! ! *************************************************************************** ! * * ! * Sulphur mechanism extension to * ! * 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 ! http://garfield.chem.elte.hu/Combustion/Combustion.html ! ! !*****Version 5.2 ******************************************************** ! ! 08/06/2005, Modified Fc term for OH+SO2(+M) = HOSO2(+M), Now temperature ! independent, more appropriate for use at higher temperatures. ! !*****Version 5.1 ******************************************************** ! ! 18/10/2003, Corrected an error in the reaction S+OH = SH+O ! !*****Version 5.0 ******************************************************** ! ! 1/5/2002, modified as a result of the publication of Glarborg et al., ! Comnbust. Flame, 127:2234-2251 (2001) (Minor changes to several ! rate coefficients, removed SO2* reactions, changes to HOSO, H2S2 ! and H2S thermodynamics) ! ! modified due to master equation calculations on H+SO2=OH+SO ! system (Hughes Blitz & Pilling. accepted for presentation in ! the 29th International Symposium on Combustion and subsequent ! publication in the Proceedings of the Combustion Institute) ! Gives new rate coefficients for the elementary reaction in this ! system, and reverted to HOSO themodynamic properties of Marshall ! et al., ! ! modified due to experimental measurements on OH+SO and OH+SO2 of Blitz ! Hughes and Pilling leading to new rate coefficients and HOSO2 ! heat of formation ! ! C/H/O thermodynamics taken from Leeds Methane mechanism v1.5 ! ! ! ! !*****Version 4.0 ******************************************************** ! ! 9/10/2000, Combined new Glarborg mechanism with our mechanism ! 10-11/2000, Added experimental measurements from School of Chemistry ! ! ! ELEMENTS H O C N AR HE S END SPECIES H2 CH4 O2 H2O CO CO2 C H CH CH3 O OH HO2 N2 AR N NH NO NO2 S SH H2S SO SO2 SO3 HSO2 HOSO HOSO2 SN S2 CS COS HSNO HSO HOS HSOH H2SO HOSHO HS2 H2S2 H2SO4 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 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 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 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 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 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 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 300.00 5000.00 1000.00 0 1 2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -7.45375000E+02 4.36600100E+00 