Hostname: page-component-cd9895bd7-dk4vv Total loading time: 0 Render date: 2024-12-26T21:07:51.077Z Has data issue: false hasContentIssue false
  • English
  • Français

Synthesis and Characterization of 5- and 6- Coordinated Alkali Pertechnetates

Published online by Cambridge University Press:  12 January 2017

Jamie Weaver ,
Chuck Soderquist ,
Paul Gassman ,
Eric Walter ,
Wayne Lukens  and
John S. McCloy
Jamie Weaver
Affiliation:
Department of Chemistry, Washington State University, Pullman, WA 99164, USA Pacific Northwest National Laboratory, Richland, WA 99352, USA
Chuck Soderquist
Affiliation:
Pacific Northwest National Laboratory, Richland, WA 99352, USA
Paul Gassman
Affiliation:
Pacific Northwest National Laboratory, Richland, WA 99352, USA
Eric Walter
Affiliation:
Pacific Northwest National Laboratory, Richland, WA 99352, USA
Wayne Lukens
Affiliation:
Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
John S. McCloy*
Affiliation:
Department of Chemistry, Washington State University, Pullman, WA 99164, USA Pacific Northwest National Laboratory, Richland, WA 99352, USA Materials Science and Engineering Program and School of Mechanical & Materials Engineering, Washington State University, Pullman, WA 99164, USA
*
*(Email: john.mccloy@wsu.edu)
Get access

Abstract

The local chemistry of technetium-99 (99Tc) in oxide glasses is important for understanding the incorporation and long-term release of Tc from nuclear waste glasses, both those for legacy defense wastes and fuel reprocessing wastes. Tc preferably forms Tc(VII), Tc(IV), or Tc(0) in glass, depending on the level of reduction of the melt. Tc(VII) in oxide glasses is normally assumed to be isolated pertechnetate TcO4- anions surrounded by alkali, but can occasionally precipitate as alkali pertechnetate salts such as KTcO4 and NaTcO4 when Tc concentration is high. In these cases, Tc(VII) is 4-coordinated by oxygen. A reinvestigation of the chemistry of alkali-technetium-oxides formed under oxidizing conditions and at temperatures used to prepare nuclear waste glasses showed that higher coordinated alkali Tc(VII) oxide species had been reported, including those with the TcO5- and TcO6- anions. The chemistry of alkali Tc(VII) and other alkali-Tc-oxides is reviewed, along with relevant synthesis conditions.

Additionally, we report attempts to make 5- and 6-coordinate pertechnetate compounds of K, Na, and Li, i.e. TcO5- and TcO6-. It was found that higher coordinated species are very sensitive to water, and easily decompose into their respective pertechnetates. It was difficult to obtain pure compounds, but mixtures of the pertechnetate and other phase(s) were frequently found, as evidenced by x-ray absorption spectroscopy (XAS), neutron diffraction (ND), and Raman spectroscopy. Low temperature electron paramagnetic resonance (EPR) measurements showed the possibility of Tc(IV) and Tc(VI) in Na3TcO5 and Na5TcO6 compounds.

It was hypothesized that the smaller counter cation would result in more stable pertechnetates. To confirm the synthesis method, LiReO4 and Li5ReO6 were prepared, and their Raman spectra match those in the literature. Subsequently, the Tc versions LiTcO4 and Li5TcO6 were synthesized and characterized by ND, Raman spectroscopy, XANES, and EXAFS. The Li5TcO6 was a marginally stable compound that appears to have the same structure as that known for Li5ReO6. Implications of the experimental work on stability of alkali technetate compounds and possible role in the volatilization of Tc are discussed.

