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Chemistry A01_TRO5187_04_SE_FM_A-i-A-xxxviiv3.1.8.indd 1 2015/12/08 3:39 PM This page intentionally left blank Chemistry A Molecular Approach Fourth Edition Nivaldo J. Tro Westmont College A01_TRO5187_04_SE_FM_A-i-A-xxxviiv3.1.8.indd 3 2015/12/08 3:39 PM Editor in Chief: Jeanne Zalesky Executive Editor: Terry Haugen Director of Development: Jennifer Hart Product Marketing Manager: Elizabeth Ellsworth Executive Field Marketing Manager: Chris Barker Development Editor: Erin Mulligan Program Manager: Sarah Shefveland Project Manager: Beth Sweeten Editorial Assistant: Lindsey Pruett Content Producer: Jackie Jacob Text and Image Permissions Project Manager: William Opaluch Program Management Team Lead: Kristen Flatham Project Management Team Lead: David Zielonka Production Management: Francesca Monaco, CodeMantra Compositor: CodeMantra Design Manager and Cover Designer: Derek Bacchus Interior Designer: Elise Lansdon Illustrators: Lachina, Inc. Photo Researcher: Eric Shrader Operations Specialist: Maura Zaldivar-Garcia Cover and Chapter Opening Illustrations: Quade Paul Copyright © 2017, 2014, 2011 Pearson Education, Inc. All rights reserved. Manufactured in the United States of America. This publication is protected by copyright, and permission should be obtained from the publisher prior to any prohibited reproduction, storage in a retrieval system, or transmission in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise. For information regarding permissions, request forms and the appropriate contacts within the Pearson Education Global Rights & Permissions department, please visit www.pearsoned.com/permissions/. Acknowledgements of third party content appear on page C-1, which constitutes an extension of this copyright page. Unless otherwise indicated herein, any third-party trademarks that may appear in this work are the property of their respective owners and any references to third-party trademarks, logos or other trade dress are for demonstrative or descriptive purposes only. Such references are not intended to imply any sponsorship, endorsement, authorization, or promotion of Pearson’s products by the owners of such marks, or any relationship between the owner and Pearson Education, Inc. or its affiliates, authors, licensees or distributors. PEARSON, ALWAYS LEARNING and MasteringChemistry are exclusive trademarks in the U.S. and/or other countries owned by Pearson Education, Inc. or its affiliates. Tro, Nivaldo J. Chemistry : a molecular approach / Tro, Nivaldo J. Fourth edition. | Boston : Pearson, [2017] | Includes bibliographical references and index. LCCN 2015040901 | ISBN 9780134112831 (0134112830 : alk. paper) LCSH : Chemistry, Physical and theoretical––Textbooks. LCC QD453.3. T759 2017 | DDC 540––dc23 LC record available at http://lccn.loc.gov/2015040901 1 2 3 4 5 6 7 8 9 10—V357—18 17 16 15 ISBN-10: 0-13-411283-0 / ISBN-13: 978-0-13-411283-1 (Student Edition) ISBN-10: 0-13-412633-5 / ISBN-13: 978-0-13412633-3 (Instructor Review Copy) www.pearsonhighered.com A01_TRO5187_04_SE_FM_A-i-A-xxxviiv3.1.8.indd 4 2015/12/08 3:39 PM About the Author Nivaldo Tro is a professor of chemistry at Westmont College in Santa Barbara, California, where he has been a faculty member since 1990. He received his Ph.D. in chemistry from Stanford University for work on developing and using optical techniques to study the adsorption and desorption of molecules to and from ­surfaces in ultrahigh vacuum. He then went on to the University of California at Berkeley, where he did postdoctoral research on ultrafast reaction dynamics in solution. Since coming to Westmont, Professor Tro has been awarded grants from the American Chemical Society Petroleum Research Fund, from Research Corporation, and from the National Science Foundation to study the dynamics of various ­processes occurring in thin adlayer films adsorbed on dielectric surfaces. He has been honored as Westmont’s outstanding teacher of the year three times and has also received the college’s outstanding researcher of the year award. Professor Tro lives in Santa Barbara with his