Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

The enthalpies of formation of alkyl carbamates: Experimental and computational redetermination

Santos, A. F. L. O. M.[Ana Filipa L.O.M.], Ribeiro da Silva, M. A. V.[Manuel A.V.]
J. Chem. Thermodyn. 2013, 57, 454-460
ABSTRACT
In the present work, a redetermination of thermochemical data of methyl carbamate and ethyl carbamate was performed by both experimental and computational techniques. Their gas-phase standard (po = 0.1 MPa) molar enthalpies of formation, DfHo m ogP, at T = 298.15 K, were derived from the standard molar enthalpies of formation, in the crystalline phase, DfHo mocrP, and from the standard molar enthalpies of sublimation, Dg crHo m at T = 298.15 K, measured, respectively, by static bomb combustion calorimetry and high temperature Calvet microcalorimetry. The experimental results were compared with computational data, calculated at the G3(MP2)//B3LYP level, as well as with values reported in the literature. At the B3LYP/6-31G(d) level of theory, the molecular structure of both carbamates was obtained.
Compounds
# Formula Name
1 CO2 carbon dioxide
2 N2 nitrogen
3 H2O water
4 O2 oxygen
5 C2H5NO2 carbamic acid, methyl ester
6 C3H7NO2 ethyl carbamate
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
  • 5
  • Molar enthalpy of vaporization or sublimation, kJ/mol ; Crystal
  • Temperature, K; Crystal
  • Crystal
  • Gas
  • Static calorimetry
  • 1
  • POMD
  • 6
  • Molar enthalpy of vaporization or sublimation, kJ/mol ; Crystal
  • Temperature, K; Crystal
  • Crystal
  • Gas
  • Static calorimetry
  • 1
  • RXND
  • 5
  • 1
  • 2
  • 3
  • 4
  • Specific internal energy of reaction at constant volume, J/g
  • Static bomb calorimetry
  • 1
  • RXND
  • 6
  • 1
  • 2
  • 3
  • 4
  • Specific internal energy of reaction at constant volume, J/g
  • Static bomb calorimetry
  • 1