Energetics of cobalt phosphate frameworks: {alpha}, {beta}, and red NaCoPO{sub 4}
- Thermochemistry Facility and Chemistry Department, University of California, Davis, CA 95616 (United States)
Thermal behavior, relative stability, and enthalpy of formation of {alpha} (pink phase), {beta} (blue phase), and red NaCoPO{sub 4} are studied by differential scanning calorimetry, X-ray diffraction, and high-temperature oxide melt drop solution calorimetry. Red NaCoPO{sub 4} with cobalt in trigonal bipyramidal coordination is metastable, irreversibly changing to {alpha} NaCoPO{sub 4} at 827 K with an enthalpy of phase transition of -17.4{+-}6.9 kJ mol{sup -1}. {alpha} NaCoPO{sub 4} with cobalt in octahedral coordination is the most stable phase at room temperature. It undergoes a reversible phase transition to the {beta} phase (cobalt in tetrahedra) at 1006 K with an enthalpy of phase transition of 17.6{+-}1.3 kJ mol{sup -1}. Enthalpy of formation from oxides of {alpha}, {beta}, and red NaCoPO{sub 4} are -349.7{+-}2.3, -332.1{+-}2.5, and -332.3{+-}7.2 kJ mol{sup -1}; standard enthalpy of formation of {alpha}, {beta}, and red NaCoPO{sub 4} are -1547.5{+-}2.7, -1529.9{+-}2.8, and -1530.0{+-}7.3 kJ mol{sup -1}, respectively. The more exothermic enthalpy of formation from oxides of {beta} NaCoPO{sub 4} compared to a structurally related aluminosilicate, NaAlSiO{sub 4} nepheline, results from the stronger acid-base interaction of oxides in {beta} NaCoPO{sub 4} (Na{sub 2}O, CoO, P{sub 2}O{sub 5}) than in NaAlSiO{sub 4} nepheline (Na{sub 2}O, Al{sub 2}O{sub 3}, SiO{sub 2}). - Graphical abstract: Relative stability of NaCoPO{sub 4} polymorphs compared to the most stable phase, {alpha} NaCoPO{sub 4}.
- OSTI ID:
- 20902487
- Journal Information:
- Journal of Solid State Chemistry, Vol. 179, Issue 12; Other Information: DOI: 10.1016/j.jssc.2006.08.007; PII: S0022-4596(06)00459-2; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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