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Physical Chemistry: A Molecular Approach

Donald A. McQuarrie University of California, Davis
John D. Simon Duke University

As the first modern physical chemistry textbook to cover quantum mechanics before thermodynamics and kinetics, this book provides a contemporary approach to the study of physical chemistry. By beginning with quantum chemistry, students will learn the fundamental principles upon which all modern physical chemistry is built.

ISBN 978-0-935702-99-6
eISBN 978-1-891389-96-2
Copyright 1997
1360 pages, Casebound


As the first modern physical chemistry textbook to cover quantum mechanics before thermodynamics and kinetics, this book provides a contemporary approach to the study of physical chemistry. By beginning with quantum chemistry, students will learn the fundamental principles upon which all modern physical chemistry is built. The text includes a special set of “MathChapters” to review and summarize the mathematical tools required to master the material Thermodynamics is simultaneously taught from a bulk and microscopic viewpoint that enables the student to understand how bulk properties of materials are related to the properties of individual constituent molecules. This new text includes a variety of modern research topics in physical chemistry as well as hundreds of worked problems and examples.

Translated into French, Italian, Japanese, Spanish and Polish.

Link to Solutions Manual

Table of Contents

  • Chapter 1. The Dawn of the Quantum Theory
    1-1. Blackbody Radiation Could Not Be Explained by Classical Physics
    1-2. Planck Used a Quantum Hypothesis to Derive the Blackbody Radiation Law
    1-3. Einstein Explained the Photoelectric Effect with a Quantum Hypothesis
    1-4. The Hydrogen Atomic Spectrum Consists of Several Series of Lines
    1-5. The Rydberg Formula Accounts for All the Lines in the Hydrogen Atomic Spectrum
    1-6. Louis de Broglie Postulated That Matter Has Wavelike Properties
    1-7. de Broglie Waves Are Observed Experimentally
    1-8. The Bohr Theory of the Hydrogen Atom Can Be Used to Derive the Rydberg Formula
    1-9. The Heisenberg Uncertainty Principle States That the Position and the Momentum of a Particle Cannot be Specified Simultaneously with Unlimited Precision
    MathChapter A / Complex Numbers
  • Chapter 2. The Classical Wave Equation
    2-1. The One-Dimensional Wave Equation Describes the Motion of a Vibrating String
    2-2. The Wave Equation Can Be Solved by the Method of Separation of Variables
    2-3. Some Differential Equations Have Oscillatory Solutions
    2-4. The General Solution to the Wave Equation Is a Superposition of Normal Modes
    2-5. A Vibrating Membrane Is Described by a Two- Dimensional Wave Equation
    MathChapter B / Probability and Statistics
  • Chapter 3. The Schrodinger Equation and a Particle In a Box
    3-1. The Schrodinger Equation Is the Equation for Finding the Wave Function of a Particle
    3-2. Classical-Mechanical Quantities Are Represented by Linear Operators in Quantum Mechanics
    3-3. The Schrodinger Equation Can be Formulated as an Eigenvalue Problem
    3-4. Wave Functions Have a Probabilistic Interpretation
    3-5. The Energy of a Particle in a Box Is Quantized
    3-6. Wave Functions Must Be Normalized
    3-7. The Average Momentum of a Particle in a Box is Zero
    3-8. The Uncertainty Principle Says That sigmapsigmax>h/2
    3-9. The Problem of a Particle in a Three-Dimensional Box is a Simple Extension of the One-Dimensional Case
    MathChapter C / Vectors
  • Chapter 4. Some Postulates and General Principles of Quantum Mechanics
    4-1. The State of a System Is Completely Specified by its Wave Function
    4-2. Quantum-Mechanical Operators Represent Classical-Mechanical Variables
    4-3. Observable Quantities Must Be Eigenvalues of Quantum Mechanical Operators
