9780935702996

Physical Chemistry: A Molecular Approach

by ;
  • ISBN13:

    9780935702996

  • ISBN10:

    0935702997

  • Format: Hardcover
  • Copyright: 7/1/1997
  • Publisher: UNIVERSITY SCIENCE BOOKS

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Table of Contents

Preface xvii(6)
To the Student xvii(2)
To the Instructor xix(4)
Acknowledgment xxiii
CHAPTER 1 / The Dawn of the Quantum Theory
1(38)
1-1. Blackbody Radiation Could Not Be Explained by Classical Physics
2(2)
1-2. Planck Used a Quantum Hypothesis to Derive the Blackbody Radiation Law
4(3)
1-3. Einstein Explained the Photoelectric Effect with a Quantum Hypothesis
7(3)
1-4. The Hydrogen Atomic Spectrum Consists of Several Series of Lines
10(3)
1-5. The Rydberg Formula Accounts for All the Lines in the Hydrogen Atomic Spectrum
13(2)
1-6. Louis de Broglie Postulated That Matter Has Wavelike Properties
15(1)
1-7. de Broglie Waves Are Observed Experimentally
16(2)
1-8. The Bohr Theory of the Hydrogen Atom Can Be Used to Derive the Rydberg Formula
18(5)
1-9. The Heisenberg Uncertainty Principle States That the Position and the Momentum of a Particle Cannot Be Specified Simultaneously with Unlimited Precision
23(2)
Problems
25(6)
MATHCHAPTER A / Complex Numbers
31(4)
Problems
35(4)
CHAPTER 2 / The Classical Wave Equation
39(34)
2-1. The One-Dimensional Wave Equation Describes the Motion of a Vibrating String
39(1)
2-2. The Wave Equation Can Be Solved by the Method of Separation of Variables
40(4)
2-3. Some Differential Equations Have Oscillatory Solutions
44(2)
2-4. The General Solution to the Wave Equation Is a Superposition of Normal Modes
46(3)
2-5. A Vibrating Membrane Is Described by a Two-Dimensional Wave Equation
49(5)
Problems
54(9)
MATHCHAPTER B / Probability and Statistics
63(7)
Problems
70(3)
CHAPTER 3 / The Schrodinger Equation and a Particle In a Box
73(42)
3-1. The Schrodinger Equation Is the Equation for Finding the Wave Function of a Particle
73(2)
3-2. Classical-Mechanical Quantities Are Represented by Linear Operators in Quantum Mechanics
75(2)
3-3. The Schrodinger Equation Can Be Formulated As an Eigenvalue Problem
77(3)
3-4. Wave Functions Have a Probabilistic Interpretation
80(1)
3-5. The Energy of a Particle in a Box Is Quantized
81(3)
3-6. Wave Functions Must Be Normalized
84(2)
3-7. The Average Momentum of a Particle in a Box Is Zero
86(2)
3-8. The Uncertainty Principle Says That XXX(p) XXX(x) > h/2
88(2)
3-9. The Problem of a Particle in a Three-Dimensional Box Is a Simple Extension of the One-Dimensional Case
90(6)
Problems
96(9)
MATHCHAPTER C / Vectors
105(8)
Problems
113(2)
CHAPTER 4 / Some Postulates and General Principles of Quantum Mechanics
115(42)
4-1. The State of a System Is Completely Specified by Its Wave Function
115(3)
4-2. Quantum-Mechanical Operators Represent Classical-Mechanical Variables
118(4)
4-3. Observable Quantities Must Be Eigenvalues of Quantum Mechanical Operators
122(3)
4-4. The Time Dependence of Wave Functions Is Governed by the Time-Dependent Schrodinger Equation
125(2)
4-5. The Eigenfunctions of Quantum Mechanical Operators Are Orthogonal
127(4)
4-6. The Physical Quantities Corresponding to Operators That Commute Can Be Measured Simultaneously to Any Precision
131(3)
Problems
134(19)
MATHCHAPTER D / Spherical Coordinates
147(6)
Problems
153(4)
CHAPTER 5 / The Harmonic Oscillator and the Rigid Rotator: Two Spectroscopic Models
157(34)
5-1. A Harmonic Oscillator Obeys Hooke's Law
157(4)
5-2. The Equation for a Harmonic-Oscillator Model of a Diatomic Molecule Contains the Reduced Mass of the Molecule
161(2)
5-3. The Harmonic-Oscillator Approximation Results from the Expansion of an Internuclear Potential Around Its Minimum
163(3)
5-4. The Energy Levels of a Quantum-Mechanical Harmonic Oscillator Are E(v) = hw(v + XXX) with v=0, 1, 2, ...
