Faculty Publications

On The Heat Of Formation Of Nitromethane

Document Type

Article

Keywords

Ab initio theory, Density functional theory, Gas phase heat of formation, Group additivity approach, Nitromethane

Journal/Book/Conference Title

Journal of Physical Organic Chemistry

Volume

21

Issue

9

First Page

747

Last Page

757

Abstract

Two experimental values (-19.3 ± 0.3 and -17.8 ± 0.1 kcal/mol) for the gas phase heat of formation (ΔfH g0) (298k) of nitromethane have been reported. Although these values differ by only 1.5 kcal/mol, substantially greater differences in theoretical and experimental results occur when these differing values are used to calculate thermodynamic properties. This is especially evident when these two values for the ΔfHg0 of nitromethane are used to calculate thermodynamic properties of polynitro compounds. For example, when density functional theory (DFT) is coupled with the use of isodesmic reactions, the ΔfHg0 of octanitrocubane is calculated to be 160.6 or 172.6 kcal/mol, depending on which value is used. It should also be appreciated that several computational theories depend upon having access to reliable experimental data for testing and development. We have examined this discrepancy using several computational models and several levels of theory. Our results coupled with a comprehensive review of the literature support the lower (-19.3 ± 0.3 kcal/mol) experimental value. This is problematic because the higher value (-17.8 ± 0.1 kcal/mol) has been used in the development and/or testing of several semiempirical quantum mechanical models as well as ab initio Gaussian theory (G2 and G3). Copyright © 2008 John Wiley & Sons, Ltd.

Original Publication Date

9-1-2008

DOI of published version

10.1002/poc.1358

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