PB87-180600
Surrogate Species Chemical Reaction
Mechanism for Urban-Scale Air Quality
Simulation Models. Volume 2
Guidelines for Using the Mechanism
Environmental Research and Technology, Inc.
Newbury Park, CA
Prepared for
Environmental Protection Agency
Research Triangle Park, NC
Apr 87
Mtrmjtion Service
-------
PDb7- 180oOO
EPA/600/3-87/014b
April 1987
A SURROGATE SPECIES CHEMICAL REACTION MECHANISM
FOR URBAN-SCALE AIR QUALITY SIMULATION MODELS
VOLUME II - GUIDELINES FOR USING THE MECHANISM
by
Frederick W. Lurmann
William P. L. Carter
Lori A. Coyner
ERT, A Resource Engineering Company, Inc.
975 Business Center Circle
Newbury Park, CA 91320
and
Statewide Air Pollution Research Center
University of California
Riverside, CA 92521
EPA Contract No. 68-02-4104
Project Officer
Marcia C. Dodge
Atmospheric Chemistry and Physics Division
Atmospheric Sciences Research Laboratory
Research Triangle Park, NC 27711
ATMOSPHERIC SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NC 27711
-------
NOTICE
The information in this document has been funded by the
United States Environmental Protection Agency under Contract
Number 68-02-4104 to ERT, Inc. It has been subject to the
Agency's peer and administrative review, and it has been
approved for publication as an EPA document. Mention of
trade names or commercial products does not constitute
endorsement or recommendation for use.
-11-
-------
ABSTRACT
A surrogate species chemical reaction mechanism for the photo-
oxidation of nonmethane organic compounds (NMOC) and nitrogen oxides
(NO ) has been developed for use in urban-scale photochemical air quality
X
simulation (AQS) models. The chemical mechanism has been evaluated
against data from 491 environmental chamber experiments conducted in
indoor and outdoor facilities. The results of the mechanism evaluation
indicate good model performance for a large number of single organic-NO
X
and multi-organic NO experiments.
A
Two versions of the chemical mechanism have been adapted for use in
photochemical AQS models. One version of the mechanism incorporates
detailed representation of the reactions of NMOC and is suitable for use
in single-cell AQS models such as the OZIPM/EKMA model. Another version
of the mechanism incorporates a more condensed representation of the
reactions of NMOC and is suitable for use in multi-cell Lagrangian and
Eulerian AQS models. Under typical urban conditions, the two versions of
the mechanism give very similar predictions for the concentrations of the
key species involved in photochemical smog.
The approach used to model the complex mixture of NMOC with this
mechanism is to use the chemical reactions of 12 common organic
precursors as surrogates for actual reactions of hundreds of different
compounds. A system of assigning individual organic compounds to the
most appropriate surrogate species have been developed. Also, speciated
ambient NMOC data from surface stations in 25 urban areas and from
aircraft samples collected upwind of four urban areas have been analyzed
to develop default NMOC speciation profiles for use with this mechanism.
Sensitivity analysis using surrogate species mechanism in the
OZIPM/EKMA model is reported. This analysis investigates the relation-
ships between model input parameters and the NMOC control requirement
predictions. The input parameters included in the analysis are NMOC
composition, NMOC/NO ratio, NMOC and ozone concentrations aloft, dilu-
X
tion rates, post-8 a.m. emission rates, future NO emission rates,
X
present-day ozone concentrations, photolysis rates, and initial concen-
trations of peroxyacetylnitrate and nitrous acid.
-111-
-------
TABLE OF CONTENTS
1. INTRODUCTION 1-1
2. IMPLEMENTATION OF THE MECHANISM 2-1
2.1 Photolytic Reactions 2-1
2.2 Special Product Coefficients and Rate Constants 2-17
2.3 Steady-State Approximations 2-24
2.4 Sample Problems 2-30
3. SPECIATION OF NMOC 3-1
3.1 Assignment of Individual Species to Classes 3-1
4. REFERENCES 4-1
APPENDIX A - PHOTOLYTIC REACTION RATE DATA
-V-
-------
LIST OF TABLES
Table Title Page
2-1 SAPRC/ERT OZIPM Chemical Mechanism Species List 2-2
2-2 SAPRC/ERT OZIPM Chemical Mechanism 2-4
2-3 SAPRC/ERT Condensed Chemical Mechanism Species List 2-8
2-4 SAPRC/ERT Condensed Chemical Mechanism 2-9
2-5 Representation of NMOC in the OZIPM Mechanism 2-12
2-6 Representation of NMOC in the Condensed Mechanism 2-15
2-7 Estimated Clear Sky Photolytic Reaction Rates 2-16
(Per Second) at the Earth's Surface
2-8 ^ Ratios of Other Clear Sky Photolytic Reaction Rates 2-16
to the NO- Photolytic Rate at the Earth's Surface
2-9 Example of Special Subroutine for the OZIPM Mechanism 2-18
2-10 Example of Special Subroutine for the Condensed 2-21
Mechanism
2-11 Characteristic Reaction Time in Urban Environments 2-25
2-12 Characteristic Time in Low NO Environments 2-26
X
2-13 Diagnostic Equations for the Steady-State Species 2-28
in the OZIPM Mechanism
2-14 Diagnostic Equations for the Steady-State Species 2-29
in the Condensed Mechanism
2-15 Input Parameters for Test Problem #1 2-32
2-16 Test Problem ttl - Constant Solar Radiation - 2-34
131 Reaction Mechanism
2-17 Input Parameters for Test Problem #2 2-38
2-18 Test Problem #2 - Constant Solar Radiation - 2-4C
94 Reaction Mechanism
2-19 Example #3 2-43
2-20 Example #4 2-69
3-1 NMOC Classes for the OZIPM Mechanism 3-2
-vi-
-------
LIST OF TABLES (continued)
Table Title Page
3-2 NMOC Classes for the Condensed Mechanism 3-2
3-3 Organic Species Classification for the OZIPM 3-4
Chemical Mechanism
3-4 Recommended Default NMOC Composition Profiles 3-11
3-5 Range of NMOC Composition Fractions 3-11
-vii-
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1. INTRODUCTION
This is the fourth volume in a series on a new atmospheric chemical
mechanism for use in photochemical air quality simulation (AQS) models.
The chemical mechanism is designed to predict the formation of ozone and
other oxidants from emissions of nonmethane organic compounds (NMOC) and
nitrogen oxides (NO ) in urban areas. It is designed for use in models
X
such as the OZIPM model (Hogo and Whitten 1986) and the Urban Airshed
Model (Reynolds et al. 1973). These models are used to develop ozone
control strategies for urban areas where ozone concentrations exceed the
National Ambient Air Quality Standard.
The new mechanism was developed by updating and extending the
Atkinson et al. (1982) and Lurmann et al. (1984, 1986) mechanisms based
on the recommendations of Atkinson and Lloyd (1984) and NASA (1985). The
mechanism employs the surrogate species approach to represent the
reactions of NMOC in ambient air. The mechanism was extensively tested
and refined using over 490 environmental chamber experiments from the
University of North Carolina (UNC) and the University of California,
Riverside (UCR) facilities. Two versions of the mechanism have been
adapted for use in atmospheric simulation models. One version, referred
to as the OZIPM mechanism, is designed for use in single cell AQS models,
that can accommodate fairly large and detailed chemical mechanisms. The
second version, referred to as the condensed mechanism, is designed for
use in multi-cell AQS models that include more sophisticated treatment of
transport processes and require smaller chemical mechanisms.
The technical basis for the new mechanism is fully documented in
companion reports. The mechanism development, evaluation protocol, and
preliminary evaluation results are described in Volumes I and II of a
report entitled "Development and Testing of a Surrogate Species Chemical
Reaction Mechanism" (Carter et al. 1986). The final mechanism evaluation
results and the adaptation of the mechanism to atmospheric models are
described in Volume I of this report.
The purpose of this report is to provide guidelines for using the
new chemical mechanism in air quality models. Included in this report are
• instructions for implementing the mechanism in AQS models.
1-1
-------
• sample problems that allow users to confirm that they have
properly implemented the chemical mechanism, and
• instructions for speciating the NMOC into the organic compound
classes used by the model.
The guidelines for implementation and NMOC speciation are provided in
Sections 2 and 3 of the report, respectively. Computer-readable listings
(files) of the mechanism are available from LRT, Inc. for a nominal cost.
These files include sample problem input data for the OZIPM computer
program.
1-2
-------
2. IMPLEMENTATION OF THE MECHANISM
The chemical mechanisms developed in this research program can be
implemented in almost all photochemical AQS models. The AQS models have
different input data formats, numerical integration procedures, and
capabilities for treating photolytic reaction rates. Some models are
able to accommodate special rate constant and product coefficient
expressions, whereas other models only accept rate data in standard
format with constant product coefficients. Furthermore, most single cell
models have the capability to read all of the mechanism data from an
input file, whereas, most sophisticated multi-cell models require the
chemistry to be implemented in "hard-wired" chemistry subroutines.
Because of these difference, it is beyond the scope of this report to
describe all the details of implementing the mechanism in different
models. However, the general features that need to be considered in all
implementations are described and sample input files for EPA's OZIPM
model (Version 3) are provided.
The two versions of the new chemical mechanism are shown in
Tables 2-1 tnrough 2-4. Tables 2-1 and 2-3 list the chemical species
that are included in the OZIPM and condensed mechanisms, respectively.
Tables 2-2 and 2-4 show the reactions, the nonphotolytic rate constants
at 298°K, and activation energies for the OZIPM and condensed mechanisms,
respectively. These rate constants are appropriate for the lower
troposphere where the atmospheric pressure is in the 700 to 1000 mb
range. The first order rate constants are given in minute and second
units. The second order rate constants are given in ppm min and cm
molecules sec units. The third order rate constants are given in
— ? —1 6 — 2 —1
ppm min and cm molecules sec units. The organic classes and
surrogate species used in the mechanism are shown in Tables 2-5 and 2-6.
2.1 Photolytic Reactions
The rates for the photolytic re?i.ctions depend on solar radiation
intensity and its spectral distribution. Atmospheric radiation levels
depend on the solar zenith angle, cloud cover, pollutant loadings,
surface albedo, and elevation above the Earth's surface. The solar
2-1
-------
TABLE 2-1
SAPRC/ERT OZIPM CHEMICAL MECHANISM SPECIES LIST
SPECIES
1. NITRIC OXIDE
2. NITROGEN DIOXIDE
3. OZONE
4. NITROUS ACID
5. NITRIC ACID
6. PERNITRIC ACID
7. NITROGEN PENTOXIDE
8. NITROGEN TRIOXIDE
9. HYDROPEROXY RADICAL
10. HYDROGEN PEROXIDE
11. CARBON MONOXIDE
12. FORMALDEHYDE
13. ACETALDEHYDE
14. PROPIONALDEHYDE
15. PEROXYACETYLNITRATE
16. PEROXYPROPIONYL NITRATE
17. TOTAL R02 RADICALS
18. TOTAL RC03 RADICALS
19. ORGANIC PEROXIDE
20. ACETONE
21. METHYL ETHYL KETONE
22. GLYOXAL
23. GLYOXAL PAN
24. METHYL GLYOXAL
25. C4-C5 ALKANES
26. >C5 ALKANES
27. ALKYL NITRATE
28. ETHENE
29. PROPENE
30. TRANS-2-BUTENE
31. TOLUENE
32. M-XYLENE
33. 1,3,5 TRI-M-BENZENE
34. DICARBONYLS
35. 0-CRESOL
36. PHENOLS
37. NITROPHENOL
STEADY-STATE SPECIES
38. OXYGEN - SINGLET D
39. OXYGEN - ATOMIC
40. HYDROXYL RADICAL
ABREVIATION
NO
N02
03
HONO
HN03
HN04
N205
N03
HO 2
H202
CO
HCHO
ALD2
RCHO
PAN
PPN
R02
RC03
ROOH
ACET
MEK
GLYX
GPAN
MGLY
ALK4
ALK7
ALKN
ETHE
PRPE
TBUT
TOLU
XYLE
TMBZ
DIAL
CRES
PHEN
NPHE
0*SD
0
OH
2-2
-------
TABLE 2-1 (Continued)
SPECIES ABREVIATION
41. ACETALDEHYDE RC03 MC03
42. PROPIONALDEHYDE RC03 PC03
43. GLYOXAL RC03 GC03
44. GENERAL R02 #1 R02R
45. GENERAL R02 #2 R202
46. ALKYL NITRATE R02 R02N
47. fHENOL R02 R02P
48. BENZALDEHYDE N-R02 BZN2
49. PHENOXY RADICAL BZO
CONSTANT SPECIES
50. WATER VAPOR H20
2-3
-------
TABLE 2-2
SAPRC/ERT OZIPM CHEMICAL MECHANISM
REACTION
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
N02 +
0
0 +
0 +
NO +
N02 +
NO +
NO +
N02 +
N205
N205 +
N02 +
N03 +
N03 +
03 +
03 +
0*SD +
0*SD
NO +
HONO +
N02 +
N02 +
HN03 +
CO +
03 +
NO +
N02 +
HN04
HN04 +
03 +
H02 +
H02 +
N03 +
N03 +
H202 +
H202 +
R02 +
RC03 +
HV
N02
N02
03
03
N03
NO
N03
H20
N03
HV
HV
HV
HV
H20
OH
HV
H20
OH
OH
OH
OH
H02
H02
OH
H02
H02
H02 +
H02
H02 +
HV
OH
NO
NO
— -> NO + 0
— > 03
---> NO
---> N03
---> N02
-— > N03
— > 2.N02
- — > 2.N02
— > N205
---> N02 + N03
— > 2.HN03
---> NO '+ N02
— -> NO
-— > N02 + 0
---> 0
— > 0*SD
— > 2. OH
— > 0
— > HONO
— > NO + OH
— -> HONO - N02 + HN03
— > HN03
— > N03
— -> H02
• — > H02
---> N02 + OH
— > HN04
---> N02 + H02
— > N02
— > OH
---> H202
H20 — > H202
— > HN03
H20 — -> HN03
— -> 2. OH
— > H02
— > NO
— > NO
MOLECULE -
CC-SEC PPM-MIN
(298 K) (298 K)
RADIATION DEPENDENT
8.12E+05 4.87E+07
9.30E-12 1.37E+04
2.23E-12 3.29E+03
1.81E-14 2.68E+01
3.23E-17 4.77E-02
1.86E-11 2.75E+04
1.02E-19 1.50E-04
1.15E-12 1.71E+03
3.47E-02 2.08E+00
l.OOE-21 1.48E-06
4.04E-16 5.98E-01
RADIATION DEPENDENT
RADIATION DEPENDENT
RADIATION DEPENDENT
RADIATION DEPENDENT
2.20E-10 3.25F.+05
7.20E+08 4.32E-HO
6.60E-12 9.75E+03
RADIATION DEPENDENT
4.00E-24 5.91E-09
1.13E-11 1.68E+04
1.28E-13 1.89E+02
2.18E-13 3.22E+02
6.78E-14 l.OOE+02
8.28E-12 1.22E+04
1.37E-12 2.02E+03
8.22E-02 4.93E+OQ
4.00E-12 5.91E+03
2.01E-15 2.96E+00
3.02E-12 4.46E+03
6.97E-30 2.54E-01
3.02E-12 4.46E+03
6.97E-30 2.54E-0]
RADIATION DEPENDENT
1.66E-12 2.45E+03
7.68E-12 1.14E+04
7.68E-12 1.14E+04
EXPRESSION
1.10E+04*EXP( 1282/T)
1.11E-13*EXP( 894/T)
1.80E-12*EXP( -1370/T)
1.20E-13*EXP( -2450/T)
8.00E-12*EXP( 252/T)
1.72E-20*EXP( 529/T)
4.62E-13*EXP( 273/T)
1 . 33E+15*EXP(- 1 1379/T)
2.50E-14*EXP( -1229/T)
4.03E-13*EXP( 833/T)
9.57E-13*EXP( 737/T)
9.40E-15*EXP( 778/T)
1.6Ge:-12*EXP( -942/T)
3.70E-12*EXP( 240/T)
1.02E-13*EXP( 773/T)
4.35E+13*EXP(-10103/T)
1.40E-14*EXP( -579/T)
2.27E-13*EXP( 771/T)
3.26E-34*EXP( 2971/T)
2.27E-13*EXP( 771/T)
3.26E-34*EXP( 2971/T)
3.10E-12*EXP( -187/T)
4.20E-12*EXP( 180/T)
4.20E-12*EXP( 180/T)
-------
TABLE 2-2 (Continued)
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.
RC03
R02
RC03
ROOH
R02
R02
RC03
HCHO
HCHO
HCHO
HCHO
HCHO
ALD2
ALD2
ALD2
MC03
MC03
MC03
MC03
MC03
PAN
RCHO
RCHO
RCHO
PC03
PC03
PC03
PC03
PC03
PPN
ACET
ACET
MEK
MEK
GLYX
GLYX
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
-h
+
+
+
+
+
+
+
+
+
-h
+
-f
-f
+
-f
+
+
+
N02
H02
H02
HV
R02
RC03
RC03
HV
HV
OH
N03
H02
OH
HV
N03
NO
N02
H02
R02
RC03
OH
HV
N03
NO
N02
H02
R02
RC03
HV
OH
HV
OH
HV
OH
REACTION
:::>
— >
— >
>
>
>
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
— >
N02
H02
H02
H02 +
2.H02 +
CO
H02 +
HN03 +
R02R +
MC03 +
CO +
HN03 +
N02 +
PAN
ROOH +
.5H02 +
H02 +
MC03 +
RC03 +
ALD2 +
HN03 +
N02 +
PPN
ROOH +
.5H02 +
H02 +
PC03 +
MC03 +
MGLY +
MC03 +
1.5R202 +
+ .5PC03 +
.13HCHO +1
.63H02 -H
OH
CO
CO
H02 +
R02
RC03
HCHO +
MC03 +
HCHO +
HCHO
HCHO +
HCHO +
N02 +
PC03
H02 +
PC03 +
ALD2 +
ALD2
ALD2 +
ALD2 +
N02 +
HCHO +
R02R +
ALD2 +
1 . 5R02 +
RC03
.87CO
.26CO +
CO
H02 + R02R •«• R02
RC03
R02R + R02
R02
RC03
RC03
CO + R02R + R02
RC03
R02R + R02
R02
RC03
RC03
RC03 + R02R + R02
R02
RC03 + R02R + R02
.5MC03 -»• .5ALD2 + .5HCHO
.37GC03 + .37RC03
MOLECULE-
CC-SEC PPM-MIN
(298 K) (298 K)
5.12E-12 7.57E+03
3.00E-12 4.43E+03
3.00E-12 4.43E+03
RADIATION DEPENDENT
l.OOE-15 1.48E+00
3.00E-12 4.43E+03
2.50E-12 3.69E+03
RADIATION DEPENDENT
RADIATION DEPENDENT
9.00E-12 1.33E+04
5.97E-16 8.82E-01
l.OOE-14 1.48E+01
1.60E-11 2.36E+04
RADIATION DEPENDENT
2.50E-15 3.69E+00
7.68E-12 1.14E+04
5.12E-12 7.57E+03
3.00E-12 4.43E+03
3.00E-12 4.43E+03
2.50E-12 3.69E+03
3.68E-04 2.21E-02
1.98E-11 2.93E+04
RADIATION DEPENDENT
2.46E-15 3.63E+00
7.68E-12 1.14E+04
5.12E-12 7.57E+03
3.00E-12 4.43E+03
3.00E-12 4.43E+03
2.50E-12 3.69E+03
3.68E-04 2.21E-02
RADIATION DEPENDENT
2.29E-13 3.39E-t-02
RADIATION DEPENDENT
9.85E-13 1.46E+03
RADIATION DEPENDENT
1.15E-11 1.70E+04
EXPRESSION
2.80E-12*EXP( 180/T)
6.00E-13*EXP( -2060/T)
6.90E-12*EXP( 250/T)
3.00E-13*EXP( -1427/T)
4.20E-12*EXP( 180/T)
2.80E-12*EXP( 180/T)
2.00E-H6*EXP(-13542/T)
8.50E-12*EXP( 252/T)
3.00E-13*EXP( -1432/T)
4.20E-12*EXP( 180/T)
2.80E-12*EXP( 180/T)
2.00E-H6*EXP(-13542/T)
1.00E-11*EXP( -1125/T)
1.20E-11*EXP( -745/T)
-------
TABLE 2-2 (Continued)
SAPRC/ERT OZIPM CHEMICAL MECHANISM
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
GLYX
GC03
GC03
GPAN
GC03
GC03
GC03
MGLY
MGLY
MGLY
ALK4
ALK7
ALKN
R02N
R02N
R02N
R02N
R202
R202
R202
R202
R02R
R02R
R02R
R02R
ETHE
ETHE
ETHE
ETHE
PRPE
PRPE
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
•f
+
+
+
+
+
+
+
N03
N02
NO
H02
R02
RC03
HV
OH
N03
OH
OH
OH
NO
H02
R02
RC03
NO
H02
R02
RC03
NO
H02
R02
RC03
OH
03
0
N03
OH
03
REACTION
!
> HN03
> GPAN
> N02
•> NO?
f n\j£f
> ROOH
> .5H02
> H02
> MC03
> MfOI
S \\\j\Jj
s mam
— ->B01*HCHO
.....
*. K .
...
+B06*R02N
>B10*HCHO
+B15*R02N
> N02
+1 .39R202
> ALKN
> ROOH
> R02
> RC03
> N02
> ROOH
> R02
> RC03
> N02
> ROOH
> .5H02
> .5H02
> R02R
> HCHO
> HCHO
> N02
> R02R
> .65HCHO
+.135R02R
+ .63H02
+ H02
+ GC03
+ CO
+ CO
+ CO
+ H02
+ CO
+ MC03
+B02*ALD2
+B07*R02R
+B11*ALD2
+B16*R02R
+ .15MEK
•H.39R02
+ MEK
+ .5H02
+ .5H02
+ H02
+ R02
+ RC03
+ R02
+ .12H02
+ H02
+ 2. HCHO
+ HCHO
+ .5ALD2
+.135R02
+ 1
-f
+
+
+
+
+
+
.26CO
CO
RC03
R02
RC03
CO
RC03
CO
+B03*RCHO
+B08*R202
+B12*RCHO
+B17*R202
-H.05RCHO
+
+
-n
+
-»•
+
+
+ .
MEK
MEK
.56HCHO
.42CO
CO
R202
ALD2
285CO
+ .37GC03 + .37RC03
+ RC03
+ RC03
+B04*ACET +B05*MEK
+B09-R02
+B13*ACET +B14*MEK
-t-B18-R02
+ .48ALD2 + .16HCHO
+ .22ALD2
+ R02R + R02
+ R02
+ R02
+ .060H +.165H02
MOLECULE-
CC-SEC
(298 K)
6.01E-16
5.12E-12
7.68E-12
3.68E-04
3.68E-04
3.00E-12
3.00E-12
2.50E-12
RADIATION
1.70E-11
2.50E-15
3.22E-12
SEE TEXT
6.16E-12
SEE TEXT
2.03E-12
7.68E-12
3.00E-12
l.OOE-15
3.00E-12
7.68E-12
3.00E-12
l.OOE-15
3.00E-12
7.68E-12
3.00E-12
l.OOE-15
3.00E-12
8.54E-12
1.74E-18
7.29E-13
1.10E-16
2.63E-11
1.13E-17
PPM-MIN
(298 K)
8.
7.
1.
2.
2.
4.
4.
3.
88E-01
57E+03
14E+04
21E-02
21E-02
43E+03
43E+03
69E+03
6,
2,
4,
2
2
EXPRESSION
.OOE-13*EXP(
.80E-12*EXP(
,20E-12*EXP(
-2058/T)
180/T)
180/T)
.OOE-H6*EXP(-13542/T)
.OOE-H6*EXP(-13542/T)
DEPENDENT
2.
3.
4.
9.
3.
1.
4.
1.
4.
1.
4.
1.
4.
1.
4.
1.
4.
1,
2,
51E+04
69E+00
76E+03
11E+03
OOE+03
14E+04
43E+03
48E+00
43E+03
14E+04
43E+03
48E+00
43E+03
14E+04
43E+03
48E+00
43E+03
, 26E+04
.57E-03
1.08E+03
1.62E-01
3.89E+04
1.67E-02
3
1
1
2
4
4
4
2
1
1
2
4
1
.OOE-13*EXP(
.05E-11*EXP(
.62E-11*EXP(
.19E-11*EXP(
.20E-12*EXP(
.20E-12*EXP(
.20E-12*EXP(
.15E-12*EXP(
.20E-14*EXP(
.04E-11*EXP(
.OOE-12*EXP(
.85E-12*EXP(
-32E-14*EXP(
-1427/T)
-353/T)
-288/T)
-709/T)
180/T)
180/T)
180/T)
411/T)
-2634/T)
-792/T)
-2923/T)
504/T)
-2105/T)
-------
TABLE 2-2 (Continued)
106. PRPE
107.
108.
109.
110.
111.
112.
113.
114.
115.
116.
117.
118.
119.
120.
121.
122.
123.
124.
125.
126.
127.
128.
129.
130.
131.
PRPE
TBUT
TBUT
TBUT
TBUT
TOLU
XYLE
TMBZ
DIAL
DIAL
CRES
CRES
R02P
R02P
R02P
R02P
BZO
BZO
BZO
PHEN
PHEN
NPHE
BZN2
BZN2
BZN2
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
•f
+
+
+
N03
OH
03
0
N03
OH
OH
OH
OH
HV
OH
N03
NO
H02
R02
RC03
N02
H02
OH
N03
N03
N02
H02
REACTION
>
i
>
>
>
^
>
j
— — — >
^
_ _ — >
H
— ;
H
_ v — **
_ _ _ >
;
;
;
•» V ^>
-.
«•. — **
}
}
^
}
• _ _ N
«. v — >
_ — — >
\
— :
.6ACET
• .4CO
N02
R02R
ALD2
• .27R02
MEK
N02
• .16CRES
M44MGLY
• .17CRES
r.316MGLY
• .17CRES
>• .86MGLY
PC03
H02
• . 2MGLY
HN03
NPHE
ROOH
> .5H02
• .5H02
NPHE
PHEN
PHEN
• .2GLYX
HN03
HN03
»
NPHE
NPHE
+ .4HCHO +
+ . 6R02
* HCHO +
+ 2.ALD2 +
+ .15CO +
+ .30HCHO
+ . 4H02
+ 2.ALD2 +
+ .16H02 +
+.114GLYX
+ .17H02 +
+.095GLYX
+ .17H02 +
+ RC03
+ CO +
+ .15R02P +
+ BZO
+ R02
+ RC03
+ .15R02P +
+ BZO
+ BZN2
.2ALD2 + .2H02 <- .6R02R
ALD2 + R202 + R02
R02
.27R02R + .120H + .21H02
R202 + R02
.84R02R + .4DIAL + .84R02
.83R02R + .83R02 + .65DIAL
.83R02R + .83R02 + .49DIAL
MC03 + RC03
.85R02R + R02
.85R02R + R02
MOLECULE-
CC-SEC
(298 K)
3.98E-12
7.57E-15
6.37E-11
2.00E-16
2.34E-11
3.79E-13
6.19E-12
2.45E-11
6.20E-11
3. OOE-11
RADIATION
4. OOE-11
2.20E-11
7.68E-12
3. OOE-12
l.OOE-15
3. OOE-12
1.50E-11
3. OOE-12
1. OOE-03
2.80E-11
3.80E-12
3.80E-12
1.50E-11
3. OOE-12
1. OOE-03
PPM-MIN
(298 K)
5.88E+03
1.12E+01
9.42E+04
2.96E-01
3.45E+04
5.61E+02
9.14E-»-03
3 . 62E+04
9.16E+04
4.43E+04
DEPENDENT
5.91E+04
3.25E+04
1.14E+04
4.43E^03
1.48E+00
4.43E+03
2.22E+04
4.43E+03
6. OOE-02
4.14E+04
5.62E+03
5.62E+03
2.22E+04
4.43E+03
6. OOE-02
EXPRESSION
1.18E-11*EXP( -324/T)
5.00E-12*EXP( -1935/T)
1.01E-11*EXP( 549/T)
9.08E-15*EXP( -1137/T)
2.26E-11*EXP( 10/T)
1.00E-11*EXP( -975/T)
2.10E-12*EXP( 322/T)
1.66E-11*EXP( 116/T)
4.20E-12*EXP( 180/T)
-------
TABLE 2-3
SAPRC/ERT CONDENSED CHEMICAL MECHANISM SPECIES LIST
SPECIES
1. NITRIC OXIDE
2. NITROGEN DIOXIDE
3. OZONE
4. NITROUS ACID
5. NITRIC ACID
6. PERNITRIC ACID
7. NITROGEN PENTOXIDE
8. NITROGEN TRIOXIDE
9. HYDROPEROXY RADICAL
10. CARBON MONOXIDE
11. FORMALDEHYDE
12. ACETALDEHYDE
13. METHYL ETHYL KETONE
14. METHYL GLYOXAL
15. PEROXYACETYLNITRATE
16. TOTAL R02 RADICALS
17. CH3C03 RADICAL
18. ALKYL NITRATE
19.
-------
TABLE 2-4
SAPRC/ERT CONDENSED CHEMICAL MECHANISM
REACTION
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
N02 +
0
0 +
0 +
NO +
N02 +
NO +
NO +
N02 +
N205
N205 +
N02 +
N03 +
N03 +
03 +
03 +
0*SD +
0*SD
NO +
HONO +
N02 +
N02 +
HN03 +
CO +
03 +
NO +
N02 +
HN04
HN04 +
03 +
H02 +
H02 +
N03 +
N03 +
R02 +
R02 *
R02 +
HV — ->
>
N02 — ->
N02 — >
03 — >
03 — >
N03 --->
NO — >
N03 — ->
>
H20 — >
N03 — >
HV --->
HV — ->
HV — >
HV — >
H20 — >
>
OH — >
1JV — >
H20 — >
OH — >
OH — >
OH -— >
OH — >
H02 — >
H02 — ->
>
OH — >
H02 — >
H02 — >
H02 + H20 — >
H02 — >
H02 + H20 — >
NO — >
H02 — >
R02 — ->
NO + 0
03
NO
N03
N02
N03
2.N02
2.N02
N205
N02 + N03
2.HN03
NO + N02
NO
N02 + 0
0
0*SD
2. OH
0
HONO
NO + OH
HONO - N02 + HN03
HN03
N03
H02
H02
N02 + OH
HN04
N02 + H02
N02
OH
HN03
HN03
NO
H02
MOLECULE-
CC-SEC PPM-MIN
(298 K) (298 K)
RADIATION DEPENDENT
7.75E+05 4.65E-KJ7
9.30E-12 1.37E+04
2.23E-12 3.29E+03
1.81E-1.4 2.68E-I-01
3.23E-17 4.77E-02
1.86E-11 2.75E+04
9.68E-20 1.43E-04
1.15E-12 1.71E+03
3.47E-02 2.08E+00
l.OOE-21 1.48E-06
4.04E-16 5.98E-01
RADIATION DEPENDENT
RADIATION DEPENDENT
RADIATION DEPENDENT
RADIATION DEPENDENT
2.20E-10 3.25E+05
7.20E+08 4.32E+10
6.60E-12 9.75E+03
RADIATION DEPENDENT
4.00E-24 5.91E-09
1.14E-11 1.68E+04
1.28E-13 1.89E+02
2.18E-13 3.22E+02
6.78E-14 l.OOE+02
8.28E-12 1.22E+04
1.37E-12 2.02E+03
8.22E-02 4.93E+00
4.00E-12 5.91E+03
2.01E-15 2.96E+00
3.02E-12 4.46E+03
6.97E-30 2.54E-01
3.02E-12 4.46E+03
6.97E-30 2.54E-01
7.68E-12 1.14E+04
3.00E-12 4.43E+03
l.OOE-15 1.48E+00
EXPRESSION
1.05E+04*EXP( 1282/T)
1.11E-13*EXP( 894/T)
1.80E-12*EXP( -1370/T)
1.20E-13*EXP( -2450/T)
8.00E-12*EXP( 252/T)
1.64E-20*EXP( 529/T)
4.62E-13*EXP( 273/T)
1.33E-H5*EXP(-I1379/T)
2.50E-14*EXP( -1229/T)
4.03E-13*EXP( 833/T)
9.58E-13*EXP( 737/T)
9.40E-15*EXP( 778/T)
1.60E-12*EXP( -942/T)
3.70E-12*EXP( 240/T)
1.02E-13*EXP( 773/T)
4.35E+13*EXP(-10103/T)
1.40E-14*EXP( -579/T)
2.27E-13*EXP( 771/T)
3.26E-34*EXP( 2971/T)
2.27E-13*EXP( 771/T)
3.26E-34*EXP( 2971/T)
4.20E-12*EXP( 180/T)
-------
TABLE 2-4 (Continued)
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
± 57.
o
R02 +
HCHO +
HCHO •»•
HCHO +
HCHO +
HCHO +
ALD2 +
ALD2 -f
ALD2 +
MC03 +
MC03 +
MC03 +
MC03 +
PAN
MEK +
HEK +
MGLY +
MGLY +
MGLY +
ALKA +
MC03
HV
HV
OH
N03
H02
OH
HV
N03
NO
N02
H02
MC03
HV
OH
HV
OH
N03
OH
58. ALKN + OH
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
R02N +
R02N +
R02N +
R02N +
R202 +
R202 +
R202 +
R202
R02R +
R02R +
R02R +
R02R +
ETHE +
ETHE +
NO
H02
R02
MC03
NO
H02
R02
MC03
NO
H02
R02
MC03
OH
03
REACTION
>
— > 2
>
>
>
>
>
>
>
>
>
>
— > 2
>
>
— -> 1.
>
>
>
MC03
.H02 + CO
CO
H02 + CO
HN03 + H02
R02R + R02
MC03
CO + HCHO
HN03 + MC03
N02 + HCHO
PAN
HCHO
.H02 + 2. HCHO
MC03 + N02
ALD2 + MC03
5R02R + 1.5R02
MC03 + H02
HC03 + CO
HN03 + MC03
-— >B01*HCHO +B02*ALD2
+ CO
+ H02 + R02R + R02
+ R02R + R02
+ R02R + R02
+ MC03 + .5ALD2 + . 5HCHO
* CO
+ CO
+B03*MEK +B04*R02N +B05*R02R
MOLECULE -
CC-SEC PPM-MIN
(298 K) (298 K)
3.00E-12 4.43E+03
RADIATION DEPENDENT
RADIATION DEPENDENT
9.00E-12 1.33E+04
5.97E-16 8.82E-01
l.OOE-14 1.48E+01
1.60E-11 2.36E-I-04
RADIATION DEPENDENT
2.50E-15 3.69E+00
7.68E-12 1.14E+04
5.12E-12 7.57E+03
3.00E-12 4.43E+03
2.50E-12 3.69E+03
3.68E-04 2.21E-02
RADIATION DEPENDENT
9.85E-13 1.46E+03
RADIATION DEPENDENT
1.70E-11 2.51E-I-04
2.50E-15 3.69E+00
SEE TEXT
+B06*R202 +B07*R02
>
>
>
>
>
>
>
>
>
>
>
>
>
>
>
N02 + .15MEK
+1.39R02
ALKN
MEK
R02 + . 5H02
HCHO + H02
N02
R02
HCHO + H02
N02 + H02
5H02 + R02
HCHO + H02
R02R + R02
HCHO + .12H02
•H.53ALD2 + .16HCHO -H.39R202
+ MEK
+ MEK
+1.56HCHO + .22ALD2
+ .42CO
2.03E-12 3.00E+03
7.68E-12 1.14E+04
3.00E-12 4.43E+03
l.OOE-15 1.48E+00
3.00E-12 4.43E+03
7.68E-12 1.14E+04
3.00E-12 4.43E+03
l.OOE-15 1.48E+00
3.00E-12 4.43E+03
7.68E-12 1.14E+04
3.00E-12 4.43E+03
l.OOE-15 1.48E+00
3.00E-12 4.43E+03
8.54E-12 1.26E*04
1.74E-18 2.57E-03
EXPRESSION
6.00E-13*EXP( -2060/T)
6.90E-12*EXP( 250/T)
3.00E-13*EXP( -1427/T)
4.20E-12*EXP( 180/T)
2.80E-12*EXP( 180/T)
2.00E+16*EXP(-13542/T)
1.20E-11*EXP( -745/T)
3.00E-13*EXP( -1427/T)
2.19E-11*EXP( -709/T)
4.20E-12*EXP( 180/T)
4.20E-12*EXP( 180/T)
4.20E-12*EXP( 180/T)
2.15E-12*EXP( 411/T)
1.20E-14*EXP( -2634/T)
-------
TABLE 2-4 (Continued)
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
93.
94.
95.