2.50000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-7.45375000E+02 4.36600100E+00 4 N N 1 0 0 0G 300.00 5000.00 1000.00 0 1 2.45026800E+00 1.06614600E-04-7.46533700E-08 1.87965200E-11-1.02598400E-15 2 5.61160400E+04 4.44875800E+00 2.50307100E+00-2.18001800E-05 5.42052900E-08 3 -5.64756000E-11 2.09990400E-14 5.60989000E+04 4.16756600E+00 4 NH H 1N 1 0 0G 300.00 5000.00 1000.00 0 1 2.76024900E+00 1.37534600E-03-4.45191400E-07 7.69279200E-11-5.01759200E-15 2 4.20782800E+04 5.85719900E+00 3.33975800E+00 1.25300900E-03-3.49164600E-06 3 4.21881200E-09-1.55761800E-12 4.18504700E+04 2.50718100E+00 4 NO O 1N 1 0 0G 300.00 5000.00 1000.00 0 1 3.24543500E+00 1.26913800E-03-5.01589000E-07 9.16928300E-11-6.27541900E-15 2 9.80084000E+03 6.41729400E+00 3.37654200E+00 1.25306300E-03-3.30275100E-06 3 5.21781000E-09-2.44626300E-12 9.81796100E+03 5.82959000E+00 4 NO2 O 2N 1 0 0G 300.00 5000.00 1000.00 0 1 4.68285900E+00 2.46242900E-03-1.04225900E-06 1.97690200E-10-1.39171700E-14 2 2.26129200E+03 9.88598500E-01 2.67060000E+00 7.83850100E-03-8.06386500E-06 3 6.16171500E-09-2.32015000E-12 2.89629100E+03 1.16120700E+01 4 S S 1 0 0 0G 300.00 5000.00 1000.00 0 1 2.90214800E+00-5.48454600E-04 2.76457600E-07-5.01711500E-11 3.15068500E-15 2 3.24942300E+04 3.83847100E+00 3.18732900E+00-1.59577600E-03 2.00553100E-06 3 -1.50708100E-09 4.93128200E-13 3.24225900E+04 2.41444100E+00 4 SH H 1S 1 0 0G 300.00 5000.00 1000.00 0 1 3.05381000E+00 1.25888400E-03-4.24916900E-07 6.92959100E-11-4.28169100E-15 2 1.58822500E+04 5.97355100E+00 4.13332700E+00-3.78789300E-04-2.77785400E-06 3 5.37011200E-09-2.39400600E-12 1.55586200E+04 1.61153500E-01 4 H2S H 2S 1 0 0G 300.00 5000.00 1000.00 0 1 2.88314700E+00 3.82783500E-03-1.42339800E-06 2.49799900E-10-1.66027300E-14 2 -3.48074300E+03 7.25816200E+00 3.07102900E+00 5.57826100E-03-1.03096700E-05 3 1.20195300E-08-4.83837000E-12-3.55982600E+03 5.93522600E+00 4 SO O 1S 1 0 0G 300.00 5000.00 1000.00 0 1 4.02107800E+00 2.58485600E-04 8.94814200E-08-3.58014500E-11 3.22843000E-15 2 -7.11962000E+02 3.45252300E+00 3.08040100E+00 1.80310600E-03 6.70502200E-07 3 -2.06900500E-09 8.51465700E-13-3.98616300E+02 8.58102800E+00 4 SO2 O 2S 1 0 0G 300.00 5000.00 1000.00 0 1 5.25449800E+00 1.97854500E-03-8.20422600E-07 1.57638300E-10-1.12045100E-14 2 -3.75688600E+04-1.14605600E+00 2.91143900E+00 8.10302200E-03-6.90671000E-06 3 3.32901600E-09-8.77712100E-13-3.68788200E+04 1.11174000E+01 4 SO3 O 3S 1 0 0G 300.00 