C. A. Laue

Extraction of the fluoride-, chloride- and bromide complexes of the elements Nb, Ta, Pa, and 105 into aliphatic amines

Abstract Previous studies of the halide complex formation of element 105 in HCl–HF mixtures and extractions into triisooctyl amine (TIOA) have been performed with the Automated Rapid Chemistry Apparatus, ARCA II. Element 105 was shown to be absorbed on the column from 12 M HCl–0.02 M HF together with its lighter homologues Nb, Ta and the pseudohomologue Pa. In elutions with 10 M HCl–0.025 M HF, 4 M HCl–0.02 M HF, and 0.5 M HCl–0.01 M HF, the extraction sequence Ta>Nb>105>Pa was observed and element 105 behaved very differently from its closest homologue Ta. As it is not possible within reasonable effort to model the many presumably mixed fluoride–chloride complexes involved in these studies, theoretical calculations were performed in the pure chloride system predicting a reversed sequence of extraction. To verify this experimentally, and in order to perform a systematic study of halide complexation of the group 5 elements, new batch extraction experiments for Nb, Ta, and Pa were performed with the quarternary ammonium salt Aliquat 336 in pure HF, HCl, and HBr solutions. Based on these results, new chromatographic column separations were elaborated to study separately the fluoride and chloride complexation of element 105 with ARCA II. In the system Aliquat 336–HF, after feeding of the activity onto the column in 0.5 M HF, element 105 did not elute in 4 M HF (Pa fraction) but showed a higher distribution coefficient close to that of Nb (and Ta). In the system Aliquat 336–HCl, after feeding onto the column in 10 M HCl, element 105 showed a distribution coefficient in 6 M HCl close to that of Nb establishing an extraction sequence Pa>Nb≥105>Ta which is theoretically predicted by considering the competition between hydrolysis and complex formation.

An EC-branch in the decay of 27-s 263Db: Evidence for the isotope 263Rf

Summary 27-s 263Db was produced in the 249Bk ( 18O, 4n) reaction at 93 MeV. The activity was transported by a He/KCl-jet to the laboratory where it was collected for 15 min and then subjected to a chemical separation specific for group-4 elements. The activity was dissolved in 0.5 M unbuffered α-HiB and eluted from a cation-exchange column. The effluent was made 9 M in HCl and group-4 tetrachlorides were extracted into TBP/Cyclohexane which was evaporated to dryness on a Ta disc. The Ta discs were assayed for α and SF activity. A SF activity with a half life on the order of 20 min was observed and assigned to the nuclide 263Rf. It is formed by electron-capture decay of 263Db with a decay branch of 3+4-1%.

Electron-capture delayed fission properties of242Es

Electron-capture delayed fission was observed in {sup 244}Es produced via the {sup 237}Np({sup 12}C,5n){sup 244}Es reaction at 81 MeV (on target) with a production cross section of 0.31{+-}0.12 {micro}b. The mass-yield distribution of the fission fragments is highly asymmetric. The average preneutron-emission total kinetic energy of the fragments was measured to be 186{+-}19 MeV. Based on the ratio of the number of fission events to the measured number of {alpha} decays from the electron-capture daughter {sup 244}Cf (100% {alpha} branch), the probability of delayed fission was determined to be (1.2{+-}0.4) x 10{sup -4}. This value for the delayed fission probability fits the experimentally observed trend of increasing delayed fission probability with increasing Q value for electron-capture.

Development of a fast and efficient separation for short-lived plutonium isotopes produced in accelerator-based irradiations

ABSTRACT A novel, fast and simple separation procedure is presented for separation of plutonium from lighter actinides and fission products. Classical methods, such as TTA-extraction and anion exchange resin techniques, were examined but failed to provide sufficient separation from lighter actinides. A successful procedure based on solid phase extraction chromatography was developed. Plutonium was effectively separated from interfering activities within 8 minutes using TEVA-resin®, a quaternary amine-based liquid anion exchanger sorbed on an inert support. Recoveries of about 70% were achieved for plutonium with decontamination factors of 105 to 10s from neptunium, uranium and thorium.