Table 1a:
Henry's Law Constants of halogen containing compounds
Species
1
2
3
4
5
6
7
8
9
Table 1a:
KH 298,
M atm-1
48
926
0.72
48
926
0.94
1.2
0.2
1.0
BrO
ClO
HBr
HOBr
HOCl
BrCl
Br
Cl
ClO2
∆H / R,
K
6077
3300
Reference
KH 1=KH 4
KH 2=KH 5
Sander and Crutzen, 1996
Sander and Crutzen, 1996
Huthwelker, 1995
Sander and Crutzen, 1996
Mozurkewich, 1986
Mozurkewich, 1986
Lide and Frederikse, 1995
Photolysis processes of halogen containing compounds in the gas phase
1
2
3
4
5
6
7
8
9
Species
α
BrO
ClO
HBr
HOBr
HOCl
BrCl
Br
Cl
ClO2
0.06
0.064
0.01
0.06
0.064
0.01
0.05
0.05
0.05
Literatur
Sander and Crutzen, 1996
αH2 = αH3
abgeschätzt
Vogt et al., 1996
Vogt et al., 1996
Sander and Crutzen, 1996
estimated equal as OH
estimated equal as OH
estimated equal as OH
Dg
[10 m2 s-1]
1.31
1.45
1.41
1.27
1.41
1.12
1.46
1.71
1.29
Literatur
5
a)
Fuller, 1986 a)
Fuller, 1986 a)
Fuller, 1986 a)
Fuller, 1986 a)
Fuller, 1986 a)
Fuller, 1986 a)
Fuller, 1986 a)
Fuller, 1986 a)
Fuller, 1986 a)
method by Fuller,1986 (T=288,15 K, p=1013,15 hPa)
Table 2a:
Photolysis processes of halogen containing compounds in the gas phase
Nr.
1
2
3
4
5
6
7
Table 2b:
Reaction
Br2 + hν→ Br + Br
HOBr + hν → Br + OH
Cl2 + hν → Cl + Cl
HOCl + hν → Cl + OH
BrCl + hν → Br + Cl
BrNO2 + hν → Br + NO2
ClNO2 + hν → Cl + NO2
jmax [s-1]
3.93 ⋅ 10-2
9.37 ⋅ 10-4
2.69 ⋅ 10-3
2.63 ⋅ 10-4
1.24 ⋅ 10-2
3.99 ⋅ 10-4
3.99 ⋅ 10-4
Reference
Röth, 1992
"
"
"
"
"
"
Reactions of halogen containing compounds in the gas phase
Reaktion
HG1
HG2
HG3
HG4
HG5
HG6
HG7
HG8
HG9
HG10
HG11
HG12
HG13
HG14
Br + O3 → BrO + O2
BrO + HO2 → HOBr + O2
BrO + O3 → Br + 2 O2
Cl + O3 → ClO + O2
ClO + HO2 → HOCl + O2
ClO + O3 → ClO2 + O2
[ M]
ClO2 → Cl + O2
CH4 + Cl → HCl + CH3
Br + HO2→ HBr + O2
Br + C2H4 (+ 2 O2)→ HBr + CH3O2 + CO2
Br + OLT →HBr + CH3O2
Br + HCHO → HBr + CO + HO2
HCl + OH → Cl
HBr + OH → Br
OLT: terminale alkenes
k298,
M-n s-1
1.16·10-12
1.43·10-11
5.0·10-17
1.21·10-11
5.5·10-12
1.4·10-17
6.2·10-13
1.1·10-13
2.0·10-12
2.5·10-14
2.5·10-14
1.16·10-11
8.0·10-13
1.0·10-11
Ea / R,
K
800
-520
260
-700
1820
1400
600
800
350
Reference
DeMore et al., 1997
Elrod et al., 1996
Atkinson et al., 1997
DeMore et al., 1997
DeMore et al., 1997
DeMore et al., 1997
Atkinson et al., 1997
DeMore et al., 1997
DeMore et al., 1997
Sander and Crutzen,1996
"
DeMore et al., 1997
DeMore et al., 1997
DeMore et al., 1997
Table 3:
Reactions of halogen containing compounds in aqueous solution
Reaction
R1
R2
R3
R4
R5
R6
R7
R8
R9
R10
R11
R12
R13
R14
R15
R16
R17
R19
R20
HO2 + HOCl → H2O + O2 + Cl
HO2 + Cl2 → Cl2- + O2 + H+
O2- + HOCl → OH- + O2 + Cl
O2- + Cl2 → Cl2- + O2
HOCl + OH → H2O + ClO
HOCl + HSO3- → HSO4- + H+ + ClHOCl +Br- → BrCl + OHHO2 + HOBr → H2O + O2 + Br
HO2 + Br2 → Br2- + O2 + H+
O2- + HOBr → OH- + O2 + Br
O2- + Br2 → Br2- + O2
HOBr + OH → H2O + BrO
HOBr + HSO3- → HSO4- + H+ + BrBrO + BrO → BrO2- + OBr- + 2 H+
BrO2- + BrO → OBr- + BrO2
Br2- + BrO2- → 2 Br- + BrO2
BrO2-+OH → BrO2+OHH+ + Cl- + HOCl → Cl2 + H2O
H+ + Br- + HOBr → Br2 + H2O
k298.
