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Principles of Inorganic Chemistry: Basics and Applications
ISBN-13: 9783031229251 / Angielski / Twarda / 2024 / 1338 str.
Principles of Inorganic Chemistry: Basics and Applications
ISBN-13: 9783031229251 / Angielski / Twarda / 2024 / 1338 str.
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This textbook provides a current and comprehensive coverage of all major topics of inorganic chemistry in a single source. It includes an analysis of the sources and preparations of the elements, their common compounds, their aqueous speciation, and their applications, while it also discusses reaction pathways and mechanisms. It includes up-to-date material, supported by over 4000 references to the original literature and to recent reviews that provide more detailed information. The material is accompanied by over 250 figures and three-dimensional representations, based on published structural details. Each chapter has worked examples and problems, with multiple inserts describing topical issues related to the material in the text. The textbook provides the instructor with a wide range of areas that can be selected to meet the background and interests of the students, while selected chapters are relevant to courses on more specialized topics, such as inorganic materials, bioinorganic chemistry, and nanomaterials. The intended readers are students, lecturers, and researchers who need a source for the current status of the area.
This textbook provides a current and comprehensive coverage of all major topics of inorganic chemistry in a single source. It includes an analysis of the sources and preparations of the elements, their common compounds, their aqueous speciation, and their applications, while it also discusses reaction pathways and mechanisms. It includes up-to-date material, supported by over 4000 references to the original literature and to recent reviews that provide more detailed information. The material is accompanied by over 250 figures and three-dimensional representations, based on published structural details. Each chapter has worked examples and problems, with multiple inserts describing topical issues related to the material in the text. The textbook provides the instructor with a wide range of areas that can be selected to meet the background and interests of the students, while selected chapters are relevant to courses on more specialized topics, such as inorganic materials, bioinorganic chemistry, and nanomaterials. The intended readers are students, lecturers, and researchers who need a source for the current status of the area.
1 Atoms and Electrons
1.1 Introduction
1.2 The Bohr Atom
1.3 Electron as a Wave
1.4 The Schrödinger Equation
1.4.1 Schrödinger Equation Solution for One-Electron Systems
1.5 Quantum Numbers1.6 Orbital Representations
1.6.1 Two-Dimensional Representations
1.6.2 Three-Dimensional Representations
1.7 Multi-Electron Atoms
1.7.1 Putting Electrons into Atomic Orbitals
1.7.2 Exceptions to Madelung's Rule2 The Periodic Table
2.1 Early Development
2.2 Structure of the Periodic Table
2.3 Periodic Trends of Some Physical Properties of Atoms
2.3.1 Ionization Energy2.3.2 Electron Affinity
2.3.3 Electronegativity
2.3.4 Covalent, Ionic, or Metallic Bonding, and Electronegativity
