JOIN US ON THE INTERNET VIA WWW, GOPHER, FTP OR EMAIL: WWW http www thomson com GOPHER gopherthomson com ” FIP. ftp thomson com Aserace of DP EMAIL — findit@krosk thomson com ‘CONCISE INORGANIC CHEMISTRY FIFTH EDITION Senior Lecturer in Inorganic Chemistry Loughborough University Blackwell© 1964, 1965, 1977, 1991, 1996,J D Lee Published by Blackwell Science Ltd Osney Mead, Oxford OX2 0EL 25 John Street, London WCIN 2BL_ 23 Ainshe Place, Edinburgh EH3 6AJ 350 Mam Street, Malden ‘MA02143.5018, USA ‘54 University Street, Carlton ‘Victoria 3053, Australia 10, ue Casimir Delavigne 75006 Pans, France Other Ednonal Offices Blackwell Wissenschafis-Verlag GmbH Kurftestendamm 57 10707 Berlin, Germany Blackwell Seience KK MG Kodenmacha Building 7-10 Kodenmacho Nihombasht Chuo-ku, Tokyo 104, Japan The nght of the Author tobe identified asthe Author of this Work has been asserted inaccordance with the ‘Copynght, Designs and Patents Act 1988 Allnights reserved No part of this publication may be reproduced, stored ina retneval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording er otherwise, except as permitted by the UK Copynght, Designs and Patents Act 1988, without the por permission of the copynght owner First published 1964 (Chapman & Hall) Second edition 1965 Third edition 1977 Reprinted 1989, 1990 Fourth edition 1991 Repnated 1992, 193, 1994 Fifth edition 1996 Repnnted 1998, 1999, 2000, 2001, 2002 (Blackwell Science) Set by Best set Typesetier Hong Kong Prated and bound in India by Gopsons Papers Lid,, Noida DISTRIBUTORS Marston Book Services Lid PO Box 269 Abingdon, Oxon OX14 4YN- (Orders Tet 01235 465500 Fax 01238 465555) USA Blackwell Science, Ine Commerce Place 350 Main Street Malden, MA 02148 5018 (Orders Tet 8007596102 781 388 8250 Fax 781 3888255) Canada Login Brothers Book Company 324 Seutkeans Crescent ‘Wonnipeg, Manitoba R3} 3T2 (Orders Tet 20483-2987) Australia Blackwell Science Pty Ltd 34 University Street Carlton, Victoria 3053 (Orders ‘Tet 393470300 Fax 393475001) A.catalogue record for this ttle isavatlable from the Bintish Library ISBN 0-632-05293-7 For further information on Blackwell Science, visit our website www blackwell-science com The Blackwell Science logossa trade mark of Blackwell Sevence Ltd, registered at the United Kingdom ‘Trade Marks Registry het! LIBRARY (AN 73812Contents Preface to the fifth edition SI units Nomenclature in the periodic table PART ONE THEORETICAL CONCEPTS AND HYDROGEN Chapter 1 Atomic structure and the periodic table The atom as a nucleus with orbital electrons Atomic spectra of hydrogen and the Bohr theory Refinements to the Bohr theory The dual nature of electrons — particles or waves The Heisenberg uncertainty principle The Schrédinger wave equation Radial and angular functions Pauli exclusion principle Build-up of the elements, Hund’s rule Sequence of energy levels Arrangement of the elements in groups in the periodic table Further reading Problems Chapter 2 Introduction to bonding Attainment of a stable configuration Types of bonds Transitions between the main types of bonding Ionic bonds Covalent bonds Oxidation numbers Coordinate bonds Double and triple bonds Metallic bonds and metallic structures Melting points Conductivity Solubility Speed of reactions XXX XXXIV XXXVCONTENTS Chapter 3 The tonic bond Structures of tome solids Radtus ratio rules Calculation of some limiting radius ratio values Coordination number 3 (planar triangle) Coordination number 4 (tetrahedral) Coordination number 6 (octahedral) Close packing, Classification of ionic structures Jom compounds of the type AX (ZnS NaC} CsCl) Structures of zinc sulphide Sodium chloride structure Caesium chlonde structure Iomc compounds of the type AX, (CaF, T:0, $:0,) Calcium fluoride (fluorite) structure Rutile structure cristobalite (silica) structure Layer structures (Cdl; CdCl, [NiAs]) Cadmium iodide structure Cadmium chlonde structure Nickel arsenide structure Structures containing polyatomic ions Amore critical look at radius ratios A cautionary word on radwus ratios Lattice energy Features of solids Stoichiometric defects Schottky defects Frenkel defects Nonstoichiometric defects Metal excess F centres Interstitial rons and electrons Metal deficiency Positive ions absent Extra interstital negative sons Semiconductors and transistors Rectihers Photovoltaic cell ‘Transistors Micro minaturized semiconductor devices — integrated circutts Further reading Probi.ms.CONTENTS vii Chapter 4. The covalent bond 