Journal of Phase Equilibria

, Volume 14, Issue 4, pp 485–493 | Cite as

Contribution to the thermochemistry of rare earth pnictides: The Sm-Bi system

  • G. Borzone
  • N. Parodi
  • R. Ferro
Section I: Basic and Applied Research


Formation enthalpies of Sm-Bi alloys (in the complete range of compositions) and Er-Bi alloys (for a few compositions) have been measured using a direct, small-furnace, isoperibolic aneroid differential calorimeter. Typical values for the reaction in the solid state at 300 K are: Sm2Bi,−88 ± 3; Sm5Bi3, −94 ± 4; Sm4Bi3, −104 ± 2; SmBi, −108 ± 2; SmBi2, −76 ± 4; and ErBi, −90 ± 5 kJ/g-atom.

The experimental data are briefly discussed, compared with those of similar rare earth compounds, and found to be in good agreement with those computed according to the Miedema model and, for the rare earth-rich alloys, also with those calculated according to the Kubaschewski suggestion based on the so-called “effective coordination number” in alloys.


Rare Earth Ferro Erbium Samarium Congruent Melting 
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Cited References

  1. 38Kub:.
    O. Kubaschewski and W. Seith, “Heats of Formation of Non Ferrous Alloys”Z. Metallkd., 30, 7–9 (1938) in German.Google Scholar
  2. 39Kub:.
    O. Kubaschewski and A. Walter, “On an Adiabatic High Temperature Calorimeter for the Determination of Alloy Formation Heats,”Z. Elektrochem. Angewandte Phys. Chem., 45(8), 630–636 (1939) in German.Google Scholar
  3. 41Kub:.
    O. Kubaschewski and F.E. Wittig, “Heat of Formation of Magnesium Telluride,”Z. Elektrochem. Angewandte Phys. Chem., 47(6), 433–438 (1941)in German.Google Scholar
  4. 43Wei:.
    F. Weibke and O. Kubaschewski,Thermochemistry of Alloys, Springer-Verlag, Berlin ( 1943) in German.Google Scholar
  5. 49Kub:.
    O. Kubaschewski and H. Villa, “Heat of Formation of Zintl Al-kaline Earth Compounds,”Z. Elektrochem. Angewandte Phys. Chem., 53(1), 32–40 (1949) in German.Google Scholar
  6. 52Wag:.
    C. Wagner,Thermodynamics of Alloys, Addison-Wesley Pub-lishing Co., Reading, MA (1952).Google Scholar
  7. 55Kub:.
    O. Kubaschewski and W. A. Dench, “The Heats of Formation in the Systems Titanium-Aluminium and Titanium-Iron,”Acta Metall., 3, 339–346 (1955).Google Scholar
  8. 58Kub1:.
    O. Kubaschewski and E.L.L. Evans,Metallurgical Thermo-chemistry, Pergamon Press, London (1958).Google Scholar
  9. 58Kub2:.
    O. Kubaschewski and H.A. Sloman, “Relations Between Physical Properties and Bond Mechanism of Intermediate Compounds,”Proceedings of the Symposium on Physical Chemistry of Metallic Solutions and Intermetallic Compounds, National Physical Laboratory, Teddington, Middlesex, England, paper 3B, 4–6 June (1958).Google Scholar
  10. 58Kub3:.
    O. Kubaschewski, “The Problem of the Stability of Intermetallic Phases,”Proceedings of the Symposium on Physical Chemistry of Metallic Solutions and Intermetallic Compounds, National Physical Laboratory, Teddington, Middlesex, England, paper 3C, 4–6 June (1958).Google Scholar
  11. 59Par:.
    W. Parrish and A.J.C. Wilson, inInternational Tables for X-Ray Crystallography, Vol. 2, J.S. Kasper and K. Lonsdale, Ed., The Kynoch Press, Birmingham, United Kingdom, 216–234 (1959).Google Scholar