5000.00 1000.00 0 1 7.05066800E+00 3.24656000E-03-1.40889700E-06 2.72153500E-10-1.94236500E-14 2 -5.02066800E+04-1.10644300E+01 2.57528300E+00 1.51509200E-02-1.22987200E-05 3 4.24025700E-09-5.26681200E-13-4.89441100E+04 1.21951200E+01 4 HSO2 H 1O 2S 1 0G 300.00 1500.00 1500.00 0 1 1.56273740E+00 2.06913890E-02-2.31120730E-05 1.26702030E-08-2.72741760E-12 2 -1.82148240E+04 1.75568200E+01 1.56273740E+00 2.06913890E-02-2.31120730E-05 3 1.26702030E-08-2.72741760E-12-1.82148240E+04 1.75568200E+01 4 HOSO H 1O 2S 1 0G 300.00 2000.00 1000.00 0 1 9.60146992E+00-2.53592657E-02 6.76829409E-05-6.34954136E-08 1.95893537E-11 2 -3.12540147E+04-1.56740934E+01 9.60146992E+00-2.53592657E-02 6.76829409E-05 3 -6.34954136E-08 1.95893537E-11-3.12540147E+04-1.56740934E+01 4 HOSO2 H 1O 3S 1 0G 300.00 2000.00 1000.00 0 1 7.62277304E+00-4.19908990E-03 3.52054969E-05-4.12715317E-08 1.40006629E-11 2 -4.69478133E+04-7.80787503E+00 7.62277304E+00-4.19908990E-03 3.52054969E-05 3 -4.12715317E-08 1.40006629E-11-4.69478133E+04-7.80787503E+00 4 SN N 1S 1 0 0G 300.00 5000.00 1000.00 0 1 3.88828700E+00 6.77842700E-04-2.72530900E-07 5.13592700E-11-3.59383600E-15 2 3.04449600E+04 4.19429100E+00 3.40734600E+00 1.79788700E-03-2.01897000E-06 3 2.10785700E-09-9.52759200E-13 3.06237300E+04 6.82148100E+00 4 S2 S 2 0 0 0G 300.00 5000.00 1000.00 0 1 3.90444300E+00 6.92573300E-04-1.23309700E-07 8.78380900E-13 1.37466200E-15 2 1.42569300E+04 4.95683400E+00 3.15767300E+00 3.09948000E-03-1.56074600E-06 3 -1.35789100E-09 1.13744400E-12 1.43918700E+04 8.59606200E+00 4 CS C 1S 1 0 0G 300.00 5000.00 1000.00 0 1 3.73743100E+00 8.18045100E-04-3.17891800E-07 5.35680100E-11-2.88619500E-15 2 3.24772500E+04 3.57655700E+00 2.93862300E+00 2.72435200E-03-2.39770700E-06 3 1.68950100E-09-6.66505000E-13 3.27399200E+04 7.84872000E+00 4 COS O 1C 1S 1 0G 300.00 5000.00 1000.00 0 1 5.19192500E+00 2.50612300E-03-1.02439600E-06 1.94391400E-10-1.37080000E-14 2 -1.84621000E+04-2.82575500E+00 2.85853100E+00 9.51545800E-03-8.88491500E-06 3 4.22099400E-09-8.55734000E-13-1.78514500E+04 9.08198900E+00 4 HSNO H 1O 1N 1S 1G 300.00 5000.00 1000.00 0 1 2.90214800E+00-5.48454600E-04 2.76457600E-07-5.01711400E-11 3.15068400E-15 2 3.24942300E+04 3.83847100E+00 3.18732900E+00-1.59577630E-03 2.00553100E-06 3 -1.50708140E-09 4.93128200E-13 3.24225900E+04 2.41444100E+00 4 HSO H 1O 1S 1 0G 300.00 1500.00 1500.00 0 1 2.58075930E+00 7.99109020E-03-5.15359720E-06 7.42028010E-10 2.44456910E-13 