THE REACTIONSOF URANIUM AND URANIUM OXIDES WITH NITROGREN OXIDES STUDIED IN MATRICES WITH INFRARED SPECTROSCOPY
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Date
1976
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Ohio State University
Abstract
The reactions of U, UO, and $UO_{2}$ with NO and $NO_{2}$ have been studied by Fourier-transform infrared spectroscopy using the matrix-isolation technique. Codeposition of vaporized UO and $UO_{2}$ with NO and with $NO_{2}$ gases in an Ar matrix at $14^\circ K$ resulted in the production of the $UO^{+}_{2}$ , molecular ion paired with either a $NO_{2}^{-}$ or $NO^{-}$ anion. Three different reactions have been observed to yield a $UO^{+}_{2}$ cation product: (1) $UO_{2} + NO_{2}, ( 2) UO_{2} + NO,$ and $( 3) UO + NO_{2}$. Infrared absorption frequencies in the range $1150-1190 cm^{-1}$ have been measured and interpreted as the stretching modes of bend (bond angle = $109^\circ$) $N^{16}O_{2}^{-}, N^{16}O^{18}O^{-}$, and $N^{18}O_{2}^{-}$ ions paired with $UO^{+}_{2}$. Infrared absorption frequencies in the range $770-900 cm^{-1}$ have been measured and interpreted as the stretching modes of bend linear $U^{16}O_{2}^{+}, U^{16}O^{18}O^{+},$ and $U^{18}O_{2}^{+}$ paired with either $NO^{-}$ or $NO_{2}^{-}$. Codeposition of sputtered uranium atoms with $NO_{2}$ yields reaction products that are not present in matrices containing U in Ar or $NO_{2}$ in Ar separately. Some tentative identifications of these reaction products have been made. Evidence for the occurrence of the reactions $U + NO_{2} \rightarrow UO + NO$ and $U + NO_{2} \rightarrow UO_{2} + N$ has been observed. Other reaction products have not been fully characterized.
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Author Institution: Chemical Engineering Division, Argonne National Laboratory