Table 5. SOCRATES Chemical reactions.

Odd hydrogen reactions a1 H + O2 + M -> HO2 + M * k0(300)=5.7e-32 n=1.6 kinf(300)=7.5e-11 m=0 a1et O1D + H20 -> OH + OH 2.2e-10 a2 H + O3 -> OH + O2 1.4e-10 exp(-470/T) a2et O1D + CH4 -> OH + CH3O2 1.5e-10 a3et O1D + H2 -> OH + H 1.0e-10 a5 O + OH -> O2 + H 2.2e-11 exp(120/T) a6 OH + O3 -> HO2 + O2 1.6e-12 exp(-940/T) a6b HO2 + O3 -> OH + 2O2 1.1e-14 exp(-500/T) a7 O + HO2 -> OH + O2 3. e-11 exp(200/T) a17 OH + HO2 -> H2O + O2 4.8e-11 exp(250/T) a19 OH + H2 -> H2O + H 5.5e-12 exp(-2000/T) a23a H + HO2 -> OH + OH 8.1e-11*0.9 a23b H + HO2 -> H2 + O2 8.1e-11*0.08 a23c H + HO2 -> H2O + O 8.1e-11*0.02 a24 H2 + O -> OH + H 8.8e-12 exp(-4200/T) a26 NO + HO2 -> NO2 + OH 3.5e-12 exp(250/T) a27 HO2 + HO2 -> H2O2 + O2 ** k1=1.7e-33 exp(1000/T)[M] k2=2.3e-13 exp(600/T) fh2o=1+1.4e-21 exp(2200/T)[H2O] a30 OH + H2O2 -> H2O + HO2 2.9e-12 exp(-160/T) a36 OH + CO -> CO2 + H 1.5e-13*(1+0.6p(mb)/1013) a40 HO2+HO2+H2O -> H2O2+O2+H2O a81 O+H2O2 -> OH+HO2 1.4e-12 exp(-2000/T) a82 OH+OH -> H2O + O 4.2e-12 exp(-240/T) a83 OH+OH+M -> H2O2 + M * k0(300)=6.9e-31 n=0.8 kinf(300)=1.5e-11 m=0 Odd nitrogen reactions b3 O + NO2 -> NO+ O2 6.5e-12 exp(120/T) b4 O3 + NO -> NO2 + O2 2.0e-12 exp(-1400/T) b6 N + NO -> N2 + O 2.1e-11 exp(100/T) b7 N + O2 -> NO + O 1.5e-11 exp(-3600/T) b9 O3 + NO2 -> NO3 + O2 1.2e-12 exp(-2450/T) b12 NO2 + NO3 + M -> N2O5 + M * k0(300)=2.2e-30 n=3.9 kinf(300)=1.5e-12 m=0.7 b22 OH + NO2 + M -> HNO3 + M * k0(300)==2.6e-30 n=3.2 kinf(300)=2.4e-11 m=1.3 b23 HO2 + NO2 + M -> HO2NO2 + M * k0(300)=1.8e-31 n=3.2 kinf(300)=4.7e-12 m=1.4 b24 HO2NO2 + M -> HO2 + NO2 + M b23/Keq Keq=2.1e-27 exp(10900/T) b27 HNO3 + OH -> H2O + NO3 *** k0=7.25e-15 exp(785/T) k2=4.1e-16 exp(1440/T) k3=1.9e-33 exp(725/T) b28 OH + HO2NO2-> H2O+NO2+O2 1.3e-12 exp(380/T) b32 N2O5 + M -> NO2 + NO3 + M b12/Keq Keq=2.7e-27exp(11000/T) b38 O1D + N2O -> N2 + O2 4.9e-11 b39 O1D + N2O -> NO + NO 6.7e-11 b71 NO3+O -> NO2+O 1.0e-11 b72 NO3+OH -> NO2+HO2 2.2e-11 b73a NO3+HO2 -> OH+NO2+O2 3.5e-12*0.8 b73b NO3+HO2 -> HNO3+O2 