Thermodynamics Research Center / ThermoML | Thermochimica Acta

Thermophysical properties and thermodynamic phase behavior of ionic liquids

Domanska, U.[Urszula]
Thermochim. Acta 2006, 448, 1, 19-30
ABSTRACT
The thermal stability of many tested ionic liquids (ILs) was investigated by the TGA and DTA curves over the wide temperature range from 200 to 780 K. The TGA curves have mainly a sigmoid shape, which can be split into three segments. The thermal decomposition of the samples was higher than 500 K. For the ammonium salts, C2BF4, or C2PF6, or C2N(CN)2, or C4Br, the temperatures of the decompositions were 583.5, 556.1, 545.1 and 525.3 K, respectively. Generally, it was found that the temperature of decomposition of investigated ionic liquid is strongly depended on the type of cation and the anion. Phase equilibria and thermophysical constants were measured also for the dialkoxy-imidazolium ILs, [(C4H9OCH2)2IM][BF4], [(C8H17OCH2)2IM][Tf2N], [(C10H21OCH2)2IM][Tf2N] and for pyridinium IL, [Pyr][BF4]. The characterization and purity of the compounds were obtained by the elemental analysis, water content (Fisher method) and differential scanning microcalorimetry (DSC) analysis. From (DSC) method, the melting points, the enthalpies of fusion, the temperatures and enthalpies of solid solid phase transitions and the half Cp temperatures of glass transition of all investigated ionic liquids were measured. The phase equilibria of these salts with common popular solvents: water, or alcohols or n-alkanes, or aromatic hydrocarbons have been measured by a dynamic method from 290K to the melting point of IL, or to the boiling point of the solvent in the whole mole fraction range, x from 0 to 1. These salts mainly exhibit simple eutectic systems with immiscibility in the liquid phase with upper critical solution temperatures (UCST), not only with aromatic hydrocarbons, cycloalkanes and n-alkanes but also with longer chain alcohols. For example the C2BF4 salt show simple eutectic system with water and simple eutectic systems with immiscibility in the liquid phase with upper critical solution temperature with alcohols. The solid liquid phase equilibria, SLE curves were correlated by means of the different GEx models utilizing parameters derived from the SLE. The root-mean-square deviations of the solubility temperatures for all calculated data depend on the particular system and the equation used.
Compounds
# Formula Name
1 C6H16BF4NO N-ethyl-2-hydroxyethyl-N,N-dimethylammonium tetrafluoroborate
2 C6H16F6NOP N-ethyl-2-hydroxyethyl-N,N-dimethylammonium hexafluorophosphate
3 C8H16N4O N-ethyl-2-hydroxyethyl-N,N-dimethylammonium dicyanamide
4 C8H20BrNO N-(2-hydroxyethyl)-N,N-dimethylbutanaminium bromide
5 C13H25BF4N2O2 1,3-bis(butoxymethyl)-1H-imidazolium tetrafluoroborate
6 C23H41F6N3O6S2 1,3-bis((octyloxy)methyl)-1H-imidazolium bis((trifluoromethyl)sulfonyl)amide
7 C26H47F6N3O6S2 1,3-bis(decyloxy)-2-methyl-1H-imidazol-3-ium bis[(trifluoromethyl)sulfonyl]azanide
8 C17H29BF4N2O2 N-decyloxymethyl-3-amido-pyridinium tetrafluoroborate
9 C4H10O butan-1-ol
10 C4H10O butan-2-ol
11 C8H18O octan-1-ol
12 C12H26O dodecan-1-ol
13 C6H14 hexane
14 C7H16 heptane
15 C2H6O ethanol
16 C6H6 benzene
17 C6H14O hexan-1-ol
18 H2O water
19 C6H12 cyclohexane
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 enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 1
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 1
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 3
  • Crystal 3
  • Crystal 2
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 1
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA:corrimp
  • 1
  • POMD
  • 1
  • Triple point temperature, K ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 1
  • Triple point temperature, K ; Crystal 3
  • Crystal 3
  • Crystal 2
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 1
  • Triple point temperature, K ; Metastable crystal
  • Metastable crystal
  • Crystal 3
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 2
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 2
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA:corrimp
  • 1
  • POMD
  • 3
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 3
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA:corrimp
  • 1
  • POMD
  • 3
  • Triple point temperature, K ; Metastable crystal
  • Metastable crystal
  • Crystal 1
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 4
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 4
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA:corrimp
  • 1
  • POMD
  • 4
  • Triple point temperature, K ; Metastable crystal
  • Metastable crystal
  • Crystal 1
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 5
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 5
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA:corrimp
  • 1
  • POMD
  • 5
  • Triple point temperature, K ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 6
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 6
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA:corrimp
  • 1
  • POMD
  • 7
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 7
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA:corrimp
  • 1
  • POMD
  • 8
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 8
  • Triple point temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA:corrimp
  • 1
  • POMD
  • 18
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 3 - 1
  • VISOBS
  • 1
  • POMD
  • 18
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 2 - 1
  • VISOBS
  • 4
  • POMD
  • 18
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 18
  • VISOBS
  • 17
  • POMD
  • 18
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 1
  • VISOBS
  • 13
  • POMD
  • 9
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 1
  • VISOBS
  • 20
  • POMD
  • 9
  • 1
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 1; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 2
  • POMD
  • 10
  • 1
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 1; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 2
  • POMD
  • 10
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 2 - 1
  • VISOBS
  • 1
  • POMD
  • 10
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 1
  • VISOBS
  • 18
  • POMD
  • 11
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 1
  • VISOBS
  • 18
  • POMD
  • 11
  • 1
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 1; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 1
  • POMD
  • 12
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 1
  • VISOBS
  • 24
  • POMD
  • 12
  • 1
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 1; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 2
  • POMD
  • 13
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 4
  • VISOBS
  • 3
  • POMD
  • 13
  • 4
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 4; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 7
  • POMD
  • 14
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 4
  • VISOBS
  • 8
  • POMD
  • 14
  • 4
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 4; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 4
  • POMD
  • 19
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 4
  • VISOBS
  • 7
  • POMD
  • 19
  • 4
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 4; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 8
  • POMD
  • 15
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 2 - 5
  • VISOBS
  • 7
  • POMD
  • 15
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 5
  • VISOBS
  • 8
  • POMD
  • 15
  • 5
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 5; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 7
  • POMD
  • 11
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 5
  • VISOBS
  • 5
  • POMD
  • 11
  • 5
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 5; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 10
  • POMD
  • 16
  • 5
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 5; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 18
  • POMD
  • 16
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 2 - 5
  • VISOBS
  • 5
  • POMD
  • 16
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 5
  • VISOBS
  • 4
  • POMD
  • 15
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 6
  • VISOBS
  • 22
  • POMD
  • 11
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 6
  • VISOBS
  • 14
  • POMD
  • 16
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 16; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 16
  • VISOBS
  • 13
  • POMD
  • 16
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 6
  • VISOBS
  • 11
  • POMD
  • 15
  • 7
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 7; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 7
  • VISOBS
  • 19
  • POMD
  • 16
  • 7
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 7; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 7
  • VISOBS
  • 17
  • POMD
  • 15
  • 8
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 8
  • VISOBS
  • 25
  • POMD
  • 9
  • 8
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 8
  • VISOBS
  • 17
  • POMD
  • 17
  • 8
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 8
  • VISOBS
  • 15
  • POMD
  • 12
  • 8
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal 1 - 8
  • VISOBS
  • 12
  • POMD
  • 12
  • 8
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 8; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 7
  • POMD
  • 16
  • 8
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 8; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 10