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Abstract

The phase diagrams of trivalent lanthanide–alkali metal halide systems range from simple eutectic systems to systems with one or several congruently or incongruently melting compounds. Using both literature information and the authors’ extensive experimental results, the LnX₃–MX binary mixture phase diagrams were screened in terms of the IP_M+/IP_Ln3+ ratio (IP_i: z_i/r_i; z_i: ionic charge; r_i: ionic radius; Ln: lanthanide, X: halide and M: alkali metal). A similar approach was conducted on the divalent LnX₂–MX lanthanide–alkali metal halide phase diagrams ranging from simple eutectic to one or more congruently melting compounds. Lanthanides being widely used as simulants of actinides, this classification can constitute a useful predictive tool for those still unexplored systems.

Keywords

Lanthanide Alkali metal Halide Mixture Phase diagram Topology Ionic potential Prediction

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References

Belyaev,

I. N.

and Doroshenko,

A. K.

. 1962. The physicochemical analysis of salt systems, 12, Rostov, Izd. Rostovsk Gos. Univ.

Bergman,

A. G.

and Zimina,

T. D.

. 1965. Zh. Neorg. Khim., 10, 2326.

Blachnik,

and Jaeger-Kasper,

. 1980. Zustandsdiagramme von Alkalibromid-Lanthanoid(III)-bromid Mischungen, Z. Anorg. Allg. Chem., 461, 74.

Bukhalova,

G. A.

and Burlakov,

A. M.

. 1966. Z. Neorg. Khim., 11, 1755.

Cartledge,

G. H.

. 1928a. Studies on the periodic system. I. The ionic potential as a periodic function, J. Am. Chem. Soc., 50, 2855.

Cartledge,

G. H.

. 1928b. Studies on the periodic system. II. The ionic potential and related properties, J. Am. Chem. Soc., 50, 2863.

Cartledge,

G. H.

. 1930. Studies on the periodic system. III. The relation between ionizing potentials and ionic potentials, J. Am. Chem. Soc., 52, 3076.

Chai,

and Zheng,

. 1990. Zhongguo Xitu Xuebao, 8, 93.

Chaogui,

, Shoulin,

and Siqiang,

. 1993a. Chem. Res. Chin. Univ., 14, 993.

10.

Chaogui,

, Shoulin,

and Siqiang,

. 1994a. Acta Chim. Sin., 52, 736.

11.

Chaogui,

, Shoulin,

and Siqiang,

. 1994b. Acta Physico-Chimica Sinica, 10, 342.

12.

Chaogui,

, Zhongdong,

and Siqiang,

. 1993b. Trans. NF Soc., 3, 33.

13.

Chen,

, Wang,

M. T.

and Wang,

S. H.

. 1997, Synthesis and structure of new iodides Cs₄EuI₆ and Rb₄EuI₆, J. Alloys Compd., 256, 112–114.

14.

Da,

Silva

, Rycerz,

, L and Gaune-Escard,

. 2001a. Thermodynamic properties of EuCl₂ and the NaCl-EuCl₂ system, Z. Naturforsch., 56A, 647–652.

15.

Da,

Silva

, Rycerz,

, L and Gaune-Escard,

. 2001b. Calorimetric investigation of MCl–EuCl₂ melts (M = Na, K, Rb), Z. Naturforsch., 56A, 653–657.

16.

Drobot,

D. V.

, Korshunov,

B. G.

and Bordulenko,

G. P.

. 1968. Zh. Neorg. Khim., 13, 1635.

17.

Dudareva,

A. G.

, Polanskaja,

O. W.

, Tenanko,

N. W.

, Ezhov,

A. I.

and Strekachinskij,

A. B.

. 1984. Zh. Neorg. Khim., 29, 2646.

18.

Dudarieva,

A. G.

, Nechitailov,

S. B.

, Babuszkina,

A. T.

, Volgin,

K. Yu

and Boguslavskii,

A. A.

. 1989. Zh. Neorg. Khim., 34, 3164.

