Concepts and Models of Inorganic Chemistry, 3rd Edition

by Bodie E. Douglas (Univ. of Pittsburgh); Darl H. McDaniel (Univ. of Cincinnati); John J. Alexander (Univ. of Cincinnati)

• ISBN13: 9780471629788
• ISBN10: 0471629782
• Edition: 3rd
• Format: Hardcover
• Copyright: 1994-02-01
• Publisher: Wiley

Summary

A clear introduction to modern inorganic chemistry, covering both theory and descriptive chemistry. Uses concepts and models as an organizing principle to facilitate students' integration of ideas. This edition contains a new chapter on group theory and offers expanded coverage of solid state. Features numerous figures and solved examples.

Table of Contents

PART I Some Basic Concepts	1	(148)
CHAPTER 1 Atomic Structure and the Periodic Table	3	(51)
1.1 Models in Chemistry	3	(2)
1.2 Historical Background	5	(3)
1.3 Atomic Structure and the Basis of the Periodic Table	8	(24)
1.4 Spectroscopic Terms and the Zeeman Effect; One-Electron Atoms	32	(2)
1.5 The Vector Model and Term Structure for Polyelectron Atoms	34	(8)
1.6 Ionization Energies	42	(4)
1.7 Electron Affinities	46	(1)
1.8 Absolute Electronegativity and Absolute Hardness	47	(3)
General References	50	(1)
Problems	51	(3)
CHAPTER 2 Molecular Models	54	(51)
2.1 Review of Covalent Bonding	54	(12)
2.2 Valence Bond (Pauling-Slater) Theory	66	(6)
2.3 Shapes of Molecules	72	(10)
2.4 Electronegativity	82	(6)
2.5 Radii of Atoms in Covalent Compounds	88	(4)
2.6 The Hydrogen Bond	92	(7)
2.7 Weak Interactions in Covalent Substances	99	(3)
General References	102	(1)
Problems	102	(3)
CHAPTER 3 Symmetry	105	(44)
3.1 Introduction	105	(1)
3.2 Symmetry Elements and Symmetry Operations	106	(8)
3.3 Introduction to Groups	114	(2)
3.4 Symmetry Point Groups	116	(11)
3.5 Class Structure, Representations, and Character Tables	127	(11)
3.6 Chemical Applications of Symmetry	138	(3)
3.7 Summary of Terminology and Notation from Symmetry and Group Theory	141	(3)
General References	144	(1)
Appendix 3.1 Matrix Representation of Transformation and Matrix Multiplication	144	(3)
Appendix 3.2 The Direct Product of Representations	147	(1)
Problems	147	(2)
PART II Bonding and Structure	149	(158)
CHAPTER 4 Discrete Molecules: Molecular Orbitals	151	(47)
4.1 Diatomic Molecules	151	(12)
4.2 Linnett's Double Quartet	163	(3)
4.3 Triatomic Molecules	166	(10)
4.4 Xenon Difluoride	176	(1)
4.5 Boron Trifluoride--A Group Theoretical Treatment	177	(8)
4.6 Diborane	185	(3)
4.7 Cyclic-Planar (Pie) Molecules	188	(5)
4.8 Basis Sets and Frontier Orbitals	193	(3)
General References	196	(1)
Problems	196	(2)
CHAPTER 5 Inorganic Solids: Ionic Models	198	(53)
5.1 Simple Ionic Solids	199	(5)
5.2 Close Packing	204	(2)
5.3 Ionic Structures Based Upon Close-Packed Arrangements	206	(5)
5.4 Radius Ratios for Stable Arrangements in Ionic Crystals	211	(1)
5.5 Common Structures of Ionic Crystals	212	(8)
5.6 Notation for Structures Based Upon Close Packing	220	(1)
5.7 Ionic Radii	221	(3)
5.8 Lattice Energy	224	(11)
5.9 Solubilities of Ionic Substances	235	(3)
5.10 Giant Molecules	238	(1)
5.11 Structures of Silicates	239	(7)
5.12 Crystal Structures of Metals	246	(2)
General References	248	(1)
