Sulfur (eBook)

Front Cover 1
Sulfer: Its Significance for Chemistry, for the Geo-, Bio- and Cosmosphere and Technology 4
Copyright Page 5
Table of Contets 10
Preface 6
Contributors 8
PART I: SULFUR: THE ELEMENT, ITS GEOCHEMISTRY AND SOME ASPECTS OF ITS HISTORY 16
CHAPTER 1. ELEMENTAL SULFUR AND RELATED HOMOCYCLIC COMPOUNDS AND IONS 18
1 . Introduction 19
2. Elemental Sulfur (Neutral Rings Sn) 20
3. Homocyclic Sulfur Cations 36
4. Homocyclic Sulfur Oxides 41
5. Homocyclic Sulfur Halide Cations 46
References 48
CHAPTER 2. SULFUR IN THE EARTH'S CRUST, ITS ORIGIN AND NATURAL CYCLE 54
1. Cosmic and Terrestrial Abundance of Sulfur 54
2. Sulfur Cycle in the Continental Crust 57
3. Sulfur Cycle in the Oceanic Crust 60
4. Isotopic Composition of Natural Sulfur 63
5. Sulfur in the Water Cycle at the Earth's Surface 67
References 68
CHAPTER 3. SULFUR IN HISTORY: THE ROLE OF SULFUR IN "BLACK POWDER" 70
1. Gunpowder - A Chinese Invention? 70
2. Technology of Black Powder in the European Middle Ages 73
3. The Composition of Black Powder and the Reaction of Its Components 74
4. The Role of Sulfur in Black Powder 75
References 81
CHAPTER 4. SULFUR IN ARTWORK: LAPIS LAZULI AND ULTRAMARINE PIGMENTS 82
1 . A Five-Thousand Years Old Pigment 82
2. The Synthesis of Ultramarine 85
3. Structure Analysis of Lapis Lazuli and of the Ultramarine Pigments 86
4. Blue Sulfur? 90
5. The Chromophores in Ultramarine-Yellow, -Green, -Violet and -Red 95
6. Chemical Behaviour of the Sulfur Species in Lapis Lazuli and in the Ultramarine Pigments 99
7. Concluding Remarks 103
Acknowledgements 103
References 103
PART II: CHEMISTRY 106
CHAPTER 5. NEW DEVELOPMENTS IN THE FIELD OF ORGANIC SULFUR CHEMISTRY 108
1 . Introduction 108
2. New Structures and New Methods for Understanding Structures 109
3. New Ideas on and New Applications of Reactions of Organosulfur Compounds 117
4. Sulfur-Containing Natural Products and Biologically Active Sulfur Compounds 131
References 134
CHAPTER 6. ORGANOMETALLIC SULFUR COMPOUNDS 136
1 . Introduction 136
2. Structural Types 137
3. Stabilisation Principles and Synthetic Approaches 139
4. Reactivity of M-SH Complexes 141
5. The M3S Electron Reservoir 144
6. Framework Reactions of Sulfur Bridged Organometallic Clusters 148
Acknowledgements 152
References 153
CHAPTER 7. THIOLATES – INTRIGUING AND VERSATILE LIGANDS FOR TRANSITION METALS 156
1 . Introduction 156
2. Mononuclear Complexes with Monodentate Thiols 157
3. Polynuclear Thiolato-Complexes 162
4. Sulfide Formation by C-S Bond Cleavage 168
5. Polydentate Thiolato-Ligands Sulfur-Sulfur Interactions
6. Redox Reactions and the Electrochemistry of Thiolato-Complexes 174
7. Sterically Hindered Thiolato-Ligands 176
8. Conclusion 178
References 178
CHAPTER 8. METAL COMPLEXES OF SULFUR AND SULFUR-NITROGEN COMPOUNDS AND THEIR CATALYTIC PROPERTIES 182
1 . Introduction 182
2. Elemental Sulfur as a Ligand 183
3. Complexes with (CH2S)3, (CH2Se)3 and (CH20)6 184
4. Sulfur-Nitrogen Species as Ligands 186
5. Metal-Catalyzed Formation of S(CN)4 193
Acknowledgements 194
References 194
CHAPTER 9. SULFIDO-COMPLEXES OF MOLYBDENUM AND TUNGSTEN: SYNTHETIC ASPECTS 196
1 . Introduction 196
2. Simple Thiometallate Anions and Their Reactions 197
3. Thiometallates as Ligands 200
4. Reactions of Thiometallates in the Presence of Thiolates 202
5. Mononuclear Complexes 204
References 207
CHAPTER 10. INTERACTION BETWEEN METAL CENTERS THROUGH SULFUR CONTAINING LIGANDS 210
1 . Introduction 210
2. Theoretical Background 211
