D. Piguet

Heterogeneous production of nitrous acid on soot in polluted air masses

Polluted air masses are characterized by high concentrations of oxidized nitrogen compounds which are involved in photochemical smog and ozone formation. The OH radical is a key species in these oxidation processes. The photolysis of nitrous acid (HNO2), in the morning, leads to the direct formation of the OH radical and may therefore contribute significantly to the initiation of the daytime photochemistry in the polluted planetary boundary layer. But the formation of nitrous acid remains poorly understood: experimental studies imply that a suggested heterogeneous formation process involving NO2 is not efficient enough to explain the observed night-time build-up of HNO2 in polluted air masses. Here we describe kinetic investigations which indicate that the heterogeneous production of HNO2 from NO2 on suspended soot particles proceeds 105 to 107 times faster than on previously studied surfaces. We therefore propose that the interaction between NO2 and soot particles may account for the high concentrations of HNO2 in air masses where combustion sources contribute to air pollution by soot and NOx emissions. We believe that the observed HNO2 formation results from the reduction of NO2 in the presence of water by C–O and C–H groups in the soot. Although prolonged exposure to oxidizing agents in the atmosphere is likely to affect the chemical activity of these groups, our observations nevertheless suggest that fresh soot may have a considerable effect on the chemical reactions occurring in polluted air.

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.

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.

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.

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.

Adsorption interaction of carrier-free thallium species with gold and quartz surfaces

Abstract The adsorption interactions of thallium and its compounds with gold and quartz surfaces were investigated. Carrier-free amounts of thallium were produced in nuclear fusion reactions of alpha particles with thick gold targets. The method chosen for the studies was gas thermochromatography and varying the redox potential of the carrier gases. It was observed that thallium is extremely sensitive to trace amounts of oxygen and water, and can even be oxidized by the hydroxyl groups located on the quartz surface. The experiments on a quartz surface with O2, He, H2 gas in addition with water revealed the formation and deposition of only one thallium species – TlOH. The adsorption enthalpy was determined to be Δ HSiO2ads(TlOH) = −134 ± 5 kJ mol−1. A series of experiments using gold as stationary surface and different carrier gases resulted in the detection of two thallium species – metallic Tl (H2 as carrier gas) and TlOH (O2, O2+H2O and H2+H2O as pure carrier gas or carrier gas mixture) with Δ HAuads(Tl) = −270 ± 10 kJ mol− and Δ HAuads(TlOH) = −146 ± 3 kJ mol−1. These data demonstrate a weak interaction of TlOH with both quartz and gold surfaces. The data represent important information for the design of future experiments with the heavier homologue of Tl in group 13 of the periodic table – element 113 (E113).

ON-LINE GAS CHROMATOGRAPHY OF MO, W AND U (OXY)CHLORIDES

By M. Gärtner, Μ. Boettger, Β. Eichler, Η. W. Gäggeler, Μ. Grantz, S. Hübener, D. T. Jost, D. Piguet, R. Dressler, A. Türler and Α. B. Yakushev 1 Labor für Radiound Umweltchemie, Universität Bern, 3000 Bern, Switzerland 2 Labor für Radiound Umweltchemie, Paul-Scherrer-Institut, 5232 Villigen, Switzerland 3 Flerov Laboratory for Nuclear Reactions, Dubna, 141980 Russia 4 Institut für Radiochemie, Forschungszentrum Rossendorf, D-01314 Dresden, Germany