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The influence of chemical parameters on the in-situ metal carbonyl complex formation studied with the fast on-line reaction apparatus (FORA)
Radiochimica Acta ( IF 1.8 ) Pub Date : 2021-04-01 , DOI: 10.1515/ract-2020-0031
Yves Wittwer 1, 2 , Robert Eichler 1 , Dominik Herrmann 1 , Andreas Türler 2
Affiliation  

A new setup named Fast On-line Reaction Apparatus (FORA) is presented which allows for the efficient investigation and optimization of metal carbonyl complex (MCC) formation reactions under various reaction conditions. The setup contains a 252 Cf-source producing short-lived Mo, Tc, Ru and Rh isotopes at a rate of a few atoms per second by its 3% spontaneous fission decay branch. Those atoms are transformed within FORA in-situ into volatile metal carbonyl complexes (MCCs) by using CO-containing carrier gases. Here, the design, operation and performance of FORA is discussed, revealing it as a suitable setup for performing single-atom chemistry studies. The influence of various gas-additives, such as CO 2 , CH 4 , H 2 , Ar, O 2 , H 2 O and ambient air, on the formation and transport of MCCs was investigated. O 2 , H 2 O and air were found to harm the formation and transport of MCCs in FORA, with H 2 O being the most severe. An exception is Tc, for which about 130 ppmv of H 2 O caused an increased production and transport of volatile compounds. The other gas-additives were not influencing the formation and transport efficiency of MCCs. Using an older setup called Miss Piggy based on a similar working principle as FORA, it was additionally investigated if gas-additives are mostly affecting the formation or only the transport stability of MCCs. It was found that mostly formation is impacted, as MCCs appear to be much less sensitive to reacting with gas-additives in comparison to the bare Mo, Tc, Ru and Rh atoms.

中文翻译:

化学参数对快速在线反应装置(FORA)研究的原位羰基金属配合物形成的影响

提出了一种名为快速在线反应装置(FORA)的新设置,它可以在各种反应条件下有效地研究和优化羰基金属络合物(MCC)的形成反应。该装置包含一个252 Cf的源,通过其3%的自发裂变衰变分支,以每秒几个原子的速率产生短寿命的Mo,Tc,Ru和Rh同位素。通过使用含CO的载气,这些原子在FORA内原位转化为挥发性金属羰基配合物(MCC)。在此,对FORA的设计,操作和性能进行了讨论,揭示了FORA是进行单原子化学研究的合适设置。研究了CO 2,CH 4,H 2,Ar 2,H 2 O和环境空气等各种气体添加剂对MCCs的形成和迁移的影响。O 2,发现H 2 O和空气会损害FORA中MCC的形成和运输,其中H 2 O最严重。Tc是一个例外,其大约130 ppmv的H 2 O导致挥发性化合物的产生和运输增加。其他气体添加剂不会影响MCC的形成和传输效率。基于与FORA相似的工作原理,使用了一种名为Miss Piggy的旧式装置,另外还研究了气体添加剂是否主要影响MCC的形成或仅影响MCC的运输稳定性。已经发现,大部分形成都受到影响,因为与裸露的Mo,Tc,Ru和Rh原子相比,MCC对与气体添加剂的反应不那么敏感。为此,约130 ppmv的H 2 O导致挥发性化合物的产生和运输增加。其他气体添加剂不会影响MCC的形成和传输效率。基于与FORA相似的工作原理,使用了一种名为Miss Piggy的旧式装置,另外还研究了气体添加剂是否主要影响MCC的形成或仅影响MCC的运输稳定性。已经发现,大部分形成都受到影响,因为与裸露的Mo,Tc,Ru和Rh原子相比,MCC对与气体添加剂的反应不那么敏感。为此,约130 ppmv的H 2 O导致挥发性化合物的产生和运输增加。其他气体添加剂不会影响MCC的形成和传输效率。基于与FORA相似的工作原理,使用了一种名为Miss Piggy的旧式装置,另外还研究了气体添加剂是否主要影响MCC的形成或仅影响MCC的运输稳定性。已经发现,大部分形成都受到影响,因为与裸露的Mo,Tc,Ru和Rh原子相比,MCC对与气体添加剂的反应不那么敏感。另外还研究了气体添加剂是否主要影响MCC的形成或仅影响MCC的运输稳定性。已经发现,大部分形成都受到影响,因为与裸露的Mo,Tc,Ru和Rh原子相比,MCC对与气体添加剂的反应不那么敏感。另外还研究了气体添加剂是否主要影响MCC的形成或仅影响MCC的运输稳定性。已经发现,大部分形成都受到影响,因为与裸露的Mo,Tc,Ru和Rh原子相比,MCC对与气体添加剂的反应不那么敏感。
更新日期:2021-04-02
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