Thermodynamic Properties and Decomposition of Lithium Hexafluoroarsenate, LiAsF6

The heat capacity of lithium hexafluoroarsenate is determined in the temperature range 50–750 K by adiabatic and differential scanning calorimetry techniques. The thermodynamic properties of LiAsF6 under standard conditions are evaluated: Cp0(298.15 K) = 162.5 ± 0.3 J/(K mol), S0(298.15 K) = 173.4 ± 0.4 J/(K mol), Φ0(298.15 K) = 81.69 ± 0.20 J/(K mol), and H0(298.15 K) – H0(0) = 27340 ± 60 J/mol. The Cp(T) curve is found to contain a lambda-type anomaly with a peak at 535.0 ± 0.5 K, which is due to the structural transformation from the low-temperature, rhombohedral phase to the high-temperature, cubic phase. The enthalpy and entropy of this transformation are 5.29 ± 0.27 kJ/mol and 10.30 ± 0.53 J/(K mol), respectively. The thermal decomposition of LiAsF6 is studied. It is found that LiAsF6 decomposes in the range 715–820 K. The heat of decomposition, determined in the range 765–820 K using a sealed crucible and equal to the internal energy change ΔUr(T), is 31.64 ± 0.08 kJ/mol.