Zhen Liu, S. Z. el Abedin, F. Endres
Apr 7, 2015
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Chemphyschem : a European journal of chemical physics and physical chemistry
Abstract
In this paper we report on the interactions of the ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate ([EMIm]TfO) with water and the solvation of zinc ions in neat [EMIm]TfO and [EMIm]TfO-water mixtures investigated by FTIR and Raman spectroscopy. The structures and physicochemical properties of the [EMIm]TfO-water mixtures are strongly dependent on the interaction between cations, anions, and water. The structure was changed from ionic-liquid-like to water-like solutions upon addition of water. In addition, zinc salts can precipitate in 0.2 M Zn(TfO)2/[EMIm]TfO upon addition of 10 % (v/v) water, presumably as a result of polarity change of the solution. The average coordination number of TfO(-) per zinc ion calculated from Raman spectra is 3.8 in neat [EMIm]TfO, indicating that [Zn(TfO)4](2-), and [Zn(TfO)3](-) complexes are present in the solution. However, in the presence of water, water interacts preferentially with the zinc ions, leading to aqueous zinc species. The solvation of zinc ions in 1-butyl-1-methylpyrrolidinium trifluoromethylsulfonate ([Py(1,4)]TfO) was also investigated. In [Py(1,4)]TfO, there are, on average, 4.5 TfO(-) anions coordinating each zinc ion, corresponding to the weak interaction between [Py(1,4)](+) cations and TfO(-) anions. The species present in [Py(1,4)]TfO are likely a mixture of [Zn(TfO)4](2-) and [Zn(TfO)5](3-).