2.3.5 Atom Size
2.3.6 Bond Valence Model
2.3.7 Ionic Radii
2.3.8 Periodic Trends in Atom Sizes
2.4 Summary of Periodic Trends
2.5 Supporting Information
3 Covalent Bonding Theories
3.1 Introduction
3.1.1 Common Terms
3.2 Lewis Electron Dot Theory
3.2.1 Electron Dot Diagrams
3.2.2 Expanded Octet
3.2.3 Nonequivalent Resonance Structures, Formal Charge, and the Octet Rule
3.2.4 Problems for the Octet Rule
3.2.5 Lewis Structures and Oxidation States
3.3 Valence Shell Electron Pair Repulsion, VSEPR, Theory
3.3.1 Geometrical Arrangements from VSEPR Theory
3.3.2 Structural Trends and VSEPR Theory
3.3.3 Problems with VSEPR Theory
3.4.4 Summary of Problems and Advances
3.4 Valence Bond Theory
3.4.1 Hybridization of Orbitals
3.4.2 Multiple Bonds and Resonance
3.4.3 Hybridization of d Orbitals
3.4.4 Summary of Problems and Advances
3.5 Molecular Orbital Theory
3.5.1 Basics of the Theory
3.5.2 Molecular Orbitals from p Valence Orbitals in Diatomic Species
3.5.3 Molecular Orbital Electronic Configurations of Diatomic Species
3.5.4 Photoelectron Spectroscopy
3.5.5 Photoelectron Spectra of O2 and N2
3.5.6 Orbital Mixing in Molecular Orbital Theory
3.5.7 Molecular Orbitals in Heteronuclear Diatomic Species
3.5.8 Molecular Orbitals in Triatomic Species
3.5.9 Molecular Orbitals for Linear and Bent Triatomic Species
3.5.10 Trihalide Anions and Related Hypervalent Species
3.5.11 Methane
3.6 Putting It All Together
3.7 Supporting Information
3.7.1 Secular Equation Solution for a Triatomic System
4 Energy
4.1 Introduction
4.1.1 Basic Thermodynamic Relationships
4.1.2 Gibbs Free Energy and the Equilibrium Constant
4.2 Bond Energies and Bond Dissociation Enthalpies
4.2.1 Average Bond Dissociation Enthalpies
4.2.2 Applications of Bond Dissociation Enthalpies
4.2.3 Bond Dissociation Enthalpies and Bonding Theory
4.3 Thermodynamics and Chemical Cycles
4.3.1 Process Chemical Cycles
4.3.2 Isothermal Chemical Cycles
4.3.3 Lattice Energies and Interatomic Distances
4.3.4 Lattice Energies and Molecular Volumes
4.3.5 Other Isothermal Cycles
5 Acids and Bases
5.1 Introduction
5.2 Brønsted or Protic Acids and Bases
5.2.1 Characteristics of Brønsted Acids and Bases
5.2.2 Strengths of Brønsted Acids and Bases
5.2.3 Strengths of Strong Brønsted Acids
5.2.4 Brønsted Superacids
5.2.5 Brønsted Superbases
5.3 Lewis Acids and Bases
5.3.1 Strengths of Lewis Acids and Bases
5.3.2 Single Reference Scales of Acidity and Basicity
5.3.3 The Dual Parameter E and C Model for Lewis Acidity and Basicity
5.3.4 Some General Trends in Lewis Acidities
5.3.5 The Hard and Soft Model for Lewis Acidity and Basicity
5.3.6 Frustrated Lewis Pairs, FLPs
6 Reaction Types and Mechanisms
6.1 Introduction
6.2 Reaction Types
6.2.1 Proton-Transfer Reactions
6.2.2 Substitution Reactions
6.2.3 Oxidation–Reduction Reactions
6.2.4 Oxidative-Addition Reactions
6.2.5 Isomerization Reactions
6.3 Kinetic Background
6.3.1 The Rate Law
6.3.2 Temperature and Pressure Effects
6.3.3 Ionic Strength Effects
6.4 Proton-Transfer Mechanisms
6.5 Substitution Reaction Mechanisms
6.6 Oxidation–Reduction Reaction Mechanisms
6.6.1 Reaction Types
6.6.2 Inner-sphere Electron Transfer
6.6.3 Outer-sphere electron transfer
6.7 Oxidative-Addition Reaction Mechanisms
6.7.1 Oxidative-Addition of X—Y Molecules
