************************************************************************ * This file gives the inorganic reactions that are pasted * * into the chemical scheme given as output. * * UPDATED for JPL 10-6 (2011) by Julia Lee-Taylor, NCAR/CU 2015 * * UPDATED for HO2 and HNO2 chem by JJ Orlando, NCAR, April 2020 * * for use with spakkextra4.f * * -------------------- * * Format of the file : * * -------------------- * * * * - END OF FILE : * * set by the keyword END * * * * - COMMENT LINE : * * must be given using a "*" has first character * * * * - THERMAL REACTION : * * The format for simple thermal reaction is : * * reactants => products : A n E ; * * with the rate constant being k = A*(T)^n*exp(-E/T) * * The unit system is : * * A : molecule - cm3 - s * * n : dimensionless * * E : Kelvin (E=Ea/R) * * * * - FALL OFF REACTION * * FALL OFF REACTION ARE GIVEN WITH THE KEYWORD "(+M)" * * The format for the fall off reaction is : * * reactants (+M)=> products (+M): a1 a2 a3 a4 ; * * B m E (parameter for k0) * * B m E (parameter for kinfinite) * * with : k0 = B*(T/300)^m*exp(-E/T) and a similar expression * * for Kinfinite. The rate constant is computed according * * to the Troe expression : * * k= [k0[M]/(1+k0[M]/kinf)] * F ^ {1/[1+[log(k0[M]/kinf)]^2]}* * Various expression for F can be set, depending on the value * * of a2 and a4 : * * - IF (a2 equal 0) THEN F=a1 * * - IF (a2 not equal 0) and (a4 not equal 0) THEN * * F=(1-a1)*exp(-T/a2) + a1*exp(-T/a3) + exp(-a4/T) * * - IF (a2 not equal 0) and (a4 equal 0) THEN * * F=(1-a1)*exp(-T/a2) + a1*exp(-T/a3) * * * * - REACTIONS WITH SPECIAL REACTION RATE * * THESE REACTIONS ARE GIVEN WITH THE KEYWORD "EXTRA" and are * * typically used for reactions involving a reactant not * * set by the system of ODE (exemple O2, H2O) or when the * * reaction has a particular expression rate * * The format for these reactions is : * * reactants + EXTRA => products : A n E ; * * ii : xx1 xx2 xx3 ... ; * * A, n, E : have the same meaning than thermal reaction * * ii : is a label (for ex. label 100 is used for O2 reactions) * * xx1, xx2, ... : is optional additionnal information (numbers) * * * * - PHOTOLYTIC REACTIONS * * THESE REACTIONS ARE GIVEN WITH THE KEYWORD "HV" * * The format is : * * reactants +HV => products : jj kk * * jj : is a label (allow to find the corresponding J values) * * labels correspond to TUV labels where applicable * * kk : multiplicating factor * ************************************************************************ * * THERMAL REACTION * ---------------- * * NASA 1997 - reaction produces 2 O2 GO3P + GO3 => NOTHING : 8.00E-12 0. 2060. ; * * NASA JPL 10-6 (2011) GO3P + GNO2 => GNO : 5.10E-12 0. -210. ; * * NASA JPL 10-6 (2011) *GO1D + GN2 => GO3P + GN2 : 2.15E-11 0. -110. ; *GO1D + GO2 => GO3P + GO2 : 3.30E-11 0. -55 ; * Since N2 and O2 are not explicitly considered, use TWO "+M" reactions: GO1D + M => GO3P + M : 1.677E-11 0.0 -110. ; JPL 10-6 (O1D + N2): A = 2.15e-11 * 78% GO1D + M => GO3P + M : 6.765E-12 0.0 -55. ; JPL 10-6 (O1D + O2): A = 3.3e-11 * 20.5% * * NASA 2000 GO3 + GNO => GNO2 : 3.00E-12 0. 1500. ; * * NASA 1997 GO3 + GNO2 => GNO3 : 1.20E-13 0. 2450. ; * * NASA 1997 GNO + GNO3 => 2. GNO2 : 1.50E-11 0. -170. ; * * IUPAC 1997 - Supp V GNO + GNO + M => 2. GNO2 : 3.30E-39 0. -530. ; * * NASA 1997 GNO2 + GNO3 => GNO + GNO2 : 4.50E-14 0. 