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Physical Chemistry
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ISBN-10 : 0935702997
ISBN-13 : 9780935702996
Physical Chemistry [Paperback] 중고
저자 McQuarrie, Donald A. | 출판사 Univ. Science Books
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Unlike most physical chemistry texts, modern physical chemistry research is based on quantum mechanics, and this state-of-the-art approach is the one adopted by McQuarrie and Simon. Quantum theory is introduced at the outset, and the molecular viewpoint of quantum chemistry informs the authors' investigation of physical chemistry's other main topic ares - thermodynamics and chemical kinetics. The book also includes examples of applications in NMR spectroscopy, lasers, photochemistry, gas-reaction dynamics and other current research topics. "At last there is a book written from a modern perspective! A real winner!" George C. Fields, Lake Forest College

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목차

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

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