! RCS file, release, date & time of last delta, author, state, [and locker] ! $Header: /project/work/rep/include/ICL/src/mech/cb05_ae4_aq/mech.def,v 1.2 2006/05/23 15:45:44 sjr Exp $ ! what(1) key, module and SID; SCCS file; date and time of last delta: ! %W% %P% %G% %U% CB05_AE4_AQ ! CB05 Mechanism ! Created from cb4_plus_mech_012005.def.txt provided by Greg Yarwood on ! 01/20/2005 ! Modified by Golam Sarwar for CMAQ implementation: ! 1) Lines were reformatted to limit the lengths within 81 spaces ! 2) Modified labels of photolysis reactions (maximum length 16 characters) ! ACROLEIN_CBIVPLUS exceeded 16 characters; all CBIVPLUS have been changed ! to CBIV05 ! Photolysis data completely revised by Greg Yarwood on 02/11/05. Using a ! combination of SAPRC99 data and IUPAC 2004. No data found for PACD ! (perxoyacetic acid) so set to zero for now. ! Modified R2, R10, and R113 by Gary Whitten on 23 Feb ’05 to conform to better ! conform to CMAQ and original CB4 of Gery et al ’89. ! Modified R103 and R104 to be same as R88 and R89 due to inconsistencies in ! trends between IUPAC ’04 and NASA ’03 concerning PAN and PPN and due to the ! differences being within the error estimates. ! Gary Whitten fixed Rxn’s 123, 137, 149, 150, and added 156 on 25 March, 2005 ! Modified R65, OH + CO, rate constant to use the IUPAC 2005 expression for N2 ! as third body (M). Implicit assumption that O2 has the same collisional ! efficiency as N2. Greg Yarwood 07/12/05. ! ! Modified the rate constants for reactions of N2O5 with H2O (R19 and R20). ! Heterognenous reaction involving N2O5 is incorporated in the aerosol module. ! Rate constants for these two reactions are set to 0.0 in the gas phase mechanism. ! Golam Sarwar 07/26/2005 ! ! Modified by Golam Sarwar 7/26/2005 to include gaseous species that ! are necessary to link gas-phase chemistry to aerosol formation. ! New species added: ! SULAER: Gives amount of sulfuric acid produced ! TOLAER: Gives total amount of TOL reacted ! XYLAER: Gives total amount of XYL reacted ! CSLAER: Gives total amount of CSL reacted ! TERPAER: Gives total amount of monoterpenes reacted ! ! Modified by Golam Sarwar 4/18/06 to use actual rate constant for RXN and ! !