Ruthenium isotope analysis

There is only one detailed kinetic study of ruthenium enantioselective hydrogenation, in this case involving (BINAP)Ru(OAc)2, and MAC [65]. The extensive study involved reaction kinetics, isotopic analysis of reaction components and products, and in-situ NMR. The derived catalytic cycle is shown in Figure 31.15, differing from the Bergens studies described above in that the intermediates -both observed and assumed - are neutral rather than cationic. Right up to the formation of the alkylruthenium intermediate, the individual steps are revers-... 

Resonance-ionization mass-spectrometry is still in the development stage in terms of its application to cosmochemistry. The Charisma instrument, which is operated by Argonne National Laboratories, uses multiple lasers to resonantly ionize only the elements of interest, which are then analyzed with a time-of-flight mass spectrometer. The Charisma instrument has made isotopic measurements of molybdenum, zirconium, strontium, ruthenium, barium and other elements in presolar grains. These measurements are made possible by the high ionization efficiency of the RIMS technique and its ability to completely eliminate isobaric interferences. Work is now underway to build a RIMS instrument that can be operated by an individual investigator in a university laboratory. If this succeeds, RIMS will play an increasing role in analysis of extraterrestrial materials. 

In some cases the so-called "Steady-State Isotopic Transient Kinetic Analysis" (SSITKA) was used for detailed investigations of reaction mechanisms. Shannon and Goodman [123] present an extensive review of this subject. Hinrichsen et al. [124] employed temperature programmed desorption to study the ammonia synthesis on ruthenium catalysts. 

Probably the most comprehensive published assay of DU used in armor pen-etrators was reported on the basis of analysis of an unfired CHARM-3 penetrator (Trueman et al. 2004). A sample from the penetrator was dissolved in 9 M HCl, spiked with U as a yield monitor, and the uranium was separated from impurities on an ion-exchange resin. The isotopic composition of uranium was determined by mass spectrometric techniques. Actinides ( - Am and Np) were determined in the uranium-free solution by gamma spectrometry and 239+24opy and Pu were measured by alpha spectrometry and their presence was confirmed by ICPMS. Technetium-99 was determined by ICPMS when rhenium was used as a carrier and interferences from iron were eliminated by precipitating with ammonia while ruthenium and molybdenum were removed by separation on a chromatographic resin. The content of these radioactive nuclides is summarized in Table 2.7. 

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