Physical Chemistry

1013 Pages·2008·12.398 MB·English

by  Ira Levine

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PHYSICAL CHEMISTRY
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PHYSICAL CHEMISTRY
Sixth Edition
Ira N. Levine
Chemistry Department
Brooklyn College
City University of New York
Brooklyn, New York
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PHYSICAL CHEMISTRY, SIXTH EDITION
Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the
Americas,NewYork,NY10020.Copyright©2009byTheMcGraw-HillCompanies,Inc.Allrights
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Some ancillaries, including electronic and print components, may not be available to customers outside
the United States.
This book is printed on recycled, acid-free paper containing 10% postconsumer waste.
1 2 3 4 5 6 7 8 9 0 QPD/QPD 0 9 8
ISBN 978–0–07–253862–5
MHID 0–07–253862–7
Publisher: Thomas Timp
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Library of Congress Cataloging-in-Publication Data
Levine, Ira N.
Physical chemistry / Ira N. Levine. -- 6th ed.
p. cm.
Includes index.
ISBN 978–0–07–253862–5 --- ISBN 0–07–253862–7 (hard copy : alk. paper) 1. Chemistry, Physical
and theoretical. I. Title.
QD453.3.L48 2009
541-- dc22 2008002821
www.mhhe.com
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To the memory of my mother and my father
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Table of Contents
Preface xiv
Chapter 1 THERMODYNAMICS 1
1.1 Physical Chemistry 1
1.2 Thermodynamics 3
1.3 Temperature 6
1.4 The Mole 9
1.5 Ideal Gases 10
1.6 Differential Calculus 17
1.7 Equations of State 22
1.8 Integral Calculus 25
1.9 Study Suggestions 30
1.10 Summary 32
Chapter 2 THE FIRST LAW OF THERMODYNAMICS 37
2.1 Classical Mechanics 37
2.2 P-VWork 42
2.3 Heat 46
2.4 The First Law of Thermodynamics 47
2.5 Enthalpy 52
2.6 Heat Capacities 53
2.7 The Joule and Joule–Thomson Experiments 55
2.8 Perfect Gases and the First Law 58
2.9 Calculation of First-Law Quantities 62
2.10 State Functions and Line Integrals 65
2.11 The Molecular Nature of Internal Energy 67
2.12 Problem Solving 70
2.13 Summary 73
Chapter 3 THE SECOND LAW OF THERMODYNAMICS 78
3.1 The Second Law of Thermodynamics 78
3.2 Heat Engines 80
3.3 Entropy 85
3.4 Calculation of Entropy Changes 87
3.5 Entropy, Reversibility, and Irreversibility 93
3.6 The Thermodynamic Temperature Scale 96
3.7 What Is Entropy? 97
3.8 Entropy, Time, and Cosmology 103
3.9 Summary 104
vi
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Chapter 4 MATERIAL EQUILIBRIUM 109
Table of Contents
4.1 Material Equilibrium 109
4.2 Entropy and Equilibrium 110
4.3 The Gibbs and Helmholtz Energies 112
4.4 Thermodynamic Relations for a System
in Equilibrium 115
4.5 Calculation of Changes in State Functions 123
4.6 Chemical Potentials and Material Equilibrium 125
4.7 Phase Equilibrium 129
4.8 Reaction Equilibrium 132
4.9 Entropy and Life 134
4.10 Summary 135
Chapter 5 STANDARD THERMODYNAMIC FUNCTIONS
OF REACTION 140
5.1 Standard States of Pure Substances 140
5.2 Standard Enthalpy of Reaction 141
5.3 Standard Enthalpy of Formation 142
5.4 Determination of Standard Enthalpies
of Formation and Reaction 143
5.5 Temperature Dependence of Reaction Heats 151
5.6 Use of a Spreadsheet to Obtain a Polynomial Fit 153
5.7 Conventional Entropies and the Third Law 155
5.8 Standard Gibbs Energy of Reaction 161
5.9 Thermodynamics Tables 163
5.10 Estimation of Thermodynamic Properties 165
5.11 The Unattainability of Absolute Zero 168
5.12 Summary 169
Chapter 6 REACTION EQUILIBRIUM IN IDEAL GAS MIXTURES 174
6.1 Chemical Potentials in an Ideal Gas Mixture 175
6.2 Ideal-Gas Reaction Equilibrium 177
