Inorganic Chemistry Principles of Structure and Reactivity Fourth Edition James E. Huheey University of Maryland Ellen A. Keiter Eastern Mlinois University Richard L. Keiter Eastern Minais University & HarperCollinsCollegePublishersFigures from the following journals are copyright © to the Americun Chemical Society: Accounts of Chemical Research, Chemicat and Engineering News, Chemical Reviews, Inorganic Chemistry, Journel of the Americen Chemical Soclety, Journal of Chetical Education, Journal of Physical Chemistry, and Orgonometallics. Grateful acknowledgment is also given to Acta Chetnica Scundinavica, The American Association for the Advancement of Science, The American Lestituie of Physics, Angewandte Chemie, The Chemical Society, The International Union of Crystallograpby. The Mineralogical Society af Americs, The National Academy of Sciences, U.S_A,, Nature, The Nobel Foundation of the Royal Academy of Science, ‘Sweden, Zelischrifi far anorganische und allgemeine Chemie, aed Zeitschrifi far Natarforscinme for the use of materials that are copyright © to them. Individual acknowledgments are given on the pages where the material occurs. Aboot the Cover ‘The crystal structure of boggsite, a secently discovered natural zeolite, is composed of sodium, calcium, aluminum, silicon, hydrogen, and oxygen, [ts unique atomic structure (of ten and twelve rings was determined by J. J. Pluth and J. V. Smith, geophysicists at the University of Chicago. Modeling tools used to construct the cover photograph are being devetoped in the Catalysis and Sorption Project of BIOSYM Technologies. Inc... San Diego, California. Structure of boggsite courtesy of Pruth, J. 3.; Smith, 1. V. Am. Mincral. 1990, 75, 501-507, und computer graphic by John M. Newsam. BIOSYM Technologies, Inc. ‘Sponsoring Editor: Jane Piro Project Coordination: Bim Street Publishing Services, Inc. Cover Design: Kay Fulton Cover Photo: Professor Join M, Newsam, BIOSYM Techuoogies, Ine. ‘Compositor: Better Graphics, Inc. Printer and Binder: R.R. Donnelley & Sons Company ‘Cover Printer: Lehigh Press Lithographers Inorganic Chemistry: Principles of Structure and Reactivity, Fousth Edition Copyright © 1993 by HarperCollins College Publishers All sights reserved. Printed in the United States of America. No pan of this book may bbe used or reproduced in any manner whatsoever without written permission. except in the case of brief quotations embodied in critical articles and reviews. For information, address HarperCollins College Publishers, 10 East S3rd Street, New York, NY 10022, Library of Congress Cataloging-in-Publication Data Huheey, James E. Inorganic chemistry: principles of structure and reactivity 7 James E. Huheey, Ellen A. Keiter, Richard L. Keiter. pom. Includes bibliographical references and index. ISBN 0-06-042995-x ‘Chemistry, Inorganic. 1. Keiter, Ellen A. Il. Keiter, Richard L._ iti, Tile. QDISL2.Hea 1993 546420 92.3608, 97 98 $8 1211 109To Catherine, Cathy, Terry, Mercedes, Thorfin, trene, Alvin, Eric, and Lise,Contents Preface xi To the Student xiv Excerpts from the Preface to the Third Edition xvi Chapter 1 What Is Inarganic Chemistry? 1 Inorganic Chemistry. the Beginnings Inorganic Chemistry, an Example 2 Chemical Structure of Zeolites and Other Chemical Systems 3 Chemical Reactivity 5 Conclusion 7 Chapter 2 The Structure af the Atom 10 The Hydrogen Atom 10 The Polyelectronic Atom 20 Chapter 3 Symmetry and Group Theary 46 Symmetry Elements and Symmetry Operations 46 Point Groups and Moleculur Symmetry 53 Irredueible Representations and Character Tables 59 Uses of Point Group Symmetry 63 Crystallography 74vi Contents Chopter 4 Bonding Models in Inorgonic Chemistry: 1. lonic Compounds 92 ‘The lonic Bond 92 Lattice Energy 99 Size Effects 112 ‘The Predictive Power of Thermochemical Calculations on Ionic Compounds 127 Covalent Character in Predominantly tonic Bonds {29 Conclusion 134 Chopter $ Bonding Models in Inarganic Chemistry: 2. The Covolent Bond 138 Valence Band Theory 139 ‘Molecular Orbita! Theory 153 Electronegativity (82 Chopter 6 The Structure and Reoctivity of Molecules 203 ‘The Structure of Molecules 203 Structure and Hybridization 220 Bond Lengths 232 Experimental Determination of Molecular Structure 233 Some Simple Reactions of Covalently Bonded Molecules 237 Chopter 7 The Solid State 2S2 The Structures of Complex Solids 253 Imperfections in Crystals 263 Conductivity in lonic Solids 266 ‘Solids Held Together by Covatens Bonding 269 Solid-State Materials with Polar Bonds 276 rer 8 Chemical Forces 290 Snternuctear Distances and Atomic Radi 290 ‘Types of Chemical Forces 296 Hydrogen Bonding 300 Effects of Chemical Forces 307Contents vii Chopter 9 Acid-Base Chemistry 318 Acid-Base Concepts 318 Measures of Acid-Base Strength 330 Hard and Soft Acids and Bases 344 Chopter 10 ‘Chemistry in Aqueous ond Nonoqueous Solvents 359 Water 360 Nonaqueous Solvents 360 Molten Satts 374 Electrode Potentials and Electromotive Forces 378 Chopter 11 Coordination Chemistry: Bonding, Spectro, ond Magnetism 387 Bonding in Coordination Compounds 391 Valence Bond Theory 391 Crystal Field Theory 394 Molecular Orbital Theory 413 Electronic Spectra of Complexes 433 Magnetic Properties of Complexes 459 Ghopter 12 ‘Coordinotion Chemistry: Structure 472 Coordination Number | 472 Coordination Number 2-473 Coordination Number 3 474 Coordination Number 4 474 Coordination Number 5 479 Coordination Number 6 488 Coordination Number 7 503 Coordination Number 8 507 ‘Higher Coordination Numbers 509 Generalizations about Coordination Numbers 511 Linkage Isomerism 513 Other Types of Isomerism S21 ‘The Chelate Effect 522viii" Contents Chapter 13 Coordination Chemistry: Reactions, Kinetics, and Mechanisms 537 Substitution Reactions in Square Planar Complexes 538 ‘Thermodynamic and Kinetic Stability 547 Kinetics of Octahedral Substitution 548. ‘Mechanisms of Redox Reactions 557 Chapter 14 Some Descriptive Chemistry of the Metals 577 General Periodic Trends 578 Chemistry of the Various Oxidation States of Transition Metals S80 ‘The Chemistry of Elements Potassium-Zinc: Comparison by Electron Configuration 582 ‘The Chemistry of the Heavier Transition Metals 587 ‘Oxidation States and EMFs of Groups 1-12 588 ‘The Lanthanide and Actinide Elements 599 Coordinalion Chemistry 608 ‘The Transactinide Elements 613 Chapter 15 Organometallic Chemistry 623 ‘The 18-Electron Rule 624 Metal Carbonyl Complexes 630 Nitrosyl Complexes 650 Dinitrogen Complexes 653 Metal Atkyls, Carbenes, Carbynes, and Carbides 655 ‘Nonaromatic Alkene and Alkyne Complexes 662 Metallocenes 669 Reactions of Organometallic Complexes 686 Catalysis by Organometallic Compounds 705 ‘Stereochemically Nonrigid Molecules 723 Conctusion 730 Chapter 16 Inargonic Chains, Rings, Cages, ond Clusters 738 Chains 738 Rings 765Cages 785 Boron Cage Compounds 789 Metal Ctusters 807 Conchusion B19 Chapter 17 The Chemistry af the Halagens and the Nable Gases 824 ‘Noble Gas Chemisiry 825 Halogens in Positive Oxidation States 837 Halides 848 Pseucohatogens 852 Electrochemistry of the Halogens and Pseudobalogens 853 GChopter 18 Periodicity 857 First- and Second-Row Anomalies 858 ‘The Use of p Orbitals in Pi Bonding 861 ‘The Use (or Not) of d Orbitals by Nonmetals 866 Reactivity and d Orbital Participation 875 Periodic Anomalies of the Nonmetals and Posttransition Metals 876 Chapter 19 The Inorganic Chemistry of Biclagical Systems 889 Energy Sources for Life 889 Metalloporphyrins and Respiration 891 Dioxygen Binding, Transport, and Utilization 895 Electron Transfer, Respiration, and Photosynthesis 91! Enzymes 919 . Nitrogen Fixation 933 * 8 ‘The Biochemistry of tron 935 “t Essential and Trace Elerents in Biological