! Mechanism for Chemiluminescent species and C3 submechanism ! Citation: Kathrotia et al., Appl. Phys. B 107, 3, 571-584 (2012) ! Contact: trupti.kathrotia(at)dlr.de ! General Nomenclature: ! P: Primary, S: Secondary, T: Tertiary, A: allyl, I: Iso, N: n ! ELEMENTS C H O N AR END SPECIES ! Species specific to Chemiluminescence and C3 subpart C C2 C2O C3 C3H C3H2 OH* CH(A) CH(B) !CH* A- and B-states C2* ! Check for duplicates in base mechanism O O2 H H2 H2O OH HCO HCCO CO CO2 CH CH2(S) CH2 CH3 CH4 C2H C2H2 C2H3 C2H4 C2H5 C2H6 AR N2 ! END THERMO ALL 200.00 1000.00 6000.00 C C 1 G 200.00 6000.00 1000.00 1 ! L 7/88 2.60558300E+00-1.95934340E-04 1.06737220E-07-1.64239400E-11 8.18705800E-16 2 8.54117420E+04 4.19238680E+00 2.55423950E+00-3.21537720E-04 7.33792230E-07 3 -7.32234870E-10 2.66521440E-13 8.54426810E+04 4.53130850E+00 4 C2 C 2 G 200.00 6000.00 1000.00 1 ! T05/09 3.43350371E+00 1.07185010E-03-3.97897382E-07 6.67457391E-11-4.10152154E-15 2 1.00178987E+05 4.10588356E+00 3.76163273E+00-2.72143299E-03 8.69879462E-06 3 -8.19304667E-09 2.62415296E-12 1.00254566E+05 3.18038623E+00 4 C2O C 2O 1 G 200.00 5000.00 1000.00 1 ! T 7/08 5.42468378E+00 1.85393945E-03-5.17932956E-07 6.77646230E-11-3.53315237E-15 2 4.45363907E+04-3.69608405E+00 2.86278214E+00 1.19701204E-02-1.80851222E-05 3 1.52777730E-08-5.20063163E-12 4.51328492E+04 8.89759099E+00 4 C3 C 3 G 200.00 6000.00 1000.00 1 ! singlet T04/09 4.80363533E+00 2.14513832E-03-1.07293374E-06 2.60738413E-10-2.01634398E-14 2 9.72408769E+04 3.89374482E-01 5.43290497E+00-4.46759757E-03 1.49323279E-05 3 -1.47954918E-08 5.01427143E-12 9.73400585E+04-1.58722640E+00 4 C3H C 3H 1 G 200.00 6000.00 1000.00 1 ! l HCCC A 7/05 6.14184491E+00 3.39661013E-03-1.21915444E-06 1.97782838E-10-1.18312807E-14 2 8.44225753E+04-6.44480148E+00 3.34917187E+00 1.65822626E-02-2.77115653E-05 3 2.51382364E-08-8.85285352E-12 8.49863168E+04 6.80362439E+00 4 C3H2 C 3H 2 G 200.00 6000.00 1000.00 1 ! H2C*-CC* T12/00 6.67324762E+00 5.57728845E-03-1.99180164E-06 3.20289156E-10-1.91216272E-14 2 7.57571184E+04-9.72894405E+00 2.43417332E+00 1.73013063E-02-1.18294047E-05 3 1.02756396E-09 1.62626314E-12 7.69074892E+04 1.21012230E+01 4 OH* H 1O 1 G 200.00 6000.00 1000.00 1 ! 2SigmaATcTA 2.75582920E+00 1.39848756E-03-4.19428493E-07 6.33453282E-11-3.56042218E-15 2 5.09751756E+04 5.62581429E+00 3.46084428E+00 5.01872172E-04-2.00254474E-06 3 3.18901984E-09-1.35451838E-12 5.07349466E+04 1.73976415E+00 4 CH(A) C 1H 1 G 200.00 6000.00 1000.00 1 ! DEG7/08 2.78220752E+00 1.47246754E-03-4.63436227E-07 7.32736021E-11-4.19705404E-15 2 1.04547060E+05 5.17421018E+00 3.47250101E+00 4.26443626E-04-1.95181794E-06 3 3.51755043E-09-1.60436174E-12 1.04334869E+05 1.44799533E+00 4 CH(B) C 1H 1 G 200.00 6000.00 1000.00 1 ! DEG7/08 3.10123129E+00 1.48670484E-03-3.88548896E-07 1.04667880E-10-4.71283513E-15 2 1.08312371E+05 3.30360492E+00 3.69510692E+00-1.80505435E-03 5.03652887E-06 3 -3.23608801E-09 6.08848851E-13 1.08268493E+05 7.40672572E-01 4 C2* C 2 G 300.00 5000.00 1000.00 1 ! 