19.

Fink,

and Seifert,

H. J.

. 1980. Z. Anorg. Allg. Chem., 466, 87.

20.

Gadzuric,

. 2006. Experimental study of thermodynamic, transport and structural properties of lanthanide bromide systems. Properties prediction by data mining statistical techniques, PhD Thesis, Université de Provence Aix-Marseille 1, France.

21.

Gadzuric,

, Ingier-Stocka,

, Rycerz,

and Gaune-Escard,

. 2005a. Phase diagram and electrical conductivity of EuBr₂–LiBr binary system., J. Alloys Compd., 397, 63–67.

22.

Gather,

and Blachnik,

. 1979. Experientia, 37, 81.

23.

Gaune-Escard,

and Rycerz,

. 2013. Unpublished Results.

24.

Gaweł,

and Josiak,

. 1994. Phase and cryometric studies of the system tin(II) chloride-uranium(IV) chloride, Bull. Pol. Acad. Chem., 42, 211–220.

25.

Gaweł,

. 1975. Ionic potentials of cations and types of phase equilibriums in metal chloride–uranium(IV) chloride systems, Roczniki Chem., 49, 699–704.

26.

Gaweł,

. 1997. Regularities of phase equilibria in the binary uranium tetrachloride systems and their thermodynamic interpretation, J. Nucl. Mater., 247, 301–303.

27.

Görlich,

. 1960. Crystallochemical systematization of condensed systems of two ionic compounds with a common anion, Bull. Acad. Pol. Sci. Ser. Sci. Chim., 888, 231–238.

28.

Igarashi,

, Kosaka,

and Iwadate,

. 1990. Denki Kagaku, 58, 469.

29.

Ingier-Stocka,

, Gadzuric,

, Rycerz,

, Golonka-Cieslak,

and Gaune-Escard,

. 2005. Phase diagram and electrical conductivity of the EuBr₂–NaBr binary system, J. Nucl. Mater., 344, 120–123.

30.

Ingier-Stocka,

, Rycerz,

, Berkani,

and Gaune-Escard,

. 2009. Thermodynamic and transport properties of the PrBr₃–MBr binary systems (M = Li, Na), J. Mol. Liq., 148, 40–44.

31.

Ingier-Stocka,

, Rycerz,

, Gadzuric,

and Gaune-Escard,

. 2008. Thermal and conductometric studies of the CeBr₃–MBr binary systems (M = Li, Na), J. Alloys Comp., 450, 162–166.

32.

Kim,

, Okamoto,

and Ogawa,

. 1998. Proc. 7th China–Japan Bilateral Conf. on ‘Molten salt chemistry and technology’, Xian, China.

33.

Klokman,

V. R.

. 1961. Types of melt diagrams of binary systems formed by radium chlorides and alkali metals, Radiokhimiya, 3, 302.

34.

Korzina,

A. G.

andrachnikova,

A.P

, Strekachinskii,

A. B.

and Krochin,

V. A.

. 1980. Zh. Neorg. Khim., 25, 1624.

35.

Kutscher,

and Schneider,

. 1971. Chemie der Seltenen Erden in geschmolzenen Alkalihalogeniden. VIII. Untersuchung der Zustandsdiagramme von Lanthaniden(III)-jodiden im Gemisch mit Alkalijodiden, Z. Anorg. Allgem. Chem., 386, 38.

36.

Mahendran,

K. H.

, Sujatha,

, Sridharan,

and Gnanasekaran,

. 2003. Studies on the phase diagram of LiBr–SrBr₂ system, J. Alloys Compd., 358, 42–47.

37.

Miller,

, Smith,

, Wang,

and Wang,

S. H.

. 1998. The synthesis and crystal structure of Rb₄TmI₆: lattice energy calculations on networks of condensed cubes, J. Alloys Compd., 265, 140–145.

38.

Mitra,

, Uebach,

and Seifert,

H. J.

. 1995. Ternary chlorides in the systems ACl/TbCl₃ (A = K, Rb, Cs), J. Solid State Chem., 115, 484–489.

