Do anions influence the polarity of protic ionic liquids?
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Shashi Kant Shukla, Nageshwar D. Khupse, Anil Kumar
Polarity studies in two classes of imidazolium-based protic ionic liquids (PILs) possessing [HSO4]−, [HCOO]−, [CH3COO]− and [CH3CH2COO]− anions were carried out using a solvatochromic method from 298.15 to 353.15 K. For 1-methylimidazolium class of PILs, ET(30) was found to be independent over the entire range of temperature, while ET(30) was noted to decrease with a rise in temperature in the case of 1-butylimidazolium class of PILs containing [CH3COO]− and [CH3CH2COO]− anions. The ET(30) value decreases in both the classes upon varying the anions ([HSO4]−, [HCOO]−, [CH3COO]− and [CH3CH2COO]−). The ET(30) value is controlled by hydrogen bond acceptor basicity, β, and dipolarity/polarizability, π*. The ET(30) value for PILs varies inversely to the strength of the coulombic interaction between ions in PILs. Strong interactions between ions lead to lower ET(30) values. Unlike the poor thermal effect on ET(30), the Kamlet–Taft parameters i.e. α, β and π* have pronounced thermal effect in the imidazolium-based PILs. Variation in the Kamlet–Taft parameters is controlled by the stabilization of ions and the degree of proton transfer from Brønsted acid to Brønsted base.
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