121286 4.13597900E+00 6.53161800E-05 1.83709900E-07-5.29508500E-11 4.71213700E-15 2 1.33059778E+05 7.47292300E-01 6.99604500E+00-7.40060200E-03 3.23470400E-06 3 4.80253500E-09-3.29591800E-12 1.32361928E+05-1.38622700E+01 4 O O 1 G 200.00 6000.00 1000.00 1 ! L 1/90 2.54363697E+00-2.73162486E-05-4.19029520E-09 4.95481845E-12-4.79553694E-16 2 2.92260120E+04 4.92229457E+00 3.16826710E+00-3.27931884E-03 6.64306396E-06 3 -6.12806624E-09 2.11265971E-12 2.91222592E+04 2.05193346E+00 4 O2 O 2 G 200.00 6000.00 1000.00 1 ! RUS 89 3.66096083E+00 6.56365523E-04-1.41149485E-07 2.05797658E-11-1.29913248E-15 2 -1.21597725E+03 3.41536184E+00 3.78245636E+00-2.99673415E-03 9.84730200E-06 3 -9.68129508E-09 3.24372836E-12-1.06394356E+03 3.65767573E+00 4 H H 1 G 200.00 6000.00 1000.00 1 ! L 6/94 2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 2.54736600E+04-4.46682850E-01 2.50000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 2.54736600E+04-4.46682850E-01 4 H2 H 2 G 200.00 6000.00 1000.00 1 ! RUS 78 2.93283050E+00 8.26598020E-04-1.46400570E-07 1.54098510E-11-6.88796150E-16 2 -8.13055820E+02-1.02431640E+00 2.34430290E+00 7.98042480E-03-1.94779170E-05 3 2.01569670E-08-7.37602890E-12-9.17924130E+02 6.83002180E-01 4 H2O H 2O 1 G 200.00 6000.00 1000.00 1 ! L 5/89 2.67703890E+00 2.97318160E-03-7.73768890E-07 9.44335140E-11-4.26899910E-15 2 -2.98858940E+04 6.88255000E+00 4.19863520E+00-2.03640170E-03 6.52034160E-06 3 -5.48792690E-09 1.77196800E-12-3.02937260E+04-8.49009010E-01 4 OH H 1O 1 G 200.00 6000.00 1000.00 1 ! IU3/03 2.83853033E+00 1.10741289E-03-2.94000209E-07 4.20698729E-11-2.42289890E-15 2 3.69780808E+03 5.84494652E+00 3.99198424E+00-2.40106655E-03 4.61664033E-06 3 -3.87916306E-09 1.36319502E-12 3.36889836E+03-1.03998477E-01 4 HCO C 1H 1O 1 G 200.00 6000.00 1000.00 1 ! CHO T 5/03 3.92001542E+00 2.52279324E-03-6.71004164E-07 1.05615948E-10-7.43798261E-15 2 3.65342928E+03 3.58077056E+00 4.23754610E+00-3.32075257E-03 1.40030264E-05 3 -1.34239995E-08 4.37416208E-12 3.87241185E+03 3.30834869E+00 4 HCCO C 2H 1O 1 G 200.00 6000.00 1000.00 1 ! T 4/09 5.91479333E+00 3.71408730E-03-1.30137010E-06 2.06473345E-10-1.21476759E-14 2 1.93596301E+04-5.50567269E+00 1.87607969E+00 2.21205418E-02-3.58869325E-05 3 3.05402541E-08-1.01281069E-11 2.01633840E+04 1.36968290E+01 4 CO C 1O 1 G 200.00 6000.00 