Phosgene: And Related Carbonyl Halides (Topics in Inorganic and General Chemistry)

Phosgene, COCl 2 is a C 1 chemical of major industrial importance. The annual production, worldwide, is more than 1 million tons; 90% of which is used in the manufacture of isocyanates and of polyurethane and polycarbonate resins. Phosgene is also extensively used as a synthetic reagent in organic chemistry, in particular in the preparation of acyl chlorides, chloroformate esters, organic carbonates and carbamoyl chlorides. Although more than 7000 papers have appeared on phosgene and some 1000 papers on its analogues, this is the first book on these interesting chemicals. It presents a critical treatise of phosgene, ranging from its discovery and subsequent use as a war gas to some potential applications of the material into the 21st century. It includes chapters on biological effects and industrial hygiene; on synthesis, formation and manufacture; analysis, uses, environmental effects, and physical and thermodynamic properties. Reactions with organic and inorganic materials are described. Four of the seventeen chapters are devoted to a description of the carbonyl halides (especially carbonyl difluoride) related to phosgene, and a special section deals collectively with the electronic structures of carbonyl halide molecules. Featuring the first-ever comprehensive discussion of the medical effects of phosgene poisoning and the most modern methods of treating exposure victims, the book will be of interest to historians and militarists and those working in the chemical industries (heavy chemicals, agricultural and pharmaceutical), university libraries, hospitals, medical research centres, museums, environmental research centres, poison units and health and safety institutions world-wide. PHOSGENE AND RELATED CARBONYL HALIDES......Page 4 Copyright Page......Page 5 FOREWORD......Page 10 PREFACE......Page 12 ABBREVIATIONS......Page 18 CONVERSION FACTORS......Page 28 PHOSGENE and related carbonyl halides......Page 29 CONTENTS......Page 30 1.1 PHOTOGENESIS......Page 50 1.2 QUIESCENCE......Page 59 1.3 THE STORM APPROACHETH......Page 60 1.4 REFINEMENTS OF EVIL......Page 63 1.5 THE STATISTICS OF DEATH......Page 82 1.6 THE ART OF WAR......Page 87 1.7 PHOSGENE AND WORLD WAR II......Page 107 1.8 PHOSGENE AND MODERN WARFARE......Page 109 1.9 PHOSGENE AND THE MODERN WORLD......Page 110 1.10 THE KRAKEN WAKES......Page 117 1.11 ACCURACY AND THE PRESS......Page 118 1.12 WHY THIS BOOK?......Page 119 2.1 SYMPTOMS OF PHOSGENE POISONING......Page 120 2.2 LUNG STRUCTURE AND FUNCTION......Page 122 2.3 EFFECTS OF PHOSGENE ON THE RESPIRATORY SYSTEM......Page 124 2.4 MEASUREMENT OF EXPOSURE DOSE......Page 125 2.5 ANIMAL EXPERIMENTS......Page 127 2.6 TREATMENT OF PHOSGENE POISONING......Page 136 2.7 PHOSGENE AS A PESTICIDE......Page 143 2.8 THE EFFECTS OF PHOSGENE ON PLANTS, SOILS AND FOODSTUFFS......Page 145 3.1 INDUSTRIAL HYGIENE......Page 148 3.2 ANALYTICAL METHODS FOR THE DETERMINATION OF PHOSGENE......Page 165 3.3 SOURCES OF PHOSGENE EMISSION......Page 179 3.4 TREATMENT OF LIQUID PHOSGENE SPILLAGES......Page 196 3.5 CASE REPORTS OF PHOSGENE POISONING......Page 198 3.6 CATASTROPHIC EMISSIONS......Page 200 3.7 ENVIRONMENTAL CONSIDERATIONS......Page 