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SANS study of third phase formation in the U(VI)-HNO{sub 3}/ TBP-n-dodecane system.

Journal Article · · Sep. Sci. Technol.
In spite of its technological importance, third phase formation in the extraction of hexavalent actinides from nitric acid solutions into alkane solutions of tri-n-butylphosphate (TBP) has received only limited attention. The focus of the few available literature works has been primarily centered on the composition of the third phase and on the stoichiometry of the metal complexes. Very little is known, on the other hand, about the structure and morphology of the third phase species of hexavalent actinides. In the present investigation, the formation of a third phase upon extraction of U(VI) by 20% TBP in deuterated n-dodecane from nitric acid solutions was studied. Chemical analyses have shown that U(VI) exists in the third phase as a species having the composition UO{sub 2}(NO{sub 3}){sub 2}{center_dot}(TBP){sub 2}{center_dot}HNO{sub 3}. Small-angle neutron scattering measurements on TBP solutions loaded with only HNO{sub 3} or with increasing amounts of U(VI) have revealed the presence, both before and after phase splitting, of relatively large ellipsoidal aggregates with the parallel and perpendicular axes having lengths up to about 64 and 15 Angstroms, respectively. The formation of these aggregates is observed in all cases, that is, when only HNO3, only UO{sub 2}(NO{sub 3}){sub 2}, or both HNO{sub 3} and UO{sub 2}(NO{sub 3}){sub 2} are extracted by the TBP solution. Upon third phase formation, the SANS data reveal the presence of smaller aggregates in both the heavy and light organic phase.
Research Organization:
Argonne National Laboratory (ANL)
Sponsoring Organization:
SC
DOE Contract Number:
AC02-06CH11357
OSTI ID:
949447
Report Number(s):
ANL/CHM/JA-41013
Journal Information:
Sep. Sci. Technol., Journal Name: Sep. Sci. Technol. Journal Issue: 12-13 ; 2003 Vol. 38; ISSN 0149-6395; ISSN SSTEDS
Country of Publication:
United States
Language:
ENGLISH

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