ETHE +
ETHE +
ALKE +
ALKE +
ALKE +
ALKE +
TOLU +
AROM +
DIAL +
DIAL +
CRES +
CRES +
R02P +
R02P +
R02P +
R02P +
BZO +
BZO +
BZO
NPHE +
BZN2 +
BZN2 +
BZN2
0
N03
OH
03
0
N03
OH
OH
OH
HV
OH
N03
NO
H02
R02
HC03
N02
H02
N03
N02
H02
REACTION
— > HCHO + H02
---> N02 + 2. HCHO
— >B08*HCHO +B09*ALD2
--->B10*HCHO +B11*ALD2
+B14*OH +B15*CO
— ->B16*CO +B17*MEK
+B21*R02R +B21*R02
— > N02 +B08*HCHO
— > .16CRES + .16H02
+.144MGLY +.114HCHO
— -> .17CRES + .17H02
+B23*MGLY +B24*HCHO
---> MC03
— > H02 + CO
> .2MGLY + .15R02P
---> HN03 + BZO
---> NPHE
>
— -> .5H02 + R02
— > HCHO + H02
— -> NPHE
>
>
— > HN03 + BZN2
>
— > NPHE
-— > NPHE
+ CO + R02R + R02
+ R202 + R02
+ R02R + R02
+B12*R02R -«-B12*R02 +B13*H02
+B18*HCHO +B19*ALD2 +B20*H02
+B09*ALD2 + R202 + R02
+ .84R02R + .4DIAL + .84R02
+.114CO
+ .83R02R + .83R02 +B22*DIAL
+B24*CO
+ MC03
+ .85R02R + R02
MOLECULE -
CC-SEC
(298 K)
7.29E-13
1.09E-16
SEE TEXT
SEE TEXT
SEE TEXT
SEE TEXT
6.19E-12
SEE TEXT
3.00E-11
RADIATION
4.00E-11
2.20E-11
7.68E-12
3.00E-12
l.OOE-15
3.00E-12
1.50E-11
3.00E-12
l.OOE-03
3.80E-12
1.50E-11
3.00E-12
l.OOE-03
PPM-MIN
(298 K)
1.08E+03
1.61E-01
9.14E+03
4.43E+04
DEPENDENT
5.91E+04
3.25E+04
1.14E+04
4.43E+03
1.48E+00
4.43E+03
2.22E+04
4.43E-f03
6.00E-02
5.62E+03
2.22E+04
4.43E+03
6.00E-02
EXPRESSION
1.04E-11*EXP( -792/T)
2.00E-12*EXP( -2925/T)
2.10E-12*EXP( 322/T)
4.20E-12*EXP( 180/T)
-------
TABLE 2-5
REPRESENTATION OF NMOC IN THE OZIPM MECHANISM
COMPOUND CLASS
ETHENE
TERMINAL ALKENES
INTERNAL ALKENES
C4-C5 ALKANES
C6+ ALKANES
MONO-ALKYLBENZENES
DI-ALKYLBENZENES
TRI-ALKYLBENZENES
FORMALDEHYDE
ACETALDEHYDE
HIGHER ALDEHYDES
HIGHER KETONES
SURROGATE SPECIES
ETHENE (ETHE)
PROPENE (PRPE)
TRANS-2-BUTENE (TBUT)
N-BUTANE* (ALK4)
N-PENTANE*
ISO-BUTANE*
ISO-PENTANE*
N-HEXANE* (ALK7)
N-HEPTANE*
N-OCTANE*
2,3-DIMETHYLBUTANE*
2-METHYLPENTANE*
2,3-DIMETHYLPENTANE*
ISO-OCTANE*
TOLUENE (TOLU)
M-XYLENE (XYLE)
MESITYLENE (TMBZ)
FORMALDEHYDE (HCHO)
ACETALDEHYDE (ALD2)
PROPIONALDEHYDE (RCHO)
METHYL ETHYL KETONE (MEK)
Rate contants and product coefficient based on a mixture of these
surrogate species.
2-12
-------
TABLE 2-6
REPRESENTATION OF NMOC IN THE CONDENSED MECHANISM
COMPOUND CLASS
ETHENE
HIGHER ALKENES
>C3 ALKANES
MONO-ALKYLBENZENES
DI-& TRI-ALKYLBENZENES
FORMALDEHYDE
HIGHER ALDEHYDES
HIGHER KETONES
SURROGATE SPECIES
ETHENE (ETHE)
PROPENE* (ALKE)
TRANS-2-BUTENE*
N-BUTANE* (ALKA)
N-PENTANE*
ISO-BUTANE*
ISO-PENTANE*
N-HEXANE*
N-HEPTANE*
N-OCTANE*
2,3-DIMETHYLBUTANE*
2-METHYLPENTANE*
2,3-DIMETHYLPENTANE*
ISO-OCTANE*
TOLUENE (TOLU)
M-XYLENE* (AROM)
MESITYLENE*
FORMALDEHYDE (HCHO)
ACETALDEHYDE (ALD2)
METHYL ETHYL KETONE (MEK)
* Rate contants and product coefficient based on a mixture of these
surrogate species.
2-13
-------
zenith angle, in turn, depends on geographic location, date, and time of
day. In most atmospheric modeling applications, detailed solar intensity
and spectral distribution data are not available so theoretical clear-sky
actinic flux values, such as those reported by Peterson (1976), are used.
In some model applications, the clear-sky values are adjusted to account
for cloud cover. However, most of the adjustment methods are very
approximate. Given the actinic fluxes, the photolytic reaction rates are
calculated from the equation
K(z,j) = I I(w,z) • A(w,j) • Q(w,j)
w
where
K = photolytic rate of species j at solar zenith angle z,
I = actinic flux for wavelength increment w and solar zenith
angle z,
A = absorption cross-section of species j for wavelength
increment w, and
Q = quantum yield of species j for wavelength increment w.
In applying this equation, it is important to perform the summation for
the smallest wavelength increment in I, A, or Q for which data are
available.
Clear sky values for the photolytic reaction rates in the mechanism
at zero elevation are shown in Table 2-7. These rates are based on the
solar actinic flux, absorption cross-section, and quantum yield data
shown in Appendix A. The ratios of other photolytic reactions rates to
the N02 photolytic rate at zero elevation are shown in Table 2-8. These
ratios are useful because the rates of other photolyic reactions are
calculated from the N0_ photolytic rate in many photochemical models.
These ratios are, of course, dependent on the solar zenith angle. Values
of the rates (and ratios) in between the zenith angles listed in the
tables can be obtained by interpolation.
The solar radiation intensity increases with elevation above the
surface. The clear-sky actinic flux typically increases 15% per 1000
meters (Peterson 1976). We recommend using elevation dependent
2-14
-------
K)
I
TABLE 2-7
ESTIMATED CLEAR SKY PHOTOLYTIC REACTION RATES (PER SECOND) AT THE EARTH'S SURFACE*
Reaction
N02 + hv --> NO + 0
N03 + hv --> NO + 02
N03 + hv --> N02 + 0
03 + hv --> 0+02
03 + hv --> 0*SD (270 K)
03 + hv --> 0*SD (300 K)
03 + hv --> 0*SD (330 K)
HONO + hv --> OH + NO
H202 + hv —> 2 OH
ROOH + hv --> OH -f H02
HCHO + hv --> H02 + CO
HCHO + hv —> H2 + CO
ALD2 + hv --> CO + CH302
RCHO + hv --> CO + C2H502
ACET + hv --> HCHO + MC03
MEK + hv --> ALD2 + MC03
BCHO + hv —> Nonreactive
GLYX + hv --> HCHO + CO
HGLY + hv --> H02 + MC03
DIAL + hv --> H02 + MC03
10
20
Solar Zenith Angle
30 40 50
60
70
78
86
8.29E-03 8.22E-03 8.02E-03 7.66E-03 7.10E-03 6.26E-03 5.05E-03 3.32E-03 1.64E-03 3.51E-04
1.87E-02 1.86E-02 1.83E-02 1.77E-02 1.70E-02 1.60E-02 1.43E-02 1.11E-02 6.65E-03 9.81E-04
1.70E-01 1.70E-01 1.70E-01 1.60E-01 1.50E-01 1.40C-01 1.30E-01 9.86E-02 5.82E-02 9.05E-03
4.57E-04 4.55E-04 4.46E-04 4.29E-04 4.06E-04 3.75E-04 3.25E-04 2.47E-04 1.46E-04 2.32E-05
3.38E-05 3.27E-05 2.94E-05 2.41E-05 1.77E-05 1.11E-05 5.30E-06 1.59E-06 3.57E-07 4.30E-08
3.78E-05 3.66E-05 3.30E-05 2.72E-05 2.03E-05 1.29E-05 6.34E-06 1.99E-06 4.59E-07 5.42E-08
4.18E-05 4.06E-05 3.67E-05 3.05E-05 2.30E-05 1.49E-05 7.55E-06 2.48E-06 6.02E-07 7.02E-08
1.63E-03 1.61E-03 1.57E-03 1.50E-03 1.38E-03 1.21E-03 9.58E-04 6.14E-04 2.96E-04 6.61E-05
7.53E-06 7.43E-06 7.07E-06 6.47E-06 5.62E-06 4.50E-06 3.15E-06 1.70E-06 7.05E-07 1.34E-07
7.53E-06 7.43E-06 7.07E-06 6.47E-06 5.62E-06 4.50E-06 3.15E-06 1.70E-06 7.05E-07 1.34E-07
3.02E-05 2.98E-05 2.83E-05 2.57E-05 2.21E-05 1.73E-05 1.18E-05 6.00E-06 2.32E-06 3.85E-07
4.63E-05 4.58E-05 4.41E-05 4.12E-05 3.68E-05 3.07E-05 2.28E-05 1.32E-05 5.85E-06 1.20E-06
4.86E-06 4.76E-06 4.41E-06 3.84E-06 3.09E-06 2.21E-06 1.30E-06 5.40E-07 1.65E-07 2.10E-08
9.84E-06 9.69E-06 9.17E-06 8.28E-06 7.05E-06 5.48E-06 3.66E-06 1.83E-06 6.98E-07 1.16E-07
1.11E-06 1.09E-06 1.02E-06 9.04E-07 7.50E-07 5.62E-07 3.56E-07 1.65E-07 5.81E-08 8.75E-09
1.58E-06 1.55E-06 1.46E-06 1.29E-06 1.07E-06 8.03E-07 5.09E-07 2.36E-07 8.30E-08 1.25E-08
4.30E-05 4.26E-05 4.12E-05 3.89E-05 3.54E-05 3.04E-05 2.34E-05 1.45E-05 6.78E-06 1.49E-06
6.46E-05 6.42E-05 6.31E-05 6.11E-05 5.80E-05 5.30E-05 4.53E-05 3.28E-05 1.78E-C5 3.42E-06
1.42E-04 1.42E-04 1.39E-04 1.35E-04 1.28E-04 1.17E-04 9.99E-05 7.19E-05 3.88E-05 7.52E-06
5.29E-04 5.23E-04 5.04E-04 4.71E-04 4.23E-04 3.55E-04 2.65E-04 1.56E-04 7.03E-05 1.50E-05
* Based on Peterson (1976) Solar Actinic Fluxes
-------
NJ
I
TABLE 2-8
RATIOS OF OTHER CLEAR SKY PHOTOLYTIC REACTION RATES TO THE N02 PHOTOLYTIC RATE AT THE EARTH'S SURFACE*
Reaction
N03 + hv —> NO * 02
N03 + hv --> N02 + 0
03 + hv --> 0+02
03 + hv --> 0*SD 270 K
03 + hv --> 0*SD 300 K
03 * hv —> 0*SD 330 K
HONO + hv --> OH + NO
H202 + hv --> 2 OH
ROOH + hv --> OH * H02
HCHO + hv --> 2 H02 + CO
HCHO + hv --> H2 + CO
ALD2 + hv --> HCHO + CH302
RCHO + hv --> ALD2 + C2H502
ACET + hv --> HCHO + MC03
MEK + hv --> ALD2 + MC03
ECHO + hv --> Nonreactive
GLYX * hv --> HCHO + H2 + CO
MGLY + hv --> H02 + MC03
DIAL + hv --> H02 + MC03
10
20
Solar Zenith Angle
30 40
50
60
70
86
2.3 2.3 2.3 2.3 2.4 2.6 2.8 3.3 4.1 2.8
20. 20. 21. 21. 22. 23. 25. 30. 36. 26.
5.52E-02 5.53E-02 5.56E-02 5.61E-02 5.71E-02 5.99E-02 6.45E-02 7.43E-02 8.90E-02 6.60E-02
4.08E-03 3.98E-03 3.66E-03 3.14E-03 2.50E-03 1.77E-03 1.05E-03 4.80E-04 2.18E-04 1.22E-04
4.56E-03 4.45E-03 4.12E-03 3.56E-03 2.86E-03 2.06E-03 1.26E-03 5.98E-04 2.80E-04 1.54E-04
5.04E-03 4.93E-03 4.58E-03 3.98E-03 3.24E-03 2.36E-03 1.49E-03 7.48E-04 3.67E-04 2.00E-04
.20 .20 .20 .20 .19 .19 .19 .18 .18 .19
9.08E-04 9.03E-04 8.82E-04 8.45E-04 7.91E-04 7.18E-04 6.25E-04 5.12E-04 4.31E-04 3.83E-04
9.08E-04 9.03E-04 8.82E-04 8.45E-04 7.91E-04 7.18E-04 6.25E-04 5.12E-04 4.31E-04 3.83E-04
3.65E-03 3.62E-03 3.53E-03 3.36t-03 3.11E-03 2.77E-03 2.33E-03 1.81E-03 1.41E-03 1.10E-03
5.59E-03 5.57E-03 5.50E-03 5.38E-03 5.19E-03 4.91E-03 4.51E-03 3.97E-03 3.57E-03 3.43E-03
5.87E-04 5.79E-04 5.51E-04 5.01E-04 4.36E-04 3.53E-04 2.58E-04 1.63E-04 1.01E-04 5.96E-05
1.19E-03 1.18E-03 1.14E-03 1.08E-03 9.94E-04 8.75E-04 7.26E-04 5.53E-04 4.27E-04 3.31E-04
1.34E-04 1.32E-04 1.27E-04 1.18E-04 1.06E-04 8.97E-05 7.05E-05 4.98E-05 3.55E-05 2.49E-05
1.91E-04 1.89E-04 1.82E-04 1.69E-04 1 S1E-04 1.28E-04 1.01E-04 7.11E-05 5.07E-05 3.56E-05
5.19E-03 5.18E-03 5.14E-03 5.09E-03 4.99E-03 4.85E-03 4.64E-03 4.36E-03 4.14E-03 4.23E-03
7.79E-03 7.B1E-03 7.87E-03 7.97E-03 8.17E-03 8.46E-03 8.97E-03 9.88E-03 1.09E-02 9.73E-03
1.72E-02 1.72E-02 1.74E-02 1.76E-02 1.80E-02 1.87E-02 1.98E-02 2.17E-02 2.37E-02 2.14E-02
6.38E-02 6.36E-02 6.29E-02 6.15E-02 5.95E-02 5.66E-02 5.25E-02 4.70E-02 4.29E-02 4.27E-02
-------
photolysis rates in multi-layer AQS models. In single-cell models,
photolytic rates appropriate for an elevation equal to one-half the
maximum mixing depth are recommended.
2.2 Special Product Coefficients and Rate Constants
The product coefficients in the alkane reactions depend on
temperature and pressure. The pressure dependency can be ignored in most
urban-scale applications. However, the temperature dependency should not
be ignored if the mechanism is going to be applied over a wide
temperature range. The values of the coefficients in reactions 85 and 86
of the OZIPM mechanism (Table 2-2) between 270 and 330°K are shown below.
Values at intermediate temperatures can be determined by linear
interpolation or by using the computer routine that was developed for
this purpose. A listing of the routine :.s given in Table 2-9.
TEMPERATURE (K)
COEFF. 270 280 290 300 310 320 330
B01
B02
BOS
B04
805
B06
B07
608
B09
BIO
Bll
B12
B13
B14
B15
B16
B17
B18
.197
.168
.115
.351
.489
.114
.886
.446
1.332
.005
.021
.215
.297
.765
.288
.701
.651
1.352
.194
.217
.132
.347
.473
.100
.900
.497
1.397
.011
.025
.226
.316
.804
.255
.737
.713
1.450
.192
.266
.149
.343
.458
.087
.913
.548
1.461
.017
.028
.238
.336
.843
.223
.774
.775
1.549
.189
.315
.166
.339
.442
.073
.927
.599
1.526
.023
.032
.249
.355
.882
.190
.810
.837
1.647
.189
.404
.192
.343
.384
.065
.935
.668
1.603
.033
.048
.265
.376
.885
.169
.831
.893
1.724
.188
.493
.218
.346
.325
.058
.942
.738
1.680
.044
.065
.280
.398
.888
.147
.852
.948
1.800
.188
.582
.244
.350
.267
.050
.950
.807
1.757
.054
.081
.296
.419
.891
.126
.873
1.004
1.877
Several product coefficients and rate constants in the condensed
mechanism (Table 2-4) depend on temperature and organic mixture
composition. While the condensed mechanism can be used with the default
composition assumptions, the recommended approach is for the user to
2-17
-------
TABLE 2-9
EXAMPLE OF SPECIAL SUBROUTINE FOR THE OZIPM MECHANISM
SUBROUTINE SPECIAL(TEMP,B)
C
C THIS ROUTINE COMPUTES THE ALKANE PRODUCT COEFFICIENTS
C FOR THE ERT/SAPRC OZIPM MECHANISM
C
C INPUTS:
C TEMP = TEMPERATURE (DEGREES K)
C OUTPUTS:
C B(J) = VARIABLE PRODUCT COEFFICIENTS FOR THE REACTIONS
C OF ALKANES
C
REAL B(18)
B(01) = CT(TEMP,0.197,0.189,0.188)
B(02) = CT(TEMP,0.168,0.315,0.582)
B(03) = CT(TEMP,0.115,0.166,0.244)
B(04) = CT(TEMP,0.351,0.339,0.350)
B(05) = CT(TEMP,0.489,0.442.0.267)
B(06) = CT(TEMP,0.114,0.073,0.050)
B(07) = CT(TEMP,0.886,0.927,0.950)
B(08) = CT(TEMP,0.446,0.599,0.807)
B(09) = B(07) + B(08)
B(10) = CT(TEMP,0.005,0.023,0.054)
B(ll) = CT(TEMP,O.C21,0.032,0.081)
B(12) = CT(TEMP,0.2:.5,0.249,0.296)
B(13) ^ CT(TEMP,0.207,0.355,0.419)
B(14) = CT(TEMP,0.765,0.882,0.891)
B(15) = CT(TEMP,0.288,0.190,0.126)
B(16) = CT(TEMP,0.701,0.810,0.873)
B(17) = CT(TEMP,0.651,0.837,1.004)
B(18) = B(16) + B(17)
RETURN
END
FUNCTION CT(TEMP,C1,C2,C3)
C LINEAR INTERPOLATION FOR 3 VALUE TABULATED FUNCTION
REAL T(3)
DATA T /270.,300.,330./
CT = Cl
IF(TEMP.LE.T(1)) RETURN
CT = C3
IF(TEMP.GE.T(3)) RETURN
IF(TEMP.LT.T(2)) THEN
SLOPE = (C2-C1)/(T(2)-T(1))
CT = Cl + SLOPE*(TEMP-T(1))
ENDIF
IF(TEMP.GE.T(2)) THEN
SLOPE = (C3-C2)/(T(3)-T(2))
CT = C2 + SLOPE*(TEMP-T(2))
ENDIF
RETURN
END
2-18
-------
estimate the average values for three composition fractions based on
region-specific ambient air NMOC data or speciated emission inventory
data. The lumped product coefficients and rate constants depend on the
ratio of C4-C5 alkanes to >C3 alkanes (X), the ratio of terminal alkenes
to >C2 alkenes (Y), and the ratio of di-alkylbenzenes to di- and
tri-alkylbenzenes (Z), where X, Y, and Z are on a mole basis. These mole
fractions are estimated from the corresponding carbon fractions (ie., XG,
Y , Z ) as shown below:
X = (Xc/4.5) / (Xc/4.5 + (l.-X
Y = (Yc/3.0) / (Yc/3.0 + (l.-Y
Z = (Zc/8.0) / (Zc/8.0 + (l.-
The lumped rate constants for reactions 57, 75-78, and 80 in Table 2-4
are then determined from the following expressions:
R57 = 1.053E-11*EXP( -354/T)*X + 1.62E-11*EXP( -289/T)*(l-X)
R75 = 4.850E-12*EXP( 504/T)*Y + 1.01E-11*EXP( 549/T)*(l-Y)
R76 = 1.320E-14*EXP(-2105/T)*Y + 9.08E-15*EXP(-1137/T)*(1-Y)
R77 = 1.180E-11*EXP( -324/T)*Y + 2.26E-11*EXT'( 10/T)*(1-Y)
R78 = 5.000E-12*EXP(-1935/T)*Y + 1.OOE-11*EXP( -975/T)*(l-Y)
R80 = 1.660E-11*EXP( 116/T)*Z + 6.20E-11*(1-Z)
The product coefficients for the same reactions are determined from the
following expressions:
B01 = 0.197*X + 0.005*(1-X) at 270°K
B02 = 0.282*X + 0.236*(1-X) "
BOS = 0.489*X + 0.765*(1-X) "
B04 = 0.114*X + 0.288*(1-X) "
BOS = 0.886*X + 0.701*(1-X) "
B06 = 0.446*X + 0.651*(1-X) "
B07 = 1.332*X + 1.352*(1-X) "
2-19
-------
B01
B02
BOS
B04
BOS
B06
B07
0.189*X H
0.481*X H
0.442*X H
0.073*X H
0.927*X H
0.599*X H
1.526*X H
- 0.023*(1-X)
i- 0.281*(1-X)
H 0.882*(1-X)
h 0.190*(1-X)
h 0.810*(1-X)
H 0.837*(1-X)
h 1.647*(1-X)
at 300°K
B01
B02
BOS
B04
BOS
B06
B07
0.188*X H
0.826*X H
0.267*X H
0.050*X H
0.950*X H
0.807*X H
1.757*X i
i- 0.054*(1-X)
i- 0.377*(1-X)
y 0.891*(1-X)
h 0.126*(1-X)
I- 0.873*(1-X)
I- 1.004*(1-X)
i- 1.877*(1-X)
at 330°K
B08
B09
BIO
Bll
B12
B13
B14
BIS
B16
B17
B18
B19
B20
321
Y
Y + 2.
0.64*Y
0.50*Y
0.13*Y
0.17*Y
0.06*Y
0 . 28*Y
0.40*Y
(1-Y)
0.40*Y
0.20*Y
0.20*Y
0.60*Y
00*(1-Y)
+ (1-Y)
+ 0.27*(1-Y)
+ 0.21*(1-Y)
+ 0.12*(1-Y)
+ 0.40*(1-Y)
B22 = 0.650*Z + 0.49*(1-Z)
B23 = 0.316*Z + 0.86*(1-Z)
B24 = 0.095*Z
The expression for the coefficients in the alkane reaction (No. 57) are
given at three temperatures. Values at intermediate temperatures can be
obtained by linear interpolation. We have found it most convenient to
implement a subroutine to calculate these rate constants and coefficients
into the AQS model software. The routine we use for this purpose is
shown in Table 2-10.
The default values of the carbons fractions are 0.43, 0.6, and 0.6
for X , Y , and Z , respectively. The default coefficients and rate
c c c
constants (at 298°K) for the lumped reactions are shown below:
2-20
-------
TABLE 2-10
EXAMPLE OF SPECIAL SUBROUTINE FOR THE CONDENSED MECHANISM
SUBROUTINE SPECIAL(TEMP,F,B,R)
C
C THIS IS THE FORTRAN?? SUBROUTINE TO COMPUTE THE VARIABLE PRODUCT
C COEFFICIENTS AND SPECIAL RATE CONSTANTS FOR THE SAPRC/ERT
C CONDENSED CHEMICAL MECHANISM.
C
C INPUTS: TEMP = TEMPERATURE IN DEGRESS KELVIN
C F(l) = XC = C4-C5 FRACTION OF UC3 ALKANES ON A CARBON BASIS
C F(2) = YC = TERMINAL ALKENE FRACTION OF 1IC2 ALKENES ON A
C CARBON BASIS
C F(3) = ZC = DI-ALKYLBENZENE FRACTION OF DI- & TRI-ALKYLBENZENES
C ON A CARBON BASIS
C
C OUTPUTS:
C B(J) = VARIABLE PRODUCT COEFFICIENTS FOR THE REACTIONS
C OF ALKANES, HIGHER ALKENES, AND HIGHER AROMATICS
C
C R(I) = RATE CONSTANTS FOR REACTIONS OF ALKANES, HIGHER
C ALKENES, AND HIGHER AROMATICS
C
REAL F(3), B(24), R(95)
C
C...COMPUTE THE FRACTIONS ON A MOLAR BASIS, WHERE
C X = C4-C5 FRACTION OF >C3 ALKANES
C Y = TERMINAL ALKENE FRACTION OF >C2 ALKENES
C Z = TRI-ALKYLBENZENE FRACTION OF DI- & TRI-ALKYLBENZENES
C
X = (F(l)/4.5) / (F(l)/4.5 + (l.-F(l))/?.)
Y = (F(2)/3. ) / (F(2)/3. + (1.
Z = (F(3)/8. ) / (F(3)/8. + (1.
XT = 1. - X
YT = 1. - Y
ZT = 1. - Z
C...COMPUTE COEFFICIENTS FOR ALKANES
B(01) = CT(TEMP,0.197,0.189,0.188)*X + CT(TEMP,0.005,0.023,0.054)*XT
B(02) = CT(TEMP,0.282,0.481,0.826)*X + CT(TEMP,0.236,0.281,0.377)*XT
B(03) = CT(TEMP,0.489,0.442,0.267)*X + CT(TEMP,0.765,0.882,0.891)*XT
B(04) = CT(TEMP,0.114,0.073,0.050)*X + CT(TEMP,0.288,0.190,0.126)*XT
B(05) = CT(TEMP,0.886,0.927,0.950)*X + CT(TEMP,0.701,0.810,0.873)*XT
B(06) = CT(TEMP,0.446,0.599,0.807)*X + CT(TEMP,0.651,0.837,1.004)*XT
B(07)
COMPUTE
B(08)
B(09)
B(10)
B(ll)
B(12)
B(13)
B(14)
B(15)
B(16)
= B(05) + B(06)
COEFFICIENT FOR HH
=
=
=
=
=
=
=
=
=
0
0
0
0
0
0
0
Y
Y +
.64*Y
.50*Y +
.13*Y +
.17*Y +
.06*Y +
.28*Y
.40*Y
2
0
0
0
.00*YT
YT
.27*YT
.21*YT
.12*YT
2-21
-------
TABLE 2-10 (Continued)
B(17)
B(18)
B(19)
B(20)
B(21)
YT
0.40*Y
0.20*Y
0.20*Y + 0.40*YT
0.60*Y
.COMPUTE COEFFICENTS FOR HIGHER AROMATICS
B(22) = 0.65*Z + 0.49*ZT
B(23) =0.316*Z + 0.86*ZT
B(24) =0.095*Z
.REACTION RATE FOR ALKA + OH IN MOLECULE-CC-SEC UNITS
R(57) = 1.053E-11*EXP( -354/T)*X + 1.62E-11*EXP(
..REACTION RATE FOR ALKE + OH IN MOLECULE-CC-SEC UNITS
R(75) = 4.850E-12*EXP( 504/T)*Y + 1.01E-11*EXP(
..REACTION RATE FOR ALKE + 03 IN MOLECULE-CC-SEC UNITS
R(76) = 1.320E-14*EXP( -2105/T)*Y + 9.08E-15*EXP(
..REACTION RATE FOR ALKE + 0 IN MOLECULE-CC-SEC UNITS
R(77) = 1.180E-11*EXP( -324/T)*Y + 2.26E-11*EXP(
..REACTION RATE FOR ALKE + N03 IN MOLECULE-CC-SEC UNITS
R(78) = 5.000E-12*EXP( -1935/T)*Y + 1.OOE-11*EXP(
..REACTION RATE FOR AROM + OH IN MOLECULE-CC-SEC UNITS
R(80) = 1.660E-11*EXP( 116/T)*Z + 6.20E-11*ZT
RETURN
END
FUNCTION CT(TEMP,C1,C2,C3)
LINEAR INTERPOLATION FOR 3 VALUE TABULATED FUNCTION
REAL T(3)
DATA T /270.,300.,330./
CT = Cl
IF(TEMP.LE.T(1)) RETURN
CT = C3
IF(TEMP.GE.T(3)) RETURN
IF(TEMP.LT.T(2)) THEN
SLOPE = (C2-C1)/(T(2)-T(1»
CT = Cl + SLOPE*(TEMP-T(1))
END IF
IF(TEMP.GE.T(2)) THEN
SLOPE = (C3-C2)/(T(3)-T(2))
CT = C2 + SLOPE*(TEMP-T(2))
ENDIF
RETURN
END
-289/T)*XT
549/T)*YT
-1137/T)*YT
10/T)*YT
-975/T)*YT
2-22
-------
ALKA + OH — > .112 HCHO +.380 ALD2 +.643 MEK +.131 R02N
+.868 R02R +.698 R202 +.157 R02
= 6740 ppm"1 min" (or 4.56E-12 cm molecule" sec" )
ALKE + OH — > .667 HCHO +1.33 ALD2 + R02R + R02
k_5 = 57300 ppm" min" (or 3.88E-11 cm molecule" sec" )
ALKE + 03 —> .427 HCHO +.667 ALD2 +.177 R02R +.177 R02
+.183 H02 + .08 OH +.187 CO
k_, = 0.110 ppm" min" (or 7.42E-17 cm molecule" sec )
ALKE + 0 — > .333 CO +.333 MEK +.267 HCHO +.133 ALD2
+.267 H02 + .40 R02R + .40 R02
= 15400 ppm"1 min"1 (or 1.04E-11 cm molecule"1 sec"1)
ALKE + N03 — > N02 +.667 HCHO +1.33 ALD2 + R202 + R02
k_D = 194 ppm" min (or 1.31E-13 cm molecule sec" )
/ o
AROM + OH --> .17 CRES + .17 H02 + .83 R02R + .83 R02
+.59 DIAL +.518 MGLY +.597 HCHO +.597 CO
kgo = 56800 ppm" min" (or 3.84E-11 cm molecule"1 sec"1)
The default rate constant expressions are
= 1.35E-11 * exp (-324/T) cm3 molecule"1 sec"1
= 6.80E-12 * exp (519/T) cm3 molecule"1 sec"1
k_e = 2.93E-14 * exp (-1782/T) cm3 molecule"1 sec"1
/b
k?? = 2.13E-11 * exp (-213/T) cm3 molecule"1 sec"1
2-23
-------
k_Q = 2.95E-11 * exp (-1615/T) cm3 molecule"1 sec"1
/o
kg0 = 2.97E-11 * exp (77/T) cm3 molecule"1 sec"1
2.3 Steady-State Approximations
Numerous species in the mechanism react so fast that their
concentrations are essentially in steady-state under most atmospheric
conditions. These species have large production and destruction rates,
but small net rates of change of concentration. The computer memory
and time requirements of AQS models can be reduced by calculating the
concentrations of these species from algebraic equations based on the
steady-state approximation rather than by numerical integration of their
differential equations. However, not all kinetic solver software systems
provide capabilities for treating species diagnostically (e.g. OZIPM and
CHEMK).
The steady-state approximation assumes a system is at chemical
equilibrium where the rate of change of concentration is zero. It is the
state where the rate of chemical production (P) is equal to the rate of
destruction (DC). With this assumption the species concentration (C) can
be calculated from the simple linear algebraic equation (for species that
do not react with themselves), as shown below.
dC/dt = P - DC = 0
C = P/D
The procedure for selecting the species for which this approximation
is valid involves examining the characteristic reaction time (1/D) of the
species over a range of conditions. In order for the approximation to be
valid, the reaction time must be smaller than the typical time step size
in the AQS model (~1 minute) under all plausible circumstances. We have
examined the reaction time for a range of radiation, temperature, and
concentrations including low NO conditions. Tables 2-11 and 2-12 list
X
typical reaction times for daylight and nighttime conditions in urban and
low NO environments, respectively, at 298°K. These characteristic
X
2-24
-------
TABLE 2-11
CHARACTERISTIC REACTION TIME IN URBAN ENVIRONMENTS
SPECIES
0*SD
0
OH
BZO
BZN2
RC03
MC03
PC03
GC03
N03
H02
R02
R02P
R02R
R202
R02N
HN04
NO
N205
N02
03
HONO
TBUT
DIAL -
CRES
PAN
PPN
GPAN
TMBZ
MGLY
PHEN
PRPE
HCHO
GLYX
XYLE
RCHO
ALD2
NPHE
ETHE
TOLU
ALK7
H202
ALK4
ALKN
ROOH
MEK
ACET
CO
HN03
REACTION TIME (MINUTES)*
DAYLIGHT NIGHTTIME
2.E-11
2.E-08
6.5E-4
0.002
0.002
0.003
0.003
0.003
0.003
0.004
0.007
0.014
0.014
0.014
0.014
0.014
0.2
0.4
0.5
2
5
10
23
25
31
45
45
45
58
76
88
110
140
140
150
170
210
270
390
580
590
1,100
1,100
1,800
2,300
2,700
7,800
17,000
28,000
2.E-11
2.E-08
4.E-04
5.E-04
5.E-04
0.002
0.002
0.002
0.002
0.005
0.005
0.035
0.035
0.035
0.035
0.035
0.2
1.5
0.5
40
15
300
130
1,200
25
45
45
45
4,500
2,300
140
2,000
8,000
5,000
11,000
12,000
16,000
140
11,000
45,000
45,000
80,000
86,000
130,000
150,000
240,000
800,000
1,300,000
2,200,000
2-25
-------
TABLE 2-12
CHARACTERISTIC REACTION TIME IN LOW NO ENVIRONMENTS
A
SPECIES
REACTION TIME (MINUTES)*
DAYLIGHT NIGHTTIME
0*SD
0
OH
BZO
BZN2
RC03
MC03
PC03
GC03
N03
H02
R02
R02P
R02R
R202
R02N
HN04
NO
N205
N02
03
HONO
TBUT
DIAL
CRES
PAN
PPN
GPAN
TMBZ
MGLY
PHEN
PRPE
HCHO
GLYX
XYLE
RCHO
ALD2
NPHE
ETHE
TOLU
ALK7
H202
ALK4
ALKN
ROOH
MEK
ACET
CO
HN03
2.E-11
2.E-08
2.E-03
0.08
0.08
0.2
0.2
0.2
0.2
0.05
0.2
10
10
10
10
10
0.2
0.2
0.5
120
30
10
23
25
3
45
45
45
58
76
18
105
130
140
145
160
210
18
370
570
580
1,100
1,100
1,800
2,300
2,700
7,800
17,000
28,000
2.E-11
2.E-08
2.E-03
0.07
0.07
0.2
0.2
0.2
0.2
0.7
0.5
10
10
10
10
10
0.2
0.2
0.5
60
1,500
600
19
1,900
60
45
45
45
3,000
3,200
110
430
6,500
6,500
7,500
6,800
8,000
970
2,700
30,000
30,000
80,000
57,000
91,000
300,000
180,000
700,000
850,000
1,450,000
2-26
-------
reaction times indicate the steady-state approximation is valid for 0*SD,
0, OH, BZO, and BZN2 at all times.
The reactions times for RC03, H02, and R02 indicate the
approximation is valid under urban NO conditions. For low NOx
X
conditions the approximation is marginally valid for RC03 and H02, and
not valid for R02 species. Since the mechanisms are invariably applied
under low NO conditions, the steady-state species must be selected so as
X
to avoid serious errors when these conditions occur. We have found,
however, that if H02 and the R02 and RC03 psuedo-species are integrated,
the individual peroxy species (R02R, R202, R02P, and R02N) and the acyl
peroxy species (MC03, PC03, and GC03 in the OZIPM mechanism) can be
accurately calculated using the steady-state approximation (Carter et al.
1986).
The HN04 and N205 reaction times at 298°K indicate the approximation
is marginally valid, however, the lifetimes of these species are strongly
dependent on temperature. For example, at 283°K (or 50°F) the reaction
times of HN04 and N205 are 1.2 and 3.6 minutes, respectively, which
eliminates them as candidates for steady-state treatment in most
photochemical model applications.
Concentrations of the N03 radical can be accurately calculated from
the approximation during daylight hours and whenever NO concentrations
are greater than 1 ppb. However, the approximation becomes marginal for
NO, when NO concentrations are low at night. Therefore, it is
recommended that NO, be included as an integrated species.
If the mechanism is applied under conditions where steady-state
treatment of HN04, N205, and N03 is valid and is used, the solution
procedure should contain a nitrogen balance calculation (or nitrogen
conservation constraint) to ensure that the approximation is not
artificially introducing significant amounts of nitrogen to the system.
The diagnostic equations for the steady-state species in the OZIPM
and condensed mechanisms are shown in Tables 2-13 and 2-14, respectively.
These equations should be evaluated in the order shown because the
concentrations of some steady-state species depend on the concentrations
of other steady-state species. These equations should be evaluated each
time chemical derivatives are calculated in the AQS model.
