B. Eichler

Chemical investigation of hassium (element 108).

The periodic table provides a classification of the chemical properties of the elements. But for the heaviest elements, the transactinides, this role of the periodic table reaches its limits because increasingly strong relativistic effects on the valence electron shells can induce deviations from known trends in chemical properties. In the case of the first two transactinides, elements 104 and 105, relativistic effects do indeed influence their chemical properties, whereas elements 106 and 107 both behave as expected from their position within the periodic table. Here we report the chemical separation and characterization of only seven detected atoms of element 108 (hassium, Hs), which were generated as isotopes 269Hs (refs 8, 9) and 270Hs (ref. 10) in the fusion reaction between 26Mg and 248Cm. The hassium atoms are immediately oxidized to a highly volatile oxide, presumably HsO4, for which we determine an enthalpy of adsorption on our detector surface that is comparable to the adsorption enthalpy determined under identical conditions for the osmium oxide OsO4. These results provide evidence that the chemical properties of hassium and its lighter homologue osmium are similar, thus confirming that hassium exhibits properties as expected from its position in group 8 of the periodic table.

Chemical properties of element 106 (seaborgium)

The synthesis, via nuclear fusion reactions, of elements heavier than the actinides, allows one to probe the limits of the periodic table as a means of classifying the elements. In particular, deviations in the periodicity of chemical properties for the heaviest elements are predicted as a consequence of increasingly strong relativistic effects on the electronic shell structure. The transactinide elements have now been extended up to element 112 (ref. 8), but the chemical properties have been investigated only for the first two of the transactinide elements, 104 and 105 (refs 9,10,11,12,13,14,15,16,17,18,19). Those studies showed that relativistic effect render these two elements chemically different from their lighter homologues in the same columns of the periodic table (Fig. 1). Here we report the chemical separation of element 106 (seaborgium, Sg) and investigations of its chemical behaviour in the gas phase and in aqueous solution. The methods that we use are able to probe the reactivity of individual atoms, and based on the detection of just seven atoms of seaborgium we find that it exhibits properties characteristic of the group 6 homologues molybdenum and tungsten. Thus seaborgium appears to restore the trends of the periodic table disrupted by relativistic effects in elements 104 and 105.

Chemical identification and properties of element 112

Summary We present results of the second experiment on the chemical identification of element 112. Similar to the first test in 2000, we aimed at the production of the spontaneously fissioning 283112 nuclei with T1/2≈3min. A natU3O8 (with some Nd) target, 2mg of U/cm2 thick, was bombarded with 233-MeV 48Ca ions (the energy in the middle of the target layer). The nuclei recoiling from the target were thermalized in flowing helium. The target chamber was connected through a 25m long capillary to detectors of α-particles and fission fragments. All the equipment and detectors were kept at ambient temperature. According to the test experiments, of all the heavy elements produced in the bombardment, only Hg, Rn and At could be transported to the detectors. The first detecting device was similar to that used earlier – an assembly of 8 pairs of PIPS detectors coated with gold. Here one would observe the decay of element 112 atoms if they like Hg adsorbed on gold. The atoms which were not retained and freely passed through the PIPS detectors entered a new, flow-through ionization chamber, 5000 cm3 in volume, optimized for detecting fission fragments. The PIPS detectors and the ionization chamber were placed inside a large assembly of 3He – filled neutron counters to detect prompt neutrons from the fission events. In 22.5 days, a beam dose of 2.8×1018 ions was accumulated. More than 95 of the simultaneously produced α-active 185Hg (T1/2=49 s) were found deposited already on the first pair of PIPS detectors; meanwhile, all the PIPSs did not detect any fission event. In the ionization chamber, eight fission events were observed in coincidence with neutron counts while the expected background was insignificant. Hence, the spontaneous fissions of the volatile activity can be conclusively attributed to the decay of element 112 produced in the fusion reaction 48Ca+ 238U, and formerly observed in Dubna physical experiments. Evaluation of the experimental data in terms of the adsorption enthalpies indicates much weaker interaction of element 112 with Au than that of Hg. One can conclude that in the given chemical environment, element 112 behaves like Rn rather than like Hg. The formation cross section of 283112 estimated from the data amounts to several pb. The experiments were carried out at the Flerov Laboratory of Nuclear Reactions at JINR in November–December 2001.

