18 PERIODIC TABLE OF THEELEMENTS VIII VIIA Group 1 2 1 H 13 14 15 16 17 2 He Period 1 hydrogen helium I II 1.0079 III IV V VI VII 4.00 IA IIA 1s1 IIIA IVA VA VIA VIIA 1s2 3 Li 4 Be 5 B 6 C 7 N 8 O 9 F 10Ne 2 lithium beryllium boron carbon nitrogen oxygen fluorine neon 6.94 9.01 10.81 12.01 14.01 16.00 19.00 20.18 2s1 2s2 2s22p1 2s22p2 2s22p3 2s22p4 2s22p5 2s22p6 11Na 12Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar 3 sodium magnesium aluminium silicon phosphorus sulfur chlorine argon 22.99 24.31 3 4 5 6 7 8 9 10 11 12 26.98 28.09 30.97 32.06 35.45 39.95 3s1 3s2 3s23p1 3s23p2 3s23p3 3s23p4 3s23p5 3s23p6 IIIB IVB VB VIB VIIB VIIIB IB IIB 19 K 20Ca 21Sc 22 Ti 23 V 24 Cr 25Mn 26Fe 27Co 28Ni 29Cu 30Zn 31Ga 32Ge 33 As 34 Se 35 Br 36 Kr 4 potassium calcium scandium titanium vanadium chromium manganese iron cobalt nickel copper zinc gallium germanium arsenic selenium bromine krypton 39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.84 58.93 58.69 63.55 65.41 69.72 72.64 74.92 78.96 79.90 83.80 d o 4s1 4s2 3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2 4s24p1 4s24p2 4s24p3 4s24p4 4s24p5 4s24p6 ri e P 37Rb 38 Sr 39 Y 40 Zr 41Nb 42Mo 43 Tc 44 Ru 45Rh 46 Pd 47Ag 48Cd 49 In 50 Sn 51Sb 52Te 53 I 54Xe 5 rubidium strontium yttrium zirconium niobium molybdenum technetium ruthenium rhodium palladium silver cadmium indium tin antimony tellurium iodine xenon 85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.07 102.90 106.42 107.87 112.41 114.82 118.71 121.76 127.60 126.90 131.29 5s1 5s2 4d15s2 4d25s2 4d45s1 4d55s1 4d55s2 4d75s1 4d85s1 4d10 4d105s1 4d105s2 5s25p1 5s25p2 5s25p3 5s25p4 5s25p5 5s25p6 55Cs 56 Ba 57La 72Hf 73 Ta 74 W 75Re 76Os 77 Ir 78 Pt 79Au 80Hg 81 Tl 82Pb 83 Bi 84Po 85 At 86Rn 6 caesium barium lanthanum hafnium tantalum tungsten rhenium osmium iridium platinum gold mercury thallium lead bismuth polonium astatine radon 132.91 137.33 138.91 178.49 180.95 183.84 186.21 190.23 192.22 195.08 196.97 200.59 204.38 207.2 208.98 (209) (210) (222) 6s1 6s2 5d16s2 5d26s2 5d36s2 5d46s2 5d56s2 5d66s2 5d76s2 5d96s1 5d106s1 5d106s2 6s26p1 6s26p2 6s26p3 6s26p4 6s26p5 6s26p6 87Fr 88 Ra 89Ac 104Rf 105Db 106Sg 107Bh 108Hs 109Mt 110 Ds 111Rg 112Cp 113 114Fl 115 116Lv 117 118 7 francium radium actinium rutherfordium dubnium seaborgium bohrium hassium meitnerium darmstadtium roentgenium copernicum flerovium livermorium (223) (226) (227) (261) (262) (266) (264) (277) (268) (271) (272) (277) (289) (293) 7s1 7s2 6d17s2 6d27s2 6d37s2 6d47s2 6d57s2 6d67s2 6d77s2 6d87s2 6d107s1 6d107s2 7s27p2 7s27p4 58Ce 59Pr 60 Nd 61Pm 62Sm 63Eu 64Gd 65Tb 66Dy 67Ho 68Er 69Tm 70 Yb 71 Lu Molarmasses(atomic weights) 6 cerium praseodymium neodymium promethium samarium europium gadolinium terbium dysprosium holmium erbium thulium ytterbium lutetium Lanthanoids quotedtothenumberof 140.12 140.91 144.24 (145) 150.36 151.96 157.25 158.93 162.50 164.93 167.26 168.93 173.04 174.97 (lanthanides) significant figuresgiven herecanberegardedas 4f15d16s2 4f36s2 4f46s2 4f56s2 4f66s2 4f76s2 4f75d16s2 4f96s2 4f106s2 4f116s2 4f126s2 4f136s2 4f146s2 5d16s2 typicalofmostnaturally occuringsamples- 90Th 91Pa 92U 93Np 94Pu 95Am 96Cm 97Bk 98 Cf 99 Es 100Fm 101Md 102No 103Lr Actinoids 7 thorium protactinium uranium neptunium plutonium americium curium berkelium californium einsteinium fermium mendelevium nobelium lawrencium 232.04 231.04 238.03 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262) (actinides) 6d27s2 5f26d17s2 5f36d17s2 5f46d17s2 5f67s2 5f77s2 5f76d17s2 5f97s2 5f107s2 5f117s2 5f127s2 5f137s2 5f147s2 6d17s2 The elements Name Symbol Atomic number Molar mass