Synthesis and characterization of red-oil from tri iso-amyl phosphate/n-dodecane/nitric acid mixtures at elevated temperature

Das, Biplab; Kumar, Shekhar; Mondal, Prasenjit; Mudali, U. Kamachi; Natarajan, R.

doi:10.1007/s10967-012-1671-8

Cited by 15 publications

(7 citation statements)

References 12 publications

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“…e cyclic alkanes are the easiest to form nitro compound, followed by n-butanol, and n-alkanes are the least reactive to form the nitro compounds. at is consistent with the previous studies [1,3,7,14]. It can be also found that the long n-alkanes are easier to react with nitric acid to form the nitro compound than those of the short ones.…”

Section: Energies Along the Reaction Pathways And Rate Constantssupporting

confidence: 93%

“…e so-called "red oil" was found following several accidents occurring when organic materials inadvertently get into the equipment and overheat with uranyl nitrate and/or nitric acid at uranium processing facilities. However, only some organic compounds can react with uranyl nitrate and/or nitric acid, forming the red oil [3,[7][8][9][10]. Since more accidents have happened due to the formation and violent decomposition of red oil [4,[8][9][10], there was a dawning realization that the formation and decomposition of red oil have become a risk.…”

Section: Introductionmentioning

confidence: 99%

“…Nazin et al reported thermal explosions in mixtures of TBP with nitric acid [14,24]. And Gordon et al studied the decomposition of red oil by simulating these accidents conditions experimentally [1,7]. Kumar et al also reported the thermal decomposition of red oil with nitric acid [25].…”

Section: Introductionmentioning

confidence: 99%

“…However, there are majority of investigations concerned with red oil experimentally, which only focus on the degradation of TBP or TBP/HNO 3 system, as well as the factors that influence these reactions. e nitrogen-containing organic materials are the most undesirable waste tank components in the "red oil" accidents, since they are energetic species in their own right [3,7]. However, there are limited investigations about them.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study on the Mechanism for the Formation of Nitro Compounds in Red Oil

Tian

Tang

et al. 2020

Journal of Chemistry

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The mechanisms involved in reactions between methane, n-hexane, n-butanol, cyclohexane, and nitric acid were explored by density functional theory calculations. All the calculations in gas phase and n-tributyl phosphate (TBP) solvent were performed at the B3LYP/6–311++G ∗ ∗ and CCSD(T)/6–311++G ∗ ∗ levels of theory. The results showed that TBP has an important effect on the reactions between nitric acid and alkanes or butanol. The reactions were considered as that the radicals (·NO2 and ·NO3 radicals are formed via the HNO3 decomposition under irradiation) initiate the H-atom depletion of the reactants (R), and the produced radicals in red oil combine with ·NO2 radical to form the nitro compounds spontaneously. The rate constants of reactions R + ·NO2 and R + ·NO3 differ substantially, the rate constants of the latter being much larger than those of the former. In the reactions of R + ·NO3, the transition states and products are 20 kJ/mol and 100 kJ/mol or more stable than the reactants, respectively, but the reactions of R + ·NO2 need to overcome energy barriers over 25 kJ/mol. The formations of products mainly depend on the reactions of R + ·NO3. For the same type of alkanes (either chain or cyclic ones), the lower the relative stabilities of carbon-centered radicals are, the more reactive the alkanes are. Cyclohexane is the most competitive species, followed by n-butanol, n-alkanes, and methane which are the least competitive.

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Section: Energies Along the Reaction Pathways And Rate Constantssupporting

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Theoretical Study on the Mechanism for the Formation of Nitro Compounds in Red Oil

Tian

Tang

et al. 2020

Journal of Chemistry

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“…In order to separate the actinides from other metals, this mixture is then transferred to a kerosene system employing organophosphorus compounds. Historically, this process has been found to generate a red colored, unspecified organic phase consisting of a trialkylphosphate and nitric acid, which is referred to as “Red Oil”. − When this material is heated above 120 °C, explosions and fires have occurred, resulting in several incidents in the United States and across the world. − Due to the potential risks within this system, a great deal of research into characterizing the properties of Red Oil and identifying the products formed during this process has been undertaken. − Studies concerning the scattering of the particulates from actinide-containing fires rely heavily on particle dispersion data collected in the early 1970s . As part of a revamping of these outdated data, this effort focused on identifying the various components of the solution system and characterizing the particulates formed during a burn event.…”

Section: Introductionmentioning

confidence: 99%

Organophosphorus-Modified Lanthanide Nitrates as Potential Actinide Oxide Aerosol Surrogates

et al. 2020

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In search of suitable simulants for aerosol uranium waste products from Plutonium Uranium Redox Extraction (PUREX) process burns, a series of lanthanide nitrate hydrates ([Ln(κ 2 -NO3)3·nH2O]) were dissolved in the presence of tributylphosphate (OP(O(CH2)3CH3)3) referred to as TBP) in kerosene or triphenylphosphate (OP(O(C6H5) referred to as TPhP) in acetone. The crystal structure of the TPhP derivatives of the lanthanide nitrate series and uranium nitrate were solved as [Ln(κ2 -NO3)3(TPhP)3] (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) and [U(O)2(κ2 -NO3)2(TPhP)2] (U), respectively. The lanthanide-TBP, Ln, and U were further characterized using FTIR spectroscopy, 31P NMR spectroscopy, thermogravimetric analysis, and X-ray fluorescence spectroscopy. Further, thermal treatment of the lanthanide-TBP, Ln, and U using a box furnace to mimic pyrolysis conditions was found by PXRD analyses to generate a phosphate phase [LnP3O9 or UP2O7) for all systems. The resultant nuclear waste fire contaminant particulates will impact both aerosol transport and toxicity assessments.

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Densities and Molar Volumes for Binary Solutions of Tri-iso-Amyl Phosphate and n-Dodecane in the Temperature Range of 283.15–363.15 K

Kumar

2024

Int J Thermophys

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Tri-n-butyl phosphate (TBP) has remained workhorse of PUREX based nuclear recycle operations since 1956. However due to its associated disadvantages like third phase formation and tendency to react violently with nitric acid at elevated temperatures generated requirement of an alternate extractant for PUREX process. Tri-iso-amyl phosphate (TiAP) has better attributes than TBP on both the counts. Density of solutions is an important process parameter for design of equipment, process operations and control and safety analysis. In this work, experimental data on the density of binary solution of tri-iso amyl phosphate and n-dodecane are reported for several temperature levels. The related volumetric parameters were also estimated from experimental data as well as Kirkwood–Buff integrals. Derivative parameters like linear coefficients of preferential solvation $$\delta_{ij(i \ne j)}^{o}$$ δ i j ( i ≠ j ) o and local mole fractions $$x_{ij(i \ne j)}$$ x i j ( i ≠ j ) at 298.15 K were also estimated and reported. Graphical Abstract

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Synthesis and characterization of red-oil from tri iso-amyl phosphate/n-dodecane/nitric acid mixtures at elevated temperature

Cited by 15 publications

References 12 publications

Theoretical Study on the Mechanism for the Formation of Nitro Compounds in Red Oil

Theoretical Study on the Mechanism for the Formation of Nitro Compounds in Red Oil

Organophosphorus-Modified Lanthanide Nitrates as Potential Actinide Oxide Aerosol Surrogates

Densities and Molar Volumes for Binary Solutions of Tri-iso-Amyl Phosphate and n-Dodecane in the Temperature Range of 283.15–363.15 K

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