Extraction behavior of Mo and W from HSO and HF/HCl solutions into toluene with Aliquat336; Sulfate and fluoride complex formation of Mo and W towards chemical studies of seaborgium (Sg)

Toyoshima, Atsushi; Mitsukai, Akina; Tsukada, Kazuaki; Oe, Kazuhiro*; Haba, Hiromitsu*; Komori, Yukiko*; Murakami, Masashi; Kaneya, Yusuke*; Sato, Daisuke*; Asai, Masato; et al.

Journal of Radioanalytical and Nuclear Chemistry, 317(1), p.421 - 430, 2018/07

https://doi.org/10.1007/s10967-018-5882-5

We have studied extraction behavior of group-6 elements Mo and W to search for suitable conditions for an on-line extraction experiment of their heavier homolog, seaborgium (Sg). Batch-wise extraction of carrier-free radiotracers Mo and W were carried out from 0.10 - 8.6 M HSO and 1.010 - 5.0 M HF/1.0 M HCl into toluene with a quaternary ammonium compound, Aliquat336. Anionic sulfate complexes of Mo and W with charge - 2 were extracted with Aliquat336 from HSO solutions with concentrations of [HSO] 2 M. In HF/1.0 M HCl, oxyfluoro complexes of Mo and W with charge - 1 were interpreted to be formed and extracted with Aliquat336. From these results, favorable conditions for the extraction of Sg are discussed.

Complex chemistry with complex compounds

Eichler, R.*; Asai, Masato; Brand, H.*; Chiera, N. M.*; Di Nitto, A.*; Dressler, R.*; Dllmann, Ch. E.*; Even, J.*; Fangli, F.*; Goetz, M.*; et al.

EPJ Web of Conferences, 131, p.07005_1 - 07005_7, 2016/12

https://doi.org/10.1051/epjconf/201613107005

In recent years gas-phase chemical studies assisted by physical pre-separation allowed for the productions and investigations of fragile single molecular species of superheavy elements. The latest highlight is the formation of very volatile hexacarbonyl compound of element 106, Sg(CO). Following this success, second-generation experiments were performed to measure the first bond dissociation energy between the central metal atom and the surrounding ligand. The method using a tubular decomposition reactor was developed and successfully applied to short-lived Mo(CO), W(CO), and Sg(CO).

Decomposition studies of group 6 hexacarbonyl complexes, 1; Production and decomposition of Mo(CO) and W(CO)

Usoltsev, I.*; Eichler, R.*; Wang, Y.*; Even, J.*; Yakushev, A.*; Haba, Hiromitsu*; Asai, Masato; Brand, H.*; Di Nitto, A.*; Dllmann, Ch. E.*; et al.

Radiochimica Acta, 104(3), p.141 - 151, 2016/03

https://doi.org/10.1515/ract-2015-2445

Conditions of the production and decomposition of hexacarbonyl complexes of short-lived Mo and W isotopes were investigated to study thermal stability of the heaviest group 6 hexacarbonyl complex Sg(CO). A tubular flow reactor was tested to decompose the hexacarbonyl complexes and to extract the first bond dissociation energies. A silver was found to be the most appropriate reaction surface to study the decomposition of the group 6 hexacarbonyl. It was found that the surface temperature at which the decomposition occurred was correlated to the first bond dissociation energy of Mo(CO) and W(CO), indicating that the first bond dissociation energy of Sg(CO) could be determined with this technique.

In situ synthesis of volatile carbonyl complexes with short-lived nuclides

Even, J.*; Ackermann, D.*; Asai, Masato; Block, M.*; Brand, H.*; Di Nitto, A.*; Dllmann, Ch. E.*; Eichler, R.*; Fan, F.*; Haba, Hiromitsu*; et al.

Journal of Radioanalytical and Nuclear Chemistry, 303(3), p.2457 - 2466, 2015/03

https://doi.org/10.1007/s10967-014-3793-7

Rapid In situ synthesis of metal carbonyl complexes has been demonstrated using short-lived isotopes produced in nuclear fission and fusion reactions. The short-lived isotopes with high recoil energy directly react with carbon-monoxides and form carbonyl complexes. Only highly volatile complexes were fast transported in a gas stream to counting and chemistry devices. Short-lived Mo, Tc, Ru, Rh, W, Re, Os, and Ir were found to form volatile carbonyl complexes, while no volataile complex of Hf and Ta were detected. This technique has been applied to a chemical investigation of the superheavy element Sg (atomic number 106), and will be applicable to various fields of nuclear science with short-lived transition metal isotopes.

Development of a new continuous dissolution apparatus with a hydrophobic membrane for superheavy element chemistry

Oe, Kazuhiro*; Attallah, M. F.*; Asai, Masato; Goto, Naoya*; Gupta, N. S.*; Haba, Hiromitsu*; Huang, M.*; Kanaya, Jumpei*; Kaneya, Yusuke*; Kasamatsu, Yoshitaka*; et al.

