The chemical bond in inorganic chemistry: the bond valence model
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| Main Author: | |
|---|---|
| Format: | Book |
| Language: | English |
| Published: |
Oxford, United Kingdom
Oxford University Press
2016
|
| Edition: | 2nd edition |
| Series: | IUCr monographs on crystallography
27 |
| Subjects: | |
| Online Access: | Inhaltsverzeichnis Klappentext |
| Physical Description: | xiii, 315 Seiten Illustrationen, Diagramme |
| ISBN: | 9780198742951 0198742959 |
Staff View
MARC
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| adam_text | Contents
1 Historical Introduction 1
1.1 Introduction 1
1.2 Chemical Bonds 2
1.3 The Ionic Model 3
1.4 Quantum Mechanics 4
1.5 The Symmetry Model 4
1.6 Topological Models 5
1.7 Pauling s Electrostatic Valence Model 6
2 The Flux Theory of the Chemical Bond 9
2.1 Introduction 9
2.2 Theoretical Foundation 11
2.2.1 The Structure of the Atom 11
2.2.2 Electrostatic Theory 14
2.2.3 The Role of Symmetry 15
2.2.4 The Core-and-Valence-Shell Picture of the Atom 16
2.3 The Chemical Bond 17
2.3.1 The Neutral Atom Model 17
2.3.2 Coordination Numbers 19
2.3.3 Bond Networks 19
2.3.4 The Ionic Model 23
2.3.5 Some Theorems 25
2.3.6 The Covalent Model 33
2.3.7 Bond Angles 35
2.3.8 The Bond Valence Model 35
3 The Bond Valence Model 36
3.1 Introduction 36
3.2 Bond Lengths 37
3.3 Coordination Number 40
3.4 Theorems of the Bond Valence Model 41
3.4.1 Valence Sum Rule 41
3.4.2 The Distortion Theorem 42
3.4.3 Lewis Acid and Base Strength 45
3.4.4 Network Equations 48
3.4.5 Networks with Non-Bipartite Graphs 50
3.4.6 Valence Maps 55
58
61
64
64
65
70
72
73
73
74
75
76
76
79
81
82
84
85
87
88
92
92
92
97
99
102
105
107
107
108
108
110
111
112
117
121
125
127
Contents
3.4.7 Bond Angles and Valence Vectors
3.5 Hard and Soft Acids and Bases
Cation Coordination Number
4.1 Introduction
4.2 Anion-Anion Repulsion
4.3 The Bonding Strength of the Anions
4.4 Availability of Counterions
4.5 Electronic Effects
4.6 Steric Constraints
4.7 Symmetry
4.8 Conclusion
Hydrogen Bonds
5.1 Introduction
5.2 The Role of Anion-Anion Repulsion
5.3 The Normal Hydrogen Bond
5.4 Short Hydrogen Bonds
5.5 Long Hydrogen Bonds
5.6 The Structural Chemistry of the Hydrogen Ion
5.7 Other Types of Hydrogen Bond
5.8 Assigning Experimental Bond Valences to Hydrogen
Bonds
Liquids
6.1 Introduction
6.2 Aqueous Solubility
6.3 Hydration of Cations
6.4 Protonation of Anions
6.5 Acidity and Alkalinity
6.6 Non-Aqueous Solutions and Melts
Electronically Distorted Structures
7.1 The Origins of Electronic Distortions
7.2 Modelling Electronically Distorted Structures
7.2.1 Multipoles
7.2.2 Flux Methods
7.2.3 Bond Valence Vectors
7.3 Main Group Atoms with Lone Pairs
7.3.1 Behaviour of Lone Pairs on Cations
7.3.2 Behaviour of Lone Pairs on Anions
7.4 Transition Metals
7.4.1 Early Transition Metal Cations with d°
or d1 Configurations
Contents xi
7.4.2 Jahn-Ieller Distorted Cations 131
7.4.3 Late Transition Metals 132
7.5 Conclusions 134
Physical Properties of Bonds 136
8.1 Introduction 136
8.2 Bond Energy 137
8.3 Atomic Radii 139
8.4 Bond Lengths and Bond Angles 140
8.5 Bond Force Constants and Thermal Vibrations 141
8.6 Thermal Expansion 144
8.7 The Effects of Pressure on the Lengths of Bonds 148
8.8 The Variation of Rq with Temperature and Pressure 150
Space and Space Groups 152
9.1 Introduction 152
9.2 The Crystal Lattice and Translational Symmetry 153
9.3 Space Groups 156
9.4 Special Positions 158
9.5 Matching the Special Positions to the Chemistry 160
9.6 The Symmetry of Bonded Neighbours 161
9.7 Conclusion 164
Modelling Inorganic Structures 165
10.1 The Problem of A Priori Modelling 165
10.2 Determining the Topology 166
