Thermodynamics Research Center / ThermoML | Fluid Phase Equilibria

Liquid-liquid equilibrium in binary and ternary mixtures containing formaldehyde, water, methanol, methylal, and poly(oxymethylene) dimethyl ethers

Schmitz, N.[Niklas], Friebel, A.[Anne], Harbou, E. v.[Erik von], Burger, J.[Jakob], Hasse, H.[Hans]
Fluid Phase Equilib. 2016, 425, 127-135
ABSTRACT
Poly(oxymethylene) dimethyl ethers (OME) are an interesting class of oxygenated fuel components and solvents for the absorption of carbon dioxide. The chemical structure of OMEn is H3C-O-(CH2O)n-CH3 with n GE 2 and the IUPAC names are methoxy(methoxymethoxy)methane (n = 2), 2,4,6,8- tetraoxanonane (n =3), and 2,4,6,8,10-pentaoxaundecane (n = 4). This work studies the liquid-liquid equilibrium (LLE) in the binary systems (water + methylal), (water + OME2), (water + OME3), and (water + OME4) and the ternary systems (water + methanol + OME2), (water + methanol + OME3), (formaldehyde + water + OME2), (formaldehyde + water + OME3), and (water + methylal + OME2) in the temperature range 280 K to 340 K. The systems were studied by gas chromatographic- and titrimetric analysis of samples that were drawn from the coexisting liquid phases, as well by in situ analysis with a medium-field NMR spectrometer. The LLE was modeled by extending a UNIFAC-based activity coefficient model of the system (formaldehyde + water + methanol + methylal) from the literature. One new structural group is introduced to represent the OME.
Compounds
# Formula Name
1 CH4O methanol
2 C3H8O2 dimethoxymethane
3 C4H10O3 2,4,6-trioxaheptane
4 C5H12O4 2,4,6,8-tetraoxanonane
5 C6H14O5 2,4,6,8,10-pentaoxaundecane
6 CH2O methanal
7 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
  • 2
  • 7
  • Mass fraction - 2 ; Liquid mixture 1
  • Temperature, K; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • Chromatography
  • 3
  • POMD
  • 2
  • 7
  • Mass fraction - 2 ; Liquid mixture 2
  • Temperature, K; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 2
  • Liquid mixture 1
  • Chromatography
  • 3
  • POMD
  • 3
  • 7
  • Mass fraction - 3 ; Liquid mixture 1
  • Temperature, K; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • Chromatography
  • 8
  • POMD
  • 3
  • 7
  • Mass fraction - 3 ; Liquid mixture 2
  • Temperature, K; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 2
  • Liquid mixture 1
  • Chromatography
  • 8
  • POMD
  • 7
  • 4
  • Mass fraction - 4 ; Liquid mixture 1
  • Temperature, K; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • Chromatography
  • 7
  • POMD
  • 7
  • 4
  • Mass fraction - 4 ; Liquid mixture 2
  • Temperature, K; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 2
  • Liquid mixture 1
  • Chromatography
  • 7
  • POMD
  • 7
  • 5
  • Mass fraction - 5 ; Liquid mixture 1
  • Temperature, K; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 1
  • Liquid mixture 2
  • Chromatography
  • 7
  • POMD
  • 7
  • 5
  • Mass fraction - 5 ; Liquid mixture 2
  • Temperature, K; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 2
  • Liquid mixture 1
  • Chromatography
  • 7
  • POMD
  • 1
  • 3
  • 7
  • Mass fraction - 1 ; Liquid mixture 2
  • Mass fraction - 1 ; Liquid mixture 1
  • Mass fraction - 3 ; Liquid mixture 1
  • Temperature, K; Liquid mixture 1
  • Mass fraction - 3; Liquid mixture 2
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 2
  • Liquid mixture 1
  • Chromatography
  • Chromatography
  • Chromatography
  • 4
  • POMD
  • 1
  • 7
  • 4
  • Mass fraction - 1 ; Liquid mixture 2
  • Mass fraction - 1 ; Liquid mixture 1
  • Mass fraction - 4 ; Liquid mixture 1
  • Temperature, K; Liquid mixture 1
  • Mass fraction - 4; Liquid mixture 2
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 2
  • Liquid mixture 1
  • Chromatography
  • Chromatography
  • Chromatography
  • 4
  • POMD
  • 6
  • 3
  • 7
  • Mass fraction - 3 ; Liquid mixture 2
  • Mass fraction - 6 ; Liquid mixture 1
  • Mass fraction - 3 ; Liquid mixture 1
  • Temperature, K; Liquid mixture 1
  • Mass fraction - 6; Liquid mixture 2
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 2
  • Liquid mixture 1
  • Chromatography
  • Chromatography
  • Chromatography
  • 4
  • POMD
  • 6
  • 7
  • 4
  • Mass fraction - 4 ; Liquid mixture 2
  • Mass fraction - 6 ; Liquid mixture 1
  • Mass fraction - 4 ; Liquid mixture 1
  • Mass fraction - 6; Liquid mixture 2
  • Temperature, K; Liquid mixture 1
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 2
  • Liquid mixture 1
  • Chromatography
  • Chromatography
  • Chromatography
  • 2
  • POMD
  • 2
  • 3
  • 7
  • Mass fraction - 3 ; Liquid mixture 2
  • Mass fraction - 3 ; Liquid mixture 1
  • Mass fraction - 2 ; Liquid mixture 1
  • Temperature, K; Liquid mixture 1
  • Mass fraction - 2; Liquid mixture 2
  • Pressure, kPa; Liquid mixture 1
  • Liquid mixture 2
  • Liquid mixture 1
  • Chromatography
  • Chromatography
  • Chromatography
  • 7