Inorganic Chemistry

865 Pages·2008·6.59 MB·English

by  James E. House

Inorganic Chemistry
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Inorganic Chemistry
James E. House
Illinois Wesleyan University
and Illinois State University
AMSTERDAM • BOSTON • HEIDELBERG • LONDON • OXFORD • NEW YORK
PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO
Academic Press is an imprint of Elsevier
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Library of Congress Cataloging-in-Publication Data
House, J. E.
Inorganic chemistry / James E. House.
p. cm.
Includes index.
ISBN 978-0-12-356786-4 (paper cover : alk. paper) 1. Chemistry, Inorganic—Textbooks. I. Title.
QD151.5.H68 2008
546—dc22
2008013083
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
ISBN: 978-0-12-356786-4
For information on all Academic Press publications
visit our Web site at www.books.elsevier.com
Printed in Canada
08 09 10 11 9 8 7 6 5 4 3 2 1
Contents
Preface xi
PART 1 Structure of Atoms and Molecules 1
CHAPTER 1 Light, Electrons, and Nuclei 3
1.1 Some Early Experiments in Atomic Physics 3
1.2 The Nature of Light 7
1.3 The Bohr Model 11
1.4 Particle-Wave Duality 15
1.5 Electronic Properties of Atoms 17
1.6 Nuclear Binding Energy 22
1.7 Nuclear Stability 24
1.8 Types of Nuclear Decay 25
1.9 Predicting Decay Modes 29
CHAPTER 2 Basic Quantum Mechanics and Atomic Structure 35
2.1 The Postulates 35
2.2 The Hydrogen Atom 44
2.3 The Helium Atom 49
2.4 Slater Wave Functions 51
2.5 Electron Confi gurations 52
2.6 Spectroscopic States 56
CHAPTER 3 Covalent Bonding in Diatomic Molecules 65
3.1 The Basic Ideas of Molecular Orbital Methods 65
3.2 The H (cid:3) and H Molecules 73
2 2
3.3 Diatomic Molecules of Second-Row Elements 76
3.4 Photoelectron Spectroscopy 83
3.5 Heteronuclear Diatomic Molecules 84
3.6 Electronegativity 87
3.7 Spectroscopic States for Molecules 91
CHAPTER 4 A Survey of Inorganic Structures and Bonding 95
4.1 Structures of Molecules Having Single Bonds 95
4.2 Resonance and Formal Charge 105
vi Contents
4.3 Complex Structures—A Preview of Coming Attractions 117
4.4 Electron-Defi cient Molecules 125
4.5 Structures Having Unsaturated Rings 127
4.6 Bond Energies 129
CHAPTER 5 Symmetry and Molecular Orbitals 137
5.1 Symmetry Elements 137
5.2 Orbital Symmetry 145
5.3 A Brief Look at Group Theory 148
5.4 Construction of Molecular Orbitals 153
5.5 Orbitals and Angles 158
5.6 Simple Calculations Using the Hückel Method 161
PART 2 Condensed Phases 177
CHAPTER 6 Dipole Moments and Intermolecular Interactions 179
6.1 Dipole Moments 179
6.2 Dipole-Dipole Forces 184
6.3 Dipole-Induced Dipole Forces 186
6.4 London (Dispersion) Forces 187
6.5 The van der Waals Equation 191
6.6 Hydrogen Bonding 193
6.7 Cohesion Energy and Solubility Parameters 203
CHAPTER 7 I onic Bonding and Structures of Solids 211
7.1 Energetics of Crystal Formation 211
7.2 Madelung Constants 216
7.3 The Kapustinskii Equation 219
7.4 Ionic Sizes and Crystal Environments 220
7.5 Crystal Structures 224
7.6 Solubility of Ionic Compounds 229
7.7 Proton and Electron Affi nities 234
7.8 Structures of Metals 237
7.9 Defects in Crystals 240
7.10 Phase Transitions in Solids 243
7.11 Heat Capacity 245
7.12 Hardness of Solids 248
CHAPTER 8 Dynamic Processes in Inorganic Solids 255
8.1 Characteristics of Solid-State Reactions 255
8.2 Kinetic Models for Reactions in Solids 258
Contents vii
8.3 Thermal Methods of Analysis 266
8.4 Effects of Pressure 267
8.5 Reactions in Some Solid Inorganic Compounds 270
8.6 Phase Transitions 272
8.7 Reactions at Interfaces 276
8.8 Diffusion in Solids 277
8.9 Sintering 280
8.10 Drift and Conductivity 282
PART 3 Acids, Bases, and Solvents 287
CHAPTER 9 A cid-Base Chemistry 289
9.1 Arrhenius Theory 289
9.2 Brønsted-Lowry Theory 292
9.3 Factors Affecting Strength of Acids and Bases 296
