R. Eichler

Chemical characterization of element 112

The heaviest elements to have been chemically characterized are seaborgium (element 106), bohrium (element 107) and hassium (element 108). All three behave according to their respective positions in groups 6, 7 and 8 of the periodic table, which arranges elements according to their outermost electrons and hence their chemical properties. However, the chemical characterization results are not trivial: relativistic effects on the electronic structure of the heaviest elements can strongly influence chemical properties. The next heavy element targeted for chemical characterization is element 112; its closed-shell electronic structure with a filled outer s orbital suggests that it may be particularly susceptible to strong deviations from the chemical property trends expected within group 12. Indeed, first experiments concluded that element 112 does not behave like its lighter homologue mercury. However, the production and identification methods used cast doubt on the validity of this result. Here we report a more reliable chemical characterization of element 112, involving the production of two atoms of 283112 through the alpha decay of the short-lived 287114 (which itself forms in the nuclear fusion reaction of 48Ca with 242Pu) and the adsorption of the two atoms on a gold surface. By directly comparing the adsorption characteristics of 283112 to that of mercury and the noble gas radon, we find that element 112 is very volatile and, unlike radon, reveals a metallic interaction with the gold surface. These adsorption characteristics establish element 112 as a typical element of group 12, and its successful production unambiguously establishes the approach to the island of stability of superheavy elements through 48Ca-induced nuclear fusion reactions with actinides.

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.

Indication for a volatile element 114

Abstract Recently, the chemical investigation of element 112 revealed a highly volatile, noble metallic behaviour, as expected for the last group 12 member of the periodic table. The observed volatility and chemical inertness were ascribed to the growing influence of relativistic effects on the chemical properties of the heaviest elements with increasing nuclear charge. Here, we report for the first time on gas phase chemical experiments aiming at a determination of element 114 properties. This element was investigated using its isotopes 287114 and 288114 produced in the nuclear fusion reactions of 48Ca with 242Pu and 244Pu, respectively. Identification of three atoms of element 114 in thermochromatography experiments and their deposition pattern on a gold surface indicates that this element is at least as volatile as simultaneously investigated elements Hg, At, and element 112. This behaviour is rather unexpected for a typical metal of group 14.

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.

IVO, a device for in situ Volatilization and On-line detection of products from heavy ion reactions

Abstract A new gaschromatographic separation system to rapidly isolate heavy ion reaction products in the form of highly volatile species is described. Reaction products recoiling from the target are stopped in a gas volume and converted in situ to volatile species, which are swept by the carrier gas to a chromatography column. Species that are volatile under the given conditions pass through the column. In a cluster chamber, which is directly attached to the exit of the column, the isolated volatile species are chemically adsorbed to the surface of aerosol particles and transported to an on-line detection system. The whole set-up was tested using short-lived osmium (Os) and mercury (Hg) nuclides produced in heavy ion reactions to model future chemical studies with hassium (Hs, Z =108) and element 112. By varying the temperature of the isothermal section of the chromatography column between room temperature and −80°C, yield measurements of given species can be conducted, yielding information about the volatility of the investigated species.

Synthesis and detection of a seaborgium carbonyl complex

A carbonyl compound that tips the scales Life is short for the heaviest elements. They emerge from high-energy nuclear collisions with scant time for detection before they break up into lighter atoms. Even et al. report that even a few seconds is long enough for carbon to bond to the 106th element, seaborgium (see the Perspective by Loveland). The authors used a custom apparatus to direct the freshly made atoms out of the hot collision environment and through a stream of carbon monoxide and helium. They compared the detected products with theoretical modeling results and conclude that hexacarbonyl Sg(CO)6 was the most likely structural formula. Science, this issue p. 1491; see also p. 1451 A special apparatus enables synthesis of a compound with carbon bonds to a short-lived element produced via nuclear reaction. [Also see Perspective by Loveland] Experimental investigations of transactinoide elements provide benchmark results for chemical theory and probe the predictive power of trends in the periodic table. So far, in gas-phase chemical reactions, simple inorganic compounds with the transactinoide in its highest oxidation state have been synthesized. Single-atom production rates, short half-lives, and harsh experimental conditions limited the number of experimentally accessible compounds. We applied a gas-phase carbonylation technique previously tested on short-lived molybdenum (Mo) and tungsten (W) isotopes to the preparation of a carbonyl complex of seaborgium, the 106th element. The volatile seaborgium complex showed the same volatility and reactivity with a silicon dioxide surface as those of the hexacarbonyl complexes of the lighter homologs Mo and W. Comparison of the product’s adsorption enthalpy with theoretical predictions and data for the lighter congeners supported a Sg(CO)6 formulation.

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.

Rapid synthesis of radioactive transition-metal carbonyl complexes at ambient conditions.

Carbonyl complexes of radioactive transition metals can be easily synthesized with high yields by stopping nuclear fission or fusion products in a gas volume containing CO. Here, we focus on Mo, W, and Os complexes. The reaction takes place at pressures of around 1 bar at room temperature, i.e., at conditions that are easy to accommodate. The formed complexes are highly volatile. They can thus be transported within a gas stream without major losses to setups for their further investigation or direct use. The rapid synthesis holds promise for radiochemical purposes and will be useful for studying, e.g., chemical properties of superheavy elements.

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.

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.