Simulated kinetics of the atmospheric removal of aniline during daytime

Chemosphere. 2020 Sep:255:127031. doi: 10.1016/j.chemosphere.2020.127031. Epub 2020 May 10.

Abstract

Oxidations of aniline (AN) initiated by OH-radicals are simulated in the temperature range 200-400 K using DFT/M06-2X/6-311++G(2df,2p) and ab initio ROCBS-QB3 levels. Chemical kinetics of such reactions were investigated based on several approaches including classical transition state theory (TST), conical variational transition state theory (CVT), and Rice-Ramsperger-Kassel-Marcus master equation (RRKM-ME) theories. Under atmospheric conditions, the reaction of OH radical with AN and the subsequent reactions with O2 molecules are investigated. The results indicate that the majority of O2 addition goes to the anti-directions with a branching ratio of 97.7% and produces the bicyclic peroxy radicals (BPRs) that can react with NO radical to form bicyclic alkoxy radicals (BARs). The latter compounds can be stabilized either by cyclization or via ring cleavage.

Keywords: Ab initio; Aniline; Atmospheric oxidation; DFT; Kinetics; OH radicals.

MeSH terms

  • Air Pollutants / analysis*
  • Aminophenols / analysis
  • Aniline Compounds / analysis*
  • Atmosphere / chemistry*
  • Hydroxyl Radical / chemistry*
  • Kinetics
  • Models, Theoretical*
  • Nitrobenzenes / analysis
  • Oxidation-Reduction
  • Photoperiod
  • Temperature

Substances

  • Air Pollutants
  • Aminophenols
  • Aniline Compounds
  • Nitrobenzenes
  • 2-aminophenol
  • Hydroxyl Radical
  • nitrobenzene
  • aniline