Table III Kinetic model developed in the present work
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This journal is © The Owner Societies 2002 Table III Kinetic property data (Electronic Supplementary Information) k= A Tn exp(-Ea/RT) A: cm3 mole –1 s-1 Ea: cal H2, O2 ,H,OH and O reactions 1. 2. 3. 4. H2 + OH = H2O + H 2.14E08 1.51 H2 + O2 = OH + OH 1.70E13 0.0 H + O2 = OH + O 1.91E14 0.0 H + O2 + M = HO2 + M 3.61E17 -0.72 H2O/18.6/ CO2/4.2/ H2/2.9/ CO/2.1/ 5. 2H + M = H2 + M 1.00E18 -1.0 6. 2H + H2 = 2H2 9.20E16 -0.6 7. 2H + H2O = H2 + H2O 6.00E19 -1.25 8. 2H + CO2 = H2 + CO2 5.49E20 -2.0 9. H + OH + M = H2O + M 8.35E21 -2.0 H2/3.333/ H2O/16.0/ CO2/5.067/ CO/2.533/ 10. H + O + M = OH + M 6.02E16 -0.6 H2O/5.0/ 11. OH + H2O2 = H2O + HO2 7.08E12 0.0 12. OH + OH = O + H2O 1.23E04 2.62 13. O + HO2 = OH + O2 1.74E13 0.0 14. O + H2 = OH + H 5.13E04 2.67 15. O + O + M = O2 + M 1.89E13 0.0 H2/3.333/ H2O/16.0/ CO2/5.067/ CO/2.533/ 16. O + OH + M = HO2 + M 1.00E17 0.0 3430 47780 16440 0 [Emdee et al. 1992] [Miller and Melius 1992] [Emdee et al. 1992] [Miller and Melius 1992] 0 0 0 0 0 [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [Baulch et al. 1992] for argon [a] 0 [Miller and Melius 1992] 1430 [Emdee et al. 1992] -1878 [Emdee et al. 1992] -400 [Emdee et al. 1992] 6290 [Emdee et al. 1992] -1790 [Tsang and Hampson 1986]; argon [a] 0 [Zhang and McKinnon 1995] Peroxyl (HO2) reactions 17. HO2 + H = H2O + O 18. HO2 + H = H2 + O2 19. HO2 + H = OH + OH 20. HO2 + OH = H2O + O2 21. HO2 + HO2 = H2O2 + O2 3.00E13 6.61E13 1.40E14 7.50E12 2.00E12 0.0 0.0 0.0 0.0 0.0 1070 2130 1073 0 0 [Baulch et al. 1992] [Emdee et al. 1992] [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] H2O2 reactions 22. H2O2 + M = OH + OH + M 1.81E16 0.0 H2/3.333/ H2O/16.0/ CO2/5.067/ CO/2.533/ 23. H2O2 + H = HO2 + H2 4.79E13 0.0 24. H2O2 + H = OH + H2O 1.00E13 0.0 25. H2O2 + O = OH + HO2 9.55E06 2.0 26. H2O2 + O = O2 + H2O 9.55E06 2.0 42920 [Baulch et al. 1992] for argon [a] 7950 [Emdee et al. 1992] 3590 [Emdee et al. 1992] 3970 [Emdee et al. 1992] 3970 [Emdee et al. 1992] HCO reactions 27. HCO + O = CO2 + H 3.00E13 28. HCO + O2 = CO2 + OH 3.31E12 29. HCO + HO2 = CO2 + OH + H 3.00E13 30. HCO + CH3O = CH3OH + CO 9.04E13 31. 2HCO = CH2O + CO 4.52E13 0.0 -0.4 0.0 0.0 0.0 0 [Miller and Melius 1992] 0 [Baulch et al. 1992] 0 [Zhang and McKinnon 1995] 0 [Tsang and Hampson 1986] 0 [Baggott et al. 1986] This journal is © The Owner Societies 2002 32. HCO + O2 = CO + HO2 33. HCO + OH = CO + H2O 34. HCO + M = H + CO + M 35. HCO + H = CO + H2 36. HCO + O = CO + OH 37. 2HCO = 2CO + H2 3.30E13 3.02E13 2.50E14 9.04E13 3.00E13 3.01E12 -0.4 0.0 0.0 0.0 0.0 0.0 0 [Miller and Melius 1992] 0 [Emdee et al. 1992] 16802 [Miller and Melius 1992] 0 [Baulch et al. 1992] 0 [Miller and Melius 1992] 0 [Zhang and McKinnon 1995] CO and CO2 reactions 38. CO + O + M = CO2 + M 6.17E14 0.0 H2/3.333/ H2O/16.0/ CO2/5.067/ CO/2.533/ 39. CO + OH = CO2 + H 6.32E06 1.50 40. CO + O2 = CO2 + O 2.51E12 0.0 41. CO + HO2 = CO2 + OH 6.03E13 0.0 3000 [Tsang and Hampson 1986] [a] -497 [Baulch et al. 1992] 47690 [Emdee et al. 1992] 22950 [Emdee et al. 1992] Methine (CH) and C reactions 42. CH + H2 = CH3 43. CH + H2 = HCH + H 44. CH + O = C + OH 45. CH + O = CO + H 46. CH + O2 = CO + OH 47. CH + O2 = HCO + O 48. CH + OH = HCO + H 49. CH + OH = C + H2O 50. CH + CO2 = HCO + CO 51. CH + H = C + H2 52. CH + H2O = CH2O + H 53. CH + H2O = CH2OH 54. C + O2 = CO + O 55. C + OH = CO + H 3.19E25 2.39E15 1.52E13 5.70E13 3.30E13 3.30E13 3.00E13 4.00E07 3.40E12 1.50E14 1.17E15 5.71E12 2.00E13 5.00E13 -4.99 -0.39 0.0 0.0 0.0 0.0 0.0 2.0 0.0 0.0 -0.75 0.0 0.0 0.0 3.43E09 2.19E08 3.31E16 1.80E13 1.23E06 4.40E06 1.18 1.8 0.0 0.0 3.0 2.0 2710 [QRRK, 20 torr]b 2890 [QRRK, 20 torr]b 4732 [Murrel and Rodriguez 1986] 0 [Miller and Melius 1992] 0 [Baulch et al. 1992] 0 [Miller and Melius 1992] 0 [Miller and Melius 1992] 3000 [Miller and Melius 1992] 690 [Miller and Melius 1992] 0 [Miller and Melius 1992] 0 [Miller and Melius 1992] -755 [Zabarnick et al. 1986] 0 [Miller and Melius 1992] 0 [Miller and Melius 1992] Formaldehyde (CH2O) reactions 56. CH2O + OH = HCO + H2O 57. CH2O + H = HCO + H2 58. CH2O + M = HCO + H + M 59. CH2O + O = HCO + OH 60. CH2O + O2 = HO2 + HCO 61. CH2O + HO2 = HCO + H2O2 -447 [Miller and Melius 1992] 3000 [Miller and Melius 1992] 81000 [Miller and Melius 1992] 3080 [Miller and Melius 1992] 52060 [Hidaka et al. 1993] 12000 [Hidaka et al. 1993] Singlet Methylene (1CH2, CH2) reactions 62. CH2 + CH4 = 2CH3 63. CH2 + H2 = CH3 + H 64. CH2 + H2O = HCH + H2O 65. CH2 + H = HCH + H 66. CH2 + O = H + H + CO 67. CH2 + O = H2 + CO 68. CH2 + O2 = CO2 + 2H 69. CH2 + O2 = O + CH2O 4.00E13 0.0 7.00E13 0.0 3.00E13 0.0 2.00E14 0.0 3.00E13 0.0 7.83E12 0.0 7.83E12 0.0 7.83E12 0.0 0 0 0 0 0 0 0 0 [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [Zhang and McKinnon 1995] [Zhang and McKinnon 1995] [Zhang and McKinnon 1995] This journal is © The Owner Societies 2002 70. CH2 + O2 = H2 + CO2 71. CH2 + O2 = H + CO + OH 72. CH2 + OH = CH2O + H 73. CH2 + CO2 = CH2O + CO 74. CH2 + HO2 = CH2O + OH 75. CH2 + H2O2 = CH3O + OH 76. CH2 + HCO = CO + CH3 77. CH2 + CH2O = HCO + CH3 78. CH2 + O = CH + OH 7.83E12 0.0 7.83E12 0.0 3.01E13 0.0 3.00E12 0.0 3.01E13 0.0 3.01E13 0.0 1.81E13 0.0 1.20E12 0.0 3.00E14 0.0 0 [Zhang and McKinnon 1995] 0 [Zhang and McKinnon 1995] 0 [Miller and Melius 1992] 0 [Miller and Melius 1992] 0 [Zhang and McKinnon 1995] 0 [Zhang and McKinnon 1995] 0 [Zhang and McKinnon 1995] 0 [Zhang and McKinnon 1995] 11923 [Frank and Just 1984] Triplet Methylene (3CH2, HCH) reactions 79. HCH + O = CO + 2H 80. HCH + O = CO + H2 81. HCH + O2 = CO2 + 2H 82. HCH + O2 = CH2O + O 83. HCH + O2 = CO2 + H2 84. HCH + O2 = CO + H2O 85. HCH + O2 = CO + OH + H 86. HCH + O2 = HCO + OH 87. HCH + OH = CH + H2O 88. HCH + OH = CH2O + H 89. HCH + CO2 = CH2O + CO 90. CH2 + M = HCH + M H/0.0/ H2O/0.0/ C2H2/0.0/ 91. HCH + HCO = CH3 + CO 92. HCH + CH3O = CH3 + CH2O 5.00E13 3.00E13 1.60E12 5.00E13 6.90E11 1.90E10 8.60E10 4.30E10 1.13E07 2.50E13 1.10E11 1.00E13 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.0 0.0 0.0 0.0 1.81E13 1.81E13 0.0 0.0 0 [Miller and Melius 1992] 0 [Miller and Melius 1992] 1000 [Miller and Melius 1992] 9000 [Miller and Melius 1992] 500 [Miller and Melius 1992] -1000 [Miller and Melius 1992] -500 [Miller and Melius 1992] -500 [Miller and Melius 1992] 3000 [Miller and Melius 1992] 0 [Miller and Melius 1992] 1000 [Miller and Melius 1992] 0 [Miller and Melius 1992] 0 [Zhang and McKinnon 1995] 0 [Zhang and McKinnon 1995] Methyl (CH3) reactions 93. CH3 + M = HCH + H + M 2.72E36 -5.309 117084 [Su and Teitelbaum 1994]c 94. CH3 + H + M = CH4 + M 6.19E23 -1.80 0 [Baulch et al. 1992, for argon] 95. CH3 + H = HCH + H2 6.03E13 0.0 15103 [Baulch et al. 1992] 96. CH3 + O = CH2O + H 7.17E13 0.0 0 [Lim/Michael '93, Marcy et al. '01]d 97. CH3 + O = HCO + H2 1.26E13 0.0 0 [Lim/Michael '93, Marcy et al. '01]d 98. CH3 + O = CH3O 1.78E14 -2.14 603 [Dean and Westmoreland 1987]e 99. CH3 + O2 = CH3O + O 7.26E11 0.39 27363 [Dean and Westmoreland 1987]e 100. CH3 + OH = CH3OH 1.24E43 -9.49 10471 [Dean and Westmoreland 1987]e 101. CH3 + OH = CH2OH + H 1.09E11 0.4 -708 [Zhang and McKinnon 1995] 102. CH3 + OH = CH3O + H 8.93E11 -0.02 13073 [Dean and Westmoreland 1987]e 103. CH3 + OH = HCH + H2O 7.50E06 2.0 5000 [Zhang and McKinnon 1995] 104. CH3 + OH = CH2O + H2 3.98E10 -0.02 8765 [Dean and Westmoreland 1987]e 105. CH3 + HO2 = CH3O + OH 1.81E13 0.0 0 [Baulch et al. 1992] 106. CH3 + HCO = CH4 + CO 2.65E13 0.0 0 [Mulenko 1987] 107. CH3 + CH2OH = CH4 + CH2O 2.41E12 0.0 0 [Tsang 1987] 108. CH3 + CH3O = CH4 + CH2O 2.41E13 0.0 0 [Tsang et al. 1986] 109. CH3 + CH2O = CH4 + HCO 7.77E-8 6.10 1970 [Baulch et al. 1994] 110. CH3 + CH3 = C2H5 + H 8.92E11 -0.005 11850 [QRRK, 20 torr]f 111. CH3 + CH3 = C2H4 + H2 1.00E16 0.0 32030 [Warnatz 1984] 112. CH3 + CH3 = C2H6 9.18E49 -11.851 11590 [QRRK, 20 torr]f This journal is © The Owner Societies 2002 Hydroxymethyl (CH2OH) reactions 113. CH2OH + M = CH2O + H + M 1.67E24 114. CH2OH +O = CH2O + OH 1.00E13 115. CH2OH + O2 = CH2O + HO2 2.41E14 116. CH2OH + OH = CH2O + H2O 1.00E13 117. CH2OH + H = CH2O + H2 2.00E13 118. CH2OH+ HO2 = CH2O + H2O2 1.20E13 119. CH2OH + HCO = CH3OH + CO 1.20E14 120. CH2OH + CH2O = CH3OH + HCO 5.54E03 121. 2CH2OH = CH3OH + CH2O 4.82E12 122. CH2OH + HCO = 2CH2O 1.81E14 -2.5 34190 [Emdee et al. 1992] 0.0 0 [Miller and Melius 1992] 0.0 5000 [Emdee et al. 1992] 0.0 0 [Miller and Melius 1992] 0.0 0 [Miller and Melius 1992] 0.0 0 [Zhang and McKinnon 1995] 0.0 0 [Zhang and McKinnon 1995] 2.81 5682 [Zhang and McKinnon 1995] 0.0 0 [Zhang and McKinnon 1995] 0.0 0 [Tsang 1987] Methoxy (CH3O) reactions 123. CH3O + M = CH2O + H + M 124. CH3O + H = CH2O + H2 125. CH3O + OH = CH2O + H2O 126. CH3O + O = CH2O + OH 127. CH3O + O2 = CH2O + HO2 128. CH3O + HO2 = CH2O + H2O2 129. CH3O + CO = CH3 + CO2 5.42E13 2.00E13 1.00E13 1.00E13 6.30E10 3.01E11 1.57E13 0.0 13490 [Baulch et al. 1994] 0.0 0 [Miller and Melius 1992] 0.0 0 [Miller and Melius 1992] 0.0 0 [Miller and Melius 1992] 0.0 2600 [Miller and Melius 1992] 0.0 0 [Zhang and McKinnon 1995] 0.0 11797 [Zhang and McKinnon 1995] Methanol (CH3OH) reactions 130. CH3OH + M = CH3 + OH + M 3.50E16 131. CH3OH + M = CH2OH + H + M 1.75E15 132. CH3OH + M = CH2 + H2O + M 7.00E15 133. CH3OH + CH3 = CH2OH + CH4 3.19E01 134. CH3OH + CH3 = CH3O + CH4 1.45E01 135. CH3OH + HO2 = H2O2 + CH2OH 9.64E10 136. CH3OH + O = OH + CH2OH 3.80E05 137. CH3OH + O = OH + CH3O 1.00E13 138. CH3OH + O2 = CH2OH + HO2 2.05E13 139. CH3OH + OH = H2O + CH2OH 1.00E13 140. CH3OH + OH = H2O + CH3O 1.00E13 141. CH3OH + CH2OH = CH3OH + CH3O 7.83E09 142. CH3OH + H = CH2OH + H2 3.98E13 143. CH3OH + H = CH3O + H2 3.98E13 144. CH3OH + HCH = CH2OH + CH3 1.58E12 0.0 0.0 0.0 3.17 3.10 0.0 2.5 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 66444 [Zhang and McKinnon 1995] 66444 [Zhang and McKinnon 1995] 66444 [Zhang and McKinnon 1995] 7172 [Zhang and McKinnon 1995] 6935 [Zhang and McKinnon 1995] 12579 [Zhang 1987] 3080 [Zhang and McKinnon 1995] 4684 [Warnatz 1984] 44717 [Zhang and McKinnon 1995] 1697 [Zhang and McKinnon 1995] 1697 [Zhang and McKinnon 1995] 12062 [Tsang 1987] 6095 [Zhang and McKinnon 1995] 6095 [Zhang and McKinnon 1995] 5736 [Zhang and McKinnon 1995] Methane (CH4) reactions 145. CH4 + O2 = CH3 + HO2 146. CH4 + H = CH3 + H2 147. CH4 + OH = CH3 + H2O 148. CH4 + O = CH3 + OH 149. CH4 + HO2 = CH3 + H2O2 7.94E13 1.48E14 1.57E07 6.92E08 1.81E11 0.0 56000 0.0 13585 1.83 2780 1.56 8490 0.0 18580 5.00E13 0.0 [Miller and Melius 1992] [Knyazev et al. 1996a] [Baulch et al. 1992] [Baulch et al. 1992] [Emdee et al. 1992] C2O and C2 reactions 150. C2O + H = CH + CO 0 [Miller and Melius 1992] This journal is © The Owner Societies 2002 151. C2O + O = CO + CO 152. C2O + OH = CO + CO + H 153. C2O + O2 = 2CO + O 154. C2 + OH = C2O + H 155. C2 + O2 = 2CO 5.00E13 2.00E13 2.00E13 5.00E13 5.00E13 0.0 0.0 0.0 0.0 0.0 0 0 0 0 0 [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] Ethynyl (C2H) reactions 156. C2H + M = C2 + H + M 157. C2H + O = CO + CH 158. C2H + O2 = HCO + CO 159. C2H + O2 = H + 2CO 160. C2H + OH = CH2 + CO 161. C2H + OH = C2+ H2O 162. C + HCH = C2H + H 163. CH + HCH= C2H + 2H 164. C2 + H2 = C2H + H 4.68E16 0.0 124000 5.00E13 0.0 0 2.41E12 0.0 0 3.52E13 0.0 0 1.81E13 0.0 0 4.00E07 2.0 8000 5.00E13 0.0 0 5.49E22 -2.41 11520 4.00E05 2.4 1000 [Colket 1986] [Miller and Melius 1992] [Zhang and McKinnon 1995] [Miller and Melius 1992] [Tsang and Hampson 1986] [Miller and Melius 1992] [Miller and Melius 1992] [Westmoreland 1986] [Miller and Melius 1992] HCCO reactions 165. HCCO + H = CH2 + CO 166. HCCO + O = 2CO + H 167. HCCO + H = HCCOH 168. HCCO + OH = C2O + H2O 169. HCCO + O2 = 2CO + OH 170. HO2 + C2H = HCCO + OH 171. C2H + O2 = HCCO + O 172. C2H + OH = HCCO + H 1.00E14 0.0 0 [Miller and Melius 1992] 1.00E14 0.0 0 [Miller and Melius 1992] 1.85E39 -8.521 6430 [QRRK, 20 torr]f 3.00E13 0.0 0 [Miller and Melius 1992] 1.46E12 0.0 2500 [Emdee et al. 1992] 1.81E13 0.0 0 [Tsang and Hampson 1986] 5.00E13 0.0 1500 [Baulch et al. 1992] 2.00E13 0.0 0 [Miller and Melius 1992] CH2CO reactions 173. CH2CO + M = HCH + CO + M 3.60E15 0.0 59235 H2/2.5/ H2O/16.0/ CO/1.9/ CO2/3.8/ CH4/16.0/ CH3OH/5.0/ 174. CH2CO + O = HCO + HCO 2.00E13 0.0 2293 175. CH2CO + O = CH2 + CO2 1.75E12 0.0 1350 176. CH2CO + H = HCCO + H2 5.00E13 0.0 8000 177. CH2CO + O = HCCO + OH 1.00E13 0.0 8000 178. CH2O + CH = CH2CO + H 9.46E13 0.0 -515 179. CH2 + CO = CH2CO 6.00E08 0.0 0 180. CH2CO + OH = HCCO + H2O 7.50E12 0.0 2000 181. CH2CO + OH = CH2O + HCO 2.80E13 0.0 0 182. CH2CO + OH = CH3O + CO 2.80E13 0.0 0 183. HCCOH + H = CH2CO + H 1.00E13 0.0 0 [Miller and Melius 1992] [Zhang and McKinnon 1995] [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [QRRK, 20 torr]f [Miller and Melius 1992] [Zhang and McKinnon 1995] [Baulch et al. 1992] [Miller and Melius 1992] Acetylene (C2H2) reactions 184. C2H2 + M = C2H + H + M 185. C2H2 + O2 = C2H + HO2 186. C2H2 + H = C2H + H2 187. C2H2 + H = CH + CH2 188. C2H2 + H2 = C2H4 4.20E16 0.0 107000 1.20E13 0.0 74475 6.03E13 0.0 27820 1.02E16 0.0 125076 1.41E41 -9.06 51130 [Miller and Melius 1992] [Zhang and McKinnon 1995] [Baulch et al. 1992] [Lee et al. 1993] [QRRK, 20 torr]g This journal is © The Owner Societies 2002 189. C2H2 + OH = C2H + H2O 190. C2H2 + OH = HCCOH + H 191. C2H2 + OH = CH2CO + H 192. C2H2 + OH = CH3 + CO 193. CH3OH + C2H = CH3O + C2H2 194. CH3OH + C2H = CH2OH + C2H2 195. C2H + CH4 = C2H2 + CH3 196. HCCO + CH = C2H2 + CO 197. HCCO + HCCO = C2H2 + 2CO 198. HO2 + C2H2 = CH2CO + OH 199. HCO + C2H = C2H2 + CO 200. C + CH3 = C2H2 + H 201. CH2 + C2H2 = HCH + C2H2 202. CH2 + CH2 = C2H2 + H2 203. CH3O + C2H = CH2O + C2H2 204. 