Physical Chemistry

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ISBN: 9780125083454 | 0125083459
Cover: Hardcover
Copyright: 3/21/2000

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This new edition of Robert G. Mortimer's Physical Chemistry has been thoroughly revised for use in a full year course in modern physical chemistry. In this edition, Mortimer has included recent developments in the theories of chemical reaction kinetics and molecular quantum mechanics, as well as in the experimental study of extremely rapid chemical reactions. While Mortimer has made substantial improvements in the selection and updating of topics, he has retained the clarity of presentation, the integration of description and theory, and the level of rigor that made the first edition so successful.

Periodic Table

xvii

Information Tables

xviii

Systems, States, and Processes

(20)

Scientific Inquiry

(1)

Systems and States

(3)

Units of Measurements. SI Units

(2)

State Functions

(3)

The Relationship between Macrostates and Microstates

(5)

Processes

(5)

Problems

(2)

The Equilibrium Macroscopic States of Gases and Liquids

(24)

Mathematical Functions and the Equilibrium Macroscopic State of a Simple System

(3)

Real Liquids and Solids

(3)

Real Gases

(4)

The Coexistence of Phases and the Critical Point

(13)

Problems

(4)

Work, Heat, and Energy: The First Law of Thermodynamics

(50)

Work and the State of a System

(7)

Heat

(2)

Internal Energy. The First Law of Thermodynamics

(3)

Calculation of Amounts of Heat and Energy Changes

(10)

Enthalpy---A Convenience Variable

(6)

Calculation of Enthalpy Changes for Non-Chemical Processes

(3)

Calculation of Enthalpy Changes for a Class of Chemical Reactions

(8)

Energy Changes of Chemical Reactions

(10)

Problems

(5)

The Second and Third Laws of Thermodynamics: Entropy

(36)

The Second Law of Thermodynamics and the Carnot Heat Engine

(6)

The Mathematical Statement of the Second Law. Entropy

102

(5)

The Calculation of Entropy Changes

107

(9)

Statistical Entropy

116

(3)

The Third Law of Thermodynamics and Absolute Entropies

119

(12)

Problems

125

(6)

The Thermodynamics of Real Systems

131

(36)

Criteria for Spontaneous Processes and for Equilibrium. The Gibbs and Helmholtz Energies

132

(5)

Fundamental Relations for Closed Simple Systems

137

(5)

Gibbs Energy Calculations

142

(4)

The Description of Multicomponent and Open Systems

146

(6)

Additional Useful Thermodynamic Identities

152

(4)

Euler's Theorem and the Gibbs--Duhem Relation

156

(11)

Problems

162

(5)

Phase Equilibrium

167

(32)

The Fundamental Fact of Phase Equilibrium

168

(2)

The Gibbs Phase Rule

170

(4)

Phase Equilibrium in a One-Component System

174

(6)

The Gibbs Energy and Phase Transitions

180

(4)

Surface Structure and Thermodynamics

184

(7)

Surfaces in Multicomponent Systems

191

(8)

Problems

195

(4)

Multicomponent Systems

199

(56)

Ideal Solutions

200

(9)

Henry's Law and Dilute Nonelectrolyte Solutions

209

(7)

The Activity and the Description of General Systems

216

(12)

Activity Coefficients in Electrolyte Solutions

228

(6)

Phase Diagrams for Nonideal Mixtures

234

(10)

Colligative Properties

244

(11)

Problems

250

(5)

The Thermodynamics of Chemical Equilibrium

255

(36)

Gibbs Energy Changes and Equilibria of Chemical Reactions. The Equilibrium Constant

256

(5)

Reactions Involving Gases and Pure Substances

261

(3)

Chemical Equilibrium in Solution

264

(2)

Equilibria in Solutions of Strong Electrolytes

266

(4)

Acid--Base Equilibrium Calculations

270

(6)

Temperature Dependence of Equilibrium Constants. The Principle of Le Chatelier

276

(4)

