B. Reactions and rates of the CB99 chemical mechanism

The Kinetic PreProcessor (KPP) is used to generate chemistry modules in FORTRAN.  To generate a module with KPP, three input files are needed: a file with all equations and reaction rates, a file with all species, and a file with specific instructions.  This appendix includes input files with equations and reaction rates for the CBIV_99 mechanism.

 

Clear sky photolysis rates are calculated according to the Roeths flux algorithm (Poppe et al, 1996):

 

PHUX(A,B,C) = A*exp(B(1-1/cosCθ))

 

with A the photolysis rate at an overhead sun (θ=0) and C a correction factor to account for the bending of solar radiation through scattering in the atmosphere. θ is the solar zenith angle (see Annex A).

 

Troe and Lindemann-Hinshelwood (LMHW) rate constants are used to relate pressure and temperature dependencies exhibited by several of the reactions in CB-IV_99 (Adelman, 1999).  The following two boxes show the source code of the Troe and LMHW functions that are called in the following reaction list.

 

 

C--- TROE function

 

      DOUBLE PRECISION FUNCTION

    +           TROE(kzero,mzero,kinf,minf,fmulti,MN2,tk)

      DOUBLE PRECISION kzero,mzero,kinf,minf,fmulti,MN2,tk,

    +                 klow,khigh

 

      klow = (kzero*(tk/300.D0)**mzero)*MN2

      khigh = kinf*(tk/300.D0)**minf

      TROE = ( klow/(1.D0+(klow/khigh))) * fmulti **

    +              ((1.D0+(DLOG10(klow/khigh))**2.D0)**(-1.D0))

      END

 

 

 

RK28 function (LMHW):

 

      DOUBLE PRECISION FUNCTION

     +          RK28(k0a,k0ea,k2a,k2ea,k3a,k3ea,MN2,tk)

      DOUBLE PRECISION k0a,k0ea,k2a,k2ea,k3a,k3ea,MN2,tk

 

      RK28 = (k0a*DEXP(k0ea/tk)) + (k3a*DEXP(k3ea/tk)*MN2) /

    +              (1.D0+((k3a*DEXP(k3ea/tk)*MN2)/(k2a*DEXP(k2ea/tk))))

      END

 

EQUATIONS {CB99 mechanism}

 

{NO2 Photolysis}

 

{ 1.} NO2 + hv = NO + O                                  

 PHUX(1.07D-2,1.01319D0,0.83330D0)

{ 2.} O + O2 + M = O3                                      

 6.D-34*(TEMP/300.D0)**(-2.3D0) ;

{ 3.} O3 + NO = NO2                                         

 2.D-12*DEXP(-1400.D0/TEMP) ;

{ 4.} O + NO2 = NO                                           

 6.5D-12*DEXP(120.D0/TEMP) ;

{ 5.} O+NO2=NO3                             

 TROE(9.D-32,-2.D0,

 2.2D-11,0.D0,0.6D0,M,TEMP) ;

{ 6.} O+NO=NO2               

 TROE(9.D-32,-1.5D0,

 3.D-11,0.D0,0.6D0,M,TEMP) ;

 

 

{Ozone Photolysis}

 

{ 7.} O3 + NO2 = NO3                                       

 1.2D-13*DEXP(-2450.D0/TEMP) ;

{ 8.} O3 + hv = O                                

 PHUX(5.36D-4,0.34764D0,0.9103D0)

{ 9.} O3 + hv = O1D                                          

 PHUX(3.22D-5,4.45037D0,0.78028D0)

{10.} O1D + M = O                                            

 1.92D-11*DEXP(126.D0/TEMP) ;

{11.} O1D + H2O = 2 OH                  

 2.2D-10 ;

{12.} O3 + OH = HO2                                        

 1.6D-12*DEXP(-940.D0/TEMP) ;

{13.} O3 + HO2 = OH                                        

 1.1D-14*DEXP(-580.D0/TEMP) ;

 

 

{NO3 Chemistry}

 

{14.} NO3 + hv = NO                                        

 PHUX(2.74D-2,0.26226D0,0.92849D0)

 

{15.} NO3 + hv = NO2 + O               

 PHUX(2.73D-1,0.29327D0,0.92401D0)

{16.} NO3 + NO = 2 NO2                  

 1.5D-11*DEXP(170.D0/TEMP) ;

