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Radiation-induced fragmentation of diamide extraction agents in ionic liquid diluents



Radiation-induced fragmentation of diamide extraction agents in ionic liquid diluents



Journal of Physical Chemistry. B 116(7): 2234-2243



N,N,N',N'-Tetraalkyldiglycolamides are extracting agents that are used for liquid-liquid extraction of trivalent metal ions in wet processing of spent nuclear fuel. This application places such agents in contact with the decaying radionuclides, causing radiolysis of the agent in the organic diluent. Recent research seeks to replace common molecular diluents (such as n-dodecane) with hydrophobic room-temperature ionic liquids (ILs), which have superior solvation properties. In alkane diluents, rapid radiolytic deterioration of diglycolamide agents can be inhibited by addition of an aromatic cosolvent that scavenges highly reactive alkane radical cations before these oxidize the extracting agent. Do aromatic ILs exhibit a similar radioprotective effect? To answer this question, we used electron paramagnetic resonance spectroscopy to study the fragmentation pathways in radiolysis of neat diglycolamides, their model compounds, and their solutions in the ILs. Our study indicates that aromatic ILs do not protect these types of solutes from extensive radiolytic damage. Previous research indicated a similar lack of protection for crown ethers, whereas the ILs readily protected di- and trialkyl phosphates (another large class of metal-extracting agents). Our analysis of these unanticipated failures suggests that new types of organic anions are required in order to formulate ILs capable of radioprotection for these classes of solutes. This study is a cautionary tale of the fallacy of analogical thinking when applied to an entirely new and insufficiently understood class of chemical materials.

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Accession: 055345176

Download citation: RISBibTeXText

PMID: 22296406

DOI: 10.1021/jp2117483


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