Dehydration of uranyl nitrate hexahydrate to uranyl nitrate trihydrate under ambient conditions as observed via dynamic infrared reflectance spectroscopy

Abstract

Uranyl nitrate is a key species in the nuclear fuel cycle, but is known to exist in different states of hydration, including the hexahydrate [UO2(NO3)2(H2O)6] (UNH) and the trihydrate [UO2(NO3)2(H2O)3] (UNT) forms. Their stabilities depend on both relative humidity and temperature. Both phases have previously been studied by infrared transmission spectroscopy, but the data were limited by both instrumental resolution and the ability to prepare the samples as pellets without desiccating it. We report time-resolved infrared (IR) measurements using an integrating sphere that allow us to observe the transformation from the hexahydrate to the trihydrate simply by flowing dry nitrogen gas over the sample. Hexahydrate samples were prepared and confirmed via known XRD patterns, then measured in reflectance mode. The hexahydrate has a distinct uranyl asymmetric stretch band at 949.0 cm -1 that shifts to shorter wavelengths and broadens as the sample dehydrates and recrystallizes to the trihydrate, first as a blue edge shoulder but ultimately resulting in a doublet band with reflectance peaks at 966 and 957 cm -1 . The data are consistent with transformation from UNH to UNT since UNT has two non-equivalent UO2 2+ sites. The dehydration of UO2(NO3)2(H2O)6 to UO2(NO3)2(H2O)3 is both a morphological and structural change that has the lustrous lime green crystals changing to the dull greenish yellow of the trihydrate. Crystal structures and phase transformation were confirmed theoretically using DFT calculations and experimentally via microscopy methods. Both methods showed a transformation with two distinct sites for the uranyl cation in the trihydrate, as opposed to a single crystallographic site in the hexahydrate.

Time-Resolved Infrared Reflectance Studies of the Dehydration-Induced Transformation of Uranyl Nitrate Hexahydrate to the Trihydrate Form

“…In this paper we have made seminal reflectance infrared observations of uranyl nitrate during the desiccation of the hexahydrate to the trihydrate, possibly even to the dihydrate. 46 Time-resolved infrared reflectance spectroscopy was employed and proved a superior approach to such dehydration studies. We report direct observation of phase transformation from UO 2 (NO 3 ) 2 (H 2 O) 6 to UO 2 (NO 3 ) 3 (H 2 O) 3 through high resolution reflectance IR measurements and in situ optical microscopy imaging, with absolute confirmation of the phase mixture via XRD.…”