    4-4. The Time Dependence of Wave Functions Is Governed by the Time-Dependent Schrodinger Equation
    4-5. The Eigenfunctions of Quantum Mechanical Operators Are Orthogonal
    4-6. The Physical Quantities Corresponding to Operators That Commute Can Be Measured Simultaneously to Any Precision
    MathChapter D / Spherical Coordinates
  • Chapter 5. The Harmonic Oscillator and the Rigid Rotator : Two Spectroscopic Models
    5-1. A Harmonic Oscillator Obeys Hooke’s Law
    5-2. The Equation for a Harmonic-Oscillator Model of a Diatomic Molecule Contains the Reduced Mass of the Molecule
    5-3. The Harmonic-Oscillator Approximation Results from the Expansion of an Internuclear Potential Around its Minimum
    5-4. The Energy Levels of a Quantum-Mechanical Harmonic Oscillator Are Ev hw(v + 1/2) with v= 0,1,2…
    5-5. The Harmonic Oscillator Accounts for the Infrared Spectrum of a Diatomic Molecule
    5-6. The Harmonic-Oscillator Wave Functions Involve Hermite Polynomials
    5-7. Hermite Polynomials Are Either Even or Odd Functions
    5-8. The Energy Levels of a Rigid Rotator Are E = h<fontsize=2></fontsize=2> 2J(J+1)/2I
    5-9. The Rigid Rotator Is a Model for a Rotating Diatomic Molecule
  • Chapter 6. The Hydrogen Atom
    6-1. The Schrodinger Equation for the Hydrogen Atom Can Be Solved Exactly
    6-2. The Wave Functions of a Rigid Rotator Are Called Spherical Harmonics
    6-3. The Precise Values of the Three Components of Angular Momentum Cannot Be Measured Simultaneously
    6-4. Hydrogen Atomic Orbitals Depend upon Three Quantum Numbers
    6-5. s Orbitals Are Spherically Symmetric
    6-6. There Are Three p Orbitals for Each Value of the Principle Quantum Number, n>= 2
    6-7. The Schrodinger Equation for the Helium Atom Cannot Be Solved Exactly
    MathChapter E / Determinants
  • Chapter 7. Approximation Methods
    7-1. The Variational Method Provides an Upper Bound to the Ground-State Energy of a System
    7-2. A Trial Function That Depends Linearly on the Variational Parameters Leads to a Secular Determinant
    7-3. Trial Functions Can Be Linear Combinations of Functions That Also Contain Variational Parameters
    7-4. Perturbation Theory Expresses the Solution to One Problem in Terms of Another Problem Solved Previously
  • Chapter 8. Multielectron Atoms
    8-1. Atomic and Molecular Calculations Are Expressed in Atomic Units
    8-2. Both Pertubation Theory and the Variational Method Can Yield Excellent Results for Helium
    8-3. Hartree-Fock Equations Are Solved by the Self-Consistent Field Method
    8-4. An Electron Has An Intrinsic Spin Angular Momentum
    8-5. Wave Functions Must Be Antisymmetric in the Interchange of Any Two Electrons
    8-6. Antisymmetric Wave Functions Can Be Represented by Slater Determinants
    8-7. Hartree-Fock Calculations Give Good Agreement with Experimental Data
    8-8. A Term Symbol Gives a Detailed Description of an Electron Configuration
    8-9. The Allowed Values of J are L+S, L+S-1, …..,|L-S|
    8-10. Hund’s Rules Are Used to Determine the Term Symbol of the Ground Electronic State
    8-11. Atomic Term Symbols Are Used to Describe Atomic Spectra
  • Chapter 9. The Chemical Bond : Diatomic Molecules
    9-1. The Born-Oppenheimer Approximation Simplifies the Schrodinger Equation for Molecules
    9-2. H2+ Is the Prototypical Species of Molecular-Orbital Theory
    9-3. The Overlap Integral Is a Quantitative Measure of the Overlap of Atomic Orbitals Situated on Different Atoms
    9-4. The Stability of a Chemical Bond Is a Quantum-Mechanical Effect
    9-5. The Simplest Molecular Orbital Treatment of H2+ Yields a Bonding Orbital and an Antibonding Orbital
    9-6. A Simple Molecular-Orbital Treatment of H2 Places Both Electrons in a Bonding Orbital
    9-7. Molecular Orbitals Can Be Ordered According to Their Energies
    9-8. Molecular-Orbital Theory Predicts that a Stable Diatomic Helium Molecule Does Not Exist