166(1)
5-5. The Harmonic Oscillator Accounts for the Infrared Spectrum of a Diatomic Molecule
167(2)
5-6. The Harmonic-Oscillator Wave Functions Involve Hermite Polynomials
169(3)
5-7. Hermite Polynomials Are Either Even or Odd Functions
172(1)
5-8. The Energy Levels of a Rigid Rotator Are E = h(2)J(J+1)/21
173(4)
5-9. The Rigid Rotator Is a Model for a Rotating Diatomic Molecule
177(2)
Problems
179(12)
CHAPTER 6 / The Hydrogen Atom
191(50)
6-1. The Schrodinger Equation for the Hydrogen Atom Can Be Solved Exactly
191(2)
6-2. The Wave Functions of a Rigid Rotator Are Called Spherical Harmonics
193(7)
6-3. The Precise Values of the Three Components of Angular Momentum Cannot Be Measured Simultaneously
200(6)
6-4. Hydrogen Atomic Orbitals Depend upon Three Quantum Numbers
206(3)
6-5. s Orbitals Are Spherically Symmetric
209(4)
6-6. There Are Three p Orbitals for Each Value of the Principal Quantum Number, n XXX 2
213(6)
6-7. The Schrodinger Equation for the Helium Atom Cannot Be Solved Exactly
219(1)
Problems
220(11)
MATHCHAPTER E / Determinants
231(7)
Problems
238(3)
CHAPTER 7 / Approximation Methods
241(34)
7-1. The Variational Method Provides an Upper Bound to the Ground-State Energy of a System
241(8)
7-2. A Trial Function That Depends Linearly on the Variational Parameters Leads to a Secular Determinant
249(7)
7-3. Trial Functions Can Be Linear Combinations of Functions That Also Contain Variational Parameters
256(1)
7-4. Perturbation Theory Expresses the Solution to One Problem in Terms of Another Problem Solved Previously
257(4)
Problems
261(14)
CHAPTER 8 / Multielectron Atoms
275(48)
8-1. Atomic and Molecular Calculations Are Expressed in Atomic Units
275(3)
8-2. Both Perturbation Theory and the Variational Method Can Yield Excellent Results for Helium
278(4)
8-3. Hartree-Fock Equations Are Solved by the Self-Consistent Field Method
282(2)
8-4. An Electron Has an Intrinsic Spin Angular Momentum
284(1)
8-5. Wave Function Must Be Antisymmetric in the Interchange of Any Two Electrons
285(3)
8-6. Antisymmetric Wave Functions Can Be Represented by Slater Determinants
288(2)
8-7. Hartree-Fock Calculations Give Good Agreement with Experimental Data
290(2)
8-8. A Term Symbol Gives a Detailed Description of an Electron Configuration
292(4)
8-9. The Allowed Values of J are L+S, L+S-1, ..., |L-S|
296(5)
8-10. Hund's Rules Are Used to Determine the Term Symbol of the Ground Electronic State
301(1)
8-11. Atomic Term Symbols Are Used to Describe Atomic Spectra
302(6)
Problems
308(15)
CHAPTER 9 / The Chemical Bond: Diatomic Molecules
323(48)
9-1. The Born-Oppenheimer Approximation Simplifies the Schrodinger Equation for Molecules
323(2)
9-2. H(+)(2) Is the Prototypical Species of Molecular-Orbital Theory
325(2)
9-3. The Overlap Integral Is a Quantitative Measure of the Overlap of Atomic Orbitals Situated on Different Atoms
327(2)
9-4. The Stability of a Chemical Bond Is a Quantum-Mechanical Effect
329(4)
9-5. The Simplest Molecular Orbital Treatment of H(+)(2) Yields a Bonding Orbital and an Antibonding Orbital
333(3)
9-6. A Simple Molecular-Orbital Treatment of H(2) Places Both Electrons in a Bonding Orbital
336(1)
9-7. Molecular Orbitals Can Be Ordered According to Their Energies
336(5)
9-8. Molecular-Orbital Theory Predicts That a Stable Diatomic Helium Molecule Does Not Exist
341(1)
9-9. Electrons Are Placed into Molecular Orbitals in Accord with the Pauli Exclusion Principle
342(2)
9-10. Molecular-Orbital Theory Correctly Predicts That Oxygen Molecules Are Paramagnetic
344(2)
9-11. Photoelectron Spectra Support the Existence of Molecular Orbitals
346(1)
9-12. Molecular-Orbital Theory Also Applies to Heteronuclear Diatomic Molecules
346(3)
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
349(6)
9-14. Electronic States of Molecules Are Designated by Molecular Term Symbols
355(3)
9-15. Molecular Term Symbols Designate the Symmetry Properties of Molecular Wave Functions
358(2)
9-16. Most Molecules Have Excited Electronic States
360(2)
Problems
362(9)
CHAPTER 10 / Bonding In Polyatomic Molecules
371(40)
10-1. Hybrid Orbitals Account for Molecular Shape
371(7)
10-2. Different Hybrid Orbitals Are Used for the Bonding Electrons and the Lone Pair Electrons in Water
378(3)
10-3. Why is BeH(2) Linear and H(2)O Bent?
