Petr Distler

Influence of diluent alkyl substitution on the extraction of Am(III) and Eu(III) by a 6,6´-bis(1,2,4-triazin-3-yl)-2,2´-bipyridine ligand dissolved in alkylated cyclohexanone diluents

Abstract Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) from Eu(III) from nitric acid solutions by the CyMe4-BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO3, 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO3, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, DAm and SFAm/Eu decreased in the order of alkyl substitution 2 > 4 ∼ 3. However, alkyl substitution of cyclohexanone significantly slows down the extraction kinetics compared to cyclohexanone, and the position of alkyl substitution was found to play an important role in the solvents properties. 3-Methylcyclohexanone was identified as the most promising of the diluents.

Characterization of solvents containing CyMe4-BTPhen in selected cyclohexanone-based diluents after irradiation by accelerated electrons

Abstract Radiation stability of CyMe4-BTPhen was examined in systems with three selected cyclohexanone-based diluents. Accelerated electrons were used as a source of ionizing radiation. The CyMe4-BTPhen radiation degradation identification and characterization of the degradation products were performed by high performance liquid chromatography (HPLC) and mass spectrometry (MS) analyses. Residual concentrations of tested ligand were determined. Moreover, extraction properties of the solvents irradiated at two different doses were compared with the extraction properties of non-irradiated solvents to estimate the influence of the presence of degradation products in the organic phase.

Separation of the Minor Actinides Americium(III) and Curium(III) by Hydrophobic and Hydrophilic BTPhen ligands: Exploiting Differences in their Rates of Extraction and Effective Separations at Equilibrium

ABSTRACT The complexation and extraction of the adjacent minor actinides Am(III) and Cm(III) by both hydrophobic and hydrophilic pre-organized 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) ligands has been studied in detail. It has been shown that Am(III) is extracted more rapidly than Cm(III) by the hydrophobic CyMe4–BTPhen ligand into different organic diluents under nonequilibrium extraction conditions, leading to separation factors for Am over Cm (SFAm/Cm) as high as 7.9. Furthermore, the selectivity for Am(III) over Cm(III) can be tuned through careful choice of the extraction conditions (organic diluent, contact time, mixing speed, ligand concentration). This “kinetic” effect is attributed to the higher presumed kinetic lability of the Am(III) aqua complex toward ligand substitution. A dependence of the Am(III)/Cm(III) selectivity on the structure of the alkyl groups attached to the triazine rings is also observed, and BTPhens bearing linear alkyl groups are less able to discriminate between Am(III) and Cm(III) than CyMe4–BTPhen. Under equilibrium extraction conditions, hydrophilic tetrasulfonated BTPhen ligands complex selectively Am(III) over Cm(III) and prevent the extraction of Am(III) from nitric acid by the hydrophobic O-donor ligand N,N,N′,N′-tetraoctyldiglycolamide, giving separation factors for Cm(III) over Am(III) (SFCm/Am) of up to 4.6. These results further underline the utility of the BTPhen ligands for the challenging separation of the chemically similar minor actinides Am(III) and Cm(III).

Modelling of the Am(III) – Cm(III) kinetic separation effect observed during metal ion extraction by bis-(1,2,4)-triazine ligands

ABSTRACT The kinetic separation effect was observed leading to a separation factor for Am(III) over Cm(III) as high as 7.9 by using 2,9-bis-(1,2,4-triazin-3-yl)-1,10-phenantroline (BTPhen) ligands in our recent study. In an attempt to explain the observed tendencies, several kinetic models were tested. A model based on mass transfer as the rate-controlling process was found to best describe the kinetic data and allowed to simulate the dependence of Am/Cm separation factor on time. The calculated values of the overall mass-transfer coefficients confirmed that the observed kinetic effect was caused by the different rates of Am(III) and Cm(III) extraction. This kinetic separation phenomenon and its explanation paves the way for potential new approaches to separation of metal ions with very similar properties, such as the adjacent minor actinides Am(III) and Cm(III).

Synthesis and screening of a novel (dppz)-BTPhen ligand for separation of Americium from Europium

A novel bis(1,2,4-triazin-3-yl)-dppz (dipyridophenazine) BTPhen ligand has been synthesised and screened for its ability to selectively extract Am(III) selectively from Eu(III) from 0.001 M – 2 M HNO3. The ligand showed preferential extraction for Am(III) over Eu(III) as the [HNO3] increased towards 2 M with a reported separation factor (SFAm/Eu) of ~ 225. The synthesis towards the dppz-BTPhen ligand employs a truncated synthetic approach, involving two one-pot reactions.