! ! *************************************************************************** ! * * ! * The Leeds methane oxidation mechanism * ! * * ! *************************************************************************** ! ! The latest version of this mechanism is always available from ! the World Wide Web: ! http://www.chem.leeds.ac.uk/Combustion/Combustion.html ! or ! http://garfield.chem.elte.hu/Combustion/Combustion.html ! !*****Version 1.5 (31st March, 2001)*************************************** ! Changes from version 1.4 ! ! All thermodynamic data were updated. ! The new data are mainly based on ! Alexander Burcat's Ideal Gas Thermochemical Database, March, 2001 ! ! ! Only reversible reactions are used ! !*****Version 1.4 (10th July 1997)**************************************** ! Changes from version 1.3 ! ! The A Factor of reaction CO+OH=>CO2+H was increased by 10% ! to simulate better CO flame speeds ! ! Thermodynamic data for CH2OH was set back to the SANDIA recommendation ! ! !*****Version 1.3 (25th July 1996)**************************************** ! Changes from version 1.2 ! ! corrected error in cec summary page for CH3 + OH = CH2(S) + H2O ! (increased x10) ! ! Went Back to original rate for reaction H+CH2OH=CH3+OH ! Set H+CH3+M=CH4+M at 80% of its cec recommendation ! ! In order to simulate ethane/O2/Ar ignition delays, altered ! C2H3+O2=HCO+HCHO to C2H3+O2=HO2+C2H2 ! ! !*****Version 1.2 (26th February 1996)************************************* ! Changes from version 1.1 ! ! corrected error in C2H6 + M => 2CH3 + M (added missing TROE values) ! ! !*****Version 1.1 (31st August, 1995)************************************** ! ! Changes from version 1.0 ! 1. Modified rate for reaction H+CH2OH=CH3+OH ! ! Version 1.0 was launched on 20th August, 1995 ! ! Authors: ! K.J. Hughes (1) ! T. Turanyi (2) ! M.J. Pilling (1) ! ! (1) School of Chemistry ! The University of Leeds ! Leeds, LS2 9JT ! UK ! ! (2) Department of Physical Chemistry ! Eotvos University (ELTE) ! H-1518 Budapest, P.O.Box 32 ! Hungary ! ! The authors are grateful for the helpful discussions to ! ! D.L. Baulch ! S. Dobe ! P.W Seakins ! S.H. Robertson ! !-------------------------------------------------------------------------- ! ! This mechanism is based on [94BAU/COB], a recent evaluation ! of a CEC task group. Data not available from [94BAU/COB] ! were looked for in the NIST and LEEDS kinetics data bases ! (see Literature for references). ! ! The rate data have been annotated with the following ! additional information: ! ! (i) Other possible channels (if any) ! ! (ii) Classification of the rate data: ! ! A very well known rate parameter ! the evaluation is based on several measurements in good agreement ! ! B evaluated data ! the evaluation is based on few and/or conflicting measurements ! ! C low temperature (T < about 1100K) indirect measurements ! ! D low temperature (T < about 1100K) direct measurements ! ! E high temperature (T > about 1100K) indirect measurement ! (shock tube or flame excitation) ! ! F high temperature (T > about 1100K) direct measurement ! (usually shock tube) ! ! T theoretical result ! no experimental data are available ! ! S estimated value ! experimental data or detailed theoretical calculations ! are not available, but a reasonable estimation can be made ! on the basis of data for analogue reactions ! ! U uncertain data ! no experimental data, no theoretical calculation, and ! no basis for a good estimation ! ! ! Double classification: ! - letter before slash stands for the overall reaction ! - letter after slash stands for the product channels ! ! e.g. A/U means well known overall reaction parameters ! with uncertain product channel ratios ! ! (iii) Uncertainty factors: ! ! In agreement with [94BAU/COB], f = log10 (k_max/k) values are used. ! The uncertainties were taken from the evaluations. When evaluated data ! were not available (cases C-U), the uncertainties were estimated. ! ! ! (iv) Temperature intervals: ! ! The indicated temperature interval stands for ! - the temperature interval of recommendation in case of A, B ! - the temperature interval of measurements in case of C to F ! - the temperature interval of assumed validity in case of T, S, U ! ! (v) Reference ! ! The referencing follows the style of the NIST database, ! even though some of the cited papers are not included there. ! !----------------------------------------------------------------------------- ! ! [94BAU/COB] use the Troe formalism for the description of fall-off curves. ! In some cases they provide a constant Fc with typical error limits ! delta Fc=+-0.1. Unfortunately CHEMKIN can not handle temperature independent ! Fc-s and therefore in these cases TROE / 1 1 1 -ln(Fc)*1500 / parameters ! were used. This is exact at 1500K and Fc remains within the error limits ! in the range of 1200K-2000K. ! !----------------------------------------------------------------------------- ! ! Following the suggestion of Warnatz [84WAR], ! all 3rd bodies are weighted as follows: ! ! N2 0.4 ! O2 0.4 ! CO 0.75 ! CO2 1.5 ! H2O 6.5 ! CH4 3.0 ! C2H6 3.0 ! Ar 0.35 ! He 0.35 ! ! Comments: ! ! - The weight of all other species is 1. ! - CH4 had a weight of 6.5 in the original recommendation of [84WAR] ! but a value of 3.0 is now generally employed ( see e.g. [92GRO/KEL]) ! - Experimental or evaluated low pressure limits (k0) have been reported ! for bath gases N2, He, Ar, and C2H6. In the few cases where N2 and Ar ! data differ, consistently the N2 data have been chosen. These cases ! are indicated in the text. ! The low pressure A factors for these reactions were scaled ! to a general collider with unit weight according to the above weighting. ! The 3rd body efficiency for He was used for the scaling, but it does not ! appear in the mechanism. ! !