▼ Eighth Edition Chemistry Principles and Reactions William L. Masterton University of Connecticut Cecile N. Hurley University of Connecticut Australia ● Brazil ● Mexico ● Singapore ● United Kingdom ● United States Copyright 2016 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it. This is an electronic version of the print textbook. Due to electronic rights restrictions, some third party content may be suppressed. Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. The publisher reserves the right to remove content from this title at any time if subsequent rights restrictions require it. For valuable information on pricing, previous editions, changes to current editions, and alternate formats, please visit www.cengage.com/highered to search by ISBN#, author, title, or keyword for materials in your areas of interest. Important Notice: Media content referenced within the product description or the product text may not be available in the eBook version. Copyright 2016 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it. Chemistry: Principles and Reactions, © 2016, 2012 Cengage Learning Eighth Edition WCN: 02-200-203 William L. Masterton, Cecile N. Hurley ALL RIGHTS RESERVED. No part of this work covered by the copyright herein Product Director: Mary Finch may be reproduced, transmitted, stored, or used in any form or by any means Product Manager: Lisa Lockwood graphic, electronic, or mechanical, including but not limited to photocopying, Content Developer: Ed Dodd recording, scanning, digitizing, taping, Web distribution, information networks, Associate Content Developer: Elizabeth Woods or information storage and retrieval systems, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without the prior Product Assistant: Karolina Kiwak written permission of the publisher. Media Developer: Brendan Killion, Lisa Weber Marketing Manager: Janet del Mundo For product information and technology assistance, contact us at Content Project Manager: Jennifer Risden Cengage Learning Customer & Sales Support, 1-800-354-9706. For permission to use material from this text or product, Art Director: Maria Epes submit all requests online at www.cengage.com/permissions. Manufacturing Planner: Judy Inouye Further permissions questions can be e-mailed to Production Service: MPS Limited [email protected]. Photo Researcher: Lumina Datamatics Text Researcher: Lumina Datamatics Library of Congress Control Number: 2014943694 Copy Editor: Chris Sabooni Student Edition: ISBN: 978-1-305-07937-3 Text Designer: Delgado and Company Cover Designer: Irene Morris Loose-leaf Edition: ISBN: 978-1-305-63261-5 Cover Image: © Dmitriev Lidiya/ Shutterstock.com Interior Design Image: © wongwean/ Cengage Learning Shutterstock.com 20 Channel Center Street Boston, MA 02210 Compositor: MPS Limited USA Cengage Learning is a leading provider of customized learning solutions with office locations around the globe, including Singapore, the United Kingdom, Australia, Mexico, Brazil, and Japan. Locate your local office at www.cengage.com/global. Cengage Learning products are represented in Canada by Nelson Education, Ltd. To learn more about Cengage Learning Solutions, visit www.cengage.com. Purchase any of our products at your local college store or at our preferred online store www.cengagebrain.com. Printed in the United States of America Print Number: 01 Print Year: 2014 Copyright 2016 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it. T o Jim, Joe, and Regina They also serve who only stand and wait. —John Milton On His Blindness Copyright 2016 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it. Brief Contents 1 Matter and Measurements 1 2 Atoms, Molecules, and Ions 22 3 Mass Relations in Chemistry; Stoichiometry 51 4 Reactions in Aqueous Solution 74 5 Gases 95 6 Electronic Structure and the Periodic Table 124 7 Covalent Bonding 155 8 Thermochemistry 187 9 Liquids and Solids 216 10 Solutions 246 11 Rate of Reaction 274 12 Gaseous Chemical Equilibrium 306 13 Acids and Bases 331 14 Equilibria in Acid-Base Solutions 360 15 Complex Ion and Precipitation Equilibria 385 16 Spontaneity of Reaction 406 17 Electrochemistry 430 18 Nuclear Reactions 465 19 Complex Ions 487 20 Chemistry