Müller / Krebs Sulfur

Its Significance for Chemistry, for the Geo-, Bio-, and Cosmosphere and Technology
1. Auflage 2016
ISBN: 978-1-4832-8989-2
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: Adobe DRM (»Systemvoraussetzungen)

E-Book, Englisch, 526 Seiten, Web PDF

Sulfur

Autoren/Hrsg.

Müller, A.

Krebs, B.

Inhaltsverzeichnis

1;Front Cover;1
2;Sulfer: Its Significance for Chemistry, for the Geo-, Bio- and Cosmosphere and Technology;4
3;Copyright Page;5
4;Table of Contets;10
5;Preface;6
6;Contributors;8
7;PART I: SULFUR: THE ELEMENT, ITS GEOCHEMISTRY AND SOME ASPECTS OF ITS HISTORY;16
7.1;CHAPTER 1. ELEMENTAL SULFUR AND RELATED HOMOCYCLIC COMPOUNDS AND IONS;18
7.1.1;1 . Introduction;19
7.1.2;2. Elemental Sulfur (Neutral Rings Sn);20
7.1.3;3. Homocyclic Sulfur Cations;36
7.1.4;4. Homocyclic Sulfur Oxides;41
7.1.5;5. Homocyclic Sulfur Halide Cations;46
7.1.6;References;48
7.2;CHAPTER 2. SULFUR IN THE EARTH'S CRUST, ITS ORIGIN AND NATURAL CYCLE;54
7.2.1;1. Cosmic and Terrestrial Abundance of Sulfur;54
7.2.2;2. Sulfur Cycle in the Continental Crust;57
7.2.3;3. Sulfur Cycle in the Oceanic Crust;60
7.2.4;4. Isotopic Composition of Natural Sulfur;63
7.2.5;5. Sulfur in the Water Cycle at the Earth's Surface;67
7.2.6;References;68
7.3;CHAPTER 3. SULFUR IN HISTORY: THE ROLE OF SULFUR IN "BLACK POWDER";70
7.3.1;1. Gunpowder - A Chinese Invention?;70
7.3.2;2. Technology of Black Powder in the European Middle Ages;73
7.3.3;3. The Composition of Black Powder and the Reaction of Its Components;74
7.3.4;4. The Role of Sulfur in Black Powder;75
7.3.5;References;81
7.4;CHAPTER 4. SULFUR IN ARTWORK: LAPIS LAZULI AND ULTRAMARINE PIGMENTS;82
7.4.1;1 . A Five-Thousand Years Old Pigment;82
7.4.2;2. The Synthesis of Ultramarine;85
7.4.3;3. Structure Analysis of Lapis Lazuli and of the Ultramarine Pigments;86
7.4.4;4. Blue Sulfur?;90
7.4.5;5. The Chromophores in Ultramarine-Yellow, -Green, -Violet and -Red;95
7.4.6;6. Chemical Behaviour of the Sulfur Species in Lapis Lazuli and in the Ultramarine Pigments;99
7.4.7;7. Concluding Remarks;103
7.4.8;Acknowledgements;103
7.4.9;References;103
8;PART II: CHEMISTRY;106
8.1;CHAPTER 5. NEW DEVELOPMENTS IN THE FIELD OF ORGANIC SULFUR CHEMISTRY;108
8.1.1;1 . Introduction;108
8.1.2;2. New Structures and New Methods for Understanding Structures;109
8.1.3;3. New Ideas on and New Applications of Reactions of Organosulfur Compounds;117
8.1.4;4. Sulfur-Containing Natural Products and Biologically Active Sulfur Compounds;131
8.1.5;References;134
8.2;CHAPTER 6. ORGANOMETALLIC SULFUR COMPOUNDS;136
8.2.1;1 . Introduction;136
8.2.2;2. Structural Types;137
8.2.3;3. Stabilisation Principles and Synthetic Approaches;139
8.2.4;4. Reactivity of M-SH Complexes;141
8.2.5;5. The M3S Electron Reservoir;144