381(6)
10-4. Photoelectron Spectroscopy Can Be Used to Study Molecular Orbitals
387(3)
10-5. Conjugated Hydrocarbons and Aromatic Hydrocarbons Can Be Treated by a XXX-Electron Approximation
390(3)
10-6. Butadiene Is Stabilized by a Delocalization Energy
393(6)
Problems
399(12)
CHAPTER 11 / Computational Quantum Chemistry
411(42)
11-1. Gaussian Basis Sets Are Often Used in Modern Computational Chemistry
411(6)
11-2. Extended Basis Sets Account Accurately for the Size and Shape of Molecular Charge Distributions
417(5)
11-3. Asterisks in the Designation of a Basis Set Denote Orbital Polarization Terms
422(3)
11-4. The Ground-State Energy of H(2) can be Calculated Essentially Exactly
425(2)
11-5. Gaussian 94 Calculations Provide Accurate Information About Molecules
427(7)
Problems
434(7)
MATHCHAPTER F / Matrices
441(7)
Problems
448(5)
CHAPTER 12 / Group Theory: The Exploitation of Symmetry
453(42)
12-1. The Exploitation of the Symmetry of a Molecule Can Be Used to Significantly Simplify Numerical Calculations
453(2)
12-2. The Symmetry of Molecules Can Be Described by a Set of Symmetry Elements
455(5)
12-3. The Symmetry Operations of a Molecule Form a Group
460(4)
12-4. Symmetry Operations Can Be Represented by Matrices
464(4)
12-5. The C(3v) Point Group Has a Two-Dimensional Irreducible Representation
468(3)
12-6. The Most Important Summary of the Properties of a Point Group Is Its Character Table
471(3)
12-7. Several Mathematical Relations Involve the Characters of Irreducible Representations
474(6)
12-8. We Use Symmetry Arguments to Predict Which Elements in a Secular Determinant Equal Zero
480(4)
12-9. Generating Operators Are Used to Find Linear Combinations of Atomic Orbitals That Are Bases for Irreducible Representations
484(5)
Problems
489(6)
CHAPTER 13 / Molecular Spectroscopy
495(52)
13-1. Different Regions of the Electromagnetic Spectrum Are Used to Investigate Different Molecular Processes
495(2)
13-2. Rotational Transitions Accompany Vibrational Transitions
497(4)
13-3. Vibration-Rotation Interaction Accounts for the Unequal Spacing of the Lines in the P and R Branches of a Vibration-Rotation Spectrum
501(2)
13-4. The Lines in a Pure Rotational Spectrum Are Not Equally Spaced
503(1)
13-5. Overtones Are Observed in Vibrational Spectra
504(3)
13-6. Electronic Spectra Contain Electronic, Vibrational, and Rotational Information
507(4)
13-7. The Franck-Condon Principle Predicts the Relative Intensities of Vibronic Transitions
511(3)
13-8. The Rotational Spectrum of a Polyatomic Molecule Depends Upon the Principal Moments of Inertia of the Molecule
514(4)
13-9. The Vibrations of Polyatomic Molecules Are Represented by Normal Coordinates
518(5)
13-10. Normal Coordinates Belong to Irreducible Representations of Molecular Point Groups
523(4)
13-11. Selection Rules Are Derived from Time-Dependent Perturbation Theory
527(4)
13-12. The Selection Rule in the Rigid Rotator Approximation Is XXXJ = XXX1
531(2)
13-13. The Harmonic-Oscillator Selection Rule Is XXXv = XXX1
533(2)
13-14. Group Theory Is Used to Determine the Infrared Activity of Normal Coordinate Vibrations
535(2)
Problems
537(10)
CHAPTER 14 / Nuclear Magnetic Resonance Spectroscopy
