Coursepack for Air Environment
Workshop in the Chemical Sciences
May 24, 2006
Instructor
Theodore S. Dibble
Associate Professor of Chemistry
SUNY-Environmental Science and Forestry
Syracuse, NY 13210
tsdibble@syr.edu
(315) 470-6596
Contents:
A.
Outline
B.
Reference works
C.
Selected pages from JPL Data Evaluation #14
D.
Data useful in teaching kinetics calculations
E.
Data on climate change
F.
Comparing the stratospheric chemistry of the halogens
G
Heterogeneous chemical kinetics
H.
Concentration data for the troposphere
I.
Lifetimes with respect to OH, O3, and NO3
J.
Degradation pathways of alkenes, oxygenates, aromatics
K.
Tropospheric photochemistry
A.
OUTLINE
I.
II.
Ozone: The Good, the Bad, and the Ugly
Atmospheric Structure and Circulation
Temperature defines the structure of the atmosphere
Pressure vs. altitude - the barometric law does not apply below ~130 km !
Atmospheric composition and units
Vertical mixing times in the global atmosphere
Global circulation patterns
Horizontal mixing times
Exercise: Distribution of CF2Cl2 and CO
Spectrometry and Photochemistry
Absorption cross-sections
Spectrometry of ozone
Solar flux versus wavelength, altitude, and Solar Zenith Angle
Quantum yields
Photolysis rate constants
Activity: Calculating photolysis rates with Excel
Kinetics: The atmosphere is not in equilibrium
Pseudo-first order approximation – Cl + O3
Steady-state approximation – ClO example
Ozone loss from CFCs
Catalytic cycles and storage
Activity: Calculating the fate of atomic chlorine
[Comparing the stratospheric chemistry of the halogens]
Chemistry of radical families are coupled
3rd order kinetics – practical
Activity: Calculating the fate of ClO
CFCs and CFC substitutes [Degradation pathways]
Ozone Hole
Ozone hole – observations
Dark and Heterogeneous chemistry [Heterogeneous Kinetics]
Tropospheric Ozone
Photostationary state relationship
CO and CH4
Lifetimes of selected VOCs
Degradation pathways of alkanes [alkenes, oxygenates]
[Relevant photochemistry]
Propagation and termination reactions
Activity: Steady state concentration of C3H7, C3H7OO and C3H7O radicals
Meteorology and air pollution
Global climate change
Window regions and saturation
Activity: Saturation at a single wavelength
III.
IV.
V.
VI.
VII.
IX.
B.
REFERENCE WORKS
Textbooks
Finlayson-Pitts, B. J. and Pitts, J. N., Jr. Chemistry of the Upper and Lower Atmosphere, 2000.
Jacob, D. Introduction to Atmospheric Chemistry
Seinfeld, J. H. and Pandis, S. N. Atmospheric Chemistry and Physics: From Air Pollution to
Climate Change 1998 (2nd edition available August 2006)
Wayne, R. P. Chemistry of Atmospheres, 3rd edition, 2000.
Warneck, P. Chemistry of the Natural Atmosphere
Key References
Atkinson, R. Gas Phase Tropospheric Chemistry of Organic Compounds, J. Phys. Chem.
Reference Data Monograph 2, 1994.
Or, for a less detailed update, see: Atkinson, R. and Arey, J. "Gas-phase tropospheric chemistry
of biogenic volatile organic compounds: a review" Atmospheric environment; 37(2, suppl.):
S197-S219, 2003.
Houghton, J. Global Warming: The Complete Briefing.
Sander, S. P., Chemical Kinetics and Photochemical Data for Use in Stratospheric Modeling,
#14, JPL Publication 02-25, 2002. http://jpldataeval.jpl.nasa.gov/download.html
Other References
Science, Vol. 276, 16 May 1997. Special issue on Tropospheric Processes.
Faraday Discussions #100, 1995.
Faraday Discussions #130, 2005.
Atmospheric Sciences: Entering the twenty-first century (National Research Council, 1998.
http://fermat.nap.edu/catalog/6021.html
Decade-to-Century-Scale Climate Variability and Change: a Science Strategy. National
Research Council, 1998. http://fermat.nap.edu/catalog/6129.html
Rethinking the Ozone Problem in Urban and Regional Air Pollution. National Research Council,
1991. http://fermat.nap.edu/catalog/1889.html
Section B
page 1 of 2
Atkinson, R. Kinetics and Mechanisms of the Gas Phase Reactions of Hydroxyl Radical with
Organic Compounds, J. Phys. Chem. Reference Data Monograph 1, 1989.
Barker, J. R., Ed. Progress and Problems in Atmospheric Chemistry, 1995.
Chameides, W. L. Biogeochemical Cycles
Hansen, L. D. and Eatough, D. J. Organic Chemistry of the Atmosphere
Hester, R. E., Air Pollution and Health
Lave, L. B. Air Pollution and Health
Newman, L. Measurement Challenges in Atmospheric Chemistry.
Okabe, H. Photochemistry of Small Molecules, 1978.
Selected Data Sources on the Web
http://www.esf.edu/chemistry/dibble/AtmosChemCalc.htm
http://www.esf.edu/chemistry/dibble/links.htm#Atmospheric
Ozone maps
http://exp-studies.tor.ec.gc.ca/e/ozone/Curr_allmap_g.htm
http://toms.gsfc.nasa.gov/ozone/ozone.html
http://lap.physics.auth.gr/ozonemaps2/
Kinetics
http://kinetics.nist.gov/index.php
http://www.iupac-kinetic.ch.cam.ac.uk/
NIST Database
IUPAC Evaluations
Documents by W. P. L. Carter on smog chemistry
http://pah.cert.ucr.edu/~carter/bycarter.htm
C.
SELECTED PAGES FROM CHEMICAL KINETICS AND
PHOTOCHEMICAL DATA FOR USE IN STRATOSPHERIC
MODELING. #14. JPL PUBLICATION 02-25, 2002.
Table of Contents
Example of Table 1 - Bimolecular Rate Constants
Example of Table 2 - Termolecular Rate Constants
Thermodynamic Tables
TABLE OF CONTENTS
INTRODUCTION
viii
I.1
Basis of the Recommendations...................................................................................................................ix
I.2
Scope of the Evaluation..............................................................................................................................ix
I.3
Format of the Evaluation .............................................................................................................................x
I.4
Computer Access.........................................................................................................................................x
I.5
Data Formats ...............................................................................................................................................x
I.6
Units ............................................................................................................................................................x
I.7
Noteworthy Changes in This Evaluation .....................................................................................................x
I.8
Acknowledgements ................................................................................................................................. xiii
I.9
References ............................................................................................................................................... xiii
SECTION 1. BIMOLECULAR REACTIONS
1-1
1.1 Introduction ............................................................................................................................................. 1-1
1.2 Uncertainty Estimates.............................................................................................................................. 1-2
1.3 Notes to Table 1..................................................................................................................................... 1-31
1.4 References ............................................................................................................................................. 1-93
SECTION 2. TERMOLECULAR REACTIONS
2-1
2.1 Introduction................................................................................................................................................2-1
2.2 Low–Pressure-Limiting Rate Constant, k ox ( T ) ..................................................................................... 2-1
2.3
2.4
2.5
2.6
2.7
2.8
Temperature Dependence of Low–Pressure Limiting Rate Constants: Tn ............................................... 2-2
High-Pressure-Limit Rate Constants, k∞(T) ............................................................................................ 2-2
Temperature Dependence of High-Pressure-Limiting Rate Constants: Tm .............................................. 2-3
Uncertainty Estimates.............................................................................................................................. 2-3
Notes to Table 2....................................................................................................................................... 2-8
References ...............................................................................................................................................2-16
SECTION 3. EQUILIBRIUM CONSTANTS
3-1
3.1 Format ..................................................................................................................................................... 3-1
3.2 Definitions ............................................................................................................................................... 3-1
3.3 Notes to Table 3....................................................................................................................................... 3-3
3.4 References ............................................................................................................................................... 3-5
SECTION 4. PHOTOCHEMICAL DATA
4-1
4.1 Format and Error Estimates ..................................................................................................................... 4-3
4.2 Halocarbon Absorption Cross Sections and Quantum Yields ................................................................. 4-3
4.3 References ........................................................................................................................................... 4-102
SECTION 5. HETEROGENEOUS CHEMISTRY ................................................................................................... 5-1
5.1 Introduction ............................................................................................................................................. 5-1
5.2 Surface Types—Acid/Water, Liquids, and Solids................................................................................... 5-2
5.3 Surface Types—Soot and Alumina ......................................................................................................... 5-2
5.4 Surface Composition and Morphology.................................................................................................... 5-3
5.5 Surface Porosity....................................................................................................................................... 5-4
5.6 Temperature Dependences of Parameters................................................................................................ 5-4
5.7 Solubility Limitations .............................................................................................................................. 5-4
5.8 Data Organization.................................................................................................................................... 5-4
5.9 Parameter Definitions .............................................................................................................................. 5-5
5.10 Mass Accommodation Coefficients for Surfaces Other Than Soot ......................................................... 5-8
5.11 Notes to Table 5-1 ................................................................................................................................... 5-9
