Behavior of molybdenum in pyrochemical reprocessing: A spectroscopic study of the chlorination of molybdenum and its oxides in chloride melts / Volkovicha V.A., Griffiths T.R., Thied R.C., Lewin B. // Journal of Nuclear Materials. - 2003. - V. 323, l. 1. - P. 93-100.

ISSN:

00223115

Type:

Article

Abstract:

The high temperature reactions of molybdenum and its oxides with chlorine and hydrogen chloride in molten alkali metal chlorides were investigated between 400 and 700 °C. The melts studied were LiCl-KCl, NaCl-CsCl and NaCl-KCl and the reactions were followed by in situ electronic absorption spectroscopy measurements. In these melts Mo reacts with Cl2 and initially produces MoCl6 2- and then a mixture of Mo(III) and Mo(V) chlorocomplexes, the final proportion depending on the reaction conditions. The Mo(V) content can be removed as MoCl5 from the melt under vacuum or be reduced to Mo(III) by Mo metal. The reaction of Mo when HCl gas is bubbled into alkali chloride melts yields only MoCl6 3-. MoO2 reacts in these melts with chlorine to form soluble MoOCl5 2- and volatile MoO2Cl 2. MoO3 is soluble in chloride melts and then decomposes into the oxychloride MoO2Cl2, which sublimes or can be sparged from the melt, and molybdate. Pyrochemical reprocessing can thus be employed for molybdenum since, after various intermediates, the end-products are chloride melts containing chloro and oxychloro anions of molybdenum plus molybdate, and volatile chlorides and oxychlorides that can be readily separated off. The reactions were fastest in the NaCl-KCl melt. The X-ray diffraction pattern of MoO2Cl2 is reported for the first time. © 2003 Elsevier B.V. All rights reserved.

Author keywords:

Index keywords:

Isotopes; Molybdenum compounds; Nuclear fuels; Spectroscopic analysis; X ray diffraction analysis; Fissile nuclides; Fission products

DOI:

10.1016/j.jnucmat.2003.08.039

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https://www.scopus.com/inward/record.uri?eid=2-s2.0-0242271824&doi=10.1016%2fj.jnucmat.2003.08.039&partnerID=40&md5=ba58e73ea6ecb375e792b00adeca3f9e

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Affiliations	Centre for Radiochemistry Research, Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom; School of Chemistry, University of Leeds, Leeds LS2 9JT, United Kingdom; British Nuclear Fuels plc (BNFL), Sellafield R and D, Seascale, Cumbria CA20 1PG, United Kingdom; Department of Rare Metals, Physical-Engineering Faculty, Ural State Technical University-UPI, 19 Mira ul., Ekaterinburg 620002, Russian Federation
References	Wilson, P.D., (1996) Nuclear Fuel Cycle, p. 166. , Oxford: Oxford University; Volkovich, V.A., May, I., Charnock, J.M., Lewin, B., (2002) Phys. Chem. Chem. Phys., 4, p. 5753; Wilson, P.D., (1996) Nuclear Fuel Cycle, p. 315. , Oxford: Oxford University; Wymer, R.G., (1999) Chemical Separation Technologies and Related Methods of Nuclear Waste Management, p. 29. , G.R. Choppin, & M.Kh. Khankhasayev. Dordrecht: Kluwer; Kleykamp, H., (1985) J. Nucl. Mater., 131, p. 221; Kleykamp, H., (1988) Nucl. Technol., 80, p. 412; Bramman, J.I., Sharpe, R.M., Thom, D., Yates, G., (1968) J. Nucl. Mater., 25, p. 201; Naito, K., Tsuji, T., Matsui, T., Date, A., (1988) J. Nucl. Mater., 154, p. 3; Imoto, S., (1986) J. Nucl. Mater., 140, p. 19; Scheffler, T.B., Hussey, C.L., Seddon, K.R., Kear, C.M., Armitage, P.D., (1983) Inorg. Chem., 22, p. 2099; Carlin, R.T., Osteryoung, R.A., (1988) Inorg. Chem., 27, p. 1482; Barnard, P.A., Sun, I.W., Hussey, C.L., (1990) Inorg. Chem., 29, p. 3670; Aleksandrov, E.P., Alekseev, A.B., Vasin, B.D., Raspopin, S.P., (1981) Izv. Vuzov, Tsvet. Met., 1, p. 66; Gabriel, J.C., Vincent, D., Bouteillon, J., Poignet, J.C., Volkovich, V.A., Griffiths, T.R., (1999) Electrochim. Acta, 44, p. 4619; Horner, S.M., Tyree S.Y., Jr., (1963) Inorg. Chem., 2, p. 568; Maslov, S.V., Vasin, B.D., (1993) Rasplavy, 3, p. 66; Vasin, B.D., Maslov, S.V., Volkovich, V.A., (1995) Rasplavy, 2, p. 47; Opal'evskii, A.A., Tychinskaya, I.I., Kuznetsova, Z.M., Samoilov, P.P., (1972) Molybdenum Halides, p. 123. , (in Russian). Novosibirsk: Nauka; (1994) CRC Handbook of Chemistry and Physics, 4. , Boca Raton: CRC; Maslov, S.V., Vasin, B.D., (1993) Rasplavy, 4, p. 37; Vasin, B.D., Volkovich, V.A., (1997) Rasplavy, 1, p. 88; Polovov, I.B., Volkovich, V.A., Shipulin, S.A., Maslov, S.V., Khokhryakov, A.A., Vasin, B.D., Griffiths, T.R., Thied, R.C., (2003) J. Mol. Liq., 103-104, p. 387; Volkovich, V.A., Bhatt, A.I., May, I., Griffiths, T.R., Thied, R.C., (2002) J. Nucl. Sci. Technol. Suppl., 3, p. 595; Gray, H.B., Hare, C.R., (1962) Inorg. Chem., 1, p. 363; Berry, L.G., (1976) Powder Diffraction File, Search Manual, Inorganic Compounds, , Joint Committee on Powder Diffraction Standards, Swarthmore; Blomstrand, C.W., (1857) J. Prakt. Chem., 71, p. 461; Berzelius, J.J., (1826) Ann. Phys. (Leipzig), 6, p. 381; Svanberg, L., Struve, H., (1848) J. Prakt. Chem., 44, p. 311; Kangro, W., Jahn, R., (1933) Z. Anorg. Chem., 210, p. 334; Zelikman, A.N., Gorovits, N.N., (1954) J. Gen. Chem. USSR, 24, p. 1879; Barrachlough, C.G., Stals, J., (1966) Aust. J. Chem., 19, p. 741; Beattie, I.R., Livingston, K.M.S., Reynolds, D.J., Ozin, G.A., (1970) J. Chem. Soc., A, p. 1210; Levason, W., Narayanaswamy, R., Ogden, J.S., Rest, A.J., Turff, J.W., (1982) J. Chem. Soc., Dalton Trans., p. 2009; Thomassen, H., Hedberg, K., (1992) J. Mol. Struct., 273, p. 197
Correspondence Address	Griffiths, T.R.; School of Chemistry, University of Leeds, Leeds LS2 9JT, United Kingdom; email: t.r.griffiths@chem.leeds.ac.uk
CODEN	JNUMA
Language of Original Document	English
Abbreviated Source Title	J Nucl Mater
Source	Scopus