A Modeling Study of Tropospheric Ozone and its Precursors
in Winter–Spring Arctic Outflow
By
Amy J. Hamlin
A DISSERTATION
Submitted in partial fulfillment of the requirements
for the degree of
DOCTOR OF PHILOSOPHY
(Engineering-Environmental)
MICHIGAN TECHNOLOGICAL UNIVERSITY
April 2002
This dissertation, “A Modeling Study of Tropospheric Ozone and its Precursors
in Winter–Spring Arctic Outflow,” is hereby approved in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY in the field of EngineeringEnvironmental.
PROGRAM Engineering-Environmental
Dr. Richard E. Honrath, Dissertation Advisor
Dr. John C. Crittenden, Program Chair
Date
Abstract
The purpose of this study is to determine the impact of winter–spring arctic outflow events
on the budgets of tropospheric NOx and ozone over the North Atlantic Ocean. Arctic
air contains elevated levels of peroxyacetyl nitrate (PAN) and non-methane hydrocarbons
during the winter–spring period; as this air flows southward, it subsides and experiences
an increase in temperature, resulting in release of NOx through thermal decomposition of
PAN. In combination with increased ultraviolet radiation as the air flows south, NOx release
results in the potential for net photochemical ozone production.
An updated version of the NCAR Master Mechanism, a detailed, explicit photochemical
model, is applied to trajectories representative of arctic outflow for the months of January
through May. Revisions were made to the gas-phase mechanism in small increments to
determine the effect of each set of revisions on simulated levels of NOx and O3 . To
determine the impact of accumulated pollutants in arctic air, two simulations are run for
each trajectory, with different initial levels of PANs (PAN and its homologs). In the first
simulation, the initial levels of PANs are typical for that month in arctic air; in the second,
initial [PANs] are set equal to zero. The difference between these simulations reflects the
effect of the elevated levels of PAN present in arctic air. This difference is used to estimate
the flux of NOx and O3 to the North Atlantic region resulting from arctic outflow.
The mechanism revisions which have the largest effect on the average levels of NOx
and O3 are the photolysis, peroxy radical, and PAN reactions. In comparison to the original
mechanism, the overall net effect of including all the revisions was a 10.3% and 0.3%
decrease in the average levels of NOx and O3 respectively, and a 38% decrease (0.35 ppb/d)
in the average net rate of ozone production. However, the effect of individual revision
subsets had a much larger effect as they have opposing effects and counteract each other.
The peroxy radical revisions had the largest effect on the level of NOx , increasing the
average level by 24% over the original mechanism. For O3 , the photolysis revisions had
the largest effect, decreasing the average level by 1% and reducing the net rate of ozone
iii
production by 0.5 ppb/day, a 49% reduction. The results indicate that revising only a few
reactions may be worse than not revising any at all. Therefore, it is important that the
impact of revisions to individual (or a family of) reactions are clearly understood, so that
possible bias in calculated results can be avoided.
During simulations of arctic outflow, peroxyacetyl nitrate (PAN) mixing ratios drop by
up to 270 pptv, increasing NOx levels up to 120 pptv. However, the released NOx is quickly
destroyed by efficient NOx loss reactions leading to formation of HNO3 and, to a lesser
extent, nitroaromatic compounds. As a result of elevated NOx , O3 levels are increased.
The net impact resulting from elevated levels of PANs in the winter–spring Arctic on the
budget of O3 over the North Atlantic is estimated to be less than 712 Gg O3 /month. While
this source is similar in magnitude to estimates of ozone produced from aircraft emissions,
both are small in comparison to the export of ozone from North America. In conclusion,
while elevated levels of pollutants in arctic outflow increase the levels of NOx and O3 in the
North Atlantic region, on a seasonal basis the impact on the budgets of NOx and O3 in this
region is small.
iv
Acknowledgments
I wish to extend my gratitude to everyone who has contributed to this work. In particular
I would like to thank my graduate advisor, Dr. Richard Honrath, for his guidance and
support throughout this research. In addition, I would also like to thank the other members
of my graduate advisory committee—Dr. Gregg Bluth, Dr. Sarah Green, and Dr. Alex
Mayer. I am grateful to Sasha Madronich (National Center for Atmospheric Research)
for providing his photochemical model, the NCAR Master-Mechanism and to Jonathan
Williams (Max-Planck Institute for Chemistry) for sharing improvements he made to the
Master-Mechanism. I thank Arve Kylling (Norwegian Institute for Air Research) for
supplying his radiative transfer models Phodis-Version 0.30 and Phodis-Version-0.40. I
thank the National Oceanic and Atmospheric Administration, Michigan Technological
University, and the Charles DeVlieg Foundation for financial support. The students, faculty,
and staff have made my experiences at Michigan Tech enjoyable and they will not be
forgotten, thank you. A very special thank you goes to my family for their support, their
encouragement, and their belief in my abilities.
v
Contents
Abstract
iii
Acknowledgments
v
List of Figures
ix
List of Tables
xiii
1
2
Introduction
1
1.1
Objective
1.2
Dissertation Overview
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
: : : : : : : : : : : : : : : : : : : : : : : : : : :
4
4
Effect of New Photochemical Rate Parameters on Simulated NOx and O3
6
2.1
Introduction
6
2.2
Model Description
2.3
Model Revisions and Their Effect on NOx and O3
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
: : : : : : : : : : : : : : : : : : : : : : : : : : : : :
7
: : : : : : : : : : : : :
11
2.3.1
Photolysis Revisions
: : : : : : : : : : : : : : : : : : : : : : : :
12
2.3.2
Inorganic Revisions
: : : : : : : : : : : : : : : : : : : : : : : :
16
2.3.3
Organic Reactions
: : : : : : : : : : : : : : : : : : : : : : : : :
20
2.3.3.1
Unsubstituted Hydrocarbons
: : : : : : : : : : : : : :
21
2.3.3.2
Radicals
: : : : : : : : : : : : : : : : : : : : : : : : :
23
2.3.3.3
Oxygen Containing Organic Compounds
vi
: : : : : : : :
36
2.3.4
2.4
3
Nitrogen Containing Organic Compounds
: : : : : : :
39
2.3.3.5
Aromatic Compounds
: : : : : : : : : : : : : : : : : :
43
: : : : : : : : : : : : : : : : : : : : :
48
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
54
Comparison of Revisions
Conclusions
Impact of Winter–Spring Arctic Outflow on the NOx and O3 Budgets of the
North Atlantic Troposphere
56
3.1
Model Description
57
3.2
Results and Discussion :
: : : : : : : : : : : : : : : : : : : : : : : : : :
65
3.2.1
: : : : : : : : : : : : : : : : : : : : : : : : : :
65
3.3
4
2.3.3.4
: : : : : : : : : : : : : : : : : : : : : : : : : : : : :
Nitrogen Oxides
3.2.1.1
Sources of NOx
3.2.1.2
Sinks of NOx
: : : : : : : : : : : : : : : : : : : : :
65
: : : : : : : : : : : : : : : : : : : : : :
70
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
79
3.2.2
Ozone
3.2.3
Flux of NOx and O3
Summary and Conclusions
: : : : : : : : : : : : : : : : : : : : : : : :
86
: : : : : : : : : : : : : : : : : : : : : : : : :
93
Summary and Conclusions
95
References
98
A Chemical Codes
111
B Mechanism Revisions: Discussion
157
B.1 Non-Troe Reactions
B.1.1
B.1.2
: : : : : : : : : : : : : : : : : : : : : : : : : : : :
Inorganic Chemistry
: : : : : : : : : : : : : : : : : : : : : : : :
B.1.1.1
Odd Oxygen
B.1.1.2
Odd Hydrogen
B.1.1.3
Inorganic Nitrogen Species
Organic Reactions
B.1.2.1
158
158
: : : : : : : : : : : : : : : : : : : : : :
158
: : : : : : : : : : : : : : : : : : : : :
158
: : : : : : : : : : : : : : :
159
: : : : : : : : : : : : : : : : : : : : : : : : :
159
Unsubstituted Hydrocarbons
vii
: : : : : : : : : : : : : :
159
B.1.2.2
Alkyl Radicals
B.1.2.3
Peroxy Radical Reactions
B.1.2.4
Alkoxy Radicals
B.1.2.5
Oxygen Containing Organics
B.1.2.6
Nitrogen Containing Organics
B.1.2.7
Aromatics
: : : : : : : : : : : : : : : : : : : : :
160
: : : : : : : : : : : : : : : :
160
: : : : : : : : : : : : : : : : : : : :
168
: : : : : : : : : : : : : :
171
: : : : : : : : : : : : :
174
: : : : : : : : : : : : : : : : : : : : : : : :
178
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
183
B.3 Photolysis
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
183
B.3.1
Ox
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
184
B.3.2
Hydroperoxides
B.3.3
Odd Nitrogen
B.3.4
Carbonyls
B.2 Troe Reactions
B.3.5
: : : : : : : : : : : : : : : : : : : : : : : : : :
184
: : : : : : : : : : : : : : : : : : : : : : : : : : :
186
: : : : : : : : : : : : : : : : : : : : : : : : : : : : :
198
: : : : : : : : : : : : : : : : : : : : : : :
198
: : : : : : : : : : : : : : : : : : : : : : : : :
211
B.3.4.1
Aldehydes :
B.3.4.2
Ketones
B.3.4.3
Unsaturated Carbonyls
Acids
: : : : : : : : : : : : : : : : :
214
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
215
C Mechanism Revisions: Tables
216
viii
List of Figures
2.1
Forward isentropic trajectory along which simulations were performed
: :
9
2.2
Effect of photolysis revisions on NOx levels
: : : : : : : : : : : : : : : :
14
2.3
Effect of photolysis revisions on O3 levels
: : : : : : : : : : : : : : : : :
14
2.4
Effect of inorganic revisions on NOx levels
: : : : : : : : : : : : : : : :
16
2.5
Effect of inorganic revisions on O3 levels
: : : : : : : : : : : : : : : : :
17
2.6
Effect of inorganic nitrogen revisions on NOx levels :
2.7
Effect of inorganic nitrogen revisions on O3 levels
2.8
Effect of inorganic nitrogen revisions on the levels of NO3
: : : : : : : :
19
2.9
Effect of inorganic nitrogen revisions on the levels of N2 O5
: : : : : : : :
19
: : : : : : :
20
2.11 Effect of revisions to unsubstituted hydrocarbon reactions on levels of NOx
21
2.12 Effect of revisions to unsubstituted hydrocarbon reactions on O3 levels
: :
22
2.13 Effect of revisions to peroxy radical reactions with NO on NOx levels
: :
25
: : :
26
: : : : : : : : : : :
18
: : : : : : : : : : : : :
18
2.10 Effect of inorganic nitrogen revisions on the levels of HNO3
2.14 Effect of revisions to peroxy radical reactions with NO on O3 levels
2.15 Effect of revisions to peroxy radical reactions with HO2 on NOx levels
2.16 Effect of revisions to peroxy radical reactions with HO2 on O3 levels
: :
27
: : :
27
2.17 Effect of revisions to peroxy radical reactions with NO3 on NOx levels
: :
29
: : :
30
: : : :
32
: : : : :
32
2.18 Effect of revisions to peroxy radical reactions with NO3 on O3 levels
2.19 Effect of revisions to peroxy radical cross reactions on NOx levels
2.20 Effect of revisions to peroxy radical cross reactions on O3 levels
ix
2.21 Effect of revisions to peroxy acyl radical reactions on PAN levels
: : : : :
33
2.22 Effect of revisions to peroxy acyl radical reactions on peroxyacetyl radical
levels
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
2.23 Effect of revisions to peroxy acyl radical reactions on NOx levels
2.24 Effect of revisions to peroxy acyl radical reactions on O3 levels
34
: : : : :
35
: : : : : :
35
2.25 Effect of revisions to peroxy acyl nitrate reactions on PAN levels
: : : : :
40
2.26 Effect of revisions to peroxy acyl nitrate reactions on NOx levels
: : : : :
41
2.27 Effect of revisions to peroxy acyl nitrate reactions on peroxyacetyl radical
levels
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
2.28 Effect of revisions to peroxy acyl nitrate reactions on O3 levels
: : : : : :
42
: : : : : : : :
43
: : : : : : : : :
44
: : : : : : : : : : : : :
45
2.29 Effect of revisions to alkyl nitrate reactions on NOx levels :
2.30 Effect of revisions to alkyl nitrate reactions on O3 levels :
2.31 Effect of aromatic revisions on nitrophenol levels
2.32 Effect of aromatic revisions on dinitrophenol levels
: : : : : : : : : : : :
45
: : : : : : : : : : : : : : : :
46
: : : : : : : : : : : : : : : : :
46
: : : : : : : : : : : : : : : : : :
49
: : : : : : : : : : : : : : : : : : :
49
2.33 Effect of aromatic revisions on NOx levels :
2.34 Effect of aromatic revisions on O3 levels :
2.35 Effect of revision subsets on NOx levels
2.36 Effect of revision subsets on O3 levels
41
2.37 Effect of adding revision subsets on O3 levels
: : : : : : : : : : : : : : :
2.38 Effect of adding revision subsets on NOx levels
: : : : : : : : : : : : : :
2.39 Effect of revising only a few reactions within each subset on NOx levels
51
51
:
53
: :
53
: : : : : : : : : : : : : : : : : : : : : : : : : : : :
59
: : : : : : : : : : : : : : : : : : : : : : : : : : : : :
60
2.40 Effect of revising only a few reactions within each subset on O3 levels
3.1
January Trajectories
3.2
March Trajectories
3.3
May Trajectories
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
61
3.4
NOy Speciation
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
66
3.5
Comparison of NOy groups as sources and sinks of NOx
x
: : : : : : : : :
68
3.6
Mechanism of benzene oxidation
: : : : : : : : : : : : : : : : : : : : :
74
3.7
Mechanism of phenol oxidation
: : : : : : : : : : : : : : : : : : : : : :
76
3.8
Average net rates of NOx production and destruction for March and May
high-PAN-decomposition simulations
3.9
: : : : : : : : : : : : : : : : : : :
Ozone mixing ratios for the January, March, and May simulations
: : : :
80
81
3.10 Effect of extending the March-high-PAN-decomposition simulation on NOy
speciation
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
88
3.11 Effect of extending the March-high-PAN-decomposition simulation on the
levels of O3
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
88
3.12 Effect of extending the May high-PAN-decomposition simulation on NOy
speciation
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
B.1 CH3 OOH Absorption Cross Section
: : : : : : : : : : : : : : : : : : : :
187
: : : : : : : : : : : : : : : : : : : : : :
188
: : : : : : : : : : : : : : : : : : : : : : : : : : : :
188
B.2 NO2 Absorption Cross Section :
B.3 NO2 Quantum Yield
B.4 NO3 Absorption Cross Section :
: : : : : : : : : : : : : : : : : : : : : :
B.5 NO3 QY: Johnston et al., 1996 vs Madronich
B.6 N2 O5 Quantum Yield
89
189
: : : : : : : : : : : : : : :
190
: : : : : : : : : : : : : : : : : : : : : : : : : : :
191
B.7 HNO2 Absorption Cross Section
: : : : : : : : : : : : : : : : : : : : : :
192
B.8 HNO4 Absorption Cross Section
: : : : : : : : : : : : : : : : : : : : : :
193
B.9 PAN Absorption Cross Section
: : : : : : : : : : : : : : : : : : : : : :
194
B.10 Methyl Nitrate Absorption Cross Section, logarithmic
B.11 Ethyl Nitrate Absorption Cross Section
: : : : : : : : : : :
195
: : : : : : : : : : : : : : : : : :
195
B.12 Ethyl Nitrate Absorption Cross Section, logarithmic
: : : : : : : : : : : :
196
B.13 Propyl Nitrate Absorption Cross Section, logarithmic
: : : : : : : : : : :
197
B.14 Propyl Nitrate Absorption Cross Section, logarithmic
: : : : : : : : : : :
197
: : : : : : : : : : : : : : : : :
199
B.15 Methyl Nitrite Absorption Cross Section
B.16 CH2 O Absorption Cross Section as a Function of Temperature
xi
: : : : : :
200
B.17 CH2 O Absorption Cross Section
: : : : : : : : : : : : : : : : : : : : : :
200
B.18 CH2 O Channel A Quantum Yield
: : : : : : : : : : : : : : : : : : : : :
201
B.19 CH2 O Channel B Quantum Yield
: : : : : : : : : : : : : : : : : : : : :
202
B.20 CH3 CHO Absorption Cross Section
: : : : : : : : : : : : : : : : : : : :
203
B.21 CH3 CHO Absorption Cross Section
: : : : : : : : : : : : : : : : : : : :
203
: : : : : : : : : : : : : : : : : : : : : : : : :
204
B.22 CH3 CHO Quantum Yield
B.23 Propanal (d031) Absorption Cross Section :
B.24 Propanal (d031) Quantum Yield
: : : : : : : : : : : : : : : :
205
: : : : : : : : : : : : : : : : : : : : : :
205
: : : : : : : : : : : : : : : :
206
B.26 n-butanal (d041) Quantum Yield, Channel A
: : : : : : : : : : : : : : :
207
B.27 n-butanal (d041) Quantum Yield, Channel B :
: : : : : : : : : : : : : : :
207
: : : : : : : : : : : : : : : :
208
: : : : : : : : : : : : : : : : : : : : :
209
B.25 n-Butanal (d041) Absorption Cross Section
B.28 i-Butanal (d042) Absorption Cross Section
B.29 Iso-butanal (d042) Quantum Yield
B.30 CHOCHO Absorption Cross Section
: : : : : : : : : : : : : : : : : : :
209
B.31 CH3 C(O)CHO Absorption Cross Section
: : : : : : : : : : : : : : : : :
210
B.32 Acetone (k031) Absorption Cross Section
: : : : : : : : : : : : : : : : :
211
: : : : : : : : : : : : : : : : : : : : : : : : : :
212
B.33 Acetone Quantum Yield
B.34 2-Butanone (k041) Absorption Cross Section
: : : : : : : : : : : : : : :
212
B.35 3-pentanone (k052) Absorption Cross Section
: : : : : : : : : : : : : : :
213
: : : : : : : : : : : : : : : : : : : :
214
B.36 Acrolein Absorption Cross Section
xii
List of Tables
2.1
Initial Conditions
2.2
Summary of Photolysis Cross-Sections
: : : : : : : : : : : : : : : : : :
13
2.3
Summary of Photolysis Quantum Yields
: : : : : : : : : : : : : : : : : :
15
2.4
Alkyl and Alkoxy Radical Reactions :
: : : : : : : : : : : : : : : : : : :
23
2.5
Alkyl Peroxy Radical Rate Constants for Reaction with HO2
2.6
Carbonyl Reaction Revisions
2.7
Alcohol Reactions
2.8
Hydroperoxide Reactions
2.9
Revised Aromatic Reactions
: : : : : : : : : : : : : : : : : : : : : : : : : : : : :
: : : : : : :
28
: : : : : : : : : : : : : : : : : : : : : : :
37
: : : : : : : : : : : : : : : : : : : : : : : : : : : : :
38
: : : : : : : : : : : : : : : : : : : : : : : : :
: : : : : : : : : : : : : : : : : : : : : : : :
2.10 Change in Mean NOx and O3 Levels for each Group of Revisions
: : : : :
2.11 Rates of Ozone Production and Destruction for each Group of Revisions
38
47
48
:
50
: : : : : : : : : : : : :
52
: : : : : : : : : : : : : : : : : : : : : : : : : : : : :
63
2.12 Important Reactions in Each Group of Revisions
3.1
Initial Conditions
3.2
Initial Conditions Continued
3.3
Ozone Production Rates
3.4
Ozone Loss Rates
3.5
Source of NOx and O3 to North Atlantic Resulting from elevated PANs in
the Arctic
10
: : : : : : : : : : : : : : : : : : : : : : : :
64
: : : : : : : : : : : : : : : : : : : : : : : : : :
83
: : : : : : : : : : : : : : : : : : : : : : : : : : : : :
85
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
3.6
Comparison of NOx Sources to the North Atlantic Troposphere
3.7
Comparison of O3 Sources to the North Atlantic Troposphere
xiii
86
: : : : : :
90
: : : : : : :
91
A.1 Functional Groups
: : : : : : : : : : : : : : : : : : : : : : : : : : : : :
111
A.2 Chemical Codes: 0031–1081
: : : : : : : : : : : : : : : : : : : : : : :
113
A.3 Chemical Codes: 1a21–1e71 :
: : : : : : : : : : : : : : : : : : : : : : :
114
A.4 Chemical Codes: 1f14–1m33
: : : : : : : : : : : : : : : : : : : : : : :
115
A.5 Chemical Codes: 1n11–1o54
: : : : : : : : : : : : : : : : : : : : : : :
116
A.6 Chemical Codes: 1o56–1v34
: : : : : : : : : : : : : : : : : : : : : : :
117
A.7 Chemical Codes: 2011–2d49
: : : : : : : : : : : : : : : : : : : : : : :
118
A.8 Chemical Codes: 2d50–2k71
: : : : : : : : : : : : : : : : : : : : : : :
119
A.9 Chemical Codes: 2l11–2nA1
: : : : : : : : : : : : : : : : : : : : : : :
120
A.10 Chemical Codes: 2o11–2p31
: : : : : : : : : : : : : : : : : : : : : : :
121
A.11 Chemical Codes: 2r61–3d48
: : : : : : : : : : : : : : : : : : : : : : : :
122
A.12 Chemical Codes: 3d51–3n49
: : : : : : : : : : : : : : : : : : : : : : :
123
A.13 Chemical Codes: 3n51–3u53
: : : : : : : : : : : : : : : : : : : : : : :
124
A.14 Chemical Codes: 3v21–7dA1
: : : : : : : : : : : : : : : : : : : : : : :
125
A.15 Chemical Codes: 7k32–8k33
: : : : : : : : : : : : : : : : : : : : : : :
126
: : : : : : : : : : : : : : : : : : : : : : : :
127
: : : : : : : : : : : : : : : : : : : : : : :
128
: : : : : : : : : : : : : : : : : : : : : : : : :
129
A.16 Chemical Codes:8k40–8o35
A.17 Chemical Codes: 8o41–BRO
A.18 Chemical Codes: C–F142
A.19 Chemical Codes: F21–MECN
A.20 Chemical Codes: N–aa33
: : : : : : : : : : : : : : : : : : : : : : :
130
: : : : : : : : : : : : : : : : : : : : : : : : :
131
A.21 Chemical Codes: ad21–ak33 :
: : : : : : : : : : : : : : : : : : : : : : :
132
A.22 Chemical Codes: ak40–an55 :
: : : : : : : : : : : : : : : : : : : : : : :
133
A.23 Chemical Codes: ao22–av56 :
: : : : : : : : : : : : : : : : : : : : : : :
134
A.24 Chemical Codes: b011–dk36
: : : : : : : : : : : : : : : : : : : : : : :
135
A.25 Chemical Codes: dk40–do49
: : : : : : : : : : : : : : : : : : : : : : :
136
A.26 Chemical Codes: do50–en72
: : : : : : : : : : : : : : : : : : : : : : :
137
A.27 Chemical Codes: eo21–gd49
: : : : : : : : : : : : : : : : : : : : : : :
138
A.28 Chemical Codes: gd51–gn55
: : : : : : : : : : : : : : : : : : : : : : :
139
xiv
A.29 Chemical Codes: go22–gv62
: : : : : : : : : : : : : : : : : : : : : : :
140
A.30 Chemical Codes: h011–hd62
: : : : : : : : : : : : : : : : : : : : : : :
141
A.31 Chemical Codes: hh51–hnA1
: : : : : : : : : : : : : : : : : : : : : : :
142
A.32 Chemical Codes: ho11–hr62
: : : : : : : : : : : : : : : : : : : : : : : :
143
A.33 Chemical Codes: hr71–ko48
: : : : : : : : : : : : : : : : : : : : : : : :
144
A.34 Chemical Codes: ko50–1v02
: : : : : : : : : : : : : : : : : : : : : : :
145
A.35 Chemical Codes: m011–n081
: : : : : : : : : : : : : : : : : : : : : : :
146
A.36 Chemical Codes: nd11–nd81
: : : : : : : : : : : : : : : : : : : : : : :
147
A.37 Chemical Codes: nk23–no46
: : : : : : : : : : : : : : : : : : : : : : :
148
A.38 Chemical Codes: no4A–nu55
: : : : : : : : : : : : : : : : : : : : : : :
149
A.39 Chemical Codes: nv32–oo49
: : : : : : : : : : : : : : : : : : : : : : :
150
A.40 Chemical Codes: oo51–pd56
: : : : : : : : : : : : : : : : : : : : : : :
151
A.41 Chemical Codes: pg21–pn55
: : : : : : : : : : : : : : : : : : : : : : :
152
A.42 Chemical Codes: po22–pv56
: : : : : : : : : : : : : : : : : : : : : : :
153
A.43 Chemical Codes: q011–sw11
: : : : : : : : : : : : : : : : : : : : : : :
154
A.44 Chemical Codes: t0A1–uv31
: : : : : : : : : : : : : : : : : : : : : : :
155
A.45 Chemical Codes: vk21–wo11
: : : : : : : : : : : : : : : : : : : : : : :
156
: : : : : : : : : : : : : : : : : : : : : : : : : : :
161
B.1 Alkyl Radical Updates
B.2 Alkyl Peroxy Radical Rate Constants for Reaction with HO2
B.3 Activation Temperatures for Peroxy Radical Self Reactions
: : : : : : :
163
: : : : : : : :
166
B.4 Comparison of Alkyl Nitrate Branching Ratios for Reaction with HO
: : :
175
: : : : : : : : : : :
179
: : : : : : : : : : : :
181
: : : : : : : : : : :
181
: : : : : : : : : : : : : : : : : : : : : : : : :
182
: : : : : : : : : : : : : : : : : : : : : : : : : : : :
182
B.5 Rate constants for the Reaction of Benzene with OH
B.6 Rate Constants for the Reaction of Phenol with OH
B.7 Rate Constants for the Reaction of Phenol with NO3
B.8 2-nitrophenol (rv62) + OH
B.9 4-nitrophenol + OH
B.10 2-nitrophenol (rv62) + NO3
: : : : : : : : : : : : : : : : : : : : : : : :
xv
183
B.11 Summary of Photolysis Data
: : : : : : : : : : : : : : : : : : : : : : : :
B.12 Parameters for the O3 Quantum Yield Equation
C.1 Odd Oxygen Reactions
C.2 Odd Hydrogen Reactions
: : : : : : : : : : : : : :
185
: : : : : : : : : : : : : : : : : : : : : : : : : :
217
: : : : : : : : : : : : : : : : : : : : : : : : :
218
: : : : : : : : : : : : : : : : : : : : : : :
219
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
220
C.3 Inorganic Nitrogen Reactions
C.4 Organic Updates
185
C.5 Alkyl Radical Updates
: : : : : : : : : : : : : : : : : : : : : : : : : : :
C.6 Peroxy radical reaction with NO
: : : : : : : : : : : : : : : : : : : : : :
221
222
C.7 Peroxy radical reactions with HO2
: : : : : : : : : : : : : : : : : : : : :
237
C.8 Peroxy radical reactions with NO2
: : : : : : : : : : : : : : : : : : : : :
247
: : : : : : : : : : : : : : : : : : : : : : : : : : : :
250
C.9 Peroxy Radical NO3
C.10 Peroxy radical reaction with methyl peroxy radical
: : : : : : : : : : : :
250
: : : : : : : : : : : : : : : : : : : : : : :
267
: : : : : : : : : : : : : : : : : : : : : : : : : :
295
: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :
296
C.11 Peroxy radical cross reactions
C.12 Alkoxy radical reactions
C.13 Carbonyls
C.14 Oxygenated Organic Updates
: : : : : : : : : : : : : : : : : : : : : : :
297
: : : : : : : : : : : : : : : : : : : : : : : : :
298
: : : : : : : : : : : : : : : : : : : : : : : : : : :
299
C.15 Hydroperoxide Reactions
C.16 Alkyl Nitrate Updates
C.17 Peroxy Acyl Nitrate Updates
: : : : : : : : : : : : : : : : : : : : : : : :
300
C.18 Revised Aromatic Reactions
: : : : : : : : : : : : : : : : : : : : : : : :
303
: : : : : : : : : : : : : : : : : : : : : : : : : : :
304
C.19 Troe Reaction Updates
xvi
Chapter 1
Introduction
Ozone is an important trace gas in the troposphere. Its photolysis is the dominant source of
the hydroxyl radical (OH), which controls the lifetime of many compounds in the troposphere,
including methane, CO, and non-methane hydrocarbons (NMHC). As a greenhouse gas, ozone has
the potential to impact climate [Fishman et al., 1979]. Additionally, as a strong oxidant, ozone can
impair the health of plants and animals.
A major focus of atmospheric chemistry studies has been to understand the processes controlling
the production and destruction of tropospheric ozone. These processes include: photochemical
production and destruction, transport, and deposition. The sources of tropospheric ozone include
stratosphere-troposphere exchange (STE) and photochemical production. It was originally believed
that tropospheric ozone was controlled by transport from the stratosphere due to the observed
gradient of ozone with altitude. However, with the occurrence of a new type of “smog” in the
Los Angeles basin, a mechanism for photochemical ozone production was proposed in the 1950’s.
Today, both processes are considered important, with photochemical ozone production dominating
in photoactive regions of the atmosphere [Lelieveld and Dentener, 2000]. Global 3-D models [Wang
1
2
et al., 1998b] suggest that an overlap in the seasonal cycles of photochemical processes (peaking in
late spring) and STE (peaking in late winter) results in the spring peak in ozone levels observed at
remote northern extratropical surface sites. This study investigates the photochemical production
of ozone in the North Atlantic troposphere.
Three components are required for the photochemical production of tropospheric ozone: nitrogen oxides (NOx = NO+NO2 ), volatile organic compounds (VOC), and light (h ). The overall
reaction schematic for ozone formation is:
VOC + NOx
+
h ! O3
+ other
products
(1.1)
where other products include peroxyacetyl nitrate (PAN), alkyl nitrates, HNO3, CO2, and H2 O.
In the remote troposphere, ozone production is dependent on the level of NOx . Levels of NOx
in the remote troposphere are typically low, partially due to its short lifetime of 1-2 days, which
limits long-range transport. An important NOx reservoir is peroxyacetyl nitrate (PAN), formed by
the reaction of NO2 with peroxyacetyl radical. The peroxyacetyl radical is most commonly formed
from acetaldehyde (CH3 CHO), acetone (CH3 COCH3 ) and biacetyl (CH3 COCOCH3 ) [Singh, 1987].
In the presence of O2 and NO2 , these compounds can lead to the production of PAN [FinlaysonPitts and Pitts, 1999]. For example, PAN is produced from acetaldehyde in the following reaction
sequence:
CH3 CHO + OH
!
CH3 CO + H2 O
(1.2)
CH3 CO + O2 + M
!
CH3 C(O)OO + M
(1.3)
CH3 C(O)OO + NO2 + M
*
)
CH3 C(O)OONO2 + M:
(1.4)
PAN is stable at low temperatures, and has a lifetime up to several months in the colder regions
3
of the atmosphere, such as the mid to upper troposphere or high latitudes. As a result, PAN can
undergo long-range transport from source regions and ultimately release NOx through its thermal
decomposition (Reaction -1.4) [Crutzen, 1979; Singh and Hanst, 1981], providing a source of NOx
in regions distant from NOx emissions. Moxim et al. [1996] estimate that more than 70% of the
NOx over half the area of Northern Hemispheric oceans during late fall through spring is due to
thermal decomposition of PAN resulting from anticyclonic subsidence.
Previous measurements demonstrate there is a seasonal cycle of a variety of pollutants in the
Arctic, including total reactive nitrogen oxides (NOy ) [Honrath and Jaffe, 1992], PAN [Barrie, 1986;
Bottenheim and Gallant, 1989; Beine and Krognes, 2000], and hydrocarbons [Solberg et al., 1996a;
Laurila and Hakola, 1996; Ariya et al., 1998], with the maximum occurring during the the late
winter–early spring. PAN is the dominant form of NOy during late winter–early spring, accounting
for 60-80% of NOy [Muthuramu et al., 1994; Ridley et al., 2000]. As arctic air containing elevated
levels of PAN flows southward, it subsides and warms [Hamlin, 1995; Honrath et al., 1996], which
is expected to result in increased rates of PAN thermal decomposition, releasing NOx .
Barrie and Bottenheim [1991] and Honrath and Jaffe [1992] suggest arctic outflow events may
significantly impact mid–latitude regions during late winter and spring, possibly contributing to
the spring ozone peak observed at remote Northern Hemispheric sites. However, the impact of
arctic outflow on the mid-latitude troposphere remains unclear. On one hand, there is evidence
for a significant impact. Fenneteaux et al. [1999] document significant enhancement of PAN and
NMHC levels at the Tropospheric Ozone Research (TOR) site in Porspoder, France, associated
with southward flow of marine air from regions north of 50 N latitude. Honrath et al. [1996]
has suggested that elevated levels of NOy , primarily in the form of PAN, may contribute to the
4
spring tropospheric ozone peak observed in the remote Northern Hemisphere. Consistent with this,
Herring et al. [1997] observed significant ozone production at Poker Flat, Alaska during spring
1995 and attributed this to the high NOx levels observed (mean 116 pptv). On the other hand,
Wang et al. [1998b] concluded that the spring ozone peak is due to a combination of transport of
ozone from the stratosphere, which peaks in winter, and tropospheric ozone production, which in
the remote atmosphere peaks in late spring, with no contribution from winter accumulation at high
latitudes. In this study, we investigate the inconsistency in the role of high-latitude accumulation
on the mid-latitude troposphere.
1.1 Objective
The objective of this research is to determine the impact of winter-spring arctic outflow events on
the NOx and O3 budgets of the North Atlantic troposphere. To achieve this objective, the photochemical evolution within representative arctic outflow events will be simulated using Lagrangian,
photochemical box-model simulations.
1.2 Dissertation Overview
Chapter 2 describes the revisions made to the gas-phase chemical mechanism and the effect these
revisions have on NOx and O3 . Chapter 3 describes the simulations and analyses performed to
determine the impact of arctic outflow events on the NOx and O3 budgets of the North Atlantic
troposphere. Chapter 4 summarizes the main results and conclusions. The appendices contain a
list of coded chemical names, a detailed account of mechanism revisions, and a complete list of the
5
revised reactions and their parameters.
Chapter 2
Effect of New Photochemical Rate
Parameters on Simulated NOx and O3
2.1 Introduction
The ability of photochemical models to accurately simulate the levels of atmospheric chemical
species is critically dependent on the gas-phase chemical mechanism. This includes both the
composition of the gas-phase mechanism (number of reactions and species, reaction pathways)
and the rate parameters (rate constants, temperature and pressure dependencies, quantum yield and
cross-sections) for those reactions.
Gas-phase mechanisms can be divided into two groups, reduced (or lumped) and explicit (or
detailed) [Seinfeld, 1988]. The lumped mechanisms are often used in complex 2-D and global
models where many calculations are required. These mechanisms typically simplify the chemistry
of volatile organic compounds; grouping similar compounds either by their structure and reactivity
6
7
characteristics (for example, carbon bond types [Gery et al., 1989]) or by their chemical nature (for
example, chemical families such as alcohols, carbonyls [Atkinson et al., 1982a; Lurmann et al., 1987;
Stockwell et al., 1997; Crassier et al., 2000]). Explicit methods such as those developed by Jenkin
et al. [1997] and Madronich and Calvert [1989] include detailed chemistry for each compound.
These mechanisms may include hundreds of species and contain thousands of reactions. These
mechanisms are particularly useful for box model simulations, as they allow detailed analysis of
photochemical pathways and intermediates.
Many advances have been made in available kinetic and mechanistic data in recent years (e.g.
[Atkinson, 1994; Atkinson, 1997; DeMore et al., 1997; Sander et al., 2000]). The effect of changes
to these parameters recommended between 1989 and 2000 are investigated on simulation results
obtained using an explicit chemical mechanism, the NCAR Master Mechanism. These changes
result in significant changes to the calculated results. The findings described below should be
relevant to other models, as the reactions which had the largest effect on the simulated levels of
NOx and O3 are included in both explicit and lumped models. Section 2.2 describes the model and
the scenario used for these simulations. The revisions made to the mechanism and the effect these
revisions have on the simulated levels of NOx and O3 are covered in Section 2.3.
2.2 Model Description
The NCAR Master Mechanism of the Gas-Phase Chemistry-Version 2.0, contains nearly 1900
species and 5000 reactions. This full chemical mechanism is reduced for the conditions of a
particular situation, based on the species included as initial conditions. For the present study,
this photochemical box model was advanced along an isentropic trajectory at 15 minute intervals,
8
providing new positional (latitude, longitude, altitude), and environmental (temperature, humidity)
data. The actinic flux was calculated using Phodis Version 0.40 [Kylling, 1995] at every 15 minute
time step along the trajectory, using the parameters described by Hamlin and Honrath [2002]. The
actinic flux was then used to determine photolysis rate constants using the routine supplied with the
NCAR Master Mechanism, JBLOCK.
In this study, the effects of revised kinetic and mechanistic parameters were investigated using
simulations of southward flowing arctic air. Results of these simulations using the fully updated
mechanism are described in Hamlin and Honrath [2002]. The May-high-PAN-decomposition
trajectory from Hamlin and Honrath [2002], shown in Figure 2.1, was chosen for these simulations
because it produces the largest flux of NOx and O3 to the North Atlantic from elevated levels of PANs
(peroxy acyl nitrates) in the arctic winter–spring. In addition, as this is a May trajectory, the actinic
flux is higher than in the months of January–April, making the actinic flux more representative of
low- to mid-latitude regions than the other simulations. Initial conditions for these simulations,
listed in Table 2.1, were based on previous measurements of arctic or subarctic air and include N2 ,
O2 , H2 , O3 , CO, CO2 , CH4, C2 –C5 NMHC, benzene, NOx , HONO, HNO3, PAN, C3 –C5 alkyl
nitrates.
The simulations analyzed here are unique in some respects (NOy speciation, high ozone, and
low temperatures). While the levels of PAN (300 ppt) in the arctic winter–spring are typical of
rural to remote regions (see Finlayson-Pitts and Pitts [1999] and references therein), the fraction
of the total NOy they represent (76%) is high. Additionally, the levels of alkyl nitrates (sum of
C3 -C5
50 ppt) is somewhat higher than observed in other regions, representing 13% of NOy in
arctic air. The large fraction of NOy that PAN and alkyl nitrates represent is partially due to the low
9
12
Altitude (km)
10
8
1
6
2
4
3
2
0
-100
45
-50
Longitude
0
50
90
45
80
70
-90
1
60
0
2
-45
50
40
3
30
4
5
Figure 2.1 Forward isentropic trajectory along which simulations were performed. This
trajectory originates on May 8, 1990, 0Z at 70 N, 80 W. Each 12-hr interval is identified
with a (+). Numerals indicate days of transport.
10
Table 2.1 Initial Conditions.
Compound
N2
O2
H2
O3
CO
CO2
CH4
C2 H2
C2 H4
C2 H6
C3 H6
C3 H8
n-butane
i-butane
n-pentane
i-pentane
Mixing Ratio
.7808*air density
.2095*air density
0.5 ppm
73 ppb
170 ppb
360 ppm
1.8 ppm
0.3 ppb
0.1 ppb
1.5 ppb
0.03 ppb
0.3 ppb
0.07 ppb
0.03 ppb
0.02 ppb
0.01 ppb
Notes
Compound
Mixing Ratio Notes
a
C6 H6
0.15 ppb
f–k
a
NOx
19 ppt
l
a
HONO
6 ppt
m
b
HNO3
16 ppt
n
c–d
PAN
300 ppt
o
c
methyl nitrate
0
p
c
ethyl nitrate
0
q
e–k
1-propyl nitrate
3.3 ppt
r–s
e–k
2-propyl nitrate
12.4 ppt
r–s
e–k
1-butyl nitrate
1.7 ppt
r–s
e–g, j–k 2-butyl nitrate
18.4 ppt
r–s
e–k
pentyl nitrate
1.0 ppt
r–s
e–j
3-methyl-2-pentyl nitrate 4.8 ppt
r–s
f–j
2-pentyl nitrate
5.4 ppt
r–s
f–j
3-pentyl nitrate
4.3 ppt
r–s
f–j
2-methyl-1-pentyl nitrate 0.8 ppt
r–s
a) Based on the composition of air [Graedel and Crutzen, 1993]. b) Oltmans [1993]. Ozone level
is altitude dependent. c) Derwent et al. [1998]. d) Novelli et al. [1998]. e) Solberg et al. [1996b],
non-ozone depletion events. f) Solberg et al. [1996a]. g) Laurila and Hakola [1996]. h) Ariya et al.
[1998]. i) Jobson et al. [1994]. j) Doskey and Gaffney [1992]. k) Hov et al. [1984]. l) Estimated from
Jaffe et al. [1991], Honrath and Jaffe [1992], Weinheimer et al. [1994], Beine et al. [1996], Rohrer et
al. [1997], and Beine et al. [1997a]. This value is consistent with NOx observed in the Arctic during
late spring [Ridley et al., 2000], but higher than Ridley’s measurements prior to arctic sunrise. (Model
results are insensitive to the initial NOx level.) m) Li [1994], light period. n) Estimated from Bottenheim
et al. [1993] period 1 and Bottenheim and Gallant [1989]. Loss reactions of HNO3 are negligible in these
simulations, so model results are insensitive to the initial level of HNO3 . o) Estimated from Bottenheim
and Gallant [1989], Bottenheim et al. [1993], Beine et al. [1997b], and Beine and Krognes [2000]. High
values were given more weight to provide an upper limit for NOx release. For this reason and to allow
for comparisons of photochemical processes by month, seasonal variations were not included. p) There
are no reported measurements of methyl nitrate in arctic or subarctic air. q) Measurements of ethyl nitrate
have not been reported for the arctic or subarctic. r) Leaitch et al. [1994]. s) Muthuramu et al. [1994].
level of NOx observed. NOx levels are typically low in aged airmasses due to rapid oxidation of
NOx . Another characteristic of the aged air arctic mass is that the speciation of the volatile organic
compounds present in the Arctic during winter-spring is more heavily weighted towards the less
reactive hydrocarbons such as acetylene, ethane, benzene, ethene, and propane than is the case for
airmasses with more recent emissions. Another unique characteristic of this simulation is the high
initial level of ozone. Ozone levels vary greatly with altitude. Levels in the winter–spring Arctic
range from 35 ppb in the lower free troposphere to 80 ppb in the upper free troposphere. As this
11
particular trajectory originates near 6 km, the initial level of ozone used is high compared to remote
and rural regions from the surface to mid-tropospheric sites. Additionally, the temperature is low
in the high-latitude free troposphere, which permits transport of reservoir species such as PAN.
The unique characteristics of the scenario simulated in this work had some effects on the results
below. In particular, the importance of ozone photolysis and alkyl nitrates were emphasized as high
levels of these species increase their loss rates. However, in most respects these simulations are
a useful model of the chemical evolution of aging polluted air and therefore applicable to other
situations as well.
2.3 Model Revisions and Their Effect on NO and O3
x
Since the NCAR Master Mechanism-Version 2.0 was created in the late 1980’s, improvements
have been made to the available kinetic data. Kinetic data have been evaluated by several groups,
including the International Union of Pure and Applied Chemistry (IUPAC) subcommittee on Gas
Kinetic Data Evaluation for Atmospheric Chemistry [Atkinson et al., 1992b], the Statewide Air
Pollution Research Center and Department of Soil and Environmental Sciences, University of
California, Riverside [Atkinson, 1994], and the NASA Panel for Data Evaluation [DeMore et al.,
1997; Sander et al., 2000]. These reviews form the basis for the revisions made to the Master
Mechanism. Additionally, the peroxy radical reactions have been extensively revised based on the
work of Kirchner and Stockwell [1996]. Altogether, more than 3200 reactions have been revised in
this work. These revisions consist primarily of new rate parameters; however, a number of changes
have also been made to the mechanism including the addition of several new reactions. Revisions
have been made to photolysis reactions, inorganic reactions and a variety of organic reactions. As
12
halogen chemistry is not expected to play a significant role in the free troposphere, halogen reactions
were not revised.
Revisions to the mechanism were made in small increments in order to determine their individual
effects on simulated levels of NOx and O3 . In this work we focus on the impact of these revisions
on levels of NOx and O3, because of ozone’s role in controlling the oxidizing capacity of the
atmosphere and of NOx ’s role in controlling the production of ozone in the remote atmosphere.
The revisions examined in detail for their effect on NOx and O3 include reactions in the following
categories: photolysis of nitrogen and oxygen containing compounds, odd oxygen, odd hydrogen,
odd nitrogen, unsubstituted hydrocarbons, organic radicals, oxygen containing organic compounds,
nitrogen containing organic compounds, and aromatic compounds. Some of these groups have been
further subdivided in order to identify which revisions have the greatest effect on simulated levels
of NOx and O3 .
2.3.1 Photolysis Revisions
Updates to the photolysis reactions were limited to absorption cross sections and quantum yields
for the nitrogen and oxygen containing compounds which were treated explicitly by Madronich
and Calvert [1989]. A list of species evaluated is shown in Tables 2.2 and 2.3. The absorption
cross sections and quantum yields for each compound were compared to values recommended by
DeMore et al. [1997] and Sander et al. [2000] to assess whether there has been a significant change
in the photolysis data since the NCAR Master Mechanism-Version 2.0 [Madronich and Calvert,
1989] was created. The reviews by Atkinson [1994] and Atkinson et al. [1992b] were used, in that
order of precedence, for compounds that were not addressed by DeMore et al. [1997] or Sander et
13
Table 2.2 Summary of Photolysis Cross-Sections.
Compound
O3
H2 O2
methylhydroperoxide
NO2
NO3
N2 O5
HONO
HNO3
HNO4
HCHO
Cross Section
Madronich and Calvert [1989] a
DeMore et al. [1997]
Madronich and Calvert [1989] b;c
Stockwell et al. [1997]
Stockwell et al. [1997]
Madronich and Calvert [1989] b
Stockwell et al. [1997]
Stockwell et al. [1997]
Madronich and Calvert [1989] b
< 300 Madronich and Calvert [1989]
300 DeMore et al. [1997]
Martinez et al. [1992] d
Martinez et al. [1992] d
Martinez et al. [1992] d
Martinez et al. [1992] d
Madronich and Calvert [1989] c
Stockwell et al. [1997] d
Martinez et al. [1992] d
Martinez et al. [1992] d
Martinez et al. [1992] d
Madronich and Calvert [1989] d
Madronich and Calvert [1989]
acetaldehyde
propanal
1-butanal
1-methyl propanal
glyoxal
methyl glyoxal
acetone
2-butanone
3-pentanone
biacetyl
acrolein
a Recommended by Sander et al. [2000]
b Recommended by DeMore et al. [1997]
c Recommended by Atkinson et al. [1992b]
d Recommended by Atkinson [1994]
al. [2000], such as C3 and larger organic compounds. Photolysis data for many compounds are still
not available. In these cases, the cross-sections and quantum yields used by Madronich and Calvert
[1989] were retained.
The revisions made to the photolysis reactions result in lower levels of NOx and O3 as shown in
Figures 2.2 and 2.3.
The mean levels of NOx and O3 are 8.4% and 1.0% lower, respectively, than
the mean NOx and O3 levels simulated using the original mechanism,the NCAR Master MechanismVersion 2. Of the changes made to the photolysis reactions, alteration of the temperature dependent
expression for calculating the quantum yield of ozone had the greatest effect, accounting for nearly
14
NOx
Concentration in ppt
80
Madronich and Calvert, Version II, 1989
Ozone Photolysis
All Photolysis Revisions
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.2 Effect of photolysis revisions on NOx levels. Levels of NOx as a function of time
along the trajectory. The solid line uses the unrevised NCAR Master Mechanism-Version 2.0.
The dotted line uses the Master Mechanism with revised O 3 photolysis. The long dashed
line indicates the sum of all the revisions to the photolysis reactions.
Ozone
74
Concentration in ppb
72
70
68
66
64
0
Madronich and Calvert, Version II, 1989
Ozone Photolysis
All Photolysis Revisions
1
2
3
Time in Days
4
5
6
Figure 2.3 Effect of photolysis revisions on O3 levels. Refer to Figure 2.2 for descriptive
information.
15
Table 2.3 Summary of Photolysis Quantum Yields.
Compound
O3
H2 O2
methylhydroperoxide
NO2
NO3
N2 O5
HONO
HNO3
HNO4
HCHO
acetaldehyde
propanal
1-butanal
1-methyl propanal
glyoxal
methyl glyoxal
acetone
2-butanone
3-pentanone
biacetyl
acrolein
Quantum Yield
Sander et al. [2000]
unity, Madronich and Calvert [1989] a
unity, Madronich and Calvert [1989] a
Madronich and Calvert [1989] a
Johnston et al. [1996] a
Madronich and Calvert [1989] a
unity, Madronich and Calvert [1989] b
unity, Madronich and Calvert [1989] b
unity, Madronich and Calvert [1989] a
Madronich and Calvert [1989] a
Madronich and Calvert [1989] c
Atkinson [1994]
Madronich and Calvert [1989]
Atkinson [1994]
Madronich and Calvert [1989] b
Atkinson et al. [1992b]
Stockwell et al. [1997] c
unity, Madronich and Calvert [1989]
unity, Madronich and Calvert [1989]
Madronich and Calvert [1989] c
Madronich and Calvert [1989]
a Recommended by DeMore et al. [1997]
b Recommended by Atkinson et al. [1992b]
c Recommended by Atkinson [1994]
the entire change in the levels of NOx and O3 . Including the “tail” for the quantum yield of O(1D)
from the photolysis of ozone between 310 and 330 nm significantly increased the ozone rate of
photolysis. In comparison to the original mechanism, this change to the ozone quantum yield
decreases the level of NOx and O3 averaged over the duration of the simulation by 8.7% and 1.0%,
respectively.
Photolysis reactions have been added for PAN and a number of alkyl nitrates. These changes are
discussed in Section 2.3.3.4 and are therefore not included in the total photolysis revisions indicated
in Figures 2.2 and 2.3.
16
NOx
80
Madronich and Calvert, Version II, 1989
Ox
HOx
NOy
All Inorganic Revisions
Concentration in ppt
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.4 Effect of inorganic revisions on NOx levels. The solid line indicates the levels
simulated using the unrevised NCAR Master Mechanism-Version 2.0. The dotted line uses
the Master Mechanism with revised reaction rate constants for the inorganic reactions of odd
oxygen compounds. The dashed line uses the Master Mechanism with revised inorganic
reactions for odd hydrogen compounds. The dot-dashed line uses the Master Mechanism
with revised inorganic reactions for odd nitrogen compounds. The long dashed line indicates
the sum of all the revisions to inorganic chemistry.
2.3.2 Inorganic Revisions
Revisions to the chemistry of inorganic species were based on the recommendations of DeMore et
al. [1997]. Reactions of odd oxygen (Ox ), O(1D), odd hydrogen (HOx ), and odd nitrogen species
(NOy ) were examined. Over 30 inorganic reactions were revised; a complete list of the reactions
examined and revised is included in Appendix B.1.1. As shown in Figures 2.4 and 2.5 the revisions
made to reactions of odd nitrogen species have a significant effect on the level of NOx and a minimal
effect on the level of O3 , while revisions made to the inorganic reactions of Ox and HOx have no
noticeable effect.
The revisions made to the inorganic nitrogen reactions which have the largest effect on the
levels of NOx (Figure 2.6) and O3 (Figure 2.7) include the following: 1) Removal of the NO3
17
O3
74
Concentration in ppb
72
70
68
66
Madronich and Calvert, Version II, 1989
Ox
HOx
NOy
All Inorganic Revisions
64
0
1
2
3
Time in Days
4
5
6
Figure 2.5 Effect of inorganic revisions on O3 levels. Refer to Figure 2.6 for descriptive
information.
thermal decomposition reaction, which is no longer believed to occur in the atmosphere [DeMore
et al., 1997]; 2) A change in the troe rate parameters for the reaction of NO2 with OH to reflect the
recommendations of DeMore et al. [1997], and 3) An increase in the N2 O5 hydrolysis rate constant
using the upper-limit gas-phase rate constant recommended by DeMore et al. [1997]. While the
rate constant is modeled as a gas-phase process, it is consistent with values used to simulate both
homogeneous and heterogeneous processes, as discussed in Section 3.2.1.2.
Removal of the NO3 thermal decomposition reaction results in higher levels of NO3 (Figure 2.8)
at night. This increases the formation rate of N2 O5 (Figure 2.9) and the conversion of NOx to HNO3
(Figure 2.10) through N2O5 hydrolysis. As a result, levels of NOx decrease, slowing the formation
of O3 . The removal of the NO3 thermal decomposition reaction decreases the mean level of NOx
by 10.9%. In addition, the increase in the rate of N2 O5 hydrolysis accentuates these changes,
decreasing the mean level of NOx by 2.7%. The changes made to the troe rate parameters for the
18
NOx
80
Madronich and Calvert, Version II, 1989
N2O5 Hydrolysis
NO3 Decomposition
NO2 + OH + M
All Inorganic Revisions
Concentration in ppt
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.6 Effect of inorganic nitrogen revisions on NOx levels. Simulated levels of NO3 are
shown as a function of time along the trajectory. The solid line indicates the levels simulated
using the unrevised NCAR Master Mechanism-Version 2.0. The dotted line uses the Master
Mechanism with the revised N2 O5 hydrolysis rate constant. The dashed line uses the Master
Mechanism without the NO3 thermal decomposition reaction. The dot-dashed line uses the
Master Mechanism with updated troe rate parameters for the reaction of NO2 + OH. The
long dashed line indicates the sum of all the revisions to inorganic chemistry.
O3
74
Concentration in ppb
72
70
68
66
Madronich and Calvert, Version II, 1989
N2O5 Hydrolysis
NO3 Decomposition
NO2 + OH + M
All Inorganic Revisions
64
0
1
2
3
Time in Days
4
5
6
Figure 2.7 Effect of inorganic nitrogen revisions on O3 levels. Refer to Figure 2.6 for
descriptive information.
19
NO3
20
Madronich and Calvert, Version II, 1989
N2O5 Hydrolysis
NO3 Decomposition
NO2 + OH + M
All Inorganic Revisions
Concentration in ppt
15
10
5
0
0
1
2
3
Time in Days
4
5
6
Figure 2.8 Effect of inorganic nitrogen revisions on the levels of NO3 . Refer to Figure 2.6
for descriptive information.
N2O5
2.5
Concentration in ppt
2.0
Madronich and Calvert, Version II, 1989
N2O5 Hydrolysis
NO3 Decomposition
NO2 + OH + M
All Inorganic Revisions
1.5
1.0
0.5
0.0
0
1
2
3
Time in Days
4
5
6
Figure 2.9 Effect of inorganic nitrogen revisions on the levels of N2 O5 . Refer to Figure 2.6
for descriptive information.
20
HNO3
200
Madronich and Calvert, Version II, 1989
N2O5 Hydrolysis
NO3 Decomposition
NO2 + OH + M
All Inorganic Revisions
Concentration in ppt
150
100
50
0
0
1
2
3
Time in Days
4
5
6
Figure 2.10 Effect of inorganic nitrogen revisions on the levels of HNO3 . Refer to Figure 2.6
for descriptive information.
reaction of NO2 with OH decreases the loss rate of NO2 , which increases the levels of NOx . For
this simulation the mean level of NOx (averaged over the duration of the simulation) was increased
by 6.4%. As a result of increased NOx levels, the levels of O3 are increased; the mean level of O3 is
increased by 0.3%. Additionally, the levels of HNO3 are decreased. When all the inorganic revisions
are included, the mean level of NOx and O3 are decreased by 10.5% and 0.02% respectively.
2.3.3 Organic Reactions
Reactions of a variety of organic species have been revised, including the reactions of unsubstituted hydrocarbons, radicals, oxygen containing organic compounds, nitrogen containing organic
compounds, and aromatic compounds.
21
NOx
Concentration in ppt
80
Madronich and Calvert, Version II, 1989
CH4
All Unsubstituted Hydrocarbon Revisions
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.11 Effect of revisions to unsubstituted hydrocarbon reactions on levels of NOx .
Levels of NOx as a function of time along the trajectory. The solid line uses the unrevised
NCAR Master Mechanism-Version 2.0. The dotted line uses the Master Mechanism with
revised methane chemistry. The dashed line uses revised unsubstituted organic chemistry.
2.3.3.1
Unsubstituted Hydrocarbons
The revisions to straight chain alkane reactions with OH and NO3 were completed through C6 .
Branched alkane reactions were also revised through C6 if data were available [Atkinson, 1994;
DeMore et al., 1997]. Alkene reactions were revised through C4 for reactions with OH, O3 , and
NO3 . Reactions of acetylene with OH, NO3 , and O3 were also examined. No other alkyne reactions
were updated, as acetylene is the only alkyne included in the NCAR Master Mechanism-Version 2.0
and the only alkyne measured in arctic air. Rate parameters recommended by DeMore et al. [1997]
were used if they were available (reactions of C3 with OH). For the remaining alkane, alkene,
and alkyne reactions, rate parameters were based on the recommendations of Atkinson [1994].
The revisions to reactions of unsubstituted hydrocarbons result in a slight decrease in the
simulated levels of NOx (Figure 2.11), and a marked decrease in O3 (Figure 2.12).
These
22
Ozone
74
Concentration in ppb
72
70
68
66
64
0
Madronich and Calvert, Version II, 1989
CH4
All Unsubstituted Hydrocarbon Revisions
1
2
3
Time in Days
4
5
6
Figure 2.12 Effect of revisions to unsubstituted hydrocarbon reactions on O3 levels. Refer
to Figure 2.11 for descriptive information.
changes are due primarily to revisions of methane chemistry. The rate constant for the reaction of
methane with OH was reduced by 21%, which increased the levels of methane and OH. In contrast,
methane levels were lowered by the addition of its reaction with NO3 . However, the increase in
the methane loss rate due to the addition of reaction with NO3 , is outweighed by the decrease in
the loss rate of methane by reaction with OH. The changes to methane chemistry alone results in
a 2.9% and 0.2% decrease in the mean levels of NO x and O3 , respectively, compared to a 2.7%
and 0.2% decrease when all unsubstituted organic revisions were included. The sum of all the
unsubstituted hydrocarbon revisions results in increased levels of OH, which increases the loss rate
of many species including NOx , accounting for its decreased mixing ratios.
23
Table 2.4 Alkyl and Alkoxy Radical Reactions.
Reaction
CH3 + O3 ! ?
CH3 + O2 ! ?
CH3 + O2 + (M) ! CH3 (OO) + (M)
C2 H5 + O2 ! C2 H4 + HO2
C2 H5 + O2 + (M) ! CH3 CH2 (OO) + (M)
HCO + O2 ! CO + HO2
CH2 (OH) + O2 ! CH2 O + HO2
CH3 O + O2 ! CH2 O + HO2
CH3 O + NO ! CH2 O + HNO
CH3 O + NO2 ! CH2 O + HNO2
CH3 O + NO2 + (M) ! CH3 3(ONO2 ) + (M)
CH3 CH2 (O) + O2 ! d021 + HO2
CH3 CH2 (O) + NO + (M) ! CH3 CH2 ONO + (M)
CH3 CH2 (O) + NO2 + (M) ! CH3 CH2 (ONO2 ) + (M)
New K298
2.6E-12
<3.0E-16
1.1E-12
<2.0E-14
7.5E-12
5.5E-12
9.1E-12
1.9E-15
< 8.0E-12
2.0E-13
1.5E-11
1.0E-14
4.7E-11
2.7E-11
New E/R
2.2E+02
0.0E+00
-1.2E+03
2.1E+03
-1.2E+03
-1.4E+02
0.0E+00
9.0E+02
0.0E+00
1.2E+03
0.0E+00
5.5E+02
0.0E+00
0.0E+00
a Recommended by DeMore et al. [1997]
b No E/R value reported, Madronich and Calvert [1989] value retained
c New reaction
d Products changed
2.3.3.2
Sources
Madronich and Calvert [1989] a
Madronich and Calvert [1989]a
DeMore et al. [1997]
DeMore et al. [1997] b
DeMore et al. [1997]
Madronich and Calvert [1989]a
DeMore et al. [1997]
DeMore et al. [1997]
DeMore et al. [1997] c
DeMore et al. [1997] d
DeMore et al. [1997]
DeMore et al. [1997]
DeMore et al. [1997]
DeMore et al. [1997]
Radicals
A limited number of revisions have been made to the chemistry of alkyl and alkoxy radicals. C2 or
smaller alkyl radical reactions with O2 that were examined are listed in Table 2.4.
Also listed in
this table are alkoxy radical reactions ( C2 ) which were revised. These revisions only affected the
mixing ratios of the radicals themselves; other species were not significantly influenced, since the
lifetimes of these radicals were already very short.
Significant revisions were made to the chemistry of peroxy radicals. Rate constants and activation temperatures (Ea /R) for peroxy radical reactions were updated using the methods developed by
Kirchner and Stockwell [1996]. These methods are described further below. Peroxy radicals may
react with NO, HO2, NO2 , with themselves (self-reaction), and any other peroxy radicals which
are present (cross-reaction). Recent studies [Canosa-Mas et al., 1996] suggest that peroxy radicals
may also react with NO3.
24
In the NCAR Master Mechanism-Version 2.0, there are 314 peroxy radicals. There is a reaction
for each peroxy radical with NO and with HO2 . Additionally, there are reactions with NO2 for the
methylperoxy radical and the acyl peroxy radicals. For simplicity, a counter scheme is used for the
cross-reactions (peroxy-peroxy radical reactions). In the NCAR Master Mechanism-Version 2.0,
each peroxy radical reacts with methylperoxy radical and 4 counters, each counter representing a
family of peroxy radicals (primary, secondary, tertiary, and acyl), as described by Madronich and
Calvert [1990].
Peroxy radical reactions with NO Peroxy radical reactions with NO were revised using
experimentally determined rate parameters where available. As suggested by Atkinson [1994], if
data were not available, the acyl peroxy radicals were assigned the measured rate parameters of
peroxy acetyl radical (k298
=
1:8 10,11 molec,1 cm3 s,1 and E/R = -360 K) [DeMore et al.,
1997] and alkyl peroxy radicals were assigned a rate constant of k298
=
4 10,12 molec,1 cm3 s,1
[Kirchner and Stockwell, 1996]. The main path for this reaction produces an alkoxy radical and
NO2 , while the second reaction path produces an alkyl nitrate:
RO2 + NO
!a
RO + NO2
!b
RONO2:
(2.1)
For larger alkyl peroxy radicals, Reaction 2.1b becomes important; for these reactions branching
ratios were calculated using the method described by Atkinson [1994].
The reaction rate constants for methyl and ethyl peroxy radicals (and several others) with NO
were increased. However, most of the reaction rate constants for alkyl peroxy radicals with NO
were decreased. These revisions have a minimal effect on the levels of NOx (Figure 2.13) and
25
NOx
100
Madronich and Calvert, Version II, 1989
Alkyl Peroxy + NO
Acyl Peroxy + NO
All Peroxy Revisions
Concentration in ppt
80
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.13 Effect of revisions to peroxy radical reactions with NO on NOx levels. Levels
of NOx as a function of time along the trajectory. The solid line uses the unrevised NCAR
Master Mechanism-Version 2.0. The dotted line uses the Master Mechanism with revised
alkyl peroxy radical reactions with NO. The dashed line uses revised acyl peroxy radical
reactions with NO. The long dashed line indicates the sum of all the revisions to the peroxy
radical reactions.
O3 (Figure 2.14), decreasing the average levels by 0.7% and 0.01%, respectively.
The reaction
rate constants for the acyl peroxy radical reactions with NO were increased. Increasing the loss
rate of the peroxyacetyl radical reduces the amount that reforms PAN, increasing the levels of NOx
(Figure 2.13) and O3 (Figure 2.14). Average levels of NOx and O3 were increased significantly, by
9.1% and 0.33%, respectively, as a result of revisions to acyl radical reactions with NO.
Peroxy radical reactions with HO2 The reactions of peroxy radicals with HO2 have been
revised (see Table C.7) using experimental data where available. If unavailable, the rate parameters
were assigned using the rate parameters of similar compounds or the average values (k298
=
1:30 10,11 molec,1 cm3 s,1 , E/R = -1300 K) determined by Kirchner and Stockwell [1996].
Each acyl peroxy reaction with HO2 has two possible pathways, one producing an acid
26
Ozone
74
Concentration in ppb
72
70
68
66
Madronich and Calvert, Version II, 1989
Alkyl Peroxy + NO
Acyl Peroxy + NO
All Peroxy Revisions
64
0
1
2
3
Time in Days
4
5
6
Figure 2.14 Effect of revisions to peroxy radical reactions with NO on O3 levels. Refer to
Figure 2.13 for descriptive information.
(RC(O)OH), the other producing a peroxy acid (RC(O)OOH).
R-C(O)OO + HO2
!a
R-C(O)OOH + O2
!b
R-C(O)OH + O3 :
(2.2)
The NCAR Master Mechanism-Version 2.0 only includes Reaction 2.2a. The second reaction
pathway, (Reaction 2.2b), was added using the branching ratios of Kirchner and Stockwell [1996],
which are in the range of values presented by DeMore et al. [1997] (kb /k=0.25–0.33).
The result of these changes was an increase in the reaction rate constants for both alkyl and
acyl peroxy radical reactions with HO2. Revisions to both alkyl and acyl peroxy radical reactions
with HO2 increased the levels of NOx and O3 as shown in Figures 2.15 and 2.16. The effects were
greatest for the acyl peroxy adjustments (average levels increased by 9.0% and 0.31%) relative to
the alkyl peroxy revisions (average levels increased by 5.2% and 0.10%).
27
NOx
100
Madronich and Calvert, Version II, 1989
Alkyl Peroxy + HO2
Acyl Peroxy + HO2
All Peroxy Revisions
Concentration in ppt
80
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.15 Effect of revisions to peroxy radical reactions with HO2 on NOx levels. Levels
of NOx as a function of time along the trajectory. The solid line uses the unrevised NCAR
Master Mechanism-Version 2.0. The dotted line uses the Master Mechanism with revised
alkyl peroxy radical reactions with HO2 . The dashed line uses revised acyl peroxy radical
reactions with HO2 . The long dashed line indicate the sum of all the revisions to the peroxy
radical reactions.
Ozone
74
Concentration in ppb
72
70
68
66
Madronich and Calvert, Version II, 1989
Alkyl Peroxy + HO2
Acyl Peroxy + HO2
All Peroxy Revisions
64
0
1
2
3
Time in Days
4
5
6
Figure 2.16 Effect of revisions to peroxy radical reactions with HO2 on O3 levels. Refer to
Figure 2.15 for descriptive information.
28
Table 2.5 Alkyl Peroxy Radical Rate Constants for Reaction with HO2 .
Parent Hydrocarbon
methylperoxy
ethylperoxy
C3 –C8 nonsubstituted
methyl alcohol
ethyl alcohol
C3 –C8 alcohol
Organic Nitrates
CH3 C(O)CH2 O2
ketones
C6 H5 CH2 O2
Aromatics
Carboxylic acids
Aldehydes
Ethers
Peroxy Acids
Hydroperoxides
PANs
k(298)
5.6 10,12
8.0 10,12
1.3 10,11
1.2 10,11
1.0 10,11
1.3 10,11
1.3 10,11
9.0 10,12
9.0 10,12
1.0 10,11
1.0 10,11
1.3 10,11
1.3 10,11
1.3 10,11
1.3 10,11
1.3 10,11
1.3 10,11
E/R
-800
-700
-1300
-2300
-1300
-1300
-1300
-1300
-1300
-980
-980
-1300
-1300
-1300
-1300
-1300
-1300
Source
[DeMore et al., 1997]
[DeMore et al., 1997]
average value from [Kirchner and Stockwell, 1996]
[Lightfoot et al., 1992]
[Lightfoot et al., 1992]
average value from [Kirchner and Stockwell, 1996]
[Kirchner and Stockwell, 1996]
[LeBras, 1997]
CH3 C(O)CH2O2
[LeBras, 1997]
C6 H5 CH2 O2
average value from [Kirchner and Stockwell, 1996]
average value from [Kirchner and Stockwell, 1996]
average value from [Kirchner and Stockwell, 1996]
average value from [Kirchner and Stockwell, 1996]
average value from [Kirchner and Stockwell, 1996]
average value from [Kirchner and Stockwell, 1996]
Peroxy radical reactions with NO2 In the NCAR Master Mechanism-Version 2.0 there are
only two reactions of alkyl peroxy radicals with NO2, those with the methylperoxy radical and
C6 H5 O2. As the rate parameters recommended by DeMore et al. [1997] for the reaction of
methylperoxy radical with NO2 are the same as those used in the Master Mechanism, that reaction
was not altered. Reactions of alkyl peroxy radicals with NO2 are typically insignificant compared
to the other reactions of alkyl peroxy radicals under most tropospheric conditions [FinlaysonPitts and Pitts, 1999], because this reaction forms peroxynitrates which rapidly undergo thermal
decomposition back to its reactants. Additional reactions were therefore not added.
Revisions to the reactions of acyl peroxy radicals with NO2 are included in the PAN revisions
discussed in Section 2.3.3.4, and are therefore not included here.
Peroxy radical reactions with NO3 Reactions of methylperoxy radical and peroxyacetyl
radical with NO3 have been added to the mechanism with rate constants of 1.2 10,12 molec,1cm3
29
NOx
100
Madronich and Calvert, Version II, 1989
Peroxy + NO3
All Peroxy Revisions
Concentration in ppt
80
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.17 Effect of revisions to peroxy radical reactions with NO3 on NOx levels. Levels of
NOx as a function of time along the trajectory. The solid line uses the unrevised NCAR Master
Mechanism-Version 2.0. The dotted line uses the Master Mechanism with the addition of
methylperoxy and peroxyacetyl radical reactions with NO 3 . The long dashed line indicates
the sum of all the revisions to the peroxy radical reactions.
s,1 and 4.0
10,12 molec,1 cm3 s,1 [Kirchner and Stockwell, 1996], respectively.
As shown in
Figures 2.17 and 2.18, the addition of these two reactions has a minimal effect on NOx and O3 ,
increasing their average levels by 0.6% and 0.06%, respectively.
Peroxy Radical-Peroxy Radical Reactions The rate constants for peroxy radical cross reactions have been revised using experimental data where available. However, most of the rate
constants for the peroxy radical cross reactions were estimated using the method recommended by
Madronich and Calvert [1990]. In this method, the peroxy radical cross reaction rate constants (k12 )
were estimated as twice the geometric average of the corresponding self-reaction rate constants, k1
and k2 , for peroxy radicals R1 O2 and R2 O2 (where R2 O2 is methylperoxy radical or a counter),
k12 = 2(k1 k2)1=2:
(2.3)
30
Ozone
74
Concentration in ppb
72
70
68
66
Madronich and Calvert, Version II, 1989
Peroxy + NO3
All Peroxy Revisions
64
0
1
2
3
Time in Days
4
5
6
Figure 2.18 Effect of revisions to peroxy radical reactions with NO3 on O3 levels. Refer to
Figure 2.17 for descriptive information.
The activation temperature, Ea12/R, for the cross reactions have large uncertainties and are calculated
from the self-reaction activation temperatures (Ea1/R and Ea2 /R) for peroxy radicals R1 O2 and R2 O2 ,
Ea12=R = Ea1=R +2 Ea2=R :
(2.4)
Peroxy radical self-reaction rate constants and Ea /R values were based on experimental data
if available [Lightfoot et al., 1992; Atkinson, 1994; Kirchner and Stockwell, 1996; DeMore et al.,
1997]. Otherwise, the self-reaction rate constant was estimated using the following equation,
k 2 10,14 exp 3:8A , 5 +
3
1 + 0:02N 2
N ;
(2.5)
developed by Kirchner and Stockwell [1996] to fit self-reaction rate constants based on carbon
number, branching structure (methyl, primary, secondary, or tertiary), and electron withdrawing
functional groups. In equation 2.5, the rate constant, k (molecule,1 cm3 s,1) is determined based
on the presence (A=1) or absence (A=0) of additional oxygen atoms in the alkyl group, the number
31
of alkyl groups on the peroxy radical carbon (), and the number of carbon atoms (N, where N=7
for peroxy radicals
C7 ).
While the only peroxy radical self-reactions treated explicitly in the
Master Mechanism involve HO2 and CH3 O2 , self-reaction rate constants are calculated for all 314
alkyl and acyl peroxy radicals for use in estimating cross-reaction rate constants using Equation 2.3.
The primary, secondary, and tertiary counters are assigned self-reaction rate constants based on the
recommendation of Atkinson [1994], while the acyl peroxy radical self-reaction rate constant used
by Madronich and Calvert [1989] was retained.
If experimental activation temperatures (Ea /R) for the self-reactions were available, they were
used. If unavailable, Ea /R values were assigned based on A, , and N using the methods of Kirchner
and Stockwell [1996]. As with the self-reaction rate constants, an Ea /R value is calculated for each
peroxy radical, for use in calculating this ratio for peroxy radical cross reactions.
In general, this procedure resulted in decreased reaction rate constants for the alkyl peroxy
radical cross reactions with the methylperoxy radical and the primary, tertiary, and acyl peroxy
radical counters, while the reaction rate constants were increased for the alkyl peroxy radical cross
reactions with the secondary peroxy radical counter. The revisions to the alkyl peroxy reactions
with methylperoxy and the counters did not have a significant effect on the levels of NOx (average
levels decreased by 0.3% and 0.1%) and O3 (average levels decreased by 0.02% and 0.01%), shown
in Figures 2.19 and 2.20.
For most of the acyl peroxy radical reactions with methylperoxy radical and the counters,
the reaction rate constants were decreased. However, the reaction rate constants were increased
for the reactions of peroxyacetyl and peroxypropionyl radicals with methylperoxy radical and the
counters. As a result, the loss rates of peroxyacetyl radical were increased, decreasing the levels of
32
NOx
100
Concentration in ppt
80
Madronich and Calvert, Version II, 1989
Alkyl Peroxy + 2011
Alkyl Peroxy + counters
Acyl Proxy +2011
Acyl Peroxy + counters
All Peroxy Revisions
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.19 Effect of revisions to peroxy radical cross reactions on NOx levels. Levels of
NOx as a function of time along the trajectory. The solid line uses the unrevised NCAR
Master Mechanism-Version 2.0. The dotted line uses the Master Mechanism with revised
rate constants for the reaction of alkyl peroxy radicals with methylperoxy radical. The dashed
line uses revised reactions rate constants for the reactions of alkyl peroxy radicals with the
counters. The dot-dashed line uses revised rate constants for the reactions of acyl peroxy
radical with methylperoxy radical. The dot-dot-dashed line uses revised rate constants for
the acyl peroxy radical reactions with the counters. The long dashed line indicates the sum
of all the revisions to the peroxy radical reactions.
Ozone
74
Concentration in ppb
72
70
68
66
Madronich and Calvert, Version II, 1989
Alkyl Peroxy + 2011
Alkyl Peroxy + counters
Acyl Proxy +2011
Acyl Peroxy + counters
All Peroxy Revisions
64
0
1
2
3
Time in Days
4
5
6
Figure 2.20 Effect of revisions to peroxy radical cross reactions on O3 levels. Refer to
Figure 2.19 for descriptive information.
33
PAN
400
Concentration in ppt
300
200
Madronich and Calvert, Version II, 1989
Acyl Peroxy + NO
100
Acyl Peroxy + HO2
Acyl Peroxy + 2011
Acyl Peroxy + Counters
Peroxyacetyl Revisions
All Peroxy Revisions
0
0
1
2
3
Time in Days
4
5
6
Figure 2.21 Effect of revisions to peroxy acyl radical reactions on PAN levels. Levels of
PAN as a function of time along the trajectory. The solid line uses the unrevised NCAR
Master Mechanism-Version 2.0. The dotted line uses the Master Mechanism with revised
acyl peroxy radical reactions with NO. The dashed line uses revised acyl peroxy radical
reactions with HO2 . The dot-dashed line indicates revisions to the reaction of acyl peroxy
radicals with methylperoxy radical. The dot-dot-dashed line uses revised reaction rate
constants for the acyl peroxy radicals with the counters. The long dashed line indicate the
sum of all the revisions to the peroxy radical reactions.
peroxyacetyl radical. (The effects on PAN of modifications of acyl peroxy + methylperoxy reactions
and of acyl peroxy + peroxy radical counter reactions are shown in Figure 2.21.) This reduces the
amount of peroxyacetyl radical available for PAN reformation (Figure 2.22) which increases the
levels of NOx (Figure 2.19) and therefore increases the production of O3 (Figure 2.20). The
revisions to the reactions of peroxy acyl radicals with methylperoxy radical significantly increased
the average NOx level by 9.2% and 4.5%, respectively, while the average level of O3 was increased
by 0.16% and 0.07%, respectively.
All Peroxy Radical Revisions The sum of all the revisions made to the chemistry of peroxy
radicals results in significantly increased levels of NOx (Figure 2.19) and O3 (Figures 2.20). The
34
Peroxyacetyl Radical
2.0
Concentration in ppt
1.5
Madronich and Calvert, Version II, 1989
Acyl Peroxy + NO
Acyl Peroxy + HO2
Acyl Peroxy + 2011
Acyl Peroxy + Counters
Peroxyacetyl Revisions
All Peroxy Revisions
1.0
0.5
0.0
0
1
2
3
Time in Days
4
5
6
Figure 2.22 Effect of revisions to peroxy acyl radical reactions on peroxyacetyl radical levels.
Refer to Figure 2.21 for descriptive information.
mean levels of NOx and O3 are increased significantly, by 23.9% and 0.7%, respectively. The
changes to the chemistry of acyl peroxy radicals have a much greater effect than the changes
made to the chemistry of alkyl peroxy radicals. Of the acyl peroxy radical reactions, the changes
to the reactions with HO2 and NO have the largest effect on the levels of NOx (Figure 2.23)
and O3 (Figure 2.24), followed closely by the changes made to the reactions with methylperoxy
radical and then the counters.
Of the acyl peroxy radical species for which reactions were
revised, the changes made to the reactions of peroxyacetyl radical have the largest impact, because
other peroxyacyl nitrates were not included in the initial conditions for this simulation. When the
peroxyacetyl radical reactions are revised, the average levels of NOx and O3 are increased by 17.7%
and 0.48%, respectively. The changes made to the reactions of acyl peroxy radicals increase the
loss rate of the peroxyacetyl radical, illustrated by the decreased levels shown in Figure 2.22. As a
result of more efficient removal of the peroxyacetyl radical, there is less available for the reaction
35
NOx
100
Concentration in ppt
80
Madronich and Calvert, Version II, 1989
Acyl Peroxy + NO
Acyl Peroxy + HO2
Acyl Peroxy + 2011
Acyl Peroxy + Counters
Peroxyacetyl Revisions
All Peroxy Revisions
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.23 Effect of revisions to peroxy acyl radical reactions on NOx levels. Refer to
Figure 2.21 for descriptive information.
O3
74
Concentration in ppb
72
70
68
Madronich and Calvert, Version II, 1989
Acyl Peroxy + NO
66
64
0
Acyl Peroxy + HO2
Acyl Peroxy + 2011
Acyl Peroxy + Counters
Peroxyacetyl Revisions
All Peroxy Revisions
1
2
3
Time in Days
4
5
6
Figure 2.24 Effect of revisions to peroxy acyl radical reactions on O3 levels. Refer to
Figure 2.21 for descriptive information.
36
with NO2 to reform PAN, decreasing PAN levels (Figure 2.21), and increasing the levels of NOx
(Figure 2.23) and O3 (Figure 2.24).
2.3.3.3
Oxygen Containing Organic Compounds
The rate parameters for reactions of carbonyls, alcohols, and organic hydroperoxides were revised.
The carbonyl reactions that were revised are shown in Table C.13. Revisions for reactions of aldehydes and ketones with OH were completed through C5 , while revisions to reactions of carboxylic
acid with OH were completed for
C3 .
In addition, reactions of
C2 aldehydes with NO3 and
HO2 were revised. The revised reactions of alcohols with OH and NO3 are shown in Table 2.7. The
reactions of C4 alcohols with OH were added to the mechanism using rate constants recommended
by Atkinson [1994] and branching ratios calculated using the methods of Atkinson [1987] and Atkinson and Aschmann [1989]. The reactions of methanol, ethanol, and propanol with NO3 were added
to the mechanism, using products based on H–atom abstraction and the recommended upper limit
rate constants from Atkinson [1994]. Several hydroperoxide reactions with OH were also revised,
as shown in Table 2.8.
The revisions to reactions of oxygen containing organic compounds primarily affected the
simulated levels of the compounds themselves. These compounds were not significant sources of
peroxy radicals and did not significantly influence levels of NOx and O3.
37
Table 2.6 Carbonyl Reaction Revisions.
Reaction
! HCO + H2 O
CH2 O + NO3 ! HCO + HNO3
CH2 O + HO2 ! CH2 (OH)(OO) + XPOO
CH2 O + O3 P ! HCO + HO
CH3 CHO + HO ! CH3 CHO(OO) + H2 O + XAOO
CH3 CHO + NO3 ! CH3 CHO(OO) + HNO3 + XAOO
CH3 CHO + O3 P ! CH3 CO + HO
CH3 CHO + NO3 ! CHOCO + HNO3
CH3 CH2 CHO + HO ! CH3 CH2 CO(OO) + H2 O + XAOO
1
CH3 CH2 CH2 CHO + HO ! 0.38 CHOCH2 CH(OO)CH3
+ 1.62 CH3 CH2 CH2 CO(OO) + 2.00 H2 O
2
CH3 CH2 CH2 CHO + HO ! 1.62 XAOO + 0.38 XSOO
CH3 CH(CH3 )CHO + HO ! CH3 CH(CH3 )CO(OO) + H2 O + XAOO
1
CH3 CH2 CH2 CH2 CHO + HO ! 0.38 CH3 CH2 CH(OO)CH2 CHO
+ 1.62 CH3 CH2 CH2 CH2 CO(OO)
2
CH3 CH2 CH2 CH2 CHO + HO ! 2.00 H2 O + 1.62 XAOO + 0.38 XSOO
1
CH3 CH(CH3 )CH2 CHO + HO ! 0.56 CHOCH2 C(OO)(CH3 )CH3
+ 1.44 CH3 CH(CH3 )CH2 CO(OO)
2
CH3 CH(CH3 )CH2 CHO + HO ! 2.00 H2 O + 1.44 XAOO + 0.56 XTOO
CH2 (OH)CHO + HO ! 0.80 CH2 (OH)CO(OO) + 0.20 CHOCHO
CH2 O + HO
+ 0.20 HO2 + 0.80 XAOO
New K298
1.0E-11
5.8E-16
5.0E-14
1.6E-13
1.4E-11
2.4E-15
4.5E-13
4.5E-15
2.0E-11
New E/R
0.0E+00
2.9E+03
-6.0E+02
1.6E+03
-2.7E+02
1.9E+03
1.1E+03
1.9E+03
-2.5E+02
Sources
Madronich and Calvert [1989] a
DeMore et al. [1997] b
DeMore et al. [1997]
Madronich and Calvert [1989] a
DeMore et al. [1997]
DeMore et al. [1997]
Madronich and Calvert [1989] a
Stockwell et al. [1997]
Atkinson [1994] b
1.2E-11
1.2E-11
2.6E-11
-2.5E+02
-2.5E+02
-4.1E+02
Atkinson [1994] c
Atkinson [1994] c
Atkinson [1994] c
1.4E-11
1.4E-11
-4.5E+02
-4.5E+02
Atkinson [1994] c
Atkinson [1994] c
1.4E-11
1.4E-11
-2.6E+02
-2.6E+02
Atkinson [1994] b
Atkinson [1994] b
9.9E-12
1.1E-11
1.7E-11
2.2E-13
3.0E-12
-2.6E+02
0.0E+00
-2.5E+02
6.9E+02
0.0E+00
Atkinson [1994] d
Atkinson [1994]
Atkinson [1994] b
DeMore et al. [1997]
Atkinson [1994]
! CHOCO + H2 O
! CH3 COCO(OO) + H2 O + XAOO
CH3 COCH3 + HO ! CH3 COCH2 (OO) + H2 O + XPOO
CH3 COCH2 (OH) + HO ! CH3 COCHO + HO2
1
CH3 CH2 COCH3 + HO ! 0.96 CH3 COCH(OO)CH3
+ 1.04 CH3 COCH2CH2 (OO) + 2.00 H2 O
5.8E-13
1.8E+02 Atkinson [1994]
2
CH3 CH2 COCH3 + HO ! 0.96 XSOO + 1.04 XPOO
5.8E-13
1.8E+02 Atkinson [1994] c
CH3 CH2 CH2 COCH3 + HO ! CH3 COCH2CH(OO)CH3 + H2 O + XSOO
4.9E-12 -7.6E+01 Atkinson [1994] e; f
CH3 CH2 COCH2 CH3 + HO ! CH3 CH2 COCH(OO)CH3 + H2 O + XSOO
2.0E-12
4.6E+02 Atkinson [1994] e;f; g
C5 H1 2CO + HO ! CH2 CH2 COCH2 CH(OO)CH3 + H2 O
9.1E-12 -1.8E+02 Atkinson [1994] e;f
CH3 COCOCH3 + HO ! CH3 COCOCH2(OO) + H2 O + XPOO
2.4E-13
4.0E+02 Atkinson [1994] c; h
CHO(OH) + HO ! CO2 + H2 O + H
4.0E-13
0.0E+00 DeMore et al. [1997]
CH3 CO(OH) + HO ! CO(OH)CH2 (OO) + H2 O + XPOO
8.0E-13 -2.0E+02 DeMore et al. [1997]
CH3 CH2 CO(OH) + HO ! CH3 CH(OO)CO(OH) + H2 O + XSOO
1.2E-12
0.0E+00 Atkinson [1994]
a Recommended by DeMore et al. [1997]
b No E/R value reported, Madronich and Calvert [1989] value retained
c E/R calculated from D+nT, not reported as an Arrhenius equation
d Branching ratio changed, used that recommended by Atkinson et al. [1992b]
e Reaction added by Williams [1994a]
f No E/R value reported, use E/R generated by Williams [1994a]
g Product changed to 2k53 from 2k52
h New reaction
CHOCHO + HO
CH3 COCHO + HO
38
Table 2.7 Alcohol Reactions.
Reaction
! 0.14 CH2 (OH) + 0.86 CH3 O + H2 O
! CH3 CHO + H2 O + HO2
CH3 CH2 CH2 (OH) + HO ! 0.23 CH3 CH(OO)CH2 (OH)
CH3 (OH) + HO
CH3 CH2 (OH) + HO
+ 0.77 CH3 CH2 CHO + 0.77 HO2 + 0.23 XSOO
! CH3 COCH3 + HO2
1
CH3 CH2 CH2 CH2 (OH) + HO ! 0.03 CH3 C(OO)(CH3 )CH2 (OH)
+ 0.39 CH2 (OH)CH2 CH(OO)CH3
2
CH3 CH2 CH2 CH2 (OH) + HO ! 0.58 CH3 CH2 CH2 CHO
CH3 CH(OH)CH3 + HO
+ 0.58 HO2 + 0.39 XSOO + 0.03 XPOO
! CH3 C(OH)(CH3 )CH2 (OO) + XPOO
! 0.14 CH2 (OH) + 0.86 CH3 O + HNO3
CH3 CH2 (OH) + NO3 ! CH3 CHO + HNO3 + HO2
CH3 CH2 CH2 (OH) + NO3 ! 0.23 CH3 CH(OO)CH2 (OH)
CH3 CH(OH)(CH3 )CH3 + HO
CH3 (OH) + NO3
New K298
8.9E-13
3.2E-12
New E/R
6.0E+02
2.4E+02
Sources
DeMore et al. [1997]
DeMore et al. [1997]
5.5E-12
5.3E-12
0.0E+00
-3.5E+01
Atkinson [1994]
Atkinson [1994] a
4.3E-12
0.0E+00
Atkinson [1994] b; c
4.3E-12
1.1E-12
<6.0E-16
<9.0E-16
0.0E+00
2.7E+02
0.0E+00
0.0E+00
Atkinson [1994]b;c
Atkinson [1994]a;b
Atkinson [1994]b
Atkinson [1994]b
<2.3E-15
0.0E+00
a E/R calculated from D+nT, not reported as an Arrhenius expression
b New Reaction
c Branching ratio calculated using Atkinson et al. [1987]
+ 0.77 CH3 CH2 CHO + 0.77 HO2 + 0.23 XSOO
Atkinson [1994]b
Table 2.8 Hydroperoxide Reactions.
Reaction
A CH (OO) + H O
!
3
2
B
CH3 (OOH) + HO ! CH2 O + HO + H2 O
CH3 CH(OOH)CH3 + HO ! 0.50 CH3 CH(OO)CH3
CH3 (OOH) + HO
+ 0.50 CH3 COCH3 + 0.50 HO + 0.50 XSOO
New K298
5.2e-12
2.2e-12
New E/R
-2.0E+02
-2.0E+02
1.0E-11
3.0E-12
0.0E+00
0.0E+00
Sources
DeMore et al. [1997] a
DeMore et al. [1997] a
Madronich and Calvert [1989] b
Atkinson [1994]
! CH3 C(OO)(CH3 )CH3 + H2 O + XTOO
a Branching ratio and products from Madronich and Calvert [1989]
b product changed from CH3CH2CH2(OO.) to CH3CH(OO)CH3 by Williams [1994a]
CH3 C(OOH)(CH3 )CH3 + HO
39
2.3.3.4
Nitrogen Containing Organic Compounds
Reactions of peroxy acyl nitrates and alkyl nitrates were revised as follows.
Peroxy Acyl Nitrate Revisions The peroxy acyl nitrate revisions include several changes
to reactions involving PAN and its homologues. The formation of PAN was changed from a
bimolecular reaction,
CH3 C(O)OO + NO2
!
CH3 C(O)OONO2;
(2.6)
*
)
CH3 C(O)OONO2 + M:
(2.7)
to a pressure dependent termolecular reaction,
CH3 C(O)OO + NO2 + M
The thermal decomposition reaction rate constant is now calculated from the equilibrium constant
and the PAN formation rate constant recommended by DeMore et al. [1997]. The NCAR Master
Mechanism-Version 2.0, included two reaction paths for the thermal decomposition of PAN,
CH3 C(O)OONO2
!a
CH3 C(O)OO + NO2
!b
+CH3 (ONO2 ) + CO2
(2.8)
:
The thermal decomposition path (Reaction 2.8b), which led to the formation of methyl nitrate was
removed, because studies by Bridier et al. [1991] indicated the only products produced from PAN
decomposition are peroxyacetyl radical and NO2, Additionally, the photolysis of PAN,
CH3 C(O)OONO2 + h
!a
CH3 C(O)OO + NO2
!b
CH3 C(O)O + NO3
(2.9)
40
PAN
Concentration in ppt
400
Madronich and Calvert, Version II, 1989
PAN
PAN Homologues
All PANs
300
200
100
0
0
1
2
3
Time in Days
4
5
6
Figure 2.25 Effect of revisions to peroxy acyl nitrate reactions on PAN levels. Levels of
PAN as a function of time along the trajectory. The solid line uses the unrevised NCAR
Master Mechanism-Version 2.0. The dotted line uses the Master Mechanism with revised
PAN chemistry. The dashed line uses the revised chemistry for the PAN homologues. The
long dashed line indicates the sum of all the revisions to the chemistry of peroxyacyl nitrates.
was added to the mechanism, using a temperature-dependent cross–section [DeMore et al., 1997]
and quantum yields of 0.77 and 0.23 for channels a and b, respectively [Mazely et al., 1997].
The revisions to PAN chemistry result in a shift toward PAN formation, increasing the levels
of PAN as shown in Figure 2.25, and decreasing the levels of NOx (Figure 2.26) and peroxyacetyl
radical (Figure 2.27). As a result of lower NOx levels, the production of O3 (Figure 2.28) is reduced.
The mean levels of NOx and O3 are decreased by 14.1% and 0.4% respectively.
Revisions were also made to the thermal decomposition and formation reactions of the larger
peroxyacyl nitrates. Experimentally determined rate parameters were used if they were available.
Otherwise, for thermal decomposition of the peroxyacyl nitrates, values recommended by Atkinson
[1994] were used (k298
=
6:1 10,04 s,1 , E/R = 1.4E+04 K). The high pressure limit rate constant
recommended by DeMore et al. [1997] (k298
=
8:6 10,12 molec,1 cm3 s,1 ) for the reaction
41
NOx
Concentration in ppt
80
Madronich and Calvert, Version II, 1989
PAN
PAN Homologues
All PANs
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.26 Effect of revisions to peroxy acyl nitrate reactions on NOx levels. Refer to
Figure 2.25 for descriptive information.
Peroxyacetyl Radical
Concentration in ppt
2.0
Madronich and Calvert, Version II, 1989
PAN
PAN Homologues
All PANs
1.5
1.0
0.5
0.0
0
1
2
3
Time in Days
4
5
6
Figure 2.27 Effect of revisions to peroxy acyl nitrate reactions on peroxyacetyl radical levels.
Refer to Figure 2.25 for descriptive information.
42
Ozone
74
Concentration in ppb
72
70
68
66
64
0
Madronich and Calvert, Version II, 1989
PAN
PAN Homologues
All PANs
1
2
3
Time in Days
4
5
6
Figure 2.28 Effect of revisions to peroxy acyl nitrate reactions on O3 levels. Refer to
Figure 2.25 for descriptive information.
of peroxyacetyl radical with NO2 was used for the peroxyacyl nitrate formation reactions where
experimental data did not exist. However, because PAN was the only peroxyacyl nitrate included
in the initial conditions for this simulation, the revisions to the chemistry of PAN homologues do
not significantly affect the levels of NOx (Figure 2.26) or O3 (Figure 2.28).
Alkyl Nitrates Loss reactions were added for C2 –C5 alkyl nitrates. For the larger alkyl nitrates,
C5 , the reaction with OH is dominant, while for smaller alkyl nitrates the photolysis reaction
becomes competitive [Roberts, 1995]. The rate parameters, products, and branching ratios for the
alkyl nitrate reactions with OH were based on the recommendations of DeMore et al. [1997] or
Atkinson [1994]. For the photolysis reactions, the cross sections and quantum yields recommended
by Atkinson [1994] were implemented using the methods described in Section 2.3.1. For completeness, reactions for the products (peroxy, alkoxy, and hydroperoxides) from these new reactions and
subsequent reactions were also added.