5.12 Gas/Surface Reaction Probabilities for Surfaces Other Than Soot........................................................ 5-16
5.13 Notes to Table 5-2 ................................................................................................................................. 5-19
iv
5.14
5.15
5.16
5.17
5.18
5.19
5.20
Soot Surface Uptake Coefficients.......................................................................................................... 5-32
Notes to Table 5-3 ................................................................................................................................. 5-32
Henry’s Law Constants for Pure Water................................................................................................. 5-35
Notes to Table 5-4 ................................................................................................................................. 5-36
Henry’s Law Constants for Acids.......................................................................................................... 5-40
Notes to Table 5-5 ................................................................................................................................. 5-40
References ............................................................................................................................................. 5-44
APPENDIX A. THERMODYNAMIC PARAMETERS ..........................................................................................A-1
A.1 Gas-phase entropy and enthalpy values...................................................................................................A-1
A.1 References ...............................................................................................................................................A-8
TABLES
Table I-1. Editions of this Publication......................................................................................................................... viii
Table I-2. Panel Members and their Major Responsibilities for the Current Evaluation............................................. viii
Table 1-1. Rate Constants for Second-Order Reactions...............................................................................................1-5
Table 2–1. Rate Constants for Termolecular Reactions...............................................................................................2-4
Table 3-1. Equilibrium Constants.............................................................................................................................. 3-2
Table 4-1. Photochemical Reactions ......................................................................................................................... 4-4
Table 4-2. Combined Uncertainties for Cross Sections and Quantum Yields........................................................... 4-6
Table 4-3. Absorption Cross Sections of O2 Between 205 and 240 nm .................................................................... 4-7
Table 4-4. Absorption Cross Sections of O3 at 273 K ............................................................................................... 4-8
Table 4-5. Parameters for the Calculation of O(1D) Quantum Yields ....................................................................... 4-9
Table 4-6. Absorption Cross Sections of HO2 ......................................................................................................... 4-10
Table 4-7. Absorption Cross Sections of H2O Vapor .............................................................................................. 4-11
Table 4-8. Absorption Cross Sections of H2O2 Vapor............................................................................................. 4-11
Table 4-9. Mathematical Expression for Absorption Cross Sections of H2O2 as a Function of Temperature......... 4-12
Table 4-10. Absorption Cross Sections of NO2 ....................................................................................................... 4-13
Table 4-11. Quantum Yields for NO2 Photolysis .................................................................................................... 4-14
Table 4-12. Absorption Cross Sections of NO3 at 298 K ........................................................................................ 4-16
Table 4-13. Mathematical Expression for Absorption Cross Sections of N2O as a Function of Temperature* ....... 4-16
Table 4-14. Absorption Cross Sections of N2O at 298 K ........................................................................................ 4-17
Table 4-15. Absorption Cross Sections of N2O5...................................................................................................... 4-18
Table 4-16. Absorption Cross Sections of HONO .................................................................................................. 4-19
Table 4-17. Absorption Cross Sections and Temperature Coefficients of HNO3 Vapor......................................... 4-20
Table 4-18. Absorption Cross Sections of HO2NO2 Vapor ..................................................................................... 4-20
Table 4-19. Absorption Cross Sections and Quantum Yields for Photolysis of CH2O ........................................... 4-21
Table 4-20. Absorption Cross Sections of CH3O2, C2H5O2, and CH3C(O)O2 ......................................................... 4-22
Table 4-21. Absorption Cross Sections of CH3OOH............................................................................................... 4-23
Table 4-22. Absorption Cross Sections of PAN ...................................................................................................... 4-25
Table 4-23. Absorption Cross Sections of FNO ...................................................................................................... 4-26
Table 4-24. Absorption Cross Sections of CCl2O, CClFO, and CF2O at 298 K...................................................... 4-27
Table 4-25. Absorption Cross Sections of Cl2 ......................................................................................................... 4-28
Table 4-26. Absorption Cross Sections of ClOO .................................................................................................... 4-29
Table 4-27. Absorption Cross Sections of OClO at the Band Peaks ....................................................................... 4-30
Table 4-28. Absorption Cross Sections of Cl2O ...................................................................................................... 4-32
Table 4-29. Absorption Cross Sections of ClOOCl at 200–250 K .......................................................................... 4-33
Table 4-30. Absorption Cross Sections of Cl2O3 ..................................................................................................... 4-34
Table 4-31. Absorption Cross Sections of Cl2O4 ..................................................................................................... 4-34
Table 4-32. Absorption Cross Sections of Cl2O6 ..................................................................................................... 4-34
v
Table 1 - page 8
A-Factora
E/R
k(298 K)a
O2(1Σ) + O3 → products
2.2×10–11
0
2.2×10–11
O2(1Σ) + H2O → products
–
–
O2(1Σ) + N → products
–
O2(1Σ) + N2 → products
O2(1Σ) + CO2 → products
g
Notes
1.2
200
A63
5.4×10–12
1.3
–
A64
–
<10–13
–
–
A65
2.1×10–15
0
2.1×10–15
1.2
200
A66
4.2×10–13
0
4.2×10–13
1.2
200
A67
O + OH → O2 + H
2.2×10–11
–120
3.3×10–11
1.2
100
B1
O + HO2 → OH + O2
3.0×10–11
–200
5.9×10–11
1.1
50
B2
O + H2O2 → OH + HO2
1.4×10–12
2000
1.7×10–15
2.0
1000
B3
→ HO2
H + O2 
M
(See Table 2-1)
H + O3 → OH + O2
1.4×10–10
470
2.9×10–11
1.25
200
B4
H + HO2 → products
8.1×10–11
0
8.1×10–11
1.3
100
B5
OH + O3 → HO2 + O2
1.7×10–12
940
7.3×10–14
1.2
80
B6
OH + H2 → H2O+ H
5.5×10–12
2000
6.7×10–15
1.1
100
B7
OH + HD → products
5.0×10–12
2130
4.0×10–15
1.2
200
B8
OH + OH → H2O + O
4.2×10–12
240
1.9×10–12
1.4
240
B9
Reaction
f(298 K)b
HO× Reactions
M

→ H2O2
(See Table 2-1)
OH + HO2 → H2O + O2
4.8×10–11
–250
1.1×10–10
1.3
100
B10
OH + H2O2 → H2O+ HO2
2.9×10–12
160
1.7×10–12
1.15
50
B11
HO2 + O3 → OH + 2O2
1.0×10–14
490
1.9×10–15
1.15
+160
–80
B12
HO2 + HO2 → H2O2 + O2
2.3×10–13
–600
1.7×10–12
1.3
200
B13
1.7×10–33[M]
–1000
4.9×10–32[M]
1.3
400
B13
–180
1.0×10–11
1.1
50
C1
M

→ H2O2 + O2
NO× Reactions
M
→ NO2
O + NO 
(See Table 2-1)
O + NO2 → NO + O2
5.6×10–12
1-8
Table 2–1. Rate Constants for Termolecular Reactions
Low-Pressure Limita
ko(T) = ko300 (T/300)–n
n
ko300
Reaction
High-Pressure Limitb
k∞(T) = k∞300 (T/300)–m
m
k∞300
f
g
Notes
1.1
50
A1
Ox Reactions
O + O2
M
(6.0) (–34)
2.4
–
–
(3.5±3.0) (–37)
2.0
0.6±0.6
–
–
A2
→ HO2
(5.7±0.5) (–32)
1.6±0.5
(7.5±4.0) (–11)
0±1.0
B1
M
(6.9) (–31)
1.0
(2.6) (–11)
0
(9.0±2.0) (–31)
1.5±0.3
(3.0±1.0) (–11)
0±1.0
(2.5) (–31)
1.8
(2.2) (–11)
0.7
(7.0±1.0) (–31)
2.6±0.3
(3.6±1.0) (–11)
0.1±0.5
(2.0) (–30)
3.0
(2.5) (–11)
0
M
(1.8±0.3) (–31)
3.2±0.4
(4.7±1.0) (–12)
1.4±1.4
M
(2.0) (–30)
4.4
(1.4) (–12)
0.7
→ O3
O(1D) Reactions
M
→ N2 O
O(1D) + N2
HOx Reactions
H + O2
M
→ H2 O 2
OH + OH
1.5
100
B2
NOx Reactions
O + NO
M
→ NO2
M
O + NO2
→ NO3
OH + NO
→ HONO
M
M
→ HONO2 (See Note)
OH + NO2
HO2 + NO2
→ HO2NO2
NO2 + NO3
→ N2 O 5
NO3
M
→ NO + O2
C1
1.3
100
C2
C3
1.3
100
C4
C5
1.2
100
See Note
C6
C7
Hydrocarbon Reactions
CH3 + O2
M
(4.5±1.5) (–31)
3.0±1.0
(1.8±0.2) (–12)
1.7±1.7
D1
M
(1.5±1.0) (–28)
3.0±1.0
(8.0±1.0) (–12)
0±1.0
D2
M
(5.5±2.0) (–30)
0.0±0.2
(8.3±1.0) (–13)
2
–2±1
D3
M
(1.0±0.6) (–28)
0.8±2.0
(8.8±0.9) (–12)
0
0±2
D4
(1.4±0.5) (–29)
3.8±1.0
(3.6±1.6) (–11)
0.6±1.0
D5
M
(5.3) (–29)
4.4
(1.9) (–11)
1.8
M
(2.8±1.0) (–27)
4.0±2.0
(5.0±1.0) (–11)
1.0±1.0
→ CH3O2
C2 H5 + O 2
→ C2 H5 O 2
OH + C2H2
→ HOCHCH
OH + C2H4
→ HOCH2CH2
CH3O + NO
→ CH3ONO
M
CH3O + NO2
→ CH3ONO2
C2H5O + NO
→ C2H5ONO
2-4
1.1
0
D6
D7
APPENDIX A. THERMODYNAMIC PARAMETERS
Table of Contents
APPENDIX A. THERMODYNAMIC PARAMETERS ..........................................................................................A-1
A.1
Gas-phase entropy and enthalpy values..................................................................................................A-1
A.1
References ..............................................................................................................................................A-8
Tables
Table A-1. Gas-phase entropy and enthalpy values for selected species at 298.15 K and 100 kPa. .........................A-1
A.1
Gas-phase entropy and enthalpy values
Table A-1 lists selected entropy and enthalpy of formation values at 298 K for a number of atmospheric
species. As much as possible, the values were taken from primary evaluations, that is, evaluations that develop a
recommended value from the original studies. Otherwise, the values were selected from the original literature, which
is referenced in the table. Often, the enthalpy of formation and the entropy values are taken from different sources,
usually due to a more recent value for the enthalpy of formation. The cited error limits are from the original
references and therefore reflect often widely varying criteria. Some enthalpy values were corrected slightly to reflect
the value of a reference compound selected for this table; these are indicated. Values that are calculated or estimated
are also indicated in the table.
