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Radiation and Climate$

Ilias Vardavas and Frederic Taylor

Print publication date: 2007

Print ISBN-13: 9780199227471

Published to Oxford Scholarship Online: January 2008

DOI: 10.1093/acprof:oso/9780199227471.001.0001

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(p.468) APPENDIX B TABLES OF REACTIONS

(p.468) APPENDIX B TABLES OF REACTIONS

Source:
Radiation and Climate
Publisher:
Oxford University Press

Table B.1 Photoionization rates and products of atmospheric species, based on the quiet-Sun irradiance in the ultraviolet and visible spectral regions at the top of the atmosphere, for global mean conditions.

Photoionization

j (s−1)

O2

N 2 + + e 9.4 × 10−8

O2 → O + O+ + e

5.5 × 10−7

N2

N 2 + + e 2.0 × 10−7

N2 → N(2D) + N+ + e

2.7 × 10−7

NO → NO+ + e

1.7 × 10−6

O → O+ + e

3.2 × 10−7

N → N+ + e

2.3 × 10−7

N(2D) → N+ + e

2.3 × 10−7

He →

He+ + e 1.0 × 10−7

(p.469)

Table B.2 Total photodissociation and photoionization rates of atmospheric species, based on the quiet-Sun irradiance in the ultraviolet and visible spectral regions at the top of the atmosphere, for global mean conditions.

Molecule

Region (nm)

j (s−1)

photodissociation

O2

100−242

3.7×10−6

O3

100−850

8.6×10−3

N2

80−103

5.9×10−7

NO

181 & 191

4.1×10−6

NO2

200−425

1.7×10−2

NO3

500−670

1.8×10−1

N2O

175−240

1.1×10−6

N2O5

200−380

6.9×10−4

CO2

105−200

7.7×10−7

HO2

190−250

6.1×10−4

H2O

69−190

1.0×10−5

H2O2

190−350

1.2×10−4

HONO

300−400

2.7×10−3

HNO3

190−350

1.4×10−4

HNO4

190−325

4.4×10−4

NH3

100−230

1.9× 10−4

CH4

100−160

6.4×10−6

CH3OOH

220−360

5.6×10−5

CH2O

300−360

3.0×10−4

Cl2

260−470

5.4×10−3

ClO

220−320

7.4×10−3

ClO2

220−280

1.2×10−2

ClONO2

196−432

7.3×10−4

ClNO2

190−370

1.2×10−2

HCl

140−220

4.9×10−6

HOCl

200−420

1.1×10−3

CH3Cl

186−216

5.5×10−7

CCl4

174−275

4.3×10−5

photoionization

O2

8−102.8

6.4×10−7

N2

8−79.6

4.7×10−7

NO

121.6

7.2×10−7

NO

8−102.6

1.0×10−6

O

8−91.0

3.2×10−7

N

8−85.2

2.3×10−7

He

8−50.4

1.0×10−7

(p.470)

Table B.3 Photodissociation rates and products of atmospheric species, based on the quiet-Sun irradiance in the ultraviolet and visible spectral regions at the top of the atmosphere, for global mean conditions.

Photolysis

j (s−1)

O2 → 2 O

3.7 × 10−6

O3 → O + O2

1.5 × 10−3

O3 → O(1D) + O2

7.1 × 10−3

NO → N + O

4.1 × 10−6

NO2 → NO + O

1.7 × 10−2

NO3 → NO + O2

2.0 × 10−2

NO3 → NO2 + O

1.6 × 10−1

N2O → N2 + O(1D)

1.1 × 10−6

N2 → N(2D) + N

5.9 × 10−7

N2O5 → NO2 + NO3

4.8 × 10−4

N2O5 → 2 NO2 + O

2.1 × 10−4

CO2 → CO + O

2.7 × 10−8

CO2 → CO + O(1D)