8.2.6;6. Framework Reactions of Sulfur Bridged Organometallic Clusters;148
8.2.7;Acknowledgements;152
8.2.8;References;153
8.3;CHAPTER 7. THIOLATES – INTRIGUING AND VERSATILE LIGANDS FOR TRANSITION METALS;156
8.3.1;1 . Introduction;156
8.3.2;2. Mononuclear Complexes with Monodentate Thiols;157
8.3.3;3. Polynuclear Thiolato-Complexes;162
8.3.4;4. Sulfide Formation by C-S Bond Cleavage;168
8.3.5;5. Polydentate Thiolato-Ligands; Sulfur-Sulfur Interactions;170
8.3.6;6. Redox Reactions and the Electrochemistry of Thiolato-Complexes;174
8.3.7;7. Sterically Hindered Thiolato-Ligands;176
8.3.8;8. Conclusion;178
8.3.9;References;178
8.4;CHAPTER 8. METAL COMPLEXES OF SULFUR AND SULFUR-NITROGEN COMPOUNDS AND THEIR CATALYTIC PROPERTIES;182
8.4.1;1 . Introduction;182
8.4.2;2. Elemental Sulfur as a Ligand;183
8.4.3;3. Complexes with (CH2S)3, (CH2Se)3 and (CH20)6;184
8.4.4;4. Sulfur-Nitrogen Species as Ligands;186
8.4.5;5. Metal-Catalyzed Formation of S(CN)4;193
8.4.6;Acknowledgements;194
8.4.7;References;194
8.5;CHAPTER 9. SULFIDO-COMPLEXES OF MOLYBDENUM AND TUNGSTEN: SYNTHETIC ASPECTS;196
8.5.1;1 . Introduction;196
8.5.2;2. Simple Thiometallate Anions and Their Reactions;197
8.5.3;3. Thiometallates as Ligands;200
8.5.4;4. Reactions of Thiometallates in the Presence of Thiolates;202
8.5.5;5. Mononuclear Complexes;204
8.5.6;References;207
8.6;CHAPTER 10. INTERACTION BETWEEN METAL CENTERS THROUGH SULFUR CONTAINING LIGANDS;210
8.6.1;1 . Introduction;210
8.6.2;2. Theoretical Background;211
8.6.3;3. Large Interaction between Copper(II) Ions Far Away from Each Other;216
8.6.4;4. Dithiooxamidato Copper(II) Dinuclear Complexes;219
8.6.5;5. Ab Initio Calculation of the Exchange Interaction in Dithiooxamide Complexes;225
8.6.6;6. Ordered Bimetallic Chains with Dithiooxalato Bridges;226
8.6.7;7. Magnetic Properties of Iron-Sulfur Complexes;228
8.6.8;8. Conclusion;233
8.6.9;References;234
8.7;CHAPTER 11. SPECTROSCOPIC ASPECTS OF SULFUR CHEMISTRY: ELECTRONIC AND RESONANCE RAMAN SPECTROSCOPY OF SULFUR-CONTAINING COMPLEXES, IONS AND RADICALS;236
8.7.1;1 . Introduction;236
8.7.2;2. Transition Metal Thiometal1ates;238
8.7.3;3. Electronic and RR Spectra of Sulfur-Donor Complexes;240
8.7.4;4. Spectroscopic Studies on Cations;243
8.7.5;5. Spectroscopic Studies on Sulfur Radical Anions;245
8.7.6;6. Conclusion;248
8.7.7;References;248
9;PART III: TECHNOLOGY AND CHEMISTRY WITH TECHNOLOGICAL RELEVANCE;250
9.1;CHAPTER 12. SULFURIC ACID – AN IMPORTANT BASIC PRODUCT IN CHEMISTRY. PROBLEMS AND RECENT DEVELOPMENTS IN PRODUCTION;252
9.1.1;1 . Introduction;252
9.1.2;2. Acid Manufacture and Reduction of Emissions;254
9.1.3;3. Raw Materials;258
9.1.4;4. Energy Recovery;260
9.1.5;5. Recycling of Spent Acids and By-Products;263
9.2;CHAPTER 13. CHEMICAL PROBLEMS OF FLUE-GAS DESULFURISATION;274