3.5e-12*0.2 b81 O+NO2+M -> NO3+M * k0(300)=9.0e-32 n=2 kinf(300)=2.2e-11 m=0 b82 NO+O+M -> NO2+M * k0(300)=9.0e-32 n=1.5 kinf(300)=3.0e-11 m=0 b84 NO+NO3 -> 2NO2 1.5e-11 exp(170/T) Carbon reactions c1 CH4 + O1D -> CH3O2 + OH 1.5e-10 c1a CH4 + O1D -> CH2O +H2 1.5e-11 c2 CH4 + OH -> CH3O2 +H2O 2.45e-12 exp(-1775/T) c5 CH3O2 + NO -> CH2O+HO2+NO2 4.2e-12 exp(180/T) c7 CH3O2 + HO2 -> CH3OOH+O2 3.8e-13 exp(800/T) c8 CH2O + OH -> CO+HO2+H2O 1.e-11 c9 CH2O + O -> CO+HO2+OH 3.4e-11 exp(-1600/T) c10 CH2O + NO3 -> CO+HO2+HNO3 6.e-13 exp(-2058/T) c14 CH3O2 + CH3O2 -> 0.6CH3OH+1.4CH2O+0.8HO2 2.5e-13 exp(190/T) c17 CH3O2H + OH -> CH3O2+H2O 0.58*3.8e-12 exp(200/T) c44 CH3O2H + OH-> CH2O+H2O+OH 0.42*3.8e-12 exp(200/T) c50 C2H6 + OH -> C2H5O2+H2O 8.7e-12 exp(-1070/T) c51 C2H6 + Cl -> HCl + C2H5 7.7e-11 exp(-90/T) c52 C2H5O2 + NO -> CH3CHO+HO2+NO2 2.6e-12 exp(365/T) c53 C2H5O2 + HO2 -> C2H5OOH+O2 7.5e-13 exp(700/T) c54 C2H5O2 + CH3O2 -> 0.7CH2O+0.8CH3CHO+HO2+0.3CH3OH +0.2C2H5OH 3.75e-13 exp(-40/T) c55 C2H5O2 + C2H5O2 -> 1.6CH3CHO+1.2HO2 +0.4C2H5OH+O2 1.5e-13 exp(-270/T) c56 C2H5O2H + OH -> 0.5(C2H5O2+CH3CHO+OH)+H2O 7.0e-12 exp(235/T) c57 CH3CHO + OH -> CH3COO2+H2O 5.6e-12 exp(270/T) c57et CH3CHO + NO3 -> CH3COO2+HNO3 1.4e-12 exp(-1900/T) c58 CH3CO3H + OH -> CH3COO2+H2O 1.e-11 c59 CH3CO3 + NO -> CH3O2+NO2+CO2 5.3e-12 exp(360/T) c60 CH3CO3 + NO2 +M -> PAN + M * k0(300)=9.7e-20 n=5.6 kinf(300)=9.0e-12 m=1.5 c61 CH3CO3 + HO2 -> 2/3(CH3CO3H+O2)+1/3(CH3COOH+O3) 4.5e-13 exp(1000/T) c62 CH3CO3 + CH3O2 -> CH3O2 + CH2O + CO2 + HO2 ***** c62 = k*kratio/(1+kratio) c63 CH3CO3 + CH3O2 -> CH3CO2H + CH2O + O2 ***** c63 = k/(1+kratio) c64 CH3CO3 + CH3CO3 -> 2CH3O2+2CO2 2.9e-12 exp(500/T) c65 PAN + OH -> CH2O2CO3NO2+H2O 1.1e-12 exp(-650/T) c66 PAN + M -> CH3COO2+NO2+M **** k0=5.2e-2 exp(-12875/T) k°=2.2e16 exp(-13435/T) fc=0.27 c67 PAN + NO -> products 1.0e-12 c68 C2H4 + OH + M -> 2/3(C3H6OHO2)+M **** k0=9.5e-20 (300/T)3.1 k°=9.5e-12 fc=exp(-T/840) c69 C2H4 + O3 -> CH2O+0.4HCOOH+0.52HO2+0.4OH +0.18CO2+0.42CO+0.12H2+0.02H2O 1.2e-14 