2-27
-------
TABLE 2-13
DIAGNOSTIC EQUATIONS FOR THE STEADY-STATE SPECIES IN THE OZIPM MECHANISM
[0*SD] = R16*[03] / (R17*[H20] + R18)
[0] = (R1*[N02] + R14*[N03] + R15*[03] + R18*[0*SD] )/( R2 f R3*
[N02] + R4*[N02] + R102*[ETHE] + R106*[PRPE] + R110*[TBUT])
[PC03] = (R60*[RCHO]*[OH] + R62*[RCHO]*[N03] + R68*[PPN]
+ 0.50*R72*[MEK*[OH] + R115*[OH]*[DIAL]) / (R63*[NO] +
R64*[N02] + R65*[H02] + R66*[R02] + R67*[RC03])
[GC03] = (.37*R74*[GLYX]*[OH] +.37*R75*[GLYX]*[N03] + R78*[GPAN])/
(R76*[N02] + R77*[NO] + R79*[H02] + R80*[R02]
+ R81*[RC03])
[R02R] = (R50*[HCHO]*[H02] + R52*[ALD2] + R54*[NO]*[MC03] +
R61*[RCHO] + R63*[NO]*[PC03] + R69*[ACET] + R70*[ACET]
*[OH] + R71*[MEK] + B07*R85*[OH]*[ALK4] + B16*R86*[OH]
*[ALK7] + R100*[OH]*[ETHE] + R102*[ETHE]*[0] + R104*[OH]
*[PRPE] + 0.13*R105*[03]*[PRPE] + 0.60*R106*[PRPE]*[0] +
R108*[OH]*[TBUT] + 0.27*R109*[03]*[TBUT] + 0.84*R112*[OH]
*[TOLU] + 0.83*R113*[OH]*[XYLE] + 0.83*R114*[OH]*[TMBZ] +
0.85*R117*[OH]*[CRES] + 0.85*R126*[OH]*[PHEN]) /
(R96*[NO] + R97*[H02] + R98*[R02] + R99*[RC03])
[R202] = (1.50*R72*[MEK]*[OH] + B08*R85*[OH]*[ALK4] + B17*R86*
[OH]*[ALK7] + 1.39*R87*[OH]*[ALKN] + R103*[N03]*[ETHE]
+ R107*[N03]*[PRPE] + R111*[N03]*[TBUT]) /
(R92*[NO] + R93*[H02] + R94*[R02] + R95*[RC03])
[R02N] = (B06*R85*[OH]*[ALK4] + B15*R86*[OH]*[ALK7]) /
(R88*[NO] + R89*[H02] + R90*[R02] + R91*[RC03])
[R02P] = (0.14*R117*[OH]*[CRES] + 0.14*R126*[OH]*[PHEN]) /
(R119*[NO] + R120*[H02] + R121*[R02] + R122*[RC03])
[BZN2] = (R128*[N03]*[NPHE]) / (R129*[N02] + R130*[H02] + R131)
[BZO] = (R118*[N03]*[CRES] + R127*[N03]*[PHEN])/
(R123*[N02] + R124*[H02] + R125)
[MC03] = (R51*[ALD2]*[OH] + R53*[ALD2]*[N03] + R59*[PAN] + R69 '
*[ACET] + R71*[MEK] + 0.50*R72*[MEK]*[OH] + R82*[MGLY] +
R83*[OH]*[MGLY] + R84*[MGLY]*[N03] + R116*[DIAL]) / (R54
*[NO] + R55*[N02] + R56*[H02] + R57*[R02] + R58*[RC03])
2-28
-------
TABLE 2-14
DIAGNOSTIC EQUATIONS FOR THE STEADY-STATE
SPECIES IN THE CONDENSED MECHANISM
[0*SD] = R16*[03] / (R17*[H20] + R18)
[0] = (R1*[N02] + R14*[N03] + R15*[03] + R18*[0*SD] /
(R2 + R3*[N02] + R4*[N02] + R73*[ETHE] + R77*[ALKE])
[OH] = (2.*R17*[0*SD]*[H20] + R20*[HONO] + R26*[NO]*[H02]
R30*[03]*[H02] + B14*R76*[03]*[ALKE]) / (R19*[NO] +
R22*[N02] + R23*[HN03] + R24*[CO] + R25*[03] + R29*
[HN04] + R41*[HCHO] + R44*[ALD2]
[MGLY] + R57*[ALKA] + R58*[ALKN]
[ALKE] + R79*[TOLU] + R80*[AROM]
[CRES]
R53*[MEK] + R55*
R71*[ETHE] + R75*
R81*[DIAL] + R83*
[R02R] = (R43*[H02]*[HCHO] + R45*[ALD2] + R47*[NO]*[MC03] +
R52*[MEK] + 1.50*R53*[MEK]*[OH] + B05*R57*[ALKA]*[OH]
+ R71*[ETHE]*[OH] + R73*[ETHE]*[0] + R75*[ALKE]*[OH]
+ B12*R76*[03]*[ALKE] + B21*R77*[ALKE]*[0] + 0.84*R79
*[TOLU]*[OH] + 0.83*R80*[AROM]*[OH] + 0.85*R83*[CRES]
*[OH]) / (R67*[NO] + R68*[H02] + R69*[R02] + R70*[MC03])
[R202J = (B06*R57*[ALKA}*[OH] + 1.39*R58*[ALKN]*[OH] + R74*[N03]
*[ETHE] + R78*[N03]*[ALKE]> / (R63*[NO] + R64*[H02] +
R65*[R02] + R66*[MC03])
[R02N] = B04*R57*[ALKA]*[OH] / (R59*[NO] + R60*[H02] + R61*[R02]
+ R62*[MC03j)
[R02P] = 0.14*R83*[CRES]*[OH] / (R85*[NO] + R86*[H02] + R87*[R02]
+ R88*[MC03])
[BZN2] = R92*[N03]*[NPHE] / (R93*[N02] + R94*[H02] + R95)
[BZO] = R84*[N03]*[CRES] / (R89*[N02] + R90*[H02] + R91)
2-29
-------
2.4 Sample Problems
Four sample problems have been generated to facilitate verification
of proper mechanism implementation. The first two cases are simple
initial value kinetic problems that should be easy to reproduce.
Constant photolytic rates and temperature are used. The emissions,
dilution, and deposition rates are zero in these examples. Tables 2-15
and 2-16 summarize the inputs and outputs for Example No. 1 which employs
the OZIPM mechanism. Tables 2-17 and 2-18 summarize the inputs and
outputs for Example No. 2 which employs the condensed chemical mechanism.
These solutions were computed using the LSODE numerical integration
procedure (Hindmarsh 1980) with a maximum step size of five minutes.
Relative and absolute error control tolerances of 0.01 and l.E-7 ppm were
used. All species except water vapor were integrated (ie., no
steady-state approximations). The user should verify that his solutions
compare well with these solutions for each hour of the simulation.
Solutions using the recommended steady-state approximations should also
compare well with those shown for all of the key species.
Two sample problems using the OZIPM computer program and the
131-step mechanism are provided in Tables 2-19 and 2-20. Each table
shows all of the inputs and outputs for the simulation. The examples are
relatively complex photochemical box model calculations. Diurnally
varying solar radiation, emission injection, dilution and entrainment of
0, and NMOC from aloft are included. The OZIPM input data formats are
described by Hugo and Whitten (1986) and, therefore, are not repeated
here. Example No. 3, shown in Table 2-19, is an OZIPM "CALC" run whose
output consists of concentrations as a function of time for a single set
of initial concentrations. Example No. 4, shown in Table 2-20, is an
OZIPM "EKMA" run where the VOC control requirement is calculated for a
specific set of input data.
The chemical mechanism input to OZIPM is identical to that shown in
Table 2-2 except for three minor changes. First, a water vapor
concentration of 20,000 ppm (the recommended default value) has been
incorporated into the rate constants for reactions 11, 17, 21, 32, and 34
instead of having OZIPM integrate the water vapor concentration. The
rate constants should be adjusted to the actual water vapor concentration
2-30
-------
for a particular application using OZIPM's RATE option. These rate
constants are ^ .culated from the following expressions:
Kn = 1.48E-06 * [H20]
K17 = 3.25E+05 * [H20]
K21 = 5.91E-09 * [H20]
K32 = K34 = 1-19E'05 * tH2°] * EXP(2971/T)
Second, since OZIPM can not accommodate temperature dependent
product coefficients, product coefficients appropriate for 300°K were
input for reactions 85 and 86 in these examples. The user should input
product coefficients for these reactions that reflect the average
temperature (within ~5°C) in the simulation.
Third, a dummy reaction (No. 132) for nonreactive hydrocarbons
(NRHC) has been included so that the sum of the concentrations of the
individual NMOC classes equals the NMOC concentration. The reaction is
needed so that the program recognizes NRHC as a species. The reaction is
not essential for using the mechanism in OZIPM.
2-31
-------
TABLE 2-15
INPUT PARAMETERS FOR TEST PROBLEM #1
Initial Concentrations (ppm):
NO
N02
ALK4
ALK7
ETHE
PRPE
TBUT
TOLU
XYLE
TMBZ
HCHO
ALD2
CO
03
H20
Temperature:
Dilution Rate:
.075
.025
.04667
.040
.015
.020
.010
.02286
.0075
.00444
.030
.010
1.0
.00001
20000.
298°K
0
Emission Rates: 0
Deposition Rates: 0
Photolytic Reaction Rates (per min)
N02
N03 to NO
N03 to N02
03 to 0
03 to 0*SD
MONO
H202
ROOM
HCHO to H02
HCHO to H2
ALD2
RCHO
ACET
MEK
GLYX
MGLY
DIAL
5.000E-01
1.130E+00
1.020E+01
2.760E-02
2.280E-03
9.800E-02
4.540E-04
4.540E-04
1.825E-03
2.795E-03
2.935E-04
5.950E-04
6.700E-05
9.550E-05
3.895E-0:?
8.600E-03
3.190E-02
2-32
-------
TABLE 2-15 (Continued)
Product Coefficients:
B01 .190
B02 .305
B03 .163
B04 .340
BOS .445
B06 .0757
B07 .924
BOS .589
B09 1.51
BIO .0218
Bll .0313
B12 .247
B13 .351
B14 .874
B15 .197
B16 .803
B17 .825
B18 1.63
2-33
-------
TEST PROBLEM #1 -
TABLE 2-16
CONSTANT SOLAR RADIATION -
131 REACTION MECHANISM
to
Ul
TIME
(MIN)
30.000
60.000
90.000
120.000
150.000
NO
H202
ACET
TBUT
MC03
4.309E-02
5.511E-07
1.157E-03
5.231E-03
2.399E-07
2.173E-02
2.567E-06
2.392E-03
2.058E-03
4.173E-07
1.292E-02
6.981E-06
3.452E-03
6.496E-04
6.111E-07
8.305E-03
1.594E-05
4.460E-03
1.554E-04
8.768E-07
5.516E-03
3.464E-05
5.488E-03
2.620E-05
1.269E-06
N02
CO
MEK
TOLU
PC03
5.044E-02
1.006E+00
2.363E-03
2.168E-02
2.382E-08
6.17SE-02
1.015E+00
4.857E-03
2.042E-02
4.110E-08
5.956E-02
1.023E+00
6.970E-03
1.935E-02
6.030E-08
5.306E-02
1.031E+00
8.957E-03
1.833E-02
9.068E-08
4.482E-02
1.039E+00
1.096E-02
1.730E-02
1.413E-07
03
HCHO
GLYX
XYLE
GC03
2.098E-02
3.217E-02
2.337E-04
6.074E-03
4.269E-10
5.083E-02
3.427E-02
4.119E-04
4.795E-03
9.819E-10
8.218E-02
3.452E-02
5.116E-04
3.873E-03
1.701E-09
1.126E-01
3.377E-02
5.720E-04
3.129E-03
2.806E-09
1.424E-01
3.246E-02
6.099E-04
2.489E-03
4.605E-09
MONO
ALD2
GPAN
TMBZ
R02R
1.141E-03
2.146E-02
1.389E-06
2.602E-03
1.411E-06
6.574E-04
2.750E-02
7.911E-06
1.430E-03
1.970E-06
3.790E-04
2.900E-02
1.784E-05
8.331E-04
2.611E-06
2.593E-04
2.845E-02
3.029E-05
4.854E-04
3.575E-06
1.934E-04
2.694E-02
4.550E-05
2.719E-04
5.098E-06
HN03
RCHO
MGLY
DIAL
R202
HN04
PAN
ALK4
CRES
R02N
CONCENTRATION (PPM)
3.734E-03
6.582E-04
1.825E-03
1.363E-03
1.994E-07
1.037E-02
1.240E-03
2.514E-03
1.439E-03
3.363E-07
1.700E-02
1.646E-03
2.494E-03
1.168E-03
5.244E-07
2.336E-02
1.961E-03
2.246E-03
9.478E-04
8.230E-07
2.942E-02
2.220E-03
1.934E-03
8.029E-04
1.321E-06
4.191E-05
9.442E-04
4.540E-02
6.197E-04
4.001E-08
8.243E-05
3.824E-03
4.400E-02
8.450E-04
6.578E-08
1.148E-04
7.251E-03
4.279E-02
6.942E-04
1.005E-07
1.461E-04
1.072E-02
4.160E-02
4.132E-04
1.546E-07
1.800E-04
1.420E-02
4.037E-02
2.107E-04
2.425E-07
N205
PPN
ALK7
PHEN
R02P
1.604E-06
8.413E-05
3.794E-02
4.006E-10
2.429E-09
1.142E-05
3.757E-04
3.574E-02
5.046E-09
5.760E-09
2.821E-05
7.120E-04
3.387E-02
1.899E-08
7.606E-09
4.649E-05
1.073E-03
3.210E-02
3.771E-08
7.416E-09
6.214E-05
1.488E-03
3.031E-02
5.065E-08
6.147E-09
N03
R02
ALKN
NPHE
BZN2
4.125E-08
1.613E-06
4.979E-04
2.273E-05
4.776E-12
2.334E-07
2.313E-06
1.019E-03
1.577E-04
1.511E-10
5.923E-07
3.143E-06
1.457E-03
4.783E-04
1.205E-09
1.094E-06
4.406E-06
1.865E-03
8.452E-04
4.428E-09
1.722E-06
6.426E-06
2.271E-03
1.033E-03
1.005E-08
OH
RC03
ETHE
0*SD
BZO
2.327E-07
2.641E-07
1.393E-02
9.625E-16
7.416E-10
2.034E-07
4.594E-07
1.279E-02
2.332E-15
4.684E-09
1.936E-07
6.731E-07
1.181E-02
3.770E-15
1.012E-08
2.013E-07
9.703E-07
1.088E-02
5.163E-15
1.247E-08
2.210E-07
1.415E-06
9.950E-03
6.534E-15
1.186E-08
H02
ROOH
PRPE
0
H20
2.049E-06
2.408E-07
1.586E-02
5.302E-10
2.000E+04
3.273E-06
1.089E-06
1.208E-02
6.643E-10
2.000E+04
4.719E-06
2.845E-06
9.287E-03
6.610E-10
2.000E+04
6.749E-06
6.330E-06
7.031E-03
6.128E-10
2.000E+04
9.830E-06
1.360E-05
5.157E-03
5.466E-10
2.000E+04
-------
TABLE 2-16 (Continued)
Ul
l/l
TIME
(MIN)
180.000
210.000
240.000
270.000
300.000
NO
H202
ACET
TBUT
MC03
3.596E-03
7.595E-05
6.576E-03
2.888E-06
1.887E-06
2.219E-03
1.764E-04
7.747E-03
1.886E-07
2.960E-06
1.239E-03
4.480E-04
8.995E-03
7.149E-09
5.025E-06
6.121E-04
1.165E-03
1.022E-02
1.552E-10
9.285E-06
2.879E-04
2.543E-03
1 . 124E-02
l.OOOE-30
1.763E-05
N02
CO
HEK
TOLU
PC03
3.587E-02
1.046E+00
1.305E-02
1.622E-02
2.303E-07
2.666E-02
1.052E+00
1.527E-02
1.507E-02
4.006E-07
1.778E-02
1.058E+00
1.759E-02
1.386E-02
7.546E-07
1.033E-02
1.063E+00
1.982E-02
1.268E-02
1.514E-06
5.508E-03
1.067E+00
2.165E-02
1.171E-02
3.010E-06
03
HCHO
GLYX
XYLE
GC03
1.722E-01
3.075E-02
6.319E-04
1.929E-03
7.699E-09
2.021E-01
2.872E-02
6.407E-04
1.441E-03
1.350E-08
2.312E-01
2.636E-02
6.363E-04
1.033E-03
2.534E-08
2.567E-01
2.382E-02
6.166E-04
7.259E-04
5.034E-08
2.738E-01
2.150E-02
5.819E-04
5.314E-04
9.897E-08
HONO
ALD2
GPAN
TMBZ
R02R
1.468E-04
2.488E-02
6.403E-05
1.424E-04
7.677E-06
1.081E-04
2.244E-02
8.644E-05
6.787E-05
1.241E-05
7.277E-05
1.978E-02
1.128E-04
2.915E-05
2.168E-05
4.123E-05
1.725E-02
1.400E-04
1.187E-05
3.879E-05
1.982E-05
1.532E-02
1.612E-04
5.451E-06
6.305E-05
HN03
RCHO
UGLY
DIAL
R202
HN04
PAN
ALK4
CRES
R02N
CONCENTRATION (PPM)
3.509E-02
2.433E-03
1.624E-03
7.076E-04
2.219E-06
4.022E-02
2.602E-03
1.348E-03
6.390E-04
3.982E-06
4.447E-02
2.718E-03
1.112E-03
5.784E-04
7.591E-06
4.745E-02
2.773E-03
9.168E-04
5.045E-04
1.414E-05
4.905E-02
2.772E-03
7.596E-04
4.117E-04
2.246E-05
2.180E-04
1.777E-02
3.904E-02
1.194E-04
3.971E-07
2.588E-04
2.144E-02
3.757E-02
8.254E-05
6.913E-07
2.876E-04
2.516E-02
3.596E-02
6.413E-05
1.273E-06
2.603E-04
2.852E-02
3.433E-02
5.302E-05
2.284E-06
1.732E-04
3.079E-02
3.294E-02
4.763E-05
3.506E-06
N205
PPN
ALK7
PHEN
R02P
7.086E-05
1.992E-03
2.843E-02
5.623E-08
6.050E-09
6.916E-05
2.616E-03
2.642E-02
6.449E-08
7.777E-09
5.523E-05
3.375E-03
2.430E-02
9.250E-08
1.200E-08
3.258E-05
4.193E-03
2.223E-02
1.699E-07
1.925E-08
1.405E-05
4.858E-03
2.054E-02
3.266E-07
2.854E-08
N03
R02
ALKN
NPHE
BZN2
2.447E-06
9.903E-06
2.689E-03
9.981E-04
1.724E-08
3.205E-06
1.640E-05
3.123E-03
8.372E-04
2.549E-08
3.824E-06
2.929E-05
3.564E-03
6.512E-04
3.544E-08
3.862E-06
5.295E-05
3.968E-03
5.013E-04
4.745E-08
3.110E-06
8.554E-05
4.263E-03
4.105E-04
5.852E-08
OH
RC03
ETHE
0*SD
BZO
2.502E-07
2.125E-06
8.993E-03
7.900E-15
1.196E-08
2.878E-07
3.374E-06
8.007E-03
9.268E-15
1.454E-08
3.225E-07
5.804E-06
7.013E-03
1.061E-14
2.022E-08
3.176E-07
1.085E-05
6.085E-03
1.177E-14
2.908E-08
2.675E-07
2.070E-05
5.343E-03
1.256E-14
3.935E-08
H02
ROOM
PRPE
0
H20
1.487E-05
2.988E-05
3.621E-03
4.730E-10
2.000E+04
2.376E-05
7.052E-05
2.407E-03
3.968E-10
2.000E+04
3.957E-05
1.860E-04
1.509E-03
3.235E-10
2.000E+04
6.166E-05
5.268E-04
9.121E-04
2.625E-10
2.000E-1-04
7.665E-05
1.365E-03
5.732E-04
2.233E-10
2.000E+04
-------
TABLE 2-16 (Continued)
NJ
I
OJ
TIME
(MIN)
330.000
360.000
390.000
420.000
450.000
NO
H202
ACET
TBUT
MC03
1
4
1
1
3
9
5
1
1
4
8
7
1
1
4
8
9
1
1
4
7
1
1
1
4
.420E-04
.236E-03
.203E-02
.OOOE-30
.186E-05
.455E-05
.947E-03
.268E-02
.OOOE-30
.353E-05
.302E-05
.607E-03
.329E-02
.OOOE-30
.709E-05
.006E-05
.217E-03
.389E-02
.OOOE-30
.780E-05
.820E-05
.079E-02
.447E-02
.OOOE-30
.759E-05
N02
CO
MEK
TOLU
~C03
2.975E-03
1.071E+00
2.307E-02
1.095E-02
5.608E-06
2.083E-03
1.074E+00
2.426E-02
1.033E-02
7.916E-06
1.866E-03
1.077E+00
2.536E-02
9.756E-03
8.879E-06
1.814E-03
1.079E+00
2.641E-02
9.197E-03
9.344E-06
1.784E-03
1.082E+00
2.744E-02
8.649E-03
9.653E-06
03
HCHO
GLYX
XYLE
GC03
2.836E-01
1.979E-02
5.407E-04
4.081E-04
1.823E-07
2.887E-01
1.882E-02
4.995E-04
3.240E-04
2.534E-07
2.922E-01
1.822E-02
4.615E-04
2.581E-04
2.786E-07
2.951E-01
1.770E-02
4.275E-04
2.048E-04
2.865E-07
2.979E-01
1.717E-02
3.967E-04
1.605E-04
2.884E-07
MONO
ALD2
GPAN
TMBZ
R02R
8.912E-06
1.401E-02
1.737E-04
2.784E-06
9.072E-05
5.105E-06
1.311E-02
1.786E-04
1.551E-06
1.059E-04
4.130E-06
1.239E-02
1.797E-04
8.718E-07
1.087E-04
3.960E-06
1.175E-02
1.794E-04
4.905E-07
1.085E-04
3.931E-06
1.114E-02
1.784E-04
2.645E-07
1.075E-04
HN03 HN04
RCHO PAN
MGLY ALK4
DIAL CRES
R202 R02N
CONCENTRATION (PPM)
4.987E-02
2.742E-03
6.320E-04
3.247E-04
3.127E-05
5.034E-02
2.698E-03
5.335E-04
2.655E-04
3.686E-05
5.071E-02
2.646E-03
4.608E-04
2.331E-04
3.911E-05
5.106E-02
2.588E-03
4.087E-04
2.150E-04
4.047E-05
5.141E-02
2.525E-03
3.699E-04
2.018E-04
4.153E-05
9.854E-05
3.184E-02
3.182E-02
4.832E-05
4.744E-06
6.869E-05
3.182E-02
3.087E-02
5.215E-05
5.454E-06
6.148E-05
3.133E-02
2.996E-02
5.362E-05
5.647E-06
5.993E-05
3.071E-02
2.905E-02
5.241E-05
5.694E-06
5.911E-05
3.008E-02
2.813E-02
5.019E-05
5.688E-06
N205
PPN
ALK7
PHEN
R02P
5.233E-06
5.278E-03
1.922E-02
5.642E-07
4.161E-08
2.808E-06
5.482E-03
1.814E-02
8.599E-07
5.449E-08
2.325E-06
5.592E-03
1.713E-02
1.123E-06
6.126E-08
2.250E-06
5.682E-03
1.615E-02
1.291E-06
6.376E-08
2.225E-06
5.772E-03
1.519E-02
1.376E-06
6.449E-08
N03
R02
ALKN
NPHE
BZN2
2.147E-06
1.220E-04
4.450E-03
3.643E-04
6.618E-08
1.661E-06
1.428E-04
4.562E-03
3.465E-04
6.933E-08
1.543E-06
1.478E-04
4.642E-03
3.393E-04
7.031E-08
1.535E-06
1.490E-04
4.708E-03
3.339E-04
7.085E-08
1.544E-06
1.491E-04
4.766E-03
3.274E-04
7.102E-08
OH
RC03
ETHE
0*SD
BZO
2.217E-07
3.744E-05
4.770E-03
1.301E-14
5.091E-08
2.079E-07
5.117E-05
4.305E-03
1.324E-14
6.057E-08
2.115E-07
5.554E-05
3.889E-03
1.340E-14
6.465E-08
2.196E-07
5.669E-05
3.506E-03
1.354E-14
6.466E-08
2.284E-07
5.677E-05
3.148E-03
1.366E-14
6.335E-08
H02
ROOM
PRPE
0
H20
8.065E-05
2.787E-03
3.748E-04
2.031E-10
2.000E+04
8.056E-05
4.720E-03
2.532E-04
1.969E-10
2.000E+04
8.061E-05
6.853E-03
1.713E-04
1.968E-10
2.000E+04
8.077E-05
9.014E-03
1.159E-04
1.981E-10
2.000E+04
8.101E-05
1.116E-02
7.683E-05
1.994E-10
2.000E+04
-------
TABLE 2-16 (Continued)
TIME
(MIN)
480.000
NO
H202
ACET
TBUT
MC03
7.661E-05
1.231E-02
1.505E-02
l.OOOE-30
N02
CO
MEK
TOLU
PC03
1.758E-03
1 . 084E+00
2.842E-02
8.114E-03
03
HCHO
GLYX
XYLE
GC03
3.004E-01
1.664E-02
3.687E-04
1.246E-04
MONO
ALD2
GPAN
TMBZ
R02R
3.929E-06
1.058E-02
1.769E-04
1.393E-07
HN03
RCHO
UGLY
DIAL
R202
HN04
PAN
ALK4
CRES
R02N
CONCENTRATION (PPM)
5.176E-02
2.457E-03
3.412E-04
1.908E-04
5.845E-05
2.946E-02
2.721E-02
4.772E-05
N205
PPN
ALK7
PHEN
R02P
2.210E-06
5.864E-03
1.426E-02
1.397E-06
N03
R02
ALKN
NPHE
BZN2
1.556E-06
1.489E-04
4.816E-03
3.191E-04
OH
RC03
ETHE
0*SD
BZO
2.374E-07
5.677E-05
2.816E-03
1.378E-14
H02
ROOM
PRPE
0
H20
8.128E-05
1.329E-02
5.036E-05
2.007E-10
4.730E-05 9.951E-06 2.890E-07 1.064E-04 4.249E-05 5.659E-06 6.454E-08 7.079E-08 6.160E-08 2.000E+04
I
OJ
-4
-------
TABLE 2-17
INPUT PARAMETERS FOR TEST PROBLEM #2
Initial Concentrations (ppm):
NO .075
N02 .025
ALKA .0827
ETHE .015
ALKE .0294
TBUT .010
TOLU .02286
AROM .01190
HCHO .030
ALD2 .010
CO 1.0
03 .00001
H20 20000.
Temperature: 298°K
Dilution Rate: 0
Emission Rates: 0
Deposition Rates: 0
Photolytic Reaction Rates (per min)
N02
N03 to NO
N03 to N02
03 to 0
03 to 0*SD
HONO
H202
ROOH
HCHO to H02
HCHO to H2
ALD2
RCHO
ACET
MEK
GLYX
MGLY
DIAL
5.000E-01
1.130E+00
1.020E+01
2.760E-02
2.280E-03
9.800E-02
4.540E-04
4.540E-04
1.825E-03
2.795E-03
2.935E-04
5.950E-04
6.700E-05
9.550E-05
3.895E-03
8.600E-03
3.190E-02
2-38
-------
TABLE 2-17
INPUT PARAMETERS FOR TEST PROBLEM #2
Initial Concentrations (ppm):
NO .075
N02 .025
ALKA .0827
ETHE .015
ALKE .0294
TBUT .010
TOLU .02286
AROM .01190
HCHO .030
ALD2 .010
CO 1.0
03 .00001
H20 20000.
Temperature: 298°K
Dilution Rate: 0
Emission Rates: 0
Deposition Rates: 0
Photolytic Reaction Rates (per min)
N02
N03 to NO
N03 to N02
03 to 0
03 to 0*SD
HONO
H202
ROOM
HCHO to H02
HCHO to H2
ALD2
RCHO
ACET
MEK
GLYX
MGLY
DIAL
5.000E-01
1.130E+00
1.020E+01
2.760E-02
2.280E-03
9.800E-02
4.540E-04
4.540E-04
1.825E-03
2.795E-03
2.935E-04
5.950E-04
6.700E-05
9.550E-05
3.895E-03
8.600E-03
3.190E-02
2-38
-------
TABLE 2-17 (Continued)
Composition:
X = .4286 Carbon Basis
Y = .6000 " "
Zcc = .6000 " "
Special Rate Constants:
R57 6.74E+03 per ppm-min
R75 5.70E+04 " "
R76 1.10E-01 " "
R77 1.54E+04 " "
R78 1.94E+02 " "
R80 5.68E+04 " "
Product Coefficients:
B01 .112
B02 .380
BOS .643
B04 .131
BOS .868
B06 .698
B07 1.57
BOS .667
B09 1.33
BIO .427
Bll .667
B12 .177
B13 .183
B14 .080
B15 .187
B16 .267
B17 .333
B18 .267
B19 .133
B20 .267
B21 .400
B22 .590
B23 .518
B24 .0597
2-39
-------
TEST PROBLEM #2
TABLE 2-18
CONSTANT SOLAR RADIATION
- 95 REACTION MECHANISM
M
O
TIME
(MIN)
30.000
60.000
90.000
120.000
150.000
NO
CO
ETHE
R202
4
1
1
1
2
1
1
3
1
1
1
5
7
1
1
9
4
1
9
1
.262E-02
.007E+00
.390E-02
.893E-07
.066E-02
.016E+00
-269E-02
.426E-07
.184E-02
.026E+00
.162E-02
.622E-07
.477E-03
.035E+00
.061E-02
.010E-07
.803E-03
.043E+00
.593E-03
.468E-06
N02
HCHO
ALKE
R02N
5.082E-02
3.417E-02
2.012E-02
3 . 544E-08
6.204E-02
3.735E-02
1.193E-02
6.343E-08
5.871E-02
3.768E-02
6.487E-03
1.032E-07
5.075E-02
3.634E-02
3.203E-03
1.646E-07
4.149E-02
3.416E-02
1.349E-03
2.676E-07
03
ALD2
TOLU
R02P
2.134E-02
2.091E-02
2.165E-02
2.683E-09
5.350E-02
2.797E-02
2.031E-02
6.943E-09
8.743E-02
3.060E-02
1.913E-02
9.412E-09
1.195E-01
3.038E-02
1.800E-02
8.869E-09
1.504E-01
2.856E-02
1.687E-02
7.394E-09
HONO
PAN
AROM
BZN2
1.172E-03
1.031E-03
8.473E-03
5.142E-12
6.750E-04
4.409E-03
5.698E-03
1.871E-10
3.876E-04
8.645E-03
3.932E-03
1.582E-09
2.624E-04
1.305E-02
2.714E-03
5.661E-09
1.890E-04
1.746E-02
1.810E-03
1.267E-08
HN03 HN04
R02 MC03
DIAL CRES
BZO H20
CONCENTRATION (PPM)
3.857E-03 4.523E-05
1.697E-06 2.664E-07
1.488E-03 6.441E-04
7.947E-10 2.000E+04
1.102E-02
2.607E-06
1.601E-03
5.407E-09
1.831E-02
3.633E-06
1.301E-03
1.178E-08
2.525E-02
5.048E-06
1.035E-03
1.411E-08
3.170E-02
7.322E-06
8.380E-04
1.310E-08
9.579E-05
4.915E-07
8.875E-04
2.000E-I-04
1.356E-04
7.579E-07
7.081E-04
2.000E+04
1.687E-04
1.132E-06
3.999E-04
2.000E+04
2.007E-04
1.692E-06
1.956E-04
2.000E+04
N205
MEK
NPHE
1.674E-06
2.089E-03
2.412E-05
1.267E-05
4.401E-03
1.772E-04
3.117E-05
6.436E-03
5.440E-04
4.976E-05
8.388E-03
9.308E-04
6.335E-05
1.036E-02
1.095E-03
N03
MGLY
0*SD
4.275E-08
1.630E-03
9.789E-16
2.578E-07
2.410E-03
2.454E-15
6.652E-07
2.504E-03
4.011E-15
1.220E-06
2.310E-03
5.484E-15
1.895E-06
2.015E-03
6.900E-15
OH
ALKA
0
2.435E-07
7.944E-02
5.597E-10
2.212E-07
7.578E-02
7.008E-10
2.167E-07
7.252E-02
6.866E-10
2.275E-07
6.934E-02
6.217E-10
2.495E-07
6.609E-02
5.420E-10
H02
ALKN
R02R
2.194E-06
4.253E-04
1.505E-06
3.786E-06
8.919E-04
2.257E-06
5.665E-06
1.299E-03
3.061E-06
8.134E-06
1.686E-03
4.137E-06
1.184E-05
2.073E-03
5.846E-06
-------
TABLE 2-18 (Continued)
to
i
TIME
(MIN)
180.000
210.000
240.000
270.000
300.000
330.000
NO
CO
ETHE
R202
3.017E-03
1.051E+00
8.564E-03
2.539E-06
1.765E-03
1.057E+00
7.508E-03
4.764E-06
9.101E-04
1.063E+00
6.464E-03
9.258E-06
4.303E-04
1.067E+00
5.554E-03
1.586E-05
2.107E-04
1.071E+00
4.858E-03
2.270E-05
1.305E-04
1.074E+00
4.325E-03
2.770E-05
N02
HCHO
ALKE
R02N
3.190E-02
3.152E-02
4.880E-04
4.610E-07
2.246E-02
2.866E-02
1.479E-04
8.595E-07
1.396E-02
2.572E-02
3.704E-05
1.656E-06
7.692E-03
2.298E-02
8.366E-06
2.810E-06
4.187E-03
2.089E-02
1.879E-06
3.991E-06
2.762E-03
1.966E-02
5.129E-07
4.839E-06
03
ALD2
TOLU
R02P
1.807E-01
2.573E-02
1.568E-02
7.615E-09
2.108E-01
2.249E-02
1.441E-02
1.043E-08
2.395E-01
1.929E-02
1.310E-02
1.680E-08
2.623E-01
1.667E-02
1.190E-02
2.536E-08
2.765E-01
1.482E-02
1.096E-02
3.537E-08
2.842E-01
1.350E-02
1.024E-02
4.580E-08
HONO
PAN
AROM
BZN2
1.389E-04
2.186E-02
1.150E-03
2.128E-08
9.818E-05
2.631E-02
6.804E-04
3.128E-08
6.135E-05
3.065E-02
3.746E-04
4.339E-08
3.144E-05
3.412E-02
2.059E-04
5.563E-08
1.444E-05
3.607E-02
1.232E-04
6.405E-08
7.816E-06
3.656E-02
8.088E-05
6.726E-08
HN03 HN04
R02 MC03
DIAL CRES
BZO H20
CONCENTRATION (PPM)
3.754E-02 2.380E-04
1.159E-05 2.609E-06
7.001E-04 1.108E-04
1.346E-08 2.000E+04
4.264E-02
2.040E-05
6.002E-04
1.697E-08
4.661E-02
3.847E-05
5.154E-04
2.387E-08
4.911E-02
6.719E-05
4.243E-04
3.296E-08
5.040E-02
1.005E-04
3.342E-04
4.240E-08
5.107E-02
1.253E-04
2.688E-04
5.033E-08
2.794E-04
4.288E-06
7.692E-05
2.000E+04
2.941E-04
7.685E-06
5.958E-05
2.000E+04
2.302E-04
1.449E-05
4.943E-05
2.000E+04
1.412E-04
2.636E-05
4.563E-05
2.000E+04
9.464E-05
3.864E-05
4.643E-05
2.000E+04
N205
MEK
NPHE
6.802E-05
1.243E-02
1.016E-03
6.140E-05
1.466E-02
8.232E-04
4.336E-05
1.697E-02
6.269E-04
2.210E-05
1.909E-02
4.825E-04
9.119E-06
2.076E-02
3.992E-04
4.628E-06
2.207E-02
3.592E-04
N03
MGLY
0*SD
2.639E-06
1.688E-03
8.288E-15
3.372E-06
1.371E-03
9.670E-15
3.816E-06
1.084E-03
1.099E-14
3.505E-06
8.444E-04
1.203E-14
2.661E-06
6.606E-04
1.268E-14
2.056E-06
5.271E-04
1.304E-14
OH
ALKA
0
2
6
4
3
5
3
3
5
3
3
5
2
2
4
2
2
4
2
.847E-07
.263E-02
.583E-10
.304E-07
.885E-02
.761E-10
.614E-07
.483E-02
.031E-10
.276E-07
.109E-02
.502E-10
.697E-07
.810E-02
.214E-10
.421E-07
.572E-02
.108E-10
H02
ALKN
R02R
1.828E-05
2.473E-03
9.047E-06
3.047E-05
2.893E-03
1.563E-05
5.155E-05
3.315E-03
2.920E-05
7.299E-05
3.674E-03
5.131E-05
8.216E-05
3.919E-03
7.777E-05
8.360E-05
4.070E-03
9.752E-05
-------
TABLE 2-18 (Continued)
I
*>
K)
TIME
(MIN)
360.000
390.000
420.000
450.000
480.000
1
1
3
3
9
1
3
3
9
1
3
3
9
1
2
3
9
1
2
3
NO
CO
ETHE
R202
.050E-04
.077E+00
.864E-03
.014E-05
-886E-05
-079E+00
.446E-03
-094E-05
.682E-05
.081E+00
.062E-03
.127E-05
.552E-05
.083E+00
.709E-03
.143E-05
.427E-05
.085E+00
.386E-03
.150E-05
N02
HCHO
ALKE
R02N
2.294E-03
1.897E-02
1.278E-07
5.235E-06
2.190E-03
1.845E-02
3.186E-08
5.345E-06
2.165E-03
1.792E-02
7.484E-09
5.369E-06
2.152E-03
1.735E-02
1.700E-09
5.363E-06
2.139E-03
1.676E-02
3.828E-10
5.337E-06
03
ALD2
TOLU
R02P
2.894E-01
1.242E-02
9.585E-03
5.300E-08
2.937E-01
1.146E-02
8.968E-03
5.548E-08
2.975E-01
1.060E-02
8.369E-03
5.573E-08
3.012E-01
9.834E-03
7.787E-03
5.528E-08
3.046E-01
9.141E-03
7.224E-03
5.461E-08
HONO
PAN
AROM
BZN2
5.600E-06
3.627E-02
5.375E-05
6.755E-08
5.124E-06
3.567E-02
3.553E-05
6.673E-08
5.080E-06
3.500E-02
2.311E-05
6.557E-08
5.125E-06
3.433E-02
1.476E-05
6.413E-08
5.180E-06
3.368E-02
9.253E-06
6.245E-08
HN03 HN04
R02 MC03
DIAL CRES
BZO H20
CONCENTRATION (PPM)
5.157E-02 7.865E-05
1.360E-04 4.508E-05
2.295E-04 4.729E-05
5.489E-08 2.000E+04
5.201E-02
1.382E-04
2.083E-04
5.546E-08
5.245E-02
1.383E-04
1.951E-04
5.421E-08
5.289E-02
1.377E-04
1.848E-04
5.244E-08
5.333E-02
1.370E-04
1.754E-04
5.056E-08
7.512E-05
4.613E-05
4.613E-05
2.000E+04
7.426E-05
4.574E-05
4.383E-05
2.000E+04
7.384E-05
4.513E-05
4.127E-05
2.000E+04
7.339E-05
4.456E-05
3.875E-05
2.000E+04
N205
MEK
NPHE
3.399E-06
2.326E-02
3.369E-04
3.205E-06
2.438E-02
3.214E-04
3.221E-06
2.547E-02
3.069E-04
3.270E-06
2.652E-02
2.922E-04
3.316E-06
2.752E-02
2.771E-04
N03
MGLY
0*SD
1.831E-06
4.278E-04
1.328E-14
1.811E-06
3.558E-04
1.347E-14
1.842E-06
3.030E-04
1.365E-14
1.881E-06
2.639E-04
1.382E-14
1.920E-06
2.341E-04
1.397E-14
OH
ALKA
0
2.393E-07
4.356E-02
2.091E-10
2.470E-07
4.147E-02
2.106E-10
2.573E-07
3.941E-02
2.128E-10
2.681E-07
3.737E-02
2.150E-10
2.792E-07
3.536E-02
2.171E-10
H02
ALKN
R02R
8.379E-05
4.180E-03
1.058E-04
8.384E-05
4.271E-03
1.072E-04
8.387E-05
4.351E-03
1.069E-04
8.389E-05
4.424E-03
1.063E-04
8.391E-05
4.487E-03
1.054E-04
-------
TABLE 2-19. EXAMPLE
OZONE ISOPLETH PLOTTING PACKAGE
WITH OPTIONAL MECHANISMS
0 Z I P M
VERSION 3.1
SEPTEMBER, 1985
M
I
-------
NJ
I
.c.