Problems	249	(2)
CHAPTER 6 Solid-State Chemistry	251	(56)
6.1 Crystal Structure	251	(13)
6.2 Defect Structures	264	(4)
6.3 Electronic Structure of Solids	268	(16)
6.4 Graphite as a Two-Dimensional Solid	284	(8)
6.5 Metals, Insulators, and Semiconductors	292	(2)
6.6 Some Limitations and Extensions of the Simple Band Theory	294	(1)
6.7 Superconductivity	295	(5)
6.8 Buckminsterfullerene	300	(3)
General References	303	(1)
Problems	304	(3)
PART III Chemical Reactions	307	(70)
CHAPTER 7 Acids and Bases	309	(41)
7.1 Models of Acids and Bases	309	(4)
7.2 Protonic Acids	313	(13)
7.3 Acid-Base Behavior of the Binary Oxides and Aqua Cations	326	(7)
7.4 Nonprotonic Concepts of Acid-Base Reactions	333	(10)
7.5 The Drago-Wayland Equation	343	(3)
7.6 Solid Acids	346	(1)
General References	347	(1)
Problems	347	(3)
CHAPTER 8 Oxidation-Reduction Reactions	350	(27)
8.1 Conventions Covering Standard States	350	(2)
8.2 Methods of Determining Changes in Free Energy	352	(1)
8.3 Schematic Representation of Galvanic Cells	353	(1)
8.4 Conventions Regarding Cells	354	(2)
8.5 Calculations Using emf Data	356	(7)
8.6 Pourbaix (or Predominance Area) Diagrams	363	(3)
8.7 Geochemistry of Manganese	366	(2)
8.8 Periodic Trends among the Transition Elements	368	(2)
8.9 Some Redox Reactions of Nonmetals	370	(2)
8.10 Equilibrium Constants from emf Data	372	(1)
General References	373	(1)
Problems	373	(4)
PART IV Coordination Chemistry	377	(182)
CHAPTER 9 Models and Stereochemistry	379	(62)
9.1 Introduction	379	(2)
9.2 Analytical Applications	381	(2)
9.3 Brief Summary of Nomenclature of Coordination Compounds	383	(1)
9.4 Stabilities of Coordination Compounds	384	(6)
9.5 Werner's Coordination Theory	390	(2)
9.6 Valence Bond Models	392	(6)
9.7 Simple Electrostatic Models of Bonding	398	(3)
9.8 The Ligand-Field Theory	401	(10)
9.9 Isomerism of Coordination Compounds	411	(2)
9.10 Coordination Number Four	413	(2)
9.11 Coordination Number Six	415	(9)
9.12 Coordination Number Five	424	(3)
9.13 Lower Coordination Numbers	427	(1)
9.14 Higher Coordination Numbers	428	(4)
9.15 Stereochemically Nonrigid and Fluxional Molecules	432	(5)
General References	437	(1)
Problems	438	(3)
CHAPTER 10 Spectra and Bonding	441	(41)
10.1 Introduction	441	(1)
10.2 Ligand-Field Spectra of Octahedral Complexes	442	(17)
10.3 Complexes of Lower Symmetry	459	(4)
10.4 Charge Transfer Bands	463	(2)
10.5 Circular Dichroism and Optical Rotatory Dispersion	465	(3)
10.6 Pictorial Molecular-Orbital Description of Bonding	468	(3)
10.7 Effects of (Pie) Bonding	471	(1)
10.8 Group Theoretical Treatment	472	(6)
10.9 Comparison of the Different Approaches to Bonding in Coordination Compounds	478	(1)
General References	478	(1)
Problems	479	(3)
CHAPTER 11 Reaction Mechanisms	482	(77)
11.1 The Kinetic Model	482	(4)
11.2 Introduction to Ligand Substitution Reactions	486	(1)
11.3 Octahedral Complexes: Ligand Substitution Reactions	487	(30)
11.4 Racemization Reactions	517	(2)
11.5 Square-Planar Complexes: Ligand Substitution Reactions	519	(9)
11.6 Catalysis of Substitution by Redox Processes	528	(1)
11.7 Redox Reactions	528	(15)
11.8 Photochemical Reactions	543	(6)
