Acetonitrile Boosts Conductivity of Imidazolium Ionic Liquids

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• 作者：Vitaly V. Chaban ; Iuliia V. Voroshylova ; Oleg N. Kalugin ; Oleg V. Prezhdo
• 刊名：The Journal of Physical Chemistry B
• 出版年：2012
• 出版时间：July 5, 2012
• 年：2012
• 卷：116
• 期：26
• 页码：7719-7727
• 全文大小：557K
• 年卷期：v.116,no.26(July 5, 2012)
• ISSN：1520-5207

文摘

We apply a new methodology in the force field generation (Phys. Chem. Chem. Phys.2011, 13, 7910) to study binary mixtures of five imidazolium-based room-temperature ionic liquids (RTILs) with acetonitrile (ACN). Each RTIL is composed of tetrafluoroborate (BF₄) anion and dialkylimidazolium (MMIM) cations. The first alkyl group of MIM is methyl, and the other group is ethyl (EMIM), butyl (BMIM), hexyl (HMIM), octyl (OMIM), and decyl (DMIM). Upon addition of ACN, the ionic conductivity of RTILs increases by more than 50 times. It significantly exceeds an impact of most known solvents. Unexpectedly, long-tailed imidazolium cations demonstrate the sharpest conductivity boost. This finding motivates us to revisit an application of RTIL/ACN binary systems as advanced electrolyte solutions. The conductivity correlates with a composition of ion aggregates simplifying its predictability. Addition of ACN exponentially increases diffusion and decreases viscosity of the RTIL/ACN mixtures. Large amounts of ACN stabilize ion pairs, although they ruin greater ion aggregates.