39.

Molodkin,

A. K.

and Dudarieva,

A. G.

. 1986. Zh. Neorg. Khim., 31, 2784.

40.

Molodkin,

A. K.

, Karagodina,

A. M.

, Nechitailov,

S. B.

, Dudarieva,

A. G.

and Krochina,

A. G.

. 1986. Zh. Neorg. Khim., 31, 789.

41.

Molodkin,

A. K.

, Strekachinskii,

A. B.

, Dudareva,

A. G.

, Ezhov,

A. I.

and Krokhina,

A. G.

. 1982. Zh. Neorg. Khim., 27, 219.

42.

Qiao,

, Mingsheng,

, Zheng,

and Duan,

. 1989. J. Univ. Sci. Technol. Beijing, 11, 601.

43.

Rejek,

, Rycerz,

, Ingier-Stocka,

and Gaune-Escard,

. 2010. Thermodynamic and transport properties of the PrBr₃–KBr binary system, J. Chem. Eng. Data, 55, 1871–1875.

44.

Riccardi,

, Sinistri,

, Campari,

and Magistris,

. 1970. Z. Naturforsch., 25A, 781.

45.

Roffe,

and Seifert,

H. J.

. 1997. Ternary chlorides in the systems ACl/HoCl₃ (A = Cs, Rb, K), J. Alloys Comp., 257, 128.

46.

Rycerz,

. 2004. Thermochemistry of lanthanide halides and compounds formed in lanthanide halide–alkali metal halide systems (in Polish), Scientific Papers of Institute of Inorganic Chemistry and Metallurgy of Rare Elements, Series Monographs 35, Wroclaw, Wroclaw University of Technology.

47.

Rycerz,

, Cieslak-Golonka,

, Ingier-Stocka,

and Gaune-Escard,

. 2003 c. Phase diagram and electrical conductivity of TbBr₃–NaBr binary system, J. Therm. Anal. Cal., 72, 231–239.

48.

Rycerz,

and Gaune-Escard,

. 2013. Unpublished results.

49.

Rycerz,

, Ingier-Stocka,

, Berkani,

and Gaune-Escard,

. 2010. Thermodynamic and transport properties of the PrBr₃–RbBr binary system, J. Alloys Comp., 501, 269–274.

50.

Rycerz,

, Ingier-Stocka,

and Cieślak-Golonka,

. 2003b. Thermal and conductometric studies of NdBr₃ and NdBr₃-LiBr binary system, J. Therm. Anal. Cal., 72, 241–251.

51.

Rycerz,

, Ingier-Stocka,

, Cieslak-Golonka,

, Wojciechowska,

, Gadzuric,

and Gaune-Escard,

. 2008a. Physicochemical properties of the EuBr₂–KBr binary system, J. Alloys Compd., 450, 157–161.

52.

Rycerz,

, Ingier-Stocka,

, Gadzuric,

, Gaune-Escard,

. 2007. Phase diagram and electrical conductivity of CeBr₃–KBr, Z. Naturforsch., 62A, 197–204.

53.

Rycerz,

, Ingier-Stocka,

, Gadzuric,

and Gaune-Escard,

. 2008b. Phase diagram and electrical conductivity of the CeBr₃–RbBr binary system, J. Alloys Comp., 450, 175–180.

54.

Rycerz,

, Ingier-Stocka,

and Gaune-Escard,

. 2009. Phase diagram and electrical conductivity of the CeBr3–CsBr binary system, J. Therm. Anal. Calorim., 97, 1015–1021.

55.

Rycerz,

, Ingier-Stocka,

, Ziółek,

, Gadzuric,

and Gaune-Escard,

. (2003a). Thermal studies of LaBr₃ and LaBr₃–LiBr binary system, Proc. Int. Symposium on ‘Ionic liquids in honour of Marcelle Gaune-Escard, Carry le Rouet, France’, Trondheim University, 83.

56.