  12. 62Kub:.
    O. Kubaschewski, “Free-Energy and Phase-Diagrams,”Thermodynamics of Nuclear Materials, International Atomic Energy Agency, Vienna, 219–241 (1962).Google Scholar
  13. 66Kub:.
    O. Kubaschewski, “The Thermodynamic Stability of Phases at High Temperatures,” Stockholm University, Ed., Högtempera-tursymposiet, Stockholm, 1–17,21–22 April(1966).Google Scholar
  14. 67Gam:.
    R.J. Gambino, “Rare-Earth-Sb and -Bi Compounds with the Gd4Bi3 (anti-Th3P4) Structure,”J. Less-Common Met., 12, 344–352 (1967).Google Scholar
  15. 67Kub:.
    O. Kubaschewski, E.L.L. Evans, and C.B. Alcock,Metallurgical Thermochemistry, Pergamon Press, London (1967).Google Scholar
  16. 71Kob:.
    V.I. Kober, V.A. Lebedev, I.F. Nichkov, S.P. Raspopin, and A.I. Belusov, “The State of Lanthanum, Cerium and Yttrium in Bismuth Solution,”Russ. J. Phys. Chem., 45(8), 1127–1129 (1971).Google Scholar
  17. 74Bor1:.
    A. Borsese, R. Capelli, S. Delfino, and R. Ferro, “Heat of Formation of La4Bi3 and LaBi Compounds,”Thermochim Acta, 9, 313–317 (1974).Google Scholar
  18. 74Bor2:.
    A. Borsese, R. Capelli, S. Delfino, and R. Ferro, “The Heat of Formation of Neodymium-Bismuth Alloys,”Thermochim. Acta., 8, 393–397 (1974).Google Scholar
  19. 74Cap:.
    R. Capelli, R. Ferro, and A. Borsese, “A Direct Isoperibol Aneroid Calorimeter,”Thermochim. Acta., 10, 13–21 (1974).Google Scholar
  20. 74Fer:.
    R. Ferro, A. Borsese, R. Capelli, and S. Delfino, “Heat of Formation of Yttrium-Bismuth Alloys,”Thermochim. Acta., 8, 387–391 (1974).Google Scholar
  21. 75Bor1:.
    A. Borsese, G. Borzone, R. Ferro, and R. Capelli, “Heat of Formation of Magnesium-Tin Alloys,”Z. Metallkd., 66, 226–227 (1975).Google Scholar
  22. 75Bor2:.
    A. Borsese, R. Ferro, R. Capelli, and S. Delfino, “Heat of Formation of Yttrium-Lead Alloys,”J. Less-Common Met., 42, 179–185 (1975).Google Scholar
  23. 75Bor3:.
    A. Borsese, R. Ferro, R. Capelli, and S. Delfino, “Heat of Formation of Praseodymium-Bismuth Alloys,”Thermochim. Acta., 11, 205–210 (1975).Google Scholar
  24. 75Fer:.
    R. Ferro, A. Borsese, R. Capelli, and S. Delfino, “Heat of Formation of Lanthanum-Lead Alloys,”Z. Anorg. Allg. Chem., 413, 279–284 (1975).Google Scholar
  25. 75Yos:.
    K. Yoshihara, J.B. Taylor, L.D. Calvert, and J.G. Despault, “Rare-Earth Bismuthides,”J. Less-Common Met., 41, 329–337 (1975).Google Scholar
  26. 76Pet:.
    S.E. Petrashkevich, V.A. Degtyar, L.A. Vnuchkova, and V.V. Serebrennikov, “Reaction of Erbium with Bismuth and Aluminium,”Nauch. Soobshch. II Vses. Konf. bo Stroeniyu i Svoistvam Metal., i Shlak. Rasplavov., Ch. 2,12 (1976) in Russian.Google Scholar
  27. 76Wan:.
    Y. Wang, E.J. Gabe, L.D. Calvert, and J.B. Taylor, “The Crystal Structureof Y5Bi3 and its Relation to the Mn5Si3 and the Yb5Sb3 Type Structures,”Acta Crystallogr., B, 32, 1440–1445 (1976).Google Scholar
  28. 77Bor1:.
    A. Borsese, A. Calabretta, S. Delfino, and R. Ferro, “Measurements of Heats of Formation in the Lanthanum-Indium System,”J. Less-Common Met., 57, 45–49 (1977).Google Scholar
  29. 77Bor2:.
