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Toward Mechanistic Understanding of Nuclear Reprocessing Chemistries by Quantifying Lanthanide Solvent Extraction Kinetics via Microfluidics with Constant Interfacial Area and Rapid Mixing

Nichols, Kevin P. and Pompano, Rebecca R. and Li, Liang and Gelis, Artem V. and Ismagilov, Rustem F. (2011) Toward Mechanistic Understanding of Nuclear Reprocessing Chemistries by Quantifying Lanthanide Solvent Extraction Kinetics via Microfluidics with Constant Interfacial Area and Rapid Mixing. Journal of the American Chemical Society, 133 (39). pp. 15721-9. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20130821-160728693

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Abstract

The closing of the nuclear fuel cycle is an unsolved problem of great importance. Separating radionuclides produced in a nuclear reactor is useful both for the storage of nuclear waste and for recycling of nuclear fuel. These separations can be performed by designing appropriate chelation chemistries and liquid-liquid extraction schemes, such as in the TALSPEAK process (Trivalent Actinide-Lanthanide Separation by Phosphorus reagent Extraction from Aqueous Komplexes). However, there are no approved methods for the industrial scale reprocessing of civilian nuclear fuel in the United States. One bottleneck in the design of next-generation solvent extraction-based nuclear fuel reprocessing schemes is a lack of interfacial mass transfer rate constants obtained under well-controlled conditions for lanthanide and actinide ligand complexes; such rate constants are a prerequisite for mechanistic understanding of the extraction chemistries involved and are of great assistance in the design of new chemistries. In addition, rate constants obtained under conditions of known interfacial area have immediate, practical utility in models required for the scaling-up of laboratory-scale demonstrations to industrial-scale solutions. Existing experimental techniques for determining these rate constants suffer from two key drawbacks: either slow mixing or unknown interfacial area. The volume of waste produced by traditional methods is an additional, practical concern in experiments involving radioactive elements, both from disposal cost and experimenter safety standpoints. In this paper, we test a plug-based microfluidic system that uses flowing plugs (droplets) in microfluidic channels to determine absolute interfacial mass transfer rate constants under conditions of both rapid mixing and controlled interfacial area. We utilize this system to determine, for the first time, the rate constants for interfacial transfer of all lanthanides, minus promethium, plus yttrium, under TALSPEAK process conditions, as a first step toward testing the molecular mechanism of this separation process.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja206020uDOIArticle
http://pubs.acs.org/doi/full/10.1021/ja206020uPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja206020uPublisherSupporting Information
ORCID:
AuthorORCID
Ismagilov, Rustem F.0000-0002-3680-4399
Additional Information: Copyright © 2011 American Chemical Society. Published In Issue: October 05, 2011. Article ASAP: September 02, 2011. Received: June 28, 2011. This work was supported by the U.S. Department of Energy, Office of Nuclear Energy, Fuel Cycle Research and Development Project under Contract DE-AC02-06CH11357. We thank Heidi Park for contributions to writing and editing this manuscript.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-06CH11357
Issue or Number:39
Record Number:CaltechAUTHORS:20130821-160728693
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20130821-160728693
Official Citation:Toward Mechanistic Understanding of Nuclear Reprocessing Chemistries by Quantifying Lanthanide Solvent Extraction Kinetics via Microfluidics with Constant Interfacial Area and Rapid Mixing Kevin P. Nichols, Rebecca R. Pompano, Liang Li, Artem V. Gelis, and Rustem F. Ismagilov Journal of the American Chemical Society 2011 133 (39), 15721-15729
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:40852
Collection:CaltechAUTHORS
Deposited By: Whitney Barlow
Deposited On:23 Aug 2013 20:25
Last Modified:03 Oct 2019 05:43

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