Inorganic Chemistry（无机化学美国经典教材） 英文版.pdf

Inorganic Chemistry This page intentionally left blankInorganic Chemistry James E.House Illinois Wesleyan University and Illinois State University AMSTERDAM BOSTON HEIDELBERG LONDON OXFORD NEW YORKPARIS SAN DIEGO SAN FRANCISCO SINGAPORE SYDNEY TOKYOAcademic Press is an imprint of Elsevier Academic Press is an imprint of Elsevier 30 Corporate Drive,Suite 400,Burlington,MA 01803,USA 525 B Street,Suite 1900,San Diego,California 92101-4495,USA 84 Theobalds Road,London WC1X 8RR,UK?This book is printed on acid-free paper.Copyright 2008,Elsevier Inc.All rights reserved.No part of this publication may be reproduced or transmitted in any form or by any means,electronic or mechanical,including photocopy,recording,or any information storage and retrieval system,without permission in writing from the publisher.Permissions may be sought directly from Elseviers Science&Technology Rights Department in Oxford,UK:phone:(?44)1865 843830,fax:(?44)1865 853333,E-mail:.You may also complete your request on-line via the Elsevier homepage(http:/),by selecting “Support&Contact”then “Copyright and Permission”and then “Obtaining Permissions.”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,InorganicTextbooks.I.Title.QD151.5.H68 2008 546dc22 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 Printed in Canada 08 09 10 11 9 8 7 6 5 4 3 2 1 Contents Preface xiPART 1 Structure of Atoms and Molecules 1CHAPTER 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 2?and H 2 Molecules 73 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 4.3 Complex StructuresA 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 Hckel Method 161PART 2 Condensed Phases 177CHAPTER 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 Ionic 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 258vi Contents 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 282PART 3 Acids,Bases,and Solvents 287CHAPTER 9 Acid-Base Chemistry 289 9.1 Arrhenius Theory 289 9.2 Brnsted-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 349PART 4 Chemistry of the Elements 353CHAPTER 11 Chemistry of Metallic Elements 355 11.1 The Metallic Elements 355 11.2 Band Theory 356 11.3 Group IA and IIA Metals 359 11.4 Zintl Phases 367 11.5 Aluminum and Beryllium 370Contents vii 11.6 The First-Row Transition Metals 372 11.7 Second-and Third-Row Transition Metals 374 11.8 Alloys 376 11.9 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 15.2 The Halogens 545 15.3 The Noble Gases 564PART 5 Chemistry of Coordination Compounds 575CHAPTER 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 599viii Contents 16.8 Complexes of Second-and Third-Row Metals 599 16.9 The 18-Electron Rule 601 16.10 Back Donation 604 16.11 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 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 Jrgensens Method 665 18.8 Charge Transfer Absorption 666 CHAPTER 19 Composition and Stability of Complexes 671 19.1 Composition of Complexes in Solution 671 19.2 Jobs 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 20.1 Synthesis of Coordination Compounds 695 20.2 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 Trans Effect 721Contents ix 20.10 Electron Transfer Reactions 725 20.11 Reactions in Solid Coordination Compounds 728CHAPTER 21 Complexes Containing Metal-Carbon and Metal-Metal Bonds 739 21.1 Binary Metal Carbonyls 739 21.2 Structures of Metal Carbonyls 742 21.3 Bonding of Carbon Monoxide to Metals 744 21.4 Preparation of Metal Carbonyls 747 21.5 Reactions of Metal Carbonyls 748 21.6 Structure and Bonding in Metal Alkene Complexes 754 21.7 Preparation of Metal Alkene Complexes 760 21.8 Chemistry of Cyclopentadienyl and Related Complexes 761 21.9 Bonding in Ferrocene 764 21.10 Reactions of Ferrocene and Other Metallocenes 767 21.11 Complexes of Benzene and Related Aromatics 770 21.12 Compounds Containing Metal-Metal Bonds 773 CHAPTER 22 Coordination Compounds in Catalysis and Biochemistry 779 22.1 Elementary Steps in Catalysis Processes 780 22.2 Homogeneous Catalysis 792 22.3 Bioinorganic Chemistry 802Appendix A:Ionization Energies 817Appendix B:Character Tables for Selected Point Groups 821Index 827x Contents No single volume,certainly not a textbook,can come close to including all of the important topics in inorganic chemistry.The fi eld is simply too broad in scope and it is growing at a rapid pace.Inorganic chemistry textbooks refl ect a great deal of work and the results of the many choices that authors must make as to what to include and what to leave out.Writers of textbooks in chemistry bring to the task backgrounds that refl ect their research interests,the schools they attended,and their personalities.In their writing,authors are really saying“this is the fi eld as I see it.