43
NOx
Concentration in ppt
80
Madronich and Calvert, Version II, 1989
RONO2
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.29 Effect of revisions to alkyl nitrate reactions on NOx levels. Levels of NOx
as a function of time along the trajectory. The solid line uses the unrevised NCAR Master
Mechanism-Version 2.0. The long dashed line indicates the revisions and additions to the
chemistry of alkyl nitrates.
Revisions to the alkyl nitrate reactions result in an increase in the level of NOx (average NOx
level increased 10.7%), shown in Figure 2.29. With the addition of loss reactions, alkyl nitrates
become a source of NOx , rather than a terminal sink. In this simulation, higher levels of NOx
increase the rate of ozone production, resulting in higher levels as shown in Figure 2.30. The mean
level of O3 is increased by 0.4%. The importance of the alkyl nitrate revisions is partially due to
the relatively high initial conditions.
2.3.3.5
Aromatic Compounds
The reactions of benzene and its products are described in detail in Section 3.2.1.2. Revisions to the
benzene mechanism are shown in Table C.18. The only loss reaction for nitrophenol in the NCAR
Master Mechanism-Version 2.0 is the reaction with NO3 . However, it is believed that reaction with
OH is the dominant gas-phase reaction [Atkinson, 1994]. Therefore, the reaction with OH (k298
44
Ozone
74
Concentration in ppb
72
70
68
66
Madronich and Calvert, Version II, 1989
RONO2
64
0
1
2
3
Time in Days
4
5
6
Figure 2.30 Effect of revisions to alkyl nitrate reactions on O3 levels. Refer to Figure 2.29
for descriptive information.
= 9 10,13 molec,1 cm3 s,1) was added to the mechanism, and the reaction rate constant of
nitrophenol with NO3 was substantially reduced from 3:8 10,12 to 2:0 10,14 molec,1 cm3 s,1 .
These changes have a significant effect on the partitioning between nitrophenol (Figure 2.31) and
dinitrophenol (Figure 2.32). As a result, the levels of NOx were increased (Figure 2.33), slightly
increasing the level of O3, as shown in Figure 2.34. The mean levels of NOx and O3 were increased
by 3.8% and 0.05%, respectively, as a result of the revisions made to the chemistry of aromatic
compounds.
45
Nitrophenol
12
Madronich and Calvert, Version II, 1989
Aromatic Revisions
Concentration in ppt
10
8
6
4
2
0
0
1
2
3
Time in Days
4
5
6
Figure 2.31 Effect of aromatic revisions on nitrophenol levels. Levels of nitrophenol as
a function of time along the trajectory. The solid line uses the unrevised NCAR Master
Mechanism-Version 2.0. The long dashed line indicates the revisions to aromatic chemistry.
Dinitrophenol
10
Madronich and Calvert, Version II, 1989
Aromatic Revisions
Concentration in ppt
8
6
4
2
0
0
1
2
3
Time in Days
4
5
6
Figure 2.32 Effect of aromatic revisions on dinitrophenol levels. Refer to Figure 2.31 for
descriptive information.
46
NOx
Concentration in ppt
80
Madronich and Calvert, Version II, 1989
Aromatic Revisions
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.33 Effect of aromatic revisions on NOx levels. Refer to Figure 2.31 for descriptive
information.
Ozone
74
Concentration in ppb
72
70
68
66
64
0
Madronich and Calvert, Version II, 1989
Aromatic Revisions
1
2
3
Time in Days
4
5
6
Figure 2.34 Effect of aromatic revisions on O3 levels. Refer to Figure 2.31 for descriptive
information.
47
Table 2.9 Revised Aromatic Reactions.
Reaction
C6 H6 + HO ! 0.21 C6 H5 (H)OH(OO) + 0.79 C6 H5 (OH) + 0.79 HO2
C6 H6 + NO3 ! C6 H5(OO) + HNO3
A
C6 H5 (OH) + HO ! C6 H5 (O) + H2 O
B
C6 H5 (OH) + HO ! C6 H5 (OH)(OH)
C6 H5 (OH) + NO3 ! C6 H5 (O) + HNO3
C6 H4 OH,NO2 + HO ! C6 H4(O),NO2 + H2 O
C6 H4 OH,NO2 + NO3 ! C6 H4 (O),NO2 + HNO3
New K298
1.2E-12
<3.0E-17
New E/R
2.1E+02
0.0E+00
2.1E-12
4.0E+02
Atkinson [1994] b
2.4E-11
3.8E-12
2.3E-11
<2.0E-14
4.0E+02
0.0E+00
0.0E+00
0.0E+00
Atkinson [1994]
Atkinson [1994]
Grosjean [1991]b
Atkinson [1994]
a New Reaction
b Branching ratio from Madronich and Calvert [1989] retained
Sources
Atkinson [1994]
Atkinson [1994] a
48
Table 2.10 Percent difference in mean NOx and O3
levels compared to the original mechanism, the NCAR
Master-Mechanism-Version 2.
Mechanism
Photolysis
Inorganic
Organic
Peroxy
PAN
RONO2
Aromatics
Net Result
% Change [NOx ]
-8.4
-10.5
-2.7
23.9
-14.1
10.7
3.8
10.3
% Change [O3 ]
-0.96
-0.02
-0.20
0.69
-0.38
0.38
0.05
-0.29
2.3.4 Comparison of Revisions
The effect of each set of revisions on the levels of NOx and O3 is shown in Figures 2.35 and 2.36.
Table 2.10 compares the magnitude of the effect of each subset of revisions on the mean level of NOx
and O3 , while Table 2.11 compares the changes to the net rate of ozone production. The simulated
levels of NOx and O3 are increased by revisions to the chemistry of peroxy radicals (Section 2.3.3.2),
alkyl nitrates (Section 2.3.3.4), and aromatics (Section 2.3.3.5), while levels of NOx and O3 are
decreased by revisions to photolysis (Section 2.3.1), PAN (Section 2.3.3.4), inorganic (Section 2.3.2)
and organic species (Sections 2.3.3.1 and 2.3.3.3). The revisions to the peroxy radical reactions,
photolysis reactions, and PAN reactions have the largest impact on the levels of NOx and O3 . While
the revisions made for each of the categories individually have large effects on NOx and O3 levels,
when all the revisions are made (shown as Net Result in Figures 2.35 and 2.36) the net effect is
much smaller, because the revisions counteract one another.
Overall, the revisions result in a 10.3% increase and 0.3% decrease in the average levels of
NOx and O3, respectively, in comparison to the original mechanism. With higher levels of NOx ,
the average rate of ozone production is increased, as shown in Table 2.11. However, the average
rate of O3 destruction is increased at an even greater rate, primarily due to the increased photolysis
49
NOx
100
Concentration in ppt
80
60
Madronich and Calvert, Version II, 1989
Photolysis
Inorganic
Organic
Peroxy
PAN
RONO2
Aromatics
Net Result
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.35 Effect of revision subsets on NOx levels. Levels of NOx as a function of time
along the trajectory. The solid line uses the unrevised NCAR Master Mechanism-Version 2.0.
The blue dotted line uses revisions only to photolysis reactions. The light blue dashed line
uses revisions to inorganic reactions. The dash-dot green line uses revisions to organic
reactions (unsubstituted HC, carbonyls, alkyl and alkoxy radicals, hydroperoxides). The
yellow dash-dot-dot line uses peroxy radical revisions. The orange dotted line uses revisions
to PAN reactions. The magenta dashed line uses revisions to alkyl nitrate reactions. The
purple dash-dotted line uses revisions to the aromatic reactions The long dashed red line
indicates the net result of using all revisions.
O3
74
Concentration in ppb
72
70
68
66
64
0
Madronich and Calvert, Version II, 1989
Photolysis
Inorganic
Organic
Peroxy
PAN
RONO2
Aromatics
Net Result
1
2
3
Time in Days
4
5
6
Figure 2.36 Effect of revision subsets on O3 levels. Refer to Figure 2.35 for descriptive
information.
50
Table 2.11 Ozone production and destruction rates in ppb/day, averaged over the duration of the trajectory.
Reaction
MM V2.0
Ozone Production Reactions
HO2 + NO
0.96
CH3 O2 + NO
0.40
RO2 + NO
0.12
production rate
1.48
Photo.
Inorg.
Org.
Peroxy
PANs
RONO2
Aromatic
Net
0.95
0.42
0.13
1.49
0.89
0.39
0.12
1.39
0.95
0.32
0.12
1.40
1.19
0.46
0.08
1.73
0.79
0.35
0.11
1.24
1.08
0.42
0.13
1.63
0.99
0.41
0.12
1.52
1.20
0.40
0.08
1.69
Ozone Destruction Reactions
1.18
H2 O+ O(1 D)
HO2 + O3
0.94
OH+ O3
0.27
NO2 + O3
0.02
destruction rate
2.41
1.53
1.04
0.30
0.02
2.89
1.18
0.92
0.26
0.01
2.37
1.18
0.96
0.28
0.02
2.44
1.19
0.92
0.29
0.02
2.44
1.17
0.92
0.25
0.01
2.36
1.19
0.96
0.28
0.02
2.46
1.19
0.94
0.27
0.02
2.42
1.54
1.05
0.34
0.02
2.95
Net Ozone Production
-0.94
-1.40
-0.98
-1.04
-0.71
-1.12
-0.83
-0.90
-1.29
rate of ozone. The overall effect is a 35% decrease (0.33 ppb/d) in the average rate of net ozone
production.
To determine whether all the groups need to be revised, simulations were run in which groups
of revisions were added one at a time, starting with the photolysis revisions, which had the largest
individual effect on the level of O3 . Revision subsets were then added in the order of the greatest to
the smallest individual effect on the average level of NOx (Table 2.10). As shown in Figure 2.37,
levels of O3 for the simulation with revised photolysis, peroxy, and PAN reactions are fairly close
to those in the simulation with all revised reactions. However, this is the result of individual effects
cancelling one another out, as NOx levels (Figure 2.38) for the same subset of revisions do not
adequately match those in the fully revised simulation. To adequately simulate both NOx and O3 ,
all the groups need to be revised.
51
O3
74
Concentration in ppb
72
70
Madronich and Calvert, Version II, 1989
Photolysis
Photo and Peroxy
Photo, Peroxy, PAN
PPP and RONO2
PPPR and Inorganics
PPPRI and Aromatics
PPPRIA and Organics
Net Result
68
66
64
0
1
2
3
Time in Days
4
5
6
Figure 2.37 Effect of adding revision subsets on O3 levels. The solid black line uses the
unrevised NCAR Master Mechanism-Version 2.0. The blue dotted line uses revisions only
to photolysis reactions. The light blue dashed line uses the previous revisions plus peroxy
radical revisions. The dash-dot green line uses the previous revisions plus the revisions
to PAN chemistry. The yellow dash-dot-dot line uses all the previous revisions plus alkyl
nitrate revisions. The orange dotted line uses all the previous revisions plus revisions
to inorganic reactions. The magenta dashed line uses the previous revisions in addition to
revisions to aromatic reactions. The purple dash-dotted line uses the previous revisions plus
revisions to the organic reactions (unsubstituted HC, carbonyls, alkyl and alkoxy radicals,
hydroperoxides). The long dashed red line indicates the net result of using all revisions.
NOx
100
Concentration in ppt
80
60
Madronich and Calvert, Version II, 1989
Photolysis
Photo and Peroxy
Photo, Peroxy, PAN
PPP and RONO2
PPPR and Inorganics
PPPRI and Aromatics
PPPRIA and Organics
Net Result
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.38 Effect of adding revision subsets on NOx levels. Refer to Figure 2.37 for
descriptive information.
52
Table 2.12 Important Reactions in Each Group of Revisions.
Group
Photolysis
Peroxy
Aromatic
Reaction
O3 + hv ! O2 + O(1 D)
CH3 C(O)OO + NO ! CH3 O2 + CO2 + NO2
CH3 C(O)OO + HO2 ! CH3 CO(OOH) + O2
CH3 C(O)OO + HO2 ! CH3 CO(OH) + O3 a
CH3 C(O)OO + NO3 ! CH3 CO(O) +NO2 + O2 a
CH3 C(O)OO + CH3 O2 ! 1.40 CH3 O + 1.40 CH3 CO(O) + 0.60 CH2 O + 0.60 CH3 CO(OH)
CH3 C(O)OO + XPOO ! 0.8 CH3 CO(O) + 0.2 CH3 CO(OH)
CH3 C(O)OO + XSOO ! 0.8 CH3 CO(O) + 0.2 CH3 CO(OH)
CH3 C(O)OO + XTOO ! CH3 CO(O)
CH3 C(O)OO + XAOO ! CH3 CO(O)
CH3 C(O)OONO2 + (M) ! CH3 C(O)OO + NO2 + (M)
CH3 C(O)OO + NO2 + (M) ! CH3 C(O)OONO2 + (M)
CH3 C(O)OONO2 + hv ! CH3 C(O)OO + NO2
CH3 C(O)OONO2 + hv ! CH3 CO(O) + NO3
CH3 C(O)OONO2 + OH! CO(OONO2 )CH2 (OO) + H2 O
removed NO3 + M ! NO + O2 + M
OH+ NO2 + (M) ! HNO3 + (M)
N2 O5 + H2 O! 2 HNO3
CH4 + OH! CH3 + H2 O
CH4 + NO3 ! CH3 + HNO3
A
nitrophenol + OH! C6H5(O) + H2 O
Alkyl Nitrates
nitrophenol + OH! dinitrophenol
nitrophenol + NO3 ! C6H5(O) + HNO3
all revisions made
PAN
Inorganic
Organic
B
Since the “Net Result” simulation includes revisions to a large number of reactions, additional
simulations were conducted to determine whether the number of necessary revisions could be
reduced by updating only the most important reaction or reactions in each category. As discussed
above, in many cases only a few reactions are responsible for a majority of the changes in NO x and O3
levels resulting from all revisions to each category. These reactions are listed in Table 2.12, and the
result of a simulation in which only those reactions were modified is shown in Figures 2.39 and 2.40.
As is apparent in Figures 2.39 and 2.40, the relatively smaller effects of the revisions to the relatively
large number of reactions not listed in Table 2.12 collectively alter the simulated NOx and O3 levels.
The key reactions increase the mean NOx level 0.49%, and decrease the mean O3 level by 0.51% in
53
NOx
80
Madronich and Calvert, Version II, 1989
Key Reactions
Net Result
Concentration in ppt
60
40
20
0
0
1
2
3
Time in Days
4
5
6
Figure 2.39 Effect of revising only a few reactions within each subset on NOx levels. Levels
of NOx as a function of time along the trajectory. The solid black line uses the unrevised
NCAR Master Mechanism-Version 2.0. The blue dotted line uses revisions to the reactions
listed in Table 9. The long dashed line indicates the net result of using all revisions.
Ozone
74
Concentration in ppb
72
70
68
66
Madronich and Calvert, Version II, 1989
Key Reactions
Net Result
64
0
1
2
3
Time in Days
4
5
6
Figure 2.40 Effect of revising only a few reactions within each subset on O3 levels. Refer to
Figure 2.39 for descriptive information.
54
comparison to the original mechanism. The difference between the results from the simulation with
only key reactions and the simulation that includes all the revisions is primarily due to revisions to
peroxy radical reaction rate constants.
2.4 Conclusions
Over 3200 reactions in the NCAR Master-Mechanism were revised in increments to determine the
effect of each subset of revisions on the simulated levels of NOx and O3 . Revisions to photolysis,
peroxy radical, and PAN reactions have the largest effects on the simulated levels of NOx and O3 .
Revising the photolysis parameters decreases the mean levels of O3 and NOx by 1.0% and 8.4%,
respectively. The revised ozone quantum yield accounts for nearly this entire change. It is expected
that in regions with a higher actinic flux, the effect of increasing the quantum yield of ozone would
be even greater. However, the initial level of ozone is relatively high due to the trajectory’s initial
altitude, which likely emphasizes the importance of the change to the O3 quantum yield relative
to scenarios with lower ozone levels. The overall effect of peroxy radical revisions increases
the removal rate of the peroxyacyl radicals (primarily peroxyacetyl radical in these simulations),
reducing the amount available for PAN reformation, which increases the levels of NOx and O3
on average by 23.9% and 0.7%, respectively. In comparison to the original mechanism, the PAN
revisions have shifted the equilibrium toward PAN formation, decreasing the levels of NOx (by
14.1% on average), and therefore decreasing the level of O3 (by 0.4% on average).
The overall effect of the revisions made to the mechanism results in a decrease in the mean levels
of NOx and O3 by 10.3% and 0.29%, respectively, while the average net rate of ozone production
was decreased by 35%. The decrease in NOx levels is primarily due to increased removal rates of
55
the peroxyacetyl radical.
The effect of many of the revision subsets are larger than the net result, as many of the individual
revisions counteract each other. As a result, if only a small number of kinetic and mechanistic
parameters are updated in a gas-phase mechanism, the change in the simulated levels of NOx and
O3 could be even larger than the net result, depending on which parameters are revised. Therefore,
our recommendation is to update the following reactions in both explicit and lumped mechanisms:
ozone photolysis, PAN reactions, peroxyacyl radical reactions, inorganic reactions, and methane
chemistry. If aromatic chemistry or organic nitrates are important to the simulation (as they are
in the case of arctic outflow) it is important to make the revisions to reactions of those species as
discussed above. Additionally, for explicit mechanisms, it is important to examine more than just
the reactions listed above, as the effects of many relatively small changes can have a significant
effect collectively. While the simulations in this chapter examined the impact of revisions for the
specific case of arctic outflow, the results are expected to be applicable to other model results, as
the reactions listed above are crucial to determining the levels of NOx and O3 and are included in
most gas-phase mechanisms (both explicit and lumped).
Chapter 3
Impact of Winter–Spring Arctic Outflow
on the NOx and O3 Budgets of the North
Atlantic Tropospherey
This chapter contains an analysis of the impact of winter–spring arctic outflow events on the
tropospheric budgets of NOx and ozone over the North Atlantic Ocean. To accomplish this, a photochemical model, the NCAR Master Mechanism-Version 2.0, is applied to isentropic trajectories
selected from the climatology developed by Honrath et al. [1996]. A description of the model
and criteria used for trajectory selection is provided in Section 3.1. This is followed by a detailed
discussion of the chemical cycling of NOx in arctic outflow events and the resulting impact on O3 .
y This chapter is based on material accepted for publication as A.J. Hamlin and R.E. Honrath, A Modeling
Study of the Impact of Winter–Spring Arctic Outflow on the NOx and O3 Budgets of the North Atlantic
Troposphere, Journal of Geophysical Research, in press, 2002.
56
57
Finally, the fluxes of NOx and O3 to the North Atlantic resulting from arctic outflow are calculated
and compared to other sources to the region.
3.1 Model Description
Trajectories for simulation were selected from the climatology of forward isentropic arctic outflow
trajectories developed by Honrath et al. [1996]. These trajectories were calculated twice daily for
the months of January–May and years 1984–1994 using methods described in detail by ? [?]. They
originate at 70 N latitude and within the longitude range of 130 W to 50 E. The climatology
includes only trajectories that have an initial southward velocity and reach the North Atlantic region
(defined here as 10–70 W and 20–50 N).
Arctic outflow events are usually the result of large-scale transport along a semipermanent long
wave trough located near the east coast of North America [Honrath et al., 1996]. The resulting
flow pattern is relatively well organized, and funnels arctic air southward over central and eastern
Canada and eastward over the North Atlantic, while subsiding in altitude. The present simulations
are meant to describe the photochemistry occurring in an air parcel that is part of such a larger outflow
airmass, of homogeneous composition. For this purpose, we use a zero-dimensional model of the
photochemistry in the air parcel, with the implicit assumption that mixing with other outflowing air
does not significantly alter concentrations during southward transport.
Photochemistry occurring over the duration of arctic outflow events was fully simulated for a
set of 15 trajectories. These trajectories were selected to span a range of chemical outcomes, based
on the relative amount of PAN decomposition and corresponding NOx release. For the purpose
of trajectory selection, the expected gross PAN decomposition rate integrated over the duration of
58
each of 22,692 trajectories from the climatology was calculated based on thermal decomposition
rates at the temperatures and pressures encountered along the trajectory, without considering any
other chemistry. Trajectories corresponding to the 16.7, 50, and 83.3 percentiles of gross PAN
decomposition were then selected for detailed analysis. The selected trajectories corresponding to
low (16.7th percentile of integrated gross PAN decomposition), median (median integrated gross
PAN decomposition), and high (83.3rd percentile of integrated gross PAN decomposition) are shown
in Figures 3.1– 3.3. Analyses were conducted for each of the five months January–May. In the
discussion below, we focus on results for January, March, and May. However, results for February
and April are consistent with those presented. The selected forward trajectories ranged in duration
from 1.5 to 8.5 days; trajectories were terminated either because they left the North Atlantic region
or because they entered the boundary layer, where the altitude of a given isentropic (potential
temperature) level is not uniquely defined.
To simulate the evolution of O3 and its precursors in arctic outflow, a photochemical box
model was applied to each of the representative trajectories. The photochemical box model was
advanced along the trajectory at 15 minute intervals, providing new positional (latitude, longitude,
altitude) and environmental (temperature, humidity) data. The model used in this study is the
NCAR Master Mechanism of the Gas Phase Chemistry-Version 2.0 [Madronich and Calvert, 1989;
Madronich and Calvert, 1990], revised as discussed in Chapter 2 The Master Mechanism is a chemically explicit photochemical model which includes over 5000 gas-phase reactions and approximately
1900 chemical species. The most significant revisions to the mechanism as used in this work include
the addition of pressure dependence to the PAN equilibrium reaction [Kirchner and Stockwell, 1996;
DeMore et al., 1997] and revision of the peroxy radical reactions [Kirchner and Stockwell, 1997;
59
12
Altitude (km)
10
8
1
6
1
4
23
1
2
2
4
3
2
4
5
5
0
-100
-50
Longitude
0
50
90
45
80
1
2
1 -90 1
3
70
60
0
-45
50
24
3
40
5
2
4
5
30
Figure 3.1 Representative arctic outflow trajectories selected to span chemical outcomes
for January. The dotted line indicates low-PAN-decomposition, the dashed line indicates median-PAN-decomposition, and the solid line indicates high-PAN-decomposition. Numerals
indicate days of transport.
60
12
Altitude (km)
10
8
1
6
4
2
1
3
2
1
2
2
4 4
3
0
-100
55
-50
Longitude
0
50
90
45
1
1
80
70
22
-90
3
60
0
1
-45
50
34
5
4 2
5
40
30
Figure 3.2 Representative arctic outflow trajectories selected to span chemical outcomes
for March. Refer to Figure 3.1 for descriptive information.
61
12
Altitude (km)
10
8
1
6
21
5
4
23
4
1
2
2
3
4
3
0
-100
6
5
45
-50
Longitude
0
50
90
45
80
1
70
21
1
3 2
2
3 -45
4
-90
60
0
5
4
5
3
50
6
40
30
4
5
Figure 3.3 Representative arctic outflow trajectories selected to span chemical outcomes
for May. Refer to Figure 3.1 for descriptive information.
62
Madronich and Calvert, 1990; Kirchner and Stockwell, 1996]. Additionally, quantum yields
and cross-sections were revised for nitrogen and oxygen-containing compounds [Atkinson, 1994;
DeMore et al., 1997; Sander et al., 2000], and rate constants were updated for reactions of nonsubstituted and mono-substituted organic compounds through C4 [Atkinson, 1994], benzene oxidation [Grosjean, 1991; Atkinson, 1994], and inorganics [DeMore et al., 1997]. These revisions are
discussed in detail in Chapter 2. Deposition and wet removal are not included in these simulations.
Thus, levels of nitric acid (and to a lesser extent, nitroaromatic compounds) build up during the simulations. This does not affect the simulation of NOx levels, as further reactions of these compounds
are insignificant in these simulations, but means that mixing ratios presented for these compounds
indicate integrated production, and should be treated as upper limits for true mixing ratios in outflowing arctic air. The chemical mechanism used in the present simulations was reduced to 719 species
and 2075 reactions by including only those reactions involving chemical species present in the
winter–spring arctic free troposphere and their products. The initial conditions were based on previous measurements of arctic or subarctic air and are shown in Tables 3.1 and 3.2. As the initial level of
ozone is altitude dependent, ranging from 35 to 80 ppbv in the arctic free troposphere [Logan, 1985;
Oltmans, 1993] and because the trajectories simulated here were meant to be representative of the
full suite of southward flowing trajectories, simulations were run for each trajectory with both a
low-initial-ozone level of 35 ppbv, and a high-initial-ozone level of 80 ppbv.
Photolysis rates were calculated at each 15 minute time step along the trajectory using actinic
fluxes calculated using Phodis Version 0.40 [Kylling, 1995]. The six-stream pseudo-spherical
radiative transfer algorithm was used, assuming clear sky conditions. Fall–winter background
aerosol vertical profiles were used for the January and February simulations, while spring–summer
63
Table 3.1 Initial Conditions.
Compound
N2
O2
H2
O3
CO
CO2
CH4
C2 H2
C2 H4
C2 H6
C3 H6
C3 H8
n-butane
i-butane
n-pentane
i-pentane
C6 H6
January–March
.7808*air density
.2095*air density
0.5 ppm
35, 80 ppb
170 ppb
360 ppm
1.8 ppm
0.8 ppb
0.4 ppb
2.7 ppb
0.03 ppb
1.4 ppb
0.6 ppb
0.33 ppb
0.2 ppb
0.25 ppb
0.26 ppb
Mixing Ratio
April
.7808*air density
.2095*air density
0.5 ppm
35, 80 ppb
170 ppb
360 ppm
1.8 ppm
0.6 ppb
0.1 ppb
2.2 ppb
0.03 ppb
0.8 ppb
0.25 ppb
0.1 ppb
0.05 ppb
0.1 ppb
0.2 ppb
May
.7808*air density
.2095*air density
0.5 ppm
35, 80 ppb
170 ppb
360 ppm
1.8 ppm
0.3 ppb
0.1 ppb
1.5 ppb
0.03 ppb
0.3 ppb
0.07 ppb
0.03 ppb
0.02 ppb
0.01 ppb
0.15 ppb
Notes
a
a
a
b
c–d
c
c
e–k
e–k
e–k
e–g, j–k
e–k
e–j
f–j
f–j
f–j
f–k
a) Based on the composition of air [Graedel and Crutzen, 1993]. b) Oltmans
[1993]. Ozone level is altitude dependent; two values were chosen to bound the range
of the free troposphere. c) Derwent et al. [1998]. d) Novelli et al. [1998]. e) Solberg
et al. [1996b], non-ozone depletion events. f) Solberg et al. [1996a]. g) Laurila and
Hakola [1996]. h) Ariya et al. [1998]. i) Jobson et al. [1994]. j) Doskey and Gaffney
[1992]. k) Hov et al. [1984].
background aerosol vertical profiles were used for the March–May simulations. A horizontal
visibility of 25 km was chosen to be representative of weak arctic haze conditions [Radke et al.,
1984]. The albedo was varied depending on the location of the box model along the trajectory:
0.8 for snow and ice encountered north of 60 N (and north of 45 N if west of 55 W); and 0.05
over the open ocean [Kondratyev, 1969]. The subarctic winter model atmosphere [Anderson et
al., 1986] used in the calculation of the actinic flux was scaled to the average monthly total ozone
column for Barrow and Fairbanks (also includes data from Poker Flat), Alaska, for the time period
covering 1986–1998. (M. Clark, 2000, personal communication, Data obtained from NOAA’s
Climate Monitoring and Diagnostics Laboratory (CMDL) Ozone and Water Vapor group web site:
http://www.cmdl.noaa.gov/ozwv).
64
Table 3.2 Initial Conditions Continued.
Mixing Ratio
Compound
January–March April
May
Notes
NOx
19 ppt
19 ppt
19 ppt
l
HONO
6 ppt
6 ppt
6 ppt
m
HNO3
16 ppt
16 ppt
16 ppt
n
PAN
300 ppt
300 ppt
300 ppt o
PPN
54 ppt
54 ppt
54 ppt
p
methyl nitrate
0
0
0
q
ethyl nitrate
0
0
0
r
1-propyl nitrate
3.3 ppt
3.3 ppt
3.3 ppt
s–t
2-propyl nitrate
12.4 ppt
12.4 ppt
12.4 ppt s–t
1-butyl nitrate
1.7 ppt
1.7 ppt
1.7 ppt
s–t
2-butyl nitrate
18.4 ppt
18.4 ppt
18.4 ppt s–t
pentyl nitrate
1.0 ppt
1.0 ppt
1.0 ppt
s–t
3-methyl-2-pentyl nitrate 4.8 ppt
4.8 ppt
4.8 ppt
s–t
2-pentyl nitrate
5.4 ppt
5.4 ppt
5.4 ppt
s–t
3-pentyl nitrate
4.3 ppt
4.3 ppt
4.3 ppt
s–t
2-methyl-1-pentyl nitrate 0.8 ppt
0.8 ppt
0.8 ppt
s–t
l) Estimated from Jaffe et al. [1991], Honrath and Jaffe [1992], Weinheimer et
al. [1994], Beine et al. [1996], Rohrer et al. [1997], and Beine et al. [1997a]. This
value is consistent with NOx observed in the Arctic during late spring [Ridley et al.,
2000], but higher than Ridley’s measurements prior to arctic sunrise. (Model results
are insensitive to the initial NOx level.) m) Li [1994], light period. n) Estimated from
Bottenheim et al. [1993] period 1 and Bottenheim and Gallant [1989]. Loss reactions
of HNO3 are negligible in these simulations, so model results are insensitive to the
initial level of HNO3 . o) Estimated from Bottenheim and Gallant [1989], Bottenheim
et al. [1993], Beine et al. [1997b], and Beine and Krognes [2000]. High values were
given more weight to provide an upper limit for NOx release. For this reason and to
allow for comparisons of photochemical processes by month, seasonal variations were
not included. p) PPN levels are 18% of PAN levels [S. Bertman, Western Michigan
University, personal communication, 2000]. q) There are no reported measurements
of methyl nitrate in arctic or subarctic air. r) Measurements of ethyl nitrate have not
been reported for the arctic or subarctic. s) Leaitch et al. [1994]. t) Muthuramu et al.
[1994].
65
3.2 Results and Discussion
3.2.1 Nitrogen Oxides
The evolution of NOy speciation along the simulated arctic outflow trajectories with low-initialozone levels is shown in Figure 3.4. (Trajectories with high-initial-ozone levels behave similarly to
those shown in terms of NOy speciation). Changes in NOy speciation are dominated by net PAN
decomposition (which is controlled by temperature) and the fate of NOx (which also depends on
sunlight intensity). There is a seasonal variation in the NOy chemistry of arctic outflow. As HNO3
is not removed from the air parcels in these simulations, decreasing amounts of PAN and increasing
amounts of HNO3 indicate the degree of NOx release and NOx processing, respectively. The amount
of processing increases from January, when only the high-PAN-decomposition simulation shows
a change in NOy speciation, to May, when the median- and high-PAN-decomposition simulations
demonstrate significant processing. There are some large peaks ( 50 pptv) in the NOx levels,
primarily in the high-PAN-decomposition simulations. A high level of NOx is maintained for
2.5 days during the May high-PAN-decomposition simulation. However, increases in NOx are
highly damped relative to the declines in PAN. The simulated NOx mixing ratios reflect the
balance between temperature-dependent PAN decomposition and a variety of NOx loss reactions.
To illustrate this balance, we now examine the budget of NOx more closely.
3.2.1.1
Sources of NOx
There are two NOy groups expected to release NOx in the remote low- to mid-troposphere: PAN
compounds and alkyl nitrates. Figure 3.5 compares the importance of these NOy groups as NOx
66
300
B
200
100
0
0.0
A
0.5
1.0
1.5
Time (day)
2.0
Jan-Median-PAN-Decomposition
400
300
B
200
500
100
0
1
2
3
4
Time (day)
B
200
100
May-Low-PAN-Decomposition
500
A
0.5
1.0
1.5
Time (day)
2.0
300
B
200
100
0
1
2
3
Time (day)
4
B
200
100
A
0
1
2
3
4
Time (day)
5
6
May-Median-PAN-Decomposition
500
A
0
5
300
0
F
E
D
C
400
F
E
D
C
400
2.5
March-Median-PAN-Decomposition
A
0
300
500
Mixing Ratio (pptv)
Mixing Ratio (pptv)
F
E
D
C
400
0
0.0
2.5
500
F
E
D
C
Mixing Ratio (pptv)
400
500
Mixing Ratio (pptv)
Mixing Ratio (pptv)
March-Low-PAN-Decomposition
F
E
D
C
Mixing Ratio (pptv)
Jan-Low-PAN-Decomposition
500
400
F
E
300
D
C
200
B
100
A
0
5
0
1
2
3
4
Time (day)
5
400
400 300
300
B
200
100
0
200
0
500
Mixing Ratio (pptv)
Mixing Ratio (pptv)
March-High-PAN-Decomposition
F
E
D
C
A
1
2
3
4
Time (day)
5
F
E
D
C
400
300
B
200
100
May-High-PAN-Decomposition
500
Mixing Ratio (pptv)
Jan-High-PAN-Decomposition
500
F
400
E
300
200
D
C
B
A
100
A
0
0
0
1
2
3
4
Time (day)
5
0
1
2
3
4
Time (day)
5
100
0
A) NOx
B) PANs
C) RONO2
D) Aromatics
E) HNO3
F) Other Inorganics
Figure 3.4 The levels of NOx , PAN and PAN homologues, alkyl nitrates, nitro–aromatic
compounds, HNO3 , and other inorganic nitrogen compounds (HNO4 , HNO2 , N2 O5 , and NO3 )
are shown as a function of time along the trajectories simulated for January, March, and May
with low-initial-ozone levels. The upper plots depict results for the low-PAN-decomposition
simulations, the center plots show the median-PAN-decomposition simulations, and the lower
plots show the high-PAN-decomposition simulations. NO, shown as the dashed line within
NOx , indicates the diurnal cycle, with peaks occurring at solar noon.
67
sources for the low-, median-, and high-PAN-decomposition simulations. The height of the each
bar indicates the magnitude of net formation of NOx from each NOy group, integrated over the
length of each trajectory and normalized by trajectory duration. As shown in Figure 3.5, PAN is
the largest source of NOx, while the PAN homologues (due to NOx release from PPN) and alkyl
nitrates are minor sources. (Results shown in Figure 3.5 are from the low-initial-ozone simulations;
results from simulations with high-initial-ozone were not qualitatively different.) In the following
sections we consider PAN, PAN homologues, and alkyl nitrates in more detail to demonstrate which
reactions are most important to the formation of NOx in winter-spring arctic outflow.
PAN The thermal decomposition of PAN is the most important source of NOx in these simulations.
The decomposition of PAN is pressure dependent and is in equilibrium with its reformation [DeMore
et al., 1997],
CH3 C(O)OONO2 + M
*
)
CH3 C(O)OO + NO2 + M:
(3.1)
PAN photolysis,
CH3 C(O)OONO2 + h
A
!
CH3 C(O)OO + NO2
B
!
CH3 CO(O) + NO3 ;
(3.2)
also releases a small amount of NOx through channel A, the dominant channel. While PAN also
reacts with OH, in these simulations this loss process is negligible in comparison to PAN thermal
decomposition, even for the trajectories at high altitudes.
Net NOx formation occurs when the PAN equilibrium is pushed out of balance by reactions
which compete for the peroxyacetyl radical. While on average the most important loss process for
68
Low PAN Decomposition
4
2
May
NO3
N2O5
HO2NO2
Nitroaromatics
RONO2
HNO3
-2
PAN
Homologues
0
PAN
Net NOx Production (ppt/day)
January
March
-4
Median PAN Decomposition
20
May
10
NO3
N2O5
HO2NO2
Nitroaromatics
RONO2
HNO3
-10
PAN
Homologues
0
PAN
Net NOx Production (ppt/day)
January
March
-20
High PAN Decomposition
50
May
25
NO3
N2O5
HO2NO2
Nitroaromatics
RONO2
HNO3
-25
PAN
Homologues
0
PAN
Net NOx Production (ppt/day)
January
March
-50
Figure 3.5 Comparison of NOy groups as sources and sinks of NOx . The height of each
bar indicates the average net NOx formation or destruction for each NOy group for the low-,
median-, and high-PAN-decomposition simulations.
69
the peroxyacetyl radical is reaction with NO2 (occurring 60–80% of the time), during the daytime
reactions with NO,
CH3 C(O)OO + NO
!
CH3 O2 + CO2 + NO2 ;
(3.3)
A
!
CH3CO(OOH) + O2
(3.4)
B
!
CH3CO(OH) + O3;
O2
and HO2 ,
CH3 C(O)OO + HO2
are equally or even more important than reaction with NO2 . Because there is no net loss of NOx and
rapid loss of CH3 C(O)OO in Reactions 3.3–3.4, the thermal decomposition of PAN (Reaction 1)
results in the buildup of NOx during the daytime, peaking at sunset. (The longitudinal movement of
the trajectories results in a variable-length diurnal cycle, which can be distinguished by examining
the levels of NO indicated by the dotted line in Figure 3.4, as peaks in NO coincide with solar noon.)
PAN Homologues Peroxypropionyl nitrate (PPN) is the only other PAN compound included in
the initial conditions. Its thermal decomposition releases NOx,
CH3CH2C(O)OONO2
!
CH3CH2(O)OO + NO2 ;
(3.5)
accounting for the net NOx formation of the PAN homologues shown in the median- and high-PANdecomposition simulations of Figure 3.5. In the May-low-PAN-decomposition simulations the rate
of PPN thermal decomposition is less than the rate of formation of other PAN homologues,
RC(O)OO + NO2
!
RC(O)OONO2 ;
resulting in a small net loss of NOx to the PAN homologues.
(3.6)
70
Alkyl Nitrates Alkyl nitrates release NOx through their photolysis
RONO2 + h
!
RO + NO2
(3.7)
ROR’ + NO2
(3.8)
and their reaction with OH,
RONO2 + OH
A
!
O2 ;B
!
R(OO)ONO2 ;
the photolysis reaction being the dominant source of NOx . As shown in Figure 3.5, alkyl nitrates are
a relatively small source of NOx , but are comparable with PAN during the low-PAN-decomposition
simulations. Their maximum contribution occurs as sunlight intensity increases in April and May.
3.2.1.2
Sinks of NOx
The sinks of NOx are compared in Figure 3.5. The largest sink for NOx in these simulations is
the formation of HNO3 , followed by formation of nitroaromatic compounds (2-nitrophenol, 2,4dinitrophenol, and nitrobenzenediol). Figure 3.4 shows a substantial increase in the level of HNO3
and nitroaromatic compounds as a function of time along each trajectory. As noted above, these
levels are upper limits of atmospheric mixing ratios, because removal terms are not taken into
account. HO2 NO2 is a temporary reservoir for NOx in these simulations, and while it generally
results in little net removal of NOx on average (Figure 3.5), levels of HO2NO2 reach up to 20 pptv
(5% of NOy ) during several simulations (Group F: Other Inorganics in Figure 3.4).
HNO3 There is a shift in the dominant mechanism of HNO3 formation from the dark, low
photochemical activity January–March simulations to the light, photochemically active May simulations. During all January–March simulations, and during the April median-PAN-decomposition
71
simulation, HNO3 formation via N2 O5 hydrolysis,
NO3 + NO2 + M
!
N2 O5
N2 O5 + H2 O
!
2HNO3 ;
(3.9)
(3.10)
is dominant. This is followed in importance by H–atom abstraction of hydrocarbons by NO 3
NO2 + O3
NO3 + RH
A
!
NO3 + O2
B
!
NO + 2O2
!
HNO3 + R
(3.11)
(3.12)
and by OH oxidation of NO2
NO2 + OH + M
!
HNO3 + M:
(3.13)
During April low- and high-PAN-decomposition and all May simulations, when the actinic flux is
larger and OH levels are higher, Reaction 3.13 becomes the dominant source of HNO3 formation,
followed by N2 O5 hydrolysis (Reactions 3.9–3.10) and H–atom abstraction (Reactions 3.11–3.12).
This finding is consistent with the modeling results of Liang et al. [1998], Dentener and Crutzen
[1993], and Wang et al. [1998c].
It is believed that N2O5 hydrolysis (Reaction 3.10) is mainly a heterogeneous reaction [Jacob,
2000], although recent studies suggest that the gas-phase reaction may also be important, especially
in regions with a low aerosol load [Mentel et al., 1996; Wahner et al., 1998; Allan et al., 1999].
A number of regional and global models have used a pseudo first-order rate constant (k= 0:1 ,
1 10,4 s,1 ) to approximate this heterogeneous reaction [Dentener and Crutzen, 1993]. The
NCAR Master Mechanism-Version 2.0 treats N2 O5 hydrolysis as a gas–phase reaction. The rate
72
constant was revised to use the gas-phase rate constant recommended by DeMore et al. [1997]
(k< 2:0 10,21 cm3 molecules,1 s,1 ). Due to the difficulty in separating the homogeneous and
heterogeneous processes of this reaction, this rate constant is an overestimate of the gas-phase-only
rate constant and is equal to 4 times the upper limit gas phase rate constant determined by Sverdrup
et al. [1987]. As a result, while N2 O5 hydrolysis is modeled as a gas phase process, the rate is
consistent with that expected for the combination of homogeneous and heterogeneous reactions.
In particular, it is consistent with the rate constant calculated by Dimitroulopoulou and Marsh
[1997] for both the heterogeneous and homogeneous processes and is within the range of the yearly
mean values calculated by Dentener and Crutzen [1993] for the reaction of N2O5 on sulfate and
sea-salt aerosols for this range of latitudes. At any rate, the results presented here are not highly
sensitive to the value of the N2O5 hydrolysis rate constant as the overall rate-limiting step in these
simulations is the formation of NO3 through the reaction of O3 with NO2. To verify this, simulations
were conducted along the January-high-PAN-decomposition trajectory in which a range of reported
N2 O5 hydrolysis rate constants were used, varying over 2 orders of magnitude [Hough, 1991;
Dimitroulopoulou and Marsh, 1997] and spanning the rate constant used in the revised NCAR
Master Mechanism. The resulting levels of NOx and O3 varied by less than 10% and 1% respectively.
Nitroaromatic Compounds As a result of oxidation of benzene present in arctic air, several nitroaromatic compounds are formed during these simulations, including 2-nitrophenol, 2nitrophenoxy, 2,4-dinitrophenol, and 1,1-dihydroxy-2-nitrate-3,5-cyclohexadiene. As shown in Figure 3.4, levels of these compounds increase from January to May and from low-PAN-decomposition
to high-PAN-decomposition simulations for each of these months. The most important component
of this group of compounds is the nitrophenols.
73
There is a significant degree of uncertainty regarding the mechanisms and products of benzene oxidation, which implies that the simulated amounts of nitroaromatics formed are somewhat
uncertain. However, the NCAR Master Mechanism-Version 2.0 accurately reflects current understanding (with several minor simplifications which are discussed below). Since nitroaromatics are
an important NOx sink in some of these simulations, the oxidation of benzene is examined here.
Benzene undergoes oxidation by OH and NO3 . Reaction with OH proceeds primarily through
addition with a minor path proceeding by H–atom abstraction. As shown in Figure 3.6, OH addition
to benzene (I) produces the hydroxycyclohexadienyl (HCHD) adduct (II). The H–atom abstraction
path results in a phenyl radical (III). This radical reacts rapidly with O2 to form a phenyl peroxy
radical (IV) that reacts with NO or NO2 to form a phenoxy radical (V), whose reactions are discussed
in more detail below.
The HCHD adduct (II) can dissociate back to its products (benzene and OH) or react with NO2 or
O2 . The reaction of HCHD with NO2, resulting in nitrobenzene (VI), is significant only when NOx
levels are high; at room temperature this corresponds to a NOx level > 3:0 1012 molecule cm,3 ,
a range typically used in environmental chamber studies [Atkinson, 1994]. Earlier studies suggest
that the HCHD adduct may also react with NO [Zellner et al., 1985], but this conclusion was
disputed [Atkinson, 1994]. The only reaction of the HCHD adduct which is important in the remote
troposphere is its reaction with O2. The reaction of HCHD with O2 results in phenol (VII), as
the major product, and hydroxy-2,4-cyclohexadienyl-6-peroxy radical (VIII). The hydroxy-2,4cyclohexadienyl-6-peroxy radical undergoes ring-opening and results in products such as glyoxal
(CHOCHO). (For a complete discussion of the reactions of the hydroxy-2,4-cyclohexadienyl-6peroxy radical, see Lay et al. [1996].)
74
OH
+ HO2
O2
(VII)
H
OH addition
OH
O2
H
NO2
(II)
H
OH
H
OO
ring opened
products
(VIII)
NO2
+ H2O
(VI)
(I)
abstraction by
OH or NO3
OO
O2
(IV)
(III)
NO
NO2
NO2
NO3
O
(V)
Figure 3.6 Mechanism of benzene oxidation.
75
In the modified version of the NCAR Master Mechanism-Version 2.0 used here, the reaction of
benzene with OH is consistent with these expected reactions. A hydrogen atom abstraction route
has been added. The addition route skips over the production of the HCHD adduct, but products
of OH addition to benzene are consistent with those expected for the HCHD adduct reaction with
O2 : phenol and the hydroxy-2,4-cyclohexadienyl-6-peroxy radical. While nitrobenzene is not
produced in the NCAR Master Mechanism, product studies indicate that there is only a small yield
(0:0336 0:0078 + (3:07 0:92) 10,16 [NO2] [Atkinson et al., 1989a]) from the reaction of
benzene with OH in the presence of NOx . Since these simulations apply to the remote atmosphere
and are characterized by low NOx levels, this is a valid simplification. Additionally, the reaction
of benzene with NO3 is not included in the NCAR Master Mechanism-Version 2.0. While it is a
minor reaction, it may be important during the night or winter, especially at high latitudes. For this
reason the reaction of benzene with NO3 was added.
Phenol (VII), the primary product of benzene oxidation, is removed quickly from the atmosphere.
Phenol reacts with OH during the day, mainly by addition but also by H–atom abstraction, and reacts
with NO3 at night. OH addition to phenol results in 1,1-benzenediol (IX), shown in Figure 3.7,
and its isomers. For simplicity, the NCAR Master Mechanism-Version 2.0 only considers 1,1benzenediol. H–atom abstraction from phenol is expected to result in the production of phenoxy
(V) and HNO3 or H2 O. It is expected that OH–addition is the dominant reaction and that H–atom
abstraction is a minor route [Atkinson, 1994]. However, in most of the simulations for January
through March, H–atom abstraction by NO3 is the dominant loss reaction for phenol, due to low
OH levels. As the actinic flux increases in April and May, OH addition to phenol becomes more
important than the reaction with NO3 . An additional loss process for phenolic compounds is wet
76
OH OH
OH OH
OO
O2
OH addition
OH
(IX)
NO
NO2
(VII)
HO2
OH OH
ONO2
O
OH
NO2
NO2
abstraction by
OH or NO3
(X)
(XI)
(V)
abstraction by
OH or NO3
OH addition
O
OH OH
NO2
NO2
OH
NO2
NO2
ring opened
products
O2,
NO
(XIV)
NO2
NO2
(XII)
OH OH
NO2
NO2
(XIII)
Figure 3.7 Mechanism of phenol oxidation.
O2
ring opened
products
77
and dry deposition. While the NCAR Master Mechanism-Version 2.0 does not include terms for
deposition, this should not largely affect the levels of gas-phase phenols. First, the lifetime of
phenol in these simulations, based on their reaction with NO3 and OH, is relatively short, ranging
from 0.2 to 2 days. Second, measurements of four phenols (phenol, 2-nitrophenol, 4-nitrophenol,
and 2,4-dinitrophenol) in the gas phase and liquid phase both in and out of clouds, indicate that the
phenols are more abundant in the gas phase than in the liquid phase [Lüttke et al., 1997].
The phenoxy radical (V) formed by H–atom abstraction from benzene or phenol may either
react with NO2 to form nitrophenol (XI) or with HO2 to reform phenol. Atkinson et al. [1992a] was
the first to report the formation of nitrophenol from the reactions of phenol with OH (0:067 0:015
yield of 2-nitrophenol) and NO3 (0:251 0:051 yield of 2-nitrophenol). While they detected only
o-nitrosubstituted nitrophenols, other researchers suggest that both 2- and 4-nitrophenol are formed
[Grosjean, 1991; Nojima et al., 1975]. For simplicity, in the NCAR Master Mechanism only
2-nitrophenol is produced; it is used to represent all mono-nitrophenols.
Benzenediol (IX), formed by the OH addition to phenol, may react with O2 or NO2 . The reaction
of benzenediol with O2 proceeds through the trans-addition of O2 . This adduct is then expected to
react again with O2 in the presence of NO, resulting in the ring-opened products glyoxal (CHOCHO)
and glyoxylic acid (CHOCOOH) [Grosjean, 1991]. In addition to these products, Madronich and
Calvert [1989] include several ring retaining products in the NCAR Master Mechanism to balance
carbons. These products include 1,1-dihydroxy-2-nitrate-3,5-cyclohexadiene (X), from addition
of NO to the peroxy radical, and 1,1-dihydroxy-2-hydroperoxy-3,5-cyclohexadiene (not shown),
which is the expected product from a peroxy radical reaction with HO2 . Wiesen et al. [1995]
suggest that polyketones may account for 25–30% of the missing carbon in aromatic oxidation. The
78
reaction of benzenediol with NO2 is expected to result in the formation of 2-nitrophenol (XI) and
4-nitrophenol. This reaction pathway is a minor source of nitrophenol.
Grosjean [1991] proposes a mechanism for further reaction of the nitrophenols which includes
OH addition and H–atom abstraction by OH and NO3. OH addition to nitrophenol results in
an adduct (XII) which may react with O2 to form ring opened products or with NO2 to form a
dinitrophenol (XIII). The H–atom abstraction from nitrophenol results in a nitrophenoxy radical
(XIV) which reacts with NO2 to form a dinitrophenol (XIII).
The chemistry of 2-nitrophenol (XI) in the modified NCAR Master Mechanism-Version 2.0
is slightly different than that proposed by Grosjean [1991]. Due to uncertainty in the reaction
pathways of nitrophenol and for simplicity, in the modified NCAR Master Mechanism the reaction of
2-nitrophenol with OH proceeds only by OH addition. Excluding the OH reaction route proceeding
by H-atom abstraction may result in an underestimation of the levels of dinitrophenol. In addition,
the reaction of HO2 with the nitrophenoxy radical (XIV) (not included by Grosjean [1991] nor
shown in Figure 3.7) is included by analogy with the phenoxy radical reaction with HO2 ; this
reaction results in nitrophenol. Furthermore, for simplicity, the reactions of 2-nitrophenol produce
2,4-dinitrophenol, skipping the intermediate adducts and lumping the theoretically formed 2,6dinitrophenol with 2,4-dinitrophenol.
While nitroaromatics are not normally considered a significant sink of NOx , the simulated
mixing ratios are consistent with those measured in the gas phase at Great Dun Fell, a rural
site in Northern England [Lüttke et al., 1997]. At Great Dun Fell, levels of mono-nitrophenols
(sum of 2- and 4-nitrophenol) were observed to be 8.7106 –1.6108 molec cm,3 , while 2,4dinitrophenol levels were 3.3105 –2.8108 molec cm,3 . In our simulations, mono-nitrophenols
79
(2-nitrophenol) were less than 3.0108 molec cm,3 , and 2,4-dinitrophenol levels were less than
1.6108 molec cm,3 .
HO2 NO2 Peroxynitric acid (HO2NO2 ) is an important NOx reservoir at cold temperatures. It is
formed by the reaction of NO2 with HO2
HO2 + NO2
*
) HO2NO2 :
(3.14)
HO2 NO2 is the dominant component in the “other inorganic nitrogen” group shown in Figure 3.4. As
shown there, several simulations have HO2 NO2 levels which reach up to 20 ppt. However, HO2NO2
is thermally unstable, and as temperature rises HO2NO2 rapidly decomposes (Reaction -3.14).
Summary of NOx Cycling The cycling of NOx in arctic air is summarized in Figure 3.8,
which shows average NOx net formation and destruction rates during the March and May-highPAN-decomposition simulations with low-initial-ozone levels. (Simulations with high-initial-ozone
levels produced qualitatively similar results.) The source of NOx is dominated by PAN thermal
decomposition, while HNO3 and nitrophenols are the main terminal sinks of NOx . As a result of
PAN decomposition, NOx levels increase significantly in many of the simulations, in some cases
remaining above 75 pptv for 2 days or more. However, even these peak NOx levels are much less
than the amount of PAN decomposed, as a result of rapid oxidation of the NOx produced.
3.2.2 Ozone
The evolution of O3 along each trajectory is shown in Figure 3.9. Each plot contains the results of
four simulations for each trajectory with varying initial levels of O3 and PANs. The initial level of
80
PANs
HNO3
N2O5
NO3
NOx
RNO2
OH
OH
NO2
RONO2
NO2
NO2
= 0.25 ppt/hr March High PAN Decomposition
= 0.25 ppt/hr May High PAN Decomposition
Figure 3.8 The average net rates of NOx production and destruction reactions are shown
for the March and May high-PAN-decomposition simulations. Rates are indicated by the
length of each arrow. (The net formation of N2 O5 from the reaction of NO3 and NO2 is shown
by two arrows directed toward N2 O5 , one from NO3 and the other from NOx .).
81
Ozone (ppb)
40
0.5
1.0
1.5
Time (day)
2.0
Ozone (ppb)
Ozone (ppb)
100
60
40
1
2
3
4
Time (day)
5
6
40
20
0
1
2
3
4
Time (day)
5
6
2.0
1
2
3
Time (day)
4
40
2
3
4
Time (day)
5
6
6
[PAN] = 300 ppt
[PAN] = 0 ppt
60
40
1
2
3
4
Time (day)
5
6
May-High-PAN-Decomposition
100
60
2
4
Time (day)
80
20
0
[PAN] = 300 ppt
[PAN] = 0 ppt
1
40
May-Median-PAN-Decomposition
5
80
20
0
60
100
[PAN] = 300 ppt
[PAN] = 0 ppt
40
[PAN] = 300 ppt
[PAN] = 0 ppt
80
20
0
2.5
March-High-PAN-Decomposition
Ozone (ppb)
Ozone (ppb)
60
1.0
1.5
Time (day)
60
100
[PAN] = 300 ppt
[PAN] = 0 ppt
80
0.5
80
20
0
January-High-PAN-Decomposition
100
40
March-Median-PAN-Decomposition
[PAN] = 300 ppt
[PAN] = 0 ppt
80
20
0
60
20
0.0
2.5
Jan-Median-PAN-Decomposition
100
80
Ozone (ppb)
60
May-Low-PAN-Decomposition
100
[PAN] = 300 ppt
[PAN] = 0 ppt
Ozone (ppb)
Ozone (ppb)
80
20
0.0
March-Low-PAN-Decomposition
100
[PAN] = 300 ppt
[PAN] = 0 ppt
Ozone (ppb)
Jan-Low-PAN-Decomposition
100
[PAN] = 300 ppt
[PAN] = 0 ppt
80
60
40
20
0
1
2
3
4
Time (day)
5
6
Figure 3.9 Ozone mixing ratios are shown as a function of time along each trajectory
for the January, March, and May simulations. Solid lines correspond to simulations with
[PANs]0 =354 pptv, dashed lines show results for simulations with [PANs]0 =0 pptv.
82
O3 within the arctic free troposphere during winter–spring ranges from approximately 35 to 80 ppb,
depending on altitude [Logan, 1985; Oltmans, 1993]. Simulations were conducted with both low
(35 ppb) and high (80 ppb) initial levels of ozone to bound the possible outcomes for each trajectory.
As shown in Figure 3.9, the ozone trends simulated range from primarily ozone destruction in the
simulations with high-initial-ozone to primarily ozone production in the simulations with a lowinitial-ozone.
The initial level of PANs (PAN plus PPN) were varied to determine the impact on the production
of ozone of elevated levels of PANs in arctic air. One set of simulations has initial levels of PANs
equal the values shown in Table 3.2 (totaling 354 ppt), the other has initial PANs equal to 0 ppt. The
difference between these simulations is due to the elevated levels of PANs in arctic air. As shown in
Figure 3.9, the elevated levels of PANs significantly increase ozone production (or decrease ozone
destruction).
Ozone is formed by
NO2 + h
!
NO + O(3 P)
(3.15)
O(3 P) + O2 + M
!
O3 + M:
(3.16)
Most of this ozone is quickly lost in the conversion of NO to NO2 ,
NO + O3
!
NO2 + O2 :
(3.17)
For net ozone production to occur, peroxy radicals must be present to convert NO to NO 2 ,
HO2 + NO
!
OH + NO2
(3.18)
CH3O2 + NO
!
CH3O + NO2
(3.19)
Ri O2 + NO
!
Ri O + NO2 :
(3.20)
83
Table 3.3 Ozone Production Rates in ppbv/day, averaged over each trajectory for simulations with
low- and (high-)initial-ozone levels.
Simulation
January
Low-PAN-decomposition
Median-PAN-decomposition
High-PAN-decomposition
March
Low-PAN-decomposition
Median-PAN-decomposition
High-PAN-decomposition
May
Low-PAN-decomposition
Median-PAN-decomposition
High-PAN-decomposition
HO2 + NO
CH3 O2 + NO
Σ(RiO2 + NO)
2.7E-02 (1.8E-02)
8.3E-03 (2.6E-03)
6.6E-02 (3.4E-02)
2.8E-03 (3.5E-03)
2.0E-03 (1.4E-03)
1.6E-02 (1.4E-02)
4.8E-03 (4.4E-03)
1.6E-03 (9.4E-04)
1.7E-02 (1.1E-02)
1.1E-01 (7.7E-02)
8.6E-02 (3.6E-02)
3.0E-01 (1.6E-01)
1.2E-02 (1.4E-02)
1.4E-02 (1.2E-02)
6.7E-02 (6.1E-02)
1.7E-02 (1.5E-02)
1.4E-02 (9.3E-03)
5.9E-02 (4.0E-02)
4.4E-01 (2.7E-01)
1.3E+00 (7.1E-01)
1.9E+00 (1.2E+00)
5.1E-02 (4.8E-02)
2.5E-01 (2.2E-01)
4.6E-01 (4.2E-01)
1.9E-01 (1.4E-02)
7.5E-02 (4.9E-02)
1.3E-01 (9.6E-02)
The production of ozone is calculated by
P(O3 ) = k3:18[NO][HO2] + k3:19[NO][CH3O2 ] + Σki [NO][Ri O2 ]:
(3.21)
The importance of each of these terms is compared in Table 3.3.
The largest source of O3 in these simulations is Reaction 3.18, accounting for 53–86% of ozone
production, followed by Reaction 3.19, which contributes 8–28% of the ozone production. While
individual reactions of C2 peroxy radicals with NO are small in comparison to HO2 and CH3 O2
together the C2 peroxy radical reactions with NO are comparable to Reaction 3.19, accounting
for 4–19% of ozone production.
Production of O3 is not directly dependent on the level of ozone (Equation 3.21). However, the
cycling of HOx is affected and in turn affects the cycling of NOx and production of O3 . Compared
to simulations with a low-initial-ozone level, simulations with a high-initial-ozone level have higher
levels of HOx , due to increased production of OH. This increases the rate of NOx cycling, resulting
in lower levels of NOx and higher levels of HNO3 . The lower NOx levels decrease the reaction
rates of Equations 3.15–3.17, decreasing the production of O3 .
84
While photolysis is the fastest ozone loss reaction, only a small fraction results in the net loss
of ozone. There are two pathways,
A O + O(3 P)
!
2
O3 + h
(3.22)
B O + O(1 D);
!
2
with channel A being dominant. The production of O(3 P) quickly reforms ozone by reaction with
O2 , Reaction 3.16. Additionally, most of channel B also reforms ozone by releasing energy in a
reaction with N2 or O2 (denoted by M),
O(1 D) + M ! O(3P) + M
(3.23)
followed by reaction 3.16. The fraction of O(1 D) which does not reform O3 results in ozone
destruction,
O(1D) + H2O ! 2OH:
(3.24)
Other reactions which result in O3 destruction include reaction of O3 with HO2 and OH,
O3 + HO2
!
OH + 2O2
(3.25)
O3 + OH
!
HO2 + O2 ;
(3.26)
ozone addition to alkenes,
R=R + O3
! ROO +
R=O
(3.27)
A
!
NO3 + O2
(3.28)
B
!
NO + O(3P)
!
NO2 + O(3 P):
and the net conversion of NO2 to NO3 ,
O3 + NO2
NO3 + h
(3.29)
85
Table 3.4 Ozone Loss Rates in ppbv/day, averaged over each trajectory for simulations with low- and
(high-)initial-ozone levels.
Simulation
January
Low-PAN-decomposition
H2 O+ O(1 D)
OH+ O3
HO2 + O3
NO2 + O3
Σ(R=R + O3 )
1.5E-03
(3.5E-03)
2.1E-03
(4.8E-03)
2.9E-02
(6.5E-02)
1.2E-03
(3.7E-03)
1.4E-03
(6.1E-03)
5.5E-03
(2.1E-02)
1.4E-02
(3.7E-02)
3.7E-02
(8.6E-02)
5.8E-02
(1.6E-01)
9.4E-04
(1.8E-03)
2.5E-03
(3.6E-03)
3.8E-03
(6.4E-03)
3.5E-03
(7.5E-03)
1.1E-02
(2.0E-02)
8.4E-03
(1.6E-02)
2.3E-02
(5.3E-02)
1.2E-02
(2.8E-02)
1.0E-01
5.3E-03
(1.9E-02)
5.5E-03
(1.9E-02)
2.0E-02
4.6E-02
(1.3E-01)
8.3E-02
(2.0E-01)
1.4E-01
1.1E-03
(2.3E-03)
3.2E-03
(4.6E-03)
6.7E-03
4.9E-03
(1.0E-02)
1.2E-02
(2.2E-02)
1.9E-02
7.0E-02
(1.5E-01)
3.9E-01
(7.9E-01)
8.7E-01
(1.7E+00)
2.5E-02
(8.0E-02)
1.0E-01
(2.8E-01)
1.6E-01
(4.1E-01)
1.9E-01
(5.4E-01)
5.4E-01
(1.4E+00)
4.7E-01
(1.2E+00)
4.3E-04
(1.2E-03)
7.2E-03
(9.3E-03)
1.5E-02
(2.0E-02)
1.7E-03
(2.9E-03)
2.2E-03
(3.3E-03)
1.8E-03
(3.0E-03)
Median-PAN-decomposition
High-PAN-decomposition
March
Low-PAN-decomposition
Median-PAN-decomposition
High-PAN-decomposition
May
Low-PAN-decomposition
Median-PAN-decomposition
High-PAN-decomposition
The loss of ozone is calculated by
L(O3 )
=
k
k
( 3:26[OH] + 3:25[HO2 ] +
Σki [R=Ri ])[O3 ] +
k3:24[O(1 D)][H2O] + (k3:28[O3 ][NO2 ] , J3:29[NO3 ]):
(3.30)
(3.31)
As shown in Table 3.4, O3 destruction in these simulations occurs mainly by reaction of HO2 with
O3 (Reaction 3.25).
As expected the loss rate of O3 is faster for simulations with high-initial-ozone
levels than low-initial-ozone levels.
The rate of net ozone production (NOP) is given by:
NOP = P(O3 ) , L(O3):
(3.32)
For the high-PAN simulations the net ozone production rate averaged over the period of simulation
(equal to the change in ozone mixing ratio over the trajectory duration normalized by trajectory
86
Table 3.5 Source of NOx and O3 to North Atlantic resulting from
elevation PANs in the Arctic.
Month
January
March
May
Flux of Air
(10 STP km3 /day)
1.9
1.5
1.3
6
NOx a a
(Gg N/month)
0.0–3.1
0.1–3.4
0.4–7.6
O3 a
(Gg O3 /month)
0.1–19.8
0.7–127.8
11.0–712.1
a Ranges of NOx and O3 fluxes are based on all original, un-
extended trajectory simulations (low- and high-initial-ozone; low-,
median-, and high-PAN-decomposition) for each month.
duration) ranges from -0.042 to 0.93 ppb/day for the simulations with low-initial-ozone and from
-0.03 to -1.6 ppb/day for the simulations with high-initial-ozone. Peak rates of net ozone production
reach up to 6.7 ppb/day. The presence of elevated PAN mixing ratios in the Arctic results in a
significant increase in ozone production: these values reflect an increased average NOP of up to
0.03 ppb/day in January, up to 0.15 ppbv/day in March, and up to 1.60 ppbv/day in May.
3.2.3 Flux of NOx and O3
To assess the impact of arctic outflow on the NOx and O3 budgets of the North Atlantic region, an
upper limit estimate of the flux of these species is calculated. The flux of NOx and O3 is estimated
from the volumetric flux of air which leaves the Arctic and reaches the North Atlantic (defined here
as 10–70 W and 20–50 N) [Honrath et al., 1996] and the amount of NOx and O3 produced as
a result of elevated levels of PANs in the Arctic. For NOx , this amount is the net amount of NOx
released from PAN and PPN (the NOx source). The ozone produced is determined by taking the
difference between the integrated net ozone production in the two simulations for each trajectory
with different initial levels of PAN and PPN: one with initial PANs set at 354 ppt and the second
with no PANs present. The range of fluxes for each month is shown in Table 3.5.
The impact
of arctic outflow on the NOx and O3 budgets of the North Atlantic is estimated in this way to be
87
< 7.6 Gg N/month and < 712 Gg O3 /month, respectively, where the upper limits would be reached
only if all arctic outflow behaved as do the low-initial-ozone, high-PAN-decomposition simulations.
Due to limitations of isentropic trajectory calculations, several of these simulations end abruptly
in the boundary layer. Subsidence into the boundary layer is expected to have two opposing effects
which may influence the flux of NOx and O3 to the North Atlantic. First, NOx and O3 loss rates
increase as a result of increased water vapor concentration. Second, the boundary layer is typically
warmer than the free troposphere. As elevated levels of PAN subside into the boundary layer, the
rate of PAN thermal decomposition is expected to increase, which may increase the impact of NOx
and O3 from the Arctic. For example, as shown in Figure 3.2, the March-high-PAN-decomposition
simulation enters the boundary layer on day 5, where it remains for 12 hours before the trajectory
terminates. During these 12 hours there is a large decrease in PAN (100 ppt) and a corresponding
(but much smaller) peak in NOx . However, there is a significant amount of PAN remaining. If
the air parcel remains intact it is likely that the PAN will continue to thermally decompose. To
determine whether this might result in significantly more ozone formation, additional simulations
were conducted, in which the trajectory was extended for 4.5 days in the boundary layer, using the
same temperature, pressure, latitude, and longitude as the last point of the trajectory. As shown
in Figure 3.10, PAN levels continue to drop, reaching a minimum of 40 ppt, resulting in relatively
high levels of NOx for 2–3 days. The increased levels of NOx contribute to increased net ozone
production for the low-initial-ozone simulations, as shown in Figure 3.11, while a reduction in net
ozone destruction is simulated for the high-initial-ozone simulations. The flux of NOx and O3 to
the North Atlantic if this extended simulation were used as the basis would be 7.9 Gg N/month
and 536 Gg O3 /month, respectively. Thus, although the resulting NOx release and O3 production
88
March-High-PAN-Decomposition
Mixing Ratio (pptv)
500
F
400
E
300
200
D
C
B
A
100
0
0
2
4
6
Time (day)
8
10
Figure 3.10 The effect of extending the duration of the March high-PAN-decomposition
trajectory (see text) upon NOy speciation is shown in the form described for Figure 3.4. A)
NOx ; B) PANs; C) RONO2 ; D) Nitroaromatics; E) HNO3 ; F) Other Inorganics.
March-High-PAN-Decomposition
Ozone (ppb)
100
[PAN] = 300 ppt
[PAN] = 0 ppt
80
60
40
20
0
2
4
6
Time (day)
8
10
Figure 3.11 The effect of extending the duration of the March high-PAN-decomposition
trajectory (see text) upon O3 levels is shown in the form described for Figure 3.9.
89
May-High-PAN-Decomposition
Mixing Ratio (pptv)
500
F
400
300
E
200
100
0
0
2
4
6
Time (day)
8
10
D
C
B
A
Figure 3.12 The effect of extending the duration of the May high-PAN-decomposition trajectory (see text) upon NOy speciation is shown in the form described for Figure 3.4 A) NOx ;
B) PANs; C) RONO2 ; D) Nitroaromatics; E) HNO3 ; F) Other Inorganics.
are increased in the extended simulation, they remain less than or approximately equal to those
calculated for the May-high-PAN-decomposition simulation.
The May-high-PAN-decomposition trajectory also ends abruptly in the boundary layer. However, as shown in Figure 3.12, extended simulations of this trajectory result in only a small increase
in the release of NOx , because most of the PAN already decomposed within the first 5.5 days of the
simulation.
The flux of NOx and O3 to the North Atlantic based on the extended May-high-PAN-decompositionsimulation would be 8.4 Gg N/month and 726 Gg O3 /month. These values are only slightly larger
than those from the original, unextended trajectories (less than 11% larger for NOx , and less than 2%
larger for O3). For this reason, and because the extended trajectory values are somewhat uncertain
(as dilution in the boundary layer is not simulated in the model), the original, unextended flux
estimates are used in the remaining discussion.
90
Table 3.6 Comparison of NOx Sources to the North Atlantic Troposphere.
Source of NOx
North America
Europe
Africa
Aircraft
Lightning
Stratosphere
Arctic, January
Arctic, May
NOx (Gg N/month)
65–115
7–90
23–85
1.8–2.3
1.4–14
0.7–4.1
< 3.1
< 7.6
Reference
Liang et al. [1998]
Whelpdale and Galloway [1994]
Whelpdale and Galloway [1994]
Baughcum et al. [1996]
Penner et al. [1991]
Roelofs and Lelieveld, Murphy and Fahey [1995, 1994]
this work
this work
The calculated upper limit flux of NOx from the Arctic to the North Atlantic (based on lowinitial-ozone, high-PAN-decomposition simulations) is compared to the flux of NOx from other
sources to the North Atlantic troposphere in Table 3.6. The upper limit estimate of NOx due to
elevated levels of PANs in arctic outflow is less than 9% of that from the surrounding continental
regions of North America, Europe, and Africa together or up to 13% of the North American export
of NOx . The largest source of NOx to the North Atlantic is export from North America. Liang et
al. [1998] estimate the export of NOx from North America is 65 to 115 Gg N/month during winter–
spring, which is 40–60% of their estimated NOy export. Other continental sources to the North
Atlantic include Europe and Africa, for which the flux of NOy to the North Atlantic is estimated
to be 16.7–150 Gg N/month and 58–142 Gg N/month, respectively [Whelpdale and Galloway,
1994]. Applying the NOx /NOy export ratio from North America as an estimate of that ratio for
European and African export results in estimated NOx fluxes of 7–90 Gg N/month from Europe
and 23–85 Gg N/month from Africa.
Free tropospheric sources of NOx to the North Atlantic include aircraft emissions, lightning,
and stratosphere–troposphere exchange (STE). Aircraft emissions of NOx over the North Atlantic
region (30–70 N, 10–70 W) are estimated to be 1.8–2.3 Gg N/month for the winter–spring
period [Baughcum et al., 1996]. For comparison, the flux of NOx from lightning is estimated using
91
Table 3.7 Comparison of O3 Sources to the North Atlantic Troposphere.
Source of Ozone
North America
Aircraft
Stratosphere
Arctic, January
Arctic, May
O3 (Gg O3 /month)
7,800–22,200
65–200
1100–11,000
< 20
< 712
Reference
Liang et al. [1998]
Baughcum et al. [1996], Flatoy and Hov [1996]
see text
this work
this work
the unit flux of NOx from lightning over the North Atlantic Ocean for January (1–10 kg N/km2 yr)
estimated by Penner et al. [1991] and the area of the North Atlantic region, defined here as
20–50 N and 70–10 W ( 1:68 107 km2). This results in a flux of 1.4–14 Gg N/month
from lightning. Estimates of the global source of NOx from the stratosphere to the troposphere
range from 20-60 Gg N/month [Murphy and Fahey, 1994 and references therein], while northern
hemisphere estimates range from 5–13 Gg N/month [Roelofs and Lelieveld, 1995]. Assuming
that 80% of the flux occurs between 20 and 50 latitude (based on the spatial distribution of the
cross-tropopause flux of Wang et al. [1998a]), scaling by area to the North Atlantic region, the flux
from the stratosphere is approximately 0.7–4.1 Gg N/month, on an annual basis. (This should be
considered a lower limit for spring, when the flux of air across the tropopause is at a maximum
[Apenzeller et al., 1996].)
While the free tropospheric sources of NOx (aircraft, lightning, and stratosphere–troposphere
exchange) are comparable to the flux from the Arctic, the free tropospheric sources are expected
to have a greater impact because of their location. These sources are emitted into the upper
troposphere and are expected to be the dominant source of NOx in that region [Lamarque et al., 1996;
Levy II et al., 1999]. In contrast, outflowing arctic air subsides and warms as it moves southward,
releasing NOx through PAN thermal decomposition in the lower to mid-troposphere, a region also
affected by combustion emissions from continental sources.
92
The sources of O3 to the North Atlantic troposphere are listed in Table 3.7. As expected from
the discussion of NOx sources, the export of pollutants from North America is the largest source
of O3 to the North Atlantic troposphere. Liang et al. [1998] estimate 1 Gmol O3 /day is exported
directly from the U.S. boundary layer during winter, and 3.9 Gmol O3/day is exported during spring.
Additional ozone is expected to form as a result of the export of NOx and PANs. This source is
estimated to be 4.8 Gmol O3 /day for winter and 11 Gmol O3/day for spring [Liang et al., 1998].
Together, the total estimated flux of O3 from North American export is thus 5.8–14.9 Gmol O3/day
(7800–22,200 Gg O3 /month) during the winter–spring period. The source of O3 from aircraft
emissions is estimated to be 65–200 Gg O3 /month. This is based on aircraft NOx emissions
[Baughcum et al., 1996] and the estimated average number of O3 molecules produced per NOx
molecule emitted from aircraft (10–25 [Flatoy and Hov, 1996]). There have been a number of global
and Northern Hemisphere estimates of the flux of ozone from the stratosphere to the troposphere.
Most of these estimates are based on the results of models [for example, Murphy and Fahey, 1994;
Wauben et al., 1998 and references therein], while some estimate the flux based on observations of
transport [Ancellet et al., 1994] or correlations of ozone with N2 O, potential vorticity, or radioactive
deposition [Danielsen and Mohnen, 1977; Murphy and Fahey, 1994]. Estimates of the global
ozone flux from the stratosphere into the troposphere range from 17 to 120 Tg O3 /month, while
estimates of the Northern Hemispheric flux range from 28 to 83 Tg O3 /month. As with the flux
of NOx from the stratosphere, these estimates are scaled by area, taking the latitudinal distribution
into account, to obtain a flux of O3 from the stratosphere into the North Atlantic troposphere of
1.1–11.0 Tg O3 /month.
The amount of O3 produced during arctic outflow, up to 328 Gg O3/month (based on the
93
maximum production in the low-initial-ozone, May-high-PAN-decomposition simulation), is similar
to the O3 produced as a result of aircraft emissions. However, these sources impact different regions
of the troposphere. The low- to mid-troposphere, the region impacted by arctic outflow, is heavily
dominated by the source of ozone from North America. Thus, while the presence of elevated PAN
levels in the Arctic is expected to significantly affect NOx and O3 levels over the North Atlantic
during arctic outflow events, this impact is small on a seasonal basis in comparison to that resulting
from outflow from the North American continent. In conclusion, it is expected that the flux of NOx
and O3 resulting from elevated levels of PAN in the Arctic does not have a significant effect on the
seasonal budget of NOx or O3 in the North Atlantic troposphere.
3.3 Summary and Conclusions
In this study, we used a photochemical model to investigate NOx cycling in arctic outflow and
its impact on the tropospheric NOx and O3 budgets over the North Atlantic Ocean. We applied
the model to a range of representative trajectories for the months of January–May. The primary
source of NOx in these simulations is the thermal decomposition of PAN, which increases from
January to May and results in peak levels of NOx reaching 120 pptv. However, the NOx released
from PAN is efficiently removed, resulting in the production of HNO3 and, to a lesser extent,
nitrophenols. Elevated levels of NOx in arctic outflow increase the rate of net ozone production
when compared to simulations which exclude initial levels of PANs. For January, March, and May
net ozone production averaged over the trajectory simulations is increased by up to 0.03 ppb/day,
up to 0.15 ppb/day, and up to 1.60 ppb/day, respectively.
The source of NOx and O3 to the North Atlantic troposphere resulting from arctic outflow was
94
estimated to be 7:6 Gg N/month and
712 Gg O3/month.
These estimates were upper limits
because seasonal variations in PAN levels have not been included and these estimates are calculated
by applying the maximum NOx release and corresponding O3 production obtained for any simulated
trajectory to all the trajectories. The NOx source resulting from arctic outflow is comparable to the
sources of NOx from stratosphere-troposphere exchange, emissions from aircraft, and lightning to
the North Atlantic troposphere. These model simulations indicate that during arctic outflow events,
elevated levels of PAN present in the arctic troposphere significantly increase NOx and O3 levels
in southward flowing arctic air. However, the North Atlantic tropospheric NOx and O3 budgets
are dominated by export from North America. As a result, on a seasonal basis and when episodic
transport from both North America and the Arctic are considered, arctic outflow is not expected to
have a significant effect on the budgets of NOx and ozone in the North Atlantic troposphere.
Chapter 4
Summary and Conclusions
The objective of this research was to determine the impact of winter-spring arctic outflow events
on the NOx and O3 budgets of the North Atlantic troposphere. To achieve this objective, the
photochemical evolution within representative arctic outflow events was simulated using lagrangian,
photochemical box-model simulations.
As there have been many improvements in the available laboratory kinetic data, the model used
in these simulations, the NCAR Master Mechanism, was revised to reflect current recommendations.
The mechanism was revised in small increments to determine the effect of mechanism revisions on
the simulated levels of NOx and O3 . The revisions to peroxy radical, PAN, and photolysis reactions
have the largest effect on the levels of NOx and O3. In comparison to the original mechanism, the
revisions to peroxy radical reactions increase the average levels of NOx and O3 by 23.9% and 0.7%,
respectively; the PAN revisions decrease the average levels of NOx and O3 by 14.1% and 0.4%,
respectively; while the photolysis revisions decrease the average levels of NO x and O3 by 8.4%
and 1.0%, respectively. The overall effect of incorporating all mechanism revisions is a smaller
95
96
change in the levels of NOx and O3 . Therefore, it is important to completely update the gas-phase
chemical mechanism. This includes updating all the chemical families, as the effects of revisions
to individual chemical families counteract each other, damping the net effect. It is also important to
update all the species within each of the families, as this work demonstrates that the sum of many
small changes have a large net effect. This work indicates that a complete revision of a gas-phase
mechanism is preferred over the practice of revising only a few key reactions of the mechanism.
To determine the impact of winter–spring arctic outflow events on the NOx and O3 budgets of the
North Atlantic troposphere, the chemical evolution of nitrogen oxides were examined in simulations
along representative trajectories. The primary source of NOx is the thermal decomposition of peroxy
acyl nitrates. The release of NOx from peroxy acyl nitrates increases from January to May and
results in peak levels of NOx reaching 120 pptv. However, the NOx released from PAN is efficiently
removed, resulting in the production of HNO3 and, to a lesser extent, nitrophenols. Elevated levels
of NOx in arctic outflow increase the production rate of ozone. The net ozone production rate
averaged over the trajectory simulations is increased for the months of January, March, and May by
up to 0.03 ppb/day, up to 0.15 ppb/day, and up to 1.60 ppb/day, respectively.
The source of NOx and O3 to the North Atlantic troposphere resulting from arctic outflow is
estimated to be 7:6 Gg N/month and 712 Gg O3 /month. While this source is comparable to
estimates of ozone produced from aircraft emissions, both are small in comparison to the export
of ozone from North America. On a seasonal basis and when episodic transport from both North
America and the Arctic are considered, arctic outflow is not expected to have a significant effect on
the budgets of NOx and ozone in the North Atlantic troposphere.
The findings of this work contribute to the understanding of the processes controlling ozone
97
production and of anthropogenic impacts on the regional and global atmosphere. The redistribution
of pollutants through the Arctic during the late winter–early spring provides a mechanism for
the transport of ozone and its precursors from regions, such as the former Soviet Union and
Eastern Europe, which would otherwise be unimportant to the North Atlantic regional budgets of
these compounds. This work, for the first time, quantifies the resulting impact of arctic outflow
events on the seasonal NOx and O3 budgets of the North Atlantic troposphere, contributing to our
understanding of the effect of anthropogenic emissions on remote regions.
Additional research is recommended in the area of model development and validation. Due
to the characteristics of the winter–spring free troposphere not all chemical families were revised
in this work. For the updated NCAR Master Mechanism to be applicable for other situations it is
recommended that the kinetic and mechanistic parameters be investigated and revised as needed
for toluene, isoprene, and halogen chemistry. Additional laboratory work is needed to improve our
understanding of aromatic chemistry. To validate the mechanism, simulations should be conducted
for comparison to environmental chamber data.
References
Allan, B. J., N. Carslaw, H. Coe, R. A. Burgess, and J. M. C. Plane, Observations of the nitrate
radical in the marine boundary layer, J. Atmos. Chem., 33, 129–154, 1999.
Ancellet, G., M. Beekmann, and A. Papayannis, Impact of a cutoff low development on downward
transport of ozone in the troposphere, J. Geophys. Res., 99, 3451–3468, 1994.
Anderson, G. P., S. A. Clough, F. X. Kneizys, J. H. Chetwynd, and E. P. Shettle, AFGL Atmospheric
Constituent Profiles (0–120 km), AFGL-TR-86-0110, AFGL (OPI), Hanscom AFB, MA 01736,
1986.
Apenzeller, C., J. R. Holton, and K. H. Rosenlof, Seasonal variation of mass transport across the
tropopause, J. Geophys. Res., 101, 15,071–15,078, 1996.
Ariya, P. A., B. T. Jobson, R. Sander, H. Niki, G. W. Harris, J. F. Hopper, and K. G. Anlauf, Measurements of C2 –C7 hydrocarbons during the Polar Sunrise Experiment 1994: Further evidence
for halogen chemistry in the troposphere, J. Geophys. Res., 103, 13,169–13,180, 1998.
Atkinson, R., Kinetics and mechanisms of the gas-phase reactions of the hydroxyl radical with
organic compounds under atmospheric conditions, Chem. Rev., 85, 69–201, 1985.
Atkinson, R., A structure-activity relationship for the estimation of rate constants for the gas-phase
reactions of OH radicals with organic compounds, Int. J. Chem. Kinet., 19, 799–828, 1987.
Atkinson, R., Kinetics and mechanisms of the gas-phase reactions of the hydroxyl radical with
organic compounds, J. Phys. Chem. Ref. Data, Monograph 1, 1989.
Atkinson, R., Gas-phase tropospheric chemistry of organic compounds: A review, Atmos. Environ.,
24a, 1–41, 1990.
Atkinson, R., Kinetics and mechanisms of the gas-phase reactions of the no3 radical with organic
compounds, J. Phys. Chem. Ref. Data, 20, 459–507, 1991.
Atkinson, R., Gas–phase tropospheric chemistry of organic compounds, J. Phys. Chem. Ref. Data,
Monograph No. 2, 1–216, 1994.
Atkinson, R., Gas–phase tropospheric chemistry of volatile organic compounds: 1. Alkanes and
alkenes, J. Phys. Chem. Ref. Data, 26, 215, 1997.
Atkinson, R., and S.M. Aschmann, Rate constants for the reactions of the OH radical with the
98
99
propyl and butyl nitrates and 1-nitrobutane at 2982 K, Int. J. Chem. Kinet., 21, 1123–1129,
1989.
Atkinson, R., and W.P.L. Carter, Reactions of alkoxy radicals under atmospheric conditions: The
relative importance of decomposition versus reaction with O2, J. Atmos. Chem., 13, 195–210,
1991.
Atkinson, R., and A.C. Lloyd, Evaluation of kinetc and mechanistic data for modeling of photochemical smog, J. Phys. Chem. Ref. Data, 13, 315–444, 1984.
Atkinson, R., A. C. Lloyd, and L. Winges,
An updated chemical mechanism for
hydrocarbon/NOx /SO2 photooxidations suitable for inclusion in atmospheric simulation models, Atmos. Environ., 16, 1341–1355, 1982a.
Atkinson, R., S.M.Aschmann, W.P.L. Carter, A.M. Winer, and J.N. Pitts Jr., Alkyl nitrate formation
from the NOx -air photooxidants of C2 –C8 n-alkanes, J. Phys. Chem., 86, 4563–4569, 1982b.
Atkinson, R., W. P. L. Carter, C. N. Plum, A. M. Winer, and J. N. Pitts Jr., Kinetics of the gas-phase
reactions of nitrate radicals with a series of aromatics at 296 2 K, Int. J. Chem. Kinet., 16,
887–98, 1984.
Atkinson, R., J. Arey, B. Zielinska, and S. M. Aschmann, Kinetics and products of the gas-phase of
OH radicals and N2 O5 with naphthalene and biphenyl, Environ. Sci. Tech., 21, 1014–1022, 1987.
Atkinson, R., S. M. Aschmann, J. Arey, and W. P. L. Carter, Formation of ring-retaining products
from the OH radical-initiated reactions of benzene and toluene, Int. J. Chem. Kinetics, 21,
801–827, 1989a.
Atkinson, R., D.L. Baulch, R.A. Cox, Jr. R.F. Hampson, J.A. Kerr, and J. Troe, IUPAC subcommittee
on gas kinetic data evaluation for atmospheric chemistry, J. Phys. Chem. Ref. Data, 18, 881,
1989b.
Atkinson, R., S.M. Aschmann, and J. Arey, Reactions of OH and NO 3 radicals with phenol, cresols,
and 2–nitrophenol at 296 2K, Environ. Sci. Tech., 26, 1397–1403, 1992a.
Atkinson, R., D. L. Baulch, R. A. Cox, R.F. Hampson Jr., J.A. Kerr, and J. Troe, Evaluated kinetic
and photochemical data for atmospheric chemistry: Supplement iv. IUPAC subcommittee on gas
kinetic data evaluation for atmospheric chemistry, J. Phys. Chem. Ref. Data, 21, 1125–1444,
1992b.
Atkinson, R., E.C. Tuazon, I. Bridier, and J. Arey, Reactions of NO 3 - naphthalene, adducts with
O2 and NO2 , Environ. Sci. Tech., 28, 605–614, 1994.
Barrie, L. A., Arctic air pollution: An overview of current knowledge, Atmos. Environ., 20, 643–663,
1986.
Barrie, L. A., and J. W. Bottenheim, Sulfur and nitrogen pollution in the arctic atmosphere, in
Pollution of the Arctic Atmosphere, edited by W. Sturges, pp. 155–183, Elsevier, New York,
1991.
Bass, A., L.C. Glasgow, C. Miller, J.P. Jesson, and S.L. Filken, Temperature dependant absorption
cross section for formaldehyde (CH2 O): The effect of formalehyde on stratospheric chlorine
chemistry, Planet. Space Sci., 28, 675–679, 1980.
100
Baughcum, S. L., T. G. Tritz, S. C. Henderson, and D. C. Pickett, Scheduled civil aircraft emission
inventories for 1992: Database development and analysis, Contractor report NASA CR-4700,
NASA, April 1996.
Beine, H. J., and T. Krognes, The seasonal cycle of peroxyacetyl nitrate (PAN) in the European
Arctic, Atmos. Environ., 34, 933–940, 2000.
Beine, H. J., M. Engardt, D. A. Jaffe, O. Hov, K. Holmén, and F. Stordal, Measurements of NOx and
aerosol particles at the Ny-Ålesund Zeppelin mountain-station on Svalbard: Influence of local
and regional pollution sources, Atmos. Environ., 30, 1067–1079, 1996.
Beine, H. J., D. A. Jaffe, F. Stordal, N. Schmidbauer, S. Solberg, M. Engardt, and K. Holmén, NOx
during ozone depletion events in the Arctic troposphere at Ny-Ålesund, Svalbard, Tellus, 49B,
556–565, 1997a.
Beine, H. J., D. A. Jaffe, J. A. Herring, J. A. Kelley, T. Krognes, and F. Stordal, High-latitude
springtime photochemistry. Part I: NOx , PAN, and ozone relationships, J. Atmos. Chem., 27,
127–153, 1997b.
Bongartz, A., J. Kames, F. Welter, and U. Schurath, Near-UV absorption cross sections and trans/cis
equilibrium of nitrous acid, J. Phys. Chem., 95, 1076–1082, 1991.
Bottenheim, J. W., and A. J. Gallant, PAN over the Arctic: Observations during AGASP-2 in April
1986, J. Atmos. Chem., 9, 301–316, 1989.
Bottenheim, J. W., L. A. Barrie, and E. Atlas, The partitioning of nitrogen oxides in the lower arctic
troposphere during spring 1988, J. Atmos. Chem., 17, 15–27, 1993.
Bridier, I., F. Caralp, H. Loirat, R. Lesclaux, B. Veyret, K. H. Becker, A. Reimer, and F. Zabel,
!
Kinetic and theoretical studies of the reactions CH3 C(O)O2 + NO2 + M CH3 C(O)O2 NO2 +M
between 248 and 393 K and between 30 and 70 torr, J. Phys. Chem., 95, 3594–3600, 1991.
Burrows, J., G.S. Tyndall, and G.K. Moortgat, Absorption spectrum of NO 3 and kinetics of the
reactions ofNO3 with NO2 , cl, and several stable atmospheric species at 298 K, J. Phys. Chem.,
89, 4848–4856, 1985.
Canosa-Mas, C., M. Fowles, P.J. Houghton, and R.P. Wayne, Absolute absorption cross-section
measurements on NO3 : Evaluation of the titration of NO3 by NO in the determination of absolute
concentrations, J. Chem. Soc. Faraday Trans. II, 83, 1465–1474, 1987.
Canosa-Mas, C. E., M.D. King, R. Lopez, C.J. Percival, R.P. Wayne, D.E. Shallcross, J.A. Pyle, and
V. Daële, Is the reaction between CH3 C(O)O2 and NO3 important in the night-time troposphere?,
J. Chem. Soc. Faraday Trans. II, 92, 2211–2222, 1996.
Cantrell, C. A., William R. Stockwell, Larry G. Anderson, Kerry L. Busarow, Dieter Perner, Art
Schmeltekopf, Jack G. Calvert, and Harold S. Johnston, Kinetic study of the NO3 –CH2 O reaction
and its possible role in nighttime tropospheric chemistry, J. Phys. Chem., 89, 1839–146, 1985.
Cantrell, C. A., James A. Davidson, Richard E. Shetter, B.A. Anderson, and Jack G. Calvert, The
temperature invariance of the NO3 absorption cross section in the 662-nm region, J. Phys. Chem.,
91, 5858–5863, 1987.
Cantrell, C. A., James A. Davidson, Anthony H. McDaniel, Richard E. Shetter, and Jack G. Calvert,
101
Temperature–dependent formaldehyde cross sectionsin the near–ultraviolet spectral region, J.
Phys. Chem., 94, 3902–3908, 1990.
Carter, W., and R. Atkinson, Alkyl nitrate formation from the atmospheric photooxidation of
alkanes; a revised estimation method, J. Atmos. Chem., 8, 165, 1989.
Cox, R., M.C. Addison, J.P. Burrows, and R. Patrick, 14th Informal Conf. Photochem., Newport
Beach, CA, March 30-April 3, 1980.
Crassier, V., K. Suhre, P. Tulet, and R. Rosset, Development of a reduced chemical scheme for use
in mesoscale meterological models, Atmos. Environ., 34, 2633–2644, 2000.
Crutzen, P. J., The role of NO and NO2 in the chemistry of the troposphere and stratosphere, Ann.
Rev. Earth Planet. Sci., 7, 443–472, 1979.
Daële, V., A. Ray, I. Vassali, G. Poulet, and G. Le Bras, Kinetic study of reactions of C2 H5O and
C2 H5O2 with NO at 298 K and 0.55–2 torr, Int. J. Chem. Kinet., 27, 1121–1133, 1995.
Dagut, P., and M.J. Kurylo, Gas phase UV absorption spectrum of methylperoxy radicals: A
reinvestigation, J. Photochem. and Photobio. A:Chem., 51, 133–140, 1990.
Danielsen, E. F., and V. A. Mohnen, DUSTSTORM report: Ozone transport and meteorological
analyses of tropopause folding, J. Geophys. Res., 82, 5867–5877, 1977.
Davidson, J., C.A. Cantrell, A.H. McDaniel, R.E. Shetter, S. Madronich, and J.G. Calvert, Visibleultraviolet absorption cross sections for NO3 scavenging in the troposphere, J. Geophys. Res.,
93, 7105–7112, 1988.
Davidson, J. A., C.A. Cantrell, R.E. Shetter, A.H. McDaniel, and J.G. Calvert, The NO3 radical
decomposition and NO3 scavenging in the troposphere, J. Geophys. Res., 95, 13963–13969,
1990.
DeMore, W. B., S. P. Sander, D. M. Golden, R. F. Hampson, M. J. Kurylo, C. J. Howard, A. R.
Ravishankara, C. E. Kolb, and M. J. Molina, Chemical kinetics and photochemical data fo
use in stratospheric modeling, evaluation number 10, Technical report, NASA Jet Propulsion
Laboratory, 1992.
DeMore, W. B., S. P. Sander, D. M. Golden, R. F. Hampson, M. J. Kurylo, C. J. Howard, A. R.
Ravishankara, C. E. Kolb, and M. J. Molina, Chemical kinetics and photochemical data for
use in stratospheric modeling, evaluation number 11, Technical report, NASA Jet Propulsion
Laboratory, 1994.
DeMore, W. B., S. P. Sander, D. M. Golden, R. F. Hampson, M. J. Kurylo, C. J. Howard, A. R.
Ravishankara, C. E. Kolb, and M. J. Molina, Chemical kinetics and photochemical data for use
in stratospheric modeling, evaluation number 12, Technical Report JPL Publication 97-4, NASA
Jet Propulsion Laboratory, 1997.
Dentener, F. J., and P. J. Crutzen, Reaction of N2O5 on tropospheric aerosols: Impact on the global
distributions of NOx , O3, and OH, J. Geophys. Res., 98, 7149–7163, 1993.
Derwent, R. G., P. G. Simmonds, S. Seuring, and C. Dimmer, Observation and interpretation of
the seasonal cycles in the surface concentrations of ozone and carbon monoxide at Mace Head,
Ireland from 1990 to 1994, Atmos. Environ., 32, 145–157, 1998.
