Thermochemistry and reactivity of rare earth metals

Abstract

Reactivity of the rare earth metals towards the different elements is described. Comments are mainly made on the thermodynamic data relevant to the formation of the binary compounds and to their trends. The different behaviour of the trivalent rare earths and of europium and ytterbium is underlined. An indication is also given for a few reactions involving more complex reagents or compounds. Comments are finally made on the use of the reported data in the discussion of the preparation and handling methods of the rare earth metals and of their alloys.

References

1. K. A. Gschneidner Jr., B. J. Beaudry and J. Capellen, in Properties and Selection: Nonferrous Alloys and Special-Purpose Materials, ASM International, Metals Park, OH, 1990, vol. 2, p. 720.
2. K. A. Gschneidner, Jr., Bull. Alloy Phase Diagrams, 1990, 11, 216.
3. Pearson's Handbook of Crystallographic Data for Intermetallic Phases, ed. P. Villars and L. D. Calvert, ASM, Metals Park, OH, vol. 1–4, 1991.
4. R. G. Haire and L. Eyring, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr., L. Eyring, G. R. Choppin and G. H. Lander, North-Holland, Amsterdam, NL, 1994, vol. 18, p. 413.
5. A. P. Bayanov, Yu. A. Afanasaev and N. M. Pogorelaya, Zh. Fiz. Khim., 1973, 47, 2105.
6. V. A. Degtyar, A. P. Bayanov, L. A. Vnuchkova and V. V. Serebrennikov, Izv. Akad. Nauk SSSR, Met., 1971, 4, 149.
7. V. A. Degtyar, L. A. Vnuchkova, A. P. Bayanov and V. V. Serebrennikov, Zh. Fiz. Khim., 1971, 45, 1594.
8. V. I. Kober, I. F. Nichkov, S. P. Raspopin and V. M. Kuz'minykh, in Thermodynamics of Metallic Systems, Alma-Ata, 1979, vol. 2, p. 67.
9. V. I. Kober, V. A. Dubinin, A. I. Kochkin, I. F. Nichkov and S. P. Raspopin, Izv. Vyssh. Uchebn. Zaved. Tsvetn. Metall., 1983, 25, 113.
10. V. I. Kober, Chem. Ztg., 1991, 115, 155.
11. L. F. Yamshchikov, V. A. Lebedev, V. I. Kober, I. F. Nichkov and S. P. Raspopin, Izv. Akad. Nauk SSSR, Met., 1977, 5, 590.
12. V. P. Vasilev, L. A. Khramtsova and V. V. Morozova, Vestn. Mosk. Univ., Ser. 2: Khim., 1986, 27, 38.
13. V. V. Serebrennikov, V. A. Novozhenov and T. M. Shkol'nikova, EZh. Fiz. Khim., 1976, 50, 2401.
14. A. Palenzona and S. Cirafici, Thermochim. Acta, 1974, 9, 419.
15. A. Borsese, A. Calabretta, S. Delfino and R. Ferro, J. Less-Common Met., 1977, 51, 45.
16. R. Ferro, S. Delfino, G. Borzone, A. Saccone and G. Cacciamani, J. Phase Equilib., 1993, 14, 273.
17. R. Ferro and G. Borzone, J. Chim. Phys., 1997, 94, 905.
18. R. Ferro, G. Borzone, G. Cacciamani and N. Parodi, Thermochim. Acta, 1998, 314, 183.
19. Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr., L. Eyring, G. R. Choppin and G. H. Lander, North-Holland, Amsterdam, NL, 1978–1998, vol. 1–25.
20. Binary Alloy Phase Diagrams, ed. T. B. Massalski, H. Okamoto, P. R. Subramanyan and L. Kacprzak, Metals Park, OH, 2nd edn., 1990, vol. 1–3.
21. Red Book. Constitutional Data and Phase Diagrams of Metallic Systems, ed. G. Petzow and G. Effenberg, Material Science International Services, Stuttgart GmbH, vol. 35–40.