---------------------------------------------------------------------------- ! ! ! Heat-of-formation, entropy, and heat capacity of species at 298.15K ! ! ! species dH S Cp source updated accuracy ! kJ/mole J/K_mole kJ/mole MM/YY ! H2 0.00 +- 0.00 [1] 130.67 28.83 R 78 A ! CH4 -74.60 +- 0.40 [1] 186.36 35.69 L 8/88 B ! C2H2 227.39 +- 1.00 [1] 200.90 44.00 L 8/88 A ! C2H4 52.29 +- 1.20 [1] 219.17 42.80 L 4/85 B ! C2H6 -83.86 +- 0.20 [1] 229.07 52.39 L 5/84 B ! C3H4 190.91 +- 8.00 [1] 243.42 58.88 L 8/89 B ! C3H6 20.41 +- 0.40 [1] 266.52 64.38 L 4/85 B ! C4H2 440.47 +- 8.00 [1] 255.96 73.64 L 9/89 C ! O2 0.00 +- 0.00 [1] 205.14 29.38 R 89 A ! H2O -241.81 +- 0.04 [1] 188.82 33.59 L 5/89 A ! H2O2 -135.88 +- 0.50 [3] 234.51 42.39 L 2/93 B ! CO -110.52 +- 0.17 [1] 197.65 29.14 R 79 A ! CO2 -393.49 +- 0.13 [1] 213.77 37.13 L 7/88 A ! CH2O -108.57 +- 0.50 [1] 218.75 35.39 L 8/88 B ! CH2CO -49.58 +- 1.70 [7] 241.88 51.74 T 6/94 B ! C 716.63 +- 0.45 [1] 158.09 20.84 L 7/88 A ! H 217.99 +- 0.006 [1] 114.71 20.79 L 6/94 A ! CH 596.40 +- 1.20 [2] 183.03 29.17 R 79 A ! CH2 390.39 +- 4.00 [1] 194.89 33.76 R 79 B ! CH2(S) 428.07 +- 2.50 [7] 188.71 33.77 C 12/87 B ! CH3 146.65 +- 0.40 [7] 193.95 38.41 L 8/88 B ! C2H 566.10 +- 2.90 [2] 213.29 42.00 T 07/00 B ! C2H3 299.72 +- 3.40 [1] 233.94 43.64 T 06/93 B ! C2H5 120.90 +- 1.60 [2] 247.10 50.48 T 12/91 B ! C3H2 476.95 +- 8.00 [1] 253.45 58.01 T 08/00 C ! H2CCCH 339.00 +- 4.00 [4] 256.64 64.89 T 5/97 B ! H2CCCCH 483.72 +- 8.00 [1] 289.69 70.01 L 9/89 C ! O 249.16 +- 0.00 [1] 161.05 21.91 L 1/90 A ! OH 37.20 +- 2.10 [8] 183.73 29.89 R 78 A ! HO2 13.81 +- 3.35 [6] 229.09 34.89 L 5/89 B ! HCO 42.00 +- 0.80 [1] 224.32 34.59 L 12/89 - ! CH3O 17.20 +- 3.80 [2] 229.38 43.51 L 8/88 B ! CH2OH -16.60 +- 4.20 [5] 243.90 48.37 T 9/92 B ! HCCO 177.39 +- 8.80 [1] 245.27 48.41 T 6/94 B ! CH2HCO 10.50 +- 9.20 [2] 267.90 54.97 T 4/83 B ! N2 0.00 +- 0.00 [1] 191.60 29.12 R 78 A ! AR 0.00 +- 0.00 [1] 154.84 20.79 L 6/88 A ! ! The NASA polynomials for thermodynamic data were taken ! from Alexander Burcat's Thermochemical Database [1]. ! In this database the source and the accuracy of data are characterized by ! symbols, given in the last three columns of the table above. ! Explanation to Burcat's notations: ! Source: ! C CHEMKIN database ! L NASA Glen (Lewis) Research Center ! R Russian Tables (TSIV) ! T Technion-Israel Inst. Technology ! Updated: ! Date when polynomial was last revised. ! Accuracy of thermodynamic data: ! A most accurate (direct summation or RRHO approximation ! with anharmonicity correction) ! B accurate (regular RRHO) ! C less accurate (RRHO calculation with estimated frequencies ! and free rotor approach) ! ! In most cases the deltaH(298.15K) values recommended by Burcat were ! accepted and then reference [1] is given in column 3. ! In other cases the deltaH(298.15K) values were revised and values ! from other sources (given in column 3) were used. ! In such cases the polynomials were corrected by program MECHMOD v1.4. ! ! References to deltaH(298.15K) data: ! ! [1] Alexander Burcat's Ideal Gas Thermochemical Database, March, 2001 ! ! [2] R. Atkinson, D.L. Baulch, R.A. Cox, R.F. Hampson, Jr., J.A. Kerr, ! M.J. Rossi, J. Troe ! Evaluated kinetic and photochemical data for atmospheric chemistry, ! organic species: Supplement VII, ! J. Phys. Chem. Ref. Data, Vol. 28, No. 2. 1999. ! [3] L.V. Gurvich, I.V. Veyts, C.B. Alcock ! Thermodynamic properties of individual substances ! Vols 1 and 2, Parts 1 and 2, ! Hemisphere, New York, 1989 ! [4] W. Tsang ! Heats of formation of organic free radicals by kinetic methods ! in: Energetics of organic free radicals, ! J.A.M. Simoes, A. Greenberg, J. F. Liebman (eds.) ! Blachie Academic and Professional, 1996 ! [5] S. Dobe, T. Berces, T. Turanyi, F. Marta, ! J. Grussdorf, F. Temps, H.Gg. Wagner ! Direct kinetic studies of the reactions Br+CH3OH and CH2OH+HBr: ! The heat of formation of CH2OH ! J.Phys.Chem, 100, 19864-19873(1996) ! [6] M. Litorja, B. Ruscic ! J.Electron Spectr.Rel.Phen., 97, 131-146(1998) ! [7] B. Ruscic, M. Litorja, R.L. Asher ! Ionization energy of methylene revisited: Improved values for the ! enthalpy of formation of CH2 and the bond dissociation energy of CH3 ! via simultaneous solution of the local thermodynamical network ! J.Phys.Chem. A, 103, 8625-8633(1999) ! [8] B. Ruscic, D. Feller, D.A. Dixon, K.A. Peterson, L.B. Harding, ! R.L. Asher, A.F. Wagner ! J.Phys.Chem. A, 105, 1-4(2001) ! ELEMENTS H O C N AR END SPECIES ! ! H/C molecules ! H2 CH4 C2H2 C2H4 C2H6 C3H4 ! allene (propadiene) CH2=C=CH2 C3H6 ! propylene C4H2 ! HCC-CCH ! ! O/H/C molecules ! O2 H2O H2O2 CO CO2 CH2O CH2CO ! H2C=C=O ! ! H/C radicals ! C H CH ! CH(X2Pi) CH2 ! CH2(X3B1) CH2(S) ! CH2(aX) CH3 C2H ! ethynyl radical C2H3 C2H5 C3H2 H2CCCH ! .CH2-CC-H propargyl radical (see [90COL/DES]) H2CCCCH ! CH2=C.-CC-H butenyn-2-yl (see [88DUR/AMO]) ! ! O/H/C radicals ! O OH HO2 HCO CH3O CH2OH HCCO ! H.C=C=O CH2HCO ! .CH2COH ! ! Buffer gases ! N2 AR ! ! Notation: ! C-C single bond ! C=C double bond ! CC triple bond ! C. lonely electron pair ! !