1000.00 1 ! RUS 79 3.04848590E+00 1.35172810E-03-4.85794050E-07 7.88536440E-11-4.69807460E-15 2 -1.42661170E+04 6.01709770E+00 3.57953350E+00-6.10353690E-04 1.01681430E-06 3 9.07005860E-10-9.04424490E-13-1.43440860E+04 3.50840930E+00 4 CO2 C 1O 2 G 200.00 6000.00 1000.00 1 ! L 7/88 4.63651110E+00 2.74145690E-03-9.95897590E-07 1.60386660E-10-9.16198570E-15 2 -4.90249040E+04-1.93489550E+00 2.35681300E+00 8.98412990E-03-7.12206320E-06 3 2.45730080E-09-1.42885480E-13-4.83719710E+04 9.90090350E+00 4 CH C 1H 1 G 200.00 6000.00 1000.00 1 ! IU3/03 2.52093690E+00 1.76536390E-03-4.61476600E-07 5.92896750E-11-3.34745010E-15 2 7.09948780E+04 7.40518290E+00 3.48975830E+00 3.24321600E-04-1.68997510E-06 3 3.16284200E-09-1.40618030E-12 7.06607550E+04 2.08428410E+00 4 CH2(S) C 1H 2 G 200.00 6000.00 1000.00 1 ! IU3/03 3.13501686E+00 2.89593926E-03-8.16668090E-07 1.13572697E-10-6.36262835E-15 2 5.05040504E+04 4.06030621E+00 4.19331325E+00-2.33105184E-03 8.15676451E-06 3 -6.62985981E-09 1.93233199E-12 5.03662246E+04-7.46734310E-01 4 CH2 C 1H 2 G 200.00 6000.00 1000.00 1 ! CH2(T) IU3/03 3.14631886E+00 3.03671259E-03-9.96474439E-07 1.50483580E-10-8.57335515E-15 2 4.60412605E+04 4.72341711E+00 3.71757846E+00 1.27391260E-03 2.17347251E-06 3 -3.48858500E-09 1.65208866E-12 4.58723866E+04 1.75297945E+00 4 CH3 C 1H 3 G 200.00 6000.00 1000.00 1 ! IU0702 2.97812060E+00 5.79785200E-03-1.97558000E-06 3.07297900E-10-1.79174160E-14 2 1.65095130E+04 4.72247990E+00 3.65717970E+00 2.12659790E-03 5.45838830E-06 3 -6.61810030E-09 2.46570740E-12 1.64227160E+04 1.67353540E+00 4 CH4 C 1H 4 G 200.00 6000.00 1000.00 1 ! g 8/99 1.65326226E+00 1.00263099E-02-3.31661238E-06 5.36483138E-10-3.14696758E-14 2 -1.00095936E+04 9.90506283E+00 5.14911468E+00-1.36622009E-02 4.91453921E-05 3 -4.84246767E-08 1.66603441E-11-1.02465983E+04-4.63848842E+00 4 C2H C 2H 1 G 200.00 6000.00 1000.00 1 ! T07/00 3.66459586E+00 3.82189487E-03-1.36509398E-06 2.13253692E-10-1.23098939E-14 2 6.72238503E+04 3.91355399E+00 2.90180321E+00 1.32859725E-02-2.80508233E-05 3 2.89300812E-08-1.07446930E-11 6.71171170E+04 6.17234595E+00 4 C2H2 C 2H 2 G 200.00 6000.00 1000.00 1 ! g 1/91 4.65878489E+00 4.88396667E-03-1.60828888E-06 2.46974544E-10-1.38605959E-14 2 2.57594042E+04-3.99838194E+00 8.08679682E-01 2.33615762E-02-3.55172234E-05 3 2.80152958E-08-8.50075165E-12 2.64289808E+04 1.39396761E+01 4 C2H3 C 2H 3 G 200.00 6000.00 1000.00 1 ! ATcT/A 4.15026763E+00 7.54021341E-03-2.62997847E-06 4.15974048E-10-2.45407509E-14 2 3.38566380E+04 1.72812235E+00 3.36377642E+00 2.65765722E-04 2.79620704E-05 3 -3.72986942E-08 1.51590176E-11 3.44749589E+04 7.91510092E+00 4 C2H4 C 2H 4 G 200.00 6000.00 1000.00 1 ! g 