THE THERMAL CONDUCTIVITY OF MOLTEN MIXTURES OF СeCl3–MCl (M = Li, Na, K, Cs) SYSTEMS

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The paper presents experimental data on the thermal conductivity of molten salt mixtures СeCl3–MCl, where M = Li, Na, K, Cs. The concentration of cerium trichloride varies from 0.25 to 0.75 mole percent in 0.25 increments. The initial salts of alkali metal chlorides were certified by DSC. The obtained values of melting temperatures are in good agreement with the literature data. Anhydrous cerium trichloride was obtained from cerium(IV) oxide in 2 stages: preparation of cerium crystalline hydrate and removal of water of crystallization. The measurements were carried out by the stationary method of coaxial cylinders in a nickel device in the temperature range individually selected for each composition. The relative measurement error does not exceed 5%. In this work, the convective and radiative contributions to heat transfer were estimated. The value of the product of Prandtl and Grashof numbers is less than 1000, which confirms the absence of convection. The calculated radiative contribution to heat transfer does not exceed 2.4%. The thermal conductivity of all investigated melts increases with increasing temperature. The concentration dependences of molten mixtures of cerium and alkali metal chlorides were obtained. The thermal conductivity decreases upon passing from Li to Cs, which is due to an increase in the radius of the alkali metal cation and, as a consequence, an increase in the interionic distance.