102
Desai, J., J. Heicklen, A. Bahta, and R. Simonaitis, The photooxidation of isobutyraldehyde vapor,
J. Phys. Chem., 34, 137–164, 1986.
Dimitroulopoulou, C., and A. R. W. Marsh, Modelling studies of NO3 nighttime chemistry and its
effects on subsequent ozone formation, Atmos. Environ., 31, 3041–3057, 1997.
Doskey, P. V., and Jeffrey Gaffney, Non-methane hydrocarbons in the arctic atmosphere at Barrow,
Alaska, Geophys. Res. Lett., 19, 381–384, 1992.
Eberhard, J., and C.J. Howard, Temperature-dependent kinetics studies of the reactions of C 2 H5O2
and n-C3 H7 O2 radicals with NO, Int. J. Chem. Kinet., 28, 731–740, 1996.
Fenneteaux, I., P. Colin, A. Etienne, H. Boudries, A. L. Dutot, P. E. Perros, and G. Toupance,
Influence of continental sources on oceanic air composition at the eastern edge of the North
Atlantic Ocean, TOR 1992-1995, J. Atmos. Chem., 32, 233–280, 1999.
Finlayson-Pitts, B. J., and J.N. Pitts, Jr., Atmospheric Chemistry: Fundamentals and Experimental
Techniques, John Wiley & Sons, 1986.
Finlayson-Pitts, B. J., and J.N. Pitts, Jr., Chemistry of the Upper and Lower Atmosphere: Theory,
Experiments, and Applications, Academic Press, 1999.
Fishman, J., V. Ramanathan, P. J. Cruzten, and S.C. Liu, Tropospheric ozone and climate, Nature,
282, 818–820, 1979.
Flatoy, F., and O. Hov, Three-dimensional model studies of the effect of NO x emissions from
aircraft on ozone in the upper troposphere over Europe and the North Atlantic, J. Geophys. Res.,
101, 1401–1422, 1996.
Forgeteg, S., S. Dobe, and T. Berces, The effect of pressure on the primary photochemical process
of n-butyraldehyde at 313 nm, React. Kinet. Catal. Lett., 9, 331–336, 1978.
Forgeteg, S., T. Berces, and S. Dobe, The kinetics and mechanism of n-butylaldehyde photolysis in
the vapor phase at 313 nm, Int. J. Chem. Kinet., 11, 219–237, 1979.
Frost, M., and I.W.M. Smith, Rate constants for the reactions of CH3 O and C2 H5 O with NO over a
range of temperature and total pressure, J. Chem. Soc. Faraday Trans. II, 86, 1757–1762, 1990a.
Frost, M., and I.W.M. Smith, Rate constants for the reactions of CH3 O and C2 H5 O with NO2 over a
range of temperature and total pressure, J. Chem. Soc. Faraday Trans. II, 86, 1751–1756, 1990b.
Gaffney, J. S., R. Fajer, G. I. Senum, and J. H. Lee, Measurement of the reactivity of OH with methyl
nitrate: Implications for prediction of alkyl nitrate-OH reaction rates, International Journal of
Chemical Kinetics, 18, 399–407, 1986.
Gardner, E., P.D. Sperry, and J.G. Calvert, Photodecomposition of acrolein in O2 - N2 mixtures, J.
Phys. Chem., 91, 1922–1930, 1987.
Gery, M. W., G. Z. Whitten, J. P. Killus, and M. C. Dodge, A photochemical kinetics mechanism
for urban and regional scale computer modeling, J. Geophys. Res., 94, 12925–12956, 1989.
Graedel, T. E., and P. J. Crutzen, Atmospheric Change: An Earth System Perspective, W. H. Freeman
and Company, 1993.
Grosjean, D., Atmospheric chemistry of toxic contaminants 1. reaction rates and atmospheric
103
persistence, J. Air Waste Manage. Assoc., 40, 1397–1402, 1990.
Grosjean, D., Atmospheric fate of toxic aromatic compounds, The Science of the Total Environment,
100, 367–414, 1991.
Hamlin, A. J., Transport of ozone precursors from the arctic troposphere to the North Atlantic
region, Master’s thesis, Michigan Technological University, 1995.
Hamlin, A. J., and R. E. Honrath, A modeling study of the impact of winter–spring arctic outflow
on the NOx and O3 budgets of the North Atlantic troposphere, J. Geophys. Res., in press, 2002.
Heicklen, J., J. Desai, A. Bahta, C. Harper, and R. Simonaitis, The temperature and wavelength
dependance of the photooxidation of propionaldehyde, J. Photochem., 34, 117–135, 1986.
Herring, J. A., D. A. Jaffe, H. J. Beine, S. Madronich, and D. R. Blake, High-latitude springtime
photochemistry. Part II: Sensitivity studies of ozone production, J. Atmos. Chem., 27, 155–178,
1997.
Honrath, R. E., and D. A. Jaffe, The seasonal cycle of nitrogen oxides in the Arctic troposphere at
Barrow, Alaska, J. Geophys. Res., 97, 20,615–20,630, 1992.
Honrath, R. E., A. J. Hamlin, and J. T. Merrill, Transport of ozone precursors from the Arctic
troposphere to the North Atlantic region, J. Geophys. Res., 101, 29,335–29,351, 1996.
Horie, O., and G.K. Moortgat, Reactions of CH3 C(O)O2 radicals with CH3 O and HO2 between 263
and 333 K, J. Chem. Soc. Faraday Trans. II, 88, 3305–3312, 1992.
Hough, A., Development of a two-dimensional global tropospheric model: Model chemistry, J.
Geophys. Res., 96, 7325–7362, 1991.
Hov, O., S. A. Penkett, I. A. A. Isaksen, and A. Semb, Organic gases in the Norwegian Arctic,
Geophys. Res. Lett., 11, 425–428, 1984.
Jacob, D. J., Heterogeneous chemistry and tropospheric ozone, Atmos. Environ., 34, 2131–2159,
2000.
Jaffe, D. A., R. E. Honrath, J. A. Herring, S.-M. Li, and J. D. Kahl, Measurements of nitrogen
oxides at Barrow, Alaska, during spring: Evidence for regional and northern hemispheric sources
of pollution, J. Geophys. Res., 96, 7395–7405, 1991.
Jenkin, M. E., R. A. Cox, G. Hayman, and L. J. Whyte, Kinetic study of the reactions methylperoxy
+ methylperoxy and methylperoxy + hydroperoxy using molecular modulation spectroscopy, J.
Chem. Soc. Faraday Trans. II, 84, 913–30, 1988.
Jenkin, M. E., S. M. Saunders, and M. J. Pilling, The tropospheric degradation of volatile organic
compounds: a protocol for mechanism development, Atmos. Environ., 31, 81–104, 1997.
Jobson, B. T., H. Niki, Y. Yokouchi, J. Bottenheim, F. Hopper, and R. Leaitch, Measurements of
C2 –C6 hydrocarbons during the Polar Sunrise Experiment: Evidence for Cl atom and Br atom
chemistry, J. Geophys. Res., 99, 25,355–25,368, 1994.
Johnston, H., C.A. Cantrell, and J.G. Calvert, Unimolecular decompositon of NO3 to form NO and
O2 and a review of N2O5 /NO3 kinetics, J. Geophys. Res., 91, 5159–5172, 1986.
Johnston, H. S., H. F. Davis, and Y. T. Lee, No3 photolysis product channels: Quantum yields from
104
observed energy thresholds, J. Phys. Chem., 100, 4713–4723, 1996.
Kerr, J. A., and D. W. Stocker, Kinetics of the reactions of hydroxyl radicals with alkyl nitrates and
with some oxygen-containing organic compounds studied under simulated atmospheric conditions, Journal of Atmospheric Chemistry, 4, 253–262, 1986.
Kirchner, F., and W. R. Stockwell, Effect of peroxy radical reactions on the predicted concentrations
of ozone, nitrogenous compounds, and radicals, J. Geophys. Res., 101, 21,007–21,022, 1996.
Kirchner, F., and W. R. Stockwell, Correction to “Effect of peroxy radical reactions on the predicted
concentrations of ozone, nitrogenous compounds, and radicals”, J. Geophys. Res., 102, 10,871,
1997.
Kondratyev, K. Y., Radiation in the Atmosphere, Academic Press, New York, 1969.
Kurylo, M., T.J. Wallington, and P.A. Ouellette, Measurements of the UV absorption cross section
for hydroperoxy and methylperoxy in gas phase, J. Photochem., 39, 201–215, 1987.
Kylling, A., Phodis, a program package for calculation of photodissociation rates in the Earth’s
atmosphere, available by anonymous ftp to kaja.gi.alaska.edu, cd pub/arve, 1995.
Lamarque, J.-F., G. P. Brasseur, P. G. Hess, and J.-F. Müller, Three-dimensional study of the
relative contributions of the different nitrogen sources in the troposphere, J. Geophys. Res., 101,
22,955–22,968, 1996.
Langford, A., and C.B. Moore, Collision complex formation in reactions of formyl radicals with
nitric oxide and oxygen, J. Chem. Phys., 80, 4211–4221, 1984.
Laurila, T., and H. Hakola, Seasonal cycle of C2 –C5 hydrocarbons over the Baltic Sea and Northern
Finland, Atmos. Environ., 30, 1597–1607, 1996.
Lay, T. H., J. W. Bozzelli, and J. H. Seinfeld, Atmospheric photochemical oxidation of benzene:
Benzene + OH and the benzene–OH adduct (hydroxyl–2,4–cyclohexadienyl) + O2, J. Phys.
Chem., 100, 6543–6554, 1996.
Leaitch, W. R., L. A. Barrie, J. W. Bottenheim, S. M. Li, P. B. Shepson, K. Muthuramu, and
Y. Yokouchi, Airborne observations related to ozone depletion at polar sunrise, J. Geophys. Res.,
99, 25,499–25,517, 1994.
LeBras, G., editor, Chemical Processes in Atmospheric Oxidation: Laboratory Studies of Chemistry
Related to Tropospheric Ozone, Springer–Verlag, New York, 1997.
Lelieveld, J., and Frank J. Dentener, What controls tropospheric ozone?, J. Geophys. Res., 105,
3531–3551, 2000.
Levy II, H., W. J. Moxim, A. A. Klonecki, and P. S. Kasibhatla, Simulated tropospheric NO x :
Its evaluation, global distribution and individual source contributions, J. Geophys. Res., 104,
26,279–26,306, 1999.
Li, S.-M., Equilibrium of particle nitrite with gas phase HONO: Tropospheric measurements in the
high Arctic during polar sunrise, J. Geophys. Res., 99, 25,469–25,478, 1994.
Liang, J., L. W. Horowitz, D. J. Jacob, Y. Wang, A. M. Fiore, J. A. Logan, G. M. Gardner, and J. W.
Munger, Seasonal budgets of reactive nitrogen species and ozone over the United States, and
105
export fluxes to the global atmosphere, J. Geophys. Res., 103, 13,435–13,450, 1998.
Lightfoot, P. D., R. Lesclaux, and B. Veyret, Flash photolysis study of the methylperoxy + methylperoxy reaction: rate constants and braching ratios from 284-573 K, J. Phys. Chem., 94, 700–707,
1990.
Lightfoot, P., R.A. Cox, J.N. Crowley, M. Destriau, G.D. Hayman, M.E. Jenkin, and G.K. Moortgat,
Organic peroxy radical: Kinetics, spectroscopy and tropospheric chemistry, Atmos. Environ.,
26A, 1806–1963, 1992.
Logan, J. A., Tropospheric ozone: Seasonal behavior, trends, and anthropogenic influence, J.
Geophys. Res., 90, 10,463–10,482, 1985.
Luke, W., and R.R. Dickerson, Direct measurements of the photolysis rate coefficient of ethyl
nitrate, Geophys. Res. Lett., 15, 1181–1184, 1988.
Luke, W., R.R Dickerson, and L.J. Nunnermacker, Direct measurements of the photolysis rate
coefficients and Henry’s law constants of several alkyl nitrates, J. Geophys. Res., 94, 14905–
14921, 1989.
Lurmann, F. W., W. P. Carter, and L. A. Coyner, A surrogate species chemical reaction mechanism
for urban–scale air quality simulation models: Vol-I Adaptation of the mechanism, Final Report,
EPA Contract No. 68-02-4104, Atmospheric Sciences Research Laboratory, Research Triangle
Park, NC., Technical report, 1987.
Lüttke, J., V. Scheer, K. Levsen, G. Wünsch, J. N. Cape, K. J. Hargreaves, R. L. Storeton-West,
K. Acker, W. Wieprect, and B. Jones, Occurence and formation of nitrated phenols in and out of
cloud, Atmos. Environ., 31, 2637–2648, 1997.
Madronich, S., and J. G. Calvert, The NCAR Master Mechanism of the gas phase chemistry—
Version 2.0, Technical Report NCAR/TN-333+STR, National Center for Atmospheric Research,
Boulder, Colorado, May 1989.
Madronich, S., and Jack G. Calvert, Permutation reactions of organic peroxy radicals in the
troposphere, J. Geophys. Res., 95, 5697–5715, 1990.
Maricq, M. M., and Joseph J. Szente, Kinetics of the reaction between ethylperoxy radicals and
nitric oxide, J. Phys. Chem., 100, 12374–12379, 1996.
Marinelli, W., D.M. Swanson, and H.S. Johnston, Absorption cross-section and line shape for the
nitrogen trioxide (O-O) band, J. Chem. Phys., 76, 2864–2870, 1982.
Martinez, R. D., A. A. Buitrago, N. W. Howell, C. H. Hearn, and J. A. Joens, The near U.V.
absorption spectra of several aliphatic aldehydes and ketones at 300 K, Atmos. Environ., 26A,
785–792, 1992.
Mazely, T. L., R. R. Friedl, and S. P. Sander, Quantum yield of NO3 from peroxyacetyl nitrate
photolysis, J. Phys. Chem., 101, 7090–7097, 1997.
McAdam, K., B. Veyret, and R. Lesclaux, UV absorption spectra of hydroperoxo (HO2 ) and
hydroperoxymethyl (C3 O2 ) radicals and the kinetics of their mutual reactions at 298 K, Chem.
Phys. Lett., 133, 39–44, 1987.
106
Meller, R., W. Raber, J.N. Crowley, M.E. Jenkin, and G.K. Moortgat, The UV-visible absorption
spectrum of methylglyoxal, J. Photochem. and Photobiol., 62, 163–171, 1991.
Mentel, T. F., D. Bleilebens, and A. Wahner, A study of nighttime nitrogen oxide oxidation in a
large reaction chamber—the fate of NO2 , N2 O5, HNO3, and O3 at different humidities, Atmos.
Environ., 30, 4007–4020, 1996.
Meyrahn, H., J. Pauly, W. Schneider, and P. Warneck, Quantum yields for the photodissociation of
acetone in air and an estimate for the life time of acetone in the lower troposphere, J. Atmos.
Chem., 4, 277–291, 1986.
Mineshos, G., and S. Glavas, Thermal decomposition of peroxypropionyl nitrate: Kinetics of the
formation of nitrogenous products, React. Kinet. Catal. Lett., 45, 305–312, 1991.
Moortgat, G., W. Seiler, and P. Warneck, Photodissociation of formaldehyde in air: carbon monoxide
and diatomic hydrogen quantum yields at 220 and 300 K, J. Chem. Phys., 78, 1185–1190, 1983.
Moortgat, G., B. Veyret, and R. Lesclaux, Kinetics of the reaction of hydroperoxo (HO 2 ) with
peroxyacetyl [CH3 C(O)O2 ] in the temperature range 253-368 K, Chem. Phys. Lett., 160, 443–
447, 1989.
Moxim, W. J., H. Levy II, and P. S. Kasibhatla, Simulated global tropospheric PAN: Its transport
and impact on NOx , J. Geophys. Res., 101, 12,621–12,638, 1996.
Murphy, D. M., and D. W. Fahey, An estimate of the flux of stratospheric reactive nitrogen and
ozone into the troposphere, J. Geophys. Res., 99, 5325–5332, 1994.
Muthuramu, K., P. B. Shepson, J. W. Bottenheim, B. T. Jobson, H. Niki, and K. G. Anlauf, Relationships between organic nitrates and surface ozone destruction during Polar Sunrise Experiment
1992, J. Geophys. Res., 99, 25,369–25,378, 1994.
Nicovich, J., and P.H. Wine, Temperature-dependent absorption cross sections for hydrogen peroxide
vapor, J. Geophys. Res., 93, 2417–2421, 1988.
Nielsen, O. J., Howard W. Sidebottom, Michael Donlon, and Jack Treacy, Rate constants for the
gas-phase reactions of OH radicals and Cl atoms with n-alkyl nitrites at atmospheric pressure and
298 K, Int. J. Chem. Kinet., 23, 1095–1109, 1991a.
Nielsen, O. J., Howard W. Sidebottom, Michael Donlon, and Jack Treacy, An absolute and realtive
rate study of the gas-phase reaction of hydroxyl radicals and cholrine atoms with n-alkyl nitrates,
Chem. Phys. Lett., 178, 163–170, 1991b.
Niki, H., P.D. Maker, C.M. Savage, and M.D. Hurley, Fourier transform infrared study of the
kinetics and mechanisms for the Cl-atom and OH-radical initiated oxidation of glycolaldehyde,
J. Phys. Chem., 91, 2174–2178, 1987.
Nojima, K., K. Fukaya, S. Fukui, and S. Kanno, Studies on photochemistry of aromatic hydrocarbons
II: The formation of nitrophenols and nitrobenzene by the photochemical reaction of benzene in
the presence of nitrogen monoxide, Chemosphere, 4, 77–82, 1975.
Novelli, P. C., K. A. Masarie, and P. M. Lang, Distributions and recent changes of carbon monoxide
in the lower troposphere, J. Geophys. Res., 103, 19015–19033, 1998.
107
Ohmori, K., K. Yamasaki, and H. Matsui, Pressure dependence of the rate constant for the reaction
of methoxyl with nitric oxide, Bull. Chem. Soc. Jpn., 66, 51–56, 1993.
Oltmans, S. J., Climatology of Arctic and Antarctic tropospheric ozone, In Niki, H., and K. H.
Becker, editors, The Tropospheric Chemistry of Ozone in the Polar Regions, volume I 7 of NATO
ASI Series, pp. 25–40, Springer-Verlag, Berlin, 1993.
Penner, J. E., C. S. Atherton, J. Dignon, S. J. Ghan, J. J. Walton, and S. Hameed, Tropospheric
nitrogen: A three-dimensional study of sources, distributions, and deposition, J. Geophys. Res.,
96, 959–990, 1991.
Plumb, I., K.R. Ryan, J.R. Steven, and M.F.R. Mulcahy, Kinetics of the reaction of C 2 H5 O2 with
NO at 295K, Int. J. Chem. Kinet., 14, 183–194, 1982.
Plum, C., E. Sanhueza, R. Atkinson, W.P.L. Carter, and J.N. Pitts Jr., Hydroxyl radical rate constants
and photolysis rate of -dicarbonyls, Environ. Sci. Tech., 17, 479, 1983.
Radke, L. F., J.H. Lyons, D.A. Hegg, P.V. Hobbs, and I.H. Bailey, Airborne observations of arctic
aerosols. I: Characteristics of arctic haze, Geophys. Res. Lett., 11, 393–396, 1984.
Ravishankara, A., and R.L. Mauldin, Temperature dependence of the NO3 cross section in the
662-nm region, J. Geophys. Res., 91, 8709–8712, 1986.
Ravishankara, A., and P.H. Wine, Absorption cross section for nitrogen trioxide between 565 and
673 nm, Chem. Phys. Lett., 101, 73–78, 1983.
Ravishankara, A., J.M. Nicovich, R.L. Thompson, and F.P. Tully, Kinetic study of the reaction of
OH with H2 and D2 from 250 to 1050 K, J. Phys. Chem., 85, 2498–2503, 1981.
Ravishankara, A., P.H. Wine, C.A. Smith, P.E. Barbone, and A. Torabi, N2 O5 photolysis: Quantum
yields for NO3 and O(3 P), J. Geophys. Res., 91, 5355–5360, 1986.
Ridley, B., J. Walega, D. Montzka, F. Grahek, E. Atlas, F. Flocke, V. Stroud, J. Deary, A. Gallant,
H. Boudries, J. Bottenheim, K. Anlauf, D. Worthy, A. L. Sumner, and P. Shepson, Is the Arctic
surface layer a source and sink of NOx in winter/spring?, J. Atmos. Chem., 36, 1–22, 2000.
Roberts, J. M., Reactive odd–nitrogen (NOy) in the atmosphere, In Singh, H. B., editor, Composition,
Chemistry, and Climate of the Atmosphere, Van Nostrand Reinhold, 1995.
Roberts, J. M., and R. W. Fajer, UV absorption cross sections of organic nitrates of potential
atmospheric importance and estimation of atmospheric lifetimes, Environ. Sci. Tech., 23, 945–
951, 1989.
Roehl, C., D. Bauer, and G.K. Moortgat, Absorption spectrum and kinetics of the acetyl peroxy
radical, J. Phys. Chem., 100, 4038–4047, 1996.
Roelofs, G., and J. Lelieveld, Distribution and budget of O 3 in the troposphere calculated with a
chemistry general circulation model, J. Geophys. Res., 100, 20983–20998, 1995.
Rogers, J. D., Ultraviolet absorption cross sections and atmospheric photodissociation rate constants
for formaldehyde, J. Phys. Chem., 94, 4011–4015, 1990.
Rohrer, F., D. Brüning, and D. H. Ehhalt, Tropospheric mixing ratios of NO obtained during
TROPOZ II in the latitude region 67N–56S, J. Geophys. Res., 102, 25,429–25,449, 1997.
108
Sander, S., Temperature dependence of the NO3 absorption spectrum, J. Phys. Chem., 90, 4135–
4142, 1986.
Sander, S., and R.T. Watson, Temperature dependence of the self-reaction of methyldioxy radicals,
J. Phys. Chem., 85, 2960–2964, 1981.
Sander, S. P., R. R. Friedl, W. B. DeMore, D. M. Golden, M. J. Kurylo, R. F. Hampson, R. E.
Huie, G. K. Moortgat, A. R. Ravishankara, C. E. Kolb, and M. J. Molina, Chemical kinetics and
photochemical data for use in stratospheric modeling, supplement to evaluation 12: Update of
key reactions, evaluation number 13, Technical report, NASA Jet Propulsion Laboratory, 2000.
Schneider, W., G.K. Moortgat, J.P. Burrows, and G. Tyndall, Absorption cross-section of nitrogen
dioxide in the UV and visible region (200-700 nm) at 298 K, J. Photochem. Photobiol., 40,
195–217, 1987.
Schurath, U., and V. Wipprecht, Reactions of peroxyacyl radicals, In Proc. 1st European Symp. on
the Physico-Chemical Behaviour of Atmospheric Pollutants, pp. 157–166, 1980.
Seinfeld, J. H., Ozone air quality models: A critical review, J. Air Poll. Control Assoc., pp. 616–645,
1988.
Simon, F. G., W. Schneider, and G. K. Moortgat, UV-absorption spectrum of the methyl radical and
the kinetics of its disproportionation reaction at 300 K, Int. J. Chem. Kinet., 22, 791–813, 1990.
Singh, H. B., Reactive nitrogen in the troposphere, Env. Sci. Tech., 21, 320–327, 1987.
Singh, H. B., and P. L. Hanst, Peroxyacetyl nitrate (PAN) in the unpolluted atmosphere: An important
reservoir for nitrogen oxides, Geophys. Res. Lett., 8, 941–944, 1981.
Solberg, S., C. Dye, N. Schmidbauer, A. Herzog, and R. Gehrig, Carbonyls and nonmethane
hydrocarbons at rural European sites from the Mediterranean to the Arctic, J. Atmos. Chem., 25,
33–66, 1996a.
Solberg, S., N. Schmidbauer, A. Semb, F. Stordal, and O. Hov, Boundary-layer ozone depletion as
seen in the Norwegian Arctic in spring, J. Atmos. Chem., 23, 301–332, 1996b.
Staffelbach, T., J.J. Orlando, G.S. Tyndall, and J.G. Calvert, The UV-visible absorption spectrum
and photolysis quantum yields of methylglyoxal, J. Geophys. Res., 100, 14189–14198, 1995.
Stockwell, W., On the HO2 + HO2 reaction: Its misapplication in atmospheric chemistry models,
J. Geophys. Res., 100, 11695–11698, June 1995.
Stockwell, W. R., P. Middleton, J.S. Chang, and X. Tang, The second generation regional acid
deposition model chemical mechanism for regional air quality modeling, J. Geophys. Res., 95,
16,343–16,367, 1990.
Stockwell, W. R., F. Kirchner, M. Kuhn, and S. Seefeld, A new mechanism for regional atmospheric
chemistry modeling, J. Geophys. Res., 102, 25,847–25,880, 1997.
Sverdrup, G. M., C. W. Spicer, and G. F. Ward, Investigation of the gas phase reaction of dinitrogen
pentoxide with water vapor, Int. J. Chem. Kinet., 19, 191–205, 1987.
Talukdar, R., S.C. Herndon, J.B. Burkholder, J.M Roberts, and A.R. Ravishankara, Atmospheric
fate of several alkyl nitrates: Part 1 Rate coefficeients of the reactions of alkyl nitrates with
109
isotopically labelled hydroxyl radicals, J. Chem. Soc. Faraday Trans. II, 93, 2787–2796, 1997.
Taylor, W., T.D. Allston, M.J. Moscato, G.B. Fazakas, R. Kozlowski, and G.A. Takacs, Atmospheric
photodissociation lifetimes for nitromethane, methyl nitrite, and methyl nitrate, Int. J. Chem.
Kinet., 12, 231–240, 1980.
Turberg, M., D.M. Giolando, C. Tilt, T. Soper, S. Mason, M. Davies, P. Klingensmith, and G.A.
Takacs, Atmospheric photochemistry of alkyl nitrates, J. Photochem. Photobiol., A51, 281–292,
1990.
Tyndall, G., John J. Orlando, and Jack G. Calvert, Upper limit for the rate coefficient for the reaction
HO2 + NO2 ! HONO + O2 , Environ. Sci. Tech., 29, 202–206, 1995.
Vaghjiani, G., and A.R. Ravishankara, Absorption cross sections of CH 3 OOH, H2O2 , and D2O2
vapors between 210 and 365 nm at 297 K, J. Geophys. Res., 94, 3487–3492, 1989.
Wahner, A., T. F. Mental, and M. Sohn, Gas-phase reaction of N2 O5 with water vapor: Importance
of heterogeneous hydrolysis of N2 O5 and surface desorption of HNO3 in a large Teflon chamber,
Geophys. Res. Lett., 25, 2169–2172, 1998.
Wang, Y., D. J. Jacob, and J. A. Logan, Global simulation of tropospheric O 3 -NOx -hydrocarbon
chemistry: 1. Model formulation, J. Geophys. Res., 103, 10713–10726, 1998a.
Wang, Y., J. A. Logan, and D. J. Jacob, Global simulation of tropospheric O 3 -NOx -hydrocarbon
chemistry: 3. Origin of tropospheric ozone and effects of nonmethane hydrocarbons, J. Geophys.
Res., 103, 10,757–10,767, 1998b.
Wang, Y., J. A. Logan, and D. J. Jacob, Global simulation of tropospheric O 3 -NOx -hydrocarbon
chemistry: 2. Model evaluation and global ozone budget, J. Geophys. Res., 103, 10727–10756,
1998c.
Wayne, R., I. Barnes, P. Biggs, J.P. Burrows, C.E. Canosa-Mas, J. Hjorth, G. LeBras, G.K. Moortgat,
D. Perner, G. Poulet, G. Restelli, and H. Sidebottom, The nitrate radical: physics, chemistry, and
the atmosphere, Atmos. Environ., 25A, 1–203, 1991.
Weinheimer, A. J., J. G. Walega, B. A. Ridley, B. L. Gary, D. R. Blake, N. J. Blake, F. S. Rowland,
G. W. Sachse, B. E. Anderson, and J. E. Collins, Meridional distributions of NOx , NOy , and
other species in the lower stratosphere and upper troposphere during AASE II, Geophys. Res.
Lett., 21, 2583, 1994.
Whelpdale, D. M., and J. N. Galloway, Sulfur and reactive nitrogen oxide fluxes in the North
Atlantic atmosphere, Global Biogeochem. Cycles, 8, 481–493, 1994.
Wiesen, E., I. Barnes, and K. H. Becker, Study of the OH-initiated degradation of the aromatic
photooxidation product 3,4-dihydroxy-3-hexene-2,5-dione, Environ. Sci. Tech., 29, 1380–1386,
1995.
Williams, J., private communication, 1994a.
Williams, J., A study of the atmospheric chemistry of alkyl nitrates, Ph.D. thesis, University of East
Anglia, 1994b.
WMO, Atmospheric ozone 1985: Assessment of our understanding of the processes controlling the
110
present distribution and change, rep. 16, chaps. 5 and 10, World Meteorological Organization,
Global Ozone Res. Monit. Prog., Geneva, 1986.
Zellner, R., B. Fritz, and M. Preidel, A cw UV laser absorption study of the reactions of the
hydroxy–cyclohexadienyl radical with NO2 and NO, Chem. Phys. Lett., 121, 412–416, 1985.
Zellner, R., B. Fritz, and K. Lorenz, Methoxy formation in the reaction of CH3 O2 radicals with no,
J. Atmos. Chem., 4, 241–251, 1986.
Appendix A
Chemical Codes
The NCAR Master Mechanism uses a coding system to identify chemical species. This coding
system, developed by Madronich and Calvert [1989], is briefly described in this appendix to aid
in the reading of reactions described in Appendix B. The chemical code is written explicitly if the
compound can be expressed unambigously in 4 characters or less (e.g., NO2, O3). Otherwise the
code is constructed based on the functional groups and the number of carbons in the molecule. The
first character indicates the most reactive functional group, the second character the second most
reactive functional group. (A list of the numbers and letters used to identify functional groups are
shown in Table A.1. This information was taken from the file README [Madronich and Calvert,
1989].) The third character in the code indicates the number of carbon atoms in the compound,
while the fourth character is a counter used to distinguish between species with the same first 3
charaters. For example c041 indicates n-butane, while c042 indicates i-butane.
Table A.1 Functional Groups [Madronich and Calvert, 1989].
0 = alkyl radicals
1 = alkoxy radicals
2 = alkyl peroxy radicals
3 = acyl peroxy radicals
4 = criegee biradicals
5-9 = misc.
a = acids
b = bromine
c = pure hydrocarbon
d = aldehydes
e = ethers, esters
f = flourine
g = peroxy acids
h = hydroperoxides
k = ketones
l = chlorine
m = amine
n = organic nitrates
o = alcohol
p = peroxy acyl nitrates
q = misc inorganic
s = sulfur
t = alpha-pinene and its derivatives
u = double bond (unsaturated)
v = nitro (-NO2)
w = nitrite (-NO)
z = non-specific hydrocarbons (C5H12)
111
112
The code names used in the NCAR Master Mechanism are listed in Tables A.2–A.45 . Also
listed in these tables are the number of atoms of carbon (C), halogens (X), hydrogen (H), nitrogen
(N), oxygen (O), and sulfur (S), the full chemical formula, and the functional groups.
These tables contain the contents from the file alphadict.dat [Madronich and Calvert, 1989].
113
Table A.2 Chemical Codes: 0031–1081 [Madronich and Calvert, 1989].
Code
(M)
0031
0032
0b11
0d21
0d22
0f14
0f15
0f16
0f24
0f25
0f26
0f27
0f28
0f29
0l11
0l12
0l21
0l23
0m11
0m21
0m22
0o11
0o21
0u22
1021
1031
1032
1041
1042
1043
1044
1051
1052
1053
1054
1055
1056
1057
1061
1062
1063
1071
1081
C
0
3
3
1
2
2
1
1
1
2
2
2
2
2
2
1
1
2
2
1
2
2
1
2
2
2
3
3
4
4
4
4
5
5
5
5
5
5
5
6
6
6
7
8
X
0
0
0
1
0
0
3
3
2
4
3
5
5
4
3
1
2
1
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
0
7
7
2
3
1
0
0
1
1
2
0
0
1
2
2
1
2
2
4
6
6
3
5
3
5
7
7
9
9
9
9
11
11
11
11
11
11
11
13
13
13
15
17
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
0
0
0
0
1
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
(M) - troe
CH3CH.CH3
CH3CH2CH2.
CH2.(Br)
CH3CO.
CHOCO.
C.(F)(Cl2)
C.(F2)(Cl)
CH.(Cl)(F)
C(F3)CH.(F)
C(F2)(Cl)CH2.
C(F3)C.(Cl2)
C(F3)C.(Cl)(F)
C(Cl)(F2)CH.(Cl)
C(Cl2)(F)CH2.
CH2.(Cl)
CH.(Cl2)
CdH(Cl)=CdH.
C(Cl3)CH2.
CH3(NH.)
CH2NH.CH3
CH3NCH3
CH2.(OH)
CH2(OH)CH2.
CdH(OH)=CdH.
CH3CH2(O.)
CH3CH2CH2(O.)
CH3CH(O.)CH3
CH3CH(CH3)CH2(O.)
CH3CH2CH2CH2(O.)
CH3CH2CH(O.)CH3
CH3C(O.)(CH3)CH3
C5H11(O.)
CH3CH(CH3)CH(O.)CH3
CH3CH2CH2CH2CH2(O.)
CH3CH2CH2CH(O.)CH3
CH3CH2CH(O.)CH2CH3
CH3CH2CH(CH3)CH2(O.)
CH3CH2C(O.)(CH3)CH3
C6H13(O.)
CH3CH(CH3)C(O.)(CH3)CH3
CH3CH(CH3)CH(CH3)CH2(O.)
C7H15(O.)
C8H17(O.)
Functional Groups
|
| 0.
| 0.
| 0.b
| 0.d
| 0.dd
| 0.fl
| 0.fl
| 0.fl
| 0.fl
| 0.fl
| 0.fl
| 0.fl
| 0.fl
| 0.fl
| 0.l
| 0.l
| 0.l
| 0.l
| 0.m
| 0.m
| 0.m
| 0.o
| 0.o
| 0.ou
| 1.
| 1.
| 1.
| 1.
| 1.
| 1.
| 1.
| 1.z
| 1.
| 1.
| 1.
| 1.
| 1.
| 1.
| 1.z
| 1.
| 1.
| 1.z
| 1.z
114
Table A.3 Chemical Codes: 1a21–1e71.
Code
1a21
1a31
1a32
1a33
1a41
1a42
1a43
1a44
1a50
1a51
1a52
1d21
1d31
1d32
1d33
1d34
1d35
1d36
1d41
1d42
1d43
1d44
1d45
1d46
1d47
1d48
1d49
1d51
1d52
1d53
1d54
1d55
1d56
1d57
1d58
1d59
1d5A
1d5B
1d61
1d62
1d81
1d82
1dA2
1e71
C
2
3
3
3
4
4
4
4
5
5
5
2
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
6
6
8
8
10
7
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
3
5
3
3
7
7
5
7
7
7
7
3
5
5
3
3
5
2
4
4
7
5
5
5
7
7
7
6
7
6
7
7
7
7
9
9
9
7
11
11
13
13
15
11
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
0
0
0
0
0
0
0
1
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
3
3
4
4
3
4
4
4
5
5
6
2
2
3
3
3
2
5
6
6
3
4
4
3
2
3
2
6
4
6
5
4
4
3
2
2
2
3
2
3
3
2
3
4
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CO(OH)CH2(O.)
CO(OH)CH(O.)CH3
CO(OH)COCH2(O.)
CO(OH)CH(O.)CHO
CH3CH2CH(O.)CO(OH)
CO(OH)CH(OH)CH2CH2(O.)
CO(OH)COCH(O.)CH3
CH2(OH)C(O.)(CO(OH))CH3
CH3COCH(OH)CH(O.)CO(OH)
CO(OH)CH(OH)CH(O.)COCH3
CO(OH)CH(OH)CH(OH)COCH2(O.)
CHOCH2(O.)
CH3CH(O.)CHO
CH2(OH)CH(O.)CHO
CHOCH(O.)CHO
CHOCOCH2(O.)
CHOCH2CH2(O.)
CO(NO2)CH(O.)CHO
CHOCH(OH)CH(O.)CO(NO2)
CO(NO2)CH(OH)CH(O.)CHO
CH2(OH)C(O.)(CH3)CHO
CHOCH(OH)CH(O.)CHO
CHOCH(OH)COCH2(O.)
CH3COCH(O.)CHO
CHOCH2CH(O.)CH3
CH2(OH)CH(O.)CH2CHO
CHOCH(CH3)CH2(O.)
CHOCH(OH)C(NO2)(O.)COCH3
CHOCH(OH)CH(O.)COCH3
CH3COC(OH)(NO2)CH(O.)CHO
CHOCH(OH)CH(OH)COCH2(O.)
CHOCH(OH)C(O.)(CH3)CHO
CH3COCH(OH)CH(O.)CHO
CH3COCH(O.)CH2CHO
CH3CH2CH(O.)CH2CHO
CHOCH2C(O.)(CH3)CH3
CHOCH(CH3)CH(O.)CH3
CHOCH2C(O.)(CH3)CHO
CHOCH(CH3)C(O.)(CH3)CH3
CHOCH(CH3)C(O.)(CH3)CH2(OH)
CHOCH2CH(COCH3)C(O.)(CH3)CH3
O’CH’CH2’CHCH2CHO’CCH3CH3
CH2(O.)CO’CH’CH2’CHCH2CHO’CCH3CH3
CH3COCOCH2OC(O.)(CH3)CH3
Functional Groups
| 1.a
| 1.a
| 1.ka
| a1.d
| 1.a
| 1.oa
| 1.ka
| o1.a
| ko1.a
| ao1.k
| aook1.
| 1.d
| 1.d
| o1.d
| d1.d
| dk1.
| d1.
| dk1.v
| k1.odv
| ko1.dv
| o1.d
| ddo1.
| 1.kod
| k1.d
| 1.d
| o1.d
| d1.
| do1.kv
| k1.od
| d1.okv
| 1.kood
| 1.ddo
| ko1.d
| k1.d
| 1.d
| d1.
| d1.
| d1.d
| d1.
| d1.o
| kd 1.
| 1.td
| 1.ktd
| kke1.
115
Table A.4 Chemical Codes: 1f14–1m33.
Code
1f14
1f15
1g21
1g40
1h51
1h52
1h53
1h71
1k31
1k33
1k40
1k41
1k42
1k44
1k45
1k46
1k47
1k48
1k4B
1k4C
1k4D
1k51
1k54
1l11
1l13
1l21
1l22
1l31
1l41
1l42
1l43
1m11
1m12
1m13
1m21
1m22
1m23
1m24
1m25
1m33
C
1
1
2
4
5
5
5
7
3
3
4
4
4
4
4
4
4
4
4
4
4
5
5
1
1
2
2
3
4
4
4
1
1
1
2
2
2
2
2
3
X
3
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
3
1
1
1
1
1
1
0
0
0
0
0
0
0
0
0
H
0
0
3
7
10
10
11
13
5
5
7
5
7
7
7
7
7
7
7
7
7
9
11
2
0
4
4
6
8
8
8
4
4
4
6
6
6
6
6
8
N
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
O
1
1
4
5
7
7
5
5
3
2
3
3
2
3
2
3
2
3
3
4
4
4
5
1
1
1
1
1
1
1
2
2
1
1
1
1
1
1
2
1
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
C(F)(Cl2)(O.)
C(F2)(Cl)(O.)
CO(OOH)CH2(O.)
CH2(OH)C(O.)(CH3)CO(OOH)
CH2(ONO2)C(OOH)(CH3)CH(O.)CH2(OH)
CH2(ONO2)CH(OOH)C(O.)(CH3)CH2(OH)
CH2(OH)CH(OOH)C(O.)(CH3)CH2(OH)
CH3C(OH)(CH3)C(O.)(CH2(OOH))COCH3
CH2(OH)COCH2(O.)
CH3COCH2(O.)
CH3COCH(OH)CH2(O.)
CH3COCOCH2(O.)
CH3CH2COCH2(O.)
CH3COCH(O.)CH2(OH)
CH3COCH(O.)CH3
CH2(OH)COCH2CH2(O.)
CH3COCH2CH2(O.)
CH2(OH)CH2COCH2(O.)
CH3CH(OH)COCH2(O.)
CH2(OH)COCH(OH)CH2(O.)
CH2(OH)CH(OH)COCH2(O.)
CH2(OH)COC(O.)(CH3)CH2(OH)
CH2(OH)C(OOH)(CH3)CH(O.)CH2(OH)
CH2(Cl)(O.)
C(Cl3)(O.)
CH2(Cl)CH2(O.)
CH3CH(Cl)(O.)
CH2(Cl)CH(O.)CH3
CH3CH(Cl)CH(O.)CH3
CH2(Cl)C(O.)(CH3)CH3
CH3CH(OH)CH(Cl)CH2(O.)
CH2(OH)(NH(O.))
CH3(NH(O.))
CH2(O.)(NH2)
CH3CH2(NH(O.))
CH3N(O.)CH3
CH3CH(O.)(NH2)
CH3(NH)CH2(O.)
CH2(OH)N(O.)CH3
CH3CH2(O.)NCH3
Functional Groups
| 1.fl
| 1.fl
| 1.g
| o1.g
| nh1.o
| o1.hn
| o1.ho
| kh1.o
| 1.ko
| k1.
| ko1.
| 1.kk
| k1.
| k1.o
| 1.k
| ok1.
| k1.
| ok1.
| ok1.
| oko1.
| 1.koo
| o1.ko
| ok1.o
| l1.
| 1.l
| l1.
| l1.
| l1.
| 1.l
| 1.l
| 1.lo
| mo1.
| m1.
| 1.m
| m1.
| m1.
| 1.m
| m1.
| om1.
| 1.m
116
Table A.5 Chemical Codes: 1n11–1o54.
Code
1n11
1n21
1n22
1n23
1n31
1n32
1n33
1n34
1n41
1n42
1n43
1n44
1n45
1n46
1n47
1n48
1n49
1n51
1n52
1n53
1n54
1nA1
1o11
1o21
1o22
1o31
1o32
1o33
1o34
1o35
1o40
1o41
1o43
1o44
1o45
1o46
1o48
1o49
1o4A
1o4B
1o4C
1o4D
1o50
1o51
1o52
1o53
1o54
C
1
2
2
2
3
3
3
3
4
4
4
4
4
4
4
4
4
5
5
5
5
10
1
2
2
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
2
2
4
4
3
6
6
6
5
6
5
6
6
8
8
6
6
8
8
10
10
16
3
5
5
7
7
7
7
7
9
9
9
9
9
9
9
9
9
9
9
9
11
11
11
11
11
N
1
1
1
1
2
1
1
1
2
1
2
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
4
5
4
4
8
4
4
5
8
6
9
7
5
4
4
5
6
4
4
6
6
4
2
2
2
3
3
2
2
2
2
2
2
2
2
2
3
3
2
3
2
3
3
3
2
3
2
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH2(ONO2)(O.)
CHOCH(ONO2)(O.)
CH2(ONO2)CH2(O.)
CH3CH(ONO2)(O.)
CO(NO2)CH(OH)CH(ONO2)(O.)
CH2(ONO2)CH(O.)CH3
CH3CH(ONO2)CH2(O.)
CH2(OH)CH(ONO2)CH2(O.)
CH3COC(NO2)(OH)CH(ONO2)(O.)
CH3COCH(OH)CH(ONO2)(O.)
CH(ONO2)(OH)C(NO2)(OH)COCH2(O.)
CH(ONO2)(OH)CH(OH)COCH2(O.)
CH2(ONO2)C(O.)(CH3)CHO
CH2(ONO2)C(O.)(CH3)CH3
CH3CH(ONO2)CH(O.)CH3
CH3COCH(O.)CH2(ONO2)
CH2(ONO2)CH(OH)COCH2(O.)
CH2(ONO2)C(O.)(CH3)CdH=CdH2
CdH2=Cd(CH3)CH(O.)CH2(ONO2)
CH2(OH)CH(O.)C(ONO2)(CH3)CH2(OH)
CH2(OH)C(O.)(CH3)CH(ONO2)CH2(OH)
C9H12CH3(O.),H(ONO2)
CH2(OH)(O.)
CH3CH(OH)(O.)
CH2(OH)CH2(O.)
CH2(OH)CH(OH)CH2(O.)
CH2(OH)CH(O.)CH2(OH)
CH2(OH)CH(O.)CH3
CH3CH(OH)CH2(O.)
CH2(OH)CH2CH2(O.)
CH3CH2CH(OH)CH2(O.)
CH2(OH)C(O.)(CH3)CH3
CH2(OH)CH2CH2CH2(O.)
CH3CH(OH)CH(O.)CH3
CH3C(OH)(CH3)CH2(O.)
CH3CH(OH)CH2CH2(O.)
CH2(OH)C(OH)(CH3)CH2(O.)
CH3CH(OH)CH(OH)CH2(O.)
CH2(OH)CH(CH3)CH2(O.)
CH2(OH)CH(OH)CH2CH2(O.)
CH2(OH)CH2CH(O.)CH3
CH2(OH)CH2CH(OH)CH2(O.)
CH2(OH)CH2CH(OH)CH(O.)CH3
CH3CH2CH2CH(O.)CH(OH)(OH)
CH2(OH)CH2CH2CH2CH2(O.)
CH2(OH)CH(CH3)CH(O.)CH2(OH)
CH2(OH)CH(CH3)CH(O.)CH3
Functional Groups
| n1.
| dn1.
| n1.
| n1.
| konv1.
| 1.n
| n1.
| on1.
| kon1.v
| kon1.
| 1.konov
| 1.kono
| n1.d
| 1.n
| 1.n
| k1.n
| 1.kon
| n1.u
| u1.n
| o1.no
| o1.no
| t1.n
| o1.
| 1.o
| o1.
| oo1.
| o1.o
| 1.o
| o1.
| o1.
| o1.
| 1.o
| 1.o
| o1.
| o1.
| o1.
| 1.oo
| 1.oo
| o1.
| 1.oo
| 1.o
| oo1.
| 1.oo
| 1.oo
| o1.
| oo1.
| o1.
117
Table A.6 Chemical Codes: 1o56–1v34.
Code
1o56
1o57
1o58
1o59
1o5A
1o5B
1o5C
1o61
1o62
1o63
1o64
1o65
1o71
1o81
1p21
1p30
1p31
1r61
1r62
1r63
1r64
1r71
1r72
1r73
1r74
1r75
1r76
1r77
1r81
1r82
1r83
1s21
1t81
1t91
1t92
1tA1
1u51
1u52
1u71
1v34
C
5
5
5
5
5
5
5
6
6
6
6
6
7
8
2
3
3
6
6
6
6
7
7
7
7
7
7
7
8
8
8
2
8
9
9
10
5
5
7
3
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
11
11
11
11
11
11
11
13
13
13
13
13
15
17
2
4
4
5
4
7
7
7
7
6
8
9
9
8
9
11
11
5
13
15
15
17
9
9
11
2
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
0
1
0
0
0
0
1
1
0
0
1
0
0
0
0
0
0
0
0
0
0
0
1
O
2
2
2
2
2
4
4
2
4
2
3
2
2
2
6
6
6
1
3
2
3
1
1
3
5
2
3
4
1
2
3
1
2
2
3
2
2
2
2
5
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
Full Chemical Formula
CH2(OH)CH2CH2CH(O.)CH3
CH3CH(OH)CH2CH2CH2(O.)
CH3CH2CH(OH)CH2CH2(O.)
CH2(OH)CH(CH3)CH2CH2(O.)
CH3CH(OH)CH(CH3)CH2(O.)
CH2(OH)C(OH)(CH3)CH(OH)CH2(O.)
CH2(OH)C(OH)(CH3)CH(O.)CH2(OH)
C6H12(O.)(OH)
CH2(OH)CH(CH2(OH))CH(CH2(OH))CH2(O.)
CH2(OH)CH(CH3)CH(CH3)CH2(O.)
CH2(OH)CH(CH3)CH(CH2(OH))CH2(O.)
CH3C(OH)(CH3)CH(CH3)CH2(O.)
C7H14(OH)(O.)
C8H16(OH)(O.)
CO(OONO2)CH2(O.)
CH2(O.)CH2CO(OONO2)
CH3CH(O.)CO(OONO2)
C6H5(O.)
C6H4(O.),NO2
C6H4(H)(OH),(H)(O.)
C6H4(OH)(OH),H(O.)
C6H5CH2(O.)
C6H4CH3,(O.)
C6H3CH3,(O.),NO2
C6H3CH3,(OH)(OH),(O.)(NO2)
C6H3CH3,H(OH),H(O.)
C6H3CH3,OH(OH),H(O.)
C6H3(O.),H(OH),CH3,NO2
C6H3CH3,(O.),CH3
C6H3CH3,H(OH),(CH3)(O.)
C6H3CH3,OH(OH),(CH3)(O.)
CH3SCH2(O.)
CH3CO’CH’CH2’CH(O.)’CCH3CH3
CH3CO’CH’CH2’CH(CH2(O.))’CCH3CH3
CH3CO’CH’CH2’CH(CH2(OH))’CCH3CH2(O.)
C9H12CH3,(O.),HOH
CdH2=Cd(CH3)CH(O.)CH2(OH)
CH2(OH)C(O.)(CH3)CdH=CdH2
CH3COCd(CH2(O.))=Cd(CH3)CH3
CO(NO2)COCH2(O.)
Functional Groups
| 1.o
| 1.o
| o1.
| o1.
| 1.o
| ooo1.
| oo1.o
| o1.z
| 1.ooo
| 1.o
| o1.o
| 1.o
| o1.z
| o1.z
| 1.p
| 1.p
| 1.p
| r1.
| r1.v
| 1.or
| r1.oo
| r1.
| r1.
| r1.v
| roo1.v
| ro1.
| roo1.
| r1.ov
| r1.
| ro1.
| roo1.
| 1.s
| kt1.
| kt1.
| kto1.
| to1.
| u1.o
| o1.u
| k1.u
| vkk1.
118
Table A.7 Chemical Codes: 2011–2d49.
Code
2011
2021
2031
2032
2041
2042
2043
2044
2051
2052
2053
2054
2055
2056
2057
2061
2062
2063
2071
2081
2a21
2a31
2a32
2a41
2a42
2a43
2a47
2a50
2a51
2a53
2d21
2d31
2d32
2d33
2d34
2d41
2d42
2d43
2d44
2d45
2d47
2d48
2d49
C
1
2
3
3
4
4
4
4
5
5
5
5
5
5
5
6
6
6
7
8
2
3
3
4
4
4
4
5
5
5
2
3
3
3
3
4
4
4
4
4
4
4
4
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
3
5
7
7
9
9
9
9
11
11
11
11
11
11
11
13
13
13
15
17
3
5
3
7
5
7
7
7
7
7
3
5
5
3
5
4
4
5
7
5
7
7
7
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
0
0
0
0
0
0
O
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
4
4
5
4
5
5
5
6
6
7
3
4
3
4
3
7
7
5
4
5
3
4
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3(OO.)
CH3CH2(OO.)
CH3CH(OO.)CH3
CH3CH2CH2(OO.)
CH3CH2CH(OO.)CH3
CH3CH2CH2CH2(OO.)
CH3C(OO.)(CH3)CH3
CH3CH(CH3)CH2(OO.)
C5H11(OO.)
CH3CH(CH3)CH(OO.)CH3
CH3CH2CH2CH2CH2(OO.)
CH3CH2CH2CH(OO.)CH3
CH3CH2CH(OO.)CH2CH3
CH3CH2CH(CH3)CH2(OO.)
CH3CH2C(OO.)(CH3)CH3
C6H13(OO.)
CH3CH(CH3)C(OO.)(CH3)CH3
CH3CH(CH3)CH(CH3)CH2(OO.)
C7H15(OO.)
C8H17(OO.)
CO(OH)CH2(OO.)
CH3CH(OO.)CO(OH)
CO(OH)COCH2(OO.)
CH3CH2CH(OO.)CO(OH)
CO(OH)COCH(OO.)CH3
CH2(OH)C(OO.)(CH3)CO(OH)
CO(OH)CH(OH)CH2CH2(OO.)
CO(OH)CH(OH)CH(OO.)COCH3
CH3COCH(OH)CH(OO.)CO(OH)
CO(OH)CH(OH)CH(OH)COCH2(OO.)
CHOCH2(OO.)
CH2(OH)CH(OO.)CHO
CH3CH(OO.)CHO
CHOCOCH2(OO.)
CHOCH2CH2(OO.)
CHOCH(OH)CH(OO.)CO(NO2)
CO(NO2)CH(OH)CH(OO.)CHO
CHOCH(OH)CH(OO.)CHO
CH2(OH)C(OO.)(CH3)CHO
CHOCH(OH)COCH2(OO.)
CHOCH2CH(OO.)CH3
CHOCH2CH(OO.)CH2(OH)
CHOCH(CH3)CH2(OO.)
Functional Groups
| 2.
| 2.
| 2.
| 2.
| 2.
| 2.
| 2.
| 2.
| 2.z
| 2.
| 2.
| 2.
| 2.
| 2.
| 2.
| 2.z
| 2.
| 2.
| 2.z
| 2.z
| 2.a
| 2.a
| 2.ka
| 2.a
| 2.ak
| o2.a
| 2.oa
| ao2.k
| koa2.
| aook2.
| d2.
| o2.d
| 2.d
| dk2.
| d2.
| k2.odv
| ko2.dv
| do2.d
| o2.d
| 2.dok
| 2.d
| 2.do
| d2.
119
Table A.8 Chemical Codes: 2d50–2k71.
Code
2d50
2d51
2d52
2d53
2d54
2d55
2d56
2d57
2d58
2d59
2d5A
2d61
2d62
2d81
2d82
2dA2
2e72
2f13
2f14
2f15
2g21
2g40
2h51
2h52
2h53
2h54
2h71
2k33
2k34
2k40
2k42
2k43
2k44
2k45
2k46
2k47
2k48
2k49
2k4B
2k4C
2k51
2k71
C
5
5
5
5
5
5
5
5
5
5
5
6
6
8
8
10
7
1
1
1
2
4
5
5
5
5
7
3
3
4
4
4
4
4
4
4
4
4
4
4
5
7
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
3
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
9
6
7
6
7
7
7
7
9
9
7
11
11
13
13
15
11
0
0
0
3
7
11
11
10
10
13
5
5
7
7
5
7
7
7
7
7
7
7
7
9
13
N
0
1
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
3
7
5
7
6
5
5
4
3
3
4
3
4
3
4
4
5
2
2
2
5
6
6
6
8
8
6
3
4
4
4
4
3
3
5
3
4
4
4
5
5
4
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CHOCH(CH3)CH(OO.)CH3
CH3COC(OO.)(NO2)CH(OH)CHO
CH3COCH(OO.)CH(OH)CHO
CH3COC(OH)(NO2)CH(OO.)CHO
CHOCH(OH)CH(OH)COCH2(OO.)
CH3COCH(OH)CH(OO.)CHO
CHOCH(OH)C(OO.)(CH3)CHO
CH3COCH(OO.)CH2CHO
CH3CH2CH(OO.)CH2CHO
CHOCH2C(OO.)(CH3)CH3
CHOCH2C(OO.)(CH3)CHO
CHOCH(CH3)C(OO.)(CH3)CH3
CHOCH(CH3)C(OO.)(CH3)CH2(OH)
’CH(OO.)’CH2’CH(CH2CHO)’C(CH3)CH3
CHOCH2CH(COCH3)C(OO.)(CH3)CH3
CH2(OO.)CO’CH’CH2’CHCH2CHO’CCH3CH3
CH3COCOCH2OC(OO.)(CH3)CH3
C(F3)(OO.)
C(F)(Cl2)(OO.)
C(F2)(Cl)(OO.)
CO(OOH)CH2(OO.)
CH2(OH)C(OO.)(CH3)CO(OOH)
CH2(OH)C(OOH)(CH3)CH(OO.)CH2(OH)
CH2(OH)CH(OOH)C(OO.)(CH3)CH2(OH)
CH2(ONO2)C(OOH)(CH3)CH(OO.)CH2(OH)
CH2(ONO2)CH(OOH)C(OO.)(CH3)CH2(OH)
CH3C(OH)(CH3)C(OO.)(CH2(OOH))COCH3
CH3COCH2(OO.)
CH2(OH)COCH2(OO.)
CH3COCH(OH)CH2(OO.)
CH3COCH(OO.)CH2(OH)
CH3COCOCH2(OO.)
CH3COCH(OO.)CH3
CH3CH2COCH2(OO.)
CH2(OH)CH(OH)COCH2(OO.)
CH3COCH2CH2(OO.)
CH2(OH)COCH2CH2(OO.)
CH2(OH)CH2COCH2(OO.)
CH3CH(OH)COCH2(OO.)
CH2(OH)COCH(OH)CH2(OO.)
CH2(OH)COC(OO.)(CH3)CH2(OH)
CH3C(OH)(CH3)CH(CH2(OO.))COCH3
Functional Groups
| d2.
| do2.kv
| k2.od
| d2.okv
| 2.kood
| ko2.d
| do2.d
| k2.d
| 2.d
| d2.
| d2.d
| d2.
| d2.o
| 2.td
| kd 2.
| 2.kd
| kke 2.
| 2.f
| 2.fl
| 2.fl
| 2.g
| 2.og
| h2.oo
| o2.ho
| nh2.o
| o2.hn
| kh2. o
| k2.
| 2.ko
| ko2.
| k2.o
| kk 2.
| k2.
| k2.
| 2.koo
| k2.
| ok2.
| ok2.
| ok2.
| oko2.
| ook2.
| o2.k
120
Table A.9 Chemical Codes: 2l11–2nA1.
Code
2l11
2l13
2l21
2l22
2l31
2l41
2l42
2l43
2m01
2m11
2m12
2m21
2m22
2m23
2m33
2n11
2n21
2n22
2n23
2n31
2n32
2n33
2n34
2n41
2n42
2n43
2n44
2n45
2n46
2n47
2n48
2n49
2n51
2n52
2n53
2n54
2nA1
C
1
1
2
2
3
4
4
4
0
1
1
2
2
2
3
1
2
2
2
3
3
3
3
4
4
4
4
4
4
4
4
4
5
5
5
5
10
X
1
3
1
1
1
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
2
0
4
4
6
8
8
8
2
4
4
6
6
6
8
2
2
4
4
3
6
6
6
5
6
5
6
8
8
6
6
6
8
8
10
10
16
N
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
2
1
1
1
2
1
2
1
1
1
1
1
1
1
1
1
1
1
O
2
2
2
2
2
2
2
3
2
2
3
2
2
3
2
5
6
5
5
9
5
5
6
9
7
10
8
5
5
6
6
7
5
5
7
7
5
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH2(Cl)(OO.)
C(Cl3)(OO.)
CH2(Cl)CH2(OO.)
CH3CH(Cl)(OO.)
CH3CH(OO.)CH2(Cl)
CH3CH(Cl)CH(OO.)CH3
CH3C(OO.)(CH3)CH2(Cl)
CH3CH(OH)CH(Cl)CH2(OO.)
NH2(OO.)
CH2(OO.)(NH2)
CH2(OH)(NH(OO.))
CH3CH(OO.)(NH2)
CH3CH2(OO.)NH
CH2(OH)N(OO.)CH3
CH3CH3CH2(OO.)N
CH2(ONO2)(OO.)
CHOCH(ONO2)(OO.)
CH2(ONO2)CH2(OO.)
CH3CH(ONO2)(OO.)
CO(NO2)CH(OH)CH(ONO2)(OO.)
CH3CH(OO.)CH2(ONO2)
CH3CH(ONO2)CH2(OO.)
CH2(OH)CH(ONO2)CH2(OO.)
CH3COC(NO2)(OH)CH(ONO2)(OO.)
CH3COCH(OH)CH(ONO2)(OO.)
CH(ONO2)(OH)C(NO2)(OH)COCH2(OO.)
CH(ONO2)(OH)CH(OH)COCH2(OO.)
CH3CH(ONO2)CH(OO.)CH3
CH3C(OO.)(CH3)CH2(ONO2)
CH2(ONO2)C(OO.)(CH3)CHO
CH3COCH(OO.)CH2(ONO2)
CH2(ONO2)CH(OH)COCH2(OO.)
CdH2=CdHC(OO.)(CH3)CH2(ONO2)
CdH2=Cd(CH3)CH(OO.)CH2(ONO2)
CH2(OH)CH(OO.)C(ONO2)(CH3)CH2(OH)
CH2(OH)C(OO.)(CH3)CH(ONO2)CH2(OH)
C9H12CH3(OO.),H(ONO2)
Functional Groups
| 2.l
| 2.l
| 2.l
| 2.l
| 2.l
| 2.l
| 2.l
| 2.ol
| m2.
| 2.m
| om2.
| o2.m
| 2. m
| om2.
| 2.m
| n2.
| dn2.
| 2.n
| n2.
| kon2.v
| 2.n
| 2.n
| o2.n
| kon2.v
| kon2.
| 2.konov
| 2.kono
| 2.n
| 2.n
| n2.d
| k2.n
| 2.kon
| n2.u
| u2.n
| o2.no
| o2.no
| t2.n
121
Table A.10 Chemical Codes: 2o11–2p31.
Code
2o11
2o21
2o31
2o32
2o33
2o34
2o35
2o40
2o42
2o43
2o44
2o45
2o46
2o48
2o49
2o4A
2o4B
2o4C
2o4D
2o50
2o51
2o52
2o53
2o54
2o55
2o56
2o57
2o58
2o59
2o5A
2o5B
2o61
2o62
2o63
2o64
2o65
2o71
2o81
2p21
2p30
2p31
C
1
2
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
7
8
2
3
3
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
3
5
7
7
7
7
7
9
9
9
9
9
9
9
9
9
9
9
9
11
11
11
11
11
11
11
11
11
11
11
11
13
13
13
13
13
15
17
2
4
4
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
O
3
3
4
3
3
3
4
3
3
3
3
3
3
4
4
3
4
3
4
4
3
3
4
4
3
3
3
3
3
5
5
3
3
4
5
3
3
3
7
7
7
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH2(OH)(OO.)
CH2(OH)CH2(OO.)
CH2(OH)CH(OO.)CH2(OH)
CH3CH(OO.)CH2(OH)
CH3CH(OH)CH2(OO.)
CH2(OH)CH2CH2(OO.)
CH2(OH)CH(OH)CH2(OO.)
CH3CH2CH(OH)CH2(OO.)
CH2(OH)CH2CH2CH2(OO.)
CH3CH(OH)CH(OO.)CH3
CH3C(OO.)(CH3)CH2(OH)
CH3C(OH)(CH3)CH2(OO.)
CH3CH(OH)CH2CH2(OO.)
CH2(OH)C(OH)(CH3)CH2(OO.)
CH3CH(OH)CH(OH)CH2(OO.)
CH2(OH)CH(CH3)CH2(OO.)
CH2(OH)CH(OH)CH2CH2(OO.)
CH2(OH)CH2CH(OO.)CH3
CH2(OH)CH2CH(OH)CH2(OO.)
CH2(OH)CH2CH(OH)CH(OO.)CH3
C5H10(OH)(OO.)
CH2(OH)CH(CH3)CH(OO.)CH3
CH2(OH)CH(CH3)CH(OO.)CH2(OH)
CH3CH2CH2CH(OO.)CH(OH)(OH)
CH3CH(OH)CH(CH3)CH2(OO.)
CH2(OH)CH2CH2CH(OO.)CH3
CH3CH(OH)CH2CH2CH2(OO.)
CH3CH2CH(OH)CH2CH2(OO.)
CH2(OH)CH(CH3)CH2CH2(OO.)
CH2(OH)C(OH)(CH3)CH(OO.)CH2(OH)
CH2(OH)C(OH)(CH3)CH(OH)CH2(OO.)
C6H12(OH)(OO.)
CH2(OH)CH(CH3)CH(CH3)CH2(OO.)
CH2(OH)CH(CH3)CH(CH2(OH))CH2(OO.)
CH2(OH)CH(CH2(OH))CH(CH2(OH))CH2(OO.)
CH3C(OH)(CH3)CH(CH3)CH2(OO.)
C7H14(OH)(OO.)
C8H16(OH)(OO.)
CO(OONO2)CH2(OO.)
CH2(OO.)CH2CO(OONO2)
CH3CH(OO.)CO(OONO2)
Functional Groups
| o2.
| o2.
| o2.o
| 2.o
| o2.
| o2.
| 2.oo
| o2.
| 2.o
| o2.
| 2.o
| 2.o
| o2.
| 2.oo
| 2.oo
| o2.
| 2.oo
| 2.o
| oo2.
| 2.oo
| o2.z
| o2.
| o2.o
| 2.oo
| 2.o
| 2.o
| 2.o
| 2.o
| o2.
| oo2.o
| ooo2.
| o2.z
| 2.o
| o2.o
| o2.oo
| 2.o
| o2.z
| o2.z
| 2.p
| 2.p
| 2.p
122
Table A.11 Chemical Codes: 2r61–3d48.
Code
2r61
2r62
2r63
2r71
2r72
2r73
2r74
2r75
2r81
2r82
2s21
2t71
2t81
2t91
2t92
2tA1
2u51
2u52
2u71
2v31
3021
3031
3041
3042
3051
3052
3053
3061
3a21
3a31
3a32
3a33
3d21
3d31
3d32
3d33
3d41
3d42
3d43
3d44
3d45
3d46
3d47
3d48
C
6
6
6
7
7
7
7
7
8
8
2
7
8
9
9
10
5
5
7
3
2
3
4
4
5
5
5
6
2
3
3
3
2
3
3
3
4
4
4
4
4
4
4
4
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
7
7
5
8
7
9
9
8
11
11
5
11
13
15
15
17
9
9
11
2
3
5
7
7
9
9
9
11
1
3
3
3
1
2
3
3
2
4
3
3
5
3
3
5
N
0
0
0
1
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
1
1
0
0
0
0
0
0
O
3
4
2
6
2
3
4
5
3
4
2
4
3
3
4
3
3
3
3
6
3
3
3
3
3
3
3
3
5
6
5
7
4
7
5
4
8
8
6
6
6
5
5
4
S
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
C6H5(H)OH/(OO.)
C6H5(OH)OH/(OO.)
C6H5(OO.)
C6H3CH3,(OH)(OH),NO2/(OO.)
C6H5CH2(OO.)
C6H4CH3,HOH/(OO.)
C6H4CH3,OHOH/(OO.)
C6H3HOH,CH3,NO2,(OO.)
C6H3CH3,HOH,CH3/(OO.)
C6H3CH3,(OH)OH,CH3/(OO.)
CH3SCH2(OO.)
CH3CO’C(OO.)’CH2’O’C(CH3)CH3
CH3CO’CH’CH2’CH(OO.)’C(CH3)CH3
CH3CO’CH’CH2’CH(CH2OO.)’CCH3CH3
CH3CO’CH’CH2’CH(CH2(OH))’CCH3CH2OO.
C9H12CH3(OO.),H(OH)
CdH2=CdHC(OO.)(CH3)CH2(OH)
CdH2=Cd(CH3)CH(OO.)CH2(OH)
CH3COCd(CH2(OO.))=Cd(CH3)CH3
CO(NO2)COCH2(OO.)
CH3CO(OO.)
CH3CH2CO(OO.)
CH3CH2CH2CO(OO.)
CH3CH(CH3)CO(OO.)
CH3CH2CH2CH2CO(OO.)
CH3CH2CH(CH3)CO(OO.)
CH3CH(CH3)CH2CO(OO.)
CH3CH(CH3)CH(CH3)CO(OO.)
CO(OH)CO(OO.)
CO(OH)CH(OH)CO(OO.)
CO(OH)CH2CO(OO.)
CO(OH)C(OH)(OH)CO(OO.)
CHOCO(OO.)
CHOC(NO2)(OH)CO(OO.)
CHOCH(OH)CO(OO.)
CHOCH2CO(OO.)
CHOCOC(NO2)(OH)CO(OO.)
CHOCH(OH)C(NO2)(OH)CO(OO.)
CHOCH(OH)COCO(OO.)
CHOCOCH(OH)CO(OO.)
CHOCH(OH)CH(OH)CO(OO.)
CHOCOCH2CO(OO.)
CHOCH2COCO(OO.)
CHOCH(CH3)CO(OO.)
Functional Groups
| ro2.
| roo2.
| r2.
| roo2.
| r2.
| r2.o
| r2.oo
| rov2.
| r2.o
| r2.oo
| 2.s
| 2.kt
| kt2.
| kt2.
| kto2.
| to2.
| o2.u
| u2.o
| k2.u
| kk2.v
| 3.
| 3.
| 3.
| 3.
| 3.
| 3.
| 3.
| 3.
| 3.a
| 3.ao
| 3.ao
| 3.aoo
| d3.
| do3.v
| do3.
| d3.
| dko3.v
| doo3.v
| dok3.
| 3.okd
| doo3.
| dk3.
| dk3.
| d3.
123
Table A.12 Chemical Codes: 3d51–3n49.
Code
3d51
3d52
3d53
3d54
3d55
3d56
3g40
3h21
3h40
3k31
3k33
3k40
3k45
3k46
3k47
3k48
3k49
3k4A
3k50
3k51
3k52
3k53
3k55
3k57
3k58
3k59
3k5A
3k5B
3k5C
3k81
3l11
3n21
3n31
3n32
3n33
3n34
3n41
3n42
3n43
3n44
3n45
3n46
3n47
3n48
3n49
C
5
5
5
5
5
5
4
2
4
3
3
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
8
1
2
3
3
3
3
4
4
4
4
4
4
4
4
4
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
3
3
5
5
7
7
5
3
7
3
3
5
5
5
5
5
5
5
7
5
5
5
5
7
7
5
7
7
7
13
0
2
1
2
2
4
3
3
4
3
4
4
6
6
6
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
1
1
1
2
2
1
2
1
1
1
1
1
O
7
7
7
7
4
4
8
5
6
5
4
5
5
6
5
5
4
6
5
6
7
7
6
6
7
5
4
5
4
5
3
6
9
7
7
6
10
9
7
10
8
8
6
7
7
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CHOCOCH(OH)COCO(OO.)
CHOCOCOCH(OH)CO(OO.)
CHOCOCH(OH)CH(OH)CO(OO.)
CHOCH(OH)CH(OH)COCO(OO.)
CHOCH(CH3)CH2CO(OO.)
CHOCH2CH(CH3)CO(OO.)
CO(OOH)C(OOH)(CH3)CO(OO.)
CH2(OOH)CO(OO.)
CH2(OH)C(OOH)(CH3)CO(OO.)
CH2(OH)COCO(OO.)
CH3COCO(OO.)
CH3CH(OH)COCO(OO.)
CH3COCH(OH)CO(OO.)
CH2(OH)COCH(OH)CO(OO.)
CH2(OH)COCH2CO(OO.)
CH2(OH)CH2COCO(OO.)
CH3COCH2CO(OO.)
CH2(OH)CH(OH)COCO(OO.)
CH3COCH(OH)CH2CO(OO.)
CH3COCOCH(OH)CO(OO.)
CH2(OH)COCOCH(OH)CO(OO.)
CH2(OH)COCH(OH)COCO(OO.)
CH3COCH(OH)COCO(OO.)
CH3COCH(OH)CH(OH)CO(OO.)
CH2(OH)COCH(OH)CH(OH)CO(OO.)
CH3COCOCH2CO(OO.)
CH3COCH2CH2CO(OO.)
CH3CH(OH)COCH2CO(OO.)
CH3COCH(CH3)CO(OO.)
CH3COCH(C(OH)(CH3)CH3)CH2CO(OO.)
CO(Cl)(OO.)
CH2(ONO2)CO(OO.)
CO(NO2)CH(ONO2)CO(OO.)
CH2(ONO2)COCO(OO.)
CHOCH(ONO2)CO(OO.)
CH3CH(ONO2)CO(OO.)
CO(NO2)CH(ONO2)CH(OH)CO(OO.)
CH3COC(NO2)(ONO2)CO(OO.)
CH3COCH(ONO2)CO(OO.)
CO(NO2)CH(OH)CH(ONO2)CO(OO.)
CH2(ONO2)COCH(OH)CO(OO.)
CHOCH(ONO2)CH(OH)CO(OO.)
CH3CH(ONO2)CH2CO(OO.)
CH2(OH)CH(ONO2)CH2CO(OO.)
CH2(OH)C(ONO2)(CH3)CO(OO.)
Functional Groups
| dkok3.
| dkko3.
| dkoo3.
| dook3.
| d3.
| d3.
| gh3.
| h3.
| oh3.
| ok3.
| k3.
| ok3.
| ko3.
| ok3.
| ok3.
| ok3.
| k3.
| ook3.
| ko3.
| kko3.
| okko3.
| okok3.
| kok3.
| koo3.
| okoo3.
| kk 3.
| k3.
| ok3.
| k3.
| k3.o
| 3.l
| n3.
| kn3.v
| nk3.
| dn3.
| n3.
| kno3.v
| kn3.v
| kn3.
| kon3.v
| nko3.
| dno3.
| 3.n
| o3.n
| on3.
124
Table A.13 Chemical Codes: 3n51–3u53.
Code
3n51
3n52
3n53
3n54
3n55
3o22
3o23
3o31
3o32
3o33
3o34
3o35
3o41
3o42
3o43
3o44
3o45
3o46
3o47
3o51
3o52
3o53
3o54
3o55
3o56
3o57
3o61
3r71
3t91
3tA1
3u31
3u32
3u41
3u42
3u43
3u44
3u51
3u52
3u53
C
5
5
5
5
5
2
2
3
3
3
3
3
4
4
4
4
4
4
4
5
5
5
5
5
5
5
6
7
9
10
3
3
4
4
4
4
5
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
5
6
5
6
6
3
3
5
5
5
5
5
7
7
7
7
7
7
7
9
9
9
9
9
9
9
11
5
13
15
2
3
2
3
5
2
4
5
5
N
2
1
2
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
1
0
0
1
1
0
0
O
10
8
10
8
9
5
4
4
5
5
6
4
4
4
4
5
4
5
4
4
4
4
4
5
4
6
4
3
4
4
7
5
6
4
3
6
6
4
4
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3COC(NO2)(ONO2)CH(OH)CO(OO.)
CH3COCH(ONO2)CH(OH)CO(OO.)
CH3COC(NO2)(OH)CH(ONO2)CO(OO.)
CH3COCH(OH)CH(ONO2)CO(OO.)
CH2(ONO2)COCH(OH)CH(OH)CO(OO.)
CH(OH)(OH)CO(OO.)
CH2(OH)CO(OO.)
CH3CH(OH)CO(OO.)
CH2(OH)CH(OH)CO(OO.)
CH3C(OH)(OH)CO(OO.)
CH2(OH)C(OH)(OH)CO(OO.)
CH2(OH)CH2CO(OO.)
CH3C(OH)(CH3)CO(OO.)
CH2(OH)CH2CH2CO(OO.)
CH3CH(OH)CH2CO(OO.)
CH2(OH)CH(OH)CH2CO(OO.)
CH3CH2CH(OH)CO(OO.)
CH2(OH)CH2CH(OH)CO(OO.)
CH2(OH)CH(CH3)CO(OO.)
CH3CH(OH)CH2CH2CO(OO.)
CH3CH2CH(OH)CH2CO(OO.)
CH2(OH)CH(CH3)CH2CO(OO.)
CH2(OH)CH2CH(CH3)CO(OO.)
CH3CH(OH)CH(OH)CH2CO(OO.)
CH3CH(OH)CH(CH3)CO(OO.)
CH2(OH)C(OH)(CH3)CH(OH)CO(OO.)
CH2(OH)CH(CH3)CH(CH3)CO(OO.)
C6H5CO(OO.)
apR2C8H13OCO(OO.)
apR1C9H15OCO(OO.)
Cd(OH)(NO2)=Cd(OH)CO(OO.)
CdH(OH)=Cd(OH)CO(OO.)
CO(NO2)CdH=Cd(OO.)CHO
CHOCdH=CdHCO(OO.)
CdH2=Cd(CH3)CO(OO.)
CHOCdH=Cd(NO2)CO(OO.)
CH3COCd(NO2)=CdHCO(OO.)
CH3COCdH=CdHCO(OO.)
CHOCdH=Cd(CH3)CO(OO.)
Functional Groups
| kno3.v
| kno3.
| kon3.v
| kon3.
| nkoo3.
| oo3.
| o3.
| o3.
| oo3.
| oo3.
| ooo3.
| o3.
| o3.
| o3.
| o3.
| oo3.
| o3.
| oo3.
| o3.
| o3.
| o3.
| o3.
| o3.
| oo3.
| o3.
| ooo3.
| o3.
| r3.
| k 3.t
| k 3.t
| ouo3.v
| ouo3.
| ku3.v
| du3.
| 3.u
| duv3.
| ku3.v
| ku 3.
| du 3.
125
Table A.14 Chemical Codes: 3v21–7dA1.
Code
3v21
3v22
3v32
3v41
3v42
3v43
3v44
3v54
3v56
4011
4021
4031
4041
4a31
4d21
4d22
4d31
4dA1
4k32
4o12
4o21
4o22
4o23
4o31
4s10
4tA2
4u41
4u42
4v11
4v21
4v31
6r61
6r71
6r72
6r73
6r74
6r81
6r82
7011
7021
7031
7041
7a31
7d21
7d22
7d31
7dA1
C
2
2
3
4
4
4
4
5
5
1
2
3
4
3
2
2
3
10
3
1
2
2
2
3
1
10
4
4
1
2
3
6
7
7
7
7
8
8
1
2
3
4
3
2
2
3
10
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
2
0
2
2
2
4
4
4
6
2
4
6
8
4
2
2
4
16
4
2
4
4
4
6
3
16
6
6
1
1
3
7
8
9
9
8
11
11
2
4
6
8
4
2
2
4
16
N
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
0
1
0
0
1
0
0
0
0
0
0
0
0
0
0
0
O
7
6
7
8
8
7
8
8
8
2
2
2
2
4
4
3
3
3
3
3
4
3
3
3
2
3
2
2
5
5
5
2
4
1
2
3
1
2
2
2
2
2
4
4
3
3
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
C(OH)(OH)(NO2)CO(OO.)
CO(NO2)CO(OO.)
CO(NO2)CH(OH)CO(OO.)
CO(NO2)COCH(OH)CO(OO.)
CO(NO2)CH(OH)COCO(OO.)
CH3COC(NO2)(OH)CO(OO.)
CO(NO2)CH(OH)CH(OH)CO(OO.)
CH3COC(NO2)(OH)COCO(OO.)
CH3COC(NO2)(OH)CH(OH)CO(OO.)
CH2.(OO.)
CH3CH.(OO.)
CH3C.(OO.)CH3
CH3CH2CH2CH.(OO.)
CH3C.(OO.)CO(OH)
CHOC.(OH)(OO.)
CHOCH.(OO.)
CH3C.(OO.)CHO
CH3COO’CH’CH2’CHCH2CHO’CCH3CH3
CH3COCH.(OO.)
CH.(OH)(OO.)
CH2(OH)C.(OH)(OO.)
CH2(OH)CH.(OO.)
CH3C.(OH)(OO.)
CH3CH2C.(OH)(OO.)
CH3S(OO.)
CH3CO’CH’CH2’CHCH2CH.(OO.)’CCH3CH3
CdH2=CdHC.(OO.)CH3
CdH2=Cd(CH3)CH.(OO.)
C.(NO2)(OH)(OO.)
CO(NO2)CH.(OO.)
CH3COC.(NO2)(OO.)
C6H5(OH)(OH)
C6H3CH3,(OH)(OH),NO2
C6H4CH3,HOH
C6H4CH3,OHOH
C6H3HOH,CH3,NO2
C6H3CH3,(H)OH,CH3
C6H3CH3,(OH)OH,CH3
[CH2OO]*
[CH3CHOO]*
[CH3C(CH3)OO]*
[CH3CH2CH2CHOO]*
[CH3C(OO)CO(OH)]*
[CHOC(OH)OO]*
[CHOCHOO]*
[CHOC(CH3)OO]*
[CH3COO’CH’CH2’CHCH2CHO’CCH3CH3]*
Functional Groups
| oo3.v
| kv3.
| ko3.v
| kko3.v
| kok3.v
| ko3.v
| koo3.v
| kok3.v
| koo3.v
| 4..
| 4..
| 4..
| 4..
| 4..a
| do4..
| 4..d
| 4..d
| 4..td
| 4..k
| o4..
| oo4..
| o4..
| 4o..
| o4..
| s4..
| 4..tk
| 4..u
| u4..
| ov4..
| k4..v
| k4..v
| ro6o.
| roo6.
| ro6.
| roo6.
| rov6.
| ro6.
| roo6.
| 7.
| 7.
| 7.
| 7.
| 7.a
| 7.do
| 7.d
| 7.d
| 7.td
126
Table A.15 Chemical Codes: 7k32–8k33.
Code
7k32
7m01
7o12
7o21
7o22
7o23
7o31
7tA2
7u41
7u42
7v21
7v31
8021
8031
8041
8042
8051
8052
8053
8061
8a21
8a31
8a32
8a33
8d21
8d31
8d32
8d33
8d41
8d42
8d43
8d44
8d45
8d46
8d47
8d48
8d51
8d52
8d53
8d54
8d55
8d56
8h21
8k31
8k33
C
3
0
1
2
2
2
3
10
4
4
2
3
2
3
4
4
5
5
5
6
2
3
3
3
2
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
5
2
3
3
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
4
1
2
4
4
4
6
16
6
6
1
3
3
5
7
7
9
9
9
11
1
3
3
3
1
2
3
3
2
4
3
3
5
3
3
5
3
3
5
5
7
7
3
3
3
N
0
1
0
0
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
3
2
3
4
3
3
3
3
2
2
5
5
2
2
2
2
2
2
2
2
4
5
4
6
3
6
4
3
7
7
5
5
5
4
4
3
6
6
6
6
3
3
4
4
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
[CH3COCHOO]*
[HNOO]*
[CH(OH)OO]*
[CH2(OH)C(OH)OO]*
[CH2(OH)CHOO]*
[CH3C(OH)OO]*
[CH3CH2C(OH)OO]*
CH3CO’CH’CH2’CHCH2CHOO’CCH3CH3]*
[CH2=CHC(CH3)OO]*
[CH2=C(CH3)CHOO]*
[(NO2)COCHOO]*
[CH3COC(NO2)OO]*
CH3CO(O.)
CH3CH2CO(O.)
CH3CH2CH2CO(O.)
CH3CH(CH3)CO(O.)
CH3CH2CH2CH2CO(O.)
CH3CH2CH(CH3)CO(O.)
CH3CH(CH3)CH2CO(O.)
CH3CH(CH3)CH(CH3)CO(O.)
CO(OH)CO(O.)
CO(OH)CH(OH)CO(O.)
CO(OH)CH2CO(O.)
CO(OH)C(OH)(OH)CO(O.)
CHOCO(O.)
CHOC(NO2)(OH)CO(O.)
CHOCH(OH)CO(O.)
CHOCH2CO(O.)
CHOCOC(NO2)(OH)CO(O.)
CHOCH(OH)C(NO2)(OH)CO(O.)
CHOCH(OH)COCO(O.)
CHOCOCH(OH)CO(O.)
CHOCH(OH)CH(OH)CO(O.)
CHOCOCH2CO(O.)
CHOCH2COCO(O.)
CHOCH(CH3)CO(O.)
CHOCOCH(OH)COCO(O.)
CHOCOCOCH(OH)CO(O.)
CHOCOCH(OH)CH(OH)CO(O.)
CHOCH(OH)CH(OH)COCO(O.)
CHOCH(CH3)CH2CO(O.)
CHOCH2CH(CH3)CO(O.)
CH2(OOH)CO(O.)
CH2(OH)COCO(O.)
CH3COCO(O.)
Functional Groups
| 7.k
| 7.m
| 7.o
| 7.oo
| 7.o
| 7.o
| 7.o
| 7.tk
| 7.u
| 7.u
| 7.kv
| 7.kv
| 8.
| 8.
| 8.
| 8.
| 8.
| 8.
| 8.
| 8.
| 8.a
| 8.ao
| 8.a
| 8.aoo
| d8.
| do8.v
| do8.
| d8.
| dko8.v
| doo8.v
| dok8.
| 8.okd
| doo8.
| dk8.
| dk8.
| d8.
| dkok8.
| dkko8.
| dkoo8.
| dook8.
| d8.
| d8.
| h8.
| ok8.
| k8.
127
Table A.16 Chemical Codes:8k40–8o35.
Code
8k40
8k45
8k46
8k47
8k48
8k49
8k4A
8k50
8k51
8k52
8k53
8k55
8k57
8k58
8k59
8k5A
8k5B
8k5C
8k81
8l11
8n21
8n31
8n32
8n33
8n34
8n41
8n42
8n43
8n44
8n45
8n46
8n47
8n48
8n51
8n52
8n53
8n54
8n55
8o22
8o23
8o31
8o32
8o33
8o34
8o35
C
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
8
1
2
3
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
2
2
3
3
3
3
3
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
5
5
5
5
5
5
5
7
5
5
5
5
7
7
5
7
7
7
13
0
2
1
2
2
4
3
3
4
3
4
4
6
6
5
6
5
6
6
3
3
5
5
5
5
5
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
1
1
1
2
2
1
2
1
1
1
1
2
1
2
1
1
0
0
0
0
0
0
0
O
4
4
5
4
4
3
5
4
5
6
6
5
5
6
4
3
4
3
4
2
5
8
6
6
5
9
8
6
9
7
7
5
6
9
7
9
7
8
4
3
3
4
4
5
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3CH(OH)COCO(O.)
CH3COCH(OH)CO(O.)
CH2(OH)COCH(OH)CO(O.)
CH2(OH)COCH2CO(O.)
CH2(OH)CH2COCO(O.)
CH3COCH2CO(O.)
CH2(OH)CH(OH)COCO(O.)
CH3COCH(OH)CH2CO(O.)
CH3COCOCH(OH)CO(O.)
CH2(OH)COCOCH(OH)CO(O.)
CH2(OH)COCH(OH)COCO(O.)
CH3COCH(OH)COCO(O.)
CH3COCH(OH)CH(OH)CO(O.)
CH2(OH)COCH(OH)CH(OH)CO(O.)
CH3COCOCH2CO(O.)
CH3COCH2CH2CO(O.)
CH3CH(OH)COCH2CO(O.)
CH3COCH(CH3)CO(O.)
CH3C(OH)(CH3)CH(COCH3)CH2CO(O.)
CO(O.)(Cl)
CH2(ONO2)CO(O.)
CO(NO2)CH(ONO2)CO(O.)
CH2(ONO2)COCO(O.)
CHOCH(ONO2)CO(O.)
CH3CH(ONO2)CO(O.)
CO(NO2)CH(ONO2)CH(OH)CO(O.)
CH3COC(NO2)(ONO2)CO(O.)
CH3COCH(ONO2)CO(O.)
CO(NO2)CH(OH)CH(ONO2)CO(O.)
CH2(ONO2)COCH(OH)CO(O.)
CHOCH(ONO2)CH(OH)CO(O.)
CH3CH(ONO2)CH2CO(O.)
CH2(OH)CH(ONO2)CH2CO(O.)
CH3COC(NO2)(ONO2)CH(OH)CO(O.)
CH3COCH(ONO2)CH(OH)CO(O.)
CH3COC(NO2)(OH)CH(ONO2)CO(O.)
CH3COCH(OH)CH(ONO2)CO(O.)
CH2(ONO2)COCH(OH)CH(OH)CO(O.)
CH(OH)(OH)CO(O.)
CH2(OH)CO(O.)
CH3CH(OH)CO(O.)
CH2(OH)CH(OH)CO(O.)
CH3C(OH)(OH)CO(O.)
CH2(OH)C(OH)(OH)CO(O.)
CH2(OH)CH2CO(O.)
Functional Groups
| ok8.
| ko8.
| ok8.
| ok8.
| ok8.
| k8.
| ook8.
| ko8.
| kko8.
| okko8.
| okok8.
| kok8.
| koo8.
| okoo8.
| kk 8.
| k8.
| ok8.
| k8.
| ok8.
| 8.l
| n8.
| kn8.v
| nk8.
| dn8.
| n8.
| kno8.v
| kn8.v
| kn8.
| kon8.v
| nko8.
| dno8.
| 8.n
| o8.n
| kno8.v
| kno8.
| kon8.v
| kon8.
| nkoo8.
| oo8.
| o8.
| o8.
| oo8.
| oo8.
| ooo8.
| o8.
128
Table A.17 Chemical Codes: 8o41–BRO.
Code
8o41
8o42
8o43
8o44
8o45
8o46
8o47
8o51
8o52
8o53
8o54
8o55
8o56
8o61
8r71
8t91
8tA1
8u31
8u32
8u41
8u42
8u43
8u44
8u51
8u52
8u53
8v21
8v22
8v32
8v41
8v42
8v43
8v44
8v54
8v56
?
BR
BR2
BRCL
BRO
C
4
4
4
4
4
4
4
5
5
5
5
5
5
6
7
9
10
3
3
4
4
4
4
5
5
5
2
2
3
4
4
4
4
5
5
0
0
0
0
0
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
2
1
H
7
7
7
7
7
7
7
9
9
9
9
9
9
11
5
13
15
2
3
2
3
5
2
4
5
5
0
2
2
2
2
4
4
4
6
0
0
0
0
0
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
1
0
0
1
1
0
0
1
1
1
1
1
1
1
1
1
0
0
0
0
0
O
3
3
3
4
3
4
3
3
3
3
3
4
3
3
2
3
3
6
4
5
3
2
5
5
3
3
5
6
6
7
7
6
7
7
7
0
0
0
0
1
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3C(OH)(CH3)CO(O.)
CH2(OH)CH2CH2CO(O.)
CH3CH(OH)CH2CO(O.)
CH2(OH)CH(OH)CH2CO(O.)
CH3CH2CH(OH)CO(O.)
CH2(OH)CH2CH(OH)CO(O.)
CH2(OH)CH(CH3)CO(O.)
CH3CH(OH)CH2CH2CO(O.)
CH3CH2CH(OH)CH2CO(O.)
CH2(OH)CH(CH3)CH2CO(O.)
CH2(OH)CH2CH(CH3)CO(O.)
CH3CH(OH)CH(OH)CH2CO(O.)
CH3CH(OH)CH(CH3)CO(O.)
CH2(OH)CH(CH3)CH(CH3)CO(O.)
C6H5CO(O.)
apR2C8H13OCO(O.)
apR1C9H15OCO(O.)
Cd(NO2)(OH)=Cd(OH)CO(O.)
CdH(OH)=Cd(OH)CO(O.)
CO(NO2)CdH=CdHCO(O.)
CHOCdH=CdHCO(O.)
CdH2=Cd(CH3)CO(O.)
CHOCdH=Cd(NO2)CO(O.)
CH3COCd(NO2)=CdHCO(O.)
CH3COCdH=CdHCO(O.)
CHOCdH=Cd(CH3)CO(O.)
CO(NO2)CO(O.)
C(OH)(OH)(NO2)CO(O.)
CO(NO2)CH(OH)CO(O.)
CO(NO2)COCH(OH)CO(O.)
CO(NO2)CH(OH)COCO(O.)
CH3COC(NO2)(OH)CO(O.)
CO(NO2)CH(OH)CH(OH)CO(O.)
CH3COC(NO2)(OH)COCO(O.)
CH3COC(NO2)(OH)CH(OH)CO(O.)
products
Br
Br2
BrCl
BrO
Functional Groups
| o8.
| o8.
| o8.
| oo8.
| o8.
| oo8.
| o8.
| o8.
| o8.
| o8.
| o8.
| oo8.
| o8.
| o8.
| r8.
| k 8.t
| k 8.t
| ouo8.v
| ouo8.
| ku8.v
| du8.
| 8.u
| duv8.
| ku8.v
| ku 8.
| du 8.
| kv8.
| oo8.v
| ko8.v
| kko8.v
| kok8.v
| ko8.v
| koo8.v
| kok8.v
| koo8.v
|
|b
| bb
| bl
|b
129
Table A.18 Chemical Codes: C–F142.
Code
C
C2H2
C2H4
C2H5
C2H6
C3H6
C3H8
C6H6
CCL3
CCL4
CF2O
CF3
CF3O
CF4
CH2O
CH3
CH3O
CH3S
CH4
CHF2
CL
CL2
CL2O
CLNO
CLO
CLO3
CLOO
CO
CO2
CS
CS2
F
F11
F12
F123
F124
F132
F141
F142
C
1
2
2
2
2
3
3
6
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
1
1
1
1
0
1
1
2
2
2
2
2
X
0
0
0
0
0
0
0
0
3
4
2
3
3
4
0
0
0
0
0
2
1
2
2
1
1
1
1
0
0
0
0
1
4
4
5
5
4
3
3
H
0
2
4
5
6
6
8
6
0
0
0
0
0
0
2
3
3
3
4
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
2
3
3
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
0
0
0
0
0
0
0
0
0
0
1
0
1
0
1
0
1
0
0
0
0
0
1
1
1
3
2
1
2
0
0
0
0
0
0
0
0
0
0
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
1
2
0
0
0
0
0
0
0
0
Full Chemical Formula
C
CdH=-CdH
CdH2=CdH2
CH3CH2.
CH3CH3
CH3CdH=CdH2
CH3CH2CH3
C6H6
C.(Cl3)
C(Cl4)
CO(F2)
C(F3)
C(F3)(O.)
C(F4)
CH2O
CH3
CH3(O.)
CH3S
CH4
CH.(F2)
Cl
Cl2
Cl2O
ClNO
ClO
ClO3
ClOO
CO
CO2
CS
CS2
F
C(F)(Cl3)
C(F2)(Cl2)
CH(Cl2)C(F3)
C(F3)CH(Cl)(F)
CH2(Cl)C(Cl)(F2)
CH3C(Cl2)(F)
CH3C(F2)(Cl)
Functional Groups
|
|u
| uc
| 0.
|c
|u
|c
|r
| 0.l
|l
| fd
| 0.f
| 1.f
|f
|d
| 0.
| 1.
|s
|c
| 0.f
|l
|l
|l
|l
|l
|l
|l
|
|
|s
|s
|f
| fl
| fl
| fl
| fl
| fl
| fl
| fl
130
Table A.19 Chemical Codes: F21–MECN.