Name Symbol Atomic number Molar mass (g mol− 1 ) (g mol−1) Actinium Ac 89 227 Manganese Mn 25 54.94 Aluminium (aluminum) Al 13 26.98 Meitnerium Mt 109 268 Americium Am 95 243 Mendelevium Md 101 258 Antimony Sb 51 121.76 Mercury Hg 80 200.59 Argon Ar 18 39.95 Molybdenun Mo 42 95.94 Arsenic As 33 74.92 Neodymium Nd 60 144.24 Astatine At 85 210 Neon Ne 10 20.18 Barium Ba 56 137.33 Neptunium Np 93 237 Berkelium Bk 97 247 Nickel Ni 28 58.69 Beryllium Be 4 9.01 Niobium Nb 41 92.91 Bismuth Bi 83 208.98 Nitrogen N 7 14.01 Bohrium Bh 107 264 Nobelium No 102 259 Boron B 5 10.81 Osmium Os 76 190.23 Bromine Br 35 79.90 Oxygen O 8 16.00 Cadmium Cd 48 112.41 Palladium Pd 46 106.42 Caesium (cesium) Cs 55 132.91 Phosphorus P 15 30.97 Calcium Ca 20 40.08 Platinum Pt 78 195.08 Californium Cf 98 251 Plutonium Pu 94 244 Carbon C 6 12.01 Polonium Po 84 209 Cerium Ce 58 140.12 Potassium K 19 39.10 Chlorine Cl 17 35.45 Praseodymium Pr 59 140.91 Chromium Cr 24 52.00 Promethium Pm 61 145 Cobalt Co 27 58.93 Protactinium Pa 91 231.04 Copernicum Cp 112 277 Radium Ra 88 226 Copper Cu 29 63.55 Radon Rn 86 222 Curium Cm 96 247 Rhenium Re 75 186.21 Darmstadtium Ds 110 271 Rhodium Rh 45 102.91 Dubnium Db 105 262 Roentgenium Rg 111 272 Dysprosium Dy 66 162.50 Rubidium Rb 37 85.47 Einsteinium Es 99 252 Ruthenium Ru 44 101.07 Erbium Er 68 167.27 Rutherfordium Rf 104 261 Europium Eu 63 151.96 Samarium Sm 62 150.36 Fermium Fm 100 257 Scandium Sc 21 44.96 Flerovium Fl 114 289 Seaborgium Sg 106 266 Fluorine F 9 19.00 Selenium Se 34 78.96 Francium Fr 87 223 Silicon Si 14 28.09 Gadolinium Gd 64 157.25 Silver Ag 47 107.87 Gallium Ga 31 69.72 Sodium Na 11 22.99 Germanium Ge 32 72.64 Strontium Sr 38 87.62 Gold Au 79 196.97 Sulfur S 16 32.06 Hafnium Hf 72 178.49 Tantalum Ta 73 180.95 Technetium Tc 43 98 Hassium Hs 108 269 Tellurium Te 52 127.60 Helium He 2 4.00 Terbium Tb 65 158.93 Holmium Ho 67 164.93 Thallium TI 81 204.38 Hydrogen H 1 1.008 Thorium Th 90 232.04 Indium In 49 114.82 Thulium Tm 69 168.93 Iodine I 53 126.90 Tin Sn 50 118.71 Iridium Ir 77 192.22 Titanium Ti 22 47.87 Iron Fe 26 55.84 Tungsten W 74 183.84 Krypton Kr 36 83.80 Uranium U 92 238.03 Lanthanum La 57 138.91 Vanadium V 23 50.94 Lawrencium Lr 103 262 Xenon Xe 54 131.29 Lead Pb 82 207.2 Ytterbium Yb 70 173.04 Lithium Li 3 6.94 Yttrium Y 39 88.91 Livermorium Lv 116 293 Zinc Zn 30 65.41 Lutetium Lu 71 174.97 Zirconium Zr 40 91.22 Magnesium Mg 12 24.31 22552233__WWHHFF__FFMM..iinndddd ii 1100//44//22001133 22::3333::2266 PPMM this page left intentionally blank Sixth Edition Duward Shriver Northwestern University Mark Weller University of Bath Tina Overton University of Hull Jonathan Rourke University of Warwick Fraser Armstrong University of Oxford 22552233__WWHHFF__FFMM..iinndddd iiiiii 1100//44//22001133 22::3333::2277 PPMM Publisher: Jessica Fiorillo Associate Director of Marketing: Debbie Clare Associate Editor: Heidi Bamatter Media Acquisitions Editor: Dave Quinn Marketing Assistant: Samantha Zimbler Library of Congress Preassigned Control Number: 2013950573 ISBN-13: 978–1–4292–9906–0 ISBN-10: 1–4292–9906–1 ©2014, 2010, 2006, 1999 by P.W. Atkins, T.L. Overton, J.P. Rourke, M.T. Weller, and F.A. Armstrong All rights reserved Published in Great Britain by Oxford University Press This edition has been authorized by Oxford University Press for sale in the United States and Canada only and not for export therefrom. First printing W. H. Freeman and Company 41 Madison Avenue New York, NY 10010 www.whfreeman.com 22552233__WWHHFF__FFMM..iinndddd iivv 1100//44//22001133 22::3333::3388 PPMM Preface Our aim in