7.5 × 10−7

HO2 → OH + O

6.1 × 10−4

H2O → O(1D) + H2

5.1 × 10−7

H2O2 → H + O

5.1 × 10−7

H2O → H + OH

3.6 × 10−6

H2O2 → 2 OH

1.2 × 10−4

HONO → NO + OH

2.7 × 10−3

HNO3 → NO2 + OH

1.4 × 10−4

HNO4 → NO2 + HO2

4.4 × 10−4

NH3 → NH2 + H

1.9 × 10−4

CH4 → CH3 + H

3.8 × 10−6

CH4 → CH2 + H2

1.3 × 10−6

CH4 → CH2 + 2 H

1.3 × 10−6

CH3OOH → CH3 + OH

5.6 × 10−5

CH2O → HCO + H

1.5 × 10−4

CH2O → CO + H2

1.5 × 10−4

Cl2 → 2 Cl

5.4 × 10−3

ClO → Cl + O

6.5 × 10−3

ClO → Cl + O(1D)

9.1 × 10−4

ClO2 → ClO + O

7.6 × 10−3

ClO2 → ClO + O(1D)

4.1 × 10−3

ClONO2 → ClO + NO2

7.3 × 10−4

ClNO2 → Cl + NO2

1.2 × 10−2

HCl → H + Cl

4.9 × 10−6

HOCl → Cl + OH

1.1 × 10−3

CH3Cl → CH3 + Cl

5.5 × 10−7

CCl4 → CCl3 + Cl

4.3 × 10−5

(p.471)

Table B.4 Oxygen and nitrogen reactions. The bimolecular forward rate constant, kf, is given, or the termolecular low pressure rate constant, k0, the high-pressure rate constant, k8 and the parameter f. (Sources: JPL 2006, IUPAC 2006, NIST 2006)

Chemical reaction

kf or k 0, k , f

O + O + M → O2 + M

5.21×10−35exp(900/T)

O + O2 + M → O3 + M

6.0×10−34(300/T)2.4

O(1D) + O2 → O + O2

3.3×10−11exp(55/T)

O(1D) + N2 →O + N2

1.8×10−11exp(110/T)

O3 + → O2 O2

8.0×10−12exp(−2060/T)

O3 + O(1D) →2 O2

1.2×10−10

O3 + O(1D) →O2 + 2 O

1.2×10−10

O3 + N → NO + O2

2.0×10−16

O3 + NO → NO2 + O2

3.0×10−12exp(−1500/T)

O3 + NO2 → NO3 + O2

1.2×10−13exp(−2450/T)

O3 + OH → HO2 + O2

1.7×10−12exp(−940/T)

O3 + HO2 → OH + 2 O2

1.0×10−14exp(−490/T)

O3 + H → OH + O2

1.4×10−10exp(−470/T)

N + O2 → NO + O

1.5×10−11exp(−3600/T)

N + O + M → NO + M

5.46×10−33exp(156/T)

NO + O + M → NO2 + M

1.0×10−31(300/T)1.6

3.0×10−11(300/T)−0.3, 0.85

NO + N → N2 + O

2.1×10−11exp(100/T)

NO2 + O → NO + O2

5.6×10−12exp(180/T)

NO2 + O + M → NO3 + M

1.3×10−31(300/T)1.5

2.3×10−11(300/T)−0.24, 0.60

NO2 + N → N2O + O

5.8×10−12exp(221/T)

NO2 + H → NO + OH

4.0×10−10exp(−340/T)

N2O + H → N2 + OH

9.22×10−14exp(−2988/T)

NO3 + O →O2 + NO2

1.0×10−11

NO3 + OH → HO2 + NO2

2.2×10−11

NO3 + NO2 + M → N2O5 + M

3.6×10−30(300/T)4.1

1.9×10−12(300/T)−0.2, 0.35

NO3 + NO →2 NO2

1.5×10−11exp(170/T)

NO3 + NO3 →2 NO2 + O2

8.5×10−13exp(−2450/T)

N2 + O(1D) + M → N2O + M

3.5×10−37(300/T)0.6

N2O + O(1D) → N2 + O2

4.7×10−11exp(20/T)

N2O + O(1D) → 2 NO

6.7×10−11exp(20/T)

