Principles of Inorganic Chemistry

Frontmatter

Chapter 1. Atoms and Electrons

Abstract

This chapter begins with the components of the atom, followed by a description of the Bohr atom and the electron as a wave. The Shrödinger equation is introduced and solved for a one-electron system. Quantum numbers and orbital representations are discussed. The process of putting electrons into orbitals is described.

Robert B. Jordan

Chapter 2. The Periodic Table

Abstract

The development and structure of the periodic table are described, along with its relationship to properties such as ionization energy, electron affinity, electronegativity, and various types of atomic radii. The types of bonding are discussed, and the bond valence method is introduced.

Robert B. Jordan

Chapter 3. Covalent Bonding Theories

Abstract

Aspects of covalent and ionic bonding are discussed. Common terms, such as valence, oxidation state, and formal charge, are defined; the rules for determination of oxidation states are given. The electron dot theory of Lewis and its applications and problems are described. The shapes of species predicted by valence shell electron pair repulsion theory and the ligand close packing model are discussed. Valence bond theory is introduced in its classical or Pauling version and its modern, more quantitative approach. The development of molecular orbital theory and its application to diatomic, triatomic, and hypervalent species are described. The bonding in methane is developed in terms of both theories. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 4. Energy

Abstract

The basic relationships among internal energy, enthalpy, free energy, entropy, and equilibrium constant are given. Bond dissociation enthalpies, their values, and their applications are introduced. Process chemical cycles and isothermal chemical cycles are described. The Born–Haber cycle is used to determine lattice energies, and the relationship of the latter to ionic radius and molecular volume is discussed. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 5. Acids and Bases

Abstract

This chapter discusses the properties of Brønsted (protic acids and bases) and Lewis acids and bases (electron pair acceptors and donors). For the Brønsted class, topics such as strength, amphoteric species, autoprotolysis, pH, superacids, and superbases, are described. For the Lewis class, the topics include acid and base strength, the hard and soft model, and frustrated Lewis pairs. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 6. Reaction Types and Mechanisms

Abstract

The reaction types discussed in this chapter are proton transfer, substitution, oxidation–reduction, oxidative-addition, and isomerization. The development of a theoretical rate law and the effects of temperature and pressure on the rate constant are outlined. For proton transfer reactions, typical rate constants and the Grotthuss mechanism are described. For substitution reactions, the nucleophilic and electrophilic classification is discussed, along with the D, I_d, I_a, and I classification system. For oxidation–reduction reactions, topics such as electron versus atom transfer, inner sphere and outer sphere electron transfer, and Marcus theory are covered. Possible oxidative-addition mechanisms are described, with examples involving the metals in Groups 8, 9, and 10. Dissociative and intramolecular mechanisms are described for linkage isomerization, geometrical isomerization, and racemization. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 7. The Solid State and Symmetry

Abstract

The elements of group theory are outlined, along with applications to vibrational spectroscopy, orbital interactions, and orbital hybridization. The structural properties and common structure types for crystalline solids are given. The radius-ratio method and its problems are discussed. Polymorphs and polytypes are defined. The properties, structures, and bonding of metals and semiconductors are discussed. The structures and special properties of spinels and perovskites are described. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 8. Introduction to Transition Metals

Abstract

For these metals, the number of valence electrons, the various oxidation states, and their colors in water are described. The typical ligands (Lewis bases) and their arrangement when coordinated to the metal (Lewis acid) are given. These species have a wide range of structures and isomers that are described in this chapter. The bonding is discussed in terms of crystal field, valence bond, and ligand field theories. The latter is used here as a basis for analyzing the colors and magnetic properties of these species. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 9. The Transition Metals: Groups 3–12

Abstract

Many properties of these elements are tabulated in this chapter, followed by descriptions of each group. These descriptions include the properties of each metal, the natural sources and preparation of the metal, the common oxidation states, the aqueous chemistry, important compounds, and applications. The coverage of this area includes references published through to mid-2021.

Robert B. Jordan

Chapter 10. Organometallic Chemistry of Transition Metals

Abstract

These compounds have at least one metal–carbon bond, but species with metal–phosphane bonds often are included in this family. The historical background is followed by descriptions of the bonding in terms of qualitative valence bond theory, molecular orbital theory, and the eighteen-electron rule. These approaches can rationalize the stability and arrangement of the ligands around the metal. The metal carbonyls and metal cyclopentadienes are important members of this family, and their bonding is described in detail. The syntheses and reactions of some representative organometallic species are described. The final section involves the use of organometallic species as catalysts for the homogeneous hydrogenation of organic substrates. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 11. The Lanthanides