22. Q. Guo and O. J. Kleppa, J. Alloys Compd., 1995, 221, 50.
23. S. V. Meschel and O. J. Kleppa, J. Alloys Compd., 1996, 238, 180.
24. G. Cacciamani, G. Borzone and R. Ferro, J. Alloys Compd., 1995, 220, 106.
25. G. Borzone, A. M. Cardinale, N. Parodi and G. Cacciamani, J. Alloys Compd., 1997, 247, 141.
26. O. Kubaschewski and C. B. Alcock, Metallurgical Thermochemistry, Pergamon Press, Oxford, 5th edn., 1979.
27. R. Capelli, R. Ferro and A. Borsese, Thermochim. Acta, 1974, 10, 13.
28. A. Borsese, G. Borzone, R. Ferro and S. Delfino, J. Less-Common Met., 1977, 55, 115.
29. R. Ferro, G. Borzone and G. Cacciamani, Thermochim. Acta, 1988, 129, 99.
30. G. Borzone, A. Borsese and R. Ferro, Z. Anorg. Allg. Chem., 1983, 501, 199.
31. G. Borzone, G. Cacciamani and R. Ferro, Metall. Trans., 1991, 22A, 2119.
32. A. Palenzona and S. Cirafici, in Analytical Calorimetry, ed. R. S. Portes and J. F. Johnson, Plenum Press, New York, 1974, vol. 3.
33. E. J. Huber, E. L. Head and C. E. Holley, J. Chim. Phys., 1957, 61, 497.
34. E. Greenberg, J. L. Settle, H. M. Feder and W. N. Hubbard, J. Chim. Phys., 1961, 65, 1168.
35. Y. C. Kim and J. Oishi, in Memoirs of the Faculty of Engineering, Kyoto, Japan, 1980, part 1, vol. XLII.
36. O. Greis and J. M. Haschke, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland. Amsterdam, NL, 1982, vol. 5, p. 435.
37. Gmelin Handbuch der Anorganischen Chemie, Seltenerdeelemente, C1, 39, 1974, p. 131.
38. L. Topor and O. J. Kleppa, High Temp. Sci., 1986, 22, 139.
39. G. Canneri and A. Rossi, Gazz. Chim. Ital., 1932, 62, 202.
40. G. Borzone, G. Cacciamani, R. Ferro, J. Charles and J. Hertz, J. Less-Common Met., 1987, 128, 297.
41. V. A. Novozhenov, T. M. Shkolnikova and V. V. Serebrennikov, Zh. Fiz. Khim., 1979, 53, 2117.
42. W. N. Hubbard, P. L. Rawlins, P. A. Connick, R. E. Stedwell and P. A. G. O'Hare, J. Chem. Thermodyn., 1983, 15, 785.
43. C. Colinet, J. Alloys Comp., 1995, 220, 76.
44. C. Colinet, A. Pasturel and K. H. J. Buschow, J. Chem. Thermodyn., 1985, 17, 1133.
45. C. Colinet and A. Pasturel, CALPHAD, 1987, 11, 323.
46. J. Schott and F. Sommer, J. Less-Common Met., 1986, 119, 307.
47. F. Sommer, J. Schott and B. Predel, J. Less-Common Met., 1986, 125, 175.
48. C. Colinet, A. Pasturel, A. Percheron-Guégan and J. C. Achard, J. Less-Common Met., 1984, 102, 167.
49. S. Watanabe and O. J. Kleppa, Metall. Trans., 1984, 15B, 357.
50. K. L. Komarek, Ber. Bunsen-Ges. Phys. Chem., 1983, 87, 709.
51. Z. Moser, in Calculation of Phase Diagrams and Thermochemistry of Alloy Phases, ed. Y. A. Chang and J. F. Smith, Conference Proceedings of the Metallurgical Society of AIME, Warrendale, PA, 1979, p. 242.
