Finney, A., Lectez, S., Freeman, C. et al. (2 more authors) (2019) Ion association in lanthanide chloride solutions. Chemistry – A European Journal, 25 (37). pp. 8725-8740. ISSN 0947-6539
Abstract
A better understanding of the solution chemistry of the lanthanide (Ln) salts in water would have wide ranging implications in materials processing, waste management, element tracing, medicine and minerals processing ‐ particularly given governmental concerns about Ln security of supply. Despite much effort, even in simple systems, the mechanisms and thermodynamics of Ln(III) association with small anions remain unclear. In the present study, molecular dynamics (MD), using a newly developed force field, provide new insights into LnCl₃(aq) solutions. (Adaptive) bias MD simulations show that the mechanisms for ion pairing change from dissociative to associative exchange depending upon cation size. Thermodynamics of association reveal that while ion pairing is favorable, the equilibrium distribution of species at low concentration is dominated by weakly bound solvent shared and solvent separated ion pairs cf. contact ion pairs, reconciling a number of contrasting observations of Ln(III)‐‐Cl association in the literature. In addition, we show that the thermodynamic stabilities of a range of inner sphere and outer sphere LnClχ coordination complexes are comparable and that the kinetics of anion binding to cations may control solution speciation distributions beyond ion pairs. The techniques adopted in this work provide a framework with which to investigate more complex solution chemistries of cations in water.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
Keywords: | Lanthanides; Rare Earth Elements; Ion Pairing; Molecular dynamics; Potential of Mean Force |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Engineering (Sheffield) > Department of Materials Science and Engineering (Sheffield) |
Funding Information: | Funder Grant number NATURAL ENVIRONMENT RESEARCH COUNCIL NE/M011232/1 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 03 May 2019 11:42 |
Last Modified: | 14 Nov 2019 15:13 |
Status: | Published |
Publisher: | Wiley |
Refereed: | Yes |
Identification Number: | 10.1002/chem.201900945 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:145658 |
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