9.2.1;1. Introduction;274
9.2.2;2. Chemistry of Sulfur;275
9.2.3;3. The Problem of Changing Oxidation States of Sulfur;285
9.2.4;4. Proposal for a Sulfur Producing Desulfurisation Process;290
9.2.5;References;291
9.3;CHAPTER 14. METAL SULFIDES IN PHOTOVOLTAIC, PHOTOELECTROCHEMICAL AND SOLAR BIOLOGICAL ENERGY CONVERSION;292
9.3.1;1. Introduction;293
9.3.2;2. Sulfur Compounds as Solar Energy Materials;294
9.3.3;3. Photovoltaic Cells Based on Sulfides;304
9.3.4;4. Photoelectrochemical Cells Based on Sulfides;306
9.3.5;5. Solar Assisted Electrolysis of Water;309
9.3.6;6. Photocatalysis and Solar Intercalation Chemistry;314
9.3.7;7. Solar Biomass Based on Sulfur Cycle;318
9.3.8;8. Stability and Reactivity of Sulfide Materials;320
9.3.9;9. Conclusion;322
9.3.10;References;322
9.4;CHAPTER 15. INORGANIC CHEMISTRY RELATED TO RUBBER VULCANISATION;326
9.4.1;1 . Introduction;326
9.4.2;2. Mechanism of Sulfur Vulcanisation;328
9.5;CHAPTER 16. BIODEGRADATION OF SULFUR MINERALS AND ITS APPLICATION FOR METAL RECOVERY;346
9.5.1;1 . Introduction;346
9.5.2;2. Microorganisms;347
9.5.3;3. Leaching Machanisms;348
9.5.4;4. Factors Influencing Bacterial Leaching Activity;350
9.5.5;5. Leaching Techniques;351
9.5.6;6. Conclusion;362
9.5.7;References;362
10;PART IV. SULFUR IN MICROBIOLOGY, BIOCHEMISTRY AND MEDICINE;364
10.1;CHAPTER 17. MICROORGANISMS AND THE SULFUR CYCLE;366
10.1.1;1. Introduction;366
10.1.2;2. The Biogeochemical Sulfur Cycle;367
10.1.3;3. The Metabolic Types and Microbial Groups Involved in the Cycle;369
10.1.4;4. The Sulfuretum;376
10.1.5;5. Fractionation of Sulfur Isotopes by Bacteria;378
10.1.6;References;378
10.2;CHAPTER 18. PHOTOTROPHIC BACTERIA AND THEIR SULFUR METABOLISM;382
10.2.1;1 . Introduction;382
10.2.2;2. Carbon and Nitrogen Metabolism;383
10.2.3;3. Ecology and Technical Application;384
10.2.4;4. Photosynthesis;384
10.2.5;5. Sulfur Metabolism;385
10.2.6;References;396
10.3;Chapter 19. CYTOCHROMES AND IRON SULFUR PROTEINS IN SULFUR METABOLISM OF PHOTOTROPHIC SULFUR BACTERIA;398
10.3.1;1 . Introduction;398
10.3.2;2. Definition of Electron Transfer Proteins;400
10.3.3;3. Enzymatic Steps of Dissimilatory Sulfur Metabolism;403
10.3.4;4. Summary and Conclusion;416
10.3.5;References;420
10.4;CHAPTER 20. SULFIDE AND OTHER SULFUR-CONTAINING LIGANDS IN METALLOPROTEINS AND ENZYMES;424
10.4.1;1. Introduction;424
10.4.2;2. Natural Sulfur-Containing Ligands;425
10.4.3;3. Metalloproteins Containing No Sulfide Ligands;428
10.4.4;4. Metalloproteins with Sulfide Ligands;450
10.4.5;References;484
10.5;CHAPTER 21. GENETIC DISEASES OF SULFUR METABOLISM IN HUMANS;494
10.5.1;1. Introduction;494
10.5.2;2. Cystathionine ß-Synthase Deficiency;498
10.5.3;References;507
11;AUTHOR INDEX;510
12;SUBJECT INDEX;512