----------------------------------80 Characters Wide--------------------------- REACTIONS[CM] = < R1> NO2 = NO + O # 1.0/; < R2> O + O2 + M = O3 + M # 6.0E-34 ^ -2.4; < R3> O3 + NO = NO2 # 3.0E-12 @ 1500.0; < R4> O + NO2 = NO # 5.6E-12 @ -180.0; < R5> O + NO2 = NO3 # 2.5E-31 ^-1.8 & 2.2E-11 ^ -0.7; < R6> O + NO = NO2 # 9.0E-32 ^ -1.5 & 3.0E-11; < R7> NO2 + O3 = NO3 # 1.2E-13 @ 2450; < R8> O3 = O # 1.0/; < R9> O3 = O1D # 1.0/; < R10> O1D + M = O + M # 2.1E-11 @ -102.; < R11> O1D + H2O = 2.000*OH # 2.2E-10; < R12> O3 + OH = HO2 # 1.7E-12 @ 940; < R13> O3 + HO2 = OH # 1.0E-14 @ 490; < R14> NO3 = NO2 + O # 1.0/; < R15> NO3 = NO # 1.0/; < R16> NO3 + NO = 2.000*NO2 # 1.5E-11 @ -170; < R17> NO3 + NO2 = NO + NO2 # 4.5E-14 @ 1260; < R18> NO3 + NO2 = N2O5 # 2.0E-30 ^ -4.4 & 1.4E-12 ^ -0.7; < R19> N2O5 + H2O = 2.000*HNO3 # 2.5E-22; < R20> N2O5 + H2O + H2O = 2.000*HNO3 # 1.8E-39; < R21> N2O5 = NO3 + NO2 # 1.0E-03 ^-3.5 @ 11000 & 9.7E+14 ^ 0.1 @ 11080 & 0.45 & 1.0; < R22> NO + NO + O2 = 2.000*NO2 # 3.3E-39 @ -530; < R23> NO + NO2 + H2O = 2.000*HONO # 5.0E-40; < R24> NO + OH = HONO # 7.0E-31 ^ -2.6 & 3.6E-11 ^ -0.1; < R25> HONO = NO + OH # 1.0/; < R26> OH + HONO = NO2 # 1.8E-11 @ 390; < R27> HONO + HONO = NO + NO2 # 1.0E-20; < R28> NO2 + OH = HNO3 # 2.0E-30 ^ -3.0 & 2.5E-11; < R29> OH + HNO3 = NO3 %2 # 2.4E-14 @ -460 & 2.7E-17 @ -2199 & 6.5E-34 @ -1335; < R30> HO2 + NO = OH + NO2 # 3.5E-12 @ -250; < R31> HO2 + NO2 = PNA # 1.8E-31 ^ -3.2 & 4.7E-12 & 0.6; < R32> PNA = HO2 + NO2 # 4.1E-5 @ 10650 & 4.8E15 @ 11170 & 0.6; < R33> OH + PNA = NO2 # 1.3E-12 @ -380; < R34> HO2 + HO2 = H2O2 %3 # 2.3E-13 @ -600 & 1.7E-33 @ -1000; < R35> HO2 + HO2 + H2O = H2O2 %3 # 3.22E-34 @ -2800 & 2.38E-54 @ -3200; < R36> H2O2 = 2.000*OH # 1.0/; < R37> OH + H2O2 = HO2 # 2.9E-12 @ 160; < R38> O1D + H2 = OH + HO2 # 1.1E-10; < R39> OH + H2 = HO2 # 5.5E-12 @ 2000.; < R40> OH + O = HO2 # 2.2E-11 @ -120.; < R41> OH + OH = O # 4.2E-12 @ 240; < R42> OH + OH = H2O2 # 6.9E-31 ^ -1.0 & 2.6E-11 ^ 0; < R43> OH + HO2 = # 4.8E-11 @ -250.; < R44> HO2 + O = OH # 3.0E-11 @ -200.; < R45> H2O2 + O = OH + HO2 # 1.4E-12 @ 2000.; < R46> NO3 + O = NO2 # 1.0E-11; < R47> NO3 + OH = HO2 + NO2 # 2.2E-11; < R48> NO3 + HO2 = HNO3 # 3.5E-12; < R49> NO3 + O3 = NO2 # 1.0E-17; < R50> NO3 + NO3 = 2.000*NO2 # 8.5E-13 @ 2450.; < R51> PNA = 0.610*HO2 + 