6.7.2 Oxidative-Addition of Organic Halides to Transition Metals
6.8 Isomerization Reaction Mechanisms
6.8.1 Linkage Isomerization
6.8.2 Geometrical Isomerization
6.9 Supporting Information
6.9.1 Rate Laws
6.9.2 Rapid-Equilibrium Assumption
6.9.3 Steady-State Assumption
7 The Solid State and Symmetry
7.1 Introduction
7.2 Some Elements of Group Theory
7.2.1 Symmetry Operations and Point Groups
7.2.2 Group Theory and Vibrational Spectroscopy
7.2.3 Selection Rules in Vibrational Spectroscopy
7.2.4 Group Theory and Orbitals
7.3 Crystalline Inorganic Solids
7.3.1 Introduction
7.3.2 Some Common Structure Types
7.3.3 Radius-Ratio Method
7.4 Metals
7.4.1 Properties of Metals
7.4.2 Structures of Metals
7.4.3 Bonding in Metals
7.5 Electrical Insulators and Semiconductors
7.6 Spinels and Perovskites
7.7 Supporting Information
7.7.1 Crystal Structures: Seeing the Picture
7.7.2 Ionic Radii
8 Introduction to Transition Metals
8.1 Introduction
8.2 Coordination Compounds
8.3 Ligand Types in Coordination Compounds
8.4 Ligand Arrangements and Isomers
8.4.1 Octahedral, Square Planar, and Tetrahedral Systems
8.4.2 Other Ligand Arrangements
8.4.3 Ionization Isomers
8.4.4 Hydrate Isomers
8.4.5 Optical Isomers
8.4.6 Meso Isomers
8.4.7 Isomer Identification and Counting
8.4.8 Conformational Isomers
8.4.9 Isomers as Templates for Open-Framework Materials
8.5 Bonding Theories for Transition Metal Complexes
8.5.1 Historical Background
8.5.2 Crystal Field Theory
8.5.3 Valence Bond Theory
8.5.4 Ligand Field Theory
8.6 Electronic Spectra: Colors
8.6.1 Electronic States and Term Symbols
8.6.2 Electronic States in an Octahedral Field8.6.3 Energy Units in Electronic Spectroscopy
8.6.4 Energies of Russell–Saunders Terms and Ligand Field States
8.6.5 Electronic Spectra of d3 and d8 Systems
8.6.6 Electronic Spectra of d6 Systems
8.7 Trends in Values of ∆ and B
8.8 Six-Coordinate Complexes of Lower Symmetry than Oh
8.9 Magnetic Properties
8.9.1 Basic Concepts and Terminology
8.9.2 Magnetic Moment and Unpaired Electrons
8.9.3 Representative Examples of Magnetic Behavior
9 The Transition Metals: Groups 3–12
9.1 Introduction: the Elements9.2 General Properties of the Transition Elements
9.3 Group 3: Scandium, Yttrium, and Lanthanum
9.4 Group 4: Titanium, Zirconium, and Hafnium
9.5 Group 5: Vanadium, Niobium, and Tantalum
9.6 Group 6: Chromium, Molybdenum, and Tungsten
9.7 Group 7: Manganese, Technetium, and Rhenium
9.8 Group 8: Iron, Ruthenium, and Osmium
9.9 Group 9: Cobalt, Rhodium, and Iridium
9.10 Group 10: Nickel, Palladium, and Platinum
9.11 Group 11: Copper, Silver, and Gold
9.12 Group 12: Zinc, Cadmium, and Mercury
10 Organometallic Chemistry of Transition Metals
10.1 What is Organometallic?
10.2 Bonding in Organometallic Systems
10.2.1 The Eighteen-Electron "Rule"
10.2.2 Arrangement of Organometallic Substituents
10.2.3 Bonding in Metal Carbonyls
10.2.4 Bonding in Metal Bis-Cyclopentadiene Species
10.3 Reactions of Organometallic Species
10.3.1 Syntheses of Mm(CO)n, M(C5H5)2, M(C6H6)2 and their Derivatives
10.3.2 Syntheses of Fe2(C5H5)2(CO)4 and Some Derivatives
10.3.4 Homogeneous Hydrogenation Catalysis
11 The Lanthanides
11.1 Introduction
11.2 Extraction and Separation of the Lanthanides
11.3 The Elements
11.4 The Lanthanide Contraction
11.5 Compounds of the Lanthanides
11.5.1 Oxides of the Lanthanides
