Chemistry of the Elements Second Edition

N. N. GREENWOOD and A. EARNSHAW School of Chemistry University of Leeds, U.K.

SJUTTERWORTH E I N E M A N N

Contents Preface to the second edition Preface to the first edition Chapter 1

Origin of the Elements. Isotopes and Atomic Weights 1.1 1.2 1.3 1.4 1.5

1.6

Chapter 2

Chemical Periodicity and the Periodic Table 2.1 2.2 2.3 2.4

Chapter 3

Introduction Origin of the Universe Abundances of the Elements in the Universe Stellar Evolution and the Spectral Classes of Stars Synthesis of the Elements 1.5.1 Hydrogen burning 1.5.2 Helium burning and carbon burning 1.5.3 The a-process 1.5.4 The e-process (equilibrium process) 1.5.5 The s- and r-processes (slow and rapid neutron absorption) 1.5.6 The p-process (proton capture) 1.5.7 The x-process Atomic Weights 1.6.1 Uncertainty in atomic weights 1.6.2 The problem of radioactive elements

Introduction The Electronic Structure of Atoms Periodic Trends in Properties 2.3.1 Trends in atomic and physical properties 2.3.2 Trends in chemical properties Prediction of New Elements and Compounds

Hydrogen 3.1 3.2

3.3

3.4

Introduction Atomic and Physical Properties of Hydrogen 3.2.1 Isotopes of hydrogen 3.2.2 Ortho- and £>ara-hydrogen 3.2.3 Ionized forms of hydrogen Preparation, Production and Uses 3.3.1 Hydrogen 3.3.2 Deuterium 3.3.3 Tritium Chemical Properties and Trends 3.4.1 The coordination chemistry of hydrogen

xix xxi 1 1 1 3 5 9 9 10 11 12 12 13 13 15 16 18

20 20 21 23 23 27 29

32 32 34 34 35 36 38 38 39 41 43 44

vi

Contents 3.5 3.6

Protonic Acids and Bases The Hydrogen Bond 3.6.1 Influence on properties 3.6.2 Influence on structure 3.6.3 Strength of hydrogen bonds and theoretical description Hydrides of the Elements

48 52 53 59 61 64

Lithium, Sodium, Potassium, Rubidium, Caesium and Francium

68

4.1 4.2

68 68 68 69 71 74 76 77 79 79 82 84 86 87 90 99 102

3.7

Chapter 4

4.3

Chapter 5

Beryllium, Magnesium, Calcium, Strontium, Barium and Radium 5.1 5.2

5.3

Chapter 6

Introduction . The Elements 4.2.1 Discovery and isolation 4.2.2 Terrestrial abundance and distribution 4.2.3 Production and uses of the metals 4.2.4 Properties of the alkali metals 4.2.5 Chemical reactivity and trends 4.2.6 Solutions in liquid ammonia and other solvents Compounds 4.3.1 Introduction: the ionic-bond model 4.3.2 Halides and hydrides 4.3.3 Oxides, peroxides, Superoxides and suboxides 4.3.4 Hydroxides 4.3.5 Oxoacid salts and other Compounds 4.3.6 Coordination chemistry 4.3.7 Imides, amides and related Compounds 4.3.8 Organometallic Compounds

Introduction The Elements 5.2.1 Terrestrial abundance and distribution 5.2.2 Production and uses of the metals 5.2.3 Properties of the elements 5.2.4 Chemical reactivity and trends Compounds 5.3.1 Introduction 5.3.2 Hydrides and halides 5.3.3 Oxides and hydroxides 5.3.4 Oxoacid salts and coordination complexes 5.3.5 Organometallic Compounds Beryllium Magnesium Calcium, Strontium and Barium

Boron 6.1 6.2

6.3

Introduction Boron 6.2.1 Isolation and purification of the dement 6.2.2 Structure of crystalline boron 6.2.3 Atomic and physical properties of boron 6.2.4 Chemical properties Borides 6.3.1 Introduction 6.3.2 Preparation and stoichiometry 6.3.3 Structures of borides

107 107 108 108 110 111 112 113 113 115 119 122 127 127 131 136

139 139 140 140 141 144 144 145 145 146 147

Contents 6.4

6.5 6.6 6.7 6.8

6.9 6.10

7

Aluminium, Gallium, Indium and Thallium 7.1 7.2

7.3

8

Boranes (Boron Hydrides) 6.4.1 Introduction 6.4.2 Bonding and topology 6.4.3 Preparation and properties of boranes 6.4.4 The chemistry of small boranes and their anions (B1-B4) 6.4.5 Intermediate-sized boranes and their anions (B5 -B9) 6.4.6 Chemistry of «Wo-decaborane, B10H14 6.4.7 Chemistry of d