TABLE 2-19 (CONTINUED)
THE INPUTS FOR THIS RUN ARE
TITL
TEST PROBLEM
MECH
ALK4
TM8Z
4.5
9.0
N02
0
0
0
NO
N02
NO
HO
N02
N205
N205
N02
N03
N03
03
03
0*SO
0*SD
NO
MONO
HOZ
N02
HN03
CO
03
NO
N02
HN04
HN04
03
H02
H02
N03
N03
H202
H202
R02
RC03
RC03
1.
42.
73.
ALK7
HCHO
7.0
1.0
HV
N02
N02
03
03
N03
NO
N03
N03
HV
HV
HV
HV
OH
HV
OH
OH
OH
OH
H02
H02
OH
H02
H02
H02
H02
H02
HV
OH
NO
NO
N02
132
13
46
82
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
« • OZIPM "CALC" RUN - 131 REACTION MECHANISM
17. 13. 0.
14. 15. 16.
47. 52. 61.
114.
ETHE PRPE T8UT TOLU
ALD2 RCHO MEK NRHC
2.0 3.0 4.0 7.0
2.0 3.0 4.0 1.0
1.NO 1.0
1.03
1.NO
1.N03
1.N02
1.N03
2.N02
2.N02
1.N205
1.N02 1. N03
2.HN03
1.NO 1. N02
1.NO
1.N02 1. 0
1.0
1 .0*50
2. OH
1.0
1 . HOMO
1.NO 1. OH
1.HOWO -1. N02 1. HN03
1.HN03
1.N03
1.H02
1.H02
1.N02 1. OH
1.HN04
1.N02 1. H02
1.N02
1.0H
1.H202
1.H202
1.HN03
1 . HN03
2. OH
1.H02
1.NO
1.NO
1.N02
303.
20.
69.
XYLE
8.0
1.01E 00
4.87E+07
1.37E+04
3.29E+03
2.68E+01
4.77E-02
2.75E+04
1.50E-04
1.71E+03
2.08E+00
3.00E-02
5.98E-01
1.00E 00
1.00E 00
1.00E 00
1.00E 00
6.50E+09
4.32E+10
9.75E+03
1.00E 00
1.17E-04
1.68E*04
1.89E+02
3.22E+02
1.00E+02
1.22E+04
2.02E+03
4.93E+00
5.91E+03
2.96E+00
4.46E+03
5.08E*03
4.46E+03
5.08E+03
1.00E 00
2.45E+03
1.14E+04
1.14E+04
7.57E*03
35.
71.
0.
•1282.
0.
-894.
1370.
2450.
•252.
•529.
-273.
11379.
0.
1229.
0.
0.
0.
0.
0.
0.
-833.
0.
0.
-737.
-778.
0.
942.
-240.
-773.
10103.
0.
579.
-771.
-2971.
-771.
•2971.
0.
187.
•180.
-180.
-180.
-------
THE INPUTS FOR TH!S RUN ARE
TABLE 2-19 (CONTINUED)
NJ
I
R02
RC03
ROOH
R02
R02
RC03
HCHO
HCHO
HCHO
HCHO
HCHO
AL02
AL02
1.
AL02
MC03
1.
MC03
MC03
MC03
MC03
PAN
RCHO
RCHO
1.
RCHO
PC03
1.
PC03
PC03
PC03
PC03
PPN
ACET
1.
ACET
HEK
1.
MEK
.5
GLYX
GLYX
.37
GLYX
.37
GC03
GC03
GPAN
GC03
GC03
H02
H02
HV
R02
RC03
RC03
HV
HV
OH
N03
H02
OH
HV
R02R
N03
NO
R02
N02
H02
R02
RC03
OH
HV
R021
N03
NO
R02
N02
H02
R02
RC03
HV
R02R
OH
HV
R02R
OH
ALD2
HV
OH
RC03
N03
GC03
N02
NO
H02
R02
40
41
42
43
44
45
46
47
48
49
50
51
52
1. R02
53
54
55
56
57
58
59
60
61
1. R02
62
63
64
65
66
67
68
69
1. R02
70
71
1. RC2
72 1
1.H02
1.H02
1.H02
2.H02
1.CO
1.H02
1.HN03
1.R02R
1 .MC03
1.CO *
1.HN03
1.N02 *
1.PAN
1.ROOH
.5H02
1.H02
1.HC03
1.RC03
1.ALD2*
1.HN03
1.N02 *
1.PPN
1.ROOH
.5H02
I.H02
1.PC03
1.HC03*
1.MGLY
1 .MC03*
.5R02R*
.5 HCHO .5
73 .
74 .
75
.37 RC03
76
77
78
79
80
13HCHO
63H02 *
1.HN03*
1.GPAN
1.N02
1.GC03
1.ROOH
.5H02
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.5
PC03
1.87
1.26
.63
OH
CO
CO
H02
R02
RC03
HCHO
MC03
HCHO
HCHO
HCHO
HCHO
N02
PC03
H02
PC03
AL02
ALD2
ALD2
ALD2
N02
HCHO
R02R
ALD2
R02
1.
CO
CO
H02
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
.5
RC03
CO
H02
RC03
R02R
R02
RC03
RC03
CO
RC03
R02R
R02
RC03
RC03
RC03
R02
RC03
MC03
4
4
1
1
4
3
1
1
1
.43E+03
.43E+03
.OOE 00
.48E+00
.43E+03
.69E+03
.OOE 00
.OOE 00
.33E+04
8.82E-01
1
2
1
3
1
7
4
4
3
2
2
1
3
1
7
4
4
3
2
1
3
1
.48E+01
.36E+04
.OOE 00
.69E+00
.14E+04
.57E+03
.43E+03
.43E+03
.69E+03
.21E-02
.93E+04
.OOE 00
.63E+00
.14E+04
.57E+03
.43E+03
.43E+03
.69E+03
.21E-02
.OOE 00
.39E+02
.OOE 00
1 .46E+03
1.00E 00
.37
1.26
GC03
CO
1.70E+04
8.88E-01
7.57E+03
1.
1.
1.
1.
H02
N02
CO
CO
1.
1.
CO
RC03
1.14E+04
2.21E-02
4.43E+03
1.
R02
4.43E+03
0
0
0
0
0
0
0
0
0
2060
0
-250
0
1427
-180
-180
0
0
0
13542
•252
0
1432
-180
-180
0
0
0
13542
0
1125
0
745
0
0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
f
,
.
f
.
.
.
2058.
-180.
-180.
13542.
0.
0.
-------
THE INPUTS FOR THIS RUN ARE
TABLE 2-19 (CONTINUED)
GC03
MGLY
1.
MGLY
MGLY
1.
ALK4
.34
ALK7
.36
ALKN
.48
R02N
R02N
R02N
R02N
R202
R202
R202
R202
R02R
R02R
R02R
R02R
ETHE
.22
ETHE
ETHE
1.
ETHE
1.
PRPE
1.
PRPE
.06
PRPE
.2
PRPE
1.
T8UT
TBUT
.12
TBUT
TBUT
1.
TOLU
.4
DIAL
DIAL
1.
RC03
HV
RC03
OH
N03
RC03
OH
ACET
OH
ACET
OH
AL02
NO
H02
R02
RC03
NO
H02
R02
RC03
NO
H02
R02
RC03
OH
ALD2
03
0
R02R
N03
R02
OH
R02
03
OH
0
H02
N03
R202
OH
03
OH
0
N03
R02
OH
DIAL
OH
HV
RC03
81
82
83
84
1.H02
1.MC03*
1 .MC03
1.HN03*
85 . 19HCHO*
.44 MEK
.07
86 .02HCHO*
.88 MEK
87
.18
1.N02 *
.16 HCHO 1.39
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
1. R02
103
104
105 .
.17 H02
106
.6 R02R
107
1. R02
108
109
.21 H02
110
111
112 .
.84 R02
113
114
1.ALKN
1.ROOH
1.R02
1.RC03
1.N02
1.ROOH
1.R02
1.RC03
1.N02
1.ROOH
.5H02
.5H02
1.R02R*
1.HCHO
1.HCHO*
1.N02 *
1.R02R*
64HCHO*
.13
.6ACET*
.4
1.N02 *
1.R02R
1.ALD2*
.27
1.MEK
1.N02 *
16CRES*
.144
1.PC03
1.H02 *
1.
1.
1.
1.
.31
R02N
.03
R02N
.15
R202
1.
.5
.5
1.
1.
1.
1.
.12
1.
2.
1.
.5
R02R
.4
CO
1.
2.
.15
R02
.4
2.
.16
MGLY
1.
1.
CO
H02
CO
MC03
ALD2
.93
ALD2
.82
MEK
1.39
MEK
H02
H02
H02
R02
RC03
R02
H02
H02
HCHO
HCHO
ALD2
.13
HCHO
.6
HCHO
ALD2
CO
.JO
H02
ALD2
H02
.114
RC03
CO
1.
1.
1.
1.
.17
R02R
.25
R02R
1.05
R02
1.
1.
1.56
.42
1.
1.
1.
.28
R02
.2
R02
1.
1.
.27
HCHO
1.
.84
GLYX
1.
RC03
CO
RC03
CO
RCHO
.6
RCHO
.84
RCHO
MEK
MEK
HCHO
CO
CO
R202
ALD2
CO
ALD2
ALD2
R02
R02R
R202
R02R
MC03
3.69E+03
1.00E 00
2.51E+04
3.69E+00
4.76E+03
R202 1 .6
9.11E+03
R202 1.84
3.00E+03
1.14E+04
4.43E+03
1 .48E+00
4.43E+03
1.14E+04
4.43E+03
1.48E+00
4.43E+03
1.14E+04
4.43E+03
1 .48E+00
4.43E+03
1.26E+04
2.57E-03
1.08E+03
1.62E-01
3.89E+04
1.67E-02
5.88E+03
1.12E+01
9.42E+04
2.96E-01
3.45E+04
5.61E+02
9.14E+03
4.43E+04
1.00E 00
0.
0.
0.
1427.
353.
R02
288.
R02
709.
-180.
0.
0.
0.
-180.
0.
0.
0.
-180.
0.
0.
0.
-411.
2634.
792.
2923.
-504.
2105.
324.
1935.
-549.
1137.
-10.
975.
-322.
0.
0.
-------
TABLE 2-19 (CONTINUED)
THE INPUTS FOR THIS RUN ARE
to
I
XYLE OH
.83 R02
THBZ OH
.83 R02
CRES OH
1. R02
CRES N03
R02P NO
R02P H02
R02P R02
R02P RC03
8ZO N02
8ZO H02
BZO
PHEN OH
1. R02
PHEN N03
NPHE N03
BZN2 N02
BZN2 H02
8ZN2
NRHC
ZENITH
1.
1.0
13.
2.8
U.
25.
15.
6.45E-02
16.
1.26E-03
20.
.19
35.
6.25E-04
42.
6.25E-04
46.
2.33E-03
47.
4.51E-03
52.
2.58E-04
61.
7.26E-04
69.
7.05E-05
71.
115
.17CRES*
.65 DIAL .316
116
.17CRES*
.49 DIAL .86
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
17.
1.0
1.0
2.3
3.3
20.
30.
5.52E-02
7.43E-02
4.56E-03
5.98E-04
.20
.18
9.08E-04
5.12E-04
9.08E-04
5.12E-04
3.65E-03
1.81E-03
5.59E-03
3.97E-03
5.87E-04
1.63E-04
1.19E-03
5.53E-04
1.34E-04
4.98E-05
1.91E-04
.2MGLY*
1.HN03
1.NPHE
1.ROOH
.5H02
.5H02
1.NPHE
1.PHEN
1.PHEN
.2GLYX*
1 . HW03
1 . HN03
1.NPHE
1.NPHE
1.NRHC
1.0
1.0
2.3
4.1
20.
36.
5.53E-02
8.90E-02
4.45E-03
2.80E-04
.20
.18
9.03E-04
4.31E-04
9.03E-04
4.31E-04
3.62E-03
1.41E-03
5.57E-03
3.57E-03
5.79E-04
1.01E-04
1.18E-03
4.27E-04
1.32E-04
3.55E-05
1.89E-04
.17 H02
UGLY .095
.17 H02
MGLY
.15 R02P
1. BZO
1. R02
1. RC03
.15 R02P
1. BZO
1. BZN2
1.0
1.0
2.3
2.8
21.
26.
5.56E-02
6.60E-02
4.12E-03
1.54E-04
.20
.19
8.82E-04
3.83E-04
8.82E-04
3.83E-04
3.53E-03
1.10E-03
5.50E-03
3.43E-03
5.51E-04
5.98E-05
1.14E-03
3.31E-04
1.27E-04
2.49E-05
1.82E-04
.83 R02R
GLYX
.83 R02R
.85 R02R
.85 R02R
1.0
2.3
21.
5.61E-02 5
3.56E-03 2
.20
8.45E-04 7
8.45E-04 7
3.36E-03 3
5.38E-03 5
5.01E-04 4
1.08E-03 9
1.18E-04 1
1.69E-04 1
3.62E+04 -116
9.16E+04 0
5.91E+04 0
3.25E+04 0
1.14E+04 -180
4.43E+03 0
1.48E+00 0
4.43E+03 0
2.22E+04 0
4.43E+03 0
6.00E-02 0
4.14E+04 0
5.62E+03 0
5.62E+03 0
2.22E+04 0
4.43E+03 0
6.00E-02 0
1.00E-10 0
1.0 1.0
2.4 2.6
22. 23.
.71E-02 5.99E-02
.86E-03 2.06E-03
.19 .19
.91E-04 7.18E-04
.91E-04 7.18E-04
-11E-03 2.77E-03
.19E-03 4.91E-03
.36E-04 3.53E-04
.94E-04 8.75E-04
.06E-04 8.97E-05
.51E-04 1.28E-04
-------
TABLE 2-19 (CONTINUED)
THE INPUTS FOR THIS RUN ARE
I
£>
00
1.01E-04
73.
8.97E-03
82.
1.98E-02
114.
5.25E-02
PLAC
7.11E-05
7.79E-03
9.88E-03
1.72E-02
2.17E-02
6.38E-02
4.70E-02
34.057
5.07E-05
7.81E-03
1.09E-02
1.72E-02
2.37E-02
6.36E-02
4.29E-02
118.24
3.56E-05
7.87E-03
9.73E-03
1.74E-02
2.14E-02
6.29E-02
4.27E-02
8.0
7.97E-03
1.76E-02
6.15E-02
1986.
8.17E-03
1.80E-02
5.95E-02
6.0
8.46E-03
1.87E-02
5.66E-02
21.
LOS ANGELES, CA
DILU
REAC
.210
.040
INIT
CO
1.00
EMIS
.25
TRAN
.001
.040
.050
.040
SPEC
250.
13.
.280
.030
2.
HONO
.0005
-4.
.167
.210
.020
.210
.020
2.
1500.
.25
.030
.020
.15
.167
.080
.180
.050
.180
.050
800.
.060
.000
.10
.083
-13.
.015
.030
.015
.030
1400.
.040
.000
.10
-13.
.030
.000
.030
.000
.160
.070
.05
.005
.000
.005
.000
.060
.070
.350
.070
.350
03 N02
CALC
2.00
0.20
1.
-------
TABLE 3-19 (CONTINUED)
THE REACTIONS
RATE CONSTANT ACT. ENERGY(K)
sj
I
VD
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
N02
0
0
0
NO
N02
NO
NO
N02
N205
N205
N02
N03
N03
03
03
0*SO
0*SD
NO
MONO
N02
N02
HN03
CO
03
NO
N02
HN04
HN04
03
H02
H02
N03
N03
H202
H202
R02
RC03
RC03
R02
RC03
ROOM
R02
R02
RC03
HCHO
HCHO
HCHO
HCHO
HCHO
4
4
4-
4
4
4
4
4
4
4
4
4
4-
4
4
4
4
4
•4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
N02
N02
03
03
N03
NO
N03
N03
OH
OH
OH
OH
OH
H02
H02
OH
H02
H02
H02
H02
H02
OH
NO
NO
N02
H02
H02
R02
RC03
RC03
OH
N03
H02
NO
03
NO
N03
N02
N03
N02
N02
N205
N02
HN03
NO
NO
N02
0
0*SD
OH
0
HONO
NO
HONO
HN03
N03
H02
H02
N02
HN04
N02
N02
OH
H202
H202
HN03
HN03
OH
H02
NO
NO
N02
H02
H02
H02
2 H02 +
CO
H02 *
HN03 +
R02R +
N03
N02
0
OH
N02
OH
H02
HN03
OH
CO
CO
H02
R02
CO
1.000E+00
4.870E+07
1.370E+04
3.290E+03
2.680E+01
4.770E-02
2.750E+04
1.500E-04
1.710E+03
2.080E+00
3.000E-02
5.980E-01
1.000E+00
1.000E+00
1.000E+00
1.000E+00
6.500E+09
4.320E+10
9.750E+03
.OOCE+00
.170E-04
.680E+04
.890E+02
3.220E+02
.OOOE+02
.220E4Q4
2.020E+03
4.930E+00
5.910E+03
2.960E+00
4.460E+03
5.080E+03
4.460E+03
5.080E+03
1.000E+00
2.450E403
1.140E+04
1.140E+04
7.570E+03
4.430E+03
4.430E+03
1.000E+00
1 .480E400
4.430E+03
3.690E+03
1.000E+00
1.000E+00
1.330E404
8.820E-01
1.480E+01
O.OOOE-01
-1.282E+03
O.OOOE-01
•8.940E+02
1 .370E+03
2.45CE+03
-2.520E+02
-5.290E+02
-2.730E+02
1.138E+04
O.OOOE-01
1.229E+03
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
-8.330E+02
O.OOOE-01
O.OOOE-01
-7.370E+02
•7.780E+02
O.OOOE-01
9.420E+02
-2.400E+02
-7.730E402
1.010E+04
O.OOOE-01
5.790E+02
-7.710E+02
-2.971E+03
-7.710E+02
-2.971E+03
O.OOOE-01
1.870E+02
-1.800E+02
-1.800E+02
-1.800E+02
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
2.060E+03
O.OOOE-01
-------
TABLE 2-19 (CONTINUED)
THE REACTIONS
RATE CONSTANT ACT. ENERGY(K)
NJ
I
Ul
O
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
ALD2 +
AL02
AL02 +
MC03 +
MC03 +
MC03 +
MC03 +
MC03 +
PAN
RCHO +
RCHO
RCHO +
PC03 +
PC03 +
PC03 +
PC03 +
PC03 +
PPN
ACET
ACET +
MEK
OH
N03
NO
N02
H02
R02
RC03
OH
N03
NO
N02
H02
R02
RC03
OH
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
MEK +
GLYX
GLYX +
GLYX +
GC03 +
GC03 +
GPAN
GC03 +
GC03 +
GC03 +
MGLY
UGLY +
MGLY +
ALK4 +
ALK7
ALKN
R02N
R02N
OH
OH
N03
N02
NO
H02
R02
RC03
OH
N03
OH
OH
OH
NO
H02
4
0.5
•+•
0.5
4
4
1.5
+ 0.5
0.13
0.63
+ 0.37
0.5
0.19
+ 0.44
+ 1.6
. 2
+ 0.88
+ 1.84
+ 0.16
MC03
CO
R02
HN03
N02
PAN
ROOH
H02
H02
MC03
RC03
AL02
R02
HN03
N02
PPN
ROOH
H02
H02
PC03
MC03
R02
MGLY
HC03
R02
R02R
HCHO
HCHO
H02
HN03
RC03
GPAN
N02
GC03
ROOH
H02
H02
MC03
HC03
HN03
HCHO
MEK
R02
HCHO
MEK
R02
N02
HCHO
ALKN
ROOH
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
1.5
0.5
1.87
1.26
0.63
0.31
0.07
. 3
0.18
0.15
1.39
RC03
HCHO
MC03
HCHO
HCHO
HCHO
HCHO
N02
PC03
H02
PC03
AL02
AL02
ALD2
AL02
N02
HCHO
R02R
ALD2
R02
PC03
CO
CO
H02
H02
N02
CO
CO
CO
H02
CO
MC03
ALD2
R02N
ALD2
R02N
MEK
R202
MEK
+ H02
+ RC03
+ R02R
+ R02
+ RC03
+ RC03
+ CO
+ RC03
+ R02R
+ R02
+ RC03
+ RC03
+ RC03
+ R02
+ RC03
+ 0.5 MC03
+ RC03
+0.37 GC03
+ 1.26 CO
+ CO
+ RC03
+ R02
+ RC03
+ CO
+ RC03
+ CO
+ 0.17 RCHO
+0.93 R02R
+0.25 RCHO
+0.82 R02R
+ 1. 5 RCHO
+ 1.39 R02
+ R02R
+ R02
2.360E+04
1. OOOE+00
3.
1.
7.
4.
690E+00
140E+04
570E+03
430E+03
4.430E+03
+ R02R
+ R02
+ R02R
+ R02R
+ 0.5 ALD2
+0.37 RC03
+0.37 GC03
+ RC03
+ RC03
+0.34 ACET
+0.60 R202
+0.36 ACET
+0.84 R202
+ 0.48 ALD2
3.
2.
2.
690E+03
210E-02
930E+04
1 .OOOE+00
3.
1.
7.
4.
4.
3.
2.
1.
3.
1.
1.
1.
1.
8.
7.
1.
2.
4.
4.
3.
1.
2.
3.
4.
9.
3.
1.
4.
630E+00
140E+04
570E+03
430E+03
430E+03
690E+03
210E-02
OOOE+00
390E+02
OOOE+00
460E+03
OOOE+00
700E+04
880E-01
570E+03
140E+04
210E-02
430E+03
430E+03
690E+03
OOOE+00
510E+04
690E+00
760E+03
110E+03
OOOE+03
140E+04
430E+03
-2.
0.
1.
-1.
-1.
0.
0.
0.
1.
-2.
0.
1.
-1.
-1.
0.
0.
0.
1.
0.
1.
0.
7.
0.
0.
2.
-1.
-1.
1.
0.
0.
0.
0.
0.
500E+02
OOOE-01
427E+03
800E+02
800E+02
OOOE-01
OOOE-01
OOOE-01
354E+04
520E+02
OOOE-01
432E+03
800E+02
800E+02
OOOE-01
OOOE-01
OOOE-01
354E+04
OOOE-01
125E+03
OOOE-01
450E+02
OOOE-01
OOOE-01
058E+03
800E+02
800E+02
354E+04
OOOE-01
OOOE-01
OOOE-01
OOOE-01
OOOE-01
1.427E+03
3.
2.
7.
•1.
0.
530E+02
880E+02
090E+02
800E+02
OOOE-01
-------
TABLE 2-19 (CONTINUED)
THE REACTIONS
RATE CONSTANT ACT. ENERGY(K)
I
U!
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
R02N
R02N
R202
R202
R202
R202
R02R
R02R
R02R
R02R
ETHE
ETHE
ETHE
ETHE
PRPE
PRPE
PRPE
PRPE
TBUT
TBUT
TBUT
TBUT
TOLU
DIAL
DIAL
XYLE
TMBZ
CRES
CRES
R02P
R02P
R02P
R02P
BZO
BZO
BZO
PHEN
PHEN
NPHE
BZN2
BZN2
8ZN2
NRHC
4
4
+
4
4
4
+
4
+
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
+
4
4
4
4
4
4
+
4-
4
R02
RC03
NO
H02
R02
RC03
NO
H02
R02
RC03
OH
03
0
N03
OH
03
0
N03
OH
03
0
N03
OH
OH
OH
OH
OH
N03
NO
H02
R02
RC03
N02
H02
OH
N03
N03
N02
H02
0.5
0.5
4
0.64
4 0.17
0.6
+ 0.6
4
+ 0.21
0.16
+ 0.84
0.17
+ 0.65
0.17
+ 0.49
0.2
0.5
0.5
0.2
R02
RC03
N02
ROOK
R02
RC03
N02
ROOK
H02
H02
R02R
HCHO
HCHO
R02
N02
R02R
HCHO
H02
ACET
R02R
N02
R02
R02R
ALD2
H02
MEK
N02
CRES
R02
PC03
H02
CRES
DIAL
CRES
DIAL
MGLY
HN03
NPHE
ROOM
H02
H02
NPHE
PHEN
PHEN
GLYX
HN03
HN03
NPHE
NPHE
NRHC
4
+
+
4
4
4
+
4
+
4-
4
4
4
4
4-
•f
4-
4
4
+
4
0.5
0.5
0.12
2
0.5
0.13
0.4
0.4
2
0.15
0.27
0.4
2
0.16
+0.144
4
4-
4
0.17
+0.316
4
4
4
4
+
4
4
4
4
0.17
0.86
0.15
0.15
H02
H02
H02
R02
RC03
R02
H02
H02
HCHO
HCHO
ALD2
R02R
HCHO
CO
HCHO
ALD2
CO
R02
H02
ALD2
H02
MGLY
RC03
CO
H02
MGLY
H02
MGLY
R02P
BZO
R02
RC03
R02P
BZO
BZN2
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
1.56
0.42
0.28
0.13
0.2
0.6
0.27
0.3
0.84
+0.114
4
4
4
4
4
4
0.83
. 95
0.83
0.85
0.85
MEK
MEK
HCHO
CO
CO
R202
ALD2
CO
R02
ALD2
R02
ALD2
R02
R02R
HCHO
R202
R02R
GLYX
MC03
R02R
GLYX
R02R
R02R
R02R
+ 0.22 ALD2
+ R02R
+ R02
+ R02
+ . 6 OH
+ 0.2 H02
+ R202
+ 0.12 OH
+ R02
+ 0.4 DIAL
+ RC03
+ 0.83 R02
+ 0.83 R02
+ R02
+ R02
1.
4.
1.
4.
1.
4.
1.
4.
1.
4.
1.
2.
1.
1.
3.
1.
5.
1.
9.
2.
3.
5.
9.
4.
1.
3.
9.
5.
3.
1.
4.
1.
4.
2.
4.
6.
4.
5.
5.
2.
4.
6.
1.
480E+00
430E+03
140E+04
430E+03
480E+00
430E+03
140E+04
430E+03
480E+00
430E+03
260E+04
570E-03
080E+03
620E-01
890E+04
670E-02
880E+03
120E+01
420E+04
960E-01
450E+04
610E+02
140E+03
430E+04
OOOE+00
620E+04
160E+04
910E+04
250E+04
140E+04
430E+03
480E+00
430E+03
220E+04
430E+03
OOOE-02
140E+04
620E+03
620E+03
220E+04
430E+03
OOOE-02
OOOE-10
O.OOOE-01
O.OOOE-01
-1.800E+02
O.OOOE-01
O.OOOE-01
O.OOOE-01
-1.800E+02
O.OOOE-01
O.OOOE-01
O.OOOE-01
-4.110E+02
2.634E+03
7.920E+02
2.923E+03
-5.040E+02
2.105E+03
3.240E+02
1 .935E+03
-5.490E+02
1.137E+03
-1.000E+01
9.750E+02
•3.220E+02
O.OOOE-01
O.OOOE-01
-1.160E+02
O.OOOE-01
O.OOOE-01
O.OOOE-01
-1.800E+02
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
-------
TABLE 2-19 (CONTINUED)
THE FOLLOWING PHOTOLYSIS RATE CONSTANTS ARE USED
REACTION SPECIES ZENITH ANGLE (DEC)
N0. 0 10 20 30 40 50 60 70 78 86
1 N02 6.00E-01 5.95E-01 5.86E-01 5.64E-01 5.32E-01 4.85E-01 4.09E-01 2.88E-01 1.55E-01 3.49E-02
13 N03 1.38E+00 1.37E+00 1.35E+00 1.30E+00 1.28E+00 1.26E+00 1.14E+00 9.51E-01 6.36E-01 9.77E-02
14 H03 1.20E+01 1.19E+01 1.23E+01 1.18E+01 1.17E+01 1.12E+01 1.02E+01 8.65E+00 5.59E+00 9.07E-01
15 03 3.31E-02 3.29E-02 3.26E-02 3.16E-02 3.04E-02 2.91E-02 2.64E-02 2.14E-02 1.38E-02 2.30E-03
16 03 2.74E-03 2.65E-0* 2.41E-03 2.01E-03 1.52E-03 9.99E-04 5.15E-04 1.72E-04 4.35E-05 5.37E-06
20 HONO 1.20E-01 1.19E-01 1.17E-01 1.13E-01 1.01E-01 9.22E-02 7.77E-02 5.19E-02 2.79E-02 6.63E-03
35 H202 5.45E-04 5.37E-04 5.16E-04 4.77E-04 4.21E-04 3.48E-04 2.55E-04 1.48E-04 6.69E-05 1.34E-05
42 ROOH 5.45E-04 5.37E-04 5.16E-04 4.77E-04 4.21E-04 3.48E-04 2.55E-04 1.48E-04 6.69E-05 1.34E-05
46 HCHO 2.19E-03 2.15E-03 2.07E-03 1.90E-03 1.65E-03 1.34E-03 9.52E-04 5.22E-04 2.19E-OA 3.84E-05
47 HCHO 3.35E-03 3.32E-03 3.22E-03 3.04E-03 2.76E-03 2.38E-03 1.84E-03 1.14E-03 5.54E-04 1.20E-04
52 AL02 3.52E-04 3.45E-04 3.23E-04 2.83E-04 2.32E-04 1.71E-04 1.05E-04 4.70E-05 1.57E-05 2.09E-06
61 RCHO 7.14E-04 7.02E-04 6.68E-04 6.09E-04 5.29E-04 4.24E-04 2.97E-04 1.59E-04 6.63E-05 1.16E-05
69 ACET 8.04E-05 7.86E-05 7.44E-05 6.66E-05 5.64E-05 4.35E-05 2.88E-05 1.44E-05 5.51E-06 8.69E-07
71 HEK 1.15E-04 1.12E-04 1.07E-04 9.53E-05 8.03E-05 6.21E-05 4.13E-05 2.05E-05 7.87E-06 1.24E-06
73 GLYX 4.67E-03 4.65E-03 4.61E-03 4.50E-03 4.34E-03 4.10E-03 3.67E-03 2.85E-03 1.69E-03 3.40E-04
82 MGLY 1.03E-02 1.02E-02 1.02E-02 9.93E-03 9.57E-03 9.07E-03 8.09E-03 6.25E-03 3.68E-03 7.47E-04
114 DIAL 3.83E-02 3.79E-02 3.68E-02 3.47E-02 3.16E-02 2.75E-02 2.15E-02 1.35E-02 6.66E-03 1.49E-03
-------
TABLE 2-19 (CONTINUED)
TEST PROBLEM #3 • OZIPM "CALC" RUM - 131 REACTION MECHANISM
PHOTOLYTIC RATE CONSTANTS CALCULATED FOR
LOS ANGELES, CA
LATITUDE 34.057
LONGITUDE 118.240
TIME ZONE 8.0
DATE 6 21 1986
TIME 800 TO 1800 LOCAL DAYLIGHT TIME
DILUTION DETERMINED FROM THE FOLLOWING
INVERSION HEIGHTS INITIAL 250. FINAL 1500.
TIMING START 800. STOP HOO.
NJ
ui MIXING HEIGHTS (AT THE BEGINNING OF EACH HOUR)
U)
TIME 800 900 1000 1100 1200 1300 HOO
HEIGHT 250.0 482.5 774.7 1048.7 1251.5 1394.8 1500.0
REACTIVITY
EMISSIONS ALK4 FRACTION .210 ALK7 FRACTION .280 ETHE FRACTION .030
EMISSIONS PRPE FRACTION .060 TBUT FRACTION .040 TOLU FRACTION .160
EMISSIONS XYLE FRACTION .060 TMBZ FRACTION .040 HCHO FRACTION .030
EMISSIONS ALD2 FRACTION .020 RCHO FRACTION .000 MEK FRACTION .000
EMISSIONS NRHC FRACTION .070
-------
TABLE 2-19 (CONTINUED)
SURFACE LATER ALK4 FRACTION .210 ALK7 FRACTION .180 ETHE FRACTION .015
SURFACE LAYER PRPE FRACTION .030 TBUT FRACTION .005 TOLU FRACTION .070
SURFACE LAYER XYLE FRACTION .040 TMBZ FRACTION .020 HCHO FRACTION .050
SURFACE LAYER ALD2 FRACTION .030 RCHO FRACTION .000 MEK FRACTION .000
SURFACE LAYER NRHC FRACTION .350
ALOFT ALK4 FRACTION .210 ALK7 FRACTION .180 ETHE FRACTION .015
ALOFT PRPE FRACTION .030 TBUT FRACTION .005 TOLU FRACTION .070
ALOFT XYLE FRACTION .040 TMBZ FRACTION .020 HCHO FRACTION .050
ALOFT AL02 FRACTION .030 RCHO FRACTION .000 MEK FRACTION .OOP
ALOFT NRHC FRACTION .350
N02/NOX .250
TRANSPORTED CONCENTRATIONS
SURFACE LAYER OZONE .000 HYDROCARBON .001 NOX .000 PPH
KJ
ui SURFACE LAYER CO 1.000 HONO .001
.fc.