Code
F21
F22
F31
FNO
FO
FO2
FONO
H
H2
H2O
H2O2
H2S
HBR
HCL
HCN
HCO
HF
HNO
HNO2
HNO3
HNO4
HNOO
HO
HO2
HOBR
HOCL
HS
HSNO
HSO
HSO2
HSO3
HV
M
MECN
C
1
1
1
0
0
0
0
0
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
X
3
3
2
1
1
1
1
0
0
0
0
0
1
1
0
0
1
0
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
H
1
1
2
0
0
0
0
1
2
2
2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0
0
3
N
0
0
0
1
0
0
1
0
0
0
0
0
0
0
1
0
0
1
1
1
1
1
0
0
0
0
0
1
0
0
0
0
0
1
O
0
0
0
1
1
2
2
0
0
1
2
0
0
0
0
1
0
1
2
3
4
2
1
2
1
1
0
1
1
2
3
0
0
0
S
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
0
0
0
Full Chemical Formula
CH(F)(Cl2)
CH(F2)(Cl)
CH2(Cl)(F)
FNO
FO
FO2
FONO
H
H2
H2O
H2O2
H2S
HBR
HCl
HCN
HCO
HF
HNO
HNO2
HNO3
HNO4
HNOO
HO
HO2
HOBr
HOCl
HS
HSNO
HSO
HSO2
HSO3
hv
M
CH3CN
Functional Groups
| fl
| fl
| fl
|f
|f
|f
|f
|
|
|
|
|s
|b
|l
|q
| 0.d
|f
|
|
|
|
| 4..m
|
|
|b
|l
|s
|s
|s
|s
|s
|
|
|q
131
Table A.20 Chemical Codes: N–aa33.
Code
N
N2
N2O
N2O4
N2O5
NA
NACL
NAO
NAO2
NAO3
NAOH
NH2
NH2O
NH3
NO
NO2
NO3
O1D
O2
O3
O3P
OCLO
OCS
S
SCL
SO
SO2
SO3
XAOO
XPOO
XSOO
XTOO
a011
a021
a031
a041
a042
a051
a052
a053
a061
aa21
aa31
aa32
aa33
C
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
1
2
3
4
4
5
5
5
6
2
3
3
3
X
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
0
0
0
0
0
0
0
0
0
0
1
2
2
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
4
6
8
8
10
10
10
12
2
4
4
4
N
1
2
2
2
2
0
0
0
0
0
0
1
1
1
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
0
0
1
4
5
0
0
1
2
3
1
0
1
0
1
2
3
1
2
3
1
2
1
0
0
1
2
3
0
0
0
0
2
2
2
2
2
2
2
2
2
4
5
4
6
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
N
N2
N2O
N2O4
N2O5
Na
NaCl
NaO
NaO2
NaO3
NaOH
NH2
NH2O
NH3
NO
NO2
NO3
O*
O2
O3
O
OClO
OCS
S
SCl
SO
SO2
SO3
a-counter
p-counter
s-counter
t-counter
CHO(OH)
CH3CO(OH)
CH3CH2CO(OH)
CH3CH2CH2CO(OH)
CH3CH(CH3)CO(OH)
CH3CH2CH2CH2CO(OH)
CH3CH2CH(CH3)CO(OH)
CH3CH(CH3)CH2CO(OH)
CH3CH(CH3)CH(CH3)CO(OH)
CO(OH)CO(OH)
CO(OH)CH(OH)CO(OH)
CO(OH)CH2CO(OH)
CO(OH)C(OH)(OH)CO(OH)
Functional Groups
|
|
|
|
|
|q
|q
|q
|q
|q
|q
|m
|m
|m
|
|
|
|
|
|
|
|l
|s
|s
| sl
|s
|s
|s
|
|
|
|
|a
|a
|a
|a
|a
|a
|a
|a
|a
| aa
| aoa
| aa
| aooa
132
Table A.21 Chemical Codes: ad21–ak33.
Code
ad21
ad31
ad32
ad33
ad34
ad35
ad41
ad42
ad43
ad44
ad45
ad46
ad47
ad48
ad49
ad51
ad52
ad53
ad54
ad55
ad56
ag21
ag31
ag32
ag33
ag40
ah21
ah31
ah32
ah41
ah42
ah43
ah44
ah50
ah51
ah52
ak31
ak33
C
2
3
3
3
3
3
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
2
3
3
3
4
2
3
3
4
4
4
4
5
5
5
3
3
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
2
3
4
4
2
4
3
5
4
4
6
4
4
6
6
4
4
6
6
8
8
2
4
4
4
6
4
6
4
8
8
6
8
8
8
8
4
4
N
0
1
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
3
6
4
3
4
5
7
7
5
5
5
4
4
3
4
6
6
6
6
3
3
5
6
5
7
7
4
4
5
4
5
5
5
6
6
7
4
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CO(OH)CHO
CO(OH)C(OH)(NO2)CHO
CO(OH)CH(OH)CHO
CO(OH)CH2CHO
CO(OH)COCHO
CO(OH)C(OH)(OH)CHO
CO(OH)C(NO2)(OH)COCHO
CO(OH)C(NO2)(OH)CH(OH)CHO
CO(OH)COCH(OH)CHO
CO(OH)CH(OH)COCHO
CO(OH)CH(OH)CH(OH)CHO
CO(OH)CH2COCHO
CO(OH)COCH2CHO
CO(OH)CH(CH3)CHO
CO(OH)CH(OH)CH2CHO
CO(OH)COCH(OH)COCHO
CO(OH)CH(OH)COCOCHO
CO(OH)CH(OH)CH(OH)COCHO
CO(OH)COCH(OH)CH(OH)CHO
CO(OH)CH2CH(CH3)CHO
CO(OH)CH(CH3)CH2CHO
CO(OH)CO(OOH)
CO(OH)CH(OH)CO(OOH)
CO(OH)CH2CO(OOH)
CO(OH)C(OH)(OH)CO(OOH)
CO(OH)C(OOH)(CH3)CO(OOH)
CO(OH)CH2(OOH)
CH3CH(OOH)CO(OH)
CO(OH)COCH2(OOH)
CH3CH2CH(OOH)CO(OH)
CH2(OH)C(OOH)(CH3)CO(OH)
CH3CH(OOH)COCO(OH)
CH2(OOH)CH2CH(OH)CO(OH)
CH3COCH(OH)CH(OOH)CO(OH)
CO(OH)CH(OH)CH(OOH)COCH3
CO(OH)CH(OH)CH(OH)COCH2(OOH)
CH2(OH)COCO(OH)
CH3COCO(OH)
Functional Groups
| da
| dova
| doa
| da
| dka
| dooa
| dkoav
| dooav
| doka
| dkoa
| dooa
| dka
| dka
| da
| doa
| dkoka
| dkkoa
| dkooa
| dooka
| da
| da
| ga
| aog
| ag
| aoog
| ahg
| ha
| ha
| hka
| ha
| oha
| hka
| hoa
| koho
| aohk
| aookh
| oka
| ka
133
Table A.22 Chemical Codes: ak40–an55.
Code
ak40
ak45
ak46
ak47
ak48
ak49
ak4A
ak4C
ak4D
ak50
ak51
ak52
ak53
ak55
ak57
ak58
ak59
ak5A
ak5B
ak5C
ak81
an21
an31
an32
an33
an34
an35
an40
an41
an42
an43
an44
an45
an46
an47
an48
an49
an4A
an4B
an51
an52
an53
an54
an55
C
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
8
2
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
6
6
6
6
6
6
6
6
4
8
6
6
6
6
8
8
6
8
8
8
14
3
2
3
3
3
5
7
4
4
5
4
5
5
7
7
7
5
7
6
7
6
7
7
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
1
1
1
1
1
2
2
1
2
1
1
1
1
1
1
1
2
1
2
1
1
O
4
4
5
4
4
3
5
3
4
4
5
6
6
5
5
6
4
3
4
3
4
5
8
6
6
6
5
5
9
8
6
9
7
7
5
6
6
6
6
9
7
9
7
8
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3CH(OH)COCO(OH)
CO(OH)CH(OH)COCH3
CO(OH)CH(OH)COCH2(OH)
CO(OH)CH2COCH2(OH)
CH2(OH)CH2COCO(OH)
CO(OH)CH2COCH3
CH2(OH)CH(OH)COCO(OH)
CH3CH2COCO(OH)
CH3COCOCO(OH)
CO(OH)CH2CH(OH)COCH3
CO(OH)CH(OH)COCOCH3
CO(OH)CH(OH)COCOCH2(OH)
CH2(OH)COCH(OH)COCO(OH)
CH3COCH(OH)COCO(OH)
CO(OH)CH(OH)CH(OH)COCH3
CO(OH)CH(OH)CH(OH)COCH2(OH)
CO(OH)CH2COCOCH3
CO(OH)CH2CH2COCH3
CH3CH(OH)COCH2CO(OH)
CO(OH)CH(CH3)COCH3
CH3C(OH)(CH3)CH(CH2CO(OH))COCH3
CO(OH)CH2(ONO2)
CO(OH)CH(ONO2)CO(NO2)
CO(OH)COCH2(ONO2)
CO(OH)CH(ONO2)CHO
CO(OH)COCH2(ONO2)
CH3CH(ONO2)CO(OH)
CH3CH2CH(ONO2)CO(OH)
CO(OH)CH(OH)CH(ONO2)CO(NO2)
CH3COC(ONO2)(NO2)CO(OH)
CH3COCH(ONO2)CO(OH)
CO(NO2)CH(OH)CH(ONO2)CO(OH)
CO(OH)CH(OH)COCH2(ONO2)
CO(OH)CH(OH)CH(ONO2)CHO
CO(OH)CH2CH(ONO2)CH3
CO(OH)CH2CH(ONO2)CH2(OH)
CH2(OH)C(ONO2)(CH3)CO(OH)
CO(OH)COCH(ONO2)CH3
CH2(ONO2)CH2CH(OH)CO(OH)
CO(OH)CH(OH)C(NO2)(ONO2)COCH3
CO(OH)CH(OH)CH(ONO2)COCH3
CH3COC(OH)(NO2)CH(ONO2)CO(OH)
CH3COCH(OH)CH(ONO2)CO(OH)
CO(OH)CH(OH)CH(OH)COCH2(ONO2)
Functional Groups
| oka
| koa
| oka
| oka
| oka
| ka
| ooka
| ka
| kk a
| koa
| kkoa
| okkoa
| okoka
| koka
| kooa
| okooa
| kk a
| ka
| oka
| ka
| oak
| na
| vkna
| nka
| dna
| nka
| na
| na
| vknoa
| knva
| kna
| vkona
| nkoa
| dnoa
| na
| ona
| ona
| nka
| noa
| kvnoa
| knoa
| kovna
| kona
| nkooa
134
Table A.23 Chemical Codes: ao22–av56.
Code
ao22
ao23
ao31
ao32
ao33
ao34
ao35
ao41
ao42
ao43
ao44
ao45
ao46
ao47
ao48
ao50
ao51
ao52
ao53
ao54
ao55
ao56
ao61
ar71
at91
atA1
au31
au32
au41
au42
au43
au44
au51
au52
au53
av11
av21
av22
av32
av41
av42
av43
av44
av54
av56
C
2
2
3
3
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
6
7
9
10
3
3
4
4
4
4
5
5
5
1
2
2
3
4
4
4
4
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
4
4
6
6
6
6
6
8
8
8
8
8
8
8
8
10
10
10
10
10
10
10
12
6
14
16
3
4
3
4
6
3
5
6
6
1
3
1
3
3
3
5
5
5
7
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
1
0
0
1
1
0
0
1
1
1
1
1
1
1
1
1
1
O
4
3
3
4
4
5
3
3
3
3
4
3
4
3
4
5
3
3
3
3
4
3
3
2
3
3
6
4
5
3
2
5
5
3
3
4
6
5
6
7
7
6
7
7
7
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH(OH)(OH)CO(OH)
CH2(OH)CO(OH)
CH3CH(OH)CO(OH)
CH2(OH)CH(OH)CO(OH)
CH3C(OH)(OH)CO(OH)
CH2(OH)C(OH)(OH)CO(OH)
CH2(OH)CH2CO(OH)
CH3C(OH)(CH3)CO(OH)
CH2(OH)CH2CH2CO(OH)
CH3CH(OH)CH2CO(OH)
CH2(OH)CH(OH)CH2CO(OH)
CH3CH2CH(OH)CO(OH)
CH2(OH)CH2CH(OH)CO(OH)
CH2(OH)CH(CH3)CO(OH)
CH2(OH)C(OH)(CH3)CO(OH)
CH2(OH)C(OH)(CH3)CH(OH)CO(OH)
CH3CH(OH)CH2CH2CO(OH)
CH3CH2CH(OH)CH2CO(OH)
CH2(OH)CH(CH3)CH2CO(OH)
CH2(OH)CH2CH(CH3)CO(OH)
CH3CH(OH)CH(OH)CH2CO(OH)
CH3CH(OH)CH(CH3)CO(OH)
CH2(OH)CH(CH3)CH(CH3)CO(OH)
C6H5CO(OH)
apR2C8H13OCO(OH)
apR1C9H15OCO(OH)
Cd(OH)(NO2)=Cd(OH)CO(OH)
CdH(OH)=Cd(OH)CO(OH)
CO(OH)CdH=CdHCO(NO2)
CO(OH)CdH=CdHCHO
CdH2=Cd(CH3)CO(OH)
CO(OH)Cd(NO2)=CdHCHO
CO(OH)CdH=Cd(NO2)COCH3
CO(OH)CdH=CdHCOCH3
CO(OH)Cd(CH3)=CdHCHO
CO(NO2)(OH)
C(OH)(OH)(NO2)CO(OH)
CO(OH)CO(NO2)
CO(OH)CH(OH)CO(NO2)
CO(NO2)COCH(OH)CO(OH)
CO(OH)COCH(OH)CO(NO2)
CO(OH)C(OH)(NO2)COCH3
CO(OH)CH(OH)CH(OH)CO(NO2)
CO(OH)COC(OH)(NO2)COCH3
CO(OH)CH(OH)C(NO2)(OH)COCH3
Functional Groups
| ooa
| oa
| oa
| ooa
| ooa
| oooa
| oa
| oa
| oa
| oa
| ooa
| oa
| ooa
| oa
| ooa
| oooa
| oa
| oa
| oa
| oa
| ooa
| oa
| oa
| ra
| k at
| k at
| ouoav
| ouoa
| vkua
| dua
| ua
| duva
| kvua
| kua
| dua
| av
| ooav
| kva
| vkoa
| vkkoa
| vkoka
| kova
| kooav
| kovka
| kooav
135
Table A.24 Chemical Codes: b011–dk36.
Code
b011
bn01
c041
c042
c051
c052
c053
c061
c062
c071
c081
d021
d031
d041
d042
d051
d052
d053
d061
dd21
dd31
dd32
dd33
dd34
dd41
dd42
dd43
dd44
dd45
dd51
dd52
dd53
dd54
dd55
dd56
dd57
dd61
ddA2
dk33
dk35
dk36
C
1
0
4
4
5
5
5
6
6
7
8
2
3
4
4
5
5
5
6
2
3
3
3
3
4
4
4
4
4
5
5
5
5
5
5
5
6
10
3
3
3
X
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
3
0
10
10
12
12
12
14
14
16
18
4
6
8
8
10
10
10
12
2
4
2
4
4
2
6
4
4
6
2
4
4
6
8
8
8
12
14
4
4
4
N
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
0
3
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
2
3
3
2
4
4
4
4
3
2
5
5
5
5
2
4
3
2
3
2
3
4
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3(Br)
BrONO2
CH3CH2CH2CH3
CH3CH(CH3)CH3
C5H12
CH3CH2CH2CH2CH3
CH3CH(CH3)CH2CH3
C6H14
CH3CH(CH3)CH(CH3)CH3
C7H16
C8H18
CH3CHO
CH3CH2CHO
CH3CH2CH2CHO
CH3CH(CH3)CHO
CH3CH2CH2CH2CHO
CH3CH(CH3)CH2CHO
CH3CH2CH(CH3)CHO
CH3CH(CH3)CH(CH3)CHO
CHOCHO
CHOCH(OH)CHO
CHOCOCHO
CHOCH2CHO
CHOC(OH)(OH)CHO
CHOCOCOCHO
CHOCH(OH)CH(OH)CHO
CHOCH(OH)COCHO
CHOCH2COCHO
CHOCH(CH3)CHO
CHOCOCOCOCHO
CHOCOCH(OH)COCHO
CHOCH(OH)COCOCHO
CHOCH(OH)CH(OH)COCHO
CHOCH(CH3)CH2CHO
CHOCH(OH)C(OH)(CH3)CHO
CHOC(OH)(CH3)CH2CHO
C5H11(OH)CO
CHOCO’CH’CH2’CHCH2CHO’CCH3CH3
CH3COCHO
CH2(OH)COCHO
CH(OH)(OH)COCHO
Functional Groups
|b
| bn
|c
|c
| cz
|c
|c
| cz
|c
| cz
| cz
|d
|d
|d
|d
|d
|d
|d
|d
| dd
| ddo
| ddk
| dd
| dood
| dkkd
| dood
| dokd
| dkd
| dd
| dkkkd
| dkokd
| dkkod
| dkood
| dd
| dood
| dod
| okddz
| dktd
| dk
| odk
| dkoo
136
Table A.25 Chemical Codes: dk40–do49.
Code
dk40
dk43
dk47
dk48
dk49
dk4A
dk4B
dk4C
dk4D
dk4E
dk51
dk52
dk53
dk54
dk57
dk58
dk59
dk5A
dk5B
dk5C
dk5D
dk5E
dk5F
dk5G
dk81
dk82
do22
do23
do31
do32
do33
do34
do35
do40
do41
do42
do43
do44
do45
do46
do48
do49
C
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
8
8
2
2
3
3
3
3
3
4
4
4
4
4
4
4
4
4
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
4
4
6
6
6
6
6
6
6
6
4
4
6
6
6
8
8
6
6
8
8
8
8
8
16
14
4
4
6
6
6
6
6
8
8
8
8
8
8
8
8
8
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
3
4
4
3
2
3
3
2
3
4
4
5
4
5
5
5
4
3
4
2
3
2
3
2
2
3
3
2
3
3
4
2
2
3
2
2
2
2
3
2
3
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3COCOCHO
CH2(OH)COCOCHO
CH2(OH)COCH(OH)CHO
CH3COCH(OH)CHO
CH3CH2COCHO
CH2(OH)COCH2CHO
CH2(OH)CH2COCHO
CH3COCH2CHO
CH3CH(OH)COCHO
CH2(OH)CH(OH)COCHO
CH3COCOCOCHO
CH2(OH)COCOCOCHO
CH3COCOCH(OH)CHO
CH2(OH)COCOCH(OH)CHO
CH2(OH)COCH(OH)COCHO
CH2(OH)COCH(OH)CH(OH)CHO
CH3COCH(OH)CH(OH)CHO
CH3COCOCH2CHO
CH3COCH(OH)COCHO
CH3CH2COCH2CHO
CH3COCH(OH)CH2CHO
CH3COCH2CH2CHO
CH3CH(OH)COCH2CHO
CH3COCH(CH3)CHO
C7H15(OH)CO
CH3COCH(C(OH)(CH3)CH3)CH2CHO
CH(OH)(OH)CHO
CH2(OH)CHO
CH2(OH)CH(OH)CHO
CH3C(OH)(OH)CHO
CH2(OH)C(OH)(OH)CHO
CH3CH(OH)CHO
CH2(OH)CH2CHO
CH3CH(OH)CH(OH)CHO
CH2(OH)CH2CH2CHO
CH3C(OH)(CH3)CHO
CH2(OH)CH(CH3)CHO
CH3CH(OH)CH2CHO
CH2(OH)CH(OH)CH2CHO
CH3CH2CH(OH)CHO
CH2(OH)CH2CH(OH)CHO
CH2(OH)C(OH)(CH3)CHO
Functional Groups
| kk d
| okkd
| okod
| kod
| dk
| okd
| okd
| kd
| okd
| dkoo
| kkkd
| okkkd
| kkod
| okkod
| okokd
| okood
| kood
| kk d
| kokd
| kd
| kod
| dk
| okd
| dk
| odkk
| kdo
| ood
| od
| ood
| ood
| oood
| od
| od
| doo
| od
| od
| od
| od
| ood
| od
| ood
| doo
137
Table A.26 Chemical Codes: do50–en72.
Code
do50
do51
do52
do53
do54
do55
do56
do57
do59
do5A
do61
do62
do63
do64
do65
do66
dr71
dt81
dt82
dt91
dt92
dtA1
dtA3
dv11
dv21
dv22
dv31
dv32
dv41
dv42
dv44
dv45
dv46
dv55
dv56
ea41
ed31
ed41
ed51
edB1
edC1
eh72
ek71
en72
C
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
7
8
8
9
9
10
10
1
2
2
3
3
4
4
4
4
4
5
5
4
3
4
5
11
12
7
7
7
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
10
10
10
10
10
10
10
10
10
10
12
12
12
12
12
12
6
12
14
14
14
16
16
1
3
1
1
3
1
3
3
5
5
5
7
6
4
6
8
18
20
12
12
11
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
0
0
0
0
0
0
0
0
1
O
4
3
2
2
2
2
3
2
2
4
3
2
4
3
2
3
1
2
2
2
3
2
3
3
5
4
5
5
6
6
6
6
5
6
6
5
3
4
4
4
4
5
4
6
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH2(OH)C(OH)(CH3)CH(OH)CHO
CH2(OH)CH(OH)CH(CH3)CHO
CH3CH(OH)CH2CH2CHO
CH3CH2CH(OH)CH2CHO
CH2(OH)CH(CH3)CH2CHO
CH2(OH)CH2CH(CH3)CHO
CH3CH(OH)CH(OH)CH2CHO
CH3CH(OH)CH(CH3)CHO
CH3C(OH)(CH3)CH2CHO
CH2(OH)CH(OH)C(OH)(CH3)CHO
CH2(OH)CH(CH2(OH))CH(CH3)CHO
CH2(OH)CH(CH3)CH(CH3)CHO
CH2(OH)CH(CH2(OH))CH(CH2(OH))CHO
CH2(OH)CH(CH3)CH(CH2(OH))CHO
CH3C(OH)(CH3)CH(CH3)CHO
CH2(OH)C(OH)(CH3)CH(CH3)CHO
C6H5CHO
’CO’CH2’CH(CH2CHO)’C(CH3)CH3
HO’CH’CH2’CHCH2CHO’CCH3CH3
CH3CO’CH’CH2’CH(CHO)’C(CH3)CH3
CH3CO’CH’CH2’CH(CH2(OH))’CCH3CHO
CH3CO’CH’CH2’CH(CH2CHO)’CCH3CH3
CH2(OH)CO’CH’CH2’CHCH2CHO’CCH3CH3
(NO2)CHO
C(NO2)(OH)(OH)CHO
CO(NO2)CHO
CO(NO2)COCHO
CO(NO2)CH(OH)CHO
CO(NO2)COCOCHO
CO(NO2)COCH(OH)CHO
CO(NO2)CH(OH)COCHO
CO(NO2)CH(OH)CH(OH)CHO
CH3COC(OH)(NO2)CHO
CH3COC(OH)(NO2)COCHO
CH3COC(OH)(NO2)CH(OH)CHO
CH3C(OH)(CO(OH))OCHO
CH3COOCHO
CH3C(OH)(CHO)OCHO
CH3C(OH)(CHO)OCOCH3
apX1C9CH16O(OH)OCHO
apX1C9CH16O(OH)OCOCH3
CH3COCOCH2OC(OOH)(CH3)CH3
CH3COCOCH2OC(CH3)(OH)CH3
CH3COCOCH2OC(CH3)(ONO2)CH3
Functional Groups
| oood
| doo
| do
| od
| od
| do
| doo
| do
| do
| oood
| doo
| od
| oood
| ood
| do
| doo
| rd
| kdt
| otd
| ktd
| ktod
| kdt
| oktd
| dv
| oodv
| kdv
| kkdv
| kodv
| kkkdv
| kkodv
| kokdv
| koodv
| dokv
| dkokv
| dookv
| oae
| ed
| edo
| oed
| eod t
| eod t
| kk eh
| kkeo
| kken
138
Table A.27 Chemical Codes: eo21–gd49.
Code
eo21
eo31
eo41
eo42
eo51
et71
etB2
etC2
eu51
eu52
eu61
eu62
f022
f024
fb11
fb12
fl11
fl12
fl14
fl15
fn01
fo11
g012
g021
g031
g041
g042
g051
g052
g053
g061
gd21
gd31
gd32
gd33
gd41
gd42
gd43
gd44
gd45
gd46
gd47
gd48
gd49
C
2
3
4
4
5
7
11
12
5
5
6
6
2
2
1
1
1
1
1
1
0
1
1
2
3
4
4
5
5
5
6
2
3
3
3
4
4
4
4
4
4
4
4
4
X
0
0
0
0
0
0
0
0
0
0
0
0
2
4
4
4
2
3
3
3
1
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
4
6
8
8
10
12
18
20
8
8
10
10
4
2
0
0
0
0
1
1
0
1
2
4
6
8
8
10
10
10
12
2
3
4
4
3
5
4
4
6
4
4
6
6
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
1
0
0
0
0
0
0
0
0
0
0
0
1
0
0
1
1
0
0
0
0
0
0
0
O
3
3
3
3
3
3
4
4
3
3
3
3
0
0
0
0
1
3
1
1
3
1
3
3
3
3
3
3
3
3
3
4
7
5
4
8
8
6
6
6
5
5
4
4
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CHOOCH2(OH)
CH3COOCH2(OH)
CH3COOCH(OH)CH3
CH3C(OH)(CH3)OCHO
CH3C(OH)(CH3)OCOCH3
CH3CO’C(OH)’CH2’O’C(CH3)CH3
apR1C9H15OCH(OH)OCHO
apR1C9H15OCH(OH)OCOCH3
CH3C(OH)(OCHO)CH=CH2
CH2=C(CH3)CH(OH)OCHO
CH3C(OH)(OCOCH3)CH=CH2
CH2=C(CH3)CH(OH)OCOCH3
CH3CH(F2)
C(F3)CH2(F)
C(Br)(Cl)(F2)
C(Br)(F3)
C(F)ClO
C(F)(Cl2)ONO2
C(F)(Cl2)(OH)
C(F2)(Cl)(OH)
FONO2
C(F3)(OH)
CHO(OOH)
CH3CO(OOH)
CH3CH2CO(OOH)
CH3CH(CH3)CO(OOH)
CH3CH2CH2CO(OOH)
CH3CH2CH2CH2CO(OOH)
CH3CH(CH3)CH2CO(OOH)
CH3CH2CH(CH3)CO(OOH)
CH3CH(CH3)CH(CH3)CO(OOH)
CO(OOH)CHO
CO(OOH)C(NO2)(OH)CHO
CO(OOH)CH(OH)CHO
CO(OOH)CH2CHO
CO(OOH)C(NO2)(OH)COCHO
CO(OOH)C(NO2)(OH)CH(OH)CHO
CO(OOH)COCH(OH)CHO
CO(OOH)CH(OH)COCHO
CO(OOH)CH(OH)CH(OH)CHO
CO(OOH)CH2COCHO
CO(OOH)COCH2CHO
CO(OOH)CH(CH3)CHO
CH3COCH2CO(OOH)
Functional Groups
| oe
| oe
| eo
| eo
| eo
| ktoe
| k eot
| k eot
| oeu
| uoe
| eou
| eou
|f
|f
| bfl
| bf
| fld
| fln
| flo
| flo
| fn
| fo
|g
|g
|g
|g
|g
|g
|g
|g
|g
| dg
| dogv
| dog
| dg
| dkogv
| doog
| dokg
| dkog
| doog
| dkg
| dkg
| dg
| dg
139
Table A.28 Chemical Codes: gd51–gn55.
Code
gd51
gd52
gd53
gd54
gd55
gd56
gg40
gh21
gh40
gh41
gk31
gk33
gk40
gk45
gk46
gk47
gk48
gk4A
gk50
gk51
gk52
gk54
gk55
gk57
gk58
gk5A
gk5B
gk5C
gk5D
gn21
gn31
gn32
gn34
gn40
gn41
gn42
gn43
gn45
gn47
gn48
gn49
gn51
gn52
gn53
gn54
gn55
C
5
5
5
5
5
5
4
2
4
4
3
3
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
2
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
4
4
6
6
8
8
6
4
8
6
4
4
6
6
6
6
6
6
8
6
6
6
6
8
8
8
8
8
6
3
2
3
5
7
4
4
5
5
7
7
4
6
7
6
7
7
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
2
1
1
1
2
2
1
1
1
1
2
2
1
2
1
1
O
7
7
7
7
4
4
8
5
6
6
5
4
5
5
6
5
5
6
5
6
7
6
7
6
7
4
5
4
5
6
9
7
6
7
10
9
7
8
6
7
10
10
8
10
8
9
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CO(OOH)COCH(OH)COCHO
CO(OOH)CH(OH)COCOCHO
CO(OOH)CH(OH)CH(OH)COCHO
CO(OOH)COCH(OH)CH(OH)CHO
CO(OOH)CH2CH(CH3)CHO
CO(OOH)CH(CH3)CH2CHO
CO(OOH)C(OOH)(CH3)CO(OOH)
CH2(OOH)CO(OOH)
CH2(OH)C(OOH)(CH3)CO(OOH)
CO(OOH)C(OOH)(CH3)CHO
CH2(OH)COCO(OOH)
CH3COCO(OOH)
CH3CH(OH)COCO(OOH)
CH3COCH(OH)CO(OOH)
CH2(OH)COCH(OH)CO(OOH)
CH2(OH)COCH2CO(OOH)
CH2(OH)CH2COCO(OOH)
CH2(OH)CH(OH)COCO(OOH)
CH3COCH(OH)CH2CO(OOH)
CH3COCOCH(OH)CO(OOH)
CH2(OH)COCOCH(OH)CO(OOH)
CH3COCH(OH)COCO(OOH)
CH2(OH)COCH(OH)COCO(OOH)
CH3COCH(OH)CH(OH)CO(OOH)
CH2(OH)COCH(OH)CH(OH)CO(OOH)
CH3COCH2CH2CO(OOH)
CH3CH(OH)COCH2CO(OOH)
CH3COCH(CH3)CO(OOH)
CH3COCOCH2CO(OOH)
CH2(ONO2)CO(OOH)
CO(NO2)CH(ONO2)CO(OOH)
CH2(ONO2)COCO(OOH)
CH3CH(ONO2)CO(OOH)
CH2(OH)C(ONO2)(CH3)CO(OOH)
CO(NO2)CH(ONO2)CH(OH)CO(OOH)
CH3COC(NO2)(ONO2)CO(OOH)
CH3COCH(ONO2)CO(OOH)
CH2(ONO2)COCH(OH)CO(OOH)
CH3CH(ONO2)CH2CO(OOH)
CH2(OH)CH(ONO2)CH2CO(OOH)
CO(NO2)CH(OH)CH(ONO2)CO(OOH)
CH3COC(NO2)(ONO2)CH(OH)CO(OOH)
CH3COCH(ONO2)CH(OH)CO(OOH)
CH3COC(NO2)(OH)CH(ONO2)CO(OOH)
CH3COCH(OH)CH(ONO2)CO(OOH)
CH2(ONO2)COCH(OH)CH(OH)CO(OOH)
Functional Groups
| dkokg
| dkkog
| dkoog
| dookg
| dg
| dg
| ghg
| gh
| ohg
| ghd
| okg
| kg
| okg
| kog
| okog
| okg
| okg
| ookg
| kog
| kkog
| okkog
| kokg
| okokg
| koog
| okoog
| kg
| okg
| kg
| kkg
| ng
| vkng
| nkg
| ng
| ong
| vknog
| kvng
| kng
| nkog
| ng
| ong
| vkong
| kvnog
| knog
| kvong
| kong
| nkoog
140
Table A.29 Chemical Codes: go22–gv62.
Code
go22
go23
go31
go32
go33
go34
go35
go40
go41
go42
go43
go44
go45
go46
go47
go50
go51
go52
go53
go54
go55
go56
go61
gr71
gt91
gtA1
gu31
gu32
gu41
gu42
gu43
gu44
gu51
gu52
gu53
gv11
gv21
gv22
gv32
gv41
gv42
gv43
gv44
gv53
gv56
C
2
2
3
3
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
6
7
9
10
3
3
4
4
4
4
5
5
5
1
2
2
3
4
4
4
4
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
4
4
6
6
6
6
6
8
8
8
8
8
8
8
8
10
10
10
10
10
10
10
12
6
14
16
3
4
3
4
6
3
5
6
6
1
3
1
3
3
3
5
5
5
7
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
1
0
0
1
1
0
0
1
1
1
1
1
1
1
1
1
1
O
5
4
4
5
4
5
6
5
4
4
5
4
4
5
4
6
4
4
4
4
5
4
4
3
4
4
7
5
6
4
3
6
6
4
4
5
7
6
7
8
8
7
8
8
8
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH(OH)(OH)CO(OOH)
CH2(OH)CO(OOH)
CH3CH(OH)CO(OOH)
CH2(OH)CH(OH)CO(OOH)
CH2(OH)CH2CO(OOH)
CH3C(OH)(OH)CO(OOH)
CH2(OH)C(OH)(OH)CO(OOH)
CH2(OH)C(OH)(CH3)CO(OOH)
CH3C(OH)(CH3)CO(OOH)
CH3CH(OH)CH2CO(OOH)
CH2(OH)CH(OH)CH2CO(OOH)
CH2(OH)CH2CH2CO(OOH)
CH3CH2CH(OH)CO(OOH)
CH2(OH)CH2CH(OH)CO(OOH)
CH2(OH)CH(CH3)CO(OOH)
CH2(OH)C(OH)(CH3)CH(OH)CO(OOH)
CH3CH(OH)CH2CH2CO(OOH)
CH3CH2CH(OH)CH2CO(OOH)
CH2(OH)CH(CH3)CH2CO(OOH)
CH2(OH)CH2CH(CH3)CO(OOH)
CH3CH(OH)CH(OH)CH2CO(OOH)
CH3CH(OH)CH(CH3)CO(OOH)
CH2(OH)CH(CH3)CH(CH3)CO(OOH)
C6H5CO(OOH)
apR2C8H13OCO(OOH)
apR1C9H15OCO(OOH)
Cd(NO2)(OH)=Cd(OH)CO(OOH)
CdH(OH)=Cd(OH)CO(OOH)
CO(NO2)CdH=CdHCO(OOH)
CO(OOH)CdH=CdHCHO
CdH2=Cd(CH3)CO(OOH)
CO(OOH)Cd(NO2)=CdHCHO
CH3COCd(NO2)=CdHCO(OOH)
CH3COCdH=CdHCO(OOH)
CO(OOH)Cd(CH3)=CdHCHO
CO(NO2)(OOH)
C(NO2)(OH)(OH)CO(OOH)
CO(NO2)CO(OOH)
CO(NO2)CH(OH)CO(OOH)
CO(NO2)COCH(OH)CO(OOH)
CO(NO2)CH(OH)COCO(OOH)
CH3COC(NO2)(OH)CO(OOH)
CO(NO2)CH(OH)CH(OH)CO(OOH)
CH3COC(NO2)(OH)COCO(OOH)
CH3COC(NO2)(OH)CH(OH)CO(OOH)
Functional Groups
| oog
| og
| og
| oog
| og
| oog
| ooog
| oog
| og
| og
| oog
| og
| og
| og
| og
| ooog
| go
| og
| og
| og
| og
| og
| og
| rg
| k gt
| k gt
| ouogv
| ouog
| kugv
| du g
| ug
| duvg
| kugv
| ku g
| du g
| gv
| oogv
| kgv
| kogv
| kkogv
| kokgv
| kogv
| koogv
| kokgv
| koogv
141
Table A.30 Chemical Codes: h011–hd62.
Code
h011
h021
h031
h032
h041
h042
h043
h044
h051
h052
h053
h054
h055
h056
h057
h061
h062
h063
h064
h071
hd21
hd31
hd32
hd33
hd34
hd41
hd42
hd43
hd44
hd45
hd46
hd47
hd49
hd50
hd51
hd52
hd53
hd54
hd55
hd56
hd57
hd58
hd5A
hd61
hd62
C
1
2
3
3
4
4
4
4
5
5
5
5
5
5
5
6
6
6
6
7
2
3
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
4
6
8
8
10
10
10
10
12
12
12
12
12
12
12
14
14
14
6
16
4
4
6
6
6
5
5
6
6
8
8
8
8
8
7
8
7
8
8
8
10
8
10
12
12
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
1
0
1
0
0
0
0
0
0
0
0
O
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
4
3
4
3
7
7
5
5
4
3
4
3
4
7
5
7
6
5
5
3
4
3
3
4
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3(OOH)
CH3CH2(OOH)
CH3CH(OOH)CH3
CH3CH2CH2(OOH)
CH3CH2CH(OOH)CH3
CH3CH2CH2CH2(OOH)
CH3C(OOH)(CH3)CH3
CH3CH(CH3)CH2(OOH)
C5H11(OOH)
CH3CH(CH3)CH(OOH)CH3
CH3CH2CH2CH2CH2(OOH)
CH3CH2CH2CH(OOH)CH3
CH3CH2CH(OOH)CH2CH3
CH3CH2CH(CH3)CH2(OOH)
CH3CH2C(OOH)(CH3)CH3
C6H13(OOH)
CH3CH(CH3)C(OOH)(CH3)CH3
CH3CH(CH3)CH(CH3)CH2(OOH)
C6H5(OOH)
C7H15(OOH)
CH2(OOH)CHO
CH2(OOH)COCHO
CH3CH(OOH)CHO
CH2(OH)CH(OOH)CHO
CH2(OOH)CH2CHO
CO(NO2)CH(OOH)CH(OH)CHO
CO(NO2)CH(OH)CH(OOH)CHO
CH2(OOH)COCH(OH)CHO
CHOCH(OH)CH(OOH)CHO
CH2(OH)C(OOH)(CH3)CHO
CH3CH(OOH)CH2CHO
CH2(OH)CH(OOH)CH2CHO
CH2(OOH)CH(CH3)CHO
CHOCH2C(OOH)(CH3)CHO
CH3COC(NO2)(OOH)CH(OH)CHO
CH3COCH(OOH)CH(OH)CHO
CH3COC(OH)(NO2)CH(OOH)CHO
CH2(OOH)COCH(OH)CH(OH)CHO
CH3COCH(OH)CH(OOH)CHO
CHOCH(OH)C(OOH)(CH3)CHO
CH3CH2CH(OOH)CH2CHO
CH3COCH(OOH)CH2CHO
CH3CH(OOH)CH(CH3)CHO
CH3C(OOH)(CH3)CH(CH3)CHO
CH2(OH)C(OOH)(CH3)CH(CH3)CHO
Functional Groups
|h
|h
|h
|h
|h
|h
|h
|h
| hz
|h
|h
|h
|h
|h
|h
| hz
|h
|h
| hr
| hz
| dh
| dkh
| hd
| ohd
| dh
| khodv
| kohdv
| hkod
| dohd
| ohd
| hd
| ohd
| dh
| dhd
| dohkv
| khod
| dhokv
| hkood
| kohd
| dohd
| hd
| khd
| dh
| hd
| hdo
142
Table A.31 Chemical Codes: hh51–hnA1.
Code
hh51
hh53
hh54
hh71
hk31
hk33
hk40
hk41
hk42
hk43
hk44
hk45
hk46
hk47
hk4B
hk4C
hk4D
hk51
hk52
hk71
hn11
hn21
hn23
hn31
hn32
hn33
hn34
hn41
hn42
hn43
hn44
hn45
hn46
hn47
hn48
hn51
hn52
hn53
hn54
hn55
hn56
hn57
hn58
hn59
hnA1
C
5
5
5
7
3
3
4
4
4
4
4
4
4
4
4
4
4
5
5
7
1
2
2
3
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
10
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
12
11
11
14
6
6
8
8
8
6
8
8
8
8
8
8
8
10
10
14
3
5
5
7
4
7
7
7
9
7
9
6
7
7
6
10
10
11
11
9
9
9
11
11
17
N
0
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
2
1
1
1
1
1
1
2
1
1
2
2
2
1
1
1
1
1
1
1
1
O
6
8
8
6
4
3
4
3
3
4
4
4
3
4
4
5
5
5
5
5
5
5
5
5
9
5
6
6
5
6
5
9
7
8
10
9
9
7
7
5
5
7
7
7
5
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH2(OH)C(OOH)(CH3)CH(OOH)CH2(OH)
CH2(OH)CH(OOH)C(OOH)(CH3)CH2(ONO2)
CH2(OH)C(OOH)(CH3)CH(OOH)CH2(ONO2)
CH3COC(OOH)(CH2(OOH))C(OH)(CH3)CH3
CH2(OH)COCH2(OOH)
CH3COCH2(OOH)
CH3COCH(OH)CH2(OOH)
CH3COCH(OOH)CH3
CH3CH2COCH2(OOH)
CH3COCOCH2(OOH)
CH3COCH(OOH)CH2(OH)
CH2(OH)COCH2CH2(OOH)
CH3COCH2CH2(OOH)
CH2(OH)CH2COCH2(OOH)
CH3CH(OH)COCH2(OOH)
CH2(OH)COCH(OH)CH2(OOH)
CH2(OH)CH(OH)COCH2(OOH)
CH2(OH)COC(OOH)(CH3)CH2(OH)
CH2(OH)C(OH)(CH3)COCH2(OOH)
CH3COC(OH)(CH2(OOH))C(OH)(CH3)CH3
CH2(ONO2)(OOH)
CH2(ONO2)CH2(OOH)
CH3CH(ONO2)(OOH)
CH3CH(OOH)CH2(ONO2)
CO(NO2)CH(OH)CH(ONO2)(OOH)
CH3CH(ONO2)CH2(OOH)
CH2(OH)CH(ONO2)CH2(OOH)
CH2(ONO2)C(OOH)(CH3)CHO
CH3C(OOH)(CH3)CH2(ONO2)
CH3COCH(OOH)CH2(ONO2)
CH3CH(ONO2)CH(OOH)CH3
CH3COC(NO2)(OH)CH(ONO2)(OOH)
CH3COCH(OH)CH(ONO2)(OOH)
CH(ONO2)(OH)CH(OH)COCH2(OOH)
CH(ONO2)(OH)C(OH)(NO2)COCH2(OOH)
CH2(OH)CH(ONO2)C(OOH)(CH3)CH2(ONO2)
CH2(OH)C(ONO2)(CH3)CH(OOH)CH2(ONO2)
CH2(OH)CH(ONO2)C(OOH)(CH3)CH2(OH)
CH2(OH)C(ONO2)(CH3)CH(OOH)CH2(OH)
CdH2=CdHC(OOH)(CH3)CH2(ONO2)
CdH2=Cd(CH3)CH(OOH)CH2(ONO2)
CH2(ONO2)C(OOH)(CH3)COCH2(OH)
CH2(OH)CH(OH)C(OOH)(CH3)CH2(ONO2)
CH2(OH)C(OH)(CH3)CH(OOH)CH2(ONO2)
C9H12CH3(ONO2),H(OOH)
Functional Groups
| ohho
| nhho
| ohhn
| khho
| okh
| kh
| koh
| kh
| kh
| kkh
| kho
| okh
| kh
| okh
| okh
| okoh
| ookh
| hko o
| ookh
| khoo
| nh
| hn
| nh
| hn
| vkonh
| nh
| onh
| nhd
| hn
| khn
| hn
| kvonh
| konh
| hkono
| noovkh
| nhno
| onhn
| ohnn
| onhn
| nhu
| uhn
| nhko
| nhoo
| oohn
| thn
143
Table A.32 Chemical Codes: ho11–hr62.
Code
ho11
ho21
ho22
ho31
ho32
ho33
ho34
ho35
ho40
ho41
ho42
ho43
ho45
ho46
ho4A
ho4B
ho4C
ho4D
ho4E
ho4F
ho50
ho51
ho52
ho53
ho54
ho56
ho57
ho58
ho59
ho5A
ho5B
ho5C
ho5D
ho61
ho62
ho63
ho64
ho71
hr61
hr62
C
1
2
2
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
7
6
6
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
4
6
6
8
8
8
8
8
10
10
10
10
10
10
10
10
10
10
10
10
12
12
12
12
12
12
12
12
12
12
12
12
12
14
14
14
14
16
8
8
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
3
3
3
4
4
3
3
3
3
3
3
3
3
3
3
4
3
4
4
4
4
3
3
4
4
3
3
3
3
5
5
3
5
4
3
5
3
3
4
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH2(OOH)(OH)
CH3CH(OH)(OOH)
CH2(OH)CH2(OOH)
CH2(OH)CH(OH)CH2(OOH)
CH2(OH)CH(OOH)CH2(OH)
CH2(OH)CH2CH2(OOH)
CH3CH(OOH)CH2(OH)
CH3CH(OH)CH2(OOH)
CH3CH2CH(OH)CH2(OOH)
CH2(OH)CH2CH2CH2(OOH)
CH3CH(OH)CH(OOH)CH3
CH3C(OOH)(CH3)CH2(OH)
CH3C(OH)(CH3)CH2(OOH)
CH3CH(OH)CH2CH2(OOH)
CH2(OH)CH(CH3)CH2(OOH)
CH2(OH)CH(OH)CH2CH2(OOH)
CH2(OH)CH2CH(OOH)CH3
CH2(OH)CH2CH(OH)CH2(OOH)
CH2(OH)C(OH)(CH3)CH2(OOH)
CH3CH(OH)CH(OH)CH2(OOH)
CH2(OH)CH2CH(OH)CH(OOH)CH3
CH2(OH)CH(CH3)CH(OOH)CH3
C5H10(OH)(OOH)
CH2(OH)CH(CH3)CH(OOH)CH2(OH)
CH3CH2CH2CH(OOH)CH(OH)(OH)
CH2(OH)CH2CH2CH(OOH)CH3
CH3CH(OH)CH2CH2CH2(OOH)
CH3CH2CH(OH)CH2CH2(OOH)
CH2(OH)CH(CH3)CH2CH2(OOH)
CH2(OH)CH(OH)C(OOH)(CH3)CH2(OH)
CH2(OH)C(OH)(CH3)CH(OOH)CH2(OH)
CH3CH(OH)CH(CH3)CH2(OOH)
CH2(OH)C(OH)(CH3)CH(OH)CH2(OOH)
CH2(OH)CH(CH3)CH(CH2(OH))CH2(OOH)
C6H12(OH)(OOH)
CH2(OH)CH(CH2(OH))CH(CH2(OH))CH2(OOH)
CH2(OH)CH(CH3)CH(CH3)CH2(OOH)
C7H14(OH)(OOH)
C6H4(OH)(OH),(H)(OOH)
C6H4(H)(OH),(H)(OOH)
Functional Groups
| ho
| oh
| oh
| ooh
| oho
| oh
| ho
| oh
| oh
| ho
| oh
| ho
| oh
| oh
| oh
| hoo
| ho
| ooh
| ooh
| ooh
| hoo
| oh
| ohz
| oho
| hoo
| ho
| ho
| oh
| oh
| ohoo
| ooho
| oh
| oooh
| hoo
| ohz
| ohoo
| ho
| ohz
| rooh
| hro
144
Table A.33 Chemical Codes: hr71–ko48.
Code
hr71
hr72
hr73
hr74
hr75
hr81
hr82
ht71
ht81
ht82
ht83
ht91
htA1
hu51
hu52
hu71
hv32
k031
k041
k051
k052
k053
k061
k062
k071
k081
kk42
kk43
kk51
ko31
ko34
ko35
ko37
ko41
ko42
ko43
ko45
ko46
ko47
ko48
C
7
7
7
7
7
8
8
7
8
8
8
9
10
5
5
7
3
3
4
5
5
5
6
6
7
8
4
4
5
3
3
3
3
4
4
4
4
4
4
4
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
9
9
10
10
8
12
12
12
18
18
14
16
18
10
10
12
3
6
8
10
10
10
12
12
14
16
6
6
8
6
6
6
6
8
8
8
8
8
8
8
N
1
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
6
5
3
4
2
3
4
4
2
3
3
3
3
3
3
3
6
1
1
1
1
1
1
1
1
1
3
2
3
3
3
4
2
2
2
3
2
3
4
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
C6H2CH3,(OH)(OH),NO2,,(H)(OOH)
C6H2CH3,(H)(OH),(H)(OOH),,NO2
C6H3CH3,(H)OH,(H)OOH
C6H3CH3,(OH)OH,(H)OOH
C6H5CH2(OOH)
C6H2CH3,(H)OH,CH3,(H)OOH
C6H2CH3,(OH)OH,CH3,(H)OOH
CH3CO’C(OOH)’CH2’O’C(CH3)CH3
C8H17(OOH)
C8H16(OH)(OOH)
apR2C8H13O(OOH)
apR1C9H15O(OOH)
C9H12CH3,OOH,HOH
CdH2=CdHC(OOH)(CH3)CH2(OH)
CdH2=Cd(CH3)CH(OOH)CH2(OH)
CH3COCd(CH2(OOH))=Cd(CH3)CH3
CO(NO2)COCH2(OOH)
CH3COCH3
CH3CH2COCH3
CH3CH2CH2COCH3
CH3CH2COCH2CH3
CH3CH(CH3)COCH3
CH3CH2CH2CH2COCH3
C5H12CO
C6H14CO
C7H16CO
CH2(OH)COCOCH3
CH3COCOCH3
CH2(OH)CH2COCOCH3
CH2(OH)COCH2(OH)
CH(OH)(OH)COCH3
CH2(OH)COCH(OH)(OH)
CH3COCH2(OH)
CH2(OH)COCH2CH3
CH3CH(OH)COCH3
CH2(OH)CH2COCH2(OH)
CH2(OH)CH2COCH3
CH2(OH)CH(OH)COCH3
CH2(OH)COCH(OH)CH2(OH)
CH3CH(OH)COCH2(OH)
Functional Groups
| rooh
| roh
| roh
| rooh
| rh
| roh
| rooh
| hkt
| htz
| ohtz
| k ht
| k ht
| th
| ohu
| uho
| khu
| kkhv
|k
|k
|k
|k
|k
|k
| kz
| kz
| kz
| kko
| kk
| kko
| oko
| koo
| okoo
| ko
| ko
| ok
| oko
| ko
| koo
| okoo
| oko
145
Table A.34 Chemical Codes: ko50–1v02.
Code
ko50
ko51
ko52
ko53
ko54
ko55
ko56
ko61
ko71
l011
l012
l013
l023
la11
ld11
ld12
ld21
ld41
lh01
lh11
lh21
lh22
lh31
lh41
lh42
lk21
lk31
lk41
ln01
lo11
lo13
lo21
lo22
lo31
lo41
lo42
lo43
lu23
lu24
lv01
lv02
C
5
5
5
5
5
5
5
6
7
1
1
1
2
1
1
1
2
4
0
1
2
2
3
4
4
2
3
4
0
1
1
2
2
3
4
4
4
2
2
0
0
X
0
0
0
0
0
0
0
0
0
1
2
3
3
1
1
2
1
1
2
1
1
1
1
1
1
1
1
1
1
1
3
1
1
1
1
1
1
3
4
1
1
H
10
10
10
10
10
10
10
12
14
3
2
1
3
1
1
0
3
7
0
3
5
5
7
9
9
3
5
7
0
3
1
5
5
7
9
9
9
1
0
0
0
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
1
1
O
3
3
2
2
4
3
2
2
2
0
0
0
0
2
1
1
1
2
2
2
2
2
2
2
2
1
1
1
3
1
1
1
1
1
1
1
2
0
0
2
2
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH2(OH)CH2CH(OH)COCH3
CH2(OH)CH(CH3)COCH2(OH)
CH2(OH)CH2CH2COCH3
CH2(OH)CH(CH3)COCH3
CH2(OH)C(OH)(CH3)COCH2(OH)
CH3CH2CH2COCH(OH)(OH)
C4H9(OH)CO
CH2(OH)CH2CH2COCH2CH3
C6H13(OH)CO
CH3(Cl)
CH2(Cl2)
CH(Cl3)
CH3C(Cl3)
CO(OH)(Cl)
CHO(Cl)
CO(Cl2)
CH2(Cl)CHO
CH3CH(OH)CH(Cl)CHO
Cl2O2
CH2(Cl)(OOH)
CH2(Cl)CH2(OOH)
CH3CH(Cl)(OOH)
C3H6(OOH)(Cl)
CH3CH(Cl)CH(OOH)CH3
CH3C(OOH)(CH3)CH2(Cl)
CH3CO(Cl)
CH2(Cl)COCH3
CH3CH(Cl)COCH3
ClONO2
CH2(Cl)(OH)
C(Cl3)(OH)
CH2(OH)CH2(Cl)
CH3CH(Cl)(OH)
CH3CH(OH)CH2(Cl)
CH3CH(OH)CH(Cl)CH3
CH3C(OH)(CH3)CH2(Cl)
CH3CH(OH)CH(Cl)CH2(OH)
CdH(Cl)=Cd(Cl2)
Cd(Cl2)=Cd(Cl2)
ClNO2
ClONO
Functional Groups
| koo
| ook
| ko
| ok
| ooko
| koo
| okz
| ko
| okz
|l
|l
|l
|l
| al
| dl
| ld
| dl
| dlo
| hl
| hl
| hl
| hl
| hlz
| hl
| hl
| kl
| kl
| kl
| ln
| lo
| lo
| lo
| lo
| lo
| lo
| lo
| olo
| ul
| ul
| lv
| lv
146
Table A.35 Chemical Codes: m011–n081.
Code
m011
m021
m022
m031
md11
md21
md31
mk21
mo01
mo11
mo12
mo21
mo22
mo23
mo31
mu11
mu21
mv11
mv21
mv22
mw11
mw21
mw22
n011
n012
n021
n031
n032
n041
n042
n043
n051
n052
n053
n054
n055
n056
n057
n061
n062
n063
n071
n081
C
1
2
2
3
1
2
3
2
0
1
1
2
2
2
3
1
2
1
2
2
1
2
2
1
1
2
3
3
4
4
4
5
5
5
5
5
5
5
6
6
6
7
8
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
5
7
7
9
3
5
7
5
3
5
5
7
7
7
9
3
5
4
6
6
4
6
6
3
3
5
7
7
9
9
9
11
11
11
11
11
11
11
13
13
13
15
17
N
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
O
0
0
0
0
1
1
1
1
1
1
2
1
1
2
1
0
0
2
2
2
1
1
1
3
4
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3(NH2)
CH2(NH2)CH3
CH3(NH)CH3
CH3NCH3CH3
CHO(NH2)
CH3(NH)CHO
CH3CHONCH3
CH3CO(NH2)
NH2OH
CH2(OH)(NH2)
CH2(OH)(NH)(OH)
CH3CH(OH)(NH2)
CH3(NH)CH2(OH)
CH2(OH)N(OH)CH3
CH2(OH)N(CH3)CH3
CdH2=NH
CdH2=NCH3
CH3(NHNO2)
CH3CH2(NHNO2)
CH3NNO2CH3
CH3(NH)N=O
CH2(NH)N=OCH3
CH3CH3NN=O
CH3(ONO2)
CH3(O2NO2)
CH3CH2(ONO2)
CH3CH2CH2(ONO2)
CH3CH(ONO2)CH3
CH3CH2CH2CH2(ONO2)
CH3CH2CH(ONO2)CH3
CH3C(ONO2)(CH3)CH3
C5H11(ONO2)
CH3CH(CH3)CH(ONO2)CH3
CH3CH2CH2CH2CH2(ONO2)
CH3CH2CH2CH(ONO2)CH3
CH3CH2CH(ONO2)CH2CH3
CH3CH2CH(CH3)CH2(ONO2)
CH3CH2C(ONO2)(CH3)CH3
C6H13(ONO2)
CH3CH(CH3)C(ONO2)(CH3)CH3
CH3CH(CH3)CH(CH3)CH2(ONO2)
C7H15(ONO2)
C8H17(ONO2)
Functional Groups
|m
|m
|m
|m
| dm
| md
| dm
| km
| mo
| om
| omo
| om
| mo
| omo
| om
| mu
| mu
| vm
| vm
| vm
| wm
| wm
| wm
|n
|n
|n
|n
|n
|n
|n
|n
| nz
|n
|n
|n
|n
|n
|n
| nz
|n
|n
| nz
| nz
147
Table A.36 Chemical Codes: nd11–nd81.
Code
nd11
nd21
nd22
nd23
nd31
nd32
nd33
nd34
nd35
nd36
nd37
nd38
nd40
nd41
nd42
nd43
nd44
nd45
nd46
nd47
nd48
nd49
nd4A
nd4B
nd4C
nd4D
nd4E
nd50
nd51
nd52
nd53
nd54
nd55
nd56
nd57
nd58
nd5A
nd5B
nd5C
nd61
nd62
nd81
C
1
2
2
2
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
5
4
5
5
5
5
5
5
5
5
5
5
5
5
6
6
8
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
1
3
3
1
2
3
3
5
5
3
5
5
7
4
4
5
4
5
5
7
7
7
4
5
7
7
5
7
6
7
6
7
7
7
7
9
9
7
9
11
11
13
N
1
1
1
1
2
1
1
1
1
1
1
1
1
2
2
1
2
1
1
1
1
1
2
1
1
1
1
1
2
1
2
1
1
1
1
1
1
1
1
1
1
1
O
4
4
5
5
7
5
5
5
4
6
5
4
4
8
7
5
8
6
6
5
4
5
9
7
5
6
6
6
8
6
8
7
5
6
6
4
4
6
6
4
5
5
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CHO(ONO2)
CH2(ONO2)CHO
CH(OH)(ONO2)CHO
CO(ONO2)CHO
CO(NO2)CH(ONO2)CHO
CHOCH(ONO2)CHO
CH2(ONO2)COCHO
CH2(OH)CH(ONO2)CHO
CH3CH(ONO2)CHO
CH(OH)(ONO2)COCHO
CH3C(OH)(ONO2)CHO
CH2(ONO2)CH2CHO
CH2(ONO2)CH(CH3)CHO
CO(NO2)CH(ONO2)CH(OH)CHO
CH3COC(ONO2)(NO2)CHO
CH3COCH(ONO2)CHO
CO(NO2)CH(OH)CH(ONO2)CHO
CHOCH(OH)CH(ONO2)CHO
CH2(ONO2)COCH(OH)CHO
CH2(OH)C(CH3)(ONO2)CHO
CH3CH(ONO2)CH2CHO
CH2(OH)CH(ONO2)CH2CHO
CH(OH)(ONO2)C(OH)(NO2)COCHO
CH(OH)(ONO2)CH(OH)COCHO
CH2(ONO2)C(OH)(CH3)CHO
CH2(ONO2)CH(OH)COCH2CHO
CH2(ONO2)CH(OH)COCHO
CHOCH2C(O2NO2)(CH3)CHO
CH3COC(NO2)(ONO2)CH(OH)CHO
CH3COCH(ONO2)CH(OH)CHO
CH3COC(OH)(NO2)CH(ONO2)CHO
CH2(ONO2)COCH(OH)CH(OH)CHO
CH3COCH(ONO2)CH2CHO
CH3COCH(OH)CH(ONO2)CHO
CHOCH(OH)C(ONO2)(CH3)CHO
CH3CH2CH(ONO2)CH2CHO
CH3CH(ONO2)CH(CH3)CHO
CH2(OH)C(ONO2)(CH3)COCHO
CH2(ONO2)CH(OH)C(OH)(CH3)CHO
CH3C(ONO2)(CH3)CH(CH3)CHO
CH2(OH)C(ONO2)(CH3)CH(CH3)CHO
CH3C(ONO2)(CH3)CH(COCH3)CH2CHO
Functional Groups
| nd
| nd
| ond
| dkn
| kndv
| dnd
| nkd
| ond
| dn
| onkd
| ond
| dn
| dn
| knodv
| kndv
| knd
| kondv
| ddon
| nkod
| ond
| nd
| ond
| dkovon
| dkoon
| nod
| dkon
| dkon
| dnd
| donkv
| knod
| dnokv
| nkood
| knd
| kond
| dond
| nd
| dn
| onkd
| nood
| nd
| ndo
| kdn
148
Table A.37 Chemical Codes: nk23–no46.
Code
nk23
nk31
nk33
nk34
nk36
nk38
nk40
nk42
nk43
nk45
nk46
nk47
nk48
nk49
nk4A
nk4B
nk4C
nk4F
nk4G
nk4I
nk4J
nk51
nn31
nn41
nn42
nn43
nn44
nn51
nn52
nn53
nnA1
no11
no21
no23
no31
no32
no33
no34
no35
no40
no42
no43
no44
no45
no46
C
2
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
3
4
4
4
4
5
5
5
10
1
2
2
3
3
3
3
3
4
4
4
4
4
4
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
3
5
5
5
3
5
7
5
7
7
7
5
7
7
7
7
7
5
7
7
7
9
6
8
8
6
6
8
8
10
16
3
5
5
7
7
7
7
7
9
9
9
9
9
9
N
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
O
4
5
5
6
5
4
5
7
4
4
5
5
5
4
5
5
6
6
6
7
6
6
6
6
6
7
7
6
6
8
6
4
4
4
5
5
4
4
4
4
4
4
4
4
4
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3CO(ONO2)
CH2(OH)COCH2(ONO2)
CH3COCH(OH)(ONO2)
CH2(OH)COCH(OH)(ONO2)
CH3COCO(ONO2)
CH3COCH2(ONO2)
CH2(OH)CH2COCH2(ONO2)
CH2(OH)COCH(OH)CO(ONO2)
CH3CH2COCH2(ONO2)
CH3COCH(ONO2)CH3
CH3COCH(ONO2)CH2(OH)
CH3COCOCH2(ONO2)
CH2(OH)COCH2CH2(ONO2)
CH3COCH2CH2(ONO2)
CH3COCH(OH)CH2(ONO2)
CH3CH(OH)COCH2(ONO2)
CH2(OH)COCH(OH)CH2(ONO2)
CH3COCH(OH)CO(ONO2)
CH3COCH(OH)CH(OH)(ONO2)
CH2(OH)COCH(OH)CH(OH)(ONO2)
CH2(OH)CH(OH)COCH2(ONO2)
CH2(OH)COC(ONO2)(CH3)CH2(OH)
CH3CH(ONO2)CH2(ONO2)
CH3CH(ONO2)CH(ONO2)CH3
CH3C(ONO2)(CH3)CH2(ONO2)
CH2(ONO2)C(ONO2)(CH3)CHO
CH3COCH(ONO2)CH2(ONO2)
CdH2=CdHC(ONO2)(CH3)CH2(ONO2)
CdH2=Cd(CH3)CH(ONO2)CH2(ONO2)
CH2(OH)CH(ONO2)C(ONO2)(CH3)CH2(OH)
C9H12CH3(ONO2),H(ONO2)
CH2(ONO2)(OH)
CH2(OH)CH2(ONO2)
CH3CH(OH)(ONO2)
CH2(OH)CH(OH)CH2(ONO2)
CH2(OH)CH(ONO2)CH2(OH)
CH3CH(OH)CH2(ONO2)
CH3CH(ONO2)CH2(OH)
CH2(OH)CH2CH2(ONO2)
CH3CH2CH(OH)CH2(ONO2)
CH2(OH)CH2CH2CH2(ONO2)
CH3CH(OH)CH(ONO2)CH3
CH3C(ONO2)(CH3)CH2(OH)
CH3C(OH)(CH3)CH2(ONO2)
CH3CH(OH)CH2CH2(ONO2)
Functional Groups
| kn
| nko
| kon
| okon
| kkn
| kn
| okn
| okono
| kn
| kn
| kno
| kk n
| okn
| kn
| kon
| okn
| okon
| kokn
| koon
| okoon
| ookn
| onko
| nn
| nn
| nn
| nnd
| knn
| nnu
| unn
| onno
| tnn
| no
| on
| on
| oon
| ono
| on
| no
| on
| on
| no
| on
| no
| on
| on
149
Table A.38 Chemical Codes: no4A–nu55.
Code
no4A
no4B
no4C
no4D
no4E
no4F
no50
no51
no52
no53
no54
no56
no57
no58
no59
no5A
no5B
no5C
no5D
no61
no62
no63
no64
no71
no81
nr61
nr71
nr72
nr73
nr74
nr75
nt71
nt81
nt91
ntA1
ntA2
nu51
nu52
nu53
nu54
nu55
C
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
6
6
6
6
7
8
6
7
7
7
7
7
7
8
9
10
10
5
5
5
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
9
9
9
9
9
9
11
11
11
11
11
11
11
11
11
11
11
11
11
13
13
13
13
15
17
5
9
9
8
8
7
11
13
15
17
17
9
9
7
9
9
N
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
1
1
1
1
1
1
1
1
1
1
1
O
4
5
4
5
5
5
5
5
4
4
5
4
4
4
4
4
6
6
6
4
4
5
6
4
4
3
4
5
7
6
3
5
4
4
4
4
4
4
4
4
4
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH2(OH)CH(CH3)CH2(ONO2)
CH2(OH)CH(OH)CH2CH2(ONO2)
CH2(OH)CH2CH(ONO2)CH3
CH2(OH)CH2CH(OH)CH2(ONO2)
CH2(OH)C(OH)(CH3)CH2(ONO2)
CH3CH(OH)CH(OH)CH2(ONO2)
CH2(OH)CH2CH(OH)CH(ONO2)CH3
CH2(OH)CH(CH3)CH(ONO2)CH2(OH)
C5H10(OH)(ONO2)
CH2(OH)CH(CH3)CH(ONO2)CH3
CH3CH2CH2CH(ONO2)CH(OH)(OH)
CH2(OH)CH2CH2CH(ONO2)CH3
CH3CH(OH)CH2CH2CH2(ONO2)
CH3CH2CH(OH)CH2CH2(ONO2)
CH2(OH)CH(CH3)CH2CH2(ONO2)
CH3CH(OH)CH(CH3)CH2(ONO2)
CH2(OH)CH(OH)C(ONO2)(CH3)CH2(OH)
CH2(OH)C(OH)(CH3)CH(ONO2)CH2(OH)
CH2(OH)C(OH)(CH3)CH(OH)CH2(ONO2)
C6H12(OH)(ONO2)
CH2(OH)CH(CH3)CH(CH3)CH2(ONO2)
CH2(OH)CH(CH3)CH(ONO2)CH2CH2(OH)
CH2(OH)CH(CH2(OH))CH(CH2(OH))CH2(ONO2)
C7H14(OH)(ONO2)
C8H16(OH)(ONO2)
C6H5,ONO2
C6H3CH3,(H)(OH),(H)(ONO2)
C6H3CH3,(OH)(OH),(H)(ONO2)
C6H2CH3,(OH)(OH),NO2,(H)(ONO2)
C6H2CH3,(H)(OH),(H)(ONO2),,NO2
C6H5CH2(ONO2)
CH3CO’C(ONO2)’CH2’O’C(CH3)CH3
apR2C8H13O(ONO2)
apR1C9H15O(ONO2)
C9H12CH3,(ONO2),HOH
C9H12CH3(OH),H(ONO2)
CdH2=CdHC(ONO2)(CH3)CH2(OH)
CdH2=Cd(CH3)CH(ONO2)CH2(OH)
CdH2=Cd(CH3)COCH2(ONO2)
CdH2=CdHC(OH)(CH3)CH2(ONO2)
CdH2=Cd(CH3)CH(OH)CH2(ONO2)
Functional Groups
| on
| noo
| no
| oon
| oon
| oon
| noo
| ono
| onz
| on
| noo
| no
| no
| on
| on
| on
| oono
| oono
| ooon
| onz
| no
| ono
| ooon
| onz
| onz
| rn
| rno
| roon
| roon
| ron
| rn
| knt
| k nt
| k nt
| ton
| ton
| onu
| uno
| uk n
| nou
| uon
150
Table A.39 Chemical Codes: nv32–oo49.
Code
nv32
nv35
nv39
nv41
nv4D
nv4E
nv4H
o011
o021
o031
o032
o041
o042
o043
o044
o052
o053
o054
o055
o056
o057
o061
o062
o063
o071
o081
oo11
oo21
oo31
oo32
oo33
oo41
oo42
oo43
oo44
oo45
oo46
oo47
oo48
oo49
C
3
3
3
4
4
4
4
1
2
3
3
4
4
4
4
5
5
5
5
5
5
6
6
6
7
8
1
2
3
3
3
4
4
4
4
4
4
4
4
4
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
4
2
4
4
4
6
6
4
6
8
8
10
10
10
10
12
12
12
12
12
12
14
14
14
16
18
4
6
8
8
8
10
10
10
10
10
10
10
10
10
N
2
2
2
2
2
2
2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
O
7
8
8
9
8
8
9
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
3
2
2
2
2
2
2
3
2
3
3
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3C(OH)(ONO2)CO(NO2)
CO(NO2)CH(OH)CO(ONO2)
CO(NO2)CH(OH)CH(OH)(ONO2)
CH2(OH)COC(NO2)(OH)CO(ONO2)
CH3COC(NO2)(OH)CO(ONO2)
CH3COC(NO2)(OH)CH(OH)(ONO2)
CH2(OH)COC(OH)(NO2)CH(OH)(ONO2)
CH3(OH)
CH3CH2(OH)
CH3CH2CH2(OH)
CH3CH(OH)CH3
CH3CH2CH(OH)CH3
CH3CH2CH2CH2(OH)
CH3C(OH)(CH3)CH3
CH3CH(CH3)CH2(OH)
CH3CH(CH3)CH(OH)CH3
CH3CH2CH2CH2CH2(OH)
CH3CH2CH2CH(OH)CH3
CH3CH2CH(OH)CH2CH3
CH3CH2CH(CH3)CH2(OH)
CH3C(OH)(CH3)CH2CH3
C6H13(OH)
CH3CH(CH3)C(OH)(CH3)CH3
CH3CH(CH3)CH(CH3)CH2(OH)
C7H15(OH)
C8H17(OH)
CH2(OH)(OH)
CH2(OH)CH2(OH)
CH3CH(OH)CH2(OH)
CH2(OH)CH(OH)CH2(OH)
CH2(OH)CH2CH2(OH)
CH3CH2CH(OH)CH2(OH)
CH2(OH)CH2CH2CH2(OH)
CH3C(OH)(CH3)CH2(OH)
CH3CH(OH)CH2CH2(OH)
CH2(OH)CH(CH3)CH2(OH)
CH2(OH)CH2CH(OH)CH2(OH)
CH3CH(OH)CH(OH)CH3
CH2(OH)C(OH)(CH3)CH2(OH)
CH3CH(OH)CH(OH)CH2(OH)
Functional Groups
| onkv
| koknv
| voon
| okonov
| kvokn
| kvoon
| okovon
|o
|o
|o
|o
|o
|o
|o
|o
|o
|o
|o
|o
|o
|o
| oz
|o
|o
| oz
| oz
| oo
| oo
| oo
| ooo
| oo
| oo
| oo
| oo
| oo
| oo
| ooo
| oo
| ooo
| ooo
151
Table A.40 Chemical Codes: oo51–pd56.
Code
oo51
oo52
oo53
oo54
oo55
oo57
oo58
oo59
oo61
oo62
oo63
oo64
oo65
oo71
oo81
p021
p031
p041
p042
p051
p052
p053
p061
pa31
pa32
pa33
pd21
pd31
pd32
pd33
pd41
pd42
pd43
pd44
pd45
pd46
pd47
pd48
pd51
pd52
pd53
pd54
pd55
pd56
C
5
5
5
5
5
5
5
5
6
6
6
6
6
7
8
2
3
4
4
5
5
5
6
3
3
3
2
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
12
12
12
12
12
12
12
12
14
14
14
14
14
16
18
3
5
7
7
9
9
9
11
3
3
3
1
2
3
3
2
4
3
3
5
3
3
5
3
3
5
5
7
7
N
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
2
1
1
2
2
1
1
1
1
1
1
1
1
1
1
1
1
O
2
2
3
2
3
3
2
4
2
2
3
4
2
2
2
5
5
5
5
5
5
5
5
8
7
9
6
9
7
6
10
10
8
8
8
7
7
6
9
9
9
9
6
6
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH3CH(OH)CH2CH2CH2(OH)
CH2(OH)CH(CH3)CH2CH2(OH)
CH3CH(OH)CH(OH)CH2CH2(OH)
CH3CH(OH)CH(CH3)CH2(OH)
CH2(OH)CH(CH3)CH(OH)CH2(OH)
CH3CH2CH2CH(OH)CH(OH)(OH)
CH3CH2CH(OH)CH2CH2(OH)
CH2(OH)CH(OH)C(OH)(CH3)CH2(OH)
C6H12(OH)(OH)
CH2(OH)CH(CH3)CH(CH3)CH2(OH)
CH2(OH)CH(CH2(OH))CH(CH3)CH2(OH)
CH2(OH)CH(CH2(OH))CH(CH2(OH))CH2(OH)
CH3C(OH)(CH3)CH(CH3)CH2(OH)
C7H14(OH)(OH)
C8H16(OH)(OH)
CH3CO(OONO2)
CH3CH2CO(OONO2)
CH3CH(CH3)CO(OONO2)
CH3CH2CH2CO(OONO2)
CH3CH2CH2CH2CO(OONO2)
CH3CH2CH(CH3)CO(OONO2)
CH3CH(CH3)CH2CO(OONO2)
CH3CH(CH3)CH(CH3)CO(OONO2)
CO(OH)CH(OH)CO(OONO2)
CO(OH)CH2CO(OONO2)
CO(OH)C(OH)(OH)CO(OONO2)
CO(OONO2)CHO
CO(OONO2)C(NO2)(OH)CHO
CO(OONO2)CH(OH)CHO
CO(OONO2)CH2CHO
CO(OONO2)C(NO2)(OH)COCHO
CO(OONO2)C(NO2)(OH)CH(OH)CHO
CO(OONO2)COCH(OH)CHO
CO(OONO2)CH(OH)COCHO
CO(OONO2)CH(OH)CH(OH)CHO
CO(OONO2)CH2COCHO
CO(OONO2)COCH2CHO
CO(OONO2)CH(CH3)CHO
CO(OONO2)COCH(OH)COCHO
CO(OONO2)CH(OH)COCOCHO
CO(OONO2)CH(OH)CH(OH)COCHO
CO(OONO2)COCH(OH)CH(OH)CHO
CO(OONO2)CH2CH(CH3)CHO
CO(OONO2)CH(CH3)CH2CHO
Functional Groups
| oo
| oo
| ooo
| oo
| ooo
| ooo
| oo
| oooo
| ooz
| oo
| ooo
| oooo
| oo
| ooz
| ooz
|p
|p
|p
|p
|p
|p
|p
|p
| aop
| ap
| aoop
| dp
| dopv
| dop
| dp
| dkopv
| doopv
| dokp
| dkop
| doop
| dkp
| dkp
| dp
| dkokp
| dkkop
| dkoop
| dookp
| dp
| dp
152
Table A.41 Chemical Codes: pg21–pn55.
Code
pg21
pg40
ph21
ph30
ph31
ph40
pk31
pk33
pk40
pk45
pk46
pk47
pk48
pk49
pk4A
pk50
pk51
pk52
pk54
pk55
pk57
pk58
pk59
pk5A
pk5B
pk5C
pn21
pn30
pn31
pn32
pn34
pn40
pn41
pn42
pn43
pn44
pn47
pn48
pn49
pn51
pn52
pn53
pn54
pn55
C
2
4
2
3
3
4
3
3
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
2
3
3
3
3
4
4
4
4
4
4
4
4
5
5
5
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
1
5
3
5
5
7
3
3
5
5
5
5
5
5
5
7
5
5
5
5
7
7
5
7
7
7
2
4
1
2
4
6
3
3
4
3
6
6
4
5
6
5
6
6
N
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
3
2
2
2
3
3
2
3
2
2
2
3
2
3
2
2
O
8
10
7
7
7
7
7
6
7
7
8
7
7
6
8
7
8
9
8
9
8
9
7
6
7
6
8
8
11
9
8
9
12
11
9
12
8
10
10
12
10
12
10
11
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CO(OOH)CO(OONO2)
CO(OOH)C(OOH)(CH3)CO(OONO2)
CH2(OOH)CO(OONO2)
CH2(OOH)CH2CO(OONO2)
CH3CH(OOH)CO(OONO2)
CH2(OH)C(OOH)(CH3)CO(ONO2)
CH2(OH)COCO(OONO2)
CH3COCO(OONO2)
CH3CH(OH)COCO(OONO2)
CH3COCH(OH)CO(OONO2)
CH2(OH)COCH(OH)CO(OONO2)
CH2(OH)COCH2CO(OONO2)
CH2(OH)CH2COCO(OONO2)
CH3COCH2CO(OONO2)
CH2(OH)CH(OH)COCO(OONO2)
CH3COCH(OH)CH2CO(OONO2)
CH3COCOCH(OH)CO(OONO2)
CH2(OH)COCOCH(OH)CO(OONO2)
CH3COCH(OH)COCO(OONO2)
CH2(OH)COCH(OH)COCO(OONO2)
CH3COCH(OH)CH(OH)CO(OONO2)
CH2(OH)COCH(OH)CH(OH)CO(OONO2)
CH3COCOCH2CO(OONO2)
CH3COCH2CH2CO(OONO2)
CH3CH(OH)COCH2CO(OONO2)
CH3COCH(CH3)CO(OONO2)
CH2(ONO2)CO(OONO2)
CH2(ONO2)CH2CO(OONO2)
CO(NO2)CH(ONO2)CO(OONO2)
CH2(ONO2)COCO(OONO2)
CH3CH(ONO2)CO(OONO2)
CH2(OH)C(ONO2)(CH3)CO(OONO2)
CO(NO2)CH(ONO2)CH(OH)CO(OONO2)
CH3COC(NO2)(ONO2)CO(OONO2)
CH3COCH(ONO2)CO(OONO2)
CO(NO2)CH(OH)CH(ONO2)CO(OONO2)
CH3CH(ONO2)CH2CO(OONO2)
CH2(OH)CH(ONO2)CH(OH)CO(OONO2)
CH2(ONO2)COCH(OH)CO(OONO2)
CH3COC(NO2)(ONO2)CH(OH)CO(OONO2)
CH3COCH(ONO2)CH(OH)CO(OONO2)
CH3COC(NO2)(OH)CH(ONO2)CO(OONO2)
CH3COCH(OH)CH(ONO2)CO(OONO2)
CH2(ONO2)COCH(OH)CH(OH)CO(OONO2)
Functional Groups
| pg
| ghp
| ph
| ph
| ph
| ohp
| okp
| kp
| okp
| kop
| okop
| okp
| okp
| kp
| ookp
| kop
| kkop
| okkop
| kokp
| okokp
| koop
| okoop
| kk p
| kp
| okp
| kp
| np
| np
| vknp
| nkp
| np
| onp
| vknop
| kvnp
| knp
| vkonp
| np
| onp
| nkop
| kvnop
| knop
| kvonp
| konp
| nkoop
153
Table A.42 Chemical Codes: po22–pv56.
Code
po22
po23
po31
po32
po33
po34
po35
po41
po42
po43
po44
po45
po46
po47
po50
po51
po52
po53
po54
po55
po56
po61
pr71
pt91
ptA1
pu31
pu32
pu41
pu42
pu43
pu44
pu51
pu52
pu53
pv21
pv22
pv32
pv41
pv42
pv43
pv44
pv53
pv56
C
2
2
3
3
3
3
3
4
4
4
4
4
4
4
5
5
5
5
5
5
5
6
7
9
10
3
3
4
4
4
4
5
5
5
2
2
3
4
4
4
4
5
5
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
3
3
5
5
5
5
5
7
7
7
7
7
7
7
9
9
9
9
9
9
9
11
5
13
15
2
3
2
3
2
5
4
5
5
2
0
2
2
2
4
4
4
6
N
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
1
2
1
2
1
2
1
1
2
2
2
2
2
2
2
2
2
O
7
6
6
7
7
8
6
6
6
6
7
6
7
6
8
6
6
6
6
7
6
6
5
6
6
9
7
8
6
8
5
8
6
6
9
8
9
10
10
9
10
10
10
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH(OH)(OH)CO(OONO2)
CH2(OH)CO(OONO2)
CH3CH(OH)CO(OONO2)
CH2(OH)CH(OH)CO(OONO2)
CH3C(OH)(OH)CO(OONO2)
CH2(OH)C(OH)(OH)CO(OONO2)
CH2(OH)CH2CO(OONO2)
CH2(OH)CH2CH2CO(OONO2)
CH3C(OH)(CH3)CO(OONO2)
CH3CH(OH)CH2CO(OONO2)
CH2(OH)CH(OH)CH2CO(OONO2)
CH3CH2CH(OH)CO(OONO2)
CH2(OH)CH2CH(OH)CO(OONO2)
CH2(OH)CH(CH3)CO(OONO2)
CH2(OH)C(OH)(CH3)CH(OH)CO(OONO2)
CH3CH(OH)CH2CH2CO(OONO2)
CH3CH2CH(OH)CH2CO(OONO2)
CH2(OH)CH(CH3)CH2CO(OONO2)
CH2(OH)CH2CH(CH3)CO(OONO2)
CH3CH(OH)CH(OH)CH2CO(OONO2)
CH3CH(OH)CH(CH3)CO(OONO2)
CH2(OH)CH(CH3)CH(CH3)CO(OONO2)
C6H5CO(OONO2)
apR2C8H13OCO(OONO2)
apR1C9H15OCO(OONO2)
Cd(NO2)(OH)=Cd(OH)CO(OONO2)
CdH(OH)=Cd(OH)CO(OONO2)
CO(NO2)CdH=CdHCO(OONO2)
CO(OONO2)CdH=CdHCHO
CO(OONO2)Cd(NO2)=CdHCHO
CdH2=Cd(CH3)CO(OONO2)
CH3COCd(NO2)=CdHCO(OONO2)
CHOCdH=Cd(CH3)CO(OONO2)
CH3COCdH=CdHCO(OONO2)
C(NO2)(OH)(OH)CO(OONO2)
CO(NO2)CO(OONO2)
CO(NO2)CH(OH)CO(OONO2)
CO(NO2)COCH(OH)CO(OONO2)
CO(NO2)CH(OH)COCO(OONO2)
CH3COC(NO2)(OH)CO(OONO2)
CO(NO2)CH(OH)CH(OH)CO(OONO2)
CH3COC(NO2)(OH)COCO(OONO2)
CH3COC(NO2)(OH)CH(OH)CO(OONO2)
Functional Groups
| oop
| op
| op
| oop
| oop
| ooop
| op
| op
| op
| op
| oop
| op
| op
| op
| ooop
| op
| po
| op
| op
| op
| op
| op
| rp
| k pt
| k pt
| ouopv
| ouop
| kupv
| du p
| duvp
| up
| kupv
| du p
| ku p
| oopv
| kpv
| kopv
| kkopv
| kokpv
| kopv
| koopv
| kokpv
| koopv
154
Table A.43 Chemical Codes: q011–sw11.
Code
q011
q012
r071
r081
rk61
rk62
rk63
rk71
rk72
rk73
rk74
ro61
ro64
ro65
ro71
ro72
ro76
ro77
ro81
ro83
ro84
rv62
rv63
rv72
rv73
rv74
rv75
rv78
rv81
rv82
s001
s011
s013
s015
s016
s017
s021
s022
s023
s024
s025
sd21
sn21
so21
sv01
sv11
sw11
C
1
1
7
8
6
6
6
7
7
7
7
6
6
6
7
7
7
7
8
8
8
6
6
7
7
7
7
7
8
8
0
1
1
1
1
1
2
2
2
2
2
2
2
2
0
1
1
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
0
1
8
10
7
6
6
8
8
7
7
6
8
8
8
8
10
10
10
12
12
5
4
7
7
6
9
9
9
9
2
3
3
3
4
4
6
7
6
7
7
4
6
6
1
3
3
N
0
0
0
0
1
0
0
0
0
1
1
0
0
0
0
0
0
0
0
0
0
1
2
1
1
2
1
1
1
1
0
0
0
0
0
0
0
0
0
0
0
0
1
0
1
1
1
O
3
3
0
0
5
3
2
2
3
5
4
1
2
3
1
1
2
3
1
2
3
3
5
2
3
5
5
4
2
3
4
2
1
3
3
2
0
1
1
3
2
1
3
1
2
2
1
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
Full Chemical Formula
NaCO3
NaHCO3
C6H5CH3
C6H4CH3,,CH3
C6H4(OH)(OH),(H)(ONO2)
C6H4(OH)(OH),(=O)
C6H4(H)(OH),=O
C6H3CH3,(H)(OH),(=O)
C6H3CH3,(OH)(OH),(=O)
C6H2CH3,(OH)(OH),NO2,,(=O)
C6H2CH3,(H)(OH),(=O),,NO2
C6H5(OH)
C6H4(H)(OH),H(OH)
C6H4(OH)(OH),H(OH)
C6H5CH2(OH)
C6H4CH3,OH
C6H3CH3,H(OH),H(OH)
C6H3CH3,OH(OH),H(OH)
C6H3CH3,OH,CH3
C6H3CH3,H(OH),(CH3)(OH)
C6H3CH3,OH(OH),(CH3)(OH)
C6H4OH,NO2
C6H3OH,NO2,,NO2
C6H4CH3,,NO2
C6H3CH3,OH,NO2
C6H2CH3,OH,NO2,,NO2
C6H3CH3,(OH)(OH),OH(NO2)
C6H3(OH),H(OH),CH3,NO2
C6H3CH3,NO2,CH3
C6H2CH3,OH,CH3,,NO2
H2SO4
CH3SO2
CH3SO
CH3SO3
CH3SO3H
CH3SOOH
CH3SCH3
CH3SOHCH3
CH3SOCH3
CH3SOHO2CH3
CH3SOOHCH3
CH3SCHO
CH3SONO2CH3
CH3SCH2(OH)
HSNO2
CH3SNO2
CH3SNO
Functional Groups
|q
|q
|r
|r
| rook
| rook
| okr
| rok
| rook
| rook
| rok
| ro
| roo
| rooo
| ro
| ro
| roo
| rooo
| ro
| roo
| rooo
| rov
| rovv
| rv
| rov
| rovv
| rooov
| roov
| rv
| rov
|s
|s
|s
|s
|s
|s
|s
|s
|s
|s
|s
| ds
| ns
| so
| sv
| vs
| ws
155
Table A.44 Chemical Codes: t0A1–uv31.
Code
t0A1
tk81
tk82
tk91
tk92
toA1
u041
u042
ud31
ud32
ud33
ud34
ud41
ud42
ud43
ud51
ud52
ud53
ud71
ud81
uk22
uk23
uk31
uk32
uk33
uk41
uk51
uk71
uo22
uo23
uo32
uo33
uo34
uo35
uo36
uo37
uo41
uo42
uo51
uo52
uo53
uu51
uv21
uv22
uv31
C
10
8
8
9
9
10
4
4
3
3
3
3
4
4
4
5
5
5
7
8
2
2
3
3
3
4
5
7
2
2
3
3
3
3
3
3
4
4
5
5
5
5
2
2
3
X
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
H
16
12
14
16
16
18
8
8
2
4
3
4
4
6
3
6
6
5
10
12
2
2
4
4
4
6
8
12
4
4
6
6
6
6
6
6
8
8
10
10
10
8
1
3
5
N
0
0
0
0
0
0
0
0
0
0
1
0
0
0
1
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
O
0
2
2
2
3
2
0
0
3
3
5
1
2
1
4
2
2
4
2
2
2
1
2
3
1
1
2
2
2
1
2
3
1
1
2
1
1
1
1
2
2
0
4
4
4
S
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Full Chemical Formula
C9H13CH3
CH3CO’CH’CH2’CO’C(CH3)CH3
CH3CO’CH’CH2’CH(OH)’C(CH3)CH3
CH3CO’CH’CH2’CH(CH2(OH))’CCH3CH3
CH3CO’CH’CH2’CH(CH2(OH))’CCH3CH2(OH)
C9H12CH3(OH),H(OH)
CH3CdH=CdHCH3
CH3Cd(CH3)=CdH2
CdO=Cd(OH)CHO
CdH(OH)=Cd(OH)CHO
Cd(NO2)(OH)=Cd(OH)CHO
CdH2=CdHCHO
CHOCdH=CdHCHO
CdH2=Cd(CH3)CHO
CO(NO2)CdH=CdHCHO
CH3COCdH=CdHCHO
CHOCdH=Cd(CH3)CHO
CH3COCd(NO2)=CdHCHO
CH3COCd(CHO)=Cd(CH3)CH3
CH3Cd(CH3)=Cd(COCH3)CH2CHO
CdH(OH)=CdO
CdH2=CdO
CH3Cd(OH)=CdO
CH2(OH)Cd(OH)=CdO
CH3CdH=CdO
CdH2=CdHCOCH3
CdH2=Cd(CH3)COCH2(OH)
CH3COCd(CH2(OH))=Cd(CH3)CH3
CdH(OH)=CdH(OH)
CdH2=CdH(OH)
CH3Cd(OH)=CdH(OH)
CH2(OH)Cd(OH)=CdH(OH)
CH3CdH=CdH(OH)
CH3Cd(OH)=CdH2
CH2(OH)CdH=CdH(OH)
CdH2=CdHCH2(OH)
CH3CH2Cd(OH)=CdH2
CH3CdH=Cd(OH)CH3
CH3CH2CH2CdH=CdH(OH)
CdH2=CdHC(CH3)(OH)CH2(OH)
CdH2=Cd(CH3)CH(OH)CH2(OH)
CdH2=Cd(CH3)CdH=CdH2
CdO=Cd(NO2)(OH)
CdH(OH)=Cd(NO2)(OH)
CH3Cd(OH)=Cd(NO2)(OH)
Functional Groups
|t
| kkt
| kto
| kto
| ktoo
| too
|u
|u
| douk
| douo
| douov
| ud
| dud
| ud
| dkuv
| ku d
| du d
| dkuv
| kdu
| kd u
| ouk
| uk
| ouk
| oouk
| uk
| ku
| uko
| kou
| ouo
| uo
| ouo
| oouo
| uo
| ou
| ouo
| ou
| ou
| ou
| uo
| uoo
| uoo
| uu
| oukv
| ouov
| ouov
156
Table A.45 Chemical Codes: vk21–wo11.
Code
vk21
vk31
vk32
vk33
vk34
vk38
w011
w021
wo11
C
2
3
3
3
3
3
1
2
1
X
0
0
0
0
0
0
0
0
0
H
3
3
3
5
5
3
3
5
3
N
1
1
1
1
1
1
1
1
1
O
5
5
4
5
5
5
1
1
2
S
0
0
0
0
0
0
0
0
0
Full Chemical Formula
CH(OH)(OH)CO(NO2)
CO(NO2)COCH2(OH)
CH3COCO(NO2)
CH3C(OH)(OH)CO(NO2)
CH3COC(OH)(OH)(NO2)
CH2(OH)COCO(NO2)
CH3(NO)
CH3CH2(N=O)
CH2(OH)(N=O)
Functional Groups
| koov
| kkov
| kkv
| ookv
| ookv
| okkv
|w
|w
| ow
Appendix B
Mechanism Revisions: Discussion
The revisions made to the NCAR Master Mechanism are described in this appendix. Non-Troe
reactions are described first, followed by Troe reactions, and then photolysis reactions. For each
family of compounds there is a brief discussion of their chemistry and a detailed discussion of
the parameters used for reactions where revisions were not straightforward. Tables containing the
revised rate (and in some cases, mechanistic) parameters are included in Appendix C.
The following reviews were used as the basis for the revisions made to the Master Mechanism:
Atkinson et al. [1992b], Atkinson [1994], DeMore et al. [1997], and Sander et al. [2000]. Revisions
made to the peroxy radical reactions were primarily based on the work of Kirchner and Stockwell
[1996]. Additionally, many of the revisions made to the chemistry of alkyl nitrates (and reactions of
subsequent products) were based on the changes made to the NCAR Master Mechanism-Version 2.0
by Williams [1994a], which formed a portion of his dissertation work [Williams, 1994b].
157
158
B.1 Non-Troe Reactions
B.1.1 Inorganic Chemistry
B.1.1.1
Odd Oxygen
Table C.1 lists the odd oxygen reactions examined, those involving O(3 P) and O(1 D). Additionally,
the rate constants, k298, and activation temperatures, Ea /R, used in the revised mechanism and
the source of these parameters are also listed in Table C.1. DeMore et al. [1997] served as the
main reference for these reactions. Many of the recommended rate parameters for these reactions
match those used in Version 2.0 of the NCAR Master Mechanism. In Table C.1 these reactions list
Madronich and Calvert [1989] as the recommended source in addition to the source used to verify
the rate parameters. While the chemistry of halogenated compounds were not completely revised,
revisions were made to these reactions if new recommendations were listed by DeMore et al. [1997]
or Atkinson et al. [1992b].
In the NCAR Master Mechanism, the reactions of O2 with O(3 P) and N2 with O(1 D) are treated
as “true” three body reactions. For these reactions, the rate constants used by Madronich and
Calvert [1989] were compared to the rate constant at 298 K calculated from the low pressure limit
rate parameters recommended by DeMore et al. [1997]. As the low pressure limit rate parameters
recommended by DeMore et al. [1997] matched those in the original mechanism, no changes were
made to these reactions.
B.1.1.2
Odd Hydrogen
The HOx reactions in Table C.2 were updated using the recommendations of DeMore et al. [1997].
HO2 + HO2 This reaction has both bimolecular and termolecular components as well as a
dependence on water vapor. Because of the complex nature of this rate constant, it is calculated in
gear.f using the following equations:
U2*1.7 10,12 *EXP( 600.*(1./TEMP - 1./298.))
RK2
=
RK3
=
FH2O
=
CUNIT* 1.4 10,21 *EXP(2200./TEMP)
R(ITYPE5(I))
=
(RK2 + RK3*DENS)*(1. + FH2O*CH2O)
U3* 4.9 10,32 *EXP(1000.*(1./TEMP - 1./298.))
The only change made in the above equations was in the bimolecular rate, RK2. The rate was
changed from 1.5E-12*EXP(600*(1/temp - 1/298), where 1.5E-12 is the rate constant at 298 K, to
the recommendation of DeMore et al. [1997], k(298) = 1.7E-12 cm3 molecule,1 sec,1 .
159
B.1.1.3
Inorganic Nitrogen Species
Reaction rate parameters for reactions involving inorganic nitrogen species were compared with the
parameters recommended by DeMore et al. [1997]. As shown in Table C.3, a number of parameters
have been altered.
NO2+ O3 The channel producing NO3 and O2 is the only channel included in the recommendation
by DeMore et al. [1997]. However, Cantrell et al. [1985] suggests that a second channel
producing NO and 2O2 is responsible for 3% of the reaction of NO2 and O3 [FinlaysonPitts and Pitts, 1986]. Stockwell et al. [1997] includes the dominant channel and uses the rate
constant recommended by DeMore et al. [1997]. Madronich and Calvert [1989] used the rate
constant which is recommended by DeMore et al. [1997] for the dominant channel as well as
3% of that rate constant for channel B. As the data used in the evaluations [DeMore et al., 1997;
Atkinson, 1994] were published prior to the creation of the Master Mechanism (1985 or earlier),
this reaction and its parameters were not altered.
