Principles of Inorganic Chemistry

An informally written, engaging textbook, first of its kind, to offer a highly physical approach to inorganic chemistry

Unlike other chemistry textbooks, whose memorization–heavy volumes often dispirit student interest, this text is designed for upper–level undergraduates (who have already taken physical chemistry) and introductory–level graduate students taking an inorganic or advanced inorganic chemistry course. Written by veteran professor and scientist, Brian W. Pfennig, Principles of Inorganic Chemistry is composed of eclectic sources from Dr. Pfennig s many years of teaching and built on a principles–based, group and molecular orbital theory approach. Covering a variety of topics from the Composition of Matter, to Models of Chemical Bonding, to Reactions of Organometallic Compounds this textbook features:

Thorough treatment of group theory, a topic usually given cursory overview in other textbooks Rigorous mathematical derivations of the underlying chemical principles Comprehensive purview of chemical bonding that compares and contrasts the traditional classification of ionic, covalent, and metallic bonding in order to allow for a more integrative treatment of their application to molecular structure, bonding, and spectroscopy Coverage of atomic and molecular term symbols, symmetry coordinates in vibrational spectroscopy using the projection operator method, polyatomic MO theory, band theory, and Tanabe–Sugano diagrams Worked examples throughout the text, unanswered problems in every chapter, and generous use of informative, colorful illustrations
For instructors who are looking for a more physical inorganic chemistry course, this textbook offers pedagogical benefits of integration and reinforcement of group theory in the treatment of other topics. Together with its unique underlying framework, the book s approach allows students to be engaged and to derive the greatest learning experience possible from topics such as frontier MO acid–base theory, band theory of solids, inorganic photochemistry, the Jahn–Teller effect, and Wade′s rules for cluster compounds, to name but a few examples. 

