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Unformatted text preview: This page intentionally left blank Descriptive Inorganic Chemistry FIFTH EDITION Geoff Rayner-Canham Sir Wilfred Grenfell College Memorial University Tina Overton University of Hull W. H. FREEMAN AND COMPANY NEW YORK Publisher: Clancy Marshall Acquisitions Editors: Jessica Fiorillo/Kathryn Treadway Marketing Director: John Britch Media Editor: Dave Quinn Cover and Text Designer: Vicki Tomaselli Senior Project Editor: Mary Louise Byrd Illustrations: Network Graphics/Aptara Senior Illustration Coordinator: Bill Page Production Coordinator: Susan Wein Composition: Aptara Printing and Binding: World Color Versailles Library of Congress Control Number: 2009932448 ISBN-13: 978-1-4292-2434-5 ISBN-10: 1-4292-1814-2 @2010, 2006, 2003, 2000 by W. H. Freeman and Company All rights reserved Printed in the United States of America First printing W. H. Freeman and Company 41 Madison Avenue New York, NY 10010 Houndmills, Basingstoke RG21 6XS, England Overview CHAPTER 1 The Electronic Structure of the Atom: A Review CHAPTER 2 An Overview of the Periodic Table 19 CHAPTER 3 Covalent Bonding 41 CHAPTER 4 Metallic Bonding 81 CHAPTER 5 Ionic Bonding 93 CHAPTER 6 Inorganic Thermodynamics 113 CHAPTER 7 Solvent Systems and Acid-Base Behavior 137 CHAPTER 8 Oxidation and Reduction 167 CHAPTER 9 Periodic Trends 191 CHAPTER 10 Hydrogen 227 CHAPTER 11 The Group 1 Elements: The Alkali Metals 245 CHAPTER 12 The Group 2 Elements: The Alkaline Earth Metals 271 CHAPTER 13 The Group 13 Elements 291 CHAPTER 14 The Group 14 Elements 315 CHAPTER 15 The Group 15 Elements: The Pnictogens 363 CHAPTER 16 The Group 16 Elements: The Chalcogens 409 CHAPTER 17 The Group 17 Elements: The Halogens 453 CHAPTER 18 The Group 18 Elements: The Noble Gases 487 CHAPTER 19 Transition Metal Complexes 499 CHAPTER 20 Properties of the 3d Transition Metals 533 CHAPTER 21 Properties of the 4d and 5d Transition Metals 579 CHAPTER 22 The Group 12 Elements 599 CHAPTER 23 Organometallic Chemistry 611 On the Web CHAPTER 24 The Rare Earth and Actinoid Elements Appendices Index 1 651w A-1 I-1 iii This page intentionally left blank Contents What Is Descriptive Inorganic Chemistry? Preface Acknowledgments Dedication xiii xv xix xxi CHAPTER 1 The Electronic Structure of the Atom: A Review 1 Atomic Absorption Spectroscopy 2 1.1 1.2 1.3 1.4 1.5 1.6 The Schrödinger Wave Equation and Its Significance Shapes of the Atomic Orbitals The Polyelectronic Atom Ion Electron Configurations Magnetic Properties of Atoms Medicinal Inorganic Chemistry: An Introduction 3 5 9 14 15 16 2.1 2.2 2.3 19 Organization of the Modern Periodic Table 21 Existence of the Elements 23 Stability of the Elements and Their Isotopes 24 The Origin of the Shell Model of the Nucleus 26 2.4 2.5 2.6 2.7 27 29 33 35 Classifications of the Elements Periodic Properties: Atomic Radius Periodic Properties: Ionization Energy Periodic Properties: Electron Affinity Alkali Metal Anions 37 2.8 37 The Elements of Life CHAPTER 3 Covalent Bonding 41 3.1 3.2 3.3 42 43 Models of Covalent Bonding Introduction to Molecular Orbitals Molecular Orbitals for Period 1 Diatomic Molecules 3.5 3.6 3.7 3.8 3.9 3.10 3.11 3.12 Molecular Orbitals for Period 2 Diatomic Molecules Molecular Orbitals for Heteronuclear Diatomic Molecules A Brief Review of Lewis