2HCH = C2H2 + H2 205. CH + HCH = C2H2 + H 206. C2H + CH2OH = C2H2 + CH2O 207. C2H + C2H = C2H2 + C2 208. C2H + CH2 = CH + C2H2 209. C2H2 + O = C2H + OH 210. C2H2 + O = HCH + CO 211. C2H2 + O = HCCO + H 212. HCH + C2H = CH + C2H2 3.37E07 5.04E05 2.18E-4 4.83E-4 1.21E12 6.03E12 1.81E12 5.00E13 1.00E13 6.03E09 6.03E13 5.00E13 4.00E13 3.01E13 2.41E13 4.02E14 2.50E12 3.61E13 1.81E12 1.81E13 3.16E15 1.40E06 5.80E06 1.81E13 2.0 2.3 4.5 4.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 -0.47 -3.68 0.0 0.0 0.0 -0.6 2.09 2.09 0.0 14000 [Miller and Melius 1992] 13500 [Miller and Melius 1992] -1000 [Miller and Melius 1992] -2000 [Miller and Melius 1992] 0 [Tsang 1987] 0 [Tsang 1987] 497 [Tsang and Hampson 1986] 0 [Miller and Melius 1992] 0 [Miller and Melius 1992] 7949 [Tsang and Hampson 1986] 0 [Tsang and Hampson 1986] 0 [Miller and Melius 1992] 0 [Miller and Melius 1992] 0 [Zhang and McKinnon 1995] 0 [Zhang and McKinnon 1995] 480 [Westmoreland 1986] 4190 [Westmoreland 1986] 0 [Tsang 1987] 0 [Tsang and Hampson 1986] 0 [Tsang and Hampson 1986] 15000 [Miller and Melius 1992] 1562 [Emdee et al. 1992] 1562 [Emdee et al. 1992] 0 [Zhang and McKinnon 1995] 2.74E22 1.21E13 3.00E13 3.00E13 3.00E13 3.09E14 3.00E13 2.00E13 7.12E21 7.30E11 3.00E13 4.58E16 1.34E06 2.00E13 3.00E13 5.00E13 1.99E13 1.81E13 1.81E13 -4.061 37040 [Knyazev et al. 1996b, 20 torr] 0.0 0 [Baulch et al. 1992] 0.0 0 [Miller and Melius 1992] 0.0 0 [Baulch et al. 1992] 0.0 0 [Baulch et al. 1992] -1.98 620 [Westmoreland 1986] 0.0 0 [Miller and Melius 1992] 0.0 0 [Frank and Just 1984] -3.9 2460 [Westmoreland 1986] 0.0 9004 [Tsang 1987] 0.0 0 [Baulch et al. 1992] -1.39 1015 [Mebel et al. 1996a] 1.61 -383 [Mebel et al. 1996a] 0.0 0 [Miller and Melius 1992] 0.0 0 [Miller and Melius 1992] 0.0 0 [Miller and Melius 1992] 0.0 0 [Fahr et al. 1999] 0.0 0 [Tsang and Hampson 1986] 0.0 0 [Zhang and McKinnon 1995] 5.07E07 1.93 Vinyl (C2H3) reactions 213. C2H3 = C2H2 + H 214. C2H3 + H = C2H2 + H2 215. C2H3 + O = CH2CO + H 216. C2H3 + O = C2H2 + OH 217. C2H3 + O = CO + CH3 218. CH + HCH = C2H3 219. CH + CH3 = C2H3 + H 220. CH2 + CH2 = C2H3 + H 221. 2HCH = C2H3 + H 222. CH2OH + C2H2 = C2H3 + CH2O 223. C2H3 + O = HCO + CH2 224. C2H3 + O2 = CH2O + HCO 225. C2H3 + O2 = C2H2 + HO2 226. C2H3 + OH = C2H2 + H2O 227. C2H3 + C2H = 2C2H2 228. C2H3 + CH = HCH + C2H2 229. C2H3 + CH3 = C2H2 + CH4 230. C2H3 + CH2 = CH3 + C2H2 231. HCH + C2H3 = CH3 + C2H2 Ethylene (C2H4) reactions 232. C2H4 + H = C2H3 + H2 12951 [Knyazev et al. 1996a] This journal is © The Owner Societies 2002 233. C2H4 + H = C2H5 8.42E08 1.49 990 [Tsang and Hampson 1986] 234. 2HCH = C2H4 1.11E20 -3.43 2070 [Westmoreland 1986] 235. HCH + CH3 = C2H4 + H 4.20E13 0.0 0 [Westmoreland 1986] 236. CH3O + C2H3 = CH2O + C2H4 2.41E13 0.0 0 [Zhang and McKinnon 1995] 237. CH2CO + CH2 = C2H4 + CO 1.60E14 0.0 0 [Miller and Melius 1992] 238. C2H3 + H2O2 = C2H4 + HO2 1.21E10 0.0 -596 [Tsang and Hampson 1986] 239. C2H3 + CH2O = C2H4 + HCO 5.43E03 2.81 5862 [Tsang and Hampson 1986] 240. C2H3 + CH2OH = C2H4 + CH2O 3.01E13 0.0 0 [Tsang 1987] 241. CH3 + CH2 = C2H4 + H 4.94E13 -0.076 94 [Westmoreland 1986] 242. CH + CH4 = C2H4 + H 6.00E13 0.0 0 [Miller and Melius 1992] 243. C2H4 + O = CH3 + HCO 1.60E09 1.2 746 [Miller and Melius 1992] 244. C2H4 + OH = C2H3 + H2O 2.02E13 0.0 5955 [Miller and Melius 1992] 245. C2H4 + OH = CH3 + CH2O 1.05E12 0.0 -916 [Zhang and McKinnon 1995] 246. C2H4 + O2 = C2H3 + HO2 4.22E13 0.0 57594 [Zhang and McKinnon 1995] 247. C2H4 + CH3 = C2H3 + CH4 4.16E12 0.0 11128 [Baulch et al. 1992] 248. C2H4 + C2H2 = 2C2H3 2.41E13 0.0 68360 [Tsang and Hampson 1986] 249. C2H3 + HCO = C2H4 + CO 9.04E13 0.0 0 [Tsang and Hampson 1986] Ethyl (C2H5) reactions 250. C2H5 + O = C2H4 + OH 5.00E13 0.0 0 [Zhang and McKinnon 1995] 251. C2H5 + O = CH2O + CH3 1.61E13 0.0 0 [Tsang and Hampson 1986] 252. HO2 + C2H5 = C2H4 + H2O2 3.01E11 0.0 0 [Tsang and Hampson 1986] 253. HCH + CH3 = C2H5 2.53E20 -3.49 2030 [Westmoreland 1986] 254. CH3 + C2H5 = C2H4 + CH4 1.95E13 -0.5 0 [Tsang and Hampson 1986] 255. CH3 + CH2 = C2H5 1.11E19 -3.20 1780 [Westmoreland 1986] 256. C2H + C2H5 = C2H2 + C2H4 1.81E12 0.0 0 [Tsang and Hampson 1986] 257. C2H5 + H = C2H4 + H2 1.81E12 0.0 0 [Tsang and Hampson 1986] 258. C2H5 + O2 = C2H4 + HO2 1.92E07 1.02 -2035 [Miller et al. 2000a] 259. 2C2H4 = C2H5 + C2H3 4.82E14 0.0 71539 [Tsang and Hampson 1986] 260. C2H5 + OH = C2H4 + H2O 2.41E13 0.0 0 [Tsang and Hampson 1986] 261. C2H5 + HO2 = CH3 + CH2O + OH 2.40E13 0.0 0 [Zhang and McKinnon 1995] 262. CH2 + C2H5 = C2H4 + CH3 9.03E12 0.0 0 [Zhang and McKinnon 1995] 263. HCH + C2H5 = CH3 + C2H4 1.81E13 0.0 0 [Zhang and McKinnon 1995] Ethane (C2H6) reactions 264. C2H6 + CH3 = C2H5 + CH4 265. C2H6 + H = C2H5 + H2 266. C2H6 + O = C2H5 + OH 267. C2H6 + OH = C2H5 + H2O 268. C2H6 + O2 = C2H5 + HO2 269. C2H6 + HO2 = C2H5 + H2O2 270. HCO + C2H5 = C2H6 + CO 271. C2H4 + C2H5 = C2H3 + C2H6 272. CH2 + C2H6 = CH3 + C2H5 273. C2H6 + HCO = C2H5 + CH2O 274. 2C2H5 = C2H6 + C2H4 275. C2H3 + C2H5 = C2H6 + C2H2 276. C2H2 + C2H5 = C2H6 + C2H 5.50E-1 5.40E02 3.00E07 8.70E09 6.03E13 2.95E11 1.21E14 6.32E02 1.20E14 4.70E04 1.39E12 4.82E11 2.71E11 4.0 3.5 2.0 1.05 0.0 0.0 0.0 3.13 0.0 2.7 0.0 0.0 0.0 8300 [Miller and Melius 1992] 5210 [Miller and Melius 1992] 5115 [Miller and Melius 1992] 1810 [Miller and Melius 1992] 51870 [Baulch et al. 1992] 14940 [Tsang and Hampson 1986] 0 [Tsang and Hampson 1986] 18010 [Tsang and Hampson 1986] 0 [Miller and Melius 1992] 18233 [Zhang and McKinnon 1995] 0 [Zhang and McKinnon 1995] 0 [Zhang and McKinnon 1995] 23446 [Zhang and McKinnon 1995] This journal is © The Owner Societies 2002 Dimethylether (CH3OCH3): Formation and Consumption 277. CH3 + CH3O = CH3OCH3 1.21E13 278. CH3OCH3 + H = CH3OCH2 + H2 1.90E13 279. CH3OCH3 + OH =CH3OCH2 + H2O 6.27E12 280. CH3OCH3 + O= CH3OCH2 + OH 5.00E13 281. CH3OCH3 + CH3 = CH3OCH2 + CH4 3.55E12 282. CH3OCH2 = CH3 + CH2O 1.60E13 0.0 0.0 0.0 0.0 0.0 0.0 0 5166 739 4571 11800 25440 [Tsang and Hampson 1986] [Faubel et al. 1979] [Tully and Droege 1987] [Herron 1988] [Batt et al. 1982] [Sehested et al. 1997] Acetaldehyde Radical (CH2CHO) reactions 283. CH + CH2O = CH2CHO 284. C2H4 + O = CH2CHO + H 285. C3H6 + O = CH2CHO + CH3 9.64E13 1.21E06 1.08E06 286. C4H8 + O = CH2CHO + C2H5 5.14E06 287. CH2CHO = CH2CO + H 288. CH2CHO = CH3CO 1.58E13 1.00E13 0.0 2.08 2.15 -517 [Baulch et al. 1992] 0 [Baulch et a 1992] -795 [Knyazev et al. 1992/ Tsang 1991]h 1.95 -596 [Koda et al.1991/ Ko et al. 1991a]i 0.0 34970 [Colket et al. 1975] 0.0 47100 [Colket et al. 1975] CH3CO Formation and Consumption 289. CH3CO = CH3 + CO 290. CH3CO + CH3 = CH3COCH3 291. CH3CO + CH3 = CH2CO + CH4 292. CH3CO + O = CH3 + CO2 293. CH3CO + OH = CH2CO + H2O 294. CH3CO + H = CH3 + HCO 8.74E42 -8.62 22424 [Tsang and Hampson 1986] 4.04E15 -0.80 0 [Tsang and Hampson 1986] 6.06E14 -0.80 0 [Hassinen et al. 1990/Tsang and Hampson 1986]j 9.64E12 0.0 0 [Tsang and Hampson 1986] 1.21E13 0.0 0 [Tsang and Hampson 1986] 3.30E13 0.0 0 [Bartels et al. 1990]k Acetaldehyde (CH3CHO) and acetone (CH3COCH3) 295. IC3H7 + HO2 = CH3CHO + CH3 + OH 2.41E13 0.0 296. IC3H7 + O = CH3CHO + CH3 4.82E13 0.0 297. IC3H7 + O = CH3COCH3 + H 4.82E13 0.0 298. C2H4 + HO2 = CH3CHO + OH 6.03E09 0.0 299. C2H5 + O = CH3CHO + H 6.62E13 0.0 300. C2H5 + O2 = CH3CHO + OH 4.55E13 -1.03 301. C2H3 + OH = CH3CHO 302. CH3CHO = CH3 + HCO 303. CH3CHO + H = CH3CO + H2 304. CH3CHO + OH = CH3CO + H2O 305. CH3CHO + O = CH3CO + OH 306. CH3CHO + CH3 = CH3CO + CH4 307. CH3CHO + CH3 = CH3COCH3 + H 3.01E13 7.00E15 4.00E13 1.00E13 5.00E12 1.99E-6 1.66E10 0.0 0.0 0.0 0.0 0.0 5.64 0.0 0 0 0 7949 0 9665 [Tsang 1988] [Tsang 1988] [Tsang 1988] [Tsang and Hampson 1986] [Baulch 1992] [Bozzelli and Dean 1990, 0.01 atm] 0 [Tsang and Hampson 1986] 81674 [Baulch 1992] 4207 [Warnatz 1984] 0 [Warnatz 1984] 1792 [Warnatz 1984] 2464 [Baulch 1992] 12398 [Liu and Laidler 1968] Propargylene (C3H2, HCCCH, triplet) reactions 308. C3H2 + O = C2H + HCO 309. C3H2 + O = C2H2 + CO 310. C3H2 + OH = C2H2 + HCO 6.80E13 1.00E14 5.00E13 0.0 0.0 0.0 0 [Warnatz et al. 1982] 0 [Miller and Melius 1992] 0 [Miller and Melius 1992] This journal is © The Owner Societies 2002 311. C3H2 + OH = CHCHCHO 3.01E13 0.0 0 [rxn. 301.] Propargyl (H2CCCH) reactions 312. H2CCCH = C3H2 + H 313. H2CCCH + H = C3H2 + H2 314. H2CCCH + OH = C3H2 + H2O 315. H2CCCH + O = C3H2 + OH 316. CH3 + C2H = H2CCCH + H 317. C2H + CH2OH = H2CCCH + OH 318. C2H + C2H5 = CH3 + H2CCCH 319. C2H2 + HCCO = H2CCCH + CO 320. H2CCCH + O2 = CH2CO + HCO 321. CH2 + C2H2 = H2CCCH + H 322. HCH + C2H2 = H2CCCH + H 323. H2CCCH + O = C2H + CH2O 5.20E12 0.0 78447 [Scherer et al. 2000] 5.00E13 0.0 1000 [Miller and Melius 1992] 2.00E13 0.0 0 [Pauwels et al. 1995] 3.20E12 0.0 0 [Warnatz et al. 1982] 2.41E13 0.0 0 [Tsang and Hampson 1986] 1.21E13 0.0 0 [Tsang 1987] 1.81E13 0.0 0 [Tsang and Hampson 1986] 1.10E11 0.0 3000 [Miller and Melius 1992] 3.00E10 0.0 2868 [Miller and Melius 1992] 8.48E25 -3.736 3774 [QRRK, 20 torr]l 1.20E13 0.0 6600 [Boehland et al. 1986] 7.17E13 0.0 0 [rxn. 96.] 2-Propynal and its radical: HCCCHO and HCCCO 324. H2CCCH + O = HCCCHO + H 325. C3H2 + O = HCCCHO 326. CHCHCHO + H = HCCCHO + H2 327. CHCHCHO + OH = HCCCHO + H2O 328. C2H + CH3CO = CH3 + HCCCO 329. HCCCHO = C2H2 + CO 330. HCCCHO + O = HCCCO + OH 331. HCCCHO + OH = HCCCO + H2O 332. C2H + CO = HCCCO 6.03E13 6.62E12 1.21E13 2.00E13 1.81E13 8.51E14 5.68E12 1.60E13 1.51E11 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0 [rxn. 335.] 3060 [rxn. 336.] 0 [rxn. 214.] 0 [rxn. 226.] 0 [rxn. 318.] 70940 [Saito et al. 1990] 1542 [rxn. 352.] 0 [rxn. 339.] 4810 [rxn. 342.] 2-propenal (acrolein, CH2CHCHO): Formation and Consumption 333. H2CCCH + OH = CH2CHCHO 3.01E13 334. HCO + C2H3 = CH2CHCHO 1.81E13 335. C3H5 + O = CH2CHCHO + H 6.03E13 336. C3H4 + O = CH2CHCO + H 6.62E12 337. C2H3 + CH3CO = CH3 + CH2CHCO 1.81E13 338. CH2CHCHO + O = CH2CHCO + OH 5.68E12 339. CH2CHCHO + OH = CH2CHCO + H2O 1.60E13 340. CH2CHCHO+C2H5=CH2CHCO+C2H6 1.20E13 341. CH2CHCHO+IC3H7=CH2CHCO+C3H8 1.02E10 342. C2H3 + CO = CH2CHCO 1.51E11 343. CH2CHCHO + H = CHCHCHO + H2 5.07E07 344. CH2CHCHO + OH = CHCHCHO + H2O 2.02E13 345. CH2CHCHO + CH3 = CHCHCHO + CH4 4.16E12 346. CHCHCHO + H = CH2CHCHO 5.36E14 347. CHCHCHO = C2H2 + HCO 2.95E12 0.0 0 [rxn. 301.] 0.0 0 [Tsang and Hampson 1986] 0.0 0 [Tsang 1991] 0.0 3060 [Aleksandrov et al. 1980] 0.0 0 [Tsang and Hampson 1986] 0.0 1542 [rxn. 352.] 0.0 0 [Maldotti et al. 1992] 0.0 12647 [rxn. 354.] 0.0 6840 [Szirovicza 1985] 0.0 4810 [Tsang and Hampson 1986] 1.93 12951 [rxn. 232.] 0.0 5955 [rxn. 244.] 0.0 11128 [rxn. 247.] 0.0 982 [m] 0.0 11110 [n] Propanal and its radical: C2H5CHO and C2H5CO 348. NC3H7 + O = C2H5CHO + H 349. NC3H7 + O2 = C2H5CHO + OH 9.64E13 1.10E08 0.0 0.0 0 [Tsang 1988]o 0 [Baker et al. 1971] This journal is © The Owner Societies 2002 350. C2H5 + HCO = C2H5CHO 351. C3H5 + OH = C2H5CHO 352. C2H5CHO + O = C2H5CO + OH 353.C2H5CHO + OH = C2H5CO + H2O 354. C2H5CHO + C2H5 = C2H5CO + C2H6 355. C2H5 + CO = C2H5CO 1.81E13 0.0 3.01E13 0.0 5.68E12 0.0 1.21E13 0.0 1.20E13 0.0 1.51E11 0.0 0 [Tsang and Hampson 1986] 0 [rxn. 301.] 