    9-9. Electrons Are Placed into Moleular Orbitals in Accord with the Pauli Exclusion Principle
    9-10. Molecular-Orbital Theory Correctly Predicts that Oxygen Molecules Are Paramagnetic
    9-11. Photoelectron Spectra Support the Existence of Molecular Orbitals
    9-12. Molecular-Orbital Theory Also Applies to Heteronuclear Diatomic Molecules
    9-13. An SCF-LCAO-MO Wave Function Is a Molecular Orbital Formed from a Linear Combination of Atomic Orbitals and Whose Coefficients Are Determined Self-Consistently
    9-14. Electronic States of Molecules Are Designated by Molecular Term Symbols
    9-15. Molecular Term Symbols Designate the Symmetry Properties of Molecular Wave Functions
    9-16. Most Molecules Have Excited Electronic States
  • Chapter 10. Bonding in Polyatomic Molecules
    10-1. Hybrid Orbitals Account for Molecular Shape
    10-2. Different Hybrid Orbitals Are Used for the Bonding Electrons and the Lone Pair Electrons in Water
    10-3. Why is BeH2 Linear and H2O Bent?
    10-4. Photoelectron Spectroscopy Can Be Used to Study Molecular Orbitals
    10-5. Conjugated Hydrocarbons and Aromatic Hydrocarbons Can Be Treated by a Pi-Electron Approximation
    10-6. Butadiene is Stabilized by a Delocalization Energy
  • Chapter 11. Computational Quantum Chemistry
    11-1. Gaussian Basis Sets Are Often Used in Modern Computational Chemistry
    11-2. Extended Basis Sets Account Accurately for the Size and Shape of Molecular Charge Distributions
    11-3. Asterisks in the Designation of a Basis Set Denote Orbital Polarization Terms
    11-4. The Ground-State Energy of H2 can be Calculated Essentially Exactly
    11-5. Gaussian 94 Calculations Provide Accurate Information About Molecules
    MathChapter F / Matrices
  • Chapter 12. Group Theory : The Exploitation of Symmetry
    12-1. The Exploitation of the Symmetry of a Molecule Can Be Used to Significantly Simplify Numerical Calculations
    12-2. The Symmetry of Molecules Can Be Described by a Set of Symmetry Elements
    12-3. The Symmetry Operations of a Molecule Form a Group
    12-4. Symmetry Operations Can Be Represented by Matrices
    12-5. The C3V Point Group Has a Two-Dimenstional Irreducible Representation
    12-6. The Most Important Summary of the Properties of a Point Group Is Its Character Table
    12-7. Several Mathematical Relations Involve the Characters of Irreducible Representations
    12-8. We Use Symmetry Arguments to Prediect Which Elements in a Secular Determinant Equal Zero
    12-9. Generating Operators Are Used to Find Linear Combinations of Atomic Orbitals That Are Bases for Irreducible Representations
  • Chapter 13. Molecular Spectroscopy
    13-1. Different Regions of the Electromagnetic Spectrum Are Used to Investigate Different Molecular Processes
    13-2. Rotational Transitions Accompany Vibrational Transitions
    13-3. Vibration-Rotation Interaction Accounts for the Unequal Spacing of the Lines in the P and R Branches of a Vibration-Rotation Spectrum
    13-4. The Lines in a Pure Rotational Spectrum Are Not Equally Spaced
    13-5. Overtones Are Observed in Vibrational Spectra
    13-6. Electronic Spectra Contain Electronic, Vibrational, and Rotational Information
    13-7. The Franck-Condon Principle Predicts the Relative Intensities of Vibronic Transitions
    13-8. The Rotational Spectrum of a Polyatomic Molecule Depends Upon the Principal Moments of Inertia of the Molecule
    13-9. The Vibrations of Polyatomic Molecules Are Represented by Normal Coordinates
    13-10. Normal Coordinates Belong to Irreducible Representation of Molecular Point Groups
    13-11. Selection Rules Are Derived from Time-Dependent Perturbation Theory
    13-12. The Selection Rule in the Rigid Rotator Approximation Is Delta J = (plus or minus) 1
    13-13. The Harmonic-Oscillator Selection Rule Is Delta v = (plus or minus) 1
    13-14. Group Theory Is Used to Determine the Infrared Activity of Normal Coordinate Vibrations
