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Title: Structural Investigation of Technetium Dibutylphosphate Species Using X-ray Absorption Fine Structure Spectroscopy

Journal Article · · Inorganic Chemistry
 [1];  [2];  [2];  [2]; ORCiD logo [3];  [3]; ORCiD logo [4];  [5]; ORCiD logo [6]; ORCiD logo [6]
  1. University of Nevada, Las Vegas, NV (United States); University of Nevada Las Vegas
  2. Graduate Center of the City University of New York, NY (United States); Hunter College of the City University of New York, NY (United States); Lehman College of the City University of New York, West, Bronx, NY (United States)
  3. Graduate Center of the City University of New York, NY (United States); Lehman College of the City University of New York, West, Bronx, NY (United States)
  4. Graduate Center of the City University of New York, NY (United States); Hunter College of the City University of New York, NY (United States)
  5. Oregon State University, Corvallis, OR (United States)
  6. University of Nevada, Las Vegas, NV (United States)
+ Show Author Affiliations

The speciation of Tc after the extraction of Tc(IV) from H2O and 1 M HNO3 by dibutylphosphoric acid (HDBP) in dodecane has been studied by X-ray absorption fine structure (XAFS) spectroscopy. Results show the formation of dimeric species with Tc2O2 and Tc2O units, and the formulas [Tc2O2(DBP·HDBP)4] (1) and [Tc2O(NO3)2(DBP)2(DBP·HDBP)2] (2) were, respectively, proposed for the species extracted from H2O and 1 M HNO3. The interatomic Tc–Tc distances found in the Tc2O2 and Tc2O units [2.55(3) and 3.57(4) Å, respectively] are similar to the ones found in Tc(IV) dinuclear species. It is likely that the speciation of Tc(IV) in dodecane is due to the extraction of a species with a Tc2O unit for (2) and to the redissolution of a Tc(IV)-DBP solid for (1). The XAFS results for (1) and (2) were compared to that obtained for the extraction of Tc(IV) with TBP/HDBP/dodecane from 0.5 M HNO3, (3) which highlight the formation of Tc mononuclear nitrate species {i.e. [Tc(NO3)3(DBP)] or [Tc(NO3)2(DBP·HDBP)]}. These results confirm the importance of the preparation and speciation of the Tc(IV) aqueous solutions prior to extraction and how much this influences and drives the final Tc speciation in organic extraction. Here, these studies outline the complexity of Tc separation chemistry and provide insights into the behavior of Tc during the reprocessing of used nuclear fuel.

Research Organization:
University of Nevada, Las Vegas, NV (United States)
Sponsoring Organization:
USDOE Office of Nuclear Energy (NE), Nuclear Energy University Program (NEUP); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); Consortium on Nuclear Security Technologies (CONNECT); U.S. Nuclear Regulatory Commission University Nuclear Leadership Program
Grant/Contract Number:
NA0003948; NE0008877; AC02-06CH11357; SC0012704
OSTI ID:
2203736
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 40 Vol. 62; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Anions
Extended X-ray absorption fine structure
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Fourier transforms
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