    A. Borsese, R. Ferro, R. Capelli, and S. Delfino, “Heats of Formation of Neodymium-Antimony Alloys,”J. Less-Common Met., 55, 77–83 (1977).Google Scholar
  30. 77Bor3:.
    A. Borsese, G. Borzone, R. Ferro, and S. Delfino, “Heats of Formation of Dysprosium-Bismuth Alloys,”J. Less-Common Met., 55, 115–120 (1977).Google Scholar
  31. 77Bor4:.
    A. Borsese, G. Borzone, A. Saccone, and R. Ferro, “Heats of Formation of Yttrium-Antimony Alloys,”J. Less-Common Met., 52, 123–128 (1977).Google Scholar
  32. 77Nom:.
    K. Nomura, H. Hayakawa, and S. Ono, “The Lanthanum-Bismuth Alloy System,”J. Less-Common Met., 52, 259–269 (1977).Google Scholar
  33. 78Bor:.
    G. Borzone, A. Borsese, A. Calabretta, and R. Ferro, “Heats of Formation of Cerium-Bismuth Alloys,”J. Less-Common Met., 58, 31–36 (1978).Google Scholar
  34. 78HuI:.
    F. Hulliger and F. Stucki, “Lattice Distorsions in Terbium Chalcogenides and Pnictides,”Z. Phys. B, 31, 391–393 (1978).ADSGoogle Scholar
  35. 78Kem:.
    B. Kempf, B. Elschner, P. Spitzli, and O. Fischer, “Superconductivity and Magnetic Ordering in Bi3Sr1-xEUx,”Phys. Rev. B, 17(5), 2163–2170 (1978).ADSGoogle Scholar
  36. 79Bor:.
    G. Borzone, A. Borsese, A. Saccone, and R. Ferro, “Heats of Formation of Lanthanum-Antimony Alloys,”J. Less-Common Met., 65, 253–262 (1979).Google Scholar
  37. 79HuI:.
    F. Hulliger,Handbook on the Physics and Chemistry of Rare Earths, Vol. IV, K.A. Gschneidner, Jr. and L. Eyring, Ed., North-Holland, Amsterdam, 153 (1979).Google Scholar
  38. 79Yam:.
    L.F. Yamshchikov, V.A. Lebedev, I.F. Nichkov, S.P. Raspopin, and B.A. Karmanov, “Thermodynamics Properties of Molten Alloys of Erbium with Low-Melting Metals,”Termodin. Svoistva Met. Rasplavov, Mater. Vses Soveshch. Termodin. Met. Splavov (Rasplavy), 4th, L.F. Kozin, IIzd. Nauka Kazakhskoi SSR, Ed., Alma-Ata, USSR,2,181–185 (1979)in Russian.Google Scholar
  39. 80And:.
    K. Andres, A. Jayaraman, R.G. Maines, F.S.L. Hsu, H.R. Ott, and E. Bucher, “A Novel Low Temperature Phase Transition in Mixed Valent Sm4Bi3,” J.E. Crow, R.P. Guertin, T.W. Mihalisin, Plenum: New York, Ed., Proceedings Cryst. Electr. Field Struct. Eff. f-Electron Syst, 1979, 327-332, (1980).Google Scholar
  40. 80Bor1:.
    A. Borsese, G. Borzone, and R. Ferro, “Thermochemistry of Binary Alloys of Rare Earths: AComparison Between Experimental and Calculated Heats of Formation,”J. Less-Common Met., 70, 213–216 (1980).Google Scholar
  41. 80Bor2:.
    G. Borzone, A. Borsese, and R. Ferro, “Heats of Formation of Gadolinium-Bismuth Alloys,”Thermoch. Acta, 41, 175–180 (1980).Google Scholar
  42. 80Hu1:.
    F. Hulliger, “Magnetic Behaviour of DyBi,”J. Magn. Magn. Mater., 15-18, 1243–1244 (1980).ADSGoogle Scholar
  43. 81Bor:.
    A. Borsese, G. Borzone, D. Mazzone, and R. Ferro, “Heats of FormationofCe-Sb Alloys,”J. Less-Common Met., 79, 57–63 (1981).Google Scholar
  44. 81Kub:.
    O Kubaschewski, “Experimental Thermochemistry of Alloys,”Physica B, 103, 101–112 (1981).Google Scholar
  45. 82Bor1:.
    G. Borzone, A. Borsese, and R. Ferro, “On the Alloying Behaviour of Cerium with Tin,”J. Less-Common Met., 85, 195–203 (1982).Google Scholar
  46. 82Bor2:.
