Pyrolysis of Organic Molecules (eBook)

Front cover 1
Pyrolysis of Organic Molecules with Applications to Health and Environmental Issues 4
Copyright page 5
Preface 6
Contents 8
Part 1. Organic Non-Polymeric Molecules: Fundamental Concepts of Pyrolysis, Risk Assessment, and Toxicology 14
Chapter 1. Introduction 16
1.1. Preliminary Information on Pyrolysis 16
1.2. Preliminary information on risk assessment and toxicology 18
1.3. References 19
Chapter 2. The Chemistry of the Pyrolytic Process 20
2.1. Basic characteristics of pyrolytic reactions 20
2.2. Elimination Reactions 21
2.3. Fragmentation and extrusion reactions 33
2.4. Rearrangement reactions 40
2.5. Other reaction types in pyrolysis 48
2.6. Pyrolysis in the presence of additional reactants or with catalysts 52
2.7. Pyrolysis of mixtures of compounds 58
2.8. References 60
Chapter 3. Physicochemical Aspects of the Pyrolytic Process 62
3.1. Thermodynamic factors in pyrolytic reactions 62
3.2. Kinetic factors in pyrolytic reactions 80
3.3. References 89
Chapter 4. Instrumentation Used in Pyrolysis 92
4.1. Optimization of the pyrolytic process for a specific goal 92
4.2. Instrumentation used in analytical pyrolysis 96
4.3. Instrumentation used in laboratory pyrolysis for synthesis purpose 107
4.4. Instrumentation used to simulate a specific pyrolytic process 109
4.5. Standardization of analytical pyrolysis techniques 110
4.6. Conditions for pyrolysis experiments in this book 112
4.7. References 115
Chapter 5. Basic Concepts Regarding Risk Assessment and Toxicology 118
5.1. Risk assessment principles 118
5.2. Toxicology principles 119
5.3. References 123
Chapter 6. The Utility of Pyrolysis Studies 124
6.1. Information from analytical pyrolysis 124
6.2. The use of pyrolysis in organic synthesis 128
6.3. Industrial and laboratory applications of pyrolysis in various processes related to burning 131
6.4. Applications of pyrolysis in forensic science 135
6.5. References 137
Part 2. Pyrolysis Products of Organic Non-Polymeric Molecules 142
Chapter 7. Pyrolysis of Hydrocarbons 144
7.1. Acyclic saturated hydrocarbons 144
7.2. Cyclic saturated hydrocarbons 174
7.3. Alkenes 182
7.4. Alkadienes and polyenes 195
7.5. Cycloalkenes 203
7.6. Alkynes 213
7.7. Aromatic hydrocarbons 217
7.8. Formation of polycyclic aromatic hydrocarbons during pyrolysis and combustion of hydrocarbons 228
7.9. References 235
Chapter 8. Pyrolysis of Halogenated Hydrocarbons 244
8.1. Chlorinated aliphatic hydrocarbons 244
8.2. Aliphatic hydrocarbons substituted with other halogens 257
8.3. Halogenated aromatic hydrocarbons 265
8.4. References 270
Chapter 9. Pyrolysis of Alcohols and Phenols 272
9.1. Alcohols 272
9.2. Enols 307
9.3. Phenols 307
9.4. Di- and poly-hydroxybenzenes 311
9.5. Alcohols and phenols with additional functional groups 319
9.6. References 324
Chapter 10. Pyrolysis of Ethers 328
10.1. Aliphatic ethers 328
10.2. Unsaturated ethers 332
10.3. Aromatic ethers 332
10.4. Ethers with one alkyl and one aryl substituent 335
10.5. Epoxides and larger cyclic ethers 342
10.6. Acetals and hemiacetals 349
10.7. References 350
Chapter 11. Pyrolysis of Peroxy Compounds 352
11.1. Hydroperoxides 352
11.2. Peroxides 353
11.3. Ozonides 355
11.4. Acyl peroxides 355
11.5. References 356
Chapter 12. Pyrolysis of Thiols and Sulfides 358
12.1. Thiols 358
12.2. Sulfides 359
12.3. Disulfides 360
12.4. References 360
Chapter 13. Pyrolysis of Amines and Imines 362
