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Formation Enthalpies of Tetravalent Lanthanide Perovskites by High Temperature Oxide Melt Solution Calorimetry

Published online by Cambridge University Press:  01 February 2011

S. V. Ushakov ,
J. Cheng ,
A. Navrotsky ,
J. R. Wu  and
S. M. Haile
S. V. Ushakov
Affiliation:
Materials Science Department, California Institute of Technology, Pasadena, CA 91125, USA
J. Cheng
Affiliation:
Thermochemistry Facility, Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, CA 95616, USA
A. Navrotsky
Affiliation:
Thermochemistry Facility, Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, CA 95616, USA
J. R. Wu
Affiliation:
Materials Science Department, California Institute of Technology, Pasadena, CA 91125, USA
S. M. Haile
Affiliation:
Materials Science Department, California Institute of Technology, Pasadena, CA 91125, USA
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Abstract

High-temperature oxide melt solution calorimetry was used to measure formation enthalpies for several compositions of perovskites of nominal stoichiometry BaPrO3 and BaCeO3. Samples were synthesized from chemical solution methods followed by calcination at 1100-1300°C. PrO2 was synthesized by oxidation of Pr6O11 in an oxygen flow at 280°C. The samples were characterized by microprobe, thermogravimetric and differential thermal analyses. Cell parameters were refined by the Rietveld method. Barium excess in the samples with respect to ideal stoichiometry was detected. Drop solution enthalpies were measured in a Calvet type twin microcalorimeter, using 3Na2O·4MoO3 solvent at 702°C. Preliminary values of the formation enthalpy of BaPrO3 and BaCeO3 from oxides were -70 ±10 kJ/mol and -51 ±10 kJ/mol, respectively. They fall on the normal trend of energetics versus Goldschmidt tolerance factor and do not show any special stabilization of BaPrO3 relative to other MLnO3 perovskites.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 718: Symposium D – Perovskite Materials , 2002 , D7.17
Copyright
Copyright © Materials Research Society 2002

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References

1. Navrotsky, A., “Thermochemistry of perovskites”, Perovskite: A structure of Great Interest to Geophysics and Material Science, ed. Navrotsky, A. and Weidner, D.J., (Geophysical Monograph 45, 1987) pp. 67–80 Google Scholar
2. Morss, L. R., Menzi, N., The Rare Earths in Modern Science and Technology. New York, 1982, p. 279–282.Google Scholar
3. Gopalan, S., Virkar, A.V., J. Electrochem. Soc., 140, 4, 1060–1065, (1993).Google Scholar
4. Cordfunke, E. H. P., Booij, A. S., Huntelaar, M. E., J. Chem. Thermodyn., 30, 4, 437–447, (1998).Google Scholar
5. Navrotsky, A., Phys. Chem. Min. 2, 89 (1977). idem, ibid. 24, 222 (1997).Google Scholar
6. Argawal, V., Lui, M., J. Mat. Sci. 32, 619–625 (1997).Google Scholar
7.PDF #241006, ICDD, 1999 Google Scholar
8. Boothroyd, A. T., Gardiner, C.H., Lister, S. J. S.,. Santini, P., Rainford, B. D., Noailles, L.D., Currie, D. B., Eccleston, R. S., and Bewley, R. I., Phys. Rev. Lett. 86, 10, 2082–2085, (2001).Google Scholar
9. Larson, A. C., Dreele, R. B. Von, “General Structure Analysis System (GSAS)”, Los Alamos National Laboratory Report LAUR 86–748 (2000).Google Scholar
10. Toby, B. H., J. Appl. Cryst. 34, 210–213 (2001).Google Scholar
11. Jacobson, A. J., Tofield, B. C. and Fender, B. E., Acta cryst. (1972) B28, 956–961 Google Scholar
12. Knight, K. S., Solid State Ionics, 74 (1994) 109–117 Google Scholar
13. Rosov, N., Lynn, J.W., Lin, Q., Cao, G., O'Reilly, J.W., Pernambuco-Wise, P. and Crow, J.E., Phys. Rev. B 45, 982–986 (1992)Google Scholar
14. Shima, D. and Haile, S. M., Solid State Ionics, 97 (1997) 443–455.Google Scholar
15. Saha, R., Babu, R., Nagarajan, K., and Mathews, C.K., Thermochimica Acta, 120, 29–39 (1987)Google Scholar
16. Majzlan, J., Navrotsky, A., and Neil, J.M., Geochimica et Cosmochimica Acta, (2002) (in press)Google Scholar
17. Gramsch, S. A., Morss, L. R., J. Chem. Thermodyn. 27(5), 551–60, (1995)Google Scholar
18. Robie, R.A., Hemingway, B.S., Thermodynamic Properties of Minerals and Related Substances at 298.15 K and 1 Bar (105 Pascals) Pressure and at Higher Temperatures; (U.S. Geol. Surv. Bull. 2131. Washington D.C., 1995).Google Scholar
19. Ushakov, S. V., Helean, K. B., Navrotsky, A., and Boatner, L. A., J. Mater. Res., 16, 9, (2001)Google Scholar
20. Goldschmidt, V. M., Naturwissenschaften, 14, 477–485, (1926)Google Scholar