Thermochemistry of alkyl pyridinium bromide ionic liquids: calorimetric measurements and calculations.

Two ionic liquids, 1-ethylpyridinium bromide (EPBr) and 1-propylpyridinium bromide (PPBr), were prepared and the structures were characterized by 1H NMR. The thermodynamic properties of EPBr and PPBr were studied with adiabatic calorimetry (AC) and thermogravimatric analysis (TG-DTG). The heat capacity was precisely measured in the temperature range from 78 to 410 K by means of a fully automated adiabatic calorimeter. For EPBr, the melting temperature, enthalpy, and entropy of solid-liquid phase transition were determined to be 391.31 +/- 0.28 K, 12.77 +/- 0.09 kJ x mol(-1), and 32.63 +/- 0.22 J x K(-1) x mol(-1), respectively, and for PPBr they were 342.83 +/- 0.69 K, 10.97 +/- 0.05 kJ x mol(-1), and 32.00 +/- 0.10 J x K(-1) x mol(-1), respectively. The thermodynamic functions (H(T)(0) - H(298.15)(0)) and (S(T)(0) - S(298.15)(0)) were derived from the heat capacity data in the experimental temperature range with an interval of 5 K. The thermostablility of the compounds was further studied by TGA measurements. The phase change behavior and thermodynamic properties were compared and estimated in a series of alkyl pyridinium bromide ionic liquids. Results indicate that EPBr has higher melting and decomposition temperature, as well as phase transition enthalpy and entropy but lower heat capacity than PPBr due to their different molecular structures.