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Inorganic Chemistry

This text follows the organization around Miessler, Fischer and Tarr's textbook, but with content built as an Open Education Resource. This text map is under construction.

Inorganic Chemistry Chemistry

Tác giả: Haas et al.
Nhà xuất bản: Duke University
Nguồn: LibreTexts
Giấy phép: CC BY
Ngôn ngữ: EN
Danh mục: Khoa học cơ bản

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01: Introduction to Inorganic Chemistry
1.01: What is Inorganic Chemistry
1.02: Inorganic vs Organic Chemistry
1.03: History of Inorganic Chemistry
1.04: Perspectives
1.05: Practice problems
02: Atomic Structure
2.01: Historical Development of Atomic Theory
2.1.01: The Periodic Table
2.1.02: Discovery of Subatomic Particles and the Bohr Atom
2.02: The Schrodinger equation particle in a box and atomic wavefunctions
2.2.01: Particle in a Box
2.2.02: Quantum Numbers and Atomic Wave Functions
2.2.03: Aufbau Principle
2.2.04: Shielding
2.03: Periodic Properties of Atoms
2.3.01: Ionization energy
2.3.02: Electron Affinity
2.3.03: Covalent and Ionic Radii
2.04: Problems (do we want this here)
03: Simple Bonding Theory
3.01: Lewis Electron-Dot Diagrams
3.1.01: Resonance
3.1.02: Breaking the octet rule with higher electron counts (hypervalent atoms)
3.1.03: Formal Charge
3.1.04: Lewis Fails to Predict Unusual Cases - Boron and Beryllium
3.02: Valence Shell Electron-Pair Repulsion
3.2.01: Lone Pair Repulsion
3.2.02: Multiple Bonds
3.2.03: Electronegativity and Atomic Size Effects
3.2.04: Ligand Close Packing
3.03: Molecular Polarity
3.04: Hydrogen Bonding
04: Symmetry and Group Theory
4.01: Symmetry Elements and Operations
4.02: Point Groups
4.2.01: Groups of Low and High Symmetry
4.2.02: Other Groups
4.03: Properties and Representations of Groups
4.3.01: Matrices
4.3.02: Representations of Point Groups
4.3.03: Character Tables
4.04: Examples and Applications of Symmetry
4.4.01: Chirality
4.4.02: Molecular Vibrations
4.P: Problems (under construction)
05: Molecular Orbitals
5.01: Formation of Molecular Orbitals from Atomic Orbitals
5.1.01: Molecular Orbitals from s Orbitals
5.1.02: Molecular Orbitals from p Orbitals
5.1.03: Molecular orbitals from d orbitals
5.1.04: Nonbonding Orbitals and Other Factors
5.02: Homonuclear Diatomic Molecules
5.2.01: Molecular Orbitals
5.2.02: Orbital Mixing
5.2.03: Diatomic Molecules of the First and Second Periods
5.2.04: Photoelectron Spectroscopy
5.03: Heteronuclear Diatomic Molecules
5.3.01: Orbital ionization energies
5.3.02: Polar bonds
5.3.03: Ionic Compounds and Molecular Orbitals
5.04: Larger (Polyatomic) Molecules
5.4.01: Bifluoride anion
5.4.02: Carbon Dioxide
5.4.03: HO
5.4.04: NH
5.4.05: CO (Revisted with Projection Operators)
5.4.06: BF
5.P: Problems
06: Acid-Base and Donor-Acceptor Chemistry
6.01: Acid-Base Models as Organizing Concepts
6.02: Arrhenius Concept
6.03: Brnsted-Lowry Concept
6.3.01: Brnsted-Lowry Concept
6.3.02: Rules of Thumb for thinking about the relationship between Molecular Structure and Brnsted Acidity and Basicity
6.3.03: The acid-base behavior of binary element hydrides is determined primarily by the element's electronegativity and secondarily by the element-hydrogen bond strength.