N2O5 + M → NO2 + NO3 + M

1.33×10−3(T /298)3.5exp(−11000/T)

9.7×1014(T /298)−0.1exp(−11080/T), 0.35

N2O5 + H2O →2 HNO3

2.5×10−22

N(2D) + O2 → NO + O

9.7×10−12exp(−186/T)

N(2D) + O → N + O

1.0×10−12

N(2D) + CO2 → NO + CO

3.6×10−13

N(2D) + CO → N + CO

6.0×10−12

N(2D) + H2 → NH + H

4.2×10−11exp(−881/T)

N(2D) + N2 → N + N2

1.7×10−14

N(2D) + NO → N2 + O

6.0×10−11

N(2D) + N2ON → 2 + NO

1.5×10−11exp(−567/T)

N(2D) → N

1.07×10−5

(p.472)

Table B.5 Ion-neutral reactions. The bimolecular forward rate constant, kf, is given. (Source: UDfA 2005)

Ion-neutral reaction

kf

N(2D)+ O 2 + → N+ + O2

4.0 × 10−10

N(2D) + e → N + e

6.0 × 10−10 (300/T e)−0.5

NO+ + e → N(2D)+ o

3.57 × 10−7(300/T e)0.85

NO+ + e → N + O +

0.63 × 10−7 (300/T e)0.85

N 2 + + O → NO+ + N(2D)

1.4 × 10−10(300/T)−0.44

N 2 + + O → O+ + N2

1.3 × 10−10

N 2 + + O2 → O2+ + N2

5.0 × 10−11

N 2 + + N → N+ + N2

1.0 × 10−11

N 2 + + NO → NO+ + N2

1.0 × 10−10

N 2 + + e → N + N(2D)