------------------------------------------------------------- ! ! Some species were not included into the mechanism, ! although their generation reactions are known: ! ! CH3CHO from (C2H5+O) ! CH3OH from (CH3+OH+M) ! C2O from (HCCO+O2),(CO+CH), and (CO2+CH) ! C3H2O from (H2CCCH+O) ! ! For these reactions alternative product channels were considered. ! !--------------------------------------------------------------- ! ! The (forward) reactions are ordered according to the above ! order of species. All reactions of H2 come first, then ! all reactions of CH4, etc. ! END THERMO ALL 300.000 1000.000 5000.000 H2 H 2 0 0 0G 200.00 6000.00 1000.00 0 1 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 CH4 H 4C 1 0 0G 200.00 6000.00 1000.00 0 1 1.63542560E+00 1.00844310E-02-3.36923690E-06 5.34972800E-10-3.15528170E-14 2 -1.00056030E+04 9.99369530E+00 5.14987920E+00-1.36710080E-02 4.91801300E-05 3 -4.84744030E-08 1.66694410E-11-1.02466480E+04-4.64132440E+00 4 C2H2 H 2C 2 0 0G 200.00 6000.00 1000.00 0 1 4.65870470E+00 4.88409490E-03-1.60835630E-06 2.46987870E-10-1.38615050E-14 2 2.56632180E+04-3.99790740E+00 8.08691080E-01 2.33613950E-02-3.55166360E-05 3 2.80145660E-08-8.50044590E-12 2.63327640E+04 1.39396710E+01 4 C2H4 H 4C 2 0 0G 300.00 5000.00 1000.00 0 1 4.39854530E+00 9.62286070E-03-3.16637760E-06 4.57476280E-10-2.36594060E-14 2 4.11532030E+03-2.46274380E+00 1.21766000E+00 1.30026750E-02 3.50374470E-06 3 -1.11555140E-08 4.72032220E-12 5.33738280E+03 1.54801690E+01 4 C2H6 H 6C 2 0 0G 300.00 5000.00 1000.00 0 1 4.70288470E+00 1.40426350E-02-4.64693770E-06 6.74737380E-10-3.50893120E-14 2 -1.26719880E+04-4.54339500E+00 1.53952600E+00 1.50408410E-02 6.68471150E-06 3 -1.33829480E-08 4.85613980E-12-1.12487660E+04 1.41073750E+01 4 C3H4 H 4C 3 0 0G 200.00 6000.00 1000.00 0 1 6.31687220E+00 1.11337280E-02-3.96293780E-06 6.35642380E-10-3.78755400E-14 2 2.01174950E+04-1.09957660E+01 2.61304450E+00 1.21225750E-02 1.85398800E-05 3 -3.45251490E-08 1.53350790E-11 2.15415670E+04 1.02261390E+01 4 C3H6 H 6C 3 0 0G 300.00 5000.00 1000.00 0 1 6.72139740E+00 1.49317570E-02-4.96523530E-06 7.25107530E-10-3.80014760E-14 2 -9.24531490E+02-1.21556170E+01 1.45751570E+00 2.11422630E-02 4.04680120E-06 3 -1.63190030E-08 7.04751530E-12 1.07402080E+03 1.73994600E+01 4 C4H2 H 2C 4 0 0G 200.00 6000.00 1000.00 0 1 8.66700350E+00 6.71663710E-03-2.35449950E-06 3.73830790E-10-2.21189140E-14 2 4.98569330E+04-2.11142050E+01-3.95185080E-01 5.19558130E-02-9.17866160E-05 3 8.05239290E-08-2.69170880E-11 5.14517090E+04 2.09691010E+01 4 O2 O 2 0 0 0G 200.00 6000.00 1000.00 0 1 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 H2O H 2O 1 0 0G 200.00 6000.00 1000.00 0 1 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 H2O2 H 2O 2 0 0G 200.00 6000.00 1000.00 0 1 4.57333537E+00 4.04984070E-03-1.29479479E-06 1.97281710E-10-1.13402846E-14 2 -1.80040975E+04 7.04278488E-01 4.27611269E+00-5.42822417E-04 1.67335701E-05 3 -2.15770813E-08 8.62454363E-12-1.77035843E+04 3.43505074E+00 4 CO O 1C 1 0 0G 200.00 6000.00 1000.00 0 1 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 O 2C 1 0 0G 200.00 6000.00 1000.00 0 1 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 CH2O H 2O 1C 1 0G 200.00 6000.00 1000.00 0 1 3.16948070E+00 6.19327420E-03-2.25059810E-06 3.65982450E-10-2.20154100E-14 2 -1.44784250E+04 6.04235330E+00 4.79370360E+00-9.90815180E-03 3.73214590E-05 3 -3.79279020E-08 1.31770150E-11-1.43089550E+04 6.02887020E-01 4 CH2CO H 2O 1C 2 0G 200.00 6000.00 1000.00 0 1 5.75779010E+00 6.34965070E-03-2.25844070E-06 3.62084620E-10-2.15690300E-14 2 -8.20537635E+03-6.10640370E+00 2.14011650E+00 1.80883680E-02-1.73242160E-05 3 9.27674770E-09-1.99150110E-12-7.26981595E+03 1.21986990E+01 4 C C 1 0 0 0G 200.00 6000.00 1000.00 0 1 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 H H 1 0 0 0G 200.00 6000.00 1000.00 0 1 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 CH H 1C 1 0 0G 200.00 6000.00 1000.00 0 1 2.52090620E+00 1.76537260E-03-4.61475810E-07 5.92885670E-11-3.34732090E-15 2 7.10230206E+04 7.40532230E+00 3.48981660E+00 3.23835540E-04-1.68899060E-06 3 3.16217330E-09-1.40609070E-12 7.06888776E+04 2.08401110E+00 4 CH2 H 2C 1 0 0G 200.00 6000.00 1000.00 0 1 2.53871220E+00 3.82254910E-03-1.28613040E-06 1.98003080E-10-1.14657430E-14 2 4.61292530E+04 8.10546480E+00 4.17936550E+00-2.21785530E-03 7.96536020E-06 3 -6.91273390E-09 2.24753180E-12 4.57508570E+04-7.61137030E-03 4 CH2(S) H 2C 1 0 0G 300.00 4000.00 1000.00 0 1 3.55288800E+00 2.06678800E-03-1.91411600E-07-1.10467330E-10 2.02134900E-14 2 5.02544011E+04 1.68657000E+00 3.97126500E+00-1.69908800E-04 1.02536890E-06 3 2.49255000E-09-1.98126600E-12 5.02983211E+04 5.75320700E-02 4 CH3 H 3C 1 0 0G 200.00 6000.00 1000.00 0 1 2.96697350E+00 5.79366720E-03-1.96948090E-06 3.05569360E-10-1.77678430E-14 2 1.65131329E+04 4.79188030E+00 3.67333750E+00 2.00205590E-03 5.78531350E-06 3 -6.98730540E-09 2.60555990E-12 1.64161969E+04 1.60183150E+00 4 C2H H 1C 2 0 0G 200.00 6000.00 1000.00 0 1 3.66459586E+00 3.82189487E-03-1.36509398E-06 2.13253692E-10-1.23098939E-14 2 6.69367375E+04 3.91355399E+00 2.90180321E+00 1.32859725E-02-2.80508233E-05 3 2.89300812E-08-1.07446930E-11 6.68300042E+04 6.17234595E+00 4 C2H3 H 3C 2 0 0G 200.00 6000.00 1000.00 0 1 4.70253100E+00 7.26422830E-03-2.58019920E-06 4.13199440E-10-2.45914920E-14 2 3.40296750E+04-1.42937140E+00 3.00196020E+00 3.03043540E-03 2.44443150E-05 3 -3.58102420E-08 1.51087000E-11 3.48681730E+04 