作者简介

K. Bobrova

Institute of High Temperature Electrochemistry of the UB RAS

编辑信件的主要联系方式.
Email: ksuybobrova@gmail.com
Russia, Yekaterinburg

V. Dokytovich

Institute of High Temperature Electrochemistry of the UB RAS

Email: ksuybobrova@gmail.com
Russia, Yekaterinburg

参考

  1. Komarov V.Ye., Smolenskiy V.V., Afonichkin V.K. Perspektivy ispol’zovaniya rasplavlennykh soley v radiokhimicheskikh tekhnologiyakh [Prospects for the use of molten salts in radiochemical technologies] // Rasplavy. 2000. № 2. Р. 59–65. [In Russian].
  2. Ogawa T., Igarashi M. Pyrochemical process in advanced nuclear programs – with emphasis on management of long-lived radionuclides, in: M. Gaune-Escard (Ed.) // Advances in Molten Salts. From Structural Aspects to Waste Processing, Begell House Inc., New York, Wallingford, 1999. P. 454–463.
  3. Inoue T., Sakamura Y., Iizuka M., Kinoshita K., Usami T., Kurata M., Yokoo T. Actinides recycle by pyrometallurgy in nuclear fuel cycle // Molten Salts XIII. Proc of Int. Symp. Electrochemical Society. Proceedings 2002-19. 2002. P. 553–562.
  4. Uozumi K., Sakamura Y., Kinoshita K., Hijikata T., Inoue T., Koyama T. Development of pyropartitioning process to recover minor actinide elements from high level liquid waste // Energy Procedia. 2011. 7. P. 437–443.
  5. Venneri F., Bowman C. Accelerator-driven systems and fast reactors in advanced nuclear fuel cycles // A Comparative Study, Rep. OCDE/NEA. 2002.
  6. Kormilitsyn M.V., Bychkov A.V., Ishunin V.S., in Proc. GLOBAL’2003, New Orleans (USA), November 16–20. 2003. P. 782–783.
  7. Kim G.-Y., Yoon D., Paek S., Kim S.-H., Kim T.-J., Ahn D.-H.. A study on the electrochemical deposition behavior of uranium ion in a LiCl–KCl molten salt on solid and liquid electrode // J. Electroanalytical Chemistry. 2012. 682. P. 128–135.
  8. Marsden K.C., Pesic B. Evaluation of the electrochemical behavior of cecl3 in molten LiCl–KCl eutectic utilizing metallic Ce as an anode // J. Electrochemical Society. 2011. 159. № 6. F111.
  9. Smolenskiy V.V., Novoselova A.V., Bove A.L. Polucheniye metallicheskogo tseriya vysokoy chistoty elektrolizom rasplava LiCl–KCl–CeCl3 [Obtaining high-purity metal cerium by electrolysis of LiCl–KCl–CeCl3 melt] // Nauchno-prakticheskaya konferentsiya “Perspektivy razvitiya metallurgii i mashinostroyeniya s ispol’zovaniyem zavershonnykh fundamental’nykh issledovaniy i NIOKR”. Yekaterinburg.2020. Р. 142–145. [In Russian].
  10. Jiang K., Shao Y., Smolenski V., Novoselova A., Liu Q., Xu M., Yan Y., Yu J., Zhang M., Wang J. Electrochemical study of reduction Ce(III) ions and production of high purity metallic cerium by electrorefining in fused LiCl–KCl eutectic // J. Electroanalytical Chemistry. 2020. 878. 114691
  11. Kim S., Lee S.-H. Electrochemical properties of NdCl3 and CeCl3 in molten LiCl–KCl eutectic salt // Appl. Sci. 2020. 10. 7252.
  12. Misra M., Raja K.S., Jaques A., Baral S. Effect of addition of multi-component lanthanides to LiCl–KCl eutectic on thermal and electrochemical properties // ECS Transactions. 2010. 33. № 7. P. 351–360.
  13. Novoselova A.V., Smolenskii V.V. Electrochemical and thermodynamic properties of lanthanides (Nd, Sm, Eu, Tm, Yb) in alkali metal chloride melts // Radiochemistry. 2013. № 3. 55. P. 243–256.
  14. Yamamura T., Mehmood M., Maekawa H., Sato Y. Electrochemical processing of rare-earth and rare metals by using molten salts // Chemistry for Sustainable Development. 2004. 12. P. 105–111.
  15. Yoon D., Phongikaroon S. Electrochemical properties and analyses of CeCl3 in LiCl–KCl eutectic salt // J. Electrochemical Society. 2015. 162. № 10. P. 237–243.
  16. Salyulev A., Potapov A., Khokhlov V., Shishkin V. The electrical conductivity of model melts based on LiCl–KCl, used for the processing of spent nuclear fuel // Electrochimica Acta. 2017. 257. P. 510–515.
  17. Takagi R., Rycerz L., Gaune-Escard M. Phase equilibrium in the LnCl3–mCl mixtures (Ln = Lanthanide; M = Alkali): Thermodynamics and electrical conductivity of the M3LnCl6 compounds // ECS Proceedings Volumes. 1996. 7. P. 439–467.
  18. Gong W., Gaune-Escard M., Rycerz L. Thermodynamic assessment of LiCl–NdCl3 and LiCl–PrCl3 quasi-binary systems // J. Alloys Compd. 2005. № 396. P. 92–99.
  19. Rycerz L., Gaune-Escard M. Mixing enthalpies of TbBr3–MBr liquid mixtures // Z. Nat. A. 2001. № 56. P. 859–864.
  20. Kapała J., Rutkowska I. Thermodynamic properties of the pseudo-binary CsCl–LnCl3 (Ln = Ce, Pr, Nd) systems // Computer Coupling of Phase Diagrams and Thermochemistry. 2004. 28. P. 275–279.
  21. Papatheodorou G.N., Kleppa O.J. Thermodynamic studies of binary charge unsymmetrical fused salt systems. Cerium(III) chloride-alkali chloride mixtures // The J. Physical Chemistry. 1974. 78. № 2. Р. 178–181.
  22. Glushko V.P., Gurvich L.V. et al. Termodinamicheskiye svoystva individual’nykh veshchestv. Spravochnoye izdaniye [Thermodynamic properties of individual substances. Reference edition]. L.: Nauka, 1982. [In Russian].
  23. Makarova L.I., Aloy A.S., Stupin D.Yu. Izucheniye vliyaniya CsBr na fazovyy perekhod CsCl emanatsionnym metodom [Study of the effect of CsBr on the phase transition of CsCl by the emanation method] // Radiokhimiya. 1969. 11. P. 116–119. [In Russian].
  24. Arell A., Roiha M., Aaltonen M. Direct determination of the transition energy of CsCl at 470°C // Phys. Kondens. Mater. 1967. № 6. P. 140–144.
  25. Bukhalova G.A., Mardirosova I.V. Diagramma sostoyaniya dvoynykh sistem iz metafosfatov i khloridov shchelochnykh metallov [State diagram of binary systems from metaphosphates and alkali metal chlorides] // Zhurnal neorganicheskoy khimii. 1967. № 12. P. 2199–2204. [In Russian].
  26. Verzhbitskiy F.R., Vasilevskaya M.M., Burov G.V., Smirnov M.V. Issledovaniye temperaturnoy zavisimosti elektricheskikh svoystv ionnykh kristallov vysokochastotnym beskontaktnym metodom [Investigation of the temperature dependence of the electrical properties of ionic crystals by a high-frequency non-contact method] // Trudy instituta elektrokhimii, Ural’skiy nauchnyy tsentr AN SSSR. 1971. № 17. P. 7–10. [In Russian].
  27. Ashcroft S.J., Mortimer C.T. The thermal decomposition of lanthanide(III) chloride hydrates // J. Less-Common Melts. 1968. P. 14–17.
  28. Hong Vu Vu, Sundstrom Johan. The dehydration schemes of rare-earth chlorides // Thermochimica Acta. 1997. 307. P. 37–43.
  29. Smirnov M.V., Khokhlov V.A., Filatov E.S. Thermal conductivity of molten alkali halides and their mixtures // Electrochimica Acta. 1987. 32. № 7. P. 1019–1026.
  30. Siegel R., Howell J. Teploobmen izlucheniyem [Heat transfer by radiation]. M.: Mir, 1975. [In Russian].
  31. Lykov A.V. Teoriya teploprovodnosti [Theory of heat conduction]. M.: Gosizdat, 1952. [In Russian].
  32. Osipova V.A. Eksperimental’noye issledovaniye protsessov teploobmena [Experimental study of heat transfer processes]. M.: Energy, 1968. [In Russian].
  33. Mellors G.W., Senderoff S. The density and electrical conductance of the molten system cerium– cerium chloride // J. Phys. Chem. 1960. 64. № 3. P. 294–300.
  34. Potapov A.M. Transportnyye svoystva rasplavlennykh khloridov lantanidov i ikh binarnykh smesey s khloridami shchelochnykh metallov [Transport properties of molten lanthanide chlorides and their binary mixtures with alkali metal chlorides]. Diss.. degree of Dr. Chem. Sciences. [In Russian].
  35. Gaune-Escard М., Bogacz A., Rycerz L., Szczepaniak W. Heat capacity of LaCl3, CeCl3, PrCl3, NdCl3, GdCl3, DyCl3 // J. Alloys Compd. 1996. 235. P. 176–181.
  36. Tosi M.P. Ordering in metal halide melts // Ann. Rev. Phys. Chem. 1993. 44. P. 173–211.
  37. Photiadis G.M., Papatheodorou G.N. Vibrational modes and structures of lanthanide halide-alkali halide binary melts: LnBr3–KBr (Ln = La, Nd, Gd) and NdCl3–ACl (A = Li, Na, K, Cs) // J. Chem. Soc. Faraday Trans. 1998. 94. № 17. P. 2605–2613.

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