547(44)
14-1. Nuclei Have Intrinsic Spin Angular Momenta
548(2)
14-2. Magnetic Moments Interact with Magnetic Fields
550(4)
14-3. Proton NMR Spectrometers Operate at Frequencies Between 60 MHz and 750 MHz
554(2)
14-4. The Magnetic Field Acting upon Nuclei in Molecules Is Shielded
556(4)
14-5. Chemical Shifts Depend upon the Chemical Environment of the Nucleus
560(2)
14-6. Spin-Spin Coupling Can Lead to Multiplets in NMR Spectra
562(8)
14-7. Spin-Spin Coupling Between Chemically Equivalent Protons Is Not Observed
570(3)
14-8. The n + 1 Rule Applies Only to First-Order Spectra
573(3)
14-9. Second-Order Spectra Can Be Calculated Exactly Using the Variational Method
576(9)
Problems
585(6)
CHAPTER 15 / Lasers, Laser Spectroscopy, and Photochemistry
591(46)
15-1. Electronically Excited Molecules Can Relax by a Number of Processes
592(3)
15-2. The Dynamics of Spectroscopic Transitions Between the Electronic States of Atoms Can Be Modeled by Rate Equations
595(6)
15-3. A Two-Level System Cannot Achieve a Population Inversion
601(2)
15-4. Population Inversion Can Be Achieved in a Three-Level System
603(1)
15-5. What Is Inside a Laser?
604(5)
15-6. The Helium-Neon Laser is an Electrical-Discharge Pumped, Continuous-Wave, Gas-Phase Laser
609(4)
15-7. High-Resolution Laser Spectroscopy Can Resolve Absorption Lines That Cannot Be Distinguished by Conventional Spectrometers
613(1)
15-8. Pulsed Lasers Can Be Used to Measure the Dynamics of Photochemical Processes
614(6)
Problems
620(7)
MATHCHAPTER G / Numerical Methods
627(7)
Problems
634(3)
CHAPTER 16 / The Properties of Gases
637(46)
16-1. All Gases Behave Ideally If They Are Sufficiently Dilute
637(5)
16-2. The van der Waals Equation and the Redlich-Kwong Equation Are Examples of Two-Parameter Equations of State
642(6)
16-3. A Cubic Equation of State Can Describe Both the Gaseous and Liquid States
648(7)
16-4. The van der Waals Equation and the Redlich-Kwong Equation Obey the Law of Corresponding States
655(3)
16-5. Second Virial Coefficients Can Be Used to Determine Intermolecular Potentials
658(7)
16-6. London Dispersion Forces Are Often the Largest Contribution to the r(-6) Term in the Lennard-Jones Potential
665(5)
16-7. The van der Waals Constants Can Be Written in Terms of Molecular Parameters
670(4)
Problems
674(9)
MATHCHAPTER H / Partial Differentiation
683(6)
Problems
689(4)
CHAPTER 17 / The Boltzmann Factor and Partition Functions
693(38)
17-1. The Boltzmann Factor Is One of the Most Important Quantities in the Physical Sciences
694(2)
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(-E(j)(N,V)/k(B)(T)
696(2)
17-3. We Postulate That the Average Ensemble Energy Is Equal to the Observed Energy of a System
698(4)
17-4. The Heat Capacity at Constant Volume Is the Temperature Derivative of the Average Energy
702(2)
17-5. We Can Express the Pressure in Terms of a Partition Function
704(3)
17-6. The Partition Function of a System of Independent, Distinguishable Molecules Is the Product of Molecular Partition Functions
707(1)
17-7. The Partition Function of a System of Independent, Indistinguishable Atoms or Molecules Can Usually Be Written as [q(V,T)](N) / N!
