Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

Thermochemical study of cyanopyrazines: Experimental and theoretical approaches

Miranda, M. S.[Margarida S.], Morais, V. M. F.[Victor M.F.], Matos, M. A. R.[M. Agostinha R.]
J. Chem. Thermodyn. 2006, 38, 5, 559-564
ABSTRACT
The standard (p? = 0.1 MPa) molar energy of combustion, at T = 298.15 K, of crystalline 2,3-dicyanopyrazine was measured by static bomb calorimetry, in oxygen atmosphere. The standard molar enthalpy of sublimation, at T = 298.15 K, was obtained by Calvet Microcalorimetry, allowing the calculation of the standard molar enthalpy of formation of the compound, in the gas phase, at T = 298.15 K: DfH?m (g) = (518.7 +- 3.4) kJ Ae mol?1. In addition, the geometries of all cyanopyrazines were obtained using density functional theory with the B3LYP functional and two basis sets: 6-31G* and 6-311G**. These calculations were then used for a better understanding of the relation between structure and energetics of the cyanopyrazine systems. These calculations also reproduce measured standard molar enthalpies of formation with some accuracy and do provide estimates of this thermochemical parameter for those compounds that could not be studied experimentally, namely the tri- and tetracyanopyrazines: the strong electron withdrawing cyano group on the pyrazine ring makes cyanopyrazines highly destabilized compounds.
Compounds
# Formula Name
1 CO2 carbon dioxide
2 N2 nitrogen
3 H2O water
4 O2 oxygen
5 C6H2N4 2,3-pyrazinedicarbonitrile
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 transition or fusion, kJ/mol ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DSC
  • 1
  • POMD
  • 5
  • Triple point temperature, K ; Crystal
  • Crystal
  • Liquid
  • Air at 1 atmosphere
  • DTA
  • 1
  • POMD
  • 5
  • Mass density, kg/m3 ; Crystal
  • Temperature, K; Crystal
  • Pressure, kPa; Crystal
  • Crystal
  • Estimation
  • 1
  • RXND
  • 5
  • 1
  • 2
  • 3
  • 4
  • Specific internal energy of reaction at constant volume, J/g
  • Static bomb calorimetry
  • 1