Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

Phase behavior of ionic liquids 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides with halogenated benzenes

Siporska, A., Szydlowski, J.
J. Chem. Thermodyn. 2015, 88, 22-29
ABSTRACT
(Liquid + liquid) miscibility temperatures as a function of composition have been determined experimentally for the binary systems formed by imidazolium based ionic liquids with bis(trifluoromethylsulfonyl) imide ([CnMIM][NTf2]: n = 3 to 10) with fluorobenzene, chlorobenzene, bromobenzene, iodobenzene and 1,2-dichlorobenzene. In addition, the phase diagrams for deuterated chlorobenzene, bromobenzene and 1,2-dichlorobenzene have been obtained. All the measured systems show the limited miscibility with the upper critical solution temperature behavior. Similarly to the other systems with the imidazolium cation the increase of the alkyl chain length in this cation improves the miscibility. The impact of the halogenobenzene is also very visible. The miscibility is improving in the order: iodobenzene less than bromobenzene less than chlorobenzene less than fluorobenzene. This arrangement corresponds to the decreasing molar volume of the substituted benzenes. The disubstituted chlorobenzene is a better solvent for ionic liquids than chlorobenzene. The replacement of hydrogen for deuterium in halogenobenzenes in all cases improves the miscibility and the isotope shifts of the UCSTs are very large.
Compounds
# Formula Name
1 C8H11F6N3O4S2 1-ethyl-3-methylimidazolium bis((trifluoromethyl)sulfonyl)imide
2 C9H13F6N3O4S2 1-methyl-3-propylimidazolium bis[(trifluoromethyl)sulfonyl]imide
3 C10H15F6N3O4S2 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
4 C11H17F6N3O4S2 1-methyl-3-pentylimidazolium bis(trifluoromethylsulfonyl)imide
5 C12H19F6N3O4S2 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide
6 C13H21F6N3O4S2 1-heptyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide
7 C14H23F6N3O4S2 1-octyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide
8 C16H27F6N3O4S2 1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide
9 C6H5Cl chlorobenzene
10 C6H5Br bromobenzene
11 C6H5I iodobenzene
12 C6H5F fluorobenzene
13 C6H4Cl2 1,2-dichlorobenzene
14 C6D5Cl chlorobenzene-d5
15 C6D5Br bromobenzene-d5
16 C6D4Cl2 1,2-dichlorobenzene-d4
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
  • 9
  • 3
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 3; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 18
  • POMD
  • 14
  • 3
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 3; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 16
  • POMD
  • 9
  • 4
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 4; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 20
  • POMD
  • 10
  • 3
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 3; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 23
  • POMD
  • 15
  • 3
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 3; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 17
  • POMD
  • 10
  • 4
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 4; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 16
  • POMD
  • 15
  • 4
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 4; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 16
  • POMD
  • 10
  • 5
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 5; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 19
  • POMD
  • 11
  • 5
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 5; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 21
  • POMD
  • 11
  • 6
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 6; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 22
  • POMD
  • 11
  • 7
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 7; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 21
  • POMD
  • 11
  • 8
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 8; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 20
  • POMD
  • 13
  • 2
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 2; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 18
  • POMD
  • 16
  • 2
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 2; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 15
  • POMD
  • 13
  • 3
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 3; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 19
  • POMD
  • 16
  • 3
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Mass fraction - 3; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 16
  • POMD
  • 12
  • 1
  • 2
  • Liquid-liquid equilibrium temperature, K ; Liquid mixture 1
  • Solvent: Mole fraction - 1; Liquid mixture 1
  • Mass fraction - 12; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • VISOBS
  • 2