Surface enthalpy of boehmite

Juraj Majzlan, Alexandra Navrotsky, William H. Casey

Research output: Contribution to journalArticlepeer-review

37 Scopus citations

Abstract

The persistence of many seemingly metastable mineral assemblages in sediments and soils is commonly attributed to their sluggish transformation to the stable-phase assemblage. Although undoubtedly kinetics plays a major role, this study shows that thermodynamic factors, particularly surface energy, significantly influence the free energy. Enthalpies of formation of boehmite samples with variable surface area were derived using high-temperature oxide-melt calorimetry. The average surface enthalpy for all faces terminating boehmite particles was calculated at +0.52 ± 0.12 J/m2. This value represents the surface enthalpy for surfaces exposed to vacuum assuming that H2O adsorbed on the surface of boehmite is loosely bound. These results show that the enthalpy of formation of boehmite may vary by ≤8 kJ/mol as a function of particle size. An overview of published values of surface energies of gibbsite, γ-Al2O3, corundum, and the results here indicates that the hydrated phases (boehmite, gibbsite) have lower surface energies than the anhydrous phases (corundum, γ-Al2O3). Lower surface energies allow the hydrated phases to maintain high surface area, i.e., small particle size. Similar surface energies of boehmite and gibbsite suggest kinetic control favoring the crystallization of boehmite or gibbsite from aqueous solution. The enthalpy of formation of bulk boehmite from the elements was calculated at -994.0 ± 1.1 kJ/mol. Combining this result with the data in existing thermodynamic databases, we confirm that bulk boehmite is metastable with respect to bulk diaspore at ambient conditions.

Original languageEnglish (US)
Pages (from-to)699-707
Number of pages9
JournalClays and Clay Minerals
Volume48
Issue number6
DOIs
StatePublished - Dec 2000
Externally publishedYes

Keywords

  • Boehmite
  • Enthalpy of formation
  • Surface enthalpy

ASJC Scopus subject areas

  • Water Science and Technology
  • Soil Science
  • Geochemistry and Petrology
  • Earth and Planetary Sciences (miscellaneous)

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