Analysis of equilibria in the extraction of cesium nitrate by calix[4]arene-bis(t-octylbenzo-crown-6) in 1,2-dichloroethane

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Abstract

The extraction of CsNO3 by the highly lipophilic calixarene-crown ether calix[4]arene-bis(t-octylbenzo-crown-6) (CABOBC6) in 1,2-dichloroethane (1,2-DCE) at 25 °C has been shown to be consistent with the formation of both 1 : 1 and 2 : 1 metal : ligand species. Variation of the aqueous-phase CsNO3 concentration up to 1.0 M and variation of the organic-phase calixarene concentration up to 0.10 M was modeled by the program SXLSQI. Formation of the organic-phase species CsBNO3 (B = calixarene) was confirmed as well as the organic-phase dissociation products CsB+ and NO-3. Good evidence for the 2 : 1 metal : ligand organic-phase species Cs2B(NO3)2 was also found, although the dissociation of nitrate from this complex was not observed. Binding of the second Cs+ cation by the ligand is approximately two orders of magnitude weaker than binding of the first Cs+ cation. The logarithm of the apparent partition ratio (log PB) of the calixarene between water and 1,2-DCE was found by 1H-NMR techniques to be > 5.1.

Original languageEnglish
Pages (from-to)21-37
Number of pages17
JournalJournal of Inclusion Phenomena
Volume36
Issue number1
DOIs
StatePublished - Jan 2000

Funding

The authors wish to thank J. C. Bryan for helpful suggestions concerning the structure of complexes of calix[4]arene-crown-6 ligands with cesium and C. F. Coleman for helpful suggestions in preparation of the manuscript. This research was sponsored by the Environmental Management Science Program, Offices of Energy Research and Environmental Management, U.S. Department of Energy, under Contract DE-AC05-96OR22464 with Oak Ridge National Laboratory, managed by Lockheed Martin Energy Research Corporation.

Keywords

  • Calixarene-crown ether
  • Cs complexation
  • Equilibrium constants
  • Modeling
  • Partition ratio
  • SXLSQI
  • Solvent extraction

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