1542 [Singleton et al. 1977] 0 [Atkinson et al. 1997]p 12647 [q] 4809 [Tsang and Hampson 1986] C3H4 (allene, CH2=C=CH2), C3H4P (propyne, CH3CCH) and C3H4CY (cyclopropene) 356. C3H4 = H2CCCH + H 357. C3H4P = H2CCCH + H 358. CH + C2H4 = C3H4 + H 359. CH2 + C2H2 = C3H4CY 360. CH2 + C2H2 = C3H4 361. CH2 + C2H2 = C3H4P 362. C3H4CY = C3H4 363. C3H4CY = C3H4P 364. C3H4 + O = CO + C2H4 365. C3H4 + OH = HCO + C2H4 366. C3H4 + CH3 = H2CCCH + CH4 367. C3H4P + CH3 = H2CCCH + CH4 368. C3H4 + H = C2H2 + CH3 369. C2H + CH3 = C3H4P 370. C2H3 + HCH = C3H4 + H 371. C3H4P + C2H = C2H2 + H2CCCH 372. C3H4 + C2H = C2H2 + H2CCCH 373. C3H4 + O = CH2O + C2H2 374. C3H4 + O = HCO + C2H3 375. C3H4P + O = CH2O + C2H2 376. C3H4P + O = HCO + C2H3 377. C3H4 + OH = CH2CO + CH3 378. C3H4P + OH = CH2CO + CH3 379. C3H4 + H = H2CCCH + H2 380. C3H4 + OH = H2CCCH + H2O 381. C3H4P + H = H2CCCH + H2 382. C3H4P + OH = H2CCCH + H2O 383. CH3 + C2H2 = C3H4P + H 2.30E12 1.34E12 1.75E15 1.66E38 7.46E39 2.62E40 1.51E14 7.08E13 1.50E13 1.00E12 2.00E12 2.00E12 2.00E13 8.07E49 3.00E13 1.00E13 1.00E13 9.00E12 9.00E12 7.50E12 7.50E12 3.37E12 4.28E11 3.00E07 2.00E07 3.00E07 2.00E07 1.92E04 0.0 69684 [Scherer et al. 2000] 0.0 69942 [Scherer et al. 2000] -0.38 100 [QRRK, 20 torr]r -8.65 6090 [QRRK, 20 torr]l -8.78 6350 [QRRK, 20 torr]l -8.86 6410 [QRRK, 20 torr]l 0.0 50400 [Karni et al. 1988] 0.0 43700 [Karni et al. 1988] 0.0 2103 [Warnatz 1984] 0.0 0 [Westbrook and Dryer 1984] 0.0 7700 [Kern et al. 1991] 0.0 7700 [Kern et al. 1991] 0.0 2400 [Kern et al. 1991] -11.305 43800 [QRRK, 20 torr]f 0.0 0 [Miller and Melius 1992] 0.0 0 [Kern et al. 1991] 0.0 0 [Kern et al. 1991] 0.0 1870 [Zhang and McKinnon 1995] 0.0 1870 [Zhang and McKinnon 1995] 0.0 2102 [Zhang and McKinnon 1995] 0.0 2102 [Zhang and McKinnon 1995] 0.0 -304 [Zhang and McKinnon 1995] 0.0 -843 [Zhang and McKinnon 1995] 2.0 5000 [Pauwels et al. 1995] 2.0 1000 [Pauwels et al. 1995] 2.0 5000 [Pauwels et al. 1995] 2.0 1000 [Pauwels et al. 1995] 2.42 12892 [Diau et al. 1994]s C3H5 (allyl, H2CCHCH2) reactions 384. CH + C2H4 = C3H5 385. C3H4 + H = C3H5 386. C3H5 + OH = C3H4 + H2O 387. C3H5 + CH2 = C4H613 + H 388. C2H + C3H5 = C2H2 + C3H4 389. C2H + C3H5 = C2H3 + H2CCCH 390. C3H5 + C2H3 = C3H4 + C2H4 391. C3H5 + C2H5 = C3H4 + C2H6 392. C2H3 + CH2OH = C3H5 + OH 393. C2H4 + HCH = C3H5 + H 1.67E34 1.20E11 6.03E12 3.01E13 1.50E-1 2.00E01 2.41E12 9.64E11 1.21E13 3.19E12 -7.60 0.69 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 3690 [QRRK, 20 torr]r 3007 [Tsang and Walker 1992] 0 [Tsang 1991] 0 [Tsang 1991] 0 [Tsang 1991] 0 [Tsang 1991] 0 [Tsang 1991] -131 [Tsang 1991] 0 [Tsang 1987] 5285 [Zhang and McKinnon 1995] This journal is © The Owner Societies 2002 394. CH3 + C2H2 = C3H5 395. C2H3 + CH3 = C3H5 + H 1.40E04 7.20E13 2.21 0.0 16500 [Diau et al. 1994]s 0 [Fahr et al. 1999] C3H6 (propene, H2CHCH3) reactions 396. C3H5 + H = C3H6 397. C3H6 + HO2 = C3H5 + H2O2 398. C3H6 + CH3 = C3H5 + CH4 399. C3H6 + O = C3H5 + OH 400. C3H6 + O = C2H5 + HCO 401. C3H6 + O2 = C3H5 + HO2 402. C3H6 + CH2OH = C3H5 + CH3OH 403. C3H6 + CH3O = C3H5 + CH3OH 404. C3H6 + C2H = C3H4P + C2H3 405. C3H6 + CH2 = C3H5 + CH3 406. C3H6 + HCO = C3H5 + CH2O 407. C3H6 + C2H5 = C3H5 + C2H6 408. C3H6 + C2H3 = C3H5 + C2H4 409. C3H5 + HCO = C3H6 + CO 410. C3H5 + CH2OH = C3H6 + CH2O 411. C3H5 + CH3O = C3H6 + CH2O 412. C3H5 + C2H3 = C3H6 + C2H2 413. C3H5 + C2H5 = C3H6 + C2H4 414. 2C3H5 = C3H4 + C3H6 415. CH2 + C2H5 = C3H6 + H 416. CH2 + C2H4 = C3H6 417. NC3H7 + H = C3H6 + H2 418. NC3H7 + OH = C3H6 + H2O 419. NC3H7 + HCH = C3H6 + CH3 420. NC3H7 + CH3 = C3H6 + CH4 421. NC3H7 + O2 = C3H6 + HO2 422. NC3H7 + CH2OH = C3H6 + CH3OH 423. NC3H7 + C2H = C3H6 + C2H2 424. NC3H7 + C2H3 = C3H6 + C2H4 425. NC3H7 + C2H5 = C3H6 + C2H6 426. NC3H7 + C3H5 = 2C3H6 427. IC3H7 + H = C3H6 + H2 428. IC3H7 + CH3 = C3H6 + CH4 429. IC3H7 + O2 = C3H6 + HO2 430. IC3H7 + OH = C3H6 + H2O 431. IC3H7 + C2H = C3H6 + C2H2 432. IC3H7 + CH2OH = C3H6 + CH3OH 433. IC3H7 + C2H3 = C3H6 + C2H4 434. IC3H7 + C2H5 = C3H6 + C2H6 435. IC3H7 + C3H5 = 2C3H6 5.80E11 9.64E03 2.21E00 6.03E10 1.21E11 6.03E13 6.03E01 9.00E01 1.21E13 7.23E11 1.08E07 2.23E00 2.21E00 6.03E13 1.81E13 3.01E13 4.82E12 2.59E12 8.43E10 9.03E12 9.03E13 1.81E12 2.41E13 1.81E12 1.14E13 1.00E12 4.82E11 6.03E12 1.21E12 1.45E12 1.45E12 3.61E12 9.41E10 1.26E11 2.41E13 3.61E12 2.89E12 1.52E14 2.30E13 2.29E13 0.236 -51 [Harding and Klippenstein 2000] 2.6 13910 [Tsang 1991] 3.5 5675 [Tsang 1991] 0.7 7633 [Tsang 1991] 0.1 8960 [Tsang 1991] 0.0 47593 [Tsang 1991] 2.95 11989 [Tsang 1991] 2.95 11987 [Tsang 1991] 0.0 0 [Tsang 1991] 0.0 6192 [Tsang 1991] 1.9 17006 [Zhang and McKinnon 1995] 3.5 6637 [Tsang 1991] 3.5 4682 [Tsang 1991] 0.0 0 [Tsang 1991] 0.0 0 [Tsang 1991] 0.0 0 [Tsang 1991] 0.0 0 [Tsang 1991] 0.0 -131 [Tsang 1991] 0.0 -262 [Tsang 1991] 0.0 0 [Zhang and McKinnon 1995] 0.0 0 [Zhang and McKinnon 1995] 0.0 0 [Tsang 1988] 0.0 0 [Tsang 1988] 0.0 0 [Tsang 1988] -0.32 0 [Tsang 1988] 0.0 5020 [Warnatz 1984] 0.0 0 [Tsang 1988] 0.0 0 [Tsang 1988] 0.0 0 [Tsang 1988] 0.0 0 [Tsang 1988] 0.0 -131 [Tsang 1991] 0.0 0 [Tsang 1988] 0.68 0 [Tsang 1988] 0.0 0 [Tsang 1988] 0.0 0 [Tsang 1988] 0.0 0 [Tsang 1988] 0.0 0 [Tsang 1988] -0.70 0 [Tsang 1988] -0.35 0 [Tsang 1988] -0.35 -131 [Tsang 1991] Formation/Consumption of n-propyl (NC3H7, CH2CH2CH3) and i-propyl (IC3H7, CH3CHCH3) 436. NC3H7 = C2H4 + CH3 437. IC3H7 = CH3 + C2H4 1.20E13 1.00E12 0.0 0.0 30303 [Tsang 1988] 34580 [Konar et al. 1968] This journal is © The Owner Societies 2002 438. C3H6 + H = NC3H7 439. C3H6 + H = IC3H7 440. C3H8 + H = NC3H7 + H2 441. C3H8 + OH = NC3H7 + H2O 442. C3H8 + O = NC3H7 + OH 443. C3H8 + CH3 = NC3H7 + CH4 444. C3H8 + H = IC3H7 + H2 445. C3H8 + OH = IC3H7 + H2O 446. C3H8 + O = IC3H7 + OH 447. C3H8 + CH3 = IC3H7 + CH4 448. NC3H7 + HCH = C2H4 + C2H5 449. IC3H7 + C2H2 = C4H613 + CH3 450. NC3H7 + C2H = H2CCCH + C2H5 1.30E13 0.0 1.30E13 0.0 1.33E06 2.54 3.16E07 1.80 1.93E05 2.68 9.04E-1 3.65 1.30E06 2.40 7.08E06 1.90 4.77E04 2.71 1.51E00 3.46 1.81E13 0.0 2.77E10 0.0 1.21E13 0.0 3261 [Tsang 1992] 1560 [Tsang 1992] 6756 [Tsang 1988] 934 [Cohen 1991] 3716 [Tsang 1988] 7154 [Tsang 1988] 4471 [Tsang 1988] -159 [Cohen 1991] 2106 [Tsang 1988] 5481 [Tsang 1988] 0 [Tsang 1988] 6504 [Tsang 1988] 0 [Tsang 1988] Propane (C3H8) chemistry 451. CH3 + C2H5 = C3H8 452. NC3H7 + H2O2 = C3H8 + HO2 453. NC3H7 + C2H3 = C2H2 + C3H8 454. NC3H7 + HCO = C3H8 + CO 455. NC3H7 + CH2OH = C3H8 + CH2O 456. NC3H7 + CH3O = C3H8 + CH2O 457. NC3H7 + CH3OH = C3H8 + CH2OH 458. NC3H7 + CH3OH = C3H8 + CH3O 459. NC3H7 + CH2O = C3H8 + HCO 460. NC3H7 + C2H5 = C3H8 + C2H4 461. NC3H7 + C2H6 = C3H8 + C2H5 462. NC3H7 + NC3H7 = C3H8 + C3H6 463. NC3H7 + C3H5 = C3H4 + C3H8 464. NC3H7 + C3H6 = C3H8 + C3H5 465. NC3H7 + C3H8 = C3H8 + IC3H7 466. IC3H7 + C2H5 = C2H4 + C3H8 467. IC3H7 + C2H6 = C3H8 + C2H5 468. IC3H7 + CH3OH = C3H8 + CH2OH 469. IC3H7 + CH3OH = C3H8 + CH3O 470. IC3H7 + CH2O = C3H8 + HCO 471. IC3H7 + H = C3H8 472. IC3H7 + H2O2 = C3H8 + HO2 473. IC3H7 + HCO = C3H8 + CO 474. IC3H7 + CH2OH = C3H8 + CH2O 475. IC3H7 + CH3O = C3H8 + CH2O 476. IC3H7 + C2H3 = C3H8 + C2H2 477. IC3H7 + NC3H7 = C3H8 + C3H6 478. IC3H7 + IC3H7 = C3H8 + C3H6 479. IC3H7 + C3H5 = C3H8 + C3H4 480. IC3H7 + C3H6 = C3H8 + C3H5 3.37E13 1.87E04 1.21E12 6.03E13 9.64E11 2.41E13 3.37E01 1.45E01 3.01E03 1.15E12 2.53E-1 1.69E12 7.23E11 2.23E00 8.44E-4 1.84E13 8.44E-1 3.19E01 1.45E01 1.08E11 2.00E13 2.89E02 1.21E14 2.35E12 1.21E13 1.52E14 5.13E13 2.11E14 4.58E12 6.62E-2 0.0 2.11 0.0 0.0 0.0 0.0 3.17 3.10 2.90 0.0 3.82 0.0 0.0 3.50 4.00 -0.35 4.20 3.70 3.10 0.0 0.0 2.83 0.0 0.0 0.0 -0.70 -0.35 -0.70 -0.35 4.00 0 [Baulch et al. 1994] 2571 [Tsang 1988] 0 [Tsang 1988] 0 [Tsang 1988] 0 [Tsang 1988] 0 [Tsang 1988] 9161 [Tsang 1988] 8942 [Tsang 1988] 5862 [Tsang 1988] 0 [Tsang 1988] 9042 [Tsang 1988] 0 [Tsang 1988] -131 [Tsang 1991] 6637 [Tsang 1991] 4726 [Tsang 1988] 0 [Tsang 1988] 8716 [Tsang 1988] 10532 [Tsang 1988] 10333 [Tsang 1988] 6955 [Tsang 1988] 0 [Warnatz 1984] 4048 [Tsang 1988] 0 [Tsang 1988] 0 [Tsang 1988] 0 [Tsang 1988] 0 [Tsang 1988] 0 [Tsang 1988] 0 [Tsang 1988] -131 [Tsang 1991] 8070 [Tsang 1991] C4H2 (diacetylene, HCCCCH, 1-,3-butadiyne) and its radical (C4H, butadiynyl) 481. C4H2 + O = C3H2 + CO 1.20E12 0.0 0 [Miller and Melius 1992] This journal is © The Owner Societies 2002 482. 2C3H2 = C4H2 + C2H2 483. C2H2 + C2H = C4H2 + H 484. C4H2 + M = C4H + H + M 485. C4H2 + C2H = C4H + C2H2 486. C4H4 + C2H = C4H2 + C2H3 2.00E13 4.12E15 3.50E17 2.00E13 1.00E13 0.0 85000 -0.490 740 0.0 80065 0.0 0 0.0 0 [Kern et al. 1991] [QRRK, 20 torr]t [Frenklach and Warnatz 1987] [Frenklach and Warnatz 1987] [Frenklach and Warnatz 1987] n-C4H3 (HCCHCCH) and i-C4H3 (H2CCCCH) reactions 487. HCCHCCH + H = H2CCCCH + H 1.00E14 0.0 0 [Miller and Melius 1992] 488. H2CCCCH + M = C4H2 + H + M 2.00E15 0.0 48000 [Miller and Melius 1992] 489. HCCHCCH + M = C4H2 + H + M 1.00E14 0.0 30000 [Miller and Melius 1992] 490. H2CCCCH + O = CH2CO + C2H 2.00E13 0.0 0 [Miller and Melius 1992] 491. H2CCCCH + O = H2C4O + H 2.00E13 0.0 0 [Miller and Melius 1992] 492. H2CCCCH + O2 = CH2CO + HCCO 1.00E12 0.0 0 [Miller and Melius 1992] 493. H2CCCCH + H = C4H2 + H2 5.00E13 0.0 0 [Miller and Melius 1992] 494. H2CCCCH + OH = C4H2 + H2O 3.00E13 0.0 0 [Miller and Melius 1992] 495. HCCHCCH + H = C4H2 + H2 2.50E13 0.0 0 [k493/2)] 496. HCCHCCH + OH = C4H2 + H2O 1.50E13 0.0 0 [[k494/2)] 497. H2CCCCH + H2 = C2H2 + C2H3 5.01E10 0.0 20000 [Colket 1986] 498. H2CCCCH + HCH = C3H4 + C2H 2.00E13 0.0 0 [Miller and Melius 1992] 499. C2H2 + C2H = HCCHCCH 1.09E32 -6.577 4090 [QRRK, 20 torr]t 500. H2CCCH + CH = H2CCCCH + H 7.00E13 0.0 0 [Miller and Melius 1992] 501. H2CCCH + CH = HCCHCCH + H 7.00E13 0.0 0 [Miller and Melius 1992] 502. C2H2 + C2H2 = HCCHCCH + H 1.00E12 0.0 65980 [Benson 1989] C4H4 (vinylacetylene, H2CCHCCH) reactions 503. C2H2 + C2H2 = C4H4 504. C2H3 + C2H3 = C4H4 + 2H 505. C2H3 + C2H2 = C4H4 + H 506. C4H4 + C2H = H2CCCCH + C2H2 507. C4H4 + C2H = HCCHCCH + C2H2 508. H2CCCH + HCH = C4H4 + H 509. C2H3 + C2H = C4H4 510. C2H4 + C2H = C4H4 + H 1.89E58 -13.60 62790 [QRRK, 20 torr]u 7.83E12 0.0 0 [Knyazev et al. 1996c] 1.91E15 -0.74 10500 [QRRK, 20 torr]v 4.00E13 0.0 0 [Kiefer et al. 1985] 4.00E13 0.0 0 [Kiefer et al. 1985] 4.00E13 0.0 0 [Miller and Melius 1992] 2.12E60 -13.452 27550 [QRRK, 20 torr]w 1.21E13 0.0 0 [Tsang and Hampson 1986] Formation of n-C4H3 (HCCHCCH) 511. C4H4 + H = HCCHCCH + H2 2.00E07 2.0 15000 [Miller and Melius 1992] 512. C4H4 + OH = HCCHCCH + H2O 7.50E06 2.0 5000 [Miller and Melius 1992] 513. C4H4 + C2H3 = C2H4 + HCCHCCH 5.00E11 0.0 16300 [Colket 1986] Formation of i-C4H3 (H2CCCCH) 514. C4H4 + H = H2CCCCH + H2 3.00E07 2.0 5000 [Miller and Melius 1992] 515. C4H4 + OH = H2CCCCH + H2O 1.00E07 2.0 2000 [Miller and Melius 1992] 516. C4H4 + C2H3 = C2H4 + H2CCCCH 5.00E11 0.0 16300 [Colket 1986] n-C4H5 (CH2CHCHCH) and i-C4H5 (CH2CHCCH2) reactions 517. C2H3 + C2H2 = CH2CHCHCH 518. CH2CHCHCH + H = C4H613 3.45E45 -11.13 1.21E14 0.0 15980 [QRRK, 20 torr]v 0 [x] This journal is © The Owner Societies 2002 519. CH2CHCCH2 + M = C4H4 + H + M 520. CH2CHCHCH + M = C4H4 + H + M 521. CH2CHCCH2 + O2 = C4H4 + HO2 522. CH2CHCHCH + O2 = C4H4 + HO2 523. CH2CHCHCH + H = CH2CHCCH2 + H 524. CH2CHCHCH + OH = C4H4 + H2O 525. CH2CHCHCH + H = C4H4 + H2 526. 2C2H3 = CH2CHCCH2 + H 527. CH2CHCCH2 + OH = C4H4 + H2O 528. CH2CHCCH2 + H = C4H4 + H2 2.00E15 1.00E14 1.20E11 1.20E11 1.00E14 2.00E07 3.00E07 4.00E13 2.00E07 3.00E07 0.0 0.0 0.0 0.0 0.0 2.0 2.0 0.0 2.0 2.0 42000 [Miller and Melius 1992] 30000 [Miller and Melius 1992] 0 [Emdee et al. 1992] 0 [Emdee et al. 1992] 0 [Miller and Melius 1992] 1000 [Miller and Melius 1992] 1000 [Miller and Melius 1992] 0 [Miller and Melius 1992] 1000 [Miller and Melius 1992] 1000 [Miller and Melius 1992] 1,3-butadiene (C4H613, CH2CHCHCH2) and i-C4H7 (I-C4H7, CH2CHCHCH3) reactions 2.27E12 -0.17 3380 [QRRK, 20 torr]y 2.11E22 -4.70 1190 [QRRK, 20 torr]y 3.16E13 0.0 34800 [Weissman and Benson 1984] 532. I-C4H7 + H = C4H613 + H2 1.81E12 0.0 0 [rxn. 257.] 533. I-C4H7 + OH = C4H613 + H2O 2.41E13 0.0 0 [rxn. 260.] 