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Complex mechanism of the gas phase reaction between formic acid and hydroxyl radical. Proton coupled electron transfer versus radical hydrogen abstraction mechanisms

AutorAnglada Rull, Josep M.
Palabras claveFormic acid
Hydroxyl radical
Gas Phase Reaction
Chemical reactions
Double proton transfer
Fecha de publicación20-jul-2004
EditorAmerican Chemical Society
CitaciónJournal of the American Chemical Society 126(31): 9809-9820 (2004)
ResumenThe gas phase reaction between formic acid and hydroxyl radical has been investigated with high level quantum mechanical calculations using DFT-B3LYP, MP2, CASSCF, QCISD, and CCSD(T) theoretical approaches in connection with the 6-311+G(2df,2p) and aug-cc-pVTZ basis sets. The reaction has a very complex mechanism involving several elementary processes, which begin with the formation of a reactant complex before the hydrogen abstraction by hydroxyl radical. The results obtained in this investigation explain the unexpected experimental fact that hydroxyl radical extracts predominantly the acidic hydrogen of formic acid. This is due to a mechanism involving a proton coupled electron-transfer process. The calculations show also that the abstraction of formyl hydrogen has an increased contribution at higher temperatures, which is due to a conventional hydrogen abstraction radical type mechanism. The overall rate constant computed at 298 K is 6.24 × 10-13 cm3 molecules-1 s-1, and compares quite well with the range from 3.2 ± 1 to 4.9 ± 1.2 × 10-13 cm3 molecules-1 s-1, reported experimentally.
Descripción12, pages, 5 figures, 2 schemes, 2 tables.-- PMID: 15291585 [PubMed].-- Printed version published Aug 11, 2004.-- Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/ja0481169
Versión del editorhttp://dx.doi.org/10.1021/ja0481169
ISSN0002-7863 (Print)
1520-5126 (Online)
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