52. V. T. Witusiewicz, V. R. Sidorko and M. V. Bulanova, J. Alloys Compd., 1997, 248, 233.
53. S. V. Meschel and O. J. Kleppa, J. Chim. Phys., 1997, 94, 928.
54. S. V. Meschel and O. J. Kleppa, J. Alloys Compd., 1997, 247, 52.
55. C. Colinet, A. Pasturel and K. H. J. Buschow, Metall. Trans., 1986, 17A, 777.
56. Q. Guo and O. J. Kleppa, J. Alloys Compd., 1995, 221, 45.
57. J. Dischinger and H.-J. Schaller, Ber. Bunsen-Ges. Phys. Chem., 1998, 102, 1167.
58. P. Chiotti and J. T. Mason, Metall. Trans., 1973, 4, 1527.
59. V. Ganesan and H. Ipser, J. Chim. Phys., 1997, 94, 986.
60. J. R. Ogren, N. J. Magnani and J. F. Smith, Trans. Metall. Soc. AIME, 1967, 239, 766.
61. J. E. Pahlman and J. F. Smith, Metall. Trans., 1972, 3, 2423.
62. R. A. Schiffman and H. F. Franzen, High Temp. Sci., 1982, 15, 179.
63. H. F. Franzen and A. V. Hariharan, J. Chem. Thermodyn., 1980, 12, 975.
64. H. F. Franzen and A. V. Hariharan, J. Chem. Phys., 1979, 70, 4907.
65. R. Hoppe, Z. Kristallogr., 1979, 150, 23; R. Hoppe and G. Meyer, Z. Metallkd., 1980, 71, 347.
66. L. R. Morss, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr., L. Eyring, G. R. Choppin and G. H. Lander, North-Holland, Amsterdam, NL, 1994, vol. 18, p. 272.
67. F. R. de Boer, R. Boom, W. C. M. Mattens, A. R. Miedema and A. K. Niessen, in Cohesion in Metals. Transition Metal Alloys, ed. F. R. de Boer and D. G. Pettifor, North-Holland, Amsterdam, 1989, vol. 1.
68. H.-F. Wu and L. Brewer, J. Alloys Compd., 1997, 247, 1.
69. L. Brewer, NATO ASI Ser., Ser. C, ed. S. P. Sinha, D. Reidel Publishing Company, 1983, vol. 109, p. 17.
70. C. Wagner, in Thermodynamics of Alloys, Addison-Wesley, Reading, MA, 1952, p. 83.
71. L. Kaufman and H. Bernstein, in Computer Calculation of Phase Diagrams, Academic Press, New York, 1970.
72. I. Ansara, Int. Met. Rev., 1979, 1, 20.
73. H. L. Lukas, E.-Th. Henig and B. Zimmermann, CALPHAD, 1977, 1, 225.
74. B. Sundman, B. Jansson and J. O. Andersson, CALPHAD, 1985, 9, 153.
75. K. A. Gschneidner Jr, J. Less-Common Met., 1969, 17, 1.
76. P. Vajda, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland, Amsterdam, NL, 1995, vol. 20, p. 207.
77. F. D. Manchester and J. M. Pitre, J. Phase Equilib., 1997, 18, 63.
78. F. D. Manchester and J. M. Pitre, J. Phase Equilib., 1996, 17, 432.
79. E. Boroch and E. Kaldis, Inorg. Chim. Acta, 1987, 140, 89.
80. E. Boroch and E. Kaldis, Z. Phys. Chem. Neue Folgue, 1989, 163, 117.
81. K. Conder, J. Schefer, E. Kaldis and Cai-Ru-Xiu, Z. Phys. Chem. Neue Folge, 1989, 163, 125.
82. J. W. Ward and J. M. Haschke, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr., L. Eyring, G. R. Choppin and G. H. Lander, North-Holland. Amsterdam, NL, 1994, vol. 18, p. 293.