Systems 941 Biochemistry of the Nonmetals 953 Medicinal Chemistry 954 ‘Summary 960 Postscript 960x Contents Appendix A The Literature af Inarganic Chemistry A-1 ‘Appendix B Units and Conversion Factors A3 Appendix C Atamic States and Term Symbals A-7 wooen dix D Choracter Tables A-13 Appendix E Band Energies and Band Lengths A-21 Appendix F__ An Overview af Standard Reduction Patenticis of the Appendix G Tenebe-Sugane Diagrams A-38 Appendix H Models, Stereachemistry, and the Use af Stereapsis A-40 Appendix - The Rules af Inarganic Nomenclature A-46 Index A-78Preface Te has been twenty years since the senior author and Harper & Row, Publishers produced the first edition of Inorganic Chemistry: Principles of Steucture ond Reac- ‘iviry. tn that time: (a) The senior author has become 20 years more senior; (b) «wo new authors have joined the project; (c) Harper & Row, Publisbers has become HarperCollins Publishers; aod, mst impostant, (d) inorganic chemistry has continued to grow from its already lusty exisience of two decades ago. It is becoming increas ingly impossible for one person ta monitor all areas of inorganic chemistry. The new authors bring so the book their interests in coordination chemistry, organometallics, and physical methods, as well as fresh viewpoints on & number of other topics. Nevertheless, the philosophy af the book remains unchanged: Ta bring to the reader the essentials af inorganic chemistry in an easily readable format with emphasis on the fact that inorganic chemistry is an exciting field of research rather than a closed body of knowledge. We three authors brought very different undergraduate experiences to the teach- ing of inorganic chemistry and she revision of this edition. One of us received a B.S. degree from a Ph.D. granting institution, one from a private non-Ph.D. tiberal arts ccotfege, and one from a public non-Ph.D. liberal arts college. We have taught under- graduate and graduate inorganic courses in a variety of settings. When we sat dewn to discuss the revision, there werea number of things that we agreed upon: (1) The book ‘would be substantially updated. (2) The material presented would continue to be thoroughly referenced, and the references would continue to sppear on the pages of interest. A relevant reference woukt not be omitted just because it had appeared in previous editions. (3) New illustrations, many from the original Hlerature, would be added. (4) A greater setection of problems, many of them new, woutd be provided. Many problems would require brary assistance, while others would cover the funda- mental aspects of cach topic. (5) A chapter on symmetry would be added. (6) Solid state chemistry would be given more emphasis. (7) The kinelics chapter would be more fully developed. (8) The descriptive and organometallic chemistry of the tan- thanides and actinides would be included in the corresponding chapters for the transition metals, General consensus (among both authors and users) comes more easily than agreement on specifics. Our discussions of the symmetry chapterare a good example. All of us agreed that the teaching of symmetry considerations at most institotions had xifor the most part been delegated to the inorganic chemists. But how much should be ‘aught, and how mutch should the remainder of the book depend upon this chapter? At a mainitaur we helieved that a good introduction to point groups was essential. We also wanted to inchide some character table applications buc not so rach that the inorganic chemistry in the book coukin’t be taught without it. Applications appear hereand there in the text but can be avoided if desired. The chapter, as completed, has ‘concentrated on farniliarizing the student with many applications of symmetry as used. bby the inorganic chemist, including spectroscopy and crystallography, without pur- Porting (a be a rigorous exposition of the subject. ‘We may anticipate an eventual consensus on the amount and place of symmetry in the chemistry curriculum, but for now we have assumed no prior bockground in the subject, We have thus tried to illustrate a wide variety of uses of symmetry without delving deeply into the background theory. We hope that those new to the topic can find a usefut introduction to the application of symmetry to problems in inorganic chemistry. On the other hand, those having previous experience with the subject may Wish to use this chapter as.a brief review. And. recognizing that things are in a state of flux, we have atternpted to make it possible to study various topics such as orbital overtep, crysial field theory, and related material, as in the past, with minimal ‘reference to symmetry if desired. Students using this book come fromm exceedingly diverse backgrounds: Some will have had extensive experience in physical and organic chemistry, perhaps even a previous course in descriptive inorganic chemistry. For many. however, this will be the first contact with inorganic chemistry, and some may have had only limited experience with bonding theory in other courses. For this reason, the early chapters present the fundamentals of aternic and molecular structure from the inorganic chemn- ist's perspective. The well-prepared reader may use these chapters as a brief review as Well as mortar to chink hetween previous blocks of knowledge. The middle chapters of the book present the “heart of inorganic chemistry,” solid-state chemisiry beyond simple salts, acid-base chemistry in a variety of solvents. and the gas phase, and ‘soordination chemistry discussed in terras of bonding, spectra, magnetism, structure, and reactions. Jn line with the philosophy of a topical appronch and flexible course content, the last six chapters of the book are essentially independent of each other, and one or more may readily be omitted depending on the inclination of the instructor and the ‘ime available, ‘The fourth edition, in its entirety, works nicely for that unfortunately rare beast. the rwo-semester course, But that means that it is balanced and should work equally well for a one-semester course—the instructor must pick and choose. We firmly believe that it is more useful to provide a large number of topics. wherein one can select the topics to be covered, than to dictate a “minimum core."” We hope the book includes the topics that all instructors find essential, but we hope that it also includes their favorite topics. It obviously incledes ours. A solutions manual that contains answers to all end-of-chapter problems accompanies the fourth edition. We would like to thank our colleagues at tbe University of Maryland at College Park (UMCP) and Eastern Illinois University (EIU) who bave helped in a multitude of ways. Professor Huheey’s colleagues who hetped with previous editions are listed in the “Excerpts fromm the Preface to the Third Edition™ (page xvi), and their ferther help is gratefully acknowledged. In addition, we would like to thank Bryan Eichhorn (UMCP}, William Harwood (UMCP), Mark McGuire (EIU), Robert Filato (UMCP), and Rinaldo Poli (UMCP) for special help with this edition. We would also ike toPrafocs —xitt thank colleagues in departments that we have visited on sabbatical leaves: Fred Hawthorne, Herb Kaesz, Charles Strouse. Joan Selverstone Valentine, and Jeff Zink (University of California at Los Angeles), and Oren Anderson, Cary Maciel, Jack Norton, Tony Rappé, and Steve Straus (Colorado State University). We would also like to thank the Chemistry Departments at UCLA and CSU, the Zoology Depariment at Southern Hlinois University. as well as our own departments for making possible sabbatical visits to take advantage of these resources. ‘We are grateful to Michael