72 Introduction 72 The Lewis theory 72 The octet rule 72 Exceptions to the octet rule 73 Sidgwick—Powell theory 74 Valence shell electron pair repulsion (VSEPR) theory 74 Effect of lone pairs 75 Effect of electronegativity 716 Isoelectronic principle 77 Some examples using the VSEPR theory 77 BF; and the [BF,]~ ion 77 Ammonia NH; Ti Water H,0 77 Phosphorus pentachloride PCI, 78 Chlorine trifluoride CIF, 78 Sulphur tetrafluoride SF, 79 The triiodide ion 17 79 Sulphur hexafiuoride SF, 80 lodine heptafluoride IF, 80 Valence bond theory 80 Hybridization 81 The extent of d orbital participation in molecular bonding 85 Sigma and pi bonds 87 Molecular orbital method 89 LCAO method * 90 s—s combinations of orbitals 90 5—p combinations of orbitals 93 P—p combinations of orbitals 94 p~d combinations of orbitals 96 d—d combinations of orbitals 96 Non-bonding combinations of orbitals 96 Rules for linear combination of atomic orbitals 97 Examples of molecular orbital treatment for homonuclear diatomic molecules 98 Hy molecule ion 99 H2 molecule 99 Hez molecule ion 99 He, molecule 99 Liz molecule 100 Be; molecule 100 Bs molecule 101 C, molecule 102 N> molecule 104 O; molecule z, 105 OF jon 105CONTENTS OF 10n F, molecule Examples of molecular orbital treatment for heteronuclear diatomic molecules NO molecule CO molecule HCI molecule Examples of molecular orbital treatment involving delocalized x bonding Carbonate ton CO}- Nitrate 10n NOF Sulphur trioxide SO3 Ozone O3 Nitrite on NOY Carbon dioxide CO2 Azide ron Ny Summary of multi centre 2 bonded structures United atom method Further reading Problems Chapter 5 The metallic bond General properties of metals Conductivity Lustre Malleability and cohesive force Crystal structures of metals Bond lengths Theones of bonding in metals Free electron theory Valence bond theory Molecular orbital or band theory Conductors insulators and semiconductors Alloys Tonic compounds Interstival alloys and related compounds Substitutional alloys Superconductivity Further reading, Problems. Chapter 6 General properties of the elements ‘Suze of atoms and rons Size of atoms Size of ions Problems with tome radn ‘Trends 1m some radia 107 107 107 199 No 2 2 n2 4 14 1s 116 16 7 17 lig 119 220 21 121 21 122 122 126 127 127 128 12g 128 131 132 132 132 135 140 144 145 146 146 146 146 148 148ix CONTENTS fix] lonization energies Ie Electron affinity 154 Born-Haber cycle . , 156 Polarizing power and polarizability — Fajans’ rules 537 Electronegativity 158 Pauling 161 Mulliken 162 Allred and Rochow Metallic character 163 Variable valency and oxidation states 164 Standard electrode potentials and electrochemical series 165 Oxidation~reduction reactions 170 The use of reduction potentials 172 The occurrence and isolation of the elements 178 Mechanical separation of elements that exist in the native form 178 Thermal decomposition methods 179 Displacement of one element by another 180 ' High temperature chemical reduction methods 181 *»,, Reduction by carbon 181 Reduction by another metal 182 Self-reduction 182 :*+ Reduction of oxides with hydrogen 182 Electrolytic reduction 182 In aqueous solution 183 In other solvents 183 In fused melts 183 Factors influencing the choice of extraction process 183 Thermodynamics of reduction processes 183 ‘ Horizontal, vertical and diagonal relationships in the periodic . table 189 urther reading 190 Problems 191 Chapter 7 Coordination compounds . 194 ouble salts and coordination compounds 194 .Werner’s work 195 More recent methods of studying complexes 198 Effective atomic numbers 200 Shapes of d orbitals 201 -Bonding of transition metal complexes 202 Valence bond theory 202 Crystal field theory 202 Molecular orbital theory 202 Valence bond theory 203 Crystal field theory 204 Octahedral complexes 305 Effects of crystal field Splitting 210CONTENTS —] Tetragonal distortion of octahedral complexes (Jahn-Teller + distortion) Square planar arrangements Tetrahedral complexes Chelates Magnetism Extension of the crystal field theory to allow for some covalency Molecular orbital theory macceptors donors Nomenctature of coorchnation compounds Isomensm Polymerization isomerism Jonzation tsomerism Hydrate isomerism Linkage ssomerism Coordination isomerism Coordination position isomerism Geometric isomerism or stereoisomerism: Optical isomerism Further reading. Problems Chapter 8 Hydrogen and the hydrides Electronic structure Position in the penodic table Abundance of hydrogen Preparation of