A comprehensive theoretical examination of primary dissociation pathways of formic acid
- 15 January 1992
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 96 (2) , 1167-1175
- https://doi.org/10.1063/1.462204
Abstract
Primary dissociation pathways have been investigated for formic acid by ab initio molecular orbital methods. Reactant, transition state, and products were fully optimized with unrestricted Hartree–Fock and unrestricted second-order Mo/ller–Plesset wave functions. The activation energy for decarboxylation of formic acid (CO2+H2) is 65.2 kcal mol−1, while that for the dehydration process (CO+H2O) is 63.0 kcal mol−1. These theoretical results suggest that the decarboxylation and dehydration processes are competitive. The activation energy barrier for isomerization of formic acid to yield dihydroxymethylene is 73.7 kcal mol−1 and may be a competitive process. Free radical initiation processes are predicted to be minor.Keywords
This publication has 29 references indexed in Scilit:
- s-cis and s-trans Conformers of formic, thioformic and dithioformic acids. An ab initio studyJournal of the Chemical Society, Faraday Transactions 2: Molecular and Chemical Physics, 1989
- Barriers to rotation adjacent to double bonds. 3. The carbon-oxygen barrier in formic acid, methyl formate, acetic acid, and methyl acetate. The origin of ester and amide resonanceJournal of the American Chemical Society, 1987
- Ab initio study of the unimolecular pyrolysis mechanisms of formic acid: additional comments based on refined calculationsJournal of the American Chemical Society, 1987
- Ab initio quantum-chemical study of the unimolecular pyrolysis mechanisms of formic acidJournal of the American Chemical Society, 1986
- Optimization of equilibrium geometries and transition structuresJournal of Computational Chemistry, 1982
- A theoretical study of paths for decomposition and rearrangement of dihydroxycarbeneJournal of Computational Chemistry, 1980
- The 1,2 hydrogen shift: a common vehicle for the disappearance of evanescent molecular speciesAccounts of Chemical Research, 1979
- Determination and analysis of the formic acid conformational hypersurfaceJournal of the American Chemical Society, 1979
- Internal rotation in some organic molecules containing methyl, amino, hydroxyl, and formyl groupsAustralian Journal of Chemistry, 1972
- The homogeneous decomposition reactions of gaseous formic acidProceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1960