W. Anderson, University of Cambridge: Anthony Arduengo, E. 1. du Pont de Nemours: B. Dubost, Pechiney Institute; Jacek Klinow- ski, University of Cambridge: John Newsam, BIOSYM Technologies: Joseph J. Pluth, University of Chicago; Arnold L. Rheingold, University of Delaware: P. Sainfort, Pechiney Institute; Charloete L. Stern, University of Illinois, Urbana- Champaign; Sir Sohn Meurig Thomas, The Royal Institution of Great Brita Scott Wilson, University of Hinois. Urbana-Champaign, for special help with illustra- tions from their work, . ‘The writing of this text has benefitted from the helpfel advice of many reviewers, ‘They include fvan Bernal, Donald H. Berry, Patricia A. Bianconi, Andrew B. Bocarsly. P. Michael Boorman, Jeremy Burdett, Ben DeGraff, Russell S. Drago, Daniel C. Harris, Roald Hoffmann, Joel F. Liebman, John Milne. ‘Terrance Murphy. Jack Pludziewicz, Philip Power. Arnold L. Rheingold, Richard Thompson, Glenn Vogel. Marc Walters, James H. Weber, and Jeff Zink. ‘We began this preface indicating “changes” that have occurred in the last two decades. We have dealt with new authorship and new inorganic chemistry above, Concerning the merger of Harper & Row, Publishers, New York, and Collins, Pub- lishers, London, the entropy generated was quite unexpected. When the dust had settled, there emerged two sterling performers: Jane Piro, Chemistry Editor, and Cate Rzasa, Project Editor, who helped us in many ways. We are happy to acknowledge ‘our debt £0 them. Finally, there are many, many faculty and students who have helped in the original writing and further development of this book, often anonymous in the brief Citation of colleagues and reviewers. They know who they are, and we hope they will accept our sincere thanks for all that they did. James E. Huheey Ellen A. Keiter Richard L. KeiterTo the Student Once afier a deparimental seminar, an older professor was heard to remark that he felt intimidated by all of the new theory and experimental spectroscopic methods: known by the new chemistry graduates. A young graduate student was stunned: she was cure il woukd take ber years just to learn enough of the chemistry that be already knew to get her degree. Meanwhile, two other professors were arguing heatedly over the relative importance of facts versus theory. One said descriptive chemistry was the most important because “facts don’t change!" “Weil, some ‘facts’ seem to change—I read yesterday that ividium is the densest element; ten years ago when 1 was a student, | was told that osmivm was the densest “They don't change as fast as theories: theories just come and go: besides, what's wrong with someone repeating an experiment and doing i bettet—getting a more accurate value?"™ “That's the point; new theories are necessary to explain new experimental data, ‘and theories give us something to test, a framework around which we can dream. . .”* “Dream! We need 2 little less ‘inspiration’ and a lot more perspiration. . ."* And so it goes. . These chemists and these arguments present a microcosm of perpetual debates in chemistry and the essence of the great difficulty in writing an upper level textbook of inorganic chemisiry. The field is vast; large numbers of inorganic articles are published every week. New synthetic techniques allow the isolation and ideraification of great numbers of highly reactive compounds. The- oretical descriptions have become increasingly sophisticated, as have spectroscopic methods, Inorganic chemistry interacts with organic, physical, and even biological chemistry. Borderlines between molecular and solid-state chemistry are rapidly disap- pearing. The older chemist may know many facts and theories but realizes it is only a small portion of the whole, The new graduate, with well-developed ls ina few areas, also has a sense of inadequacy, Perhaps the student faced with his or her first advanced inorganic course feels this most acutely. The textbook for the course reflects ihe instructor's choice of what portion of inorganic chemistry should be taught, what mix of facts and theory, and what relative weight of traditional and new science. Authors also make their choices and those are seen in the variety of available texlbooks on the market. Some are heavily factual, usually bulky, and especially useful for finding out something about all of the principal compounds of a particular ‘element. Others present a blend of fact and theory but minimize the book bulk byTo the Student oxy timiting each topic to a few paragraphs. This has the advantage of including most topics but the disadvantage of having to look elsewhere for a futter development. Any single book, of course, bas this problem to a certain degree, thus the need for many references. Our book, Inorganic Chemistry: Principles of Siracture and Reactivity, fourth edition, is also a blend of fact and theory, but we think itis large enough for a full meal. ‘There is no reason to expect a book that deals with the chemistry of 109 elements to be Smaller than a standard organic chemistry textbook! We've enjoyed writing this book; we hope that you will enjoy reading it. If youdo, ‘we'd like to bear from you. James E. Huhecy Billen A. Keiter Richard L. KeiterExcerpts from the Preface to the Third Edition Ichas been my very good fortune to have had contact with exceptional teachers and researchers when U was an undergraduate (Thomas B. Cameron and Hans H. Jafié, University of Cincinnati) and a graduate student (John C. Bailar, Jr., Theodore L. Brown, and Russell S. Drago, University of IIlinois); and to have had stimulating and ‘hetpful colleagues where | have taught (William D. Hobey and Rober C. Plumb, Worcester Polytechnic Institute; Jon M. Bellama, Alfred C. Boyd, Samuel O. Grim, James V. McArdle, Gerald Ray Miller, Car} L, Rollinson, Nancy S. Rowan, and John A, Tosseil, University of Maryland). | have benefitted by having had a variety of students, undergraduate, graduate, and thesis advisees, who never let me relax with a false feeling that f “knew it all.” Finally, it has been my distinct privilege to have had the meaning of research and education exemplified to me by my graduate thesis advisor, Therald Moeller, and to have had a most patient and understanding friend, ‘Hobart M. Smith, who gave me the joys of a second profession while infecting me with the "muhi itch.”” Professors Moeller and Smith, through their teaching, research, and writing, planted the seeds thst grew into this volume. Four librarians, George W. Black, Jr., of Southern tHinois University at Carbon- dale, and Sylvia D. Evans, Elizabeth W. McElroy, and Elizabeth K. Tomlinson, of the University of Maryland, helped greatly with retrieval and use of the literature. & should like to give special thanks to Gerald Ray Miller who read the entire manuscript ‘and proofs at the very beginning, and who has been a ready source of consultation through all editions. Caroline L. Evans made substantial contributions to the contents of this book and will always receive my appreciation. Finally, the phrase “best friend and severest crit jis so hackneyed through casual and unthinking use, paraiteled only by its ravity in the realty, that 1 hesitate to proffer jl. ‘The concept of two men wrangling over manuscripts, impassioned to the point of-literufly (check Webster's) calling each other's idees “poppycock” may seem incompatible with a friendship ‘soon to enter its second quarter-century. If you think so, you must choose to ignore my many trips to Southern Illinois University to work with Ron Brandon, to visit with him and his family, to return home with both my emotional and intellectual “bat- teries” recharged. My family has contributed much to this book, both