1/00 3.99182724E+00 1.04833908E-02-3.71721342E-06 5.94628366E-10-3.53630386E-14 2 4.26865851E+03-2.69081762E-01 3.95920063E+00-7.57051373E-03 5.70989993E-05 3 -6.91588352E-08 2.69884190E-11 5.08977598E+03 4.09730213E+00 4 C2H5 C 2H 5 G 200.00 6000.00 1000.00 1 ! IU1/07 4.32195633E+00 1.23930542E-02-4.39680960E-06 7.03519917E-10-4.18435239E-14 2 1.21759475E+04 1.71103809E-01 4.24185905E+00-3.56905235E-03 4.82667202E-05 3 -5.85401009E-08 2.25804514E-11 1.29690344E+04 4.44703782E+00 4 C2H6 C 2H 6 G 200.00 6000.00 1000.00 1 ! g 8/88 4.04666411E+00 1.53538802E-02-5.47039485E-06 8.77826544E-10-5.23167531E-14 2 -1.24473499E+04-9.68698313E-01 4.29142572E+00-5.50154901E-03 5.99438458E-05 3 -7.08466469E-08 2.68685836E-11-1.15222056E+04 2.66678994E+00 4 AR AR 1 G 200.00 6000.00 1000.00 1 ! L 6/88 2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -7.45375000E+02 4.37967490E+00 2.50000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-7.45375000E+02 4.37967490E+00 4 N2 N 2 G 200.00 6000.00 1000.00 1 ! G 8/02 2.95257637E+00 1.39690040E-03-4.92631603E-07 7.86010195E-11-4.60755204E-15 2 -9.23948688E+02 5.87188762E+00 3.53100528E+00-1.23660988E-04-5.02999433E-07 3 2.43530612E-09-1.40881235E-12-1.04697628E+03 2.96747038E+00 4 END TRANSPORT ALL C 0 80.000 2.750 0.000 0.000 0.000 C2 1 209.000 4.100 0.000 0.000 2.500 C2O 1 232.400 3.828 0.000 0.000 1.000 C3 1 209.000 4.100 0.000 0.000 2.500 C3H 1 373.300 4.424 0.000 0.000 1.000 C3H2 1 373.300 4.424 0.000 0.000 1.000 OH* 1 80.000 2.750 0.000 0.000 0.000 CH(A) 1 80.000 2.750 0.000 0.000 0.000 CH(B) 1 80.000 2.750 0.000 0.000 0.000 C2* 1 209.000 4.100 0.000 0.000 2.500 O 0 80.000 2.750 0.000 0.000 0.000 O2 1 107.400 3.458 0.000 1.600 3.800 H 0 145.000 2.050 0.000 0.000 0.000 H2 1 38.000 2.920 0.000 0.790 280.000 H2O 2 572.400 2.605 1.844 0.000 2.100 OH 1 80.000 2.750 0.000 0.000 0.000 HCO 2 498.000 3.590 0.000 0.000 0.000 HCCO 2 436.000 3.970 0.000 0.000 2.000 CO 1 98.100 3.650 0.000 1.950 1.800 CO2 1 244.000 3.763 0.000 2.650 2.100 CH 1 80.000 2.750 0.000 0.000 0.000 CH2(S) 1 141.400 3.746 0.000 0.000 13.000 CH2 1 141.400 3.746 0.000 0.000 13.000 CH3 2 141.400 3.746 0.000 0.000 13.000 CH4 2 141.400 3.746 0.000 2.600 13.000 C2H 1 209.000 4.100 0.000 0.000 2.500 C2H2 1 209.000 4.100 0.000 0.000 2.500 C2H3 2 209.000 4.100 0.000 0.000 2.500 C2H4 2 243.000 4.050 0.000 0.000 2.000 C2H5 2 246.000 4.320 0.000 0.000 2.000 C2H6 2 246.000 4.320 0.000 0.000 2.000 AR 0 136.500 3.330 0.000 0.000 0.000 N2 1 97.530 3.621 0.000 1.760 4.000 END REACTIONS KJOULES/MOLE MOLES !****************************************** !**** Formation Reaction OH* !