njit-etd2003-111 - New Jersey Institute of Technology

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2 Acetaldehyde (AH3AO3) is of particular interest in atmospheric chemistry because it is formed as a product of the reaction of 03 and/or OH with naturally occurring, nonmethane hydrocarbons, especially higher olefins such as isoprene and terpenes. 3 °4 The photo-oxidation of hydrocarbons in photochemical smog also produces acetaldehyde as a major intermediate product. Acetaldehyde is, in addition, a significant product of incomplete combustion processes in diesel engines, aircraft exhausts, power plants, waste combustion, and many other oxidation processes. Acetaldehyde is also one of the important oxidation products of ethane and ethylene. Acetaldehyde and acetyl radicals are important intermediates in the overall breakdown processes of higher molecular weight and C1 hydrocarbons to CH2O, CO, CO2, and CH2O. Acetylperoxy radicals, AH3A(0)00 (often represented as CH3CO3• or CH3C03), are formed as a result of CH 3CO3 radical reaction with 02 and subsequent stabilization of the energized adduct. These peroxy radicals play an important role in atmospheric photooxidation processes: These stabilized peroxy radicals react with NO„ when it is present in the atmosphere and in the clean troposphere with other peroxy radicals. Acetylperoxy radicals are the precursor of peroxyacetylnitrite (PAN) an important constituent of photochemical smog and an air pollutant having important physiological effects. PAN is formed by combination with N025:
3 Because of its thermal stability at lower temperatures and its photochemical inertness under tropospheric conditions, PAN can act as a temporary reservoir for NO„ and serve as a carrier for transport in colder regions of the troposphere. 1.2 Previous Studies One absolute measurement of k1 has been reported in the literature; McDade et al. in 1-4 Corr He at 298 K. The high-pressure limit value of k1 = (3.01 ± 1.5) x 10 12 cm3/(mol s) recommended by the IUPAC panel is based on the absolute measurements of McDade et al. and the pressure dependence of the C2H5 + 02 reaction.' The results from two other studies, on the relative reactivity of CH3C.O with 02 and C12 5, and on the rate constant for CH3C00 with C12, 8 have been combined to give a high-pressure limit rate constant of k1 = (1.9 ± 0.4) x 10 12 cm3/(mol s) at room temperature. Tyndall et al. studied the reaction of the OH radical with methyl glyoxal and acetaldehyde in a low-pressure (ca. 3 Corr) flow reactor between 260 and 333 K. They report rate constants for OH abstractions from the parent molecules and also report data on further reactions of the radicals formed from the abstractions. They infer that only the acetyl radical is formed (no indication of formyl methyl radical) and further reaction of acetyl radical with 02 leads to noticeable regeneration of 0H based on observations showing reduced loss of the OH versus time. Chamber experiments by the same group at atmospheric pressure using FTIR detection showed no evidence of 0H radical production.9
Page 1 and 2: Copyright Warning & Restrictions Th
Page 3 and 4: ABSTRACT THERMOCHEMISTRY AND KINETI
Page 5 and 6: THERMOCHEMISTRY AND KINETIC ANALYSI
Page 7 and 8: APPROVAL PAGE THERMOCHEMISTRY AND K
Page 9 and 10: Lee, J.; Bozzelli, J. W.; Sawerysyn
Page 11 and 12: ACKNOWLEDGMENT First and foremost,
Page 13 and 14: TABLE OF CONTENTS (Continued) Chapt
Page 19 and 20: LIST OF TABLES Table Page 3.1 Activ
Page 21 and 22: LIST OF TABLES (Continued) Table Pa
Page 23 and 24: LIST OF FIGURES Figure Page 2.1 Pot
Page 25 and 26: LIST OF FIGURES (Continued) Figure
Page 27: CHAPTER 1 INTRODUCTION 1.1 Backgrou
Page 31 and 32: 5 based on work of Gutman's researc
Page 33 and 34: CHAPTER 2 THERMOCHEMICAL KINETICS 2
Page 35 and 36: 9 Gaussian function is termed uncon
Page 37 and 38: 1 1 5teinfeld et al.22 and Robinson
Page 39 and 40: The Lindemann theory, unfortunately
Page 41 and 42: 15 energies and phases of the speci
Page 43 and 44: 17 In RRK theory, the assumption is
Page 45 and 46: 19 The basic idea of the treatment
Page 47 and 48: 21 2.3.6 QRRK Analysis for Unimolec
Page 49 and 50: 23 Comparisons of ratios of these p
Page 51 and 52: 25 and atmospheric pressure; but di
Page 53 and 54: 27 information. Zero-point vibratio
Page 55 and 56: 29 enthalpies of reactant and produ
Page 57 and 58: 31 3.2.4 Kinetic Analysis The poten
Page 59 and 60: 3.3.2 Enthalpy of Formation (Arif°
Page 61: 35 incorporated in the estimation o
Page 67: 41 similar well depths 35.3 and 35.