6.3 Temperature Dependence
of the Equilibrium Constant 182
6.4 Ideal-Gas Equilibrium Calculations 186
6.5 Simultaneous Equilibria 191
6.6 Shifts in Ideal-Gas Reaction Equilibria 194
6.7 Summary 198
Chapter 7 ONE-COMPONENT PHASE EQUILIBRIUM
AND SURFACES 205
7.1 The Phase Rule 205
7.2 One-Component Phase Equilibrium 210
7.3 The Clapeyron Equation 214
7.4 Solid–Solid Phase Transitions 221
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7.5 Higher-Order Phase Transitions 225
Table of Contents
7.6 Surfaces and Nanoparticles 227
7.7 The Interphase Region 227
7.8 Curved Interfaces 231
7.9 Colloids 234
7.10 Summary 237
Chapter 8 REAL GASES 244
8.1 Compression Factors 244
8.2 Real-Gas Equations of State 245
8.3 Condensation 247
8.4 Critical Data and Equations of State 249
8.5 Calculation of Liquid–Vapor Equilibria 252
8.6 The Critical State 254
8.7 The Law of Corresponding States 255
8.8 Differences Between Real-Gas and Ideal-Gas
Thermodynamic Properties 256
8.9 Taylor Series 257
8.10 Summary 259
Chapter 9 SOLUTIONS 263
9.1 Solution Composition 263
9.2 Partial Molar Quantities 264
9.3 Mixing Quantities 270
9.4 Determination of Partial Molar Quantities 272
9.5 Ideal Solutions 275
9.6 Thermodynamic Properties of Ideal Solutions 278
9.7 Ideally Dilute Solutions 282
9.8 Thermodynamic Properties
of Ideally Dilute Solutions 283
9.9 Summary 287
Chapter 10 NONIDEAL SOLUTIONS 294
10.1 Activities and Activity Coefficients 294
10.2 Excess Functions 297
10.3 Determination of Activities
and Activity Coefficients 298
10.4 Activity Coefficients on the Molality and Molar
Concentration Scales 305
10.5 Solutions of Electrolytes 306
10.6 Determination of Electrolyte Activity Coefficients 310
10.7 The Debye–Hückel Theory of Electrolyte Solutions 311
10.8 Ionic Association 315
10.9 Standard-State Thermodynamic Properties
of Solution Components 318
10.10 Nonideal Gas Mixtures 321
10.11 Summary 324
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Chapter 11 REACTION EQUILIBRIUM IN NONIDEAL SYSTEMS 330
Table of Contents
11.1 The Equilibrium Constant 330
11.2 Reaction Equilibrium in Nonelectrolyte Solutions 331
11.3 Reaction Equilibrium in Electrolyte Solutions 332
11.4 Reaction Equilibria Involving Pure Solids
or Pure Liquids 337
11.5 Reaction Equilibrium in Nonideal Gas Mixtures 340
11.6 Computer Programs for Equilibrium Calculations 340
11.7 Temperature and Pressure Dependences of the
Equilibrium Constant 341
11.8 Summary of Standard States 343
11.9 Gibbs Energy Change for a Reaction 343
11.10 Coupled Reactions 345
11.11 Summary 347
Chapter 12 MULTICOMPONENT PHASE EQUILIBRIUM 351
12.1 Colligative Properties 351
12.2 Vapor-Pressure Lowering 351
12.3 Freezing-Point Depression
and Boiling-Point Elevation 352
12.4 Osmotic Pressure 356
12.5 Two-Component Phase Diagrams 361
12.6 Two-Component Liquid–Vapor Equilibrium 362
12.7 Two-Component Liquid–Liquid Equilibrium 370
12.8 Two-Component Solid–Liquid Equilibrium 373
12.9 Structure of Phase Diagrams 381
12.10 Solubility 381
12.11 Computer Calculation of Phase Diagrams 383
12.12 Three-Component Systems 385
12.13 Summary 387
Chapter 13 ELECTROCHEMICAL SYSTEMS 395
13.1 Electrostatics 395
13.2 Electrochemical Systems 398
13.3 Thermodynamics of Electrochemical Systems 401
13.4 Galvanic Cells 403
13.5 Types of Reversible Electrodes 409
13.6 Thermodynamics of Galvanic Cells 412
13.7 Standard Electrode Potentials 417
13.8 Liquid-Junction Potentials 421
13.9 Applications of EMF Measurements 422
13.10 Batteries 426
13.11 Ion-Selective Membrane Electrodes 427
13.12 Membrane Equilibrium 429
13.13 The Electrical Double Layer 430
13.14 Dipole Moments and Polarization 431
13.15 Bioelectrochemistry 435
13.16 Summary 436