tangible and intangible, visible and (except to me) invisible. My parents have toterated and provided much over theExcarpts from tho Profoce to the Thied Edition xvii years, inctuding love, support, and watching their dining room become an impromptu office; often the same week as holiday dinners. My sister, Cathy Donaldson, and her husband, Terry, themselves university teachers, have both answered and posed questions ranging from biotogy to chemicat engineering. More important, they “have been there” when f needed their unique help. To all of these go my deepest gratitude and thanks. Jones E. HuheeyChapte r Inorganic Chemistry, the Beginnings What Is Inorganic Chemistry? [tis customary for chemistry books to begin with questions of this type—questions that are usually difficult or impossible to answer in simple “twenty-five-words-or-less” definitions. Simple pictures, whether of words or of art, cannot portray all aspects of a subject. We most recently had this impressed upon us when our editor asked ‘us f0 suggest some aspect of inorganic chemistry for the cover of this book. The very natwre of @ cover implies a relatively simple, single item, such as a molecule, a struc- ture, a reaction, or a property (or pethaps a simple combination of two or three of these). Should we choose the structure of the new high-temperature superconductors which recently geined a Nobel Prize for their discoverers? You probably have read. about them in the popular press and wordered why “high temperature” was colder than a Siberian winter! Should we choose a metal “cluster compound” that acts, at ‘the molecular level, like a microscopic fragment of the metal? How about an inorganic molecule that is optically active (that's not a subject limited to organic chemistry), or carboxypeptidase A (that's an enzyme, but interest in it is certainly not timited to biochemists)? Maybe a symmetrical crystal of a compound like sodium thiosulfate, photographer's “hypo.” or a multicolor. polarized micrograph of an inorganic com- pound. But no single design can possibly portray the many, varied aspects of in- organic chemistry. tn the same way, any short and simple definition of a complex subject és apt to be disappointing and even misleading. So let's just try to see where inorganic chemistry came from, what an inorganic chemist does, and, perhaps, where the subject is going, ‘The term inorganic chemistry originally meant nonliving chemistry, and it was that part of chemistry that bad arisen from the arts and recipes dealing with minerals, and ores. It began by finding naturally occurring substances that tad usefut prop- erties, such as flint or chert that could be worked into tools (middle Pleistocene, ca. 5 x 10* years ago or less). This search continues (see below), but now it is included in the sciences of mineralogy and geology. Chemistry deals more with the changes that can be effected in materials. One of the most important early reactions was the 1Inorganic Chemistry, ‘an Example ie Chemietey? Feduction of metal oxides, carbonates, and sulfides to the Jee metals:* 2CufOH),CO, + 26 —+ 4Cu + 4CO, + 20 an [Copper/Bronze Age. ca. 4500-7500 years ago] Fej0, 420 —+ 3Fe +2CO, (2) [tron Age. Irom ca. 4500-3500 years ago to present] This was the first example of applied redox chemistry, but to this day the gain and {oss of electrons is central to inorganic chemistry. ‘The terms exidation, reduction, and use (irom “basic metal oxide”) are all intimately related to these early metallurgical processes. [The term acid is derived from vinegar (L.. ccecum).] Much of this early work was strictly pragmatic without any theory as We would understand it. It was necessary to be able to identify the best and richest ores, to be able to distinguish between superficial resemblances. The familiar properties of foof's gotd, iron pyrites, FeS,, as compared with the element gold is a well-known example. Some minerals such as the 2eolites were poorly understood The name comes from the Greek words for boiling (Fe1v) and stone (71000) because, when heated, water boils away from these minerals in the form of steam. How a solid stone could also be partly liquid water wes, of course, mystifying. The answer seemed t0 be of no practical concern, 60 this question was relegated to “pure” or “basic” chemistry. Wanting to choose a single chemical system, somehow representative of inorganic chemistry, for our cover, we have picked a zeolite. The term may not be familiar to you. However. one or more zeolites are almost certainly to be found in every chemical esearch laboratory, in your home, and in many major industrial provesses. They. themselves, are the subject of chemicat research from structural determinations to catalysis to the inorganic chemical aspects of nutrition. The particular zeolite ilfestrated on the cover is Bogasive, a compound of sodium, calcium, aluminum, siticon, hydrogen, and oxygen. It had been known for only a few ‘months when this book went to press. Yet between the time that the earliest obser= vations were made on “boiling stones” (1756) and the discovery of boggsite, other zeolites had achieved major chemical importance. If your home has a water-softening unit, it contains a zzolite or # related compound. “Hard water” contains metal cations that interfere with the actions of soaps and synthetic detergents, The mazerial in the watct softenct exchanges Na” into the water, while removing Mg” *, Ca**. and other metal ions:? Mg?* + Ca?* + Na,Z —> CaMpz +4Na~ (13) "The first chemical resctions such us the discovery of tre, were not consciously applied as “urs and rccipes™ that led to chemisiy, Perhips the aldext concious application of chemistry by hurmins was that of the action of yeasts on augur in baking and brewing, ct the somewhat less wel defined process of cooking. 11 was discovered along the Columbia River, Washington, by a group of amaieur mineratogsts [Mofo ‘A. Sclence 1990. 247, 1413, Howard, D. Gz Tachernich, R, We, Smith, J. Vs; Klein G. L Arm Minera 1990, 75, 1200-1204] and! the structure determined 1 the University of Chicago (Ptuih, J. Smith, 4. Am Mtnerd. 1999, 75, 3-507] 2The symbol Z. represents al of vba aeolive structure except the exchangeable Na” ions,Chemicol Structure of Zeolites and Other Chemical Systems a ‘This discovery was made in the 1850s, and it was the first ion exchange water-softening process utilized commonly. The ion exchangers used today in home softening units are closely related in structure ond exchange properties, but are more stable for long- term use. More recently, synthetic zeolites have made their appeurance in a closely related, yet quite distinct, application. Not everyone, even in areas of quite hard water, has a water softener. In an effort to counter the negative effects of hard water, manlac- turers early adopted the practice of adding “builders” to soaps and synthetic deter- gents. At fiest these were carbonates (“washing sode") and borates (“borax”), More. recently, these have been polyphosphates, [0sPO(PO3},]"~ (a = a + 3), which com- plexed the hard water cations, that is, (ie¢ them up so that they did not interfere with the cleaning process. ‘The synthesis of polyphosphates ard the study of their chelating properties with Mg?*, Ca?*, and other eations, are other aspects of inos- ganic chemistry. However, pliosphate is one of the three main ingredients of fertilizer.