1260. ; * * NASA JPL 10-6 (2011), unchanged *GHO + GHNO2 => GNO2 : 1.80E-11 0. 390. ; * Updated to Burkholder et al. (1992) GHO + GHNO2 => GNO2 : 2.80E-12 0. -260. ; * * NASA JPL 10-6 (2011) GHO + GNO3 => GHO2 + GNO2 : 2.20E-11 0. 0. ; * * NASA 1997 GHO + GCO => GHO2 + GCO2 : 1.50E-13 0. 0. ; * * NASA 1997 GHO + GCO + M => GHO2 + GCO2 : 3.66E-33 0. 0. ; * * NASA JPL 10-6 (2011) GHO + GO3 => GHO2 : 1.70E-12 0. 940. ; * * JPL 10-6 (2011) *GHO2 + GNO => GHO + GNO2 : 3.50E-12 0. -270. ; * JPL 10-6 (2011), updated to JPL 15-10 (2015) GHO2 + GNO => GHO + GNO2 : 3.30E-12 0. -270. ; * * NASA 1997 GHNO4 + GHO => GNO2 : 1.30E-12 0. -380. ; * * JPL 10-6 (2011) GHO2 + GO3 => GHO : 1.00E-14 0. 490. ; * * JPL 10-6 (2011) - see also rxn EXTRA 501 GHO2 + GHO2 => GH2O2 : 3.00E-13 0. -460. ; * * JPL 10-6 (2011) - see also rxn EXTRA 501 GHO2 + GHO2 + M => GH2O2 + M : 2.10E-33 0. -920. ; * * NASA 1997 GNO3 + GHO2 => 0.8 GHO + 0.8 GNO2 + 0.2 GHNO3 : 3.50E-12 0. 0. ; * * NASA 1997 GNO3 + GNO3 => 2. GNO2 : 8.50E-13 0. 2450. ; * * JPL 10-6 (2011) GH2O2 + GHO => GHO2 : 1.80E-12 0. 0. ; * * NASA 2000 GHO + GHO2 => NOTHING : 4.80E-11 0. -250. ; * * JPL 10-6 (2011) (note different products: previously HO2) GHO + GH2 => GH2O + GH : 2.8E-12 0. 1800. ; * * Reactions from Li et al (2015), after JPL 10-6 : relevant for PAM GO1D + GCO2 => GO3P + GCO2 : 7.500E-11 0. -115. ; GO1D + GO3 => 2.00 GO2 : 1.200E-10 0. 0. ; GO1D + GO3 => 2.00 GO3P + GO2 : 1.200E-10 0. 0. ; GO1D + GH2 => GHO + GH : 1.200E-10 0. 0. ; GO3P + GHO => GH + GO2 : 2.200E-10 0. -180. ; GO3P + GHO2 => GHO + GO2 : 3.000E-11 0. -200. ; GO3P + GH2O2 => GHO2 + GO2 : 1.400E-12 0. 2000. ; GO3 + GH => GHO + GO2 : 1.400E-10 0. 470. ; GHO2 + GH => 2.00 GHO : 7.200E-11 0. 0. ; GHO2 + GH => GO3P + GH2O : 1.600E-12 0. 0. ; GHO2 + GH => GO2 + GH2 : 6.900E-12 0. 0. ; GO3P + GNO3 => GNO2 + GO2 : 1.000E-11 0. 0. ; GNO2 + GH => GHO + GNO : 4.000E-10 0. 340. ; GHO + GHO => GH2O + GO3P : 0.180E-11 0.0 0. ; * * FALL OFF REACTIONS * ------------------ * * NASA 2000 GO3P + GNO (+M) => GNO2 (+M) : 0.6 0. 0. 0. ; 9.00E-32 1.5 0. 3.00E-11 0.0 0. * * JPL 10-6 (2011) GO3P + GNO2 (+M) => GNO3 (+M) : 0.6 0. 0. 0. ; 2.50E-31 1.8 0. 2.20E-11 0.7 0. * * NASA 2000 GNO2 + GNO3 (+M)=> GN2O5 (+M) : 0.6 0. 0. 0. ; 2.00E-30 4.4 0. 1.40E-12 0.7 0. * * NASA 2000 Keq = 3.0E-27exp(10991/T) GN2O5 (+M) => GNO2 + GNO3 (+M) : 0.6 0. 0. 0. ; 6.67E-04 4.4 10991 4.67E+14 0.7 10991 * * NASA 1997 GHO + GNO (+M) => GHNO2 (+M) : 0.6 0. 0. 0. ; 7.00E-31 2.6 0. 3.60E-11 0.1 0. * * JPL 10-6 (2011) GHO + GNO2 (+M) => GHNO3 (+M) : 0.6 0. 0. 0. ; 1.80E-30 3.0 0. 2.80E-11 0.0 0. * * JPL 10-6 (2011) GHO2 + GNO2 (+M) => GHNO4 (+M) : 0.6 0. 0. 0. ; 2.00E-31 3.4 0. 2.90E-12 0.0 0. * * IUPAC 1997 GHNO4 (+M) => GHO2 + GNO2 (+M) : 0.6 0. 0. 0. ; 5.00E-06 0.0 10000 2.61E+15 0.0 10900 * * JPL 10-6 (2011) GHO + GSO2 (+M) => GHO2 + GSULF (+M) : 0.6 0. 0. 0. ; 3.30E-31 4.3 0. 1.60E-12 0.0 0. * * Reaction 48 from Li et al (2015), after JPL 10-6 : relevant for PAM GH + GO2 (+M) => GH2O2 (+M) : 0.6 0. 0. 0. ; 4.40E-32 1.3 0. 0.75E-10 0.2 0. * * Reaction 49 from Li et al (2015), after JPL 10-6 : relevant for PAM GHO + GHO (+M) => GH2O2 (+M) : 0.6 0. 0. 0. ; 6.900E-31 -1.0 0. 