11.5.2 Halides of the Lanthanides
11.5.3 Organometallic Lanthanides
12 Groups 1 & 2
12.1 Introduction: the Elements
12.2 Natural Sources and Preparation of the Elements
12.2.1 Hydrogen
12.2.2 Lithium
12.2.3 Sodium
12.2.4 Potassium, Rubidium, and Cesium
12.2.5 Beryllium
12.2.6 Magnesium
12.2.7 Calcium
12.2.8 Strontium and Barium
12.3 Structures, Properties, and Uses of the Elements12.3.1 Hydrogen
12.3.2 The Alkali Metals
12.3.3 The Alkaline Earth Metals
12.4 Binary Compounds with Oxygen
12.4.1 The Oxide and Peroxide of Hydrogen
12.4.2 Oxides of the Alkali Metals
12.4.3 Oxides of the Alkaline Earth Metals
12.4.4 Peroxides of the Alkali and Alkaline Earth Metals
12.4.5 Superoxides of the Alkali Metals
12.4.6 Ozonides of the Alkali Metals
12.5 Aqueous ions
12.5.1 The Hydrated Proton
12.5.2 Aqueous Cations
12.5.3 Aqueous Anions
12.6 Binary Carbides of the Metals of Groups 1 and 2
12.7 Binary Nitrides of the Metals of Groups 1 and 2
13 Group 1313.1 Introduction: the Elements
13.2 Natural Sources and Preparation of the Elements
13.2.1 Boron
13.2.2 Aluminum
13.2.3 Gallium, Indium, and Thallium
13.3 Structures, Properties, and Uses of the Elements
13.3.1 Boron
13.3.2 Aluminum
13.3.3 Gallium, Indium, and Thallium
13.4 Oxides
13.4.1 General Features
13.4.2 Boron Oxides
13.4.3 Aluminum Oxides
13.4.4 Gallium and Indium Oxides
13.4.5 Thallium Oxides
13.5 Borates, Boric Acid, and Their Derivatives
13.5.1 Borate Anion Structures13.5.2 Boric Acid and Metaboric Acid Structures
13.5.3 Boric Acid and its Esters in Aqueous Solution
13.5.4 Boronic Acids13.6 Aluminum, Gallium, and Indium Hydroxides and Aqua Ions
13.6.1 Aluminum Hydroxide
13.6.2 Aqueous Al(III)
13.6.3 Gallium and Indium Hydroxides and Aqua Ions
13.7 Borides
13.8 Nitrides
13.8.1 Boron Nitride
13.8.2 Aluminum Nitride
13.8.3 Gallium Nitride
13.8.4 Indium Nitride
13.9 Carbides
13.9.1 Boron Carbide
13.9.2 Aluminum Carbide
13.10 Hydrides
13.10.1 Tetrahydride Anions of Boron and Aluminum
13.10.2 Boron Hydrides
13.10.3 Boron Hydride Derivatives
13.10.4 Carboranes
13.10.5 Metallacarboranes
13.10.6 Aluminum Hydride
13.11 Halides
13.11.1 Properties and Structures
13.11.2 Trihalides as Lewis Acids
13.12 Organic Derivatives
13.12.1 Properties and Structures
13.12.2 Activators for Olefin Polymerization
13.12.3 Fluorinated Organoboron Derivatives
13.12.4 Organoboron Derivatives in Hydroboration and C—C Bond Formation
14 Group 14
14.1 Introduction: the Elements
14.2 Natural Sources and Preparation of the Elements
14.2.1 Carbon
14.2.2 Silicon
14.2.3 Germanium
14.2.4 Tin
14.2.5 Lead
14.3 Structures, Properties, and Uses of the Elements
14.3.1 Common Allotropes of Carbon
14.3.2 Fullerenes
14.3.3 Carbon Nanotubes
14.3.4 Graphene
14.3.5 Silicon
14.3.6 Germanium
14.3.7 Tin
14.3.8 Lead
14.4 Oxides
14.4.1 The Gaseous Monoxides
14.4.2 The Solid Monoxides
14.4.3 Carbon Dioxide
14.4.4 Silicon Dioxide or Silica, SiO2
14.4.5 Germanium Dioxide, GeO2
14.4.6 Dioxides of Tin and Lead, SnO2 and PbO2
14.5 Oxoacids, Oxoanions, and Aqueous Cations
14.5.1 Carbon Oxoacids and Oxoanions
14.5.2 Silicon Oxoacids and Oxoanions
14.5.3 Germanium Oxoacids and Oxoanions
14.5.4 Tin and Lead aqua Cations and Oxoanions
14.6 Halides
14.6.1 The Tetrahalides
14.6.2 The Dihalides
14.6.3 Lewis Base Adducts with Group 14 Halides14.7 Organic Derivatives of Si, Ge, S, and Pb