ALOFT OZONE .080 HYDROCARBON .050 NOX .000 PPM
CONTINUOUS EMISSIONS (EXPRESSED AS FRACTION OF THE INITIAL PRECURSORS)
SPECIES HOUR 1234
VOC FRACTION .150 .100 .100 .050
NOX FRACTION .250 .167 .167 .083
-------
TABLE 2-19 (CONTINUED)
TEST PROBLEM #3 - OZIPM "CALC" RUN - 131 REACTION MECHANISM
INITIAL CONCENTRATIONS
CO MONO
1.000E+00 5.000E-04
THE ERROR TOLERANCE IS 3.000E-03
THE TEMPERATURE USED IS 3.030E+02
THE MIXING HEIGHT IS 2.50E+02
THE RATE CONSTANTS USED WERE
3.661E-01
3.000E-02
1.170E-04
4.274E+03
4.430E+03
NJ 2.328E+04
l
S 2.402E-04
3.248E-05
3.690E+03
4.430E+03
2.974E-03
5.921E+02
1 .480E+00
6.000E-02
THE PHOTOLYSIS
1
47
THE PHOTOLYTIC
3.661E-
1.575E-
4.536E+07
6.401E-01
1.613E+04
4.309E+03
2.123E-04
7.983E-05
3.930E+00
1.521E+03
7.459E-03
1.129E+04
1.128E+03
8.978E+03
4.430E+03
1.000E-10
REACTIONS ARE
13
52
RATE CONSTANTS
01 1.059E+00
03 7.983E-05
1.370E+04
1.059E+00
1.810E+02
4.274E+03
1.480E+00
3.993E+00
1.129E+04
3.381E-03
2.510E+04
4.430E+03
1.905E-01
4.430E+04
2.220E+04
14
61
ARE
9.614E+00
2.402E-04
3.131E+03
9.614E+00
3.220E+02
4.309E+03
4.430E+03
1.129E+04
7.495E+03
1.700E+04
3.993E+00
1.480E+00
3.783E+04
1.845E-02
4.430E+03
15
69
2.437E-02
2.269E-05
2.891E+01
2.437E-02
1.054E+02
2.123E-04
3.690E+03
7.495E+03
4.430E+03
9.952E-01
4.854E+03
4.430E+03
1.876E-02
3.597E+04
6.000E-02
16
71
3.523E
3.248E
5.463E-02
3.523E-04
1.204E+04
2.476E+03
7.771E-04
4.430E+03
4.430E+03
7.495E+03
9.256E+03
1.129E+04
5.986E+03
9.160E+04
4.140E+04
20
73
•04 6.815E
•05 3.381E
2.712E+04
6.500E+09
1.935E+03
1.129E+04
1.575E-03
4.430E+03
3.690E+03
1.129E+04
3.120E+03
4.430E+03
1.247E+01
5.910E+04
5.620E+03
35
82
-02 2.123E-04
•03 7.459E-03
1.457E-04
4.320E+10
8.626E+00
1.129E+04
1 .330E+04
3.690E+03
4.678E-02
4.678E-02
1.129E+04
1.480E+00
9.138E+04
3.250E+04
5.620E+03
42
114
2.123E-04
1.845E-02
1.684E+03
9.310E+03
5.910E+03
7.495E+03
9.886E-01
4.678E-02
2.269E-05
4.430E+03
4.430E+03
4.430E+03
3.152E-01
1.129E+04
2.220E+04
46
7.771E
3.906E+00
6.815E-02
3.056E+00
4.430E+03
1.480E+01
2.889E+04
3.608E+02
4.430E+03
1.480E+00
1.232E+04
3.448E+04
4.430E+03
4.430E+03
•04
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT )
NHOC
TOTAL
800. 2.00100
NMOC/
NOX
10.00501
NOX
TOTAL
.20000
N02
FRACTION
.25000
03
(INSTANT)
.00000
N02
(INSTANT)
.05000
NJ
I
l/l
CT>
TIME N02 NO 0 03 N03
INTERVAL CO H02 HN04 H202 R02
HC03 PAN RCHO PC03 PPN
GPAN ALK4 R02N R202 ALK7
CRES DIAL XYLE TMBZ R02P
8.000E+02 5.000E-02 1.500E-01 O.OOOE-01 O.OOOE-01 O.OOOE-01
1.000E-10 1.000E+00 O.OOOE-01 O.OOOE-01 O.OOOE-01 O.OOOE-01
O.OOOE-01 O.OOOE-01 O.OOOE-01 O.OOOE-01 O.OOOE-01
O.OOOE-01 9.338E-02 O.OOOE-01 O.OOOE-01 8.003E-02
O.OOOE-01 O.OOOE-01 1.500E-02 8.891E-03 O.OOOE-01
NET RATES -1.886E-02 1.736E-02 1.831E-02 9.431E-04 O.OOOE-01
•1.165E-02 9.492E-05 O.OOOE-01 O.OOOE-01 1.598E-06
O.OOOE-01 O.OOOE-01 O.OOOE-01 O.OOOE-01 O.OOOE-01
O.OOOE-01 -8.400E-04 O.OOOE-01 O.OOOE-01 -7.282E-04
O.OOOE-01 O.OOOE-01 -1.364E-04 -8.128E-05 O.OOOE-01
THE REACTION RATES ARE
1.83E-02 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 3.28E-06
O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 3.41E-05 5.85E-06 O.OOE-01
O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01 O.OOE-01 4.67E-05 9.46E-05 O.OOE-01 O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 C.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O-OOE-01 O.OOE-01
O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 O.OOE-01 1.40E-11
THE PHOTOLYTIC RATE CONSTANTS ARE
3.661E-01 1.059E+00 9.614E+00 2.437E-02 3.523E-04
1.575E-03 7.983E-05 2.402E-04 2.269E-05 3.248E-05
THE CURRENT MIXING HEIGHT IS 250.00
THE CURRENT TEMPERATURE IS 303.00
THE CURRENT ZENITH ANGLE IS 64.10
N205
RC03
ACET
ALKN
8ZO
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
6.815E-02
3.381E-03
HN03
ROOH
MGLY
ETHE
NPHE
O.OOOE-01 0.
O.OOOE-01 6.
O.OOOE-01 0.
3.001E-02 4.
O.OOOE-01 0.
5.850E-06 0.
O.OOOE-01 -6.
O.OOOE-01 0.
-2.743E-04 -3.
O.OOOE-01 0.
O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01
1.60E-06 O.OOE-01
O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01
O.OOE-01 O.OOE-01
2.123E-04
7.459E-03
0*SD
HCHO
MEK
PRPE
PHEN
OOOE-01
005E-02
OOOE-01
001E-02
OOOE-01
OOOE-01
681E-04
OOOE-01
658E-04
OOOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
O.OOE-01
2.123E-04
1.845E-02
OH
R02R
GLYX
TBUT
BZN2
O.OOOE-01 5.
O.OOOE-01 2.
O.OOOE-01 0.
2.000E-02 4.
O.OOOE-01 1.
3.408E-05 -3.
1.598E-06 -1.
O.OOOE-01 0.
-1.851E-04 -4.
O.OOOE-01 -1.
O.OOE-01 O.OOE
O.OOE-01 O.OOE
O.OOE-01 O.OOE
O.OOE-01 O.OOE
O.OOE-01 O.OOE
O.OOE-01 O.OOE
O.OOE-01 O.OOE
O.OOE-01 O.OOE
O.OOE-01 O.OOE
7.771E-04
HONO
ALD2
GC03
TOLU
NRHC
OOOE-04
002E-02
OOOE-01
572E-02
403E-01
412E-05
787E-04
OOOE-01
189E-04
098E-03
-01
-01
-01
•01
-01
-01
-01
-01
-01
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT )
900.
NMOC
TOTAL
1.12006
NMOC/
NOX
9.60915
NOX
TOTAL
.11656
N02
FRACTION
.72542
03
(INSTANT)
.04239
N02
(INSTANT)
.08456
NJ
I
TIME N02 NO 0
INTERVAL CO H02 HN04
MC03 PAN RCHO
GPAN ALK4 R02N
CRES DIAL XYLE
9.000E+02 8.456E-02 3.201E-02 9.147E-10
1.000E+01 5.201E-01 2.134E-06 4.022E-05
2.663E-07 2.007E-03 9.809E-04
3.225E-06 5.407E-02 3.931E-08
7.682E-04 1.559E-03 6.905E-03
NET RATES -2.606E-04 -8.199E-04 -1.678E-04
-4.658E-03 -1.265E-06 1.821E-06
3.223E-08 5.578E-05 8.974E-06
1.153E-07 -4.338E-04 4.060E-08
•8.611E-07 -9.007E-06 -8.563E-05
THE REACTION RATES ARE
4.01E-02 4.15E-02 1.06E-06 2.42E-07 3.92E-02 1.
1.22E-03 3.84E-05 5.14E-06 3.42E-05 4.58E-05 6.
3.65E-08 2.76E-07 1.95E-08 1.96E-08 1.92E-09 1.
4.20E-12 2.17E-09 3.11E-10 5.08E-05 9.12E-05 8.
1.99E-09 2.85E-10 9.39E-05 4.36E-06 3.95E-07 8.
2.06E-07 8.25E-07 1.33E-06 8.57E-07 6.86E-11 2.
4.04E-05 6.34E-05 3.25E-07 1.42E-05 3.72E-10 9.
1.83E-09 3.08E-05 2.05E-06 1.68E-08 6.51E-10 1.
1.06E-05 4.HE-05 3.82E-05 3.87E-05 6.98E-06 5.
3.03E-12 1.25E-07 1.23E-07 6.21E-13 3.94E-12 9.
THE PHOTOLYTIC RATE CONSTANTS ARE
4.739E-01 1.250E+00 1.103E+01 2
2.298E-03 1.595E-04 4.031E-04 4
THE CURRENT NIXING HEIGHT IS 482.50
THE CURRENT TEMPERATURE IS 303.00
THE CURRENT ZENITH ANGLE IS 51.79
03 N03
H202 R02
PC03 PPN
R202 ALK7
TMBZ R02P
4.239E-02 2.103E-07
7.164E-07 1.685E-06
2.355E-08 1.730E-04
2.167E-07 4.456E-02
2.745E-03 2.898E-09
1.097E-03 4.385E-06
3.176E-08 -4.447E-07
4.528E-08 5.190E-06
2.327E-07 -3.905E-04
-5.432E-05 9.137E-11
96E-04 1.82E-04 1.49E-07
61E-05 9.89E-06 2.10E-04
93E-09 2.39E-10 2.73E-10
11E-05 8.25E-09 1.25E-06
10E-10 8.51E-06 1.49E-05
97E-07 1.69E-07 1.51E-07
80E-14 5.05E-11 7.83E-05
03E-04 1.41E-05 9.71E-08
25E-06 1.05E-06 2.74E-11
10E-12
.875E-02 9.066E-04
.097E-05 5.851E-05
N205
RC03
ACET
ALKN
BZO
7.461E-06
2.903E-07
1.754E-03
6.780E-04
2.808E-09
5.097E-07
7.953E-08
1.976E-05
7.425E-06
-2.166E-08
2.99E-05 2
2.21E-07 2
6.09E-04 1
1.00E-04 4
2.23E-10 1
4.43E-12 3
2.05E-09 5
4.65E-08 6
7.23E-15 3
9.032E-02
4.045E-03
HN03 0*SO
ROOH HCHO
MGLY MEK
ETHE PRPE
NPHE PHEN
7.925E-03 7.907E-16
3.497E-07 3.968E-02
2.247E-03 3.528E-03
1.624E-02 1.773E-02
1.057E-04 2.561E-09
1.498E-04 -8.626E-07
1.523E-08 -2.244E-04
1.728E-06 3.916E-05
-1.520E-04 -2.390E-04
5.187E-06 1.513E-10
.91E-05 2.24E-07 1.14E-08
.58E-05 6.87E-07 8.22E-04
.05E-04 1.84E-04 1.59E-08
.47E-06 2.35E-08 9.62E-05
.76E-10 2.52E-11 8.09E-06
.50E-12 5.02E-13 2.01E-05
.40E-13 2.79E-10 5.15E-04
.16E-05 5.86E-C5 1.38E-07
.73E-12 5.27E-06 2.65E-11
3.331E-04 3.331E-04
8.943E-03 2.652E-02
OH HONO
R02R ALD2
GLYX GC03
TBUT TOLU
BZN2 NRHC
1.537E-07 7.324E-04
1.426E-06 2.802E-02
3.279E-04 4.684E-10
4.385E-03 2.540E-02
6.566E-11 9.101E-02
-6.792E-07 -1.741E-05
•7.183E-07 -1.900E-05
2.324E-06 1.913E-09
•1.408E-04 -2.236E-04
1.702E-09 -5.511E-04
2.63E-07 2.32E-06
3.49E-04 3.47E-04
2.74E-09 1.17E-10
1.69E-04 2.52E-09
7.19E-08 9.73E-08
8.67E-06 1.89E-09
1.35E-08 3.56E-12
5.46E-07 3.51E-05
1.68E-10 1.63E-11
1.279E-03
-------
TIME
(LOT )
1000.
NHOC
TOTAL
.72683
NMOC/
NOX
10.51088
NOX
TOTAL
.06915
N02
FRACTION
.84094
03
(INSTANT)
.09256
N02
(INSTANT)
.05815
NJ
I
Ul
CD
TIME N02 NO
INTERVAL CO H02
MC03 PAN
GPAN ALK4
CRES DIAL
1.000E+03 5.815E-02 1.100E-02
1.000E+01 3.401E-01 4.334E-06
6.779E-07 4.803E-03
1.108E-05 3.619E-02
3.953E-04 9.141E-04
NET RATES -9.622E-04 4.023E-04
-1.911E-03 4.975E-06
1.116E-06 4.018E-05
1.547E-07 -1.982E-04
-7.484E-06 -8.788E-06
THE REACTION RATES ARE
3.11E-02 3.40E-02 5.97E-07 1.36E-07
2.82E-03 1.44E-04 1.88E-05 1.25E-04
6.21E-08 1.23E-06 8.03E-08 8.10E-08
1.48E-11 1.04E-08 2.04E-09 4.88E-05
9.51E-09 1.86E-09 2.25E-04 6.86E-06
4.20E-07 1.46E-06 1.65E-06 1.20E-06
3.27E-05 4.91E-05 5.74E-07 1.09E-05
8.51E-09 2.29E-05 2.74E-06 8.43E-09
7.54E-06 2.91E-05 2.36E-05 1.53E-05
9.94E-11 2.64E-06 2.71E-06 4.03E-11
THE PHOTOLYTIC RATE CONSTANTS ARE
5.340E-01 1.277E+00 1.
2.779E-03 2.352E-04 5.
THE CURRENT MIXING HEIGHT IS 774
THE CURRENT TEMPERATURE IS 303
THE CURRENT ZENITH ANGLE IS 39
0
HN04
RCHO
R02N
XYLE
7.493E-10
5.644E-05
1.274E-03
8.747E-08
3.523E-03
1.470E-05
4.852E-07
2.786E-06
2.722E-07
•3.638E-05
2.94E-02 2.
1.91E-05 2.
1.67E-08 1.
8.12E-05 7.
6.81E-07 4.
3.39E-10 7.
1.68E-09 4.
1.71E-09 5.
4.35E-06 1.
1.26E-10 6.
171E+01 3
341E-04 5
.73
.00
.40
03 N03
H202 R02
PC03 PPN
R202 ALK7
TMBZ R02P
9.256E-02 9.006E-07
4.912E-06 3.165E-06
6.340E-08 4.395E-04
4.872E-07 2.849E-02
8.984E-04 5.082E-09
1.187E-03 -1.875E-06
1.256E-07 8.920E-06
1.949E-07 4.272E-06
1.566E-06 -1.794E-04
-1.556E-05 2.174E-08
94E-04 2.69E-04 1.76E-08
70E-05 6.80E-06 1.75E-04
68E-08 2.08E-09 2.271-09
24E-05 2.60E-08 1.87E-06
51E-09 7.87E-06 2.76E-05
44E-07 2.12E-07 5.18E-07
10E-13 2.88E-10 6.05E-05
83E-05 1.44E-05 3.71E-08
16E-05 6.31E-07 9.76E-11
82E-12
.044E-02 1.552E-03
.706E-05 8.130E-05
N205
RC03
ACET
ALKN
BZO
2.221E-05
7.430E-07
2.594E-03
9.874E-04
8.793E-09
6.534E-07
1.317E-06
1.199E-05
3.996E-06
2.175E-07
8.82E-05 8
5.06E-07 2
3.93E-04 9
1.00E-04 5
1.22E-09 8
3.28E-11 2
9.35E-09 2
9.29E-08 8
2.38E-14 1
1.017E-01
4.356E-03
HN03 0*SO
ROOH HCHO
MGLY MEK
ETHE PRPE
NPHE PHEN
1.499E-02 2.889E-15
2.322E-06 2.921E-02
1.791E-03 5.167E-03
9.969E-03 8.272E-03
5.223E-04 1.964E-08
1.012E-04 2.950E-08
5.926E-08 -1.337E-04
-1.138E-05 2.293E-05
-7.060E-05 -1.008E-04
6.012E-06 3.204E-10
.68E-05 6.66E-07 3.35E-08
.04E-05 1.82E-06 5.74E-04
.22E-05 3.24E-04 6.08E-08
.43E-06 8.30E-08 8.42E-05
.89E-10 1.74E-10 2.06E-05
.39E-11 4.68E-12 1.72E-05
.28E-12 1.60E-09 3.21E-04
.58E-06 1.47E-05 1.30E-08
.67E-11 1.14E-05 1.69E-10
4.244E-04 4.244E-04
9.596E-03 3.185E-02
OH HONO
R02R ALD2
GLYX GC03
TBUT TOLU
BZN2 NRHC
1.863E-07 2.659E-04
2.585E-06 2.307E-02
3.782E-04 1.706E-09
5.040E-04 1.620E-02
2.097E-09 6.82IE-02
•t.475E-05 -2.861E-06
7.060E-06 -1.123E-04
7.694E-08 6.216E-09
-1.562E-05 -1.025E-04
-6.413E-08 -2.478E-04
1.15E-06 1.05E-05
4.88E-04 4.87E-04
1.43E-08 9.85E-10
2.95E-04 1.30E-08
1.48E-07 1.74E-07
8.37E-06 6.44E-09
4.96E-08 1.21E-11
2.69E-07 2.71E-05
5.28E-10 1.51E-10
1.670E-03
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT )
1100.
NMOC
TOTAL
NMOC/
NOX
.54572 12.44048
NOX
TOTAL
.04387
N02
FRACTION
.87349
03
(INSTANT)
.12965
NO?
(INSTANT)
.03832
TIME N02 NO 0
INTERVAL CO H02 HN04
MC03 PAN RCHO
GPAN ALK4 R02N
CRES DIAL XYLE
1.100E+03 3.832E-02 5.550E-03 5.797E-10
1.000E+01 2.654E-01 8.260E-06 7.096E-05
1.386E-06 7.086E-03 1.432E-03
2.308E-05 2.784E-C2 ^.6VOE-07
1.579E-04 6.025E-04 1.944E-03
NET RATES -2.615E-04 -9.502E-05 4.117E-06
•7.741E-04 8.05Ti-07 6.379E-08
2.277E-07 T./65E-05 2.761E-06
2.493F-07 -1.062E-04 4.652E-08
-2.028E-06 -3.110E-06 -2.094E-05
THE REACTION RATES ARE
2.19E-02 2.63E-02 3.04E-07 6.95E-08 2.08E-02 2.
4.14E-03 2.77E-04 3.62E-05 2.41E-04 1.40E-05 1.
1.13E-07 3.27E-06 2.92E-07 2.94E-07 5.56E-08 5.
5.57E-11 4.21E-08 8.86E-09 4.56E-05 7.24E-05 8.
3.77E-08 7.93E-09 3.32E-04 1.12E-05 9.00E-07 8.
6.72E-07 2.79E-06 1.73E-06 1.75E-06 5.98E-10 1.
3.65E-05 5.19E-05 1.08E-06 1.18E-05 6.92E-09 1.
3.35E-08 2.29E-05 2.65E-06 4.49E-09 2.06E-09 4.
7.22E-06 2.13E-05 1.89E-05 8.18E-06 2.52E-06 8.
2.81E-10 5.85E-06 5.86E-06 2.52E-10 4.13E-10 5.
THE PHOTOLYTIC RATE CONSTANTS ARE
5.715E-01 1.311E+00 1.199E+01 3
3.098E-03 2.954E-04 6.282E-04 6
THE CURRENT MIXING HEIGHT IS 1048.69
THE CURRENT TEMPERATURE IS 303.00
THE CURRENT ZENITH ANGLE IS 27.15
03 N03
H202 R02
PC03 PPN
R202 ALK7
TMBZ R02P
1.296E-01 1.575E-06
2.175E-05 6.136E-06
1.585E-07 7.636E-04
1.068E-06 2.072E-02
3.304E-04 6.111E-09
5.885E-04 -8.691E-07
4.775E-07 1.305E-06
9.242E-L.8 6.871E-06
2.619E-07 -1.024E-04
-6.397E-06 -4.423E-09
71E-04 2.37E-04 4.49E-09
89E-05 4.48E-06 1.67E-04
60E-08 1.07E-08 1.46E-08
40E-05 3.64E-08 2.86E-06
86E-09 9.92E-06 4.55E-05
42E-06 3.09E-07 1.08E-06
72E-12 1.30E-09 6.69E-05
15E-05 9.87E-06 1.41E-08
08E-06 3.83E-07 2.24E-10
84E-12
.197E-02 2.136E-03
.908E-05 9.901E-05
2.
1.
3.
1.
9.
1.
3.
1.
5.
4.
1.
1.
3.
1.
5.
1.
3.
7.
5.
1.
4.
N205
RC03
ACET
ALKN
B7.0
576E-05
550E-06
4S4E-03
285E-03
447E-09
332E-07
228E-07
736E-05
856E-06
490E-08
02E-04 1
03E-06 2
84E-04 9
09E-04 5
80E-09 4
81E-10 1
91E-08 9
96E-08 3
55E-14 4
149E-01
534E-03
HN03 0*SD
ROOM HCHO
MGLY MEK
ETHE PRPE
NPHE PHEN
2.103E-02 5.572E-15
1.052E-05 2.337E-02
1.234E-03 6.792E-03
6.870E-03 4.057E-03
6.607E-04 3.173E-08
1.061E-04 -3.842E-09 -
2.360E-07 -7.693E-05
-7.477E-06 3.254E-05
-4.145E-05 -5.322E-05 •
5.512E-08 1.557E-10 •
.01E-04 7.73E-07 3.86E-08
.31E-05 3.69E-06 5.52E-04
.71E-05 4.45E-04 2.25E-07
.13E-06 1.09E-07 8.68E-05
.31E-09 9.06E-10 3.57E-05
.34E-10 2.82E-11 1.24E-05
.70E-12 7.33E-09 3.05E-04
.13E-06 5.18E-06 2.53E-09
.20E-11 8.04E-06 3.46E-10
4.899E-04 4.899E-04
1.002E-02 3.541E-02
OH HONO
R02R ALD2
GLYX GC03
TBUT TOLU
BZN2 NRHC
2.704E-07 1.647E-04
4.873E-06 1.737E-02
3.817E-04 4.934E-09
1.267E-04 1.178E-02
6.885E-09 5.840E-02
1.549E-06 -1.096E-06
1.002E-06 -8.254E-05
1.148E-07 2.808E-09
2.776E-06 -5.810E-05
1.079E-08 -1.146E-04
2.06E-06 1.89E-05
6.13E-04 6.12E-04
5.67E-08 5.15E-09
3.98E-04 5.07E-08
2.39E-07 3.37E-07
8.37E-06 7.76E-09
1.78E-07 4.43E-11
1.18E-07 2.86E-05
5.67E-10 3.55E-10
1.953E-03
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT )
1200.
NMOC
TOTAL
.43031
NMOC/
NOX
17.89621
NOX
TOTAL
.02404
N02
FRACTION
.90144
03
(INSTANT)
.16968
N02
(INSTANT)
.02168
NJ
I
CTi
O
TIME N02 NO
INTERVAL CO H02
MC03 PAN
GPAN ALK4
CRES DIAL
1.200E+03 2.168E-02 2.370E-03
2.500E+00 2.368E-01 1.957E-05
3.307E-06 9.875E-03
4.469E-05 2.240E-02
8.602E-05 4.530E-04
NET RATES -2.938E-04 -4.599E-05
•3.054E-04 1.372E-07
-6.039E-08 5.300E-05
4.787E-07 -9.157E-05
-8.470E-07 -2.551E-06
THE REACTION RATES ARE
1.28E-02 1.88E-02 1.23E-07 2.81E-08
5.56E-03 4.29E-04 5.61E-05 3.73E-04
2.39E-07 1.01E-05 1.64E-06 1.65E-06
3.43E-10 2.58E-07 5.41E-08 4.04E-05
2.23E-07 4.67E-08 4.62E-04 1.93E-05
1.01E-06 5.97E-06 1.76E-06 2.76E-06
4.63E-05 6.03E-05 2.27E-06 1.40E-05
1.97E-07 2.45E-05 2.36E-06 2.18E-09
8.55E-06 1.69E-05 1.40E-05 3.13E-06
6.35E-10 7.88E-06 7.88E-06 1.42E-09
THE PHOTOLYT1C RATE CONSTANTS ARE
5.906E-01 1.359E+00 1.
3.268E-03 3.338E-04 6.
THE CURRENT MIXING HEIGHT IS 1251
THE CURRENT TEMPERATURE IS 303
THE CURRENT ZENITH ANGLE IS 15
0 03 N03
HN04 H202 R02
RCHO PC03 PPN
R02N R202 ALK7
XYLE TMBZ R02P
4.135E-10 1.697E-01 2.406E-06
9.504E-05 1.021E-04 1.522E-05
1.569E-03 5.056E-07 1.387E-03
5.248E-07 3.041E-06 1.529E-02
9.119E-04 8.007E-05 1.210E-08
7.668E-08 7.185E-04 3.271E-09
6.126E-07 2.895E-06 2.176E-07
1.396E-06 -1.303E-08 1.415E-05
7.139E-09 4.206E-08 -9.193E-05
•1.547E-05 -3.055E-06 1.449E-10
1.16E-02 2.01E-04 1.55E-04 8.18E-10
9.40E-06 1.27E-05 2.54E-06 1.49E-04
2.01E-07 2.03E-07 5.38E-08 1.08E-07
6.26E-05 1.09E-04 4.55E-08 5.54E-06
1.07E-06 1.48E-08 1.35E-05 8.21E-05
9.12E-10 2.67E-06 4.40E-07 2.09E-06
4.55E-08 1.18E-11 8.90E-09 8.13E-05
2.14E-09 2.62E-05 5.17E-06 4.02E-09
2.17E-06 6.73E-06 3.24E-07 1.05E-09
9.83E-10 5.33E-12
219E+01 3.275E-02 2.530E-03
846E-04 7.648E-05 1.096E-04
.47
.00
.97
N205
RC03
ACET
ALKN
BZO
2.234E-05
3.829E-06
4.769E-03
1.711E-03
1.397E-08
-1.641E-07
-7.376E-08
2.561E-05
7.904E-06
-2.363E-10
8.78E-05 8.
2.13E-06 3.
4.07E-04 1.
1.25E-04 4.
4.38E-08 3.
1.42E-09 1.
2.64E-07 6.
4.87E-08 6.
2.73E-13 2.
1.179E-01
4.631E-03
HN03 0*SO OH
ROOH HCHO R02R
MGLY MEK CLYX
ETHE PRPE TBUT
NPHE PHEN BZN2
2.758E-02 8.637E-15 4.261E-07
5.160E-05 1.915E-02 1.164E-05
8.412E-04 9.206E-03 3.810E-04
4.672E-03 1.625E-03 1.706E-05
5.831E-04 4.696E-08 1.638E-08
1.037E-04 3.492E-09 1.158E-07
1.508E-06 -7.703E-05 1.686E-07
-6.433E-06 4.612E-05 -2.579E-07
-3.658E-05 -3.395E-05 -1.498E-06
-2.148E-06 4.807E-10 -9.021E-10
73E-05 6.70E-07 3.34E-08 3.27E-06
25E-05 7.62E-06 5.58E-04 8.21E-04
02E-04 6.22E-04 1.32E-06 3.32E-07
21E-06 1.21E-07 8.85E-05 5.37E-04
41E-08 7.14E-09 6.49E-05 3.65E-07
11E-09 2.32E-10 8.60E-06 9.00E-06
85E-11 5.16E-08 3.11E-04 1.01E-06
64E-07 9.12E-07 2.43E-10 2.43E-08
05E-10 6.72E-06 1.21E-09 8.38E-10
5.271E-04 5.271E-04 2.112E
1.022E-02 3.736E-02
MONO
ALD2
GC03
TOLU
NRHC
1.079E-04
1.263E-02
1.644E-08
8.710E-03
5.327E-02
-1.032E-06
-8.390E-05
-4.266E-10
•5.184E-05
-8.068E-05
2.93E-05
8.20E-04
2.72E-08
2.87E-07
7.33E-07
8.08E-09
2.62E-10
3.33E-05
8.28E-10
-03
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT )
1300.
NMOC
TOTAL
NMOC/
NOX
.33500 42.37859
NOX
TOTAL
.00790
N02
FRACTION
.92735
03
(INSTANT)
.20912
N02
(INSTANT)
.00733
TIME N02 NO 0 03 N03
INTERVAL CO H02 HN04 H202 R02
MC03 PAN RCHO PC03 PPN
GPAN ALK4 R02N R202 ALK7
CRES DIAL XYLE TMBZ R02P
1.300E+03 7.331E-03 5.743E-04 2.590E-10 2.091E-01 2.586E-06
1.000E+01 2.249E-01 5.921E-05 9.736E-05 8.729E-04 5.656E-05
1.206E-05 1.292E-02 1.528E-03 2.512E-06 2.473E-03
7.989E-05 1.747E-02 2.026F-06 1.230E-05 1.038E-02
5.419E-05 2.980E-04 2.879E-04 8.419E-06 4.199E-08
NET RATES -1.732E-04 -1.886E-05 5.443E-08 5.218E-04 1.066E-07
-1.380E-04 9.784E-07 -3.208E-07 2.707E-05 4.798E-07
-1.892E-06 3.956E-05 -2.482E-06 -4.807E-07 1.878E-05
5.806E-07 -7.228E-05 9.519E-09 4.925E-08 -7.022E-05
-3.403E-07 -2.642E-06 -6.211E-06 -3.101E-07 9.334E-11
THE REACTION RATES ARE
4.36E-03 1.17E-02 2.60E-08 5.95E-09 3.47E-03 8.37E-05 4.03E-05 4.80E-11
6.88E-03 5.52E-04 7.22E-05 4.80E-04 3.18E-06 5.01E-06 8.58E-07 7.03E-05
3.42E-07 3.78E-05 1.50E-05 1.51E-05 6.54E-07 6.60E-07 4.68E-07 1.28E-06
4.73E-09 3.67E-06 7.91E-07 3.11E-05 4.78E-05 1.14E-04 3.69E-08 1.27E-05
3.02E-06 6.51E-07 6.04E-04 2.62E-05 1.07E-06 1.55E-08 1.63E-05 1.38E-04
1.36E-06 1.09E-05 1.55E-06 3.38E-06 8.60E-10 4.43E-06 5.23E-07 3.74E-06
5.04b-05 5.71E-05 4.01E-06 1.31E-05 5.31E-07 1.70E-10 1.31E-07 7.97E-05
2.74E-06 2.04E-05 1.73E-06 8.15E-10 1.37E-09 9.12E-06 1.59E-06 6.29E-10
7.85E-06 1.13E-05 6.16E-06 4.58E 07 1.90E-06 4.55E-06 2.72E-07 1.10E-08
2.11E-09 6.38E-06 6.38E-06 1.03E-08 2.35E-09 4.97E-12
THE PHOTOLYTIC RATE CONSTANTS ARE
5.V48E-01 1.368E+00 1.193E+01 3.290E-02 2.638E-03
3.311E-03 3.437E-04 7.008E-04 7.838E-05 1.122E-04
THE CURRENT MIXING HEIGHT IS 1394.76
THE CURRENT TEMPERATURE IS 303.00
THE CURRENT ZENITH ANGLE IS 10.68
8
1
6
2
2
-2
•2
2
5
-3
3
3
3
1
6
2
3
1
3
1
4
N205
RC03
ACET
ALKN
BZO
.179E-06
.464E-05
.444E-03
.163E-03
.797E-08
.693E-07
.377E-06
.650E-05
.993E-06
.771E-09
.19E-05 3
.43E-06 4
.67E-04 9
.10E-04 2
.59E-07 6
.12E-08 2
.23E-06 1
.31E-08 4
.52E-12 2
.189E-01
.647E-03
HN03 0*SD
ROOM HCHO
MGLY MEK
ETHE PRPE
NPHE PHEN
3.187E-02 1.110E-14
5.129E-04 1.445E-02
5.000E-04 1.210E-02
2.790E-03 4.054E-04
4.393E-04 1.453E-07
3.456E-05 2.491E-08
1.766E-05 -7.411E-05
-4.637E-06 4.391E-05 -
•2.565E-05 -1.058E-05 -
-2.183E-06 3.117E-09 -
.19E-05 2.45E-07 1.21E-08
.30E-05 1.31E-05 4.09E-04
.49E-05 8.04E-04 1.48E-05
.73E-06 8.22E-08 7.82E-05
.29E-07 1.36E-07 1.16E-04
.02E-08 4.36E-09 5.12E-06
.03E-09 7.97E-07 2.74E-04
.73E-08 5.74E-08 7.78E-12
.72E-09 4.55E-06 7.34E-09
5.366E-04 5.366E-04
1.023E-02 3.781E-02
5
4
3
8
3
2
4
1
1
4
3
8
3
6
5
7
1
1
1
OH MONO
R02R ALD2
GLYX GC03
TBUT TOLU
BZN2 NRHC
.944E-07 4.209E-05
.220E-05 7.955E-03
.343E-04 8.069E-08
.708E-07 5.940E-03
.918E-08 4.965E-02
.660E-07 -1.030E-06
.207E-07 -6.384E-05
.216E-06 -1.470E-08
.703E-08 -3.956E-05
.419E-09 -4.644E-05
.54E-06 3.08E-05
.40E-04 8.40E-04
.84E-06 2.75E-07
.62E-04 3.16E-06
.05E-07 1.38E-06
.46E-06 5.16E-09
.11E-05 3.53E-09
.33E-09 3.17E-05
.68E-09 3.58E-09
2.151E-03
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT }
1400.
NMOC
TOTAL
NMOC/
NOX
.27925 100.37181
NOX
TOTAL
.00278
N02
FRACTION
.93821
03
(INSTANT)
.22455
N02
(INSTANT)
.00261
TIME
INTERVAL
1 .400E+03
9.628E+00
NET RATES
N02
CO
HC03
GPAN
CRES
2.610E-03
2.180E-01
3.244E-05
9.327E-05
4.305E-05
-5.159E-05
-9.893E-05
-3.776E-05
2.557E-07
-1.261E-07
NO
H02
PAN
ALK4
DIAL
1.719E-04
7.554E-05
1.298E-02
1.417E-02
1.703E-04
-3.280E-05
•1.535E-06
1.427E-05
-4.525E-05
-1.553E-06
0
HN04
RCHO
R02N
XYLE
2.067E-10
4.332E-05
1.334E-03
3.526E-06
1.046E-04
-8.171E-07
7.740E-06
•3.358E-06
-4.127E-07
-1.666E-06
2
3
7
2
3
1
4
-8
•2
-2
03
H202
PC03
R202
TMBZ
.245E-01
.227E-03
.810E-06
.238E-05
.066E-06
.223E-04
.014E-05
.395E-06
.568E-06
.516E-08
N03
R02
PPN
ALK7
R02P
1.517E-06
1.100E-04
2.989E-03
7.365E-03
7.873E-08
1.441E-06
-8.403E-06
9.908E-06
-3.909E-05
•7.986E-09
N205
RC03
ACET
ALKN
BZO
1.842E-06
4.023E-05
7.531E-03
2.309E-03
3.785E-08
-5.824E-07
-4.663E-05
1.355E-05
1.010E-06
-8.252E-08
HN03
ROOH
MGLY
ETHE
NPHE
3.203E-02
2.712E-03
3.082E-04
1.746E-03
3.504E-04
-8.607E-06
4.618E-05
-2.306E-06
-1.294E-05
-9.783E-07
0*SO
HCHO
MEK
PRPE
PHEN
1.121E-14
1.150E-02
1.381E-02
1.204E-04
3.882E-07
•2.515E-08
-2.783E-05
2.014E-05
-2.320E-06
3.481E-09
OH
R02R
GLYX
TBUT
BZN2
4.824E-07
8.405E-05
2.549E-04
5.700E-07
5.329E-08
6.124E-06
-5.4HE-06
•1.263E-06
•2.772E-09
-1.210E-07
MONO
ALD2
GC03
TOLU
NRHC
1.111E-05
5.686E-03
2.410E-07
4.237E-03
•..747E-02
-2.396E-07
-2.281E-05
-2.790E-07
-2.217E-05
-3.059E-05
to
I
THE REACTION RATES ARE
1.54E-03 9.38E-03 7.39E-09 1.69E-09 1.12E-03 3.20E
7.34E-03 5.57E-04 7.29E-05 4.84E-04 7.72E-07 1.31E
1.23E-07 5.18E-05 2.44E-05 2.46E-05 4.90E-07 4.94E
1.79E-08 1.96E-05 5.97E-06 2.41E-05 3.74E-05 7.38E
1.58E-05 4.82E-06 6.07E-04 1.86E-05 9.04E-07 7.95E
1.50E-06 1.01E-05 1.18E-06 2.09E-06 3.85E-10 4.71E
3.32E-05 3.29E-05 3.47E-06 6.84E-06 1.18E-06 5.74E
1.50E-05 1.04E-05 1.17E-06 4.07E-10 5.05E-10 2.20E-
3.64E-06 6.33E-06 1.81E-06 1.35E-07 1.23E-06 2.12E
3.31E-09 2.99E-06 3.09E-06 1.78E-08 3.20E-09 4.75E-12
05 7.07E
06 3.05E
07 1.69E
05 1.73E
09 1.52E
06 4.68E
10 6.28E
06 5.07E
06 1.53E
06 4.30E
07 2.03E
06 3.85E
1.29E
1.53E
07 4.36E
07 4.34E
07 1.49E
07 2.63E
08
05
12 6.67E
05 2.80E-
06 2.13E
05 6.38E
•04 2.61E
•06 8.06E
•05 7.49E
10 2.28E
•08 1.28E
08 1
20E-06
39E-05
81E-05
87E-06
81E-06
17E-07
64E-09
51E-08
40E-08
5.53E
1.14E
7.87E
3.44E
1.16E
3.58E
3.99E
4.03E
2.19E
08 2.54E
•05 1.56E
•04 3.68E
•08 6.29E
•06 1.40E
08 3.15E
06 1.63E
08 4.06E
•06 1.27E
09 2.06E
04 3.82E
05 1.35E
05 6.35E
04 5.69E
06 3.73E
04 2.81E
12 5.12E
08 2.27E
-06 1
-07 1
06
05
10
09
86E-05
,74E-04
,42E-06
,09E-05
.31E-06
.87E-09
.37E-08
.84E-05
.75E-09
THE PHOTOLYTIC RATE CONSTANTS ARE
5.886E-01 1.355E+00
3.249E-03 3.292E-04
THE CURRENT MIXING HEIGHT IS
THE CURRENT TEMPERATURE IS
THE CURRENT ZENITH ANGLE IS
1.226E+01
6.774E-04
1500.00
303.00
17.79
3.267E-02
7.561E-05
2.481E-03
1.083E-04
1.176E-01
4.623E-03
5.227E-04
1.021E-02
5.227E-04
3.715E-02
2.093E-03
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT )
1500.
