! Supplementary Material (ESI) for PCCP ! This journal is (c) the Owner Societies 2009 ! rate coefficients obtained from the ME ! Judit Zádor, Ahren W. Jasper and James A. Miller ! The Reaction between Propene and Hydroxyl ! Physical Chemistry Chemical Physics, 2009 ! units are cal, molecule, s, K, cm ! format of the rate coeffients is a double Arrhenius expression ! k = A (T/T0)^B exp(-C/(RT)) + D (T/T0)^E exp(-F/(RT)) ! T0 = 1 K ! R = 1.987 cal / mol / K ! ************* ! ABSTRACTION * ! ************* ! allyl ! ----- c3h6 + oh = allyl + h2o -2.07e-16 1.73 925 dup c3h6 + oh = allyl + h2o 3.12e-17 2.03 684 dup ! propen-1-yl ! ----------- c3h6 + oh = propen-1-yl + h2o 1.26e-20 2.80 2193 dup c3h6 + oh = propen-1-yl + h2o 1.68e-24 3.51 -101 dup ! propen-2-yl ! ----------- c3h6 + oh = propen-2-yl + h2o 7.76e-20 2.47 1748 dup c3h6 + oh = propen-2-yl + h2o 9.50e-31 2.61 -3086 dup ! *************************************************************************************** ! ADDITION * ! goes almost exclusively to the two initial wells (terminal and central addition), * ! with ~50-50% branching. * ! At each pressure the first fit is valid for 50-500 K, while the second for 500-3000 K * ! *************************************************************************************** ! 50-500 K ! -------- c3h6 + oh = c3h7o 3.81E+04 -5.77 1683 PLOG/ 0.0013 3.81E+04 -5.77 1683/ PLOG/ 0.01 3.14E+53 -22.2 13751/ PLOG/ 0.013 1.46E+58 -23.7 15265/ PLOG/ 0.025 3.37E-04 -2.82 263/ PLOG/ 0.1 2.96E+30 -16.59 3552/ PLOG/ 0.1315 1.07E+23 -13.62 2834/ PLOG/ 1 2.62E+07 -7.311 1324/ PLOG/ 10 7.82E+04 -6.28 1079/ PLOG/ 100 7.82E+04 -6.28 1079/ dup c3h6 + oh = c3h7o 9.55E+00 -4.81 511 PLOG/ 0.0013 9.55E+00 -4.81 511/ PLOG/ 0.01 1.10E-03 -3.04 298/ PLOG/ 0.013 6.74E-04 -2.95 283/ PLOG/ 0.025 2.55E+44 -18.83 13105/ PLOG/ 0.1 5.68E-06 -2.13 127/ PLOG/ 0.1315 3.15E-06 -2.03 106/ PLOG/ 1 9.26E-08 -1.47 -20/ PLOG/ 10 2.33E-08 -1.25 -68/ PLOG/ 100 2.33E-08 -1.25 -68/ dup ! 500-3000 K ! ---------- c3h6 + oh = c3h7o 5.10E+54 -20.7 32402 PLOG/ 0.0013 5.10E+54 -20.7 32402/ PLOG/ 0.01 6.06E+53 -20 33874/ PLOG/ 0.013 2.35E+52 -19.58 32874/ PLOG/ 0.025 8.14E+49 -18.79 31361/ PLOG/ 0.1 2.29E+44 -17.01 27909/ PLOG/ 0.1315 1.60E+43 -16.64 27162/ PLOG/ 1 4.31E+35 -14.17 23079/ PLOG/ 10 1.67E+30 -12.23 22976/ PLOG/ 100 3.18E+24 -10.23 23772/ dup c3h6 + oh = c3h7o 1.42E+36 -15.84 11594 PLOG/ 0.0013 1.42E+36 -15.84 11594/ PLOG/ 0.01 1.61E+36 -15.51 12898/ PLOG/ 0.013 6.17E+35 -15.34 12913/ PLOG/ 0.025 5.87E+34 -14.93 12936/ PLOG/ 0.1 2.99E+32 -14.04 12945/ PLOG/ 0.1315 8.82E+31 -13.85 12887/ PLOG/ 1 3.43E+26 -12.04 11493/ PLOG/ 10 1.42E+18 -9.35 8921/ PLOG/ 100 5.08E+08 -6.31 6088/ dup ! ********************************************************************************************** ! BACKDISSOCIATION this is an equilibrium constant in the same format as the rate coefficients * ! terminal 7.36e-25 -0.30 -27414 5.20e-30 1.43 -28013 * ! central 1.02e-23 -1.10 -28390 2.17e-30 1.49 -28888 * ! To calculate the rate of backdissotiation, thermodynamic data, consistent with our PES * ! has to be used. * ! ********************************************************************************************** ! ********************************************************************** ! BIMOLECULAR * ! the sum of all propene + OH bimolecular products, except abstraction * ! ********************************************************************** c3h6 + oh = products 3.51E-18 1.98 2439 PLOG/ 0 3.51E-18 1.98 2439/ PLOG/ 0.0013 -8.17E-16 1.18 1060/ PLOG/ 0.01 3.54E-18 1.98 2477/ PLOG/ 0.013 4.95E-18 1.94 2581/ PLOG/ 0.025 1.45E-17 1.81 2926/ PLOG/ 0.1 6.70E-16 1.36 4252/ PLOG/ 0.1315 3.26E-15 1.16 4707/ PLOG/ 1 4.92E-11 0 8132/ PLOG/ 10 3.61E-08 -0.73 12175/ PLOG/ 100 7.50E-04 -1.83 18784/ dup c3h6 + oh = products 4.49E-10 -1.73 -214 PLOG/ 0 4.49E-10 -1.73 -214/ PLOG/ 0.0013 3.68E-18 1.99 484/ PLOG/ 0.01 1.46E-20 1.97 -526/ PLOG/ 0.013 1.15E-21 2.32 -683/ PLOG/ 0.025 5.07E-21 1.97 -589/ PLOG/ 0.1 4.17E-25 3.34 -930/ PLOG/ 0.1315 4.91E-28 4.44 -1217/ PLOG/ 1 1.46E-28 4.76 -223/ PLOG/ 10 7.36E-29 4.81 612/ PLOG/ 100 1.12E-26 4.25 3044/ dup ! **************************************************************** ! BIMOLECULAR rate coefficients for selected individual channels * ! **************************************************************** ! allyl alcohol ! ------------- c3h6 + oh = allyl alcohol + h PLOG/ 0 -1.31E-09 -4.50E-01 10996/ PLOG/ 0.0013 -1.74E-09 -4.90E-01 11043/ PLOG/ 0.01 -1.75E-09 -4.90E-01 11053/ PLOG/ 0.013 -1.77E-09 -4.90E-01 11060/ PLOG/ 0.025 -1.09E-08 -7.00E-01 11615/ PLOG/ 0.1 -1.04E-08 -6.60E-01 11794/ PLOG/ 0.1315 -8.36E-09 -6.20E-01 11782/ PLOG/ 1 1.34E-07 -1 15339/ PLOG/ 10 2.07E-01 -2.68 20993/ PLOG/ 100 3.45E+01 -3.16 26266/ dup c3h6 + oh = allyl alcohol + h PLOG/ 0 3.80E-11 0.07 10580/ PLOG/ 0.0013 4.43E-11 0.05 10611/ PLOG/ 0.01 4.57E-11 0.05 10623/ PLOG/ 0.013 4.77E-11 0.04 10634/ PLOG/ 0.025 2.64E-10 -0.16 11125/ PLOG/ 0.1 5.14E-10 -0.22 11407/ PLOG/ 0.1315 6.27E-10 -0.24 11458/ PLOG/ 1 1.52E-16 1.42 10087/ PLOG/ 10 6.07E-19 2.14 10410/ PLOG/ 100 1.36E-21 2.84 10481/ dup ! vinyl alcohol ! ------------- c3h6 + oh = vinyl alcohol + ch3 4.06E-17 1.55 2310 PLOG/ 0 4.06E-17 1.55 2310/ PLOG/ 0.0013 1.11E-16 1.42 2708/ PLOG/ 0.01 6.24E-16 1.21 3068/ PLOG/ 0.013 2.00E-15 1.06 3326/ PLOG/ 0.025 2.70E-14 0.72 3950/ PLOG/ 0.1 3.47E-12 0.13 5407/ PLOG/ 0.1315 8.52E-12 0.02 