nitric acid; Oil; Organic chemistry; Oxidation; Phosphates; Reaction pathway; Solvents; Spectrum analysis; Thermal hazards; Tri butyl phosphate; Thermal hazards; Tri butyl phosphate; Nitric acid; Accelerating rate calorimeter; Reaction pathway; Diluents
• ISSN: 0957-5820; 1744-3598
• DOI: 10.1016/j.psep.2018.03.028

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•Focus to bring deeper insight in predicitng the reason for red oil explosions.•Mechanistic pathway for the red oil forming reaction is validated.•Accelerating Rate Calorimeter was used to study the thermal behavior.•Strength of nitric acid was found to alter the reaction pathway.•Revealed the diluents undergoing exothermic reaction even in absence of Tribuyl Phosphate.
Tributyl phosphate and its degradation products saturated with nitric acid and exposed to elevated temperatures lead to an accidental condition known as “reactive red oil formation”. The present study aims at elucidating the chemical pathway of this reaction in an Accelerating Rate Calorimeter (ARC). The thermal characteristics obtained from ARC coupled with end product analysis using spectroscopic techniques proved that red-oil forming mechanisms varied as per the concentration of nitric acid. The chemical pathway for red oil formation was found to occur through the oxidation of butanol at lower temperatures and with dilute nitric acid, the predominant path was via butyl nitrite intermediate at higher temperatures. Independent ARC experiments with butanol and butyl nitrite with nitric acid validated the mechanism. This study also revealed that most of the diluents employed for TBP undergo exothermic reaction with nitric acid, even in the absence of TBP.