13.1. Primary amines 362
13.2. Secondary and tertiary amines 364
13.3. Salts of amines 368
13.4. Quaternary ammonium hydroxides and salts 370
13.5. Amines containing other functional groups 373
13.6. Imines 375
13.7. References 376
Chapter 14. Pyrolysis of Other Nitrogen Containing Compounds 378
14.1. Nitro and nitroso compounds 378
14.2. Hydroxylamines, oxyamines, and N-alkoxyammonium hydroxide derivatives 386
14.3. Oximes and oxime derivatives 387
14.4. Amine N-oxides and nitrones 393
14.5. Hydrazines and hydrazones 394
14.6. Azo, diazo, and azoxy derivatives 399
14.7. Azides 405
14.8. References 406
Chapter 15. Pyrolysis of Aldehydes and Ketones 410
15.1. Aldehydes 410
15.2. Ketones 421
15.3. Ketenes 427
15.4. Thioaldehydes and thioketones 429
15.5. References 430
Chapter 16. Pyrolysis of Carbohydrates 432
16.1. Monosaccharides 432
16.2. Disaccharides 455
16.3. Carbohydrates with additional functional groups 460
16.4. References 482
Chapter 17. Pyrolysis of Carboxylic Acids 484
17.1. Monocarboxylic acids 484
17.2. Di- and polycarboxylic acids 495
17.3. Hydroxy acids 503
17.4. Carboxylic acids with other additional functionalities or groups 522
17.5. Salts of carboxylic acids 531
17.6. Thio acids 538
17.7. References 538
Chapter 18. Pyrolysis of Amino Acids and Small Peptides 540
18.1. Amino acids 540
18.2. Betaines 585
18.3. Small peptides 586
18.4. References 590
Chapter 19. Pyrolysis of Various Derivatives of Carboxylic Acids 592
19.1. Organic acid esters 592
19.2. Inorganic esters 608
19.3. Lactones 614
19.4. Organic acid anhydrides 620
19.5. Acyl chlorides 622
19.6. Amides and imides 624
19.7. Lactams 631
19.8. Hydroxamic acids and hydrazides 631
19.9. Nitriles and isocyanides 633
19.10. Thioesters and thioamides 635
19.11. References 637
Chapter 20. Pyrolysis of Derivatives of Carbonic Acid with Nitrogenous Functionalities 642
20.1. Amides of carbonic acid (carbamates and ureas) 642
20.2. Guanidine and related compounds 653
20.3. Hydrazides of carbonic acid 653
20.4. Nitriles of carbonic acid (cyanates and isocyanates) 654
20.5. References 655
Chapter 21. Pyrolysis of Aromatic Heterocyclic Compounds 656
21.1. Aromatic heterocycles containing oxygen 656
21.2. Aromatic heterocycles containing nitrogen 663
21.3. Aromatic heterocycles containing sulfur 682
21.4. Aromatic heterocycles containing different heteroatoms 685
21.5. References 687
Chapter 22. Pyrolysis of Other Compounds with Heteroatoms 690
22.1. Boron-containing compounds 690
22.2. Silicon-containing compounds 690
22.3. Phosphorus and arsenic-containing compounds 693
22.4. Sulfur-containing compounds 697
22.5. Organometallic molecules and compounds of other elements 699
22.6. References 701
Part 3. Elements of Toxicology for Selected Classes of Pyrolysis Products 704
Chapter 23. Toxicological and Environmental Aspects of Polycyclic Aromatic Hydrocarbons (PAHs) and Related Compounds 706
23.1. PAHs with two condensed cycles 706
23.2. PAHs with more than two cycles 706
23.3. PAHs with additional functionalities 711
23.4. References 711
Chapter 24. Toxicological and Environmental Aspects of Dioxin-Like Compounds 714
24.1. Halogenated Aromatc hydrocarbons (PCBs and PBBs) 714
24.2. Halogenated dibenzo-p-dioxins and dibenzofurans 717
24.3. References 719
Chapter 25. Toxicological Aspects of Aromatic Heterocyclic Amines 720
25.1. Heterocyclic aromatic amines 720
25.2. References 722
Index 724