General References	549	(1)
Problems	549	(10)
PART V Organometallic Chemistry	559	(144)
CHAPTER 12 General Principles	561	(53)
12.1 Introduction	562	(1)
12.2 Carbonyl Complexes	562	(15)
12.3 Bonding of Organic Ligands to Metals	577	(20)
12.4 Experimental Evidence for Back-Donation	597	(6)
12.5 Structural Characterization of Organometallic Compounds	603	(2)
12.6 The Isolobal Analogy	605	(1)
12.7 Dihydrogen Complexes	606	(3)
General References	609	(1)
Problems	609	(5)
CHAPTER 13 Survey of Organometallic Compounds	614	(39)
13.1 Some Chemistry of Olefin Complexes	614	(1)
13.2 Alkyne Complexes	615	(4)
13.3 Allyl Complexes	619	(3)
13.4 Butadiene Complexes	622	(4)
13.5 Cyclic (Pie) Complexes	626	(9)
13.6 Compounds with Metal-Carbon (Sigma) Bonds	635	(11)
13.7 Compounds with Multiple Metal-Carbon Bonds	646	(4)
General References	650	(1)
Problems	650	(3)
CHAPTER 14 Organometallic Reactions, Mechanisms, and Catalysis	653	(50)
14.1 Fundamental Reactions	653	(32)
14.2 Homogeneous Catalysis by Soluble Transition Metal Complexes	685	(12)
General References	697	(1)
Problems	697	(6)
PART VI Selected Topics	703
CHAPTER 15 Chemistry and Periodic Trends among Metals	705	(55)
15.1 General Periodic Trends among Metals	705	(3)
15.2 Group 1 (IA)--The Alkali Metals	708	(10)
15.3 Group 2 (IIA)--The Alkaline Earth Metals	718	(6)
15.4 Group 11 (IB)--The Coinage Metals	724	(5)
15.5 Group 12 (IIB)--The Zinc Subgroup	729	(3)
15.6 Group 3 (IIIA)--The Scandium Family and Rare Earths	732	(5)
15.7 The Actinide Metals	737	(1)
15.8 Transition Metals, Groups 4-7 (IVA-VIIA)	738	(9)
15.9 Groups 8, 9, and 10 (Group VIII)	747	(4)
15.10 Compounds Containing Metal-Metal Bonds	751	(6)
General References	757	(1)
Problems	757	(3)
CHAPTER 16 Chemistry of Some Nonmetals	760	(56)
16.1 General Periodic Trends for Nonmetals	760	(1)
16.2 Nitrogen and Phosphorus	761	(12)
16.3 Oxygen, Sulfur, and Selenium	773	(16)
16.4 The Halogens	789	(18)
16.5 The Noble Gases	807	(5)
General References	812	(1)
Problems	813	(3)
CHAPTER 17 Cluster and Cage Compounds	816	(72)
17.1 Introduction	816	(3)
17.2 The Bonding Problem in Boranes	819	(4)
17.3 Structures of the Boron Hydrides	823	(3)
17.4 Molecular Orbital Description of Bonding in Boron Hydrides	826	(6)
17.5 Heteroboranes	832	(2)
17.6 Chemistry of the Boranes	834	(7)
17.7 Synthesis of Boron Hydrides	841	(2)
17.8 Carboranes	843	(4)
17.9 Some Chemistry of Group 13	847	(7)
17.10 Cluster Compounds	854	(23)
17.11 Electron-Precise Compounds and their Relation to Clusters	877	(2)
General References	879	(1)
Problems	880	(8)
CHAPTER 18 Bioinorganic Chemistry	888
18.1 Essential Elements	888	(5)
18.2 Oxygen Utilization	893	(8)
18.3 Supply and Storage of Iron	901	(4)
18.4 Oxidation-Reduction Processes	905	(5)
18.5 Metalloenzymes	910	(9)
18.6 Vitamin B(12)	919	(3)
18.7 Nitrogenase	922	(2)
18.8 Photosynthesis	924	(2)
18.9 Roles of Na^+, K^+, Mg^2+, Ca^2+, and Ion Pumps	926	(1)
General References	927	(1)
Problems	928
APPENDIX A Units	A-1
APPENDIX B Nomenclature of Inorganic Chemistry	B-1
APPENDIX C Character Tables	C-1
APPENDIX D Tanabe-Sugano Diagrams	D-1
APPENDIX E Standard Half-Cell emf Data	E-1
INDEX	I-1