1.17 × 10−7 (300/T e)0.3

N 2 + + CO2 CO 2 + + N2

7.7 × 10−11

N 2 + + CO → CO+ +N2

7.7 × 10−11

N+ + O2 → O + NO+ 2.63 × 10−10

N+ + O2 O 2 + + NO+

3.11 × 10−10

N+ + NO → NO+ + N

4.51 × 10−10

N+ NO → N 2 + + N

7.9 × 10−11

N+ + N → N 2 +

3.71 × 10−18(300/T)−0.24

N+ + CO2 CO 2 + + N

7.5 × 10−10

N+ + CO2 → CO+ NO

2.5 × 10−10

N++Co → CO+ + N

8.25 × 10−10

N+ + CO → NO+ + C

1.45 × 10−10

N+ + e → N

4.0 × 10−12(300/T e)0.58

O 2 + + No → NO+ + O2

4.6 × 10−10

O 2 + N → NO+ + O

1.8 × 10−10

O 2 + + C → + O2

5.2 × 10−11

O 2 + + C → CO+ + O

5.2 × 10−11

O 2 + + e → O + o

1.9 × 10−7(300T e)0.7

O+ + O2 O 2 + + O

1.9 × 10−11

O+ + N2 → NO+ + N

1.2 × 10−12

O+ + NO → NO+ + O

1.3 × 10−12

O+ + CO2 O 2 + + CO

9.4 × 10−10

O+ + CO → CO+ + o

4.9 10−12(300T)−0.5

O+ + C → CO+

4.69 × 10−11(300/T)3.08

O+ + e → O

3.24 × 10−12(300/T e)0.66

CO 2 + + O → O 2 + + CO

1.64 × 10−10

CO 2 + + O → O+ + CO2

9.62 × 10−11

CO 2 + + O2 O 2 + + CO2

5.3 × 10−11

CO 2 + + NO → CO2 + NO+

1.2 × 10−10

CO 2 + + e → CO + O

3.80 × 10−7(300/T e)0.5

CO+ + N → NO+ + C

2.0 × 10−11

CO+ + NO → NO+ + CO

3.3 × 10−10

CO+ + O2 CO 2 + + CO

1.2 × 10−10

CO+ + O → + CO

1.4 × 10−10

CO+ + CO2 CO 2 + + CO

1.0 × 10−9

CO+ + C → CO+ + CO

1.1 × 10−10

CO+ + e → C + O

2.0 × 10−7(300/T e)0.48

C+ + CO2 → CO+ + CO

1.1 × 10−9

C+ + e → C

4.67 × 10−12(300/T e)0.6

He+ + CO → C+ + O + He

1.6 × 10−9

He+ + CO2 → + O + He

8.7 × 10−10

He+ + CO2 → O+ + CO + He

1.0 × 10−10

He+ + CO2 CO 2 + + He

1.21 × 10−10

He+ + Co2 O 2 + + C + He

1.1 × 10−11

He+ + CO2 → C+ + O2 + He

4.0 × 10−11

He+ + C → C+ + He

6.3 × 10−15

He+ + e → He

2.36 × 10−12(300/T e)0.64

(p.473)

Table B.6 Hydrogen reactions. The bimolecular forward rate constant, kf, is given, or the termolecular low pressure rate constant, k0, the high-pressure rate constant, k and the parameterf. (Sources: JPL 2006, IUPAC 2006, NIST 2006)

Chemical reactions

kf or k0,k,f

H + O2 + M→HO2 + M

5.4×10−32(300/T)1.8

9.5×10−11(300/T)−0.44, 0.5

H + H + M→H2 + M

8.85×10−33(T/298)−0.6

H + OH + M→H2O + M

6.87×10−31(T/298)−2

H + HO2→2 OH

7.2×10−11

H + HO2 H2 + O2

6.9×10−12

H + HO2 H2O + O

1.6×10−12

OH + O→O2 + H

2.2×10−11exp(120/T)

OH + NO + M→HONO + M

7.4×10−31(300/T)2.4

3.3×10−11(300/T)0.3, 0.81

OH + NO2 + MHNO3 + M

3.0×10−30(300/T)3.0,

4.1×10−11, 0.4

2 OH→H2O + O

6.2×10−14(T/298)2.6exp(946/T)

2 OH + M→H2O2 + M

6.9×10−31(300/T)

2.6×10−11

HO2 + O→OH + O2

3.0×10−11exp(200/T)

HO2 + OH→H2O + O2

4.8×10−11exp(250/T)

HO2 + NO→NO2 + OH

3.5×10−12exp(250/T)

HO2 + NO2 + M→HNO4 + M

2.0×10−31(300/T)3.4

2.9×10−12(300/T)1.1, 0.6

HO2 + CO→CO2 + OH

5.96×10−11(T /298)0.5exp(−11498/T)

2 HO2→H2O2 + O2

3.5×10−13exp(430/T)

2 HO2 + M→H2O2 + O2 + M

1.9×10−33exp(980/T)

H2 + O→OH + H

1.54×10−9exp(−9742/T)

H2 + OH→H2O + H

5.5×10−12exp(−2000/T)

H2 + O(1D)→OH + H

1.1×10−10

H2 + HO2™H2O2 + H

5.0×10−11exp(−13098/T)

H2O + O(1D)2 OH

1.63×10−10exp(60/T)

H2O2 + O→OH + HO2

1.4×10−12exp(−2000/T)

H2O2 + OH→H2O + HO2

2.9×10−12exp(−160/T)

HONO + OH→H2O + NO2

1.8×10−11exp(−390/T)

HNO3 + OH→H2O + NO3

1.5×10−13

HNO4 + M→HO2 + NO2 + M

4.1×10−5exp(−10600/T)

4.8×1015exp(−111170/T), 0.6

HNO4 + O→OH + NO2 + O2

7.8×10−11exp(−3400/T)

HNO4 + OH→H2O + NO2 + O2

1.9×10−12exp(272/T)

NH3 + OH→NH2 + H2O

1.7×10−12exp(−710/T)

NH3 + O(1D)→NH2 + OH

2.5×10−10

NH2 + H + M→NH3 + M

3.0×10−30

NH2 + O→HNO + H

9.15×10−11(T/298)−0.49exp(−166/T)

