njit-etd2003-111 - New Jersey Institute of Technology

More documents

Recommendations

Info

BIOGRAPHICAL SKETCH Author: Jongwoo Lee Degree: Doctor of Philosophy Date: August 2003 Undergraduate and Graduate Education: • Doctor of Philosophy in Chemical Engineering, New Jersey Institute of Technology, Newark, NJ, 2003 • Master of Science in Chemical Engineering, New Jersey Institute of Technology, Newark, NJ, 1999 • Bachelor of Science in Chemical Engineering, Yonsei University, Seoul, Korea, 1995 Major: Chemical Engineering Publications: Lee, J.; Bozzelli, J. W., "Thermochemical and Kinetic Analysis of the Formyl Methyl Radical + 02 Reaction System" Journal of Physical Chemistry A, Volume 107, Issue 19, 2003, pp. 3778-3791. Lee, J.; Bozzelli, J. W., "Reaction of H + Ketene to Formyl Methyl and Acetyl Radicals and Reverse Dissociations" International Journal of Chemical Kinetics, Volume 35, Issue 1, 2003, pp. 20-44. Lee, J.; Chen, C.; Bozzelli, J. W., "Thermochemical and Kinetic Analysis of the Acetyl Radical (CH3C.O) + 0 2 Reaction System" Journal of Physical Chemistry A, Volume 106, Issue 31, 2002, pp. 7155-7170. iv
Lee, J.; Bozzelli, J. W.; Sawerysyn, J. P., "Ab initio Calculations and Thermochemical Analysis on Cl Atom Abstractions of Chlorine from Chiorocarbons and the Reverse Alkyl Abstractions: C1 2 + R• H Cl + RCA" International Journal of Chemical Kinetics, Volume 32, Issue 9, 2000, pp. 548-565. Presentations: Lee, J.; Bozzelli, J. W.; Pitz, W., "Thermochemical Properties, Reaction Pathways, and Kinetics of the Ally' Radical with 0 2 Reaction System", AIChE Annual Meeting; Indianapolis, IN; November 3-8, 2002, 392a, Oral Presentation. Lee, J.; Bozzelli, J. W., "Thermochemical Properties, Reaction Pathways, and Kinetics of the Formyl Methyl Radical + 02 Reaction System", AIChE Annual Meeting; Indianapolis, IN; November 3-8, 2002, 223b, Poster. Lee, J.; Bozzelli, J. W., "Thermochemical Properties, Reaction Pathways, and Kinetics of the Ketene + H Reaction System", AIChE Annual Meeting; Indianapolis, IN; November 3-8, 2002, 373ab, Poster. Lee, J.; Bozzelli, J. W., "Thermochemical Properties, Reaction Pathways, and Kinetics of the Acetyl Radical + 02 Reaction System", 17th International Symposium on Gas Kinetics; Essen, Germany; August 24-29, 2002, AP.10, Poster. Lee, J.; Bozzelli, J. W., "Thermodynamic Properties of Acetyl and Ethyl Hydroperoxides and Peroxyacetyl and Peroxyethyl Nitrite", 223rd ACS National Meeting; Orlando, FL; April 7-11, 2002, 180, Poster. Lee, J.; Bozzelli, J. W., "Thermodynamic and Kinetic Analysis using Ab initio Calculations on Formyl Methyl Radical + 02 Reaction System", Fifth International Conference on Chemical Kinetics; Gaithersburg, MD; July 16-20, 2001, 295-296, Oral Presentation. Lee, J.; Bozzelli, J. W.; Pitz, W., "Thermochemical and Kinetic Analysis on Allyl Radical + 02 Reaction System", Fifth International Conference on Chemical Kinetics; Gaithersburg, MD; July 16-20, 2001, 157-158, Poster. Lee, J.; Bozzelli, J. W.; Sawerysyn, J. P., "Ab initio Calculations and Thermodynamic Analysis on Cl Atom Abstractions of Chlorine from Chiorocarbons and the Reverse Alkyl Abstractions: C1 2 + R. 4---> Cl. + RCA", The Fall Technical Meeting of the Eastern States Section of the Combustion Institute; Raleigh, NC; October 10-13, 1999, 41-44, Oral Presentation.
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: APPROVAL PAGE THERMOCHEMISTRY AND K
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
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

Create successful ePaper yourself

Delete template?

Save as template?