wife, Ann, and their four children, Michael, Ali, Kyle, and Kaden. To Michael, Ali, Kyle, and Kaden v A01_TRO5187_04_SE_FM_A-i-A-xxxviiv3.1.8.indd 5 2015/12/08 3:39 PM Brief Contents 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 Matter, Measurement, and Problem Solving Atoms and Elements Molecules, Compounds, and Chemical Equations Chemical Quantities and Aqueous Reactions Gases Thermochemistry The Quantum-Mechanical Model of the Atom Periodic Properties of the Elements Chemical Bonding I: The Lewis Model Chemical Bonding II: Molecular Shapes, Valence Bond Theory, and Molecular Orbital Theory Liquids, Solids, and Intermolecular Forces Solids and Modern Materials Solutions Chemical Kinetics Chemical Equilibrium Acids and Bases Aqueous Ionic Equilibrium Free Energy and Thermodynamics Electrochemistry Radioactivity and Nuclear Chemistry Organic Chemistry Biochemistry Chemistry of the Nonmetals Metals and Metallurgy Transition Metals and Coordination Compounds ii 44 86 138 196 248 296 336 382 426 484 532 570 622 674 722 778 838 888 938 978 1028 1062 1100 1126 Appendix I  Common Mathematical Operations in Chemistry A-1 Appendix II Useful Data A-5 Appendix III  Answers to Selected Exercises A-15 Appendix IV Answers to In-Chapter Practice Problems A-54 Glossary G-1 Photo and Text Credits C-1 Index I-1 vi A01_TRO5187_04_SE_FM_A-i-A-xxxviiv3.1.8.indd 6 2015/12/08 3:39 PM Interactive Media Contents Interactive Worked Examples (IWEs) https://media.pearsoncmg.com/ph/esm/esm_tro_chemistry_4/media/index.html 1.5 1.6 1.8 1.9 1.10 1.12 2.3 2.5 2.8 2.9 3.3 3.11 3.13 3.16 3.18 3.21 3.23 4.1 4.3 4.5 4.6 4.8 4.10 5.5 5.7 5.8 5.12 5.15 6.2 6.3 6.5 6.7 6.8 6.11 7.2 7.3 7.5 7.7 8.4 8.5 8.6 Determining the Number of Significant Figures in a Number Significant Figures in Calculations Unit Conversion Unit Conversions Involving Units Raised to a Power Density as a Conversion Factor Problems with Equations Atomic Numbers, Mass Numbers, and Isotope Symbols Atomic Mass The Mole Concept—Converting between Mass and Number of Atoms The Mole Concept Writing Formulas for Ionic Compounds Using the Nomenclature Flow Chart to Name Compounds The Mole Concept—Converting between Mass and Number of Molecules Chemical Formulas as Conversion Factors Obtaining an Empirical Formula from Experimental Data Determining an Empirical Formula from Combustion Analysis Balancing Chemical Equations Stoichiometry Limiting Reactant and Theoretical Yield Calculating Solution Concentration Using Molarity in Calculations Solution Stoichiometry Writing Equations for Precipitation Reactions Ideal Gas Law I Density Molar Mass of a Gas Gases in Chemical Reactions Graham’s Law of Effusion Temperature Changes and Heat Capacity Thermal Energy Transfer Measuring ∆Erxn in a Bomb Calorimeter Stoichiometry Involving ∆H Measuring ∆Hrxn in a Coffee-Cup Calorimeter ∆H°rxn and the Standard Enthalpies of Formation Photon Energy Wavelength, Energy, and Frequency Quantum Numbers I Wavelength of Light for a Transition in the Hydrogen Atom Writing Electron Configurations from the Periodic Table Atomic Size Electron Configurations and Magnetic Properties for Ions 8.8 9.4 9.6 9.7 9.8 9.10 9.11 10.2 10.4 10.5 10.8 10.10 11.1 11.2 11.3 11.5 12.4 13.3 13.4 13.5 13.6 13.9 14.2 14.4 14.8 14.9 15.1 15.5 15.8 15.9 15.12 15.14 16.1 First Ionization Energy Writing Lewis Structures Writing Lewis Structures for Polyatomic Ions Writing Resonance Structures Assigning Formal Charges Writing Lewis Structures for Compounds Having Expanded Octets Calculating ∆Hrxn from Bond Energies Predicting Molecular Geometries Predicting the Shape of Larger Molecules Determining Whether a Molecule Is Polar Hybridization and Bonding Scheme Molecular Orbital Theory Dipole–Dipole Forces Hydrogen Bonding Using the Heat of Vaporization in Calculations Using the Two-Point Form of the Clausius–Clapeyron Equation to Predict the Vapor Pressure at a Given Temperature Relating Density to Crystal Structure Using Parts by Mass in Calculations Calculating Concentrations Converting between Concentration Units Calculating the Vapor Pressure of a Solution Containing a Nonelectrolyte and Nonvolatile