  • Chapter 14. Nuclear Magnetic Resonance Spectroscopy
    14-1. Nuclei Have Intrinsic Spin Angular Momenta
    14-2. Magnetic Moments Interact with Magnetic Fields
    14-3. Proton NMR Spectrometers Operate at Frequencies Between 60 MHz and 750 MHz
    14-4. The Magnetic Field Acting upon Nuclei in Molecules Is Shielded
    14-5. Chemical Shifts Depend upon the Chemical Environment of the Nucleus
    14-6. Spin-Spin Coupling Can Lead to Multiplets in NMR Spectra
    14-7. Spin-Spin Coupling Between Chemically Equivalent Protons Is Not Observed
    14-8. The n+1 Rule Applies Only to First-Order Spectra
    14-9. Second-Order Spectra Can Be Calculated Exactly Using the Variational Method
  • Chapter 15. Lasers, Laser Spectroscopy, and Photochemistry
    15-1. Electronically Excited Molecules Can Relax by a Number of Processes
    15-2. The Dynamics of Spectroscopic Transitions Between the Electronic States of Atoms Can Be Modeled by Rate Equations
    15-3. A Two-Level System Cannot Achieve a Population Inversion
    15-4. Population Inversion Can Be Achieved in a Three-Level System
    15-5. What is Inside a Laser?
    15-6. The Helium-Neon Laser is an Electrical-Discharge Pumped, Continuous-Wave, Gas-Phase Laser
    15-7. High-Resolution Laser Spectroscopy Can Resolve Absorption Lines that Cannot be Distinguished by Conventional Spectrometers
    15-8. Pulsed Lasers Can by Used to Measure the Dynamics of Photochemical Processes
    MathChapter G / Numerical Methods
  • Chapter 16. The Properties of Gases
    16-1. All Gases Behave Ideally If They Are Sufficiently Dilute
    16-2. The van der Waals Equation and the Redlich-Kwong Equation Are Examples of Two-Parameter Equations of State
    16-3. A Cubic Equation of State Can Describe Both the Gaseous and Liquid States
    16-4. The van der Waals Equation and the Redlich-Kwong Equation Obey the Law of Corresponding States
    16-5. The Second Virial Coefficient Can Be Used to Determine Intermolecular Potentials
    16-6. London Dispersion Forces Are Often the Largest Contributer to the r-6 Term in the Lennard-Jones Potential
    16-7. The van der Waals Constants Can Be Written in Terms of Molecular Parameters
  • Chapter 17. The Boltzmann Factor And Partition Functions
    17-1. The Boltzmann Factor Is One of the Most Important Quantities in the Physical Sciences
    17-2. The Probability That a System in an Ensemble Is in the State j with Energy Ej (N,V) Is Proportional to e-Ej(N,V)/kBT
    17-3. We Postulate That the Average Ensemble Energy Is Equal to the Observed Energy of a System
    17-4. The Heat Capacity at Constant Volume Is the Temperature Derivative of the Average Energy
    17-5. We Can Express the Pressure in Terms of a Partition Function
    17-6. The Partition Function of a System of Independent, Distinguishable Molecules Is the Product of Molecular Partition Functions
    17-7. The Partition Function of a System of Independent, Indistinguishable Atoms or Molecules Can Usually Be Written as [q(V,T)]N/N!
    17-8. A Molecular Partition Function Can Be Decomposed into Partition Functions for Each Degree of Freedom
    MathChapter I / Series and Limits
  • Chapter 18. Partition Functions And Ideal Gases
    18-1. The Translational Partition Function of a Monatomic Ideal Gas is (2pi mkBT /h2) 3/2V
    18-2. Most Atoms Are in the Ground Electronic State at Room Temperature
    18-3. The Energy of a Diatomic Molecule Can Be Approximated as a Sum of Separate Terms
    18-4. Most Molecules Are in the Ground Vibrational State at Room Temperature
    18-5. Most Molecules Are in Excited Rotational States at Ordinary Temperatures
    18-6. Rotational Partition Functions Contain a Symmetry Number
    18-7. The Vibrational Partition Function of a Polyatomic Molecule Is a Product of Harmonic Oscillator Partition Functions for Each Normal Coordinate
