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Title: Surveying Phase Modifier Functional Groups for Applications to Ln(III) Separations

Journal Article · · ACS Omega
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Colorado School of Mines, Golden, CO (United States)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States)
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The application of N,N,N',N'-tetraoctyl diglycolamide (TODGA) in solvent extraction systems for lanthanide (Ln) separations is well understood. In these systems, the formation of a third phase has motivated the use of phase modifiers to enable higher concentrations of H+ and Ln common to industrial processes. Several different phase modifiers with applications to diglycolamide (DGA) systems have previously been reported, with a focus on tri-n-butyl phosphate (TBP), N,N'-dihexylactanamide (DHOA), N,N-dioctyl-2-hydroxyacetamide (DOHyA), N,N'-dimethyl-N,N'-dioctylhexylethoxy malonamide (DMDOHEMA), and octanol. While the primary utility of phase modifiers is the increased metal loading, they can have significant effects on the metal distribution ratios, which are well described by the energetics of the extraction process itself. However, the mechanisms by which phase modifiers impact distribution ratios are not generally understood. This work considers the ability of phase modifiers to affect Ln distribution ratios by using phase modifiers with two different functional groups (–Cl and –C≡N) and an octyl alkyl chain in a TODGA and n-dodecane system. Determining the effect of chlorooctane and octane nitrile is important for understanding how phase modifier functional groups and their hydrogen bonding interactions affect Ln extraction. Through combining distribution ratio measurements with organic phase spectroscopic investigations, the impact of chlorooctane and octane nitrile on Ln extraction and their inner-sphere complexes is reported. The addition of either chlorooctane or octane nitrile to TODGA in n-dodecane decreases Ln extraction while maintaining the same inner-sphere Ln complex. The lack of change in inner-sphere Ln-TODGA coordination upon incorporation of phase modifiers and the significant impact of these phase modifiers on distribution ratios suggest the importance of a supramolecular structure. Understanding the role of chlorooctane and octane nitrile on the organic phase structure at longer length scales has been identified as an avenue for future investigations.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS); USDOE Office of Science (SC), Office of Workforce Development for Teachers & Scientists (WDTS)
Grant/Contract Number:
AC02-06CH11357; SC0014664; SC0022217
OSTI ID:
2476558
Journal Information:
ACS Omega, Journal Name: ACS Omega Journal Issue: 46 Vol. 9; ISSN 2470-1343
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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