Solute Boiling Point Elevation Determining the Order and Rate Constant of a Reaction The First-Order Integrated Rate Law: Determining the Concentration of a Reactant at a Given Time Using the Two-Point Form of the Arrhenius Equation Reaction Mechanisms Expressing Equilibrium Constants for Chemical Equations Finding Equilibrium Constants from Experimental Concentration Measurements Finding Equilibrium Concentrations When You Know the Equilibrium Constant and All but One of the Equilibrium Concentrations of the Reactants and Products Finding Equilibrium Concentrations from Initial Concentrations and the Equilibrium Constant Finding Equilibrium Concentrations from Initial Concentrations in Cases with a Small Equilibrium Constant The Effect of a Concentration Change on Equilibrium Identifying Brønsted–Lowry Acids and Bases and Their Conjugates vii A01_TRO5187_04_SE_FM_A-i-A-xxxviiv3.1.8.indd 7 2015/12/08 3:39 PM viii       Interactive Media Contents Calculating pH from [h3o + ] or [oh-] Finding the [h3o +] of a Weak Acid Solution Finding the pH of a Weak Acid Solution in Cases Where the x is small Approximation Does Not Work 16.8 Finding the Equilibrium Constant from pH 16.9 Finding the Percent Ionization of a Weak Acid 16.12 Finding the [oh-] and pH of a Weak Base Solution 16.14 Determining the pH of a Solution Containing an Anion Acting as a Base 17.2 Calculating the pH of a Buffer Solution as an Equilibrium Problem and with the Henderson– Hasselbalch Equation 17.3 Calculating the pH Change in a Buffer Solution after the Addition of a Small Amount of Strong Acid or Base 17.4 Using the Henderson–Hasselbalch Equation to Calculate the pH of a Buffer Solution Composed of a Weak Base and Its Conjugate Acid 17.6 Strong Acid–Strong Base Titration pH Curve 17.7 Weak Acid–Strong Base Titration pH Curve 17.8 Calculating Molar Solubility from Ksp 16.3 16.5 16.7 18.4 Calculating Gibbs Free Energy Changes and Predicting Spontaneity from ∆H and ∆S 18.5 Calculating Standard Entropy Changes (∆S°rxn) 18.6 Calculating the Standard Change in Free Energy for a Reaction Using ∆G°rxn = ∆H°rxn - T∆S°rxn 18.10 Calculating ∆Grxn under Nonstandard Conditions 18.11 The Equilibrium Constant and ∆G°rxn 19.2 Half-Reaction Method of Balancing Aqueous Redox Equations in Acidic Solution 19.3 Balancing Redox Reactions Occurring in Basic Solution 19.4 Calculating Standard Potentials for Electrochemical Cells from Standard Electrode Potentials of the HalfReactions 19.6 Relating ∆G° and E°cell 20.1 Writing Nuclear Equations for Alpha Decay 20.2 Writing Nuclear Equations for Beta Decay, Positron Emission, and Electron Capture 20.4 Radioactive Decay Kinetics 20.5 Radiocarbon Dating 21.3 Naming Alkanes Key Concept Videos (KCVs) https://media.pearsoncmg.com/ph/esm/esm_tro_chemistry_4/media/index.html 1.1 1.3 1.8 2.3 2.6 2.9 3.5 3.6 3.11 4.2 4.3 4.6 5.3 5.4 5.6 5.8 6.3 6.4 6.6 7.2 7.4 7.5 8.3 8.4 8.6 9.5 9.7 9.8 10.2 10.3 Atoms and Molecules Classifying Matter Solving Chemical Problems Atomic Theory Subatomic Particles and ­Isotope Symbols The Mole Concept Naming Ionic Compounds Naming Molecular Compounds Writing and Balancing Chemical Equations Reaction Stoichiometry Limiting Reactant, Theoretical Yield, and Percent Yield Reactions in Solution Simple Gas Laws and Ideal Gas Law Simple Gas Laws and Ideal Gas Law Mixtures of Gases and Partial Pressures Kinetic Molecular Theory The First Law of T­ hermodynamics Heat Capacity The Change in Enthalpy for a Chemical Reaction The Nature of Light The Wave Nature of Matter Quantum Mechanics and the Atom: Orbitals and Quantum Numbers Electron Configurations Writing an Electron Configuration based on an Element’s Position on the Periodic Table Periodic Trends in the Size of Atomic Effective Nuclear Charge The Lewis Model for Chemical Bonding Writing Lewis Structures for Molecular Compounds Resonance and Formal Charge VSEPR Theory VSEPR Theory: The Effect of Lone Pairs A01_TRO5187_04_SE_FM_A-i-A-xxxviiv3.1.8.indd 8 10.6 10.7 11.3 11.5 11.7 11.8 12.3 13.4 13.5 13.6 14.3 14.4 14.5 15.3 15.8 15.9 16.3 16.6 16.8 17.2 17.2 17.4 18.3 18.6 18.7 19.4 19.5 20.3 Valence Bond Theory