Thermodynamics Research Center / ThermoML | Thermochimica Acta

Differential scanning calorimetry determination of phase diagrams and water activities of aqueous carboxylic acid solutions

Noshadi, Sajjad, Sadeghi, Rahmat
Thermochim. Acta 2018, 663, 46-52
ABSTRACT
We have investigated the solid-liquid equilibria phase diagrams and water activities of the several carboxylic acid/water binary systems using differential scanning calorimetry (DSC) method. These mixtures were formed by water and low molecular weight carboxylic acids (formic acid, acetic acid, propionic acid and butyric acid). Water activities of the investigated solutions were obtained from the freezing point depression data in the range of the ice melting envelope. The experimental results indicated that all the aqueous carboxylic acid systems present a eutectic point in their respective phase diagrams. The activity coefficients of two components in the liquid phase were used to adjust the parameters of the Wilson and NRTL models. For all of the investigated systems, the best correlations of the solid-liquid equilibrium data have been determined by using the NRTL model. Finally, the phase behaviors of the systems were compared to the ideal state and the influence of the chemical structure of the carboxylic acids on the magnitude of the deviation from the ideal state was discussed.
Compounds
# Formula Name
1 CH2O2 formic acid
2 C2H4O2 acetic acid
3 C3H6O2 propanoic acid
4 C4H8O2 butanoic acid
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
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 2
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 3
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 4
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • 1
  • Eutectic temperature, K ; Liquid
  • Liquid
  • Crystal - 5
  • Crystal - 1
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • DTA
  • 8
  • POMD
  • 5
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 1; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 5
  • DTA
  • 6
  • POMD
  • 5
  • 2
  • Eutectic temperature, K ; Liquid
  • Liquid
  • Crystal - 5
  • Crystal - 2
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • 2
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 2; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 2
  • DTA
  • 10
  • POMD
  • 5
  • 2
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 2; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 5
  • DTA
  • 7
  • POMD
  • 5
  • 3
  • Eutectic temperature, K ; Liquid
  • Liquid
  • Crystal - 5
  • Crystal - 3
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 3; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 3
  • DTA
  • 7
  • POMD
  • 5
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 3; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 5
  • DTA
  • 9
  • POMD
  • 5
  • 4
  • Eutectic temperature, K ; Liquid
  • Liquid
  • Crystal - 5
  • Crystal - 4
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 4
  • DTA
  • 6
  • POMD
  • 5
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 5
  • DTA
  • 12