Problems
and Solutions
to accompany
McQuarrie and Simon
PHYSICAL CHEMISTRY: A MOLECULAR APPROACH
Heather Cox
b
University Science Books
Sausalito, California
University Science Books
55D Gate Five Road
Sausalito, CA 94965
Fax: (415) 332-5393
www.uscibooks.com
Production Manager: Susanna Tadlock
Designer: Robert Ishi
Illustrator: John Choi
Compositor: Eigentype
Printer & Binder: Edwards Brothers
This book is printed on acid-free paper.
Copyright ©1997 by University Science Books
ISBN 0-935702-43-1
Reproduction or translation of any part of this work beyond
that permitted by Section107 or 108 of the 1976 United States
Copyright Act without the permission of the copyright owner
is unlawful. Requests for permission or further information
should be addressed to the Permissions Department,
University Science Books.
Printed in the United States of America
1098765
4
Contents
Preface
vii
Acknowledgments _ viii
CHAPTER 1 / The Dawn of the Quantum Theory
MATHCHAPTER A / Complex Numbers
1
19
CHAPTER 2 / The Classical Wave Equation
27
MATHCHAPTER B / Probability and Statistics
47
CHAPTER 3 / The Schrédinger Equation and a Particle ina Box
MATHCHAPTER C / Vectors
51
77
CHAPTER 4 / Some Postulates and General Principles of Quantum Mechanics
MATHCHAPTER D / Spherical Coordinates
83
115
CHAPTER 5 / The Harmonic Oscillator and the Rigid Rotator: Two Spectroscopic Models
CHAPTER 6 / The Hydrogen Atom 155
MATHCHAPTER E / Determinants
197
CHAPTER 7 / Approximation Methods
CHAPTER 8 / Multielectron Atoms
203
243
CHAPTER 9 / The Chemical Bond: Diatomic Molecules
CHAPTER 10/ Bonding in Polyatomic Molecules
CHAPTER 11 / Computational Quantum Chemistry
MATHCHAPTER F / Matrices
277
301
339
359
CHAPTER 12 / Group Theory: The Exploitation of Symmetry
CHAPTER 13 / Molecular Spectroscopy
369
395
CHAPTER 14 / Nuclear Magnetic Resonance Spectroscopy
429
CHAPTER 15 / Lasers, Laser Spectroscopy, and Photochemistry
MATHCHAPTER G / Numerical Methods
473
CHAPTER 16/ The Properties of Gases
481
MATHCHAPTER H / Partial Differentiation
453
517
CHAPTER 17 / The Boltzmann Factor and Partition Functions
MATHCHAPTER I / Series and Limits 549
CHAPTER 18 / Partition Functions and Ideal Gases
557
527
121
vi
Contents
CHAPTER 19 / The First Law of Thermodynamics
585
MATHCHAPTER J / The Binomial Distribution and Stirling's Approximation
CHAPTER 20/ Entropy and the Second Law of Thermodynamics
CHAPTER 21 / Entropy and the Third Law of Thermodynamics
CHAPTER 22 / Helmholtz and Gibbs Energies
CHAPTER 23 / Phase Equilibria
679
721
CHAPTER 24 / Solutions |: Liquid-Liquid Solutions
755
CHAPTER 25 / Solutions II: Solid-Liquid Solutions
793
CHAPTER 26 / Chemical Equilibrium
823
CHAPTER 27 / The Kinetic Theory of Gases
CHAPTER 28 / Chemical Kinetics I: Rate Laws
869
893
CHAPTER 29 / Chemical Kinetics Il: Reaction Mechanisms
CHAPTER 30 / Gas-Phase Reaction Dynamics
963
CHAPTER 31 / Solids and Surface Chemistry
989
925
621
647
615