Descriptive Inorganic, Coordination, and Solid State Chemistry

by Rodgers, Glen E.

• ISBN13: 9780125920605
• ISBN10: 0125920601
• Edition: 2nd
• Format: Hardcover
• Copyright: 2002-01-07
• Publisher: Brooks Cole

Summary

This class-tested text introduces the basics of coordination, solid state, and descriptive main-group chemistry in a uniquely accessible manner, featuring a "less is better than more" approach. The approach offers instructors the opportunity to build upon and present concepts and applications that they find particularly important and fascinating. Consistent with the philosophy that less is better than more, this book does not contain traditional chapters reviewing or expanding on atomic and molecular structure and other topics previously and adequately developed in most introductory courses. As a result, the book moves directly into the presentation of topics central to inorganic chemistry. Written for students, with a conversational prose that is enjoyable and easy to understand, this book presents not only the basic theories and methods of inorganic chemistry (in three self-standing sections), but also a great deal of the history and the applications of the discipline. The author's presentation does not assume prerequisites of organic or physical chemistry.

Table of Contents

The Evolving Realm of Inorganic Chemistry	1	(6)
Summary	6	(1)
Part I Coordination Chemistry	7	(144)
An Introduction to Coordination Chemistry	9	(24)
The Historical Perspective	10	(2)
The History of Coordination Compounds	12	(6)
Early Compounds	12	(1)
The Blomstrand--Jørgensen Chain Theory	13	(2)
The Werner Coordination Theory	15	(3)
The Modern View of Coordination Compounds	18	(3)
An Introduction to the Nomenclature of Coordination Compounds	21	(12)
Summary	25	(1)
Problems	26	(7)
Structures of Coordination Compounds	33	(24)
Stereoisomers	33	(4)
Octahedral Coordination Spheres	37	(7)
Compounds with Monodentate Ligands	37	(3)
Compounds with Chelating Ligands	40	(4)
Square Planar Coordination Spheres	44	(1)
Tetrahedral Coordination Spheres	45	(1)
Other Coordination Spheres	45	(3)
Structural Isomers	48	(9)
Summary	50	(1)
Problems	51	(6)
Bonding Theories for Coordination Compounds	57	(36)
Early Bonding Theories	58	(2)
The Lewis Acid-Base Definition	58	(1)
Crystal Field, Valence-Bond, and Molecular Orbital Theories	59	(1)
Crystal Field Theory	60	(9)
Shapes of 3d Orbitals	60	(4)
Octahedral Fields	64	(2)
Tetragonally Distorted Octahedral and Square Planar Fields	66	(2)
Tetrahedral Fields	68	(1)
Consequences and Applications of Crystal Field Splitting	69	(24)
Crystal Field Splitting Energies versus Pairing Energies	69	(2)
Crystal Field Stabilization Energies	71	(1)
Factors Affecting the Magnitude of the Crystal Field Splitting Energies	72	(4)
Magnetic Properties	76	(3)
Absorption Spectroscopy and the Colors of Coordination Compounds	79	(3)
Summary	82	(2)
Problems	84	(9)
Rates and Mechanisms of Reactions of Coordination Compounds	93	(34)
A Brief Survey of Reaction Types	93	(4)
Labile and Inert Coordination Compounds	97	(1)
Substitution Reactions of Octahedral Complexes	98	(13)
Possible Mechanisms	98	(3)
Experimental Complications	101	(1)
Evidence for Dissociative Mechanisms	102	(5)
Explanation of Inert versus Labile Complexes	107	(4)