* and too much phosphorus leads to the eutrophication of lakes and streams. In art ef= fort to reduce the amount of phosphates used. manufacturers stasted using 4 synthetic zeolite in detergents in the form of microscopic powder to adsorb these unwanted cations. Today, this is che largest usage of zeolites on a tonnage bas. Lest you be muttering, “So out with phosphate pollution, in with zeolite po lution", zeotites seem to be one of the few things we can add to the ecosystem without negative consequences, The very structures of zeolites make them thermodyramically Unstable, and they degrade readily to more stable «luminosilicates that are aaturally occurring cliys, But that rises other interesting questions: If they are metastable, why do they form, rather than their more stable decomposition products? How can wwe synthesize ther? Another use of zeolites has becn as “molecular sieves” ‘This very descriptive, if slightly misleading, name comes from & remarkable property of these zeolites: their ability to selectively adsorb molecules on the basis of their size A mixture of gases may be separated according ta their molecular weights (sizes) just as @ course mixture may be separated by & mechanical sieve Some chemistry labs now have “exhaust-less hoods” that selectively adsorb targer, noxious molecules, but are inert to. smaller, ubiquitous molecules such as water, dinitrogen (Nj) and dioxygen (0). There are zeolites that have a special affinily for small molecules tlike § 0) but exclude larger molecules, They are thus exetltent drying agents for various knboratory solvents. Before we can understand how these molecular interetions can take place, we must understand the structures of 2cotites. Important for at least @ century, the use of struc tural information to understand chemistry is more important now than ever before. The determination of chemical structures is a combination of careful experimental technique and of abstract reasoning, Because we have seen pictures of "tinker-toy” ‘molecules all our lives in TV commercials and company logos, itis almost impossible for us to realize that it has not been long in terms of human history since arguments ‘were made that such structures could not be studied (or even could not exist) because it was impossible to see atoms (if they existed). The crystsllographer’s ability to tke a crystal in hand and to determine the arrangement of invisible atoms (Fig. 1l}is # + When you buy an ordinary "5-105" fertilizer, yos are buying nilogen (5%, expressed as N}, posphate (16°, exprosced us PO), and pocassium (5%, expressed 28 KO}4 janie Chemtstey? Fig. 1.1 The structure of the synthetic zealne ZSM-5: (2) microscopic crystals; (b) an eleciron micrograph of the area marked in (af; (c} the crystal structure of ZSM-S relmed 10 the electron micrograph. {Courtesy of J. M. Thomas. Royal Inssixute of Chemistry,| sriumph of abstract reasoning. The determination of the structures of molecules and extended structures is fundamental to the understanding of inorganic chemistry. It is not possible to think of modern inorganic chemistry in terms of simple equations such as Eq. 11 to 13: A three-dimensional view of the arrangement of atoms is necessary. ‘One of the unifying factors in the delermination of chemical structures has been the use of symmetry and group theory. One has only t0 look at the structure of boggsite to sec that it is highly symmetncal, but symmetry is even more basic to chemistry than that. Symmetry aids the inorganic chemist in applying a variety of methods for the determination of structures. Symmetry is even more fundamental ‘The very universe seems to hinge upon concepts of symmetry. The solid-state chemist and solid-state physicist have also developed other tech- niques for examining and manipulating solids and surfaces. Of particular interest recently is a technique known as scanning tunneling microscopy (STM) which allows us 10 sce and even to move individual atoms.* The atoms are imaged ard moved by electrostatic means (Fig. 1.2).° Although chemistry is portrayed, correctly, in terms of single atoms or groups of atoms, it is practiced in terms of moles (6 x 10** atoms}, millimoles (6 x 107° atoms), or even nanomoles (6 x 10* atoms), seldom less. But Perhaps the horizon of atorn-by-atom chemistry is not far away * Some people object 10 the use of the verb “lo sce” in this context, correctly arguing that sine the wave: Jength of visible ight is much greater than the ardor of magnitude of motzcules, the Itler cannot be seen directly. but must be etocironiclty imaged. True, but every year hundreds of millions of people “yee” the Super Boul on TV! What's the diference? © Eigler, D. Ms Schweizer, 6. K. Nature (999, 44, 526-526,Chemical Reactivity 13) {4} Fig. 1.2 Scanning tunneling micrographs of the movement of xenon atoms xdsorted on a nickel surlace The nickel azon's are not imaged. Each letter is $ im from top to) Bottom, [Coonesy of D. M. Bicker. IBM | Alshough it is not possible for the chemist to absolutely control the movement of individual atoms or molecules in zeolite structures, the nature of the structure isell resuilts in chatsnels tht direct the molecular motions (Fig, 1.3), Furthermore, the sizes and shapes of the channels determine which molecules can form most ceadily, and which can kine readily, A molecule that eatnot leave (Fig, 1.4} is apt to reset further, This may have important consequences: A catalyst {ZSM-S} thar is structurally se tated to boggsite is used in the alkylation of toluene by methanol to form pure-xylene The methanol can provide methyl grotips te meke ab iheee (ortho, mets, and pares Fig. 1.3 Staeosiew of the structure of boegsie Now the channels romning in the « direction. For belp in seeing stereaveens, sev Appendix H. [From Plu, 3 Js Smit, 3. ¥. Arn, Mineral, (990, 75, $0) S07. Reproduced with pertsssics}Fig, 1.4 meta-Xylene (left) ond pore-xylene (right) ie 8 channel in the sprtheric zeo\ie satolyst Z5M-S. [From Thomas.2 M_ Angew. Chem. In, Bd. Engl, 1988, 27, 1673-1601 Reproduced with permission} xylene isomers. The “near” para isomer leaves readily (Fig. 15} but the angulir onthe and meta isomers do not. They may react further, that is, rearrange, and af pare-xylene forms. it may then feave.” In a related process. ZSM-5 may be used so convert methanol mto a high- octane gosoline. Petroleum-poor countries like New Zealand and South Africa are currently using this process t0 produce gasoline. If the production of para-xylene and gasoline sounds too much like “organic chemistry” for the introduction to aa inorganic texthook, it must be painted otit thar there i a large branch of chemistry, Fig, 1.5 Ilhustration of shape selectivity. [Csicsery, 8. M. Chem Brit. 985, 24, 473-427, Repreduced with permission.) 7 So, i lie of “chemical tweezers” (STM and relied apparatus) we claim to effect partir steroor ‘chemical syniteses by sing speciily shaped zeolites Bur st is state that these speciily shaped seo: sre aise syrshesiesd-—withour “chemasal tweezers”. How? The answer isnot ay difBeul a i may seemsConclusion Whot ts inorgonic Chemistry? 7 called “organometallic chemistry,” that deals with an area intermediate belween inorganic and organic chemistry and broadly overlapping both. Both organic and inorganic chemists work in organometallic chemistry, with the broad generalization often being that the products are “organic” and mostly of interest to the organic chemist, and the intermediates and catalysis are of more interest to the inorganic chemist. Zeolites may be used in purely inorganic catalysis, however. One reaction that may be used to reduce air pollution from mixed nitrogen oxides, NO,, in the indus- trial production of nitric acid is catalytic reduction by ammonia over zeolitic catalysts: NO, + 4xNH, —+ (3 + 2x)N; + 6xH,0 Ga) ‘The seriously polluting nitrogen oxides are thus reduced to two harmless molecules, ‘The strong bond energies of the dinitrogen motecule and the water molecule are the driving forces; the zeolitic catalyst, in the ideal case, provides the pathway without being changed in the process. A related catalytic removal of NO from automobile exhaust may come about from the reaction: 2N0 SHE, Ny +O, as) using a Cu(])/Cullt) exchanged zeolite as a redox catalyst.