Thermodynamics Research Center / ThermoML | Thermochimica Acta

A new analysis method for improving collection of vapor-liquid equilibrium (VLE) data of binary mixtures using differential scanning calorimetry (DSC)

Khoshooei, Milad Ahmadi, Sharp, Dave, Maham, Yadollah, Afacan, Artin, Dechaine, Greg Paul
Thermochim. Acta 2018, 659, 232-241
ABSTRACT
The method specified in ASTM E1782-14 for using differential scanning calorimetry (DSC) to measure vapor pressure of liquid samples can be extended to binary mixtures to gather vapor-liquid equilibrium (VLE data). In previous studies, the main uncertainty was in determining the transition temperature due to evaporation of the liquid sample prior to its actual boiling point. Using lids with a pinhole on the sample pan can only mitigate the adverse effect of pre-boiling. Present work shows evaluating the second derivative of temperature difference between the sample and reference temperature instead of the heat-flow curve eliminates the aforementioned drawback in the result analysis. The results obtained using the proposed method were benchmarked against published data and excellent agreement with published data indicates that this technique can be reliably used for experimental measurement of binary VLE data. Also, the results showed to be reproducible and thermodynamically consistent.
Compounds
# Formula Name
1 CH4O methanol
2 C3H8O propan-2-ol
3 C6H12 cyclohexane
4 C7H8 toluene
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
  • 1
  • Vapor or sublimation pressure, kPa ; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Gas
  • DSC
  • 1
  • POMD
  • 2
  • Vapor or sublimation pressure, kPa ; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Gas
  • DSC
  • 1
  • POMD
  • 3
  • Vapor or sublimation pressure, kPa ; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Gas
  • DSC
  • 1
  • POMD
  • 4
  • Vapor or sublimation pressure, kPa ; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Gas
  • DSC
  • 1
  • POMD
  • 5
  • Boiling temperature at pressure P, K ; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • DSC
  • 13
  • POMD
  • 1
  • 5
  • Boiling temperature at pressure P, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • DSC
  • 14
  • POMD
  • 2
  • 5
  • Boiling temperature at pressure P, K ; Liquid
  • Mole fraction - 2; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • DSC
  • 24
  • POMD
  • 3
  • 4
  • Boiling temperature at pressure P, K ; Liquid
  • Mole fraction - 3; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Gas
  • DSC
  • 16