ABSTRACT
The determination and quantification of halide impurities in ionic liquids is highly important because halide ions can significantly influence the chemical and physical properties of ionic liquids. The use of impure ionic liquids in fundamental studies on solvent extraction or catalytic reactions can lead to incorrect experimental data. The detection of halide ions in solution by total reflection X-ray fluorescence (TXRF) has been problematic because volatile hydrogen halide (HX) compounds are formed when the sample is mixed with the acidic metal standard solution. The loss of HX during the drying step of the sample preparation procedure gives imprecise and inaccurate results. A new method based on an alkaline copper standard Cu(NH3)4(NO3)2 is presented for the determination of chloride, bromide, and iodide impurities in ionic liquids. The 1-butyl-3-methylimidazolium ([C4mim]) ionic liquids with the anions acetate ([C4mim][OAc]), nitrate ([C4mim][NO3]), trifluoromethanesulfonate ([C4mim][OTf]), and bis(trifluoromethylsulfonyl)imide ([C4mim][Tf2N]) were synthesized via a halide-free route and contaminated on purpose with known amounts of [C4mim]Cl, [C4mim]Br, [C4mim]I, or potassium halide salts in order to validate the new method and standard.
ABSTRACT
An accurate quantitative determination of halide ions X (X = Cl, Br, I) in aqueous solution by total reflection X-ray fluorescence (TXRF) is not possible using the traditional acidic internal standards. In general, the standard solutions are highly acidic (e.g., Ga(NO3)3 in HNO3) to avoid precipitation of hydroxides of the standard element and to obtain a stable and reliable standard. In acidic solutions, dissolved halide salts can exchange their cation for a proton. The resulting volatile HX compounds can evaporate during the drying procedure of the TXRF sample preparation. In this technical note, we show that an alkaline Cu(NH3)4(NO3)2 standard can be used for the determination of chlorine, bromine and iodine without facing problems of HX evaporation.