hydrogen Properties of molecular hydrogen Isotopes of hydrogen Ortho and para hydrogen Hydrides Tonic or salt-ltke hydndes Covalent hydndes Metallic (or interstitial) hydrides Intermediate hydrides ‘The hydrogen ton Hydrogen bonding Acids and bases. Arshemus theory Acids and bases in proton solvents Bronsted—Lowry theory Lewis theary The solvent system ‘The Lux—Flood definition ‘The Usanowch definiuon Hard and soft acids and bases 214 217 219 222 225 226 227 229 229 230 232 232 232 233 233 233 234 24 234 236 240 240 240 241 Zl 243 245 248 248 249 250 252 254 254 255 256 258 260 262 265 265 267 267 267CONTENTS [xi] Further reading eee Problems PART TWO THE s-BLOCK ELEMENTS 273 Chapter 9 Group 1 — the alkali metais 275 Introduction 275 Occurrence and abundance 276 Extraction of the metals 277 Uses of Group t metais and their compounds 278 Electronic structure 280 Size of atoms and ions 280 Density 280 Ionization energy 281 Electronegativity and bond type 281 Born—Haber cycle: energy changes in the formation of ionic compounds 282 Structures of the metals, hardness and cohesive energy 285 ‘ Melting and boiling points ‘ 286 Flame colours and spectra 286 Colour of compounds 287 Chemical properties 288 Reaction with water 288 Reaction with air 289 Reaction with dinitrogen 289 Oxides, hydroxides, peroxides and superoxides 290 Reaction with air 290 Normal oxides — monoxides 290 Hydroxides 290 Peroxides and superoxides 291 Sulphides 293 Sodium hydroxide 294 Sodium hydrogencarbonate (sodium bicarbonate) 294 Sodium sulphate 294 Oxosalts -— carbonates, bicarbonates, nitrates and nitrites 255 Halides and polyhalides 296 Hydrides 297 Solubility and hydration 298 Solutions of metals in liquid ammonia 302 Compounds with carbon 303 Organic and organometallic compounds 303 Complexes, crowns and crypts 305 Biological importance 308 Differences between lithium and the other Group 1 elements 309 Further reading 311 Problems 312xu CONTENTS Chapter 10 The chlor-alkali industry Leblanc process Weldon and Deacon processes Electrolytic processes Diaphragm cell Mereury cathode cell Quantities Sodium carbonate The Solvay (or ammonta—soda) process Further reading Problems Chapter 11 Group 2 - the alkaline earth elements Introduction Electronic structure Occurrence and abundance Extraction of the metals Dow sea water process Dow natural brine process Size of atoms and ions Jonization energy Electronegativity Hydration energies Anomalous behaviour of berylium . Solubility and lattice energy Solutions of the metals in liquid ammonia Chemical properties Reaction with water Hydroxides. Hardness of water Reaction with acids and bases Oxides and peroxides Sulphates Nitrates Hydrides Hakdes Nitrides Carbides Insoluble salts Organometallic compounds Complexes Brofogeal role of Mg?* and Ca?* ifferences between berythum Farther reading ty and the other Group 2 clements Problems 315 U5 317 37 318 v9 321 321 323 324 324 325 325 326 326 327 1329 329 329 330 331 331 332 334 335 335 335 337 338 338 341 342 32 344 345 346 347 M7 Ho 353 353 354 354PART THREE THE p-BLOCK ELEMENTS 357 Chapter 12 The group 13 elements , 359 General properties 359 Occurrence and abundance 360 Extraction and uses of the elements 360 Extraction of boron 360 Uses of boron 361 Extraction of aluminium 362 Uses of aluminium 363 Gallium, indium and thallium 363 Oxidation states and type of bonds 364 The (+111) oxidation state 364 The (+1) oxidation state -— the ‘inert pair effect’ 365 The (+11) oxidation state 366 Melting points, boiling points and structures 366 Size of atoms and ions 367 Electropositive character 368 Ionization energy 369 Reactions of boron 370 Reactions of the other elements 370 Reaction with water and air 370 Reaction with acids and alkalis 371 Reaction with dioxygen 372 Reaction with the halogens and sulphate 372 Alums 372 Cement 373 Reactions of Ga, In and Tl 373 Some properties of thallium(I) 373 Compounds of boron and oxygen 374 Boron sesquioxide and the borates 374 Acidic properties of H;BO3 or B(OH); 375 Structures of borates 376 Borax 377 Sodium peroxoborate 379 Isopolyacids of B, Si and P 379 Qualitative analysis of boron compounds 380 Fluoboric acid 380 Borides 380 The other Group 13 oxides 381 Qualitative analysis of alummium 382 Amphoteric behaviour ~ aluminates 382 Tetrahydridoborates (borohydrides) 383 Trihalides 385 Dihalides 388 Monohalides 388Complexes Dufferences between boron and the other elements Boron hydrides Compounds known Preparation Reactions