NO3 + M DeMore et al. [1997] notes that thermal decomposition of NO3 has been suggested
by Johnston et al. [1986] and Davidson et al. [1990] to occur. However, there is also evidence
suggesting that the thermal barrier for dissociation is too great to overcome in the atmosphere, at
47.3 kcal mol,1 . Madronich and Calvert [1989] include this reaction. However, due to the evidence
which suggests that this reaction does not take place and the lack of a recommendation by DeMore
et al. [1997], this reaction is removed from calculations by placing an “x” in the flag position of
dragon.mch.
NO2 + HO2 While no rate parameters are recommended, DeMore et al. [1997] includes the
following as a new reaction:
(B.1)
HO2 + NO2 ! HONO + O2 :
The recommendation for this reaction is based on the study of Tyndall et al. [1995]. As Tyndall et
al. [1995] found no evidence for the occurrance of this reaction in the atmosphere, it was not added
to the mechanism.
B.1.2 Organic Reactions
B.1.2.1
Unsubstituted Hydrocarbons
Reactions of methane and NMHC through C6 which do not contain reactive functional groups are
shown in Table C.4. These include reactions of alkanes, alkenes, and alkynes with OH and NO3
as well as ozone reactions for the alkenes and alkynes. Reactions of the nonspecific hydrocarbons
(c051, c061, c071, etc) were not altered. Rate parameters are available for a number of alkanes
160
not included in the original Master Mechanism (2,2-Dimethylpropane, n-hexane, 2-methylpentane,
3-methylpentane, 2,2-dimethylbutane, cyclohexane and n-hexane) [Atkinson, 1994]. These hydrocarbons were not added at this time because these hydrocarbons have not been observed in arctic
air.
Alkene reactions with OH, O3 , and NO3 are complete through C4 . Rate parameters are available [Atkinson, 1994] for the following alkenes which are not included in the original Master
Mechanism: 2-methylpropene, 1-pentene, cis- and trans-2-pentene, 3-methyl-1-butene, 2-methyl1-butene, 2-methyl-2-butene, 1-hexene, 2-methyl-1-pentene, 2-methyl-2-pentene, and trans-4methyl-2-pentene. These alkenes have not been observed in arctic air and were therefore not
added at this time.
The major loss processes of alkynes include reaction with OH, NO3, and O3 . The only alkyne
included in the master mechanism is C2 H2 . However, Atkinson [1994] lists rate data for propyne,
1-butyne, and 2-butyne. As acetylene is the only alkyne measured in arctic air, reaction of propyne
and butyne were not added. While the reaction with ozone is of negligible importance as a loss
process [Atkinson, 1994] (rate constants are on the order of 10,20 cm3 molecule,1s,1 ) the reaction
of acetylene with O3 was added to the Mechanism for completeness. The major products of the
reaction of C2 H2 with O3 are believed to be CO, CO2 , and HCOOH [DeMore et al., 1997].
For several of the NMHC, rate parameters are reported in the form of K=CTn exp ,D=T .
To compare these rate parameters to those used by Madronich and Calvert [1989], the Arrhenius
parameters A and B are calculated using the following expressions [Atkinson, 1994]:
A
B
B.1.2.2
=
=
CT n exp n
D + nT:
(B.2)
(B.3)
Alkyl Radicals
The overwhelming fate of the alkyl radicals (produced as a result of H-atom abstraction) is reaction
with O2 to form peroxy radicals. On average, 0.05% for C2 H5 , the reaction results in the production
of an alkene and HO2 , through the decomposition of the excited [RO2 ] radical.
C2H5 ! [C2H5 O2]
M CHO
!
[C2 H5 O2 ]
2 5 2
[C2 H5 O2 ]
! C2H4 + HO2
(B.4)
(B.5)
(B.6)
The alkyl radical reactions examined are listed in Table C.5.
B.1.2.3
Peroxy Radical Reactions
The peroxy radical reactions were updated using the methods of Kirchner and Stockwell [1996]. The
updated reactions include alkyl peroxy radical and acyl peroxy radicals with NO and HO2 , as well
161
Table B.1 Alkyl Radical Updates.
Reaction
0XCH3 O3
0XCH3 O2
0 CH3 O2 (M)
0 C2H5 O2
0 C2H5 O2 (M)
0 HCO O2
0 0o11 O2
k298
!
!
!
!
!
!
!
E/R
?
?
2011 (M)
C2H4 HO2
2021 XPOO (M)
CO HO2
CH2O HO2
Reference
2.6E-12 2.2E+02
<3.0E-16 0.0E+00
1.1E-12 -1.2E+03
<2.0E-14 0.0E+00
7.5E-12 -1.2E+03
5.5E-12 -1.4E+02
9.1E-12 0.0E+00
a Recommended by DeMore et al. [1997]
Madronich and Calvert [1989] a
Madronich and Calvert [1989]a
DeMore et al. [1997], see Table C.19
DeMore et al. [1997]
DeMore et al. [1997], See Table C.19
Madronich and Calvert [1989]a
DeMore et al. [1997]
as peroxy radical cross reactions. The rate constants at 298 K and the “activation temperatures,”
Ea /R, were updated as needed. The new rate constants and activation temperatures are listed in
Tables C.6–C.6. Each peroxy radical is believed to react with itself (self–reaction), any of the other
peroxy radicals which are present (cross–reaction), HO2 , NO, and NO2 . Recent work [LeBras, 1997;
Canosa-Mas et al., 1996] suggests that the peroxy radicals may also react with NO3 .
Reactions with NO The revised rate parameters for the reactions of peroxy radicals with NO
are shown in Table C.6. For the reaction of peroxy radicals with NO, experimental kinetic data
were used if available. If data were not available, as suggested by Atkinson [1994] the acyl peroxy
radicals were assigned the measured rate parameters of peroxy acetyl radical (k = 1.8 10,11 and
E/R = -3.6E+02 [DeMore et al., 1997]). For the alkyl peroxy radicals, the rate constants were set
equal to 4.010,12 molecule,1 cm3 s,1 [Kirchner and Stockwell, 1996]. For the reaction of the
larger alkyl peroxy radicals with NO there are two possible reaction pathways.
RO2 + NO
RO2 + NO
M
,!
,!
RONO2
(B.7)
RO + NO2
(B.8)
The rate constant ratio ka /(ka+kb ) depends on temperature, and pressure, and the number of carbons
in the molecule. The branching ratio of the rate constants for secondary alkyl peroxy radical can be
determined using the following Equation [Atkinson, 1994]:
0
1
300
,m
ka = B
B@ Yo [M](T=300) ,mo CCA F z
kb
where,
1+
(B.9)
Y300
o [M](T=300) o
Y300
1 (T=300),m1
8 "
<
:1 + log
,m
Y300
o [M](T=300) o
Y300
1 (T=300),m1
!#29
=,1
;
z
=
Y300
o
=
en
=
number of carbon atoms in the peroxy radical
n
(B.10)
(B.11)
(B.12)
162
and based on the evaluation of Atkinson [1994],
Y300
1
mo
m1
F
=
=
0:826
1:94 10,22cm3 molecule,1
=
0:97
=
0
=
=
(B.13)
(B.14)
(B.15)
(B.16)
8:1
(B.17)
0:411
(B.18)
The branching ratios for primary and tertiary peroxy radicals were calculated from the secondary
ratio, using the relations,
ka=kb)primary 0:40(ka=kb)secondary
(ka =kb)tertiary 0:30(ka=kb)secondary:
(
(B.19)
(B.20)
Note that the rate constant ratio calculated in this manner may be too high for –hydroxyalkyl
peroxy radicals [Atkinson, 1994].
Methylperoxy Radical Reaction with Nitric Oxide (CH3(OO.) + NO) The reaction
of CH3 O2 with NO is believed to result mainly in NO2 and CH3 O. Ravishankara et al. [1981]
report that at least 80% of the reaction results in NO2 production. Zellner et al. [1986] report the
yield of CH3 O to be 1.0 0.2. Williams [1994a] added a channel which produces methyl nitrate
(CH3 ONO2 , n011). However, in the absence of data showing this channel exists, the channel was
not included in model updates.
Ethylperoxy Radical Reaction with Nitric Oxide (CH3CH2 (OO.) + NO) Plumb et
al. [1982] report the channel which produces NO2 is responsible for at least 80% of the all C2 H5 O2 .
Maricq and Szente [1996] report, “The small negative temperature dependence is consistent with the
accepted mechanism of the reaction proceeding through a C2 H5 O2 NO adduct.” They also report,
“The product study of Atkinson et al. [1982b] shows that the reaction between these radicals and
NO proceeds to greater than 98% via the channel
C2 H5 O2 + NO ! C2 H5 O + NO2
(B.21)
C2 H5O2 + NO + M ! C2 H5ONO2 + M”
(B.22)
and that less than 2% occurs by
[Eberhard and Howard, 1996] report the branching ratio, kB:21/(kB:21+kB:22), is 0.014 for the
C2 H5 O2 radical [Atkinson et al., 1982b] and 0.02 for the n-C3 H7 O2 radical [Carter and Atkinson,
1989]. Eberhard and Howard [1996] also report that the negative temperature dependence can be
explained by the “formation of a bound reaction intermediate
RO2 + NO ! [ROONO]
! RO + NO2
(B.23)
163
Table B.2 Summary of Rate constants for Alkyl Peroxy Radicals with HO2 .
Functional Group
RACM Code
HC3P–HC5P
alcohol
alcohol
alcohol
org. nitrates
ketones
aromatics
acids
aldehydes
Ether
peroxy acid
hydroperoxides
PAN
unsaturated
nitro
OLP2
OLTP–OLIP
OLNN–OLND
KETP
TOLP,XYLP
Master-Mech Code
2011
2021
2031–2081
2o11
2o21
2o31–2o81
2n11–2nA1
2k33–2k71
2r61–2r82, 2t71–2tA1
2a21–2a53
2d21–2dA2
2e72
2g21,2g40
2h51–2h71
2p21–2p31
2u51–2u71
2v31
k at 298 K
5.6 10,12
8.0 10,12
1.3 10,11
1.2 10,11
1.0 10,11
1.3 10,11
1.3 10,11
9.0 10,12
1.0 10,11
1.3 10,11
1.3 10,11
1.3 10,11
1.3 10,11
1.3 10,11
1.3 10,11
1.3 10,11
1.3 10,11
E/R
-800
-700
-1300
-2300
-1300
-1300
-1300
-980
-1300
-1300
-1300
-1300
-1300
-1300
-1300
-1300
as postulated for the HO2 + NO and CH3 O2 + NO reactions.” Williams [1994a] added a reaction
channel resulting in the production of ethylnitrate (CH3 CH2 ONO2, n021). Because this reaction
pathway is believed to be insignificant, it was not included in model updates.
Reactions with HO2 Experimentally determined kinetic data were used for the reaction of
peroxy radicals with HO2 if available. Because there are so few available measurements, many
peroxy radicals are assigned the measured value of the peroxy radicals that they are most similar to,
following the methods of Kirchner and Stockwell [1996]. Table B.2 summarizes the rate constants
assigned to various groups of peroxy radicals for their reaction with HO2 . For many of the RO2
+ HO2 reactions Kirchner and Stockwell [1996] used an average E/R and rate constant. The E/R
value was the average of (CH3 )3 CCH2 O2 , c-C5 C9 O2 , and c-C6 H11O2 . The rate constant was an
average of the reactions for C2 H5O2 , HOCH2 CH2 O2 , (CH3 )3 CCH2 O2 , c-C5 C9 O2 , c-C6 H11O2 ,
and C6 H5CH2 O2 . These average values were assigned to peroxy radicals from alkanes (HC3P,
HC5P, HC8P), peroxy radicals from alkenes (OLTP, OLIP), and from alkene adducts with NO3
(OLNN, OLND). Peroxy radicals from ketones (KETP) and ethyl peroxy radical (OLP2) use only
the averaged E/R value, while their rate constants are based on measurements. The reaction rate
of ketones with HO2 are set equal to the reaction rate of CH3 C(O)CH2 O2 (2k33) with HO2. The
rate constants and E/R values for the reaction of aromatic compounds with HO2 are treated as
C6 H5 CH2 O2.
Each peroxy acyl radical reaction with HO2 has two possible reaction pathways [DeMore et al.,
1994; Kirchner and Stockwell, 1996], one producing a peroxy acid, -C(O)OOH, Reaction B.24, and
the other producing an acid, -C(O)OH, Reaction B.25.
R-C(O)OO + HO2
,!
R-C(O)OOH + O2
(B.24)
164
,!
R-C(O)OH + O3
(B.25)
Reaction pathway B.25 was not included in Stockwell et al. [1990]’s original mechanism or in
the Master Mechanism [Madronich and Calvert, 1989]. This second reaction pathway was added
using the rate constant, E/R value, and branching ratio recommended by [Kirchner and Stockwell,
1996] for the peroxy acetyl radical (3021). The rate constants and E/R values for reactions like
Reaction B.24 which were included in the Master Mechanism were altered to use the rate constants
recommended by Kirchner and Stockwell [1996]. A full list of the peroxy radical reactions with
HO2 is shown in Table C.7.
CH3 C(O)O2 + HO2 There are a number of recommendations for the reaction of peroxyacetyl radical with HO2 . The rate constant and activation temperature recommended by DeMore
et al. 1994, 1997 and Lightfoot et al. [1992] are taken from the study by Moortgat et al. [1989].
However, Lightfoot et al. [1992] suggests that their recommended rate constant may be too large.
In their model RACM, Stockwell et al. [1997] use the parameters from LeBras [1997] rather than
DeMore et al. [1994]. LeBras [1997] lists the rate constant for 3021 + HO2 from Moortgat et al.
[1989] as well as a study performed by Moortgat which was submitted as a 1991 LACTOZ annual
report. Due to the additional data taken into consideration, the model was altered to use the rate
constant used by Kirchner and Stockwell [1996], which is based on LeBras [1997].
Reactions with NO2 In the NCAR Master Mechanism-Version 2.0 there are only two reactions
of alkyl peroxy radicals with NO2 , the methylperoxy radical and C6 H5 O2. As the rate parameters
recommended by DeMore et al. [1997] for the reaction of methylperoxy radical with NO2 are
the same as those used in the Master Mechanism, that reaction was not altered. Reaction of alkyl
peroxy radicals with NO2 are typically insignificant compared to the other reactions of alkyl peroxy
radicals under most tropospheric conditions [Finlayson-Pitts and Pitts, 1999], as this reaction forms
peroxynitrates which rapidly undergo thermal decomposition back to reactants. Additional reactions
were therefore not added.
For the reactions of peroxy acyl radicals with NO2 experimentally determined rate parameters
were used if they were available. The high pressure limit rate constant recommended by DeMore
et al. [1997] (k298 = 8:6 10,12 molec,1 cm3 s,1 ) for the reaction of peroxyacetyl radical with
NO2 was used where experimental data did not exist.
Reactions with NO3 Only those peroxy radicals which have experimentally determined rate
constants for their reaction with NO3, methyl peroxy (2011) and peroxy acetyl (p021), were added
at this time. The reactions added are shown in Table C.9.
Self-reactions Rate constants and Ea /R values for reactions of peroxy radicals with themselves
were updated with experimentally determined data if available. Kirchner and Stockwell [1996]
provide a list of experimental measurements which were used in their study.
165
If an experimentally determined rate constant was not available, the following equation was used to
estimate the rate constant for peroxy radical self-reactions.
k 2 10,14 exp 3:8A , 5 + 1 + 03:02N 2 N
(B.26)
where,
k
A
A
N
=
rate constant in molecule,1 cm3 s,1
=
0, if there are no additional oxygen atoms in the alkyl group
=
1, if there are additional oxygen atoms in the alkyl group
=
number of alkyl or alkoxy groups connected to the C-O-O group
=
number of carbon atoms in the alkyl peroxy radical, N 7.
This equation was developed by Kirchner and Stockwell [1996] to fit the rate constants of peroxy
self reactions based on the following parameters: carbon number, branching structure (methyl,
primary, secondary, or tertiary), and electron withdrawing functional groups. Generally, as the
carbon number increases the rate constant increases, due to an increased stability of the transitional
states of the larger radicals. Steric effects decrease the rate constants in the order of methyl >
primary > secondary > tertiary.
There are several limitations to the use of Equation B.26. First, there are no measured rate
constants for peroxy radicals with a carbon number greater than 7. As recommended by Kirchner
and Stockwell [1996], if N> 7, the rate constant was estimated using equation B.26 with N set equal
to 7. This exception was applied to a number of peroxy radicals, including: 2081, 2d81, 2d82,
2dA2, 2nA1, 2o81, 2r81, 2r82, 2t81, 3k81, 3t91, and 3tA1.
The second limitation of using Equation B.26 involves the location of additional oxygen atoms.
Equation B.26 was developed from measurements of peroxy radicals with the oxygen atom attached
to or to the C-O-O group. It is not possible to know if the equation holds for peroxy radicals
containing an electron withdrawing group further away. For the compounds which have an additional
oxygen not attached to or to the C-O-O group, the parameter A was set equal to zero as
recommended by Kirchner and Stockwell [1996].
Third, Kirchner and Stockwell [1996] note that the rate constant is probably overestimated for
peroxy radicals containing 4 or more carbons which are derived from terminal HO-alkene adducts.
The authors recommend an upper limit of 8.0 10,12 molecule,1 cm3 s,1 for these reactions. In
the master–mechanism, none of the species with 4 or more carbons exceed the recommended upper
limit.
There are a number of non-specific species in the Master Mechanism which have the form
of Cx Hy (OO), where there are a number of possible isomers. For these compounds, a family
self-reaction rate constant was assigned based on the family assignments used by Madronich and
Calvert [1989]. Madronich and Calvert [1989]’s primary, secondary, and tertiary assignments were
also followed for the aromatic compounds (2r61, 2r62, 2r63, 2r71, 2r72, 2r73, 2r74, 2r75, 2r81,
2r82) and alpha-pinene and its derivatives (2tA1, 3r71, 3t91, 3tA1).
166
Table B.3 Activation Temperatures for Peroxy Radical Self
Reactions.
If A=0, use Equation B.27.
If A=0 because the O group is terminal, Ea /R = -1000 K.
If A=1, then Ea /R = 1000 K.
If N>7, then Ea /R = -2000 k.
There were two compounds, 2m12 and 2m23, in the master mechanism where the peroxy group
was attached to a nitrogen atom rather than a carbon. Because Equation B.26 was developed only
with alkyl peroxy and acyl peroxy radicals, I didn’t feel that it could be used to calculate the selfreaction rate for these two compounds. The rate constants for these two compounds were unaltered
from Madronich and Calvert [1989].
If experimental activation temperatures (E/R) are available, they were used. Otherwise E/R
was assigned following the methods of Kirchner and Stockwell [1996] which is summarized in
Table B.3.
Kirchner and Stockwell [1996] developed Equation B.27 to estimate the activation temperature
(Ea /R), for self-reactions of species with no additional oxygen atoms in the alkyl group.
Ea=R 2800 , 700 N , 1300
(B.27)
Since there are no experimental values which are less than -2000 K, this is used as the limiting value
for large N. If there is an additional oxygen atom, then Kirchner and Stockwell [1996] recommend
using an Ea /R value of 1000 K.
Methylperoxy Radical Self Reaction The recommendation of DeMore et al. [1997] is
unchanged from the recommendation made in 1994 [DeMore et al., 1994]. The self reaction has
been estimated using UV absorption techniques to measure k/ . DeMore et al. [1997] calculate the
rate constant using the average at 250 nm from Sander and Watson [1981], Kurylo et al. [1987],
Dagut and Kurylo [1990], Jenkin et al. [1988], Lightfoot et al. [1990] and the weighted average of
k/ at 250 nm from Cox et al. [1980], Sander and Watson [1981], McAdam et al. [1987], Kurylo
et al. [1987], Jenkin et al. [1988], Lightfoot et al. [1990], and Simon et al. [1990]. DeMore et
al. [1997] admits some apprehension about using this technique, “It is not clear whether the above
procedure of recalculating k using an average value of is valid. Therefore, the quoted error limits
encompass the values of k calculated by various authors.”
Kirchner and Stockwell [1996] use the recommendation from Lightfoot et al. [1992]. Lightfoot
et al. [1992] includes more studies and more recent studies in their review than DeMore et al.
[1997]. Because it is a detailed review of peroxy radical chemistry the model was altered to use the
self reaction rate parameters recommended by Lightfoot et al. [1992].
Cross-reactions In the master mechanism, methyl peroxy radical cross reactions are treated
explicitly. A list of these reactions and their revised rate parameters are shown in Table C.10.
A counter scheme is used for all other peroxy radical cross reactions as described by Madronich
167
and Calvert [1990]. The counter scheme involves dividing the peroxy radicals into the following
families: primary, secondary, tertiary, and acyl. Each peroxy radical reacts with each of the counters,
shown in Table C.11. The rate constants for the cross reactions are determined by taking twice the
geometric average (Equation B.28) of the self–reaction rate constants. (For the counters this is the
recommended self-reaction rate of the family to which the peroxy radicals belongs.)
k12 = 2(k1k2 )1=2
(B.28)
where, ki is the self–reaction rate constant for the family of each of the peroxy radicals, and k12 is
the cross–reaction rate constant for the two peroxy radicals.
Kirchner and Stockwell [1996] also recommend using Equation B.28 to calculate the cross
reaction rate constants. They chose to treat the peroxy cross reactions with methyl peroxy radical
(2011) and peroxy acetyl radical (3021) explicitly because 2011 and 3021 are the most prevalent
organic peroxy radicals. In addition, the self reactions of 2011 and 3021, and their cross–reactions
2011 + 3021, 2011 + RO2, and 3021 + RO2, have been shown to be the most important peroxy-peroxy
radical reactions [Stockwell et al., 1990; Stockwell, 1995]. No other peroxy radical cross reactions
were included by Kirchner and Stockwell [1996] because of “their apparently low importance”
[Stockwell et al., 1990].
To determine whether it is important to treat peroxy acetyl radical (3021) cross reactions
explicitly, as Kirchner and Stockwell [1996] do, the loss rates for the peroxy acetyl radical were
examined for a simulation typical of arctic outflow events. For the peroxy acetyl radical, reactions
with NO, NO2, and HO2 were significantly faster than reactions with methylperoxy radical and
the counters. For peroxy radicals the reactions with NO and HO2 are typically the fastest with the
reactions with the counters being the slowest. Of the reactions of peroxy radicals with the counters,
the reaction with the peroxy acyl counter is typically fastest. At this time explicit reactions of
peroxy radicals with peroxy acetyl radical were not added.
The counter method was modified to obtain better estimates of the cross reaction rate constants
for all peroxy radicals. Instead of using the generalized family rate constants for both the peroxy
radical and the counter in Equation B.28, the self–reaction rate constant calculated in Section B.1.2.3
was used for the peroxy radical rate constant and the family rate constant was used for the counter.
The family rate constants recommended by Atkinson [1994] were used for primary, secondary, and
tertiary counters, while the acyl counter rate was from Madronich and Calvert [1990].
The activation temperature terms, Ea/R, for cross reactions have large uncertainties. As in
Kirchner and Stockwell [1996] the Ea/R values are calculated using Equation B.29.
Ea=R
=
Ea1=R + Ea2=R
2
(B.29)
CH3O2 + CH3 C(O)O2 The reaction of methyl peroxy radical with peroxyacetyl radical has two
paths [DeMore et al., 1997]:
CH3C (O)O2 + CH3 O2 !a CH3 C (O)O + CH3 O + O2
!b CH3 C (O)OH + CH2O + O2
(B.30)
(B.31)
168
There seems to be some disagreement over the branching ratios for this reaction. Horie and Moortgat
[1992] found ka/kb=2.2106 exp-3280/T = 5.96 at 298 K. Roehl et al. [1996] recommends
ka/kb=0.9 at 298 K and Atkinson [1994] suggests that the pathways have equal importance. However,
Maricq and Szente [1996] suggest that channel b is the only pathway operable below 298 K. The
branching ratio used by Madronich and Calvert [1989] is within this range of values with ka/kb=2.3
at 298 K. Therefore, no alteration of the branching ratio was made. The rate constant recommended
by DeMore et al. [1997] was used.
B.1.2.4
Alkoxy Radicals
Alkoxy radicals can react with O2 , NO, or NO2, decompose, or isomerize. The reaction with O2 is
dominant for the small, simple alkoxy radicals, while for larger alkoxy radicals, decomposition and
isomerization become more important. The reactions with NO and NO 2 are of minor importance.
Due to the difficulty in estimating the importance of the various reactions for each alkoxy radical
and the estimated unimportance of these reactions to ozone production in arctic outflow events, the
rate parameters for the alkoxy radicals remain largely unchanged. Below is a discussion of the
reactions that alkoxy radicals undergo along with a description of steps that were taken to verify
that the type of reaction makes little difference to ozone chemistry in arctic outflow.
Reaction with O2 The reaction of alkoxy radicals with O2 produces a carbonyl and HO2.
R1 CH(O: )R2 + O2
!
R1COR2 + HO2
(B.32)
Atkinson [1994] recommends a rate constant for the reaction of O2 with primary alkoxy radicals
k(RCH2 O + O2 )
=
=
6:0 10,14e,(550=T) cm3molecule,1 s,1
9:5 10,15cm3 molecule,1 at 298 K
(B.33)
(B.34)
and for secondary alkoxy radicals
k(R1R2CH2O + O2 )
=
=
6:0 10,14e,(550=T) cm3molecule,1 s,1
9:5 10,15cm3 molecule,1 at 298 K.
(B.35)
(B.36)
However, these recommendations only apply to alkoxy radicals formed from alkanes. Atkinson
[1990] has slightly different recommendations, but applies them to substituted alkoxy radicals.
Atkinson [1994] also reviews expressions derived for the reaction with O2 using the number of
abstractable H atoms and the heat of reaction. The following expression is proposed by Atkinson
and Carter [1991]
k(RO + O2 ) = 1:3 10,19 ne,(0:32∆HO ) cm3molecule,1 s,1
2
(B.37)
at 298 K, where n is the number of abstractable H atoms and ∆HO2 is the heat of reaction. Atkinson
[1994] uses this expression in the comparison of alkoxy radical reactions. In order to estimate the
169
rate constant for the reaction with O2 , the heats of reaction must be determined. As there are only a
handful of these values [Atkinson et al., 1992b], an estimation technique must be used. Alternatively,
the recommendation for primary and secondary alkoxy radicals could be used, although explicit
treatment of these species would be lost.
Atmospheric Implication The alkoxy radical reactions with O2 produce HO2 radicals, an
important source of OH, converting NO to NO2 in the process.
HO2 + NO ! NO2 + OH
(B.38)
Photolysis of carbonyls, formed from alkoxy radical reactions with O2, also produce HO2 . However,
this is an insignificant route for HO2 formation.
To determine whether the formation of HO2 from alkoxy radicals is important, the rate of
HO2 formed from the alkoxy radicals was compared to the total rate of formation of HO2 . For the
simulation used, the maximum rate of formation of HO2 is 700 pptv/hr. The sum of the maximum
rates of formation of HO2 from alkoxy radicals is 34 pptv/hr. If all the alkoxy radicals formed are
assumed to react completely with O2, there is a negligible effect on the rate of HO2 formation, and
therefore the effect on OH levels is negligible.
Decomposition The decomposition of alkoxy radicals results in a carbonyl and an alkyl radical
which in the presence of O2 becomes a peroxy radical.
R1C(O: )(R2)R3
decomposition
!
!
R:1 + O2
R:1 + R2 COR3
R1(OO: )
(B.39)
(B.40)
Isomerization The larger alkoxy radicals may also isomerize, producing alkyl radicals which
react with O2, resulting in substituted alkylperoxy radicals.
R1CH2CH2 CH2 CH(O: )R2
:
R1 CHCH2CH2 CH(OH)R2
:
isomerization
!
R1CHCH2 CH2 CH(OH)R2
O2
:
!
R1C(OO )HCH2 CH2 CH(OH)R2
(B.41)
(B.42)
The alkoxy radical isomerizations and decompositions in the presence of O2 result in the production
of peroxy radicals. The peroxy radicals will convert an additional NO molecule to NO2 without
consuming an O3 molecule, before becoming a different alkoxy radical, which may then react with
O2 , decompose, or isomerize.
Comparison of the first order rate constants indicate that the branching ratios used by Madronich
and Calvert [1989] for the unsubstituted alkoxy radicals and the single alkoxy radical containing a
ketone are in agreement with those estimated by Atkinson and Carter [1991] which are tabulated
in Atkinson [1994]. However, for the alkoxy radicals containing an alcohol group, the branching
ratios estimated by Atkinson and Carter [1991] were very different than those used by Madronich
and Calvert [1989], and some even result in different dominant reaction pathways.
170
To determine whether the branching ratio of alkoxy radicals is significant to peroxy radical
production, the formation rate of alkoxy radicals is compared to the formation of peroxy radicals.
The sum of the peroxy radical rate of formation is 230 pptv/hr, while the alkoxy radical rate of
formation is only 34 pptv/hr. Therefore, it is believed that the alkoxy radical branching ratios have
a negligible affect on the production of peroxy radicals in arctic outflow events.
Reaction with NO and NO2 Alkoxy radicals may also react with NO to produce alkyl nitrites,
carbonyls and HNO, or react with NO2 to produce alkyl nitrates, carbonyls, and nitrous acid
(HONO).
R1CH(O: )R2 + NO
R1CH(O: )R2 + NO2
!a
!b
!a
!b
R1CH(R2 )ONO
(B.43)
R1COR2 + HNO
(B.44)
R1CH(R2 )ONO2
(B.45)
R1COR2 + HONO
(B.46)
Methoxy Radical Reaction with Nitric Oxide (CH3O + NO) The reaction of methoxy
radical (CH3 O) with NO mainly results in the formation of methyl nitrite, CH3 ONO, with a fraction
decomposing into CH2 O and HNO. It is difficult to derive a bimolecular rate constant because the
fraction which decomposes is dependent on temperature and pressure. However, DeMore et al.
[1997] were able to determine an upper limit of k< 8E-12 cm2molecule,1 s,1 from the studies by
Frost and Smith [1990a] and Ohmori et al. [1993]. The reaction of methoxy with nitric oxide was
not included in the Master Mechanism [Madronich and Calvert, 1989]. Both the bimolecular and
termolecular reactions were added to the mechanism, with parameters taken from DeMore et al.
[1997].
CH3 O + NO
CH3 O + NO + (M)
!
!
CH2 O + HNO
(B.47)
CH3 ONO
(B.48)
Methyl nitrite (CH3 ONO, w012) was added to alphadict.dat. As alkyl nitrites photolyze rapidly
RONO + hv
! RO + NO
(B.49)
and to prevent a buildup of methyl nitrite, the photolysis reaction of methyl nitrite which produces
CH3 O and NO was added, using twice the cross section of HNO2 and a quantum yield of unity.
See Section B.3.3 for further discussion of the photolysis of added alkyl nitrites.
Methoxy Radical Reaction with Nitrogen Dioxide (CH3O + NO2 ) DeMore et al.
[1997] recommends both a bimolecular and termolecular pathway for the reaction of methoxy
radical with NO2 :
CH3 O + NO2
CH3 O + NO + (M)
!
!
CH2 O + HONO
CH3 ONO2 :
(B.50)
(B.51)
171
The bimolecular reaction (B.50) was a new reaction in DeMore et al. [1997], however the reaction “is
not meant to represent a bimolecular metathesis reaction.” It represents the fraction of the reaction
which yields CH2 O and HONO [DeMore et al., 1997]. In the original mechanism there was a
bimolecular reaction which resulted in the production of CH3 ONO2 (n011). The mechanism was
changed to use the kinetic and mechanistic parameters recommended by DeMore et al. [1997]. This
includes changing the bimolecular reaction to a termolecular reaction (keeping the same products)
and adding a new bimolecular reaction resulting in CH2 O and HONO.
Ethoxy Radical Reaction with Nitric Oxide (CH3CH2(O.) + NO) The reaction of ethoxy
radical with NO was not included in the Master Mechanism [Madronich and Calvert, 1989]. The
recommendation of DeMore et al. [1997] for this reaction is based on the studies of Frost and
Smith [1990a] for the high pressure measurements and Daële et al. [1995] for the low pressure
measurements scaled to fit an expression summing the bimolecular and termolecular reactions.
The bimolecular channel has not yet been verified, but has an estimated rate constant of 10,12 .
The model was altered to include the following termolecular reaction using the rate parameters
recommended by DeMore et al. [1997].
CH3 CH2 O + NO + (M) ! CH3 CH2 ONO + (M)
(B.52)
Like methyl nitrite, a photolysis reaction was added for the ethyl nitrite (CH3 CH2 ONO, w022)
formed. See Section B.3.3 for more information on the photolysis parameters.
Ethoxy Radical Reaction with Nitrogen Dioxide (CH3CH2 (O.) + NO2) The recommendation of DeMore et al. [1997] for the high pressure rate constant of C2 H5 O + NO2 to form
C2 H5 ONO2 is based on the work of Frost and Smith [1990b], while the other values are estimated.
This reaction was altered from a bimolecular reaction to a termolecular reaction as recommended
by DeMore et al. [1997]. Rate parameters are listed in Tables C.14 and C.19.
B.1.2.5
Oxygen Containing Organics
The reactions involving oxygenated organic compounds, such as carbonyls, alcohols, carboxylic
acids, and hydroperoxides, which were examined are shown in Tables C.13–C.14.
Carbonyls In the atmosphere, carbonyls photolyze and react with OH, NO3, and HO2 . The
photolysis reactions are discussed in Section B.3.4. The thermal carbonyl reactions which were
examined are shown in Table C.13.
Reaction with OH The carbonyl reactions with OH occur by H–atom abstraction. For aldehydes
the relatively weak aldehydic hydrogen is abstracted [Finlayson-Pitts and Pitts, 1999]. DeMore et
al. [1997] provide rate constants for C1–C3 aldehydes while Atkinson [1994] provided rate constants
172
for C1–C5 aldehydes. The only compound in these reviews that was not included in the master
mechanism [Madronich and Calvert, 1989] was 2,2-dimethylpropanal (CH3 C(CH3 )(CH3 )CHO).
The reactions of OH with the ketones are complete through C5. Atkinson [1994] lists rate constants
for C6 and larger ketones. However, the reactions were not added to the mechanism, as this update
focuses on C4 compounds.
CH2(OH)CHO (do23) + OH As indicated in Table C.13, the branching ratio for this reaction
was changed. The reaction proceeds through H-atom abstraction from the C-H bonds.
CH2 (OH)CHO + HO
A
!
B
!
H2 O + HOCH2 C.(O)
H2 O + HOC.HCHO ! CHOCHO
(B.53)
(B.54)
Atkinson et al. [1992b] recommends the branching ratio obtained by Niki et al. [1987]. The branching ratio is 80% through Channel A, Equation B.53 and 20% through Channel B, Equation B.54. In
the Master Mechanism [Madronich and Calvert, 1989], it is assumed that the HOCH2 C.O formed
in Equation B.53 reacts with O2 to produce a peroxy acetyl radical.
HOCH2 C.(O) + O2
! HOCH2 C(O)OO.
(B.55)
A temperature dependence for the reaction of do23 with OH was not reported by Atkinson et
al. [1992b] or Atkinson [1994]. As most of the other species with aldehyde and alcohol functional
groups included in the Master Mechanism [Madronich and Calvert, 1989] show no temperature
dependence, the E/R value for do23 was set equal to zero.
CH3COCOCH3 (kk43) + OH The reaction of biacetyl (CH3 COCOCH3 , kk43) with OH was
added to the mechanism. The rate constant was set equal to that recommended by Atkinson [1994].
The products were based on the reaction occurring by H–atom abstraction followed by the addition
of O2 .
C2 H5COC2H5 (k052) + HO Williams [1994a] added the reaction of 3-pentanone
(CH3 CH2 COCH2 CH3 , k052) with OH, leading to the production of 4-peroxy-2-pentanone
(CH3 COCH2 CH(OO.)CH3 , 2k52). To be consistent with the location of the ketone group, the
product was changed to 2-peroxy-3-pentanone (CH3 CH2 COCH(OO.)CH3 , 2k53).
C5 H12CO (k062) + HO While k062 is a non-specific C6 ketone formed from non–specific
compounds, the reaction products are consistent with the reaction of 3-hexanone with OH. The
rate constant for k062 + OH was set equal to the geometric average of the hydroxyl reactions of
2-hexanone and 3-hexanone reported by Atkinson [1994].
Reaction with NO3 The NO3 reactions, which also proceed through H–atom abstraction are
expected to be of minimal importance with rate constants on the order of 10,17 to 10,15. However,
173
they may become significant in nighttime chemistry. Rate constant data are available only for
aldehydes: formaldehyde, acetaldehyde, and glyoxyl [Atkinson, 1994]. The reactions which were
revised are shown in Table C.13.
Reaction with HO2 The reaction of HO2 has been shown to occur for several aldehydes:
formaldehyde (CH2 O), acetaldehyde (CH3 CHO, d021), and gloxal ((CHO)2 , dd21) [Atkinson,
1994]. The reaction with HO2 is expected to proceed through addition followed by isomerization
of the intermediate, resulting in a peroxy radical, e.g.,
CH2 O + HO2
! [HOOCH2 O.] ! CH2 (OH)(OO).
(B.56)
This type of reaction is expected to be unimportant due to the rapid decomposition of the peroxy
radicals back to HO2 and the aldehyde. While Atkinson [1994] provides rate parameters for the
reaction of HO2 with acetaldehyde and glyoxyl, the peroxy radicals do not exist in the Master
Mechanism. Because these reactions are believed to be negligible, they were not added.
Alcohols The reaction of alcohols with OH and NO3 are shown in Table C.14. Madronich and
Calvert [1989] include the reaction of C1–C3 alcohols with OH. The reactions of C4 alcohols were
added to the mechanism, using the rate constants provided by Atkinson [1994]. Branching ratios
were calculated using Atkinson, Atkinson and Aschmann [1987, 1989]. Products were assigned
assuming the reactions proceed through H–atom abstraction from both the C-H and O-H bonds.
While rate constants for C5 alcohols were also tabulated by Atkinson [1994], these reactions were
not added.
While the reaction of alcohols with NO3 are slow, upper limits have been determined for C1–C3
compounds. The reaction of methanol, ethanol, and propanol with NO3 were added. The products
of these reactions are based on H–atom abstraction.
Carboxylic Acids The reactions of carboxylic acids with OH which were examined are in
Table C.14. Recommendations were only available for only a few species. The reaction with OH is
slow with a lifetime due to OH removal being 30–50 days [Atkinson, 1994]. It is most likely that
these compounds will be removed by wet or dry deposition.
Hydroperoxides The hydroperoxide-containing organic compounds that were changed or verified are listed in Table C.15. A number of hydroperoxide reactions (photolysis and reaction with
OH) were added by Williams [1994a]. These reactions were added to provide a loss reaction for the
hydroperoxides formed from the new alkyl nitrate reactions. The photolysis reactions are discussed
in Section B.3.2.
The reactions added by Williams [1994a] were included in the changes to the mechanism. The
rate constants used fall within the range of other nitrate-containing hydroperoxide reactions included
in the original mechanism.
174
h031 + OH The product was changed by Williams [1994a] from CH3 CH2 CH2 (OO.) (2032)
to CH3 CH(OO.)CH3 (2031), which is consistent with H-atom abstraction from the OOH group.
CH3 CH(OOH)CH3 + HO ! 0:5CH3CH(OO)CH3 + 0.5 CH3 COCH3 + 0.5 HO
B.1.2.6
(B.57)
Nitrogen Containing Organics
Alkyl Nitrates The major loss processes of alkyl nitrates are reaction with OH and photolysis.
For larger alkyl nitrates, C5, the reaction with OH is dominant, while for smaller alkyl nitrates
the photolysis reaction becomes competitive [Roberts, 1995].
The alkyl nitrate reaction with OH proceeds through H–atom abstraction from a C–H bond,
producing alkyl radicals. The radicals then react with O2 in the presence of NO to produce an
alkoxy nitrate, shown here for ethyl nitrate.
CH3 CH2 (ONO2 ) + HO
CH2 CH2 (ONO2 )
CH2 (OO)CH2 (ONO2 ) + NO
!
O2
!
!
CH2 CH2 (ONO2 )
CH2 (OO)CH2 (ONO2)
CH2 (O)CH2 (ONO2) + NO2
(B.58)
(B.59)
(B.60)
Table C.16 summarizes the changes made to the alkyl nitrate rate constants for their reaction with
OH.
Photolysis of alkyl nitrates result in the cleavage of the O–NO2 bond, producing an alkoxy
radical and NO2 .
(B.61)
CH3 CH2 (ONO2 ) + hv ! CH2 CH2 (O) + NO2
The lifetime for C2-C4 alkyl nitrates considering photolysis is 15–30 days [Atkinson, 1994].
Photolysis reactions were added for C2-C5 alkyl nitrates (n021, n031, n032, n041, n042, n053,
n054, n055), using the reactions Williams [1994a] generated. Additionally, a photolysis reaction
was added for n043. The photolysis reactions produce alkoxy radicals and NO2 . The absorption
cross sections and quantum yields were set to match the recommendations of Atkinson [1994]. The
photolysis of alkyl nitrates is discussed further in Section B.3.3.
Hydroxyl radical reactions with the following C2–C5 alkyl nitrates were added to the Master
Mechanism: n021, n031, n032, n041, n042, n053, n054, n055. The reactions were generated by
Williams [1994a] using a mechanism generator. The reactions proceed through H–atom abstraction.
If an abstractable hydrogen is on the carbon attached to the nitrate, this results in the production of
a carbonyl and NO2 .
(B.62)
CH3 (ONO2 ) + HO ! CH2 O + NO2
Overall rate constants were compared to DeMore et al. [1997] for n011 and n021; Talukdar et
al. [1997] for n021 and n031; and Atkinson [1994] for all others except n054 for which there were
no rate constants available. Atkinson [1994] recommends using the method developed by Atkinson
[1987] as revised by Atkinson and Aschmann [1989] to estimate the product distribution of the
175
Table B.4 Comparison of Alkyl Nitrate Branching Ratios.
RONO2
n021
product
CH2(O2 )CH2(ONO2)
CH3CHO + NO2
Total
n031
CH2(OO.)CH2CH2(ONO2)
CH3CH(OO.)CH2(ONO2)
CH3CH2CHO + NO2
n032
CH2(OO.)CH(ONO2)CH3
CH3COCH3 + NO2
n041
CH2(OO.)CH2CH2CH2(ONO2)
CH3CH(OO.)CH2CH2(ONO2)
CH3CH2CH(OO.)CH2(ONO2)
CH3CH2CH2CHO + NO2
Total
Total
Total
n042
CH2(OO.)CH2CH(ONO2)CH3
CH3CH(OO.)CH(ONO2)CH3
CH3CH2COCH3 + NO2
CH3CH2CH(ONO2)CH2(OO.)
n053
CH2(OO.)CH2CH2CH2CH2(ONO2)
CH3CH(OO.)CH2CH2CH2(ONO2)
CH3CH2CH(OO.)CH2CH2(ONO2)
CH3CH2CH2CH(OO.)CH2(ONO2)
CH3CH2CH2CH2CHO + NO2
Total
Total
n054
CH2(OO.)CH2CH2CH(ONO2)CH3
CH3CH(OO.)CH2CH(ONO2)CH3
CH3CH2CH(00.)CH(ONO2)CH3
CH3CH2CH2COCH3 + NO2
CH3CH2CH2CH(ONO2)CH2(OO.)
Total
n055
CH2(OO.)CH2CH(ONO2)CH2CH3
CH3CH(OO.)CH(ONO2)CH2CH3
CH3CH2COCH2CH3 + NO2
Total
Atkinson
4.32E-14
1.5084E-13
1.94e-13
5.573E-14
2.51E-14
1.946E-13%
5.017e-13
4.32E-14
3.394E-13
3.73e-13
1.858E-13
1.081E-12
3.243E-13
1.786E-12
3.737E-12
1.858E-13
2.514E-13
5.48E-13
1.028E-12
2.013E-12
1.858E-13
1.08E-12
1.3945E-12
3.243E-13
1.9458E-13
3.179E-12
1.8576E-13
1.08102E-12
2.27014E-13
2.3607E-13
3.024E-14
1.76E-12
1.858E-13
2.514E-13
4.249E-13
8.62E-13
%
22%
78%
11.1%
50.1%
38.8%
11.6%
88.4%
10.4%
60.5%
18.2%
10.9%
18.0%
24.4%
53.3%
4.2%
Williams
5.5E-14
4.3E-13
4.85E-13
2.7E-13
2.9E-13
1.7E-13
7.3E-13
6.0E-14
1.8E-13
2.4E-13
%
11.3%
88.7%
1.3E-12
90.9%
87.8%
1.3E-13
1.43E-12
2.0E-13
1.8E-13
2.5E-13
9.1%
12.2%
1.65E-12
22.2%
24.4%
53.3%
37.0%
39.7%
23.3%
25%
75%
31.7%
28.6%
39.7%
6.3E-13
5.8%
34.0%
43.9%
10.2%
6.1%
1.1E-12
1.4E-12
This work
22%
78%
1.8E-13
11.1%
50.1%
38.8%
7.3E-13
11.6%
88.4%
2.9e-13
9.2E-13
44%
56%
43.6%
56.4%
6.1%
1.81E-12
2.5E-12
10.6%
61.4%
12.9%
13.4%
1.7%
1.2E-12
2.7E-13
2.7E-13
69.0%
15.5%
15.5%
70.0%
14.7%
15.3%
21.5%
29.2%
49.3%
1.74E-12
3.8E-13
3.6E-13
3.1E-13
1.05E-12
36.2%
34.3%
29.5%
1.74E-12
21.5%
29.2%
49.3%
1.12E-12
176
reaction of C4 alkyl nitrates with OH. This technique was used for comparison to the branching
ratios used by Williams [1994a], shown in Table B.4.
The dominant branches used by Williams [1994a] were the same as those calculated using the
estimation technique [Atkinson and Aschmann, 1989] for all of the added alkyl nitrate reactions
with OH except for n055. The common dominant branches resulted from H–atom abstraction on
secondary carbons or CH(ONO2 ). In addition, the branching ratios from Williams [1994a] and
Atkinson and Aschmann [1989] where within 20% of each other.
Methyl Nitrate, n011 There is a large discrepancy between measured rates for the reaction of
methyl nitrate with hydroxyl. The rates measured by Kerr and Stocker [1986] and Nielsen et al.
[1991a] are 10 times larger than the rates measured by Gaffney et al. [1986] and Talukdar et al.
[1997]. The recommendation of Atkinson [1990] is based on the rate measured by Gaffney et al.
[1986]. DeMore et al. [1997] favor the lower values of Gaffney et al. [1986] and Talukdar et al.
[1997] due to the extensive study of Talukdar et al. [1997]. DeMore et al. [1997] recommends
the temperature dependence of Talukdar et al. [1997]. The mechanism was revised to use the
parameters recommended by DeMore et al. [1997].
Ethyl Nitrate, n021 Like methyl nitrate, there is a large difference in the measured rate constants.
The rate constant measured by Kerr and Stocker [1986] and Nielsen et al. [1991b] is about 3 times
larger than that measured by Talukdar et al. [1997]. The rate constant recommended by DeMore
et al. [1997] is based on the study of Talukdar et al. [1997]. This rate at 298 K is consistent with
that calculated using the estimation technique of Atkinson, Atkinson and Aschmann [1987, 1989].
Williams [1994a] used the value measured by Kerr and Stocker [1986]. The model was altered to
use the rate constant and temperature dependence recommended by DeMore et al. [1997]. The rate
measured by Talukdar et al. [1997] is reported as k = A1 exp(,E1=RT ) + A2 exp(,E2=RT ),
which was fit to the Arrhenius equation by DeMore et al. [1997].
n-Propyl Nitrate, n031 The rate constant was changed to use the value from Atkinson [1994]
which is based on the work of Kerr and Stocker [1986], Atkinson [1989], and Nielsen et al. [1991a].
This rate may be too high because it is based on studies which were had a much larger rate for
methyl and ethyl nitrate than the current recommendations of DeMore et al. [1997]. The estimation
technique [Atkinson, 1987; Atkinson and Aschmann, 1989] was used to determine the branching
ratios.
i-Propyl Nitrate, n032 Atkinson [1994] lists a rate constant of 4.910,13 cm3 molecule,1 s,1
at 298 K for the reaction of i-propyl nitrate with OH. This rate constant was studied extensively by
Talukdar et al. [1997] who report a temperature dependent rate of:
k(T )
k(298)
=
=
4:3 10,12 exp(,1250=T ) + 2:5 10,13 exp(,32=T )
2:9 10,13 cm3 molecule,1 s,1
(B.63)
(B.64)
177
The mechanism was revised to use the temperature dependent rate determined by Talukdar et al.
[1997]. Arrhenius parameters were determined using the linear fit of the plot of 1/T vs ln(K) over
the temperature range of 220-410 K. This produces the following:
kn032+HO (T )
kn032+HO (298 K )
=
=
8:5 10,13 exp(,306=T ) for T=220-410 K
3:0 10,13
(B.65)
(B.66)
The model was altered to use the rate constant at 298 K from Talukdar et al. [1997]’s temperature
dependent rate equation, the branching ratio estimated from Atkinson, Atkinson and Aschmann
[1987, 1989], and the temperature dependence from the Arrhenius fit of the rate reported by
Talukdar et al. [1997].
C4 and C5 Alkyl Nitrates The rate constants for the C4 and C5 alkyl nitrates with OH are from
Atkinson [1994]. The branching ratios were estimated using the estimation technique of Atkinson and
Aschmann [1989]. The fraction of the reaction which proceeded through a channel which was not
added by Williams [1994a], was added to a channel of the same type of H–atom abstraction, if it existed. For example for n042, the channel which produces CH3CH2CH(ONO2)CH2(OO.) is H–atom
abstraction on a primary carbon. The fraction which goes through this channel, 4.2%, is added to the
more dominant primary H–atom abstraction channel which produces CH2(OO.)CH2CH(ONO2)CH3.
If there are no other similar reactions, for example neither primary H–atom abstraction channels
were previously included in the n054 reaction with OH, the fraction was proportionately split between the remaining channels. The branching ratios used in this work are included in Table B.4.
The branching ratios used are similar, within 20%, to those used by Williams [1994a].
For the C4 and C5 alkyl nitrate reactions with OH, E/R values were not reported by Atkinson
[1994] due to a lack of available temperature dependent data. Because most of the activation
temperatures generated by Williams [1994a] are close to or within the range of E/R values for
methyl and i-propyl nitrate, the activation temperatures from Williams [1994a] were used.
Atkinson [1994] listed rate constants for the reaction of a number of alkyl nitrates with HO
which were not added to the Master Mechanism due to their size, C5, and the absence of data
suggesting these compounds are present in arctic air at non-negligible levels. These alkyl nitrates
include: 2-methyl-3-butyl nitrate (n052), 2,2-Dimethyl-1-propyl nitrate, 2-hexyl nitrate, 3-hexyl
nitrate, cyclohexyl nitrate, 2-Methyl-2-pentyl nitrate, 3-Methyl-2-pentyl nitrate, 3-heptyl nitrate,
and 3-octyl nitrate.
nd50 The structure of a functional group in the compound nd50, formed by NO reaction with
2d5A, was changed in the alphadict.dat file from a peroxy nitrate group (O2 NO2 ) to a nitrate group
(ONO2 ).
Peroxy Acyl Nitrates The changes made to the peroxy acyl nitrates are shown in Table C.17.
178
PAN The formation of PAN is listed in DeMore et al. [1997] as being best described by the
Troe expression. The decomposition is calculated from the equilibrium constant also provided by
DeMore et al. [1997]. The pathway which produced methyl nitrate, n011, was removed as it is
believed the only products from the decomposition are peroxyacetyl radical and NO2 [DeMore et
al., 1997].
PPN Atkinson [1994] reported the thermal decomposition of PPN as measured by Schurath
and Wipprecht [1980] and Mineshos and Glavas [1991]. The model was altered to use the geometric
average of rate constants at 298 and the arithmetic average for the temperature dependence.
Other Peroxy Acyl Nitrates For the thermal decomposition of larger peroxy acyl nitrates,
Atkinson [1994] recommends k = 41016 exp (,13600=T ). Madronich and Calvert [1989], assigned the same rate constant and activation temperature to all the peroxy acyl nitrates, except for
pr71, which is the only aromatic peroxy acyl nitrate. The rate constants for all the peroxy acyl
nitrates (p*** species) were changed to the recommendation of Atkinson [1994] except for p021,
p031, and pu44 for which measurements exist and pr71 which remained unaltered. The compound
pr71 is the only aromatic peroxy acyl nitrate and had a different rate constant than the other peroxy
acyl nitrates in the original mechanism.
B.1.2.7
Aromatics
The only aromatic reactions examined are those of benzene and the resulting compounds. Table C.18
is a summary of the changes made to the aromatic chemistry.
Benzene Oxidation The oxidation of benzene by OH is believed to result in the the formation of
hydroxycyclohexadienal (HCHD) adduct. This HCHD adduct can dissociate back to its products,
react with NO2, or react with O2. There have been several inconsistent results concerning the
importance of the NO2 and O2 reactions with the HCHD adduct. Atkinson [1994] suggests that
HCHD reacts rapidly with NO2 and that this reaction is significant if the concentration of NO2 is
greater than 3:0 1012 molecule cm,3 . Earlier studies suggest that the HCHD adduct also reacts
with NO [Zellner et al., 1985]. However, Atkinson [1994] believes that there was an impurity in
NO used in the study of Zellner et al. [1985]. In addition, no reaction with NO was observed by
Zetsch and co-workers [Atkinson, 1994].
In the Master Mechanism, the oxidation of benzene by the hydroxyl radical does not include
the formation of the adduct and the possible reaction of the adduct with NO2 or dissociation of
the adduct. The oxidation of benzene in the Master Mechanism effectively results in the products
of the HCHD radical reaction with oxygen, producing hydroxyl-2,4-cyclohexadienyl-6-peroxy and
phenol, discussed in Sections B.1.2.7 and B.1.2.7, respectively.
To determine whether the reaction of the HCHD radical with NO2 is competitive with the
reaction of the HCHD radical with O2 in typical arctic air, the psuedo-first-order rate constants were
179
compared for the two reactions. The concentrations of NO2 and O2 were based on the maximum
levels reached during the model simulation for the April 4, 1993 trajectory.
NO2]max
[O2 ]max
[
=
=
1:248 109 molecules cm,3
5:424 10 molecules cm,3
18
(B.67)
(B.68)
The rate constants reported by Atkinson [1994] are:
K(HCHD+NO )
K(HCHD+O )
2
=
2
=
2:75 10,11 cm3 molecules,1 s,1
1:6 10,16cm3 molecules,1 s,1 :
(B.69)
(B.70)
The resulting rates are
NO2] K(HCHD+NO )
[O2 ] K(HCHD+O )
[
2
=
2
=
0:03432s,1
867:84s,1:
(B.71)
(B.72)
The reaction of the HCHD adduct with NO2 is much less likely to occur than the reaction
with O2 in this NOx limited case, as illustrated by the much slower rate constant. As the reaction
of the HCHD radical with NO2 occurs less than 0.004% of the time under these conditions, it
will not affect the calculated concentrations of the nitrogen oxide containing aromatic compounds.
Therefore, it was deemed unnecessary to add the HCHD adduct and its reaction with NO2 to the
Master Mechanism.
The kinetic data, shown in Table B.5, is consistent with the rate constant included in the Master
Mechanism. However, the temperature dependence (B or E/R) in the Master Mechanism was
changed to 2:1 102 , the value recommended by Atkinson [1994].
Table B.5 Rate constants for the Reaction of Benzene with OH.
Rate Constant (298 K)
cm3
2.06 x 10,11 molec
,s
cm3
1.2 x 10,12 molec
,s
cm3
1.23 x 10,12 molec
,s
cm3
1.2 x 10,12 molec
,s
Temperature Dependence
7.57 x 10,12 exp(-529/T)
B = 208 K
E/R = 3.0 x 102 K
Reference
[Atkinson, 1985]
[Grosjean, 1991]
[Atkinson, 1994], [Atkinson, 1990]
[Madronich and Calvert, 1989]
The branching ratio for the reaction of C6 H6 with OH recommended by Atkinson [1994] is for
the abstraction pathway, which accounts for 5% of the reaction. The H–atom abstraction path was
not included in the mechanism created by Madronich and Calvert [1989]. This reaction pathway
was added to the mechanism, using the branching ratio and rates recommended by Atkinson [1994].
Benzene + NO3 The reaction of benzene with NO3 was added to the mechanism. The
products were based on H–atom abstraction in the presence of oxygen. The rate constant was set to
the value recommended by Atkinson [1994].
180
Hydroxyl-2,4-cyclohexadienyl-6-peroxy As an original product of benzene oxidation by
OH, the hydroxyl-2,4-cyclohexadienyl-6-peroxy molecule may: 1) dissociate back to its reactants
(benzene and OH), 2) react to form phenol and HO2 , 3) form 2,4-hexadiene-1,6-dial and OH, or 4)
isomerize to one of the bicyclic peroxy adducts.
The bicyclic peroxy adducts react with O2 to form another set of peroxy radicals, which become
alkoxy radicals after the terminal oxygen is removed by NO, eventually resulting in the ring–opened
products, glyoxal and butene–1,4–dial. Other products which are produced during O2–addition to
benzene include phenol and 2,4–hexadiene–1,6–dial, a straight chain unsaturated dialdehyde [Lay
et al., 1996].
In the Master Mechanism, the hydroxyl–2,4–cyclohexadienyl–6–peroxy radical mainly reacts
with NO to form the ring opened products glyoxal and butene–1,4–dial, skipping the formation
of the peroxy radicals, their rearrangement and transformation to alkoxy radicals. This reaction is
assumed to take place in the presence of oxygen, however oxygen is not included explicitly in the
reaction.
Other ultimate products produced in the mechanism [Madronich and Calvert, 1989]
from the reaction of hydroxyl–2,4–cyclohexadienyl–6–peroxy radical include: HO2,NO2 ,
hr62 (C6 H4 (H)(OH),(H)(OOH)), ro64 (C6 H4 (H)(OH),H(OH)), rk63 (C6 H4 (H)(OH),=O) , and
o011(CH3 OH).
The master mechanism seems to be consistent with the most recent kinetic data review [Atkinson,
1994]. For this reason, the reaction of hydroxyl-2,4-cyclohexadienyl-6-peroxy (2r61) with oxygen
and subsequent reactions were left unaltered.
Phenol Phenol, produced from the reaction of benzene with OH, can react with NO3 through
H–atom abstraction or with the OH radical either by addition or H–atom abstraction. The main
reaction of phenol is OH addition, producing 1,1-benzenediol. The reactions of 1,1-benzendiol are
discussed in Section B.1.2.7. The H–atom abstraction either by OH or NO3 produces a phenoxy
radical and H2 O or HNO3 , respectively.
Phenol + OH The rate constants for the reaction of phenol with OH are listed in Table B.6.
The rate constants reported in the literature do not distinguish between the addition and H–atom
abstraction reactions. According to Atkinson [1994], the H–atom abstraction accounts for about
9% of the OH reaction with phenol. This is in fairly good agreement with the branching ratio
used by Madronich and Calvert [1989], 7.8% for abstraction and 92.2% for addition. The rate
constant for the reaction of OH with phenol was changed to the recommendation of Atkinson
[1994], 2:63 10,11 . Keeping the same branching ratio as Madronich and Calvert [1989], Kadd
= 2:43 10,11 and Kabs = 2:05 10,12 .
Atkinson [1994] proposes a temperature dependent rate constant (E/R=405 K), which is incorporated into the mechanism. Over the temperature range given, the rate constant for phenol + OH
varies from 3:53 10,11 at 245 K to 2:65 10,11 at 296 K.
181
Table B.6 Rate Constants for the Reaction of Phenol with OH.
K (298 K)
2:6 10,11
2:2 10,12
2:6 10,11
2:63 10,11
Temp. Dependence
6:75 10,12 exp(405/T)
Reference
Master Mechanism
Master Mechanism
[Grosjean, 1991]
[Atkinson, 1994]
Notes
Add.
Abs.
Add. + Abs.
Add. + Abs., 245-296K
Table B.7 Rate Constants for the Reaction of Phenol with NO3 .
K (298 K)
3:6 10,12
3:6 10,12
3:92 10,12
3:78 10,12
Temp. Dependence
Reference
Master Mechanism
[Grosjean, 1991]
[Atkinson et al., 1992b]
[Atkinson, 1994]
Notes
+/- 35%
Phenol + NO3 For the reaction of phenol with NO3 , the rate constants are listed in Table B.7.
The rate constant recommended by Atkinson [1994] is based on a unit–weighted average of the rate
constants reported in Atkinson et al. [1992b] and Atkinson et al. [1984]. The recommended value
is different than that reported previously by Atkinson [1991]. There are no reported temperature
dependencies in the literature or in the master mechanism. The rate constant for the reaction of
phenol (ro61) with NO3 was set equal to the recommendation of Atkinson [1994], 3:8 10,12.
1,1-benzenediol Radical The 1,1-benzenediol radical reacts either with O2 or NO2 .
1,1-benzenediol + O2 According to Grosjean [1991], reaction of 1,1-benzenediol with O2
results in the trans-addition of O2 . This adduct then reacts with more O2 followed by NO2 , resulting
in the ring-opened products, CHOCH=CHCHO and CHOCOOH. The major products formed in
the Master Mechanism [Madronich and Calvert, 1989] from the O2 addition to 1,1-benzenediol is
2-nitro-1,1-benzenediol (rk61) and the ring-opened products, CHOCH=CHCHO and CHOCOOH.
The mechanism also results in additional products including: C6H4(OH)(OH),(=O) (rk62), 1,1benzenediol (2r62), CH3OH (o011), and (C6H4(OH)(OH),H(OH) (ro65).
1,1-benzenediol + NO2 The reaction of 1,1-benzenediol (6r61) with NO2 results in the
formation of 2-nitrophenol and 4-nitrophenol. For simplicity in the Master Mechanism, this reaction
results in rv62 (2-nitrophenol) only. As no data were available to suggest the reaction or rate constant
as incorrect, this reaction was not altered. The chemistry of nitrophenol formed through this reaction
is discussed below.
Nitrophenol As a result of the reaction of 1,1-benzenediol with NO2, nitrophenol is formed.
According to Grosjean [1991] nitrophenol can react with OH, by addition or H–atom abstraction,
or with NO3 by H–atom abstraction.
182
Table B.8 2-nitrophenol (rv62) + OH.
K (298 K)
not included
2:3 10,13
9:0 10,13
Temp. Dependence
none reported
none reported
none reported
K (298 K)
not included
3:4 10,13
Temp. Dependence
none reported
none reported
Reference
Master Mechanism
Grosjean [1991]
[Atkinson, 1994]
Notes
[Grosjean, 1990]
Table B.9 4-nitrophenol + OH.
Reference
Master Mechanism
Grosjean [1991]
Notes
[Grosjean, 1990]
Nitrophenol + OH The reaction of OH with nitrophenol may proceed either by addition
or H-atom abstraction. The OH addition to nitrophenol results in an adduct. This adduct may
react with O2 to produce ring-opened products or react with NO2 resulting in the formation of 2,6dinitrophenol (rv63), an end-product in the Master Mechanism. The H–atom abstraction reaction
of nitrophenol with OH produces a nitrophenoxy radical. The nitrophenoxy radical reacts with NO2
which also results in the formation of 2,6-dinitrophenol. The reaction of nitrophenol with OH was
not included in the master mechanism [Madronich and Calvert, 1989]. However, it was deemed
important to add this reaction. The reaction with the hydroxyl radical occurs during the daytime,
while reaction with the nitrate radical occurs mainly during the night, so it is important to include
both reactions. The reaction of 2-nitrophenol with OH was added to the mechanism, but the reaction
of 4-nitrophenol was not. As shown in Tables B.8 and B.9 the reaction of 4-nitrophenol is two
orders of magnitude slower than the reaction with 2-nitrophenol.
The reaction of 2-nitrophenol (rv62) with OH was added to the mechanism, using the rate
constant recommended by Grosjean [1991], K = 2:3 10,11. The products for this reaction are
based on H-atom abstraction: H2O and nitrophenoxy (C6 H3O: ,NO2; 1r62). For simplicity, phenoxy
was not included as a product because it produces the same compound that nitrophenoxy (1r62)
does, dinitrophenol. Nitrophenoxy (1r62) reacts with NO2 to produce rv63 (2,4-dinitrophenol).
The reaction of HO2 with the nitrophenoxy radical (not included in the mechanism proposed
by Grosjean [1991]) is included by analogy with the phenoxy radical reaction with HO2; this
reaction results in nitrophenol. Furthermore, for simplicity, the reactions of 2-nitrophenol produce
2,4-dinitrophenol, skipping the intermediate adducts and lumping the theoretically formed 2,6dinitrophenol with 2,4-dinitrophenol.
While nitroaromatics are not normally considered a significant sink of NOx , the simulated
mixing ratios are consistent with those measured in the gas phase at Great Dun Fell, a rural
site in Northern England [Lüttke et al., 1997]. At Great Dun Fell, levels of mono-nitrophenols
(sum of 2- and 4-nitrophenol) were observed to be 8.7106 –1.6108 molec cm,3 , while 2,4dinitrophenol levels were 3.3105 –2.8108 molec cm,3 . In our simulations, mono-nitrophenols
(2-nitrophenol) were less than 3.0108 molec cm,3 , and 2,4-dinitrophenol levels were less than
1.6108 molec cm,3 .
183
Nitrophenol + NO3 For reaction of 2-nitrophenol with NO3, the rate constant reported by
Atkinson et al. [1992b] is much lower than that used by Madronich and Calvert [1989], as shown
in Table B.10. The rate constant was changed to the recommendation of Atkinson et al. [1992b].
Table B.10 2-nitrophenol (rv62) + NO3 .
K (298 K)
3:8 10,12
< 2 10,14
Temp. Dependence
none reported
none reported
Reference
Master Mechanism
[Atkinson et al., 1992b]
Notes
B.2 Troe Reactions
The troe reactions which were investigated are listed in Table C.19.
Thermal Decomposition of NO3 The decomposition of NO3 was removed from the mechanism by placing an “x” in the flag position. DeMore et al. [1997] suggests that this reaction will
not occur in the atmosphere because “the barrier to thermal dissociation is 47.3 kcal mol,1.”
B.3 Photolysis
The updates to the photolysis reactions were limited to absorption cross sections and quantum yields
for nitrogen- and oxygen- containing compounds which are treated explicitly by Madronich and
Calvert [1989] or added by Williams [1994a]. The absorption cross sections and quantum yields for
each compound were compared to values recommended by DeMore et al. [1997] to assess whether
there has been a significant change in the photolysis data since the Master Mechanism-Version 2.0
[Madronich and Calvert, 1989] was created. The reviews by Atkinson [1994] and Atkinson et al.
[1992b] were used, in that order of preference, for compounds which are not included in DeMore
et al. [1997], such as C3 and larger compounds. Photolysis data for many compounds are still not
available. In this case, the values used by Madronich and Calvert [1989] were retained
If there was a significant change in the absorption cross sections or quantum yields, a combination of interpolation and averaging was used to resolve the recommended values onto Isaksen’s
wavelength integration grid. For several compounds the values used in the model RACM [Stockwell
et al., 1997] matched those recommended by DeMore et al. [1997], Atkinson [1994], or Atkinson
et al. [1992b]. In this case, it was convenient to use Stockwell et al. [1997]’s data because the
absorption cross sections and quantum yields were already resolved onto Isaksen’s grid.
Table B.11 is a listing of the compounds which were evaluated. The most notable changes—
those that require programming—include the addition of PAN photolysis, separation of NO3 pho-
184
tolysis into two channels, addition of temperature dependence for HNO3 , H2O2 , CH2 O, and PAN
absorption cross sections (subroutines in jblock.f), and alteration of the temperature dependent
expression for calculating ozone quantum yields.
Williams [1994a] also made several changes to the Master Mechanism photolysis reactions.
The weighting factors of the alkyl nitrates were changed and several new alkyl nitrates were added.
However, these changes were not used as discussed in Section B.3.3.
The remaining portion of this section is divided according to the following compounds and
groups of compounds: Ox , hydroperoxides, odd nitrogen, carbonyls, and acids. Each subsection contains a comparison of available photolysis data for each compound treated explicitly by
Madronich and Calvert [1989] in the cross section (rxs.dat) and quantum yield (rqy.dat) data files.
B.3.1 Ox
Ozone The recommendation for the absorption cross section data for ozone by DeMore et al.
[1997], DeMore et al. [1994], and DeMore et al. [1992] is based on WMO [1986]. Because the
absorption cross section of ozone was well characterized before the Master Mechanism was created,
the values used by Madronich and Calvert [1989] are still valid.
There is a new temperature dependent expression for the calculation of ozone quantum yields
[Sander et al., 2000]. The new quantum yield of O(1 D) includes a “tail” between 310 and 330 nm.
For = 248–300 nm, the new recommended quantum yield is 0.95. For = 300–330 nm, the
following temperature dependent expression is recommended:
" 4# T 4 " ( , ) 2 #
( , 01 )
2
02
+ a2
(T; ) = a1 exp ,
exp ,
!1
300
kT exp ,
!2
3 " ( , 03) 2 #
+a3 exp ,
+ 0:06:
kT exp ,
!
3
The parameters for the above equation are listed in Table B.12. For = 330–345 nm, a constant
temperature independent quantum yield of 0.06 is recommended for atmospheric conditions. Above
345 nm, the quantum yield is zero. The subroutine used to calculate ozone quantum yields
(GET O3 QY) was altered to use the recommendation of Sander et al. [2000].
B.3.2 Hydroperoxides
Hydrogen Peroxide, H2O2 The absorption cross section data for hydrogen peroxide recommended by DeMore et al. [1997] is the same as in previous evaluations [DeMore et al., 1994;
DeMore et al., 1992]. The recommendation is listed at two temperatures, 298 and 355 K, and a
185
Table B.11 Summary of Photolysis Data.
Compound
O3
H2 O2
methyl hydroperoxide (h011)
NO2
NO3
N2 O5
HNO2
HNO3
HNO4
PAN (p021)
methyl nitrate (n011)
ethyl nitrate (n021)
1-propyl nitrate (n031)
2-propyl nitrate (n032)
1-butyl nitrate (n041)
2-butyl nitrate (n042)
1-pentyl nitrate (n053)
2-pentyl nitrate (n054)
3-pentyl nitrate (n055)
CH2 O
acetaldehyde (d021)
propanal (d031)
1-butanal (d041)
1-methyl propanal (d042)
glyoxal (dd21)
methyl glyoxal (dk33)
acetone (k031)
2-butanone (k041)
3-pentanone (k052)
biacetyl (kk43)
acrolein (ud34)
Cross Section
Madronich and Calvert [1989]a
DeMore et al. [1997]
Madronich and Calvert [1989]a;b
Stockwell et al. [1997]
Stockwell et al. [1997]
Madronich and Calvert [1989]a
Stockwell et al. [1997]
Stockwell et al. [1997]
Madronich and Calvert [1989]a
DeMore et al. [1997]
Madronich and Calvert [1989]b
Madronich and Calvert [1989]b
Atkinson et al. [1992b]
Atkinson et al. [1992b]
1-propyl nitrate
2-propyl nitrate
1-propyl nitrate
2-propyl nitrate
2-propyl nitrate
< 300 Madronich and Calvert [1989]
300 DeMore et al. [1997]
Martinez et al. [1992]c
Martinez et al. [1992]c
Martinez et al. [1992]c
Martinez et al. [1992]c
Madronich and Calvert [1989]b
Stockwell et al. [1997]c
Martinez et al. [1992]c
Martinez et al. [1992]c
Martinez et al. [1992]c
Madronich and Calvert [1989]c
Madronich and Calvert [1989]
a Recommended by DeMore et al. [1997].
b Recommended by Atkinson et al. [1992b].
c Recommended by Atkinson [1994].
Table B.12 Parameters for the O3
Quantum Yield Equation.
Index
1
2
3
ai
0.887
2.35
57
oi
302
311.1
313.9
i
820
1190
!i
7.9
2.2
7.4
Quantum Yield
Sander et al. [2000]
unity, Madronich and Calvert [1989]a
unity, Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Johnston et al. [1996]a
Madronich and Calvert [1989]a
unity, Madronich and Calvert [1989] b
unity, Madronich and Calvert [1989]b
unity, Madronich and Calvert [1989]a
DeMore et al. [1997]
unity, Madronich and Calvert [1989]b
unity, Madronich and Calvert [1989]b
unity, Madronich and Calvert [1989]b
unity, Madronich and Calvert [1989]b
unity, Madronich and Calvert [1989]
unity, Madronich and Calvert [1989]
unity, Madronich and Calvert [1989]
unity, Madronich and Calvert [1989]
unity, Madronich and Calvert [1989]
Madronich and Calvert [1989]a
Madronich and Calvert [1989]c
Atkinson [1994]
Madronich and Calvert [1989]
Atkinson [1994]
Madronich and Calvert [1989]b
Atkinson et al. [1992b]
Stockwell et al. [1997]c
Madronich and Calvert [1989]c
Madronich and Calvert [1989]
186
temperature dependent expression is given for =260–350 nm and T=200–400 K:
7
X
An n + (1 , )
(; T ) 1021
=
=
[1 + exp(
n=0
4
X
n=0
,1265=T )],1
Bn n
(B.73)
(B.74)
where T is temperature in K, is wavelength in nm, and An and Bn are constants. This expression
is based on the work of Nicovich and Wine [1988] which was published after the evaluations used
by Madronich and Calvert [1989]. The difference between the values at 298 and 355 K ranged
from 1–23% difference, depending on wavelength. Because the temperature in typical arctic outflow
simulations is about 50 degrees cooler than the listed 298 values, a subroutine was added to calculate
the temperature dependent H2O2 cross sections.
The quantum yield of H2O2 is believed to be unity [DeMore et al., 1997], which is the value
used by Madronich and Calvert [1989].
Methyl Hydroperoxide, CH3 OOH (h011) The recommendation of DeMore et al. [1997]
remains unchanged from the previous evaluations [DeMore et al., 1994; Atkinson et al., 1992b].
While these evaluations are all based on a study conducted by Vaghjiani and Ravishankara [1989],
Atkinson et al. [1992b] provides a more complete list of values. As shown in Figure B.1, the values
used by Madronich and Calvert [1989] are equal to those recommended by Atkinson et al. [1992b]
except at the peak, where Madronich and Calvert [1989] have a lower value due to averaging
over wavelength intervals. The absorption cross section used by Madronich and Calvert [1989] is
satisfactory.
The quantum yield of CH3 OOH is believed to be unity [DeMore et al., 1997], which is the value
used by Madronich and Calvert [1989].
Other Hydroperoxides The photolysis reactions for a number of nitrate containing hydroperoxides (hn35–hn5f) were added by Williams [1994a]. These hydroperoxides were formed from
alkyl nitrate reactions introduced into the mechanism by Williams [1994a]. As was done for the
smaller hn** compounds, the absorption cross sections are set equal to methyl hydroperoxide (h011)
and the quantum yields are set to unity.
B.3.3 Odd Nitrogen
Nitrogen Dioxide, NO2 The current recommendation for the NO2 absorption cross section
[DeMore et al., 1997] is unchanged from the earlier recommendation [DeMore et al., 1994]. This
recommendation is based on work by Schneider et al. [1987] for = 200–274 nm and Davidson
et al. [1988] for = 274–420 nm and includes the following temperature dependence in the
wavelength range of 274–420 nm:
= (0C ) + A T
(B.75)
187
Figure B.1 CH3 OOH Absorption Cross Section.
where A is the temperature coefficient (wavelength dependent) and T is temperature ( C). There
are no limits given for the temperature range. As the temperature increases, the absorption cross
section decreases. However, the effect of temperature is negligible: even with a 50 decrease in the
temperature, there is less than a 2.5% change in the absorption cross sections.
Figure B.2 shows that there are slight differences between Madronich and Calvert [1989] and
DeMore et al. [1997] (T=0 C), while Stockwell et al. [1997] and DeMore et al. [1997] are equal.
The absorption cross section data used by Stockwell et al. [1997] is based on the recommendation
of DeMore et al. [1994]. The model was updated to include the non–temperature dependent NO2
absorption cross sections used by Stockwell et al. [1997].
The NO2 quantum yields recommended by DeMore et al. [1997] remain unchanged from recent
evaluations [DeMore et al., 1994; DeMore et al., 1992]. As shown in Figure B.3, the values used by
Madronich and Calvert [1989] match those used by Stockwell et al. [1997], and recommended by
DeMore et al. [1997]. In the absence of new data, the NO2 quantum yield data given by Madronich
and Calvert [1989]was used.
NO3 The NO3 absorption cross sections recommended by DeMore et al. [1997] remain unchanged
from the earlier recommendation [DeMore et al., 1994]. The recommended cross section at 662 nm
was determined from the studies by Marinelli et al. [1982], Ravishankara and Wine [1983],
Burrows et al. [1985], Ravishankara and Mauldin [1986], Sander [1986], Cantrell et al. [1987],
and Canosa-Mas et al. [1987]. While for = 600–670 nm, the absorption cross section values are
based only on Ravishankara and Mauldin [1986], Sander [1986], and Canosa-Mas et al. [1987].
188
Figure B.2 NO2 Absorption Cross Section.
Figure B.3 NO2 Quantum Yield.
189
Figure B.4 NO3 Absorption Cross Section.
The absorption cross section values used in the model RACM [Stockwell et al., 1997] are taken from
the review by Wayne et al. [1991]. The values recommended in the review [Wayne et al., 1991] are
based on Sander [1986] and normalized to the absorption cross section at 662 nm from the studies
by Ravishankara and Mauldin [1986], Sander [1986], Cantrell et al. [1987], and Canosa-Mas et
al. [1987].
The NO3 absorption cross sections used by Stockwell et al. [1997] are slightly higher than those
used by Madronich and Calvert [1989], as shown in Figure B.4. Both Stockwell et al. [1997] and
Madronich and Calvert [1989] have much lower peaks than recommended by DeMore et al. [1994].
This is due to the intervals that are reported by the different sources. DeMore et al. [1994] report
absorption cross section in 1 nm intervals from 600 to 670 nm, while Stockwell et al. [1997] and
Madronich and Calvert [1989] report values at 5–10 nm intervals in this wavelength range. The
model was altered to use the NO3 absorption cross sections from Stockwell et al. [1997], because
their values matched the average values of DeMore et al. [1994] better than the values used by
Madronich and Calvert [1989].
There are two channels for the NO3 photolysis reaction [DeMore et al., 1997; Stockwell et al.,
1997; Wayne et al., 1991]:
A NO + O
!
2
B
NO3 + hv ! NO2 + O
NO3 + hv
(B.76)
(B.77)
In the Master Mechanism these channels are simulated with a constant branching ratio:
NO3 + hv
! 0:89NO2 + 0:11NO + 0:89O:
(B.78)
190
Figure B.5 NO3 QY: Johnston et al., 1996 vs Madronich.
DeMore et al. [1997] have a new recommendation for NO3 photolysis rates for both channels.
The photolysis rates were are taken from Johnston et al. [1996] and calculated for the stratosphere
with a solar zenith angle of zero. For wavelength specific quantum yield data, DeMore et al. [1997]
recommend the tabulation by Johnston et al. [1996], in which quantum yields are reported for
=585–640 nm at 190, 230, and 298K. Comparing the quantum yields for the sum of channels
from Johnston et al. [1996] at 298 K to Madronich and Calvert [1989]’s quantum yields for one
channel (Figure B.5) the values from Johnston et al. [1996] drop to zero in the same wavelength
range. However, this drop occurs more rapidly at first then slows creating a curve rather than the
straight line representation as in Madronich and Calvert [1989], resulting in a maximum difference
of 60%. The model was changed to include both NO3 photolysis channels and the quantum yields
from Johnston et al. [1996] which were averaged and centered on Isaksen’s grid wavelengths.
N2 O5 The recommendation for N2 O5 cross sections in DeMore et al. [1997] is the same as the
earlier recommendation [DeMore et al., 1994], and is equal to the values used by Madronich and
Calvert [1989].
For N2 O5 quantum yields, the recommendation of DeMore et al. [1997] has not changed from
earlier recommendations [DeMore et al., 1994; DeMore et al., 1992]. There are two channels for
N2 O5 photodissociation:
A
!
B
N2 O5 + hv !
N2 O5 + hv
NO3 + NO + O(3P)
(B.79)
NO3 + NO2
(B.80)
191
Figure B.6 N2 O5 Quantum Yield.
The quantum yield for NO3 production is near unity and the yields for O and NO increase at shorter
wavelengths, while yields for NO2 decrease. Ravishankara et al. [1986] report O quantum yields
at four wavelengths. Three of these four quantum yields are less than 0.2% different than the values
used by Madronich and Calvert [1989], and the fourth quantum yield is 10% different. Figure B.6,
shows the N2O5 quantum yields for channel A.
HNO2 The recommendation of DeMore et al. [1997] for HNO2 absorption cross sections is the
same as earlier recommendations [DeMore et al., 1994; DeMore et al., 1992]. This recommendation
was first made by DeMore et al. [1992] and is based on the work of Bongartz et al. [1991]. Stockwell
et al. [1997] use the values recommended by DeMore et al. [1994]. Figure B.7 shows that there are
differences at the peaks between Madronich and Calvert [1989] and DeMore et al. [1997], while
Stockwell et al. [1997] and DeMore et al. [1997] are equal. Because Stockwell et al. [1997] matches
DeMore et al. [1997], the model was changed to include the HNO2 absorption cross sections used
by Stockwell et al. [1997].
Atkinson et al. [1992b] report an HNO2 quantum yield of unity, which is the value used by
Madronich and Calvert [1989].
HNO3 DeMore et al. [1997]’s recommendation for the HNO3 absorption cross section is the
same as the earlier recommendation [DeMore et al., 1994] except at = 314 nm. The following
temperature dependence for the absorption cross section of HNO3 was first included in DeMore et
192
Figure B.7 HNO2 Absorption Cross Section.
al. [1994]’s recommendation:
(; T ) = (; 298) exp[B() (T , 298)]
(B.81)
where B is a wavelength dependent constant and T is temperature in K. The effect of temperature
is important for the temperature ranges experienced during arctic outflow events: at 250 K the
HNO3 absorption cross section is negligible. A subroutine was added to jblock.f to calculate the
temperature dependent absorption cross section for HNO3 based on the data reported by DeMore et
al. [1997].
Atkinson et al. [1992b] report an HNO3 quantum yield of unity, which is the value used by
Madronich and Calvert [1989].
HNO4 The recommendation for the absorption cross section for HO2 NO2 by DeMore et al.
[1997] is the same as the earlier recommendations [DeMore et al., 1994; DeMore et al., 1992]. As
shown in Figure B.8, the values used by Madronich and Calvert [1989] are equal to the recommended
values [DeMore et al., 1997].
DeMore et al. [1997] recommend quantum yields of 0.33 for the production of OH and NO3
and a yield of 0.67 for the production of HO2 and NO2 . These quantum yields are taken into account
by Madronich and Calvert [1989] as stoichiometric coefficients in the mechanism.
HNO4 + hv
! 0:67HO2 + 0:33OH + 0:33NO3 + 0:67NO2
(B.82)
193
Figure B.8 HNO4 Absorption Cross Section.
PAN, CH3C(O)OONO2 (p021) The photodissociation of PAN is a new entry in DeMore et al.
[1997]. It is believed to proceed as follows:
!A
B
CH3 C(O)OONO2 + hv !
CH3 C(O)OONO2 + hv
CH3C(O)O2 + NO2
(B.83)
CH3C(O)O + NO3
(B.84)
The recommended absorption cross section [DeMore et al., 1997] has the following temperature
dependence:
T) )
ln( ((298
)
=
B (T , 298)
(B.85)
(B.86)
Rearranging this becomes,
(T )
=
(298) exp[B (T , 298)]
(B.87)
where B is a wavelength dependent constant and T is temperature in K. The temperature dependence
applies for T = 250–289 K. As shown in Figure B.9, at 250 K the absorption cross section is
negligible, it is on the order of 10 ,60 near the peak at 200 nm.
The model was altered to use the temperature-dependent PAN cross sections from DeMore et
al. [1997]. A combination of averaging and interpolation were used to resolve the data, (298K )
and B, onto Isaksen’s wavelength integration grid. A subroutine (GET p021 XS) was added to
calculate the temperature dependent absorption cross section as a function of wavelength.
194
Figure B.9 PAN Absorption Cross Section.
The quantum yield for channel A is 0.83 0.09, while for channel B the quantum yield is
0.3 0.1 [DeMore et al., 1997]. To conserve mass, the quantum yields were set to 0.77 and 0.23
for channels A and B, respectively [Mazely et al., 1997].
Methyl Nitrate, CH3ONO2 (n011) Atkinson [1994]’s recommendation for the absorption
cross section for methyl nitrate is the same as the earlier recommendation [Atkinson et al., 1992b].
This recommendation is based on work done by Roberts and Fajer [1989]. The absorption cross
section used by Madronich and Calvert [1989] for methyl nitrate matches Atkinson et al. [1992b]’s
recommendation quite well as shown in Figure B.10. In the absence of data indicating the values
are in error, use the absorption cross sections given by Madronich and Calvert [1989] for methyl
nitrate.
The quantum yield for methyl nitrate is presumed to be equal to unity due to a lack of structure
in the absorption spectra [Atkinson et al., 1992b].
Ethyl Nitrate, CH3CH2 ONO2 (n021) The recommendation [Atkinson, 1994] for ethyl nitrate
absorption cross sections is equal to the earlier recommendation of Atkinson et al. [1992b], which
is based on the studies of Turberg et al. [1990] and Roberts and Fajer [1989]. The absorption cross
section for ethyl nitrate added by Williams [1994a] is 1.33 times the cross section of methyl nitrate
(n011). Figure B.11 shows that within the wavelength range of 270–330 nm the approximation is
similar to the values recommended by Atkinson et al. [1992b]. However, Atkinson et al. [1992b]
provide recommended values for a much larger range, 185–330 nm, as shown in Figure B.12. Below
195
Figure B.10 Methyl Nitrate Absorption Cross Section, logarithmic.
Figure B.11 Ethyl Nitrate Absorption Cross Section.
196
Figure B.12 Ethyl Nitrate Absorption Cross Section, logarithmic.
260 nm the cross section values are much higher (approximately 2 orders of magnitude) than those
used above 260 nm. However, the contribution of the absorption cross section for wavelengths less
than 260 nm to the rate of photolysis (J value) is negligible as demonstrated for propyl nitrate below.
Therefore the approximation (1.33*n011 xs) added by Williams [1994a] was not altered.
While no recommendation has been made, the quantum yield for ethyl nitrate has been assumed
to be equal to unity due to a lack of structure in the absorption spectra [Atkinson et al., 1992b]. This
is supported by measurements of the rate of NO2 formation resulting from ethyl nitrate photolysis
[Luke and Dickerson, 1988; Luke et al., 1989] and calculated rates assuming = 1 for = 290–
340 nm [Atkinson et al., 1992b].
Propyl Nitrate, C3H7 ONO2 The recommendation of Atkinson et al. [1992b] is unchanged in
Atkinson [1994]. The absorption cross sections for both n- and i-propyl nitrate are based on work
done by Turberg et al. [1990] and Roberts and Fajer [1989]. In the model RACM, Stockwell et
al. [1997] use a mixture of 20% n-propyl and 80% i-propyl nitrate, to represent the absorption
cross section of organic nitrates. The cross sections used by Stockwell et al. [1997] were based on
Atkinson [1994]. The cross section of n-propyl nitrate is shown in Figures B.13 and B.14. The
model was altered to use the absorption cross sections recommended by Atkinson et al. [1992b] for
n- and i-propyl nitrate.
While no recommendation has been made, the quantum yield for n-propyl nitrate has been
assumed to be equal to unity due to a lack of structure in the absorption spectra [Atkinson et al.,
1992b]. This is supported by measurements of the rate of NO2 formation resulting from n-propyl
197
Figure B.13 Propyl Nitrate Absorption Cross Section, logarithmic.
Figure B.14 Propyl Nitrate Absorption Cross Section, logarithmic.
198
nitrate photolysis [Luke and Dickerson, 1988; Luke et al., 1989] and calculated rates assuming = 1 for = 290–340 nm [Atkinson et al., 1992b]. There are no measurements for i-propyl nitrate
photodissociation products or quantum yields; however, the quantum yield is assumed to be equal
to 1 for =290–330 nm [Atkinson et al., 1992b].
Other Alkyl Nitrates No recommendations are provided by DeMore et al. [1997], Atkinson
[1994], or Atkinson et al. [1992b] for the photolysis parameters for propyl, pentyl, or larger alkyl
nitrates. For the absorption cross sections of n-butyl nitrate (n041) Williams [1994a] used 2.0 times
the cross section of methyl nitrate (n011).
Several investigators have noticed trends in the absorption cross section of alkyl nitrates. Roberts
and Fajer [1989] note an increase in absorption cross section both with increasing carbon number
and degree of substitution. Williams [1994b] also notes an increase in the cross section with
increasing carbon number, but suggested that this increase becomes smaller with each additional
carbon due to the inductive effect. Additionally, Williams [1994b] observed that the cross sections
of the primary alkyl nitrates are similar, and suggested that this may also be the case for secondary
nitrates. Based on the general trends of carbon number and degree of substitution, to obtain a lower
limit for the absorption cross sections of alkyl nitrates larger than C3 without recommendations,
the primary alkyl nitrates (n041 and n053) are set equal to those of n-propyl nitrate (n031) as
recommended by Atkinson et al. [1992b]. The absorption cross section for secondary (n042, n054,
and n055) and tertiary (n043) alkyl nitrates are set equal to those of i-propyl nitrate (n032) cross
section that was recommended by Atkinson et al. [1992b].
In the absence of data for butyl and pentyl nitrates, the quantum yields were set equal to unity
similar to the smaller alkyl nitrates.
Alkyl Nitrites Methyl (w012) and ethyl nitrite (w012) were added to the master mechanism.
As alkyl nitrites photolyze rapidly, photolysis reactions were added for these compounds. The
absorption cross sections were set equal to 2 times the cross section for HNO2 and the quantum
yield was set equal to unity. This results in cross section values similar to the methyl nitrite cross
section measured by Taylor et al. [1980], as shown in Figure B.15.
B.3.4 Carbonyls
B.3.4.1
Aldehydes
Formaldehyde, CH2 O The recommendation by DeMore et al. [1997] for formaldehyde absorption cross sections is the same as the earlier recommendation [DeMore et al., 1994]. The
recommendation by DeMore et al. [1997] is based on Cantrell et al. [1990] and is temperature
dependent. Figure B.16 shows that the difference between the cross sections at 223 and 298 C is
minimal at most wavelengths. However, the percent difference is larger than 10 % and as large as
199
Figure B.15 Methyl Nitrite Absorption Cross Section.
95% at most of the peaks, minima, and for recommended temperature dependence:
> 335 nm.
Therefore it is important to include the
(T ) = A + B 10,3T
(B.88)
where A and B are wavelength specific temperature dependent constants, T is temperature in C,
and (T) is the cross section at T, in 10,20 cm2 . This temperature dependent expression is valid
only for temperatures between -50 and 20C and for wavelengths between 300 and 360 nm.
Figure B.17 compares formaldehyde absorption cross sections used by Madronich and Calvert
[1989] and Stockwell et al. [1997] to the recommendation of DeMore et al. [1997]. Below 300 nm,
the values used by Madronich and Calvert [1989] are slightly lower than those used in RACM
[Stockwell et al., 1997]. The values used by Madronich and Calvert [1989] are apparently based
on Moortgat et al. [1983] and Bass et al. [1980], which are the sources of the recommendation
of DeMore et al. [1997]. Stockwell et al. [1997] use only the work by Moortgat et al. [1983] for
wavelengths less than 300 nm. Comparing the 10 nm averages of Bass et al. [1980] and Moortgat
et al. [1983], as listed in Rogers [1990], Bass et al. [1980] is slightly lower than Moortgat et
al. [1983], which would explain the difference between Stockwell et al. [1997] and Madronich
and Calvert [1989]. The Master Mechanism was changed to include the temperature dependent
expression from DeMore et al. [1997] for = 300–360 nm and to use Madronich and Calvert
[1989] for < 300 nm.
The recommendation for formaldehyde quantum yields has not changed in the most recent
reviews [DeMore et al., 1997; DeMore et al., 1994; DeMore et al., 1992] and is based on an
200
Figure B.16 CH2 O Absorption Cross Section as a Function of Temperature.
Figure B.17 CH2 O Absorption Cross Section.
201
Figure B.18 CH2 O Channel A Quantum Yield.
evaluation of data from the late 1970s performed by Madronich in 1991 [DeMore et al., 1997].
There are two product channels for the photodissociation of formaldehyde:
A HCO + H
CH2O + hv !
B CO + H
CH2O + hv !
2
(B.89)
(B.90)
The quantum yield data for channel B is temperature and pressure dependent for > 330 nm.
Stockwell et al. [1997] use quantum yields from Atkinson et al. [1994] for < 300 nm, and from
DeMore et al. [1994] for > 300 nm. Since Figures B.18 and B.19 show good agreement between
Madronich and Calvert [1989], DeMore et al. [1997], and Stockwell et al. [1997] for the quantum
yields of channel A and B, respectively, for wavelengths greater than 270 nm, the quantum yields
for formaldehyde in the Master Mechanism were not altered.
Acetaldehyde, CH3 CHO, (d021) DeMore et al. [1997] does not include a recommendation for
acetaldehyde or any of the larger carbonyls. Atkinson [1994]’s recommendation for the cross section
of acetaldehyde is based on the work of Martinez et al. [1992] and supersedes the recommendation
of Atkinson et al. [1992b]. In the model RACM [Stockwell et al., 1997], the chemistry of the
compound ALD is treated as acetaldehyde and the absorption cross section are taken from Martinez
et al. [1992].
Figure B.20 shows that the difference between the acetaldehyde absorption cross sections of
Madronich and Calvert [1989] and Martinez et al. [1992] is at the peak at 210 nm. Madronich and
202
Figure B.19 CH2 O Channel B Quantum Yield.
