Thermodynamics Research Center / ThermoML | Fluid Phase Equilibria

(Solid + liquid) and (liquid + liquid) phase equilibria of (IL + water) binary systems. The influence of the ionic liquid structure on mutual solubility

Krolikowska, M.[Marta]
Fluid Phase Equilib. 2014, 361, 273-281
ABSTRACT
In this work binary (solid + liquid) and (liquid + liquid) phase equilibria measurements for the new ionic liquids: 1-ethyl-3-methylimidazolium tricyanomethanide, [EMIM][TCM], 1-butyl-3-methylimidazolium tricyanomethanide, [BMIM][TCM], 1-butyl-1-methyl-pyrrolidinium tricyanomethanide, [BMPYR][TCM], 1-butyl-1-methylmorpholinium tricyanomethanide, [BMMOR][TCM], trihexyltertadecylphosphonium tricyanomethanide, [P6,6,6,14][TCM] with water over a wide temperature range and at atmospheric pressure have been determined using dynamic method. In order to discuss the influence of the ionic liquid structure on mutual miscibility with water the phase equilibria for 1-butyl- 1-methyl-pyrrolidinium trifluoromethanesulfonate, [BMPYR][CF3SO3], 1-butyl-1-methylpyrrolidinium tetracyanoborate, [BMPYR][TCB] and 1-butyl-3-methylimidazolium dicyanamide, [BMIM] [DCA] were detected. For the tested binary systems with immiscibility gap the parameters of the LLE correlation have been derived using the NRTL equation. For the binary mixtures of water and [EMIM][TCM], [BMIM][DCA] and [BMPYR][CF3SO3] the complete miscibility in the liquid phase over whole composition range was observed. For these systems the (solid + liquid) phase equilibria have been correlated by means of NRTL, UNIQUAC and Wilson equations. The influence of the ionic liquid structure on water solubility was discussed. Additionally the basic thermal characterization of pure ionic liquids that is: the glass transition temperature, the change of heat capacity at the glass-transition temperature, temperature and enthalpy of phase transition and temperature and enthalpy of melting were determined using DSC technique. Decomposition temperature was detected by thermograwimetry.
Compounds
# Formula Name
1 C10H11N5 1-ethyl-3-methyl-1H-imidazolium tricyanomethanide
2 C12H15N5 1-butyl-3-methylimidazolium tricyanomethane
3 C10H15N5 1-butyl-3-methylimidazolium dicyanamide
4 C13H20N4 1-butyl-1-methylpyrrolidinium tricyanomethanide
5 C13H20BN5 1-butyl-1-methylpyrrolidinium tetracyanoborate
6 C10H20F3NO3S 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate
7 C13H20N4O 4-butyl-4-methylmorpholinium tricyanomethanide
8 C36H68N3P trihexyltetradecylphosphonium tricyanomethanide
9 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
  • 1
  • Normal melting temperature, K ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 1
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal 1
  • Crystal 1
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 1
  • Triple point temperature, K ; Crystal 2
  • Crystal 2
  • Crystal 1
  • Air at 1 atmosphere
  • DTA
  • 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
  • Triple point temperature, K ; Glass
  • Glass
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 2
  • Triple point temperature, K ; Glass
  • Glass
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 4
  • Triple point temperature, K ; Glass
  • Glass
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 4
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • VISOBS
  • 1
  • POMD
  • 5
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 5
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • VISOBS
  • 1
  • POMD
  • 6
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • VISOBS
  • 1
  • POMD
  • 7
  • Triple point temperature, K ; Glass
  • Glass
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 8
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 8
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 9
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • VISOBS
  • 1
  • POMD
  • 9
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Crystal - 9
  • Liquid
  • Crystal - 9
  • VISOBS
  • 18
  • POMD
  • 9
  • 2
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 2; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 2
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 23
  • POMD
  • 9
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 3; Liquid
  • Pressure, kPa; Crystal - 9
  • Liquid
  • Crystal - 9
  • VISOBS
  • 18
  • POMD
  • 9
  • 4
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 4; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 2
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 21
  • POMD
  • 9
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Crystal - 4
  • Liquid
  • Crystal - 4
  • VISOBS
  • 7
  • POMD
  • 9
  • 5
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 5; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 2
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 18
  • POMD
  • 9
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Crystal - 5
  • Liquid
  • Crystal - 5
  • VISOBS
  • 11
  • POMD
  • 9
  • 6
  • Eutectic composition: mole fraction - 6 ; Liquid
  • Liquid
  • Crystal - 6
  • Air at 1 atmosphere
  • Crystal - 9
  • Derived from phase diagram analysis
  • 1
  • POMD
  • 9
  • 6
  • Eutectic temperature, K ; Liquid
  • Liquid
  • Crystal - 6
  • Crystal - 9
  • Air at 1 atmosphere
  • Derived from phase diagram analysis
  • 1
  • POMD
  • 9
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Crystal - 6
  • Liquid
  • Crystal - 6
  • VISOBS
  • 12
  • POMD
  • 9
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Crystal - 9
  • Liquid
  • Crystal - 9
  • VISOBS
  • 19
  • POMD
  • 7
  • 9
  • Monotectic temperature, K ; Crystal - 9
  • Crystal - 9
  • Liquid mixture 1
  • Liquid mixture 2
  • Air at 1 atmosphere
  • Derived from phase diagram analysis
  • 1
  • POMD
  • 7
  • 9
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 7; Liquid
  • Pressure, kPa; Crystal - 9
  • Liquid
  • Crystal - 9
  • VISOBS
  • 31
  • POMD
  • 7
  • 9
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 7; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 2
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 11
  • POMD
  • 9
  • 8
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mole fraction - 8; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 2
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 6