534. C2H3 + C2H3 = C4H613 2.00E13 0.0 0 [Colket et al. 1989] 535. C3H6 + C2H3 = C4H613 + CH3 7.23E11 0.0 5010 [Tsang 1991] 536. C4H613 + H2CCCH = CH2CHCHCH + C3H4 1.00E13 0.0 22500 [Kern et al. 1988] 537. C4H613 + O = C2H4 + CH2CO 1.00E12 0.0 0 [Pitz and Westbrook 1986] 538. C4H613 + O = C3H4 + CH2O 1.00E12 0.0 0 [Pitz and Westbrook ‘86] 539. C4H613 + OH = C3H5 + CH2O 1.00E12 0.0 0 [Pitz and Westbrook ‘86] 540. C4H613 + OH = C2H5 + CH2CO 1.00E12 0.0 0 [Pitz and Westbrook ‘86] 529. C2H3 + C2H4 = C4H613 + H 530. C2H3 + C2H4 = I-C4H7 531. I-C4H7 = C4H613 + H 1-butyne (C4H6-1, H2CCCCH) Formation and Consumption 541. H2CCCH + CH3 = C4H6-1 542. C3H6 + C2H = C4H6-1 + CH 543. C4H6-1 = C4H612 544. C4H6-1 + O = C3H6 + CO 5.42E13 1.21E13 2.50E13 2.00E13 0.0 0.0 0.0 0.0 0 0 65000 1659 [Fahr and Nayak 2000] [Tsang 1991] [Hidaka et al. 1995a] [Cvetanovic 1987] 1,2-butadiene (C4H612, H2CCCHCH3) Formation and Consumption 545. H2CCCH + CH3 = C4H612 546. C4H612 = C4H613 547. C4H612 + H = C3H4 + CH3 548. C4H612 + H = C3H4P + CH3 3.61E13 0.0 2.50E13 0.0 6.00E12 0.0 6.00E12 0.0 0 63000 2100 2100 [Fahr and Nayak 2000] [Hidaka et al. 1995b] [Hidaka et al. 1995b] [Hidaka et al. 1995b] 1-butene (C4H8, CH2CHCH2CH3) Formation and Consumption 549. I-C4H7 + H = C4H8 550. C4H8 = C3H5 + CH3 1.00E14 1.10E16 0.0 0.0 5.00E13 1.00E07 0.0 2.0 0 [z] 77692 [Knyazev and Slagle 2001] H2C4O reactions 551. H2C4O + H = C2H2 + HCCO 552. H2C4O + OH = CH2CO + HCCO 3000 [Miller and Melius 1992] 2000 [Miller and Melius 1992] This journal is © The Owner Societies 2002 C5H3 (cyclopentatrienyl) reactions 553. C5H4 + H = C5H3 + H2 554. C5H4 + OH = C5H3 + H2O 555. C5H4 + O = C5H3 + OH 556. C5H3 + H = C5H4 557. C5H3 + O2 = C2H2 + HCCO + CO 1.00E06 1.00E06 1.00E06 1.00E14 1.00E12 2.50 2.0 2.50 0.0 0.0 5000 0 3000 0 0 [Alzueta et al. 1998] [Alzueta et al. 1998] [Alzueta et al. 1998] [Alzueta et al. 2000] [Alzueta et al. 1998] C5H3(L) (1,3-pentadiyne-5-yl, HCCCCCH2) and C5H2(L) (HCC-CC-CH) reactions 558. C4H2 + HCH = C5H3(L) + H 559. C4H2 + CH2 = C5H3(L) + H 560. C4H2 + CH = C5H2(L) + H 561. C5H3(L) + H = C5H2(L) + H2 1.30E13 3.00E13 1.00E14 6.03E13 0.0 0.0 0.0 0.0 0 0 0 15103 [Miller and Melius 1992] [Miller and Melius 1992] [Miller and Melius 1992] [rxn. 95.] 2.095 0.0 0.0 0.0 0.0 2.0 2.71 0.0 15842 [rxn. 644.] 4571 [rxn. 647.] 14694 [rxn. 645.] 15060 [aa] 2259 [rxn. 590.] 0 [rxn. 593.] 1106 [rxn. 595.] 6000 [estimate, present work] C5H4 (cyclopentatriene) reactions 562. C5H5 + H = C5H4 + H2 563. C5H5 + OH = C5H4 + H2O 564. C5H5 + O = C5H4 + OH 565. C5H5 + CH3 = C5H4 + CH4 566. C5H4H + H = C5H4 + H2 567. C5H4H + OH = C5H4 + H2O 568. C5H4H + O = C5H4 + OH 569. C5H4 = C5H4(L) 3.23E07 2.11E13 2.00E13 2.00E12 2.80E13 3.08E06 4.77E04 1.00E13 C5H4(L) (1,2-pentadiene-4-yne, CH2CCHCCH) reactions 570. C5H5(L) + H = C5H4(L) + H2 571. C5H5(L) + OH = C5H4(L) + H2O 572. C5H5(L) + CH3 = C5H4(L) + CH4 1.81E12 2.41E13 1.95E13 0.0 0.0 -0.50 0 [rxn. 257.] 0 [rxn. 260.] 0 [rxn. 254.] Cyclopentadienyl (C5H5), C5H4H (cyclic: -CH2CCHCHCH-), C5H5(L) (2-penten-4-ynyl, CH2CHCHCCH) 573. C5H5 + H = C5H6 574. C5H5 = H2CCCH + C2H2 575. C5H5 = C5H4H 576. C5H4H = H2CCCH + C2H2 577. C5H5 = C5H5(L) 578. C5H5 + O = CH2CHCHCH + CO 579. C5H5 + O = C5H5O 580. C5H5 + CH3 = C5H5CH3 2.71E63 2.79E79 5.17E80 3.40E80 1.64E96 7.27E13 1.84E03 3.43E52 -14.79 -18.30 -20.40 -19.20 -23.50 -0.28 1.03 -12.49 21050 130834 96185 102265 137409 470 -6960 12000 [QRRK, 20 torr]ab [Moskaleva and Lin 2000] [Moskaleva and Lin 2000] [Moskaleva and Lin 2000] [Moskaleva and Lin 2000] [QRRK, 20 torr]ab [QRRK, 20 torr]ab [QRRK, 20 torr]ac Cyclopenadienone (C5H4O), C5H4OH and C5H5OH reactions 581. C5H5 + O = C5H4O + H 582. C5H5O = C5H4O + H 583. C5H5O = CH2CHCHCH + CO 584. C5H5 + OH = C5H4OH + H 585. C5H4O + H = C5H4OH 586. C5H4OH + O2 = C5H4O + HO2 6.71E13 -0.03 40 [QRRK, 20 torr]ab 2.90E32 -6.50 21220 [Alzueta et al. 2000] 1.10E79 -19.62 66250 [Alzueta et al. 2000] 2.15E30 -4.61 25050 [QRRK, 20 torr]ab 1.10E69 -16.018 37130 [QRRK, 20 torr]f 3.00E13 0.0 5000 [Alzueta et al. 2000] This journal is © The Owner Societies 2002 587. C5H4O + H = CH2CHCHCH + CO 588. C5H4O + O = C4H4 + CO2 589. C5H4O = 2C2H2 + CO 2.10E61 1.00E13 1.10E47 -13.27 0.0 -9.63 40810 [Alzueta et al. 2000] 2000 [Alzueta et al. 2000] 99500 [Wang and Brezinsky 1998] Cyclopentadiene (C5H6) reactions 590. C5H6 + H = C5H5 + H2 2.80E13 0.0 591. C5H6 + H = C5H4H + H2 2.80E13 0.0 592. C5H6 + H = C3H5 + C2H2 6.60E14 0.0 593. C5H6 + OH = C5H5 + H2O 3.08E06 2.0 594. C5H6 + OH = C5H4H + H2O 3.08E06 2.0 595. C5H6 + O = C5H5 + OH 4.77E04 2.71 596. C5H6 + O = C5H4H + OH 4.77E04 2.71 597. C5H6 + O2 = C5H5 + HO2 4.00E13 0.0 598. C5H6 + HO2 = C5H5 + H2O2 1.10E04 2.60 599. C5H6 + CH3 = C5H5 + CH4 1.80E-1 4.0 600. C5H6 + CH3 = C5H4H + CH4 1.80E-1 4.0 601. C5H6 + C2H3 = C5H5 + C2H4 1.20E-1 4.0 602. C5H6 + C6H5 = C5H5 + C6H6 1.00E-1 4.0 603. C5H6 + C10H7*1 = C5H5 + C10H8 1.00E-1 4.0 604. C5H6 + C10H7*2 = C5H5 + C10H8 1.00E-1 4.0 605. C5H6 + CH2CHCHCH = C5H5 + C4H613 1.20E-1 4.0 606. C5H6 + CH2CHCCH2 = C5H5 + C4H613 6.00E12 0.0 607. C5H6 + C3H5 = C5H5 + C3H6 2.00E-1 4.0 608. C3H5 + C5H5 = C5H6 + C3H4 1.00E12 0.0 2259 [Roy et al. 1998] 35139 [ad] 12345 [Roy et al. 1998] 0 [Zhong and Bozzelli 1998] 32880 [ad] 1106 [Zhong and Bozzelli 1998] 33986 [ad] 37150 [Zhong and Bozzelli 1998] 12900 [Zhong and Bozzelli 1998] 0 [Zhong and Bozzelli 1998] 32880 [ad] 0 [Zhong and Bozzelli 1998] 0 [Zhong and Bozzelli 1998] 0 [rxn. 602.] 0 [rxn. 602.] 0 [Zhong and Bozzelli 1998] 0 [Emdee et al. 1992] 0 [Zhong and Bozzelli 1998] 0 [Dean 1990] 1,3,5-hexatriyne (C6H2, HCCCCCCH, triacetylene) reactions 609. C6H2 + M = C6H + H + M 610. C6H2 + OH = C6H + H2O 611. C6H2 + C2H = C6H + C2H2 612. C6H2 + C2H = C4H + C4H2 613. C4H2 + C2H = C6H2 + H 614. 2C3H2 = C6H2 + H2 5.00E16 0.0 80065 [Frenklach and Warnatz 1987] 1.10E13 0.0 7003 [Frenklach and Warnatz 1987] 2.00E13 0.0 0 [Frenklach and Warnatz 1987] 1.00E13 0.0 0 [Frenklach and Warnatz 1987] 4.98E40 -7.66 21910 [QRRK, 20 torr]f 2.00E13 0.0 85000 [Kern et al. 1991] Hexendiynyl (C6H3, HCCCCCHCH) reactions 615. C4H2 + C2H = C6H3 616. C6H2 + H = C6H3 617. C6H3 + H = C6H2 + H2 3.76E63 -14.722 27250 [QRRK, 20 torr]f 2.74E56 -12.585 29690 [QRRK, 20 torr]f 2.00E13 0.0 0 [Frenklach and Warnatz 1987] 3-hexen-1,5-diyne (C6H4, HCCCHCHCCH) and benzyne reactions 618. C6H4 + H = C6H3 + H2 619. C6H3 + H = C6H4 620. C6H4 + OH = C6H3 + H2O 621. C6H4 + C2H = C6H3 + C2H2 622. HCCHCCH + C2H2 = BENZYNE + H 623. HCCHCCH + C2H2 = C6H4 + H 624. C6H4 + H = C6H5(L) 1.50E14 0.0 10205 [Frenklach and Warnatz 1987] 9.55E67 -15.959 31510 [QRRK, 20 torr]f 7.00E13 0.0 3011 [Frenklach and Warnatz 1987] 2.00E13 0.0 0 [Frenklach and Warnatz 1987] 1.64E09 0.73 12180 [Westmoreland et al. 1989] 2.96E02 3.33 9620 [Westmoreland et al. 1989] 1.41E67 -15.609 20940 [QRRK, 20 torr]f This journal is © The Owner Societies 2002 Phenyl (C6H5), aliphatic C6H5 (C6H5(L)) and benzyne reactions 625. C6H5(L) + H = C6H4 + H2 626. HCCHCCH + C2H2 = C6H5(L) 627. HCCHCCH + C2H2 = C6H5 628. H2CCCCH + C2H3 = C6H5 + H 629. C6H5 + O2 = C6H5O + O 630. C6H5 + HO2 = C6H5O + OH 631. C6H5(L) = C6H5 632. C6H5 + O = C5H5 + CO 633. C6H5 + CH2O = C6H6 + HCO 634. C6H5 + H = C6H6 635. C6H5 + H = BENZYNE + H2 636. C6H5 = BENZYNE + H 637. C6H5 = C6H4 + H 2.00E13 0.0 0 [Frenklach and Warnatz 1987] 1.73E11 -0.41 4030 [Westmoreland et al. 1989] 3.33E24 -3.89 9210 [Westmoreland et al. 1989] 6.00E12 0.0 0 [Pope and Miller 2000] 2.39E21 -2.62 4400 [QRRK, 20 torr]ae 5.00E13 0.0 1000 [Leung and Lindstedt 1995] 1.66E11 0.0 16350 [Dewar et al. 1987] 9.00E13 0.0 0 [Frank et al. 1994] 1.75E10 0.0 0 [Yu and Lin 1993] 8.02E19 -2.011 1968 [Mebel et al. 2001, 100 torr] 4.40E-13 7.831 9261 [Mebel et al. 2001, 100 torr] 6.11E45 -8.857 94310 [Madden et al. 1997, 380 torr] 1.45E77 -17.10 129500 [Madden et al. 1997, 380 torr] Benzene (C6H6) and fulvene (C6H6F) reactions 638. H2CCCH + H2CCCH = C6H6 639. C4H4 + C2H3 = C6H6 + H 640. C3H4 + H2CCCH = C6H6 + H 641. CH2CHCHCH + C2H2 = C6H6 + H 642. CH2CHCHCH + C2H3 = C6H6 + H2 643. C4H4 + C2H2 = C6H6 644. C6H6 + H = C6H5 + H2 645. C6H6 + O = C6H5 + OH 646. C6H6 + O = C6H5O + H 647. C6H6 + OH = C6H5 + H2O 648. C6H6 + O2 = C6H5 + HO2 649. C6H5 + CH4 = C6H6 + CH3 650. C6H6F = C6H6 651. C6H6F + H = C6H6 + H 652. C6H6 + OH = C6H5OH + H 0 [Marinov et al. 1996]af 2510 [Kubitza et al. 1994, cited in Lindstedt and Skevis 1997] 2.20E11 0.0 2000 [Wu and Kern 1987] 1.90E07 1.47 4910 [Westmoreland et al. 1989] 2.80E-7 5.63 -1890 [Westmoreland et al. 1989] 4.47E11 0.0 30010 [Chanmugathas and Heicklen 1986] 3.23E07 2.095 15842 [ag] 2.00E13 0.0 14704 [Leidreiter and Wagner 1989] 2.40E13 0.0 4668 [Ko et al. 1991b] 2.11E13 0.0 4571 [Madronich and Felder 1985] 6.30E13 0.0 60000 [Emdee et al. 1992] 6.00E12 0.0 12320 [Tokmakov et al. 1999] 7.59E13 0.0 73853 [Melius et al. 1992] 3.00E12 0.5 2000 [Marinov et al. 1997] 1.59E19 -1.82 12800 [QRRK, 20 torr]ah 3.00E12 1.90E12 0.0 0.0 1,3-cyclohexadiene (C6H813), 1,4-cyclohexadiene (C6H814) and hexadienyl 653. CH2CHCHCH + C2H2 = C6H7 654. CH3 + C5H5 = C6H7 + H 655. C6H7 + H = C6H6 + H2 656. C6H7 + C6H5 = 2C6H6 657. C6H7 + H = C6H813 658. C6H7 + H = C6H814 659. 2C6H7 = C6H813 + C6H6 660. 2C6H7 = C6H814 + C6H6 661. C6H813 + O2 = C6H7 + HO2 662. C6H814 + H = C6H7 + H2 663. C6H813 = C6H6 + H2 664. C6H814 = C6H6 + H2 665. C2H3 + CH2CHCHCH = C6H813 1.96E19 2.44E41 1.00E13 1.00E12 6.00E13 6.00E13 1.94E15 1.67E15 8.13E11 2.80E13 4.70E13 1.05E12 5.50E15 -3.35 -7.989 0.0 0.0 0.0 0.0 -1.0 -1.0 0.0 0.0 0.0 0.0 -1.67 5240 39259 0 0 0 0 0 0 24840 2259 61600 42690 1470 [Westmoreland et al. 1989] [Dean 1990] [Louw and Lucas 1973] [Louw and Lucas 1973] [Berho et al. 1999]ai [Berho et al. 1999]ai [aj] [aj] [Mulder and Louw 1985] [rxn. 590.] [Orchard and Thrush 1974] [Ellis and Frey 1966] [Westmoreland et al. 1989] This journal is © The Owner Societies 2002 666. C4H613 + C2H2 = C6H814 2.30E12 0.0 35000 [Westmoreland et al. 1989] Phenoxy (C6H5O) reactions 667. C6H5O+H=C6H5OH 668. C6H5O=C5H5+CO 669. C6H5+OH=C6H5O+H 670. C6H5O+O=C5H5+CO2 4.43E60 -13.232 30010 [QRRK, 20 torr]f, ak 2.51E11 0.0 43900 [Lin and Lin 1986] 5.00E13 0.0 0 [Miller and Melius 1992] 1.00E13 0.0 0 [Alzueta et al. 2000] Phenol (C6H5OH) and hydoxyphenyl (C6H4OH) reactions 671. C6H5OH = C5H6 + CO 1.00E12 672. C6H5OH + H = C6H5O + H2 1.15E14 673. C6H5OH + O = C6H5O + OH 2.81E13 674. C6H5OH + HO2= C6H5O + H2O2 3.00E13 675. C6H5OH + C2H3 = C2H4 + C6H5O 6.00E12 676. C6H5OH + CH2CHCHCH = C4H613 + C6H5O 6.00E12 677. C6H5OH + CH2CHCCH2= C4H613 + C6H5O 6.00E12 678. C6H5OH + C6H5=C6H6+C6H5O 4.91E12 679. C6H5O + C5H6 = C5H5 + C6H5OH 3.16E11 680. C6H5OH + OH = H2O + C6H5O 1.39E08 681. C6H5OH + OH = H2O + C6H4OH 1.41E13 682. C6H5OH + H = H2 + C6H4OH 1.67E14 683. C5H5 + CO = C6H4OH 3.77E42 0.0 60802 [Horn et al. 1998] 0.0 12400 [Emdee et al. 1992] 0.0 7352 [Emdee et al. 1992] 0.0 15000 [Bittker 1991] 0.0 0 [Emdee et al. 1992] 0.0 0 [Emdee et al. 1992] 0.0 0 [Emdee et al. 1992] 0.0 4400 [Emdee et al. 1992] 0.0 8000 [Emdee et al. 1992] 1.43 -962 [Shandross et al. 1996b] 0.0 4571 [Shandross et al. 1996b] 0.0 16000 [Shandross et al. 1996b] -9.865 73120 [QRRK, 20 torr]f ortho- and para-benzoquinones (OC6H4O2 and PC6H4O2) reactions 684. C6H5 + O2 = OC6H4O2 + H 685. C6H5O + O = OC6H4O2 + H 686. C6H5O + O = PC6H4O2 + H 687. OC6H4O2 = C5H4O + CO 688. PC6H4O2 = C5H4O + CO 689. PC6H4O2 = C5H4 + CO2 690. PC6H4O2 + H = C5H5O + CO 691. PC6H4O2 + H = C6H3O2 + H2 692. PC6H4O2 + O = C6H3O3 + H 693. PC6H4O2 + O = C6H3O2 + OH 694. PC6H4O2 + OH = C6H3O2 + H2O 695. C6H3O2 + H = PC6H4O2 696. C6H3O2 + H = 2C2H2 + 2CO 697. C6H3O2 + O = C2H2 + HCCO + 2CO 698. C6H3O3 = C2H2 + HCCO + 2CO 699. C6H3O3 + H= C2H2 + CH2CO + 2CO 3.00E13 8.50E13 8.50E13 1.00E12 3.70E11 3.50E12 2.50E13 2.00E12 1.50E13 1.40E13 1.00E06 1.00E14 1.00E14 1.00E14 1.00E12 1.00E14 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.0 0.0 0.0 0.0 0.0 0.0 9000 [Alzueta et al. 2000] 0 [Alzueta et al. 2000] 0 [Alzueta et al. 2000] 40000 [Alzueta et al. 2000] 59000 [Alzueta et al. 2000] 67000 [Alzueta et al. 2000] 4700 [Alzueta et al. 2000] 8100 [Alzueta et al. 2000] 4530 [Alzueta et al. 2000] 14700 [Alzueta et al. 2000] 4000 [Alzueta et al. 2000] 0 [Alzueta et al. 2000] 0 [Alzueta et al. 1998] 0 [Alzueta et al. 1998] 50000 [Alzueta et al. 1998] 0 [Alzueta et al. 2000] Benzyl (C7H7, C6H5CH2) reactions 700. C6H5 + CH3 = C7H7 + H 701. C4H4 + H2CCCH = C7H7 702. C7H7 + C6H5OH = C7H8 + C6H5O 703. C7H7 + HO2 = C6H5 + CH2O + OH 4.44E33 -5.45 24290 5.39E51 -12.20 7120 1.05E11 0.0 9500 5.00E12 0.0 0 [QRRK 20 torr]al [QRRK, 20 torr]f [Emdee et al. 1992] [Hippler et al. 1990] This journal is © The Owner Societies 2002 Toluene (C7H8, C6H5CH3) reactions 704. C7H7 + H = C7H8 705. C6H5 + CH3 = C7H8 706. C7H8 + O2 = C7H7 + HO2 707. C7H8 + OH = C7H7 + H2O 708. C7H8 + H = C7H7 + H2 709. C7H8 + H = C6H6 + CH3 710. C7H8 + CH3 = C7H7 + CH4 711. C7H8 + C6H5 = C7H7 + C6H6 712. C7H8 + C2H3 = C7H7 + C2H4 713. CH2CHCHCH + C3H4 = C7H8 + H 714. CH2CHCHCH + C3H4P = C7H8 + H 2.59E14 0.0 0 [Baulch et al. 1994] 1.07E65 -15.64 22720 [QRRK, 20 torr]al 3.00E14 0.0 41400 [Emdee et al. 1992] 1.26E13 0.0 2583 [Emdee et al. 1992] 1.20E14 0.0 8235 [Emdee et al. 1992] 1.20E13 0.0 5148 [Emdee et al. 1992] 3.16E11 0.0 9500 [Emdee et al. 1992] 2.10E12 0.0 4400 [Emdee et al. 1992] 3.98E12 0.0 8000 [Zhang and McKinnon 1995] 2.00E11 0.0 3700 [Kern et al. 1988] 3.16E11 0.0 3700 [Cole et al. 1984] HYDROXYTOLUENE (C7H8O) 715. C6H5O + CH3 = C7H8O 716. C7H8O + H = C7H8 + OH 717. C7H8O + H = C6H5OH + CH3 1.00E12 2.21E13 1.20E13 0.0 0.0 0.0 0 [Lin and Lin 1986] 7910 [Emdee et al. 1992] 5148 [Emdee et al. 1992] 1.58E13 3.98E15 6.03E12 7.83E12 3.98E14 0.0 0.0 0.0 0.0 0.0 0 83660 1810 0 29410 2.00E13 0.0 0 [Hippler et al. 1990] 1.21E13 1.21E13 0.0 0.0 0 [rxn. 277.] 