Citation: FU Su-Zhen, CHEN Qing-De, SHEN Xing-Hai. Aggregation Behavior of 1-Alkyl-3-methylimidazolium Tetrafluoroborate Ionic Liquids in Aqueous Solutions[J]. Acta Physico-Chimica Sinica, ;2011, 27(08): 1913-1918. doi: 10.3866/PKU.WHXB20110713 shu

Aggregation Behavior of 1-Alkyl-3-methylimidazolium Tetrafluoroborate Ionic Liquids in Aqueous Solutions

1.
Beijing National Laboratory for Molecular Sciences, Radiochemistry and Radiation Chemistry Key Laboratory of Fundamental Science, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China

Received Date: 12 April 2011
Available Online: 20 May 2011
Fund Project: 国家自然科学基金(20871009) (20871009)

The aggregation behavior of 1-alkyl-3-methylimidazolium tetrafluoroborate ([Cnmim][BF₄]) ionic liquids in aqueous solutions was investigated by isothermal titration calorimetry (ITC), fluorescence quenching, and conductivity methods. The critical micelle concentration (cmc), the changes of the enthalpy (ΔH_mic), the Gibbs free energy (ΔG_mic), and the entropy (ΔS_mic) for the micelle formation and the mean aggregation number of the micelles at different concentrations were obtained. We found that entropy was the principle driving force leading to the micellization of these types of ionic liquids. The increase in alkyl chain length led to a decrease in ΔG_mic, favoring the formation of micelles. Furthermore, by combining with the aqueous solution data for [C_nmim]X (X=Cl^-, Br^-), the effect of anions on the aggregation behavior of the ionic liquids was investigated. The increase in the hydrophobicity and the volume of the anions favored the formation of micelles when the ionic liquids contained identical cations. This is believed to result from the decrease in electrostatic repulsion between the head groups in the micelles because of the relatively strong binding between the anions and the cations. With respect to [C₁₂mim][BF₄], the addition of β-cyclodextrin (β-CD) caused an increase in its cmc and a decrease in ΔH_mic and ΔS_mic; while the presence of KBF₄ caused a decrease in cmc and ΔH_mic, and an increase in ΔS_mic.
- Ionic liquids,
- 1-Alkyl-3-methylimidazolium tetrafluoroborate,
- Isothermal titration calorimetry,
- Fluorescence,
- Conductivity
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