Abstract

The lanthanide series, officially known as the lanthanoid series, consists of the elements from lanthanum to lutetium. The atomic electronic configurations involve the filling of the 4f, 5d, and 6s orbitals. The properties of the metals are tabulated, their preparations, and the common oxidation states of their ions are discussed. The extraction of the lanthanides from their mineral sources and their separation by solvent extraction are described. The preparations and properties of the oxide and halide salts are described, along with the chemical and structural effects of the lanthanide contraction. The many recent advances in the organometallic compounds of the lanthanides are discussed. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 12. Groups 1 and 2

Abstract

This chapter covers the nonradioactive elements of Group 1 (H to Cs), known as the alkali metals, and Group 2 (Be to Ba), known as the alkaline earth metals. Many properties of these elements are presented in tables. There is extensive coverage of the natural sources and preparations of these elements, their structures, properties, and uses. The binary compounds with oxygen, carbon, and nitrogen are described in detail. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 13. Group 13

Abstract

This chapter covers the elements of Group 13 (B to Tl). There is extensive coverage of the natural sources and preparations of these elements, their structures, properties, uses, and biological effects. Their compounds with oxygen, nitrogen, hydrogen, and halides are described in detail. The coverage also includes the metal borides, boric acid and its many derivatives, carboranes, and the aqueous species of their ions. The preparations, structures, and reactions of their organic derivatives also are described. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 14. Group 14

Abstract

This chapter covers the elements of Group 14 (C to Pb). Many properties of these elements are tabulated. There is extensive coverage of the natural sources and preparations of these elements, their structures, properties, uses, and biological effects. The allotropes of carbon, graphite, fullerenes, nanotubes, and graphene get special mention. Their compounds with oxygen, halides, amines, and nitrides are described in detail, as are their oxoanions and aqueous cations. The preparations, structures, and reactions of their organic derivatives are covered. The formation of single, double, and triple bonds, catenation, for Si, Ge, and Pb, are discussed and compared to the C analogues. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 15. Group 15

Abstract

This chapter covers the elements of Group 15 (N to Bi). Many properties of these elements are tabulated. There is extensive coverage of the natural sources and preparations of these elements, their structures, properties, uses, and biological effects. Their compounds with oxygen, hydrogen, halides, and the nitrides with other elements are described in detail, as are their oxoanions and aqueous cations. The structures of their organic derivatives are discussed, and the synthesis and properties of amines and phosphanes are given in detail because these compounds are common ligands in coordination and organometallic chemistry, respectively. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 16. Group 16

Abstract

This chapter covers the nonradioactive elements of Group 16 (O to Te), commonly called the chalcogens. Many properties of these elements are tabulated. There is extensive coverage of the natural sources and preparations of these elements, their structures, properties, uses, and biological significance. The properties of dioxygen and ozone are discussed, as are the peroxides, superoxides, and ozonide ions, the oxides, oxoacids, and oxoanions of S, Se, and Te. Further coverage includes the halides, hydrides, oxohalides, nitrides of sulfur, and organic derivatives. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 17. Group 17

Abstract

This chapter covers the nonradioactive elements of Group 17 (F to I), commonly called the halogens. Many properties of these elements are tabulated. There is extensive coverage of the natural sources and preparations of these elements, their structures, properties, uses, and biological effects. The structures, syntheses, reactions, and structures of the large family of their oxides, oxoacids, and oxoanions are described. Species with halogen–halogen bonds, either with the same halogen (polyhalogens) or with the different halogens (polyinterhalogens) are discussed with regard to their synthesis, structure, and bonding. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 18. Group 18

Abstract

This chapter covers the nonradioactive elements of Group 18 (He to Xe), now called the noble gases. Many properties of these elements are tabulated. The coverage includes the natural sources and preparations of these elements, their structures, properties, and uses. The properties of the fluorides of Xe and Kr, the oxides and oxoanions of Xe, and the oxofluorides of Xe are described. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 19. Bioinorganic Chemistry

Abstract

Bioinorganic chemistry is a huge area, and the coverage in this chapter is limited to selected examples of biologically active species in mammals. The essential and possibly essential elements are tabulated, along with their amounts. The biological functions of the main group elements are discussed, and the function of iodide and selenium in selenocysteine to produce thyroxine is described in detail. The biological functions of transition metals are discussed. Detailed examples are given for the function of Zn in carbonic anhydrase and peptidases, of cobalt in coenzyme B₁₂, and of iron in hemoglobin and cytochrome P450s. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Chapter 20. Nanomaterials

Abstract

Many elements and compounds have been prepared as nanosized particles in various shapes and sizes on the 1 to ~100 nm scale. This chapter describes the general methods for their preparation and for the study of their growth, size, and color. Systems that are described in detail include nanoparticles of gold, silver, copper, iron, platinum, palladium, and silicon. Details also are given for metal–oxide and binary semiconductor nanoparticles. Finally, the biological effects and applications of nanomaterials are described. The coverage of these topics includes references published through to mid-2021.

Robert B. Jordan

Backmatter