************************************************************************ * This file gives the inorganic reactions that are pasted * * in the chemical scheme given as output. * * * * -------------------- * * 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) * * kk : multiplicating factor * ************************************************************************ * * ------------- * CH4 chemistry * ------------- * * IUPAC 1999 *GCH4 + GHO => GCH3O2 : 2.15E-12 0. 1735 ; * Updated to JPL 15-10 (2015), in April 2020 by JJO GCH4 + GHO => GCH3O2 : 2.45E-12 0. 1775 ; * kinetics data from Tyndall et al. 2001 - Branching ratio * for the radical channel=0.37 (recommended by Tyndall at 298K) * GCH3O2 + GCH3O2 => GCH3OH + GCH2O : 6.00E-14 0. -390. ; * GCH3O2 + GCH3O2 => 2 GCH3O : 3.50E-14 0. -390. ; * Updated April 2020 by JJO to take into account T-dep of branching ratio * (Tyndall, 2001, as rec by JPL 2015) GCH3O2 + GCH3O2 => GCH3OH + GCH2O : 2.20E-14 0. -690. ; GCH3O2 + GCH3O2 => 2 GCH3O : 5.70E-13 0. 440. ; * * Tyndall 2001 GCH3O2 + GNO => GCH3O + GNO2 : 2.80E-12 0. -300. ; * * IUPAC 1999 GCH3O2 + GNO3 => GCH3O + GNO2 : 1.30E-12 0. 0. ; * * Tyndall 2001 GCH3O2 + GHO2 => GCH3OOH : 4.10E-13 0. -750. ; * * rate constant is multiplied by [O2] *GCH3O + EXTRA => GCH2O + GHO2 : 7.20E-14 0. 1080. ; * 300 : ; GCH3O + OXYGEN => GCH2O + GHO2 : 7.20E-14 0. 1080. ; * * ---------------------- * CH3OH chemistry * ---------------------- * * IUPAC 1999 GCH3OH + GHO => 0.85 GCH2O + 0.85 GHO2 + 0.15 GCH3O : 3.10E-12 0. 360. ; * * IUPAC 1999 GCH3OH + GNO3 => GCH2O + GHO2 + GHNO3 : 9.4E-13 0. 2650. ; * * ---------------------- * CH3OOH chemistry * ---------------------- * * reference GCH3OOH + HV => GCH3O + GHO : 7300 1 ; * * IUPAC 1999 * GCH3OOH + GHO => GHO + GCH2O : 1.00E-12 0. -190. ; * GCH3OOH + GHO => GCH3O2 : 1.90E-12 0. -190. ; * Updated to JPL 2015, in April 2020 by JJO GCH3OOH + GHO => GHO + GCH2O : 1.10E-12 0. -200. ; GCH3OOH + GHO => GCH3O2 : 2.70E-12 0. -200. ; * * ---------------------- * CH3ONO chemistry * ---------------------- * GV01000 + HV => GNO + GCH3O : 40000 1 ; GV01000 + GHO => GH2O + GCH2O + GNO : 0.301E-12 0. 0. ; * * ---------------------- * CH3ONO2 chemistry * ---------------------- * * IUPAC 1999 (GN0101=CH3(ONO2)) GCH3O + GNO2 (+M) => GN01000 (+M) : 0.44 0. 0. 0. ; 9.0E-29 4.5 0. 1.9E-11 0. 0. * * reference GN01000 + HV => GCH3O + GNO2 : 100 1 ; * * IUPAC 1999 * GN01000 + GHO => GCH2O + GNO2 : 4.00E-13 0. 845 ; * Updated to JPL 2015, in April 2020 by JJO GN01000 + GHO => GCH2O + GNO2 : 8.00E-13 0. 