Structures Partial Bond Order Formal Charge Valence-Shell Electron-Pair Repulsion Rules The Valence-Bond Concept Network Covalent Substances Intermolecular Forces 46 50 51 53 54 54 59 61 63 The Origins of the Electronegativity Concept 65 3.13 3.13 66 72 Molecular Symmetry Symmetry and Vibrational Spectroscopy Transient Species—A New Direction for Inorganic Chemistry 74 3.15 Covalent Bonding and the Periodic Table 78 CHAPTER 4 CHAPTER 2 An Overview of the Periodic Table 3.4 44 Metallic Bonding 81 4.1 4.2 4.3 4.4 4.5 81 82 84 86 87 Metallic Bonding Bonding Models Structure of Metals Unit Cells Alloys Memory Metal: The Shape of Things to Come 88 4.6 4.7 89 90 Nanometal Particles Magnetic Properties of Metals CHAPTER 5 Ionic Bonding 93 5.1 5.2 5.3 5.4 5.5 93 95 96 99 5.6 The Ionic Model and the Size of Ions Hydrated Salts Polarization and Covalency Ionic Crystal Structures Crystal Structures Involving Polyatomic Ions The Bonding Continuum Concrete: An Old Material with a New Future 105 106 109 v vi Contents 8.8 CHAPTER 6 Inorganic Thermodynamics 6.1 6.2 6.3 6.4 Thermodynamics of the Formation of Compounds Formation of Ionic Compounds The Born-Haber Cycle Thermodynamics of the Solution Process for Ionic Compounds Formation of Covalent Compounds 113 114 120 122 8.9 8.10 8.11 8.12 8.13 Electrode Potentials as Thermodynamic Functions Latimer (Reduction Potential) Diagrams Frost (Oxidation State) Diagrams Pourbaix Diagrams Redox Synthesis Biological Aspects 124 127 CHAPTER 9 The Hydrogen Economy 128 Periodic Trends 6.6 129 9.1 9.2 9.3 6.5 Thermodynamic versus Kinetic Factors CHAPTER 7 Solvent Systems and Acid-Base Behavior 137 7.1 7.2 138 142 Solvents Brønsted-Lowry Acids Antacids 144 7.3 147 Brønsted-Lowry Bases 9.4 9.5 Group Trends Periodic Trends in Bonding Isoelectronic Series in Covalent Compounds Trends in Acid-Base Properties The (n) Group and (n ! 10) Group Similarities 177 178 180 182 184 185 191 192 195 199 201 202 Chemical Topology 206 9.6 Isomorphism in Ionic Compounds 207 209 210 Cyanide and Tropical Fish 148 New Materials: Beyond the Limitations of Geochemistry 7.4 148 9.7 Superacids and Superbases 150 Lithium and Mental Health 211 7.5 7.6 7.7 7.8 7.9 153 155 156 158 161 9.8 9.9 9.10 9.11 9.12 The “Knight’s Move” Relationship The Early Actinoid Relationships The Lanthanoid Relationships “Combo” Elements Biological Aspects 212 215 216 217 221 Thallium Poisoning: Two Case Histories 223 Trends in Acid-Base Behavior Acid-Base Reactions of Oxides Lewis Theory Pearson Hard-Soft Acid-Base Concepts Applications of the HSAB Concept Biological Aspects Diagonal Relationships CHAPTER 8 Oxidation and Reduction 167 CHAPTER 10 8.1 8.2 8.3 167 168 Hydrogen 227 10.1 10.2 228 229 8.4 8.5 8.6 Redox Terminology Oxidation Number Rules Determination of Oxidation Numbers from Electronegativities The Difference between Oxidation Number and Formal Charge Periodic Variations of Oxidation Numbers Redox Equations 169 171 172 173 Isotopes of Hydrogen Nuclear Magnetic Resonance Isotopes in Chemistry 230 10.3 Properties of Hydrogen 231 Searching the Depths of Space for the Trihydrogen Ion 233 10.4 10.5 233 237 Hydrides Water and Hydrogen Bonding Chemosynthesis: Redox Chemistry on the Seafloor 175 Water: The New Wonder Solvent 238 8.7 176 10.6 239 Quantitative Aspects of Half-Reactions Clathrates Contents 10.7 Biological Aspects of Hydrogen Bonding 241 Is There Life Elsewhere in Our Solar System? 