the sixth edition of I norganic Chemistry is to provide a comprehensive and contemporary introduction to the diverse and fascinating subject of inorganic chemistry. Inorganic chemistry deals with the properties of all of the elements in the periodic table. These elements range from highly reactive metals, such as sodium, to noble metals, such as gold. The nonmetals include solids, liquids, and gases, and range from the aggressive oxidizing agent fl uorine to unreactive gases such as helium. Although this variety and diversity are features of any study of inorganic chemistry, there are underlying patterns and trends which enrich and enhance our understanding of the discipline. These trends in reactivity, structure, and properties of the elements and their compounds provide an insight into the landscape of the periodic table and provide a foundation on which to build a detailed understanding. Inorganic compounds vary from ionic solids, which can be described by simple applica- tions of classical electrostatics, to covalent compounds and metals, which are best described by models that have their origin in quantum mechanics. We can rationalize and interpret the properties and reaction chemistries of most inorganic compounds by using qualitative models that are based on quantum mechanics, such as atomic orbitals and their use to form molecular orbitals. Although models of bonding and reactivity clarify and systema- tize the subject, inorganic chemistry is essentially an experimental subject. New inorganic compounds are constantly being synthesized and characterized through research projects especially at the frontiers of the subject, for example, organometallic chemistry, materials chemistry, nanochemistry, and bioinorganic chemistry. The products of this research into inorganic chemistry continue to enrich the fi eld with compounds that give us new perspec- tives on structure, bonding, reactivity, and properties. Inorganic chemistry has considerable impact on our everyday lives and on other sci- entifi c disciplines. The chemical industry is strongly dependent on it. Inorganic chemistry is essential to the formulation and improvement of modern materials such as catalysts, semiconductors, optical devices, energy generation and storage, superconductors, and advanced ceramics. The environmental and biological impacts of inorganic chemistry are also huge. Current topics in industrial, biological, and sustainable chemistry are men- tioned throughout the book and are developed more thoroughly in later chapters. In this new edition we have refi ned the presentation, organization, and visual repre- sentation. All of the book has been revised, much has been rewritten, and there is some completely new material. We have written with the student in mind, including some new pedagogical features and enhancing others. The topics in Part 1, Foundations , have been updated to make them more accessible to the reader with more qualitative explanation accompanying the more mathematical treat- ments. Some chapters and sections have been expanded to provide greater coverage, par- ticularly where the fundamental topic underpins later discussion of sustainable chemistry. Part 2, The elements and their compounds , has been substantially strengthened. The section starts with an enlarged chapter which draws together periodic trends and cross references forward to the descriptive chapters. An enhanced chapter on hydrogen, with reference to the emerging importance of the hydrogen economy, is followed by a series of chapters traversing the periodic table from the