Fluorine-Containing Free Radicals. Kinetics and Dynamics of Reactions

Title Page......Page 1
Copyright......Page 2
ACS Symposium Series......Page 3
FOREWORD......Page 4
PdftkEmptyString......Page 0
PREFACE......Page 5
Production of F 2PJ atoms......Page 7
Measurement of Atom Concentrations: absolute concentrations.......Page 8
Measurement of Atom Concentrations: Atomic Resonance......Page 10
Measurement of atom concentrations: Mass spectrometry.......Page 14
Addition of Fluorine Atoms to Spin-Paired Inorganic Molecules.......Page 17
a) Hydrogen Abstraction......Page 18
c) Halogen Abstraction.......Page 19
Production and reactions of FO radicals.......Page 21
Production and reactions of NF......Page 25
References......Page 27
2 Reactions of Radioactive 18F with Alkenes, Alkynes, and Other Substrates......Page 30
Experimental Aspects of Radioactive 18F Studies.......Page 31
18F Reactions with Alkenes and Alkynes.......Page 33
Product Analyses and Identification of Reaction Channels.......Page 37
Absolute Rate and Cross Section Measurements.......Page 40
Addition to Asymmetric Olefins.......Page 44
Isotope Effects in Fluorine-Alkene Reactions.......Page 54
Equilibration of Energy During the Reaction of Fluorine Atoms with Ethylene.......Page 58
Summary and Comments.......Page 59
Literature Cited......Page 60
3 Radiotracer Studies of Thermal Hydrogen Abstraction Reactions by Atomic Fluorine......Page 63
Experimental.......Page 64
Results.......Page 71
Discussion.......Page 76
Appendix I.......Page 101
Acknowledgement.......Page 103
Literature Cited.......Page 104
Sources of Fluoroalkyl Radicals......Page 108
Experimental Methods......Page 111
Absolute Rates......Page 113
Relative Rates......Page 115
Theoretical Treatment......Page 123
Model Calculations of Α-factors by Transition State Theory......Page 124
Molecular Orbital Treatment......Page 125
Literature Cited......Page 126
I. CF Radical Reactions......Page 129
II. CHF Radical Reactions......Page 133
III. CF2 Radical Reactions......Page 140
Literature Cited......Page 149
6 Ion-Molecule Reactions Involving Fluorine-Containing Organic Compounds......Page 153
Reactions in Perfluorinated Alkanes......Page 154
Reactions in Perfluorinated Olefins......Page 157
Reactions in Partially Fluorinated Ethylenes......Page 159
Reactions in Partially Fluorinated Alkanes......Page 162
Reactions of Fluorinated Ions with Other Organic Compounds......Page 168
Thermochemical Information about Fluorinated Species Derived from Ion-Molecule Reactions......Page 178
Literature Cited......Page 186
7 Crossed Molecular Beam Studies of Fluorine Chemistry......Page 189
Experimental Method......Page 190
Examples of Experimental Results......Page 195
II. Substitution Reactions of F Atoms with Unsaturated Hydrocarbons.......Page 197
III. Other Examples.......Page 209
Literature Cited......Page 217
8 Molecular Beam Studies with F+ Ions......Page 220
Experimental......Page 221
Charge Transfer Reaction F+(Ne,F)Ne+.......Page 222
Reaction of the F+ With Molecular Hydrogen.......Page 224
Dynamics of the Reaction F+(D2,D)FD+.......Page 228
Reaction of F+ with CH4.......Page 232
Literature Cited......Page 233
9 Energy Disposal in Reactions of Fluorine Atoms with Polyatomic Hydride Molecules as Studied by Infrared Chemiluminescence......Page 235
Basics of the Infrared Chemiluminescence Technique......Page 236
Vibrational Energy Disposal......Page 240
Models for Vibrational Energy Disposal......Page 243
Rotational Energy Disposal......Page 255
R-H Bond Dissociation Energies......Page 262
Energy Disposal with Excited Reagents......Page 264
Energy Disposal from Unimolecular Reactions......Page 265
Acknowledgments......Page 267
APPENDIX I, Radiative Transition Probabilities for HF......Page 268
Literature Cited......Page 274
10 Potential Energy Surfaces for Fluorine-Hydrogen Systems......Page 279
F + H2 → FH + H......Page 280
H + FH → HF + H......Page 284
H + F2 and F + HF......Page 285
Concluding Remarks......Page 287
Literature Cited......Page 290
11 Thermochemistry of Fluorocarbon Radicals......Page 292
Thermochemistry of Fluorocarbon Radicals......Page 293
Discussion......Page 304
Acknowledgement......Page 307
Literature Cited......Page 308
12 Chemistry of High Energy Atomic Fluorine: Steady State Kinetic Theory Model Calculations for the 18F + H2 Reaction III......Page 310
Background Theory.......Page 311
The Steady State Hot Atom Kinetic Theory.......Page 314
Steady State Theory Model Calculations.......Page 319
The Pure H2 Reaction System.......Page 321
Moderated H2 Reaction Systems.......Page 329
H. Literature Cited.......Page 339
13 Electron Spin Resonance Studies of Fluorine-Containing Radicals in Single Organic Crystals......Page 343
Molecular Dynamics......Page 351
Mechanism of Radical Formation......Page 366
Literature Cited......Page 377
14 ESR Spectra and Structure of Inorganic Fluorine-Containing Free Radicals (1)......Page 380
Analysis of ESR Spectra......Page 381
Predicting Hyperfine Interactions......Page 386
Semi-occupied Orbital of Inorganic Fluorine Radicals......Page 388
Preparation of Inorganic Fluorine-Containing Radicals......Page 389
Tri-coordinated Fluoride Radicals......Page 391
Tetra-coordinated Fluoride Radicals......Page 392
Penta-coordinated Fluoride Radicals......Page 396
Hexafluoride Radicals......Page 399
Literature Cited......Page 401
Acknowledgments......Page 403
A......Page 404
C......Page 405
E......Page 407
F......Page 408
H......Page 409
I......Page 410
N......Page 411
Q......Page 412
R......Page 413
T......Page 414
V......Page 415
Z......Page 416