{17.} NO3 + NO2 = NO + NO2                        

 4.5D-14*DEXP(-1260.D0/TEMP) ;

{18.} NO3+NO2=N2O5     

TROE(2.2D-30,-3.9D0,

1.5D-12,-0.7D0,0.6D0,M,TEMP) ;

{19.} N2O5 = NO3 + NO2

 RCONST(18) /

(2.7D-27* DEXP(11000.D0/TEMP)) ;

{20.} N2O5 + H2O = HNO3 + HNO3              

 1.5D-21;

 

 

{HONO Chemistry}

 

{21.} NO + NO + O2 = 2 NO2                          

 3.3D-39*DEXP(530.D0/TEMP) ;

{22.} NO + NO2 + H2O = 2 HONO  

 4.4D-40 ;

{23.} OH+NO=HONO

 TROE(7.D-31,-2.6D0,

 3.6D-11,-0.1D0,0.6D0,M,TEMP) ;

{24.} HONO + hv = OH + NO                          

 0.1975D0 * RCONST(1) ;

{25.} OH + HONO = NO2                 

 1.8D-11*DEXP(-390.D0/TEMP) ;

{26.} HONO + HONO = NO + NO2 

 1.D-20;

 

 

{OH/HO2 Termination Reactions}

 

{27.} OH + NO2 = HNO3

 TROE(2.6D-30,-2.9D0,

 7.5D-11,-0.6D0,0.41D0,M,TEMP);

{28.} OH+HNO3=NO3

 RK28(7.2D-15,785.D0,4.1D-16,1440.D0,1.9D-33,725.D0,M);

{29.} HO2 + NO = OH + NO2                          

 3.5D-12*DEXP(250.D0/TEMP);

{30.} HO2+NO2=PNA

 TROE(1.8D-31,-3.2D0,

 4.7D-12,-1.4D0,0.6D0,M,TEMP) ;

{31.} PNA = HO2 + NO2   

 RCONST(30) /

(2.1D-27* DEXP(10900.D0/TEMP)) ;

{32.} OH + PNA = NO2                                    

 1.3D-12*DEXP(380.D0/TEMP) ;

{33.} HO2 + HO2 = H2O2                 

 2.3D-13*DEXP(600.D0/TEMP) ;

{34.} HO2 + HO2 + M = H2O2                        

 1.7D-33*DEXP(1000.D0/TEMP) ;

{35.} H2O2 + hv = 2 OH                                   

 PHUX(7.78D-6,1.91463D0,0.7981D0)

{36.} OH + H2O2 = HO2                                   

 2.9D-12*DEXP(-190.D0/TEMP) ;

 

 

{Propagation Reactions}

 

{37.} OH + CO  = HO2

 1.5D-13*(TEMP/300.D0)*                (1.D0+0.6D0*PATM) ;

{38.} OH + CH4 = XO2 + HCHO + HO2         

 2.45D-12*DEXP(-1775.D0/TEMP) ;

 

 

{Formaldehyde Reactions}

 

{39.} HCHO + OH  = HO2 + CO                      

 8.6D-12*DEXP(20.D0/TEMP) ;

{40.} HCHO + hv = 2 HO2 + CO                      

PHUX(4.05D-5,2.06917D0,0.80267D0)

{41.} HCHO + hv = CO                                     

PHUX(4.92D-5,1.60973D0,0.80184D0)

{42.} HCHO + O = OH + HO2 + CO

 3.4D-11*DEXP(-1600.D0/TEMP) ;

{43.} HCHO + NO3 = HNO3 + HO2 + CO      

 2.D-12*DEXP(-2430.D0/TEMP) ;

 

 

{Higher Aldehyde Chemistry}

 

{44.} ALD2 + O  = C2O3 + OH                        

 1.8D-11*DEXP(-1100.D0/TEMP) ;

{45.} ALD2 + OH = C2O3                 

 5.6D-12*DEXP(270.D0/TEMP) ;

{46.} ALD2 + NO3 = C2O3 + HNO3               

 1.4D-12*DEXP(-1900.D0/TEMP) ;

{47.} ALD2 + hv = HCHO + XO2 + CO + 2 HO2       

 PHUX(5.4D-6,2.52915D0,0.79722D0)

 

 

{PAN Chemistry}

 