NMOC
TOTAL
NMOC/
NOX
.25520 122.61586
NOX
TOTAL
.00208
N02
FRACTION
.94395
03
(INSTANT)
.23705
N02
(INSTANT)
.00196
I
O>
Ul
TIME N02 NO
INTERVAL CO H02
MC03 PAN
GPAN ALK4
CRES DIAL
1.500E+03 1.965E-03 1.166E-04
1.000E+01 2.244E-01 7.279E-05
3.719E-05 1.208E-02
9.159E-05 1.240E-02
3.347E-05 1.172E-04
NET RATES -3.449E-06 -1.215E-06
9.760E-05 5.694E-08
•9.657E-07 -1.743E-05
•8.674E-08 -2.689E-05
-1.777E-07 -6.398E-07
THE REACTION RATES ARE
1.11E-03 9.07E-03 5.38E-09 1.23E-09
7.52E-03 4.84E-04 6.32E-05 4.20E-04
8.47E-08 5.27E-05 2.26E-05 2.28E-05
1.84E-08 2.32E-05 8.12E-06 2.00E-05
1.84E-05 6.44E-06 5.65E-04 1.55E-05
1.49E-06 1.05E-05 9.01E-07 1.52E-06
2.69E-05 2.37E-05 3.36E-06 4.39E-06
1.79E-05 6.63E-06 8.49E-07 2.72E-10
2.32E-06 4.09E-06 6.67E-07 1.49E-08
3.95E-09 2.44E-06 2.42E-06 1.79E-08
0 03
HN04 H202
RCHO PC03
R02N R202
XYLE TM8Z
1.999E-10 2.370E-01 1.
3.209E-05 5.642E-03 1.
1.202E-03 9.919E-06 3.
3.333E-06 2.207E-05 5.
4.150E-05 3.637E-07 7.
8.188E-07 1.749E-04 2.
•1.446E-07 3.653E-05 -1.
-2.237E-06 -3.505E-07 5.
-1.067E-08 -6.540E-08 -2.
-6.667E-07 -1.488E-08 -3.
7.99E-04 2.54E-05 4.48E-06
4.85E-07 7.38E-07 2.30E-07
4.41E-07 4.44E-07 2.71E-06
3.20E-05 6.22E-05 1.47E-08
7.38E-07 6.69E-09 1.31E-05
2.82E-10 4.20E-06 3.75E-07
1.07E-06 5.50E-10 6.93E-07
3.25E-10 6.20E-07 1.63E-07
8.83E-07 1.54E-06 9.57E-08
3.33E-09 4.75E-12
N03
R02
PPN
ALK7
R02P
416E-06
115E-04
110E-03
729E-03
268E-08
784E-08
454E-07
620E-07
368E-05
572E-10
1.98E-12
1.42E-05
6.24E-06
1.13E-05
1.46E-04
4.28E-06
2.91E-05
4.39E-11
2.34E-08
1
4
8
2
3
-4
-1
1
1
-1
4
2
1
5
3
9
7
6
1
N205
RC03
ACET
ALKN
BZO
.192E-06
.692E-05
.603E-03
.411E-03
-514E-08
.876E-09
.273E-06
-570E-05
.029E-06
.712E-09
.69E-06 4
.68E-06 3
.47E-04 6
.12E-05 1
.20E-06 4
-19E-08 1
.12E-06 3
.48E-10 2
.20E-11 1
HN03 0*SO
ROOM HCHO
MGLY MEK
ETHE PRPE
NPHE PHEN
3.315E-02 9.727E-15
5.721E-03 1.048E-02
2.244E-04 1.545E-02
1.205E-03 3.670E-05
3.064E-04 4.960E-07
1.669E-05 1.686E-07
4.850E-05 -1.437E-05
-1.045E-06 2.296E-05
-7.476E-06 -7.840E-07
-7.893E-07 3.225E-10
.66E-06 3.58E-08 1.78E-09
.23E-05 1.12E-05 1.02E-04
.18E-05 6.91E-04 3.60E-05
.41E-06 2.79E-08 4.90E-05
.90E-06 1.72E-06 1.45E-04
.41E-07 4.94E-08 2.23E-06
.64E-09 4.59E-06 1.13E-04
.23E-10 4.09E-10 3.77E-14
.51E-08 1.53E-06 1.13E-08
4
8
2
5
5
1
•6
-8
-6
-3
1
2
1
5
5
2
2
4
2
OH
R02R
GLYX
TBUT
BZN2
.466E-07
.605E-05
.OOOE-04
.469E-09
.551E-08
.986E-09
.910E-08
.363E-07
.365E-10
.103E-09
.84E-06 1
.77E-04 2
.51E-05 2
.48P-04 1
.78E-07 1
.52E-06 1
.77E-05 1
.59E-12 1
.11E-09 9
HONO
ALD2
GC03
TOLU
NRHC
6.507E-06
4.925E-03
2.851E-07
3.321E-03
4.747E-02
-2.313E-08
-9.462E-06
-8.903E-09
-1.332E-05
O.OOOE-01
.68E-05
.77E-04
.75E-06
.20E-05
.39E-06
.27E-09
.42E-08
.33E-05
.17E-09
THE PHOTOLYTIC RATE CONSTANTS ARE
5.660E-01 1.301E+00
3.051E-03 2.858E-04
THE CURRENT MIXING HEIGHT IS
THE CURRENT TEMPERATURE IS
THE CURRENT ZENITH ANGLE IS
1.188E+01
6.141E-04
1500.00
303.00
29.31
3.173E-02
6.720E-05
2.040E-03
9.626E-05
1.134E-01
4.506E-03
4.800E-04
9.952E-03
4.800E-04
3.488E-02
1.910E-03
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT )
1600.
NHOC
TOTAL
NMOC/
NOX
.23663 115.05038
NOX
TOTAL
.00206
N02
FRACTION
.94781
03
(INSTANT)
.24676
N02
(INSTANT)
.00195
TIME
INTERVAL
1.600E+03
1.000E+01
NET RATES
N02
CO
MC03
GPAN
CRES
1.949E-03
2.297E-01
3.391E-05
8.315E-05
2.281E-05
-3.547E-06
7.392E-05
-1.330E-07
-1.515E-07
-1.555E-07
NO
H02
PAN
ALK4
DIAL
1.073E-04
6.449E-05
1.095E-02
1.093E-02
8.762E-05
4.481E-06
2.646E-07
-1.700E-05
-2.060E-05
•3.971E-07
0
HN04
RCHO
R02N
XYLE
1.933E-10
2.821E-05
1.071E-03
2.588E-06
1.722E-05
1.748E-05
-9.107E-08
-1.909E-06
-9.095E-09
-2.405E-07
03
H202
PC03
R202
TMBZ
2.468E-01
7.542E-03
9.660E-06
1.785E-05
4.822E-08
1.202E-04
2.535E-05
-1.155E-07
-6.425E-08
-1.715E-09
N03
R02
PPN
ALK7
R02P
1.542E-06
9.536E-05
3.050E-03
4.514E-03
4.721E-08
-3.145E-09
-2.071E-07
-1.55AE-06
-1.622E-05
-2.274E-10
N205
RC03
ACET
AL
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT )
1700.
NMOC
TOTAL
NMOC/
NOX
.22497 102.38159
NOX
TOTAL
.00220
N02
FRACTION
.95294
03
(INSTANT)
.25397
N02
(INSTANT)
.00209
TIME
INTERVAL
1.700E+03
1 .OOOE+01
NET RATES
N02
CO
MC03
GPAN
CRES
2.094E-03
2.332E-01
2.894E-05
7.406E-05
1.432E-05
3.931E-06
5.217E-05
2.301E-09
-1.613E-07
-1.355E-07
NO
H02
PAN
ALK4
DIAL
1.034E-04
5.331E-05
1.004E-02
9.968E-03
7.007E-05
-3.175E-07
-2.121E-07
-1.548E-05
-1.433E-05
-2.629E-07
0
HN04
RCHO
R02N
XYLE
1.838E-10
2.506E-05
9.802E-04
1.839E-06
9.052E-06
5.730E-06
-1.815E-07
-1.362E-06
•1.259E-08
-9.642E-08
03
H202
PC03
R202
TMBZ
2.540E-01
8.644E-03
8.517E-06
1.310E-05
1.374E-08
1.100E-04
1.535E-05
-5.356E-08
-8.883E-08
-3.726E-10
N03
R02
PPN
ALK7
R02P
1.821E-06
7.590E-05
2.916E-03
3.791E-03
2.448E-08
5.007E-08
-3.765E-07
-2.764E-06
-1.039E-05
•2.148E-10
N205
RC03
ACET
ALKN
B20
1.630E-06
3.737E-05
9.916E-03
2.440E-03
1.836E-08
7.901E-09
-4.957E-08
7.179E-06
-1.074E-07
-8.216E-09
HN03
ROOM
MGLY
ETHE
NPHE
3.486E-02
1.000E-02
1.497E-04
6.416E-04
1.918E-04
1.218E-05
2.369E-05
-4.340E-07
-2.825E-06
-1.068E-06
0*SD
HCHO
MEK
PRPE
PHEN
4.062E-15
9.133E-03
1.714E-02
4.659E-06
3.274E-07
1.550E-08
-7.337E-06
7.879E-06
-7.450E-08
-1.926E-09
OH
R02R
GLYX
TBUT
BZN2
2.961E-07
6.095E-05
1.257E-04
O.OOOE-01
4.215E-08
5.814E-08
-2.749E-07
-4.475E-07
O.OOOE-01
-8.776E-09
HONO
ALD2
GC03
TOLU
NRHC
6.075E-06
4.275E-03
2.105E-07
2.224E-03
4.747E-02
-2.476E-09
-2.558E-06
4.140E-10
-5.914E-06
O.OOOE-01
THE REACTION RATES ARE
9.61E-04 8.34E-03 5.27E-09 1.20E-09 7.59E-04 2.91E-05 5.11E-06 1.56E
7.19E-03 2.02E-04 2.64E-05 1.75E-04 2.85E-07 5.33E-07 2.45E-07 1.00E
4.39E-08 4.14E-05 1.21E-05 1.22E-05 4.15E-07 4.18E-07 2.71E-06 6.34E
8.53E-09 1.26E-05 5.15E-06 1.09E-05 2.00E-05 3.60E-05 1.64E-08 7.21E
9.73E-06 3.99E-06 4.70E-04 8.39E-06 3.68E-07 7.01E-09 9.94E-06 1.34E
9.25E-07 7.72E-06 4.98E-07 6.33E-07 2.28E-10 3.30E-06 2.46E-07 3.46E
1.43E-05 1.04E-05 2.25E-06 2.15E-06 4.34E-07 2.07E-10 3.05E-07 1.53E
1.01E-05 2.34E-06 4.85E-07 1.33E-10 2.23E-10 5.22E-08 2.22E-08 5.13E
9.19E-07 1.77E-06 9.64E-08 3.73E-10 2.51E-07 8.47E-07 2.86E-08 5.78E-
3.35E-09 1.96E-06 1.96E-06 9.95E-09 2.53E-09 4.75E-12
THE PHOTOLYTIC RATE CONSTANTS ARE
4.588E-01 1.231E+00
2.187E-03 1.449E-04
THE CURRENT MIXING HEIGHT IS
THE CURRENT TEMPERATURE IS
THE CURRENT ZENITH ANGLE IS
12 6.
05 1.
06 8.
42E-06
87E-06
86E-05
95E-05
01E-06
97E-08
09E-06
06E-10
09 2.75E-12
6.37E
2.22E
4.36E
6.20E
2.86E
7.08E
1.47E
O.OOE
4.05E-
06 4.89E
05 7.92E
05 5.87E
07 3.11E
06 1.17E
08 2.90E
09 2.17E
01 O.OOE
09 8.54E
08 2.44E
06 6.64E
04 1.79E
08 3.38E
06 1.36E
-08 1.31E-
06 7.11E-
01 O.OOE-
07 4.34E-
09 2.24E
05 2.16E
05 8.83E
05 4.54E
04 3.74E
06 1.11E
05 1.44E
01 O.OOE
09 1.10E-
06 1.
04 2,
06 3,
04 6.
07 1,
06 1.
05 6.
01 5.
09 4.
98E-05
16E-04
14E-06
83E-06
06E-06
09E-09
85E-09
91E-06
01E-09
1.085E+01
3.757E-04
1500.00
303.00
54.00
2.830E-02
3.776E-05
7.950E-04
5.399E-05
8.767E-02
3.964E-03
3.136E-04
8.761E-03
3.136E-04
2.529E-02
1.196E-03
-------
TABLE 2-19 (CONTINUED)
TIME
(LOT )
1800.
NMOC
TOTAL
NMOC/
NOX
.21773 87.53822
NOX
TOTAL
.00249
N02
FRACTION
.96344
03
(INSTANT)
.25964
N02
(INSTANT)
.00240
NJ
I
CTi
TIME
INTERVAL
1 .800E+03
1.000E+01
NET RATES
N02
CO
MC03
GPAN
CRES
2.396E-03
2.355E-01
2.316E-05
6.510E-05
6.632E-06
5.426E-06
3.034E-05
-1.446E-07
-1.363E-07
-1.124E-07
NO
H02
PAN
ALK4
DIAL
9.092E-05
3.793E-05
9.178E-03
9.340E-03
5.757E-05
2.854E-07
-2.814E-07
-1.344E-05
-7.787E-06
-1.614E-07
0
HN04
RCHO
R02N
XYLE
1.531E-10
2.040E-05
9.202E-04
1.142E-06
5.691E-06
-9.130E-07
-1.062E-07
-7.454E-07
-1.245E-08
-3.516E-08
03
H202
PC03
R202
TMBZ
2.596E-01
9.247E-03
6.908E-06
8.319E-06
5.289E-09
7.795E-05
6.673E-06
-4.026E-08
-8.625E-08
-8.322E-11
N03
R02
PPN
ALK7
R02P
2.495E-06
5.476E-05
2.724E-03
3.350E-03
7.974E-09
2.209E-08
-3.768E-07
-3.358E-06
-5.326E-06
-2.674E-10
N205
RC03
ACET
ALKN
BZO
2.553E-06
3.006E-05
1.022E-02
2.432E-03
1.011E-08
2.131E-08
-1.822E-07
3.732E-06
•1.309E-07
8.023E-10
HN03
ROOK
MGLY
ETHE
NPHE
3.549E-02
1.101E-02
1.268E-04
5.209E-04
1.228E-04
9.118E-06
1.221E-05
-3.476E-07
-1.504E-06
-1.169E-06
0*SD
HCHO
MEK
PRPE
PHEN
1.457E-15
8.892E-03
1.745E-02
2.213E-06
2.057E-07
-2.036E-07
-1.458E-06
3.605E-06
-2.523E-08
-2.043E-09
OH
R02R
GLYX
TBUT
BZN2
1.718E-07
4.530E-05
1.045E-04
O.OOOE-01
3.223E-08
8.796E-08
•2.779E-07
-2.899E-07
O.OOOE-01
7.059E-10
HONO
ALD2
GC03
TOLU
NRHC
6.509E-06
4.212E-03
1.620E-07
1.973E-03
4.747E-02
1.927E-08
-4.925E-08
-1.425E-09
-3.042E-06
O.OOOE-01
THE REACTION RATES ARE
8.15E-04 6.94E-03 5.03E-09 1.15E-09 6.83E-04 3.40E-05 6.15E-06 1.20E
6.04E-03 7.22E-05 9.47E-06 6.29E-05 1.45E-07 4.07E-07 2.80E-07 6.64E
2.07E-08 3.01E-05 6.15E-06 6.20E-06 4.04E-07 4.08E-07 1.75E-06 3.93E
4.44E-09 7.29E-06 3.33E-06 6.07E-06 1.26E-05 2.03E-05 2.19E-08 4.99E
5.62E-06 2.57E-06 4.29E-04 4.57E-06 1.93E-07 9.02E-09 7.09E-06 1.24E
4.87E-07 4.56E-06 3.35E-07 3.05E-07 2.60E-10 2.91E-06 1.66E-07 3.05E
7.79E-06 5.33E-06 1.30E-06 1.17E-06 1.92E-07 9.26E-11 1.52E-07 8.54E
6.03E-06 1.10E-06 4.02E-07 9.00E-11 2.48E-10 1.44E-08 1.08E-08 2.03E
4.38E-07 9.63E-07 3.52E-08 8.32E-11 6.73E-08 5.38E-07 8.18E-09 1.34E
2.88E-09 1.72E-06 1.71E-06 5.42E-09 1.93E-09 4.75E-12
THE PHOTOLYTIC RATE CONSTANTS ARE
3.401E-01 1.016E+00
1.422E-03 6.709E-05
THE CURRENT MIXING HEIGHT IS
THE CURRENT TEMPERATURE IS
THE CURRENT ZENITH ANGLE IS
•12 1.01E
•06 1.10E
•06 5.62E
•06 1.68E
04 1.16E
•06 2.72E
06 1.40E
12 6.88E
09 6.46E
05 9.97E
06 1.30E
05 3.08E
05 2.83E
06 1.68E
08 3.93E
06 6.74E
11 O.OOE-
13 1.06E-
06 7.66E
05 4.TOE
05 5.40E
07 4.20E
06 7.66E
08 1.80E
10 1.11E-
01 O.OOE
09 5.38E
08 3.a3E
06 4.15E
04 9.20E
08 2.38E
07 1.27E
08 8.96E
06 4.65E
01 O.OOE
07 1.70E
0» 2.
05 1.
06 5.
05 4.
53E
76E
05E
16E
04 2.00E-07 6
07 5.47E
05 7.61E
01 O.OOE
09 6.06E
-07
•06
-01
-10
31E-05
76E-04
08E-06
89E-06
33E-07
26E-09
67E-09
04E-06
46E-09
9.272E+00
2.102E-04
1500.00
303.00
66.27
2.327E-02
1.953E-05
2.780E-04
2.793E-05
6.245E-02
3.204E-03
1.887E-04
7.062E-03
1.887E-04
1.673E-02
6.830E-04
MAXIMUM 03 NOT REACHED, THE LAST ONE HOUR AVERAGE WAS .25701 PPM.
MAXIMUM ONE HOUR AVE N02 = .08230 CENTERED AT 855. LOT
-------
TABLE 2-19 (CONTINUED)
.300+-
N)
I
CT>
c
0
N
C
E
N
T
R
A
T
I
0
N
P
P
H
.270
.240
.210
.180
.150
.120
.090
.060
.030
0 00 0 0
0 0 00
00 0 0
00 0
000 0
0 00 0
00
00
oo
00
.000+---
800.
1
I
I
I
+
I
0 00 01
I
1
+
I
I
I
I
+
I
I
I
I
•f
I
I
I
I
+
I
I
I
I
•f
I
I
I
I
+
I
I
I
I
+
I
I
900.
1000.
1100.
03
1200. 1300. UOO. 1500.
TIME (LOT)
TEST PROBLEM #3 - OZIPM "CALC" RUN
CONCENTRATION AS A FUNCTION OF TIME
1600.
1700.
131 REACTION MECHANISM
1800.
-------
TABLE 2-19 (CONTINUED)
KJ
I
oo
c
0
N
C
E
N
T
R
A
T
I
0
N
P
P
H
.100+-
.090
.080+
.070+
.060
.050+
.040
.030
.020
.010
0 0
0
00
00
00
00
00
I
0 I
000 I
0000000000000000000000000 01
.000+---
800.
900.
1000.
1100. 1200. 1300. UOO. 1500. 1600. 1700.
TIME (LOT)
TEST PROBLEM #3 - OZIPM "CALC" RUN - 131 REACTION MECHANISM
N02 CONCENTRATION AS A FUNCTION OF TIME
1800.
-------
TABLE 2-20. EXAMPLE #4
OZOME ISOPLETH PLOTTING PACKAGE
WITH OPTIONAL MECHANISMS
0 Z I P M
VERSION 3.1
SEPTEMBER, 1985
K)
I
CTi
-------
THE INPUTS FOR THIS RUN ARE
TABLE
to
I
TITL
MECH
ALK4
TMBZ
4.5
9.0
N02
0
0
0
NO
N02
NO
NO
N02
N205
N205
N02
N03
N03
03
03
0*SO
0*SD
NO
MONO
N02
N02
HN03
CO
03
NO
N02
HN04
HN04
03
H02
H02
N03
N03
H202
H202
R02
RC03
RC03
TEST PROBLEM
1.
42.
73.
AIK7
HCHO
7.0
1.0
HV
N02
N02
03
03
N03
NO
N03
N03
HV
HV
HV
HV
OH
HV
OH
OH
OH
OH
H02
H02
OH
H02
H02
H02
H02
H02
HV
OH
NO
NO
N02
132.
13.
46.
82.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
#4 - OZIPM "EKMA" RUN - 131 REACTION MECHANISM
17. 13. 0.
14. 15. 16.
47. 52. 61.
114.
ETHE PRPE TBUT TOLU
ALD2 RCHO MEK NRHC
2.0 3.0 4.0 7.0
2.0 3.0 4.0 1.0
1.NO 1.0
1.03
1.NO
1.N03
1.N02
1.N03
2.N02
2.N02
1.N205
1.N02 1. N03
2.HN03
1.NO 1. N02
1.NO
1.N02 1. 0
1.0
1.0*SO
2. OH
1.0
1.HONO
1.NO 1. OH
1.HONO -1. N02 1. HN03
1.HN03
1.N03
1.H02
1.H02
1.N02 1. OH
1.HN04
1.N02 1. H02
1.N02
1.0H
1.H202
1.H202
1.HN03
1.HN03
2. OH
1.H02
1.NO
1.NO
1.N02
303.
20.
69.
XYLE
8.0
1.00E 00
4.87E+07
1.37E+04
3.29E+03
2.68E+01
4.77E-02
2.75E+04
1.50E-04
1.71E+03
2.08E+00
3.00E-02
5.98E-01
1.00E 00
1.00E 00
1.00E 00
1.00E 00
6.50E+09
4.32E+10
9.75E+03
1.00E 00
1.17E-04
1.68E+04
1.89E+02
3.22E+02
1.00E+02
1.22E+04
2.02E+03
4.93E*00
5.91E+03
2.96E«00
4.46E+03
5.08E+03
4.46E»03
5.08E+03
1.00E 00
2.45E*03
1.14E+04
1.14E+04
7.57E+03
35.
71.
0
•1282
0
-894
1370
2450
•252
-529
-273
11379
0
1229
0
0
0
0
0
0
•833
0
0
•737
-778
0
942
•240
-773
10103
0
579
•771
-2971
•771
-2971
0
187
•180
-180
•180
-------
THE INPUTS FOR THIS RUM ARE
TABLE 2-20 (CONTINUED)
R02
RC05
ROOM
R02
R02
RC03
HCHO
HCHO
HCHO
HCHO
HCHO
AL02
ALD2
1.
A102
MC03
1.
MC03
MC03
HC03
MC03
PAN
RCHO
RCHO
1.
RCHO
PC03
1.
PC03
PC03
PC03
PC03
PPM
ACET
1.
ACET
MEK
1.
MEK
.5
GLYX
GLYX
.37
GLYX
.37
GC03
GC03
GPAN
GC03
GC03
H02
H02
HV
R02
RC03
RC03
HV
HV
OH
N03
H02
OH
HV
R02R
M03
NO
R02
N02
H02
R02
RC03
OH
HV
R02R
N03
NO
R02
N02
H02
R02
RC03
HV
R02R
OH
HV
R02R
OH
AL02
HV
OH
RC03
N03
GC03
N02
NO
H02
R02
40
41
42
43
44
45
46
47
48
49
50
51
52
1. R02
53
54
55
56
57
58
59
60
61
1. R02
62
63
64
65
66
67
68
69
1. R02
70
71
1. R02
72
1
1
1
2
1
1
1
1
1
1
1
1
1
1
.
1
1
1
1
1
1
1
1
.
1.
.5 HCHO
73
74
75
.H02
.H02
.H02
.H02
.CO
.H02
.HN03
.R02R
.MC03
.CO *
.HN03
.N02 *
.PAN
.ROOH
5H02
.H02
.MC03
.RC03
.ALD2*
.HN03
.N02 *
.(• N
.ROOH
5H02
.H02
.PC03
.MC03*
.MGLY
.MC03*
5R02R*
.5
. 13HCHO
.63H02 *
1
.HN03*
1.
1.
1.
1.
1.
1.
1.
1.
1.
.
.
.
.
.
.
.
.
1.
1.
1.
1.
1.
1.
1.
1.5
PC03
1.87
1.26
.63
OH
CO
CO
H02
R02
RC03
HCHO
MC03
HCHO
HCHO
HCHO
HCHO
N02
PC03
H02
PC03
AL02
AL02
ALD2
AL02
N02
HCHO
R02R
ALD2
R02
1.
CO
CO
H02
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
1.
.5
RC03
.37
1.26
CO
H02
RC03
R02R
R02
RC03
RC03
CO
RC03
R02R
R02
RC03
RC03
RC03
R02
RC03
MC03
GC03
CO
4
4
1
1
4
3
1
1
1
8
1
2
1
3
1
7
4
4
3
2
2
1
3
1
7
4
4
3
.43E*03
.43E+03
.OOE 00
.48E+00
.43E+03
.69E+03
.OOE 00
.OOE 00
.33E+04
.82E-01
.48E+01
.36E+04
.OOE 00
.69E+00
.14E+04
.57E+03
.43E+03
.43E+03
.69E+03
.21E-02
.93E*04
.OOE 00
.63E+00
.14E+04
.57E+03
.43E+05
.43E+03
.69E+03
2.21E-02
1
3
1
1
1
1
8
.OOE 00
.39E+02
.OOE 00
.46E+03
.OOE 00
.70E+04
.88E-01
0.
0.
0.
0.
0.
0.
0.
0.
0.
2060.
0.
-250.
0.
1427.
-180.
-180.
0.
0.
0.
13542.
-252.
0.
1432.
-180.
-180.
0.
0.
0.
13542.
0.
1125.
0.
745.
0.
0.
2058.
.37 RC03
76
77
78
79
80
1
1
1
1
.
.GPAN
.N02
.GC03
.ROOH
5H02
1.
1.
1.
1.
H02
N02
CO
CO
1.
1.
1.
CO
RC03
R02
7
1
2
4
4
.57E+03
.14E+04
.21E-02
.43E+03
.43E«03
•180.
-180.
13542.
0.
0.
-------
THE INPUTS FOR THIS RUN ARE
TABLE 2-20 (CONTINUED)
ro
I
GC03
HGLY
1.
HGLY
MGLY
1.
ALK4
.34
ALK7
.36
ALKN
.48
R02N
R02N
R02N
R02N
R202
R202
R202
R202
R02R
R02R
R02R
R02R
ETHE
.22
ETHE
ETHE
1.
ETHE
1.
PRPE
1.
PRPE
.06
PRPE
.2
PRPE
1.
TBUT
TBUT
.12
TBUT
TBUT
1.
TOLU
.4
DIAL
DIAL
1.
RC03
HV
RC03
OH
N03
RC03
OH
ACET
OH
ACET
OH
ALD2
NO
H02
R02
RC03
NO
H02
R02
RC03
NO
H02
R02
RC03
OH
ALD2
03
0
R02R
N03
R02
OH
R02
03
OH
0
H02
N03
R202
OH
03
OH
0
N03
R02
OH
DIAL
OH
HV
RC03
81
82
83
84
85 .
.44 MEK
86 .
.88 MEK
87
1
1
1
1
.H02
.MC03*
.MC03
.HN03*
19HCHO*
.07
02HCHO*
1
.16 HCHO
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
1. R02
103
104
105 .
.17 H02
106
.6 R02R
107
1. R02
108
109
.21 H02
110
111
112 .
.84 R02
113
114
1
1
1
1
1
1
1
1
1
1
.
.
1
i
1
1
1
.18
.N02 *
1.39
.ALKN
.ROOM
.R02
.RC03
.N02
.ROOH
.R02
.RC03
.N02
.ROOH
5H02
5H02
.R02R*
.HCHO
.HCHO*
.N02 *
.R02R*
64HCHO*
.
1
1
1
1
1
.13
6ACET*
.4
.N02 *
.R02R
.AL02*
.27
.MEK
.N02 *
16CRES*
1
1
.144
.PC03
.H02 *
1.
1.
1.
1.
.31
R02N
.03
R02N
.15
R202
1.
.5
.5
1.
1.
1.
1.
.12
1.
2.
1.
.5
R02R
.4
CO
1.
2.
.15
R02
.4
2.
.16
MGLY
1.
1.
CO
H02
CO
MC03
ALD2
.93
ALD2
.82
MEK
1.39
MEK
H02
H02
H02
R02
RC03
R02
H02
H02
HCHO
HCHO
ALD2
.13
HCHO
.6
HCHO
ALD2
CO
.30
H02
ALD2
H02
.114
RC03
CO
1.
1.
1.
1.
.17
R02R
.25
R02R
1.05
R02
1.
1.
1.56
.42
1.
1.
1.
.28
R02
.2
R02
1.
1.
.27
HCHO
1.
.84
GL'rX
1.
RC03
CO
RC03
CO
RCHO
.6
RCHO
.84
RCHO
MEK
MEK
HCHO
CO
CO
R202
ALD2
CO
ALD2
ALD2
R02
R02R
R202
R02R
MC03
3.69E+03
1
2
3
4
.OOE CO
.51E+04
.69E+00
.76E+03
R202 1.6
9
.11E+03
R202 1.84
3
1
4
1
4
1
4
1
4
1
4
1
4
1
2
1
.OOE+03
.14E+04
.43E+03
.48E+00
.43E+03
.14E+04
.43E»03
.48E+00
.43E+03
.14E+04
.43E+03
.48E+00
.43E+03
.26E+04
.57E-03
.08E+03
1.62E-01
3
1
5
1
9
2
3
5
9
4
1
.89E*04
.67E-02
.88E+03
.12E+01
.42E+04
.96E-01
.45E+04
.61E+02
.14E+03
.43E+04
.OOE 00
0
0
0
1427
353
R02
288
R02
709
•180
0
0
0
•180
0
0
0
-180
0
0
0
-411
2634
792
2923
•504
2105
324
1935
•549
1137
•10
975
•322
0
0
-------
TABLE 2 20 (CONTINUED)
THE INPUTS FOR THIS RUN ARE
XYLE OH
.83 R02
THBZ OH
.83 R02
CRES OH
1. R02
CRES NC3
R02P NO
R02P H02
R02P R02
R02P RC03
BZO N02
BZO H02
BZO
PHEN OH
1. R02
PHEN N03
NPHE N03
BZN2 N02
BZN2 H02
BZN2
NRHC
ZENITH
1.
1.0
13.
2.3
14.
25.
15.
6.45E-02
16.
1.26E-03
20.
.19
35.
6.25E-04
42.
6.25E-04
46.
2.33E-03
47.
4.51E-03
52.
2.58E-04
61.
7.26E-04
69.
7.05E-05
71.
115
.17CRES*
.65 DIAL .316
116
.17CRES*
.49 DIAL .86
117
118
119
: 1^0
121
122
123
124
125
126
127
128
129
130
131
132
17.
1.0
1.0
2.3
3.3
20.
30.
5.52E-02
7.43E-02
4.56E-03
5.98E-04
.20
.18
9.08E-04
5.12E-04
9.08E-04
5.12E-04
3.65E-03
1.81E-03
5.59E-03
3.97E-03
5.87E-04
1.63E-04
1.19E-03
5.53E-04
1.34E-04
4.98E-05
1.9IE-04
.2MGL1T*
1.HN03
1.NPHE
1.ROOH
.5H02
.5H02
1.NPHE
1.PHEN
1.PHEN
.2GLYX*
I . HN03
1.HN03
1.*PHE
I.NPht
1.NRHC
1.0
1.0
2.3
4.1
20.
36.
5.53E-02
8.90E-02
4.45E-03
2.80E-04
.20
.18
9.03E-04
4.31E-04
9.03E-04
4.31E-04
3.62E-03
1.41E-03
5.57E-03
3.57E-03
5.79E-04
1.01E-04
1.18E-03
4.27E-04
1.32E-04
3.55E-05
1 . 89E • 04
.17 H02
MGLY .095
.17 H02
MGLY
.15 R02P
1. BZO
1. R02
1. RC03
.15 R02P
1. BZO
1. BZN2
1.0
1.0
2.3
2.8
21.
26.
5.56E-02
6.60E-02
4.12E-03
1.54E-04
.20
.19
8.82E-04
3.83E-04
8.82E-04
3.83E-04
3.53E-03
1.10E-03
5.50E-03
3.43E-03
5.51E-04
5.98E-05
1.14E-03
3.31E-04
1.27E-04
2.49E-C";
1.82E-04
.83 R02R
GLTX
.83 R02R
.8S R02R
.85 R02R
1.0
2.3
21.
5.61E-02 5
3.56E-03 2
.20
3.62E+04 -
9.16E+04
5.91E+04
3.25E+04
1.14E+04 -
4.43E+03
1.48E+00
4.43E+03
2.22E+04
4.«3E*03
6.0CE-02
4.14E-04
5.62E+03
5.62E+03
2.22E+04
4.43E->03
6.00E-02
1 OOE-10
1.0 1.0
2.4 2.6
22. 23.
.71E-02 5.99E
116
0
0
0
180
0
0
0
0
0
0
0
0
0
0
0
0
0
-02
.86E-03 2.06E-03
.19 .19
8.45E-04 7.91E-04 7.18E
8.45E-04 7
3.36E-03 3
5.38E-03 5
5.01E-04 4
.91E-04 7.18E
.11E-03 2.77E
.19E-03 4.91E
.36E-04 3.53E
1.08E-03 9.94E-04 8.75E
1.18E-04 1
1.69E-04 1
.06E-04 8.97E
.SIE-G- 1.28E
•04
-04
•03
-03
-04
-04
•05
•04
-------
TABLE 2-20 (CONTINUED)
THE INPUTS FOR THIS RUN ARE
1.01E-04 7.11E-05 5.07E-05 3.56E-05
K)
I
-O
73.
8.97E-03
82.
1.98E-02
114.
5.25E-02
PLAC
WASHINGTON.
OKU
REAC
.260
.030
INIT
CO
1.00
EMIS
.15
TRAN
.001
.080
.030
.020
EKMA
.000
7.79E-03
9.88E-03
1.72E-02
2.17E-02
6.38E-02
4.70E-02
39.000
O.C.
250.
13.
.230
.030
1.
-5.
.15
.260
.030
.300
.000
.210
.060
7.81E-03
1.09E-02
1.72E-02
2.37E-02
6.36E-02
4 . 29E - 02
77.00
1000.
.25
.020
.020
.10
.15
.060
.230
.030
.200
.040
8.0
.001
7.87E-03
9.73E-03
1.74E-02
2.14E-02
6.29E-02
4.27E-02
5.0
800.
.040
.000
.10
.075
-13.
.020
,020
.020
.020
.030
7.97E-03
1.76E-02
6.15E-02
1986.
1200.
.020
.000
.10
.075
•13.
.040
.000
.010
.000
1.0
8.17E 03
1.80E-02
5.95E-02
8.0
.180
.090
.05
.020
.000
.000
.000
8.46E-03
1.87E-02
5.66E-02
21.
