Thermodynamics Research Center, ThermoML : Journal of Chemical and Engineering Data

Solid-Liquid Phase Equilibrium and Thermodynamic Analysis of N,N'-Diethylthiourea in Different Solvent Systems

Yao, M.[Menghui], Li, W.[Wenlong], Shi, P.[Peng], Li, W.[Wanya], Wang, L.[Lingyu], Zhou, L.[Lina], Tang, W.[Weiwei]
J. Chem. Eng. Data 2019, 64, 12, 6031-6040
ABSTRACT
In this work, the solid-liquid phase equilibrium of N, N'-Diethylthiourea (DETU) was investigated in different solvent systems from both solid-state structure and solution thermodynamics. The single crystal structure of DETU was determined for the first time, and the intermolecular hydrogen bonding N-HS interactions are dominant in the crystal packing. The thermodynamic equilibrium solubility was determined by the gravimetric method in twelve solvents (methanol, ethanol, n-propanol, isopropanol, nbutanol, sec-butylalcohol, n-pentanol, acetone, butanone, methyl acetate, ethyl acetate, and acetonitrile) from 283.15 K to 323.15 K. It was found that the solubility in alcohols decreases with increasing the length of carbon chain and follows the rule of "like dissolves like", whereas in non-alcohol solvents the rule does not apply. The experimental data were further correlated by the modified Apelblat equation, h equation and NRTL model. All the correlation derivations are lower than 5%, and the NRTL model receives the best fitting performance. Furthermore, the thermodynamic functions of mixing including enthalpy, entropy, and Gibbs energy were derived, and the results expectedly suggest a spontaneous and entropy-driven mixing process. All the crystallographic and thermodynamic data reported in this study will provide the fundamental data for designing and optimizing the crystallization of DETU.
Compounds
# Formula Name
1 C5H12N2S N,N'-diethylthiourea
2 CH4O methanol
3 C2H6O ethanol
4 C3H8O propan-1-ol
5 C3H8O propan-2-ol
6 C4H10O butan-1-ol
7 C4H10O butan-2-ol
8 C5H12O pentan-1-ol
9 C3H6O acetone
10 C4H8O butanone
11 C3H6O2 methyl ethanoate
12 C4H8O2 ethyl acetate
13 C2H3N acetonitrile
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
  • Mass density, kg/m3 ; Crystal
  • Temperature, K; Crystal
  • Pressure, kPa; Crystal
  • Crystal
  • X-ray diffraction
  • 1
  • POMD
  • 1
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 1
  • Molar enthalpy of transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 1
  • 2
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 3
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 4
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 5
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 6
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 7
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 8
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 9
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 10
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 11
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 12
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9
  • POMD
  • 1
  • 13
  • Mole fraction - 1 ; Liquid
  • Temperature, K; Liquid
  • Pressure, kPa; Liquid
  • Liquid
  • Crystal - 1
  • gravimetric
  • 9