Comparisons of Plutonium, Thorium, and Cerium Tellurite Sulfates

Abstract

The hydrothermal reaction of PuCl3 or CeCl3 with TeO2 in the presence of sulfuric acid under the comparable conditions results in the crystallization of Pu(TeO3)(SO4) or Ce2(Te2O5)(SO4)2, respectively. Pu(TeO3)(SO4) and its isotypic compound Th(TeO3)(SO4) are characterized by a neutral layer structure with no interlamellar charge-balancing ions. However, Ce2(Te2O5)(SO4)2 possesses a completely different dense three-dimensional framework. Bond valence calculation and UV-vis-NIR spectra indicate that the Ce compound is trivalent whereas the Pu and Th compounds are tetravalent leading to the formation of significantly different compounds. Pu(TeO3)(SO4), Th(TeO3)(SO4), and Ce2(Te2O5)(SO4)2 represent the first plutonium/thorium/cerium tellurite sulfate compounds. Our study strongly suggests that the chemistries of Pu and Ce are not the same, and this is another example of the failure of Ce as a surrogate.

Incorporation of Sulfate or Selenate Groups into Oxotellurates(IV): I. Calcium, Cadmium, and Strontium Compounds

“…So far, only a few metal oxotellurate(IV) phases with additional X O 4 groups have been reported, mostly prepared under hydrothermal conditions. This includes the sulfates Al 2 (OH) 2 (SO 4 )(TeO 3 ), Fe 2 (TeO 3 ) 2 (SO 4 )(H 2 O) 3 , Cu 7 (OH) 6 (TeO 3 ) 2 (SO 4 ) 2 , Cu 7 TeO 4 (SO 4 ) 5 KCl, the series RE 2 M (TeO 3 ) 2 (SO 4 ) 2 ( RE = rare earth metal; M = Cu, Co, Zn),, Pu(TeO 3 )(SO 4 ), Th(TeO 3 )(SO 4 ), Ce 2 (Te 2 O 5 )(SO 4 ) 2 , M 2 (TeO 3 )(SO 4 )H 2 O ( M = Co, Mn), and BiCu 2 (TeO 3 )(SO 4 )‐(OH) 3 , and to a much lesser extend the selenates Sc 2 (TeO 3 )‐(SeO 3 )(SeO 4 ) (also comprising an oxoselenate(IV) group), Bi 2 (TeO 3 ) 2 (SeO 4 ) and the already noted mercury compounds Hg 3 (SeO 4 )(TeO 3 ) 2 and Hg 3 (SeO 4 )(Te 4 O 10 ) …”

Synthesis, Structure, and Optical Properties of BiCu2(TeO3)(SO4)(OH)3

“…In our recent research, we tried to find new tellurite‐sulfate compounds by selecting lanthanide and other +3 cations sulfates as model compounds with the partial substitution of TeO 3 2– for SO 4 2– . In fact, to date only a few telluri(a)te‐sulfate minerals and synthetic compounds such as poughite Fe 2 (TeO 3 ) 2 (SO 4 ) · 3H 2 O,22,23 nabokoite Cu 7 (TeO 4 )(SO 4 ) 5 · KCl,24 Cu 7 (OH) 6 (TeO 3 ) 2 (SO 4 ) 2 ,25 Al 2 (OH) 2 (TeO 3 )(SO 4 ),26 M 2 (TeO 3 )(SO 4 ) · H 2 O ( M = Co, Mn),27 M 3 (TeO 3 )(SO 4 )(OH) 2 · 2H 2 O ( M = Ni, Co),28 Pu(TeO 3 )(SO 4 ), Th(TeO 3 )(SO 4 ),29 Pb 10 Te 6 O 20 (OH) 14 (SO 4 ) · 5H 2 O,30 and Pb 2 Cu 4 Te 2 O 10 (OH) 2 (SO 4 )(H 2 O)31 have been reported. Among these compounds, only the last two compounds are tellurate‐sulfate minerals containing Te 6+ .…”

Origins of the odd optical observables in plutonium and americium tungstates

“…The band in the Ce complex leads to the observed yellow color. While yellow Ce( iii ) complexes are known, it is more typical for Ce( iii ) oxoanion complexes to be colorless 15,17,18,20,45,46. The broad absorption of the Pu complex proceeds into what appears to be the 4 L 13/2 and 4 M 15/2 peaks around 600 nm and the 6 F 3/2 peak ∼660 nm.…”

“…In order to uncover the underlying ligand properties that determine whether or not significant differences between 4f and 5f elements are expressed, we have also prepared a number of actinide oxoanion compounds that span both the lanthanide and actinide series 17–20. Currently, some of the most promising oxoanions are those with large hyperpolarizabilities; a quantified value of the susceptibility of a M–O bond to the electric field from impinging light that is calculated from phase-matched second-harmonic generation data 21.…”