Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids

• 来源期刊: 科学通报(英文版)
• 学科: 化学
• 年，卷（期）: 2012,（21）
• 页码范围: 2752-2758
• 页数: 7页
• 分类号: O626.23
• 语种: 中文

摘要

The reactions of imidazolium-based ionic liquids having different substituent groups on the ring with hydrated electrons (eaq-),hydroxyl radicals (·OH),and sulfate anion radicals (SO4·-) were investigated using nanosecond pulse radiolysis techniques.The spectra of these ionic liquids on reaction with eaq-all exhibited a similar peak at about 320 nm,and a typical peak for eaq-in aqueous ionic liquid solutions.The reaction rate constants for 1,3-disubstituted imidazolium-based ionic liquid hexafluorophosphates (BMIPF 6) with eaq-were deduced to be 10 10 L mol-1s-1,however the values were lower for trisubstituted ionic liquids.For example,the rate constant for 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMIBF 4) was 5.5*10 9 L mol-1s-1.Imidazolium-based ionic liquids reacted with hydroxyl radicals via adducts to produce a mixture of isomeric OH adducts,and the pk a value of the OH adducts was deduced to be 8.4±0.4 for 1-butyl-3-methylimdazolium tetrafluoroborate (BMIBF 4).Moreover,imidazolium cations were also oxidized by SO4·-to produce bivalent cation radicals,which exhibit a peak at 320 nm,and these rate constants are of the same order of magnitude,i.e.,10 9 L mol-1s-1,except that for 1-(2-hydroxyethyl)-3-methylimdazolium tetrafluoroborate with SO4·-(k=2.8*10 8 L mol-1 s-1).Theoretical calculations were carried out to estimate the structures of the products of reduction by eaq- and the results were related to the experimental data.