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Title

Mechanism for the gas-phase reaction between formaldehyde and hydroperoxyl radical. A theoretical study

AuthorsAnglada Rull, Josep M.; Domingo, Víctor M.
KeywordsGas-phase reaction
Formaldehyde
Hydroperoxyl radical
Hydrogen abstraction
Pre-reactive complexes
Issue Date3-Nov-2005
PublisherAmerican Chemical Society
CitationJournal of Physical Chemistry A 109(47): 10786–10794 (2005)
AbstractWe present a high-level theoretical study on the gas-phase reaction between formaldehyde and hydroperoxyl radical carried out using the DFT-B3LYP, QCISD, and CCSD(T) theoretical approaches in connection with the 6-311+G(d,p), 6-311+G(2df,2p), and aug-cc-pVTZ basis sets. The most favorable reaction path begins with the formation of a pre-reactive complex and produces the peroxy radical CH2(OO)OH in a process that is computed to be exothermic by 16.8 kcal/mol. This reaction involves a process in which the oxygen terminal of the HO2 moiety adds to the carbon of formaldehyde, and, simultaneously, the hydrogen of the hydroperoxyl group is transferred to the oxygen of the carbonyl in a proton-coupled electron-transfer mechanism. Our calculations show that this transition state lies below the sum of the energy of the reactants, and we computed a rate constant at 300 K of 9.29 × 10-14 cm3 molecule-1 s-1, which is in good agreement with the experimental results. Also of interest in combustion chemistry, we studied the hydrogen abstraction process by HO2, the result of which is the formation of HCO + H2O2. We found two reaction paths with activation enthalpies close to 12 kcal/mol. For this process, we computed a rate constant of 1.48 × 10-16 cm3 molecule-1 s-1 at 700 K, which also agrees quite well with experimental results.
Description9 pages, 4 figures, 4 tables.-- PMID: 16863128 [PubMed].-- Printed version publidshed Dec 1, 2005.-- Supporting information available at: http://pubs.acs.org/doi/suppl/10.1021/jp054018d
Publisher version (URL)http://dx.doi.org/10.1021/jp054018d
URIhttp://hdl.handle.net/10261/15683
DOI10.1021/jp054018d
ISSN1089-5639
E-ISSN1520-5215
Appears in Collections:(IQAC) Artículos

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