title: Radiation induced redox reactions and fragmentation of constituent ions in ionic liquids. 2. Imidazolium cations.
abstract: In part 1 of this study, radiolytic degradation of constituent anions in ionic liquids (ILs) was examined. The present study continues the themes addressed in part 1 and examines the radiation chemistry of 1,3-dialkyl substituted imidazolium cations, which currently comprise the most practically important and versatile class of ionic liquid cations. For comparison, we also examined 1,3-dimethoxy- and 2-methyl-substituted imidazolium and 1-butyl-4-methylpyridinium cations. In addition to identification of radicals using electron paramagnetic resonance spectroscopy (EPR) and selective deuterium substitution, we analyzed stable radiolytic products using (1)H and (13)C nuclear magnetic resonance (NMR) and tandem electrospray ionization mass spectrometry (ESMS). Our EPR studies reveal rich chemistry initiated through "ionization of the ions": oxidation and the formation of radical dications in the aliphatic arms of the parent cations (leading to deprotonation and the formation of alkyl radicals in these arms) and reduction of the parent cation, yielding 2-imidazolyl radicals. The subsequent reactions of these radicals depend on the nature of the IL. If the cation is 2-substituted, the resulting 2-imidazolyl radical is relatively stable. If there is no substitution at C(2), the radical then either is protonated or reacts with the parent cation forming a C(2)-C(2) σσ*-bound dimer radical cation. In addition to these reactions, when methoxy or C(α)-substituted alkyl groups occupy the N(1,3) positions, their elimination is observed. The elimination of methyl groups from N(1,3) was not observed. Product analyses of imidazolium liquids irradiated in the very-high-dose regime (6.7 MGy) reveal several detrimental processes, including volatilization, acidification, and oligomerization. The latter yields a polymer with m/z of 650 ± 300 whose radiolytic yield increases with dose (~0.23 monomer units per 100 eV for 1-methyl-3-butylimidazolium trifluorosulfonate). Gradual generation of this polymer accounts for the steady increase in the viscosity of the ILs upon irradiation. Previous studies at lower dose have missed this species due to its wide mass distribution (stretching out to m/z 1600) and broad NMR lines, which make it harder to detect at lower concentrations. Among other observed changes is the formation of water immiscible fractions in hydrophilic ILs and water miscible fractions in hydrophobic ILs. The latter is due to anion fragmentation. The import of these observations for use of ILs as extraction solvents in nuclear cycle separations is discussed.
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S. Cass Ave, Argonne, Illinois 60439, USA. shkrob@anl.gov
authors.forename: Ilya A
authors.initials: IA
authors.lastname: Shkrob
authors.forename: Timothy W
authors.initials: TW
authors.lastname: Marin
authors.forename: Sergey D
authors.initials: SD
authors.lastname: Chemerisov
authors.forename: Jasmine L
authors.initials: JL
authors.lastname: Hatcher
authors.forename: James F
authors.initials: JF
authors.lastname: Wishart