Electrochemical Study on Aluminum Speciation in Lewis Acidic Chloroaluminate-Bis(trifluoromethylsulfonyl)amide Mixed Ionic Liquids

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Aluminum species forming in Lewis acidic chloroaluminate and bis(trifluoromethylsulfonyl)amide (TFSA⁻) mixed ionic liquids having 1-butyl-3-methylimidazolium (BMI⁺) was investigated by potentiometry and Raman spectroscopy. A decrease in the concentration of [Al₂Cl₇]⁻ and an increase in that of [AlCl₄]⁻ with addition of BMITFSA into acidic BMICl-AlCl₃ were observed by Raman spectroscopy. The redox potential of Al(III)/Al in BMICl-AlCl₃ (1:2 in molar ratio) was found to be −0.68 V vs. an Ag|Ag(I) reference electrode, which was corresponding to −0.25 V vs. the ferrocene/ferrocenium couple at 25°C. The potentiometry of an Al electrode in the mixed ionic liquids with different compositions using the Ag|Ag(I) reference electrode suggested formation of a mixed ligand aluminum complex, Al(TFSA)Cl₂, indicating the instability of [Al₂Cl₇]⁻ against TFSA⁻.