Complete Table-of-Contents for

Physical Chemistry

A Molecular Approach

 Donald A. McQuarrie
University of California, Davis

John D. Simon
Duke University

• 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

  Problems

   

  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

  Problems

   

  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 sigma_psigma_x>h/2

  3-9. The Problem of a Particle in a Three-Dimensional Box is a Simple Extension of the One-Dimensional Case

  Problems

   

  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

  Problems

   

  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 E_v = 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 ²J(J+1)/2I

  5-9. The Rigid Rotator Is a Model for a Rotating Diatomic Molecule

  Problems

• 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

  Problems

   

  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

  Problems

• 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

  Problems

• 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

  Problems

• 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

  Problems

• 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

  Problems

   

  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 C_3V 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

  Problems

• 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

  Problems

• 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

  Problems

• 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

  Problems

   

  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

  Problems

• 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 E_j (N,V) Is Proportional to e^-Ej(N,V)/k_B^T

  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

  Problems

   

  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 mk_BT /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

  Problems

• 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 delta_rH is Given in Terms of the Heat Capacities of the Reactants and Products

  Problems

   

  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 q_rev, 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 = k_B 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 = k_B in W is Analogous to the Thermodynamic Formula dS = deltaq_rev/T

  Problems

• 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. delta_trsS = delta_trsH / T_trs at a Phase Transition

  21-4. The Third Law of Thermodynamics Asserts That C_P -> 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

  Problems

• 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

  Problems

• 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

  Problems

• 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

  Problems

• 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

  Problems

• 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 delta_r G And Not That of delta_r G^o 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

  Problems

• 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

  Problems

• 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

  Problems

• 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

  Problems

• 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) +D₂ (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

  Problems

• 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 NH₃ (g) Can Be Surface Catalyzed

  Problems

  Answers to the Numerical Problems

  lllustration Credits

  Index