    18-8. The Form of the Rotational Partition Function of a Polyatomic Molecule Depends Upon the Shape of the Molecule
    18-9. Calculated Molar Heat Capacities Are in Very Good Agreement with Experimental Data
  • Chapter 19. The First Law of Thermodynamics
    19-1. A Common Type of Work is Pressure-Volume Work
    19-2. Work and Heat Are Not State Functions, but Energy is a State Function
    19-3. The First Law of Thermodynamics Says the Energy Is a State Function
    19-4. An Adiabatic Process Is a Process in Which No Energy as Heat Is Transferred
    19-5. The Temperature of a Gas Decreases in a Reversible Adiabatic Expansion
    19-6. Work and Heat Have a Simple Molecular Interpretation
    19-7. The Enthalpy Change Is Equal to the Energy Transferred as Heat in a Constant-Pressure Process Involving Only P-V Work
    19-8. Heat Capacity Is a Path Function
    19-9. Relative Enthalpies Can Be Determined from Heat Capacity Data and Heats of Transition
    19-10. Enthalpy Changes for Chemical Equations Are Additive
    19-11. Heats of Reactions Can Be Calculated from Tabulated Heats of Formation
    19-12. The Temperature Dependence of deltarH is Given in Terms of the Heat Capacities of the Reactants and Products
    MathChapter J / The Binomial Distribution and Stirling’s Approximation
  • Chapter 20. Entropy and The Second Law of Thermodynamics
    20-1. The Change of Energy Alone Is Not Sufficient to Determine the Direction of a Spontaneous Process
    20-2. Nonequilibrium Isolated Systems Evolve in a Direction That Increases Their Disorder
    20-3. Unlike qrev, Entropy Is a State Function
    20-4. The Second Law of Thermodynamics States That the Entropy of an Isolated System Increases as a Result of a Spontaneous Process
    20-5. The Most Famous Equation of Statistical Thermodynamics is S = kB ln W
    20-6. We Must Always Devise a Reversible Process to Calculate Entropy Changes
    20-7. Thermodynamics Gives Us Insight into the Conversion of Heat into Work
    20-8. Entropy Can Be Expressed in Terms of a Partition Function
    20-9. The Molecular Formula S = kB in W is Analogous to the Thermodynamic Formula dS = deltaqrev/T
  • Chapter 21. Entropy And The Third Law of Thermodynamics
    21-1. Entropy Increases With Increasing Temperature
    21-2. The Third Law of Thermodynamics Says That the Entropy of a Perfect Crystal is Zero at 0 K
    21-3. deltatrsS = deltatrsH / Ttrs at a Phase Transition
    21-4. The Third Law of Thermodynamics Asserts That CP -> 0 as T -> 0
    21-5. Practical Absolute Entropies Can Be Determined Calorimetrically
    21-6. Practical Absolute Entropies of Gases Can Be Calculated from Partition Functions
    21-7. The Values of Standard Entropies Depend Upon Molecular Mass and Molecular Structure
    21-8. The Spectroscopic Entropies of a Few Substances Do Not Agree with the Calorimetric Entropies
    21-9. Standard Entropies Can Be Used to Calculate Entropy Changes of Chemical Reactions
  • Chapter 22. Helmholtz and Gibbs Energies
    22-1. The Sign of the Helmholtz Energy Change Determines the Direction of a Spontaneous Process in a System at Constant Volume and Temperature
    22-2. The Gibbs Energy Determines the Direction of a Spontaneous Process for a System at Constant Pressure and Temperature
    22-3. Maxwell Relations Provide Several Useful Thermodynamic Formulas
    22-4. The Enthalpy of an Ideal Gas Is Independent of Pressure
    22-5. The Various Thermodynamic Functions Have Natural Independent Variables
    22-6. The Standard State for a Gas at Any Temperature Is the Hypothetical Ideal Gas at One Bar
    22-7. The Gibbs-Helmholtz Equation Describes the Temperature Dependance of the Gibbs Energy
    22-8. Fugacity Is a Measure of the Nonideality of a Gas
  • Chapter 23. Phase Equilibria
    23-1. A Phase Diagram Summarizes the Solid-Liquid-Gas Behavior of a Substance
    23-2. The Gibbs Energy of a Substance Has a Close Connection to Its Phase Diagram
