Energetics of formation of alkali and ammonium cobalt and zinc phosphate frameworks
- Peter A. Rock Thermochemistry Laboratory, Chemistry Department, NEAT ORU, University of California at Davis, Davis, CA 95616 (United States)
Alkali and ammonium cobalt and zinc phosphates show extensive polymorphism. Thermal behavior, relative stabilities, and enthalpies of formation of KCoPO{sub 4}, RbCoPO{sub 4}, NH{sub 4}CoPO{sub 4}, and NH{sub 4}ZnPO{sub 4} polymorphs are studied by differential scanning calorimetry, high-temperature oxide melt solution calorimetry, and acid solution calorimetry. {alpha}-KCoPO{sub 4} and {gamma}-KCoPO{sub 4} are very similar in enthalpy. {gamma}-KCoPO{sub 4} slowly transforms to {alpha}-KCoPO{sub 4} near 673 K. The high-temperature phase, {beta}-KCoPO{sub 4}, is 5-7 kJ mol{sup -1} higher in enthalpy than {alpha}-KCoPO{sub 4} and {gamma}-KCoPO{sub 4}. HEX phases of NH{sub 4}CoPO{sub 4} and NH{sub 4}ZnPO{sub 4} are about 3 kJ mol{sup -1} lower in enthalpy than the corresponding ABW phases. There is a strong relationship between enthalpy of formation from oxides and acid-base interaction for cobalt and zinc phosphates and also for aluminosilicates with related frameworks. Cobalt and zinc phosphates exhibit similar trends in enthalpies of formation from oxides as aluminosilicates, but their enthalpies of formation from oxides are more exothermic because of their stronger acid-base interactions. Enthalpies of formation from ammonia and oxides of NH{sub 4}CoPO{sub 4} and NH{sub 4}ZnPO{sub 4} are similar, reflecting the similar basicity of CoO and ZnO. - Graphical abstract: Relationship between enthalpy of formation from oxides and acid-base interaction for cobalt phosphates, zinc phosphates, and aluminosilicates with related frameworks. They exhibit similar trends, but the enthalpies of formation of phosphates are more exothermic than those of aluminosilicates because of stronger acid-base interactions.
- OSTI ID:
- 21043855
- Journal Information:
- Journal of Solid State Chemistry, Vol. 181, Issue 1; Other Information: DOI: 10.1016/j.jssc.2007.10.017; PII: S0022-4596(07)00432-X; Copyright (c) 2007 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
Similar Records
Energetics of cobalt phosphate frameworks: {alpha}, {beta}, and red NaCoPO{sub 4}
Unraveling the formation mechanism of NaCoPO4 polymorphs