of the baranes Hydroboration Reaction with ammonia Some other reactions of boranes Structures of the boranes Organometallic compounds Further reading Problems Chapter 13 The group 14 elements Introduction Occurrence of the elements Extraction and uses of the elements Carbon Sikcon Germanum Tin Lead Structure and allotropy of the elements Differences between carbon silicon and the semaiming clements Carbon dating Physical propernes: Covalent radi Tomzation energy Melting points Metalic and non metallic character Four covalent compounds Chemical reactivity Inert pair effect ‘Standard reduct:on potentials Graphite compounds Carbides Salt lke carbides Interstinal carbides Covalent carbides Oxygen compounds Carbon monoxide CO Carbon donde CO, Carbon suboxides Carbonates ‘The carbon eycle Sulphides 389 389 390 390 390 32 392 393 395 395 397 398 400 402 402 403 403 403 404 405 405 any 410 ay all att 412 4i2 412 an 413 414 44 Al6 417 418 Ns 419 419 423 425 425 427 428CONTENTS Oxides of silicon 430 Oxides of germanium, tin and lead 432 Silicates 432 Occurrence in the earth’s crust 432 Soluble silicates 433 Principles of silicate structures 434 Classification of silicates 434 Orthosilicates (neso-silicates) 435 Pyrosilicates (soro-silicates, disilicates) 436 Cyclic silicates 436 Chain silicates 437 Sheet silicates (phyllo-silicates) 440 Three-dimensional silicates 443 Silicates in technology 445 Alkali silicates 445 Cement 445 Ceramics 445 Glass 446 Organosilicon compounds and the silicones 446 * . Organosilicon compounds 446 "Preparation of organosilicon compounds 447 Silicones 448 Hydrides 451 Cyanides 453 Complexes 455 Internal x bonding using d orbitals 456 Tetrahalides 457 Carbon 457 Freons 458 Silicon 459 Germanium, tin and lead 460 Catenated halides . 461 Dihalides 461 Cluster compounds 462 Reaction mechanisms 462 Organic derivatives 463 Further reading 464 Problems 466 Chapter 14 The group 15 elements 468 Electronic structure and oxidation states 468 Occurrence, extraction and uses 468 Nitrogen 468 Phosphorus 470 Arsenic, antimony and bismuth 471 General properties and structures of the elements 472 Nitrogen 472XVI CONTENTS: ‘The mtrogen cycle Phosphorus Arsenic, antimony and bismuth Bond type Metallic and non-metallic character Reactivity Hydrides Ammonia NHa Ammonium salts Phosphine PH; Arsine AsHy, stibine SbH, and bismuthine BiH, Structure of the hydrides Donor properties Hydrazine N2Ha Hydroxylamine NH,OH Liquid ammonia as a solvent Hydrogen azide and the azides Standard reduction potentials Fertilizers Nitrogen fixation Cyanamide process Haber ~Bosch prov.ss. Urea Phosphate fertilizers Haldes Trihalides Pentahahdes Oxides of nitrogen Nitrous oxide N,O Nutric oxide NO Nitrogen sesquioxide NO, Nitrogen dioxide NO, and dinitrogen tetroxide N,04 Dunitrogen pentoxide N;O; Oxoacids of mtrogen Nitrous acd HNO, Nitric acid HNO, Oxides of phosphorus, arsenic and bismuth Troxdes Pentoxides ‘Other oxides Oxoaeids of phosphorus The phosphoric acid series ‘Orthophosphone acids Polyphosphates Long chain polyphosphates - linear metaphosphates Metaphosphates—cyclophosphates Hypaphosphoric acid HyP,0,, 473 A74 475 476 477 478 478 479 480 481 481 481 482 433 485 486 487 490 489 489 492 492 494 494 494 494 496 498 499 499 S01 501 503 503 503 504 508 508 509 S511 511 5 su 513 516 S17 SIR[cones fei] The phosphorous acid series 519 Orthophosphorous acid H3PO3 519 Metaphosphorous acid (HPO3),, 520 Hypophosphorous acid H;PO, 520 Major uses of phosphates 520 Sulphides of phosphorus 521 P,S; $22 P,Sio 523 Phosphazenes and cyclophosphazenes (phosphonitrilic compounds) 524 Organometallic compounds 526 Further reading 527 Problems 529 Chapter 15 Group 16 —- the chalcogens $32 General properties 532 Electronic structure and oxidation states 533 Abundance of the elernents 534 Extraction and uses of the elements 535 Extraction and separation of dioxygen 535 Uses of dioxygen 335 Extraction of sulphur 536 Acid rain and SO; 538 Uses of sulphur 539 Extraction and uses of selenium and tellurium 539 Discovery and production of polonium 540 Structure and allotropy of the elements 540 Oxygen 540 Sulphur 541 Selenium, tellurium and polonium 543 Chemistry of ozone 543 Oxidation states (+II), (+1V) and (+ VI) 545 Standard reduction potentials 546 Bond lengths and pr—dz bonding 546 Differences between oxygen and the other elements 547 General properties of oxides 547 Normal oxides 547 Peroxides 548 Suboxides 548 Basic oxides 548 Amphoteric oxides 549 