njit-etd2003-111 - New Jersey Institute of Technology

More documents

Recommendations

Info

LIST OF FIGURES (Continued) Figure Page 8.7 CH3CH25CH2CH3 dissociation k vs. 1000/T at 1 atm 240 A.1 CH3C(0)00 dissociation k vs. 1000/T at lam 243 A.2 CH3C(0)00 dissociation k vs. pressure at 298K 244 A.3 CH3C(0)00 dissociation k vs. pressure at 1000K 245 A.4 C01-12C(-O)00H dissociation k vs. 1000/T at lam 246 A.5 C0142C(0)0OH dissociation k vs. pressure at 298K 247 A.6 C0142C(0)0OH dissociation k vs. pressure at 1000K 248 A.7 Potential barriers for internal rotation in CH3C(0)00N02 at B3LYP/6-31G(d') level of theory 249 A.8 Potential barriers for internal rotation in C2HS00N02 at B3LYP/6-31G(d') level of theory 251 B.1 C(00•)H2CHO dissociation k vs. 1000/T at lam 257 B.2 C(00•)H2CHO dissociation k vs. pressure at 298K 258 B.3 C(00•)H2CHO dissociation k vs. pressure at 1000K 259 B.4 C(0OH)H2C.O dissociation k vs. 1000/T at lam 260 B.5 C(00H)H2C00 dissociation k vs. pressure at 298K 261 B.6 C(00H)H2C00 dissociation k vs. pressure at 1000K 262 E.1 Collision efficiency vs. temperature for C.H2CHO stabilization in CH2C0 + H reaction system 298 E.2 Collision efficiency vs. temperature for CH 3C(0)00 stabilization in CH3C*0 + 02 reaction system 299
CHAPTER 1 INTRODUCTION 1.1 Background Important initial products from pyrolysis, oxidation, or photochemical reactions of saturated and unsaturated hydrocarbons are the corresponding radicals. The subsequent reactions of the hydrocarbon radicals with molecular oxygen are complex and often difficult to study experimentally. These reactions often represent the principal pathways of the radical conversion in hydrocarbon combustionl°2 and atmosphere oxidation. Acetaldehyde (CH3CHO) and the radical species that result through loss of hydrogen atoms from the carbon sites in CH3AH0 are common products (intermediates) from oxidation of higher molecular weight hydrocarbon species in combustion and in atmospheric chemistry. Oxidation of methane also forms these species as a result of methyl radical combination and subsequent reactions of the ethane. The association reaction of these radicals with molecular oxygen (302) will form chemically activated peroxy adducts that can be stabilized, or the adduct may react via either isomerization or dissociation to new products before stabilization. The adducts can also dissociate back to initial reactants. These reactions are complex, because of competition between the pressure dependent stabilization versus unimolecular reaction to new products or reverse dissociation.l'2 The isomerization, dissociation and bimolecular reactions of the stabilized adduct provide further complexity. The reactions of radicals from acetaldehyde with oxygen also serve as model reactions for some reaction paths of larger aldehydic molecule systems. 1
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: LIST OF FIGURES (Continued) Figure
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.
Page 72: 46 is more than one order of magnit
Page 78 and 79:
52 c) 0 E E 0 0) O 0.001 0.01 0.1 1
Page 80 and 81:
54 (3) Comparison of Dissociation R
Page 83 and 84:
57 3.3.9 Acetyl Radical Unimolecula
Page 85:
59 Table 10 Detailed Mechanism (Con
Page 88 and 89:
62 3.3.11 CH3C.0 Importance of CH3C
Page 90 and 91:
64 Figure 3.12 Chemkin kinetic calc
Page 92 and 93:
Figure 3.13 Chemkin kinetic calcula
Page 94 and 95:
66 3.4 Summary Thermochemical prope
Page 96 and 97:
68 mbar. Abstraction from the methy
Page 98 and 99:
70 accuracy of theoretically evalua
Page 100 and 101:
72 Ab initio calculations for ZPVE
Page 102 and 103:
74 4.2.4 Kinetic Analysis Thermoche
Page 104 and 105:
76 H4 atom is in a bridge structure
Page 106 and 107:
Table 4.1 Enthalpies of Formation f
Page 108 and 109:
Figure 4.1 Bond dissociation energy
Page 110:
82 CBS-QllB3LYPl6-31G(d) calculatio
Page 114 and 115:
86 4.3.5 Comparison of C0142CHO + 0
Page 116:
88 Table 4.8 Resulting Rate Constan
Page 119:
91 (-1) c'E U O 0.5 1.0 1.5 2.0 2.5
Page 122 and 123:
94 The barrier is determined to be
Page 124:
96 4.3.10 Detailed Mechanism of For
Page 127 and 128:
99 Data on concentration versus tim
Page 129 and 130:
101 4.3.11 C01-12CH0 Comparison of
Page 131 and 132:
103 was included in the bimolecular
