Skip to main content
U.S. flag

An official website of the United States government

Official websites use .gov
A .gov website belongs to an official government organization in the United States.

Secure .gov websites use HTTPS
A lock ( ) or https:// means you’ve safely connected to the .gov website. Share sensitive information only on official, secure websites.

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

Published

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
Volume
73

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 May 24, 2024)

Issues

If you have any questions about this publication or are having problems accessing it, please contact reflib@nist.gov.

Created December 20, 2013, Updated November 10, 2018