Acidic oxides ” $49 Neutral oxides 549 Reactions between oxides 549 Oxides of sulphur, selenium, tellurium and polonium 551 Dioxides MO, Trioxides MO, 531 553fen] CONTENTS Other oxides Detergents Oxoacids of sulphur Sulphurous acid senes Sulphunc acid series Thionc acid series Peroxoacid series Oxoacids of selenium and tellunum Oxohalides Thionyl compounds Sulphury! compounds Hydndes Water Other hydrides Peroxides and polysulphides Hydrogen peroxide Hahdes Compounds of sulphur and nitrogen +, Organo denvatives Further reading 7. Problems Chapter 16 Group 17 - the halogens Introduction Occurrence and abundance Extraction and uses of the elements Fluorine Chlonne Bromine Todine Astatine Size of atoms and ions. Tomzation energy ‘Type of bonds formed and oxidation states Melting and bowling points Bond energy in X, molecule Oxtdiing power Reaction with water Reactivity of the elements Hydrogen halides HX KE HCt HBrand HI Halides Tonic halides Molecular (covalent) halides 554 554 556 557 559 562 563 563 564 564 564 565 569 569 570 572 575 577 S78 580 582 582 583 584 584 587 588 589 590 SOL 591 592 593 594 594 596 597 599 599 601 605 605 605CONTENTS xix Bridging halides 606 Preparation of anhydrous halides 606 Direct reaction of the elements 606 Reacting the oxide with carbon and the halogen 606 Reaction of metal with anhydrous HX 607 Reaction of oxides with halogen compounds 607 Halogen exchange 607 Dehydrating hydrated halides 607 Halogen oxides 607 OF, Oxygen difluoride 608 OF, Dioxygen difluoride 608 Ci,O Dichlorine monoxide 609 CiO; Chlorine dioxide 610 Chlorine perchlorate Cl-C1O, 611 C1,0¢ Dichlorine hexoxide 611 Dichlorine heptoxide ClO, 611 Oxides of bromine 612 Oxides of iodine 612 Standard reduction potentials 613 Oxoacids 614 Hypohalous acids HOX 615 Halous acids HXO, 616 Halic acids HXO, 617 Perhalic acids HXO, 618 Strength of the oxoacids 621 Interhalogen compounds 621 AX compounds 622 AX; compounds 623 AXs compounds 626 AX; compounds 627 Polyhalides 627 Basic properties of the halogens 629 Pseudohalogens and pseudohalides 631 Further reading 632 Problems 633 Chapter 17 Group 18 ~ the noble gases 635 Name of group and their electronic structures 635 Occurrence and recovery of the elements 635 Uses of the elements Physical properties 636 Special properties of helium 637 Chemical properties of the noble gases 637 Molecular ions formed under excited conditions oon Clathrate compounds 38 Chemistry of xenon oe Xenon fluoride complexes 639 642all CONTENTS Structure and bonding in xenon compounds XeF, XeFy XeF, Valediction Further reading Problems PART FOUR THE d-BLOCK ELEMENTS Chapter 18 An introduction to the transition elements Introduction Metallic character Variable oxidation state Stability of the various oxidation states: Complexes Size of atoms and rons Density Melting and boiling points Reactivity of metals Tonzation energies Colour Palanzaton Incompletely filled d or f shell Magnetic properties Measurement of magnetic moments Anexample Catalytic properties Nonstoichiometry Abundance Differences between the first row and the other ta rows Maetal-metal banding and cluster compounds Stability of oxidation states Complexes Size Magnetism Abundance Further reading Problems Chagter 19 Groug 3 — the seandium group Introduction Occurrence, separation, extraction and uses Oxidation state Sue Chemicat properties 643 643 645 647 647 ag 649 651 653 653 654 654 656 657 659 661 66! 661 661 662 662 662 663 669 671 672 673 674 674 675 615 675 675 676 676 677 679 679 679 680 681 681(SS CONTENTS xX1 Complexes 8 Further reading Chapter 20 Group 4 — the titanium group 684 Introduction 684 Occurrence and abundance 684 Extraction and uses 685 Kroll process 686 The van Arkel—de Boer method 686 Oxidation states 687 Size 687 Reactivity and passive behaviour 688 Standard reduction potentials 688 (+IV) state 689 Oxides 689 Mixed oxides 690 Peroxides 691 Halides 691 (+UD state 692 Organometallic compounds 694 Ziegler—Natta catalysts 694 Other compounds 695 Further reading 696 Chapter 21 Group 5 - the vanadium group 697 Introduction 697 Abundance, extraction and uses 697 Oxidation states 699 Size 699 General properties 699 Colour 700 Compounds with nitrogen, carbon and hydrogen 700 Halides 701 (+V) halides 701 (+IV) halides 703 (+I) halides 704 Spectra 704 Nb and Ta halides 705 (+11) halides 705 Standard reduction potentials 706 Oxides 707 (+V) oxides 707 (+IV) oxides 708 (+ITD oxides 709 {+1]) oxides 709 Vanadates 709 Low oxidation