of the Metals 506 21 Chemistry of the Nonmetals 525 22 Organic Chemistry 547 23 Organic Polymers, Natural and Synthetic 576 Appendix 1 Units, Constants, and Reference Data 599 Appendix 2 Properties of the Elements 605 Appendix 3 Exponents and Logarithms 607 Appendix 4 Molecular Orbitals 613 Appendix 5 Answers to Even-Numbered and Challenge Questions and Problems 619 Index/Glossary 641 iv Copyright 2016 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it. Contents 1 Matter and Measurements 1 5-5 Gas Mixtures: Partial Pressures and Mole Fractions 110 1-1 Matter and Its Classifications 2 5-6 Kinetic Theory of Gases 114 1-2 Measurements 7 5-7 Real Gases 120 The Human Side: Antoine Lavoisier 15 Beyond the Classroom: Measurement of Blood 1-3 Properties of Substances 15 Pressure 122 Beyond the Classroom: Arsenic 20 Summary Problem 123 Summary Problem 21 Questions and Problems 123a Questions and Problems 21a 6 Electronic Structure and the 2 Atoms, Molecules, and Ions 22 Periodic Table 124 2-1 Atoms and the Atomic Theory 22 6-1 Light, Photon Energies, and Atomic 2-2 Components of the Atom 23 Spectra 125 The Human Side: John Dalton 24 6-2 The Hydrogen Atom 130 2-3 Quantitative Properties of the Atom 26 6-3 Quantum Numbers 133 2-4 Introduction to the Periodic Table 33 6-4 Atomic Orbitals; Shapes and Sizes 138 2-5 Molecules and Ions 35 6-5 Electron Configurations in Atoms 138 2-6 Formulas of Ionic Compounds 41 The Human Side: Glenn Theodore Seaborg 142 2-7 Names of Compounds 43 6-6 Orbital Diagrams of Atoms 143 Beyond the Classroom: Mastering the Peri‘god‘ic Table 48 6-7 Electron Arrangements in Monatomic Summary Problem 50 Ions 145 Questions and Problems 50 6-8 Periodic Trends in the Properties of Atoms 148 Beyond the Classroom: Why Do Lobsters Turn Red When Cooked? 153 3 Mass Relations in Chemistry; Summary Problem 154 Stoichiometry 51 Questions and Problems 154a 3-1 The Mole 51 3-2 Mass Relations in Chemical Formulas 58 3-3 Mass Relations in Reactions 63 7 Covalent Bonding 155 Beyond the Classroom: Hydrates 71 7-1 Lewis Structures; The Octet Rule 156 Summary Problem 73 The Human Side: Gilbert Newton Lewis 165 Questions and Problems 73 7-2 Molecular Geometry 166 7-3 Polarity of Molecules 174 7-4 Atomic Orbitals; Hybridization 178 4 Reactions in Aqueous Solution 74 Beyond the Classroom: The Noble Gases 184 Summary Problem 185 4-1 Precipitation Reactions 75 Questions and Problems 186 4-2 Acid-Base Reactions 80 4-3 Oxidation-Reduction Reactions 87 The Human Side: Svante August Arrhenius 87 Beyond the Classroom: Antacids 93 8 Thermochemistry 187 Summary Problem 94 8-1 Principles of Heat Flow 188 Questions and Problems 94a 8-2 Measurement of Heat Flow; Calorimetry 192 8-3 Enthalpy 195 8-4 Thermochemical Equations 196 5 Gases 95 8-5 Enthalpies of Formation 202 8-6 Bond Enthalpy 207 5-1 Measurements on Gases 96 8-7 The First Law of Thermodynamics 209 5-2 The Ideal Gas Law 98 Beyond the Classroom: Energy Balance in the Human 5-3 Gas Law Calculations 100 Body 213 5-4 Stoichiometry of Gaseous Reactions 105 Summary Problem 215 The Human Side: Amadeo Avogadro 109 Questions and Problems 215 v Copyright 2016 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it. vi CONTENTS 9 Liquids and Solids 216 13 Acids and Bases 331 9-1 Comparing Solids, Liquids, and Gases 216 13-1 Brønsted-Lowry Acid-Base Model 331 9-2 Liquid-Vapor Equilibrium 217 13-2 The Ion Product of Water 333 9-3 Phase Diagrams 223 13-3 pH and pOH 333 9-4 Molecular Substances; Intermolecular 13-4 Weak Acids and Their Equilibrium Forces 226 Constants 339 9-5 Network Covalent, Ionic, and Metallic 13-5 Weak Bases and Their Equilibrium Solids 232 Constants 348 9-6 Crystal Structures 238 13-6 Acid-Base Properties of Salt Solutions 352 The Human Side: Dorothy Crowfoot Hodgkin 241 13-7 Extending the Concept of Acids and Bases: Beyond the Classroom: Supercritical Carbon Dioxide 243 The Lewis Model 355 Summary Problem 245 Beyond the Classroom: Organic Acids and Bases 356 Questions and Problems 245 Summary Problem 359 Questions and Problems 359a 10 Solutions 246 10-1 Concentration Units 246 14 Equilibria in Acid-Base Solutions 360 10-2 Principles of Solubility 255 14-1 Buffers 360 10-3 Colligative Properties