Valence Bond Theory: Hybridization Intermolecular Forces Vaporization and Vapor P ­ ressure Heating Curve for Water Phase Diagrams Unit Cells: Simple Cubic, Body–Centered Cubic, and Face–Centered Cubic Solution Equilibrium and the Factors Affecting Solubility Solution Concentration: Molarity, Molality, Parts by Mass and Volume, Mole Fraction Colligative Properties The Rate Law for a Chemical Reaction The Integrated Rate Law The Effect of Temperature on Reaction Rate The Equilibrium Constant Finding Equilibrium Concentrations from Initial Concentrations Le Châtelier’s Principle Definitions of Acids and Bases Finding the [h3o + ] and pH of Strong and Weak Acid ­Solutions The Acid–Base Properties of Ions and Salts Buffers Finding pH and pH Changes in Buffer Solutions The Titration of a Weak Acid and a Strong Base Entropy and the Second Law of Thermodynamics The Effect of ∆H, ∆S, and T on Reaction Spontaneity Standard Molar Entropies Standard Electrode Potentials Cell Potential, Free Energy, and the Equilibrium Constant Types of Radioactivity 2015/12/08 3:39 PM Contents Preface xxii 1 Matter, Measurement, and Problem Solving 2 Atoms and Elements 44 xxxiv 1.1 Atoms and Molecules 1 1.2 The Scientific Approach to Knowledge 3 The Nature of Science Thomas S. Kuhn and Scientific Revolutions 5 1.3 The Classification of Matter 5 The States of Matter: Solid, Liquid, and Gas 6 Classifying Matter according to Its Composition: Elements, Compounds, and Mixtures 7   Separating Mixtures 8   1.4 Physical and Chemical Changes and Physical and Chemical Properties 9 1.5 Energy: A Fundamental Part of Physical and Chemical Change 12 1.6 The Units of Measurement 13 Standard Units 13   The Meter: A Measure of Length 14   The Kilogram: A Measure of Mass 14   The Second: A Measure of Time 14   The Kelvin: A Measure of Temperature 15   Prefix Multipliers 17   Derived Units: Volume and Density 17  Calculating Density 19   Chemistry and Medicine Bone Density 20 1.7 The Reliability of a Measurement 20 Counting Significant Figures 22   Exact Numbers 22   Significant Figures in Calculations 23  Precision and Accuracy 25   Chemistry in Your Day Integrity in Data Gathering 26 1.8 Solving Chemical Problems 26 Converting from One Unit to Another 26   General Problem-Solving Strategy 28   Units Raised to a Power 30  Order-of-Magnitude Estimations 31   Problems Involving an Equation 32   Chapter in Review Self-Assessment Quiz 33  Key Terms 34   Key Concepts 35  Key Equations and Relationships 35   Key Learning Outcomes 36   Exercises Review Questions 36  Problems by Topic 36   Cumulative Problems 40  Challenge Problems 41   Conceptual Problems 42   Questions for Group Work 42  Data Interpretation and Analysis 43   Answers to Conceptual Connections 43   2.1 Brownian Motion: Atoms Comfirmed 45 2.2 Early Ideas About the Building Blocks of Matter 47 2.3 Modern Atomic Theory and the Laws That Led to It 47 The Law of Conservation of Mass 47   The Law of Definite Proportions 48   The Law of Multiple Proportions 49   John Dalton and the Atomic Theory 50   Chemistry in Your Day Atoms and Humans 50 2.4 The Discovery of the Electron 51 Cathode Rays 51   Millikan’s Oil Drop Experiment: The Charge of the Electron 52   2.5 The Structure of the Atom 53 2.6 Subatomic Particles: Protons, Neutrons, and Electrons in Atoms 55 Elements: Defined by Their Numbers of Protons 56   Isotopes: When the Number of Neutrons Varies 57   Ions: Losing and Gaining Electrons 59   Chemistry in Your Day Where Did Elements Come From? 60 2.7 Finding Patterns: The Periodic Law and the Periodic Table 60 Modern Periodic Table Organization 62   Ions and the Periodic Table 64   Chemistry and Medicine The Elements of Life 65 2.8 Atomic Mass: The Average Mass of an Element’s Atoms 65 Mass Spectrometry: Measuring the Mass of Atoms and Molecules 66   Chemistry in Your Day Evolving Atomic Masses 68 2.9 Molar Mass: Counting Atoms by Weighing Them 69 The Mole: A Chemist’s “Dozen” 69   Converting between Number of Moles and Number of Atoms 70   Converting between Mass and Amount (Number of Moles) 71   ix A01_TRO5187_04_SE_FM_A-i-A-xxxviiv3.1.8.indd 9 2015/12/08 3:39 PM