2 -3.79766780E+03 1.22267030E+01 2.58075930E+00 7.99109020E-03-5.15359720E-06 3 7.42028010E-10 2.44456910E-13-3.79766780E+03 1.22267030E+01 4 HOS H 1O 1S 1 0G 300.00 1500.00 1500.00 0 1 2.63736730E+00 7.89119090E-03-8.11726030E-06 4.24833820E-09-8.57901160E-13 2 -1.07268870E+03 1.17096820E+01 2.63736730E+00 7.89119090E-03-8.11726030E-06 3 4.24833820E-09-8.57901160E-13-1.07268870E+03 1.17096820E+01 4 HSOH H 2O 1S 1 0G 300.00 1500.00 1500.00 0 1 2.56764410E+00 1.13805210E-02-5.86673240E-06-5.94700410E-10 8.74383290E-13 2 -1.55712560E+04 1.17663990E+01 2.56764410E+00 1.13805210E-02-5.86673240E-06 3 -5.94700410E-10 8.74383290E-13-1.55712560E+04 1.17663990E+01 4 H2SO H 2O 1S 1 0G 300.00 1500.00 1500.00 0 1 1.95805190E+00 9.72652010E-03 6.84131700E-07-6.23437200E-09 2.41665770E-12 2 -6.67708890E+03 1.47834510E+01 1.95805190E+00 9.72652010E-03 6.84131700E-07 3 -6.23437200E-09 2.41665770E-12-6.67708890E+03 1.47834510E+01 4 HOSHO H 2O 2S 1 0G 300.00 1500.00 1500.00 0 1 1.19038220E+00 2.56447350E-02-2.66228420E-05 1.34796650E-08-2.64746290E-12 2 -3.37448860E+04 1.90954940E+01 1.19038220E+00 2.56447350E-02-2.66228420E-05 3 1.34796650E-08-2.64746290E-12-3.37448860E+04 1.90954940E+01 4 HS2 H 1S 2 0 0G 300.00 5000.00 1395.00 0 1 5.10949802E+00 1.61440788E-03-5.59150857E-07 8.75419872E-11-5.10877907E-15 2 1.07861033E+04 4.66519398E-01 3.24915375E+00 6.72607196E-03-6.12427074E-06 3 2.88457020E-09-5.42122152E-13 1.13627566E+04 1.01981642E+01 4 H2S2 H 2S 2 0 0G 300.00 5000.00 1395.00 0 1 6.23682403E+00 3.17137220E-03-1.08859887E-06 1.69375472E-10-9.84045085E-15 2 -4.06812922E+02-6.92943476E+00 3.15971698E+00 1.19631659E-02-1.11173543E-05 3 5.43915901E-09-1.06004978E-12 5.26704992E+02 9.07002520E+00 4 H2SO4 H 2O 4S 1 0G 200.00 6000.00 1000.00 0 1 1.14077640E+01 6.47450160E-03-2.26841850E-06 3.60607600E-10-2.13733800E-14 2 -9.23511920E+04-3.21413070E+01 1.58786610E+00 4.08823660E-02-4.88457630E-05 3 2.90145030E-08-6.68589150E-12-9.00400150E+04 1.66877800E+01 4 END REACTIONS MOLES KELVINS ! ! ! ! 1 H2S+M = S+H2+M 1.600E+24 -2.6100 44800.00 N2/1.5/ SO2/10/ H2O/10/ ! [01GLA/ALZ] ! ! 2 H2S+H = SH+H2 1.200E+07 2.1000 350.00 ! 293 - 2237K [92YOS/KOS] ! ! 3 H2S+O = SH+OH 7.500E+07 1.7500 1460.00 ! [01GLA/ALZ] ! ! 4 H2S+OH = SH+H2O 2.700E+12 0.0000 0.00 ! [91TYN/RAV] ! ! 5 H2S+S = 2SH 8.300E+13 0.0000 3700.00 ! [01GLA/ALZ] ! ! 6 H2S+S = HS2+H 2.000E+13 0.0000 3723.84 ! [01GLA/ALZ] ! ! 7 S+H2 = SH+H 1.400E+14 0.0000 9700.00 ! [01GLA/ALZ] ! ! 