NH2 + NO→H2O + N2

4.0×l0−12exp(450/T)

NH2 + O2→H2O + NO

6.0×10−21

NH2 + NO2→H2O + N2O

2.1×10−12exp(650/T)

NH2 + H→H2 + NH

1.05×10−10exp(−4448/T)

NH + O→N + OH

1.0×10−11

NH + NO→N2 + O + H

4.9×10−11

NH + NO2 N2O + OH

3.5×10−13exp(1140/T)

HNO + H→NO + H2

4.48×10−11(T/298)0.72exp(−327/T)

HNO + OH→NO + H2O

5.0×10−11

HNO + O→OH + NO

3.8×10−11

(p.474)

Table B.7 Chlorine reactions. The bimolecular forward rate constant, kf, is given, or the termolecular low pressure rate constant, k0, the high-pressure rate constant, k8 and the parameter f. (Sources: JPL 2006, IUPAC 2006, NIST 2006)

Chemical reactions

kf or k0, k, f

Cl + O3 → ClO + O2

2.3 × 10−11exp(−200/T)

Cl + O2 + M → ClO2 + M

2.2 × 10−33(300/T)3.1

1.8 × 10−10, 0.6

Cl + NO2 + M → ClNO2 + M

1.8 × 10−31(300/T)2.0

1.0 × 10−10(300/T), 0.6

Cl + CH4 →HCl + CH3

7.3 × 10−12exp(−1280/T)

Cl + HO2 → OH + ClO

4.1 × 10−11exp(−450/T)

Cl + HO2 → HCl + O2

1.8 × 10−11exp(171/T)

Cl + H2O2 → HCl + HO2

1.1 × 10−11exp(−980/T)

Cl + H2 → HCl + H

3.05 × 10−11exp(−2270/T)

Cl + HNO4 → HCl + NO2 + O2

1.0 × 10−13

Cl + NO3 → ClO + NO2

2.4 × 10−11

Cl + CH2 → OHCl + HCO

8.1 × 10−11exp(−30/T)

Cl + HOCl → Cl2 + OH

2.5 × 10−12exp(−130/T)

Cl + CH3Cl → CH2Cl + HCl

2.17 × 10−11exp(−1130/T)

Cl + ClONO2 → Cl2 + NO3

6.5 × 10−12exp(136/T)

Cl + CH3OH → CH3O + HCl

5.5 × 10−11

Cl2 + OH → Cl + HOCl

1.4 × 10−12exp(−900/T)

Cl2 + O(1D) → ClO + Cl

1.99 × 10−10

ClO + NO2 + M → ClONO2 + M

1.8 × 10−31(300/T)3.4

1.5 × 10−11(300/T)1.9, 0.6

ClO + O → Cl + O2

2.8 × 10−11exp(85/T)

ClO + O3 → ClO2 + O2

1.0 × 10−12exp(−5000/T)

ClO + NO → NO2 + Cl

6.4 × 10−12exp(290/T)

ClO + NO3 → NO2 + ClO2

4.7 × 10−13

ClO + HO2 → HOCl + O2

2.7 × 10−12exp(220/T)

ClO + OH → HO2 + Cl

7.4 × 10−12exp(270/T)

ClO + OH → HCl + O2

6.0 × 10−13exp(230/T)

ClO + H2 → HOCl + H

1.0 × 100−19

ClO + ClO → ClO2 + Cl

3.0 × 10−11exp(−2450/T)

ClO + ClO → O2 + Cl2

1.0 × 10−12exp(−1590/T)

ClO2 + M → Cl + O2

2.8 × 10−10exp(−1820/T)

ClO2 + O → ClO + O2

2.4 × 10−12exp(−960/T)

ClO2 + NO → ClO + NO2

2.5 × 10−12exp(−600/T)

ClO2 + OH → HOCl + O2

4.5 × 10−13exp(800/T)