708(5)
17-8. A Molecular Partition Function Can Be Decomposed into Partition Functions for Each Degree of Freedom
713(3)
Problems
716(7)
MATHCHAPTER I / Series and Limits
723(5)
Problems
728(3)
CHAPTER 18 / Partition Functions and Ideal Gases
731(34)
18-1. The Translational Partition Function of an Atom in a Monatomic Ideal Gas Is (2XXXmk(B)T/h(2))(3/2)V
731(2)
18-2. Most Atoms Are in the Ground Electronic State at Room Temperature
733(4)
18-3. The Energy of a Diatomic Molecule Can Be Approximated as a Sum of Separate Terms
737(3)
18-4. Most Molecules Are in the Ground Vibrational State at Room Temperature
740(3)
18-5. Most Molecules Are in Excited Rotational States at Ordinary Temperatures
743(3)
18-6. Rotational Partition Functions Contain a Symmetry Number
746(3)
18-7. The Vibrational Partition Function of a Polyatomic Molecule Is a Product of Harmonic Oscillator Partition Functions for Each Normal Coordinate
749(3)
18-8. The Form of the Rotational Partition Function of a Polyatomic Molecule Depends upon the Shape of the Molecule
752(2)
18-9. Calculated Molar Heat Capacities Are in Very Good Agreement with Experimental Data
754(3)
Problems
757(8)
CHAPTER 19 / The First Law of Thermodynamics
765(52)
19-1. A Common Type of Work is Pressure-Volume Work
766(3)
19-2. Work and Heat Are Not State Functions, but Energy Is a State Function
769(4)
19-3. The First Law of Thermodynamics Says the Energy Is a State Function
773(1)
19-4. An Adiabatic Process Is a Process in Which No Energy as Heat Is Transferred
774(3)
19-5. The Temperature of a Gas Decreases in a Reversible Adiabatic Expansion
777(2)
19-6. Work and Heat Have a Simple Molecular Interpretation
779(1)
19-7. The Enthalpy Change Is Equal to the Energy Transferred as Heat in a Constant-Pressure Process Involving Only P-V Work
780(3)
19-8. Heat Capacity Is a Path Function
783(3)
19-9. Relative Enthalpies Can Be Determined from Heat Capacity Data and Heats of Transition
786(1)
19-10. Enthalpy Changes for Chemical Equations Are Additive
787(4)
19-11. Heats of Reactions Can Be Calculated from Tabulated Heats of Formation
791(6)
19-12. The Temperature Dependence of XXX(r)H Is Given in Terms of the Heat Capacities of the Reactants and Products
797(3)
Problems
800(9)
MATHCHAPTER J / The Binomial Distribution and Stirling's Approximation
809(5)
Problems
814(3)
CHAPTER 20 / Entropy and the Second Law of Thermodynamics
817(36)
20-1. The Change of Energy Alone Is Not Sufficient to Determine the Direction of a Spontaneous Process
817(2)
20-2. Nonequilibrium Isolated Systems Evolve in a Direction That Increases Their Disorder
819(2)
20-3. Unlike q(rev') Entropy Is a State Function
821(4)
20-4. The Second Law of Thermodynamics States That the Entropy of an Isolated System Increases as a Result of a Spontaneous Process
825(4)
20-5. The Most Famous Equation of Statistical Thermodynamics Is S = k(B) In W
829(4)
20-6. We Must Always Devise a Reversible Process to Calculate Entropy Changes
833(5)
20-7. Thermodynamics Gives Us Insight into the Conversion of Heat into Work
838(2)
20-8. Entropy Can Be Expressed in Terms of a Partition Function
840(3)
20-9. The Molecular Formula S = k(B) In W Is Analogous to the Thermodynamic Formula dS = XXXq(rev)/T
843(1)
Problems
844(9)
CHAPTER 21 / Entropy and the Third Law of Thermodynamics
853(28)
21-1. Entropy Increases with Increasing Temperature
853(2)
21-2. The Third Law of Thermodynamics Says That the Entropy of a Perfect Crystal Is Zero at O K
855(2)
21-3. XXX(trs)S = XXX(trs)H/T(trs) at a Phase Transition
857(1)
21-4. The Third Law of Thermodynamics Asserts That C(p) XXX 0 as T XXX 0
858(1)
21-5. Practical Absolute Entropies Can Be Determined Calorimetrically
859(2)
21-6. Practical Absolute Entropies of Gases Can Be Calculated from Partition Functions
861(4)
21-7. The Values of Standard Entropies Depend upon Molecular Mass and Molecular Structure
865(3)
21-8. The Spectroscopic Entropies of a Few Substances Do Not Agree with the Calorimetric Entropies
868(1)
21-9. Standard Entropies Can Be Used to Calculate Entropy Changes of Chemical Reactions
869(1)
Problems
870(11)
CHAPTER 22 / Helmholtz and Gibbs Energies
881(44)
22-1. The Sign of the Helmholtz Energy Change Determines the Direction of a Spontaneous Process in a System at Constant Volume and Temperature