Chemical Reactions and Biological Systems

280

(11)

Problems

285

(6)

The Thermodynamics of Electrical Systems

291

(28)

The Chemical Potential and the Electric Potential

292

(1)

Electrochemical Cells at Equilibrium

293

(7)

Half-Cell Potentials and Cell Potentials

300

(7)

The Determination of Activity Coefficients of Electrolytes

307

(5)

Thermodynamic Information from Electrochemistry

312

(7)

Problems

315

(4)

Gas Kinetic Theory. The Molecular Theory of Dilute Gases at Equilibrium

319

(46)

The Model System for a Dilute Gas

320

(4)

The Velocity Probability Distribution

324

(9)

The Distribution of Molecular Speeds

333

(4)

The Pressure of an Ideal Gas

337

(4)

Wall Collisions and Effusion

341

(2)

The Model System with Potential Energy

343

(4)

The Hard-Sphere Gas

347

(10)

The Molecular Structure of Liquids

357

(8)

Problems

359

(6)

Transport Processes

365

(36)

The Macroscopic Description of Nonequilibrium States

366

(2)

Transport Processes

368

(12)

Transport Processes in the Hard-Sphere Gas

380

(5)

The Structure of Liquids and Transport Processes in Liquids

385

(5)

Transport in Electrolyte Solutions

390

(11)

Problems

397

(4)

The Rates of Chemical Reactions

401

(34)

The Macroscopic Description of Chemically Reacting Systems

402

(2)

Forward Reactions with one Reactant

404

(8)

Forward Reactions with More Than One Reactant

412

(5)

Inclusion of a Reverse Reaction. Chemical Equilibrium

417

(3)

Consecutive Reactions and Competing Reactions

420

(4)

The Experimental Study of Fast Reactions

424

(11)

Problems

430

(5)

Chemical Reaction Mechanisms

435

(58)

Reaction Mechanisms and Elementary Processes in Gases

436

(2)

Elementary Reactions in Liquid Solutions

438

(6)

The Temperature Dependence of Rate Constants. The Collision Theory of Bimolecular Gaseous Reactions

444

(6)

Reaction Mechanisms and Rate Laws

450

(13)

Some Additional Mechanisms, Including Chain and Photochemical Mechanisms. Competing Mechanisms

463

(6)

Catalysis

469

(12)

Experimental Molecular Study of Chemical Reactions

481

(12)

Problems

487

(6)

The Principles of Quantum Mechanics. I. Classical Waves and the Schrodinger Equation

493

(46)

Classical Mechanics

494

(3)

Classical Waves

497

(10)

The Old Quantum Theory

507

(7)

De Broglie Waves and the Schrodinger Equation

514

(8)

The Particle in a Box. The Free Particle

522

(9)

The Harmonic Oscillator

531

(8)

Problems

534

(5)

The Principles of Quantum Mechanics. II. The Postulates of Quantum Mechanics

539

(34)

The First Two Postulates of Quantum Mechanics

540

(1)

Mathematical Operators

541

(5)

Postulate 3. Mathematical Operators Corresponding to Mechanical Variables in Quantum Mechanics

546

(3)

Postulate 4. Expectation Values

549

(16)

Postulate 5. The Determination of the State of a System

565

(8)

Problems

569

(4)

The Electronic States of Atoms. I. The Hydrogen Atom and the Simple Orbital Approximation for Multielectron Atoms

573

(46)

The Hydrogen Atom and the Central Force System. Angular Momentum

574

(8)

The Wave Functions of the Hydrogen Atom

582

(15)

The Helium Atom in the ``Zero-Order'' Orbital Approximation

597

(13)

Atoms with More Than Two Electrons

610

(9)

Problems

616

(3)

The Electronic States of Atoms. II. Higher-Order Approximations for Multielectron Atoms

619

(28)

The Variation Method and Its Application to the Helium Atom

620

(5)

The Perturbation Method and Its Application to the Helium Atom

625

(2)

