Thermodynamics Research Center / ThermoML | Fluid Phase Equilibria

Measurement and PC-SAFT modeling of solid-liquid equilibrium of deep eutectic solvents of quaternary ammonium chlorides and carboxylic acids

Pontes, Paula V.A., Crespo, Emanuel A., Martins, Monia A.R., Silva, Liliana P., Neves, Catarina M.S.S., Maximo, Guilherme J., Hubinger, Miriam Dupas, Batista, Eduardo A.C., Pinho, Simao P., Coutinho, Joao A.P., Sadowski, Gabriele, Held, Christoph
Fluid Phase Equilib. 2017, 448, 69-80
ABSTRACT
In this study the solid-liquid equilibria (SLE) of 15 binary mixtures composed of one of three different symmetrical quaternary ammonium chlorides and one of five different fatty acids were measured. The experimental data obtained showed extreme negative deviations to ideality causing large melting-temperature depressions (up to 300K) that are characteristic for deep eutectic systems. The experimental data revealed that cross-interactions between quaternary ammonium salt and fatty acid increase with increasing alkyl chain length of the quaternary ammonium chloride and with increasing chain length of the carboxylic acid. The pronounced decrease of melting temperatures in these deep eutectic systems is mainly caused by strong hydrogen-bonding interactions, and thermodynamic modeling required an approach that takes hydrogen bonding into account. Thus, the measured phase diagrams were modelled with perturbed-chain statistical associating theory based on the classical molecular homonuclear approach. The model showed very good agreement with the experimental data using a semi-predictive modeling approach, in which binary interaction parameters between quaternary ammonium chloride and carboxylic acid correlated with chain length of the components. This supports the experimental findings on the phase behavior and interactions present in these systems and it allows estimating eutectic points of such highly non-ideal mixtures.
Compounds
# Formula Name
1 C4H12ClN tetramethylammonium chloride
2 C8H20ClN tetraethylammonium chloride
3 C12H28ClN tetrapropylammonium chloride
4 C10H20O2 decanoic acid
5 C12H24O2 dodecanoic acid
6 C14H28O2 tetradecanoic acid
7 C16H32O2 hexadecanoic acid
8 C18H36O2 octadecanoic acid
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
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 2
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 2
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 3
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 3
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 4
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 4
  • 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
  • DTA
  • 1
  • POMD
  • 5
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 6
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 6
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 7
  • Normal melting temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 7
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 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
  • 1
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • There were three separate methods used - please see original paper for them.
  • 7
  • POMD
  • 1
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 4
  • There were three separate methods used - please see original paper for them.
  • 4
  • POMD
  • 1
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • There were three separate methods used - please see original paper for them.
  • 7
  • POMD
  • 1
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 5
  • There were three separate methods used - please see original paper for them.
  • 6
  • POMD
  • 1
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • There were three separate methods used - please see original paper for them.
  • 6
  • POMD
  • 1
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 6
  • There were three separate methods used - please see original paper for them.
  • 7
  • POMD
  • 7
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 7; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • There were three separate methods used - please see original paper for them.
  • 5
  • POMD
  • 7
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 7; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 7
  • There were three separate methods used - please see original paper for them.
  • 8
  • POMD
  • 8
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • There were three separate methods used - please see original paper for them.
  • 5
  • POMD
  • 8
  • 1
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 8
  • VISOBS
  • 4
  • POMD
  • 2
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 2
  • There were three separate methods used - please see original paper for them.
  • 9
  • POMD
  • 2
  • 4
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 4
  • There were three separate methods used - please see original paper for them.
  • 4
  • POMD
  • 2
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 2
  • There were three separate methods used - please see original paper for them.
  • 9
  • POMD
  • 2
  • 5
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 5
  • There were three separate methods used - please see original paper for them.
  • 6
  • POMD
  • 2
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 2
  • There were three separate methods used - please see original paper for them.
  • 9
  • POMD
  • 2
  • 6
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 6
  • There were three separate methods used - please see original paper for them.
  • 6
  • POMD
  • 2
  • 7
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 7; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 7
  • There were three separate methods used - please see original paper for them.
  • 8
  • POMD
  • 2
  • 7
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 7; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 2
  • There were three separate methods used - please see original paper for them.
  • 9
  • POMD
  • 2
  • 8
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 2
  • There were three separate methods used - please see original paper for them.
  • 5
  • POMD
  • 2
  • 8
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 8
  • There were three separate methods used - please see original paper for them.
  • 7
  • POMD
  • 4
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 3
  • There were three separate methods used - please see original paper for them.
  • 8
  • POMD
  • 4
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 4; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 4
  • There were three separate methods used - please see original paper for them.
  • 3
  • POMD
  • 5
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 3
  • There were three separate methods used - please see original paper for them.
  • 7
  • POMD
  • 5
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 5; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 5
  • There were three separate methods used - please see original paper for them.
  • 9
  • POMD
  • 6
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 3
  • There were three separate methods used - please see original paper for them.
  • 7
  • POMD
  • 6
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 6; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 6
  • There were three separate methods used - please see original paper for them.
  • 9
  • POMD
  • 7
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 7; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 3
  • There were three separate methods used - please see original paper for them.
  • 7
  • POMD
  • 7
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 7; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 7
  • There were three separate methods used - please see original paper for them.
  • 9
  • POMD
  • 8
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 3
  • There were three separate methods used - please see original paper for them.
  • 6
  • POMD
  • 8
  • 3
  • Solid-liquid equilibrium temperature, K ; Liquid
  • Mole fraction - 8; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 8
  • There were three separate methods used - please see original paper for them.
  • 8
  • POMD
  • 1
  • 9
  • (Relative) activity - 9 ; Liquid
  • Mole fraction - 9; Liquid
  • Pressure, kPa; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Calculated from EMF cell potential
  • 5
  • POMD
  • 1
  • 9
  • Mass density, kg/m3 ; Liquid
  • Mole fraction - 1; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Vibrating tube method
  • 30
  • POMD
  • 3
  • 9
  • (Relative) activity - 9 ; Liquid
  • Mole fraction - 9; Liquid
  • Pressure, kPa; Liquid
  • Temperature, K; Liquid
  • Liquid
  • Calculated from EMF cell potential
  • 5
  • POMD
  • 3
  • 9
  • Mass density, kg/m3 ; Liquid
  • Mole fraction - 3; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Vibrating tube method
  • 31
  • POMD
  • 2
  • 9
  • Mass density, kg/m3 ; Liquid
  • Mole fraction - 2; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Vibrating tube method
  • 31