States 710xxii CONTENTS Organometallic compounds Further reading Chapter 22 Group 6 - the chromium group Introduction Abundance, extraction and uses Oxidation states General properties Standard reduction potentials (+VI) state ‘Chromate and dichromate Peroxo compounds Chromium trioxide (chromic acid) MoQ, and WO, Mixed oxides Oxohalides Halides (+) state (4IV) state (4111) state Chromium Spectra Molybdenum and tungsten (+11) state (+1) state Zero state, (-1) and (-11) Chromates, molybdates and tungstates Tungsten bronzes Biological importance Further reading Chapter 23 Group 7 — the manganese group Introduction Abundance, extraction and wus Oxidation states Standard reduction potentials General properties Lower oxidation states (41H) state CATH) state (FIV) state GEV) state (+VI) state (+ VII) state Biological importance Further reading TN 7m 713 ny ng ns 716 nT 78 718 ny m9 720 720 721 724 724 7m 123 72h Ta 724 725 72 77 728 ™ 732 7 734 734 734 736 mW 737 79 740 742 745 748 748 748 751 751CC CONTENTS [xxiii Chapter 24 Group 8 — the iron group , a Iron, cobalt and nickel groups 353 Introduction to the iron group 3 Abundance, extraction and uses ios Extraction of iron 755 Blast furnace 736 Reactions involved 737 Steel making 354 Puddling 957 Bessemer and Thomas processes Siemens open hearth processes 758 Siemens electric are furnace 758 Basic oxygen process 759 Phase diagram 760 Production figures and uses 760 Extraction of ruthenium and osmium 760 Oxidation states 760 General properties 761 Low oxidation states 763 (+ID state 765 Oxides 765 Halides 765 Complexes 766 (+11) state 769 Oxides and hydrated oxides 770 Halides IMM Complexes 772 Ruthenium and osmium 773 (+IV) and higher states : IB (+V) state 773 (+VI) state 714 (+ VIII) state 774 Bioinorganic chemistry of iron 7715 Haemoglobin 15 Myoglobin 77 Cytochromes 7 Ferretin 778 Catalases and peroxidases 778 Ferredoxins 778 Haemerythrin 779 Cyclopentadieny| and related compounds 779 Further reading 781 Chapter 25 Group 9 — the cobalt group 783 Occurrence. extraction and uses 783 Oxidation states 785pexwy] | CONTENTS General properties. Lower oxidation states (+1) state (411) state (HII) state (41V) state (+¥) and (+V1) states Further reading, Chapter 26 Group 10 ~ the nickel group Introduction Occurrence extraction and uses Nickel Palladium and plannum Oxidation states General properties Low valency states (-[) (0) (+1) (41D) state (+11) state (4IV) state (4+V) and (+VI) states Horizontal compansons in the tan cobalt and nickel groups Further reading Chapter 27 Group 11 —the copper group comage metals Introduction Abundance extraction and uses of the elements Copper Silver Gold Oxidation states Standard reduction potentrals General properties (41) state Photography (41D state (FIL) state (4V) state Biologicat role of copper Further reading Chapter 28 Group 12 - the zinc group Introduction Abundance and occurrence Extraction und uses Extraction of zine Extraction of cadmium 785 787 788 790 794 798 799 799 800 800 800 892 803 805 806 BIE 813 8l4 814 815 Bt6 816 R16 817 818 1s 819 820 820 822 826 827 831 832 832 833 835 835 836 836 836 837CONTENTS XXV Extraction of mercury 837 Uses of zinc 838 Uses of cadmium 838 Uses of mercury 838 Oxidation states 839 Size 839 Jonization energies 840 Genera) properties 840 Standard reduction potentials 842 Oxides 842 Dihalides 843 Complexes 845 Mercury (+1) compounds 846 X-ray diffraction 847 Equilibrium constant 848 Concentration cell 848 Raman spectra 849 Magnetic properties 849 Cryoscopic measurements 849 Polycations 849 Organometallic compounds 850 Biological rote of zinc 851 Toxicity of cadmium and mercury 852 Further reading 854 Problems (Chapters 19-28) 854 PART FIVE THE fBLOCK ELEMENTS 857 Chapter 29 The lanthanide series 859 Introduction 859 Electronic structure 859 Oxidation states 860 Abundance and number of isotopes 861 Extraction and uses 862 Separation of the lanthanide elements 864 Precipitation 864 Thermal reaction 864 Fractional crystallization 864 Complex formation 864 Solvent extraction 865 Valency change 865 Ton exchange 866 Chemical properties of (+111 compounds 866 Oxidation state (+1V) 868 Oxidation stat (+11) Wee 869 Solubility 870 Colour and spectra 870bowl | CONTENTS: Magnetic properties + B72" Lanthanide contraction 874 Complexes 875 Further reac ne 877 Prablems 878 Chapter 30 The actinides 879 Electron structure und postion in the periodic table 879 Oxidation states, 881 Occurrence and prep iraton of