242 10.8 242 Element Reaction Flowchart CHAPTER 11 The Group 1 Elements: The Alkali Metals 11.1 11.2 11.3 Group Trends Features of Alkali Metal Compounds Solubility of Alkali Metal Salts 245 246 247 249 Mono Lake 250 11.4 11.5 11.6 11.7 11.8 11.9 252 255 256 257 259 261 Lithium Sodium Potassium Oxides Hydroxides Sodium Chloride Salt Substitutes 261 11.10 11.11 11.12 11.13 11.14 262 262 264 264 Potassium Chloride Sodium Carbonate Sodium Hydrogen Carbonate Ammonia Reaction Ammonium Ion as a Pseudo– Alkali-Metal Ion 11.15 Biological Aspects 11.16 Element Reaction Flowcharts 265 265 266 CHAPTER 12 The Group 2 Elements: The Alkaline Earth Metals 12.1 12.2 12.3 12.4 12.5 12.6 12.7 Group Trends Features of Alkaline Earth Metal Compounds Beryllium Magnesium Calcium and Barium Oxides Calcium Carbonate Biomineralization: A New Interdisciplinary “Frontier” 284 12.10 12.11 12.12 12.15 284 285 286 287 Calcium Sulfate Calcium Carbide Biological Aspects Element Reaction Flowcharts CHAPTER 13 The Group 13 Elements 291 13.1 13.2 13.3 292 293 294 Group Trends Boron Borides Inorganic Fibers 295 13.4 295 Boranes Boron Neutron Capture Therapy 298 13.5 13.6 13.7 13.8 13.9 13.10 13.11 13.12 300 301 306 307 308 309 309 311 Boron Halides Aluminum Aluminum Halides Aluminum Potassium Sulfate Spinels Aluminides Biological Aspects Element Reaction Flowcharts CHAPTER 14 The Group 14 Elements 14.1 14.2 14.3 Group Trends Contrasts in the Chemistry of Carbon and Silicon Carbon 315 316 316 318 The Discovery of Buckminsterfullerene 322 271 14.4 14.5 325 326 272 275 276 278 279 280 Moissanite: The Diamond Substitute 327 14.6 14.7 328 330 271 How Was Dolomite Formed? 281 12.8 12.9 282 283 Cement Calcium Chloride vii Isotopes of Carbon Carbides Carbon Monoxide Carbon Dioxide Carbon Dioxide, Supercritical Fluid 332 14.8 14.9 14.10 14.11 14.12 333 335 335 338 339 Carbonates and Hydrogen Carbonates Carbon Sulfides Carbon Halides Methane Cyanides viii 14.13 14.14 14.15 14.16 14.17 Contents Silicon Silicon Dioxide Silicates Aluminosilicates Silicones 339 341 343 345 349 Inorganic Polymers 350 14.18 14.19 14.20 14.21 351 352 353 354 Tin and Lead Tin and Lead Oxides Tin and Lead Halides Tetraethyllead TEL: A Case History 355 14.22 Biological Aspects 14.23 Element Reaction Flowcharts 356 359 CHAPTER 15 The Group 15 Elements: The Pnictogens 15.1 15.2 Group Trends Contrasts in the Chemistry of Nitrogen and Phosphorus Overview of Nitrogen Chemistry 363 364 365 368 CHAPTER 16 The Group 16 Elements: The Chalcogens 16.1 16.2 16.3 Group Trends Contrasts in the Chemistry of Oxygen and Sulfur Oxygen Oxygen Isotopes in Geology 16.4 409 410 411 412 412 Bonding in Covalent Oxygen Compounds Trends in Oxide Properties Mixed-Metal Oxides 418 419 421 New Pigments through Perovskites 422 16.7 16.8 16.9 16.10 16.11 16.12 Water Hydrogen Peroxide Hydroxides The Hydroxyl Radical Overview of Sulfur Chemistry Sulfur 422 424 424 426 426 427 Cosmochemistry: Io, the Sulfur-Rich Moon 428 431 432 16.5 16.6 The First Dinitrogen Compound 369 16.13 Hydrogen Sulfide 16.14 Sulfides 15.4 369 Disulfide Bonds and Hair 432 Propellants and Explosives 370 15.5 371 16.15 16.16 16.17 16.18 16.19 16.20 16.21 16.22 16.23 16.24 434 437 438 440 441 443 445 445 446 448 15.3 Nitrogen Nitrogen Hydrides