Effect of alkyl chain length on the thermal properties and toxicity of n-alkyl-ammonium nitrate ionic liquids (n = 2, 3, 4, 5, 6, 8) for energy applications

Abstract

The most currently used ionic liquids (ILs) are protic ionic liquids (PILs), subject to extensive investigation regarding their physical properties. These compounds along with their mixtures with other substances such as salts and solvents, serve as electrolytes in next generation electrochemical smart devices, and emerge as viable candidates to replace conventional Heat Transfer Fluids (HTFs) in various energy applications. Despite the extensive number of studies, important information about this kind of compounds is still unknown, such as the effect of alkyl chain length on thermal and thermophysical properties, as well as toxicity. This work, extending previous studies of our group, summarizes the liquid range, heat capacity and acute toxicity level of six ammonium ILs: specifically, n-alkyl-ammonium nitrate ILs with increasing alkyl chain length (n = 2, 3, 4, 5, 6, 8). For this study, the synthesis of the three ILs with the longest alkyl chain was performed, along with DSC, TGA and toxicity measurements. It was observed that an increase in alkyl chain length resulted in a decrease in short-term thermal stability and an increase in melting temperature, indicating a reduction in the liquid range. A compensation effect between enthalpy and entropy of melting was observed for the studied chain lengths. The isobaric specific and molar heat capacities increase with temperature for all the compounds studied here, and good correlations were obtained between molar heat capacity and the number of carbon atoms in the alkyl chain for every temperature. Finally, most of the ILs are non-toxic, although toxicity increases with alkyl chain length.