Thermodynamic properties and polymorphism of 1-alkyl-3-methylimidazolium bis(triflamides)

Heat capacities in a range of temperatures of (5 to 370) K, enthalpies and temperatures of phase transitions for 1-ethyl-3-methylimidazolium bis(triflamide) ([C2mim][NTf2]) and 1-octyl-3-methylimidazolium bis(triflamide) ([C8mim][NTf2]) have been determined by adiabatic calorimetry. [C2mim][NTf2] has been found to form four crystalline phases with different fusion temperatures. Formation of the phases can be controlled by the temperature of annealing during crystallization. [C8mim][NTf2] forms three sequences of crystalline modifications, each including two polymorphs. Based on results of the measurements, thermodynamic functions for the compounds under study have been calculated.A heat-capacity anomaly near T = 230 K reported earlier for [C4mim][NTf2] and [C6mim][NTf2] have been found in some crystalline modifications of both the studied compounds. The position of the anomaly depends on the temperature of annealing of the crystals.