exp(-2630/T) c70 C3H6 + OH + M -> C3H6OHO2+M **** k0=8.0e-27 (300/T)3.5 kinf=3.0e-11 fc=exp(-T/433) c71 C3H6 + O3-> 0.1CH3COOH+0.08CH4+0.585HO2+0.2875CH3O2 +0.37CO+0.5325CH2O+0.4575OH+0.06H2 +0.5CH3CHO+0.2HCOOH+0.33CO2 6.5e-15 exp(-1900/T) c72 C3H6 + NO3 -> C3H6NO3 4.0e-15 c73 C3H6OHO2 + NO -> CH3CHO+CH2O+NO2+HO2 4.2e-12 exp(180/T) c74 C3H6OHO2 + HO2 -> C3H6OHOOH+O2 6.5e-13 exp(650/T) c75 C3H6OHOOH + OH -> 0.5(C3H6OHO2+CH3COCH2OH+OH) +H2O 3.8e-12 exp(200/T) Chlorine reactions d0 OH + CH3Cl -> CH2Cl + H2O 4.1e-12 exp(-1400/T) d2 Cl + O3 -> ClO + O2 2.9e-12 exp(-260/T) d3 ClO + O -> Cl + O2 3.0e-11 exp(70/T) d4 ClO + NO -> NO2 + Cl 6.4e-12 exp(290/T) d5 Cl + CH4 -> HCl + CH3O2 1.1e-11 exp(-1400/T) d6 Cl + H2 -> HCl + H 3.7e-11 exp(-2300/T) d7 Cl + HO2 -> HCl + O2 1.8e-11 exp(170/T) d8 ClO + OH -> Cl + HO2 1.1e-11 exp(120/T)*0.93 d10 Cl + CH2O -> HCl+CO+HO2 8.1e-11 exp(-30/T) d11 OH + HCl -> H2O + Cl 2.6e-12 exp(-350/T) d31 ClO + NO2 + M -> ClONO2 + M * k0(300)=1.8e-31 n=3.4 kinf(300)=1.5e-11 m=1.9 d32 O + ClONO2 -> NO3 + ClO 2.9e-12 exp(-800/T) d33 ClO + HO2 -> HOCl + O2 4.8e-13 exp(700/T) d34 OH + HOCl -> H2O + ClO 3.0e-12 exp(-500/T) d35 O + HOCl -> OH + ClO 1.7e-13 d36 Cl + NO2 + M -> ClNO2 + M * k0(300)=1.8e-31 n=2 kinf(300)=1.0e-10 m=1 d37 Cl + HOCl -> OH + Cl2 2.5e-12 exp(-130/T) d46 ClO+OH -> HCl+O2 1.1e-11 exp(120/T)*0.07 d47 ClO+ClO -> Cl+OClO 3.5e-13 exp(-1370/T) d48 ClO+ClO -> Cl2+O2 1.0e-12 exp(-1590/T) d50 CH3CCl3 + OH -> 3 Cl + products 1.8e-12 exp(-1550/T) d52 HCFC22 + OH -> Cl + products 1.0e-12 exp(-1600/T) d60 ClO + ClO + M -> Cl2O2 + M * k0(300)=2.2e-32 n=3.1 kinf(300)=3.5e-12 m=1 d61 Cl2O2 + M -> ClO + ClO + M d60/Keq Keq=1.3e-27 exp(8744/T) d62 OClO + OH -> HOCl + O2 4.5e-13 exp(800/T) d63 Cl + OClO -> ClO + ClO 3.4e-11 exp(160/T) d64 OClO + O -> ClO + O2 2.4e-12 exp(-960/T) d65 OClO + NO -> NO2 + ClO 2.5e-12 exp(-600/T) d71 O1D+Cl2 -> ClO+Cl 2.8e-10 d72 Cl2O2+Cl -> Cl2+Cl+O2 1.0e-10 d73 NO3+Cl -> NO2+ClO 2.4e-11 d74 NO3+ClO -> NO2+Cl+O2 4.7e-13 d75 O1D+HCl -> OH+Cl 1.5e-10 d81 OH+Cl2 -> HOCl +Cl 