9.4 Acid-Base Character of Oxides 301
9.5 Proton Affi nities 302
9.6 Lewis Theory 305
9.7 Catalytic Behavior of Acids and Bases 309
9.8 The Hard-Soft Interaction Principle (HSIP) 313
9.9 Electronic Polarizabilities 323
9.10 The Drago Four-Parameter Equation 324
CHAPTER 10 Chemistry in Nonaqueous Solvents 331
10.1 Some Common Nonaqueous Solvents 331
10.2 The Solvent Concept 332
10.3 Amphoteric Behavior 335
10.4 The Coordination Model 335
10.5 Chemistry in Liquid Ammonia 336
10.6 Liquid Hydrogen Fluoride 342
10.7 Liquid Sulfur Dioxide 345
10.8 Superacids 349
PART 4 Chemistry of the Elements 353
CHAPTER 11 Chemistry of Metallic Elements 355
1 1.1 The Metallic Elements 355
1 1.2 Band Theory 356
1 1.3 Group IA and IIA Metals 359
1 1.4 Zintl Phases 367
1 1.5 Aluminum and Beryllium 370
viii Contents
1 1.6 The First-Row Transition Metals 372
1 1.7 Second- and Third-Row Transition Metals 374
1 1.8 Alloys 376
1 1.9 Chemistry of Transition Metals 379
11.10 The Lanthanides 387
CHAPTER 12 Organometallic Compounds of the Main Group Elements 395
12.1 Preparation of Organometallic Compounds 396
12.2 Organometallic Compounds of Group IA Metals 398
12.3 Organometallic Compounds of Group IIA Metals 400
12.4 Organometallic Compounds of Group IIIA Metals 403
12.5 Organometallic Compounds of Group IVA Metals 408
12.6 Organometallic Compounds of Group VA Elements 409
12.7 Organometallic Compounds of Zn, Cd, and Hg 410
CHAPTER 13 Chemistry of Nonmetallic Elements I. Hydrogen, Boron, Oxygen and Carbon 415
13.1 Hydrogen 415
13.2 Boron 422
13.3 Oxygen 433
13.4 Carbon 444
CHAPTER 14 Chemistry of Nonmetallic Elements II. Groups IVA and VA 463
14.1 The Group IVA Elements 463
14.2 Nitrogen 480
14.3 Phosphorus, Arsenic, Antimony, and Bismuth 497
CHAPTER 15 Chemistry of Nonmetallic Elements III. Groups VIA to VIIIA 523
15.1 Sulfur, Selenium, and Tellurium 523
1 5.2 The Halogens 545
15.3 The Noble Gases 564
PART 5 Chemistry of Coordination Compounds 575
CHAPTER 16 Introduction to Coordination Chemistry 577
16.1 Structures of Coordination Compounds 577
16.2 Metal-Ligand Bonds 582
16.3 Naming Coordination Compounds 583
16.4 Isomerism 585
16.5 A Simple Valence Bond Description of Coordinate Bonds 592
16.6 Magnetism 597
16.7 A Survey of Complexes of First-Row Metals 599
Contents ix
1 6.8 Complexes of Second- and Third-Row Metals 599
1 6.9 The 18-Electron Rule 601
1 6.10 Back Donation 604
1 6.11 Complexes of Dinitrogen, Dioxygen, and Dihydrogen 609
CHAPTER 17 Ligand Fields and Molecular Orbitals 617
17.1 Splitting of d Orbital Energies in Octahedral Fields 617
17.2 Splitting of d Orbital Energies in Fields of Other Symmetry 621
17.3 Factors Affecting Δ 625
17.4 Consequences of Crystal Field Splitting 627
17.5 Jahn-Teller Distortion 630
17.6 Spectral Bands 631
17.7 Molecular Orbitals in Complexes 633
CHAPTER 18 Interpretation of Spectra 645
18.1 Splitting of Spectroscopic States 645
18.2 Orgel Diagrams 650
18.3 Racah Parameters and Quantitative Methods 652
18.4 The Nephelauxetic Effect 655
18.5 Tanabe-Sugano Diagrams 658
18.6 The Lever Method 662
18.7 Jørgensen’s Method 665
18.8 Charge Transfer Absorption 666
CHAPTER 19 Composition and Stability of Complexes 671
1 9.1 Composition of Complexes in Solution 671
19.2 Job’s Method of Continuous Variations 673
19.3 Equilibria Involving Complexes 675
19.4 Distribution Diagrams 681
19.5 Factors Affecting the Stability of Complexes 685
CHAPTER 20 Synthesis and Reactions of Coordination Compounds 695
2 0.1 Synthesis of Coordination Compounds 695
2 0.2 Substitution Reactions in Octahedral Complexes 701
20.3 Ligand Field Effects 708
20.4 Acid-Catalyzed Reactions of Complexes 712
20.5 Base-Catalyzed Reactions of Complexes 713
20.6 The Compensation Effect 715
20.7 Linkage Isomerization 716
20.8 Substitution in Square Planar Complexes 719
20.9 The T rans Effect 721