of Nonelectrolytes 260 14-2 Acid-Base Indicators 371 10-4 Colligative Properties of Electrolytes 269 14-3 Acid-Base Titrations 374 Beyond the Classroom: Maple Syrup 272 Beyond the Classroom: Acid Rain 382 Summary Problem 273 Summary Problem 384 Questions and Problems 273 Questions and Problems 384 11 Rate of Reaction 274 15 Complex Ion and Precipitation 11-1 Meaning of Reaction Rate 274 Equilibria 385 11-2 Reaction Rate and Concentration 277 15-1 Complex Ion Equilibria; Formation Constant 11-3 Reactant Concentration and Time 283 (Kf) 385 11-4 Models for Reaction Rate 289 15-2 Solubility; Solubility Product Constant The Human Side: Henry Eyring 292 (Ksp) 388 11-5 Reaction Rate and Temperature 293 15-3 Precipitate Formation 394 11-6 Catalysis 296 15-4 Dissolving Precipitates 399 11-7 Reaction Mechanisms 298 Beyond the Classroom: Qualitative Analysis 403 Beyond the Classroom: The Ozone Story 302 Summary Problem 405 Summary Problem 304 Questions and Problems 405 Questions and Problems 305 16 Spontaneity of Reaction 406 12 Gaseous Chemical Equilibrium 306 16-1 Spontaneous Processes 407 12-1 The N2O4–NO2 Equilibrium System 307 16-2 Entropy, S 409 12-2 The Equilibrium Constant Expression 310 16-3 Free Energy, G 413 12-3 Determination of K 315 The Human Side: J. Willard Gibbs 415 12-4 Applications of the Equilibrium Constant 318 16-4 Standard Free Energy Change, ΔG° 415 12-5 Effect of Changes in Conditions on an 16-5 Effect of Temperature, Pressure, and Equilibrium System 323 Concentration on Reaction Spontaneity 419 Beyond the Classroom: An Industrial Application of 16-6 The Free Energy Change and the Equilibrium Gaseous Equilibrium 328 Constant 424 Summary Problem 330 16-7 Additivity of Free Energy Changes; Coupled Questions and Problems 330a Reactions 425 Beyond the Classroom: Rubber Elasticity: An Entropic Phenomenon 427 Summary Problem 429 Questions and Problems 429 Copyright 2016 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it. CONTENTS vii 17 Electrochemistry 430 21 Chemistry of the Nonmetals 525 21-1 The Elements and Their Preparation 526 17-1 Oxidation-Reduction Reactions Revisited 431 21-2 Hydrogen Compounds of Nonmetals 530 17-2 Voltaic Cells 435 21-3 Oxygen Compounds of Nonmetals 534 17-3 Standard Voltages 439 21-4 Oxoacids and Oxoanions 537 17-4 Relations Between E°, ΔG°, and K 446 Beyond the Classroom: Arsenic and Selenium 545 17-5 Effect of Concentration on Voltage 448 Summary Problem 546 17-6 Electrolytic Cells 452 Questions and Problems 546a 17-7 Commercial Cells 456 The Human Side: Michael Faraday 458 Beyond the Classroom: Fuel Cells: The Next Step in Chemical-to-Electrical-Energy Conversion? 461 22 Organic Chemistry 547 Summary Problem 464 22-1 Saturated Hydrocarbons: Alkanes 548 Questions and Problems 464 22-2 Unsaturated Hydrocarbons: Alkenes and Alkynes 553 22-3 Aromatic Hydrocarbons and Their 18 Nuclear Reactions 465 Derivatives 556 22-4 Functional Groups 558 18-1 Nuclear Stability 465 22-5 Isomerism in Organic Compounds 566 18-2 Radioactivity 467 22-6 Organic Reactions 571 The Human Side: Marie and Pierre Curie 473 Beyond the Classroom: Cholesterol 573 18-3 Rate of Radioactive Decay 473 Summary Problem 575 18-4 Mass-Energy Relations 476 Questions and Problems 575a 18-5 Nuclear Fission 480 18-6 Nuclear Fusion 483 Beyond the Classroom: Biological Effects of Radiation 485 23 Organic Polymers, Natural and Summary Problem 486 Synthetic 576 Questions and Problems 486 23-1 Synthetic Addition Polymers 577 23-2 Synthetic Condensation Polymers 580 23-3 Carbohydrates 583 19 Complex Ions 487 23-4 Proteins 587 Beyond the Classroom: DNA Fingerprinting 595 19-1 Composition of Complex Ions 488 Summary Problem 597 19-2 Naming Complex Ions and Coordination Questions and Problems 597 Compounds 492 19-3 Geometry of Complex Ions 494 19-4 Electronic Structure of Complex Ions 498 Appendices The Human Side: Alfred Werner 498 Beyond the Classroom: Chelates: Natural and 1 Units, Constants, and Reference Data 599 Synthetic 503 2 Properties of the Elements 605 Summary Problem 505 3 Exponents and Logarithms 607 Questions and Problems 505 4 Molecular Orbitals 613 5 Answers to Even-Numbered and Challenge Questions and Problems 619 20 Chemistry