14.9 Catenation
14.9.1 Catenation with Single Bonds
14.9.2 Catenation with Double Bonds
14.9.3 Catenation with Triple Bonds
14.10 Amines and Nitrides
14.10.1 Amines14.10.2 Nitrides
15 Group 15
15.1 Introduction: the Elements
15.2 Natural Sources and Preparation of the Elements
15.2.1 Nitrogen
15.2.2 Phosphorus
15.2.3 Arsenic, Antimony, and Bismuth
15.3 Structures, Properties, and Uses of the Elements
15.3.1 Dinitrogen or Nitrogen
15.3.2 Phosphorus
15.3.3 Arsenic, Antimony, and Bismuth
15.4 Oxides
15.4.1 Oxides of Nitrogen
15.4.2 Oxides of Phosphorus
15.4.3 Oxides of Arsenic, Antimony, and Bismuth
15.5 Oxoacids and Oxoanions
15.6 Hydrides
15.6.1 The AH3 Hydrides: Properties and Structures
15.6.2 Ammonia
15.6.3 Hydrazine
15.6.4 Diazene
15.6.5 Hydroxylamine
15.6.6 Nitroxyl
15.6.7 Hydrides of Phosphorus, Arsenic, Antimony, and Bismuth
15.7 Halides
15.7.1 The Trihalides, AX3
15.7.2 The Pentahalides, AX5
15.7.3 The Oxohalides, OAX3
15.7.4 Mixed Halides of Phosphorus: Halogen Exchange
15.7.5 Phosphorus(III) Halide Derivatives: Phosphenium Ions
15.8 Binary Nitrides
15.8.1 Classification of Nitrides
15.8.2 Preparations and Uses of Some Nitrides
15.8.3 Structures of Representative Nitrides
15.9 Organic Amines, Phosphanes, and Related Compounds
15.9.1 Organic Derivatives of the AL3 Type
15.9.2 Organic Derivatives of the AL5 Type
15.9.3 Preparations and Uses of Some Organic Amines and Phosphanes
15.9.4 Phosphanes as Ligands in Organometallic Chemistry
16 Group 16
16.1 Introduction: the Elements
16.2 Natural Sources and Preparation of the Elements
16.2.1 Oxygen
16.2.2 Sulfur
16.2.3 Selenium and Tellurium
16.3 Structure, Properties, and Uses of the Elements
16.3.1 Dioxygen or Oxygen
16.3.2 Singlet Oxygen
16.3.3 Ozone and Covalent Ozonides
16.3.4 Sulfur
16.3.5 Selenium, Tellurium, and Polonium
16.4 Oxides, Oxo Acids, and Oxo Anions
16.4.1 Oxo Anions of Oxygen
16.4.2 Oxides, Oxo Acids, and Oxo Anions of Sulfur
16.4.3 Oxides, Oxo Acids, and Oxo Anions of Selenium and Tellurium
16.5 Halides and Oxo halides
16.6 Hydrides
16.8 Organic Derivatives
17 Group 17
17.1 Introduction: the Elements
17.2 Natural Sources and Preparation of the Elements
17.2.1 Fluorine
17.2.2 Chlorine
17.2.3 Bromine
17.2.4 Iodine
17.3 Structures, Properties, and Uses of the Elements
17.4 Oxides, Oxoacids, and Oxoanions
17.4.1 Oxygen Halides, Hypohalous Acids, and Hypohalites
17.4.2 The Halogen Dioxides
17.4.3 The Halites and Halous Acids
17.4.4 The Halates and Halic Acids
17.4.5 The Perhalates and Perhalic Acids
17.5 The Interhalogens
17.5.1 Properties of Some Interhalogens
17.5.2 Unusual Structures of Some Interhalogens18 Group 18
18.1 Introduction: the Elements
18.2 Natural Sources and Preparation of the Elements
18.2.1 Helium
18.2.2 Neon, Argon, Krypton, and Xenon
18.3 Stuctures, Properties, and Uses of the Elements
18.3.1 Helium
18.3.2 Neon, Argon, Krypton, and Xenon
18.4 Chemical Derivatives of Noble Gases
18.4.1 Binary Fluorides of Xenon and Krypton
18.4.2 Binary Oxides and Oxo-anions of Xenon
18.4.3 Oxofluorides of Xenon
19 Bioinorganic Chemistry
19.1 Introduction
19.2 Functions of Some Main Group Elements
19.2.1 Iodine and Selenium
19.3 Functions of Some Transition Metals
19.3.1 Zinc in Human Carbonic Anhydrase, hCA II
19.3.2 Zinc in Peptidases