“In these regards,this book is similar to others.When teaching a course in inorganic chemistry,certain core topics are almost universally included.In addition,there are numerous peripheral areas that may be included at certain schools but not at oth-ers depending on the interests and specialization of the person teaching the course.The course content may even change from one semester to the next.The effort to produce a textbook that presents cover-age of a wide range of optional material in addition to the essential topics can result in a textbook for a one semester course that contains a thousand pages.Even a“concise”inorganic chemistry book can be nearly this long.This book is not a survey of the literature or a research monograph.It is a text-book that is intended to provide the background necessary for the reader to move on to those more advanced resources.In writing this book,I have attempted to produce a concise textbook that meets several objectives.First,the topics included were selected in order to provide essential information in the major areas of inor-ganic chemistry(molecular structure,acid-base chemistry,coordination chemistry,ligand fi eld theory,solid state chemistry,etc.).These topics form the basis for competency in inorganic chemistry at a level commensurate with the one semester course taught at most colleges and universities.When painting a wall,better coverage is assured when the roller passes over the same area several times from different directions.It is the opinion of the author that this technique works well in teaching chemistry.Therefore,a second objective has been to stress fundamental principles in the discussion of several topics.For example,the hard-soft interaction principle is employed in discussion of acid-base chemistry,stability of complexes,solubility,and predicting reaction products.Third,the presentation of topics is made with an effort to be clear and concise so that the book is portable and user friendly.This book is meant to present in convenient form a readable account of the essentials of inorganic chemistry that can serve as both as a textbook for a one semester course upper level course and as a guide for self study.It is a textbook not a review of the literature or a research monograph.There are few references to the original literature,but many of the advanced books and monographs are cited.Although the material contained in this book is arranged in a progressive way,there is fl exibility in the order of presentation.For students who have a good grasp of the basic principles of quantum mechanics and atomic structure,Chapters 1 and 2 can be given a cursory reading but not included in the required course material.The chapters are included to provide a resource for review and self study.Chapter 4 presents an overview structural chemistry early so the reader can become familiar with many types of inorganic structures before taking up the study of symmetry or chemistry of specifi c elements.Structures of inorganic solids are discussed in Chapter 7,but that material could easily be studied xi Preface before Chapters 5 or 6.Chapter 6 contains material dealing with intermolecular forces and polarity of molecules because of the importance of these topics when interpreting properties of substances and their chemical behavior.In view of the importance of the topic,especially in industrial chemistry,this book includes material on rate processes involving inorganic compounds in the solid state(Chapter 8).The chapter begins with an overview of some of the important aspects of reactions in solids before considering phase transitions and reactions of solid coordination compounds.It should be an acknowledged fact that no single volume can present the descriptive chemistry of all the elements.Some of the volumes that attempt to do so are enormous.In this book,the presenta-tion of descriptive chemistry of the elements is kept brief with the emphasis placed on types of reac-tions and structures that summarize the behavior of many compounds.The attempt is to present an overview of descriptive chemistry that will show the important classes of compounds and their reac-tions without becoming laborious in its detail.Many schools offer a descriptive inorganic chemistry course at an intermediate level that covers a great deal of the chemistry of the elements.Part of the rationale for offering such a course is that the upper level course typically concentrates more heav-ily on principles of inorganic chemistry.Recognizing that an increasing fraction of the students in the upper level inorganic chemistry course will have already had a course that deals primarily with descriptive chemistry,this book is devoted to a presentation of the principles of inorganic chemistry while giving an a brief overview of descriptive chemistry in Chapters 1215,although many topics that are primarily descriptive in nature are included in other sections.Chapter 16 provides a survey of the chemistry of coordination compounds and that is followed by Chapters 1722 that deal with structures,bonding,spectra,and reactions of coordination compounds.The material