Page 72: 46 is more than one order of magnit
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52 c) 0 E E 0 0) O 0.001 0.01 0.1 1
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54 (3) Comparison of Dissociation R
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57 3.3.9 Acetyl Radical Unimolecula
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59 Table 10 Detailed Mechanism (Con
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62 3.3.11 CH3C.0 Importance of CH3C
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64 Figure 3.12 Chemkin kinetic calc
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Figure 3.13 Chemkin kinetic calcula
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66 3.4 Summary Thermochemical prope
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68 mbar. Abstraction from the methy
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70 accuracy of theoretically evalua
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72 Ab initio calculations for ZPVE
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74 4.2.4 Kinetic Analysis Thermoche
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76 H4 atom is in a bridge structure
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Table 4.1 Enthalpies of Formation f
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Figure 4.1 Bond dissociation energy
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82 CBS-QllB3LYPl6-31G(d) calculatio
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86 4.3.5 Comparison of C0142CHO + 0
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88 Table 4.8 Resulting Rate Constan
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91 (-1) c'E U O 0.5 1.0 1.5 2.0 2.5
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94 The barrier is determined to be
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96 4.3.10 Detailed Mechanism of For
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99 Data on concentration versus tim
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101 4.3.11 C01-12CH0 Comparison of
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103 was included in the bimolecular
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105 equation of for falloff. Reacti
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107 Another important route to C2H2
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109 Chis study focuses on the react
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111 The working reactions for estim
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113 (hp is the Planck constant and
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115
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119
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121
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123 The activation energies and ent
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125
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127 Che hydrogen atom also can add
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129
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131 Carr et al.132 and Slemr et al.
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133 5.3.5.3 Results of Chemical Act
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135
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137
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139
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141 2) Comparison of Rate Constants
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143
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CHAPTER 6 THERMOCHEMICAL PROPERTIES
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147 and thus a structure than may h
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149
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151 Values of the coefficients (B o
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153 Che transition state (CS) struc
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155 C2 bonds lengthen to 2.27 and 1
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Che TS structure, TC.YCCOO, represe
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159 Comparison of bond lengths (A)
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Table 6.1 Enthalpies of Formation f
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163 enthalpy of formation for the p
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165 Entropy and heat capacities are
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167
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169 unstable intermediate {YC=CCOI}
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171
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173
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175
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7.1 Overview Thermodynamic properti
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183 and chlorobenzene, respectively
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185 vibrational energies (ZPVE) whi
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Table 7.2 C12 + Radicals > Products
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189
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1 dl 1
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193 Table 7.4 Thermodynamic and Kin
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195
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197 identical adjustment in each of
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199
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201 Figure 7.4 and the above descri
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203 7.4.6 Thermodynamics of Literat
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] 205
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207
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209 The more exothermic C12 + R. re
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211 trends of Eafwd vs AHrxn,nd and
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213 systems HCl molecular eliminati
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215
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8.3.2 Enthalpies of Formation Entha
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219 Table 8.2 Comparison of Enthalp
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AJPrxn,298 221 Table 8.4 Reaction E
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223 between reactant and transition
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225
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227
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229 Table 8.6 Ideal Gas Phase Therm
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values available. If not, the value
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233 8.4.4.1 Retro-ene Reaction. The
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235 The CH 3 CH2SCH2CH3 also can un
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237 8.4.4.4 Thermodynamic and Kinet
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239
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241 For CH3CH2SCH2CH3 dissociation,
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243 O E E 0) O (1ATM) 1000/T (K)
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245
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■ ■.■
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APPENDIX B GEOMETRIES AND C(000)H2C
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44
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257
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261 O EM c U O 0.0001 0.001 0.01 0.
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APPENDIX C GEOMETRIES, VIBRATIONAL
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265
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267
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769
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271 Table C.2 Vibrational Frequenci
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273 Table CH3CH2SCH2CH3 D.1 Total E
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275 Table D.2 Coefficients of Trunc
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277 Table D.3 Vibrational Frequenci
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Table D.4 Thermodynamic and Kinetic
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287 E.1 ChemRate ChemRate" is a pro
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4. Specification of reaction [Clica
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291 E.1.2.2 Output EDample for Chem
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102
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295 where s represents the number o
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297
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299
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301 (19) Foresman, J. B.; Frisch, A
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303 (57) Rienstra-Kiracofe, J. C.;
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305 (89) Reid, R. C.; Prausnitz, J.
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307 (123) Peeters, J.; Devriendt, K
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309 (159) Cox, J. D. , Pilcher, G.
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311 4-92) Yamada, T., Bozzeili, J.
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