8 SH+O = H+SO 1.000E+14 0.0000 0.00 ! [01GLA/ALZ] ! ! 9 SH+OH = S+H2O 1.000E+13 0.0000 0.00 ! [01GLA/ALZ] (estimate) ! ! 10 SH+HO2 = HSO+OH 1.000E+12 0.0000 0.00 ! [01GLA/ALZ] ! ! 11 SH+O2 = HSO+O 1.900E+13 0.0000 9000.00 ! [01GLA/ALZ] ! ! 12 S+OH = H+SO 4.000E+13 0.0000 0.00 ! [01GLA/ALZ] ! ! 13 S+O2 = SO+O 5.200E+06 1.8100 -600.00 ! [01GLA/ALZ] ! ! 14 2SH = S2+H2 1.000E+12 0.0000 0.00 ! [01GLA/ALZ] ! ! 15 SH+S = S2+H 1.000E+13 0.0000 0.00 ! [01GLA/ALZ] ! ! 16 S2+M = 2S+M 4.800E+13 0.0000 38800.00 ! [80HIG/SAI] ! ! 17 S2+H+M = HS2+M 1.000E+16 0.0000 0.00 N2/1.5/ SO2/10/ H2O/10/ ! [01GLA/ALZ] ! ! 18 S2+O = SO+S 1.000E+13 0.0000 0.00 ! [01GLA/ALZ] ! ! 19 HS2+H = S2+H2 1.200E+07 2.1000 352.42 ! [01GLA/ALZ] ! ! 20 HS2+O = S2+OH 7.500E+07 1.8000 1460.00 ! [01GLA/ALZ] ! ! 21 HS2+OH = S2+H2O 2.700E+12 0.0000 0.00 ! [01GLA/ALZ] ! ! 22 HS2+S = S2+SH 8.300E+13 0.0000 3700.00 ! [01GLA/ALZ] ! ! 23 HS2+H+M = H2S2+M 1.000E+16 0.0000 0.00 N2/1.5/ SO2/10/ H2O/10/ ! [01GLA/ALZ] ! ! 24 H2S2+H = HS2+H2 1.200E+07 2.1000 360.00 ! [01GLA/ALZ] ! ! 25 H2S2+O = HS2+OH 7.500E+07 1.8000 1460.00 ! [01GLA/ALZ] ! ! 26 H2S2+OH = HS2+H2O 2.700E+12 0.0000 0.00 ! [01GLA/ALZ] ! ! 27 H2S2+S = HS2+SH 8.300E+13 0.0000 3700.00 ! [01GLA/ALZ] ! ! 28 SO3+H = HOSO+O 2.500E+05 2.9200 25300.00 ! [01GLA/ALZ] ! ! 29 SO3+O = SO2+O2 2.000E+12 0.0000 10000.00 ! [01GLA/ALZ] ! ! 30 SO3+SO = 2SO2 1.000E+12 0.0000 5000.00 ! [01GLA/ALZ] ! ! 31 SO+O(+M) = SO2(+M) 3.200E+13 0.0000 0.00 N2/1.5/ SO2/10/ H2O/10/ LOW / 1.200E+21 -1.54 0.00 / TROE / 0.5500 1.0e-30 1e+30 / ! [01GLA/ALZ] ! ! 32 SO2+O(+M) = SO3(+M) 9.200E+10 0.0000 1200.00 LOW / 2.400E+28 -4.00 2640.00 / ! [01GLA/ALZ] ! ! ! Modified to have a temperature independent Fc term. The value obtained for ! the relatively narrow temperature range of its determination (up to 370K) is not ! appropriate to extrapolate to high temperatures. Also modified kinf expression ! to be exactly consistent with what finally appeared in the paper, this was a ! negligible change. ! 33 SO2+OH(+M) = HOSO2(+M) 5.7306E+12 -0.2700 0.00 LOW / 1.688E+27 -4.09 0.00 / ! TROE / 1.0000E+00 1.0000E+30 4.1200E+02 / TROE / 0.47 1e-30 1e30 / ! [03BLI/HUG] ! ! 34 SO2+OH = HOSO+O 3.900E+08 1.8900 38200.00 ! [96GLA/KUB] ! ! 35 SO2+OH = SO3+H 4.900E+02 2.6900 12000.00 ! [96GLA/KUB] ! ! 36 SO2+CO = SO+CO2 2.700E+12 0.0000 24300.00 ! [01GLA/ALZ] ! ! 39 SO+M = S+O+M 4.000E+14 0.0000 54000.00 N2/1.5/ SO2/10/ H2O/10/ ! [01GLA/ALZ] ! ! 