Thermodynamic study on the U(VI) complexation with dicarboxylates by calorimetry

A. Kirishima, Y. Onishi, N. Sato, O. Tochiyama

Research output: Contribution to journalArticlepeer-review

21 Citations (Scopus)

Abstract

The thermodynamic quantities (ΔG, ΔH and ΔS) of U(VI) complexation with oxalate, malonate, succinate, glutarate, adipate, phthalate, tartronate and malate, and of Eu(III) complexation with succinate, glutarate and adipate were determined by potentiometric and calorimetric titration techniques. The obtained thermodynamic quantities indicated that these complexation reactions are mainly driven by the entropy changes while the enthalpy changes are nearly zero or preventing the complexation. The thermodynamic quantities of 1:1 U(VI) complexes with 5 dicarboxylates having different carbon chain lengths (-OOC-(CH2) n-COO-) showed an interesting tendency, that is, -ΔH decreased and T ΔS increased systematically with increasing the length of the carbon chain from n = 2 to 6. The comparison of T ΔS values of 1:1 carboxylate formation with U(VI) and Eu(III) showed that T ΔS of U(VI) were always lager than those of Eu(III). The entropies of 1:1 complex formation of U(VI) with hydroxycarboxylates were always smaller than those with carboxylates of the same carbon chain length, while the enthalpies of uranyl hydroxycarboxylates were always larger. This tendency was also observed in the protonation and the complex formation of Eu(III).

Original languageEnglish
Pages (from-to)581-589
Number of pages9
JournalRadiochimica Acta
Volume96
Issue number9-11
DOIs
Publication statusPublished - 2008 Nov 28

Keywords

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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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