Haber and Scientific Morality 374 15.6 15.7 15.8 15.9 15.10 15.11 15.12 15.13 377 378 379 384 385 386 389 390 Nitrogen Ions The Ammonium Ion Nitrogen Oxides Nitrogen Halides Nitrous Acid and Nitrites Nitric Acid and Nitrates Overview of Phosphorus Chemistry Phosphorus Nauru, the World’s Richest Island 391 15.14 15.15 15.16 15.17 15.18 15.19 393 393 394 395 399 399 Phosphine Phosphorus Oxides Phosphorus Chlorides Phosphorus Oxo-Acids and Phosphates The Pnictides Biological Aspects Paul Erhlich and His “Magic Bullet” 401 15.29 Element Reaction Flowcharts 402 Sulfur Oxides Sulfites Sulfuric Acid Sulfates and Hydrogen Sulfates Other Oxy-Sulfur Anions Sulfur Halides Sulfur-Nitrogen Compounds Selenium Biological Aspects Element Reaction Flowcharts CHAPTER 17 The Group 17 Elements: The Halogens 453 17.1 17.2 17.3 Group Trends Contrasts in the Chemistry of Fluorine and Chlorine Fluorine The Fluoridation of Water 17.4 17.5 454 455 458 459 Hydrogen Fluoride and Hydrofluoric Acid 460 Overview of Chlorine Chemistry 462 Contents 17.6 17.7 17.8 17.9 17.10 Chlorine Hydrochloric Acid Halides Chlorine Oxides Chlorine Oxyacids and Oxyanions 463 464 465 469 471 Swimming Pool Chemistry 473 The Discovery of the Perbromate Ion 474 17.11 Interhalogen Compounds and Polyhalide Ions 17.12 Cyanide Ion as a Pseudo-halide Ion 17.13 Biological Aspects 17.14 Element Reaction Flowcharts 475 477 478 481 CHAPTER 18 The Group 18 Elements: The Noble Gases 18.1 18.2 18.3 18.4 Group Trends Unique Features of Helium Uses of the Noble Gases A Brief History of Noble Gas Compounds 487 488 489 489 491 Is It Possible to Make Compounds of the Early Noble Gases? 492 18.5 18.6 18.7 18.8 18.9 492 494 495 495 496 Xenon Fluorides Xenon Oxides Other Noble Gas Compounds Biological Aspects Element Reaction Flowchart CHAPTER 19 Transition Metal Complexes 19.1 19.2 19.3 19.4 Transition Metals Introduction to Transition Metal Complexes Stereochemistries Isomerism in Transition Metal Complexes 499 499 521 19.9 19.10 19.11 19.12 19.13 521 523 525 526 More on Electronic Spectra Ligand Field Theory Thermodynamic versus Kinetic Factors Synthesis of Coordination Compounds Coordination Complexes and the HSAB Concept 19.14 Biological Aspects 527 529 CHAPTER 20 Properties of the 3d Transition Metals 20.1 20.2 20.3 20.4 20.5 Overview of the 3d Transition Metals Group 4: Titanium Group 5: Vanadium Group 6: Chromium Group 7: Manganese 533 534 536 537 538 544 Mining the Seafloor 545 20.6 20.7 20.8 20.9 20.10 20.11 549 558 562 563 569 572 Group 8: Iron Group 9: Cobalt Group 10: Nickel Group 11: Copper Biological Aspects Element Reaction Flowcharts CHAPTER 21 Properties of the 4d and 5d Transition Metals 21.1 21.2 Comparison of the Transition Metals Features of the Heavy Transition Metals Group 4: Zirconium and Hafnium Group 5: Niobium and Tantalum Group 6: Molybdenum and Tungsten Group 7: Technetium and Rhenium 579 580 581 584 585 586 587 500 502 503 Technetium: The Most Important Radiopharmaceutical 588 21.7 21.8 21.9 21.10 21.11 21.12 589 590 591 591 591 594 506 19.5 19.6 507 19.7 19.8 The Earth and Crystal Structures 21.3 21.4 21.5 21.6 Platinum Complexes and Cancer Treatment Naming Transition Metal Complexes An Overview of Bonding Theories of Transition Metal Compounds Crystal Field Theory Successes of Crystal Field Theory ix 510 511 517 The Platinum Group Metals