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Thermochemistry of rare-earth orthophosphates

Published online by Cambridge University Press:  31 January 2011

S. V. Ushakov ,
K. B. Helean ,
A. Navrotsky  and
L. A. Boatner
S. V. Ushakov
Affiliation:
Thermochemistry Facility, Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, California 95616–8779
K. B. Helean
Affiliation:
Thermochemistry Facility, Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, California 95616–8779
A. Navrotsky*
Affiliation:
Thermochemistry Facility, Department of Chemical Engineering and Materials Science, University of California at Davis, Davis, California 95616–8779
L. A. Boatner
Affiliation:
Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831–6056
*
a)Address correspondence to this author.
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Abstract

The enthalpies of formation for the compounds (RE3+)PO4, (where RE = Sc, Y, La–Nd, Sm–Lu) were determined by oxide-melt solution calorimetry. Calorimetric measurements were performed in a Calvet-type twin microcalorimeter in sodium molybdate (3Na2O · 4MoO3) and lead borate (2PbO · 2B2O3) solvents at 975 K. The experiments were carried out using both powdered single crystals grown by a flux technique and powders synthesized by precipitation. Formation enthalpies were derived from the drop-solution enthalpies for (RE)PO4, RE oxides, and P2O5. Enthalpies of formation for the (RE)PO4 compounds with respect to the oxides at 298 K become more negative with increasing RE3+ ionic radius; i.e., in going from ScPO4 (−209.8 ± 1.0 kJ/mol), to LuPO4 (−263.9 ± 1.9 kJ/mol), to LaPO4 (−321.4 ± 1.6 kJ/mol). From structural considerations, a similar trend is expected for the isostructural RE vanadates and arsenates, as well as for the tetravalent actinide orthosilicates.

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Articles
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Journal of Materials Research , Volume 16 , Issue 9 , September 2001 , pp. 2623 - 2633
Copyright
Copyright © Materials Research Society 2001

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