0 [rxn. 277.] 1.21E13 0.0 0 [rxn. 277.] Benzaldehyde (C6H5CHO) and benzoyl (C6H5CO) 718. C7H7 + O = C6H5CHO + H 719. C6H5CHO = C6H5CO + H 720. C6H5CHO + O = C6H5CO + OH 721. C6H5CHO + OH=C6H5CO + H2O 722. C6H5CO = C6H5 + CO [Brezinsky et al. 1984] [Grela and Colussi 1986] [Baulch et al. 1994] [Baulch et al. 1994]am [Solly and Benson 1971] Benzylalcohol (C6H5CH2OH) 723. C7H7 + OH = C6H5CH2OH Methylphenylether (C6H5OCH3) 724. C6H5O + CH3 = C6H5OCH3 725. C6H5 + CH3O = C6H5OCH3 Biphenylether (C6H5OC6H5) 726. C6H5+C6H5O=C6H5OC6H5 Phenylacetylene (C8H6, C6H5C2H) and triplet phenylcarbene (C6H5CH) 727. C6H6 + C2H = C8H6 + H 728. C6H5 + C2H2 = C8H6 + H 729. C8H6 + H = A1C2H*2 + H2 730. C8H6 + OH = A1C2H*2 + H2O 731. C8H6 + CH3 = A1C2H*2 + CH4 732. A1C2H*2 + H = C8H6 733. C6H5 + C2H = C8H6 734. C6H5+C4H4 = C8H6 + C2H3 735. CH2CHCHCH + C4H2 = C8H6 + H 736. HCCHCCH + C4H2 = A1C2H*2 1.00E12 0.0 0 [Colket 1986] 8.32E22 -2.68 17400 [Richter et al. 2001]an 3.23E07 2.095 15842 [rxn. 644.] 2.11E13 0.0 4571 [rxn. 647.] 1.67E12 0.0 15057 [Marinov et al. 1996] 8.02E19 -2.011 1968 [rxn. 633.] 2.54E17 -1.489 1541 [Zhang and McKinnon 1995] 3.20E11 0.0 1350 [Harris et al. 1988] 3.16E11 0.0 1800 [Cole et al. 1984] 3.33E24 -3.89 9210 [rxn. 627.] This journal is © The Owner Societies 2002 8.56E44 -10.50 13220 [Richter et al. 2001]an 1.21E14 0.0 0 [QRRK, 20 torr]ao 2.74E22 -4.061 37040 [rxn. 213.] 3.60E12 0.0 633 [Eichholtz et al. 1994] 1.00E13 0.0 0 [estimate, present work] 6.03E13 0.0 15103 [rxn. 95.] 1.00E13 0.0 0 [estimate, present work] 1.00E13 0.0 0 [estimate, present work] 737. C6H5 + C2H2 = C6H5CHCH 738. C6H5CHCH + H = C8H6 + H2 739. C6H5CHCH = C8H6 + H 740. C8H6 + O = C6H5CH + CO 741. C6H5CH + H = C7H7 742. C7H7 + H = C6H5CH + H2 743. C6H5CH + O = C6H6 + CO 744. C6H5CH + OH = C6H6 + HCO Styrene (C8H8, C6H5C2H3) reactions 745. C6H5 + C2H3 = C8H8 746. C6H5CHCH + H = C8H8 747. C6H5 + C4H4 = C8H8 + C2H 748. C6H5 + C4H613 = C8H8 + C2H3 749. C4H4 + C4H4 = C8H8 750. CH2CHCHCH + C4H4 = C8H8 + H 751. C8H8 = C6H6 + C2H2 752. C6H5 + C2H4 = C8H8 + H 753. C8H8 + H = C6H5CHCH + H2 754. C8H8 + OH = C6H5CHCH + H2O 755. C6H6 + C2H3 = C8H8 + H 756. C6H5 + C2H2 = C8H7*2 757. C8H7*2 + H = C8H8 1.75E49 -10.314 24270 [QRRK, 20 torr]f 4.80E10 -0.74 -7630 [QRRK, 20 torr]ao 3.20E11 0.0 1900 [Harris et al. 1988] 3.20E11 0.0 1900 [Harris et al. 1988] 1.50E14 0.0 38000 [Lundgard and Heicklen 1984] 3.16E11 0.0 600 [Cole et al. 1984] 1.58E11 0.0 58440 [Müller-Markgraf and Troe 1988] 2.51E12 0.0 6200 [Fahr and Stein 1988] 5.07E07 1.93 12951 [rxn. 232.] 2.02E13 0.0 5955 [rxn. 244.] 7.94E11 0.0 6400 [Fahr and Stein 1988] 7.90E51 -12.41 17770 [Richter et al. 2001]an 8.02E19 -2.011 1968 [rxn. 633.] Phenylethane (C8H10, C6H5C2H5) reactions 758. C7H7 + CH3 = C8H10 759. C8H10 + H = C6H6 + C2H5 760. C8H10 + OH = C8H8 + H2O + H 761. C8H10 + H = C8H8 + H2 + H 762. C8H10 + O2 = C8H8 + HO2 + H 763. C8H10 = C8H8 + H2 1.19E13 1.20E13 8.34E12 8.00E13 2.00E14 5.01E12 0.0 0.0 0.0 0.0 0.0 0.0 221 5100 2583 8235 41400 64000 [Brand et al. 1990] [Zhang and McKinnon 1995] [Emdee et al. 1992] [Emdee et al. 1992] [Emdee et al. 1992] [Clark and Price 1970] Biphenyl (C12H10) reaction 764. C6H5 + C6H5 = C12H10 765. C6H5 + C6H6 = C12H10 + H 766. C12H10 + H = C12H9 + H2 767. C12H10 + OH = C12H9 + H2O 768. C6H5 + H2CCCH = C6H5C3H2 + H 769. C6H5C3H2 + H2CCCH = C12H9 + H 770. C12H9 + H = C12H10 5.94E42 -8.83 1.90E76 -18.90 3.23E07 2.095 2.11E13 0.0 3.00E12 0.0 3.00E12 0.0 1.17E33 -5.57 13830 [QRRK, 20 torr]ap 39470 [Park et al. 1999]aq 15842 [rxn. 644.] 4571 [rxn. 647.] 0 [D’Anna and Violi 1998] 0 [D’Anna and Violi 1998] 8760 [QRRK, 20 torr]ar Naphthalene (C10H8), 1-napththyl (C10H7*1), 2-naphthyl (C10H7*2), 1-naphthyne (A2T1, C10H6) and 2-naphthyne (A2T2, C10H6) 771. 2C5H5 = C10H8 + 2H 5.00E12 0.0 8000 [as] 772. C6H5 + HCCHCCH = C10H8 1.51E75 -17.845 39600 [QRRK, 20 torr]f 773. C7H7 + H2CCCH = C10H8 + H + H 3.00E12 0.0 0 [D’Anna and Violi 1998] This journal is © The Owner Societies 2002 774. A1C2H*2 + C2H2 = C10H7*1 775. C6H5 + HCCHCCH = C10H7*2 + H 776. C10H8 + H = C10H7*1 + H2 777. C10H8 + H = C10H7*2 + H2 778. C10H8 + OH = C10H7*1 + H2O 779. C10H8 + OH = C10H7*2 + H2O 780. C10H8 + CH3 = C10H7*1 + CH4 781. C10H8 + CH3 = C10H7*2 + CH4 782. C10H7*1 + H = C10H8 783. C10H7*1 + H = A2T1 + H2 784. C10H7*2 + H = C10H8 785. C10H7*2 + H = A2T2 + H2 4.67E06 1.787 1.84E72 -16.129 3.23E07 2.095 3.23E07 2.095 2.11E13 0.0 2.11E13 0.0 2.00E12 0.0 2.00E12 0.0 8.02E19 -2.011 4.40E-13 7.831 8.02E19 -2.011 4.40E-13 7.831 3262 [at] 57630 [QRRK, 20 torr]f 15842 [rxn. 644.] 15842 [rxn. 644.] 4571 [rxn. 647.] 4571 [rxn. 647.] 15060 [au] 15060 [au] 1968 [rxn. 633.] 9261 [rxn. 634.] 1968 [rxn. 633.] 9261 [rxn. 634.] Formation of A21C6H4 (C10H6C6H4) and A22C6H4 (C10H6C6H4) 786. A2T1 + BENZYNE = A21C6H4 787. A2T2 + BENZYNE = A22C6H4 4.58E41 -8.73 4.58E41 -8.73 12740 [QRRK, 20 torr]av 12740 [QRRK, 20 torr]av Indene (INDENE, C9H8), 1-indenyl (INDENE*, C9H7), 1-,2-napthoxy (C10H7O-1, C10H7O-2) and 1,2-naphthol (C10H7OH-1, C10H7OH-2) 788. C10H7*1 + O2 = C10H7O-1 + O 2.39E21 -2.62 789. C10H7*1 + OH = C10H7O-1 + H 5.00E13 0.0 790. C10H7*2 + O2 = C10H7O-2 + O 2.39E21 -2.62 791. C10H7*2 + OH = C10H7O-2 + H 5.00E13 0.0 792. C10H7O-1 + H = C10H7OH-1 4.43E60 -13.232 793. C10H7OH-1 + H = C10H7O-1 + H2 1.15E14 0.0 794. C10H8 + OH = C10H7OH-1 + H 1.59E19 -1.82 795. C10H7OH-1 + OH = C10H7O-1 + H2O 1.39E08 1.43 796. C10H7O-2 + H = C10H7OH-2 4.43E60 -13.232 797. C10H7OH-2 + H = C10H7O-2 + H2 1.15E14 0.0 798. C10H8 + OH = C10H7OH-2 + H 1.59E19 -1.82 799. C10H7OH-2 + OH = C10H7O-2 + H2O 1.39E08 1.43 800. C10H7O-1 = INDENE* + CO 2.51E11 0.0 801. C10H7O-2 = INDENE* + CO 2.51E11 0.0 802. INDENE + H = INDENE* + H2 1.48E14 0.0 803. INDENE + OH = INDENE* + H2O 1.57E07 1.83 804. INDENE + O = INDENE* + OH 6.92E08 1.56 805. INDENE* + H = INDENE 2.00E14 0.0 806. C7H7 + C2H2 = INDENE + H 3.20E11 0.0 807. INDENE* + O = C6H5CHCH + CO 1.00E14 0.0 4400 [rxn. 628.] 0 [rxn. 669.] 4400 [rxn. 628.] 0 [rxn. 669.] 30010 [rxn. 667.] 12400 [rxn. 672.] 12800 [rxn. 652.] -962 [rxn. 680.] 30010 [rxn. 667.] 12400 [rx. 672.] 12800 [rxn. 652.] -962 [rxn. 680.] 43900 [rxn. 668.] 43900 [rxn. 668.] 13585 [rxn. 146.] 2780 [rxn. 147.] 8490 [rxn. 148.] 0 [Marinov et al. 1996] 7000 [Marinov et al. 1996] 0 [Marinov et al. 1996] 1-, 2-Methylnapththalene (A2CH3-1, A2CH3-2) and their radicals (A2CH2-1, A2CH2-2) 808. C10H7*1 + CH3 = A2CH2-1 + H 809. C10H7*2 + CH3 = A2CH2-2 + H 810. C10H7*1 + CH3 = A2CH3-1 811. C10H7*2 + CH3 = A2CH3-2 812. A2CH2-1 + H = A2CH3-1 813. A2CH2-2 + H = A2CH3-2 814. A2CH3-1 + H = C10H8 + CH3 1.70E36 -5.91 34630 [QRRK, 20 torr]aw 1.70E36 -5.91 34630 [QRRK, 20 torr]aw 3.05E52 -11.80 17660 [QRRK, 20 torr]aw 3.05E52 -11.80 17660 [QRRK, 20 torr]aw 1.00E14 0.0 0 [Marinov et al. 1996] 1.00E14 0.0 0 [Marinov et al. 1996] 1.20E13 0.0 5148 [Marinov et al. 1996] This journal is © The Owner Societies 2002 815. A2CH3-2 + H = C10H8 + CH3 1.20E13 0.0 5148 [Marinov et al. 1996] 1--naphthylacetylene (A2C2H-1, C10H7C2H) and 2-naphthylacetylene (A2C2H-2, C10H7C2H) 816. C10H7*1 + C2H2 = A2C2H-1 + H 817. C10H7*2 + C2H2 = A2C2H-2 + H 818. A2VINP + H = A2C2H-2 + H2 9.60E-9 6.44 1.01E26 -3.44 1.21E14 0.0 8620 [Richter et al. 2001]an 20230 [QRRK, 20 torr]ax 0 [rxn. 738.] 2-vinylnaphthalene (A2C2H3-2, C10H7C2H3) and its radical (A2VINP, C10H7CHCH) 819. C10H7*2 + C2H4 = A2C2H3-2 + H 820. C10H8 + C2H3 = A2C2H3-2 + H 821. C10H7*2 + C2H2 = A2VINP 822. A2VINP = A2C2H-2 + H 823. A2VINP + H = A2C2H3-2 2.51E12 0.0 6200 [rxn. 752.] 7.94E11 0.0 6399 [rxn. 755.] 2.77E46 -10.90 14210 [QRRK, 20 torr]ax 2.74E22 -4.061 37040 [rxn. 213.] 4.80E10 -0.74 -7630 [rxn. 746.] Biphenylene (BIPHEN, C6H4C6H4) and acenapthylene (A2R5, C12H8) 824. BENZYNE + BENZYNE = BIPHEN 825. BIPHENH = BIPHEN + H 826. BIPHENH + H = BIPHEN + H2 827. BIPHENH = A2R5 + H 828. C10H7*1 + C2H2 = A2R5 + H 4.60E12 1.30E16 6.02E12 1.00E13 3.57E24 0.0 0 [Porter and Steinfeld 1968] 0.0 33203 [ay] 0.0 0 [az] 0.0 20000 [Richter et al. 2000]ba -3.176 14861 [Richter et al. 2001]an Acenaphthene (A2R5H2, C12H10) and 1-acenaphthenyl (HA2R5, C12H9) 829. C10H7*1 + C2H4 = A2R5H2 + H 830. C10H7*1 + C2H2 = HA2R5 831. HA2R5 + H = A2R5 + H2 832. HA2R5 + OH = A2R5 + H2O 833. HA2R5 + H = A2R5H2 834. A2R5H2 + H = HA2R5+H2 835. A2R5H2 + OH = HA2R5 + H2O 836. A2R5H2 = A2R5 + H2 2.51E12 0.0 6200 7.74E45 -10.85 13470 1.81E12 0.0 0 2.41E13 0.0 0 1.00E14 0.0 0 5.40E02 3.5 5210 8.70E09 1.05 1810 4.70E13 0.0 61600 [rxn. 752.] [Richter et al. 2001]an [rxn. 257.] [rxn. 260.] [bb] [rxn. 265.] [rxn. 267.] [Orchard and Thrush 1973] Phenanthrene (A3, C14H10) 837. C12H9 + C2H2 = A3 + H 838. INDENE* + C5H5 = A3 + 2H 1.87E07 5.00E12 HACA Pathway 839. A2C2H-2 + H = A2C2H-2*1 + H2 3.23E07 840. A2C2H-2 + OH = A2C2H-2*1 + H2O 2.11E13 841. A2C2H-2*1 + C2H2 = A3*1 4.67E06 842. A2C2H-1 + H = A2C2H-1*2 + H2 3.23E07 843. A2C2H-1 + OH = A2C2H-1*2 + H2O 2.11E13 844. A2C2H-1*2 + C2H2= A3*4 4.67E06 1.787 0.0 3262 [bc] 8000 [rxn. 771.]bd 2.095 15842 [ag] 0.0 4571 [rxn. 647.] 1.787 3262 [at] 2.095 15842 [ag] 0.0 4571 [rxn. 647.] 1.787 3262 [at] Ring-Ring Condensation (Appel et al. 2000) 845. C8H6 + C6H5 = A3 + H 9.55E11 0.0 4308 [be] 846. A1C2H*2 + C6H6 = A3 + H 9.55E11 0.0 4308 [be] This journal is © The Owner Societies 2002 847. A3 + H = A3*1 + H2 848. A3 + H = A3*2 + H2 849. A3 + H = A3*4 + H2 850. A3 + H = A3*9 + H2 851. A3 + OH = A3*1 + H2O 852. A3 + OH = A3*2 + H2O 853. A3 + OH = A3*4 + H2O 854. A3 + OH = A3*9 + H2O 855. A3*1 + H = A3 856. A3*2 + H = A3 857. A3*4 + H = A3 858. A3*9 + H = A3 3.23E07 3.23E07 3.23E07 3.23E07 2.11E13 2.11E13 2.11E13 2.11E13 2.15E19 2.15E19 2.15E19 2.15E19 2.095 2.095 2.095 2.095 0.0 0.0 0.0 0.0 -1.55 -1.55 -1.55 -1.55 15842 15842 15842 15842 4571 4571 4571 4571 1700 1700 1700 1700 [ag] [ag] [ag] [ag] [rxn. 647.] [rxn. 647.] [rxn. 647.] [rxn. 647.] [ar] [ar] [ar] [ar] Anthracene (A3L, C14H10) 859. A2C2H-2 + H = A2C2H-2*3 + H2 860. A2C2H-2 + OH = A2C2H-2*3 + H2O 861. A2C2H-2*3 + C2H2 = A3L*1 862. C10H7*2 + C4H2 = A3L*2 863. A3L + H = A3L*1 + H2 864. A3L + OH = A3L*1 + H2O 865. A3L*1 + H = A3L 866. A3L + H = A3L*2 + H2 867. A3L + OH = A3L*2 + H2O 868. A3L*2 + H = A3L 869. A3L + H = A3L*9 + H2 870. A3L + OH = A3L*9 + H2O 871. A3L*9 + H = A3L 872. A3L = A3 3.23E07 2.095 2.11E13 0.0 4.67E06 1.787 4.67E06 1.787 3.23E07 2.095 2.11E13 0.0 2.15E19 -1.55 3.23E07 2.095 2.11E13 0.0 2.15E19 -1.55 3.23E07 2.095 2.11E13 0.0 2.15E19 -1.55 7.94E12 0.0 15842 [ag] 4571 [rxn. 647.] 3262 [at] 3262 [at] 15842 [ag] 4571 [rxn. 647.] 1700 [ar] 15842 [ag] 4571 [rxn. 647.] 1700 [ar] 15842 [ag] 4571 [rxn. 647.] 