Calvert [1989] include a small peak near 210 nm, which is not present in the data from Martinez et
al. [1992]. This small peak near 200 nm is about 0.5% the size of the main peak around 300 nm,
and has a negligible effect on the J values. At the main peak near 290 nm, Martinez et al. [1992]
have a double peak which is approximately 10% larger than the values used by Madronich and
Calvert [1989].
To be consistent with the higher aldehydes and to check the method used to resolve the data
onto Isaksen’s wavelength grid, the Master Mechanism was changed to use the absorption cross
section data from Martinez et al. [1992]. To resolve the absorption cross section values given by
Martinez et al. [1992] onto Isaksen’s grid, a combination of interpolation and averaging was used.
Linear interpolation was used if there were fewer data points than grid points. If there was more
than one point from Martinez et al. [1992] in a grid interval, then the cross sections were averaged
and centered over the intervals. As shown in Figure B.21, the values which were generated match
those used by Stockwell et al. [1997] with 5.2% difference, except at the outer edge of the peak
(below 203 nm and above 330 nm).
The quantum yield data for acetaldehyde recommended by Atkinson [1994] is the same as the
earlier recommendation [Atkinson et al., 1992b], and is based on the work of Atkinson and Lloyd
[1984]. In the model RACM, Stockwell et al. [1997] use the recommendation from Atkinson [1994].
As shown in Figure B.22, the quantum yield data for Stockwell et al. [1997] is very close to that
used by Madronich and Calvert [1989] for > 265 nm. While Stockwell et al. [1997] begins to
rise from zero about 10 nm after Madronich and Calvert [1989], no information is provided for the
wavelengths where they differ. Note that these differences occur at low wavelengths ( < 265 nm),
203
Figure B.20 CH3 CHO Absorption Cross Section.
Figure B.21 CH3 CHO Absorption Cross Section.
204
Figure B.22 CH3 CHO Quantum Yield.
so the impact on the J values are negligible. In the absence of new data, the quantum yield data
given by Madronich and Calvert [1989] for acetaldehyde was used.
Propanal, CH3 CH2CHO, (d031) Atkinson [1994] recommends the absorption cross section
from Martinez et al. [1992] for propanal. Figure B.23 shows that Madronich and Calvert [1989]
and Martinez et al. [1992] use similar cross sections. However, Martinez et al. [1992] has a double
peak which is shifted slightly toward longer wavelengths, whereas Madronich and Calvert [1989]
have a single peak. To be consistent with the other carbonyls, the model was altered to use the
absorption cross sections from Martinez et al. [1992] resolved onto Isaksen’s grid for propanal.
The quantum yields for propanal used by Madronich and Calvert [1989] are equal to acetaldehyde quantum yields (channel A). The recommendation of Atkinson [1994] refers to the earlier
evaluation [Atkinson et al., 1992b], and is based on the work of Heicklen et al. [1986] who report
the following quantum yields at 298K: 0.89 at 294 nm, 0.85 at 302 nm, 0.50 at 313 nm, 0.26 at
325 nm, and 0.15 at 334 nm. Figure B.24, shows the approximation used by Madronich and Calvert
[1989] is significantly different than the recommendation of Atkinson et al. [1992b]. The model was
altered to treat the quantum yield of propanal explicitly using the values recommended by Atkinson
et al. [1992b] and the pressure dependence of formaldehyde.
1-Butanal, CH3 CH2CH2 CHO (d041) Atkinson [1994] recommends the cross section data
from Martinez et al. [1992] for 1-butanal. The values used by Madronich and Calvert [1989] have
a smaller peak than recommended by Martinez et al. [1992], as shown in Figure B.25. The model
205
Figure B.23 Propanal (d031) Absorption Cross Section.
Figure B.24 Propanal (d031) Quantum Yield.
206
Figure B.25 n-Butanal (d041) Absorption Cross Section.
was altered to use n-butanal cross sections from Martinez et al. [1992].
According to Atkinson [1994], the quantum yields of n-butanal have been studied by Forgeteg
et al. [1978] and Forgeteg et al. [1979]. For the production of C2 H4 and CH3 CHO (channel B), the
quantum yield is reported to be 0.18 at 313 nm, while for the production of C3 H7 and HCO (channel
A) the quantum yield is 0.3 at 313 nm. Madronich and Calvert [1989] assume the quantum yields
to be 0.25 and 0.75 times the quantum yield of acetaldehyde, respectively.
For the production of C3 H7 and HCO (channel A) the quantum yield is 0.3 at 313 nm, while
for the production of C2 H4 and CH3 CHO (channel B), the quantum yield is reported to be 0.18 at
313 nm. Madronich and Calvert [1989] assume the quantum yield for channel A to be 0.75 times
the quantum yield of acetaldehyde and 0.25 times acetaldehyde for channel B. At the single point
reported, the values used by Madronich and Calvert [1989] are low (0.17 and 0.06). The model was
altered to use the quantum yield of acetaldehyde used by Madronich and Calvert [1989], scaled to
the values recommended by Atkinson [1994] at 313 nm. The new weighting factors are 1.32 for
channel A and 0.791 for channel B. Figures B.26 and B.27 compare the values used by Madronich
and Calvert [1989] and the new quantum yields for channels A and B, respectively.
2-Butanal, CH3CH(CH3)CHO (d042) Atkinson [1994] recommends the cross section values
measured by Martinez et al. [1992]. Figure B.28 shows that the values used by Madronich and
Calvert [1989] are nearly identical to Martinez et al. [1992], except at the peak near 190 nm. The
model was altered to use the i-butanal cross sections from Martinez et al. [1992].
207
Figure B.26 n-butanal (d041) Quantum Yield, Channel A.
Figure B.27 n-butanal (d041) Quantum Yield, Channel B.
208
Figure B.28 i-Butanal (d042) Absorption Cross Section.
Atkinson [1994] reports the quantum yields of i-butanal have been measured by Desai et al.
[1986]. For the production of (CH3 )2 CH and HCO, the quantum yields were reported to be: 0.2
at 253.7 nm, 0.45 at 280.3 nm, 0.55 at 302.2 nm, 0.88 at 312.8 nm, 0.88 at 326.1 nm, and 0.69 at
334.1 nm. The quantum yields used by Madronich and Calvert [1989] are equal to the acetaldehyde
values. Figure B.29, shows that the approximation used by Madronich and Calvert [1989] is
significantly different than that measured by Desai et al. [1986]. The model was altered to treat the
quantum yield of propanal explicitly using the values measured by Desai et al. [1986] resolved on
Isaksen’s wavelength grid.
Glyoxal, CHOCHO (dd21) The recommendation from Atkinson et al. [1992b] is the same as
their previous evaluation [Atkinson et al., 1989b] and is based on the work of Plum et al. [1983].
In the model RACM, Stockwell et al. [1997] take the absorption cross sections for glyoxal from
Atkinson et al. [1992b]. Figure B.30 shows that Stockwell et al. [1997] and Madronich and Calvert
[1989] have the same values while Atkinson et al. [1992b]’s recommendation is slightly different.
As this difference is due to averaging over the given wavelength intervals, the glyoxal absorption
cross sections used by Madronich and Calvert [1989] are retained.
The effective quantum yield for glyoxal reported by Plum et al. [1983] is 0.029 [Atkinson et
al., 1992b]. This quantum yield only applies to tropospheric conditions for = 325–470 nm. The
quantum yield measured by Langford and Moore [1984] at 308 nm is recommended for < 325 nm
[Atkinson et al., 1992b]. Because the sum of quantum yields used by Madronich and Calvert [1989]
( = 0:02877) is equal to that measured by Plum et al. [1983], the quantum yields from Madronich
209
Figure B.29 Iso-butanal (d042) Quantum Yield.
Figure B.30 CHOCHO Absorption Cross Section.
210
and Calvert [1989] for glyoxal were used.
Methylglyoxal, CH3C(O)CHO (dk33) The recommendation of Atkinson [1994] for the absorption cross section of methylglyoxal remains the same as the earlier recommendation [Atkinson
et al., 1992b]. This recommendation is based on the work of Meller et al. [1991]. Stockwell et al.
[1997] uses Atkinson [1994] and Staffelbach et al. [1995]. Figure B.31 indicates that the absorption
cross section for Stockwell et al. [1997] matches Atkinson et al. [1992b] and is significantly larger
than the absorption cross sections used by Madronich and Calvert [1989]. The model was altered
to use the methylglyoxal cross sections used by Stockwell et al. [1997].
Figure B.31 CH3 C(O)CHO Absorption Cross Section.
The recommendation of Atkinson [1994] for the quantum yield of methylglyoxal remains
unchanged from the earlier recommendation [Atkinson et al., 1992b]. This recommendation is
based on the work of Plum et al. [1983], who measured the rate of methylglyoxal photolysis.
The recommendation of Atkinson et al. [1989b] is also based on Plum et al. [1983], however,
the quantum yields recommended by Atkinson et al. [1989b] and Atkinson et al. [1992b] are not
equal, due to the different recommendations they make for the absorption cross sections. To remain
consistent with the measurements of Plum et al. [1983], Atkinson et al. [1992b] recommend the
quantum yield be decreased by a factor of 2 to offset the increased absorption cross sections. The
model was altered to reflect the recommendation of Atkinson et al. [1992b].
Other Aldehydes No recommendations were made for benzaldehyde (dr71) by DeMore et al.
[1997], Atkinson [1994], or Atkinson et al. [1992b]. In the absence of new data, the values used by
211
Figure B.32 Acetone (k031) Absorption Cross Section.
Madronich and Calvert [1989] were not changed.
B.3.4.2
Ketones
Acetone, CH3COCH3 (k031) Atkinson [1994] recommends the work of Martinez et al. [1992]
for the absorption cross section of acetone. Stockwell et al. [1997] also use the cross sections from
Martinez et al. [1992]. As shown in Figure B.32, Madronich and Calvert [1989] have a larger peak
near 280 nm than Martinez et al. [1992] and Stockwell et al. [1997]. The model was altered to use
the absorption cross sections measured by Martinez et al. [1992] for acetone.
The recommendation for quantum yield data for acetone by Atkinson [1994] and Atkinson et
al. [1992b] are based on Meyrahn et al. [1986]. Stockwell et al. [1997] use the recommendation
of Atkinson [1994], which is significantly different than the constant value used by Madronich and
Calvert [1989], as shown in Figure B.33. The acetone quantum yield from Stockwell et al. [1997],
which matches the recommendation of Atkinson et al. [1992b], was used.
2-butanone, CH3CH2 COCH3 (k041) Atkinson [1994] recommends Martinez et al. [1992]
where the absorption cross section for 2-butanone was measured and tabulated for the wavelength
region 200–330 nm. Figure B.34 shows that Madronich and Calvert [1989] have a slightly higher
peak near 280 nm than Martinez et al. [1992]. The model was altered to use absorption cross
section of Martinez et al. [1992] for 2-butanone.
212
Figure B.33 Acetone Quantum Yield.
Figure B.34 2-Butanone (k041) Absorption Cross Section.
213
Figure B.35 3-pentanone (k052) Absorption Cross Section.
According to Atkinson [1994], there are no data available for the photodissociation quantum
yields for the higher ketones. In the absence of new data, the values used byMadronich and Calvert
[1989] were not changed.
3-Pentanone, CH3CH2 COCH2CH3 (k052) Atkinson [1994] recommends the absorption
cross section values measured by Martinez et al. [1992]. Figure B.35 shows that Martinez et
al. [1992] is significantly larger than Madronich and Calvert [1989] at both peaks. The model was
altered to use the absorption cross sections measured by Martinez et al. [1992] for 3-pentanone.
According to Atkinson [1994], there are no data available for the photodissociation quantum
yields for the higher ketones. In the absence of new data, the pentanone quantum yields used by
Madronich and Calvert [1989] were not changed.
Biacetyl, CH3 COCOCH3 (kk43) Atkinson [1994] recommends the work of Plum et al. [1983]
for the cross section of biacetyl. As this source was published prior to the creation of the Master
Mechanism, the biacetyl absorption cross sections from Madronich and Calvert [1989]was used.
The quantum yield of biacetyl determined by Plum et al. [1983] is 0.158 for 325 nm
[Atkinson, 1994]. While for = 280–330 nm, the average quantum yield derived by Cox et al.
[1980] is 0.98 0.15. The quantum yield used by Madronich and Calvert [1989] is equal to 0.158.
As both of the studies were published in the early 1980s and the values used by Madronich and
Calvert [1989] are equal to the values measured by Plum et al. [1983], the biacetyl quantum yield
214
Figure B.36 Acrolein Absorption Cross Section.
from Madronich and Calvert [1989] was used.
B.3.4.3
Unsaturated Carbonyls
Acrolein, CH2=CHCHO (ud34) There are no recommendations for the cross section of
acrolein in Atkinson [1994], Atkinson et al. [1992b] or DeMore et al. [1997]. In the model
RACM [Stockwell et al., 1997], the compound MACR represents methacrolein and other unsaturated
monoaldehydes. However, the absorption cross section for MACR is treated as acrolein by Stockwell
et al. [1997] and is based on the work of Gardner et al. [1987]. Figure B.36 shows that the values
used by Stockwell et al. [1997] are very similar to the absorption cross sections used by Madronich
and Calvert [1989], except at the peak near 230 nm. Because this peak is also reported in Gardner
et al. [1987], it appears that Stockwell et al. [1997] didn’t include the peak due to its negligible
effect on the J values. The absorption cross sections from Madronich and Calvert [1989] were
retained.
The quantum yield data used by Stockwell et al. [1997] is based on data measured by Gardner
et al. [1987]. These values match the quantum yield data used by Madronich and Calvert [1989].
In the absence of new data, the quantum yield data given by Madronich and Calvert [1989] for
acrolein were not changed.
215
Other Unsaturated Carbonyls No recommendations were found for the following unsaturated carbonyls treated explicitly by Madronich and Calvert [1989]: CH3 COCOCH3 (kk43),
CHOCH=CHCHO (ud41), CH3 COCH=CHCHO (ud51), and CHOCH=C(CH3 )CHO (ud52). In
the absence of new data, the values used by Madronich and Calvert [1989] were not changed.
B.3.5 Acids
No recommendations were found for the following acids treated explicitly by Madronich and Calvert
[1989]: pyruvic acid (ak33), glyoxalic acid (ad21), and oxalic acid (aa21). In the absence of new
data, the values used by Madronich and Calvert [1989]were not changed.
Appendix C
Mechanism Revisions: Tables
This appendix contains the tables of revised rate parameters discussed in Appendix B.
216
217
Table C.1 Odd Oxygen Reactions.
Reaction
i O3 + O3P ! 2.00 O2
i O2 + O3P + M ! O3 + M
u C2H2 + O3P ! ?
A
i O3 + O1D ! 2.00 O2
k298
8.0E-15
6.1E-34
1.4E-13
1.2E-10
E/R
2.1E+03
-6.8E+02
1.6E+03
0.0E+00
i O3 + O1D ! O2 +2.00 O3P
i H2O + O1D ! 2.00 HO
iXN2 + O1D + M ! N2O + M
i N2 + O1D ! N2 + O3P
i O2 + O1D ! O2 + O3P
i CO2 + O1D ! CO2 + O3P
i H2 + O1D ! HO + H
A
c CH4 + O1D ! CH3 + HO
1.2E-10
2.2E-10
3.5E-37
2.6E-11
4.0E-11
1.1E-10
1.1E-10
1.4E-10
0.0E+00
0.0E+00
-1.8E+02
-1.1E+02
-7.0E+01
-1.2E+02
0.0E+00
0.0E+00
c CH4 + O1D ! CH2O + H2
m NH3 + O1D ! NH2 + HO
l CL2+ O1D ! 0.25 CL2 + 0.75 CLO + 0.75 CL + 0.25 O3P
l ld12+ O1D ! 2.00 ?
f HF+ O1D ! F + HO
f fl11+ O1D ! 2.00 ?
A
f CF2O+ O1D ! CO2 + F2
1.4E-11
2.5E-10
2.8E-10
3.6E-10
1.4E-10
1.9E-10
2.2E-11
0.0E+00
0.0E+00
0.0E+00
0.0E+00
0.0E+00
0.0E+00
0.0E+00
f CF2O+ O1D ! COF2+ O3P
b HBR + O1D ! 0.80 HBR + 0.20 BR + 0.20 HO + 0.80 O3P
1
l HCL + O1D ! 0.20 HCL+0.46 CLO + 0.46 H + 0.20 O3P
2
l HCL + O1D ! 1.34 CL + 1.34 HO
5.2E-11
1.5E-10
7.5E-11
7.5E-11
0.0E+00
0.0E+00
0.0E+00
0.0E+00
B
B
B
a Recommended by DeMore et al. [1997]
b E/R not reported by DeMore et al. [1997]
c Reaction was separated into 2 channels and products were added
Reference
Madronich and Calvert [1989] a
Madronich and Calvert [1989]a; b
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a;b
Madronich and Calvert [1989]a
DeMore et al. [1997]
DeMore et al. [1997]
DeMore et al. [1997]
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Atkinson et al. [1992b]a; c
Atkinson et al. [1992b]a;c
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
218
Table C.2 Odd Hydrogen Reactions.
Reaction
i H + O2 + (M) ! HO2 + (M)
iXH + O3 ! HO + O2
iXHO + O3P ! H + O2
i HO + O3 ! HO2 + O2
i HO + HO ! H2O + O3P
i HO + HO + (M) ! H2O2 + (M)
iXHO2 + O3P ! HO + O2
i HO2 + O3 ! HO + 2.00 O2
iXHO2+ H ! 0.10 H2 + 1.80 HO + 0.10 O2
i HO2 + HO ! H2O + O2
isHO2 + HO2 ! H2O2 + O2
i H2 + HO ! H2O + H
iXH2O2 + O3P ! HO2 + HO
i H2O2 + HO ! H2O + HO2
isCO + HO ! CO2 + H
k298
1.2E-12
2.9E-11
3.3E-11
6.8E-14
1.9E-12
5.9E-12
5.9E-11
2.0E-15
8.1E-11
1.1E-10
1.7E-12
6.7E-15
1.7E-15
1.7E-12
2.4E-13
a Recommended by DeMore et al. [1997]
b No E/R reported, use Madronich and Calvert [1989]
c See Table C.19
E/R
-1.0E+03
4.7E+02
-1.2E+02
9.4E+02
2.4E+02
-6.2E+02
-2.0E+02
5.0E+02
0.0E+00
-2.5E+02
-6.0E+02
2.0E+03
2.0E+03
1.6E+02
0.0E+00
Reference
Madronich and Calvert [1989]a;b;c
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
DeMore et al. [1997]b;c
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
DeMore et al. [1997]
DeMore et al. [1997]
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
DeMore et al. [1997]
Madronich and Calvert [1989]a
219
Table C.3 Inorganic Nitrogen Reactions.
Reaction
i N + O2 ! NO + O3P
i N + O3 ! NO + O2
i NO + O3 ! NO2 + O2
i NO + N ! N2 + O3P
i NO2 + O3P ! NO + O2
A
i NO2 + O3 ! NO3 + O2
k298
8.5E-17
<2.0E-16
1.8E-14
3.0E-11
9.7E-12
3.2E-17
E/R
3.6E+03
0.0E+00
1.4E+03
-1.0E+02
-1.2E+02
2.5E+03
i NO2 + O3 ! NO + 2.00 O2
i NO2 + N ! N2O + O3P
i NO3 + M ! NO + O2 + M
i NO3 + HO ! NO2 + HO2
i NO3 + NO3 ! 2.00 NO2 + O2
i NO3 + O3P ! NO2 + O2
i NO3 + NO ! 2.00 NO2
i NO3 + NO2 ! NO2 + NO + O2
i NO3 + NO2 + (M) ! N2O5 + (M)
iXN2O5 + O3P ! ?
iXHNO3 + O3P ! HO + NO3
iXHNO4 + O3P ! ?
A
i N2O + O1D ! N2 + O2
9.7E-19
1.2E-11
1.2E-22
2.2E-11
2.3E-16
1.0E-11
2.6E-11
6.6E-16
1.3E-12
< 3.0E-16
< 3.0E-17
8.6E-16
4.9E-11
2.5E+03
-2.2E+02
6.8E+03
0.0E+00
2.5E+03
0.0E+00
-1.7E+02
1.3E+03
-5.6E+02
0.0E+00
0.0E+00
3.4E+03
0.0E+00
i N2O + O1D ! 2.00 NO
i HNO2 + HO ! H2O + NO2
isHNO3 + HO ! H2O + NO3
i HNO4 + HO ! H2O + NO2 + O2
i H + NO2 ! HO + NO
i HO + NO + (M) ! HNO2 + (M)
i HO + NO2 + (M) ! HNO3 + (M)
i HO2 + NO ! HO + NO2
i HO2 + NO3 ! HNO3 + O2
i HNO2 + O3 ! HNO3 + O2
i H2O + N2O5 ! 2.00 HNO3
m NH3 + HO ! NH2 + H2O
A
m NH2 + O2 ! 2m01 + XPOO
6.7E-11
4.5E-12
1.3E-13
4.6E-12
1.3E-10
7.3E-12
1.1E-11
8.1E-12
3.5E-12
<5.0E-19
<2.0E-21
1.6E-13
5.8E-21
0.0E+00
3.9E+02
-7.8E+02
-3.8E+02
3.4E+02
-1.0E+03
-1.4E+03
-2.5E+02
0.0E+00
0.0E+00
0.0E+00
7.1E+02
0.0E+00
m NH2 + O2 ! H2O + NO
m NH2 + O3 ! NH2O + O2
m NH2 + HO2 ! ?
m NH2 + NO ! H2O + N2
m NH2 + NO2 ! H2O + N2O
i CO + NO3 ! CO2 + NO2
q HCN + O3P ! ?
q HCN + HO ! ?
q MECN + HO ! ?
1.9E-22
1.9E-13
3.4E-11
1.8E-11
1.9E-11
< 4.0E-19
1.5E-17
3.1E-14
2.3E-14
0.0E+00
9.3E+02
0.0E+00
-4.5E+02
-6.5E+02
0.0E+00
4.0E+03
4.0E+02
1.1E+03
B
B
B
Reference
DeMore et al. [1997]
DeMore et al. [1997]
Madronich and Calvert [1989] a
DeMore et al. [1997]
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]b
DeMore et al. [1997]
Madronich and Calvert [1989] c
DeMore et al. [1997] d
DeMore et al. [1997]d
Madronich and Calvert [1989]a
DeMore et al. [1997]
DeMore et al. [1997]e
DeMore et al. [1997]f
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
DeMore et al. [1997]
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
DeMore et al. [1997]d
DeMore et al. [1997]f
DeMore et al. [1997]f
DeMore et al. [1997]
DeMore et al. [1997] g
Madronich and Calvert [1989]a
DeMore et al. [1997]
DeMore et al. [1997]
DeMore et al. [1997]h
DeMore et al. [1997]h
DeMore et al. [1997]
Madronich and Calvert [1989]a
DeMore et al. [1997]
DeMore et al. [1997]
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
Madronich and Calvert [1989]a
DeMore et al. [1997]
a Recommended by DeMore et al. [1997]
b see text
c Reaction no longer included in calculations, see text
d New Reaction
e Reaction pathway not firmly established, Arrhenius expression provided, also a three body reaction path
f See Table C.19
g products changed
h Branching ratio based on Madronich and Calvert [1989]
220
Table C.4 Organic Updates.
Reaction
c CH4 + HO ! CH3 + H2O
c CH4 + NO3 ! CH3 + HNO3
c C2H6 + HO ! C2H5 + H2O
c C2H6 + NO3 ! C2H5 + HNO3
1
c C3H8 + HO ! 1.5 2031 + 0.5 2032 + 2. H2O
2
c C3H8 + HO ! 1.5 XSOO + 0.50 XPOO
1
c C3H8 NO3 ! 1.50 2031 0.50 2032 2.00 HNO3
2
c C3H8 NO3 ! 1.50 XSOO + 0.50 XPOO
1
c c041 + HO ! 1.72 2041 + 0.28 2042 + 2. H2O
2
c c041 + HO ! 1.72 XSOO + 0.28 XPOO
c c041 + NO3 ! 2041 + HNO3 + XSOO
c c042 + HO ! 2043 + H2O + XTOO
c c042 + NO3 ! 2043 + HNO3 + XTOO
1
c c052 + HO ! 0.18 2053 + 1.10 2054 + 0.72 2055
2
c c052 + HO ! 0.18 XPOO + 1.82 XSOO
c c052 + NO3 ! 2054 + HNO3 + XSOO
1
c c053 + HO ! 0.54 2052 0.28 2056 1.18 2057
2
c c053 + HO ! 0.28 XPOO 0.54 XSOO 1.18 XTOO
c c053 + NO3 ! 2057 + HNO3 + XTOO
1
c c062 + HO ! 1.84 2062 0.16 2063 2.00 H2O
2
c c062 + HO ! 1.84 XTOO 0.16 XPOO
c c062 + NO3 ! 2062 + HNO3 + XTOO
u C2H2 + HO + (M) ! dd21 HO (M)
u C2H2 + O3 ! ?
u C2H4 + HO + (M) ! 0o21 (M)
u C2H4 + NO3 ! 2n22 + XPOO
u C2H4 + O3 ! 7011 + CH2O
u C3H6 + HO ! 0.65 2o32 + 0.35 2o33 +
k298
6.3E-15
< 1.0E-18
2.4E-13
1.4E-18
5.5E-13
5.5E-13
8.5E-18
8.5E-18
E/R
1.8E+03
0.0E+00
1.1E+03
1.3E+03
6.6E+02
6.6E+02
0.0E+00
0.0E+00
1.3E-12
1.3E-12
4.6E-17
2.3E-12
1.1E-16
2.0E-12
5.6E+02
5.6E+02
3.3E+03
8.5E+02
3.1E+03
3.7E+02
2.0E-12
8.1-17
3.7E+02
3.9E+03
2.0E-12
2.0E-12
1.6E-16
3.0E-12
3.0E-12
4.3E-16
7.5E-13
1.0E-20
8.2E-12
2.0E-16
1.7E-18
2.6E-11
5.3E+02
5.3E+02
3.9E+03
8.4E+01
8.4E+01
3.1E+03
1.3E+03
4.1E+03
-1.2E+01
2.9E+03
2.6E+03
-5.0E+02
9.5E-15
1.1E-17
1.2E+03
1.9E+03
6.0E-11
3.7E-13
1.5E-16
3.1E-11
-5.2E+02
2.1E+02
1.0E+03
-4.7E+02
1.2E-14
9.6E-18
8.4E+02
1.7E+03
Reference
DeMore et al. [1997]
Atkinson [1994] a;b
DeMore et al. [1997]
Atkinson [1994]a;b
DeMore et al. [1997]
DeMore et al. [1997]
Atkinson [1994]a;b
Atkinson [1994]a;b
Madronich and Calvert [1989] c;d
Madronich and Calvert [1989]c;d
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]d
Atkinson [1994]d
Atkinson [1994] e
Atkinson [1994]e
Atkinson [1994]e
Atkinson [1994]e
Atkinson [1994]d
Atkinson [1994]d
Atkinson [1994]e
Madronich and Calvert [1989]e;f ; g
DeMore et al. [1997]b
DeMore et al. [1997]e;g
Atkinson [1994]d
DeMore et al. [1997]
Atkinson [1994]
+ 0.35 XPOO + 0.65 XSOO
u C3H6 + NO3 ! 2n32 + XSOO
u C3H6 + O3 ! 0.50 7021 + 0.50 d021
+ 0.50 7011 + 0.50 CH2O
u u041 + HO ! 2o43 + XSOO
u u041 + NO3 ! 2n45 XSOO
u u041 + O3 ! 7021 d021
u u042 + HO ! 0.50 2o44 + 0.50 2o45
Atkinson [1994]
DeMore et al. [1997]
Atkinson [1994] h
Atkinson [1994]h;i
Atkinson [1994]h
Atkinson [1994]
+ 0.50 XPOO + 0.50 XTOO
u u042 + NO3 ! 2n46 XTOO
u u042 + O3 ! 0.50 7031 + 0.50 k031 +
0.50 7011 + 0.50 CH2O
a products based on h-atom abstraction
b New Reaction
c Recommended by Atkinson [1994]
d E/R calculated from D+nT, not reported as Arrhenius equation
e No E/R value reported, use value from Madronich and Calvert [1989]
f Recommended by DeMore et al. [1997]
g see Table C.19
h average of cis and trans isomers
i E/R for trans isomer
Atkinson [1994]
Atkinson [1994]
221
Table C.5 Alkyl Radical Updates.
Reaction
0XCH3 O3
0XCH3 O2
0 CH3 O2 (M)
0 C2H5 O2
0 C2H5 O2 (M)
0 HCO O2
0 0o11 O2
k298
!
!
!
!
!
!
!
E/R
?
?
2011 (M)
C2H4 HO2
2021 XPOO (M)
CO HO2
CH2O HO2
a Recommended by DeMore et al. [1997]
Reference
2.6E-12 2.2E+02
<3.0E-16 0.0E+00
1.1E-12 -1.2E+03
<2.0E-14 0.0E+00
7.5E-12 -1.2E+03
5.5E-12 -1.4E+02
9.1E-12 0.0E+00
Madronich and Calvert [1989] a
Madronich and Calvert [1989]a
DeMore et al. [1997], see Table C.19
DeMore et al. [1997]
DeMore et al. [1997], See Table C.19
Madronich and Calvert [1989]a
DeMore et al. [1997]
222
Table C.6 Peroxy radical reaction with NO.
2 2n11 NO
2 2011 NO
2 2o11 NO
2 2m11 NO
2 2m12 NO
2 2n21 NO
2 2p21 NO
2 2d21 NO
2 2a21 NO
2 2g21 NO
2 2n22 NO
2 2n23 NO
2 2021 NO
2 2021 NO
2 2o21 NO
2 2m21 NO
2 2m22 NO
2 2m23 NO
2 2m23 NO
2 2v31 NO
2 2d33 NO
2 2d33 NO
2 2a32 NO
2 2a32 NO
2 2n31 NO
2 2n35 NO
2 2d32 NO
2 2d32 NO
2 2d34 NO
2 2d34 NO
2 2k33 NO
2 2k33 NO
2 2a31 NO
2 2a31 NO
2 2d31 NO
2 2d31 NO
2 2k34 NO
2 2k34 NO
2 2n32 NO
2 2n33 NO
2 2n34 NO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
1
!
2
!
!
A
B
!
A
!
B
!
!
!
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
!
!
!
Reaction
1n11 NO2 -1.00 XPOO
CH3O NO2
1o11 NO2 -1.00 XPOO
CH2O NH2 NO2 -1.00 XPOO
1m11 NO2 -1.00 XSOO
1n21 NO2 -1.00 XSOO
1p21 NO2 -1.00 XPOO
1d21 NO2 -1.00 XPOO
1a21 NO2 -1.00 XPOO
1g21 NO2 -1.00 XPOO
1n22 NO2 -1.00 XPOO
1n23 NO2 -1.00 XSOO
n021
1021 NO2 -1.00 XPOO
1o22 NO2 -1.00 XPOO
d021 NH2 NO2 -1.00 XSOO
0m11 CH2O NO2 -1.00 XPOO
2.00 w011 2.00 CH2O 2.00 HO2 2.00 NO2
k2 98 E/R
4.0E-12 0.0E+00
7.7E-12 -2.8E+02
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
8.2E-14 -3.7E+02
8.7E-12 -3.7E+02
9.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
2.0E-12 0.0E+00
-2.00 XTOO
CH2O 2.00 CO 2.00 NO2 -1.00 XPOO
2.0E-12 0.0E+00
4.0E-12 0.0E+00
1d34 NO2 -1.00 XPOO
nd33 -1.00 XPOO
3.9E-12 0.0E+00
8.0E-14 0.0E+00
1a32 NO2 -1.00 XPOO
an34 -1.00 XPOO
1n31 NO2 -1.00 XSOO
1n35 NO2 -1.00 XPOO
1d31 NO2 -1.00 XSOO
3.9E-12 0.0E+00
8.0E-14 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
3.8E-12 0.0E+00
nd35 -1.00 XSOO
1d35 NO2 -1.00 XPOO
1.9E-13 0.0E+00
3.9E-12 0.0E+00
nd38 -1.00 XPOO
1k33 NO2 -1.00 XPOO
8.0E-14 0.0E+00
3.9E-12 0.0E+00
nk38 -1.00 XPOO
an35 -1.00 XSOO
8.0E-14 0.0E+00
1.9E-13 0.0E+00
1a31 NO2 -1.00 XSOO
1d32 NO2 -1.00 XSOO
3.8E-12 0.0E+00
3.8E-12 0.0E+00
nd34 -1.00 XSOO
1k31 NO2 -1.00 XPOO
1.9E-13 0.0E+00
3.9E-12 0.0E+00
nk31 -1.00 XPOO
0.04 nn31 0.96 1n32 0.96 NO2 -1.00 XSOO
d021 CH2O 2.00 NO2 -1.00 XPOO
do23 CH2O 2.00 NO2 -1.00 XSOO
8.0E-14 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
a Reaction added by Williams [1994a]
Source
DeMore et al. [1997]
didn’t use, added by williams
DeMore et al. [1997]
Kirchner and Stockwell [1996]
a
223
Table C.6 (continued) Peroxy radical reaction with NO
2 2031 NO
2 2031 NO
2 2032 NO
2 2032 NO
2 2o32 NO
2 2o32 NO
2 2o33 NO
2 2o33 NO
2 2o34 NO
2 2o34 NO
2 2o31 NO
2 2o31 NO
2 2o35 NO
2 2o35 NO
2 2m33 NO
2 2p30 NO
2 2p30 NO
2 2p31 NO
2 2p31 NO
2 2d41 NO
2 2d41 NO
2 2d42 NO
2 2d42 NO
2 2k43 NO
2 2k43 NO
2 2a42 NO
2 2a42 NO
2 2d43 NO
2 2d43 NO
2 2d45 NO
2 2d45 NO
2 2g40 NO
2 2g40 NO
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
!
A
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
!
Reaction
k2 98 E/R
1032 NO2 -1.00 XSOO
n032 -1.00 XSOO
4.1E-12 0.0E+00
2.0E-13 0.0E+00
1031 NO2 -1.00 XPOO
n031 -1.00 XPOO
3.9E-12 0.0E+00
8.0E-14 0.0E+00
1o33 NO2 -1.00 XSOO
no34 -1.00 XSOO
3.8E-12 0.0E+00
1.9E-13 0.0E+00
1o34 NO2 -1.00 XPOO
no33 -1.00 XPOO
3.9E-12 0.0E+00
8.0E-14 0.0E+00
1o35 NO2 -1.00 XPOO
no35 -1.00 XPOO
3.9E-12 0.0E+00
8.0E-14 0.0E+00
1o32 NO2 -1.00 XSOO
no32 -1.00 XSOO
3.8E-12 0.0E+00
1.9E-13 0.0E+00
1o31 NO2 -1.00 XPOO
no31 -1.00 XPOO
0m22 CH2O NO2 -1.00 XPOO
1p30 NO2 -1.00 XPOO
3.9E-12 0.0E+00
8.0E-14 0.0E+00
4.0E-12 0.0E+00
3.9E-12 0.0E+00
pn30 -1.00 XPOO
1p31 NO2 -1.00 XSOO
8.0E-14 0.0E+00
3.8E-12 0.0E+00
pn34 -1.00 XSOO
1d41 NO2 -1.00 XSOO
1.9E-13 0.0E+00
3.7E-12 0.0E+00
nd41 -1.00 XSOO
1d42 NO2 -1.00 XSOO
3.4E-13 0.0E+00
3.7E-12 0.0E+00
nd44 -1.00 XSOO
dk40 HO2 NO2 -1.00 XPOO
3.4E-13 0.0E+00
3.9E-12 0.0E+00
nk47 -1.00 XPOO
1a43 NO2 -1.00 XSOO
1.4E-13 0.0E+00
3.7E-12 0.0E+00
an4A -1.00 XSOO
1d44 NO2 -1.00 XSOO
3.4E-13 0.0E+00
3.7E-12 0.0E+00
nd45 -1.00 XSOO
1d45 NO2 -1.00 XPOO
3.4E-13 0.0E+00
3.9E-12 0.0E+00
nd46 -1.00 XPOO
1g40 NO2 -1.00 XTOO
1.4E-13 0.0E+00
3.9e-12 0.0E+00
gn40 -1.00 XTOO
1.1e-13 0.0E+00
a Branching ratio from Madronich and Calvert [1989]
Source
Kirchner and Stockwell [1996] a
224
Table C.6 (continued) Peroxy radical reaction with NO
Reaction
1n41 NO2 -1.00 XSOO
!
1n43 NO2 -1.00 XPOO
k2 98 E/R
4.0E-12 0.0E+00
4.0E-12 0.0E+00
1n45 NO2 -1.00 XTOO
nn43 -1.00 XTOO
3.9E-12 0.0E+00
1.1E-13 0.0E+00
1n48 NO2 -1.00 XSOO
nn44 -1.00 XSOO
1n42 NO2 -1.00 XSOO
1n44 NO2 -1.00 XPOO
1n4a NO2 -1.00 XSOO
1n4b NO2 -1.00 XPOO
1d47 NO2 -1.00 XSOO
nd48 -1.00 XSOO
3.7E-12 0.0E+00
3.4E-13 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
3.7E-12 0.0E+00
3.4E-13 0.0E+00
1d49 NO2 -1.00 XPOO
nd40 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1k45 NO2 -1.00 XSOO
nk45 -1.00 XSOO
3.7E-12 0.0E+00
3.4E-13 0.0E+00
1k42 NO2 -1.00 XPOO
nk43 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1k47 NO2 -1.00 XPOO
nk49 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1a41 NO2 -1.00 XSOO
an40 -1.00 XSOO
3.7E-12 0.0E+00
3.4E-13 0.0E+00
1d43 NO2 -1.00 XTOO
nd47 -1.00 XTOO
3.9E-12 0.0E+00
1.1E-13 0.0E+00
1d48 NO2 -1.00 XSOO
nd49 -1.00 XSOO
3.7E-12 0.0E+00
3.4E-13 0.0E+00
1k40 NO2 -1.00 XPOO
nk4A -1.00 XPOO
3.9E-12 0.0E+00
1.4E-14 0.0E+00
1k44 NO2 -1.00 XSOO
nk46 -1.00 XSOO
3.7E-12 0.0E+00
3.4E-13 0.0E+00
1k46 NO2 -1.00 XPOO
nk48 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1k48 NO2 -1.00 XPOO
nk40 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
2 2n41 NO
2 2n43 NO
!
2 2n47 NO
2 2n47 NO
!
2 2n48 NO
2 2n48 NO
2 2n42 NO
2 2n44 NO
2 2n4a NO
2 2n4b NO
2 2d47 NO
2 2d47 NO
2 2d49 NO
2 2d49 NO
2 2k44 NO
2 2k44 NO
2 2k45 NO
2 2k45 NO
2 2k47 NO
2 2k47 NO
2 2a41 NO
2 2a41 NO
2 2d44 NO
2 2d44 NO
2 2d48 NO
2 2d48 NO
2 2k40 NO
2 2k40 NO
2 2k42 NO
2 2k42 NO
2 2k48 NO
2 2k48 NO
2 2k49 NO
2 2k49 NO
A
B
!
A
!
B
!
!
!
!
!
A
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
!
a Reaction added by Williams [1994a]
Source
a
a
225
Table C.6 (continued) Peroxy radical reaction with NO
2 2k4B NO
2 2k4B NO
2 2a43 NO
2 2a43 NO
2 2a47 NO
2 2a47 NO
2 2k46 NO
2 2k46 NO
2 2k4C NO
2 2k4C NO
2 2n45 NO
2 2n45 NO
2 2n46 NO
2 2n46 NO
2 2041 NO
2 2041 NO
2 2042 NO
2 2042 NO
2 2043 NO
2 2043 NO
2 2o40 NO
2 2o40 NO
2 2o42 NO
2 2o42 NO
2 2o43 NO
2 2o43 NO
2 2o44 NO
2 2o44 NO
2 2o45 NO
2 2o45 NO
2 2o46 NO
2 2o46 NO
2 2o4A NO
2 2o4A NO
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
Reaction
k2 98 E/R
1k4B NO2 -1.00 XPOO
3.9E-12 0.0E+00
nk4B -1.00 XPOO
1a44 NO2 -1.00 XTOO
1.4E-13 0.0E+00
3.9E-12 0.0E+00
an49 -1.00 XTOO
1a42 NO2 -1.00 XPOO
an4B -1.00 XPOO
1.1E-13 0.0E+00
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1k4D NO2 -1.00 XPOO
nk4J -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1k4C NO2 -1.00 XPOO
nk4C -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1n47 NO2 -1.00 XSOO
nn41 -1.00 XSOO
3.7E-12 0.0E+00
3.4E-13 0.0E+00
1n46 NO2 -1.00 XTOO
nn42 -1.00 XTOO
3.9E-12 0.0E+00
1.1E-13 0.0E+00
1043 NO2 -1.00 XSOO
n042 -1.00 XSOO
3.7E-12 0.0E+00
3.5E-13 0.0E+00
1042 NO2 -1.00 XPOO
n041 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1044 NO2 -1.00 XTOO
n043 -1.00 XTOO
3.9E-12 0.0E+00
1.1E-13 0.0E+00
1o40 NO2 -1.00 XPOO
no40 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1o43 NO2 -1.00 XPOO
no42 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1o44 NO2 -1.00 XSOO
no43 -1.00 XSOO
3.7E-12 0.0E+00
3.4E-13 0.0E+00
1o41 NO2 -1.00 XTOO
no44 -1.00 XTOO
3.9E-12 0.0E+00
1.1E-13 0.0E+00
1o45 NO2 -1.00 XPOO
no45 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1o46 NO2 -1.00 XPOO
no46 -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
1o4A NO2 -1.00 XPOO
no4A -1.00 XPOO
3.9E-12 0.0E+00
1.4E-13 0.0E+00
Source
Kirchner and Stockwell [1996] a
Kirchner and Stockwell [1996] b
a Branching ratio calculated using methods of Kirchner and Stockwell [1996]
b Branching ratio from Kirchner and Stockwell [1996], see text
226
Table C.6 (continued) Peroxy radical reaction with NO
2 2o4C NO
2 2o4C NO
2 2o48 NO
2 2o48 NO
2 2o49 NO
2 2o49 NO
2 2o4B NO
2 2o4B NO
2 2o4D NO
2 2o4D NO
2 2d51 NO
2 2d51 NO
2 2d53 NO
2 2d53 NO
2 2d57 NO
2 2d57 NO
2 2d5A NO
2 2d5A NO
2 2d5A NO
2 2d52 NO
2 2d52 NO
2 2d55 NO
2 2d55 NO
2 2d56 NO
2 2d56 NO
2 2d54 NO
2 2d54 NO
2 2n51 NO
2 2n51 NO
2 2n52 NO
2 2n52 NO
2 2n55 NO
2 2n56 NO
2 2n57 NO
2 2n58 NO
2 2n59 NO
2 2n5a NO
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
1A
!
2A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
!
!
!
!
!
!
Reaction
k2 98 E/R
1o4C NO2 -1.00 XPOO
3.9E-12 0.0E+00
no4C -1.00 XPOO
1o48 NO2 -1.00 XPOO
1.4E-13 0.0E+00
3.9E-12 0.0E+00
no4E -1.00 XPOO
1o49 NO2 -1.00 XPOO
1.4E-13 0.0E+00
3.9E-12 0.0E+00
no4F -1.00 XPOO
1o4B NO2 -1.00 XPOO
1.4E-13 0.0E+00
3.9E-12 0.0E+00
no4B -1.00 XPOO
1o4D NO2 -1.00 XPOO
1.4E-13 0.0E+00
3.7E-12 0.0E+00
no4D -1.00 XPOO
1d51 NO2 -1.00 XTOO
3.4E-13 0.0E+00
3.8E-12 0.0E+00
nd51 -1.00 XTOO
1d53 NO2 -1.00 XSOO
1.7E-13 0.0E+00
3.5E-12 0.0E+00
nd53 -1.00 XSOO
1d57 NO2 -1.00 XSOO
5.2E-13 0.0E+00
3.5E-12 0.0E+00
nd55 -1.00 XSOO
2.00 dk33 2.00 2d21 2.00 NO2 2.00 XPOO
5.2E-13 0.0E+00
1.9E-12 0.0E+00
-2.00 XTOO
nd50 -1.00 XTOO
1.9E-12 0.0E+00
1.7E-13 0.0E+00
1d52 NO2 -1.00 XSOO
nd52 -1.00 XSOO
3.5E-12 0.0E+00
5.2E-13 0.0E+00
1d56 NO2 -1.00 XSOO
nd56 -1.00 XSOO
3.5E-12 0.0E+00
5.2E-13 0.0E+00
1d55 NO2 -1.00 XTOO
nd57 -1.00 XTOO
3.8E-12 0.0E+00
1.7E-13 0.0E+00
1d54 NO2 -1.00 XPOO
nd54 -1.00 XPOO
1n51 NO2 -1.00 XTOO
3.8E-12 0.0E+00
2.3E-13 0.0E+00
3.8E-12 0.0E+00
nn51 -1.00 XTOO
nn52 -1.00 XSOO
1.7E-13 0.0E+00
5.2E-13 0.0E+00
1n52 NO2 -1.00 XSOO
1n55 NO2 -1.00 XSOO
1n56 NO2 -1.00 XSOO
1n57 NO2 -1.00 XSOO
1n58 NO2 -1.00 XSOO
1n59 NO2 -1.00 XSOO
1n5a NO2 -1.00 XPOO
3.5E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
a Reaction added by Williams [1994a]
Source
a
a
a
a
a
a
227
Table C.6 (continued) Peroxy radical reaction with NO
2 2d50 NO
2 2d50 NO
2 2d58 NO
2 2d58 NO
2 2u51 NO
2 2u51 NO
2 2u52 NO
2 2u52 NO
2 2k51 NO
2 2k51 NO
2 2k61 NO
2 2k52 NO
2 2k53 NO
2 2n53 NO
2 2n53 NO
2 2n54 NO
2 2n54 NO
2 2h53 NO
2 2h53 NO
2 2h54 NO
2 2h54 NO
2 2051 NO
2 2051 NO
2 2052 NO
2 2052 NO
2 2053 NO
2 2053 NO
2 2054 NO
2 2054 NO
2 2055 NO
2 2055 NO
2 2056 NO
2 2056 NO
2 2057 NO
2 2057 NO
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
!
!
!
A
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
!
Reaction
k2 98 E/R
1d5A NO2 -1.00 XSOO
nd5A -1.00 XSOO
3.5E-12 0.0E+00
5.2E-13 0.0E+00
1d58 NO2 -1.00 XSOO
nd58 -1.00 XSOO
3.5E-12 0.0E+00
5.2E-13 0.0E+00
1u52 NO2 -1.00 XTOO
nu51 -1.00 XTOO
3.8E-12 0.0E+00
1.7E-13 0.0E+00
1u51 NO2 -1.00 XSOO
nu52 -1.00 XSOO
3.5E-12 0.0E+00
5.2E-13 0.0E+00
1k51 NO2 -1.00 XTOO
nk51 -1.00 XTOO
1k61 NO2 -1.00 XSOO
1k52 NO2 -1.00 XSOO
1k53 NO2 -1.00 XSOO
1n53 NO2 -1.00 XSOO
3.8E-12 0.0E+00
1.7E-13 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
3.5E-12 0.0E+00
nn53 -1.00 XSOO
1n54 NO2 -1.00 XTOO
5.2E-13 0.0E+00
3.8E-12 0.0E+00
nn53 -1.00 XTOO
1h51 NO2 -1.00 XSOO
1.7E-13 0.0E+00
3.5E-12 0.0E+00
hn51 -1.00 XSOO
1h52 NO2 -1.00 XTOO
5.2E-13 0.0E+00
3.8E-12 0.0E+00
hn52 -1.00 XTOO
1051 NO2 -1.00 XSOO
1.7E-13 0.0E+00
3.5E-12 0.0E+00
n051 -1.00 XSOO
1052 NO2 -1.00 XSOO
5.2E-13 0.0E+00
3.5E-12 0.0E+00
n052 -1.00 XSOO
1053 NO2 -1.00 XPOO
n053 -1.00 XPOO
5.2E-13 0.0E+00
3.8E-12 0.0E+00
2.3E-13 0.0E+00
1054 NO2 -1.00 XSOO
n054 -1.00 XSOO
3.5E-12 0.0E+00
5.2E-13 0.0E+00
1055 NO2 -1.00 XSOO
n055 -1.00 XSOO
3.5E-12 0.0E+00
5.2E-13 0.0E+00
1056 NO2 -1.00 XPOO
n056 -1.00 XPOO
3.8E-12 0.0E+00
2.3E-13 0.0E+00
1057 NO2 -1.00 XTOO
n057 -1.00 XTOO
3.8E-12 0.0E+00
1.7E-13 0.0E+00
a Reaction added by Williams [1994a]
Source
a
a
a
228
Table C.6 (continued) Peroxy radical reaction with NO
2 2o51 NO
2 2o51 NO
2 2o52 NO
2 2o52 NO
2 2o55 NO
2 2o55 NO
2 2o56 NO
2 2o56 NO
2 2o57 NO
2 2o57 NO
2 2o58 NO
2 2o58 NO
2 2o59 NO
2 2o59 NO
2 2o50 NO
2 2o50 NO
2 2o53 NO
2 2o53 NO
2 2o54 NO
2 2o54 NO
2 2h51 NO
2 2h51 NO
2 2h52 NO
2 2h52 NO
2 2o5A NO
2 2o5A NO
2 2o5B NO
2 2o5B NO
2 2a51 NO
2 2a51 NO
2 2a50 NO
2 2a50 NO
2 2a53 NO
2 2a53 NO
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
Reaction
k2 98 E/R
1o52 NO2 -1.00 XSOO
3.5E-12 0.0E+00
no52 -1.00 XSOO
1o54 NO2 -1.00 XSOO
5.2E-13 0.0E+00
3.5E-12 0.0E+00
no53 -1.00 XSOO
1o5A NO2 -1.00 XPOO
5.2E-13 0.0E+00
3.8E-12 0.0E+00
no5A -1.00 XPOO
1o56 NO2 -1.00 XSOO
2.3E-13 0.0E+00
3.5E-12 0.0E+00
no56 -1.00 XSOO
1o57 NO2 -1.00 XPOO
5.2E-13 0.0E+00
3.8E-12 0.0E+00
no57 -1.00 XPOO
1o58 NO2 -1.00 XPOO
2.3E-13 0.0E+00
3.8E-12 0.0E+00
no58 -1.00 XPOO
1o59 NO2 -1.00 XPOO
2.3E-13 0.0E+00
3.8E-12 0.0E+00
no59 -1.00 XPOO
1o50 NO2 -1.00 XSOO
2.3E-13 0.0E+00
3.5E-12 0.0E+00
no50 -1.00 XSOO
1o53 NO2 -1.00 XSOO
5.2E-13 0.0E+00
3.5E-12 0.0E+00
no51 -1.00 XSOO
1o51 NO2 -1.00 XSOO
5.2E-13 0.0E+00
3.5E-12 0.0E+00
no54 -1.00 XSOO
hk51 HO2 NO2 -1.00 XSOO
5.2E-13 0.0E+00
3.5E-12 0.0E+00
hn53 -1.00 XSOO
1h53 NO2 -1.00 XTOO
5.2E-13 0.0E+00
3.8E-12 0.0E+00
hn54 -1.00 XTOO
1o5C NO2 -1.00 XSOO
1.7E-13 0.0E+00
3.5e-12 0.0E+00
no5C -1.00 XSOO
1o5B NO2 -1.00 XPOO
5.2e-13 0.0E+00
3.8e-12 0.0E+00
no5D -1.00 XPOO
1a50 NO2 -1.00 XSOO
an54 -1.00 XSOO
2.3e-13 0.0E+00
3.5E-12 0.0E+00
5.2E-13 0.0E+00
1a51 NO2 -1.00 XSOO
an52 -1.00 XSOO
3.5E-12 0.0E+00
5.2E-13 0.0E+00
1a52 NO2 -1.00 XPOO
an55 -1.00 XSOO
3.8E-12 0.0E+00
2.3E-13 0.0E+00
Source
229
Table C.6 (continued) Peroxy radical reaction with NO
2 2r63 NO
2 2r61 NO
2 2r61 NO
!
2 2r62 NO
2 2r62 NO
!
2 2r62 NO
2 2d61 NO
2 2d61 NO
2 2d61 NO
2 2d62 NO
2 2d62 NO
2 2d62 NO
2 2061 NO
2 2061 NO
2 2062 NO
2 2063 NO
2 2o61 NO
2 2o61 NO
2 2o62 NO
2 2o63 NO
2 2o64 NO
2 2o64 NO
2 2r72 NO
2 2r72 NO
2 2r75 NO
2 2r75 NO
2 2r75 NO
2 2r75 NO
2 2r75 NO
2 2r71 NO
2 2r71 NO
2 2r71 NO
2 2r73 NO
2 2r73 NO
2 2r73 NO
2 2r73 NO
2 2r73 NO
1
!
2
!
A
A
!
B
!
1A
!
2A
!
B
!
1A
!
2A
!
B
!
A
!
B
!
1
2
!
!
A
B
!
!
!
!
A
B
!
A
!
B
!
1A
!
2A
!
1B
!
2B
!
!
!
A
1B
!
2B
!
1A
!
2A
!
1B
!
2B
!
!
!
Reaction
1r61 NO2 -1.00 XTOO
2.00 ud41 2.00 dd21 2.00 HO2 2.00 NO2
-2.00 XSOO
k2 98 E/R
4.0E-12 0.0E+00
2.0E-12 0.0E+00
2.0E-12 0.0E+00
2.00 ud41 2.00 ad21 2.00 HO2 2.00 NO2
-2.00 XSOO
1.6E-12 0.0E+00
1.6E-12 0.0E+00
rk61 -1.00 XSOO
2.00 k031 2.00 2d32 2.00 NO2 2.00 XSOO
7.9E-12 0.0E+00
1.9E-12 0.0E+00
-2.00 XTOO
nd61 -1.00 XTOO
2.00 ko37 2.00 2d32 2.00 NO2 2.00 XSOO
1.9E-12 0.0E+00
2.8E-13 0.0E+00
1.9E-12 0.0E+00
-2.00 XTOO
nd62 -1.00 XTOO
1.9E-12 0.0E+00
2.8E-13 0.0E+00
1061 NO2 -1.00 XSOO
n061 -1.00 XSOO
0.17 n062 0.83 1062 0.83 NO2 -1.00 XTOO
0.17 n063 0.83 1063 0.83 NO2 -1.00 XPOO
3.2E-12 0.0E+00
7.9E-13 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
1o61 NO2 -1.00 XPOO
no61 -1.00 XPOO
0.17 no62 0.83 1o63 0.83 NO2 -1.00 XPOO
0.17 no63 0.83 1o64 0.83 NO2 -1.00 XPOO
1o62 NO2 -1.00 XPOO
3.6E-12 0.0E+00
3.6E-13 0.0E+00
4.0E-12 0.0E+00
4.0E-12 0.0E+00
3.6E-12 0.0E+00
no64 -1.00 XPOO
1r71 NO2 -1.00 XPOO
3.6E-13 0.0E+00
3.5E-12 0.0E+00
nr75 -1.00 XPOO
2.00 ud53 2.00 dd21 2.00 HO2 2.00 NO2
5.5E-13 0.0E+00
1.1E-12 0.0E+00
-2.00 XTOO
2.00 ud43 2.00 dk33 2.00 HO2 2.00 NO2
-2.00 XTOO
C nr74 -1.00 XTOO
1.1E-12 0.0E+00
7.5E-13 0.0E+00
7.5E-13 0.0E+00
4.2E-13 0.0E+00
nr73 -1.00 XTOO
ud51 ud43 ak33 av22
4.2E-13 0.0E+00
1.8E-12 0.0E+00
2.00 HO2 2.00 NO2 -2.00 XTOO
2.00 ud41 2.00 dk33 2.00 HO2 2.00 NO2
1.8E-12 0.0E+00
2.1E-12 0.0E+00
-2.00 XTOO
2.00 ud51 2.00 dd21 2.00 HO2 2.00 NO2
2.1E-12 0.0E+00
7.5E-13 0.0E+00
-2.00 XTOO
C nr71 -1.00 XTOO
7.5E-13 0.0E+00
4.2E-13 0.0E+00
Source
230
Table C.6 (continued) Peroxy radical reaction with NO
2 2r74 NO
2 2r74 NO
2 2r74 NO
2 2r74 NO
2 2r74 NO
2 2u71 NO
2 2u71 NO
2 2t71 NO
2 2e72 NO
2 2e72 NO
2 2h71 NO
2 2h71 NO
2 2071 NO
2 2071 NO
2 2o71 NO
2 2o71 NO
2 2r81 NO
2 2r81 NO
2 2r82 NO
2 2r82 NO
2 2t81 NO
2 2t81 NO
2 2d82 NO
2 2d82 NO
2 2081 NO
2 2081 NO
2 2o81 NO
2 2o81 NO
2 2t91 NO
2 2t91 NO
2 2nA1 NO
2 2nA1 NO
2 2tA1 NO
2 2tA1 NO
A
2A
!
1B
!
2B
!
1
!
!
1
!
2
!
!
1
!
2
!
1
!
2
!
A
B
!
A
!
B
!
!
1
!
2
!
1
!
2
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
A
!
B
!
Reaction
k2 98 E/R
2.00 ud41 2.00 ak33 2.00 HO2 2.00 NO2
-2.00 XTOO
1.1E-12 0.0E+00
1.1E-12 0.0E+00
2.00 ud51 2.00 ad21 2.00 HO2 2.00 NO2
-2.00 XTOO
C nr72 -1.00 XTOO
0.46 nt71 1.54 2t71 1.54 NO2 1.54 XTOO
-2.00 XPOO
0.23 en72 0.77 2e72 0.77 NO2 -0.23 XTOO
0.40 en72 1.60 dk40 1.60 HO2 1.60 NO2
1.60 k031 -2.00 XTOO
7.5E-13 0.0E+00
7.5E-13 0.0E+00
4.2E-13 0.0E+00
2.0E-12 0.0E+00
2.0E-12 0.0E+00
4.0E-12 0.0E+00
2.0E-12 0.0E+00
2.0E-12 0.0E+00
2.00 hk43 2.00 k031 2.00 HO2 2.00 NO2
-2.00 XTOO
1071 NO2 -1.00 XSOO
2.0E-12 0.0E+00
2.0E-12 0.0E+00
2.9E-12 0.0E+00
n071 -1.00 XSOO
1o71 NO2 -1.00 XPOO
1.1E-12 0.0E+00
3.5E-12 0.0E+00
no71 -1.00 XPOO
ud51 2.00 dk33 2.00 HO2 2.00 NO2
ud52 -2.00 XTOO
ud51 ud52 2.00 ak33 2.00 NO2
2.00 HO2 -2.00 XTOO
5.5E-13 0.0E+00
2.0E-12 0.0E+00
2.0E-12 0.0E+00
2.0E-12 0.0E+00
2.0E-12 0.0E+00
1t81 NO2 -1.00 XSOO
nt81 -1.00 XSOO
2.6E-12 0.0E+00
1.4E-12 0.0E+00
1d81 NO2 -1.00 XTOO
nd81 -1.00 XTOO
3.4E-12 0.0E+00
5.6E-13 0.0E+00
1081 NO2 -1.00 XSOO
n081 -1.00 XSOO
2.6E-12 0.0E+00
1.4E-12 0.0E+00
1o81 NO2 -1.00 XSOO
no81 -1.00 XSOO
2.6E-12 0.0E+00
1.4E-12 0.0E+00
1t91 NO2 -1.00 XPOO
nt91 -1.00 XPOO
3.2E-12 0.0E+00
8.2E-13 0.0E+00
1nA1 NO2 -1.00 XTOO
nnA1 -1.00 XTOO
3.3E-12 0.0E+00
7.1E-13 0.0E+00
1tA1 NO2 -1.00 XTOO
ntA1 -1.00 XTOO
3.3E-12 0.0E+00
7.1E-13 0.0E+00
Source
231
Table C.6 (continued) Peroxy radical reaction with NO
3 3v22 NO
!
3 3d21 NO
3 3d21 NO
3 3a21 NO
3 3n21 NO
3 3n21 NO
3 3v21 NO
3 3v21 NO
3 3021 NO
3 3o23 NO
3 3o23 NO
!
3 3h21 NO
3 3h21 NO
3 3o22 NO
3 3o22 NO
3 3n31 NO
3 3d31 NO
3 3d31 NO
3 3n32 NO
3 3n33 NO
1
2
!
!
1
!
2
!
1
!
2
!
!
1
!
2
!
1
!
2
!
1
!
2
!
!
1
!
2
!
!
1
!
2
3 3n33 NO
3 3u31 NO
3 3u31 NO
3 3v32 NO
3 3v32 NO
3 3d33 NO
!
3 3d33 NO
3 3k33 NO
3 3a32 NO
3 3d32 NO
!
3 3d32 NO
3 3k31 NO
3 3u32 NO
3 3u32 NO
3 3a31 NO
3 3a31 NO
3 3a33 NO
3 3n34 NO
1
!
2
!
1
!
2
!
1
!
2
!
!
1
!
2
!
!
1
!
2
!
1
!
2
!
!
!
Reaction
CO2 CO 2.00 NO2 -1.00 XAOO
k2 98 E/R
2.0E-11 0.0E+00
2.00 CO2 2.00 CO 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 CO2 HO2 NO2 -1.00 XAOO
2.00 2n11 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 av11 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2011 CO2 NO2 -1.00 XAOO
2.00 CH2O 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.8E-11 -3.6E+02
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.00 CH2O 2.00 CO2 2.00 HO 2.00 NO2
-2.00 XAOO
2.00 a011 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
dv22 CO2 2.00 NO2 -1.00 XAOO
2.00 dv22 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
3n21 CO2 NO2
2.00 2n21 2.00 CO2 2.00 NO2 2.00 XSOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 uv21 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 dv22 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 2d21 2.00 CO2 2.00 NO2 2.00 XPOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
3021 CO2 NO2
8a32 NO2 -1.00 XAOO
2.00 dd21 2.00 CO2 2.00 HO2 2.00 NO2
1.0E-11 0.0E+00
2.0E-11 0.0E+00
2.0E-11 0.0e+00
1.0E-11 0.0E+00
-2.00 XAOO
3o23 CO2 NO2
1.0E-11 0.0E+00
2.0E-11 0.0E+00
2.00 uk22 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 ad21 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
8a33 NO2 -1.00 XAOO
8n34 NO2 -1.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0e+00
2.0E-11 0.0e+00
2.0E-11 0.0e+00
Source
DeMore et al. [1997]
232
Table C.6 (continued) Peroxy radical reaction with NO
Reaction
1
3 3031 NO
3 3031 NO
3 3o31 NO
3 3o31 NO
3 3o35 NO
!
3 3o35 NO
3 3o32 NO
3 3o32 NO
3 3o33 NO
3 3o33 NO
3 3o34 NO
!
3 3o34 NO
3 3u41 NO
3 3u44 NO
3 3d41 NO
!
3 3d41 NO
3 3v41 NO
3 3v41 NO
3 3v42 NO
3 3u42 NO
3 3d46 NO
3 3d46 NO
3 3d47 NO
3 3d43 NO
3 3d44 NO
3 3d44 NO
3 3n42 NO
3 3n41 NO
3 3n41 NO
3 3n44 NO
3 3n44 NO
3 3n49 NO
3 3n43 NO
3 3v43 NO
3 3v43 NO
3 3d42 NO
3 3d42 NO
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
!
!
1
!
2
!
1
!
2
!
!
!
1
!
2
!
!
!
1
!
2
!
!
1
!
2
!
1
!
2
!
!
!
1
!
2
!
1
!
2
!
k2 98 E/R
2.00 2021 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 d021 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 2o21 2.00 CO2 2.00 NO2 2.00 XPOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 do23 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 a021 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 ao23 2.00 CO2 2.00 HO2 2.00 NO2
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
1d36 CO2 NO2 -1.00 XAOO
1d36 CO2 NO2 -1.00 XAOO
2.00 dv31 2.00 CO2 2.00 HO2 2.00 NO2
1.0E-11 0.0E+00
2.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 dv31 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
3v32 CO2 NO2
1d33 CO2 NO2 -1.00 XAOO
2.00 2d33 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
3d33 CO2 NO2
3d32 CO2 NO2
2.00 dd32 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
vk32 CO2 2.00 NO2 -1.00 XAOO
2.00 nd31 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 2n31 2.00 CO2 2.00 NO2 2.00 XSOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
ko37 2.00 NO2 -1.00 XAOO CO2
dk33 CO2 2.00 NO2 -1.00 XAOO
2.00 vk32 2.00 CO2 2.00 HO2 2.00 NO2
1.0E-11 0.0E+00
2.0E-11 0.0e+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 dv32 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
Source
233
Table C.6 (continued) Peroxy radical reaction with NO
Reaction
1
3 3n45 NO
3 3n45 NO
3 3n46 NO
3 3n46 NO
!
3 3v44 NO
3 3v44 NO
3 3u43 NO
3 3d48 NO
3 3d48 NO
3 3k49 NO
3 3k49 NO
3 3k40 NO
3 3k45 NO
3 3k45 NO
!
3 3k47 NO
3 3k47 NO
3 3k48 NO
3 3d45 NO
3 3d45 NO
3 3k46 NO
3 3k46 NO
3 3k4A NO
3 3n47 NO
2
!
1
!
2
!
1
2
!
!
1
!
2
!
1
!
2
!
!
1
!
2
!
1
!
2
!
!
1
!
2
!
1
!
2
!
!
1
!
2
3 3n47 NO
3 3n48 NO
3 3n48 NO
3 3041 NO
3 3041 NO
3 3042 NO
!
3 3042 NO
3 3o41 NO
3 3o41 NO
3 3o42 NO
3 3o42 NO
!
3 3o43 NO
3 3o43 NO
!
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
k2 98 E/R
2.00 nd33 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 nd32 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.00 dv32 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
1k33 CO2 NO2 -1.00 XAOO
2.00 2d32 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
2.00 2k33 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
3o31 CO2 NO2
2.00 dk33 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.00 2k34 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
3o35 CO2 NO2
2.00 dd31 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 dk35 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
3o32 CO2 NO2
2.00 2n33 2.00 CO2 2.00 NO2 2.00 XPOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 2n34 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
2.00 2032 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 2031 2.00 CO2 2.00 NO2 2.00 XSOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 k031 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 2o34 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.00 2o33 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
Source
234
Table C.6 (continued) Peroxy radical reaction with NO
Reaction
1
3 3o45 NO
3 3o45 NO
3 3o47 NO
3 3o47 NO
3 3o44 NO
!
3 3o44 NO
3 3o46 NO
3 3o46 NO
3 3h40 NO
3 3h40 NO
3 3g40 NO
!
3 3g40 NO
3 3d51 NO
!
3 3d52 NO
3 3d52 NO
3 3u51 NO
3 3v54 NO
3 3u52 NO
3 3u53 NO
3 3k59 NO
3 3k51 NO
3 3k51 NO
3 3k55 NO
3 3d53 NO
3 3d53 NO
3 3d54 NO
3 3k52 NO
3 3k52 NO
3 3k53 NO
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
!
1
!
2
!
!
!
!
!
!
1
!
2
!
!
1
!
2
!
!
1
!
2
!
!
1
3 3n51 NO
3 3n51 NO
3 3n53 NO
3 3n53 NO
3 3n52 NO
!
3 3n52 NO
3 3n54 NO
3 3n54 NO
!
2
!
1
!
2
!
1
!
2
1
!
2
!
k2 98 E/R
2.00 d031 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 2o32 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
2.00 2o35 2.00 CO2 2.00 NO2 2.00 XPOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 do35 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 ko37 2.00 NO2 -2.00 XAOO 2.00 HO
2.00 CO2
2.00 gk33 2.00 NO2 -2.00 XAOO 2.00 HO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0e+00
1.0E-11 0.0e+00
1.0E-11 0.0e+00
2.00 CO2
3d44 CO2 NO2
1.0E-11 0.0e+00
2.0E-11 0.0E+00
2.00 dd41 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
dk40 CO2 2.00 NO2 -1.00 XAOO
3v43 CO2 NO2
1d46 CO2 NO2 -1.00 XAOO
1d46 CO2 NO2 -1.00 XAOO
8k59 NO2 -1.00 XAOO
2.00 dk40 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
3k45 CO2 NO2
2.00 dd43 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
3d45 CO2 NO2
2.00 dk43 2.00 CO2 2.00 HO2 2.00 NO2
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
2.0E-11 0.0E+00
2.0E-11 0.0E+00
2.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
3k46 CO2 NO2
1.0E-11 0.0E+00
2.0E-11 0.0E+00
2.00 nd42 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 2n41 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
2.00 nd43 2.00 CO2 2.00 HO2 2.00 NO2
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 2n42 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
Source
235
Table C.6 (continued) Peroxy radical reaction with NO
Reaction
1
3 3v56 NO
3 3v56 NO
!
3 3n55 NO
3 3n55 NO
3 3d55 NO
3 3d55 NO
3 3d56 NO
!
3 3d56 NO
3 3k5A NO
3 3k5A NO
3 3k5C NO
3 3k5C NO
3 3k50 NO
!
3 3k50 NO
3 3k5B NO
3 3k5B NO
3 3k57 NO
3 3k57 NO
!
3 3k58 NO
3 3k58 NO
3 3051 NO
3 3051 NO
3 3052 NO
3 3052 NO
!
3 3053 NO
3 3053 NO
3 3o51 NO
3 3o51 NO
3 3o52 NO
!
3 3o52 NO
3 3o53 NO
3 3o53 NO
3 3o54 NO
3 3o54 NO
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
k2 98 E/R
2.00 dv46 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.00 nd46 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 2d49 2.00 CO 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 2d47 2.00 CO2 2.00 NO2 2.00 XSOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 2k47 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 2k44 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
2.00 2k40 2.00 CO2 2.00 NO2 2.00 XPOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 2k4B 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 dk48 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.00 dk47 2.00 CO2 2.00 HO2 2.00 NO2
-2.00 XAOO
2.00 2042 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 2041 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.00 2044 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 2o46 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 2o40 2.00 CO2 2.00 NO2 2.00 XPOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 2o4A 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
2.00 2o4C 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
Source
236
Table C.6 (continued) Peroxy radical reaction with NO
Reaction
1
3 3o56 NO
3 3o56 NO
3 3o55 NO
3 3o55 NO
!
3 3o57 NO
3 3o57 NO
3 3061 NO
3 3061 NO
3 3o61 NO
!
3 3o61 NO
3 3r71 NO
3 3r71 NO
3 3t91 NO
3 3t91 NO
3 3tA1 NO
!
3 3tA1 NO
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
k2 98 E/R
2.00 2o43 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
2.00 2o49 2.00 CO2 2.00 NO2 2.00 XPOO
-2.00 XAOO
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
2.00 do49 2.00 NO2 -2.00 XAOO 2.00 HO2
2.00 CO2
2.00 2052 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
2.00 2o52 2.00 CO2 2.00 NO2 2.00 XSOO
1.0E-11 0.0e+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
2.00 2r63 2.00 CO2 2.00 NO2 2.00 XTOO
-2.00 XAOO
2.00 2t81 2.00 CO2 2.00 NO2 2.00 XSOO
-2.00 XAOO
2.00 2t91 2.00 CO2 2.00 NO2 2.00 XPOO
1.0E-11 0.0E+00
3.5E-12 0.0E+00
3.5E-12 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
1.0E-11 0.0E+00
-2.00 XAOO
1.0E-11 0.0E+00
Source
237
Table C.7 Peroxy radical reactions with HO2 .
2 2n11 HO2
2 2011 HO2
2 2o11 HO2
2 2p21 HO2
2 2d21 HO2
2 2a21 HO2
2 2g21 HO2
2 2n22 HO2
2 2n23 HO2
2 2021 HO2
2 2o21 HO2
2 2v31 HO2
2 2d33 HO2
2 2a32 HO2
2 2n31 HO2
2 2n35 HO2
2 2d32 HO2
2 2d34 HO2
2 2k33 HO2
2 2a31 HO2
2 2d31 HO2
2 2k34 HO2
2 2n32 HO2
2 2n33 HO2
2 2n34 HO2
Reaction
hn11 -1.00 XPOO
!
h011 O2
!
ho11 O2 -1.00 XPOO
!
ph21 -1.00 XPOO
!
hd21 -1.00 XPOO
!
ah21 -1.00 XPOO
!
gh21 -1.00 XPOO
!
hn21 O2 -1.00 XPOO
!
hn23 -1.00 XSOO
!
h021 O2 -1.00 XPOO
!
ho22 O2 -1.00 XPOO
!
hv32 -1.00 XPOO
!
hd31 -1.00 XPOO
!
ah32 O2 -1.00 XPOO
!
hn32 -1.00 XSOO
!
hn35 -1.00 XPOO
!
hd32 -1.00 XSOO
!
hd34 -1.00 XPOO
!
hk33 O2 -1.00 XPOO
!
ah31 -1.00 XSOO
!
hd33 -1.00 XSOO
!
hk31 -1.00 XPOO
!
hn31 O2 -1.00 XSOO
!
hn33 -1.00 XPOO
!
hn34 -1.00 XSOO
!
k2 98 E/R
1.3E-11 -1.3E+03
5.6E-12 -8.0E+02
1.2E-11 -2.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
8.0E-12 -7.0E+02
1.0E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
9.0E-12 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
9.0E-12 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
a E/R set to average E/R for peroxy radicals, see text
b Reaction added by Williams [1994a]
c E/R set to average E/R for peroxy radicals, see text
Source
DeMore et al. [1997]
Kirchner and Stockwell [1996]
DeMore et al. [1997]
Kirchner and Stockwell [1997] a
b
Kirchner and Stockwell [1996] c
238
Table C.7 (continued) Peroxy radical reactions with HO2
2 2031 HO2
2 2032 HO2
2 2o32 HO2
2 2o33 HO2
2 2o34 HO2
2 2o31 HO2
2 2o35 HO2
2 2p30 HO2
2 2p31 HO2
2 2d41 HO2
2 2d42 HO2
2 2k43 HO2
2 2a42 HO2
2 2d43 HO2
2 2d45 HO2
2 2g40 HO2
2 2n41 HO2
2 2n43 HO2
2 2n47 HO2
2 2n48 HO2
2 2n42 HO2
2 2n44 HO2
2 2n4a HO2
2 2n4b HO2
2 2d47 HO2
2 2d49 HO2
2 2k44 HO2
2 2k45 HO2
2 2k47 HO2
2 2a41 HO2
2 2d44 HO2
2 2d48 HO2
2 2k40 HO2
2 2k42 HO2
2 2k48 HO2
2 2k49 HO2
2 2k4B HO2
2 2a43 HO2
2 2a47 HO2
2 2k46 HO2
2 2k4C HO2
2 2n45 HO2
2 2n46 HO2
Reaction
h031 O2 -1.00 XSOO
!
h032 O2 -1.00 XPOO
!
ho34 O2 -1.00 XSOO
!
ho35 O2 -1.00 XPOO
!
ho33 O2 -1.00 XPOO
!
ho32 -1.00 XSOO
!
ho31 -1.00 XPOO
!
ph30 -1.00 XPOO
!
ph31 -1.00 XSOO
!
hd41 -1.00 XSOO
!
hd42 -1.00 XSOO
!
hk43 O2 -1.00 XPOO
!
ah43 -1.00 XSOO
!
hd44 O2 -1.00 XSOO
!
hd43 -1.00 XPOO
!
gh40 -1.00 XTOO
!
hn45 -1.00 XSOO
!
hn48 -1.00 XPOO
!
hn41 -1.00 XTOO
!
hn43 O2 -1.00 XSOO
!
hn46 -1.00 XSOO
!
hn47 -1.00 XPOO
!
hn49 -1.00 XSOO
!
hn4a -1.00 XPOO
!
hd46 -1.00 XSOO
!
hd49 -1.00 XPOO
!
hk41 O2 -1.00 XSOO
!
hk42 O2 -1.00 XPOO
!
hk46 -1.00 XPOO
!
ah41 -1.00 XSOO
!
hd45 O2 -1.00 XTOO
!
hd47 -1.00 XSOO
!
hk40 -1.00 XPOO
!
hk44 O2 -1.00 XSOO
!
hk45 -1.00 XPOO
!
hk47 -1.00 XPOO
!
hk4B -1.00 XPOO
!
ah42 -1.00 XTOO
!
ah44 -1.00 XPOO
!
hk4D -1.00 XPOO
!
hk4C -1.00 XPOO
!
hn44 O2 -1.00 XSOO
!
hn42 O2 -1.00 XTOO
!
a Reaction added by Williams [1994a]
k2 98 E/R
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
9.0E-12 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
Source
a
a
239
Table C.7 (continued) Peroxy radical reactions with HO2
2 2041 HO2
2 2042 HO2
2 2043 HO2
2 2044 HO2
2 2o40 HO2
2 2o42 HO2
2 2o43 HO2
2 2o44 HO2
2 2o45 HO2
2 2o46 HO2
2 2o4A HO2
2 2o4C HO2
2 2o48 HO2
2 2o49 HO2
2 2o4B HO2
2 2o4D HO2
2 2d51 HO2
2 2d53 HO2
2 2d57 HO2
2 2d5A HO2
2 2d52 HO2
2 2d55 HO2
2 2d56 HO2
2 2d54 HO2
2 2n51 HO2
2 2n52 HO2
2 2n55 HO2
2 2n56 HO2
2 2n57 HO2
2 2n58 HO2
2 2n59 HO2
2 2n5a HO2
2 2d50 HO2
2 2d58 HO2
2 2u51 HO2
2 2u52 HO2
2 2k51 HO2
2 2k61 HO2
2 2k52 HO2
2 2k53 HO2
2 2n53 HO2
2 2n54 HO2
2 2h53 HO2
2 2h54 HO2
Reaction
h041 O2 -1.00 XSOO
!
h042 O2 -1.00 XPOO
!
h043 O2 -1.00 XTOO
!
h044 O2 -1.00 XPOO
!
ho40 -1.00 XPOO
!
ho41 O2 -1.00 XPOO
!
ho42 O2 -1.00 XSOO
!
ho43 O2 -1.00 XTOO
!
ho45 -1.00 XPOO
!
ho46 -1.00 XPOO
!
ho4A -1.00 XPOO
!
ho4C -1.00 XPOO
!
ho4E -1.00 XPOO
!
ho4F -1.00 XPOO
!
ho4B -1.00 XPOO
!
ho4D -1.00 XPOO
!
hd51 -1.00 XTOO
!
hd53 -1.00 XSOO
!
hd58 -1.00 XSOO
!
hd50 -1.00 XTOO
!
hd52 -1.00 XSOO
!
hd55 O2 -1.00 XSOO
!
hd56 O2 -1.00 XTOO
!
hd54 -1.00 XPOO
!
hn55 O2 -1.00 XTOO
!
hn56 O2 -1.00 XSOO
!
hn5a O2 -1.00 XSOO
!
hn5b O2 -1.00 XSOO
!
hn5c O2 -1.00 XSOO
!
hn5d O2 -1.00 XSOO
!
hn5e O2 -1.00 XSOO
!
hn5f O2 -1.00 XPOO
!
hd5A -1.00 XSOO
!
hd57 -1.00 XSOO
!
hu51 O2 -1.00 XTOO
!
hu52 O2 -1.00 XSOO
!
hk51 -1.00 XTOO
!
hk61 O2 -1.00 XSOO
!
hk53 O2 -1.00 XSOO
!
hk54 O2 -1.00 XSOO
!
hn54 -1.00 XSOO
!
hn53 -1.00 XTOO
!
hh53 -1.00 XSOO
!
hh54 -1.00 XTOO
!
a New Reaction, added by Williams [1994a]
k2 98 E/R
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
9.0E-12 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
Source
a
a
a
a
a
a
a
a
a
240
Table C.7 (continued) Peroxy radical reactions with HO2
2 2051 HO2
2 2052 HO2
2 2053 HO2
2 2054 HO2
2 2055 HO2
2 2056 HO2
2 2057 HO2
2 2o51 HO2
2 2o52 HO2
2 2o55 HO2
2 2o56 HO2
2 2o57 HO2
2 2o58 HO2
2 2o59 HO2
2 2o50 HO2
2 2o53 HO2
2 2o54 HO2
2 2h51 HO2
2 2h52 HO2
2 2o5A HO2
2 2o5B HO2
2 2a51 HO2
2 2a50 HO2
2 2a53 HO2
2 2r63 HO2
2 2r61 HO2
2 2r62 HO2
2 2d61 HO2
2 2d62 HO2
2 2061 HO2
2 2062 HO2
2 2063 HO2
2 2o61 HO2
2 2o62 HO2
2 2o63 HO2
2 2o64 HO2
2 2r72 HO2
2 2r75 HO2
2 2r71 HO2
2 2r73 HO2
2 2r74 HO2
2 2u71 HO2
2 2t71 HO2
2 2e72 HO2
2 2h71 HO2
Reaction
h051 O2 -1.00 XSOO
!
h052 O2 -1.00 XSOO
!
h053 -1.00 XPOO
!
h054 -1.00 XSOO
!
h055 -1.00 XSOO
!
h056 -1.00 XPOO
!
h057 -1.00 XTOO
!
ho52 O2 -1.00 XSOO
!
ho51 O2 -1.00 XSOO
!
ho5C O2 -1.00 XPOO
!
ho56 -1.00 XSOO
!
ho57 -1.00 XPOO
!
ho58 -1.00 XPOO
!
ho59 -1.00 XPOO
!
ho50 -1.00 XSOO
!
ho53 -1.00 XSOO
!
ho54 -1.00 XSOO
!
hh51 -1.00 XSOO
!
hh51 -1.00 XTOO
!
ho5B -1.00 XSOO
!
ho5D -1.00 XPOO
!
ah50 -1.00 XSOO
!
ah51 -1.00 XSOO
!
ah52 -1.00 XPOO
!
h064 O2 -1.00 XTOO
!
hr62 -1.00 XSOO
!
hr61 -1.00 XSOO
!
hd61 -1.00 XTOO
!
hd62 -1.00 XTOO
!
h061 O2 -1.00 XSOO
!
h062 O2 -1.00 XTOO
!
h063 O2 -1.00 XPOO
!
ho62 O2 -1.00 XPOO
!
ho64 -1.00 XPOO
!
ho61 O2 -1.00 XPOO
!
ho63 O2 -1.00 XPOO
!
hr75 O2 -1.00 XPOO
!
hr72 -1.00 XTOO
!
hr71 -1.00 XTOO
!
hr73 O2 -1.00 XTOO
!
hr74 O2 -1.00 XTOO
!
hu71 O2 -1.00 XPOO
!
ht71 O2 -1.00 XTOO
!
eh72 O2 -1.00 XTOO
!
hh71 -1.00 XTOO
!
k2 98 E/R
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.0E-11 -9.8E+02
1.0E-11 -9.8E+02
1.0E-11 -9.8E+02
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.0E-11 -9.8E+02
1.0E-11 -9.8E+02
1.0E-11 -9.8E+02
1.0E-11 -9.8E+02
1.0E-11 -9.8E+02
1.3E-11 -1.3E+03
1.0E-11 -9.8E+02
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
Source
241
Table C.7 (continued) Peroxy radical reactions with HO2
2 2071 HO2
2 2o71 HO2
2 2r81 HO2
2 2r82 HO2
2 2t81 HO2
2 2081 HO2
2 2o81 HO2
2 2t91 HO2
2 2nA1 HO2
2 2tA1 HO2
3 3v22 HO2
3 3d21 HO2
3 3a21 HO2
3 3n21 HO2
3 3v21 HO2
3 3021 HO2
3 3o23 HO2
3 3h21 HO2
3 3o22 HO2
3 3n31 HO2
3 3d31 HO2
3 3n32 HO2
3 3u31 HO2
3 3v32 HO2
3 3d33 HO2
3 3k33 HO2
3 3a32 HO2
3 3d32 HO2
3 3k31 HO2
3 3u32 HO2
3 3a31 HO2
3 3a33 HO2
3 3n34 HO2
3 3031 HO2
3 3o31 HO2
3 3o35 HO2
3 3o32 HO2
3 3o33 HO2
3 3o34 HO2
3 3u41 HO2
3 3u44 HO2
3 3d41 HO2
3 3v41 HO2
3 3v42 HO2
3 3u42 HO2
Reaction
h071 O2 -1.00 XSOO
!
ho71 O2 -1.00 XPOO
!
hr81 -1.00 XTOO
!
hr82 -1.00 XTOO
!
ht83 O2 -1.00 XSOO
!
ht81 O2 -1.00 XSOO
!
ht82 O2 -1.00 XSOO
!
ht91 O2 -1.00 XPOO
!
hnA1 O2 -1.00 XTOO
!
htA1 O2 -1.00 XTOO
!
gv22 -1.00 XAOO
!
gd21 O2 -1.00 XAOO
!
ag21 -1.00 XAOO
!
gn21 -1.00 XAOO
!
gv21 -1.00 XAOO
!
g021 O2 -1.00 XAOO
!
go23 -1.00 XAOO
!
gh21 -1.00 XAOO
!
go22 -1.00 XAOO
!
gn31 -1.00 XAOO
!
gd31 -1.00 XAOO
!
gn32 -1.00 XAOO
!
gu31 -1.00 XAOO
!
gv32 -1.00 XAOO
!
gd33 -1.00 XAOO
!
gk33 O2 -1.00 XAOO
!
ag32 -1.00 XAOO
!
gd32 -1.00 XAOO
!
gk31 -1.00 XAOO
!
gu32 -1.00 XAOO
!
ag31 -1.00 XAOO
!
ag33 -1.00 XAOO
!
gn34 -1.00 XAOO
!
g031 O2 -1.00 XAOO
!
go31 -1.00 XAOO
!
go33 -1.00 XAOO
!
go32 -1.00 XAOO
!
go34 -1.00 XAOO
!
go35 -1.00 XAOO
!
gu41 -1.00 XAOO
!
gu44 -1.00 XAOO
!
gd41 -1.00 XAOO
!
gv41 -1.00 XAOO
!
gv42 -1.00 XAOO
!
gu42 O2 -1.00 XAOO
!
k2 98 E/R
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.0E-11 -9.8E+02
1.0E-11 -9.8E+02
1.0E-11 -9.8E+02
1.3E-11 -1.3E+03
1.3E-11 -1.3E+03
1.0E-11 -9.8E+02
1.3E-11 -1.3E+03
1.0E-11 -9.8E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
Source
Kirchner and Stockwell [1997]
242
Table C.7 (continued) Peroxy radical reactions with HO2
3 3d46 HO2
3 3d47 HO2
3 3d43 HO2
3 3d44 HO2
3 3n42 HO2
3 3n41 HO2
3 3n44 HO2
3 3n49 HO2
3 3n43 HO2
3 3v43 HO2
3 3d42 HO2
3 3n45 HO2
3 3v44 HO2
3 3u43 HO2
3 3d48 HO2
3 3k49 HO2
3 3k40 HO2
3 3k45 HO2
3 3k47 HO2
3 3k48 HO2
3 3d45 HO2
3 3k46 HO2
3 3k4A HO2
3 3n47 HO2
3 3n48 HO2
3 3041 HO2
3 3042 HO2
3 3o41 HO2
3 3o42 HO2
3 3o43 HO2
3 3o45 HO2
3 3o47 HO2
3 3o44 HO2
3 3o46 HO2
3 3h40 HO2
3 3g40 HO2
3 3d51 HO2
3 3d52 HO2
3 3u51 HO2
3 3v54 HO2
3 3u52 HO2
3 3u53 HO2
3 3k59 HO2
3 3k51 HO2
3 3k55 HO2
Reaction
gd46 -1.00 XAOO
!
gd47 -1.00 XAOO
!
gd43 -1.00 XAOO
!
gd44 -1.00 XAOO
!
gn42 -1.00 XAOO
!
gn41 -1.00 XAOO
!
gn49 -1.00 XAOO
!
gn40 -1.00 XAOO
!
gn43 -1.00 XAOO
!
gv43 -1.00 XAOO
!
gd42 -1.00 XAOO
!
gn45 -1.00 XAOO
!
gv44 -1.00 XAOO
!
gu43 -1.00 XAOO
!
gd48 -1.00 XAOO
!
gd49 -1.00 XAOO
!
gk40 -1.00 XAOO
!
gk45 -1.00 XAOO
!
gk47 -1.00 XAOO
!
gk48 -1.00 XAOO
!
gd45 -1.00 XAOO
!
gk46 -1.00 XAOO
!
gk4A -1.00 XAOO
!
gn47 -1.00 XAOO
!
gn48 -1.00 XAOO
!
g042 O2 -1.00 XAOO
!
g041 O2 -1.00 XAOO
!
go41 O2 -1.00 XAOO
!
go44 -1.00 XAOO
!
go42 -1.00 XAOO
!
go45 -1.00 XAOO
!
go47 -1.00 XAOO
!
go43 -1.00 XAOO
!
go46 -1.00 XAOO
!
gh40 -1.00 XAOO
!
gg40 -1.00 XAOO
!
gd51 -1.00 XAOO
!
gd52 -1.00 XAOO
!
gu51 -1.00 XAOO
!
gv53 -1.00 XAOO
!
gu52 O2 -1.00 XAOO
!
gu53 O2 -1.00 XAOO
!
gk5D -1.00 XAOO
!
gk51 -1.00 XAOO
!
gk54 -1.00 XAOO
!
k2 98 E/R
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
Source
243
Table C.7 (continued) Peroxy radical reactions with HO2
3 3d53 HO2
3 3d54 HO2
3 3k52 HO2
3 3k53 HO2
3 3n51 HO2
3 3n53 HO2
3 3n52 HO2
3 3n54 HO2
3 3v56 HO2
3 3n55 HO2
3 3d55 HO2
3 3d56 HO2
3 3k5A HO2
3 3k5C HO2
3 3k50 HO2
3 3k5B HO2
3 3k57 HO2
3 3k58 HO2
3 3051 HO2
3 3052 HO2
3 3053 HO2
3 3o51 HO2
3 3o52 HO2
3 3o53 HO2
3 3o54 HO2
3 3o56 HO2
3 3o55 HO2
3 3o57 HO2
3 3061 HO2
3 3o61 HO2
3 3r71 HO2
3 3t91 HO2
3 3tA1 HO2
3 3v22 HO2
3 3d21 HO2
3 3a21 HO2
3 3n21 HO2
3 3v21 HO2
3 3021 HO2
3 3o23 HO2
3 3h21 HO2
3 3o22 HO2
3 3n31 HO2
3 3d31 HO2
3 3n32 HO2
Reaction
gd53 -1.00 XAOO
!
gd54 -1.00 XAOO
!
gk52 -1.00 XAOO
!
gk55 -1.00 XAOO
!
gn51 -1.00 XAOO
!
gn53 -1.00 XAOO
!
gn52 -1.00 XAOO
!
gn54 -1.00 XAOO
!
gv56 -1.00 XAOO
!
gn55 -1.00 XAOO
!
gd55 -1.00 XAOO
!
gd56 -1.00 XAOO
!
gk5A -1.00 XAOO
!
gk5C -1.00 XAOO
!
gk50 -1.00 XAOO
!
gk5B -1.00 XAOO
!
gk57 -1.00 XAOO
!
gk58 -1.00 XAOO
!
g051 O2 -1.00 XAOO
!
g053 O2 -1.00 XAOO
!
g052 O2 -1.00 XAOO
!
go51 -1.00 XAOO
!
go52 -1.00 XAOO
!
go53 -1.00 XAOO
!
go54 -1.00 XAOO
!
go56 -1.00 XAOO
!
go55 -1.00 XAOO
!
go50 -1.00 XAOO
!
g061 -1.00 XAOO
!
go61 -1.00 XAOO
!
gr71 O2 -1.00 XAOO
!
gt91 O2 -1.00 XAOO
!
gtA1 O2 -1.00 XAOO
!
av22 O3 -1.00 XAOO
!
ad21 O3 -1.00 XAOO
!
aa21 O3 -1.00 XAOO
!
an21 O3 -1.00 XAOO
!
av21 O3 -1.00 XAOO
!
a021 O3 -1.00 XAOO
!
ao23 O3 -1.00 XAOO
!
ah21 O3 -1.00 XAOO
!
ao22 O3 -1.00 XAOO
!
an31 O3 -1.00 XAOO
!
ad31 O3 -1.00 XAOO
!
an32 O3 -1.00 XAOO
!
a New Reaction
k2 98 E/R
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
7.3E-12 -5.5E+02
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
Source
a
a
a
a
a
Kirchner and Stockwell [1997]a
a
a
a
a
a
a
244
Table C.7 (continued) Peroxy radical reactions with HO2
3 3u31 HO2
3 3v32 HO2
3 3d33 HO2
3 3k33 HO2
3 3a32 HO2
3 3d32 HO2
3 3k31 HO2
3 3u32 HO2
3 3a31 HO2
3 3a33 HO2
3 3n34 HO2
3 3031 HO2
3 3o31 HO2
3 3o35 HO2
3 3o32 HO2
3 3o33 HO2
3 3o34 HO2
3 3u41 HO2
3 3u44 HO2
3 3d41 HO2
3 3v41 HO2
3 3v42 HO2
3 3u42 HO2
3 3d46 HO2
3 3d47 HO2
3 3d43 HO2
3 3d44 HO2
3 3n42 HO2
3 3n41 HO2
3 3n44 HO2
3 3n49 HO2
3 3n43 HO2
3 3v43 HO2
3 3d42 HO2
3 3n45 HO2
3 3v44 HO2
3 3u43 HO2
3 3d48 HO2
3 3k49 HO2
3 3k40 HO2
3 3k45 HO2
3 3k47 HO2
3 3k48 HO2
3 3d45 HO2
Reaction
au31 O3 -1.00 XAOO
!
av32 O3 -1.00 XAOO
!
ad33 O3 -1.00 XAOO
!
ak33 O3 -1.00 XAOO
!
aa32 O3 -1.00 XAOO
!
ad32 O3 -1.00 XAOO
!
ak31 O3 -1.00 XAOO
!
au32 O3 -1.00 XAOO
!
aa31 O3 -1.00 XAOO
!
aa33 O3 -1.00 XAOO
!
an35 O3 -1.00 XAOO
!
a031 O3 -1.00 XAOO
!
ao31 O3 -1.00 XAOO
!
ao35 O3 -1.00 XAOO
!
ao32 O3 -1.00 XAOO
!
ao33 O3 -1.00 XAOO
!
ao34 O3 -1.00 XAOO
!
au41 O3 -1.00 XAOO
!
au44 O3 -1.00 XAOO
!
ad41 O3 -1.00 XAOO
!
av41 O3 -1.00 XAOO
!
av42 O3 -1.00 XAOO
!
au42 O3 -1.00 XAOO
!
ad46 O3 -1.00 XAOO
!
ad47 O3 -1.00 XAOO
!
ad43 O3 -1.00 XAOO
!
ad44 O3 -1.00 XAOO
!
an42 O3 -1.00 XAOO
!
an41 O3 -1.00 XAOO
!
an44 O3 -1.00 XAOO
!
an49 O3 -1.00 XAOO
!
an43 O3 -1.00 XAOO
!
av43 O3 -1.00 XAOO
!
ad42 O3 -1.00 XAOO
!
an45 O3 -1.00 XAOO
!
av44 O3 -1.00 XAOO
!
au43 O3 -1.00 XAOO
!
ad48 O3 -1.00 XAOO
!
ad49 O3 -1.00 XAOO
!
ak40 O3 -1.00 XAOO
!
ak45 O3 -1.00 XAOO
!
ak47 O3 -1.00 XAOO
!
ak48 O3 -1.00 XAOO
!
ad45 O3 -1.00 XAOO
!
a New Reaction
k2 98 E/R
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
Source
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
245
Table C.7 (continued) Peroxy radical reactions with HO2
3 3k46 HO2
3 3k4A HO2
3 3n47 HO2
3 3n48 HO2
3 3041 HO2
3 3042 HO2
3 3o41 HO2
3 3o42 HO2
3 3o43 HO2
3 3o45 HO2
3 3o47 HO2
3 3o44 HO2
3 3o46 HO2
3 3h40 HO2
3 3g40 HO2
3 3d51 HO2
3 3d52 HO2
3 3u51 HO2
3 3v54 HO2
3 3u52 HO2
3 3u53 HO2
3 3k59 HO2
3 3k51 HO2
3 3k55 HO2
3 3d53 HO2
3 3d54 HO2
3 3k52 HO2
3 3k53 HO2
3 3n51 HO2
3 3n53 HO2
3 3n52 HO2
3 3n54 HO2
3 3v56 HO2
3 3n55 HO2
3 3d55 HO2
3 3d56 HO2
3 3k5A HO2
3 3k5C HO2
3 3k50 HO2
3 3k5B HO2
3 3k57 HO2
3 3k58 HO2
Reaction
ak46 O3 -1.00 XAOO
!
ak4A O3 -1.00 XAOO
!
an47 O3 -1.00 XAOO
!
an48 O3 -1.00 XAOO
!
a041 O3 -1.00 XAOO
!
a042 O3 -1.00 XAOO
!
ao41 O3 -1.00 XAOO
!
ao42 O3 -1.00 XAOO
!
ao43 O3 -1.00 XAOO
!
ao45 O3 -1.00 XAOO
!
ao47 O3 -1.00 XAOO
!
ao44 O3 -1.00 XAOO
!
ao46 O3 -1.00 XAOO
!
ah42 O3 -1.00 XAOO
!
ag40 O3 -1.00 XAOO
!
ad51 O3 -1.00 XAOO
!
ad52 O3 -1.00 XAOO
!
au51 O3 -1.00 XAOO
!
av53 O3 -1.00 XAOO
!
au52 O3 -1.00 XAOO
!
au53 O3 -1.00 XAOO
!
ak59 O3 -1.00 XAOO
!
ak51 O3 -1.00 XAOO
!
ak54 O3 -1.00 XAOO
!
ad53 O3 -1.00 XAOO
!
ad54 O3 -1.00 XAOO
!
ak52 O3 -1.00 XAOO
!
ak55 O3 -1.00 XAOO
!
an51 O3 -1.00 XAOO
!
an53 O3 -1.00 XAOO
!
an52 O3 -1.00 XAOO
!
an54 O3 -1.00 XAOO
!
av56 O3 -1.00 XAOO
!
an55 O3 -1.00 XAOO
!
ad55 O3 -1.00 XAOO
!
ad56 O3 -1.00 XAOO
!
ak5A O3 -1.00 XAOO
!
ak5C O3 -1.00 XAOO
!
ak50 O3 -1.00 XAOO
!
ak5B O3 -1.00 XAOO
!
ak57 O3 -1.00 XAOO
!
ak58 O3 -1.00 XAOO
!
a New Reaction
k2 98 E/R
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
Source
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
246
Table C.7 (continued) Peroxy radical reactions with HO2
3 3051 HO2
3 3052 HO2
3 3053 HO2
3 3o51 HO2
3 3o52 HO2
3 3o53 HO2
3 3o54 HO2
3 3o56 HO2
3 3o55 HO2
3 3o57 HO2
3 3061 HO2
3 3o61 HO2
3 3r71 HO2
3 3t91 HO2
3 3tA1 HO2
Reaction
!
a051 O3 -1.00 XAOO
!
a052 O3 -1.00 XAOO
!
a053 O3 -1.00 XAOO
!
ao51 O3 -1.00 XAOO
!
ao52 O3 -1.00 XAOO
!
ao53 O3 -1.00 XAOO
!
ao54 O3 -1.00 XAOO
!
ao56 O3 -1.00 XAOO
!
ao55 O3 -1.00 XAOO
!
ao57 O3 -1.00 XAOO
!
a061 O3 -1.00 XAOO
!
ao61 O3 -1.00 XAOO
!
ar71 O3 -1.00 XAOO
!
at91 O3 -1.00 XAOO
!
atA1 O3 -1.00 XAOO
a New Reaction
k2 98 E/R
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
2.7E-12 -2.6E+03
Source
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
247
Table C.8 Peroxy radical reactions with NO2 .
