title: Thermal effect on C-H stretching vibrations of the imidazolium ring in ionic liquids.
abstract: We have studied temperature dependent IR spectra of the C-H stretching modes of the imidazolium ring in [bmim][PF(6)], [bmim][Tf(2)N], [emim][Tf(2)N], [hmim][Tf(2)N], and [bmim][BF(4)]. Temperatures in this study are from 278 to 348 K at an interval of 10 K. Spectra of the C-H stretching modes have been deconvoluted using our previous computer program of the Voigt-lineshape function. Frequency shifts, Lorentzian spectral widths, and band absorbance were examined as a function of temperature. In order to interpret the observed behaviors, we have developed a simple mechanical model as well as a chemical equilibrium model. The model analyses suggest that enthalpy changes for the cluster and/or ion-pair breaking reactions in the liquid state are several kJ mol(-1) endothermic, and the degree of dissociations of ion pairs or hydrogen bonded clusters is in the range from 0.3 to 0.9 with different magnitudes for the five ionic liquids.
authors.affiliation: DuPont Fluoroproducts Laboratory, Chestnut Run Plaza 711, Wilmington, DE 19880, USA. akimichi.yokozeki@usa.dupont.com
authors.forename: A
authors.initials: A
authors.lastname: Yokozeki
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Kasprzak
authors.forename: Mark B
authors.initials: MB
authors.lastname: Shiflett