Comparison of reactivity based on intercalation and host lattice reconstruction. Two routes for the conversion of the lamellar solid hydrogen uranyl phosphate to a lamellar hydrate of uranyl phosphate
The solid-state structural change accompanying intercalation can be profound and have been used to analyze interactions of guest species with host lattices. The authors and others have studied hydrogen uranyl phosphate (HUP), HUO/sub 2/PO/sub 4/, and demonstrated that the lamellar solid readily undergoes intercalative ion-exchange reactions, eq 1. Typically, the protons residing between the (1/n)M/sup n/ + HUO/sub 2/PO/sub 4/ ..-->.. M/sub 1/n/UO/sub 2/PO/sub 4/ + H/sup +/ (1) (UO/sub 2/PO/sub 4/)/sub n//sup n-/ sheets can be exchanged simply by slurrying the HUP powder in an aqueous solution containing the ion to be intercalated. It occurred to the authors that use of UO/sub 2//sup 2 +/ as the intercalant in eq 1 would lead to formation of uranyl phosphate (UP), (UO/sub 2/)/sub 3/(PO/sub 4/)/sub 2/. Furthermore, the report that UP can be prepared from an aqueous HUP slurry by thermal decomposition, eq 2, provided us with a 3HUO/sub 2/PO/sub 4/ ..-->.. H/sub 3/PO/sub 4/ + (UO/sub 2/)/sub 3/(PO/sub 4/)/sub 2/ (2) novel opportunity to compare two pathways to the same product. They report herein that can be quantitatively converted by intercalation (eq 1) or host lattice reconstruction (eq 2) to a common lamellar hydrate of UP; both reactions are reversible at room temperature. Moreover, an Arrhenius treatment of calculated rates for the forward reactions supports the notion that they proceed by quite different mechanisms.
- Research Organization:
- Univ. of Wisconsin, Madison
- OSTI ID:
- 6539162
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Journal Issue: 10 Vol. 109:10; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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360602 -- Other Materials-- Structure & Phase Studies
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400702* -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ACTINIDE COMPOUNDS
ARRHENIUS EQUATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CLATHRATES
COHERENT SCATTERING
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
EQUATIONS
EXPERIMENTAL DATA
HYDRATES
HYDROGEN COMPOUNDS
INFORMATION
INFRARED SPECTRA
KINETICS
MEDIUM TEMPERATURE
NUMERICAL DATA
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS COMPOUNDS
POWDERS
REACTION KINETICS
SCATTERING
SOLIDS
SPECTRA
URANIUM COMPOUNDS
URANYL COMPOUNDS
URANYL PHOSPHATES
X-RAY DIFFRACTION