REACTIONS OF HEXAFLUORIDES OF URANIUM, NEPTUNIUM, AND PLUTONIUM WITH NITROGEN-OXIDES AND OXYFLUORIDES - SYNTHESIS AND CHARACTERIZATION OF (NO)[NPF6] AND (NO)[PUF6]
Pg. Eller et al., REACTIONS OF HEXAFLUORIDES OF URANIUM, NEPTUNIUM, AND PLUTONIUM WITH NITROGEN-OXIDES AND OXYFLUORIDES - SYNTHESIS AND CHARACTERIZATION OF (NO)[NPF6] AND (NO)[PUF6], Journal of alloys and compounds, 269(1-2), 1998, pp. 50-56
A comparative study has been performed of the reactions of nitric oxid
e (NO), nitrogen dioxide (NO2), nitrosyl fluoride (FNO), nitryl fluori
de (FNO2), and nitrogen oxytrifluoride (F3NO) with the hexafluorides o
f uranium, neptunium, and plutonium. Significant chemical differences
among the hexafluorides were found. Thus, UF6 and excess NO reacted at
room temperature to form the nitrosonium salt (NO)[UF6], the same U(V
) product formed from the reaction of UF6 with excess NO2. Excess NO r
eacted rapidly with NpF6 to form poorly crystalline Np(IV) solids, but
with an equimolar amount of PuF6 at reduced temperature NO reacted to
yield a mixture of Pu(IV) species and the new compound (NO)[PuF6]. Wi
th NpF6, FNO reacted only under photolytic conditions to give (NO)[NpF
6], whereas PuF6 oxidized FNO to give F3NO and a mixture of (NO)[PuF6]
and Pu(IV) solids. No reaction was observed between NpF6 or PuF6 with
FNO2. Likewise, no reaction was observed between F3NO and the actinid
e hexafluorides, even under photolytic conditions. (C) 1998 Elsevier S
cience S.A.