{48.} C2O3 + NO = HCHO + XO2 + HO2 + NO2       

 5.3D-12*DEXP(360.D0/TEMP) ;

{49.} C2O3+NO2=PAN

 TROE(2.7D-28,-7.1D0,

 1.2D-11,-0.9D0,0.3D0,M,TEMP) ;

{50.} PAN = C2O3 + NO2

 RCONST(49) /

(9.D-29* DEXP(14000.D0/TEMP) ;

{51.} 2 C2O3 = 2 HCHO + 2 XO2 + 2 HO2

 2.8D-12*DEXP(530.D0/TEMP) ;

{52.} C2O3 + HO2 = 0.25 O3                            

 4.3D-13*DEXP(1040.D0/TEMP) ;

 

 

{Paraffin Chemistry}

 

{53.} PAR + OH =  0.87 XO2 + 0.13 XO2N + 0.11 HO2 + 0.11 ALD2 + 0.76 ROR - 0.11 PAR               

 8.1D-13 ;

{54.} ROR = 1.1 ALD2 + 0.96 XO2 + 0.94 HO2 + 0.04 XO2N + 0.02 ROR - 2.10 PAR      

 1.D+15*DEXP(-8000.D0/TEMP) ;

{55.} ROR =  HO2                                              

 1.6D+3 ;

{56.} ROR + NO2 =  NTR                 

 1.5D-11 ;

 

 

{Olefin Chemistry}

 

{57.} O + OLE = 0.49 ALD2 + 0.29 HO2 + 0.19 XO2 + 0.2 CO + 0.2 HCHO + 0.007 XO2N + 0.61 PAR + 0.1 OH                          

 4.D-12 ;

{58.} OH + OLE = 0.71 HCHO + 0.95 ALD2 + 0.71 XO2 + 0.95 HO2  - 0.71PAR                     

 TROE(8.D-27,-3.5D0,

 3.D-11,0.D0,0.5D0,M,TEMP) ;

{59.} O3 + OLE = 0.52 ALD2 + 0.86 HCHO + 0.08 H2O2 + 0.3947 CO + 0.42 HO2 + 0.45 XO2 + 0.6 CH4 + 0.3 OH - PAR                       

 5.5D-15*DEXP(-1880.D0/TEMP) ;

{60.} NO3 + OLE = 0.91 XO2 + HCHO + ALD2 + 0.09 XO2N + NO2 - PAR

 4.6D-13*DEXP(-1155.D0/TEMP) ;

 

 

{Ethene Chemistry}

 

{61.} O + ETH = 0.6 XO2 + 0.95 CO + 1.55 HO2 + 0.35 OH

 1.04D-11*DEXP(-792.D0/TEMP) ;

{62.} OH + ETH = XO2 + 1.56 HCHO + HO2 + 0.22ALD2         

 TROE(7.D-29,-3.1D0,

 9.D-12,0.D0,0.7D0,M,TEMP) ;

{63.} O3 + ETH = 1.02 HCHO + 0.325 CO + 0.08 HO2 + 0.08 OH + 0.02 H2O2

 9.14D-15*DEXP(-2580.D0/TEMP) ;

 

 

{Aromatic Chemistry}

 

{64.} OH + TOL = 0.08 XO2 + 0.36 CRES + 0.44 HO2 + 0.56 TO2

1.81D-12*DEXP(355.D0/TEMP) ;

{65.} TO2 + NO =  0.9 NO2 + 0.9 OPEN + 0.9 HO2 + 0.1 NTR    

 8.1D-12 ;

{66.} TO2 = HO2 + CRES                 

 4.2D0 ;

{67.} OH + CRES = 0.4 CRO + 0.6 XO2 + 0.6 HO2 + 0.3 OPEN 

 4.1D-11 ;

{68.} NO3 + CRES = CRO + HNO3 

 2.2D-11 ;

{69.} CRO + NO2 = NTR   

 1.4D-11 ;

{70.} OH + XYL = 0.7 HO2 + 0.1 XO2 + 0.2 CRES + 0.8 MGLY + 1.10 PAR + 0.3 TO2                       

 1.7D-11*DEXP(116.D0/TEMP) ;

{71.} OH + OPEN = XO2 + C2O3 + 2 HO2 + 2 CO + HCHO

 3.D-11 ;

{72.} OPEN + hv = C2O3 + CO + HO2            

 6.D0*RCONST(40) ;

