2nd Edition

# Physical Chemistry A Modern Introduction, Second Edition

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Designed for a two-semester introductory course sequence in physical chemistry, **Physical Chemistry: A Modern Introduction, Second Edition** offers a streamlined introduction to the subject. Focusing on core concepts, the text stresses fundamental issues and includes basic examples rather than the myriad of applications often presented in other, more encyclopedic books. Physical chemistry need not appear as a large assortment of different, disconnected, and sometimes intimidating topics. Instead, students should see that physical chemistry provides a coherent framework for chemical knowledge, from the molecular to the macroscopic level.

The book offers:

*Novel organization to foster student understanding,*giving students the strongest sophistication in the least amount of time and preparing them to tackle more challenging topics*Strong problem-solving emphasis,*with numerous end-of-chapter practice exercises, over two dozen in-text worked examples, and a number of clearly identified spreadsheet exercises*A quick review in calculus,*via an appendix providing the necessary mathematical background for the study of physical chemistry*Powerful streamlined development of group theory and advanced topics in quantum mechanics*, via appendices covering molecular symmetry and special quantum mechanical approaches

Preface

Acknowledgments

Author

Guide for Students

List of Special Examples

World of Atoms and Molecules

Introduction to Physical Chemistry

Theory and Experiment in Physical Chemistry

Atomic and Molecular Energies

Configurations, Entropy, and Volume

Energy, Entropy, and Temperature

Distribution Law Derivation

Conclusions

Point of Interest: James Clerk Maxwell

Exercises

Bibliography

Ideal and Real Gases

The Ideal Gas Laws

Collisions and Pressure

Nonideal Behavior

Thermodynamic State Functions

Energy and Thermodynamic Relations

Conclusions

Point of Interest: Intermolecular Interactions

Exercises

Bibliography

Changes of State

Pressure–Volume Work

Reversibility, Heat, and Work

Entropy

The Laws of Thermodynamics

Heat Capacities

Joule–Thomson Expansion

Conclusions

Point of Interest: Heat Capacities of Solids

Exercises

Bibliography

Phases and Multicomponent Systems

Phases and Phase Diagrams

The Chemical Potential

Clapeyron Equation

First- and Second-Order Phase Transitions

Conclusions

Point of Interest: Josiah Willard Gibbs

Exercises

Bibliography

Activity and Equilibrium of Gases and Solutions

Activities and Fugacities of Gases

Activities of Solutions

Vapor Pressure Behavior of Solutions

Equilibrium Constants

Phase Equilibria Involving Solutions

Conclusions.

Point of Interest: Gilbert Newton Lewis

Exercises.

Bibliography

Chemical Reactions: Kinetics, Dynamics, and Equilibrium

Reaction of Atoms and Molecules

Collisions and Transport

Rate Equations

Rate Laws for Complex Reactions

Temperature Dependence and Solvent Effects

Reaction Thermodynamics

Electrochemical Reactions

Conclusions

Point of Interest: Galactic Reaction Chemistry

Exercises

Bibliography

Vibrational Mechanics of Particle Systems

Classical Particle Mechanics and Vibration

Vibration in Several Degrees of Freedom

Quantum Phenomena and Wave Character

Quantum Mechanical Harmonic Oscillator

Harmonic Vibration of Many Particles

Conclusions

Point of Interest

Exercises

Bibliography

Molecular Quantum Mechanics

Quantum Mechanical Operators

Information from Wavefunctions

Multidimensional Problems and Separability

Particles with Box and Step Potentials

Rigid Rotator and Angular Momentum

Coupling of Angular Momenta

Variation Theory

Perturbation Theory

Conclusions

Point of Interest: The Quantum Revolution

The Solvay Conference

Exercises

Bibliography

Vibrational–Rotational Spectroscopy

Molecular Spectroscopy and Transitions

Vibration and Rotation of a Diatomic Molecule

Vibrational Anharmonicity and Spectra

Rotational Spectroscopy

Harmonic Picture of Polyatomic Vibrations

Polyatomic Vibrational Spectroscopy

Conclusions

Point of Interest: Laser Spectroscopy

Exercises

Bibliography**Electronic Structure**.

Hydrogen and One-Electron Atoms

Orbital and Spin Angular Momentum

Atomic Orbitals and Atomic States

Molecules and the Born–Oppenheimer Approximation

Antisymmetrization of Electronic Wavefunctions

Molecular Electronic Structure

Visible–Ultraviolet Spectra of Molecules

Properties and Electronic Structure

Conclusions

Point of Interest: John Clarke Slater

Exercises

Bibliography

Advanced Texts and Monographs

Statistical Mechanics

Statistical Mechanics

Probability

Ensembles and Arrangements

Distributions and the Chemical Potential

Molecular Partition Functions

Thermodynamic Functions

Heat Capacities

Conclusions

Point of Interest: Lars Onsager

Exercises

Bibliography

Magnetic Resonance Spectroscopy

Magnetic Resonance Spectroscopy

Nuclear Spin States

Nuclear Spin–Spin Coupling

Electron Spin Resonance Spectra

Extensions of Magnetic Resonance

Conclusions

Point of Interest: The NMR Revolution

Exercises

Bibliography

Introduction to Surface Chemistry

Introduction to Surface Chemistry

Interfacial Layer and Surface Tension

Adsorption and Desorption

Langmuir Theory of Adsorption

Temperature and Pressure Effects on Surfaces

Surface Characterization Techniques

Conclusions

Point of Interest: Irving Langmuir

Exercises

Bibliography

Appendix A: Mathematical Background

Appendix A: Mathematical Background

**Appendix B: Molecular Symmetry**

**Appendix C: Special Quantum Mechanical Approaches**

**Appendix D: Table of Integrals**.

**Appendix E: Table of Atomic Masses and Nuclear Spins**

**Appendix F: Fundamental Constants and Conversion of Units**

**Appendix G: Tables**.

**Appendix H: Points of Interest**.

**Appendix I: Atomic Masses and Percent Natural Abundance of Light Elements**.

**Appendix J: Values of Constants**

**Appendix K: The Greek Alphabet**

**Answers to Selected Exercises**

**Index**

### Biography

**William M. Davis** received his BSc (honors) in chemistry from the University of Western Ontario, London, Canada, and his MSc and PhD from the University of Guelph, Ontario, Canada. He taught lecture and laboratory sections of general, physical, and inorganic chemistry at several Canadian universities before moving to Texas to take up a tenure-track position at The University of Texas at Brownsville, where he taught general, physical, inorganic, analytical, organic, and environmental chemistry for 10 years. In 2008, he moved to Texas Lutheran University, where he is currently an Associate Professor and Chair of Chemistry and holds the George Kieffer Fellowship in Science. Dr. Davis’s research interests include application of computational and analytical chemistry techniques to systems of environmental and biochemical interest.