9.33044950E+00 4 C2H5 H 5C 2 0 0G 200.00 6000.00 1000.00 0 1 4.28788140E+00 1.24338930E-02-4.41391190E-06 7.06541020E-10-4.20351360E-14 2 1.23269670E+04 8.46025830E-01 4.30585800E+00-4.18336380E-03 4.97072700E-05 3 -5.99058740E-08 2.30484780E-11 1.31122260E+04 4.71002360E+00 4 C3H2 H 2C 3 0 0G 200.00 6000.00 1000.00 0 1 5.69445684E+00 6.53821901E-03-2.35907266E-06 3.82037384E-10-2.29227460E-14 2 5.49264274E+04-6.96163733E+00 3.18167129E+00-3.37611741E-04 3.95343765E-05 3 -5.49792422E-08 2.28335240E-11 5.61816758E+04 9.06482468E+00 4 H2CCCH H 3C 3 0 0G 200.00 6000.00 1000.00 0 1 7.14221880E+00 7.61902005E-03-2.67459950E-06 4.24914801E-10-2.51475415E-14 2 3.80693414E+04-1.25848435E+01 1.35110927E+00 3.27411223E-02-4.73827135E-05 3 3.76309808E-08-1.18540923E-11 3.92663770E+04 1.52058924E+01 4 H2CCCCH H 3C 4 0 0G 298.15 6000.00 1000.00 0 1 8.47620790E+00 8.87823270E-03-3.03284120E-06 4.73583020E-10-2.77166270E-14 2 5.47565400E+04-1.71705510E+01 2.41732470E+00 2.41047820E-02-1.28134700E-05 3 -2.86062370E-09 3.91945270E-12 5.65064760E+04 1.44711070E+01 4 O O 1 0 0 0G 200.00 6000.00 1000.00 0 1 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 OH H 1O 1 0 0G 200.00 6000.00 1000.00 0 1 2.83864607E+00 1.10725586E-03-2.93914978E-07 4.20524247E-11-2.42169092E-15 2 3.68599690E+03 5.84452662E+00 3.99201543E+00-2.40131752E-03 4.61793841E-06 3 -3.88113333E-09 1.36411470E-12 3.35711894E+03-1.03925458E-01 4 HO2 H 1O 2 0 0G 200.00 6000.00 1000.00 0 1 4.17226590E+00 1.88120980E-03-3.46292970E-07 1.94685160E-11 1.76091530E-16 2 2.13222508E+02 2.95779740E+00 4.30178800E+00-4.74902010E-03 2.11579530E-05 3 -2.42759610E-08 9.29206700E-12 4.46212417E+02 3.71670100E+00 4 HCO H 1O 1C 1 0G 200.00 6000.00 1000.00 0 1 3.64896209E+00 3.08090819E-03-1.12429876E-06 1.86308085E-10-1.13951828E-14 2 3.71209048E+03 5.06147406E+00 4.22118584E+00-3.24392532E-03 1.37799446E-05 3 -1.33144093E-08 4.33768865E-12 3.83956496E+03 3.39437243E+00 4 CH3O H 3O 1C 1 0G 200.00 6000.00 1000.00 0 1 4.26533080E+00 7.85764060E-03-2.84104380E-06 4.60451900E-10-2.76319060E-14 2 1.65605687E+02 3.93099470E-01 3.26523370E+00 3.30316650E-03 1.70488010E-05 3 -2.27096300E-08 8.80717680E-12 8.38550421E+02 7.42573570E+00 4 CH2OH H 3O 1C 1 0G 200.00 6000.00 1000.00 0 1 4.72398695E+00 6.50832540E-03-2.24240605E-06 3.51742805E-10-2.06424726E-14 2 -3.81156740E+03 1.47350104E+00 4.73864580E+00 1.27132491E-03 1.46005656E-05 3 -1.83666166E-08 7.07708694E-12-3.56200591E+03 2.65277676E+00 4 HCCO H 1O 1C 2 0G 200.00 6000.00 1000.00 0 1 5.84690060E+00 3.64059600E-03-1.29590070E-06 2.07969190E-10-1.24000220E-14 2 1.92484960E+04-5.29165330E+00 2.33501180E+00 1.70100830E-02-2.20188670E-05 3 1.54064470E-08-4.34550970E-12 2.00502990E+04 1.19767290E+01 4 CH2HCO H 3O 1C 2 0G 300.00 5000.00 1000.00 0 1 5.97566990E+00 8.13059140E-03-2.74362450E-06 4.07030410E-10-2.17601710E-14 2 -1.26585075E+03-5.03208790E+00 3.40906240E+00 1.07385740E-02 1.89149250E-06 3 -7.15858310E-09 2.86738510E-12-2.34695926E+02 9.57145350E+00 4 N2 N 2 0 0 0G 200.00 6000.00 1000.00 0 1 2.95254070E+00 1.39688380E-03-4.92625770E-07 7.86000910E-11-4.60749780E-15 2 -9.23937530E+02 5.87182210E+00 3.53096280E+00-1.23659500E-04-5.02993390E-07 3 2.43527680E-09-1.40879540E-12-1.04696370E+03 2.96743910E+00 4 AR AR 1 0 0 0G 200.00 6000.00 1000.00 0 1 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 END REACTIONS MOLES KJOULES/MOLE ! ! Methane flame mechanism ! H2 + CH2(S) = CH3 + H 7.23E13 0.00 0.00 ! A 0.3 300 - 1000 [94BAU/COB] ! H2 + O = OH + H 5.12E04 2.67 26.27 ! A 0.2 300 - 2500 [94BAU/COB] ! H2O + H = H2 + OH 4.52E08 1.6 77.08 ! A 0.2 300-2500 [94BAU/COB] ! CH4 + O2 = CH3 + HO2 3.97E13 0.00 238.04 ! B 1.0 500-2000 [94BAU/COB] ! CH4 + C = CH + CH3 5.00E13 0.00 100.48 ! U 1.0 [86GLA/MIL] ! CH4 + H = CH3 + H2 1.32E04 3.00 33.63 ! A 0.05 300-2500 [94BAU/COB] ! CH4 + CH = C2H4 + H 3.01E13 0.00 -1.66 ! ! B 1.0 200-700 [94BAU/COB] ! CH4 + CH2 = CH3 + CH3 4.30E12 0.00 42.00 ! D 1.0 296-707 [85BOH/DOB] ! CH4 + CH2(S) = CH3 + CH3 7.00E13 0.00 0.00 ! D 1.0 298 [80ASH/FUL], [83LAN/PET] ! CH4 + C2H = CH3 + C2H2 1.81E12 0.00 0.00 ! CH4+C2H=>(CH3+C2H2)(H+C3H4) ! B/U 1.0 298 [94BAU/COB] ! CH4 + O = CH3 + OH 7.23E08 1.56 35.5 ! A 0.2 300-2500 [94BAU/COB] ! CH4 + OH = CH3 + H2O 1.57E07 1.83 11.64 ! A 0.15 250-2500 [94BAU/COB] ! CH4 + HO2 = CH3 + H2O2 9.03E12 0.00 103.43 ! B 0.3 600-1000 [94BAU/COB] ! C2H2 + C2H2 = H2CCCCH+ H 2.00E09 0.00 242.00 ! S 1.0 700-1300 [88DUR/AMO] ! C2H2 + O2 = C2H + HO2 1.20E13 0.00 312.00 ! S 0.7 300-2500 [86TSA/HAM] ! ! H2 + C2H = C2H2 + H 1.08E13 0.00 9.06 ! B 0.4 300-2500 [94BAU/COB] ! C2H2 + H (+M) = C2H3 (+M) 8.43E12 0.00 10.81 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! A 0.3 200- 400 [94BAU/COB] LOW / 3.43E18 0.0 6.15 / ! scaled for He; the original data: ! 1.20E18 0.0 6.15 (He) B 0.5 200- 400 [94BAU/COB] TROE / 1 1 1 1231 / ! B 0.1 200- 400 [94BAU/COB] (Fc= 0.44) ! C2H2 + CH = C2H + CH2 2.11E14 0.00 -0.51 ! C2H2+CH=>(C2H+CH2)(C3H2+H) ! B/U 1.0 200- 700 [94BAU/COB] ! C2H2 + CH2 = C3H4 1.20E13 0.00 27.69 ! B 0.3 300-1000 [94BAU/COB] ! C2H2 + CH2(S) = H2CCCH + H 1.75E14 0.00 0.00 ! C2H2+CH2(S)=>(CH2CCH2);(CH3CCH);(H2CCCH+H) ! B/U 0.7 300-1000 [94BAU/COB] ! C2H2 + C2H = C4H2 + H 9.03E13 0.00 0.00 ! B 0.5 300-2700 [94BAU/COB] ! C2H2 + O = CH2 + CO 2.17E06 2.1 6.57 C2H2 + O = HCCO + H 5.06E06 2.1 6.57 ! A/A overall: 0.2 295-2500 [94BAU/COB] ! k2/k=0.7+-0.2 ! ! C2H2 + OH = C2H + H2O 6.00E13 0.00 54.04 ! C2H2+OH=>(H2O+C2H);(H+CH2CO);(C2H2OH) ! k(1+2)= 6.02E13 0.00 54.04 B/U 1.0 1000-2000 [94BAU/COB] ! channel#3 is important at low temperature and high pressure ! C2H2 + M = C2H + H + M 1.14E17 0.00 447.00 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! B 0.5 1500-3500 [84WAR] (Ar) 4.00E16 0.00 447.00 ! C2H4 + H = C2H3 + H2 5.42E14 0.00 62.36 ! A 0.5 700-2000 [94BAU/COB] ! C2H4 + H (+M) = C2H5 (+M) 3.97E09 1.28 5.40 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! A 0.3 200-1100 [94BAU/COB] LOW / 1.35E19 0.00 3.16 / ! scaled for He; the original data: ! 