njit-etd2003-111 - New Jersey Institute of Technology

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ABSTRACT THERMOCHEMISTRY AND KINETIC ANALYSIS ON RADICALS OF ACETALDEHYDE + 02, ALLYL RADICAL + 02 AND DIETHYL AND CHLORODIETHYL SULFIDES by Jongwoo Lee Thermochemical properties for reactants, intermediates, products and transition states important in the radicals of acetaldehyde + 02 and allyl radical + 02 reaction systems are analyzed with density functional and ab initio calculations, to evaluate the reaction paths and kinetics in oxidation and pyrolysis. Ketene is one important product resulting from acetaldehyde oxidation; thus thermochemistry plus isomerization and conversion reactions of ketene are also analyzed. Enthalpies of formation are determined using isodesmic reaction analysis at the CBSQ composite and density functional levels. Entropies and heat capacities are determined using geometric parameters and vibration frequencies obtained at the HF/6-31G(d') or B3LYP/6-31G(d,p) level of theory. Internal rotor contributions are included in calculation of entropy, S°298, and heat capacities, Cp(T). Rate constants are estimated as a function of pressure and temperature using multifrequency quantum Rice-Ramsperger-Kassel analysis for k(E) and master equation analysis for falloff. A mechanism for pyrolysis and oxidation of acetaldehyde and its' corresponding radicals is constructed. The competition between reactions of radicals of acetaldehyde with 02 versus unimolecular decomposition is evaluated versus temperature and pressure. Thermodynamic parameters, enthalpies, entropies and heat capacities are evaluated for C1 and C2 chiorocarbon molecules and radicals. These thermodynamic
Page 1: Copyright Warning & Restrictions Th
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 and 28: CHAPTER 1 INTRODUCTION 1.1 Backgrou
Page 29 and 30: 3 Because of its thermal stability
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
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27 information. Zero-point vibratio
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29 enthalpies of reactant and produ
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31 3.2.4 Kinetic Analysis The poten
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3.3.2 Enthalpy of Formation (Arif°
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35 incorporated in the estimation o
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41 similar well depths 35.3 and 35.
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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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117
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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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177
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179
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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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259
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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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