5723/ PLOG/ 1 1.45E-03 -2.35 11290/ PLOG/ 10 3.77E-26 4.03 1952/ PLOG/ 100 1.08E-01 -2.58 19256/ dup c3h6 + oh = vinyl alcohol + ch3 2.16E-20 2.11 308 PLOG/ 0 2.16E-20 2.11 308/ PLOG/ 0.0013 2.14E-18 1.65 1233/ PLOG/ 0.01 3.03E-20 2.1 1162/ PLOG/ 0.013 3.39E-21 2.48 1128/ PLOG/ 0.025 4.78E-22 2.8 1152/ PLOG/ 0.1 2.32E-23 3.21 1208/ PLOG/ 0.1315 1.28E-23 3.29 1216/ PLOG/ 1 1.87E-20 2.5 3238/ PLOG/ 10 4.01E-05 -1.74 13107/ PLOG/ 100 5.48E-25 3.7 3665/ dup ! propen-1-ol ! ----------- c3h6 + oh = propen-1-ol + h 2.89E-14 0.69 6864 PLOG/ 0 2.89E-14 0.69 6864/ PLOG/ 0.0013 1.08E-13 0.53 7292/ PLOG/ 0.01 3.77E-14 0.66 6968/ PLOG/ 0.013 3.01E-14 0.69 6884/ PLOG/ 0.025 3.43E-14 0.68 6899/ PLOG/ 0.1 5.20E-13 0.36 7785/ PLOG/ 0.1315 1.21E-12 0.26 8071/ PLOG/ 1 4.83E-09 -0.74 11079/ PLOG/ 10 7.49E-05 -1.86 15763/ PLOG/ 100 6.29E-03 -2.3 20501/ dup c3h6 + oh = propen-1-ol + h 2.92E-18 1.57 4133 PLOG/ 0 2.92E-18 1.57 4133/ PLOG/ 0.0013 5.77E-18 1.53 4288/ PLOG/ 0.01 1.79E-17 1.34 4576/ PLOG/ 0.013 1.62E-17 1.33 4589/ PLOG/ 0.025 8.53E-18 1.36 4594/ PLOG/ 0.1 5.20E-19 1.69 4603/ PLOG/ 0.1315 2.31E-19 1.8 4603/ PLOG/ 1 1.71E-22 2.83 4530/ PLOG/ 10 5.65E-26 3.89 4390/ PLOG/ 100 7.40E-30 5.03 4132/ dup ! propen-2-ol ! ----------- c3h6 + oh = propen-2-ol + h 8.52E-21 2.42 2447 PLOG/ 0 8.52E-21 2.42 2447/ PLOG/ 0.0013 1.55E-20 2.35 2635/ PLOG/ 0.01 6.77E-20 2.17 3048/ PLOG/ 0.013 1.07E-19 2.11 3186/ PLOG/ 0.025 4.26E-19 1.94 3598/ PLOG/ 0.1 2.51E-17 1.44 4816/ PLOG/ 0.1315 5.44E-17 1.35 5084/ PLOG/ 1 2.58E-14 0.62 7544/ PLOG/ 10 2.45E-29 4.75 2168/ PLOG/ 100 6.40E-05 -1.85 19219/ dup c3h6 + oh = propen-2-ol + h 7.30E-27 3.67 -518 PLOG/ 0 7.30E-27 3.67 -518/ PLOG/ 0.0013 4.76E-24 2.92 625/ PLOG/ 0.01 8.03E-25 2.98 704/ PLOG/ 0.013 5.19E-25 3.04 721/ PLOG/ 0.025 1.55E-26 3.62 677/ PLOG/ 0.1 7.70E-29 4.48 687/ PLOG/ 0.1315 4.50E-29 4.56 707/ PLOG/ 1 1.27E-30 5.05 874/ PLOG/ 10 4.38E-09 -0.8 12728/ PLOG/ 100 8.08E-28 4.32 4020/ dup ! acetaldehyde ! ------------ c3h6 + oh = acetaldehyde + ch3 1.48E-02 -4.56 464 PLOG/ 0 1.48E-02 -4.56 464/ PLOG/ 0.0013 -7.37E-17 0.89 540/ PLOG/ 0.01 3.11E-05 -2.96 4951/ PLOG/ 0.013 4.33E-09 -1.67 3823/ PLOG/ 0.025 5.49E-10 -1.29 3996/ PLOG/ 0.1 1.57E-09 -1.3 5272/ PLOG/ 0.1315 2.67E-09 -1.35 5603/ PLOG/ 1 8.58E-08 -1.67 8264/ PLOG/ 10 8.52E-06 -2.11 12359/ PLOG/ 100 1.23E-04 -2.29 17262/ dup c3h6 + oh = acetaldehyde + ch3 1.27E-21 2.24 -1676 PLOG/ 0 1.27E-21 2.24 -1676/ PLOG/ 0.0013 1.15E-18 1.49 -536/ PLOG/ 0.01 9.86E-21 2.01 -560/ PLOG/ 0.013 1.83E-21 2.22 -680/ PLOG/ 0.025 1.77E-22 2.5 -759/ PLOG/ 0.1 1.30E-24 3.1 -919/ PLOG/ 0.1315 5.09E-25 3.22 -946/ PLOG/ 1 5.24E-28 4.05 -1144/ PLOG/ 10 1.26E-29 4.49 -680/ PLOG/ 100 9.05E-29 4.22 1141/ dup