881(3)
22-2. The Gibbs Energy Determines the Direction of a Spontaneous Process for a System at Constant Pressure and Temperature
884(4)
22-3. Maxwell Relations Provide Several Useful Thermodynamic Formulas
888(5)
22-4. The Enthalpy of an Ideal Gas Is Independent of Pressure
893(3)
22-5. The Various Thermodynamic Functions Have Natural Independent Variables
896(3)
22-6. The Standard State for a Gas at Any Temperature Is the Hypothetical Ideal Gas at One Bar
899(2)
22-7. The Gibbs-Helmholtz Equation Describes the Temperature Dependence of the Gibbs Energy
901(4)
22-8. Fugacity Is a Measure of the Nonideality of a Gas
905(5)
Problems
910(15)
CHAPTER 23 / Phase Equilibria
925(38)
23-1. A Phase Diagram Summarizes the Solid-Liquid-Gas Behavior of a Substance
926(7)
23-2. The Gibbs Energy of a Substance Has a Close Connection to Its Phase Diagram
933(2)
23-3. The Chemical Potentials of a Pure Substance in Two Phases in Equilibrium Are Equal
935(6)
23-4. The Clausius-Clapeyron Equation Gives the Vapor Pressure of a Substance As a Function of Temperature
941(4)
23-5. Chemical Potential Can Be Evaluated from a Partition Function
945(4)
Problems
949(14)
CHAPTER 24 / Chemical Equilibrium
963(48)
24-1. Chemical Equilibrium Results when the Gibbs Energy Is a Minimum with Respect to the Extent of Reaction
963(4)
24-2. An Equilibrium Constant Is a Function of Temperature Only
967(3)
24-3. Standard Gibbs Energies of Formation Can Be Used to Calculate Equilibrium Constants
970(2)
24-4. A Plot of the Gibbs Energy of a Reaction Mixture Against the Extent of Reaction Is a Minimum at Equilibrium
972(2)
24-5. The Ratio of the Reaction Quotient to the Equilibrium Constant Determines the Direction in which a Reaction Will Proceed
974(2)
24-6. The Sign of XXX(r)G And Not That of XXX(r)G(XXX) Determines the Direction of Reaction Spontaneity
976(1)
24-7. The Variation of an Equilibrium Constant with Temperature Is Given by the Van't Hoff Equation
977(4)
24-8. We Can Calculate Equilibrium Constants in Terms of Partition Functions
981(4)
24-9. Molecular Partition Functions and Related Thermodynamic Data Are Extensively Tabulated
985(7)
24-10. Equilibrium Constants for Real Gases Are Expressed in Terms of Partial Fugacities
992(2)
24-11. Thermodynamic Equilibrium Constants Are Expressed in Terms of Activities
994(4)
Problems
998(13)
CHAPTER 25 / The Kinetic Theory of Gases
1011(36)
25-1. The Average Translational Kinetic Energy of the Molecules in a Gas Is Directly Proportional to the Kelvin Temperature
1011(5)
25-2. The Distribution of the Components of Molecular Speeds Are Described by a Gaussian Distribution
1016(6)
25-3. The Distribution of Molecular Speeds Is Given by the Maxwell-Boltzmann Distribution
1022(4)
25-4. The Frequency of Collisions That a Gas Makes with a Wall Is Proportional to Its Number Density and to the Average Molecular Speed
1026(3)
25-5. The Maxwell-Boltzmann Distribution Has Been Verified Experimentally
1029(2)
25-6. The Mean Free Path Is the Average Distance a Molecule Travels Between Collisions
1031(6)
25-7. The Rate of a Gas-Phase Chemical Reaction Depends Upon the Rate of Collisions in which the Relative Kinetic Energy Exceeds Some Critical Value
1037(2)
Problems
1039(8)
CHAPTER 26 / Chemical Kinetics I: Rate Laws
1047(44)
26-1. The Time Dependence of a Chemical Reaction Is Described by a Rate Law
1048(3)
26-2. Rate Laws Must Be Determined Experimentally
1051(3)
26-3. First-Order Reactions Show an Exponential Decay of Reactant Concentration with Time
1054(4)
26-4. The Rate Laws for Different Reaction Orders Predict Different Behaviors for the Time-Dependent Reactant Concentration
1058(4)
26-5. Reactions Can Also Be Reversible
1062(1)
26-6. The Rate Constants of a Reversible Reaction Can Be Determined Using Relaxation Methods
1062(9)
26-7. Rate Constants Are Usually Strongly Temperature Dependent
1071(4)
26-8. Transition-State Theory Can Be Used to Estimate Reaction Rate Constants
1075(4)
Problems
1079(12)
CHAPTER 27 / Chemical Kinetics II: Reaction Mechanisms
1091(48)
27-1. A Mechanism is a Sequence of Single-Step Chemical Reactions called Elementary Reactions
1092(1)
27-2. 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
1093(3)
27-3. When Are Consecutive and Single-Step Reactions Distinguishable?