Keywords

extended x-ray absorption fine structure(EXAFS)neutron scatteringnuclear materials
Type
Articles
Information
MRS Advances , Volume 2 , Issue 10: Scientific Basis for Nuclear Waste Management XL , 2017 , pp. 525 - 542
Copyright
Copyright © Materials Research Society 2017 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

Vienna, J.D., Ryan, J.V., Gin, S. and Inagaki, Y., Int. J. Appl. Glass Sci. 4, 283 (2013).Google Scholar
Icenhower, J.P., Qafoku, N.P., Zachara, J.M. and Martin, W.J., Amer. J. Science 310, 721 (2010).Google Scholar
Darab, J.G. and Smith, P.A., Chem. Mater. 8, 1004 (1996).Google Scholar
Weaver, J., Localized chemistry of 99Tc in simulated low activity waste glass, Department of Chemistry, PhD dissertation, Washington State University, Pullman, WA (2016).Google Scholar
Soderquist, C.Z., Schweiger, M.J., Kim, D.-S., Lukens, W.W. and McCloy, J.S., J. Nucl. Mater. 449, 173 (2014).Google Scholar
Gassman, P.L., McCloy, J.S., Soderquist, C.Z. and Schweiger, M.J., J. Raman Spectrosc. 45, 139 (2014).Google Scholar
Baumgartner, F., Krebs, K. and Merte, B., Investigations concerning the source term for the emission of fission products and transuranic elements from the highly radioactive waste in the temperature region between 200 and 1100 0 C, Savannah River Lab., Aiken, SC (USA)DP-TR–90 (1984).Google Scholar
Bibler, N.E., Fellinger, T.L., Marra, S.L., O’Drisscoll, R.J., Ray, J.W. and Boyce, W.T. in Scientific basis for nuclear waste management XXIII, edited by Smith, R. W. and Shoesmith, D. W., (Mater. Res. Soc. Symp. Proc. 608, Boston, MA, 2000), pp. 697.Google Scholar
Migge, H. in Scientific Basis for Nuclear Waste Management XIII, edited by Oversby, V. M. and , P. W.Brown, , (Mater. Res. Soc. Symp. Proc. 176, Boston, MA, 1990), pp. 411.Google Scholar
Keller, C. and Kanellakopulos, B., J. Inorg. Nucl. Chem. 27, 787 (1965).Google Scholar
Kanellakopulos, B., The ternary oxide of 3-to 7-valent technetium with alkalis, Kernforschungszentrum. Inst. Radiochem., Karlsruhe, Germany, IssueAEC Accession No. 31424, Rept. No. KFK-197 (1964).Google Scholar
Schwochau, K., Technetium: Chemistry and Radiopharmaceutical Applications, (Wiley, 2000).Google Scholar
Keller, C. and Wassilopulos, M., Radiochim. Acta 5, 87 (1966).CrossRefGoogle Scholar
Rard, J.A., Sandino, C.A. and Östhols, E., Chemical thermodynamics of technetium, (North-Holland, 1999).Google Scholar
Kemmitt, R.D.W. and Peacock, R.D., The chemistry of manganese, technetium, and rhenium: Pergamon texts in inorganic chemistry, (Pergamon Press, 1973).Google Scholar
German, K.E., Kryuchkov, S.V. and Belyaeva, L.I., Izv. Akad. Nauk SSSR, Ser. Khim. 10, 2387 (1987).Google Scholar
Shklovskaya, R.M., Arkhipov, S.M. and Kidyarov, B.I., Zh. Neorg. Khim. 24, 2287 (1979).Google Scholar
Abakumov, A.M., Rozova, M.G., Shpanchenko, R.V., Mironov, A.V., Antipov, E.V. and Bramnik, K.G., Solid State Sci. 3, 581 (2001).Google Scholar
Keller, C. and Kanellakopulos, B., Radiochim. Acta 1, 107 (1963).CrossRefGoogle Scholar
Busey, R.H. and Keller, O.L. Jr., J. Chem. Phys. 41, 215 (1964).Google Scholar
