Decomposition of the Tributyl Phosphate-Nitrate Complexes

Abstract

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Aeriometallurgical Extraction of Rare Earth Elements from a NdFeB Magnet Utilizing Supercritical Fluids

“…With the data above combined, the stoichiometry of the chelating agents was determined as the following: X 6 = −1, TBP­(H 2 O) 0.387 (HNO 3 ) 1.224 ; X 6 = 0, TBP­(H 2 O) 0.405 (HNO 3 ) 1.352 ; X 6 = +1, TBP­(H 2 O) 0.560 (HNO 3 ) 1.969 . At the studied temperatures (35–55 °C for a maximum of 2 h), the TBP–HNO 3 complex was expected to be stable. , However, careful safety precautions must be taken while handling this system because, in a pressure vessel, there is a risk of exothermic reactions between TBP and HNO 3 . Depending on the pressure, acid concentration, and residence time, the onset temperature for exothermic self-accelerating oxidation processes in TBP–HNO 3 mixtures is 117 °C and potentially lower depending if alcohols are present, which could result in hazardous reactions under certain reaction conditions. , As such, particular care and caution must be taken to ensure that experiments are carried out within safe operating parameters.…”

“…At the studied temperatures (35−55 °C for a maximum of 2 h), the TBP− HNO 3 complex was expected to be stable. 25,26 However, careful safety precautions must be taken while handling this system because, in a pressure vessel, there is a risk of exothermic reactions between TBP and HNO 3 . Depending on the pressure, acid concentration, and residence time, the onset temperature for exothermic self-accelerating oxidation processes in TBP−HNO 3 mixtures is 117 °C27 and potentially lower depending if alcohols are present, which could result in hazardous reactions under certain reaction conditions.…”

Initial concepts on energetics and mass releases during nonnuclear explosive events in fuel cycle facilities

“…Tables 3.6, 3.7, and 3.8 present data from Nichols (1960) on red oil explosions. Table 3.6 presents the heat of reaction of 100% tributyl phosphate and 10,7 M nitric acid at various temperatures.…”

“…Table 3,7 is a series of correction factors for concentration effects to be used for other tributyl phosphate and nitric acid concentrations. For example, "red oil" prepared from 30% tributyl phosphate and 4 M nitric acid would have a correction factor of 0.20, If the mixture is assumed to explode at 140°C, the heat of reaction would be (0,20)(367) = 73,4 Btu/lb or 41 cal/g, "Red oil" under these conditions would be about 4% as powerful an explosive as TNT, The maximum explosive power of "red oil" would be if a mixture formed from concentrated nitric acid and 100% TBP exploded at 160°C, The explosion of 1 lb of "red oil" under these conditions would be equivalent to about 0,23 lb of TNT, The effect of temperature upon the heat of reaction of "red oil" indicates that it may be desirable to estimate the actual temperature at which the Frequency factor x (s'-^) 43 x 10^ 24 x 10^ 7.6 x lo' (a) Nichols (1960) reaction occurs. The calculation below is taken from Nichols (1960) and is based on a heat balance for the reactor vessel.…”