Phosgene (eBook)

Front Cover 1
PHOSGENE AND RELATED CARBONYL HALIDES 4
Copyright Page 5
CONTENTS 30
CHAPTER 1. HISTORY OF PHOSGENE 50
1.1 PHOTOGENESIS 50
1.2 QUIESCENCE 59
1.3 THE STORM APPROACHETH 60
1.4 REFINEMENTS OF EVIL 63
1.5 THE STATISTICS OF DEATH 82
1.6 THE ART OF WAR 87
1.7 PHOSGENE AND WORLD WAR II 107
1.8 PHOSGENE AND MODERN WARFARE 109
1.9 PHOSGENE AND THE MODERN WORLD 110
1.10 THE KRAKEN WAKES 117
1.11 ACCURACY AND THE PRESS 118
1.12 WHY THIS BOOK? 119
CHAPTER 2. BIOLOGICAL ACTIVITY OF PHOSGENE 120
2.1 SYMPTOMS OF PHOSGENE POISONING 120
2.2 LUNG STRUCTURE AND FUNCTION 122
2.3 EFFECTS OF PHOSGENE ON THE RESPIRATORY SYSTEM 124
2.4 MEASUREMENT OF EXPOSURE DOSE 125
2.5 ANIMAL EXPERIMENTS 127
2.6 TREATMENT OF PHOSGENE POISONING 136
2.7 PHOSGENE AS A PESTICIDE 143
2.8 THE EFFECTS OF PHOSGENE ON PLANTS, SOILS AND FOODSTUFFS 145
CHAPTER 3. INDUSTRIAL HYGIENE, ANALYTICAL METHODS AND ENVIRONMENTAL ISSUES 148
3.1 INDUSTRIAL HYGIENE 148
3.2 ANALYTICAL METHODS FOR THE DETERMINATION OF PHOSGENE 165
3.3 SOURCES OF PHOSGENE EMISSION 179
3.4 TREATMENT OF LIQUID PHOSGENE SPILLAGES 196
3.5 CASE REPORTS OF PHOSGENE POISONING 198
3.6 CATASTROPHIC EMISSIONS 200
3.7 ENVIRONMENTAL CONSIDERATIONS 208
CHAPTER 4. INDUSTRIAL MANUFACTURE AND USES 214
4.1 INDUSTRIAL MANUFACTURE 214
4.2 PURIFICATION OF COMMERCIAL PHOSGENE 222
4.3 STORAGE 222
4.4 TREATMENT OF PHOSGENE EFFLUENTS 223
4.5 ENGINEERING PRACTICES 229
4.6 ASSAYING 235
4.7 INDUSTRIAL USES 239
CHAPTER 5. SYNTHESIS AND FORMATION OF PHOSGENE 270
5.1 SYNTHESIS OF PHOSGENE FROM CARBON MONOXIDE 271
5.2 SYNTHESIS OF PHOSGENE FROM HALOGENATED HYDROCARBONS 290
5.3 SYNTHESIS OF PHOSGENE FROM CARBONACEOUS MATERIALS 305
5.4 SYNTHESIS OF PHOSGENE FROM CARBON DIOXIDE, CARBONYL SULFIDE OR CARBON DISULFIDE 306
5.5 SYNTHESIS OF PHOSGENE FROM OTHER CARBONYL HALIDES 307
5.6 SYNTHESIS OF PHOSGENE FROM OXYGENATES (OXYGEN-CONTAINING ORGANIC COMPOUNDS) 307
5.7 SYNTHESIS OF PHOSGENE BY MISCELLANEOUS METHODS 311
5.8 SYNTHESIS OF LABELLED PHOSGENE 311
CHAPTER 6. THERMODYNAMIC AND PHYSICAL PROPERTIES 314
6.1 THERMOCHEMICAL PROPERTIES 314
6.2 THERMAL PROPERTIES 324
6.3 MECHANICAL PROPERTIES 328
6.4 OPTICAL PROPERTIES 334
6.5 ELECTRICAL AND MAGNETIC PROPERTIES 334
6.6 SOLUBILITY AND VAPOUR-LIQUID EQUILIBRIA 336
CHAPTER 7. STRUCTURAL AND SPECTROSCOPIC PROPERTIES 356
7.1 STRUCTURAL DETERMINATIONS 356
7.2 VIBRATIONAL SPECTROSCOPY 358
7.3 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 362
7.4 NUCLEAR QUADRUPOLE RESONANCE SPECTROSCOPY 367
7.5 MASS SPECTROMETRY 368
CHAPTER 8. DISSOCIATION, DISMUTATION AND PHOTOCHEMISTRY OF PHOSGENE 370
8.1 DISSOCIATION OF PHOSGENE 370
8.2 DISMUTATION OF PHOSGENE 377
8.3 PHOTOCHEMISTRY OF PHOSGENE 383
CHAPTER 9. REACTIONS WITH INORGANIC COMPOUNDS 388
9.1 MAIN GROUP HALIDES AND OXIDE HALIDES 388
9.2 TRANSITION METAL HALIDES AND OXIDE HALIDES 405
9.3 LANTHANIDE AND ACTINIDE HALIDES AND OXIDE HALIDES 410
9.4 MAIN GROUP OXIDES AND SULFIDES 412
9.5 TRANSITION METAL OXIDES AND SULFIDES 420