1000. ; * * ---------------------- * CH3OONO2 chemistry (Orlando/JMLT sensitivity tests, 2020) * ---------------------- * GN01002 => GNO2 + GCH3O2 : 5.60E+15 0. 104400. ; * * ---------------------- * formaldehyde chemistry * ---------------------- * * reference GCH2O + HV => GCO + 2 GHO2 : 110 1 ; GCH2O + HV => GH2 + GCO : 17 1 ; * * IUPAC 99 * GCH2O + GHO => GCO + GHO2 : 8.60E-12 0. -20. ; * Updated to JPL 2015, April 2020 by JJO GCH2O + GHO => GCO + GHO2 : 5.50E-12 0. -125 ; * * reference GCH2O + GNO3 => GHNO3 + GCO + GHO2 : 5.80E-16 0. 0. ; * * ----------------------- * CH2(OH)(ONO2) chemistry * ----------------------- * The chemistry of this compound has to be checked. * It's produced during the oxidation of alkanes. * For the moment, the constants are the same as CH3OH. * It's assumed that only a reaction with OH occurs. * GNO1000 + GHO => GHCOOH + GNO2 : 3.10E-12 0. 0. ; * * ---------------------- * formic acid chemistry * ---------------------- * * IUPAC 1999 GHCOOH + GHO => GHO2 + GCO2 : 4.50E-13 0. 0. ; * * --------------------- * Chemistry of HCO(OOH) * --------------------- * * this species is produced as a minor product * during the oxidation of some HC. We assume * that this species behaves like CH3-CO(OOH). * RO2+RO2 reactions are not considered (minor reaction * channel for a very minor species). * * use rate for CH3OOH + HO => CH3OO. + H2O GHCOO2H + GHO => GHCOO2 : 1.90E-12 0. -190. ; * * Photolysis values of CH3OOH GHCOO2H + HV => GHO2 + GHO + GCO2 : 40100 1 ; * * use rate for CH3CO(OO.) (IUPAC 1999) GHCOO2 + GHO2 => 0.7 GHCOO2H + 0.3 GHCOOH + 0.3 GO3 : 4.3E-13 0. -1040. ; * * use rate for CH3CO(OO.) (Tyndall 2001) GHCOO2 + GNO => GHO2 + GNO2 + GCO2 : 8.10E-12 0. -270. ; * * use rate for CH3CO(OO.) (Canosa-Mas) * previous version *GHCOO2 + GNO3 => GCH3O2 + GCO2 + GNO2 : 5.00E-12 0. 0. ; * corrected version GHCOO2 + GNO3 => GHO2 + GCO2 + GNO2 : 5.00E-12 0. 0. ; * * use rate for CH3CO(OO.) GHCOO2 + GCH3O2 => 1.37 GHO2 + 1.37 GCO2 + 1.37 GCH3O : 5.00E-12 0. 0. ; GHCOO2 + GCH3O2 => 0.63 GHCOOH + 0.63 GCH2O : 5.00E-12 0. 0. ; * * use rate for CH3CO(OO.) (Tyndall 2001) [P01000 = CHO(OONO2) ] GHCOO2 + GNO2 (+M) => GP01000 (+M) : 0.6 0. 0. 0. ; 8.50E-29 6.5 0. 1.10E-11 1.0 0. * values for PAN decomposition GP01000 (+M) => GHCOO2 + GNO2 (+M) : 0.3 0. 0. 0. ; 4.90E-03 0.0 12100. 5.40E+16 0.0 13830. * * reference GP01000 + HV => GHCOO2 + GNO2 : 1400 1 ; * * --------------------- * Chemistry of CH2(OOH)(OO.), CH2(OH)(OO.), CO(OOH)(OO.) * --------------------- * 2O1000 = CH2(OH)(OO.) * 2H1000 = CH2(OOH)(OO.) * 2N1000 = CO(ONO2)(OO.) * 2H1001 = CO(OOH)(OO.) * these species are produced as minor products * during the oxidation of some MT. We assume * the following: * G2H1000 + GHO2 => GCH2O + GHO + GHO2 : 4.3E-13 0. -1040. ; G2H1000 + GNO => GCH2O + GHO2 + GNO2 : 9.00E-12 0. 