1196
27-4. The Steady-State Approximation Simplifies Rate Expressions by Assuming That d[I]/dt = 0, where I Is a Reaction Intermediate
1101(2)
27-5. The Rate Law for a Complex Reaction Does Not Imply a Unique Mechanism
1103(5)
27-6. The Lindemann Mechanism Explains How Unimolecular Reactions Occur
1108(5)
27-7. Some Reaction Mechanisms Involve Chain Reactions
1113(3)
27-8. A Catalyst Affects the Mechanism and Activation Energy of a Chemical Reaction
1116(3)
27-9. The Michaelis-Menten Mechanism Is a Reaction Mechanism for Enzyme Catalysis
1119(4)
Problems
1123(16)
CHAPTER 28 / Gas-Phase Reaction Dynamics
1139(42)
28-1. The Rate of a Bimolecular Gas-Phase Reaction Can Be Calculated Using Hard-Sphere Collision Theory and an Energy-Dependent Reaction Cross Section
1139(5)
28-2. A Reaction Cross Section Depends upon the Impact Parameter
1144(3)
28-3. The Rate Constant for a Gas-Phase Chemical Reaction May Depend on the Orientations of the Colliding Molecules
1147(1)
28-4. The Internal Energy of the Reactants Can Affect the Cross Section of a Reaction
1148(1)
28-5. A Reactive Collision Can Be Described in a Center-of-Mass Coordinate System
1149(5)
28-6. Reactive Collisions Can Be Studied Using Crossed Molecular Beam Machines
1154(2)
28-7. The Reaction F(g) + D(2)(g) XXX DF(g) + D(g) Can Produce Vibrationally Excited DF(g) Molecules
1156(2)
28-8. The Velocity and Angular Distribution of the Products of a Reactive Collision Provide a Molecular Picture of the Chemical Reaction
1158(7)
28-9. Not All Gas-Phase Chemical Reactions Are Rebound Reactions
1165(3)
28-10. The Potential-Energy Surface for the Reaction F(g) + D(2)(g) XXX DF(g) + D(g) Can Be Calculated Using Quantum Mechanics
1168(3)
Problems
1171(10)
CHAPTER 29 / Solids and Surface Chemistry
1181(56)
29-1. The Unit Cell Is the Fundamental Building Block of a Crystal
1181(1)
29-2. The Orientation of a Lattice Plane Is Described by Its Miller Indices
1181(10)
29-3. The Spacing Between Lattice Planes Can Be Determined from X-Ray Diffraction Measurements
1191(7)
29-4. The Total Scattering Intensity Is Related to the Periodic Structure of the Electron Density in the Crystal
1198(5)
29-5. The Structure Factor and the Electron Density Are Related by a Fourier Transform
1203(2)
29-6. A Gas Molecule Can Physisorb or Chemisorb to a Solid Surface
1205(2)
29-7. Isotherms Are Plots of Surface Coverage as a Function of Gas Pressure at Constant Temperature
1207(6)
29-8. The Langmuir Isotherm Can Be Used to Derive Rate Laws for Surface-Catalyzed Gas-Phase Reactions
1213(4)
29-9. The Structure of a Surface is Different from That of a Bulk Solid
1217(2)
29-10. The Reaction Between H(2)(g) and N(2)(g) to Make NH(3)(g) Can Be Surface Catalyzed
1219(2)
Problems
1221(16)
Answers to the Numerical Problems 1237(20)
Illustration Credits
1257(2)
Index 1259

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Intimidating April 22, 2014
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