2 2011 NO2 (M)
2 2r63 NO2
3 3v22 NO2
3 3d21 NO2
3 3a21 NO2
3 3n21 NO2
3 3v21 NO2
3 3021 NO2 (M)
3 3o23 NO2
3 3h21 NO2
3 3o22 NO2
3 3n31 NO2
3 3d31 NO2
3 3n32 NO2
3 3u31 NO2
3 3v32 NO2
3 3d33 NO2
3 3k33 NO2
3 3a32 NO2
3 3d32 NO2
3 3k31 NO2
3 3u32 NO2
3 3a31 NO2
3 3a33 NO2
3 3n34 NO2
3 3031 NO2
3 3o31 NO2
3 3o35 NO2
3 3o32 NO2
3 3o33 NO2
3 3o34 NO2
3 3u41 NO2
3 3u44 NO2
3 3d41 NO2
3 3v41 NO2
3 3u42 NO2
3 3d46 NO2
3 3d47 NO2
3 3d43 NO2
3 3d44 NO2
3 3n42 NO2
3 3n41 NO2
3 3n44 NO2
3 3n49 NO2
3 3n43 NO2
Reaction
n012 (M)
!
1r61 NO3 -1.00 XTOO
!
pv22 -1.00 XAOO
!
pd21 -1.00 XAOO
!
pg21 -1.00 XAOO
!
pn21 -1.00 XAOO
!
pv21 -1.00 XAOO
!
p021 -1.00 XAOO (M)
!
po23 -1.00 XAOO
!
ph21 -1.00 XAOO
!
po22 -1.00 XAOO
!
pn31 -1.00 XAOO
!
pd31 -1.00 XAOO
!
pn32 -1.00 XAOO
!
pu31 -1.00 XAOO
!
pv32 -1.00 XAOO
!
pd33 -1.00 XAOO
!
pk33 -1.00 XAOO
!
pa32 -1.00 XAOO
!
pd32 -1.00 XAOO
!
pk31 -1.00 XAOO
!
pu32 -1.00 XAOO
!
pa31 -1.00 XAOO
!
pa33 -1.00 XAOO
!
pn34 -1.00 XAOO
!
p031 -1.00 XAOO
!
po31 -1.00 XAOO
!
po35 -1.00 XAOO
!
po32 -1.00 XAOO
!
po33 -1.00 XAOO
!
po34 -1.00 XAOO
!
pu41 -1.00 XAOO
!
pu43 -1.00 XAOO
!
pd41 -1.00 XAOO
!
pv41 -1.00 XAOO
!
pu42 -1.00 XAOO
!
pd46 -1.00 XAOO
!
pd47 -1.00 XAOO
!
pd43 -1.00 XAOO
!
pd44 -1.00 XAOO
!
pn42 -1.00 XAOO
!
pn41 -1.00 XAOO
!
pn44 -1.00 XAOO
!
pn40 -1.00 XAOO
!
pn43 -1.00 XAOO
!
a Recommended by DeMore et al. [1997]
k2 98 E/R
4.0E-12 -1.8E+03
7.0E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0e+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0e+00
8.6E-12 0.0e+00
8.6E-12 0.0e+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
Source
Madronich and Calvert [1989]a
Madronich and Calvert [1989]
248
Table C.7 (continued) Peroxy radical reactions with NO2
3 3v43 NO2
3 3d42 NO2
3 3n45 NO2
3 3v44 NO2
3 3u43 NO2
3 3d48 NO2
3 3k49 NO2
3 3k40 NO2
3 3k45 NO2
3 3k47 NO2
3 3k48 NO2
3 3d45 NO2
3 3k46 NO2
3 3k4A NO2
3 3n47 NO2
3 3n48 NO2
3 3041 NO2
3 3042 NO2
3 3o41 NO2
3 3o42 NO2
3 3o43 NO2
3 3o45 NO2
3 3o47 NO2
3 3o44 NO2
3 3o46 NO2
3 3h40 NO2
3 3g40 NO2
3 3d51 NO2
3 3d52 NO2
3 3u51 NO2
3 3v54 NO2
3 3u52 NO2
3 3u53 NO2
3 3k59 NO2
3 3k51 NO2
3 3k55 NO2
3 3d53 NO2
3 3d54 NO2
3 3k52 NO2
3 3k53 NO2
3 3n51 NO2
3 3n53 NO2
3 3n52 NO2
3 3n54 NO2
3 3v56 NO2
Reaction
!
pv43 -1.00 XAOO
!
pd42 -1.00 XAOO
!
pn49 -1.00 XAOO
!
pv44 -1.00 XAOO
!
pu44 -1.00 XAOO
!
pd48 -1.00 XAOO
!
pk49 -1.00 XAOO
!
pk40 -1.00 XAOO
!
pk45 -1.00 XAOO
!
pk47 -1.00 XAOO
!
pk48 -1.00 XAOO
!
pd45 -1.00 XAOO
!
pk46 -1.00 XAOO
!
pk4A -1.00 XAOO
!
pn47 -1.00 XAOO
!
pn48 -1.00 XAOO
!
p042 -1.00 XAOO
!
p041 -1.00 XAOO
!
po42 -1.00 XAOO
!
po41 -1.00 XAOO
!
po43 -1.00 XAOO
!
po45 -1.00 XAOO
!
po47 -1.00 XAOO
!
po44 -1.00 XAOO
!
po46 -1.00 XAOO
!
ph40 -1.00 XAOO
!
pg40 -1.00 XAOO
!
pd51 -1.00 XAOO
!
pd52 -1.00 XAOO
!
pu51 -1.00 XAOO
!
pv53 -1.00 XAOO
!
pu53 -1.00 XAOO
!
pu52 -1.00 XAOO
!
pk59 -1.00 XAOO
!
pk51 -1.00 XAOO
!
pk54 -1.00 XAOO
!
pd53 -1.00 XAOO
!
pd54 -1.00 XAOO
!
pk52 -1.00 XAOO
!
pk55 -1.00 XAOO
!
pn51 -1.00 XAOO
!
pn53 -1.00 XAOO
!
pn52 -1.00 XAOO
!
pn54 -1.00 XAOO
!
pv56 -1.00 XAOO
k2 98 E/R
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
Source
249
Table C.7 (continued) Peroxy radical reactions with NO2
3 3n55 NO2
3 3d55 NO2
3 3d56 NO2
3 3k5A NO2
3 3k5C NO2
3 3k50 NO2
3 3k5B NO2
3 3k57 NO2
3 3k58 NO2
3 3051 NO2
3 3052 NO2
3 3053 NO2
3 3o51 NO2
3 3o52 NO2
3 3o53 NO2
3 3o54 NO2
3 3o56 NO2
3 3o55 NO2
3 3o57 NO2
3 3061 NO2
3 3o61 NO2
3 3r71 NO2
3 3t91 NO2
3 3tA1 NO2
Reaction
!
pn55 -1.00 XAOO
!
pd55 -1.00 XAOO
!
pd56 -1.00 XAOO
!
pk5A -1.00 XAOO
!
pk5C -1.00 XAOO
!
pk50 -1.00 XAOO
!
pk5B -1.00 XAOO
!
pk57 -1.00 XAOO
!
pk58 -1.00 XAOO
!
p051 -1.00 XAOO
!
p052 -1.00 XAOO
!
p053 -1.00 XAOO
!
po51 -1.00 XAOO
!
po52 -1.00 XAOO
!
po53 -1.00 XAOO
!
po54 -1.00 XAOO
!
po56 -1.00 XAOO
!
po55 -1.00 XAOO
!
po50 -1.00 XAOO
!
p061 -1.00 XAOO
!
po61 -1.00 XAOO
!
pr71 -1.00 XAOO
!
pt91 -1.00 XAOO
!
ptA1 -1.00 XAOO
k2 98 E/R
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
8.6E-12 0.0E+00
Source
250
Table C.9 Peroxy Radical Reactions with NO3 .
2 2011 NO3
3 3021 NO3
!
!
Reaction
CH3O NO2 O2 -1.00 XPOO
8021 NO2 O2 -1.00 XAOO
k2 98 E/R
1.2E-12 0.0E+00
4.0E-12 0.0E+00
Source
Kirchner and Stockwell [1996] a
Kirchner and Stockwell [1996]a
a Products from Canosa-Mas et al. [1996]
Table C.10 Peroxy radical reactions with methyl peroxy radical.
2011 2011
2011 2021
2011 2021
!
1
!
2
!
1
2011 2031
2011 2031
2011 2032
2011 2032
2011 2041
2011 2041
!
2011 2042
2011 2042
2011 2043
2011 2043
2011 2044
!
2011 2044
2011 2051
2011 2051
2011 2052
2011 2052
2011 2053
!
2011 2053
2011 2054
2011 2054
!
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
Reaction
0.80 CH3O 0.60 CH2O 0.60 o011
0.96 CH3O 0.96 1021 0.52 CH2O 0.52 o021
0.52 d021 0.52 o011 -2.00 XPOO
0.96 CH3O 0.96 1032 0.52 CH2O 0.52 o032
0.52 k031 0.52 o011 -2.00 XSOO
CH3O 1031 0.50 CH2O 0.50 o031
0.50 d031 0.50 o011 -2.00 XPOO
CH3O 1043 0.50 CH2O 0.50 o041
0.50 k041 0.50 o011 -2.00 XSOO
CH3O 1042 0.50 CH2O 0.50 o042
0.50 d041 0.50 o011 -2.00 XPOO
k2 98 E/R
3.7E-13 -4.2E+02
1.0E-13 -1.6E+02
1.0E-13 -1.6E+02
2.0E-14 8.8E+02
2.0E-14 8.8E+02
3.8E-13 -5.1E+02
3.8E-13 -5.1E+02
1.8E-15 5.4E+02
1.8E-15 5.4E+02
0.60 o043 -2.00 XTOO
CH3O 1044 0.50 CH2O 0.50 o044
2.2E-14 -8.6E+02
2.2E-14 -8.6E+02
3.3E-15 1.7E+03
3.3E-15 1.7E+03
2.2E-14 -8.6E+02
0.50 d042 0.50 o011 -2.00 XPOO
CH3O 1051 0.50 CH2O 0.50 o054
0.50 k051 0.50 o011 -2.00 XSOO
CH3O 1052 0.50 CH2O 0.50 o052
0.50 k053 0.50 o011 -2.00 XSOO
CH3O 1053 0.50 CH2O 0.50 o053
2.2E-14 -8.6E+02
1.6E-15 1.9E+02
1.6E-15 1.9E+02
1.6E-15 1.9E+02
1.6E-15 1.9E+02
1.9E-14 -1.2E+03
0.50 d051 0.50 o011 -2.00 XPOO
CH3O 1054 0.50 CH2O 0.50 o054
0.50 k051 0.50 o011 -2.00 XSOO
1.9E-14 -1.2E+03
1.6E-15 1.9E+02
1.6E-15 1.9E+02
1.40 CH3O 1.40 1044 0.60 CH2O
Source
Lightfoot et al. [1992]
a;b
c
d;e
d;e
f
a 2021 self reaction rate from Kirchner and Stockwell [1996] based on Lightfoot et al. [1992]
b E/R calculated from self–reaction activation temperature
c 2031 self reaction rate from Kirchner and Stockwell [1996], from Lightfoot et al. [1992]
d upper limit for 2032 self reaction rate from Kirchner and Stockwell [1996], from Lightfoot et al. [1992]
e E/R calculated from estimated self-reaction activation temperatures
f 2043 self reaction rate from Kirchner and Stockwell [1996], from LeBras [1997]
251
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 2055
2011 2055
!
2011 2056
2011 2056
2011 2057
2011 2057
2011 2061
2011 2061
!
2011 2062
2011 2062
2011 2063
2011 2063
2011 2071
!
2011 2071
2011 2081
2011 2081
2011 2a21
2011 2a21
2011 2a31
!
2011 2a31
2011 2a41
2011 2a41
2011 2a42
2011 2a42
!
2011 2g21
2011 2g21
2011 2u51
2011 2u51
2011 2u52
2011 2u52
!
2011 2u71
2011 2u71
2011 2e72
2011 2e72
2011 2d21
!
2011 2d21
2011 2d31
2011 2d31
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
k2 98 E/R
CH3O 1055 0.50 CH2O 0.50 o055
0.50 k052 0.50 o011 -2.00 XSOO
1.6E-15 1.9E+02
1.6E-15 1.9E+02
CH3O 1056 0.50 CH2O 0.50 o056
0.50 d053 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1057 0.60 CH2O
0.60 o057 -2.00 XTOO
CH3O 1061 0.50 CH2O 0.50 o061
0.50 k062 0.50 o011 -2.00 XSOO
1.9E-14 -1.2E+03
1.9E-14 -1.2E+03
1.3E-16 1.6E+03
1.3E-16 1.6E+03
1.4E-15 -1.6E+02
1.4E-15 -1.6E+02
1.40 CH3O 1.40 1062 0.60 CH2O
0.60 o062 -2.00 XTOO
CH3O 1063 0.50 CH2O 0.50 o063
0.50 d061 0.50 o011 -2.00 XPOO
CH3O 1071 0.50 CH2O 0.50 o071
1.1E-16 1.2E+03
1.1E-16 1.2E+03
1.7E-14 -1.6E+03
1.7E-14 -1.6E+03
1.2E-15 -5.1E+02
0.50 k071 0.50 o011 -2.00 XSOO
CH3O 1081 0.50 CH2O 0.50 o081
0.50 k081 0.50 o011 -2.00 XSOO
CH3O 1a21 0.50 CH2O 0.50 ao23
0.50 ad21 0.50 o011 -2.00 XPOO
CH3O 1a31 0.50 CH2O 0.50 ao34
1.2E-15 -5.1E+02
1.2E-15 -1.2E+03 a
1.2E-15 -1.2E+03 a
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.4E-14 2.9E+02
0.50 ak33 0.50 o011 -2.00 XSOO
CH3O 1a41 0.50 CH2O 0.50 ao45
0.50 ak4C 0.50 o011 -2.00 XSOO
CH3O 1a43 0.50 CH2O 0.50 ak40
0.50 ak4D 0.50 o011 -2.00 XSOO
1.4E-14 2.9E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
CH3O 1g21 0.50 CH2O 0.50 go23
0.50 gd21 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1u52 0.60 CH2O 0.60 uo52
-2.00 XTOO
CH3O 1u51 0.50 CH2O 0.50 uo52
0.50 uk51 0.50 o011 -2.00 XSOO
1.9E-13 2.9E+02
1.9E-13 2.9E+02
8.7E-16 2.9E+02
8.7E-16 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
CH3O 1u71 0.50 CH2O 0.50 uk71
0.50 ud71 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1e71 0.60 CH2O 0.60 ek71
-2.00 XTOO
CH3O 1d21 0.50 CH2O 0.50 do23
1.5E-14 -7.1E+02
1.5E-14 -7.1E+02
7.0E-16 2.9E+02
7.0E-16 2.9E+02
1.9E-13 2.9E+02
0.50 dd21 0.50 o011 -2.00 XPOO
CH3O 1d32 0.50 CH2O 0.50 do31
0.50 dk35 0.50 o011 -2.00 XSOO
1.9E-13 2.9E+02
1.4E-14 2.9E+02
1.4E-14 2.9E+02
a E/R calculated from estimated self-reaction activation temperatures
Source
252
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 2d32
2011 2d32
2011 2d33
2011 2d33
!
2011 2d34
2011 2d34
2011 2d41
2011 2d41
2011 2d42
!
2011 2d42
2011 2d43
2011 2d43
2011 2d44
2011 2d44
2011 2d45
!
2011 2d45
2011 2d47
2011 2d47
2011 2d48
2011 2d48
!
2011 2d49
2011 2d49
2011 2g40
2011 2g40
2011 2d50
2011 2d50
!
2011 2d51
2011 2d51
2011 2d52
2011 2d52
2011 2d53
!
2011 2d53
2011 2d54
2011 2d54
2011 2d55
2011 2d55
2011 2d56
!
2011 2d56
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
k2 98 E/R
CH3O 1d31 0.50 CH2O 0.50 do34
0.50 dk33 0.50 o011 -2.00 XSOO
CH3O 1d34 0.50 CH2O 0.50 dk35
0.50 dd32 0.50 o011 -2.00 XPOO
1.4E-14 2.9E+02
1.4E-14 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
CH3O 1d35 0.50 CH2O 0.50 do35
0.50 dd33 0.50 o011 -2.00 XPOO
CH3O 1d41 0.50 CH2O 0.50 dv45
0.50 dv42 0.50 o011 -2.00 XSOO
CH3O 1d42 0.50 CH2O 0.50 dv45
2.5E-14 -7.1E+02
2.5E-14 -7.1E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
0.50 dv44 0.50 o011 -2.00 XSOO
CH3O 1d44 0.50 CH2O 0.50 dd42
0.50 dd43 0.50 o011 -2.00 XSOO
1.40 CH3O 1.40 1d43 0.60 CH2O 0.60 do49
-2.00 XTOO
CH3O 1d45 0.50 CH2O 0.50 dk47
1.2E-14 2.9E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
1.0E-15 2.9E+02
1.0E-15 2.9E+02
1.5E-13 2.9E+02
0.50 dd43 0.50 o011 -2.00 XPOO
CH3O 1d47 0.50 CH2O 0.50 do44
0.50 dk4C 0.50 o011 -2.00 XSOO
CH3O 1d48 0.50 CH2O 0.50 do45
0.50 dk4A 0.50 o011 -2.00 XSOO
1.5E-13 2.9E+02
1.8E-15 -7.1E+02
1.8E-15 -7.1E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
CH3O 1d49 0.50 CH2O 0.50 do43
0.50 dd45 0.50 o011 -2.00 XPOO
1.40 1g40 1.40 CH3O 0.60 go43 0.60 CH2O
-2.00 XTOO
CH3O 1d5A 0.50 CH2O 0.50 do57
0.50 dk5G 0.50 o011 -2.00 XSOO
2.2E-14 -7.1E+02
2.2E-14 -7.1E+02
1.0E-15 2.9E+02
1.0E-15 2.9E+02
1.6E-15 -7.1E+02
1.6E-15 -7.1E+02
1.40 CH3O 1.40 1d51 0.60 CH2O 0.60 dv56
-2.00 XTOO
CH3O 1d52 0.50 CH2O 0.50 dk59
0.50 dk53 0.50 o011 -2.00 XSOO
CH3O 1d53 0.50 CH2O 0.50 dv56
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
0.50 dv55 0.50 o011 -2.00 XSOO
CH3O 1d54 0.50 CH2O 0.50 dk58
0.50 dd54 0.50 o011 -2.00 XPOO
CH3O 1d56 0.50 CH2O 0.50 dk59
0.50 dk5B 0.50 o011 -2.00 XSOO
1.40 CH3O 1.40 1d55 0.60 CH2O 0.60 dd56
1.1E-14 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
8.7E-16 2.9E+02
-2.00 XTOO
8.7E-16 2.9E+02
Source
253
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 2d57
2011 2d57
2011 2d58
2011 2d58
2011 2d59
!
2011 2d59
2011 2d5A
2011 2d5A
2011 2d61
2011 2d61
!
2011 2d62
2011 2d62
2011 2d82
2011 2d82
2011 2h51
2011 2h51
!
2011 2h52
2011 2h52
2011 2h53
2011 2h53
2011 2h54
!
2011 2h54
2011 2h71
2011 2h71
2011 2v31
2011 2v31
2011 2a32
!
2011 2a32
2011 2k33
2011 2k33
2011 2k34
2011 2k34
!
2011 2k40
2011 2k40
2011 2k42
2011 2k42
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
k2 98 E/R
CH3O 1d57 0.50 CH2O 0.50 dk5D
0.50 dk5A 0.50 o011 -2.00 XSOO
CH3O 1d58 0.50 CH2O 0.50 do53
0.50 dk5C 0.50 o011 -2.00 XSOO
1.40 CH3O 1.40 1d59 0.60 CH2O 0.60 do59
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.6E-15 -7.1E+02
1.6E-15 -7.1E+02
1.3E-16 -7.1E+02
-2.00 XTOO
1.40 CH3O 1.40 1d5B 0.60 CH2O 0.60 dd57
-2.00 XTOO
1.40 CH3O 1.40 1d61 0.60 CH2O 0.60 do65
-2.00 XTOO
1.3E-16 -7.1E+02
8.7E-16 2.9E+02
8.7E-16 2.9E+02
1.1E-16 -7.1E+02
1.1E-16 -7.1E+02
1.40 CH3O 1.40 1d62 0.60 CH2O 0.60 do66
-2.00 XTOO
1.40 CH3O 1.40 1d81 0.60 CH2O 0.60 dk82
-2.00 XTOO
CH3O 1k54 0.50 CH2O 0.50 ho5A
0.50 hk51 0.50 o011 -2.00 XSOO
7.6E-16 2.9E+02
7.6E-16 2.9E+02
1.0E-16 -1.2E+03
1.0E-16 -1.2E+03
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.40 CH3O 1.40 1h53 0.60 CH2O 0.60 ho5B
-2.00 XTOO
CH3O 1h51 0.50 CH2O 0.50 hn58
0.50 hn57 0.50 o011 -2.00 XSOO
1.40 CH3O 1.40 1h52 0.60 CH2O 0.60 hn59
8.7E-16 2.9E+02
8.7E-16 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
8.7E-16 2.9E+02
-2.00 XTOO
1.40 CH3O 1.40 1h71 0.60 CH2O 0.60 hk71
-2.00 XTOO
CH3O 1v34 0.50 CH2O 0.50 vk31
0.50 dv31 0.50 o011 -2.00 XPOO
CH3O 1a32 0.50 CH2O 0.50 ak31
8.7E-16 2.9E+02
6.8E-16 2.9E+02
6.8E-16 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
0.50 ad34 0.50 o011 -2.00 XPOO
CH3O 1k33 0.50 CH2O 0.50 ko37
0.50 dk33 0.50 o011 -2.00 XPOO
CH3O 1k31 0.50 CH2O 0.50 ko31
0.50 dk35 0.50 o011 -2.00 XPOO
1.7E-13 2.9E+02
1.9E-12 2.9E+02
1.9E-12 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
CH3O 1k40 0.50 CH2O 0.50 ko46
0.50 dk48 0.50 o011 -2.00 XPOO
CH3O 1k44 0.50 CH2O 0.50 ko46
0.50 kk42 0.50 o011 -2.00 XSOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
Source
a
a
b
b
a E/R calculated from estimated self-reaction activation temperatures
b 2k33 self reaction rate from Kirchner and Stockwell [1996] from Lightfoot et al. [1992]
254
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 2k43
2011 2k43
2011 2k44
2011 2k44
!
2011 2k45
2011 2k45
2011 2k46
2011 2k46
2011 2k47
2011 2k47
!
2011 2k48
2011 2k48
2011 2k49
2011 2k49
2011 2k4B
!
2011 2k4B
2011 2k4C
2011 2k4C
2011 2k51
2011 2k51
2011 2k52
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
2011 2k52
2011 2k53
2011 2k53
2011 2l11
2011 2l11
!
2011 2l21
2011 2l21
2011 2l22
2011 2l22
2011 2l31
2011 2l31
!
2011 2l41
2011 2l41
2011 2l42
2011 2l42
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
k2 98 E/R
CH3O 1k41 0.50 CH2O 0.50 kk42
0.50 dk40 0.50 o011 -2.00 XPOO
CH3O 1k45 0.50 CH2O 0.50 ko42
0.50 kk43 0.50 o011 -2.00 XSOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
CH3O 1k42 0.50 CH2O 0.50 ko41
0.50 dk49 0.50 o011 -2.00 XPOO
CH3O 1k4D 0.50 CH2O 0.50 ko47
0.50 dk4E 0.50 o011 -2.00 XPOO
CH3O 1k47 0.50 CH2O 0.50 ko45
0.50 dk4C 0.50 o011 -2.00 XPOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
2.2E-14 -7.1E+02
2.2E-14 -7.1E+02
CH3O 1k46 0.50 CH2O 0.50 ko43
0.50 dk4A 0.50 o011 -2.00 XPOO
CH3O 1k48 0.50 CH2O 0.50 ko43
0.50 dk4B 0.50 o011 -2.00 XPOO
CH3O 1k4B 0.50 CH2O 0.50 ko48
2.2E-14 -7.1E+02
2.2E-14 -7.1E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
0.50 dk4D 0.50 o011 -2.00 XPOO
CH3O 1k4C 0.50 CH2O 0.50 ko47
0.50 dk47 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1k51 0.60 CH2O 0.60 ko54
-2.00 XTOO
CH3O kk52 0.50 CH2O 0.50 ko57
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
8.7E-16 2.9E+02
8.7E-16 2.9E+02
1.6E-15 -7.1E+02
0.50 kk52 0.50 o011 -2.00 XSOO
CH3O kk53 0.50 CH2O 0.50 ko58
0.50 kk53 0.50 o011 -2.00 XSOO
CH3O 1l11 0.50 CH2O 0.50 lo11
0.50 ld11 0.50 o011 -2.00 XPOO
1.6E-15 -7.1E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
3.7E-13 -1.2E+03
3.7E-13 -1.2E+03
CH3O 1l21 0.50 CH2O 0.50 lo21
0.50 ld21 0.50 o011 -2.00 XPOO
CH3O 1l22 0.50 CH2O 0.50 lo22
0.50 lk21 0.50 o011 -2.00 XSOO
CH3O 1l31 0.50 CH2O 0.50 lo31
0.50 lk31 0.50 o011 -2.00 XSOO
2.8E-14 -1.6E+02
2.8E-14 -1.6E+02
2.8E-14 -1.6E+02
2.8E-14 -1.6E+02
2.1E-15 8.9E+02
2.1E-15 8.9E+02
CH3O 1l41 0.50 CH2O 0.50 lo41
0.50 lk41 0.50 o011 -2.00 XSOO
1.40 CH3O 1.40 1l42 0.60 CH2O 0.60 lo42
-2.00 XTOO
1.8E-15 5.4E+02
1.8E-15 5.4E+02
1.5E-16 1.9E+03
1.5E-16 1.9E+03
a Reaction added byWilliams [1994a]
Source
a
a
a
a
255
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 2l43
2011 2l43
2011 2m01
2011 2m01
!
2011 2m11
2011 2m11
2011 2m12
2011 2m12
2011 2m21
2011 2m21
!
2011 2m22
2011 2m22
2011 2m23
2011 2m23
2011 2m33
!
2011 2m33
2011 2n11
2011 2n11
2011 2n21
2011 2n21
2011 2n22
!
2011 2n22
2011 2n23
2011 2n23
2011 2n31
2011 2n31
!
2011 2n32
2011 2n32
2011 2n33
2011 2n33
2011 2n34
2011 2n34
!
2011 2n35
2011 2n35
2011 2n41
2011 2n41
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
k2 98 E/R
CH3O 1l43 0.50 CH2O 0.50 lo43
0.50 ld41 0.50 o011 -2.00 XPOO
CH3O NH2O 0.50 CH2O 0.50 mo01
0.50 HNO 0.50 o011 -2.00 XPOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
3.9E-13 -8.6E+02
3.9E-13 -8.6E+02
CH3O 1m13 0.50 CH2O 0.50 mo11
0.50 md11 0.50 o011 -2.00 XPOO
CH3O 1m11 0.50 CH2O 0.50 mo12
0.50 wo11 0.50 o011 -2.00 XSOO
CH3O 1m23 0.50 CH2O 0.50 mo21
0.50 mk21 0.50 o011 -2.00 XSOO
3.7E-13 -1.2E+03
3.7E-13 -1.2E+03
1.3E-14 0.0E+00
1.3E-14 0.0E+00
2.8E-14 -1.6E+02
2.8E-14 -1.6E+02
CH3O 1m24 0.50 CH2O 0.50 mo22
0.50 md21 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1m25 0.60 CH2O
0.60 mo23 -2.00 XTOO
CH3O 1m33 0.50 CH2O 0.50 mo31
2.8E-14 -1.6E+02
2.8E-14 -1.6E+02
2.4E-15 0.0E+00
2.4E-15 0.0E+00
2.5E-14 -5.1E+02
0.50 md31 0.50 o011 -2.00 XPOO
CH3O 1n11 0.50 CH2O 0.50 no11
0.50 nd11 0.50 o011 -2.00 XPOO
CH3O 1n21 0.50 CH2O 0.50 nd22
0.50 nd23 0.50 o011 -2.00 XSOO
CH3O 1n22 0.50 CH2O 0.50 no21
2.5E-14 -5.1E+02
1.5E-12 2.9E+02
1.5E-12 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
0.50 nd21 0.50 o011 -2.00 XPOO
1n23 CH3O 0.50 no23 0.50 CH2O
0.50 nk23 0.50 o011 -2.00 XSOO
CH3O 1n31 0.50 CH2O 0.50 nv39
0.50 nv35 0.50 o011 -2.00 XSOO
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
CH3O 1n32 0.50 CH2O 0.50 no33
0.50 nk38 0.50 o011 -2.00 XSOO
CH3O 1n33 0.50 CH2O 0.50 no34
0.50 nd35 0.50 o011 -2.00 XPOO
CH3O 1n34 0.50 CH2O 0.50 no32
0.50 nd34 0.50 o011 -2.00 XSOO
1.4E-14 2.9E+02
1.4E-14 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
CH3O 1n35 0.50 CH2O 0.50 no35
0.50 nd38 0.50 o011 -2.00 XPOO
CH3O 1n41 0.50 CH2O 0.50 nv4E
0.50 nv4D 0.50 o011 -2.00 XSOO
2.5E-14 -7.1E+02
2.5E-14 -7.1E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
a Reaction added by Williams [1994a]
Source
Madronich and Calvert [1989]
Madronich and Calvert [1989]
Madronich and Calvert [1989]
Madronich and Calvert [1989]
a
a
256
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 2n42
2011 2n42
!
2011 2n43
2011 2n43
2011 2n44
2011 2n44
2011 2n45
2011 2n45
!
2011 2n46
2011 2n46
2011 2n47
2011 2n47
2011 2n48
!
2011 2n48
2011 2n49
2011 2n49
2011 2n4a
2011 2n4a
2011 2n4b
!
2011 2n4b
2011 2n51
2011 2n51
2011 2n52
2011 2n52
!
2011 2n53
2011 2n53
2011 2n54
2011 2n54
2011 2n55
2011 2n55
!
2011 2n56
2011 2n56
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
k2 98 E/R
CH3O 1n42 0.50 CH2O 0.50 nk4G
0.50 nk4F 0.50 o011 -2.00 XSOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
CH3O 1n43 0.50 CH2O 0.50 nv4H
0.50 nd4A 0.50 o011 -2.00 XPOO
CH3O 1n44 0.50 CH2O 0.50 nk4I
0.50 nd4B 0.50 o011 -2.00 XPOO
CH3O 1n47 0.50 CH2O 0.50 no43
0.50 nk45 0.50 o011 -2.00 XSOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.2E-14 2.9E+02
1.2E-14 2.9E+02
1.40 CH3O 1.40 1n46 0.60 CH2O 0.60 no45
-2.00 XTOO
1.40 CH3O 1.40 1n45 0.60 CH2O 0.60 nd4C
-2.00 XTOO
CH3O 1n48 0.50 CH2O 0.50 nk4A
1.0E-15 2.9E+02
1.0E-15 2.9E+02
1.0E-15 2.9E+02
1.0E-15 2.9E+02
1.2E-14 2.9E+02
0.50 nk47 0.50 o011 -2.00 XSOO
CH3O 1n49 0.50 CH2O 0.50 nk4C
0.50 nd4E 0.50 o011 -2.00 XPOO
CH3O 1n4a 0.50 CH2O 0.50 nk49
0.50 no46 0.05 o011 -2.00 XSOO
CH3O 1n4b 0.50 CH2O 0.50 nd48
1.2E-14 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.8E-15 -7.1E+02
1.8E-15 -7.1E+02
1.5E-13 2.9E+02
0.50 no4C 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1n51 0.60 CH2O 0.60 nu54
-2.00 XTOO
CH3O 1n52 0.50 CH2O 0.50 nu55
0.50 nu53 0.50 o011 -2.00 XSOO
1.5E-13 2.9E+02
1.3E-16 -7.1E+02
1.3E-16 -7.1E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
CH3O 1n53 0.50 CH2O 0.50 no5B
0.50 nk51 0.50 o011 -2.00 XSOO
1.40 CH3O 1.40 1n54 0.60 CH2O 0.60 no5C
-2.00 XTOO
CH3O 1n55 0.50 CH2O 0.50 no57
0.50 nk52 0.50 o011 -2.00 XSOO
1.1E-14 2.9E+02
1.1E-14 2.9E+02
8.7E-16 2.9E+02
8.7E-16 2.9E+02
1.6E-15 -7.1E+02
1.6E-15 -7.1E+02
CH3O 1n56 0.50 CH2O 0.50 no58
0.50 nk53 0.50 o011 -2.00 XSOO
1.6E-15 -7.1E+02
1.6E-15 -7.1E+02
a Reaction added by Williams [1994a]
Source
a
a
a
a
a
a
a
a
257
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
2011 2n57
1
!
2
2011 2n57
2011 2n58
2011 2n58
2011 2n59
2011 2n59
!
2011 2n5a
2011 2n5a
2011 2nA1
2011 2nA1
2011 2o11
2011 2o11
!
2011 2o21
2011 2o21
2011 2o31
2011 2o31
2011 2o32
!
2011 2o32
2011 2o33
2011 2o33
2011 2o34
2011 2o34
2011 2o35
!
2011 2o35
2011 2o40
2011 2o40
2011 2a43
2011 2a43
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
k2 98 E/R
CH3O 1n57 0.50 CH2O 0.50 no5E
1.6E-15 -7.1E+02
0.50 nk54 0.50 o011 -2.00 XSOO
CH3O 1n58 0.50 CH2O 0.50 no5F
0.50 nk55 0.50 o011 -2.00 XSOO
CH3O 1n59 0.50 CH2O 0.50 no5G
0.50 nk56 0.50 o011 -2.00 XSOO
1.6E-15 -7.1E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
CH3O 1n5a 0.50 CH2O 0.50 no5H
0.50 nd58 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1nA1 0.60 CH2O 0.60 ntA2
-2.00 XTOO
CH3O 1o11 0.50 CH2O 0.50 oo11
0.50 a011 0.50 o011 -2.00 XPOO
1.9E-14 -7.1E+02
1.9E-14 -7.1E+02
6.8E-16 -1.2E+03
6.8E-16 -1.2E+03
1.5E-12 2.9E+02
1.5E-12 2.9E+02
CH3O 1o22 0.50 CH2O 0.50 oo21
0.50 do23 0.50 o011 -2.00 XPOO
CH3O 1o32 0.50 CH2O 0.50 oo32
0.50 ko31 0.50 o011 -2.00 XSOO
CH3O 1o33 0.50 CH2O 0.50 oo31
9.2E-13 2.9E+02
9.2E-13 2.9E+02
1.4E-14 2.9E+02
1.4E-14 2.9E+02
1.4E-14 2.9E+02
0.50 ko37 0.50 o011 -2.00 XSOO
CH3O 1o34 0.50 CH2O 0.50 oo31
0.50 do34 0.50 o011 -2.00 XPOO
CH3O 1o35 0.50 CH2O 0.50 oo33
0.50 do35 0.50 o011 -2.00 XPOO
CH3O 1o31 0.50 CH2O 0.50 oo32
1.4E-14 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
2.5E-14 -7.1E+02
2.5E-14 -7.1E+02
1.7E-13 2.9E+02
0.50 do31 0.50 o011 -2.00 XPOO
CH3O 1o40 0.50 CH2O 0.50 oo41
0.50 do46 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1a44 0.60 CH2O 0.60 ao48
-2.00 XTOO
1.7E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.0E-15 2.9E+02
1.0E-15 2.9E+02
Source
a
a
a
a
a
a
a
a
b
b
b;c
b;c
b;d
b;d
a Reaction added by Williams [1994a]
b E/R calculated from estimated self-reaction activation temperatures
c 2o11 self reaction rate from Kirchner and Stockwell [1996] from Lightfoot et al. [1992]
d 2o21 self reaction rate from Kirchner and Stockwell [1996] from Lightfoot et al. [1992]
258
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 2o42
2011 2o42
2011 2o43
2011 2o43
!
2011 2o44
2011 2o44
2011 2o45
2011 2o45
2011 2o46
!
2011 2o46
2011 2a47
2011 2a47
2011 2o48
2011 2o48
2011 2o49
!
2011 2o49
2011 2o4A
2011 2o4A
2011 2o4B
2011 2o4B
!
2011 2o4C
2011 2o4C
2011 2o4D
2011 2o4D
2011 2o50
2011 2o50
!
2011 2o51
2011 2o51
2011 2o52
2011 2o52
2011 2o53
!
2011 2o53
2011 2o54
2011 2o54
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
k2 98 E/R
Source
CH3O 1o43 0.50 CH2O 0.50 oo42
0.50 do41 0.50 o011 -2.00 XPOO
CH3O 1o44 0.50 CH2O 0.50 oo47
0.50 ko42 0.50 o011 -2.00 XSOO
2.2E-14 -7.1E+02
2.2E-14 -7.1E+02
5.6E-13 2.9E+02
5.6E-13 2.9E+02
a ;b
a;b
1.40 CH3O 1.40 1o41 0.60 CH2O 0.60 oo43
-2.00 XTOO
CH3O 1o45 0.50 CH2O 0.50 oo43
0.50 do42 0.50 o011 -2.00 XPOO
CH3O 1o46 0.50 CH2O 0.50 oo44
1.0E-15 2.9E+02
1.0E-15 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
2.2E-14 -7.1E+02
0.50 do44 0.50 o011 -2.00 XPOO
CH3O 1a42 0.50 CH2O 0.50 ao46
0.50 ad49 0.50 o011 -2.00 XPOO
CH3O 1o48 0.50 CH2O 0.50 oo48
0.50 do49 0.50 o011 -2.00 XPOO
CH3O 1o49 0.50 CH2O 0.50 oo49
2.2E-14 -7.1E+02
2.2E-14 -7.1E+02
2.2E-14 -7.1E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
0.50 do40 0.50 o011 -2.00 XPOO
CH3O 1o4A 0.50 CH2O 0.50 oo45
0.50 do43 0.50 o011 -2.00 XPOO
CH3O 1o4B 0.50 CH2O 0.50 oo46
0.50 do45 0.50 o011 -2.00 XPOO
1.5E-13 2.9E+02
2.2E-14 -7.1E+02
2.2E-14 -7.1E+02
2.2E-14 -7.1E+02
2.2E-14 -7.1E+02
CH3O 1o4C 0.50 CH2O 0.50 oo44
0.50 ko45 0.50 o011 -2.00 XPOO
CH3O 1o4D 0.50 CH2O 0.50 oo47
0.50 do48 0.50 o011 -2.00 XPOO
CH3O 1o50 0.50 CH2O 0.50 oo53
0.50 ko50 0.50 o011 -2.00 XSOO
1.8E-15 -7.1E+02
1.8E-15 -7.1E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
CH3O 1o52 0.50 CH2O 0.50 oo51
0.50 ko56 0.50 o011 -2.00 XSOO
CH3O 1o54 0.50 CH2O 0.50 oo54
0.50 ko53 0.50 o011 -2.00 XSOO
CH3O 1o53 0.50 CH2O 0.50 oo55
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
0.50 ko51 0.50 o011 -2.00 XSOO
CH3O 1o51 0.50 CH2O 0.50 oo57
0.50 ko55 0.50 o011 -2.00 XSOO
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
a upper limit for 2o43 self reaction rate from Kirchner and Stockwell [1996], from LeBras [1997]
b E/R calculated from estimated self–reaction activation temperatures
259
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 2o55
2011 2o55
!
2011 2o56
2011 2o56
2011 2o57
2011 2o57
2011 2o58
2011 2o58
!
2011 2o59
2011 2o59
2011 2o5A
2011 2o5A
2011 2o5B
!
2011 2o5B
2011 2a51
2011 2a51
2011 2a50
2011 2a50
2011 2a53
!
2011 2a53
2011 2o61
2011 2o61
2011 2o62
2011 2o62
!
2011 2o63
2011 2o63
2011 2o64
2011 2o64
2011 2o65
2011 2o65
!
2011 2o71
2011 2o71
2011 2o81
2011 2o81
2011 2p21
!
2011 2p21
2011 2p30
2011 2p30
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
k2 98 E/R
CH3O 1o50 0.50 CH2O 0.50 oo54
0.50 do57 0.50 o011 -2.00 XPOO
1.9E-14 -7.1E+02
1.9E-14 -7.1E+02
CH3O 1o56 0.50 CH2O 0.50 oo51
0.50 ko52 0.50 o011 -2.00 XSOO
CH3O 1o57 0.50 CH2O 0.50 oo51
0.50 do52 0.50 o011 -2.00 XPOO
CH3O 1o58 0.50 CH2O 0.50 oo58
0.50 do53 0.50 o011 -2.00 XPOO
1.6E-15 -7.1E+02
1.6E-15 -7.1E+02
1.9E-14 -7.1E+02
1.9E-14 -7.1E+02
1.9E-14 -7.1E+02
1.9E-14 -7.1E+02
CH3O 1o59 0.50 CH2O 0.50 oo52
0.50 do54 0.50 o011 -2.00 XPOO
1o5C CH3O 0.50 oo59 0.50 CH2O
0.50 ko54 0.50 o011 -2.00 XSOO
1o5B CH3O 0.50 oo59 0.50 CH2O
1.9E-14 -7.1E+02
1.9E-14 -7.1E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.3E-13 2.9E+02
0.50 do50 0.50 o011 -2.00 XPOO
1a50 CH3O 0.50 ak57 0.50 CH2O
0.50 ak51 0.50 o011 -2.00 XSOO
1a51 CH3O 0.50 ak57 0.50 CH2O
0.50 ak51 0.50 o011 -2.00 XSOO
1a52 CH3O 0.50 ak58 0.50 CH2O
1.3E-13 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.1E-14 2.9E+02
1.3E-13 2.9E+02
0.50 ad53 0.50 o011 -2.00 XPOO
CH3O 1o61 0.50 CH2O 0.50 oo61
0.50 dd61 0.50 o011 -2.00 XPOO
CH3O 1o63 0.50 CH2O 0.50 oo62
0.50 do62 0.50 o011 -2.00 XPOO
1.3E-13 2.9E+02
1.1E-13 2.9E+02
1.1E-13 2.9E+02
1.7E-14 -7.1E+02
1.7E-14 -7.1E+02
CH3O 1o64 0.50 CH2O 0.50 oo63
0.50 do64 0.50 o011 -2.00 XPOO
CH3O 1o62 0.50 CH2O 0.50 oo64
0.50 do63 0.50 o011 -2.00 XPOO
CH3O 1o65 0.50 CH2O 0.50 oo65
0.50 do65 0.50 o011 -2.00 XPOO
1.7E-14 -7.1E+02
1.7E-14 -7.1E+02
1.7E-14 -7.1E+02
1.7E-14 -7.1E+02
1.7E-14 -7.1E+02
1.7E-14 -7.1E+02
CH3O 1o71 0.50 CH2O 0.50 oo71
0.50 ko71 0.50 o011 -2.00 XPOO
CH3O 1o81 0.50 CH2O 0.50 oo81
0.50 dk81 0.50 o011 -2.00 XSOO
CH3O 1p21 0.50 CH2O 0.50 po23
1.0E-13 2.9E+02
1.0E-13 2.9E+02
8.3E-15 -1.2E+03
8.3E-15 -1.2E+03
1.9E-13 2.9E+02
0.50 pd21 0.50 o011 -2.00 XPOO
1p30 CH3O 0.50 po35 0.50 CH2O
0.50 pd33 0.50 o011 -2.00 XPOO
1.9E-13 2.9E+02
2.5E-14 -7.1E+02
2.5E-14 -7.1E+02
a E/R calculated from estimated self-reaction activation temperatures
Source
a
a
260
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 2p31
2011 2p31
!
2011 2t71
2011 2t71
2011 2t81
2011 2t81
2011 2d81
2011 2d81
!
2011 2t91
2011 2t91
2011 2t92
2011 2t92
2011 2tA1
!
2011 2tA1
2011 2dA2
2011 2dA2
2011 2r61
2011 2r61
2011 2r62
!
2011 2r62
2011 2r63
2011 2r63
2011 2r71
2011 2r71
!
2011 2r72
2011 2r72
2011 2r73
2011 2r73
2011 2r74
2011 2r74
!
2011 2r81
2011 2r81
2011 2r82
2011 2r82
2011 2s21
!
2011 2s21
2011 2r75
2011 2r75
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
k2 98 E/R
1p31 CH3O 0.50 po31 0.50 CH2O
0.50 pk33 0.50 o011 -2.00 XSOO
1.4E-14 2.9E+02
1.4E-14 2.9E+02
1.40 CH3O 1.40 2e72 0.60 CH2O 0.60 et71
-0.60 XTOO
CH3O 1t81 0.50 CH2O 0.50 tk82
0.50 tk81 0.50 o011 -2.00 XSOO
CH3O 1d82 0.50 CH2O 0.50 dt82
0.50 dt81 0.50 o011 -2.00 XSOO
1.0E-16 -7.1E+02
1.0E-16 -7.1E+02
1.2E-15 -1.2E+03
1.2E-15 -1.2E+03
1.2E-15 -1.2E+03
1.2E-15 -1.2E+03
CH3O 1t91 0.50 CH2O 0.50 tk91
0.50 dt91 0.50 o011 -2.00 XPOO
CH3O 1t92 0.50 CH2O 0.50 tk92
0.50 dt92 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1tA1 0.60 CH2O 0.60 toA1
1.5E-14 -1.2E+03
1.5E-14 -1.2E+03
1.5E-14 -1.2E+03
1.5E-14 -1.2E+03
6.8E-16 -1.2E+03
-2.00 XTOO
CH3O 1dA2 0.50 CH2O 0.50 dtA3
0.50 ddA2 0.50 o011 -2.00 XPOO
CH3O 1r63 0.50 CH2O 0.50 ro64
0.50 rk63 0.50 o011 -2.00 XSOO
CH3O 1r64 0.50 CH2O 0.50 ro65
6.8E-16 -1.2E+03
1.0E-13 -1.2E+03
1.0E-13 -1.2E+03
9.3E-15 2.9E+02
9.3E-15 2.9E+02
9.3E-15 2.9E+02
0.50 rk62 0.50 o011 -2.00 XSOO
1.40 CH3O 1.40 1r61 0.60 CH2O 0.60 ro61
-2.00 XTOO
1.40 CH3O 1.40 1r74 0.60 CH2O 0.60 rv75
-2.00 XTOO
9.3E-15 2.9E+02
1.1E-16 1.2E+03
1.1E-16 1.2E+03
1.0E-16 -7.1E+02
1.0E-16 -7.1E+02
CH3O 1r71 0.50 CH2O 0.50 ro71
0.50 dr71 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1r75 0.60 CH2O 0.60 ro76
-2.00 XTOO
1.40 CH3O 1.40 1r76 0.60 CH2O 0.60 ro77
-2.00 XTOO
1.7E-12 -1.1E+03
1.7E-12 -1.1E+03
1.0E-16 -7.1E+02
1.0E-16 -7.1E+02
1.0E-16 -7.1E+02
1.0E-16 -7.1E+02
1.40 CH3O 1.40 1r82 0.60 CH2O 0.60 ro83
-2.00 XTOO
1.40 CH3O 1.40 1r83 0.60 CH2O 0.60 ro84
-2.00 XTOO
CH3O 1s21 0.50 CH2O 0.50 so21
1.0E-16 -1.2E+03
1.0E-16 -1.2E+03
1.0E-16 -1.2E+03
1.0E-16 -1.2E+03
2.8E-14 -1.6E+02
0.50 sd21 0.50 o011 -2.00 XPOO
1.40 CH3O 1.40 1r77 0.60 CH2O 0.60 rv78
-2.00 XTOO
2.8E-14 -1.6E+02
1.0E-16 -7.1E+02
1.0E-16 -7.1E+02
a E/R calculated from estimated self-reaction activation temperatures
b 2r72 self reaction rate from Kirchner and Stockwell [1996] from LeBras [1997]
Source
a
a
a
a
a
a
a
a
a
a
a
a
b
a
a
a
a
261
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 3021
2011 3021
!
2011 3031
2011 3031
2011 3a31
2011 3a31
2011 3a32
2011 3a32
!
2011 3a33
2011 3a33
2011 3n34
2011 3n34
2011 3041
!
2011 3041
2011 3042
2011 3042
2011 3h40
2011 3h40
2011 3g40
!
2011 3g40
2011 3051
2011 3051
2011 3052
2011 3052
!
2011 3053
2011 3053
2011 3061
2011 3061
2011 3a21
2011 3a21
!
2011 3u31
2011 3u31
2011 3u32
2011 3u32
2011 3u41
!
2011 3u41
2011 3u42
2011 3u42
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
k2 98 E/R
1.40 CH3O 1.40 8021 0.60 CH2O 0.60 a021
-2.00 XAOO
5.5E-12 -6.4E+02
5.5E-12 -6.4E+02
1.40 CH3O 1.40 8031 0.60 CH2O 0.60 a031
-2.00 XAOO
1.40 CH3O 1.40 8a31 0.60 CH2O 0.60 aa31
-2.00 XAOO
1.40 CH3O 1.40 8a32 0.60 CH2O 0.60 aa32
-2.00 XAOO
2.5E-12 2.9E+02
2.5E-12 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.40 CH3O 1.40 8a33 0.60 CH2O 0.60 aa33
-2.00 XAOO
1.40 CH3O 1.40 8n34 0.60 CH2O 0.60 an35
-2.00 XAOO
1.40 CH3O 1.40 8041 0.60 CH2O 0.60 a041
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.5E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8042 0.60 CH2O 0.60 a042
-2.00 XAOO
1.40 ko37 0.60 ah42 1.40 CH3O 0.60 CH2O
-2.00 XAOO 1.40 HO 1.40 CO2
1.40 gk33 0.60 ag40 1.40 CH3O 0.60 CH2O
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
-2.00 XAOO 1.40 HO 1.40 CO2
1.40 CH3O 1.40 8051 0.60 CH2O 0.60 a051
-2.00 XAOO
1.40 CH3O 1.40 8052 0.60 CH2O 0.60 a052
-2.00 XAOO
1.5E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.40 CH3O 1.40 8053 0.60 CH2O 0.60 a053
-2.00 XAOO
1.40 CH3O 1.40 8061 0.60 CH2O 0.60 a061
-2.00 XAOO
1.40 CH3O 1.40 8a21 0.60 CH2O 0.60 aa21
-2.00 XAOO
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.1E-13 2.9E+02
1.1E-13 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.40 CH3O 1.40 8u31 0.60 CH2O 0.60 au31
-2.00 XAOO
1.40 CH3O 1.40 8u32 0.60 CH2O 0.60 au32
-2.00 XAOO
1.40 CH3O 1.40 8u41 0.60 CH2O 0.60 au41
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.2E-14 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8u42 0.60 CH2O 0.60 au42
-2.00 XAOO
1.2E-14 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
Source
DeMore et al. [1997] a
DeMore et al. [1997]
b;c
a 3021 self reaction rate from Kirchner and Stockwell [1996], from Lightfoot et al. [1992]
b 3031 self reaction rate from Kirchner and Stockwell [1996], from LeBras [1997]
c E/R calculated from estimated self-reaction activation temperatures
262
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 3u43
2011 3u43
!
2011 3u44
2011 3u44
2011 3u51
2011 3u51
2011 3u52
2011 3u52
!
2011 3u53
2011 3u53
2011 3d21
2011 3d21
2011 3d31
!
2011 3d31
2011 3d32
2011 3d32
2011 3d33
2011 3d33
2011 3d41
!
2011 3d41
2011 3d42
2011 3d42
2011 3d43
2011 3d43
!
2011 3d44
2011 3d44
2011 3d45
2011 3d45
2011 3d46
2011 3d46
!
2011 3d47
2011 3d47
2011 3d48
2011 3d48
2011 3d51
!
2011 3d51
2011 3d52
2011 3d52
2011 3d53
2011 3d53
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
k2 98 E/R
1.40 CH3O 1.40 8u43 0.60 CH2O 0.60 au43
-2.00 XAOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.40 CH3O 1.40 8u44 0.60 CH2O 0.60 au44
-2.00 XAOO
1.40 CH3O 1.40 8u51 0.60 CH2O 0.60 au51
-2.00 XAOO
1.40 CH3O 1.40 8u52 0.60 CH2O 0.60 au52
-2.00 XAOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.40 CH3O 1.40 8u53 0.60 CH2O 0.60 au53
-2.00 XAOO
1.40 CH3O 1.40 8d21 0.60 CH2O 0.60 ad21
-2.00 XAOO
1.40 CH3O 1.40 8d31 0.60 CH2O 0.60 ad31
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.7E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8d32 0.60 CH2O 0.60 ad32
-2.00 XAOO
1.40 CH3O 1.40 8d33 0.60 CH2O 0.60 ad33
-2.00 XAOO
1.40 CH3O 1.40 8d41 0.60 CH2O 0.60 ad41
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.5E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8d42 0.60 CH2O 0.60 ad42
-2.00 XAOO
1.40 CH3O 1.40 8d43 0.60 CH2O 0.60 ad43
-2.00 XAOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.40 CH3O 1.40 8d44 0.60 CH2O 0.60 ad44
-2.00 XAOO
1.40 CH3O 1.40 8d45 0.60 CH2O 0.60 ad45
-2.00 XAOO
1.40 CH3O 1.40 8d46 0.60 CH2O 0.60 ad46
-2.00 XAOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.40 CH3O 1.40 8d47 0.60 CH2O 0.60 ad47
-2.00 XAOO
1.40 CH3O 1.40 8d48 0.60 CH2O 0.60 ad48
-2.00 XAOO
1.40 CH3O 1.40 8d51 0.60 CH2O 0.60 ad51
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.3E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8d52 0.60 CH2O 0.60 ad52
-2.00 XAOO
1.40 CH3O 1.40 8d53 0.60 CH2O 0.60 ad53
-2.00 XAOO
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
Source
263
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 3d54
2011 3d54
2011 3d55
2011 3d55
!
2011 3d56
2011 3d56
2011 3h21
2011 3h21
2011 3v22
!
2011 3v22
2011 3k31
2011 3k31
2011 3v32
2011 3v32
2011 3k33
!
2011 3k33
2011 3k40
2011 3k40
2011 3v41
2011 3v41
!
2011 3v42
2011 3v42
2011 3v43
2011 3v43
2011 3v44
2011 3v44
!
2011 3k45
2011 3k45
2011 3k46
2011 3k46
2011 3k47
!
2011 3k47
2011 3k48
2011 3k48
2011 3k49
2011 3k49
2011 3k4A
!
2011 3k4A
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
k2 98 E/R
1.40 CH3O 1.40 8d54 0.60 CH2O 0.60 ad54
-2.00 XAOO
1.40 CH3O 1.40 8d55 0.60 CH2O 0.60 ad55
-2.00 XAOO
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.40 CH3O 1.40 8d56 0.60 CH2O 0.60 ad56
-2.00 XAOO
1.40 CH3O 1.40 8h21 0.60 CH2O 0.60 ah21
-2.00 XAOO
1.40 CH3O 1.40 8v21 0.60 CH2O 0.60 av22
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8k31 0.60 CH2O 0.60 ak31
-2.00 XAOO
1.40 CH3O 1.40 8v32 0.60 CH2O 0.60 av32
-2.00 XAOO
1.40 CH3O 1.40 8k33 0.60 CH2O 0.60 ak33
1.9E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8k40 0.60 CH2O 0.60 ak40
-2.00 XAOO
1.40 CH3O 1.40 8v41 0.60 CH2O 0.60 av41
-2.00 XAOO
1.7E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.40 CH3O 1.40 8v42 0.60 CH2O 0.60 av42
-2.00 XAOO
1.40 CH3O 1.40 8v43 0.60 CH2O 0.60 av43
-2.00 XAOO
1.40 CH3O 1.40 8v44 0.60 CH2O 0.60 av44
-2.00 XAOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.40 CH3O 1.40 8k45 0.60 CH2O 0.60 ak45
-2.00 XAOO
1.40 CH3O 1.40 8k46 0.60 CH2O 0.60 ak46
-2.00 XAOO
1.40 CH3O 1.40 8k47 0.60 CH2O 0.60 ak47
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8k48 0.60 CH2O 0.60 ak48
-2.00 XAOO
1.40 CH3O 1.40 8k49 0.60 CH2O 0.60 ak49
-2.00 XAOO
1.40 CH3O 1.40 8k4A 0.60 CH2O 0.60 ak4A
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
-2.00 XAOO
1.5E-13 2.9E+02
Source
264
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 3k50
2011 3k50
2011 3k51
2011 3k51
!
2011 3k52
2011 3k52
2011 3k53
2011 3k53
2011 3v54
!
2011 3v54
2011 3k55
2011 3k55
2011 3v56
2011 3v56
2011 3k57
!
2011 3k57
2011 3k58
2011 3k58
2011 3k59
2011 3k59
!
2011 3k5A
2011 3k5A
2011 3k5B
2011 3k5B
2011 3k5C
2011 3k5C
!
2011 3l11
2011 3l11
2011 3n21
2011 3n21
2011 3n31
!
2011 3n31
2011 3n32
2011 3n32
2011 3n33
2011 3n33
2011 3n41
!
2011 3n41
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
k2 98 E/R
1.40 CH3O 1.40 8k50 0.60 CH2O 0.60 ak50
-2.00 XAOO
1.40 CH3O 1.40 8k51 0.60 CH2O 0.60 ak51
-2.00 XAOO
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.40 CH3O 1.40 8k52 0.60 CH2O 0.60 ak52
-2.00 XAOO
1.40 CH3O 1.40 8k53 0.60 CH2O 0.60 ak53
-2.00 XAOO
1.40 CH3O 1.40 8v54 0.60 CH2O 0.60 av54
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8k55 0.60 CH2O 0.60 ak55
-2.00 XAOO
1.40 CH3O 1.40 8v56 0.60 CH2O 0.60 av56
-2.00 XAOO
1.40 CH3O 1.40 8k57 0.60 CH2O 0.60 ak57
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8k58 0.60 CH2O 0.60 ak58
-2.00 XAOO
1.40 CH3O 1.40 8k59 0.60 CH2O 0.60 ak59
-2.00 XAOO
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.40 CH3O 1.40 8k5A 0.60 CH2O 0.60 ak5A
-2.00 XAOO
1.40 CH3O 1.40 8k5B 0.60 CH2O 0.60 ak5B
-2.00 XAOO
1.40 CH3O 1.40 8k5C 0.60 CH2O 0.60 ak5C
-2.00 XAOO
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.40 CH3O 1.40 8l11 0.60 CH2O 0.60 la11
-2.00 XAOO
1.40 CH3O 1.40 8n21 0.60 CH2O 0.60 an21
-2.00 XAOO
1.40 CH3O 1.40 8n31 0.60 CH2O 0.60 an31
2.5E-12 2.9E+02
2.5E-12 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.7E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8n32 0.60 CH2O 0.60 an32
-2.00 XAOO
1.40 CH3O 1.40 8n33 0.60 CH2O 0.60 an33
-2.00 XAOO
1.40 CH3O 1.40 8n41 0.60 CH2O 0.60 an41
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.5E-13 2.9E+02
-2.00 XAOO
1.5E-13 2.9E+02
Source
265
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 3n42
2011 3n42
!
2011 3n43
2011 3n43
2011 3n44
2011 3n44
2011 3n45
2011 3n45
!
2011 3n46
2011 3n46
2011 3n47
2011 3n47
2011 3n48
!
2011 3n48
2011 3n49
2011 3n49
2011 3n51
2011 3n51
2011 3n52
!
2011 3n52
2011 3n53
2011 3n53
2011 3n54
2011 3n54
!
2011 3n55
2011 3n55
2011 3o22
2011 3o22
2011 3o23
2011 3o23
!
2011 3v21
2011 3v21
2011 3o31
2011 3o31
2011 3o32
!
2011 3o32
2011 3o33
2011 3o33
2011 3o34
2011 3o34
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
k2 98 E/R
1.40 CH3O 1.40 8n42 0.60 CH2O 0.60 an42
-2.00 XAOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.40 CH3O 1.40 8n43 0.60 CH2O 0.60 an43
-2.00 XAOO
1.40 CH3O 1.40 8n44 0.60 CH2O 0.60 an44
-2.00 XAOO
1.40 CH3O 1.40 8n45 0.60 CH2O 0.60 an45
-2.00 XAOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.40 CH3O 1.40 8n46 0.60 CH2O 0.60 an46
-2.00 XAOO
1.40 CH3O 1.40 8n47 0.60 CH2O 0.60 an47
-2.00 XAOO
1.40 CH3O 1.40 8n48 0.60 CH2O 0.60 an48
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
-2.00 XAOO
1.40 ko37 0.60 an49 1.40 CH3O 0.60 CH2O
-2.00 XAOO 1.40 NO2 1.40 CO2
1.40 CH3O 1.40 8n51 0.60 CH2O 0.60 an51
-2.00 XAOO
1.40 CH3O 1.40 8n52 0.60 CH2O 0.60 an52
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8n53 0.60 CH2O 0.60 an53
-2.00 XAOO
1.40 CH3O 1.40 8n54 0.60 CH2O 0.60 an54
-2.00 XAOO
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.40 CH3O 1.40 8n55 0.60 CH2O 0.60 an55
-2.00 XAOO
1.40 CH3O 1.40 8o22 0.60 CH2O 0.60 ao22
-2.00 XAOO
1.40 CH3O 1.40 8o23 0.60 CH2O 0.60 ao23
-2.00 XAOO
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.40 CH3O 1.40 8v22 0.60 CH2O 0.60 av21
-2.00 XAOO
1.40 CH3O 1.40 8o31 0.60 CH2O 0.60 ao31
-2.00 XAOO
1.40 CH3O 1.40 8o32 0.60 CH2O 0.60 ao32
1.9E-13 2.9E+02
1.9E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8o33 0.60 CH2O 0.60 ao33
-2.00 XAOO
1.40 CH3O 1.40 8o34 0.60 CH2O 0.60 ao34
-2.00 XAOO
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.7E-13 2.9E+02
Source
266
Table C.10 (continued) Peroxy radical reactions with methyl peroxy radical
Reaction
1
2011 3o35
2011 3o35
!
2011 3o41
2011 3o41
2011 3o42
2011 3o42
2011 3o43
2011 3o43
!
2011 3o44
2011 3o44
2011 3o45
2011 3o45
2011 3o46
!
2011 3o46
2011 3o47
2011 3o47
2011 3o51
2011 3o51
2011 3o52
!
2011 3o52
2011 3o53
2011 3o53
2011 3o54
2011 3o54
!
2011 3o55
2011 3o55
2011 3o56
2011 3o56
2011 3o57
2011 3o57
!
2011 3o61
2011 3o61
2011 3t91
2011 3t91
2011 3tA1
!
2011 3tA1
2011 3r71
2011 3r71
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
!
2
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
!
1
2
!
1
!
2
!
1
!
2
1
!
2
!
k2 98 E/R
1.40 CH3O 1.40 8o35 0.60 CH2O 0.60 ao35
-2.00 XAOO
1.7E-13 2.9E+02
1.7E-13 2.9E+02
1.40 CH3O 1.40 8o41 0.60 CH2O 0.60 ao41
-2.00 XAOO
1.40 CH3O 1.40 8o42 0.60 CH2O 0.60 ao42
-2.00 XAOO
1.40 CH3O 1.40 8o43 0.60 CH2O 0.60 ao43
-2.00 XAOO
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.40 CH3O 1.40 8o44 0.60 CH2O 0.60 ao44
-2.00 XAOO
1.40 CH3O 1.40 8o45 0.60 CH2O 0.60 ao45
-2.00 XAOO
1.40 CH3O 1.40 8o46 0.60 CH2O 0.60 ao46
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8o47 0.60 CH2O 0.60 ao47
-2.00 XAOO
1.40 CH3O 1.40 8o51 0.60 CH2O 0.60 ao51
-2.00 XAOO
1.40 CH3O 1.40 8o52 0.60 CH2O 0.60 ao52
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.5E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
-2.00 XAOO
1.40 CH3O 1.40 8o53 0.60 CH2O 0.60 ao53
-2.00 XAOO
1.40 CH3O 1.40 8o54 0.60 CH2O 0.60 ao54
-2.00 XAOO
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.40 CH3O 1.40 8o55 0.60 CH2O 0.60 ao55
-2.00 XAOO
1.40 CH3O 1.40 8o56 0.60 CH2O 0.60 ao56
-2.00 XAOO
1.40 do49 0.60 ao50 1.40 CH3O 0.60 CH2O
-2.00 XAOO 1.40 HO2 1.40 CO2
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.3E-13 2.9E+02
1.40 CH3O 1.40 8o61 0.60 CH2O 0.60 ao61
-2.00 XAOO
1.40 CH3O 1.40 8t91 0.60 CH2O 0.60 at91
-2.00 XAOO
1.40 CH3O 1.40 8tA1 0.60 CH2O 0.60 atA1
1.1E-13 2.9E+02
1.1E-13 2.9E+02
1.0E-13 -1.2E+03 a
1.0E-13 -1.2E+03 a
1.0E-13 -1.2E+03a
-2.00 XAOO
1.40 CH3O 1.40 8r71 0.60 CH2O 0.60 ar71
-2.00 XAOO
1.0E-13 -1.2E+03a
1.0E-13 2.9E+02
1.0E-13 2.9E+02
a E/R calculated from estimated self-reaction activation temperatures
Source
267
Table C.11 Peroxy radical cross reactions.