Rulfs, C.L., Hirsch, R.F. and Pacer, R.A., Nature 199, 66 (1963).Google Scholar
Smith, W.T., Cobble, J.W. and Boyd, G.E., J. Amer. Chem. Soc. 75, 5773 (1953).Google Scholar
Webb, S.M., Physica Scripta 2005, 1011 (2005).CrossRefGoogle Scholar
Ravel, B. and Newville, M., J. Synchr. Rad. 12, 537 (2005).Google Scholar
Neuefeind, J., Feygenson, M., Carruth, J., Hoffmann, R. and Chipley, K.K., Nucl. Instrum. Meth. B 287, 68 (2012).Google Scholar
Toby, B., J. Appl. Cryst. 34, 210 (2001).Google Scholar
Lukens, W.W., Bucher, J.J., Edelstein, N.M. and Shuh, D.K., Environ. Sci. Technol. 36, 1124 (2002).Google Scholar
Levitskaia, T.G., Chatterjee, S., Pence, N.K., Romero, J., Varga, T., Engelhard, M.H., Du, Y., Kovarik, L., Arey, B.W., Bowden, M.E. and Walter, E.D., Env. Sci. Nano 3, 1003 (2016).CrossRefGoogle Scholar
Kirmse, R. and Abram, U., Isotopenpraxis Isot. Environ. Health Stud. 26, 151 (1990).Google Scholar
Mogare, K.M., Klein, W., Schilder, H., Lueken, H. and Jansen, M., , Z. Anorg. Allg. Chem. 632, 2389 (2006).CrossRefGoogle Scholar
Betz, T. and Hoppe, R., Anorg, Z.. Allg. Chem. 512, 19 (1984).Google Scholar
Morss, L.R., Appelman, E.H., Gerz, R.R. and Martin-Rovet, D., J. Alloys Compd. 203, 289 (1994).Google Scholar
Baud, G., Besse, J.P., Chevalier, R. and Gasperin, M., J. Solid State Chem. 29, 267 (1979).Google Scholar
Crumpton, T.E., Mosselmans, J.F.W. and Greaves, C., J. Mater. Chem. 15, 164 (2005).CrossRefGoogle Scholar
Baran, E.J., Monatshefte für Chemie 108, 891 (1977).Google Scholar
Ulbricht, K. and Kriegsmann, H., Anorg, Z.. Allg. Chem. 538, 193 (1968).CrossRefGoogle Scholar
Scholder, R. and Huppert, K.L., Anorg, Z.. Allg. Chem. 334, 209 (1964).CrossRefGoogle Scholar
Vielhaber, E. and Hoppe, R., Anorg, Z.. Allg. Chem. 610, 7 (1992).Google Scholar
Duquenoy, G., Rev. Chim. Miner. 8, 683 (1971).Google Scholar
Chretien, A. and Duquenoy, G., Acad, C. R.. Sci., Paris, Ser. C 268, 509 (1969).Google Scholar
Hauck, J., Naturforsch, Z.. B 24, 1064 (1969).Google Scholar
Hauck, J., Naturforsch, Z.. B 23, 1603 (1968).Google Scholar
Sobotka, B.M., Mudring, A.-V. and Moeller, A., Anorg, Z.. Allg. Chem. 630, 2377 (2004).Google Scholar
Childs, B., Poineau, F., Czerwinski, K. and Sattelberger, A., J. Radioanal. Nucl. Chem. 306, 417 (2015).Google Scholar
Langowski, M.H., Darab, J.G. and Smith, P.A., Volatility literature of chlorine, iodine, cesium, strontium, technetium, and rhenium; technetium and rhenium volatility testing, Pacific Northwest National Laboratory, Richland, WA, PNNL-11052 (1996).Google Scholar
Colton, R., The chemistry of rhenium and technetium, (Interscience Publishers, 1965).Google Scholar
Vida, J., The chemical behavior of technetium during treatment of high-level radioactive waste [translated from German by JR Jewett], Battelle Pacific Northwest Laboratory, Richland, WA, PNL-TR-497 (1994).Google Scholar
Rard, J.A., Critical Review of the Chemistry and Thermodynamics of Technetium and Some of its Inorganic Compounds and Aqueous Species, Lawrence Livermore National Laboratory, Livermore, CA, UCRL-53440 (1983).Google Scholar