Table A-1. Gas-phase entropy and enthalpy values for selected species at 298.15 K and 100 kPa.
SPECIES
H
H2
O(3P)
O(1D)
O2
O2(1∆g)
O2(1Σg+)
O3
OH
HO2
H2O
H2O2
N(4S)
N2
NH
NH2
NH3
NH2OH
NH2NO2
NO
N2O
NO2
NO3
N2O3
N2O4
N2O5
HNO
∆Hf(298 K)
kJ mol–1
217.998±0.006
0.00
249.18±0.10
438.05±0.1
0.00
94.29±0.01
156.96±0.01
141.8±2
37.20±0.38
13.8±3.3
–241.826±0.040
–135.88±0.22
472.68±0.40
0.00
357±1
186±1
–45.94±0.35
–40.2±9.2
–26±10
91.29±0.17
81.6±0.5
34.19±0.5
73.7±1.4
86.6±1
11.1±1
13.3±1.5
107.1±2.5
∆Hf(298 K)
kcal mol–1
52.103±.001
0.00
59.56±0.02
104.70±0.03
0.00
22.54±0.01
37.51±0.01
33.9±0.5
8.89±0.09
3.3±0.8
–57.798±0.010
–32.48±0.05
112.973±0.10
0.00
85.3±0.3
44.5±0.3
–10.98±0.08
–9.6±2.2
–6.2±3
21.82±0.04
19.50±0.12
8.17±0.1
17.6±0.3
20.7±0.3
2.65±0.25
3.18±0.36
25.6±0.6
A-1
S(298 K)
J K–1 mol–1
114.717±0.002
130.680±0.003
161.059±0.003
S(298 K)
cal K–1 mol–1
27.418±.0.001
31.233±0.001
38.194±0.001
205.152±0.005
49.033±0.001
239.01
183.74
229.1
188.835±0.010
234.52
153.301±0.003
191.609±0.004
181.25±0.04
194.71±0.05
192.77±0.05
236.18
268.54
210.76
220.01
240.17
258.4±1.0
314.74
340.45
355.7±7
57.12
43.91
54.76
45.133±.002
56.05
36.640±0.001
45.796±0.001
43.32±0.01
46.54±0.01
46.07±0.01
56.45
64.18
50.37
52.58
57.40
61.76±0.24
75.22
81.37
85.01±2
Referencea, b, c
[28]
[28]
[28]
[70]
[28]
[36]
[36]
[33]
[33,87]
[35,58]
[28]
[33]
[28]
[28]
[4]
[4]
[28]
[5]
[33]
[5,22]
[33]
[33]
[1,29]
[33]
[33]
[33]
[5]
SPECIES
HONO
HONO2
HO2NO
HO2NO2
C
CH
CH2(3B1)
CH2(1A1)
CH3
CH4
CN
HCN
C2N2
CH2NH2
CH3NH2
CH2NO
NH2CO
NCO
HNCO
CO
CO2
HCO
CH2O
HCOO
C(O)OH
HC(O)OH
CH3O
CH3O2
CH2OH
CH3OH
CH3OOH
CH2NO2
CH3NO2
CH3ONO
CH3ONO2
C2H
C2H2
C2H2OH
C2H3
C2H4
C2H5
C2H6
CH2CN
CH3CN
CH2CO
CH3CO
CH2CHO
CH3CHO
CH3CH2O
(CHO)2
∆Hf(298 K)
kJ mol–1
–78.45±0.8
–133.9±0.6
–23.8
–53.1±2.5
716.68±0.45
597.37±1.3
390.4±0.8
428.0±0.8
146.65±0.29
–74.48±0.41
440±5
132±4
309.1±0.8
149±8
–23.4±1.0
157±4
–15.1±4
151±14
–104±12
–110.53±0.17
–393.51±0.13
44.15±0.43
–108.7±0.05
127
–193
–378.8±0.5
17.15±3.8
9.0±5.1
–11.5±1.3
–201.0±0.6
–139.0±8.1
147.3
–74.3±0.6
–64.0
–122.2±4.3
565.3±2.9
227.4±0.8
121±11
299±5
52.4±0.5
120.9±1.7
–83.85±0.29
252.6±4
74.04±0.37
–49.58±0.88
–10.0±1.2
10.5±9.2
–166.1±0.5
–15.5±3.3
–212±0.8
∆Hf(298 K)
kcal mol–1
–18.75±0.2
–32.0±0.1
–5.7
–12.7±0.6
171.29±0.11
142.77±0.3
93.31±0.2
102.3±0.2
35.05±0.07
–17.80±0.10
105±1
31.5±1
73.9±0.2
35.6±2
–5.6±0.3
37.5±1
–3.6±1
36±3
– 24.8±2.8
–26.42±0.04
–94.05±0.03
10.55±0.10
–25.98±0.01
30
–45
–90.54±0.1
4.1±0.9
2.15±1.2
–2.75±0.31
–48.04±0.14
–33.2±1.9
35.2
–17.8±0.2
–15.3
–29.2±1.1
135.1±0.7
54.35±0.2
28.9±2.6
71.5±.1
12.52±0.12
28.9±0.4
–20.04±0.07
60.4±1.0
17.70±0.09
–11.85±0.21
–2.4±0.3
2.5±2.2
39.7±0.1
–3.7±0.8
–50.7±0.2
A-2
S(298 K)
J K–1 mol–1
254.07
266.88
274
294±3
158.100±0.001
183.04
194.90
S(298 K)
cal K–1 mol–1
60.72
63.78
65.6
70.3±0.7
37.787±0.001
43.75
46.58
193.96
186.38
202.64
201.82
242.20
46.36
44.55
48.43
48.24
57.89
242.89
58.05
232.38
237.97±0.8
197.660±0.004
213.785±0.010
224.34
218.76
244.7
251.6
248.87
232.86
55.54
56.9±0.2
47.242±0.001
51.096±0.002
53.62
52.28
58.5
60.1
59.48
55.655
244.170±0.018
239.865
58.358±0.004
57.329
272.48
275.2
284.3
301.9
209.73
200.93
65.12
65.8
67.95
72.15
50.13
48.02
219.316
250.52
229.162
52.418
59.88
54.771
245.12±0.8
58.59±0.2
263.95
63.09
Referencea, b, c
[33]
[33]
[61], calc.
[84]
[28]
[33]
[88]
[39]
[33,88]
[31,82]
[33]
[33]
[33]
[62], corr.
[31,79]
[96], calc.
[96], calc.
[75], corr., [33]
[97], corr.,[102]
[28]
[28]
[8], corr., [33]
[33]
[106], calc.