40 SO+H+M = HSO+M 5.000E+15 0.0000 0.00 N2/1.5/ SO2/10/ H2O/10/ ! [96GLA/KUB] ! ! 41 HOSO(+M) = SO+OH(+M) 9.940E+21 -2.5400 38190.00 LOW / 1.156E+46 -9.02 26647.00 / TROE / 9.5000E-01 2.9890E+03 1.1000E+00 / ! [02HUG/BLI] ! ! SO+OH = SO2+H 1.077E+17 -1.35 0 ! new experimental measurement from Chemistry department in Leeds ! [00BLI/MCK] ! ! ! 43 SO+O2 = SO2+O 7.600E+03 2.3700 1500.00 ! [01GLA/ALZ] ! ! 44 2SO = SO2+S 2.000E+12 0.0000 2000.00 ! [96GLA/KUB] ! ! 45 HSO+H = HSOH 2.500E+20 -3.1400 460.00 ! [96GLA/KUB] ! ! 46 HSO+H = SH+OH 4.900E+19 -1.8600 785.00 ! [96GLA/KUB] ! ! 47 HSO+H = S+H2O 1.600E+09 1.3700 -170.00 ! [96GLA/KUB] ! ! 48 HSO+H = H2SO 1.800E+17 -2.4700 25.00 ! [96GLA/KUB] ! ! 49 HSO+H = H2S+O 1.100E+06 1.0300 5230.00 ! [96GLA/KUB] ! ! 50 HSO+H = SO+H2 1.000E+13 0.0000 0.00 ! [01GLA/ALZ] ! ! 51 HSO+O+M = HSO2+M 1.100E+19 -1.7300 -25.00 ! [96GLA/KUB] ! ! 52 HSO+O = SO2+H 4.500E+14 -0.4000 0.00 ! [96GLA/KUB] ! ! 53 HSO+O+M = HOSO+M 6.900E+19 -1.6100 800.00 ! [96GLA/KUB] ! ! 54 HSO+O = O+HOS 4.800E+08 1.0200 2700.00 ! [96GLA/KUB] ! ! 55 HSO+O = OH+SO 1.400E+13 0.1500 150.00 ! [96GLA/KUB] ! ! 56 HSO+OH = HOSHO 5.200E+28 -5.4400 1600.00 ! [96GLA/KUB] ! ! 57 HSO+OH = HOSO+H 5.300E+07 1.5700 1900.00 ! [01GLA/ALZ] ! ! 58 HSO+OH = SO+H2O 1.700E+09 1.0300 235.00 ! [96GLA/KUB] ! ! 59 HSO+O2 = SO2+OH 1.000E+12 0.0000 5000.00 ! [96GLA/KUB] ! ! 60 HSOH = SH+OH 2.800E+39 -8.7500 37800.00 ! [96GLA/KUB] ! ! 61 HSOH = S+H2O 5.800E+29 -5.6000 27400.00 ! [96GLA/KUB] ! ! 62 HSOH = H2S+O 9.800E+16 -3.4000 43500.00 ! [96GLA/KUB] ! ! 63 H2SO = H2S+O 4.900E+28 -6.6600 36000.00 ! [96GLA/KUB] ! ! 64 H+SO2(+M) = HOSO(+M) 3.119E+08 1.6100 3606.00 LOW / 2.662E+38 -6.43 5577.00 / TROE / 8.2000E-01 1.3088E+05 2.6600E+02 / ! [02HUG/BLI] ! ! 66 HOSO+M = O+HOS+M 2.500E+30 -4.8000 60000.00 ! [96GLA/KUB] ! ! 67 HOSO+H = SO2+H2 3.000E+13 0.0000 0.00 ! [01GLA/ALZ] ! ! 68 HOSO+H = SO+H2O 6.300E-10 6.2900 -960.00 ! [01GLA/ALZ] ! ! 69 HOSO+OH = SO2+H2O 1.000E+12 0.0000 0.00 ! [01GLA/ALZ] ! ! 70 HOSO+O2 = HO2+SO2 1.000E+12 0.0000 500.00 ! [01GLA/ALZ] ! ! 71 HSO2+H = SO2+H2 3.000E+13 0.0000 0.00 ! [01GLA/ALZ] ! ! 72 HSO2+OH = SO2+H2O 1.000E+13 0.0000 0.00 ! [01GLA/ALZ] ! ! 73 HSO2+O2 = HO2+SO2 1.000E+13 0.0000 0.00 ! [01GLA/ALZ] ! ! 74 H+SO2(+M) = HSO2(+M) 1.060E+09 1.4800 594.60 LOW / 1.251E+31 -5.17 1563.00 / TROE / 4.5000E-01 9.3550E+02 4.2700E+01 / ! [02HUG/BLI] ! ! 75 HOSO2 = HOSO+O 5.400E+18 -2.3400 53500.00 ! [96GLA/KUB] ! ! 