Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

Quaternary phosphonium-based ionic liquids: Thermal stability and heat capacity of the liquid phase

Ferreira, A. F., Simoes, P. N., Ferreira, A. G. M.
J. Chem. Thermodyn. 2012, 45, 1, 16-27
ABSTRACT
In spite of the great importance of calorimetric data on phosphonium-based ionic liquids (PBILs), the information available in the literature is quite limited. This work reports the study of the thermal stability and the determination of heat capacity of the following (PBILs): tributyl(methyl)phosphonium methyl sulfate, [(C4)3PC1][MeSO4], trihexyl-tetradecylphosphonium chloride, [(C6)3PC14][Cl], trihexyl-tetradecyl- phosphonium dicyanamide, [(C6)3 PC14][DCA], trihexyl-tetradecylphosphonium bis((trifluoromethyl) sulfonyl) imide, [(C6)3 PC14][NTf2], and trihexyl-tetradecylphosphonium tris(pentafluoroethyl) trifluorophosphate, [(C6)3 PC14][FAP]. Measurements on the well-known IL 1-ethyl-3-methylimidazoliumbis(( trifluoromethyl)sulfonyl)imide, [EMIM][NTf2], were also performed for comparative purposes. The thermal stability was assessed by conventional and high resolution modulated thermogravimetric analysis within the interval (303 to 873) K. The heat capacity was measured by modulated differential scanning calorimetry within the range (310 to 515) K with an uncertainty in the range (1 to 5) J K 1 mol 1. The experimental results were correlated using polynomial expressions. The Joback method for predicting ideal gas heat capacities was used in conjunction with the principle of corresponding states and the modified Lydersen Joback Reid method to predict the heat capacity of the ILs. The methods due to Valderrama et al. were also used with the same purpose.
Compounds
# Formula Name
1 C32H68ClP trihexyl(tetradecyl)phosphonium chloride
2 C34H68N3P tetradecyl(trihexyl)phosphonium dicyanamide
3 C14H33O4PS tributylmethylphosphonium methyl sulfate
4 C34H68F6NO4PS2 trihexyl(tetradecyl)phosphonium bis[(trifluoromethyl)sulfonyl]imide
5 C38H68F18P2 trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate
6 C8H11F6N3O4S2 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide
Datasets
The table above is generated from the ThermoML associated json file (link above). POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied; the numbers refer to the table of compounds on the left.
Type Compound-# Property Variable Constraint Phase Method #Points
  • POMD
  • 1
  • Molar heat capacity at constant pressure, J/K/mol ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Small sample (50 mg) DSC
  • 104
  • POMD
  • 2
  • Molar heat capacity at constant pressure, J/K/mol ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Small sample (50 mg) DSC
  • 63
  • POMD
  • 3
  • Molar heat capacity at constant pressure, J/K/mol ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Small sample (50 mg) DSC
  • 50
  • POMD
  • 4
  • Molar heat capacity at constant pressure, J/K/mol ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Small sample (50 mg) DSC
  • 110
  • POMD
  • 5
  • Molar heat capacity at constant pressure, J/K/mol ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Small sample (50 mg) DSC
  • 143
  • POMD
  • 6
  • Molar heat capacity at constant pressure, J/K/mol ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Small sample (50 mg) DSC
  • 75