[106]
[33,106]
[11,33]
[46]
[41]
[33]
[46]
[31]
[31,79]
[98]
[79,98]
[11,33]
[33]
[32]
[99]
[33]
[11,33]
[33,82]
[52]
[2,102]
[88]
[11]
[11]
[31,79]
[11]
[30]
SPECIES
C2H5O
C2H5O2
C2H5OOH
CH2CH2OH
CH3CHOH
C2H5OH
CH3COO
CH2C(O)OH
CH3C(O)O
CH3C(O)OH
CH3C(O)O2
CH3C(O)O2NO2
HOCH2COOH
CH3OCH2
CH3OCH3
CH2(OH)CH2OH
CH3OOCH3
(HOCO)2
C3H5
C3H6
n–C3H7
i–C3H7
i–C3H7O2
C3H8
C2H5CHO
CH3COCH3
n-C4H10
(CH3COO)2
F
F2
HF
HOF
FO
FOF
OFO
FOO
FOOF
FONO
FNO
FNO2
FONO2
CF
CHF
CF2
CF3
CF4
CHF3
CHF2
CH2F2
CH2F
∆Hf(298 K)
kJ mol–1
–17.2
–27.4±9.9
–175.4±12.9
–31±7
–63.7±4
–234.8±0.5
–190
–243
–192.5
–432.8±0.5
–154.4
–240.1
–583±10
–13.0±4
–184.1±0.5
–392.2±4.0
–125.5±5.0
–731.8±2.0
166.1±4.3
20.0±0.7
100±2
86.6±2.0
–65.4±11.3
–104.68±0.50
–185.6±0.8
–217.1±0.7
-125.65±0.67
–500±10
79.38±0.30
0.00
–273.30±0.70
–98.3±4.2
109±10
24.5±2
380±20
25.4±2
19.2±2.0
67
–65.7
–79
10±2
244.1±10
143.1±12
–184±8
–465.7±2.1
–933.20±0.75
–692.9±2.1
–239±4
–452.7±0.8
–32±8
∆Hf(298 K)
kcal mol–1
–4.1
–6.6±2.4
–41.9±3.1
–7.5±1.7
–15.2±1
–56.12±0.12
–45
58
–46.0
–103.4±0.1
–36.9
–57.4
–139±3
–3.1±1
–44.0±0.1
93.7±1.0
–30.0±1.2
–174.9±0.5
39.7±1.0
4.78±0.2
24±0.5
20.7±0.5
–15.6±2.7
–25.02±0.12
44.4±0.2
51.9±0.2
-30.03±0.16
–120±3
18.94±0.07
0.00
–65.32±0.17
–23.5±1.0
26±3
5.86±0.5
90.8±5
6.07±0.5
4.59±0.5
16
–15.70
–19.0
2.5±0.5
58.3±2.4
34.2±3.0
–44.0±2
–111.3±0.5
–223.04±0.18
–165.6±0.5
–57.1±1.0
–108.2±0.2
–7.6±2
A-3
S(298 K)
J K–1 mol–1
S(298 K)
cal K–1 mol–1
281.622
284.9
238.4
67.309
68.1
57.0
332.67
79.51
318.6±5.0
76.1±1.2
267.34
303.81
63.90
72.61
320.6±5.0
248±15
266.6
76.6±1.2
59.3±3.6
63.72
281±5
67.2±1.2
270.20
304.51
295.46
309.91
390.7±6.0
158.751±0.004
202.791±0.005
173.799±0.003
226.77±0.21
216.40±0.3
247.46±0.4
251±1
259.5±0.2
277.2±0.2
64.58
70.62
74.07
93.4±1.4
37.942±0.001
48.468±0.001
41.539±0.001
54.20±0.05
51.72±0.07
59.14±0.1
60.0±0.3
62.02±0.05
66.25±0.05
248.0
277.1
290
213.03±0.04
234.87
240.83±0.04
264.56
261.454
259.67
258.50
246.59
236.52
59.27
66.24
70
50.92±0.01
56.14
57.56±0.01
63.23
62.49
62.06
61.78
58.94
56.53
Referencea, b, c
[62]
[46]
[46]
[32]
[62]
[33]
[106], calc.
[106]
[63], calc.
[18,79]
[63], calc.
[63], calc.
[30]
[62], corr.
[31,79]
[31,79]
[30]
[30]
[94]
[17,79]
[99]
[95]
[46]
[16,82]
[31,79]
[31,79]
[31,82]
[30]
[28]
[28]
[28]
[22]
[21]
[21]
[21], calc.
[21]
[21]
[6], est
[98]
[98]
[22], est.
[22,33]
[33,83]
[22,83]
[33,89]
[28]
[33,89]
[81]
[85]
[81]
SPECIES
CH3F
FCO
CHFO
CF2O
CF3O
CF2O2
CF3O2
CF3OH
CF3OOCF3
CF3OF
CH2CH2F
CH3CHF
CH3CH2F
CH2FCH2F
CH2FCHF
CH2FCHF2
CHF2CHF2
CH2CF3
CH3CF3
CHF2CH2
CH3CF2
CH3CHF2
CHFCF3
CH2FCF3
CF2CF3
CHF2CF3
C2F6
Cl
Cl2
HCl
ClO
ClOO
OClO
ClO3
ClClO
ClOCl
ClOOCl
ClClO2
ClOClO
Cl2O3
HOCl
ClNO
ClNO2
cis–ClONO
trans–ClONO
ClO2NO
ClONO2
FCl
CHCl
CCl2
∆Hf(298 K)
kJ mol–1
–238±8
–161.2±8.1
–383±7
–607.9±7.1
–624±8
–427±6
-612.5±15.4
–911±8
–1434±11
–724±8
59.4±8
–70.3±8
–277.4±4.2
–432±25
235.5
–665±4
–860±24
–517.1±5
–745.6±1.7
–277
–302.5±8.4
–500.1±6.3
–697
–896±8
–891±5
–1105±5
–1344.3±3.4
121.301±0.008
0.00
–92.31±0.10
101.63v0.1
98.0v4
94.6v1.2
194±12
90±30
81.3±1.8
127.6±2.9
154.2
175.5
150±6
–74.8±1.2
52.7±0.5
12.5±1.0
–64.4±6.3
75.3±6.3
102
22.9±2.0
–55.70±0.31
326±8
230±8
∆Hf(298 K)
kcal mol–1
–56.8±2
–38.5±2.0
–91.6±1.7
–145.3±1.7
–149±2
–102±1.5
146±4
–218±2
–343±3
–173±2
–14.2±2
–16.8±2
–66.3±1
–103.2±6
56.28
–158.9±1
–205.6±5.7
–123.6±1.2
–178.2±0.4
–66.3
–72.3±2
–119.7±1.5
–166.5
–214.1±2
–213±1.3
–264±1.1
–321.3±0.8
28.992±0.002
0.00
–22.06±0.02
24.29±0.03
23.4±1
22.6±0.3
46±3
22±7
19.4±0.4
30.5±0.7
36.9
41.9
35.8±1.5
–17.9±0.3
12.6±0.1
3.0±0.3
15.4±1.5
18.0±1.5
24.3
5.5±0.5
13.31±0.07
78.0±2.0
55.0±2.0
A-4
S(298 K)
J K–1 mol–1
222.78
S(298 K)
cal K–1 mol–1
53.246
246.82
258.97
58.99
61.89
279.7
274.0
265.1
66.86
65.48
63.4
293.3
70.11
320.3
306.8
287.3
297.8
290.3
282.4
326.2
316.2
76.6
73.32
68.67
71.17
69.39
67.50
77.97
75.58
333.7
331.8
165.190±0.004
223.081±0.010
186.902±0.005
225.07±0.5
269.32±0.5
256.84±0.1
270.75±0.5
278.8±2.0
79.76
79.30
39.481±0.001
53.318±0.002
44.671±0.001
53.79±0.12
64.37±0.1
61.39±0.03
64.71±0.1
66.6±0.5
301.0±5.0
294±2
309±2
390±20
236.50±0.42
261.58
272.23
71.9±1.2
70.3±0.5
73.9±0.5
94±5
56.52±0.10
62.52
65.06
316
302.38
217.94
234.88
265.03
75.5
72.27
52.09
56.85
63.34
Referencea, b, c
[85], H est.
[44]
[91],calc., [33]
[91],calc., [33]
[91], calc.
[48], calc.
[56]
[91]
[91]
[91]
[66],[25], calc.
[66], [26], calc.
[59], est. [33]
[42]
[27]
[51], corr.
[64], corr. [31]
[25,104]
[23]
[25], calc.
[80], [26], S calc
[23]
[27], H corr.
[23], H est.
[105]
[23]
[23,89]
[28]
[28]
[28]
[22]
[22]
[22,72]
[22]
[22]
[34]
[22,72]
[55],calc., [22]
[55],calc., [22]
[14]
[22,34]
[33]
[33]
[54], calc.
[54], calc.
[61], calc.