the elements 882 Preparation of the actmdes 883 General properties B86 Thorium 887 Protacunium 889 Uranium 890) Occurrence 891 Extraction $91 Nuclear fission 895 Chemical properties 893 Hydrides 893 Oxides 804 Huahdes 804 Neptunium plutonium and americium 895 The Jater uctinide elements, 896 Further extension of the penodic table 898 Further reading 900 Problems 901 PART SIX OTHER TOPICS 903 Chapter 31 The aromre nucleus 905 Steucture of the nucleus 905 Liquid drop model 905 Shell model 906 Forces in the pucteus 907 Stability and the ratio of neutrans to protons 908 Modes of decay 909 Beta emission 909 Neutron emission 910 Positron emission 910 Orbital or K-clectron capture 910 Proton emission on Gamma radiation. ol Half hife period ail Binding energy and quctear stability 912 Alpha decay 913 Radwactive displacement baws 5CONTENTS | xxv Radioactive decay series Thorium (477) series Neptunium (41 + 1) series Uranium (41 + 2) series Actinium (4 + 3) series Induced nuclear reactions Nuclear fission Chain reaction Critical mass The story behind production of the atomic bomb Separation of isotopes Thermal diffusion Electromagnetic separation of UCI, using a mass spectrometer Gaseous diffusion of UF, Using a gas centrifuge to separate “SUF, and SUF, Bomb making Nuclear power stations Moderators Fuel Types of reactor in use Gas cooled thermal reactors Magnox reactors Advanced gas cooled reactors High temperature reactor Water cooled thermal reactors Canadian deuterium uranium reactor Pressurized water reactor Boiling water reactor Steam generating heavy water reactor Fast breeder reactors Nuclear fusion Thermonuclear weapons ‘Contralled fusion reactions The genesis of the elements Some applications of radioactive isotopes Some units and definitions Further reading Problems Chapter 32 Spectra Energy levels in an atom Coupling of orbital angular momenta Pp configuration p® configuration @ configuration Coupling of spin angular mamenta 915 916 916 916 916 917 918 919 920 920 920 92) 921 92] 921 922 923 923 924 924 924 924 924 924 925 925 925 925 925 925 925 927 927 928 932 934 935 935 938 938 940) 940) 94] 94) y42 nN NWxvi | CONTENTS prord* case 942 pord* case 942 Spin orbit coupling 943 Spin orbit coupling p? case 943 Determining the ground state terms— Hund s rules 946 Hole formulation 97 Derivation of the term symbol for a closed subshell 948 Derivation of the terms for a d® configuration 948 Calculation of the number of microstates 950 Electronic spectra of transition metal complexes 951 Laporte ‘orbital’ selection rule 951 Spin selection rule 952 Splitting of electronic energy levels and spectroscopic states 953 Spectra of d' and d” tons 984 Spectra of d? and dons 958 Spectra of d tons 965 Tanabe~Sugano diagrams 967 Further reading 970 Problems 971 Appendix A Abundance of the elements in the earth’s crust 973 Appendix B Melting points of the elements 974 Appendix C_ Borling points of the elements 976 Appendix D Densities of the solid and hquid elements 978 Appendix E Electronic structures of the elements 980 Appendix F Some average single bond energies and some double and triple bond energies 983 Appendix G Solubilites of main geoup compounds in water 984 Appendix H_ Atomic weights based on ?C = 12 000 985 Appendix! Values of some fundamental physical constants 987 AppendixJ Electrical resistivity of the elements at the stated temperature 988 Appendix K Tap fifty chemcals in the USA, 1995 989 Appendix LL tnorgamic chemicals manufactured in large ronnages worldwide 991(ONTENTS eg] Appendix M Minerals used in large amounts 993 Appendix N Hardness of minerals — Mohs’ scale 995 Appendix O Standard textbooks 997 Index 999Preface to the fifth edition Tes 32 years since the first edition of Concise /norgante Chemustry = a long life for any book The size of the book has gradually but inevitably grown, bur ] am pleased that this, the fifth ed:tion, is no larget than the fourth edison Robert Baden Powell (the founder of the Scout movement) said ‘So much to do, so little time to do 1” ) might paraphrase this 10 ‘So much to write, so little space to wnite it! Perhaps the size has reached a Plateas and who knows — a future edition may be smaller! ‘The aims of the fifth edition remam exactly the same as those of the first edition * To provide a modern textbook of morgane chemustry that ts long enough to cover the essenuals, yet short enough to be interesting © To provide a stnple and Jogical framework into which the reader should be