Vibrational spectra of some group Vb halides—II

Studies of Flerovium and Element 115 Homologs with Macrocyclic Extractants

“…Due to relativistic effects, there is a possibility for a stable Bi + oxidation state due to the splitting of the p-orbitals and the development of a double inert pair effect, Bi + : 6s 2 6p1/2 2 6p3/2 0 . However, due to the fact relativistic effects are small for Bi, the Bi + state is not apparently chemically stable [154]. In aqueous solutions Bi is shown to only form mononuclear species.…”

“…The elements of the group vary drastically as the group is descended, with the lighter elements being nonmetals, the heavier elements being metallic in character, and elements in the middle exhibiting semi-metallic character. As in the group 14 elements, the tendency of the heavier group members to show increasing stability of the lower oxidation state can be attributed to the inertpair effect [154]. At this time, with the exception of generator studies by Guseva et al Bismuth is the heaviest element with a stable isotope.…”

“…In nitric acid solutions metallic Bi tends to form a nitrate complex (Bi(NO3)3) as well as has the possibility of complex ion formation for high nitric acid concentration. However, a Bi(NO3)3•5H2O species can crystallize out easily [154]. For tracer levels of Bi 3+ (less than 10 -7 M) in 1M HNO3, Bi(NO3)n 3-n , Bi(OH) (NO3)n 2-n , Bi(OH)2(NO3)n 1-n , and Bi(OH)3(NO3)n nform [155].…”

“…This can be attributed to unfavorable charge distribution compared to that of SnCl6 2possibly due to the size increase. In HNO3 Bi tends to form a large number of both cationic and anionic complexes or neutral complexes, which do not interact with the crown ether [154,155]. In nitric acid Bi most likely exists as Bi(NO3)3, which, since the analogous Pb(NO3)2 complex does extract, may be hindered due to steric factors from interaction with the crown core [154].…”