****************************************** CH +O2 =CO +OH* 1.800E+11 0.0 0.0 H + O + M = OH* + M 1.500E+13 0.000 25.000 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.40 /CO /0.75 /CO2 /1.5 /CH4 /0.66 / !****************************************** !**** Consumption Reactions of OH* !****************************************** OH* =OH 1.450E+06 0.0 0.0 OH* +O2 =OH +O2 2.100E+12 0.5 -2.02 OH* +H2O =OH +H2O 5.930E+12 0.5 -3.61 OH* +H2 =OH +H2 2.950E+12 0.5 -1.86 OH* +CO2 =OH +CO2 2.760E+12 0.5 -4.06 OH* +CO =OH +CO 3.230E+12 0.5 -3.30 OH* +CH4 =OH +CH4 3.360E+12 0.5 -2.66 OH* +OH =OH +OH 6.010E+12 0.5 -3.19 OH* +H =OH +H 1.310E+13 0.5 -0.7 OH* +AR =OH +AR 1.690E+12 0.0 17.32 !****************************************** !**** Formation Reaction CH(A) !****************************************** C2H +O2 =CO2 +CH(A) 3.200E+11 0.0 6.7 C2H +O =CO +CH(A) 2.500E+12 0.0 0.0 C2 +OH =CO +CH(A) 1.110E+13 0.0 0.0 C +H +M =CH(A) +M 3.630E+13 0.00 0.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.40 /CO /0.75 /CO2 /1.5 /CH4 /0.66 / !****************************************** !**** Formation Reaction CH(B) !****************************************** C2H +O2 =CO2 +CH(B) 4.270E+10 0.0 6.7 C2H +O =CO +CH(B) 3.330E+11 0.0 0.0 C2 +OH =CO +CH(B) 1.480E+12 0.0 0.0 C +H +M =CH(B) +M 4.840E+12 0.00 0.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.40 /CO /0.75 /CO2 /1.5 /CH4 /0.66 / !****************************************** !**** Consumption Reactions of CH* !****************************************** !****************************************** !**** Radiative Decay CH(A) and CH(B) !****************************************** CH(A) =>CH 1.860E+06 0.0 0.0 CH(B) =>CH 2.500E+06 0.0 0.0 !****************************************** !**** NonReactive Deactivation CH* !****************************************** !----A state CH(A) +O2 =CH +O2 2.480E+06 2.14 -7.2 CH(A) +CO2 =CH +CO2 2.400E-01 4.30 -7.1 CH(A) +CO =CH +CO 2.440E+12 0.50 0.0 CH(A) +CH4 =CH +CH4 1.730E+13 0.0 0.7 CH(A) +H2O =CH +H2O 5.300E+13 0.0 0.0 CH(A) +H =CH +H 2.010E+14 0.0 5.7 CH(A) +OH =CH +OH 7.130E+13 0.0 5.7 CH(A) +H2 =CH +H2 1.470E+14 0.5 5.7 CH(A) +AR =CH +AR 3.130E+11 0.0 0.0 !--- B state CH(B) +H2O =CH +H2O 5.300E+13 0.0 0.0 CH(B) +H =CH +H 2.010E+14 0.0 5.7 CH(B) +OH =CH +OH 7.130E+13 0.0 5.7 CH(B) +CO =CH +CO 2.440E+12 0.50 0.0 CH(B) +H2 =CH +H2 1.470E+14 0.5 5.7 CH(B) +O2 =CH +O2 3.900E+13 0.0 0.0 CH(B) +CO2 =CH +CO2 4.000E+13 0.0 0.0 CH(B) +CH4 =CH +CH4 1.650E+13 0.0 0.0 CH(B) +AR =CH +AR 6.600E+11 0.0 0.0 !---- CH(B) - CH(A) CH(B) =>CH(A) 5.000E+07 0.0 0.0 !****************************************** !**** Formation Reaction C2* !****************************************** CH2(S) + C = H2 + C2* 2.400E+12 0.000 0.000 C3 +O =CO +C2* 4.200E+11 0.0 0.0 !