Influence of Aqueous Phase Acidity on Ln(III) Coordination by N,N,N',N'-Tetraoctyldiglycolamide
Here, this study highlights the importance of combining distribution ratio measurements with multiple spectroscopic techniques to provide a more comprehensive understanding of organic phase Ln coordination chemistry. Solvent extraction investigations with N,N,N',N'-tetraoctyldiglycolamide (TODGA) in n-heptane reveal the sensitivity of Ln complexation to the HNO3 concentration. Distribution ratio measurements in tandem with UV–Vis demonstrated that increasing the concentration of HNO3 above 0.5 M with a constant NO3– of 1 M increases the number of coordinating TODGA molecules, from a 1:2 to a 1:3 Ln:TODGA complex. At each concentration of HNO3 considered herein (from 0.01 to 1 M), Eu lifetime analysis demonstrated no evidence of H2O coordination. Results from Fourier transform infrared investigations suggest the presence of inner-sphere NO3– under low concentrations of HNO3 when the 1:2 Ln:TODGA complex is present. Increasing the HNO3 concentration above 0.5 M increases the propensity for outer-sphere interactions by removing the coordinated NO3– and saturating the Ln coordination sphere with three TODGA molecules, resulting in the well-established cationic, trischelate homoleptic [Ln(TODGA)3]3+ complex. This work demonstrates the importance in considering the NO3– source for solvent extraction systems. In particular, for systems with an affinity for outer-sphere interactions with molar concentrations of HNO3, changing the NO3– source can change the inner-sphere coordination of the Ln complex, which, in turn, affects the separation efficacy.
- Research Organization:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS)
- Grant/Contract Number:
- AC02-06CH11357; SC0014664; SC0022217
- OSTI ID:
- 2505052
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 23 Vol. 63; ISSN 0020-1669
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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