0.260E-10 0.0 0. *---------------------- * SPECIAL REACTION RATE * --------------------- * * NASA JPL 10-6 (2011) - rate constant is mult. by [O2] and [M] * from JPL10-6: k300 = 6.0E-34, n = 2.4, form k=k300(T/300)^-n * Convert to form k = A.T^b.EXP(-E/R/T) as follows: * A = k300/(300^-n), n = -b * (Conversion is exact because (E/R) = 0) GO3P + EXTRA => GO3 : 5.29E-28 -2.4 0. ; 100 : ; * * JPL 10-6 (2011) - rate constant is mult. by [H2O] GO1D + EXTRA => 2. GHO : 1.63E-10 0. -60. ; 500 : ; * * NASA 2000 - rate constant is k=k0+k3[M]/(1+k3[M]/k2) * k0 is given just after the reaction * k2 is the first 3 numbers after the label * k3 is the last 3 numbers after the label GHO + GHNO3 + EXTRA => GNO3 : 2.40E-14 0. -460. ; 550 : 2.7E-17 0. -2199 6.5E-34 0. -1335 ; * * JPL 10-6 (2011) - rate const is k = (k1 + k2[M])(1 + k3[H2O]) * k1 and k2 are given above. * k3 (JPL 10-6) is 1.4E-21 0. -2200 * multiplying k3 by k1 and k2 gives values for use in spakkextra4.f: * k1k3 is the first set of 3 numbers * k2k3 is the 3 numbers after the label GHO2 + GHO2 + EXTRA => GH2O2 : 4.2E-34 0. -2660. ; 501 : 2.94E-54 0. -3120. ; *--------------------------------- * PHOTOLYTIC REACTIONS * -------------------- * SAPRC 99 GO3 + HV => GO1D : 02 1 ; * * SAPRC 99 GO3 + HV => GO3P : 03 1 ; * * SAPRC 99 GNO2 + HV => GNO + GO3P : 04 1 ; * * SAPRC 99 GNO3 + HV => GNO : 05 1 ; * * SAPRC 99 GNO3 + HV => GNO2 + GO3 : 06 1 ; * * SAPRC 99 GH2O2 + HV => 2. GHO : 11 1 ; * * Stutz et al., 2000 GHNO2 + HV => GHO + GNO : 12 1 ; * * SAPRC 99 GHNO3 + HV => GHO + GNO2 : 13 1 ; * * SAPRC 99 GHNO4 + HV => 0.61 GHO2 + 0.61 GNO2 + 0.39 GHO + 0.39 GHNO3 : 14 1 ; * * OFR GO2 + HV => 2. GO3P : 15 1 ; * * OFR GH2O + HV => GHO2 + GHO : 16 1 ; * * end of file END ======================================================================= References : ------------ IUPAC 1997 : Atkinson R., D.L. Baulch, R.A. Cox, R.F. Hampson, J.A. Kerr, M. Rossi, J. Troe, Evaluated kinetic, photochemical and heterogeneous data dor atmospheric chemistry : Supplement V, IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry, J. Phys. Chem. Ref. Data, 521-1011, 1997 JPL 2011 : Sander S.P., R.R. Friedl, J.R. Barker, D.M. Golden, M.J. Kurylo, P.H. Wine, J.P.D. Abbatt, J.B. Burkholder, C.E. Kolb, G.K. Moortgat, R.E. Huie, V.L. Orkin, Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation No. 17, JPL Publication 10-6, Jet Propulsion Laboratory, Pasadena, Califonia Li, R. et al, J Phys Chem A, 1990, 4418-4432, doi:10.1021/jp509534k, 2015. NASA 1997 : DeMore W.B., S.P. Sander, D.M. Golden, R.F. Hampson, M.J. Kurylo, C.J. Howard, A.R. Ravishankara, C.E. Kolb, M.J. Molina, Chemical kinetics and photochemical data for use in stratospheric modeling, JPL Publication 97-4, Jet Propulsion Laboratory, Pasadena, Califonia NASA 2000 : Sander S.P., R.R. Friedl, W.B. DeMore, A.R. Ravishankara, D.M. Golden, C.E. Kolb, M.J. Kurylo, R.F. Hampson, R.E. Huie, M.J. Molina, G.K. Moortgat, Chemical kinetics and photochemical data for use in stratospheric modeling, JPL Publication 00-3, Jet Propulsion Laboratory, Pasadena, Califonia Stutz J., E.S. Kim, U. Platt, P. Bruno, C. Perrino and A. Febo, UV-visible absorption cross section of nitrous acid, Journal of Geophysical Research, 14585-14592, 2000 Troe J., Analysis of the temperature and pressure dependence of the reaction HO+NO2+M <=> HONO2+M, International Journal of Chemical Kinetic, 878-889, 2001