Redox, or Electron Transfer, Reactions	111	(4)
Outer-Sphere Mechanisms	111	(2)
Inner-Sphere Mechanisms	113	(2)
Substitution Reactions in Square Planar Complexes: The Kinetic Trans Effect	115	(12)
Summary	118	(1)
Problems	119	(8)
Applications of Coordination Compounds	127	(24)
Applications of Monodentate Complexes	127	(3)
Two Keys to the Stability of Transition Metal Complexes	130	(3)
Hard and Soft Acids and Bases	130	(1)
The Chelate Effect	131	(2)
Applications of Multidentate Complexes	133	(3)
Chelating Agents as Detergent Builders	136	(1)
Bioinorganic Applications of Coordination Chemistry	137	(14)
Oxygen Transport	138	(2)
Therapeutic Chelating Agents for Heavy Metals	140	(3)
Platinum Antitumor Agents	143	(1)
Summary	144	(1)
Problems	145	(6)
Part II Solid-State Chemistry	151	(64)
Solid-State Structures	153	(40)
Types of Crystals	153	(4)
Ionic Crystals	153	(2)
Metallic Crystals	155	(1)
Covalent Network Crystals	155	(1)
Atomic-Molecular Crystals	156	(1)
A Type Crystal Lattices	157	(10)
Space Lattices and Unit Cells	157	(1)
A Type Lattices	158	(9)
ABn-Type Crystal Lattices	167	(13)
Cubic, Octahedral, and Tetrahedral Holes	168	(1)
Radius Ratios	169	(2)
Ionic Radii	171	(1)
AB Structures	172	(6)
AB2 Structures	178	(2)
Structures Involving Polyatomic Molecules and Ions	180	(2)
Defect Structures	182	(1)
Spinel Structures: Connecting Crystal Field Effects with Solid-State Structures	182	(11)
Summary	185	(1)
Problems	185	(8)
Solid-State Energetics	193	(22)
Lattice Energy: A Theoretical Evaluation	193	(7)
Lattice Energy: Thermodynamic Cycles	200	(6)
Electron Affinities	203	(1)
Heats of Formation for Unknown Compounds	204	(2)
Thermochemical Radii	206	(1)
Lattice Energies and Ionic Radii: Connecting Crystal Field Effects with Solid-State Energetics	206	(9)
Summary	209	(1)
Problems	210	(5)
Part III Descriptive Chemistry of the Representative Elements	215	(334)
Building a Network of Ideas to Make Sense of the Periodic Table	217	(26)
The Periodic Law	218	(10)
Effective Nuclear Charge	220	(3)
Atomic Radii	223	(1)
Ionization Energy	224	(1)
Electron Affinity	225	(2)
Electronegativity	227	(1)
The Uniqueness Principle	228	(3)
The Small Size of the First Elements	228	(1)
The Increased Likelihood of Pi Bonding in the First Elements	229	(1)
The Lack of Availability of d Orbitals in the First Elements	230	(1)
The Diagonal Effect	231	(2)
The Inert-Pair Effect	233	(2)
Metal, Nonmetal, and Metalloid Regions	235	(8)
Summary	235	(2)
Problems	237	(6)
Hydrogen and Hydrides	243	(24)
The Origin of the Elements (and of Us!)	243	(3)
Discovery, Preparation, and Uses of Hydrogen	246	(2)
Isotopes of Hydrogen	248	(3)
Radioactive Processes Involving Hydrogen	251	(3)
Alpha and Beta Decay, Nuclear Fission, and Deuterium	251	(2)
Tritium	253	(1)
Hydrides and the Network	254	(4)
Covalent Hydrides	255	(1)
Ionic Hydrides	256	(1)
Metallic Hydrides	257	(1)
The Role of Hydrogen in Various Alternative Energy Sources	258	(9)
The Hydrogen Economy	258	(2)
Nuclear Fusion	260	(1)
Summary	260	(1)
Problems	261	(6)
Oxygen, Aqueous Solutions, and the Acid-Base Character of Oxides and Hydroxides	267	(36)
Oxygen	267	(4)
Discovery	267	(2)
Occurrence, Preparation, Properties, and Uses	269	(2)
Water and Aqueous Solutions	271	(7)
The Structure of the Water Molecule	271	(1)
Ice and Liquid Water	272	(2)