76 HOSO2 = SO3+H 1.400E+18 -2.9100 27600.00 ! [96GLA/KUB] ! ! 77 HOSO2+H = SO2+H2O 1.000E+12 0.0000 0.00 ! [01GLA/ALZ] ! ! 78 HOSO2+O = SO3+OH 5.000E+12 0.0000 0.00 ! [01GLA/ALZ] ! ! 79 HOSO2+OH = SO3+H2O 1.000E+12 0.0000 0.00 ! [96GLA/KUB] (estimate) ! ! 80 HOSO2+O2 = HO2+SO3 7.800E+11 0.0000 330.00 ! [96GLA/KUB] ! ! 81 HOSHO = HOSO+H 6.400E+30 -5.8900 37100.00 ! [96GLA/KUB] ! ! 82 HOSHO = SO+H2O 1.200E+24 -3.5900 30000.00 ! [96GLA/KUB] ! ! 83 HOSHO+H = HOSO+H2 1.000E+12 0.0000 0.00 ! [96GLA/KUB] ! ! 84 HOSHO+O = HOSO+OH 5.000E+12 0.0000 0.00 ! [96GLA/KUB] ! ! 85 HOSHO+OH = HOSO+H2O 1.000E+12 0.0000 0.00 ! [96GLA/KUB] ! ! ! ! ! extra reactions from our mechanism ! ! ! C+SO2 = CO+SO 4.156E+13 0.00 0.00 ! [91DOR/CAU] ! ! HOSO2+H = SO3+H2 1.0E+12 0.00 0.00 ! [91CHA/GOD] ! ! ! S+CH4 = SH+CH3 6.0e14 0 12078.42 ! estimate, based on [96GLA/KUB] value for S+H2 ! ! ! H2S+CH3 = CH4+SH 1.8E11 0 1177.53 ! linear fit to NIST values ! ! ! ! pointed out to us that the Wendt et al. value applied to the reverse! !S+OH = SH+O 6.3e11 0.5 4030.55 SH+O = S+OH 6.3e11 0.5 4030.55 ! [83WEN/WOO] ! ! ! C+H2S = CH+SH 1.2e14 0 4450.32 ! estimate by KJH ! ! ! O+COS = CO+SO 1.93e13 0 2328.6 ! fit to NIST data ! ! O+CS = CO+S 1.626E+14 0.00 760.16 ! [92ATK/BAU] ! ! ! COS+M = CO+S+M 1.43E14 0 30700.02 ! fit to NIST Data ! ! O+COS = CO2+S 5E+13 0.00 5530.43 ! [88SIN/CVE] ! ! ! SH+O2 = SO+OH 1.0e12 0 5032.48 ! [96GLA/KUB] estimate ! ! ! CH+SO = CO+SH 1.0e13 0.00 0.00 ! [89PFE/CHU] estimate ! ! ! ! SO3+S = SO+SO2 5.120E+11 0.00 0.00 ! [78MUL/SCH] ! ! ! ! SH+NO = SN+OH 1.0E+13 0.00 8900.65 ! [91CHA/GOD] estimate, modified by KJH for new calculation of delta H ! ! ! S+NO = SN+O 1e12 0.5 17500.6 ! [83WEN/WOO] ! ! ! SH+NH = SN+H2 1.0E+14 0.00 0.00 ! [91CHA/GOD] estimate ! ! ! N+SO = NO+S 6.31E+11 0.50 1010.34 ! [83WEN/WOO] estimate ! ! ! N+SH = SN+H 6.31E+11 0.50 4030.55 ! [83WEN/WOO] estimate ! ! ! ! !!SN+NO = N2+SO 1.0E+14 0.00 0.00 ! [91CHA/GOD] estimate ! SN+NO = N2+SO 1.807e10 0 0 ! new experimental measurement from Chemistry department in Leeds ! (SN+NO => products) ! ! SN+O2 = SO+NO 3e8 0 0 ! new experimental measurement from Chemistry department in Leeds ! (SN+O2 => products) ! ! SN+NO2=S+NO+NO 4.068e15 -0.9805 0 ! new experimental measurement from Chemistry department in Leeds ! (SN+NO2 => products) ! ! N+SN = N2+S 6.3e11 0.5 0 ! [83WEN/WOO] ! ! ! SO2+NO2 = NO+SO3 4.25e-19 8.9 3797.21 ! fit to