1700 [ar] 65000 [Colket and Seery 1994] Footnotes a determined by Shandross (1996a) based on Baulch et al. (1992). b QRRK computation using the modified strong collision approach (Chang et al. 2000). Software was provided by J. W. Bozzelli (New Jersey Institute of Technology). The rate constant for the entrance channel (CH+H2) was taken from Brownsword (1997) while hydrogen loss from the initial adduct (CH3 3CH2 + H) was described by means of the rate constant determined by Su and Teitelbaum (1994). c low pressure limit. d Total rate constant taken from Lim and Michael (1993), product channels and branching ratios from Marcy et al. (2001). e rate constants given for 20 torr. f QRRK computation (Dean et al. 1991) based on input parameter of Shandross (1995a). This journal is © The Owner Societies 2002 g QRRK computation (Chang et al. 2000). Use of rate constant suggested by Tsang and Hampson (1986) for high pressure limit of entrance channel. The rate constant of reverse reaction was determined by means of equilibrium constant. No additional product channels were taken into account. h Use of branching ratio determined by Knyazev et al. (1992) in combination with total rate constant recommended by Tsang (1991). i Branching factor suggested by Koda et al. (1991) in conjuction with total rate 1-butene + O rate constant measured by Ko et al. (1991a). j Measured by Hassinen et al. (1990) in respect to acetone formation (rxn. 292.). Combination of relative rate constant with recommendation of Tsang and Hampson (1986) for CH3CO + CH3 CH3COCH3. k Total rate constant of CH3CO + H reactions. Depending on temperature and pressure, also CH3CHO (high pressure) and CH2CO + H (high temperature) might be formed. See discussion in Bartels et al. (1990). l QRRK computation (Chang et al. 2000). Use of rate constant reported by Böhland et al. (1986) for entrance channel forming chemically activated cyclopropene. Description of isomerization to allene and propyne by means of rate constants determined by Karni et al. (1988) while rate constants deduced by Scherer et al. (2000) were used for hydrogen loss from allene and propyne to propargyl. m rate constant suggested by Durán et al. (1988) for C2H3 + H C2H4. n determined by Cadman et al. (1970) for C2H5CO C2H5 + CO. o Total rate constant attributed to dominant product channel. p rate constant includes all product channels. An upper limit for the formation of C2H5CO + H2O of 1.57 1013 cm3 mole-1 s-1 at 302 K was deduced by Kerr and Stocker (1985). measured by McAdam and Walker (1987) relative to C2H5 + O2 C2H4 + HO2. Absolute rate constant determined in conjunction with recommendation of Tsang and Hampson (1986) for the latter reaction. q r QRRK computation (Chang et al. 2000). Use of rate constant determined by Thiesemann et al. (2001) for entrance channel (9.99 1014 T-0.31 cm3 mole-1 s-1). C3H5 allene + H is the only product channel and was described by means of the rate constant determined by Tsang and Walker (1992), i.e., 1.50 1011 T0.84 exp(-59.81 kcal/RT) s-1. s no signifcant pressure dependence of propyne and allenyl formation via CH3 + C2H2. t QRRK computation (Dean et al. 1991). Input parameter taken from Shandross et al. (1996). Rate constants of entrance channel to chemically activated n-C4H3 (9.64 1013 cm3 mole-1 s-1) and hydrogen loss to 1,3-butadiyne (1.14 1014 exp(-40.13 kcal/RT) s-1) are in close agreement with literature data. Van Look and Peters (1995) measured C2H2 + C2H products to be 7.83 (1.2) 1013 cm3 mole-1 s-1 while Weissman and Benson (1984) suggested 1.0 1014 exp(-40.74 kcal/RT) s-1 for hydrogen loss from n-C4H3. u QRRK computation (Chang et al. 2000). Rate constants for formation of chemically activated C4H4 and subsequent 1,1-elimination of H2 were taken from Kiefer et al. (1988). Direct formation of 1,3butadiyne was not included in the present model. However, its contribution might be significant under certain conditions and should be considered in future work. This journal is © The Owner Societies 2002 v QRRK computation (Chang et al. 2000). Rate constant for entrance channel taken from Miller et al. (2000b). C4H4 + H is only product (besides stabilization), rate constant for hydrogen loss from n-C4H5 was taken from Colket et al. (1989). w QRRK computation (Dean et al. 1991). Rate constant for formation of chemically activated vinylacetylene (1.0 1014 cm3 mole-1 s-1) taken from Duran et al. (1988). No product channels besides stabilization. x Deduced by Fahr et al. (1991) for C2H3 + H C2H4. y QRRK computation (Chang et al. 2000). Rate constant for entrance channel taken from Fahr and Stein (1988). The rate constant describing hydrogen loss from C4H7 to 1,3-butadiene suggested by Weissman and Benson (1984) was used. z Rate constant determined by Sillesen et al. (1993) for C2H4 + H C2H5. aa Deduced for benzene + CH3 phenyl + CH4 by Zhang et al. (1989). ab QRRK computation (Chang et al. 2000). Input parameter given by Zhong and Bozzelli (1998). ac QRRK computation (Chang et al. 2000). Use of k= 1.38 1013 exp (-46cal/RT) cm3 mole-1 s-1, derived for C6H5 + CH3 C6H5CH3 by Tokmakov et al. (1999). No exit channels besides collisional stabilization. ad Activation energy increased by difference between heats of formation of 2-cylcopentadienyl (C5H4H) and 1-cyclopentadienyl (C5H5), i.e., 32.88 kcal mole-1. ae QRRK computation (Chang et al. 2000). Input parameter given by DiNaro et al. (2000). af Based on the work of Scherer et al. (2000), benzene and not phenyl + H, as assumed by Marinov et al. (1996), was taken as dominant product channel of propargyl self-combination. For details, see text. Deduced via equilibrium constant of benzene + H phenyl + H2 using the rate constant for phenyl + H2 determined by Mebel et al. (1997). ag ah QRRK computation (Chang et al. 2000). Similar to Shandross et al. (1996a/1996b) but use of improved QRRK treatment. Rate constant for entrance channel taken from He et al. (1988). ai The reaction C6H7 + H can lead to the formation of 1,3- as well as 1,4-cyclohexadiene due to the delocalisation of the free electron of cyclohexadienyl. A total rate constant for the formation of both isomers of 1.2 1014 mole cm-3 s-1, independent of temperature, was given by Berho et al. (1999). An equal contribution of both product channels was assumed in the present work. Total rate constant of C6H7 + C6H7 products was determined to be 5.38 1015 T-1.0 cm3 mole-1 s-1 by Berho et al. (1999). Relative contributions of the formation of 1,3-cyclohexadiene (36%) and 1,4cyclohexadiene (31%) were based on James and Suart (1968). aj ak No exit channel besides stabilization. The rate constant k= 2.5 1014 cm3 mole-1 s-1 was used for the formation of chemically activated phenol. This value is in excellent agreement with those suggested by Baulch et al. (1992) and Davis et al. (1996), i.e., 2.53 1014 and 2.5 1014 cm3 mole-1 s-1 at 1000 and from 1000 to 1200 K, respectively. al QRRK computation (Chang et al. 2000). Use of k= 1.38 1013 exp(-46cal/RT) cm3 mole-1 s-1, derived by Tokmakov et al. (1999), for entrance reaction. Hydrogen loss from toluene to benzyl + H was described by k= 3.60 1015 exp(-89.42kcal/RT) s-1, deduced by Braun-Unkhoff et al. (1988). am Products not given by Baulch et al. (1994). an QRRK computation (Chang et al. 2000), 20 torr. This journal is © The Owner Societies 2002 ao QRRK computation (Chang et al. 2000). The rate constant determined by Fahr et al. (1991) for C 2H3 + H (k= 1.21 1014 cm3 mole-1 s-1) was used for the formation of chemically activated C6H5C2H3. The rate constant for phenylacetylene formation by elimination of H2 (C6H5C2H3 C6H5C2H + H2) was estimated to be k= 1.10 1014 exp(-40kcal/RT) s-1. ap QRRK computation (Chang et al. 2000). Use of k= 1.39 1013 exp(-111cal/RT) cm3 mole-1 s-1, determined by Park and Lin (1997) for the formation chemically activated biphenyl. No product channel besides collisional stabilization. aq fit of data provided for 40 torr between 500 and 2500 K. ar QRRK computation (Chang et al. 2000). Description of the formation of the chemically activated recombination product using k= 2.2 1014 cm3 mole-1 s-1, deduced by Ackermann et al. (1990) for C6H5 + H at 300 K/1bar and assumed to be close to the high-pressure limit. Hydrogen abstraction was not taken into account. as based on Marinov et al. (1998). Pre-exponential factor adjusted to the low by a factor of four. at Estimate. High pressure limit determined by O. A. Mazyar for 1-naphthyl + acetylene in Richter et al. (2001) divided by four. au Derived by Zhang et al. (1989) for benzene + CH3 phenyl + CH4. av QRRK computation (Chang et al. 2000). Use of k= 4.6 1012 cm3 mole-1 s-1, the rate constant of benzene dimerization measured by Porter and Steinfeld (1968), for the formation of the chemically activated adduct. Isomerization to acephenanthrylene, aceanthrylene and fluoranthene was included in the QRRK analysis. aw QRRK computation (Chang et al. 2000) for 1-naphthyl + CH3. Use of k= 1.38 1013 exp(-46cal/RT) cm3 mole-1 s-1, derived by Tokmakov et al. (1999) for phenyl + CH3. Hydrogen loss from the chemically activated 1-methylnaphthalene was described using k= 3.60 1015 exp (-89.42kcal/RT) s-1, deduced for toluene by Braun-Unkhoff et al. (1988). ax QRRK computation (Chang et al. 2000). Use of input parameter as described in Richter et al. (2001) for 1-naphthyl + C2H2 but without formation of five-membered ring species. ay suggested by Mebel et al. (1997) for C6H7 benzene + H. az suggested by Mebel et al. (1997) for C6H7 + H benzene + H2. ba estimate. bb deduced by Sillesen et al. (1993) for C2H5 + H C2H6. bc Estimate. High pressure limit determined for 1-naphthyl + acetylene in Richter et al. (2001). bd based on Marinov et al. (1998). Pre-exponential factor adjusted to the low by a factor of two. be The concept of ring-ring condensation was suggested by Appel et al. (2000). The rate constant determined by Park et al. (1999) for the C6H5 + C6H6 reaction and expected to be close to the high pressure limit was used. This journal is © The Owner Societies 2002 References Ackermann, L., Hippler, H., Pagsberg, P., Reihs, C. and Troe, J. Pulse Radiolysis, Flash Photolysis, and Shock Wave Study of the Recombination H + Benzyl Toluene at 300 and 1300-1650 K. J. Phys. Chem. 94, 5247-5251 (1990). Aleksandrov, E. N., Arutyunov, V. S. and Kozlov, S. N. Study of the Reaction of Oxygen Atoms with Allene. Kinet. Catal. 21, 1327 (1980). Alzueta, M. U., Oliva, M. and Glarborg, P. Parabenzoquinone Pyrolysis and Oxidation in a Flow Reactor. Int. J. Chem. Kinet. 30, 683-697 (1998). Alzueta, M. U., Glarborg, P. and Dam-Johansen, K. Experimental and Kinetic Modeling Study of the Oxidation of Benzene. Int. J. Chem. Kinet. 32, 498-522 (2000). Appel, J., Bockhorn, H. and Frenklach, M. Kinetic Modeling of Soot Formation with Detailed Chemistry and Physics: Laminar Premixed Flames of C2 Hydrocarbons. Combust. Flame 121, 122-136 (2000). Atkinson, R., Baulch, D. L., Cox, R. A., Hampson, R. F., Jr., Kerr, J. A., Rossi, M. J. and Troe, J. Evaluated kinetic, photochemical and heterogeneous data for atmospheric chemistry: supplement V, IUPAC subcommittee on gas kinetic data, evaluation for atmospheric chemistry. J. Phys. Chem. Ref. Data 26, 521-1011 (1997). Baggott, J. E., Frey, H. M., Lightfoot, P. D. and Walsh, R. The absorption cross section of the HCO radical at 614.59 nm and the rate constant for HCO+HCO H2CO+CO. Chem. Phys. Lett. 132, 225 (1986). Baker, R. R., Baldwin, R. R. and Walker, R.W. The Use of the H2 + O2 Reaction in Determining the Velocity Constants of Elementary Reactions in Hydrocarbon Oxidation. Proc. Combust. Inst. 13, 291299 (1971). Bartels, M., Edelbüttel-Einhaus, J. and Hoyermann, K. The detection of CH3CO, C2H5, and CH3CHO by REMPI/mass spectrometry and the application to the study of the reactions H + CH3CO and O + CH3CO. Proc. Combust. Inst. 23, 131-138 (1990). Batt, L., Alvarado-Salinas, G., Reid, I. A. B., Robinson, C. and Smith, D. B. The Pyrolysis of Dimethyl Ether and Formaldehyde. Proc. Combust. Inst. 19, 81-87 (1982). Baulch, D. L., Drysdale, D D., Horne, D. G. and Lloyd, A. C. Evaluated Kinetic Data for High Temperature Reactions. Volume 1 Homogeneous Gas Phase Reactions of the H2-O2 System. Butterworth & Co, London, 1972. Baulch, D. L., Cobos, C. J., Cox, R. A., Esser, C., Frank, P., Just, Th., Kerr, J. A., Pilling, M. J., Troe, J., Walker, R. W., Warnatz, J. Evaluated kinetic data for combustion modelling. J. Phys. Chem. Ref. Data 21, 411 – 734 (1992). Baulch, D. L., Cobos, C. J., Cox, R. A., Frank, P., Hayman, G., Just, Th., Kerr, J. A., Murrells, T., Pilling, M. J., Troe, J., Walker, R. W. and Warnatz, J. Evaluated kinetic data for combusion modelling. Supplement I. J. Phys. Chem. Ref. Data 23, 847-1033 (1994). Benson, S. W. The mechanism of the reversible reaction: 2C2H2 = vinyl acetylene and the pyrolysis of butadiene. Int. J. Chem. Kinet. 