Product study of the OH, NO3, and O3 initiated atmospheric photooxidation of propyl vinyl ether

Environ Sci Technol. 2006 Sep 1;40(17):5415-21. doi: 10.1021/es0605422.

Abstract

A product study is reported on the gas-phase reactions of OH and NO3 radicals and ozone with propyl vinyl ether (PVE). The experiments were performed in a 405 L borosilicate glass chamber in synthetic air at 298 +/- 3 K using long path in situ FTIR spectroscopy for the analysis of the reactants and products. In the presence of NO(x) (NO + NO2) the main products for the OH-radical initiated oxidation of PVE were propylformate and formaldehyde with molar formation yields of 78.6 +/- 8.8% and 75.9 +/- 8.4%, respectively. In the absence of NO(x) propylformate and formaldehyde were formed with molar formation yields of 63.0 +/- 9.0% and 61.3 +/- 6.3%, respectively. In the reaction of NO3 radicals with PVE propylformate 52.7 +/- 5.9% and formaldehyde 55.0 +/- 6.3% were again observed as major products. The ozonolysis of PVE led to the production of propylformate, formaldehyde, hydroxyperoxymethyl formate (HPMF; HC(O)OCH2OOH), and CO with molar formation yields of 89.0 +/- 11.4%, 12.9 +/- 4.0%, 13.0 +/- 3.4%, and 10.9 +/- 2.6%, respectively. The formation yield of OH radicals in the ozonolysis of PVE was estimated to be 17 +/- 9%. Simple atmospheric degradation mechanisms are postulated to explain the formation of the observed products.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Atmosphere
  • Hydroxyl Radical / chemistry*
  • Nitric Oxide / chemistry*
  • Oxidation-Reduction
  • Ozone / chemistry*
  • Photochemistry
  • Vinyl Compounds / chemistry*

Substances

  • Vinyl Compounds
  • propyl vinyl ether
  • Nitric Oxide
  • Hydroxyl Radical
  • Ozone