208 4.1 INDUSTRIAL MANUFACTURE......Page 214 4.3 STORAGE......Page 222 4.4 TREATMENT OF PHOSGENE EFFLUENTS......Page 223 4.5 ENGINEERING PRACTICES......Page 229 4.6 ASSAYING......Page 235 4.7 INDUSTRIAL USES......Page 239 CHAPTER 5. SYNTHESIS AND FORMATION OF PHOSGENE......Page 270 5.1 SYNTHESIS OF PHOSGENE FROM CARBON MONOXIDE......Page 271 5.2 SYNTHESIS OF PHOSGENE FROM HALOGENATED HYDROCARBONS......Page 290 5.3 SYNTHESIS OF PHOSGENE FROM CARBONACEOUS MATERIALS......Page 305 5.4 SYNTHESIS OF PHOSGENE FROM CARBON DIOXIDE, CARBONYL SULFIDE OR CARBON DISULFIDE......Page 306 5.6 SYNTHESIS OF PHOSGENE FROM OXYGENATES (OXYGEN-CONTAINING ORGANIC COMPOUNDS)......Page 307 5.8 SYNTHESIS OF LABELLED PHOSGENE......Page 311 6.1 THERMOCHEMICAL PROPERTIES......Page 314 6.2 THERMAL PROPERTIES......Page 324 6.3 MECHANICAL PROPERTIES......Page 328 6.5 ELECTRICAL AND MAGNETIC PROPERTIES......Page 334 6.6 SOLUBILITY AND VAPOUR-LIQUID EQUILIBRIA......Page 336 7.1 STRUCTURAL DETERMINATIONS......Page 356 7.2 VIBRATIONAL SPECTROSCOPY......Page 358 7.3 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY......Page 362 7.4 NUCLEAR QUADRUPOLE RESONANCE SPECTROSCOPY......Page 367 7.5 MASS SPECTROMETRY......Page 368 8.1 DISSOCIATION OF PHOSGENE......Page 370 8.2 DISMUTATION OF PHOSGENE......Page 377 8.3 PHOTOCHEMISTRY OF PHOSGENE......Page 383 9.1 MAIN GROUP HALIDES AND OXIDE HALIDES......Page 388 9.2 TRANSITION METAL HALIDES AND OXIDE HALIDES......Page 405 9.3 LANTHANIDE AND ACTINIDE HALIDES AND OXIDE HALIDES......Page 410 9.4 MAIN GROUP OXIDES AND SULFIDES......Page 412 9.5 TRANSITION METAL OXIDES AND SULFIDES......Page 420 9.6 LANTHANIDE AND ACTINIDE OXIDES......Page 425 9.7 MAIN GROUP ELEMENTS......Page 428 9.8 TRANSITION ELEMENTS AND ACTINIDES......Page 434 9.9 ORGANOMETALLICS......Page 436 9.10 HYDRIDE DERIVATIVES......Page 442 9.11 AMIDES......Page 447 9.12 MISCELLANEOUS REACTIONS......Page 448 9.13 PHOSGENITE......Page 451 CHAPTER 10. REACTIONS WITH ORGANIC COMPOUNDS......Page 458 10.1 REACTIONS WITH HYDROCARBONS......Page 459 10.2 REACTIONS WITH NITROGEN COMPOUNDS......Page 468 10.3 REACTIONS WITH OXYGEN COMPOUNDS......Page 511 10.4 REACTIONS WITH ORGANOSILICON COMPOUNDS......Page 543 10.5 REACTIONS WITH ORGANOPHOSPHORUS AND RELATED COMPOUNDS......Page 556 10.6 REACTIONS WITH ORGANOSULFUR COMPOUNDS......Page 562 10.7 POLYMER CHEMISTRY......Page 571 10.8 SYNTHESIS OF RADIOLABELLED COMPOUNDS......Page 573 11.2 CONDUCTIVITY OF LIQUID PHOSGENE......Page 578 11.3 PHOSGENE AS A NON-AQUEOUS SOLVENT......Page 579 12.1 PHOSGENE SUBSTITUTES......Page 582 12.2 HOMOLOGUES......Page 587 13.1 BIOLOGICAL ACTIVITY OF CARBONYL DIFLUORIDE......Page 592 13.2 INDUSTRIAL HYGIENE......Page 597 13.3 ANALYTICAL METHODS FOR THE DETERMINATION OF CARBONYL DIFLUORIDE......Page 600 13.5 ENVIRONMENTAL CONSIDERATIONS......Page 602 13.6 POTENTIAL USES OF CARBONYL DIFLUORIDE......Page 603 13.7 SYNTHESIS AND FORMATION OF CARBONYL DIFLUORIDE......Page 605 13.8 THERMODYNAMIC AND PHYSICAL PROPERTIES......Page 644 13.9 STRUCTURAL DETERMINATIONS......Page 660 13.10 SPECTROSCOPY......Page 661 13.11 THERMAL DECOMPOSITION......Page 665 13.12 PHOTOCHEMICAL DECOMPOSITION......Page 667 13.13 REACTIONS WITH INORGANIC COMPOUNDS......Page 668 13.14 REACTIONS WITH ORGANIC