Ab initio and kinetic modeling studies of formic acid oxidation

Paul Marshall, Peter Glarborg

Research output: Contribution to journalJournal articleResearchpeer-review

Abstract

A detailed chemical kinetic model for oxidation of formic acid (HOCHO) in flames has been developed, based on theoretical work and data from literature. Ab initio calculations were used to obtain rate coefficients for reactions of HOCHO with H, O, and HO2. Modeling predictions with the mechanism have been compared to the experimental results of de Wilde and van Tiggelen (1968) who measured the laminar burning velocities for HOCHO flames over a range of stoichiometries and dilution ratios. The modeling predictions are generally satisfactory. The governing reaction mechanisms are outlined based on calculations with the kinetic model. Formic acid is consumed mainly by reaction with OH, yielding OCHO, which dissociates rapidly to CO2 + H, and HOCO, which may dissociate to CO + OH or CO2 + H, or react with H, OH, or O2 to form more stable products. The branching fraction of the HOCHO + OH reaction, as well as the fate of HOCO, determines the oxidation rate of formic acid. At lower temperatures HO2, formed from HOCO + O2, is an important chain carrier and modeling predictions become sensitive to the HOCHO + HO2 reaction. © 2014 The Combustion Institute.
Original languageEnglish
JournalProceedings of the Combustion Institute
Volume35
Issue number1
Pages (from-to)153–160
Number of pages8
ISSN1540-7489
DOIs
Publication statusPublished - 2015

Keywords

  • Mechanical Engineering
  • Physical and Theoretical Chemistry
  • Chemical Engineering (all)
  • Ab initio calculations
  • flame speed
  • Formic acid
  • Kinetic model

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