****************************************** !**** Destruction Reaction C2* !****************************************** !****************************************** !**** Radiative Decay C2* !****************************************** C2* = C2 1.000E+07 0.000 0.000 !****************************************** !**** NonReactive Deactivation C2* !****************************************** C2* + O2 = C2 + O2 4.800E+13 0.000 0.000 C2* + CO2 = C2 + CO2 4.800E+13 0.000 0.000 C2* + H2O = C2 + H2O 4.800E+13 0.000 0.000 C2* + CO = C2 + CO 4.800E+13 0.000 0.000 C2* + CH4 = C2 + CH4 4.800E+13 0.000 0.000 C2* + H2 = C2 + H2 4.800E+13 0.000 0.000 C2* + AR = C2 + AR 4.800E+13 0.000 0.000 !********** C3 Submechanism********************* ! for prediction of correct C3 species imp for C2* formation !****************************************** !**** C Reactions !****************************************** C +H2O =HCO +H 3.000E+12 0.0 0.0 C +OH =H +CO 5.000E+13 0.0 0.0 C +OH =CH +O 2.410E+14 0.0 91.0 C +CH =C2 +H 1.000E+13 0.0 0.0 C +CH2(S) =C2 +H2 3.000E+12 0.0 0.0 C +CH2 =C2 +H2 3.000E+12 0.0 0.0 !****************************************** !**** C2 Reactions !****************************************** C2H +O =C2 +OH 1.200E+13 0.0 0.0 C2H +H =C2 +H2 6.200E+13 0.0 73.00 C2 +OH =C2O +H 5.000E+13 0.0 0.0 C2 +O2 =CO +CO 9.000E+12 0.0 4.1 C2 +O =CO +C 1.000E+14 0.0 0.0 C2 +OH =CH +CO 5.000E+13 0.0 0.0 C2 +CH4 =C2H +CH3 3.000E+13 0.0 2.47 C2 +C2H2 =C2H +C2H 1.000E+14 0.0 0.0 C2 +C2H4 =C2H +C2H3 1.000E+14 0.0 0.0 C2 +C2H6 =C2H +C2H5 5.000E+13 0.0 0.0 !****************************************** !**** C2O Reactions !****************************************** C2 + O2 = C2O + O 2.000E+14 0.0 33.800 CH + CO = C2O + H 1.900E+11 0.0 0.0 C2O + O = CO + CO 4.800E+13 0.0 0.000 C2O + OH = CH + CO2 2.000E+13 0.0 0.000 !****************************************** !**** C3 Reactions !****************************************** C +C2H =C3 +H 2.000E+16 -1.0 0.0 C2 +CH =C3 +H 5.000E+13 0.0 0.0 C3 +OH =CO +C2H 8.000E+13 0.0 0.0 C3 +O2 =CO2 +C2 9.000E+11 0.0 91.5 C3 +O =CO +C2 5.000E+13 0.0 0.0 !****************************************** !**** C3H2 Reactions !****************************************** CH +C2H2 =C3H2 +H 9.368E+13 0.0 -2.09 C3H +H2 =C3H2 +H 4.000E+05 2.4 4.187 C3H2 +O =HCO +C2H 4.000E+13 0.0 0.0 C3H2 +OH =HCO +C2H2 1.000E+13 0.0 0.0 !****************************************** !**** C3H Reactions !****************************************** C3 +H2 =C3H +H 4.050E+05 2.4 92.0 CH +C2H =C3H +H 5.000E+13 0.0 0.0 C3H +O =CO +C2H 4.000E+13 0.0 0.0 C3H +OH =CO +C2H2 2.000E+13 0.0 0.0 C3H +O2 =CO +HCCO 3.000E+13 0.0 0.0 END