Complexation Enhancement Drives Water-to-Oil Ion Transport: A Simulation Study

Journal Article · Wed Nov 23 00:00:00 EST 2016 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201604470· OSTI ID:1373589

Qiao, Baofu  ^[1]; Ferru, Geoffroy ^[1]; Ellis, Ross J. ^[2]

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1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne Illinois 60439 USA
2. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne Illinois 60439 USA; Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge Tennessee 37831 USA

We address the structures and energetics of ion solvation in aqueous and organic solutions to understand liquid-liquid ion transport. Atomistic molecular dynamics (MD) simulations with polarizable force field are performed to study the coordination transformations driving lanthanide (Ln(III)) and nitrate ion transport between aqueous and an alkylamide-oil solution. An enhancement of the coordination behavior in the organic phase is achieved in contrast with the aqueous solution. In particular, the coordination number of Ce3+ increases from 8.9 in the aqueous to 9.9 in the organic solutions (from 8 in the aqueous to 8.8 in the organic systems for Yb3+). Moreover, the local coordination environ ment changes dramatically. Potential of mean force calculations show that the Ln(III)-ligand coordination interaction strengths follow the order of Ln(III-)nitrate> Ln(III)-water>Ln(III)-DMDBTDMA. They increase 2-fold in the lipophilic environment in comparison to the aqueous phase, and we attribute this to the shedding of the outer solvation shell. Our findings highlight the importance of outer sphere interactions on the competitive solvation energetics that cause ions to migrate between immiscible phases; an essential ingredient for advancing important applications such as rare earth metal separations. Some open questions in simulating the coordination behavior of heavy metals are also addressed.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL (United States)
• Sponsoring Organization: USDOE Office of Science - Office of Basic Energy Sciences - Chemical Sciences, Geosciences, and Biosciences Division
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 1373589
• Journal Information: Chemistry - A European Journal, Vol. 23, Issue 2; ISSN 0947-6539
• Publisher: ChemPubSoc Europe
• Country of Publication: United States
• Language: English