Solubility of Substances in Water	274	(3)
Self Ionization of Water	277	(1)
The Acid-Base Character of Oxides and Hydroxides in Aqueous Solution	278	(7)
Oxides: General Expectations from the Network	278	(1)
Oxides in Aqueous Solution (Acidic and Basic Anhydrides)	279	(3)
The E-O-H Unit in Aqueous Solution	282	(1)
An Addition to the Network	283	(2)
The Relative Strengths of Oxoacids and Hydroacids in Aqueous Solution	285	(4)
Oxoacids	285	(1)
Nomenclature of Oxoacids and Corresponding Salts (Optional)	285	(3)
Hydroacids	288	(1)
Ozone	289	(2)
The Greenhouse Effect and Global Warming	291	(12)
Summary	295	(1)
Problems	296	(7)
Group 1A: The Alkali Metals	303	(28)
Discovery and Isolation of the Elements	303	(3)
Fundamental Properties and the Network	306	(4)
Hydrides, Oxides, Hydroxides, and Halides	306	(2)
Application of the Uniqueness Principle and Diagonal Effect	308	(2)
Reduction Potentials and the Network	310	(7)
Peroxides and Superoxides	317	(4)
Peroxides	317	(4)
Superoxides	321	(1)
Reactions and Compounds of Practical Importance	321	(1)
Selected Topic in Depth: Metal-Ammonia Solutions	322	(9)
Summary	325	(1)
Problems	326	(5)
Group 2A: The Alkaline-Earth Metals	331	(24)
Discovery and Isolation of the Elements	331	(5)
Calcium, Barium, and Strontium	333	(1)
Magnesium	333	(1)
Beryllium	334	(1)
Radium	334	(2)
Fundamental Properties and the Network	336	(5)
Hydrides, Oxides, Hydroxides, and Halides	338	(1)
Uniqueness of Beryllium and Diagonal Relationship to Aluminum	339	(2)
Reactions and Compounds of Practical Importance	341	(4)
Beryllium Disease	341	(1)
Radiochemical Uses	342	(1)
Metallurgical Uses	342	(1)
Fireworks and X Rays	343	(1)
Hard Water	344	(1)
Selected Topic in Depth: The Commercial Uses of Calcium Compounds	345	(10)
CaCO3 (Limestone)	345	(3)
CaO (Quicklime) and Ca(OH)2 (Slaked Lime)	348	(1)
Summary	349	(1)
Problems	350	(5)
The Group 3A Elements	355	(32)
Discovery and Isolation of the Elements	355	(4)
Boron	355	(1)
Aluminum	356	(1)
Gallium	357	(1)
Indium and Thallium	358	(1)
Fundamental Properties and the Network	359	(6)
Hydrides, Oxides, Hydroxides, and Halides	361	(4)
Structural Aspects of Boron Chemistry	365	(4)
Allotropes	365	(1)
Borides	366	(2)
Borates	368	(1)
Aluminum, Gallium, Indium, and Thallium: Reactions and Compounds of Practical Importance	369	(4)
Aluminum Metal and Alloys	369	(2)
Alums	371	(1)
Alumina	372	(1)
Gallium, Indium, and Thallium Compounds	372	(1)
Selected Topic in Depth: Electron-Deficient Compounds	373	(14)
Summary	380	(2)
Problems	382	(5)
The Group 4A Elements	387	(40)
Discovery and Isolation of the Elements	387	(4)
Carbon, Tin, and Lead	388	(2)
Silicon	390	(1)
Germanium	390	(1)
Fundamental Properties and the Network	391	(5)
Hydrides	392	(2)
Oxides and Hydroxides	394	(1)
Halides	395	(1)
An Eighth Component of the Interconnected Network: pπ-dπ Bonding Involving Elements of the Second and Third Periods	396	(3)
Reactions and Compounds of Practical Importance	399	(11)
Diamond, Graphite, and the Graphenes	399	(6)
Tin Disease	405	(1)
Radiochemical Uses	406	(1)
Carbon Compounds	407	(1)
Lead Compounds and Toxicology	408	(2)
Silicates, Silica, and Aluminosilicates	410	(5)
Silicates and Silica	410	(3)
Aluminosilicates	413	(2)
Selected Topics in Depth: Semiconductors and Glass	415	(12)
Semiconductors	415	(3)
Glass	418	(1)
