Physics – Chemical Physics
Scientific paper
2007-03-02
Physics
Chemical Physics
24 pages + 9 figures + supplement; submitted to J Am Chem Soc
Scientific paper
The radiation- and photo- chemistry of room temperature ionic liquids (ILs) composed of ammonium, phosphonium, pyrrolidinium, and imidazolium cations and bis(triflyl)amide, dicyanamide, and bis(oxalato)borate anions, have been studied using low-temperature Electron Paramagnetic Resonance (EPR). Several classes of radicals have been identified and related to reactions of the primary radiolytically generated electrons and holes. Large yields of terminal and penultimate C-centered radicals are observed in the aliphatic chains of the phosphonium, ammonium and pyrrolidinium cations, but not for imidazolium cation. This pattern can be accounted for by efficient deprotonation of a hole trapped on the cation (the radical dication) that competes with rapid charge transfer to a nearby anion. The latter leads to the formation of stable N- or O-centered radicals. The electrons either react with the protic impurity (for nonaromatic cations) yielding H atoms or the aromatic moiety (for imidazolium cations). Excitation of bis(triflyl)amide anion is shown to yield trifluoromethyl radical; the yield of this radical in radiolysis, though, is low (< 10% of the alkyl radical yield). In terms of their radiation chemistry, neat ILs appear to be intermediate between organic liquids and ionic solids. Addition of 10-40 wt% of trialkylphoshate (a common extraction agent for nuclear cycle separations) has relatively little effect on the fragmentation of the ILs. Radiation induced dealkylation of the phosphate is prominent, but the yield of the alkyl radical fragments derived from the phosphates is < 4% of the yield of the radical fragments drived from the solvent. We discuss the implication of these results for the radiation stability of nuclear cycle extraction systems based upon the IL diluents.
Chemerisov Sergey D.
Shkrob Ilya A.
Wishart James F.
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