    G. Borzone, A. Borsese, and R. Ferro, “Thorium Bismuthides: Crystal Structures and Thermochemistry,“J. Less-Common Met., 84, 165–172 (1982).Google Scholar
  47. 82Bor3:.
    G. Borzone, A. Borsese, G. Zanicchi, and R. Ferro, “Determination of Heats of Formation of Praseodymium Antimonides,”J. Therm. Anal., 25, 433–440 (1982).Google Scholar
  48. 82Sch:.
    R.A. Schiffman and H.F. Franzen, “Thermodynamics of Congruently Subliming Cerium-Antimony,”High Temp. Sci., 15, 179–185 (1982).Google Scholar
  49. 83Bor1:.
    G. Borzone, A. Borsese, and R. Ferro, “A Contribution to the Study of the Alloying Behaviour of the Rare Earths with Tin,”Z. Anorg. Allg, Chem., 501, 199–208 (1983).Google Scholar
  50. 83Bor2:.
    G. Borzone, A. Borsese, and R. Ferro, “Contribution to Alloy Calorimetry of the Rare Earths,”Gazzetta Chimica Italiana, 113, 235–238 (1983).Google Scholar
  51. 83Vik:.
    G.Sh. Viksman and S.P. Gordienko, “Evaporation of Praseodymium Monobismuthide,”Poroshk. Metall. (Kiev), 11, 63–65 (1983) in Russian.Google Scholar
  52. 84Co1:.
    C. Colinet, A. Pasturel, A. Percheron-Guégan, and J.C. Achard, “Enthalpies of Formation of Liquid and Solid Binary Alloys of Lead, Antimony and Bismuth with Rare Earth Elements,”J. Less-Common Met., 102, 239–249 (1984).Google Scholar
  53. 85Bor:.
    G. Borzone, A. Borsese, S. Delfino, and R. Ferro, “Antimony Compounds of the Rare Earths: Heats of Formation of Sm-Sb Alloys,”Z. Metallkd, 76, 208–213 (1985).Google Scholar
  54. 85Fer:.
    R. Ferro, “Contribution to the Thermodynamics of Rare-Earth Binary Alloys,”J. Less-Common Met., 110, 53–60 (1985).Google Scholar
  55. 85Kob:.
    V.I. Kober, V.A. Dubinin, and S.P. Raspopin, “Thermodynamic Properties of Saturated Solutions of Europium with Bismuth, Lead and Tin,”Zh. Fiz. Khim., 59(9), 2124–2126 (1985) in Russian.Google Scholar
  56. 85Leg:.
    J.M. Léger, K. Oki, J. Rossat-Mignod, and O. Vogt, “Structural Transition and Volume Compression of CeBi up to 20 GPa,”J. Phys. (Orsay), 46, 889–894 (1985).Google Scholar
  57. 85Mak:.
    T.F. Maksudova, P.G. Rustamov, and O.M. Aliev, “The Ytterbium-Bismuth System,”J. Less-Common Met., 109, L19-L23 (1985).Google Scholar
  58. 85Sad:.
    F.M. Sadigov, O.M. Aliyev, and P.G. Rustamov, “The Phase Diagram of the Sm-Bi System,”J. Less-Common Met., 113, L17-L19 (1985).Google Scholar
  59. 85Yam1:.
    L.F. Yamshchikov, V.A. Lebedev, and A.N. Klepikov, “Thermodynamics Properties of Sc-Bi Alloys,”Izv. Akad. Nauk SSSR, Met., 4, 202–204 (1985) in Russian.Google Scholar
  60. 85Yam2:.
    L.F. Yamshchikov, V.A. Lebedev, S.P. Raspopin, and, P.A. Arkhipov, “Thermodynamics of Formation of HoBi and HoSb,”Izv V.U.Z. Tsvetn. Metall., (6), 106–108 (1985) in Russian.Google Scholar
  61. 86Bor:.
    G. Borzone, G. Cacciamani, A. Saccone, S. Delfino, and R. Ferro, “Contribution to the Thermochemistry of the Bismuthides of the Rare Earths,” Università degli Studi di Ferrara, Ed., Proceedings of Journées de Calorimétrie d'Analyse Thermique et de Thermodynamique Chimique, 349-352, Ferrara 27–30 Ottobre 1986 (1986).Google Scholar
  62. 87Ber:.
    H. Bergmann, Ed., “Sc, Y, La-Lu Rare Earth Elements. Compounds with Te, Po,”Gmelin Handbook of Inorganic Chemistry, C10, 8th ed., Spring-Verlag, Berlin (1987).Google Scholar
