Theoretical investigation on the mechanisms and kinetics of OH/NO3-initiated atmospheric oxidation of vanillin and vanillic acid

Abstract

Vanillin and vanillic acid are two kinds of lignin pyrolysis products that are generated by biomass combustion. The gas-phase oxidation mechanisms of vanillin and vanillic acid initiated by OH/NO3 radicals were investigated by using density functional theory (DFT) at M06–2X/6-311+G(3df,2p)//M06–2X/6-311+G(d,p) level. The initial reactions of vanillin and vanillic acid with OH/NO3 radicals can be divided into two patterns: OH/NO3 addition and H-atom abstraction. For vanillin reacted with OH radical, the OH addition mainly occurs at C2-position to produce highly chemically activated intermediate (IM2). The oxidation products 3,4-dihydroxy benzaldehyde, malealdehyde, methyl hydrogen oxalate, methylenemalonaldehyde, carbonyl and carbonyl compounds are formed by the subsequent reactions of IM2. H-atom abstracting from aldehyde group occurs more easily than from the other positions. In addition, vanillin reacting with NO3 radicals principally proceeds via NO3-addition at C1 sites and H-atom abstracting from OH group (C1) to generate HNO3. The primary reaction mechanisms of vanillic acid with OH/NO3 radicals were similar to vanillin. The Rice-Ramsperger-Kassel-Marcus (RRKM) theory was performed to calculate the rate constants of the significant elementary reactions. The total rate constants for OH-initiated oxidation of vanillin and vanillic acid are 5.72 × 10−12 and 5.40 × 10−12 cm3 molecule−1 s−1 at 298 K and 1 atm. The atmospheric lifetimes were predicted to be 48.56 h and 51.44 h, respectively. As a supplement, the kinetic calculations of NO3 radicals with two reactants were also discussed. This work investigates the atmospheric oxidation processes of vanillin and vanillic acid, and hopes to provide useful information for further experimental research.