Group 8: Ruthenium and Osmium Group 9: Rhodium and Iridium Group 10: Palladium and Platinum Group 11: Silver and Gold Biological Aspects x Contents CHAPTER 22 The Group 12 Elements 599 22.1 22.2 22.3 22.4 600 600 603 605 Group Trends Zinc and Cadmium Mercury Biological Aspects Mercury Amalgam in Teeth 607 22.5 608 Element Reaction Flowchart 23.1 23.2 23.3 23.4 23.5 Introduction to Organometallic Compounds Naming Organometallic Compounds Counting Electrons Solvents for Organometallic Chemistry Main Group Organometallic Compounds 611 612 612 613 614 615 Grignard Reagents 618 The Death of Karen Wetterhahn 623 23.6 Organometallic Compounds of the Transition Metals 23.7 Transition Metal Carbonyls 23.8 Synthesis and Properties of Simple Metal Carbonyls 23.9 Reactions of Transition Metal Carbonyls 23.10 Other Carbonyl Compounds 23.11 Complexes with Phosphine Ligands 23.12 Complexes with Alkyl, Alkene, and Alkyne Ligands Vitamin B12—A Naturally Occurring Organometallic Compound 23.13 Complexes with Allyl and 1,3-Butadiene Ligands 23.14 Metallocenes 23.15 Complexes with "6-Arene Ligands 23.16 Complexes with Cycloheptatriene and Cyclooctatetraene Ligands 623 625 630 632 633 634 635 638 639 640 642 643 643 644 CHAPTER 24 ON THE WEB The Rare Earth and Actinoid Elements 24.1 24.2 CHAPTER 23 Organometallic Chemistry 23.17 Fluxionality 23.18 Organometallic Compounds in Industrial Catalysis The Group 3 Elements The Lanthanoids 651w 653w 653w Superconductivity 655w 23.3 24.4 656w 659w The Actinoids Uranium A Natural Fission Reactor 661w 24.5 662w The Postactinoid Elements APPENDICES Appendix 1 Appendix 2 Appendix 3 Appendix 4 Appendix 5 Appendix 6 Appendix 7 Appendix 8 Thermodynamic Properties of Some Selected Inorganic Compounds Charge Densities of Selected Ions Selected Bond Energies Ionization Energies of Selected Metals Electron Affinities of Selected Nonmetals Selected Lattice Energies Selected Hydration Enthalpies Selected Ionic Radii A-1 A-13 A-16 A-18 A-20 A-21 A-22 A-23 ON THE WEB Appendix 9 Standard Half-Cell Electrode Potentials of Selected Elements A-25w ON THE WEB Appendix 10 Electron Configuration of the Elements INDEX A-35w I-1 What Is Descriptive Inorganic Chemistry? D escriptive inorganic chemistry was traditionally concerned with the properties of the elements and their compounds. Now, in the renaissance of the subject, with the synthesis of new and novel materials, the properties are being linked with explanations for the formulas and structures of compounds together with an understanding of the chemical reactions they undergo. In addition, we are no longer looking at inorganic chemistry as an isolated subject but as a part of essential scientific knowledge with applications throughout science and our lives. Because of a need for greater contextualization, we have added more features and more applications. In many colleges and universities, descriptive inorganic chemistry is offered as a sophomore or junior course. In this way, students come to know something of the fundamental properties of important and interesting elements and their compounds. Such knowledge is important for careers not only in pure or applied chemistry but also in pharmacy, medicine, geology, and environmental science. This course can then be followed by a junior or senior course that focuses on the theoretical principles