    23-3. The Chemical Potentials of a Pure Substance in Two Phases in Equilibrium Are Equal
    23-4. The Clausius-Clapeyron Equation Gives the Vapor Pressure of a Substance As a Function of Temperature
    23-5. Chemical Potential Can be Evaluated From a Partition Function
  • Chapter 24. Solutions I: Liquid-Liquid Solutions
    24-1. Partial Molar Quantities Are Important Thermodynamic Properites of Solutions
    24-2. The Gibbs-Duhem Equation Relates the Change in the Chemical Potential of One Component of a Solution to the Change in the Chemical Potential of the Other
    24-3. The Chemical Potential of Each Component Has the Same Value in Each Phase in Which the Component Appears
    24-4. The Components of an Ideal Solution Obey Raoult’s Law for All Concentrations
    24-5. Most Solutions are Not Ideal
    24-6. The Gibbs-Duhem Equation Relats the Vapor Pressures of the Two Components of a Volatile Binary Solution
    24-7. The Central Thermodynamic Quantity for Nonideal Solutions is the Activity
    24-8. Activities Must Be Calculated with Respect to Standard States
    24-9. We Can Calculate the Gibbs Energy of Mixing of Binary Solutions in Terms of the Activity Coefficient
  • Chapter 25. Solutions II: Solid-Liquid Solutions
    25-1. We Use a Raoult’s Law Standard State for the Solvent and a Henry’s Law Standard State for the Solute for Solutionsof Solids Dissolved in Liquids
    25-2. The Activity of a Nonvolatile Solute Can Be Obtained from the Vapor Pressure of the Solvent
    25-3. Colligative Properties Are Solution Properties That Depend Only Upon the Number Density of Solute Particles
    25-4. Osmotic Pressure Can Be Used to Determine the Molecular Masses of Polymers
    25-5. Solutions of Electrolytes Are Nonideal at Relatively Low Concentrations
    25-6. The Debye-Hukel Theory Gives an Exact Expression of 1n gamma(plus or minus) For Very Dilute Solutions
    25-7. The Mean Spherical Approximation Is an Extension of the Debye-Huckel Theory to Higher Concentrations
  • Chapter 26. Chemical Equilibrium
    26-1. Chemical Equilibrium Results When the Gibbs Energy Is a Minimun with Respect to the Extent of Reaction
    26-2. An Equilibrium Constant Is a Function of Temperature Only
    26-3. Standard Gibbs Energies of Formation Can Be Used to Calculate Equilibrium Constants
    26-4. A Plot of the Gibbs Energy of a Reaction Mixture Against the Extent of Reaction Is a Minimum at Equilibrium
    26-5. The Ratio of the Reaction Quotient to the Equilibrium Constant Determines the Direction in Which a Reaction Will Proceed
    26-6. The Sign of deltar G And Not That of deltaGo Determines the Direction of Reaction Spontaneity
    26-7. The Variation of an Equilibrium Constant with Temperature Is Given by the Van’t Hoff Equation
    26-8. We Can Calculate Equilibrium Constants in Terms of Partition Functions
    26-9. Molecular Partition Functions and Related Thermodynamic Data Are Extensively Tabulated
    26-10. Equilibrium Constants for Real Gases Are Expressed in Terms of Partial Fugacities
    26-11. Thermodynamic Equilibrium Constants Are Expressed in Terms of Activities
    26-12. The Use of Activities Makes a Significant Difference in Solubility Calculations Involving Ionic Species
  • Chapter 27. The Kinetic Theory of Gases
    27-1. The Average Translational Kinetic Energy of the Molecules in a Gas Is Directly Proportional to the Kelvin Temperature
    27-2. The Distribution of the Components of Molecular Speeds Are Described by a Gaussian Distribution
    27-3. The Distribution of Molecular Speeds Is Given by the Maxwell-Boltzmann Distribution
    27-4. The Frequency of Collisions that a Gas Makes with a Wall Is Proportional to its Number Density and to the Average Molecular Speed
    27-5. The Maxwell-Boltzmann Distribution Has Been Verified Experimentally
    27-6. The Mean Free Path Is the Average Distance a Molecule Travels Between Collisions