4.71E18 0.00 3.16 (He) A 0.3 300- 800 [94BAU/COB] TROE / 0.76 40 1025/ ! (for He) A 0.1 300- 800 [94BAU/COB] ! C2H4 + CH = C3H4 + H 1.32E14 0.00 -1.44 ! C2H4+CH=>(C3H4+H)(CH2+C2H3) ! B/U 1.0 200- 700 [94BAU/COB] ! C2H4 + CH2(S) = C3H6 9.64E13 0.00 0.00 ! B 0.5 300-1000 [94BAU/COB] ! ! C2H4 + CH3 = CH4 + C2H3 4.16E12 0.00 46.56 ! B 0.5 400-3000 [94BAU/COB] ! C2H4 + O = H + CH2HCO 4.74E06 1.88 0.75 C2H4 + O = CH3 + HCO 8.13E06 1.88 0.75 C2H4 + O = CH2CO + H2 6.80E05 1.88 0.75 ! C2H4+O=>(H+CH2CHO);(HCO+CH3);(CH2O+CH2);CH2CO+H2) ! A/B overall: 0.3 300-2000 [94BAU/COB] ! k1/k= 0.35+-0.05 k2/k=0.6+-0.10 k3/k=0 k4/k=0.05+-0.10 ! C2H4 + OH = C2H3 + H2O 2.05E13 0.00 24.86 ! B 0.5 650-1500 [94BAU/COB] ! C2H4 + M = C2H2 + H2 + M 9.97E16 0.00 299.32 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! B 0.3 1500-3200 [94BAU/COB] (Ar) 3.49E16 0.00 299.32 ! C2H4 + M = C2H3 + H + M 7.40E17 0.00 404.09 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! B 0.5 1500-3200 [94BAU/COB] (Ar,Kr) 2.59E17 0.00 404.09 ! C2H6 + H = C2H5 + H2 1.45E09 1.5 31.01 ! A 0.3 300-2000 [94BAU/COB] ! C2H6 + CH = C2H4 + CH3 1.08E14 0.00 -1.10 ! C2H6+CH=>(C2H4+CH3)(C3H6+H) ! B/U 1.0 200- 700 [94BAU/COB] ! C2H6 + CH2(S) = CH3 + C2H5 2.40E14 0.00 0.00 ! D 1.0 298 [83LAN/PET] ! C2H6 + CH3 = C2H5 + CH4 1.51E-7 6.0 25.30 ! A 0.2 300-1500 [94BAU/COB] ! C2H6 + O = C2H5 + OH 1.00E09 1.5 24.28 ! A 0.15 300-1200 [94BAU/COB] ! C2H6 + OH = C2H5 + H2O 7.23E06 2.00 3.62 ! A 0.1 250-2000 [94BAU/COB] ! C2H6 + HO2 = H2O2 + C2H5 1.32E13 0.00 85.63 ! B 0.3 500-1000 [94BAU/COB] ! C4H2 + O = C3H2 + CO 7.89E12 0.00 5.64 ! D 1.0 210- 423 [86MIT/NAV] ! C4H2 + OH = C3H2 + HCO 6.68E12 0.00 -1.71 ! C4H2+OH=>(C3H2+HCO)(C4H+H2O) ! D/U 0.3 296- 688 [84PER] ! O2 + CO = CO2 + O 1.26E13 0.00 196.90 ! F 0.7 1000-1400 [91KOI] ! O2 + CH2O = HCO + HO2 6.02E13 0.00 170.11 ! B 0.5 700-1000 [94BAU/COB] ! O2 + C = CO + O 1.20E14 0.00 16.71 ! F 0.18 1500-4200 [91DEA/DAV] ! O2 + H + M = HO2 + M 2.10E18 -0.8 0.00 N2/0.67/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/0.0/ CH4/3.0/ C2H6/3.0/ AR/0.29/ ! not scaled because rate data refer to H2 ! [94BAU/COB] gives 3rd body efficiencies for N2 and Ar ! B 0.5 300-2000 [94BAU/COB] (H2) 2.10E18 -0.8 0.00 ! O2 + H + H2O = HO2 + H2O 6.89E15 0.0 -8.73 ! D 1.0 298- 639 [89HSU/AND] ! O2 + H = OH + O 9.756E13 0.00 62.11 ! A 0.3 300-5000 [94BAU/COB] ! O2 + CH = CO + OH 1.66E13 0.00 0.00 O2 + CH = CO2 + H 1.66E13 0.00 0.00 ! O2+CH=>(CO+OH)(CO2+H)(HCO+O)(CO+H+O) ! k(overall)= 3.31E13 0.00 0.00 B/U 0.5 300-2000 [94BAU/COB] ! O2 + CH2 = CO2 + H2 5.43E12 0.00 6.24 O2 + CH2 = CO2 + H + H 5.43E12 0.00 6.24 O2 + CH2 = CO + OH + H 8.15E12 0.00 6.24 O2 + CH2 = CO + H2O 1.48E12 0.00 6.24 O2 + CH2 = CH2O + O 4.20E12 0.00 6.24 ! O2+CH2=>(CO2+H2)(CO2+H+H)(CO+OH+H)(CO+H2O)(CH2O+O) ! k(overall)= 2.47E13 0.00 6.24 A 0.5 300-1000 [94BAU/COB] ! [94ALV/MOO] have measured the branching ratios at 298K: ! k(1+2)/k= 0.40+0.09-0.07; k(3+4)/k=0.34+-0.06; ! k(3)/k=0.30+-0.05; k(5)/k=0.16+-0.04 (The sum is 0.9) ! Based on the above numbers, the following branching ratios are used here: ! k(1)/k=0.22; k(2)/k=0.22; k(3)/k=0.33; k(4)/k=0.06; k(5)/k=0.17 ! O2 + CH2(S) = CO + OH + H 3.13E13 0.00 0.00 ! O2+CH2(S)=>(CO+H+OH);(CO2+H2);(CO+H2O);(CH2+O2) ! k(overall)= 3.13E13 0.00 0.00 A/U 0.5 300-1000 [94BAU/COB] ! O2 + CH3 = CH2O + OH 3.31E11 0.00 37.42 ! B 0.5 1000-2500 [94BAU/COB] ! ! O2 + C2H = HCCO + O 9.05E12 0.00 0.00 O2 + C2H = CO2 + CH 9.05E12 0.00 0.00 ! O2+C2H=>(HCCO+O)(CO2+CH);(2CO+H);(C2HO+O);(CO+HCO) ! k(overall)= 1.81E13 0.00 0.00 B/U 0.5 300 [94BAU/COB] ! According to the measurements of Seakins et al (unpublished) ! (HCCO+O)(CO2+CH) are the two most likely channels ! ! O2 + C2H3 = CH2O + HCO 5.42E12 0.00 0.00 O2 + C2H3 = C2H2 + HO2 5.42E12 0.00 0.00 ! O2+C2H3=>(CH2O+HCO);(C2H2+HO2);(C2H3O+O) ! k(overall)= 5.42E12 0.00 0.00 B/U 0.5 300-2000 [94BAU/COB] ! (CH2O+HCO) seems to be the most important channel, but ! (C2H2+HO2) might be important at high temperature ! ! In order to get any sort of reasonable prediction of ignition delay times ! in ethane/O2/Ar mixtures, it was necessary to have the HO2+C2H2 product ! channel despite the lack of evidence for it. ! ! O2 + C2H5 = C2H4 + HO2 1.02E10 0.00 -9.15 ! A 0.3 600-1200 [94BAU/COB] ! O2 + C3H2 = HCO + HCCO 1.00E13 0.00 0.00 ! U 1.0 [89MIL/BOW] ! O2 + H2CCCH = CH2CO + HCO 3.01E10 0.00 12.00 ! D 1.0 500- 900 [88SLA/GUT] ! O2 + HCO = HO2 + CO 3.01E12 0.00 0.00 ! O2+HCO=>(CO+HO2);(OH+CO2);(HCO3) ! k(overall)= 3.01E12 0.00 0.00 A/U 0.3 300-2500 [94BAU/COB] ! According to the measurements of Dobe et al. (unpublished) ! (HO2+CO) is the main channel until 600K ! O2 + CH3O = CH2O + HO2 2.17E10 0.00 7.32 ! A 0.3 300-1000 [94BAU/COB] ! O2 + CH2OH = CH2O + HO2 1.57E15 -1.00 0.00 DUPLICATE O2 + CH2OH = CH2O + HO2 7.23E13 0.00 14.97 DUPLICATE ! A 0.3 300-1200 [94BAU/COB] ! The rate is given as the sum of two expressions, ! hence the reaction is duplicated. ! O2 + HCCO = CO + CO + OH 1.63E12 0.00 3.58 ! O2+HCCO=>(2CO+OH);(C2O+HO2) ! k(overall)= 1.63E12 0.00 3.58 B/U 0.7 300-550 [94BAU/COB] ! H2O2 + H = HO2 + H2 1.69E12 0.00 15.71 ! A 0.3 300-1000 [94BAU/COB] ! H2O2 + H = OH + H2O 1.02E13 0.00 14.97 ! A 0.3 300-1000 [94BAU/COB] ! H2O2 + O = OH + HO2 6.62E11 0.00 16.63 ! A 0.3 300- 500 [94BAU/COB] ! H2O2 + OH = H2O + HO2 7.83E12 0.00 5.57 ! A 0.5 300-1000 [94BAU/COB] ! OH + OH (+ M) = H2O2 (+ M) 7.23E13 -0.37 0.00 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! B 0.5 200-1500 [94BAU/COB] LOW /5.53E19 -0.76 0.00 / ! scaled for N2; the original data: ! 