and the use of spectroscopy to a greater depth than is covered in a descriptive text. In fact, the theoretical course builds nicely on the descriptive background. Without the descriptive grounding, however, the theory becomes sterile, uninteresting, and irrelevant. Education has often been a case of the “swinging pendulum,” and this has been true of inorganic chemistry. Up until the 1960s, it was very much pure descriptive, requiring exclusively memorization. In the 1970s and 1980s, upper-level texts focused exclusively on the theoretical principles. Now it is apparent that descriptive is very important—not the traditional memorization of facts but the linking of facts, where possible, to underlying principles. Students need to have modern descriptive inorganic chemistry as part of their education. Thus, we must ensure that chemists are aware of the “new descriptive inorganic chemistry.” xi This page intentionally left blank Preface Inorganic chemistry goes beyond academic interest: it is an important part of our lives. I norganic chemistry is interesting—more than that—it is exciting! So much of our twenty-first-century science and technology rely on natural and synthetic materials, often inorganic compounds, many of which are new and novel. Inorganic chemistry is ubiquitous in our daily lives: household products, some pharmaceuticals, our transportation—both the vehicles themselves and the synthesis of the fuels—battery technology, and medical treatments. There is the industrial aspect, the production of all the chemicals required to drive our economy, everything from steel to sulfuric acid to glass and cement. Environmental chemistry is largely a question of the inorganic chemistry of the atmosphere, water, and soil. Finally, there are the profound issues of the inorganic chemistry of our planet, the solar system, and the universe. This textbook is designed to focus on the properties of selected interesting, important, and unusual elements and compounds. However, to understand inorganic chemistry, it is crucial to tie this knowledge to the underlying chemical principles and hence provide explanations for the existence and behavior of compounds. For this reason, almost half the chapters survey the relevant concepts of atomic theory, bonding, intermolecular forces, thermodynamics, acid-base behavior, and reduction-oxidation properties as a prelude to, and preparation for, the descriptive material. For this fifth edition, the greatest change has been the expansion of coverage of the 4d and 5d transition metals to a whole chapter. The heavier transition metals have unique trends and patterns, and the new chapter highlights these. Having an additional chapter on transition metals also better balances the coverage between the main group elements and the transition elements. Also, the fifth edition has a second color. With the addition of a second color, figures are much easier to understand, and tables and text are easier to read. On a chapter-by-chapter basis, the significant improvements are as follows: Chapter 1: The Electronic Structure of the Atom: A Review The Introduction and Section 1.3, The Polyelectronic Atom, have been revised. Chapter 3: Covalent Bonding Section 3.11, Network Covalent Substances, has a new subsection: Amorp...
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