  63. 87Bor:.
    G. Borzone, G. Cacciamani, R. Ferro, J. Charles, and J. Hertz, “A Contribution to the Study of the Alloying Behaviour of the Rare Earths with Zinc,”J. Less-Common Met., 128, 297–312 (1987).Google Scholar
  64. 87Kob:.
    V.I. Kober, I.F. Nichkov, and S.P. Raspopin, “Thermodynamic Properties of Samarium Intermetallic Compounds with High Contents of the Low-Melting Metal,”Ivz. VU.Z. Tsvetn. Metall, 5, 116–118 (1987) in Russian.Google Scholar
  65. 87Mor:.
    A. Morisson and C. Petot, “Determination of the Free Enthalpy of Formation of LaBi2 and CeBi2,”Thermochim Acta, 115, 167–173 (1987) in French.Google Scholar
  66. 87Vik:.
    G.Sh. Viksman and S.P. Gordienko, “Thermodynamic Characteristics of La, Pr, Nd and Gd Monobismuthides,”Poroshk. Metall (Kiev), 7, 63–65 (1987) in Russian.Google Scholar
  67. 88Boe:.
    F.R. de Boer, R. Boom, W.C.M. Mattens, A.R. Miedema, and A.K. Niessen, “Cohesion and Structure,” Vol. I,Cohesion in Metals. Transition Metal Alloys, F.R. de Boer and D.G. Pettifor, Ed., North-Holland Publishing Co., Amsterdam, NL (1988).Google Scholar
  68. 88Fer:.
    R. Ferro, G. Borzone, and G. Cacciamani, “On the Thermochemistry of the Rare Earth Antimonides. The Dy-Sb System,”Thermo-chim. Acta, 129, 99–113 (1988).Google Scholar
  69. 89Cac:.
    G. Cacciamani, G. Borzone, A. Saccone, and R. Ferro, “Heat Content of Magnesium-Lead Alloys,”J. Less-Common Met., 154, 109–113 (1989).Google Scholar
  70. 89Gam:.
    M. Gambino, P. Rebouillon, J.P. Bros, G. Borzone, G. Cacciamani, and R. Ferro, “High Temperature Heat Capacity of CePb3, LaPb3 and NdPb3,”J. Less-Common Met., 154, 195–205 (1989) in French.Google Scholar
  71. 89Gsc:.
    K.A. Gschneidner, Jr. and F.W. Calderwood, “The Bismuth-Rare Earth Systems,”Bull. Alloy Phase Diagrams, 10(4), 419–459 (1989).Google Scholar
  72. 90Mas:.
    T.B. Massalski, P.R. Subramanian, H. Okamoto, and L. Kacprzak, Ed.,Binary Alloy Phase Diagrams, 2nd ed., Vol 1–3, ASM International, Materials Park, OH ( 1990).Google Scholar
  73. 91Bor:.
    G. Borzone, G. Cacciamani, and R. Ferro, “Heats of Formation of Aluminium-Cerium Intermetallic Compounds,”Metall. Trans. A, 22, 2119–2123 (1991).Google Scholar
  74. 91 Vi1:.
    P. Villars and L.D. Calvert,Pearson’s Handbook of Crystallographk Data for Intermetallic Phases, 2nd ed., Vol 1–4, ASM International, Materials Park, OH (1991 ).Google Scholar
  75. 92Par:.
    N. Parodi, G. Borzone, G. Cacciamani, B. Brusasco, and R. Ferro, “On the Thermodynamics of the Samarium Bismuthides,”Proceedings of XVII Congresso Nazionale della Società Chimica Italiana (Januachem92), 1013–1014, Genova 25–30, Ottobre 1992 (1992).Google Scholar
  76. 93Vas:.
    V. Vassiliev, M. Gambino, J.P. Bros, G.Borzone,G. Cacciamani, and R. Ferro, “Thermodynamic Investigation and Optimization of the Y-Pb Alloy System,”J. Phase Equilibria, 14(2), 142–149 (1993).Google Scholar

Copyright information

© ASM International 1993

Authors and Affiliations

  • G. Borzone
    • 1
  • N. Parodi
    • 1
  • R. Ferro
    • 1
  1. 1.Istituto di Chimica GeneraleUniversità di Genova Viale Benedetto XVGenovaItaly

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