Page 133 and 134:
105 equation of for falloff. Reacti
Page 135 and 136:
107 Another important route to C2H2
Page 137 and 138:
109 Chis study focuses on the react
Page 139 and 140:
111 The working reactions for estim
Page 141 and 142:
113 (hp is the Planck constant and
Page 143 and 144:
115
Page 145 and 146:
117
Page 147 and 148:
119
Page 149 and 150:
121
Page 151 and 152:
123 The activation energies and ent
Page 153 and 154:
125
Page 155 and 156:
127 Che hydrogen atom also can add
Page 157 and 158:
129
Page 159 and 160:
131 Carr et al.132 and Slemr et al.
Page 161 and 162:
133 5.3.5.3 Results of Chemical Act
Page 163 and 164:
135
Page 165 and 166:
137
Page 167 and 168:
139
Page 169 and 170:
141 2) Comparison of Rate Constants
Page 171 and 172:
143
Page 173 and 174:
CHAPTER 6 THERMOCHEMICAL PROPERTIES
Page 175 and 176:
147 and thus a structure than may h
Page 177 and 178:
149
Page 179 and 180:
151 Values of the coefficients (B o
Page 181 and 182:
153 Che transition state (CS) struc
Page 183 and 184:
155 C2 bonds lengthen to 2.27 and 1
Page 185 and 186:
Che TS structure, TC.YCCOO, represe
Page 187 and 188:
159 Comparison of bond lengths (A)
Page 189 and 190:
Table 6.1 Enthalpies of Formation f
Page 191 and 192:
163 enthalpy of formation for the p
Page 193 and 194:
165 Entropy and heat capacities are
Page 195 and 196:
167
Page 197 and 198:
169 unstable intermediate {YC=CCOI}
Page 199 and 200:
171
Page 201 and 202:
173
Page 203 and 204:
175
Page 205 and 206:
177
Page 207 and 208:
179
Page 209 and 210:
7.1 Overview Thermodynamic properti
Page 211 and 212:
183 and chlorobenzene, respectively
Page 213 and 214:
185 vibrational energies (ZPVE) whi
Page 215 and 216:
Table 7.2 C12 + Radicals > Products
Page 217 and 218:
189
Page 219 and 220:
1 dl 1
Page 221 and 222:
193 Table 7.4 Thermodynamic and Kin
Page 223 and 224:
195
Page 225 and 226:
197 identical adjustment in each of
Page 227 and 228:
199
Page 229 and 230:
201 Figure 7.4 and the above descri
Page 231 and 232:
203 7.4.6 Thermodynamics of Literat
Page 233 and 234:
] 205
Page 235 and 236:
207
Page 237 and 238:
209 The more exothermic C12 + R. re
Page 239 and 240:
211 trends of Eafwd vs AHrxn,nd and
Page 241 and 242:
213 systems HCl molecular eliminati
Page 243 and 244:
215
Page 245 and 246:
8.3.2 Enthalpies of Formation Entha
Page 247 and 248:
219 Table 8.2 Comparison of Enthalp
Page 249 and 250:
AJPrxn,298 221 Table 8.4 Reaction E
Page 251 and 252:
223 between reactant and transition
Page 253 and 254:
225
Page 255 and 256:
227
Page 257 and 258:
229 Table 8.6 Ideal Gas Phase Therm
Page 259 and 260:
values available. If not, the value
Page 261 and 262:
233 8.4.4.1 Retro-ene Reaction. The
Page 263 and 264:
235 The CH 3 CH2SCH2CH3 also can un
Page 265 and 266:
237 8.4.4.4 Thermodynamic and Kinet
Page 267 and 268:
239
Page 269 and 270:
241 For CH3CH2SCH2CH3 dissociation,
Page 271 and 272:
243 O E E 0) O (1ATM) 1000/T (K)
Page 273 and 274:
245
Page 275 and 276:
247
Page 277 and 278:
249
Page 279 and 280:
■ ■.■
Page 281 and 282:
APPENDIX B GEOMETRIES AND C(000)H2C
Page 283 and 284:
44
Page 285 and 286:
257
Page 287 and 288:
259
Page 289 and 290:
261 O EM c U O 0.0001 0.001 0.01 0.
Page 291 and 292:
APPENDIX C GEOMETRIES, VIBRATIONAL
Page 293 and 294:
265
Page 295 and 296:
267
Page 297 and 298:
769
Page 299 and 300:
271 Table C.2 Vibrational Frequenci
Page 301 and 302:
273 Table CH3CH2SCH2CH3 D.1 Total E
Page 303 and 304:
275 Table D.2 Coefficients of Trunc
Page 305 and 306:
277 Table D.3 Vibrational Frequenci
Page 307 and 308:
Table D.4 Thermodynamic and Kinetic
Page 309 and 310:
Page 311 and 312:
Page 313 and 314:
Page 315 and 316:
287 E.1 ChemRate ChemRate" is a pro
Page 317 and 318:
4. Specification of reaction [Clica
Page 319 and 320:
291 E.1.2.2 Output EDample for Chem
Page 321 and 322:
102
Page 323 and 324:
295 where s represents the number o
Page 325 and 326:
297
Page 327 and 328:
299
Page 329 and 330:
301 (19) Foresman, J. B.; Frisch, A
Page 331 and 332:
303 (57) Rienstra-Kiracofe, J. C.;
Page 333 and 334:
305 (89) Reid, R. C.; Prausnitz, J.
Page 335 and 336:
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.
show all

njit-etd2003-111 - New Jersey Institute of Technology

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?