all NIST data ! ! SO+NO2 = SO2+NO 8.432E+12 0.00 0.00 ! [92ATK/BAU] ! ! ! ! SN+O = SO+N 6.31E+11 0.50 4030.55 ! [83WEN/WOO] ! ! S+NH = SH+N 1.0E+13 0.00 0.00 ! [89PFE/CHU] estimate ! ! !NH+SO = NO+SH 1.0e13 0.00 0.00 ! [89PFE/CHU] estimate ! NH+SO = NO+SH 3.012e13 0 0 ! new experimental measurement from Chemistry department in Leeds ! (NH+SO => products) ! ! HSO+NO2 = HOSO+NO 5.8E12 0 0 ! [96GLA/KUB] ! ! SO3+H2O = H2SO4 7.230E+08 0.0000 0.00 ! [94REI/ARN] ! ! ************ references ******************** ! ! ! ! ! [01GLA/ALZ] ! M.U. Alzueta, R. Bilbao and P. Glarborg ! Combust. Flame, 127:2234 2001 ! ! ! NIST ! Mallard WG, Westley F, Herron JT, Hampson RF ! NIST Chemical Kinetics Database, ver 6.0 ! NIST Standard Reference Data, Gaithersburg, MD (1994) ! (now 2nd quarter 1998) ! ! ! [91DOR/CAU] ! G. Dorthe, Ph. Caubet, Th. Vias, B. Barrere and J. Marchais ! J.Phys.Chem., 95,5109-5116,1991 ! ! ! [96GLA/KUB] ! P. Glarborg, D. Kubel, K. Dam-Johansen, H-M. Chiang and J.W. Bozzelli ! Int.J.Chem.Kinet., 28,773-790,1996 ! ! ! [91CHA/GOD] ! H.K. Chagger, P.R. Goddard, P.Murdoch and A.Williams ! Fuel, 70,1137,1991 ! ! ! [92YOS/KOS] ! M. Yoshimura, M. Koshi, H. Matsui, K. Kamiya and H. Umeyama, ! Chem.Phys.Lett., 199, 1992, vol 189 ! ! ! ! [91TYN/RAV] ! G.S. Tyndall and A.R. Ravishankara, ! Int.J.Chem.Kinet., 23,483,1991 ! ! ! [83WEN/WOO] ! J.O.L. Wendt, E.C. Wootan and T.L. Corley ! Combust. Flame, 49,261,1983 ! ! ! ! [92ATK/BAU] ! R. Atkinson, D.L. Baulch, R.A. Cox, R.F. Hampson Jr., J.A. Kerr and J. Troe ! J.Phys.Chem.Ref.Data, 21,1125,1992 ! ! ! [87CRA/MUR] ! W. Craven and J.N. Murrell ! J.Chem.Soc.Faraday Trans.2, 83,1733,1987 ! ! ! [80HIG/SAI] ! T. Higashihara, K. Saito and I. Murakami ! Bull.Chem.Soc.Jpn., 15,53,1980 ! ! ! [78MUL/SCH] ! C.H. Muller III, K. Schofield, M. Steinberg and H.P. Broida ! 17th. Int. Symp. Combust., 867,1978 ! ! [02HUG/BLI] K.J. Hughes, M.A.Blitz, M.J.Pilling, S.H. Robertson ! 'A Master Equation Model for the Determination of Rate Coefficients ! In the H+SO2 System' Accepted for 29th International Symposium on ! Combustion. ! ! [03BLI/HUG] M.A. Blitz, K.J. Hughes, M.J. Pilling, J. Phys. Chem. A, 107 (2003) 1971 ! 'Determination of the high-pressure limiting rate coefficient and enthalpy of ! reaction for OH+SO2' ! ! ! [00BLI/MCK] M.A. Blitz, K.W. McKee, and M.J. Pilling, ! Proc.Combust.Inst., 28,2491,2000 ! ! [94REI/ARN] T.Reiner, F.Arnold, J.Chem.Phys., 101,7399, 1994 ! END