[3]
[33]
[33,83]
[33,83]
SPECIES
CCl3
CCl3OH
CCl3O
CCl3O2
CCl4
CHCl3
CHCl2
CHCl2O2
CH2Cl
CH2ClO2
CH2Cl2
CH3Cl
ClCO
CHClO
CCl2O
CHFCl
CH2FCl
CFCl
CFCl2
CFCl3
CF2Cl2
CF3Cl
CHFCl2
CHF2Cl
CF2Cl
CFClO
CH2ClCOOH
C2H3Cl
CH3CHFCl
CH2CF2Cl
CH3CF2Cl
C2Cl4
1,1–C2H2Cl2
Z–1,2–C2H2Cl2
E–1,2–C2H2Cl2
C2HCl3
CH2CCl3
1,1,1–C2H3Cl3
1,1,2–C2H3Cl3
1,1,1,2–C2H2Cl4
1,1,2,2–C2H2Cl4
C2HCl5
CH3CCl2
CH3CCl2O2
CH3CHCl2
CH2CH2Cl
CH3CHCl
CH3CH2Cl
C2Cl6
Br
∆Hf(298 K)
kJ mol–1
71.1±2.5
–293±20
–43.5±20
–20.9±8.9
–95.6±2.5
–102.9±2.5
89.0±3.0
–17±7
117.3±3.1
–4v11
–95.1±2.5
–81.9±0.6
–24.9±4.2
–164±20
–220.9
–61±10
–264±8
31v13
–89.1±10.0
–285.3
–494.1
–709.2±2.9
–285±9
–484.8
–279±8
–429±20
–427.6±1.0
22±3
–313.4±2.6
–318
–536.2±5.2
–18.8±4
2.4±2.0
–3±2
–0.5±2.0
–19.1±3.0
71.5±8
–144.6±2.0
–148.0±4.0
–152.3±2.4
–156.7±3.5
–155.9±4.3
42.5±1.7
–69.7±4
–130.6±3.0
93.0±2.4
76.5±1.6
–112.1±0.7
–142±4
111.870±12
∆Hf(298 K)
kcal mol–1
17.0±0.6
–70.0±5
–10.4±5
–5.0±2.1
–22.8±0.6
–24.6±0.6
21.3±0.7
–4!2
28.0±0.7
–1±3
–22.8±0.6
–19.6±0.2
–5.9±1.0
–38±5
–52.8
–14.5±2.4
–63.2±2
7.4±3.2
–21.3±2.4
–68.2
–118.1
–169.5±0.7
–68.1±2.1
–115.6
–66.7±2
–103±5
–102.2±0.2
5.3±0.7
–74.9±0.6
–75.9
–128.2±1.2
–4.5±1
0.6±0.5
–0.7±0.5
–0.1±0.5
–.6±0.7
17.1±2
–34.6±0.5
–35.4±0.9
–36.4±0.6
–37.5±0.8
–37.3±1.0
10.2±0.4
–16.7±1
–31.2±0.7
22.2±0.6
18.2±0.4
–26.8±0.2
–34.0±1
26.74±0.03
A-5
S(298 K)
J K–1 mol–1
303.24
S(298 K)
cal K–1 mol–1
72.47
309.90
295.51
280±7
74.069
70.63
66.9±2
271±7
64.5±2
270.31
227.15
266.0
259.07
283.8
64.606
54.290
63.6
61.92
67.82
264.3
259.032
63.17
61.91
309.9
300.7
285.2
293.0
280.8
74.06
71.87
68.16
70.04
67.11
276.70
325.9±5.0
66.13
77.9±1.2
322.08
307.1
341.03
76.98
73.41
81.51
325.20
77.72
320.03
76.488
288±5
68.8±1.1
305.05
271±7
279±6
275.78
398.62
175.018±0.004
72.908
64.8±2
66.7±1.4
65.913
95.27
41.830±0.001
Referencea, b, c
[37]
[90], calc.
[90], calc
[46]
[38,85][60]
[60,85]
[92]
[92]
[92]
[92]
[60,85]
[60,85]
[22,57]
[33], H est,
[98]
[100]
[24,100], H est.
[33,83]
[100]
[24], corr.
[24], corr.
[24,89]
[24], H est.
[24], H est.
[68]
[33]
[30]
[60]
[47]
[77]
[47,77]
[33,38]
[60]
[60]
[60]
[31,78]
[86]
[15,47,60]
[60]
[60]
[60]
[60]
[92]
[45], corr.
[15,47]
[93]
[92]
[15,60]
[33,38]
[28]
Br2(g)
∆Hf(298 K)
kJ mol–1
30.91±0.11
∆Hf(298 K)
kcal mol–1
7.39±0.03
HBr
Br2O
HOBr
BrO
–36.29±0.16
106.2±2.5
–60.5±1.1
126.2±1.7
–8.67±0.04
25.4±0.6
–14.5±0.3
30.2±0.4
OBrO
163.9±4.4
BrOO
SPECIES
S(298 K)
J K–1 mol–1
S(298 K)
cal K–1 mol–1
Referencea, b, c
245.468±0.005
58.668±0.001
[28]
198.700±0.004
47.490±0.001
232.97±0.1
55.681±0.023
[28]
[34]
[34]
[19,103]
39.2±1.1
271±2
64.8±0.5
[19,43], est.
108±40
26±10
289±3
69.1±0.7
[19]
BrO3
221±50
53±12
285±2
68.1±0.5
[19], est.
BrOBr
107.6±3.5
25.7±0.8
290.8±2
69.50±0.48
BrBrO
168±20
40±5
313±2
74.8±0.5
[19], est.
273.66±0.8
65.41±0.2
228.985
240.046
54.729
57.372
330.67
79.03
334.57
294
245.85±0.25
80.0
70.23
58.76±0.06
287.3±0.4
68.66±0.09
358.06
337.0±5.0
180.787±0.004
85.6
80.5±1.2
43.209±0.001
[102]
[53], calc.
[53], calc.
[53], calc.
[76]
[33]
[33]
[100]
[13]calc.,[33]
[100]
[33]
[13], calc.
[49]
[10]
[67] corr.
[47,50]
[69]
[47]
[89]
[13,33]
[30]
[28]
BrNO
Z–BrONO
E–BrONO
BrNO2
BrONO2
BrF
BrCl
CH2Br
CHBr3
CHBr2
CBr3
CH2Br2
CH3Br
CH2CH2Br
CH3CHBr
CH3CH2Br
CH3CBr2
CH3CBr2H
CF3Br
CBr4
CH2BrCOOH
I
[19]
82.17±0.8
71.9
88.3
45.2
42.3±6.3
–58.9±1.0
14.79±0.16
169±4
23.8±4.5
188.9
235±25
–11.1±5.0
–37.7±1.5
135.6±6.7
127±4
–61.5±1.0
140.2±5.4
26.7±1.9
–641.4±2.3
83.9±3.4
–383.5±3.1
106.76±0.04
19.64±0.2
17.19
21.1
10.8
10.1±1.5
–14.08±0.3
3.53±0.04
40.4±1.0
5.7±1.1
45.0±2.2
56±6
–2.7±1.2
–9.02±0.36
32.4±1.6
30.4±1
–14.7±0.3
33.5±1.3
6.4±0.5
–153.3±0.5
20.0±0.8
–91.7±0.7
25.52±0.01
I2
62.42±0.08
14.92±0.02
260.687±0.005
62.306±0.001
[28]
HI
26.50±0.10
6.33±0.03
206.590±0.004
49.376±0.001
[28]
HOI
–69.6±5.4
–16.6±1.3
255.0±0.1
60.95±0.03
[12,34]
IO
OIO
IOO
IO3
IOI
IIO
IOOI
IIOO
IOIO
OIIO
INO
115.9±5.0
77±15
96.6±15
242±50
92.4±15
134.1±15
156.8±15
103.0±15
124.2±15
224.0±15
121±4
27.7±1.2
18±4
23±4
58±12
22.1±4
32.1±4
37.5±4
24.6v4
29.7±4
53.5±4
29.0±1
239.6±0.1
279.9
308.4
293±4
306.5
317.8
337.0
339.9
349.7
356.3
282.8±4
57.27±0.03
66.9
73.7
70.0±1.0
73.3
76.0
80.5
81.2
83.6
85.2
67.6±1
[9,34]
[65], calc.
[65], calc.
[20], est.
[65]
[65]
[65], calc.
[65], calc.
[65], calc.
[65], calc.
[101]
A-6
SPECIES
INO2
ICl
IBr
CH3I
CH2I2
CF3I
CH3CH2I
S
∆Hf(298 K)
kJ mol–1
60.2±4
17.506±0.105
40.88±0.08
13.76±0.12
118.4±0.1
–586.2±2.1
–7.5±0.9
277.17±0.15
∆Hf(298 K)
kcal mol–1
14.4±1
4.184±0.025
9.77±0.02
3.29±0.03
28.30±0.03
–140.1±0.5
–1.79±0.2
66.25±0.04
S(298 K)
J K–1 mol–1
S(298 K)
cal K–1 mol–1
Referencea, b, c
294±6
427.567
258.95
253.70±0.25
70.3±1.5
102.191
61.89
60.635±0.06
[101]
[22]
[22]
[49]
309.41±1.34
307.78
295.52±0.42
73.95±0.32
73.56
70.63±0.10
[49]
[33,89]
[47,50]
167.829±0.006
40.112±0.002
[28]
[28]
S2
128.6±0.3
30.74±.07
228.167±0.010
54.533±0.003
HS
195.55
46.74
[74],
corr.,
[33]
142.80±2.85
34.13±0.68
[28]
H2S
–20.6±0.5
–4.92±0.12
205.81±0.05
49.19±0.01
SO
221.94
53.04
[33]
4.78±0.25
1.14±0.06
[28]
SO2
–296.81±0.20
–70.94±0.05
248.223±0.050
59.327±0.012
SO3
256.541
61.315
[33]
–395.9±0.7
–94.62±0.17
HSO
[7]
–6.1±2.9
–1.5±0.7
H2SO4
299.282
71.530
[33]
–733±2
–175.2±0.5
CS
210.55
50.32
[33]
279.775±0.75
66.87±0.18
CS2
237.882
56.855
[33]
116.7±1.0
27.9±0.2
[71]
CS2OH
110.5±4.6
26.4±1.1
321±20
77±5
CH3S
[73], corr.
125.0±1.8
29.87±0.44
CH3SH
255.14
60.98
[31,79]
–22.9±0.7
–5.47±0.17
CH2SCH3
[40]
136.8±5.9
32.7±1.4
CH3SCH3
285.96
68.35
[31,79]
–37.4±0.6
–8.94±0.2
CH3SSCH3
336.80
80.50
[31,79]
–24.7±1.0
–5.9±0.3
OCS
231.644
55.36
[33]
–141.7±2
–33.9±0.5
Notes:
a. Error limits are estimates from the original references.
b. If two references are given for a substance, the first refers to the enthalpy value while the second to the
entropy.
c. The terms “calc” and “est” indicate that the value is calculated or estimated. The term “corr” indicates
that an enthalpy value has been adjusted to reflect the value chosen in this table for a reference
substance.