ClO2 + Cl → 2ClO

1.2 × 10−11

ClO2 + Cl → Cl2 + O2

2.3 × 10−10

ClONO2 + O → ClO + NO3

2.9 × 10−12exp(−800/T)

ClONO2 + OH → HOCl + NO3

1.2 × 10−12exp(−330/T)

ClNO2 + OH → HOCl + NO2

2.4 × 10−12exp(−1250/T)

HCl + O(1D) → Cl + OH

1.5 × 10−10

HCl + O → OH + Cl

1.0 × 10−11exp(−3300/T

HCl + OH → H2O + Cl

2.6 × 10−12exp(−350/T)

HOCl + O → ClO + OH

1.7 × 10−13

HOCl + OH → ClO + H2O

3.0 × 10−12exp(−500/T

CH3Cl + OH → H2O + CH2Cl

2.4 × 10−12exp(−1250/T)

CH2Cl + OC → H2O + Cl

1.49 × 10−10exp(−176/T)

CCl4 + O(1D)→ 4 Cl + CO

3.3 × 10−10

(p.475)

Table B.8 Carbon reactions. The bimolecular forward rate constant, kf, is given, or the termolecular low pressure rate constant, k0, the high-pressure rate constant, k8 and the parameter f. P0 = 1 bar. (Sources: JPL 2006, IUPAC 2006, NIST 2006)

Chemical reactions

kf or 0, k , f

HCO + O2 → CO + HO2

5.2 × 10−12

CO + OH → H + CO2

1.3 × 10−13(1 + 0.6 P/P 0)(300/ T)

CO + O + M → CO2 + M

1.7 × 10−33exp(–1510/ T)

CO + H + M → HCO + M

5.29 × 10−34 exp(–372/ T)

CO2 + O(1D) → CO2 + O 7.4 × 10−11

CO2 + O(1D) → CO + O2

2.01 × 10−10

CO2 + O → CO + O2

2.81 × 10−11exp(–26499/T)

CO2 + H → CO + OH

2.51 × 10−10exp(−13300/T)

CO2 + N → CO + NO

3.2 × 1−13exp(–1711/ T)

CO2 + C →2 CO

1.0 × 10−15

C + O2 → CO + O

1.0 × 10−9

CO2 + CH2 → CH2O + CO

1.4 × 10−14

CH4 + O(1D) →CH3 + OH

1.125 × 10−10

CH4 + O(1D) → CH3O + H

3.0 × 10−11

CH4 + O(1D) → CH2O + H2

7.5 × 10−12

CH4 + OCH3 + OH

5.63 × 10−10exp(−6230/T)

CH4 + OHCH3 + H2O

2.45 × 10−12exp(−1775/T)

CH3 + OCH2O + H

1.1 × 10−10

CH3 + O3 CH3O + O2

5.4 × 10−12exp(−220/T)

CH2 + H2 CH3 + H

6.9 × 10−15

CH3 + O2 + MCH3O2 + M

1.0 × 10−30(300/T)3.3

1.8 × 10−12(300/T)−1.1, 0.27

CH3O + O2 CH2O + HO2

3.9 × 10−14exp(−900/T)

CH3O + NOCH2O + HNO

8.0 × 10−12

CH3O + NO2 CH2O + HONO

1.1 × 10−11exp(−1200/T)

CH3O2 + OCH3O + O2

4.3 × 10−11

CH3O2 + NONO2 + CH3O

2.8 × 10−12exp(287/T)

CH3O2 + HO2 CH3OOH + O2

3.8 × 10−13exp(780/T)

CH3O2 + CH3O2 2 CH3O + O2

5.94 × 10−14exp(390/T)

CH3O2 + CH3O2 CH2O + CH3OH + O2

3.56 × 10−14exp(390/T)

CH3OH + OHCH3O + H2O

2.9 × 10−12exp(−345/T)

CH3OOH + OHCH3O2 + H2O

3.8 × 10−12exp(200/T)

CH2O + OHCO + OH

3.4 × 10−11exp(−1600/T)

CH2O + OHH2O + HCO

5.5 × 10−12exp(125/T)

(p.476)