Determination of Chlorides in Ionic Liquids by Wavelength Dispersive X-ray Fluorescence Spectrometry

The synthesis of ionic liquids (ILs) usually involves two steps: (i) quaternization of a precursor followed by (ii) a salt metathesis reaction to introduce the desired anion. A consequence of the second step is that most ILs still contain some amount of the initial anion, often chloride. In this work, wavelength dispersive X-ray fluorescence (WDXRF) spectrometry is presented for the direct measurement of chlorides in ILs. The WDXRF settings were optimized, and the system was calibrated for the detection of chloride in several analogues of the commercially available IL Aliquat 336, [A336][X] (with X = I-, Br-, NO3-, or SCN-). The Cl K alpha intensity showed excellent linearity for samples with a conversion >0.80 (approximately Cl < 8000 ppm). Synthetic quality control samples showed that the instrumental error and deviations induced by the calibration procedure were small with maximum values of 1 and 5%, respectively. Detection and quantification limits depended strongly on the matrix (i.e., anion system and dilution) but were relatively low: 42-191 and 127-578 ppm Cl, respectively. Compared with other analytical techniques used for this purpose, the strengths of WDXRF include its ease of use, rapid measurements, the near absence of sample preparation steps, and versatility in terms of anion systems and chloride concentration range.