A-7
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A-10
D.
DATA USEFUL IN TEACHING KINETICS CALCULATIONS FOR
STRATOSPHERIC CHEMISTRY
Extracted from:
Kinetics and Photochemical Data for Use in
Stratospheric Modeling. #12
JPL Publication 97-4 2002.
Solar Fluxes
Temperature and Pressure Profiles
Concentration Profiles
Photolysis Rate Constants
APPENDIX 3: SOLAR FLUXES AND SPECIES PROFILES
Figures 6 and 7 show data for solar irradiances and fluxes. These were provided by Kenneth
Minschwaner. The solar irradiances are from measurements by the Solar Ultraviolet Spectral Irradiance
Monitor (SUSIM) for λ ≤ 400 nm (VanHoosier et al. [6]), and by Neckel and Labs [5] for 400 < λ ≤ 600
nm. The SUSIM measurements are spectrally degraded to 2 nm full width half-maximum to correspond to
the resolution of the Neckel and Labs data. Additionally, a normalization factor that varies linearly from
1.17 at 400 nm to 1.0 at 440 nm has been applied to the Neckel and Labs irradiances in order to match
SUSIM values at 400 nm. Irradiances from 110 to 120 nm are based on measurements by Mount and
Rottman [4] and Woods and Rottman [8]. Values below 110 nm are not plotted.
The solar fluxes are computed from the sum of the direct, attenuated solar beam plus angularly
integrated scattered radiation. Fluxes at 0, 20, 30, 40, and 50 km are based on the solar irradiances,
assuming a solar zenith angle of 30° and the U.S. Standard Atmosphere (1976). Molecular and aerosol
scattering are taken into account; the latter process is appropriate for "moderate volcanic" conditions (Fenn
et al. [2]). The surface albedo is 0.3. Ozone cross sections follow the recommendations herein; oxygen
cross sections in the Herzberg continuum are taken from Yoshino et al. [9]; Schumann-Runge band
absorption is determined using the high-resolution treatment of Minschwaner et al. [3], with fluxes
spectrally degraded to 1.0 nm resolution.
The species and "J" value profiles presented in Figures 8-16 were provided by Peter Connell. They
were generated by the LLNL 2-D model of the troposphere and stratosphere. The temperature profile is an
interpolation to climatological values. Surface source gas boundary conditions are those for the year 1990,
as reported in chapter 6 of the WMO/UNEP report [7]. The equatorial tropopause source gas mixing ratios
are: total chlorine 3.4 ppb, total fluorine 1.6 ppb, total bromine 18 ppt, methane 1.67 ppm, and nitrous
oxide 309 ppb. The kinetic parameters used were consistent, to the extent possible, with the current
recommendations. Representations of sulfate aerosol and polar stratospheric heterogeneous processes
which were included are hydrolysis of nitrogen pentoxide and chlorine and bromine nitrate and reaction of
hydrogen chloride with chlorine nitrate and hypochlorous acid. The model run represents a periodic
steady-state atmosphere with 1990 surface abundances of source gases.
The "J" values were calculated with a clear sky, two-stream radiative transfer model with
wavelength binning of 5 nm above 310 nm and 500 cm-1 below. Surface reflectance includes the effect of
average cloudiness on the albedo. Oxygen cross sections in the Schumann-Runge region were calculated
by the method of Allen and Frederick [1], corrected for the Herzberg continuum values of Yoshino et al.
[9].
The fluxes and profiles are given to provide "order of magnitude" values of important photochemical
parameters. They are not intended to be standards or recommended values.
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258
Figure 6. Solar Irradiance
259
Figure 7. Actinic Flux at Several Altitudes
260
Altitude (km)
10
30
20
100
10
200
220
240
Temperature (K)
260
280
1018
261
Figure 8. Temperature and Density
40
Total Density (molecules/cm3)
Pressure (mb)
50
TEMPERATURE (March 15 - 40 N)
1
1017
OXYGEN and HYDROGEN SPECIES (March 15 - Local Noon - 40 N)
50
H*108
1017
40
Total Density
Altitude (km)
O(3P)
O3
30
O(1D)*108
CH4
1018
20
H2O
H2O2
10
106
108
1010
Number Density (molecules/cm3)
1012
1014
262
OH
Figure 9. Number Densities of Oxygen and Hydrogen Species
HO2
NITROGEN SPECIES (March 15 - Local Noon - 40 N)
50
NO
Total Density
Altitude (km)
HO2NO2
30
NO2
HNO3
N2O
1018
NO3*106
20
ClONO2
N2O5
10
106
107
108
109
1010
Number Density (molecules/cm3)
1011
1012
263
1017
40
Figure 10. Number Densities of Nitrogen Species
N(4S)*108
CHLORINE SPECIES (March 15 - Local Noon - 40 N)
50
HCl
Total Density
Altitude (km)
ClONO2
30
Cl
ClO
1018
20
10
104
105
106
107
108
3
Number Density (molecules/cm )
109
264
1017
40
Figure 11. Number Densities of Chlorine Species
HF
OTHER SPECIES (March 15 - Local Noon - 40 N)
Total Density
Altitude (km)
30
1018
CFCl3
20
10
106
107
CF2Cl2
108
109
1010
Number Density (molecules/cm3)
CO
1011
1012
265
1017
40
Figure 12. Number Densities of CFCl 3, CF2Cl2, and CO
50
SELECTED "J" VALUES (March 15 - Local Noon - 40 N)
50
H2O
20
10
10-14
10-13
10-12
10-11
10-10
Photolysis rate coefficient (sec-1)
10-9
10-8
266
O2
30
Figure 13. J-Values for O2 and H 2O
Altitude (km)
40
SELECTED "J" VALUES (March 15 - Local Noon - 40 N)
50
CFCl3
CCl4
20
10
10-10
10-9
10-8
10-7
10-6
Photolysis rate coefficient (sec-1)
10-5
10-4
267
Altitude (km)
N2O
30
Figure 14. Selected J-Values
CF2Cl2
40
SELECTED "J" VALUES (March 15 - Local Noon - 40 N)
50
H2O2
Altitude (km)
HOBr
30
HNO3
ClONO2
20
HO2NO2
10
10-7
10-6
N2O5
10-5
10-4
Photolysis rate coefficient (sec-1)
HOCl
10-3
10-2
268
Figure 15. Selected J-Values
40
E.
DATA ON CLIMATE CHANGE
Extracted from:
2002 Summary Report of the Intergovernmental
Panel on Climate Change
Indicators of the human influence on the atmosphere during the Industrial Era
Global Warming Potentials
The global mean radiative forcing of the climate system
Variations of the Earth's surface temperature
Simulated annual global mean surface temperatures
Indicators of the human influence on the atmosphere
during the Industrial Era
Figure 2: Long records of past changes in
(a) Global atmospheric concentrations of three well mixed
greenhouse gases
(a) shows changes in the atmospheric
CO2 (ppm)
360
the influence of anthropogenic emissions.
concentrations of carbon dioxide (CO2), methane
(CH4), and nitrous oxide (N2O) over the past 1000
1.5
Carbon dioxide
atmospheric composition provide the context for
years. The ice core and firn data for several sites in
Antarctica and Greenland (shown by different
340
1.0
symbols) are supplemented with the data from direct
320
atmospheric samples over the past few decades
0.5
300
280
(shown by the line for CO2 and incorporated in the
curve representing the global average of CH4). The
0.0
estimated positive radiative forcing of the climate
260
0.5
0.4
1500
0.3
1250
0.2
1000
0.1
750
N2O (ppb)
310
0.0
Radiative forcing (Wm−2)
Methane
1750
CH4 (ppb)
Atmospheric concentration
system from these gases is indicated on the right-
0.15
Nitrous oxide
hand scale. Since these gases have atmospheric
lifetimes of a decade or more, they are well mixed,
and their concentrations reflect emissions from
sources throughout the globe. All three records show
effects of the large and increasing growth in
anthropogenic emissions during the Industrial Era.
(b) illustrates the influence of industrial emissions on
atmospheric sulphate concentrations, which produce
negative radiative forcing. Shown is the time history
of the concentrations of sulphate, not in the
atmosphere but in ice cores in Greenland (shown by
0.10
lines; from which the episodic effects of volcanic
290
0.05
eruptions have been removed). Such data indicate
the local deposition of sulphate aerosols at the site,
0.0
270
reflecting sulphur dioxide (SO2) emissions at
mid-latitudes in the Northern Hemisphere. This
250
1000
record, albeit more regional than that of the
1200
1400
1600
1800
2000
globally-mixed greenhouse gases, demonstrates the
Year
large growth in anthropogenic SO2 emissions during
the Industrial Era. The pluses denote the relevant
200
Sulphur
50
100
25
0
1600
0
1800
Year
2000
SO2 emissions (Millions of
tonnes sulphur per year)
Sulphate concentration
6
(mg SO42– per tonne of ice)
(b) Sulphate aerosols deposited in Greenland ice
regional estimated SO2 emissions (right-hand scale).