® To return to the problem of the general invisibility of atoms, how does the chem ist follow the cousse of a reaction if the molecules cannot be imaged? One way is to use spectroscopy. Thus the conversion of methanol, first to dimethyl ether, then to the higher aliphatic and aromatic compounds found in gasoline, can be followed by nuclear magnetic resonance (NMR) spectroscopy (Fig, 1.6). As the reaction proceeds, the concentration of the methanol (as measured by the intensity of the NMR peak at 550 ppm) steadily decreases. The first product, dimethyl ether (860 ppm), increases at first and then decreases as the aliphatic and aromatic products eventually predaminate. ‘So why did we pick bogasite for the cover? Is it “the most important” inorganic com- pound known? Certainly not! {t is currently known from only one locality and in the form of extremely small crystal fragments.? It is unlikely that it occurs anywhere ‘on earth in sufficient quantities ta be commercially important. Yet its discovery adds to our knowledge of the structural possibilities of zcolites and the canditions under which they form, And if we know enough about the structure of a material, we can usually synthesize it if we try hard enough. The synthesis of zeolites has progressed, though it must be admitted that there is much yet to be understood in the process. Boggsite is enough like ZSM-5. yes different, that it has attracted considerable atten- tion, There is currently a massive effort in the chemical industry to try ta synthesize this very interesting material, '@ It may become an important industrial catalyst. Then again, it may not—only time will answer that question. * twamoto. M: Vahico. H Tanda, K.:Mizun,N.:Mine. ¥.:Kagowa.$. Pye. Chem, (996, 05.5227— 33, ° Part of the dificuty in determining the crystal strecture was in picking oot a suitable erystat fragment from the enatrix in which it was imbedded. Only one was found, 007 x WOS x 6 mm in sae. See ouinote 2 © Alper Science 1990, 248, 1190-118erstaley? ppm trom THS Fig. 1.6 Solidstatc “C NMR reveals the successive steps in the conversion of methanol to gasoline over zeolite ZSM-5. The methanol, resonating at 50 ppm, is first dehydrated to dimethyl ether 160 ppm). Subsequent carbon-carbon bond formation leads to a bost of aliphatie (—10 to 30 ppm) and aromatic (aot shown} compounds. (Modified from Anderson, MW. Klinowski, J.J Am. Chen. Soc. 1990, 112, 10-16. Reproduced with permission.)What ts Inorgente Chem ye 8 As was pointed out at the beginning of the chapter, many other subjects could have been chosen for the cover: the new high-temperature superconductors, metal cluster compounds, an optically active inorganic molecule, a bioinonganic enzyme (see bow far inorganic chemistry has come from the days when it meant “non-living”, ‘er a crystal of photographer's hypo. tnvleed, all of these have been used on the covers of recent inorganic textbooks (one reason why we chose something different), and all ‘of them are as appropriate on the one hand, and as limited in scope on the other, as boggsite. They will all be discussed in the following chapters. If there is one thought that you should take away with you alter reading this chaprer, and eventually this book, it is the amazing diversity of inorganic chemistry. It deals with 109 elements, each unique. It is thus impossible in a single chapter to do more than scratch the surfuce of inorganic chemistry: Structure, reactivity, catalysis, thermodynamic stability. sym- metry, experimental techniques, gas-phase, solution, and solid-state chernistry: they are all part of the process. However, it is hoped that some idea of the scope of the subject may have been formed. The following chapters in this book attempt (0 pro~ vide the reader with sufficient basic knowledge of the structure and reactivity of inor ganic systems to ensure a more comprehensive understanding. 11 Fora recent review of zeolite entulysis, see Thomas. J. M. Sei. Amer, (992, 266 44), HC2-tI8,Chape e t The Structure of the Atom Atomic structure is fundamental (© inorganic chemistry, perhaps more so even than organic chemistry because of the variety of elements and their eleciron config- trations that must be dealt with. [t will be assumed that readers will have brought with them [rom carlicr courses some knowledge of quuntur mechanicul concepts such as the wave equation, the carticle-in-a-box, and atomic spectroscopy. The Hydrogen Atom 19 ‘When the Schrodinger equation is solved for tbe hydrogen atom. it is found that there are three characteristic quantum numbers x, f, and m, (as expectes! for a three- dimensional system). The allowed values for these quitntum numbers and their reti- tion to the physical system will be discussed below, but for now they may be taken as a set of rhrce inteyers specifying a particular situation. Each soletion found for a different set of wf, and my is called an eigeafiection and represents an orbital in the hydrogen atom. In order to plot the complete wave functions. one would in general require a four-dimensional graph with coordinates for each of the three spatial dimensions (x.y. 5 oF 4.0, 6) and a fourth value, the wave function, In order to cireumvent this problem and also to make it easier to visualize the actual distribution of electrons within the atom, it is common to break down the wave function, , into ehree parts, each of which is a function of bet a single vari- able. It is most convenient to use polar coordinates, so one obtains HE, 6, @) = Rir)- ©(0)- (4) (2) where (7) gives the dependence of Y upon distance from the nucleus and © and ® sive the angular dependence.The Radial Wave Function, R ‘The radial functions for the first three orbitals! in the hydrogen atom are Zye a~2(2) ets Is orbital where Z is the nuclear charge, ¢ is the base of natural logarithms. and do is the radius of the first Bohr orbit. According to the Bohr theory, this was an immutable radius, bbut in wave mechanics itis simply the “most probable” radius for the electron to be located. [ts value, 529 pm, is determined by do = h?/4z?me?, where h is Planck's constant and mand ¢ are the mass and charge of the electron, respectively. In hydro- gen, Z = I, but similar orbitals may be constructed where Z > | for other elements. For many-clectron atoms, exact solutions of the wave equation are impossible to ‘obtain, and these “hydrogen-like” orbitals arc often used as a first approximation.” Although the radiat functions may appear formidable, the important aspects may be made apparent by grouping the constants. For a given atom, Z will be constant and may be combined with the other constants, resulting in considerable simplification: = 1 = 0m naLt=Qm=0 R= Ker 1s orbital Qt =O m= Jen#2 2s orbital R= K.