Effects of anion and alkyl chain length of cation on the thermophysical properties of imidazolium-based ionic liquid

Abstract

Abstract This study focused on the effects of anions and the alkyl chain length of cations on the thermophysical properties of imidazolium-based ionic liquid (ILs). The data were obtained from references and the NIST database. The studied parameters include the melting temperature (Tm), glass transition temperature (Tg), decomposition temperature (Td), enthalpy of fusion (ΔHm), and thermal conductivity ( λ ). The variations of Tm with the anions in [C16MIM][A] where A = Br, Cl, BF4, PF6, and TFO, generally decreased with increasing anion radius, except for A = PF6, due to strong hydrogen bonds for the sake of an F atom. The values of the critical temperatures (Tm, Tg, and Td) generally show a strong variation with the number of carbon atom or alkyl chain length (the number of n in [CnMIM][A] for A = BF4, NTf2, and PF6). The variation of Tm corresponding to n shows non-monotonous variations. This characteristic is the result of the combination of interaction potentials in the crystalline and liquid phases. The variation of Tg corresponding to n shows even–odd alternation, presumably due to the competition between the electrostatic and van der Waals forces. Many types of ILs have a relatively high Td value, enabling them to remain in the liquid state above 400 °C, they have excellent catalytic activity and dynamic properties. The variation of Td with n appears different to that of Tm. Furthermore, the variation of ΔHm with n seems to follow that of Tm. This behaviour is in accordance with the thermodynamic relation between ΔHm, Tm, and the entropy of the system. The values of λ varied weakly with the alkyl chain length, and strongly depend on the type of anion.