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Chemical Structure| 83242-95-9 Chemical Structure| 83242-95-9

Structure of 83242-95-9

Chemical Structure| 83242-95-9

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Holiski, Connor K ; Mastren, Tara ; Shusterman, Jennifer A ;

Abstract: Separating trivalent f-block elements remains a central challenge due to their similar ionic radii and chemical behaviors. Historically, these separations have been achieved using single extractants, either alone or in combination with ion exchange chromatography. However, recent studies, including this work, have explored the potential of using synergic combinations of multiple extractants to enhance extraction and separation efficiencies for trivalent actinide separations. This study investigated synergic solvent extraction (SX) systems for extracting and separating americium and curium using three neutral organophosphorus ligands: octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine (CMPO), dibutyl N,N-diethylcarbamylmethylenephosphonate (DBDECMP), and dihexyl N,N-diethylcarbamylmethylenephosphonate (DHDECMP), combined with either (HTTA, pKa = 6.25) or 4-benzoyl-3-methyl-1-phenyl-2-pyrazolin-5-one (HP, pKa = 3.95). Distribution ratios (D) were determined for 241Am3+ and 242Cm3+ as functions of nitric acid pH using 1,2-dichloroethane as the solvent. The combination of these ligands resulted in varying degrees of synergy as demonstrated by their synergic extraction enhancement coefficients (SEC). A maximum separation factor (SFAm/Cm) of 2.65 ± 0.21 was achieved with 0.05 M HTTA and 0.05 M DBDECMP at pH 2.50. This extractant combination was impregnated into an inert macroporous support at various ligand ratios using rotary evaporator methods to produce novel extraction chromatographic (EXC) resins. Various parameters affecting the adsorption of 241Am3+ and 242Cm3+ onto EXC resins, such as solution pH, ionic strength, contact time, γ-irradiation dose, and temperature, were studied. Metal extraction and synergism were retained upon conversion to EXC resins, with increasing extraction observed at higher pH levels. Thermodynamic studies showed increased adsorption and decreased Gibbs free energy (ΔG) with rising temperature. Kinetic investigations indicated rapid and consistent uptake after 10 minutes. The EXC resins exhibited excellent metal retention in preliminary column experiments, demonstrating a promising potential to separate americium and curium with a maximum decontamination factor of 88. Overall, this work successfully demonstrated the identification and conversion of synergic SX systems into novel synergic EXC resins for adjacent trivalent actinide separations.

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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 [ 83242-95-9 ]

CAS No. :83242-95-9
Formula : C24H42NO2P
M.W : 407.57
SMILES Code : O=C(N(CC(C)C)CC(C)C)CP(C1=CC=CC=C1)(CCCCCCCC)=O
MDL No. :MFCD00079653
InChI Key :SGZRFMMIONYDQU-UHFFFAOYSA-N
Pubchem ID :158335

Safety of [ 83242-95-9 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P264-P280-P302+P352-P304+P340-P305+P351+P338
 

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