Thermochemical study of the ethylpyridine and ethylpyrazine isomers.
The standard (p(o) = 0.1 MPa) molar energies of combustion in oxygen, at T = 298.15 K, of four liquids: 2-ethylpyridine, 4-ethylpyridine, ethylpyrazine and 2,3-diethylpyrazine were measured by static bomb calorimetry in an oxygen atmosphere. The values of the standard molar enthalpies of vaporization, at T = 298.15 K, were obtained by Calvet microcalorimetry, allowing the calculation of the standard molar enthalpies of formation of the compounds, in the gas phase, at T= 298.15 K: 2-ethylpyridine (79.4 +/- 2.6) kJ mol(-1); 4-ethylpyridine (81.0 +/- 3.4) kJ mol(-1); ethylpyrazine (146.9 +/- 2.8) kJ mol(-1); and 2,3-diethylpyrazine (80.2 +/- 2.9) kJ mol(-1). The most stable geometries of all ethylpyridine and ethylpyrazine isomers were obtained using the density functional theory with the B3LYP functional and two basis sets: 6-31G* and 6-311G**. These calculations were then used to obtain estimates of the enthalpies of formation of all isomers, including those not experimentally studied, through the use of isodesmic reactions. A discussion of the relationship between structure and energetics of the isomers is also presented.
Morais
Victor M F
VM
Centro de Investigação em Química, Departamento de Química, Faculdade de Ciências da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto, Portugal.
Miranda
Margarida S
MS
Matos
M Agostinha R
MA