19.3.3 Cobalt in Coenzyme B12
19.3.4 Cobalt in a Mutase and a Synthase
19.3.5 Iron in Porphyrins and Hemoglobin
19.3.6 Iron in Cytochrome P450s
20 Nanomaterials
20.1 Introduction
20.2 Formation of Nanomaterials
20.2.1 Rate of Growth
20.2.2 Surface Energy and Growth
20.2.3 Determination of the Sizes of Nanoparticles
20.2.4 Colors of Nanoparticles
20.3 Synthesis and Properties of Some Nanomaterials
20.3.1 Synthesis of Gold Nanoparticles, Au NPs
20.3.2 Synthesis of Silver Nanoparticles, Ag NPs
20.3.3 Synthesis of Copper Nanoparticles, Cu NPs
20.3.4 Synthesis of Iron Nanoparticles, Fe NPs
20.3.5 Synthesis of Palladium and Platinum Nanoparticles, Pd NPs and Pt NPs
20.3.6 Synthesis of Silicon Nanoparticles, SiNPs
20.3.7 Synthesis of Metal–Oxide Nanoparticles
20.3.8 Synthesis of Binary Semiconductor Nanoparticles
20.4 Biological Uses and Effects of Nanomaterials
Robert B. Jordan received an Honors B.Sc. in chemistry from the University of Western Ontario, now Western University, in 1961 and proceeded to postgraduate work at the University of Chicago under the inspiring direction of Professor Henry Taube (Nobel Prize 1983). In 1962–63, he moved with Professor Taube to Stanford University to complete his postgraduate research for which he was awarded a Ph.D. from the University of Chicago in 1964. This was followed by a postdoctoral appointment with Professor John. P. Hunt at Washington State University, where he learned the basics of NMR in paramagnetic systems, with the assistance of Professor Harold Dodgen, and met his future wife. He was appointed as Assistant Professor in Chemistry at the University of Alberta in 1965, where he continued to serve until retirement in 2005. During this time, he was promoted to Associate and then Full Professor in 1971 and 1978, respectively, and was Department Chairman from 1984 to 1989. The help of many graduate students and several collaborators resulted in the publication of 132 papers. He also authored the book titled "Reaction Mechanisms of Inorganic and Organometallic Systems" which has been published in three editions in 1991, 1998, and 2007.
This textbook provides a current and comprehensive coverage of all major topics of inorganic chemistry in a single source. It includes an analysis of the sources and preparations of the elements, their common compounds, their aqueous speciation, and their applications, while it also discusses reaction pathways and mechanisms. It includes up-to-date material, supported by over 4000 references to the original literature and to recent reviews that provide more detailed information. The material is accompanied by over 250 figures and three-dimensional representations, based on published structural details. Each chapter has worked examples and problems, with multiple inserts describing topical issues related to the material in the text. The textbook provides the instructor with a wide range of areas that can be selected to meet the background and interests of the students, while selected chapters are relevant to courses on more specialized topics, such as inorganic materials, bioinorganic chemistry, and nanomaterials. The intended readers are students, lecturers, and researchers who need a source for the current status of the area.
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