9.6 LANTHANIDE AND ACTINIDE OXIDES 425
9.7 MAIN GROUP ELEMENTS 428
9.8 TRANSITION ELEMENTS AND ACTINIDES 434
9.9 ORGANOMETALLICS 436
9.10 HYDRIDE DERIVATIVES 442
9.11 AMIDES 447
9.12 MISCELLANEOUS REACTIONS 448
9.13 PHOSGENITE 451
CHAPTER 10. REACTIONS WITH ORGANIC COMPOUNDS 458
10.1 REACTIONS WITH HYDROCARBONS 459
10.2 REACTIONS WITH NITROGEN COMPOUNDS 468
10.3 REACTIONS WITH OXYGEN COMPOUNDS 511
10.4 REACTIONS WITH ORGANOSILICON COMPOUNDS 543
10.5 REACTIONS WITH ORGANOPHOSPHORUS AND RELATED COMPOUNDS 556
10.6 REACTIONS WITH ORGANOSULFUR COMPOUNDS 562
10.7 POLYMER CHEMISTRY 571
10.8 SYNTHESIS OF RADIOLABELLED COMPOUNDS 573
CHAPTER 11. PHOSGENE AS A NON-AQUEOUS SOLVENT 578
11.1 PHYSICAL PROPERTIES OF LIQUID PHOSGENE 578
11.2 CONDUCTIVITY OF LIQUID PHOSGENE 578
11.3 PHOSGENE AS A NON-AQUEOUS SOLVENT 579
CHAPTER 12. PHOSGENE SUBSTITUTES AND HOMOLOGUES 582
12.1 PHOSGENE SUBSTITUTES 582
12.2 HOMOLOGUES 587
CHAPTER 13. CARBONYL DIFLUORIDE 592
13.1 BIOLOGICAL ACTIVITY OF CARBONYL DIFLUORIDE 592
13.2 INDUSTRIAL HYGIENE 597
13.3 ANALYTICAL METHODS FOR THE DETERMINATION OF CARBONYL DIFLUORIDE 600
13.4 TYPICAL ASSAY OF COMMERCIAL CARBONYL DIFLUORIDE 602
13.5 ENVIRONMENTAL CONSIDERATIONS 602
13.6 POTENTIAL USES OF CARBONYL DIFLUORIDE 603
13.7 SYNTHESIS AND FORMATION OF CARBONYL DIFLUORIDE 605
13.8 THERMODYNAMIC AND PHYSICAL PROPERTIES 644
13.9 STRUCTURAL DETERMINATIONS 660
13.10 SPECTROSCOPY 661
13.11 THERMAL DECOMPOSITION 665
13.12 PHOTOCHEMICAL DECOMPOSITION 667
13.13 REACTIONS WITH INORGANIC COMPOUNDS 668
13.14 REACTIONS WITH ORGANIC COMPOUNDS 688
CHAPTER 14. CARBONYL DIBROMIDE 712
14.1 BIOLOGICAL ACTIVITY 712
14.2 ENVIRONMENTAL HAZARDS 712
14.3 FORMATION 713
14.4 THERMODYNAMIC AND PHYSICAL PROPERTIES 714
14.5 STRUCTURAL AND SPECTROSCOPIC PROPERTIES 718
14.6 REACTIONS WITH INORGANIC COMPOUNDS 720
14.7 REACTIONS WITH ORGANIC COMPOUNDS 722
CHAPTER 15. CARBONYL DIIODIDE 726
15.1 EVIDENCE FOR THE PRESENCE OF CARBONYL DIIODIDE IN THE ESSENTIAL OIL OF Asparagopsis taxiformis 726
15.2 ATTEMPTED SYNTHESES OF CARBONYL DIIODIDE 727
15.3 ESTIMATED PHYSICAL AND THERMODYNAMIC PROPERTIES FOR CARBONYL DIIODIDE 728
CHAPTER 16. ASYMMETRIC CARBONYL HALIDES 732
16.1 CARBONYL CHLORIDE FLUORIDE 733
16.2 CARBONYL BROMIDE FLUORIDE 770
16.3 CARBONYL BROMIDE CHLORIDE 781
16.4 CARBONYL FLUORIDE IODIDE 785
16.5 CARBONYL CHLORIDE IODIDE 787
16.6 CARBONYL BROMIDE IODIDE 788
CHAPTER 17. ELECTRONIC STRUCTURE OF THE CARBONYL HALIDES 792
17.1 THEORETICAL DESCRIPTIONS OF THE ELECTRONIC STRUCTURE OF THE CARBONYL HALIDES 792
17.2 PHOTOELECTRON STUDIES 807
17.3 ELECTRONIC ABSORPTION 823
17.4 FLUORESCENCE 829
17.5 PHOSPHORESCENCE 830
17.6 REACTIVITY PATTERNS 831
REFERENCES 834
I.C.I. REPORTS 904
APPENDICES 910
A1 PHOSGENE: INDUSTRIAL OUTPUT 912
A2 CARBONYL HALIDES: SUPPLIERS OF RESEARCH QUANTITIES 916
A3 REGISTRY NUMBERS AND SYNONYMS 918
A4 CHARACTER TABLES (C2v and Cs) 922
A5 LABORATORY PREPARATIONS OF THE CARBONYL HALIDES 924
INDEX 930