2.21E19 -0.76 0.00 (N2) A 0.4 250-1400 [94BAU/COB] TROE /1 1 1 1040/ ! A 0.2 200-1500 [94BAU/COB] (Fc=0.5 for Ar) ! There are alternative rate data in [94BAU/COB] for H2O as a bath gas ! CO + O + M = CO2 + M 1.54E15 0.00 12.56 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for N2; the original data: ! B 0.4 300-2500 [86TSA/HAM] (N2) 6.17E14 0.00 12.56 ! CO + OH = CO2 + H 1.66E07 1.30 -3.20 ! A 0.5 250-2000 [76BAU/DRY] increased by 10% ! ! The [94BAU/COB] suggests 6.32E06 1.5 -2.08 A 0.5 300-2000 ! but [94MCL/SMI] claims that the [94BAU/COB] evaluation is based on wrong ! flame velocity measurements and the data of [76BAU/DRY] give better ! description of accurate flame velocity measurements and are in better ! agreement to direct kinetic measurements. ! [76BAU/DRY] suggests: ! k(cm**3 mol**-1 s**-1)= 10**7.18 T**1.3 exp(+385/T) ! valid for 250-2000K, unc= +-20%(at 300K) - +-50%(above 1000K) ! Note, that this expression was misprinted in [76BAU/DRY] ! the [76BAU/DRY] value: ! CO + OH = CO2 + H 1.51E07 1.30 -3.20 ! ! (10/7/97) the [76BAU/DRY] was increased by 10% to describe CO+OH flame velocities. ! ! CO + HO2 = CO2 + OH 1.51E14 0.00 99.02 ! B 0.3 300-2500 [86TSA/HAM] ! CO + CH = HCCO 2.77E11 0.00 -7.15 ! CO+CH=>(HCCO)(H+C2O) ! B/U 1.0 300-1000 [94BAU/COB] ! CO2 + CH = HCO + CO 3.43E12 0.00 2.87 ! CO2+CH=>(HCO+CO)(C2O+OH) ! B/U 1.0 300-1000 [94BAU/COB] ! CO2 + CH2 = CH2O + CO 2.35E10 0.00 0.00 ! B 0.2 300-2500 [86TSA/HAM] ! CH2O + H = HCO + H2 1.26E08 1.62 9.06 ! A 0.3 300-1700 [94BAU/COB] ! CH2O + CH = CH2 + HCO 9.64E13 0.00 -2.16 ! CH2O+CH=>(CH2+HCO)(CH2CO+H)(CH2CHO) ! k(overall)= 9.64E13 0.00 -2.16 B/U 1.0 300-700 [94BAU/COB] ! CH2O + CH3 = CH4 + HCO 7.83E-08 6.1 8.23 ! A 0.2 300-2000 [94BAU/COB] ! CH2O + O = HCO + OH 4.16E11 0.57 11.56 ! A 0.3 250-2200 [94BAU/COB] ! CH2O + OH = HCO + H2O 3.43E09 1.18 -1.87 ! A 0.5 300-3000 [94BAU/COB] ! CH2O + HO2 = H2O2 + HCO 3.01E12 0.00 54.71 ! B 0.5 600-1000 [94BAU/COB] ! CH2O + M = HCO + H + M 1.40E36 -5.54 404.58 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ CH2O + M = H2 + CO + M 3.26E36 -5.54 404.58 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! CH2O+M=>(HCO+H+M);(H2+CO+M) ! k(1+2; original)= 1.63E36 -5.54 404.58 B/B 0.3 1700-3200 [94BAU/COB] ! k(1+2; scaled)= 4.66E36 -5.54 404.58 ! k(2)/k= 0.7+-0.4 T=2000-3000K ! CH2CO + H = CH3 + CO 1.81E13 0.00 14.13 ! CH2CO+H=>(CH3+CO)(CH2CHO)(H2+HCCO) ! k(overall)= 1.81E13 0.00 14.13 B/U 1.0 200-2000 [94BAU/COB] ! k2/k is considered small => channel#2 is neglected ! channel#3 may be important at high temperature ! CH2CO + O = CH2 + CO2 1.33E12 0.00 5.65 CH2CO + O = CH2O + CO 4.58E11 0.00 5.65 CH2CO + O = HCO + H + CO 2.52E11 0.00 5.65 CH2CO + O = HCO + HCO 2.52E11 0.00 5.65 ! CH2CO+O=>(CH2+CO2)(CH2O+CO)(HCO+H+CO)(HCO+HCO) ! k(overall)= 2.29E12 0.00 5.65 B/U 0.3 230-500 [94BAU/COB] ! Information about branching ratios: ! [83WAS/HAT] k(2)/k = 20%+-10% ! [92OEH] k(1)/k = 58%+-10% ! (0.5 k(3)+k(4))/k = 21%+-5% ! We use here k(1)/k= 0.58, k(2)/k= 0.20, k(3)/k= 0.11, and k(4)/k= 0.11 ! CH2CO + OH = CH3 + CO2 2.52E12 0.00 0.00 CH2CO + OH = CH2OH + CO 4.68E12 0.00 0.00 ! CH2CO+OH=>(CH3+CO2)(CH2OH+CO)(CH3O+CO)(HCO+CH2O)(HCCO+H2O)(CH2O+H+CO) ! k(overall)= 7.20E12 0.00 0.00 D/U 296 [92OEH/TEM] ! According to the measurements of [94GRU/NOL] ! k(2)/k=0.60+-0.10; k(4)/k<0.02; k(5)/k<0.01; estimated: k(1)/k= 0.25 ! We use here k(1)/k= 0.35 and k(2)/k= 0.65 ! CH2CO + M = CH2 + CO + M 6.57E15 0.00 241.03 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! E 1.0 1650-1850 [86FRA/BHA] (Ar) 2.30E15 0.00 241.03 ! CH2CO + M = HCCO + H + M 1.14E9 0.00 0.00 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! E 1.0 2000-2300 [86FRA/BHA] 4.00E8 0.00 0.00 ! C + CH2 = C2H + H 5.00E13 0.00 0.00 ! U 1.0 [89MIL/BOW] ! C + CH3 = C2H2 + H 5.00E13 0.00 0.00 ! C+CH3=>(C2H2+H)(C2H+H2) ! U/U 1.0 [89MIL/BOW] ! C + OH = CO + H 5.00E13 0.00 0.00 ! U 1.0 [89MIL/BOW] ! H + H + M = H2 + M 1.87E18 -1.00 0.00 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ H2/0.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! B 0.5 300-2500 [94BAU/COB] (Ar) 6.53E17 -1.00 0.00 ! H + H + H2 = H2 + H2 9.79E16 -0.60 0.00 ! B 0.5 100-5000 [94BAU/COB] ! H + CH = C + H2 8.43E12 0.00 0.00 ! D 1.0 297 [89BEC/ENG] ! H + CH2 = CH + H2 6.02E12 0.00 -7.48 ! B 0.7 300-3000 [94BAU/COB] ! H + CH2(S) = CH2 + H 2.00E14 0.00 0.00 ! H+CH2(S)=>(CH2+H)(CH+H2) ! U/U 1.0 [89MIL/BOW] ! H + CH3 (+M) = CH4 (+M) 1.688E14 0.00 0.00 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ LOW / 1.408E24 -1.8 0.0 / ! The data of [94BAU/COB] gave too low methane flame velocities and ! therefore both the high-pressure and low-pressure A factors ! were decresased by 50%. - modified to 80% of cec recommendation ! when the error in CH3+OH=CH2(S)+H2O was corrected, along with going ! back to the original H+CH2OH=CH3+OH ! ! the original [94BAU/COB] data: ! 