of the Metals 506 20-1 Metallurgy 506 20-2 Reactions of the Alkali and Alkaline Earth Index/Glossary 641 Metals 513 20-3 Redox Chemistry of the Transition Metals 516 Beyond the Classroom: Essential Metals in Nutrition 522 Summary Problem 524 Questions and Problems 524 Copyright 2016 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it. Preface It is always difficult for an author to praise the virtues of one’s own book. I could tell the instructors that the book is so inspiring that students will be turned on to chemistry with little or no effort on the instructor’s part. I doubt you would be- lieve that. I could also tell you that the text is so clearly written, so attuned to the students in the twenty-first century that your students will learn chemistry with little or no effort on their part. You certainly would not believe that. I can tell you that the two goals in writing this edition have been to make it as clear and as in- teresting as possible. I hope you believe that, because it is true. Today’s freshmen are quite different from those of a few years ago. Text messaging and TwitterTM have strongly influenced sentence length and structure. In current writing and conversation, short sentences or sentence fragments convey straight-to-the-point information. Multimedia presentations are a way of life. This edition, like the seventh, is written to be fully in tune with today’s technology and speech. Why Write a Short Book? Rising tuition costs, depleted forests, and students’ aching backs have kept me steadfast in my belief that it should be possible to cover a text completely (or at least almost completely) in a two-semester course. The students (and their par- ents) justifiably do not want to pay for 1000-page books with material that is never discussed in the courses taught with those texts. The common perception is that a short book is a low-level book. I believe, however, that treating general concepts in a concise way can be done without sacrificing depth, rigor, or clarity. The criterion for including material continues to be its importance and relevance to the student, not its difficulty. To achieve this, the following guidelines are used. 1. Eliminate repetition and duplication wherever possible. Like its earlier edi- tions, this text uses ■■Only one method for balancing redox reactions, the half-equation method introduced in Chapter 17. ■■Only one way of working gas-law problems, using the ideal gas law in all cases (Chapter 5). ■■Only one way of calculating ΔH (Chapter 8), using enthalpies of formation. ■■Only one equilibrium constant for gas-phase reactions (Chapter 12), the thermodynamic constant K, often referred to as K . This simplifies not only p the treatment of gaseous equilibrium but also the discussion of reaction spontaneity (Chapter 16) and electrochemistry (Chapter 17). 2. Relegate to the Appendices or Beyond the Classroom essays topics ordinarily covered in longer texts. Items in this category include ■■MO (molecular orbital) theory (Appendix 4). Experience has shown (and continues to show) that although this approach is important to chemical bonding, most general chemistry students do not understand it but only memorize the principles discussed in the classroom. ■■Nomenclature of organic compounds. This material is of little value in a beginning course and is better left to a course in organic chemistry. ■■Qualitative analysis. This is summarized in a few pages in an essay in Chap- ter 15 in the Beyond the Classroom section. An extended discussion of the qualitative scheme and the chemistry behind it belongs in a laboratory manual, not a textbook. ■■Biochemistry. This material is traditionally covered in the last chapter of general chemistry texts. Although there are several biochemical topics in- cluded in the text (among them a discussion of heme in Chapter 19 and viii Copyright 2016 Cengage Learning. All Rights Reserved. May not be copied, scanned, or duplicated, in whole or in part. Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s). Editorial review has deemed that any suppressed content does not materially affect the overall learning experience. Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it.