0.610*NO2 + 0.390*OH + 0.390*NO3 # 1.0/; < R52> HNO3 = OH + NO2 # 1.0/; < R53> N2O5 = NO2 + NO3 # 1.0/; < R54> XO2 + NO = NO2 # 2.6E-12 @ -365; < R55> XO2N + NO = NTR # 2.6E-12 @ -365; < R56> XO2 + HO2 = ROOH # 7.5E-13 @ -700; < R57> XO2N + HO2 = ROOH # 7.5E-13 @ -700; < R58> XO2 + XO2 = # 6.8E-14; < R59> XO2N + XO2N = # 6.8E-14; < R60> XO2 + XO2N = # 6.8E-14; < R61> NTR + OH = HNO3 + HO2 + 0.330*FORM + 0.330*ALD2 + 0.330*ALDX - 0.660*PAR # 5.9E-13 @ 360.; < R62> NTR = NO2 + HO2 + 0.330*FORM + 0.330*ALD2 + 0.330*ALDX - 0.660*PAR # 1.0/; < R63> ROOH + OH = XO2 + 0.500*ALD2 + 0.500*ALDX # 3.01E-12 @ -190; < R64> ROOH = OH + HO2 + 0.500*ALD2 + 0.500*ALDX # 1.0/; < R65> OH + CO = HO2 %3 # 1.44E-13 @ 0.0 & 3.43E-33 @ 0.0; < R66> OH + CH4 = MEO2 # 2.45E-12 @ 1775; < R67> MEO2 + NO = FORM + HO2 + NO2 # 2.8E-12 @ -300; < R68> MEO2 + HO2 = MEPX # 4.1E-13 @ -750; < R69> MEO2 + MEO2 = 1.370*FORM + 0.740*HO2 + 0.630*MEOH # 9.5E-14 @ -390; < R70> MEPX + OH = 0.700*MEO2 + 0.300*XO2 + 0.300*HO2 # 3.8E-12 @ -200; < R71> MEPX = FORM + HO2 + OH # 1.0/; < R72> MEOH + OH = FORM + HO2 # 7.3E-12 @ 620; < R73> FORM + OH = HO2 + CO # 9.0E-12; < R74> FORM = 2.000*HO2 + CO # 1.0/; < R75> FORM = CO # 1.0/; < R76> FORM + O = OH + HO2 + CO # 3.4E-11 @ 1600; < R77> FORM + NO3 = HNO3 + HO2 + CO # 5.8E-16; < R78> FORM + HO2 = HCO3 # 9.7E-15 @ -625; < R79> HCO3 = FORM + HO2 # 2.4E+12 @ 7000; < R80> HCO3 + NO = FACD + NO2 + HO2 # 5.6E-12; < R81> HCO3 + HO2 = MEPX # 5.6E-15 @ -2300; < R82> FACD + OH = HO2 # 4.0E-13; < R83> ALD2 + O = C2O3 + OH # 1.8E-11 @ 1100; < R84> ALD2 + OH = C2O3 # 5.6E-12 @ -270; < R85> ALD2 + NO3 = C2O3 + HNO3 # 1.4E-12 @ 1900; < R86> ALD2 = MEO2 + CO + HO2 # 1.0/; < R87> C2O3 + NO = MEO2 + NO2 # 8.1E-12 @ -270; < R88> C2O3 + NO2 = PAN # 2.7E-28 ^ -7.1 & 1.2E-11 ^ -0.9 & 0.3; < R89> PAN = C2O3 + NO2 # 4.9E-3 @ 12100 & 5.4E16 @ 13830 & 0.3; < R90> PAN = C2O3 + NO2 # 1.0/; < R91> C2O3 + HO2 = 0.800*PACD + 0.200*AACD + 0.200*O3 # 4.3E-13 @ -1040; < R92> C2O3 + MEO2 = 0.900*MEO2 + 0.900*HO2 + FORM + 0.100*AACD # 2.0E-12 @ -500; < R93> C2O3 + XO2 = 0.900*MEO2 + 0.100*AACD # 4.4E-13 @ -1070 ; < R94> C2O3 + C2O3 = 2.000*MEO2 # 2.9E-12 @ -500; < R95> PACD + OH = C2O3 # 4.0E-13 @ -200; < R96> PACD = MEO2 + OH # 0.0/; < R97> AACD + OH = MEO2 # 