www.elsolucionario.net www.elsolucionario.net 4/9/08 12:32 PM Page i www.elsolucionario.net PHYSICAL CHEMISTRY www.elsolucionario.net lev38627_fm.qxd 4/9/08 12:32 PM Page ii www.elsolucionario.net www.elsolucionario.net lev38627_fm.qxd 4/9/08 12:32 PM Page iii www.elsolucionario.net PHYSICAL CHEMISTRY Sixth Edition Ira N Levine Chemistry Department Brooklyn College City University of New York Brooklyn, New York www.elsolucionario.net lev38627_fm.qxd lev38627_fm.qxd 4/9/08 12:32 PM Page iv www.elsolucionario.net PHYSICAL CHEMISTRY, SIXTH EDITION Published by McGraw-Hill, a business unit of The McGraw-Hill Companies, Inc., 1221 Avenue of the Americas, New York, NY 10020 Copyright © 2009 by The McGraw-Hill Companies, Inc All rights reserved Previous editions © 2002, 1995, 1988, 1983, and 1978 No part of this publication may be reproduced or distributed in any form or by any means, or stored in a database or retrieval system, without the prior written consent of The McGraw-Hill Companies, Inc., including, but not limited to, in any network or other electronic storage or transmission, or broadcast for distance learning Some ancillaries, including electronic and print components, may not be available to customers outside the United States QPD/QPD ISBN 978–0–07–253862–5 MHID 0–07–253862–7 Publisher: Thomas Timp Senior Sponsoring Editor: Tamara L Hodge Director of Development: Kristine Tibbetts Senior Developmental Editor: Shirley R Oberbroeckling Marketing Manager: Todd L Turner Project Coordinator: Melissa M Leick Senior Production Supervisor: Sherry L Kane Senior Designer: David W Hash Cover Designer: Ron E Bissell, Creative Measures Design Inc Supplement Producer: Melissa M Leick Compositor: ICC Macmillan Inc Typeface: 10.5/12 Times Printer: Quebecor World Dubuque, IA 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) Chemistry, Physical and theoretical I Title QD453.3.L48 2009 541 dc22 2008002821 www.mhhe.com www.elsolucionario.net This book is printed on recycled, acid-free paper containing 10% postconsumer waste 4/9/08 12:32 PM Page v www.elsolucionario.net To the memory of my mother and my father www.elsolucionario.net lev38627_fm.qxd lev38627_fm.qxd 4/9/08 12:32 PM Page vi www.elsolucionario.net Table of Contents Chapter xiv THERMODYNAMICS 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.10 Chapter Chapter vi Physical Chemistry Thermodynamics Temperature The Mole Ideal Gases Differential Calculus Equations of State Integral Calculus Study Suggestions Summary 1 10 17 22 25 30 32 THE FIRST LAW OF THERMODYNAMICS 37 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.11 2.12 2.13 37 42 46 47 52 53 55 58 62 65 67 70 73 Classical Mechanics P-V Work Heat The First Law of Thermodynamics Enthalpy Heat Capacities The Joule and Joule–Thomson Experiments Perfect Gases and the First Law Calculation of First-Law Quantities State Functions and Line Integrals The Molecular Nature of Internal Energy Problem Solving Summary THE SECOND LAW OF THERMODYNAMICS 78 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 78 80 85 87 93 96 97 103 104 The Second Law of Thermodynamics Heat Engines Entropy Calculation of Entropy Changes Entropy, Reversibility, and Irreversibility The Thermodynamic Temperature Scale What Is Entropy? Entropy, Time, and Cosmology Summary www.elsolucionario.net Preface lev38627_fm.qxd 4/9/08 12:32 PM Page vii www.elsolucionario.net vii MATERIAL EQUILIBRIUM 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 Chapter STANDARD THERMODYNAMIC FUNCTIONS OF REACTION 5.1 5.2 5.3 5.4 140 REACTION EQUILIBRIUM IN IDEAL GAS MIXTURES 174 6.4 6.5 6.6 6.7 Chapter 115 123 125 129 132 134 135 143 151 153 155 161 163 165 168 169 6.1 6.2 6.3 Chemical Potentials in an Ideal Gas Mixture Ideal-Gas Reaction Equilibrium Temperature Dependence of the Equilibrium Constant Ideal-Gas Equilibrium Calculations Simultaneous Equilibria Shifts in Ideal-Gas Reaction Equilibria Summary ONE-COMPONENT PHASE EQUILIBRIUM AND SURFACES 7.1 7.2 7.3 7.4 The Phase Rule One-Component Phase Equilibrium The Clapeyron Equation Solid–Solid Phase Transitions Table of Contents 109 110 112 Standard States of Pure Substances Standard Enthalpy of Reaction Standard Enthalpy of Formation Determination of Standard Enthalpies of Formation and Reaction Temperature Dependence of Reaction Heats Use of a Spreadsheet to Obtain a Polynomial Fit Conventional Entropies and the Third Law Standard Gibbs Energy of Reaction Thermodynamics Tables Estimation of Thermodynamic Properties The Unattainability of Absolute Zero Summary 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 Chapter Material Equilibrium Entropy and Equilibrium The Gibbs and Helmholtz Energies Thermodynamic Relations for a System in Equilibrium Calculation of Changes in State Functions Chemical Potentials and Material Equilibrium Phase Equilibrium Reaction Equilibrium Entropy and Life Summary 109 140 141 142 175 177 182 186 191 194 198 205 205 210 214 221 www.elsolucionario.net Chapter lev38627_fm.qxd 4/9/08 12:32 PM Page viii www.elsolucionario.net viii Chapter REAL GASES 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 8.10 Chapter Compression Factors Real-Gas Equations of State Condensation Critical Data and Equations of State Calculation of Liquid–Vapor Equilibria The Critical State The Law of Corresponding States Differences Between Real-Gas and Ideal-Gas Thermodynamic Properties Taylor Series Summary SOLUTIONS 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 Chapter 10 Higher-Order Phase Transitions Surfaces and Nanoparticles The Interphase Region Curved Interfaces Colloids Summary Solution Composition Partial Molar Quantities Mixing Quantities Determination of Partial Molar Quantities Ideal Solutions Thermodynamic Properties of Ideal Solutions Ideally Dilute Solutions Thermodynamic Properties of Ideally Dilute Solutions Summary NONIDEAL SOLUTIONS 10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.8 10.9 10.10 10.11 Activities and Activity Coefficients Excess Functions Determination of Activities and Activity Coefficients Activity Coefficients on the Molality and Molar Concentration Scales Solutions of Electrolytes Determination of Electrolyte Activity Coefficients The Debye–Hückel Theory of Electrolyte Solutions Ionic Association Standard-State Thermodynamic Properties of Solution Components Nonideal Gas Mixtures Summary 225 227 227 231 234 237 244 244 245 247 249 252 254 255 256 257 259 263 263 264 270 272 275 278 282 283 287 294 294 297 298 305 306 310 311 315 318 321 324 www.elsolucionario.net 7.5 7.6 7.7 7.8 7.9 7.10 Table of Contents ... Mechanics The Canonical Ensemble Canonical Partition Function for a System of Noninteracting Particles Canonical Partition Function of a Pure Ideal Gas The Boltzmann Distribution Law for Noninteracting... equation to solving problems To use an equation properly, one must understand it Understanding involves not only knowing what the symbols stand for but also knowing when the equation applies and... equation to solving problems To use an equation properly, one must understand it Understanding involves not only knowing what the symbols stand for but also knowing when the equation applies and