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Title: Chemical Trends in Solid Alkali Pertechnetates

Abstract

Insight into the solid-state chemistry of pure technetium-99 (99Tc) oxides is required in the development of a robust immobilization and disposal system for nuclear waste stemming from the radiopharmaceutical industry, from the production of nuclear weapons, and from spent nuclear fuel. However, because of its radiotoxicity and the subsequent requirement of special facilities and handling procedures for research, only a few studies have been completed, many of which are over 20 years old. In this study, we report the synthesis of pure alkali pertechnetates (sodium, potassium, rubidium, and cesium) and analysis of these compounds by Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), solid-state nuclear magnetic resonance (static and magic angle spinning), and neutron diffraction. The structures and spectral signatures of these compounds will aid in refining the understanding of 99Tc incorporation into and release from nuclear waste glasses. NaTcO4 shows aspects of the relatively higher electronegativity of the Na atom, resulting in large distortions of the pertechnetate tetrahedron and deshielding of the 99Tc nucleus relative to the aqueous TcO4-. At the other extreme, the large Cs and Rb atoms interact only weakly with the pertechnetate, have closer to perfect tetrahedral symmetry at the Tc atom, and have very similarmore » vibrational spectra, even though the crystal structure of CsTcO4 is orthorhombic while that of RbTcO4 is tetragonal. Further trends are observed in the cell volume and quadrupolar coupling constant« less

Authors:
 [1];  [2]; ORCiD logo [2];  [2];  [2]; ORCiD logo [3];  [4];  [5]; ORCiD logo [6]
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  1. Department of Chemistry, Washington State University, Pullman, Washington 99164, United States, Pacific Northwest National Laboratory, Richland, Washington 99352, United States
  2. Pacific Northwest National Laboratory, Richland, Washington 99352, United States
  3. Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  4. U.S. Department of Energy (DOE), Office of River Protection, Richland, Washington 99352, United States
  5. Department of Chemistry, Washington State University, Pullman, Washington 99164, United States
  6. Department of Chemistry, Washington State University, Pullman, Washington 99164, United States, Pacific Northwest National Laboratory, Richland, Washington 99352, United States, Materials Science and Engineering Program and School of Mechanical & Materials Engineering, Washington State University, Pullman, Washington 99164, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1344320
Alternate Identifier(s):
OSTI ID: 1344529; OSTI ID: 1408420; OSTI ID: 1508096
Report Number(s):
PNNL-SA-121324
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC0576RL01830; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Name: Inorganic Chemistry Journal Volume: 56 Journal Issue: 5; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Weaver, Jamie, Soderquist, Chuck Z., Washton, Nancy M., Lipton, Andrew S., Gassman, Paul L., Lukens, Wayne W., Kruger, Albert A., Wall, Nathalie A., and McCloy, John S. Chemical Trends in Solid Alkali Pertechnetates. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.6b02694.
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Weaver, Jamie, Soderquist, Chuck Z., Washton, Nancy M., Lipton, Andrew S., Gassman, Paul L., Lukens, Wayne W., Kruger, Albert A., Wall, Nathalie A., & McCloy, John S. Chemical Trends in Solid Alkali Pertechnetates. United States. https://doi.org/10.1021/acs.inorgchem.6b02694
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Weaver, Jamie, Soderquist, Chuck Z., Washton, Nancy M., Lipton, Andrew S., Gassman, Paul L., Lukens, Wayne W., Kruger, Albert A., Wall, Nathalie A., and McCloy, John S. Tue . "Chemical Trends in Solid Alkali Pertechnetates". United States. https://doi.org/10.1021/acs.inorgchem.6b02694.
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@article{osti_1344320,
title = {Chemical Trends in Solid Alkali Pertechnetates},
author = {Weaver, Jamie and Soderquist, Chuck Z. and Washton, Nancy M. and Lipton, Andrew S. and Gassman, Paul L. and Lukens, Wayne W. and Kruger, Albert A. and Wall, Nathalie A. and McCloy, John S.},
abstractNote = {Insight into the solid-state chemistry of pure technetium-99 (99Tc) oxides is required in the development of a robust immobilization and disposal system for nuclear waste stemming from the radiopharmaceutical industry, from the production of nuclear weapons, and from spent nuclear fuel. However, because of its radiotoxicity and the subsequent requirement of special facilities and handling procedures for research, only a few studies have been completed, many of which are over 20 years old. In this study, we report the synthesis of pure alkali pertechnetates (sodium, potassium, rubidium, and cesium) and analysis of these compounds by Raman spectroscopy, X-ray absorption spectroscopy (XANES and EXAFS), solid-state nuclear magnetic resonance (static and magic angle spinning), and neutron diffraction. The structures and spectral signatures of these compounds will aid in refining the understanding of 99Tc incorporation into and release from nuclear waste glasses. NaTcO4 shows aspects of the relatively higher electronegativity of the Na atom, resulting in large distortions of the pertechnetate tetrahedron and deshielding of the 99Tc nucleus relative to the aqueous TcO4-. At the other extreme, the large Cs and Rb atoms interact only weakly with the pertechnetate, have closer to perfect tetrahedral symmetry at the Tc atom, and have very similar vibrational spectra, even though the crystal structure of CsTcO4 is orthorhombic while that of RbTcO4 is tetragonal. Further trends are observed in the cell volume and quadrupolar coupling constant},
doi = {10.1021/acs.inorgchem.6b02694},
journal = {Inorganic Chemistry},
number = 5,
volume = 56,
place = {United States},
year = {Tue Feb 21 00:00:00 EST 2017},
month = {Tue Feb 21 00:00:00 EST 2017}
}
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https://doi.org/10.1021/acs.inorgchem.6b02694
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