The Self-Consistent Field Method

627

(2)

Excited States of the Helium Atom

629

(3)

Atoms with More than Two Electrons

632

(15)

Problems

642

(5)

The Electronic States of Molecules

647

(74)

The Born--Oppenheimer Approximation. The Hydrogen Molecule Ion

648

(7)

LCAO-MOs---Molecular Orbitals That Are Linear Combinations of Atomic Orbitals

655

(5)

Homonuclear Diatomic Molecules

660

(12)

Heteronuclear Diatomic Molecules

672

(10)

Symmetry in Polyatomic Molecules. Groups of Symmetry Operators

682

(8)

Electronic Structure of Polyatomic Molecules

690

(19)

More Advanced Treatments of Molecular Electronic Structure

709

(12)

Problems

715

(6)

Translational, Rotational, and Vibrational States of Atoms and Molecules

721

(30)

Translational Motions of Atoms

722

(2)

The Nonelectronic States of Diatomic Molecules

724

(12)

Rotation and Vibration in Polyatomic Molecules

736

(7)

The Equilibrium Populations of Molecular States

743

(8)

Problems

746

(5)

Spectroscopy and Photochemistry

751

(66)

Emmission/Absorption Spectroscopy and Energy Levels

752

(9)

The Spectra of Atoms

761

(1)

Rotational and Vibrational Spectra of Diatomic Molecules

762

(7)

Electronic Spectra of Diatomic Molecules

769

(2)

Spectra of Polyatomic Molecules

771

(4)

Fluorescence, Phosphorescence, and Photochemistry

775

(6)

Other Types of Spectroscopy

781

(11)

Magnetic Resonance Spectroscopy

792

(14)

Fourier Transform Spectroscopy

806

(11)

Problems

811

(6)

Equilibrium Statistical Mechanics

817

(80)

The Quantum Statistical Mechanics of a Sample System of Four Harmonic Oscillators

818

(5)

The Probability Distribution for a Dilute Gas

823

(5)

The Probability Distribution and the Molecular Partition Function

828

(8)

The Calculation of Molecular Partition Functions

836

(9)

Calculations of Thermodynamic Functions of Dilute Gases

845

(13)

Chemical Equilibrium in Dilute Gases

858

(4)

The Activated Complex Theory of Bimolecular Chemical Reactions in Dilute Gases

862

(10)

The Canonical Ensemble

872

(9)

Classical Statistical Mechanics

881

(16)

Problems

892

(5)

The Structure of Solids and Liquids

897

(50)

General Features of Solids

898

(8)

Crystal Vibrations

906

(7)

The Electronic Structure of Crystalline Solids

913

(7)

The Structure of Liquids

920

(7)

Polymer Formation and Conformation

927

(9)

Rubber Elasticity

936

(4)

Polymers in Solution

940

(7)

Problems

943

(4)

Some Additional Theories of Nonequilibrium Processes

947

(30)

Theories of Unimolecular Chemical Reactions

948

(4)

The Molecular Case History of a Chemical Reaction

952

(2)

Theories of Transport Processes in Fluid Systems

954

(4)

Nonequilibrium Electrochemistry

958

(12)

Electrical Conductivity in Solids

970

(7)

Problems

975

(2)

Appendixes

977

(120)

A. Tables of Numerical Data

977

(24)

B. Some Useful Mathematics

1001

(20)

C. A Short Table of Integrals

1021

(4)

D. Classical Mechanics

1025

(6)

E. Some Derivations of Thermodynamic Formulas and Methods

1031

(6)

F. Some Mathematics in Quantum Mechanics

1037

(8)

G. The Perturbation Method

1045

(2)

H. The Huckel Method

1047

(4)

I. Matrix Representations of Groups

1051

(10)

J. Symbols Used in This Book

1061

(8)

K. Answers to Selected Exercises and Problems

1069

(28)

Additional Reading

1097

(8)

Index

1105

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Physical Chemistry

Summary

Table of Contents

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