[Based upon (a) Chapter 3, Figure 3.2b (CO2);
Chapter 4, Figure 4.1a and b (CH4) and Chapter 4,
Figure 4.2 (N2O) and (b) Chapter 5, Figure 5.4a]
Table 3: Direct Global Warming Potentials (GWPs) relative to carbon dioxide (for gases for which the lifetimes have been adequately characterised).
GWPs are an index for estimating relative global warming contribution due to atmospheric emission of a kg of a particular greenhouse gas compared
to emission of a kg of carbon dioxide. GWPs calculated for different time horizons show the effects of atmospheric lifetimes of the different gases.
[Based upon Table 6.7]
Gas
a
b
Lifetime
(years)
Global Warming Potential
(Time Horizon in years)
20 yrs
100 yrs
1
1
62
23
275
296
500 yrs
1
7
156
Carbon dioxide
Methanea
Nitrous oxide
CO2
CH4
N2 O
12.0b
114 b
Hydrofluorocarbons
HFC-23
HFC-32
HFC-41
CHF3
CH2F2
CH3F
260
5.0
2.6
9400
1800
330
12000
550
97
10000
170
30
HFC-125
HFC-134
HFC-134a
HFC-143
HFC-143a
HFC-152
HFC-152a
HFC-161
CHF2CF3
CHF2CHF2
CH2FCF3
CHF2CH2F
CF3CH3
CH2FCH2F
CH3CHF2
CH3CH2F
29
9.6
13.8
3.4
52
0.5
1.4
0.3
5900
3200
3300
1100
5500
140
410
40
3400
1100
1300
330
4300
43
120
12
1100
330
400
100
1600
13
37
4
HFC-227ea
HFC-236cb
HFC-236ea
HFC-236fa
HFC-245ca
HFC-245fa
HFC-365mfc
HFC-43-10mee
CF3CHFCF3
CH2FCF2CF3
CHF2CHFCF3
CF3CH2CF3
CH2FCF2CHF2
CHF2CH2CF3
CF3CH2CF2CH3
CF3CHFCHFCF2CF3
33
13.2
10
220
5.9
7.2
9.9
15
5600
3300
3600
7500
2100
3000
2600
3700
3500
1300
1200
9400
640
950
890
1500
1100
390
390
7100
200
300
280
470
Fully fluorinated species
SF6
CF4
C2F6
C3F8
C4F10
c-C4F8
C5F12
C6F14
3200
50000
10000
2600
2600
3200
4100
3200
15100
3900
8000
5900
5900
6800
6000
6100
22200
5700
11900
8600
8600
10000
8900
9000
32400
8900
18000
12400
12400
14500
13200
13200
Ethers and Halogenated Ethers
CH3OCH3
0.015
1
1
<<1
HFE-125
HFE-134
HFE-143a
CF3OCHF2
CHF2OCHF2
CH3OCF3
150
26.2
4.4
12900
10500
2500
14900
6100
750
9200
2000
230
HCFE-235da2
HFE-245fa2
HFE-254cb2
HFE-7100
HFE-7200
H-Galden 1040x
HG-10
HG-01
CF3CHClOCHF2
CF3CH2OCHF2
CHF2CF2OCH3
C4F9OCH3
C4F9OC2H5
CHF2OCF2OC2F4OCHF2
CHF2OCF2OCHF2
CHF2OCF2CF2OCHF2
2.6
4.4
0.22
5.0
0.77
6.3
12.1
6.2
1100
1900
99
1300
190
5900
7500
4700
340
570
30
390
55
1800
2700
1500
110
180
9
120
17
560
850
450
The methane GWPs include an indirect contribution from stratospheric H2O and O3 production.
The values for methane and nitrous oxide are adjustment times, which incorporate the indirect effects of emission of each gas on its own lifetime.
47
The global mean radiative forcing of the climate system
for the year 2000, relative to 1750
2
Halocarbons
N2O
Aerosols
Warming
CH4
1
CO2
Tropospheric
ozone
Black
carbon from
fossil
fuel
burning
Mineral
Dust
Aviation-induced
Solar
Contrails Cirrus
0
Cooling
Radiative forcing (Watts per square metre)
3
Stratospheric
ozone
−1
Organic
carbon Biomass
burning
Sulphate from
fossil
fuel
burning
Landuse
(albedo)
only
Aerosol
indirect
effect
−2
High Medium Medium Low
Very
Low
Very
Low
Very Very
Low Low
Very
Low
Very
Low
Very Very
Low Low
Level of Scientific Understanding
Figure 3: Many external factors force climate change.
These radiative forcings arise from changes in the atmospheric composition, alteration of surface reflectance by land use, and variation in the output
of the sun. Except for solar variation, some form of human activity is linked to each. The rectangular bars represent estimates of the contributions of
these forcings − some of which yield warming, and some cooling. Forcing due to episodic volcanic events, which lead to a negative forcing lasting
only for a few years, is not shown. The indirect effect of aerosols shown is their effect on the size and number of cloud droplets. A second indirect
effect of aerosols on clouds, namely their effect on cloud lifetime, which would also lead to a negative forcing, is not shown. Effects of aviation on
greenhouse gases are included in the individual bars. The vertical line about the rectangular bars indicates a range of estimates, guided by the
spread in the published values of the forcings and physical understanding. Some of the forcings possess a much greater degree of certainty than
others. A vertical line without a rectangular bar denotes a forcing for which no best estimate can be given owing to large uncertainties. The overall
level of scientific understanding for each forcing varies considerably, as noted. Some of the radiative forcing agents are well mixed over the globe,
such as CO2, thereby perturbing the global heat balance. Others represent perturbations with stronger regional signatures because of their spatial
distribution, such as aerosols. For this and other reasons, a simple sum of the positive and negative bars cannot be expected to yield the net effect
on the climate system. The simulations of this assessment report (for example, Figure 5) indicate that the estimated net effect of these perturbations
is to have warmed the global climate since 1750. [Based upon Chapter 6, Figure 6.6]
8
Figure 1: Variations of the Earth’s
Variations of the Earth's surface temperature for:
surface temperature over the last
140 years and the last millennium.
(a) the past 140 years
(a) The Earth’s surface temperature is
Departures in temperature (°C)
from the 1961 to 1990 average
0.8
shown year by year (red bars) and
GLOBAL
approximately decade by decade (black
line, a filtered annual curve suppressing
0.4
fluctuations below near decadal
time-scales). There are uncertainties in
the annual data (thin black whisker
bars represent the 95% confidence
0.0
range) due to data gaps, random
instrumental errors and uncertainties,
uncertainties in bias corrections in the
−0.4
ocean surface temperature data and
also in adjustments for urbanisation over
Data from thermometers.
−0.8
1860
the land. Over both the last 140 years
and 100 years, the best estimate is that
1880
1900
1920
1940
1960
1980
2000
the global average surface temperature
has increased by 0.6 ± 0.2°C.
Year
(b) Additionally, the year by year (blue
curve) and 50 year average (black
(b) the past 1,000 years
curve) variations of the average surface
temperature of the Northern Hemisphere
NORTHERN HEMISPHERE
for the past 1000 years have been
0.5
reconstructed from “proxy” data
Departures in temperature (°C)
from the 1961 to 1990 average
calibrated against thermometer data (see
list of the main proxy data in the
diagram). The 95% confidence range in
the annual data is represented by the
0.0
grey region. These uncertainties increase
in more distant times and are always
much larger than in the instrumental
record due to the use of relatively sparse
−0.5
proxy data. Nevertheless the rate and
duration of warming of the 20th century
has been much greater than in any of
the previous nine centuries. Similarly, it
−1.0
is likely7 that the 1990s have been the
Data from thermometers (red) and from tree rings,
corals, ice cores and historical records (blue).
warmest decade and 1998 the warmest
year of the millennium.
1000
1200
1400
1600
Year
1800
2000
[Based upon (a) Chapter 2, Figure 2.7c
and (b) Chapter 2, Figure 2.20]
3
(a) Natural
(b) Anthropogenic
1.0
1.0
Temperature anomalies (°C)
Temperature anomalies (°C)
Simulated annual global mean surface temperatures
model
observations
0.5
0.0
−0.5
−1.0
1850
1900
1950
0.5
0.0
−0.5
−1.0
1850
2000
model
observations
1900
Year
1950
2000
Year
Temperature anomalies (°C)
(c) All forcings
1.0
model
observations
0.5
0.0
−0.5
−1.0
1850
1900
1950
2000
Year
Figure 4: Simulating the Earth’s temperature variations, and comparing the results to measured changes, can provide insight into the
underlying causes of the major changes.
A climate model can be used to simulate the temperature changes that occur both from natural and anthropogenic causes. The simulations
represented by the band in (a) were done with only natural forcings: solar variation and volcanic activity. Those encompassed by the band in (b) were
done with anthropogenic forcings: greenhouse gases and an estimate of sulphate aerosols, and those encompassed by the band in (c) were done with
both natural and anthropogenic forcings included. From (b), it can be seen that inclusion of anthropogenic forcings provides a plausible explanation
for a substantial part of the observed temperature changes over the past century, but the best match with observations is obtained in (c) when both
natural and anthropogenic factors are included. These results show that the forcings included are sufficient to explain the observed changes, but do
not exclude the possibility that other forcings may also have contributed. The bands of model results presented here are for four runs from the same
model. Similar results to those in (b) are obtained with other models with anthropogenic forcing. [Based upon Chapter 12, Figure 12.7]
11
F.
