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Chemical Structure| 112724-94-4 Chemical Structure| 112724-94-4

Structure of 112724-94-4

Chemical Structure| 112724-94-4

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Sosulin, Ilya S ; Lisouskaya, Aliaksandra ;

Abstract: The thermal evolution of electron-beam-induced radicals generated in neat di-n-butyl N,N-diethylcarbamoylphosphonate (DBDECP), N,N-bis(2-ethylhexyl)butanamide (DEHBA), dioctyl phosphate (DOP), tributyl phosphate (TBP), and N,N,N′,N′-tetraoctyl diglycolamide (TODGA), and TBP/dodecane extraction system was investigated using electron paramagnetic resonance (EPR) spectroscopy over the temperature range of 108−220 K. Density functional theory (DFT) calculations were employed to support the experimental results, clarifying radical structures and energetics of their thermal transformations. The stability of radicals as temperature increased varied significantly depending on the ligand structure. The diglycol- or amide-centered radicals, such as those found in TODGA and DEHBA, exhibited higher thermal stability than the alkyl radicals. This increased stability is attributed to the greater steric hindrance in the latter species. Calculated energy barriers (∼20 kcal/mol) suggested that thermal evolution predominantly involves conformational rearrangements of the radicals, rather than transformations of the radical structure itself. Additionally, trace amounts of oxygen led to the conversion of carbon-centered radicals into peroxide radicals during thermal annealing. The peroxide radicals formed decomposed more rapidly at elevated temperatures. This study provides important mechanistic insights into the radiolytic degradation of nuclear waste extraction ligands, helping to advance the development of more radiation-resistant solvents for nuclear waste separation processes.

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Ilya S. Sosulin ; Aliaksandra Lisouskaya ;

Abstract: Radical intermediates derived from di-n-butyl N,N-diethylcarbamoylphosphonate (DBDECP), N,N-bis(2-ethylhexyl)butanamide (DEHBA), dioctyl phosphate (DOP), tributyl phosphate (TBP), N,N,N,N-tetraoctyl diglycolamide (TODGA), and octyl(phenyl)-N,N-diiso-butylcarbamoylmetliylphosphine oxide (CMPO), were examined by EPR spectroscopy at 77 K. In all cases, carbon-centered radicals originating from alkyl or amide compounds were consistently identified in the experimental spectra. The spectral assignment was based on the advanced quantum chemical calculation at the DFT(B3LYP)/L1a_3 level of theory allowing determination the approximate conformations of the radicals involved. The measured kinetics exhibit a linear accumulation of radicals up to an irradiation dose of 1 kGy. The relative yield of stabilized radicals in organic phosphates (TBP, DOP) is approximately three times higher than in amide (DEHBA) or carbamoyl phosphonate (DBDECP) samples. The proposed approach for estimating radiation stability can be expanded to other compounds or mixtures relevant to nuclear waste separation, as well as other substances of particular interest.

Keywords: Radiation stability ; Ligands ; Nuclear waste separation ; EPR spectroscopy ; DFT ; Quantum-chemical calculations

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Product Details of [ 112724-94-4 ]

CAS No. :112724-94-4
Formula : C20H41NO
M.W : 311.55
SMILES Code : CCCC(N(CC(CC)CCCC)CC(CC)CCCC)=O
MDL No. :N/A
InChI Key :ZXHLGQVRYKTEHM-UHFFFAOYSA-N
Pubchem ID :533363

Safety of [ 112724-94-4 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338
 

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