10.2.1 Space-Based Approaches 168
10.2.2 Chemistry-Based Approaches 173
10.2.3 Valence Maps 191
10.3 Refining the Geometry 191
10.4 Modelling Defect Structures 193
10.5 Modelling Glasses 196
10.6 Example of an A Priori Modelling: Beryl 197
10.7 Conclusion 202
Steric Strain 203
11.1 The Origins of Steric Strain 203
î 1.2 Measurement of Steric Strain 206
î 1.3 Relaxation of Steric Strain 208
11.3.1 Relaxation of the Geometry 209
11.3.2 Relaxation by Defects 209
11.3.3 Electronic Relaxation 210
11.3.4 Effects of Temperature and Displacive Phase
Transitions 211
xii Contents
11.3.5 Changing the Bond Graph—Reconstructive
Phase Transitions 212
1 1.3.6 Summary of Relaxations 213
11.4 Incommensurate Structures 213
12 Applications 217
12.1 Introduction 217
12.2 Crystallography 218
12.2.1 Structure Determination 218
12.2.2 Analysis of Crystal Structures 220
12.3 Physics 222
12.3.1 Pcrovskitc-Rclatcd Solids 223
12.3.2 Electrical Properties 227
12.3.3 Magnetic Properties 232
12.3.4 Other Physical Properties 233
12.4 Chemistry 233
1 2.4.1 Non-Diffraction Techniques 233
12.4.2 Heterogeneous Catalysis 234
12.4.3 Esterification and Hydrolysis 236
12.4.4 Education 237
12.5 Mineralogy 238
12.5.1 Soil Chemistry 239
12.5.2 Zeolites 242
12.5.3 Glasses 242
12.6 Materials 242
12.6.1 Crystal Growth 242
12.6.2 Surfaces and Interfaces 243
12.7 Biology 245
12.7.1 Enzymes 245
12.7.2 Calcium and Sodium Binding by Proteins 247
12.8 Databases 249
13 Chemical Implications of the Bond Valence Model 250
13.1 Historical Development of the Bond Theory 250
13.2 The Complementary Natures of the Flux
and Quantum Theories 252
13.3 Properties of the Bond Flux 255
13.4 Relationship to Other Chemical Models 258
13.5 Conclusion 260
Appendix 1 Determining Bond Valence Parameters 261
A1.1 Introduction 261
A 1.2 Determination of Bond Valence Parameters 262
A1.2.1 Methods of Determining Bond Valences 262
Contents xiii
Al .2.2 Selection of riie Target Set of Observed Atomic
Environments 263
A 1.2.3 Refinement 264
A 1.2.4 Special Cases 266
A 1.3 Other Expressions 267
Appendix 2 Space Group Spectra 269
Appendix 3 Refcodes for Crystal Structures 278
Appendix 4 Glossary 283
References 291
Index 311
The bond valence model, a description of acid-base bonding, is widely used for analysing and
modelling the structures and properties of solids and liquids. Unlike other models of inorganic
chemical bonding, the bond valence model is simple, intuitive and predictive, and is accessible
to anyone with a pocket calculator and a secondary schcxil command of chemistry and physics.
This new edition of llu՝ Chemical Bond in in organic Chemistry: llje Bond Valence d/w/r/derives
the rules of the bond valence model, as well as those of the traditional covalent, ionic and popular
YSEPR models, by identifying the chemical bond with the electrostatic flux linking the bonded
atoms. It shows how chemical properties arise naturally from the conflict between the constraints
of chemistry and those of three-dimensional space. Most of the new edition is devoted to showing
how to apply these ideas to real materials including crystals, liquids, glasses and surfaces. The work
includes detailed examples of applications, and the final chapter explores the relationship between
the flux and quantum theories of the bond.
i his ni-: v KnmoN:
• Describes Flux Theory of the Chemical Bond, a new approach to all models of chemical
bonding useful for teaching
• Updates and extends the chapters on the application of these rules to real systems
• Includes worked examples
David Brown is Professor F.meritus at the Department of Physics and Astronomy, McMaster
University, Hamilton, Ontario, Canada.