2.11E14 0.00 0.00 B 0.3 300-1000 [94BAU/COB] ! 6.17E23 -1.8 0.0 (Ar) /low pressure limit/ ! B 0.3 300-1000 [94BAU/COB] ! when scaled for Argon: ! LOW / 1.76E24 -1.8 0.0 / ! TROE / 0.37 3315 61 / ! B 0.1 300-1000 [94BAU/COB] !There are alternative rate data in [94BAU/COB] for He and C2H6 as bath gases ! H + C2H3 = C2H2 + H2 1.20E13 0.00 0.00 ! B 0.5 300-2500 [94BAU/COB] ! CH3 + CH3 = C2H5 + H 3.01E13 0.00 56.54 ! B 0.6 1300-2500 [94BAU/COB] ! H + O + M = OH + M 1.18E19 -1.0 0.00 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for N2; the original data: ! S 0.7 300-2500 [86TSA/HAM] 4.71E18 -1.0 0.00 ! H + OH + M = H2O + M 5.53E+22 -2.0 0.00 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/2.55/ CH4/3.0/ C2H6/3.0/ AR/0.15/ ! scaled for N2; the original data: ! B 0.5 300-3000 [94BAU/COB] 2.21E+22 -2.0 0.00 !There are alternative rate data in [94BAU/COB] for H2O and Ar as bath gases !The 3rd body efficiencies for H2O and Ar were deduced from these data ! H + HO2 = H2 + O2 4.28E13 0.00 5.90 ! A 0.3 300-1000 [94BAU/COB] ! H + HO2 = OH + OH 1.69E14 0.00 3.66 ! A 0.3 300-1000 [94BAU/COB] ! H + HO2 = H2O + O 3.01E13 0.00 7.20 ! A 0.3 300-1000 [94BAU/COB] ! H + HCO = CO + H2 9.03E13 0.00 0.00 ! A 0.3 300-2500 [94BAU/COB] ! H + CH3O = CH2O + H2 1.81E13 0.00 0.00 ! A 0.5 300-1000 [94BAU/COB] ! ! ! ! ! H + CH2OH = CH3 + OH 1.15E14 0.00 6.00 H + CH2OH = CH3 + OH 1.02E13 0.00 0.00 H + CH2OH = CH2O + H2 3.08E13 0.00 0.00 ! ! the original data of Dobe et al [94DOB/BER] gave too low a flame velocity !therefore the activation energy is increased to 6kJ/mol, an estimate of !the theoretical maximum, while adjusting the A-factor to keep the same value !for the room temperature measurement of this reaction. - Correcting the error !in CH3+OH=CH2(S)+H2O meant that this alteration was no longer required in !order to predict the stoichiometric methane/air flame velocity, so we went !back to the original expression. ! ! The original data: ! ! H + CH2OH = CH3 + OH 1.02E13 0.00 0.00 ! H + CH2OH = CH2O + H2 3.08E13 0.00 0.00 ! H+CH2OH=>(CH3+OH)(CH2O+H2) ! k(overall)= 4.1E13 0.00 0.00 D 298 [94DOB/BER] ! k(1)/k= 0.25+-0.05 [94DOB/BER] ! H + HCCO = CH2 + CO 1.51E14 0.00 0.00 ! B 0.4 300-2500 [94BAU/COB] ! CH + CH2 = C2H2 + H 4.00E13 0.00 0.00 ! U 1.0 [89MIL/BOW] ! CH + CH3 = C2H3 + H 3.00E13 0.00 0.00 ! U 1.0 [89MIL/BOW] ! CH + C2H3 = CH2 + C2H2 5.00E13 0.00 0.00 ! U 1.0 [89MIL/BOW] ! CH + O = CO + H 3.97E13 0.00 0.00 ! A 0.5 300-2000 [94BAU/COB] ! CH + OH = HCO + H 3.00E13 0.00 0.00 ! U 1.0 [89MIL/BOW] ! CH + HCCO = C2H2 + CO 5.00E13 0.00 0.00 ! CH+HCCO=>(C2H2+CO)(C2H+HCO) ! U/U 1.0 [89MIL/BOW] ! CH2 + CH2 = C2H2 + H2 1.20E13 0.00 3.33 CH2 + CH2 = C2H2 + H + H 1.08E14 0.00 3.33 ! CH2+CH2=>(C2H2+H2);(C2H2+H+H) ! k(overall)= 1.20E14 0.00 3.33 B/B 0.5 300-3000 [94BAU/COB] ! k2/k=0.9+-0.1 ! CH2 + CH3 = C2H4 + H 4.22E13 0.00 0.00 ! B 0.4 300-3000 [94BAU/COB] ! CH2 + C2H3 = C2H2 + CH3 1.81E13 0.00 0.00 ! S 0.5 300-2500 [86TSA/HAM] ! CH2 + O = CO + H + H 7.20E13 0.00 0.00 CH2 + O = CO + H2 4.80E13 0.00 0.00 ! CH2+O=>(CO+2H);(CO+H2) 1.20E14 0.00 0.00 ! A/B 0.7 300-2500 [94BAU/COB] ! k1/k=0.6+-0.3 ! CH2 + OH = CH2O + H 1.81E13 0.00 0.00 ! U 0.5 300-2500 [86TSA/HAM] ! CH2 + HCO = CH3 + CO 1.81E13 0.00 0.00 ! U 0.5 300-2500 [86TSA/HAM] ! CH2 + HCCO = C2H3 + CO 3.00E13 0.00 0.00 ! U/U 1.0 [86GLA/MIL] ! CH2 + HCCO = C2H + CH2O 1.00E13 0.00 8.37 ! U/U 1.0 [86GLA/MIL] ! CH2(S) + M = CH2 + M 1.51E13 0.00 0.00 N2/.4/ O2/.4/ CO/.75/ CO2/1.5/ H2O/6.5/ CH4/.48/ C2H2/3.2/ C2H4/1.6/ C2H6/1.44/ AR/.24/ ! scaled for N2; the original data: ! B 0.3 300-2000 [94BAU/COB] 6.02E12 0.00 0.00 ! 3rd body efficiences for CH4,C2H2,C2H4,C2H6,Ar were taken from [94BAU/COB] ! CH3 + CH3 (+M) = C2H6 (+M) 3.61E13 0.00 0.00 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! A 0.3 300-2000 [94BAU/COB] LOW / 3.63E41 -7.0 11.56 / ! scaled for Ar; the original data: ! 1.27E41 -7.0 11.56 (Ar) A 0.3 300-2000 [94BAU/COB] TROE / 0.62 73 1180 / ! A 0.1 300-2000 [94BAU/COB] ! CH3 + O = CH2O + H 8.43E13 0.00 0.00 ! A 0.2 300-2500 [94BAU/COB] ! ! CH3 + OH = CH2(S) + H2O 7.23E13 0.00 11.64 ! B 0.5 300-1000 [94BAU/COB] ! corrected factor of ten error on cec summary page ! ! CH3 + HO2 = CH3O + OH 1.80E13 0.00 0.00 ! B 0.7 300-2500 [94BAU/COB] ! CH3 + HCO = CH4 + CO 1.20E14 0.00 0.00 ! B 0.3 300-2500 [86TSA/HAM] ! CH3 + M = CH2 + H + M 2.91E16 0.00 379.14 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! B 0.5 1500-3000 [94BAU/COB] (Ar) 1.02E16 0.00 379.14 ! C2H + C2H3 = C2H2 + C2H2 1.90E13 0.00 0.00 ! S 0.5 300-2500 [86TSA/HAM] !