4.0E-13 @ -200; < R98> ALDX + O = CXO3 + OH # 1.3E-11 @ 870; < R99> ALDX + OH = CXO3 # 5.1E-12 @ -405; ALDX + NO3 = CXO3 + HNO3 # 6.5E-15; ALDX = MEO2 + CO + HO2 # 1.0/; CXO3 + NO = ALD2 + NO2 + HO2 + XO2 # 6.7E-12 @ -340; CXO3 + NO2 = PANX # 2.7E-28 ^ -7.1 & 1.2E-11 ^ -0.9 & 0.3; PANX = CXO3 + NO2 # 4.9E-3 @ 12100 & 5.4E16 @ 13830 & 0.3; PANX = CXO3 + NO2 # 1.0/; PANX + OH = ALD2 + NO2 # 3.0E-13; CXO3 + HO2 = 0.800*PACD + 0.200*AACD + 0.200*O3 # 4.3E-13 @ -1040; CXO3 + MEO2 = 0.900*ALD2 + 0.900*XO2 + HO2 + 0.100*AACD + 0.100*FORM # 2.0E-12 @ -500; CXO3 + XO2 = 0.900*ALD2 + 0.100*AACD # 4.4E-13 @ -1070.; CXO3 + CXO3 = 2.000*ALD2 + 2.000*XO2 + 2.000*HO2 # 2.9E-12@-500; CXO3 + C2O3 = MEO2 + XO2 + HO2 + ALD2 # 2.9E-12@-500; PAR + OH = 0.870*XO2 + 0.130*XO2N + 0.110*HO2 + 0.060*ALD2 - 0.110*PAR + 0.760*ROR + 0.050*ALDX # 8.1E-13; ROR = 0.960*XO2 + 0.600*ALD2 + 0.940*HO2 - 2.100*PAR + 0.040*XO2N + 0.020*ROR + 0.500*ALDX # 1.E+15 @ 8000.; ROR = HO2 # 1.6E+3; ROR + NO2 = NTR # 1.5E-11; O + OLE = 0.200*ALD2 + 0.300*ALDX + 0.300*HO2 + 0.200*XO2 + 0.200*CO + 0.200*FORM + 0.010*XO2N + 0.200*PAR + 0.100*OH # 1.E-11 @ 280.; OH + OLE = 0.800*FORM + 0.330*ALD2 + 0.620*ALDX + 0.800*XO2 + 0.950*HO2 - 0.700*PAR # 3.2E-11; O3 + OLE = 0.180*ALD2 + 0.740*FORM + 0.320*ALDX + 0.220*XO2 + 0.100*OH + 0.330*CO + 0.440*HO2 - 1.000*PAR # 6.5E-15 @ 1900.; NO3 + OLE = NO2 + FORM + 0.910*XO2 + 0.090*XO2N + 0.560*ALDX + 0.350*ALD2 - 1.000*PAR # 7.0E-13 @ 2160.; O + ETH = FORM + 1.700*HO2 + CO + 0.700*XO2 + 0.300*OH # 1.04E-11 @ 792; OH + ETH = XO2 + 1.560*FORM + 0.220*ALDX + HO2 # 1.0E-28 ^-0.8 & 8.8E-12; O3 + ETH = FORM + 0.630*CO + 0.130*HO2 + 0.130*OH + 0.370*FACD # 1.2E-14 @ 2630; NO3 + ETH = NO2 + XO2 + 2.0*FORM # 3.3E-12 @ 2880.; IOLE + O = 1.240*ALD2 + 0.660*ALDX + 0.100*HO2 + 0.100*XO2 + 0.100*CO + 0.100*PAR # 2.3E-11; IOLE + OH = 1.300*ALD2 + 0.700*ALDX + HO2 + XO2 # 1.0E-11 @ -550.; IOLE + O3 = 0.650*ALD2 + 0.350*ALDX + 0.250*FORM + 0.250*CO + 0.500*O + 0.500*OH + 0.500*HO2 # 8.4E-15 @ 1100.; IOLE + NO3 = 1.180*ALD2 + 0.640*ALDX + HO2 + NO2 # 9.6E-13 @ 270.; TOL + OH = 0.440*HO2 + 0.080*XO2 + 0.360*CRES + 0.560*TO2 + TOLAER # 1.8E-12 @ -355; TO2 + NO = 0.900*NO2 + 0.900*HO2 + 0.900*OPEN + 0.100*NTR # 8.1E-12; TO2 = CRES + HO2 # 4.2; OH + CRES = 