21, 233 (1989). Berho, F., Rayez, M.-T. and Lesclaux, R. UV Absorption Spectrum and Self-Reaction Kinetics of the Cyclohexadienyl Radical, and Stability of a Series of Cyclohexadienyl-Type Radicals. J. Phys. Chem. A 103, 5501-5509 (1999). Bittker, D. A. Detailed Mechanism for Oxidation of Benzene. Combust. Sci. and Tech. 79, 49-72 (1991). Böhland, T., Temps, F., and Wagner, H. Gg. Kinetics of the Reactions of CH2 (X 3B1)-Radicals with C2H2 and C4H2 in the Temperature Range 296 K T 700 K. Proc. Combust. Inst. 21, 841-850 (1986). This journal is © The Owner Societies 2002 Bozzelli, J. W. and Dean, A. M. Chemical Activation Analysis of the Reaction of C2H5 with O2. J. Phys. Chem. 94, 3313-3317 (1990). Brand, U., Hippler, H., Lindemann, L. and Troe, J. C-C and C-H bond splits of laser-excited aromatic molecules. 1. Specific and thermally averaged rate constants. J. Phys. Chem. 94, 6305-6316 (1990). Braun-Unkhoff. M., Frank, P. and Just, Th. A Shock Tube Study on the Thermal Decomposition of Toluene and of the Phenyl Radical at High Temperatures. Proc. Combust. Inst. 22, 1053-1061 (1988). Brezinsky, K., Litzinger, T. A. and Glassman, I. The high temperature oxidation of the methyl side chain of toluene. Int. J. Chem. Kinet. 16, 1053 (1984). Brownsword, R. A., Canosa, A., Rowe, B. R., Sims, I. R., Stewart, D. W. A., Symonds, A. C. and Travers, D. Kinetics over a wide range of temperature (13-744 K); Rate constants for the reactions of CH(=0) with H2 and D2 and for the removal of CH(=1) by H2 and D2. J. Chem. Phys. 106, 76627677 (1997). Cadman, P., Dodwell, C., Trotman-Dickenson, A. F. and White, A. J. The kinetics of hydrogen abstraction by difluoroamino-radicals, from propionaldehyde, and n- and iso-butyraldehyde, and their acyl radical decompositions. J. Chem. Soc. A, 2371 (1970). Chang, A. Y., Bozzelli, J. W. and Dean, A. M. Kinetic Analysis of Complex Chemical Activation and Unimolecular Dissociation Reactions Using QRRK Theory and the Modified Strong Collision Approximation. Z. Phys. Chem. 214, 1533-1568 (2000). Chanmugathas, C. and Heicklen, J. Pyrolysis of Acetylene-Vinylacetylene Mixtures between 400 and 500 C. Int. J. Chem. Kinet. 18, 701-718 (1986). Clark, W. D. and Price, S. J. Free-radical and molecular processes in the pyrolysis of ethylbenzene. Can. J. Chem. 48, 1059 (1970). Cohen, N. Are reaction rate coefficients additive? Revised transition state theory calculations for OH + alkane reactions. Int. J. Chem. Kinet. 23, 397-417 (1991). Cole, J. A., Bittner, J. D., Longwell, J. P. and Howard, J. B. Formation Mechanisms of Aromatic Compounds in Aliphatic Flames. Combust. Flame 56, 51-70 (1984). Colket, M. B., Naegeli, D. W. and Glassman, I. High-Temperature Pyrolysis of Acetaldehyde. Int. J. Chem. Kinet. 7, 223 (1975). Colket, M. B. The Pyrolysis of Acetylene and Vinylacetylene in a Single-Pulse Shock Tube. Proc. Combust. Inst. 21, 851-864 (1986). Colket, M. B., Seery, D. J. and Palmer, H. B. The pyrolysis of acetylene initiated by acetone. Combust. Flame 75, 343-366 (1989). Colket, M. B. and Seery, D. J. Reaction Mechanisms for Toluene Pyrolysis. Proc. Combust. Inst. 25, 883-891 (1994). Cvetanovic, R. J. Evaluated chemical kinetic data for the reactions of atomic oxygen O(3P) with unsaturated hydrocarbons. J. Phys. Chem. Ref. Data 16, 261–326 (1987). D’Anna, A. and Violi, A. A Kinetic Model for the Formation of Aromatic Hydrocarbons in Premixed Laminar Flames. Proc. Combust. Inst. 27, 425-433 (1998). Davis, S. G.,Wang, H., Brezinsky, K. and Law, C. K. Laminar flame speeds and oxidation kinetics of benzene-air and toluene-air flames. Proc. Combust. Inst. 26, 1025-1033 (1996). Dean, A. M. and Westmoreland, P. R. Bimolecular QRRK Analysis of Methyl Radical Reactions. Int. J. Chem. Kinet. 19, 207-228 (1987). Dean, A. M. Detailed Kinetic Modeling of Autocatalysis in Methane Pyrolysis. J. Phys. Chem. 94, 1432-1439 (1990). Dean, A. M., Bozzelli, J. W. and Ritter, E. R. CHEMACT: A Computer Code to Estimate Rate Constants for Chemically-Activated Reactions. Combust. Sci. and Tech. 80, 63-85 (1991). Dewar, M. J. S., Gardiner, W. C., Frenklach, M. and Oref, I. Rate Constant for Cyclization/Decyclization of the Phenyl Radical. J. Am. Chem. Soc. 109, 4456-4457 (1987). This journal is © The Owner Societies 2002 Diau, E. W., Lin, M. C. and Melius, C. F. A theoretical study of the CH3+C2H2 reaction. J. Chem. Phys. 101, 3923-3927 (1994). DiNaro, J. L., Howard, J. B., Green, W. H., Tester, J. W., Bozzelli, J. W. Elementary Reaction Mechanism for Benzene Oxidation in Supercritical Water. J. Phys. Chem. A 104, 10576-10586 (2000). Durán, R. P., Amorebieta, V. T. and Colussi, A. J. Is the Homogeneous Thermal Dimerization of Acetylene a Free-Radical Chain Reaction? Kinetic and Thermochemical Analysis. J. Phys. Chem. 92, 636-640 (1988). Eichholtz, M., Schneider, A., Stucken, D.-V., Vollmer, J.-T. and Wagner, H. Gg. The Reactions of Phenylacetylenes with O(3P) in the Gas Phase. Proc. Combust. Inst. 25, 859-866 (1994). Ellis, R. J. and Frey, H. M. The thermal unimolecular isomerisation of bicyclo[3,1,0]hex-2-ene and decomposition of cyclohexa-1,4-diene. J. Chem. Soc. A, 553-556 (1966). Emdee, J. L., Brezinsky, K. and Glassman, I. A Kinetic Model for the Oxidation of Toluene near 1200 K. J. Phys. Chem. 96, 2151-2161 (1992). Fahr, A. and Stein, S. E. Reactions of vinyl and phenyl radicals with ethyne, ethene and benzene. Proc. Combust. Inst. 22, 1023-1029 (1988). Fahr, A., Laufer, A., Klein, R, and Braun, W. Reaction Rate Determinations of Vinyl Radical Reactions with Vinyl, Methyl, and Hydrogen Atoms. J. Phys. Chem. 95, 3218-3224 (1991). Fahr, A., Laufer, A. H. and Tardy, D. C. Pressure Effect on CH3 and C2H3 Cross-Radical Reactions. J. Phys. Chem. A 103, 8433-8439 (1999). Fahr, A. and Nayak, A. Kinetics and Products of Propargyl (C3H3) Radical Self-Reactions and Propargyl-Methyl Cross-Combination Reactions. Int. J. Chem. Kinet. 32, 118-124 (2000). Faubel, C., Hoyermann, K., Ströfer, E. und Wagner, H.Gg. Untersuchungen zur Reaktion von Wasserstoffatomen mit Dimethyläther, Diäthyläther und tert. Butyl-Methyl-äther in der Gasphase. Ber. Bunsenges. Phys. Chem. 83, 532-538 (1979). Frank, P. and Just, Th. High temperature kinetics of ethylene-oxygen reaction. Proc. Int. Symp. Shock Tubes Waves 14, 706 (1984). Frank, P., Herzler, J., Just, Th. and Wahl, C. High-Temperature Reactions of Phenyl Oxidation. Proc. Combust. Inst. 25, 833-840 (1994). Frenklach, M. and Warnatz, J. Detailed Modeling of PAH Profiles in a Sooting Low-Pressure Acetylene Flame. Combustion Sci. and Tech. 51, 265-283 (1987). Grela, M. A. and Colussi, A. J. Kinetics and Mechanism of the Thermal Decomposition of Unsaturated Aldehydes: Benzaldehyde, 2-Butenal, and 2-Furaldehyde. J. Phys. Chem. 90, 434-437 (1986). Harding, L. B. and Klippenstein, S. J. Theoretical Kinetic Estimates for the Recombination of Hydrogen Atoms with Propargyl and Allyl Radicals. Proc. Combust. Inst. 28, 1503-1509 (2000). Harris, S. J., Weiner, A. M., and Blint, R. J. Formation of Small Aromatic Molecules in a Sooting Ethylene Flame. Combust. Flame 72, 91-109 (1988). Hassinen, E., Kalliorinne, K. and Koskikallio, J. Kinetics of reactions between methyl and acetyl radicals in gas phase produced by flash photolysis of acetic anhydride. Int. J. Chem. Kinet. 22, 741 (1990). He, Y. Z., Mallard, W. G. and Tsang, W. Kinetics of hydrogen and hydroxyl radical attack on phenol at high temperatures. J. Phys. Chem. 92, 2196-2201 (1988). Herron, J.T. Evaluated chemical kinetic data for the reactions of atomic oxygen O(3P) with saturated organic compounds in the gas phase. J. Phys. Chem. Ref. Data 17, 967 (1988). Hidaka, Y., Taniguchi, T., Tanaka, H., Kamesawa, T., Inami, K. and Kawano, H. Shock-tube study of CH2O pyrolysis and oxidation. Combust. Flame 92, 365-376 (1993). Hidaka, Y., Higashihara, T., Oki, T. and Kawano, H. Thermal Decomposition of 1-Butyne in Shock Waves. Int. J. Chem. Kinet. 27, 321-330 (1995). Hidaka, Y., Higashihara, T., Oki, T. and Kawano, H. Thermal Decomposition of 1,2-Butadiene in Shock Waves. Int. J. Chem. Kinet. 27, 331-341 (1995). This journal is © The Owner Societies 2002 Hippler, H., Reihs, C. and Troe, J. Shock tube UV absorption study of the oxidation of benzyl radicals. Proc. Combust. Inst. 23, 37-43 (1990). Horn, C., Roy, K., Frank, P. and Just, Th. Shock Tube Study on the High-Temperature Pyrolysis on Phenol. Proc. Combust. Inst. 27, 321-328 (1998). James, D. G. L. and Suart, R.D. Kinetic study of the cyclohexadienyl radical. Part 3.-Mutual interaction and thermal decomposition. Trans. Faraday Soc. 64, 2752 (1968). Karni, M., Oref, I., Barzilai-Gilboa, S., and Lifshitz, A. Isomerization of Cyclopropene to Allene and Propyne at Elevated Temperatures. Experimental, ab Initio, and Model Calculations. J. Phys. Chem. 92, 6924-6929 (1988). Kern, R. D., Singh, H. J. and Wu, C. H. Thermal Decomposition of 1,2-Butadiene. Int. J. Chem. Kinet. 20, 731-747 (1988). Kern,R. D., Xie, K., and Chen, H. The Reactions of Propargyl Chloride and 1,5 Hexadiyne Behind reflected Shock Waves. Preps. Pap. – Am. Chem. Soc. Div. Fuel Chem. 36, 1423-1432 (1991) Kerr, J. A. and Stocker, D. W. The kinetics and mechanism of the photo-oxidation of propionaldehyde under simulated atmospheric conditions. J. Photochem. 28, 475 (1985). Kiefer, J. H., Wei, H. C., Kern, R. D., and Wu, C. H. Int. J. Chem. Kinet. 17, 225 (1985). Kiefer, J. H., Mitchell, K. I., Kern, R. D. and Yong, J. N. Unimolecular dissociation of vinylacetylene: A molecular reaction. J. Phys. Chem. 92, 677-685 (1988). Knyazev, V. D., Arutyunov, V. S. and Dedeneev, V. I. The mechanism of O(3P) atom reaction with ethylene and other simple olefins.Int. J. Chem. Kinet. 24, 545-561 (1992). Knyazev, V. D., Bencsura, Á., Stoliarov, S. I., and Slagle, I. R. Kinetics of the C2H3 + H2 H + C2H4 and CH3 + H2 H + CH4 Reactions. J. Phys. Chem. 100, 11346-11354 (1996). Knyazev, V. D. and Slagle, I. R. Experimental and Theoretical Study of the C2H3 H + C2H2 Reaction. Tunneling and the Shape of Falloff Curves. J. Phys. Chem. 100, 16899-16911 (1996). Knyazev, V. D., Stoliarov, S. I., and Slagle, I. R. Kinetics of the Reaction of Vinyl Radicals with Acetylene. Proc. Combust. Inst. 26, 513-519 (1996). Knyazev, V. D. and Slagle, I. R. Kinetics of the Reactions of Allyl and Propargyl Radicals with CH 3. J. Phys. Chem. A 105, 3196-3204 (2001). Ko, T., Adusei, G. Y. and Fontijn, A. Kinetics of the reactions between O(3P) and 1-butene from 335 to 1110 K. J. Phys. Chem. 95, 9366-9370 (1991). Ko, T., Adusei, G. Y. and Fontijn, A. Kinetics of the O(3P) + C6H6 Reaction over a wide Temperature Range. J. Phys. Chem. 95, 8745-8748 (1991). Koda, S., Endo, Y., Tsuchiya, S. and Hirota, E. Branching ratios in O(3P) reactions of terminal olefins studied by kinetic microwave absorption spectroscopy. J. Phys. Chem. 95, 1241 (1991). Konar, R. S., Marshall, R. M.and Purnell, J. H. Initiation of isobutane pyrolysis. Trans. Faraday Soc. 64, 405-413 (1968). Kubitza, Ch., Schmitt, P. and Homann, K. H. Formation of higher hydrocarbons by reactions of vinyl radicals. Poster presented at the Twenty-Fifth Symposium (International) on Combustion, Irvine, CA, 1994. Lee, K. Y., Yang, M. H. and Puri, I. K. Numerical Simulation of Stoichiometric Premixed Flames Burning CH3Cl/CH4/Air Mixtures at Atmospheric Pressure with a Full and Short Reaction Mechanism and Comparison of the Flame Speeds with Experimental Results. Combust. Flame 92, 419-439 (1993). Leidreiter, H. I. and Wagner, H. Gg. An Investigation of the Reaction beween O(3P) and Benzene at High Temperatures. Z. Phys. Chem. N. F. 165, 1-7 (1989). Leung, K. M. and Lindstedt, R. P. Detailed kinetic modelling of C1 – C3 alkane diffusion flames. Combust. Flame 102, 129 (1995). Lim, K. P. and Michael, J. V. The thermal decomposition of CH3Cl using the Cl-atom absorption method and the bimolecular rate constant of O + CH3 (1609-2002 K) with a pyrolysis photolysis-shock tube technique. J. Chem. Phys. 98, 3919-3928 (1993). This journal is © The Owner Societies 2002 Lin, C.