    27-7. The Rate of a Gas-Phase Chemical Reaction Depends Upon the Rate of Collisions in Which the Relative Kinetic Energy Exceeds Some Critical Value
  • Chapter 28. Chemical Kinetics I : Rate Laws
    28-1. The Time Dependence of a Chemical Reaction Is Described by a Rate Law
    28-2. Rate Laws Must Be Determined Experimentally
    28-3. First-Order Reactions Show an Exponential Decay of Reactant Concentration with Time
    28-4. The Rate Laws for Different Reaction Orders Predict Different Behaviors for the Time-Dependent Reactant Concentration
    28-5. Reactions Can Also Be Reversible
    28-6. The Rate Constants of a Reversible Reaction Can Be Determined Using Relaxation Techniques
    28-7. Rate Constants Are Usually Strongly Temperature Dependent
    28-8. Transition-State Theory Can Be Used to Estimate Reaction Rate Constants
  • Chapter 29. Chemical Kinetics II : Reaction Mechanisms
    29-1. A Mechanism is a Sequence of Single-Step Chemical Reactions called Elementary Reactions
    29-2. The Principle of Detailed Balance States that when a Complex Reaction is at Equilibrium, the Rate of the Forward Process is Equal to the Rate of the Reverse Process for Each and Every Step of the Reaction Mechanism
    29-3. When Are Consecutive and Single-Step Reactions Distinguishable?
    29-4. The Steady-State Approximation Simplifies Rate Expressions yy Assuming that d[I]/dt=0, where I is a Reaction Intermediate
    29-5. The Rate Law for a Complex Reaction Does Not Imply a Unique Mechanism
    29-6. The Lindemann Mechanism Explains How Unimolecular Reactions Occur
    29-7. Some Reaction Mechanisms Involve Chain Reactions
    29-8. A Catalyst Affects the Mechanism and Activation Energy of a Chemical Reaction
    29-9. The Michaelis-Menten Mechanism Is a Reaction Mechanism for Enzyme Catalysis
  • Chapter 30. Gas-Phase Reaction Dynamics
    30-1. The Rate of Bimolecular Gas-Phase Reaction Can Be Calculated Using Hard-Sphere Collision Theory and an Energy-Dependent Reaction Cross Section
    30-2. A Reaction Cross Section Depends Upon the Impact Parameter
    30-3. The Rate Constant for a Gas-Phase Chemical Reaction May Depend on the Orientations of the Colliding Molecules
    30-4. The Internal Energy of the Reactants Can Affect the Cross Section of a Reaction
    30-5. A Reactive Collision Can Be Described in a Center-of-Mass Coordinate System
    30-6. Reactive Collisions Can be Studied Using Crossed Molecular Beam Machines
    30-7. The Reaction F(g) +D(g) => DF(g) + D(g) Can Produce Vibrationally Excited DF(g) Molecules
    30-8. The Velocity and Angular Distribution of the Products of a Reactive Collision Provide a Molecular Picture of the Chemical Reaction
    30-9. Not All Gas-Phase Chemical Reactions Are Rebound Reactions
    30-10. The Potential-Energy Surface for the Reaction F(g) + D2(g) => DF(g) + D(g) Can Be Calculated Using Quantum Mechanics
  • Chapter 31. Solids and Surface Chemistry
    31-1. The Unit Cell Is the Fundamental Building Block of a Crystal
    31-2. The Orientation of a Lattice Plane Is Described by its Miller Indices
    31-3. The Spacing Between Lattice Planes Can Be Determined from X-Ray Diffraction Measurements
    31-4. The Total Scattering Intensity Is Related to the Periodic Structure of the Electron Density in the Crystal
    31-5. The Structure Factor and the Electron Density Are Related by a Fourier Transform
    31-6. A Gas Molecule Can Physisorb or Chemisorb to a Solid Surface
    31-7. Isotherms Are Plots of Surface Coverage as a Function of Gas Pressure at Constant Temperature
    31-8. The Langmuir Isotherm Can Be Used to Derive Rate Laws for Surface-Catalyzed Gas-Phase Reactions
    31-9. The Structure of a Surface is Different from that of a Bulk Solid
    31-10. The Reaction Between H2(g) and N 2(g) to Make NH(g) Can Be Surface Catalyzed
    Answers to the Numerical Problems
    lllustration Credits


