Sequestration of the tributyl phosphate complex of europium nitrate in the clay hectorite. A 31P NMR study

Cynthia J Hartzell, S. W. Yang, Roderic A Parnell, D. E. Morris

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Abstract

The behaviour of organic complexes of actinides and lanthanides in clays plays an important role in environmental remediation. Application of 31P NMR to distinguish Eu(NO)3)3-complexed tributyl phosphate from uncomplexed tributyl phosphate (TBP) facilitates an understanding of the fate of these species in the clay hectorite. Solution 31P NMR studies show dramatic shifts of -156.0 to -172.9 ppm for Eu(NO3)36H2O dissolved in TBP at TBP:Eu ratios 1:1 to 1:2.5. Pure TBP exhibits 31P chemical shift of -0.3 ppm. Mixtures with higher TBP:Eu ratios display lines progressively downfield of -156.0 ppm, reflecting exchange of complexed and free TBP. The Eu(NO3)3-complexed TBP adsorbed into hectorite displays a 31P chemical shift of -180.7 to -193.8 ppm. Clays adsorbed with solutions that are 3.1, 5:1 and 7:1 TBP:Eu display peaks due to complex as well as peaks in the range -4 to -6 ppm attributed to uncomplexed TBP. No evidence of exchange is observed. Spectra of the TBP-adsorbed clay give a TBP line at -0.7 ppm which changes slightly to --5.0 after exchange with Eu(NO3)3. The Eu(NO3)3-exchanged hectorite displays a line at -17.6 ppm after adsorption of TBP. Neither of the latter two samples show indication of complex formation. The hectorite samples exposed to TBP or the complex display (001) d spacings of 17.9-18.4 A compared to 12.3-12.5 A for hectorite which has not been exposed to TBP.

Original languageEnglish (US)
Pages (from-to)4205-4210
Number of pages6
JournalJournal of Physical Chemistry
Volume99
Issue number12
StatePublished - Jan 1 1995

Fingerprint

Europium
europium
Nitrates
clays
nitrates
phosphates
Clay
Phosphates
Nuclear magnetic resonance
nuclear magnetic resonance
tributyl phosphate
clay
hectorite
Chemical shift
chemical equilibrium
Display devices
Actinoid Series Elements
Lanthanoid Series Elements
Actinides

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

Sequestration of the tributyl phosphate complex of europium nitrate in the clay hectorite. A 31P NMR study. / Hartzell, Cynthia J; Yang, S. W.; Parnell, Roderic A; Morris, D. E.

In: Journal of Physical Chemistry, Vol. 99, No. 12, 01.01.1995, p. 4205-4210.

Research output: Contribution to journalArticle

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