njit-etd2003-111 - New Jersey Institute of Technology

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LIST OF TABLES (Continued) Table Page 8.3 Enthalpies of Formation for Reference Molecules in the Isodesmic Reactions 220 8.4 Reaction Enthalpies and Enthalpies of Formation in the Isodesmic Reactions 221 8.5 Comparison of Activation Energies (Units in kcal/mol) 223 8.6 Ideal Gas Phase Thermodynamic Properties Obtained by B3LYP/6-31G(d,p) Calculationa 228 8.7 Bond Energies at 298K 232 B.1 Geometries of Radicals and TS Optimized at MP2/6-31G(d') a 254 C.1 Geometries of Intermediate Radicals and Transition States Optimized at B3LYP/6-31G(d,p) 264 C.2 Vibrational Frequencies and Moments of Inertia at B3LYP/6-31G(d,p) level 270 D.1 Total Energy and Internal Rotation Barriers of CH 3CH2SCH2CH 3 and CH3CH2SCH2CH3 273 D.2 Coefficients of Truncated Fourier Series Expansions for Internal Rotation Potentialsa 275 D.3 Vibrational Frequencies and Moments of Inertia at B3LYP/6-31G(d,p) level 276 D.4 Thermodynamic and Kinetic Analysis vs. Temperature in Retro-ene and HC1 Eliminations 278 D.5 Thermodynamic and Kinetic Analysis vs. Temperature in Bond Cleavage Reactions 284 Dviii
LIST OF FIGURES Figure Page 2.1 Potential energy diagram of CH3C*O + 02 18 3.1 Potential energy diagram CH3C*O + 02 39 3.2 Bond dissociation energy of CH3C(=O)OOH (Units : kcal/mol) 40 3.3 CH3C.O +02 -> products k vs. 1000/T at latm 47 3.4 CH3C*O +02 -> products k vs. pressure at 298K 48 3.5 CH3C.O +02 -> products k vs. pressure at 1000K 49 3.6 Comparison of rate constants between Chemaster and ChemRate with pressure in 800K with CH3C(0)00 dissociation 52 3.7 Comparison of rate constants between Chemaster and ChemRate with pressure in 1000K with CH 3C(0)00 dissociation 53 3.8 Comparison of rate constants between Chemaster and ChemRate with pressure in 800K with C.H2C(-----O)0OH dissociation 55 3.9 Comparison of rate constants between Chemaster and ChemRate with pressure in 1000K with C*H2C(0)0OH dissociation 56 3.10 Potential energy diagram of acetyl and formyl methyl radical unimolecular isomerization/ dissociations (Units : kcal/mol) 57 3.11 Chemkin kinetic calculations: concentration vs. time 60 3.12 Chemkin kinetic calculations: concentration vs. time 64 3.13 Chemkin kinetic calculations: concentration vs. time 65 4.1 Bond dissociation energy of C(00H)H2CHO (Units : kcal/mol) 80 4.2 Potential energy diagram C01-12CHO + 02 85 4.3 C01-12CHO + 02 -> products k vs. 1000/T at lam 91 4.4 C01-12CHO + 02 -> products k vs. pressure at 298K 92 4.5 C01-12CHO + 02 -> products k vs. pressure at 1000K 93 DiD
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: LIST OF TABLES (Continued) Table Pa
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
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.
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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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247
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249
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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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Page 311 and 312:
Page 313 and 314:
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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
Page 337 and 338:
309 (159) Cox, J. D. , Pilcher, G.
Page 339:
311 4-92) Yamada, T., Bozzeili, J.
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