.080
.05
.180
.090
.100
.290
-------
TABLE 2-20 (CONTINUED)
THE REACTIONS
RATE CONSTANT ACT. ENERGY(K)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
N02
0
0
0
NO
N02
NO
NO
N02
N205
N205
N02
N03
N03
03
03
0*SD
0*SO
NO
HONO
N02
N02
HN03
CO
03
NO
N02
HN04
HN04
03
H02
H02
N03
N03
H202
H202
R02
RC03
RC03
R02
RC03
ROOH
R02
R02
RC03
HCHO
HCHO
HCHO
HCHO
HCHO
N02
N02
03
03
N03
NO
N03
N03
OH
OH
OH
OH
OH
H02
H02
OH
H02
H02
H02
H02
H02
OH
NO
NO
N02
H02
H02
R02
RC03
RC03
OH
N03
H02
NO
03
NO
N03
N02
N03
N02
N02
N205
N02
HKI03
NO
NO
N02
0
0*SO
OH
0
HONO
NO
HONO
HN03
N03
H02
H02
N02
HN04
N02
N02
OH
H202
H202
HN03
HN03
OH
H02
NO
NO
N02
H02
H02
H02
2 H02
CO
H02
HN03
R02R
N03
N02
0
OH
N02
OH
H02
HN03
OH
CO
CO
H02
R02
CO
1.000E+00
4.870E+07
1.370E+04
3.290E+03
2.680E+01
4.770E-02
2.750E+04
1.500E-04
1.710E+03
2.080E+00
3.000E-02
5.980E-01
1.000E+00
1.000E+00
1.000E+00
1.000E+00
6.500E+09
4.320E+10
9.750E+03
1.000E+00
.170E-04
.680E+04
.890E+02
.220E+02
.OOOE+02
.220E+04
2.020E+03
4.930E+OC
5.910E+03
2.960E*00
4.460E+03
5.080E+03
4.460E+03
5.080E+03
1.000E+00
2.450E+03
1.140E+04
1.140E*04
7.570E+03
4.430E+03
4.430E+03
1.000E+00
1.480E+00
4.430E+03
3.690E+03
1.000E+00
1.000E+00
1.330E+04
8.820E-01
1.480E+01
O.OOOE-01
-1.282E+03
O.OOOE-01
-8.940E*02
1 .370E+03
2.450E+03
-2.520E+02
-5.290E+02
-2.730E+02
1.138E*04
O.OOOE-01
1.229E+03
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
-8.330E+02
O.OOOE-01
O.OOOE-01
-7.370E+02
-7.780E+02
O.OOOE-01
9.420E+02
-2.400E+02
-7.730E+02
1.010E+04
O.OOOE-01
5.790E+02
-7.710E+02
-2.971E+03
-7.710E+02
-2.971E+03
O.OOOE-01
1.870E+02
-1.800E+02
-1.800E+02
-1.800E+02
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
O.OOOE-01
2.060E+03
O.OOOE-01
-------
TABLE 2-20 (CONTINUED)
THE REACTIONS
10
I
51
52
53
54
55
56
57
58
59
60
61
62
63
(A
65
66
67
68
69
70
71
AL02 +
AL02
AL02
MC03
MC03
MC03
MC03
MC03
PAN
RCHO +
RCHO
RCHO +
PC03 +
PC03 +
PC03 +
PC03 +
PC03 +
PPN
ACET
ACET +
HFK
OH
N03
NO
N02
H02
R02
RC03
OH
N03
NO
N02
H02
R02
RC03
OH
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
M6K +
GITX
GLYX +
GLYX +
GC03 +
GC03 +
GPAN
GC03 +
GC03 +
GC03 +
HGLY
MGLY +
MGLY +
ALK4 +
ALK7 +
ALKN
R02N
R02N
OH
OH
N03
N02
NO
H02
R02
RC03
OH
N03
OH
OH
OH
NO
H02
MC03
CO
R02
HN03
N02
PAN
ROOH
0.5 H02
H02
MC03
RC03
AL02
R02
HN03
N02
PPN
ROOH
0.5 H02
H02
PC03
MC03
R02
MGLY
HC03
R02
1.5 R02R
0.5 HCHO
0.13 HCHO
0.63 H02
HN03
0.37 RC03
GPAN
N02
GC03
ROOH
0.5 H02
H02
MC03
HC03
HN03
0.19 HCHO
0.44 HEK
1.6 R02
. 2 HCHO
0.88 HEK
1.84 R02
N02
0.16 HCHO
ALKN
ROOH
4-
4-
+
4
4-
4-
4
4-
4-
4-
4-
4-
4-
4-
4-
4-
4-
4
4-
+ 1.5
+ 0.5
+ 1.87
+ 1.26
+ 0.63
+
4
+
4
4
+
4-
4
+ 0.31
+ 0.07
+ . 3
+ 0.18
+ 0.15
+ 1.39
4
RC03
HCHO
MC03
HCHO
HCHO
HCHO
HCHO
N02
PC03
H02
PC03
ALD2
ALD2
AL02
ALD2
N02
HCHO
R02R
AL02
R02
PC03
CO
CO
H02
H02
N02
CO
CO
CO
H02
CO
HC03
ALD2
R02N
ALD2
R02N
HEK
R202
HEK
+ H02
+ RC03
+ R02R
+ R02
+ RC03
+ RC03
+ CO
+ RC03
+ R02R
+ R02
+ RC03
+ RC03
+ RC03
+ R02
+ RC03
+ 0.5 HC03
+ RC03
+0.37 GC03
+ 1.26 CO
+ CO
+ RC03
+ R02
+ RC03
+ CO
+ RC03
+ CO
+ 0.17 RCHO
+0.93 R02R
+ 0.25 RCHO
+0.82 R02R
+1.5 RCHO
+ 1.39 R02
+ R02R
+ R02
+ R02R
+ R02
+ R02R
+ R02R
+ 0.5 ALD2
+0.37 RC03
+0.37 GC03
+ RC03
+ RC03
+ 0.34 ACET
+ 0.60 R202
+ 0.36 ACET
+ 0.84 R202
+ 0.48 AL02
2.3606+04
1. OOOE+00
3.6906+00
1.140E+04
7.5706+03
4.4306+03
4.430E+03
3.6906+03
2.2106-02
2.930E+04
1.0006+00
3.6306+00
1.1406+04
7.570E+03
4.430E+03
4.4306+03
3.690E+03
2.210E-02
1. OOOE+00
3.390E+02
1. OOOE+00
1.460E+03
1. OOOE+00
1.700E+04
8.8806-01
7.570E+03
1.140E+04
2.2106-02
4.430E+03
4.430E+03
3.690E+03
1.0006+00
2.5106+04
3.690E+00
4 . 760E+03
9.110E+03
3.000E+03
1.140E+04
4.430E+03
RATE CONSTANT ACT. ENERGY(IC)
-2.500E+02
0.OOOE-01
1.4276+03
-1.8006+02
-1.8006+02
0.OOOE-01
0.0006-01
0.0006-01
1.3546+04
-2.5206+02
0.OOOE-01
1.4326+03
-1.8006+02
-1.800E+02
0.0006-01
0.0006-01
0.0006-01
1.3546+04
0.OOOE-01
1.1256+03
0.0006-01
7.4506+02
0.OOOE-01
0.OOOE-01
2.0586+03
-1.800E+02
-1.800E+02
1.3546+04
0.0006-01
0.OOOE-01
0.OOOE-01
0.OOOE-01
0.OOOE-01
1.427E+03
3.530E+02
2.880E+02
7.090E+02
-1.8006+02
0.0006-01
-------
TABLE 2-20 (CONTINUED)
THE REACTIONS
RATE CONSTANT ACT. ENERGY(K)
ro
I
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
1C7
108
109
110
111
112
113
114
115
R02N
R02N
R202
R202
R202
R202
R02R
R02R
R02R
R02R
ETHE
ETHE
ETHE
ETHE
PRPE
PRPE
PRPE
PRPE
TBUT
TBUT
TBUT
TBUT
TOLU
DIAL
DIAL
XYLE
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
•f
4
R02
RC03
NO
H02
R02
RC03
NO
H02
R02
RC03
OH
03
0
N03
OH
03
0
N03
OH
03
0
N03
OH
OH
OH
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
TMBZ +
CRES +
CRES +
R02P +
R02P +
R02P +
R02P +
BZO +
BZO +
BZO
PHEN +
PHEN +
NPHE +
BZN2 *
BZN2 +
BZN2
NRHC
OH
OH
N03
NO
H02
R02
RC03
N02
H02
OH
N03
N03
N02
H02
0.5
0.5
0.64
0.17
0.6
0.6
0.21
0.16
0.84
0.17
0.65
0.17
0.49
0.2
0.5
0.5
0.2
R02
RC03
N02
ROOH
R02
RC03
N02
ROOH
H02
H02
R02R
HCHO
HCHC
R02
N02
R02R
HCHO
H02
ACET
R02R
N02
R02
R02R
AL02
H02
MEK
N02
CRES
R02
PC03
H02
CRES
DIAL
CRES
DIAL
MGLY
HN03
NPHE
ROOH
H02
H02
NPHE
PHEN
PHEN
GLYX
HN03
HN03
NPHE
NPHE
NRHC
4
4
4
4
4
4
4
4
4
4
+
+
4
4
4
4
4
4
4
4
4
+0
4
4
4
+0
•»
•f
+
-f
+
+
+
•f
-f
0.5
0.5
0.12
2
0.5
0.13
0.4
0.4
2
0.15
0.27
0.4
2
0.16
.144
0.17
.316
0.17
0.86
0.15
0.15
H02
H02
H02
R02
RC03
R02
H02
H02
HCHO
HCHO
ALD2
R02R
HCHO
CO
HCHO
ALD2
CO
R02
H02
ALD2
H02
MGLY
RC03
CO
H02
MGLY
H02
MGLY
R02P
BZO
R02
RC03
R02P
BZO
BZN2
4
4
4 1.56
+ 0.42
4
4
4
4 0.28
+ 0.13
+ 0.2
+ 0.6
4
4
+ 0.27
«• 0.3
4
+ 0.84
+0.114
4
+ 0.83
+ . 95
+ 0.83
+ 0.85
+ 0.85
MEK
ME<
HCHO
CO
CO
R202
ALD2
CO
R02
ALD2
R02
ALD2
R02
R02R
HCHO
R202
R02R
GLYX
MC03
R02R
GLYX
R02R
R02R
R02R
+ 0.22 ALD2
+ R02R
+ R02
+ R02
+ . 6 OH
+ 0.2 H02
+ R202
+ 0.12 OH
+ R02
+ 0.4 DIAL
+ RC03
+ 0.83 R02
+ 0.83 R02
+ R02
+ R02
1
4
1
4
1
4
1
4
1
4
1
2
1
1
3
1
5
1
9
2
3
5
9
4
1
3
9
5
3
1
4
1
4
2
4
6
4
5
5
2
4
6
1
.480E+00
.430E+03
.140E+04
.430E+03
.480E+00
.430E+03
.140E+04
.430E+03
.480E+00
.430E+03
.260E+04
.570E-03
.080E+03
.620E-01
.890E+04
.670E-02
.880E+03
.120E+01
.420E+04
.960E-01
.450E+04
.610E+02
.140E+03
.430E+04
.OOOE+00
.620E+04
.160E+04
.910E+04
.250E+04
.140E+04
.430E+03
.480E+00
.430E+03
.220E+04
.430E+03
.OOOE-02
. 140E+04
.620E+03
.620E+03
.220E+04
.430E+03
.OOOE-02
.OOOE-10
O.OOOE-01
O.OOOE-01
-1.800E+02
O.OOOE-01
O.OOOE-01
O.OOOE-01
-1.800E+02
O.OOOE-01
O.OOOE-01
0
-4
2
7
2
-5
2
3
1
-5
1
•1
9
•3
0
0
-1
0
0
0
-1
0
0
0
0
0
0
0
0
0
0
0
0
0
.OOOE-01
.110E+02
.634E+03
.920E+02
.923E+03
.040E+02
.105E+03
.240E+02
.935E+03
.490E+02
.137E+03
.OOOE+01
.750E+02
.220E+02
.OOOE-01
.OOOE-01
.160E+02
.OOOE-01
.OOOE-01
.OOOE-01
.800E+02
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
.OOOE-01
-------
TABLE 2-20 (CONTINUED)
THE FOLLOWING PHOTOLYSIS RATE CONSTANTS ARE USED
REACTION SPECIES ZENITH ANGLE (DEC)
NO. 0 10 20 30 40 50 60 70 78 86
1 N02 6.00E-01 5.95E-01 5.86E-01 5.64E-01 5.32E-01 4.85E-01 4.09E-01 2.88E-01 1.55E-01 3.49E-02
13 N03 1.38E+00 1.37E+00 1.35E+00 1.30E+00 1.28E+00 1.26E+00 1.14E+00 9.51E-01 6.36E-01 9.77E-02
14 N03 1.20E+01 1.19E+01 1.23E+01 1.18E+01 1.17E+01 1.12E+01 1.02E+01 8.65E+00 5.59E+00 9.07E-01
15 03 3.31E-02 3.29E-02 3.26E-02 3.16E-02 3.04E-02 2.91E-02 2.64E-02 2.KE-02 1.38E-02 2.30E-03
16 03 2.74E-03 2.65E-03 2.41E-03 2.01E-03 1.52E-03 9.99E-04 5.15E-04 1.72E-OA 4.35E-05 5.37E-06
20 HONO 1.20E-01 1.19E-01 1.17E-01 1.13E-01 1.01E-01 9.22E-02 7.77E-02 5.19E-02 2.79E-02 6.63E-03
35 H202 5.45E-04 5.37E-04 5.16E-04 4.77E-04 4.21E-04 3.48E-04 2.55E-04 1.48E-04 6.69E-05 1.34E-05
42 ROOM 5.45E-04 5.37E-04 5.16E-04 4.77E-04 4.21E-04 3.48E-04 2.55E-04 1.48E-04 6.69E-05 1.34E-05
46 HCHO 2.19E-03 2.15E-03 2.07E-03 1.90E-03 1.65E-03 1.34E-03 9.52E-04 5.22E-04 2.19E-04 3.84E-05
47 HCHO 3.35E-03 3.32E-03 3.22E-03 3.04E-03 2.76E-03 2.38E-03 1.84E-03 1.14E-03 5.54E-04 1.20E-04
V 52 AL02 3.52E-04 3.45E-04 3.23E-04 2.83E-04 2.32E-04 1.71E-04 1.05E-04 4.70E-05 1.57E-05 2.09E-06
^j
00 61 RCHO 7.14E-04 7.02E-04 (S.68E-04 6.09E-04 5.29E-04 4.24E-04 2.97E-04 1.59E-04 6.63E-05 1.16E-05
69 ACET 8.04E-05 7.86E-05 7.44E-05 6.66E-05 5.64E-05 4.35E-05 2.88E-05 1.44E-05 5.51E-06 8.69E-07
71 MEK 1.15E-04 1.12E-04 1.07E-04 9.53E-05 8.03E-05 6.21E-05 4.13E-05 2.05E-05 7.87E-06 1.24E-06
73 GLYX 4.67E-03 4.65E-03 4.61E-03 4.50E-03 4.34E-03 4.10E-03 3.67E-03 2.85E-03 1.69E-03 3.40E-04
82 MGLY 1.03E-02 1.02E-02 1.02E-02 9.93E-03 9.57E-03 9.07E-03 8.09E-03 6.25E-03 3.68E-03 7.47E-04
114 DIAL 3.83E-02 3.79E-02 3.68E-02 3.47E-02 3.16E-02 2.75E-02 2.15E-02 1.35E-02 6.66E-03 1.49E-03
-------
N)
I
-O
TABLE 2-20 (CONTINUED)
TEST PROBLEM #4 - OZIPM "EKMA" RUN - 131 REACTION MECHANISM
PHOTOLYTIC RATE CONSTANTS CALCULATED fOS
WASHINGTON, D.C.
LATITUDE 39.000
LONGITUDE 77.000
TIME ZONE 5.0
DATE 8 21 1986
TIME 800 TO 1800 LOCAL DAYLIGHT TIME
DILUTION DETERMINED FROM THE FOLLOWING
INVERSION HEIGHTS INITIAL 250. FINAL 1000.
TIMING START 800. STOP 1200.
MIXING HEIGHTS (AT THE BEGINNING OF EACH HOUR)
TIME 800 900 1000 1100 1200
HEIGHT 250.0 449.5 679.6 869.6 1000.0
REACTIVITY
EMISSIONS ALK4 FRACTION .260 ALK7 FRACTION .230 ETHE FRACTION .020
EMISSIONS PRPE FRACTION .O'iO TBUT FRACTION .020 TOLU FRACTION .180
EMISSIONS XYLE FRACTION .080 TMBZ FRACTION .030 HCHO FRACTION .030
EMISSIONS ALD2 FRACTION .020 RCHO FRACTION .000 MEK FRACTION .000
EMISSIONS NRHC FRACTION .090
-------
TABLE 2-20 (CONTINUED)
SURFACE LAYER ALK4 FRACTION .260 ALK7 FRACTION .230 ETHE FRACTION .020
SURFACE LAYER PRPE FRACTION .040 TBUT FRACTION .020 TOLU FRACTION .180
SURFACE LAYER KYLE FRACTION .080 TMBZ FRACTION .030 HCHO FRACTION .030
SURFACE LAYER ALD2 FRACTION .020 RCHO FRACTION .000 MEK FRACTION .000
SURFACE LAYER NRHC FRACTION .090
ALOFT ALK4 FRACTION .300 ALK7 FRACTION .200 ETHE FRACTION .020
ALOFT PRPE FRACTION .010 TBUT FRACTION .000 TOLU FRACTION .100
ALOFT XYLE FRACTION .020 TMBZ FRACTION .000 HCHO FRACTION .040
ALOFT ALD2 FRACTION .020 RCHO FRACTION .000 MEK FRACTION .000
ALOFT NRHC FRACTION .290
N02/NOX .250
TRANSPORTED CONCENTRATIONS
to
J-, SURFACE LAYER OZONE .000 HYDROCARBON .001 NOX .000 PPM
O
SURFACE LAYER CO 1.000
ALOFT OZONE .060 HYDROCARBON .030 NOX .000 PPM
CONTINUOUS EMISSIONS (EXPRESSED AS FRACTION OF THE INITIAL PRECURSORS)
SPECIES HOUR 12345
VOC FRACTION .100 .100 .100 .050 .050
NOX FRACTION .150 .150 .150 .075 .075
-------
TABLE 2-20 (CONTINUED)
EKHA CALCULATIONS ARE PERFORMED TO ESTIMATE
SITE-SPECIFIC VOC CONTROL REQUIREMENTS
BASE YEAR OZONE .210 PPM
BASE YEAR NMOC/NOX 8.000
ANTICIPATED CHANGE IN NOX .000 PERCENT
FUTURE OZONE TRANSPORTED ALOFT .060 PPM
FUTURE NMOC TRANSPORTED ALOFT .030 PPMC
FUTURE NOX TRANSPORTED ALOFT .000 PPM
FUTURE OZONE IN THE SURFACE LAYER .000 PPM
FUTURE NMOC IN THE SURFACE LAYER .001 PPMC
FUTURE NOX IN THE SURFACE LAYER .000 PPM
THE FOLLOWING SIMULATIONS WERE DONE.
NJ
1
03
*—•
NMOC
1.00000
1.06969
1.13349
.11335
.54299
.99075
.73470
.76186
.75745
NOX
.12500
.13371
.14169
.14169
.14169
.14169
.14169
.14169
.14169
RATIO
8.00000
8.00000
8.00000
.80000
3.83234
6.99258
5.18538
5.37711
5.34600
03
.19632
.20346
.20980
.02505
.07154
.18472
.11399
.12116
.11996
TIME
NOT MAX
NOT MAX
NOT MAX
1218.
NOT MAX
NOT MAX
NOT MAX
NOT MAX
NOT MAX
VOC CONTROL REQUIREMENT IS 33.2 PERCENT
-------
3. SPECIATION OF NONMETHANE ORGANIC COMPOUNDS
Knowledge of NMOC speciation is essential for modeling urban ozone
air quality with up-to-date chemical mechanisms. Most photochemical air
quality simulation models require NMOC speciation information for
emissions, initial concentrations, and boundary concentrations. The
speciation data needs to be compiled using the NMOC classification scheme
that is used by the specific mechanism incorporated into the simulation
model. The NMOC classes in the SAPRC/ERT OZIPM mechanism are shown in
Table 3-1. Also shown in the table are the molecular weights and number
of carbons per molecule of the surrogate species used to represent each
class of compounds. Photochemical models require this information to
convert concentrations and emissions from mass and molar carbon units to
molar units.
The classification scheme shown in Table 3-1 is also recommended for
the initial compilation of data for use with the condensed mechanism
since proper use of that mechanism requires knowledge of the splits
between the two alkane classes, the two higher alkene classes, and the
two higher aromatic classes. Final inputs for the condensed mechanism
should be classified into the classes shown in Table 3-2.
3.1 Assignment of Individual Species to Classes
The assignment of individual organic species to the organic classes
in the OZIPM mechanism is shown in Table 3-3. Given detailed chemical
speciation for either emissions or ambient concentrations, the individual
species should be classified according to the assignments shown in the
table. Unlike the Carbon Bond approach, where almost all species are
divided into two or more classes, all of the carbon in individual species
is assigned to one compound class in this classification scheme. The
only exceptions to this are propane, methanol, and benzene, which are
split between the C4-C5 alkanes and nonreactive classes. Also included
in the table are estimates of the uncertainty in the assignments. The
uncertainty is expressed on a scale of 0 to 4, where 0 indicates that the
species is treated explicitly in the mechanism, and 4 indicates that
reactivity is totally unknown.
3-1
-------
TABLE 3-1
NMOC CLASSES FOR THE OZIPM MECHANISM
Compound Class
Ethene
Terminal Alkenes
Internal Alkenes
C4-C5 Alkanes
C6+ Alkanes
Mono-AlkyIbenzenes
Di-AlkyIbenzenes
Tri-AlkyIbenzenes
Formaldehyde
Acetaldehyde
Higher Aldehydes
Ketones
Nonreactive
ETHE
PRPE
TBUT
ALK4
ALK7
TOLU
XYLE
TMBZ
HCHO
ALD2
RCHO
MEK
NROG
Molecular
Weight
28.
42.
56.
65.
100.
92.
106.
120.
30.
46.
58.
72.
15.
No. of Carbons
Per Molecule
2
3
4
4.5
7
7
8
9
1
2
3
4
1
TABLi' 3-2
NMOC CLASSES FOR THE CONDENSED MECHANISM
Compound Class
Ethene
Higher Alkenes
C4+ Alkanes
Mono-Alkylbenzenes
Higher Aromatics
Formaldehyde
Higher Aldehydes
Ketones
Nonreactive
ol
ETHE
ALKE
ALKA
TOLU
AROM
HCHO
ALD2
MEK
NROG
Molecular
Weight
28.
47.6*
84.9*
92.
111.6*
30.
46.
72.
15.
No. of Carbons
Per Molecule
2
3.4*
5.92*
7
8.4*
1
2
4
1
^Default values. Speciated emissions inventory data should be
used, if available, to determine more accurate values.
3-2
-------
TABLE 3-3
ORGANIC SPECIES CLASSIFICATION FOR THE OZIPM CHEMICAL MECHANISM
ID No.
Compound Name
Uncertainty
Classification Classification
43814
43820
43813
45225
45208
99016
45207
43218
46201
43213
98104
43268
98111
98113
98005
43245
98037
43267
99901
43224
43312
43269
43296
43276
43299
98033
43291
43280
43279
43234
98001
43274
98054
98055
43277
43271
43278
98110
43308
98108
98051
43452
43311
98002
98112
43310
1,2
1,]
i,:
i,:
i,:
i,:
i,:
i,:
i,<
1-1
i-i
i-i
i-i
i-i
1-1
i-i
1-1
1-1
i-<
i-i
i-',
1-1
2,;
2,;
2,;
2,;
2,;
2,:
2,:
2,:
2,:
2,:
2,<
2,<
2.'
2,'
2,
2-
2-
2-
2-
2-
2-
2-
2-
2-
1,1-TRICHLOROETHANE
1,2-TRICHLOROETHANE
1-DICHLOROETHANE
2,3-TRIMETHYLBENZENE
2,4-TRIMETHYLBENZENE
2-DICHLOROPROPANE
3,5-TRIMETHYLBENZENE
3-BUTADIENE
4-DIOXANE
BUTENE
CHLOROBUTANE
DECENE
ETHOXY-2-PROPANOL
HEPTANOL
HEPTENE
HEXENE
METHYLCYCLOHEXANE
NONENE
OCTENE
PENTENE
T-2-0-4-TM-CYCLOPENTANE
UNDECENE
2,3-TRIMETHYLPENTANE
2,4-TRIMETHYLPENTANE
2,5-TRIMETHYLPENTANE
2,5-TRIMETHYLHEXANE
2-DIMETHYBUTANE
3,3-TRIMETHYLPENTANE
3,4-TRIMETHYLPENTANE
3-DIMETHYL-l-BUTENE
3-DIMETHYLBUTANE
3-DIMETHYLPENTANE
4,4-TRIMETHYL-l-PENTENE
4,4-TRIMETHYL-2-PENTENE
4-DIMETHYLHEXANE
4-DIMETHYLPENTANE
5-DIMETHYLHEXANE
(-BUTOXYETHOXY)-ETHANOL
BUTYLETHANOL
BUTYLTETRAHYDROFURAN
CHLOROTOLUENE
ETHOXYETHYL ACETATE
ETHOXYETHANOL
ETHYL-1-BUTENE
ETHYL-1-HEXANOL
METHOXYETHANOL
NONREACTIVE 1
NONREACTIVE 1
NONREACTIVE 1
TRI-ALKYL BENZENE 1
TRI-ALKYL BENZENE 1
NONREACTIVE 1
TRI-ALKYL BENZENE 0
INTERNAL ALKENES 2
C6+ ALKANES 2
TERMINAL ALKENES 1
C4-C5 ALKANES 2
TERMINAL ALKENES 3
C6+ ALKANES 2
C6+ AIKANES 1
TERMINAL ALKENES 3
TERMINAL ALKENES 3
C6+ ALKANES 1
TERMINAL ALKENES 3
TERMINAL ALKENES 3
TERMINAL ALKENES 2
C6+ ALKANES 1
TERMINAL ALKENES 3
C6+ ALKANES 1
C6+ ALKANES 1
C6+ ALKANES 1
C6+ ALKANES 1
C6+ ALKANES 1
C6+ ALKANES 1
C6+ ALKANES 1
TERMINAL ALKENES 2
C6+ ALKANES 1
C6+ ALKANES 1
TERMINAL ALKENES 3
INTERNAL ALKENES 3
C6+ ALKANES 1
C6+ ALKANES 1
C6+ ALKANES 1
C6+ ALKANES 2
C6+ ALKANES 1
C6+ ALKANES . 2
MONO-ALKYL BENZENE 2
C6+ ALKANES 3
C6+ ALKANES 2
TERMINAL ALKENES 2
C6+ ALKANES 1
C6+ ALKANES 2
3-3
-------
TABLE 3-3 (continued)
ID No.
Compound Name
43229 2-METHYL PENTANE
98076 2-METHYL-3-HEXANONE
98004 2-METHYL-2-PENTENE
43228 2-METHYL-2-BUTENE
98040 2-METHYL-1-PENTENE
43225 2-METHYL-l-BUTENE
43275 2-METHYLHEXANE
98032 3,5,5-TRIMETHYLHEXANE
98105 3-(CHLOROMETHYL)-HEPTANE
99021 3-CARENE*
98041 3-HEPTENE
43230 3-METHYL PENTANE
43223 3-METHYL-l-BUTENE
43270 3-METHYL-T-2-PENTENE
43211 3-METHYL-1-PENTENE
43298 3-METHYLHEPTANE
43295 3-METHYLHEXANE
43293 4-METHYL-T-2-PENTENE
43297 4-METHYLHEPTANE
98042 4-NONENE
45221 A-METHYLSTYRENE
98025 A-PINENE*
98097 A-TERPINEOL*
43503 ACETALEHYDE
43404 ACETIC ACID
43551 ACETONE**
43702 ACETONITRILE
43206 ACETYLENE
43505 ACROLEIN (ACRYLIC ALDHYDE)
43704 ACRYLONITRILE
98085 ALKYL SUBSTITUTED CYCLOHEXANE
99001 ALLYL CHLORIDE
98015 ANTHRACENE
98020 B-METHYLSTYRENE
98026 B-PINENE*
45201 BENZENE
45402 BENZOIC ACID
98024 BENZYL CHLORIDE
99017 BROMODICHLOROMETHANE
99019 BROMOFORM
98080 BUTANDIOL
98074 BUTYL CELLOSOLVE
43510 BUTYRALDEHYDE
98086 C2 ALKYL DECALIN
98084 C2 ALKYL INDAN
43512 C5 ALDEHYDE
98075 C5 ESTER
98095 C6 ALDEHYDE
Classification
C6+ ALKANES
KETONEi
INTERNAL ALKENES
INTERNAL ALKENES
TERMINAL ALKENES
TERMINAL ALKENES
C6+ ALKANES
C6+ ALKANES
C6+ ALKANES
INTERNAL ALKENES
INTERNAL ALKENES
C6+ ALKANES
TERMINAL ALKENES
INTERNAL ALKENES
TERMINAL ALKENES
C6+ ALKANES
C6+ ALKANES
INTERNAL ALKENES
C6+ ALKANES
INTERNAL ALKENES
TERMINAL ALKENES
INTERNAL ALKENES
INTERNAL ALKENES
ACETALDEHYDE
NONREACTIVE
KETONES
NONREACTIVE
NONREACTIVE
ACETALDEHYDE
ETHENE
C6+ ALKANES
ETHENE
TRI-ALKYL BENZENE
INTERNAL ALKENES
TERMINAL ALKENES
NONREACTIVE 70%
C6t ALKANES 30%
NONREACTIVE
MONO-ALKYL BENZENE
NONREACTIVE
NONREACTIVE
C6+ ALKANES
C6+ ALKANES
HIGHER ALDEHYDES
C6+ ALKANES
DI-ALKYL BENZENE
HIGHER ALDEHYDES
C4-C5 ALKANES
HIGHER ALDEHYDES
Uncertainty
Classification
1
1
2
1
3
2
1
1
2
3
3
1
1
2
2
1
1
2
1
3
3
3
3
0
2
1
1
2
3
3
2
3
3
3
3
3
3
3
1
1
2
2
1
2
3
2
3
2
3-4
-------
TABLE 3-3 (continued)
ID No.
Compound Name
Uncertainty
Classification Classification
98093 C6 ESTER
98096 CARBITOL
98030 CARBON SULFIDE
43807 CARBON TETRABROMIDE
43804 CARBON TETRACHLORIDE
98031 CARBONYL SULFIDE
98087 CARVOMENTHENE*
98088 CARVONE*
43443 CELLOSOLVE ACETATE
99020 CHLORODIBROMOMETHANE
43825 CHLORODIFLUOROMETHANE (F-22)
43830 CHLOROFLUOROHYDROCARBONS
43803 CHLOROFORM
43827 CHLOROPENTAFLUOROETHANE (F-115)
43826 CHLOROTRIFLUOROHETHANE (F-13)
43217 CIS-2-BUTENF.
43227 CIS-2-PENTENE
43227 CIS-3-PENTENE
98019 CRYOFLOURANE (F 114)
43264 CYCLOHEXANONE
43248 CYCLOHEXANE
43273 CYCLOHEXENE
43292 CYCLOPENTENE
43242 CYCLOPENTANE
43207 CYCLOPROPANE
98027 D-LIMONENE*
43320 DIACETONE ALCOHOL
99015 DIBENZOFURAN
98107 DIBUTYL ETHER
43823 DICHLORODIFLUOROMETHANE (F-12)
43802 DICHLOROMETHANE
43828 DICHLOROTETRAFLUOROETHANE
98062 DIETHYLCYCLOHEXANE
43450 DIMETHYL FORMAMTDE
98018 DIMETHYL ETHER
98059 DIMETHYLCYCLOHEXANE
45103 DIMETHYLETHYLBENZENE
98091 DIMETHYLHEPTANE
98012 DIMETHYLNAPHTHALENE
98017 DM-2,3,DH-1H-INDENE
99006 EPICHLOROHYDRIN
43202 ETHANE
43433 ETHYL ACETATE
43438 ETHYL ACRYLATE
43302 ETHYL ALCOHOL
43812 ETHYL CHLORIDE
43351 ETHYL ETHER
98106 ETHYL ISOPROPYL ETHER
43219 ETHYLACETYLENE
C6+ ALKANES
C6+ ALKANES
NONREACTIVE
NONREACTIVE
NONREACTIVE
NONREACTTVE
INTERNAL ALKENE
INTERNAL ALKENE
C6+ ALKANES
NONREACTIVE
NONREACTIVE
NONREACTIVE
NONREACTIVE
NONREACTIVE
NONREACTIVE
INTERNAL ALKENES
INTERNAL ALKENES
INTERNAL ALKENES
NONREACTIVE
KETONES
C6+ ALKANES
INTERNAL ALKENES
INTERNAL ALKENES
C4-C5 ALKANES
NONREACTIVE
INTERNAL ALKENES
HIGHER KETONE
DI-ALKYL BENZENE
C6+ ALKANES
NONREACTIVE
NONREACTIVE
NONREACTIVE
C6+ ALKANES
DI-ALKYL BENZENE
C4-C5 ALKANES
C6+ ALKANES
TRI-ALKYL BENZENE
C6+ ALKANES
TRI-ALKYL BENZENE
TRI-ALKYL BENZENE
NONREACTIVE
NONREACTIVE
C4-C5 ALKANES
TERMINAL ALKENE
C4-C5 ALKANES
NONREACTIVE
C4-C5 ALKANES
C6+ ALKANES
ETHENE
3
2
4
0
0
1
3
3
3
1
1
3
1
0
0
1
1
1
1
2
1
2
2
1
1
3
3
3
1
0
1
0
1
4
1
1
1
1
3
3
2
2
3
3
1
1
1
1
3
3-5
-------
TABLE 3-3 (continued)
Uncertainty
ID No. Compound Name Classification Classification
43721 ETHYLAMINE
45203 ETHYLBENZENE
43288 ETHYLCYCLOHEXANE
98057 ETHYLCYCLOPENTANE
99014 ETHYLENE DIBROMIDE
43601 ETHYLENE OXIDE
43815 ETHYLENE DICHLORIDE
43370 ETHYLENE GLYCOL
43203 ETHYLENE
98011 ETHYLNAPHTHALENE
43502 FORMALDEHYDE
99902 FURAN
43368 GLYCOL
43367 GLYCOL ETHER
99903 GLYOXAL**
43232 HEPTANE
98077 HEPTANONE
99007 HEXACHLOROCYCLOPENTADIENE
43231 HEXANE
43371 HEXYLENE GLYCOL
98044 INDAN
98048 INDENE
98115 ISOAMYL ISOBUTYRATE
43214 ISOBUTANE
43451 ISOBUTYL ISOBUTYRATE
43446 ISOBUTYL ACETATE
43306 ISOBUTYL ALCOHOL
98047 ISOBUTYLBENZENE
43215 ISOBUTYLENE
98036 ISOBUTYRALDEHYDE
99904 ISOMERS OF HEPTENE
43105 ISOMERS OF HEXANE
43106 ISOMERS OF HEPTANE
99905 ISOMERS OF HEXENE
45102 ISOMERS OF XYLENE
45105 ISOMERS OF BUTYLBENZENE
43108 ISOMERS OF NONANE
45106 ISOMERS OF DIETHYLBENZENE
43110 ISOMERS OF UNDECANE
43122 ISOMERS OF PENTANE
45104 ISOMERS OF ETHYLTOLUENE
43112 ISOMERS OF DODECANE
43107 ISOMERS OF OCTANE
43109 ISOMERS OF DECANE
99906 ISOMERS OF OCTENE
43243 ISOPRENE*
98043 ISOPROPYLBENZENE (CUMENE)
43444 ISOPROPYL ACETATE
43304 ISOPROPYL ALCOHOL
DI-ALKYL BENZENE 4
MONO-ALKYL BENZENE 1
C6+ ALKANES 1
C6+ ALKANES 1
NONREACTIVE 2
NONREACTIVE 2
NONREACTIVE 2
C4-C5 ALKANES 3
ETHENE 0
TRI-ALKYL BENZENE 3
FORMALDEHYDE 0
DI-ALKYL BENZENE 3
C4-C5 ALKANES 3
C6+ ALKANES 2
FORMALDEHYDE 2
C6+ ALKANES 1
KETONES 1
NONREACTIVE 2
C6+ ALKANES 1
C6+ ALKANES 2
DI-ALKYL BENZENE 3
TRI-ALKYL BENZENE 3
C6+ ALKANES 3
C4-C5 ALKANES 1
C6+ ALKANES 3
C4-C5 ALKANES 3
C4-C5 ALKANES 1
MONO-ALKYL BENZENE 1
TERMINAL ALKENES 2
HIGHER ALDEHYDES 1
INTERNAL ALKENES 3
C6+ ALKANES 1
C6+ ALKANES 1
INTERNAL ALKENES 3
DI-ALKYL BENZENE 3
MONO-ALKYL BENZENE 3
C6+ ALKANES 1
DI-ALKYL BENZENE 3
C6+ ALKANES 2
C4-C5 ALKANES 1
DI-ALKYL BENZENE 3
C6+ ALKANES 2
C6+ ALKANES 1
C6+ ALKANES 2
INTERNAL ALKENES 3
INTERNAL ALKENES 2
MONO-ALKYL BENZENE 1
C4-C5 ALKANES 3
C4-C5 ALKANES 1
3-6
-------
TABLE 3-3 (continued)
ID No.