M-n s-1
7.5·106
1.0·109
7.5·106
1.0·109
2.0·109
7.6·108
1.6·103
1.0·109
1.1·108
3.5·109
5.6·109
2.0·109
5.0·109
2.8·109
4.0·108
8·107
1.8·109
2.1·104
1.6·1010
Reference
kR2 = kR1
Bjergbakke et al., 1981
Long and Bielski, 1980
kR4 = kR2
kR5 = kR12
kHSO3-=kSO32- (Fogelman et al., 1989)
Kumar, 1987
estimated (Sutton and Downes, 1972)
Sutton and Downes, 1972
Schwarz and Bielski, 1986
Sutton and Downes, 1972
Kläning and Wolff, 1985
kHSO3-=kSO32- (Fogelman et al., 1989)
Klaning and Wolff, 1985
Amichai and Treinin, 1970
Buxton and Dainton, 1968
Buxton and Dainton, 1968
Wang and Margerum, 1994
Eigen and Kustin, 1962
Table 4:
Aqueous Phase equilibria
Equilibrium
E1
HOBr
H+ + BrO-
K,
M
2.0·10-9
E2
HOCl
H+ + ClO-
3.0·10-8
Atkins, 1996
E3
BrCl (+H2O)
1.8·10-5
Wang et al,, 1994
E4
Br2Cl-
BrCl + Br-
5.6·10-5
Wang et al,, 1994
E5
BrCl2-
BrCl + Cl-
1.6·10-1
Wang et al,, 1994
E6
Br2Cl-
Br2 + Cl-
7.7·10-1
Wang et al,, 1994
E7
BrCl2-
Cl2 + Br-
7.7·10-1
estimated equal as E6
E8
HBr
1.0·109
Atkins, 1990
E9
HBrO2
1.3·10-5
Field, 1986
E10
2 HOBr
6.7·10-12
Field, 1986
E11
HOBr+HBrO2
1.7
Field, 1986
E12
2 HBrO2
3.0·1011
Field, 1986
E13
Br2O4+H2O
52.6
Field, 1986
E14
Br2O4
5.3·10-5
Field, 1986
HOBr + Cl- + H+
H++BrH+ + BrO2H+ + Br- + HBrO2
2 H++Br- +BrO3-
H+ + BrO3- + HOBr
H++BrO3-+HBrO2
2 BrO2
Reference
Atkins, 1990
k(hin) 298/s-1
k(rück) 298/
M-n s-1
1.0·102
5.0·1010
1.5·103
5.0·1010
1.0·105
5.6·109
4.3·105
7.7·109
1.3·109
7.7·109
5.9·109
7.7·109
5.9·109
7.7·109
5.0·1011
5.0·102
6.3·105
5.0·1010
2.0·10-5
3.0·106
3.2
2.0
3.0·103
1.0·10-8
2.2·103
42
7.4·104
1.4·109
Reference
calculated based on K
estimated
calculated based on K
estimated
Wang et al,, 1994
calculated based on K
calculated based on K
estimated equal as E4
calculated based on K
estimated equal as E4
calculated based on K
estimated equal as E4
calculated based on K
Wang et al,, 1994
estimated (limitation by diffusion)
calculated based on K
calculated based on K
abgeschätzt
Field and Försterling, 1986
Field and Försterling, 1986
Field and Försterling, 1986
Field and Försterling, 1986
Field and Försterling, 1986
Field and Försterling, 1986
Field and Försterling, 1986
Field and Försterling, 1986
Field and Försterling, 1986
Field and Försterling, 1986
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