The influence of chemical parameters on the in-situ metal carbonyl complex formation studied with the fast on-line reaction apparatus (FORA)

We introduce a novel thick-target concept tailored to the extraction of refractory 4d and 5d transition metal radionuclides of molybdenum, technetium, ruthenium and tungsten for radioactive ion beam production. Despite the more than 60-year old history of thick-target ISOL mass-separation facilities like ISOLDE, the extraction of these most refractory elements as radioactive ion beam has so far not been successful. In ordinary thick ISOL targets, their radioisotopes produced in the target are stopped within the condensed target material. Here, we present a concept which overcomes limitations associated with this method. We exploit the recoil momentum of nuclear reaction products for their release from the solid target material. They are thermalized in a carbon monoxide-containing atmosphere, in which volatile carbonyl complexes form readily at ambient temperature and pressure. This compound serves as volatile carrier for transport to the ion source. Excess carbon monoxide is removed by cryogenic gas separation to enable low pressures in the source region, in which the species are ionized and hence made available for radioactive ion beam formation. The setup is operated in batch mode. Initially, we investigate the feasibility of the approach with isotopes of more than 35s half-life. At the cost of reduced efficiency, the concept could also be applied to isotopes with half-lives of at least one to 10s. We report parameter studies of the key processes of the method, which validate this concept and which define the parameters for the setup. This would allow for the first time the extraction of radioactive molybdenum, tungsten and several other transition metals at thick-target ISOL facilities.

show abstract

“…In addition, impurities (e.g. oxygen or humidity) in the reactive gas reduce the chemical yield [28].…”

Section: The Target Conceptmentioning

confidence: 99%

A concept for the extraction of the most refractory elements at CERN-ISOLDE as carbonyl complex ions

et al. 2022

View full text Add to dashboard Cite

show abstract

The influence of physical parameters on the in-situ metal carbonyl complex formation studied with the Fast On-line Reaction Apparatus (FORA)

et al. 2021

Self Cite

View full text Add to dashboard Cite

The Fast On-line Reaction Apparatus (FORA) was used to investigate the influence of various reaction parameters onto the formation and transport of metal carbonyl complexes (MCCs) under single-atom chemistry conditions. FORA is based on a 252Cf-source producing short-lived Mo, Tc, Ru and Rh isotopes. Those are recoiling from the spontaneous fission source into a reaction chamber flushed with a gas-mixture containing CO. Upon contact with CO, fission products form volatile MCCs which are further transported by the gas stream to the detection setup, consisting of a charcoal trap mounted in front of a HPGe γ-detector. Depending on the reaction conditions, MCCs are formed and transported with different efficiencies. Using this setup, the impact of varying physical parameters like gas flow, gas pressure, kinetic energy of fission products upon entering the reaction chamber and temperature of the reaction chamber on the formation and transport yields of MCCs was investigated. Using a setup similar to FORA called Miss Piggy, various gas mixtures of CO with a selection of noble gases, as well as N2 and H2, were investigated with respect to their effect onto MCC formation and transport. Based on this measurements, optimized reaction conditions to maximize the synthesis and transport of MCCs are suggested. Explanations for the observed results supported by simulations are suggested as well.

show abstract

The influence of gas purification and addition of macro amounts of metal-carbonyl complexes on the formation of single-atom metal-carbonyl-complexes

et al. 2021

View full text Add to dashboard Cite

Using the Fast On-line Reaction Apparatus (FORA), the influence of various gas-purification columns onto the formation of metal carbonyl complexes (MCCs) under single-atom chemistry conditions was investigated. MCCs were synthesized from single atoms of Mo, Tc, Ru and Rh being produced by the spontaneous fission of 252Cf and recoiling into a CO-gas containing carrier gas atmosphere. The in-situ synthesized MCCs were volatile enough to be transported by the carrier gas to a charcoal trap where they were adsorbed and their subsequent decay was registered by γ-spectrometry. It was found that the type and combination of purification columns used to clean the applied CO-gas strongly influences the obtained formation and transport yields for all MCCs. With the exception of Rh-carbonyl, intense gas-purification strategies resulted in reduced formation and transport yields for MCCs in comparison with less efficient or even completely missing purification setups. It was postulated that the observed reduction in yield might depend on the content of Fe(CO)5 and Ni(CO)4, as well as potentially other MCCs, in the CO-gas, being formed by the interaction between CO and the steel-surfaces of FORA as well as from impurities in the used charcoal traps. Subsequently, it was shown that macro amounts of Fe(CO)5, Ni(CO)4, Mo(CO)6 and Re2(CO)10 added to the used process gas indeed increase significantly the overall yields for MCCs produced by 252Cf fission products. Ni(CO)4 appeared the most potent to increase the yield. Therefore, it was used in more detailed investigations. Using isothermal chromatography, it was shown that Ni(CO)4 does not affect the speciation of carbonyl species produced by the 252Cf fission product 104Mo. For 107Tc, 110Ru and 111Rh a speciation change cannot be excluded. For 111Rh a speciation change cannot be excluded. An inter-carbonyl transfer mechanism is suggested boosting the formation of MCCs. The current discovery might allow for new opportunities in various research fields, which are currently restricted by the low overall yields for MCCs produced under single-atom chemistry conditions. Examples are the chemical investigation of transactinides or the generation of radioactive ion beams from refractory metals at accelerators.

show abstract

The influence of chemical parameters on the in-situ metal carbonyl complex formation studied with the fast on-line reaction apparatus (FORA)

Cited by 4 publications

References 37 publications

A concept for the extraction of the most refractory elements at CERN-ISOLDE as carbonyl complex ions

A concept for the extraction of the most refractory elements at CERN-ISOLDE as carbonyl complex ions

The influence of physical parameters on the in-situ metal carbonyl complex formation studied with the Fast On-line Reaction Apparatus (FORA)

The influence of gas purification and addition of macro amounts of metal-carbonyl complexes on the formation of single-atom metal-carbonyl-complexes

Contact Info

Product

Resources

About