6.3.04: Brnsted-Lowry Superacids and the Hammett Acidity Function
6.3.05: Thermodynamics of Solution-Phase Brnsted Acidity and Basicity
6.3.06: Thermodynamics of Gas Phase Brnsted Acidity and Basicity
6.3.07: The Acidity of an Oxoacid is Determined by the Electronegativity and Oxidation State of the Oxoacid's Central Atom
6.3.08: High Charge-to-Size Ratio Metal Ions Act as Brnsted Acids in Water
6.3.09: The Solvent System Acid Base Concept
6.3.10: Acid-Base Chemistry in Amphoteric Solvents and the Solvent Leveling Effect
6.3.11: Non-nucleophilic Brnsted-Lowry Superbases
6.04: Lewis Concept and Frontier Orbitals
6.4.01: The frontier orbital approach considers Lewis acid base reactions in terms of the donation of electrons from the base's highest occupied orbital into the acid's lowest unoccupied orbital.
6.4.02: All other things being equal electron withdrawing groups tend to make Lewis acids stronger and bases weaker while electron donating groups tend to make Lewis bases stronger and acids weaker
6.4.03: The electronic spectra of charge transfer complexes illustrate the impact of frontier orbital interactions on the electronic structure of Lewis-Acid base adducts
6.4.04: Substances' solution phase Lewis Basicity towards a given acid may be estimated using the enthalphy change for dissociation of its adduct with a reference acid of similar hardness.
6.4.05: In the boron triflouride affinity scale the enthalphy change on formation of an adduct between the base and boron triflouride is taken as a measure of Lewis basicity.
6.4.06: Lewis base strength may also be estimated by measuring structural or energy changes on formation of a Lewis acid-base complex as illustrated by efforts to spectroscopically assess of the strengths of halogen bonds
6.4.07: Bulky groups weaken the strength of Lewis acids and bases because they introduce steric strain into the resulting acid-base adduct.
6.4.08: Frustrated Lewis pair chemistry uses Lewis acid and base sites within a molecule that are sterically restricted from forming an adduct with each other.
6.05: Intermolecular Forces
6.5.01: Host-Guest Chemistry and - stacking interactions
6.5.02: Hydrogen bonds may be considered as a special type of Lewis acid-base interaction in which a Lewis acid hydrogen ion is shared between Lewis bases
6.06: Hard and Soft Acids and Bases
6.6.01: Quantitative Measures of Hardness Softness and Acid-Base Interactions from a Hard Soft Acid-Base Principle perspective involve orbital energies and or apportioning acid-base bonding in terms of electrostatic and covalent factors
6.6.02: Hard-Hard and Soft-Soft preferences may be explained and quantified in terms of electrostatic and covalent and electronic stabilization on the stability of Lewis acid-base adducts
07: The Crystalline Solid State
7.01: Molecular Orbitals and Band Structure
7.1.01: Prelude to Electronic Properties of Materials - Superconductors and Semiconductors
7.1.02: Metal-Insulator Transitions
7.1.03: Periodic Trends- Metals Semiconductors and Insulators
7.1.04: Semiconductors- Band Gaps Colors Conductivity and Doping
7.1.05: Semiconductor p-n Junctions
7.1.06: Diodes LEDs and Solar Cells
7.1.07: Amorphous Semiconductors
7.1.08: Discussion Questions
7.1.09: Problems
7.1.10: References
7.02: Formulas and Structures of Solids
7.2.01: The Solid State of Matter
7.2.02: Lattice Structures in Crystalline Solids
7.03: Superconductivity
7.3.01: Superconductors
7.04: Bonding in Ionic Crystals
7.05: Imperfections in Solids
7.5.01: Imperfections