Compound Name
Uncertainty
Classification Classification
98089 ISOPULEGONE*
98056 ISOVALERALDEHYDE
43119 LACTOL SPIRITS
98022 M-CRESOL (3-M-BENZENOL)**
98045 M-DIETHYLBENZENE
45212 M-ETHYLTOLUENE
45205 M-XYLENE
99008 MALEIC ANHYDRIDE
43201 METHANE
43432 METHYL ACETATE
43301 METHYL ALCOHOL
43445 METHYL AMYL ACETATE
43561 METHYL AMYL KETONE
43819 METHYL BROMIDE
43801 METHYL CHLORIDE
43552 METHYL ETHYL KETONE
98114 METHYL ISOBUTYRATE
43560 METHYL ISOBUTYL KETONE
43559 METHYL N-BUTYL KETONE
43209 METHYLACETYLENE
98016 METHYLANTHRACENE
43262 METHYLCYCLOPENTANE
43261 METHYLCYCLOHEXANF.
43272 METHYLCYCLOPENTENE
43805 METHYLENE BROMIDE
98010 METHYLNAPHTHALENE
45234 METHYLPROPYLBENZENE
43118 MINERAL SPIRITS
45801 MONOCHLOROBENZENE
43212 N-BUTANE
43305 N-BUTYL ALCOHOL
43435 N-BUTYL ACETATE
43238 N-DECANE
43255 N-DODECANE
43220 N-PENTANE
98063 N-PENTYLCYCLOHEXANE
43303 N-PROPYL ALCOHOL
45209 N-PROPYLBENZENE
45101 NAPHTHA
98046 NAPHTHALENE
99009 NITROBENZENE
43235 NONANE
98021 0-CRESOL (2-M-BENZENOL)**
45211 0-ETHYLTOLUENE
45204 0-XYLENE
43233 OCTANE
98023 P-CRESOL (4-M-BENZENOL)**
TERMINAL ALKENES
HIGHER ALDEHYDES
C6+ ALKANES
MOMO-ALKYL BENZENE
DI-ALKYL BENZENE
DI-ALKYL BENZENE
DI-ALKYL BENZENE
NONREACTIVE
NONREACTIVE
NONREACTIVE
NONREACTIVE 50%
C4-C5 ALKANES 50%
C6+ ALKANES
KETONES
NONREACTIVE
NONREACTIVE
KETONES
C4-C5 ALKANES
KETONES
KETONES
ETHENE
TRI-ALKYL BENZENE
C6+ ALKANES
C6+ ALKANES
INTERNAL ALKENES
NONREACTIVE
TRI-ALKYL BENZENE
DI-ALKYL BENZENE
MONO-ALKYL BENZENE
NONREACTIVE
C4-C5 ALKANES
C4-C5 ALKANES
C4-C5 ALKANES
C6+ ALKANES
C6+ ALKANES
C6+ ALKANES
C6+ ALKANES
C4-C5 ALKANES
MONO-ALKYL BENZENE
MONO-ALKYL BENZENE
TRI-ALKYL BENZENE
NONREACTIVE
C6+ ALKANES
MONO-ALKYL BENZENE
DI-ALKYL BENZENE
DI-ALKYL BENZENE
C6+ ALKANES
MONO-ALKYL BENZENE
3
2
4
2
1
1
0
2
1
2
3
3
1
1
1
0
3
1
1
3
3
1
1
3
0
3
1
4
3
1
1
3
2
2
1
2
1
1
4
3
3
1
2
1
1
1
2
3-7
-------
TABLE 3-3 (continued)
ID No.
Compound Name
Uncertainty
Classification Classification
45807 P-DICHLOROBENZENE
45206 P-XYLENE
98094 PENTYL ALCOHOL
43817 PERCHLOROETHYLENE
45300 PHENOLS**
98028 PHTHALIC ANHYDRIDE
43208 PROPADIENE
43204 PROPANE
43504 PROPIONALDEHYDE
43434 PROPYL ACETATE
45108 PROPYLBENZENE
98109 PROPYLCYCLOHEXANONE
43602 PROPYLENE OXIDE
43369 PROPYLENE GLYCOL
43205 PROPYLENE
98013 PROPYLNAPHTHALENE
45216 SEC-BUTYLBENZENE
45220 STYRENE
98116 SUBSTITUTED C7 ESTER (C12)
98117 SUBSTITUTED C9 ESTER (C12)
43123 TERPENES*
98079 TERPINENE*
45215 TERT-BUTYLBENZENE
43309 TERT-BUTYL-ALCOHOL
43390 TETRAHYDROFURAN
45232 TETRAMETHYLBENZENE
45202 TOLUENE
99018 TRANS-1,2-DICHLOROETHENE
43216 TRANS-2-BUTENE
43227 TRANS-2-PENTENE
43226 TRANS-2-PENTENE
43227 TRANS-3-PENTENE
45233 TRI/TETRAALKYL BENZENE
43821 TRICHLOROTRIFLUOROETHANE
43811 TRICHLOROFLUOROMETHANE
43824 TRICHLOROETHYLENE
45107 TRIMETHYLBENZENE
43740 TRIMETHYL AMINE
98060 TRIMETHYLCYCLOHEXANE
98058 TRIMETHYLCYCLOPENTANE
98014 TRIMETHYLNAPHTHALENE
43822 TRIMETHYLFLUOROSILANE
43241 UNDECANE
43860 VINYL CHLORIDE
45401 XYLENE BASE ACIDS
NONREACTIVE ' 3
DI-ALKYL BENZENE 1
C4-C5 ALKANES 1
NONREACTIVE 1
MONO-ALKYL BENZENE 3
DI-ALKYL BENZENE 3
TERMINAL ALKENES 3
NONREACTIVE 50%
C4-C5 ALKANES 50% 3
HIGHER ALDEHYDES 1
C4-C5 ALKANES 3
MONO-ALKYL BENZENE 1
KETONES 2
C4-C5 ALKANES 3
C4-C5 ALKANES 2
TERMINAL ALKENES 0
TRI-ALKYL BENZENE 3
MONO-ALKYL BENZENE 1
TERMINAL ALKENES 3
C6+ ALKANES 3
C6+ ALKANES 3
INTERNAL ALKENES 3
INTERNAL ALKENES 3
MONO-ALKYL BENZENE 1
C4-C5 ALKANES 1
C6+ ALKANES 1
TRI-ALKYL BENZENE 1
MONO-ALKYL BENZENE 0
ETHENE 3
INTERNAL ALKENES 0
INTERNAL ALKENES 1
INTERNAL ALKENES 1
INTERNAL ALKENES 1
TRI-ALKYL BENZENE 1
NONREACTIVE 0
NONREACTIVE 0
ETHENE 3
TRI-ALKYL BENZENE 1
TRI-ALKYL BENZENE 4
C6+ ALKANES 1
C6+ ALKANES 1
TRI-ALKYL BENZENE 3
NONREACTIVE 1
C6+ ALKANES 2
ETHENE 3
DI-ALKYL BENZENE 4
*Biogenic compound.
**These species can either be represented by the assigned class or
explicitly.
3-8
-------
TABLE 3-3 (continued)
Uncertainty Classifications:
0 = Explicitly represented in mechanism (for reactive compounds),
or known not to react in the troposphere (for nonreactive compounds)
1 = Representation shown is probably a good approximation
2 = Representation shown may not be a good approximation, but the
mechanism does not contain more appropriate species.
3 = Representation shown is probably a poor approximation, but the
mechanism does not contain more appropriate species.
4 = Appropriate representation is unknown.
3-9
-------
Chemical structure is largely the basis for the assignment of the
individual species to classes. Alkanes are assigned to one of the alkane
classes on the basis of carbon number. Alkenes are assigned based on the
position of the double bond within the molecule (i.e., on whether the
double bond is located in the terminal position or in an internal
position). The aromatics are assigned based on the number of alkyl
groups attached to the benzene ring. Aldehydes are assigned on the basis
of carbon number. However, about 20% of the compounds on the list are
not kinetically or structurally similar to any of the surrogate species.
These are the species that have been assigned a high uncertainty rating
(3 or 4) in Table 3-3. The assignments for these species are primarily
based on similarity between their OH rate constants (when available) and
the OH rate constants of the surrogate species in the mechanism and,
secondarily, on similarity of structure and reactivity of products (when
known). The OH rate constants were obtained from Atkinson (1986).
Although these compounds represent 20% of the species on the list, it is
unlikely that they represent a significant (i.e., more than 5%) fraction
of NMOC in urban areas.
VOC emission inventories can be speciated using published data.
Emission speciation profiles are available for a moderate number of
stationary and some mobile sources in the "Volatile Organic Compound
Species Data Manual" (EPA 1980) and "Improvements of the Emission
Inventory for ROG and NO in the SoCAB" (Oliver and Peoples 1985).
X
Additional speciation data for mobile sources are available from EPA's
"Forty-Six Car Study" (EPA 1985). Profiles for stationary sources are
generally assigned on the basis of Source Classification Code (SCC). The
detailed profiles can be transformed to NMOC class profiles using the
assignments shown in Table 3-3.
Speciated ambient NMOC data are needed for photochemical modeling.
Region-specific data should be employed in the modeling whenever
possible. Recognizing that speciated NMOC ambient data are often not
available default speciation profiles have been developed for NMOC in the
surface layer and aloft. These profiles are shown in Table 3-4. They
are based on analysis of surface data from 25 urban areas and aircraft
data from 4 urban areas (Lurmann et al. 1987). Plausible ranges of the
speciation fractions are shown in Table 3-5. The ranges generally
3-10
-------
TABLE 3-4
RECOMMENDED DEFAULT NMOC COMPOSITION PROFILES
Carbon Fractions of NMOC
Compound Class
C4-C5 Alkanes
C6+ Alkanes
Ethene
Terminal Alkenes
Internal Alkenes
Mono-alkyIbenzenes
Di-alylbenzenes
Tri-alkyIbenzenes
Formaldehyde
Acetaldehyde
Unreactive
Surface Layer Alofl
.21
.28
.03
.06
.04
.16
.06
.04
.03
.02
.07
.21
.18
.015
.03
.005
.07
.04
.02
.05
.03
.35
TABLE 3-5
RANGE OF NMOC COMPOSITION FRACTIONS
Carbon Fractions of NMOC
Compound Class
C4-C5 Alkanes
C6+ Alkanes
Ethene
Terminal Alkenes
Internal Alkenes
Mono-alkyIbenzenes
Di-alylbenzenes
Tri-alkyIbenzenes
Formaldehyde
Acetaldehyde
Unreactive
Surface
.11 -
.14 -
.015 -
.03 -
.02 -
.08 -
.03 -
.02 -
.015 -
.01 -
.04 -
Layer
.31
.42
.045
.09
.06
.24
.09
.06
.06
.04
.11
Aloft
.11 - .
.09 - .
.0 - .
.0 - .
.0 - .
.04 - .
.0 - .
.0 - .
.01 - .
.01 - .
.15 - .
31
27
03
045
01
11
06
04
08
08
75
3-11
-------
reflected ±50% variations about the mean fractions. If ambient samples
shown variations beyond these ranges (particularly the upper values),
then the sample may reflect strong influence by local point sources and
may not be representative of the entire urban area.
3-12
-------
4. REFERENCES
Atkinson, R., A.C. Lloyd and L. Winges 1982. Atmos. Environ., ^6: 1341.
Atkinson, R. and A.C. Lloyd 1984. J. Phys. Chem. Ref Data, 13: 315.
Atkinson, R. 1986. Kinetics and Mechanisms of the Gas Phase Reactions of
the Hydroxyl Radical with Organic Compounds Under Atmospheric
Conditions. Chem. Rev., 86: 69-201.
Carter, W.P.L., F.W. Lurmann, R. Atkinson, and A.C. Lloyd 1986.
Development and Testing of a Surrogate Species Chemical Reaction
Mechanism, Volumes I & II. EPA-600/3-86-031. U.S. Environmental
Protection Agency, Research Triangle Park, NC.
EPA 1980. Volatile Organic Compound
EPA-450-80-015. U.S. Environmental
Triangle Park, NC.
(VOC) Species Data Manual.
Protection Agency, Research
Hindmarsh, Alan C. 1980. LSODE and LSODI, Two New Initial Value Ordinary
Differential Equation Solvers, ACM-Signum Newsletter, Vol. 15,
No. 4, pp 10-11.
Hogo, H. and G.Z. Whitten 1986. Guidelines for Using OZIPM-3 with CBM-X
or Optional Mechanisms, Vol. 1 - Description of the Ozone Isopleth
Plotting Package/Version 3. EPA/600/3-86/004. U.S. Environmental
Protection Agency, Research Triangle Park, NC.
Lonneman, W.A. 1986. Comparison of 0600-0900 AM Hydrocarbon Composition
From 29 Cities. Proceedings of the 1986 EPA/APCA Symposium on
Measurements of Toxic Air Pollutants. APCA Publication VIP-7 and
EPA/600/9-86/013, pp. 419-430. U.S. Environmental Protection
Agency, Research Triangle Park, NC.
Lurmann, F.W., A.C. Lloyd and R. Atkinson 1984. ADOM/TADAP Model
Development Program, Volume 6, Gas Phase Chemistry. ERT Document
No. P-B980-530, July.
Lurmann, F.W., A.C. Lloyd and R. Atkinson 1986. A Chemical Mechanism for
Use in Long Range Transport/Acid Deposition Computer Modeling.
J. Geophys. Res., 91:P10:10,905
NASA 1985. Chemical Kinetics and Photochemical Data for Use in
Stratospheric Modeling, Evaluation No. 7, Jet Propulsion Laboratory
Publication 85-37, National Aeronautics and Space Administration.
Oliver, W.R. and S.H. Peoples 1985. Improvement of the Emission
Inventory for Reactive Organic Gasses and Oxides of Nitrogen in the
Couth Coast Air Basin. Systems Applications, Inc., San Rafael, CA
and Radian Corp., Sacramento, CA.
4-1
-------
Peterson, J.T. 1976. Calculated Actinic Fluxes (290-700 nm) for Air
Pollution Photochemistry Applications. EPA-600/4-76-025, June.
Reynolds, S.D., J.H. Seinfeld, and P.M. Roth 1973. Mathematical Modeling
of Photochemical Air Pollution - I: Formulation of the Model.
Atmos. Environ., 7:1033-1061.
WSU 1986. Nonmethane Organic Carbon Concentrations in Air Masses
Advected Into Urban Areas in the United States. Data Report for EPA
Grant No. CR812208. Washington State University, Pullman, WA.
4-2
-------
APPENDIX A
PHOTOLYTIC REACTION RATE DATA
-------
TABLE A-1
SOLAR ACTINIC FLUXES FOR ZERO ELEVATION AND BEST ESTIMATE ALBEDO*
WAVELENGTH
BAND (urn)
.295 -.300
.300-. 305
.305-. 310
.310-. 315
.315-. 320
.320-. 325
.325-. 330
.330 -.335
.335 -.340
.340 -.345
.345-. 350
.350-. 355
.355-. 360
.360 -.365
.365 -.370
.370 -.375
.375 -.380
.380 -.385
.385 -.390
.390-. 395
.395-. 400
.400-. 405
.405-. 410
.410-. 415
.415-. 420
.420-. 430
.430-. 440
.440-. 450
.450-. 460
.460-. 470
.470-. 480
.480-. 490
.490-. 500
.500-. 510
.510-. 520
.520-. 530
.530-. 540
.540-. 550
.550-. 560
.560-. 570
.570-. 580
.580 -.600
.600-. 620
.620-. 640
.640-. 660
.660-. 680
.680-. 700
EXP
14
14
14
14
14
14
14
14
14
14
14
14
14
14
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
15
16
16
16
16
16
16
0
0.041
0.39E
1.41
3.14
4.35
5.48
7.89
8.35
8.24
8.89
8.87
10.05
9.26
10.25
1.26
1.14
1.27
1.05
.15
.19
.44
.73
.94
2.05
2.08
4.08
4.20
4.87
5.55
5.68
5.82
5.78
5.79
5.99
5.88
5.98
5.98
5.88
5.94
5.99
6.12
1.25
1.26
1.27
1.30
1.33
1.33
10
0.038
0.381
1.37
3.10
4.31
5.41
7.79
8.25
8.16
8.80
8.79
9.96
9.18
10.16
1.25
1.13
1.26
1.04
1.15
1.18
1.43
1.72
1.93
2.04
2.07
4.06
4.18
4.85
5.51
5.65
5.79
5.75
5.76
5.96
5.86
5.95
5.95
5.85
5.91
5.96
6.09
1.24
1.26
1.26
1.30
1.33
1.32
20
0.030
0.331
1.25
2.91
4.10
5.19
7.51
7.98
7.91
8.54
8.54
9.70
8.94
9.91
1.22
1.10
1.23
1.02
1.12
1.16
1.40
1.69
1.90
2.00
2.03
3.99
4.11
4.77
5.43
5.57
5.70
5.67
5.68
5.87
5.77
5.87
5.87
5.77
5.83
5.88
6.00
1.22
1.24
1.24
1.28
1.31
1.30
SOLAR ZENITH ANGLE
30 40 50 60
0.019
0.255
1.05
2.58
3.74
4.80
7.01
7.50
7.46
8.09
8.11
9.22
8.52
9.46
1.17
1.06
1.18
0.980
1.08
1.11
1.35
1.63
1.83
1.93
1.96
3.87
3.99
4.64
5.27
5.42
5.55
5.53
5.54
5.71
5.62
5.72
5.72
5.62
5.68
5.73
5.85
1.19
1.21
1.17
1.25
1.28
1.27
0.009
0.167
0.80
2.13
3.21
4.23
6.27
6.76
6.78
7.38
7.43
8.48
7.86
8.76
1.08
0.983
1.10
0.917
1.01
1.05
.28
.53
.73
.83
.86
3.67
3.80
4.43
5.03
5.17
5.31
5.29
5.31
5.47
5.38
5.48
5.48
5.40
5.44
5.49
5.61
1.14
1.16
1.10
1.20
1.23
1.23
0.003
0.084
0.513
1.56
2.52
3.43
5.21
5.72
5.79
6.36
6.44
7.39
6.88
7.71
0.958
0.873
0.983
0.820
0.909
0.943
1.15
1.39
1.57
1.66
1.70
3.36
3.49
4.09
4.64
4.79
4.91
4.93
4.96
5.09
5.02
5.11
5.12
5.04
5.08
5.13
5.24
.1.07
1.08
1.10
1.13
1.16
1.16
0.000
0.027
0.244
0.922
1.67
2.43
3.83
4.30
4.43
4.93
5.04
5.83
5.47
6.17
0.772
0.708
0.802
0.673
0.750
0.783
0.962
1.16
1.32
1.41
1.44
2.87
3.01
3.54
4.02
4.17
4.32
4.33
4.37
4.47
4.43
4.52
4.52
4.46
4.49
4.54
4.63
0.951
0.963
0.980
1.01
1.04
1.04
70
0.000
0.004
0.064
0.357
0.793
1.29
2.17
2.54
2.69
3.04
3.15
3.69
3.50
3.99
0.505
0.467
0.535
0.453
0.510
0.537
0.666
0.809
0.926
0.993
1.03
2.07
2.19
2.61
2.99
3.12
3.26
3.29
3.34
3.41
3.40
3.47
3.48
3.44
3.46
3.50
3.57
0.737
0.748
0.771
0.803
0.828
0.839
78
0.000
0.001
0.011
0.090
0.264
0.502
0.928
1.15
1.25
1.44
1.51
1.77
1.69
1.94
0.247
0.230
0.265
0.226
0.257
0.273
0.341
0.418
0.482
0.522
0.543
.11
.20
.45
.67
.77
.87
.90
.95
.99
2.00
2.04
2.05
2.03
2.04
2.06
2.10
0.439
0.448
0.473
0.502
0.527
0.541
86
0.000
0.000
0.002
0.009
0.030
0.073
0.167
0.241
0.282
0.333
0.352
0.414
0.391
0.444
0.055
0.051
0.058
0.049
0.054
0.057
0.070
0.085
0.097
0.104
0.107
0.216
0.229
0.272
0.312
0.325
0.341
0.339
0.344
0.340
0.340
0.336
0.326
0.317
0.312
0.306
0.301
0.064
0.065
0.074
0.086
0.096
0.104
THE SECOND COLUMN (EXP) LISTS THE POWER OF TEN BY WHICH ALL ENTRIES SHOULD BE MULTIPLIED.
DATA FROM PETERSON (1976).
A-1
-------
Table A-2
Photolytic Data for N02 + hv ••> NO + 0
Wavelength
(urn)
.295
.300
.305
.310
.315
.320
.325
.330
.335
.340
.345
.350
.355
.360
.365
.370
.375
.376
.377
.378
.379
.380
.381
.382
.383
.384
.385
.386
.387
.388
.389
.390
.391
.392
.393
.394
.395
.396
.397
.398
.399
.400
.401
.402
.403
.404
.405
.406
.407
.408
.409
.410
.411
.415
.420
.425
Absorption
Cross -sect ion*
9.67E-20
1.17E-19
1.66E-19
1.76E-19
2.25E-19
2.54E-19
2.79E-19
2.9VE-19
3.45E-19
3.88E-19
4.07E-19
4.10E-19
5.13E-19
4.51E-19
5.78E-19
5.42E-19
5.35E-19
5.48E-19
5.61E-19
5.73E-19
5.86E-19
5.99E-19
5.98E-19
5.97E-19
5.96E-19
5.95E-19
5.94E-19
5.95E-19
5.96E-19
5.98E-19
5.99E-19
6.00E-19
5.98E-19
5.96E-19
5.93E-19
5.91E-19
5.89E-19
6.06E-19
6.24E-19
6.41E-19
6.59E-19
6.76E-19
6.67E-19
6.58E-19
6.50E-19
6.41E-19
6.32E-19
6.21E-19
6.10E-19
5.99E-19
5.88E-19
5.77E-19
5.88E-19
6.30E-19
6.23E-19
6.00E-19
Quantum
Yield
.984
.980
.976
.972
.968
.964
.960
.956
.952
.948
.944
.940
.936
.932
.928
.850
.770
.780
.920
.820
.870
.900
.810
.700
.680
.700
.770
.840
.750
.810
.780
.800
.880
.840
.900
.900
.840
.830
.820
.770
.780
.680
.650
.620
.570
.420
.320
.330
.250
.200
.190
.150
.100
.067
.023
.000
2
in cm per molecule
A-2
-------
Table A-3
Photolytic Data for N03 + hv •-> NO + 02
Wavelength
(um)
.585
.590
.595
.600
.605
.610
.615
.620
.625
.630
.635
.640
Absorption
Cross-section
2.77E-18
5.14E-18
4.08E-18
2.83E-18
3.45E-18
1.48E-18
1.96E-18
3.58E-18
9.25E-18
5.66E-18
1.45E-18
1.11E-18
Quantum
Yield
.000
.250
.400
.250
.200
.200
.100
.100
.050
.050
.030
.000
Table A-4
Photolytic Data for N03 + hv •-> N02 + 0
Wavelength
(urn)
.400
.405
.410
.415
.420
.425
.430
.435
.440
.445
.450
.455
.460
.465
.470
.475
.480
.485
.490
.495
.500
.505
.510
.515
.520
.525
.530
.535
.540
.545
.550
.555
.560
.565
.570
.575
.580
.585
.590
.595
.600
.605
.610
.615
.620
.625
.630
.635
Absorption
Cross-section
O.OOE-01
3.00E-20
4.00E-20
5.00E-20
8.00E-20
1.00E-19
1.30E-19
1.80E-19
1.90E-19
2.20E-19
2.80E-19
3.30E-19
3.70E-19
4.30E-19
5.10E-19
6.00E-19
6.40E-19
6.90E-19
8.80E-19
9.50E-19
1.01E-18
1.10E-18
1.32E-18
1.40E-18
1.45E-18
1.48E-18
1.94E-18
2.04E-18
1.81E-18
1.81E-18
2.36E-18
2.68E-18
3.07E-18
2.53E-18
2.54E-18
2.74E-18
3.05E-18
2.77E-18
5.14E-18
4.08E-18
2.83E-18
3.45E-18
1.45E-18
1.96E-18
3.58Er18
9.25E-18
5.66E-18
1.45E-18
Quantum
Yield
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
.750
.600
.550
.400
.300
.250
.200
.150
.050
.000
A-3
-------
Table A-5
Photolytic Data for 03 + hv •-> 0(10) + 02 at 270 K
Wavelength
(urn)
.260
.270
.280
.290
.300
.305
.310
.313
.315
.317
.320
Absorption
Cross-section
1.07E-17
7.74E-18
3.79E-18
1.34E-18
3.80E-19
1.88E-19
9.80E-20
7.50E-20
5.2DE-20
4.16E-20
2.60E-20
Quantum
Yield
.900
.900
.900
.900
.900
.860
.460
.160
.070
.030
.000
Table A-6
•> 0(10) + 02 at 300 K
Wavelength
(urn)
.260
.270
.280
.290
.300
.305
.310
.313
.315
.317
.320
A' . -• ption
Cross-section
1.07E-17
7.74E-18
3.79E-18
1.34E-18
3.80E-19
1.88E-19
9.80E-20
7.50E-20
5.20E-20
4.16E-20
2.60E-20
Quantum
Yield
.900
.900
.900
.900
.900
.890
.560
.260
.130
.050
.000
Table A-7
Photolytic Data for 03 + hv •-> 0(10) + 02 at 330 <
Wavelength
(urn)
Absorption
Cross-section
.260
.270
.280
.290
.300
.305
.310
.313
.315
.317
.320
.322
1.07E-17
7.74E-18
3.79E-18
1.34E-18
3.80E-19
1.88E-19
9.80E-20
7.50E-20
5.20E-20
4.16E-20
2.60E-20
2.30E-20
Quantum
Yield
.900
.900
.900
.900
.900
.900
.630
.360
.220
.120
.030
.000
A-4
-------
Table A-8
Photolytic Data for 03 + hv ••> 0(3P) + 02
Wavelength
(urn)
.260
.270
.280
.290
.300
.310
.320
.330
.340
.350
.355
.400
.450
.500
.550
.600
.650
.660
.670
.680
.690
.700
Absorption
Cross-section
1.07E-07
7.74E-18
3.79E-18
1.34E-18
3.16E-19
9.80E-20
2.60E-20
6.70E-21
1.70E-21
4.00E-22
O.OOE-01
O.OOE-01
1.60E-22
1.34E-21
3.32E-21
5.06E-21
2.45E-21
2.13E-21
1.82E-21
1.50E-21
1.19E-21
8.70E-22
Quantum
Yield
.100
.100
.100
.100
.100
.443
.000
.000
.000
.000
.000
1.000
1.000
1.000
.000
.000
.000
.000
.000
.000
1.000
1.000
Table A-9
Photolytic Data for H202 + hv ••> 2 OH
Wavelength
(urn)
.250
.255
.260
.265
.270
.275
.280
.285
.290
.295
.300
.305
.310
.315
.320
.325
.330
.335
.340
.345
.350
.355
Absorption (
Cross- sect ion
8.30E-20
6.70E-20
5.20E-20
4.20E-20
3.20E-20
2.50E-20
2.00E-20
1.50E-20
1.13E-20
8.70E-21
6.60E-21
4.90E-21
3.70E-21
2.80E-21
2.00E-21
1.50E-21
1.20E-21
9.00E-22
7.00E-22
5.00E-22
3.00E-22
3.00E-22
Juantum
Yield
1.000
.000
.000
.000
.000
.000
.000
.000
.000
.000
.000
.000
.000
.000
.000
1.000
t.ooo
1.000
1.000
1.000
1.000
.000
A-5
-------
Table A-10
Photolytic Data for HOMO + hv ••> NO + OH
Wavelength
(urn)
.311
.312
.313
.314
.315
.316
.317
.318
.319
.320
.321
.322
.323
.324
.325
.326
.327
.328
.329
.330
.331
.332
.333
.334
.335
.336
.337
.338
.339
.340
.341
.342
.343
.344
.345
.346
.347
.348
.349
.350
.351
Absorption
Cross-section
O.OOE-01
2.00E-21
4.20E-21
4.60E-21
4.20E-21
3.00E-21
4.60E-21
3.60E-20
6.10E-20
2.10E-20
4.27E-20
4.01E-20
3.93E-20
4.01E-20
4.04E-20
3.13E-20
4.12E-20
7.55E-20
6.64E-20
7.29E-20
8.70E-20
1.38E-19
5.91E-20
5.91E-20
6.45E-20
5.91E-20
4.58E-20
1.91E-19
1.63E-19
1.05E-19
8.70E-20
3.35E-19
2.01E-19
1.02E-19
8.54E-20
8.32E-20
8.20E-20
7.49E-20
7.13E-20
6.83E-20
1.74E-19
Quantum
Yield
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
Wavelength
(urn)
.352
.353
.354
.355
.356
.357
.358
.359
.360
.361
.362
.363
.364
.365
.366
.367
.368
.369
.370
.371
.372
.373
.374
.375
.376
.377
.378
.379
.380
.381
.382
.383
.384
.385
.386
.387
.388
.389
.390
.391
.392
Absorption
Cross -sect ion
1.KE-19
3.71E-19
4.96E-19
2.46E-19
1.19E-19
9.35E-20
7.78E-20
7.29E-20
6.83E-20
6.90E-20
7.32E-20
9.00E-20
1.21E-19
1.33E-19
2.13E-19
3.52E-19
4.50E-19
2.93E-19
1.19E-19
9.46E-20
8.85E-20
7.44E-20
4.77E-20
2.70E-20
1.90E-20
1.50E-20
1.90E-20
5.80E-20
7.78E-20
1.14E-19
1.40E-19
1.72E-19
1.99E-19
1.90E-19
1.19E-19
5.65E-20
3.20E-20
1.90E-20
1.20E-20
5.00E-21
O.OOE-01
QUcTtum
Yie'd
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
1.000
A-6
-------
Table A-11
Photolytic Data for HCHO + hv ••> 2 H02 + CO
Wavelength
(urn)
.240
.250
.260
.270
.280
.290
.300
.310
.320
.330
.340
Absorption
Cross-section
3.00E-22
1.30E-21
4.70E-21
8.60E-21
1.86E-20
2.51E-20
2.62E-20
2.45E-20
1.85E-20
1.76E-20
1.18E-20
Quantum
Yield
.210
.240
.300
.400
.590
.710
.780
.770
.620
.310
.000
Table A-12
Photolytic Data for HCHO + hv
Table A-13
Photolytic Data for ALD2 + hv
•> H2 + CO
Wavelength
(urn)
.240
.250
.260
.270
.280
.290
.300
.310
.320
.330
.340
.350
.360
.370
Absorption
Cross -sect ion
3.00E-22
1.30E-21
4.70E-21
8.60E-21
1.86E-20
2.51E-20
2.62E-20
2.45E-20
1.85E-20
1.76E-20
1.18E-20
4.20E-21
6.00E-22
O.OOE-01
Quantum
Yield
.420
.460
.480
.460
.350
.260
.220
.230
.380
.690
.690
.400
.120
.000
•> HCHO + H02 + R02R + CO
Wavelength
(urn)
.260
.270
.280
.290
.295
.300
.305
.310
.315
.320
.325
.330
Absorption
Cross-section
2.16E-20
3.46E-20
4.32E-20
4.76E-20
4.45E-20
4.03E-20
3.42E-20
2.72E-20
2.09E-20
1.60E-20
1.13E-20
6.80E-21
Quantum
Yield
.310
.380
.590
.550
.490
.415
.325
.235
.150
.075
.030
.000
A-7
-------
Table A-14
Photolytic Data for RCHO + hv -•> ALD2 + H02 + R02R + CO
Wavelength
(urn)
.280
.290
.300
.310
.320
.330
.340
.345
Absorption
Cross-section
5.26E-20
5.77E-20
5.05E-20
3.68E-20
1.66E-20
6.49E-21
1.44E-21
O.OOE-01
Quantum
Yield
.200
.200
.200
.200
.200
.200
.200
.200
Table A-15
Photolytic Data for ACET + hv ••> HCHO + R02R + MC03
Wavelength
(urn)
.210
.220
.230
.240
.250
.260
.270
.280
.290
.300
.310
.320
.330
.340
Absorption
Cross-section
1.10E-21
1.20E-21
4.60E-21
1.30E-20
2.68E-20
4.21E-20
5.54E-20
5.92E-20
5.16E-20
3.44E-20
1.53E-20
4.60E-21
1.10E-21
O.OOE-01
Quantum
Yield
.070
.070
.070
.070
.070
.070
.070
.070
.070
.070
.070
.070
.070
.070
Table A-16
Photolytic Data for MEK + hv ••> ALD2 + R02R + MC03
Wavelength
(urn)
.210
.220
.230
.240
.250
.260
.270
.280
.290
.300
.310
.320
.330
.340
Absorption
Cross- sect ion
1.10E-21
1.20E-21
4.60E-21
1.30E-20
2.68E-20
4.21E-20
5.54E-20
5.92E-20
5.16E-20
3.44E-20
1.53E-20
4.60E-21
1.10E-21
O.OOE-01
Quantum
Yield
.100
.100
.100
.100
.100
.100
.100
.100
.100
.100
.100
.100
.100
.100
Table A-17
Photolytic Data for DIAL + hv
•> H02 + CO + MC03
Wavelength
.200
.350
.360
Absorption
Cross -sect ion
7.90E-20
7.90E-20
7.90E-20
Quantum
Yield
1.000
1.000
0.000
A-8
-------
Table A-18
Photolytic Data for GLYX+ hv -•> .13 HCHO + .87 H2 + 1.87 CO
Wavelength
(urn)
.230
.235
.240
.245
.250
.255
.260
.265
.270
.275
.280
.285
.290
.295
.300
.305
.310
.312
.315
.320
.325
.327
.330
.335
.340
.355
.360
.365
.370
.375
.380
.382
.384
.386
.388
.390
.391
.392
.393
.394
.395
.396
.397
.398
.399
.400
.401
.402
.403
.404
.405
.406
.407
.408
.409
.410
.411
.411
.412
.413
.413
Absorption
Cross-section
2.87E-21
2.87E-21
4.30E-21
5.73E-21
8.60E-21
1.15E-20
1.43E-20
1.86E-20
2.29E-20
2.58E-20
2.87E-20
3.30E-20
3.15E-20
3.30E-20
3.58E-20
2.72E-20
2.72E-20
2.87E-20
2.29E-20
1.43E-20
1.15E-20
1.43E-20
1.15E-20
2.87E-21
O.OOE-01
O.OOE-01
2.29E-21
2.87E-21
8.03E-21
1.00E-20
1.72E-20
1.58E-20
1.49E-20
1.49E-20
2.87E-20
3.15E-20
3.24E-20
3.04E-20
2.23E-20
2.63E-20
3.04E-20
2.63E-20
2.43E-20
3.24E-20
3.04E-20
2.84E-20
3.24E-20
4.46E-20
5.27E-20
4.26E-20
3.04E-20
3.04E-20
2.84E-20
2.43E-20
2.84E-20
6.08E-20
5.07E-20
6.08E-20
4.86E-20
8.31E-20
6.48E-20
Quantum
Yield
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
Wavelength
(urn)
.414
.414
.415
.415
.416
.417
.418
.419
.420
.421
.421
.422
.422
.423
.424
.425
.426
.426
.427
.428
.429
.430
.431
.432
.433
.434
.434
.435
.436
.436
.437
.438
.438
.439
.440
.441
.442
.443
.444
.445
.446
.447
.448
.449
.450
.451
.451
.452
.453
.454
.455
.455
.456
.457
.458
.458
.459
.460
.460
.461
.462
Absorption
Cross -sect ion
7.50E-20
8.11E-20
8.11E-20
6.89E-20
4.26E-20
4.86E-20
5.88E-20
6.69E-20
3.85E-20
5.67E-20
4.46E-20
5.27E-20
1.05E-19
8.51E-20
6.08E-20
7.29E-20
1.18E-19
1.30E-19
1.07E-19
1.66E-19
4.05E-20
5.07E-20
4.86E-20
4.05E-20
3.65E-20
4.05E-20
6.08E-20
5.07E-20
8.11E-20
1.I3E-19
5.27E-20
I.C'IE-19
1.38E-19
7.70E-20
2.47E-19
8.11E-20
6.08E-20
7.50E-20
9.32E-20
1.13E-19
5.27E-20
2.43E-20
2.84E-20
3.85E-20
6.08E-20
1.09E-19
9.32E-20
1.22E-19
2.39E-19
1.70E-19
3.40E-19
4.05E-19
1.01E-19
1.62E-20
1.22E-20
1.42E-20
4.05E-21
4.05E-21
6.08E-21
2.03E-21
O.OOE-01
Quantum
Yield
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
.029
A-9
-------
Table A-19
Photolytic Data for MGLY + hv ••> H02 + CO + MC03
Wavelength
(urn)
.220
.225
.230
.235
.240
.245
.250
.255
.260
.265
.270
.275
.280
.285
.290
.295
.300
.305
.310
.315
.320
.325
.330
.335
.350
.354
.358
.360
.362
.364
.366
.368
.370
.372
.374
.376
.378
.380
.382
.384
.386
.383
.390
.392
Absorption
Cross-section
2.10E-21
2.10E-21
4.21E-21
7.57E-21
9.25E-21
8.41E-21
9.25E-21
9.25E-21
9.67E-21
1.05E-20
1.26E-20
1.43E-20
1.51E-20
1.43E-20
1.47E-20
1.18E-20
1.14E-20
9.25E-21
6.31E-21
5.47E-21
3.36E-21
1.68E-21
8.41E-22
O.OOE-01
O.OOE-01
4.21E-22
1.26E-21
2.10E-21
2.10E-21
2.94E-21
3.36E-21
4.21E-21
5.47E-21
5.89E-21
7.57E-21
7.99E-21
8.83E-21
1.01E-20
1.09E-20
1.35E-20
1.51E-20
1.72E-20
2.06E-20
2.10E-20
Quantum
Yield
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
Wavelength
(urn)
.394
.396
.398
.400
.402
.404
.406
.408
.410
.412
.414
.416
.418
.420
.422
.424
.426
.428
.430
.432
.434
.436
.438
.440
.441
.442
.443
.433
.444
.445
.446
.447
.448
.449
.450
.451
.452
.453
.454
.456
.458
.460
.464
.468
Absorpt i on
Cross-section
2.31E-20
2.48E-20
2.61E-20
2.78E-20
2.99E-20
3.20E-20
3.79E-20
3.95E-20
4.33E-20
4.71E-20
4.79E-20
4.88E-20
5.05E-20
5.22E-20
5.30E-20
5.17E-20
5.30E-20
5.22E-20
5.55E-20
5.13E-20
5.68E-20
6.22E-20
6.06E-20
5.47E-20
6.14E-20
5.47E-20
5.55E-20
6.81E-20
5.97E-20
5.13E-20
4.88E-20
5.72E-20
5.47E-20
6.56E-20
5.05E-20
3.03E-20
4.29E-20
2.78E-20
2.27E-20
1.77E-20
8.41E-21
4.21E-21
1.68E-21
O.OOE-01
Quantum
Yield
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
.107
A-10
------- |