Journal of Radioanalytical and Nuclear Chemistry, 303(2), p.1317 - 1320, 2015/02

https://doi.org/10.1007/s10967-014-3469-3

A new technique for continuous dissolution of nuclear reaction products transported by a gas-jet system was developed for superheavy element (SHE) chemistry. In this technique, a hydrophobic membrane is utilized to separate an aqueous phase from the gas phase. With this technique, the dissolution efficiencies of short-lived radionuclides of Mo and W were measured. Yields of more than 80% were observed for short-lived radionuclides at aqueous-phase flow rates of 0.1-0.4 mL/s. The gas flow-rate had no influence on the dissolution efficiency within the studied flow range of 1.0-2.0 L/min. These results show that this technique is applicable for on-line chemical studies of SHEs in the liquid phase.

Measurement of the Md/Md reduction potential studied with flow electrolytic chromatography

Toyoshima, Atsushi; Li, Z.*; Asai, Masato; Sato, Nozomi; Sato, Tetsuya; Kikuchi, Takahiro; Kaneya, Yusuke; Kitatsuji, Yoshihiro; Tsukada, Kazuaki; Nagame, Yuichiro; et al.

Inorganic Chemistry, 52(21), p.12311 - 12313, 2013/11

https://doi.org/10.1021/ic401571h

The reduction behavior of mendelevium (Md) was studied using a flow electrolytic chromatography apparatus. By applying appropriate potentials on the chromatography column, the more stable Md is reduced to Md. The reduction potential of the Md + e Md couple was determined to be -0.160.05 V vs. a normal hydrogen electrode.

Efficiency calibration of Ge detector for I and Cs in soil samples and a simplified calculation of cascade summing corrections for volume source

Asai, Masato; Kaneya, Yusuke*; Sato, Tetsuya; Tsukada, Kazuaki; Oe, Kazuhiro; Sato, Nozomi; Toyoshima, Atsushi

Journal of Nuclear and Radiochemical Sciences (Internet), 12(1), p.5 - 10, 2012/06

http://www.radiochem.org/paper/JN121/jn12103.pdf

To measure radioactivities in soil contaminated by the accident of the Fukushima Daiichi Nuclear Power Plant, efficiency calibration of Ge detectors for I, Cs, and Cs in volume sources was investigated. -ray detection efficiencies for these nuclei were determined precisely using standard soil samples containing Cs, Cs, Hf, and Zr. These standard sources were prepared by admixing radioactive solutions with soil, and point sources were made from the same solutions to determine their radioactivity concentrations. Cascade summing corrections for rays of Cs in soil samples were evaluated experimentally. To easily calculate the cascade summing corrections for volume sources, we examined a simplified method using averaged efficiencies, and evaluated its validity through a comparison of the calculated correction factors with the experimental ones.

Determination of redox potential of mendelevium (Md)

Toyoshima, Atsushi; Li, Z.*; Asai, Masato; Sato, Nozomi; Sato, Tetsuya; Oe, Kazuhiro; Kikuchi, Takahiro; Kaneya, Yusuke*; Kitatsuji, Yoshihiro; Tsukada, Kazuaki; et al.

no journal, , 

Redox potential of mendelevium (Md) was determined with flow electrolytic chromatography. Mendelevium-255 with a half-life of 27 min was produced in the Cm(B, 4) reaction at the JAEA tandem accelerator. Reaction products transported by a KCl/He gas-jet method were collected on a chemistry apparatus. After removing KCl with HDEHP column chromatography, elution behavior of Md in 0.10 M HCl was investigated with a flow electrolytic column apparatus at the applied potentials between -0.3 and -0.6 V vs. a Ag/AgCl reference electrode. At -0.3 V, elution behavior of Md was the same as that of Bk, showing that the stable Md was not reduced to the divalent state. At -0.6 V, elution of Md was quite similar to that of Sr, demonstrating that Md was successfully reduced to Md. From the behavior of Md against the applied potentials, we evaluated its redox potential to be -0.400.03 V.

Surface-ionization of lanthanides for the measurement of the first ionization potential of Lr

Sato, Nozomi; Asai, Masato; Tsukada, Kazuaki; Sato, Tetsuya; Toyoshima, Atsushi; Li, Z.*; Oe, Kazuhiro; Kikuchi, Takahiro; Kaneya, Yusuke*; Schdel, M.; et al.

no journal, , 

The first ionization potential (IP) of the last actinide, lawrencium (Lr), is predicted to be lower than those of other actinides. To determine the IP of Lr based on the surface ionization comparison technique, we are developing a surface-ionization-type ion-source coupled to a gas-jet transport system at the Isotope Separator On-Line at the JAEA tandem accelerator facility. In the present study, we measured ionization efficiencies of lanthanides as a function of ion-source temperature to examine the applicability of our apparatus to the IP measurement. It was found that the obtained ionization efficiency of each lanthanide element is affected by an ionization potential as well as a boiling point.

Redox studies of the heaviest elements using an electrolytic column apparatus

Toyoshima, Atsushi; Oe, Kazuhiro; Asai, Masato; Miyashita, Sunao; Sato, Tetsuya; Sato, Nozomi; Kaneya, Yusuke*; Kitatsuji, Yoshihiro; Tsukada, Kazuaki; Nagame, Yuichiro; et al.

no journal, ,