(The original [86TSA/HAM] rate estimation referred to the overall reaction.) ! C2H + O = CH + CO 1.00E13 0.00 0.00 ! B 1.0 300-2500 [94BAU/COB] ! C2H + OH = HCCO + H 2.00E13 0.00 0.00 ! U/U 1.0 [89MIL/BOW] ! ! C2H+OH=>CH2+CO 1.81E13 0.00 0.00 B* 0.7 300-2500 C2H + OH = CH2 + CO 1.81E13 0.00 0.00 ! U/U 0.7 300-2500 [86TSA/HAM] ! C2H3 + O = CO + CH3 3.00E13 0.00 0.00 ! C2H3+O=>(CO+CH3)(OH+C2H2)(HCO+CH2) ! B/U 0.5 300-2000 [94BAU/COB] ! probably channel#1 is dominant ! C2H3 + OH = C2H2 + H2O 5.00E12 0.00 0.00 ! U 1.0 [89MIL/BOW] ! C2H5 + O = CH2O + CH3 6.62E13 0.00 0.00 ! C2H5+O=>(CH3CHO+H);(CH2O+CH3) ! k(overall)= 6.62E13 0.00 0.00 B/U 0.5 300-2500 [94BAU/COB] ! k2/k= 0.17+-0.2 at 300K ! This reaction produces mainly CH3CHO, at least near room temperature. ! However, we do not want to include CH3CHO in this mechanism. ! The overall rate is used for a good account of the removal of radicals ! C2H5 and O ! H2CCCH + O = C2H2 + CO + H 1.39E14 0.00 0.00 ! D 1.0 295- 750 [91SLA/GUT] ! [91SLA/GUT] have suggested (C3H2O+H) as products, ! but a fast decomposition of C3H2O to C2H2 and CO is assumed. ! H2CCCH + OH = C3H2 + H2O 2.00E13 0.00 0.00 ! U 1.0 [89MIL/BOW] ! H2CCCCH+M = C4H2 + H + M 1.12E16 0.00 194.62 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for N2; the original data: ! T 1.0 700-1300 [88DUR/AMO] 4.46E15 0.00 194.62 ! O + O + M = O2 + M 5.40E13 0.00 -7.48 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! A 0.114 200-4000 [86TSA/HAM] (Ar) 1.89E13 0.00 -7.48 ! O + HO2 = O2 + OH 3.19E13 0.00 0.00 ! A 0.5 300-1000 [94BAU/COB] ! O + HCO = CO + OH 3.01E13 0.00 0.00 ! A 0.3 300-2500 [94BAU/COB] ! O + HCO = CO2 + H 3.01E13 0.00 0.00 ! A 0.3 300-2500 [94BAU/COB] ! O2 + CH3 = CH3O + O 4.40E13 0.00 131.37 ! B 0.5 300-2500 [94BAU/COB] ! reduced x3 from cec recommendation, improved ignition delay ! calculations in methane/oxygen/argon, (no effect in flame speed ! calculations) ! O + CH3O = CH2O + OH 1.81E12 0.00 0.00 ! O+CH3O=>(O2+CH3)(OH+CH2O) 1.51E13 0.00 0.00 ! B/B 0.7 300-1000 [94BAU/COB] ! k2/k= 0.12+-0.1 at 300K ! O + CH2OH = CH2O + OH 9.03E13 0.00 0.00 ! D 1.0 300 [88GRO/RIE2] ! O + HCCO = H + CO + CO 9.64E13 0.00 0.00 ! A 0.3 300-2500 [94BAU/COB] ! OH + OH = O + H2O 1.51E09 1.14 0.42 ! A 0.2 250-2500 [94BAU/COB] ! OH + HO2 = H2O + O2 2.89E13 0.00 -2.08 ! A 0.5 300-2000 [94BAU/COB] ! OH + HCO = H2O + CO 1.02E14 0.00 0.00 ! B 0.3 300-2500 [94BAU/COB] ! OH + CH3O = CH2O + H2O 1.81E13 0.00 0.00 ! S 0.7 300-2500 [86TSA/HAM] ! OH + CH2OH = CH2O + H2O 2.41E13 0.00 0.00 ! S 0.5 300-2500 [86TSA/HAM] ! The uncertainty of 0.3 suggested by [86TSA/HAM] was increased ! OH + HCCO = HCO + HCO 1.00E13 0.00 0.00 OH + HCCO = CH2O + CO 1.00E13 0.00 0.00 ! U/U 1.0 ! HO2 + HO2 = H2O2 + O2 4.22E14 0.00 50.14 DUPLICATE ! A 0.4 850-1250 [94BAU/COB] ! HO2 + HO2 = H2O2 + O2 1.32E11 0.00 -6.82 DUPLICATE ! A 0.15 550- 850 [94BAU/COB] ! HCO + HCO = CH2O + CO 3.01E13 0.00 0.00 ! B 0.3 300 [94BAU/COB] ! HCO + M = H + CO + M 4.49E14 0.00 65.93 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! A 0.5 600-2500 [94BAU/COB] (Ar) 1.57E14 0.00 65.93 ! CH3O + M = CH2O + H + M 1.55E14 0.00 56.46 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! B 0.3 300-1700 [94BAU/COB] (Ar) 5.42E13 0.00 56.46 ! CH2OH + M = CH2O + H + M 1.26E16 0.00 125.60 N2/0.4/ O2/0.4/ CO/0.75/ CO2/1.5/ H2O/6.5/ CH4/3.0/ C2H6/3.0/ AR/0.35/ ! scaled for Ar; the original data: ! E 1.0 1372-1842 [89HID/OKI2] 4.40E15 0.00 125.60 ! HCCO + HCCO = C2H2 + CO + CO 1.00E13 0.00 0.00 ! U/U 1.0 [89MIL/BOW] ! !============================================================================ ! ! Data bases: ! ! NIST ! Mallard WG, Westley F, Herron JT, Hampson RF, Fizzell DH ! NIST Chemical Kinetics Database, ver 6.0 ! NIST Standard Reference Data, Gaithersburg, MD (1994) ! ! LEEDS ! Baulch DL ! Reaction Kinetics Database ! School of Chemistry, The University of Leeds ! ! ! Literature ! ! [94ALV/MOO] ! Alvarez RA, Moore CB ! J.Phys.Chem.,98,174-183(1994) ! ! [80ASH/FUL] ! Ashfold MNR., Fullstone MA, Hancock G, Ketley GW ! Chem.Phys.,55,245(1980) ! ! [94BAU/COB] ! Baulch DL, Cobos CJ, Cox RA, Frank P, Hayman G, Just TH, Kerr JA, Murrels T ! Pilling MJ, Troe J, Walker RW, Warnatz J ! Combust.Flame 98,59-79(1994) ! ! [76BAU/DRY] ! Baulch DL, Drysdale DD, Duxbury J, Grant S ! Evaluated Kinetic Data for High Temperature Reactions ! Butterworth, London, 1976, Vol.3 ! ! [89BEC/ENG] ! Becker KH, Engelhardt B, Wiesen P ! Chem.Phys.Lett., 154,342(1989) ! ! [85BOH/DOB] ! Bohland T, Dobe S, Temps F, Wagner HGg ! Ber.Bunsenges.Phys.Chem., 89, 1110(1985) ! ! [90COL/DES] ! Collin GJ, Deslauriers H, De Mare GR, Poirier RA ! J.Phys.Chem., 94, 134-141(1990) ! ! [91DEA/DAV] ! Dean AJ, Davidson DF, Hanson RK ! J.Phys.Chem.,95,183(1991) ! ! [94DOB/BER] ! Dobe S, Berces T, Temps F, Wagner HGg, Ziemer H ! J.Phys.Chem., 98, 9792-9800(1994) ! ! [94DOB/TUR] ! Dobe S, Turanyi T, Berces T, Marta F ! Abstracts of the 13th International Symposium on Gas Kinetics ! Dublin, 11-16th September, 1994 ! Paper D36 (pp.319-321), 1994 ! ! [88DUR/AMO] ! Duran RP, Amorebieta VT, Colussi AJ ! J.Phys.Chem., 92,636(1988) ! ! [86FRA/BHA] ! Frank P, Bhaskaran KA, Just Th ! J.Phys.Chem., 90,2226(1986) ! ! [86GLA/MIL] ! Glarborg P.,Miller JA, Kee RJ ! Combust Flame 65,177(1986) ! ! [92GRO/KEL] ! Grotheer HH, Kelm S, Driver HST, Hutcheon RJ, Lockett RD, Robertson GN ! Ber.Bunsenges.Phys.Chem.,96,1360-1376(1992) ! ! [88GRO/RIE2] ! Grotheer HH, Riekert G, Walter D, Just Th ! Chem.Phys.Lett.,148,530(1988) ! ! [94GRU/NOL] ! Grussdorf J, Nolte J, Temps F, Wagner HGg ! Ber.Bunsenges.Phys.Chem.,98,546-553(1994) ! ! [89HID/OKI2] ! Hidaka Y, Oki T, Kawano H ! J.Phys.Chem.,93,7134(1989) ! ! [89HSU/AND] ! Hsu KJ, Anderson SM, Durant JL, Kaufman F ! J.Phys.Chem.,93,1018-1021(1989) ! ! [91KOI] ! Koike T ! Bull.Chem.Soc.Jpn., 64,1726-1730(1991) ! ! [83LAN/PET] ! Langford AO, Petek H, Moore CB ! J.Chem.Phys.,78,6650(1983) ! ! [94MCL/SMI] ! McLean IC, Smith DB, Taylor SC ! Proceedings of the 25th Symposium (Int.) on Combustion ! The Combustion Institute, Pittsburgh, 1994, in press ! ! [89MIL/BOW] ! Miller JA, Bowman CT ! Prog.Energy Comb.Sci.,15,287(1989) ! ! [86MIT/NAV] ! Mitchell MB, Nava DF, Stief LJ ! 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