M. Lane

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.

Chemical Studies of Rutherfordium (Element 104) : Part II. Solvent Extraction into Tributylphosphate from HBr Solutions

The chemical properties of element 104, rutherfordium (Rf), and its group 4 homologs and other tetravalent cations were studied by solvent extraction into tributylphosphate (TBP) from various concentrations of HBr and HCl. Since bromide is a larger and softer (more polarizable) anion than chloride, the stability of Rfbromide complexes was expected to differ from the stability of Rf-chloride complexes, and a comparison of the two systems was undertaken. Our studies showed that the extraction trend decreased in the order Zr > Hf > Rf/Ti for HBr, compared to Zr > Hf > Rf > Ti for HCl, showing that Rf and Ti did not extract as well in either system, probably because they hydrolyzed more easily than Zr and Hf.

Chemical Studies of Rutherfordium (Element 104) : Part III. Solvent Extraction into Triisooctylamine from HF Solutions

The extraction of element 104, rutherfordium (Rf), and its group 4 homologs into 0.25 M triisooctylamine (TIOA) in o,m,p-xylene from various concentrations of hydrofluoric acid was studied. This extraction system was of particular interest because all group 4 cations studied formed complexes with the same coordination number (CN) of 6. Therefore, species extracted were similar and the extractability depends on the radii of the fluoride complexes. The studies showed that the extractability for the group 4 elements in this system decreases in the order Ti > Zr ~ Hf > Rf, in inverse order from the decrease in ionic radii Rf > Zr ~ Hf > Ti. This order is different than the order in the hydrolysis, TBP-HC1, and TBP-HBr extraction systems where Rf, due to decreasing CN, behaves more similarly to Ti than to Zr and Hf.

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.

Production cross sections of105261Hafrom the250Cf(15N,4n)and243Am(22Ne,4n)reactions

We have measured the production cross section of 1.8-s {sup 261}Ha from two different reactions. It was produced in the {sup 250}Cf({sup 15}N,4n) reaction at 84 MeV and in the {sup 243}Am({sup 22}Ne,4n) reaction at 116 MeV. Our rotating wheel system with a special parent-daughter stepping mode was used to detect {alpha}-{alpha} correlations between {sup 261}Ha and {sup 257}Lr. We measured 13 and 9 correlations in the two reactions, respectively. Assuming a 100{percent} {alpha} branch, we have determined the production cross section of {sup 261}Ha to be 0.51{plus_minus}0.20thinspnb in the {sup 250}Cf({sup 15}N,4n) reaction at 84 MeV, and 0.25{plus_minus}0.11thinspnb in the {sup 243}Am({sup 22}Ne,4n) reaction at 116 MeV. Based on the number of fission events observed in the latter reaction, we have been able to set an upper limit of 18{percent} for the spontaneous fission branch of {sup 261}Ha. {copyright} {ital 1998} {ital The American Physical Society}

Production cross sections of {sub 105}{sup 261}Ha from the {sup 250}Cf({sup 15}N,4n) and {sup 243}Am({sup 22}Ne,4n) reactions

We have measured the production cross section of 1.8-s {sup 261}Ha from two different reactions. It was produced in the {sup 250}Cf({sup 15}N,4n) reaction at 84 MeV and in the {sup 243}Am({sup 22}Ne,4n) reaction at 116 MeV. Our rotating wheel system with a special parent-daughter stepping mode was used to detect {alpha}-{alpha} correlations between {sup 261}Ha and {sup 257}Lr. We measured 13 and 9 correlations in the two reactions, respectively. Assuming a 100{percent} {alpha} branch, we have determined the production cross section of {sup 261}Ha to be 0.51{plus_minus}0.20thinspnb in the {sup 250}Cf({sup 15}N,4n) reaction at 84 MeV, and 0.25{plus_minus}0.11thinspnb in the {sup 243}Am({sup 22}Ne,4n) reaction at 116 MeV. Based on the number of fission events observed in the latter reaction, we have been able to set an upper limit of 18{percent} for the spontaneous fission branch of {sup 261}Ha. {copyright} {ital 1998} {ital The American Physical Society}

Production cross sections of Ha-105261 from the Cf-250 (N-15, N-4n) and Am-243 (Ne-22, Ne-4n) reactions

We have measured the production cross section of 1.8-s {sup 261}Ha from two different reactions. It was produced in the {sup 250}Cf({sup 15}N,4n) reaction at 84 MeV and in the {sup 243}Am({sup 22}Ne,4n) reaction at 116 MeV. Our rotating wheel system with a special parent-daughter stepping mode was used to detect {alpha}-{alpha} correlations between {sup 261}Ha and {sup 257}Lr. We measured 13 and 9 correlations in the two reactions, respectively. Assuming a 100{percent} {alpha} branch, we have determined the production cross section of {sup 261}Ha to be 0.51{plus_minus}0.20thinspnb in the {sup 250}Cf({sup 15}N,4n) reaction at 84 MeV, and 0.25{plus_minus}0.11thinspnb in the {sup 243}Am({sup 22}Ne,4n) reaction at 116 MeV. Based on the number of fission events observed in the latter reaction, we have been able to set an upper limit of 18{percent} for the spontaneous fission branch of {sup 261}Ha. {copyright} {ital 1998} {ital The American Physical Society}