Alkene Reaction With Ozone

33 Pages·2002·0.07 MB·English

by  Jill Nomura

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