Thermodynamics Research Center / ThermoML | Journal of Chemical and Engineering Data

Thermodynamic Study of Aggregation of Cholinium Perfluoroalkanoate Ionic Liquids

Florindo, C.[Catarina], Tome, L. C.[Liliana C.], Marrucho, I.[Isabel]
J. Chem. Eng. Data 2016, 61, 12, 3979-3988
ABSTRACT
To advance the ionic liquid (IL) platform to tailor fluorinated surfactant properties, the aim of this work is to evaluate the surfactant properties of cholinium-based salts bearing perfluoroalkanoate anions. Novel surfactant ILs containing the cholinium cation [Ch]+ combined with different perfluoroalkanoate anions, namely perfluoropentanoate [PFPent]-, perfluorohexanoate [PFHex]-, perfluoroheptanoate [PFHept]-, and perfluorooctanoate [PFOct]-, were synthesized. The critical micelle concentrations (CMCs) were determined using an ionic conductivity method, at different temperatures. Thermodynamic parameters of micellization were also evaluated. The results indicate that the CMC value decreases in a linear manner with the increment of the fluoroalkyl chain length in the anion. The evaluation of the thermodynamic parameters shows that the micellization is spontaneous and entropically driven and that the enthalpy of micellization is very small. It was also observed that the introduction of the cholinium cation in these surfactants allows for smaller CMC values when compared to that of other tetraalkylammonium-based surfactants with the same fluorinated anions, in short to more efficient and green surfactants. This result is probably due to counterion association and not to counterion binding to micelle surface.
Compounds
# Formula Name
1 C10H14F9NO3 (2-hydroxyethyl)trimethylammonium perfluoropentanoate
2 C11H14F11NO3 (2-hydroxyethyl)trimethylammonium perfluorohexanoate
3 C12H14F13NO3 (2-hydroxyethyl)trimethylammonium perfluoroheptanoate
4 C13H14F15NO3 (2-hydroxyethyl)trimethylammonium perfluorooctanoate
5 H2O water
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
  • 5
  • 1
  • Electrical conductivity, S/m ; Liquid
  • Temperature, K; Liquid
  • Molality, mol/kg - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Alternating current cell with electrodes
  • 177
  • POMD
  • 5
  • 2
  • Electrical conductivity, S/m ; Liquid
  • Temperature, K; Liquid
  • Molality, mol/kg - 2; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Alternating current cell with electrodes
  • 148
  • POMD
  • 5
  • 3
  • Electrical conductivity, S/m ; Liquid
  • Temperature, K; Liquid
  • Molality, mol/kg - 3; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Alternating current cell with electrodes
  • 131
  • POMD
  • 4
  • 5
  • Electrical conductivity, S/m ; Liquid
  • Temperature, K; Liquid
  • Molality, mol/kg - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Alternating current cell with electrodes
  • 204