Overhead Slides for Chapter 12, Part 2 of Fundamentals of Atmospheric Modeling by Mark Z. Jacobson Department of Civil & Environmental Engineering Stanford University Stanford, CA 94305-4020 January 30, 2002 Alkene Reaction With Ozone Ethene H H O 37% C O + C O H H H H O C C + O Formaldehyde Criegee biradical 3 O O H H H H O* H2C CH2 63% C O + C O H H Ethene Ethene molozonide Formaldehyde Excited Criegee biradical (12.89) Criegee biradical reaction + NO H H O C O C O H H NO Criegee biradical 2 Formaldehyde (12.90) Excited criegee biradical decomposition 60% CO + H O 2 H O* H C O C O 21% CO + H 2 2 H H O* + O 2 Excited Criegee Excited formic 19% CO + OH + HO2 biradical acid (12.91) Alkene Reaction With Ozone Propene H H C 3 O 7.5% C O + C O H H Formaldehyde Methyl criegee biradical H H3C O* C O + C O 42.5% H H O H Formaldehyde Excited methyl criegee O O C CH + O biradical 2 3 H C CH CH H C H 3 2 3 O H C 3 C O + C O 18.5% H H Propene Propene molozonide Acetaldehyde Criegee biradical H C H 3 O* C O + C O 33.5% H H Acetaldehyde Excited criegee biradical (12.92) Alkene Reaction With Ozone Methylcriegee biradical reaction + NO H C H C 3 O 3 C O C O H H NO 2 Methyl criegee Acetaldehyde biradical (12.93) Excited methylcriegee biradical decomposition 16% CH + CO 4 2 H3C O* H3C C O C O 64% CH + CO + OH 3 H H O* 20% CH O + HO + CO 3 2 Excited methyl criegee Excited acetic biradical acid (12.94) Alkene Reaction With Nitrate Ethene --> nitrated organic radicals O O O + NO O H H + NO3 H O N + O2 H O O N H O O N C C C CH O C CH O C CH O H H 2 2 2 H H NO H 2 Ethene Ethyl nitrate radical Ethylperoxy nitrate Ethoxy nitrate radical radical (12.95) Propene --> nitrated organic radicals O O O O + NO H H + NO3 H O N + O2 H O O N H O O N H C C C H C CH2 O C CH2 O C CH2 O 3 H3C H3C NO H3C 2 Propene Propyl nitrate radical Propylperoxy nitrate Propoxy nitrate radical radical (12.96) Aromatic Reaction With Hydroxyl Radical Toluene oxidation CH 2 H C O O 2 + O + OH 2 Benzylperoxy 8% radical H O 2 Benzyl O CH radical 3 O CH H 3 OH CH 3 Toluene-hydroxyl- + O + OH H 2 radical adduct Toluene 92% OH CH 3 OH o-Hydroxytoluene + HO 2 o-Cresol (12.97) Aromatic Reaction With Hydroxyl Radical Benzylperoxy radical reaction with NO H2C O O CH + NO + O 2 NO HO H C O O 2 2 2 Benzoxy Benzaldehyde radical O H C O N 2 + NO O Benzylperoxy radical Benzyl nitrate (12.98) Toluene-hydroxyl radical adduct reaction O CH CH O 3 3 O + NO H H OH OH NO 2 Toluene-hydroxyl radical adduct (12.99) Fate of Cresol Cresol --> methylphenylperoxy radical and nitrocresol CH 3 + OH, 2O 2 O O CH 3 2HO 2 OH Methylphenylperoxy radical CH 3 CH 3 OH + OH o-Cresol O + NO2 O N H O 2 O Methylphenoxy m-Nitrocresol radical (12.100) Terpene Reaction With OH HO HO CH CH H 3 3 C C CH C O (4) O (1) O C CH 23.6% H2C C O 16.4% H 2 H 2 2 O O CH O HC C 3 + OH, O2 (2) O CH3 (5) H CH3 12.3% HO CH C 21.2% C C OH H2C CH2 C CH H2C C H 2 H 2 2 Isoprene H CH3 (6) H CH3 (3) 12.3% HO C C CC O O 14.1% O O C C CC OH H2 H2 H2 H2 Isoprene peroxy radicals (12.101) All six products convert NO to NO 2 Terpene Reaction With OH Methacrolein production via second product (12.102) O O CH + NO + O2 H CH3 H 3 CH C C C + C O HO C CH O CH2 H H2 2 NO2 HO2 Isoprene peroxy radical Methacrolein Formaldehyde Methylvinylketone production via fifth product (12.103) O H O CH3 + NO + O2 H CH3 H C C C C + C O OH H C C H2C O H 2 H NO HO 2 2 2 Isoprene peroxy radical Methylvinylketone Formaldehyde