PREFACE

ACKNOWLEDGEMENTS

1 THE COMPOSITION OF MATTER

1.1 Early descriptions of matter

1.2 Visualizing atoms

1.3 The periodic table

1.4 The standard model

References

Exercises

2 THE STRUCTURE OF THE NUCLEUS

2.1 The nucleus

2.2 Nuclear binding energies

2.3 Nuclear reactions: fusion and fission

2.4 Radioactivity and the band of stability

2.5 The shell model of the nucleus

2.6 The origin of the elements

References

Exercises

3 A BRIEF REVIEW OF QUANTUM THEORY

3.1 The wavelike properties of light

3.2 Problems with the classical model of the atom

3.3 The Bohr model of the atom

3.4 Implications of wave–particle duality

3.5 Postulates of quantum mechanics

3.6 The Schrödinger equation

3.7 The particle in a box problem

3.8 The harmonic oscillator problem

References

Exercises

4 ATOMIC STRUCTURE

4.1 The hydrogen atom

4.2 Polyelectronic atoms

4.3 Electron spin and the Pauli principle

4.4 Electron configurations and the periodic table

4.5 Atomic term symbols

4.6 Shielding and effective nuclear charge

References

Exercises

5 PERIODIC PROPERTIES OF THE ELEMENTS

5.1 The modern periodic table

5.2 Radius

5.3 Ionization energy

5.4 Electron affinity

5.5 The uniqueness principle

5.6 Diagonal properties

5.7 The metal–nonmetal line

5.8 Standard reduction potentials

5.9 The inert–pair effect

5.10 Relativistic effects

5.11 Electronegativity

References

Exercises

6 AN INTRODUCTION TO CHEMICAL BONDING

6.1 The bonding in molecular hydrogen

6.2 Lewis structures

6.3 Covalent bond energies and bond lengths

6.4 Resonance

6.5 Polar covalent bonding

References

Exercises

7 MOLECULAR GEOMETRIES

7.1 The VSEPR model

7.2 The ligand close–packing model

7.3 A comparison of the VSEPR and LCP models

References

Exercises

8 MOLECULAR SYMMETRY

8.1 Symmetry elements and symmetry operations

8.2 Symmetry groups

8.3 Molecular point groups

8.4 Representations

8.5 Character tables

8.6 Direct products

8.7 Reducible representations

References

Exercises

9 VIBRATIONAL SPECTROSCOPY

9.1 Overview of vibrational spectroscopy

9.2 Selection rules for IR and Raman–active modes

9.3 Determining the symmetries of the normal modes of vibration

9.4 Generating symmetry coordinates using the projection operator method

9.5 Resonance Raman spectroscopy

References

Exercises

10 COVALENT BONDING

10.1 Valence bond theory

10.2 Molecular orbital theory: diatomics

10.3 Molecular orbital theory: polyatomics

10.4 Molecular orbital theory: pi orbitals

10.5 Molecular orbital theory: more complex examples

10.6 Borane and carborane cluster compounds

References

Exercises

11 METALLIC BONDING

11.1 Crystalline lattices

11.2 X–ray diffraction

11.3 Closest–packed structures

11.4 The free electron model of metallic bonding

11.5 Band theory of solids

11.6 Conductivity in solids

11.7 Connections between solids and discrete molecules

References

Exercises

12 IONIC BONDING

12.1 Common types of ionic solids

12.2 Lattice enthalpies and the Born–Haber cycle

12.3 Ionic radii and Pauling s rules

12.4 The silicates

12.5 Zeolites

12.6 Defects in crystals

References

Exercises

13 STRUCTURE AND BONDING

13.1 A re–examination of crystalline solids

13.2 Intermediate types of bonding in solids

13.3 Quantum theory of atoms in molecules (QTAIM)

References

Exercises

14 STRUCTURE AND REACTIVITY

14.1 An overview of chemical reactivity

14.2 Acid–bases reactions

14.3 Frontier molecular orbital theory

14.4 Oxidation–reduction reactions

14.5 A generalized model of chemical reactivity

References

Exercises

15 AN INTRODUCTION TO COORDINATION COMPOUNDS

15.1 A historical overview of coordination chemistry

15.2 Types of ligands and nomenclature

15.3 Stability constants

15.4 Coordination numbers and geometries

15.5 Isomerism

15.6 Magnetic properties of coordination compounds

References

Exercises

16 STRUCTURE, BONDING, AND SPECTROSCOPY OF COORDINATION COMPOUNDS

16.1 Valence bond theory

16.2 Crystal field theory

16.3 Ligand field theory

16.4 Angular overlap model

16.5 Molecular term symbols

16.6 Tanabe–Sugano diagrams

16.7 Electronic spectroscopy of coordination compounds

16.8 The Jahn–Teller effect

References

Exercises

17  REACTIONS OF COORDINATION COMPOUNDS

17.1 Kinetics overview

17.2 Octahedral substitution reactions

17.3 Square planar substitution reactions

17.4 Electron transfer reactions

17.5 Inorganic photochemistry

References

Exercises

18  STRUCTURE AND BONDING IN ORGANOMETALLIC COMPOUNDS

18.1 Introduction to organometallic chemistry

18.2 Electron counting and the 18–electron rule

18.3 Carbonyl ligands

18.4 Nitrosyl ligands

18.5 Hydride and dihydrogen ligands

18.6 Phosphine ligands

18.7 Ethylene and related ligands

18.8 Cyclopentadiene and related ligands

18.9 Carbenes, carbynes, and carbidos

References

Exercises

19 REACTIONS OF ORGANOMETALLIC COMPOUNDS

19.1 Some general principles

19.2 Organometallic reactions involving changes at the metal

19.3 Organometallic reactions involving changes at the ligand

19.4 Metathesis reactions

19.5 Commercial catalytic processes

19.6 Organometallic photochemistry

19.7 The isolobal analogy and metal–metal bonding in organometallic clusters

References

Exercises

APPENDICES

Appendix A: Derivation of the classical wave equation

Appendix B: Character tables

Appendix C: Direct product tables

Appendix D: Correlation tables

Appendix E: The 230 space groups

Brian W. Pfennig, PhD, received his undergraduate B.S. degree in chemistry at Albright College in 1988. He earned his Ph.D. in 1992 in the field of physical inorganic chemistry at Princeton University with Dr. Andrew B. Bocarsly, studying the photochemistry of organometallic sandwich compounds and electron transfer in multinuclear mixed–valence coordination compounds. Dr. Pfennig has held a number of different teaching appointments at small liberal arts colleges, including Franklin & Marshall College, Haverford College, Vassar College, and Ursinus College. During his 20–year teaching career, he has taught general chemistry, an accelerated one–semester general chemistry course, both introductory and advanced inorganic chemistry, bio–inorganic chemistry, and inorganic and organometallic photochemistry, as well as serving as the general chemistry laboratory coordinator at Ursinus College for the past 10 years. He is also actively engaged in research with undergraduates in the areas of inorganic photochemistry, electrochemistry, and electron transfer processes occurring in multinuclear mixed–valence coordination compounds. He has also published several papers in the area of chemical education.