7.06: Silicates
7.6.01: Silicon
7.07: Thermodynamics of Ionic Crystal Formation
7.7.01: Lattice Energy
7.7.02: Lattice Energy - The Born-Haber cycle
7.7.03: Lattice Enthalpies and Born Haber Cycles
7.7.04: The Born-Lande' equation
7.P: Problems
08: Chemistry of the Main Group Elements
8.01: General Trends in Main Group Chemistry
8.1.01: The Periodic Table is an Organizing Concept in Main Group Chemistry
8.1.1.01: The metal-nonmetal-metalloid distinction and the metal-nonmetal line are useful for thinking about trends in elements' physical properties
8.1.1.02: There are qualitative differences in the chemistry of the elements in the first two rows and those in the rest of the periodic table
8.1.02: Electronegativity increases and radius decreases towards the upper left of the periodic table with electron withdrawing substituents and with oxidation state
8.1.03: Ionization energy roughly increases towards the upper left of the periodic table but is also influenced by orbital energy and pairing energy effects
8.1.04: As may be seen from considering element's redox diagrams main group elements (aside from the noble gases) generally are more oxidizing towards the upper left of the periodic table and more reducing towards the lower right of the periodic table
8.1.4.01: Latimer Diagrams summarize elements' redox properties on a single line
8.1.4.02: Frost Diagrams show how stable element's redox states are relative to the free element
8.1.4.03: Pourbaix Diagrams are Redox Phase Diagrams that Summarize the most stable form of an element at a given pH and solution potential
8.02: What are the main group elements and why should anyone care about them
8.03: Group 1 The Alkali Metals
8.3.01: Alkali Metals' Chemical Properties
8.04: Hydrogen
8.4.01: Hydrogen's Chemical Properties
8.05: Group 2 The Alkaline Earth Metals
8.5.01: Preparation and General Properties of the Alkaline Earth Elements
8.5.02: Alkaline Earth Metals' Chemical Properties
8.06: Group 13 (and a note on the post-transition metals)
8.6.01: Properties of the Group 13 Elements and Boron Chemistry
8.6.02: Heavier Elements of Group 13 and the Inert Pair Effect
8.07: Group 14
8.7.01: The Group 14 Elements and the many Allotropes of Carbon
8.7.02: Inorganic Compounds of the Group 14 Elements
8.7.03: Chemistry of Carbon (Z6)
8.7.04: Chemistry of Silicon (Z14)
8.7.4.01: Silicates
8.7.4.02: Silicon and Group 14 Elements
8.7.05: Chemistry of Germanium (Z32)
8.7.06: Chemistry of Tin (Z50)
8.7.07: Chemistry of Lead (Z82)
8.7.7.01: Lead Acetate
8.7.7.02: Lead Plumbate
8.08: Group 15
8.8.01: The Group 15 Elements
8.8.02: Compounds of the Group 15 Elements
8.09: The Nitrogen Family
8.9.01: General Properties and Reactions
8.9.1.01: Nitrogen Group (Group 5) Trends
8.9.02: Chemistry of Nitrogen (Z7)
8.9.03: Chemistry of Phosphorus (Z15)
8.9.04: Chemistry of Arsenic (Z33)
8.9.05: Chemistry of Antimony (Z51)
8.9.06: Chemistry of Bismuth (Z83)
8.9.07: Chemistry of Moscovium (Z115)
8.10: Group 16
8.10.01: The Group 16 Elements
8.10.1.01: Compounds of the Group 16 Elements
8.10.1.02: The Group 16 Elements
8.11: The Oxygen Family (The Chalcogens)
8.11.01: General Properties and Reactions
8.11.1.01: Oxygen Group (Group VIA) Trends
8.11.02: Chemistry of Oxygen (Z8)
8.11.2.01: Ozone
8.11.2.1.01: Important properties of ozone
8.11.2.1.02: Ozone Layer and Ozone Hole
8.11.03: Chemistry of Sulfur (Z16)
8.11.04: Chemistry of Selenium (Z34)
8.11.05: Chemistry of Tellurium (Z52)
8.11.06: Chemistry of Polonium (Z84)