s-block metals through the p block to the Group 18 gases. Each of these chapters is organized into two sections: The essentials describes the fundamental chemistry of the elements and T he detail provides a more thor- ough, in-depth account. This is followed by a series of chapters discussing the fascinating chemistry of the d- block and, fi nally, the f-block elements. The descriptions of the chemical properties of each group of elements and their compounds are enriched with illustrations of current research and applications. The patterns and trends that emerge are rationalized by drawing on the principles introduced in Part 1. Part 3, Frontiers , takes the reader to the edge of knowledge in several areas of current research. These chapters explore specialized subjects that are of importance to industry, materials science, and biology, and include catalysis, solid state chemistry, nanomaterials, metalloenzymes, and inorganic compounds used in medicine. 22552233__WWHHFF__FFMM..iinndddd vv 1100//44//22001133 22::3333::3388 PPMM vi Preface We are confi dent that this text will serve the undergraduate chemist well. It provides the theoretical building blocks with which to build knowledge and understanding of inorganic chemistry. It should help to rationalize the sometimes bewildering diversity of descriptive chemistry. It also takes the student to the forefront of the discipline with frequent discus- sion of the latest research in inorganic chemistry and should therefore complement many courses taken in the later stages of a program. 22552233__WWHHFF__FFMM..iinndddd vvii 1100//44//22001133 22::3333::3399 PPMM Acknowledgments We have taken care to ensure that the text is free of errors. This is diffi cult in a rap- idly changing fi eld, where today's knowledge is soon replaced by tomorrow’s. Many of the fi gures in Chapters 26 and 27 were produced using PyMOL software (W.L. DeLano, The PyMOL Molecular Graphics System, DeLano Scientifi c, San Carlos, CA, USA, 2002). We thank colleagues past and present at Oxford University Press—Holly Edmundson, Jonathan Crowe, and Alice Mumford—and at W. H. Freeman—Heidi Bamatter, Jessica Fiorillo, and Dave Quinn—for their help and support during the writing of this text. Mark Weller would also like to thank the University of Bath for allowing him time to work on the text and numerous illustrations. We acknowledge and thank all those colleagues who so willingly gave their time and expertise to a careful reading of a variety of draft chapters. Mikhail V. Barybin, University of Kansas Deborah Kays, U niversity of Nottingham Byron L. Bennett, I daho State University Susan Killian VanderKam, P rinceton University Stefan Bernhard, C arnegie Mellon University Michael J. Knapp, U niversity of Massachusetts – Amherst Wesley H. Bernskoetter, B rown University Georgios Kyriakou, U niversity of Hull Chris Bradley, T exas Tech University Christos Lampropoulos, U niversity of North Florida Thomas C. Brunold, U niversity of Wisconsin – Madison Simon Lancaster, U niversity of East Anglia Morris Bullock, Pacifi c Northwest National Laboratory John P. Lee, University of Tennessee at Chattanooga Gareth Cave, N ottingham Trent University Ramón López de la Vega, F lorida International University David Clark, Los Alamos National Laboratory Yi Lu, U niversity of Illinois at Urbana-Champaign William Connick, University of Cincinnati Joel T. Mague, T ulane University Sandie Dann, Loughborough University Andrew Marr, Queen’s University Belfast Marcetta Y. Darensbourg, T exas A&M University Salah S. Massoud, University of