Influence of gamma irradiation on hydrophobic room-temperature ionic liquids [BuMeIm]PF6 and [BuMeIm](CF3SO2)2N

Abstract

Stability of neat hydrophobic Room-Temperature Ionic Liquids (RTIL) [BuMeIm]X, where [BuMeIm]⁺ is 1-butyl-3-methylimidazolium and X⁻ is PF₆⁻, and (CF₃SO₂)₂N⁻, was studied under gamma radiolysis (¹³⁷Cs) in an argon atmosphere and in air. It was found that the density, surface tension, and refraction index of RTILs are unchanged even by an absorbed dose of approximately 600 kGy. Studied RTILs exhibit considerable darkening when subjected to gamma irradiation. The light absorbance of ionic liquids increases linearly with the irradiation dose. Water has no influence on radiolytic darkening. A comparative study of [BuMeIm]X and [Bu₄N][Tf₂N] leads to the conclusion that the formation of colored products is related to gamma radiolysis of the [BuMeIm]⁺ cation. The radiolytic darkening kinetics of RTILs is influenced by the anions as follows: Cl⁻ < (CF₃SO₂)₂N⁻ < PF₆⁻. Electrospray ionization mass spectrometry and NMR analysis reveal the presence of nonvolatile radiolysis products at concentrations below 1 mol% for an absorbed dose exceeding 1200 kGy. Initial step of BuMeIm⁺ cation radiolysis is the loss of the Bu˙ group, the H˙ atom from the 2 position on the imidazolium ring, and the H˙ atom from the butyl chain. Radiolysis of ionic liquid anions yields F˙ and CF₃˙ from PF₆⁻ and [Tf₂N]⁻, respectively. Recombinations of these primary products of radiolysis lead to various polymeric and acidic species.