2021 XPOO
2021 XSOO
2021 XTOO
2021 XAOO
2031 XPOO
2031 XSOO
2031 XTOO
2031 XAOO
2032 XPOO
2032 XSOO
2032 XTOO
2032 XAOO
2041 XPOO
2041 XSOO
2041 XTOO
2041 XAOO
2042 XPOO
2042 XSOO
2042 XTOO
2042 XAOO
2043 XPOO
2043 XSOO
2043 XTOO
2043 XAOO
2044 XPOO
2044 XSOO
2044 XTOO
2044 XAOO
2051 XPOO
2051 XSOO
2051 XTOO
2051 XAOO
2052 XPOO
2052 XSOO
2052 XTOO
2052 XAOO
2053 XPOO
2053 XSOO
2053 XTOO
2053 XAOO
2054 XPOO
2054 XSOO
2054 XTOO
2054 XAOO
2055 XPOO
2055 XSOO
2055 XTOO
2055 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1021 0.20 o021 0.20 d021
0.60 1021 0.20 o021 0.20 d021
0.80 1021 0.20 d021
0.80 1021 0.20 d021
0.60 1032 0.20 o032 0.20 k031
0.60 1032 0.20 o032 0.20 k031
0.80 1032 0.20 k031
0.80 1032 0.20 k031
0.60 1031 0.20 o031 0.20 d031
0.60 1031 0.20 o031 0.20 d031
0.80 1031 0.20 d031
0.80 1031 0.20 d031
0.60 1043 0.20 o041 0.20 k041
0.60 1043 0.20 o041 0.20 k041
0.80 1043 0.20 k041
0.80 1043 0.20 k041
0.60 1042 0.20 o042 0.20 d041
0.60 1042 0.20 o042 0.20 d041
0.80 1042 0.20 d041
0.80 1042 0.20 d041
0.80 1044 0.20 o043
0.80 1044 0.20 o043
1044
1044
0.60 1044 0.20 o044 0.20 d042
0.60 1044 0.20 o044 0.20 d042
0.80 1044 0.20 d042
0.80 1044 0.20 d042
0.60 1051 0.20 o054 0.20 k051
0.60 1051 0.20 o054 0.20 k051
0.80 1051 0.20 k051
0.80 1051 0.20 k051
0.60 1052 0.20 o052 0.20 k053
0.60 1052 0.20 o052 0.20 k053
0.80 1052 0.20 k053
0.80 1052 0.20 k053
0.60 1053 0.20 o053 0.20 d051
0.60 1053 0.20 o053 0.20 d051
0.80 1053 0.20 d051
0.80 1053 0.20 d051
0.60 1054 0.20 o054 0.20 k051
0.60 1054 0.20 o054 0.20 k051
0.80 1054 0.20 k051
0.80 1054 0.20 k051
0.60 1055 0.20 o055 0.20 k052
0.60 1055 0.20 o055 0.20 k052
0.80 1055 0.20 k052
0.80 1055 0.20 k052
k2 98 E/R
2.6E-13 0.0E+00
3.6E-14 0.0E+00
2.3E-15 0.0E+00
8.9E-13 0.0E+00
3.3E-14 0.0E+00
4.7E-15 0.0E+00
3.0E-16 0.0E+00
1.2E-13 0.0E+00
6.2E-13 0.0E+00
8.8E-14 0.0E+00
5.6E-15 0.0E+00
2.2E-12 0.0E+00
3.0E-15 0.0E+00
4.2E-16 0.0E+00
2.7E-17 0.0E+00
1.0E-14 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
5.5E-15 0.0E+00
7.8E-16 0.0E+00
4.9E-17 0.0E+00
1.9E-14 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
2.6E-15 0.0E+00
3.7E-16 0.0E+00
2.3E-17 0.0E+00
9.0E-15 0.0E+00
2.6E-15 0.0E+00
3.7E-16 0.0E+00
2.3E-17 0.0E+00
9.0E-15 0.0E+00
3.2E-14 0.0E+00
4.5E-15 0.0E+00
2.8E-16 0.0E+00
1.1E-13 0.0E+00
2.6E-15 0.0E+00
3.7E-16 0.0E+00
2.3E-17 0.0E+00
9.0E-15 0.0E+00
2.6E-15 0.0E+00
3.7E-16 0.0E+00
2.3E-17 0.0E+00
9.0E-15 0.0E+00
Source
268
Table C.11 (continued) Peroxy Radical Cross Reactions
2056 XPOO
2056 XSOO
2056 XTOO
2056 XAOO
2057 XPOO
2057 XSOO
2057 XTOO
2057 XAOO
2061 XPOO
2061 XSOO
2061 XTOO
2061 XAOO
2062 XPOO
2062 XSOO
2062 XTOO
2062 XAOO
2063 XPOO
2063 XSOO
2063 XTOO
2063 XAOO
2071 XPOO
2071 XSOO
2071 XTOO
2071 XAOO
2081 XPOO
2081 XSOO
2081 XTOO
2081 XAOO
2a21 XPOO
2a21 XSOO
2a21 XTOO
2a21 XAOO
2a31 XPOO
2a31 XSOO
2a31 XTOO
2a31 XAOO
2a41 XPOO
2a41 XSOO
2a41 XTOO
2a41 XAOO
2a42 XPOO
2a42 XSOO
2a42 XTOO
2a42 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1056 0.20 o056 0.20 d053
0.60 1056 0.20 o056 0.20 d053
0.80 1056 0.20 d053
0.80 1056 0.20 d053
0.80 1057 0.20 o057
0.80 1057 0.20 o057
1057
1057
0.60 1061 0.20 o061 0.20 k062
0.60 1061 0.20 o061 0.20 k062
0.80 1061 0.20 k062
0.80 1061 0.20 k062
0.80 1062 0.20 o062
0.80 1062 0.20 o062
1062
1062
0.60 1063 0.20 o063 0.20 d061
0.60 1063 0.20 o063 0.20 d061
0.80 1063 0.20 d061
0.80 1063 0.20 d061
0.60 1071 0.20 o071 0.20 k071
0.60 1071 0.20 o071 0.20 k071
0.80 1071 0.20 k071
0.80 1071 0.20 k071
0.60 1081 0.20 o081 0.20 k081
0.60 1081 0.20 o081 0.20 k081
0.80 1081 0.20 k081
0.80 1081 0.20 k081
0.60 1a21 0.20 ao23 0.20 ad21
0.60 1a21 0.20 ao23 0.20 ad21
0.80 1a21 0.20 ad21
0.80 1a21 0.20 ad21
0.60 1a31 0.20 ao34 0.20 ak33
0.60 1a31 0.20 ao34 0.20 ak33
0.80 1a31 0.20 ak33
0.80 1a31 0.20 ak33
0.60 1a41 0.20 ao45 0.20 ak4C
0.60 1a41 0.20 ao45 0.20 ak4C
0.80 1a41 0.20 ak4C
0.80 1a41 0.20 ak4C
0.60 1a43 0.20 ak40 0.20 ak4D
0.60 1a43 0.20 ak40 0.20 ak4D
0.80 1a43 0.20 ak4D
0.80 1a43 0.20 ak4D
k2 98 E/R
3.2E-14 0.0E+00
4.5E-15 0.0E+00
2.8E-16 0.0E+00
1.1E-13 0.0E+00
2.1E-16 0.0E+00
3.0E-17 0.0E+00
1.9E-18 0.0E+00
7.4E-16 0.0E+00
2.3E-15 0.0E+00
3.2E-16 0.0E+00
2.0E-17 0.0E+00
7.9E-15 0.0E+00
1.9E-16 0.0E+00
2.7E-17 0.0E+00
1.7E-18 0.0E+00
6.5E-16 0.0E+00
2.8E-14 0.0E+00
3.9E-15 0.0E+00
2.5E-16 0.0E+00
9.6E-14 0.0E+00
2.0E-15 0.0E+00
2.9E-16 0.0E+00
1.8E-17 0.0E+00
7.0E-15 0.0E+00
2.0E-15 0.0E+00
2.9E-16 0.0E+00
1.8E-17 0.0E+00
7.0E-15 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
2.3E-14 0.0E+00
3.2E-15 0.0E+00
2.0E-16 0.0E+00
7.9E-14 0.0E+00
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
Source
269
Table C.11 (continued) Peroxy radical cross reactions
2g21 XPOO
2g21 XSOO
2g21 XTOO
2g21 XAOO
2g40 XPOO
2g40 XSOO
2g40 XTOO
2g40 XAOO
2u51 XPOO
2u51 XSOO
2u51 XTOO
2u51 XAOO
2u52 XPOO
2u52 XSOO
2u52 XTOO
2u52 XAOO
2u71 XPOO
2u71 XSOO
2u71 XTOO
2u71 XAOO
2e72 XPOO
2e72 XSOO
2e72 XTOO
2e72 XAOO
2d21 XPOO
2d21 XSOO
2d21 XTOO
2d21 XAOO
2d31 XPOO
2d31 XSOO
2d31 XTOO
2d31 XAOO
2d32 XPOO
2d32 XSOO
2d32 XTOO
2d32 XAOO
2d33 XPOO
2d33 XSOO
2d33 XTOO
2d33 XAOO
2d34 XPOO
2d34 XSOO
2d34 XTOO
2d34 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1g21 0.20 go23 0.20 gd21
0.60 1g21 0.20 go23 0.20 gd21
0.80 1g21 0.20 gd21
0.80 1g21 0.20 gd21
0.80 1g40 0.20 go40
0.80 1g40 0.20 go40
1g40
1g40
0.80 1u52 0.20 uo52
0.80 1u52 0.20 uo52
1u52
1u52
0.60 1u51 0.20 uo52 0.20 uk51
0.60 1u51 0.20 uo52 0.20 uk51
0.80 1u51 0.20 uk51
0.80 1u51 0.20 uk51
0.60 1u71 0.20 uk71 0.20 ud71
0.60 1u71 0.20 uk71 0.20 ud71
0.80 1u71 0.20 ud71
0.80 1u71 0.20 ud71
0.80 1e71 0.20 ek71
0.80 1e71 0.20 ek71
1e71
1e71
0.60 1d21 0.20 do23 0.20 dd21
0.60 1d21 0.20 do23 0.20 dd21
0.80 1d21 0.20 dd21
0.80 1d21 0.20 dd21
0.60 1d32 0.20 do31 0.20 dk35
0.60 1d32 0.20 do31 0.20 dk35
0.80 1d32 0.20 dk35
0.80 1d32 0.20 dk35
0.60 1d31 0.20 do34 0.20 dk33
0.60 1d31 0.20 do34 0.20 dk33
0.80 1d31 0.20 dk33
0.80 1d31 0.20 dk33
0.60 1d34 0.20 dk35 0.20 dd32
0.60 1d34 0.20 dk35 0.20 dd32
0.80 1d34 0.20 dd32
0.80 1d34 0.20 dd32
0.60 1d35 0.20 do35 0.20 dd33
0.60 1d35 0.20 do35 0.20 dd33
0.80 1d35 0.20 dd33
0.80 1d35 0.20 dd33
k2 98 E/R
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
1.6e-15 0.0e+00
2.3e-16 0.0e+00
1.5e-17 0.0e+00
5.6e-15 0.0e+00
1.4E-15 0.0E+00
2.0E-16 0.0E+00
1.3E-17 0.0E+00
4.9E-15 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
2.5E-14 0.0E+00
3.5E-15 0.0E+00
2.2E-16 0.0E+00
8.6E-14 0.0E+00
1.1E-15 0.0E+00
1.6E-16 0.0E+00
1.0E-17 0.0E+00
3.9E-15 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
2.3E-14 0.0E+00
3.2E-15 0.0E+00
2.0E-16 0.0E+00
7.9E-14 0.0E+00
2.3E-14 0.0E+00
3.2E-15 0.0E+00
2.0E-16 0.0E+00
7.9E-14 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
4.1E-14 0.0E+00
5.9E-15 0.0E+00
3.7E-16 0.0E+00
1.4E-13 0.0E+00
Source
270
Table C.11 (continued) Peroxy radical cross reactions
2d41 XPOO
2d41 XSOO
2d41 XTOO
2d41 XAOO
2d42 XPOO
2d42 XSOO
2d42 XTOO
2d42 XAOO
2d43 XPOO
2d43 XSOO
2d43 XTOO
2d43 XAOO
2d44 XPOO
2d44 XSOO
2d44 XTOO
2d44 XAOO
2d45 XPOO
2d45 XSOO
2d45 XTOO
2d45 XAOO
2d47 XPOO
2d47 XSOO
2d47 XTOO
2d47 XAOO
2d48 XPOO
2d48 XSOO
2d48 XTOO
2d48 XAOO
2d49 XPOO
2d49 XSOO
2d49 XTOO
2d49 XAOO
2d50 XPOO
2d50 XSOO
2d50 XTOO
2d50 XAOO
2d51 XPOO
2d51 XSOO
2d51 XTOO
2d51 XAOO
2d52 XPOO
2d52 XSOO
2d52 XTOO
2d52 XAOO
2d53 XPOO
2d53 XSOO
2d53 XTOO
2d53 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1d41 0.20 dv45 0.20 dv42
0.60 1d41 0.20 dv45 0.20 dv42
0.80 1d41 0.20 dv42
0.80 1d41 0.20 dv42
0.60 1d42 0.20 dv45 0.20 dv44
0.60 1d42 0.20 dv45 0.20 dv44
0.80 1d42 0.20 dv44
0.80 1d42 0.20 dv44
0.60 1d44 0.20 dd42 0.20 dd43
0.60 1d44 0.20 dd42 0.20 dd43
0.80 1d44 0.20 dd43
0.80 1d44 0.20 dd43
0.80 1d43 0.20 do49
0.80 1d43 0.20 do49
1d43
1d43
0.60 1d45 0.20 dk47 0.20 dd43
0.60 1d45 0.20 dk47 0.20 dd43
0.80 1d45 0.20 dd43
0.80 1d45 0.20 dd43
0.60 1d47 0.20 do44 0.20 dk4C
0.60 1d47 0.20 do44 0.20 dk4C
0.80 1d47 0.20 dk4C
0.80 1d47 0.20 dk4C
0.60 1d48 0.20 do45 0.20 dk4A
0.60 1d48 0.20 do45 0.20 dk4A
0.80 1d48 0.20 dk4A
0.80 1d48 0.20 dk4A
0.60 1d49 0.20 do43 0.20 dd45
0.60 1d49 0.20 do43 0.20 dd45
0.80 1d49 0.20 dd45
0.80 1d49 0.20 dd45
0.60 1d5A 0.20 do57 0.20 dk5G
0.60 1d5A 0.20 do57 0.20 dk5G
0.80 1d5A 0.20 dk5G
0.80 1d5A 0.20 dk5G
0.80 1d51 0.20 dv56
0.80 1d51 0.20 dv56
1d51
1d51
0.60 1d52 0.20 dk59 0.20 dk53
0.60 1d52 0.20 dk59 0.20 dk53
0.80 1d52 0.20 dk53
0.80 1d52 0.20 dk53
0.60 1d53 0.20 dv56 0.20 dv55
0.60 1d53 0.20 dv56 0.20 dv55
0.80 1d53 0.20 dv55
0.80 1d53 0.20 dv55
k2 98 E/R
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
1.6E-15 0.0E+00
2.3E-16 0.0E+00
1.5E-17 0.0E+00
5.6E-15 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
3.0E-15 0.0E+00
4.2E-16 0.0E+00
2.7E-17 0.0E+00
1.0E-14 0.0E+00
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
2.6E-15 0.0E+00
3.7E-16 0.0E+00
2.3E-17 0.0E+00
9.0E-15 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
Source
271
Table C.11 (continued) Peroxy radical cross reactions
2d54 XPOO
2d54 XSOO
2d54 XTOO
2d54 XAOO
2d55 XPOO
2d55 XSOO
2d55 XTOO
2d55 XAOO
2d56 XPOO
2d56 XSOO
2d56 XTOO
2d56 XAOO
2d57 XPOO
2d57 XSOO
2d57 XTOO
2d57 XAOO
2d58 XPOO
2d58 XSOO
2d58 XTOO
2d58 XAOO
2d59 XPOO
2d59 XSOO
2d59 XTOO
2d59 XAOO
2d5A XPOO
2d5A XSOO
2d5A XTOO
2d5A XAOO
2d61 XPOO
2d61 XSOO
2d61 XTOO
2d61 XAOO
2d62 XPOO
2d62 XSOO
2d62 XTOO
2d62 XAOO
2d82 XPOO
2d82 XSOO
2d82 XTOO
2d82 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1d54 0.20 dk58 0.20 dd54
0.60 1d54 0.20 dk58 0.20 dd54
0.80 1d54 0.20 dd54
0.80 1d54 0.20 dd54
0.60 1d56 0.20 dk59 0.20 dk5B
0.60 1d56 0.20 dk59 0.20 dk5B
0.80 1d56 0.20 dk5B
0.80 1d56 0.20 dk5B
0.80 1d55 0.20 dd56
0.80 1d55 0.20 dd56
1d55
1d55
0.60 1d57 0.20 dk5D 0.20 dk5A
0.60 1d57 0.20 dk5D 0.20 dk5A
0.80 1d57 0.20 dk5A
0.80 1d57 0.20 dk5A
0.60 1d58 0.20 do53 0.20 dk5C
0.60 1d58 0.20 do53 0.20 dk5C
0.80 1d58 0.20 dk5C
0.80 1d58 0.20 dk5C
0.80 1d59 0.20 do59
0.80 1d59 0.20 do59
1d59
1d59
0.80 1d5B 0.20 dd57
0.80 1d5B 0.20 dd57
1d5B
1d5B
0.80 1d61 0.20 do65
0.80 1d61 0.20 do65
1d61
1d61
0.80 1d62 0.20 do66
0.80 1d62 0.20 do66
1d62
1d62
0.80 1d81 0.20 dk82
0.80 1d81 0.20 dk82
1d81
1d81
k2 98 E/R
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.4E-15 0.0E+00
2.0E-16 0.0E+00
1.3E-17 0.0E+00
4.9E-15 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
2.6E-15 0.0E+00
3.7E-16 0.0E+00
2.3E-17 0.0E+00
9.0E-15 0.0E+00
2.1E-16 0.0E+00
3.0E-17 0.0E+00
1.9E-18 0.0E+00
7.4E-16 0.0E+00
1.4E-15 0.0E+00
2.0E-16 0.0E+00
1.3E-17 0.0E+00
4.9E-15 0.0E+00
1.9E-16 0.0E+00
2.7E-17 0.0E+00
1.7E-18 0.0E+00
6.5E-16 0.0E+00
1.3E-15 0.0E+00
1.8E-16 0.0E+00
1.1E-17 0.0E+00
4.3E-15 0.0E+00
1.7E-16 0.0E+00
2.4E-17 0.0E+00
1.5E-18 0.0E+00
5.8E-16 0.0E+00
Source
272
Table C.11 (continued) Peroxy radical cross reactions
2h51 XPOO
2h51 XSOO
2h51 XTOO
2h51 XAOO
2h52 XPOO
2h52 XSOO
2h52 XTOO
2h52 XAOO
2h53 XPOO
2h53 XSOO
2h53 XTOO
2h53 XAOO
2h54 XPOO
2h54 XSOO
2h54 XTOO
2h54 XAOO
2h71 XPOO
2h71 XSOO
2h71 XTOO
2h71 XAOO
2v31 XPOO
2v31 XSOO
2v31 XTOO
2v31 XAOO
2a32 XPOO
2a32 XSOO
2a32 XTOO
2a32 XAOO
2k33 XPOO
2k33 XSOO
2k33 XTOO
2k33 XAOO
2k34 XPOO
2k34 XSOO
2k34 XTOO
2k34 XAOO
2k40 XPOO
2k40 XSOO
2k40 XTOO
2k40 XAOO
2k42 XPOO
2k42 XSOO
2k42 XTOO
2k42 XAOO
2k43 XPOO
2k43 XSOO
2k43 XTOO
2k43 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1k54 0.20 ho5A 0.20 hk51
0.60 1k54 0.20 ho5A 0.20 hk51
0.80 1k54 0.20 hk51
0.80 1k54 0.20 hk51
0.80 1h53 0.20 ho5B
0.80 1h53 0.20 ho5B
1h53
1h53
0.60 1h51 0.20 hn58 0.20 hn57
0.60 1h51 0.20 hn58 0.20 hn57
0.80 1h51 0.20 hn57
0.80 1h51 0.20 hn57
0.80 1h52 0.20 hn59
0.80 1h52 0.20 hn59
1h52
1h52
0.80 1h71 0.20 hk71
0.80 1h71 0.20 hk71
1h71
1h71
0.60 1v34 0.20 vk31 0.20 dv31
0.60 1v34 0.20 vk31 0.20 dv31
0.80 1v34 0.20 dv31
0.80 1v34 0.20 dv31
0.60 1a32 0.20 ak31 0.20 ad34
0.60 1a32 0.20 ak31 0.20 ad34
0.80 1a32 0.20 ad34
0.80 1a32 0.20 ad34
0.60 1k33 0.20 ko37 0.20 dk33
0.60 1k33 0.20 ko37 0.20 dk33
0.80 1k33 0.20 dk33
0.80 1k33 0.20 dk33
0.60 1k31 0.20 ko31 0.20 dk35
0.60 1k31 0.20 ko31 0.20 dk35
0.80 1k31 0.20 dk35
0.80 1k31 0.20 dk35
0.60 1k40 0.20 ko46 0.20 dk48
0.60 1k40 0.20 ko46 0.20 dk48
0.80 1k40 0.20 dk48
0.80 1k40 0.20 dk48
0.60 1k44 0.20 ko46 0.20 kk42
0.60 1k44 0.20 ko46 0.20 kk42
0.80 1k44 0.20 kk42
0.80 1k44 0.20 kk42
0.60 1k41 0.20 kk42 0.20 dk40
0.60 1k41 0.20 kk42 0.20 dk40
0.80 1k41 0.20 dk40
0.80 1k41 0.20 dk40
k2 98 E/R
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.4E-15 0.0E+00
2.0E-16 0.0E+00
1.3E-17 0.0E+00
4.9E-15 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.4E-15 0.0E+00
2.0E-16 0.0E+00
1.3E-17 0.0E+00
4.9E-15 0.0E+00
1.1E-15 0.0E+00
1.6E-16 0.0E+00
1.0E-17 0.0E+00
3.9E-15 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.9E-12 0.0E+00
4.1E-13 0.0E+00
2.6E-14 0.0E+00
1.0E-11 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
Source
273
Table C.11 (continued) Peroxy radical cross reactions
2k44 XPOO
2k44 XSOO
2k44 XTOO
2k44 XAOO
2k45 XPOO
2k45 XSOO
2k45 XTOO
2k45 XAOO
2k46 XPOO
2k46 XSOO
2k46 XTOO
2k46 XAOO
2k47 XPOO
2k47 XSOO
2k47 XTOO
2k47 XAOO
2k48 XPOO
2k48 XSOO
2k48 XTOO
2k48 XAOO
2k49 XPOO
2k49 XSOO
2k49 XTOO
2k49 XAOO
2k4B XPOO
2k4B XSOO
2k4B XTOO
2k4B XAOO
2k4C XPOO
2k4C XSOO
2k4C XTOO
2k4C XAOO
2k51 XPOO
2k51 XSOO
2k51 XTOO
2k51 XAOO
2k52 XPOO
2k52 XSOO
2k52 XTOO
2k52 XAOO
2k53 XPOO
2k53 XSOO
2k53 XTOO
2k53 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1k45 0.20 ko42 0.20 kk43
0.60 1k45 0.20 ko42 0.20 kk43
0.80 1k45 0.20 kk43
0.80 1k45 0.20 kk43
0.60 1k42 0.20 ko41 0.20 dk49
0.60 1k42 0.20 ko41 0.20 dk49
0.80 1k42 0.20 dk49
0.80 1k42 0.20 dk49
0.60 1k4D 0.20 ko47 0.20 dk4E
0.60 1k4D 0.20 ko47 0.20 dk4E
0.80 1k4D 0.20 dk4E
0.80 1k4D 0.20 dk4E
0.60 1k47 0.20 ko45 0.20 dk4C
0.60 1k47 0.20 ko45 0.20 dk4C
0.80 1k47 0.20 dk4C
0.80 1k47 0.20 dk4C
0.60 1k46 0.20 ko43 0.20 dk4A
0.60 1k46 0.20 ko43 0.20 dk4A
0.80 1k46 0.20 dk4A
0.80 1k46 0.20 dk4A
0.60 1k48 0.20 ko43 0.20 dk4B
0.60 1k48 0.20 ko43 0.20 dk4B
0.80 1k48 0.20 dk4B
0.80 1k48 0.20 dk4B
0.60 1k4B 0.20 ko48 0.20 dk4D
0.60 1k4B 0.20 ko48 0.20 dk4D
0.80 1k4B 0.20 dk4D
0.80 1k4B 0.20 dk4D
0.60 1k4C 0.20 ko47 0.20 dk47
0.60 1k4C 0.20 ko47 0.20 dk47
0.80 1k4C 0.20 dk47
0.80 1k4C 0.20 dk47
0.80 1k51 0.20 ko54
0.80 1k51 0.20 ko54
1k51
1k51
0.60 1k52 0.20 ko57 0.20 kk52
0.60 1k52 0.20 ko57 0.20 kk52
0.80 1k52 0.20 kk52
0.80 1k52 0.20 kk52
0.60 1k53 0.20 kk53 0.20 ko58
0.60 1k53 0.20 kk53 0.20 ko58
0.80 1k53 0.20 kk53
0.80 1k53 0.20 kk53
a Reaction added by Williams [1994a]
k2 98 E/R
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-12 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
1.4E-15 0.0E+00
2.0E-16 0.0E+00
1.3E-17 0.0E+00
4.9E-15 0.0E+00
2.6E-15 0.0E+00
3.7E-16 0.0E+00
2.3E-17 0.0E+00
9.0E-15 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
Source
a
a
a
a
a
a
a
a
274
Table C.11 (continued) Peroxy radical cross reactions
2l11 XPOO
2l11 XSOO
2l11 XTOO
2l11 XAOO
2l21 XPOO
2l21 XSOO
2l21 XTOO
2l21 XAOO
2l22 XPOO
2l22 XSOO
2l22 XTOO
2l22 XAOO
2l31 XPOO
2l31 XSOO
2l31 XTOO
2l31 XAOO
2l41 XPOO
2l41 XSOO
2l41 XTOO
2l41 XAOO
2l42 XPOO
2l42 XSOO
2l42 XTOO
2l42 XAOO
2l43 XPOO
2l43 XSOO
2l43 XTOO
2l43 XAOO
2m01 XPOO
2m01 XSOO
2m01 XTOO
2m01 XAOO
2m11 XPOO
2m11 XSOO
2m11 XTOO
2m11 XAOO
2m12 XPOO
2m12 XSOO
2m12 XTOO
2m12 XAOO
2m21 XPOO
2m21 XSOO
2m21 XTOO
2m21 XAOO
2m22 XPOO
2m22 XSOO
2m22 XTOO
2m22 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1l11 0.20 lo11 0.20 ld11
0.60 1l11 0.20 lo11 0.20 ld11
0.80 1l11 0.20 ld11
0.80 1l11 0.20 ld11
0.60 1l21 0.20 lo21 0.20 ld21
0.60 1l21 0.20 lo21 0.20 ld21
0.80 1l21 0.20 ld21
0.80 1l21 0.20 ld21
0.60 1l22 0.20 lo22 0.20 lk21
0.60 1l22 0.20 lo22 0.20 lk21
0.80 1l22 0.20 lk21
0.80 1l22 0.20 lk21
0.60 1l31 0.20 lo31 0.20 lk31
0.60 1l31 0.20 lo31 0.20 lk31
0.80 1l31 0.20 lk31
0.80 1l31 0.20 lk31
0.60 1l41 0.20 lo41 0.20 lk41
0.60 1l41 0.20 lo41 0.20 lk41
0.80 1l41 0.20 lk41
0.80 1l41 0.20 lk41
0.80 1l42 0.20 lo42
0.80 1l42 0.20 lo42
1l42
1l42
0.60 1l43 0.20 lo43 0.20 ld41
0.60 1l43 0.20 lo43 0.20 ld41
0.80 1l43 0.20 ld41
0.80 1l43 0.20 ld41
0.60 NH2O 0.20 mo01 0.20 HNO
0.60 NH2O 0.20 mo01 0.20 HNO
0.80 NH2O 0.20 HNO
0.80 NH2O 0.20 HNO
0.60 1m13 0.20 mo11 0.20 md11
0.60 1m13 0.20 mo11 0.20 md11
0.80 1m13 0.20 md11
0.80 1m13 0.20 md11
0.60 1m11 0.20 mo12 0.20 wo11
0.60 1m11 0.20 mo12 0.20 wo11
0.80 1m11 0.20 wo11
0.80 1m11 0.20 wo11
0.60 1m23 0.20 mo21 0.20 mk21
0.60 1m23 0.20 mo21 0.20 mk21
0.80 1m23 0.20 mk21
0.80 1m23 0.20 mk21
0.60 1m24 0.20 mo22 0.20 md21
0.60 1m24 0.20 mo22 0.20 md21
0.80 1m24 0.20 md21
0.80 1m24 0.20 md21
k2 98 E/R
6.2E-13 0.0E+00
8.7E-14 0.0E+00
5.5E-15 0.0E+00
2.1E-12 0.0E+00
4.7E-14 0.0E+00
6.6E-15 0.0E+00
4.2E-16 0.0E+00
1.6E-13 0.0E+00
4.7E-14 0.0E+00
6.6E-15 0.0E+00
4.2E-16 0.0E+00
1.6E-13 0.0E+00
3.4E-15 0.0E+00
4.8E-16 0.0E+00
3.0E-17 0.0E+00
1.2E-14 0.0E+00
3.0E-15 0.0E+00
4.2E-16 0.0E+00
2.7E-17 0.0E+00
1.0E-14 0.0E+00
2.4E-16 0.0E+00
3.5E-17 0.0E+00
2.2E-18 0.0E+00
8.4E-16 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
6.3E-13 0.0E+00
9.0E-14 0.0E+00
5.7E-15 0.0E+00
2.2E-12 0.0E+00
6.2E-13 0.0E+00
8.7E-14 0.0E+00
5.5E-15 0.0E+00
2.1E-12 0.0E+00
2.4E-14 0.0E+00
1.6E-15 0.0E+00
3.0E-16 0.0E+00
9.8E-14 0.0E+00
4.7E-14 0.0E+00
6.6E-15 0.0E+00
4.2E-16 0.0E+00
1.6E-13 0.0E+00
4.7E-14 0.0E+00
6.6E-15 0.0E+00
4.2E-16 0.0E+00
1.6E-13 0.0E+00
Source
275
Table C.11 (continued) Peroxy radical cross reactions
2m23 XPOO
2m23 XSOO
2m23 XTOO
2m23 XAOO
2m33 XPOO
2m33 XSOO
2m33 XTOO
2m33 XAOO
2n11 XPOO
2n11 XSOO
2n11 XTOO
2n11 XAOO
2n21 XPOO
2n21 XSOO
2n21 XTOO
2n21 XAOO
2n22 XPOO
2n22 XSOO
2n22 XTOO
2n22 XAOO
2n23 XPOO
2n23 XSOO
2n23 XTOO
2n23 XAOO
2n31 XPOO
2n31 XSOO
2n31 XTOO
2n31 XAOO
2n32 XPOO
2n32 XSOO
2n32 XTOO
2n32 XAOO
2n33 XPOO
2n33 XSOO
2n33 XTOO
2n33 XAOO
2n34 XPOO
2n34 XSOO
2n34 XTOO
2n34 XAOO
2n35 XPOO
2n35 XSOO
2n35 XTOO
2n35 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.80 1m25 0.20 mo23
0.80 1m25 0.20 mo23
1m25
1m25
0.60 1m33 0.20 mo31 0.20 md31
0.60 1m33 0.20 mo31 0.20 md31
0.80 1m33 0.20 md31
0.80 1m33 0.20 md31
0.60 1n11 0.20 no11 0.20 nd11
0.60 1n11 0.20 no11 0.20 nd11
0.80 1n11 0.20 nd11
0.80 1n11 0.20 nd11
0.60 1n21 0.20 nd22 0.20 nd23
0.60 1n21 0.20 nd22 0.20 nd23
0.80 1n21 0.20 nd23
0.80 1n21 0.20 nd23
0.60 1n22 0.20 no21 0.20 nd21
0.60 1n22 0.20 no21 0.20 nd21
0.80 1n22 0.20 nd21
0.80 1n22 0.20 nd21
0.60 1n23 0.20 no23 0.20 nk23
0.60 1n23 0.20 no23 0.20 nk23
0.80 1n23 0.20 nk23
0.80 1n23 0.20 nk23
0.60 1n31 0.20 nv39 0.20 nv35
0.60 1n31 0.20 nv39 0.20 nv35
0.80 1n31 0.20 nv35
0.80 1n31 0.20 nv35
0.60 1n32 0.20 no33 0.20 nk38
0.60 1n32 0.20 no33 0.20 nk38
0.80 1n32 0.20 nk38
0.80 1n32 0.20 nk38
0.60 1n33 0.20 no34 0.20 nd35
0.60 1n33 0.20 no34 0.20 nd35
0.80 1n33 0.20 nd35
0.80 1n33 0.20 nd35
0.60 1n34 0.20 no32 0.20 nd34
0.60 1n34 0.20 no32 0.20 nd34
0.80 1n34 0.20 nd34
0.80 1n34 0.20 nd34
0.60 1n35 0.20 no35 0.20 nd38
0.60 1n35 0.20 no35 0.20 nd38
0.80 1n35 0.20 nd38
0.80 1n35 0.20 nd38
a Reaction added by Williams [1994a]
k2 98 E/R
5.0E-15 0.0E+00
3.0E-16 0.0E+00
6.0E-17 0.0E+00
1.9E-14 0.0E+00
4.1E-14 0.0E+00
5.9E-15 0.0E+00
3.7E-16 0.0E+00
1.4E-13 0.0E+00
2.5E-12 0.0E+00
3.5E-13 0.0E+00
2.2E-14 0.0E+00
8.6E-12 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.3E-14 0.0E+00
3.2E-15 0.0E+00
2.0E-16 0.0E+00
7.9E-14 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
4.1E-14 0.0E+00
5.9E-15 0.0E+00
3.7E-16 0.0E+00
1.4E-13 0.0E+00
Source
a
a
a
a
276
Table C.11 (continued) Peroxy radical cross reactions
2n41 XPOO
2n41 XSOO
2n41 XTOO
2n41 XAOO
2n42 XPOO
2n42 XSOO
2n42 XTOO
2n42 XAOO
2n43 XPOO
2n43 XSOO
2n43 XTOO
2n43 XAOO
2n44 XPOO
2n44 XSOO
2n44 XTOO
2n44 XAOO
2n45 XPOO
2n45 XSOO
2n45 XTOO
2n45 XAOO
2n46 XPOO
2n46 XSOO
2n46 XTOO
2n46 XAOO
2n47 XPOO
2n47 XSOO
2n47 XTOO
2n47 XAOO
2n48 XPOO
2n48 XSOO
2n48 XTOO
2n48 XAOO
2n49 XPOO
2n49 XSOO
2n49 XTOO
2n49 XAOO
2n4a XPOO
2n4a XSOO
2n4a XTOO
2n4a XAOO
2n4b XPOO
2n4b XSOO
2n4b XTOO
2n4b XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1n41 0.20 nv4E 0.20 nv4D
0.60 1n41 0.20 nv4E 0.20 nv4D
0.80 1n41 0.20 nv4D
0.80 1n41 0.20 nv4D
0.60 1n42 0.20 nk4G 0.20 nk4F
0.60 1n42 0.20 nk4G 0.20 nk4F
0.80 1n42 0.20 nk4F
0.80 1n42 0.20 nk4F
0.60 1n43 0.20 nv4H 0.20 nd4A
0.60 1n43 0.20 nv4H 0.20 nd4A
0.80 1n43 0.20 nd4A
0.80 1n43 0.20 nd4A
0.60 1n44 0.20 nk4I 0.20 nd4B
0.60 1n44 0.20 nk4I 0.20 nd4B
0.80 1n44 0.20 nd4B
0.80 1n44 0.20 nd4B
0.60 1n47 0.20 no43 0.20 nk45
0.60 1n47 0.20 no43 0.20 nk45
0.80 1n47 0.20 nk45
0.80 1n47 0.20 nk45
0.80 1n46 0.20 no45
0.80 1n46 0.20 no45
1n46
1n46
0.80 1n45 0.20 nd4C
0.80 1n45 0.20 nd4C
1n45
1n45
0.60 1n48 0.20 nk4A 0.20 nk47
0.60 1n48 0.20 nk4A 0.20 nk47
0.80 1n48 0.20 nk47
0.80 1n48 0.20 nk47
0.60 1n49 0.20 nk4C 0.20 nd4E
0.60 1n49 0.20 nk4C 0.20 nd4E
0.80 1n49 0.20 nd4E
0.80 1n49 0.20 nd4E
0.60 1n4a 0.20 nk49 0.20 no46
0.60 1n4a 0.20 nk49 0.20 no46
0.80 1n4a 0.20 nk49
0.8 1n4a 0.20 nk49
0.60 1n4b 0.20 nd48 0.20 no4C
0.60 1n4b 0.20 nd48 0.20 no4C
0.80 1n4b 0.20 nd48
0.80 1n4b 0.20 nd48
a Reaction added by Williams [1994a]
k2 98 E/R
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
1.6E-15 0.0E+00
2.3E-16 0.0E+00
1.5E-17 0.0E+00
5.6E-15 0.0E+00
1.6E-15 0.0E+00
2.3E-16 0.0E+00
1.5E-17 0.0E+00
5.6E-15 0.0E+00
2.0E-13 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
3.0E-15 0.0E+00
4.2E-16 0.0E+00
2.7E-17 0.0E+00
1.0E-14 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
Source
a
a
a
a
a
a
a
a
277
Table C.11 (continued) Peroxy radical cross reactions
2n51 XPOO
2n51 XSOO
2n51 XTOO
2n51 XAOO
2n52 XPOO
2n52 XSOO
2n52 XTOO
2n52 XAOO
2n53 XPOO
2n53 XSOO
2n53 XTOO
2n53 XAOO
2n54 XPOO
2n54 XSOO
2n54 XTOO
2n54 XAOO
2n55 XPOO
2n55 XSOO
2n55 XTOO
2n55 XAOO
2n56 XPOO
2n56 XSOO
2n56 XTOO
2n56 XAOO
2n57 XPOO
2n57 XSOO
2n57 XTOO
2n57 XAOO
2n58 XPOO
2n58 XSOO
2n58 XTOO
2n58 XAOO
2n59 XPOO
2n59 XSOO
2n59 XTOO
2n59 XAOO
2n5a XPOO
2n5a XSOO
2n5a XTOO
2n5a XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.80 1n51 0.20 nu54
0.80 1n51 0.20 nu54
1n51
1n51
0.60 1n52 0.20 nu55 0.20 nu53
0.60 1n52 0.20 nu55 0.20 nu53
0.80 1n52 0.20 nu53
0.80 1n52 0.20 nu53
0.60 1n53 0.20 no5B 0.30 nk51
0.60 1n53 0.20 no5B 0.30 nk51
0.80 1n53 0.20 nk51
0.80 1n53 0.20 nk51
0.80 1n54 0.20 no5C
0.80 1n54 0.20 no5C
1n54
1n54
0.60 1n55 0.20 nk52 0.20 no57
0.60 1n55 0.20 nk52 0.20 no57
0.80 1n55 0.20 nk52
0.80 1n55 0.20 nk52
0.60 1n56 0.20 nk53 0.20 no58
0.60 1n56 0.20 nk53 0.20 no58
0.80 1n56 0.20 nk53
0.80 1n56 0.20 nk53
0.60 1n57 0.20 nk54 0.20 no5E
0.60 1n57 0.20 nk54 0.20 no5E
0.80 1n57 0.20 nk54
0.80 1n57 0.20 nk54
0.60 1n58 0.20 nk55 0.20 no5F
0.60 1n58 0.20 nk55 0.20 no5F
0.80 1n58 0.20 nk55
0.80 1n58 0.20 nk55
0.60 1n59 0.20 nk56 0.20 no5G
0.60 1n59 0.20 nk56 0.20 no5G
0.80 1n59 0.20 nk56
0.80 1n59 0.20 nk56
0.60 1n5a 0.20 nd58 0.20 no5H
0.60 1n5a 0.20 nd58 0.20 no5H
0.80 1n5a 0.20 nd58
0.80 1n5a 0.20 no5H
a Reaction added by Williams [1994a]
k2 98 E/R
2.1E-16 0.0E+00
3.0E-17 0.0E+00
1.9E-18 0.0E+00
7.4E-16 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.7e-14 0.0e+00
2.4e-15 0.0e+00
1.6e-16 0.0e+00
6.0e-14 0.0e+00
1.4e-15 0.0e+00
2.0E-16 0.0e+00
1.3e-17 0.0e+00
4.9e-15 0.0e+00
2.6e-15 0.0e+00
3.7E-16 0.0E+00
2.3e-17 0.0e+00
9.0e-15 0.0e+00
2.6e-15 0.0e+00
3.7E-16 0.0E+00
2.3e-17 0.0e+00
9.0e-15 0.0e+00
2.6e-15 0.0e+00
3.7E-16 0.0E+00
2.3e-17 0.0e+00
9.0e-15 0.0e+00
1.7e-14 0.0e+00
2.5e-15 0.0e+00
1.6e-16 0.0e+00
6.0e-14 0.0e+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6e-16 0.0e+00
6.0e-14 0.0e+00
3.2E-14 0.0E+00
4.5E-15 0.0E+00
2.8E-16 0.0e+00
1.1E-13 0.0e+00
Source
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
a
278
Table C.11 (continued) Peroxy radical cross reactions
2nA1 XPOO
2nA1 XSOO
2nA1 XTOO
2nA1 XAOO
2o11 XPOO
2o11 XSOO
2o11 XTOO
2o11 XAOO
2o21 XPOO
2o21 XSOO
2o21 XTOO
2o21 XAOO
2o31 XPOO
2o31 XSOO
2o31 XTOO
2o31 XAOO
2o32 XPOO
2o32 XSOO
2o32 XTOO
2o32 XAOO
2o33 XPOO
2o33 XSOO
2o33 XTOO
2o33 XAOO
2o34 XPOO
2o34 XSOO
2o34 XTOO
2o34 XAOO
2o35 XPOO
2o35 XSOO
2o35 XTOO
2o35 XAOO
2o40 XPOO
2o40 XSOO
2o40 XTOO
2o40 XAOO
2a43 XPOO
2a43 XSOO
2a43 XTOO
2a43 XAOO
2o42 XPOO
2o42 XSOO
2o42 XTOO
2o42 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.80 1nA1 0.20 ntA2
0.80 1nA1 0.20 ntA2
1nA1
1nA1
0.60 1o11 0.20 oo11 0.20 a011
0.60 1o11 0.20 oo11 0.20 a011
0.80 1o11 0.20 a011
0.80 1o11 0.20 a011
0.60 1o22 0.20 oo21 0.20 do23
0.60 1o22 0.20 oo21 0.20 do23
0.80 1o22 0.20 do23
0.80 1o22 0.20 do23
0.60 1o32 0.20 oo32 0.20 ko31
0.60 1o32 0.20 oo32 0.20 ko31
0.80 1o32 0.20 ko31
0.80 1o32 0.20 ko31
0.60 1o33 0.20 oo31 0.20 ko37
0.60 1o33 0.20 oo31 0.20 ko37
0.80 1o33 0.20 ko37
0.80 1o33 0.20 ko37
0.60 1o34 0.20 oo31 0.20 do34
0.60 1o34 0.20 oo31 0.20 do34
0.80 1o34 0.20 do34
0.80 1o34 0.20 do34
0.60 1o35 0.20 oo33 0.20 do35
0.60 1o35 0.20 oo33 0.20 do35
0.80 1o35 0.20 do35
0.80 1o35 0.20 do35
0.60 1o31 0.20 oo32 0.20 do31
0.60 1o31 0.20 oo32 0.20 do31
0.80 1o31 0.20 do31
0.80 1o31 0.20 do31
0.60 1o40 0.20 oo41 0.20 do46
0.60 1o40 0.20 oo41 0.20 do46
0.80 1o40 0.20 do46
0.80 1o40 0.20 do46
0.80 1a44 0.20 ao48
0.80 1a44 0.20 ao48
1a44
1a44
0.60 1o43 0.20 oo42 0.20 do41
0.60 1o43 0.20 oo42 0.20 do41
0.80 1o43 0.20 do41
0.80 1o43 0.20 do41
k2 98 E/R
1.1E-15 0.0E+00
1.6E-16 0.0E+00
1.0E-17 0.0E+00
3.9E-15 0.0E+00
2.5E-12 0.0E+00
3.5E-13 0.0E+00
2.2E-14 0.0E+00
8.6E-12 0.0E+00
1.5E-12 0.0E+00
2.1E-13 0.0E+00
1.4E-14 0.0E+00
5.2E-12 0.0E+00
2.3E-14 0.0E+00
3.2E-15 0.0E+00
2.0E-16 0.0E+00
7.9E-14 0.0E+00
2.3E-14 0.0E+00
3.2E-15 0.0E+00
2.0E-16 0.0E+00
7.9E-14 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
4.1E-14 0.0E+00
5.9E-15 0.0E+00
3.7E-16 0.0E+00
1.4E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
1.6E-15 0.0E+00
2.3E-16 0.0E+00
1.5E-17 0.0E+00
5.6E-15 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
Source
279
Table C.11 (continued) Peroxy radical cross reactions
2o43 XPOO
2o43 XSOO
2o43 XTOO
2o43 XAOO
2o44 XPOO
2o44 XSOO
2o44 XTOO
2o44 XAOO
2o45 XPOO
2o45 XSOO
2o45 XTOO
2o45 XAOO
2o46 XPOO
2o46 XSOO
2o46 XTOO
2o46 XAOO
2a47 XPOO
2a47 XSOO
2a47 XTOO
2a47 XAOO
2o48 XPOO
2o48 XSOO
2o48 XTOO
2o48 XAOO
2o49 XPOO
2o49 XSOO
2o49 XTOO
2o49 XAOO
2o4A XPOO
2o4A XSOO
2o4A XTOO
2o4A XAOO
2o4B XPOO
2o4B XSOO
2o4B XTOO
2o4B XAOO
2o4C XPOO
2o4C XSOO
2o4C XTOO
2o4C XAOO
2o4D XPOO
2o4D XSOO
2o4D XTOO
2o4D XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1o44 0.20 oo47 0.20 ko42
0.60 1o44 0.20 oo47 0.20 ko42
0.80 1o44 0.20 ko42
0.80 1o44 0.20 ko42
0.80 1o41 0.20 oo43
0.80 1o41 0.20 oo43
1o41
1o41
0.60 1o45 0.20 oo43 0.20 do42
0.60 1o45 0.20 oo43 0.20 do42
0.80 1o45 0.20 do42
0.80 1o45 0.20 do42
0.60 1o46 0.20 oo44 0.20 do44
0.60 1o46 0.20 oo44 0.20 do44
0.80 1o46 0.20 do44
0.80 1o46 0.20 do44
0.60 1a42 0.20 ao46 0.20 ad49
0.60 1a42 0.20 ao46 0.20 ad49
0.80 1a42 0.20 ad49
0.80 1a42 0.20 ad49
0.60 1o48 0.20 oo48 0.20 do49
0.60 1o48 0.20 oo48 0.20 do49
0.80 1o48 0.20 do49
0.80 1o48 0.20 do49
0.60 1o49 0.20 oo49 0.20 do40
0.60 1o49 0.20 oo49 0.20 do40
0.80 1o49 0.20 do40
0.80 1o49 0.20 do40
0.60 1o4A 0.20 oo45 0.20 do43
0.60 1o4A 0.20 oo45 0.20 do43
0.80 1o4A 0.20 do43
0.80 1o4A 0.20 do43
0.60 1o4B 0.20 oo46 0.20 do45
0.60 1o4B 0.20 oo46 0.20 do45
0.80 1o4B 0.20 do45
0.80 1o4B 0.20 do45
0.60 1o4C 0.20 oo44 0.20 ko45
0.60 1o4C 0.20 oo44 0.20 ko45
0.80 1o4C 0.20 ko45
0.80 1o4C 0.20 ko45
0.60 1o4D 0.20 oo47 0.20 do48
0.60 1o4D 0.20 oo47 0.20 do48
0.80 1o4D 0.20 do48
0.80 1o4D 0.20 do48
k2 98 E/R
9.4E-13 0.0E+00
1.3E-13 0.0E+00
8.4E-15 0.0E+00
3.3E-12 0.0E+00
1.6E-15 0.0E+00
2.3E-16 0.0E+00
1.5E-17 0.0E+00
5.6E-15 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
3.6E-14 0.0E+00
5.1E-15 0.0E+00
3.2E-16 0.0E+00
1.3E-13 0.0E+00
3.0E-15 0.0E+00
4.2E-16 0.0E+00
2.7E-17 0.0E+00
1.0E-14 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
Source
280
Table C.11 (continued) Peroxy radical cross reactions
2o50 XPOO
2o50 XSOO
2o50 XTOO
2o50 XAOO
2o51 XPOO
2o51 XSOO
2o51 XTOO
2o51 XAOO
2o52 XPOO
2o52 XSOO
2o52 XTOO
2o52 XAOO
2o53 XPOO
2o53 XSOO
2o53 XTOO
2o53 XAOO
2o54 XPOO
2o54 XSOO
2o54 XTOO
2o54 XAOO
2o55 XPOO
2o55 XSOO
2o55 XTOO
2o55 XAOO
2o56 XPOO
2o56 XSOO
2o56 XTOO
2o56 XAOO
2o57 XPOO
2o57 XSOO
2o57 XTOO
2o57 XAOO
2o58 XPOO
2o58 XSOO
2o58 XTOO
2o58 XAOO
2o59 XPOO
2o59 XSOO
2o59 XTOO
2o59 XAOO
2o5A XPOO
2o5A XSOO
2o5A XTOO
2o5A XAOO
2o5B XPOO
2o5B XSOO
2o5B XTOO
2o5B XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1o50 0.20 oo53 0.20 ko50
0.60 1o50 0.20 oo53 0.20 ko50
0.80 1o50 0.20 ko50
0.80 1o50 0.20 ko50
0.60 1o52 0.20 oo51 0.20 ko56
0.60 1o52 0.20 oo51 0.20 ko56
0.80 1o52 0.20 ko56
0.80 1o52 0.20 ko56
0.60 1o54 0.20 oo54 0.20 ko53
0.60 1o54 0.20 oo54 0.20 ko53
0.80 1o54 0.20 ko53
0.80 1o54 0.20 ko53
0.60 1o53 0.20 oo55 0.20 ko51
0.60 1o53 0.20 oo55 0.20 ko51
0.80 1o53 0.20 ko51
0.80 1o53 0.20 ko51
0.60 1o51 0.20 oo57 0.20 ko55
0.60 1o51 0.20 oo57 0.20 ko55
0.80 1o51 0.20 ko55
0.80 1o51 0.20 ko55
0.60 1o50 0.20 oo54 0.20 do57
0.60 1o50 0.20 oo54 0.20 do57
0.80 1o50 0.20 do57
0.80 1o50 0.20 do57
0.60 1o56 0.20 oo51 0.20 ko52
0.60 1o56 0.20 oo51 0.20 ko52
0.80 1o56 0.20 ko52
0.80 1o56 0.20 ko52
0.60 1o57 0.20 oo51 0.20 do52
0.60 1o57 0.20 oo51 0.20 do52
0.80 1o57 0.20 do52
0.80 1o57 0.20 do52
0.60 1o58 0.20 oo58 0.20 do53
0.60 1o58 0.20 oo58 0.20 do53
0.80 1o58 0.20 do53
0.80 1o58 0.20 do53
0.60 1o59 0.20 oo52 0.20 do54
0.60 1o59 0.20 oo52 0.20 do54
0.80 1o59 0.20 do54
0.80 1o59 0.20 do54
0.60 1o5C 0.20 oo59 0.20 ko54
0.60 1o5C 0.20 oo59 0.20 ko54
0.80 1o5C 0.20 ko54
0.80 1o5C 0.20 ko54
0.60 1o5B 0.20 oo59 0.20 do50
0.60 1o5B 0.20 oo59 0.20 do50
0.80 1o5B 0.20 do50
0.80 1o5B 0.20 do50
k2 98 E/R
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
3.2E-14 0.0E+00
4.5E-15 0.0E+00
2.8E-16 0.0E+00
1.1E-13 0.0E+00
2.6E-15 0.0E+00
3.7E-16 0.0E+00
2.3E-17 0.0E+00
9.0E-15 0.0E+00
3.2E-14 0.0E+00
4.5E-15 0.0E+00
2.8E-16 0.0E+00
1.1E-13 0.0E+00
3.2E-14 0.0E+00
4.5E-15 0.0E+00
2.8E-16 0.0E+00
1.1E-13 0.0E+00
3.2E-14 0.0E+00
4.5E-15 0.0E+00
2.8E-16 0.0E+00
1.1E-13 0.0E+00
1.7E-14 0.0E+00
2.5E-15 0.0E+00
1.6E-16 0.0E+00
6.0E-14 0.0E+00
2.1e-13 0.0e+00
3.0e-14 0.0e+00
1.9e-15 0.0e+00
7.3e-13 0.0e+00
Source
281
Table C.11 (continued) Peroxy radical cross reactions
2a51 XPOO
2a51 XSOO
2a51 XTOO
2a51 XAOO
2a50 XPOO
2a50 XSOO
2a50 XTOO
2a50 XAOO
2a53 XPOO
2a53 XSOO
2a53 XTOO
2a53 XAOO
2o61 XPOO
2o61 XSOO
2o61 XTOO
2o61 XAOO
2o62 XPOO
2o62 XSOO
2o62 XTOO
2o62 XAOO
2o63 XPOO
2o63 XSOO
2o63 XTOO
2o63 XAOO
2o64 XPOO
2o64 XSOO
2o64 XTOO
2o64 XAOO
2o65 XPOO
2o65 XSOO
2o65 XTOO
2o65 XAOO
2o71 XPOO
2o71 XSOO
2o71 XTOO
2o71 XAOO
2o81 XPOO
2o81 XSOO
2o81 XTOO
2o81 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1a50 0.20 ak57 0.20 ak55
0.60 1a50 0.20 ak57 0.20 ak55
0.80 1a50 0.20 ak55
0.80 1a50 0.20 ak55
0.60 1a51 0.20 ak57 0.20 ak55
0.60 1a51 0.20 ak57 0.20 ak55
0.80 1a51 0.20 ak55
0.80 1a51 0.20 ak55
0.60 1a52 0.20 ak58 0.20 ad53
0.60 1a52 0.20 ak58 0.20 ad53
0.80 1a52 0.20 ad53
0.80 1a52 0.20 ad53
0.60 1o61 0.20 oo61 0.20 dd61
0.60 1o61 0.20 oo61 0.20 dd61
0.80 1o61 0.20 dd61
0.80 1o61 0.20 dd61
0.60 1o63 0.20 oo62 0.20 do62
0.60 1o63 0.20 oo62 0.20 do62
0.80 1o63 0.20 do62
0.80 1o63 0.20 do62
0.60 1o64 0.20 oo63 0.20 do64
0.60 1o64 0.20 oo63 0.20 do64
0.80 1o64 0.20 do64
0.80 1o64 0.20 do64
0.60 1o62 0.20 oo64 0.20 do63
0.60 1o62 0.20 oo64 0.20 do63
0.80 1o62 0.20 do63
0.80 1o62 0.20 do63
0.60 1o65 0.20 oo65 0.20 do65
0.60 1o65 0.20 oo65 0.20 do65
0.80 1o65 0.20 do65
0.80 1o65 0.20 do65
0.60 1o71 0.20 oo71 0.20 ko71
0.60 1o71 0.20 oo71 0.20 ko71
0.80 1o71 0.20 ko71
0.80 1o71 0.20 ko71
0.60 1o81 0.20 oo81 0.20 dk81
0.60 1o81 0.20 oo81 0.20 dk81
0.80 1o81 0.20 dk81
0.80 1o81 0.20 dk81
k2 98 E/R
1.7e-14 0.0e+00
2.5e-15 0.0e+00
1.6e-16 0.0e+00
6.0e-14 0.0e+00
1.7e-14 0.0e+00
2.5e-15 0.0e+00
1.6e-16 0.0e+00
6.0e-14 0.0e+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
1.9E-13 0.0E+00
2.6E-14 0.0E+00
1.7E-15 0.0E+00
6.4E-13 0.0E+00
2.8E-14 0.0E+00
3.9E-15 0.0E+00
2.5E-16 0.0E+00
9.6E-14 0.0E+00
2.8E-14 0.0E+00
3.9E-15 0.0E+00
2.5E-16 0.0E+00
9.6E-14 0.0E+00
2.8E-14 0.0E+00
3.9E-15 0.0E+00
2.5E-16 0.0E+00
9.6E-14 0.0E+00
2.8E-14 0.0E+00
3.9E-15 0.0E+00
2.5E-16 0.0E+00
9.6E-14 0.0E+00
1.7E-13 0.0E+00
2.3E-14 0.0E+00
1.5E-15 0.0E+00
5.7E-13 0.0E+00
1.4E-14 0.0E+00
1.9E-15 0.0E+00
1.2E-16 0.0E+00
4.7E-14 0.0E+00
Source
282
Table C.11 (continued) Peroxy radical cross reactions
2p21 XPOO
2p21 XSOO
2p21 XTOO
2p21 XAOO
2p30 XPOO
2p30 XSOO
2p30 XTOO
2p30 XAOO
2p31 XPOO
2p31 XSOO
2p31 XTOO
2p31 XAOO
2t71 XPOO
2t71 XSOO
2t71 XTOO
2t71 XAOO
2t81 XPOO
2t81 XSOO
2t81 XTOO
2t81 XAOO
2d81 XPOO
2d81 XSOO
2d81 XTOO
2d81 XAOO
2t91 XPOO
2t91 XSOO
2t91 XTOO
2t91 XAOO
2t92 XPOO
2t92 XSOO
2t92 XTOO
2t92 XAOO
2tA1 XPOO
2tA1 XSOO
2tA1 XTOO
2tA1 XAOO
2dA2 XPOO
2dA2 XSOO
2dA2 XTOO
2dA2 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1p21 0.20 po23 0.20 pd21
0.60 1p21 0.20 po23 0.20 pd21
0.80 1p21 0.20 pd21
0.80 1p21 0.20 pd21
0.60 1p30 0.20 po35 0.20 pd33
0.60 1p30 0.20 po35 0.20 pd33
0.80 1p30 0.20 pd33
0.80 1p30 0.20 pd33
0.60 1p31 0.20 po31 0.20 pk33
0.60 1p31 0.20 po31 0.20 pk33
0.80 1p31 0.20 pk33
0.80 1p31 0.20 pk33
0.80 2e72 0.20 et71
0.80 2e72 0.20 et71
2e72
2e72
0.60 1t81 0.20 tk82 0.20 tk81
0.60 1t81 0.20 tk82 0.20 tk81
0.80 1t81 0.20 tk81
0.80 1t81 0.20 tk81
0.60 1d82 0.20 dt82 0.20 dt81
0.60 1d82 0.20 dt82 0.20 dt81
0.80 1d82 0.20 dt81
0.80 1d82 0.20 dt81
0.60 1t91 0.20 tk91 0.20 dt91
0.60 1t91 0.20 tk91 0.20 dt91
0.80 1t91 0.20 dt91
0.80 1t91 0.20 dt91
0.60 1t92 0.20 tk92 0.20 dt92
0.60 1t92 0.20 tk92 0.20 dt92
0.80 1t92 0.20 dt92
0.80 1t92 0.20 dt92
0.80 1tA1 0.20 toA1
0.80 1tA1 0.20 toA1
1tA1
1tA1
0.60 1dA2 0.20 dtA3 0.20 ddA2
0.60 1dA2 0.20 dtA3 0.20 ddA2
0.80 1dA2 0.20 ddA2
0.80 1dA2 0.20 ddA2
k2 98 E/R
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
4.1E-14 0.0E+00
5.9E-15 0.0E+00
3.7E-16 0.0E+00
1.4E-13 0.0E+00
2.3E-14 0.0E+00
3.2E-15 0.0E+00
2.0E-16 0.0E+00
7.9E-14 0.0E+00
1.7E-16 0.0E+00
2.4E-17 0.0E+00
1.5E-18 0.0E+00
5.8E-16 0.0E+00
2.0E-15 0.0E+00
2.9E-16 0.0E+00
1.8E-17 0.0E+00
7.0E-15 0.0E+00
2.0E-15 0.0E+00
2.9E-16 0.0E+00
1.8E-17 0.0E+00
7.0E-15 0.0E+00
2.5E-14 0.0E+00
3.5E-15 0.0E+00
2.2E-16 0.0E+00
8.6E-14 0.0E+00
2.5E-14 0.0E+00
3.5E-15 0.0E+00
2.2E-16 0.0E+00
8.6E-14 0.0E+00
1.1E-15 0.0E+00
1.6E-16 0.0E+00
1.0E-17 0.0E+00
3.9E-15 0.0E+00
1.7E-13 0.0E+00
2.3E-14 0.0E+00
1.5E-15 0.0E+00
5.7E-13 0.0E+00
Source
283
Table C.11 (continued) Peroxy radical cross reactions
2r61 XPOO
2r61 XSOO
2r61 XTOO
2r61 XAOO
2r62 XPOO
2r62 XSOO
2r62 XTOO
2r62 XAOO
2r63 XPOO
2r63 XSOO
2r63 XTOO
2r63 XAOO
2r71 XPOO
2r71 XSOO
2r71 XTOO
2r71 XAOO
2r72 XPOO
2r72 XSOO
2r72 XTOO
2r72 XAOO
2r73 XPOO
2r73 XSOO
2r73 XTOO
2r73 XAOO
2r74 XPOO
2r74 XSOO
2r74 XTOO
2r74 XAOO
2r81 XPOO
2r81 XSOO
2r81 XTOO
2r81 XAOO
2r82 XPOO
2r82 XSOO
2r82 XTOO
2r82 XAOO
2s21 XPOO
2s21 XSOO
2s21 XTOO
2s21 XAOO
2r75 XPOO
2r75 XSOO
2r75 XTOO
2r75 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.60 1r63 0.20 ro64 0.20 rk63
0.60 1r63 0.20 ro64 0.20 rk63
0.80 1r63 0.20 rk63
0.80 1r63 0.20 rk63
0.60 1r64 0.20 ro65 0.20 rk62
0.60 1r64 0.20 ro65 0.20 rk62
0.80 1r64 0.20 rk62
0.80 1r64 0.20 rk62
0.80 1r61 0.20 ro61
0.80 1r61 0.20 ro61
1r61
1r61
0.80 1r74 0.20 rv75
0.80 1r74 0.20 rv75
1r74
1r74
0.60 1r71 0.20 ro71 0.20 dr71
0.60 1r71 0.20 ro71 0.20 dr71
0.80 1r71 0.20 dr71
0.80 1r71 0.20 dr71
0.80 1r75 0.20 ro76
0.80 1r75 0.20 ro76
1r75
1r75
0.80 1r76 0.20 ro77
0.80 1r76 0.20 ro77
1r76
1r76
0.80 1r82 0.20 ro83
0.80 1r82 0.20 ro83
1r82
1r82
0.80 1r83 0.20 ro84
0.80 1r83 0.20 ro84
1r83
1r83
0.60 1s21 0.20 so21 0.20 sd21
0.60 1s21 0.20 so21 0.20 sd21
0.80 1s21 0.20 sd21
0.80 1s21 0.20 sd21
0.80 1r77 0.20 rv78
0.80 1r77 0.20 rv78
1r77
1r77
k2 98 E/R
1.5E-14 0.0E+00
2.2E-15 0.0E+00
1.4E-16 0.0E+00
5.3E-14 0.0E+00
1.5E-14 0.0E+00
2.2E-15 0.0E+00
1.4E-16 0.0E+00
5.3E-14 0.0E+00
1.9E-16 0.0E+00
2.7E-17 0.0E+00
1.7E-18 0.0E+00
6.5E-16 0.0E+00
1.7E-16 0.0E+00
2.4E-17 0.0E+00
1.5E-18 0.0E+00
5.8E-16 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-12 0.0E+00
1.7E-16 0.0E+00
2.4E-17 0.0E+00
1.5E-18 0.0E+00
5.8E-16 0.0E+00
1.7E-16 0.0E+00
2.4E-17 0.0E+00
1.5E-18 0.0E+00
5.8E-16 0.0E+00
1.7E-16 0.0E+00
2.4E-17 0.0E+00
1.5E-18 0.0E+00
5.8E-16 0.0E+00
1.7E-16 0.0E+00
2.4E-17 0.0E+00
1.5E-18 0.0E+00
5.8E-16 0.0E+00
4.7E-14 0.0E+00
6.6E-15 0.0E+00
4.2E-16 0.0E+00
1.6E-13 0.0E+00
1.7E-16 0.0E+00
2.4E-17 0.0E+00
1.5E-18 0.0E+00
5.8E-16 0.0E+00
Source
284
Table C.11 (continued) Peroxy radical cross reactions
3021 XPOO
3021 XSOO
3021 XTOO
3021 XAOO
3031 XPOO
3031 XSOO
3031 XTOO
3031 XAOO
3041 XPOO
3041 XSOO
3041 XTOO
3041 XAOO
3042 XPOO
3042 XSOO
3042 XTOO
3042 XAOO
3051 XPOO
3051 XSOO
3051 XTOO
3051 XAOO
3052 XPOO
3052 XSOO
3052 XTOO
3052 XAOO
3053 XPOO
3053 XSOO
3053 XTOO
3053 XAOO
3061 XPOO
3061 XSOO
3061 XTOO
3061 XAOO
3a21 XPOO
3a21 XSOO
3a21 XTOO
3a21 XAOO
3a31 XPOO
3a31 XSOO
3a31 XTOO
3a31 XAOO
3a32 XPOO
3a32 XSOO
3a32 XTOO
3a32 XAOO
3a33 XPOO
3a33 XSOO
3a33 XTOO
3a33 XAOO
Reaction
0.80 8021 0.20 a021
!
0.80 8021 0.20 a021
!
8021
!
8021
!
0.80 8031 0.20 a031
!
0.80 8031 0.20 a031
!
8031
!
8031
!
0.80 8041 0.20 a041
!
0.80 8041 0.20 a041
!
8041
!
8041
!
0.80 8042 0.20 a042
!
0.80 8042 0.20 a042
!
8042
!
8042
!
0.80 8051 0.20 a051
!
0.80 8051 0.20 a051
!
8051
!
8051
!
0.80 8052 0.20 a052
!
0.80 8052 0.20 a052
!
8052
!
8052
!
0.80 8053 0.20 a053
!
0.80 8053 0.20 a053
!
8053
!
8053
!
0.80 8061 0.20 a061
!
0.80 8061 0.20 a061
!
8061
!
8061
!
0.80 8a21 0.20 aa21
!
0.80 8a21 0.20 aa21
!
8a21
!
8a21
!
0.80 8a31 0.20 aa31
!
0.80 8a31 0.20 aa31
!
8a31
!
8a31
!
0.80 8a32 0.20 aa32
!
0.80 8a32 0.20 aa32
!
8a32
!
8a32
!
0.80 8a33 0.20 aa33
!
0.80 8a33 0.20 aa33
!
8a33
!
8a33
!
k2 98 E/R
4.1E-12 0.0E+00
5.8E-13 0.0E+00
3.7E-14 0.0E+00
1.4E-11 0.0E+00
4.1E-12 0.0E+00
5.8E-13 0.0E+00
3.7E-14 0.0E+00
1.4E-11 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
1.9E-13 0.0E+00
2.6E-14 0.0E+00
1.7E-15 0.0E+00
6.4E-13 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
Source
285
Table C.11 (continued) Peroxy radical cross reactions
3u31 XPOO
3u31 XSOO
3u31 XTOO
3u31 XAOO
3u32 XPOO
3u32 XSOO
3u32 XTOO
3u32 XAOO
3u41 XPOO
3u41 XSOO
3u41 XTOO
3u41 XAOO
3u42 XPOO
3u42 XSOO
3u42 XTOO
3u42 XAOO
3u43 XPOO
3u43 XSOO
3u43 XTOO
3u43 XAOO
3u44 XPOO
3u44 XSOO
3u44 XTOO
3u44 XAOO
3u51 XPOO
3u51 XSOO
3u51 XTOO
3u51 XAOO
3u52 XPOO
3u52 XSOO
3u52 XTOO
3u52 XAOO
3u53 XPOO
3u53 XSOO
3u53 XTOO
3u53 XAOO
3d21 XPOO
3d21 XSOO
3d21 XTOO
3d21 XAOO
3d31 XPOO
3d31 XSOO
3d31 XTOO
3d31 XAOO
3d32 XPOO
3d32 XSOO
3d32 XTOO
3d32 XAOO
Reaction
0.80 8u31 0.20 au31
!
0.80 8u31 0.20 au31
!
8u31
!
8u31
!
0.80 8u32 0.20 au32
!
0.80 8u32 0.20 au32
!
8u32
!
8u32
!
0.80 8u41 0.20 au41
!
0.80 8u41 0.20 au41
!
8u41
!
8u41
!
0.80 8u42 0.20 au42
!
0.80 8u42 0.20 au42
!
8u42
!
8u42
!
0.80 8u43 0.20 au43
!
0.80 8u43 0.20 au43
!
8u43
!
8u43
!
0.80 8u44 0.20 au44
!
0.80 8u44 0.20 au44
!
8u44
!
8u44
!
0.80 8u51 0.20 au51
!
0.80 8u51 0.20 au51
!
8u51
!
8u51
!
0.80 8u52 0.20 au52
!
0.80 8u52 0.20 au52
!
8u52
!
8u52
!
0.80 8u53 0.20 au53
!
0.80 8u53 0.20 au53
!
8u53
!
8u53
!
0.80 8d21 0.20 ad21
!
0.80 8d21 0.20 ad21
!
8d21
!
8d21
!
0.80 8d31 0.20 ad31
!
0.80 8d31 0.20 ad31
!
8d31
!
8d31
!
0.80 8d32 0.20 ad32
!
0.80 8d32 0.20 ad32
!
8d32
!
8d32
!
k2 98 E/R
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.0E-14 0.0E+00
2.8E-15 0.0E+00
1.8E-16 0.0E+00
6.9E-14 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
Source
286
Table C.11 (continued) Peroxy radical cross reactions
3d33 XPOO
3d33 XSOO
3d33 XTOO
3d33 XAOO
3d41 XPOO
3d41 XSOO
3d41 XTOO
3d41 XAOO
3d42 XPOO
3d42 XSOO
3d42 XTOO
3d42 XAOO
3d43 XPOO
3d43 XSOO
3d43 XTOO
3d43 XAOO
3d44 XPOO
3d44 XSOO
3d44 XTOO
3d44 XAOO
3d45 XPOO
3d45 XSOO
3d45 XTOO
3d45 XAOO
3d46 XPOO
3d46 XSOO
3d46 XTOO
3d46 XAOO
3d47 XPOO
3d47 XSOO
3d47 XTOO
3d47 XAOO
3d48 XPOO
3d48 XSOO
3d48 XTOO
3d48 XAOO
3d51 XPOO
3d51 XSOO
3d51 XTOO
3d51 XAOO
3d52 XPOO
3d52 XSOO
3d52 XTOO
3d52 XAOO
Reaction
0.80 8d33 0.20 ad33
!
0.80 8d33 0.20 ad33
!
8d33
!
8d33
!
0.80 8d41 0.20 ad41
!
0.80 8d41 0.20 ad41
!
8d41
!
8d41
!
0.80 8d42 0.20 ad42
!
0.80 8d42 0.20 ad42
!
8d42
!
8d42
!
0.80 8d43 0.20 ad43
!
0.80 8d43 0.20 ad43
!
8d43
!
8d43
!
0.80 8d44 0.20 ad44
!
0.80 8d44 0.20 ad44
!
8d44
!
8d44
!
0.80 8d45 0.20 ad45
!
0.80 8d45 0.20 ad45
!
8d45
!
8d45
!
0.80 8d46 0.20 ad46
!
0.80 8d46 0.20 ad46
!
8d46
!
8d46
!
0.80 8d47 0.20 ad47
!
0.80 8d47 0.20 ad47
!
8d47
!
8d47
!
0.80 8d48 0.20 ad48
!
0.80 8d48 0.20 ad48
!
8d48
!
8d48
!
0.80 8d51 0.20 ad51
!
0.80 8d51 0.20 ad51
!
8d51
!
8d51
!
0.80 8d52 0.20 ad52
!
0.80 8d52 0.20 ad52
!
8d52
!
8d52
!
k2 98 E/R
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
Source
287
Table C.11 (continued) Peroxy radical cross reactions
3d53 XPOO
3d53 XSOO
3d53 XTOO
3d53 XAOO
3d54 XPOO
3d54 XSOO
3d54 XTOO
3d54 XAOO
3d55 XPOO
3d55 XSOO
3d55 XTOO
3d55 XAOO
3d56 XPOO
3d56 XSOO
3d56 XTOO
3d56 XAOO
3h21 XPOO
3h21 XSOO
3h21 XTOO
3h21 XAOO
3h40 XPOO
3h40 XSOO
3h40 XTOO
3h40 XAOO
3g40 XPOO
3g40 XSOO
3g40 XTOO
3g40 XAOO
3v22 XPOO
3v22 XSOO
3v22 XTOO
3v22 XAOO
3k31 XPOO
3k31 XSOO
3k31 XTOO
3k31 XAOO
3v32 XPOO
3v32 XSOO
3v32 XTOO
3v32 XAOO
3k33 XPOO
3k33 XSOO
3k33 XTOO
3k33 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.80 8d53 0.20 ad53
0.80 8d53 0.20 ad53
8d53
8d53
0.80 8d54 0.20 ad54
0.80 8d54 0.20 ad54
8d54
8d54
0.80 8d55 0.20 ad55
0.80 8d55 0.20 ad55
8d55
8d55
0.80 8d56 0.20 ad56
0.80 8d56 0.20 ad56
8d56
8d56
0.80 8h21 0.20 ah21
0.80 8h21 0.20 ah21
8h21
8h21
0.80 ko37 0.20 ah42 0.80 HO 0.80 CO2
0.80 ko37 0.20 ah42 0.80 HO 0.80 CO2
ko37 HO CO2
ko37 HO CO2
0.80 gk33 0.20 ag40 0.80 HO 0.80 CO2
0.80 gk33 0.20 ag40 0.80 HO 0.80 CO2
gk33 HO CO2
gk33 HO CO2
0.80 8v21 0.20 av22
0.80 8v21 0.20 av22
8v21
8v21
0.80 8k31 0.20 ak31
0.80 8k31 0.20 ak31
8k31
8k31
0.80 8v32 0.20 av32
0.80 8v32 0.20 av32
8v32
8v32
0.80 8k33 0.20 ak33
0.80 8k33 0.20 ak33
8k33
8k33
k2 98 E/R
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
2.4e-13 0.0e+00
3.4e-14 0.0e+00
2.2e-15 0.0e+00
8.4e-13 0.0e+00
2.4e-13 0.0e+00
3.4e-14 0.0e+00
2.2e-15 0.0e+00
8.4e-13 0.0e+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
Source
288
Table C.11 (continued) Peroxy radical cross reactions
3k40 XPOO
3k40 XSOO
3k40 XTOO
3k40 XAOO
3v41 XPOO
3v41 XSOO
3v41 XTOO
3v41 XAOO
3v42 XPOO
3v42 XSOO
3v42 XTOO
3v42 XAOO
3v43 XPOO
3v43 XSOO
3v43 XTOO
3v43 XAOO
3v44 XPOO
3v44 XSOO
3v44 XTOO
3v44 XAOO
3k45 XPOO
3k45 XSOO
3k45 XTOO
3k45 XAOO
3k46 XPOO
3k46 XSOO
3k46 XTOO
3k46 XAOO
3k47 XPOO
3k47 XSOO
3k47 XTOO
3k47 XAOO
3k48 XPOO
3k48 XSOO
3k48 XTOO
3k48 XAOO
3k49 XPOO
3k49 XSOO
3k49 XTOO
3k49 XAOO
3k4A XPOO
3k4A XSOO
3k4A XTOO
3k4A XAOO
Reaction
0.80 8k40 0.20 ak40
!
0.80 8k40 0.20 ak40
!
8k40
!
8k40
!
0.80 8v41 0.20 av41
!
0.80 8v41 0.20 av41
!
8v41
!
8v41
!
0.80 8v42 0.20 av42
!
0.80 8v42 0.20 av42
!
8v42
!
8v42
!
0.80 8v43 0.20 av43
!
0.80 8v43 0.20 av43
!
8v43
!
8v43
!
0.80 8v44 0.20 av44
!
0.80 8v44 0.20 av44
!
8v44
!
8v44
!
0.80 8k45 0.20 ak45
!
0.80 8k45 0.20 ak45
!
8k45
!
8k45
!
0.80 8k46 0.20 ak46
!
0.80 8k46 0.20 ak46
!
8k46
!
8k46
!
0.80 8k47 0.20 ak47
!
0.80 8k47 0.20 ak47
!
8k47
!
8k47
!
0.80 8k48 0.20 ak48
!
0.80 8k48 0.20 ak48
!
8k48
!
8k48
!
0.80 8k49 0.20 ak49
!
0.80 8k49 0.20 ak49
!
8k49
!
8k49
!
0.80 8k4A 0.20 ak4A
!
0.80 8k4A 0.20 ak4A
!
8k4A
!
8k4A
!
k2 98 E/R
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
Source
289
Table C.11 (continued) Peroxy radical cross reactions
3k50 XPOO
3k50 XSOO
3k50 XTOO
3k50 XAOO
3k51 XPOO
3k51 XSOO
3k51 XTOO
3k51 XAOO
3k52 XPOO
3k52 XSOO
3k52 XTOO
3k52 XAOO
3k53 XPOO
3k53 XSOO
3k53 XTOO
3k53 XAOO
3v54 XPOO
3v54 XSOO
3v54 XTOO
3v54 XAOO
3k55 XPOO
3k55 XSOO
3k55 XTOO
3k55 XAOO
3v56 XPOO
3v56 XSOO
3v56 XTOO
3v56 XAOO
3k57 XPOO
3k57 XSOO
3k57 XTOO
3k57 XAOO
3k58 XPOO
3k58 XSOO
3k58 XTOO
3k58 XAOO
3k59 XPOO
3k59 XSOO
3k59 XTOO
3k59 XAOO
3k5A XPOO
3k5A XSOO
3k5A XTOO
3k5A XAOO
Reaction
0.80 8k50 0.20 ak50
!
0.80 8k50 0.20 ak50
!
8k50
!
8k50
!
0.80 8k51 0.20 ak51
!
0.80 8k51 0.20 ak51
!
8k51
!
8k51
!
0.80 8k52 0.20 ak52
!
0.80 8k52 0.20 ak52
!
8k52
!
8k52
!
0.80 8k53 0.20 ak53
!
0.80 8k53 0.20 ak53
!
8k53
!
8k53
!
0.80 8v54 0.20 av54
!
0.80 8v54 0.20 av54
!
8v54
!
8v54
!
0.80 8k55 0.20 ak55
!
0.80 8k55 0.20 ak55
!
8k55
!
8k55
!
0.80 8v56 0.20 av56
!
0.80 8v56 0.20 av56
!
8v56
!
8v56
!
0.80 8k57 0.20 ak57
!
0.80 8k57 0.20 ak57
!
8k57
!
8k57
!
0.80 8k58 0.20 ak58
!
0.80 8k58 0.20 ak58
!
8k58
!
8k58
!
0.80 8k59 0.20 ak59
!
0.80 8k59 0.20 ak59
!
8k59
!
8k59
!
0.80 8k5A 0.20 ak5A
!
0.80 8k5A 0.20 ak5A
!
8k5A
!
8k5A
!
k2 98 E/R
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
Source
290
Table C.11 (continued) Peroxy radical cross reactions
3k5B XPOO
3k5B XSOO
3k5B XTOO
3k5B XAOO
3k5C XPOO
3k5C XSOO
3k5C XTOO
3k5C XAOO
3l11 XPOO
3l11 XSOO
3l11 XTOO
3l11 XAOO
3n21 XPOO
3n21 XSOO
3n21 XTOO
3n21 XAOO
3n31 XPOO
3n31 XSOO
3n31 XTOO
3n31 XAOO
3n32 XPOO
3n32 XSOO
3n32 XTOO
3n32 XAOO
3n33 XPOO
3n33 XSOO
3n33 XTOO
3n33 XAOO
3n34 XPOO
3n34 XSOO
3n34 XTOO
3n34 XAOO
3n41 XPOO
3n41 XSOO
3n41 XTOO
3n41 XAOO
3n42 XPOO
3n42 XSOO
3n42 XTOO
3n42 XAOO
3n43 XPOO
3n43 XSOO
3n43 XTOO
3n43 XAOO
3n44 XPOO
3n44 XSOO
3n44 XTOO
3n44 XAOO
Reaction
0.80 8k5B 0.20 ak5B
!
0.80 8k5B 0.20 ak5B
!
8k5B
!
8k5B
!
0.80 8k5C 0.20 ak5C
!
0.80 8k5C 0.20 ak5C
!
8k5C
!
8k5C
!
0.80 8l11 0.20 la11
!
0.80 8l11 0.20 la11
!
8l11
!
8l11
!
0.80 8n21 0.20 an21
!
0.80 8n21 0.20 an21
!
8n21
!
8n21
!
0.80 8n31 0.20 an31
!
0.80 8n31 0.20 an31
!
8n31
!
8n31
!
0.80 8n32 0.20 an32
!
0.80 8n32 0.20 an32
!
8n32
!
8n32
!
0.80 8n33 0.20 an33
!
0.80 8n33 0.20 an33
!
8n33
!
8n33
!
0.80 8n34 0.20 an35
!
0.80 8n34 0.20 an35
!
8n34
!
8n34
!
0.80 8n41 0.20 an41
!
0.80 8n41 0.20 an41
!
8n41
!
8n41
!
0.80 8n42 0.20 an42
!
0.80 8n42 0.20 an42
!
8n42
!
8n42
!
0.80 8n43 0.20 an43
!
0.80 8n43 0.20 an43
!
8n43
!
8n43
!
0.80 8n44 0.20 an44
!
0.80 8n44 0.20 an44
!
8n44
!
8n44
!
k2 98 E/R
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
4.1E-12 0.0E+00
5.8E-13 0.0E+00
3.7E-14 0.0E+00
1.4E-11 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
Source
291
Table C.11 (continued) Peroxy radical cross reactions
3n45 XPOO
3n45 XSOO
3n45 XTOO
3n45 XAOO
3n46 XPOO
3n46 XSOO
3n46 XTOO
3n46 XAOO
3n47 XPOO
3n47 XSOO
3n47 XTOO
3n47 XAOO
3n48 XPOO
3n48 XSOO
3n48 XTOO
3n48 XAOO
3n49 XPOO
3n49 XSOO
3n49 XTOO
3n49 XAOO
3n51 XPOO
3n51 XSOO
3n51 XTOO
3n51 XAOO
3n52 XPOO
3n52 XSOO
3n52 XTOO
3n52 XAOO
3n53 XPOO
3n53 XSOO
3n53 XTOO
3n53 XAOO
3n54 XPOO
3n54 XSOO
3n54 XTOO
3n54 XAOO
3n55 XPOO
3n55 XSOO
3n55 XTOO
3n55 XAOO
3v21 XPOO
3v21 XSOO
3v21 XTOO
3v21 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.80 8n45 0.20 an45
0.80 8n45 0.20 an45
8n45
8n45
0.80 8n46 0.20 an46
0.80 8n46 0.20 an46
8n46
8n46
0.80 8n47 0.20 an47
0.80 8n47 0.20 an47
8n47
8n47
0.80 8n48 0.20 an48
0.80 8n48 0.20 an48
8n48
8n48
0.80 ko37 0.20 an49 0.80 NO2 0.80 CO
0.80 ko37 0.20 an49 0.80 NO2 0.80 CO
ko37 NO2 CO2
ko37 NO2 CO2
0.80 8n51 0.20 an51
0.80 8n51 0.20 an51
8n51
8n51
0.80 8n52 0.20 an52
0.80 8n52 0.20 an52
8n52
8n52
0.80 8n53 0.20 an53
0.80 8n53 0.20 an53
8n53
8n53
0.80 8n54 0.20 an54
0.80 8n54 0.20 an54
8n54
8n54
0.80 8n55 0.20 an55
0.80 8n55 0.20 an55
8n55
8n55
0.80 8v22 0.20 av21
0.80 8v22 0.20 av21
8v22
8v22
k2 98 E/R
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
Source
292
Table C.11 (continued) Peroxy radical cross reactions
3o22 XPOO
3o22 XSOO
3o22 XTOO
3o22 XAOO
3o23 XPOO
3o23 XSOO
3o23 XTOO
3o23 XAOO
3o31 XPOO
3o31 XSOO
3o31 XTOO
3o31 XAOO
3o32 XPOO
3o32 XSOO
3o32 XTOO
3o32 XAOO
3o33 XPOO
3o33 XSOO
3o33 XTOO
3o33 XAOO
3o34 XPOO
3o34 XSOO
3o34 XTOO
3o34 XAOO
3o35 XPOO
3o35 XSOO
3o35 XTOO
3o35 XAOO
3o41 XPOO
3o41 XSOO
3o41 XTOO
3o41 XAOO
3o42 XPOO
3o42 XSOO
3o42 XTOO
3o42 XAOO
3o43 XPOO
3o43 XSOO
3o43 XTOO
3o43 XAOO
3o44 XPOO
3o44 XSOO
3o44 XTOO
3o44 XAOO
Reaction
0.80 8o22 0.20 ao22
!
0.80 8o22 0.20 ao22
!
8o22
!
8o22
!
0.80 8o23 0.20 ao23
!
0.80 8o23 0.20 ao23
!
8o23
!
8o23
!
0.80 8o31 0.20 ao31
!
0.80 8o31 0.20 ao31
!
8o31
!
8o31
!
0.80 8o32 0.20 ao32
!
0.80 8o32 0.20 ao32
!
8o32
!
8o32
!
0.80 8o33 0.20 ao33
!
0.80 8o33 0.20 ao33
!
8o33
!
8o33
!
0.80 8o34 0.20 ao34
!
0.80 8o34 0.20 ao34
!
8o34
!
8o34
!
0.80 8o35 0.20 ao35
!
0.80 8o35 0.20 ao35
!
8o35
!
8o35
!
0.80 8o41 0.20 ao41
!
0.80 8o41 0.20 ao41
!
8o41
!
8o41
!
0.80 8o42 0.20 ao42
!
0.80 8o42 0.20 ao42
!
8o42
!
8o42
!
0.80 8o43 0.20 ao43
!
0.80 8o43 0.20 ao43
!
8o43
!
8o43
!
0.80 8o44 0.20 ao44
!
0.80 8o44 0.20 ao44
!
8o44
!
8o44
!
k2 98 E/R
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
3.1E-13 0.0E+00
4.4E-14 0.0E+00
2.8E-15 0.0E+00
1.1E-12 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.8E-13 0.0E+00
3.9E-14 0.0E+00
2.5E-15 0.0E+00
9.6E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
Source
293
Table C.11 (continued) Peroxy radical cross reactions
3o45 XPOO
3o45 XSOO
3o45 XTOO
3o45 XAOO
3o46 XPOO
3o46 XSOO
3o46 XTOO
3o46 XAOO
3o47 XPOO
3o47 XSOO
3o47 XTOO
3o47 XAOO
3o51 XPOO
3o51 XSOO
3o51 XTOO
3o51 XAOO
3o52 XPOO
3o52 XSOO
3o52 XTOO
3o52 XAOO
3o53 XPOO
3o53 XSOO
3o53 XTOO
3o53 XAOO
3o54 XPOO
3o54 XSOO
3o54 XTOO
3o54 XAOO
3o55 XPOO
3o55 XSOO
3o55 XTOO
3o55 XAOO
3o56 XPOO
3o56 XSOO
3o56 XTOO
3o56 XAOO
3o57 XPOO
3o57 XSOO
3o57 XTOO
3o57 XAOO
3o61 XPOO
3o61 XSOO
3o61 XTOO
3o61 XAOO
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
0.80 8o45 0.20 ao45
0.80 8o45 0.20 ao45
8o45
8o45
0.80 8o46 0.20 ao46
0.80 8o46 0.20 ao46
8o46
8o46
0.80 8o47 0.20 ao47
0.80 8o47 0.20 ao47
8o47
8o47
0.80 8o51 0.20 ao51
0.80 8o51 0.20 ao51
8o51
8o51
0.80 8o52 0.20 ao52
0.80 8o52 0.20 ao52
8o52
8o52
0.80 8o53 0.20 ao53
0.80 8o53 0.20 ao53
8o53
8o53
0.80 8o54 0.20 ao54
0.80 8o54 0.20 ao54
8o54
8o54
0.80 8o55 0.20 ao55
0.80 8o55 0.20 ao55
8o55
8o55
0.80 8o56 0.20 ao56
0.80 8o56 0.20 ao56
8o56
8o56
0.80 do49 0.20 ao50 0.80 HO2 0.80 CO2
0.80 do49 0.20 ao50 0.80 HO2 0.80 CO2
do49 HO2 CO2
do49 HO2 CO2
0.80 8o61 0.20 ao61
0.80 8o61 0.20 ao61
8o61
8o61
k2 98 E/R
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.4E-13 0.0E+00
3.4E-14 0.0E+00
2.2E-15 0.0E+00
8.4E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9E-15 0.0E+00
7.3E-13 0.0E+00
2.1E-13 0.0E+00
3.0E-14 0.0E+00
1.9e-15 0.0e+00
7.3E-13 0.0E+00
1.9E-13 0.0E+00
2.6E-14 0.0E+00
1.7E-15 0.0E+00
6.4E-13 0.0E+00
Source
294
Table C.11 (continued) Peroxy radical cross reactions
3t91 XPOO
3t91 XSOO
3t91 XTOO
3t91 XAOO
3tA1 XPOO
3tA1 XSOO
3tA1 XTOO
3tA1 XAOO
3r71 XPOO
3r71 XSOO
3r71 XTOO
3r71 XAOO
Reaction
0.80 8t91 0.20 at91
!
0.80 8t91 0.20 at91
!
8t91
!
8t91
!
0.80 8tA1 0.20 atA1
!
0.80 8tA1 0.20 atA1
!
8tA1
!
8tA1
!
0.80 8r71 0.20 ar71
!
0.80 8r71 0.20 ar71
!
8r71
!
8r71
!
k2 98 E/R
1.7E-13 0.0E+00
2.3E-14 0.0E+00
1.5E-15 0.0E+00
5.7E-13 0.0E+00
1.7E-13 0.0E+00
2.3E-14 0.0E+00
1.5E-15 0.0E+00
5.7E-13 0.0E+00
1.7E-13 0.0E+00
2.3E-14 0.0E+00
1.5E-15 0.0E+00
5.7E-13 0.0E+00
Source
295
Table C.12 Alkoxy radical reactions.
Reaction
1 CH3O O2
!
CH2O HO2
1 CH3O NO
!
CH2O HNO
1 CH3O NO2
!
CH2O HNO2
1 CH3O NO2 (M) ! n011 (M)
1 1021 O2
!
d021 HO2
1 1021 NO (M)
!
w022 (M)
1 1021 NO2 (M)
!
n021 (M)
1 1n35 O2
!
nd38 HO2
1 1n35
!
do35 NO2
1 1n4a O2
!
nk49 HO2
1 1n4a
!
do44 NO2
1 1n4a
!
d021 2n22 XPOO
1 1n4a
!
nd38 2011
1 1n4b O2
!
nd48 HO2
1 1n4b
!
ko45 NO2
1 1n4b
!
2n33 CH2O XPOO
1 1n55
!
do52 NO2
1 1n55
!
d021 2n35 XPOO
1 1n56
!
2021 nd38
1 1n56
!
d031 2n22 XPOO
1 1n56 O2
!
nk53 HO2
1 1k52
!
d021 2k33 XPOO
1 1k52
!
2011 2k47 XPOO
1 1k52 O2
!
kk52 HO2
1 1k53
!
d021 3031
1 1k53 O2
!
kk53 HO2
1 1k61
!
d021 2k45 XPOO
1 1k61
!
dk5C 2011
1 1k61 O2
!
kk61 HO2
1 1n57
!
d021 2n33 XPOO
1 1n57
!
2011 nd48 XPOO
1 1n58
!
d031 d021 NO2
1 1n58
!
nd35 2021 XPOO
1 1n59
!
d021 d031 NO2
1 1n59
!
2n5b
1 1n59 O2
!
nk56 HO2
1 1n5a
!
2n5c
1 1n5a O2
!
nd58 HO2
k2 98 E/R
1.9E-15 9.0E+02
< 8.0E-12 0.0E+00
2.0E-13 1.2E+03
1.5E-11 0.0E+00
1.0E-14 5.5E+02
4.7E-11 0.0E+00
2.7E-11 0.0E+00
8.2E-15 9.5E+02
3.4E+03 5.3E+03
1.2E-15 2.5E+03
3.4E+03 5.3E+03
2.6E+05 6.6E+03
2.0E+04 7.4E+03
8.2E-15 9.5E+02
1.7E+03 5.3E+03
1.7E+03 8.1E+03
1.5E+07 2.6E+03
2.6E+05 6.6E+03
4.3E+05 6.5E+03
4.3E+05 6.5E+03
1.2E-15 2.5E+03
1.1E+05 5.5E+03
1.3E+03 4.1E+03
1.2E-15 2.5E+03
3.3E+05 4.3E+03
1.2E-15 2.5E+03
1.1E+05 5.5E+03
3.2E+03 6.6E+03
1.2E-15 2.5E+05
2.6E+05 6.6E+03
2.0E+04 7.4E+03
1.0E+07 5.5E+03
3.3E+05 6.6E+03
6.8E+06 5.7E+03
1.3E+05 4.9E+03
1.2E-15 2.5E+03
1.5E+07 2.6E+03
8.2E-15 9.5E+02
Source
DeMore et al. [1997]
DeMore et al. [1997]a
DeMore et al. [1997] b
[DeMore et al., 1997], See Table C.19
DeMore et al. [1997]
DeMore et al. [1997], see Table C.19
DeMore et al. [1997], see Table C.19
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
a New Reaction
b products changed, see text
c New reaction, added by Williams [1994a] as a result of new reactions of alkyl nitrates
296
Table C.13 Carbonyls.
d CH2O + HO
d CH2O + NO3
d CH2O + HO2
d CH2O + O3P
d d021 + HO
d d021 + NO3
d d021 + O3P
d dd21 + NO3
d d031 + HO
d d041 + HO
d d041 + HO
d d042 + HO
d d051 + HO
d d051 + HO
d d052 + HO
d d052 + HO
d do23 + HO
Reaction
!
HCO + H2O
!
HCO + HNO3
!
2o11 + XPOO
!
HCO + HO
!
3021 + H2O + XAOO
!
3021 + HNO3 + XAOO
!
0d21 + HO
!
0d22 + HNO3
!
3031 + H2O + XAOO
1
!
2
!
!
1
!
2
!
1
!
2
0.38 2d47 + 1.62 3041 + 2.00 H2O
1.62 XAOO + 0.38 XSOO
3042 + H2O + XAOO
0.38 2d58 + 1.62 3051 + 2.00 H2O
1.62 XAOO + 0.38 XSOO
0.56 2d59 + 1.44 3053 + 2.00 H2O
k2 98 E/R
1.0E-11 0.0E+00
5.8E-16 2.9E+03
5.0E-14 -6.0E+02
1.6E-13 1.6E+03
1.4E-11 -2.7E+02
2.4E-15 1.9E+03
4.5E-13 1.1E+03
4.5E-15 1.9E+03
2.0E-11 -2.5E+02
1.2E-11 -2.5E+02
1.2E-11 -2.5E+02
2.6E-11 -4.1E+02
1.4E-11 -4.5E+02
Source
Madronich and Calvert [1989]a
DeMore et al. [1997] b
DeMore et al. [1997]
Madronich and Calvert [1989]a
DeMore et al. [1997]
DeMore et al. [1997]
Madronich and Calvert [1989]a
Stockwell et al. [1997]
Atkinson [1994] b
Atkinson [1994] c
Atkinson [1994]c
Atkinson [1994]c
Atkinson [1994]c
1.4E-11 -4.5E+02
1.4E-11 -2.6E+02
1.4E-11 -2.6E+02
9.9E-12 -2.6E+02
Atkinson [1994]c
Atkinson [1994] b
Atkinson [1994]b
Atkinson [1994] b;d
!
1.44 XAOO + 0.56 XTOO
!
0.80 3o23 + 0.20 dd21 +
+ 0.20 HO2 + 0.80 XAOO
d dd21 + HO
d dk33 + HO
k k031 HO
k ko37 HO
!
0d22 + H2O
3k33 + H2O + XAOO
2k33 H2O XPOO
dk33 HO2
1.1E-11 0.0E+00
1.7E-11 -2.5E+02
2.2E-13 6.9E+02
3.0E-12 0.0E+00
Atkinson [1994]
Atkinson [1994]b
DeMore et al. [1997]
Atkinson [1994]
k k041 HO
k k041 HO
k k051 HO
k k052 HO
k k062 HO
k kk43 + HO
!
0.96 2k44 1.04 2k47 2.00 H2O
5.8E-13 1.8E+02
5.8E-13 1.8E+02
4.9E-12 -7.6E+01
2.0E-12 4.6E+02
9.1E-12 -1.8E+02
2.4E-13 4.0E+02
Atkinson [1994]
Atkinson [1994]c
Atkinson [1994] e;f
Atkinson [1994]e;f;g
Atkinson [1994]e;f
Atkinson [1994] c;h
!
!
!
1
2
!
!
!
!
!
0.96 XSOO + 1.04 XPOO
2k52 H2O XSOO
2k53 H2O XSOO
2k61 H2O
2k43 + H2O + XPOO
a Recommended by DeMore et al. [1997]
b No E/R value reported, use Madronich and Calvert [1989]
c E/R calculated from D+nT, not reported as an Arrhenius equation
d Branching ratio changed, used that recommended by Atkinson et al. [1992b]
e Reaction added by Williams [1994a]
f No E/R value reported, use E/R generated by Williams [1994a]
g Product changed to 2k53 from 2k52
h New reaction
297
Table C.14 Oxygenated Organic Updates.
Reaction
o o011 + HO
o o021 + HO
o o031 + HO
o o032 + HO
o o042 HO
o o042 HO
o o043 HO
o o011 + NO3
o o021 + NO3
o o031 + NO3
a a011 HO
a a021 HO
a a031 HO
!
0.14 0o11 + 0.86 CH3O + H2O
!
d021 + H2O + HO2
!
0.23 2o32 + 0.77 d031 + 0.77 HO2 + 0.23 XSOO
!
k031 + HO2
1
2
>
0.03 2o42 0.39 2o4c 0.58 d041 0.58 HO2
!
0.39 XSOO 0.03 XPOO
2o45 XPOO
0.14 0o11 0.86 CH3O HNO3
d021 HNO3 HO2
!
0.23 2o32 0.77 d031 0.77 HO2 0.23 XSOO
!
CO2 H2O H
2a21 H2O XPOO
2a31 H2O XSOO
!
!
!
k2 98 E/R
8.9E-13 6.0E+02
3.2E-12 2.4E+02
5.5E-12 0.0E+00
5.3E-12 -3.5E+01
4.3E-12 0.0E+00
4.3E-12 0.0E+00
1.1E-12 2.7E+02
<6.0E-16 0.0E+00
<9.0E-16 0.0E+00
<2.3E-15 0.0E+00
4.0E-13 0.0E+00
8.0E-13 -2.0E+02
1.2E-12 0.0E+00
a E/R calculated from D+nT, not reported as an Arrhenius expression
b New Reaction
c branching ratio calculated using Atkinson et al. [1987]
Source
DeMore et al. [1997]
DeMore et al. [1997]
Atkinson [1994]
Atkinson [1994]a
Atkinson [1994]b;c
Atkinson [1994]b;c
Atkinson [1994]a;b
Atkinson [1994]b
Atkinson [1994]b
Atkinson [1994]b
DeMore et al. [1997]
DeMore et al. [1997]
Atkinson [1994]
298
Table C.15 Hydroperoxide Reactions.
h h011 HO
h h011 HO
h h031 HO
h h043 HO
h hn35 HO
h hn35 HO
h hn49 HO
h hn49 HO
h hn4a HO
h hn4a HO
h hn5a HO
h hn5a HO
h hn5b HO
h hn5b HO
h hn5c HO
h hn5c HO
h hn5d HO
h hn5d HO
h hn5e HO
h hn5e HO
h hn5f HO
h hn5f HO
h hk53 HO
h hk53 HO
h hk54 HO
h hk54 HO
h hk61 HO
h hk61 HO
Reaction
k2 98 E/R
!
A
B
!
2011 H2O
5.2e-12 -2.0E+02
CH2O HO H2O
!
0.50 2031 0.50 k031 0.50 HO 0.50 XSOO
!
2043 H2O XTOO
nd38 HO
2n35 XPOO
nk49 HO
2n4a XSOO
nd48 HO
2n4b XPOO
nk52 HO
2n55 XSOO
nk53 HO
2n56 XSOO
nk54 HO
2n57 XSOO
nk55 HO
2n58 XSOO
nk56 HO
2n59 XSOO
nd58 HO
2n5a XPOO
2k52 H2O XSOO
kk52 HO
2k53 H2O XSOO
kk53 HO
2k61 H2O XSOO
kk61 HO
2.2e-12 -2.0E+02
1.0E-11 0.0E+00
3.0E-12 0.0E+00
5.0E-12 2.9E+02
3.9E-12 2.2E+02
5.0E-12 2.9E+02
3.9E-12 2.2E+02
5.0E-12 2.9E+02
3.9E-12 2.2E+02
1.1E-11 -1.9E+02
3.8E-12 2.2E+02
1.4E-11 -2.7E+02
3.8E-12 2.2E+02
1.1E-11 -1.9E+02
3.9E-12 2.2E+02
2.3E-12 2.7E+03
3.9E-12 2.2E+02
1.9E-12 3.5E+02
4.1E-12 2.2E+02
5.1E-12 2.9E+02
4.0E-12 2.2E+02
3.8E-12 2.2E+02
3.6E-11 -5.5E+02
3.9E-12 2.2E+02
6.5E-12 -3.3E+01
3.9E-12 2.2E+02
3.7E-11 -5.5E+02
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
a Branching ratio and products from Madronich and Calvert [1989]
b product changed from 2032 to 2031 by Williams [1994a]
c k and E/R set equal to hn4a values
d New Reaction, see text
Source
DeMore et al. [1997] a
same as reaction above
Madronich and Calvert [1989] b
Atkinson [1994]
added by Williams [1994a]
added by Williams [1994a]
c added by Williams [1994a]
c;d
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
added by Williams [1994a]
299
Table C.16 Alkyl Nitrate Updates.
n n011 + HO
n n021 + HO
n n021 + HO
n n031 HO
n n031 HO
n n031 HO
n n032 + HO
n n032 + HO
n n041 + HO
n n041 + HO
n n042 HO
n n042 HO
n n042 HO
n n053 HO
n n053 HO
n n053 HO
n n054 HO
n n054 HO
n n054 HO
n n055 HO
n n055 HO
n n055 HO
Reaction
!
CH2O+ NO2+ H2O
!
2n22+ XPOO
!
d021+ NO2
!
2n35 XPOO
!
2n32 XSOO
!
d031 NO2
!
2n33+ XPOO
!
k031+ NO2
!
2n4a+ XSOO
!
d041+ NO2
!
2n4b XPOO
!
2n45 XSOO
!
k041 NO2
!
2n55 XSOO
!
2n56 XSOO
!
d051 NO2
!
2n57 XSOO
!
k051 NO2
!
2n58 XSOO
!
2n59 XSOO
!
2n5a XPOO
!
k052 NO2
k2 98 E/R
2.4E-14 8.9E+02
4.0E-14 4.5E+02
1.4E-13 4.5E+02
8.1E-14 8.2E+02
3.7E-13 8.3E+02
2.8E-13 9.7E+02
3.5E-14 3.1E+02
2.6E-13 3.1E+02
1.5E-12 2.9E+02
2.1E-13 9.7E+02
2.0E-13 8.2E+02
2.3E-13 8.3E+02
4.9E-13 5.0E+02
8.1E-13 2.9E+02
1.0E-12 2.1E+02
1.3E-13 2.5E+02
1.2E-12 2.9E+02
2.7E-13 5.0E+02
2.6E-13 7.5E+02
3.3E-13 8.3E+02
2.4E-13 8.2E+02
5.5E-13 4.2E+02
Source
DeMore et al. [1997]
DeMore et al. [1997]a;b
DeMore et al. [1997]a;b
Atkinson [1994]b;c
Atkinson [1994]b;c
Atkinson [1994]b;c
Talukdar et al. [1997]a;b
Talukdar et al. [1997]a;b
Atkinson [1994]a;b;c
Atkinson [1994]a;b;c;d
Atkinson [1994]a;b;c
Atkinson [1994]a;b;c
Atkinson [1994]a;b;c
Atkinson [1994]a;b;c
Atkinson [1994]a;b;c
Atkinson [1994]b;e;f
Atkinson and Aschmann [1989]a;b
Atkinson and Aschmann [1989]a;b
Atkinson and Aschmann [1989]a;b
Atkinson [1994]a;b;c
Atkinson [1994]a;b;c
Atkinson [1994]a;b;c
a Reaction added by Williams [1994a]
b Branching ratio calculated using estimation technique of Atkinson and Aschmann [1989]
c No E/R reported, used E/R values generated by Williams [1994a]
d Product changed from do41 to d041
e New Reaction
f E/R set equal to average of E/R in other 2 channels added by Williams [1994a]
300
Table C.17 Peroxy Acyl Nitrate Updates.
p p021 + HO
3 3021 NO2 (M)
p p021 (M)
p pv22
p pd21
p pg21
p pn21
p pv21
p po23
p po22
p pn31
p pd31
p pn32
p pu31
p pv32
p pd33
p pk33
p pd32
p pk31
p pu32
p pn34
p po31
p po35
p po32
p po33
p po34
p pu41
p pu43
p pd41
p pv41
p pv42
p pu42
p pd46
p pd47
p pd43
p pd44
p pn42
p pn41
p pn44
p pn43
p pn40
p pv43
p pd42
p pn49
p pv44
p pd48
Reaction
!
2p21 + H2O + XPOO
!
p021 -1.00 XAOO (M)
!
3021 NO2 XAOO (M)
!
3v22 + NO2 + XAOO
!
3d21+ NO2+ XAOO
!
3a21+ NO2+ XAOO
!
3n21+ NO2+ XAOO
!
3v21+ NO2+ XAOO
!
3o23+ NO2+ XAOO
!
3o22+ NO2+ XAOO
!
3n31+ NO2+ XAOO
!
3d31+ NO2+ XAOO
!
3n32+ NO2+ XAOO
!
3u31+ NO2+ XAOO
!
3v32+ NO2+ XAOO
!
3d33+ NO2+ XAOO
!
3k33+ NO2+ XAOO
!
3d32+ NO2+ XAOO
!
3k31+ NO2+ XAOO
!
3u32+ NO2+ XAOO
!
3n34+ NO2+ XAOO
!
3o31+ NO2+ XAOO
!
3o35+ NO2+ XAOO
!
3o32+ NO2+ XAOO
!
3o33+ NO2+ XAOO
!
3o34+ NO2+ XAOO
!
3u41+ NO2+ XAOO
!
3u44+ NO2+ XAOO
!
3d41+ NO2+ XAOO
!
3v41+ NO2+ XAOO
!
3v42+ NO2+ XAOO
!
3u42+ NO2+ XAOO
!
3d46+ NO2+ XAOO
!
3d47+ NO2+ XAOO
!
3d43+ NO2+ XAOO
!
3d44+ NO2+ XAOO
!
3n42+ NO2+ XAOO
!
3n41+ NO2+ XAOO
!
3n44+ NO2+ XAOO
!
3n43+ NO2+ XAOO
!
3n49+ NO2+ XAOO
!
3v43+ NO2+ XAOO
!
3d42+ NO2+ XAOO
!
3n45+ NO2+ XAOO
!
3v44+ NO2+ XAOO
!
3d48+ NO2+ XAOO
k2 98 E/R
<4.0E-14 0.0E+00
8.6E-12 0.0E+00
4.6E-04 0.0E+00
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
Source
DeMore et al. [1997]
DeMore et al. [1997], See Table C.19
DeMore et al. [1997], See Table C.19
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
301
Table C.17 (continued) Peroxy Acyl Nitrate Updates
p pk49
p pk40
p pk45
p pk47
p pk48
p pd45
p pk46
p pk4A
p pn47
p pn48
p p041
p p042
p po41
p po42
p po43
p po45
p po47
p po44
p po46
p ph40
p pg40
p pd51
p pd52
p pu51
p pv53
p pu52
p pu53
p pk59
p pk51
p pk54
p pd53
p pd54
p pk52
p pk55
p pn51
p pn53
p pn52
p pn54
p pv56
p pn55
p pd55
p pd56
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
3k49+ NO2+ XAOO
3k40+ NO2+ XAOO
3k45+ NO2+ XAOO
3k47+ NO2+ XAOO
3k48+ NO2+ XAOO
3d45+ NO2+ XAOO
3k46+ NO2+ XAOO
3k4A+ NO2+ XAOO
3n47+ NO2+ XAOO
3n48+ NO2+ XAOO
3042+ NO2+ XAOO
3041+ NO2+ XAOO
3o42+ NO2+ XAOO
3o41+ NO2+ XAOO
3o43+ NO2+ XAOO
3o45+ NO2+ XAOO
3o47+ NO2+ XAOO
3o44+ NO2+ XAOO
3o46+ NO2+ XAOO
3h40+ NO2+ XAOO
3g40+ NO2+ XAOO
3d51+ NO2+ XAOO
3d52+ NO2+ XAOO
3u51+ NO2+ XAOO
3v54+ NO2+ XAOO
3u53+ NO2+ XAOO
3u52+ NO2+ XAOO
3k59+ NO2+ XAOO
3k51+ NO2+ XAOO
3k55+ NO2+ XAOO
3d53+ NO2+ XAOO
3d54+ NO2+ XAOO
3k52+ NO2+ XAOO
3k53+ NO2+ XAOO
3n51+ NO2+ XAOO
3n53+ NO2+ XAOO
3n52+ NO2+ XAOO
3n54+ NO2+ XAOO
3v56+ NO2+ XAOO
3n55+ NO2+ XAOO
3d55+ NO2+ XAOO
3d56+ NO2+ XAOO
k2 98 E/R
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
Source
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
302
Table C.17 (continued) Peroxy Acyl Nitrate Updates
p pk5A
p pk5C
p pk50
p pk57
p pk58
p p051
p p052
p p053
p po50
p po51
p po52
p po53
p po54
p po56
p po55
p p061
p po61
p pt91
p ptA1
p p031
p pu44
p pr71
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
!
Reaction
3k5A+ NO2+ XAOO
3k5C+ NO2+ XAOO
3k50+ NO2+ XAOO
3k57+ NO2+ XAOO
3k58+ NO2+ XAOO
3051+ NO2+ XAOO
3052+ NO2+ XAOO
3053+ NO2+ XAOO
3o57+ NO2+ XAOO
3o51+ NO2+ XAOO
3o52+ NO2+ XAOO
3o53+ NO2+ XAOO
3o54+ NO2+ XAOO
3o56+ NO2+ XAOO
3o55+ NO2+ XAOO
3061+ NO2+ XAOO
3o61+ NO2+ XAOO
3t91+ NO2+ XAOO
3tA1+ NO2+ XAOO
3031+ NO2+ XAOO
3u43+ NO2+ XAOO
3r71+ NO2+ XAOO
a Average of reported values
k2 98 E/R
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
6.1E-04 1.4E+04
4.7E-04 1.3E+04
3.5E-04 1.3E+04
1.6E-04 1.3E+04
Source
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994]
Atkinson [1994] a
Atkinson [1994]
Madronich and Calvert [1989]
303
Table C.18 Revised Aromatic Reactions.
Reaction
C6 H6 + HO ! 0.21 C6 H5 (H)OH(OO) + 0.79 C6 H5 (OH) + 0.79 HO2
C6 H6 + NO3 ! C6 H5(OO) + HNO3
A
C6 H5 (OH) + HO ! C6 H5 (O) + H2 O
B
C6 H5 (OH) + HO ! C6 H5 (OH)(OH)
C6 H5 (OH) + NO3 ! C6 H5 (O) + HNO3
C6 H4 OH,NO2 + HO ! C6 H4(O),NO2 + H2 O
C6 H4 OH,NO2 + NO3 ! C6 H4 (O),NO2 + HNO3
New K298
1.2E-12
<3.0E-17
New E/R
2.1E+02
0.0E+00
2.1E-12
4.0E+02
Atkinson [1994] b
2.4E-11
3.8E-12
2.3E-11
<2.0E-14
4.0E+02
0.0E+00
0.0E+00
0.0E+00
Atkinson [1994]
Atkinson [1994]
Grosjean [1991]b
Atkinson [1994]
a New Reaction
b Branching ratio from Madronich and Calvert [1989] retained
Sources
Atkinson [1994]
Atkinson [1994] a
304
Table C.19 Troe Reaction Updates.
Reaction
i H + O2 + (M) ! HO2 + (M)
i HO HO (M) ! H2O2 (M)
i HO NO (M) ! HNO2 (M)
i HO NO2 (M) ! HNO3 (M)
i NO O3P (M) ! NO2 (M)
i NO2 O3P (M) ! NO3 (M)
i NO3 NO2 (M) ! N2O5 (M)
u C2H2 HO (M) ! dd21 HO (M)
u C2H4 + HO + (M) ! 0o21 (M)
0 CH3 O2 (M) ! 2011 (M)
0 C2H5 O2 (M) ! 2021 XPOO (M)
1 CH3O NO (M) ! w012 (M)
1 CH3O NO2 (M) ! n011 (M)
1 1021 NO (M) ! w022 (M)
1 1021 NO2 (M) ! n021 (M)
2 2011 NO2 (M) ! n012 (M)
3 3021 NO2 (M) ! p021 -1.00 XAOO (M)
p p021 (M) ! 3021 NO2 XAOO (M)
n n012 (M) ! 2011 NO2 (M)
k298, E/R a
Reference
Troe Parameters b
1.2E-12 -1.0E+03
Madronich and Calvert [1989]c
5.7e-32 1.6 7.5e-11 0.0 0.6 1. 0.
5.9E-12 -6.2E+02
DeMore et al. [1997]d
6.2e-31 1.0 2.6e-11 0.0 0.6 1. 0.
[DeMore et al., 1997]d
7.3E-12 -1.0E+03
7.0e-31 2.6 3.6e-11 0.1 0.6 1. 0.
[DeMore et al., 1997]d
8.5E-12 -1.4E+03
2.5e-30 4.4 1.6e-11 1.7 0.6 1. 0.
[Madronich and Calvert, 1989]c
1.6E-12 -8.6E+02
9.0e-32 1.5 3.0e-11 0.0 0.6 1. 0.
[Madronich and Calvert, 1989]c
1.6E-12 -1.1E+03
9.0e-32 2.0 2.2e-11 0.0 0.6 1. 0.
[DeMore et al., 1997]d;e
1.3E-12 -5.6E+02
2.2e-30 3.9 1.5e-12 0.7 0.6 1. 0.
7.5E-13 1.3E+03
Madronich and Calvert [1989]c;e
5.5E-30 0.0 8.3E-13 -2. 0.6 1. 0.
8.2E-12 -1.2E+01
DeMore et al. [1997]d
1.0E-28 0.8 8.8E-12 0.0 0.6 1. 0.
1.1E-12 -1.2E+03
DeMore et al. [1997]d
4.5E-31 3.0 1.8E-12 1.7 0.6 1. 0.
7.5E-12 -1.2E+03
DeMore et al. [1997]d;e
1.5E-28 3.0 8.0E-12 0.0 0.6 1. 0.
[DeMore et al., 1997]e;f
2.5E-11 0.0E+00
1.4e-29 3.8 3.6e-11 0.6 0.6 1.0 0.
[DeMore et al., 1997]e
1.5E-11 0.0E+00
1.1e-28 4.0 1.6e-11 1.0 0.6 1. 0.
[DeMore et al., 1997]e
4.7E-11 0.0E+00
2.8e-27 4.0 5.0e-11 1.0 0.6 1.0 0.
[DeMore et al., 1997]e;f
2.7E-11 0.0E+00
2.0e-27 4.0 2.8e-11 1.0 0.6 1. 0.
4.0E-12 -1.8E+03
Madronich and Calvert [1989]c
1.5E-30 4.0 6.5E-12 2.0 0.6 1. 0.
8.6E-12 0.0E+00
DeMore et al. [1997]e
9.7e-29 5.6 9.3e-12 1.5 0.6 1.0 0.
4.6E-04 0.0E+00
DeMore et al. [1997]e
9.7e-29 5.6 9.3e-12 1.5 0.6 2.3e-08 1.4e+04
1.5E+00 9.4E+03
Madronich and Calvert [1989]c
1.5e-30 4.0 6.5e-12 2.0 0.6 2.7e-12 1.1e+04
a these values not actually used
b AK0300, AN, AKI300, AM, BAS, AEQUIL, TEQUIL. Where AK0300 = zero pressure 300 K rate
constant (third order); AN = temperature exponent for zero pressure rate constant; AKI300 = high pressure
300 K rate constant (second order); AM = temperature exponent for high pressure rate constant; BAS = base
of exponentiation (0.6 for most); AEQUIL = pre-exponential of equilibrium constant; TEQUIL = activation
temperature of equilibrium constant
c Recommended by DeMore et al. [1997]
d E/R from Madronich and Calvert [1989]
e No E/R value reported
f New reaction