Thermochromatographic studies of mercury and radon on transition metal surfaces

Abstract In preparation for the experimental investigation of chemical properties of element 112 model studies were conducted based on the assumed similarity of element 112 to either the noble gas Rn or the transition metal Hg, its supposed lighter homologue in group 12. The adsorption behavior of elemental Hg on the transition metals Ag, Au, Ni, Pd, and Pt were investigated experimentally by off-line gas thermochromatography. The deduced adsorption data of Hg were compared with new values calculated using the Eichler–Miedema model. The observed sequence of increasing Hg-metal-interactions for Ag < Ni < Au < Pd < Pt confirms the predicted trend. The only exception was Pd, on which Hg was calculated to adsorb at a higher temperature than on Pt. Difficulties to obtain reproducible clean surfaces of Ag, Ni, Pd, and Pt led to the choice of Au as the best metal surface suitable to adsorb Hg. For fast on-line gas thermochromatography studies on metallic surfaces a new set-up was developed based on the In-situ Volatilization and On-line detection technique (IVO). This set-up was tested in on-line thermochromatographic investigations with short-lived Hg isotopes and 219Rn, using Au or Pd as stationary surfaces. An overall efficiency of about 60% and a transportation time less than 25 s was determined for this newly designed IVO. A separation factor of more than 106 was estimated for non-volatile species.

First Measurement of a Thermochemical Property of a Seaborgium Compound.

With only a few atoms of seaborgium (Sg, element 106), in the form of volatile SgO(2)Cl(2), it was possible to determine the sublimation enthalpy of this compound using gas chromatography. Furthermore, it was demonstrated that in Group 6 Sg is chemically more similar to W than to Mo.

Investigation of evaporation characteristics of polonium and its lighter homologues selenium and tellurium from liquid Pb-Bi-eutecticum

Summary The evaporation behaviour of polonium and its lighter homologues selenium and tellurium dissolved in liquid Pb-Bi-eutecticum (LBE) has been studied at various temperatures in the range from 482 K up to 1330 K under Ar/H2 and Ar/H2O-atmospheres using γ-ray spectroscopy. Polonium release in the temperature range of interest for technical applications is slow. Within short term (1 h) experiments measurable amounts of polonium are evaporated only at temperatures above 973 K. Long term experiments reveal that a slow evaporation of polonium occurs at temperatures around 873 K resulting in a fractional polonium loss of the melt around 1% per day. Evaporation rates of selenium and tellurium are smaller than those of polonium. The presence of H2O does not enhance the evaporation within the error limits of our experiments. The thermodynamics and possible reaction pathways involved in polonium release from LBE are discussed.

Gas phase chemistry of technetium and rhenium oxychlorides

The chloride and oxychloride chemistry of the group 7 elements Tc and Re was investigated in order to develop an experimental approach to a gas chemical characterisation of bohrium (Bh, element 107). In thermochromatography experiments with trace amounts of 101,104Tc and 183,184Re the formation of one volatile compound was observed in O2/HCl containing carrier gas, which was attributed to MO3Cl (M = Tc, Re). From the measured deposition temperatures the adsorption enthalpies on quartz surfaces ΔHads(TcO3Cl) = -51 ± 3 kJ/mol and ΔHads(ReO3Cl) = -62 ± 3 kJ/mol were evaluated. The sublimation enthalpies were derived using an empirical correlation between Δ Hads and ΔHsubl: ΔHsubl(TcO3Cl) = 49±10 kJ/mol and ΔHsubl(ReO3Cl) = 67±10 kJ/mol. A fast gas chemical separation technique for highly volatile compounds of short-lived isotopes based on isothermal gas solid adsorption chromatography (OLGA-principle) was developed. With a modified OLGA device, model studies with the short-lived nuclides 106,107,108Tc and 169,170,174,176Re were carried out in preparation of an experimental gas chemical investigation of bohrium (Bh, element 107). Separation times of less than 3 s were achieved. A good separation of the oxychlorides of group 7 elements from chloride and oxychloride compounds of 152-155Er, 151-154Ho (as models for actinide elements), 98-101Nb, 99-102Zr (as models for light transactinide elements), 218Po, and 214Bi was accomplished in this chemical system.

