Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2011-04-14

Experimental and computational thermochemical study of barbituric acids: structure-energy relationship in 1,3-dimethylbarbituric acid.

María Victoria Roux, Rafael Notario, Concepción Foces-Foces, Manuel Temprado, Francisco Ros, Vladimir N Emel'yanenko, Sergey P Verevkin

Index: J. Phys. Chem. A 115(14) , 3167-73, (2011)

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Abstract

This paper reports an experimental and computational thermochemical study on 1,3-dimethylbarbituric acid. The value of the standard (p° = 0.1 MPa) molar enthalpy of formation in the gas phase at T = 298.15 K has been determined. The energy of combustion was measured by static bomb combustion calorimetry, and from the result obtained, the standard molar enthalpy of formation in the crystalline state at T = 298.15 K was calculated as -639.6 ± 1.9 kJ·mol(-1). The enthalpy of sublimation was determined using a transference (transpiration) method in a saturated N(2) stream and a value of the enthalpy of sublimation at T = 298.15 K was derived as 92.3 ± 0.6 kJ·mol(-1). From these results a value of -547.3 ± 2.0 kJ·mol(-1) for the gas-phase enthalpy of formation at T = 298.15 K was determined. Theoretical calculations at the G3 and G4 levels were performed, and a study on molecular and electronic structure of the compound has been carried out. Calculated enthalpies of formation are in very good agreement with the experimental value.