-Y. and Lin, M. C. Thermal Decomposition of Methyl Phenyl Ether in Shock Waves: The Kinetics of Phenoxy Radical Reactions. J. Phys. Chem. 90, 425-431 (1986). Lindstedt, R. P. and Skevis, G. Chemistry of Acetylene Flames. Combust. Sci. and Tech. 125, 73-137 (1997). Liu, M. T. H. and Laidler, K. J. Elementary processes in the acetaldehyde pyrolysis. Can. J. Chem. 46, 479 (1968). Louw, R. and Lucas, H. J. Vapour Phase Chemistry of Arenes. I Thermolysis of benzene and derivatives; the effect of additives. Evidence for free radical chain processes. Rec. Trav. Chim. 92, 5571 (1973). Lundgard, R. and Heicklen, J. Pyrolysis of Vinylacetylene between 300 and 450 ºC. Int. J. Chem. Kinet. 16, 125-148 (1984). Madden, L. K., Moskaleva, L. V., Kristyan, S. and Lin, M. C. Ab Initio MO Study of the Unimolecular Decomposition of the Phenyl Radical. J. Phys. Chem. A 101, 6790-6797 (1997). Madronich, S. and Felder, W. Kinetics and Mechanism of the Reaction of OH with C6H6 over 7901410 K. J. Phys. Chem. 89, 3556-3561 (1985). Maldotti, A., Chiorboli, C., Bignozzi, C.A., Bartocci, C. and Carassiti, V. Photooxidation of 1,3Butadiene Containing Systems: Rate Constant Determination for the Reaction of Acrolein with OH Radicals. Int. J. Chem. Kinet. 12, 905 (1980). Marcy, T. P., Dìaz, R. R., Heard, D., Leone, S. R., Harding, L. B. and Klippenstein, S. J. Theoretical and experimental investigation of the dynamics of the production of CO from the CH3 + O and CD3 + O reactions. J. Phys. Chem. A 105, 8361-8369 (2001). Marinov, N. M., Pitz, W. J., Westbrook, C. K., Castaldi, M. J. and Senkan, S. M. Modeling of Aromatic and Polycyclic Aromatic Hydrocarbon Formation in Premixed Methane and Ethane Flames. Combust. Sci. and Tech. 116-117, 211-287 (1996). Marinov, N. M., Castaldi, M. J., Melius, C. F. and Tsang, W. Aromatic and Polycyclic Aromatic Hydrocarbon Formation in a Premixed Propane Flame. Combust. Sci. and Tech. 128, 295-342 (1997). Marinov, N. M., Pitz, W. J., Westbrook, C. K., Vincitore, A. M., Castaldi, M. J., and Senkan, S. M. Aromatic and Polycyclic Aromatic Hydrocarbon Formation in a Laminar Premixed n-Butane Flame. Combust. Flame 114, 192-213 (1998). McAdam, K. G. and Walker, R. W. Arrhenius Parameters for the reaction C2H5 + O2 C2H4 + HO2. J. Chem. Soc. Faraday Trans. 2 83, 1509 (1987). Mebel, A. M., Diau, E. W. G., Lin, M. C., and Morokuma, K. Ab Initio and RRKM Calculations for Multichannel Rate Constants of the C2H3 + O2 Reaction. J. Am. Chem. Soc. 118, 9759-9771 (1996). Mebel, A. M., Lin, M. C., Yu, T. and Morokuma, K. Theoretical Study of Potential Energy Surface and Thermal Rate Constants for the C6H5 + H2 and C6H6 + H Reactions. J. Phys. Chem. A 101, 3189– 3196 (1997). Mebel, A. M., Lin, M. C., Chakraborty, D., Park, J., Lin, S. H. and Lee, Y. T. Ab initio molecular orbital/Rice-Ramsperger-Kassel-Marcus theory study of multichannel rate constants for the unimolecular decomposition of benzene and the H+C6H5 reaction over the ground electronic state. J. Chem. Phys. 114, 8421-8435 (2001). Melius, C. F., Miller, J. A. and Evleth, E. M. Unimolecular Reaction Mechanisms Involving C3H4, C4H4, and C6H6 Hydrocarbon Species. Proc. Combust. Inst. 24, 621-628 (1992). Miller, J. A. and Melius, C. F. Kinetic and Thermodynamic Issues in the Formation of Aromatic Compounds in Flames of Aliphatic Fuels, Combust. Flame 91, 21-39 (1992). Miller, J. A., Klippenstein, S. J. and Robertson, S. H. A Theoretical Analysis of the Reaction between Ethyl and Molecular Oxygen. Proc. Combust. Inst. 28, 1479-1486 (2000). Miller, J. A., Klippenstein, S. J. and Robertson, S. H. A Theoretical Analysis of the Reaction between Vinyl and Acetylene: Quantum Chemistry and Solution of the Master Equation. J. Phys. Chem. A 104, 7525-7536 (2000). This journal is © The Owner Societies 2002 Moskaleva, L. V. and Lin, M. C. Unimolecular Isomerization/Decomposition of Cyclopentadienyl and Related Bimolecular Reverse Process: Ab Initio MO/Statistical Theory Study. J. Comput. Chem. 21, 415-425 (2000). Müller-Markgraf, W. and Troe, J. Thermal Decomposition of Ethylbenzene, Styrene, and Bromophenylethane: UV Absorption Study in Shock Waves. J. Phys. Chem. 92, 4914-4922 (1988). Mulder, P. and Louw, R. Vapour-phase chemistry of arenes. Part 10. Formation of phenols in air oxidation of benzene, chlorobenzene, m-dichlorobenzene, and benzonitrile in the presence of cyclohexa-1,3-diene at ca. 600 K. J. Chem. Soc. Perkin Trans. 2, 1135 (1985). Mulenko, S.A. The application of an intracavity laser spectroscopy method for elementary processes study in gas-phase reactions. Rev. Roum. Phys. 32, 173 (1987). Murrell, J.N. and Rodriguez, J.A. Predicted rate constants for the exothermic reactions of ground state oxygen atoms and CH radicals. J. Mol. Struct. THEOCHEM. 139, 267 (1986). Orchard, S. E. and Thrush, B. A. Photochemical studies of unimolecular processes. VI. The unimolecular reactions of C6H8 isomers and the interpretation of their photolyses. Proc. R. Soc. London A 337, 257-274 (1974). Park, J. and Lin, M. C. Kinetics for the Recombination of Phenyl Radicals. J. Phys. Chem. A 101, 1418 (1997). Park, J., Burova, S., Rodgers, A. S., and Lin, M. C. Experimental and Theoretical Studies of the C6H5 + C6H6 Reaction. J. Phys. Chem. A 103, 9036-9041 (1999). Pauwels, J.-F., Volponi, J. V. and Miller, J. A. The Oxidation of Allene in a Low-Pressure H2/O2/ArC3H4 Flame. Combust. Sci. and Tech. 110-111, 249-276 (1995). Pitz, W. J. and Westbrook, C. K. Chemical Kinetics of the High Pressure Oxidation of n-Butane and Its Relation to Engine Knock. Combust. Flame 63, 113-133 (1986). Pope, C. J. and Miller, J. A. Exploring Old and New Benzene Formation Pathways in Low-Pressure Premixed Flames of Aliphatic Fuels. Proc. Combust. Inst. 28, 1519-1527 (2000). Porter, G. and Steinfeld, J. I. Rate of Dimerisation of Gaseous Benzyne. J. Chem. Soc. (A), 877-878 (1968). Richter, H., Benish, T. G., Mazyar, O. A., Green, W. H. and Howard, J. B. Formation of Polycyclic Aromatic Hydrocarbons and their Radicals in a Nearly Sooting Premixed Benzene Flame. Proc. Combust. Inst. 28, 2609-2618 (2000). Richter, H., Mazyar, O., Sumathy, R., Green, W. H., Howard, J. B. and Bozzelli, J. W. Detailed Kinetic Study of the Growth of Small Polycyclic Aromatic Hydrocarbons I. 1-Naphthyl+Ethyne. J. Phys. Chem. A 105, 1561-1573 (2001). Roy, K., Horn. C., Frank, P., Slutsky, V. G. and Just. T. High-Temperature Investigations on the Pyrolysis of Cyclopentadiene. Proc. Combust. Inst. 27, 329-336 (1998). Saito, K., Mochizuki, Y., Yoshinobu, I. and Imamura, A. On the thermal unimolecular decomposition of propynal. Chem. Phys. Lett. 167, 347 (1990). Scherer, S., Just, T. and Frank, P. High Temperature Investigations on Pyrolytic Reactions of Propargyl Radicals. Proc. Combust. Inst. 28, 1511-1518 (2000). Sehested, J., Sehested, K., Platz, J., Egsgaard, H. and Nielsen, O. J. Oxidation of dimethyl ether: absolute rate constants for the self reaction of CH3OCH2 radicals, the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals. Int. J. Chem. Kinet. 29, 627-636 (1997). Singleton, D. L., Irwin, R. S. and Cvetanovic, R. J. Arrhenius Parameters for the Reactions of O(3P) Atoms with Several Aldehydes and the Trend in Aldehydic C-H Bond Dissociation Energies. Can. J. Chem. 55, 3321 (1977). Shandross, R. A. “Experimental and Theoretical Study of Hydrogen and Benzene Destruction Chemistries”, PhD thesis, Massachusetts Institute of Technology, 1996. This journal is © The Owner Societies 2002 Shandross, R. A., Longwell, J. P. and Howard, J. B. Destruction of Benzene in High-Temperature Flames: Chemistry of Benzene and Phenol. Proc. Combust. Inst. 26, 711-719 (1996). Sillesen, A., Ratajczak, E. and Pagsberg, P. Kinetics of the reactions H+C2H4 C2H5, H+C2H5 2CH3 and CH3+C2H5 products studied by pulse radiolysis combined with infrared diode laser spectroscopy. Chem. Phys. Lett. 201, 171-177 (1993). Solly, R. K. and Benson, S. W. Kinetics of the gas-phase unimolecular decomposition of the benzoyl radical. J. Am. Chem. Soc. 93, 2127 (1971). Su, J. Z. and Teitelbaum, H. The Rate of Methyl Radical Decomposition at High Temperatures and Pressures. Int. J. Chem. Kinet. 26, 159-169 (1994). Szirovicza, L. Kinetics of some reactions of vinyl and isopropyl radicals in the gas-phase. Int. J. Chem. Kinet. 17, 117 (1985). Thiesemann, H., Clifford, E. P., Taatjes, C. A. and Klippenstein, S. J. Temperature Dependence and Kinetic Isotope Effects in the CH (CD) + C2H4 (C2D4) Reaction between 295 and 726 K. J. Phys. Chem. A 105, 5393-5401 (2001). Tokmakov, I. V., Park, J., Gheyas, S., and Lin, M. C. Experimental and Theoretical Studies of the Reaction of the Phenyl Radical with Methane. J. Phys. Chem. A 103, 3636-3645 (1999). Tsang, W. and Hampson, R.F. Chemical kinetic data base for combustion chemistry. Part I. Methane and related compounds. J. Phys. Chem. Ref. Data 15, 1087 (1986). Tsang, W. Chemical kinetic data base for combustion chemistry. Part 2. Methanol. J. Phys. Chem. Ref. Data 16, 471 (1987). Tsang, W. Chemical kinetic data base for combustion chemistry. Part 3. Propane. J. Phys. Chem. Ref. Data 17, 887 (1988). Tsang, W. Chemical kinetic data base for combustion chemistry. Part V. Propene. J. Phys. Chem. Ref. Data 20, 221-273 (1991). Tsang, W. Chemical kinetic data base for hydrocarbon pyrolysis. Ind. Eng. Chem. 31, 3-8 (1992). Tsang, W. and Walker, J. A. Pyrolysis of 1,7-Octadiene and the Kinetic and Thermodynamic Stability of Allyl and 4-Pentenyl Radicals, J. Phys. Chem. 96, 8378-8384 (1992). Tully, F.P. and Droege, A.T. Kinetics of the reactions of the hydroxyl radical with dimethyl ether and diethyl ether. Int. J. Chem. Kinet. 19, 251 (1987). Van Look, H. and Peeters, J. Rate coefficients of the reactions of C2H with O2, C2H2, and H2O between 295 and 450 K. J. Phys. Chem. 99, 16284-16289 (1995). Wang, H. and Brezinsky, K. Computational Study on the Thermochemistry of Cyclopentadiene Derivatives and Kinetics of Cyclopentadienone Thermal Decomposition. J. Phys. Chem. A 102, 15301541 (1998). Warnatz, J., Bockhorn, H., Möser, A. and Wenz. H. W. Experimental Investigations and Computational Simulation of Acetylene-Oxygen Flames from Near Stoichiometric to Sooting Conditions. Proc. Combust. Inst. 19, 197-209 (1982). Warnatz, J. Rate coefficients in the C/H/O system. Combustion Chemistry (ed. W. C. Gardiner, Jr.), Springer-Verlag, New York 1984, 197. Weissman, M. and Benson, S. W. Pyrolysis of methyl chloride, a pathway in the chlorine-catalyzed polymerization of methane. Int. J. Chem. Kinet. 16, 307 (1984). Westbrook, C. K. and Dryer, F. L. Chemical Kinetic Modeling of Hydrocarbon Combustion. Prog. Energy Comb. Sci. 10, 1-57 (1984). Westmoreland, P. R. “Experimental and Theoretical Analysis of Oxidation and Growth Chemistry in a Fuel-Rich Acetylene Flame”, PhD thesis, Massachusetts Institute of Technology, 1986. Zabarnick, S., Fleming, J.W. and Lin, M.C. Temperature dependence of CH radical reactions with H2O and CH2O. Proc. Combust. Inst. 21, 713-719 (1986). Westmoreland. P. R., Dean, A. M., Howard, J. B. and Longwell, J. P. Forming Benzene in Flames by Chemically Activated Isomerization. J. Phys. Chem. 93, 8171-8180 (1989). This journal is © The Owner Societies 2002 Wu, C. H. and Kern, R. D. Shock Tube Study of Allene Pyrolysis. J. Phys. Chem. 91, 6291-6296 (1987). Yu, T. and Lin, M. C. Kinetics of Phenyl Radical Reactions Studied by the “Cavity-Ring-Down” Method. J. Am. Chem. Soc. 115, 4371-4372 (1995). Zhang, H. X., Ahonkhai, S. I. and Back, M. H. Rate constants for abstraction of hydrogen from benzene, toluene, and cyclopentane by methyl and ethyl radicals over the temperature range 650-770 K. Can. J. Chem. 67, 1541-1549 (1989). Zhang, H.-Y. and McKinnon, J. T. Elementary Reaction Modeling of High Temperature Benzene Combustion. Combust. Sci. and Tech. 107, 261-300 (1995). Zhong, X. and Bozzelli, J. W. Thermochemical and Kinetic Analysis of the H, OH, HO2, O, and O2 Association Reactions with Cyclopentadienyl Radical. J. Phys. Chem. A 102, 3537-3555 (1998).
