Physical Chemistry, 6th Edition

lev38627_fm.qxd 4/9/08 12:32 PM Page i PHYSICAL CHEMISTRY lev38627_fm.qxd 4/9/08 12:32 PM Page ii lev38627_fm.qxd 4/9/08 12:32 PM Page iii PHYSICAL CHEMISTRY Sixth Edition Ira N. Levine Chemistry Department Brooklyn College City University of New York Brooklyn, New York lev38627_fm.qxd 4/9/08 12:32 PM Page iv 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. 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 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) 1. Chemistry, Physical and theoretical. I. Title. QD453.3.L48 2009 541-- dc22 2008002821 www.mhhe.com lev38627_fm.qxd 4/9/08 12:32 PM Page v To the memory of my mother and my father lev38627_fm.qxd 4/9/08 12:32 PM Page vi Table of Contents Preface Chapter 1 xiv THERMODYNAMICS 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 1.10 Chapter 2 Chapter 3 vi Physical Chemistry Thermodynamics Temperature The Mole Ideal Gases Differential Calculus Equations of State Integral Calculus Study Suggestions Summary 1 1 3 6 9 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