Effect of Water on Structure of Hydrophilic Imidazolium-Based Ionic Liquid

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Abstract

The state of water in room-temperature ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI(+)BF(4)(-)), has been investigated by measurements of absorption and desorption isotherms, attenuated total reflectance infrared (ATR-IR) spectroscopy, and (2)H NMR relaxation method. The absorption enthalpies of water for the ionic liquid were estimated from the absorption isotherms. The enthalpies in the water mole fraction range of x(w) approximately 0.3. In addition, the activation energies for the rotational motion of a water molecule estimated from the (2)H NMR relaxation rates have indicated that the motion of water molecules in EMI(+)BF(4)(-)-D(2)O solutions gradually becomes freer with increasing water content from x(w) = 0.10 to 0.30, but is retarded again at x(w) = 0.33. Therefore, all the present findings have suggested that the state of water molecules in EMI(+)BF(4)(-) significantly changes at x(w) approximately 0.3. On the other hand, to directly observe the effect of water on structure of EMI(+)BF(4)(-), LAXS experiments have been made on EMI(+)BF(4)(-)-water solutions. It has been suggested that the interactions between the C(2) atom within the imidazolium ring of EMI(+) and BF(4)(-) are strengthened with increasing water content, while those at the C(4) and C(5) atoms weaken. Thus, the present LAXS experiments have clarified the beginning of formation of ion pair in EMI(+)BF(4)(-) by adding water at the molecular level.

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