Principles of Inorganic Chemistry

Citation

Pfennig, B. W. (2021). Principles of Inorganic Chemistry (2nd ed.). Wiley.

Chapter Summary

The second edition has thirteen chapters in about 830 pages, followed by eleven appendixes and an index. Each chapter ends with exercises and a bibliography, and chapters contain "In-Depth" subsections that carry derivations for readers who want the mathematics. The sequence runs from atoms (structure of matter, the atom, periodicity) to bonding (an introduction, geometry, symmetry and spectroscopy, then valence bond and molecular orbital theory), to solids, to reactivity (acid–base and redox), and finally to coordination and organometallic chemistry. The publisher says the redesigned book reorganises the first edition to aid learning and retention.

Chapters 1–3: The Structure of Matter; The Structure of the Atom; The Periodicity of the Elements

Chapter 1 covers atomism, the anatomy of the atom, the periodic table, the nucleus, nuclear reactions, radioactive decay and the origin of the elements. Chapter 2 builds the quantum picture of the atom from the wave-like properties of light and matter through the particle in a box, the Schrödinger equation, the hydrogen atom, spin and the topological atom. Chapter 3 applies this to polyelectronic atoms: electron configurations, shielding, ionization energy, electron affinity, radii, polarizability, hardness, electronegativity, and effects such as the inert-pair effect and relativistic effects.

Chapters 4–5: An Introduction to Chemical Bonding; Molecular Geometry

Chapter 4 defines the chemical bond and covers its thermodynamic driving force, Lewis structures, bond lengths and energies, resonance, electronegativity, the triangle of bonding and the atoms-in-molecules model. Chapter 5 treats molecular geometry: X-ray crystallography, Linnett's double quartet theory, VSEPR theory, the ligand close-packing model and a comparison of VSEPR and LCP.

Chapter 6: Symmetry and Spectroscopy

A long chapter on symmetry elements and operations, point groups, representations and character tables, direct products, the great orthogonality theorem, the selection rules of IR and Raman spectroscopy, the symmetries of normal modes, and the generation of symmetry coordinates by the projection operator method.

Chapter 7: Structure and Bonding in Molecules

Valence bond theory (including hybridization), molecular orbital theory, and the complementarity of the two. It follows the symmetry chapter, so molecular orbitals can be discussed in symmetry terms.

Chapter 8: Structure and Bonding in Solids

Crystal structures, metallic bonding, ionic bonding and the types of crystalline solids.

Chapter 9: Chemical Structure and Reactivity

Acid–base chemistry, redox chemistry and a generalised view of chemical reactivity.

Chapters 10–11: Coordination Chemistry; Reactions of Coordination Compounds

Chapter 10 gives an overview of coordination chemistry, the models of bonding in coordination compounds and their electronic spectroscopy. Chapter 11 introduces kinetics and reaction coordinate diagrams, then octahedral and square-planar substitution and electron-transfer reactions.

Chapters 12–13: Organometallic Chemistry; Reactions of Organometallic Compounds

Chapter 12 introduces organometallic chemistry through electron counting and the 18-electron rule, then carbonyl, nitrosyl, hydride and dihydrogen, phosphine, ethylene and related, cyclopentadienyl and carbene, carbyne and carbido ligands. Chapter 13 covers reactions at the metal and at the ligand, metathesis, organometallic catalytic cycles and the isolobal analogy.

Appendixes

Derivations of the classical wave equation and the Schrödinger equation, the postulates of quantum mechanics, atomic and molecular term symbols, character and direct product tables, the diagonalization method for reducing representations, correlation tables, the harmonic oscillator model and the 230 space groups.

Key Concepts

Chapters 1–5

• Atomic and periodic structure: electron configurations and the properties that follow from them.
• Models of the chemical bond: Lewis structures, VSEPR, the ligand close-packing model and atoms in molecules.

Chapters 6–9

• Point groups and character tables: the tools for classifying molecular symmetry.
• Valence bond and molecular orbital theory: two complementary descriptions of bonding in molecules.
• Solid-state bonding: metallic and ionic bonding in crystals.
• Acid–base and redox chemistry: the main frameworks for reactivity.

Chapters 10–13

• Coordination bonding models and electronic spectra: how metal–ligand bonding is described and probed.
• Substitution and electron-transfer mechanisms: how coordination compounds react.
• The 18-electron rule and the isolobal analogy: organising ideas for organometallic compounds.

Critical Analysis

Strengths

• Principles-first design. The publisher describes a principles-based approach with theoretical depth, and the contents bear this out: atomic structure and periodicity are developed before bonding, and bonding before solids, reactivity and coordination chemistry.
• Symmetry and group theory in depth. Chapter 6 is a full treatment of point groups, character tables, the great orthogonality theorem and symmetry coordinates, which later chapters use for molecular orbitals and spectra.
• Comparison of models. The publisher notes the new emphasis on comparing the strengths and weaknesses of chemical models and on the links between valence bond and molecular orbital theory; the contents include a chapter section titled "The Complementarity of VBT and MOT" and a treatment of atoms in molecules.
• Support for different readers. Worked examples, exercises of varied difficulty, and "In-Depth" derivations give a path for readers who want the mathematics.

Limitations

• Descriptive chemistry is limited. The contents contain no group-by-group survey of the elements; readers who want that will pair the book with a descriptive text.
• Length and mathematical level. At about 830 pages with eleven appendixes, and with derivations in the In-Depth sections, the book is demanding; Chapters 6–7 need patience with group theory.
• Organometallic chemistry is introductory. Chapters 12–13 give a brief first look and are not a substitute for a specialised text.

Where It Fits in the Course

In the inorganic chemistry course this is the principles-and-theory text at the undergraduate level. Rayner-Canham and Overton's Descriptive Inorganic Chemistry surveys the chemistry of the elements group by group after laying down some principles, and is the natural companion for the descriptive side. Housecroft's Inorganic Chemistry and the Inorganic Chemistry of Shriver, Weller, Overton, Armstrong and Rourke are broader texts that combine physical-inorganic principles with systematic descriptive chemistry; the publisher singles out Pfennig's thorough treatment of group theory, term symbols, polyatomic molecular orbital theory, band theory and Tanabe–Sugano diagrams. Scerri's The Periodic Table: A Very Short Introduction is a short orientation. Crabtree's The Organometallic Chemistry of the Transition Metals is the graduate-level continuation of Chapters 12–13.

How to Use This Book

The publisher describes the book as suited to sophomore-level students, and as ideal for senior undergraduates and first-year graduate students through its in-depth boxed discussions; it also says the book will be useful for students of physical chemistry, materials science and chemical physics. General chemistry is the starting point; Chapter 2 develops the quantum mechanics it needs from the wave nature of light.

A practical plan:

• Core: Chapters 1–5 for atoms, periodicity and bonding, then Chapter 7 for molecular orbitals.
• Group theory: Chapter 6 before Chapter 7 if the course makes use of symmetry; the In-Depth sections can be skipped on a first pass.
• Reactivity and metals: Chapter 9, then Chapters 10–11 for coordination chemistry, and Chapters 12–13 for organometallics.
• Optional: Chapter 8 for solids and the appendixes (term symbols, space groups) for reference.
• Work the exercises at the end of each chapter alongside the worked examples.