(2 - 2lalma0 Re Kye 2p orbital The most apparent feature of the radial wave functions is that they all repee- sent an exponential “decay”, and that for = 2 the decay is slower than for a= 1. This may be generalized for all radiat fa They decay as e™™*. For this rea- son, the radius of the various orbitals (actually, the most prohable radius) increases with increasing n, A socond feature is the presence of a node in the 2s radial function. Al r= 2dg/Z, R = 0 and the vale of the radial function changes from positive 10 negative. Again, this may be generalized: s orbitals have n— I nodes, p orbitals have n= 2 nodes, etc. The radial functions for the hydrogen ts, 2s, and 2p orbitals are shown in Fig. 21. Because we are principally interested in the probubilty of finding electrons at ‘various points in space, we shall be more concerned with the squares of the radial functions than with the functions themselves. It is the square of the wave function "The complote wave functions in terme of the quantum numbers m and Fue given by Pauling, L. The Nature of' rhe Chenical Bout; Cornell University, Mhnes, NY, 1960 (n-= 1-6) aed Ponerield, WW. norgonic Chemistry: A Unified Approacl, Addisoor Westey: Reading. MA. 1984 fo = 1-31 2 The use of bydropersike orbits for muticlecizon slams vegies cleciron-cleciron repulsion. an this sy often be u serious oversimplifintion tee popes 20-25).14-2: The Stewelure of the Atom Angular Wave Functions Jn between, x and R both have finite values, so there isa maximum in the plot of probability (4nr7R?) as a function of r. This maximum occurs at r = ay, the value of the Bohr radius. Similar probability functions (including the factor 4x1”) [or the 2s, 2p, 3s, 3p, and 3d orbitals are also shows in Fig. 24. Note that although the radial function for the 2s orbital is both positive (r < 2dg/Z) and negative (r > 2ao/Z), the probability func- tion is everywhere positive (as of course it must be to have any physical meaning) as a result of the squaring operation, ‘The presence of a node in the wave function indicales a point in space at which the probability of finding the electron has gone to zero, This raises the interesting question, “How does the electron get from one side of the node to the other if it can never be found exactly at the node?" This is not a valid question as pored, presupposes our macroscopically prejudiced view that the electron is a particle. If ‘we consider the electron to be a standing wave, no problem arises because it simul taneousty exists on both sides of a node. Consider a vibrating string on an instrument such as a guitar. If the string is stopped at the twelfth fret the note will go up one ‘octave because the wavelength has been shortened by one-half Although it is experi- mentally difficult {a finger is not an infinitesimally smatl point! itis possible to sound the same note on either half of the octave-stopped siting. This vibration ean be con- ‘inuous through the Rode at the fret. In fact. 09 she open string, overtones occur at ‘the higher harmonics such that nodes cocur at various points along the string. Nodes are quite common to wave behavior, and conceptual problems arise only when we Uy t0 think of the electron as 2 “hard” particte with a definite position. Does the presence of one or more nodes and maxima have any chemical effect? ‘The answer depends upon the aspect of bonding in which we are interested. We shall see later that covalent bonding depends critically upon the overiup of orbitals. Con- ceivably, if one atom had a maximum in its cadial wave function overlapping with a region with a node (minimum) in the wave function of a second atom, the overlap ‘would be poor.* However, in every case in which careful catculations have been made, it has been found that the nodes tie t00 close to the nucleus 10 affect the bonding appreciably. ‘The presence of nodes and small “subnodal maxima” does have a profound cf feet on the energy of electrons in different orbitals. An electron in an orbital with these subnodal maxima (particularly s orbitals with higher values of 1) are said to be penetrating. that is. chey have considerable electron density in the Tegion of the ssucleus. This ix the fundamental reason for the ordecing of the energy levels in poly- electronic atoms: Is, 2s, 2p. 3s. 3p, ets. (see pages 20-22). ‘The angular part of the wave function determines the shape of the electron cloud and varies depending upon the type of orbital involved (3, p,d.or f) and its orien- tation in space. However, for a given type of orbital, such 2s s of p,, the angular ‘wave function is independent of the principal quantum number or energy level, Some Specifically, the averiap imtegro is tbe integra J ¥,'¥ydr, of the two wave functions (Sec Eq. 5.31). At te nade the produet will eo 90 zero, and it wall have small values ia the region of the node,y Fig. 2.8 Angular probability fonction for hydrogenlike p orbitals. ‘Only two dimensions of the three-dimensional function have been shown, 15 Fig. 2.8 Angular part of the wave funetion for hhydrogen-iike s orbitals re, Hef and p orbitals (eighth Only two dimensions of the three dimensional function have been shown. typical angular functions are 1=0m,=0 @0=[1/(4nj] sorbita} l=1m=0 ©O=[3/(6n)}!? cos 0 p. orbital Am=0 — OO= [S/(I6nI]"3 cos? 9-1) dx orbital ‘The angular functions for the s and p, orbital are dlustrated in Fig 2.5. For an s orbital, ©@ is independent of angle and is of constant value, Hence this graph is Gireular or, more properly, in three dimensions-—spherical, For the p, orbital we ‘obtain two tangent spheres. The p, and p, orbitals arc identical in shape but are oriented along the x and y axes, respectively. We shall defer extensive treatment of the d orbitals (Chapter 11) and f orbitals (Chapter 14) unit bond formation in coor- dination compounds is discussed, simply noting here that ¢he basic angular function {or d orbitals is four-lobed and that for f orbitals is six-tobed (sce Fig. 29) ‘We ase most interested in the probability of finding. an electron, und so we shall wish 10 examine the function @#0° since it corresponds ta the angular part of ¥?, When the angular functions are squared, different orbitals change in different ways. For an s orbital squaring causes no chunge in shape since the function is everywhere the same: thes another sphere is obtained. For both p and d orbitals, howcver, the plot tends to become more clongated (sce Fig, 26) ‘The mening of Figs. 2.5 and 26 is easily misinterpreted. Neither ane has any direct physical meaning, Both are graphs of mathematical fonctions, just as Figs. 22and 2.4 are. Both may be used to obtain information about the probsble distri- ‘bution of electrons, but neither may in any way be regarded as 2 “picture” ofan. orbi- tal. It is an unfortunate fact that fuzzy drawings of Figs. 25 or 2.6 are often presented “orbitals”. Now one can define an orbital in any way ane wishes, corresponding to RR, Ob, or O70, but it should be realized shat Figs, 22, 24,25, und 26 are mathematical functions and drawing them fuzzily does itor represent ah atom. (Chemists tend to shink in terms of electron clouds, and hence ¥* probably gives the best intuitive “picture” of an orbital. Methods of showing the total probability of Snding an electron including both radial and angular probabilities are shown in Figs. 27-29. Although clectron density may be shown cither by shading (Fig. 2.7) or by contours of equal electron density (Figs. 28 and 2.9), only the latter method is quan- tatively accurate.2-The Strveture of the Atom Fig. 27 {a) Pictor o xr plane I representation of the electron density in 9 hydrogen like 2p orbinal compared with Ib] he eleciron density contours for she hydrogen-like 2p, orbital of carbon ‘Contour values are relative to the electron dersity maximum The xy plane is a nodal sustce. The sipns (+ and —} refer to those ofthe original wove function. [The contour diagram is from Ogryzlo, E. A; Porter, G. B. J. Chem Educ, 1963, 4,258, Reproduced with permission.] Fig. 2.8 The electron density contoues for the Inydrogen-like 3p, orbital of carbon, Contour values are relative 20 the electron density mtatmum. The xy plane and a sphere of radius 52:pm (dashed Fine) ture nodal sucfuces, The signs (+ and —)refer to those of the original wave function. [The eontour diagram is from