3. Large Interaction between Copper(II) Ions Far Away from Each Other 216
4. Dithiooxamidato Copper(II) Dinuclear Complexes 219
5. Ab Initio Calculation of the Exchange Interaction in Dithiooxamide Complexes 225
6. Ordered Bimetallic Chains with Dithiooxalato Bridges 226
7. Magnetic Properties of Iron-Sulfur Complexes 228
8. Conclusion 233
References 234
CHAPTER 11. SPECTROSCOPIC ASPECTS OF SULFUR CHEMISTRY: ELECTRONIC AND RESONANCE RAMAN SPECTROSCOPY OF SULFUR-CONTAINING COMPLEXES, IONS AND RADICALS 236
1 . Introduction 236
2. Transition Metal Thiometal1ates 238
3. Electronic and RR Spectra of Sulfur-Donor Complexes 240
4. Spectroscopic Studies on Cations 243
5. Spectroscopic Studies on Sulfur Radical Anions 245
6. Conclusion 248
References 248
PART III: TECHNOLOGY AND CHEMISTRY WITH TECHNOLOGICAL RELEVANCE 250
CHAPTER 12. SULFURIC ACID – AN IMPORTANT BASIC PRODUCT IN CHEMISTRY. PROBLEMS AND RECENT DEVELOPMENTS IN PRODUCTION 252
1 . Introduction 252
2. Acid Manufacture and Reduction of Emissions 254
3. Raw Materials 258
4. Energy Recovery 260
5. Recycling of Spent Acids and By-Products 263
CHAPTER 13. CHEMICAL PROBLEMS OF FLUE-GAS DESULFURISATION 274
1. Introduction 274
2. Chemistry of Sulfur 275
3. The Problem of Changing Oxidation States of Sulfur 285
4. Proposal for a Sulfur Producing Desulfurisation Process 290
References 291
CHAPTER 14. METAL SULFIDES IN PHOTOVOLTAIC, PHOTOELECTROCHEMICAL AND SOLAR BIOLOGICAL ENERGY CONVERSION 292
1. Introduction 293
2. Sulfur Compounds as Solar Energy Materials 294
3. Photovoltaic Cells Based on Sulfides 304
4. Photoelectrochemical Cells Based on Sulfides 306
5. Solar Assisted Electrolysis of Water 309
6. Photocatalysis and Solar Intercalation Chemistry 314
7. Solar Biomass Based on Sulfur Cycle 318
8. Stability and Reactivity of Sulfide Materials 320
9. Conclusion 322
References 322
CHAPTER 15. INORGANIC CHEMISTRY RELATED TO RUBBER VULCANISATION 326
1 . Introduction 326
2. Mechanism of Sulfur Vulcanisation 328
CHAPTER 16. BIODEGRADATION OF SULFUR MINERALS AND ITS APPLICATION FOR METAL RECOVERY 346
1 . Introduction 346
2. Microorganisms 347
3. Leaching Machanisms 348
4. Factors Influencing Bacterial Leaching Activity 350
5. Leaching Techniques 351
6. Conclusion 362
References 362
PART IV. SULFUR IN MICROBIOLOGY, BIOCHEMISTRY AND MEDICINE 364
CHAPTER 17. MICROORGANISMS AND THE SULFUR CYCLE 366
1. Introduction 366
2. The Biogeochemical Sulfur Cycle 367
3. The Metabolic Types and Microbial Groups Involved in the Cycle 369
4. The Sulfuretum 376
5. Fractionation of Sulfur Isotopes by Bacteria 378
References 378
CHAPTER 18. PHOTOTROPHIC BACTERIA AND THEIR SULFUR METABOLISM 382
1 . Introduction 382
2. Carbon and Nitrogen Metabolism 383
3. Ecology and Technical Application 384
4. Photosynthesis 384
5. Sulfur Metabolism 385
References 396
Chapter 19. CYTOCHROMES AND IRON SULFUR PROTEINS IN SULFUR METABOLISM OF PHOTOTROPHIC SULFUR BACTERIA 398
1 . Introduction 398
2. Definition of Electron Transfer Proteins 400
3. Enzymatic Steps of Dissimilatory Sulfur Metabolism 403
4. Summary and Conclusion 416
References 420
CHAPTER 20. SULFIDE AND OTHER SULFUR-CONTAINING LIGANDS IN METALLOPROTEINS AND ENZYMES 424
1. Introduction 424
2. Natural Sulfur-Containing Ligands 425
3. Metalloproteins Containing No Sulfide Ligands 428
4. Metalloproteins with Sulfide Ligands 450
References 484
CHAPTER 21. GENETIC DISEASES OF SULFUR METABOLISM IN HUMANS 494
1. Introduction 494
2. Cystathionine ß-Synthase Deficiency 498
References 507
AUTHOR INDEX 510
SUBJECT INDEX 512