{73.} O3 + OPEN = 0.03 ALD2 + 0.62 C2O3 + 0.7 HCHO + 0.03 XO2 + 0.69 CO + 0.08 OH + 0.76 HO2 + 0.2 MGLY

 5.4D-17*DEXP(-500.D0/TEMP) ;

{74.} OH + MGLY = XO2 + C2O3   

 1.7D-11 ;

{75.} MGLY + hv = C2O3 + CO + HO2           

 6.D0*RCONST(40) ;

 

 

{Isoprene Chemistry Condensed}

 

{76.} ISOP + O = 0.75 ISPD + 0.5 HCHO + 0.25 XO2 + 0.25 HO2 + 0.25 C2O3 + 0.25 PAR               

 3.6D-11 ;

{77.} ISOP + OH = 0.912 ISPD + 0.629 HCHO + 0.991 XO2 + 0.912 HO2+0.088XO2N                           

 2.54D-11*DEXP(407.6D0/TEMP) ;

{78.} ISOP + O3 = 0.65 ISPD + 0.6 HCHO + 0.2 XO2 + 0.066 HO2 + 0.266 OH + 0.2 C2O3 + 0.15 ALD2 + 0.35 PAR + 0.066 CO

7.86D-15*DEXP(-1912.D0/TEMP) ;

{79.} ISOP + NO3 = 0.2 ISPD + 0.8 NTR + XO2 + 0.8 HO2 + 0.2 NO2 + 0.8 ALD2 + 2.4 PAR      

 3.03D-12*DEXP(-448.D0/TEMP) ;

{80.} ISOP + NO2 = 0.2 ISPD + 0.8 NTR + XO2 + 0.8 HO2 + 0.2 NO + 0.8 ALD2 + 2.4 PAR      

 1.5D-19 ;

 

 

{Operator Chemistry}

 

{81.} XO2 + NO = NO2                                     

 3.D-12*DEXP(280.D0/TEMP) ;

{82.} XO2 + XO2 = PROD                

 2.5D-13*DEXP(190.D0/TEMP) ;

{83.} XO2N + NO = NTR                  

 3.D-12*DEXP(280.D0/TEMP) ;

{84.} SO2+OH=HO2+SULF

 TROE(3.D-31,-3.3D0,

 1.5D-12,0.D0,0.6D0,M,TEMP) ;

{85.} SO2  = SULF                                             

 1.4D-6 ;

{86.} MEOH + OH = HCHO + HO2 

 6.7E-12*DEXP(600.D0/TEMP) ;

{87.} ETOH + OH = 0.11 HCHO + 0.945 ALD2 + HO2 + 0.055 XO2                                

 7.D-12*DEXP(235.D0/TEMP) ;

{88.} XO2 + HO2 = PROD                

 3.8D-13*DEXP(800.D0/TEMP) ;

{89.} XO2N + HO2 = PROD                             

 3.8D-13*DEXP(800.D0/TEMP) ;

{90.} XO2N + XO2N = PROD                          

 2.5D-13*DEXP(190.D0/TEMP) ;

{91.} XO2N + XO2 = PROD                             

 2.D0*2.5D-13*DEXP(190.D0/TEMP) ;

 

 

{Additional Isoprene Chemistry}

 

{92.} ISPD + OH = 1.565 PAR + 0.167 HCHO + 0.713 XO2 + 0.503 HO2 + 0.334 CO + 0.168 MGLY + 0.273 ALD2 + 0.498 C2O3

 3.36D-11 ;

{93.} ISPD + O3 = 0.114 C2O3 + 0.15 HCHO + 0.85 MGLY + 0.154 HO2 + 0.268 OH + 0.064 XO2 + 0.020 ALD2 + 0.360 PAR + 0.225 CO  

 7.11D-18 ;

{94.} ISPD + NO3 = 0.357 ALD2 + 0.282 HCHO + 1.282 PAR + 0.925 HO2 + 0.643 CO + 0.850 NTR + 0.075 C2O3 + 0.075 XO2 + 0.075 HNO3

 1.D-15 ;

{95.} ISPD + hv = 0.333 CO + 0.067 ALD2 + 0.9 HCHO + 0.832 PAR + 1.033 HO2 + 0.7 XO2 + 0.967 C2O3

 1.70D-4*RCONST(1);