Schilling,

and Meyer,

. 1996. Z. Anorg. Allg. Chem., 622, 759.

57.

Schilling,

, Kunert,

, Schleid,

and Meyer,

. 1992. Z. Anorg. Allg. Chem., 618, 7.

58.

Seifert,

H. J.

, Fink,

and Thiel,

. 1985. Thermodynamic properties of double chlorides in the systems ACl/LaCl3 (A = Na, K, Rb, Cs), J. Less Common Met., 110, 139.

59.

Seifert,

H. J.

, Fink,

and Uebach,

. 1988. Properties of double chlorides in the systems ACl/NdCl3 (A = Na–Cs), J. Thermal Anal., 33, 625–632.

60.

Seifert,

H. J.

and Sandrock,

. 1990. Z. Anorg. Allg. Chem., 587, 110.

61.

Seifert,

H. J.

, Sandrock,

and Thiel,

. 1986. Thermochemical studies on the systems ACI/CeCI3 (A = Na–Cs), J.Thermal Anal., 31, 1309–1318.

62.

Seifert,

H. J.

, Sandrock,

and Thiel,

. 1991. Z. Anorg. Allg. Chem., 598/599, 307.

63.

Seifert,

H. J.

, Sandrock,

and Uebach,

. 1987. Z. Anorg. Allg. Chem., 555, 143.

64.

Seifert,

H. J.

, Sandrock,

and Uebach,

., 1995. Acta Chim. Scand., 49, 653.

65.

Seifert,

H. J.

and Yuan,

. 1991. J. Less Common Met., 170, 135.

66.

Sharpe,

A. G.

. 1986. Inorganic Chemistry, New York, NY, USA, Longman.

67.

Shurginov,

E.A.

1969. Proceedings of IX Scientific Conference of Aspirants, Exact and Natural Science Series, Izd. Rostovsk. Gos. Univ., Rostov, 37.

68.

Sun,

and Qiao,

. 2002. Rare Met. 21, 1.

69.

Tang,

Z. J.

, Yang,

H. Z.

and Wang,

S. H.

. 1986. J. Chin. Rare Earths (in Chinese), 41, 71.

70.

Thiel,

and Seifert,

H. J.

. 1988. Properties of double chlorides in the systems ACl/SmCl3 (A = Na–Cs), Thermochim. Acta, 133, 275–282.

71.

Thoma,

R.E.

1962. Cation size effects in complex fluoride compound formation, Inorg. Chem., 1, 220–226.

72.

Tokarev,

M. V.

. 1956. Nauchn. Zap. Voroshilovgradsk. Ped. Inst., 6, 3.

73.

Vogel,

. 1972. Z. Anorg. Allg. Chem., 388, 43.

74.

Wang,

L. T.

, Jiang,

S. B.

and Wang,

S. H.

. 1993. Chem. J. Chinese U. (in Chinese), 24, 1263.

75.

Wang,

M. T.

and Wang,

S. H.

. 1997. Rb4YbI6 Synthesis and Crystal Structure. J. Solid State Chem., 128, 66.

76.

Wang,

S. H.

and Zhao,

. 1987. J. Chinese Rare Earths (in Chinese), 127, 219.

77.

Wang,

S. H.

, Tang,

Z. J.

, Jiang,

S. B.

and Yang,

H. Z.

. 1984. J. Chinese Rare Earths (in Chinese), 21, 25.

78.

Wang,

X. D.

and Wang,

S. H.

. 1991. Chem. J. Chinese U. (in Chinese), 22, 239.

79.

Wojakowska,

. 1993. Equilibrium phase diagrams and electrical conductivity in tin dihalides systems (in Polish), Wroclaw, Medical University, Ed. 62/1993.

80.

Zheng,

and Seifert,

H. J.

. 1998. Ternary chlorides in the systems ACl/TmCl₃ (A = Cs, Rb, K), J.Solid State Chem., 135, 127–131.

Compound formation in lanthanide–alkali metal halide systems

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