Reference M atm -1 H / R,

Transcription

1 Table 1a: Henry's Law Constants of halogen containing compounds Species K H 298, M atm 1 H / R, K 1 BrO 48 K H 1 =K H 4 2 ClO 926 K H 2 =K H 5 3 HBr Sander and Crutzen, HOBr 48 Sander and Crutzen, HOCl 926 Huthwelker, BrCl 0.94 Sander and Crutzen, Br 1.2 Mozurkewich, Cl 0.2 Mozurkewich, ClO Lide and Frederikse, 1995 Table 1a: Photolysis processes of halogen containing compounds in the gas phase Species α Literatur D g Literatur [10 5 m 2 s 1 ] 1 BrO 0.06 Sander and Crutzen, Fuller, 1986 a) 2 ClO α H2 = α H Fuller, 1986 a) 3 HBr 0.01 abgeschätzt 1.41 Fuller, 1986 a) 4 HOBr 0.06 Vogt et al., Fuller, 1986 a) 5 HOCl Vogt et al., Fuller, 1986 a) 6 BrCl 0.01 Sander and Crutzen, Fuller, 1986 a) 7 Br 0.05 estimated equal as OH 1.46 Fuller, 1986 a) 8 Cl 0.05 estimated equal as OH 1.71 Fuller, 1986 a) 9 ClO estimated equal as OH 1.29 Fuller, 1986 a) a) method by Fuller,1986 (T=288,15 K, p=1013,15 hpa)

2 Table 2a: Photolysis processes of halogen containing compounds in the gas phase Nr. Reaction j max [s 1 ] 1 Br 2 + hν Br + Br Röth, HOBr + hν Br + OH " 3 Cl 2 + hν Cl + Cl " 4 HOCl + hν Cl + OH " 5 BrCl + hν Br + Cl " 6 BrNO 2 + hν Br + NO " 7 ClNO 2 + hν Cl + NO " Table 2b: Reactions of halogen containing compounds in the gas phase E / R, Reaktion k 298, M n s 1 a K HG1 Br + O 3 BrO + O DeMore et al., 1997 HG2 BrO + HO 2 HOBr + O Elrod et al., 1996 HG3 BrO + O 3 Br + 2 O Atkinson et al., 1997 HG4 Cl + O 3 ClO + O DeMore et al., 1997 HG5 ClO + HO 2 HOCl + O DeMore et al., 1997 HG6 ClO + O 3 ClO2 + O DeMore et al., 1997 HG7 [ M] ClO 2 Cl + O Atkinson et al., 1997 HG8 CH 4 + Cl HCl + CH DeMore et al., 1997 HG9 Br + HO 2 HBr + O DeMore et al., 1997 HG10 Br + C 2 H 4 (+ 2 O 2 ) HBr + CH 3 O 2 + CO Sander and Crutzen,1996 HG11 Br + OLT HBr + CH 3 O " HG12 Br + HCHO HBr + CO + HO DeMore et al., 1997 HG13 HCl + OH Cl DeMore et al., 1997 HG14 HBr + OH Br DeMore et al., 1997 OLT: terminale alkenes

3 Table 3: Reactions of halogen containing compounds in aqueous solution Reaction k 298. M n s 1 R1 HO 2 + HOCl H 2 O + O 2 + Cl k R2 = k R1 R2 HO 2 + Cl 2 Cl 2 + O 2 + H Bjergbakke et al., 1981 R3 O 2 + HOCl OH + O 2 + Cl Long and Bielski, 1980 R4 O 2 + Cl 2 Cl 2 + O k R4 = k R2 R5 HOCl + OH H 2 O + ClO k R5 = k R12 R6 HOCl + HSO 3 HSO 4 + H + + Cl k HSO3 =k SO32 (Fogelman et al., 1989) R7 HOCl +Br BrCl + OH Kumar, 1987 R8 HO 2 + HOBr H 2 O + O 2 + Br estimated (Sutton and Downes, 1972) R9 HO 2 + Br 2 Br 2 + O 2 + H Sutton and Downes, 1972 R10 O 2 + HOBr OH + O 2 + Br Schwarz and Bielski, 1986 R11 O 2 + Br 2 Br 2 + O Sutton and Downes, 1972 R12 HOBr + OH H 2 O + BrO Kläning and Wolff, 1985 R13 HOBr + HSO 3 HSO 4 + H + + Br k HSO3 =k SO32 (Fogelman et al., 1989) R14 BrO + BrO BrO 2 + OBr + 2 H Klaning and Wolff, 1985 R15 BrO 2 + BrO OBr + BrO Amichai and Treinin, 1970 R16 Br 2 + BrO 2 2 Br + BrO Buxton and Dainton, 1968 R17 BrO 2 +OH BrO 2 +OH Buxton and Dainton, 1968 R19 H + + Cl + HOCl Cl 2 + H 2 O Wang and Margerum, 1994 R20 H + + Br + HOBr Br 2 + H 2 O Eigen and Kustin, 1962

4 Table 4: Aqueous Phase equilibria Equilibrium K, M k (hin) 298/ s 1 k (rück) 298 / M n s 1 E1 HOBr H + + BrO Atkins, estimated E2 HOCl H + + ClO Atkins, estimated E3 BrCl (+H 2 O) HOBr + Cl + H Wang et al,, Wang et al,, E4 Br 2 Cl BrCl + Br Wang et al,, E5 BrCl 2 BrCl + Cl Wang et al,, E6 Br 2 Cl Br 2 + Cl Wang et al,, E7 BrCl 2 Cl 2 + Br estimated equal as E Wang et al,, 1994 E8 HBr H + +Br Atkins, estimated (limitation by diffusion) E9 HBrO 2 H + + BrO Field, abgeschätzt E10 2 HOBr H + + Br + HBrO Field, E11 HOBr+HBrO 2 2 H + +Br +BrO Field, E12 2 HBrO 2 H + + BrO 3 + HOBr Field, E13 Br 2 O 4 +H 2 O H + +BrO 3 +HBrO Field, E14 Br 2 O 4 2 BrO Field,

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