Abstract
Technetium is a hazardous fission product with a long half-life. In vitrification of nuclear waste, technetium tends to be lost substantially by evaporation [1], and the formation of gaseous Tc oxides is assumed to be the reason. Reliable thermochemical treatment of the problem is difficult, since data on the Tc-O system are surprisingly scarce [2]. Therefore, the system Re-O is treated for comparison. Key thermodynamic data for the condensed rhenium oxides exist [3,4,5] as well as measurements on the sublimation and the evaporation of the oxides [6–11]. Consistency of the different data is investigated by assessing the sublimation data of solid Re2O7, using them to calculate other sublimation equilibria and to compare the results with published measurements. Then a predominance area diagram is constructed and discussed with respect to the pressures of the gaseous oxides and their dependence on the temperature, oxygen partial pressure, and condensed oxide phase present. Predominance area diagrams of the Tc-O system are calculated and critically discussed. Owing to the small amout of available data, the possible existence of solid TcO3 is discussed. Comparison with the system Re-O is used to clarify, where further investigations need to be done.
Similar content being viewed by others
References
A. Jouan, J.P. Moncouyoux, S. Halaszovich, EUR 10650, 1986
J.A. Rard, UCRL - 53440,1983.
E.G. King, D.W. Richardson and R.V. Mrazek, BM-RJ-7323, 1969.
J.M. Stuve and M.J. Ferrante, BM-8199, 1976.
L.B. Pankratz, BM-672, 1982.
J.E. Battles, G.E. Gunderson, R.K. Edwards, J. Phys.Chem.72, 3963 (1968).
H.B. Skinner and A.W. Searcy, J. Phys. Chem. 77, 1578 (1973).
W.T. Smith, L.E. Line, and W.A. Bell, J. Am. Chem. Soc. 74, 4964 (1952).
O. Glemser, A. Müller und U. Stöcker, Z. anorg. allg. Chem 333, 26 (1964).
H. Martens und S. Ziegenbalg, Z. anorg. allg. Chem. 401, 145 (1973).
H. Oppermann, Z. anorg. allg. Chem. 523, 135 (1985).
J.I. Franco und H. Kleykamp, Berichte Bunsen-Ges. 75, 934 (1971).
R.H. Busey, J. Am. Chem. Soc. 78, 3263 (1956).
T.N. Rezukhina and T.J. Gorshkova, Zhurnal Fiz. Khimii, 54, 2688 (1980) [Russ. J. Phys. Chem., 54, 1537 (1980)]
H.L. Schick, Thermodynamics of Certain Refractory Compounds. Vol. II, Academic Press, New York and London, 1966.
M. Studier, J. Phys. Chem. 66, 189 (1962)
G.A. Semenov and K.V. Ovchiunikov, Zhr. Obsch. Khim. 35, 1517 (1965) [J. General Chem. USSR, 35, 1521 (1965)].
J.E. Franklin and R.E. Stickney, High Temp. Sci. 3, 401 (1971).
T.B. Lindemer.Th.M. Besmann, C.E. Johnson, J.Nucl.Mat. 100, 178(1981).
O. Kubaschewski and C.B. Alcock, Metallurgical Thermochemistry, 5th ed. (Pergamon Press, Oxford, New York, 1979), p. 191.
JANAF Thermochemical Tables 3rd ed. in: J. Phys. and Chem. Ref. Data 14 (1985) Suppl. 1.
J. Barin, O. Knacke and O. Kubaschewski, Thermochemical Properties of Inorganic Substances (Springer-Verlag, Berlin, 1973, Suppl. 1976).
D. Schab, Freiberger Forschungshefte, B 158, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1971.
J.W. Cobble, W. T. Smith, G.E. Boyd, J. Am. Chem. Soc. 75, 5777 (1953).
K.H. Gayer, A. Y. Herrell and R.H. Busey, J. Chem. Therm. 8, 959 (1976).
W.T. Smith, J.W. Cobble, G.E. Boyd, J. Amer. Chem. Soc. 75, 5773 (1953).
G.E. Boyd, J.W. Cobble, C.M. Nelson and W.T. Smith, J. Am. Chem. Soc. 74, 556 (1952).
H.K. Kugler and C. Keller (editors), Gmelin Handbook of Inorganic Chemistry. 8th ed., Technetium, Suppl. Vol. 2, Springer Verlag, 1983
The NEA Thermochemical Data Base Project (NEA-TDB), OECD Nuclear Energy Agency, Data Bank, F - 91191 Gif-sur-Yvette, France
G.E. Boyd, J. Chem. Education, 36, 3 (1959)
D.D. Wagman et al., The NBS tables in J. Phys. Chem.Ref. Data, 11 (1982), Suppl. 2, p. 196
O. Müller, W.B. White and R. Roy, J. Inorg. Nucl. Chem., 26, 2075 (1964)
H. Kleykamp, KfK-Nachr. Jahrgang 12 4 (1980), p.37
L. Brewer, G.M. Rosenblatt, Chem. Rev. 61, 257 (1961)
C.M. Nelson, G.E. Boyd, W.T. Smith,J. Am. Chem. Soc. 76, 348 (1954)
K. Schwochau, Radiochimica Acta, 32, 139 (1983)
M. Farber et al., Combustion and Flames, 22, 191 (1974)
V.D. Budon and A.L. Tseft, Izvest. Akad. Nauk Kazakh, SSR, Ser. Met. Obogashch. i Ogneuporov 3, 49 (1958); Chem. Abstr., 54, 20392e (1960)
V.I. Deev and V.I. Smirnow, Proc. Acad. Sci. USSR, Chem. Sect. (in English), 140, 961(1961)
H. Nechemkin, A.N. Kurtz and C.F. Hiskey, J. Am. Chem. Soc. 73, 2829 (1951)
E. Freude, W. Lutze, C. Rüssel and H.A. Schaeffer, this conference
H. Lammertz, E. Merz, St. Halaszovich, Scientific Basis for Nuclear Waste Management VIII, MRS, Pittsburg, PA, 1985, p. 823–829
N.E. Bibler, A.R. Jurgensen, Scientific Basis for Nuclear Waste Management XI, MRS, Pittsburg, PA, 1987, p. 585–593
D.J. Bradley, C.O. Harvey, R.P. Turcotte, PNL-3152, 1979.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Migge, H. Thermochemical Comparison of the Systems Re-O and Tc-O. MRS Online Proceedings Library 127, 205–213 (1988). https://doi.org/10.1557/PROC-127-205
Published:
Issue Date:
DOI: https://doi.org/10.1557/PROC-127-205