Summary	419	(2)
Problems	421	(6)
Group 5A: The Pnicogens	427	(40)
Discovery and Isolation of the Elements	427	(3)
Antimony and Arsenic	428	(1)
Phosphorus	429	(1)
Bismuth	429	(1)
Nitrogen	430	(1)
Fundamental Properties and the Network	430	(8)
The Uniqueness Principle	430	(2)
Pπ-dπ Bonding Involving Elements of the Second and Third Periods	432	(2)
Other Network Components	434	(1)
Hydrides	434	(1)
Oxides and Oxoacids	435	(2)
Halides	437	(1)
A Survey of Nitrogen Oxidation States	438	(9)
Nitrogen (-3) Compounds: Nitrides and Ammonia	438	(2)
Nitrogen (-2): Hydrazine, N2H4	440	(1)
Nitrogen (-1): Hydroxylamine, NH2OH	441	(1)
Nitrogen (+1): Nitrous Oxide, N2O	442	(1)
Nitrogen (+2): Nitric Oxide, NO	443	(2)
Nitrogen (+3): Dinitrogen Trioxide, N2O3, and Nitrous Acid, HNO2	445	(1)
Nitrogen (+4): Nitrogen Dioxide, NO2	445	(1)
Nitrogen (+5): Dinitrogen Pentoxide, N2O5, and Nitric Acid, HNO3	446	(1)
Reactions and Compounds of Practical Importance	447	(7)
Nitrogen Fixation	447	(2)
Nitrates and Nitrites	449	(1)
Nitrogen Air Bags	450	(1)
Matches and Phossy Jaw	451	(1)
Phosphates	452	(2)
Selected Topic in Depth: Photochemical Smog	454	(13)
Summary	460	(1)
Problems	461	(6)
Sulfur, Selenium, Tellurium, and Polonium	467	(28)
Discovery and Isolation of the Elements	467	(3)
Sulfur	468	(1)
Tellurium and Selenium (Earth and Moon)	469	(1)
Polonium	469	(1)
Fundamental Properties and the Network	470	(7)
Hydrides	472	(1)
Oxides and Oxoacids	473	(2)
Halides	475	(2)
Allotropes and Compounds Involving Element-Element Bonds	477	(4)
Allotropes	477	(1)
Polycations and Anions	478	(1)
Catenated Halides and Hydrides	479	(1)
Catenated Oxoacids and Corresponding Salts	480	(1)
Sulfur Nitrides	481	(2)
Reactions and Compounds of Practical Importance	483	(2)
Sodium-Sulfur Batteries	483	(1)
Photoelectric Uses of Selenium and Tellurium	484	(1)
Sulfuric Acid	485	(1)
Selected Topic in Depth: Acid Rain	485	(10)
Summary	488	(2)
Problems	490	(5)
Group 7A: The Halogens	495	(34)
Discovery and Isolation of the Elements	495	(4)
Chlorine	495	(2)
Iodine	497	(1)
Bromine	497	(1)
Fluorine	498	(1)
Astatine	499	(1)
Fundamental Properties and the Network	499	(7)
Hydrides	502	(2)
Halides	504	(1)
Oxides	505	(1)
Oxoacids and Their Salts	506	(4)
Hypohalous Acids, HOX, and Hypohalites, OX-	506	(2)
Halous Acids, HOXO, and Halites, XO-2	508	(1)
Halic Acids, HOXO2, and Halates, XO-3	508	(1)
Perhalic Acids, HOXO3, and Perhalates, XO-4	509	(1)
Neutral and Ionic Interhalogens	510	(4)
Reactions and Compounds of Practical Importance	514	(3)
Fluoridation	514	(2)
Chlorination	516	(1)
Bleaches	516	(1)
Bromides	517	(1)
Selected Topic in Depth: Chlorofluorocarbons (CFCs)-A Threat to the Ozone Layer	517	(12)
Summary	521	(2)
Problems	523	(6)
Group 8A: The Noble Gases	529	(20)
Discovery and Isolation of the Elements	529	(4)
Argon	530	(1)
Helium	531	(1)
Krypton, Neon, and Xenon	532	(1)
Radon	532	(1)
Fundamental Properties and the Network	533	(2)
Compounds of Noble Gases	535	(5)
History	535	(1)
Fluorides	536	(2)
Structures	538	(1)
Other Compounds	539	(1)
Physical Properties and Elements of Practical Importance	540	(2)
Selected Topic in Depth: Radon as a Carcinogen	542	(7)
Summary	543	(2)
Problems	545	(4)
A Word about Sources	549	(6)
Credit References	555	(2)
Lists of Figures, Tables, Formulas, and Constants	557	(4)
Index	561