1.4e-12 exp(-900/T) d82 Cl + ClONO2 -> Cl2 + NO3 6.5e-12 exp(135/T) d83 HO2+Cl -> OH+ClO 4.1e-11 exp(-450/T) d84 Cl+H2O2 -> HCl+HO2 1.1e-11 exp(-980/T) d85 O+HCl -> Cl+OH 1.0e-11 exp(-3300/T) d87 ClONO2+OH -> HOCl + NO3 1.2e-12 exp(-330/T) d90 O1D + CFCl3 -> products 2.3e-10 d91 O1D + CF2Cl2 -> products 1.4e-10 d101 CFC10 + O(1D) -> CCl2O + Cl2 3.3e-10 d102 CFC11 + O(1D) -> CClFO + Cl2 2.3e-11 d103 CFC12 + O(1D) -> CF2O + Cl2 1.4e-10 d104 CFC113 + O(1D) -> CClFO + CF2O + Cl2 2.e-10 d105 CFC114 + O(1D) -> 2 CF2O + Cl2 1.3e-10 d106 CFC115 + O(1D) -> CF2O + HF + Cl 5.e-11 d107 HCFC-22 + O(1D) -> CF2O + Cl 1.e-10 d108 CCl2O + O(1D) -> Cl2 + products 3.6e-10 d109 CClFO + O(1D) -> HF + Cl + products 1.9e-10 d110 CF2O + O(1D) -> 2 HF + products 7.4e-11 Bromine reactions e0 CH3Br + OH -> H2O + Br + products 4.0e-12 exp(-1470/T) e1 CHBr3 + OH -> H2O + 3 Br + products 1.6e-13 exp(-710/T) e2 Br + O3 -> BrO + O2 1.7e-11 exp(-800/T) e3 BrO + O -> Br + O2 1.9e-11 exp(230/T) e4 BrO + NO -> NO2 + Br 8.8e-12 exp(260/T) e5a BrO + ClO -> OClO + Br 1.6e-12 exp(430/T) e5b BrO + ClO -> Br + Cl + O2 2.9e-12 exp(220/T) e5c BrO + ClO -> BrCl + O2 5.8e-13 exp(170/T) e6 BrO + BrO -> 2Br + O2 1.5e-12 exp(230/T) e7 Br + HO2 -> HBr + O2 1.5e-11 exp(-600/T) e8 Br + OClO -> BrO + ClO 2.6e-11 exp(-1300/T) e9 Br+CH2O -> HBr+ CO + HO2 1.7e-11 exp(-800/T) e11 OH + HBr -> H2O + Br 1.1e-11 e13 BrO + NO2 + M -> BrONO2 + M * k0(300)=5.2e-31 n=3.2 kinf(300)=6.9e-12 m=2.9 e15 BrO + HO2 -> HOBr + O2 3.4e-12 exp(540/T) e71 O1D+HBr -> OH+Br 1.5e-10 e72 BrO+OH -> HO2+Br 7.5e-11 e81 O+HBr -> Br+OH 5.8e-12 exp(-1500/T) e91 ha-1301 + O(1D) -> Br + 3HF + prod. 1.e-10 e92 ha-1211 + O(1D) -> Br + Cl + prod. 1.5e-10 e93 CH3Br + O(1D) -> Br + prod. 1.8e-10 Oxygen reactions hk1 O + O + M -> O2 + M 4.23e-28 [M]/T2 hk2 O + O2 + M -> O3 + M 6.0e-34*(300/T)2.3*[M] hk3 O + O3 -> O2 + O2 8.0e-12 exp(-2060/T) hk4 O1D + N2 -> O + N2 1.8e-11 exp(110/T) hk5 O1D + O2 -> O + O2 3.2e-11 exp(70/T) hk7 O1D + O3 -> O2 + O2 1.2e-10 hk21 O1D+N2 +M -> N2O +M 3.5e-37*(300*T)0.6*[M]