8.11.07: Chemistry of Livermorium (Z116)
8.12: Group 17 (The Halogens)
8.12.01: Compounds of the Group 17 Elements (Halogens)
8.12.02: The Group 17 Elements (Halogens)
8.13: The Halogens
8.13.01: Physical Properties of the Halogens
8.13.1.01: Atomic and Physical Properties of Halogens
8.13.1.02: General Properties of Halogens
8.13.1.03: Halogen Group (Group 17) Trends
8.13.1.04: Physical Properties of the Group 17 Elements
8.13.02: Chemical Properties of the Halogens
8.13.2.01: Halide Ions as Reducing Agents
8.13.2.02: Halogens as Oxidizing Agents
8.13.2.03: Interhalogens
8.13.2.04: More Reactions of Halogens
8.13.2.05: Oxidizing Ability of the Group 17 Elements
8.13.2.06: Testing for Halide Ions
8.13.2.07: The Acidity of the Hydrogen Halides
8.13.03: Chemistry of Fluorine (Z9)
8.13.04: Chemistry of Chlorine (Z17)
8.13.4.01: The Manufacture of Chlorine
8.13.05: Chemistry of Bromine (Z35)
8.13.06: Chemistry of Iodine (Z53)
8.13.07: Chemistry of Astatine (Z85)
8.14: The Noble Gases
8.14.01: History usage properties and distribution of the elements
8.14.02: Properties of Nobel Gases
8.14.2.01: Noble Gas (Group 18) Trends
8.14.03: Chemistry of the Group 18 (Noble Gas) Elements
8.14.04: Reactions of Nobel Gases
8.14.05: Chemistry of Helium (Z2)
8.14.06: Chemistry of Neon (Z10)
8.14.07: Chemistry of Argon (Z18)
8.14.08: Chemistry of Krypton (Z36)
8.14.09: Chemistry of Radon (Z86)
8.14.10: Chemistry of Xenon (Z54)
8.P: Problems
09: Coordination Chemistry I - Structure and Isomers
9.01: Prelude to Coordination Chemistry I - Structure and Isomers
9.02: History
9.03: Nomenclature and Ligands
9.04: Isomerism
9.05: Coordination Numbers and Structures
9.06: Coordination Frameworks
9.P: Problems
10: Coordination Chemistry II - Bonding
10.01: Evidence for Electronic Structures
10.1.01: Thermodynamic Data
10.1.02: Magnetic Susceptibility
10.1.03: Electronic Spectra
10.1.04: Coordination Number and Molecular Shapes
10.02: Bonding Theories
10.2.01: Crystal Field Theory
10.03: Ligand Field Theory
10.3.01: Ligand Field Theory - Molecular Orbitals for an Octahedral Complex
10.3.02: Orbital Splitting and Electron Spin
10.3.03: Ligand Field Stabilization Energy
10.3.04: Tetrahedral Complexes
10.3.05: Square-Planar Complexes
10.04: Angular Overlap
10.4.01: Sigma Bonding in the Angular Overlap Model
10.4.02: Pi Acceptors in the Angular Overlap Model
10.4.03: Pi Donors in the Angular Overlap Model
10.4.04: The Spectrochemical Series
10.4.05: The Magnitude of Parameters e e and
10.4.06: The Magnetochemical Series
10.05: The Jahn-Teller Effect
10.06: Four- and Six-Coordinate Preferences
10.07: Other Shapes
10.P: Problems
11: Coordination Chemistry III - Electronic Spectra
11.01: Absorption of Light
11.1.01: Beer-Lambert Absorption Law
11.02: Quantum Numbers of Multielectron Atoms
11.2.01: Finding Microstates and Term Symbols
11.2.02: Spin-Orbit Coupling
11.03: Electronic Spectra of Coordination Compounds
11.3.01: Selection Rules
11.3.02: Correlation Diagrams
11.3.03: Tanabe-Sugano Diagrams
11.3.04: Symmetry labels for split terms
11.3.05: Applications of Tanabe-Sugano Diagrams
11.3.06: Tetrahedral Complexes
11.3.07: Charge-Transfer Spectra
11.3.08: Applications of Charge-Transfer
12: Coordination Chemistry IV - Reactions and Mechanisms
12.01: Introduction to Reactions of Metal Complexes
12.02: Substitutions Reactions
12.2.01: Introduction to Substitution Reactions
12.2.02: Inert and Labile Complexes
12.2.03: Mechanistic Possibilities
12.03: Kinetics Hint at the Reaction Mechanism