83. G. G. Libowitz and A. J. Maeland, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland. Amsterdam, NL, 1979, vol. 3, p. 299.
84. K. H. J. Buschow, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland, Amsterdam, NL, 1979, vol. 6, p. 1.
85. T. Sakai, M. Matsuoka and C. Iwakura, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland, Amsterdam, NL, 1995, vol. 21, p. 133.
86. M. Gasgnier, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr., L. Eyring, North-Holland, Amsterdam, NL, 1995, vol. 20, p. 105.
87. E. A. Leon-Escamilla and J. D. Corbett, J. Alloys Compd., 1994, 206, L15.
88. N. N. Greenwood and A. Earnshaw, in Chemistry of the Elements, ed. Pergamon Press, Oxford, UK, 1986.
89. A. Simon, H. J. Mattausch, G. J. Miller, W. Bauhofer and R. K. Kremer, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland, Amsterdam, NL, 1991, vol. 15, p. 191.
90. G. K. Johnson, R. G. Pennell, K.-Y. Kim and W. N. Hubbard, J. Chem. Thermodyn., 1980, 12, 125.
91. P. G. McCormick, T. Alonso, F. J. Lincoln, T. C. Parks and G. B. Schaffer, in Rare Earths Resources, Science, Technology and Applications, ed. R. G. Bautista and N. Jackson, The Minerals, Metals & Materials Society, Warrendale, Pennsylvania, USA, 1991, p. 247.
92. T. Alonso, Y. Liu, M. P. Dallimore and P. G. McCormick, Scr. Metall. Mater., 1993, 29, 55.
93. C. Hurtgen and D. Brown, J. Chem. Soc., Dalton Trans., 1980, 70.
94. L. R. Morss and T. G. Spence, Z. Anorg. Allg. Chem., 1992, 616, 162.
95. Gmelin Handbuch der Anorganischen Chemie, Seltenerdeelemente, C6, 39, 1978, p. 164.
96. K. A. Gschneidner, Jr., N. Kippenhan and O. D. Mc Masters, in Thermochemistry of the Rare Earths, ed. Molybdenum Corporation of America, New York, 1973; K. A. Gschneidner, Jr. and N. Kippenhan, in Thermochemistry of the Rare Earths: Carbides, Nitrides and Sulfides for Steelmaking, ed. Molybdenum Corporation of America, New York, 1971.
97. K. A. Gschneidner, Jr. and B. J. Beaudry, Scr. Metall. Mater., 1991, 25, 745.
98. K. A. Gschneidner, Jr. and F. W. Calderwood, Bull. Alloy Phase Diagrams, 1988, 9, 658.
99. M. S. Chandrasekharaiah and K. A. Gingerich, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland, Amsterdam, NL, 1989, vol. 12, p. 409.
100. N. E. Ryan, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland, Amsterdam, NL, 1995, vol. 21, p. 93.
101. A. Biswas, I. G. Sharma, G. B. Kale and D. K. Bose, Metall. Mater. Trans., 1998, 29B, 309.
102. G. Borzone, A. M. Cardinale, G. Cacciamani and R. Ferro, Z. Metallkd., 1993, 84, 635.
103. P. Wu and A. D. Pelton, J. Alloys Compd., 1992, 179, 259.
104. T. Takeshita, B. J. Beaudry, K. A. Gschneidner, Jr., in The Rare Earths in Modern Science and Technology, ed. G. J. McCarthy, H. B. Silber and J. J. Rhyne, Plenum Press, New York, 1992, vol. 3, p. 255.
105. V. Marx and T. Petzel, J. Less-Common Met., 1990, 163, 199.
106. E. Kaldis, B. Steinmann, B. Fritzler, E. Jilek and A. Wisard, in The Rare Earths in Modern Science and Technology, ed. G. J. McCarthy, H. B. Silber and J. J. Rhyne, Plenum Pub. Corp., New York, 1982, p. 227.