0.400*CRO + 0.600*XO2 + 0.600*HO2 + 0.300*OPEN + CSLAER # 4.1E-11; CRES + NO3 = CRO + HNO3 + CSLAER # 2.2E-11; CRO + NO2 = NTR # 1.4E-11; CRO + HO2 = CRES # 5.5E-12; OPEN = C2O3 + HO2 + CO # 9.0/; OPEN + OH = XO2 + 2.000*CO + 2.000*HO2 + C2O3 + FORM # 3.0E-11; OPEN + O3 = 0.030*ALDX + 0.620*C2O3 + 0.700*FORM + 0.030*XO2 + 0.690*CO + 0.080*OH + 0.760*HO2 + 0.200*MGLY # 5.4E-17 @ 500.; OH + XYL = 0.700*HO2 + 0.500*XO2 + 0.200*CRES + 0.800*MGLY + 1.100*PAR + 0.300*TO2 + XYLAER # 1.7E-11 @ -116.; OH + MGLY = XO2 + C2O3 # 1.8E-11; MGLY = C2O3 + HO2 + CO # 1.0/; O + ISOP = 0.750*ISPD + 0.500*FORM + 0.250*XO2 + 0.250*HO2 + 0.250*CXO3 + 0.250*PAR # 3.6E-11; OH + ISOP = 0.912*ISPD + 0.629*FORM + 0.991*XO2 + 0.912*HO2 + 0.088*XO2N # 2.54E-11 @ -407.6; O3 + ISOP = 0.650*ISPD + 0.600*FORM + 0.200*XO2 + 0.066*HO2 + 0.266*OH + 0.200*CXO3 + 0.150*ALDX + 0.350*PAR + 0.066*CO # 7.86E-15 @ 1912; NO3 + ISOP = 0.200*ISPD + 0.800*NTR + XO2 + 0.800*HO2 + 0.200*NO2 + 0.800*ALDX + 2.400*PAR # 3.03E-12 @ 448; OH + ISPD = 1.565*PAR + 0.167*FORM + 0.713*XO2 + 0.503*HO2 + 0.334*CO + 0.168*MGLY + 0.252*ALD2 + 0.210*C2O3 + 0.250*CXO3 + 0.120*ALDX # 3.36E-11; O3 + ISPD = 0.114*C2O3 + 0.150*FORM + 0.850*MGLY + 0.154*HO2 + 0.268*OH + 0.064*XO2 + 0.020*ALD2 + 0.360*PAR + 0.225*CO # 7.1E-18; NO3 + ISPD = 0.357*ALDX + 0.282*FORM + 1.282*PAR + 0.925*HO2 + 0.643*CO + 0.850*NTR + 0.075*CXO3 + 0.075*XO2 + 0.150*HNO3 # 1.0E-15; ISPD = 0.333*CO + 0.067*ALD2 + 0.900*FORM + 0.832*PAR + 1.033*HO2 + 0.700*XO2 + 0.967*C2O3 # 0.0036/; TERP + O = 0.150*ALDX + 5.12*PAR + TERPAER # 3.6E-11; TERP + OH = 0.750*HO2 + 1.250*XO2 + 0.250*XO2N + 0.280*FORM + 1.66* PAR + 0.470*ALDX + TERPAER # 1.5E-11 @ -449.; TERP + O3 = 0.570*OH + 0.070*HO2 + 0.760*XO2 + 0.180*XO2N + 0.240*FORM + 0.001*CO + 7.000*PAR + 0.210*ALDX + 0.390*CXO3 + TERPAER # 1.2E-15 @ 821.; TERP + NO3 = 0.470*NO2 + 0.280*HO2 + 1.030*XO2 + 0.250*XO2N + 0.470*ALDX + 0.530*NTR + TERPAER # 3.7E-12 @ -175.; SO2 + OH = SULF + HO2 + SULAER # 3.0E-31 ^-3.3 & 1.5E-12; OH + ETOH = HO2 + 0.900*ALD2 + 0.050*ALDX + 0.100*FORM + 0.100*XO2 # 6.9E-12 @ 230; OH + ETHA = 0.991*ALD2 + 0.991*XO2 + 0.009*XO2N + HO2 # 8.7E-12 @ 1070; NO2 + ISOP = 0.200*ISPD + 0.800*NTR + XO2 + 0.800*HO2 + 0.200*NO + 0.800*ALDX + 2.400*PAR # 1.5E-19; END MECH