Enthalpies of formation of nitromethane and nitrobenzene: New experiments vs quantum chemical calculations

Published

September 11, 2013

Author(s)

Vladimir Diky, Sergey Verevkin, Vladimir Emel?yanenko, Olga Dorofeeva

Abstract

Enthalpy of combustion of highly pure nitromethane and nitrobenzene have been measured with the precise combustion calorimetry. Enthalpies of vaporization for both compounds were collected and evaluated. New internally consistent experimental data set of values for nitromethane and nitrobenzene was compared with the results of one of the most accurate first-principles G4 method applied to both atomization and isodesmic reactions. It was shown that the values calculated using the atomization reaction procedure are underestimated by 6.6 kJ.mol-1 for nitromethane and 9.1 kJ.mol-1 for nitrobenzene. Isodesmic reaction scheme strongly supports the internal consistency of new experimental data. Simple “corrected atomization procedure” to derive the reliable theoretical enthalpies of formation directly from the G4 atomization reaction values has been tested and recommended as the alternative to the bond separation and isodesmic reactions.

Citation

Journal of Chemical Thermodynamics

Pub Type

Journals

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DOI Link

Keywords

Combustion calorimetry, Enthalpy of formation, Enthalpy of vaporization, Vapour pressure, G4 quantum chemical calculations

Citation

Diky, V. , Verevkin, S. , Emel?yanenko, V. and Dorofeeva, O. (2013), Enthalpies of formation of nitromethane and nitrobenzene: New experiments vs quantum chemical calculations, Journal of Chemical Thermodynamics, [online], https://doi.org/10.1016/j.jct.2013.12.013 (Accessed September 20, 2024)