Stoichiometry of An(iii)-DMDOHEMA complexes formed during solvent extraction.
Dalton Trans
; 47(32): 10906-10914, 2018 Aug 14.
Article
in En
| MEDLINE
| ID: mdl-30043815
ABSTRACT
N,N'-Dimethyl,N,N'-dioctylhexylethoxymalonamide (DMDOHEMA) is used to separate An(iii) and Ln(iii) from fission products in several liquid-liquid extraction processes that aim at recycling actinides. The stoichiometry of the extracted complexes is important for a complete understanding of the processes. The presented work focuses on the complexation of Cm(iii) with DMDOHEMA studied by TRLFS in mono- and biphasic (solvent extraction) systems. The formation of [Cm(DMDOHEMA)n]3+ (n = 1-3) in 1-octanol containing 1.7 mol L-1 of water with log ß'1 = 2.6 ± 0.3, log ß'2 = 4.0 ± 0.5, log ß'3 = 4.3 ± 0.5 was confirmed. In addition, fluorescence lifetime measurements indicated the formation of a 1 4 complex. Furthermore, solvent extraction experiments were performed, varying the proton and nitrate concentrations. TRLFS measurements of organic phases confirmed the existence of two species, [Cm(DMDOHEMA)3(NO3)(H2O)1-2]2+ (dominant at high proton and nitrate concentrations) and [Cm(DMDOHEMA)4(H2O)]3+ (dominant at low proton and nitrate concentrations). To support the proposed stoichiometries, vibronic side-band spectroscopy (VSBS) was employed, allowing the observation of vibrations of functional groups coordinated to the probed metal ion. Clear differences between the vibronic side bands of the 1 3 and 1 4 complex in the range of 900-1300 cm-1 were observed. Vibrational spectra calculated by DFT complimented the experimental data and confirmed the proposed stoichiometries. They revealed a monodentate coordination mode of the nitrate and two water molecules in the 1 3 complex.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Dalton Trans
Journal subject:
QUIMICA
Year:
2018
Document type:
Article
Affiliation country:
Germany