“McQuarrie and Simon have developed an excellent modern physical chemistry course that should inspire us to rethink our curriculum.”
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-Benjamin Goldstein, a chemistry major at Princeton University

“A true double thumbs up! Throughout my entire undergraduate study, both thermodynamic and reaction kinetics were conducted in a very classical manner. Whereas most of the advanced courses, thermo. and reaction kinetics, conducted here in CMU are basically dealing with all kinds of microscopic phenomena. Your book has served as a very good platform to link up my previous experiences with my current study.”
-Lim Jit Kang, a Graduate Student at Carnegie Mellon University

Donald A. McQuarrie University of California, Davis

As the author of landmark chemistry books and textbooks, Donald McQuarrie's name is synonymous with excellence in chemical education.  From his classic text on Statistical Mechanics to his recent quantum-first tour de force on Physical Chemistry, McQuarrie's best selling textbooks are highly acclaimed by the chemistry community.  McQuarrie received his PhD from the University of Oregon, and is Professor Emeritus from the Department of Chemistry at the University of California, Davis.  

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John D. Simon Duke University

John D. Simon became the first George B. Geller Professor of Chemistry at Duke University in 1998. He is currently Chair Chemistry Department at Duke and a faculty member of the Biochemistry, and Ophthalmology Departments of the Duke Medical Center. John graduated from Williams College in 1979 with a B.A. in Chemistry and received his Ph.D. from Harvard University in 1983. After a postdoctoral fellowship with Professor Mostafa El-Sayed at UCLA, John joined the faculty of the Department of Chemistry at UCSD in 1985.

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