0. ; G2H1000 + GNO3 => GCH2O + GHO2 + GNO2 : 1.00E-12 0. 0. ; G2H1000 + GCH3O2 => 2. GCH2O + 2. GHO2 : 2.00E-12 0. 0. ; G2H1000 + GCH3O2 => GCOHOOH + GCH2O : 1.00E-12 0. 0. ; G2H1000 + GCH3O2 => GHCOO2H + GCH3OH : 1.00E-12 0. 0. ; * G2O1000 => GCH2O + GHO2 : 1E+6 0. 0. ; G2N1000 => GCO2 + GNO2 : 1E+6 0. 0. ; G2H1001 => GCO2 + GHO : 1E+6 0. 0. ; * * * -------------------------- * Decomposition of HCO(ONO2), HCO(NO2), CO(ONO2)(OOH), CO(OH)(OH), CO(OH)(ONO2) * -------------------------- * DV1000 = HCO(NO2) * ND1000 = HCO(ONO2) * AO1000 = CO(OH)(OH) * AN1000 = CO(OH)(ONO2) * HN1000 = CO(ONO2)(OOH) * * these species are produced as minor products * during the oxidation of some cyclic /terpenoid HC. * We assume that they decompose immediately * GDV1000 => GCO + GHO2 + GNO2 : 1.0E+01 0. 0. ; GND1000 => GCO2 + GHO2 + GNO2 : 1.0E+01 0. 0. ; GHN1000 => GCO2 + GHO2 + GNO2 : 1.0E+01 0. 0. ; GAO1000 => GCO2 + GH2O : 1.0E+01 0. 0. ; GAN1000 => GCO2 + GHO + GNO2 : 1.0E+01 0. 0. ; * ------------------------------------------------------ * Reactions of stable C1 Criegee intermediate CH2.(OO.) * ------------------------------------------------------ * with water G4CH2OO + EXTRA => 0.375 GCH2O + 0.375 GH2O2 + 0.625 GHCOOH : 1.5E-16 0. 0. ; 500 : ; * with water dimers G4CH2OO + EXTRA => 0.375 GCH2O + 0.375 GH2O2 + 0.625 GHCOOH : 5.5e-12 0. 0. ; 502 : ; * with SO2 G4CH2OO + GSO2 => GCH2O + GSULF : 3.7e-11 0. 0. ; * with NO G4CH2OO + GNO => GCH2O + GNO2 : 6.0e-14 0. 0. ; * with NO2 G4CH2OO + GNO2 => GCH2O + GNO3 : 3.0e-12 0. 0. ; * with CO G4CH2OO + GCO => GCH2O + GCO2 : 1.0e-21 0. 0. ; * with HCl * G4CH2OO + GHCL => GCH2O + GCLOH : 4.6e-11 0. 0. ; * with HNO3 G4CH2OO + GHNO3 => GCH2O + GHNO4 : 5.4e-10 0. 0. ; * with O3 G4CH2OO + GO3 => GCH2O + 2.0 GO2 : 4.0e-13 0. 0. ; * with itself G4CH2OO + G4CH2OO => GCH2O + GO2 : 7.4e-11 0. 0. ; * end of file END ======================================================================= References : ------------ IUPAC 1999 : Atkinson R., D.L. Baulch, R.A. Cox, R.F. Hampson, J.A. Kerr, M. Rossi, Evaluated kinetics and photochemical data for atmospheric chemistry, organic species : Supplement VII, IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry, J. Phys. Chem. Ref. Data, 191-392, 1999 Tyndall, G.S. ; Cox, R.A. ; Granier, C. ; Lesclaux, R. ; Moortgat, G.K. ; Pilling, M.J. ; Ravishankara, A.R. ; Wallington, T.J., Atmospheric chemistry of small organic peroxy radicals, J. Geophys. Res., 12,157-12,181, 2001