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

  • Jamie Weaver (a1) (a2), Chuck Soderquist (a2), Paul Gassman (a2), Eric Walter (a2), Wayne Lukens (a3) and John S. McCloy (a1) (a2) (a4)...
Abstract
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.

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Corresponding author
*(Email: john.mccloy@wsu.edu)
References
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1 Vienna J.D., Ryan J.V., Gin S. and Inagaki Y., Int. J. Appl. Glass Sci. 4, 283 (2013).
2 Icenhower J.P., Qafoku N.P., Zachara J.M. and Martin W.J., Amer. J. Science 310, 721 (2010).
3 Darab J.G. and Smith P.A., Chem. Mater. 8, 1004 (1996).
4 Weaver J., Localized chemistry of 99Tc in simulated low activity waste glass, Department of Chemistry, PhD dissertation, Washington State University, Pullman, WA (2016).
5 Soderquist C.Z., Schweiger M.J., Kim D.-S., Lukens W.W. and McCloy J.S., J. Nucl. Mater. 449, 173 (2014).
6 Gassman P.L., McCloy J.S., Soderquist C.Z. and Schweiger M.J., J. Raman Spectrosc. 45, 139 (2014).
7 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).
8 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.
9 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.
10 Keller C. and Kanellakopulos B., J. Inorg. Nucl. Chem. 27, 787 (1965).
11 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).
12 Schwochau K., Technetium: Chemistry and Radiopharmaceutical Applications, (Wiley, 2000).
13 Keller C. and Wassilopulos M., Radiochim. Acta 5, 87 (1966).
14 Rard J.A., Sandino C.A. and Östhols E., Chemical thermodynamics of technetium, (North-Holland, 1999).
15 Kemmitt R.D.W. and Peacock R.D., The chemistry of manganese, technetium, and rhenium: Pergamon texts in inorganic chemistry, (Pergamon Press, 1973).
16 German K.E., Kryuchkov S.V. and Belyaeva L.I., Izv. Akad. Nauk SSSR, Ser. Khim. 10, 2387 (1987).
17 Shklovskaya R.M., Arkhipov S.M. and Kidyarov B.I., Zh. Neorg. Khim. 24, 2287 (1979).
18 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).
19 Keller C. and Kanellakopulos B., Radiochim. Acta 1, 107 (1963).
20 Busey R.H. and Keller O.L. Jr., J. Chem. Phys. 41, 215 (1964).
21 Rulfs C.L., Hirsch R.F. and Pacer R.A., Nature 199, 66 (1963).
22 Smith W.T., Cobble J.W. and Boyd G.E., J. Amer. Chem. Soc. 75, 5773 (1953).
23 Webb S.M., Physica Scripta 2005, 1011 (2005).
24 Ravel B. and Newville M., J. Synchr. Rad. 12, 537 (2005).
25 Neuefeind J., Feygenson M., Carruth J., Hoffmann R. and Chipley K.K., Nucl. Instrum. Meth. B 287, 68 (2012).
26 Toby B., J. Appl. Cryst. 34, 210 (2001).
27 Lukens W.W., Bucher J.J., Edelstein N.M. and Shuh D.K., Environ. Sci. Technol. 36, 1124 (2002).
28 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).
29 Kirmse R. and Abram U., Isotopenpraxis Isot. Environ. Health Stud. 26, 151 (1990).
30 Mogare K.M., Klein W., Schilder H., Lueken H. and Jansen M., Z. Anorg. Allg. Chem. 632, 2389 (2006).
31 Betz T. and Hoppe R., Anorg Z.. Allg. Chem. 512, 19 (1984).
32 Morss L.R., Appelman E.H., Gerz R.R. and Martin-Rovet D., J. Alloys Compd. 203, 289 (1994).
33 Baud G., Besse J.P., Chevalier R. and Gasperin M., J. Solid State Chem. 29, 267 (1979).
34 Crumpton T.E., Mosselmans J.F.W. and Greaves C., J. Mater. Chem. 15, 164 (2005).
35 Baran E.J., Monatshefte für Chemie 108, 891 (1977).
36 Ulbricht K. and Kriegsmann H., Anorg Z.. Allg. Chem. 538, 193 (1968).
37 Scholder R. and Huppert K.L., Anorg Z.. Allg. Chem. 334, 209 (1964).
38 Vielhaber E. and Hoppe R., Anorg Z.. Allg. Chem. 610, 7 (1992).
39 Duquenoy G., Rev. Chim. Miner. 8, 683 (1971).
40 Chretien A. and Duquenoy G., Acad C. R.. Sci., Paris, Ser. C 268, 509 (1969).
41 Hauck J., Naturforsch Z.. B 24, 1064 (1969).
42 Hauck J., Naturforsch Z.. B 23, 1603 (1968).
43 Sobotka B.M., Mudring A.-V. and Moeller A., Anorg Z.. Allg. Chem. 630, 2377 (2004).
44 Childs B., Poineau F., Czerwinski K. and Sattelberger A., J. Radioanal. Nucl. Chem. 306, 417 (2015).
45 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).
46 Colton R., The chemistry of rhenium and technetium, (Interscience Publishers, 1965).
47 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).
48 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).
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