Determination of the thermodynamic quantities of uranium(VI)-carboxylate complexes by microcalorimetry

Akira Kirishima, Yuko Onishi, Nobuaki Sato, Osamu Tochiyama

Research output: Contribution to journalArticlepeer-review

17 Citations (Scopus)

Abstract

Potentiometric and microcalorimetric titration techniques were applied for the determination of the Gibbs free energies and enthalpies of the protonation and U(VI) complexation of some carboxylic acids (formic, acetic, glycolic, and propionic acids) in 1.0 M NaClO4 solution at 25 °C. By using the values of ΔG determined by potentiometric titrations, the results of calorimetric titrations were analyzed to give the values of ΔH and ΔS. These enthalpy values indicated that the protonation and uranyl(VI) complexation of these carboxylates were mainly entropy-driven, that is, {divides}-TΔS{divides} ≫ {divides}ΔH{divides} in ΔG = ΔH - TΔS. The comparison of TΔSm values for uranyl acetate and glycolate complexation with those for europium(III) complexation revealed that the complexation of U(VI) was accompanied by larger entropy changes due to the limited space in its coordination sphere caused by the steric hindrance of two oxygens in the linear dioxo structure of uranyl ion.

Original languageEnglish
Pages (from-to)1432-1438
Number of pages7
JournalJournal of Chemical Thermodynamics
Volume39
Issue number11
DOIs
Publication statusPublished - 2007 Nov

Keywords

  • Carboxylic acid
  • Enthalpy
  • Entropy
  • Stability constant
  • Uranium(VI) complex

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Materials Science(all)
  • Physical and Theoretical Chemistry

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