able to fit factual knowledge, and extrapolate from this to predict unknown facts © To fill the gap between school books and final year honours degree chemistry texts * The book 1s aimed primarily at first or second year degree students in chemistry at UK universities, but will alse be useful for those domg chemistry as ancilfary subjects, and also for BTECH courses and Part 1 Grad RIC in technical colleges Some parts will be usable by good sist form students * Above all t ts intended to be easy ta read and understand, and 1s based on desesptiye Shemstry combined with some of the reasons why ‘The structure of the book 1s unchanged, compnsing six sections theoretical concepts and hydrogen, s block, P-block, d-block, f block, and Other topics As previously, there is a very large and comprehensive Index, and a large table of contents Every chapter has been updated and the groups of elements are pow labelled from 1 to 18 tn accordance with TUPAC nomenclature Descnptive mateniat necessarily fas a large place, but the book attempts so show the reasons for the structure, properties and reactsans of compotnds, wherever this 48 possible with elementary methods Most chapters include a section on further reading, wsth easy to[ PREFACE TO THE FIFTH EDITION understand articles (in journals such as the Journal of Chemical Education, Chemistry in Britain and Education in Chemistry), references to specialized textbooks, and review articles (such as Quarterly Reviews, Coordination Chemistry Reviews, and the proceedings of specialist conferences and symposia). There is a very small number of references to articles in the primary literature, where these have special or historical significance. Examples include the use of Eliingham diagrams, the Sidgwick~ Powell theory of molecular shape, and the discovery of ferrocene and of warm superconductors. Chemistry has always been, and stil! is, a practical subject. The adage ‘where there's muck there’s money” holds particularly true for the chemi- cal industry. Unless chemicals were needed and used in large amounts there would be no chemical industry. and hence no students in chemistry, no teachers af chemistry, and no need for textbooks. An American professor told me he divided inorganic chemistry books into two types: theoretical and practical. In deciding how to classify any particular book, he first looked to see if the extraction of the two most produced metals (Fe and Al) was adequately covered, what impurities were likely to be present, and how the processing was adapted to remove them. Second, he looked to see if the treatment of the bonding in xenon compounds and ferrocene was longer than that of the production of ammonia. Third, he looked to see if the production and uses of phosphates were covered adequately. This book is intentionally what my American friend would call the ‘practical’ type. For some years there has been a trend for chemistry teaching to become more theoretical. There is always theo- retical interest in another interesting oxidation state or another unusual complex, but the balance of this book is tilted to ensure that they do not exclude the commonplace, the mundane and the commercially important. T think it is important that students are aware of which chemicals are commercially important, especially those produced in very large tonnages, Linked to this is what are they used for, the processes by which they are manufactured and where the raw materials come from. This relates college chemistry to the real world, but regrettably few books cover these details. The data on tonnages of chemicals produced and the main sources of minerals have been completely updated. Data are mainly from World Mineral Statistics, published by the British Geological Survey, and from the Industrial Statistics Yearbook published by the United Nations, New York, and from direct contact with about 250 firms. The figures vary only Slightly from year to year, and illustrate the general scale of use and main sources of raw materials. Not only is the production of major chemicals such as H2S0,, NH3, NaOH, Clo, O2 and N2 adequately covered, but re cic en Srp and are aca Chemistry is exciting, and is ite on all around g Nene covered: but fascinating applications are alse “described and 2 Many smaller scale é o described and explained. These in- clude baking powder, photography, supercond uctors, transistors. photo- copiers. carbon dating. the atomic bomb, uses } of radioisotopes and many TI a