The effect of C2 substitution on melting point and liquid phase dynamics of imidazolium based-ionic liquids: insights from molecular dynamics simulations

Journal Article · Sun Jan 01 04:00:00 EST 2012 · Physical Chemistry Chemical Physics. PCCP (Print)

DOI:https://doi.org/10.1039/c2cp41964e· OSTI ID:1211238

Zhang, Y; Maginn, EJ

Using molecular dynamics simulations, the melting points and liquid phase dynamic properties were studied for four alkyl-imidazolium-based ionic liquids, 1-n-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), 1-n-butyl-2,3-dimethylimidazolium hexafluorophosphate ([BMMIM][PF6]), 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM][PF6]), and 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate ([EMMIM][PF6]), respectively. Experimentally it has been observed that the substitution of a methyl group for a hydrogen at the C2 position of the cation ring leads to an increase in both the melting point and liquid phase viscosity, contrary to arguments that had been made regarding associations between the ions. The melting points of the four ionic liquids were accurately predicted using simulations, as were the trends in viscosity. The simulation results show that the origin of the effect is mainly entropic, although enthalpy also plays an important role.

• Sponsoring Organization: USDOE Advanced Research Projects Agency - Energy (ARPA-E)
• DOE Contract Number: AR0000094
• OSTI ID: 1211238
• Journal Information: Physical Chemistry Chemical Physics. PCCP (Print), Journal Name: Physical Chemistry Chemical Physics. PCCP (Print) Journal Issue: 35 Vol. 14; ISSN 1463-9076
• Country of Publication: United States
• Language: English