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• W2037343568 abstract "The ϵ -Al 13 Keggin aluminum hydroxide clusters are essential models in establishing molecular pathways for geochemical reactions. Enthalpies of formation are reported for two salts of aluminum centered ϵ-Keggin clusters, Al 13 selenate, (Na(AlO 4 )Al 12 (OH) 24 (SeO 4 ) 4 •12H 2 O) and Al 13 sulfate, (NaAlO 4 Al 12 (OH) 24 (SO 4 ) 4 •12H 2 O). The measured enthalpies of solution, ΔH sol , at 28 °C in 5 N HCl for the ε -Al 13 selenate and sulfate are −924.57 (± 3.83) and −944.30 ( ± 5.66) kJ·mol -1 , respectively. The enthalpies of formation from the elements, Δ H f ,el , for Al 13 selenate and sulfate are −19,656.35 ( ± 67.30) kJ·mol -1 , and −20,892.39 ( ± 70.01) kJ·mol -1 , respectively. In addition, Δ H f ,el for sodium selenate decahydrate was calculated using data from high temperature oxide melt solution calorimetry measurements: −4,006.39 ( ± 11.91) kJ·mol -1 . The formation of both ε -Al 13 Keggin cluster compounds is exothermic from oxide-based components but energetically unfavorable with respect to a gibbsite-based assemblage. To understand the relative affinity of the ϵ-Keggin clusters for selenate and sulfate, the enthalpy associated with two S-Se exchange reactions was calculated. In the solid state, selenium is favored in the Al 13 compound relative to the binary chalcogenate, while in 5 N HCl, sulfur is energetically favored in the cluster compound compared to the aqueous solution. This contribution represents the first thermodynamic study of ε -Al 13 cluster compounds and establishes a method for other such molecules, including the substituted versions that have been created for kinetic studies. Underscoring the importance of ε -Al 13 clusters in natural and anthropogenic systems, these data provide conclusive thermodynamic evidence that the Al 13 Keggin cluster is a crucial intermediate species in the formation pathway from aqueous aluminum monomers to aluminum hydroxide precipitates." @default.
• W2037343568 created "2016-06-24" @default.
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• W2037343568 date "2011-08-18" @default.
• W2037343568 modified "2023-10-17" @default.
• W2037343568 title "Energetics of Al ₁₃ Keggin cluster compounds" @default.
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• W2037343568 doi "https://doi.org/10.1073/pnas.1111243108" @default.
• W2037343568 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/3169149" @default.
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• W2037343568 hasPublicationYear "2011" @default.
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