Louisiana at Lafayette David Evans, University of Hull Charles A. Mebi, Arkansas Tech University Stephen Faulkner, U niversity of Oxford Catherine Oertel, O berlin College Bill Feighery, IndianaUniversity – South Bend Jason S. Overby, College of Charleston Katherine J. Franz, D uke University John R. Owen, University of Southampton Carmen Valdez Gauthier, F lorida Southern College Ted M. Pappenfus, University of Minnesota, Morris Stephen Z. Goldberg, A delphi University Anna Peacock, University of Birmingham Christian R. Goldsmith, A uburn University Carl Redshaw, U niversity of Hull Gregory J. Grant, University of Tennessee at Chattanooga Laura Rodríguez Raurell, U niversity of Barcelona Craig A. Grapperhaus, University of Louisville Professor Jean-Michel Savéant, U niversité Paris Diderot – Paris 7 P. Shiv Halasyamani, University of Houston Douglas L. Swartz II, K utztown University of Pennsylvania Christopher G. Hamaker, I llinois State University Jesse W. Tye, Ball State University Allen Hill, University of Oxford Derek Wann, U niversity of Edinburgh Andy Holland, Idaho State University Scott Weinert, O klahoma State University Timothy A. Jackson, University of Kansas Nathan West, University of the Sciences Wayne Jones, State University of New York – Binghamton Denyce K. Wicht, Suffolk University 22552233__WWHHFF__FFMM..iinndddd vviiii 1100//44//22001133 22::3333::3399 PPMM About the book Inorganic Chemistry provides numerous learning features to help you master this wide- ranging subject. In addition, the text has been designed so that you can either work through the chapters chronologically, or dip in at an appropriate point in your studies. The text’s Book Companion Site provides further electronic resources to support you in your learning. The material in this book has been logically and systematically laid out, in three dis- tinct sections. Part 1, F oundations, outlines the underlying principles of inorganic chem- istry, which are built on in the subsequent two sections. Part 2, T he elements and their compounds, divides the descriptive chemistry into ‘essentials’ and ‘detail’, enabling you to easily draw out the key principles behind the reactions, before exploring them in greater depth. Part 3, F rontiers, introduces you to exciting interdisciplinary research at the fore- front of inorganic chemistry. The paragraphs below describe the learning features of the text and Book Companion Site in further detail. Organizing the information Key points The key points outline the main take-home message(s) of the section that follows. These will help you to focus on the prin- cipal ideas being introduced in the text. Context boxes Context boxes demonstrate the diversity of inorganic chem- istry and its wide-ranging applications to, for example, advanced materials, industrial processes, environmental chemistry, and everyday life. Further reading Each chapter lists sources where further information can be found. We have tried to ensure that these sources are easily available and have indicated the type of information each one provides. Resource section At the back of the book is a comprehensive collection of resources, including an extensive data section and informa- tion relating to group theory and spectroscopy. Notes on good practice In some areas of inorganic chemistry the nomenclature com- monly in use today can be confusing or archaic—to address this we have included short “notes on good practice” that make such issues clearer for the student. 22552233__WWHHFF__FFMM..iinndddd vviiiiii 1100//44//22001133 22::3333::3399 PPMM