Ogryzlo, EA, Poner, G.B. J. Chem, Educ. 1963, 40, 256-261, Reproduced with permission }The Ht ” ZN Fig. 29 Angular wave functions of s. 9, and f orbitals illustrating gerade ond ungerade symmetry: 1a} x orbital, gerade, (6) p orbital, ungerade: (c} pictorial representation of symmetry of p orbital (d} d,, orbital, yerade, (e) pictorial representation of syrametry of d orbital: (F) das orbital, gerade; (g) fs orbital, wngerade, Symmetry of Orbitals Since ©76? is termed an angular probability function. the question may prop- erly be asked what its true meaning is. if not a “picture” of electron distribution, Like any other graph, it simply plots the value of a function (©70") versus the variable (@ or 8 6) [fone chooses an angle 6, the probability that the electron will be found in that direction (summed over all distances) is proportional to the magnitude of the ‘yector connecting the origin with the functional plot at that angle. in Fig. 29 are shown sketches of the angular parts of the wave funetions for 5 p, d. and f orbitals. The signs in the lobes represent the sign of the wave Junction in those directions For example, in the p, orbital, for 0= 90°, cos@ = 0 and for 90° < 8 < 270°, cos 8 is negative. The signs of the wave functions are very important when considering the overlap of two bonding orbitals. ft is customary to speak of the symmetry ef orbitals as gerade or ungerade, These German words meaning even ard uneven refer to the operation shown in the sketches—inversion about | on moving from any point A to the equivalent point B on the opposite side of the18 -2-The Structure of the Atom Energies of Orbitals center the sign of the wave function does not change, the orbital is said 10 be gerade. ‘The $ orbital is 2 trivial cnse in which the sige of the angular wave function is every- where the same. The d orbitals (only two of which are shown here) are also yerade. ‘The p orbitals, however, are unsyrametrical with respect to inversion and the sign changes on going from A to Bj hence the symmetry is ungernde. Likewise, f orbitats fare ungerade, Another way of referring to the symmetry properties of these orbitals is to say that s avd @ orbitals have a center of symmetry, and that p and f orbitals do not. Tn addition to symmetry with respect to inversion about the center, orbitals ave other symmetry properties with respect to other symmetry operations. These. ‘will be discussed in Chapter 3. At should be noted that most textbooks, including this one, generally portray the symmetry of orbitals as in Fig. 2.93-g with wave functions plotted and the signs marked. However, an exceedingly common practice in the original literature of both jorganic and organic chemistry is to indicate the signs of the wave functions by the shading of stylized orbitals. Fig, 2.9¢ indicates the symmetry of a p orbital and 29¢ ad orbital by this convention. Attention should be called to a rather confusing practice that chemists com- monly use. {n Figs. 27 and 28 it will be noted that srvall plus and minus signs appetr. Although the figure refers to the probability of finding the electron snd thus must be everywhere positive, the signs + and — refer to the sign of the original wave func- tion, ¥, in these regions of space. In Fig. 28, for example, in addition to the inversion resulting from the ungerade p orbital, there isa second node (actually a spherical nodal surfice) at a distance of 6 ag/Z resulting from the radial wave function. Although this practice may seem confusing, it is useful anc hence has ben accepted. The‘? plot is uscful in attempting lo visvalize the physical “picture” of the atom, but the sign of ¥ is important with respect to bonding.’ ‘The energy levels of the hydrogen atom are found wo he determined solely by the principal quantum number, and their relationship is the same as found for a Bohr ston 2n?me* Ee RE es) where mis the mass of the cleciron, ¢ is the electronic charge, is the principal quan- tum number, and /ris Planck's constant. Quantization of energy and angular momen- tum were introduced as assumptions by Bohr, but chey follow naturally from the Wave treatment The quantum number n may have any positive, integral value from one 10 infinity: n=1234...,00 ‘The lowest (most negative) energy corresponds to the minimum value of m {n= 1) and the energies increase (become less negative) with increasing n until the contin tuum is reached (n= co}, Here the electron is no longer bound to the atom and thus is no longer quantized, but may have any amount of kinelic enerey. The allowed values of {range from zero to n — |: 12O123..jn-1 See Orchin, M; Jal, H. H; The Jmporcace of Anciboniing Orbital; Houghton Milf: Boston, 1967; 5-9, lor & good discussion of this point.‘The quantum number ! is a measure of the orbital angular momentum of the elec- tron and determines the “shape” of the orbital. The types of orbitals are designated by the Fetters smh f.g..... corresponding to the values of f= 1.2.3.4... spectroscopic notation {see page 26) and the re- ‘mainder follow alphabetically. tn the previous section we have seen the various ant gular wave functions and the resulting distribution. of electrons. The nature of the ‘angular wave function is determined by the value of the quantum number £ ‘The number of equivatent ways that orbitals can be oriented in space is equal to 21+ 1. tn the absence of an electric or magnetic field these orientations are degenerate, that is, they are identical in energy. Consider, for example, the p orbital, It is possible to have @ p orbital in which the maximum electron density lies on the z-axis and the 2o-plane isa nodal plane. Equivalent orientations have the maximum electron density tatong the x- or y-axis. Application of a magnetic Field splits the degeneracy of the set of three p orbitals. The magnetic quantum reanber, m, is retated to the component of angular momentum along a chosen axis—for example, the = axis—and determines the orientation of the orbital in space, Values of m range irom 1 to +t: imps hab QE ER HE Thus for f= 1, m= - 1,0, +1, and there are three p orbitals possible, py, Py» and p.. Similnely. for |= 2d orbitals), m = -2, ~1.0, +1, +2,and fort = 3(f orbitals), m= 3-2-1041, +2 43° It is an interesting fact chat just as the single s orbital is spherically symmetric. the summation of electron density of a set of three p orbitals, five d orbitals, or seven F orbitals is also spherical (Unsold’s theorem) Thus, although it might appear as though an atom such as neon with a filled set of s and p orbitals woutd have s “lumpy” electron cloud, the total probability distribution is perfectly spherical. From the above mules we may obtain the allowed values of n, J, and m, We have seen previously (page 10} tat a set of particular values for these three quantum num- bers determines an eigenfunction or orbital for the bydrogen atom. The possible orbitals are therefore 1s orbital 2s orbital ay.2) orbitals 3s orbital 3P.a.2 orbitals m= HZ WO ENGL Bhar yaoi nayey OMbitaN” m =0 4s orbital ‘We can now summarize the refation between the quantum numbers n, 2, andl m and the physical pictures of electron distribution in orbitals by a few simple rules. It ‘6 Athough the p, tal ds ortsats correspond 10 m = 0. there Ts no similar One Lo-one correspundence for Ie her orbitals und atherwatuesofm. The functions are corptex form and mus be formed into new, linear comblaslons forthe real p snd «orbitals. See tooce, W. J. Physical Chentry, Prentice-Hall Englewood CUM NJ 1972; 640: Atkins, P. W, Physical Chemistry the Freeman: San Francisco, 1990: (p62; igi B. N. frnradvetion to Lund Fieut Witey: New York, 1966: po 9=tS, These orbital ave sketched and discussed further in Chapter 1.