Physico-chemical characterization of seaborgium as oxide hydroxide

Seaborgium (Sg; element 106) was studied in comparison with tungsten in the O2-H2O(g)/SiO2(s)-system using high temperature on-line isothermal gas chromatography. The 21-s nuclide 266Sg was produced in the 248Cm+22Ne reaction at a beam energy of 119 MeV. The reaction products were continuously transported by a He(MoO3)-jet to the chromatography apparatus HITGAS. Group 6 element oxide hydroxide molecules volatile at temperatures above 1000 K were formed at 1325 K by adding humid oxygen as reactive gas. 266Sg was unambiguously detected after gas chromatographic separation by measuring 266Sg-262Rf mother-daughter α-sf correlations. The experimental results demonstrate the volatility of Sg in humid oxygen, presumably as Sg oxide hydroxide, a behavior typical for both U(VI) and the group 6 elements.

Chemical procedure applied for the identification of Rf/Db produced in the 48Ca +243Am reaction

Summary A chemical separation procedure for Rf/Db is described which was applied to a long-lived decay product from the nuclear fusion reaction 48Ca+ 243Am. A 1.2 mg thick 243Am target was bombarded by 247 MeV 48Ca particles. The recoiling products were collected in a thick Cu catcher for about one day and then subjected to a chemical separation procedure that included an ion exchange from dilute HF solutions. Final samples were prepared on 30 μg/cm2 thick polyethylene (PE) foils and counted in 4π-geometry for α-particles and spontaneous fission (SF) coincidences. The detector arrays were surrounded by 3He detectors to also assay prompt neutrons. Decontamination factors from actinides of about 105 were achieved. Group 6 (W) to 14 (Pb) elements as models for their heavier homologues were shown to be separated from the Rf/Db fraction with more than 90%. In eight final samples, representing a total beam dose of 3.4 × 1018 particles, 15 SF events were detected. The decay pattern points to a single component with a half-life of ≈32h, which shows a chemical behavior similar to the lighter homologues of group 4 and 5 elements.

Evidence for relativistic effects in the chemistry of element 104

Abstract On the basis of thermodynamic extrapolations, the first transactinide element 104 (Rf=rutherfordium 1 ) is expected to form volatile tetrachlorides of lower volatility than those of the homologous element Hf. In contrast, relativistic calculations predict a higher volatility of RfCl 4 compared to HfCl 4 . The nuclides 261 Rf and 165 Hf, with identical half-lives of 78 s, were simultaneously produced at the U-400 cyclotron of the Flerov Laboratory of Nuclear Reactions (FLNR), Dubna, Russia, by bombarding a mixed 248 Cm/ 152 Gd target with 18 O ions. With the on-line gas chemistry apparatus (OLGA), the retention behavior of volatile Rf- and Hf-chloride in a quartz chromatography column was investigated. The results showed that Rf forms chlorides of higher volatility than those of Hf, in agreement with relativistic calculations. In addition, the behavior of element 104 was investigated in chlorinating, oxygen containing carrier gas, in order to answer the question whether a volatile compound of the form RfOCl 2 exists. The results of our experiments give strong evidence for a transport reaction mechanism where RfOCl 2 exists only in the condensed phase and not in the gas phase.