107. V. F. Golnik and S. P. Gordienko, Zh. Fiz. Khim, 1979, 53, 618.
108. R. Hanhs and M. M. Faktor, Trans. Faraday Soc., 1967, 63, 1130.
109. G. Borzone, A. Borsese and R. Ferro, Gazz. Chim. Ital., 1983, 113, 235.
110. M. Gambino, J. P. Bros, V. Vasilev, F. Sommer, G. Borzone, N. Parodi, G. Cacciamani and R. Ferro, Pure Appl. Chem., 1995, 67, 1831.
111. K. A. Gschneidner, Jr. and A. H. Daane, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland, Amsterdam, NL, 1988, vol. 11, p. 409.
112. M. I. Ivanov, T. F. Karpova and N. Yu. Dalago, Izv. Akad. Nauk SSSR, Neorg. Mater., 1980, 16, 830.
113. R. Hultgren, P. D. Desai, D. T. Hawkins, M. Gleiser and K. K. Kelley, in Selected Values of the Thermodynamic Properties of Binary Alloys, American Society for Metals, Metals Park, OH, 1973.
114. G. Cacciamani, A. Saccone, G. Borzone, S. Delfino and R. Ferro, Thermochim. Acta, 1992, 199, 17.
115. R. Ferro, A. Saccone and G. Borzone, J. Rare Earths, 1997, 15, 45.
116. C. Colinet, A. Pasturel and K. H. J. Buschow, Metall. Trans, 1987, 18A, 903.
117. C. Colinet and A. Pasturel, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland, Amsterdam, 1994, vol. 19, p. 479.
118. K. T. Jacob and Y. Waseda, Mater. Trans., JIM, 1990, 31, 135.
119. A. Palenzona and S. Cirafici, Thermochim. Acta, 1978, 25, 252.
120. F. Meyer-Liautaud, A. Pasturel, C. Allibert and C. Colinet, J. Less-Common Met., 1985, 110, 75.
121. G. Qi, K. Itagaki, S. Mey and P. J. Spencer, Z. Metallkd., 1989, 80, 883.
122. F. Sommer and M. Keita, J. Less-Common Met., 1987, 136, 95.
123. W. Bronger and W. Klemm, Z. Anorg. Chem., 1962, 319, 58.
124. V. Contardi, R. Marazza, G. Rambaldi, G. Zanicchi and R. Ferro, Z. Metallkd., 1991, 82, 169.
125. K. Fitzner and O. J. Kleppa, Metall. Mater. Trans., 1997, 28A, 187.
126. K. A. Gschneidner, Jr., Bull. Alloy Phase Diagrams, 1983, 4, 129.
127. A. Iandelli and A. Palenzona, in Handbook on the Physics and Chemistry of Rare Earths, ed. K. A. Gschneidner, Jr. and L. Eyring, North-Holland, Amsterdam, NL, 1979, vol. 2, p. 1.
128. K. A. Gschneidner, Jr, J. Less-Common Met., 1969, 17, 13.
129. F. Sommer, B. Predel, G. Borzone, N. Parodi and R. Ferro, Intermetallics, 1995, 3, 15.
130. G. Borzone, R. Ferro, N. Parodi and A. Saccone, Gazz. Chim. Ital., 1995, 125, 26.
131. A. Ochai, S. Nakai, A. Oyamada, T. Suzuki and T. Kasuya, J. Magn. Magn. Mater., 1985, 47–48, 570.
132. K. A. Gschneidner, Jr. and O. D. McMasters, Monatsch Chem., 1971, 102, 1499.
133. A. Percheron-Guegan, J. C. Achard, O. Gorochov, E. Gonzalez-Gimenez and P. Imbert, J. Less-Common Met., 1974, 37, 1.
134. K. R. Bauchspiess, W. Boksch, E. Holland-Moritz, H. Launois, R. Pot and D. Wohlleben, in Valence Fluctuations in Solids, ed. L. M. Falicov, W. Hanke and M. B. Maple, Amsterdam, 1981, p. 417.