12.3.01: Rate Law for Dissociative Mechanisms
12.3.02: Rate Laws for Interchange Mechanisms
12.3.03: Rate Law for Associative Mechanisms
12.3.04: Preassociation Complexes
12.3.05: Activation Parameters
12.3.06: Some Reasons for Differing Mechanisms
12.04: Experimental Evidence in Octahedral Substitutions
12.4.01: Dissociation
12.4.02: Linear Free Energy Relationships
12.4.03: Associative Mechanisms
12.4.04: The conjugate base mechanism
12.4.05: The Kinetic Chelate Effect
12.05: Stereochemistry of Octahedral Reactions
12.5.01: Substitution in trans-en octahedral complexes
12.5.02: Substitution in cis-en octahedral complexes
12.5.03: Isomerization of Chelate Rings
12.06: Substitutions in Square Planar Complexes
12.6.01: Kinetics and Stereochemistry of Square Planar Reactions
12.6.02: Evidence for Associative Reactions
12.07: The Trans Effect
12.08: Redox Mechanisms
12.8.01: Outer Sphere Electron Transfer
12.8.02: Inner Sphere Electron Transfer
12.09: Reactions of Coordinated Ligands
12.9.01: Metal-catalyzed Hydrolysis
12.9.02: Template Reactions
12.9.03: Electrophilic Substitutions
13: Organometallic Chemistry
13.01: Introduction to Organometallic Chemistry
13.02: Nomenclature Ligands and Classification
13.03: Electron Counting in Organometallic Complexes
13.3.01: The 18 Electron Rule
13.3.02: Simplifying the Organometallic Complex by Deconstruction
13.04: Survey of Organometallic Ligands
13.4.01: Carbon Monoxide (Carbonyl Complexes)
13.4.02: Ligands similar to CO
13.4.03: Hydrides and Dihydrogen Complexes
13.05: Bonding between Metal Atoms and Organic Pi Systems
13.5.01: Linear Systems
13.5.02: Cyclic systems
13.5.03: Odd-numbered Systems
13.5.04: Fullerene Complexes
13.06: Metal-Carbon Bonds
13.6.01: Metal Alkyls
13.6.02: Carbenes
13.6.03: Carbyne (Alkylidyne) Complexes
13.6.04: Carbido and Cumulene Complexes
13.6.05: Carbon Wires- Polyyne and Polyene Bridges
13.07: Characterization of Organometallic Complexes
14: Organometallic Reactions and Catalysis
14.01: Reactions Involving Gain or Loss of Ligands
14.1.01: Ligand Dissociation and Substitution
14.1.02: Oxidative Addition
14.1.03: Reductive Elimination
14.1.04: Sigma Bond Metathasis
14.1.05: Application of Pincer Ligands
14.02: Reactions Invloving Modification of Unsaturated Ligands
14.2.01: Introduction to Insertion
14.2.02: CO Insertions (Alkyl Migration)
14.2.03: Migratory Insertion-12-Insertions
14.2.04: -Elimination Reactions
14.2.05: Abstraction and Addition
14.03: Organometallic Catalysts
14.3.01: Catalytic Deuteration
14.3.02: Hydroformylation
14.3.03: Monsanto Acetic Acid Process
14.3.04: Wacker (Smidt) Process
14.3.05: Hydrogenation by Wilkinson's Catalyst
14.3.06: Olefin Metathesis
14.04: Heterogeneous Catalysts
14.4.01: Ziegler-Natta Polymerizations
14.4.02: Water-Gas Shift Reaction
14.05: Problems
14.5.01: Concept Review Questions Chapter 12
14.5.02: Homework Problems Chapter 12
15: Parallels between Main Group and Organometallic Chemistry
15.01: Parallels between Main Group and Binary Carbonyl Complexes
15.02: The Isolobal Analogy
15.2.01: Extensions of the Analogy
15.2.02: Some Applications of the Isolobal Analogy
15.03: Metal-Metal Bonds
15.3.01: Metal-Metal Multiple Bonds
15.04: Cluster Compounds
15.4.01: Boranes
15.4.02: Heteroboranes
15.4.03: Metallaboranes and Metallacarboranes
15.4.04: Carbonyl Clusters
15.4.05: Carbon-Centered Clusters
15.4.06: Additional Comments on Clusters
15.05: Problems
16: Appendix
16.01: Periodic Table
16.02: Character Tables
16.03: Tanabe-Sugano Diagrams