RKVIKWS;
Mn ¡he Chemical Bond in inorganic Chemistry, one of the principal architects of the bond-vale nee
mcxfcl, I. David Brown, develops the kind of consistent theoretical framework the model once
lacked. It provides justification for an astonishing range of applications, which are also discussed
in some detail. This book should be required reading for any researcher attempting to employ
bond-valence concepts, because it includes all the tools and examples needed to apply the model
in profound and surprising ways. The concepts presented are simple enough that the book may also
be used to help even undergraduate students adopt a more intuitive and productive understanding
i f ch e m i ca I b n d i n g.
Prof. Barry R. Bickmore, Brigham Young University *
*For scientists working on solids, this hook is essential reading. The bond-valence model prov ides
a pow erful yet intuitive approach to understanding the variation in atomic arrangements and
physical properties of crystalline and related materials. In this second edition of his now classic
book, I. David Brown clarifies the relations between the bond-valence model and other approaches
to chemical bonding. He emphasizes the insight that the model can provide to the structures and
chemical compositions of crystalline solids, and describes how processes such as crystallization,
adsorption and dissolution can lx՝ nuxlelled.’
Frank Hawthorne, University of Manitoba
OXFORD
UNIVERSITY PRESS
ISBN 978-0-19-874295-1
I
9 780198 742951
www.oup.com
|
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| spelling | Brown, I. David Verfasser (DE-588)1126061891 aut The chemical bond in inorganic chemistry the bond valence model I. David Brown, Professor Emeritus, Department of Physics and Astronomy, McMaster University, Hamilton, Ontario 2nd edition Oxford, United Kingdom Oxford University Press 2016 xiii, 315 Seiten Illustrationen, Diagramme txt rdacontent n rdamedia nc rdacarrier IUCr monographs on crystallography 27 Mathematisches Modell Chemical bonds Mathematical models Inorganic compounds Chemische Bindung (DE-588)4009843-6 gnd rswk-swf Anorganische Verbindungen (DE-588)4002147-6 gnd rswk-swf Anorganische Verbindungen (DE-588)4002147-6 s Chemische Bindung (DE-588)4009843-6 s DE-604 IUCr monographs on crystallography 27 (DE-604)BV005455767 27 Digitalisierung UB Bayreuth - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=029772236&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis Digitalisierung UB Bayreuth - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=029772236&sequence=000002&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA Klappentext |
| spellingShingle | Brown, I. David The chemical bond in inorganic chemistry the bond valence model IUCr monographs on crystallography Mathematisches Modell Chemical bonds Mathematical models Inorganic compounds Chemische Bindung (DE-588)4009843-6 gnd Anorganische Verbindungen (DE-588)4002147-6 gnd |
| subject_GND | (DE-588)4009843-6 (DE-588)4002147-6 |
| title | The chemical bond in inorganic chemistry the bond valence model |
| title_auth | The chemical bond in inorganic chemistry the bond valence model |
| title_exact_search | The chemical bond in inorganic chemistry the bond valence model |
| title_full | The chemical bond in inorganic chemistry the bond valence model I. David Brown, Professor Emeritus, Department of Physics and Astronomy, McMaster University, Hamilton, Ontario |
| title_fullStr | The chemical bond in inorganic chemistry the bond valence model I. David Brown, Professor Emeritus, Department of Physics and Astronomy, McMaster University, Hamilton, Ontario |
| title_full_unstemmed | The chemical bond in inorganic chemistry the bond valence model I. David Brown, Professor Emeritus, Department of Physics and Astronomy, McMaster University, Hamilton, Ontario |
| title_short | The chemical bond in inorganic chemistry |
| title_sort | the chemical bond in inorganic chemistry the bond valence model |
| title_sub | the bond valence model |
| topic | Mathematisches Modell Chemical bonds Mathematical models Inorganic compounds Chemische Bindung (DE-588)4009843-6 gnd Anorganische Verbindungen (DE-588)4002147-6 gnd |
| topic_facet | Mathematisches Modell Chemical bonds Mathematical models Inorganic compounds Chemische Bindung Anorganische Verbindungen |
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