COMPARING THE STRATOSPHERIC CHEMISTRY OF THE HALOGENS
h
10
20
25
30
40
50
T
222
215
218
223
240
268
[M]
8.50E+18
2.00E+18
9.00E+17
3.00E+17
1.00E+17
1.70E+16
[O2]
1.8E+18
4.2E+17
1.9E+17
6.3E+16
2.1E+16
3.6E+15
[O3]
1.5E+12
7.5E+12
7.0E+12
5.0E+12
7.0E+11
8.0E+10
[CH4]
2.0E+13
4.0E+12
2.0E+12
7.0E+11
7.0E+10
8.0E+09
h
10
20
25
30
40
50
T
222
215
218
223
240
268
[M]
8.50E+18
2.00E+18
9.00E+17
3.00E+17
1.00E+17
1.70E+16
[O2]
1.8E+18
4.2E+17
1.9E+17
6.3E+16
2.1E+16
3.6E+15
[O3]
1.5E+12
7.5E+12
7.0E+12
5.0E+12
7.0E+11
8.0E+10
[CH4]
2.0E+13
4.0E+12
2.0E+12
7.0E+11
7.0E+10
8.0E+09
[H2O]
1.E+15
1.0E+13
6.0E+12
3.0E+12
8.0E+11
2.0E+11
Atomic Chlorine
k'O2
k'O3
6.4E+04 1.3E+01
3.7E+03 6.5E+01
7.4E+02 6.1E+01
8.0E+01 4.5E+01
7.9E+00 6.9E+00
1.9E-01 8.8E-01
k'CH4
4.0E-01
6.5E-02
3.5E-02
1.4E-02
2.3E-03
4.7E-04
Atomic Chlorine
%O2
%O3
100%
0.0%
98%
1.7%
92%
7.6%
64%
36.2%
54%
46.4%
18%
81.9%
Atomic Fluorine
k'O2
k'O3
9.6E+04 1.2E+01
5.5E+03 5.7E+01
1.1E+03 5.3E+01
1.2E+02 3.9E+01
1.2E+01 5.9E+00
3.1E-01 7.5E-01
k'CH4
9.9E+02
1.9E+02
9.7E+01
3.5E+01
3.8E+00
4.9E-01
k'H2O
1.4E+04
1.4E+02
8.4E+01
4.2E+01
1.1E+01
2.8E+00
%O2
86%
93%
82%
51%
37%
7%
This makes use of the JPL Data Evaluation and the material in Section D of this coursepack.
%CH4
0.001%
0.002%
0.004%
0.012%
0.015%
0.044%
Atomic Fluorine
%O3
%CH4
0.0%
0.895%
1.0%
3.237%
4.0%
7.252%
16.7% 14.863%
17.9% 11.496%
17.2% 11.186%
%H2O
13%
2%
6%
18%
34%
65%
G.
HETEROGENEOUS CHEMICAL KINETICS
The rate, Rcoll, of collision of a gas phase species, A, with the surface of aerosol
particles is given by
Rcoll =
vave
× [A] × Surface area per unit volume
4
...where vave (meters/sec) is the average gas kinetic speed of species A:
vave =
8 RT
πM
R is the gas constant (8.314 Joules mol-1 K-1)
M is the molecular mass in kg/mole
[A] is the concentration of A in molecules cm-3.
Surface area per unit volume is usually expressed in µm2 cm-3 air.
So watch the units conversions!
The rate, Rrxn, of reaction of a gas phase species, A, aerosol particles = γ × Rcoll
=γ×
vave
× [A] × Surface area per unit volume
4
...where γ is the reactive uptake coefficient (see Section 5 of the JPL Data
Evaluation). The value of γ varies between 0 and 1, and represents the fraction of
collisions that result in reaction.
γ may be a complex function of composition and temperature of the particle,
and is generally time dependent.
The lifetime, τ, of A with respect to heterogeneous reaction is
γ×
vave
× Surface area per unit volume
4
H.
CONCENTRATION DATA IN THE TROPOSPHERE
On an Alabama pine
plantation in 1990. Part of
the "Rural Ozone in the
Southern Environment"
study.
Atlantic Ocean, 1997. Data
over the range from 1-11
kilometers in altitude, not
just ground level.
H. Singh, et al., J. Geophys.
Res. 2000.
Boulder, Co, 1991.
[n-butane] = 0-2 ppbv
[m+p-xylene]= 0-0.8 ppbv
[NOy] = 1-100 ppbv
P. D. Goldan, et al., J.
Geophys. Res. 1995.
I.
LIFETIMES WITH RESPECT TO OH, O3, NO3, AND PHOTOLYSIS
Reactant concentrations used for lifetime calculations
Species
[OH]
[O3]
[NO3]
Concentration
molecules cm-3
mole fraction
1.60E+06
7.00E+11
30 ppbv
4.80E+08
20 pptv
Description
global daytime average
global 24-hour average
global night-time average
Room temperature lifetimes (in hours, except where specified)
Species
n-butane
1-butene
trans-2-butene
benzene
toluene
Formaldehyde
1-butanol
Acetone
2-methyl-1,3-butadiene
(isoprene)
α-pinene
naphthalene
dibenzo-p-dioxin
1,2,3,4-tetrachloro-dibenzop-dioxin
OH
68 hrs
5.6
2.7
145
29
18
20
789
1.7
O3
41 hrs
2
31
NO3
48 hrs
1.5
8510
0.9
3.2
6.9
17.4
217.0
4.6
0.1
*
* Rate of loss = - kobs [naphthalene][NO3][NO2]
kobs ~ 10-28 cm6 molecule-2 s-1
hν
4 hrs
38 days
-
J.
DEGRADATION PATHWAYS OF ALKANES, ALKENES,
OXYGENATES, AND AROMATICS
Reference: Atkinson, R. Gas Phase Tropospheric Chemistry of Organic Compounds, J. Phys.
Chem. Reference Data Monograph 2, 1994.
+
. OH
.
.
CH2
CH
1 and 2-butyl radical
O2
O2
OO.
OO .
NO
NO
ONO2
.
O
+ NO
+
CH3CH2 .
O2
ONO2
butyl nitrate
O.
HOO .
NO2
O2
O
+
butoxy radical
+
2
O2
O
1 and 2-butylperoxy radical
H.
..
..
O
+
... O
HOO.
. CH
OH
2
O2
Section J Degradation Pathways
page 1 of 4
+
. OH
.
Alkenes : OH mostly adds to an
sp2 hybridized carbon in preference
to H-atom abstraction. The
subsequent chemistry is similar to
that of the radicals derived from
abstraction, except for the presence
of the hydroxyl group.
The preferred site of abstraction
is the one leading to the more
stable radicals: tertiary > secondary
> primary.
OH
O2
OO.
OH
NO
.
O
ONO2
+
NO2
OH
OH
O
+
.
OH
O2
O
Section J Degradation Pathways
+
HOO
page 2 of 4
Alcohols:
OH mainly abstracts from the substituted site:, and the subsequent reaction
with O2 does not yield a peroxy radical.
OH
+ . OH
CHOH
.
CH
.
O
O2
OH
+
HOO
OH
O2
OO .
OO .
.
CH
OH
OH
O2
Aldehydes
The preferred site of abstraction is the aldehylic hydrogen. The reaction of
the subsequent peroxy radical with NO2 yields relative stable products, unlike the
situation with other peroxy radicals
.
CH3CH=O
. CH3 +
+
CO2
+ NO2
CH3C(=O)
OH
NO
Compare
CH3C(=O)OO.
O2
CH3C(=O)OO.
(peroxyacetylnitrate = PAN)
CH3C(=O)OONO2
NO2
lifetime ~1 hour
CH CH OO.
3
Section J Degradation Pathways
2
NO2
CH3CH2OONO2
lifetime ~1 second
page 3 of 4
Aromatics
Reaction with OH dominated by OH addition, but subsequent mechanism
(and many of the final products) of this path are not known.. The products of the
H-atom abstraction path are established.
H
OH
.
OH
O2
H
?
(and para and meta isomers)
I have not drawn all the
resonance structures
OH
. CH
CH2OO .
2
O2
Section J Degradation Pathways
CH2O
NO
.
CH=O
O2
+
HOO
K.
TROPOSPHERIC PHOTOCHEMISTRY
HONO + hν → OH + NO (Major OH source in the a.m.)
HONO2 + hν → OH + NO2 (very slow in comparison to deposition)
N2O5 + hν → NO2 + NO3
(slow with respect to thermal decomposition)
RONO2 + hν → RO + NO2
(τ = days to weeks, somewhat slower than RONO2 + OH)
HOOH + hν → 2 OH
(τ ~ ________ )
NO3 + hν → NO2 + O or NO + O2 (absorbs strongly in the red, τ = seconds)
H2C=O + hν → H + HC=O (45%) (τ = hours)
→ H2 + CO
(55%)
RCH=O + hν → R + HC=O (τ = days)
RC(=O)OONO2 + hν →
RC(=O)OO + NO2 (slower than thermal dissociation)
RC(=O)O + NO3