COMPOUNDS......Page 688 14.2 ENVIRONMENTAL HAZARDS......Page 712 14.3 FORMATION......Page 713 14.4 THERMODYNAMIC AND PHYSICAL PROPERTIES......Page 714 14.5 STRUCTURAL AND SPECTROSCOPIC PROPERTIES......Page 718 14.6 REACTIONS WITH INORGANIC COMPOUNDS......Page 720 14.7 REACTIONS WITH ORGANIC COMPOUNDS......Page 722 15.1 EVIDENCE FOR THE PRESENCE OF CARBONYL DIIODIDE IN THE ESSENTIAL OIL OF Asparagopsis taxiformis......Page 726 15.2 ATTEMPTED SYNTHESES OF CARBONYL DIIODIDE......Page 727 15.3 ESTIMATED PHYSICAL AND THERMODYNAMIC PROPERTIES FOR CARBONYL DIIODIDE......Page 728 CHAPTER 16. ASYMMETRIC CARBONYL HALIDES......Page 732 16.1 CARBONYL CHLORIDE FLUORIDE......Page 733 16.2 CARBONYL BROMIDE FLUORIDE......Page 770 16.3 CARBONYL BROMIDE CHLORIDE......Page 781 16.4 CARBONYL FLUORIDE IODIDE......Page 785 16.5 CARBONYL CHLORIDE IODIDE......Page 787 16.6 CARBONYL BROMIDE IODIDE......Page 788 17.1 THEORETICAL DESCRIPTIONS OF THE ELECTRONIC STRUCTURE OF THE CARBONYL HALIDES......Page 792 17.2 PHOTOELECTRON STUDIES......Page 807 17.3 ELECTRONIC ABSORPTION......Page 823 17.4 FLUORESCENCE......Page 829 17.5 PHOSPHORESCENCE......Page 830 17.6 REACTIVITY PATTERNS......Page 831 REFERENCES......Page 834 I.C.I. REPORTS......Page 904 APPENDICES......Page 910 A1 PHOSGENE: INDUSTRIAL OUTPUT......Page 912 A2 CARBONYL HALIDES: SUPPLIERS OF RESEARCH QUANTITIES......Page 916 A3 REGISTRY NUMBERS AND SYNONYMS......Page 918 A4 CHARACTER TABLES (C2v and Cs)......Page 922 A5 LABORATORY PREPARATIONS OF THE CARBONYL HALIDES......Page 924 INDEX......Page 928 Phosgene, COCl 2 is a C 1 chemical of major industrial importance. The annual production, worldwide, is more than 1 million tons; 90% of which is used in the manufacture of isocyanates and of polyurethane and polycarbonate resins. Phosgene is also extensively used as a synthetic reagent in organic chemistry, in particular in the preparation of acyl chlorides, chloroformate esters, organic carbonates and carbamoyl chlorides. Although more than 7000 papers have appeared on phosgene and some 1000 papers on its analogues, this is the first book on these interesting chemicals. It presents a critical treatise of phosgene, ranging from its discovery and subsequent use as a war gas to some potential applications of the material into the 21st century. It includes chapters on biological effects and industrial hygiene; on synthesis, formation and manufacture; analysis, uses, environmental effects, and physical and thermodynamic properties. Reactions with organic and inorganic materials are described. Four of the seventeen chapters are devoted to a description of the carbonyl halides (especially carbonyl difluoride) related to phosgene, and a special section deals collectively with the electronic structures of carbonyl halide molecules. Featuring the first-ever comprehensive discussion of the medical effects of phosgene poisoning and the most modern methods of treating exposure victims, the book will be of interest to historians and militarists and those working in the chemical industries (heavy chemicals, agricultural and pharmaceutical), university libraries, hospitals, medical research centres, museums, environmental research centres, poison units and health and safety institutions world-wide